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Redox Resins Based on Vinyl-9 10-anthraquinones.

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Thus, barbituric acid affords 5,6-(2'-methy1-3'-phenylfurano)uracil, m.p. 268 "C (decomp.) in 75 % yield. Similarly, indane- 1,3-dione yields 1,2-(2'-methyl-3'-phenylfurano)oxoindene (85 %; m.p. 147-148 "C), 4-hydroxycoumarin yields
3,4 - (2'- methyl - 3'- pheny1furano)coumarin (65 %; m.p.
199 "C), and 4-hydroxycarbostyril yields 3,4-(2'-methyl-3'phenylfuran0)-carbostyril (60 %; m.p. 264 "C).
Received, September 10th. 1962 [Z 357/184 IE]
[l] Part IV of the series "Furans and Pyrans" by K. E. Schulte,
J. Reisch et al.
121 Parts I and 11: K . E. Schulte, J. Reisch, and A. Mock, Arch.
Pharmaz. 295, 621,645 (1962); Part 111: K. E. Schulte. J. Reisch,
and K . H. Kauder, ibid., in press.
91 "C), which is isomeric with I, probably on account of geometric isomerism of the chlorine atoms: this assumption is
supported by the infrared spectra of the two compounds. In
addition to methyl phthalate, thermal cleavage of I affords
mainly the solid trans,trans-l,4-dichlorobutadiene("1; m.p.
37-38 "C) obtained by Criegee [2]. Thermal decomposition
of compound I1 gives a liquid (b.p. 34 "C/2 mm Hg), which
yields meso-dichlorosuccinicacid on ozonolysis and therefore
i s cis-l,2-dichlorocyclobutene(IV). On shaking a solution in
ether of IV with 1 % sodium amalgam at room temperature,
the dimer (CsHs) of cyclobutadiene was obtained in cn. 30%
yield and was identified by its infrared spectrum [3], by eleIV
Preparation of Solutions of Anhydrous Perchloric
Acid in Halogenated Hydrocarbons and of
Perchloric Acid Monohydrate
Na(Hg)
------+
(1111)
-
El Tll
mentary analysis, and by the infrared spectrum [5] of its
silver nitrate complex C4H4.AgN03 [4]. Treatment of the
solid 1,4-dichlorobutadiene with sodium amalgam under the
same conditions left most of it in an unchanged state.
By Prof. Dr. F. Klages and P. Hegenberg
Received, October lst, 1962
Institut fur Organische Chemie
der Universitat Miinchen (Germany)
The preparation of solutions of anhydrous perchloric acid in
organic solvents was hitherto very laborious and often also
dangerous, since pure perchloric acid explodes very easily [l].
By extracting a mixture of oleum and 70 % perchloric acid
with methylene or ethylene chloride, fairly concentrated
perchloric acid solutions are readily obtained (ground glass
joints must not be greased). For example, up to 90 % of the
perchloric acid can be extracted with methylene chloride
from a mixture of one part by volume of 70 % perchloric acid
and four parts by volume of 25 % fuming sulfuric acid. The
solutions contain up to 0.3 g of HClO4 per cm3 according
to the quantity of solvent used and fume strongly in air. In
the mixture proportions specified, they are almost free of
sulfuric acid (molar ratio H2S04/HC104 = 0.004: 1) and are
absolutely dry, since traces of water immediately precipitate
insoluble perchloric acid monohydrate. A fairly pure monohydrate (m. p. 48-49 "C) can be produced by passing in
moist air, if no more than 50 % of the perchloric acid contained in the solution is allowed to be converted. Otherwise,
there is the danger of aggregation of the monohydrate
Received, October lst, 1962
[Z 360/1931
precipitate.
[l] M. Gomberg, J. h e r . chem. SOC. 45, 418 (1923).
The Dimer of Cyclobutadiene
By Prof. Dr. C. D. Nenitzescu, Dr. Margarete Avram,
Elise Marica, I. G. Dinulescu, and G. Mateescu
Chemical Institute of the Academy of the R. P. R.
Bucharest (Rumania)
The Diels-Alder reaction between cyclooctatetraene dichloride and dimethyl acetylenedicarboxylate gives, besides the
adduct I (m.p. 126OC) [l], a second compound I1 (m.p.
[l] W. Reppe, 0.Schlichting, K. Klager, and T. Toepel, Liebigs
Ann. Chem. 560, 1 (1948).
[2] R. Criegee, W. H3rnuL and W . D. ScheNenberg, Chem. Ber.
86, 126 (1953).
[3] M. Avram, G. Mateescu, I. G. Dinulescu, E. Marica, and C. D.
Nenitzescu, Tetrahedron Letters 1961, No. 1, 21.
[4] M. Avram, E. Marica, and C. D. Nenitzescu, Chem. Ber. 92,
1088 (1959).
[ 5 ] H. P. Fritz, J. F. W. MeOmie, and N. Sheppard, Tetrahedron
Letters 1960, No. 26, 35.
Redox Resins Based on Vinyl-9,lO-anthraquinones
By Prof. Dr. G. Manecke and Dip1.-Chem. W. Storck
Fritz-Haber-Institut der Max-Planck-Gesellschaft
Berlin-Dahlem (Germany)
We have succeeded in obtaining cross-linked polymers of 2vinyl-9,lO-anthraquinone(I) and styrene with divinylbenzene
as cross-linking agent in practically quantitative yield by
thermal copolymerisation in dimethyl sulfoxide. After
sulfochlorination and subsequent saponification, these give
insoluble redox resins which show only limited swelling in
water. (I) has been prepared by pyrolysis of 2-(wacetoxyethy1)anthraquinone [l]; it is also obtainable by another way
[2,3]. Use of dimethyl sulfoxide as solvent permits variation
of the monomer ratio within wide limits. Addition of nbutylacetate gives polymers with a micropore structure. 2Vinylanthraquinone can be replaced by 1-vinylanthraquinone
[4] but this copolymerises less readily so that the redox
capacities attainable lie appreciably lower. These new redox
resins are stable over the entire pH range and possess a very
low redox potential. They can be reduced easily in alkaline
medium with sodium dithionite or sodium borohydride.
Oxidation is possible with compounds of redox potential
No.
I
Mole ratio of I
to sum of
comonomers
1: 10 micropore
Ill
[Z 358/187 IE]
1:lO
1:3
1:2
1:l
1:l
1:l
Mole- %
crossliking
agent
12.5
12.5
6.0
6.0
8.0
6.0
4.0
Exchange
capacity [*I
tmcs.lrrl
Redox
capacity [**I
b e s . 181
4.375
4.491
3.563
3.080
2.021
2.042
2.084
1.24
1.00
2.57
3.23
4.75
4.33
4.13
[*I Neutral salt splitting of oxidized form determined with 2 N KCI
solution.
II
IV
Angew. Chem. internal. Edit. / VoL I (1962) No. 12
I**] Determined by oxidation with 0.05 M Fe3+ in 2 N &SO4
PI.
659
below 0.7 V. Stronger oxidizing agents in the usual analytical
concentrations slowly attack the resins on prolonged exposure. The Table shows the characteristics of the resins
after four oxidation-reduction cycles.
Resins 1 and 2 both have a redox potential of & = 175 & 1
mV. Oxidative titration was carried out with Ce4+ in 0.1 N
sulfuric acid in the presence of 1 % anthraquinone-2-sulfonic
acid. The index potentials are 14 mV. The titration curve
corresponds to a reversible bivalent redox system.
Received, October Sth, 1962 [Z 362/189 IE]
[l] G . Manecke and W. Storck, Chem. Ber. 94, 3239 (1961).
[2] A. Btienne, G. Izoret, and F. Moritz, C. R.hebd. SCances Acad.
Sci. 249, 708 (1959).
[3] M. Fernandez-Refojo, Yue-Liang Pan, K. A . Kuhn, and H. G.
Cassidy, J. org. Chemistry 25, 416 (1960).
[4]L. W. Butz, E. W. J. Butz, and A . M . Gaddis, J. org. Chemistry
5, 171 (1940).
[ 5 ] G. Manecke, 2.Electrochem., Ber. Bunsenges. physik. Chem.
57, 189 (1953).
Reactive Silyl-substituted Alkyl Sulfanes
By Dr. M. Wieber and Prof. Dr. M. Schmidt
Institut fur Anorganische Chemie
der Universitat Marburg/Lahn (Germany)
On cleavage with dry hydrogen chloride, 1,1,4,4-tetramethyl1,4-disila-2,5-disulfacyclohexane[I] gives quantitatively 2
moles of dimethylchlorosiiylmethylthioi(I), a highly reactive
organofunctional chlorosilane.
CH3
I
I
CH3
It is oxidised by sulfuryl chloride to the disulfide (11)
according to the equation:
CH3
+
2 (0 sozc1z -+
Forschungslaboratorium der Dewey & Almy AG.,
Zurich (Switzerland)
Earlier work has shown that butadiene dioxide (I) adds onto
compounds with active hydrogen atoms, e. g. primary or
secondary amines, exclusively in 1,4-position. It therefore
appeared possible that addition of hydrazine or substituted
hydrazines onto butadiene dioxide would yield 4,5-dihydroxypiperidazines.
\o/
\\
-+
/
\o/
+ so2-t 2 HCl
AH3
+ ClS,Cl+
(I) + 2 HCI
CH3
CH3
CH3
CHI
I
I
+ CI-Si-CH2-S-S,-S-CHZ-Si-CI
I
Compound I1 and its higher homologues are colorless liquids
(yellow a t increased sulfur content); only I1 can be distilled
without decomposition (b.p. 14OoC/1 mm). The new sulfane derivatives react with many other compounds because
of the labile nature of the silicon-halogen bond. Thus,
hydrolysis results in the formation of sulfur chains of definite
composition joined by disiloxane bridges:
- CH3
I
.I
CH3
--ii4-ii-CHz-Sy-CH2-
,/
CH2-CH-CH-CHz
(ID
Condensation with chlorosulfanes leads to higher sulfane
derivatives:
(I)
By Dr. R. Gabler and Dr. H. R. Meyer
CH3
c~-$i<Hz-s-s-cH2sli.<~
kH3
Ring-closure Reaction of Butadiene Dioxide with
Hydrazines to Give New Pyrazolidine and
Piperidazine Derivatives
(I)
Cl-Si-CH2-SH
RHN-NHR
Ill
HO-,,,NH
AH,
AH3
Received, October 8th. 1962
HO,in/CH1OH
-
IZ 365/194 IEI
[l] M. Schrniur and M . Wieber, Inorg. Chem., I , 909 (1962).
"
13)
I
I
OH Li
(4)
R
Dimerisation of Piperidinoacetonitrile under the
Influence of a Grignard Reagent
reduction
2 H3CNHz
_ _ j CH2-CH-CH-CHzOH
CHz-CH-CH-CHz
ci
4
AH
I
I
&€I
b H NH
LHJ
CH3
By Prof. Dr. H. Thies, Priv.-Doz. Dr. H. Schonenberger,
and y.Qasba
(5)
With hydrazine itself in aqueous soIution at 20°C, 4 3 dihydroxypiperidazine was in fact obtained and identified
by reductive ring cleavage to give 1,4 - diaminobutane
2,3-diol. Starting from (f)-butadiene dioxide, trans-4,5-dihydroxypiperidazine (2) is formed (m. p. 233 "C, decornp.),
while the meso-compound gives rise to the cis-isomer.
Unexpectedly, the addition of sym-dimethylhydrazine onto
(&)-butadiene dioxide led to a 1:l-adduct not identical with
the compound obtained by N,N'-methylation of (2) with
formaldehyde. Investigation of the structure showed that 1,3a d d i t i o n had taken place here, giving the pyrazolidine
derivative (3), R = CH3, in 80 % yield. The 5-membered
ring structure of (3) was indicated by reductive opening of the ring to give (5), m.p. 110 "C, which proved to be
identical with the reaction product obtainable from 1,3-dichlorobutane-2,4-dioI (4) and methylamine.
N,N'-Diethylhydrazine and hydrazobenzene also form 1 :1adducts with meso- or (f)-butadiene dioxide in yields of
70-80 %, so that a general and preparatively interesting ring
closure reaction seems to occur. Determination of the constitution of the last two adducts has not yet been completed,
but there are many indications that they also have 5-membered
ring (pyrazolidine) structures.
Institut fur Pharmazie und Lebensmittelchemie
der Universitat Mtinchen (Germany)
-
Received, October Sth, 1962
660
[Z 370/199 IEI
Reaction of piperidinoacetonitrile (1) with t-butylmagnesium
chloride unexpectedly gave rise to a hitherto unknown
(2), an oil
compound, 3-amino-2,4-dipiperidinocroto~itrile
which distils without decomposition in vacuo, b.p. 169 "C/0.3
mm Hg and which crystallizes in the cold to form colorless
rhombic platelets (m.p. 86-87 "C) when crystallized from
isopropanol (yield 71 %). Compound (2) is formed from (I)
by dimerization, the C-atom of the C = N group of one m o l e
cule becoming linked to the a-C-atom of the second molecule.
Ill
Ill
N
N
(11
(2)
131
Its constitution is indicated by its infrared spectrum, its
behaviour with nitrous acid, and its synthesis by the method
of Thompson [l].
Angew. Chem. internat. Edit.
Vol. I (1962) I No. I2
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