Sulfuryl chloride → 4-Chloro-2-methoxycarbonylmethoxyimino-3-oxobutyric acid

HRID 1154270Notes

Reaction equation

HRID 1154270 reaction equation
[CH3:1][O:2][C:3]([CH2:5][O:6][N:7]=[C:8]([C:16](=[O:18])[CH3:17])[C:9]([O:11]C(C)(C)C)=[O:10])=[O:4].S(Cl)([Cl:22])(=O)=O>C(O)(=O)C>[Cl:22][CH2:17][C:16](=[O:18])[C:8](=[N:7][O:6][CH2:5][C:3]([O:2][CH3:1])=[O:4])[C:9]([OH:11])=[O:10]

Participants

4

Reactant 2

HCID 24648Sulfuryl chlorideHCID 53440798tert-Butyl 2-[(2-methoxy-2-oxoethoxy)imino]-3-oxobutanoate

Product 1

HCID 248204364-Chloro-2-methoxycarbonylmethoxyimino-3-oxobutyric acid

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To a solution of tert-butyl 2-methoxycarbonylmethoxyimino-3-oxobutyrate (syn isomer) (51.9 g) in glacial acetic acid (52 ml) was slowly added sulfuryl chloride (72.2 ml) at 40° C. with stirring. The reaction mixture was stirred at the same temperature for an hour. The resultant solution was concentrated under reduced pressure and the residual oil was dissolved in ethyl acetate (300 ml). The ethyl acetate layer was washed with 10% hydrochloric acid once and washed with a saturated aqueous solution of sodium chloride four times. The separated organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The residual oil was diluted with n-hexane (100 ml) and evaporated under reduced pressure. The white crystalline precipitates were washed with diisopropyl ether (100 ml). The precipitates were collected by filtration, dried under reduced pressure to give crystalline 4-chloro-2-methoxycarbonylmethoxyimino-3-oxobutyric acid (syn isomer) (13.4 g), mp. 127° to 128.5° C.

Workup

  1. customat 40° C.
  2. stirringThe reaction mixture was stirred at the same temperature for an hour
  3. concentrationThe resultant solution was concentrated under reduced pressure
  4. dissolutionthe residual oil was dissolved in ethyl acetate (300 ml)
  5. washThe ethyl acetate layer was washed with 10% hydrochloric acid once
  6. washwashed with a saturated aqueous solution of sodium chloride four times
  7. dry with materialThe separated organic layer was dried over magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. additionThe residual oil was diluted with n-hexane (100 ml)
  10. customevaporated under reduced pressure
  11. customThe white crystalline precipitates
  12. washwere washed with diisopropyl ether (100 ml)
  13. filtrationThe precipitates were collected by filtration
  14. customdried under reduced pressure

Sources & evidence

ORD record
ord-a42936b0550c4fe3903dff9c16bced8e
Source dataset
uspto-grants-1984_12
Patent number
US04487927

Reaction notes

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