Methyl 4-cyano-2-methyl-5-nitrobenzoate → Methyl 5-amino-4-cyano-2-methylbenzoate
Reaction equation
[C:1]([C:3]1[C:12]([N+:13]([O-])=O)=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5]([CH3:16])[CH:4]=1)#[N:2]>C(O)(=O)C.[Fe]>[NH2:13][C:12]1[C:3]([C:1]#[N:2])=[CH:4][C:5]([CH3:16])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8]Participants
Reactant 1
Product 1
Reagents, catalysts & solvents 2
Conditions
- Temperature
- 45 °C
Procedure
To a solution of methyl 4-cyano-2-methyl-5-nitrobenzoate (14.8 g, 0.0672 mol) in acetic acid (250 mL) was added iron powder (22.5 g, 0.40 mol). The reaction mixture was heated to 45° C. and stirred for 1 h, at which time it was cooled to room temperature. The reaction mixture was filtered through a bed of celite, and the filter cake rinsed with ethyl acetate. The volume of the filtrate was reduced by half and then partitioned between water and ethyl acetate. The organic layer was washed with 10% lithium chloride followed by saturated aqueous sodium bicarbonate. The organic layer was further washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was triturated with hexanes to afford methyl 5-amino-4-cyano-2-methylbenzoate (11.7 g, 91%) as a bright yellow powder. 1H NMR (400 MHz, CDCl3): 7.28 (s, 1H), 7.26 (s, 1H), 4.35 (br s, 2H), 3.89 (s, 3H), 2.43 (s, 3H). MS (EI) for C10H10N2O2: 191 (MH+).
Workup
- temperaturewas cooled to room temperature
- filtrationThe reaction mixture was filtered through a bed of celite
- washthe filter cake rinsed with ethyl acetate
- custompartitioned between water and ethyl acetate
- washThe organic layer was washed with 10% lithium chloride
- washThe organic layer was further washed with brine
- dry with materialdried over anhydrous magnesium sulfate
- filtrationfiltered
- concentrationconcentrated
- customThe residue was triturated with hexanes
Sources & evidence
- ORD record
- ord-8af1536ff29d4759b1bcd98611888295
- Source dataset
- uspto-grants-2011_09
- Patent number
- US08012956B2
Reaction notes
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