Carbon Dioxide → 2-(Chloromethyl)-3-methyl-4-nitropyridine 1-oxide

HRID 35449Notes

Reaction equation

HRID 35449 reaction equation
S(=O)(=O)(O)O.C(=O)=O.[N+:9]([O-:12])(O)=[O:10].[Cl:13][CH2:14][C:15]1[C:20]([CH3:21])=[CH:19][CH:18]=[CH:17][N+:16]=1[O-:22]>C(Cl)Cl>[Cl:13][CH2:14][C:15]1[C:20]([CH3:21])=[C:19]([N+:9]([O-:12])=[O:10])[CH:18]=[CH:17][N+:16]=1[O-:22]

Participants

6

Reactant 4

HCID 280Carbon DioxideHCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 221514452-Chloromethyl-3-methylpyridine 1-oxide

Product 1

HCID 17146902-(Chloromethyl)-3-methyl-4-nitropyridine 1-oxide

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

300 ml of concentrated sulphuric acid are added slowly while cooling with dry ice to 230 ml of concentrated nitric acid (68%; d=1.41), whereby the temperature of the mixture does not exceed 5°. A solution of 38.7 g (0.25 mol) of 2-chloromethyl-3-methylpyridine 1-oxide is added thereto and the mixture is stirred at 80° for 2 hours. The reaction mixture is poured on to a mixture of ice and methylene chloride, the aqueous phase is washed several times with methylene chloride and the methylene chloride solution is extracted with 10% sodium bicarbonate solution. The organic phase is dried with sodium sulphate and concentrated. The residue is recrystallized from ethyl acetate, there being obtained 2-chloromethyl-3-methyl-4-nitropyridine 1-oxide. The product exhibits a melting point of 126°-129°.

Workup

  1. customdoes not exceed 5°
  2. washthe aqueous phase is washed several times with methylene chloride
  3. extractionthe methylene chloride solution is extracted with 10% sodium bicarbonate solution
  4. dry with materialThe organic phase is dried with sodium sulphate
  5. concentrationconcentrated
  6. customThe residue is recrystallized from ethyl acetate, there

Sources & evidence

ORD record
ord-4d13f21485a94c8eb711db21abdb7d3d
Source dataset
uspto-grants-1988_08
Patent number
US04766133

Reaction notes

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