Sulfuric Acid → Tris(1,1-dimethylethyl)phosphine

HRID 1297571Notes

Reaction equation

HRID 1297571 reaction equation
[C:1]([P:5](Cl)[C:6]([CH3:9])([CH3:8])[CH3:7])([CH3:4])([CH3:3])[CH3:2].[C:11](Cl)([CH3:14])([CH3:13])[CH3:12].[Mg].S(=O)(=O)(O)O>O1CCCC1.[Cu]Cl.C1(C)C=CC=CC=1>[C:1]([P:5]([C:11]([CH3:14])([CH3:13])[CH3:12])[C:6]([CH3:9])([CH3:8])[CH3:7])([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 4

HCID 1118Sulfuric AcidHCID 10486tert-BUTYL CHLORIDEHCID 139566Di-tert-butylchlorophosphine2×HCID 5462224Magnesium

Product 1

HCID 83681Tris(1,1-dimethylethyl)phosphineYield 90.9%

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

In a 200 ml four-necked flask thoroughly purged with nitrogen, 9.0 g (0.05 mol) of di-tert-butylphosphinous chloride, 0.05 g (0.0005 mol (corresponding to 1% by mol)) of copper(I) chloride and 20 ml of tetrahydrofuran were placed. To the contents of the flask, a Grignard reagent solution previously prepared from 6.0 g (0.065. mol) of tert-butyl chloride and 1.9 g (0.078 mol) of metallic magnesium in 50 ml of tetrahydrofuran was dropwise added over a period of 1 hour with maintaining the temperature at 20° C. to 25° C. After the dropwise addition was completed, stirring was conducted at a temperature of 35° C. to 40° C. for 3 hours. Then, disappearance of di-tert-butylphosphinous chloride was confirmed by gas chromatography. Thereafter, 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 111° C. to 113° C. under reduced pressure of 15 Torr were collected. As a result, 9.2 g (purity: 99.0%) of the aimed tri-tert-butylphosphine was obtained as an oily substance. The yield was 90.2%.

Workup

  1. additionwas dropwise added over a period of 1 hour
  2. temperaturewith maintaining the temperature at 20° C. to 25° C
  3. additionAfter the dropwise addition
  4. customliquid separation
  5. washThen, the organic layer was washed with water
  6. dry with materialdried over anhydrous sodium sulfate
  7. distillationThe solvent was distilled off under reduced pressure
  8. distillationfollowed by further distillation
  9. distillationThen, fractions given by distillation at 111° C. to 113° C. under reduced pressure of 15 Torr
  10. customwere collected

Sources & evidence

ORD record
ord-485dadd027e64d48891b3130640cbaf2
Source dataset
uspto-grants-2007_07
Patent number
US07250535B2

Reaction notes

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