Dimethyl Sulfide → 2-(4-Chlorophenyl)-2-[1-(4-chlorophenyl)-2-methylpropan-2-yl]oxirane

HRID 1638371Notes

Reaction equation

HRID 1638371 reaction equation
S([O:6][CH3:7])(OC)(=O)=O.CSC.[Cl:11][C:12]1[CH:17]=[CH:16][C:15]([CH2:18][C:19]([C:22]([C:24]2[CH:29]=[CH:28][C:27]([Cl:30])=[CH:26][CH:25]=2)=O)([CH3:21])[CH3:20])=[CH:14][CH:13]=1.C[O-].[Na+]>C(#N)C>[Cl:11][C:12]1[CH:13]=[CH:14][C:15]([C:18]2([C:19]([CH3:21])([CH3:20])[CH2:22][C:24]3[CH:25]=[CH:26][C:27]([Cl:30])=[CH:28][CH:29]=3)[CH2:7][O:6]2)=[CH:16][CH:17]=1

Participants

6

Reactant 4

HCID 1068Dimethyl SulfideHCID 6497Dimethyl SulfateHCID 10942334Sodium MethoxideHCID 132174061,3-Bis(4-chlorophenyl)-2,2-dimethylpropan-1-one

Product 1

HCID 132174072-(4-Chlorophenyl)-2-[1-(4-chlorophenyl)-2-methylpropan-2-yl]oxiraneYield 85.2%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

A solution of 59.2 g (0.47 mol) of dimethyl sulphate and 32 g (0.517 mol) of dimethyl sulphide in 270 ml of acetonitrile is stirred for 5 days at room temperature. A solution of 81.5 g (0.2655 mol) of 4-chlorophenyl 4-chlorophenyl-tert.-butyl ketone in 80 ml of acetonitrile is then added dropwise at 20° to 25° C., in the course of approx. 2 hours 28.7 g (0.53 mol) of sodium methylate are added at the same temperature. The total reaction mixture is stirred for 12 hours and thereafter concentrated in vacuo. The residue is stirred overnight with a mixture of 200 ml of ethyl acetate and 150 ml of water. The organic phase is separated off, dried over sodium sulphate and concentrated in vacuo. 72.6 g (85.2% of theory) of crude 2-(4-chlorophenyl)-2-(4-chlorophenyl-tert.-butyl)-oxirane are obtained and this compound is directly reacted further. ##STR155## 85 g (0.466 mol) of 4-chlorophenyl isopropyl ketone, 31.3 g (0.56 mol) of potassium hydroxide and 5 g of tetrabutylammonium bromide in 120 ml of toluene are heated to the reflux temperature, and a solution of 75 g (0.466 mol) of 4-chlorobenzyl chloride in 60 ml of toluene is added dropwise. The reaction mixture is stirred under reflux for a further 12 hours, cooled, and washed with water, and the organic phase is dried over sodium sulphate and concentrated in vacuo. 81.5 g (60% of theory) of 4-chlorophenyl 4-chlorophenyl-tert.-butyl ketone of refractive index nD20 =1,5711 are obtained.

Workup

  1. additionare added at the same temperature
  2. customThe total reaction mixture
  3. concentrationconcentrated in vacuo
  4. stirringThe residue is stirred overnight with a mixture of 200 ml of ethyl acetate and 150 ml of water
  5. customThe organic phase is separated off
  6. dry with materialdried over sodium sulphate
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-a1bbe328f04e41438d637cf4605b2581
Source dataset
uspto-grants-1989_11
Patent number
US04879385

Reaction notes

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