Hydrochloric Acid → Phosphine, cyclohexyldiphenyl-

HRID 979713Notes

Reaction equation

HRID 979713 reaction equation
[CH:1]1([Mg]Cl)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[C:9]1([P:15](Cl)Cl)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[C:18]1([Mg]Br)[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.Cl.[OH-].[NH4+]>CCOCC.O>[CH:1]1([P:15]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 12573Phenyl phosphorus dichlorideHCID 14923Ammonium HydroxideHCID 178418255HCID 178418255, compoundHCID 178478990HCID 178478990, compound

Product 1

HCID 80756Phosphine, cyclohexyldiphenyl-Yield 70%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent3×

Procedure

154 ml of a 1.72 Molar titrated solution of 0.266 mole of cyclohexylmagnesium chloride in ether was added dropwise to a stirred solution of 47.54 g (0.2656 mole) of phenyldichlorophosphine in 400 ml of anhydrous ether, maintained at +10° C. under an inert atmosphere. After the addition was complete the mixture was stirred for 15 minutes at +10° C. A 2.0 Molar solution of 0.319 mole of phenylmagnesium bromide in 159 ml of ether was then added dropwise at a temperature of between +10° and +22° C. The mixture was warmed to reflux for one-half hour, then cooled to +6° C. and treated dropwise with 160 ml of water then 14 ml of concentrated hydrochloric acid. The mixture was made basic with 10 ml of concentrated ammonium hydroxide (to pH=9) and the ether phase was separated, dried with magnesium sulfate and concentrated to yield a yellow waxy solid. Recrystallization from ethanol gave cyclohexyldiphenylphosphine. MP=52.5°-57.5° C., 31P-NMR δ=-1.97 ppm (relative intensity 999.93) and δ=-1.25 ppm (dicyclohexylphenylphosphine impurity-relative intensity=13.25), Yield=about 70%.

Workup

  1. temperaturemaintained at +10° C. under an inert atmosphere
  2. additionAfter the addition
  3. temperatureThe mixture was warmed
  4. temperatureto reflux for one-half hour
  5. temperaturecooled to +6° C.
  6. customthe ether phase was separated
  7. dry with materialdried with magnesium sulfate
  8. concentrationconcentrated
  9. customto yield a yellow waxy solid
  10. customRecrystallization from ethanol

Sources & evidence

ORD record
ord-792c2b6409194917a0709dfa6ed8296a
Source dataset
uspto-grants-1987_05
Patent number
US04668823

Reaction notes

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