Reactions of perfluorobenzocycloalkenes with ethyl cyanoacetate and methyllithium and some transformations of the products.

Sinyakov, V.; Zonov, Ya.; Karpov, V.; Beregovaya, I.; Platonov, V.

Reactions of perfluorobenzocycloalkenes (ArF) with methyllithium and ethyl cyanoacetate involved replacement of fluorine atoms in positions 3 and 4 of perfluorocyclobutabenzene, position 5 of perfluoroindan, and position 6 of perfluorotetralin by CH and CH(CN)COOEt groups. Hydrolysis of the resulting esters ArCH(CN)COOEt gave the corresponding perfluoroarylacetic acids ArCHCOOH which were converted into dichloroacetyl chlorides ArCClCOCl by treatment with PCl. The reaction of ArCClCOCl with SbF produced trifluoromethyl derivatives ArCF. Decarboxylation of ArCClCOOH in DMF afforded dichloromethyl derivatives ArCClH which reacted with CsF on heating to form difluoromethyl analogs ArCFH.

METHYL acetate; METHYLLITHIUM; CYCLOALKANES; FLUORINE; HYDROLYSIS; ACETIC acid

Russian Journal of Organic Chemistry, 2013, Vol 49, Issue 7, p1010

1070-4280

Academic Journal

10.1134/S1070428013070099