Effect of the Reactants Molar Ratio on the Kinetics of Cycloaddition of 2,3-Dimethylbuta-1,3-diene to methylacrylate

I. S. Kostiv1 kostiv.irina [at] gmail.com
G. A. Marshalok2 marescalcus [at] i.ua
  1. Chemical Engeeniring Department, National University “Lviv Polytechnic”, st. Bandery 12, Lviv, 79013 Ukraine
  2. Jan and Jedrzej Sniadecki University of Technology and Life Sciences in Bydgoszcz, POLAND, Bydgoszcz, 7, prof. S. Kaliskiego Al
Abstract 

The cycloaddition reaction between 2,3-dimethylbuta-1,3-diene and methylacrylate proceeds by the second order kinetics. The rate constants increase with the increase in the excess of one of the reactants. The change in the effective rate constants is described by the Michaelis–Menten equation indicating that the reaction proceeds through the initial equilibrium stage of formation of an intermediate complex which then transforms into the product. The effective rate constants, the equilibrium constants of formation of the intermediate complex, and the rate constant of its transformation into the reaction product were determined, as well as the thermodynamic parameters of the formation of the intermediate complex and the activation parameters of the transformation of the intermediate complex into the product. The limiting stage of the reaction is established and itsmechanism is suggested

Keywords 
2,3-dimethylbuta-1,3-diene
methylacrylate
methyl-3
4-dimethylcyclohex-3-ene-1-carboxylate
cycloaddition reaction
Michaelis–Menten equation
effective rate constants
intermediate complex
limiting stage
References 

[1] J.M. Velazquez, S.R. Hertenstein, J.R. Clare, and M.N. Green, US Patent 2010/0152083, 2010.

[2] J. Smets, M. Newman, H. Schenk, and P. Haspeter, US Patent 2008/0200359, 2008.

[3] І.S. Polyova, I.P. Polyuzhin, G.O. Marshalok and A.I. Gladii, “Analytical control of process obtaining R-allyl-1,3,4-trimethylcyclohex-3-encarboxylate by method gas-liquid hromatografy” Abstract of Papers, III Ukrainian Sci. Conf. of Students and Aspirants “Khimichny Karazinski Chitaniya 2011,” p. 41, Kharkov, 2011.

[4] R. Shmid, and V.N. Sapunov, “Neformal’naya kinetika (Unformal Cinetics)”, Moscow: Mir, p.264, 1985.

[5] R. Jasinski, M. Kwiatnowska and A. Baranski, “Мechanistyczne aspekty nieuzgodnionych (4+2)pelektronowych cykloaddycji”, Wiadom. Chemiczne, vol. 61, no. 7–8, p. 485-514, 2007.

[6] R.B. Woodward, and T.J Katz, “Studies of amineinduced ring opening of some mesoionic xanthines” Tetrahedron, vol. 5, no. 1, p. 70, 1959.

[7] L. Hammett, “Physical Organic Chemistry”, New York: McGraw-Hill, p.105, 1970.

[8] A.Coda Corsico, G. Desimoni, E. Ferrari, P. Righetti, and G. Tacconi, “Solvent effect as the result of frontier molecular orbital interaction-1 : The dielsalder reaction between 1,4-naphthoquinone and 2,3 dimethylbutadiene”, Tetrahedron, vol. 40, no. 9, p. 1611-1615, 1984.

[9] G. Desimoni, G. Faita, P. Righetti, and G. Tacconi, “Diels-Alder Reactions in Micellar”, Media J. Chem. Soc., Perkin Trans. 2, no. 3, p. 437-441, 1989.