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173.Журнал Сибирского федерального университета. Сер. Химия №3 2011

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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Журнал Сибирского федерального университета
2011
Journal of Siberian Federal University
4 (3)
Химия
Chemistry
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Editorial Advisory Board
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CONTENTS / СОДЕРЖАНИЕ
Alexey M. Melnikov and Olga N. Kononova
Kinetics of Simultaneous Recovery of Platinum (II,IV) and
Rhodium (III) from Sulfate-Chloride Solutions on some Anion
Exchangers
? 207 ?
Л.Т. Денисова, В.М. Денисов, Л.Г. Чумилина
b?=,?%??L?2",? !=?C?="%" Bi2O3-SiO2 c ??!?K!%?
? 216 ?
В.И. Шарыпов, Л.И. Гришечко, Л.С. Тарасова,
С.В. Барышников, А. Селзард, Б.Н. Кузнецов
h?????%"=?,? 2?!?,???*%?% !=??%???, %K!=??%" ?,??,?=,
"/??????/. ,? ?!?"??,?/ %?,?/ !=??,??/?, ??2%?=?,
? 221 ?
Д.Г. Слащинин, Ю.А. Алемасов, Д.И. Илюшкин,
В.А. Соколенко, М.С. Товбис, С.Д. Кирик
p?=*?,
=?*,?,!%"=?,
C?!?=??????/.
пара?,2!%?%-??%?%"
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С.А. Кузнецова, Г.П. Скворцова,
Е.С. Скурыдина, Ю.Н. Маляр, О.А. Ханчич
b?, ?,? 3??%",L =?,?,!%"=?, C!%C,%?%"%L *,??%2%L K?!??2/
*%!/ K?!??/ , ?? =*2,"=?,, ?= "/.%? , ?%?2=" .*?2!=*2%"
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В.В. Риваненков, С.С. Лалетина, Т.В. Шулимович,
А.М. Шор, Е.А. Шор, В.А. Наслузов
??%!?2,???*%? ,?3???,? =??%!K?,, ??K%???,. ?=?2,? ?%?%2=
?= ?,?!%*?,?,!%"=??%L C%"?!.?%?2, %*?,?= =???,?,
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Editorial board for Chemistry:
Nikolai V. Chesnokov
Lubov? K. Altunina
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Vasiliy A. Babkin
Vicente Cebolla
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Zinfer R. Ismagilov
Sergey V. Kachin
Sergey D. Kirik
Wolfgang Klose
Vladimir I. Kovalchuk
Vladimir A. Likholobov
Yuri L. Mikhlin
Gennady L. Pashkov
Anatoly I. Rubailo
Tatyana V. Ryazanova
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Tatyana G. Shendrik
Jean V. Weber
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Е.О. Игнатьева, Е.М. Дворянова, И.К. Гаркушин
o!%??%?,!%"=?,? , .*?C?!,???2=???%? C%?2"?!????,?
-=?%"%?% *%?C??*?= ?,?2??/ NaF-NaI-Na2WO4
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А.В. Сидорак, А.А. Шубин,
В.В. Иванов, Н.С. Николаева
q,?2?? C%!%?*%" Zn2SnO4 2?!?%%K!=K%2*%L ?%%?=?????/.
?%??,???,L
? 285 ?
И.В. Осипова, Г.А. Глущенко, В.Г. Исакова,
Е.А. Гончарова, А.С. Крылов, С.М. Жарков,
Э.А. Петраковская, Г.Н. Чурилов
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Т.А. Фроленко, Е.С. Семиченко,
М.Г. Мельникова, Н.А. Гаврилова, Г.А. Субоч
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Е.С. Семиченко, Г.А. Субоч
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Journal of Siberian Federal University. Chemistry 3 (2011 4) 207-215
~~~
??? 541.183 : 543.426
Kinetics of Simultaneous Recovery
of Platinum (II,IV) and Rhodium (III)
from Sulfate-Chloride Solutions
on some Anion Exchangers
Alexey M. Melnikov and Olga N. Kononova*
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041 Russia 1
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
The paper is devoted to the kinetics of sorption concentration of platinum (II,IV) and rhodium (III)
in their simultaneous presence in freshly prepared or stored sulfate-chloride solutions on some
macroporous anion exchangers with different chemical structure.
It was shown that the process rate is high, although it is slightly reduced in case of stored solutions.
The rate of platinum sorption concentration in the presence of rhodium on investigated resins is higher
than of rhodium in the presence of platinum. The sorption process was controlled by gel diffusion for
all the anion exchangers studied.
Keywords: platinum, rhodium, sorption, kinetics of sorption.
Introduction
To date, the growing demand for platinum group metals (PGM) stipulated their intensive mining
and expansion of supplies of secondary raw materials (spent automobile catalysts, catalysts from
chemical industry, electronic scrap and wastes of ore-dressing plants on noble metal-containing
deposits). Low concentrations of PGM in solutions obtained after breakdown of such raw materials
cause the application of sorption methods, known not only for their efficiency and selectivity, but also
for environmental safety [1,2]. The successful industrial application of ion exchangers requires not
only investigating their sorption properties, but also their kinetic behavior, as the satisfactory rate is
one of the essential factors for resins? technological use.
The recovery of PGM from products of processing of secondary raw materials occurs often by
means of sulfuric acid and sulfate solutions. In these solutions, platinum and rhodium exist in the form
of sulfate complexes, which are more kinetically inert, compared to corresponding chloride complexes,
especially of rhodium [1,3]. The sulfate complexes of platinum and rhodium are hardly sorbed and,
*
1
Corresponding author E-mail address: cm2@bk.ru
© Siberian Federal University. All rights reserved
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Alexey M. Melnikov and Olga N. Kononova. Kinetics of Simultaneous Recovery of Platinum (II,IV) and Rhodium (III)?
therefore, the sulfate solutions of PGM are needed to be activated before the sorption. Basically, the
dopes of sodium chloride or autoclave-cured chlorination are used for this purpose [4-7]. However, the
addition of hydrochloric acid to sulfate solutions of PGM facilitates the activation of these solutions
without any additional expenses. The investigations [1,6,8] have shown that the sulfate complexes of
PGM are absent in these systems. Based on that, we considered the recovery of platinum and rhodium
from sulfate-chloride solutions as an important matter of scientific and practical interest.
Our previous investigations [6,8] were focused on rhodium recovery from sulfate-chloride
systems, however, we did not covered the kinetics of its recovery in the presence of platinum. The
present work is devoted to investigation of kinetics of simultaneous sorption concentration of platinum
and rhodium from sulfate-chloride solutions on anion exchangers with different chemical structure.
Experimental
For the purpose of investigation, we selected several anion exchangers: AM-2B (Russia), Purolite
S 985 and A 500 (Purolite Ltd, U.K.). These sorbents revealed the best sorption properties to PGM in
our previous investigations [8,9]. The functional groups of Purolite A 500 are quaternary ammonia
base (QAB), Purolite S 985 contains the polyamine groups, whereas the functionality of AM-2B is
based on tertiary amino groups (~ 75 %) and of QAB (~ 25 %). The anion exchangers AM-2B and
Purolite A 500 are synthesized on the basis of styrene and divinylbenzene (DVB). Purolite S 985
possesses the matrix on the basis of polyacrylate and DVB.
The initial rhodium stock solution with concentration 9.709 mmol/L in 6 M HCl was prepared by
sintering of metallic rhodium quantity (0.25 g) with 5-fold excess (in mass) of BaO2 [3]. The content
of rhodium in the solution obtained was determined by a gravimetric method using sulfuric acid and
thiourea [3]. The initial platinum stock solution with concentration 9.669 mmol/L in 6 M HCl was
prepared by dissolution of accurately weighed quantity of H2PtCl6 in concentrated hydrochloric acid
[3].
The sulfate-chloride solution was prepared by addition of sulfuric acid to chloride solution of
platinum and rhodium. The initial concentrations of HCl and H2SO4 in the solutions obtained were
equal to each other.
Before use, anion exchangers were prepared according to standard methods [10] and loaded with
1 M NaCl aiming to convert the resins into the chloride form.
The sorption of noble metals was carried out from sulfate-chloride solutions with different acids
concentrations (0.01 ? 2.0 mol/L). The ratio of hydrochloric and sulfuric acids was 1 : 1. The initial
concentration of platinum and rhodium in these solutions was 0.25 mmol/L.
The kinetic behavior of anion exchangers towards platinum and rhodium was investigated as
follows. The resin quantities (0.1 g) were mixed with 10.0 mL of Pt / Rh chloride or sulfate-chloride
solution, and then the suspensions were intensively stirred at > 800 rev/min. The saturation times were
0.5; 1; 2; 3; 5; 15; 30; 45; 60; 180; 360 and 1440 min. After a certain time period, the resins were quickly
filtered off and the concentrations of noble metals in solution were determined spectrophotometrically
with tin (II) chloride and potassium iodide [3]. Using the results obtained, the degree of saturation (F)
of the resins as well as the process rate (? in mmol/g?s) were calculated as follows:
F
Qt
,
Qf
(1)
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Alexey M. Melnikov and Olga N. Kononova. Kinetics of Simultaneous Recovery of Platinum (II,IV) and Rhodium (III)?
Q
ai
,
ti
(2)
where Qt and Q ? are the amounts (in mmol) of platinum or rhodium sorbed to time t and at equilibrium,
respectively; ai is quantity (in mmol) of platinum or rhodium sorbed to time ti (in s) per 1 g of the
resin.
Then the kinetic curves were plotted on the coordinates F = f(t) and v = f(t). After that, the halfexchange times (t1/2, in s) were determined at F = 0.5.
The interpretation of results on kinetics was carried out using the Boyd-Adams? method [11-13],
according to which the formal kinetic coefficient (B) was calculated from:
B
(1.06) 2 � F 2
.
t
(3)
If the process is controlled by gel diffusion, the function Bt = f(t) should be linear. The diffusion
coefficients (D, in cm2/s) were calculated according to the equation:
D
r2
,
4S 2 � t1 / 2
(4)
where r is radius of resin grain (in cm).
The results obtained in the present work were subjected to statistical processing according to
conventional procedures [14,15]. The average experimental error was less than 5 %.
Results and discussion
It is known [1,3] that sulfate solutions contain the varied ionic forms of platinum and rhodium.
There are very stable polymeric aquahydroxo-complexes as well as polynuclear aquahydroxo-sulfates,
such as [ Pt 2 ( H 2 O) 2 ( SO4 ) 4 ]2 , [ Rh( H 2 O) 2 ( SO4 ) 2 ] , [ Rh(OH )( H 2 O)( SO4 ) 2 ]2 etc.
The presence of PGM sulfate complexes in solution causes the pronounced complication during
recovery of these metals, given that the majority of analytical methods for noble metals separation
are developed for chloride systems. They cannot be used for sulfuric acid media, because the kinetic
inertness of PGM sulfate complexes is higher than inertness of chloride ones. For this reason, these
solutions should be activated by adding sodium chloride or by autoclave-cured chlorination. However,
now it is found that sulfate-chloride solutions supersede the activation of sulfate solutions, and besides,
this process is rather easy [4-8].
Based on the electron absorption spectra of initial Pt / Rh sulfate-chloride solutions and on the data
from reference [1], we have determined that both freshly prepared solutions and solutions stored over
3 months do not contain sulfate complexes of these metals. The chloride complexes, such as [PtCl6 ]2 ,
[RhCl6 ]3 , [ Pt (OH )Cl5 ]2 , [ Pt (OH ) 6 ]2 , [ Rh( H 2O) 2 Cl4 ] etc., are present in the system. During a storage
of these solutions, the aquachloro- and hydroxocomplexes of platinum and rhodium, for example,
[ Pt ( H 2O) n Cl6n ]n2 , [ Pt (OH ) n Cl6n ]2 , [ Rh(OH ) n Cl6n ]n3 , [ Rh( H 2 O) n Cl6n ]n3 , where n 1 6 , arrive in
these media as a result of hydrolysis and aquation (the so-called ?ageing? processes) [1].
We have studied in our previous work [9] the ion exchange equilibria and kinetics of simultaneous
sorption concentration of platinum (II,IV) and rhodium (III) from freshly prepared and stored chloride
solutions on some anion exchangers. We have determined that the resins possessed good kinetic
# 209 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexey M. Melnikov and Olga N. Kononova. Kinetics of Simultaneous Recovery of Platinum (II,IV) and Rhodium (III)?
properties and the ion exchange was limited by gel diffusion. The isotherms of sorption of noble metals
from sulfate-chloride solutions are similar to the isotherms of Pt / Rh sorption from chloride systems,
proving the selectivity of the used resins.
The data on kinetic investigation of platinum and rhodium sorption from sulfate-chloride freshly
prepared solutions on example of anion exchanger Purolite A 500 are presented in Fig. 1. The kinetic
dependencies for the other resins are similar to these curves. It can be seen from these data that the
anion exchanger studied possess good kinetic properties, since the process rate is high. For instance,
over a period of 20 min, the resins are saturated on average with platinum complexes to 69 ? 79 % and
with rhodium ions to 57 ? 76 % from their total exchange capacity. For comparison, these resins are
saturated in 20 min to 53 ? 80 % and 38 ? 77 % with platinum and rhodium, respectively, while their
sorption proceeds from chloride media.
Fig. 1. Kinetic dependences of rates of sorption concentration of platinum in the presence of rhodium (a) and
of rhodium in the presence of platinum (b) on anion exchanger Purolite A 500 from freshly prepared sulfatechloride solutions with different acidity 1 ? 0.01 M HCl / H2SO4; 2 ? 0.1 M HCl / H2SO4; 3 ? 2.0 M HCl / H2SO4
(C(Pt) = C(Rh)) = 0.25 mmol/L)
# 210 #
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Alexey M. Melnikov and Olga N. Kononova. Kinetics of Simultaneous Recovery of Platinum (II,IV) and Rhodium (III)?
The rate of sorption concentration in weak acid solutions is higher than in strong acid ones.
Such behavior of strong basic anion exchanger Purolite A 500 can be explained by competition
between complex anions of rhodium and platinum and chloride ions during ion exchange process.
Correspondingly, the lesser the concentration of Cl? - ions is in solution, the weaker is their competing
effect. As a result, an increase in Pt / Rh sorption is observed.
As for the weak basic resin Purolite S 985 and intermediate anion exchanger AM-2B, they behave
similarly, i.e. their sorption ability towards Pt / Rh complexes grows with the decrease in acidity of
contacting solution. This effect can be explained by the increase in deprotonation of the nitrogen atom
in functional amine group, which increases the complexation ability of these sorbents [16].
It should be also noted that the recovery of platinum and rhodium from strong acid solutions
proceeds with high process rate. The lower rate of rhodium (III) sorption in the presence of platinum
(II,IV) can be explained by higher kinetic inertness of its chloride complexes, especially in weak acid
solutions. It is known [1,3] that the neutral and charged aqua complexes [ Rh( H 2O)3 Cl3 ]0 , [ Rh( H 2O) 2 Cl4 ] ,
[ Rh( H 2O)Cl5 ]2 are present in such solutions.
The study on kinetics of Pt / Rh sorption from stored sulfate-chloride solutions is of special
interest, because these solutions are often used in the industry during PGM recovery. The data obtained
(Table 1) show that the rate of sorption from solutions, stored over 3 months, decreases in comparison
with freshly prepared ones. This can be explained by formation of kinetically inert hydroxo- and
aqua complexes of platinum and rhodium. However, on the whole, the rate of Pt / Rh recovery from
stored solutions remains on a high level. Thus, over of 20 min, the anion exchangers investigated are
saturated from their total exchange capacity on the average to 51 ? 60 % and to 35 ? 46 % by platinum
and rhodium, respectively. These values correlate with the results, which we have obtained earlier for
chloride stored solutions (45 ? 59 % and 34 ? 55 % for Pt and Rh, respectively).
It can be seen from the data presented in Table 1 that the sorption concentration process proceeds
with the rate of order of 10 -5 mmol/g?s. The half-exchange time in the case of Pt recovery is much
shorter than for Rh sorption. Therefore, the kinetic parameters are in agreement with our insight into
the selectivity of investigated anion exchangers.
It can be also seen from Table 1 that the complexing sorbent Purolite S 985 reveals the best kinetic
properties among the studied resins, owing to its ability for simultaneous ion exchange and complex
formation in weak acidic media.
With the storage of Pt / Rh solutions, the sorption rate decreases, the half-exchange time is longer
than in case of freshly prepared solutions. We consider it takes place because of formation of kinetically
inert complexes of noble metals.
It should be noted that sorption of platinum and rhodium from stored sulfate-chloride solutions
proceeds with higher rate than the recovery of these metals from stored chloride media, whereas in
freshly prepared systems the rates of these processes are almost equal. Probably this phenomenon can
be explained by lesser exposure to hydrolysis in sulfate-chloride solutions than in chloride systems.
The kinetics type during sorption concentration of platinum and rhodium from freshly prepared
and stored sulfate-chloride solutions was determined using the classical Boyd-Adams? model with
the corresponding criteria [11-13]. Fig.2 contains the dependencies Bt f (t ) for anion exchanger
Purolite A 500, which are consistent with the above-mentioned model for gel kinetics of ion exchange.
These dependencies for the other sorbents investigated are also linear. Therefore, the Pt / Rh sorption
# 211 #
AM-2B
Purolite S 985
Purolite A 500
Trade name
5.18
2.80
174
9.11
6.41
307
13.21
2.98
D � 10 8 , cm 2 / s
Q � 10 5 mmol / g � s
t1 / 2 , s
D � 10 8 , cm 2 / s
Q � 10 5 mmol / g � s
t1 / 2 , s
D � 10 8 , cm 2 / s
Q � 10 mmol / g � s
5
306
Rt
2.02
8.31
488
3.76
8.71
182
1.23
2.41
658
Rh
Freshly prepared
t1 / 2 , s
Kinetic parameters
0.74
3.21
1.62
1.63
2.77
572
0.72
1.25
1270
Rt
Chloride solutions
Stored
0.59
3.03
1340
1.34
2.48
639
0.54
1.16
1364
Rh
5.46
14.09
162
7.31
10.09
157
5.07
9.97
159
Rt
2.99
9.28
246
3.92
8.57
185
3.66
8.38
189
Rh
Freshly prepared
1.32
8.18
496
2.28
5.48
289
1.08
2.72
583
Rt
Stored
Sulfate-chloride solutions
0.78
3.21
1264
1.11
1.68
945
0.81
1.50
1055
Rh
Table 1. Kinetic parameters of simultaneous sorption concentration of Pt (II, IV) and Rh (III) from freshly prepared and stored chloride and sulfate-chloride solutions
( C ( Pt ) C ( Rh) 0.25 mmol/L, C ( HCl ) C ( H 2 SO4 ) 0.01 mol/L)
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexey M. Melnikov and Olga N. Kononova. Kinetics of Simultaneous Recovery of Platinum (II,IV) and Rhodium (III)?
Fig. 2. Dependences of Bt function on time according to Boyd-Adams? model for gel diffusion kinetics of Pt / Rh
sorption from sulfate-chloride solutions on anion exchanger Purolite A 500 1 ? Pt in the presence of Rh (freshly
prepared solution); 2 ? Rh in the presence of Pt (freshly prepared solution); 3 ? Pt in the presence of Rh (stored solution);
4 ? Rh in the presence of Pt (stored solution) (C(Pt) = C(Rh) =0.25 mmol/L; C(HCl) = C(H2SO4) =0.01 mol/L)
Fig.3. Dependences of saturation degree Fon t during Pt / Rh sorption from sulfate-chloride solutions on anion
exchanger Purolite A 500 1 ? Pt in the presence of Rh (freshly prepared solution); 2 ? Rh in the presence of Pt
(freshly prepared solution); 3 ? Pt in the presence of Rh (stored solution); 4 ? Rh in the presence of Pt (stored
solution) (C(Pt) = C(Rh) = 0.25 mmol/L; C(HCl) = C(H2SO4) = 0.01 mol/L)
is controlled by gel diffusion (i.e. inter-diffusion of ions exchanged in a resin bead). The dependencies
F f ( t ) are also linear at small values of saturation degree F (Fig.3), and indicate the gel diffusion
as well.
It should be noted that kinetics type during Pt / Rh sorption from sulfate-chloride freshly prepared
and ?aged? solutions on anion exchangers investigated is in agreement with gel kinetics during sorption
of these metal complexes from chloride solutions, which we have studied in our previous work [9].
# 213 #
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Alexey M. Melnikov and Olga N. Kononova. Kinetics of Simultaneous Recovery of Platinum (II,IV) and Rhodium (III)?
The main kinetic parameters of simultaneous Pt / Rh sorption are summarized in Table 1. The
average diffusion coefficients are of the order of 10 -8 cm2/s. Their values are higher for platinum
sorption in the presence of rhodium, than for rhodium sorption in the presence of platinum under the
same conditions. Such order of diffusion coefficients is in agreement with the data obtained for kinetics
on selective ion exchangers [11,12,16].
Conclusions
The simultaneous sorption concentration of platinum (II,IV) and rhodium (III) from freshly
prepared and stored sulfate-chloride solutions was investigated in dependence on initial concentrations
of hydrochloric and sulfuric acids. The high rate of this process revealed in freshly prepared solutions,
is decreased slightly in stored solutions. The rates of platinum sorption in presence of rhodium on the
anion exchangers investigated are greater than the rates of rhodium sorption in presence of platinum
under the same conditions. The whole ion exchange is controlled by gel diffusion for all the studied
resins.
The results allow recommending the anion exchangers Purolite S 985 and A 500 as well as
AM-2B for application in improved technological schemes for utilization of spent platinum-rhodium
catalysts.
References
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Moscow: Editorial URSS, 2003. 592 p.
2. Radomskiy S.M., Radomskaya V.I., Moiseenko V.G. Sorption of noble metals on non-specific
sorbents. Non-ferrous metals. 2006. No. 6. P. 57 ? 61.
3. Ginzburg S.I., Ezerskaya N.A., Prokofieva I.V. Analytical chemistry of platinum group metals.
Moscow: Nauka, 1972. 617 p.
4. Kononov Y.S., Lystsova V.L., Kononova O.N., Parshikova G.N. Kinetics of sorption of
rhodium from sulfate solutions on weaki basic anion exchanger AN-31. Theory and praxis of sorption
processes. 1987. No. 18. P. 67 ? 71.
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I.B., Boychinova E.S. Sorption of rhodium (III) from chloride and chloride-sulfate solutions. J. of
?pplied ?hemistry. 1992, V. 65 (6). P. 1300 ? 1302.
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sulfate solutions. Chemistry and chemical technology. 1993. No. 6. P. 61 ? 67.
8. Kononova O.N., Glebova A.S., Melnikov A.M., Kashirin D.M., Konontsev S.G. Sorption
recovery of rhodium (III) from chloride and chloride-sulfate solutions. J. of applied chemistry. 2010,
V. 83 (10). P. 1628 ? 1634.
9. Kononova O.N., Melnikov A.M., Borisova T.V., Krylov A.S. Simultaneous ion exchange
recovery of platinum and rhodium from chloride solutions. Hydrometallurgy. 2011. V. 105. P. 341 ?
349.
# 214 #
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Alexey M. Melnikov and Olga N. Kononova. Kinetics of Simultaneous Recovery of Platinum (II,IV) and Rhodium (III)?
10. Polyanskiy N.G., Gorbunov G.V., Polyanskaya N.L. Methods for investigation of ion
exchangers. Moscow: Khimiya, 1976. 208 p.
11. Helfferich F. Ion exchange. New York: McGraw Hill, 1962. 530 p/
12. Helfferich F. Ion exchange kinetics. In: J.A. Marinsky (Ed.). Ion exchange. A series of
advances. New York: McGraw Hill, 1966. P. 281 ? 331.
13. Kokotov Y.A., Pasechnik V.A. Ion exchange equilibrium and kinetics of ion exchange.
Leningrad: Khimiya, 1979. 348 p.
14. Pollard J.H. A handbook of numerical and statistical techniques. Cambridge: Cambridge
University Press, 1977. 343 p.
15. Harris D.C. Quantitative chemical analysis. New York: Freeman and Co., 1996. P. 51.
16. Saldadze K.M., Kopylova-Valova V.D. Complex-forming ion exchangers. Moscow: Nauka,
1980. 562 p.
???????? ??????????? ?????????? ??????? (II,IV)
? ????? (III) ?? ?????????-????????? ?????????
?? ????????? ?????????
?.?. ?????????, ?.?. ????????
????????? ??????????? ???????????,
?????? 660041, ??????????, ??. ?????????, 79
??????? ???????? ???????????? ???????????????? ??????? (II,IV) ? ????? (III) ???
?????????? ??????????? ?? ??????????????????? ? ??????????? ?????????-?????????
????????? ?????????? ?????????????? ?????????? ????????? ?????????? ?????????.
???????? ??????? ???????? ?????????? ????? ????????, ??????? ????????? ????????? ???
???????????? ?????????. ???????? ???????????? ???????????????? ??????? ? ???????????
????? ?? ??????????? ????????? ????????? ??????? ??? ????? ? ??????????? ???????.
??????????? ??????? ?????????????? ??????? ????????? ??? ???? ????????? ?????????.
???????? ?????: ???????, ?????, ???????, ???????? ???????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 3 (2011 4) 216-220
~~~
??? 532.614+546.873
?????????????? ?????????
Bi2O3-SiO2 c ????????
?.?. ????????,
?.?. ???????*, ?.?. ????????
????????? ??????????? ???????????,
?????? 660041, ??????????, ??. ?????????, 791
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
??????? ?????????? ?????????????? ????????? Bi2O3-SiO2 ? ???????? ??????? ???????
?????. ???????????, ??? ??? ?????? ??? ??? ????? ??????????? ????????? ??????????? ??
???????.
???????? ?????: ??????????, ??????? ????, ???????, ?????? ??????? ? ???????.
????????
????????? ????????? ?????????? Bi12MO20 (M = Si, Ti, Ge), ??????????? ??????? ??????????????????? ??????????, ?????????? ????? ??????????, ?? ?????????? ???????, ???????
?????????????????????? [1, 2]. ??????????? ?????? ? ????? ?????????? ???????????? ???????????????? ??????, ??? ????? ????????? ??????????? ????? ??????? ???????????? ????????????? ?? ? ??????????? ?????? ? ????????? ?????????? ?????????? ? ???????? ??????? [3].
??????? ????? ??????? ?? ??????????? ?????? ? ?????????? ??????????? ?? ???????. ?????
??????? ????????? ?????? [3, 4]. ????????? Bi12SiO20 : Ag ???????? ??????? ????????????
????? ????????????????????? ??????????? (001). ?????????? ??????? ? ??????????? ?????????? ?????????? 0,01 ? 0,1 ????.%. ???? ??????????? ??????? ??????????? ???????? ??????????
Bi12SiO20 ?? ???????????? ?????????????? ????????????? ??????????? ??????????, ??????????? ?????? ? ?????? ??? ??????????? ???????. ??????????? ??????????? ????????????? ?????????????? ????????? «?????? (??????????? ???????????? ???????) ? ???????? (???????
???????????? ???????)» ?????????? ??????????.
??? ?? ?????, ??????????? ?????????????? ????????? Bi2O3-SiO2 ? ???????? ? ??????????
??????? ?? ???????. ??????? ????? ????????? ?????? ???????? ???????????? ???????????
?????????????? ????????? Bi2O3-SiO2 ? ??????? ????????.
*
1
Corresponding author E-mail address: antluba@mail.ru
© Siberian Federal University. All rights reserved
# 216 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????? ?????????????? ????????? Bi2O3-SiO2 c ????????
?????????? ? ?? ??????????
?????????? Ag ?????????? Bi2O3-SiO2 ??????? ?? ??????? ??????? ??????? ????? ???
?????????? ??????? ??????? ? ???????? [5]. ?????????? ??????, ?????????? ?????????????
Canon EOS 400 Digital, ???????????? ?? ??????????. ??? ????????????? ???????? ????????????
Bi2O3 ? SiO2 ????? «??.?».
???????????? ?? ??????????? ?????????????? Ag ? ?????????? Bi2O3-SiO2, ???????????
0; 1; 10; 14,28; 20; 30 ? 33 ???.% SiO2 (????? ??????? ?????????? SiO2 ???????????? ??
?????????????? ?????????, ??? ??? ??-?? ???????????? ????????? ????????? Bi2O3-SiO2 [6]
18
4????
4????
??????????? ????????????? ????? ????????? ??????????? ????????? ???????), ?????????
? ??????????? ?? ???????. ???????????, ??? ?????? ????? ???????, ? ????? ????????
? ??????????? 1; 10; 14,28 ???.% SiO2 ????? ? ?????? ???????? ? ???????? ??????????? ??
??? ???????????. ?????? ???????? ?? Ag ???????? ????????? ?????????? ???? ??????????
(???????).
?
16
18
14
14
12
12
10
10
8
8
6
6
4
4
2
2
0
100
200
4????
0
300
400
?
16
W, c
0
0
200
400
600
800
1000
W, c
?
20
15
10
5
0
0
500
1000
1500
2000 W, c
???????? ?????????? ????????? ??????? Bi2O3 ? SiO2 ?? ???????: ? ? 20, ? ? 30, ? ? 33 ???. % SiO2
??????????????
# 217 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????? ?????????????? ????????? Bi2O3-SiO2 c ????????
??? ?? ?????, ? ???????? ??????? ??? ???????? ????????? ??????????? ?? ???????.
?? ??????? ???????, ??? ? ?????? ?????????? ? ????????? SiO2 ?????????? ??????????
??????? ??????????. ??? ????? ???? ??????? ? ????????? ????????? Bi2O3-SiO2. ???????
SiO2 ?? ???????? ?????? ??????? ??????? ???????? ?????? [7]. ?????????? ???? ????????
???? ????????? ? ??????????? ???????????? SiO2 ?? 38 ???.% ????? ???? ?????????? ???
?????????? ??????????? ?????????, ? ?????????????, ?????????? ??????????? ?????????
(???? ????????????? ???????? ????????), ??? ? ???????????? ????? ??????? ??????????
???????????, ??????????? ??? ????????? [8]. ?????? ?????????? ???????? ? ??????? Bi2O3 ?
SiO2 ??????????? ?? ?????, ??? ????????? ?? ??????? ??? ????????? ??????????? ?????????
[1, 9]. ??? ????? ????????????????? ? ????????????? ? ????? ????????? ??????? ??????????
????????, ???????????? ????????? [8].
??????? Bi2O3 ? SiO2 ????? ??????????? ?????????????? ? ???????? ???????? ???? ???? ?
??????? (Bi2O3) ? ??????-??????? (Bi2O3 ? SiO2) ?? ?????-?????????? (????????, ??????????
? 20 ???.% SiO2) ? ?????-?????????? (????????, ?????????? ? 30 ???.% SiO2). ???, ??????????, ??????????????? ? ?????????? ?????????? ??????? ???????? ??????? ? ???????.
???????? ???????????????? ??????? ????????? ?????? Bi2O3 ????? ????????? ????????? ?
???????? ~ 4 ???.% Ag. ?????? ??????? ????? ???? ???????, ??? ??? ? ??????? Ag - Bi2O3 ??
??????? (??? ? ? ???????? ?????????????) ?????????? ?????????, ????????? ? ??????? Bi2O3
[10]. ???????, ??? ? ??????? Ag ? Bi ? O ????? ?????????????? ?????????? Ag5BiO4, Ag3BiO3,
Ag18Bi4O12, Ag25Bi3O18 [10]. ??????? ?? ? ?????? Bi2O3 ????? ??????????? ?????????????? ????
?? ???????????. ?? ?????????, ??? ??? ??????? ? ?? ??????????? ????????????.
????????? ????? ???????? ?????????? ????? ?? ??????????? ?????????????? ? ??????????
????????? (? ??? ????? ? ????????????) ???????? ? ? ?????? ??????? [11 ? 14]. ?????????
????? ? ???????? ? ???????? ???????? ? ????????? ????? ????????? ???????????? ????????
[15 ? 19].
????????????? ???????????? ??????? ??????? ? ???????? ????????? ???????? ??????
????????????????? ??????????? ????????????? ????????? ????? ??????????????? ??????
[20]. ????? ??????????????? ????????? Bi2O3 ??? ?????????????? ? ????????? ?? Ag ?? ??????
?????? ???????????????? ??????????? [21] ????? ???? ???????????? ? ???? ?????????
???????:
O њ 2VBiccc 3VOxx ,
(1)
Ag 2O њ 2AgcBic OO 2VOxx .
(2)
???? ???????, ?????????? ???? ? ?????????? ?????????? Bi2O3, ???????????? ?????
?????? AgcBic ? ????????????? ???????. ?? ????????? ???????? ? ?????????? ????????????
???????????? ?????????? ???????? ??????? VBiccc . ???????? ??????? ??????????
?????????????? Ag ? Bi12SiO20. ? ????, ??-????????, ??????? ????????? ??????? ??????? Bi2O3 ?
SiO2. ? ?????????? (1) ? (2) VBiccc ? ???????? ???????, VO?? ? ?????? ?????????????? ???????????
????????, O O ? ???????? ? ???????? ??????????.
??????? ?????????? Ag ?????????? Bi2O3 ? SiO2 ????? ???? ??????? ?? ????????? [5,
22]: ??? ??????? ????????? ?????????????? ????????? ???????? ??????? ??????? ??????????
# 218 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????? ?????????????? ????????? Bi2O3-SiO2 c ????????
(? < 90°) ????? ??????????? ??? ???????? ?????????? ???; ??? ?????? ????????? ??????????????
????????? ??????????? ????????? ?????????? ? < 90° ???????? ? ??? ????????? ??????????
???. ???????, ??? ?????????? ?????????????? ??????? ? ???????????? ?????? ?????????????
??? ?????????????? ????? ??????? ? ?????????? ?????? [23].
?????? ??????????
1. ?????? ?.?., ?????? ?.?., ?????? ?.?. ? ??. ????????? Bi12MxO20±? ?? ??????????
?????????. ??????, ????????, ????????. ?.: ????, 2004. 316 ?.
2. ?????? ?.?., ???????? ?.?., ??????? ?.?. ?????????????????? ?????????????????
????? ? ?????????? ? ?????????? ????????? ??????????. ?.: ?????, 1983. 226 ?.
3. ???????? ?.?., ??????? ?.?. ??????????? ?????????? BSO : Ag // ???. ?????. ????????? ??????????? ???????. 2007. ? 2. ?. 45 ? 48.
4. Panchenko T.V., Kopylova S.Yu. Photochromic properties of the doped Bi12SiO20 crystals //
Ferroelectrics. 2005. V. 322. P. 69 ? 74.
5. ???? ?.?., ??????? ?.?. ??????-?????????? ?????? ?????????? ? ??????????. ?.:
?????, 1976. 232 ?.
6. Fei Y. T., Fan S. J, Sun R.Y. et al. Crystallizing behavior of Bi2O3?SiO2 system // J. Mater. Sci.
Lett. 2000. V. 19. P. 893 ? 895.
7. ??????? ?.?., ????????? ?.?. ??????-?????????? ???????? ??????? Bi2O3?SiO2 ?
??????? ? ?????? ?????????? // ????????. 1996. ? 2. ?. 69 ? 74.
8. ???? ?.?., ????? ?.?. ?????????? ????? ???????????????????? ?????????. ?.: ???????????, 1966. 703 ?.
9. ?????????? ?.?., ???????? ?.?., ???????? ?.?. ? ??. ??????? Bi2O3?SiO2 // ???. ??
????. ???????. ?????????. 1968. ?. 4. ? 8. ?. 1374 ? 1375.
10. Assal J., Hallstedt B., Gauckler L.T. Experimental phase diagram study and thermodynamic
optimization of the Ag ? Bi ? O system // J. Am. Ceram. Soc. 1999. V. 82. ? 3. P. 711 ? 715.
11. ??????? ?.?., ?????? ?.?., ???????? ?.?. ? ??. ???????????? ??????????? ?????????????? ????????? ?? ?????? ?????? ??????? ? ???????? ????????? ? ???????? // ???????.
?????????. 1991. ?. 27. ? 4. ?. 763 ? 765.
12. Lezal D., Pedlikova J., Kostka P. et al. Heavy metal oxide glasses: preparation and physical
properties // J. Non-Cryst. Solids. 2001. V. 294. P. 288 ? 295.
13. Sanz O., Haro ? Poniatowski E., Ganzalo J. et al. Influence of the meting conditions of heavy
metal oxide glasses containing bismuth oxide on their optical absorption // J. Non-Cryst. Solids. 2006.
V. 352. P. 761 ? 768.
14. ??????? ?.?., ??????? ?.?., ????????? ?.?. ? ??. ??????? ? ??? ??????. ????????????:
??? ???, 2011. 368 ?.
15. Serezhkina S.V. Potapenko L.T., Bokshits Yu. V. Et. Al. Preparation of silver nanoparticles
in oxide matrices derived by the sol-gel method // Glas. Phys. Chem. 2003. V. 29. ? 5. P. 484 ?
489.
16. Sharonov M.Yu., Bykov A.B., Petricevic V. et. al. Spectroscopic study of optical centers
formed in Bi-, Pb-, Sb-, Sn-, Te- and In-doped germanat glasses // Optics Lett. 2008. V. 33. ? 18. P.
2131 ? 2133.
# 219 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????? ?????????????? ????????? Bi2O3-SiO2 c ????????
17. ??????? ?.?., ?????? ?.?., ?????? ?.?. ? ??. ???????????????????? ???????? ?
Eu ? ?????????? ???????? ??????? ? ????????????? ??????? ? ?????? // ????. ???. ?????.
2009. ?. 83. ? 3. ?. 528 ? 533.
18. ???????? ?.?., ??????? ?.?., ???????? ?.?. ? ??. ???????????? ??????????? ???????? ???????????? ?????????? ??????? ??????????? GeO2?Eu2O3?Ag // ???. ??. ????. 2010. ?.
52. ? 7. ?. 1278 ? 1282.
19. Panchenko T.V., Truseyeva N.A., Osefsky Yu. G. Color centers in Bi12SiO20 single crystals //
Ferroelectrics. 1992. V. 129. P. 113 ? 118
20. ??????? ?.?., ???? ?.?., ?????? ?.?. ??????????? ?????????????????? ?????? ? ???????? ????????? // ????. ???. ?????. 1965. ?. 39. ? 4. ?. 966 ? 972.
21. ?????? ?. ????? ????????????? ??????????. ?.: ???, 1969. 554 ?.
22. ?????? ?.?. ?????????? ??????? ? ????????????? ?????????. ????: ??????? ?????,
1972. 196 ?.
23. ??????? ?.?., ????????? ?.?., ??????? ?.?. ? ??. ???????? ? ???????? ?????????????
???????. ????????????: ??? ???, 1999. 498 ?.
Interaction of Bi2O3-SiO2 Melts with Silver
Liubov T. Denisova,
Viktor M. Denisov and Liubov G. Chumilina
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
Contact interaction of Bi2O3- SiO2 melts with silver was investigated by the sessile drop method. It was
found that these oxides spread over the silver surface at its melting temperature .
Keywords: wetting, contact angle, silver, bismuth oxide, silicon oxide.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 3 (2011 4) 221-232
~~~
??? 54-16, 67.08
???????????? ???????????? ??????????
???????? ???????, ??????????
?? ????????? ????? ?????????? ????????
?.?. ????????*, ?.?. ?????????, ?.?. ?????????,
?.?. ???????????, ?. ????????, ?.?. ?????????,?
?
???????? ????? ? ?????????? ?????????? ?? ???,
?????? 660049, ??????????, ??. ? ??????, 42
?
???????????? ??????? ????? ?? ???
?????? 660036, ??????????, ?????????????, 50
?
???????? ???? ??????
??????? 7198, 27 ??? ?? ????? ?????
?
????????? ??????????? ???????????,
?????? 660041, ??????????, ?????????, 79 1
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
??????? ???????? ???????????? ?????????? ????????, ?????????? ?? ????????? ?????
?????????? ?????????, ??????? ????????? ???????????????? ? ?? ????????????
??????????? ? ??????? ? ????????????.
? ???????? ???????????? ?????????? ???????? ??????? ?????????????? ??? ?????????
???????? ??????????: ? ??????? 250?311°? ? 364?407 °?. ? ?????? ??????? ????????????
???????????? ????????? ????????????, ??? ?????? ?? ??? ????????????? ???????
???????????? ?????????? ???????????? ?????????????????? ??????, ? ?????? ?
?????????? ???????? ????????? ??????? ? ????????, ??? ??????????????????, ??? ?
??? ??????. ?????? ?????? ?????? ???????? ???????????? ????? ? ??????? ????????????
?????????? ????????????????? ??????? (?????? ????? 16 ???. %). ???????????, ??? ??????
????????? ??????? ?? ????????? ????? ????????? ???????????? ??????? ?? ??? ???????????
??????????? ? ???????? ???????????? ??????????? ? ???????. ???????????? ???????
????????? (57,2?57,6 ???. %) ?????????? ??? ????????????????? ???????. ?????????? ?????
?????? ?????????, ?????????? ?? 180 °? (26,0?28,5 ???.%) ??????? ??? ????????? ???????.
???????? ?????: ??????, ?????, ??????????? ??????????, ????????????? ??????, ????????,
??????.
*
1
Corresponding author E-mail address: sharypov@icct.ru
© Siberian Federal University. All rights reserved
# 221 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ???????????? ???????????? ?????????? ???????? ????????
????????
???????????? ???????? ? ??????????? ??????????????? ? ???????? ????????? ??????????????? ????????? ????? ??? ???????????? ?????????? ???????, ???????? ??????
? ????????? ?????????? ? ??????? ??????????? ??????????. ????? ?? ???????? ??????????? ???????? ???????? ??????, ??? ?????????? ?????????? 25-30 ???. % ? ???????
? 19-23 ???. % ? ?????????? ??????? ?????????. ???????????? ? ????????? ?????
???????? ?????????? ??????????? ????????? ?????????? ?? ????????????? ? ???????
???????? ??????????????? ?????????, ??? ???? ?????? ???????? ? ???????? ???????????????? ??????.
? ???? ????????????? ????????, ???????????? ??? ?????????? ???????, ???????????? ??????? ???????????? ????????? ????????????????? ?????????????, ??????? ?????
?? ?????????????? ??? ?????????? ???????? ?????? [1, 2]. ??????????? ???????????????
??????? ? ????????????????? ???????? ????? ???? ???????????? ???????????? ????????. ???????????? ? ???? ????????? ?????? ????????, ??? ???????, ????????? ??????????. ??????? ??????????????? ????-, ????????????? ???????? [3], ? ??????? ????????,
?????????? ?? ?????? ??????, ???????????? ??????????? ??????????? ?? ?????????
???????, ? ?????????? ??????????????? ???????? ? ??????? ? ???????? ??????? ?????????.
?????????? ??????????? ??????? ???????????????? ????????????? ??????? ???????
???????? ??? ??????????? ???????????? ? ??????????????? ???????. ????????? ???????????? ??????????? ???????????? ??????? ???????? ?-?????????????????, ??????????? ?
???????????? ??????????????? ???????, ??????? ????????? ????? ????? ?????????? ?-?
? ?-?-???????, ??????? ??????????????? ????????????? ??????? ????????????? ???????? [4].
????????, ??? ? ???????? ???????? ????????????? ??????? ????? ???? ????????? ??????? ?
??????????????, ??????? ?????????????? [5]. ????? ???????? ????????? ??????? ?? ?????????
???????? ??? ?? ????????? ? ???????????? ????, ??????? ????????????? ???????????? ??????? ???????, ??????????? ?? ????????? ??? ??? ???? ????????? ???????? [6]. ?????? ?????
???????? ???????????? ??? ????? ???????? ? ????????????? ?? ?????????????, ??? ? ????????
????????? ???????.
????????, ??? ??????????? ?????????? ??????? ????????? ??????????????? ??
???????????????????? ?????????, ??? ???? ???????????? ????? ????????? ???????????? ?????????? ???????????????? ? ???????????? ???????, ?????????? ? ???????????
??????, ???????????? ? ??????? ????????? [7]. ???????????? ??????????? ?????????
??????? ????? ???? ?????????? ? ???????????? ????????????????? ?????????, ???? ??????????????? ???? ? ?????? ? ???????????? ?????????????????? ????????? ??? ?????.
??? ?????????? ?????? ??????? ????????? ??????????? ??????????? ??????? ????????
? ????? ????????????? ??? ? ??????????? ???????, ??????????????? ??????????? ????????? ???????????. ? ???????? ????? ??????? ???? ??????????? ???????? [8, 9], 9,10??????????????? [10], ????????????? ??????????? [11], ?????? ????????????? ??????
[12-14].
? ????????? ?????? ????????? ???????????? ??????????? ??????????? ???????? ???????, ?????????? ?? ????????? ????? ?????????? ????????.
# 222 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ???????????? ???????????? ?????????? ???????? ????????
????????? ? ??????
? ?????? ?????????????? ????????? ????? ?????????? 3,9 ???.%, c ???????? ????? 2 ??,
????????????? ? ???????????? ???????????.
????????? ????????? ??????? ?? ????????? ????? ????????? ????? ????????????????
????????? ???????????? ?? ????????, ????????? ? ?????? [15]. ?? ????????? ????????? ?????? ??????????????? ?? ??????? ??????? ? ???????? ???????? ? ???????? ?????? ?? ????????, ????????? ? ?????? [6]. ?????????? ?????? ???????????? ????? ??????? ???????????
?????. ????? ????????? ??????? ????? 6,6±0,3 ???.%.
?????????????? ?????? ???????? ?? ?????? ???????? ? ??????????? ???????? [16]. ?
?????? ???????? ???? ????????? ????? ???????????? ????????? ? ??????? ? ????? ????????? ?? 3 ?. ????? ??????????????? ??????? ????????? 20,8±1,7 ???.%.
???????????????? ?????? ???????? ?? ??? ????????, ????????????? ? ???????? ?????????????? ????????? ?????, ?????? 24,7 ???.% ??3???? + 5,3 ???.% ?2?2 + 2 ???.% H2SO4
[17, 18]. ?????????? ??????? ????????? ????????? ??????????? ???????? ? ???? (????? ????
? 20 ??? ?????? ?????? ???????????). ? ?????????? ?????? ??????? ? ??????. ????? ???????
????????? ??????? ??? ??????????? ?? ??????? ??????? ? ?????????? ?? ??????????? ????.
????? ????????????????? ??????? ? 8 ? 13 ???.%.
?????????? ?????? ??????????? ???????? ??????? ?????????? ? ??????? ???????????
HCNS-0 EA FLASHTM1112 (????. 1).
??????? ??????????? ??????? ???????????? ????????????? ? ?????????????? ??-?????
???????????? «Vektor 22» ????? Bruker. ????????? ???????????? ?????????? ????????? ??
????????? OPUS/YR (?????? 2,2). ??????? ??????? (3 ??) ??? ??????? ???????? ? ???? ???????? ? ??????? KBr.
??????????? ???????? ???????? ??????????? ? ??????? ??????????? ????????????????
STA ? 449C Jupiter «NETZSCH», ???????????? ? ????-????????????? QMS 403C A?ol?s. ????????????? ???????/???????-???????? ????????? (TG ? DST ?????? ???? S) ? ????????? ?
??????????? (Al2O3) ??????? ? ??????????? ????????. ??????? ?????? 8,5±0,2 ?? ???????????? ?????????? ?? 40 ?? 1000 °? ?? ????????? 10 °? /??? ? ???????????? ????????? ??????
?? ????????? ?????? 40 ??/???.
???????????????? ???????? ? ??????? ? ???????????? ????????? ?? ??????????? ????????? ???????? 0,25 ?. ? ???????? ????????? 4 ? ???????, 0,13 ???? ??????. ????? ???????? ???????? ?????????? ????????? ? ????????? ????????????? ??????????? ?????? ??? ????????
??????? 1. ?????????? ?????? ??????????? ???????? ???????
??? ???????
??????????, ???.%*
?????????, ???.%*
?
?
?
????????????????
62,7
33,0
5,2
0,1
????????
61,9
31,9
5,5
0,1
??????????????
64,6
30,4
5,2
0,6
*? ??????? ?? ????????? ????? ??????
# 223 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ???????????? ???????????? ?????????? ???????? ????????
???????. ??????????? ?????????? ????????????? ?????????? 400 °? ??? ?????????????????
1 ?. ???????? ??????? ????????? ? 6 °? /???. ?? ?????? ???????? ??????? ?????? ??????????
???????? ???????????. ??????? ???????? ?????????? 4 ? 6 ???.
????? ?????????? ???????????? ? ?????????? ???? ?? ????????? ??????????? ?????
?????????????? ???????????? ????????? ???????? ? ?????????, ?????? ???? ?????????? ? ?????????????? ???????????? ???-80-1 ? ??????????-????????????. ?????????? ?? ? ??4 ???????????? ?? ???????? ??????? ?????? 2 ? ? ????????? ?????? CaA 5?? ??? ??????????? 25 °?
? ?????????????? ??????. ??? ??????????? ??2 ? ?????????????? ????? ?2-?3 ????????????
???????? ??????? ?????? 2 ? ? ????????? «Porapak-Q» ? ?????? ???????????????? ??????????? ? ????????? 50 ? 150 °? (???????? ??????? ??????????? 20 °? /???). ? ???????? ???????????? ???????????? ??????? ??? ???????? ?????? 35-40 ??3/???.
?????????? ????????? ????????????? ?????????? ?????????? ??????? ? ?????????? ??
??????. ??????????????? ??????? ??????? ?????????????? ??? ?? ????????????? ?? ??? ???,
???? ?????????? ?? ?????? ??????????. ?? ????????? ?????????? ???????????? ????????, ?
???????? ???????? ?? ?????????? ????? ?????? ??? ???????? (0,2 ?? ??. ??.) ??? ?????????
???????????. ????? ?????????, ??????????? ??? ???????????? ???? 180 °?, ?????????? ??????? ???????. ?????? ? ??????? ???????? ?????????? ?? ????????-?????? ????????? ? ??????????. ?? ???????? ????? ???????? ??????? ? ???????????? ??????? ???????????? ???????
????????? ??????? ? ?????? ? ???????????? ????????. ????? ?????????, ?????????? ??
180 °?, ?????????? ?? ????????: ??????? ????????? ??????? ? (????? ?????????, ???????????
??? ???????????? ???? 180 °? + ????? ???????????? ?????????, ???????????? ??? ?????????? ???????).
?????????? ? ??????????
???????????? ???????? ??????? ???????? ??-????????????? ????????, ??? ?? ???????
???????? ????????? ???????? ???????? ????? ?????????? (????. 2). ????????? ????? ????
????????? ? ???????????? ? ????????????? ??????? [19 ? 22]. ???????????? ???????? ? ???????? ???????? ??????????? ? ??????? ?????????? ?=? ?????, ????????? ? ?????? ????????????? ????? (1738-1709 ??-1). ?????????? ??????? ????????????? ???? ?????? ?????????? ???
??????? ????????????????? ???????, ???????? ? 1,5 ? 3 ???? ????, ??? ? ???????? ??????????????? ? ????????? ????????, ??????????????. ????????????? ????? ?????????? ? ???????
1430-1422 ??-1, ??????? ????? ???? ???????? ? ?????????????? ?????????? ? ????????????
???????, ??????????? ? ???? ???????????????? > ?????????????? >> ????????. ? ???????
??????????????? ??????? ??????????? ??????? ????????????? ????? ?????????? ? ???????
1605-1593 ??-1, ??????????? ??? ?-?-????????? ????????? ?????????????? ??????. ???????????? ???????? ??????????? ????? ? ??????? 1128-1125 ??-1, ??? ??????????? ?????? ?????????? ????????? ????????? ?-?-??????, ??????????? ??? ????????? ????????????? ????? ?
????????????? ????????? ????????? ?-?-?. ??????? ???? ????? ????????? ?? ???????????
????????????? ?????????? ?????????????????? ?????????????? ????? ? ???????????????? ?
?????????????? ????????. ??????????? ????????????? ????? ?????????? ??? 1270 ? 1330 ??-1
????? ???????????? ??? ?????? ??????? ??????????? ? ???????????? ????? [23]. ??? ????????????????? ??????? ??? ?????????? 0,83, ??????????????? ? 0,44, ????????? ? 0,40.
# 224 #
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?.?. ???????, ?.?. ????????? ???????????? ???????????? ?????????? ???????? ????????
??????? 2. ????????? ????? ?????????? ? ??-???????? ???????? ????????, ?????????? ?? ?????????
????? ?????????? ?????????
????????? ??????
?????????? (?? -1)
3460-3412
3000-2842
????????? ?????? ??????????
????????? ????????? ?? (??????????? ? ?????????? ????? ??-??????,
??????? ??????)
????????? ????????? ? ? ? ? ????????? ? ??????????? ??????? (?????? ???
????? ?????????? ?????? ? ~2945 ??-1 (??.)
? ~2850 ??-1 (??)
1738-1709
????????? ????????? ????????????? ?=?
1605-1593
?-? ? ????????? ????????? ?????????????? ?????? + ?=? ????????? ?????????
1515-1505
?-? ? ????????? ????????????? ????????? ?????????
1470-1460
1430-1422
1370-1365
1330-1325
?????????????? ????????? ?????
? ?? (?????????????)
?-? ? ????????? ????????????? ????????? ????????? ? ?-? ??????????????
???????????? ??????????????? ??????????? ? ???????????? ???????
?????????????? ????????? ?????
?-? (????????????)
????????? ????????? ????????????? ??????
1270-1275
????????? ????????? ???????????? ??????
1128-1125
????????????? ?-? ? ??????????? ?????????????? ????????? (???????? ???
???????????? ???????) + ?-? ????????? ????????? ?? ????????? ??????? +
?-?-? ????????????? ????????? ?????????
1085-1030
?????????????? ????????? ?????? ?-? ? ?-?
???????????? ?????????? ???????? ??????? ??????? ???????????????? ????????, ???
??????? ?? ???????????? ?????????? ????? ???? ???????? ?? ??? ?????? (???. 1). ?????? ?????? ???????? ????????? ??????????? ?? ???????????????? ?????? ?????? ????? ? ???? ????
??? 311 °? ? ???????? ?????????? ????????????????? ???????. ?? ??????? ???? ?????? ? ???????? ?????????? ??????????????? ? ????????? ???????? ????????? ???????? ?? ???????????????? ?????? ?????? ????? ??? 270 ? 250 °?, ??????????????. ?????? ??????, ????????,
??? ???? ????? ??????? ??????????????? ???? ??????????? ?????? ? ??????? ??????????
364 ? 407 °?, ??? ???? ???????? ?????????? ??????????????? ? ????????? ???????? ? ?????
???????? ?????? ????????? 3,4 ? 3,5 ? 2,1 ???.% /??? ??? ????????????????? ???????.
?????? ????????? ???????? ????????? ???????????? ??????? ?? ?????????? ?? ???????????? ???????????, ???????????? ?? ??????????? ????????????????????? ????????????
(????. 3). ???????????? ?????????? ???????? ??????????? ? ??????? ???????? ??? ?? ??????
1, ??? ? ????????? (?????? 1 + ?????? 2), ???? ???????? ??? ????????????????? ???????. ??????????? ?????????? ?????????? ??? ????????? ??????? ??????????? ???? ??????????????? ??????????? ??? ????????????????? ? ??????????????? ????????.
??????? ???????? ?????????? ???????? ????????????? ??????? ????-?????????????.
????? ??????????? ???? ??? ?????????? ? ???????????? ? ???????, ???????????? ? ??????
[24]. ?? ??????? 2 ? ???????? ???????? ????????? ?????? ????????? ????????????? ???????
# 225 #
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???. 1. ???????????????? ?????? ?????? ????? ??? ???????? ???????, ?????????? ?? ?????????
?????: 1 ? ????????????????, 2 ? ???????? ? 3 ? ?????????????? ????????
??????? 3. ?????????? ???????????? ?????????? ????????,
????????????????????? ???????????? ???????? ????????
??? ???????
????????????
??????????? ??????????, 0?
?????? 1
??
???????????
??????? ?????????, ???.%
?????? 2
?????? 1
?????????
????????????????
311
407
13,0
61,4
????????
250
364
4,4
60,2
??????????????
270
378
4,3
55,2
??????? 4. ???????????? ????????????? ??????????? ???? (???????? ???????) ?????????
????????????????? ????????? ???????????? ?????????? ????????
????????????????
??4
m/z = 16
5,910
H 2O
m/z = 18
36,065
1210
CO2
m/z = 44
28,027
????????
4,699
25,763
1,647
7,083
??????????????
8,320
31,656
1,257
18,604
??? ???????
HCHO
m/z = 30
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ???????????? ???????????? ?????????? ???????? ????????
???. 2. ?????? ????????? ????????????? ??????? ???? ?? ??????????? ???????? ????????????
?????????? ????????????????? ???????: 1 ? m/z ? 18; 2 ? m/z ? 44; 3 ? m/z ? 16
???? ??? ????????????? ???? ?? ??????????? ???????????? ?????????? ?????????????????
???????. ?????, ??? ???????? ??????? ????????????? ????? ??????? ? m/z ? 18 ? m/z ? 44,
?????????? ?????????????? ? ?2? ? ??2. ?? ?????? ????????? ????????????? ??????? ???
m/z ? 18 ????? ???????? ????????? ????????. ??????, ??? 98 °?, ????????, ????????????? ???????? ???????? ???? ??? ????? ???????. ??????, ? ??????? 180 ? 600 °?, ????????????? ??????
? ?????? ??????? ?????????? ???????, ? ???????????? ????????? ?????????? ??????? ?????????. ??? ???? ? ???? ??????? ??????????? ????????????? ??2 ? ????. ?????? ???????, ? ?????????? ??? 700 °?, ?? ?????????????? ????????????? ???????? ????? ? ???????? ??????? ?
??????????? ??????? ???????????.
? ??????? 4 ????????? ???????????? ????????????? ??????????? ????. ??? ?????????????? ???????? ????? ?? ??????? ????? ????????? ??????? ????????????? ??? ??????
?????, ????????? ?????????????? ??????????? ?? ??????? ???????. ?? ??????? 4 ???????,
??? ? ???? ??????????? ???????? ?????????? ?????????? ?????? ?????????? ??? ??????????? ?????????? ??????????????? ???????, ??? ???? ??? ???? ???????? ???????? ?????
?????? ?????????? ?? ?????? ??????. ?????????? ?????????? H 2O ? ??2 ?????????? ? ?????? ?????????? ????????????????? ???????, ??????? ???????????, ??? ???????????? ?????
???? ??????? ?????????? ?? ?????? ?????? ? 17,7 ? 21,4 % ?? ?????? ?????????? H 2O ? ??2,
??????????????. ??? ?????? ??????????, ??? ??????????? ??????? ????????? ? ????????
??????????? ?????????? ???????? ?????????? ? ?????????? ?????????? ??????, ??????????
# 227 #
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?.?. ???????, ?.?. ????????? ???????????? ???????????? ?????????? ???????? ????????
??????? 5. ?????? ???????????? ????????? ????? ???????????? ??????????? ???????? ? ?????????????
??????
??, ???.%
??2,
???.%
??4,
???. %
?2?4,
???. %
?2?6,
???. %
?3?8.
???. %
????????????????
1,17
45,18
0,43
0,91
10,35
41,95
????????
3,21
26,92
1,01
0,70
12,22
55,91
??????????????
3,90
25,48
1,78
0,69
10,61
17,41
??? ???????
??????? 6. ?????? ???????????? ????????? ????? ???????????? ??????????? ???????? ? ????????
??????
??, ???.%
??2,
???.%
??4,
???. %
?2?4,
???. %
?2?6,
???. %
?3?8.
???. %
4,95
73,49
2,39
4,47
14,69
-
????????
9,22
40,94
7,78
11,77
30.29
-
??????????????
11,72
45,21
7,44
8,31
27,31
-
??? ???????
????????????????
????????. ???????? ???????????? ?????? ? ???? ??????? ?????????? ??? ???????? ??????? ????? ??????????? ????????? ????? ? ??????????? ????? ???????: ??? 250 °? ? ? ? ? ? ?
?- ????????? ???????, ??? 300 °? ? ??? ? ?? ? ?-?????????? ???????, ? ????? ????? ???????????? ????????: ??? 170 ? 220 °? ????????????? ??????? ?? ? ????, ??? 250 °?, ????????????? ??????? ?? ? ???? [7]. ????? ????, ????? ????????? ??????? ???????????????????,
?????????? ?????????? ????????????? ????? ? ??????? ????????????????? ??????? ????
???????? ???? ????, ??? ?????????? ??????????? ???????????? ???????? ??????? ???????
??-?????????????.
??????? ??????? ???? ??????????? ???????????? ??????????? ? ????? ????????? ?
?????????????? ???????. ???????? ?????? ??? ????? ???????????? ????????? ???????????????? ??????? ???????????? ??? ???????? ????????? ???????, ??? ? ????? ?????????????
?????? ? ????????? ??? ??????????????. ?? ?????? 5 ? 6 ???????, ??? ??? ?????????? ????????????? ? ???????? ?????? ???? ????? ???????, ????? ? ??????, ? ????????????? ? ???????
? ???????? ????????. ?????????? ????????, ????????, ??????? ? ??????????? ????????????
??????? ? ???????????? ?????????? ????????????? ???????????? ?????????, ????????
????????? ?????? ??? ????? ???????? ?????. ??????? ????? ??????? ???????? ? ?????? ?????? ??????? ? ?????? ? ???????????????? ????????.
?????? ????????? ??????? ????????? ???????????? ??????? ?? ??? ??????? ????????? ?
????? ?????? ????????? (???. 3). ???????????? ???????? ????????? 57,2 ? 57,6 ???.% ????
?????????? ? ?????? ? ???????????????? ???????? ? ?????????????? ?????????????? ? ????????? ???????, ??????????????. ???????? ??????? ?????? ???????????? ?????? ?????????
26,0 ? 28,5 ???.% ???? ???????? ? ?????? ?? ???????? ????????. ?????????????? ??????,
????????????????? ???????? ???????????????? ??????????, ????? ?????????? ??????? ????????? ? ????? ?????? ?????????.
# 228 #
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?.?. ???????, ?.?. ????????? ???????????? ???????????? ?????????? ???????? ????????
???. 3. ??????? ??????? ????????? ??????? ?? ????????? ????? ?? ?????????? ??? ????????????????
(?) ? ???????? ??????, (?) ? ????????????? ??????: 1 ? ??????? ?????????; 2 ? ????? ??????? ??????
?????????, ??????? ???? 180 °?; 3 ? ????? ??????? ?????? ?????????, ?????????? ?? 180 °?; 4 ?
????? ????. ??????????? ??????????? ???????? ??????? ????????? ??? 400 °? ? ??????? ????????
5M??
??????
1. ??????????? ??????????? ???????? ???????? ???????, ?????????? ?????????? ???????? ?? ????????? ?????. ???????????????? ?????? ??????????????? ??????? ???????????
????????????? ?????, ?????????????? ? ????????????? ??????????? ??????. ????? ????????? ??????? ????????? ???????????? ??????? ?? ????????????? ?????????? ? ??? ??????????? ? ???????????? ??????.
2. ? ???????? ???????????? ?????????? ???????? ??????? ????? ??????? ???????? ???
??????. ??????, ??????? ???????? ???????? ?????????? ? ??????? 250 ? 311 °?, ???????????
??????????? ???????????? ?????????? ???????????? ?????????????????? ??????, ??????, ?
?????????? ???????? ?????????? ? ??????? 364 ? 407 °?, ????????????? ?????????? ????????
????????? ??????? ? ??????????? ??? ?????????????????? ??????, ??? ? ?????? ?-?. ????????, ??? ?????? ?????? ?????? ???????? ???????????? ????? ? ??????? ???????????? ?????????? ????????????????? (?????? ????? 16 ???.%) ???????.
3. ?????????? ??????? ???????????? ??????????? ???????? ??????? ? ????? ??????? ? ???????????? ??? 400 °?. ????? ????????? ??????? ????????? ???????????? ??????? ?? ??? ??# 229 #
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?.?. ???????, ?.?. ????????? ???????????? ???????????? ?????????? ???????? ????????
????????? ??????????? ? ???? ????????. ???????????? ???????? ??????? ????????? ????
?????????? ??? ????????????????? ??????? (57,2 ? 57,6 ???.%), ?????????? ????? ??????
?????????, ?????????? ?? 180 °? (26,0 ? 28,5 ???.%), ??????? ??? ????????? ???????.
??????????? ??????????? ???????, ????????????????????? ? ??-??????????????????
???????????? ???????? ??????? ???????????? c ?????????????? ??????????? HCNS-0 EA
FLASH TM1112, ??????????? ???????????????? STA 449C Jupiter ? ??-????? ???????????? Vector 22 (Bruker) ????????????? ????????????? ?????? ????????????? ???????????
?? ???.
?????? ????????? ??? ????????? ????????? ?????????? ??????????????? ???????????? ?????????? ??? «?????????? ??????? ??????????», ?????? ? 3.8.
?????? ??????????
1. Clark J.H., Budarin V., Deswarte F.E.I. Green chemistry and the biorefinery: a partnership for
a sustainable future. Green Chem. 2006. V. 8. P. 853-860.
2. ??????? ?.?., ???????? ?.?. ?????????? ??????? (?????). ?????? ?????????? ?????. 2010. ?. 83. ???. 2. ?. 175 ? 194.
3. Zmierczak W. W., Miller J. D. Processes for catalytic conversion lignin to liquid bio-fuels.
International Patent WO 2006/119357 U.S .2006.
4. Calvo-Flores F.G., Dobado J.A., Lignin as renewable raw material. ChemSusChem. 2010. V.3.
P.1227-1235.
5. Chen R., Wu G., Self-condensation of oxidized lignosulfonate. II. Condensation behaviors. J.
Appl. Polym. Sci. 1991. V.42. P. 2073?2079.
6. ??????? ?.?. ????? ????????? ? ?? ?????????. ?.: ?????, 1953. 670 ?.
7. ???????? ?.?. ??????? ?????????: ??????, ????????, ????????, ????? ????????.
?.: ????. ????-???, 1990. 312 ?.
8. Connors W. J., Johanson L. N., Sarkanen K. V., Winslow P. Thermal Degradation of Kraft
Lignin in Tetralin. Holzforschung. 1980. V. 34. P. 29 ? 37.
9. Vasilakos N. P., Austgen D. M. Hydrogen-donor solvents in biomass liquefaction. Ind. Eng.
Chem. Proc. Des. Dev. 1985. V.24. P. 304 ? 311.
10. Dorrestijn E., Kranenburg M., Poinsot D., Mulder P. Lignin depolymerization in hydrogen
donor solvents. Holzforschung. 1999. V. 53. P. 611 ? 616.
11. ??????? ?.?., ??????????? ?.?., ???????? ?.?., ?????????? ?.?., ????? ?., ?????
?.?. ????????? ???????????? ?????????????? ?????? ?????????? ????????? ????????????? ? ???????????? ???????. ????? ? ????????? ??????????? ????????. 2003. ? 11. ?.429 ?
436.
12. Katritzky A. R., Nichols D. A., Siskin M., Murugan R., Balasubramanian M. Reactions in
high-temperature aqueous media. Chem. Rev. 2001. V. 101. P. 837-92.
13. Yu J., Savage P. E. Decomposition of formic acid under hydrothermal condition. Ind. Eng.
Chem. Res. 1998. V. 37. P. 2 ? 10.
14. Brieger G., Nestrick T. Y. Catalytic Transfer Hydrogenation. Chem. Rev. 1974. V.74. P. 567580.
# 230 #
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?.?. ???????, ?.?. ????????? ???????????? ???????????? ?????????? ???????? ????????
15. ????????? ?.?. ????? ????????? ? ?? ???????? ???????????. ???????.: ??????,
2002. 50 ?.
16. ?????????? ?.?., ????????? ?.?., ???????? ?.?. ???????????? ?????? ?? ????? ????????? ? ?????????: ??????? ??????? ??? ?????. ?., 1991. 320 ?.
17. ???????? ?.?. ?????????? ??????? ????????? ??????? ??????? ?? ?????? ??????? ?
?????? ????. ??????? ?????? ???. 2009. ?2. ?.156 ? 164.
18. ????????? ?.?. ??????????? ???????? ?????????????? ????????? ????? ????????
???????? ? ??????????? ????????? ???????? ? ?????-?????????? ????????????// ??????? ?????? ???. 2008. ?1. ?.181 ? 189.
19. ?????? ?.?. ????? ????????? ? ????????????? ?????????. ???.: ??????, 1999. 628 ?.
20. ????????? ?.?. ?????????? ? ???????? ????? ???????. ?.: ?????, 1973. 297 ?.
21. ??????? ?.?. ??-??????? ???????. ?.: ?????, 1975. 632 ?.
22. ????????? ?.?., ??????? ?.?., ???????? ?.?. ?????? ???????????? ????????? ? ?? ???????????. ???????: ???-?? ???. ???. ??-??, 2002.160 ?.
23. ?????? ?., ?????? ?. ????????? (?????, ???????????????, ???????): ???. ? ????.
?.:?????? ????-???, 1988. Fengel D., Wegener G. Wood (Chemistry, Ultrastructure, Reactions).
Berlin,New York: Walter de Gruyter, 1984.
24. Jakab E., Faix O., Till F. Thermal decomposition of lignins studied by thermogravimetry /
mass spectrometry. J.Anal. Appl. Pyrol. 1997. V.40-41. P.171-186.
Investigation of Thermal Decomposition
of Lignin Samples Isolated from Aspen Wood
by Various Methods
Victor I. Sharypova,
Liudmila I. Grishechkoa, Liudmila S. Tarasovab,
Sergei V. Baryshnikova, Alain Celzard? and Boris N. Kuznetsova,d
a
Institute of Chemistry and Chemical Technology SB RAS,
42 st. K. Marx, Krasnoyarsk, 660049 Russia
b
Krasnoyarsk Scientific Center SB RAS
50 Akademgorodok, Krasnoyarsk, 660036 Russia
c
Institut Jean Lamour ? UMR CNRS,
27, rue du Merle Blanc, Epinal, 7198 France
d
Siberian Federal University,
79, Svobodny, Krasnoyarsk, 660041 Russia
Processes of thermal decomposition of lignin isolated from aspen wood by different methods and their
thermal dissolution with ethanol and isopropanol at 400 °C were studied.
According to tandem thermogravimetry data two maximum of thermal decomposition rate of the lignin
samples were recorded in the temperature range between 250-311 °C and 364-407 °C. Taking into
# 231 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ???????????? ???????????? ?????????? ???????? ????????
account the composition of gaseous products formed, it was suggested that the first of them corresponds
to cleavage of relatively thermal unstable oxygen containing chemical bonds, while the second accords
to a destruction of the basic structure of lignin with the rupture both of oxygen containing bonds and
C?C bonds. The first stage had the dominant influence (weight loss 16 wt. %) in the decomposition
of Organosolv lignin. It was established that the method of lignin isolation from aspen wood had a
significant effect on its reactions ability in the process of thermal dissolution in alcohols. The maximum
degree of conversion was observed for the Organosolv lignin (57.2 ? 57.6 wt.%). The highest yield of
liquid products boiling up to 180 °C (26.0 ? 28.5 wt.%) was obtained with Alkali lignin.
Keywords: lignin, aspen wood, thermal decomposition, aliphatic alcohol, products, composition.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 3 (2011 4) 233-247
~~~
??? 547.754.83+519.876.5+543.442.3
??????? ????????????? ?????????????
????-??????????????
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?.?. ???????, ?.?. ??????,?
?
????????? ??????????????? ??????????????? ???????????,
?????? 660049, ?. ??????????, ??.????, 82,
?
???????? ????? ? ?????????? ??????????
?????????? ????????? ?????????? ???????? ????
?????? 660049, ?. ??????????, ??.?????? 42,
?
????????? ??????????? ???????????,
?????? 660041, ?. ??????????, ??.????????? 79 1
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
???????????? ? ???????????????? ??????? ??????????? ??????????? ?????????????
4-?????????????? ? ??????? ????????????? ?????????? ???????? ?? ??????? ???????? ????
2,6-??(???????????????)-3,5-???????-4-?????????????. ???????? ?? ?????? ???????????????
?????? ??????-???? ????????, ??? ????????????? ????? ?????? ? ??????? ???????
??????????? ?? ????? ????????? ????????????? ??????, ?????? ? ??? ?????? ??????
??????? ????????? ????????????? ????????? ?? ?????????????????? ????????????? ??
????? ????????? ????????????? ? ???????????? ?????? ???????????. ????????????????
????????? ??????? ????????????? ? ???????????? ????????????? ??????????????.
?????????? ???????? ??????? ? ??????????? ????????????? ?????????, ??? 1?????????????? ? ????-?????????????. ??????? ???????????????? ????????????????????
??????? ??????????? ??????????????? ????????? ?????? ?? ????????? ????????????? ?
?????????? ????? 3,5-??(??????????????)-2,6-???????-1,4-??????????-1-?????? (?15H19NO6)
(I). ???????????????????? ?????????: a =7.3322(6) Е, b = 10.5039(12) Е, c = c 21.1520(20)
Е, ? = 93.742(6)°, V = 1625.58(2) Е33 Z=4, ??.??. P21/c. ????? ? ????????????? ????????
????????? ? ?????? ???????????? ??????? ?????-????? ? ??????????? «???????» ?
«??????» ???????????. ????????? ????????? ????????? ??????? ?????????. ???????????,
??? ????????????? ?????????? ?? ????????? ?????????????. ??????????????? ?????????
???????????? ?????????? ??????? ??????? (I) ????? ??? ? ? ???????? ?????????? ?????
*
1
Corresponding author E-mail address: Tovbis@bk.ru, Kirik@icct.ru
© Siberian Federal University. All rights reserved
# 233 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ????????????? ????????????? ????-??????????????
?????????? ? ??????? ?? ?????????? 3.63 Е ?? ???? ???????? ?????? ?????? ???????? ?? 180?
?????? ??? ???????. ???????? ??????? (I) ??????, ??? ????????????? ?????? ?????????????
? ????????? ?????? ? ????? ?-?????????? ? ????????????. ?????????????????? ??????
????????? ??????????? ??????????????? ??????. ?????? ?????????? ???????? ?????????????
????? ????? ????????? ????????? ?????? 1,4-??????????-1-???????, ??? ????????????
??????? ??? 1?-????????????? ? ????-?????????????.
???????? ?????: ??????????????? ?????????????, ?????????????, ?????????????, ?????????
????? 1,4-??????????-1-???????, ??????????????????? ?????? ??????????????, ?????????????????? ??????? ?? ?????? ??????-????, ??? 1H-?????????????, ????-?????????????.
???????? ??? ????????????? ?????????????? (???.1), ???????????? ? ???? ????? ? ?????????? ????????????. ? ????????? ???????????????? ????? ??????????????? ??????????
???????????? [1]. ??? ?? ???????????? ?????????? ?-??????????? [2], ????????? ??????????? ??????? ????? ?????????? ? ??????-???????????????? ?????????????? ? ????????
??????????????????? ?????????? [3].
??????? ??????? ???????????????? ???????????????????? ??????? ??????????? ??????????????? ????????? ???? ? 2,6-????????????????-3,5-???????-4-??????????????? ?????
(???. 2), ?????????????? ???????????????? ???? [4,5]. ????????, ??? ? ???????????????
????????? ?????? ????? ????????? ?? ???????????? ?????????? ?? ????? ????????? ???????????: ????? ????, ???? ?? ?????????????????? ????? ??????????? ?? ? ????????? ??????????? ??????, ? ????? ??????????????? ? ???, ??? ??????? ???????? ????? ??????????????????
????? ? ??????????? ?????. ?????????????, ???????????? ? ????????? ??????????? ??????, ????? ???????????? ?????. ???????????? ???????? ???????? ??, ??? ????? ?????????
? ?????, ????????? ?? ??????? ????? ?? ??????????: d(K-O)=2,50 A ? d(K-N)=2,66A, ????????? ???????? ? ??????????????? ????? ?????. ??????????? ?????????? ????? ????
???????????????? ??? ??????????? ??????? ????? ??-?????? NO-??????. ?????????????
??????????? ????? ???????? ??? ??????????? ??????? ?????, ??? ???????? ???????-????,
???, ??-????????, ??????? ??????? ? ???????? ?? ??? ??????????? ?????????????? ??????.
???????? ??????????? ???????? ????? ???????????? ??????????????, ????????? ????????
OH
ROOC
COOR
H3C
CH3
NO
I (a-f)
R = Me (a), Et (b), Pr (c), Bu (d), i-Bu (e), i-Am (f)
???. 1. ???????????? ????????? ????????????? ??????????????, ?????????????? ? ????????? ??????
# 234 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ????????????? ????????????? ????-??????????????
???. 2. ???????? ????????? ???????? ???? 2,6-????????????????-3,5-???????-4-????????????? ?????
??? a (??????????? ??????). ????? ???????? ?? ???????? [4]
OR'
OK
R'-I
a
-KI
H3C
CH3
H3C
COOR
ROOC
COOR
ROOC
CH3
NO
NO
III (a-l)
II (a-f)
O
R = Me (a), Et (b), Pr (c), Bu (d), i-Bu (e), i-Am (f)
ROOC
COOR
b
CH3
H3C
N-O-R'
IV (a-l)
a: R=R'=Me; b: R=Me, R'=Et; c: R=Et, R'=Me; d: R=R'=Et; e: R=Pr, R'=Me;
f: R=Pr, R'=Et; g: R=Bu, R'=Me; h: R=Bu, R'=Et; i: R=i-Bu, R'=Me;
j: R=i-Bu, R'=Et; k: R=i-Am, R'=Me; l: R=i-Am, R'=Et.
???. 3. ????????? ??????????? ??????? ????????????? ????? ????????????? ??????????????
????????????? ??????????? ??????????? ??????????? ????? ? ???????? ? ????? ??????????. ? ?????????, ?????? ????? ???? ????????? ? ???, ??? ????? ?????????????? ????????
???? ????????????? ?????????????? ?????????? ????????: ?? ????? ????????? ????????????? ?????? ??? ?? ????? ????????? ?????????????? ????? ????????? ???????????
??????? ???????????? ?? ???. 3.
# 235 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ????????????? ????????????? ????-??????????????
??????? ????????????? ??????? (?????????????????) ?????????????? ???????? ?????. ????? ????????????? ??????????? ????????? ????????? ? ???? ???????????? ???????????????????????? (????). ??? ????????????? ?????????? ???? ???? ????????
??????? ??? ??????? ????????? ???? ????, ? ???????? ?????? ? ???????? ???? ????
[6]. ????????? ???? ???? ????? ?????????? ??? ????????????? ??????????? ?????????
?????? ?-??????????????????? ? ???????? ? ??????????? ?????? [7] ? ??? ???????? ??????????? ? ?????????? ????? [8]. ? ?????? [9] ???????? ???? ?????? ???????? ??? ?????????????
???? ???????? ? ??????????? ?-???????????????????, ?????? ????? ?? ????????, ??? ???
???????? ???????? ? ??????????? ?????? ??????? ?????????? ?-?????????????, ?.?. ????????????? ????? ????????? ? ?? ?????????? ??????????. ?? ?????????? ?????????? ???? ???????
?-????????????? ? ????????? [10], ??? ???? ?????????? ?-?????????????. ????? ???????, ???????????????? ???????????? ??? ????????? ??????????? ???????. ??????? ?????? ???????
???????????, ?? ?????? ?? ????? ?????? ?????? ??????? ????????????? ????-??????????????
??????????????????.
??????????? ???????? ?????????? ???? ??????? ????????????? ? ????????? ?????? ????????? ????? ?????????. ??????????? ????????????? ????????-?????????? ???????????
???????? ??????????????-??????? ? ????????? ?????? ????????? ????????? ?? ???????????
???????. ???????????????? ????????? ????????????? ???? ???????? ????? ????????????? ??????????????. ???????? ????????? ????????????? ??????????? ? ?????????????? ?????? ???????????????? ???????????????????? ???????, ????-????????????? ? ??? 1?-?????????????.
????????????????? ?????
1. ??????
????????????? ?????????? 2,6-??(???????????????)-3,5-???????-4-??????????????.
???????? ???? ???????????????? ????-?????????????? (0,1 ?) ?????????????? ? ????? ??????????? ??????????? ????? (2 ??), ???????? ???????? ????? ? ??????? ???????????? ???????? ???? ????-?????????????. ????? ???????? ? ???????? ????????????? ??? ????????????? ? ??????? ????? ??? ??????????? ????????, ??? ???? ???? ??????????? ????? ?????????
?? ???????? ?? ???????. ??????? ????????? ? ??????? ???????. ?????? ?????????????? ????
?????? ????? ???????????????, ???????? ?????????. ????????? ???????? ??????? ?? ??????????? ??????????? ????? ????????? ?????????? ?? ? ???????? ?? ????????????? ? ??????????? ??????????????????? ?? ???????????? ?????. ?? ???? ??????? ??????? ??? ??????? ?????. ?????????? ??????? ????????????? ?????? ??? ???????? ??? ????????? ???????????.
???? ????????? ????????? ??????-?????????? ? ???????????? ?????? ?????????? ???????.
????????????? 2,6-??(???????????????)-3,5-???????-4-?????????????? ????????? ??? ??????????? ???????? ? ?????????????.
????????? ???? 3,5-??(???????????????)-2,6-???????-1,4-??????????-1-?????? (IV
a). ????? 52 %, ?????? ?????????, ?.??. 117 ? 118 °?. ?????? ??? 1? (CDCl3), ?, ?.?.: 2.24 ?
(3?, Ph??3), 2.38 ? (3?, Ph??3), 3.902 ? (3?, COO??3), 3.907 ? (3?, COO??3), 4.25 ? (3?, NO??3).
????-??????, m/z (I???., %): 281 (17) [M]+, 250 (41), 234 (32), 218 (29), 190 (16), 120(21), 97(25), 67
(100), 59 (37), 57(56), 55(46), 43 (68), 41 (36), 39 (48).
# 236 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ????????????? ????????????? ????-??????????????
???????? ???? 3,5-??(???????????????)-2,6-???????-1,4-??????????-1-?????? (IV
b). ????? 17 %, ?????? ?????????, ?.??. 86 ? 87 °?. ?????? ??? 1? (CDCl3), ?, ?.?.: 1.43 ? (3?,
NO?2?5), 2.25 ? (3?, Ph??3), 2.40 ? (3?, Ph??3), 3.902 ? (3?, COO??3), 3.907 ? (3?, COO??3),
4.50 ? (2?, NO?2?5). ????-??????, m/z (I???., %): 295 (35) [M]+, 264 (55), 250 (63), 234 (49), 218 (55),
190 (38), 67 (100), 59 (33), 43 (40).
????????? ???? 3,5-??(??????????????)-2,6-???????-1,4-??????????-1-?????? (IV
?). ????? 55 %, ?????? ?????????, ?.??. 115 ? 116 °?. ?????? ??? 1? (CDCl3), ?, ?.?.: 1.371 ?
(3?, COO?2?5), 1.378 ? (3?, COO?2?5), 2.24 ? (3?, Ph??3), 2.38 ? (3?, Ph??3), 4.24 c (3?, NO??3),
4.379 ? (2?, COO?2?5), 4.383 ? (2?, COO?2?5). ????-??????, m/z (I???., %): 309 (25) [M]+, 264 (71),
219 (68), 204 (85), 188 (41), 67 (100), 66 (34), 57 (22), 55 (23), 43 (61), 39 (69).
???????? ???? 3,5-??(??????????????)-2,6-???????-1,4-??????????-1-?????? (IV d).
????? 80 %, ?????? ?????????, ?.??. 95 ? 96 °?. ?????? ??? 1? (CDCl3), ?, ?.?.: 1.367 ? (3?,
COO?2?5), 1.373 ? (3?, COO?2?5), 1.42 ? (3?, NO?2?5), 2.24 ? (3?, Ph??3), 2.40 ? (3?, Ph??3),
4.375 ? (2?, COO?2?5), 4.378 ? (2?, COO?2?5), 4.48 ? (3?, NO?2?5). ????-??????, m/z (I???., %):
323 (17) [M]+, 279 (28), 278 (60), 233 (56), 220 (47), 205 (48), 204 (100), 188 (28), 177 (21), 120 (17), 67
(73), 43 (22).
????????? ???? 3,5-??(??????????????????)-2,6-???????-1,4-??????????-1-??????
(IV e). ????? 60 %, ?????? ?????????, ?.??. 55 ? 56 °?. ?????? ??? 1? (CDCl3), ?, ?.?.: 1.01 ?
(6?, 2COO?3?7), 1.75-1.77 ??. ? (4?, 2COO?3?7), 2.24 ? (3?, Ph??3), 2.38 ? (3?, Ph??3), 4.24 ?
(3?, NO??3), 4.28 ? (4?, 2COO?3?7). ????-??????, m/z (I???., %): 337 [M]+.
????????
????
3,5-??(??????????????????)-2,6-???????-1,4-??????????-1?????? (IV f). ????? 72 %, ?????? ?????????, ?.??. 92 ? 93 °?. ?????? ??? 1? (CDCl 3), ?,
?.?.: 0.99 ? (6?, 2COO?3?7), 1.43 ? (3?, NO?2?5), 1.75-1.77 ??. ? (4 ?, 2COO?3?7), 2.24 ? (3?,
Ph?? 3), 2.40 ? (3?, Ph?? 3), 4.29 ? (4?, 2 COO?3?7), 4.49 ? (2?, NO?2?5). ????-??????, m/z
(I???., %): 351 [M]+.
????????? ???? 3,5-??(?????????????????)-2,6-???????-1,4-??????????-1-??????
(IV g). ????? 46 %, ?????? ?????????, ?.??. 53 ? 55 °?. ?????? ??? 1? (CDCl3), ?, ?.?.: 0.960
? (3H, COO-?4?9), 0.964 ? (3H, COO-?4?9), 1.40-1.44 ? (4H, 2COO-?4?9), 1.65-1.71 ? (4H, 2COO?4?9), 2.23 ? (3?, Ph??3), 2.38 ? (3?, Ph??3), 4.23 ? (3?, NO??3), 4.317 ? (2?, COO-?4?9), 4.320 ?
(2?, COO-?4?9). ????-??????, m/z (I???., %): 365 (30) [M]+, 310 (35), 292 (97), 236 (77), 219 (83), 205
(20), 188 (31), 120 (20), 67 (66), 57 (100), 43 (56), 41 (90).
???????? ???? 3,5-??(?????????????????)-2,6-???????-1,4-??????????-1-??????
(IV h). ????? 47 %, ?????? ?????????, ?.??. 68 ? 70 °?. ?????? ??? 1? (CDCl 3), ?, ?.?.:
0.960 ? (3H, COO-? 4?9), 0.965 ? (3H, COO-? 4?9), 1.41-1.42 ? (4H, 2COO-? 4?9), 1.43 ? (3?,
NO?2?5), 1.71-1.76 ? (4H, 2COO-? 4?9), 2.23 ? (3?, Ph?? 3), 2.39 ? (3?, Ph?? 3), 4.310 ? (2?,
COO-? 4?9), 4.317 ? (2?, COO-? 4?9), 4.48 ? (2?, NO?2?5). ????-??????, m/z (I???., %): 379 (26)
[M]+, 324 (33), 306 (100), 250 (75), 233 (90), 205 (57), 188 (39), 120 (21), 67 (74), 57 (94), 43 (48),
41 (95).
????????? ???? 3,5-??(????????????????????)-2,6-???????-1,4-??????????-1?????? (IV i). ????? 49 %, ?????? ?????????, ?.??. 86 ? 87 °?. ?????? ??? 1? (CDCl3),
?, ?.?.: 0.988 ? (6?, COO-i-?4?9), 0.995 ? (6?, COO-i-?4?9), 2.043 ?(2?, 2COO-i-?4?9), 2.24 ?
(3?, Ph??3), 2.39 ? (3?, Ph??3), 4.106 ? (2?, COO-i-?4?9), 4.110 ? (2?, COO-i-?4?9), 4.24 ? (3?,
# 237 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ????????????? ????????????? ????-??????????????
NO??3). ????-??????, m/z (I???., %): 365 (10) [M]+, 101 (21), 74 (23), 57 (100), 56 (45), 44 (21), 43
(44), 41 (45).
???????? ???? 3,5-??(????????????????????)-2,6-???????-1,4-??????????-1-??????
(IV j). ????? 52 %, ?????? ?????????, ?.??. 55 ? 56 °?. ?????? ??? 1? (CDCl3), ?, ?.?.: 0.986 ?
(6?, COO-i-?4?9), 0.992 ? (6?, COO-i-?4?9), 1.43 ? (3?, NO?2?5), 2.04 ? (2?, 2COO-i-?4?9), 2.24
? (3?, Ph??3), 2.40 ? (3?, Ph??3), 4.12 ? (4?, 2COO-i-?4?9), 4.48 ? (2?, NO?2?5). ????-??????,
m/z (I???., %): 379 (17) [M]+, 306 (64), 250 (53), 233 (66), 232 (40), 205 (45), 204 (38), 188 (31), 67 (66),
57 (100), 43 (47), 41 (91).
????????? ???? 3,5-??(???????????????????)-2,6-???????-1,4-??????????-1-??????
(IV k). ????? 86 %, ?????? ?????????, ?.??. 74 ? 75 °?. ?????? ??? 1? (CDCl3), ?, ?.?.: 0.953 ?
(6?, COO-i-?5?11), 0.958 ? (6?, COO-i-?5?11), 1.63 ?(4?, 2COO-i-?5?11), 1.74 ?(2?, 2COO-i-?5?11),
2.23 ? (3?, Ph??3), 2.37 ? (3?, Ph??3), 4.346 ? (2?, COO-i-?5?11), 4.349 ? (2?, COO-i-?5?11), 4.23 ?
(3?, NO??3). ????-??????, m/z (I???., %): 393 (5) [M]+, 307 (65), 306 (43), 305 (35), 237 (27), 236 (45),
219 (100), 218 (33), 188 (22), 120 (11), 71 (31), 67 (26), 43 (89), 41 (32), 39 (12).
???????? ???? 3,5-??(???????????????????)-2,6-?????????????????-1-?????? (IV
l). ????? 83 %, ?????? ?????????, ?.??. 60 ? 61 °?. ?????? ??? 1? (CDCl3), ?, ?.?.: 0.956 ? (6?,
COO-i-?5?11), 0.959 ? (6?, COO-i-?5?11), 1.43 ? (3?, NO?2?5), 1.63 ? (4?, 2COO-i-?5?11), 1.75 ?
(2?, 2COO-i-?5?11), 2.23 ? (3?, Ph??3), 2.39 ? (3?, Ph??3), 4.35 ? (4?, 2COO-i-?5?11), 4.48 ? (2?,
NO?2?5). ????-??????, m/z (I???., %): 407 (6) [M]+, 321 (65), 320 (44), 319 (36), 251 (24), 250 (42), 233
(100), 232 (27), 188 (23), 67 (25), 43 (89), 41 (26), 39 (8).
2. ??????? ?????? ???1?- ? ????-????????
??????? ???1? ???????? ?? ??????? Avance III 600 Bruker ? ????? ?????????????????.
????-??????? ?????????????? ?? ??????? Finnigan MAT 8200.
3. ???????? ????????-?????????? ????????
????????-?????????? ??????????? ??????????? ? ?????????????? ???????????? ????????? FireFly [11] ?????????????? ??????? ??????-???? ? ?????? 6-31G ? ??????????
???????-?????? ??????? ??????? [12-15].
4. ???????? ???????????????????? ??????????? ????????? ?????????? ?????
3,5-??(??????????????)-2,6-???????-1,4-??????????-1-??????
?????????? ????????????? ?????? ???????? ? ?????????????? Cu K?-????????? ??
????????????? X?Pert PRO ? ?????????? PIXcel (Panalytical), ?????????? ?????????? ??????????????. ??????? ????????? ? ???????? ?????? ? ?????????????? ??????? ?????? ???????
??????. ??????? ??????: ???????? ?? 3 ?? 90° ?? 2?, ????? 0,013°, ?t ? 50?.
????????? ???????????? ??????? ?????????? ? ???????? ??? ?????? ????????, ????????? ? ??????? [16, 17]. ????? ?????? ????????? ??????????? ??????? ?????-?????
? ????????? FOX [18]. ? ???????? ???????? ?????? ???? ???????????? ????????? ??????
?14H17NO6 [19]. ????????? ????????? ?????????? ????????? ????????? ??????????? ??????????????? ???????? ? ??????? ????????? FullProf [19]. ??? ??????????? ????????????
?????????????????? ????????? ?????????? ??????? ????????? ??????????? ??????# 238 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ????????????? ????????????? ????-??????????????
?????? ?? ?????????? ???????? (?????????? ??????????) ????????????? ??????????? ?
??????? ??????? ?????????????. ???????? ????????? ??????????? ????? ???????, ?????
??? ??????????? ????????? ??????? ????????? ? ????????? ???????????????? ???????
???????? ????????? ?????????? ? ????? ?????????????? ? ?????????. «??????» ??????????? ????????? ???????? ????????? ????????? ???????, ??????? ??????????? ??? ????????? ????????? ????????? ????????? ??????. ??????????? ?????????? ????? ?? ?????????.
????????? ????????? ?????????????? ????? ???????????? ?????? ??????? ???????????
[21]. ? ?????????????? ????????? XP [24] ?? ????????? ????? ????????? ? ?????? ????????? ???? ????????? ????? ????????, ?????? ????????????? ? ??????????????? ?????????.
???????? ????????? ?????? ?????????? ? ?????????? ???????????. ????????? ????????????
????? ??????????? ????????????????? ???????????????? ??? ????????? ?????? ????????? ??????????? ?? ???. 4. ? ??????? 1 ????????? ???????????????????? ??????????????
????????? ?????????? ????? 3,5-??(??????????????)-2,6-???????-1,4-??????????-1-?????? ,
? ?? ???. 5 ? 6 ???????? ??????????????? ????????.
??????? 1. ???????????????????? ????????? ?????????? ????? 3,5-??(??????????????)-2,6-???????1,4-??????????-1-?????? (I) ? ?????????????? ???????????????????? ??c?????????
???????????? ???????
?15H19NO6
???????????? ???
309,31
???????????????? ??????
P21/c
7,3305(3)
a, ?
b, ?
10,5034(8)
c, ?
21,1531(17)
?, ????.
90
?, ????.
93.785(5)
90
?, ????.
1625,14(19)
?????, ?3
4
????? ?????????? ?????? ?? ??????
????????? d???, ?/??3
1,264
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295
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X?Pert PRO
Cu K?
?????????
?1 = 1,54056, ?2 = 1,54439
????? ?????, ?
7,017? 89,983
??????? ?????? 2?, ????.
?????????? ?????
3192
?????????? ?????????
3369
72
?????????? ?????????? ??????????
Rp, %
6,86
Rwp, %
9,42
Rexp, %
7,42
S = Rwp /Rexp
1,27
# 239 #
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???. 4. ????????????????? (?????), ??????????? (???????? ?????) ? ?????????? ??????????????,
??????????????? ??????????? ??????? ????????? ?14H16KNO6 . ????????? ???????????? ?????????
??????? ????????????? ????????. ?? ??????? ? ??????? ??????? ?????????????? ? ???????????
????????
???. 5. ????????? ???????? ?????????? ????? 3,5-??(??????????????)-2,6-???????-1,4-??????????-1?????? (?15H19NO6)
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ????????????? ????????????? ????-??????????????
???. 6. ??????? ??????? ?????????? ????? 3,5-??(??????????????)-2,6-???????-1,4-??????????-1-??????
? ??????????????? ???????
?????????? ? ??????????
????????, ??? ? ??????? ????????????? ?????????????? ??????? ??? ?????????????
?????? ? ????? ????????? ?????????????? ? ?????????????, ? ?????? ????????-???????????
??????? ??????????? ??????????? ???? ????????? ??????????? ???????? ????????????????????? ?? ???????? ?? ?????? ???????.
? ??????? 2 ???????????? ???????? ????????? ????????? ?? ?????????? ??????????????
? ?????????????, ?????????? ? ?????????? ??????????? ???????? ???????. ? ????? ??????
???????? ??????? ?? ????????????? ??????? ???????????????? ?????????????? ??????????
??????? ?? ????? ????????? ????????????? ??????. ? ??????? ?????????? ?????? ??????????
0,17?. ?????? ??????????????????? ????? ? ???? (Me, ?,Am) ???????? ???? ? ??????????
?????????? ???????? ?????? ?? ??????????????? ???????, ???, ????????, ??????? ? ??????????? ?????????? ?? ?-?????? ? ?????????? ???????. ????????? ???????????? ??? ?????????? ?????????????? ?? ????? ????????? ????????????? ?????? ????? ???? ??????????????? ??????????? ?????? ????????????.
# 241 #
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?.?. ????????, ?.?. ????????? ??????? ????????????? ????????????? ????-??????????????
??????? 2. ??????????? ?????? ????????????? ???????
?????
???????? ??????????????
???????? ?????????????
IIa
-0,545
-0,373
IIb
-0,539
-0,374
IIc
-0,539
-0,376
IId
-0,523
-0,389
IIe
-0,536
-0,372
??????? 3. ???????? ?????? ??????? ??????? ????????????? ????-?????????????????????? ? ?????????
?????? ????-?????????????????????
????????
???????? ???????, ?????? (?III-EIV)
IIIa ? Iva
0,0135
IIIb ? Ivb
0,0040
IIIc ? Ivc
0,0049
IIId ? IVd
0,0062
IIIe ? Ive
0,0047
IIIf ? Ivf
0,0061
IIIg ? Ivg
0,0010
IIIh ? Ivh
0,0063
? ?????? ???????, ????????????? ??????????? ???????? ????????? ????????? ????????????? ?????????????? ? ????????? ?????? ??????? ???????, ?????????????? ?? ?????
????????? ????????????? ???? ????????????? (????. 3), ??????????????? ? ??????? ?????????????? ?????? ????????? ????????????? ?? ?????????????, ? ?????????? ???? ?????? ?????????????? ????? ????????????? ????-?????????????????????.
????????????????? ????????? ????? ????????????? ???? ????????? ?? ??????? ???????? ????? ?????????????? ? ????????? ???????? ? ????? ??????????? ?????. ?? ???? ??????? ???? ???????? ??????????????? ???????? ????????????? ??????? ?????. ?????? ????????? ??? ??????????? ????-??????????????????? ???????????, ??????? ????????? ?
????????????????? ?????. ? ?????? ????-??????? ????????????? ???????????? ???, ?????
??????????????? ???????????? ????? ?????????? ?????, ? ????????? ????????? ????????,
???????????? ? ?????????? ???????????? ?????. ??????????????? ????????? ?????????? ????? 3,5-??(??????????????)-2,6-???????-1,4-??????????-1-?????? (?15H19NO6) ???? ??????????
??????????????????? ????????, ?? ???????????????????? ???????. ???????? ????? ???????????? ????????? (???. 4). ? ??????????????? ?????? ?????????? ?????? ?????????? ?????????? ???????, ?????? ???????? ????????????. ????????? ??????????????????? ?????
????????? ??????????? ??????????????? ??????, ???????, ??????????????, ?????????? ????:
79.89 ? ? 76.84?. ???????????? ????????????? ?? ?????? ??????? ????????? ??????. ??????
?????? ??????????? (=O, -CH3, -CH3, =NO(CH3) ) ????????? ? ????????? ??????. ??????????# 242 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ????????????? ????????????? ????-??????????????
??????? 4. ???????? ?????????? ?????????? ? ????????? ?????????? ????? 3,5-??(??????????????)2,6-???????-1,4-??????????-1-??????
???? ?
???? ?
d(A-B), (? )
???? ?
???? ?
d(A-B), (? )
1
2
3
1
2
3
O14
C8
1,338
C6
C5
1,446
O14
C20
1,464
C6
C11
1,514
O15
C12
1,220
C7
C6
1,355
O13
C8
1,211
C7
C2
1,451
O1
C2
1,199
C7
C12
1,502
O16
C12
1,342
C8
O13
1,211
O16
C18
1,451
C8
O14
1,338
O17
N10
1,399
C8
C3
1,497
O17
C22
1,430
C9
C4
1,506
C2
O1
1,199
C11
C6
1,514
C2
C3
1,445
C12
O15
1,220
C2
C7
1,451
C12
O16
1,342
C3
C4
1,351
C12
C7
1,502
C3
C2
1,445
C18
O16
1,451
C3
C8
1,497
C18
C19
1,476
C4
C3
1,351
C19
C18
1,476
C4
C5
1,452
C20
O14
1,464
C4
C9
1,506
C20
C21
1,481
C5
N10
1,300
C21
C20
1,481
C5
C6
1,446
C22
O17
1,430
C5
C4
1,452
N10
C5
1,300
C6
C7
1,355
N10
O17
1,399
??? ??????, ??-????????, ????? ?-?????????? ? ????????????, ??? ??????????? ? ??????? ????????? ????????? ??????????? ??????, (d(?3-?2) =1.44(1) Е, d(?3-?2) =1.35(1) Е). ???????????
?????????? C2-O1 (1.20Е) ? C5-N10 (1.30Е) ????? ????????? ?? ????????????? ??????? ??????
? ??????? ????????? ???????????? ? ????????????? ?????. ?????? ?????????? ??????????
? ???? ????????? ? ????. 4, 5.
??????????????? ????????? ???????????? ?????????? ??????? ??????? ????? ??? ?
(???. 6). ? ??????? ???????? ????????????? ?? ?????, ????????? ??????? ?????????. ?????????? ????? ??????????? ?????????? ????? ? ????? ?????????? 3,63 Е. ?????????? ?????
???????????, ??????? ??????????? ??????? ???????? ??????????? ?????????? ???????? ??????? ? ?????? ?? ??????????? ?????????.
?????? ?????????? ? ???????? ?????? ???? ???????? ??? ??????? ??? 1?-????????.
???? ?? ??? 1?-???????? ?????????? ?????????, ?????????, ??? ?? ???? ??????? ???????????? ????????? ????? ??????????????? ???????????? (???. 3, ???? b). ? ???????? ???
1
? ??????? ????????? ????? ?????? ? ??????? ????????? ????? ????????????? ???????# 243 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? 5. ???????? ???? ????? ??????? ? ????????? ?????????? ????? 3,5-??(??????????????)-2,6???????-1,4-??????????-1-??????
???? A
???? B
???? ?
???? (ABC)
???? A
???? B
???? ?
???? (ABC)
1
2
3
4
1
2
3
4
C8
O14
C20
121.06
C7
C6
C5
120.12
C12
O16
C18
123.01
C7
C6
C11
121.87
N10
O17
C22
107.43
C5
C6
C11
117.94
O1
C2
C3
120.30
C6
C7
C2
119.90
O1
C2
C7
119.96
C6
C7
C12
120.26
C3
C2
C7
119.69
C2
C7
C12
119.64
C4
C3
C2
120.52
O13
C8
O14
119.98
C4
C3
C8
120.74
O13
C8
C3
121.45
C2
C3
C8
118.69
O14
C8
C3
118.56
C3
C4
C5
119.67
O15
C12
O16
119.89
C3
C4
C9
116.09
O15
C12
C7
120.86
C5
C4
C9
124.22
O16
C12
C7
119.23
N10
C5
C6
124.11
O16
C18
C19
102.37
N10
C5
C4
115.93
O14
C20
C21
107.59
C6
C5
C4
119.94
C5
N10
O17
122.28
???. 7. ??? 1?-?????? ?????????? ????? 3,5-??(??????????????)-2,6-???????-1,4-??????????-1-??????.
?? ??????????? ????????? ??????? ? ??????? 1,37 ?.?. ? ? ??????? 4,38 ?.?. ????? «???????» ????????
????????? ? ??????????? ????? ????????????? ???????????? ??-?? ???- ???? ???????????????? ??
????????? ? ????????????? ??????
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ????????????? ????????????? ????-??????????????
????? ????????? ???????????????? ??-?? ???- ???? ???????????????? ???? ????????????
?? ????????? ? ????????????? ??????, ??-?? ???? ??? ??????????? ??????????? ? ??????
?????????. ?? ???? ??????? ??????? ???? ????????? ????? ?????? ?? ??? ??????? ?????????? ?????????????, ? ??????? ???????????. ? ?? ?? ????? ????????? ?????? ????? ??????
?? ?????????? ??????? ????????????? ???????????, ??????? ?? ??????? ???? ???????
??????. ???, ????????? ?????? ????? ?????? ??????????? ????? ????????? ? ?????? ????,
???????? ? ????? ????????? ? ?????? ???? ? ????? ????????? ? ???????. ????? ??????? ?????? ????????? ?????????????? ????, ??? ????????????? ?????? ?? ???? ??????? ?? ?????
????????? ?????????????.
??? 1?-?????? ?????????? ????? 3,5-??(??????????????)-2,6-???????-1,4-??????????1-?????? ??????????? ?? ???. 7. ??? 1?-????????? ?????? ?????? ?????????????? ??-??
???- ???? ???????????????? ?? ????????? ? ????????????? ?????? ? ???? ??????? ? ????
????????? ? ?????????? ?????????????? ? ??????????? 2,24 ? 2,38 ?.?. ?????????? ??????? ???????? ????????????? ????? ?? ??? ?? ??????? ???? «???????» ???????: ???????? ?
??????????? 1,371 ? 1,378 ?.?., ? ????? ???????? 4,379 ? 4,383 ?.?. ?????? ????????? ??????
??????-??????? ? ?????????? 4,24.
????? ???????, ? ?????????? ???????????? ???????????? ???????????, ???, ???????? ??
??????? ??????????? ?????? ?? ????? ????????? ??????????????, ??????? ?????????????
????????????? ?????????????? ????????? ?? ????? ????????? ????????????? ? ???????????? ????????????? ????? ???????? ????????? ?????? ??????????????? ????????????.
???????????? ????????? ??? ?????????? ????????? ???????????? ??????????? ?
????? ?? (???. ????????? ? 02.740.11.0269 ? ? ?2263) ? ?????????????? ?????? ?? ????????????? ?????? (ICDD, ????? ? 10-93).
?????? ??????????
1. ????? ?.?., ????????? ?.?., ?????? ?.?. ??????????? ???????????????-????????????
????-?????????????? // ?????? ???????????? ?????. 2007. 43. 545-548.
2. ???????? ?.?., ?????? ?.?., ???? ?.?., ????? ?.?., ????????? ?.?. ??????????????
???????????? ????????????? ?-?????????????? // ?????? ???????????? ?????. 2010. 46. 527529.
3. Eiden F., Leister H.P., Mayer D. 5-Aminoacetamido-4,6-dimethyl-2-hydroxy-isophtals?urediethylester: Synthese und Untersuchung antiarrhythmischer Eigenschaften // Arzneimittel-Forschung.
1983. 33. 101-105.
4. ???????? ?.?., ???????? ?.?., ?????? ?.?., ????? ?.?. ??????????? ? ??????????????? ?-?????????????? ?? ?????? ???????????????????? ???????// ?????? ???, ?????
«?????». 2010. 3. 45-57.
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nitrosophenolic structure // J.Chem.Soc. 1932. ? 5. P. 1395-1398.
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de l?elimination de l?alcool // Bull.Soc.Chim.France. 1972. P. 4061-4067.
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Molecular Electronic Structure System // J. Comput. Chem. 1993. 14. 1347-1363.
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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ????????????? ????????????? ????-??????????????
Alkylation of Persubstituted para-Ninrosophenols
Dimitri G.Slaschinina, Yuri A.Alemasov,
Dimitri I.Ilushkina, William A.Sokolenkob,
Michael S.Tovbisa and Sergei D.Kirikb,c
a
Siberian State Technological University,
82. Mira, Krasnoyarsk, 660049 Russia
b
Institute of Chemistry and Chemical Technology,
42 Marx St., Krasnoyarsk, 660049 Russia
c
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
Theoretical and experimental approaches were applied for the investigation of reactivity of
persubstituted 4-nitrosophenols in the reaction with alkyl haloids by example of potassium salt of 2,6di (alkoxy carbonyl)-3,5-dimethyl-4-nitrosophenol. Using unempirical Hartry-Fock approach it was
shown that negative charge of the anion locates in much extend on oxygen of hydroxyl group, where as
the estimation of a total energy of alkylated products points out benefit of alkylation onto oxygen atom
of nitroso group yielding quinonoxime ester.
The methylating and ethylating reactions of persubstituted nitrosophenols were carried out. The
obtained products were investigated using X-ray diffraction, 1? NMR and mass-spectroscopy. The
crystal structure of methyl ether of 2,6-di (alkoxy carbonyl)-3,5-dimethyl 1,4-benzoquinone-1-oxime
(?15H19NO6) (I) was determined by X-ray powder diffraction technique. The unit cell parameters are:
a =7.3322(6) Е, b = 10.5039(12) Е, c = c 21.1520(20) Е, ? = 93.742(6)°, V = 1625.58(2) Е33 Z=4, Sp.Gr.
P21/c. The structure modeling was carried out in direct space by Monte?Carlo approach applying
rigid and soft restrictions. Structure refinement was completed by Rietveld method. It was established
the alkylation was directed into oxygen atom of nitroso group. The molecules(I) in crystal structure
are packed in columns along axis a with pairwise convergence in column up to the distance of 3.63 Е
due to turn of every second molecules around the axis on 180o. In the molecular structure the methyl
oxime group is oriented in the benzene plane and have ?-conjugation with the ring. Ethoxycarbonyl
groups are turned nearly perpendicular to the ring. Other obtained compounds have a structure of
alkyl ether of 1,4-benzoquinone-1-oxime, that was proved by 1? NMR spectroscopy.
Keywords: hexasubstituted nitrosophenols, alkylation, nitrosophenols, alkyl ethers of
1,4-benzoquinone-1-oximes, polycrystalline X-ray diffraction analysis, Hartree-Fock quantumchemical calculations, 1? NMR spectroscopy, mass spectrometry.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 3 (2011 4) 248-256
~~~
??? 547.914.4+581.192.2
??????? ??????? ????????????
??????????? ???????? ??????? ???? ??????
? ?? ????????? ?? ????? ? ?????? ??????????
?.?. ??????????,?*,
?.?. ??????????, ?. ?. ??????????,
?. ?. ??????, ?.?.???????
?
???????? ????? ? ?????????? ?????????? ?? ???,
?????? 660049, ??????????, ??. ?. ??????, 42
?
????????? ??????????? ???????????,
?????? 660041, ??????????, ??. ?????????, 79
?
?????????? ???????????????
??????????? ??????? ? ???????,
?????? 141221, ?????????? ???., ?????????? ?????,
?. ?????????, ??. ???????, 99 1
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
??????? ??????? ??????? ???????????? ??????????? ???????? ??????? ???? ?????? ? ee
??????????????? ????????? ?????????? ??????? ????? ?? ????? ? ?????? ??????????
????????????? ?????????. ???????????, ??? ? ??????????? ?? ??????? ???????????? ?????
???????? ????????? ? ?????? ??????????? ???????????? ????????, ??????????????
????????, ???????? ? ???????. ????????, ??? ???????? ? ?????????? ???????????
???????????? ???????? 85-91 % ??????? ?? ???????? ??????? ??????? 2-5 ?? ? ??????????????
?????????????? ??????? ??????? 10-20 ??. ????????? ???????????? ????????
???????????? ???????? ??????????? ???????, FTIR, ??? ? ?13???-?????????????.
???????? ?????: ??????? ???? ??????, ????????????, ??????????? ???????, ???????????
????????, ?????????, ?????????? ???.
????????? ???????????? ??????? ? ??? ??????????? ???????? ??????? ????????
????????????? ??????????. ????????, ??? ??????? ???????? ???????????????? ??????????,
?????????????????, ???????????????, ??????????? ? ?????????????????? ???????????. ?
????????? ????? ????????????? ????? 240 ??????????? ????????, ?????????? ??????? ???-
*
1
Corresponding author E-mail address: ksa@icct.ru
© Siberian Federal University. All rights reserved
# 248 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ?????????? ??????? ??????? ???????????? ??????????? ???????? ??????? ???? ???????
??????????????? ??????????, ? ??? ????? ???????????, ??????????? ???????, ????????????????, ?????????????? ?????????? ? ??????? ????? ???????? [1-9].
????????? ??????? ????????? ?????? ???????? ??????????, ? ????????, ?? ????????
???????????? ???????? ? ??????? ???????????? ?????????????? ?????? ????????? ???????? ??
??????? ?????? [6, 10, 11].
???????? ?????????? ????????????? ??????? ????????? ???????? ???????? ?? ???????
???? ??????, ?????????? ?? ?????????? ?????? ?????????? ???????? ?? ??????? ? ??? ???????????? ????????, ??????????? ? ???????? ????????? [12-16].
?? ??????? ????????? ????????? ???????? ?? ??????? ???? ?????? ???? ????????, ??? ??????????????? ??????????????? ????????? ??????? ?????????? ??????? ????? ? ????????
«????????? ?????????????» ? ??????? 60 ? ????????? ????????? ????????????????? ????????
???????????? ?? 30 ??? [15].
??????????? ??????? ?????? ? ?????? ????????? ???????????? ? ???????????? ????????????????????? ???????, ????? ??? ?????????, ?????????, ?????????, ? ????? ???????? ???????. ????? ????, ??????????? ??????? ???????????? ????? ??????? ? ????????? ????????,
??????? ???????????? ? ???????? ???????????? ????????? [17].
????????? ??????? ? ??????????? ??????? ???????? ????????????? ?????????????????
???????????, ?? ??????????? ???????? ? ??????????? ???????? ? ????? ????????? ????? ????????????????? ????????. ????? ????, ?? ???????? ? ?????????? ???????? ??????????? ???????? ????? ?????????????? ??? ???????? ????? ??????????? ????????.
? ??????????? ????? ????? ?? ????????? ? ???????? ??????? ????????????? ?????????? ?? ??????? ???? ?????? [12-16, 18-21] ????? ?????? ?????? ???????? ???????? ???????
??????? ??????????????? ??????????????? ????????? ?????????? ??????? ????? ???????????? ??????? ???? ?????? ? ?? ???????????? ??????????? ???????? ?? ????? ? ?????? ?????????? ??????????.
??????????? ???????? ? 3 ?, 28 ? ??????????? ? ??? 20 (29)- ?? (1) ? ??????? ???? ??????????? ??????? ? ???????? (???. 1).
???. 1. ????????? ???????????? ????????
# 249 #
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?.?. ?????????, ?.?. ?????????? ??????? ??????? ???????????? ??????????? ???????? ??????? ???? ???????
???????? ????????????
? ???????? ????????? ????? ???????????? ??????? ???? ?????? Betula pendula Roth, ???????????? ?? ??????? 2-5, 10-20 ??, ? ???????, ?????????????? ?????????? ??????? ?????.
????????? ??????? ?????????? ??????? ????? ? ???????? «????????? ?????????????» ????????? ?? ?????????, ????????? ? ??????? [22, 23]. ?????? ??????????? ??????? ??????? ???
???????? ?? ????????? ? ????? ????????? ????????? ?? ?????, ????????? ? ?????? [15].
??????????? ???????? ????????????? ? ????????????????????? ?? ??????? ? ??????????? ??????????????? ???? ????? ??-? ?? ????????, ????????? ? ??????? [13].
?????? ?????????? ????????? ?? ??????? ???????????? 6890N (Agilent, ???). ???????
????????????? ???? ??????????: ??????????? ??????? ??-5 ?????? 30 ?, ?????????? ??????? 0,32 ??. ???-???????? ? ????; ???????? ?????? ? 1,5 ??/???; ??????????? ????? ???? ?
250 є?; ????????? ??????????? ? 180 є?, ?????? ??????????? ?? 320 є? ?? ????????? 10 є?/???,
10 ??? ?????????????? ??????. ???????? ????????-????????????? (???).
?????????? ?????? ???????????? ???????? ????????? ? ?????????????? ???????????
??????????? FLASHTM 1112.
??-?????????????????? ???????????? ???????????? ???????? ????????? ?? FTIR-????? ?
???????????? Vector 22 (Bruker). ????????? ???????? ?????????? ? ????????? ?????? ? ??????????? ???????. ????????? ???????????? ?????????? ????????? ? ?????????????? ????????? OPUS/Y (?????? 2.2).
???- ? 13?-???-??????? ???? ????? ?? ???????????? Bruker Avance 600 ??? ??????? 600
MHz=(1H), ???????????? ? CDCl3.
?????????? ? ??????????
??? ????????? ???????????? ??????? ???? ?????? ? ??????????? ??????? ?????? ? ??????????? ???????? ? ??????? ????????? ????? ??????? ???????????? ? ?????????? ???????????? ????????.
??? ????????? ???????????? ???????? ? ?????????? ??????? ??????????? ???????????
(??????????? ????? ??????? ? ?????? ??????????? ???????) ?? 1:10 ?? 1:30, ??????? ??????????? ??????? (2-5 ? 10?20 ??) ? ????????????????? ????????????.
??? ??????????? (??) 1:10 ????? ???????? ???????????? ??????? ??????? ???????????
???????? ???????? 31 % ?? ????? ?.?.?. , ? ??????????? ?????? ??????????? ??????? ? 2 ????
(?? 1:20) ????? ???????? ?????????? ?? 45 % ?? ????? ?.?.?. ?????????? ?????? ???????????
??????? ? 3 ???? (?? 1:30) ?? ??????? ? ????????????? ????????? ?????? ????????, ???????
??????????? ????? ????????????? ???? ????????? ??? ?? 1:20.
??????? ??????? ??????????? ? ????????????????? ???????????? ??????? ?????? ??????????? ???????? ?? ????? ????????? ???????????? ?? ???. 2.
? ??????????? ????????????????? ???????????? ??????? ??????? ??????????? ???????? ?????????? ????? ?????????. ?????? ?????????? ????? ????????? 40-43 % ?? ????? ?.?.?.
??????? ??? ???????? ??????? ??????? 2-5 ?? ? 48-50 % ?? ????? ?.?.?. ??? ??????? ???????
10?20 ?? ??? ????????????????? 6-8 ?. ??????? ????????? ? ??????? ???????????? ???????
????????? ???? ???? ?????? ? ????? ?????????? ?????? ??? ???????????? ??????????? ???????, ??????? ????? ???????? ?????? ??? ??????? ??????? 10?20 ?? [15,24].
# 250 #
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50
1
45
2
40
35
30
25
20
0
2
4
6
8
10
????????????????? ????????????, ?
???. 2. ??????? ??????? ??????????? ??????? ? ????????????????? ?? ???????????? ???????????
???????? ?? ????? ?????????: 1 ? ??????? ??. 2-5 ??; 2 ? ??????? ??. 10-20 ??
???. 3. ??????? ????????????????? ???????????? ??????? ??????? 2-5 ?? ??????? ???????????
???????? ?? ?????? ?????????: 1 ? ??????????? ????????, 2 ? ????????????? ???????? ; 3 ? ???????;
4 ? ??????
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ?????????? ??????? ??????? ???????????? ??????????? ???????? ??????? ???? ???????
? ??????? 1 ? ?? ??????? 3 ???????????? ?????? ?? ?????? ? ??????? ????????? ???????????? ???????? ??????? ??????? ??????????? ????????.
? ??????? ????????? ???????????? ??????? ??????? ??????????? ???????? ???? ?????????? ????????? ??????????: ??????????? ????????, ????????????? ????????, ???????,
??????.
?????????????? ? ????. 1 ? ?? ???. 3 ?????? ??????????????? ? ???, ??? ? ???????????
????????????????? ???????????? ???????? ??????? ??????? 2-5 ?? ?? 12 ? ?????????? ???????????? ???????? ? ???????? ????????????? ?? 13 ?? 91 % ?? ????? ????????, ? ?????????
??????????? ?????????: ?????????????? ???????? ?? 60 ?? 7, ???????? ? ?? 22 ?? 1, ? ???????
?? 7 ?? 1 ????. %. ??? ??????? ??????? 10-20 ?? ? ??????????? ????????????????? ???????????? ?? 8 ?, ?????????? ???????????? ???????? ? ???????? ????????????? ?? 8 ?? 51 ????. %,
? ?????????? ????????? ??????????? ?????????: ?????????????? ???????? ?? 64 ?? 7, ???????? ? ?? 33 ?? 3, ? ??????? ? ?? 5 ?? 1 ????. %.
? ????? ?????????????? ???????? ???????????? ??????? ??????? ??????????? ???????? ? ?????????? ?????? ????????? ???? ????????? ??????????????? ????????? ???????
?????????? ??????? ????? ??????? «?????????» ????????????? [18, 25]. ? ??????? 2 ????????? ??????, ?????????????? ??????? ??????? ??????????????? ????????? ??????? ??????
??????? 10-20 ?? ?????????? ??????? ????? ? ???????????? ???????????? ???????????
???????? ?? ????? ? ?????? ?????????. ?? ??????? ???????, ??? ??????????????? ?????????
??????? ???? ?????? ????????? ????????? ????????????????? ???????????? ?? 30 ??? ? ???????? ????? ???????? ?? 47 % ????? ?.?.?.. ??????? ????????, ??? ???????? ???????????
??????? ???????? ???????? ????????????? ???????? (64 %), ? ?????????? ???????????? ???????? ? ???????? ?????????? 20 %.
??? ?????????? ????????????????? ???????????? ?????????????? ?????????????? ?????????? ??????? ????? ??? 240 є? ??????? ???? ?????? ?? 8 ? ????? ????????
?????????? ?? 54 % ????? ?.?.?., ? ?????????? ? ??? ???????????? ???????? ??????????
86 %.
?????????? ? ????????????????????? ?? ????????? ?????? ??????????? ???????? (3?-,
28-???????????-???-20(29)-??-1) ???????????? ????? ??????? ?????? ????? ? ????????????
????????? 149 є?.
??????? 1. ??????? ????????????????? ???????????? ???????? ??????? ??????? 2-5 ?? ???????
??????????? ???????? ?? ????? ? ?????? ?????????
?????? ?????????, % ????? ????????*
?????????????????
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????? ?????????, %
?? ????? ?.?.?.
???
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23
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58
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85
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45
91
7
1
1
??? ? ??????????? ????????, ??? ? ????????????? ????????.
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??????? 2. ??????? ????????????????? ????????? ? ???????????? ??????? ??????? 10-20 ??
??????????? ???????? ?? ????? ? ?????? ?????????*
?????????????????
????????????, ?
0,5
4,0
8,0
?????????????????
?????????, ?
?????
?????????,
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?????? ?????????, % ?? ????? ????????
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52
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45
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8
????????????????
???????
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????????????? ????????
?? ????????? ?????? ??????????? ??????? ?????????????????????? ???????????? ???????? ???????, %:(?) 80, (?) 10, (?) 10. ?????????, %:(?) 78, (?) 11, (?) 11.
??-?????? ???????????? ???????? ???????? ????????? ?.?. (?, ??-1): 3067,02 (?=?);
2956,98; 2871,82 (?-?); 1735,79; 1641,88 (?=?); 1461,80; 1423,84; 1389,97; 1355,27 (?-?); 1276,09;
1261,10; 1185,80; 1148,72; 1105,54; 1083,88 (?-?-?).
?????? 13?-??? ???????????? ???????? (CDCl3, ??, ?,): 174.92, 174.30, 150.17, 109.86,
80.63, 62.56, 55.39, 50.30, 48.91, 47.44, 46.44, 42.71, 40.91,38.38, 37.89, 37.57, 37.08, 34.56, 34.13,
29.80, 29.61, 28.08, 27.96, 27.74, 27.05, 25.18, 23.72, 20.81, 19.13, 18.17, 16.53, 16.15, 16.04, 14.75, 9.35,
9.24.
?????? ??? ???????????? ???????? (CDCl3, ??, ?,): 4.71m(1H,=CH2); 4.61m(1H,=CH2);
4.49dd(J 10.75 ??. J 5.65 ??, H3); 4.29dd(1H, J 12.1??, J 1.4 ??, H28); 3.87d(1H, J 12.1 ??, H28);
2.49(1H,ddd, J 11.2, J 11.2 , 5.76 ??, H19); 2.37(2H,q, J7.56 ??,); 2.345q, 2.347q (2H.J 7.54 ? J 7.64
??,) H32, H35; 1.70(3H,H30); 1.18t, 1,17t(6H,2CH3, J11.2 ??, H33 , H36); 1.16s,0.99s, 088s, 0.86s,
0.86s(15H,5CH3, H23, H24, H25, H26, H27).
?????? 13?-??? ???????????? ???????? ????? 36 ????????, ??? ????????????? ????????????? C36H54O4. ? ??????? ?? ???????? ??????????? ???????? ????? 6 ?????????????? ???????? ????????????? ?????: 174.92 ? 174.30 ?? (??? ???????????? ?????? C31, C34), 28.08 ?
27.74 (??? ???????????, C32 ? ?35), 9.35 ? 9.24 (??? ????????? ?????? ?33 ? ?36). ?????????
??????? ??????? ???????????? ???????? ?????? ? ???????? ??????? ????????? ????????. ???
?????????, ??? ????? ???????? ??????? ?? ?????????? ? ???? ???????.
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? ??????? ?? ???????? ? ??????? ??? ???????????? ???????? ??????? ???????, ???????
?? ?????????? ???????, ?????????? ????-????????? ??????????? ????????? ? ???? ????????????? ???????: 2.37q(CH2), 2.345q , 2.347q(CH2), 1.17t ? 1.18t (2CH3). ??? ??????? ??????????? ?????? ? ????? ?? ????????????? ????? ????????? ?? ????????????? ???????????????
????????.
??????
????????? ????????????? ?????? ? ??????? ????????? ???????????? ??????? ??????????? ???????? ???????? ? ?????????????? ?????????? ??????? ????? ? ???????? «?????????
?????????????» ??????? ???? ??????.
????????? ??????? ???????????? ???????, ??????????? ???????? ???????? ? ?????????? ??????? ? ?????????? ??????????? ???????????? ???????? ? ?????????????? ????????.
????????, ??? ???????? ? ?????????? ??????????? ???????????? ???????? (85-91 %) ??????? ?? ???????? ??????? ??????? 2-5 ?? ? ?????????????? ?????????????? ??????? ??????? 1020 ??.
???????????, ??? ??????????????? ????????? ??????? ??????? 10?20 ?? ?????????? ??????? ????? ????????? ????????? ????????????????? ???????????? ? 16 ??? ? ???????? ??????? ? ??????? 47 % ?? ????? ?.?.?., ??? ???? ???????? ??????????? ???????? ?????????????
???????? (64 ????. %).
????????? ???????????? ???????? ???????????? ???????? ??????????? ???????, FTIR.
??? ? ?13???-?????????????.
?????? ??????????
1. ????????? ?.?., ?????????? ?.?., ??????? ?.?. ? ??. ????????????????? ????????
?????????????? ???? ?????? // ????????????????? ? ??????????? ????????????. 1993. ?. 56.
?4. ?. 53?55.
2. ????????? ?.?., ??????? ?.?., ????? ?.?., ??????? ?.?. ? ??. ??????? ? ??? ???????????. ????? ? ????????????? ?????????? // ????? ? ????????? ??????????? ????????. 2005.
?13. ?. 1?30.
3. ??????? ?.?., ?????? ?.?., ??????????? ?.?. ? ??. ?????? ? ????????????????? ?????????? ????????????? ??????? ??????????? ??????? ? 28-????-???????????? // ?????????????????????? ??????. 2004. ?. 38. ?3. ?. 31?34.
4. Hisashi Matsuda, Atsushi Ishikado, Norihisa Nishida et al. Hepatoprotective, superoxide
scavenging and antioxidantive activities of aromatic constituents from the bark of betula platyphylla
var. japonica // Bioorganic & Medicinal Chemistry Letters. 1998. V. 8. P. 2939?2944.
5. ??????? ?.?., ?????? ?.?., ??????????? ?.?. ? ??. ?????? ? ??????????????? ????????
??????????? ????????? ?????????????? // ??????-???????????????? ??????. 2004. ?. 38.
?7. ?. 10 ? 14.
6. ????? ?.?., ???????? ?.?., ?????? ?.?. ? ??. ?????? ??????????????? ???????????
??????????? ? ??????????? ?????? ? ?? ????????????????? ?????????? // ???????????????
?????. 2005. ?. 31, ?3. ?. 320?325
# 254 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ?????????? ??????? ??????? ???????????? ??????????? ???????? ??????? ???? ???????
7. Patent 7041701 (US). Triterpenoid derivatives / M. Hajduch, J. Sarek / 09.04.2006.
8. Maurya S.K., Devi S., Pandey V.B., Khosa R.I. Content of betulin and betulinic acid,
antiturmor agents Zizyphus species // Fitoterapia. 1989. V. 60, ?5. P. 468?469.
9. Fulda S., Scaffidi C., Susin S.A. Activation of mitichondria and release of mitochondrial
apoptogenic factors by betulinic acid // J. Biol. Chem. 1998. V. 8, ?51. P. 33942?33948.
10. ?????? ?2150473 (??). ?????? ????????? ????????? ?????????? / ?.?. ????????,
?.?. ???????? / ?????. 10.06.2000.
11. Patent 2001-288222 (Japan). Polymer obtained from betulin and its production method /
K. Kobubshi, H. Kensetsu / 16.10.2001.
12. ?????? ?2324700 (??). ?????? ????????? ????????? ?????????? / ?.?. ?????????,
?.?. ????????, ?.?. ????????, ?.?. ?????????, ?.?. ????????? / ?????. 20.05.2008.
13. ?????? ?2415148 (??). ?????? ????????? ???????????? ?????????? / ?.?. ?????????,
?.?. ?????????, ?.?. ????????, ?.?. ????????? / ?????. 27.03.2011.
14. ????????? ?.?., ????????? ?.?., ???????? ?.?., ?????? ?.?., ???????? ?.?., ?????????
?.?. ????????? ????????? ???????? ?? ??????? ???? ?????? ? ???????? ??? ??????????????? ?????????? // ?????? ?????????? ???????????? ????????????. ?????. 2008. ?. 1. ?2. ?. 151?165.
15. ????????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?., ???????? ?.?. ??????? ??????? ?????????????? ? ??????????????? ????????? ??????? ???? ?????? ?? ????? ?
?????? ????????????? ????????? // ?????? ?????????? ???????????? ????????????. ?????.
2010. ?. 3. ?2. ?. 174?182.
16. ????????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?., ????????? ?.?., ???????? ?.?. ?????????? ???????? ????????? ???????? ???????? ?? ???? ?????? // ????? ? ????????? ??????????? ????????. 2010. ?. 18. ?3. ?. 313?320.
17. ?????? ?., ????? ?.?. ????? ???????????? ?????: ???. ? ????. ?.: ?????, 1983. ?. 4.
728 ?.
18. ???????? ?.?., ????????? ?.?., ?????????? ?.?., ???????? ?.?., ???????? ?.?. ????????????????? ??????? ?????????, ???????? ??????? ? ??????? ?????????? ????????? ???? //
????? ? ????????? ??????????? ????????. 2005. ?. 13. ?3. ?.391?400.
19. ????????? ?.?., ?????? ?.?., ???????? ?.?., ??????? ?.?. ???????? ??????? ? ??????????????? ??????? ??????????? ? ??????????? ?????????? ??????? // ??????? ?????????????
???????????????? ????????????, ???????????? ?????. 2005. ?2. ?. 113?118.
20. ????????? ?.?., ???????? ?.?., ???????? ?.?., ?????? ?.?., ???????? ?.?., ????????? ?.?., ???????? ?.?. ???????? ??????? ??????????? ????????? ??????? ? ??? ???????????????????????? ??????? // ????? ????????????? ?????. 2008. ?1. ?. 45?49.
21. ????????? ?.?., ????????? ?.?., ???????? ?.?., ??????? ?.?., ?????? ?.?. ????????
??????? ??????????? ????????? ??????? ? ??? ???????-????????????????? ??????? // ?????
????????????? ?????. 2010. ?1. ?. 137?141.
22. ???????? ?.?. ????????????? ? ?????????? ??????? ?????? ????????? ?????????????
// ????? ?????????. 1987. ?7. ?. 3?21.
23. ????????? ?.?., ???????????? ?.?., ???????? ?.?. ?????? ? ??????????? ????????
??????????? ??????????????????? ????????? ?????, ??? ? ?????// ????? ? ????????? ??????????? ????????. 2001. ?. 9. ?5. ?. 655?665.
# 255 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ?????????? ??????? ??????? ???????????? ??????????? ???????? ??????? ???? ???????
24. ???????????? ???? ???????? ???????? / ??? ???. ?.?. ????????. ?.: ???????????? ??
????, 1941. ?. 132-133
25. ???????? ?.?., ?????????? ?.?., ?????? ?.?., ????????? ?.?. ????????? ????????
? ???????? ?? ???? ??????, ?????????????? ? ???????? «????????? ?????????????» // ?????
????????????? ?????. 1998. ?1. ?. 5?9.
Influence of Conditions
of Outer Birch Bark Acylation and Activation
on the Yield and Composition of Extracts
Svetlana A. Kuznetsovaa,b,
Galina P. Skvortsovaa, Evgeniya S. Skurydinaa,
Yuriy N. Malyara and ?leg ?. Hanchichc
a
Institute of Chemistry and Chemical Technology SB RAS
42 K. Marx st., Krasnoyarsk, 660049 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
c
Russian State University of Tourism and Service
99, Glavnaya st., Cherkizovo, Pushkino district,
Moscow region, 141221 Russia
It was studied the influence of conditions of outer birch bark acylation by propionic acid and activation
of overheated steam on the yield and composition of triterpene derived products. It was established
that depending on the acylation conditions could be obtained the extracts with different contents of
betulin dipropionate, betulin monopropionate, betulin and lupeol. It was shown that the extracts with
the highest contents of betulin dipropionate 85-91 % was obtained from the initial birch bark the
fraction of 2-5 mm and pre-activated birch bark the fraction of 10-20 mm. The structure of betulin
dipropionate was confirmed by elemental analysis, FTIR spectroscopy, PMR and C13 NMR.
Keywords: birch bark, acylation, propionic acid, betulin dipropionate, activation, overheated steam.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 3 (2011 4) 257-268
~~~
??? 544.18
????????????? ???????? ?????????
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?? ?????????????????? ???????????
?????? ????????
?.?. ???????????*, ?.?. ?????????,
?.?. ??????????, ?.?. ????,
?.?. ????,?, ?.?. ?????????
?
???????????? ??????????????? ???????? ???????????,
?????? 660049, ??????????, ??. ????, 90
?
???????? ????? ? ?????????? ??????????
?????????? ????????? ???,
?????? 660049, ??????????, ??. ?. ??????, 42
?
????????? ??????????? ???????????,
?????? 660041, ??????????, ??. ?????????, 79 1
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
?????????? ??????????? ????????? ????????????? ?????????? ?????????, ??????? ?
???????? ?????? ?? ??????????? ?-Al2O3 (0001), ?????????? ?1- ? ?3-????????????? ??????. ???
??????? ?????????? ??????? ????????, ?????????? ? ?????????? ???????????? ?????????,
?????????? ????????-?????????????? ????? ??????????? ????????? ? ??????????
?????????. ???????? ?????????? ????????? ? ????????? ?????????, ????????????? ?
????????? 0,81-1,74 ??, ??????????????? ???????????????? ??????? ? ?????????????? ?1??-????????, ??????? ?? 0,24-0,79 ?? ????? ???????????, ??? ??????????????? ?????????
Aun ?? ???????????????????? ???????????.
???????? ?????: ????? ??????????? ?????????, ???????? ??????, ????? ????????, ??????
??????????? ????????.
????????
????????? ???????? ?????? ???????? ?? ?????????? ??????, ???????????? ?? ??????????? ???????, ???????????? ??????? ? ???????? ???????? ??????? ????????????? ???????????
?????? ????????????-????????????????? ??????? [1-6]. ?? ????????? ? ?????????? ??????
*
1
Corresponding author E-mail address: rivanenkovvv@gmail.com
© Siberian Federal University. All rights reserved
# 257 #
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d-???????? ???? ?? ???????, ???????? ?????? ???????? ????????? ? ????????? ? ???????
????? ?????? ??????????? ? ???????? ????????? ? ???????? ???????. ?????????????? ????
????????? ? ?????????? ???????? ??????????? ????? ??????????? ???????? ?? ??????????
??????????. ? ????????? ????????????? ????????????? ??????? ????????? ??????? ?????? ??
????????? ???????? ????????????: ?????????????? MgO (001) [7-12], ????????????????? TiO2
(110) [13-17], ???????? ZnO (0001), ????????????????? ?????????? ?????????? [18], ? ????????
[19. 20] ? ?? ???????? ????????? SiO2 [21-23].
?????? ?? ???????????? ???????????, ??????????? ?????? ???????? ????? ????????????? ??? ???????? ???????????????? ???????? ??? ????????? ?????? [24]. ??????? ?? ??????
????????? ???????????? ????????? ??????????? ?????? ?????? ?? ????????????????????
???????????? ?-Al2O3 (0001) ? ?-Al2O3 (001) [25-26]. ??? ??? ??????????? ?????? ???????? ?
??????????? ????? ? ??????? ??? ??????? ??????? ???????????? ????????????????? [27],
?? ???????? ? ??????? ???????????? ?????????????? ??????????? ????????? ?????? ? ?????????????? ???????? ?? ???????? ?????????????????? ??????????? ?????? ????????.
??????? ???????, ??? ??????? ???????? ? ?????? ????????????? ????????????? ????? ??
?????????? ???????? ??????????? d-???????? ????? ??????????? ?? ???????????? ?? ????????? ? ?????????? ?? ???????????????????? ???????????? [19-20]. ? ?????? ???????, ????????????? ????????????? ?????? ????? ??????? ????????????? ?????????????? ? ?????????
????????? ????????? ?????? ?? ???? ????????? ????????? ???????? ????????????????????? ?????? ??????.
? ?????? ?????? ???????? ??????, ????????????? ?? ??????? ???????? ? ?????????????
?3-??-????? ?? ????????????? ??????? ?????? ???????? ? ????????????? ????? ????????
??????????. ????? ???? ??????????? ????????? ????????? ??????, ???????????????? ?? ??????????? ?1-??-?????. ? ?????????, ????????????? ?????????????? Aun (?=1-3) ? ????????
?????????????????? ???????????? ?-Al2O3 (0001). ???????? ??? ?????????? ????????? ????????????? ?????????? ?????????? ??????, ???? ?????????? ???????? ??????? ? ??? ????????? ?????????? ???????? ??????.
?????? ????????
??????????? ????????????? ?????? ?1 ? ?3 (?????????) ???? ???????? ????? ?????????????? ????????? ????? ???????? H2O ?? ????????????????????? ??????????? ?-Al2O3 (0001)
(???.1) [28]. ????????? ???????? ????????, ???????????? ? ???? ?????, ??????????? ??? ??????????? ???? [29], ????????????? ???????????? ? ??????? ?????? ???????? ???? [30]. ??
???????????? ????????? ????????-????????????/???????????-???????????? (??/??) ????? ??????????? ???????? [31], ? ??????? ??????? ????????? ????????-???????????? ?????? ???????? ??????????? ??? ?????????? ???????????? ????????? (EPE). ????? ???? ???????
????????????????? ???????? ??????????????????? (?????????????) ? ??????????????????
(???????????????????) ?????????????? ????? ?????????? ????????? ???????. ??-???????
???????? ?????????????????? ??????????? ?????? ???????? ?????????????? ? ???? ???????? (Al??*)11Al9O11(OH)2. ??????????? ??????? ? ????????? ??/??-??????? ????????????????
????? ????????? ?? ??????????????? ????? ???????????? ?????????? ???????? Al??*,
??????? ??????????? ? ??????? ????????????? ????????????????? ? ?????? ???????????
# 258 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ????????? ????????????? ???????? ????????? ????????? ?????? ???????
???. 1. ?????? ???????? ?????????????????? ??????????? ?-Al2O3 (0001) ? ?????????????? ????????
?1 ? ?3
(softcore) [32], ?? ?? ????? ??????? ???????? ???????. ??? ???????? ??????????????????
??????????????????? ?????????????? ?????????????? ?????????? ?????? ????? ??????? ?????? ???????? [29]. ???????????? ??????? ????????? ???? ???????????? ?????????? ????????????????? ??????? ????? ????? Al??* ? O2? ???????? MM ??????? [29]. ????? ????????
????????? ????????? ??????? ? [29, 31].
??? ??????? ????????? ? ????????-?????????????? ??????????? ???????-??????????? [33, 34] ? ?????????????? ?????????? ?? ?????????? ??????????? ????????? ?????????????????????? ??????????? BP86 [35, 36]. ??? ???????? ????????? ????????? ???? ???????????? ???????? ?????? ??????????????? ????????? ??????? ??? ?????? ? (6s1p/4s1p)
[37, 39], ? (9s5p2d/5s4p2d) [37, 38], ?l (12s9p2d/6s4?2d) [37, 38]. ??? Au ????????? ??? ??
???????? ?????, ??? ? ? ????? ?????????? ?????????????: (21s1711d7f/11s10p7d3f) [19, 20,
40, 41]. ????? ?????? ? ????????-??????????? ?????????????? ?????????? ? ??????????????
????????????? ???????? ??????????? ????????? [42]. ? ?????????????? ????? LCGTO-FFDF (Linear Combination of Gaussian-Type Orbitals Fitting-Functions Density Functional) ??????????????? ??????????????? ???????? ????? ????????? ?? ???????????? ????? ??????????????? ??????????? ????????? ? ??????????? ?????? [42]. ????? ????, ? ??????? ?????? ????
????????? ???? «???????????????» ????????? ?- ? d-???? (??? ? ?????? ?-????), ????????????????? ? ???? ?????????????? ?????????? ? ????????????? 2,5, ??????? ? 0,1 ? 0,2 ?.?.,
??????????????. ??????? ? ???????? ????????? ???????????? ? ????-?????????????? ??????.
??????????? ????????? ???????? ? ??????? ????????????? ??????????? ?? ??????? ?
???????????? ???????? ?????????? ??? ? ?????????????? ????????????? ??????????? ?????? ??????? ??????? ??????? [43]. ??????? ????? ????????????? ?????????? ????????????
? ?????? ???????? ?? ???????????? ???????? ??????? (BSSE) [44]. ??? ??????? ??????????
????? ???????????? ??????? ??????, ?????????? ????? ??????????????? ???????????????????
?????????? ?????? ???????? (PDC) [45].
# 259 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ????????? ????????????? ???????? ????????? ????????? ?????? ???????
?????????? ?????????? ???????????
???????????? ??????????? ????????? ?????????? ????????????? ?????????? ?un (n =1-3)
???????? ?? ???. 2. ? ??????? 1 ??????? ??????????????? ?????????????? ???? ????????, ?
??? ????? ??????? ????????? ?? ????????? ? ????? ??????? ????????????? ????????? ? ??????????????? ?????????? (? ?? ???????? ?????????).
????????? ?????????
?????????? ??? ?????????? ????????? ??????????????? ????????? ??????. ? ?????????
1? ???? ???????? ?3-?? ?????? ??????????? ?? ??????? ????? Au ? ?????? ????? Au1-H1 =
158,5 ??. ??????? AuH ?????????????? ?? ???? ??????????? ???????: ?????? O1 ?????? ?1-??
? ?????? ????? Au1-O1= 224,5 ?? ? ?????? O2 ???????? Al2O3 ? Au1-O2=213,9 ??. ? ?????????
1? ???? Au ????????????? ?????? ???? ????????????? ????? ?? ??????? ????? O4 ???????? ?
??????????? Au1-O4=214,9 ??. ???? ???????? ????? ?????????? ????????? ?????????? ?? ????????? ?? ???????? Al3 ???????? ????, Au1-Al3=243,9 ??. ????????? ????? ???????? ?????????
?????? ?? ????????? ??????????? ????????? ?????? ?? ???????????????????? ???????????
?-Al2O3 (0001) [25]. ? ????????? 1? ???? ?????? ????????????? ?? ??????? ??????????? ?????
???. 2. ????????? ???????? ?????????? ?????????? ???????? (1? ? 1?), ?????? (2? ? 1?) ? ??????? ??????
(3? ? 3?) ?? ???????? ?????????????????? ??????????? ?-Al2O3 (0001). ??????? ?????????? ?????????
????? (??. ????? ? ????. 1)
# 260 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ????????? ????????????? ???????? ????????? ????????? ?????? ???????
??????? 1. ???????? ???????? ?????????? ????????????? ?????????? ?????????? ?????? ?? ????????
?????????????????? ??????????? ?-Al2O3 (0001): ????? ?????? (??), ??????????? ?????? q (e), ???????
????????? Eads (??)
Eads
1?
1?
1?
0,81
0,68
0,34
Au1-Au 2
2?
2?
2?
2?
2?
Au -Au
0,94
0,62
0,43
0,33
1,63
1,22
0,61
254,7
264,2
256,6
320,3
276,0
260,6
262,9
258,4
255,5
279,1
224,5
Au -O
213,9
2
264,5
269,1
203,3
Au -O
203,3
208,3
212,5
158,5
201,5
176,2
Au1-Al2
2
Au -Al
2
Au -Al
3
156,8
174,6
178,5
174,0
172,5
243,9
275,8
258,5
268,0
274,3
249,3
97,3
97,0
97,3
98,6
101,3
-0,13
0,00
O2-H2
0,00
q(Au 2)
0,00
254,9
270,6
265,8
255,4
-0,25
-0,11
-0,12
0,35
-0,03
-0,33
0,74
0,09
0,08
0,04
-0,30
0,07
0,05
0,23
0,11
-0,12
-0,17
-0,07
-0,42
0,42
q(Au )
-0,13
255,5
-0,21
3
0,00
266,9
258,0
Au3-Al3
q(Au n)
229,4
268,4
Au1-Al3
q(Au1)
210,4
211,7
177,8
Au 2-H2
O -H
222,9
224,9
212,2
Au1-H2
1
218,2
231,1
Au 2-O3
1
204,7
214,9
4
2
202,1
225,9
Au1-O3
1
3?
1,74
3
Au1-O1
1
3?
253,1
Au1-Au3
2
3?
-0,01
0,17
0,14
0,01
0,07
0,99
?????? ?3-??, ? Au-H1=201,5 ??. ????? ????? ?3-?? ? 1? ??????? ????????? ?? ????????? ? 1?,
? 98,6 ?? 101,3 ??. ???????? 1? ????????????? ?????????????? ??????????????? ????? ??????
? ????????? ??????????? ???????, ??? Au1-Al2=268,4 ??.
???????? 1? ??? ????????? ??? ???????? ?????????? ? ???????? ????????? 0,81 ??. ???????? 1? ?? 0,13 ?? ????? ????????, ? 1? ????????? ??? ?? 0,34 ?? ???? ?? ???????. ???????
????????? 1? ? 1? ?? 0,36 ? 0,23 ?? ??????, ??????????????, ??? ???????????? ??????? ????????? ???????? ?????? ?? ???????????????????? ???????????, 0,45 ?? [25].
????????? ???????
???????? ???? ???????? ?????????? ???????? ??? ????????????? ?????????? ?u2 (???. 2,
????. 1). ????????? 2? ?????????? ?????????, ???????????? ??? ???????????????????? ??????????? ?-Al2O3 (0001) [25], ????? ????? ?????? ???????? ?? ??????????????? ? ??????????????
?????????????? ????????. A??? Au1 ???????? ???????? ????? ? ?????? ????????? ???????,
Au1-O3=208,3 ??; ????? ????, ?? ?????????????? ? ?????????? ?l ????????, Au1-Al3=275,8 ??.
A??? ?u2 ?????????????? ? ???????? Al3, ?u2-Al3=268 ??. ??????? ????????? ??? 2?, 0,94 ??,
# 261 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ????????? ????????????? ???????? ????????? ????????? ?????? ???????
??????????? ????????? ? ??????? ??? ?????????, ????????????? ?? ???????????????????? ??????????? ?-Al2O3 (0001), 0,95 ?? [25].
???????? ?????????? ?????????? ???????????????? ?u2 ????????? ???????? 2?, ??????? ??????????????? ????? ??????? ? ?????????, ?????????????? ???????????? Au1 ?? ??????????? ?????? ?1-?? ??????, Au1-O1= 203,3 ??, ? ???????????? ?u2 ?? ??????? Al3, ?u2Al3=258,5 ??. ? ???????????? ???????? ????????? 1,74 ?? ?????? ???????? ???????? ????????
?????????? ?????????? ?????? ??????; ?????????????? ? ????????? ????? ?? 0,79 ?? ???????,
??? ? 2?.
? ???????????? ???????? ????? 0,62 ?? ???????? 2? ???????? ?????? ????? ?? ???????????? ????? ??????????????? ???????, ?? ??????? ?? ?? 0,32 ?? ????, ??? 2?. ??? ?????????
????????? ???????? ?? 2?, ????? ???? ???????? ?? ?????? ?3-?? ???????????? ? ??????????
???????????? ?????????? ????????? ?? ??????? ??????: Au1-H1=177,8 ?? ? Au2-H1=176,2 ??.
??? ?????????? ???????? ?? 20 ?? ??????? ????????? ?????? Au-H, ???, ????????, ? ????????? 1?. ?? ????????? ? 2? ????? Au1-?u2 ?????????? ?? 11 ??, ?? 264,2 ??, ? ?? ????? ??? ?????
?u2-Al3 ?????????? ?????? ?? 9 ??, ?? 249,3 ??. ?????????????? ?u2 ? ????? ?? ???????????
??????? ???????? ????????, ?u2-?3=212,2 ??, ???????????? ???????????? ????????? 2?.
???? ???? ???????? ?????? ?3-?? ????????? ? ??????? ????????? ?????? ?u2, ?? ????????? ????????? 2?. ?? ????????? ? 2?, ? 2? ??????????? ????? Au1-H1 ? ?u2-Al3. ????? ?u2-H1
??????????? ?? 156,8 ??, ??? ?????? ? ?????????? Au1-H1 ? ????????? 1?. ????? Au1-O1 ??????????? ?? ???????????? ???????? 202,1 ??; ????? ??????????? ????? ????? ? ???????????
??????? ???????? ????????, ?u2-O3= 211,7 ??. ?????? 2? ?? 0,19 ?? ????? ????????, ??? ?????? 2? (????. 1).
??????????????? ????????? 2? ? ?????????? H1 ? ????? Au-Au ???????? ? ??????????? ????????? 2?. ??? ??????????? ?????????????? ???????? ??????? 0,29 ??; ????????? 2?
?? 0,10 ?? ????? ?????????, ??? 2?. ???????????? ??????? ?????? Au1-H1 ? ?u2-?1 ??????????
174,6 ? 174,0 ?? ??????????????, ??? ??????? ??????, ??? ? 2?. ???????? Au-H-Au ?????? ?
???????????? ???????? ?????? ? ??????????? ???????, ?u2-Al3=258,0 ??, ? ????? ???????????? ???????? ??????? Au1 ? ???????????? ???????? (Au1-O1 ? 212,5 ??, Au1-O2 ? 224,9 ??,
Au1-O3 ? 225,9 ??; ????. 1). A??? Au1 ????????? ? ?????????? ????????? ??? ???????????
????????????? ??????????? ???, ??? ?????????? ?? ?????? ?? ??????????? ?????? ??????????
??????? ??????? 253 ??.
????????? ????????
??? ???????? ?????? ???? ?????????? ??? ?????????? ??????????? ?????????, ?????????? ?? ???????? ???????? (???. 2, ????. 1). ???????? 3? ? ????????????? ??????? ?3 ???????? ????? ??????????, E??? = 1,63 ??. ? ???? ????????? Au3 ???????? ? ???????????? ????
????? Au1-?1=204,7 ?? ? ??? ????? ?u2-Al2=266,9 ?? ? Au3-Al3 = 270,6 ??. ????? ?????? Au-Au
? ???????????? Au3 ????????? ? ????????? 258,4 ? 279,1 ??. ?????? ?????? ? ????????? 3? ???????? ????? ?????? ? ??????? ????????. ????? ???????, ??? ????????? ?????????? ?????????
????????? Au3 ?? ????????? ???????????????????? ??????????? ?-Al2O3 (0001), ??? ????????
???? ?????????? ????????? ??????? ??????? ?????????, E???=1,39 ?? [25]. ??? ????????? 3?
?????????? E???=1,22 ??, ??? ?? 0,41 ?? ????, ??? ? 3? (????. 1). ????? Au1-O3 ? 3? ?????? 210,4
# 262 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ????????? ????????????? ???????? ????????? ????????? ?????? ???????
?? ?? 6 ?? ??????? ??????????? ?????????? Au-O ? 3?. ? ?????? ???????, ??????????, ??? ? 3?
??? ????? ???????? ????? Au-Al ?? 5-11 ?? ?????? ??????????????? ?????????? ? 3? (????. 1).
??????? ???????? ? ?????? ?3-?? ? ?????????? ????????? ?? ?????? ?????? ???????? ?
??????? ????? Au-Au. ????? ???????, ???????? Au3 ? ?????????? H, ??? ?? ??? ? ? ?????? 2?,
??????????. ????????? 3? ????????? ???????? ????? ????????? H (?? ?3-??) ? ????? Au1-Au3;
???? ???????? ???????? ???????? ??????????, ???????? ?? 1,0 ?? ???? ?? ??????? ????????? 3? ? ?? 0,6 ?? ???? ????????? 3?. ????????? ? ???????????? ????????? Au1-H1-?u2 ? 3?
???????????? ??????????? ?????????? ????????? 2?. ? ?????????, ???? Au1 ?????????? ???
??????? ???????????? O2-O3-?4 ? ??????? ?????? Au-? ? ???????? 222,9-231,1 ??. ????? ?u2 ?
Au3 ??????????????? ? ???????????? ?????????: Au2-Al2 = 254,9 ??, Au3-Al3 =255,4 ??.
????????? ? ??????? ????????? ? ?????????????
???????? ??????????????? ???????, ????????? ???????? ??????, ?????????? ?? ???????????????????? ??????????? ?????? ????????, ????? ????????? ????????????? ??????????? ?????? [25]. ??? ????????? ?un (n = 1-6) ?? ???????????????????? ??????????? ?-Al2O3
(0001) ?????????? ??????????? ?????? ? ????????? ?? -0,09 ?? -0,14 e. ??? ?????? ?un (n =1-4)
?? ?-Al2O3 (001) ???? ???????? ????????? ????? ????????????? ??????????? ??????, ?? -0,17
?? -0,30 ?. ??? ?????????? ????????? ? ?????? ???????????? ? PDC ????????? ?????????????
??????????, ??????????????? ? ????????? ??????: ??????????????? 1? (-0,13 ?), 2? (-0,12 ?),
2? (-0,17 ?) ? ????????????? 2? (-0,07 ?), 2d (-0,42 ?). ? ?????, ??????? ? ???? ???????????
??????, ???????????? ??? ?????? ?????????? ?????? ??????: ????????????? 1? ? ??????????????? 1? ? 3?; ??????????? ? ??????????? ????????????. ? ?????? ???????, ? ?????????
?????? ???? ??????? ????????? ????????? ?????? ? ?????????????? ???????????? ????????:
??????????????? ???????? 3? (0,07 ?) ? ????????????? ????????? 2e (0,42 ?), 3? (0,99 ?).
?? ?????? ??????? ??????? ?????? ???????? ? ????????? ????????????? ????? ?? ???????????? ? ???????? ???????? d-???????? ???????? ????????????? ????????, ????? ??? ?????
????????????? ??? ??????????????? ? ?????????? ??????????? ????????? ?????? d-??????? ?
???????? ????????-?????????? ????????? ??????? [19, 20, 46]. ??????, ?? ????????? ? ??????? d-?????????, ??????????? ????????????? ?????? ?????? ?? ???????? ???????? ???????
[19, 20]. ?? ??????? ??????????????????? ?????????? ???????? 1?, ? ?????? H1 ?? ????? ??????,
??????? ????????????? ??????????? ????? ?? ??????????????? ????????? ?????? ?? ???
?????? (????. 1). ??????????? ????? ????? 0,00 ?, ??? ????? ???? ?? 0,12 e ??????, ??? ?????
????? ?????? ? ????????? 1?, ????? ???? ?????? ?????????????? ?? ?????? ????????. ?????
????, ???? ?????????? ????????????? ??????????? ?????? ?0,07 ? ?0,42 ? ??? ????????????? ??????? ?????? 2c ? 2d. ??? ?????? ??????????, ??? ??????? ?????? ???????? ? ?????
?3-?? ?-Al2O3 (0001) ?? ??????????????? ???????? ?????? ?? ???????? ? ????????? ?????????????????? ??????. ? ?????? ???????, ??? ?????????? 2? ? 3? ?????????? ??????? ????????????? ??????????? ?????? ?? ????????? ??????, 0,42 ? 0,99 ? ??????????????, ? ??????? H1
????? ??????????? ?????? ????????? Au-H-Au. ????????????? ?? ??? ????????? ? ??????????????????? ?????????? ?????? ???????? ??????????? (????. 1).
? ???????????? ??????? ????????????? ???? ??????? ? ???? ??????????? ?????? ??????? ?????? ? ????????????? ????????? 1?, 2?, 2? ???????????? ????????? ???????????
# 263 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ????????? ????????????? ???????? ????????? ????????? ?????? ???????
????? ????????? ?????? ????????? ??????? ??????? ?????????. ??? ?? ????? ?????????????
??????? ????????????, ??? ??? ? ????? ??????? ??????? ??? ????????????? ??????????????????? ???? ?? ????????? ?????????? ?? ??????????????? ??????? ?????????? ???????? ??????,
? ?? ??????????? ????????? ?????????. ????? ????, ? ????????? ???????????? ??????????
? ???????? ???????? ??? ??????, ??? ? ?????? ????????, ????????????????? ??????, ????????? ???????????? ??????-????????? ?????? ?????? ??-??????, ???????????, ????????????
? ??????? ???????? ?????? ? ???????. ?????? ??????? ???????, ??? ??????? ??????, ????????????????? ? OH-????????, ???????? ????? ????????-???????????, ??? ???????? ??????
?? ???????????????????? ???????????, ? ?? ?????????? ?????????? ???????? ? ??????????????????? ?????????.
????????-?????????? ????????????? ???????? 2? ? 3? ?? 0,6 ?? ????? ?????????, ??? ??????????????? ???????? 2? ? 3?. ????????????? ???????????? ?????? ????????????? ? ??????????????? ????????? ?????? ?? ?????? ???????? ?????????????????? ??????????? ?-Al2O3
(0001) ????? ???? ???????? ?? ????????????? ???????????? ?????? Au6, ??????????????? ??
?????? ????????????? ?????? ?????????????????? ??????? ???????? [20]. ????? ??????????
?????????? ?????? ??????? Au6/zeo(3H) ????????????????? ? ????????????? ?????? Au6(3H)/
zeo, ??????? ??????? ?????????? ?? 0,28 ?? ? ?????? ?????????? ?????? ???????? ? ???????????? ? ??????? ????????? ?????? ? ?????? ???????? H ????? ? ?3-?? ??????. ???????, ???
????? ????????? ????????????? ????? ?? ??????????? ?????? ???????? ?????? ?3-?? ??
?-Al2O3 (0001) ??? ?-Al2O3 (111) ????????? ??????????? ??????? ???? [27]. ??? ???????? ?????
????????? ?????, ???????? ?3-?? ?? ?-Al2O3 (001) [27], ????????????? ???????????? ?????????
?????? ? ????????????? ????????? ?????? ????????. ??????? ?????, ??? ? ??????????? ???????? ???????? ?????? ???????????? ????????????? ??????, ??-????????, ???????????. ???
???????? ?????? ???? ?????? ???????? ?????????? ????????????? ???????? 1a. ??? ??????
?????? ??????????????? ???????? 2? ?? 0,3 ?? ????? ????????, ??? ????????????? 2?. ???
??????? ??????, ? ???? ???????, ??????????????? ???????? 3? ?? 0,6 ?? ????? ???????? ??
????????? ? ????????????? 3?.
? ?????? Au6(3H)/zeo ???????? ???????? ?????????? Au-? ????? ????? ~214 ?? [20]. ???
?????????? ???????? ? ?????? ??????, 212-214 ??, ? ?????????? 1?, 2?, 2?, ? ??????? ?????? ????????? ? ????????????? ?????????. ?, ????????, ??? ??????????????? ????????? Au6, ??????????????? ?? ????????? ????????, ???? ????? ???????? ?????????? Au-O, 270 ?? ???????
??????? ?????? ? ??????????????? ????????? ?? ??????????? ?????? ????????. ? ???????
???????????? ??????? EXAFS ????????? ?????? ?? ??????????????????? ???????? ??????
???????? ???? ???????, ??? ?????????? Au-O ????????? ? ???????? ?? 204 ?? ?? 210 ?? [47].
???????????? ???? ?????????? Au-O ?? ??????????? ??????? ?1-??, 202-205 ?? ? ??????????
2?, 2?, 2? ? 3? ?????? ? ??????? ?????????????????? ??????. ????? ???????? ????????????
?????????? ? ??????????-?????????? ????????? ?????? ????? ??????? ?????? ? ???????????? ???????? ????????, 208-215 ?? ??? ?????????? 1?, 1?, 2?, 2?, 2?, ? 3?, ????? ? ???????? ?????????????????? ???????. ?????? ?????? ?? ???????????? ????????????? ??????? ?
????????-?????????? ????????????? ????????? 2? ? 3?, ??????????? ??? ???????? ??????????? ????????????? ??????????? ?????? ???????? ????? ???????, ????? ????? ?????????
Au-? ???? ???????????. ???????????? ???????? ???? ?????????? 223-253 ??.
# 264 #
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?.?. ??????????, ?.?. ????????? ????????????? ???????? ????????? ????????? ?????? ???????
??????????
? ?????? ???????? ?????? ?? ???????????? ????????????? ? ??????????????? ????
?????????? ?????? (???????, ?????, ??????), ??????????????? ?? ??????????? ???????? ?????????????????? ?-Al2O3 (0001). ????? ????????, ??????????????? ???????? ?????? ????
???????? ???????? ???????????. ???? ??????? ????????, ??? ??????????? ??????? ??????
?? ?????? ???????? ??????????????? ? ?????????????? ?????????????? ????????, ???????
????? ?????????? ?????????, ??? ???????????? ?? ???????????????????? ???????????. ???
?un (n =1-3) ?????????????? ???????????? ?????????? 0,25-0,8 ??. ??????? ????????? ?? ?????
?????????? ???????? ? ????????? ?????????? ?????????? 1,63 ? 1,74 ?? ??????????????, ? ??
????? ??? ?? ????????????? ?????????? ???????? ??? ???????? ????? 0,81 ??.
??????? ????????? ? ?????????????? ???????? ????????? ?????????????????????? ?????????? ???? ???. ?????? ?????????? ?? ??? ?? ?????????? ????????? (?????? ? 22.51
????????? ??????????????? ???????????? ?????????? ???). ?.?. ???????? ???????? ???????????? ??????????????? ????? ? ??? ?? ?????????????? ?????????? ????????? (?????
???????? ?????????????? ???????? ??????? ??????).
?????? ??????????
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?.?. ??????????, ?.?. ????????? ????????????? ???????? ????????? ????????? ?????? ???????
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The Computational Study
of Small Gold Species Adsorbed
on Hydroxylated Alumina Surfaces
Vladimir V. Rivanenkov,a Svetlana S. Laletinab,
Tatyana V. Shulimovichb, Alexey M. Shorb,
Elena A. Shorb,c and Vladimir A. Nasluzovb
a
Krasnoyarsk State Agrarian University,
90 Mira st., Krasnoyarsk, 660049 Russia
b
Institute of Chemistry and Chemical Technology SB RAS,
42 K. Marx st., Krasnoyarsk, 660049 Russia
c
Siberian Federal University,
79 Svobodniy pr., Krasnoyarsk, 660041 Russia
We calculated equilibrium structures for adsorption complexes of gold monomers, dimers, and trimers
on a ?-Al2O3(0001) model surface, partially covered by ?1 and ?3 hydroxyl groups. We applied a
scalar-relativistic gradient-corrected density functional method to cluster models of the support that
were embedded in an elastic polarizable environment. The most stable structures, with calculated
adsorption energies in the range 0.81?1.74 eV, feature coordination bonds to surface ?1-OH group and
are 0.24?0.79 eV more stable than the corresponding Aun complexes on a dehydrated surface. Isomeric
rearrangements of the most stable complexes are hindered by barriers of 0.65?1.08 eV.
Keywords: Density functional theory, gold clusters, alumina, embedding cluster models.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 3 (2011 4) 269-275
~~~
??? 544.18, 539.193
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? ?????? ? ??????????? ???????? ???????,
????????????? ??-?? ??????? ????? ??????????? ?????????? ?????
?.?. ????????* , ?.?. ????????,?
?
????????? ??????????????? ??????????????? ???????????,
?????? 660049, ??????????, ??. ????, 82
?
????????? ??????????? ???????????,
?????? 660041, ??????????, ??. ?????????, 79 1
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
????????-?????????? ??????? ?????? ??????????? ????????? B3LYP/6-31G(p,d) ??????????
???????????? ? ??????????? ???????? ?????????? ??????? ???????, ???????????? ??-??
??????? ????- ? ??????????? ?????????? ?????. ????????, ??? ????? ??????? ? ??????
???????? ??????????????? ??????????????? ? ??????? ????????, ??? ? ?????????????. ???
???? ????? ??????? ????????? ? ???????? ???????, ? ?????????? ???????? ? ? ????????
?????????? ?????????. ???????? ??????? ?????????? ??????? ? ?????? ? ????- ? ????????????
???????? ??????????? ???, ??? ?? ????? ???????? ???? ??????? ????? ? ????????????
?????? ????????? ???????????? ????????? ?????????, ??????????? ???????? ? ??????
???????? ??? ??????????????, ??? ????? ??????????? ? ???? ???????????? ?????.
???????? ?????: ?????????? ?????????????, ??????????? ????????, ?????? ???????????
?????????, ????????-?????????? ?????????????.
????????
????????? ?????????? ???????????? (??????????, ??????????, ???????), ???????? ??????? ?????????? ????????, ???????? ????????? ???????? ????? ????????????, ??????????
? ????????? ???? [1-10]. ? ???????? ???????? ??????????? ????????????? ???????? ????????
???????? ???????? ??????????? ?????????????, ???????????? ??????????? ? ?????????? ????? ?????????? ??? ???????? ????????????? ???????? ? ????? ??? ??????????? ????????????? ? ???? ?????????????? ???????. ???, ????????, ? ?????? [1] ???? ????????, ??? ????????
C60 ? ????? ??? ????? ??????? ?????? ?? ??????????? ????? ????????? ? ???????? ??????????-
*
1
Corresponding author E-mail address: kpo1980@gmail.com
© Siberian Federal University. All rights reserved
# 269 #
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?? ??? ?????????? ??????? ???? ? ????????? ????????? ???????????? ? ?????????? ???????
???????? ???????. ? ??????? [2-4] ???????????? ?????????? ????????????, ??? ???? ????????
??????? ???????? ?????????? ??????? H2, ???????????? ??????? Sc ? Ti ?? ????????????
?????????? ???????? (???) ? ??????????. ????????? ?????????, ?????????????? ???????? ???????????? ? ?????? ???????????, ????? ???????????????? ?????????? ???????? ???
????? ?????? ????????? 3d-????????? [5] ? ???????? ?????????? ?????? [11, 12], ??? ????????? ???? ??????? ?? ?????????? ??????????? ???????? ????????? ?? ???? ??????? ????????.
????? ????????, ??? ??????????? ????????? ????????? ????????????? ???????? ???????? ???????? ????????????? ?? ????????, ????? ?????????? ????? ????? ??????? ???????
????? ???????? ????? ? ?? ????? ??????????? ?? ????????? ?? ???????????, ?????????? ?
?????????????. ??? ??????????? ???? ????? ???????????? ?????? [6, 7] ?? ????????????? ???????? ????????? ???????????? ?????????????? ???? ?? ?? ???????, ?? ?? ??? ??????????
???????, ?? ???? ?? ????????, ????????? ?? ????????????? ?????????? ????? (??????????). ?
?????? ???????, ???? ????????, ??? ?????????? ?????????? ????????? C60 ? ??????? ?????????? ????????, ??????????????? ??? ??? ???????????? ??????????? ???????? (???????????)
[8], ??? ? ??? ??????? ????? ??????? ???????? [1, 9], ????? ???? ????????. ??????????? ???????, ??? ? ?????????? ?????????????, ?????????? ?????? ?????????? ??????????? ??????
(?????????), ????? ????????????????? ? ??????? ?????????? ????????? ?????, ?????? ??????
? ???. ? ?????? ??????????????, ????????, ????? ????? ??????????? ? ????? ???????????
???????????? ?????????????? ????????. ???????? ???????? ?????????? ???????? ????????
??????? ?????????? ? ????????????? ????????? ??????????? [13, 14].
????? [10] ???? ???? ????????, ??? ?????????????? ?????? ?????????? ????????? ? ?????????? ????????????, ?????????? ????- ? ??????????? ??????, ???????? ???????, ??? ? ????????????, ?????????? ?????? ???????????? ??????. ??? ???? ???? ????????? ?????????????, ??? ?????????? ????????? ?????????? ?????? ???????? ??????????? ?????????????
??????????????? ? ???????????? ???????? ?????????? ? ??????????. ? ?????????????? ?????
?????? ?????????? ?????????? ??????????? ??????? ????????????, ??? ????? ????? ????????
?????????? ????????????? ? ????????? ??????? ??????????? ?????????? ?????? ??????? ?
?????? ? ???????????????? ??????????? ???????????.
??????? ? ?????? ????????????
??????? ???????????? ? ??? ????????? ?????????? ????????. ?? ???????? ????? ???????
????????? ???????. ? ???????? ???????? ????? ????????? ???? ??????????? ?????????? ?????, ??? ? ????? ?????? ? ???? ???? ???????? ? ???????? (????????? 7-6), ?? ?????? ? ????????
? ???????? (????????? 5-6), ? ??????? ? ???????? ? ???????? (????????? 5-7) (???. 1). ????????? ???? ???????????? ????? ?????????????? ?????? ??????-????? (Stone-Wales) ??????????
????????? [15]. ????????? ???????? ????? ???? ???????????? ?????????? ????????????, ?
?????? ??????????? ? ?? ??????????? ????????, ?????? ?? ????????? ??? ????? ???? ????????????? ???????? ????? ?????? ?? ?????? ????????, ????? ?????? ??????? ???????? ??????
?? ???????? ?????. ??? ???? ???????????? ?????????? ????? ?????????? ?????? ???????
????? ???? ??????? ??????? ????????. ???? ? ?????? ??????????????? ?????????????? ?????? ???????? ?????? ? ?????????? ??????????? ???????? ???????? ?????.
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???. 1. ??????????? ??????? ??????????? ????????. ??????? 1 ? 2 ???????? ???????????
?????????????? ?????? ????????
????? ??????? (Sc) ? ?????? (Ti) ?? ??????????? ????????????? ??? ??? ?????, ??? ? ???
?????? ??????? ? ?????????? 1 ? 2 ?????????????? (???. 1). ? ????????? 5-6 ??? ??????????
?????? ?? ????? (????????) ???????, ?????????? ?????????????? ? ????????? ?????????. ?
????????? 5-7 ????? ??????????????? ???????????? ?????? ???????? (Me) ?????? ? ????? ???????, ????????? ??????? ???????? ???????, ? ????????? ?? ?????????????? ? ???????????? ?
?????? ??????? ??? ?? ???????????. ? ????????? 6-7 ?????? Me ?????????? ? ????? ??????,
????????? ??? ?? ?????????, ??? ??????????? ????????? ????? ????????????? ???????? ????????. ??????? ? ?????? ???????? ????????? 4 ????? ?????????????? Sc ? Ti ? ????????????,
??? ???? ????????? 3 ? 4 ????????????? ?????????? 1 ? 2 ? ??????????????? ??????? ?????????.
????????????? ??????????????? ? ???????????? ???????? ????????? ???????? ????????? ? ????????-?????????? ?????? NWChem [16] ??????? ?????? ??????????? ?????????
(DFT) ? ?????????????? ???????-??????????????? ?????????? B3LYP [17] ? ???????? ??????
6-31G(p,d).
?????????? ? ??????????
?????? ?????????? ??????????????? ?????????? ???????? ?? ???????? ? ??????? ???????
(????. 1), ??? ? ???????? ?????????????? ?????? ????? ??????????? ????????????? ??????????? ?????. ?? ???? ?????????? ???????? ??????????? ????????? ? ??????? ?????? ????????
? ???????????? ??????????? ?????????? ?????? ????? ???? ? ??????? ???????. ??? ????
??????????? ??????????????? ? ?????????? ???????? ??????? ?????????? (Eb) ? ???????? ???????????? ?????? (q) ????? Me ??? ???????? ?? ????? ????????? ? ?????? ? ? ??????????? q
????????????? Eb.
????????? ?????????????? ?????? Sc ? Ti ? ???????????? ?????????, ???????, ??? ????????? ?????????? ??????? ??????????? ?? ???? ??????? ??????, ??? ???????. ???????? ????????????? ??????? ????? ???????? ??????? ???????? ??????????? ????????? ? ???????
?????????? ????????? ? ?????? Ti, ?????? ? ?????? Sc, ??? ??????? ?? ????????? ?? ??????????????? ??????????? ??????? (????. 1).
# 271 #
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??????? 1. ??????? ?????* ? ??????????? ?????? ?????? Sc ? Ti ? ??????????? ???????????
????????? ?????
???????
?????????
5-6
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Sc
q, ?.?.
Ti
Sc
Ti
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1,97
2,22
0,60
0,72
4
1,36
1,72
0,40
0,26
??????????: * ? ?? ?????? ?????? [10].
??????? 2. ????????? ??????????? ??????? ?????? ??????????? ?????????? ??? ?????????? ??????
?????????
?????????
?????
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
5-6
-0,01
-0,01
-0,01
-0,01
-0,02
-0,02
-0,02
-0,02
-0,02
?
?
5-7
-0,02
-0,01
-0,02
-0,01
-0,02
-0,02
-0,02
-0,01
-0,02
-0,01
?
6-7
-0,01
-0,01
-0,01
-0,01
-0,02
-0,02
-0,02
0,00
-0,02
0,00
-0,02
? ?????? ???????, ??????? ????????, ??? ??????????? ?????? ?????? Me ? ??????????
?? ??????????? 5-6 ? 6-7 ?????? ? ?????????, ????? ?????????? ?????????????? ??????? ?
?????? ? ????- ? ???????????? ??????????? ????????, ??? ? ????????? ?????????????? ?
????????????? ????????. ? ????????? 5-7 ???????? ??????? ?????????? Sc ? Ti ??????????? ? ??????????? ???????, ??? ? ???????????. ??? ????? ??????? ?? ???????? ???????
????? ? ??????????? ??????? ?????? Me ? ??????????????? ???????????. ??? ???????????
??????, ??-?? ??????? ??????????? ?????? ??????????, ???? ????????? ??????????????
??????? ????????? ?????????? ????????? ? ????????? ????????????? ???????. ?????????? ?????????????? ???????? ?????????? ? ??? ?????? ?????????. ????????? ???????????
??????? (????. 2) ?????? ???????? (???. 1) ??????????????? ??????????? ??? ????? ????????
??? ????, ??? ??????????? ????? ? ??????? ??????? ?????????????? ????? ??????? ??? ??
???, ? ???????? ??????????? ????? ??????? ?????????????? ??????? ? ??????. ???, ????????, ? ????????? 5-6 ??????? ?????????? ????????????? ??????????? ??????? ???????????
? ?????? C5, C6, C7, C8 ? C9, ?????????? ????????. ? ????????? 6-7 ? ? ?????? C5, C6, C7, C9,
C11, ???????? ? ?????? ?????????. ?? ???? ????? ?????????, ??? ???????? ??????? ?????????? ?????? Sc ? Ti, ??????????? ? ???????? ??????? ??????????, ? ????- ? ????????????
????????, ??? ? ????????????, ?????????? ?? ??????? ????, ??? ????? ???????? ??????
????? ???????? ????? ??????????? ???????????? ?????????? ?? ????????? ? ???????????? ?????????.
# 272 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????? ??????? ??????????? ?????????? ?????? ??????? ? ?????? ? ??????????? ????????...
???. 2. ??????????? ?????? ????????? ???????????? ????????
???????? ?????? ????? [18] ???????? ? ??????? ?????????????? ????? ?????????? ???????????? ????????? ??????? ??????????? ???????????? ???????? ?????? ?????????? ? ?????? ????????? ???????????? ???????? (????) ?????????. ?? ??????? 2 ???????, ??? ? ???????????? ???? ????????? ???????? ?????????? ????? ?????? ????? ????????? ? ??????????
5-6 ? 5-7 ? ????? ????????? ? ????????? 6-7. ?????? ???? ?????????, ?????? ?????????????
??????????? ????? ? ??????? ??????? ????????????? ??? ?????????? ????????? ?????? ?
?????? ???? ?????.
??????????
??? ?????????????? ?????? ??????? ? ?????? ? ???????????????? ??????????? ?????????? ?????? ????????? ? ???????? ??????? ??????????, ? ?????? ? ??????????, ???????????
???????? ????? ??????? ?? ?????? ????????? ???????????? ????????. ????????? ? ?? ???????????? ? ?????????? 5-6 ? 6-7 ?????? ?????????? ????? ????? ???????? ??????????????
????- ? ??????????? ?????, ?????? ????? ????????????, ?????????? ?? ?????????????? ???????????? ?????? ?????????? ? ??????? ???????, ??? ???????? ? ????? ???????? ??????????
?????? ???????? ? ????.
??????????? ?????????? ??????????? ? ?????? ????????? 5-7, ??? ????? ???????? ???????????? ?????? ?????? ??????? ????? ? ???????????? ?????? ???????????? ???????? ????
?????????, ?????? ????? ????????????.
?????????????
?????? ???????? ????????????? ????????????????? ?????????????????? ?????? ?????????? ???????? ???? ?? ?????????????? ??????????? ????????????? ??????????? ??????????. ?????? ????????? ??? ????????? ??????????? ??????? ????????? «??????? ? ???????????????????? ????? ????????????? ??????» ?? 2009-2013 ????.
?????? ??????????
1. Huang L., Liu Y.-Ch., Gubbins K.E., Nardelli M.B. Ti-decorated C60 as catalyst for hydrogen
generation and storage // Applied Physics Letters. 2010. Vol. 96. ? 6. P. 063111.
# 273 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????? ??????? ??????????? ?????????? ?????? ??????? ? ?????? ? ??????????? ????????...
2. Yildirim T., Ciraci S. Titanium-decorated carbon nanotubes as a potential high-capacity
hydrogen storage medium // Physical Review Letters. 2005. Vol. 94. ? 17. P. 175501.
3. Durgun E., Ciraci S., Zhou W. et al. Transition-metal-ethylene complexes as high-capacity
hydrogen-storage media // Physical Review Letters. 2006. Vol. 97. ? 22. P. 226102.
4. Han S.S., Goddard III W.A. Lithium-doped metal-organic frameworks for reversible H2
storage at ambient temperature // Journal of the American Chemical Society. 2007. Vol. 129. ? 27. P.
8422-8423.
5. Zhang Y., Dai H. Formation of metal nanowires on suspended single-walled carbon nanotubes
// Applied Physics Letters. 2000. Vol. 77. ? 19. P. 3015-3017.
6. Krasnov P.O., Ding F., Singh A.K. et al. Clustering of Sc on SWNT and reduction of hydrogen
uptake: ab-initio all-electron calculations // The Journal of Physical Chemistry C (Letters). 2007. Vol.
111. ? 49. P. 17977-17980.
7. Kuzubov A.A., Krasnov P.O., Kozhevnikova T.A. et al. Peculiarities of the decoration of
carbon nanotubes with transition metal atoms // Russian Journal of Physical Chemistry B. 2011. Vol. 5.
? 1. P. 163-167.
8. Zhao Y., Kim Y.-H., Dillon A.C. et al. Hydrogen storage in novel organometallic buckyballs
// Physical Review Letters. 2005. Vol. 94. ? 15. P. 155504.
9. Shin W.H., Yang S.H., Goddard III W.A. et al. Ni-dispersed fullerenes: Hydrogen storage and
desorption properties // Applied Physics Letters. 2006. Vol. 88. ? 5. P. 053111.
10. ??????? ?.?., ???????? ?.?., ??????? ?.?. ?????????????? ?????? ??????? ? ??????
? ?????????? ????????????, ?????????? ??????????? ? ??????????? ?????? // ?????? ????????????????? ? ????????????? ??????. 2012. ?. 141. ? 1 (??????? ? ??????).
11. Kubas G.J., Ryan R.R., Swanson B.I. et al. Characterization of the first examples of isolable
molecular hydrogen complexes, M(CO)3(PR3)2(H2) (M = molybdenum or tungsten; R = Cy or isopropyl).
Evidence for a side-on bonded dihydrogen ligand // Journal of the American Chemical Society. 1984.
Vol. 106. ? 2. P. 451-452.
12. Kubas G.J. Molecular hydrogen complexes: coordination of a ?-bond to transition metals //
Accounts of Chemical Research. 1988. Vol. 21. ? 3. P. 120-128.
13. Vanderbilt D., Tersoff J. Negative-curvature fullerene analog of C60 // Physical Review Letters.
1992. Vol. 68. ? 4. P. 511-513.
14. Park N., Yoon M., Berber S. et al. Magnetism in all-carbon nanostructures with negative
Gaussian curvature // Physical Review Letters. 2003. Vol. 91. ? 23. P. 237204.
15. Stone A.J., Wales D.J. Theoretical studies of icosahedral C60 and some related species //
Chemical Physics Letters. 1986. Vol. 128. ? 5-6. P. 501?503.
16. Kendall R.A., Aprа E., Bernholdt D.E. et al. High performance computational chemistry: An
overview of NWChem a distributed parallel application // Computer Physics Communications. 2000.
Vol. 128. ? 1-2. P. 260-283.
17. Becke A.D. Density-functional thermochemistry. III. The role of exact exchange // The Journal
of Chemical Physics. 1993. Vol. 98. ? 7. P. 5648-5652.
18. Fukui K., Yonezawa T., Shingu H. A molecular orbital theory of reactivity in aromatic
hydrocarbons // The Journal of Chemical Physics. 1952. Vol. 20. ? 4. P. 722-725.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????? ??????? ??????????? ?????????? ?????? ??????? ? ?????? ? ??????????? ????????...
The Nature of Chemical Bonding of Scandium
and Titanium Atoms
with Graphene Cluster Models Curved by the Presence
of Five- and Seven-Fold Carbon Rings
Pavel O. Krasnova and Alexandr A. Kuzubova,b
a
Siberian State Technological University,
82 Mira, Krasnoyarsk, 660049 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
Molecular and electronic structure of graphene cluster models curved by the presence of five- and
seven-fold carbon rings was carried out by quantum-chemical method of density functional theory
B3LYP/6-31G(p,d). It was shown that scandium and titanium atoms interact more preferable with these
rings than with six-fold ones. At the same time metal atoms act as electron donors, and carbon clusters
act as acceptors. Much stronger binding of scandium and titanium by the five- and seven-fold rings can
be explained by a fact that their carbon atoms contribute more considerably to the generation of lowest
unoccupied molecular orbitals of clusters, accepting electron from metal atoms at the interaction,
than atoms of six-fold rings conjugated with other two mentioned types of rings.
Keywords: carbon nanostructures, electronic structure, density functional theory, quantum-chemical
simulation.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 3 (2011 4) 276-284
~~~
??? 543.572.3:541.123.3
??????????????? ? ?????????????????
????????????? ???????? ?????????
??????? NaF-NaI-Na2WO4
?.?. ?????????,
?.?. ?????????, ?.?. ????????*
????????? ??????????????? ??????????? ???????????
?????? 443100 ?. ??????, ??. ?????????????????, 244 1
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
????????? ??????????????? ???????? ????????? ??????? NaF-NaI-Na2WO4 ?? ?????? ???????
????????? ?????????? ? ???????????????? ???????? NaF-Na?-Na2WO4 (? ? Cl, Br, I).
?????????? ???????? ??????????????? ????????????? ??????? ????????? ?? ?????????
???????? ????? ?????????? ????- ? ???????????????? ??????, ?????????????? ??????? ??
????????? ?????????, ? ????? ?????????? ???? ????????????.
??????? ????????????????? ???????????? ??????? ??????????? ???????????????? ???????
NaF-NaI-Na2WO4, ?????????? ??????????? ?????????, ?????? ??????? ????????????? ?????,
??????? ??????? ??????????.
???????? ?????: ???????????????? ??????????? ??????, ??????? ??????????, ?-? ?????????,
?????????.
????????
???????? ????????????????? ??????? ?????? ????????? ???????? ??????? ????????????,
??????????? ??? ????????????? ?????????? ? ???????? ????? ??????????????? ?????????,
?????????? ?? ????????????? ?????? ????????? [1, 2]. ???? ???????? ????????, ??????????
??????? ????, ??????????? ? ??????? ???????????? ? ????? ????????? ????? ??????? ??????????. ?????????? ?-?-???????? ?????????? ????????? ???????? ????????? ???????? ???????,
?????????? ?????? ????????????? ?????????? ? ????????? ?????????? ??????????.
?????? ??????? ????????????
? ?????? ???????? ????????????? ?????? ????? ?????????? ???????????????? (Na?Na2MoO4 (? ? Cl, Br, I)) ? ???????????????? (NaF-Na?-Na2MoO4 (? ? Cl, Br, I)) ??????, ??-
*
1
Corresponding author E-mail address: windy22@mail.ru
© Siberian Federal University. All rights reserved
# 276 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ?????????? ??????????????? ? ????????????????? ????????????? ???????? ?????????...
?????????? ??????? ?????????-???? ? ??????????????????, ??????????????? ??????????
??????????? ?????? ????????. ? ???? ???????????????? ?????? ??????????? ????????? ??????????? ????????? ?????????? ?? NaCl ?? NaI, ??? ???????? ? ????????? ??????????? ????????? ??????? ????????: ?2 606 ?? > ?5 526 ?? > ?6 502 ?? (???. 1) [3-5]. ? ??????? Na2MoO4-NaCl
???????????? ?????????? ????????????? ????????? ? ?????????? ??? ????????????? ?????.
??? ?????????? ??????? ???? ??????? ????????? ? ?????????? ???????????? ?????????, ???
??? ???????????? ??????? ????? ????? ??????? ??????? ??????????. ? ?????????? ? ??????????? ??????? ??? ??????????????? ????? ?????????? ?????????, ?????????? ????????
????????????? ??????? ??? ??????? ?????????? ? ???????.
???????????????? ??????? (???. 1) ???? ?????????? ??????????? NaF ? ?????????
???? ???????????????? ????????. ???? ????????, ??? ????????? ????????????? ???????????????? ???????? ? ?????????? ???????? ?? ?????? ???????????? ??????? ???????????
????????? ?????? ???? NaF-Na?-Na2MoO4 (? ? Cl, Br, I) [5, 6], ?????? ?????? ?? ????????????
? ??????????? ????????? ???????????????? ????????????? ?????. ??? ???? ?????????? ???????? ?????????? NaF ??????? ??????????? ????????? ??????? ?????????. ????? ??? ??????
??? ?????? ???????????? ??????????, ???????????? ??????? ????????? ?????? ?? ??????????
??????, ??? ?????????? ????????? ??????????? (?????? ??? ?????????? ????? ????? ?? [3, 7]
? NaI?Na2WO4 ? NaF?NaI?Na2MoO4 ???? ??????????? ???????? ?????). ????????, ??? ?????????? ????????? ???????? ??????? (???. 2).
????? ???????, ?? ????????? ???????????????? ?????? ???? ?-?-???????? ?????? ???????????????? ???? NaF-NaCl-Na2WO4? NaF-NaBr-Na2WO4 ? ??? ????????? ??? ? ???????????
?????, ??? ? ???????? ??????????????????? ???? ????????? MoO42-, ?????? ???????????? ??????? ????????? ????????? ??????????????? ??????? NaF-NaI-Na2WO4. ? ??? ????? ?????????????? ??????????? ??????? ????????????? ? ??????????????? ????? (??????? ?? ???. 2 ???????
?????????).
???. 1. ???? ??????: Na?-Na2MoO4 ? NaF-Na?-Na2MoO4 (? ? Cl, Br, I)
# 277 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ?????????? ??????????????? ? ????????????????? ????????????? ???????? ?????????...
???. 2. ???? ??????: Na?-Na2WO4 ? NaF-Na?-Na2WO4 (? ? Cl, Br, I)
?????? ????????????? ???????? ????????? ????????? ? ?????? ???????????? ???????? ??????????????? ??????????? ????????? ???????????????? ????????, ?????????? ?? ??????????
??????????? ??????????? ????????? ??????? ????????? ?? ??????? ??????? ???????? (Cl-, Br-,
I-) [8]. ????????????? ????????????? ? ???????? ????????? ???????? ??????? ??????? ????????
? ??????? [9, 10]. ??? ???????????????? ?????? Na?-Na2MoO4 (? ? Cl, Br, I) ???????? ??????????? «??????????? ????????? ????????? ? ?????? ?????? ????????», ??????? ???????????? ??
???. 2 ? ? ????. 1. ??? ???????????????? ?????? ???? NaF?Na? ?Na2MoO4 ????? ???????????
??????????? ????? ???????????? ????????? ????????? ? ????????? ??????? ??????? ????????
(???. 3, ????. 1). ??????????? ??????????? ????????? ??? ?????? ?????? ?????????? ????????
MS Excel, Table curve ? Corel DRAW. ??? ???? ???????????????? ?????? Na?-Na2WO4 (? ? Cl,
Br, I) ???????? ??????????? ?????????? ? ?????????? ????????? ??? ??????? ?????????????
???????? (???. 4, ????. 1). ?????????? ?????????????? ???? ???? ??????? ?????????????, ???
??? ???????? ? ???????????????? ???????? ???? NaF?Na??Na2WO4 ???????? ???????????
????????? ???????. ?? ????????? ????? ???????? ??????????? ??????????? ????????? ???????????????? ????????? ? ??????? ??????? ????????, ?????? ??????? ??????????? ?? ???. 3,
????. 1. ? ?????????? ???????????? ??? ???????????????? ??????? NaF-NaI-Na2WO4 ????????
????????????? ???????? ??????????? ????????? ??????? ????????? t??(E*) = 540 ??.
??????????? ??????? ????????? ????????? ???????????? ??? ??????????????? ???????
(????. 1).
?????????? ???????? ??????? ??????? I- ? ?????????, ??????????? ? ????. 1, ????????
????????? ?????? ???????????????? ?????????: 38 % NaI, 60 % Na2WO4 ?, ??????????????,
2 % NaF.
????????????????? ?????
??? ????????????? ??????????? ???????? ? ?????????? ????????????? ????? ?????????????? ?????????? ???????????????? ??????????? ???????????????? ??????? NaF-NaI-Na2WO4,
??????????? ???????? ??????? ??????????? ?? ???. 5.
# 278 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???. 3. ??????????? «??????????? ????????? ????????? ? ?????? ?????? ????????» ? ????? ?????? Na?Na2MoO4 ? NaF?Na??Na2MoO4 (? ? Cl, Br, I)
???. 4. ??????????? «??????????? ????????? ????????? ? ?????? ?????? ????????» ? ????? ?????? Na?Na2WO4 ? NaF?Na??Na2WO4 (? ? Cl, Br, I)
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ?????????? ??????????????? ? ????????????????? ????????????? ???????? ?????????...
??????? 1. ????????? ??? ??????? ?????????? ????????? ? ??????? ???????? ? ????? ??????: Na?-Na2?O4
? NaF-Na?-Na2?O4 (? ? Cl, Br, I; ? ? Mo, W)
????????? ??????????? y = ar(?-)2 ? br(?-) + c, ??? ?= t(e);
t(E); X(e); X(E)
???????
??????????
??????????
? ???????
??? ??????
Na?-Na2MoO4
Na?-Na2WO4
NaF?Na??Na2MoO4
NaF?Na??Na2WO4
???????????
a
b
??????
c
a
b
c
Na?
1111,1
4722,2
5513,1
-239,32
-995,56
-998,93
Na2MoO4
-
-
-
239,32
995,56
1098,9
Na?
948,72
3996,7
4744,9
-98,291
-467,22
- 513,16
Na2WO4
-
-
-
98,291
467,22
613,16
Na?
1179,5
4940
5657,3
-322,65
-1363,1
-1404,1
Na2MoO4
-
-
210,47
893,47
1013,7
Na?
961,54
4025
4741,2
-213,68
-938,89
-992,37
Na2WO4
-
-
-
70,513
339,17
465,88
???. 5. ??????????? ???????? ??????? NaF-NaI-Na2CrO4 ? ???????????? ???????????????? ??????? MN
?????????? ????????? ??????? ??????? ???????? ??? ???????????????? ???????
(???. 5). ??????????? ????? ?????????? ???????, ??? ???????????????? ??????? NaF-NaI ?
NaI-Na2WO4 ?????????????? ???? [3, 4]. ? ??????? NaF-Na2WO4 ?????????? ????????? ? ???????????, ?????????? ??????????????? ????????? ?????????? D3 [4, 11]. ?????????????, ??
??????? ?????????? ???????????????? ?????? ? ??????? ?????? NaF-NaCl-Na2WO4 ? NaFNaBr-Na2WO4 ????? ????????????, ??? ? ???????????????? ??????? NaF-NaI-Na2WO4 ?????????? ??????? ????????? ? ???????????.
????????????????? ???????????? ????????? ??????? ????????????????? ????????????
??????? (???) ?? ????????? ? ??????????? ?????????? [12]. ???????? ???????? ????????????
# 280 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ?????????? ??????????????? ? ????????????????? ????????????? ???????? ?????????...
«???» (NaF, Na2WO4), «??» (NaI) ???? ?????????????? ??????????. ??????????? ?????????
??????? ? ??????????? ??????????? ??????????????? ?????????? ?????? [13]. ???????????? ????????? ? ??????????? ?????????? ???????????. ??????? ?????? ? ???????? ???????????? ???????????? ???????, %.
??? ?????????? ????? ????????????? ?????????? ? ???????????????? ??????? NaFNaBr-Na2WO4 ? ???????????? ? ????????? ???????????-????????????????? ?????? (????)
[14] ?????? ??????????????? ?????? M [75 % NaI; 25 % NaF] ? N [75 % NaI; 25 % Na2WO4],
?????????? ????? ??? ????????? ???????. ????????????????? ???????????? ??????? MN ????????? ?????????? ??????????? ?? ??? ???????????????? ????????????? ????? P 5 566 ? E 8
538 ? ????? k ??????????? ? ?????????????? ?????? e8P5 (???. 6).
????????? ????????, ????????? ?? ??????? NaI ? ?????????? ????? ????? ???????????
?????? ????????? ?????????????? P 5 ? E 8 ?? ??????? MN, ?????????? ?????????????? ????????????? ????? (???. 4, 5): ?8 538 ?? ??? ?????????? ??????????? 2 % NaF, 40 % NaI, 58 %
Na2WO4; ??????????? ????????? ????????? P5 ????????? 566 ?? ??? ?????????? ???????????
10 % NaF, 67 % NaI, 23 % Na2WO4. ??? ?????? ????????? ????????? ??????? Na2WO4 ?NaF?
NaBr ???????? ??????? ??????? (????. 2). ??????? ????? P?1 ? P'2, ??????????????? ?????????
?/? ? ?/? ? Na2WO4, ?? ???????????? ? ???????? ???????????.
?????????? ???????????
? ?????? ????????? ??????????????? ????????? ????????? ????? ?? ????????? ???????????????? ??????? NaF-NaI-Na2WO4. ???? ??????????? ???? ????- ? ???????????????? ??????
Na?-Na2?O4 ? NaF-Na?-Na2?O4 (?=Cl, Br, I; ?=Cr, Mo, W), ??????????????? ?? ???????? ? ?????? ??????? ????????? ??? ??????????????? ???????, ????????????? ?????? ?? ???????????
?????. ??????? ????????????? ?? ??????????? ? ??????? ??????? ????????? ? ???????????,
???. 6. ?-?-????????? ???????????????? ??????? MN ??????? NaF-NaI-Na2WO4
# 281 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???. 7. ?-?-????????? ???????????????? ???????
???. 8. ?-?-????????? ???????????????? ???????
NaBr ? E 6?E6 ??????? NaF-NaI-Na2WO4
NaI? P ?P2 ??????? NaF-NaI-Na2WO4
??????? 2. ??????? ?????????? ? ??????? NaF?NaI?Na2WO4
??????? ?????????
??????? ??????????
???????? ????????????
?????????
????????? E8
???-Na2WO4+D2+NaI
?????????????
??????????? P5
?+NaF?NaBr +D2
?????????????
??????????? P'2
?+?-Na2WO4??-Na2WO4+D2
??????????????
??????????? P'1
?+?-Na2WO4??-Na2WO4+D2
??????????????
?????? e13P'1
???-Na2WO4+D2
??????????????
?????? P'1P'2
???-Na2WO4+D2
??????????????
?????? P'1E8
???-Na2WO4+D2
??????????????
?????? e12E8
???-Na2WO4+NaI
??????????????
?????? p2P5
??NaF+D2
??????????????
?????? e8P5
??NaF+NaI
??????????????
???? p2P2e8NaFp2
??NaF
????????????
???? p2P5E8e13p2
?? D2
????????????
???? e13P'2p'2Na2WO4e13
???-Na2WO4
????????????
???? p'2P'2P'1 p'1 p'2
???-Na2WO4
????????????
???? e12EP'2p'2e12
???-Na2WO4
????????????
???? e12E8P5e8NaIe12
??NaI
????????????
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ?????????? ??????????????? ? ????????????????? ????????????? ???????? ?????????...
??????? 3. ?????????????? ?????????, ?????????? ? ?????????? ???????? ? ??????????????????
???????????? NaF?NaI?Na2WO4
??????? NaF?NaI?Na2WO4
?????????????? ????????
?????????????????
??????
??????????? ????????? ?????????, oC
540
538
NaF
2
2
?????? ?????????, ?????.% NaI
38
40
60
58
Na2WO4
??? ? ?????????? ???? ???????????? ?????????????????? ??????????????. ??????????, ?????????? ??? ??????????????? ????????????? ????????? ? ?????????????? ??????? ??????
???????? ????????? ? ??????? ?????????? ?????, ?????????? ??????? ?????????? ? ???????????? ???????????? (????. 3).
? ?????? ?????? ??????? ???????? ???????????????? ??????? NaF-NaI-Na2WO4. ?? ????????? ?????? ?-x-???????? ??????????????? ???????? ???????? ??????? ?????????????????
??? ?, ?, ? ??????????? Na2WO4, ???????????, ??????????????, ??? ????????????: ??? 589 ??,
??? 576 ??. ???????? ??????? ??????????? ????? ?????? ????????????????? ???: NaF, NaI,
D3, ?-Na2WO4, ??Na2WO4 ? ??Na2WO4 ??????? ???????????? ?? ???? ?????????????? ??????,
?????????? ? ???? ????????????? ?????? ?6 538 ?? ? P5 566 ?? ? ???? ?????? ? ????????? ?/?
? ?/?. ???????????? ???? ?????????????? ????????????? ???????? ???????????? ?????????? ?
??????? ??????.
?????? ????????? ? ?????? ?????????? ??? «??????? ? ??????-?????????????? ????? ????????????? ??????» ?? 2009 ? 2013 ????.
?????? ??????????
1. ??????? ?.?. ????????????????? ??????????. ?.: ???????????????, 1991. ? 264 ?.
2. ???????? ?.?. ?????????? ????????? ????: ??????? ??????? ??? ????????????????????? ?????????????? ?????. ?.: ?????? ?????, 1990. ? 240 ?.
3. ????????????? ?.?., ??????? ?.?., ?????? ?.?., ?????????? ?.?. ?????????? ?? ????????? ?????? ?? ????????? ?????????????? ?????. ?.: ???-?? ?? ????, 1961. ?.1.-845 ?.
4. ????????? ?.?., ????????? ?.?. ????????? ????????? ??????? ??????. ?. III. ??????? ??????? ? ????? ????????. ?.: ???????????, 1979. ? 204 ?.
5. ?????????? ?.?., ??????? ?.?., ????????? ?.?. ??????? ?????????? ? ??????? NaClNaBr-Na2MoO4 // ????. ???????. ?????. 2007. ?. 52. ???. 3. ?. 427?430.
6. ?????? ?.?., ???????? ?.?., ??????? ?.?., ???????? ?.?. ??????????? ?????? ???????
Na//F, Cl, MoO4 // ????. ???????. x???? 1976. ?. 21. ???. 9. ?. 2506?2510.
7. ?????? ?.?. ??????????? ??????????? ???????????? ????????????????? ??????. ??????: ?????. ???. ????. ??-?, 1997. ? 308 ?.
8. ??????????? ?.?., ?????? ?.?. ???????? ????????: ??????? ??????? ??? ?????. ?.:
?????? ?????, 1978. ? 84 ?.
# 283 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ?????????? ??????????????? ? ????????????????? ????????????? ???????? ?????????...
9. ???????? ?.?., ??????????? ?.?., ???????? ?.?. ?????? ????????? ? ???????????????? ??????? LiBr-FrBr ? ?????? ?????? ?? ???? LiBr-?Br (? ? Na, K, Rb, Cs)// ???. ?????. ????? ? ???. ??????????. 2004. ?.47. ???. 9. ?. 28-31.
10. ???????? ?.?., ????????? ?.?., ????????? ?.?., ??????????? ?.?. ??????, ??????????????? ? ????????????????? ???????????? ????? ?????? ?? ??????????? ???????? ? ???????????????? ?????????. ????????????: ??? ???, 2006. ? 148 ?.
11. ????????????? ?.?., ??????? ?.?., ?????? ?.?., ?????????? ?.?. ?????????? ?? ????????? ?????? ?? ????????? ?????????????? ?????. ?.: ???-?? ?? ????, 1961. ?.2. ? 585 ?.
12. ?????? ?.?. ???????? ? ??????????? ??????. ??????: ?? «??????», 1996. ? 270 ?.
13. ??????????? ????????? ???????: ?????????? / ??? ???. ?.?. ??????. ?.: ??????.
???. X. ?. 2. 1981. ? 300 ?.
14. ?????? ?.?., ???????? ?.?. ???????????-???????????????? ????? ???????????? ???????????? ?????????? ? ???????????????? ????????????????? ????????. ????????, 1977.
68 ?. ? ???. ? ?????? 12.04.77, ? 1372 ? 77.
Prediction and Studied of the Phase Complex
of NaF-NaI-Na2WO4 System
Elena O. Ignatieva,
Ekaterina M. Dvoryanova and Ivan K. Garkushin
Samara State Technical University
General and Inorganic Chemistry Subdepartment
244 Molodogvardeiskaya st., Samara, 443100 Russia.
Prediction of the phase complex of system NaF-NaI-Na2WO4 has been holded on the basis of phase
equilibrium in the row of ternary systems NaF-NaHa -Na2WO4 (Hal ? Cl, Br, I). We have methods
for prediction characteristic of a ternary eutectic on basis of series exploration the single-type twocomponent and ternary system, comparative research its liquidus character, as well as building a
series of dependencies.
The three-component system NaF-NaI-Na2WO4 has been studied by the differential thermal analysis.
As a result we have defined melting point temperature, and the compositions ternary eutectic mixture.
We also have described the non and invariant equilibria.
Keywords: the differential thermal analysis, phase equilibrium, T-?-diagram, eutectic.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 3 (2011 4) 285-293
~~~
??? 546.05
?????? ???????? Zn2SnO4
??????????????? ???????????? ??????????
?.?. ???????, ?.?. ?????*,
?.?. ??????, ?.?. ?????????
????????? ??????????? ???????????
?????? 660041, ??????????, ??. ?????????, 79 1
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
???????????? ?????????? ???????????? ????????? ??????? ???????????????? ????????
???????? ????? ??????????????? ????????? ?????????? ?? ???????? ??????????
????? (?????????????????) ? ???????????????? ?????? ????? (IV). ????????????
?????????? ????? ??????????? ???????? ???????????? (??/???), ???????????????? (???),
??????????????????????? (???) ??????? ? ????????? ??????????? ??????????? (???).
?????????????? ???????? ?????? ? ??????? 2 ? ? ????????? 673-1223 ? ????????, ??? ??????
???????? ???????? ?????? Zn2SnO4 ??????????? ??? ???????????? ???? 1100 ?, ? ??? 1223 ?
????? ???????? ?????????? ????? 83 %. ??? ?????? ??????????? ???????? ??????????
?? ?????? Zn2SnO4 ???????? ?? 50-200 ??. ???????????? ????????????? ??????? ?????? ???
????????????? ?????????? ????? Cu/Zn2SnO4, ?????????? ???? ?????????????.
???????? ?????: ??????? ?????, ???????, ?????????? ?????????, ???, ????????, ??????.
????????
??????????? ????? (Zn2SnO4) ??????????? ??? ???????? ??? ??????? ???????? [1, 2], ???????? ????????????? [3] ? ?.?. ?????? ????????????? ???????????? ??? ????????????? ?????
????? ?????????? ? ???????? ???????? ???? ? ?????????????????? ?????????? ???????/?????
? ????/????? ??? ???????????? ???????????? ???????? ?????? ??????. ?????? ??????????
Zn2SnO4 ????? ???? ???????????, ???? ????? ????? ??????? ???????????? ? ????????? ??????????? ? ????????????? ???????. ? ????? ? ???? ??????????? ??? ????????????? ? ???????????? ??????? ??????? ?? ?????? ????????? ?????????? ????? ??????/????? ?? ????????
???????????.
??????????? ????? ???????? ??????????????? ?????????, ??????? ???????????? ???????????? ?????? [4-6], ????????? ??????? [7, 8], ?????????????? ????????? ?????????? ?????
*
1
Corresponding author E-mail address: Ashubin@sfu-kras.ru
© Siberian Federal University. All rights reserved
# 285 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????? ?????? ???????? Zn 2SnO4 ??????????????? ???????????? ??????????
[3, 9, 10] ? ??. ? ?????? ?????? ??????? ??????? ??????? ????? ? ????? ????????? ? ????????????????? ??????????? ? ?????????? ?????????? ? ?????????????? ??????????? ?????????
??? ??????? ??????????? ? ?????????????? ?????????????. ?????? ????? ????? ??????????
?????? ? ??????????, ?????????????? ? ????? ?? ???????????? ?????????? ????????? ????
???????. ????? ??????????? ????????? ????? (???) ???????? ????? ? ?????????, ? ??? ??????? ???????? ?????????? ?????????? ?????? ?????, ? ?? ??? ? ?????? ????????????? ???????? ? ????????? ??????????.
? ?????? ??????? ??????????? ?????????? ?????? ??? ??? ??????? ?????????????????
???????????? ?????. ?????? ???????? ????????? ? ??????? ????????? ?????????? ???????????? ?????????? ????? ? ????? ?????? ??????????, ????? ???????, ?????????? ??????????? ????????? ???????? ? ???????-????????? ????????, ??? ??? ?? ??????????? ????????? ??????
?? ?????????????? ????????? ?????????.
????????????????? ?????
? ???????? ???????? ??????????? ???????????? ???? ? ?????? ????? (IV) ???????????
SnCl4?5H2O, ?????? ????? ???????? Zn(CH3COO)2?2H2O ? ????????? ? ???????? ???????
(NH4)2CO3 (??? ???????? ???????????? «??»). ??? ?????????? ?????? ?????????? ? ????, ? ???????????? ???????? ???????? (CH3COONH4 ? NH4Cl) ? ?????????? ????????? ???????????
??? ??????????? ?? ???????????? ??????????? ??? ??????????? ?????????????? [11, 12].
???????? ?????????????? ???????? ????? ????? (???????????? 0,8 M) ? ????? (1,6 ?), ?
????????? ?? ??????? ????????????????? ??????????? ZnO:SnO2=2:1, ?????????, ????? ????
?????????? ????????? ??????? (NH4)2CO3 (3?) ? 10 %-? ????????, ??????? ??????????? ?????? ????????? ????????. ??????? ????? ?????? ??? ??????????? ????????? ????. ?????? ??????????????? ? ?????? ??? ??????????? 383 ? ? ??????? 10 ?. ??????? ??????????? Zn:Sn ?
??????????? ??????????, ???????? ???, ?????????? ????? 2,03, ??? ??????????????? ? ??????
????????? ???????????. ?? ??????????? ?????? ??????????? ???????? ???????????? ?????????? ??????? ????? (?????? STA Jupiter 449C (Netzsch), ?????? ???????????: ?????????
??????, ?????? Ar 15 ??/???; ?????????? ??????, ???????? ??????? 10 ?/???, ????? ??????? ?
????? 10 ??).
??????????? ?????? ????? ??????????? ?? ??????? ? ??????? 2 ? ? ???? ??????????: 673,
773, 873, 973, 1073, 1173, 1223 ?. ?????????? ??????? ???? ????? ???? ?????????? ?? ??????????? ??????. ??? ??????? ????????? ???????????, ???????????????? ? ?????????????????
???????. ??????????????? ?????? ????????? ?? ????????????? X`Pert-Pro (PANalytical), ?????????? ????????????? ??????? ? ?????? ?????? (?=0,15406 Е). ?????????????? ?????????????? ? ????????? ????? 2? 5-800 ? ????? 0,0260. ?????????????? ??????????? ??? ?????????
?? ??????????? ????? ? ??????????? ???????????? ??????????? Match! 1.9a. ??????????
?????? ???????? ???????????? ??????? ?????????????????????? ?????????????, ?????????
??????????? ? ???????? ?????????? ARL Advant`X (????????????? ?????? ? ???????? ??????,
???????? 3,6 ???). ?????????? ????????? ?? ???????????? ???????? ????????? ????????????????? ??????? ??????????????? ?????????? ??? ????????????? ???????????? ??????????? UniQuant 5. ??????????? ?????????????? ?? ????????? ??????????? ?????????? JEOL
JSM-7001F. ??????? ??????? ???????? ?? ??????????? ??????????? ??????.
# 286 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????? ?????? ???????? Zn 2SnO4 ??????????????? ???????????? ??????????
?????????? ? ??????????
??????????? ?????? ???????????? ?????. ?? ???. 1 ????????? ?? ? ??? ?????? ?????????? ??? ????????????? ?????????? ???????? ??????? Zn2SnO4. ?? ???. 1 ?????, ??? ???????????, ?? ??????? ????, ?????? ???????? ???????????????? ???????? ????? ??????? ?
??????????????? ?? ??????????? ? ?????????? ????? ?????????? 392, 518, 676 ? 817 ?. ?????? ?????? ????? ????????? ????? 11,5 % ?????????? ??? ??? ??????????? ????? 350 ? ? ????????????? ??? ~600 ?. ? ????????? 600-750 ? ?????????? ?????????? ?? 4,36 %. ? ????? ?
??????? ????????? ?????????? 750-1040 ? ??????????? ??????? ????????? ????? ?? 3,57 %.
????? ????, ? ??????? ?????????? 1160-1240 ? ?????????????? ??? ?????? ???????????.
????????, ??? ???????? ? ??????????? ?????? ???????????? ??????? ???????? ?????????? ??????????? ?????, ???????????? ?????????. ? ??????????????? ???????? ?????????? ?????? ?????? ?????? ???????? ?? ????????? ?????, ??????? ????? ?????????? ? ????
Zn5(OH)6(CO3)2, ??????????????? ???? Zn3CO3(OH)4·2H2O, Zn4CO3(OH)6·H2? [13], ? ????? ?????????? ????? (IV) ? ????? ?-????????? ??????? SnO2·xH2? (??? ?=1?2 [14]).
? ??????????? ?? ??????? ????????? ? ??????? ?????????? ????????????????? ????? ??????????? ???????????? ??????? ???????? ???????? ?????????? ??? ?????????? ?? ??????
????? [15]. ???????? ?????? [16], ?????????? Zn3(OH)4CO3 ?????????? ??? 493 ?, Zn4(OH)6CO3
????? ???????????? ???????? ?????????? ??? 525 ? [13, 17]. ??????????????? ?????
Zn4(OH)6CO3·H2? ????????????? ????? ????????? ?????????? ???????????? ????? 340 ? [18].
??????????? ?????????? ZnCO3, ?? ?????? [19, 20], ?????????? ????? 573 ?, ? ??? ?????????
??????????? ????????? [21] ??????? ????????? ??????? ????????: ???????? ???????? ?????
540 ?, ????? ???????? ?????????? ~480-600 ?. ????????? ????? ??????????? ? ????????? 373523 ? [14].
????? ???????, ??????????????? ?????? ???????????? ??????? ???????????? ????? ????????? ???????????????-???????????? ?????????? ? ??????????????????? ???????????
?? /%
??? /(???/??)
n ????
0.4
788
100
98
96
- ??
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94
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86
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84
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1196
82
[2]
400
500
600
700
800
900
??????????? /?
1000
1100
???. 1. ?? ? ??? ?????? ?????????? ???????????? ????? ????? ?????
# 287 #
1200
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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????? ?????? ???????? Zn 2SnO4 ??????????????? ???????????? ??????????
??? ?????????? ?????. ? ????? ???????? ??????????????? ??????? ????????????? ? ???????? ? ??/???-??????, ??????? ?????? ?????? ?????????? ????????????????. ?????? ???
?????????? ??????? ????????.
??????????? ??? 392 ? 518 ? ??????? ??????? ? ?????????? ????????????????? ?????.
?????? ?? ??????????? ?????? ????? ? 11,5 % (???. 1) ????? ????????????, ??? ???? ? ??????
????????? ??????????????? ? ???? ?????????? Zn4(OH)6CO3, ???? ??????????? ??????? [18],
??? ?????????????? ???? ??? ??????? ??? ?????. ??? ?????????? ????????? ?? ?????????
???????
Zn4(OH)6CO3= 4ZnO + CO2+ 3H2O,
(1)
? ???????????? ? ??????? ????????? ???????? ?????? ????? ??????? ?? ???? ????? ?????????? (? ?????? ??? ?????????? ? ?????) ?????????? ????? 12 %. ???????? (1) ?????????, ??????????, ? ??? ???????? ?????. ?? ?????? ??????????? ?????? ????????????????? ? ????????? ?????????? ?????????? (????????????? ???????? 350-460 ? ? ?????? ????? ?????
3 %):
Zn4(OH)6CO3 = ZnCO3 + 3 Zn(OH)2,
(2)
Zn(OH)2 = ZnO + H2O.
(3)
?? ?????? ????? (????????????? ???????? 460-600 ? ? ?????? ????? ????? 8,5 %) ?????????? ????????????? ?????? ?????????? ?????????? (3) ? ?????????:
ZnCO3 = ZnO + CO2.
(4)
? ????????????? ????????? ?????????? ?????????? ? ?????????????? ZnO, ????????
?????? ?? ??????? ?? ?????????? ?? ??????, ? ?????, ??-????????, ????? ????? ?????????
???????????? ????????? ???????. ??? ??????? ? 676, 788 ? 818 K ? ????? ???? ???????? ?
???????? ???????? ??????????? ????????????? ????????? ??????? ? ????????? ???????
????? ????? 8 %, ? ????? ?????????????? SnO2 (??????????????? ??? 788 K). ???????? [14],
??? ???????????? ????????? ??????? ??????????? ? ??????? ????????? ?????????? ?????? ??
???????? ??????? (900 ?).
???????? ?????????????? SnO2 ? ???????? ????? ? ZnO ?????? [3] ????????? ??????????
????? 940 ?. ? ?????? [22] ????????, ??? ?????????????? SnO2 ??? ?????????? ??????????
????????? ??????? ?????????? ???? 670 ?, ? ???????? ??????????? SnO2 ? ??????????????
?????????? ????? ???? ???????? ??? ??????????? ????? 800 ?. ??????? ?????????? ??????????????? ??? ??? 788 ? ????? ??????????? ??????? ???????? ?????????????? SnO2. ???
?????????????? ? ??????????? ?????? ????????? ????????? ?????? ????? ??? ???????????
873 ? ?? ?????????????? (???. 2).
????? ???????, ?? 673 ? (??????????? ??????????? ?????? ????????) ??????????? ?????????? ???????????????? ????????? ????? ? ???????? ?????????? ????? ????? (IV) ? ???????????????????? ????. ????????? ??????????? ?????? ???????? ?????? ?? 1223 ? ??????????
??????? ? ???????? ???????????? SnO2·xH2?. ??????????? ???????? ??????????????? ? ??????????? ?? ??????????? ?????? ??????????? ????.
# 288 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????? ?????? ???????? Zn 2SnO4 ??????????????? ???????????? ??????????
R
R
R
R
R
R
R
R
R
R
1223
R
R
R
R
R
R
R
R
R
R
R
1073
?????????????
R
R
1173
R
R
R
973
R
R
R
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R
R
R
873
R
R
R
R
R
R
R
773
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R
R
R
673
20
30
40
50
2 T , ????.
60
70
???. 2. ?????????????? ?????, ?????????? ? ??????? 2 ? ??? ????????? ????????????, ?: * ? Zn 2SnO4,
+ ? SnO2, o ? ZnO
? ?????? ?????????? ??????????? ???????????? ??????? ???????, ??????????? ??? ?????????? ????????? ?? ????????, ????? ???? ???????????? ? ????????? ????:
SnCl4 + 2(NH4)2CO3 + xH2O = SnO2·xH2O ? + 2CO2? + 4NH4Cl,
(5)
4Zn(CH3COO)2 + 4(NH4)2CO3 + 4H2O = Zn4(OH)6CO3 H2O? +
+ 8CH3COONH4 +3CO2.?
(6)
??????????????? ??????. ? ????. 1 ? ?? ???. 2 ????????? ?????????? ??? ??? ??????,
?????????? ??? ???????????? ? ????????? 673-1223 ?. ?? ??????????? ????. 1 ?????, ??? ???????????? ?????? ???????? ????? ??????? ??????????? ??? ??????????? ???? 1073 ?. ????
???? ??????????? ???????????? ???? ???? ??????? ????? (IV) ? ?????.
? ????????, ?????????? ??? ???????????? 673 ? 773 ?, ???????????? ??????? ?????????? ???????? ???? ???????? ?????. ???? ????? 873 ? ???????? ??????????????? ???? SnO2
??????? ???????????, ??? ?????? ? ?????????? ????? ?????? ?????? ?? ??????????? 1073 ?.
??? ?????????? ????????? ??????????? ?????? ????? ???????? ????? ?? ??????????????,
??? ? ????? ?????? ?????, ??????????? ????????? ?, ? ???????????? ? ???? ?????????? ???????? ???? ???????? ???????? ?????. ??? ??????????? 1173 ? ?? 2 ? ?????? ???????? ?????????
???????? ?? 40 % ? ????????? ~83 % ??? 1223 ?. ???, ? ?????, ????????????? ????????????
??????: ?????? Zn2SnO4 ?? ???????????? ????? ???????? ZnO ? SnO2 ??? ? 1273 ? ? ??????? 4
? ????????? ?????? [5], ? ??? ?????? ????????????? ??????? ?? ????????????? ??????? ??????
??????? ZnSn(OH)6 ????????? ????? ?????? ??????????? 1070? (??? ???? ?? ?????? ??????????
?? ??????? ???????? 70 ?? ??????????? ??????? Zn2SnO4 ????? 10 ??) [3]. ???? ????? ?????? ? ??????????? ????? ?????? ??????????? ??????? ???????? [23]: ???????????? ??????????
????? ? ????? ???????? ????????????? ??????????? Zn2SnO4 ??? ??? 517 ?, ?? ????? ???????? ?? ??????????????? ????????? ??????????? ???????, ??? 1173 ?.
# 289 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????? ?????? ???????? Zn 2SnO4 ??????????????? ???????????? ??????????
??????? 1. ??????? ?????? ????????????????? ???????? ?? ??????????? ???
???????????
??????????????, ?
?????????? ??? ? ????????, ???.????
ZnO
SnO2
Zn 2SnO4
673
1
-
-
773
1
-
-
873
0,88
0,12
-
973
0,80
0,20
-
1073
0,59
0,41
-
1173
0,17
0,41
0,42
1223
0,09
0,08
0,83
?????????????? ???????? ??????????? ??/??? ? ??? ???????. ??????????? ?????? ????
??????????? ?????? ?????????????? ???????? ????? ????? 788? (???. 1), ??? ????, ?? ??????
???, ?????? ??? 673 ? 773 ? ?? ???????? ? ???????????? ??????????????? ???? SnO2 ? ??????????? ?????? ??? ???????????, ??????? ?????????? ??? 873 ?. ????? ????, ??????????
????? 1200 ? ??? ??????????? ? ???????????? ??? ????? ??????? ? ????????? ??????? ? ?????????????? ???????? ????? (???. 2).
??????????? ????????. ??? ????????? ??????? ? ?????????? ?????????? ?????????
??????? ???? ??????????? ????????????????? ????????????. ?? ???. 3 ???????????? ?????????????? ???????? ??????????? ???????????? ????? ? ???????, ??????????? ?? ??????????????? ??? 1223 ?. ????????? ???????????? ????? ??????? ??????? ?? ??????? ????????
????? 100 ??? (???. 3? ? b). ? ?????????? ????????? ? ?????????? ???????????? ?????????????? ??? ?????????????? ???????? ??????? ???????????, ??????? ??????? ?????????????
?? ?????? ?? ???????? ??? (???. 3c). ???????? ?????????? ?????? ????? ??????? ????? ??????
???????????? ????? ?????? ??????????, ????????? ?? ???????????????? ?????? ??????? 50200 ?? (???. 3d).
????? ?????????????? ???????????? ??????????? ?? ?????? ???????? ??? ????????? ?????????? ???????????? ?????????? [15, 24] ? ??????????? ??????????? ??????? ?????????? ?
??????????? ???????? ???????????? ???????????????? ??????? (? ?????? ?????? Zn2SnO4).
??? ?????????????? ??????? ?????????????? ??????? ???????? ????? ??????????? ?? ?????????. ??? ??????????? ???????????? ????????? ? ???? ??????? ????????? ????? ???????
???????????. ? ?????? [5] ?????? ???????? ???????? Zn2SnO4 ? ????????????? ??????????
90-92 % ????? ???????? ???????????? ?????????? ???????? ??? 1523-1573 ? ??? ???????? ??
??????? ZnO ? ??????? 2 ?.
???????????? ????????????? ????????? ????? ????????? ??????????? ????????????
????? ?? ??????? ??????? ???? ? ????? ????????? ????? Cu/10Zn 2SnO4 ??? ????????????
?????????. ??????? ??????? ??????? ? ?????????? ??????? ??? ????? ??????? ? ??????
??? 1173 ? ? ??????? 2 ?. ???-?????? ??????? ?????? ????????????? ??????? ? ????????????
???????? ??????? ???????. ????? ?????????? ????? ???????? ??????? ??? ????????? ????????? Cu/Zn 2SnO4 ? ?????????? ?????????????? ???????????????? ????????? ????????
??????.
# 290 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????? ?????? ???????? Zn 2SnO4 ??????????????? ???????????? ??????????
(?)
(b)
(c)
(d)
???. 3. ???-??????????? ????????????? ?????????? (?, b), ??????????? ??????? (c) ? ?????????? ??
?????? Zn 2SnO4 ????? ?????????????? ??? 1223? (d)
??????????
?????? ???????? ?????? Zn2SnO4 ??? ?????????????? ?? ??????? ? ??????? 2 ? ????????????????? ????? ????????? ?????????? ?????????? ????? (Zn4(OH)6CO3·H2?) ? ?????
(SnO2·xH2?) ??????????? ??? ???????????? ???? 1100 ?, ? ??? 1223 ? ????? ???????? ?????????? ???? 80 %. ????? ?????? ????????? ?????? ???????? ?????????? (10-20 ???) ??
?????? Zn2SnO4 ???????? 50-200 ??. ?????? ???????? ??????? ????? ?????????? ??????????
????????????? ?????? ???????? ????????? ???????? ?? ??????????? ?????????????? ???????
(????, ???????) ? ???? ??????????? ? ?????????? ???????????? ??????????????? ??????????
??????????????????? ??????????.
?????? ???????? ????????????? ?.?. ?????? ? ?.?. ???? ?? ?????????? ???????????????? ? ??????????-????????????????? ???????.
?????? ????????? ? ?????? ??????? 2.1.2/531 ???? «???????? ???????? ??????????
?????? ????? (2009-2010 ????)».
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????? ?????? ???????? Zn 2SnO4 ??????????????? ???????????? ??????????
?????? ??????????
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12. ??????????? ?.?., ????????? ?.?., ?????? ?.?. ??????? ?????????? ?? ?????. ????:
??????? ?????, 1974, 991 ?.
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19. ?????????? ??????. ?.2. ???????? ???????? ?????????????? ? ???????????? ??????????/ ??? ???. ?.?. ???????????. ?.: ?????, 1971. 1168 ?.
20. Wu W., Jiang Q. Preparation of nanocrystalline zinc carbonate and zinc oxide via solid-state
reaction at room temperature// Materials Letters. 2006. V.60. ?.2791-2794.
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Some Aspects of Zn2SnO4 Powders Synthesis
by Thermotreatment of Coprecipitated Compounds
Andrey V. Sidorak, Alexander A. Shubin,
Viktor V. Ivanov and Natalya S. Nikolayeva
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041 Russia
The results of investigation of Zn2SnO4 superfine powders synthesis processes by thermaltreatment
of coprecipitated zinc and tin (IV) compounds from solutions are shown. The coprecipitated powder
mixtures were studied by TG/DSC, XRD, XRF and SEM methods. Thermaltreatment of the precipitate
samples in range of 673 ? 1223K for 2 h revealed that the synthesis of Zn2SnO4 proper oxide can be
observed at above 1100 K and the materials yield is about 83 % at 1223 K. The porous agglomerates
of Zn2SnO4 particles about 50 ? 200 nm in size are formed under the annealing. The given method was
tested to prepare Cu/Zn2SnO4 powder mixture and it showed its efficiency.
Keywords: zinc stannat, powders, chemical precipitate, thermolysis, synthesis.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 3 (2010 4) 294-300
~~~
??? 542.06:533.9...15
???????????? ?????????? ?? ??????????
????????????? ???? ? ?????????? ????????,
???????????? ??? ???????????????? ???????
? ??????????????? ??????? ???????
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?.?. ????????, ?.?. ??????????, ?,
?.?. ???????, ?.?. ???????, ?,
?.?. ?????????????, ?.?. ????????, ?*
?
?????????? ?????????? ???????? ???? ???????? ??????
??. ?.?. ?????????? ?????????? ????????? ???
?????? 660036, ??????????, ??. ?????????????, 50, ???.38
?
????????? ??????????? ???????????
?????? 660041, ??????????, ??. ?????????, 79 1
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
? ?????? ???????????? ?????????? ???????????? ?????????? ?? ?????????? ?????????????
???? ? ?????????? ????????. ??????? ???? ???????? ? ?????? ?????????-???????? ??????
??????????????? (66 ???) ???? ??? ??????????? ????????. ??????????-????????????????
??????????? ?????????? ????????, ??? ??? ????? ???? (??????, ??????) ????????? ?? 20 ??
50 ??, ???????? ?????????? ????????? ???????? ?? 5 ?? 15 ??. ?????????? ???????? ???????
?? ??????????? ?????????? ????? ? ???????????????? ??????????? ????? ???????????
??????????? 3.37 Е.
???????? ?????: ???????????????? ??????, ????????????? ???????????, ?????????? ????????,
??????????????? ??????.
????????
????????????? ???????????, ????????????????? ??????? ?????????? ????? ????????????? ?????? ? ????? ???????? ?????? ? ?????????? ??????? ?????????? ???????????,
??????? ? ??????? ?????????? ? ?????????? ?????, ????????, ????????? ? ?????????.
??? ???????????? ?? ???????????? ?????????? ? ?????????? ???????????? ?????????? ?
?????????? ???????. ??????????????? ????????????? ??????????? ????? ????????? ??
*
1
Corresponding author E-mail address: Churilov@iph.krasn.ru
© Siberian Federal University. All rights reserved
# 294 #
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?.?. ???????, ?.?. ????????? ???????????? ?????????? ?? ?????????? ????????????? ???? ? ?????????? ?????????
????????, ??????? ????????, ??????, ??????, ?????? ???? ? ????????? [1-3]. ??????, ?????? ???????????? ????????? ?? ?????? ????????????? ?????????? ?????? ? ??????????
?????, ?? ? ???????????? ?? ??????? ???????????????? ? ????????? ? ??????? ????????????? ??????????? [4]. ????????????? ???????????, ???????? ???????? ??????????
?????????, ????? ???? ???????????? ? ????????? ?????????, ????????? ???????????,
????????? ????????, ???????? ?????????, ??????????? ? ?.?. ???????????, ??????????
???? 3d ??????? (??????, ???????, ??????), ???????????? ????????? ??????? ??-?? ?? ????????? ???????. ? ?????????? ?????? ??????? ????????? ??????? ??????? ?????????? ??
?????????? ????????????? ???? ? ?????????? ????????: ??????? ??????, ?????????????
??????, ?????????????? ???????? ??????, ?????, ???????, ?????????? ????????? ?? ??????? ????, ????? ? ?????? [5-9]. ?????? ? ???????? ??????? ????????????? ??????????,
???????? ?????????? ?????????, ??????????: ?????????? ??????????, ???????, ????????, ???????? ??????? ? ????????????? ???????. ????????? ?????????? ?? ??????????
????????????? ???? ? ?????????? ???????? ??????? ?????????? ?????????? ? ??????????
???????? ???????.
? ???? ?????? ???????????? ?????????? ???????????? ?????????? ?? ?????????? ????????????? ???? (??????, ??????) ? ?????????? ????????, ?????????? ??????? ????????????????? ??????? ? ??????????????? (66 ???) ???? ???????????? ????????. ?????????
?????????? ?????????????? ?? ??????????? ???????? ??????????? ??????? ???????, ?????
????????? ? ??????? ? ??????? ????????.
????????????????? ?????
?????????? ?????????, ?????????? ?????? ? ??????, ??????? ? ?????????-????????
?????? ??????????????? (66 ???) ???? ??? ??????????? ???????? ?????. ????????? ???
??????? ??????????? ?????????? ???????? ??????? ???? ????? [10]. ?????????? ????????
?????????? ? ?????? ????????? ?????? ?? ?????????? ??????????. ?????????????? ???????????????? ???????: ?????? (Ni ? 98,6 % ???.) ? ???????? ?????? 0,5 ??? ? ?????? (Fe ?
98,7 % ???.) ? ???????? ?????? 60 ???. ??????????? ????????? ? ?????? ???????????
???????? (??????, ??????) ? ???????? ?????????? 1:7. ?? ?????? ???????????????????????
??????? ?????????? ?????????? ??????? ? ?????????? ??????????? ???? ??????: ???
???????? Ni ? 1,5 % ???. ? ??? ???????? Fe ? 6 % ???. ????????? ?????????? ?? ??????????
????????????? ???? ? ?????????? ???????? ?????????????? ????? ????????? ???????????
?????????? ? ????????????????? ??????? ??????? ? ??????? 3,5 ?, ????? ??????????????
?????? ???????????? ??????? ???????? ? ???????? ????? ?? ????. ?????????? ?????????? ??????? ? ?????????? ???????????? ??? ???????? Ni ????????? 10,6 % ???., ??? ???????? Fe ? 5,8 % ???.
????????? ? ?????? ???????? ??????????? ????????: ?????????? ????????????? ????????? (???????????? ????-4, Cu K?), ??????????????????????? ??????? (???????????
Bruker Pioneer S4), ??????????????? ????????? (??) (Horiba Jobin Yvon T64000, ????? ?????
????????? ??????????? 514,5 ??), ???????????? ?????????? ????????? (?????-???????????
Elexys E580 Bruker). ??????????? ???????? ???? ???????? ?? ??????????? ???????????
?????????? ? ??????? ???????? JEOL JSM-7001F.
# 295 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ???????????? ?????????? ?? ?????????? ????????????? ???? ? ?????????? ?????????
?????????? ? ??????????
?? ??????? 1 ???????????? ??????????-???????????????? ??????????? ????????? ??????, ???????? ?????????? ?????????. ??????? ????? ????????????? ???? ????????? ?? 20
?? 50 ?? ? ?????????? ???????? ???????? ?? 5 ?? 15 ??. ?????????? ???????? ??????? ??
??????????? ?????????? ?????.
?? ?????????????? ?????? ??????, ???????? ?????????? ?????????, ???????????? ????????????? ????????? ??? 2?=44.4, 51.8 ? 76.4 °, ??????????????? ?????????? ????????? ??????, ? ????????????? ????????? ??? 2?=26.4, 42.4 ? 44.5 °, ??????????????? ?????????????? ????????? ??????? (???. 2-1). ??????, ?????? ?????????????? ????????? ?? ?????????
??????? (002) ?? 26.4 °, ???????????????? ??????????? ?????????? 3.37 Е, ??????????? ????????????? ????????? ??????? ????????????? (25.7, 24.8, 24.2, 23.8 ? 23.2 °), ??????????????? ???????????? ??????????? ?????????? (3.45, 3.58, 3.67, 3.74 ? 3.82 Е). ?? ??????????????
?????? ??????, ???????? ?????????? ?????????, ???????????? ????????????? ?????????
??? 2?=44.7, 65.1 ? 82.4 °, ??????????????? ?????????? ????????? ??????, ? ?????????????
?????????, ??????????????? ?????????????? ????????? ???????, ??? ?? ??? ? ?????? ????????? ?????????? (???. 2-2). ??????????? ????????????? ????????? ?? ????????? ???????
(002) ??????? ????????????? (25.8, 25.3, 24.3 ? 23.5 °), ??????????????? ???????????? ??????????? ?????????? (3.45, 3.52, 3.65 ? 3.78 Е).
????????????, ??????????? ??????? ??????????????? ?????????, ????????? ??????????
??????? ???????????? ???????? ? ????????????. ??-??????? ?????? ?????? ? ??????, ????????
?????????? ?????????, ?????? G-?????? (1580 ??-1), ??????????????? ?????????????? ?????????? ?????? ????????, ??????????? ?? ?????????? ?????????, ???????? D-?????? (1350 ??-1),
??????????????? ??????? ???????? ? ?????????? ?????????? (???. 3). ??????????? D-??????
? ??-???????? ?????????? ?? ?????????? ????????????? ???? ? ?????????? ???????? ??????????? ???????? ?????????? ??? ????????? ?????? (???? ? ????). ????????? IG/ID ??? ??????
???. 1. ??????????-???????????????? ??????????? ????????? ??????????, ???????? ??????????
????????? ? ?????? ???????????
# 296 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ???????????? ?????????? ?? ?????????? ????????????? ???? ? ?????????? ?????????
???. 2. ?????????????? ?????? ?????? (1) ? ?????? (2), ???????? ?????????? ?????????
???. 3. ??????? ??????????????? ????????? ?????? ?????? (1) ? ?????? (2), ???????? ??????????
?????????
?????? ? ??????, ???????? ?????????? ?????????, ????????? 1,06 ? 1,00, ??????????????, ???
??????????? ? ????????????? ??????? ??? ????????????? ?????? (??????, ??????, ???????),
???????? ?????????? ?????????, ?????????? ??????? ????????? ??????? [9].
??? ?????? ?????? ? ??????, ???????? ?????????? ?????????, ??????????? ?????????????? ????? ???????????? ?????????? ?????????, ??? ????? ???? ??????????? ?????????
???????????? ?????? (???. 4). ????????????? ??????????? ????? ???????????? ??????????
????????? ????????, ??? ??????? ?????? ????????? ?????????????????? ????????, ? ?????? ?
??????????????. g-?????? ??????????? ???????? ? ???????, ?????????? ????????? ???????,
???????? 2,0034, ? ?????????? ???????? ??????? ? 2,0008.
# 297 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ???????????? ?????????? ?? ?????????? ????????????? ???? ? ?????????? ?????????
???. 4. ??????? ?????????? ????????? ?????? ?????? (?) ? ?????? (?), ???????? ?????????? ?????????
??????????
? ?????? ???????????? ?????????? ???????????? ?????????? ?? ?????????? ????????????? ???? ? ?????????? ????????, ?????????? ??????? ????????????????? ??????? ? ??????????????? (66 ???) ???? ???????????? ????????. ?????????????????? ??????? ?????? ?
?????????????? ??????? ?????? ????? ????????????? ???? ????????? ?? 20 ?? 50 ?? ? ?????????? ???????? ???????? ?? 5 ?? 15 ??. ?????????? ???????? ??????? ?? ??????????? ?????????? ????? ? ???????????????? ??????????? ????? ??????????? ??????????? 3.37 Е.
??????????, ?????????? ???????? ???????????????? ??????? ? ??????????????? ?????????,
????????, ??? ?????????? ????? ?????????? ????????? ??????? ?????? ? ?????? ???????
?????????? ????????? ? ????? ??????????? ????????.
?????? ????????? ??? ????????? ????????? ???? (?????? ? 09-03-00383-?).
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Synthesis, growth mechanism and magnetic properties of SiO2-coated Co nanocapsules. Acta
Materialia. 2007. V. 55. P. 3727-3733.
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of 5-Fluorouracil: Preparation, characterization and cytotoxicity studies. Colloids and Surfaces B:
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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ???????????? ?????????? ?? ?????????? ????????????? ???? ? ?????????? ?????????
Investigation of Nanoparticles
with Metallic Core-Carbon Shell Structure Created
at Plasma-Chemical Synthesis
in High Frequency Arc Discharge
Irina V. Osipovaa, Gariy A. Glushchenkoa,
Viktoriya G. Isakovaa, Elena A. Goncharovaa, b,
Alexander S. Krylova, Sergey M. Zharkova, b,
Eleonora A. Petrakovskayaa and Grigory N. Churilova, b
a
L.V. Kirensky Institute of Physics SB RAS
50/38 Akademgorodok, Krasnoyarsk, 660036 Russia
b
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041 Russia
The results of investigations of nanoparticles with metallic core-carbon shell structures are presented
in the work. They were created in the flow of carbon-helium plasma of high frequency (66 kHz) arc at
the atmospheric pressure. The electron microscopy micrograph of the nanoparticles showed that they
have core (nickel, iron) diameter from 20 to 50 nm covered by the carbon shell of thickness from 5 to
15 nm. The carbon shell consists of spherical graphitic layers with preferred distance 3.37 Е between
graphitic layers.
Keywords: plasma-chemical synthesis, metallic nanoparticles, carbon shell, high frequency plasma.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 3 (2011 4) 301-306
~~~
??? 547.314
?????? ???????? ?????-N-??????????????????
?.?. ????????, ?.?. ?????????*,
?.?. ??????????, ?.?. ?????????, ?.?. ?????
????????? ??????????????? ??????????????? ???????????,
?????? 660049, ??????????, ??. ????, 82 1
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
1-(1-?????????)-3,5-???????-4-???????-1H-??????? ? 1-(1-?????????)-5-?????-4-???????3-?????-1H-??????? ????????????? ????????????????? 2-????????????-1,3-????????? ?
??????????????? ??????????????????.
1-(1-?????????)-3-?????-4-???????-1H-??????? ??????? ????????????????? ??????????????
?????????????????? ? ????????? ?????????????? 4,4-??????????????-2-??? ? ??????
?????.
??? ?????????????? ??????????????? 4-???????????????? ????????-???????? ? ???????????
???????????? Pd/C ???????? ??????????????? 4-?????????????.
????????
?????:
2-????????????-1,3-???????;
3-????????????-2,4-??????????;
2-????????????-3-????????????; 1-(1-?????????)-3,5-???????-4-???????-1H-???????; 1-(1?????????)-5-?????-4-???????-3-?????-1H-???????; 1-(1-?????????)-3-?????-4-???????1H-???????.
????????, ??? ???????? ?????????????? ????????? ? ???????????? ?????????? ???????? ? ??????????? ?? ????????????? ??????????, ??????? ? ????? ???????? ?? [1, 2].
N-?????????????????????? ? ?????????????? ? 4-? ????????? ?? ?????????? ??????? ????
??????????, ???? ??? ???????????? ??? ????????????? ??????????, ????????? N-??????????4-??????????????? ? N-?????????-3,5-???????-4-?????????????? ???????? ?????????????
?????????? [3, 4]. ????????????? ????? ?????????????? ? ???????????, ??? ????????? ???? ?
4-?????-N-???????????????????????, ? ????? ? ???????? ???? ??????????, ???????, ? ????
???????, ????? ???? ???????? ????? ?????????????? ??????????????.
????? ????? ?????? ????? ???????? ?????? ??????? N-?????????-4-???????????????? ?
N-?????????-4-??????????????.
*
1
Corresponding author E-mail address: imidazol5@yandex.ru
© Siberian Federal University. All rights reserved
# 301 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ?????????? ?????? ???????- ? ?????-N-??????????????????
?????????? ? ??????????
????????????? ???????? ??????????? ??? ????????? N-?????????-4-????????????????
????? ????? ????????????? ?????????????????? (1), ????? ??? ???????????????? ? ????????????????? ? 1,3-?????????? ??? ??????? N-?????????????????? [5]. ?????? ??? ?????????????? ?????????????? (1) ? 3-??????????????????-2,4-?????? (2) ??????????? ????????
???????? ?? ??????????, ??? ????? ???? ??????? ? ??????????????? 1,3-???????? (2) ? ??????
????? [6] ? ????????? ?????????? ?????????????????? ??? ??????????????. ? ????? ? ????
? ???????????????? ? 1,3-????????? (2) ???????????? ??????????????? ??????????????????, ?????????????? ??????????? ?????? ??????????? ?????? ? ?????????? ???????? ?????????????? (1). ???????????????? ??????? ????????? ??? ????????? ??????????? ? ???????
? ???????????? 1-(1-?????????)-3,5-???????-4-???????-1?-???????? (3) ? ??????? 40 % (???.
1). ? ??????????? ??????? ?? 2-????????????-1-??????????-1,3-????? ???????????? 1-(1?????????)-5-?????-4-???????-3-?????-1?-??????? (4) (???. 1).
?????? N-?????????-3-?????-4-??????????????? ??????????? ?????????????????
2-????????????-3-???????????? (5) ? ??????????????? (1). ???????????? (5), ?????????? ??????????????? ?????????????? 3-???????????? ? ?????? ?????, ??????? ? ??????? ? ??????????????? (1) ??? ????????? ?? ??????????? ????? (???. 2). ???????????? ????? ??????,
???????????????? ?????????????????? 2-????????????-3-????????????, ???????? ? ?????
????????? ??? ?????????? ???????? ???????? 1-(1-?????????)-3-?????-4-???????-1?-???????
(6) ????-???????? ????? (??? 3).
?????? ??????????? ????????????? ???????????? ??????? ????????????? ? ??????????????? ????????? (3), (4), (6). ? ??????????? ???????? ?????????? (3), (4) ? (6) ? ??????? 660680 ?? ????????? ??? ?????????? n,?* ???????? ????????????? NO-??????. ? ??????? ??? 1?
?????????? (6) ? CDCl3 ?????? ??????? ???????? ????????? ? ??????? 7,16 ?.?. ??????? ???????? ????????? ?????? ? 3-? ????????? ?????????? (3), (6) ??????????? ? ???? ????????? 3,24
? 3,35 ?.?. ??????????????, ? ?????? ???????? ????????? ?????? ? ????????? 5 ?????????? (3),
O
HN
NH3
NO
O
2HCl
Me
1-Ad
R
KOH Me
-H2O
R
N
OH
R=Me, Ph
N
N
1-Ad
3 R= Me
4 R=Ph
???. 1. ?????? 1-(1-?????????)-4-???????-1?-?????????
Me
Me
OMe
Me
O
HCl, H2O
O
OMe
NaNO2, H
O
H
O
H
5
???. 2. ?????? 2-????????????-3-???????????? (5)
# 302 #
O
NOH
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ?????????? ?????? ???????- ? ?????-N-??????????????????
NO
(5)
Me
NH2NH-(1-Ad) 2HCl
N
1-Ad
N
69%
6
???. 3. ?????? ??????????????? (6)
NO
H2N
R1
R
NH2NH3 OH
R1
R
Pd/C
N
N
N
1Ad
N
1-Ad
3 R=R 1=Me;
4 R=Me, R 1 =Ph;
6 R=H, R 1=Me.
7 R=R 1=Me;
8 R=Me, R 1 =Ph;
9 R=H, R1=Me.
???. 4. ?????????????? ???????????????? (3), (4) ? (6)
(4) ? 2,30 ?.?., 2,26 ?.?. ??????????????. ? ??????? ???? ???? ?????????? ??????????? ???????
???????? ?????????????? ????????? ? ??????? 1,6-2,4 ?.?. ? ??????? ??? 1? ?????????? (4)
???????????? ????????????? ??????? ???????? ?????????? ???????????.
?????????????? ?????????????? ???????? 1-(1-?????????)-4-????????????? ??????????????? ??????? ??????????????? 4-????????????????, ????????? ????????? ?????????????
????? ????????? ????????????? ?????????? ?, ????? ????, ??????????? ????????? ??????? ?
?????? ??????? ?????????? ????? ??????????????.
?? ????????? (3), (4) ? (6) ??? ?????????????? ????????-???????? ? ??????????? ???????????? (Pd/C) ?????????? ??????????????? ???????????????? (7), (8), (9) ? ??????? 51-95 %.
?????? ? ???????? 1-(1-?????????)-4-?????????????? (7), (8), (9) ???????????? ??????
??? 1? ? ????-?????????????.
? ???????? ??? 1? ?????????? (7-9) ???????????? ????????? ??????? ???????? ????????????? ??????????? ? ??????? 2,45-2,65 ?.?. ?????????? ?????? ??????? ????????????
???? ?????????? (9) ? CDCl3 ???? ?????? 7,15 ?.?. ?????? ???????? ????????? ?????? ? 3-?
????????? ?????????????? (7), (9) ?????????? ?? 2,37 ? 2,39 ?.?. ??????????????, ????? ???
?????????? ?????? ????????? ?????? ? 5-? ????????? ??????? ?? 2,19 (?????????? (7)) ?
2,26 a?.?. (?????????? (8)). ? ??????? ?????????? (7), (8), (9) ??????????? ??????? ????????
?????????????? ????????? ? ??????? 1,76-2,28 ?.?.
????????????????? ?????
??????????? ?????? ??????? ?? ???????????????? Helios Omega ? ????????? ???????
1 ?? ??? ???????????? 0,5Ч10 -4 ????/? ? ??????? 200-450 ?? ? ???????????? 1Ч10 -2 ????/? ?
# 303 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ?????????? ?????? ???????- ? ?????-N-??????????????????
??????? 600 ? 750 ?? ? ???????. ???-??????? 1? ? 13? (600,13 ? 150,9 ???) ???? ????????
?? ???????????? Bruker Avance III 600. ????-?????? ??????????????? ?? ????-????????????
Finnigan 8200. 3-????????????-2,4-?????????? ???????????? ?? ???????? [7]. ??? ??????????
????????????? ???????????? ?????????? ????? Silicagel L 100/400 (????? Chemapol).
1-(1-?????????)-4-???????-1?-???????? (3, 4). ????? ????????. ? ???????? 0,61 ?
(2,56 ?????) ?????????????? ?????????????????? ? 14 ?? ?????? ???????? ??????? 0,145 ?
(2,55 ?????) ?????? ???? ? 3 ?? ??????, ????? (2,6 ?????) 2-????????????-1,3-???????? ? ????????? 12 ? (??? ?????????? (3)) ??? 24 ? (??? ?????????? (4)) ??? 24 ??. ?????????????
????? ?????? ?????????? ?????, ???????? ??????? ?? 5 ?? ??????, ???????? ?? 0 ??, ???????? ?????? ?????????????. ??? ????????? ???????????? ??????? ??????? ?????? ???????? ??
?????????????????? ??????? (2Ч50 ??) ? 50 ? ??????????. ??????: ?????? ? ?????????? (49:1).
????-??????? ?????????, ?????????? ? ???????, ??????????.
1-(1-?????????)-3,5-???????-4-???????-1?-??????? (3). ????? 0,26 ? (40 %). ?. ??.
?
127 ?. ??????????? ??????, ?????., ?? (?): 308 (16620), 661 (60). ?????? ??? 1?, ?, ?.?.: 1,821,83 ? (6?, ??2), 2,22 ? (3?, ??), 2,30 ??. ? (3?, ??3), 2,40-2,41 ? (6?, ??2), 3,24 ??. ? (3?, ??3).
????-??????, m/z (I???., %): 259 (68) [?]+, 135 (100), 125 (14), 107 (14), 93 (23), 79 (24), 67 (11), 55
(14).
1-(1-?????????)-5-?????-4-???????-3-?????-1?-??????? (4). ????? 0,21 ? (35 %). ?. ??.
182 ??. ??????????? ??????, ?????., ?? (?): 309 (14740), 674 (50). ?????? ??? 1?, ?, ?.?.: 1,64-1,70 ?
(6?, ??2), 2,14 ? (3?, ??), 2,20 ? (6?, ??2), 2,26 ??. ? (3?, ??3), 7,52-7,56 ? (3?, ?????.), 7,647,65 ? (3?, ?????.).
1-(1-?????????)-3-?????-4-???????-1?-??????? (6). ????? 0,66 ? 4,4-??????????????2-??? (5 ?????) ? 5 ?? 1 ? ??????? ??????? (5 ?????) ???????????? ??? 20 °? 0,5 ?, ????????
?? 0 °? ? ? ??????? 0,5 ? ???????? ?? ?????? ??????? 0,38 ? (5,5 ?????) ??????? ?????? ?
3 ?? ????. ????? ?? ??????????? ????? ?????? ?????? ????? ? ??????? ????????????? ??????,
? ???????? ??????? 0,89 ? (3,75 ?????) ?????????????? ?????????????????? ? 20 ?? ????.
??????????? ????? ?????????? 10 ??? ??? 20 °?. ???????? ?????? ??????-???????? ?????
?????????????, ?????????? ? 20 ?? ?????? ? ????????? ?? ??????? ???? 3 ?. ????? ??????? ?
??????? ?? ?????? ???????? 5 ??, ???????? ?????? ?????????????. ????-??????? ?????????,
?????????? ? ???????, ??????????. ????? 0,63 ? (69 %). ?. ??. 142 ?? (??????). ???????????
??????, ?????., ?? (?): 309 (16500), 680 (56) ?????? ??? 1?, ?, ?.?.: 1,82-1,83 ? (6?, ??2), 2,31 ? (3?,
??), 2,40-2,41 ? (6?, ??2), 3,35 ??. ? (3?, ??3), 7,16 ??. ?. (1?, ?????). ???????, %: C 69,11, H 8,01,
N 17,83. C14H19N3O ?????????, %: C 68,54, H 7,81, N 17,13. M 245,32.
1-(1-?????????)-4-?????-1?-???????? (7-9). ????? ????????. ? ???????? 1 ?????
1-(1-?????????)-4-???????-1?-???????? (3, 4, 6) ? 30 ?? ?????? ????????? 0,1 ? ????????????
(0,5 %-???? Pd/C), ???????????? 0,5 ?, ????? ??? ??????????? ????????????? ???????? 0,4
?? 85 %-???? ????????-???????. ????? ?????????????? ???????? ???????????? ??? 0,5 ?,
????????????? ???????????, ???????? ??????? ? ???????, ??????? ?????????????? ??????.
???????? ??????? ?? 10 ??, ???????? ?????? ?????????????, ??????? 1 ?? ???????. ???????????? ?????????, ?????????? ? ?????, ???????.
1-(1-?????????)-4-?????-3,5-???????-1?-??????? (7). ????? 0,125 ? (51 %). ?. ??. 103?
104 ?. ?????? ??? 1?, ?, ?.?.: 1,76 ? (6?, ??2), 2,19 ? (3?, ??3), 2,21 ? (3?, ??), 2,26-2,27 ? (6?,
# 304 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ?????????? ?????? ???????- ? ?????-N-??????????????????
??2), 2,37 ? (3?, ??3), 2,45 ??. ? (2?, NH2). ????-??????, m/z (I???., %): 245 (100) [?]+, 135 (72), 111
(68), 107 (8), 93 (20), 91 (12), 79 (21), 77 (12), 70 (28), 67 (8), 55 (7).
1-(1-?????????)-4-?????-5-?????-3-?????-1?-??????? (8). ????? 0,29 ? (95 %). ?. ??.
?
171 ?. ?????? ??? 1?, ?, ?.?.: 1,56-1,62 ? (6?, ??2), 2,04 ? (3?, ??), 2,07 ? (6?, ??2), 2,26 ?
(3?, ??3), 2,47 ??. ? (2?, NH2), 7,33-7,35 ? (2?, ?????.), 7,43-7,47 ? (3?, ?????.). ????-??????, m/z
(I???., %): 307 (100) [?]+, 173 (35), 135 (50), 104 (20), 93 (15), 79 (19), 77 (17).
1-(1-?????????)-4-?????-3-?????-1?-??????? (9). ????? 0,14 ? (60 %). ?. ??. 114 ??.
?????? ??? 1?, ?, ?.?.: 1,76 ? (6?, ??2), 2,22 ? (3?, ??), 2,27-2,28 ? (6?, ??2), 2,39 ? (3?, ??3),
2,65 ??. ? (2?, NH2), 7,15 ? (1?, ?????). ????-??????, m/z (I???., %): 231 (100) [?]+, 135 (50), 97 (30),
93 (11), 91 (8), 79 (12), 77 (8), 56 (6).
?????? ???????? ????????????? ?.?. ??????????? (???? ????? ??? ?? ???) ??
?????? ???-????????.
?????? ??????????
1. ??????? ?.?., ?????? ?.?., ???????? ?.?. ???????????? ???????????. ????????? : ????? ?????????. ???. ????., 2001. 320 ?.
2. ??????????????? ?????????? ??????????????????? ???????????? / ?.?. ????????,
?.?. ??????, ?.?. ???????, ?.?. ???????, ?.?. ?????????, ?.?. ???????, ?.?. ??????? // ???.????. ????. 2002. ?. 36, ? 1. ?. 5-7.
3. Heterocyclic compounds : ???. 2827415 ??? : Cl 167-33 / Freeman W.A., Pain D.L., Slack R.. ?
? 603809 ; ????. 13.08.1956 ; ????. 18.03.1958.
4. Improvements in or relating to pyrazole compounds and compositions containing them : ???.
786753 ?????????????? : C07D231/38, ?07D 231/00 / Freeman W.A., Slack R. ? ? GB 19550004249
1950212 ; ????. 12.02.1955 ; ?????. 27.11.1957.
5. ?????????? ?.-?.?., ???????? ?.?. ????? ??????????????????. ????? 2. ???????????
????????????????? // ????. 1999. ?. 35, ???. 2. ?. 183-220.
6. Green A.L., Saville B. The reaction of oximes with isopropylmethylphosphonofluoridate //
J. Chem. Soc. 1956. P. 3887-3892.
7. ??????? ?. ?????? ???????????? ? ???????????? ?????. ?.: ??????????, 1952. ?. 293.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ?????????? ?????? ???????- ? ?????-N-??????????????????
Synthesis of Nitrosoand Amino-N-Adamantylpirazoles
Timofey A. Frolenko,
Elena S. Semichenko, Maria G. Melnikova,
Natalia A. Gavrilova and George A. Suboch
Siberian State Technological University
82 Mira, Krasnoyarsk, 660049 Russia
Synthesis of 1-(1-adamantyl)-3,5-dimethyl-4-nitroso-1H-pyrazole and 1-(1-adamantyl)-5-methyl-4nitroso-3-phenyl-1H-pyrazole done by the cyclocondensation of 2-hydroxyimino-1,3-diketones and
adamantylhydrazine dihydrochloride. Synthesis of 1-(1-adamantyl)-3-methyl-4-nitroso-1H-pyrazole
done by reaction of unstable 2-hydroxyimino-3-oxobutanal and adamantylhydrazine hydrochloride.
2-Hydroxyimino-3-oxobutanal obtained by nitrosation of 4,4-dimethoxybutan-2-one in an acid medium.
The 2-(hydroxyimino)-3-oxobutanal was injected into the cyclocondensation without isolation from
the reaction mixture.1-(1-?damantyl)-4-amino-1H-pyrazoles were synthesized through the chemical
reduction of synthesized 4-nitrosopyrazoles with hydrazine hydrate in the presence of Pd/C.
Keywords:
1-(1-adamantyl)-3,5-dimethyl-4-nitroso-1H-pyrazole;
1-(1-adamantyl)-5-methyl-4nitroso-3-phenyl-1H-pyrazole; 1-(1-adamantyl)-3-methyl-4-nitroso-1H-pyrazole; 2-hydroxyimino1,3-diketone; 3-hydroxyimino-2,4-pentanedione; 2-(hydroxyimino)-3-oxobutanal.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 3 (2011 4) 307-315
~~~
??? 547.442.3
?????????? ? ???????? ??????????
3-????????????-2,4-???????????
?.?. ?????????, ?.?. ????????????,
?.?. ??????????*, ?.?. ??????
?
????????? ??????????????? ??????????????? ???????????,
?????? 660049, ??????????, ??. ????, 82
?
??????????? ??????????????-??????????????? ????
«?????» ??? ?? ???
?????? 660049, ??????????, ??. ????, 53 1
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
??? ?????????????? 3-????????????-2,4-??????????? ? ?????????????? (???????????????)
??????? ?????????? ????????? ????? (3-????????????-2-???????????). ?? ?????????
?????? 1H ? 13C ???-???????? ? ?????????? ???????? 1H -13C ???? ? 1H -15N ???? ???????????
????????? ????????? 4-??????????????-3-??????????????????-2-??? ? 4-????????????????3-??????????????????-2-???. ????????? ??????? ???????? ????????? ????? ?? ???????????
?????????? ? ?????????? ????? ???????-???????????? ? ????????????-??????????????
???????.
???????? ?????: 3-????????????-2,4-??????????; 4-??????????????-3-??????????????????2-??; 4-????????????????-3-??????????????????-2-??; ????????? ?????; ???????????
??????????; ???; ????; HSQC.
????????, ??? ? ???????????????? ???????????????? 2-????????????-1,3-????????? ?
??????? ? ???????? ?????????? 3,5-???????????? 4-??????????????. ??????? ???????? ???
??????? ??????, ? ??????? ?????????? ??? ???????? ?????????? [1-3]. ?????? ??? ??????????
??????? 3-????????????-2,4-??????????? ? ???????? ? ?????????????? (???????????????)
??????? ? ????? ??? ???? ???? ???????? ????? ??????????????? ??????????, ?? ???????
?????????????? ????????. ?? ????????? ?????? ?? ??????????? ????????? ????? ??? ?????????????? 2-????????????-1,3-????????? ? ???????????? ??? ????????? [4, 5] ????? ????????????, ??? ?????????? ?????????? ???????? ?????????? ??????? 3-????????????-2,4??????????? ? ???????. ????? ?????? ???????????? ????? ?????? ? ???????????? ????????
*
1
Corresponding author E-mail address: imidazol5@yandex.ru
© Siberian Federal University. All rights reserved
# 307 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
????????? ?????????????? 3-????????????-2,4-??????????? ? ?????????????? ??? ??????????????? ???????. ???????????? ???????????? ?????? ???????????? ??????? ??????????? ????????? ????? ? ??????????????? ???????? ??????????????? ????????????, ??????????????, ????????? ? ?????? ???????? [6, 7].
?????????? ? ??????????
?????????????? ?????? ????????????? ? ????????? ??????????? ????????? ?????
???? ?????? ???? ?? ?????????? ???????????? ?????? ? 3-????????????-2,4-????????????
(???. 1). ??? ????? ? ???????? 3-????????????-2,4-??????????? ? ????? ???????? ????????????? ?????????? ?????????? ?????????????? ????? ? ??????????? ????? ???????????? ???
20 є? ? ??????? 2 ?, ????? ???? ????????????? ?????????????? ????? ???????.
?????? ?????????? ????????? ????? (I), (II) ??????????? ???????????? ???????????? ?
???????-????-?????????????.
??? ??????????? ? ?????????? ? ?????? ?????????? (I), (II) ?????????? ???????????????? ????????. ??? ?????????? ?????????????? ??? ????????? ????????? ?????????? ????? ????????. ???????? ???? ??? ???????? ????? ??? ????????? ?????, ??????????? ??
3-????????????-2,4-??????????? ? ???????????. ?????? ????????? ??? ??????? ? ????????
? ????????? 4-???????????-3-????????????-2,4-??????????? ?????????? ????? ???????????
??????????? ? ?????????, ?? ??????? ?????? ??????? ???????????? ? ??????????? ??????????? ???? (?????????????????? ?????????? ?????) [4]. ?????? ????? ????????????? ??????
??????? ?? ??????????? ?????????? ??????? ?????????? ??????????? ? ?(2) (???. 1), ? ???????
???????????, ?????????? ? ??????? ?????? ?????, ?? ?????????. ????? ????, ??????????????
??????????? ????? ??????????? ? ????????? ??????????? ?????? ?????????? ????????,
??????????? ?? ????????? ???? (????????? ????-????????? ??????????????) ? ?????????
?? ? ???????? ? ????????? ???????????. ??????????? ?????????????? ?????? ?????????
???????? ?????? ?????????? ????? ????????? ? ?????????? ? ??? ????? ????? ???????????
??????????? ????????? ????????.
??? ????????? ????? 3-????????????-2,4-??????????? (I), (II) ???????? ???????????
??????? ?????????????????-???????? (??, ?Z, ZE, ZZ), ????????? ???????-???????????
???? (Z, E) ? ???????????????? ??????? (III) (???. 2). ???? ??????????? ????? ??? ???
???????????? ??????? ?????????? ? ???????? ? ??????????????? ??????????? ????? ????
(????. 1, 2).
Me
O
(1)?H
NR
3
C (2)
RNH2
O
NOH
????
O
R= i-Pr, Cy
Me
C (3)
C (4)
C (5) H3
???. 1. ?????? ????????? ????? ?? 3-????????????-2,4-???????????
# 308 #
NOH
I R = Cy
II R = i-Pr
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
?? ????????? ???????? ??? 13C, 13C-APT (Attached Proton Test) ? ?????????????? ???????? 1H -13C ???? (Heteronuclear Multiple Bond Correlation) ? 1H- 13C HSQC (Heteronuclear Single
Quantum Coherence) ? CDCl3 ??????? ?????????? «?????????» ????????? ?????????? (I), ??????????? ?? ???????????????? ? 3-????????????-2,4-???????????.
? ???????? 13C ? 13C-APT ?????????? (I) ????????? ?????? ??????????? ????? (????. 1).
? ??????? 13C-APT ??? ???? ????????????? (CH, CH3) ? ???? ????? ? ???? (C, CH2). ???????
O
O
O
OH
O
OH
N
Me
N
N
O
Me
OH
Me
N
Me
H
Me
R
N
Me
R
Me
N
R
EE
N
ZE
EZ
O
N
ON
Me
Z
OH
H
Me
R
C
O
H
N
Me
ON
C
O
ZZ
R
Me
Me
N
Me
Me
N
E
N
R
R
III
???. 2. ??????? ????????? ????? 3-????????????-2,4-???????????
??????? 1. ?????????? ?????? ??? 1H, 13C ? 15N (?DCl3) ?????????? (I)
?????????? (I)
C=O
? 1H, ?.?.
(????*, ??)
-
Int*
? 13C, ?.?.
? 15N, ?.?.
-
199,5
-
>C=NOH
-
-
161,3
-
>C=N
-
-
152,1
-
CH (Cy)
3,71 p (J 4,79 ??)
1,23
53,7
-
CH2 (Cy)
1,51-1,40 m
1,6
32,4
-
2,59 s
3,43
27,6
-
CH2 (Cy)
1,66-1,65 m
2,59
25,0
-
CH2 (Cy)
CH3
1,90-1,81 m
2,5
23,9
CH3
2,43 s
3,74
16,1
202,8 (?N=)
NOH
18,50 b
1,0
-
-
*Int ????????????? ????????????? ????? 1H ???.
**???? ? ????????? ????-????????? ??????????????.
# 309 #
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?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
??????? 2. ?????????? ?????? ??? 1H, 13C ? 15N (?DCl3) ?????????? (II)
?????????
?????????? (II)
C=O
? 1H, ?.?.
(????*, ??)
-
Int*
? 13C, ?.?.
? 15N, ?.?.
-
199,8
-
C=O'
-
-
199,2
-
>C=NOH
-
-
161,7
-
>C=N
-
-
151,9
-
CH (i-Pr)
4,06 m (J 6,55 ??)
1,0
46,9
-
CH' (i-Pr)
3,10 m
0,05
46,9
-
CH3
2,59 s
3,01
27,5
-
CH3'
2,49 s
0,22
27,5
-
CH3 (i-Pr)
1,35 d (J 6,67 ??)
6,68
22,6
-
CH3' (i-Pr)
1,12 d (J 5,06 ??)
0,38
22,6
-
CH3
2,45 s
2,99
16,1
215 (?N=)
CH3'
2,10 s
0,17
16,1
322 (?N<)
NOH
18,59 b
0,87
-
-
*Int ????????????? ????????????? ????? 1H ???.
**???? ?????????? ????-????????? ??????????????.
? ??????????? 13C 161.3 ? 152.2 ?.?. ?????????? ??? ????????, ???????????? ? sp2 -??????????????? ??????, ? ???????? ? ????????? C(3) ? C(2) (???. 1) . ?????? ??????? 1H -13C HMBC ?????
???????????? ?????????????, ??? C(2) ?????? ??????????? ? ????????? ? C(3). ??????????????
?????? ?????????? (I) 1H -13C ????, ???????????????? ??? ???????? ??????? 8 ??, ???????
?????-??? ??? ???????? ? ?????????? ??????? (?, ?.?.) 199,5 ?.?., ?????????? ? ???????? C(4)
???????????? ??????.
????????? ?? ??????????? ????? ???? ????? (1H- 13C HSQC) ???????? ?????????? ?????????? ??????? ????????????? ????? ??????? APT 16,1 ? 27,6 ?.?. ? ?????????? ?????? 2,43 ?
2,59 ?.?. ??? ?????? ??????? ??? ????????? ????? ? ??????????????? ?? ?????????? (?(1) ?
?(5), ???. 1) ? ?????????? ??????. ????????? ???????, ?????? ??????? ????????? ?? 2,59 ?.?.,
??????? ? ???????????? ?????? ????????, ??? ?????????????? ???????? ??????? ??????????
(1H -13C ????) ???? ???????? ? ????????? ? ???????? 199,5 ?.?. ? ???? ??????? 6-7 ??. ????????? ??????? 2,43 ?.?. ??????????????? ? ????????? 152,1 ?.? (???? 6-7 ??) ? ? ?????????
161,3 ?.?. (???? 1,5-2 ??).
??? 13C 53,7 ?.?. ??????? ? ??????? ?????????? ???????? ????????????. ?? ??????? 13C- 1H
HSQC ???? ??? ???????????? ?????????? ? ????????? ???????????? 3,71 ?.?. ??? ??????
???????? 1H -13C ???? ? 1H- 13C HSQC ?????????? ???? 32,4, 25,0 ? 23,9 ?.?, ? ????? ???????????????? ? ???? ??????????? 1,51-1,40, 1,66-1,65 ? 1,90-1,81 ?.?. ??????????????, ???????? ?
???????? ?? ?????????????? ? ?????????? ???????? ????????????.
? ??????? 15N-1? HMBC (???. 3, ????. 1) ??????? ??????????? ?????-??? (202,8 ?.?.), ??????????????? sp2 -???????????????? ????? ?? ?????????? ???? ?????????? ? ?????????????
? ????????? 2,43 ?.?.
# 310 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
???. 3. ?????????????? ?????? 15N-1? HMBC ?????????? (I)
????? ???????, «?????????» ????????? ????????? ????? (I) ???????? ????????????
?????? (?=O) ? ??? ?????????, ? ??????? ??????? ?????? ? ?????? ????? ? sp2-????????? ????????? (>C=N-). ????? ????, ??????? ??? ????????? ??????, ???? ?? ??????? ???????????? ?
?????????, ? ?????? ? ? ????????, ????????? ? ??????????? c ??????????????? ????????????
(>C=N-Cy). ???? ??????? ????????????? ??????? ? ??-??????? ?????????? (I) ? ??????????
????? ?????????? 1685, 1665, 1635 ??-1, ??????? ????? ???? ???????? ? ????????? ??????????
???????????? (?=O), ??????? (?=N) ? ?????????????? (?=NOH) ?????.
?????????? ? ??????? ? ?????????????? ??????????? ??????????? ???? ??????????
(I) ? ???????? ?????????? ???????? ?? ????????? ???????? ??? ? ?????????????? ?????????? ???????? 1H -13C ???? ? 1H -15N ???? ??? ????????? ????????? ????????.
? ???????? ??? 1? ? 13? ?????????? (I) (????. 1) ??????? ?????? ???? ????? ????????, ???
??????????????? ? ??????? ???? ?????? ???????, ???? ?????????? ??????????, ????? ?????
???????? ????? ??????? ? ????? ??????? ?????? ???.
????????? ??? 18,5 ?.?. ? ??????? ??? 1H ?????????? (I) ????? ??????? ? ???????, ????????????? ???? ?????????? ????????? ? ?????????? ??????????? ???????. ????? ????????? ????? ????????? ?? ???????? ???????? 199,5 ?.?. ?????????? ??? ???????????? ??????,
???????????? ? ??????????? ?????????? ?????. ??????? ?????? ?????????? 3350-4200 ??-1
? ??-??????? ?????????? (I) ? ?????????? ?????? ?????????????? ?????????????? ?????????????????? ?????????? ?????. ? ?????? ???????-??????????? ????? ? ??????? ??? 1H
?????????? (I) ??? ????????? ??????????? ?????? ???? ??????????? ???? 18,5 ?.?., ??????
??? ??????????? ????? ???? ??????????? ??????? ???????. ?? ?? ???????? ? ???????? ?????????????? ? ????????? ???????, ????????? ? ???????????? ???????. ????? ? ???????, ??????
# 311 #
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?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
?????????????????-???????? ????? (??), ???????-??????????? ???? (Z), (?) ??? ????? ??
??? ?????? ?? ????????? ???????????? ??????? ?????????? (I) ? ??????????, ? ??????? ??????? ??????????? ??? ?????????? ?? 539 ??, ??????????? ? n,?* ???????? ????????????? NO?????? [2].
????? 15N 202,8 ?.?. ???????????? ????????????? ????? ? ???????? ?????.
????????? ???????? ??? ? ?????? ??????????? ? ??-???????? ?????????? (I) ? ?????????? ????????? ??????? ????? ? ??????? ??????????? ??????????, ?????????? ???????????
???? ? ????, ?? ???? EE-?????????????????-???????? ????? ? Z- ? E-???????-?????????
????, ????? ????? ??????? ????? ??????? ? ????? ??????? ?????? ???.
«?????????» ????????? ?????????? (II), ??????????? ?? 3-????????????-2,4-???????????
? ??????????????, ?????????? ?? ????????? ?????? ??? 13C, 13C-APT ? ??????????????
???????? 1H -13C ????, 1H- 13C HSQC ? ?DCl3. ? ???????? 13C ? 13C-APT ?????????? (II) ????????? 7 ????? (????. 2). ???? 161,7 ? 151,9 ?.?. ????????????? ???????????? ?????? ????????.
??????? ???????? ????????????? ?????? ????????? ?? 22,6 ? 46,9 ?.?., ????????? ????? ? ??
16,1 ? 27,5 ?.?. ?????????????? ?????? ?????????? (II) 13C- 1H ????, ???????????????? ???
???????? 8 ??, ??????? ?????????????? ?????-???? ??? ???????? 199,8, 199,2 ?.?., ??????????
? ????????? ???????????? ?????.
?????? 13C 16,1 ?.?. ?? ??????????? ????? ???? ????? (13C- 1H HSQC) ????????????? ???????? ???????? 2,45 ?.?. ?????? ???????? ?? 27,5 ?.?. ????? ?????-??? ? ????????? ????????
2,59 ?.?. ??????? ?????????? ? ??????? 13C- 1H ???? (????????? 8 ??) ???????? ????? ???????? ????????? ??????, ??????? ?????? ?? 2,59 ?.?., ? ????????????? ???????? ? ???????? ??
199,8 ?.?. ????????? ??????? 2,49 ?.?. ?????? ??????? ??????????????? ? ???????????? ????????? 199,2 ?.?. ???? ?? ????????? ??????? ??????????? ? ???????????? ????????? 161,7 ?.?.
? ????? ? 151,9 ?.?. ??? ?????? ????????? ??????? ? ????? ???????? ????????? ??? ????????
16,1 ?.?. (??????? 2,45 ?.?.) ? ???????????? ???????? 161,7, 151,9 ?.?., ???????????? ???????
199,8 ?.?. ? ????????? ??????? 27,49 ?.?. (??????? 2,59 ?.?.).
??????? ????????? ?????? (2,10 ?.?.) ????? ??????? ????? ? ?????????? 161,7 ?.?. ? ?????? ? 151,9 ?.?. ?? ???? ????????? ????????? ??????? 27,5 ?.?. (??????? 2,49 ?.?.) ???????????? ???????? 199,2, 161,7, 151,9 ?.?. ? ????????? ??????? 16,1 ?.?. (??????? 2,10 ?.?.) ????????
? ?????? ?????????, ????????????? ?????????? ??????? ??????, ??? ??????.
? ??????? 15N-HMBC ????????? ??? ???? 15N 215 ?.?. ? 322 ?.?., ??????????????? sp2- ?
3
sp -???????????????? ?????? ?????, ?????????????? (????. 2, ???. 4). ???? ????? ? ????????
?? 215 ?.?. ????? ?????-???? ? ?????????? ????????? ?????????????? ????????? (1,35 ?.?.)
? ????????? ???????? (2,45 ?.?.). ?????? 15N 322 ?.?. ????????????? ? ????????? ????????
2,10 ?.?.
????? ???????, ? ??????? 1H ??? ?????????? (II) ????? ???????? ??? ???? ??????? ??????????? ????????? ????? (?????? - ?H3-C=O , CH3-C=N, (CH3)2 CH; ??????, ?????????? ?
????. 2 ??????? ? - ?H3-C=O , CH3-C-N?, (CH3)2CH), ??????????????? ?????? ??????????.
??? ????????? ? ?????????????-???????? ?????? (???????????? ??????? ???) ???? ????????? ????????? ????? 2,59 ? 2,45 ?.?., ? ? Z ? E-???????-????????? ????? ????? 2,49 ?
2,10 ?.?., ????? ??????? ????? ? ??????????? ??????????? ???????????? ???? ??????????.
??? ??????? ???????????? ?????? ?? ???????????? ?????????????? ?????? ???????????
# 312 #
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?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
???. 4. ?????????????? ?????? 15N-1? HMBC ?????????? (II)
????? ????????? ????????, ?????? ?? ?????????????, ??? ? ????????? ?????? ????? ? ?????? ???? ???????? ? ????????????? ????????? ???????? ????????? ???? ?????. ????????
????????? ??????????? ???????? ????? ???????? ?????????????-???????? ???? ? Z ?
E-???????-?????????: ????????? ???????? ?????????????? ????????? ? 96,15 % (4,06 ?.?.) ?
3,85 % (3,10 ?.?.), ????????? ???????? ?????????? ? 94,61 % (1,35 ?.?.) ? 5,38 % (1,12 ?.?.). ???
????????? ???????? ?????????????? ????? ?? ??????????? ????????? ?? ????????? ??????
????? ? ????????? ? ?????? C=C ? ?=N. ??????????? ?????????????? ????????? ????????
?????????????-???????? ???? ? Z ? E-???????-????????? ????????? ? 93,25 % (2,59 ?.?.) :
6,76 % (2,43 ?.?.) ? 94,65 % (2,45 ?.?.) : 5,34 % (2,10 ?.?.).
??????? ????????? ??????? (III) (???. 2) ? ????????? ?????????? (I) ? (II) ? ?????????? ??
?????????????? ????????? 13C ???, ? ??????? ????????? ???????????? ????????? ?????????
????????? ???????? ???????????? ?????????????.
??????? ? ???????? ?????????? (II) ? ?????????? Z ? E-???????-????????? ?????????? ????????????? ?????????????? ??????????? ????????, ? ??????? ??????? ??????????? ??? ?????????? ? ??????? 530-540 ??, ??????????? ? n,?* -???????? ?????????????
NO-?????? [4].
????? ???????, ????????? ???????? ??? ? ?????? ???????????? ??????? ?????????
?????? ????? ? ??????? ? ?????????? ??????? ????? (??) ? ???????-????????? ????
(Z), (?) ?????????? (I), ????? ????? ??????? ????? ??????? ? ????? ??????? ??????
???. ? ?????????? ?????????? (II) ??????????????? ????????? ? ??????? ?????. ? ????????? ?????????? (I) ? (II) ? ?????????? ??????? ???????-???????? ????? ?? ??????????????.
# 313 #
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?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
????????????????? ?????
??????? ??? 1? ? 13? ?????????????? ?? ??????? Bruker Avance III (600 ???), ???????
??????? 600,13 (1?) ? 125,86 ??? (13?). ???????????? ????????? ?????? 5 ?? ? z-??????????.
??????? ???????????????? ??? 223 ? ? ??????????? ????????????? ???? ?? ??????? ???????????? (?DCl3), ? ???????? ??????????? ????????? ???????????? ??? ?????????? ???????? ???????????? (?? 7,26, ?? 70). ????????? ???????? ? ???????? ??? ??????? ?? ????????? ????????
1
?, 13?, 13C-APT ? ?????????? ???????? ????????????? 1?-13? ?????????? ?? ?????? ? ??????? ?????????? ????-????????? ?????????????? ????, 1?-13? HSQC ?????????????. ??? ?????????? ?????????? ????????????? ???????????? ??????????? ?????????? ?????????????????? ?? ?????????? ????????????. ???????-????-?????????????????? ?????? ?????????? ??
??????? ???????????? Agilent Technologies ????? ???????-??????? (???) ?????? 6890N ?
????-??????????? ?????????? Agilent Technologies: ??????? ????????? ??????????? ??-5??
(30 ? ? 0,25 ??), ??????? ???? ?????? 0,33 ???; ????-??????????? ???????? ??????? ? ??????
???????????? ????? (70 ??) ? ???????????? ??????????? ??????????? ? ?????????? ?? ???????
??????? ????.
????? ???????? ????????????? ?????????? 3-????????????-2,4-???????????.
????? 1,032 ? (8 ?????) 3-????????????-2,4-??????????? ? 8 ????? ????? ???????????? 2 ?
??? 22 0?. ???????? ?????? ?????????????.
4-????????????????-3-??????????????????-2-?? (I). ????? ?????????. ????? 1,57 ?
(94 %), ?. ??. 163-166 0?. ??????????? ?????? (????????????, ? ????. ?? (?)): ?HCl3, 539 (30).
?? ??????, ??Cl3 , ?, ???1: 3350-4200 ? (NH, NOH), 1850 ? (?=N), 1685 ?, 1665 c, 1635 (?=?,
?=N, ?=NOH). ???????, %: C 61,87, H 8,96, N 12,53 C11H18N2O2. ?????????, % : ? 62,83, ? 8,63,
N 13,32. ? 210,27 ????-??????, m/z (I???., %): 210,1 (32) [M]+, 193,1 (87), 167,1 (100), 151,1 (8),
137,1 (6.5), 127,0 (15), 109,1 (3,5), 94,1 (4), 83,1 (97), 69,1 (15), 55,1 (87). ?????????: C11H18N2O2 =
210,14.
4-??????????????-3-??????????????????-2-?? (II). ????? ?????????. ????? 1,16 ?
(85 %), ?. ??. 151-156 0?. ??????????? ?????? (????????????, ? ????. ?? (?)): ?HCl3, 537 (48).
?? ??????, ??Cl3, ?, ???1: 2600 ? (NH, NOH), 1850 ? (?=N), 1685 ?, 1668 c, 1637 (?=?, ?=N,
?=NOH). ???????, %: C 56,15, 56,06 H 8,07, 8,09 N 16,50, 16,45 C8H14N2O2. ?????????, %: C 56,45,
H 8,29, N 16,46. ????-??????, m/z (I???., %): 170,1 (17) [M]+, 153,1 (25), 127,1 (90), 111,1 (6), 85,1
(100), 69,1 (18). ?????????: C8H14N2O2 = 170,11.
?????? ??????????
1. ????????? ?.?., ????? ?.?., ???????? ?.?. ???????????? ???????????? ???????????????? 3-????????????-2,4-??????????? ? ???????? ? ?????????????? // ?????? ???. 2011. ?. 4,
? 1. ?. 89-99.
2. ?????? ???????- ? ???????????????? N- ????????????????????????? / ?.?. ?????????, ?.?. ????????, ?.?. ?????????, ?.?. ????? // ?O??. 2008. ?. 44. ???. 5. ?. 659662.
3. ?????? ?-??????????????? ?? ????????????? ???????????????? / ?.?. ?????, ?.?. ??????, ?.?. ?????????, ?.?. ????????, ?.?. ????????, ?.?. ?????????, ?.?. ????????? // ???. ?????. ????? ? ???. ??????. 2005. ?. 48, ? 8. ?. 119-123.
# 314 #
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?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
4. Veronese A.C., Scrimin P., Bergamini P. J. Vicinal Multifunctional Compounds. Tautomerism
and Isomerism in the Condensation Products of 2-Hydroxyimino-3-oxobutanal or 3-Hydroxyiminopentane-2,4-dione with Benzylamines // Chem. Soc., Perkin Trans I. 1982. Vol. 4. P. 1013.
5. Aly M.M., Imam S.M. Characterization of Copper(II), Nickel(II), Cobalt(II) and Palladium(II)
Complexes of Vicinal Oxime-Imine Ligands; Induced Chelate Isomerism in the Same Molecule of the
Nickel(II) Complex // Monatsh. Chem. 1995. Vol. 126. P. 173-185.
6. Application of Schiff's bases in organic synthesis / Liu Xiao-Lan, Liu Yong-Hong, Shi YaoCheng, Jian Pan-Ming // Chin. J. Org. Chem. 2002. Vol. 22, ? 7. ?. 482-488.
7. Novel 5-(4-Substituted-phenyldiazenyl)-1,3,2?4-oxazaborines and Their Rearrangement to
1,2,4,3?4-Triazaborines / M. Pe?kovб, P. ?im?nek, V. Bertolasi, V. Machбek, A. Lyka // Organometallics. 2006. Vol. 25, N 8. P. 2025?2030.
Tautomerism and Isomerism Monoimines
of 3-Hydroxyimino-2,4-Pentandione
Anna S. Kositsynaa, Alexander A. Kondrasenkob,
Elena S. Semichenkoa and George A. Subocha
a
Siberian State Technological University,
82 Mira, Krasnoyarsk, 660049 Russia
b
Special Designing and Technological Bureau
?Nauka? KSC SB RAS,
53, Mira ave, Krasnoyarsk, 660049, Russia
In the interaction of 3-hydroxyiminopentan-2,4-dione with isopropylamine or cyclohexylamine
are formed Schiff base (3-hydroxyimino-2-iminoketones). Based on the visible, I.r., 1H ? 13C
NMR, 1H-13C ???? ? 1H-15N ???? spectral data «backbone» structures of 4-isopropylimino3-hydroxyiminopentan-2-one and 4-cyclohexylimino-3-hydroxyiminopentan-2-one elucidated.
The influence of the structure of Schiff bases on the tautomeric equilibrium in chloroform between
hydroxyimino-iminoketones and nitroso-enaminones forms are discussed.
Keywords: 3-hydroxyiminopentan-2,4-dione; 3-(hydroxyimino)-4-(isopropylimino)pentan-2-one;
4-(cyclohexylimino)-3-(hydroxyimino)pentan-2-one; Schiff bases; tautomeric equilibria; NMR;
????; HSQC.
?? ?????????? (???. 2-2). ??????????? ????????????? ????????? ?? ????????? ???????
(002) ??????? ????????????? (25.8, 25.3, 24.3 ? 23.5 °), ??????????????? ???????????? ??????????? ?????????? (3.45, 3.52, 3.65 ? 3.78 Е).
????????????, ??????????? ??????? ??????????????? ?????????, ????????? ??????????
??????? ???????????? ???????? ? ????????????. ??-??????? ?????? ?????? ? ??????, ????????
?????????? ?????????, ?????? G-?????? (1580 ??-1), ??????????????? ?????????????? ?????????? ?????? ????????, ??????????? ?? ?????????? ?????????, ???????? D-?????? (1350 ??-1),
??????????????? ??????? ???????? ? ?????????? ?????????? (???. 3). ??????????? D-??????
? ??-???????? ?????????? ?? ?????????? ????????????? ???? ? ?????????? ???????? ??????????? ???????? ?????????? ??? ????????? ?????? (???? ? ????). ????????? IG/ID ??? ??????
???. 1. ??????????-???????????????? ??????????? ????????? ??????????, ???????? ??????????
????????? ? ?????? ???????????
# 296 #
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?.?. ???????, ?.?. ????????? ???????????? ?????????? ?? ?????????? ????????????? ???? ? ?????????? ?????????
???. 2. ?????????????? ?????? ?????? (1) ? ?????? (2), ???????? ?????????? ?????????
???. 3. ??????? ??????????????? ????????? ?????? ?????? (1) ? ?????? (2), ???????? ??????????
?????????
?????? ? ??????, ???????? ?????????? ?????????, ????????? 1,06 ? 1,00, ??????????????, ???
??????????? ? ????????????? ??????? ??? ????????????? ?????? (??????, ??????, ???????),
???????? ?????????? ?????????, ?????????? ??????? ????????? ??????? [9].
??? ?????? ?????? ? ??????, ???????? ?????????? ?????????, ??????????? ?????????????? ????? ???????????? ?????????? ?????????, ??? ????? ???? ??????????? ?????????
???????????? ?????? (???. 4). ????????????? ??????????? ????? ???????????? ??????????
????????? ????????, ??? ??????? ?????? ????????? ?????????????????? ????????, ? ?????? ?
??????????????. g-?????? ??????????? ???????? ? ???????, ?????????? ????????? ???????,
???????? 2,0034, ? ?????????? ???????? ??????? ? 2,0008.
# 297 #
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?.?. ???????, ?.?. ????????? ???????????? ?????????? ?? ?????????? ????????????? ???? ? ?????????? ?????????
???. 4. ??????? ?????????? ????????? ?????? ?????? (?) ? ?????? (?), ???????? ?????????? ?????????
??????????
? ?????? ???????????? ?????????? ???????????? ?????????? ?? ?????????? ????????????? ???? ? ?????????? ????????, ?????????? ??????? ????????????????? ??????? ? ??????????????? (66 ???) ???? ???????????? ????????. ?????????????????? ??????? ?????? ?
?????????????? ??????? ?????? ????? ????????????? ???? ????????? ?? 20 ?? 50 ?? ? ?????????? ???????? ???????? ?? 5 ?? 15 ??. ?????????? ???????? ??????? ?? ??????????? ?????????? ????? ? ???????????????? ??????????? ????? ??????????? ??????????? 3.37 Е.
??????????, ?????????? ???????? ???????????????? ??????? ? ??????????????? ?????????,
????????, ??? ?????????? ????? ?????????? ????????? ??????? ?????? ? ?????? ???????
?????????? ????????? ? ????? ??????????? ????????.
?????? ????????? ??? ????????? ????????? ???? (?????? ? 09-03-00383-?).
?????? ??????????
1. Fung K.K., Qin B., Zhang X.X. Passivation of alpha-Fe nanoparticle by epitaxial gammaFe2O3 shell. Materials Science and Engineering A. 2000. V. 286. P. 135-138.
# 298 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ???????????? ?????????? ?? ?????????? ????????????? ???? ? ?????????? ?????????
2. Zhang X.F., Dong X.L., Huang H., Lv B., Zhu X.G., Lei J.P., Ma S., Liu W., Zhang Z.D.
Synthesis, growth mechanism and magnetic properties of SiO2-coated Co nanocapsules. Acta
Materialia. 2007. V. 55. P. 3727-3733.
3. Zhu L., Ma J., Jia N., Zhao Y., Shen H. Chitosan-coated magnetic nanoparticles as carriers
of 5-Fluorouracil: Preparation, characterization and cytotoxicity studies. Colloids and Surfaces B:
Biointerfaces. 2009. V. 68. P. 1-6.
4. Xu Z.P., Zeng Q.H., Lu G.Q., Yu A.B. Inorganic nanoparticles as carriers for efficient cellular
delivery. Chemical Engineering Science. 2006. V. 61. P. 1027-1040.
5. Dravid V.P., Host J.J., Teng M.H., Elliott B.R., Hwang J.-H., Johnson D.L., Mason T.O.,
Weertman J.R. Controlled-size nanocapsules. Nature. 1995. V. 374. P. 602.
6. Jacob D.S., Genish I., Klein L., Gedanken A. Carbon-coated core shell structured copper
and nickel nanoparticles synthesized in an ionic liquid. J. Phys. Chem. B. 2006. V. 110. N 36. P. 1771117714.
7. Wu W., Zhu Z., Liu Z., Xie Y., Zhang J., Hu T. Preparation of carbon-encapsulated iron carbide
nanoparticles by an explosion method. Carbon. 2003. V. 41. N 2. P. 317-321.
8. Wang J.N., Zhang L., Yu F., Sheng Z.M. Synthesis of carbon encapsulated magnetic
nanoparticles with giant coercivity by a spray pyrolysis approach. J. Phys. Chem. B. 2007. V. 111. N 8.
P. 2119-2124.
9. Byeon J.H., Park J.H., Yoon K.Y., Hwang J. Ambient spark generation to synthesize carbon
encapsulated metal nanoparticles in continuius aerosol manner. Nanoscale. 2009. V. 1. P. 339-343.
10. Churilov G.N. Synthesis of fullerenes and other nanomaterials in arc discharge. Fullerenes,
Nanotubes and Carbon Nanostructures. 2008. V. 16. P. 395-403.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ???????????? ?????????? ?? ?????????? ????????????? ???? ? ?????????? ?????????
Investigation of Nanoparticles
with Metallic Core-Carbon Shell Structure Created
at Plasma-Chemical Synthesis
in High Frequency Arc Discharge
Irina V. Osipovaa, Gariy A. Glushchenkoa,
Viktoriya G. Isakovaa, Elena A. Goncharovaa, b,
Alexander S. Krylova, Sergey M. Zharkova, b,
Eleonora A. Petrakovskayaa and Grigory N. Churilova, b
a
L.V. Kirensky Institute of Physics SB RAS
50/38 Akademgorodok, Krasnoyarsk, 660036 Russia
b
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041 Russia
The results of investigations of nanoparticles with metallic core-carbon shell structures are presented
in the work. They were created in the flow of carbon-helium plasma of high frequency (66 kHz) arc at
the atmospheric pressure. The electron microscopy micrograph of the nanoparticles showed that they
have core (nickel, iron) diameter from 20 to 50 nm covered by the carbon shell of thickness from 5 to
15 nm. The carbon shell consists of spherical graphitic layers with preferred distance 3.37 Е between
graphitic layers.
Keywords: plasma-chemical synthesis, metallic nanoparticles, carbon shell, high frequency plasma.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 3 (2011 4) 301-306
~~~
??? 547.314
?????? ???????? ?????-N-??????????????????
?.?. ????????, ?.?. ?????????*,
?.?. ??????????, ?.?. ?????????, ?.?. ?????
????????? ??????????????? ??????????????? ???????????,
?????? 660049, ??????????, ??. ????, 82 1
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
1-(1-?????????)-3,5-???????-4-???????-1H-??????? ? 1-(1-?????????)-5-?????-4-???????3-?????-1H-??????? ????????????? ????????????????? 2-????????????-1,3-????????? ?
??????????????? ??????????????????.
1-(1-?????????)-3-?????-4-???????-1H-??????? ??????? ????????????????? ??????????????
?????????????????? ? ????????? ?????????????? 4,4-??????????????-2-??? ? ??????
?????.
??? ?????????????? ??????????????? 4-???????????????? ????????-???????? ? ???????????
???????????? Pd/C ???????? ??????????????? 4-?????????????.
????????
?????:
2-????????????-1,3-???????;
3-????????????-2,4-??????????;
2-????????????-3-????????????; 1-(1-?????????)-3,5-???????-4-???????-1H-???????; 1-(1?????????)-5-?????-4-???????-3-?????-1H-???????; 1-(1-?????????)-3-?????-4-???????1H-???????.
????????, ??? ???????? ?????????????? ????????? ? ???????????? ?????????? ???????? ? ??????????? ?? ????????????? ??????????, ??????? ? ????? ???????? ?? [1, 2].
N-?????????????????????? ? ?????????????? ? 4-? ????????? ?? ?????????? ??????? ????
??????????, ???? ??? ???????????? ??? ????????????? ??????????, ????????? N-??????????4-??????????????? ? N-?????????-3,5-???????-4-?????????????? ???????? ?????????????
?????????? [3, 4]. ????????????? ????? ?????????????? ? ???????????, ??? ????????? ???? ?
4-?????-N-???????????????????????, ? ????? ? ???????? ???? ??????????, ???????, ? ????
???????, ????? ???? ???????? ????? ?????????????? ??????????????.
????? ????? ?????? ????? ???????? ?????? ??????? N-?????????-4-???????????????? ?
N-?????????-4-??????????????.
*
1
Corresponding author E-mail address: imidazol5@yandex.ru
© Siberian Federal University. All rights reserved
# 301 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ?????????? ?????? ???????- ? ?????-N-??????????????????
?????????? ? ??????????
????????????? ???????? ??????????? ??? ????????? N-?????????-4-????????????????
????? ????? ????????????? ?????????????????? (1), ????? ??? ???????????????? ? ????????????????? ? 1,3-?????????? ??? ??????? N-?????????????????? [5]. ?????? ??? ?????????????? ?????????????? (1) ? 3-??????????????????-2,4-?????? (2) ??????????? ????????
???????? ?? ??????????, ??? ????? ???? ??????? ? ??????????????? 1,3-???????? (2) ? ??????
????? [6] ? ????????? ?????????? ?????????????????? ??? ??????????????. ? ????? ? ????
? ???????????????? ? 1,3-????????? (2) ???????????? ??????????????? ??????????????????, ?????????????? ??????????? ?????? ??????????? ?????? ? ?????????? ???????? ?????????????? (1). ???????????????? ??????? ????????? ??? ????????? ??????????? ? ???????
? ???????????? 1-(1-?????????)-3,5-???????-4-???????-1?-???????? (3) ? ??????? 40 % (???.
1). ? ??????????? ??????? ?? 2-????????????-1-??????????-1,3-????? ???????????? 1-(1?????????)-5-?????-4-???????-3-?????-1?-??????? (4) (???. 1).
?????? N-?????????-3-?????-4-??????????????? ??????????? ?????????????????
2-????????????-3-???????????? (5) ? ??????????????? (1). ???????????? (5), ?????????? ??????????????? ?????????????? 3-???????????? ? ?????? ?????, ??????? ? ??????? ? ??????????????? (1) ??? ????????? ?? ??????????? ????? (???. 2). ???????????? ????? ??????,
???????????????? ?????????????????? 2-????????????-3-????????????, ???????? ? ?????
????????? ??? ?????????? ???????? ???????? 1-(1-?????????)-3-?????-4-???????-1?-???????
(6) ????-???????? ????? (??? 3).
?????? ??????????? ????????????? ???????????? ??????? ????????????? ? ??????????????? ????????? (3), (4), (6). ? ??????????? ???????? ?????????? (3), (4) ? (6) ? ??????? 660680 ?? ????????? ??? ?????????? n,?* ???????? ????????????? NO-??????. ? ??????? ??? 1?
?????????? (6) ? CDCl3 ?????? ??????? ???????? ????????? ? ??????? 7,16 ?.?. ??????? ???????? ????????? ?????? ? 3-? ????????? ?????????? (3), (6) ??????????? ? ???? ????????? 3,24
? 3,35 ?.?. ??????????????, ? ?????? ???????? ????????? ?????? ? ????????? 5 ?????????? (3),
O
HN
NH3
NO
O
2HCl
Me
1-Ad
R
KOH Me
-H2O
R
N
OH
R=Me, Ph
N
N
1-Ad
3 R= Me
4 R=Ph
???. 1. ?????? 1-(1-?????????)-4-???????-1?-?????????
Me
Me
OMe
Me
O
HCl, H2O
O
OMe
NaNO2, H
O
H
O
H
5
???. 2. ?????? 2-????????????-3-???????????? (5)
# 302 #
O
NOH
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?.?. ????????, ?.?. ?????????? ?????? ???????- ? ?????-N-??????????????????
NO
(5)
Me
NH2NH-(1-Ad) 2HCl
N
1-Ad
N
69%
6
???. 3. ?????? ??????????????? (6)
NO
H2N
R1
R
NH2NH3 OH
R1
R
Pd/C
N
N
N
1Ad
N
1-Ad
3 R=R 1=Me;
4 R=Me, R 1 =Ph;
6 R=H, R 1=Me.
7 R=R 1=Me;
8 R=Me, R 1 =Ph;
9 R=H, R1=Me.
???. 4. ?????????????? ???????????????? (3), (4) ? (6)
(4) ? 2,30 ?.?., 2,26 ?.?. ??????????????. ? ??????? ???? ???? ?????????? ??????????? ???????
???????? ?????????????? ????????? ? ??????? 1,6-2,4 ?.?. ? ??????? ??? 1? ?????????? (4)
???????????? ????????????? ??????? ???????? ?????????? ???????????.
?????????????? ?????????????? ???????? 1-(1-?????????)-4-????????????? ??????????????? ??????? ??????????????? 4-????????????????, ????????? ????????? ?????????????
????? ????????? ????????????? ?????????? ?, ????? ????, ??????????? ????????? ??????? ?
?????? ??????? ?????????? ????? ??????????????.
?? ????????? (3), (4) ? (6) ??? ?????????????? ????????-???????? ? ??????????? ???????????? (Pd/C) ?????????? ??????????????? ???????????????? (7), (8), (9) ? ??????? 51-95 %.
?????? ? ???????? 1-(1-?????????)-4-?????????????? (7), (8), (9) ???????????? ??????
??? 1? ? ????-?????????????.
? ???????? ??? 1? ?????????? (7-9) ???????????? ????????? ??????? ???????? ????????????? ??????????? ? ??????? 2,45-2,65 ?.?. ?????????? ?????? ??????? ????????????
???? ?????????? (9) ? CDCl3 ???? ?????? 7,15 ?.?. ?????? ???????? ????????? ?????? ? 3-?
????????? ?????????????? (7), (9) ?????????? ?? 2,37 ? 2,39 ?.?. ??????????????, ????? ???
?????????? ?????? ????????? ?????? ? 5-? ????????? ??????? ?? 2,19 (?????????? (7)) ?
2,26 a?.?. (?????????? (8)). ? ??????? ?????????? (7), (8), (9) ??????????? ??????? ????????
?????????????? ????????? ? ??????? 1,76-2,28 ?.?.
????????????????? ?????
??????????? ?????? ??????? ?? ???????????????? Helios Omega ? ????????? ???????
1 ?? ??? ???????????? 0,5Ч10 -4 ????/? ? ??????? 200-450 ?? ? ???????????? 1Ч10 -2 ????/? ?
# 303 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ?????????? ?????? ???????- ? ?????-N-??????????????????
??????? 600 ? 750 ?? ? ???????. ???-??????? 1? ? 13? (600,13 ? 150,9 ???) ???? ????????
?? ???????????? Bruker Avance III 600. ????-?????? ??????????????? ?? ????-????????????
Finnigan 8200. 3-????????????-2,4-?????????? ???????????? ?? ???????? [7]. ??? ??????????
????????????? ???????????? ?????????? ????? Silicagel L 100/400 (????? Chemapol).
1-(1-?????????)-4-???????-1?-???????? (3, 4). ????? ????????. ? ???????? 0,61 ?
(2,56 ?????) ?????????????? ?????????????????? ? 14 ?? ?????? ???????? ??????? 0,145 ?
(2,55 ?????) ?????? ???? ? 3 ?? ??????, ????? (2,6 ?????) 2-????????????-1,3-???????? ? ????????? 12 ? (??? ?????????? (3)) ??? 24 ? (??? ?????????? (4)) ??? 24 ??. ?????????????
????? ?????? ?????????? ?????, ???????? ??????? ?? 5 ?? ??????, ???????? ?? 0 ??, ???????? ?????? ?????????????. ??? ????????? ???????????? ??????? ??????? ?????? ???????? ??
?????????????????? ??????? (2Ч50 ??) ? 50 ? ??????????. ??????: ?????? ? ?????????? (49:1).
????-??????? ?????????, ?????????? ? ???????, ??????????.
1-(1-?????????)-3,5-???????-4-???????-1?-??????? (3). ????? 0,26 ? (40 %). ?. ??.
?
127 ?. ??????????? ??????, ?????., ?? (?): 308 (16620), 661 (60). ?????? ??? 1?, ?, ?.?.: 1,821,83 ? (6?, ??2), 2,22 ? (3?, ??), 2,30 ??. ? (3?, ??3), 2,40-2,41 ? (6?, ??2), 3,24 ??. ? (3?, ??3).
????-??????, m/z (I???., %): 259 (68) [?]+, 135 (100), 125 (14), 107 (14), 93 (23), 79 (24), 67 (11), 55
(14).
1-(1-?????????)-5-?????-4-???????-3-?????-1?-??????? (4). ????? 0,21 ? (35 %). ?. ??.
182 ??. ??????????? ??????, ?????., ?? (?): 309 (14740), 674 (50). ?????? ??? 1?, ?, ?.?.: 1,64-1,70 ?
(6?, ??2), 2,14 ? (3?, ??), 2,20 ? (6?, ??2), 2,26 ??. ? (3?, ??3), 7,52-7,56 ? (3?, ?????.), 7,647,65 ? (3?, ?????.).
1-(1-?????????)-3-?????-4-???????-1?-??????? (6). ????? 0,66 ? 4,4-??????????????2-??? (5 ?????) ? 5 ?? 1 ? ??????? ??????? (5 ?????) ???????????? ??? 20 °? 0,5 ?, ????????
?? 0 °? ? ? ??????? 0,5 ? ???????? ?? ?????? ??????? 0,38 ? (5,5 ?????) ??????? ?????? ?
3 ?? ????. ????? ?? ??????????? ????? ?????? ?????? ????? ? ??????? ????????????? ??????,
? ???????? ??????? 0,89 ? (3,75 ?????) ?????????????? ?????????????????? ? 20 ?? ????.
??????????? ????? ?????????? 10 ??? ??? 20 °?. ???????? ?????? ??????-???????? ?????
?????????????, ?????????? ? 20 ?? ?????? ? ????????? ?? ??????? ???? 3 ?. ????? ??????? ?
??????? ?? ?????? ???????? 5 ??, ???????? ?????? ?????????????. ????-??????? ?????????,
?????????? ? ???????, ??????????. ????? 0,63 ? (69 %). ?. ??. 142 ?? (??????). ???????????
??????, ?????., ?? (?): 309 (16500), 680 (56) ?????? ??? 1?, ?, ?.?.: 1,82-1,83 ? (6?, ??2), 2,31 ? (3?,
??), 2,40-2,41 ? (6?, ??2), 3,35 ??. ? (3?, ??3), 7,16 ??. ?. (1?, ?????). ???????, %: C 69,11, H 8,01,
N 17,83. C14H19N3O ?????????, %: C 68,54, H 7,81, N 17,13. M 245,32.
1-(1-?????????)-4-?????-1?-???????? (7-9). ????? ????????. ? ???????? 1 ?????
1-(1-?????????)-4-???????-1?-???????? (3, 4, 6) ? 30 ?? ?????? ????????? 0,1 ? ????????????
(0,5 %-???? Pd/C), ???????????? 0,5 ?, ????? ??? ??????????? ????????????? ???????? 0,4
?? 85 %-???? ????????-???????. ????? ?????????????? ???????? ???????????? ??? 0,5 ?,
????????????? ???????????, ???????? ??????? ? ???????, ??????? ?????????????? ??????.
???????? ??????? ?? 10 ??, ???????? ?????? ?????????????, ??????? 1 ?? ???????. ???????????? ?????????, ?????????? ? ?????, ???????.
1-(1-?????????)-4-?????-3,5-???????-1?-??????? (7). ????? 0,125 ? (51 %). ?. ??. 103?
104 ?. ?????? ??? 1?, ?, ?.?.: 1,76 ? (6?, ??2), 2,19 ? (3?, ??3), 2,21 ? (3?, ??), 2,26-2,27 ? (6?,
# 304 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ?????????? ?????? ???????- ? ?????-N-??????????????????
??2), 2,37 ? (3?, ??3), 2,45 ??. ? (2?, NH2). ????-??????, m/z (I???., %): 245 (100) [?]+, 135 (72), 111
(68), 107 (8), 93 (20), 91 (12), 79 (21), 77 (12), 70 (28), 67 (8), 55 (7).
1-(1-?????????)-4-?????-5-?????-3-?????-1?-??????? (8). ????? 0,29 ? (95 %). ?. ??.
?
171 ?. ?????? ??? 1?, ?, ?.?.: 1,56-1,62 ? (6?, ??2), 2,04 ? (3?, ??), 2,07 ? (6?, ??2), 2,26 ?
(3?, ??3), 2,47 ??. ? (2?, NH2), 7,33-7,35 ? (2?, ?????.), 7,43-7,47 ? (3?, ?????.). ????-??????, m/z
(I???., %): 307 (100) [?]+, 173 (35), 135 (50), 104 (20), 93 (15), 79 (19), 77 (17).
1-(1-?????????)-4-?????-3-?????-1?-??????? (9). ????? 0,14 ? (60 %). ?. ??. 114 ??.
?????? ??? 1?, ?, ?.?.: 1,76 ? (6?, ??2), 2,22 ? (3?, ??), 2,27-2,28 ? (6?, ??2), 2,39 ? (3?, ??3),
2,65 ??. ? (2?, NH2), 7,15 ? (1?, ?????). ????-??????, m/z (I???., %): 231 (100) [?]+, 135 (50), 97 (30),
93 (11), 91 (8), 79 (12), 77 (8), 56 (6).
?????? ???????? ????????????? ?.?. ??????????? (???? ????? ??? ?? ???) ??
?????? ???-????????.
?????? ??????????
1. ??????? ?.?., ?????? ?.?., ???????? ?.?. ???????????? ???????????. ????????? : ????? ?????????. ???. ????., 2001. 320 ?.
2. ??????????????? ?????????? ??????????????????? ???????????? / ?.?. ????????,
?.?. ??????, ?.?. ???????, ?.?. ???????, ?.?. ?????????, ?.?. ???????, ?.?. ??????? // ???.????. ????. 2002. ?. 36, ? 1. ?. 5-7.
3. Heterocyclic compounds : ???. 2827415 ??? : Cl 167-33 / Freeman W.A., Pain D.L., Slack R.. ?
? 603809 ; ????. 13.08.1956 ; ????. 18.03.1958.
4. Improvements in or relating to pyrazole compounds and compositions containing them : ???.
786753 ?????????????? : C07D231/38, ?07D 231/00 / Freeman W.A., Slack R. ? ? GB 19550004249
1950212 ; ????. 12.02.1955 ; ?????. 27.11.1957.
5. ?????????? ?.-?.?., ???????? ?.?. ????? ??????????????????. ????? 2. ???????????
????????????????? // ????. 1999. ?. 35, ???. 2. ?. 183-220.
6. Green A.L., Saville B. The reaction of oximes with isopropylmethylphosphonofluoridate //
J. Chem. Soc. 1956. P. 3887-3892.
7. ??????? ?. ?????? ???????????? ? ???????????? ?????. ?.: ??????????, 1952. ?. 293.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ?????????? ?????? ???????- ? ?????-N-??????????????????
Synthesis of Nitrosoand Amino-N-Adamantylpirazoles
Timofey A. Frolenko,
Elena S. Semichenko, Maria G. Melnikova,
Natalia A. Gavrilova and George A. Suboch
Siberian State Technological University
82 Mira, Krasnoyarsk, 660049 Russia
Synthesis of 1-(1-adamantyl)-3,5-dimethyl-4-nitroso-1H-pyrazole and 1-(1-adamantyl)-5-methyl-4nitroso-3-phenyl-1H-pyrazole done by the cyclocondensation of 2-hydroxyimino-1,3-diketones and
adamantylhydrazine dihydrochloride. Synthesis of 1-(1-adamantyl)-3-methyl-4-nitroso-1H-pyrazole
done by reaction of unstable 2-hydroxyimino-3-oxobutanal and adamantylhydrazine hydrochloride.
2-Hydroxyimino-3-oxobutanal obtained by nitrosation of 4,4-dimethoxybutan-2-one in an acid medium.
The 2-(hydroxyimino)-3-oxobutanal was injected into the cyclocondensation without isolation from
the reaction mixture.1-(1-?damantyl)-4-amino-1H-pyrazoles were synthesized through the chemical
reduction of synthesized 4-nitrosopyrazoles with hydrazine hydrate in the presence of Pd/C.
Keywords:
1-(1-adamantyl)-3,5-dimethyl-4-nitroso-1H-pyrazole;
1-(1-adamantyl)-5-methyl-4nitroso-3-phenyl-1H-pyrazole; 1-(1-adamantyl)-3-methyl-4-nitroso-1H-pyrazole; 2-hydroxyimino1,3-diketone; 3-hydroxyimino-2,4-pentanedione; 2-(hydroxyimino)-3-oxobutanal.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 3 (2011 4) 307-315
~~~
??? 547.442.3
?????????? ? ???????? ??????????
3-????????????-2,4-???????????
?.?. ?????????, ?.?. ????????????,
?.?. ??????????*, ?.?. ??????
?
????????? ??????????????? ??????????????? ???????????,
?????? 660049, ??????????, ??. ????, 82
?
??????????? ??????????????-??????????????? ????
«?????» ??? ?? ???
?????? 660049, ??????????, ??. ????, 53 1
Received 2.09.2011, received in revised form 9.09.2011, accepted 16.09.2011
??? ?????????????? 3-????????????-2,4-??????????? ? ?????????????? (???????????????)
??????? ?????????? ????????? ????? (3-????????????-2-???????????). ?? ?????????
?????? 1H ? 13C ???-???????? ? ?????????? ???????? 1H -13C ???? ? 1H -15N ???? ???????????
????????? ????????? 4-??????????????-3-??????????????????-2-??? ? 4-????????????????3-??????????????????-2-???. ????????? ??????? ???????? ????????? ????? ?? ???????????
?????????? ? ?????????? ????? ???????-???????????? ? ????????????-??????????????
???????.
???????? ?????: 3-????????????-2,4-??????????; 4-??????????????-3-??????????????????2-??; 4-????????????????-3-??????????????????-2-??; ????????? ?????; ???????????
??????????; ???; ????; HSQC.
????????, ??? ? ???????????????? ???????????????? 2-????????????-1,3-????????? ?
??????? ? ???????? ?????????? 3,5-???????????? 4-??????????????. ??????? ???????? ???
??????? ??????, ? ??????? ?????????? ??? ???????? ?????????? [1-3]. ?????? ??? ??????????
??????? 3-????????????-2,4-??????????? ? ???????? ? ?????????????? (???????????????)
??????? ? ????? ??? ???? ???? ???????? ????? ??????????????? ??????????, ?? ???????
?????????????? ????????. ?? ????????? ?????? ?? ??????????? ????????? ????? ??? ?????????????? 2-????????????-1,3-????????? ? ???????????? ??? ????????? [4, 5] ????? ????????????, ??? ?????????? ?????????? ???????? ?????????? ??????? 3-????????????-2,4??????????? ? ???????. ????? ?????? ???????????? ????? ?????? ? ???????????? ????????
*
1
Corresponding author E-mail address: imidazol5@yandex.ru
© Siberian Federal University. All rights reserved
# 307 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
????????? ?????????????? 3-????????????-2,4-??????????? ? ?????????????? ??? ??????????????? ???????. ???????????? ???????????? ?????? ???????????? ??????? ??????????? ????????? ????? ? ??????????????? ???????? ??????????????? ????????????, ??????????????, ????????? ? ?????? ???????? [6, 7].
?????????? ? ??????????
?????????????? ?????? ????????????? ? ????????? ??????????? ????????? ?????
???? ?????? ???? ?? ?????????? ???????????? ?????? ? 3-????????????-2,4-????????????
(???. 1). ??? ????? ? ???????? 3-????????????-2,4-??????????? ? ????? ???????? ????????????? ?????????? ?????????? ?????????????? ????? ? ??????????? ????? ???????????? ???
20 є? ? ??????? 2 ?, ????? ???? ????????????? ?????????????? ????? ???????.
?????? ?????????? ????????? ????? (I), (II) ??????????? ???????????? ???????????? ?
???????-????-?????????????.
??? ??????????? ? ?????????? ? ?????? ?????????? (I), (II) ?????????? ???????????????? ????????. ??? ?????????? ?????????????? ??? ????????? ????????? ?????????? ????? ????????. ???????? ???? ??? ???????? ????? ??? ????????? ?????, ??????????? ??
3-????????????-2,4-??????????? ? ???????????. ?????? ????????? ??? ??????? ? ????????
? ????????? 4-???????????-3-????????????-2,4-??????????? ?????????? ????? ???????????
??????????? ? ?????????, ?? ??????? ?????? ??????? ???????????? ? ??????????? ??????????? ???? (?????????????????? ?????????? ?????) [4]. ?????? ????? ????????????? ??????
??????? ?? ??????????? ?????????? ??????? ?????????? ??????????? ? ?(2) (???. 1), ? ???????
???????????, ?????????? ? ??????? ?????? ?????, ?? ?????????. ????? ????, ??????????????
??????????? ????? ??????????? ? ????????? ??????????? ?????? ?????????? ????????,
??????????? ?? ????????? ???? (????????? ????-????????? ??????????????) ? ?????????
?? ? ???????? ? ????????? ???????????. ??????????? ?????????????? ?????? ?????????
???????? ?????? ?????????? ????? ????????? ? ?????????? ? ??? ????? ????? ???????????
??????????? ????????? ????????.
??? ????????? ????? 3-????????????-2,4-??????????? (I), (II) ???????? ???????????
??????? ?????????????????-???????? (??, ?Z, ZE, ZZ), ????????? ???????-???????????
???? (Z, E) ? ???????????????? ??????? (III) (???. 2). ???? ??????????? ????? ??? ???
???????????? ??????? ?????????? ? ???????? ? ??????????????? ??????????? ????? ????
(????. 1, 2).
Me
O
(1)?H
NR
3
C (2)
RNH2
O
NOH
????
O
R= i-Pr, Cy
Me
C (3)
C (4)
C (5) H3
???. 1. ?????? ????????? ????? ?? 3-????????????-2,4-???????????
# 308 #
NOH
I R = Cy
II R = i-Pr
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
?? ????????? ???????? ??? 13C, 13C-APT (Attached Proton Test) ? ?????????????? ???????? 1H -13C ???? (Heteronuclear Multiple Bond Correlation) ? 1H- 13C HSQC (Heteronuclear Single
Quantum Coherence) ? CDCl3 ??????? ?????????? «?????????» ????????? ?????????? (I), ??????????? ?? ???????????????? ? 3-????????????-2,4-???????????.
? ???????? 13C ? 13C-APT ?????????? (I) ????????? ?????? ??????????? ????? (????. 1).
? ??????? 13C-APT ??? ???? ????????????? (CH, CH3) ? ???? ????? ? ???? (C, CH2). ???????
O
O
O
OH
O
OH
N
Me
N
N
O
Me
OH
Me
N
Me
H
Me
R
N
Me
R
Me
N
R
EE
N
ZE
EZ
O
N
ON
Me
Z
OH
H
Me
R
C
O
H
N
Me
ON
C
O
ZZ
R
Me
Me
N
Me
Me
N
E
N
R
R
III
???. 2. ??????? ????????? ????? 3-????????????-2,4-???????????
??????? 1. ?????????? ?????? ??? 1H, 13C ? 15N (?DCl3) ?????????? (I)
?????????? (I)
C=O
? 1H, ?.?.
(????*, ??)
-
Int*
? 13C, ?.?.
? 15N, ?.?.
-
199,5
-
>C=NOH
-
-
161,3
-
>C=N
-
-
152,1
-
CH (Cy)
3,71 p (J 4,79 ??)
1,23
53,7
-
CH2 (Cy)
1,51-1,40 m
1,6
32,4
-
2,59 s
3,43
27,6
-
CH2 (Cy)
1,66-1,65 m
2,59
25,0
-
CH2 (Cy)
CH3
1,90-1,81 m
2,5
23,9
CH3
2,43 s
3,74
16,1
202,8 (?N=)
NOH
18,50 b
1,0
-
-
*Int ????????????? ????????????? ????? 1H ???.
**???? ? ????????? ????-????????? ??????????????.
# 309 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
??????? 2. ?????????? ?????? ??? 1H, 13C ? 15N (?DCl3) ?????????? (II)
?????????
?????????? (II)
C=O
? 1H, ?.?.
(????*, ??)
-
Int*
? 13C, ?.?.
? 15N, ?.?.
-
199,8
-
C=O'
-
-
199,2
-
>C=NOH
-
-
161,7
-
>C=N
-
-
151,9
-
CH (i-Pr)
4,06 m (J 6,55 ??)
1,0
46,9
-
CH' (i-Pr)
3,10 m
0,05
46,9
-
CH3
2,59 s
3,01
27,5
-
CH3'
2,49 s
0,22
27,5
-
CH3 (i-Pr)
1,35 d (J 6,67 ??)
6,68
22,6
-
CH3' (i-Pr)
1,12 d (J 5,06 ??)
0,38
22,6
-
CH3
2,45 s
2,99
16,1
215 (?N=)
CH3'
2,10 s
0,17
16,1
322 (?N<)
NOH
18,59 b
0,87
-
-
*Int ????????????? ????????????? ????? 1H ???.
**???? ?????????? ????-????????? ??????????????.
? ??????????? 13C 161.3 ? 152.2 ?.?. ?????????? ??? ????????, ???????????? ? sp2 -??????????????? ??????, ? ???????? ? ????????? C(3) ? C(2) (???. 1) . ?????? ??????? 1H -13C HMBC ?????
???????????? ?????????????, ??? C(2) ?????? ??????????? ? ????????? ? C(3). ??????????????
?????? ?????????? (I) 1H -13C ????, ???????????????? ??? ???????? ??????? 8 ??, ???????
?????-??? ??? ???????? ? ?????????? ??????? (?, ?.?.) 199,5 ?.?., ?????????? ? ???????? C(4)
???????????? ??????.
????????? ?? ??????????? ????? ???? ????? (1H- 13C HSQC) ???????? ?????????? ?????????? ??????? ????????????? ????? ??????? APT 16,1 ? 27,6 ?.?. ? ?????????? ?????? 2,43 ?
2,59 ?.?. ??? ?????? ??????? ??? ????????? ????? ? ??????????????? ?? ?????????? (?(1) ?
?(5), ???. 1) ? ?????????? ??????. ????????? ???????, ?????? ??????? ????????? ?? 2,59 ?.?.,
??????? ? ???????????? ?????? ????????, ??? ?????????????? ???????? ??????? ??????????
(1H -13C ????) ???? ???????? ? ????????? ? ???????? 199,5 ?.?. ? ???? ??????? 6-7 ??. ????????? ??????? 2,43 ?.?. ??????????????? ? ????????? 152,1 ?.? (???? 6-7 ??) ? ? ?????????
161,3 ?.?. (???? 1,5-2 ??).
??? 13C 53,7 ?.?. ??????? ? ??????? ?????????? ???????? ????????????. ?? ??????? 13C- 1H
HSQC ???? ??? ???????????? ?????????? ? ????????? ???????????? 3,71 ?.?. ??? ??????
???????? 1H -13C ???? ? 1H- 13C HSQC ?????????? ???? 32,4, 25,0 ? 23,9 ?.?, ? ????? ???????????????? ? ???? ??????????? 1,51-1,40, 1,66-1,65 ? 1,90-1,81 ?.?. ??????????????, ???????? ?
???????? ?? ?????????????? ? ?????????? ???????? ????????????.
? ??????? 15N-1? HMBC (???. 3, ????. 1) ??????? ??????????? ?????-??? (202,8 ?.?.), ??????????????? sp2 -???????????????? ????? ?? ?????????? ???? ?????????? ? ?????????????
? ????????? 2,43 ?.?.
# 310 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
???. 3. ?????????????? ?????? 15N-1? HMBC ?????????? (I)
????? ???????, «?????????» ????????? ????????? ????? (I) ???????? ????????????
?????? (?=O) ? ??? ?????????, ? ??????? ??????? ?????? ? ?????? ????? ? sp2-????????? ????????? (>C=N-). ????? ????, ??????? ??? ????????? ??????, ???? ?? ??????? ???????????? ?
?????????, ? ?????? ? ? ????????, ????????? ? ??????????? c ??????????????? ????????????
(>C=N-Cy). ???? ??????? ????????????? ??????? ? ??-??????? ?????????? (I) ? ??????????
????? ?????????? 1685, 1665, 1635 ??-1, ??????? ????? ???? ???????? ? ????????? ??????????
???????????? (?=O), ??????? (?=N) ? ?????????????? (?=NOH) ?????.
?????????? ? ??????? ? ?????????????? ??????????? ??????????? ???? ??????????
(I) ? ???????? ?????????? ???????? ?? ????????? ???????? ??? ? ?????????????? ?????????? ???????? 1H -13C ???? ? 1H -15N ???? ??? ????????? ????????? ????????.
? ???????? ??? 1? ? 13? ?????????? (I) (????. 1) ??????? ?????? ???? ????? ????????, ???
??????????????? ? ??????? ???? ?????? ???????, ???? ?????????? ??????????, ????? ?????
???????? ????? ??????? ? ????? ??????? ?????? ???.
????????? ??? 18,5 ?.?. ? ??????? ??? 1H ?????????? (I) ????? ??????? ? ???????, ????????????? ???? ?????????? ????????? ? ?????????? ??????????? ???????. ????? ????????? ????? ????????? ?? ???????? ???????? 199,5 ?.?. ?????????? ??? ???????????? ??????,
???????????? ? ??????????? ?????????? ?????. ??????? ?????? ?????????? 3350-4200 ??-1
? ??-??????? ?????????? (I) ? ?????????? ?????? ?????????????? ?????????????? ?????????????????? ?????????? ?????. ? ?????? ???????-??????????? ????? ? ??????? ??? 1H
?????????? (I) ??? ????????? ??????????? ?????? ???? ??????????? ???? 18,5 ?.?., ??????
??? ??????????? ????? ???? ??????????? ??????? ???????. ?? ?? ???????? ? ???????? ?????????????? ? ????????? ???????, ????????? ? ???????????? ???????. ????? ? ???????, ??????
# 311 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
?????????????????-???????? ????? (??), ???????-??????????? ???? (Z), (?) ??? ????? ??
??? ?????? ?? ????????? ???????????? ??????? ?????????? (I) ? ??????????, ? ??????? ??????? ??????????? ??? ?????????? ?? 539 ??, ??????????? ? n,?* ???????? ????????????? NO?????? [2].
????? 15N 202,8 ?.?. ???????????? ????????????? ????? ? ???????? ?????.
????????? ???????? ??? ? ?????? ??????????? ? ??-???????? ?????????? (I) ? ?????????? ????????? ??????? ????? ? ??????? ??????????? ??????????, ?????????? ???????????
???? ? ????, ?? ???? EE-?????????????????-???????? ????? ? Z- ? E-???????-?????????
????, ????? ????? ??????? ????? ??????? ? ????? ??????? ?????? ???.
«?????????» ????????? ?????????? (II), ??????????? ?? 3-????????????-2,4-???????????
? ??????????????, ?????????? ?? ????????? ?????? ??? 13C, 13C-APT ? ??????????????
???????? 1H -13C ????, 1H- 13C HSQC ? ?DCl3. ? ???????? 13C ? 13C-APT ?????????? (II) ????????? 7 ????? (????. 2). ???? 161,7 ? 151,9 ?.?. ????????????? ???????????? ?????? ????????.
??????? ???????? ????????????? ?????? ????????? ?? 22,6 ? 46,9 ?.?., ????????? ????? ? ??
16,1 ? 27,5 ?.?. ?????????????? ?????? ?????????? (II) 13C- 1H ????, ???????????????? ???
???????? 8 ??, ??????? ?????????????? ?????-???? ??? ???????? 199,8, 199,2 ?.?., ??????????
? ????????? ???????????? ?????.
?????? 13C 16,1 ?.?. ?? ??????????? ????? ???? ????? (13C- 1H HSQC) ????????????? ???????? ???????? 2,45 ?.?. ?????? ???????? ?? 27,5 ?.?. ????? ?????-??? ? ????????? ????????
2,59 ?.?. ??????? ?????????? ? ??????? 13C- 1H ???? (????????? 8 ??) ???????? ????? ???????? ????????? ??????, ??????? ?????? ?? 2,59 ?.?., ? ????????????? ???????? ? ???????? ??
199,8 ?.?. ????????? ??????? 2,49 ?.?. ?????? ??????? ??????????????? ? ???????????? ????????? 199,2 ?.?. ???? ?? ????????? ??????? ??????????? ? ???????????? ????????? 161,7 ?.?.
? ????? ? 151,9 ?.?. ??? ?????? ????????? ??????? ? ????? ???????? ????????? ??? ????????
16,1 ?.?. (??????? 2,45 ?.?.) ? ???????????? ???????? 161,7, 151,9 ?.?., ???????????? ???????
199,8 ?.?. ? ????????? ??????? 27,49 ?.?. (??????? 2,59 ?.?.).
??????? ????????? ?????? (2,10 ?.?.) ????? ??????? ????? ? ?????????? 161,7 ?.?. ? ?????? ? 151,9 ?.?. ?? ???? ????????? ????????? ??????? 27,5 ?.?. (??????? 2,49 ?.?.) ???????????? ???????? 199,2, 161,7, 151,9 ?.?. ? ????????? ??????? 16,1 ?.?. (??????? 2,10 ?.?.) ????????
? ?????? ?????????, ????????????? ?????????? ??????? ??????, ??? ??????.
? ??????? 15N-HMBC ????????? ??? ???? 15N 215 ?.?. ? 322 ?.?., ??????????????? sp2- ?
3
sp -???????????????? ?????? ?????, ?????????????? (????. 2, ???. 4). ???? ????? ? ????????
?? 215 ?.?. ????? ?????-???? ? ?????????? ????????? ?????????????? ????????? (1,35 ?.?.)
? ????????? ???????? (2,45 ?.?.). ?????? 15N 322 ?.?. ????????????? ? ????????? ????????
2,10 ?.?.
????? ???????, ? ??????? 1H ??? ?????????? (II) ????? ???????? ??? ???? ??????? ??????????? ????????? ????? (?????? - ?H3-C=O , CH3-C=N, (CH3)2 CH; ??????, ?????????? ?
????. 2 ??????? ? - ?H3-C=O , CH3-C-N?, (CH3)2CH), ??????????????? ?????? ??????????.
??? ????????? ? ?????????????-???????? ?????? (???????????? ??????? ???) ???? ????????? ????????? ????? 2,59 ? 2,45 ?.?., ? ? Z ? E-???????-????????? ????? ????? 2,49 ?
2,10 ?.?., ????? ??????? ????? ? ??????????? ??????????? ???????????? ???? ??????????.
??? ??????? ???????????? ?????? ?? ???????????? ?????????????? ?????? ???????????
# 312 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????????? ?????????? ? ???????? ?????????? 3-????????????-2,4-???????????
???. 4. ?????????????? ?????? 15N-1? HMBC ?????????? (II)
????? ????????? ????????, ?????? ?? ?????????????, ??? ? ????????? ?????? ????? ? ?????? ???? ???????? ? ????????????? ????????? ???????? ????????? ???? ?????. ????????
????????? ??????????? ???????? ????? ???????? ?????????????-???????? ???? ? Z ?
E-???????-?????????: ????????? ???????? ?????????????? ????????? ? 96,15 % (4,06 ?.?.) ?
3,85 % (3,10 ?.?.), ????????? ???????? ?????????? ? 94,61 % (1,35 ?.?.) ? 5,38 % (1,12 ?.?.). ???
????????? ???????? ?????????????? ????? ?? ??????????? ????????? ?? ????????? ??????
????? ? ????????? ? ?????? C=C ? ?=N. ??????????? ?????????????? ????????? ????????
?????????????-???????? ???? ? Z ? E-???????-????????? ????????? ? 93,25 % (2,59 ?.?.) :
6,76 % (2,43 ?.?.) ? 94,65 % (2,45 ?.?.) : 5,34 % (2,10 ?.?.).
??????? ????????? ??????? (III) (???. 2) ? ????????? ?????????? (I) ? (II) ? ?????????? ??
?????????????? ????????? 13C ???, ? ??????? ????????? ???????????? ????????? ?????????
????????? ???????? ???????????? ?????????????.
??????? ? ???????? ?????????? (II) ? ?????????? Z ? E-???????-????????? ?????????? ????????????? ?????????????? ??????????? ????????, ? ??????? ??????? ??????????? ??? ?????????? ? ??????? 530-540 ??, ??????????? ? n,?* -???????? ?????????????
NO-?????? [4].
????? ???????, ????????? ???????? ??? ? ?????? ???????????? ??????? ?????????
?????? ????? ? ??????? ? ?????????? ??????? ????? (??) ? ???????-????????? ????
(Z), 
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