Back
 OJPC  Vol.2 No.2 , May 2012
Hydroxyalkylation of Cyclic Imides with Oxiranes Part I. Kinetics of Reaction in Presence of Triethylamine as Catalyst
Abstract: Literature describes kinetics of reactions of alcohols, phenols, carboxylic acids, amines and amides with oxiranes such as ethylene oxide and propylene oxide. However, there is no information regarding kinetic of reaction of imides with oxiranes. In this article the kinetics of the reaction of cyclic monoimides: succinimide, phtalimide, and glutarimide, with ethylene and propylene oxides in presence of triethylamine in aprotic solvent was studied. The rate laws for those processes were established based upon on dilatometric measurements. I was said that cyclic monoimides react with oxiranes in presence of triethylamine to give N-(2-hydroxyalkyl)imides as major product. This product react further with oxiranes in consecutive reaction. The kinetics of the reaction of cyclic mono-imides with oxiranes obey the following rate law: V = k1/2 c1/2cat c3/2imide c1/2oxirane. Based upon kinetic data the following orders of reactivity of imides and oxiranes were obtained: phtalimide ≥ succinimide > glutarimide and ethylene oxide > propylene oxide. The solvent (DMF, DMSO and dioxane) effect was also studied. From temperature dependences the thermodynamic parameters: activation energy, enthalpy and entropy from linear Eyring plots were obtained.
Cite this paper: 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, 2012, pp. 88-96. doi: 10.4236/ojpc.2012.22012.
References

[1]   A. Kirrmann, J. Cantacuzene and P. Duhamel, “Chimie Organique, Vol. 2. Fonctions Simples”, WNT, Warsaw, 1980, pp. 225-226.

[2]   R. Steele, A. Katzakian, J. Scigliano and E. Hamel, “Imide Oxirane Reactions,” US Patent No. 3962182, 1976.

[3]   J. Billman and E. Parker, “Amino Acids. I. Glycine,” Journal o the American Chemical Society, Vol. 65, No. 5, 1943, pp.761-762. doi:10.1021/ja01245a008

[4]   K. Yanagi and S. Akiyoshi, “Notes: Hydroxyethylation of Imides,” The Journal of Organic Chemistry, Vol. 24, No. 8, 1959, pp. 1122-1123. doi:10.1021/jo01090a601

[5]   N. Schoenfeldt, “Grenzflaechenactive Aethylenoxid— Addukte,” Wissenschaftliche Verlagsgesellschaft MBH, Stuttgart, 1976.

[6]   R. Cornwell, “Composition Capable of Being Molded and Being Cast into Films,” US Patent No. 2487105, 1949.

[7]   M. Kucharski and J. Lubczak, “Polyurethane Foams Based on Reaction Products of Ethylene Oxide with 1,3,5-Tris(Hydroxymethyl) Isocyanurate,” Polimery, Vol. 30, No. 9, 1985, pp. 354-361.

[8]   P. Tawney, “N-methylol maleimide,” US Patent No. 2526517, 1950.

[9]   G.Weitzel, F. Schneider, A. Fretzdorf, K. Seynsche and H. Finger, “Futher Tumor Inhibiting Compounds. I. Cytostatic Effects of Nand S-Hydroxy-Methyl Compounds,” Zeitung Physiologische Chemie, No. 334, 1963, pp. 1-25.

[10]   S. Kucharski, “Nonionic Surfactants. I. Preparation of Poly(Oxyethylene) Alcohols,” Wiadomo?ci Chemiczne, Vol. 25, No. 8, 1971, pp. 579-594.

[11]   N. Lebedev and I. Baranov, “Reaction Involving α-Oxides. X. Kinetics and Mechanism of the Reaction of Ethylene Oxide and Alcohols under the Conditions of Base Catalysis,” Kinetika i Kataliz, Vol. 7, No. 4, 1966, pp. 619-626.

[12]   N. Lebedev and V. Shvets, “Mechanism of Ethylene Oxide Reactions with Phenols,” Kinetika i Kataliz, Vol. 9, No. 3, 1968, pp. 504-510.

[13]   V. Shvets and I. Y. Lykov, “Kinetics and Mechanism of the Reaction of Ethylene Oxide with n-Decyl Mercaptan during Basic Catalysis,” Kinetika i Kataliz, Vol. 12, No. 2, 1971, pp. 347-355.

[14]   V. Shvets and I. Y. Lykov, “Kinetics and Mechanism of the Noncatalytic Reaction of Ethylene Oxide with n-Decyl Mercaptan,” Kinetika i Kataliz, Vol. 12, No. 4, 1971, pp. 883-888.

[15]   V. Shvets, A. Romashkin and V. Yudina, “Kinetics and Mechanism of the Reaction of Ethylene Oxide with Terephthalic Acid during Catalysis by Tetraal-Kylammonium Halides,” Kinetika i Kataliz, Vol. 14, No. 4, 1973, pp. 928-932.

[16]   N. Lebedev and K. Guskov, “Reaction of α-Oxides. II. Kinetics of the Reactions of Ethylene Oxides with Acetic and Monochloroacetic Acids,” Kinetika i Kataliz, Vol. 5, No. 4, 1963, pp. 116-127.

[17]   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

[18]   N. Lebedev and M. Smirnova, “Mechanism of the Acid Catalysis of the Reaction of Ethylene Oxide with Amines,” Zhurnau Obshchei Khimii, Vol. 39, No.12, 1969, pp. 2732-2737.

[19]   A. Weindenbacher, S. Serban and E. Weindenbacher, “Kinetics of Ethoxylation Reactions in Series of Primary Aliphatic-Amines,” Revista de Chimie, Vol. 29, No. 3, 1978, pp. 204-209.

[20]   N. Iranpoor, I. Mohammadpoor-Baltork and F. S. Zardaloo, “Ceric Ammonium Nitrate an Efficient Catalyst for Mild and Selective Opening of Epoxides in the Presence of Water Thiols and Acetic Acid,” Tetrahedron, Vol. 47, No. 47, 1991, pp. 9861-9866. doi:10.1016/S0040-4020(01)80723-7

[21]   C. Moberg, L. Rakos, and L. Tottie, “Stereospecific Lewis Acid Catalyzed Methanolysis of Styrene Oxide,” Tetrahedron Letters, Vol. 33, No. 16, 1992, pp. 2191-2194. doi:10.1016/0040-4039(92)88174-4

[22]   C. C. Price and D. D. Carmelite, “Reactions of Epoxides in Dimethyl Sulfoxide Catalyzed by Potassium t-Butoxide,” Journal of the American Chemical Society, Vol. 88, No. 17, 1966, pp. 4039-4044. doi:10.1021/ja00969a026

[23]   A. Bukowska and W. Bukowski, “A Highly Regio-Selective Catalyst of Epichlorohydrin Acidolysis,” Journal of Chemical Technology & Biotechnology, Vol. 73, No. 4, 1998, pp. 341-344. doi:10.1002/(SICI)1097-4660(199812)73:4<3C341::AID-JCTB960>3.0CO;2-6

[24]   A. Guy, J. Doussot, C. Ferroud, R. Garreau and A. Godefroy-Falguieres, “Regioselective Ring Opening of Epoxides with Lithium Azide,” Synthesis, Vol. 9, 1992, pp. 821-822. doi:10.1055/s-1992-26233

[25]   M. Brunner, L. Mussmann and D. Vogt, “Kinetic Resolution of Oxiranes by Use of Chiral Lewis Acid Catalysts,” Synlett, Vol. 12, 1993, pp. 893-894. doi:10.1055/s-1993-22641

[26]   E. Knaggs, “Alkanoloamides in Soft Detergents,” Soap Chemical Specialties, Vol. 40, No. 12, 1964, pp. 79-83.

[27]   H.Grossmann, “Die Beeinflussung der Reaktion bei der Oxaethylierung von Fettsaeuremonoaethanolamiden,” Fette, Seifen, Anstrichmittel, Vol. 74, No. 1, 1972, pp. 58-63. doi:10.1002/lipi.19720740111

[28]   S. Kanoh, M. Naka, T. Nishimura and M. Motoi, “Isomerization of Cyclic Ethers Having a Carbonyl Functional Group: New Entries into Different Heterocyclic Compounds,” Tetrahedron, Vol. 58, No. 35, 2002, pp. 7049-7064. doi:10.1016/S0040-4020(02)00701-9

[29]   K. Frisch, D. Tummers and A. Nijenhuis, “Tris-(N-β-Hydroxypropyl) Isocyanurate,” Europe Patent No. 3620, 1979.

[30]   A. Slaczka 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. 4067-4074. doi:10.1002/app.26742

[31]   E. Chmiel-Szukiewicz, “Polyetherols Obtained from 6-Aminouracil and Oxiranes,” Journal of Applied Polymer Science, Vol. 103, No. 3, 2007, pp. 1466-1472. doi:10.1002/app.25100

[32]   J. Lubczak, “Reactions in the System (Hydroxymethyl)Melamines-Oxiranes: Addition,” Indian Journal of Chemistry, Vol. 33B, 1994, pp. 125-131.

[33]   K. Schwetlick, “Kinetische Methoden zur Unter-Suchung von Reactionsmechanismen,” VEB, Deutscher Verlag der Wissenschaften, Berlin, 1971.

 
 
Top