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

HRID 1765616ノート

反応式

HRID 1765616 の反応式
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

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒3 回

実験手順

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 thiosulphate solution (2×30 mL), water (30 mL) and brine (30 mL), dried over sodium sulphate and evaporated. The residue was triturated with diethyl ether to give the title compound (0.25 g) as a cream solid. TLC RF=0.43 (ethyl acetate/heptane 1:1). MS: 424 (MH+).

後処理

  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

出典と根拠

ORDレコード
ord-dc2b755fb5184795bf8fbeaf34c0cdeb
出典データセット
uspto-grants-2007_06
特許番号
US07227020B2

反応ノート

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