Phenylboronic Acid → 3-Methoxy-4-nitro-1,1′-biphenyl

HRID 1773494Notes

Reaction equation

HRID 1773494 reaction equation
[K].Cl[C:3]1[CH:4]=[CH:5][C:6]([N+:11]([O-:13])=[O:12])=[C:7]([O:9][CH3:10])[CH:8]=1.[C:14]1(B(O)O)[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>CO.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Cl-].C(C1C=CC=C(C(C)C)C=1[N+]1C=CN(C2C(C(C)C)=CC=CC=2C(C)C)C=1)(C)C>[CH3:10][O:9][C:7]1[CH:8]=[C:3]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH:4]=[CH:5][C:6]=1[N+:11]([O-:13])=[O:12]

Participants

9

Reactant 3

HCID 66827Phenylboronic AcidHCID 811105-Chloro-2-nitroanisoleHCID 5462222Potassium

Product 1

HCID 42831993-Methoxy-4-nitro-1,1′-biphenylYield 114.8%

Reagents, catalysts & solvents 5

HCID 74236Tetrabutylammonium BromideCatalystHCID 27349131,3-Bis(2,6-diisopropylphenyl)imidazolium chlorideCatalystHCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 887MethanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

A solution of potassium methoxyde (0.56 g, 7.98 mmol) in anhydrous methanol (5 mL) was added at 0° C. to a mixture of 5-chloro-2-nitroanisole (0.5 g, 2.66 mmol), phenylboronic acid (0.42 g, 3.44 mmol), bis(dibenzylideneacetone)palladium (47 mg, 0.082 mmol), 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (35 mg, 0.082 mmol) and tetrabutylammonium bromide (86 mg, 0.267 mmol) in anhydrous toluene (20 mL). The reaction mixture was stirred at 60° C. for 24 hours, and then was partitioned between ethyl acetate and water. The organic layer was separated and washed with brine, dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The crude residue was purified on a silica gel plug (EtOAc/hexane, 20/80) to give 0.7 g of 3-methoxy-4-nitro-biphenyl as a yellow oil.

Workup

  1. customwas partitioned between ethyl acetate and water
  2. customThe organic layer was separated
  3. washwashed with brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. customevaporated under reduced pressure
  7. customThe crude residue was purified on a silica gel plug (EtOAc/hexane, 20/80)

Sources & evidence

ORD record
ord-9f3b3890667f4e7baf5e204f2a675e92
Source dataset
uspto-grants-2016_02
Patent number
US09255110B2

Reaction notes

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