1-AZA-1,3-ENYNES IN SYNTHESIS OF SUBSTITUTED
131
ethynal tert-butylimine in 50 ml of methanol was
added at stirring 0.01 mol of a solution of sym-
metrically substituted 2-mercaptobenzimidazole in
10 ml of DMF. After 2 h the mixture was concentrated.
The residue was dissolved in 50 ml of ethanol, mixed
with 5 ml of water, and refluxed for 1–2 min. After
cooling the fine-crystalline precipitate appears. To
obtain single crystals for X-ray analysis methanol was
NMR spectrum, δ, ppm: 1.32 s (9Н), 3.94 s (6Н), 6.43
d (1Н, 3JНН 5.82 Hz), 6.52 d (1Н, 3JНН 7.99 Hz), 6.57–
6.63 m (2Н), 6.93–6.98 m (1Н). 13С NMR spectrum,
δC, ppm: 29.22, 36.43, 55.90, 73.47, 103.18, 104.09,
112.96, 123.71, 134.79, 141.07, 141.82, 143.82,
144.14. Found, %: С 60.5; N 8.3. C16H20· N2О3S.
Calculated, %: С 60.0; N 8.7.
7,8-Dimethoxy-2-tret-butyl-4H-[1,3]thiazino[3,2-
1
used as solvent. Yield 85%, mp 188°С. Н NMR
1
a]benzimidazol-4-ol (IVe). Yield 85%, mp 226°С. Н
spectrum, δ, ppm: 3.94 s (6Н), 6.43 d (1Н, 3JНН 5.82 Hz),
NMR spectrum, δ, ppm: 1.32 s (9Н), 3.91 s (3Н), 3.93
3
6.52 d (1Н, JНН 7.99 Hz), 6.57–6.63 m (2Н), 6.93–
3
3
s (3Н), 6.04 d (1Н, JНН 5.81 Hz), 6.22 d (1Н, JНН
7.26 Hz), 6.53–6.59 m (2Н), 6.77–6.81 m (1Н). 13С
NMR spectrum, δC, ppm: 29.32, 36.55, 55.74, 55.93,
73.07, 94.80, 100.62, 126.94, 136.40, 141.23, 145.92,
146.50. Found, %: С 59.7; N 8.4. C16H20N2О3S.
Calculated, %: С 59.9; N 8.7.
6.98 m (1Н), 7.45–7.49 m (3Н), 7.60-7.63 m (2Н). 13С
NMR spectrum, δC, ppm: 55.93, 73.80, 103.47, 104.12,
116.54, 123.47, 126.08, 128.78, 129.30, 130.61,
134.71, 136.06, 141.13, 142.90, 144.20. Found, %: С
63.4; N 8.3. C18H16N2 О3S. Calculated, %: С 63.5; N 8.2.
The important crystal data of compound II are
given in Table 3.
7,8-Dimethyl-2-tert-butyl-4H-[1,3]thiazino[3,2-a]-
benzimidazol-4-ol (IVf). Yield 80%, mp 188°С. Н
1
NMR spectrum, δ, ppm: 1.33 s (9Н), 2.35 s (3Н), 2.38
Compounds IVb–IVf were prepared similarly.
3
s (3Н), 5.96 d (1Н, JНН 4.36 Hz), 6.32–6.37 m (1Н),
7,8-Dimethoxy-2-phenyl-4H-[1,3]thiazino[3,2-a]-
benzimidazol-4-ol (IVb). Yield 85%, mp 245°С. Н
6.69 d (1Н, 3JНН 8.72 Hz), 7.25 s (1Н), 7.37 s (1Н). 13С
NMR spectrum, δC, ppm: 19.97, 29.30, 73.12, 110.86,
112.56, 117.57, 129.54, 130.26, 131.78, 141.07,
141.42, 143.12. Found, %: С 66.4; N 9.3. C16H20N2ОS.
Calculated, %: С 66.6; N 9.7.
1
NMR spectrum, δ, ppm: 3.85 s (3Н), 3.89 s (3Н), 6.36
3
d (1Н, JНН 4.36 Hz), 6.56–6.60 m (1Н), 7.02 d (1Н,
3JНН 9.45 Hz), 7.07 s (1Н), 7.25 s (1Н), 7.44–7.47 m
(3Н), 7.61–7.63 m (2Н). 13С NMR spectrum, δC, ppm:
56.04, 73.35, 94.96, 100.75, 116.52, 126.14, 127.03,
129.05, 129.60, 130.10, 136.09, 136.40, 140.73,
REFERENCES
146.22, 146.74. Found, %:
C18H16N2О3S. Calculated, %: С 63.5; N 8.2.
С
63.6;
N
8.1.
1. Stadnichuk, M.D., Khramchikhin, A.V., Piterskaya, Yu.L.,
and Suvorova, I.V., Zh. Obshch. Khim., 1999, vol. 69,
no. 4, p. 616.
7,8-Dimethyl-2-phenyl-4H-[1,3]thiazino[3,2-a]-
benzimidazol-4-ol (IVc). Yield 80%, mp 210°С. Н
1
2. Usanova, E.A., Khramchikhin, A.V., and Stadnichuk, M.D.,
Zh. Obshch. Khim., 2000, vol. 70, no. 7, p. 1120.
NMR spectrum, δ, ppm: 2.37 s (3Н), 2.40 s (3Н), 6.38
3
d (1Н, JНН 5.08 Hz), 6.53-6.57 m (1Н), 6.95 d (1Н,
3. Shimizu, M., Hachiya, I., and Mizota, I., Chem.
Commun., 2009, vol. 1, p. 874.
3JНН 9.45 Hz), 7.30 s (1Н), 7.25 s (1Н), 7.44–7.47 m
13
(4Н), 7.61–7.63 m (2Н). С NMR spectrum, δC, ppm:
4. Karpov, M.V., Khramchikhin, A.V., and Stadnichuk, M.D.,
20.03, 73.40, 111.10, 116.52, 117.65, 118.43, 124.47,
126.06, 127.25, 127.62, 128.80, 129.34, 130.13,
130.70, 131.75, 136.14, 141.15, 142.37. Found, %: С
70.5; N 9.4. C18H16N2ОS. Calculated, %: С 70.1; N 9.1.
Zh. Obshch. Khim., 2005, vol. 75, no. 3, p. 523.
5. Awasthi, A.K., Boys, M.L., Cain-Janicki, K.J., Col-
son, P.-J., Doubleday, W.W., Duran, J.E., and Farid, P.N.,
J. Org. Chem., 2005, vol. 70, no. 14, p. 5387.
6. Karpov, M.V., Khramchikhin, A.V., and Stadnichuk, M.D.,
6,9-Dimethoxy-2-tret-butyl-4H-[1,3]thiazino[3,2-
a]benzimidazol-4-ol (IVd). Yield 85%, mp 146°С. Н
1
Zh. Obshch. Khim., 2005, vol. 75, no. 9, p. 1579.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 1 2011