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Photosensitized oxygenation of some benzyl sulfides. The role of persulfoxide
Author(s) -
Bonesi Sergio M.,
Freccero Mauro,
Albini Angelo
Publication year - 1999
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/(sici)1099-1395(199909)12:9<703::aid-poc178>3.0.co;2-l
Subject(s) - chemistry , benzaldehyde , sulfide , intramolecular force , sulfoxide , hydrogen sulfide , medicinal chemistry , benzene , benzyl alcohol , photochemistry , hydrogen , sulfur , organic chemistry , catalysis
Benzyl ethyl sulfide ( 6a ) is photo‐oxidized to benzaldehyde in benzene, whereas diethyl sulfide is known to give inefficiently the sulfoxide under these conditions. Oxidative CS cleavage is the main process also with benzhydryl ethyl sulfide ( 6c ), but not with α‐methylbenzyl ethyl sulfide ( 6b ), which mainly gives the sulfoxide. The carbonyl derivatives reasonably arise from S ‐hydroperoxy ylides ( 3 ). Consistently with this finding, calculations at the PM3 level suggest that the first intermediate, the persulfoxide ( 1 ), undergoes intramolecular hydrogen transfer when an activated α‐hydrogen is available and gives 3 . This is the case for the above benzyl sulfides (Δ H ≠ for the process decreases with decreasing CH BDE). However, only some of the persulfoxide conformations are correctly oriented for this rearrangement, and this may slow this process and make other reactions compete, as happens with 6b . Copyright © 1999 John Wiley & Sons, Ltd.