Reactivity of o-aminomethylphenols in the Menshutkin reaction
- 46 Downloads
The kinetics of the reaction of o-aminomethylphenols and dimethylbenzylamine with alkyl halides have been studied. The rate of quaternization of the amino group depends on the steric conditions in the nucleophilic and electrophilic reagents, the basicity of the nucleophile, the length and degree of branching of the hydrocarbon chains in the alkyl halides, and on the presence of an intramolecular hydrogen bond (IHB) between the amino nitrogen atom and the phenolic hydroxyl group.
The sharp decrease in the reactivity of the o-aminomethylphenols compared with the benzylamine in protonic dipolar solvents is due to an increase in the strength of the IHB in these media.
Compared with aprotic dipolar solvents, the reactivity of o-dimethylaminomethylphenol in alcohols is increased due to weakening of the IHB. Dimethylbenzylamine has low reactivity in alcohols due to its specific solvation by alcohols.
KeywordsAlcohol Hydrocarbon Nitrogen Atom Halide Sharp Decrease
Unable to display preview. Download preview PDF.
- 1.N. A. Shishkina, K. A. Derstuganova, L. A. Kudryavtseva, V. E. Bel'skii, and B. E. Ivanov, Izv. Akad. Nauk SSSR, Ser. Khim., 1259–1264 (1976).Google Scholar
- 2.V. E. Bel'skii, L. A. Kudryavtseva, N. A. Shishkina, T. A. Zyablikova, A. V. Il'yasov, and B. E. Ivanov, Izv. Akad. Nauk SSSR, Ser. Khim., 331–334 (1977).Google Scholar
- 3.A. M. Kuliev, M. A. Salimov, F. N. Mamedov, and N. Yu. Ibragimov, Dokl. Akad. Nauk SSSR,184, 1141–1143 (1969).Google Scholar
- 4.L. A. Kudryavtseva, A. B. Teitel'baum, N. A. Shishkina, A. N. Vereshchagin, and B. E. Ivanov, Izv. Akad. Nauk SSSR, Ser. Khim., 1302–1305 (1979).Google Scholar
- 5.P. D. Gardner, H. S. Rafsanjani, and L. Rand, J. Am. Chem. Soc.,81, 3364–3367 (1959).Google Scholar
- 6.J. Brugion and H. Christol, C. R. Acad. Sci.,256, 3149–3152 (1963).Google Scholar
- 7.M. Wacselman, G. Decodts, and M. Vilkas, C. R. Acad. Sci.,266, Ser. C, 135–138 (1968).Google Scholar
- 8.B. E. Ivanov, S. V. Samurina, A. B. Ageeva, L. A. Valitova, and V. E. Bel'skii, Zh. Obshch. Khim.,49, 1973–1978 (1979).Google Scholar
- 9.S. Yukitani, K. Mamoru, and N. Kenji, Nippon Kagaku Kaishi, J. Chem. Soc. Jpn., Chem. Ind. Chem., 1123–1126 (1978).Google Scholar
- 10.A. M. Kuliev, R. K. Gadzhiev, F. A. Mamedov, and I. I. Namazov, “Synthesis of quaternary ammonium salts,” in: Lubricant Additives (ed. by A. M. Kuliev et al.) [in Russian], Izd. AN AzSSR, Baku (1969), pp. 115–117.Google Scholar
- 11.A. B. Teitel'baum, L. A. Kudryavtseva, V. E. Bel'skii, and B. E. Ivanov, Izv. Akad. Nauk SSSR, Ser. Khim., 2253–2261 (1980).Google Scholar
- 12.C. K. Ingold, Structure and Mechanism in Organic Chemistry, Cornell Univ. Press (1969).Google Scholar
- 13.A. J. Gordon and R. A. Ford, Chemist's Companion: A Handbook of Practical Data, Techniques, and References, Wiley-Interscience (1973).Google Scholar
- 14.H. Reichart, Solvents in Organic Chemistry [Russian translation], Khimiya, Leningrad (1973), p. 137.Google Scholar
- 15.H. Mechette, E. Zakowicz, V. Bustos, and V. Ronchietto, Chem. Commun., 825–826 (1979).Google Scholar
- 16.Ya. Yu. Akhadov, Dielectric Properties of Pure Liquids [in Russian], Izd. Standartov (1972), p. 412.Google Scholar
- 17.V. P. Andreev, E. M. Vuka, E. V. Kochetkova, L. A. Remizova, and I. A. Favorskaya, Zh. Org. Khim.,15, 464–467 (1979).Google Scholar
- 18.M. H. Abraham, J. Chem. Soc., B, 299–308 (1971).Google Scholar
- 19.V. A. Savelova and L. M. Litvinenko, Reactivity of Organic Compounds [in Russian], Vol. 5, Izd. Tartusk. Univ. (1968), pp. 838–861.Google Scholar
- 20.S. G. Éntelis and R. P. Tiger, Kinetics of Liquid-Phase Reactions. Quantitative Allowance for Effect of Medium [in Russian], Khimiya, Moscow (1973), p. 194.Google Scholar
- 21.P. Haberfield, A. Nudelman, A. Blom, A. Romm, and H. Ginsberg, J. Org. Chem.,36, 1792–1795 (1971).Google Scholar