Acetic Acid → (1,1'-Biphenyl)-3-carboxylic acid, 3'-amino-, methyl ester

HRID 1624197Notes

Reaction equation

HRID 1624197 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([C:10]2[CH:15]=[CH:14][CH:13]=[C:12]([C:16]([O:18][CH3:19])=[O:17])[CH:11]=2)[CH:7]=[CH:8][CH:9]=1)([O-])=O.C(O)(=O)C>C(O)C.O.[Fe]>[NH2:1][C:4]1[CH:5]=[C:6]([C:10]2[CH:15]=[CH:14][CH:13]=[C:12]([C:16]([O:18][CH3:19])=[O:17])[CH:11]=2)[CH:7]=[CH:8][CH:9]=1

Participants

6

Reactant 2

HCID 176Acetic AcidHCID 11708671Methyl 3-(3-nitrophenyl)benzoate

Product 1

HCID 1394215(1,1'-Biphenyl)-3-carboxylic acid, 3'-amino-, methyl esterYield 67.2%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

Iron (35 g, 625.00 mmol, 5.02 equiv.) was added to a solution of methyl 3′-nitrobiphenyl-3-carboxylate (32 g, 124.40 mmol, 1.00 equiv.) in ethanol (300 mL) and water (50 mL). At about 50° C., acetic acid (38 g, 633.33 mmol, 5.09 equiv.) was added dropwise to the stirred solution. The solution was heated at reflux for about 60 minutes. After filtering the solution, the filtrate was concentrated in vacuo, and then water (250 mL) and ethyl acetate (250 mL) was added. The organic phase was separated and the mother liquid was extracted with ethyl acetate (3×200 mL). The organic layers were combined, dried over anhydrous sodium sulfate and concentrated in vacuo. The resulting crude residue was purified by silica gel column chromatography (ethyl acetate/petroleum ether (1:7)) to give the title product as a light yellow solid (19 g, yield=67%). 1H NMR (300 MHz, CDCl3) δ: 8.28 (s, 1H), 8.03 (d, J=1.8 Hz, 1H), 7.76 (d, J=1.8 Hz, 1H), 7.51 (t, J=7.8 Hz, 1H), 7.29 (m, 1H), 7.03 (d, J=7.8 Hz, 1H), 6.97 (s, 1H), 6.78 (d, J=7.8 Hz, 1H), 3.98 (s, 3H).

Workup

  1. temperatureThe solution was heated
  2. temperatureat reflux for about 60 minutes
  3. filtrationAfter filtering the solution
  4. concentrationthe filtrate was concentrated in vacuo
  5. additionwater (250 mL) and ethyl acetate (250 mL) was added
  6. customThe organic phase was separated
  7. extractionthe mother liquid was extracted with ethyl acetate (3×200 mL)
  8. dry with materialdried over anhydrous sodium sulfate
  9. concentrationconcentrated in vacuo
  10. customThe resulting crude residue was purified by silica gel column chromatography (ethyl acetate/petroleum ether (1:7))

Sources & evidence

ORD record
ord-c96a5f6c72c24afb925560850c2099d6
Source dataset
uspto-grants-2014_07
Patent number
US08778998B2

Reaction notes

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