Trichlorovinylamines, chlorination

Chlorination of enamincs has also been reported (42,118). Thus the trichlorovinylamine (170) has been chlorinated to 171, which was not isolated but treated with hydrogen sulfide to give the thioamide (172) (118). 

The method of Ficini [156], involving treatment of the readily available trichloiovinylamines [157] with three equivalents of alkyllithium, gives access to yneamines with a terminal triple bond. At low temperatures the trichlorovinylamine is dechlorinated with one equivalent of alkyllithium. The subsequent displacement of chlorine by lithium in the intermediary CIOCNR2 takes place when the reaction mixture is heated under reflux. Since part of the... 

N,N-Diethyl-l,2,2-trichlorovinylamine undergoes certain reactions which involve the 1-chlorine atom. Acids and alcohols are converted to their respective chlorides. Aniline converts the vinylamine to N,N-diethyl-N -phenyl-2,2-dichloroacetamidine.3... 

Chlorination /-Butylhypochlorite. Catechyl phosphorus trichloride. N-Chlorosuccinimide. Cupric chloride. N,N-Diethyl-l,2,2-trichlorovinylamine. Iodobenzene dichloride. Mesyl chloride. Sulfuryl chloride. 

Speziale and Smith reacted iminium chlorides, obtained from enamines and hydrogen chloride, with hydrogen sulfide, and the corresponding thioamides were obtained in good yield. Likewise, addition of chlorine to trichlorovinylamines yields the trichloroiminium chlorides C, which are readily converted to the corresponding thioamide (Cl) by means of H2S... 

N,N-Diethyl-l,2,2-trichlorovinylamine is an effective reagent for the replacement of hydroxyl by chlorine. The yields are good in the cases of carboxylic acids, and prim., sec., and tert. alcohols. Inversion of configuration takes place with optically active compounds giving products of high optical purity. The reaction with amines yields amidines. F. e., also carboxylic acid chlorides, s. A. J. Speziale and R. C. Freeman, Am. Soc. 82, 909 (I960). 

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