Tetrabutylammonium Fluoride → 3-(3-Hydroxy-3-methylbut-1-ynyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carbonitrile

HRID 1505956ノート

反応式

HRID 1505956 の反応式
[OH:1][C:2]([CH3:29])([CH3:28])[C:3]#[C:4][C:5]1[CH:27]=[N:26][C:8]2[N:9](COCC[Si](C)(C)C)[C:10]3[CH:15]=[N:14][C:13]([C:16]#[N:17])=[CH:12][C:11]=3[C:7]=2[CH:6]=1.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1>[OH:1][C:2]([CH3:29])([CH3:28])[C:3]#[C:4][C:5]1[CH:27]=[N:26][C:8]2[NH:9][C:10]3[CH:15]=[N:14][C:13]([C:16]#[N:17])=[CH:12][C:11]=3[C:7]=2[CH:6]=1

参加物

4

反応物 2

HCID 2724141Tetrabutylammonium FluorideHCID 58266403HCID 58266403、化合物

生成物 1

HCID 582665973-(3-Hydroxy-3-methylbut-1-ynyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carbonitrile収率 12.2%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
60 °C

実験手順

A solution of 3-(3-hydroxy-3-methylbut-1-ynyl)-9-(2-trimethylsilanyl-ethoxymethyl)dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile (254 mg, 0.624 mmol) in THF (12 mL) was treated with TBAF (3.7 mL, 12.5 mmol) and heated to 60° C. for 24 h. The reaction mixture was allowed to cool to ambient temperature and the solvent removed in vacuo. The resultant residue was dissolved in DCM, absorbed onto silica gel, and purified by flash chromatography (Biotage, 25 g, 1-100% EtOAc in heptane). The light orange solid was further purified by preparative HPLC (5-85% MeCN in water (0.1% NH4OH) over 30 min, 35 mL/min) to afford the title compound as an off-white solid (21 mg, 12%). 1H NMR (DMSO-D6, 400 MHz,): 12.99 (s, 1H), 9.04 (s, 1H), 8.93 (s, 1H), 8.86 (d, J=2.0 Hz, 1H), 8.69 (d, J=2.0 Hz, 1H), 5.53 (s, 1H), 1.55 (s, 6H). LCMS (Method D): RT=9.66 min, M+H+=277.

後処理

  1. temperatureto cool to ambient temperature
  2. customthe solvent removed in vacuo
  3. dissolutionThe resultant residue was dissolved in DCM
  4. customabsorbed onto silica gel
  5. custompurified by flash chromatography (Biotage, 25 g, 1-100% EtOAc in heptane)
  6. customThe light orange solid was further purified by preparative HPLC (5-85% MeCN in water (0.1% NH4OH) over 30 min, 35 mL/min)

出典と根拠

ORDレコード
ord-591c749fe6524f6a8bd284a8ccb34d60
出典データセット
uspto-grants-2015_12
特許番号
US09216980B2

反応ノート

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