SYNTHESE ET REACTIVITE DES PERFLUOROALKYL-3 ALKYLTHIO-3 PROPENOATES D'ETHYLE: THIOPHENES ET β-thioxoesters perfluoroalkyles

Article abstract of DOI:10.1016/S0040-4020(01)87467-6

The action of thiols with perfluoroalkylated α,Sb-unsaturated compounds (ethyl 3-F-alkyl propynoates 1 and ethyl 3-F-alkyl propenoates 2) was investigated and the reactivity of the adducts reported.The mono-adducts Z and E formed by the action of thiols with 1 were unambiguously identified by 19F-NMR.In addition to the expected alkenes Z and E, the reaction of 1 with ethyl mercaptoacetate led to ethyl 2-F-alkyl-4-hydroxy-3-thiophenecarboxylate 7.The cyclisation of ethyl 3-F-alkyl-3-(methoxycarbonylmethyltio)propenoate Z in basic medium afforded methyl 5-F-alkyl-3-hydroxy-2-thiophenecarboxylate 8, whereas in similar conditions ethyl 3-F-alkyl-3-(methoxycarbonylethylthio)propenoate led to ethyl 3-F-alkyl-3-mercaptopropenoate as a first example of β-thioxoesters bearing a sulfur atom on the α-carbon of the perfluoroalkylated chain.