62926-06-1Relevant articles and documents
Carbophilic reactions of amines or methanol with thioaldehyde-S-oxides
Baudin, Jean-Bernard,Commenil, Marie-Gabrielle,Julia, Sylvestre A.,Lome, Robert,Ruel, Odile
, p. 1127 - 1141 (2007/10/03)
Correspondence and reprints Reaction of primary aliphatic amines with 7-ethylenic thioaldehyde-S-oxides la,b affords the corresponding imines 2a,b via a carbophilic addition of amine. When treated with sodium methoxide (1 equiv) and an excess of a primary amine, some methyl sulfinates 3 or 6, bearing a benzylic or allylic chain on the sulfur, are converted into imines 4 or 7. Treatment of the methyl sulfinates 3 with methoxide anion in THF or methanol generally affords a mixture of aldehydes 9, the corresponding dimethylacetals 14, a,a'-dimethoxydisulfides 10, esters 11, thionoesters 12 and methyl a-methoxysulfinates 15, whose ratios depend on the conditions. The formation of these compounds is best explained by a deprotonationelimination of the methyl sulfinates into the corresponding thioaldehyde-S-oxides; which then undergo a carbophilic addition of methoxide anion or methanol. Several possible reaction paths from the so-formed a-methoxysulfenate anions IX are discussed for their conversion into the final compounds. unsaturated sulfinic ester / elimination / thioaldehyde-S-oxide / imine / aldehyde / a,a -dimethoxydisulflde / thionoester / methyl u-methoxysulflnate Eisevier,.
