REACTION OF ORGANOZINC REAGENTS
1921
C15H11ClN2O4. Calculated, %: C 56.53; H 3.48;
N 8.79.
VIa VIh except that instead of 2-arylmethylenemalo-
nic acid dinitrile methyl ester of a 2-aryl-3-cyanopro-
penoic acid has been used.
Dimethyl 3-(4-methoxyphenyl)-2,2-dicyanocyc-
lopropane-1,1-dicarboxylate (Vd). Yield 67%, mp
Trimethyl 3-(4-bromophenyl)-2-cyanocyclopro-
1
101 102 C. IR spectrum (mineral oil), , cm : 1725,
pane-1,1,2-tricarboxylate (Vi). Yield 68%, mp 92
1
1
2245. H NMR spectrum, , ppm: 3.75 s (6H, CH3O,
93 C. IR spectrum (mineral oil), , cm : 1730, 2235.
1H NMR spectrum, , ppm: 3.66 s (3H, COOCH3),
3.77 s (3H, COOCH3), 3.83 s (1H, CH), 3.87 s (3H,
COOCH3), 7.15 d (2H, 4-BrC6H4), 7.45 d (2H,
4-BrC6H4). Found, %: C 48.47; H 3.50; N 3.49.
C16H14BrNO6. Calculated, %: C 48.50; H 3.56;
N 3.54.
COOCH3), 3.91 s (1H, CH), 3.95 s (3H, COOCH3),
6.78 7.22 m (4H, MeOC6H4). Found, %: C 61.07;
H 4.43; N 8.84. C16H14N2O5.Calculated, %: C 61.14;
H 4.49; N 8.91.
Diethyl 3-phenyl-2,2-dicyanocyclopropane-1,1-
dicarboxylate (Ve). Yield 69%, mp 71 72 C. IR
1
1
spectrum (mineral oil), , cm : 1720, 2240. H NMR
spectrum, , ppm (J, Hz): 1.16 t, 1.36 t (6H,
COOCH3CH2, J 7.4), 3.91 s (1H, CH), 4.14 q, 4.40 q
(4H, COOCH3CH2, J 7.4), 7.16 7.29 m (5H, C6H5).
Found, %: C 65.30; H 5.11; N 8.89. C17H16N2O4.
Calculated, %: C65.38; H 5.16; N 8.97.
Trimethyl 3-(3-bromophenyl)-2-cyanocyclopro-
pane-1,1,2-tricarboxylate (Vj). Yield 65%, mp 104
1
106 C. IR spectrum (mineral oil), , cm : 1730, 2245.
1H NMR spectrum, , ppm: 3.68 s (3H, COOCH3),
3.75 s (3H, COOCH3), 3.82 s (1H, CH), 3.87 s (3H,
COOCH3), 7.08 7.45 m (4H, 3-BrC6H4). Found, %: C
48.40; H 3.48; N 3.47. C16H14BrNO6. Calculated, %:
C 48.50; H 3.56; N 3.54.
Diethyl 3-(4-bromophenyl)-2,2-dicyanocyclo-
propane-1,1-dicarboxylate (Vf). Yield 70%, mp 86
1
87 C. IR spectrum (mineral oil), , cm : 1725, 2240.
Trimethyl 3-(2,4-dichlorophenyl)-2-cyanocyclo-
1H NMR spectrum, , ppm (J, Hz): 1.20 t, 1.42 t (6H,
COOCH3CH2, J 7.4), 3.84 s (1H, CH), 4.16 q, 4.40 q
(4H, COOCH3CH2, J 7.4), 7.12 7.49 m (4H, BrC6H4).
Found, %: C 52.12; H 3.77; N 7.09. C17H15BrN2O4.
Calculated, %: C 52.19; H 3.86; N 7.16.
propane-1,1,2-tricarboxylate (Vk). Yield 66%, mp
1
116 117 C. IR spectrum (mineral oil), , cm : 1735,
2245. 1H NMR spectrum.: (400 MHz), , ppm (J, Hz):
3.78 s (3H, COOCH3); 3.81 d (1H, CH, J 1.0); 3.83 s
(3H, COOCH3); 3.94 s (3H, COOCH3); 7.29 dd (1H,
H5 , J 8.4, 2.0); 7.34 d.d (1H, H6 , J 8.4, 1.0); 7.46 d
(1H, H3 , J 2.0). 13C NMR (100 MHz, , ppm, J, Hz):
31.32 d (C2, J 2.5); 37.90 d.d (C3, J 169.7, 4.6);
47.34 d (C1, J 3.0); 53.72 q (MeO, J 148.4); 53.85 q
(MeO, J 149.0); 54.81 q (MeO, J 149.2); 112.03 d
(CN, J 4.4); 126.28 d.d.d (C1 , J 7.9, (C4 , J 10.4, 3.9,
2.5); 162.81 d.q (CO, J 5.0, 4.1); 163.87 d.q (CO, J
5.7, 4.0); 164.55 d.q (CO, J 5.2, 4.0). Found, %: C
49.73; H 3.3.35; N 3.59. C16H13Cl2NO6. Calculated,
%: C 49.76; H 3.3.39; N 3.63.
Diethyl 3-(4-chlorophenyl)-2,2-dicyanocyclo-
propane-1,1-dicarboxylate (Vg). Yield 69%, mp 85
1
87 C. IR spectrum (mineral oil), , cm : 1725, 2240.
1H NMR spectrum, , ppm (J, Hz): 1.19 t, 1.43 t (6H,
COOCH3CH2, J 7.4), 3.86 s (1H, CH), 4.16 q, 4.40 q
(2H, COOCH3CH2, J 7.4), 7.17 7.26 m (4H, ClC6H4).
Found, %: C 58.79; H 4.30; N 8.02. C17H15ClN2O4.
Calculated, %: C 58.88; H 4.36; N 8.08.
Diethyl 3-(4-methoxyphenyl)-2,2-dicyanocyclo-
propane-1,1-dicarboxylate (Vh). Yield 67%, mp 75
1
77 C. IR spectrum (mineral oil), , cm : 1725, 2240.
ACKNOWLEDGMENTS
1H NMR spectrum, , ppm, (J, Hz): 1.20 t, 1.42 t (6H,
COOCH3CH2, J 7.4), 3.75 s (3H, CH3O), 3.85 s (1H,
CH), 4.16 q, 4.39 q (4H, COOCH3CH2, J 7.4), 6.76
7.23 m (4H, MeOC6H4). Found, %: C 63.04; H 5.24;
N 8.11. C18H18N2O5. Calculated, %: C 63.15; H 5.30;
N 8.18.
This research was financially supported by the
Russian Foundation of Basic Research (projects
no. 04-03-96036, 04-03-97505).
REFERENCES
3-Aryl-2-cyanocyclopropane-1,1,2-tricarboxylic
acid trialkyl esters (Vi Vk). The procedure is similar
to a technique used for preparation of compounds
1. Gaudemar-Bordone F., Gaudemar M., Bull. Soc. Chim.
France., 1971, vol. 10, p. 4188.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 12 2006