Dimethyl Sulfoxide → Benzyl 4-methylidenepiperidine-1-carboxylate

HRID 1781998

Reaktionsgleichung

Reaktionsgleichung von HRID 1781998
[H-].[Na+].O=[C:4]1[CH2:9][CH2:8][N:7]([C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[O:11])[CH2:6][CH2:5]1.O.[CH3:21]S(C)=O>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH2:21]=[C:4]1[CH2:9][CH2:8][N:7]([C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[O:11])[CH2:6][CH2:5]1

Komponenten

6

Edukt 4

HCID 679Dimethyl Sulfoxide3×HCID 962WaterHCID 24758Sodium hydrideHCID 643496Benzyl 4-oxopiperidine-1-carboxylate

Produkt 1

HCID 15519136Benzyl 4-methylidenepiperidine-1-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 74505Methyltriphenyliphosphonium bromideKatalysator

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

A sodium hydride (13.2 g) was added to an anhydrous dimethylsulfoxide (176 mL) and the mixture was heated for 2 hours at 60° C. After cooling, to a suspension of methyltriphenylphosphonium bromide (110.4 g) in dimethylsulfoxide (120 mL) was added the reaction mixture, and the mixture was stirred for 30 minutes at room temperature. To the reaction mixture was added a solution of benzyl 4-oxo-1-piperidinecarboxylate (60 g) in dimethylsulfoxide (150 mL), the mixture was stirred for 1 hour at 50° C. After cooling, to the mixture was added water (2.5 L) and the mixture was extracted with ethyl acetate (1.5 L). The organic layer was washed with a saturated aqueous solution of ammonium chloride (0.5 L) and a saturated aqueous solution of sodium chloride (0.5 L), dried and then concentrated. The obtained residue was purified by column chromatography on silica gel (n-hexane:ethyl acetate:chloroform=9:1:1) to give the title compound (51.1 g) having the following physical data.

Aufarbeitung

  1. additionwas added the reaction mixture
  2. stirringthe mixture was stirred for 1 hour at 50° C
  3. temperatureAfter cooling, to the mixture
  4. extractionthe mixture was extracted with ethyl acetate (1.5 L)
  5. washThe organic layer was washed with a saturated aqueous solution of ammonium chloride (0.5 L)
  6. dry with materiala saturated aqueous solution of sodium chloride (0.5 L), dried
  7. concentrationconcentrated
  8. customThe obtained residue was purified by column chromatography on silica gel (n-hexane:ethyl acetate:chloroform=9:1:1)

Quellen und Nachweise

ORD-Eintrag
ord-976196165fb343849eb72f934f0676e2
Quelldatensatz
uspto-grants-2009_03
Patentnummer
US07498323B2

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