Abstract
The kinetics of the reaction of N,N’-diphenyl-1,4-beznoquinone diimine with thiophenol in a chlorobenzene—propan-1-ol binary solvent at 343 K was studied spectrophotometrically. The nature of the solvent has a pronounced effect on the reaction rate. On going from chlorobenzene to propan-1-ol, the overall reaction rate increases nearly by an order of magnitude. The reaction has a complex mechanism and follows the two directions. The first direction is the chain reaction with the rate increasing upon addition of an initiator. The second direction is non-chain reaction between the reagents; the initiator does not affect the rate of this reaction. A gross rate constant of the non-chain reaction and the rate constants of some elementary steps of the chain reaction were determined. Based on the obtained results, the overall reaction rate, the rates of both chain and non-chain reactions were calculated depending on the content of propan-1-ol in the binary solvent, concentration of the reagents, and the rate of initiating reaction induced by initiator. It is found that an increase in the propan-1-ol content increases the role of the non-chain process.
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References
The Chemistry of the Quinoid Compounds, Ed. S. Patai, John Wiley and Sons, London—New York—Sydney—Toronto, 1974, Vol. 1, P. 1—2, 1247 pp.
The Chemistry of the Quinoid Compounds, Eds S. Patai, Z. Rappoport, John Wiley and Sons, Chichester—New York— Brisbane—Toronto—Singapore, 1988, Vol. 2, Parts 1—2, 1675 pp.
L. Abraham, R. Joshi, P. Pardasani, R.T. Pardasani, J. Brazil. Chem. Soc., 2011, 22, 385.
E. T. Denisov, I. B. Afanas’ev, Oxidation and Antioxidants in Organic Chemistry and Biology, CRC Press—Taylor and Francis Group, Boca Raton, FL, 2005, 989 pp.
Y. Kumagai, J. Health Sci., 2009, 55, 887.
D. W. Potter, J. A. Hinson, Mol. Pharmacol., 1986, 30, 33.
M. D. Mashkovski, Lekarstvennye sredstva [Medicines], 15th ed., Novaya Volna, Moscow, 2005, 1200 pp. (in Russian).
J. M. Snell, A. Weissberger, J. Am. Chem. Soc., 1939, 61, 450.
G. B. Afanas’eva, E. V. Tsoi, O. N. Chupakhin, E. O. Sidorov, S. V. Konovalov, Zh. Org. Khim., 1985, 21, 1926 [J. Org. Chem. USSR (Engl. Transl.), 1985, 21].
M. K. Vadnere, L. Maggiora, M. P. Mertes, J. Med. Chem., 1986, 29, 1714.
A. A. Kutyrev, V. V. Moskva, Russ. Chem. Rev., 1991, 60, 72.
A. V. Gadomska, V. T. Varlamov, Dokl. Phys. Chem. (Engl. Transl.), 2011, 439, 150 [Dokl. Akad. Nauk, 2011, 439, 767].
A. V. Gadomska, S. Ya. Gadomsky, V. T. Varlamov, Kinet. Catal. (Engl. Transl.), 2012, 53, 525 [Kinet. Katal., 2012, 53, 550].
V. T. Varlamov, A. V. Gadomska, Russ. J. Phys. Chem. A (Engl. Transl.), 2015, 89, 616 [Zh. Fiz. Khim., 2015, 89, 629].
V. T. Varlamov, S. Ya. Gadomsky, A. V. Gadomska, Kinet. Catal. (Engl. Transl.), 2015, 56, 276 [Kinet. Katal., 2015, 56, 277].
S. Ya. Gadomsky, V. T. Varlamov, Russ. Chem. Bull. (Int. Ed.), 2007, 56, 2376 [Izv. Akad. Nauk, Ser. Khim., 2007, 2296].
A. V. Gadomska, V. T. Varlamov, Russ. J. Gen. Chem. (Engl. Transl.), 2014, 84, 1299 [Zh. Obshch. Khim., 2014, 84, 1102].
V. T. Varlamov, Kinet. Catal. (Engl. Transl.), 2001, 42, 759 [Kinet. Katal., 2001, 42, 836].
O. W. Maender, C. J. Rostek, A. R. Katritzky, H. H. Odens, M. V. Voronkov, US Pat. No. 7,718,722, 2010; http:// www.google.com/patents/US7718722.
I. R. Gelling, G. T. Knight, Plastic Rubber Proc., 1977, 2, 83.
C. Walling, W. Helmreich, J. Am. Chem. Soc., 1959, 81, 1144.
O. Turunc, M. A. R. Meier, Eur. J. Lipid Sci. Technol., 2013, 115, 41.
O. Ito, K. Nogami, M. Matsuda, J. Phys. Chem., 1981, 85, 1365.
O. Ito, Reactions of Aromatic Thiyl Radicals, in The Chemistry of Free Radicals. S-Centered Radicals, Ed. Z. B. Alfassi, John Wiley and Sons, Chichester—New York—Weinheim—Brisbane—Singapore—Toronto, 1999, Ch. 6.
C. Chatgilialoglu, K.-D. Asmus, Sulfur-Centered Reactive Intermediates in Chemistry and Biology, NATO ASI Series A: Life and Science, Plenum Press, New York, 1990, 197, 327.
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Varlamov, V.T., Gadomska, A.V. Effects of a composition of a binary solvent chlorobenzene—propan-1-ol on the mechanism of the reaction between N,N’-diphenyl-1,4-benzoquinone diimine and thiophenol. Russ Chem Bull 65, 2046–2052 (2016). https://doi.org/10.1007/s11172-016-1550-5
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DOI: https://doi.org/10.1007/s11172-016-1550-5