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Structure and Absolute Configuration of an Organo-Iron Compound Having Iron as Chiral Center.

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Table 2 . Physical data or compounds ( 6 ) to (X).
~~
X
(6Cl)
(6h)
(61.)
(611)
(61,)
(b/)
(hl)
(6h)
(hi)
lhl, I
(61)
(6111)
1611)
Ih<iJ
(611
INCliC
pCH,--C,,H,-N
C,,Hs-N
/I-H;C>OZC-C,H,-N
p-CI-CbH,-N
I?-Br-C,>H,-N
p-NC-C,H,-N
p-O,N-C,H,-N
CoH5-CO-NH-N
3-Pyridyl-CO-NH-N
C,H5-CH-CO-NH-N
NC-CH2-CO-NH-N
C,,H,-NH-N
p-02N-C,,H4-NH-N
3.5-(02NI>C,H3-N H -N
17)
(Xtl)
(
x /I )
(X1.)
("1)
(NCIIC
2.4.6-Trioxopel.liydroI .3-diariti-5-ylidene
C,>HS--C'O-NH-N
1.4-lOrN)iC,H3-NH-N
M.p.
["CI
Yield
Color
249- -250
15X 159
55
18
17
34
4x
37
35
52
54
54
26
53
49
36
51
red
bright yellon
bright yellow
yellow
yellon
yellow
119
1x2
184
204
I84
203
237
226
201
128
134
234
280
130
279
266
256
270
[<'<>I
120
183
I85
205
I X5
204
238
127
202
229
135
235
28 I
yellow
Received: August 30. 1976 [Z 569 IE]
revised: October 4. 1976
German version: Angew. Chem. XX. XI0 11976)
CAS Registry numbers:
I / ). 3216-47-5: ( 2 1 , . 26461-80-3: / 3 ) , 10245-72-4: ( 4 ~ ) 60788-83-2:
.
(4h).
10245-71-3: f.511). 60788-85-4: ( 5 h ) . 60788-87-6. ( 6 ~ 0 .60788-88-7: ( f i b ) .
yellow
yellow
yellow
yellou
yellow
yellow
biolet
60788-894: ( 6 ~ 1 60788-90-1:
.
(611). 60788-91-2: ( h i , ) . 60788-92-3: ( 6 / ) .
60788-93-4: f/i<q).60788-94-5: ( f i l l ) , 60788-95-6: ( 6 ; ) . 60788-96-7: ( O X ) .
60788-974: ( 6 1 ) . 60788-9X-9: ( 6 i i i ) . 60788-99-0: (611). 60789-00-6: ( 6 t i ) .
60789-0 1-7: ( 6 /I 1.60789-02-8: f 7 1.60789-03-9: (<'t[f ).60789-04-0: ( X h ). 6078905- I : (XC.). 60789-06-1: ( X d ) . 60789-07-3: 2-bromo-3.4-dihydro-5-oxo-5Hnaplitho[I.H-h~~]thiophene. 10245-73-5: triethyloxoninm tetrafluoroborate.
368-39-X
\,lolet
132
39
16
\
167
257
271
96
black-red
red-ye1low
\w~let
79
92
Synthesis of ( X u ) : A mixture of ( 5 b ) (1 mmol) and monosodiomalononitrile ( I mmol) in anhydrous tetrahydrofuran
(10ml) is heated under reflux for 24 h. The solvent is removed
and the residue chromatographed with benzene an a column
packed with silica gel 60 (Merck). After removal of benzene
from the eluate ( X u ) is obtained in 16 x) yield.
lolet
red-violet
[I]
[2]
[3]
Esprriiiieiitd:
Synthesis of ( 3 ) : (2) is dissolved in 90'%, acetic acid (3.5
liters) and the solution warmed to 75°C. A solution of Br2
( I mol) in 90'%, acetic acid is then added dropwise and the
mixture stirred for 30min at 75°C. The cooled solution is
poured into 15 liters of water and the resulting precipitate
of (3) dried and recrystallized from methanol; yield 90
m.p. 116-1 17°C.
Synthesis of ( 4 u ) : A mixture of (3) (0.653mol) and S0Cl2
(640ml) is heated under reflux for I h. Excess SO2CI2 is
removed, the residue taken up in 4.18 liters anhydrous CH2C12
and the resulting solution cooled to - 10°C and treated portionwise with AIC13 (0.848mol). The mixture is stirred for
3 h at -5°C. treated with 60g N a 2 S 0 4 . 1 0 H 2 0 and stirred
for a further 4 h at -5°C. I t is then washed with H20.
three times with N a H C 0 3 solution, and the CH2C12 solution
finally dried over MgS04. After removal of CH2CI2the residue
(orange-yellow crystals) is recrystallized from acetic acid : yield
84 m.p. 108-1 10°C.0.0754mol of this substance is heated
under reflux for 3 h with 0.468 mol chloranil in 1.5 liters /cr'tbutanol. The reaction mixture is then filtered, the tert-butanol
removed, and the residue taken up in CHCI,; the resulting
solution is washed four times with H 2 0 , four times with
5 NaOH, a further two times with water, and finally dried
over MgS04. After removal of CH2CI2the remaining orange
crystals are recrystallized from acetic acid; yield 75
m.p.
163--164°C.
Synthesis of ( 5 u ) : A stirred solution of ( 4 u ) (1.89mmol)
in anhydrous dichloroethane is treated at 35-40°C with
1.89mmol triethyloxonium tetrafluoroborate. The resulting
deep ruby-red solution is stirred for 20min. cooled to O"C,
and treated with anhydrous ether, whereupon ( 5 u ) precipitates as a finely crystalline salt which is used immediately
in further reactions. Yield 70 to 80%.
Synthesis of ( 5 h ) : A stirred solution of (4h)14] (1.91 mmol)
in anhydrous dichloroethane (4ml) is treated at 35 to 40°C
with 1.91 mmol triethyloxonium tetrafluoroborate. After 1 h
aqueous ethanol is added, whereupon the orange-red salt
( 5 h ) precipitates. Yield 71 %, m.p. 160-162°C.
Synthesis of ( 6 a ) : CH2(CN)2(1.89mmol) is added to a
stirred solution of ( 5 u ) (1.89mmol) in anhydrous CH3CN
( I 0 ml) at room temperature. Hunig base (3.78 mmol) is added
to the mixture, which is stirred for 1 h and then allowed to
stand overnight at - 15°C. Red crystals.precipitate; yield 55%.
[4]
[5]
Based o n lectures by R . Nridiriii in Haifa. Hamburg, Heidelberg. Jerusalem. Rehovot. and Tel-Aviv.
E. Cmpmqiw and E. S. Nc&s. J. Heterocycl. Chem. 2, 231 11965): P.
Cqqmorir, Bull. Soc. Chim. Fr. l Y 4 Y . 382: F . F . B l i d r and G. S/irc,ts.
J. A m . Chem. Soc. 70. 3768 (1948): S. .4tdi1111, J . Mo.>\, and G. J
.Wor.fiil. ihrtl. 70. 3075 11948).
S. Hiitit</and E . i W / l . Justus Liebigs Ann. Chem. 732. 7'(1970).
D. G. H~~II~I/I(?~IIc
and Q . N . Ptwrrr.. Aust. J. Chem. / Y . 1909 (1966).
See C J . ~ S.
.
ffiiiiiq and E . W ~ J / /Justus
/.
Liebigs Ann. Chem. 732. 26
I19701.
Structure and Absolute Configuration of an Organo-Iron
Compound Having Iron as Chiral Center[']
'I<),
By M. George R e i ~ i i ~l r, m Beriia/, Hrnri Bruriner, and
Mui?fred Muschio/[*]
The absolute configurations are known of optically active
organo-Mo compounds with square pyramidal coordination
around the metal atom['] and of ferrocene derivative^'^] in
which the metal atom is not the chiral center. We now describe
the structure and absolute configuration of compound (1 ),
in which the iron atom is bonded to four different ligandsf4].
'z,,
x,
I%,,
776
Compound ( I )crystallizes in the orthorhombic space group
P21212twith u= 11.201(3), b=14.817(7), and c= 18.976(3)A;
V=3149.36A3; d,,,=1.12(2) and d,,,,=1.10 g/cm3 for a unit
cell with four molecules. A total of4422 independent reflections
was collected with a computer-controlled diffractometer using
monochromatized Mo-Ka radiation .;( = 0.71069 A) to
2 0 1 6 0 " . The structure was solved and refined using 2194
reflections for which I ( h k / ) > 3g[I(hk/)]. The final R ( F ) and
R,(F) values were, respectively, 0.066 and 0.072. The absolute
configuration of ( 1 ) was determined by- refinement of the
entire data set with the two possible enantiomeric configura~~
.
[*] Dr. M. G. Reisner a n d Prof. Dr. 1. Bernal [**]
Chemistry Department. University of Houston
Houston, Texas 77004 ( U S A )
Prof. Dr. H. Brunner a n d M. Muschiol
lnstitut Iur Chemie der UniversitPt
Universitiitsstrasse 3 I , D-8400 Regensburp (Germany)
[**I Recipient o f a US Senior Scientist Award administered by the Alexander
von Humboldt-Foundation: present address(1976-1977): lnstitut fur Chemie
der Universitiit. Universitiitsstrasse 3 I . D-8400 Regensburg,lGerman,y~.
A i l g t w . Chriii. lilt.
E d . Em)/. 1 V i l . / 5 ( 1 9 7 6 ) No. I 2
tions as models and by direct measurement of those 26 Friedel
pairs (four measurements for each pair) for which the differences between FcalC(/k/),
Fo(hk/),and Fo(hkj)was largest. Both
methods give the same result. The absolute configuration
absolute
of ( I ) , shown in Figure 1, also confirms the
configurations of the three chiral centers in the menthyl moiety.
Trifluoroacetylationof Amines with N-TrifluoroacetylNylon 66"l
By Hermann Schuttenberg and Rolf C. Schulzl*]
Reaction of poly(hexamethy1eneadipamide)(Nylon 66) with
trifluoroacetic anhydride affords high yields of a product which
is soluble in tetrahydrofuran (THF), dioxane, chlorinated hyi
drocarbons, acetone, acetonitrile, or dimethylformamide,
(DMF). Elemental analysis and IR and NMR spectra are
consistent with the substance being a polymer containing
the repeating unit (1 ).
When treated with water at room temperature the polymer
liberates trifluoroacetic acid quantitatively; no detectable
degradation of the polyamide chain occurs, either during the
synthesis of ( I ) or on treatment with water. The polyamide
content of ( 1 ) can be determined by titration of the liberated
trifluoroacetic acid; it agrees up to 98 "/, with the elemental
analysis. Hydrolysis with D,012] furnishes a NyIon 66 extensively deuterated at the nitrogen. Similarly to low molecular
N-trifluoroacetyl compounds[", ( I ) can also be employed
for the trifluoroacetylation of amines (2).
IP,
ili
/,"
It1,
Sf1
-I
+ K\lOll
(i(i
+
,{2'
p
'
h-(:
/ q-,, I
P i
'C' I. ,,
L?J
F I ~ .I . Structure aiid absolute configuration of i l l . [2Ii-,,<0.
The Fe-C(C,Hs) distances average to 2.113(21) A ; other
interesting distances are: Fe-P= 2.214(2). Fe-COOR
1.825(6), Fe-CO = 1.670(7). and C-0 (in CO) = 1.206(9)A.
The distances and angles within the triphenylphosphane and
menthyl groups compare well with accepted literature values.
With the extension of the R,S-system[bJto polyhapto ligands
in organometallic complexes[71the priority sequence of the
ligands in ( I ) is CsH5 > P(ChHS)3> C O O C l o H t 9 > CO.
The configuration at the Fe atom consequently is (S).
Received: October I . 1976 [Z 570 I E ]
G c r m m version: Angeu. Cheni HK. X47 11976)
Part 2 of the srriea "Absolute Configurationa of Organonictallic Compounds". Part I : Ref. [?a].
Also Part 45 of tlie series "Optically
Acti\eTr;inaition Metal Complexes". Part 44: H . B r i i i i i w r a n d W S f ~ q i ~ .
Bull. Soc. Chim. Belg.. in press. M . C . R m i ~ c , rand I. BerriiiI thank
tlie Welch Found;ition and the National Scicnce Foundation for support
of this study.- H Brrrrrirw and M . Mii.sdiio/ thank the Deutsche For-.
schungsgemeinschaft and the Fonds der Chemischen Industrie for support
or thls uork.
al S . .1. l.liPIm(i. I . B w i i d . H . Briiiiiic,r. and W 4. H~~riiii~iirii.
Angew.
Cheni. cS?. 379 (1975). A n g w . Chem. Int. Ed. Engl. 14. 353 ilY75):
b) W! B I ~ W. Diriixr. .A. 7: Liri. m d G . Hiitrri~~i.,Angcw. Chem. S?I.
51 I (1976): Angeu. Cheni. Int. Ed. En$ 15. 495 (1976).
C i.iviiirti,. k: Dii.uirr\oi.. J . Priir(i\. B. G ~ i i i ~ / r ~ ~aiid
r i ~ i rR, Bmii.\,\iiv.
Acta Crystallogr. Sect. B 29. 1504 11973): 1.. I.. B d r d I ~ ~R.. B,rii. G
M/ G o L d . R . 7: O p i L i i i w . and 1. K L y i . I . Am. Chem. Soc. 95. 4x2
(197.31 The determination of the absolute coiifiguratioii of Fe complexes
chi!-a1 at the metal atom is mentioned 111 the litei-iitiire aitliout gr\iiig
details: T C. F/iwiI. F. J . DiSliiifi. mid D. L. )ifiIc\. .I Chem. Soc
Chem. Commun. iY7.5. 336: 4 . Dlii koii and N . , M w r ~ i i .I.
~ ~Organomet.
~ .
Chem. 74. C I7 1974).
H Briiiiiiei. and E. Sdiiuidr. .I. Organomet. Cheni. 21. P 5 3 (1970). 50.
119 11973).
1: PrrIov. Helv. Chim. Acta 36. 30X 11953): E. J . Gohr and 11. I ( ; r m i .
Acta Crystnllopr. I S . 1074 (1962).
R. S. CiiIiii. C . IiiqoIiI, and C: P r h y . Angcu. Chem. 7 X 413 119661:
Angeu. Chem. Int. Ed. t n g l . .i.385 (1966).
K . Sliiirlci and M . C . lhiird. .I.Am. Chem. Soc. Y7. 6599 (1975).
Table I . Reactions of i l i with amines 121 for the preparation of trrnuoroacetamides 131 Reaction medium: acetonitrile: room temperature, duration of
reaction 12h: Xields and melting points of crude products.
.~
~.
Aminc ( 2 )
~.
~
Yield of /J')
I",,]
M.p. ["C]
[Lit -m p J
Ref.
~-
Benzylamine
91
L-( - )-r-Methyibenzylaminc 93
Aniline
ii-Hexylaminc
Hexiimethylenediamiiie
Piperidine
p-Nit roaniline
89
95
96
95
40
73 74 [74 751
9 5 ~96 196 -OX]
86--87 189 901
4 [El]
I19 I20 [I21
[a1
3
[a1
[5]
161
[5]
PI
1231 [5]
[51
171
[a] Identified by comparison of the I R specrra and by gas chromatography
with authentic samples.
To carry out the reaction, ( l ) is suspended in acetonitrile.
During the course of the reaction Nylon 66 is formed and can
be easily separated by filtration. On concentrating the filtrate
the corresponding trifluoroacetamide ( 3 ) is obtained (see
Table 1).
Remarkably, ( 1 ) reacts only slowly, if at all. with some
amines, even though these amines react readily with trifluoroacetic anhydride. This selectivity can be exploited for the
separation of mixtures of amines. Alcohols can likewise be
converted into the trifluoroacetyl derivatives with ( I ).
E.uperimer7 ta 1:
Synthesis of ( 1 ): Trifluoroacetic acid anhydride (10ml) is
added with vigorous stirring at 0°C to a suspension of finely
~
[*I
-.
Dr. H. Schuttenberg
Calle 502. entre 1 2 ~ 1 3
Gonnet-La Plata (Argentina)
Prof. Dr. R. C . Schtilz ['I
Institut fGr Organische Chemie der Universitiit
J.-.I.-Bechei--Weg I X, 20. D-6500 Mainz (Germany)
['IAuthor to whom correspondence should be addressed.
177
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