Ethanol → 2-Methylamino3-nitro-6-phenylpyridine

HRID 55541

Reaction equation

HRID 55541 reaction equation
C(=O)([O-])[O-].[Na+].[Na+].Cl[C:8]1[N:13]=[C:12]([NH:14][CH3:15])[C:11]([N+:16]([O-:18])=[O:17])=[CH:10][CH:9]=1.B([O-])([O-])O[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.C(O)C>[OH-].[OH-].[Pd+2].C1(C)C=CC=CC=1>[CH3:15][NH:14][C:12]1[C:11]([N+:16]([O-:18])=[O:17])=[CH:10][CH:9]=[C:8]([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[N:13]=1

Participants

7

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 107500946-chloro-N-methyl-3-nitropyridin-2-amineHCID 19793864Phenylborate

Product 1

HCID 104895752-Methylamino3-nitro-6-phenylpyridineYield 7,773.9%

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 1140TolueneSolvent

Conditions

Temperature
105 °C

Procedure

50 ml of a 2N aqueous solution of sodium carbonate and 0.34 g of 20% w/w palladium hydroxide on charcoal were added to a solution of 5.0 g of 6-chloro-2-methylamino-3-nitropyridine (prepared as described in Preparation 66) and 3.9 g of phenyl borate in 80 ml of a 1:1 by volume mixture of ethanol and toluene, and the resulting mixture was stirred at 105° C. for 4.5 hours. At the end of this time, the reaction mixture was filtered to remove the palladium hydroxide on charcoal. The filtrate was concentrated by evaporation under reduced pressure, and the concentrate was diluted with water, after which it was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate, after which the solvent was removed by distillation under reduced pressure. The residue was crystallized by trituration with ethanol, to give 475 g of the title compound, melting at 98°-99° C.

Workup

  1. filtrationAt the end of this time, the reaction mixture was filtered
  2. customto remove the palladium hydroxide on charcoal
  3. concentrationThe filtrate was concentrated by evaporation under reduced pressure
  4. additionthe concentrate was diluted with water
  5. extractionafter which it was extracted with ethyl acetate
  6. washThe extract was washed with water
  7. dry with materialdried over anhydrous sodium sulfate
  8. customafter which the solvent was removed by distillation under reduced pressure
  9. customThe residue was crystallized by trituration with ethanol

Sources & evidence

ORD record
ord-3d62ed38c2974e79a7fb0852201ac7ad
Source dataset
uspto-grants-1997_04
Patent number
US05624935

Linked notes

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