Kinetic Study of Reactions between Nitrile Oxides with Simple Cycloalkynes with DFT Method

Document Type: Research Article

Author

Department of Chemistry Faculty of Science, Islamic Azad University, Tehran East Branch, Tehran, I.R. IRAN

Abstract

In this study, reactions of the simple cycloalkynes with substituted Nitrile Oxides, by DFT method will be discussed. The investigation of the structural properties, theoretical thermodynamic and kinetic data, i.e., the activation free energies(DG*), the free energies changes of reaction(DrG) and rate constants of the reactions (k) in 298 K and effects of Electron-withdrawing and electron-donating groups on the interaction of the LUMO with the HOMO of the dipole and dipolarophile will be presented. The results show an increase in the HOMO-LUMO energy gaps (DE) & DG* also decreasing the DrG & k by increasing the ring size of cycloalkynes.

Keywords

Main Subjects


[1] (a) Fringuelli F., Taticchi A., “The Diels–Alder Reaction: Selected Practical Methods”, John Wiley & Sons, Inc., Chichester, (2002).

(b) Kobayashi S., Jørgensen K.A., “Cycloaddition Reactions in Organic Synthesis”, Wiley-VCH Verlag GmbH: Weinheim, (2001).

(b) Tsoungas P.G., "Advances in Heterocyclic Compounds",  92: Academic Press (2002).

(c) Lyapkalo I.M., Ioffe S., Synthesis of Heterocycles via Cycloadditions II, Russ. Chem. Rev., 67: 467-   (1998).

(d) Gilchrist T.L., Wood J.E., “In Comprehensive Heterocyclic Chemistry II”; Boulton, A. J. (Ed.), Pergamon Press: Oxford, Vol. 6, pp. 279-299 (1996).

(e) Gilchrist T.L., Nitroso-Alkenes and Nitroso-Alkynes, Chem. Soc. Rev., 12: 53-73 (1983).

[3] Reviews: (a) Attanasi O.A., De Crescentini L., Favi G., Filippone P., Mantellini F., Perrulli F.R., Santeusanio S., Cultivating the Passion to Build Heterocycles from 1,2‐Diaza‐1,3‐dienes: the Force of Imagination; Eur. J. Org. Chem., 3109 (2009).

(b) Attanasi O.A., De Crescentini L., Filippone P., Mantelilini F., Santeusanio S., 1,2-Diaza-1,3-Butadienes; Just a Nice Class of Compounds, or Powerful Tools in Organic Chemistry? Reviewing an Experience, Arkivoc, (xi), 274 (2002).

[4] (a) Rai K.M.L., Synthesis of Heterocycles via Cycloadditions I Top. Heterocycl. Chem., 13, 1 (2008).

(b) Jäger V., Colinas P.A., “Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products; The Chemistry of Heterocyclic Compounds”, Padwa A., Pearson W.H. (Eds.), John Wiley & Sons, Inc.: New York, 59: 363-472 (2002).

(c) Gothelf K.V., Jørgensen K.A., Chem. Rev., 98: 863 (1998,).

(d) Easton C.J., Hughes C.M.M., Savage G.P., Simpson G.W., In Cycloaddition Reactions of Nitrile Oxides with Alkenes, Katritzky, A. R., Ed.; Adv. Heterocycl. Chem. 60: 261-327 (1994).

(e) Caramella P., Grünanger P., In 1,3-Dipolar Cycloaddition Chemistry; Padwa, A., Ed.; John Wiley & Sons, Inc., New York, 1: 291-392 (1984).

[5] Huisgen R., Kinetics and Mechanism of 1,3‐Dipolar CycloadditionsAngew. Chem. Int. Ed., 2(11): 633–645 (1963).

[6] Huisgen R., 1,3‐Dipolar Cycloadditions. Past and Future; Angew Chem Int Ed, 2(10): 565–598 (1963).

[7] 1,3-Dipolar cycloaddition;  From Wikipedia, The Free Encyclopedia [8] Huisgen R., Cenetary Lecture. -1,3-dipolar  Cycloadditions. In: “Proceedings of the Chemical society of London”, p 357 (1961).

[9] Patton GC., Development and Applications of click Chemistry; November 8, (2004) (and the literature cited there in). http://www.scs.uiuc.edu, Online

[10] van Steenis DJVC, David ORP, van Strijdonck GPF, van Maarseveen JH, Reek JNH.  Click-chemistry
as an Efficient Synthetic Tool for the Preparation of Novel Conjugated Polymers
; Chem Commun, 34: 4333–4335 ((2005).

[11] Dirks A.J., van Berkel S.S., Hatzakis N.S., Opsteen J.A., van Delft F.L., Cornelissen J.J.L.M., Rowan A.E., van Hest J.C.M., Rutjes F.P.J.T., Preparation of Biohybrid Amphiphiles via the Copper Catalysed Huisgen [3 + 2] Dipolar Cycloaddition Reaction, Chem. Commun., 33: 4172–4174 (2005)  (and the literature cited there in)

[12] Huisgen R., Hauck H., Gashey R., Seidl H., 1.3‐Dipolare Cycloadditionen, XLIII. Isoxazolidine aus Nitronen mit α.β‐ungesättigten Carbonestern oder Nitrilen; Reply. Chem. Ber., 101: 2568–2584 (1968).

[13] Huisgen R., Gashey R., Hauck H., Seidl H,. 1.3‐Dipolare Cycloadditionen, XLI. Anlagerung der Nitrone an Styrol; Orientierung und räumlicher Ablauf;; Chem. Ber., 101: 2548–2558 (1968) .

[14] Huisgen R., Gashey R., Hauck H., Seidl H., 1.3‐Dipolare Cycloadditionen, XLII. Additionen der Nitrone an Weitere Arylkonjugierte Äthylene Sowie an Vinyläther; Chem. Ber., 101: 2559–2567 (1968).

[15] Lan Y., Zou L., Cao Y., Houk K.N., Computational Methods To Calculate Accurate Activation and Reaction Energies of 1,3-Dipolar Cycloadditions of 24 1,3-Dipoles; J. Phys. Chem. A, 115:13906–13920 (2011).

[16] Ess D.H., Houk K.N., Theory of 1,3-Dipolar Cycloadditions: Distortion/Interaction and Frontier Molecular Orbital Models; J. Am. Chem. Soc., 130: 10187–10198, (2008).

[17] Ess D.H., Jones G.O., Houk K.N., Catalitic Cycloaddition Reactions; Adv. Synth. Catal., 348: 2337–2361 (2006).

[18] Xu L., Doubleday C.E., Houk K.N., Dynamics of 1,3-Dipolar Cycloadditions: Energy Partitioning of Reactants and Quantitation of Synchronicity; J. Am. Chem. So.c, 132: 3029–3037 (2010).

[19] Ess D.H., Hayden A.E., Kla¨rner F-G., Houk K.N., Theory of 1,3-Dipolar Cycloadditions: Distortion/Interaction and Frontier Molecular Orbital Models; J. Org. Chem., 73: 7586–759 (2008).

[21] Taherpour A.A., Kvaskoff D., Bernhardt P.V., Wentrup C., 9-Azidoacridine and 9-acridinylnitrene, J. Phys. Org. Chem., 23: 382–389 (2010).

[24] Taherpour A.A., Faraji M., Molbank M577, (2008).

[25] Taherpour A.A., Shfeei H., Rajaeian E., Ab Initio Studies of Molozonide Formation in 1,3-Dipolar Cycloaddition Reactions Between C7-C10 Membered Simple Cycloalkynes and O3; Orient. J. Chem., 27(3): 885–893 (2011).

[27] Vollhardt K.P.C., “Organic Chemistry”; W. H. Freeman & Company, New York (1987) .

[28] Carey F.A., Organic Chemistry; McGraw-Hill, Higher Education, 5th edn (International Edition (2003).

[29] Frisch M.J., etal; Gaussian 09, A.01. Gaussian Inc.,Wallingford CT(2009)

[30] McQuarrie DA, Simon JD, “Physical Chemistry”, University Science Books, Sausalito (1999).