Toluene → Di-tert-butyl(2-methoxyphenyl)phosphane

HRID 1297562Notes

Reaction equation

HRID 1297562 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[O:8][CH3:9].[Mg].[C:11]([P:15](Cl)[C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:14])([CH3:13])[CH3:12].C1(C)C=CC=CC=1>O1CCCC1.[Cu](Cl)Cl.O>[C:11]([P:15]([C:16]([CH3:19])([CH3:18])[CH3:17])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[O:8][CH3:9])([CH3:14])([CH3:13])[CH3:12]

Participants

8

Reactant 4

HCID 1140TolueneHCID 113582-BromoanisoleHCID 139566Di-tert-butylchlorophosphine2×HCID 5462224Magnesium

Product 1

HCID 22925368Di-tert-butyl(2-methoxyphenyl)phosphaneYield 94.3%

Reagents, catalysts & solvents 3

HCID 24014Cupric ChlorideCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

In a 300 ml four-necked flask thoroughly purged with nitrogen, a Grignard reagent solution previously prepared from 12.1 g (0.065 mol) of 2-bromoanisole and 2.1 g (0.085 mol) of metallic magnesium in 65 ml of tetrahydrofuran, and 0.13 g (0.0010 mol (corresponding to 2% by mol)) of copper(II) chloride were placed. To the contents of the flask, 9.0 g (0.05 mol) of di-tert-butylphosphinous chloride was dropwise added as it is without being dissolved in a solvent, 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 50° C. for 3 hours. After the temperature of the reaction solution was returned to room temperature, gas chromatography analysis was carried out, and as a result, di-tert-butylphosphinous chloride was present in trace amounts. Thereafter, 65 ml of toluene and 50 ml of water 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 11.9 g (purity: 95.0%) of the aimed di-tert-butyl(2-methoxyphenyl)phosphine was obtained. The yield was 89.7%.

Workup

  1. customIn a 300 ml four-necked flask thoroughly purged with nitrogen
  2. dissolutionwithout being dissolved in a solvent, over a period of 1 hour
  3. temperaturewith maintaining the temperature at 25° C. to 30° C
  4. additionAfter the dropwise addition
  5. customwas returned to room temperature
  6. customliquid separation
  7. washThen, the organic layer was washed with water
  8. dry with materialdried over anhydrous sodium sulfate
  9. distillationThe solvent and a low-boiling component were distilled off under reduced pressure

Sources & evidence

ORD record
ord-7ae3a91df6f34b55a74b6a5835fb9b82
Source dataset
uspto-grants-2007_07
Patent number
US07250535B2

Reaction notes

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