Kinetics and mechanisms of the Bamberger rearrangement. Part 4. Rearrangement of sterically hindered phenylhydroxylamines to 4-aminophenols in aqueous sulphuric acid solution

Takaaki Sone, Kazuhiro Hamamoto, Yoshiyuki Seiji, Seiji Shinkai, Osamu Manabe

研究成果: Contribution to journalArticle査読

21 被引用数 (Scopus)

抄録

The rates of the Bamberger rearrangement of sterically hindered phenylhydroxylamines have been determined in aqueous sulphuric acid solution and the substituent effects (in particular, the steric effects) are discussed. The rate constants for phenylhydroxylamines with 2-substituents (Me, Cl, I) satisfied the Taft equation: log krel = ρ*σ* - δEs with ρ* - 1.93 and δ - 1.16. The result shows that steric hindrance of the substituents, in addition to the electron-donating effect, has an accelerating effect on the rates of the Bamberger rearrangement. The rate constants for 3-substituted 2-methylphenylhydroxylamines were generally greater than those for 5-substituted 2-methylphenylhydroxylamines. The difference was attributed to the ' buttressing effect ' of neighbouring 3-substituents. This is the first example of steric acceleration of the Bamberger rearrangement.

本文言語英語
ページ(範囲)1596-1598
ページ数3
ジャーナルJournal of the Chemical Society, Perkin Transactions 2
12
DOI
出版ステータス出版済み - 1981
外部発表はい

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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