Theoretical studies on the gas-phase elimination kinetics of 2-arylethyl N,N-dimethylcarbamates [(CH3)2NCOOCH2CH2Z, Z = 4-CH3C6H4, 4-CH3OC6H4, 4-NO2C6H4]

Rafael J. Castellar H, M. Loroño, Tania Córdova, Gabriel Chuchani

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

Resumen

The gas-phase elimination kinetics of 2-arylethyl N,N-dimethylcarbamates, (CH3)2NCOOCH2CH2Ar, has been studied at the ab initio MP2/6-31G and MPW1PW91/6-31G(d,p) levels of theory. These carbamates produce N,N-dimethylcarbamic acid and the corresponding 4-substituted styrene in a rate determining step. The unstable intermediate N,N-dimethylcarbamic acid rapidly decarboxylate through a four-membered cyclic transition state to give dimethylamine . These calculations imply a concerted, non-synchronous six-membered cyclic transition state type of mechanism. The present results support the fact that the acidity of the benzylic hydrogen as an important factor for faster elimination rates.

Idioma originalInglés
Páginas (desde-hasta)109-115
Número de páginas7
PublicaciónJournal of Molecular Structure: THEOCHEM
Volumen811
N.º1-3
DOI
EstadoPublicada - 1 jun 2007

Huella

Profundice en los temas de investigación de 'Theoretical studies on the gas-phase elimination kinetics of 2-arylethyl N,N-dimethylcarbamates [(CH<sub>3</sub>)<sub>2</sub>NCOOCH<sub>2</sub>CH<sub>2</sub>Z, Z = 4-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>, 4-CH<sub>3</sub>OC<sub>6</sub>H<sub>4</sub>, 4-NO<sub>2</sub>C<sub>6</sub>H<sub>4</sub>]'. En conjunto forman una huella única.

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