Nitric Acid → 6-(4-Formyl-2-methoxy-5-nitrophenoxy)hexyl acetate

HRID 987393Notes

Reaction equation

HRID 987393 reaction equation
[C:1]([O:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][O:11][C:12]1[CH:17]=[CH:16][C:15]([CH:18]=[O:19])=[CH:14][C:13]=1[O:20][CH3:21])(=[O:3])[CH3:2].[N+:22]([O-])([OH:24])=[O:23]>C(O)(=O)C>[C:1]([O:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][O:11][C:12]1[CH:17]=[C:16]([N+:22]([O-:24])=[O:23])[C:15]([CH:18]=[O:19])=[CH:14][C:13]=1[O:20][CH3:21])(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 180087926-(4-Formyl-2-methoxyphenoxy)hexyl acetate

Product 1

HCID 180087936-(4-Formyl-2-methoxy-5-nitrophenoxy)hexyl acetateYield 92%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A 250 mL round bottom flask was charged with 3 (10 g, 34 mmol) and was then placed in an ice bath. To this was added a 20% v/v solution of fuming nitric acid in acetic acid (40 mL total volume) at a rate of 1.0 mL/minute with stirring. At the end of addition the bath was removed, the reaction was protected from light, and stirred at room temperature for 4 hours. At this time the solution was poured over crushed ice (200 mg). Water was added and the product was extracted with ethyl acetate (3×200 mL). The combined organics were washed with brine (1×200 mL), saturated sodium bicarbonate (1×200 mL), and water (1×200 mL), dried over magnesium sulfate, and filtered. The solvent was evaporated in vacuo to give 10.6 g of 4 (92%) as an orange-red solid. Rf=0.80 (33% ethyl acetate/hexane). Mp 79.8-81.5° C. 1H NMR (400 MHz, DMSO-d6): δ7.69 (s, 1), 7.37 (s,1), 4.17 (pt, J=6.4, 6.8 Hz, 2), 4.0 (t, J=6.8 Hz, 2), 3.95 (s,3), 1.99 (s, 3), 1.77 (m, 2), 1.59 (m, 2), 1.45-1.37 (m, 4) ppm.

Workup

  1. customwas then placed in an ice bath
  2. additionAt the end of addition the bath
  3. customwas removed
  4. stirringstirred at room temperature for 4 hours
  5. additionAt this time the solution was poured
  6. customover crushed ice (200 mg)
  7. additionWater was added
  8. extractionthe product was extracted with ethyl acetate (3×200 mL)
  9. washThe combined organics were washed with brine (1×200 mL), saturated sodium bicarbonate (1×200 mL), and water (1×200 mL)
  10. dry with materialdried over magnesium sulfate
  11. filtrationfiltered
  12. customThe solvent was evaporated in vacuo

Sources & evidence

ORD record
ord-b499794e7f8c4c4d921c8a9da9a89de2
Source dataset
uspto-grants-2003_10
Patent number
US06632641B1

Reaction notes

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