Diethyl Ether → 4-Nitro-o-toluic acid

HRID 1739763Notes

Reaction equation

HRID 1739763 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(OCC)C.CCCCCC>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>[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

9

Reactant 4

HCID 3283Diethyl EtherHCID 8058HexaneHCID 11430Potassium CarbonateHCID 2347812-Iodo-3-nitrotoluene

Product 1

HCID 747904-Nitro-o-toluic acidYield 31.2%

Reagents, catalysts & solvents 4

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 962WaterSolvent2×HCID 6228DimethylformamideSolventHCID 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 monoxideand 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 IN hydrohloric 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 fom 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 fom diethyl ether/hexane

Sources & evidence

ORD record
ord-17abf3654c85439e829010aff9aec9b0
Source dataset
uspto-grants-1999_10
Patent number
US05968942

Reaction notes

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