Water → 4'-Methyl-2-nitro-1,1'-biphenyl

HRID 1080733Notes

Reaction equation

HRID 1080733 reaction equation
[C:1]1([CH3:10])[CH:6]=[CH:5][C:4](B(O)O)=[CH:3][CH:2]=1.Br[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[N+:18]([O-:20])=[O:19].O.C(O)(C)C>[OH-].[Na+].C1C=CC=CC=1>[CH3:10][C:1]1[CH:6]=[CH:5][C:4]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[N+:18]([O-:20])=[O:19])=[CH:3][CH:2]=1

Participants

7

Reactant 4

HCID 962WaterHCID 3776IsopropanolHCID 113411-Bromo-2-nitrobenzeneHCID 79799Tolylboronic acid

Product 1

HCID 104431944'-Methyl-2-nitro-1,1'-biphenylYield 78.3%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 14798Sodium HydroxideSolvent

Procedure

A vigorously stirred mixture of 4-tolylboronic acid (34 g, 0.25 mol) and 2-bromo-1-nitrobenzene (34 g, 0.168 mol) in a mixture of 5N sodium hydroxide (170 mL), water (57 mL), isopropanol (215 mL) and benzene (1080 mL) under a nitrogen atmosphere was treated with (tetrakis)triphenylphosphine palladium (0) (11.9 g). The stirred bilayer reaction mixture was heated at reflux for 3 hours. The cooled reaction mixture was filtered through Celite and the filter cake washed with fresh benzene. The organic layer was separated and washed with water (3×), dried over magnesium sulfate and filtered. The filtrate was evaporated under vacuum and the residue (46.1 g) purified by preparative high pressure liquid chromatography on silica gel, eluting with hexane/ethyl acetate (20:1), to give 28.05 g of the product. EI-MS: calculated for C13H11NO2 213; found 213 (M+). 1H NMR (400 MHz, CDCl3); 2.38 (s, 3H), 7.20 (m, 4H), 7.43 (m, 2H), 7.59 (t, 1H), 7.8 (d, 1H).

Workup

  1. customThe stirred bilayer reaction mixture
  2. temperaturewas heated
  3. temperatureat reflux for 3 hours
  4. customThe cooled reaction mixture
  5. filtrationwas filtered through Celite
  6. washthe filter cake washed with fresh benzene
  7. customThe organic layer was separated
  8. washwashed with water (3×)
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. customThe filtrate was evaporated under vacuum
  12. customthe residue (46.1 g) purified by preparative high pressure liquid chromatography on silica gel
  13. washeluting with hexane/ethyl acetate (20:1)

Sources & evidence

ORD record
ord-c312b918f55e4337a42cf727970388b8
Source dataset
uspto-grants-1996_12
Patent number
US05583130

Reaction notes

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