Methanol → 1,1-Diphenylethylene

HRID 2287293Notes

Reaction equation

HRID 2287293 reaction equation
[C:1]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)(=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:15]1COCC1.[Cl-].[NH4+].CO>C1(C)C=CC(S(O)(=O)=O)=CC=1.C1(C)C=CC=CC=1>[C:2]1([C:1]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[CH2:15])[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 887MethanolHCID 3102Benzophenone2×HCID 8028TetrahydrofuranHCID 25517Ammonium Chloride

Product 1

HCID 107401,1-Diphenylethylene

Reagents, catalysts & solvents 2

HCID 6101p-Toluenesulfonic acidCatalystHCID 1140TolueneSolvent2×

Procedure

To this reaction mixture was added dropwise a liquid mixture of 182.2 g (1.1 mol) of benzophenone (8a; Ar=R=Ph) and 365 ml of dry THF at 35 to 40° C. over a period of 30 minutes. This mixture was stirred at that temperature for 2 hours and for further 13 hours to complete the reaction. The reaction mixture was poured into 1.4 kg of cooled 10% aqueous ammonium chloride solution with cooling with ice. This mixture was stirred for 30 minutes, allowed to stand, and then subjected to liquid separation, followed by washing with aqueous common salt solution, drying with magnesium sulfate, and concentration to obtain 200.2 g of a crude carbinol (theoretical yield based on the benzophenone, 98.6%). Into a 1-liter reaction flask were introduced 200.2 g of the crude carbinol, 400 ml of toluene, and 1 g of p-toluenesulfonic acid (PTSA). Azeotropic dehydration was conducted for 2 hours with toluene refluxing (94-116° C.). After cooling, this reaction mixture was washed with water, with 2% aqueous soda ash solution, and then with water, dried with magnesium sulfate, and concentrated to obtain 190.1 g of crude 1,1-diphenylethylene. This crude reaction product was distilled with a Claisen flask equipped with a vigreux to obtain 174.1 g of 1,1-diphenylethylene (9a; Ar=R=Ph). b.p., 103° C./1 mmHg.

Workup

  1. additionTo this reaction mixture was added dropwise
  2. customthe reaction
  3. temperaturewith cooling with ice
  4. stirringThis mixture was stirred for 30 minutes
  5. customsubjected to liquid separation
  6. washby washing with aqueous common salt solution
  7. dry with materialdrying with magnesium sulfate, and concentration
  8. customto obtain 200.2 g of a crude carbinol (
  9. customtheoretical yield
  10. customInto a 1-liter reaction flask
  11. temperatureAfter cooling
  12. washthis reaction mixture was washed with water, with 2% aqueous soda ash solution
  13. dry with materialwith water, dried with magnesium sulfate
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-ca1fbbbdcf9f4effa1d5946503c21736
Source dataset
uspto-grants-2000_07
Patent number
US06083651

Reaction notes

Loading…