Sodium Hydroxide → Ethanone, 1-(1,3-benzodioxol-5-yl)-, oxime

HRID 1258128Notes

Reaction equation

HRID 1258128 reaction equation
[OH-:1].[Na+].Cl.[NH2:4]O.[CH3:6][C:7]([C:9]1[CH:14]=[CH:13][C:12]2[O:15][CH2:16][O:17][C:11]=2[CH:10]=1)=O>C(O)C>[O:15]1[C:12]2[CH:13]=[CH:14][C:9]([C:7](=[N:4][OH:1])[CH3:6])=[CH:10][C:11]=2[O:17][CH2:16]1

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 76622AcetopiperoneHCID 443297Hydroxyamine hydrochloride

Product 1

HCID 4661893Ethanone, 1-(1,3-benzodioxol-5-yl)-, oximeYield 89.9%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
80 °C

Procedure

Powdered sodium hydroxide (6.6 g, 170 mmol, 9.0 equiv) and hydroxylamine hydrochloride (3.8 g, 55 mmol, 3.0 equiv) were sequentially added to a stirred suspension of and 3,4-(methylenedioxy)acetophenone (9) (3.0 g, 18 mmol, 1.0 equiv) in ethanol (32 mL) and distilled water (13 mL) at 25° C. The reaction vessel was equipped with a reflux condenser and heated to 80° C. via oil bath for 3 h. The reaction mixture was cooled to 25° C., diluted with saturated aqueous ammonium chloride (400 mL), and the product was extracted with dichloromethane (5×125 mL). The combined organic layers were dried (sodium sulfate), gravity filtered, and concentrated by rotary evaporation. The residue was purified by rinsing with cold dichloromethane followed by vacuum filtration to afford 12 (2.9 g, 87% yield) as an off-white crystalline solid. Rf=0.41 (25% ethyl acetate in hexane); 1H NMR (500 MHz, CDCl3) δ 7.77 (s, 1H, OH), 7.18 (d, 1H, J=1.5 Hz, ArH), 7.10 (dd, 1H, J=6, 1.5 Hz, ArH), 6.81 (d, 1H, J=6 Hz, ArH), 5.99 (s, 2H, OCH2O), 2.24 (s, 3H, CH3); IR (neat film) 3296 (w, br), 3228 (w, br), 2907 (w), 1505 (s), 1266 (s), 1227 (s), 1037 (s) cm−1; HRMS (EI) m/z: Calcd for C9H9NO3 (M+) 179.0582; observed 179.0584.

Workup

  1. distillationdistilled water (13 mL) at 25° C
  2. customThe reaction vessel was equipped with a reflux condenser
  3. temperatureThe reaction mixture was cooled to 25° C.
  4. additiondiluted with saturated aqueous ammonium chloride (400 mL)
  5. extractionthe product was extracted with dichloromethane (5×125 mL)
  6. dry with materialThe combined organic layers were dried (sodium sulfate), gravity
  7. filtrationfiltered
  8. concentrationconcentrated by rotary evaporation
  9. customThe residue was purified
  10. washby rinsing with cold dichloromethane
  11. filtrationfollowed by vacuum filtration

Sources & evidence

ORD record
ord-c683b47b345f4c68b9a90f6fd64a6d0f
Source dataset
uspto-grants-2013_06
Patent number
US08466142B2

Reaction notes

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