REACTIONS OF 2-THIENYLMETHYLIDENE-6-(2-HALOPHENYLMETHYLIDENE)...
1747
3-(2-thienyl)-7-(2-chlorobenzylidene)-3,3a,4,5,6,7-
hexahydro-2H-indazole (IVb) were similarly prepared.
Yield 68%, mp 132–134°C. IR spectrum, ν, cm–1: 3352
(NH), 3116 [CH(Th)], 3018–3065 [CH(Ph)], 721–700
Th). Found, %: C 72.45; H 5.34. C18H15FOS. Calculated,
%: C 72.48; H 5.03.
2-(2-Thienylmethylene)-6-(2-chlorobenzylidene)-
cyclohexanone (II) was similarly obtained. Yield 58%,
mp 83–85°C. IR spectrum, ν, cm–1: 1645 (C=O), 1600
(C=C), 764–721 [CS(Th)]. 1H NMR spectrum, δ, ppm:
1.58–2.01 m (2H, H4), 2.73–3.06 m (4H, H3,5), 8.04 s
(1H, =CHTh), 7.98 s (1H, =CHAr), 7.14–7.52 m (4H,
Ar), 7.52–7.62 m (3H, Th). Found, %: C 73.27; H 4.07.
C18H15FOS. Calculated, %: C 73.10; H 4.35.
1
[CS(Th)]. H NMR spectrum, δ, ppm: 4.72 d, 5.08 d
(1H, H3, J 14.0, 13.6 Hz), 3.14 d, 2.82 d (1H, H3a, J 12,
12 Hz), 6.97 s (1H, =CHTh), 1.07–1.59 m (2H, H4),
1.80–2.33 m (1H, H5), 2.43–2.92 m (1H, H6), 7.03–7.34 m
(4H,Ar), 7.03–7.34 m (3H, Th), 7.41 s (1H, NH). Found,
%: C 70.02; H 5.19; N 9.19. C18H17FN2S. Calculated, %:
C 69.68; H 4.84; N 9.03.
7-(2-Thienylmethylene)-3-(2-fluorophenyl)-
3,3a,4,5,6,7-hexahydro-2H-indazole (IIIa),
3-(2-thienyl)-7-(2-fluorobenzylidene)-3,3a,4,5,6,7-
hexahydro-2H-indazole (IIIb). To a boiling solution
of 0.5 g (1.7 mmol) of dienone I in 30 ml of 2-propanol
was added 0.42 ml (8.5 mmol) of hydrazine hydrate. The
reaction mixture was boiled for 50 min. The precipitated
yellow crystals were washed with a large amount of wa-
ter. Yield 0.33 g (63%), mp 118–120°C. IR spectrum, ν,
cm–1: 3340 (NH), 3105 [CH(Th)], 3022–3074 [CH(Ph)],
721–700 [CS(Th)]. 1H NMR spectrum, δ, ppm: 4.72 d,
4.85 d (1H, H3, J 13.6, 13.6 Hz), 3.15 d, 2.99 d (1H, H3a,
J 16,16 Hz), 6.64 s (1H, =CHTh), 1.21–1.63 m (2H, H4),
1.76–2.15 m (1H, H5), 2.30–3.07 m (1H, H6), 7.00–7.54 m
(4H,Ar), 7.00–7.54 m (3H, Th), 7.72 s (1H, NH). Found,
%: C 70.02; H 5.19; N 9.19. C18H17FN2S. Calculated, %:
C 69.68; H 4.84; N 9.03.
IR spectra of compounds were recorded on a Fourier
spectrophotometer FSM-1201 (from pellets with KBr),
1H NMR spectra, on a spectrometer Varian 400 MHz in
CDCl3 (internal reference TMS). The reaction progress
was monitored and the purity of the compounds was
checked by TLC on Silufol UV-254 plates (eluent hex-
ane–diisopropyl ether–chloroform, 3 : 1 : 1).
REFERENCES
1. Vatsadze, S.Z., Golikov, A.G., Kriven’ko, A.P., and
Zyk, N.V., Usp. Khim., 2008, vol. 77, p. 707.
2. Fomina, Yu.A., Cand. Sci. (Chem.) Dissertation, Sara-
tov, 2008.
3. Fomina, Yu.A., Golikov, A.G., and Kriven’ko, A.P., Zh.
Org. Khim., 2008, vol. 44, p. 715.
4. Bugaev,A.A., Golikov,A.G., Fomina, Yu.A., Egorov, S.V.,
and Kriven’ko,A.P., Izv. VUZov, Ser. Khim. & Khim. Tekh-
nol., 2005, vol. 48, p. 84.
7-(2-Thienylmethylene)-3-(2-chlorophenyl)-
3,3a,4,5,6,7-hexahydro-2H-indazole (IVa),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010