Ammonium sulfamate → Diethyl 5-ethylpyridine-2,3-dicarboxylate

HRID 3918

Reaction equation

HRID 3918 reaction equation
[CH3:1][CH2:2][C:3]([CH:5]=O)=[CH2:4].Cl[CH:8]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[C:9](=O)[C:10]([O:12][CH2:13][CH3:14])=[O:11].S(=O)(=O)([O-])[NH2:22].[NH4+]>C(O)C>[CH2:2]([C:3]1[CH:4]=[C:8]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[C:9]([C:10]([O:12][CH2:13][CH3:14])=[O:11])=[N:22][CH:5]=1)[CH3:1]

Participants

5

Reactant 3

HCID 24482Ammonium sulfamateHCID 70203EthylacroleinHCID 10998635Diethyl 2-chloro-3-oxobutanedioate

Product 1

HCID 10857926Diethyl 5-ethylpyridine-2,3-dicarboxylateYield 86%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A stirred mixture of ethacrolein, (4.2 g, 0.05 mol), diethyl 3-chloro-2-oxo-butanedioate, (11.2 g, 0.05 mol) and ammonium sulfamate, (15.4 g, 0.135 mol) in ethanol (37 mL) is heated at reflux. After 15 hours the mixture is cooled to room temperature and the solvent removed by distillation under reduced pressure. The residue is treated with water and extracted with ethyl acetate. The organic phase is separated and concentrated in vacuo and the residue purified by column chromatography on silica gel using 4:1 hexane-ethyl acetate as the eluent to give 10.8 g (75% yield) of the title product as an oil which is shown to be 95% pure by a gas chromatography assay.

Workup

  1. temperatureis heated
  2. temperatureat reflux
  3. customthe solvent removed by distillation under reduced pressure
  4. additionThe residue is treated with water
  5. extractionextracted with ethyl acetate
  6. customThe organic phase is separated
  7. concentrationconcentrated in vacuo
  8. customthe residue purified by column chromatography on silica gel using 4:1 hexane-ethyl acetate as the eluent

Sources & evidence

ORD record
ord-b5d15bfc6ae942d6b4900629eb592e0d
Source dataset
uspto-grants-1988_02
Patent number
US04723011

Linked notes

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