CASCADE TRANSFORMATIONS OF (2,2-DIARYL-3,3-DICHLOROAZIRIDIN-1-YL)ACETATES
569
and the mixture was filtered. The filtrate was washed
with cold water (3 20 ml), dried over MgSO4, the
solvent was evaporated to give orange oily substance
(390 mg). The residue was submitted to column
chromatography that provided 0.125 g of compound
V, yield 21%, mp 169 171 C (from ether hexane).
bromide (0.52 g, 3 mmol), and benzyltriethyl-
ammonium chloride (0.07 g, 0.31 mmol) in aceto-
nitrile (3 ml) was added at vigorous stirring the
powdered potassium hydroxide (0.225 g, 4 mmol),
maintaining the temperature at 21 23 C with the use
of a cooling bath. The mixture was stirred at this
temperature for 2 h, then 30 ml of ether was added,
and the mixture was filtered. The filtrate was washed
with cold water (3 20 ml), dried over MgSO4, the
solvent was evaporated, and from the residue com-
pound VII was isolated by crystallization (0.102 g,
1
IR spectrum (CCl4), cm : 3030, 2950, 2215 (CN),
1740 (C=O), 1590, 1095. 1H NMR spectrum
(CDCl3), , ppm: 3.11 s (3H, CH3), 3.39 s (3H,
CH3O), 6.15 d (2H, J 8.4 Hz), 6.40 d (2H, J 8.4 Hz),
7.00 d (2H, J 8.4 Hz), 7.08 d (2H, J 9.1 Hz), 7.12
7.18 m (4H), 7.35 d (2H, J 8.4 Hz), 7.46 d (2H,
J 8.4 Hz). 13C NMR spectrum (CDCl3), , ppm:
39.4 (CH3N), 51.7 (OCH3), 115.7 (CN), 127.8,
128.0, 128.3, 129.1, 130.0, 131.6, 132.8, 133.6,
134.6, 134.9, 135.0, 135.5, 136.4, 137.6, 138.1,
139.0 (C=C, CPh); 166.4 (C=O). Found, %:
C 63.60; H 3.68; N 4.35. C32H22Cl4N2O2. Calculat-
ed, %: C 63.18; H 3.64; N 4.60.
33 %). mp 166 168 C (EtOH). UV spectrum,
,
nm (log ): 257 (4.27), 313 (3.99), 393 (3.65).maIxR
1
spectrum (CHCl3), cm : 2210 (CN), 1714 (C=O).
1H NMR spectrum (CDCl3), , ppm: 3.19 s (3H,
MeO), 4.58 s (2H, CH2), 6.24 d (2H, Ph, J 7.0 Hz),
6.43 d (2H, Ph, J 7.2 Hz), 7.58 6.99 m (21H, Ph).
13C NMR spectrum (CDCl3), , ppm: 50.8 (CH3O),
55.5 (CH2N), 116.6, (CN), 126.9, 127.0, 127.1,
127.5, 127.7, 127.9, 128.0, 128.2, 128.6, 128.9,
129.3, 129.8, 130.0, 132.7, 133.1, 135.9, 137.6,
138.5, 138.8, 140.2, 141.6, 142.7 (C=C, CPh);
167.3 (C=O). Found, %: C 83.56; H 5.64; N 4.81.
C38H30N2O2. Calculated, %: C 83.49; H 5.53;
N 5.12.
Methyl 3,3-diphenyl-2-[N-allyl-N-(2,2-diphenyl-
1-cyanovinyl)amino]acrylate (VI). To a mixture of
aziridine IIa (0.383 g, 1.14 mmol), allyl bromide
(1.48 g, 12 mmol), and benzyltriethylammonium
chloride (0.07 g, 0.31 mmol) in acetonitrile (3 ml)
was added at vigorous stirring the powdered potas-
sium hydroxide (0.225 g, 4 mmol), maintaining the
temperature at 21 23 C with the use of a cooling
bath. The mixture was stirred at this temperature for
2 h, then 30 ml of ether was added, and the mixture
was filtered. The filtrate was washed with cold water
(3 20 ml), dried over MgSO4, the solvent was
evaporated to give orange oily substance (210 mg).
From this residue compound VI was isolated by
crystallization from ethanol (0.103 g, 36 %). mp
166 168 C (EtOH). UV spectrum, max, nm (log ):
257 (4.43), 310 (4.10), 409 (3.83). IR spectrum
4-Benzhydrylidene-2,3,4,7,8,9,10,11-octahydro-
1H-3a,5,11a-triazabenzo[ef]heptalen-7-one
(IX).
To a solution of aziridine IIb (155 mg, 0.46 mmol) in
acetonitrile (1 ml) was added dropwise a solution of
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (70 mg,
0.46 mmol) in acetonitrile (1 ml). The mixture self-
heated and gave rise to red compound IX which
crystallized at completion of the reaction. Yield
100 mg (57%). The same reaction was carried out in
cyclohexane using 140 mg, 0.92 mmol of DBU. The
reaction continued for 3 h, and compound IX crystal-
lized in the course of the process. Yield 163 mg
(93%). mp 234 235 C (from ether). IR spectrum
1
(CHCl3), cm : 2210 (CN), 1721 (C=O). 1H NMR
spectrum (CDCl3), , ppm: 3.26 s (3H, MeO), 4.00 d
(2H, CH2N, J 6.7 Hz), 5.38 5.28 m (2H, CH2=),
6.44 6.11 m (1H, CH=), 6.18 d (2H, Ph, J 7.0 Hz),
6.43 d (2H, Ph, J 7.3 Hz), 7.26 6.90 m (10H, Ph),
7.48 7.31 m (6H, Ph). 13C NMR spectrum (CDCl3),
, ppm: 51.1 (CH3O), 54.2 (CH2N), 116.0, 116.1,
120.1, 126.9, 127.0, 127.2, 127.7, 127.9, 128.2,
128.6, 128.9, 129.8, 129.9, 130.2, 132.2, 133.2,
134.7, 137.6, 138.5, 140.3, 141.4, 142.0 (CN, C=C,
CPh); 167.1 (C=O). Found, %: C 82.47; H 5.51;
N5.16. C34H28N2O2. Calculated, %: C 82.23; H5.68;
N 5.64.
1
(CHCl3), cm : 3030, 2875, 1645, 1580 (C=O).
1H NMR spectrum (CDCl3), , ppm: 1.73 m (2H,
CH2), 1.89 m (2H, CH2), 2.01 m (2H, CH2), 2.47 t
(2H, CH2, J 5.9 Hz), 3.33 t (2H, CH2, J 5.9 Hz),
3.42 m [4H, (CH2)2], 7.24 7.46 m (10H, Ph), 9.22 s
(1H, CH). 13C NMR spectrum (CDCl3), , ppm:
20.5, 21.1, 25.6, 27.9, 35.9, 49.0, 54.4, 94.8 (C7a),
126.5, 126.7, 126.8, 127.6, 128.2, 130.2, 131.1
(CPh); 131.8 (C6), 138.4 (C1 ), 139.8, 141.5(CPh);
147.3 (C4), 162.8 (C11b), 173.9 (C=O). Mass spec-
trum, m/z (Irel, %): 383(54) [M]+ , 354(4), 306(9)
[M-Ph]+ , 177(8), 163(3), 152(100), 151(100),137(36),
124(23), 123(46), 110(15), 109(11), 96(57), 95(13),
93(39), 89(7), 88(6), 86(7), 70(18), 69(23), 68(19),
66(13), 57(21), 55(32), 54(21), 43(50), 41(79), 39(18),
Methyl
2-[N-benzyl-N-(2,2-diphenyl-1-cyano-
vinyl)amino]-3,3-diphenylacrylate (VII). To a mix-
ture of aziridine Ia (0.383 g, 1.14 mmol), benzyl
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 4 2003