Sulfuric Acid → 2-(Di-tert-butylphosphino)biphenyl

HRID 1297563Notes

Reaction equation

HRID 1297563 reaction equation
[C:1]([P:5](Cl)[C:6]([CH3:9])([CH3:8])[CH3:7])([CH3:4])([CH3:3])[CH3:2].Br[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=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:23]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[C:13]1[CH:12]=[CH:17][CH:16]=[CH:15][CH:14]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 4

HCID 1118Sulfuric AcidHCID 163292-BromobiphenylHCID 139566Di-tert-butylchlorophosphine2×HCID 5462224Magnesium

Product 1

HCID 27342152-(Di-tert-butylphosphino)biphenylYield 88.5%

Reagents, catalysts & solvents 3

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

Procedure

In a 500 ml four-necked flask thoroughly purged with nitrogen, 9.0 g (0.05 mol) of di-tert-butylphosphinous chloride, 0.07 g (0.0005 mol (corresponding to 1% by mol)) of copper(I) bromide and 50 ml of tetrahydrofuran were placed. To the contents of the flask, a Grignard reagent solution previously prepared from 14.0 g (0.060 mol) of 2-bromobiphenyl and 1.7 g (0.072 mol) of metallic magnesium in 100 ml of tetrahydrofuran was dropwise added over a period of 1 hour with maintaining the temperature at 30° C. to 35° C. After the dropwise addition was completed, stirring was conducted at a reflux temperature for 4 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, 30 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 and a low-boiling component were distilled off under reduced pressure to obtain coarse crystals. The coarse crystals were recrystallized from MeOH to obtain 13.2 g (purity: 99.0%) of the aimed di-tert-butyl(2-phenylphenyl)phosphine. The yield was 87.5%. Melting point: 84-85° C.

Workup

  1. additionwas dropwise added over a period of 1 hour
  2. temperaturewith maintaining the temperature at 30° C. to 35° 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 and a low-boiling component were distilled off under reduced pressure
  9. customto obtain coarse crystals
  10. customThe coarse crystals were recrystallized from MeOH

Sources & evidence

ORD record
ord-9c12fd31a60c49809b83af334474ffce
Source dataset
uspto-grants-2007_07
Patent number
US07250535B2

Reaction notes

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