Diethyl Ether → 4-Nitro-o-toluic acid

HRID 491377Notes

Reaction equation

HRID 491377 reaction equation
I[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[CH:4][C:3]=1[CH3:11].[C:12](=O)([O-:14])[O-:13].[K+].[K+].[C]=O.C(OCC)C>O.CN(C)C=O.C(OCC)(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd](Cl)Cl.CCCCCC>[N+:8]([C:7]1[CH:6]=[CH:5][C:4]([C:12]([OH:14])=[O:13])=[C:3]([CH3:11])[CH:2]=1)([O-:10])=[O:9]

Participants

10

Reactant 4

HCID 3283Diethyl EtherHCID 11430Potassium CarbonateHCID 2347812-Iodo-3-nitrotolueneHCID 178418416HCID 178418416, compound

Product 1

HCID 747904-Nitro-o-toluic acidYield 31.2%

Reagents, catalysts & solvents 5

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 962WaterSolvent2×HCID 6228DimethylformamideSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of 1.0 g (3.8 mmol) of 2-iodo-nitrotoluene, 2.1 g (15.2 mmol) potassium carbonate and 27 mg (0.038 mmol) of palladium(II) dichloride bis(triphenylphosphine) in a mixture of 5 mL of water and 10 mL of N,N-dimethylformamide. This was placed in a Fisher/Porter bottle under 15 psig of carbon monoxide and heated at 70° C. for 16 hours. The solution became homogeneous when heated. The reaction was cooled, diethyl ether and water was added, the organic layer separated and discarded. The aqueous layer was acidified with 1N hydrochloric acid, extracted with ethyl acetate, washed with water, brine, dried over magnesium sulfate, filtered and concentrated to yield 0.5 g of crude material. This dissolved in ethyl acetate, hexane added and the resulting brown solid discarded. The filtrate was concentrated, and then recrystallized form diethyl ether/hexane to afford 215 mg of 4-nitro-2-methylbenzoic acid, m/e=182(M+H).

Workup

  1. temperatureheated
  2. temperatureThe reaction was cooled
  3. customthe organic layer separated
  4. extractionextracted with ethyl acetate
  5. washwashed with water, brine
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto yield 0.5 g of crude material
  10. concentrationThe filtrate was concentrated
  11. customrecrystallized form diethyl ether/hexane

Sources & evidence

ORD record
ord-495b5468a8094b04a759e27800c34101
Source dataset
uspto-grants-2009_05
Patent number
US07531538B2

Reaction notes

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