Hydrazine hydrate (1:1) → Methyl 3-amino-2-fluorobenzoate

HRID 1670920Notes

Reaction equation

HRID 1670920 reaction equation
[F:1][C:2]1[C:11]([N+:12]([O-])=O)=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].O.NN>C1COCC1.CO.[Ni]>[NH2:12][C:11]1[C:2]([F:1])=[C:3]([CH:8]=[CH:9][CH:10]=1)[C:4]([O:6][CH3:7])=[O:5]

Participants

6

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 13470961Methyl 2-fluoro-3-nitrobenzoate

Product 1

HCID 46311080Methyl 3-amino-2-fluorobenzoate

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of methyl 2-fluoro-3-nitrobenzoate (78 g) in THF (400 ml) and methanol (100 ml) was added Raney Ni (40 g), the mixture was heated to 70° C., and then 25 ml of hydrazine hydrate (N2H4.H2O, 85%) was added dropwise. The reaction was monitored by TLC, when the starting material was totally consumed the addition of hydrazine was stop. The mixture was cooled to rt and filtered, the filtrate was concentrated under vacuum to leave a brown oil, which was purified by chromatography (SiO2, 300-400 mesh, PE: EtOAc=11:2) to afford the title compound was obtained as a yellow oil (45 g, 68%). 1H NMR (300 MHz, DMSO) δ ppm 6.96 (m, 3H), 5.36 (s, 2H), 3.81 (s, 3H).

Workup

  1. customwas totally consumed
  2. additionthe addition of hydrazine
  3. temperatureThe mixture was cooled to rt
  4. filtrationfiltered
  5. concentrationthe filtrate was concentrated under vacuum
  6. customto leave a brown oil, which
  7. customwas purified by chromatography (SiO2, 300-400 mesh, PE: EtOAc=11:2)

Sources & evidence

ORD record
ord-f0e615bbddfc4378985a100743aeea8b
Source dataset
uspto-grants-2011_08
Patent number
US07994185B2

Reaction notes

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