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Page 1 of 11 RSC Advances RSC Advances This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. This Accepted Manuscript will be replaced by the edited, formatted and paginated article as soon as this is available. You can find more information about Accepted Manuscripts in the Information for Authors. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. www.rsc.org/advances Page 1 of 11 RSC Advances RSC Advances RSC Publishing ARTICLE New prospects for the synthesis of N-alkyl phosphonate/phosphonic acid-bearing oligo-chitosan Cite this: DOI: 10.1039/x0xx00000x N. Illy, G. Couture, R. Auvergne, S. Caillol, G. David and B. Boutevin Received 00th January 2012, N-phosphonomethylation reactions of oligo-chitosan were performed according to Moedritzer and Accepted 00th January 2012 Kabachnik-Fields conditions. The different Moedritzer reaction conditions used did not allowed the DOI: 10.1039/x0xx00000x phosphonomethylation. On the contrary, the Kabachnik-Fields reactions led to oligo-chitosan methyl phosphonated derivatives. In addition, novel dialkyl phosphoryl oligo-chitosan were synthesized in water www.rsc.org/ at room temperature via epoxy-amine reactions of oligo-chitosan with dialkyl (3-(oxiran-2- ylmethoxy)propyl) phosphonates. This simple and efficient synthetic method provides a new approach for the preparation of phosphonated oligo-chitosan derivative. Then, the hydrolysis of the phosphonated compounds to generate the phosphonic acid moities was investigated. The mildest conditions were Manuscript determined in order to avoid the chitosan backbone degradation. All the products were characterized by 1H and 31 P NMR analyses. Introduction are some other common applications. Several techniques to synthesize phosphorous-containing chitosan derivatives have 1 Chitosan is the fully or partially deacetylated form of chitin the already been published due to their interesting biological and second most abundant natural polysaccharide derived from physico-chemical properties, for example bactericidal 22 , flame exoskeletons of crustaceans and also cell walls of fungi and retardant 23 and heavy metal-chelating properties 24 . 2 insects . With the poly(lysine), chitosan is one of the very few Phosphorylation of the hydroxyl functions from chitosan to Accepted polymer from a natural origin which has primary amino groups yield phosphate groups has been performed according to along its backbone. This low-cost biopolymer possesses very several ways: i/phosphorylated chitosan can be prepared by interesting properties, for instance it is known to be heating chitosan with orthophosphoric acid and urea in DMF 25, 3 4 5 biocompatible , biodegradable in the human body , non toxic 26 , ii/ by reacting chitosan with phosphorous pentoxide in the 6 and antibacterial . presence of methane sulfonic acid 27, 28 , iii/ or in a 29 Interest in chitosan materials is quite recent compared to H3PO 4/Et 3PO 4/hexanol mixture . Chitosan alkyl phosphates cellulose, which has an age-long exploitation history. were also synthesized through the use of chlorophosphates: Therefore, chitosan is one of the most promising materials diethyl chlorophosphate 30 or 2-chloro-2-oxo-1,2,3- derived from renewable resources and is currently explored dioxaphospholane 31 . Less commonly phosphate-functionalized 7 very intensively . In the last decades unmodified chitosan has chitosan derivatives can be synthesized by grafting Advances been widely used in a variety of applications: for example as polymerization of mono (2-methacryloyl oxyethyl) acid 8 9 10 11 wound dressing , in tissue engineering , cosmetics , food or phosphate initiated by ceric ammonium nitrate 32 or directly via 12 13 textile industry , and in waste water treatment . Specific Michael addition with mono-(2-acryloyloxyethyl) groups can also be introduced to achieve original chitosan phosphonate 33 . Few papers deal with the synthesis of phosphate derivatives with new physicochemical properties and improved and amidophosphate chitosan derivatives by Atherton Todd RSC performances for selected applications. For instance, reaction 34, 35 . quaternized chitosan and PEGylated chitosan copolymers have Phosphate and phosphoramide groups have excellent chelating 14 been studied for anion exchange membrane synthesis and for properties but they are not very stable toward hydrolysis. In 15 drug delivery applications , respectively. Similarly, general, phosphonate groups are much less sensitive towards 16 carboxymethylated chitosan was used in tissue engineering . hydrolysis than phosphates 36 . Therefore, even if they are Phosphorous containing polymers have numerous potential slightly less efficient as chelating agent, it could be of great applications as they exhibit interesting properties in term of interest to introduce phosphonate or phosphonic acid groups 17, 18 adhesion and thus are excellent anti-corrosion compounds . onto chitosan. The phosphonation of chitosan has been studied 19 20 21 Ion-exchange resins , dental adhesives and fire retardant according to several pathways (Scheme 1). Phosphonation of This journal is © The Royal Society of Chemistry 2013 RSC Advances , 2014, 00 , 1-3 | 1 RSC Advances Page 2 of 11 ARTICLE RSC Advances the hydroxyl functions was carried out with 2-chloro ethyl not complete. Chitosan was also derivatized by the reaction of phosphonic acid (Scheme 1-A) 37 . Recently, Lebouc et al. 38 its primary amine groups with molecules containing carboxylic reported two different reactions with chitosan amino groups acid moieties. For instance by using 1-ethyl-3-(3- that led to alkyl-phosphonate-containing derivatives: alkylation dimethylaminopropyl) carbodiimide (EDC) mediated coupling with a halogeno-phosphonate compound (Scheme 1-C) and reaction, 2-carboxyethyl phosphonic acid was covalently Michael addition using a tetraethyl vinylidenebisphosphonate grafted onto chitosan (Scheme 1-B) 39 . This reaction proceeds in (Scheme 1-D). These coupling reactions are characterized by very smooth condition and is almost quantitative. Nevertheless, high yields and soft conditions. However, they are performed in the use of an expensive coupling reagent may not be suitable THF on 6-O-triphenylmethyl-chitosan and thus require for large scale reactions. additional protection and deprotection steps that appear to be Manuscript Accepted Scheme 1: Preparation methods of phosphonated chitosan 37-39 . Currently, the most common chitosan phosphonation reaction is (Scheme 2). We first tried to introduce in one step phosphonic the Moedritzer reaction. Numerous papers report the acid groups according to a Moedritzer-type reaction40 . Then, we introduction of α-aminomethylphosphonic acid groups onto followed two-steps reactions pathways: i/during the first step, chitosan using this reaction 40-51 . However, the results of these alkyl phosphonate groups were introduced either according to a papers are sometimes contradictory. In fact, some authors claim Kabachnik-Fields reaction or according to epoxy-amine Advances a regioselective functionalization of the primary amines 40 in reactions of oligo-chitosan with dialkyl (3-(oxiran-2- contradiction to others who also report the esterification ylmethoxy)propyl) phosphonates, ii/ then, the dealkylation of reaction of the hydroxyl groups 41 . More recently, Lebouc et the phosphonic ester functions was investigated. Numerous al. 46 noticed the predominance of a side reaction, the papers show that chitosan primary amine groups react with methylation of the amines leading to N-methyl and N,N- epoxide compounds 52 but to our knowledge, it is the first time RSC dimethyl chitosan. In contrast to Moedritzer reaction, the that the epoxy-amine reaction has been used to introduce synthesis of α-aminomethylphosphonate by Kabachnik-Fields phosphonate groups onto oligo-chitosan. All the products reaction was not much studied in spite of the interest of such synthesized were fully characterized by 1H and 31 P NMR and groups 41 . IR spectroscopies and their thermal properties were assessed. In this paper, different strategies were used to synthesize aminoalkyl phosphonic acid (phosphonated) oligo-chitosans 2 |RSC Advances , 2014, 00 , 1-3 This journal is © The Royal Society of Chemistry 2012 Page 3 of 11 RSC Advances ARTICLE RSC Advances Manuscript Accepted Advances Scheme 2: Syntheses of phosphonic acid-containing chitosan described in this paper: Moedritzer reaction (I), Kabachnik-Fields reaction (II) followed by hydrolysis (III) and epoxy-amine reaction (IV-V) followed by hydrolysis (VI-VII). phosphonate (Specific Polymers), and diethyl (3-(oxiran-2- RSC Experimental Part ylmethoxy)propyl) phosphonate (Specific Polymers) were used Materials as received. Ultra-pure water was obtained from a Millipore Milli-Q purification system. Chitosan (“652”, shrimp shell origin, degree of deacetylation = Oligo-chitosan (degree of deacetylation
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