Pyridine → 4-Bromo-3-nitrobenzaldoxime

HRID 1958651Notes

Reaction equation

HRID 1958651 reaction equation
[Br:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].N1C=CC=CC=1.Cl.[NH2:20][OH:21]>CO.C(OCC)(=O)C.C(=O)([O-])O.[Na+]>[Br:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[N:20][OH:21])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11]

Participants

7

Reactant 3

HCID 1049PyridineHCID 443297Hydroxyamine hydrochlorideHCID 8087924-Bromo-3-nitrobenzaldehyde

Product 1

HCID 731663754-Bromo-3-nitrobenzaldoximeYield 67%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 8857Ethyl AcetateSolventHCID 516892Sodium BicarbonateSolvent

Procedure

To a solution of 4-bromo-3-nitro-benzaldehyde (commercially available) (10 g, 43.5 mmol) in methanol (28 ml) under a nitrogen atmosphere was added pyridine (7.74 g, 97.8 mmol) and hydroxylamine hydrochloride (6.04 g, 86.94 mmol). The reaction mixture was stirred at ambient temperature for 16 hours. The reaction mixture was diluted with a mixture of ethyl acetate and aqueous sodium hydrogen carbonate (saturated). The phases were separated and the aqueous phase was extracted twice with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 1:3) to give 4-bromo-3-nitro-benzaldehyde oxime (5.34 g, 67% yield). 1H-NMR (CDCl3, 400 MHz): 8.11 (s, 1H), 8.05 (d, 1H), 7.75 (d, 1H), 7.62 (m, 2H).

Workup

  1. customThe phases were separated
  2. extractionthe aqueous phase was extracted twice with ethyl acetate
  3. dry with materialThe combined organic phases were dried over sodium sulfate
  4. concentrationconcentrated
  5. customThe residue was purified by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 1:3)

Sources & evidence

ORD record
ord-893f7ef6452447ee9f5b1f181c905e23
Source dataset
uspto-grants-2013_04
Patent number
US08410145B2

Reaction notes

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