Chloride → HCID 68476398, compound

Participants

Reaction Steps

225 g cyclohexyl chloride and 750 ml diethylether are mixed. 100 ml of this mixture is added to 48.0 g magnesium turnings, and the reaction is started by adding 1 ml 1,2-dibromethane. The remaining cyclohexyl chloride mixture is added to the magnesium turnings within 3.5 hours under cooling at 38-40° C. The suspension is stirred again for one hour, cooled down to room temperature, and the cyclohexyl magnesium chloride solution is decanted from the remaining magnesium turnings. 156.7 g of the Grignard solution obtained in this manner is mixed with 120 ml tetrahydrofuran and slowly added to a mixture of 18.1 g phosphorus trichloride and 60 ml tetrahydrofuran at −20° C., and to an additional 100 ml tetrahydrofuran 20° C. After one hour of stirring at 37° C., the reaction mixture is added to 110 ml of a 15% ammonium chloride solution in water and 70 ml water at 20° C. The lower phase is separated and discarded. To the organic phase is added 10.1 g carbon disulfide. During this process, a reddish-brown precipitate is obtained, which is filtered off after 3 days, and washed three times each with 20 ml petrolether. After drying the solid at 35° C. under vacuum, 25.4 g (54%) of a tricyclohexylphosphine carbon disulfide adduct (CAS-Nr.: 4635-58-9) is obtained as a reddish-brown solid. From a mixture of 17.8 g of the tricyclohexyl phosphine carbon disulfide adduct and 100 ml ethanol, 80 ml of solvent is distilled off at 78-79° C. The oily residue is taken up in 80 ml tert-butylmethylether, and the tricyclohexyl phosphine solution is treated with hydrogen chloride at 20° C. The resulting suspension is diluted with 70 ml tert-butylmethylether. After complete precipitation of the tricyclohexyl phosphine as hydrochloride salt the solvent is evaporated off, and the solid residue is taken up in 100 ml tert-butylmethylether. The solid is filtered off, washed twice with 10 ml tert-butylmethylether each, and dried at 0.02 mbar. 13.1 g of a colorless hygroscopic solid is obtained. It contains 22.5% chloride so that it is assumed that in addition to the hydrochloride an additional equivalent hydrogen chloride is bound in the crystal (calculated for PCy3*2 HCl: 20.1% chloride). If a sample of the solid is left at open atmosphere, it will melt after one hour.

Provenance & Evidence