Oxalic Acid → 2-(2-Methoxy-5-phenylsulphonylphenyl)-5-[1-(1-piperidinyl)ethyl]-1H-pyrrole oxalate

HRID 259761

Reaktionsgleichung

Reaktionsgleichung von HRID 259761
[C:1]([N:4]1[CH2:9][CH2:8][CH2:7][CH2:6][CH2:5]1)(=O)[CH3:2].P(Cl)(Cl)(Cl)=O.[CH3:15][O:16][C:17]1[CH:22]=[CH:21][C:20]([S:23]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)(=[O:25])=[O:24])=[CH:19][C:18]=1[C:32]1[NH:33][CH:34]=[CH:35][CH:36]=1.[BH4-].[Na+].[C:39]([OH:44])(=[O:43])[C:40]([OH:42])=[O:41]>ClCCCl.CCOC(C)=O.CO.O>[C:39]([OH:44])(=[O:43])[C:40]([OH:42])=[O:41].[CH3:15][O:16][C:17]1[CH:22]=[CH:21][C:20]([S:23]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)(=[O:25])=[O:24])=[CH:19][C:18]=1[C:32]1[NH:33][C:34]([CH:1]([N:4]2[CH2:9][CH2:8][CH2:7][CH2:6][CH2:5]2)[CH3:2])=[CH:35][CH:36]=1

Komponenten

10

Edukt 5

HCID 971Oxalic AcidHCID 120581-AcetylpiperidineHCID 24813Phosphorus oxychlorideHCID 4311764Sodium borohydrideHCID 224030852-(2-Methoxy-5-phenylsulphonylphenyl)-1H-pyrrole

Produkt 1

HCID 224031232-(2-Methoxy-5-phenylsulphonylphenyl)-5-[1-(1-piperidinyl)ethyl]-1H-pyrrole oxalate

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 111,2-DichloroethaneLösungsmittel2×HCID 887MethanolLösungsmittel2×HCID 962WaterLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To 1-acetylpiperidine (0.61 ml) under argon, was added phosphorus oxychloride (0.45 ml) at ambient temperature. After stirring for 0.5 h 1,2-dichloroethane (10 ml) was added and the mixture cooled to 0° C. A solution of 2-(2-methoxy-3-phenylsulphonylphenyl)-1H-pyrrole (D25) (1.0 g) in 1,2-dichloroethane (10 ml) was added dropwise over 0.3 h. Stirring was continued at 0° C. for 3 h and at ambient temperature for 18 h. The mixture was cooled to 0° C. and sodium borohydride (1 g) added portionwise over 0.16 h. Stirring was continued at ambient temperature for 2.5 h before the mixture was cooled to 0° C. Water (5 ml) followed by MeOH (5 ml) was added dropwise followed by dilution with more water (50 ml). The mixture was extracted with dichloromethane (3×200 ml) and the combined extracts dried (Na2SO4) and evaporated in vacuo. Methanol (10 ml) and concentrated HCl (4.8 ml) were added and the mixture stirred for 4 h. Water (100ml) was added and the solution basified with NaOH (10%) and extracted with dichloromethane (3×200 ml). Combined extracts were dried (Na2SO4) and evaporated in vacuo. This material was dissolved in EtOAc and added to a hot solution of oxalic acid (1 equivalent) in EtOAc. Sufficient MeOH was added to dissolve the precipitated solid and the resultant solution cooled to give the title compound (E38) (0.27 g).

Aufarbeitung

  1. additionwas added
  2. temperatureThe mixture was cooled to 0° C.
  3. stirringStirring
  4. waitwas continued at ambient temperature for 2.5 h before the mixture
  5. temperaturewas cooled to 0° C
  6. additionwas added dropwise
  7. extractionThe mixture was extracted with dichloromethane (3×200 ml)
  8. dry with materialthe combined extracts dried (Na2SO4)
  9. customevaporated in vacuo
  10. additionMethanol (10 ml) and concentrated HCl (4.8 ml) were added
  11. stirringthe mixture stirred for 4 h
  12. additionWater (100ml) was added
  13. extractionextracted with dichloromethane (3×200 ml)
  14. dry with materialCombined extracts were dried (Na2SO4)
  15. customevaporated in vacuo
  16. dissolutionThis material was dissolved in EtOAc
  17. dissolutionto dissolve the precipitated solid

Quellen und Nachweise

ORD-Eintrag
ord-dde6b5b342a94237bcdaab88700876d2
Quelldatensatz
uspto-grants-1996_06
Patentnummer
US05523299

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