Diethyl Ether → HCID 19974684, compound

HRID 1451379Notes

Reaction equation

HRID 1451379 reaction equation
[CH2:1]([Sn](CCCC)(CCCC)C(C)=C)[CH2:2][CH2:3]C.Br[C:18]1[CH:25]=[C:22]([CH:23]=[O:24])[C:21]([O:26][CH3:27])=[CH:20][CH:19]=1.CCOCC.[F-].[K+]>C1(C)C=CC=CC=1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:2]([C:20]1[CH:19]=[CH:18][CH:25]=[C:22]([CH:23]=[O:24])[C:21]=1[O:26][CH3:27])([CH3:3])=[CH2:1]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 906845-Bromo-2-methoxybenzaldehydeHCID 522689Potassium FluorideHCID 10871254Stannane, tributyl(1-methylethenyl)-

Product 1

HCID 19974684HCID 19974684, compoundYield 51%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolvent2×

Procedure

Tri-n-butyl-isopropenyltin (12.1 g, 36.6 mmol) dissolved in toluene (10 ml) was added to a mixture of 5-bromo-o-anisaldehyde (6.00 g, 27.9 mmol), tetrakis(triphenylphosphine)-palladium (1.21 g, 1.05 mmol), and 2,6-t-butyl-4-methylphenol (10 mg) in toluene (50 ml) under nitrogen at room temperature. This mixture was heated at reflux for 7 h. Ether and aq. KF solution (80 ml) were added to the reaction mixture, and the resulting solution was stirred for 3 h. Insoluble materials were removed by filtration through Celite. The filtrate was extracted with ether, and the organic phase was washed with 1N-NaHSO4, aq. NaHCO3 and brine. The extracts were dried over Na2SO4, and concentrated by evaporation. The residual oil was purified by chromatography (SiO2, 140 g, 5% EtOAc-hexane) to afford -isopropenyl-o-anisaldehyde as a yellow oil (2.49 g, 51%). 1H NMR δ: 10.47 (s, 1H), 7.93 (d, J=2.6 Hz, 1H), 7.69 (dd, J=8.8, 2.6 Hz, 1H), 6.96 (d, J=8.8 Hz, 1H), 5.35 (br. s, 1H), 5.07 (m, 1H), 3.94 (s, 3H), 2.15 (m, 3H).

Workup

  1. temperatureThis mixture was heated
  2. temperatureat reflux for 7 h
  3. customInsoluble materials were removed by filtration through Celite
  4. extractionThe filtrate was extracted with ether
  5. washthe organic phase was washed with 1N-NaHSO4, aq. NaHCO3 and brine
  6. dry with materialThe extracts were dried over Na2SO4
  7. concentrationconcentrated by evaporation
  8. customThe residual oil was purified by chromatography (SiO2, 140 g, 5% EtOAc-hexane)

Sources & evidence

ORD record
ord-20480bed494f4bfaac802009093179f9
Source dataset
uspto-grants-1997_02
Patent number
US05604241

Reaction notes

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