Water → Ethyl (4-mercapto-2-methylphenoxy)acetate

HRID 860636Notes

Reaction equation

HRID 860636 reaction equation
Cl[Si](Cl)(C)C.[CH2:6]([O:8][C:9](=[O:23])[CH2:10][O:11][C:12]1[CH:17]=[CH:16][C:15]([S:18](Cl)(=O)=O)=[CH:14][C:13]=1[CH3:22])[CH3:7].CN1CCN(C)C1=O.O>ClC(Cl)C.ClCCCl.[Zn]>[CH2:6]([O:8][C:9](=[O:23])[CH2:10][O:11][C:12]1[CH:17]=[CH:16][C:15]([SH:18])=[CH:14][C:13]=1[CH3:22])[CH3:7]

Participants

8

Reactant 4

HCID 962WaterHCID 6398DichlorodimethylsilaneHCID 66611,3-Dimethyl-2-imidazolidinoneHCID 11415129Ethyl 4-chlorosulfonyl-2-methylphenoxyacetate

Product 1

HCID 16641178Ethyl (4-mercapto-2-methylphenoxy)acetate

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 111,2-DichloroethaneSolventHCID 63651,1-DichloroethaneSolvent

Conditions

Temperature
52 °C

Procedure

This compound can also be made by the following procedure: To a stirred suspension of Zn powder (10 μm, 78.16 g, 1.2 mol) and dichlorodimethyl silane (154.30 g, 145.02 mL, 1.2 mol) in 500 mL of dichloroethane is added a solution of (4-chlorosulfonyl-2-methyl-phenoxy)-acetic acid ethyl ester (100 g, 0.34 mol) and 1,3-dimethylimidazolidin-2-one (116.98 g, 112.05 mL, 1.02 mol) in 1 L of DCE. Addition is at a rate so as to maintain the internal temperature at ˜52° C., cooling with chilled water as necessary. After addition is complete, the mixture is heated at 75° C. for 1 hour. It is then cooled to room temperature, filtered and concentrated iv. Add MTBE, washed twice with saturated LiCl solution concentrate iv again. Take up the residue in CH3CN, ish with hexane (4×) and concentrate iv to yield a biphasic mixture. Let stand in a separatory funnel and separate layers, keeping the bottom layer for product. Filtration through a plug of silica gel (1 Kg, 25% EtOAc/hexane) and subsequent concentration yielded 61 g (79%) of a clear, colorless oil.

Workup

  1. additionAddition
  2. additionAfter addition
  3. temperaturethe mixture is heated at 75° C. for 1 hour
  4. temperatureIt is then cooled to room temperature
  5. filtrationfiltered
  6. concentrationconcentrated iv
  7. washAdd MTBE, washed twice with saturated LiCl solution
  8. concentrationconcentrate iv again
  9. concentrationish with hexane (4×) and concentrate iv
  10. customto yield a biphasic mixture
  11. customseparate layers
  12. filtrationFiltration
  13. concentrationthrough a plug of silica gel (1 Kg, 25% EtOAc/hexane) and subsequent concentration
  14. customyielded 61 g (79%) of a clear, colorless oil

Sources & evidence

ORD record
ord-2872b492a9574bfa98b5e742feb526f7
Source dataset
uspto-grants-2006_12
Patent number
US07153878B2

Reaction notes

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