Nucleophilic Ion Pairs. 5. Facile Cleavage of Amide Substrates by a Hydroxamate Anion in Aprotic Solvents. Efficient Inhibition by Minute Amounts of Water

Seiji Shinkai, Naotoshi Nakashima, Toyoki Kunitake

研究成果: Contribution to journalArticle査読

5 被引用数 (Scopus)

抄録

A quaternary ammonium salt of the hydroxamate anion was found to cleave several N-methylanilide substrates very readily at room temperature in dry, aprotic media. In contrast, the reaction was very slow in protic media and, for example, a rate difference of >105 was observed between dimethylformamide and formamide media for the reaction of N-methyl-p-nitroacetanilide and tetraethylammonium N-methylmyristohydroxamate. The reaction was efficiently suppressed by minute amounts of water and a kinetic isitope effect (KH2O/KD2O) of 1.3-1.5 was observed for some substrates. These results indicate that both the nucleophilic attack and the proton transfer to the tetrahedral intermediate were facilitated in dry, aprotic media. The reaction of the hydroxamate and p-nitrophenyl acetate was facilitated in dry, aprotic media and in aqueous cationic micelles. Thus, the complete suppression of the amide cleavage in the cationic micelle was attributed to the inefficient proton transfer to the tetrahedral intermedate.

本文言語英語
ページ(範囲)5887-5892
ページ数6
ジャーナルJournal of the American Chemical Society
100
18
DOI
出版ステータス出版済み - 1978

All Science Journal Classification (ASJC) codes

  • 触媒
  • 化学 (全般)
  • 生化学
  • コロイド化学および表面化学

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