Dimethyl Sulfide → 2-[2-(4-Chlorophenoxy)propan-2-yl]-2-(4-chlorophenyl)oxirane

HRID 1638374Notes

Reaction equation

HRID 1638374 reaction equation
S(OC)(O[CH3:5])(=O)=O.CSC.[Cl:11][C:12]1[CH:30]=[CH:29][C:15]([O:16][C:17]([C:20]([C:22]2[CH:27]=[CH:26][C:25]([Cl:28])=[CH:24][CH:23]=2)=[O:21])([CH3:19])[CH3:18])=[CH:14][CH:13]=1.C[O-].[Na+]>C(#N)C>[Cl:28][C:25]1[CH:26]=[CH:27][C:22]([C:20]2([C:17]([O:16][C:15]3[CH:14]=[CH:13][C:12]([Cl:11])=[CH:30][CH:29]=3)([CH3:19])[CH3:18])[CH2:5][O:21]2)=[CH:23][CH:24]=1

Participants

6

Reactant 4

HCID 1068Dimethyl SulfideHCID 6497Dimethyl SulfateHCID 10942334Sodium MethoxideHCID 198424902-(4-Chlorophenoxy)-1-(4-chlorophenyl)-2-methylpropan-1-one

Product 1

HCID 198424852-[2-(4-Chlorophenoxy)propan-2-yl]-2-(4-chlorophenyl)oxiraneYield 76%

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 at room temperature for 5 days. A solution of 87 g of 4-chlorophenyl 2-(p-chlorophenoxy)-prop-2-yl 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 introduced at the same temperature, and the mixture is stirred for a further 12 hours and then concentrated. 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. 49 g (76% of theory) of crude 2-(4 chlorophenyl)-2-[2-(p-chlorophenoxy)-prop-2-yl]-oxirane are obtained, and this compound is directly reacted further. ##STR158## 52 g (0.3982 mol) of p-chlorophenol and 55 g (0.3982 mol) of potassium carbonate in 400 ml of toluene are heated under reflux for 2 hours in a water separator. The mixture is cooled to 40° C., and a solution of 2-bromo-prop-2-yl 4-chlorophenyl ketone in 170 ml of toluene is added dropwise. This reaction mixture is stirred for a further 5 hours at 100° C. and then cooled, water is added and the organic phase is separated off. This is washed with dilute sodium hydroxide solution and water, dried over sodium sulphate and concentrated. 87 g (85% of theory) of crude 4-chlorophenyl 2-(p-chlorophenoxy)-prop-2-yl ketone are obtained, and this compound is directly reacted further. ##STR159## 1 ml of hydrogen bromide/glacial acetic acid is added to 65.5 g (0.36 mol) of 4-chlorophenyl isopropyl ketone in 200 ml of chloroform, and 57.5 g (0.36 mol) of bromine are then added dropwise at 30° C. The mixture is stirred for a further 30 minutes at room temperature, and thereafter concentrated in vacuo. 86.6 g (92% of theory) of crude 2-bromo-prop-2-yl 4-chlorophenyl ketone are obtained, and this compound is directly reacted further.

Workup

  1. concentrationconcentrated
  2. stirringThe residue is stirred overnight with a mixture of 200 ml of ethyl acetate and 150 ml of water
  3. customThe organic phase is separated off
  4. dry with materialdried over sodium sulphate
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-ec97c6d869fc416d8f707c2fca52beae
Source dataset
uspto-grants-1989_11
Patent number
US04879385

Reaction notes

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