Tetrahydrofuran → Methyl 4,5-diamino-3-fluoro-2-(2-methyl-phenylamino)benzoate

HRID 992387Notes

Reaction equation

HRID 992387 reaction equation
[NH2:1][C:2]1[C:11]([N+:12]([O-])=O)=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([NH:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=2[CH3:22])[C:3]=1[F:23].O1CCCC1>CO>[NH2:1][C:2]1[C:11]([NH2:12])=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([NH:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=2[CH3:22])[C:3]=1[F:23]

Participants

4

Reactant 2

HCID 8028TetrahydrofuranHCID 22180129Methyl 4-amino-3-fluoro-5-nitro-2-(2-toluidino)benzoate

Product 1

HCID 22180093Methyl 4,5-diamino-3-fluoro-2-(2-methyl-phenylamino)benzoateYield 96.4%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a mixture comprised of methyl 4-amino-3-fluoro-2-(2-methyl-phenylamino)-5-nitrobenzoate (2.52 g, 0.00789 mol), tetrahydrofuran (50 ml), methanol (50 ml) and washed Raney nickel (0.5 g) was initially applied 48.6 psi of hydrogen gas at 30.2° C. in a shaker for 4 hours 48 minutes. The mixture was filtered and the filtrate concentrated in vacuo to afford 2.20 g of a salmon-colored amorphous solid; 96% yield; 1H-NMR (400 MHz; DMSO) δ7.84 (s, 1H), 7.04 (d, 1H, J=7.1 Hz), 6.98 (d, 1H, J=1.2 Hz), 6.95-6.91 (m, 1H), 6.68-6.64 (m, 1H), 6.40-6.36 (m, 1H), 5.39 (s, 2H), 4.73 (s, 2H), 3.66 (s, 3H), 2.21 (s, 3H); 19F-NMR (376 MHz; DMSO) δ−139.66 (s).

Workup

  1. washwashed Raney nickel (0.5 g)
  2. customat 30.2° C.
  3. customfor 4 hours
  4. custom48 minutes
  5. filtrationThe mixture was filtered
  6. concentrationthe filtrate concentrated in vacuo

Sources & evidence

ORD record
ord-3db1b12adfc5410286e89308d3a45520
Source dataset
uspto-grants-2002_10
Patent number
US06469004B1

Reaction notes

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