Dimethyl Sulfide → 2-tert-Butyl-2-[(4-chlorophenoxy)methyl]oxirane

HRID 1165705Notes

Reaction equation

HRID 1165705 reaction equation
CSC.S([O:9][CH3:10])(OC)(=O)=O.C[O-].[Na+].[Cl:14][C:15]1[CH:28]=[CH:27][C:18]([O:19][CH2:20][C:21](=O)[C:22]([CH3:25])([CH3:24])[CH3:23])=[CH:17][CH:16]=1>C(#N)C>[Cl:14][C:15]1[CH:28]=[CH:27][C:18]([O:19][CH2:20][C:21]2([C:22]([CH3:23])([CH3:24])[CH3:25])[CH2:10][O:9]2)=[CH:17][CH:16]=1

Participants

6

Reactant 4

HCID 1068Dimethyl SulfideHCID 6497Dimethyl SulfateHCID 905182-Butanone, 1-(4-chlorophenoxy)-3,3-dimethyl-HCID 10942334Sodium Methoxide

Product 1

HCID 127636212-tert-Butyl-2-[(4-chlorophenoxy)methyl]oxiraneYield 84%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent3×

Procedure

A solution of 162 ml (2.2 mols) of dimethyl sulphide in 400 ml of absolute acetonitrile was added to a solution of 189 ml (2.0 mols) of dimethyl sulphate in 1,200 ml of absolute acetonitrile at room temperature. The reaction mixture was stirred overnight at room temperature. 118.8 g (2.2 mols) of sodium methylate were thereafter added to the mixture. The mixture was stirred for 30 minutes, and a solution of 272 g (1.2 mols) of 1-(4-chlorophenoxy)-3,3-dimethyl-butan-2-one in 600 ml of absolute acetonitrile was added dropwise to it during the course of 30 minutes. The reaction mixture was further stirred overnight and was then concentrated, and the residue was partitioned between water and ethyl acetate. The organic phase was separated off, washed twice with water and once with saturated sodium chloride solution, dried over sodium sulphate and concentrated, and the residue was distilled in vacuo. 242.4 g (84% of theory) of 2-(4-chlorophenoxy-methyl)-2tert.-butyl-oxirane of boiling point 115°-122° C./0.003 mm Hg and melting point 50°-52° C. were obtained.

Workup

  1. stirringThe mixture was stirred for 30 minutes
  2. waitThe reaction mixture was further stirred overnight
  3. concentrationwas then concentrated
  4. customthe residue was partitioned between water and ethyl acetate
  5. customThe organic phase was separated off
  6. washwashed twice with water and once with saturated sodium chloride solution
  7. dry with materialdried over sodium sulphate
  8. concentrationconcentrated
  9. distillationthe residue was distilled in vacuo

Sources & evidence

ORD record
ord-720681b86c394c51889ee23ba0742d44
Source dataset
uspto-grants-1990_03
Patent number
US04911750

Reaction notes

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