Gas‐phase elimination kinetics of 1‐substituted ethyl acetates. Effect of polar substituents at the α carbon of secondary acetates

The kinetics of the gas‐phase elimination of two 2‐haloethyl methanesulphonates were determined in a static system over the temperature range 310–380°C and pressure range 26–174 Torr. The reactions in seasoned vessels, with the free‐radical inhibitor propene and/or toluene always present, are homogeneous and unimolecular, and follow a first‐order rate law. The rate coefficients are given by the Arrhenius equations: for 2‐bromoethyl methanesulphonate log k1 (s−1) = (11·70 ± 0·43)–(172·8 ± 4·8) kJ mol−1 (2·303RT)−1 and for 2‐chloroethyl methanesulphonate log k1 (s−1) = (11·67 ± 0·50)–(173·9 ± 6·0) kJ mol−1 (2·303RT)−1. The bromo compound was found to be more reactive than the chloro compound. At 340°C, for Br k1 = 9·46 × 10−4 s−1 and for Cl k1 = 7·12 × 10−4 s−1. Apparently, electronic factors seem to be operating in these elimination reactions.

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Structural effects on gas-phase reactivities

Chuchani¹,

Mishima²,

Notario³

et al. 1999

Advances in Quantative Structure - Property Relationships Volume 2

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Gas‐phase elimination kinetics of 1‐substituted ethyl acetates. Effect of polar substituents at the α carbon of secondary acetates

Cited by 3 publications

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ChemInform Abstract: GAS‐PHASE ELIMINATION KINETICS OF 1‐SUBSTITUTED ETHYL ACETATES. EFFECT OF POLAR SUBSTITUENTS AT THE α CARBON OF SECONDARY ACETATES

ChemInform Abstract: GAS‐PHASE ELIMINATION KINETICS OF 1‐SUBSTITUTED ETHYL ACETATES. EFFECT OF POLAR SUBSTITUENTS AT THE α CARBON OF SECONDARY ACETATES

Electronic factors in the elimination kinetics of 2‐halosubstituted methanesulphonates in the gas phase

Structural effects on gas-phase reactivities

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