69079-30-7

Upstream product

• 74-93-1 methylthiol 
• 134916-82-8 N-phenyl-methyl-(trimethylsilyl)ketenimine 
• 58276-22-5 methyl N-phenyl ethanimidothioate 
• 74-88-4 methyl iodide 
• 925-90-6 ethylmagnesium bromide 
• 103-72-0 phenyl isothiocyanate 

Downstream Products

• 91914-45-3 N-(methylthio-l propene-l yl) N-phenyl carbamate d'ethyle 
• 111515-19-6 N-methyl-N-phenyl-1-(methylthio)prop-1-enylamine 
• 14752-72-8 1,N-Diphenylpropanimine 
• 80598-98-7 N-(methylthio-l propene-l yl) N-trimethylsilyl aniline 
• 219584-93-7 [1-Ethyl-pent-(Z)-ylidene]-phenyl-amine 

Relevant academic research and scientific papers

Nucleophilic and electrophilic additions to silylated ketenimines generated from imidothioesters

The reactivity of stable silylated N-phenyl ketenimines towards some nucleophilic (organometallics, alcohols, thiols) and electrophilic reagents (PhSCl) were studied. Imino-coumarines (via tandem nucleophilic-electrophilic additions with Peterson olefination) and new phenylthio-and silyl-substituted ketenimines have been prepared.

CARBON-CARBON BOND FORMATION AND KETENIMINE SYNTHESIS FROM N-PHENYL IMIDOTHIOESTERS.

Methyl N-phenyl ethanimidothioate 1 and its α-silylated homologue 2 are metallated into lithiated enaminates which can be regioselectively monoalkylated at -78 deg C on the α-carbon atom.Imidothioester 2, treated at higher temperatures by 2 equivalents of BuLi, leads, after alkylation or hydrolysis, to stable silylated N-phenyl ketenimines.Formation of ketenimines are also observed by flash thermolysis of 2 or of the silylated S,N-ketene acetal 10.

METALLATION ET ALKYLATION DES THIOIMIDOESTERS: APPLICATION EN SYNTHESE

Alkylation of delocalized anions resulting from metallation of N-phenyl thioimidoesters (precursors of dithioesters and thiolesters) takes place on nitrogen with "saturated" thioimidoesters (alkane thiomidates).On the contrary, unsaturated thiomidoesters (α or β-ethylenic, α-arylated) are regioselectively alkylated on the α carbon atom by alkyl or allylic halides.The possibilities for synthesis offered by successive uses of the reactivities of thioimidoester and dithioester functions (allowing in particular two electrophilic additions on two vicinal carbons) are illustrated by syntheses of terpenic compounds lavandual (and lavandulol) and ar-curcumene.