Ethyl 4-thiomethylbenzoylformate → Hydroxyimino-(4-methylsulfanyl-phenyl)-acetic acid ethyl ester

HRID 1358158Notes

Reaction equation

HRID 1358158 reaction equation
[CH2:1]([O:3][C:4](=[O:15])[C:5]([C:7]1[CH:12]=[CH:11][C:10]([S:13][CH3:14])=[CH:9][CH:8]=1)=O)[CH3:2].Cl.[OH:17][NH3+:18]>N1C=CC=CC=1.O.C(OCC)(=O)C>[CH2:1]([O:3][C:4](=[O:15])[C:5](=[N:18][OH:17])[C:7]1[CH:12]=[CH:11][C:10]([S:13][CH3:14])=[CH:9][CH:8]=1)[CH3:2]

Participants

6

Reactant 2

HCID 2758911Ethyl 4-thiomethylbenzoylformateHCID 22029257Hydroxyammonium hydrochloride

Product 1

HCID 86759070Hydroxyimino-(4-methylsulfanyl-phenyl)-acetic acid ethyl ester

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1049PyridineSolventHCID 8857Ethyl AcetateSolvent

Procedure

22.4 g (0.1 mol) of (4-Methylsulfanyl-phenyl)-oxo-acetic acid ethyl ester and 7.6 g (0.1 mol) of hydroxylammonium hydrochloride are dissolved in 180 ml of pyridine and the mixture is stirred at room temperature for 16 hours. The yellowish solution is diluted with water and ethyl acetate, the organic phase separated and the aqueous phase extracted several times with ethyl acetate. The combined organic extracts are washed with diluted hydrogen chloride and water and the solvent is evaporated. 24 g (100%) of crude hydroxyimino-(4-methylsulfanyl-phenyl)-acetic acid ethyl ester (66:34 mixture of the E and Z-isomers) are thus obtained and used in the next step without further purification. The structure is confirmed by the 1H-NMR spectrum (in CDCl3). δ[ppm]: 7.46 (d,2H), 7.19 (d,2H), 4.44 (E) and 4,32 (Z) (two d,2H) 2.47 (Z) and 2.46 (E) (s,3H) 1.37 (E) and 1.28 (Z) (t,3H).

Workup

  1. customthe organic phase separated
  2. extractionthe aqueous phase extracted several times with ethyl acetate
  3. washThe combined organic extracts are washed with diluted hydrogen chloride and water
  4. customthe solvent is evaporated
  5. addition24 g (100%) of crude hydroxyimino-(4-methylsulfanyl-phenyl)-acetic acid ethyl ester (66:34 mixture of the E and Z-isomers)
  6. customare thus obtained
  7. customused in the next step without further purification

Sources & evidence

ORD record
ord-483b8f347ab3438886084192823a267a
Source dataset
uspto-grants-2003_07
Patent number
US06596445B1

Reaction notes

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