Hydroxylamine → Methyl 5-[amino(hydroxyimino)methyl]-2-fluorobenzoate

HRID 219841Notes

Reaction equation

HRID 219841 reaction equation
[C:1]([C:3]1[CH:4]=[CH:5][C:6]([F:13])=[C:7]([CH:12]=1)[C:8]([O:10][CH3:11])=[O:9])#[N:2].[NH2:14][OH:15].O.CCOCC>CCO>[NH2:2][C:1](=[N:14][OH:15])[C:3]1[CH:4]=[CH:5][C:6]([F:13])=[C:7]([CH:12]=1)[C:8]([O:10][CH3:11])=[O:9]

Participants

6

Reactant 4

HCID 787HydroxylamineHCID 962WaterHCID 3283Diethyl EtherHCID 55265274Methyl 5-cyano-2-fluorobenzoate

Product 1

HCID 72307478Methyl 5-[amino(hydroxyimino)methyl]-2-fluorobenzoateYield 98%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a suspension of methyl 5-cyano-2-fluorobenzoate, obtained in step 2 (804.60 mg; 4.49 mmol; 1 eq.) in EtOH (8.05 mL) was added hydroxylamine (50% in water) (1.35 mL; 22.46 mmol; 5 eq.). The reaction mixture was stirred at RT for 1 h40. Water (25 mL) was added followed by Et2O (25 mL). Aqueous layer was extracted with Et2O (2×25 mL). The combined organic layers were then washed with NaCl sat. solution and dried over magnesium sulfate, filtered and concentrated to afford the title compound as a yellow solid (931 mg; 98%). 1H NMR (DMSO-d6, 300 MHz) δ 9.78 (br s, 1H), 8.21 (dd, J=7.1, 2.4 Hz, 1H), 7.96-7.91 (m, 1H), 7.38 (dd, J=10.8, 8.8 Hz, 1H), 5.97 (br s, 2H), 3.87 (s, 3H). HPLC (Method A), Rt 0.92 min (purity: 90.6%). LC/MS (Method B): 211.1 (M−H)−; 213.0 (M+H)+.

Workup

  1. extractionAqueous layer was extracted with Et2O (2×25 mL)
  2. washThe combined organic layers were then washed with NaCl sat. solution
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-65828ec8a3a54301816d3ece7f6662e7
Source dataset
uspto-grants-2012_06
Patent number
US08202865B2

Reaction notes

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