Novel triazenes and triazolines from the base-catalyzed hydrolysis of 1,3-dialkyl-3-acyltriazenes

Richard H. Smith, Brian D. Wladkowski, Julie A. Herling, Timothy D. Pfaltzgraff, Jesse Taylor, Erin J. Thompson, Brunon Pruski, John R. Klose, Christopher J. Michejda

Research output: Contribution to journalArticle

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Abstract

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 acid-catalyzed. 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.

Original languageEnglish (US)
Pages (from-to)6448-6454
Number of pages7
JournalJournal of Organic Chemistry
Volume57
Issue number24
StatePublished - 1992
Externally publishedYes

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Triazenes
Hydrolysis
Derivatives
Decomposition
Deuterium
Isotopes
Catalysis
Buffers
Acids

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Smith, R. H., Wladkowski, B. D., Herling, J. A., Pfaltzgraff, T. D., Taylor, J., Thompson, E. J., ... Michejda, C. J. (1992). Novel triazenes and triazolines from the base-catalyzed hydrolysis of 1,3-dialkyl-3-acyltriazenes. Journal of Organic Chemistry, 57(24), 6448-6454.

Novel triazenes and triazolines from the base-catalyzed hydrolysis of 1,3-dialkyl-3-acyltriazenes. / Smith, Richard H.; Wladkowski, Brian D.; Herling, Julie A.; Pfaltzgraff, Timothy D.; Taylor, Jesse; Thompson, Erin J.; Pruski, Brunon; Klose, John R.; Michejda, Christopher J.

In: Journal of Organic Chemistry, Vol. 57, No. 24, 1992, p. 6448-6454.

Research output: Contribution to journalArticle

Smith, RH, Wladkowski, BD, Herling, JA, Pfaltzgraff, TD, Taylor, J, Thompson, EJ, Pruski, B, Klose, JR & Michejda, CJ 1992, 'Novel triazenes and triazolines from the base-catalyzed hydrolysis of 1,3-dialkyl-3-acyltriazenes', Journal of Organic Chemistry, vol. 57, no. 24, pp. 6448-6454.
Smith RH, Wladkowski BD, Herling JA, Pfaltzgraff TD, Taylor J, Thompson EJ et al. Novel triazenes and triazolines from the base-catalyzed hydrolysis of 1,3-dialkyl-3-acyltriazenes. Journal of Organic Chemistry. 1992;57(24):6448-6454.
Smith, Richard H. ; Wladkowski, Brian D. ; Herling, Julie A. ; Pfaltzgraff, Timothy D. ; Taylor, Jesse ; Thompson, Erin J. ; Pruski, Brunon ; Klose, John R. ; Michejda, Christopher J. / Novel triazenes and triazolines from the base-catalyzed hydrolysis of 1,3-dialkyl-3-acyltriazenes. In: Journal of Organic Chemistry. 1992 ; Vol. 57, No. 24. pp. 6448-6454.
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AU - Klose, John R.

AU - Michejda, Christopher J.

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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 acid-catalyzed. 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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