Eliminations Forming Carbon-Heteroatom Multiple Bonds. Base-Promoted Dehydrochlorination of N-Chlorobenzylmethylamines

Richard A. Bartsch; Bong Rae Cho

doi:10.1021/ja00507a025

Eliminations Forming Carbon-Heteroatom Multiple Bonds. Base-Promoted Dehydrochlorination of N-Chlorobenzylmethylamines

Richard A. Bartsch, Bong Rae Cho

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

31 Citations (Scopus)

Abstract

Reactions of N-chlorobenzylmethylamines, 1, with MeONa-MeOH and t-BuOK-t-BuOH have been studied kinetically. The eliminations are quantitative and regiospecific, producing only benzylidenemethylamines. The reactions are first order in base and first order in chloramine and an E2 mechanism is evident. Reactions of I with MeONa-MeOH and t-BuOK-t-BuOH give Hammett p values of + 1.52 and +1.68, respectively. From eliminations of PhCD₂N(Cl)CH₃ and its un-deuterated analogue induced by MeONa-MeOH and t-BuOK-t-BuOH, kH/kD values of 5.1-6.5 were calculated. For eliminations from N-halobenzylmethylamines, k_Br/k_Cl = 11.9 and 10.8 were observed with MeONa-MeOH and t-BuOK-t-BuOH, respectively. Comparison of these results with those for eliminations from 2-halo-l-phenylpropanes provides insight into closely related imine- and alkene-forming eliminations.

Original language	English
Pages (from-to)	3587-3591
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	101
Issue number	13
DOIs	https://doi.org/10.1021/ja00507a025
Publication status	Published - 1979 Jun 1
Externally published	Yes

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Eliminations Forming Carbon-Heteroatom Multiple Bonds. Base-Promoted Dehydrochlorination of N-Chlorobenzylmethylamines",

abstract = "Reactions of N-chlorobenzylmethylamines, 1, with MeONa-MeOH and t-BuOK-t-BuOH have been studied kinetically. The eliminations are quantitative and regiospecific, producing only benzylidenemethylamines. The reactions are first order in base and first order in chloramine and an E2 mechanism is evident. Reactions of I with MeONa-MeOH and t-BuOK-t-BuOH give Hammett p values of + 1.52 and +1.68, respectively. From eliminations of PhCD2N(Cl)CH3 and its un-deuterated analogue induced by MeONa-MeOH and t-BuOK-t-BuOH, kH/kD values of 5.1-6.5 were calculated. For eliminations from N-halobenzylmethylamines, kBr/kCl = 11.9 and 10.8 were observed with MeONa-MeOH and t-BuOK-t-BuOH, respectively. Comparison of these results with those for eliminations from 2-halo-l-phenylpropanes provides insight into closely related imine- and alkene-forming eliminations.",

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AU - Bartsch, Richard A.

AU - Cho, Bong Rae

PY - 1979/6/1

Y1 - 1979/6/1

N2 - Reactions of N-chlorobenzylmethylamines, 1, with MeONa-MeOH and t-BuOK-t-BuOH have been studied kinetically. The eliminations are quantitative and regiospecific, producing only benzylidenemethylamines. The reactions are first order in base and first order in chloramine and an E2 mechanism is evident. Reactions of I with MeONa-MeOH and t-BuOK-t-BuOH give Hammett p values of + 1.52 and +1.68, respectively. From eliminations of PhCD2N(Cl)CH3 and its un-deuterated analogue induced by MeONa-MeOH and t-BuOK-t-BuOH, kH/kD values of 5.1-6.5 were calculated. For eliminations from N-halobenzylmethylamines, kBr/kCl = 11.9 and 10.8 were observed with MeONa-MeOH and t-BuOK-t-BuOH, respectively. Comparison of these results with those for eliminations from 2-halo-l-phenylpropanes provides insight into closely related imine- and alkene-forming eliminations.

AB - Reactions of N-chlorobenzylmethylamines, 1, with MeONa-MeOH and t-BuOK-t-BuOH have been studied kinetically. The eliminations are quantitative and regiospecific, producing only benzylidenemethylamines. The reactions are first order in base and first order in chloramine and an E2 mechanism is evident. Reactions of I with MeONa-MeOH and t-BuOK-t-BuOH give Hammett p values of + 1.52 and +1.68, respectively. From eliminations of PhCD2N(Cl)CH3 and its un-deuterated analogue induced by MeONa-MeOH and t-BuOK-t-BuOH, kH/kD values of 5.1-6.5 were calculated. For eliminations from N-halobenzylmethylamines, kBr/kCl = 11.9 and 10.8 were observed with MeONa-MeOH and t-BuOK-t-BuOH, respectively. Comparison of these results with those for eliminations from 2-halo-l-phenylpropanes provides insight into closely related imine- and alkene-forming eliminations.

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Eliminations Forming Carbon-Heteroatom Multiple Bonds. Base-Promoted Dehydrochlorination of N-Chlorobenzylmethylamines

Abstract

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