Effect of high pressure on the reaction of dipolar 1,3-cycloaddition between 4-nitrophenyl cyanate and benzyl azide and the role of the solvent
The observed volume activation effect (ΔV0≠) of the reaction of dipolar 1,3-cycloraddition between 4-nitrophenyl cyanate and benzyl azide in acetonitrile is a function of the ratio of the reagents and is 40–60% of the change in the volume in the reaction (ΔV0).
The accelerating effect of high pressure increases in conducting the reaction in conditions of the existence of the solvent (benzene) in the supercooled state; ¦ΔV0≠¦ is only 15% less than ¦ΔV0¦.
In consideration of the change in the viscosity with a change in the pressure (ΔVη≠), the volume activation effect (ΔVr≠) is similar to the volume effect of the reaction studied (ΔV0), which supports a cyclic transition state.
KeywordsViscosity Benzene Acetonitrile High Pressure Transition State
Unable to display preview. Download preview PDF.
- 1.V. M. Zhulin and E. B. Zhuravleva, Dokl. Akad. Nauk SSSR,290, No. 2, 383 (1986).Google Scholar
- 2.H. A. Kramers, Physica,7, 284 (1940).Google Scholar
- 3.Ya. B. Zel'dovich, Zh. Éksp. Teor. Fiz.,12, 525 (1942).Google Scholar
- 4.J. Jonas, Accounts Chem. Res.,17, 74 (1984).Google Scholar
- 5.S. Glasstone, C. Leidler, and H. Eyring, The Theory of Absolute Reaction Rates [Russian translation], Inostr. Lit., Moscow (1948).Google Scholar
- 6.E. A. Melvin-Hughes, Equilibrium and Kinetics of Reactions in Solutions [Russian translation], Khimiya, Moscow (1975).Google Scholar
- 7.R. B. Dow, Phil. Magazine,28, No. 189, 403 (1939).Google Scholar
- 8.V. M. Zhulin, Z. G. Makarova, M. M. Krayushkin, et al., Dokl. Akad. Nauk SSSR,280, 917 (1985).Google Scholar
- 9.V. M. Zhulin, Z. G. Makarova, N. V. Klimentova, et al., Vysokomol. Soedin. A,24, 2621 (1982).Google Scholar
- 10.H. G. Parkhurst and J. Jonas, J. Chem. Phys.,63, 2705 (1975).Google Scholar
- 11.I. Artaki and J. Jonas, J. Chem. Phys.,82, 3360 (1985).Google Scholar
- 12.G. I. Nikishin, S. S. Spektor, G. P. Shakhovskoi, et al., Izv. Akad. Nauk SSSR, Ser. Khim., 1664 (1976).Google Scholar
- 13.V. M. Zhulin, M. G. Gonikberg, and V. N. Zagorbinina, Izv. Akad. Nauk SSSR, Otd. Khim. Nauk, 716 (1962).Google Scholar
- 14.B. S. El'yanov and E. M. Vasylvitskaya, Rev. Phys. Chem. Jpn.,50, 174 (1980).Google Scholar