Nitric Acid → HCID 11777262, compound

HRID 1844104Notes

Reaction equation

HRID 1844104 reaction equation
FC1C=C(CC(O)=O)C=CC=1.[N+:12]([O-:15])([OH:14])=O.[OH-].[Na+].[F:18][C:19]1[C:20]([N+]([O-])=O)=[C:21]([CH2:28][C:29]([O:31][CH3:32])=[O:30])[C:22]([N+:25]([O-:27])=[O:26])=[CH:23][CH:24]=1.COC1C([N+]([O-])=O)=CC([N+]([O-])=O)=C(CC(OC)=O)C=1>S(=O)(=O)(O)O.CO>[CH3:32][O:31][C:29](=[O:30])[CH2:28][C:21]1[CH:20]=[C:19]([F:18])[C:24]([N+:12]([O-:15])=[O:14])=[CH:23][C:22]=1[N+:25]([O-:27])=[O:26]

Participants

8

Reactant 5

HCID 944Nitric AcidHCID 14798Sodium HydroxideHCID 676173-Fluorophenylacetic acidHCID 10355750HCID 10355750, compoundHCID 11777261HCID 11777261, compound

Product 1

HCID 11777262HCID 11777262, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 1118Sulfuric AcidSolvent3×

Conditions

Temperature
27.5 °C

Procedure

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]−.

Workup

  1. additionwas added drop wise during 1 hour
  2. additionAfter the addition
  3. additionthe resultant yellow slurry was poured onto ice
  4. filtrationfiltered
  5. customto give 21 gm of an off white solid
  6. customThis solid obtained
  7. temperaturethe solution was heated
  8. temperatureat reflux for 5 hours
  9. temperaturecooled in an ice bath
  10. additionby dropwise addition of 2.5
  11. customMost of the methanol was removed by rotary evaporator and remainder solution
  12. customwas partitioned with ethyl acetate and water
  13. customAfter removing the aqueous phase the organic layer
  14. dry with materialwas dried with anhydrous sodium sulfate or magnesium sulfate
  15. filtrationfiltered over celite and
  16. concentrationconcentrated
  17. customto give light brown oil
  18. temperaturecomprised of the following three compounds (listed in order of increasing polarity by tlc)
  19. customThe compounds were separated by flash chromatography (ethyl acetate/hexane 15-50%)

Sources & evidence

ORD record
ord-85682f34e4e246b7bbe3c4789a6a33e8
Source dataset
uspto-grants-2015_02
Patent number
US08946282B2

Reaction notes

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