19170-17-3Relevant academic research and scientific papers
REACTION OF 2-ALKOXY-1,3-DIENES WITH ALKYL AND ARYL HYDROSULFIDES
Kobesheva, N. I.,Kheruze, Yu. I.,Petrov, A. A.
, p. 1226 - 1232 (2007/10/02)
The reactions of 2-methoxy-, 2-ethoxy-, 2-isopropoxy-, and 2-tert-butoxy-1,3-butadienes with ethyl hydrosulfide and of 2-methoxy-1,3-butadiene with methyl hydrosulfide under the conditions of nucleophilic reaction (sodium, methanol) were investigated.The reactions of 2-methoxy- and 2-ethoxy-1,3-butadienes with phenyl and ethyl hydrosulfides and also of 2-methoxy- and 2-tert-butoxy-1,3-butadienes with methyl hydrosulfide were carried out under radical conditions.During nucleophilic reaction attack by the thiyl radical takes place exclusively at the terminal carbon atom of the unsubstituted double bond in accordance with the distribution of electron density in the molecule of the dienyl ether; a mixture of 2-alkoxy-4-alkyl-thio-2-butene and 2-alkoxy-4-alkylthio-1-butene is formed.In the case of radical addition a mixture of isomers with preferential addition of the thiyl radical at the terminal atom of the α-alkoxyvinyl group is formed, and the 2-alkoxy-1-alkyl(aryl)thio-2-butene formed here isomerizes to 2-alkoxy-1-alkyl(aryl)thio-1-butene.
