Dérivés phosphoniques polycycliques : synthèse et étude d’interactions supramoléculaires
(2012)
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- Authors
- Supervisors
- Marchand-Brynaert, Jacqueline
- Abstract
- (en) This PhD work makes part of the « Action de Recherche Concertée » program (ARC number 08/13-009) which consists of organic or inorganic guest molecules insertion in a known polymer matrix endowed with pH-responsible properties, and the study of the non covalent interactions occurring between the guest molecules and the polymer matrix. Two complementary axes have been developed in order to answer to these problematics: the synthesis and characterization of phosphonated products on the one hand, and the preparation and the study of “guest / host” materials on the other hand. In a first time, it was necessary to have access to small water-soluble molecules (or molecules soluble in polar solvents) for compatibility with the host matrix in order to prepare “host / guest” materials. New phosphonated products were obtained by a methodology based on the Diels-Alder (DA) reaction using diethyl 1-phosphono-1,3-butadiene. The limits of reactivity of this diene in the Diels-Alder reaction have been highlighted. We were particularly interested in cycloadducts obtained by DA reaction between diethyl 1-phosphono-1,3-butadiene and N-fonctionnalized maleimides as dienophiles, giving access to cycloadducts featuring a « half-cage » particular shape. These molecules revealed to behave as excellent ligands of di- and trivalent cations (thank to a HRMS-ESI study). Many synthetic assays did not allow the preparation of 2-phosphonated diene, but a methodology based on the Horner-Wadsworth-Emmons reaction gave access to 1-phosphonated 3(4-di)-alkylsubstituted dienes, which were tested in Diels-Alder reaction with 3 representative dienophiles. Original bi- and tricyclic molecules were prepared using this method. Reactions sequences, such as Diels-Alder cycloaddition / first functionalization / second functionalization, gave access to linear or cyclic phosphonated multifunctionalized molecules. A particular attention was paid to the dialkylphosphonate deprotection to phosphonic acid function. Indeed, molecules with dialkyl phosphonate or phosphonic acid groups are used in multiple application domains, such as medicinal chemistry, agrochemistry, materials and polymers chemistry. In a second part, phosphonated synthetic products were selected as guest molecules of the host polymer matrix. A detailed study was realised about Eu(III) coordination complexes with ligands featuring a phosphonic ester function, their insertions into the host polymer matrix giving access to hybrids materials. The non covalent interactions between guest molecules and the host polymer matrix were evidenced using various analytical methods, such as X ray diffraction, infrared spectroscopy, 31P NMR and photoluminescence. Furthermore, the insertion of a phosphonated molecule bearing a pyrene fluorophore group revealed particularly interesting: this molecule could be a probe equipped with an anchorage function (PO(OEt)2) targeting the hydrophilic zones or metallic cations, and a pyrene motif able to give information about the pyrene environment polarity, near the anchorage group, thanks to the analysis of emission spectra.
- Affiliations
Citations
Villemin, E. (2012). Dérivés phosphoniques polycycliques : synthèse et étude d’interactions supramoléculaires. https://hdl.handle.net/2078.5/163342