Reactions of N-halogenobenzylmethylamines with triethylamine in acetonitrile. Effect of leaving group upon the imine-forming transition state

Bong-Rae Cho, Sung Keon Namgoong, Tae Rin Kim

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Abstract

Reactions of N-halogenobenzylmethylamines (1) and (2) with Et 3N-MeCN have been investigated kinetically. Eliminations from (1) and (2) were quantitative and regiospecific, producing only benzylidenemethylamines. For the elimination reaction of (1) with Et 3N, k H/k D 5.7, ρ 0.88, ΔH‡ 9.1 kcal mol -1, and ΔS‡ -42.4 cal mol -1 K -1 were determined. The transition-state structure is assessed as being highly symmetric with similar extents of C ß-H and N α-Cl bond cleavage, little carbanionic character, and significant π-bond formation. The structure of the transition state changes only slightly with the change in the leaving group from Cl to Br.

Original languageEnglish
Pages (from-to)853-856
Number of pages4
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number7
Publication statusPublished - 1987 Dec 1

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Imines
triethylamine
acetonitrile

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Reactions of N-halogenobenzylmethylamines with triethylamine in acetonitrile. Effect of leaving group upon the imine-forming transition state",
abstract = "Reactions of N-halogenobenzylmethylamines (1) and (2) with Et 3N-MeCN have been investigated kinetically. Eliminations from (1) and (2) were quantitative and regiospecific, producing only benzylidenemethylamines. For the elimination reaction of (1) with Et 3N, k H/k D 5.7, ρ 0.88, ΔH‡ 9.1 kcal mol -1, and ΔS‡ -42.4 cal mol -1 K -1 were determined. The transition-state structure is assessed as being highly symmetric with similar extents of C {\ss}-H and N α-Cl bond cleavage, little carbanionic character, and significant π-bond formation. The structure of the transition state changes only slightly with the change in the leaving group from Cl to Br.",
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T1 - Reactions of N-halogenobenzylmethylamines with triethylamine in acetonitrile. Effect of leaving group upon the imine-forming transition state

AU - Cho, Bong-Rae

AU - Namgoong, Sung Keon

AU - Kim, Tae Rin

PY - 1987/12/1

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N2 - Reactions of N-halogenobenzylmethylamines (1) and (2) with Et 3N-MeCN have been investigated kinetically. Eliminations from (1) and (2) were quantitative and regiospecific, producing only benzylidenemethylamines. For the elimination reaction of (1) with Et 3N, k H/k D 5.7, ρ 0.88, ΔH‡ 9.1 kcal mol -1, and ΔS‡ -42.4 cal mol -1 K -1 were determined. The transition-state structure is assessed as being highly symmetric with similar extents of C ß-H and N α-Cl bond cleavage, little carbanionic character, and significant π-bond formation. The structure of the transition state changes only slightly with the change in the leaving group from Cl to Br.

AB - Reactions of N-halogenobenzylmethylamines (1) and (2) with Et 3N-MeCN have been investigated kinetically. Eliminations from (1) and (2) were quantitative and regiospecific, producing only benzylidenemethylamines. For the elimination reaction of (1) with Et 3N, k H/k D 5.7, ρ 0.88, ΔH‡ 9.1 kcal mol -1, and ΔS‡ -42.4 cal mol -1 K -1 were determined. The transition-state structure is assessed as being highly symmetric with similar extents of C ß-H and N α-Cl bond cleavage, little carbanionic character, and significant π-bond formation. The structure of the transition state changes only slightly with the change in the leaving group from Cl to Br.

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