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

HRID 1836695Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1836695
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

Komponenten

5

Edukt 2

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

Produkt 1

HCID 31574624-(3-hydroxy-3-methylbut-1-yn-1-yl)benzaldehydeAusbeute 96,3 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysator

Reaktionsbedingungen

Temperatur
40 °C

Versuchsvorschrift

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 Schlenk flask. The flask was then evacuated and purged with argon (3 times) on the Schlenk 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). The 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, 135.9, 192.3; IR (film) v (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).

Aufarbeitung

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

Quellen und Nachweise

ORD-Eintrag
ord-147e2f3bc8a643c283e800731be13943
Quelldatensatz
uspto-grants-2004_08
Patentnummer
US06777516B2

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