Abstract
The unimolecular reactions of methyl acetate and its sulphur analogues, S-methyl and O-methyl monothioacetate and methyl dithioacetate, were investigated using the semi-empirical MNDO method with respect to ketene-thioketene formation and 1,3-methyl migration. For methyl acetate, 1,3-methyl migration of the methyl ester was calculated to be more favourable than ketene formation. S-Methyl monothioacetate undergoes ketene formation preferentially while O-methyl monothioacetate rearranges via 1,3-methyl migration to the more thermodynamically stable S-methyl isomer. Methyl dithioacetate also prefers methyl migration; however, unlike the other three compounds, the theoretical results condtradict earlier reported experimental results.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 237-241 |
| Number of pages | 5 |
| Journal | Journal of the Chemical Society, Perkin Transactions 2 |
| Issue number | 2 |
| State | Published - 1987 |
| Externally published | Yes |
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An MNDO study of the unimolecular reactions of methyl acetate and its sulphur analogues. / Lebrilla, Carlito B; Schwarz, Helmut.
In: Journal of the Chemical Society, Perkin Transactions 2, No. 2, 1987, p. 237-241.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - An MNDO study of the unimolecular reactions of methyl acetate and its sulphur analogues
AU - Lebrilla, Carlito B
AU - Schwarz, Helmut
PY - 1987
Y1 - 1987
N2 - The unimolecular reactions of methyl acetate and its sulphur analogues, S-methyl and O-methyl monothioacetate and methyl dithioacetate, were investigated using the semi-empirical MNDO method with respect to ketene-thioketene formation and 1,3-methyl migration. For methyl acetate, 1,3-methyl migration of the methyl ester was calculated to be more favourable than ketene formation. S-Methyl monothioacetate undergoes ketene formation preferentially while O-methyl monothioacetate rearranges via 1,3-methyl migration to the more thermodynamically stable S-methyl isomer. Methyl dithioacetate also prefers methyl migration; however, unlike the other three compounds, the theoretical results condtradict earlier reported experimental results.
AB - The unimolecular reactions of methyl acetate and its sulphur analogues, S-methyl and O-methyl monothioacetate and methyl dithioacetate, were investigated using the semi-empirical MNDO method with respect to ketene-thioketene formation and 1,3-methyl migration. For methyl acetate, 1,3-methyl migration of the methyl ester was calculated to be more favourable than ketene formation. S-Methyl monothioacetate undergoes ketene formation preferentially while O-methyl monothioacetate rearranges via 1,3-methyl migration to the more thermodynamically stable S-methyl isomer. Methyl dithioacetate also prefers methyl migration; however, unlike the other three compounds, the theoretical results condtradict earlier reported experimental results.
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UR - http://www.scopus.com/inward/citedby.url?scp=5244245604&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:5244245604
SP - 237
EP - 241
JO - Journal of the Chemical Society, Perkin Transactions 2
JF - Journal of the Chemical Society, Perkin Transactions 2
SN - 1470-1820
IS - 2
ER -