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

HRID 1281046노트

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HRID 1281046 반응식
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

참가 물질

5

반응물 2

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

생성물 1

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

시약·촉매·용매 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 178418476HCID 178418476, 화합물촉매

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온도
40 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-40973ab1a0444397a223d7a41721e16c
출처 데이터셋
uspto-grants-2002_09
특허 번호
US06451942B1

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