Diethyl Ether → 4-Methoxy-2-nitro-biphenyl

HRID 617405Notes

Reaction equation

HRID 617405 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].[C:13]1(B(O)O)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C(=O)([O-])[O-].[Na+].[Na+].CCOCC>C(COC)OC.[Cl-].[Na+].O.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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:9][O:8][C:5]1[CH:6]=[CH:7][C:2]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[C:3]([N+:10]([O-:12])=[O:11])[CH:4]=1

Participants

8

Reactant 4

HCID 3283Diethyl EtherHCID 10340Sodium CarbonateHCID 66827Phenylboronic AcidHCID 792884-Bromo-3-nitroanisole

Product 1

HCID 114019374-Methoxy-2-nitro-biphenylYield 44%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst2×HCID 80711,2-DimethoxyethaneSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A magnetically stirred suspension of 4-bromo-3-nitroanisole (64.41 g, 278 mmol), phenylboronic acid (36.15 g, 296 mmol), and tris(dibenzylideneacetone)dipalladium(0) in dimethoxyethane (375 mL)/2 N sodium carbonate solution (517 mL) was stirred for 3 d under nitrogen. Additional tris(dibenzylideneacetone)-dipalladium(0) (0.5 g) was added and the suspension was stirred for 12 h, treated with Et2O (200 mL) and brine (200 mL), and the layers were separated. The aqueous layer was further extracted with fresh Et2O (2×300 mL), the combined organic extracts were filtered through Celite with diethyl ether elution, washed with water (500 mL) and brine (500 mL), dried (K2CO3), filtered, and concentrated in vacuo to afford 27.89 g (44%) of the title compound: 1H NMR (300 MHz, CDCl3) δ 3.88 (s, 3H), 7.12 (dd, J=8, 2 Hz, 1H), 7.23-7.29 (m, 2H), 7.32-7.42 (m, 5H).

Workup

  1. stirringthe suspension was stirred for 12 h
  2. customthe layers were separated
  3. extractionThe aqueous layer was further extracted with fresh Et2O (2×300 mL)
  4. filtrationthe combined organic extracts were filtered through Celite with diethyl ether elution
  5. washwashed with water (500 mL) and brine (500 mL)
  6. dry with materialdried (K2CO3)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-baf521aabdc94c1e9fd477bb995d4f9f
Source dataset
uspto-grants-1999_09
Patent number
US05948817

Reaction notes

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