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Competition between decarboxylation and isomerization in the C 3 H 5 O 2 + energy surface. Justification of the experimental results by molecular orbital calculations on the solvated ions
Author(s) -
Rajadell Fernando,
Planelles Josep,
Tomás Francisco,
Asensio Gregorio,
Miranda Miguel A.,
Sabater María J.
Publication year - 1994
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610070502
Subject(s) - decarboxylation , chemistry , isomerization , protonation , catalysis , solvent , ion , computational chemistry , molecular orbital , photochemistry , organic chemistry , molecule
In constrast with recent molecular orbital calculations on the decarboxylation of O ‐protonated 2‐oxetanone, this experimental work indicates that no decarboxylation of this cation occurs in sulphuric acid solution up to 150°C, but instead a clean isomerization to protonated acrylic acid takes place. Parallel theoretical work shows that the gas‐phase model is too crude to account successfully for the experimental facts obtained in acidic media. However, the latter are well reproduced when the effect of the solvent is taken into account. The present findings do not necessarily invalidate the reaction mechanism currently accepted to explain the rate enhancement and change of stereochemistry accompanying the decarboxylation of 3,4‐disubstituted 2‐oxetanones under acid catalysis.