Lithium Hexamethyldisilazide → 9-Benzenesulfonyl-5-hydroxy-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carbonitrile

HRID 1888385ノート

反応式

HRID 1888385 の反応式
C[Si]([N-][Si](C)(C)C)(C)C.[Li+].CO[C:13]([C:15]1[C:23]2[C:18](=[N:19][CH:20]=[CH:21][CH:22]=2)[N:17]([S:24]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)(=[O:26])=[O:25])[C:16]=1[CH2:33][N:34]([CH2:45][C:46]#[N:47])S(C1C=CC(C)=CC=1)(=O)=O)=[O:14]>C1COCC1>[C:27]1([S:24]([N:17]2[C:16]3[CH:33]=[N:34][C:45]([C:46]#[N:47])=[C:13]([OH:14])[C:15]=3[C:23]3[CH:22]=[CH:21][CH:20]=[N:19][C:18]2=3)(=[O:25])=[O:26])[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1

参加物

4

反応物 2

HCID 2733832Lithium HexamethyldisilazideHCID 582667731-benzenesulfonyl-2-{[cyanomethyl(toluene-4-sulfonyl)amino]methyl}-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester

生成物 1

HCID 582663029-Benzenesulfonyl-5-hydroxy-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carbonitrile

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-30 °C

実験手順

Lithium bis(trimethylsilyl)amide (9.6 mL, 1N solution in THF, 9.60 mmol) was added dropwise to a cooled (−78° C.) suspension of 1-benzenesulfonyl-2-{[cyanomethyl(toluene-4-sulfonyl)amino]methyl}-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester (1.72 g, 3.19 mmol) in dry THF (50 mL). The reaction mixture was allowed to warm to −30° C., stirred at −30° C. for 2 h, before warming to ambient temperature. The reaction mixture was quenched with saturated aqueous ammonium chloride solution (30 mL) and water (50 mL). The aqueous phase was extracted with DCM (2×20 mL) and the combined organic phase was washed with brine and concentrated in vacuo. The resultant solid was triturated with THF (2×4 mL) to afford the title compound. The filtrate was purified by flash chromatography (silica, 5 g column, Si-SPE, ethyl acetate then 10-20% MeOH in DCM) to afford the remaining title compound. The two batches of material were combined to afford a yellow solid (1.03 g, 90%). LCMS (Method B): RT=3.26 min, M+H+=351.

後処理

  1. temperaturea cooled
  2. temperaturebefore warming to ambient temperature
  3. customThe reaction mixture was quenched with saturated aqueous ammonium chloride solution (30 mL) and water (50 mL)
  4. extractionThe aqueous phase was extracted with DCM (2×20 mL)
  5. washthe combined organic phase was washed with brine
  6. concentrationconcentrated in vacuo
  7. customThe resultant solid was triturated with THF (2×4 mL)

出典と根拠

ORDレコード
ord-6a57ade0512f43538bc310d0a7584004
出典データセット
uspto-grants-2013_08
特許番号
US08501765B2

反応ノート

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