Hydroxyamine hydrochloride → 5435-68-7

HRID 864318Notes

Reaction equation

HRID 864318 reaction equation
Cl.[NH2:2][OH:3].[N+:4]([C:7]1[CH:8]=[C:9]([C:13](=O)[C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH:10]=[CH:11][CH:12]=1)([O-:6])=[O:5]>O.N1C=CC=CC=1>[N+:4]([C:7]1[CH:8]=[C:9](/[C:13](=[N:2]\[OH:3])/[C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH:10]=[CH:11][CH:12]=1)([O-:6])=[O:5]

Participants

5

Reactant 2

HCID 443297Hydroxyamine hydrochlorideHCID 19418714HCID 19418714, compound

Product 1

HCID 63990485435-68-7Yield 16.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1049PyridineSolvent

Procedure

Ethyl (Z)-3-nitro-alpha-hydroxyiminophenylacetate can be obtained in the following manner: a solution of 62 g of hydroxylamine hydrochloride in 200 cm3 of water is added to a solution of 10 g of ethyl 3-nitrophenyl-glyoxylate in 250 cm3 of pyridine and the mixture is brought for 2 hours to a temperature near to 100° C. The reaction mixture is concentrated under reduced pressure (1.2 kPa). The residue is diluted with 250 cm3 of water and extracted with 250 cm3 of ethyl acetate. The organic phase is washed with a 1N aqeuous solution of hydrochloric acid, dried over magnesium sulphate, filtered and evaporated to dryness to give a white solid. This solid is purified by chromatography on a column of diameter 4 cm containing 500 cm3 of silica, eluting with a cyclohexane/ethyl acetate mixture and collecting fractions of 100 cm3. The fractions between 1 and 1.2 liters are combined and concentrated to dryness to give 1.8 g of ethyl (E)-3-nitro-alpha-hydroxyiminophenylacetate in the form of a colorless oil; the fractions between 1.4 and 1.6 liters are combined and concentrated to dryness to give 2.5 g of ethyl (Z)-3-nitro-alpha-hydroxyiminophenylacetate in the form of a solid which is used as such in the subsequent syntheses.

Workup

  1. concentrationThe reaction mixture is concentrated under reduced pressure (1.2 kPa)
  2. additionThe residue is diluted with 250 cm3 of water
  3. extractionextracted with 250 cm3 of ethyl acetate
  4. washThe organic phase is washed with a 1N aqeuous solution of hydrochloric acid
  5. dry with materialdried over magnesium sulphate
  6. filtrationfiltered
  7. customevaporated to dryness
  8. customto give a white solid
  9. customThis solid is purified by chromatography on a column of diameter 4 cm
  10. additioncontaining 500 cm3 of silica
  11. washeluting with a cyclohexane/ethyl acetate mixture
  12. customcollecting fractions of 100 cm3
  13. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-70803ebe3ae644fdb56dbb876c4fec2e
Source dataset
uspto-grants-1996_10
Patent number
US05563136

Reaction notes

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