Nucleophilic ion pairs. Part II. Micellar catalysis of proton abstraction by hydroxamate anions

Seiji Shinkai, Toyoki Kunitake

研究成果: Contribution to journalArticle査読

20 被引用数 (Scopus)

抄録

Hydroxamate anions in a cat ionic (cetyltrimethylammonium bromide. CTAB) micelle were found to serve as excellent catalysts for proton abstraction from oc-ketols. Proton removal from benzoin by N-methylmyristohydroxamateanion (MMHA) in the CTAB micelle was 3 500 times faster than the corresponding reaction in a non-micellar system, and 56 times faster than that by the much more basic hydroxide ion. A similar, dramatic rate enhancement was attainable by addition of small amounts of CTAB or methyltri-n-octylammonium chloride (TMAC) to MMHA solubilized in aqueous non-ionic micelles. On the other hand, the MMHA,NEt 4 ion pair in organic solvents was also effective for proton abstraction. MMHA,NEt4 in highly dehydrated acetonitrile gave a rate 103 higher than that in aqueous media. Minute amounts of H 2O and Nal efficiently quenched the reaction in dry organic solvents, and it was inhibited in protic solvents. It was suggested from these experimental data that the rate enhancement of MMHA in the presence of a cationic micelle largely stems from formation of a hydrophobic ion pair which is loose and desolvated in the micellar phase.

本文言語英語
ページ(範囲)980-985
ページ数6
ジャーナルJournal of the Chemical Society, Perkin Transactions 2
9
DOI
出版ステータス出版済み - 1976

All Science Journal Classification (ASJC) codes

  • 化学 (全般)

フィンガープリント

「Nucleophilic ion pairs. Part II. Micellar catalysis of proton abstraction by hydroxamate anions」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

引用スタイル