2-Methyl-3-butyn-2-ol → 4-(3-hydroxy-3-methylbut-1-yn-1-yl)benzaldehyde

HRID 1281046ノート

反応式

HRID 1281046 の反応式
Br[C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1.[CH3:10][C:11]([OH:15])([C:13]#[CH:14])[CH3:12]>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>[CH3:10][C:11]([OH:15])([CH3:12])[C:13]#[C:14][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1

参加物

5

反応物 2

HCID 82582-Methyl-3-butyn-2-olHCID 707414-Bromobenzaldehyde

生成物 1

HCID 31574624-(3-hydroxy-3-methylbut-1-yn-1-yl)benzaldehyde収率 96.3%

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
40 °C

実験手順

4-Bromobenzaldehyde (3.0 g, 16 mmol), Pd(PPh3)2Cl2 (110 mg, 0.170 mmol) and CuI (16 mg, 0.07 mmol) were placed in a Schienk flask. The flask was then evacuated and purged with argon (3 times) on the Schienk line. Then freshly distilled and degassed TEA (32 mL) was added, and after purging with argon, 2-methyl-3-butyn-2-ol (1.90 mL, 19.4 mmol) was added. The reaction mixture was stirred for 2 h at 40° C. (The progress of the reaction was monitored by GC-MS). T he reaction mixture was evaporated to dryness and then chromatographed (silica, CH2Cl2). Bulb-to-bulb distillation (93-95° C., 0.001 mm Hg) gave a pale yellowish oil (2.90 g, 95%). 1H NMR (CDCl3) δ 1.61 (s, 6H), 2.23 (brs, 1H), 7.52 (AB/2, J=8.1 Hz, 2H), 7.79 (AB/2, J=8.1 Hz, 2H), 9.02 (s, 1H); 13C NMR δ 31.9, 66.1, 81.9, 98.8, 129.8, 130.1, 132.7, 35.9, 192.3; IR (film)ν(cm−1) 790.4, 830.1, 906.3, 963.4, 1014.3, 1046.1, 1165.9, 1207.0, 1273.4, 1303.0, 1373.0, 1457.6, 1563.8, 1603.6, 1700.0, 2228.1, 2735.0, 2837.8, 2934.1, 2982.2, 3413.3; MS (EI+) m/z 188 (M+,35%), 173 (100%), 159 (10%); EI-MS obsd 188.0835, calcd exact mass 188.0837 (C12H12O2).

後処理

  1. customThe flask was then evacuated
  2. custompurged with argon (3 times) on the Schienk line
  3. distillationThen freshly distilled
  4. customdegassed TEA (32 mL)
  5. additionwas added
  6. additionwas added
  7. customT he reaction mixture
  8. customwas evaporated to dryness
  9. customchromatographed (silica, CH2Cl2)
  10. distillationBulb-to-bulb distillation (93-95° C., 0.001 mm Hg)

出典と根拠

ORDレコード
ord-40973ab1a0444397a223d7a41721e16c
出典データセット
uspto-grants-2002_09
特許番号
US06451942B1

反応ノート

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