Ammonium nitrate → 1,1-Diethoxy-2-butene

HRID 1944566Notes

Reaction equation

HRID 1944566 reaction equation
[CH:1](=O)/[CH:2]=[CH:3]/C.[CH:6]([O:13][CH2:14][CH3:15])([O:10][CH2:11][CH3:12])OCC.[N+]([O-])([O-])=O.[NH4+]>CCO.CCOC(C)=O>[CH2:14]([O:13][CH:6]([O:10][CH2:11][CH3:12])[CH:1]=[CH:2][CH3:3])[CH3:15]

Participants

6

Reactant 3

HCID 22985Ammonium nitrateHCID 31214Ethyl orthoformateHCID 447466Crotonaldehyde

Product 1

HCID 997781,1-Diethoxy-2-buteneYield 89%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

Crotonaldehyde (23.64 mL, 285.35 mmol), triethyl orthoformate (57.02 mL, 342.42 mmol) and ammonium nitrate (2.28 g, 28.54 mmol) were combined in 60 mL EtOH. After 22 h at ambient temperature, the reaction was diluted with EtOAc (60 mL) and washed with saturated sodium bicarbonate solution (40 mL). The aqueous layer was back extracted with EtOAc (20 mL). The combined organics were washed with brine (40 mL), dried over Na2SO4, filtered and concentrated in vacuo to give 36.5 g (89%) of 1,1-diethoxybut-2-ene. 1H NMR (CDCl3, 400 MHz) 5.84 (m, 1H); 5.54 (m, 1H); 4.82 (d, J=5.7 Hz, 1H); 3.64 (m, 2H); 3.49 (m, 2H); 1.73 (m, 3H); 1.21 (m, 6H).

Workup

  1. washwashed with saturated sodium bicarbonate solution (40 mL)
  2. extractionThe aqueous layer was back extracted with EtOAc (20 mL)
  3. washThe combined organics were washed with brine (40 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-0d61e61556834235ad87380cc435a00a
Source dataset
uspto-grants-2013_03
Patent number
US08394837B2

Reaction notes

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