Sodium Carbonate → 2-Carbomethoxy-6-nitro-2'-methoxy-biphenyl

HRID 51432

Reaction equation

HRID 51432 reaction equation
Cl[C:2]1[C:11]([N+:12]([O-:14])=[O:13])=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[CH3:15][O:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1B(O)O.C(=O)([O-])[O-].[Na+].[Na+]>C1COCC1.[Al].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>[C:4]([C:3]1[CH:8]=[CH:9][CH:10]=[C:11]([N+:12]([O-:14])=[O:13])[C:2]=1[C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][C:17]=1[O:16][CH3:15])([O:6][CH3:7])=[O:5]

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 27339582-Methoxyphenylboronic acidHCID 10751184Methyl 2-chloro-3-nitrobenzoate

Product 1

HCID 227404432-Carbomethoxy-6-nitro-2'-methoxy-biphenylYield 69.5%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 5359268AluminumSolvent

Procedure

A solution of methyl 2-chloro-3-nitrobenzoate (2.16 g, 10.0 mM), 2-methoxybenzeneboronic acid (1.64 g, 10.5 mM), tetrakis(triphenylphosphine)palladium (0) (584 mg, 0.5 mM), and 2 M aqueous sodium carbonate (10.5 mL, 21.0 mM) in 50 mL of THF was wrapped in aluminum foil and stirred at reflux for 27 hours. The THF was removed in vacuo and the residue dissolved in ethyl acetate. The mixture was washed with with H2O, 1 N HCl, H2O, sat. NaHCO3, and saturated brine, dried over magnesium sulfate, filtered, and concentrated. The resultant light brown oil was purified by column chromatography on silica (elution with gradient toluene/ethyl acetate) to afford 2.0 g (69%) of 2-carbomethoxy-6-nitro-2′-methoxy-biphenyl as a yellow-orange solid. 1H NMR (CDCl3) δ8.05 (d, 1H, J=8 Hz), 7.95 (d, 1H, J=8 Hz), 7.55 (t, 1H, J=8 Hz), 7.35 (t, 1H, J=8 Hz), 7.05 (d, 1H, J=8 Hz), 7.0 (t, 1H, J=8 Hz), 6.9 (d, 1H, J=8 Hz), 3.7 (s, 3H), and 3.6 (s, 3H). IR (KBr, cm−1) 1730, 1538, 1499, 1366, 1298, 1271, 1130, 774, 765, 759, 752, and 707. MS (ES) m/e 288.

Workup

  1. temperatureat reflux for 27 hours
  2. customThe THF was removed in vacuo
  3. dissolutionthe residue dissolved in ethyl acetate
  4. washThe mixture was washed with with H2O, 1 N HCl, H2O, sat. NaHCO3, and saturated brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe resultant light brown oil was purified by column chromatography on silica (elution with gradient toluene/ethyl acetate)

Sources & evidence

ORD record
ord-4c59ee4e2d2b4b46a25e5b6e76fcd145
Source dataset
uspto-grants-2004_03
Patent number
US06713645B1

Linked notes

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