Nitric Acid → Ethyl 5-methyl-2,4-dinitrobenzoate

To a mixture of HNO3 (95%, 80 mL) and H2SO4 (98%, 80 mL) was slowly added 3-methylbenzoic acid (50 g, 0.37 mol) at 0° C. After addition, the mixture was stirred for 1.5 h while maintaining the temperature below 30° C. The mixture was poured into ice-water and stirred for 15 min. The precipitate was collected via filtration and washed with water to give a mixture of 3-methyl-2,6-dinitro-benzoic acid and 5-methyl-2,4-dinitro-benzoic acid (70 g, 84%). To a solution of this mixture in EtOH (150 mL) was added dropwise SOCl2 (53.5 g, 0.45 mol). The mixture was heated at reflux for 2 h and concentrated to dryness under reduced pressure. The residue was dissolved in EtOAc (100 mL) and extracted with 10% Na2CO3 solution (120 mL). The organic layer was found to contain 5-methyl-2,4-dinitro-benzoic acid ethyl ester while the aqueous layer contained 3-methyl-2,6-dinitro-benzoic acid. The organic layer was washed with brine (50 mL), dried over Na2SO4 and concentrated to dryness to provide 5-methyl-2,4-dinitro-benzoic acid ethyl ester (20 g, 20%).

1. customat 0° C
2. additionAfter addition
3. temperaturewhile maintaining the temperature below 30° C
4. stirringstirred for 15 min
5. filtrationThe precipitate was collected via filtration
6. washwashed with water
7. customto give
8. temperatureThe mixture was heated
9. temperatureat reflux for 2 h
10. concentrationconcentrated to dryness under reduced pressure
11. dissolutionThe residue was dissolved in EtOAc (100 mL)
12. extractionextracted with 10% Na2CO3 solution (120 mL)
13. washThe organic layer was washed with brine (50 mL)
14. dry with materialdried over Na2SO4
15. concentrationconcentrated to dryness

ORD-Eintrag

ord-ce1cf721aba64c96863ffa6f5d92b758

Quelldatensatz

uspto-grants-2014_06

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08741925B2