Nitrobenzene → 3-Methyl-4'-nitro-1,1'-biphenyl

HRID 849301Notes

Reaction equation

HRID 849301 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)([O-:3])=[O:2].[CH3:10][C:11]1[CH:12]=[C:13](B(O)O)[CH:14]=[CH:15][CH:16]=1>CC(C)=O.O.CC([O-])=O.CC([O-])=O.[Pd+2]>[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([C:15]2[CH:14]=[CH:13][CH:12]=[C:11]([CH3:10])[CH:16]=2)=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

6

Reactant 2

HCID 7416NitrobenzeneHCID 27339503-Tolylboronic acid

Product 1

HCID 105605343-Methyl-4'-nitro-1,1'-biphenylYield 85%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 180AcetoneSolventHCID 962WaterSolvent

Procedure

To a mixture of 4-nitrobenzene (3.0 g, 14.8 mmol) and 3-methylphenylboronic acid (2.06 g, 15.1 mmol) in 35 mL of acetone and 40 mL of water was added K2CO3.1.5H2O (5.93 g, 37.5 mmol) and Pd(OAc)2 (101 mg, 0.50 mmol). The deep black mixture was refluxed for 6 hr and then cooled. The mixture was extracted with ether and the organic layer was passed through a layer of celite. The pale yellow solution was dried over Na2SO4 and evaporated to dryness. The residue was recrystallized from hot methanol to give pale yellow crystals (2.68 g, 85%). m.p.59-60° C.1H NMR (CDCl3) δ 8.26 (d, 8.7 Hz, 2H), 7.70 (d, 8.7 Hz, 2H), 7.41 (m, 3H), 7.26 (d, 7.1 Hz, 1H), 2.43 (s, 1H). 13C NMR (CDCl3) δ 147.6, 146.8, 138.8, 138.6, 129.6, 128.9, 128.0, 127.6, 124.4, 123.9, 21.4. LRMS (EI) for C13H11NO2 213 (M+, intensity 100); HRMS (EI) calcd 213.0789, obsd 213.0778.

Workup

  1. temperatureThe deep black mixture was refluxed for 6 hr
  2. temperaturecooled
  3. extractionThe mixture was extracted with ether
  4. dry with materialThe pale yellow solution was dried over Na2SO4
  5. customevaporated to dryness
  6. customThe residue was recrystallized from hot methanol

Sources & evidence

ORD record
ord-822c351b3e044262bc5d25869f29b051
Source dataset
uspto-grants-2000_01
Patent number
US06011175

Reaction notes

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