108369-78-4Relevant articles and documents
Carbon-Skeletal Anionic Rearrangements of Tertiary Benzylic Amines: Geometric and Electronic Requirements for Generating the Spiroazacyclopropane Intermediate
Eisch, John J.,Dua, Suresh K.,Kovacs, Csaba A.
, p. 4437 - 4444 (2007/10/02)
In order to determine the scope and mechanism for the base-promoted rearrangement of tertiary amines, a wide variety of benzylic amines were treated with n-BuLi in THF or TMEDA, n-BuLi-KO-t-Bu mixtures, or KH.The following amines were examined: benzyldimethylamine, benzylmethylphenylamine, benzyldiphenylamine, N-benzylcarbazole, N-benzyl-1,2,3,4-tetrahydrocarbazole, N-benzyl-1,1a,2,3,4,4a-cis-hexahydrocarbazole, N-(2-phenylethyl)carbazole, N-(3-phenylpropyl)carbazole, N-(2-chloroethyl)carbazole, N-benzyl-9,9-dimethyl-9,10-dihydroacridine, N-benzyl-o,o'-iminodibenzyl, 9-(diphenylamino)fluorene, 9-anilino-9-phenylfluorene, 9-(methylphenylamino)fluorene, and diphenyl(diphenylmethyl)amine.In certain cases, ethylation products were obtained from the interaction of intermediate carbanions with ethylene generated by the decomposition of THF.The results are interpreted in terms of intramolecular shifts of aryl groups from nitrogen to benzylic carbon proceeding by way of a bridging aryl transition state or intermediate.
