Ammonium formate → Benzyl 2-(3,4-diaminobenzoyl)benzoate

HRID 2367107Notes

Reaction equation

HRID 2367107 reaction equation
[NH2:1][C:2]1[CH:25]=[CH:24][C:5]([C:6]([C:8]2[CH:23]=[CH:22][CH:21]=[CH:20][C:9]=2[C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[O:11])=[O:7])=[CH:4][C:3]=1[N+:26]([O-])=O.C([O-])=O.[NH4+]>O1CCCC1.O.[Fe]>[NH2:26][C:3]1[CH:4]=[C:5]([CH:24]=[CH:25][C:2]=1[NH2:1])[C:6]([C:8]1[CH:23]=[CH:22][CH:21]=[CH:20][C:9]=1[C:10]([O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=[O:11])=[O:7]

Participants

6

Reactant 2

HCID 2723923Ammonium formateHCID 67044429Benzyl 2-(4-amino-3-nitrobenzoyl)benzoate

Product 1

HCID 67044774Benzyl 2-(3,4-diaminobenzoyl)benzoateYield 977.4%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
80 °C

Procedure

A 1 L three-neck flask equipped with a mechanical stirrer was charged with a mixture of benzyl 2-(4-amino-3-nitrobenzoyl)benzoate (50 g, 133 mmole), iron powder (74 g, 1.30 mol), and ammonium formate (167 g, 2.60 mol) in tetrahydrofuran (300 mL) and water (200 mL). The mixture was stirred vigorously at 80° C. for 90 minutes, cooled to room temperature and filtered through celite. The celite was washed with ethyl acetate (500 mL), and the filtrate was partitioned. The organic portion was washed with 2N sodium hydroxide (2×100 mL), water, brine, dried over sodium sulfate and concentrated in-vacuo to afford benzyl 2-(3,4-diaminobenzoyl)benzoate (47 g, 1.30 mol) as a brown oil. 1H NMR (400 MHz, d6-DMSO): 7.94 (d, 1H), 7.70-7.66 (m, 1H), 7.61-7.58 (m, 1H), 7.37-7.21 (m, 6H), 6.98 (s, 1H), 6.70 (d, 1H), 6.47 (d, 1H), 5.54 (s, 2H), 5.09 (s, 2H), 4.72 (s, 2H); MS (EI) for C21H18N2O3: 349 (MNa+)

Workup

  1. customA 1 L three-neck flask equipped with a mechanical stirrer
  2. temperaturecooled to room temperature
  3. filtrationfiltered through celite
  4. washThe celite was washed with ethyl acetate (500 mL)
  5. customthe filtrate was partitioned
  6. washThe organic portion was washed with 2N sodium hydroxide (2×100 mL), water, brine
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated in-vacuo

Sources & evidence

ORD record
ord-285db0030edb4409b56bb163407e2f53
Source dataset
uspto-grants-2014_04
Patent number
US08697737B2

Reaction notes

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