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

HRID 1836695Notes

Reaction equation

HRID 1836695 reaction equation
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

Participants

5

Reactant 2

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalyst

Conditions

Temperature
40 °C

Procedure

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).

Workup

  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)

Sources & evidence

ORD record
ord-147e2f3bc8a643c283e800731be13943
Source dataset
uspto-grants-2004_08
Patent number
US06777516B2

Reaction notes

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