Sulfuric Acid → Di-tert-butylphenylphosphine

HRID 1297560Notes

Reaction equation

HRID 1297560 reaction equation
[C:1]([P:5](Cl)[C:6]([CH3:9])([CH3:8])[CH3:7])([CH3:4])([CH3:3])[CH3:2].Cl[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[Mg].S(=O)(=O)(O)O>O1CCCC1.[Cu]Br.C1(C)C=CC=CC=1>[C:1]([P:5]([C:6]([CH3:9])([CH3:8])[CH3:7])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 4

HCID 1118Sulfuric AcidHCID 7964ChlorobenzeneHCID 139566Di-tert-butylchlorophosphine2×HCID 5462224Magnesium

Product 1

HCID 316378Di-tert-butylphenylphosphineYield 89.5%

Reagents, catalysts & solvents 3

HCID 24593copper(I) bromideCatalystHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

In a 300 ml four-necked flask thoroughly purged with nitrogen, 40 ml of tetrahydrofuran, 18.1 g (0.1 mol) of di-tert-butylphosphinous chloride and 0.14 g (0.001 mol (corresponding to 1% by mol)) of copper(I) bromide were placed. To the contents of the flask, a Grignard reagent solution previously prepared from 13.5 g (0.12 mol) of chlorobenzene and 3.5 g (0.14 mol) of metallic magnesium in 100 ml of tetrahydrofuran was dropwise added over a period of 1 hour with maintaining the temperature at 25° C. to 30° C. After the dropwise addition was completed, stirring was conducted at a temperature of 35° C. to 40° C. for 3 hours. After the temperature of the reaction solution was returned to room temperature, disappearance of di-tert-butylphosphinous chloride was confirmed by gas chromatography. Thereafter, 40 ml of toluene and 30 ml of a 5% sulfuric acid aqueous solution were added to the reaction solution to perform liquid separation. Then, the organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, followed by further distillation. Then, fractions given by distillation at 110° C. to 112° C. under reduced pressure of 5 Torr were collected. As a result, 19.9 g (purity: 99.0%) of the aimed di-tert-butylphenylphosphine was obtained as a viscous oily substance. The yield was 89.0%.

Workup

  1. additionwas dropwise added over a period of 1 hour
  2. temperaturewith maintaining the temperature at 25° C. to 30° C
  3. additionAfter the dropwise addition
  4. customwas returned to room temperature
  5. customliquid separation
  6. washThen, the organic layer was washed with water
  7. dry with materialdried over anhydrous sodium sulfate
  8. distillationThe solvent was distilled off under reduced pressure
  9. distillationfollowed by further distillation
  10. distillationThen, fractions given by distillation at 110° C. to 112° C. under reduced pressure of 5 Torr
  11. customwere collected

Sources & evidence

ORD record
ord-f0310134a06c4f9b9d383b9f0b0ea11c
Source dataset
uspto-grants-2007_07
Patent number
US07250535B2

Reaction notes

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