Sulfuric Acid → Di-tert-butyl(ethyl)phosphane

HRID 1297567Notes

Reaction equation

HRID 1297567 reaction equation
[C:1]([P:5](Cl)[C:6]([CH3:9])([CH3:8])[CH3:7])([CH3:4])([CH3:3])[CH3:2].O1CC[CH2:13][CH2:12]1.C([Mg]Cl)C.S(=O)(=O)(O)O>[Cu]Br.C1(C)C=CC=CC=1>[C:1]([P:5]([C:6]([CH3:9])([CH3:8])[CH3:7])[CH2:12][CH3:13])([CH3:4])([CH3:3])[CH3:2]

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 8028Tetrahydrofuran2×HCID 139566Di-tert-butylchlorophosphine2×HCID 178461633HCID 178461633, compound

Product 1

HCID 12603439Di-tert-butyl(ethyl)phosphaneYield 88.2%

Reagents, catalysts & solvents 2

HCID 24593copper(I) bromideCatalystHCID 1140TolueneSolvent

Procedure

In a 300 ml four-necked flask thoroughly purged with nitrogen, 18.1 g (0.1 mol) of di-tert-butylphosphinous chloride, 0.28 g (0.002- mol (corresponding to 2% by mol)) of copper(I) bromide and 60 ml of tetrahydrofuran were placed. To the contents of the flask, 55 ml (0.11 mol) of a tetrahydrofuran solution of ethylmagnesium chloride having a concentration of 2 mol/liter 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 the same temperature for 2 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, 50 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 92° C. to 95° C. under reduced pressure of 20 Torr were collected. As a result, 15.7 g (purity: 98.0%) of the aimed di-tert-butylethylphosphine was obtained as an oily substance. The yield was 88.2%.

Workup

  1. temperaturewith maintaining the temperature at 25° C. to 30° C
  2. additionAfter the dropwise addition
  3. customwas returned to room temperature
  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 92° C. to 95° C. under reduced pressure of 20 Torr
  10. customwere collected

Sources & evidence

ORD record
ord-51611efcba3c4d72830cbd0fb4ae9a0f
Source dataset
uspto-grants-2007_07
Patent number
US07250535B2

Reaction notes

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