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Hydrochloric Acid → Methyl (2-chlorophenyl)(6,7-dihydro-4H-thieno[3,2-c]pyridin-5-yl)acetate hydrochloride hydrate

HRID 568129
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 568129
Cl.[S:2]1[CH:6]=[CH:5][CH:4]=[C:3]1[CH2:7][CH2:8][NH:9][CH:10]([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1[Cl:21])[C:11]([O:13][CH3:14])=[O:12].[C:22](=O)([O-])O.[Na+].C=O.Cl>O.C(O)=O.CC(C)=O.ClCCCl>[OH2:12].[ClH:21].[Cl:21][C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=1[CH:10]([N:9]1[CH2:8][CH2:7][C:3]2[S:2][CH:6]=[CH:5][C:4]=2[CH2:22]1)[C:11]([O:13][CH3:14])=[O:12]
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

9

Edukt 4

HCID 313Hydrochloric AcidHCID 712FormaldehydeHCID 516892Sodium BicarbonateHCID 24820193Methyl 2-(2-chlorophenyl)-2-((2-(thiophen-2-yl)ethyl)amino)acetate hydrochloride

Produkt 1

HCID 86756347Methyl (2-chlorophenyl)(6,7-dihydro-4H-thieno[3,2-c]pyridin-5-yl)acetate hydrochloride hydrateAusbeute 86,6 %

Reagenzien, Katalysatoren, Lösungsmittel

4
HCID 111,2-DichloroethaneLösungsmittelHCID 180AcetoneLösungsmittelHCID 284Formic AcidLösungsmittelHCID 962WaterLösungsmittel

Versuchsvorschrift

To 28.4 g (0.082 mol) of methyl [2-(2-thienyl)ethylamino](2-chlorophenyl)acetate hydrochloride, prepared according to example 9. or 10., are added 50 ml of 1,2-dichloroethane and the solution of 7.5 g (0.09 mol) of sodium hydrogen carbonate in 100 ml of water. The mixture is stirred well, the phases are separated, the aqueous phase is washed with 2×30 ml of 1,2-dichloroethane, the combined organic layer is dried over anhydrous sodium sulfate and the solvent is removed in vacuo. The residual 25 g material (acetate base) is dissolved in 90 ml of formic acid, to the solution 4 g (0.13 mol) of paraformaldehyde is added and the mixture is stirred at 50° C. for 20 minutes. The majority of the formic acid is then distilled off in vacuo, the residue is dissolved in the mixture of 100 ml of water and 100 ml of 1,2-dichloroethane, the phases are separated, the aqueous phase is extracted again with 30 ml of 1,2-dichloroethane, the combined organic phase is shaken well with 100 ml of 5% sodium hydrogen carbonate solution, the phases are separated and the organic phase is dried over anhydrous sodium sulfate and evaporated in vacuo. The residue is dissolved in 45 ml of acetone and to the solution 6.5 ml (0.077 mol) of conc. hydrochloric acid is added at 5-10° C., under cooling. The product slowly crystallizes. The mixture is stirred for 1 hour at 0-10° C., then the crystals are filtered off, washed with 2×10 ml of acetone and dried. Weight: 26.7 g (theoretical: 30.8 g) Yield: 86.6%, mp.: 138-140° C. (literature mp: 130-140° C.). The product was identified by elementary analysis, IR spectrum, 1H-NMR investigation and melting point determination.

Aufarbeitung

  1. customthe phases are separated
  2. washthe aqueous phase is washed with 2×30 ml of 1,2-dichloroethane
  3. dry with materialthe combined organic layer is dried over anhydrous sodium sulfate
  4. customthe solvent is removed in vacuo
  5. additionis added
  6. stirringthe mixture is stirred at 50° C. for 20 minutes
  7. distillationThe majority of the formic acid is then distilled off in vacuo
  8. dissolutionthe residue is dissolved in the mixture of 100 ml of water and 100 ml of 1,2-dichloroethane
  9. customthe phases are separated
  10. extractionthe aqueous phase is extracted again with 30 ml of 1,2-dichloroethane
  11. stirringthe combined organic phase is shaken well with 100 ml of 5% sodium hydrogen carbonate solution
  12. customthe phases are separated
  13. dry with materialthe organic phase is dried over anhydrous sodium sulfate
  14. customevaporated in vacuo
  15. additionis added at 5-10° C.
  16. temperatureunder cooling
  17. customThe product slowly crystallizes
  18. stirringThe mixture is stirred for 1 hour at 0-10° C.
  19. filtrationthe crystals are filtered off
  20. washwashed with 2×10 ml of acetone
  21. customdried

Quellen und Nachweise

ORD-Eintrag
ord-1e7cd6ce43434b1aabce2be49a4cc52a
Quelldatensatz
uspto-grants-2001_01
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US06180793B2

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