Benzyne with tertiary amines

Products derived from intermediate zwitter-ions have been obtained in the reactions of benzynes with tertiary amines 1>. Benzyne generated by the reaction of -butyl-lithium with fluorobenzene interacts with AT.Af-dimethylaniline to yield iV-methyl diphenylamine and AT-ethyl diphenylamine 132,133). Using the reaction of chlorobenzene with n-butyl-lithium to generate benzyne resulted in the formation of increased amounts of 2-A7,AT-dimethylaminobiphenyl 132,133)... 

Reaction of benzyne with tertiary aliphatic amines to give anilines via Sommelet-Hauser and/or Stevens-type rearrangements of the intermediate ylid has been documented.362 363... 

Use has been made of the C-N cleavage in the conversion of the bicyclic tertiary amines, derived from the 4tc + 2tc cycloaddition of pyrroles and isoindoles with benzynes, into aromatic systems, e.g. naphthalen-l,4-imines and anthracen-9,10-imines yield naphthalenes and anthracenes with the extrusion of the nitrogen bridge [24] in yields which are higher than those obtained by standard oxidation procedures. 

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