Theoretical Determination of the Active Sites of Naphthalene, Nitronaphthalene, Methoxynaphthalene, Quinoline and Isoquinoline in Cycloaddition Reaction with C20 Fullerene

Document Type : Research Article

Author

Chemistry Department, Faculty of Basic Science, Ayatollah Boroujerdi University, Boroujerd,, I.R. IRAN

Abstract

In this research, a theoretical study on the cycloaddition reaction of the C20 fullerene and certain fused bicyclic aromatic compounds including naphthalene, 2-methoxynaphthalene, 2-nitronaphthalene, quinoline, and isoquinoline was carried out with the aims of functionalization possibility of the fullerene and investigation of the reactivity and regioselectivity. For this purpose, the [4+2] cycloaddition reaction between the above mentioned aromatic systems and fullerene was studied in which, the fullerene and aromatic systems act as dienophile and diene, respectively. Except for the naphthalene, two possible reaction paths were considered for the aromatic systems in which, the substituent- or heteroatom-containing ring reacts in one path and the ring without substituent or heteroatom reacts in another one. The thermodynamic and kinetic parameters of each reaction path were calculated using optimization of the reactants, products, and transition states geometries. In order to study the reactivity of different positions of the naphthalene, 2-nitronaphthalene, 2-methoxynaphthalene, quinoline, and isoquinoline, three different methods were used including calculation of the Parr as well as Fukui functions and the value of the contribution of different atoms in the HOMO of the aromatic system. The results indicated that the Fukui functions can completely describe the reactivity of different positions of the above aromatic compounds. Also, the Parr functions and the contribution value of different atoms in HOMO can satisfactorily describe the reactivities in the corresponding cycloaddition reactions. The Global Electron Density Transfer (GEDT) value was also calculated for the reactions and the results revealed that the reactions are polar in character and the electron density is transferred from the aromatic compound toward the fullerene. Finally, the calculation of the synchronicity showed that the reactions of fullerene with the naphthalene and the heteroatom-containing ring in the quinoline and isoquinoline are more synchronous in comparison to the other ones.

Keywords

Main Subjects


 [1] Kroto H.W., Heath J.R., O’Brien S.C., Curl R.F., Smalley R.E., C60: Uckminsterfullerene, Nature, 318:162−163 (1985).
[2] Prinzbach H., Weiler A., Landenberger P., Wahl F., Wörth J., Scott L.T., Gelmont M., Olevano D., Issendorff B.V., Gas-phase Production and Photoelectron Spectroscopy of the Smallest Fullerene, Nature, 407: 60-63 (2000).
[3] Prinzbach H., Wahl F., Weiler A., Landenberger P., Worth J., Scott L.T., Gelmont M., Olevano D., Sommer F., Issendorff B. von, C20 Carbon Clusters: Fullerene-Boat-Sheet Generation, Mass Selection, Photoelectron Characterization, Chem. Eur. J., 12: 6268-6280 (2006).
[4] Jin Z., Gehrig D., Dyer-Smith C., Heilweil E.J., Laquai F., Bonn M., Turchinovich D., Ultrafast Terahertz  Photoconductivity of Photovoltaic Polymer−Fullerene Blends: A Comparative Study Correlated with Photovoltaic Device Performance, J. Phys. Chem. Lett., 5: 3662−3668 (2014).
[5] Oosterhout S.D., Savikhin V., Zhang J., Zhang Y., Burgers M.A., Marder S.R., Bazan G.C., Toney M.F., Mixing Behavior in Small Molecule:Fullerene Organic Photovoltaics, Chem. Mater., 29: 3062-3069 (2017).
[7] Keypour H., Noroozi M., Rashidi A., Shariati Rad M., Application of Response Surface Methodology  for Catalytic Hydrogenation of Nitrobenzene to Aniline Using Ruthenium Supported Fullerene Nanocatalyst, Iran. J. Chem. Chem. Eng. (IJCCE), 34: 21-32 (2015).
[8] Schneider N.S., Darwish A.D., Kroto H.W., Taylor R., Walton D.R.M., Formation of Fullerols Via Hydroboration of Fullerene-C60, J. Chem. Soc. Chem. Commun., 463−464 (1994).
[9] Nie, B., Hasan K., Greaves M.D., Rotello V.M., Reversible Covalent Attachment of C60 to a Furan-Functionalized Resin, Tetrahedron Lett., 36: 3617-3618 (1995).
[10] Zhang Y., Dai T., Wang M., Vecchio D., Chiang L.Y., Hamblin M.R., Potentiation of Antimicrobial Photodynamic Inactivation Mediated by a Cationic Fullerene by Added Iodide: in Vitro and in Vivo Studies, Nanomedicine (Lond.), 10: 603–614 (2015).
[11] Nakamura S., Mashino T., Biological Activities of Water-soluble Fullerene Derivatives, J. Phys. Conf. Ser., 159: 012003 (2009).
[12] Hsieh F.-Y., Zhilenkov A.V., Voronov I.I., Khakina E.A., Mischenko D.V., Troshin P.A., Hsu S.-H., Water-Soluble Fullerene Derivatives as Brain Medicine: Surface Chemistry Determines If They Are Neuroprotective and Antitumor, ACS Appl. Mater. Interfaces, 9: 11482-11492 (2017).
[13] Hirsch A., "Fullerenes and Related Structures", Springer, Berlin, (1999).
[15] Sarova G.H., Berberan-Santos M.N., Kinetics of the Diels–Alder Reaction Between C60 and Acenes, Chem. Phys. Lett., 397: 402–407 (2004).
[16] Wang G.-W., Chen Z.-X., Muratac Y., Komatsu K., [60] Fullerene Adducts with 9-Substituted Anthracenes: Mechanochemical Preparation and Retro Diels–Alder Reaction, Tetrahedron, 61: 4851–4856 (2005).
[19] Soleymani, M. Theoretical Study of the Possibility of Functionalization of C20 Fullerene with Simplest Ketene CH2CO, J. Struct. Chem., 60: 524-535 (2019).
[20] Soleymani M., Dashti Khavidaki H., Inactivation Possibility of Pyrene by C20 Fullerene Via Cycloaddition Reactions: A Theoretical Study, Comp. Theor. Chem., 1112: 37–45 (2017).
[22] Böhlendorf B., Bedorf N., Jansen R., Trowitzsch-Kienast W., Höfle G., Forche E., Gerth K., Irschik H., Kunze B., Reichenbach H., Antibiotics from Gliding Bacteria. LXXIII. Indole and Quinoline Derivatives as Metabolites of Tryptophan in Myxobacteria, Eur. J. Org. Chem., 1996: 49-53 (1996).
[23] Orjala J., Gerwick W.H., Two Quinoline Alkoloids from the Caribbean Cyanobacterium Lyngbya Majuscule, Phytochem., 45: 1087-1090 (1997).
[24] Padoley K.V., Mudliar S.N., Pandey R.A., Heterocyclic Nitrogenous Pollutants in the Environment and their Treatment Options-An Overview, Bioresour. Technol., 99: 4029–4043 (2008).
[26] Neuwoehner J., Reineke A.-K., Hollender J., Eisentraeger A., Ecotoxicity of Quinoline and Hydroxylated Derivatives and their Occurrence in Groundwater of a Tar-Contaminated field Site, Ecotoxicol. Environ. Safety, 72: 819-827 (2009).
[27] Sideropoulos A.S., Specht S.M., Evaluation of Microbial Testing Methods for the Mutagenicity of Quinoline and its Derivatives, Curr. Microbiol., 11: 59–65 (1984).
[28] Ogunsola O.M., Decomposition of Isoquinoline and Quinoline by Supercritical Water, J. Hazard. Mater., 74: 187–195 (2000).
[29] Jianlong W., Xiangchun Q., Liping H., Yi Q., Hegemann W., Microbial Degradation of Quinoline by Immobilized Cells of Burkholderia Pickettii, Water Res., 36: 2288-2296 (2002).
[30] Kohsari, S., Mashayekhi, M., Farajpour, E., Quinoline Biodegradation by Bacillus Licheniformis Strain CRC-75, Iran. J. Chem. Chem. Eng. (IJCCE), 29(2): 151-158 (2010).
[31] Chang L., Zhang Y., Gan L., Xu H., Yan N., Liu R., Rittmann B.E., Internal Loop Photo-Biodegradation Reactor Used for Accelerated Quinoline Degradation and Mineralization, Biodegradation, 25:, 587–594 (2014).
[35] Geerlings P., De Proft F., Langenaeker W., Conceptual Density Functional Theory, Chem. Rev., 103: 1793-1874 (2003).
[36] Ayers, P.W., Parr, R.G., A theoretical Perspective on the Bond Length Rule of Grochala, Albrecht, and Hoffmann, J. Phys. Chem. A, 104: 2211-2220 (2000).
[38] Soleymani M., Sabzyan H., Bagherzadeh M., Ahmadi H., Voltammetric Studies on 2-oxo-1,2,3,4-Tetrahydropyrimidin-5-Carboxamides: Substituent Effects, J. Phys. Chem. A,115: 8264-8270 (2011).
[39] Frisch M.J., et al. Gaussian 09, Revision A.1, Gaussian Inc., Wallingford, CT, (2009).
[41] Peng C., Ayala P.Y., Schlegel H.B., Frisch M.J., Using Redundant Internal Coordinates to Optimize Equilibrium Geometries and Transition States, J. Comput. Chem., 17: 49-56 (1996).
[42] Gonzalez C., Schlegel H.B., Reaction Path Following in Mass-Weighted Internal Coordinates, J. Phys. Chem., 94: 5523-5527 (1990).
[43] Eyring H., The Activated Complex In Chemical Reactions, J. Chem. Phys., 3: 107-115 (1935).
[44] Lecea B., Arrieta A., Roa G., Ugalde J.M., Cossio F.P., Catalytic and Solvent Effects on the Cycloaddition Reaction Between Ketenes and Carbonyl Compounds to form 2-Oxetanones, J. Am. Chem. Soc., 116: 9613-9619 (1994).
[45] Reed A.E., Curtiss L.A., Weinhold F., Intermolecular Interactions from a Natural Bond Orbital, Donor-Acceptor Viewpoint, Chem. Rev., 88: 899-926 (1988).
[46] Parr R.G., Szentpaly L.V., Liu S., Electrophilicity Index, J. Am. Chem. Soc., 121: 1922–1924 (1999).
[47] Domingo, L.R., Chamorro E., Pe´rez, P., Understanding the Reactivity of Captodative Ethylenes in Polar Cycloaddition  Reactions. A Theoretical Study,  J. Org. Chem., 73: 4615–4624 (2008).
[49] Baekelandt, B.G., Cedillo, A., Parr, R.G., Reactivity Indices and Fluctuation Formulas in Density Functional Theory: Isomorphic Ensembles and a New Measure of Local Hardness, J. Chem. Phys., 103: 8548-8556 (1995).
[50] Domingo L.R., Pérez P., Sáez J.A., Understanding the Local Reactivity in Polar Organic Reactions Through Electrophilic and Nucleophilic Parr Functions, RSC Adv., 3: 1486–1494 (2013).
[51] Chamorro E., Pérez P., Domingo L.R., On the Nature of Parr Functions to Predict the Most Reactive Sites Along Organic Polar Reactions, Chem. Phys. Lett., 582: 141-143 (2013).
[52] Yang W., Mortier W.J., The Use of Global and Local Molecular Parameters for the Analysis of the Gas-Phase Basicity of Amines, J. Am. Chem. Soc., 108: 5708-5711 (1986).
[53] Domingo L.R., Aurell M.J., Pêrez P., Contreras R., Quantitative Characterization of the Local Electrophilicity of Organic Molecules. Understanding the Regioselectivity on Diels-Alder Reactions, J. Phys. Chem. A, 106: 6871-6875 (2002).
[54] Pêrez P., Domingo L.R., Duque-Noreňa M., Chamorro E., A Condensed-to-Atom Nucleophilicity Index. An Application to the Director Effects on the Electrophilic Aromatic Substitutions, J. Mol. Struct. THEOCHEM, 895: 86-91 (2009).