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

HRID 407329

반응식

HRID 407329 반응식
[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

참가 물질

9

반응물 5

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

생성물 1

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

시약·촉매·용매 3

HCID 3283Diethyl Ether용매HCID 8028Tetrahydrofuran용매2회HCID 8078Cyclohexane용매

반응 조건

온도
-78 °C

실험 절차

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%).

후처리

  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

출처 및 근거

ORD 기록
ord-2b04432a85644bff9db0ac1ffd348bdf
출처 데이터셋
uspto-grants-2014_06
특허 번호
US08754233B2

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