3-Bromopyridine → 4-Benzothiazol-2-YL-5-pyridin-3-YL-1H-pyrazol-3-ylamine

HRID 57270

Reaktionsgleichung

Reaktionsgleichung von HRID 57270
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([Li])[CH:2]=1.[Li]CCCC.Br[C:14]1[CH:15]=[N:16][CH:17]=[CH:18][CH:19]=1.S1C2C=CC=CC=2[N:22]=[C:21]1[C:29](=[C:32]([S:35][CH3:36])SC)[C:30]#[N:31].[NH4+:37].[Cl-]>C1COCC1.C1CCCCC1.CCOCC>[S:35]1[C:36]2[CH:2]=[CH:3][CH:4]=[CH:5][C:6]=2[N:1]=[C:32]1[C:29]1[C:30]([NH2:31])=[N:37][NH:22][C:21]=1[C:14]1[CH:15]=[N:16][CH:17]=[CH:18][CH:19]=1

Komponenten

9

Edukt 5

HCID 122863-BromopyridineHCID 25517Ammonium ChlorideHCID 28077272-Benzothiazol-2-yl-3,3-bis-methylsulfanylacrylonitrileHCID 178418339ButyllithiumHCID 178418470HCID 178418470, Verbindung

Produkt 1

HCID 667682744-Benzothiazol-2-YL-5-pyridin-3-YL-1H-pyrazol-3-ylamineAusbeute 65 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 3283Diethyl EtherLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×HCID 8078CyclohexaneLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

A yellow suspension of 3-pyridinyl lithium in THF was prepared according to the literature (Cama, L. D.; Wildonger, K. J.; Guthikonda, R.; Ratcliffe, R. W.; Christensen, B. G. Tetrahedron (1983), 39, 2531) by adding n-BuLi (0.25 mL of a 2 M solution in cyclohexane, 0.5 mmol) to a solution of 3-bromopyridine (87 mg, 0.5 mmol) in anhydrous ether (3 mL) at −78° C. To this slurry was rapidly added 2-benzothiazol-2-yl-3,3-bismethylsulfanylacrylonitrile (140 mg, 0.5 mmol) in anhydrous THF (5 mL) under argon. The resulting mixture was stirred at −78° C. for 1 hour, and then slowly warmed up to room temperature and stirred at that temperature for 2 hours. Upon completion of the reaction, the mixture was poured into a saturated NH4Cl aqueous solution. The aqueous phase was extracted with ethyl acetate. The organic phase was washed with brine, dried over magnesium sulfate, filtered and evaporated. The crude material was then purified by flash chromatography eluting with CH2Cl2:MeOH=1:0-19:1 to yield 100 mg (65%) of the desired product as a brown oil. MS (m/z, ES+): 310 (M+1, 25%), 263 (M−46, 100%).

Aufarbeitung

  1. customwas prepared
  2. temperatureslowly warmed up to room temperature
  3. stirringstirred at that temperature for 2 hours
  4. customUpon completion of the reaction
  5. extractionThe aqueous phase was extracted with ethyl acetate
  6. washThe organic phase was washed with brine
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. customevaporated
  10. customThe crude material was then purified by flash chromatography
  11. washeluting with CH2Cl2

Quellen und Nachweise

ORD-Eintrag
ord-70915a15398141a5a91c7e411a0d5d51
Quelldatensatz
uspto-grants-2016_09
Patentnummer
US09434720B2

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