Elimination reactions of N-alkyl-N-chlorothenylamines promoted by MeONa-MeOH and Et2NH-MeCN. Effect of the β-aryl group on the imine-forming transition state

Sang Yong Pyun, Dong Choon Lee, Yoon Je Seung, Bong-Rae Cho

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Abstract

Elimination reactions of N-alkyl-N-chlorothenylamines 1-4 with MeONa-MeOH and Et2NH-MeCN have been studied kinetically. The elimination reactions are regiospecific, producing only the conjugated imines. The reactions are second order and exhibit substantial values of Hammett ρ and k H/kD, and an E2 mechanism is evident. The relative rates of elimination for Me/Et/i-Pr/i-Bu substituents are 1/0.5/0.2/0.02 with MeONa-MeOH and 1/0.4/0.2/0.06 with Et2NH-MeCN. The transition state structure changes toward more product-like as the base is changed from MeONa-MeOH to Et2NH-MeCN. Comparison with existing data reveals that the structure of the transition state is relatively insensitive to the β-aryl group variation.

Original languageEnglish
Pages (from-to)5327-5330
Number of pages4
JournalJournal of Organic Chemistry
Volume70
Issue number13
DOIs
Publication statusPublished - 2005 Jun 24

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Elimination reactions of N-alkyl-N-chlorothenylamines promoted by MeONa-MeOH and Et2NH-MeCN. Effect of the β-aryl group on the imine-forming transition state. / Pyun, Sang Yong; Lee, Dong Choon; Seung, Yoon Je; Cho, Bong-Rae.

In: Journal of Organic Chemistry, Vol. 70, No. 13, 24.06.2005, p. 5327-5330.

Research output: Contribution to journalArticle

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abstract = "Elimination reactions of N-alkyl-N-chlorothenylamines 1-4 with MeONa-MeOH and Et2NH-MeCN have been studied kinetically. The elimination reactions are regiospecific, producing only the conjugated imines. The reactions are second order and exhibit substantial values of Hammett ρ and k H/kD, and an E2 mechanism is evident. The relative rates of elimination for Me/Et/i-Pr/i-Bu substituents are 1/0.5/0.2/0.02 with MeONa-MeOH and 1/0.4/0.2/0.06 with Et2NH-MeCN. The transition state structure changes toward more product-like as the base is changed from MeONa-MeOH to Et2NH-MeCN. Comparison with existing data reveals that the structure of the transition state is relatively insensitive to the β-aryl group variation.",
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AB - Elimination reactions of N-alkyl-N-chlorothenylamines 1-4 with MeONa-MeOH and Et2NH-MeCN have been studied kinetically. The elimination reactions are regiospecific, producing only the conjugated imines. The reactions are second order and exhibit substantial values of Hammett ρ and k H/kD, and an E2 mechanism is evident. The relative rates of elimination for Me/Et/i-Pr/i-Bu substituents are 1/0.5/0.2/0.02 with MeONa-MeOH and 1/0.4/0.2/0.06 with Et2NH-MeCN. The transition state structure changes toward more product-like as the base is changed from MeONa-MeOH to Et2NH-MeCN. Comparison with existing data reveals that the structure of the transition state is relatively insensitive to the β-aryl group variation.

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