TY - JOUR
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
Y1 - 1987
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, kH/kD 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 Cß-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, kH/kD 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 Cß-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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U2 - 10.1039/p29870000853
DO - 10.1039/p29870000853
M3 - Article
AN - SCOPUS:37049086338
SN - 1472-779X
SP - 853
EP - 856
JO - Journal of the Chemical Society. Perkin Transactions 2
JF - Journal of the Chemical Society. Perkin Transactions 2
IS - 7
ER -