Methyl 4-iodobenzoate → Methyl 4-(5-hydroxypentynyl)benzoate

HRID 385256ノート

反応式

HRID 385256 の反応式
I[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1.[CH2:12]([OH:17])[CH2:13][CH2:14][C:15]#[CH:16]>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>[OH:17][CH2:12][CH2:13][CH2:14][C:15]#[C:16][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1

参加物

5

反応物 2

HCID 69273Methyl 4-iodobenzoateHCID 793464-Pentyn-1-ol

生成物 1

HCID 11974394Methyl 4-(5-hydroxypentynyl)benzoate収率 69%

試薬・触媒・溶媒 2

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

反応条件

温度
90 °C

実験手順

Methyl 4-iodobenzoate (13.1 g, 60 mmol), PdCl2(PPh3)2 (2.0 g, 3 mmol), and CuI (855 mg, 4.5 mmol) were added to TEA (60 mL). The mixture is degassed while stirring by bubbling N2 vigorously into the solution. Pent-4-yn-1-ol (5.5 g, 66 mmol) was added by syringe. The mixture was heated at 90° C. overnight. After cooling, the crude mixture was concentrated by rotary evaporation and pumped on the high vacuum for 1 h. The oil was dissolved in DCM and adsorbed onto Celite followed by purification by chromatography (gradient 10-100% EtOAc/Hexanes) to give the title compound as a light yellow powder (9 g, 69%). 1H NMR (400 MHz, CDCl3) δ 7.95 (dd, 2H, J=9.0, 1.5 Hz), 7.44 (dd, 2H, J=9.0, 1.5 Hz), 3.90 (s, 3H), 3.85 (m, 2H), 2.57 (t, 2H, J=5.5 Hz), 1.87 (m, 2H), 1.42 (t, 1H, J=5.5 Hz); ES/MS calcd. for C13H15O3+ 219.1. found m/z=219 (M+H)+.

後処理

  1. customThe mixture is degassed
  2. customby bubbling N2 vigorously into the solution
  3. temperatureAfter cooling
  4. concentrationthe crude mixture was concentrated by rotary evaporation
  5. dissolutionThe oil was dissolved in DCM
  6. customfollowed by purification by chromatography (gradient 10-100% EtOAc/Hexanes)

出典と根拠

ORDレコード
ord-b63fd9690e1a4ae690cdae58583f9dcd
出典データセット
uspto-grants-2013_02
特許番号
US08367829B2

反応ノート

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