Dissertations / Theses on the topic 'Alcools gras – Synthèse (chimie)'
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Violleau, Frédéric. "Étude d'un procédé de synthèse et de décomposition en dérivés chlorés de chloroformiates, optiquement actifs ou non, en présence de chlorure d'hexaalkylguanidinium." Toulouse, INPT, 2000. http://www.theses.fr/2000INPT018C.
Fernandes, Beiramar Jorge Miguel. "Etude de la promotion des catalyseurs CuZnAl pour la production d’alcools supérieurs à partir du biosyngaz." Electronic Thesis or Diss., Lille 1, 2013. http://www.theses.fr/2013LIL10170.
This PhD thesis addresses design of novel catalysts for conversion of syngas obtained from biomass into alcohols. It is shown that the catalytic performance of copper-zinc catalysts in carbon monoxide hydrogenation is principally affected by dispersion of copper metallic phase. The performance of these catalysts is strongly affected by promotion with different elements. The activity of the promoted catalysts was correlated with the reducibility of copper phase; the ease of copper reduction leads to more active catalysts. In addition, promotion with iron, chromium and manganese significantly modifies the reaction selectivity. A spectacular increase in carbon monoxide hydrogenation rate was observed on iron-containing catalysts and was attributed to the formation of iron carbide species. Increasing iron content in the catalysts led to higher alcohols productivity and was also accompanied by significant activity in water gas-shift reaction. The catalysts exhibited relative stability in the presence of sulphur containing syngas
Najem, Leïla-Isabelle. "De l'épibromohydrine à la synthèse d'éthers glycidyliques à partir d'alcools gras et étherification du glycérol." Toulouse, INPT, 1994. http://www.theses.fr/1994INPT044G.
Coowar, Djalil. "Cellules souches et maladies neurodégénératives : Conception et synthèse d'inducteurs de différenciation cellulaire." Université Louis Pasteur (Strasbourg) (1971-2008), 2003. http://www.theses.fr/2003STR13211.
In a search for inducers of neuronal differentiation to treat neurodegenerative diseases such as Alzheimer's disease or Amyotrophic Lateral Sclerosis, a series of indole fatty alcohols (IFA) were synthesised. These molecules combine a long chain w-alkanol with an antioxidant core. Melatonin being a well-known antioxidant, the indole ring bearing or not methoxy groups on the benzene moiety was chosen. A Wittig reaction between indole-3-carboxaldehydes and long chain phosphorous ylides was the key step in the preparation of these IFAs. These compounds were then investigated for their free radical scavenger property and their effect on the differentiation of neural stem cells-derived neurospheres. The presence of the hydroxyl group was essential to increase the antioxidant potency of IFAs compared to melatonin. Additionally, we showed that 5MIFA18 promotes the differentiation of neural stem cells-derived neurospheres into neurons at a concentration of 10 nM. Our results suggest that this effect is likely to exert on neuronal progenitors rather than on uncommitted precursors, with 5MIFA18 promoting their differentiation. This finding supports the notion that this molecule acts as a neurotrophic factor. Analysis of the expression of the Notch pathway genes in neurospheres treated during differentiation with 5MIFA18 revealed a significant decrease in the transcription of Notch 4 gene receptor. We hence develop a new synthesis for C-5 substituted indole fatty alcohols using a Suzuki reaction
Pop, Laura Ancuta. "Synthèse stéréosélective d'hétéroaryl alcools et alanines." Phd thesis, INSA de Rouen, 2011. http://tel.archives-ouvertes.fr/tel-00940020.
Brochette, Sandrine. "Sonocatalyse en chimie des sucres : effets des ultrasons sur la glucosylation des alcools gras et l'oxydation du saccharose." Lyon 1, 1997. http://www.theses.fr/1997LYO10222.
Bouilleau, Laurent. "Utilisation en synthèse d'organolithiens allyliques alpha et gamma fonctionnels." Poitiers, 1999. http://www.theses.fr/1999POIT2343.
Goma, Doncescu Nathalie. "Synthèse enzymatique de cires en milieux concentrés." Compiègne, 1997. http://www.theses.fr/1997COMP1022.
Wax ester production has been investigated. Transesterification reaction has been realized from methyl ester mix (vegetable oils of rape and sunflower) and stearyl alcohol with Lipozyme. The alcoholysis reaction is controlled in solvent-free medium that is exclusively composed of the reactants and the enzyme. The transesterification is performed by simply mixing the two substrates in a temperature-controlled water bath under stirring. High yields are obtained with a Iow amount of Lipozyme, rate conversion from 80 to 100 % depending on molar ratio in 2 hours at the temperature of 60 °C. The balance between optimal working temperature and the molar ratio of substrates in such a complex medium appears to be 60 °C with a molar ratio I methyl oleate : stearyl alcohol of I 1: 0,5I. Substrate inhibition due to stearyl alcohol has been confirmed by a study of kinetic parameters. More, external diffusional limitations have been showed (reaction medium/surface of enzymatic support). Then, after evaluation, optimization of process has been performed. The validation of results has been verified at a large-scale process. Another enzymatic preparation has been tested. Novozym permits to obtain optimal yield for the equimolar mixing. This advantage directly led to a final product exempted of substrates. More, catalytic efficiency of Novozym (0,213 min-1) is higher than catalytic efficiency of Lipozyme (0,144 min-1). Finally, transesterification reaction has been examined with the elimination of the co-product formed, the methanol in proportion of producing. The two immobilised enzymes have been investigated in covered reactor, cap-opened reactor and under vacuum. More rapid is the methanol elimination, higher is the rate production of stearyl oleate. The use of substrate ratio S 1/Sz=l leads to direct stearyl waxes production exempted from reactive using simple but efficient way
Prakesh, Michaël. "Synthèse stéréocontrôlée de fluorés allyliques via les fluorés propargyliques. Application à la synthèse d'analogues fluorés de lipides." Rennes 1, 2002. http://www.theses.fr/2002REN10140.
Fernandes, Beiramar Jorge Miguel. "Etude de la promotion des catalyseurs CuZnAl pour la production d’alcools supérieurs à partir du biosyngaz." Thesis, Lille 1, 2013. http://www.theses.fr/2013LIL10170/document.
This PhD thesis addresses design of novel catalysts for conversion of syngas obtained from biomass into alcohols. It is shown that the catalytic performance of copper-zinc catalysts in carbon monoxide hydrogenation is principally affected by dispersion of copper metallic phase. The performance of these catalysts is strongly affected by promotion with different elements. The activity of the promoted catalysts was correlated with the reducibility of copper phase; the ease of copper reduction leads to more active catalysts. In addition, promotion with iron, chromium and manganese significantly modifies the reaction selectivity. A spectacular increase in carbon monoxide hydrogenation rate was observed on iron-containing catalysts and was attributed to the formation of iron carbide species. Increasing iron content in the catalysts led to higher alcohols productivity and was also accompanied by significant activity in water gas-shift reaction. The catalysts exhibited relative stability in the presence of sulphur containing syngas
Pasco, Morgane. "Synthèse asymétrique de diamines cyclopentaniques polyfonctionnelles : des outils pour l'étude d'interactions avec l'ARN." Paris 5, 2010. http://www.theses.fr/2010PA05P626.
In the laboratory, functionalized 1,3-cyclopentanic diamines have been developped to design new RNA ligands by mimicking the central framework of aminoglycosides. These diamines are easily obtained after functionalization of bicyclic hydrazines and cleavage of the N-N bond. Different synthetic routes has been explored to allow a regio-, diastereo- and in some cases enantioselective introduction of a fluorine atom on these polynitrogenated compounds. Binding experiments using 19F NMR highlighted a supramolecular chiral recognition phenomenon between the fluorinated diamines and RNA. This led to a split of the signal correlated with the location of the fluorine nucleus and the structure of the RNA. Fluorinated diaminocyclopentanes could then serve as useful probes for the study of ligand-RNA interactions. The desymmetrisation of meso 1,3- cyclopentanic diamines using allylic substitution reactions has been studied as well. With the use of iridium catalysis, the efficiency of the resolution of the two amines proved to be very low, and only stereochemistry of the allylic position has been fully controlled. However, the linear monoallylated product could been obtained with an enantiomeric exces up to 61 % using palladium catalysis
Huguenot, Florent. "Réactivité d'imines et d'oxazolidines fluorées chirales : application à la synthèse d'aminoacides et d'aminoalcools fluorés énantiopurs : thèse pour le doctorat en sciences spécialité Chimie Organique." Reims, 2004. http://theses.univ-reims.fr/exl-doc/GED00000050.pdf.
This thesis falls under the field of organofluorinated chemistry and the asymmetrical synthesis. We studied various original methodologies of synthesis of di- and trifluoromethyl enantiopur compounds starting from chiral fluorinated oxazolidines and ketimines. The trifluoromethyl ketimines and oxazolidines are prepared by reaction of the fluoral or trifluorométhyl ketones with chiral amines or aminoalcohols. The difluoromethyl analogues are obtained by exploiting the electrophilic properties of difluoroenoxysilanes. The reduction of fluorinated oxazolidines by the hydrides is completely stereoselective, which gives access to enantiopur di- and trifluoromethyl amines. Oxazolidines with Lewis acid form in situ iminium species, which give access to the a-aminonitriles, precursors of enantiopur a-amino acids and 1,2-diamines, and acces to b-aminoesters and the b-aminoketones, precursors of enantiopur b-amino acids and 1,3-aminoalcohols
Harfouche, Joyce. "Nouvelles méthodologies de synthèse de ligands NN, NNO, et nos chiraux : utilisation en catalyse asymétrique homogène pour la réduction de cétones." Lyon 1, 2005. http://www.theses.fr/2005LYO10147.
Gravil, Sébastien. "Utilisation d'enzymes en synthèse organique : accès à des alcools allyliques et époxydes d'esters d'énols chiraux, acétates de pyranose de configuration anomérique fixée." Clermont-Ferrand 2, 2004. http://www.theses.fr/2004CLF21521.
Wang, Jingjuan. "Design of efficient catalysts for hydrogenation of carbon oxides to alcohols and olefins." Electronic Thesis or Diss., Lille 1, 2012. http://www.theses.fr/2012LIL10052.
Catalytic hydrogenation of carbon monoxide and carbon dioxide leads to valorisation of syngas which can be produced from fossil and renewable resources. This thesis addresses design of new catalysts for synthesis of alcohols and olefins from syngas containing carbon monoxide and carbon dioxide. Catalyst characterization has demonstrated formation of bimetallic particles in copper-cobalt mixed supported catalysts and enrichment of metallic particles with copper on the outer surface in the reduced catalysts. Comparison with catalytic data suggests that these bimetallic particles probably contain the active sites for the synthesis of alcohols from syngas. The supports (SiO2, Al2O3 and carbon nanotubes), and some promoters, especially iron, also have a very strong influence on the catalyst performance. Promotion with iron also increases productivity of Rh catalysts in the synthesis of ethanol from syngas. The formation of interfaces between the iron and rhodium seems to improve the selectivity of this reaction to ethanol, while carbon monoxide conversion principally depends on rhodium dispersion. The Fe/ZrO2 catalysts promoted with potassium showed a very important selectivity for the synthesis of olefins from carbon dioxide. This increase in selectivity was attributed to the synergy between iron and oxidized species Fe0/χ-Fe5C2 which are involved in this reaction
Hanbali, Mazen. "Composés hybrides w-alcanol / hydroquinone à activité neurotrophique. Synthèse et étude des propriétés physicochimiques et biologiques." Phd thesis, Université Louis Pasteur - Strasbourg I, 2005. http://tel.archives-ouvertes.fr/tel-00116946.
Une approche thérapeutique novatrice serait l'utilisation de composés hybrides portant deux activités distinctes. Une activité neurotrophique permettant la neuro-régénération et une activité antioxydante assurant la neuro-protection en piégeant les radicaux libres.
Dans cet objectif, cinq séries de molécules hybrides combinant une chaîne grasse Ω-hydroxylée et des noyaux quinol ont été synthétisés. Les alcools gras quinoliques (QFA) C-alkylés, comportant des noyaux quinol polyméthoxylés, ont été obtenu par couplage de Sonogashira entre des arylbromures et des alcynes vrais. Les homologues N- ou O-alkylés ont été obtenus par des réactions de type SN2.
Les molécules synthétisés possèdent de très bonnes activités antioxydantes sous leurs formes déméthylés dépassant d'un facteur 100 l'activité antioxydante du Trolox®. Par ailleurs, le QFA15 portant une chaîne latérale à 15 atomes de carbones, est capable de promouvoir une croissance axonale très importante, aussi bien sur substrat permissif que sur substrat inhibiteur tel les protéines de myéline ou la Sema3A. Des études préliminaires du mécanisme d'action ont permis de conclure que le QFA15 sollicite les nucléotides cycliques.
Nguyen, Tien Thao. "Development of perovskite catalysts for the synthesis of higher alcohols from syngas." Thesis, Université Laval, 2007. http://www.theses.ulaval.ca/2007/24583/24583.pdf.
Louis, Kévin. "Synthèse et fonctionnalisation d'aldéhydes issus de la coupure d'esters gras insaturés." Thesis, Poitiers, 2013. http://www.theses.fr/2013POIT2290/document.
A high interest has been devoted to the use of renewable carbon in the chemical industry. The goal of this work is the substitution of fossil oils by vegetable oils to synthesize bio sourced monomers for polyesters and polyamides production. The synthesis of methyl 9-oxononanoate as a platform molecule from fatty acid methyl esters of rapeseed oil was carried out in solvent free ozonolysis at room temperature. Intermediary ozonides was reduced to aldehydes by catalytic hydrogenation under H2 pressure and in the presence of Pd(5)/C catalyst giving a 92% carbonyl yield. This process was applied to a wide range of unsaturated esters with a chain length within 9 and 13 carbon atoms. This process allows the selective conversion of renewable materials to value added chemicals, in mild conditions and in the presence of a recyclable catalyst. Moreover, the co products are non toxic and valuable. Hydrogenation of aldehyde group was performed in the presence of methanol at 50°C under hydrogen pressure. Raney Nickel and Pd(5)/C exhibit a yield to methyl 9 hydroxynonanoate higher than 90%. Reductive amination of the aldehyde functional group was investigated with success in the presence of NH3(g) and Pd(5)/C at 50°C in methanol to produce primary amino ester. The amount of ammoniac is directly correlated to the selectivity of the reaction. As a consequence a minimum amount of 3 eq. of ammoniac is required to avoid the formation of secondary amino-ester
Abidli, Abdelnasser. "Design of novel well-defined organorhenium heterogeneous catalyst for unsaturated fatty acid derivatives self-metathesis." Doctoral thesis, Université Laval, 2015. http://hdl.handle.net/20.500.11794/26473.
Sustainable C-C bond forming reactions have been among the highest target of catalysis science and technology. In this scope, metathesis reaction has been gaining enormous attention due to the efficiency of the transformation process. Therefore, a great progress has been made in this area by developing several homogeneous and heterogeneous catalysts as well as distinct metathesis reaction approaches. This allows an easier and more sustainable design for various synthesis strategies in different fields including organic synthesis, polymer science, etc. However, the development of robust metathesis catalysts for large scale applications is still a challenging task. Taking this into account, this research presented in this doctoral dissertation is focusing on the synthesis of new heterogeneous metathesis catalysts. Therefore, methyltrioxorhenium (MTO) was supported on various alumina-based materials. The synthesized catalysts' performance was studied though methyl oleate self-metathesis, chosen as a model bulky functionalized substrate, in order to evaluate the active species tolerance to functional groups as well as to evaluate its diffusion inside the mesoporous channels. First, highly organized ZnCl2-modified OMA supports were successfully prepared through a sol-gel method followed by a post-synthesis modification via wet-impregnation process. MTO supported on these catalytic supports were found o be highly active for methyl oleate self-metathesis, displaying higher reaction rate and products selectivity compared to the conventional wormhole-like alumina-based catalysts. This improvement is ascribed to enhanced mass transfer phenomena inside the organized mesoporous network. Afterwards, we have developed efficient one-pot synthesis route ZnCl2-modified OMA supports. Interestingly, this approaches allowed access to numerous highly ordered ZnCl2-modified OMA supports with better synthesis yields and improved textural and surface properties. Moreover, these enhanced features allowed the MTO-based catalyst supported on these one-step prepared materials to exhibit higher metathesis reaction performance compared to ZnCl2-modified OMA supports prepared via the two-steps processes. However, spectroscopic investigations revealed the formation of similar surface active species for all the prepared catalytic supports. These characterizations guided us to study and propose a comprehensive mechanism of metathesis products formation pathways as well as the metathesis catalytic cycle, demonstrating the steric hindrance effect on the catalysts interface that governed the reaction selectivity. The synthesis of the 3 wt.% MTO/ZnCl2-OMA catalysts allowed us to efficiently perform metathesis reaction using renewable feedstock (e.g. fatty acid esters derived from vegetable oils), offering access to a variety of functionalized monomers which could be used for further transformations such as the synthesis of value-added bio-based polymers (e.g. bioplastics, biosurfactants).
Hémelaere, Rémy. "Mise au point de réactions tandems catalytiques incluant une étape d'isomérisation pour la synthèse de molécules naturelles." Thesis, Rennes 1, 2013. http://www.theses.fr/2013REN1S173/document.
Some of the new challenges of modern synthetic chemistry are: atom economy, employment of catalytic processes, avoidance of toxic reactants and limitation of purification steps. A lot of work has been devoted to the development of tandem reactions. A new reactivity could be generated in a molecule thanks to an isomerisation (or migration) reaction of an alkene. This reaction often needs an hydride specie which comes from a transition metal catalyst. This PhD thesis is about the development of new tandem reactions in which at least one step is an isomerisation of an olefin. A great attention has been dedicated to the synthesis of vinylboronates especially with a cross-metathesis strategy. These intermediates are of great importance in organic chemistry and can be useful in a wide range of reactions. One of those reactions is the transformation of vinylboronates to allylboronates thanks to an isomerisation step. Allylboronates can then react with aldehydes to generate homoallylic alcohols with total diastereoselectivity. These new reactions have found applications in total synthesis of natural molecules with a 2,3-dihydrobenzofuran core
Oukessou, Mohamed. "Synthèse, dérivation et évaluation de pharmacophores hybrides Alcynyl-TriAzolyCarbinols N-glycosylés." Toulouse 3, 2014. http://thesesups.ups-tlse.fr/2387/.
The alkenyl-alkynylcarbinol function (AAC) is a key pharmacophore encountered in natural products extracted from marine sponges, the petrosiacetylenes, exhibiting various biological properties, and in particular a remarkable cytotoxicity on tumor cells. In a different context, the 1H-1,2,3-triazole (TA) core is a peptido-mimetic motif identified in several enzymatic inhitors, for example of beta-lactamases in the Tazobacatm(r) drug. The fusion -or intimate hybridization-and glyco-conjugation of these two pharmacophores is envisaged in unprecedented structures like N-glycosylated bis(1H-1,2,3 triazolyl)carbinols (BTACs), alkynyl-triazolylcarbinols (ATAC = ATAC(y)), or alkenyl-triazolylcarbinols (ATAC(e)). Such molecules were synthesized by Huisgen reaction of glycosyl azides, functional at the primary or anomeric position of O-protected (D)-ribose, (D)-galactose, or (D)-glucose units, with dialkynylcarbinols (DAC) and AAC substrates substituted in various manners at positions 1 and 3. These [2+3] cycloaddition dipolarophiles proved to react regio-selectively in standar click-chemistry conditions (CuSO4,5H2O + sodium ascorbate, in ethanol/water mixtures). The principle has been generalized to trialkynylcarbinol substrates, and the reactivity of the tris-(N-benzyl-1H-1,2,3-triazolyl)carbinol product, Taz3C-OH, was studied. In the presence of trifluoroacetic anhydride, the latter carbinol dissociates to the corresponding tris(triazolyl)carbenium - for which the term "trizyl cation" is coined, by analogy with the trityl cation-, whose SN1 reactivity with various O-, N-, S-and Cnucleophiles was found to selectively produce new structures, which are heterocyclic analogues of known or unknown triphenylmethane derivatives. Among the described new compounds, a few ATACs and BTACs were selected and tested for their inhibition activity towards enzymes (a-glucosidase and sphingosine kinase) or cytotoxicity towards tumor cells (adenocarcinome)
Balland, Hervé. "Conception d'amphiphiles trimodulaires à partir de produits de la biomasse." Nancy 1, 2003. http://www.theses.fr/2003NAN10172.
In order to valorise the vegetable productions and to obtain biodegradable molecules, new amphiphilic agents with single hydrophobic tails have been synthesized from natural sugar, and derivated. The peptidic part between the hydrophilic head and the hydrophobic tail allows the adjustement of the hydrophilic-lipophilic balance. The strategy of synthesis is based on trimodular synthesis method. Our synthetic approach consists in a preparation of the hydrophilic part independently of the hydrophobic one, these are then linked together. Objectives of our works are the synthesis and the evaluation of these molecules in order to use them in pharmaceutical industry and to valorise farm-products. By using biodegradables substances from the biomass, we find outlets in superfluous vegetable productions by creating original compounds of large consumption. That is why one of the concerns in the execution of our works is the mastery of the production costs of these amphiphilic agents
Zhang, Jidong. "Utilisation des N-oxydes dérivés d'amino-alcools pour la synthèse de N-H pyrrolidines substituées en position 2, 3 ou 4 et pour l'α-fonctionnalisation d'amines secondaires." Paris 11, 1989. http://www.theses.fr/1989PA112213.
Azomethine ylids generated from tertiary amine oxides by double deprotonation are the only azomethine ylids able to undergo intermolecular 3+2 cycloaddition with non-activated olefins. Thus, 3- or 4-substituted or 3, 4-disubstituted N-alkyl pyrrolidines can be obtained by a simple and direct method. It was important to develop this method for preparing N-H pyrrolidines found in natural products. In the first pan of this thesis, demethylation of N-methyl pyrrolidines was attempted using a variety of literature methods. However none of them appeared suitable for our purpose, mainly because of the lability of the 5 membered heterocyclic ring. Then, we looked for an amine oxide which could easily undergo 3+2 cycloaddition and whose N-alkyl group could be removed under mild conditions. We found that β-amino alcohol (protected) derived amine oxides gave good yields of the corresponding pyrrolidines. Hofmann elimination of the quatemary ammonium salt followed by debenzylation gave quantitatively the N-H pyrrolidines substituted in positions 2, 3 or 4. This methodology is used for the synthesis of a precursor of kainic acid and one of its analogues. In the second part, we propose an original and general method for functionalisation of secondary amines at α-position. β-amino alcohol (unprotected) derived amine oxides treated with t-butyllithium give oxazolidines after intramolecular trapping of the intermediate immonium by the alcoholate. Opening of the oxazolidine ring by a Grignard reagent and removal of the amino alcohol moiety (according to the sequence described above) give access to α-alkylated amines. Several exemples are reponed
Chemin, Maud. "Valorisation des xylanes du bois : vers la synthèse de copolymères amphiphiles bio-sourcés." Thesis, Bordeaux, 2014. http://www.theses.fr/2014BORD0302/document.
This thesis work aims to add value to xylans by designing new bio-based amphiphilic polymers.Beechwood xylans were first fully characterized before their acidic hydrolysis. The hydrolysis conditions were optimized in order to obtain well-defined xylooligosaccharides, oligomeric chains of about six xylose units that have only one methylglucuronic acid unit positioned at the non-reductive chain end. Periodate oxidation of xylans was also studied in order to form new aldehyde groups within the xylan backbone in a controlled manner. The xylooligomers were then functionalized from their reductive end with an azide or an allyl group, providing the ability to couple these oligomers to fatty acid derivatives using ‘click chemistry’.The obtained amphiphilic oligomers were finally studied according to their surfactant and self-assembly properties. Their wetting properties were found to be very good, comparable to those found with Tween®80. Moreover, they self-assembled in both chloroform and water, where their structures were characterized via DLS and TEM. The resulting particles formed had a spherical micellar morphology, with a d ≤ 50 nm. However, it was found that the particles had a tendency to form large aggregates, particularly in chloroform. The aggregates could be easily removed, either by filtration or by dilution of the sample, as the forces that govern the aggregation are low enough to allow dissociation with increasing solvent volume.As previously mentioned, this thesis work led to the synthesis of bio-based amphiphilic oligomers starting from xylans, which are a potential byproduct in the paper/pulp industry. Thanks to their surfactant properties, numerous applications can be found for such a ‘green’ surfactant. Their biocompatibility added with their self-assembly nature in aqueous media makes them an attractive molecule for active substance delivery applications
Bruniaux, Sophie. "Nouveaux hydrotropes biosourcés : conception, synthèse et propriétés physico-chimiques en milieu hautement salin." Thesis, Compiègne, 2017. http://www.theses.fr/2017COMP2378.
Historically, chemical industry was based on fossil ressources, but alternative processes have been developed since the nineteens to be green and to answer to the environmental eco-responsibility questions. In this context, a collaboration work between three public laboratories and the SAS PIVERT emerged to find new biosourced hydrotropes starting from various polyols – such as glycerol, main byproduct of the fuel production – and resistant to high saline conditions. A specific design was defined by our physico-chemical partner for the synthesis of hydrotropes. Differents approaches were used to obtain these compounds, such as a new method of methylation using sub/supercritical methanol with a phase of optimization, and another about the scope of the reaction that reduced the reaction steps. The transposition of the reductive alkylation of various alcohols was also realized – using a heterogeneous catalysis – with the obtention of various ethers, in continuous flow conditions, by the intermediate of the use of the HCube Pro from ThalesNano
Diaf, Ilhem. "Développement de nouveaux processus de cyclisation de dérivés alléniques catalysés par des triflates métalliques et synthèse de molécules odorantes." Thesis, Nice, 2014. http://www.theses.fr/2014NICE4124.
Novel processes of metal triflate-catalyzed cyclizations of functionalized allenes are presented. Two strategies have been developed. In a first part, the intramolecular carbonyl-ene reaction with γ-allenic ketones is described. This reaction proceeds under very mild conditions using only 1 mol% of bismuth(III) triflate. The scope of this reaction was extended to several γ-allenic ketone derivatives, featuring various substitution patterns. The resulting dienols were successfully engaged in a Diels-Alder reaction allowing the formation of polycyclic functionalized frameworks in good yields with excellent regio- and diastereoselectivities. In a second part, the metal triflate-catalyzed cyclization of allenic-enol ethers is described. This reaction gives access to cyclopentene derivatives in good yields using only 0.1 mol% of bismuth(III) triflate. Dihydrofuran derivatives could also be formed using this strategy. This cycloisomerisation reaction proceeds through an initial enol ether activation, followed by the nucleophilic attack of the allene moiety. This reactivity could be inverted using a gold(I) catalyst, in the presence of an exogenous nucleophile, allowing the formation of different products. Within our interest in flavor and fragrance chemistry, allenic acetates and alcohols have been synthesized and subjected to olfactive evaluation, revealing dominant fruity and floral notes. Green and woody undertones have been detected as well
Garenne, David. "Etude d'un système de transition basé sur des acides gras dans les processus d’encapsulation de biomolécules : vers un nouveau modèle de cellule minimale." Thesis, Bordeaux, 2016. http://www.theses.fr/2016BORD0365/document.
Compartmentalization is of importance for our understanding of the emergence of life on earth but also for the development and design of minimal cells. Coacervation phenomenon allows spontaneous sequestration by molecular diffusion from aqueous medium but do not allow encapsulation of molecule inside. On the contrary, vesicular systems do not allow spontaneous encapsulation of molecules inside. Here we introduce a model built from saturated long chain fatty acids. This system can form both membranous vesicles and membrane free coacervated droplets that result from clouding by decreasing ph. We have shown that a large amount of proteins is encapsulated into vesicles after pre-crowding into coacervated. Encapsulation of enzyme in vesicles allow to increase the reaction rate compared to the reaction rate in diluted medium. Synthesis of proteins by cell-free system and metabolic reactions with proteins of mollicutes have not clearly been shown but they represent an essential element in the development of a minimal cell
Vignon, Paul. "Catalyseurs homogènes et hétérogènes à base de ruthénium pour la métathèse d’oléfines issues de ressources renouvelables." Thesis, Lille 1, 2013. http://www.theses.fr/2013LIL10037.
Production of materials from renewable raw materials is urgent by the decreasing availability of fossil fuels. This need has motivated the emergence of the concept of bio-refinery that certain products obtained in large quantities are derivatives of fatty acids (Fatty Acid Methyl Ester, FAME). These FAMEs are mainly produced by hydrolysis of triglycerides and have already found many application areas. In the context of optimal use of different products by bio-refineries, FAMEs modifications can be implemented thanks to catalysis, including olefin metathesis, taking advantage of the internal double bond present in these compounds. Significant efforts have been made on the ethenolysis of [Delta]9 FAME into [Alpha]-olefins, as these have a wide range of applications, but also on reducing the carbon chain size by reaction with small olefins (C4). Moreover, in order to limit metal contamination of products and to allow catalyst recycling, the use of heterogeneous catalyst is of high interest. We thus prepared heterogenized commercial ruthenium catalysts. These heterogeneous catalysts were prepared in a two-step procedure: modification of the catalyst or the silica and catalysts grafting by ligand exchange on silica. The reactions studied in this thesis concern self-metathesis, ethenolysis and various cross-metatheses of methyl oleate and FAME bio-derived sources using homogeneous catalysts and their grafted analogs. Despite the impossibility of recycling performance, heterogeneous catalysts have achieved our reactions efficiently and some of these reactions are the first example of such transformations with heterogeneous catalysis
Vaton-Chanvrier, Laurence. "Synthèse et greffage sur silice de dérivés de l'acide cholique. Evaluation de l'énantiosélectivité par chromatographie liquide haute performance." Rouen, 1999. http://www.theses.fr/1999ROUES078.
Torre, Aurélien de la. "Synthèses totales de neurofuranes et dihomo-isofuranes." Thesis, Montpellier 1, 2014. http://www.theses.fr/2014MON13513/document.
Arachidonic acid (AA, C20 :4, n-6) and docosahexaenoïc acid (DHA, C22 :6, n-3) are phospholipidic membranes polyinsaturated fatty acids. During and oxidative stress, these are metabolized into tetrahydrofuran-containing compounds, known as isofurans (IsoFs) for AA and neurofurans (NeuroFs) for DHA. We were interested in the total synthesis of these compounds in the aim of getting access to novel biomarkers of the oxidative stress. Towards the same goal, we envisaged the total synthesis of potential analog structures coming from adrenic acid (AdA, C22 :4, n-6), that we named dihomo-isofurans (dihomo-IsoFs)
Lebarbe, Thomas. "Synthèse de nouveaux polyesters "verts" issus de ressources oléagineuses : application au renfort au choc du poly(L-lactide)." Phd thesis, Université Sciences et Technologies - Bordeaux I, 2013. http://tel.archives-ouvertes.fr/tel-00965638.
Batt, Frédéric. "Approches synthétiques vers le mycothiazole-4,19-diol : utilisation du palladium en synthèse organique." Phd thesis, Université Claude Bernard - Lyon I, 2009. http://tel.archives-ouvertes.fr/tel-00654585.
Durand, Pierre-Luc. "Fatty acids as a source of original aliphatic polycarbonate materials." Thesis, Bordeaux, 2017. http://www.theses.fr/2017BORD0710.
Fatty acids were derivatized with the objective to design bio-based aliphatic polycarbonate(APC) materials. To that purpose, two platforms of lipidic 6-membered cyclic carbonates were prepared following synthetic routes either involving the ring-closure of a malonate intermediate or the coupling reaction between a fatty acid and 2-amino-1,3-propanediol. The ring-openingpolymerization (ROP) of these cyclic carbonates was next investigated. The first platform of 6CCswas polymerized in the presence of Sn(Oct)2 as catalyst, yielding low Tg aliphatic polycarbonates ranging from -61°C to -26°C with respect to the size of the pendant aliphatic side chains. The polymerization of the second lipidic 6CC platform was performed in a controlled fashion using DBU/Schreiner thiourea as catalytic system. Taking advantage of the presence of unsaturation functions on the linear bio-based APCs, cross-linked polycarbonate materials were then prepared.Several cross-linking methods were tested such as the irreversible thiol-ene coupling, the thermoreversible Diels-Alder reaction and the photo-reversible [2+2] cyclo-addition reaction between two cinnamate moieties. Fatty acid-based cross-linked APCs were thus designed and characterized; the latter exhibit tunable physico-chemical properties as a function of the monomer structure and the cross-linking density
Pierre, Anne-Sophie. "Le métabolisme des acides gras monoinsaturés et la prolifération des cellules cancéreuses coliques : rôle de la Stéaroyl-CoA Désaturase-1 et effets des isomères conjugués de l'acide linoléique." Phd thesis, Université de Bourgogne, 2012. http://tel.archives-ouvertes.fr/tel-01017782.
Dorich, Stéphane. "Synthèse totale de la pactamycine et d’une sélection d’analogues, progrès vers la synthèse totale de la daphniglaucine C et brève étude d’une transposition allylique réductrice." Thèse, 2013. http://hdl.handle.net/1866/10129.
Although pactamycin was first isolated as a potential antitumoral drug, further studies highlighted its capacities in inhibiting protein synthesis, and thus its potency as an antibacterial agent. Furthermore, it was recently discovered that some of its analogs display promising antiprotozoal activity. The present thesis reports and details the first total synthesis of pactamycin, pursued in the Hanessian lab over the last few years, as well as the preparation of a selection of analogs thereby tested for their biological properties. Daphniglaucin C belongs to a large family of natural compounds isolated from the leaves of daphniphyllum over the last decade. Although relatively little is known as to the biological activity of daphniglaucin C, its synthesis poses an obvious and interesting challenge for organic chemists. En route towards its total synthesis, the use of several methods for the formation of quaternary centers was explored. Moreover, an atypical reductive allylic transposition, catalyzed by palladium from unactivated allylic alcohols, was studied and used to generate a variety of polysubstituted pyrrolidines.