Acetic Acid → Methyl 3-amino-5-fluoro-2-hydroxybenzoate

HRID 415169Notes

Reaction equation

HRID 415169 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([N+:13]([O-])=O)[C:5]([OH:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].C(O)(=O)C.[H][H]>C(OCC)(=O)C.[Pd]>[NH2:13][C:4]1[C:5]([OH:12])=[C:6]([CH:11]=[C:2]([F:1])[CH:3]=1)[C:7]([O:9][CH3:10])=[O:8]

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 57336604Methyl 5-fluoro-2-hydroxy-3-nitrobenzoateHCID 178418361HCID 178418361, compound

Product 1

HCID 66620434Methyl 3-amino-5-fluoro-2-hydroxybenzoateYield 101%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A suspension of methyl 5-fluoro-2-hydroxy-3-nitrobenzoate (2.3 g, 10.7 mmol), acetic acid (2 mL) and 10% Pd/C (0.23 g) in ethyl acetate (50 mL) was stirred at 25° C. over 1 atm hydrogen for 4 hr. The mixture was filtered and the filtrate was concentrated to give crude product. The crude product was purified by chromatography (silica gel, petroleum ether/ethyl acetate=100:1 to 20:1) to give methyl 3-amino-5-fluoro-2-hydroxybenzoate (2.0 g, yield 100%) as a light yellow solid. 1H-NMR (400 MHz, CDCl3-d) δ 3.95 (s, 3H), 3.98-4.13 (s, br, 2H), 6.60-6.63 (dd, J1=9.4 Hz, J2=2.4 Hz, 1H), 6.86-6.89 (dd, J1=8.8 Hz, J2=2.8 Hz, 1H), 10.70 (s, 1H); LC-MS (ESI) m/z 186 [M+1]+.

Workup

  1. filtrationThe mixture was filtered
  2. concentrationthe filtrate was concentrated
  3. customto give crude product
  4. customThe crude product was purified by chromatography (silica gel, petroleum ether/ethyl acetate=100:1 to 20:1)

Sources & evidence

ORD record
ord-4f3edbac0eb44da1a15e556ed6ae6bbd
Source dataset
uspto-grants-2012_01
Patent number
US08088760B2

Reaction notes

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