Sodium Methoxide → 2-t-Butoxycarbonylmethoxyimino-2-(3-chloro-4-hydroxyphenyl)acetic acid

HRID 463840Notes

Reaction equation

HRID 463840 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:9](=O)[C:10]([OH:12])=[O:11])[CH:5]=[CH:6][C:7]=1[OH:8].[C:14]([O:18][C:19]([CH2:21][O:22][NH2:23])=[O:20])([CH3:17])([CH3:16])[CH3:15].C[O-].[Na+]>CO>[C:14]([O:18][C:19]([CH2:21][O:22][N:23]=[C:9]([C:4]1[CH:5]=[CH:6][C:7]([OH:8])=[C:2]([Cl:1])[CH:3]=1)[C:10]([OH:12])=[O:11])=[O:20])([CH3:17])([CH3:16])[CH3:15]

Participants

5

Reactant 3

HCID 10942334Sodium MethoxideHCID 12919121tert-Butyl (aminooxy)acetateHCID 129611392-(3-Chloro-4-hydroxyphenyl)-2-oxoacetic acid

Product 1

HCID 1361491122-t-Butoxycarbonylmethoxyimino-2-(3-chloro-4-hydroxyphenyl)acetic acidYield 79.1%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

A mixture of 2-(3-chloro-4-hydroxyphenyl)glyoxylic acid (2.0 g.), O-t-butoxycarbonylmethylhydroxylamine (1.62 g.) and methanol (20 ml.) was adjusted to pH 5 to 6 by adding an 1N methanol solution of sodium methoxide and stirred for 3 hours at ambient temperature. The reaction mixture was concentrated to dryness under reduced pressure and the residue was dissolved in an 1N aqueous solution of sodium hydroxide to adjust to pH 7.0. The aqueous solution was washed with ether, adjusted to pH 2.0 with 10% hydrochloric acid under ice-cooling and extracted with ether. The extract was washed with water and dried over magnesium sulfate. The solution was concentrated to dryness under reduced pressure to give crystals of 2-t-butoxycarbonylmethoxyimino-2-(3-chloro-4-hydroxyphenyl)acetic acid (syn isomer) (2.6 g.), mp 116° to 118° C. (dec.).

Workup

  1. concentrationThe reaction mixture was concentrated to dryness under reduced pressure
  2. dissolutionthe residue was dissolved in an 1N aqueous solution of sodium hydroxide
  3. washThe aqueous solution was washed with ether
  4. temperaturecooling
  5. extractionextracted with ether
  6. washThe extract was washed with water
  7. dry with materialdried over magnesium sulfate
  8. concentrationThe solution was concentrated to dryness under reduced pressure

Sources & evidence

ORD record
ord-2e74ef3c846a4494aac5618916fa4ebe
Source dataset
uspto-grants-1985_10
Patent number
US04544653

Reaction notes

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