Sulfuric Acid → di-tert-butyl(1-naphthyl)phosphine

HRID 1297565Notes

Reaction equation

HRID 1297565 reaction equation
[C:1]([P:5](Cl)[C:6]([CH3:9])([CH3:8])[CH3:7])([CH3:4])([CH3:3])[CH3:2].Br[C:12]1[C:21]2[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=2)[CH:15]=[CH:14][CH:13]=1.[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:20]1[C:21]2[C:16](=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH:17]=[CH:18][CH:19]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 4

HCID 1118Sulfuric AcidHCID 70011-BromonaphthaleneHCID 139566Di-tert-butylchlorophosphine2×HCID 5462224Magnesium

Product 1

HCID 12118702di-tert-butyl(1-naphthyl)phosphineYield 86.6%

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 1140TolueneSolvent2×HCID 8028TetrahydrofuranSolvent2×

Procedure

In a 500 ml four-necked flask thoroughly purged with nitrogen, 18.1 g (0.1 mol) of di-tert-butylphosphinous chloride, 0.20 g (0.002 mol (corresponding to 2% by mol)) of copper(I) chloride, 20 ml of tetrahydrofuran and 20 ml of toluene were placed. To the contents of the flask, a Grignard reagent solution previously prepared from 24.8 g (0.12 mol) of 1-bromonaphthalene and 3.5 g (0.14 mol) of metallic magnesium in 180 ml of tetrahydrofuran 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 65° C. for 3 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, 30 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 to obtain an oily substance. The oily substance was recrystallized from 150 ml of methanol to obtain 23.6 g (purity: 98.5%) of the aimed di-tert-butyl(1-naphthyl)phosphine as white crystals. The yield was 85.4%. Melting point: 95-97° C.

Workup

  1. additionwas dropwise added over a period of 1 hour
  2. temperaturewith maintaining the temperature at 25° C. to 30° 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. customto obtain an oily substance
  10. customThe oily substance was recrystallized from 150 ml of methanol

Sources & evidence

ORD record
ord-55513c3f27ac4287b37c14251e4c771e
Source dataset
uspto-grants-2007_07
Patent number
US07250535B2

Reaction notes

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