Nitric Acid → HCID 11777262, compound

Participants

Reaction Conditions

Reaction Steps

m-Fluorophenyl acetic acid (15.00 gm) was dissolved in concentrated sulfuric acid (30 mL). A solution consisting of 90% nitric acid (18 mL) and concentrated sulfuric acid (22.5 mL) was added drop wise during 1 hour while maintaining the internal temperature between 20-35° C. After the addition, the solution was stirred for an additional 20 hours at 35° C. and the resultant yellow slurry was poured onto ice and filtered to give 21 gm of an off white solid. This solid obtained (mix of nitro acids) was dissolved in methanol (250 mL). Sulfuric acid (1 mL) was added and the solution was heated at reflux for 5 hours and then cooled in an ice bath. The pH was brought to ca 5 by dropwise addition of 2.5; N sodium hydroxide. Most of the methanol was removed by rotary evaporator and remainder solution was partitioned with ethyl acetate and water. After removing the aqueous phase the organic layer was dried with anhydrous sodium sulfate or magnesium sulfate, filtered over celite and concentrated to give light brown oil comprised of the following three compounds (listed in order of increasing polarity by tlc): methyl (3-fluoro-2,6-dinitrophenyl)acetate, methyl (5-fluoro-2,4-dinitrophenyl) acetate and methyl (5-methoxy-2,4-dinitrophenyl)acetate. The compounds were separated by flash chromatography (ethyl acetate/hexane 15-50%). (1) Methyl (3-fluoro-2,6-dinitrophenyl) acetate; 1H NMR (DMSO-d6) 400 MHz, δ: 3.645 (s, 3H), 4.056 (s, 2H), 7.909 (dd, J=8.8 & 9.2 Hz, 1H), 8.490 (dd, J=7.6 & 8.0 Hz, 1H). MS (ESI): m/z 256.8 [M−H]−. (2) Methyl (5-fluoro-2,4-dinitrophenyl) acetate; YD; 32%, Rf: 0.39 (EA:Hx: 3.0:7.0). 1H NMR (DMSO-d6) 400 MHz, δ: 3.637 (s, 3H), 4.223 (s, 2H), 7.923 (d, J=11.6 Hz, 1H), 8.832 (d, J=6.8 Hz, 1H). (C9H7FN2O6.1/9CH3COOC2H5) C, H, N. MS (ESI): m/z 256.8 [M−H]−. (3) Methyl (5-methoxy-2,4-dinitrophenyl) acetate; 1H NMR (DMSO-d6) 400 MHz, δ: 3.635 (s, 3H), 4.051 (s, 3H), 4.214 (s, 2H), 7.628 (s, 1H), 8.714 (s, 1H). MS (ESI); m/z 268.9 [M−H]−.

Provenance & Evidence