Hostname: page-component-78c5997874-4rdpn Total loading time: 0 Render date: 2024-11-13T01:54:27.353Z Has data issue: false hasContentIssue false
  • English
  • Français

Clay-Polymer Nanocomposite-Supported Brominating Agent

Published online by Cambridge University Press:  01 January 2024

Hany El-Hamshary ,
Adel I. Selim ,
Nehal A. Salahuddin  and
Hamada S. Mandour
Hany El-Hamshary*
Affiliation:
Chemistry Department, Faculty of Science, Tanta University, Tanta, 31527, Egypt Department of Chemistry, College of Science, King Saud University, Riyadh, Saudi Arabia
Adel I. Selim
Affiliation:
Chemistry Department, Faculty of Science, Tanta University, Tanta, 31527, Egypt
Nehal A. Salahuddin
Affiliation:
Chemistry Department, Faculty of Science, Tanta University, Tanta, 31527, Egypt
Hamada S. Mandour
Affiliation:
Chemistry Department, Faculty of Science, Tanta University, Tanta, 31527, Egypt
*
*E-mail address of corresponding author: hany_elhamshary@science.tanta.edu.eg
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

The conventional methods of direct bromination of organic compounds with elemental bromine have several major drawbacks such as handling difficulty, corrosive effect, and toxicity, in addition to over-bromination and problems with isolation of products from the reaction mixture. Supported catalysts and reagents have become popular in the synthesis of organic chemicals over recent decades because they have overcome almost all of the drawbacks noted above. In the present study, a new clay polymer nanocomposite (CPN)-supported brominating agent was prepared from montmorillonite (Mnt) and styrene-co-vinyl pyridinium polymer. The reagent was obtained by the direct interaction of a two-fold excess of poly(styrene-co-N-methyl-4-vinylpyridinium) bromide with Na-montmorillonite (NaMnt) through ion exchange between Na+ of the NaMnt and pyridinium ions in the copolymer to provide CPN3 with free methylpyridinium bromide side chains. The structure of the CPN3 prepared was characterized by infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Treatment of the CPN3 with bromine using the bromide ions which remained led to the perbromide-supported reagent, CPN4. The activity of the resulting CPN4 brominating reagent was examined through direct bromination of some alkenes, arenes, and carbonyl compounds and compared with the effectiveness of a crosslinked polymeric perbromide reagent. The yields obtained from application of the reagent were moderate to excellent. The advantages of this reagent, such as stability at room temperature, ease of regeneration from the polymeric by-product, and the yields of the brominated products, confirm the viability of using a CPN-supported brominating agent as a reactive reagent in organic chemistry synthesis.

Keywords

BrominationClay-Polymer NanocompositeMontmorillonitePoly(vinylpyridine)
Type
Article
Information
Clays and Clay Minerals , Volume 63 , Issue 4 , August 2015 , pp. 328 - 336
Copyright
Copyright © Clay Minerals Society 2015

References

Akelah, A. Slim, A. and El-Hamshary, H., 1988 Synthesis of pyridine and quinoline derivatives of poly(methyl methacrylate): Their uses as brominating agents European Polymer Journal 24 1111–1114.CrossRefGoogle Scholar
Bergaya, F. Detellier, C. Lambert, J.-F. and Lagaly, G., 2013 Introduction to Clay Polymer Nanocomposites (CPN) Amsterdam Elsevier.CrossRefGoogle Scholar
Cainelli, G. Manescalchi, F. and Panunzio, M., 1976 Polymer-supported reagents. The use of anion-exchange resins in the synthesis of primary and secondary alkyl fluorides from alkyl halides or alkyl methanesulfonates Synthesis 472–473.CrossRefGoogle Scholar
Colthup, N. Daly, L. and Wiberley, S., 1990 Introduction to Infrared and Raman Spectroscopy San Diego, California, USA Academic Press.Google Scholar
Cullity, B., 1967 Elements of X-ray Diffraction New York Addison-Wesley.Google Scholar
Gelbard, G., Clark, J. and Macquarrie, D., 2002 Polymer-supported reagents Handbook of Green Chemistry and Technology UK Blackwell Science Ltd.Google Scholar
Gribble, G.W., 2003 The diversity of naturally produced organohalogens Chemosphere 52 289–297.CrossRefGoogle ScholarPubMed
Han, C.D., 2009 On the mechanisms leading to exfoliated nanocomposites prepared by mixing Advances in Polymer Science 231 1–75.CrossRefGoogle Scholar
Hassanein, M. Akelah, A. Slim, A. and El-Hamshary, H., 1989 Chemically modified poly(methyl methacrylate) resin-bound triphenyl-phosphonium bromide as halogencarrier in the bromination of organic compounds European Polymer Journal 25 1083–1085.CrossRefGoogle Scholar
Hassanein, M. El-Hamshary, H. Salahuddin, N. and Abu-El-Fotoh, A., 2005 Oxidation of 2-mercaptoethanol catalyzed by cobalt(II) phthalocyaninetetrasulfonate supported on poly-N-alkyl-4-vinylpyridinium/montmorillonite intercalates Journal of Molecular Catalysis A: Chemical 234 45–50.CrossRefGoogle Scholar
Hodge, P., 2005 Synthesis of organic compounds using polymer-supported reagents, catalysts, and/or scavengers in bench top flow systems Industrial & Engineering Chemistry Research 44 8542–8553.CrossRefGoogle Scholar
Jeffery, G.H. Bassett, J. Mendham, J. and Denney, R.C., 1989 Vogel’s Textbook of Quantitative Chemical Analysis 5th edition New York John Wiley & Sons Inc 980.Google Scholar
Kirschning, A. Monenschein, H. and Wittenberg, R., 2001 Functionalized polymers — emerging versatile tools for solution-phase chemistry and automated parallel synthesis Angewandte Chemie International Edition 40 650–679.3.0.CO;2-C>CrossRefGoogle ScholarPubMed
Kornmann, X. Lindberg, H. and Berglund, A.L., 2001 Synthesis of epoxy—clay nanocomposites. Influence of the nature of the curing agent on structure Polymer 42 4493–4499.CrossRefGoogle Scholar
Nagendrappa, G., 2011 Organic synthesis using clay and claysupported catalysts Applied Clay Science 53 106–138.CrossRefGoogle Scholar
Nguyen, Q.T. and Baird, D.G., 2006 Preparation of polymer—clay nanocomposites and their properties Advances in Polymer Technology 25 270–285.CrossRefGoogle Scholar
Odian, G., 2004 Principles of Polymerization 4th edition New Jersey Wiley-Interscience.CrossRefGoogle Scholar
Ray, S.S. and Okamoto, M., 2003 Polymer/layered silicate nanocomposites: A review from preparation to processing Progress in Polymer Science 28 1539–1641.Google Scholar
Rossberg, M. Lendle, W. Pfleiderer, G. Tögel, A. Torkelson, T.R. and Beutel, K.K., 2011 Chloromethanes Ullmann’s Encyclopedia of Industrial Chemistry Weinheim, Germany Wiley-VCH.Google Scholar
Salahuddin, N. and Akelah, A., 2002 Synthesis and characterization of polystyrene-maleic anhydride montmorillonite nanocomposites Polymers for Advanced Technologies 13 339–345.CrossRefGoogle Scholar
Sasson, Y., 2009 Formation of Carbon—Halogen Bonds Weinheim, Germany Wiley-VCH.Google Scholar
Sherrington, D.C. Craig, D.J. Dagleish, J. Domlin, J. and Meeham, G.V., 1977 Highly crosslinked polymeric reagents. Polymer-supported phosphines and their use in the conversion of alcohols to chloroalkanes European Polymer Journal 13 73–76.CrossRefGoogle Scholar
Solinas, A. and Taddei, M., 2007 Solid-supported reagents and catch-and-release techniques in organic synthesis Synthesis 16 2409–2453.Google Scholar
Tamami, B. and Borujen, K.P., 2009 Poly(vinylpyridine) supported reagents: A review Iranian Polymer Journal 18 191–206.Google Scholar
Varma, S.R., 2002 Clay and clay-supported reagents in organic synthesis Tetrahedron 58 1235–1255.CrossRefGoogle Scholar
Vogel, A.I. Furniss, B.S. Hannaford, A.J. Smith, P.W.G. and Tatchell, A.R., 1989 Vogel’s Textbook of Practical Organic Chemistry 5th edition New York John Wiley & Sons Inc.Google Scholar
Wu, G. Yang, F.Y. Tan, Z. and Ge, H., 2012 Synthesis of montmorillonite modified acrylic impact modifiers and toughening of poly(vinyl chloride) Iranian Polymer Journal 21 793–798.CrossRefGoogle Scholar
Zarchi, M.A.K. and Ebrahimi, N., 2012 Facile and one-pot synthesis of aryl azides via diazotization of aromatic amine using cross-linked poly(4-vinylpyridine)-supported nitrite ion and azidation by a sandmeyer-type reaction Iranian Polymer Journal 21 591–599.CrossRefGoogle Scholar