Formic Acid → HCID 178497005, compound

HRID 31964Notes

Reaction equation

HRID 31964 reaction equation
[CH3:1][O:2][C:3](=[O:23])[C:4]1[CH:9]=[C:8]([N+:10]([O-])=O)[C:7]([NH2:13])=[C:6]([F:14])[C:5]=1[NH:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[CH3:22].[CH:24](O)=O>CCO.[OH-].[OH-].[Pd+2]>[CH3:1][O:2][C:3]([C:4]1[C:5]([NH:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=2[CH3:22])=[C:6]([F:14])[C:7]2[NH:13][CH:24]=[N:10][C:8]=2[CH:9]=1)=[O:23]

Participants

5

Reactant 2

HCID 284Formic Acid2×HCID 22180129Methyl 4-amino-3-fluoro-5-nitro-2-(2-toluidino)benzoate

Product 1

HCID 178497005HCID 178497005, compound

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalyst2×HCID 702EthanolSolvent

Conditions

Temperature
95 °C

Procedure

4-Amino-3-fluoro-5-nitro-2-o-tolylamino-benzoic acid methyl ester 5a (1.57 g, 4.92 mmol), formic acid (25 mL, 26.5 mmol) and 20% Pd(OH)2/C (1.57 g, 2.95 mmol) in 25 mL EtOH are heating with stirring to 95° C. After 16 hours, the reaction mixture is cooled to room temperature and 0.5 g 20% Pd(OH)2/C and 10 mL formic acid added. The reaction mixture is heated to 95° C. with stirring. After 16 hours, the reaction mixture is cooled to room temperature and filtered through Celite rinsing with EtOH. The filtrate is concentrated under reduced pressure until the desired product precipitates. The desired product is collected by filtration. The filtrate is concentrated again until more desired product precipitates. The product is collected by filtration. Repeated EtOH concentration, product filtration several times. Recovered 1.09 g (74%) pure desired product: MS APCI (+) m/z 300 (M+1) detected; MS APCI (−) m/z 298 (M−1) detected.

Workup

  1. temperaturethe reaction mixture is cooled to room temperature
  2. temperatureThe reaction mixture is heated to 95° C.
  3. stirringwith stirring
  4. waitAfter 16 hours
  5. temperaturethe reaction mixture is cooled to room temperature
  6. filtrationfiltered through Celite
  7. washrinsing with EtOH
  8. concentrationThe filtrate is concentrated under reduced pressure until the desired product
  9. customprecipitates
  10. filtrationThe desired product is collected by filtration
  11. concentrationThe filtrate is concentrated again until more desired product
  12. customprecipitates
  13. filtrationThe product is collected by filtration
  14. concentrationRepeated EtOH concentration, product filtration several times
  15. customRecovered 1.09 g (74%) pure desired product

Sources & evidence

ORD record
ord-b6cf37c8a1b841189626baf68c1abf51
Source dataset
uspto-grants-2008_09
Patent number
US07425637B2

Reaction notes

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