2-Nitrobiphenyl → 2-Amino-6-phenyl-nitrobenzene

HRID 7090

Reaction equation

HRID 7090 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)([O-:3])=[O:2].Cl.CO[NH2:19].CC(C)([O-])C.[K+]>CN(C=O)C.[Cu]Cl>[NH2:19][C:9]1[CH:8]=[CH:7][CH:6]=[C:5]([C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=2)[C:4]=1[N+:1]([O-:3])=[O:2]

Participants

6

Reactant 3

HCID 68292-NitrobiphenylHCID 521874O-Methylhydroxylamine hydrochlorideHCID 23665647Potassium tert-butoxide

Product 1

HCID 105127972-Amino-6-phenyl-nitrobenzeneYield 27.1%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 6228DimethylformamideSolvent2×

Procedure

A suspension of 2-nitrobiphenyl (2.061 g, 10.34 mmol) and O-methylhydroxylamine hydrochloride (1.088 g, 13.02 mmol) in DMF (15 mL) was added to a cold (0° C.) solution of potassium tert-butoxide (5.993 g, 53.40 mmol) and copper(I) chloride (0.246 g, 2.48 mmol) in DMF (35 mL). The cooling bath was removed and the resultant slurry was stirred at room temperature for 20 hours. The reaction mixture was poured into saturated aqueous NH4Cl (50 mL) and the mixture was extracted with CH2Cl2 (4×50 mL). The combined organic extracts were dried (Na2SO4) and concentrated. Purification of the crude material by column chromatography on silica gel (4:1 hexanes-ethyl acetate followed by 2:1 hexanes-ethyl acetate) provided 0.600 g (27%) 2-amino-6-phenyl-nitrobenzene as a yellow oil. 1H NMR (CDCl3) □ 4.99 (br s, 2H), 6.70 (dd, 1H, J=7.2, 1.2 Hz), 6.80 (dd, 1H, J=8.4, 1.2 Hz), 7.29–7.41 (m, 6H).

Workup

  1. customThe cooling bath was removed
  2. additionThe reaction mixture was poured into saturated aqueous NH4Cl (50 mL)
  3. extractionthe mixture was extracted with CH2Cl2 (4×50 mL)
  4. dry with materialThe combined organic extracts were dried (Na2SO4)
  5. concentrationconcentrated
  6. customPurification of the crude material by column chromatography on silica gel (4:1 hexanes-ethyl acetate followed by 2:1 hexanes-ethyl acetate)

Sources & evidence

ORD record
ord-754b34941ad244829017dcc78f4df6f3
Source dataset
uspto-grants-2006_08
Patent number
US07084155B2

Linked notes

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