Hydrogen Peroxide → 4'-METHOXY-2-NITROBIPHENYL

HRID 1489141Notes

Reaction equation

HRID 1489141 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6](B(O)O)=[CH:5][CH:4]=1.Br[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[N+:19]([O-:21])=[O:20].C([O-])([O-])=O.[Na+].[Na+].OO>CCO.C1C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[N+:19]([O-:21])=[O:20])=[CH:5][CH:4]=1

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 10340Sodium CarbonateHCID 113411-Bromo-2-nitrobenzeneHCID 201262(4-Methoxyphenyl)boronic acid

Product 1

HCID 112646854'-METHOXY-2-NITROBIPHENYLYield 104%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 241BenzeneSolventHCID 702EthanolSolvent

Procedure

A solution of 4-methoxyphenylboronic acid (11.0 g, 72 mmol) in 95% EtOH (100 mL) was added to a solution of (Ph3P)4Pd (2.25 g, 2.0 mmol) and 1-bromo-2-nitrobenzene (13.0 g, 65 mmol) in benzene (300 mL). A solution of Na2CO3 (2M, 150 mL, 300 mmol) was added, and the resulting mixture was refluxed with vigorous stirring overnight. The reaction mixture was then cooled, 30% H2O2 (20 mL) was added, and stirring was continued for 1 h. The resulting mixture was extracted with Et2O, the organic extract was rinsed with brine, dried (Na2SO4), and the solvent was removed in vacuo. The residue was taken up in CH2Cl2 :hexane 1:3, filtered through silica gel, and the biphenyl was eluted with CH2Cl2 :Hexane 1:1. The solvent was removed in vacuo to afford a yellow solid (15.5 g, quantitative yield): mp 48°-50° C.; [Jones, B.; Chapman, F., J. Chem. Soc. 1829-1832 (1952)]1H NMR (CDCl3) δ7.78 (d, 1H, J=8.4 Hz), 7.57 (t, 1H, J=7.8 Hz), 7.42 (m, 2H), 7.24 (d, 2H, J=9.0 Hz 6.94 (d, 2H, J=9.0 Hz), 3.83 (s, 3H); 13C NMR (CDCl3) δ159.70, 149.42, 135.85, 132.13, 131.92, 129.49, 129.12, 127.72, 123.99, 114.22, 55.31. Anal. Calcd for C13H11NO3 : C, 68.11; H, 4.84; N, 6.11. Found: C, 68.42; H, 4.79; N, 5.83.

Workup

  1. temperaturethe resulting mixture was refluxed
  2. temperatureThe reaction mixture was then cooled
  3. stirringstirring
  4. waitwas continued for 1 h
  5. extractionThe resulting mixture was extracted with Et2O
  6. extractionthe organic extract
  7. washwas rinsed with brine
  8. dry with materialdried (Na2SO4)
  9. customthe solvent was removed in vacuo
  10. filtrationfiltered through silica gel
  11. washthe biphenyl was eluted with CH2Cl2 :Hexane 1:1
  12. customThe solvent was removed in vacuo

Sources & evidence

ORD record
ord-5963885794ec40149f350c770f1222d4
Source dataset
uspto-grants-1997_10
Patent number
US05677328

Reaction notes

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