A Comparative Kinetic and Mechanistic Study on the Oxidation Behaviour of Halogenated Fluorenes by Permanganate in Alkaline Medium
Science Journal of Chemistry
Volume 4, Issue 6, December 2016, Pages: 69-78
Received: Aug. 28, 2016;
Accepted: Oct. 10, 2016;
Published: Nov. 1, 2016
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Ahmed Fawzy, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia; Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
Rabab J. Jassas, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Ismail I. Althagafi, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Saleh A. Ahmed, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia; Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
Hatem M. Altass, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
The oxidation kinetics of fluorene (Fl) and its halogenated derivatives, namely, 2,7-dichlorofluorene (Fl-Cl), 2,7-dibromofluorene (Fl-Br) and 2,7-diiodofluorene (Fl-I), using potassium permanganate in alkaline medium has been studied spectrophotometrically at a constant ionic strength of 0.1 mol dm-3 and at 25 °C. A first order kinetics has been observed in these reactions with respect to [permanganate]. Fractional-first order dependences of the reactions on the [reductants] and [alkali] were revealed. No significant effect on the reaction rates by increasing ionic strength was recorded. Intervention of free radicals was observed in the reactions. The reactions mechanism describing the kinetic results has been proposed which involves formation of 1:1 intermediate complexes between fluorene derivatives and the active species of permanganate. The final reactions products were identified by GC/MS and FT-IR analyses in all cases as the corresponding ketones (9H-fluorenone derivatives). Under comparable experimental conditions, the order of the oxidation rate of fluorine derivatives was: Fl > Fl-I > Fl-Br > Fl-Cl. The reactions constants involved in the different steps of the reactions mechanism have been evaluated. With admiration to rate-limiting step of these reactions, the activation parameters were recorded and discussed.
Rabab J. Jassas,
Ismail I. Althagafi,
Saleh A. Ahmed,
Hatem M. Altass,
A Comparative Kinetic and Mechanistic Study on the Oxidation Behaviour of Halogenated Fluorenes by Permanganate in Alkaline Medium, Science Journal of Chemistry.
Vol. 4, No. 6,
2016, pp. 69-78.
Thormann T, Rogojerov M, Jordanov B, Thulstrup EW (1999) Vibrational polarization spectroscopy of fluorene: alignment in stretched polymers and nematic liquid crystals, J. Mol. Str. 509:93-99.
Environmental contaminants encyclopedia fluorene entry July 1, 1997.
Li X, Lü H, Wang S, Guo J, Li J (2011) Sensitizers of dye-sensitized solar cells, Prog. Chem., 23:569-588.
Ma Z, Ding J, Cheng Y, Xie Z, Wang L, Jing X, Wang F (2011) Synthesis and characterization of red light-emitting electrophosphorescent polymers with different triplet energy main chain, Polymer, 52:2189-2197.
Wang HY, Qian Q, Lin KH, Peng B, Huang W, Liu F, Wei W (2012) Stable and good color purity white light-emitting devices based on random fluorene/spirofluorene copolymers doped with iridium complex, J. Polym. Sci.B, 50:180-188.
Yang XH, Wu FI, Neher D, Chien CH, Shu CF (2008) Polyfluorene-based semiconductors combined with various periodic table elements for organic electronics, Chem. Mater., 20:1629-1635.
Kucherak OA, Didier P, Mély Y, Klymchenko AS (2010) Fluorene Analogues of Prodan with Superior Fluorescence Brightness and Solvatochromism, J. Phys. Chem. Lett., 1:616-620.
Cheng YJ, Yang SH, Hsu CS (2009) Synthesis of conjugated polymers for organic solar cell applications, Chem. Rev., 109:5868-5923.
Xing X, Zhang L, Liu R, Li S, Qu B, Chen Z (2012) A deep-blue emitter with electron transporting property to improve charge balance for organic light-emitting device, ACS Appl. Mater. Interf., 4:2877-2883.
Pina J de, Melo JSS, Egkert A, Scherf U (2015) Unusual photophysical properties of conjugated, alternating indigo–fluorene copolymers, J. Mater. Chem. A, 3:6373-6381.
Fromm R, Ahmed SA, Hartmann Th, Huch V, Abdel-Wahab AA, Dürr A (2001) Eur. J. Org. Chem., 21:4077-4085.
Ahmed SA, Abdel-Wahab AA, Dürr H (2003) CRC Handbook of organic photochemistry and photobiology, Horspool WM, Lenci F edn, CRC press, New York, 2nd edn, Chapter 96, p 1.
Ahmed SA, Hartmann Th, Dürr H (2008) Photochromism of dihydroindolizines: Part VIII. First holographic image recording based on di- & tetrahydroindolizines photochromes, J. Photochem. Photobiol., 200:50-56.
Ahmed SA, Pozzo JL (2008) Photochromism of dihydroindolizines Part IX. First attempts towards efficient self-assembling organogelators based on photochromic dihydroindolizines and N-acyl-I,-amino acid units, J. Photochem. Photobiol., 200:57-67.
Stewart R (1965) Oxidation in Organic Chemistry, Part A (ed.) Wiberg KB, New York, Academic Press.
Jose TP, Nandibewoor ST, Tuwar SM (2005) Mechanism of oxidation of L-histidine by heptavalent manganese in alkaline medium. E-J. Chem., 2: 75 -85.
Fawzy A, Ashour SS, Musleh MA, Base-catalyzed oxidation of L-asparagine by alkaline permanganate and the effect of alkali-metal ion catalysts: kinetics and mechanistic approach, React. Kinet. Mech. Catal., 111 (2014) 443-460.
Fawzy A, Shaaban MR (2014) Kinetic and mechanistic investigations on the oxidation of N’-heteroaryl unsymmetrical formamidines by permanganate in aqueous alkaline medium. Transition Met. Chem. 39: 379-386.
Fawzy A, Zaafarany IA, Alfahemi J, Tirkistani FA (2015) Base-catalyzed oxidation of aminotriazole derivative by permanganate ion in aqueous alkaline medium: a kinetic study. Int. J. Inn. Res. Sci. Eng. Tech., 4: 6802-6814.
Asghar BH, Fawzy A (2014) Kinetic, mechanistic, and spectroscopic studies of permanganate oxidation of azinyl-formamidines in acidic medium, with autocatalytic behavior of manganese(II). J. Saudi Chem. Soc., in press.
Fawzy A, Ashour SS, Musleh MA (2014) Kinetics and mechanism of oxidation of L-histidine by permanganate ions in sulfuric acid medium. Int. J. Chem. Kinet. 46: 370-381.
Ahmed GA, Fawzy A, Hassan RM (2007) Spectrophotometric evidence for the formation of short-lived hypomanganate(V) and manganate(VI) transient species during the oxidation of K-carrageenan by alkaline permanganate. Carbohydr. Res., 342: 1382-1386.
Zaafarany IA, Fawzy A, Ahmed GA, Ibrahim SA, Hassan RM, Takagi HD (2010) Further evidence for detection of short-lived transient hypomanganate(V) and manganate(VI) intermediates during oxidation of some sulfated polysaccharides by alkaline permanganate using conventional spectrophotometeric techniques. Carbohydr. Res., 345: 1588-1593.
Hassan RM, Fawzy A, Alarifi A, Ahmed GA, Zaafarany IA, Takagi HD (2011) Base-catalyzed oxidation of some sulfated macromolecules: kinetics and mechanism of formation of intermediate complexes of short-lived manganate (VI) and/or hypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganate. J. Mol. Catal. A, 335: 38-45.
Hassan RM, Dahy A, Ibrahim S, Zaafarany IA, Fawzy A (2012) Oxidation of some macromolecules. Kinetics and mechanism of oxidation of methyl cellulose polysaccharide by permanganate ion in acid perchlorate solutions. Ind. Eng. Chem. Res., 51: 5424–5432.
Gardner KA, Kuehnert LL, Mayer JM (1997) Hydrogen atom abstraction by permanganate: oxidations of arylalkanes in organic solvents. Inorg. Chem., 36: 2069-2078.
Ahmed SA (2004) Photochromism of dihydroindolizines.III synthesis and photochromic behavior of novel photochromic dihydroindolizines incorporating a cholesterol moiety, Monatsh. Chem., 135:1173-1181.
Ahmed SA, Khairou KS, Asghar BH, Muathen HA, Nahas NMA, Al Shreef HF (2014) Photochromism of tetrahydroindolizines. Part XIV: Synthesis of cis-fixed conjugated photochromic pyridazinopyrrolo[1,2-b] isoquinolines incorporating carbon-rich linkers, Tetrahed. Lett., 55:2190-2197.
Vogel I.A (1978) A Text book of quantitative inorganic analysis. 4th edn ELBS and Longman, New York, p 352.
Simandi KI, Jaky M, Schelly ZA (1984) Short-lived manganate(VI) and manganate(V) intermediates in the permanganate oxidation of sulfite ion, J. Am. Chem. Soc., 106: 6866-6867.
Simandi LI, Jaky M, Savage CR, Schelly ZA (1985) Kinetics and mechanism of the permanganate ion oxidation of sulfite in alkaline solutions. The nature of short-lived Intermediates, J. Am. Chem. Soc., 107: 4220-4224.
Cotton FA, Wilkinson G (1980) Advanced Inorganic Chemistry, pp 747, John Wiley and Sons, New York.
Hassan RM (1993) Alginate polyelectrolyte ionotropic gels. XIV. Kinetics and mechanism of formation of intermediate complex during the oxidation of alginate polysaccharide by alkaline permanganate with a spectrophotometric evidence of manganate(VI) transient species. J. Polym. Sci. A, 31: 51-59.
Panari RG, Chougale RB, Nandibewoor ST (1998) Oxidation of mandelic acid by alkaline potassium permanganate. A kinetic study, J. Phys. Org. Chem., 11: 448-454.
De Oliveira LA, Toma HE, Giesbrecht E (1976) Kinetics of oxidation of free and coordinated dimethylsulfoxide with permanganate in aqueous solution, Inorg. Nucl. Chem. Lett., 2: 195-203.
Michaelis L, Menten ML (1913) The kinetics of invertase action. Biochem. Z. 49: 333–369.
Frost AA, Person RG (1973) Kinetics and Mechanism, 147 pp. Wiley Eastern, New Delhi; Amis ES (1966) Solvent effect on reaction rates and mechanism, pp. 28, Academic Press, New York.
Laidler K (1965) Chemical Kinetics. pp 123, McGraw-Hill, New York.
Hicks KW, Toppen DL, Linck RG (1972) Inner-sphere electron-transfer reactions of vanadium(II) with azidoamine complexes of cobalt(III). Inorg. Chem. 11: 310-315.