Chloride → HCID 68476398, compound

HRID 1889208Notes

Reaction equation

HRID 1889208 reaction equation
C(=S)=S.[CH:4]1([P:10]([CH:17]2[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]2)[CH:11]2[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]2)[CH2:9][CH2:8][CH2:7][CH2:6][CH2:5]1.[Cl-:23].Cl.C1(P(C2CCCCC2)C2CCCCC2)CCCCC1>C(O)C>[Cl-:23].[CH:17]1([PH+:10]([CH:4]2[CH2:5][CH2:6][CH2:7][CH2:8][CH2:9]2)[CH:11]2[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]2)[CH2:18][CH2:19][CH2:20][CH2:21][CH2:22]1

Participants

6

Reactant 4

HCID 312Chloride2×HCID 313Hydrochloric Acid3×HCID 75806TricyclohexylphosphineHCID 102297Phosphine, tricyclohexyl-, compd. with carbon disulfide (1:1)

Product 1

HCID 68476398HCID 68476398, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

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.

Workup

  1. distillationis distilled off at 78-79° C
  2. additionthe tricyclohexyl phosphine solution is treated with hydrogen chloride at 20° C
  3. additionThe resulting suspension is diluted with 70 ml tert-butylmethylether
  4. customAfter complete precipitation of the tricyclohexyl phosphine as hydrochloride salt the solvent
  5. customis evaporated off
  6. filtrationThe solid is filtered off
  7. washwashed twice with 10 ml tert-butylmethylether each, and
  8. customdried at 0.02 mbar
  9. custom13.1 g of a colorless hygroscopic solid is obtained
  10. waitIf a sample of the solid is left at open atmosphere, it

Sources & evidence

ORD record
ord-9012d6880e9144179321dbfda814b959
Source dataset
uspto-grants-2013_08
Patent number
US08501985B2

Reaction notes

Loading…