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Fragmentation and isomerization reactions of phenyl substituted 2‐oxo‐1,3,2‐dioxathianes (trimethylene sulfites)
Author(s) -
Olsen Robert J.,
Lewis Timothy A.,
Mehta Manish A.,
Stack Jeffrey G.
Publication year - 1986
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570230428
Subject(s) - chemistry , isomerization , fragmentation (computing) , benzaldehyde , substituent , medicinal chemistry , ionic bonding , boron trifluoride , photochemistry , organic chemistry , ion , catalysis , computer science , operating system
The preparation and Grob‐like fragmentation of several phenyl substituted 2‐oxo‐1,3,2‐dioxathianes (trimethylene sulfites) have been examined. Preparation of the 4,4,6‐triphenyl derivatives gives a chair S = O equatorial isomer which fragments readily in polar solvents to produce benzaldehyde and 1,1‐diphenylethylene. Isomerization to an unreactive twist boat isomer occurs as a minor reaction in solution and in the solid state on prolonged storage. Activation parameters and substituent effects on the fragmentation reaction are consistent with an ionic mechanism. The diphenyl derivatives react only in the presence of boron trifluoride etherate giving mainly isomerization to the stable chair, S = O axial form; fragmentation is a minor pathway.