ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 8, pp. 1247−1248. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.L. Gein, N.V. Nosova, A.V. Vagapov, L.F. Gein, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 8, pp. 1228−1229.
SHORT
COMMUNICATIONS
Synthesis of 2,6-diaryl-3-benzoyl-4-hydroxy-4-phenyl-1,1-cyclo-
hexanedinitriles
V. L. Geina, N. V. Nosovaa, A. V. Vagapova, and L. F. Geinb
aPerm State Pharmaceutical Academy, Perm, 614990 Russia
e-mail: geinvl48@mail.ru
bPerm State Medical Academy, Perm, Russia
Received December 6, 2010
DOI: 10.1134/S1070428011080227
We found that the reaction of chalcones Ia, Ib with
malononitrile in the presence of KOH in ethanol solution
at room temperature gave rise to 2,6-diaryl-3-benzoyl-
4-hydroxy-4-phenyl-1,1-cyclohexanedinitriles IIa, IIb.
In the first stage apparently the malononitrile adds to the
double bond of the chalcone to form the intermediate
compound A that along the mechanism suggested for the
cycloketols formation [1] undergoes the cyclization into
cyclohexanedinitriles IIa, IIb.
Their IR spectra contain absorption bands of the stretch-
ing vibrations of OH group in the region 3408–3445 cm–1,
of carbonyl group in the region 1644–1650 cm–1, and also
of cyano groups in the region 2350–2360 cm –1.
In the 1H NMR spectra of compounds IIa, IIb along-
side the signals of the aromatic protons signals appear
of the CH2 group in the position 5 as two doublets of
doublets at 2.05–2.16 and 4.35–4.65 ppm, of the proton
of the CH group in the position 6 of the ring as a triplet
at 3.14–3.26 ppm, of protons from two CH groups in the
positions 2 and 3 of the alicycle as two doublets with the
centers at 4.67–4.92 and 4.59– 4.83 ppm, and a singlet
of the hydroxy group proton at 5.72–5.82 ppm.
Compounds IIa, IIb are crystalline substances soluble
in DMSO, DMF, ethanol, butanol, acetonitrile, and in-
soluble in water.
O
Mass spectrum of compound IIa contains peaks of
fragment ions, m/z: 253 [C6H5COCHCHC6H5NO2]+, 224
[C6H5COCH2COC6H5]+, 105 [C6H5CO]+, 77 [C6H5]+
that confirm the assumed structure The fragmentation of
compound IIb is of similar character.
R
R
H
N
N
Ph
Ph
O
R
N
N
+
Ph
H
Iа, Ib
3-Benzoyl-4-hydroxy-2,6-di(3-nitrophenyl)-4-phe-
nylcyclohexane-1,1-dicarbonitrile (IIa). To a mixture of
0.005 mol of 3-nitrobenzalacetophenone and 0.005 mol
of malononitrile was added 30 ml of 0.1% ethanol solu-
tion of KOH, the mixture was heated to dissolution and
left standing for 24 h at room temperature. The separated
precipitate was filtered off, washed with water, and re-
crystallized. Yield 0.66 g (23%), mp 166–168°C (ace-
tonitrile). IR spectrum, ν, cm–1: 3408 (OH), 2350 (CN),
1644 (C=O). 1H NMR spectrum, δ, ppm: 2.16 d.d (1H,
C5HAHC, J 2.7, 13.9 Hz ), 3.26 t (1H, C6H, J 13.9 Hz),
4.65 d.d (1H,C5HAHC, J 2.7, 13.9 Hz ), 4.83 d (1H, C2H,
O
А
R
O
CN
CN
Ph
HO
Ph
R
IIа, IIb
R = 3-NO2 (a), 4-F (b).
1247
Gein
