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Unexpected Migration and O to S Benzylic Shift of Thiocarbamate‐containing Salicylaldehyde Derivatives.
Author(s) -
Mangue Jordan,
Dubreucq Quentin,
Pécaut Jacques,
Ménage Stéphane,
Torelli Stéphane
Publication year - 2016
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201601374
Subject(s) - thiocarbamate , chemistry , aldehyde , thiocarbamates , steric effects , reactivity (psychology) , salicylaldehyde , ring (chemistry) , aryl , medicinal chemistry , organic chemistry , stereochemistry , catalysis , medicine , schiff base , alternative medicine , alkyl , pathology
Abstract : An unexpected reactivity of the O ‐dimethylthiocarbamate function has been evidenced concomitantly with the reduction of an aldehyde function presents at its ortho (o‐) position. A systematic study using various substrates showed the exclusive formation of the rearranged compounds after 24 h and confirmed that the only‐reduced compounds are reaction intermediates. However, electronic/steric contributions of the aromatic ring substituents on the composition of the reaction mixture (reduction of the aldehyde vs . migration) were observed at the early stage of the reaction (2 h). These new benzyl S ‐thiocarbamates compounds could be of particular interest as precursors for not trivial and functionalized free methylthiobenzyl alcohols.