Reactions of 1-cyano-1-methylethyl radicals produced by the decomposition of α, α'-azobisisobutyronitrile were investigated in oxalyl, acetyl and benzoyl chlorides. In oxalyl chloride, a compound of molecular formula C9H12OCl2N2 was isolated in 20% yield. The structure of the compound was established by degradation. In the case of acetyl chloride, N-isobutyryl-α-aminoisobutyroamide was obtained in 10% yield. The former is thought to have resulted from reaction of oxalyl chloride with the keteneimine, which is produced by combination of two 1-cyano-1-methylethyl radicals. The latter arises apparently from hydrolysis of the keteneimine during treatment. Benzoyl chloride did not undergo any reactions with 1-cyano-1-methylethyl radicals. The reaction mechanism is discussed.
Reactions of 1-cyano-1-methylethyl radicals produced by the decomposition of α, α'-azobisisobutyronitrile were investigated in benzenesulphonyl, ethanesulphonyl and phenylmethanesulphonyl chlorides. 1-Cyano-1-methylethyl radicals abstracted a chlorine atom from a molecule of benzensulphonyl chloride and α-cyanoisopropyl phenyl sulphone was obtained. No sulphur dioxide was detected. In ethanesulphonyl and phenylmethanesulphonyl chlorides, N-isobutyryl-α-aminoisobutyronitrile and the corresponding amide were isolated. These compounds arise apparently from hydrolysis of the keteneimine, during treatment, which is produced by combination of two 1-cyano-1-methylethyl radicals. Though phenylmethanesulphonyl chloride decomposes thermally by itself, the thermal decomposition was accelerated by addition of azobisnitrile. The reaction mechanism is discussed.
A series of addition-Compounds as an isocyanate generator was synthesized by reaction of tetramethylenediisocyanate or methylene di-(p-phenylene) diisocyanate with a active hydrogen compound. The active hydrogen compounds used here were phenol, m-cresol, diethyl malonate, ethyl acetoacetate, ethyl cganoacetate, α-pyrrolidone, ε-caprolactam, and sodium hydrogen sulfite. As a qualitative test for easiness of thermal dissociation, diamine test was made and the same result was obtained as that of Cellit test as reported. by Petersen.
Syntheses of vat dyes containing carbazole ring were made by condensation 2, 3-dichloro-and 5-nitro-2, 3-dichloro-1, 4-naphthoquinone with aromatic primary amine by dehydrochlorination, substitution of the ortho position of imino group with bromine, then dehalogenation and cyclization with the use of activated copper. The aromatic primary amines used for formation of carbazole ring were p-toluidine, β-naphthylamine, benzidine, o-dianisidine, and 1, 5-dimainoanthraquinone. Since the condensation of 1, 5-diaminoanthraquinone and dichloro naphthoquinone was difficult, 1, 4-additive reaction of the naphthoquinone was applied.