Sodium Carbonate → Methyl 5-nitrobiphenyl-2-carboxylate

HRID 2121183Notes

Reaction equation

HRID 2121183 reaction equation
Cl[C:2]1[CH:11]=[C:10]([N+:12]([O-:14])=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[C:15]1(B(O)O)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.C(=O)([O-])[O-].[Na+].[Na+]>O1CCOCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:7][O:6][C:4](=[O:5])[C:3]1[CH:8]=[CH:9][C:10]([N+:12]([O-:14])=[O:13])=[CH:11][C:2]=1[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 66827Phenylboronic AcidHCID 83343Methyl 2-chloro-4-nitrobenzoate

Product 1

HCID 15406987Methyl 5-nitrobiphenyl-2-carboxylateYield 82.1%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
92.5 °C

Procedure

A mixture of methyl 2-chloro-4-nitrobenzoate (44.2 g, 205 mmol), phenylboronic acid (27.5 g, 226 mmol), sodium carbonate (2.0 M in water, 123 mL, 246 mmol), and bis(triphenylphosphine)palladium(II) chloride (2.8 g, 4 mmol) in dioxane (300 mL) was degassed by nitrogen, and heated at 90-95° C. for 20 hours. The reaction mixture was diluted with ether (500 mL) and ethyl actate (500 mL), washed with water (2 times, 200 mL each) and brine, dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The residue was recrystalized from hexane-ethyl acetate (1/1) to give 2-phenyl-4-nitrobenzoic acid methyl ester as a white solid (43.3 g). The mother liquid from the recrystalization was concentrated in vacuo, and the residue was purified by column chromataography (80:15:5 hexane-chloroform-ethyl acetate) to yield an additional 5.2 g of the desired compound (total yield 48.5 g, 92%). 1H NMR (300 MHz, CDCl3) δ 8.25 (d, 1H), 8.24 (dd, 1H), 7.94 (dd, 1H), 7.44 (m, 3H), 7.35 (m, 2H), 3.67 (s, 3H).

Workup

  1. customwas degassed by nitrogen
  2. additionThe reaction mixture was diluted with ether (500 mL) and ethyl actate (500 mL)
  3. washwashed with water (2 times, 200 mL each) and brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was recrystalized from hexane-ethyl acetate (1/1)

Sources & evidence

ORD record
ord-55cbe10f29894b55918c02d61a7db16a
Source dataset
uspto-grants-2004_02
Patent number
US06693123B2

Reaction notes

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