Sulfuric Acid → Di-tert-amylcyclohexylphosphine

HRID 1297573Notes

Reaction equation

HRID 1297573 reaction equation
[C:1]([P:6](Cl)[C:7]([CH2:10][CH3:11])([CH3:9])[CH3:8])([CH2:4][CH3:5])([CH3:3])[CH3:2].[CH:13]1(Cl)[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1.[Mg].S(=O)(=O)(O)O>O1CCCC1.[Cu]Cl.C1(C)C=CC=CC=1>[C:1]([P:6]([C:7]([CH2:10][CH3:11])([CH3:9])[CH3:8])[CH:13]1[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1)([CH2:4][CH3:5])([CH3:3])[CH3:2]

Participants

8

Reactant 4

HCID 1118Sulfuric AcidHCID 10952ChlorocyclohexaneHCID 5462224MagnesiumHCID 23032008Di-tert-amylphosphinous chloride

Product 1

HCID 22925481Di-tert-amylcyclohexylphosphineYield 96.7%

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

In a 300 ml four-necked flask thoroughly purged with nitrogen, 10.4 g (0.05 mol) of di-tert-amylphosphinous chloride, 0.10 g (0.001 mol (corresponding to 2% by mol)) of copper(I) chloride and 30 ml of tetrahydrofuran were placed. To the contents of the flask, a Grignard reagent solution previously prepared from 8.3 g (0.060 mol) of cyclohexyl chloride and 2.0 g (0.08 mol) of metallic magnesium in 50 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 a temperature of 35° C. to 40° C. for 6 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 and a low-boiling component were distilled off under reduced pressure to obtain 12.4 g (purity: 94.9%) of the aimed di-tert-amylcyclohexylphosphine 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 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 and a low-boiling component were distilled off under reduced pressure

Sources & evidence

ORD record
ord-b131fcae618b4d9db60a8b5908619afd
Source dataset
uspto-grants-2007_07
Patent number
US07250535B2

Reaction notes

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