Ethyl Thioglycolate → (2,4-Dichloro-phenoxymethylsulfanyl)-acetic acid

HRID 390789Notes

Reaction equation

HRID 390789 reaction equation
C([O:3][C:4](=[O:7])[CH2:5][SH:6])C.[H-].[Na+].[Cl:10][C:11]1[CH:16]=[C:15]([Cl:17])[CH:14]=[CH:13][C:12]=1[O:18][CH2:19]Cl>CN(C=O)C>[Cl:10][C:11]1[CH:16]=[C:15]([Cl:17])[CH:14]=[CH:13][C:12]=1[O:18][CH2:19][S:6][CH2:5][C:4]([OH:3])=[O:7]

Participants

5

Reactant 3

HCID 12185Ethyl ThioglycolateHCID 24758Sodium hydrideHCID 12353529Chloromethyl 2,4-dichlorophenyl ether

Product 1

HCID 68579334(2,4-Dichloro-phenoxymethylsulfanyl)-acetic acidYield 57%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of mercapto-acetic acid ethyl ester (2.4 g, 19.86 mmol) in dry DMF (20 mL) was added NaH (556 mg, 23.27 mmol, 60% in mineral oil). The mixture was stirred for 30 min. at room temperature followed by dropwise addition of 2,4-dichloro-1-chloromethoxy-benzene (3.5 g, 16.55 mmol), stirring was continued for 16 hrs at ambient temperature. The reaction was quenched by addition of water (50 mL) and extracted with diethyl ether (2×50 mL). The combined organic phases were washed with saturated aq. ammonium chloride (50 mL), dried (Na2SO4), filtered and evaporated in vacuo. The residue was dissolved in EtOH (20 mL) and to this solution was added aq. 32% NaOH (1 mL) and water (10 mL). Stirring was continued for 16 hrs at room temperature. The volatiles were evaporated in vacuo, water (20 mL) was added followed by washing with diethyl ether (20 mL). The aqueous phase was acidified to pH˜1 with conc. HCl followed by extraction with diethyl ether (2×25 mL). The combined organic phases were dried (Na2SO4), filtered and the solvent evaporated in vacuo affording 2.5 g (57%) of crude (2,4-dichloro-phenoxymethylsulfanyl)-acetic acid as a solid.

Workup

  1. stirringstirring
  2. waitwas continued for 16 hrs at ambient temperature
  3. customThe reaction was quenched by addition of water (50 mL)
  4. extractionextracted with diethyl ether (2×50 mL)
  5. washThe combined organic phases were washed with saturated aq. ammonium chloride (50 mL)
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. customevaporated in vacuo
  9. dissolutionThe residue was dissolved in EtOH (20 mL) and to this solution
  10. additionwas added aq. 32% NaOH (1 mL) and water (10 mL)
  11. stirringStirring
  12. waitwas continued for 16 hrs at room temperature
  13. customThe volatiles were evaporated in vacuo, water (20 mL)
  14. additionwas added
  15. washby washing with diethyl ether (20 mL)
  16. extractionfollowed by extraction with diethyl ether (2×25 mL)
  17. dry with materialThe combined organic phases were dried (Na2SO4)
  18. filtrationfiltered
  19. customthe solvent evaporated in vacuo

Sources & evidence

ORD record
ord-a453e45a758147478180b7c069703a00
Source dataset
uspto-grants-2013_02
Patent number
US08383683B2

Reaction notes

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