Acetic Acid → Methyl 4-amino-3-methoxyiminomethylbenzoate

HRID 2301234Notes

Reaction equation

HRID 2301234 reaction equation
C(O)(=O)C.[CH3:5][O:6][N:7]=[CH:8][C:9]1[CH:10]=[C:11]([CH:16]=[CH:17][C:18]=1[N+:19]([O-])=O)[C:12]([O:14][CH3:15])=[O:13]>C(OCC)(=O)C.[Fe]>[NH2:19][C:18]1[CH:17]=[CH:16][C:11]([C:12]([O:14][CH3:15])=[O:13])=[CH:10][C:9]=1[CH:8]=[N:7][O:6][CH3:5]

Participants

5

Reactant 2

HCID 176Acetic Acid2×HCID 53889174Methyl 3-methoxyiminomethyl-4-nitrobenzoate

Product 1

HCID 54574630Methyl 4-amino-3-methoxyiminomethylbenzoate

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 8857Ethyl AcetateSolvent

Procedure

In a 5-liter three-necked round-bottomed flask was placed 0.9 l of 5% aqueous acetic acid and 157 g (2.8 moles) of iron. To the resulting well-stirred mixture was added 166.6 g (0.7 moles) of the previously prepared methyl 3-methoxyiminomethyl-4-nitrobenzoate dissolved in 0.9 l of ethyl acetate followed by dropwise addition of 0.9 l of acetic acid while keeping the temperature below 35 C. The resulting mixture was stirred at 35° C. for 30 minutes and filtered through diatomaceous earth. The filtrate was poured into 5 l of water. The aqueous phase was separated and washed with ethyl ether (2×500 mL). The combined organic layers were washed sequentially with water (4×500 mL), saturated aqueous sodium bicarbonate (2×500 mL), water (2×500 mL), and brine (1×400 mL). The organic layer was dried over anhydrous magnesium sulfate and the solvent removed using a rotary evaporator yielding 130 g of the expected methyl 4-amino-3-methoxyiminomethylbenzoate.

Workup

  1. customIn a 5-liter three-necked round-bottomed flask was placed
  2. stirringThe resulting mixture was stirred at 35° C. for 30 minutes
  3. filtrationfiltered through diatomaceous earth
  4. additionThe filtrate was poured into 5 l of water
  5. customThe aqueous phase was separated
  6. washwashed with ethyl ether (2×500 mL)
  7. washThe combined organic layers were washed sequentially with water (4×500 mL), saturated aqueous sodium bicarbonate (2×500 mL), water (2×500 mL), and brine (1×400 mL)
  8. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  9. customthe solvent removed
  10. customa rotary evaporator

Sources & evidence

ORD record
ord-bbf2ccfbc846485985ce1accbb02ed76
Source dataset
uspto-grants-2002_12
Patent number
US06500405B1

Reaction notes

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