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: ジャーナルへの寄稿記事

23 引用 (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.

元の言語英語
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
発行部数12
出版物ステータス出版済み - 1981
外部発表Yes

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Rate constants
Kinetics
Acids
Electrons
4-aminophenol
phenylhydroxylamine

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

これを引用

Kinetics and mechanisms of the Bamberger rearrangement. Part 4. Rearrangement of sterically hindered phenylhydroxylamines to 4-aminophenols in aqueous sulphuric acid solution. / Sone, Takaaki; Hamamoto, Kazuhiro; Seiji, Yoshiyuki; Shinkai, Seiji; Manabe, Osamu.

:: Journal of the Chemical Society, Perkin Transactions 2, 番号 12, 1981, p. 1596-1598.

研究成果: ジャーナルへの寄稿記事

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abstract = "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.",
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T1 - Kinetics and mechanisms of the Bamberger rearrangement. Part 4. Rearrangement of sterically hindered phenylhydroxylamines to 4-aminophenols in aqueous sulphuric acid solution

AU - Sone, Takaaki

AU - Hamamoto, Kazuhiro

AU - Seiji, Yoshiyuki

AU - Shinkai, Seiji

AU - Manabe, Osamu

PY - 1981

Y1 - 1981

N2 - 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.

AB - 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.

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