Pyrolysis kinetics of ethyl fluoroacetate in the gas phase

The molecular gas-phase elimination kinetics of the series CI (CH,).COOH (n = 1-4), show changes in mechanisms from polar five-centered intramolecular displacement of the CI leaving group by the acidic hydrogen of the COOH to neighboring group participation of the oxygen carbonyl of the COOH group. The mechanisms for the series 2-, 3-and 4-chlorobutyric acids are explained similarly as above. The leaving chloride at the 2-position of acetic, propionic, and butyric acids is displaced by the hydrogen of the COOH group through a prevaling path of a five-centered cyclic transition-state mechanism. This type of mechanism is also described for the pyrolysis of 2-hydroxy-, 2-alkoxy-, 2-phenoxy-, and 2-acetoxycarboxylic acids. The ease with which the groups at the 2-position of acetic and propionic acids are displaced by the H of COOH give rise theThese two sequences differ only in the OH leaving group position. Additional work on glycolic acid pyrolysis is needed to explain the above differences.

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Homogeneous, unimolecular, gas-phase elimination of leaving groups at the alkoyl side of carboxylic acids

Chuchani

Rotinov

Domínguez

et al. 1996

J. Phys. Org. Chem.

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Linear correlation of polar substituents in the gas‐phase pyrolyses of ethyl α‐substituted acetates

Rotinov

Chuchani

1984

Int J of Chemical Kinetics

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Several mechanisms in the elimination kinetics of ω‐chlorocarboxylic acids in the gas phase

Chuchani

Martín

Rotinov

et al. 1995

J of Physical Organic Chem

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The kinetics of the gas‐phase pyrolysis of ω‐chlorocarboxylic acids were examined in a seasoned static reaction vessel and in the presence of at least twice the amount of the free radical inhibitor cyclohexene or toluene. In conformity with the available experimental data on rate determination, these reactions proved to be unimolecular and obeyed a first‐order rate law. The presence of the primary chlorine leaving group in Cl(CH2)nCOOH (n = 1–4) showed a change in mechanism from intramolecular displacement of the Cl leaving group by the acidic hydrogen of the COOH to anchimeric assistance of the carbonyl COOH to the CCl bond polarization in the transition state. This mechanistic consideration is nearly the same for the series of 2‐, 3‐, and 4‐chlorobutyric acids. The chlorine atom at the 2‐position of acetic, propionic and butyric acids is dehydrochlorinated through a prevailing reaction path involving a polar five‐membered cyclic transition state.

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Pyrolysis kinetics of ethyl fluoroacetate in the gas phase

Cited by 4 publications

References 9 publications

Homogeneous, unimolecular, gas-phase elimination of leaving groups at the alkoyl side of carboxylic acids

Homogeneous, unimolecular, gas-phase elimination of leaving groups at the alkoyl side of carboxylic acids

Linear correlation of polar substituents in the gas‐phase pyrolyses of ethyl α‐substituted acetates

Several mechanisms in the elimination kinetics of ω‐chlorocarboxylic acids in the gas phase

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