Decyanation of 5-alkyl-6-aryl-4-oxocyclohexane-1,1,2,2-tetracarbonitriles

Full text of DOI:10.1023/A:1020882402873

Russian Journal of Organic Chemistry, Vol. 38, No. 7, 2002, pp. 1068 1069. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 7, 2002,
pp. 1111 1112.
Original Russian Text Copyright
2002 by Sheverdov, Ershov, Nasakin, Tafeenko.
SHORT
COMMUNICATIONS
Decyanation of 5-Alkyl-6-aryl-4-oxocyclohexane-
1,1,2,2-tetracarbonitriles
V. P. Sheverdov, O. V. Ershov, O. E. Nasakin, and V. A. Tafeenko
Ul’uanov Chuvash State University, Moskovskii pr. 15, Cheboksary, 428015 Russia
e-mail: ershov@chuvsu.ru
Received September 12, 2001
4-Oxocyclohexane-1,1,2,2-tetracarbonitriles are
formed by reaction of tetracyanoethylene with , -un-
saturated ketones [1, 2]. By the action of water they
are converted into 5-hydroxy-7-oxo-6-azabicyclo-
[3.2.1]octane-1,2,2-tricarbonitriles. We have revealed
unusual decyanation of tetracyanocyclohexanones
Ia Id to tricyanocyclohexanones IIIa IIId in the
presence of sulfuric acid. This is the first example of
selective elimination of only one cyano group in the
series of polycyanoalkanes, which occurs in acid
medium. Analogous known reactions require the pres-
ence of reducing agents [3, 4]. Selective decyanation
of one cyano group in position 2 is explained by its
intramolecular interaction with the carbonyl group.
We have also found that such interaction gives rise
to 5-hydroxy-7-oxo-6-azabicyclo[3.2.1]octane-1,2,2-
tricarbonitriles IIa IId not only by the action of water
on cyclohexanones Ia Id [1] but also on heating of
compounds I with 5% aqueous sulfuric acid. Treat-
ment of Ia Id with H2SO4 under more severe condi-
tions leads to formation of tricyanocyclohexanones
IIIa IIId (Scheme 1).
That the transformation I III involves inter-
mediate formation of azabicyclooctanes IIa IId was
confirmed by the conversion of compounds II into
III. Intermediates IVa IVd shown in Scheme 1 are
formed via retro-cyclization of IIa IId, which was
described by us previously [1]. Hydrolysis of amides
IVa IVd and subsequent decarboxylation of the cor-
responding carboxylic acids yield the final products,
tricyanocyclohexanones IIIa IIId.
5-Hydroxy-4-methyl-7-oxo-3-phenyl-6-azabi-
cyclo[3.2.1]octane-1,2,2-tricarbonitrile (IIa). Tetra-
cyanocyclohexanone Ia, 0.01 mol, was dissolved in
a mixture of 5 ml of dioxane and 5 ml of 5% sulfuric
acid, and the solution was heated for 10 min under
reflux. The mixture was diluted with 50 ml of water,
and the precipitate was filtered off, washed with
water, 2-propanol, and diethyl ether, and dried in
Scheme 1.
I IV, R = Me (a, c), Pr (b, d); Ar = Ph (a, b), MeOC6H4 (c, d).
1070-4280/02/3807-1068$27.00 2002 MAIK Nauka/Interperiodica

DECYANATION OF 5-ALKYL-6-ARYL-4-OXOCYCLOHEXANE-.. .
1069
air. Yield 91%, mp 223 224 C (decomp.; from
2-propanol). IR spectrum, , cm : 3525 (OH); 3340,
C 69.72; H 5.12; N 14.35. C17H15N3O2. Calculated,
%: C 69.61; H 5.15; N 14.33.
1
1615 (NH); 2270 (C N); 1705 (C O).
Compounds IIb IId were synthesized and purified
in a similar way.
6-p-Methoxyphenyl-5-methyl-4-oxocyclohexane-
1,1,2-tricarbonitrile (IIIc). Yield 79%, mp 168
169 C (from 2-propanol). IR spectrum, , cm : 2270,
1
5-Hydroxy-7-oxo-3-phenyl-4-propyl-6-azabi-
cyclo[3.2.1]octane-1,2,2-tricarbonitrile (IIb). Yield
95%, mp 211 212 C (decomp.; from 2-propanol). IR
spectrum, , cm : 3535 (OH); 3335, 1645 (NH);
2270 (C N); 1710 (C O).
2265 (C N); 1705 (C O). 1H NMR spectrum
(DMSO-d6), , ppm: 7.36 d (2H, o-H, J = 8.5 Hz),
7.03 d (2H, m-H, J = 8.5 Hz), 4.66 d.d (1H, CHCN,
J = 15.0, 6.5 Hz), 3.83 s (3H, OCH3), 3.74 d (1H,
CHAr, J = 14.0 Hz), 3.21 d.q (1H, CHMe, J = 14.0,
6.5 Hz), 3.07 d.d (1H, COCH2, J = 15.0, 4.5 Hz),
2.99 t (1H, COCH2, J = 15.0 Hz), 0.78 d (3H, CH3,
J = 6.5 Hz). Mass spectrum, m/z: M+ 293. Found, %:
C 69.72; H 5.12; N 14.35. C17H15N3O2. Calculated,
%: C 69.61; H 5.15; N 14.33.
1
5-Hydroxy-3-p-methoxyphenyl-4-methyl-7-oxo-
6-azabicyclo[3.2.1]octane-1,2,2-tricarbonitrile (IIc).
Yield 95%, mp 228 229 C (decomp.; 2-propanol). IR
1
spectrum, , cm : 3450 (OH); 3330, 1625 (NH);
2280 (C N); 1710 (C O).
6-p-Methoxyphenyl-5-propyl-4-oxocyclohexane-
1,1,2-tricarbonitrile (IIId). Yield 71%, mp 171
172 C (from 2-propanol). IR spectrum, , cm :
5-Hydroxy-3-p-methoxyphenyl-7-oxo-4-propyl-
6-azabicyclo[3.2.1]octane-1,2,2-tricarbonitrile (IId).
Yield 95%, mp 185 186 C (decomp.; from i-PrOH).
IR spectrum, , cm : 3510 (OH); 3350, 1645 (NH);
2275 (C N); 1710 (C O).
1
2270 (C N); 1710 (C O). 1H NMR spectrum
(DMSO-d6), , ppm: 7.49 d (2H, o-H, J = 8.5 Hz),
7.1 d (2H, m-H, J = 8.5 Hz), 4.48 d.d (1H, CHCN,
J = 15.0, 6.5 Hz), 3.83 s (3H, OCH3), 3.8 d (1H,
CHAr, J = 13.5 Hz), 3.21 d.t (1H, CHPr, J = 13.5,
6.5 Hz), 3.07 d.d (1H, COCH2, J = 12.5, 4.5 Hz),
2.99 t (1H, COCH2, J = 12.5 Hz), 1.4 1.0 m (4H,
CH2CH2CH3), 0.8 d (3H, J = 6.5 Hz, CH2CH2CH3).
Mass spectrum, m/z: M+ 321. Found, %: C 71.02;
H 5.99; N 13.08. C19H19N3O2. Calculated, %:
C 71.01; H 5.96; N 13.08.
1
5-Methyl-4-oxo-6-phenylcyclohexane-1,1,2-tri-
carbonitrile (IIIa). To a solution of 0.01 mol of tetra-
cyanocyclohexanone Ia or azabicyclooctane IIa in
5 ml of dioxane we added under continuous stirring
5 ml of 30% sulfuric acid. The mixture was heated
for 24 48 h under reflux and diluted with 50 ml of
water, and the precipitate was filtered off, washed
with water and 2-propanol, and dried in air. Yield
76%, mp 165 166 C (from 2-propanol). IR spectrum,
The progress of reactions and the purity of products
were monitored by TLC on Silufol UV-254 plates.
The IR spectra were recorded on a UR-20 instrument
1
1
, cm : 2265 (C N), 1710 (C O). H NMR spec-
trum (DMSO-d6), , ppm: 7.51 7.22 m (5H, Ph),
4.6 d.d (1H, CHCN, J = 15.0, 6.5 Hz), 3.85 d (1H,
CHAr, J = 14.0 Hz), 3.47 m (1H, CHMe), 3.12 d.d
(1H, COCH2, J = 15.0, 6.5 Hz), 3.01 t (1H, COCH2,
J = 15.0 Hz), 0.82 d (3H, CH3, J = 6.5 Hz). Mass
spectrum, m/z: M+ 263. Found, %: C 73.02; H 4.91;
N 15.92. C16H13N3O. Calculated, %: C 72.99; H 4.98;
N 15.96. Compounds IIIb IIId were synthesized in
a similar way.
1
in mineral oil. The H NMR spectra were recorded
on a Bruker AM-300 spectrometer at 300 MHz using
DMSO-d6 as solvent. The molecular weights were
determined by mass spectrometry using a Finnigan
Mat Incos 50 instrument (70 eV).
REFERENCES
1. Sheverdov, V.P., Ershov, O.V., Nasakin, O.E., Cher-
nushkin, A.N., Tafeenko, V.A., and Firgang, S.I.,
Tetrahedron, 2001, vol. 57, no. 27, pp. 5815 5824.
4-Oxo-6-phenyl-5-propylcyclohexane-1,1,2-tri-
carbonitrile (IIIb). Yield 81%, mp 176 177 C (from
1
2-propanol). IR spectrum, , cm : 2270 (C N), 1705
(C O). 1H NMR spectrum (DMSO-d6), , ppm:
7.48 7.21 m (5H, Ph), 4.44 d.d (1H, CHCN, J = 13.0,
5.5 Hz), 3.81 d (1H, CHAr, J = 14.0 Hz), 3.47 d.t
(1H, CHPr, J = 14.0, 6.5 Hz), 3.09 d.d (1H, COCH2,
J = 13.0, 4.5 Hz), 2.95 t (1H, COCH2, J = 13.0 Hz),
1.35 1.0 m (4H, CH2CH2CH3), 0.81 d (3H, CH3,
J = 6.8 Hz). Mass spectrum, m/z: M+ 291. Found, %:
2. Sheverdov, V.P., Ershov, O.V., Nasakin, O.E., Cher-
nushkin, A.N., and Tafeenko, V.A., Russ. J. Org.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 7 2002