Methane → Methyl 3-amino-2-{[(2'-cyano[1,1'-biphenyl]-4-yl)methyl]amino}benzoate

HRID 1977389Notes

Reaction equation

HRID 1977389 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[C:9]1[CH:14]=[CH:13][C:12]([CH2:15][NH:16][C:17]2[C:26]([N+:27]([O-])=O)=[CH:25][CH:24]=[CH:23][C:18]=2[C:19]([O:21][CH3:22])=[O:20])=[CH:11][CH:10]=1)#[N:2].C.O.NN>CO.C1COCC1>[NH2:27][C:26]1[C:17]([NH:16][CH2:15][C:12]2[CH:13]=[CH:14][C:9]([C:4]3[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=3[C:1]#[N:2])=[CH:10][CH:11]=2)=[C:18]([CH:23]=[CH:24][CH:25]=1)[C:19]([O:21][CH3:22])=[O:20]

Participants

6

Reactant 3

HCID 297MethaneHCID 24654Hydrazine hydrate (1:1)HCID 15654651Methyl 2-{[(2'-cyano[1,1'-biphenyl]-4-yl)methyl]amino}-3-nitrobenzoate

Product 1

HCID 15654653Methyl 3-amino-2-{[(2'-cyano[1,1'-biphenyl]-4-yl)methyl]amino}benzoate

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of methyl 2-[[(2′-cyanobiphenyl-4-yl)methyl]amino]-3-nitrobenzoate (10 g), FeCl3.6H2O (0.1 g), activated charcoal (1 g) in a mixture of methanol (100 ml) and THF (50 ml) was heated under reflux for 30 min. Hydrazine hydrate (7.2 ml) was added dropwise to the reaction mixture and the mixture was then heated under reflux for 14 hours. The insoluble material was removed from the reaction mixture by filtration and the filtrate was concentrated to dryness. Aqueous sodium bicarbonate was added to the resulting residue and the mixture was extracted with ethyl acetate. The extract was washed with water, dried and evaporated to dryness. The residue was purified by column chromatography on silica gel to give crystals. Recrystallization from isopropyl ether afforded pale yellow needles (6.0 g, 64%), m.p. 110-111° C.

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 30 min
  3. temperaturethe mixture was then heated
  4. temperatureunder reflux for 14 hours
  5. customThe insoluble material was removed from the reaction mixture by filtration
  6. concentrationthe filtrate was concentrated to dryness
  7. additionAqueous sodium bicarbonate was added to the resulting residue
  8. extractionthe mixture was extracted with ethyl acetate
  9. washThe extract was washed with water
  10. customdried
  11. customevaporated to dryness
  12. customThe residue was purified by column chromatography on silica gel
  13. customto give crystals
  14. customRecrystallization from isopropyl ether afforded pale yellow needles (6.0 g, 64%), m.p. 110-111° C.

Sources & evidence

ORD record
ord-ab8609d3d72047ac922c2345fb9c8cf8
Source dataset
uspto-grants-2001_05
Patent number
US06232334B1

Reaction notes

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