Amination of Phenylketene Revisit. Substituent Effect on Reactivity
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<jats:title>Abstract</jats:title> <jats:p>The asymmetric stretching frequencies of the ketene group of the m,p-substituted phenylketenes were found to be correlated with σ. The substituent effects for the second-order rate constants of phenylketenes with various amines were not correlated linearly with any single substituent constants. The curved σ°-correlations with a plateau at a high reactivity region were observed for meta-substituents and p-chloro. The substituent effects including para-π-acceptors were described in terms of the Yukawa–Tsuno equation modified by a quadratic term as an approximation. The resultant ρ value decreases significantly from 2.92 for 2,2,2-trifluoroethylamine to 0.83 for benzylamine while an r− value increases from 0.50 to 1.10. The opposite change of ρ and r− with amines was interpreted by the dual electronic interactions between substituents and positive/negative charges at the zwitterionic transition structure. According to this interpretation, benzylamine with small ρ value and large r− value attributes to early transition state and larger ρ value with smaller r− value for 2,2,2-trifluoroethylamine attributes to late transition state.</jats:p>
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- Bulletin of the Chemical Society of Japan
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Bulletin of the Chemical Society of Japan 86 (7), 856-863, 2013-07
Tokyo : Chemical Society of Japan
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詳細情報 詳細情報について
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- CRID
- 1522543655428503552
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- NII論文ID
- 10031183250
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- NII書誌ID
- AA00580132
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- ISSN
- 00092673
- 13480634
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- NDL書誌ID
- 024672039
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- 本文言語コード
- en
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- NDL 雑誌分類
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- ZP1(科学技術--化学・化学工業)
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- データソース種別
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- NDL
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