MRC  Vol.4 No.3 , July 2015
Effect of Cosolvent in a Nucleophilic Substitution Reaction Using Organoclay in Triphase Catalytic System
Abstract: A remarkable rate enhancement technique has been devised for a typical nucleophilic displacement reaction by using triphase catalytic materials based on tetraoctylammonium exchange forms of hectorite clay. Pseudo-first order rate constants (kobs) for the conversion of 1-bromobutane to the corresponding chloride under triphase conditions using the clay catalyst in the presence of various polar cosolvents have been observed. The results here have shown that the addition of a cosolvent increases the catalytic activity of the triphase system by several fold. In addition, the results have demonstrated that each cosolvent has a unique concentration for achieving an optimum reaction rate.
Cite this paper: Shabestary, N. , Chapple, C. , Rensing, D. , Doan, T. , Khazaeli, S. , Sabo, M. and Beach, A. (2015) Effect of Cosolvent in a Nucleophilic Substitution Reaction Using Organoclay in Triphase Catalytic System. Modern Research in Catalysis, 4, 78-85. doi: 10.4236/mrc.2015.43010.

[1]   Regen, S.L. (1979) Dreiphasen-Katalyse. Angewandte Chemie, 91, 464-472.

[2]   Regen, S.L. (1975) Triphase Catalysis. Journal of the American Chemical Society, 97, 5956-5957.

[3]   Shabestary, N., Rensing, D.T., Reed, D.N., Austiff, A.F. and Cox, M.D. (2014) Triphase Catalysis Based on Gemini Surfactant-Clay Intercalates. Modern Research in Catalysis, 3, 26-34.

[4]   Murugan, E. and Gopinath, P. (2009) Triphase Catalytic Activity of a New Insoluble Multi-Site Phase Transfer Catalyst in C-alkylation of Dihydrocarvone—A Kinetic Study. Journal of Molecular Catalysis A: Chemical, 309, 12-20.

[5]   Ragaini, V., Verzella, G., Ghignone, A. and Colombo, G. (1986) Fixed-Bed Reactors for Phase-Transfer Catalysis. A Study of a Liquid-Liquid-Solid Reaction. Industrial Engineering Chemistry Process Design and Development, 25, 878-885.

[6]   Dutta, N.N., Borthakur, S. and Patil, G.S. (1992) Triphase Catalysis for Recovery of Phenol from an Aqueous Alkaline Stream. Industrial Engineering Chemistry Research, 31, 2727-2731.

[7]   Dutta, N.N. and Pangarkur, V.G. (1994) Liquid-Liquid-Solid Reactions: Esterification of Phenol with Benzoyl Chloride Using a Polymer-Supported Phase Transfer Catalyst. Reactive Polymers, 22, 9-17.

[8]   Yadav, G.D. and Naik, S.S. (2000) Clay-Supported Liquid-Liquid-Solid Phase Transfer Catalysis: Synthesis of Benzoic Anhydride. Organic Process Research & Development, 4, 141-146.

[9]   Danao, S.P., Thorat, R.T. and Nageshwar, G.D. (2005) Kinetics of Oxidation of Phenethyl Alcohol by Triphase Catalysis. Indian Chemical Engineer, 47, 156-160.

[10]   Dutta, N.N., Ghosh, A.C. and Mathur, R.K. (1997) Rate-Limiting. In: Halpern, M.E., Ed., American Chemical Society Publication, Symposium Series 659, Chapter 20, American Chemical Society, Washington DC, 261-276.

[11]   Pinnavaia, T.J. (1992) Organoclay Triphase Catalysts. U.S. Patent 5,099,054.

[12]   Regen, S.L. and Besse, J.J. (1979) Liquid-Solid-Liquid Triphase Catalysis. Consideration of the Rate-Limiting Step, Role of Stirring, and Catalyst Efficiency for Simple Nucleophilic Displacement. Journal of the American Chemical Society, 101, 4059-4063.

[13]   Venturello, P., Tundo, P. and Angeletti, E. (1982) Anion-Exchange Properties of Ammonium Salts Immobilized on Silica Gel. Journal of the American Chemical Society, 104, 6547-6551.

[14]   Venturello, P., Tundo, P. and Angeletti, E. (1982) Phase-Transfer Catalysts Immobilized and Adsorbed on Alumina and Silica Gel. Journal of the American Chemical Society, 104, 6551-6555.

[15]   Cornelis, A., Laszlo, P. and Pennetreau, P. (1983) Some Organic Syntheses with Clay Supported Reagents. Clay Minerals, 18, 437-445.

[16]   Kadkhodayan, A. and Pinnavaia, T.J. (1983) Clay Intersalation Compounds for Selective Triphase Catalysis: Reaction of Alkyl Bromide with NaCl. Journal of Molecular Catalysis, 21, 109-117.

[17]   Cornelis, A. and Laszlo, P. (1982) Clay-Supported Reactions; II. Quaternary Ammonium-Exchanged Montmorillonite as Catalyst in the Phase-Transfer Preparation of Symmetrical Formaldehyde Acetals. Synthesis, 2, 162-163.

[18]   Lin, C.L. and Pinnavaia, T.J. (1991) Organo Clay Assemblies for Triphase Catalysis. Chemistry Materials, 3, 213-215.

[19]   Regen, S.L., Nigam, A. and Besse J. (1978) Triphase Catalysis. Insolubilized Hexamethylphosphoramide as a Solid Solvent. Tetrahedron Letters, 19, 2757-2760.

[20]   Tomoi, M., Ikeda, M. and Kakiuchi, H. (1978) Polymer-Supported Phosphoric Triamides as Catalysts for Phase-Transfer Reactions. Tetrahedron Letters, 19, 3757-3758.

[21]   Regen, S.L., Mehrota, A. and Singh, A. (1981) Poly(acrylamide)-Based Solid-Phase Cosolvents. Journal of Organic Chemistry, 46, 2182-2184.

[22]   Mills, J.G. and Zwarich, M.A. (1972) Recognition of Interstratified Clays. Clays and Clay Minerals, 20, 169-174.

[23]   Hradil, J. and Svec, F. (1984) Phase Transfer Catalysis. Polymer Bulletin, 11, 159-164.

[24]   Telford, S., Schlunt, P. and Chau, P.C. 1986) Mechanism of Polymer-Supported Phase-Transfer Catalysis. Effect of Phase Ratios on Low-Percent Ring Substitution Microporous Polystyrene Resin. Macromolecules, 19, 2435-2439.

[25]   Ruckenstein, E. and Hong, L. (1992) Hydrophilic Recognition by Polymer-Supported Phase Transfer Catalysts and Its Effect on Reaction Activity and Selectivity. Journal of Catalysis, 136, 378-391.

[26]   Svec, F. (1988) What Is the Real Mechanism of Polymer-Supported Phase-Transfer Catalysis. Pure and Applied Chemistry, 60, 377-386.

[27]   Shabestary, N., Khazaeli, S. and Long, N. (2005) Triphase Catalytic Reactions Using Clay Intercalates. International Journal of Science & Technology (Scientia Iranica), 12, 290-294.