167965-53-9Relevant academic research and scientific papers
Reaction of thioglycolate with α-fluoro-β-(phenylthio)enones (or -enals): Synthesis of substituted α-carboxy-γ-fluorothiophenes
Andres, Didier F.,Laurent, Eliane G.,Marquet, Bernard S.
, p. 1049 - 1052 (2007/10/03)
A new synthetic method to substituted α-carboxy-γ-fluorothiophenes 2F is reported. They were prepared by the reaction between two equivalents of methyl thioglycolate anion and α-fluoro-β-(phenylthio)enones (or -enals) 1F, in DMSO (70°C) in yields ranging from 41% to 85%. We show from the reaction of (Z)-α-fluoro-β-(phenylthio)but-enone 1aF, that cyclisation to fluorothiophene 2aF occurs via the formation of stable enolates of α-fluoro-β-(dithianyl)butanone.
ANODIC FUNCTIONALIZATION OF VINYL SULFIDES. FORMAL ACCESS TO GEM OR VICINAL ARYL THIOETHER DICATIONS
Andres, Didier F.,Laurent, Eliane G.,Marquet, Bernard S.,Benotmane, Hassiba,Bensadat, Abdelkader
, p. 2605 - 2618 (2007/10/02)
The anodic oxidation of a number of vinyl thioethers has been performed in CH3CN-Et3N,3HF.Results clearly show that the reactivity of the vinyl sulfide radical cation depends on several factors as structure of substrates and nucleophilic conditions.For example a dimerization occurred from the unsubstituted vinyl sulfide 1a (CH2=CH-SPh) whereas α,β- and/or β,β-difluoro sulfides were obtained from substituted homologues.In order to understand this reactivity the anodic behaviour of 1a and 1b (Ph-CH=CH-SPh) has been especially analysed in two other nucleophilic media (CH3OH/Et3N,3HF and AcOH/AcOK) leading respectively to methoxylation and acetoxylation of starting compounds.Comparison with electrofluorination results has allowed us to propose a mechanism involving an intermediary episulfonium ion which could explain the formation and ratio of the products isolated.Key Words: vinyl sulfides; enol thioethers; anodic oxidation; electrochemistry; fluorination; methoxylation; acetoxylation; formal dication; fluorosulfides
