Concerning the Regiochemical Course of the Diels−Alder Reaction in Supercritical Carbon Dioxide

Renslo, Adam R.; Weinstein, Randy D.; Tester, Jefferson W.; Danheiser, Rick

doi:10.1021/jo9704523

Cited by 50 publications

(44 citation statements)

References 26 publications

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“…Generally, visual phase observation is used to verify the presence (or absence) of another phase. 14,26,28 However, this approach does not guarantee a single-phase environment, or even correct phase identification, since the visual observation of a small amount of liquid phase is difficult. 26 The effects of the reagents on the phase behavior (such as the limited solubilities, phase boundaries and the critical point shift) are expected to vanish at very low concentrations of the reactants.…”

Section: Introductionmentioning

confidence: 99%

Kinetics of a Diels−Alder Reaction of Maleic Anhydride and Isoprene in Supercritical CO₂

et al. 2001

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The kinetics of the reaction of maleic anhydride and isoprene in supercritical carbon dioxide was studied over an extended concentration range, from 5 × 10 -5 to 1.3 × 10 -2 mole fractions of both maleic anhydride and isoprene at 60 °C and pressure 100 atm. The apparent rate constant of the reaction was found to be concentration dependent, in contradiction with the literature data. The results are interpreted in terms of limited solubility of maleic anhydride in supercritical CO 2 . The solubility of maleic anhydride in supercritical carbon dioxide was directly measured by sampling and analyzing the supercritical phase. The observed sharp increase in the apparent rate constant of the reaction between maleic anhydride and isoprene correlates with the solubility of maleic anhydride in supercritical carbon dioxide. The interpretation was confirmed using visual observations of the phase behavior. The rate constant of the reaction measured under the true supercritical, single phase, conditions is k x ) (17.0 ( 1.3) hr -1 (mole fraction units, 60 °C, pressure 100 atm).

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Section: Introductionmentioning

confidence: 99%

Kinetics of a Diels−Alder Reaction of Maleic Anhydride and Isoprene in Supercritical CO₂

et al. 2001

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“…[12][13][14][15][16] This type of reaction is especially appropriate for investigation of kinetic solvent effects in supercritical fluids because of the wealth of reactant systems scrutinized in liquid solvents. 17,18 The reaction generally produces a single adduct with few if any byproducts, and the mechanism of the reaction is well understood.…”

Section: Introductionmentioning

confidence: 99%

Rate Variations of a Hetero-Diels−Alder Reaction in Supercritical Fluid CO₂

Thompson

Gläser

Bush

et al. 1999

Ind. Eng. Chem. Res.

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The hetero-Diels-Alder reaction between anthracene and excess 4-phenyl-1,2,4-triazoline-3,5-dione has been investigated in supercritical CO 2 at 40°C and pressures between 75 and 216 bar. Bimolecular reaction rate constants have been measured via fluorescence spectroscopy by following the decrease in anthracene concentration with reaction time. The reaction rate is elevated in the vicinity of the critical pressure. This difference is consistent with local composition enhancement and can be modeled with the Peng-Robinson equation of state.

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“…Renslo et al 39 have examined the reaction selectivity in some Diels -Alder reactions in scCO 2 and conventional solvents. They showed that the product distribution in scCO 2 at pressures of 49 -118 bar and at temperatures of 50 and 150 8C was very similar to that obtained in conventional solvents such as toluene.…”

Section: Diels -Alder Reactionsmentioning

confidence: 99%

Recent advances in the application of supercritical fluids for carbon–carbon bond formation in organic synthesis

2004

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Concerning the Regiochemical Course of the Diels−Alder Reaction in Supercritical Carbon Dioxide

Cited by 50 publications

References 26 publications

Kinetics of a Diels−Alder Reaction of Maleic Anhydride and Isoprene in Supercritical CO₂

Kinetics of a Diels−Alder Reaction of Maleic Anhydride and Isoprene in Supercritical CO₂

Rate Variations of a Hetero-Diels−Alder Reaction in Supercritical Fluid CO₂

Recent advances in the application of supercritical fluids for carbon–carbon bond formation in organic synthesis

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Concerning the Regiochemical Course of the Diels−Alder Reaction in Supercritical Carbon Dioxide

Cited by 50 publications

References 26 publications

Kinetics of a Diels−Alder Reaction of Maleic Anhydride and Isoprene in Supercritical CO2

Kinetics of a Diels−Alder Reaction of Maleic Anhydride and Isoprene in Supercritical CO2

Rate Variations of a Hetero-Diels−Alder Reaction in Supercritical Fluid CO2

Recent advances in the application of supercritical fluids for carbon–carbon bond formation in organic synthesis

Contact Info

Product

Resources

About

Kinetics of a Diels−Alder Reaction of Maleic Anhydride and Isoprene in Supercritical CO₂

Kinetics of a Diels−Alder Reaction of Maleic Anhydride and Isoprene in Supercritical CO₂

Rate Variations of a Hetero-Diels−Alder Reaction in Supercritical Fluid CO₂