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

doi:10.1021/jo050368k

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

* Honorary professors

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

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/k_D, 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 language	English
Pages (from-to)	5327-5330
Number of pages	4
Journal	Journal of Organic Chemistry
Volume	70
Issue number	13
DOIs	https://doi.org/10.1021/jo050368k
Publication status	Published - 2005 Jun 24

ASJC Scopus subject areas

Organic Chemistry

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title = "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",

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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year = "2005",

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T1 - 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

AU - Pyun, Sang Yong

AU - Lee, Dong Choon

AU - Seung, Yoon Je

AU - Cho, Bong Rae

PY - 2005/6/24

Y1 - 2005/6/24

N2 - 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.

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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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

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