Reaction of tetracyanoethylene with 2-substituted cyclohexanones

Article abstract of DOI:10.1023/A:1020801612443

Reactions of 2-methylcyclohexanone and menthone with tetracyanoethylene gave 2-(1,1,2,2-tetracyanoethyl)cyclohexanones which underwent quantitative transformation in the solid phase into 3,4-cyanosubstituted 2-aminopyrans in 2-3 days at room temperature.

Full text of DOI:10.1023/A:1020801612443

Russian Journal of Organic Chemistry, Vol. 38, No. 7, 2002, pp. 1001 1004. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 7, 2002,
pp. 1043 1046.
Original Russian Text Copyright
2002 by Sheverdov, Ershov, Nasakin, Chernushkin, Tafeenko.
Reaction of Tetracyanoethylene
with 2-Substituted Cyclohexanones
V. P. Sheverdov, O. V. Ershov, O. E. Nasakin,
A. N. Chernushkin, and V. A. Tafeenko
Ul’yanov Chuvash State University, Moskovskii pr. 15, Cheboksary, 428015 Russia
e-mail: ershov@chuvsu.ru
Received September 12, 2001
Abstract Reactions of 2-methylcyclohexanone and menthone with tetracyanoethylene gave 2-(1,1,2,2-tetra-
cyanoethyl)cyclohexanones which underwent quantitative transformation in the solid phase into 3,4-cyano-
substituted 2-aminopyrans in 2 3 days at room temperature. 2-Methyl-2-(1,1,2,2-tetracyanoethyl)cyclohexa-
none reacted with hydroiodic acid to afford 8a-hydroxy-2-iodo-4a-methyl-1,4,4a,5,6,7,8,8a-octahydroquino-
line-3,4,4-tricarbonitrile. The reaction of 2,2 -methylenedi(cyclohexanone) with tetracyanoethylene resulted
in formation of 7-imino-4,5-tetramethylene-2 -oxo-6-oxabicyclo[3.2.1]octane-2-spiro-1 -cyclohexane-1,8,8-tri-
carbonitrile.
As follows from the data summarized in [1], cyclic
carbonyl compounds were involved mainly in reac-
tions with , -unsaturated nitriles. This is explained
by higher reactivity of cyclic ketones as compared to
open-chain analogs. Cyclic ketones are used as initial
compounds for the synthesis of fused pyran deriva-
tives [2 4]. Substituted tetrahydrobenzo[b]pyrans are
formed in 10 min by reaction of cyclohexanone with
, -unsaturated nitriles in boiling ethanol in the pres-
ence of triethylamine [3]. Derivatives of dihydrofuran
[5] and pyridine [6 9] were obtained in two steps
from cyclohexanone and tetracyanoethylene.
Reactions of linear ketones, such as acetone,
methyl ethyl ketone, and diethyl ketone, with tetra-
cyanoethylene take 6 24 h. Cyclohexanone reacts
with tetracyanoethylene much more vigorously (in
1 2 min) [10, 11]. Wide application of tetracyano-
ethylene in reactions with carbonyl compounds with
the goal of obtaining carbo- and heterocycles [1 10]
stimulates our further studies in this field and
emphasizes prospects in the use of these reactions
for modification of organic compounds possessing
a CR13C(O)CHR22 fragment.
We have found that, unlike unsubstituted cyclo-
hexanone, reactions of 2-substituted cyclohexanones
with tetracyanoethylene either occur under different
conditions or yield unexpected products. The reaction
of tetracyanoethylene with 2-substituted cyclohexa-
nones, including 2-chlorocyclohexanone, was reported
for the first time in [11]. Instead of the expected
2-chloro-2-(1,1,2,2-tetracyanoethyl)cyclohexanone,
6,6,7,7-tetracyanospiro[2.4]heptan-1-one was isolated.
Cyclohexanone reacts with tetracyanoethylene to give
2-(1,1,2,2-tetracyanoethyl)cyclohexanone; the latter
undergoes complete decomposition in 5 7 days at
room temperature [10, 11].
The present work continues our studies on tetra-
cyanoethylation of 2-substituted cyclohexanones. As
substrates we used 2-methylcyclohexanone, menthone
(2-isopropyl-5-methylcyclohexanone), and 2,2 -
methylenedi(cyclohexanone). The reactions were
carried out in dioxane in the presence of hydrochloric
Scheme 1.
1070-4280/02/3807-1001$27.00 2002 MAIK Nauka/Interperiodica

1002
SHEVERDOV et al.
Scheme 2.
acid. From 2-methylcyclohexanone in 3 h we obtained
90% of 2-methyl-2-(1,1,2,2-tetracyanoethyl)cyclo-
hexanone (I) (Scheme 1), i.e., tetracyanoethylation of
2-methylcyclohexanone occurs at position 2.
An unusual transformation was revealed when
cyclohexanone I was stored for 1 2 days at room
temperature. As a result, 2-amino-4a-methyl-4a,5,6,7-
tetrahydro-4H-chromene-3,4,4-tricarbonitrile (II) was
formed in quantitative yield (Scheme 1).
Analogous transformations were observed in the
tetracyanoethylation of menthone. The latter reacted
with tetracyanoethylene to afford 69% of 6-isopropyl-
2-(1,1,2,2-tetracyanoethyl)-3-methylcyclohexanone
(III) which was quantitatively converted into 2-amino-
8-isopropyl-5-methyl-6,7-dihydro-5H-chromene-3,4-
dicarbonitrile (IV) on storage in the solid state
(Scheme 2).
proposed by us in [8]: an analogous structure was
assumed to be the last intermediate.
The reaction of 2,2 -methylenedi(cyclohexanone)
with tetracyanoethylene occurs under mild conditions
and at a high rate. The product is oxabicyclo[3.2.1]-
octane-7,8,8-tricarbonitrile VI which is formed in
high yield. The main difference of this reaction from
those described above is intramolecular interaction
between the acid dicyanomethyl fragment CH(CN)2
and the carbonyl group, leading to closure of two
rings (Scheme 4).
Scheme 4.
The reaction with HI indicates high reactivity of
ketone I. Stirring of 2-methyl-2-(1,1,2,2-tetracyano-
ethyl)cyclohexanone (I) in concentrated hydroiodic
acid for 1 2 h gave 83% of 8a-hydroxy-2-iodo-5-
methyl-1,4,4a,5,6,7,8,8a-octahydroquinoline-3,4,4-tri-
carbonitrile (V) (Scheme 3).
Scheme 3.
The structure of compounds I VI was confirmed
by the data of IR and H NMR spectroscopy and mass
spectrometry. The structure of product VI was proved
by X-ray analysis.
1
This reactions provides a support for the scheme
of formation of 2-iodocyanopyridines by reaction
of , , , -tetracyanoalkanones with HI, which was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 7 2002

REACTION OF TETRACYANOETHYLENE WITH 2-SUBSTITUTED CYCLOHEXANONES
1003
Structure of the molecule of 7-imino-4,5-tetramethylene-2 -oxo-6-oxabicyclo[3.2.1]octane-2-spiro-1 -cyclohexane-1,8,8-tricarbo-
nitrile (VI) according to the X-ray diffraction data.
EXPERIMENTAL
1.58 m (6H, CH2CH2, CH(CH3)2, CHCH3, 1.44 d
(3H, CH3, J = 6.4), 0.93 d (3H, CH3, J = 6.0), 0.85 d
(3H, CH3, J = 6.0). IR spectrum, , cm : 1705, 2270.
1
The IR spectra were recorded on a UR-20 spec-
1
trometer in mineral oil. The H NMR spectra were
2-Amino-4a-methyl-4a,5,6,7-tetrahydro-4H-
chromene-3,4,4-tricarbonitrile (II) and 2-amino-8-
isopropyl-5-methyl-6,7-dihydro-5H-chromene-3,4-
dicarbonitrile (IV) (general procedure). Compound
I or III, 0.01 mol, was kept for 2 3 days at room
temperature.
obtained on a Bruker AM-300 instrument (300 MHz)
in DMSO-d6. The molecular weights were determined
from the mass spectra which were run on a Finnigan
Mat Incos 50 instrument (70 eV). The unit cell param-
eters and reflection intensities for a single crystal of
VI were measured on a Siemens P3/PC four-circle
diffractometer ( MoK irradiation, graphite mono-
chromator, /2 scanning). The progress of reactions
and the purity of products were monitored by TLC
on Silufol UV-254 plates.
Compound II. Yield 98%, mp 197 198 C. 1H
NMR spectrum, , ppm: 6.12 s (2H, NH2), 2.71 m
(1H, CHCH2), 2.7 1.8 m [6H, (CH2)3], 0.98 s (3H,
1
CH3). IR spectrum, , cm : 2215, 2270, 3225, 3310.
Mass spectrum: m/z 240 [M]+.
2-Methyl-2-(1,1,2,2-tetracyanoethyl)cyclohexa-
none (I) and 6-isopropyl-3-methyl-2-(1,1,2,2-tetra-
cyanoethyl)cyclohexanone (III) (general procedure).
2-Methylcyclohexanone or menthone, 0.02 mol, and
3 4 drops of concentrated hydrochloric acid were
added to 0.01 mol of tetracyanoethylene in 20 ml
of dioxane. After 24 h, 100 ml of water was added,
and the precipitate was filtered off and washed with
2-propanol and ether.
1
Compound IV. Yield 99%, mp 211 212 C. H
NMR spectrum, , ppm: 7.68 s (2H, NH2), 3.04 m
(1H, CHCH3), 2.68 2.42 m [4H, (CH2)2], 1.53 m
[1H, CH(CH3)2], 1.15 d (3H, CH3, J = 6.2), 0.92 d
1
(6H, CH3, J = 6.5). IR spectrum, , cm : 2210, 3215,
3295. Mass spectrum: m/z 255 [M]+.
8a-Hydroxy-2-iodo-4a-methyl-1,4,4a,5,6,7,8,8a-
octahydroquinoline-3,4,4-tricarbonitrile (V). A mix-
ture of 3.68 g (0.01 mol) of 2-methyl-2-(1,1,2,2-tetra-
cyanoethyl)cyclohexanone (I) and 10 15 ml of con-
centrated hydroiodic acid was stirred for 2 h at 20 C.
The mixture was diluted with 40 ml of water, and the
precipitate was filtered off and washed with water and
2-propanol. Yield 83%, mp 178 179 C. 1H NMR
spectrum, , ppm: 9.24 s (1H, NH), 8.97 s (1H, OH),
1.86 1.24 m [8H, (CH2)4], 0.98 s (3H, CH3). IR
Compound I. Yield 90%, mp 168 167 C. 1H NMR
spectrum, , ppm: 6.35 s (1H, CH), 2.6 m (2H,
CH2CO), 1.74 1.29 m [8H, (CH2)4], 0.94 s (3H, Me).
1
IR spectrum, , cm : 1710, 2270.
1
Compound III. Yield 69%, mp 145 146 C. H
NMR spectrum, , ppm: 7.01 s [1H, CH(CN)2], 3.81 d
(1H, CHCO, J = 7.9), 2.52 m (1H, CH2CHCO), 2.27
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 7 2002

1004
SHEVERDOV et al.
1
spectrum, , cm : 2220, 2270, 3200, 3410. Mass
4. Assy, M.G. and Abdel-Ghani, E., Pol. J. Chem.,
spectrum: m/z 368 [M]+.
1995, vol. 69, no. 5, pp. 685 690.
5. Nasakin, O.E., Nikolaev, E.G., Terent’ev, P.B.,
Bulai, A.Kh., and Kalandarishvili, A.G., Khim.
Geterotsikl. Soedin., 1985, no. 8, pp. 1027 1030.
7-Imino-4,5-tetramethylene-2 -oxo-6-oxabicyclo-
[3.2.1]octane-2-spiro-1 -cyclohexane-1,8,8-tricarbo-
nitrile (VI). 2,2 -Methylenedi(cyclohexanone), 2.08 g
(0.01 mol), and 3 4 drops of concentrated hydro-
chloric acid were added to 1.28 g (0.01 mol) of tetra-
cyanoethylene in 20 ml of dioxane. After 12 h, the
mixture was diluted with 50 ml of water, and the pre-
cipitate was filtered off and washed with 2-propanol
and ether. Yield 85%, mp 218 219 C. IR spectrum,
6. Nasakin, O.E., Nikolaev, E.G., Terent’ev, P.B.,
Bulai, A.Kh., Khaskin, B.A., and Mikhailov, V.K.,
Khim. Geterotsikl. Soedin., 1984, no. 11, p. 1574.
7. Nasakin, O.E., Nikolaev, E.G., Terent’ev, P.B.,
Bulai, A.Kh., and Lavrent’eva, I.V., Khim. Getero-
tsikl. Soedin., 1987, no. 5, pp. 653 656.
1
, cm : 1700, 2260, 3280. Mass spectrum: m/z 336
8. Nasakin, O.E., Nikolaev, E.G., Moiseeva, I.V.,
Ershov, O.V., Chernushkin, A.N., and Tafeen-
ko, V.A., Russ. J. Gen. Chem., 1999, vol. 69, no. 2,
pp. 291 300.
[M]+. Crystallographic data: space group P21/c; unit
cell parameters ( 90 C): a = 8.932(2), b = 10.008(5),
c = 19.404(3)
;
= 90 , = 93.56(10) , = 90 ;
V = 1731.2(10) 3; z = 4; R = 0.0436.
9. Nasakin, O.E., Sheverdov, V.P., Ershov, O.V.,
Moiseeva, I.V., Lishchikov, A.N., Khrustalev, V.N.,
and Antipin, M.Yu., Mendeleev Commun., 1997,
pp. 112 113.
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