Preparation method of 1-methyl-3,5-dinitro-2-pyridone_Industrial additives

Background and overview of the preparation method of 1-methyl-3,5-dinitro-2-pyridone

1-Methyl-3,5-dinitro-2-pyridone is an organic intermediate. 1-methyl-pyridine monomethyl sulfate can be prepared from pyridine as raw material, and then oxidized to obtain 1- Methyl-2-pyridone is finally nitrated to obtain 1-methyl-3,5-dinitro-2-pyridone.

Preparation method of 1-methyl-3,5-dinitro-2-pyridone

Preparation method of 1-methyl-3,5-dinitro-2-pyridone Preparation of 1-methyl-pyridine monomethyl sulfate

Methyl sulfate (30 mL, 39.8 g, 0.315 mol) was added dropwise to anhydrous pyridine (25.0 g, 0.316 mol). The mixture was stirred at room temperature for 10 min and then at 100 °C for 2 h. The mixture was cooled to room temperature to give crude 1-methyl-pyridinemonomethylsulfate (64.7 g, quant.), which was used without further purification.

Preparation method of 1-methyl-3,5-dinitro-2-pyridone Preparation of 1-methyl-2-pyridone

A solution of 1-methyl-pyridinemonomethylsulfate (50g, 0.243mol) in water (54mL) was cooled to 0°C. Prepare a solution of potassium ferricyanide (160g, 0.486mol) in water (320mL) and a solution of sodium hydroxide (40g, 1.000mol) in water (67mL) respectively, and add them dropwise from two separate funnels to a well-stirred 1 -Methyl-pyridine monomethyl sulfate solution was added at a rate such that the temperature of the reaction mixture did not rise above 10°C. The rates of addition of the two solutions were adjusted so that when half the potassium ferricyanide solution was added the entire sodium hydroxide solution had been added. After the addition was complete, the reaction mixture was allowed to warm to mica room temperature and stirred overnight. Dry sodium carbonate (91.6g) was added and the mixture was stirred for 10 min. The organic layer was separated and the aqueous layer was extracted with CH2Cl2 (100mL x 3). The organic layers were combined, dried, and concentrated to give 1-methyl-2-pyridone (25.0 g, 94%), which was used without further purification.

Preparation method of 1-methyl-3,5-dinitro-2-pyridone Preparation of 1-methyl-3,5-dinitro-2-pyridone

Add 1-methyl-2-pyridone (25.0g, 0.229mol) to sulfuric acid (500mL) at 0°C. After stirring for 5 min, nitric acid (200 mL) was added dropwise at 0°C. After addition, the reaction mixture was slowly raised to 100 °C and then maintained for 5 h. The reaction mixture was poured into ice, basified to pH 8 with potassium carbonate, and extracted with CH2Cl2 (100 mL x 3). The organic layers were combined, dried over Na2SO4, and concentrated to obtain 1-methyl-3,5 rubidium tetrafluoroborate-dinitro-2-pyridone (12.5 g, 28%), which was used without further purification.

References

[1] [Chinese invention] CN201080056022.X 4-oxo-1H-quinoline-3-carboxamide as an ATP-binding cassette transporter regulator