3-R-2-Thioxo-1,2,3,4,5,6,7,8-octahydrobenzo[b]thieno[2,3-d]pyrimidin-4-ones (6'a-g). A solution of
the respective 3-ethoxycarbonyl-2-(N-R-thioureido)-4,5,6,7-tetrahydrobenzo[b]thiophene (10 mmol) and
potassium hydroxide (1.12 g, 20 mmol) in ethanol (20 ml) was boiled for 3-4 h. The reaction mixture was
poured into water, neutralized with glacial acetic acid, and cooled. The precipitate was filtered off.
2-R-Amino-4(H)-5,6,7,8-tetrahydrobenzo[b]thieno[2,3-d]-1,3-thiazin-4-ones (7a, b). Compound
2e,k (10 mmol) was dissolved in concentrated sulfuric acid (15 ml), and the solution was left at 18-20°C for
24 h. It was then poured into iced water (100 ml) and neutralized with ammonia. The precipitate was filtered
off.
The Picrate of 3-Ethoxycarbonyl-2-[4-(p-tert-butyl)-3-phenyl-2-thiazolinylideneamino]-4,5,6,7-
tetrahydrobenzo[b]thiophene (9). Compound 2b (3.6 g, 10 mmol) and p-tert-butyl-α-bromoacetophenone
(2.53 g, 10 mmol) were boiled in ethanol (25 ml) for 4 h and cooled. A saturated solution of picric acid was
added, and the precipitate was filtered off.
S-Substituted
3-R-2-Mercapto-3,4,5,6,7,8-hexahydrobenzo[b]thieno[2,3-d]pyrimidin-4-ones
(8a',b'). To a solution of the potassium salt 6 (10 mmol) in ethanol (20-30 ml) [ready prepared or obtained by
dissolving compound 6' (10 mmol) in an alcohol solution (20-30 ml) of potassium hydroxide (0.056 g,
10 mmol)] we added the alkylating agent (10 mmol). The reaction mixture was left at 20°C for 20-24 h, and the
precipitate was filtered off.
Di[3-(5-chloro-2-pyridyl)-4-oxo-3H-5,6,7,8-tetrahydrobenzo[b]thieno[2,3-d]pyrimidin-2-ylthio]-
methane (10). To a solution of methylene chloride (0.85 g, 10 mmol) in ethanol (10 ml) we added dropwise
with stirring a solution of the potassium salt 6m (10 mmol) in aqueous ethanol (20 ml). The mixture was left at
20°C for 24 h and was then boiled for 1 h and cooled. The precipitate was filtered off. Yield 52%;
mp 295-296°C (from DMF). 1H NMR spectrum, δ, ppm (J, Hz): 1.68-1.82 [8H, m, 2 (CH2)4]; 2.65-2.83 [8H, m,
2 (CH2)4]; 4.90 (2H, s, CH2); 7.72 (2H, d, J = 8.7, HPy); 8.70 [2H, s, 6-H (5-Cl-Py)2]. Found %: N 12.0; S 18.46.
C31H24Cl2N6O2S4. Calculated %: N 11.81; S 18.00.
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