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Theoretical studies of substituent effects on thermal eliminations of aryl ethyl carbonates and S ‐aryl O ‐ethyl thiocarbonates
Author(s) -
Kim Chang Kon,
Lee BonSu,
Lee Ikchoon
Publication year - 1993
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.610060404
Subject(s) - chemistry , substituent , aryl , medicinal chemistry , ring (chemistry) , thermal decomposition , pyrolysis , polar effect , leaving group , organic chemistry , photochemistry , catalysis , alkyl
Substituent effects on the thermal elimination reactions of carbonates and thiocarbonates were investigated MO theoretically using the AM1 method. For both substrates, an electron‐withdrawing group is found to facilitate the decomposition. A two‐step process is favoured by carbonates, whereas one‐ and two‐step processes can compete in the pyrolysis of thiocarbonates. The ability to transmit substituent effect is greater with oxygen (carbonates) than with sulphur (thicarbonates) in contrast to the experimental results of Taylor and co‐workers. Modelling studies with replacement of the phenyl ring with a vinyl group are found to be justified in this type of work.