Potassium Carbonate → 2-Methyl-3-nitropyridine

HRID 473401

Reaction equation

HRID 473401 reaction equation
Cl[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[CH:4][N:3]=1.[CH3:11]B(O)O.C(=O)([O-])[O-].[K+].[K+]>C1OCCOC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:11][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[CH:4][N:3]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 796132-Chloro-3-nitropyridineHCID 139377Methylboronic Acid

Product 1

HCID 3293602-Methyl-3-nitropyridine

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

2-Chloro-3-nitropyridine (20 g, 126.18 mmol), methane boronic acid (9.8 g, 164 mmol), tetrakis(triphenylphosphine)palladium (11.66 g, 10 mmol) and potassium carbonate (51.48 g, 378.6 mmol) were all mixed in 1-4 dioxane (500 mL), degasified and heated to 100° C. for 48 h under N2. Work up was carried out by allowing the reaction mass to cool to ambient temperature and quenched with water and extracted with ethyl acetate. The aqueous layer was back extracted with ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure to give a solid. The solid was further purified by silica gel column chromatography using 6% of ethyl acetate in hexane as eluent to give 2-methyl-3-nitropyridine as an off white solid: 1H-NMR (CDCl3) δ: 2.9 (s, 3H), 7.4 (m, 1H), 8.3 (d, 1H), 8.7 (d, 1H).

Workup

  1. temperatureto cool to ambient temperature
  2. customquenched with water
  3. extractionextracted with ethyl acetate
  4. extractionThe aqueous layer was back extracted with ethyl acetate
  5. dry with materialThe combined organic layers were dried over anhydrous Na2SO4
  6. concentrationconcentrated under reduced pressure
  7. customto give a solid
  8. customThe solid was further purified by silica gel column chromatography

Sources & evidence

ORD record
ord-076d1b40a1ae403aa7a33901cb7b6f77
Source dataset
uspto-grants-2014_01
Patent number
US08633313B2

Linked notes

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