HCID 67403247, compound → HCID 67402411, compound

HRID 906194Notes

Reaction equation

HRID 906194 reaction equation
[I:1][C:2]1[C:11]([N+:12]([O-])=O)=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([C:15]([F:18])([F:17])[F:16])[CH:3]=1.[I:19][C:20]1[CH:29]=[CH:28][C:23]([C:24]([O:26][CH3:27])=[O:25])=[C:22]([C:30]([F:33])([F:32])[F:31])[C:21]=1[N+:34]([O-])=O>C(O)(=O)C.[Fe]>[NH2:12][C:11]1[C:2]([I:1])=[CH:3][C:4]([C:15]([F:16])([F:17])[F:18])=[C:5]([CH:10]=1)[C:6]([O:8][CH3:9])=[O:7].[NH2:34][C:21]1[C:22]([C:30]([F:33])([F:31])[F:32])=[C:23]([CH:28]=[CH:29][C:20]=1[I:19])[C:24]([O:26][CH3:27])=[O:25]

Participants

6

Reactant 2

HCID 67403247HCID 67403247, compoundHCID 67403929HCID 67403929, compound

Product 2

HCID 67402411HCID 67402411, compoundHCID 67403170HCID 67403170, compound

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 176Acetic AcidSolvent

Procedure

A mixture of methyl 4-iodo-5-nitro-2-(trifluoromethyl)benzoate (desired) and methyl 4-iodo-3-nitro-2-(trifluoromethyl)benzoate as obtained in step 3 (1.7 g, 4.53 mmol) in acetic acid (20 mL) was treated with iron powder (1.5 g, 26.8 mmol) at 45° C. for 2 h. The reaction mixture was cooled to ambient temperature and was filtered through celite. The filter cake was washed with ethyl acetate and the filtrate was concentrated. The residue was diluted with ethyl acetate, washed with saturated sodium bicarbonate and brine, dried over sodium sulfate, then filtered and concentrated to afford a brown oil which was purified by column chromatography (silica gel, 10-30% ethyl acetate in hexanes) to afford the two regioisomers methyl 5-amino-4-iodo-2-(trifluoromethyl)benzoate (major) and methyl 3-amino-4-iodo-2-(trifluoromethyl)benzoate (minor) in a 4:1 ratio (1.484 g, 4.30 mmol, 95% yield). 1H NMR for desired (major) isomer (400 MHz, CDCl3): δ 7.96 (s, 1H), 7.06 (s, 1H), 4.55 (br s, 2H), 3.90 (s, 3H); GCMS for C9H7F31NO2: 345 (M+).

Workup

  1. filtrationwas filtered through celite
  2. washThe filter cake was washed with ethyl acetate
  3. concentrationthe filtrate was concentrated
  4. additionThe residue was diluted with ethyl acetate
  5. washwashed with saturated sodium bicarbonate and brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto afford a brown oil which
  10. customwas purified by column chromatography (silica gel, 10-30% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-bdb10607faec4742ba7dc773a1fa4e72
Source dataset
uspto-grants-2011_09
Patent number
US08012956B2

Reaction notes

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