3-Butyn-1-OL → 4-(4-Chloro-2-methoxy-phenyl)-but-3-yn-1-ol

HRID 2383996ノート

反応式

HRID 2383996 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][C:3]=1[O:9][CH3:10].[CH2:11]([OH:15])[CH2:12][C:13]#[CH:14]>N1CCCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[Cl:8][C:5]1[CH:6]=[CH:7][C:2]([C:14]#[C:13][CH2:12][CH2:11][OH:15])=[C:3]([O:9][CH3:10])[CH:4]=1

参加物

6

反応物 2

HCID 135663-Butyn-1-OLHCID 179848451-Bromo-4-chloro-2-methoxybenzene

生成物 1

HCID 591924974-(4-Chloro-2-methoxy-phenyl)-but-3-yn-1-ol収率 77%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418397HCID 178418397、化合物触媒HCID 31268Pyrrolidine溶媒2 回

反応条件

温度
80 °C

実験手順

To a stirred solution of 2-bromo-5-chloroanisole (2 g, 9 mmol), Pd(PPh3)4 (520 mg, 0.45 mmol), and CuI (400 mg) in pyrrolidine (20 mL) was added a solution of 3-butyn-1-ol (1.26 g, 18 mmol) in pyrrolidine (30 mL). The reaction mixture was stirred at 80° C. for 6 h, and then concentrated in vacuo. The resulting residue was extracted with ethyl acetate and the organic phase was washed with 1N hydrochloric acid, followed by water, then brine, and dried over sodium sulfate. Upon removal of the solvent under reduced pressure, the crude product was subjected to column chromatography on silica gel (gradient elution with 0%-40% EtOAc/hexane) to give 4-(4-chloro-2-methoxy-phenyl)-but-3-yn-1-ol as a colorless oil (1.46 g, 76.7%). 1H NMR (300 MHz, CDCl3) δ ppm 7.29 (d, J=8.2 Hz, 1H), 6.88 (dd, J=8.2, 1.6 Hz, 1H), 6.85 (d, J=1.6 Hz, 1H), 3.87 (s, 3H), 3.82 (t, J=6.2 Hz, 2H), 2.73 (t, J=6.2 Hz, 2H), 1.92 (br. s, 1H).

後処理

  1. concentrationconcentrated in vacuo
  2. extractionThe resulting residue was extracted with ethyl acetate
  3. washthe organic phase was washed with 1N hydrochloric acid
  4. dry with materialbrine, and dried over sodium sulfate
  5. customUpon removal of the solvent under reduced pressure

出典と根拠

ORDレコード
ord-8f7255a983da46bb96a281ca02e96eee
出典データセット
uspto-grants-2012_09
特許番号
US08263656B2

反応ノート

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