Water → tert-Butyldiphenylphosphine

HRID 979714Notes

Reaction equation

HRID 979714 reaction equation
[C:1]([Mg]Cl)([CH3:4])([CH3:3])[CH3:2].[C:7]1([P:13](Cl)Cl)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[C:16]1([Mg]Br)[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.O>CCOCC>[C:1]([P:13]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 962WaterHCID 12573Phenyl phosphorus dichlorideHCID 178418255HCID 178418255, compoundHCID 178418310HCID 178418310, compound

Product 1

HCID 80102tert-ButyldiphenylphosphineYield 46%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

466 ml of a 1.06 Molar titrated solution of 494 mmoles of t-butylmagnesium chloride in 466 ml of ether was added dropwise to a stirred solution of 88.4 g (494 mmoles) of phenyldichlorophosphine in 750 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., then the reaction mixture was allowed to gradually warm to ambient temperature. A Grignard mixture of 741 mmoles of phenylmagnesium bromide (prepared from 116.4 g of bromobenzene and 19.8 g of magnesium turnings in 450 ml of anhydrous ether) was added dropwise at +27° C., and the reaction mixture was then refluxed for 18 hours. The mixture was cooled to +18° C., and 340 ml of water was added dropwise at a temperature of between +18° C. and +36° C. After treatment with concentrated hydrochloric acid and ammonium hydroxide distillation gives t-butyldiphenylphosphine. 31P-NMR(delta)=17.53 ppm (relative intensity 1000.59), Yield=about 46%, BP=120°-125° C. at 0.2 torr.

Workup

  1. temperaturemaintained at +10° C. under an inert atmosphere
  2. additionAfter the addition
  3. additionwas added dropwise at +27° C.
  4. temperaturethe reaction mixture was then refluxed for 18 hours
  5. temperatureThe mixture was cooled to +18° C.
  6. distillationAfter treatment with concentrated hydrochloric acid and ammonium hydroxide distillation

Sources & evidence

ORD record
ord-4422829bdba242618a5c19b45aecfe47
Source dataset
uspto-grants-1987_05
Patent number
US04668823

Reaction notes

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