OXIDATION OF THE N,N–DIMETHYLANILINE BY PEROXYNONANIC ACID IN ORGANIC SOLVENTS

V. Dutka, G. Midyana, Yu. Dutka, O. Pal'chikova


DOI: http://dx.doi.org/10.30970/vch.6301.383

Abstract


The rate of oxidation reaction of the N,N–dimethylaniline with peroxynonanic acid in various organic solvents was studied. It has been found the effective rate constants (k) and the activation energy (Eakt) of the studied process. Between the parameters of the transition state ΔН≠ and ΔЅ≠ is some linear relationship, indicating the presence of the compensation effect in our series of experiments. The rate of oxidation and activation energy inflation of solvation peroxyacid and N,N–dimethylaniline. The reaction medium affects the rate of oxidation. Correlation equations between the rate constants of the reactions in the study and the physic-chemical parameters of the solvents were proposed.

The correlation equation for effective rate constants and the basic physic-chemical parameters of solvents at 313 K has the form:

lgk = 5.0118 – (8.8421 ± 0.0008)f(n) + (0.8624 ± 0.0001)f(ε) – (0.0039 ± 0.0000)B – (0.0368 ± 0.0000)ET + (0.0036 ± 0.0000)δ2 – (0.0032 ± 0.0000)VM.

N=7; R=1.0; S=0.000; F=10.8537.

The polarizability, basicity (B), ET, VM and δ2 of solvent have effect on the oxidation process. Correlation equations for effective rate constants for other temperatures are similar.

The correlation equation for effective energies of activation (Eakt) and the basic physicochemical parameters of solvents has the form:

lgЕаkt = 0.8844 + (0.0008 ± 0.0003)B + (0.0142 ± 0.0031)ET.

N=7; R=0.9592; S=0.0409; F=86.3553.

The basicity (B) and ET parameters of solvent have an effect on the energy of the activation process. The proposed correlation equations relate the parameters of the transition state of the oxidation process and the physic-chemical parameters of solvents.

 

Keywords: N,N–dimethylaniline, oxidation reaction, peroxynonanic acid, rate constant, activation energy, correlation equation.


References


Antonovskii V. L. Organic peroxide initiators. Moscow: Khimiya, 1972. 448 p. (in Russian).

Tolstikov G. A. Hydroperoxide Oxidation. Moscow: Nauka, 1974. 200 р. (in Russian).

Prilezhaeva E. N. Prilezhaev Reaction: Electrophilic Oxidation. Moscow: Khimiya, Nauka, 1974. 332 p. (in Russian).

Iwanchov S. S. Radical polymerization. Moscow: Khimiya. 1985. Р. 279 (in Russian).

Parker W. E., Riccuti C, Ogg C. L., Swern D. Peroxides II. Preparation, characterization and polarographic behavior of long-chain aliphatic peracids // J. Am. Chem. Soc. 1955. Vol. 77, Nо 15. P. 4037-4041. DOI: https://doi.org//10/1021/ja01620a023

Antonovskii V. L., Buzulanova M. M. Analitical Chemistry of Organic Peroxide Compounds. Moscow: Khimiya, 1978. 308 p. (in Russian).

Weinberger A., Proskauer E. S., Riddick J. A. and Toops E. E. J. Organic Solvents. Physical Properties and methods of Purifications. New York: Intersci., 1955. 2nd ed. 520 p.

Gordon F. J., Ford R. F. The chemist’s Companion. New York: Wiley, 1972. 541 p.

Koppel I. A., Palm V. A. The influence of solvent on organic reactivity // Advances in Linear Free Energy Relationships. Springer, Boston, MA, 1972. P. 203–280.

Makitra R. G., Turovsky A. A., Zaikov E. E. Correlation Analysis in Chemistry of Solution. Utrecht–Boston: VSP, 2004. 319 p.

Makitra R. G., Pirig Ja. N., Kivelyuk R. Available from VINITI. Мoscow: 1986. No. 628–В86 (in Russian).

Dutka V. S., Matsyuk N. V., Dutka Yu. V. Influence of a Reaction Medium on the Oxidation of Aromatic Nitrogen–Containing Compounds by Peroxyacids // Russ. J. Phys. Chem. A. 2011. Vol. 85(1). Р. 45–50. DOI: https://doi.org/10.1134/S0036024411010079

Dutka V., Midyana G., Pal’chikova O., Dutka Yu., Nagornyak I. Influence of organic solvents on rate of oxidation of the quinoline by peroxydecanic acid // Proc. Shevchenko Sci. Soc. Chem. Sci. 2019. Vol. LVI. P. 89–100.DOI: https://doi.org/0.37827/ntsh.chem.2019.56089

Dutka V., Matsyuk N., Zastavska G., Matsyuk M. Effect of solvent on the oxidation acridine peroxydekanoic acid // Visnyk Lviv Univ. Ser. Chem. 2015. Vol. 56. P. 313–318.

Dutka V., Midyana G., Dutka Yu., Pal’chikova O. Oxidation of nitrogen-containing compounds by peroxy acids // Proc. Shevchenko Sci. Soc. Chem. Sci. 2021. Vol. LXVI. P. 34–46. DOI: https://doi.org/10.37827/ntsh.chem2021.66034


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