Sodium dithionite initiated fluoroalkylation of trimethoxybenzenes, mesitylene and pyrroles with BrCF2CF2Br

Sodium dithionite initiated reaction of 1,2-dibromotetrafluoroethane with 1,3,5-trimethoxybenzene (1a) in an acetonitrile–water mixture proceeded efficiently at ambient temperature to give 1-(2-bromotetrafluoroethyl)-2,4,6-trimethoxybenzene (2) almost quantitatively. Similar reaction with 1,2,3-trimethoxybenzene (1b) gave only reasonable yield of regioisomers of (2-bromotetrafluoroethyl)-trimethoxybenzenes 3 and 4 and small amount of a substitution product of the central trimethoxy group, 1-(2-bromotetrafluoroethyl)-2,6-dimethoxybenzene (5). The reaction with mesitylene (6) gave complex mixtures from which, depending on the temperature and a mesitylene/BrCF2CF2Br ratio, the expected (2-bromotetrafluoroethyl)mesitylene (8) or a dimeric product, 4,4′-bis(2-bromo-1,1,2,2-tetrafluoroethyl)-1,3,5,1′,3′,5′-hexamethylbicyclohexyl-2,5,2′,5′-tetraene (7), were isolated in a yield of 18 and 13%, respectively. The reactions of BrCF2CF2Br with pyrrole (9) and 1-methylpyrrole (11) gave the respective alkylated compounds, 2-(2-bromotetrafluoroethyl)pyrrole (10) and 2-(2-bromotetrafluoroethyl)-1-methylpyrrole (12) in over 70% yields; the former was found to be fairly unstable. The reactivity of the terminal bromine atom in 1-(2-bromotetrafluoroethyl)-2,4,6-trimethoxybenzene (2) was also investigated.

Sodium dithionite initiated reaction of 1,2-dibromotetrafluoroethane with 1,3,5-trimethoxybenzene (1a) in an acetonitrile–water mixture proceeded efficiently at ambient temperature to give 1-(2-bromotetrafluoroethyl)-2,4,6-trimethoxybenzene (2) almost quantitatively. Similar reaction with 1,2,3-trimethoxybenzene (1b) gave only reasonable yield of regioisomers of (2-bromotetrafluoroethyl)-trimethoxybenzenes 3 and 4 and small amount of a substitution product of the central trimethoxy group, 1-(2-bromotetrafluoroethyl)-2,6-dimethoxybenzene (5). The results of the reactions with mesithylene (6) gave complex mixtures from which, depending on the temperature and a mesithylene/BrCF2CF2Br ratio, the expected (2-bromotetrafluoroethyl)mesithylene (8) or a dimeric product, 4,4′-bis(2-bromo-1,1,2,2-tetrafluoroethyl)-1,3,5,1′,3′,5′-hexamethylbicyclohexyl-2,5,2′,5′-tetraene (7), were isolated in a 18 and 13%, respectively. The reactions of BrCF2CF2Br with pyrrole (9) and 1-methylpyrrole (11) gave the respective alkylated compounds, 2-(2-bromotetrafluoroethyl)pyrrole (10) and 2-(2-bromotetrafluoroethyl)-1-methylpyrrole (12) in over 70% yields; the former was found to be fairly unstable. The reactivity of the terminal bromine atom in 1-(2-bromotetrafluoroethyl)-2,4,6-trimethoxybenzene (2) was also investigated.Figure optionsDownload as PowerPoint slide