Ammonium sulfamate → Ethyl 2-chloromethyl-5-ethylnicotinate

HRID 1032818

Reaktionsgleichung

Reaktionsgleichung von HRID 1032818
[CH2:1]([O:3][C:4](=[O:11])[CH:5](Cl)[C:6]([CH2:8][Cl:9])=O)[CH3:2].[CH2:12]([C:14](=[CH2:17])[CH:15]=O)[CH3:13].S(=O)(=O)([O-])[NH2:19].[NH4+]>C(O)C>[Cl:9][CH2:8][C:6]1[N:19]=[CH:15][C:14]([CH2:12][CH3:13])=[CH:17][C:5]=1[C:4]([O:3][CH2:1][CH3:2])=[O:11]

Komponenten

5

Edukt 3

HCID 24482Ammonium sulfamateHCID 70203EthylacroleinHCID 101546Ethyl 2,4-dichloro-3-oxobutanoate

Produkt 1

HCID 14600680Ethyl 2-chloromethyl-5-ethylnicotinateAusbeute 43,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 702EthanolLösungsmittel

Versuchsvorschrift

A solution of 61 g of ethyl-2,4-dichloroacetoacetate (0.306 mol) and 30 g of 2-ethylacrolein (0.357 mol) in 500 mL of absolute ethanol is mixed with 85.5 g of ammonium sulfamate (0.75 mol), and the stirred mixture is heated at reflux for 90 minutes. The reaction is concentrated in vacuo and the residue is partitioned between ethyl acetate and water. The organic phase is concentrated in vacuo, and the residue is chromatographed on silica gel using hexane-ethyl acetate mixtures to give 50 g of crude product. This material is purified by extraction into aqueous hydrochloric acid, washing with hexanes, making the aqueous phase basic with cold ammonium hydroxide, and extracting with hexanes to afford 30 g of the title product as an oil (43%), having elemental analysis calculated for C11H14ClNO2 % C 58.03, H 6.20, N 6.15, Cl 15.57 found % C 58.29, H 6.30, N 6.02, Cl 15.49.

Aufarbeitung

  1. temperaturethe stirred mixture is heated
  2. temperatureat reflux for 90 minutes
  3. concentrationThe reaction is concentrated in vacuo
  4. customthe residue is partitioned between ethyl acetate and water
  5. concentrationThe organic phase is concentrated in vacuo
  6. customthe residue is chromatographed on silica gel
  7. customto give 50 g of crude product
  8. customThis material is purified by extraction into aqueous hydrochloric acid
  9. washwashing with hexanes
  10. extractionextracting with hexanes

Quellen und Nachweise

ORD-Eintrag
ord-d17ece7ac57c423dbc0adc55fcf61259
Quelldatensatz
uspto-grants-1990_09
Patentnummer
US04959476

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