Tertiary amines nucleophilicity in quaternization reaction with benzyl chloride





hydrazide, nucleophilicity, tertiary amines, quaternization, reversible processes


Quaternization reaction of tertiary amines with benzyl chloride was investigated. Reaction orders with respect to the reactants were determined. Kinetic scheme of quaternization reaction was found to be corresponding to reversible process. An influence of amines basicity and steric factor of alkyl substituent bound to the nitrogen atom on tertiary amines reactivity as nucleophiles was studied. It was shown that the rate constants of direct reaction step may serve as a measure of nucleophilicity of amines.

Author Biographies

Ksenia S. Yutilova, Donetsk National University, 21 600-richcha Str., Vinnytsia 21021

Department of Organic Chemistry, Postgraduate Student

Stanislav G. Bakhtin, Donetsk National University, 21 600-richcha Str., Vinnytsia 21021

Department of Organic Chemistry, Postgraduate Student

Olena M. Shved, Donetsk National University, 21 600-richcha Str., Vinnytsia 21021

Chair of the Department of Organic Chemistry, Doctor of Chemical Sciences, Docent

Yulia M. Bespalko, Donetsk National University, 21 600-richcha Str., Vinnytsia 21021

Department of Organic Chemistry, Associate Professor, Vice Dean, Candidate of Chemical Sciences (PhD)


Mingfa, Y., Tao, W., Na, Q., & Daping, Q. (2012) Controllable ring-opening polymerization of trimethy-lene carbonate catalyzed by aliphatic tertiary amines in the presence of benzyl alcohol or F127. Polymer International, 61(10), 1525–1531. doi: 10.1002/pi.4240

Kas'yan, L. I., Turov, A. V., Karat, L. D., Prid'ma, S. A., Pal'chikov, V. A., Svyatenko, L. K., & Okovityi, S. I. (2011). Experimental and theoretical study on the reaction of bicyclo[2.2.1]hept-5-en-endo-2-ylmethan-amine with glycidyl ethers. Russ. J. Org. Chem., 47(1), 74–82. doi:10.1134/s1070428011010088

Sinelnikova, M. A., Shved, E. N., Usachov, V. V., & Oleynik, N. M. (2010). [Modeling the mechanism of amine catalysis of epichlorohydrin acidolysis with aliphatic and aromatic carboxylic acids]. Teor. i eksp. khim. – Theoretical and experimental chemistry, 46(3), 164–170 (in Russian).

Choe, Y.-S., Park, S.-W., Park, D.-W., & Kim, S.-S. (2010). Reaction Kinetics of Carbon Dioxide with Phenyl Glycidyl Ether by TEA-CP-MS41 Catalyst. J. Jpn. Petrol. Inst., 53(3), 160–166. doi: 10.1627/jpi.53.160

Klopman, G. (Ed.). (1974). Chemical Reactivity and Reaction Paths. New York: Wiley.

Palm, V. A. (1977). [Fundamentals of quantitative theory of organic reactions]. Leningrad, USSR: Khimiya (in Russian).

Zhou, X.-Y., Rong, C.-Y., Lu, T., & Liu, S.-B. (2014). Hirshfeld Charge as a Quantitative Measure of Electrophilicity and Nucleophilicity: Nitrogen-Containing Systems. Acta Physico-Chimica Sinica, 30(11), 2055–2062. doi: 10.3866/PKU.WHXB201409193

Takayama, C., Fujita, T., & Nakajima, M. (1979). Quantitative separation of electronic and steric substituent effects in reactions between aliphatic amines and electron acceptors. J. Org. Chem., 44(16), 2871–2879. doi: 10.1021/jo01330a011

Firago, D. S. (2011). [Kinetic study of quaternization reaction of 1-methylimidazole with 1-brombutane in acetonitrile]. Sb. rabot 67 nauchnoy conf. stud. i asp. BGU, 17-20.05.2010, Minsk. V 3 ch. Ch. 1. – Works digest of 67th student and post-graduate student scientific conference of Belarus State University, May 17th–20th 2010, Minsk. In 3 parts. P. 1. Minsk, Belarus. 221–225 (in Russian).

Arnett, E. M., & Reich, R. (1980). Electronic effects on the Menshutkin reaction. A complete kinetic and thermos-dynamic dissection of alkyl transfer to 3- and 4-substituted pyridines. J. Amer. Chem. Soc., 102(18), 5892–5902. doi: 10.1021/ja00538a031

Juravlyov, O. E., Verolaynen, N. V., & Voronchihina, L. I. (2012). [Synthesis and biological activity of N-alkyl-piperi-dinium quarternary salts]. Vestn. Tver. Gos. Univ.: Khim. – Bull. Tver State University: Chem., (14), 78–85 (in Russian).

Bekker, H., Bekkert, R., Berger, V., Gevald, K., Gents, F., Gluh, R., Domshke, G., Zailer, E., Mayer, R., Mets, P., Muller, K., Pafel, D., Faighenel, E., Faust, Yu., Fisher, M., Habiher, V., Shvetlik, K., Shmidt, G., Sholberg, K., & Tseppenfeld, G. (1992). [Organicum]. Moscow, USSR: Mir (in Russian).

Nikolsky, B. P. (1964) [Reference Book in Chemistry]. Moscow–Leningrad, USSR: Khimia (in Russian).

Umland, F., Yansen, A., Tirig, D., & Vyunsh, G. (1975). [Complex compounds in analytic chemistry. Theory and practice of using]. Moscow, USSR: Mir (in Russian).