Hexen-2-al → Diethyl 4-n-propylpyridine-2,3-dicarboxylate

HRID 1936695Notes

Reaction equation

HRID 1936695 reaction equation
Cl[CH:2]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[C:3](=O)[C:4]([O:6][CH2:7][CH3:8])=[O:5].[CH3:15][C:16](=O)[CH:17]=[CH:18][CH2:19][CH3:20].S(=O)(=O)([O-])[NH2:23].[NH4+]>C(O)C>[CH2:17]([C:18]1[CH:19]=[CH:20][N:23]=[C:3]([C:4]([O:6][CH2:7][CH3:8])=[O:5])[C:2]=1[C:10]([O:12][CH2:13][CH3:14])=[O:11])[CH2:16][CH3:15]

Participants

5

Reactant 3

HCID 12990Hexen-2-alHCID 24482Ammonium sulfamateHCID 10998635Diethyl 2-chloro-3-oxobutanedioate

Product 1

HCID 22462372Diethyl 4-n-propylpyridine-2,3-dicarboxylateYield 21%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A solution of diethyl 3-chloro-2-oxosuccinate (137.4 g, 0.69 mol), hexen-2-al (72.5 g, 0.74 mol) and ammonium sulphamate (190.2 g, 1.66 mol) in ethanol (450 ml) was stirred under reflux for 36 hours and then filtered. The filtrate was evaporated under vacuum, the resulting residue dissolved in water (500 ml) and this solution extracted with ethyl acetate (6×500 ml). The combined organic extracts were dried (MgSO4) and evaporated under vacuum, then the resulting residue was chromatographed on silica gel (50 g), using an ethyl acetate in hexane elution gradient (0-20% ethyl acetate), to give the title compound as an orange oil (34.1 g, 21%). Rf 0.20 (ethyl acetate:hexane, 20:80).

Workup

  1. temperatureunder reflux for 36 hours
  2. filtrationfiltered
  3. customThe filtrate was evaporated under vacuum
  4. dissolutionthe resulting residue dissolved in water (500 ml)
  5. extractionthis solution extracted with ethyl acetate (6×500 ml)
  6. dry with materialThe combined organic extracts were dried (MgSO4)
  7. customevaporated under vacuum
  8. customthe resulting residue was chromatographed on silica gel (50 g)
  9. washan ethyl acetate in hexane elution gradient (0-20% ethyl acetate)

Sources & evidence

ORD record
ord-cc0872dd258b48ea86be6a68f141cca7
Source dataset
uspto-grants-2002_05
Patent number
US06391885B1

Reaction notes

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