Phosphorus oxychloride → 1-Chloro-4-hydroxy-isoquinoline-3-carboxylic acid butyl ester

HRID 250303Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 250303
[CH2:1]([O:5][C:6]([C:8]1[N:9]=[C:10](O)[C:11]2[C:16]([C:17]=1[OH:18])=[CH:15][CH:14]=[CH:13][CH:12]=2)=[O:7])[CH2:2][CH2:3][CH3:4].P(Cl)(Cl)([Cl:22])=O>>[CH2:1]([O:5][C:6]([C:8]1[N:9]=[C:10]([Cl:22])[C:11]2[C:16]([C:17]=1[OH:18])=[CH:15][CH:14]=[CH:13][CH:12]=2)=[O:7])[CH2:2][CH2:3][CH3:4]

Komponenten

3

Edukt 2

HCID 24813Phosphorus oxychloride2×HCID 1784508431,4-Dihydroxy-isoquinoline-3-carboxylic acid butyl ester

Produkt 1

HCID 860145021-Chloro-4-hydroxy-isoquinoline-3-carboxylic acid butyl ester

Versuchsvorschrift

A mixture of 17.3 g (66.2 mmol) of 1,4-dihydroxy-isoquinoline-3-carboxylic acid butyl ester and 100 ml of phosphorous oxychloride was stirred at ambient temperature for 1 h, and then heated slowly with stirring in the course of 2 h to reflux temperature. The mixture was refluxed gently with stirring for 30 min. After cooling to room temperature the excess phosphorous oxychloride was evaporated in vacuo, and the residue was dissolved in 100 ml of ethyl acetate. The solution was poured into 300 ml of a saturated aqueous sodium bicarbonate solution with stirring. The precipitate formed was removed by vacuum filtration. The organic phase was separated, and the aqueous phase was extracted with 3×100 ml of ethyl acetate. The combined aqueous phases were dried over sodium sulfate, filtered through a pad of silica gel and evaporated in vacuo to give a brown oil that solidified later. 11.37 g of the title compound were obtained; 1H NMR (CDCl3): δ=11.91 (s, 1H), 8.41 (m, 1H), 8.29 (m, 1H), 7.83 (m, 2H), 4.49 (t, 2H), 1.84 (m, 2H), 1.48 (m, 2H), 0.99 (t, 3H).

Aufarbeitung

  1. temperatureheated slowly
  2. stirringwith stirring in the course of 2 h
  3. temperatureto reflux temperature
  4. temperatureThe mixture was refluxed gently
  5. stirringwith stirring for 30 min
  6. customwas evaporated in vacuo
  7. dissolutionthe residue was dissolved in 100 ml of ethyl acetate
  8. additionThe solution was poured into 300 ml of a saturated aqueous sodium bicarbonate solution
  9. stirringwith stirring
  10. customThe precipitate formed
  11. customwas removed by vacuum filtration
  12. customThe organic phase was separated
  13. extractionthe aqueous phase was extracted with 3×100 ml of ethyl acetate
  14. dry with materialThe combined aqueous phases were dried over sodium sulfate
  15. filtrationfiltered through a pad of silica gel
  16. customevaporated in vacuo
  17. customto give a brown oil that

Quellen und Nachweise

ORD-Eintrag
ord-35a53cb8c16349fc98d0fd569bf241c5
Quelldatensatz
uspto-grants-2011_01
Patentnummer
US07863292B2

Notizen zur Reaktion

Wird geladen…