3,3-Dimethyl-1-butyne → 2-(6-Chloro-4-(3,3-dimethylbut-1-ynyl)pyridin-3-ylamino)ethanol

HRID 513089ノート

反応式

HRID 513089 の反応式
[Cl:1][C:2]1[N:7]=[CH:6][C:5]([NH:8][CH2:9][CH2:10][OH:11])=[C:4](I)[CH:3]=1.[CH3:13][C:14]([CH3:18])([CH3:17])[C:15]#[CH:16]>CCN(CC)CC.[Cu]I>[Cl:1][C:2]1[N:7]=[CH:6][C:5]([NH:8][CH2:9][CH2:10][OH:11])=[C:4]([C:16]#[C:15][C:14]([CH3:18])([CH3:17])[CH3:13])[CH:3]=1

参加物

5

反応物 2

HCID 135123,3-Dimethyl-1-butyneHCID 579081632-(6-Chloro-4-iodopyridin-3-ylamino)ethanol

生成物 1

HCID 579081822-(6-Chloro-4-(3,3-dimethylbut-1-ynyl)pyridin-3-ylamino)ethanol収率 29.1%

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 8471Triethylamine溶媒

実験手順

To a solution of 2-(6-chloro-4-iodopyridin-3-ylamino)ethanol (14.5 g, 49 mmol) in Et3N (200 mL) were added 3,3-dimethyl-but-1-yne (12.0 g, 146 mol), CuI (0.9 g, 4.9 mmol) and Pd(PPh3)Cl2 (3.4 g, 4.9 mmol) under N2 atmosphere. The mixture was refluxed overnight and quenched with H2O (100 mL). The organic layer was separated and the aqueous layer was extracted with ethyl acetate (100 mL×3). The combined organic layers were washed with brine, dried over anhydrous Na2SO4 and purified by chromatography on silica gel (3% ethyl acetate in petroleum ether as eluant) to afford 2-(6-chloro-4-(3,3-dimethylbut-1-ynyl)pyridin-3-ylamino)ethanol (3.6 g, 29%). 1H-NMR (CDCl3, 300 MHz) δ 7.74 (s, 1H), 7.11 (s, 1H), 4.77 (br s, 1H), 3.92-3.90 (m, 2H), 3.78-3.36 (m, 2H), 1.34 (s, 9H).

後処理

  1. temperatureThe mixture was refluxed overnight
  2. customquenched with H2O (100 mL)
  3. customThe organic layer was separated
  4. extractionthe aqueous layer was extracted with ethyl acetate (100 mL×3)
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over anhydrous Na2SO4
  7. custompurified by chromatography on silica gel (3% ethyl acetate in petroleum ether as eluant)

出典と根拠

ORDレコード
ord-436e8244c3174dc2ada1e3492a2dc271
出典データセット
uspto-grants-2015_08
特許番号
US09102672B2

反応ノート

読み込み中…