Iodine → 2-iodo-1-tosyl-1H-pyrrolo[2,3-b]pyridine-4-carbonitrile

HRID 2182243노트

반응식

HRID 2182243 반응식
C(NC(C)C)(C)C.C([Li])CCC.[C:13]1([CH3:33])[CH:18]=[CH:17][C:16]([S:19]([N:22]2[C:26]3[N:27]=[CH:28][CH:29]=[C:30]([C:31]#[N:32])[C:25]=3[CH:24]=[CH:23]2)(=[O:21])=[O:20])=[CH:15][CH:14]=1.[I:34]I>O1CCCC1.O>[I:34][C:23]1[N:22]([S:19]([C:16]2[CH:15]=[CH:14][C:13]([CH3:33])=[CH:18][CH:17]=2)(=[O:21])=[O:20])[C:26]2[N:27]=[CH:28][CH:29]=[C:30]([C:31]#[N:32])[C:25]=2[CH:24]=1

참가 물질

7

반응물 4

HCID 807IodineHCID 7912DiisopropylamineHCID 224772881H-Pyrrolo[2,3-B]pyridine-4-carbonitrile, 1-[(4-methylphenyl)sulfonyl]-HCID 178418339Butyllithium

생성물 1

HCID 224773222-iodo-1-tosyl-1H-pyrrolo[2,3-b]pyridine-4-carbonitrile수율 48.6%

시약·촉매·용매 2

HCID 962Water용매HCID 8028Tetrahydrofuran용매3회

실험 절차

A stirred solution of diisopropylamine (0.38 mL) in tetrahydrofuran (7 mL), at −70° C. and under nitrogen, was treated with a solution of n-butyllithium in hexanes (1.06 mL, 2.5M) over 5 minutes, whilst maintaining the temperature below −65° C. After stirring for 20 minutes the mixture was added, at −70° C., to a solution of 1-(toluene-4-sulfonyl)-1H-pyrrolo[2,3-b]pyridine-4-carbonitrile (0.65 g, Reference Example 63) in tetrahydrofuran (15 mL) and stirred at −70° C. for 45 minutes. A solution of iodine (0.9 g) in tetrahydrofuran (10 mL) was then added at −70° C. The reaction mixture was allowed to warm up to room temperature over 1 hour, and stirred for 18 hours, then treated with water (10 mL). The reaction mixture was evaporated in vacuo and the residue partitioned between ethyl acetate (75 mL) and water (50 mL). The insoluble material was filtered, washed with ether and dried in vacuo to give the title compound (0.45 g) as a white solid. The filtrate was separated and the organics washed sequentially with saturated sodium thiosulfate solution (2×30 mL), water (30 mL) and brine (30 mL), dried over sodium sulfate and evaporated. The residue was triturated with diethyl ether to give a further quantity of the title compound (0.25 g) as a cream solid. TLC RF=0.43 (ethyl acetate/heptane 1:1). MS: 424 (MH+).

후처리

  1. temperaturewhilst maintaining the temperature below −65° C
  2. stirringstirred at −70° C. for 45 minutes
  3. stirringstirred for 18 hours
  4. customThe reaction mixture was evaporated in vacuo
  5. customthe residue partitioned between ethyl acetate (75 mL) and water (50 mL)
  6. filtrationThe insoluble material was filtered
  7. washwashed with ether
  8. customdried in vacuo

출처 및 근거

ORD 기록
ord-a522877d76b243389c493120596c724b
출처 데이터셋
uspto-grants-2005_05
특허 번호
US06897207B2

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