Reactivity of 1,1,2,2-tetracyano-3-(2,2-dimethylhydrazino)cyclopentanes toward amines

Article abstract of DOI:10.1023/A:1020482323596

Substituted 1,1,2,2-tetracyano-3-(2,2-dimethylhydrazino)cyclopentanes were reacted with amines to synthesize substituted 1,5,5-tricyano-4-(2,2-dimethylhydrazino)-1-cyclopentenes and 5-cyano-2-(dicyanomethylene)-1-(dimethylamino)pyrrolidines.

Full text of DOI:10.1023/A:1020482323596

Russian Journal of General Chemistry, Vol. 72, No. 6, 2002, pp. 909 911. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 6, 2002,
pp. 972 974.
Original Russian Text Copyright
2002 by Sheverdov, Bulkin, Ershov, Nasakin, Tafeenko.
Reactivity
of 1,1,2,2-tetracyano-3-(2,2-dimethylhydrazino)cyclopentanes
Toward Amines
V. P. Sheverdov, V. V. Bulkin, O. V. Ershov, O. E. Nasakin, and V. A. Tafeenko
Ul’yanov Chuvash State University, Cheboksary, Chuvashia, Russia
Received August 28, 2000
Abstract Substituted 1,1,2,2-tetracyano-3-(2,2-dimethylhydrazino)cyclopentanes were reacted with amines
to synthesize substituted 1,5,5-tricyano-4-(2,2-dimethylhydrazino)-1-cyclopentenes and 5-cyano-2-(dicyano-
methylene)-1-(dimethylamino)pyrrolidines.
1,1,2,2-tetracyano-3-(2,2-dimethylhydrazino)cyclo-
pentanes have been prepared by reactions of 1,1,2,2-
tetracyanoethane with dimethylhydrazones of , -
unsaturated aldehydes [1]. They exhibit a very high
reactivity, undergoing an exceptionally facile C2 C3
bond cleavage [2]. This bond is cleaved even when
substituted tetracyanocyclopentanes are dissolved in
organic solvents [3]. Therewith, the C3 signal in the
13C NMR spectra is broadened [1]. The decyclization
of tetracyanocyclopentane Ia by the C2 C3 bond have
been proved by the formation of salt II on mixing of Ia
with equimolar amount of triethylamine in dioxane [1].
H3C
NC
N(C2H5)3
H2C CH=N N(CH3)2
+
NHN(CH3)2
HCl
H3C CH C(CN)2 C(CN)2 NH(C2H5)3
NC
CN
NC
Ia
II
Since the Ia
II conversion occurs at room
amines at higher temperatures.
temperature within 1 2 min, we considered it interest-
ing to study the decyclization and to perform reactions
of the CN, C=N, and C(CN)2 functional groups with
Heating of cyclopentanes Ia Ic in dioxane with
triethylamine at a 1:(0.0005 0.0007) molar ratio gave
cyclopentenes Va Vc (Table 1).
Table 1. IR and 13C NMR spectra and elemental analyses of compounds Va Vc and VIa VIc
1
IR spectrum, , cm
Chemical shift, C, ppm
Comp.
no.
C1
C2
C3
C4
C5
C6
CN
Va
Vb
Vc
VIa
VIb
VIc
3230, 2239, 1650
3210, 2228, 1612
3250, 2227, 1628
2228, 2220, 1584
2230, 2220, 1585
2229, 2221, 1600
102.05 170.63
100.68 165.36
94.01 150.16
175.0
40.5
66.20
66.36
65.45
33.64
35.53
34.5
47.54
50.0
48.08
38.2
45.29
45.13
112.46
115.25, 114.79, 113.14
113.69
116.02, 120.8, 119.06
116.41, 114.07, 118.30
117.11, 119.16
39.38
35.65
45.13
47.82
42.8
51.2
52.06
50.36
171.09
174.5
1070-3632/02/7206-0909$27.00 2002 MAIK Nauka/Interperiodica

910
SHEVERDOV et al.
Table 1. (Contd.)
Found, %
H
Calculated, %
H
Compound no.
Formula
C
N
C
N
Va
Vb
Vc
VIa
VIb
VIc
61.35
69.33
62.89
61.34
69.27
64.19
6.11
5.43
4.89
6.11
5.46
7.05
32.54
25.23
26.23
32.55
25.27
28.76
C11H13N5
C16H15N5
C14H13N5O
C11H13N5
C16H15N5
C13H17N5
61.38
69.29
62.91
61.38
69.30
64.18
6.09
5.45
4.90
6.09
5.45
7.04
32.53
25.25
26.20
32.53
25.25
28.78
R
H2C CH=N N(CH3)2
R CH C(CN)2 C(CN)2
+
BH
B
NC
NHN(CH3)2
NC
NC
CN
Ia Ic
IIIa IIIc
R
H2C CH=N N(CH3)2
NC
B
NHN(CH3)2
CN
R CH C=C
CN
CN
CN
NC
CN
IVa IVc
Va Vc
HCN B
CN
R
H2C CH NHN(CH3)2
CN
NC
NC
CN
R CH C=C
CN
HCN
N
CN
N(CH3)2
VIa VIc
VIIa VIIc
R = CH3 (Va, VIa), C6H5 (Vb, VIb), 2-furyl (Vc), C3H7 (VIc).
This reaction, as the reactions of cyclopentanes I
with N(C2H5)3, yielding compounds like II, involves
intermediates IIIa IIIc.
mediates IVa IVc, thus yielding labile compounds
VIIa VIIc and then pyrrolidines VIa VIc. The struc-
tures of compounds Va Vc and VIa VIc were proved
by X-ray diffraction and 13C NMR and IR spectro-
scopy (Table 1).
It is known that the tetracyanoethanide anion forms
a tricyanovinyl fragment [4 8]. Therefore, we suppose
that the second stage involves decyanation to give
intermediates IVa IVc and final products Va Vc.
Probably, the action of triethylamine and other
bases on cyclopentanes Ia Ic consists in that it
ensures formation of salts IIIa IIIc in the beginning
of the reaction. Salts IIIa IIIc are unstable and con-
vert into Va Vc or VIa VIc, depending on the reac-
tion conditions.
A different reaction pathway was observed on
treatment of cyclopentanes I with a 2 3-fold excess
of N(C2H5)3 in 2-propanol water, followed by heating
of the reaction mixture to boiling. The reaction pro-
ducts were pyrrolidines VIa VIc. Probably, the first
two stages of this reaction are similar to the formation
of cyclopentenes Va Vc. The HCN liberated in the
course of the reaction adds to the C=N bond of inter-
Compared with N(C2H5)3, ammonia and other
amines [C2H5NH2, (C2H5)2NH] react with compounds
Ia Ic, yielding cyclopentenes Va Vc and pyrrolidines
VIa VIc, for a longer time. The highest yields of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 6 2002

REACTIVITY OF 1,1,2,2-TETRACYANO-3-(2,2-DIMETHYLHYDRAZINO)CYCLOPENTANES
911
Table 2. Reaction times, yields, and melting points of compounds Va Vc and VIa VIc
Reaction time, min
Yield, %
Comp.
no.
mp,
C
a
a
NH3
5 7
NH2Eta
NH(Et)2
5 7
N(Et)3
5 6
NH3
NH2Eta
NH(Et)2
N(Et)3
Va
Vb
Vc
VIa
VIb
VIc
32
33
21
51
33
41
15
24
9
15
14
18
35
38
25
43
27
33
42
47
33
42
30
38
102 103
126 127
148 149
169 170
165
5 7
25 30
25 30
20 25
10 15
118 119
a
Aqueous solution.
pyrrolidines VIa VIc are from cyclopentanes Ia Ic
and ammonia. Comparable yields of cyclopentenes
Va Vc and pyrrolidines VIa VIc were obtained with
N(C2H5)3 and NH(S2N5)2. In the other cases, the
yields are lower than with N(C2H5)3 (Table 2).
washed with 15 20 ml of a 1:1 2-propanol water
mixture, and recrystallized from 2-propanol.
Substituted 5-cyano-2-(dicyanomethylene)-1-
(dimethylamino)pyrrolidines VIa VIc. A mixture of
0.01 mol of cyclopentane Ia Ic, 35 ml of 2-propanol,
10 ml of water, and 0.02 0.03 mol of base was
heated under reflux for 10 30 min. After the reaction
was complete, the reaction mixture was cooled to 0
5 C, diluted with 60 ml of water, the precipitate was
filtered off, washed with 25 30 ml of 2-propanol, and
recrystallized from 2-propanol.
Cyclopentenes Va Vc and pyrrolidines VIa Vc
present interest in terms of antiviral activity [9].
EXPERIMENTAL
The IR spectra were obtained on a UR-20 instru-
ment in Vaseline oil. The 13C NMR spectra were
measured in CD3CN on a WH-90 instrument
(22.63 MHz) with broad-band proton decoupling and
off-resonance decoupling; the reference was HMDS.
REFERENCES
1. Nasakin, O.E., Sheverdov, V.P., Lukin, P.M., Tafeen-
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vol. 28, no. 9, pp. 1841 1849.
X-ray diffraction study of compound Va was
performed on a DAR-UM diffractometer, CuK radia-
tion, direct method, Rentgen-75 program. The X-ray
diffraction study of compound VIa was performed a
CAD-4 four-circle diffractometer. The structures were
solved by direct methods using the MULTAN
program of the SDP package.
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Principal crystallographic data for compound Va:
a 10.577(2), b 6.980(2), c 15.884(3)
;
100.38(2) ,
V 1150.9 3, Z 4, space group P21/b, R 0.078.
Principal crystallographic data for compound VIa: a
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10.553(4), b 23.906(16), c 9,750(2)
;
95.12 , V
2455.2 3, Z 8, space group P21S, R 0.043.
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no. 10, pp. 848 849.
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A
mixture of
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100 ml of water. The precipitate was filtered off,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 6 2002