Theoretical Calculation of Thermodynamic and Kinetic Quantities for 1,3 Dipolar Cycloaddition Reactions Between Nitrile Sulfides R–CNS (R = H, CH3, Ph and Ph(CH3)3) with 7–10 Membered Simple Cycloalkynes

  • Elahe Rajaeian
  • Elham Mirzaei
  • Avat Arman TaherpourEmail author
Research Paper


The 1,3-dipolar cycloaddition reactions also known as the Huisgen cycloaddition are one of the most widely used and versatile preparative methods in hetrocyclic chemistry. In this study, the reactivity and strain energy effect of the simple cycloalkynes with substituted Nitrile sulfides R–CNS (R = H, CH3, Ph and Ph(CH3)3) will be discussed in light of computational studies using DFT methods (B3LYP/6-31G*). The investigation of the structured properties, theoretical thermodynamic and kinetic data of the reactions in 298 K will be presented. The results show increase in the ∆G* by increasing the ring size and decreasing the strain energy of cycloalkynes. Also, the rate constants and the free energy changes in reactions increase as the size of the ring decreases. The relationships of the deviation of the internal bond angle (DIBA, in degrees), π-strain (S π ) (in kcal mol−1), the bond angle of Csp3–C ≡ C (θº) and ΔG #(kcal mol−1) for the series of cycloalkynes I-1 to I-4 have investigated.


Isothiazole Cycloalkynes Nitrile sulfide 1,3-dipolar cycloaddition reaction DFT-B3LYP Molecular orbital calculations Ab initio 



The corresponding author gratefully acknowledges from Theoretical and Computational Research Center of Chemistry Faculty of Razi University-Kermanshah-Iran, The authors gratefully acknowledge the Medical Biology Research Center and Kermanshah University of Medical Sciences, Kermanshah.


  1. Bak B, Christianseen JJ, Nieleen OJ, Svanholt H (1977) Acta Chem Scand A31:666CrossRefGoogle Scholar
  2. Carey FA, Sundberg RJ (2007) Advanced organic chemistry, 5th edn. Springer Science, New YorkGoogle Scholar
  3. Dirks AJ, van Berkel SS, Hatzakis NS, Opsteen JA, van Delft FL, Cornelissen JJLM, Rowan AE, van Hest JCM, Rutjes FPJT, Nolte RJM (2005) Chem Commun 33:4172–4174 (and the literature cited there in) CrossRefGoogle Scholar
  4. Domingo LR, Pe´rez P, Contreras R (2006) Eur J Org Chem 2:498–506CrossRefGoogle Scholar
  5. Ess DH, Houk KN (2008) J Am Chem Soc 130:10187–10198CrossRefGoogle Scholar
  6. Ess DH, Jones GO, Houk KN (2006) Adv Synth Catal 348:2337–2361CrossRefGoogle Scholar
  7. Ess DH, Hayden AE, Kla¨rner FG, Houk KN (2008) J Org Chem 73:7586–7759CrossRefGoogle Scholar
  8. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Zakrzewski VG, Montgomery JA Jr, Stratmann RE, Burant JC, Dapprich S, Millam JM, Daniels AD, Kudin KN, Strain MC, Farkas O, Tomasi J, Barone V, Cossi M, Cammi R, Mennucci B, PomelliC Adamo C, Clifford S, Ochterski J, Petersson GA, Ayala PY, Cui Q, Morokuma K, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Cioslowski J, Ortiz JV, Baboul AG, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Gomperts R, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Gonzalez C, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Andres JL, Gonzalez C, Head-Gordon M, Replogle ES, Pople JA (1998) Gaussian 98 Revision A.7. Gaussian Inc., PittsburghGoogle Scholar
  9. Huisgen R (1961) Cenetary lecture-1,3-dipolar cycloadditions. In: Proceedings of the chemical society of London, p 357Google Scholar
  10. Huisgen R (1963) Angew Chem Int Ed 2(10):565–598CrossRefGoogle Scholar
  11. Huisgen R, Hauck H, Gashey R, Seidl H (1968a) Chem Ber 101:2568–2584CrossRefGoogle Scholar
  12. Huisgen R, Gashey R, Hauck H, Seidl H (1968b) Chem Ber 101:2548–2558CrossRefGoogle Scholar
  13. Huisgen R, Gashey R, Hauck H (1968c) Seidl H Chem Ber 101:2559–2567CrossRefGoogle Scholar
  14. Johnson RP, Daoust KJ (1995) J Am Chem Soc 117:362CrossRefGoogle Scholar
  15. Lan Y, Zou L, Cao Y, Houk KN (2011) J Phys Chem A 115:13906–13920CrossRefGoogle Scholar
  16. McQuarrie DA, Simon JD (1999) Physical chemistry. University Science Books, SausalitozbMATHGoogle Scholar
  17. Patton GC (2004) Development and applications of click chemistry. Accessed 8 Nov 2004. (and the literature cited there in)
  18. Sakai S, Nguyen MT (2004) J Phys Chem A 108(42):9169–9179CrossRefGoogle Scholar
  19. Taherpour AA, Faraji M (2008) Molbank M 577Google Scholar
  20. Taherpour AA, Kheradmand K (2009) J Heterocyclic Chem 46:131–133CrossRefGoogle Scholar
  21. Taherpour AA, Kvaskoff D, Bernhardt PV, Wentrup C (2010) J Phys Org Chem 23:382–389Google Scholar
  22. Taherpour AA, Shfeei H, Rajaeian E (2011) Orient J Chem 27(3):885–893Google Scholar
  23. Taherpour AA, Rajaeian E, Shafiei H, Malekdar M (2013) Struct Chem 24(2):523–534CrossRefGoogle Scholar
  24. Van Steenis DJVC, David ORP, van Strijdonck GPF, van Maarseveen JH (2005) Reek JNH Chem Commun 34:4333–4335CrossRefGoogle Scholar
  25. Vollhardt KPC (1987) Organic chemistry. W. H. Freeman & Company, New YorkGoogle Scholar
  26. Xu L, Doubleday CE (2010) Houk KN J Am Chem Soc 132:3029–3037CrossRefGoogle Scholar

Copyright information

© Shiraz University 2016

Authors and Affiliations

  • Elahe Rajaeian
    • 1
  • Elham Mirzaei
    • 1
  • Avat Arman Taherpour
    • 2
    • 3
    Email author
  1. 1.Chemistry Department, Science FacultyIslamic Azad University, Arak BranchArakIran
  2. 2.Department of Organic Chemistry, Faculty of ChemistryRazi UniversityKermanshahIran
  3. 3.Medical Biology Research CenterKermanshah University of Medical SciencesKermanshahIran

Personalised recommendations