6562
A. V. Shastin et al. / Tetrahedron 56 (2000) 6557±6563
50 mmol) was added dropwise over 10 min, maintaining the
temperature at 208C. The reaction mixture was stirred for
4 h and quenched with water (300 ml); any aldazine 3a±p
that precipitated was ®ltered off. The reaction products were
extracted with hexane (50 ml£3). The extracts were dried
over sodium sulphate, hexane was evaporated and the
residue was puri®ed by column chromatography.
1-(2,2-Dichlorovinyl)-2,6-dichlorobenzene 2k. Yield 79%,
n2D0 1.5850 (lit.2 n2D0 1.5853).
1-(2,2-Dichlorovinyl)-2,4-dichlorobenzene
2l.
The
compound was obtained as colourless crystals, yield 62%,
mp 49±508C. IR (Nujol) (n, cm21) 1620 (CvC). 1H NMR
(CDCl3) d 7.65 (dd, 3J8.5 Hz, 5J0.6 Hz, 1H, CH-6), 7.43
(d, 4J2.1 Hz, 1H, CH-3), 7.28 (dd, 3J8. 5 Hz, 4J2.1 Hz,
1H, CH-5), 6.99 (s, 1H, Ar±CHvC). 13C NMR (CDCl3) d
134.80 (C-2), 134.21 (C-4),130.78 (C-3), 130.44 (C-1),
129.39 (C-5), 127.02 (C-6), 124.70 (C-10), 124.28 (CCl2).
Anal. Calcd for C8H4Cl4 (%): C, 39.72; H, 1.67. Found: C,
40.18; H, 1.56.
The known compounds 2a, 2b, 2c, 2g, 2h, 2i, 2k, 2m, 2n,
2o, 3a, 3c, 3e, 3k, 3m, 3o and 3p were identi®ed by com-
parison of the spectral data and melting point or boiling
point with those described in the literature.
1-(2,2-Dichlorovinyl)-4-nitrobenzene 2a. Yield 79%, mp
948C (lit.2 948C).
1-(2,2-Dichlorovinyl)-benzene 2m. Yield 27%, n2D0 1.5880
(lit.2 n2D0 1.5874).
1-(2,2-Dichlorovinyl)-3-nitrobenzene 2b. Yield 67%, mp
548C (lit.6 53±558C).
4-(2,2-Dichlorovinyl)-N,N-dimethylaniline 2n. Yield
26%, mp 70±718C (lit.2 mp 70±718C).
4-(2,2-Dichlorovinyl)-benzonitrile 2c. Yield 78%, mp
73±748C (lit.6 75±768C).
1-(2,2-Dichlorovinyl)-4-methoxybenzene 2o. Yield 49%,
n2D0 1.5978 (lit.6 n2D0 1.5975).
3-(2,2-Dichlorovinyl)-benzonitrile 2d. The compound was
obtained as colourless crystals, yield 70%, mp 33±348C
(from EtOH); IR (Nujol) (n, cm21): 2240 (CN), 1620
(CvC). 1H NMR (CDCl3) d 7.83 (dd, 4J1.8 Hz,
2-(2,2-Dichlorovinyl)-4-nitrophenole 2p The compound
was obtained as colourless crystals, yield 14%, mp 153±
1558C. IR (Nujol) (n, cm21) 1630 (CvC), 1530 (NO2),
3
4
1
4J1.8 Hz, 1H, CH-2), 7.73 (ddd, J8.0 Hz, J1.8 Hz,
1380 (O±H). H NMR (CDCl3) d 10.96 (s, 1H, OH), 8.62
4J1.8 Hz, 1H, CH-6), 7.59 (ddd, 3JHH7.8 Hz,
(d, 4J2.8 Hz, 1H, CH-3), 8.04 (dd, 3J9.0 Hz, 4J2.8 Hz,
1H, CH-5), 7.09 (s, 1H, CH), 7.01 (d, 1H, CH-6,
3J9.0 Hz). 13C NMR (CDCl3) d 160.47 (C-1), 139.12
(C-4), 124.76 (C-10), 124.20 (C-5), 121.78 (C-3), 121.62
(CCl2), 120.15 (C-2), 114.92 (C-6). Anal. Calcd for
C8H5Cl2NO3 (%): C, 41.06; H, 2.15. Found: C, 41.32; H,
2.30.
4
3
4J1.5 Hz, J1.5 Hz, 1H, CH-4), 7.49 (dd, J8.0 Hz,
3J7.8 Hz, 1H, CH-5), 6.85 (s, 1H, Ar±CHvC). 13C
NMR (CDCl3) d 134.50 (C-1), 132.60 (C-2), 131.84
(C-6), 131.66 (C-4), 129.38 (C-5), 126.40 (C-10), 123.85
(CCl2), 118.25 (CN), 112.84 (C-3). Anal. Calcd for
C9H5Cl2N (%): C, 54.58; H, 2.54. Found: C, 54.38; H, 2.48.
1-(2,2-Dichlorovinyl)-4-bromobenzene 2e. The compound
was obtained as colourless crystals, yield 57%, mp 24±258C
(from EtOH); IR (Nujol) (n, cm21) 1620 (CvC). 1H NMR
(CDCl3) d 7.45 (d, 3J8.6 Hz, 2H, CH-2,6), 7.35 (d,
3J8.6 Hz, 2H, CH-3,5), 6.74 (s, 1H, Ar±CHvC). 13C
NMR (CDCl3) d 132.12 (C-1), 131.59 (C-3,5), 130.04
(C-2,6), 127.41 (C-10), 122.46 (C-4), 121.73 (CCl2). Anal.
Calcd for C8H5Cl2Br (%): C, 38.14; H, 2.00. Found: C,
38.42; H, 2.01.
4-Nitrobenzaldehyde (4-nitrobenzylidene)hydrazone 3a.
Yield 17%, mp 296±2978C (lit.22 296±2978C).
4-Formylbenzonitrile
4-cyanobenzylidene)hydrazone
3c. Yield 17%, mp 318±3208C (lit.23 296±2978C).
4-Bromobenzaldehyde (4-bromobenzylidene)hydrazone
3e. Yield 40%, mp 222±2248C (lit.24 223.5±224.58C).
2,6-Dichlorobenzaldehyde (2,6-dichlorobenzylidene)hy-
1-(2,2-Dichlorovinyl)-3-bromobenzene 2f. The compound
was obtained as colourless liquid, yield 66%, n1D7 1.6220. IR
(Nujol) (n, cm21) 1630 (CvC). 1H NMR (CDCl3) d 7.63 (s,
drazone 3k. Yield 15%, mp 152±1538C (lit.25 1538C).
Benzaldehyde (benzylidene)hydrazone 3m. Yield 68%,
mp 92±938C (lit.26 93±948C).
3
1H, CH-2), 7.40 (m, 2H, CH-4,6), 7.18 (dd, J8.0 Hz,
3J8.0 Hz, 1H, CH-5), 6.73 (s, 1H, Ar±CHvC). 13C
NMR (CDCl3) d 135.11 (C-1), 131.30 (C-6), 131.25
(C-4), 129.82 (C-5), 127.09 (C-10), 127.06 (C-2), 122.44
(CCl2). Anal. Calcd for C8H5Cl2Br (%): C, 38.14; H, 2.00.
Found: C, 38.16; H, 1.96.
4-Methoxybenzaldehyde (4-methoxybenzylidene)hydra-
zone 3o. Yield 44%, 167±1688C (lit.27 168±1698C).
2-Hydroxy-5-nitro-benzaldehyde
(2-hydroxy-5-nitro-
benzylidene)hydrazone 3p. Yield 80%, mp 2988C (lit.21
3008C).
1-(2,2-Dichlorovinyl)-4-chlorobenzene 2g. Yield 74%, nD20
1.5930 (lit.1 nD20 1.5914).
1-(2,2-Dichlorovinyl)-3-chlorobenzene 2h. Yield 65%, bp
103±1058C/1 Torr, n1D7 1.5970 (lit.6 103±1058C/1 Torr).
Acknowledgements
Financial support from the Russian Foundation for Basic
Research (Grant No. 00-03-32760a) is gratefully acknowl-
edged.
1-(2,2-Dichlorovinyl)-2-chlorobenzene 2i. Yield 64%, nD20
1.5793 (lit.1 nD20 1.5793).