Sulfuric Acid → Di-tert-butyl(2,4,6-trimethylphenyl)phosphane

HRID 1297564Notes

Reaction equation

HRID 1297564 reaction equation
[C:1]([P:5](Cl)[C:6]([CH3:9])([CH3:8])[CH3:7])([CH3:4])([CH3:3])[CH3:2].[C:11]1([CH3:20])[CH:16]=[C:15]([CH3:17])[CH:14]=[C:13]([CH3:18])[C:12]=1Br.[Mg].S(=O)(=O)(O)O>O1CCCC1.[Cu]Cl.C1(C)C=CC=CC=1>[C:1]([P:5]([C:6]([CH3:9])([CH3:8])[CH3:7])[C:12]1[C:13]([CH3:18])=[CH:14][C:15]([CH3:17])=[CH:16][C:11]=1[CH3:20])([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 4

HCID 1118Sulfuric AcidHCID 684732-BromomesityleneHCID 139566Di-tert-butylchlorophosphineHCID 5462224Magnesium

Product 1

HCID 22925511Di-tert-butyl(2,4,6-trimethylphenyl)phosphaneYield 90%

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
73 °C

Procedure

In a 300 ml four-necked flask thoroughly purged with nitrogen, 20 ml of tetrahydrofuran, 9.0 g (0.05 mol) of di-tert-butylphosphinous chloride and 0.05 g (0.0005 mol (corresponding to 1% by mol)) of copper(I) chloride were placed. To the contents of the flask, a Grignard reagent solution previously prepared from 14.9 g (0.075 mol) of mesityl bromide and 2.2 g (0.090 mol) of metallic magnesium in 100 ml of tetrahydrofuran was dropwise added over a period of 1 hour at 50° C. After the dropwise addition was completed, stirring was conducted under reflux at 73° C. for 4 hours. After the temperature of the reaction solution was returned to room temperature, 40 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. After the solvent was distilled off under reduced pressure, a small amount of MeOH was added, and the whole system was cooled to −30° C. to precipitate solids. The solids were filtered off to obtain 11.9 g (purity: 97.5%) of the aimed di-tert-butyl(2,4,6-trimethylphenyl)phosphine as white solids. The yield was 88.0%. Melting point: 36-37° C.

Workup

  1. additionwas dropwise added over a period of 1 hour at 50° 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. distillationAfter the solvent was distilled off under reduced pressure
  8. additiona small amount of MeOH was added
  9. temperaturethe whole system was cooled to −30° C.
  10. customto precipitate solids
  11. filtrationThe solids were filtered off

Sources & evidence

ORD record
ord-9f58df2eef8747569224126728a1046f
Source dataset
uspto-grants-2007_07
Patent number
US07250535B2

Reaction notes

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