Ethanol → HCID 44549262, compound

HRID 2377046Notes

Reaction equation

HRID 2377046 reaction equation
S(=O)(=O)(O)[OH:2].[CH3:6][C:7]1[C:12]([N+:13]([O-:15])=[O:14])=[CH:11][N:10]=[C:9]([C:16]#N)[CH:8]=1.[CH2:18]([OH:20])[CH3:19]>>[CH3:6][C:7]1[C:12]([N+:13]([O-:15])=[O:14])=[CH:11][N:10]=[C:9]([C:16]([O:20][CH2:18][CH3:19])=[O:2])[CH:8]=1

Participants

4

Reactant 3

HCID 702EthanolHCID 1118Sulfuric AcidHCID 230001714-Methyl-5-nitropyridine-2-carbonitrile

Product 1

HCID 44549262HCID 44549262, compoundYield 56%

Procedure

Concentrated sulfuric acid (768 mL) was added slowly to ethanol (1.6 L) with cooling (exothermic reaction!). 4-Methyl-5-nitropyridine-2-carbonitrile (62.4 g, 0.38 mol) was added to the cold solution. After the addition was complete, the solution was refluxed under nitrogen for 2 h. Part of the solvent (500 mL) was removed using an oil pump at 30° C. The remaining thick solution was poured onto ice (1 kg). After stirring for 15 min, the mixture was extracted with ether (2×1 L) and multiple times with dichloromethane. At first, the organic layer was the TOP layer. As the extraction continued, the organic layer changed from the top layer to the bottom layer due to change in density as less ethanol was extracted. The combined organic extracts were dried (magnesium sulfate) and concentrated. Recrystallization from hexanes yielded 44.4 g (56%) of the desired product. 1H NMR (300 MHz, CDCl3) δ ppm 1.46 (t, 3H, J=7.5 Hz), 2.71 (s, 3H), 4.51 (q, 2H, J=7.5 Hz), 8.13 (s, 1H), 9.22 (s, 1H). LCMS: (APCI, M+H+)=209

Workup

  1. temperaturewith cooling
  2. custom(exothermic reaction!)
  3. additionAfter the addition
  4. temperaturethe solution was refluxed under nitrogen for 2 h
  5. customPart of the solvent (500 mL) was removed
  6. customat 30° C
  7. additionThe remaining thick solution was poured onto ice (1 kg)
  8. extractionthe mixture was extracted with ether (2×1 L) and multiple times with dichloromethane
  9. extractionAs the extraction
  10. extractionwas extracted
  11. dry with materialThe combined organic extracts were dried (magnesium sulfate)
  12. concentrationconcentrated
  13. customRecrystallization from hexanes

Sources & evidence

ORD record
ord-32b6ea71f54949b7a50ee79d0c96740e
Source dataset
uspto-grants-2008_12
Patent number
US07468375B2

Reaction notes

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