Thionyl Chloride → ethyl (2Z)-2-amino-2-[2-(2,5-difluorophenyl)acetyl]oxyiminoacetate

HRID 1918560Notes

Reaction equation

HRID 1918560 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[CH2:9][C:10]([OH:12])=[O:11].S(Cl)([Cl:15])=O.[NH2:17]/[C:18](=[N:24]\[OH:25])/[C:19]([O:21][CH2:22][CH3:23])=[O:20].C(N(CC)C(C)C)(C)C>C(Cl)(Cl)Cl.ClCCl>[F:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[CH2:9][C:10]([Cl:15])=[O:12].[NH2:17]/[C:18](=[N:24]\[O:25][C:10](=[O:11])[CH2:9][C:3]1[CH:4]=[C:5]([F:8])[CH:6]=[CH:7][C:2]=1[F:1])/[C:19]([O:21][CH2:22][CH3:23])=[O:20]

Participants

8

Reactant 4

HCID 24386Thionyl ChlorideHCID 81531DiisopropylethylamineHCID 5228232,5-Difluorophenylacetic acidHCID 9614369Ethyl 2-oximinooxamate

Product 2

HCID 27583202,5-Difluorophenylacetyl chlorideHCID 140579266ethyl (2Z)-2-amino-2-[2-(2,5-difluorophenyl)acetyl]oxyiminoacetateYield 89.3%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
-10 °C

Procedure

2-(2,5-difluorophenyl)acetyl chloride was prepared by heating overnight a suspension of 2,5-difluorophenylacetic acid (0.865 g; 3.67 mmol) and thionyl chloride (1.34 mL; 18.15 mmol) in chloroform (30 mL) at 80° C. After evaporation of the solvent and the excess of the thionyl chloride under reduced pressure, the residue was dissolved in dried dichloromethane (10 mL). This solution was added to a suspension of (Z)-ethyl 2-amino-2-(hydroxyimino)acetate (0.500 g; 3.67 mmol) and N,N-diisopropylethylamine (1.03 mL; 5.87 mmol) in dry dichloromethane (20 mL) cooled at −10° C. and stirred for 10 minutes. The mixture was stirred at room temperature for 23 h and poured into a mixture of ice/water. The white precipitate is filtered off and washed with dichloromethane and dried under reduced pressure to afford 0.469 g (45%) of (Z)-ethyl 2-amino-2-(2-(2,5-difluorophenyl)acetoxyimino)acetate as a white solid.

Workup

  1. temperatureby heating overnight
  2. customAfter evaporation of the solvent
  3. dissolutionthe excess of the thionyl chloride under reduced pressure, the residue was dissolved in dried dichloromethane (10 mL)
  4. stirringThe mixture was stirred at room temperature for 23 h
  5. filtrationThe white precipitate is filtered off
  6. washwashed with dichloromethane
  7. customdried under reduced pressure

Sources & evidence

ORD record
ord-946d0e5a846645d1b74471c7724b6d9e
Source dataset
uspto-grants-2013_12
Patent number
US08618138B2

Reaction notes

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