Phenylcarbonimidoyl dichloride

A useful route to 2,1,3-benzothiadiazoles is the F -catalyzed cyclization of l-(4-X-C6F4)-3-trimethylsilyl-l, 3-diaza-2-thiallenes [90JFC(50)359]. Fluoride ion catalysis is also used in the formation of heterocycles from pentafluorobenzoyl and -phenoxy compounds (81BCJ3447). Pentafluoro-phenylcarbonimidoyl dichloride with primary amines gave guanidines,... 

In the high temperature chlorination of N-methylaniline 126 a mixture of tetrachloro-phenylcarbonimidoyl dichloride 127 and perchlorodiphenylcarbodiimide 128 is obtained. ... 

A) Phenyl isocyanate (I) is chlorinated in chloroform, and the /i-chloro-phenylcarbonimidoyl dichloride (II) obtained is reacted with dimethylamine to give p-chlorophenylimino chlorocarbonic acid dimethylamide (III). This is treated with... 

In 1874 Sell and Zierold obtained phenylcarbonimidoyl dichloride I in the reaction of phenylisothiocyanate II with chlorine. Several years later, Nef ( 8,109 prepared carbonimidoyl dichlorides by addition of chlorine to isocyanides, such as phenyl isocyanide III. This relationship between I and isocyanides (isonitriles) led to the frequently used term isocyanide dichlorides for the compounds under discussion. 

Phenylcarbonimidoyl dichloride To a solution of 67.5 g (0.5 mole) of phenyl isothiocyanate in 200 ml of carbon tetrachloride chlorine is added with stirring and ice-cooling below 3°C until the chlorine is no longer absorbed (approximately three to four hours). The solvent and sulfur dichloride, formed in the reaction, are removed by distillation, and vacuum distillation of the residue yields 74-78 g (85-90%) of phenylcarbonimidoyl dichloride, b.p. 103-106°C (31 mm). 

The reaction of carbonimidoyl dichlorides with excess water results in complete hydrolysis with formation of the corresponding amine and carbon dioxide ( ). This reaction affords isocyanate as an intermediate, as evidenced by the isolation of 1,3-diphenylurea from the reaction mixture, obtained by treating phenylcarbonimidoyl dichloride with water In the reaction of tetrameric cyanogen chloride with water at 20°C 2-amino-4,6-dichloro-l,3,5-triazine (LXXXVI) is obtained, whereas at 100 C total hydrolysis to cyanuric acid (LXXXVII) occurs... 

The reaction of phenylcarbonimidoyl dichloride with acetic acid was investigated by Sell and Zierold and by Nef who obtained acetanilide from the reaction mixture. Dyson and Harrington isolated substantial amounts of 1,3-diphenylurea and thus concluded that phenyl isocyanate... 

However, from benzaldoxime and phenylcarbonimidoyl dichlorides a mixture of phenyl isocyanate, benzonitrile, and aniline hydrochloride is obtained. 

The reaction of phenylcarbonimidoyl dichloride with sodium azide yields 5-chlorophenyltetrazole (CXVII) and the corresponding azide (CXVIII), depending upon the stoichiometry ( 2.i26 ... 

Phenylcarbonimidoyl dichloride readily adds chlorine to the phenyl ring to produce 1,2,3,4,5,6-hexachlorocyclohexylcarbonimidoyl dichloride (CXXIX) in high yield... 

---