Eliminations forming carbon-heteroatom multiple bonds. Base-promoted dehydrochlorination of N-chlorobenzylmethylamines

Richard A. Bartsch, Bong-Rae Cho

Research output: Contribution to journalArticle

30 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 1 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 undeuterated 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-1-phenylpropanes provides insight into closely related imine- and alkene-forming eliminations.

Original languageEnglish
Pages (from-to)3587-3591
Number of pages5
JournalJournal of the American Chemical Society
Volume101
Issue number13
Publication statusPublished - 1979 Dec 1
Externally publishedYes

Fingerprint

Imines
Alkenes
Olefins
Carbon
chloramine

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Eliminations forming carbon-heteroatom multiple bonds. Base-promoted dehydrochlorination of N-chlorobenzylmethylamines. / Bartsch, Richard A.; Cho, Bong-Rae.

In: Journal of the American Chemical Society, Vol. 101, No. 13, 01.12.1979, p. 3587-3591.

Research output: Contribution to journalArticle

@article{bb2b420c309547a5a6f5f8537c49923d,
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 1 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 undeuterated 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-1-phenylpropanes provides insight into closely related imine- and alkene-forming eliminations.",
author = "Bartsch, {Richard A.} and Bong-Rae Cho",
year = "1979",
month = "12",
day = "1",
language = "English",
volume = "101",
pages = "3587--3591",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "13",

}

TY - JOUR

T1 - Eliminations forming carbon-heteroatom multiple bonds. Base-promoted dehydrochlorination of N-chlorobenzylmethylamines

AU - Bartsch, Richard A.

AU - Cho, Bong-Rae

PY - 1979/12/1

Y1 - 1979/12/1

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 1 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 undeuterated 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-1-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 1 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 undeuterated 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-1-phenylpropanes provides insight into closely related imine- and alkene-forming eliminations.

UR - http://www.scopus.com/inward/record.url?scp=0000966618&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000966618&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000966618

VL - 101

SP - 3587

EP - 3591

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 13

ER -