1-Chloro-4-(chloromethyl)benzene → 1,3-Bis(4-chlorophenyl)-2,2-dimethylpropan-1-one

HRID 1638372Notes

Reaction equation

HRID 1638372 reaction equation
[CH:1]([C:4]([C:6]1[CH:11]=[CH:10][C:9]([Cl:12])=[CH:8][CH:7]=1)=[O:5])([CH3:3])[CH3:2].[OH-].[K+].[Cl:15][C:16]1[CH:23]=[CH:22][C:19]([CH2:20]Cl)=[CH:18][CH:17]=1>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1>[Cl:15][C:16]1[CH:23]=[CH:22][C:19]([CH2:20][C:1]([C:4]([C:6]2[CH:7]=[CH:8][C:9]([Cl:12])=[CH:10][CH:11]=2)=[O:5])([CH3:3])[CH3:2])=[CH:18][CH:17]=1

Participants

6

Reactant 3

HCID 77231-Chloro-4-(chloromethyl)benzeneHCID 14797Potassium HydroxideHCID 728651-(4-Chlorophenyl)-2-methylpropan-1-one

Product 1

HCID 132174061,3-Bis(4-chlorophenyl)-2,2-dimethylpropan-1-oneYield 60%

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 1140TolueneSolvent2×

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. customthis compound is directly reacted further
  2. temperatureunder reflux for a further 12 hours
  3. temperaturecooled
  4. washwashed with water
  5. dry with materialthe organic phase is dried over sodium sulphate
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-62f9d9d94db5448db52c8d5a3b69afc3
Source dataset
uspto-grants-1989_11
Patent number
US04879385

Reaction notes

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