Triethylamine → 3-((Trimethylsilyl)ethynyl)phenol

HRID 1917006ノート

反応式

HRID 1917006 の反応式
CCN(CC)CC.I[C:9]1[CH:10]=[C:11]([OH:15])[CH:12]=[CH:13][CH:14]=1.[CH3:16][Si:17]([C:20]#[CH:21])([CH3:19])[CH3:18].CCCCCC.CC(C)=O>C1COCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[CH3:16][Si:17]([CH3:19])([CH3:18])[C:20]#[C:21][C:9]1[CH:10]=[C:11]([OH:15])[CH:12]=[CH:13][CH:14]=1

参加物

8

反応物 4

HCID 8471TriethylamineHCID 122723-IodophenolHCID 66111TrimethylsilylacetyleneHCID 21880519Acetone hexane

生成物 1

HCID 220877193-((Trimethylsilyl)ethynyl)phenol収率 100%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

To a stirred solution of PdCl2(PPh3)2 (46 mg, 0.04 mmol), CuI (15 mg, 0.08 mmol), and Et3N (0.303 g, 0.42 mL, 3 mmol) in 10 mL of THF under nitrogen was added 3-iodophenol (0.440 g, 2 mmol) by syringe. The reaction mixture was cooled to 0° C., and trimethylsilylacetylene (0.206 g, 0.30 mL, 2.1 mmol) was added dropwise over 30 min. The reaction mixture was stirred at room temperature overnight and was filtered through Celite to remove Pd and Cu catalysts. Column chromatography (n-hexane/Acetone 6:1) yielded 3-(2-(trimethylsilyl)ethynyl)phenol (380 mg, 2.0 mmol, >99%) as a light brown oil. This compound was diluted with THF (6 mL) and MeOH (6 mL), and 10% aqueous KOH (6 mL) was added. After stirring for 2 hr, the reaction mixture was neutralized by 1 N HCl and evaporated, extracted with CH2Cl2, and dried (Na2SO4). Column chromatography (n-hexane/acetone 5:1) yielded 3-ethynylphenol (162.8 mg, 70%) as a yellow oil.

後処理

  1. filtrationwas filtered through Celite
  2. customto remove Pd and Cu catalysts

出典と根拠

ORDレコード
ord-2f0c787ebf264b77b35d29c4c134180e
出典データセット
uspto-grants-2013_12
特許番号
US08618162B2

反応ノート

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