EFFECT OF SUBSTITUTED BENZANILIDES ADDITIVES ON THE SPEED OF CATALYZED BY TETRABUTOXYTIITANE AND POLYBUTOXYTIТANATE REACTION OF ANILINE WITH BENZOIC ACID
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Keywords

tetrabutoxytitanium, polybutoxytitanates, HNMR spectroscopy, rate constant, benzanilide, Hammett equation.

How to Cite

Shteinberg, L. Y. (2019). EFFECT OF SUBSTITUTED BENZANILIDES ADDITIVES ON THE SPEED OF CATALYZED BY TETRABUTOXYTIITANE AND POLYBUTOXYTIТANATE REACTION OF ANILINE WITH BENZOIC ACID. Ukrainian Chemistry Journal, 85(1), 19-31. https://doi.org/10.33609/0041-6045.85.1.2019.19-31

Abstract

The catalytic synthesis of benzanilide by the interaction of benzoic acid with aniline is an important model reaction of direct catalytic amidation that has been intensively developed recently in the field  of the concept of «green chemistry», and its study is an urgent task.

     In the framework of solving this problem the effect of the final product - benzanilide, and its substituted on catalysis by tetrabutoxytitanium and its partial hydrolysis products (polybutoxytitanates) was studied. With an increase in the concentration of the preliminary addition of benzanilide, the initial rate of catalytic interaction of benzoic acid with aniline decreases monotonically.

     Benzanilide itself does not catalyze the amidation process, does not hydrolyze under reaction conditions by water, and does not undergo other changes in the reaction mass.

     The kinetics of the formation of benzanylide in the presence of additives of a number of substituted benzanilides, containing electron-withdrawing substituents, showed higher values ​​of the reaction rate constants as compared to that for the formation of benzanilide in the absence of any additives. This suggests the presence of two routes of catalysis: the coordination route (polarization of the carbonyl group of the benzoic acid due to the interaction with the atom of titanium) and acid route. The latter can be associated with the formation of complexes due to the coordination of the titanium atom of the catalyst with the carbonyl group of the substituted benzanilide, the appearance of a relatively acidic NH=group and catalysis of conjugate acid: the titanium-containing catalyst + the corresponding substituted benzanilide.

     The formation of such a catalytic complex, by the example of a pair of benzanilide + tetrabutoxytitanium, was confirmed by the NMR 1H spectroscopy method.

     Catalysis of aniline acylation with benzoic acid in the presence of additions meta= and para=substituted benzanilides correlates well with the Hammett equation with two straight line segments with ρ=0.478 and ρ=-0.235, with a maximum, indicating a different effect of substituted benzanilides containing electron-donating and strong electron-withdrawing substitutes on the complexation with tetrabutoxytitanium and polybutoxytitanium and the change in their catalytic activity.

     The decrease in the rate of the catalytic formation of benzanilide is especially pronounced with the addition of ortho=substituted benzanilides, containing strong electron-withdrawing substituents, which at the same time have a high steric effect.

https://doi.org/10.33609/0041-6045.85.1.2019.19-31
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References

Lundberg H., Tinnis F., Selander N., Adolfsson H. Catalytic amide formation from non-activated carboxylic acids and amines. Chem. Soc. Rev. 2014. 43: 2714.

Allen С.L. Catalytic approaches to the synthesis of amide bonds. Thesis doctor of philosophy. University of Bath. 2012. P.1-239.

Shteinberg L.Ya., Marshalova V.V., Dibrova V.M., Shein S.M. The effect of the components of the reaction mixture on the hydrolytic stability of tetrabutoxy titanium - catalyst for the benzanilide synthesis. Zhurn. оbsh. khimii. 2008. 78(9): 1463.

Shteinberg L.Ya., Marshalova V.V., Dibrova V.M., Shein S.M. Influence of addition of benzoic acid on catalytic activity of tetrabutoxytitan in the synthesis of benzanilide. Ibid. 2011. 81(9): 1506.

Shteinberg L.Ya., Marshalova V.V., Shein S.M. The effect of the benzoic acid con-centration on the rate of the tetrabutoxytitanium-catalyzed reaction of the benzanilide formation. Ibid. 2012. 82(5): 798.

Shteinberg L.Ya., Dibrova V.M., Shein S.M. Influence of anilines concentration on the speed of the tetrabutoxytitans catalyzed reaction of the benzanilides production. Ukr. Khim. Zhurn. 2013. 79(4): 55.

Shteinberg L.Ya. Influence of anilines concentration on speed of the benzanilides formation, catalyzed by hydrolysis products of tetrabutoxytitane.Ibid. 2017. 83(12): 1.

Shteinberg L.Ya., Коndratov S.А., Shein S.M. Metallocomplex catalysis in the acylation of aniline with substituted benzoic acids. Zhurn. organ. khimii. 1988. 24(9): 1968.

Shteinberg L.Ya., Shein S.M., Mishenko S.Ye. Influence of tetrabutoxytitan «aging» on catalytic activity in the acylation reaction of aniline by benzoic acid. Ibid. 1995. 31 (2): 233.

Коndratov S.А. Chemical modification of polymethylene urea. Diss. doct. khim. nauk. Rubezhnoye – 2002. [in Ukrainian].

Galpern G.М., Kreshkov А.P., Теplova V.V., Sulpovar А.А., Seryanova S.Ye., Yanduganova N.P. Determination of carboxylic anilides by potentiometric titration of nonaqueous solutions. Zhurn. anаlitich. khimii. 1977. 32(3): 586.

Lucht S., Stumpe J., Rutloh M. Triple fluorescence of substituted benzanilides in solution and in solid states. J. Fluоrescence.1998. 8(2): 153.

Chenevert R., Plante R. Photochemical rearrangement of acetanilide, benzanilide and ethyl phenyl carbonate in the presence of P-cyclodextrin. Can. J. Chem. 1983. 61 (6): 1092.

Kaboudin B., Abedi Ya. Fries rearrangement of anilides in the presence of phos- phorus pentoxide in methanesulfonic acid. Organic preparations and procedures international. 2009. 41(3): 229.

Ogata S., Mochizuki A., Kakimoto M., Imai Y. Synthesis of amides and amidines by reaction of carboxylic acids and amines in the presence of polyphosphoric acid trimethylsilyl. Bull.Chem.Soc. Jpn. 1986. 59(7): 2171.

Litvinenko L.M., Oleynik N.M. Organic catalysts and homogeneous catalysis. (Kyiv: Naukova dumka, 1981). [in Russian].

Bender М.L., Bergeron R.J., Комiyama М. The Bioorganic chemistry of enzymatic catalysis. (Мoscow: Mir, 1987). [in Russian].

Panchenkov G.M., Lebedev V.P. Chemical kinetics and catalysis. Training for uni-versities. (Мoscow: Chimiya, 1985).[in Russian].

Shmid R., Sapuov V.N. Non-formal kinetics. In search of ways of chemical reac-tions. (Мoscow: Mir, 1985). [in Russian].

Feng J.-K., Lin T.-H., Tang G.-Q., Li Z.-R. A theoretical study of proton-transfer reaction of benzanilide 1. The cis, trans tautomerization and dimerization of amide and imidic acid. Acta Chimica Sinica. 1991. 49(2): 142.

Sapunov V.N., Lemman G.М., Lebedev N.N. Mechanism of esterification of phtha-lic anhydride by alcohols during catalysis with tetrabutoxytitanium. Izv. vuzov.Chimiya i chim. thechnol. 1976. 19(5): 696.

Garkusha-Bozhko I..P., Oleynik N.M., Litvinenko L.M. Compounds of tin (IV) – catalysts of reaction of peptides production. Effect of basicity and concentration of amine components. Zhurn. organ. khimii. 1982. 18(11): 2340.

Paul R.C., Sreenathan B.R., Chadha S.L. Structure of donor-acceptor complexes-I: Complexes of Lewis acids with amides. J. Inorg. Nucl. Chem. 1966. 28(5): 1225.

Zhdanov Yu.А., Minkin V.I. Correlation analysis in organic chemistry. (Rostov: Publishing house of Rostov University, 1966). [in Russian].

Chiu F.C.K., Lo C.M.Y. Observation of Amide Anions in Solution by Electro-spray Ionization Mass Spectrometry. J. Amer. Soc. Mass Spectrometry. 2000. 11(12): 1061.

Sivakumar K., Stalin T., Rajendiran N. Dual fluorescence of diphenyl carbazide and benzanilide: Effect of solvents and pH on electronic spectra. Spectrochimica Acta. Part A. Mol. Biomol. Spectrosc. 2005. 62(4-5): 991.

Shteinberg L.Ya., Kondratov S.A., Shein S.M. The effect of solvents in the cataly-zed reaction of aniline with benzoic acid. Zhurn. organ. khimii. 2005. 41(7): 312.

Malhotra K.C., Mahajan K.C., Chaughry S.C. Lewis acid character of naphthoxydes of titanium (IV). Indian J. Chem. 1984. 23(23): P.348.

Durfee L.D., Latesky S.L., Rothwell I.P., Huffman J.C., Folting K. Chemical and elect-rochemical reduction of titanium (IV) aryloxides. Inorg Chem. 1985. 24(26): 4569.

Mishra S.K., Suryaprakash N. Intramolecular hydrogen bonding involving organic fluorine: NMR investigations corroborated by DFT-based theoretical calculations. Molecules. 2017. 22: 423.

Marov I.N., Kostromina N.A. EPR and NMR in the chemistry of coordination compounds. (Moscow: Science, 1979). [in Russian].

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