Aldoxime → methyl N-[2-chloro-5-(1-hydroxyiminoethyl)benzyl]carbamate

HRID 2414257Notes

Reaction equation

HRID 2414257 reaction equation
N[C:2]1[CH:3]=[CH:4][C:5]([Cl:14])=[C:6]([CH:13]=1)[CH2:7][NH:8][C:9](=[O:12])[O:10][CH3:11].N([O-])=O.[Na+].C([O-])(=O)C.[Na+].[CH:24](=[N:26][OH:27])[CH3:25]>Cl.S([O-])([O-])(=O)=O.[Cu+2].O.C(OCC)(=O)C.C1(C)C=CC=CC=1>[Cl:14][C:5]1[CH:4]=[CH:3][C:2]([C:24](=[N:26][OH:27])[CH3:25])=[CH:13][C:6]=1[CH2:7][NH:8][C:9](=[O:12])[O:10][CH3:11]

Participants

8

Reactant 4

HCID 7863AldoximeHCID 517045Sodium AcetateHCID 12151321HCID 12151321, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 86641517methyl N-[2-chloro-5-(1-hydroxyiminoethyl)benzyl]carbamateYield 21.9%

Reagents, catalysts & solvents 3

HCID 24462Copper SulfateCatalystHCID 313Hydrochloric AcidSolventHCID 86606854toluene EtOAc waterSolvent

Procedure

10.7 g of methyl N-[5-amino-2-chlorobenzyl]carbamate was dissolved in 33 g of 14% hydrochloric acid, followed by stirring at room temperature for 1 hour. 7 ml of an aqueous solution of 3.8 g of sodium nitrite was dropwise added to the solution with stirring at from 0 to 5° C. The formed diazonium salt was dropwise added to a mixed solvent of water/ethyl acetate/toluene (80 ml/40 ml/40 ml) of 21.7 g of sodium acetate, 2.6 g of copper sulfate and 5.9 g of acetaldoxime with vigorously stirring at from 0 to 5° C. over a period of 15 minutes, followed by stirring at room temperature further for 2 hours. The reaction solution was acidified with hydrochloric acid, extraction with ethyl acetate was carried out, followed by washing with water, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, the obtained crude crystals were washed with a mixed solvent of ether/ethyl acetate to obtain 2.8 g of methyl N-[2-chloro-5-(1-hydroxyiminoethyl)benzyl]carbamate as colorless crystals (m.p. 124-127° C.).

Workup

  1. stirringwith stirring at from 0 to 5° C
  2. stirringwith vigorously stirring at from 0 to 5° C. over a period of 15 minutes
  3. stirringby stirring at room temperature further for 2 hours
  4. extractionThe reaction solution was acidified with hydrochloric acid, extraction with ethyl acetate
  5. washby washing with water
  6. dry with materialthe organic layer was dried over anhydrous magnesium sulfate
  7. distillationThe solvent was distilled off under reduced pressure
  8. customthe obtained crude crystals
  9. washwere washed with a mixed solvent of ether/ethyl acetate

Sources & evidence

ORD record
ord-6a54509fd603433191c5c8ca439370ea
Source dataset
uspto-grants-2004_11
Patent number
US06812229B1

Reaction notes

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