In the conversion of N-substituted benzenesulfonyl-N'-alkylthioureas into the corresponding chloroformamidines upon treatment with chlorine, di-(N-substituted benzenesulfonyl-N'-alkylformamidino) -disulfides were formed as intermediates. Thus, the reaction conditions have been established so as to obtain the disulfides almost quantitatively. Some of the reactions of the disulfides were also studied, as follows : (1) Upon treatment with water, an equimolar mixture of the original thiourea, the corresponding urea, and sulfur was obtained. (2) Upon treatment with methanol, an equimolar mixture of the thiourea, the corresponding O-methylisourea, and sulfur was obtained. (3) Upon treatment with an alkylamine, an equimolar mixture of the thiourea, the corresponding guanidine, and sulfur was obtained. (4) Upon chlorination, the corresponding chloroformamidine was formed almost quantitatively. (5) Upon reduction, the original thiourea was formed almost quantitatively. Some N-substituted benzenesulfonyl-N'-alkylureas, antihypertentive agents, were synthesized in a good yield directly from the intermediate disulfides.
p-Vinyl-(β-N, N-dimethylamino)-propiophenone (3), p-vinyl-(β-piperidino)-propiophenone (5), β-(p-vinylbenzoyl)-propionitrile (4), and 1-phenyl-3-(p-vinylphenyl)-pyrazoline (7) were synthesized. (3) and (5) are new styrene derivatives containing Mannich base structure in para positions. (3) was polymerized in benzene to obtain a polymer with intrinsic viscosity of 0.18 dl. g-1 (benzene, 30°C). A small amount of (7) was bulk copolymerized with styrene to obtain a fluorescent polystyrene. Copolymerization of (3) with divinylbenzene and aminomethylation of p-vinylacetophenone-divinylbenzene copolymer gave anion-exchange resins with capacities of 3.71 meq/g and 3.64 meq/g, respectively.
It was found that 3-nitrophthalic acid (1) was reduced to 3-aminophthalic acid (2) in the presence of 5% palladium-charcoal in glacial acetic acid under the atmospheric pressure at room temperature. 3-Acetylaminophthalic anhydrde (3) was synthesized in 90% yield (based on 1) by heating (2) in a mixture of acetic anhydride and glacial acetic acid. (3) was hydrolyzed to 3-acetylaminophthalic acid, mp 210211°C (dec.), in hot water.