Abstract
The influence of the temperature and external pressure on the rate of the Diels—Alder reaction between 9,10-dimethylanthracene and maleic anhydride was studied in the series of solvents with wide intervals of viscosity (0.3—43.2 mPa s), dielectric constant (2—38), and internal pressure (3—8.8 kbar). At a standard pressure these properties of the solvent exert a weak and irregular effect on the reaction rate constant and activation enthalpy and entropy. The effect of the external pressure on the rate constant was studied in a high-pressure (up to 1 kbar) optical cell in acetonitrile and silicon oil and in a barostat cell (up to 6 kbar, toluene, silicon oil). Close values of the activation volume were obtained in all solvents. In toluene the reaction rate increases smoothly in the whole pressure interval. In more viscous silicon oil a similar dependence is observed up to 3 kbar, and the reaction rate decreases sharply with the further increase in the pressure and viscosity because of the diffusion control of the process.
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Kiselev, V.D., Kashaeva, E.A., Shihab, M.S. et al. Diffusion control of the Diels—Alder reaction rate at elevated pressures. Russian Chemical Bulletin 53, 45–50 (2004). https://doi.org/10.1023/B:RUCB.0000024827.64458.0f
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DOI: https://doi.org/10.1023/B:RUCB.0000024827.64458.0f