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

doi:10.1016/j.theochem.2006.11.035

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

Biomateriales y productos naturales: química y aplicaciones

Research output: Contribution to journal › Article › peer-review

Abstract

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.

Original language	English
Pages (from-to)	109-115
Number of pages	7
Journal	Journal of Molecular Structure: THEOCHEM
Volume	811
Issue number	1-3
DOIs	https://doi.org/10.1016/j.theochem.2006.11.035
State	Published - 1 Jun 2007

Keywords

Arylethyl N,N-dimethylcarbamates
Gas-phase elimination
MP2/6-31G and MPW1PW91/6-31G(d,p) calculations
Mechanism

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@article{743a5ea2368d4d69a90216ec521a4856,

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

abstract = "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.",

keywords = "Arylethyl N,N-dimethylcarbamates, Gas-phase elimination, MP2/6-31G and MPW1PW91/6-31G(d,p) calculations, Mechanism",

author = "{Castellar H}, {Rafael J.} and M. Loro{\~n}o and Tania C{\'o}rdova and Gabriel Chuchani",

year = "2007",

month = jun,

day = "1",

doi = "10.1016/j.theochem.2006.11.035",

language = "Ingl{\'e}s",

volume = "811",

pages = "109--115",

journal = "Computational and Theoretical Chemistry",

issn = "2210-271X",

publisher = "Elsevier BV",

number = "1-3",

}

Theoretical studies on the gas-phase elimination kinetics of 2-arylethyl N,N-dimethylcarbamates [(CH₃)₂NCOOCH₂CH₂Z, Z = 4-CH₃C₆H₄, 4-CH₃OC₆H₄, 4-NO₂C₆H₄]. / Castellar H, Rafael J.; Loroño, M.; Córdova, Tania; Chuchani, Gabriel.

In: Journal of Molecular Structure: THEOCHEM, Vol. 811, No. 1-3, 01.06.2007, p. 109-115.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Theoretical studies on the gas-phase elimination kinetics of 2-arylethyl N,N-dimethylcarbamates [(CH3)2NCOOCH2CH2Z, Z = 4-CH3C6H4, 4-CH3OC6H4, 4-NO2C6H4]

AU - Castellar H, Rafael J.

AU - Loroño, M.

AU - Córdova, Tania

AU - Chuchani, Gabriel

PY - 2007/6/1

Y1 - 2007/6/1

N2 - 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.

AB - 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.

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KW - MP2/6-31G and MPW1PW91/6-31G(d,p) calculations

KW - Mechanism

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U2 - 10.1016/j.theochem.2006.11.035

DO - 10.1016/j.theochem.2006.11.035

M3 - Artículo

AN - SCOPUS:34248144978

VL - 811

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EP - 115

JO - Computational and Theoretical Chemistry

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SN - 2210-271X

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