Hydrochloric Acid → Methyl 4-(4'-amino-3'-methoxy-1,1'-biphenyl-4-yl)-2,2-dimethyl-4-oxobutanoate

HRID 9557Notes

Reaction equation

HRID 9557 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:12]2[CH:17]=[CH:16][C:15]([C:18](=[O:27])[CH2:19][C:20]([CH3:26])([CH3:25])[C:21]([O:23][CH3:24])=[O:22])=[CH:14][CH:13]=2)[CH:6]=[CH:7][C:8]=1[N+:9]([O-])=O.Cl>C(O)C.[Fe]>[NH2:9][C:8]1[CH:7]=[CH:6][C:5]([C:12]2[CH:13]=[CH:14][C:15]([C:18](=[O:27])[CH2:19][C:20]([CH3:26])([CH3:25])[C:21]([O:23][CH3:24])=[O:22])=[CH:16][CH:17]=2)=[CH:4][C:3]=1[O:2][CH3:1]

Participants

5

Reactant 2

HCID 313Hydrochloric AcidHCID 21985714Methyl 4-(3'-methoxy-4'-nitro-1,1'-biphenyl-4-yl)-2,2-dimethyl-4-oxobutanoate

Product 1

HCID 21985857Methyl 4-(4'-amino-3'-methoxy-1,1'-biphenyl-4-yl)-2,2-dimethyl-4-oxobutanoateYield 67%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 702EthanolSolvent

Procedure

To a solution of methyl 4-(3′-methoxy-4′-nitro-1,1′-biphenyl-4-yl)-2,2-dimethyl -4-oxobutanoate (670 mg, 1.80 mmol) in 85% aqueous ethanol (27 mL) was added iron powder (1.01 g, 18.04 mmol) and 2 N aqueous HCl (0.9 mL, 1.8 mmol), and the resulting suspension was heated at reflux for 2.5 h. The mixture was then cooled to rt, and filtered through a pad of Celite®. Water was added, the mixture was extracted with ethyl acetate, and the combined organic phases were dried over anhydrous sodium sulfate. Solvent was removed under reduced pressure and the residue was triturated with ethyl acetate/hexane to afford methyl 4-(4′-amino-3′-methoxy-1,1′-biphenyl-4-yl)-2,2-dimethyl-4-oxobutanoate (410 mg, 67%). LC-MS ret. time 2.58 min, m/z 342.1 (MH+); 1H NMR (300 MHz, CDCl3) δ 1.31 (s, 6H), 3.28 (s, 2H), 3.66 (s, 3H), 3.90 (s, 3H), 6.75 (d, 1H), 7.02–7.09 (m, 2H), 7.59 (d, 2H), 7.94 (d, 2H).

Workup

  1. temperaturethe resulting suspension was heated
  2. temperatureat reflux for 2.5 h
  3. filtrationfiltered through a pad of Celite®
  4. additionWater was added
  5. extractionthe mixture was extracted with ethyl acetate
  6. dry with materialthe combined organic phases were dried over anhydrous sodium sulfate
  7. customSolvent was removed under reduced pressure
  8. customthe residue was triturated with ethyl acetate/hexane

Sources & evidence

ORD record
ord-3c4822aa92be40e0b6bc55a8704b5cb2
Source dataset
uspto-grants-2006_08
Patent number
US07091228B2

Reaction notes

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