Sodium hydride → N-Methyl-4-ethynyl-4-(4-fluoro-2-nitrophenoxy)piperidine

HRID 1193550

Reaktionsgleichung

Reaktionsgleichung von HRID 1193550
[Na+].CS([CH2-])=O.[H-].[Na+].[CH3:8][N:9]1[CH2:14][CH2:13][C:12]([C:16]#[CH:17])([OH:15])[CH2:11][CH2:10]1.F[C:19]1[CH:24]=[CH:23][C:22]([F:25])=[CH:21][C:20]=1[N+:26]([O-:28])=[O:27]>CS(C)=O>[CH3:8][N:9]1[CH2:14][CH2:13][C:12]([C:16]#[CH:17])([O:15][C:19]2[CH:24]=[CH:23][C:22]([F:25])=[CH:21][C:20]=2[N+:26]([O-:28])=[O:27])[CH2:11][CH2:10]1

Komponenten

6

Edukt 4

HCID 24758Sodium hydrideHCID 677672,5-DifluoronitrobenzeneHCID 14190994-Piperidinol, 4-ethynyl-1-methyl- (6CI, 7CI, 8CI, 9CI)HCID 10154010Methane, sulfinylbis-, ion(1-), sodium

Produkt 1

HCID 14281483N-Methyl-4-ethynyl-4-(4-fluoro-2-nitrophenoxy)piperidineAusbeute 54 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 679Dimethyl SulfoxideLösungsmittel

Versuchsvorschrift

To a stirred solution of dimsyl sodium prepared from 43.0 g of sodium hydride (50% in oil, washed three times with hexanes) and 1100 ml of dimethylsulfoxide was added, in aliquots, 125 g of N-methyl-4-ethynyl-4-piperidinol at a rate such that the temperature remained below 23°. When the addition was complete, 167 g of 2,5-difluoronitrobenzene was added slowly dropwise at a rate such that the temperature remained below 21°. When the addition was complete, the mixture was poured into ice, extracted twice with ether, washed with saturated sodium chloride solution, and dried over anhydrous magnesium sulfate. The mixture was filtered and the filtrate was concentrated. The residue was filtered through 800 g of silica gel (70-250 mesh) and eluted with 3 l of 10% methanol/dichloromethane. Evaporation of solvent provided an oil, which crystallized on standing to yield 134 g (54%) of product. Recrystallization from cyclohexane provided the analytical sample, mp 70°-73°.

Aufarbeitung

  1. customremained below 23°
  2. additionWhen the addition
  3. customremained below 21°
  4. additionWhen the addition
  5. additionthe mixture was poured into ice
  6. extractionextracted twice with ether
  7. washwashed with saturated sodium chloride solution
  8. dry with materialdried over anhydrous magnesium sulfate
  9. filtrationThe mixture was filtered
  10. concentrationthe filtrate was concentrated
  11. filtrationThe residue was filtered through 800 g of silica gel (70-250 mesh)
  12. washeluted with 3 l of 10% methanol/dichloromethane
  13. customEvaporation of solvent
  14. customprovided an oil, which
  15. customcrystallized

Quellen und Nachweise

ORD-Eintrag
ord-115ef21ea1824b1c9100e3f018ca65c2
Quelldatensatz
uspto-grants-1989_03
Patentnummer
US04810792

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