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

HRID 1728630Notes

Reaction equation

HRID 1728630 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:27]([N+:28]([O-])=O)=[CH:26][CH:25]=[CH:24][C:18]=2[C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:11][CH:10]=1)#[N:2]>C(O)C>[NH2:28][C:27]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:24]=[CH:25][CH:26]=1)[C:19]([O:21][CH2:22][CH3:23])=[O:20]

Participants

3

Reactant 1

HCID 12018931Ethyl 2-{[(2'-cyano[1,1'-biphenyl]-4-yl)methyl]amino}-3-nitrobenzoate

Product 1

HCID 15654655Ethyl 3-amino-2-(((2'-cyano-[1,1'-biphenyl]-4-yl)methyl)amino)benzoateYield 79%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of ethyl 2-[(2'cyanobiphenyl-4-yl]-methyl]amino-3-nitrobenzoate (10.4 g) in ethanol (50 ml) was added stannous dichloride dihydrate (28.1 g) and the mixture was stirred at 80° C for two hours. The solvent was evaporated to dryness. To the ice-cooling mixture of the residue in ethyl acetate (300 ml) was added dropwise 2N NaOH (500 ml) with stirring. The aqueous layer was extracted with ethyl acetate (200 ml×2). The organic layers were combined, washed with water, and dried. The solvent was evaporated to dryness and the residue was purified by column chromatography on silica gel to give crystals. Recrystallization from ethyl acetate-hexane gave colorless crystals (7.3 g, 79%), m.p. 104°-105° C.

Workup

  1. customThe solvent was evaporated to dryness
  2. temperatureTo the ice-cooling
  3. additionmixture of the residue in ethyl acetate (300 ml)
  4. additionwas added dropwise 2N NaOH (500 ml)
  5. stirringwith stirring
  6. extractionThe aqueous layer was extracted with ethyl acetate (200 ml×2)
  7. washwashed with water
  8. customdried
  9. customThe solvent was evaporated to dryness
  10. customthe residue was purified by column chromatography on silica gel
  11. customto give crystals
  12. customRecrystallization from ethyl acetate-hexane

Sources & evidence

ORD record
ord-81f6724b386642c184e0fcb47c22cd02
Source dataset
uspto-grants-1994_07
Patent number
US05328919

Reaction notes

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