Back
 OJPC  Vol.2 No.2 , May 2012
Hydroxyalkylation of Cyclic Imides with Oxiranes. Part II. The Mechanism of Reaction in Presence of Triethylamine
Abstract: The mechanism of reaction of cyclic monoimides with oxiranes was established based upon kinetic studies and product analysis. It has been established that the reaction proceeds through initial formation of an adduct of imide and triethylamine. The crucial bond in adduct has ionic character; in non-aqueous solvents it is present as ion pair, while in water the adduct dissociate and free ions are present. The adduct enables the proton transfer from imide to oxirane. The rate determining step is reaction of imide and this adduct. Different values of entropy of transition states obtained from thermodynamic calculations suggest slightly different structure of transition state of rate determining step.
Cite this paper: J. Lubczak, "Hydroxyalkylation of Cyclic Imides with Oxiranes. Part II. The Mechanism of Reaction in Presence of Triethylamine," Open Journal of Physical Chemistry, Vol. 2 No. 2, 2012, pp. 97-102. doi: 10.4236/ojpc.2012.22013.
References

[1]   J. Lubczak, “Hydroxyalkylation of Cyclic Imides with Oxiranes. Part I. Kinetics of Reaction in Presence of Triethylamine as Catalyst,” Open Journal of Physical Chemistry, Vol. 2, No. 2, 2002, p. 2.

[2]   L. Shechter and J. Wynstra, “Glycidyl Ether Reactions with Alcohols, Phenols, Carboxylic Acids, and Acid Anhydrides,” Industrial and Engineering Chemistry, Vol. 48, No. 1, 1956, pp. 86-93. doi:10.1021/ie50553a028

[3]   S. Blum, P. Walsh and R. Bergman, “Epoxide-Opening and Group-Transfer Reactions Mediated by Monomeric Zirconium Imido Complexes,” Journal of American Chemical Society, Vol. 125, No. 47, 2003, pp. 14276-14277. doi:10.1021/ja037267t

[4]   L.-Z. Dai and M. Shi, “A Gold(I)-Catalyzed Intramolecular Reaction of Propargylic/Homopropargylic Alcohols with Oxirane,” Chemistry—A European Journal, Vol. 14, No. 23, 2008, pp. 7011-7018. doi:10.1002/chem.200701954

[5]   N. Iranpoor, H. Firouzabadi, R. Azadi and F. Ebrahimzadeh, “Regioselective Synthesis of vic-Halo Alcohols and Symmetrical or Unsymmetrical vic-Dihalides from Epoxides Using Triphenylphosphine N-Halo Imides,” Canadian Journal of Chemistry, Vol. 84, No. 1, 2006, pp. 69-75. doi:10.1139/v05-261

[6]   J. F. Larrow and E. N. Jacobsen, “Asymmetric Processes Catalyzed by Chiral (Salen)Metal Complexes,” Topics in Organometallic Chemistry, No. 6, 2004, pp. 123-152. doi:10.1007/b11772

[7]   K. Schwetlick, “Kinetische Methoden zur Untersuchung von Reactionsmechanismen”, VEB, Deutscher Verlag der Wissenschaften, Berlin 1971.

[8]   I. Cisek-Cicirko and J. Lubczak, “Reactions of Hydroxymethyl Derivatives of Uric Acid with Oxiranes. II. an Analysis of Reaction Course and Product Structure,” Journal of Applied Polymer Science, Vol. 83, No. 9, 2002, pp. 1955-1962. doi:10.1002/app.10108

[9]   A. ?l?czka and J. Lubczak, “Hydroxyalkylation of Barbituric Acid. II. Synthesis of Polyetherols with Pyrimidine Ring,” Journal of Applied Polymer Science, Vol. 106, No. 6, 2007, pp. 4067-1074. doi:10.1002/app.26742

[10]   M. Kucharski, J. Lubczak and E. Rokaszewski, “Addition of Oxiranes to Hydroxymethyl Derivatives of Isocyanuric Acid,” Chemia Stosowana, Vol. 27, No. 1-2, 1983, pp. 65-77.

[11]   J. Lubczak, “Reactions of Hydroxymethyl Derivatives of Uric Acid with Oxiranes: Recognition of Mechanism Based on Kinetic Studies,” International Journal of Chemical Kinetics, Vol. 38, No. 5, 2006, pp. 345-350. doi:10.1002/kin.20167

 
 
Top