Pivalic acid → 2-Nitrodibenzofuran

HRID 1750902Notes

Reaction equation

HRID 1750902 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([O:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[CH:6][CH:5]=1)([O-:3])=[O:2].C(=O)([O-])[O-].[K+].[K+].C(O)(=O)C(C)(C)C.[OH-].[Na+]>O.C(OCC)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]2[O:10][C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=3[C:8]=2[CH:9]=1)([O-:3])=[O:2]

Participants

8

Reactant 4

HCID 6417Pivalic acidHCID 11430Potassium CarbonateHCID 121101-Nitro-4-phenoxybenzeneHCID 14798Sodium Hydroxide

Product 1

HCID 887292-NitrodibenzofuranYield 73.6%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

In a 1 L round-bottom flask, 1-nitro-4-phenoxybenzene (50 g, 232 mmol), potassium carbonate (3.21 g, 23.23 mmol), palladium acetate (2.61 g, 11.62 mmol), and 280 mL of pivalic acid were added. The mixture was heated to 120° C. in air. After 3 days the reaction mixture was cooled in an ice bath. 125 mL of 50% sodium hydroxide solution was added slowly in portions over time. The black emulsion was diluted with a large amount of water and ethyl acetate, filtered through Celite. The organic layer was separated, dried over magnesium sulfate, and filtered. The solvent was evaporated and pre-adsorbed onto Celite. The Celite mixture was purified by silica gel plug eluting with 10% to 50% dichloromethane in hexanes. 36.4 g (63% yield) desired product was obtained.

Workup

  1. temperatureAfter 3 days the reaction mixture was cooled in an ice bath
  2. filtrationfiltered through Celite
  3. customThe organic layer was separated
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. customThe solvent was evaporated and pre-adsorbed onto Celite
  7. customThe Celite mixture was purified by silica gel plug
  8. washeluting with 10% to 50% dichloromethane in hexanes

Sources & evidence

ORD record
ord-61a70ff645354aecb72bacc11351fe28
Source dataset
uspto-grants-2015_10
Patent number
US09156870B2

Reaction notes

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