Dans le but de réduire l’utilisation des solvants organiques dans les réactions et dans la purification, nous avons envisagé de coupler la synthèse supportée sur PEGs dans l’eau aux microréacteurs en flux continu et à l’ultrafiltration comme technique de purification. Dans un premier temps nous avons synthétisé des 3,4-dihydropyrimidin-2-ones (DHPMs) en utilisant comme étape clef la réaction multicomposant de Biginelli avec un aldéhyde supporté sur PEG. Dans ce but, nous avons trouvé que la liaison du PEG au 4-carboxybenzaldehyde, décrite dans le CH2Cl2, a lieu dans le PEG fondu (70 °C) en absence de solvant. La synthèse des DMPMs a ensuite été réalisée dans l’eau et dans le PEG fondu, à partir de l’aldéhyde supporté, et les produits finaux ont été isolés après saponification. Cette synthèse a ensuite été optimisée en microréacteurs en flux continu dans l’eau et la purification des adduits supportés a été réalisée par ultrafiltration dans l’eau.La stratégie décrite ci-dessus a été appliquée à des synthèses multi-étapes, la réaction de Baylis-Hillmann étant l’étape clef pour la préparation de tétrahydro-1,3-oxazine, tétrazoles, 1,4-oxazepin-3-ones et tétrahydro-1,3-pyrimidin-4-ones, composés dotés d'une activité biologique potentielle. Les synthèses de tétrahydro-1,3-oxazines et d’un tétrazole ont d’abord été optimisées par lots avec les purifications réalisées par ultrafiltration dans l’eau, puis adaptées en microréacteurs en flux continu.Tous les adduits supportés sur PEG ont été caractérisés par RMN et MALDI-Tof, et des nouvelles méthodes d’analyse RMN ont été mises au point afin de réduire l’intensité des signaux dus au PEG et de faciliter l’étude des molécules supportées.En conclusion nous avons développé la synthèse supportée, en milieux éco-compatibles de DHPMs, tétrahydro-1,3-oxazines et d’un tétrazole, par lots et en microréacteurs en flux continu, en utilisant les réactions de Biginelli et Baylis-Hillmann comme étapes clefs. Toutes les purifications ont été réalisées par ultrafiltration dans l’eau, afin de réduire l’utilisation de solvants organiques. / Aiming to avoid the use of volatile organic solvents in both the reaction and the separation steps, we envisioned to couple the use of PEGs as support to continuous flow chemistry and ultrafiltration in water as separation technique. First, we synthesized 3,4-dihydropyrimidin-2-(1H)-ones (DHPMs) exploiting the Biginelli multicomponent reaction starting from PEG-supported aldehyde. For this purpose, we found that the linkage of 4-carboxybenzaldehyde to PEG4000, described in the literature to occur in CH2Cl2, takes place in melted PEGs (70 °C) in the absence of solvent. We developed a novel organic solvent free synthesis of DHPMs via the Biginelli reaction of PEG-supported aldehyde, and we isolate the final products via saponification. Then, the same Biginelli reaction was carried out in continuous flow micro-reactor using water as the solvent and the supported products were isolated by ultrafiltration.The above mentioned strategy was also applied to multistep syntheses, the Baylis-Hillman reaction being the key-step for the preparation of tetrahydro-1,3-oxazine, tetrazoles, 1,4-oxazepin-3-ones, and tetrahydro-1,3-pyrimidin-4-ones, compounds endowed with potential biological activity. The preparations of tetrahydro-1,3-oxazines and tetrazole were first optimized in batch with the purifications performed by ultrafiltration in water, then adapted to the continuous flow micro-reactor synthesis.All PEG-supported compounds were characterized by NMR and MALDI-TOF MS spectrometry. Moreover, in order to facilitate the analysis of PEG-supported product, we developed new NMR methods that help to reduce the intensity of PEG signals.In conclusion, we performed the PEG-supported organic solvent-free synthesis of DHPMs, tetrahydro-1,3-oxazines, and a tetrazole derivative, in batch as well as in continuous flow microreactor, using Biginelli and Baylis-Hillman reactions as key steps. All purifications were carried out by ultrafiltration in water, to avoid the use of organic solvents.

Fossils fuels are highly demanded in everyday life domestically or industrially. Fossil fuels are finite resources and they are rapidly depleting, as such alternative renewable feedstocks are sought to replace fossil fuels. Tall oil from paper processing and cashew nut shell liquid from the cashew nut industry are the two major renewable sources we studied, they are both waste byproducts, and have the potential to be converted into value-added materials. Tall oil from the paper industry mainly contained tall oil fatty acid, and under isomerising methoxycarbonylation with palladium catalyst, dimethyl 1,19-dimethyl nonadecanedioate can be obtained. This difunctional ester, dimethyl 1,19-dimethyl nonadecanedioate, is converted to diols, secondary and primary diamines by a hydrogenation reaction with ruthenium complexes of 1,1,1-tris(diphenylphosphinometyl)ethane (triphos) as catalysts in the presence of water, amine or aqueous ammonia respectively. In the case of aqueous ammonia it is necessary to use a two step reaction via diol to obtain 1,19-diaminononadecane. Diesters, diols and diamines are useful precursors for the synthesis of polyesters and polyamides. Difunctional substrates with 8-19 carbon chains are all tolerated under the reaction conditions and are successfully converted to the corresponding diols and diamines in high yields. Under similar hydrogenation conditions with the same ruthenium catalyst, cyclic products were predominantly produced with decreased chain length. N-heterocycles, which are important building blocks for the synthesis of drug molecules, were formed from the hydrogenation of diesters with 4-7 carbon chains in the presence of an amine. Another polymer precursor, ε-caprolactam, which is the precursor for Nylon 6, is obtained in a reasonable yield from both adipic acid and adipate esters together with aqueous ammonia in the presence of ruthenium catalyst. Cashew nut shell liquid was also converted into useful medical drugs, such as norfenefrine, rac-phenylephrine, etilefrine and fenoprofene in reasonable yields. Most of these drug molecules have been formed from 3-vinylphenol by catalytic hydroxyamination followed by methylation or ethylation. 3-Vinylphenol was synthesised from cardanol by ethenolysis to 3-non-8-enylphenol followed by isomerising ethenolysis, whilst the N-alkylation reactions used methyl or ethyl triflate to avoid dialkylation. Fenoprofene was formed by firstly O-phenylating cardanol then ethenolysis followed by isomerising ethenolysis to form 1-phenoxy-3-vinylbenzene. Methoxycarbonyation followed by hydrolysis formed the final product in good yield. Our methods start from renewable waste materials and avoid unpleasant reagents in the original stoichiometric synthesis of those drugs, for example, cyanide is no longer essential for the synthesis of fenoprofene.

Contaminantes orgânicos há tempos são normalmente encontrados em baixíssimas concentrações no meio ambiente. Compostos orgânicos monoaromáticos, derivados dos subprodutos do petróleo, frequentemente são encontrados próximos a postos de combustíveis, onde há constantes vazamentos nos tanques de armazenamento. Poluentes emergentes, como exemplo os fármacos, também são temas constantes de pesquisas, devido à baixa taxa de degradação dos mesmos, mesmo após submetidos a sistemas de tratamento convencionais. Assim, a busca por técnicas de remediação, que visem a completa remoção de poluentes em baixas concentrações e metodologias analíticas que permitam o isolamento e detecção de tais compostos se torna essencial. Esse trabalho tem como uma de suas finalidades otimizar e aplicar um sistema de remoção de compostos orgânicos monoaromáticos presentes em solo, utilizando CO2 no estado supercrítico. A SPME-GC-MS foi otimizada e validada para a etapa de extração, com separação e quantificação por GC-MS dos contaminantes remanescentes após o solo ser submetido ao processo de remediação. Outro etapa do projeto, está relacionada com a determinação de sulfonamidas em lodo de esgoto. Para isso, um método rápido, fácil, barato e robusto de extração foi otimizado e validado, obtendo bons limites de quantificação (10-25 ng g-1) e detecção (4-9 ng g-1), com precisão e exatidão satisfatórios, de acordo com os valores estabelecidos pela ANVISA. Ainda com o propósito de determinar sulfonamidas em lodo de esgoto, um método LC online foi desenvolvido. A finalidade é promover o clean-up da matriz e extração dos analitos em um sistema de extração em fase sólida capilar online. Para isso, fez uso de duas colunas capilares (530 µm x 6,0 cm) dispostas em série, inseridas em um sistema cromatográfico capilar acoplado a detecção por espectrometria de massas. A primeira coluna teve como finalidade a retenção de interferentes presentes na amostra utilizando para isso, uma fase polimérica Strata-X. Já a segunda coluna, extraiu as sulfonamidas de interesse utilizando, para isso, uma fase polimérica aniônica Oasis Max. O extrato inserido no sistema de extração em fase sólida onlineera composto por 100 % solvente orgânico (acetonitrila); utilizando diferentes porcentagens de acetonitrila na etapa de carregamento, foi possível realizar clean-up adequado da amostra. A eluição dos analitos foi feita utilizando-se fase móvel acidificada. Com esse sistema, melhorou-se em até 30 % a extração de alguns compostos. Todos os métodos de preparo de amostra utilizados no trabalhos seguem a tendência atual sugerida pelo conceito do green chemistry. / The determination of organic contaminants in environmental matrices has long been a challenge for the scientific community, due to the very low concentrations they are present. Monoaromatic organiccompounds derived from petroleum sub-products are still a concern, because they are often found in environmental sites near gas stations, where there are constant leaks in storage tanks. Emerging pollutants,which include personal care products and pharmaceuticals, are also constant subject of research due to their low degradation rate, even after conventional treatment systems. Moreover, the research forremediation techniques aimed at complete removal of pollutants at low concentrations, as weel as new analytical methodologies for isolation and detection of such compounds are, both, essential. This workaims to optimize and apply a system to remove monoaromatic organic compounds present in soil, using CO2 in the supercritical state. As an analytical tool, SPME was optimized and validated with separation and quantification by GC-MS of selected contaminants remaining after the remediation process. Another research work developed is related to the determination of sulfonamides in sewage sludge.Firstly a methodology based on QuEChERS extraction method was optimized and validated, obtaining good results as limits of quantification, LOQ (10-25 ng g-1) and detection, LOD (4-9 ng g-1) withsatisfactory accuracy and precision, according to the values established by ANVISA. Still working to determine sulfonamides in sewage sludge, a new online sample preparation method was developed. Thepurpose of this method is to promote the matrix clean-up and concentration analytes in a capillary SPE system. It was used two capillary columns (500 µm x 6.0 cm) arranged in series in a capillarychromatographic system coupled to mass spectrometry. The first column was intended to retain interferences present in the sample, using a Strata-X polymer phase. The second column extracted sulfonamidesof interest, making use of an anionic polymer phase (Oasis MAX). The extract inserted in the online SPE system was composed of 100% organic solvent (acetonitrile); using different percentages of ACNwith appropriately pH at the loading stage, it was possible to achieve a satisfatory sample clean-up. The elution of the analytes was performed using an acidified mobile phase. This system improved by up to30% extraction yield of some compounds. All sample preparation methods used in the works follow the current trend suggested by the green chemistry concept.

<p>The challenge for the future was defined by the Brundtland Commission (1987) and by the Rio Declaration (1992), in which the fundamental principles for achieving a sustainable development were provided. Sustainable chemistry can be defined as the contribution of chemistry to the implementation of the Rio Declaration. This thesis shows how Pressurized Fluid Extraction (PFE) can be utilized in chemical analysis, and how this correlates to Green Chemistry.</p><p>The reliability and efficiency of the PFE technique was investigated for a variety of analytes and matrices. Applications discussed include: the extraction of the antioxidant Irganox 1076 from linear low density polyethylene, mobile forms of phosphorus in lake sediment, chlorinated paraffins from source-separated household waste, general analytical method for pesticide residues in rape seed, total lipid content in cod muscle, and squalene in olive biomass. Improved or comparable extraction yields were achieved with reduced time and solvent consumption. The decrease in use of organic solvents was 50-90%, resulting in minimal volatile organic compounds emissions and less health-work problem. Due to higher extraction temperatures and more efficient extractions, the selection of solvent is not as important as at lower temperatures, which makes it possible to choose less costly, more environmentally and health beneficial solvents. In general, extraction times are reduced to minutes compared to several hours. As a result of the very short extraction times, the amount of co-extracted material is relatively low, resulting in fewer clean-up step and much shorter analysis time. Selective extractions could be obtained by varying the solvent or solvent mixture and/or using adsorbents. </p><p>In this thesis, the PFE technique was compared to the twelve principles of Green Chemistry, and it was shown that it follows several of the principles, thus giving a major contribution to sustainable chemistry. </p>

Vinyltrialkoxysilanes are grafted onto polyolefins via a radical mechanism; in a subsequent step, the pendant alkoxysilanes hydrolyze and condense upon exposure to water, resulting formation of crosslinks. Straight chain hydrocarbons were used as model compounds to investigate the regioselectivity of vinyltrimethoxysilane grafting. To stabilize the water-sensitive grafted products, the methoxy groups were substituted using phenyllithium. It was found that this reaction must be carried out for a minimum of three days to ensure full substitution. The grafted products were then separated on a weight basis using semi-preparative HPLC. Analysis of the di-grafted fraction using edited HSQC and HSQC-TOCSY NMR showed that radical propagation occurs via 1,4- and 1,5-intramolecular hydrogen shifts along the hydrocarbon backbone, resulting in multiple grafts per backbone. Post-combustion carbon capture targets CO₂ emissions from large point sources for capture and sequestration. A new class of potential carbon capture agents known as reversible ionic liquids (RevILs) has been synthesized and evaluated in terms of potential performance parameters (e.g. CO₂ capacity, viscosity, enthalpy of regeneration). These RevILs are silylated amines, which react with CO₂ to form a salt comprising an ammonium cation and a carbamate anion that is liquid at room temperature. Structural modifications of the basic silylamine skeleton result in drastic differences in the performance of the resulting RevIL. Systematic variation of the silylated amines allowed determination of a structure-property relationship, and continued iterations will allow development of an ideal candidate for scale-up. The properties and potential applications of gold nanoparticles (AuNP) are highly dependent on their size and shape. These properties are commonly controlled during liquid-phase synthesis through the use of capping agents, which must be removed following synthesis. Reverse micelles can also be used to control the morphology of AuNP during their synthesis. When RevILs are used in the formation of these reverse micelles, either as the disperse phase or as the surfactant, the built-in switch can be used to release the nanoparticles following their synthesis. This release on command could decrease the post-synthetic steps required to clean and purify AuNP prior to use. We have successfully synthesized AuNP using a number of different RevILs.

The challenge for the future was defined by the Brundtland Commission (1987) and by the Rio Declaration (1992), in which the fundamental principles for achieving a sustainable development were provided. Sustainable chemistry can be defined as the contribution of chemistry to the implementation of the Rio Declaration. This thesis shows how Pressurized Fluid Extraction (PFE) can be utilized in chemical analysis, and how this correlates to Green Chemistry. The reliability and efficiency of the PFE technique was investigated for a variety of analytes and matrices. Applications discussed include: the extraction of the antioxidant Irganox 1076 from linear low density polyethylene, mobile forms of phosphorus in lake sediment, chlorinated paraffins from source-separated household waste, general analytical method for pesticide residues in rape seed, total lipid content in cod muscle, and squalene in olive biomass. Improved or comparable extraction yields were achieved with reduced time and solvent consumption. The decrease in use of organic solvents was 50-90%, resulting in minimal volatile organic compounds emissions and less health-work problem. Due to higher extraction temperatures and more efficient extractions, the selection of solvent is not as important as at lower temperatures, which makes it possible to choose less costly, more environmentally and health beneficial solvents. In general, extraction times are reduced to minutes compared to several hours. As a result of the very short extraction times, the amount of co-extracted material is relatively low, resulting in fewer clean-up step and much shorter analysis time. Selective extractions could be obtained by varying the solvent or solvent mixture and/or using adsorbents. In this thesis, the PFE technique was compared to the twelve principles of Green Chemistry, and it was shown that it follows several of the principles, thus giving a major contribution to sustainable chemistry.

Main group polycations and transition metal clusters had traditionally been synthesized via high-temperature routes by performing reactions in melts or by CTR, at room-temperature or lower temperature by using so-called superacid solvents, and at room-temperature in benzene–GaX3 media. Considering the major problems associated with higher temperature routes (e.g. long annealing time, risk of product decomposition, and low yield) and taking into account the toxicity of benzene and liquid SO2 in room-temperature or lower temperature synthesis, a soft and sustainable chemical approach has been developed, employing a Lewis-acidic IL [bmim]Cl/AlCl3. This new alternative reaction medium has proven to be an excellent solvent system for the single–step synthesis of main group polycations and transition metal clusters. X-ray diffraction and Raman spectroscopy have been used for the structural characterization of the isolated compounds. Physical properties and quantum chemical calculations of some of the compounds have also been carried out.

Environmentally benign alternatives for solvents and catalysts are essential for the development of sustainable chemical processes. Toward this end, we focused our research on the design of novel solvents and catalysts that reduce the environmental impact of these important materials. In this research, we develop switchable and tunable systems that couple reaction and separation to ease the processing requirements for product isolation and catalyst recovery. The switchable solvents use a ¡°switch¡± to transition from non-volatile, polar, aprotic solvents to volatile gases that can be easily separated. This allows us to facilitate reactions within the solvent and then enable easy separation through activation of the switch. We have used these materials for numerous reaction applications, including difficult reactions involving highly immiscible compounds. We also extended the work to acid-catalyzed reactions, in which we can avoid wasteful neutralization processes that are often associated with homogeneous acid catalysis. The tunable solvents use carbon dioxide pressure to ¡°tune¡± into desired solvent properties. We enable this through the dissolution of carbon dioxide into organic solvents, which generates gas-expanded liquids with solvent properties highly dependent on the carbon dioxide pressure. We can use this effect to couple homogeneous reaction with heterogeneous separation, allowing for recovery of expensive catalysts and ligands. In this work, we assess the possibilities of using liquid polyethylene glycol in the tunable systems, studying the phase behavior and industrial applications.

Laccase (benzenediol:oxygen oxidoreductase, EC 1.10.3.2), a multi-copper-containing oxidoreductase enzyme, is able to catalyze the oxidation of various low-molecular weight compounds, specifically, phenols and anilines. Due to their high stability, selectivity for phenolic substructures, and mild reaction conditions, laccases are attractive for fine chemical synthesis. In this study, new green domino syntheses were developed by conducting the reaction in an aqueous medium, an environmentally-friendly solvent, and using laccase as a biocatalyst. The first study presents a work on the synthesis of naphthoquinones in the aqueous medium. Herein, laccase was used to oxidize o- and p-benzenediols to generate o- and p-benzoquinones in situ. These quinones then underwent Diels-Alder and oxidation reactions to finally generate napthoquinone products. This reaction system can yield naphthoquinones in up to 80% yield. The next part of this thesis reports the cascade synthesis of benzofuran derivatives from the reaction of catechols and 1,3-dicarbonyl compounds via oxidation-Michael addition in the presence of laccase and Sc(OTf)3/SDS in an aqueous medium. Depending on the substrates, one-pot yields of benzofurans averaged 50-79%. From an environmental concern, this system still produced a hazardous waste from the transition metal catalyst. Therefore, the development of alternative methodologies to replace the lanthanide metal catalyst in this synthesis is a high priority to enhance the overall green chemistry aspect. As a consequence, lipase was used as a catalyst to replace Sc(OTf)3 for the synthesis of benzofuran derivatives. In addition, this catalytic system was also used to catalyze the reaction of anilines and catechol. In the last part of this thesis, laccase was applied to the modification of high-lignin softwood kraft pulp. This modification demonstrates the potential of laccase-facilitated grafting of amino acids to high lignin content pulps to improve their physical properties in paper products which resulted from the increase of carboxylic acid group of the fibers. In this study, a variety of amino acids were examined. Laccase-histidine treatment provided the best yield of acid groups on pulp fiber and was used in the preparation of handsheets for physical strength testing. Laccase-histidine-treated pulp showed an increase in the strength properties of the resulting paper.

Σκοπός της εργασίας αυτής είναι η ανάλυση του νέου νομικού καθεστώτος διαχείρισης και ελέγχου των χημικών ουσιών σε ευρωπαϊκό επίπεδο και η ανάδειξη των ποικίλων διακυβευμάτων που αυτό θέτει. Το νέο αυτό νομικό καθεστώς, παρά την μακροχρόνια διαβούλευση του, δεν είναι τελικά απαλλαγμένο από αδυναμίες και προβλήματα εφαρμογής. Πρόκειται για τον νέο κανονισμό REACH (αρχικά του Registration, Evaluation and Authorisation of Chemicals) ή κανονισμό 1907/2006/ΕΚ. Ο κανονισμός REACH αποτελεί ένα ενιαίο ευρωπαϊκό νομοθέτημα για την καταχώριση, την αξιολόγηση, την αδειοδότηση και τους περιορισμούς των χημικών ουσιών, αντικαθιστώντας 40 διαφορετικά υφιστάμενα νομοθετικά μέτρα. Η εργασία χωρίζεται στην εισαγωγή, σε έξι κεφάλαια και τέλος τα συμπεράσματα. Στην εισαγωγή παρουσιάζεται η υφιστάμενη νομοθεσία της ευρωπαϊκής ένωσης για τις χημικές ουσίες, τα προβλήματα από την εφαρμογή της καθώς και η ανάγκη για ένα νέο νομοθετικό πλαίσιο το οποίο θα αντικαταστήσει το υφιστάμενο και θα έχει ως πρωταρχικό σκοπό την προστασία της ανθρώπινης υγείας και του περιβάλλοντος. Αναφορά γίνεται στην βιώσιμη ανάπτυξη και την πράσινη χημεία, καθώς αποτελούν βασικούς πυλώνες του κανονισμού. Επίσης παρουσιάζονται οι βασικές αρχές του κανονισμού (αρχή της προφύλαξης, της υποκατάστασης κλπ) καθώς και οι επιδιωκόμενοι στόχοι από την εφαρμογή του. Στο πρώτο κεφάλαιο γίνεται μια αναλυτική παρουσίαση της αρχής της προφύλαξης, η οποία αποτελεί βασική και θεμελιώδης αρχή του κανονισμού. Γίνεται αναφορά στην σχέση της με την αρχή της πρόληψης, στην πορεία της μέσα στο ευρωπαϊκό δίκαιο και στη διατροφική πολιτική της ευρωπαϊκής ένωσης καθώς και η αντιμετώπισή της από το ελληνικό δικαιικό σύστημα. Στο δεύτερο κεφάλαιο παρουσιάζεται αναλυτικά η οικοδόμηση του κανονισμού REACH, μέσω των σημαντικότερων χρονολογικών γεγονότων που άλλοτε ενίσχυσαν και άλλοτε αποδυνάμωσαν το κανονισμό, ικανοποιώντας κάθε φορά και διαφορετικά συμφέροντα ή απαιτήσεις, έως την οριστικοποίηση του τελικού του κειμένου. Ειδική αναφορά γίνεται στο ρόλο του Παγκόσμιου Οργανισμού Εμπορίου για τη διαμόρφωση του τελικού κειμένου του κανονισμού. Στη συνέχεια, στο τρίτο κεφάλαιο, παρουσιάζονται αναλυτικά το πεδίο εφαρμογής του κανονισμού, τα θεσμικά όργανα και οι αρμοδιότητές τους καθώς και οι βασικές διατάξεις του κανονισμού, η καταχώριση, η αξιολόγηση, η αδειοδότηση και περιορισμοί των χημικών ουσιών. Ακολουθεί το τέταρτο κεφάλαιο, όπου παρουσιάζεται ο κανονισμός CLP (αρχικά του Classification, Labelling, Packaging) για την ταξινόμηση, την επισήμανση και συσκευασία χημικών ουσιών και μειγμάτων ή κανονισμός 1272/2008/EK. Ο κανονισμός CLP συμπληρώνει και τροποποιεί τον κανονισμό REACH στο κενό που παρουσιάζει όσον αφορά την ταξινόμηση, την σήμανση και τη συσκευασία των χημικών ουσιών και τον εναρμονίζει με το Παγκόσμιο Εναρμονισμένο Σύστημα ταξινόμησης και επισήμανσης για τις χημικές ουσίες και τα μείγματα των Ηνωμένων Εθνών. Στο πέμπτο κεφάλαιο γίνεται μια αναλυτική αποτίμηση του κανονισμού REACH, καθώς παρουσιάζονται και αναλύονται τόσο οι θετικές του όψεις όσο και οι αδυναμίες του. Αναλυτική αναφορά γίνεται στο κόστος εφαρμογής του κανονισμού καθώς και στα οικονομικά οφέλη που προκύπτουν από την εφαρμογή του. Επίσης παρουσιάζοντα τα προβλήματα ερμηνείας και εφαρμογής του κανονισμού. Ακολουθεί το έκτο κεφάλαιο, στο οποίο γίνεται αναφορά στην εφαρμογή του κανονισμού REACH στην Ελλάδα καθώς παρουσιάζεται η υπεύθυνη αρμόδια αρχή για την εφαρμογή του κανονισμού και ο ρόλος της, το πεδίο εφαρμογής του κανονισμού (επιχειρήσεις χημικών προϊόντων) καθώς και ο ρόλος του Συνδέσμου Ελληνικών Χημικών Βιομηχανιών. Τέλος στα συμπεράσματα γίνεται μια συγκεντρωτική παρουσίαση και σύγκριση των αρνητικών και θετικών χαρακτηριστικών του κανονισμού και αποτιμάται ο βαθμός της επίτευξης των αρχικών στόχων του μέσα στο χρονικό διάστημα από την ημερομηνία εφαρμογής του έως σήμερα. Επίσης παρουσιάζεται πως ο κανονισμός REACH αποτελεί καινοτόμο νομοθετικό εργαλείο στα χέρια της διοίκησης αν και αποδυναμωμένος σε σχέση με το αρχικό του κείμενο και την αρχική πεποίθηση για ολοκληρωμένη και υψηλού επιπέδου προστασία της ανθρώπινης υγείας και του περιβάλλοντος. / Aim of this work is the analysis of new legal regime of management and control of chemical substances in European level and the emergence of diverse implications that this poses. This new legal regime, despite its long-lasting consultation, is not finally exempted from weaknesses and problems of application. This is the new REACH Regulation (initials of the Registration, Evaluation and Authorisation of Chemicals) or regulation 1907/2006/EC. REACH is a uniform European legislation on the registration, evaluation, authorisation and restriction of chemicals, replacing 40 different existing legislative measures. The work is divided into the introduction, six chapters and finally conclusions. The introduction presents the existing EU legislation on chemicals, the problems of implementation as well as the need for a new legal framework which will replace the existing and will have as fundamental aim the protection of human health and environment. Reference is made to sustainable development and green chemistry, which are key pillars of the regulation. It also presents the basic principles of the regulation (precautionary principle, substitution principle, etc) as well as the objectives pursued by its application. In the first chapter becomes an analytic presentation of precaution principle, which constitutes basic and fundamental principle of regulation. Reference is made in relation to the prevention principle, in European law and food policy in the European Union as well as its confrontation from Greek law system. In the second chapter is presented in detail the construction of REACH regulation, by means of the most important chronological facts that sometimes reinforced and sometimes watered down regulation, satisfying each time and different interests or requirements, until the finalization of the final text. Special reference to the role of the World Trade Organization is made for the configuration of final text of regulation. Afterwards, in the third chapter, are presented in detail the field of application of regulation, the institutional bodies and their competences as well as the basic provisions of regulation, the registration, evaluation, authorisation and restriction of chemicals. Fourth chapter follows, where regulation CLP is presented (initials of the Classification, Labeling and Packaging) for the classification, labeling and packaging of substances and mixtures or regulation 1272/2008/EC. Regulation CLP supplements and modifies regulation REACH in the void that it presents with regard to the classification, labeling and packing of chemical substances and it harmonizes REACH with the World Harmonized System of classification and labeling for the chemical substances and mixtures of United Nations. In the fifth chapter becomes an analytic assessment of regulation REACH, while are presented and analyzed both positive aspects and weaknesses. A detailed reference becomes in the cost of implementing the regulation and to the economic benefits arising from its application. Also the problems in the interpretation and application of the regulation are presented. Following the sixth chapter, in which reference is made in the implementation of reach in Greece as the responsible authority for the application of the regulation and its role, the field of application of regulation (enterprises of chemical products) as well as the role of the Association of Greek Chemical Industries. Finally, in the conclusions is a summary and comparison of negative and positive characteristics of regulation and evaluation of the extent of the initial objectives within the period from the date of application until now. It also shows that REACH is an innovative legislative tool in the hands of the administration, although weak compared to the initial text, and the initial conviction for integrated and high level of protection of human health and environment.