95502-91-3

Upstream product

• 121726-26-9 N-phenyl butene-3 imidothioate de methyle 
• 103-72-0 phenyl isothiocyanate 
• 1730-25-2 (E)-1-propenylmagnesium bromide 
• 74-88-4 methyl iodide 
• 13154-14-8 1-propenylmagnesium bromide 

Downstream Products

• 70369-25-4 (methyl-4 phenyl)-3 butanedithioate de methyle 
• 95502-98-0 methyl-3 N-phenyl pentanimidothioate de methyle 
• 95503-00-7 dimethyl-3,4 N-phenyl pentanimidothioate de methyle 
• 95503-03-0 methyl-3 N-phenyl pentene-4 imidothioate de methyle 
• 95502-92-4 methyl-3 N-phenyl heptanimidothioate de methyle 
• 95502-95-7 trimethyl-3,4,4 N-phenyl pentanimidothioate de methyle 
• 121726-44-1 phenylthio-3 butanedithioate de methyle 
• 121726-34-9 N-aniline 
• 95503-05-2 dimethyl-3,7 N-phenyl octene-6 imidothioate de methyle 
• 121726-36-1 N-aniline 
• 121726-41-8 methyl-3 (methyl-4 cyclohexene-3 yl)-5 hexene-5 thioate de S-methyle 
• 121726-46-3 phenylsulfonyl-3 butanedithioate de methyle 
• 121726-43-0 N-phenyl phenylthio-3 butanimidothioate de methyle 
• 95503-02-9 (methyl-4 phenyl)-3 N-phenyl butanimidothioate de methyle 

Relevant academic research and scientific papers

Reactions des organolithiens et des reactifs de Grignard avec les N-phenyl imidothioesters et les dithioesters α-insatures

The reactivity of α-unsaturated N-phenyl imidothioesters towards organomagnesium and lithium compounds was studied.From an α or β-non ramified imidothioester (methyl N-phenyl 2-butenimidothioate) 1,4-additions were observed with alkyl-, vinyl- and aryl-Grignard reagents, alkyllithium and lithiated limonene, and with benzenethiolate and benzenesulfinate anions.After sulfhydrolysis, new β-ramified or functionalized dithioesters were isolated and one of them was used in a synthesis of 2,6-dimethyl-1,7-octadiene-4-one.A 1,2-addition, with inversion of the allylic chain, was observed with allylic Grignard reagents, followed by a second 1,2-addition to the imine formed after elimination of magnesium methylthiolate.This double addition was not observed with prenylmagnesium bromide, the reaction of which with methyl 3-methyl N-phenyl 2-butenimidothioate led, after hydrolysis, to artemisia ketone.The regoiselectivities of the additions of organometallics to methyl 2-butenedithioate (prepared in situ from methyl phenylsulfonyl-3 butanedithioate) were also examined and they appeared completely different to those observed with the corresponding imidothioester; a thiophilic addition was the first step in the reaction of methyllithium or ethylmagnesium bromide and 1,4-γ-additions were observed with allylic Grignard reagents.

Synthese de cetones a partir de N-phenyl imidothioesters et par l'intermediaire de cetenimines

The thermal decomposition of metallated N-phenyl imidothioesters (lithium or magnesium alkylthio-enaminates generated by either deprotonation or 1,4-addition) led to ketenimines which were trapped in situ by organo-lithium or magnesium compounds to give metallated imines, readily hydrolysed into ketones.This sequence allowed the use of imidothioesters as acyl cation equivalents and also successive and regioselective > 1,3-additions of two different organometallics to an α-unsaturated imidothioester.Ar-turmerone, 2,6-dimethyl-2,7-octadien-4-one, iso-artemisia ketone, α-atlantone and other unsymmetrical ketones were synthesized by this procedure.