Dichloromethane → Methyl 3-methyl-4'-nitrobiphenyl-4-carboxylate

HRID 2356789Notes

Reaction equation

HRID 2356789 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([CH3:12])[CH:3]=1.[N+:13]([C:16]1[CH:21]=[CH:20][C:19](B(O)O)=[CH:18][CH:17]=1)([O-:15])=[O:14].C([O-])([O-])=O.[Na+].[Na+].ClCCl>C1(C)C=CC=CC=1.CCOC(C)=O.O.O1CCOCC1>[CH3:12][C:4]1[CH:3]=[C:2]([C:19]2[CH:20]=[CH:21][C:16]([N+:13]([O-:15])=[O:14])=[CH:17][CH:18]=2)[CH:11]=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7]

Participants

9

Reactant 4

HCID 6344DichloromethaneHCID 10340Sodium CarbonateHCID 27735524-Nitrophenylboronic acidHCID 22031226Methyl 4-bromo-2-methylbenzoate

Product 1

HCID 59385226Methyl 3-methyl-4'-nitrobiphenyl-4-carboxylateYield 111.4%

Reagents, catalysts & solvents 4

HCID 962WaterSolvent2×HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of methyl 4-bromo-2-methylbenzoate (1.00 g, 4.37 mmol) and 4-nitrophenylboronic acid (2.91 g, 17.5 mmol) in toluene (12 mL) was added Na2CO3 (3.70 g, 34.9 mmol), 1,1′-bis(diphenylphosphino)ferrocenepalladium(II) chloride complex with dichloromethane (0.71 g, 0.87 mmol), 1,4-dioxane (6 mL), and water (6 mL). The mixture was heated at reflux for 3 h and then allowed to cool to rt. The mixture was diluted with EtOAc and water, and the organic layer was isolated, dried over MgSO4, and concentrated in vacuo. The material was purified by column chromatography (25% EtOAc in hexanes), yielding 1.32 g (89%) of the title compound. GC/MS m/z 271 (M+); retention time 13.00 min. 1H NMR (400 MHz, CD2Cl2) 2.65 (s, 3H), 3.95 (s, 3H), 7.52 (d, 2H), 7.78 (d, 2H), 8.11 (d, 1H), 8.30-8.39 (m, 2H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 3 h
  3. customthe organic layer was isolated
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated in vacuo
  6. customThe material was purified by column chromatography (25% EtOAc in hexanes)

Sources & evidence

ORD record
ord-aa9949d7a1474b38b5216d609f02e494
Source dataset
uspto-grants-2010_07
Patent number
US07759376B2

Reaction notes

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