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 |
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Pages (from-to) | 109-115 |
Number of pages | 7 |
Journal | Journal of Molecular Structure: THEOCHEM |
Volume | 811 |
Issue number | 1-3 |
DOIs | |
State | Published - 1 Jun 2007 |
Externally published | Yes |
Bibliographical note
Copyright:Copyright 2007 Elsevier B.V., All rights reserved.
Keywords
- Arylethyl N,N-dimethylcarbamates
- Gas-phase elimination
- Mechanism
- MP2/6-31G and MPW1PW91/6-31G(d,p) calculations