2,1,3-Benzoxadiazole-4-carbaldehyde → HCID 178509375, Verbindung

HRID 489448Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 489448
[N:1]1[O:2][N:3]=[C:4]2[C:9]([CH:10]=O)=[CH:8][CH:7]=[CH:6][C:5]=12.[NH2:12][C:13]1[CH:17]=[CH:16][NH:15][N:14]=1.[C:18]([CH2:20][C:21]([CH:23]1[CH2:32][CH2:31][CH2:30][CH2:29][C:24]21[O:28][CH2:27][CH2:26][O:25]2)=O)#[N:19]>C(#N)C>[N:1]1[O:2][N:3]=[C:4]2[C:9]([CH:10]3[C:20]([C:18]#[N:19])=[C:21]([CH:23]4[CH2:32][CH2:31][CH2:30][CH2:29][C:24]54[O:28][CH2:27][CH2:26][O:25]5)[NH:12][C:13]4=[N:14][NH:15][CH:16]=[C:17]34)=[CH:8][CH:7]=[CH:6][C:5]=12

Komponenten

5

Edukt 3

HCID 102908732,1,3-Benzoxadiazole-4-carbaldehydeHCID 22265391HCID 22265391, VerbindungHCID 178418806HCID 178418806, Verbindung

Produkt 1

HCID 178509375HCID 178509375, VerbindungAusbeute 59,5 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

To a solution of ethyl 2-cyclohexanonecarboxylate (25 g) in toluene (200 mL) was added ethyleneglycol (10.1 g) and p-toluenesulfonic acid (2.8 g) at room temperature and the mixture was heated under reflux with Dean-Stark apparatus for five hours. The reaction mixture was cooled to room temperature, the solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (eluent:hexane-ethyl acetate (10:1)) to give ethyl 1,4-dioxa-spiro[4,5]decane-6-carboxylate (31 g) as a colorless oil. To a solution of acetonitrile (7.2 g) in THF (700 mL) was added n-BuLi (160 mmol) at −78° C. Further, ethyl 1,4-dioxa-spiro[4,5]decane-6-carboxylate (31 g) was added and the mixture was stirred for an hour. After acidification with hydrochloric acid, the mixture was extracted with ethyl acetate. The solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (eluent:hexane-ethyl acetate (10:1)) to give 1-cyano-2-(1,4-dioxa-spiro[4,5]decan-6-yl)ethan-2-one (14.5 g) as a colorless oil. A solution of 2,1,3-benzoxadiazole-4-aldehyde (0.8 g), 3-aminopyrazole (0.5 g) and 1-cyano-2-(1,4-dioxa-spiro[4,5]-decan-6-yl)ethan-2-one (1.2 g) in acetonitrile (10 mL) was heated under reflux overnight. The reaction mixture was cooled to room temperature, and the precipitated crystals were collected by filtration to give 4-(2,1,3-benzoxadiazol-4-yl)-5-cyano-4,7-dihydro-6-(1,4-dioxa-spiro[4,5]decan-6-yl)-2H-pyrazolo[3,4-b]pyridine (1.3 g) as colorless crystals.

Aufarbeitung

  1. temperatureunder reflux overnight
  2. filtrationthe precipitated crystals were collected by filtration

Quellen und Nachweise

ORD-Eintrag
ord-a6ebd8af02dd4ccba040f6c1e8a9f415
Quelldatensatz
uspto-grants-2005_12
Patentnummer
US06977262B2

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