チュガエフ反応則に反する転位とトランス・脱離反応(第5報) : 2-Dialkylaminoalkyl N, N-DimethylthionocarbamatesのN, N-Dimethylthiolcarbamatesへの熱転位

概要

論文の詳細を見る
Details are given on previously reported rearrangement of alkyl N, N-dimethylthionocarbamates holding a neighboring anchimeric group at β-position of alkyl group to the corresponding N, N-dimethylthiolcarbamates.^<2)> Several 2-dialkylaminoalkyl N, N-di-methylthionocarbamates were thermally treated. When the dimethylamino group and the thionocarbamate group of these compounds were in the antiparallel coplanarity, they underwent rearrangement to the corresponding N, N-dimethylthiolcarbamates, while the compounds with both groups situated in the cis relationship did not undergo this rearrangement. A pair of position isomers, DL-1-dimethylamino-2-propyl N, N-dimethylthionocarbamate (XVII) and DL-2-dimethyl-amino-1-propyl N, N-dimethylthionocarbamate (XVIII), gave the same rearrangement product, DL-2-dimethylamino-1-propyl N, N-dimethylthiolcarbamate (XX). These findings are correspond to those reported earlier on dialkylaminoalkyl S-methyl xanthates.^<4a, b)> This analogy between xanthates and thionocarbamates further supports the reaction mechanism^<4b)> postulated previously for this kind of rearrangement.
公益社団法人日本薬学会の論文
1969-11-25