TY - JOUR
T1 - Novel Triazenes and Triazolines from the Base-Catalyzed Hydrolysis of 1,3-Dialky1-3-acyltriazenes
AU - Smith, Richard H.
AU - Wladkowski, Brian D.
AU - Herling, Julie A.
AU - Pfaltzgraff, Timothy D.
AU - Taylor, Jesse E.
AU - Thompson, Erin J.
AU - Pruski, Brunon
AU - Klose, John R.
AU - Michejda, Christopher J.
PY - 1992/11/1
Y1 - 1992/11/1
N2 - The products and mechanism of hydrolytic decomposition of a series of 1,3-dialkyl-3-acyltriazenes were studied in alkaline buffers. In general the mechanism of decomposition involves deacylation leading to the formation of the parent 1,3-dialkyltriazene. The solvent deuterium isotope effect (kH2O/kD2O) is less than 1.0, indicating specific base catalysis. A plausible mechanistic explanation is rapid reversible attack by hydroxide ion, followed by rate-limiting heterolysis of the N(1)-acyl bond. The resultant, 1,3-dialkyltriazene is somewhat unstable under the reaction conditions and undergoes subsequent hydrolysis, a reaction previously shown to be specific acidcatalyzed. When the N(1) alkyl group is 2-chloroethyl, unusual products are obtained. For the 3-acetyl and 3-carbethoxy derivatives, the initial deacylation product, 1-(2-chloroethyl)-3-methyltriazene, efficiently cyclizes to form 1-methyltriazoline. The 3-(methylcarbamoyl) derivative does not deacylate, but instead undergoes dehydrohalogenation to 1-vinyl-3-methyl-3-(methylcarbamoyl)triazene.
AB - The products and mechanism of hydrolytic decomposition of a series of 1,3-dialkyl-3-acyltriazenes were studied in alkaline buffers. In general the mechanism of decomposition involves deacylation leading to the formation of the parent 1,3-dialkyltriazene. The solvent deuterium isotope effect (kH2O/kD2O) is less than 1.0, indicating specific base catalysis. A plausible mechanistic explanation is rapid reversible attack by hydroxide ion, followed by rate-limiting heterolysis of the N(1)-acyl bond. The resultant, 1,3-dialkyltriazene is somewhat unstable under the reaction conditions and undergoes subsequent hydrolysis, a reaction previously shown to be specific acidcatalyzed. When the N(1) alkyl group is 2-chloroethyl, unusual products are obtained. For the 3-acetyl and 3-carbethoxy derivatives, the initial deacylation product, 1-(2-chloroethyl)-3-methyltriazene, efficiently cyclizes to form 1-methyltriazoline. The 3-(methylcarbamoyl) derivative does not deacylate, but instead undergoes dehydrohalogenation to 1-vinyl-3-methyl-3-(methylcarbamoyl)triazene.
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U2 - 10.1021/jo00050a016
DO - 10.1021/jo00050a016
M3 - Article
AN - SCOPUS:2142783652
SN - 0022-3263
VL - 57
SP - 6448
EP - 6454
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 24
ER -