Sulfuric Acid → Benzyl-di-t-butylphosphine

HRID 1297572Notes

Reaction equation

HRID 1297572 reaction equation
[CH2:1](Cl)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Mg].[C:10]([P:14](Cl)[C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:13])([CH3:12])[CH3:11].S(=O)(=O)(O)O>O1CCCC1.[Cu](Br)Br.C1(C)C=CC=CC=1>[C:10]([P:14]([C:15]([CH3:18])([CH3:17])[CH3:16])[CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)([CH3:13])([CH3:12])[CH3:11]

Participants

8

Reactant 4

HCID 1118Sulfuric AcidHCID 7503Benzyl ChlorideHCID 139566Di-tert-butylchlorophosphineHCID 5462224Magnesium

Product 1

HCID 11170394Benzyl-di-t-butylphosphineYield 89.7%

Reagents, catalysts & solvents 3

HCID 24611Copper bromide (CuBr2)CatalystHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

In a 200 ml four-necked flask thoroughly purged with nitrogen, a Grignard reagent solution previously prepared from 8.2 g (0.065 mol) of benzyl chloride and 2.1 g (0.085 mol) of metallic magnesium in 50 ml of tetrahydrofuran, and 0.055 g (0.0003 mol (corresponding to 0.6% by mol)) of copper(II) bromide 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 at a temperature in the vicinity of 40° C. After the dropwise addition was completed, stirring was conducted at a temperature of 40° C. to 45° C. for 3 hours. After the temperature of the reaction solution was returned to room temperature, 20 ml of toluene and 20 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 145° C. to 150° C. under reduced pressure of 0.5 Torr were collected. As a result, 10.6 g (purity: 98.5%) of the aimed di-tert-butylbenzylphosphine was obtained as an oily substance. The yield was 88.3%.

Workup

  1. customIn a 200 ml four-necked flask thoroughly purged with nitrogen
  2. dissolutionwithout being dissolved in a solvent, over a period of 1 hour at a temperature in the vicinity of 40° 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 145° C. to 150° C. under reduced pressure of 0.5 Torr
  11. customwere collected

Sources & evidence

ORD record
ord-e7e0005408464992a6686289334aeff5
Source dataset
uspto-grants-2007_07
Patent number
US07250535B2

Reaction notes

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