Upon treatment with alkali, N-substituted benzenesulfonyl-N'-alkyl-chloroform-amidines were found to give the corresponding carbodiimides in the presence of hydrophobic solvents, such as chloroform and benzene, etc., in a theoretical yield. When N-substituted benzenesulfonyl-N'-alkyl-chloroformamidine was heated above its melting point, hydrogen chloride was liberated and the corresponding carbodii-mide was produced.The above mentioned carbodiimides were again converted back to the original chloroformamidines when treated with hydrogen chloride.N-substituted benzenesulfonyl-N'-alkyl-urea, used as an antihypertentive agent, O-methylisourea, and guanidines were prepared in good yields from the carbodii- mides as obtained above.
When N-substituted benzenesulfonyl-N'-alkyl thiourea is treated with water in the presence of selenium dioxide, the corresponding urea and red selenium are formed in a theoretical yield. Furthermore, upon treatment with methanol, amines, or butylmercaptan the thiourea gave the corresponding O-methylisourea, uanidines, or S-butylisothiourea in a good yield in one-step process.Since selenium dioxide is soluble in water as well as most of the organic solve-nts, the above mentioned reaction proceeds with ease at room temperature.The reaction between selenium dioxide and thiourea has not been reported in the literature to date. It is assumed that the reaction takes place through an inte-rmediate carbodiimide with subsequent attack by the nucleophillic reagent. A small IR absorption peak attributable to carbodiimide was noted at 2150 cm-1 in a chlor-oform solution of thiourea and selenium dioxide to support this assumption. Attempts to isolate the carbodiimide from such mixtures, however, failed.
An ordinary photochlorination of 1, 1-dichloroethane gave 1, 1, 1-trichloroethane and 1, 1, 2-trichloroethane in a yield of 75% and 22%, respectively.In the present study, it was found that the selectivity for 1, 1, 1-trichloroethane was markedly improved when carbon disulfide was bresent. Such effects of carbon disulfide varied depending on its concentration and the reaction temperatures. When 1, 1-dichloroethane was photochlorinated in the presence of 8 mol/1 carbon disulfide, 1, 1, 1-trichloroethane was obtained with a selectivity of 85-90% over a temperature range from 18°C to 45°C. The rate of the reaction decreased in the presence of carbon disulfide.
Copolyamides containing 2-methylpiperazine were obtained through condensation polymerization of either 2-methylpiperazinium terephthalate or adipate withcaprol-actam or hexamethylene diammonium adipate. The usual V-shape relationships-were observed between the melting points of the copolyamides and their composi-tions. The melt-spun fibers, prepared by using Koka Flow Tester, showed higher moisture regain than Nylon 6 and 66.