Aniline → Methyl 4-amino-3-fluoro-5-nitro-2-(phenylamino)benzoate

HRID 1749197Notes

Reaction equation

HRID 1749197 reaction equation
[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[C:7]([NH2:13])=[C:6]([F:14])[C:5]=1F.[NH2:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>>[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[C:7]([NH2:13])=[C:6]([F:14])[C:5]=1[NH:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

3

Reactant 2

HCID 6115AnilineHCID 2759749Benzoic acid, 4-amino-2,3-difluoro-5-nitro-, methyl ester

Product 1

HCID 44122658Methyl 4-amino-3-fluoro-5-nitro-2-(phenylamino)benzoate

Conditions

Temperature
125 °C

Procedure

4-Amino-2,3-difluoro-5-nitrobenzoic acid methyl ester (23.48 g, 101.1 mmol) was suspended in xylenes (125 ml) and aniline (92 ml, 1011 mmol) was added. The reaction mixture was stirred at 125° C. for 16 hours under N2. The reaction mixture was cooled to room temperature and solids precipitated out of solution. The solids were collected by filtration and washed with xylenes and then diethyl ether. Recovered 22.22 g (72.78 mmol) of yellow solid which was pure desired product. The filtrate was concentrated under reduced pressure, redissolved in methylene chloride and flushed through a plug of silica gel eluting with methylene chloride. The desired fractions were concentrated under reduced pressure to give a brown solid which was triturated with diethyl ether to give 5.47 g (17.91 mmol) of yellow solid which was pure desired product. Combined product yield was 27.69 g (90%). MS APCI (−) m/z 304 (M−1) detected.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. customsolids precipitated out of solution
  3. filtrationThe solids were collected by filtration
  4. washwashed with xylenes

Sources & evidence

ORD record
ord-5310e3f3742a4c94ae2240a5320920b9
Source dataset
uspto-grants-2015_10
Patent number
US09156795B2

Reaction notes

Loading…