Dissertations / Theses on the topic 'Ether(alkyl allyl)'

The present dissertation covers the total synthesis of viridiofungin triesters and studies toward the total synthesis of xeniolide F. In both cases, sigmatropic rearrangements of α-allyloxy substituted α,β-unsaturated esters are employed: for the viridiofungin ester synthesis a [2,3]-Wittig rearrangement and for the xeniolide F synthesis a catalytic asymmetric Claisen rearrangement CAC. For both rearrangement reactions the historical development, main characteristic and important variations are discussed. The viridiofungin triester synthesis represents a convergent and highly flexible route toward these natural products. The [2,3]-Wittig rearrangement allowed the diastereoselective synthesis of the polar head group with two adjacent stereogenic centers. The E-configured double bond was formed by a Julia-Kocienski olefination. During the studies toward the total synthesis of xeniolide F a new, diastereoselective strategy for the generation of allyl vinyl ethers with E-configured vinyl ether double bond was established employing rhodium catalyzed OH-insertion and an E-selective Horner-Wadsworth-Emmons olefination. Under the conditions of the catalytic asymmetric Claisen rearrangement (CAC) this highly substituted allyl vinyl ether rearranged diastero- and enantioselectively to the corresponding a-keto ester. This example clearly illustrates the high potential of the CAC as synthetic tool for natural product synthesis
In der vorliegenden Arbeit wird die Totalsynthese von Tirestern der Viridiofungine A, A2 und A4 sowie die Synthese eines Schlüsselintermediates für die Totalsynthese von Xeniolid F dargestellt. In beiden Fällen wird ausgehend von einem α-allyloxysubstituierten α,β-ungesättigten Ester eine Umlagerungsreaktion als Schlüsselschritt eingesetzt: im Falle der Viridiofunginester eine diastereoselektive [2,3]-Wittig-Umlagerung, bei den Arbeiten zur Totalsynthese von Xeniolid F eine diastero- und enantioselektive, katalytische Claisenumlagerung. Für beide Umlagerungsreaktionen werden ausführlich die theoretischen Hintergründe sowie die historische Entwicklung und wichtige Varianten besprochen. Mit der Viridiofungintriestersynthese wird eine konvergente und bezüglich der lipophilen Seitenkette sehr flexible Syntheseroute vorgestellt. Die [2,3]-Wittig-Umlagerung konnte dabei erfolgreich für die diastereoselektive Synthese der hochsubstituierten, polaren Kopfgruppe der Viridiofunginester mit zwei benachbarten stereogenen Zentren (davon eines quartär) eingesetzt werden. Zur Bildung der E-konfigurierten Doppelbindung wurde die Julia-Kocienskie-Olefinierung ausgenutzt. Bei den Arbeiten zur Totalsynthese von Xeniolid F wurde eine neuartige Strategie zur diastereoselektiven Synthese eines Allylvinylethers mit E-konfigurierter Vinyletherdoppelbindung eingesetzt. Die Horner-Wadsworth-Emmons-Olefinierung (HWE-Olefinierung) generierte dabei E-selektiv die Vinyletherdoppelbindung. Das für die HWE-Olefinierung benötigte Phosphonat wurde durch rhodiumkatalysierte OH-Insertion aus einem Allylalkohol und einem Diazaphosphonoacetat hergestellt. Der hochsubstituierte Allylvinylether wurde unter den Bedingungen der katalytisch asymmetrischen Claisenumlagerung umgesetzt und führte mit exzellenter Diastereo- und Enantioselektivität zum entsprechenden α-Ketoester. Anhand dieses Beispiels konnte das Potential der katalytisch asymmetrischen Claisenumlagerung zum Aufbau von hochfunktionalisierten Bausteinen für die Naturstoffsynthese verdeutlicht werden

The study of the polymerization of alkyl vinyl ethers initiated by HI/I₂ catalyst is directed into two areas: the kinetics of the polymerization and the strategy of amine functionalized prepolymer synthesis. The polymerization reactions show living behavior in nonpolar solvents at low temperatures. The observed rate of polymerization under reaction conditions is linearly dependent on the initial concentration of hydrogen iodide and iodine, respectively. However, the monomer concentration does not influence the rate of polymerization(apparent zero-order). Two possible reaction schemes are proposed from the observed rate equation and attempts are made to distinguish them by using UV/visible spectroscopy and carbon-13 NMR spectroscopy. In both schemes a reversible interaction between a monomer and an iodine molecule is postulated as a necessary elemental reaction to fit the observed expression for the rate of polymerization. From spectroscopic analysis results, the interaction between the iodide compound(chain end) and the iodine molecule seems to be very weak compared to the interaction between the monomer and the iodine molecule. A synthetic strategy for amine functionalized prepolymer synthesis has been developed via a series of model reactions. Incorporation of a styrenic monomer at the propagating chain end of living poly(alkyl vinyl ethers) provides a convenient intermediate synthesis of a relatively stable amine functionalized prepolymer. Proper selection of substituents at the styrenic monomer optimizes the cross addition reaction and amination reactions. Linear alkylamines with lower carbon numbers are used in the amination reaction in order to promote the nucleophilic substitution reaction and to minimize possible elimination reactions. A series of amine functionalized oligomers are synthesized by employing the synthetic strategy in combination with the previous kinetic result of the homopolymerization. For oligomers, incorporation of a few units of ethyl vinyl ethers at the chain end facilitates the cross addition reaction. Synthesized amines are characterized by various spectroscopic methods. Then, titrated molecular weights show good agreement with their theoretical molecular weights in several cases.
Ph. D.

One purpose of this study was to understand the oxidation metabolites of zeaxanthin, another was to prepare, purify, and characterize a series of 3'-alkyl lutein ethers for use as internal standards. Studies have proven that lutein and zeaxanthin are two of the principal carotenoids in human serum and the only carotenoids found in the retina, but their metabolism and transport in the human body are still only poorly understood. In vitro oxidation of zeaxanthin with MnO2 produced three components. They were characterized by HPLC, UV/Vis, MS, NMR and identified as all-trans rhodoxanthin and its cis-isomers. 3'-alkyl lutein ethers have been utilized as internal standards for carotenoid analysis in human serum and macular tissue. Nine 3'-alkyl lutein ethers were prepared by reaction of lutein with the corresponding acidified alcohols. The purified products were characterized by HPLC, UV/Vis, MS for the first time, and the resulting lutein ethers showed similar properties to lutein with increasing retention times as the alkyl chain lengthened. This provides us alternatives in selecting internal standards.

A comparative synthetic study of a series of six 1,2,3,4,5-pentaphenyl-2,4-cyclopentadiene alkyl ethers was investigated. It was determined that the most efficient route to these ethers was not the most generally accepted route to ethers - the Williamson Reaction - but rather a solvolysis reaction between 1-bromo-1,2,3,4,5-pentaphenyl-2,4-cyclopentadiene and the appropriate alcohol. Thermal rearrangement of the ethers had been expected to rearrange by a [1,5]-sigmatropic shift of the phenyl group in the 1-position to yield the corresponding enol ether. However, this appeared to occur only as a trace in some cases. Rather, the major product of the thermal rearrangements of these ethers was actually the elimination product, the hydrocarbon, 1,2,3,4,5-pentaphenyl-2,4-cyclopentadiene. The elimination is most likely the result of a retro-ene reaction.
Ph. D.
incomplete_metadata

L'etude de la toxicite de molecules tensioactives originales derivees du glucose a ete realisee chez la souris. Certains composes, les o-alkyl-3 et les desoxy-3 s-alkyl 1,2 ; d glucofurannose montrent des proprietes anesthesiques, myorelaxantes et anticonvulsivantes. In vitro, ces composes exercent un effet spasmolytique sur le duodenum de rat, suppriment l'activite cardiaque du cur de rat, et suppriment la contractilite du muscle squelettique (soleus) de souris. Une etude electrophysiologique realisee sur fibres musculaires et sur neurone d'ecrevisse montre que ces composes abolissent les potentiels d'action dependant du calcium et l'influx calcique transmembranaire. Etudies en condition de whole cell clamp sur myotubes de souris, ils bloquent les courants portes par les ions barium a travers les canaux calciques de types t et l

Functionalization of hydrocarbons via a free-radical based allyl transfer reaction using various allyl bromide substrates has been previously studied. The work described in this dissertation focuses on the replacement of Br by phthalimido-N-oxyl (PINO ) which helps make this chemistry environmentally friendly. To replace Br with PINO , replacement of previously used allyl-bromide substrates with new allyl-PINO substrates were necessary. Various allyl- PINO compounds were synthesized and the use of these allyl-phthalimido-N-oxyl (allyl-PINO) compounds for the functionalization of various alkyl aromatic hydrocarbons is demonstrated.
Kinetic studies were performed to observe the efficiency of the new chain reaction compared to the previously reported studies with allyl-bromides. We recently discovered that these allyl substrates are useful for the functionalization of ethers and acetals. The functionalization of various cyclic and acyclic ethers was performed using these allyl transfer reactions. This reaction was also performed in-solution, which allowed us to perform these reactions at low reagent concentrations. Kinetic chain lengths were measured for these reactions. High chain lengths were observed for all used ethers. Kinetic studies to investigate the rate of radical addition-elimination processes were performed using laser flash photolysis and competition kinetics. These experiments helped us to measure the reactivity and selectivity of PINO as a chain carrier in comparison with Br .
Additionally, a new competition experiment was designed to study the relative rate constant for
the 􀈕-fragmentation process. For this experiment a novel substrate that contains two leaving
groups, Br and PINO , was synthesized, and the relative rates of elimination of Br vs PINO
were compared.
Ph. D.

A primeira parte desta Tese incluiu a funcionalização em solução de polietileno linear de média densidade (LMDPE) com alil glicidil éter (AGE), na presença de peróxido de benzoíla (BPO) como iniciador de reações radicalares. A caracterização foi feita por espectroscopia no infravermelho com transformada de Fourier (FTIR) e o grau de funcionalização (GF) foi estimado por meio de duas curvas de calibração. Foi observado efeito do tipo de solvente sobre o GF. A segunda parte consistiu na funcionalização superficial por radiação ultravioleta (UV). Como monômeros foram usados AGE, anidrido maléico (MAH) e anidrido tetraidroftálico (THFAH). Como iniciadores, BPO e benzofenona (BP). A caracterização das superfícies foi realizada por medidas de ângulo de contato. THFAH apresentou a melhor performance. A terceira tratou da funcionalização por processamento reativo do LMDPE com AGE, na presença de BPO. A caracterização se deu por FTIR e o GF foi estimado conforme descrito acima. A funcionalização foi confirmada (indiretamente) por calorimetria diferencial exploratória, que evidenciou a diminuição do grau de cristalinidade com a funcionalização. Não foi possível confirmar a funcionalização por meio de análise elementar, termogravimetria e difração de raios X. A fragmentação das cadeias do LMDPE funcionalizado do ensaio 13 (e 13A) foi evidenciada por decréscimo no torque e nas propriedades mecânicas. Contudo, o índice de fluidez, surpreendentemente, diminuiu. Os valores relativamente superiores de resistência à tração e módulo de Young dos compósitos e blendas obtidos com LMDPE funcionalizado, contra os obtidos com LMDPE virgem, evidenciaram a interação favorável entre os grupos epóxidos inseridos nas cadeias do LMDPE e os grupos hidroxilas presentes no polissacarídeo. O aumento da adesão entre a matriz polimérica e as fibras de celulose foi confirmado por microscopia eletrônica de varredura e, qualitativamente, por quantidades relativamente maiores de resíduos remanescentes após extração em xileno sob refluxo.
The first part of this work included the functionalization in solution of linear medium density polyethylene (LMDPE) with allyl glycidyl ether (AGE), in the presence of benzoyl peroxide (BPO) as free radical reaction initiator. The characterization was made by Fourier transform infrared spectroscopy (FTIR) and the degree of functionalization was estimated by means of two calibration curves. The type of solvent influenced the DF. The second part comprised the surface functionalization by ultraviolet (UV) radiation. AGE, maleic anhydride (MAH) and tetrahydrophthalic anhydride (THFAH) were used as monomers and BPO and benzophenone (BP) as initiators. Contact angle measurements were used to characterize the surfaces. THFAH showed the best performance. The third part dealt with the functionalization by reactive processing of LMDPE with AGE, in the presence of BPO. FTIR was used to characterize the samples and the degree of functionalization was estimated as described above. The functionalization was (indirectly) confirmed by differential scanning calorimetry. The degree of crystallinity decreased with the functionalization. The functionalization couldn?t be confirmed by elemental analysis, thermogravimetry and X-ray diffraction. The chain scissions of the chemical modified LMDPE of trial 13 (and 13A) were evidenced by reduction of torque and mechanical properties. However, the melt flow index diminished. The favorable interaction between epoxide groups inserted on LMDPE chains and hydroxyl groups present in polysaccharide caused the increase in tensile strength and Young?s modulus values for composites and blends in relation to those obtained with virgin LMDPE. The increase in adhesion between the polymeric matrix and cellulose fibers was also confirmed by scanning electron microscopy and, qualitatively, by relatively large amounts of remaining residues after extraction in refluxing xylene.

This thesis concerns the development of metal-free applications using diaryliodonium salts. The first project describes an arylation protocol of allylic and benzylic alcohols in aqueous media. The method proceeds under mild conditions and the ether products were obtained in moderate to good yields. The methodology was also expanded to include arylation of phenols, giving diaryl ethers in good to excellent yields. In the second project, an arylation method that included a wider range of aliphatic alcohols was developed. The scope of accessible alkyl aryl ethers was studied and included a comparative study of phenylation and nitrophenylation of various alcohols. Finally, a formal metal-free synthesis of butoxycain was performed, illustrating the applicability of the developed method. The third project focused on the limitations and side reactions occurring in Chapter 2 and 3. First, an approach to access symmetric diaryl ethers via arylation of hydroxide was presented. This reaction gave rise to a number of side products, which we hypothesized to originate from aryne-type intermediates. A mechanism for the formation of these side products was suggested, supported by trapping and deuterium labeling experiments. Oxidation of the alcohol to the corresponding ketone was also observed and the mechanism of this interesting side reaction was investigated. The latter was suggested to proceed via an intramolecular oxidation without the involvement of radicals or arynes. The fourth project covers a method to synthesize highly sterically congested alkyl aryl ethers via arylation of tertiary alcohols using diaryliodonium salts. The method displayed a broad scope of tertiary alcohols and was also suitable for fluorinated alcohols. The final project detailed in this thesis deals with C-arylation with diaryliodonium salts, showcasing nitroalkanes as well as a nitro ester as suitable nucleophiles for metal-free arylation.

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 3: Manuscript.

Certaines Bacteria synthétisent des phospholipides particuliers dont la structure possède des caractéristiques communes aux lipides des Bacteria et des Archaea : les éthers de glycérol bactériens (AGE). Le caractère singulier de ces lipides et leur structure chimique thermostable leur permettent d'être assez bien préservés dans l'environnement à la mort des cellules, et suggèrent leur potentiel à constituer de bons marqueurs biogéochimiques et/ou environnementaux. Cependant, très peu d'informations sont actuellement disponibles concernant les modes de formation et le rôle des AGE dans les membranes bactériennes. Au cours de cette thèse, nous avons étudié la composition lipidique de différentes souches pures de bactéries anaérobies sulfato-réductrices capables de synthétiser des AGE et cultivées dans différentes conditions contrôlées de température, pH et salinité. Diverses modifications structurales des AGE ont notamment été mises en évidence en réponse à des variations des conditions de croissance, dont certaines spécifiques d'une adaptation, et linéairement corrélées, à la température ou à la salinité. Les différents résultats démontrent l'implication des AGE dans l'adaptation membranaire en réponse à des variations physico-chimiques du milieu, et permettent d'envisager l'utilisation de la distribution structurale des AGE dans des échantillons naturels comme indicateur de conditions environnementales. L'analyse de la composition en AGE d'échantillons issus de différents écosystèmes actuels et anciens, caractérisés par des conditions environnementales contrastées a permis de vérifier le potentiel de certains AGE à être utilisés comme indicateurs de variations de conditions (paléo)environnementales
Some Bacteria synthesize particular phospholipids, called glycerol ether lipids (AGE) which have a chemical structure at the intersection of the Bacteria and Archea domains. The singular nature of these lipids and their thermostable chemical structure allow them to be well preserved in the environment following bacterial lysis, and suggest their potential to constitute good biogeochemical and/or environmental biomarkers. However, very little information is currently available concerning the modes of formation and the role of AGEs in bacterial membranes. In this thesis, we studied the lipid composition of various pure strains of anaerobic sulfate-reducing bacteria able to synthesize AGEs, grown under various controlled conditions of temperature, pH and salinity. Various structural modifications of AGE were observed in response to variations in growth conditions, some of which being specific to, and linearly correlated with, changes in temperature or salinity. The results demonstrate the involvement of AGEs in membrane adaptation to changes in the physico-chemical conditions, and suggest the use of the structural distribution of AGEs in natural samples as an indicator of environmental conditions. The analysis of the AGE content of samples from different actual and past ecosystems, allowed confirming the potential of AGEs to be used as indicators of variations of (paleo)environmental conditions

Les acylsilanes sont les composés «acyl-métal» présentant la chimie la plus diversifiée. Cette thèse porte d'une part sur de nouvelles synthèses (méthodes et produits) d'acylsilanes, d'autre part sur l'étude de leur réactivité. Plus particulièrement, des allyl- et vinyl(acyl)silanes et des bis(acylsilanes) à silicium internes étaient ciblés. Une synthèse basée sur l'hydrolyse d'éthers d'énol ou d'ènethiol C-silylés s'est révélée peu performante pour des bis(acylsilanes), mais apporte une contribution originale à la panoplie des méthodes de synthèse d'acylsilanes. Deux méthodes ont été étudiées pour la synthèse d'allyl- et vinyl(acyl)silanes. Une séquence silylation/déthiocétalisation du 2-phényl-[1,3]-dithiane a permis de préparer les allyl- et vinyl(benzoyl)silanes, et la méthode à été étendue à d'autres allyl(acyl)silanes. Une séquence silylation/alkylation du 1-phénoxyméthyl-1H-benzotriazole a conduit efficacement aux allyl- et vinyl(acyl)silanes à longue chaîne alkyle. Les allyl- et vinyl(acyl)silanes se sont révélés peu réactifs en métathèse. Cependant la métathèse cyclisante appliquée aux dérivés bis(insaturés) du benzotriazole a donné des intermédiaires cycliques avec de très bons rendements. La métathèse croisée appliquée à un allylsilane dérivé du benzotriazole a permis d'obtenir, après hydrolyse, le bis(acylsilane) correspondant. Les allyl(diméthyl)(acyl)silanes présentent une réactivité photochimique inédite comparée à celle des acyl(trialkyl)silanes. Les allyl(acyl)silanes donnent, par réaction de Paternò-Büchi intramoléculaire totalement régiosélective, des 1-alkyl-2,2-diméthyl-6-oxa-2- sila-bicyclo[2. 2. 0]hexanes, un nouveau type de structure bicyclique
Acylsilanes are «acyl-metal» compounds having the most varied chemistry. This PhD concerns, on the one hand, new synthesis (methods and products) of acylsilanes, on the other hand the study of their reactivity. A method of synthesis based on the hydrolysis of C-silyl enol or enethiol ethers proved to be inappropriate for the preparation of bis(acylsilanes), but provided an original contribution to the array of the acylsilanes synthetic methods. The synthesis of allyl- and vinyl(acyl)silanes and allyl- and vinyl(aroyl)silanes was performed from two types of precusors. Allyl- and vinyl(benzoyl)silanes were prepared by a sequence of silylation/dithioketalisation of 2-phenyl-[1,3]-dithiane and the methodology was extended to aliphatic allyl(acyl)silanes. A sequence silylation/alkylation applied to 1-phenoxyméthyl-1Hbenzotriazole led to allyl- and vinyl(acyl)silanes bearing a long alkyl chain in satisfactory yields. Allyl- and vinyl(acyl)silanes proved to have a poor reactivity in metathesis whatever the Grubbs catalyst used. However ring closing metathesis applied to bis(unsaturated) benzotriazole derivatives led to cyclic intermediates in very good yields. Cross-metathesis applied to an allysilane derived from benzotriazole led, after deprotection, to the expected bis(acylsilane). Allyl(dimethyl)(acyl)silanes exhibited an unexpected reactivity compared with the usual reactivity of acyl(trialkyl)silanes. UV irradiation of allyl(acyl)silanes gave 1-alkyl-2,2-diméthyl-6-oxa-2-sila-bicyclo[2. 2. 0]hexanes, a new type of bicyclic structure, by a totally regioselective intramolecular Paternò-Büchi reaction

Chez l'homme, de nombreuses pathologies sont liees a des dysfonctionnements du transport cellulaire du d-glucose. Les techniques d'imagerie etant un outil precieux pour detecter ces anomalies de transport, la synthese d'analogues du d-glucose radiomarques a l'iode (emetteur gamma) et utilisables en imagerie spect, a ete entreprise selon deux approches : la premiere repose sur l'utilisation du motif beta-iodoethoxyle qui a ete introduit sur diverses positions (1, 4, 5 et 6) du glucose. La seconde consiste a conserver tous les hydroxyles du glucose en introduisant le motif iode a partir des carbones du squelette. Ceci a ete effectue avec un motif iodomethyle sur les positions 3 et 6 ainsi que para-iodophenyle sur cette derniere. Tous les derives prepares ont fait l'objet d'une evaluation biologique, au moins preliminaire, sans toutefois presenter les proprietes d'un traceur du d-glucose, a l'exception du 6-deoxy-6-iodo-d-glucose (6-dig). Ce dernier, dont l'evaluation biologique sera poursuivie, a pu etre prepare a une echelle multi-grammes.

Le dédoublement par cristallisation préférentielle de dérivés 5-alkyl-5-alkylhydantoïnes : 5-éthyl-5-méthylhydantoïne (12H), et des dérivés 5-méthyl-5-(4-Xphényl)hydantoïnes : X = méthyle (17H), chloro (pCl61H), méthoxy (pMeO61H) et bromo (pBr61H) est réalisé selon le procédé auto-ensemencé AS3PC à une échelle de 35mL puis étendu à 2 litres pour les dérivés 12H et pBr61H. Le suivi de l'évolution de la population de particules pendant la cristallisation permet de conclure que l'effet d'entraînement n'est pas le fait d'un mécanisme unique. Pour le dérivé 12H, il est le résultat d'une action combinée de croissance cristalline et de nucléations. Dans le cas du dérivé pBr61H, seule la croissance cristalline est observée.

Álcoois primários sulfatados de cadeia longa, usualmente na forma de sais de sódio, são tensoativos de grande interesse comercial utilizados em diversas formulações de higiene pessoal e limpeza doméstica. Eles são produzidos comercialmente através da reação de álcoois etoxilados com trióxido de enxofre seguida de imediata neutralização com hidróxido de sódio. O produto formado é uma solução neutra de álcool primário etoxilado sulfatado em água. Sabe-se que a armazenagem desse produto por longos períodos de tempo em temperaturas elevadas pode levar à hidrólise completa, mas, em condições normais de uso e temperatura ambiente é esperado que o produto seja resistente à hidrólise. No entanto observou-se que algumas amostras comerciais de lauril éter sulfato de sódio que foram estocadas por diferentes períodos de tempo em frascos fechados à temperatura ambiente sofreram hidrólise em intervalos de tempo relativamente curtos. Isso leva à hipótese de que o comportamento de hidrólise seria influenciado por outras variáveis além da temperatura e do tempo de estocagem. O presente trabalho consistiu em identificar as variáveis de maior impacto na reação de hidrólise por meio de experimentos planejados. O teor de ativos foi acompanhado ao longo da reação para avaliar o efeito da presença de eletrólitos, de material insulfatado, em diferentes temperaturas, variando-se o pH inicial por meio da adição de ácido clorídrico. O comportamento da reação de hidrólise observado foi compatível com aquele descrito na literatura para o dodecil sulfato de sódio. A hidrólise apresentou-se como sendo autocatalítica, com a aceleração da taxa de reação provavelmente causada pela presença de íons hidrogênio liberados na reação. Foi possível identificar que as variáveis de maior efeito na reação foram: pH inicial, o teor de cloreto de sódio e a temperatura. O modelo de troca iônica em pseudo-fase foi utilizado para o tratamento dos resultados experimentais e mostrou-se adequado tendo sido, portanto, utilizado para prever o comportamento de estabilidade do produto à temperatura ambiente e nas condições em que o produto é normalmente comercializado. Um modelo empírico de redes neurais foi desenvolvido com sucesso para prever o comportamento do pH ao longo do tempo para as condições estudadas.
Long-chain primary alkyl sulfuric acids, usually as their sodium salts, are important commercial surfactants used in a large number of household and personal care formulations. They are commercially produced by treatment of mixtures of ethoxylated fatty alcohols with sulfur trioxide followed by immediate neutralization with sodium hydroxide, a neutral aqueous mixture of sodium primary alkyl ether sulfate is obtained. It is known that prolonged storage of the material at elevated temperature can lead to complete hydrolysis but under normal use and typical environmental conditions the product is expected to be resistant to hydrolysis. In spite of that it has been observed that some commercial samples of sodium lauryl ether sulfate stored for different periods of time in sealed containers at room temperature have undergone hydrolysis in a relatively short period of time which leads to the hypothesis that the hydrolysis behavior would be strongly influenced by variables other than temperature and storage time. The present work consisted of identifying the process variables with the most significant effect on the acid hydrolysis by using experimental design. The rate of hydrolysis has been followed acidimetrically to evaluate the effect of electrolytes as well as the concentration of unsulfated matter at different temperatures, over a wide initial pH range, under the presence of added hydrochloric acid. The pattern of kinetic behaviour observed was broadly the same as previously described for the sodium dodecyl sulfate. The hydrolysis presented the characteristic autocatalytic form, the catalysis presumably arising from the production of hydrogen sulfate ions. It was possible to observe that the most significant effects on the rate of hydrolysis were the initial pH, the total amount of sodium chloride and the temperature. The results were also discussed in terms of the ion-exchange pseudophase model of the micelle reaction. Accordingly to the fitting of parameters that was carried out it is possible to conclude that the pseudo-phase ion-exchange theory is found to account satisfactorily for the results reported and it was used to predict the stability behavior of the product at room temperature and under normal commercial conditions. A neural network based model was also successfully developed in order to predict the pH behavior in the conditions studied.

Ce memoire presente les syntheses d'acyl-2 methoxy-4 phenols (a) d'alkyl-2 methoxy-4 phenols (b), d'alkyl-3 methoxy -4phenols (c), d'alkoxy-4 phenols (d) d'acide (hydroxy-4' phenyl)-3 methyl-2 propionique (e), d'acide (hydroxy-4' phenyl)-3 hydroxy-2 propionique, d'hydroxy-7 carboxy-3 tetrahydro-1,2,3,4 isoquinoleine et d'acide hydroxy-4 phenylpropargylique(f). L'etude "in vivo" (cobayes) et "in vitro" des proprietes hypopigmentantes des composes a, b, c, d, e et f. L'etude "in vivo" et "in vitro" des proprietes hypopigmentantes de substances naturelles : arbutine, luteoline, abscissine

Les reactifs organomanganeux rmnx(x=cl, br, i; r=n-, sec- t-alkyl, alcenyl, aryl, alcynyl) s'additionnent aux aldehydes et cetones fonctionnels pour donner selectivement les alcools correspondant avec d'excellents rendements. Les reactifs rmnz(z=nphme) enolisent les cetones avec une excellente regioselectivite. Les enolates manganeux ainsi prepares sont tres aisement acyles, silyles, alkyles, hydroxyalkyles, avec des rendements de 60% a 90%, a la temperature ambiante

L'action des organocuprates associés à BF::(3) sur des acétals chiraux constitue une voie très originale de synthèse des alcools secondaires optiquement actifs. Les dianons des acides diethylphono 2 alcoiques réagissent avec les aldéhydes par réaction de wittig-horner et conduisent très stéréosélectivement aux acides alpha éthyléniques trisubstitués. L'action des organocuprates sur les chlorures d'acide diethylphosphono-2 alcanoïques, constitue une voie de synthèse très générale des beta cétiogisogibates alpha substitués

博士
國立臺灣科技大學
高分子系
98
ABSTRACT In this study, a series of modified surfactants were prepared and the surface activities were investigated. It relied mainly on surface activity of nonionic polyoxyethylenated stearyl ether. The content includes two kinds of new function modified surfactants. Part 1 contains the preparation of biodegradable modified surfactants by reacting dextrin-derived with polyoxyethylenated stearyl ether. The surface active properties for fabrics were improved for application in dyeing industry. Besides the increasing surface activity of surfactants, can to improve the whiteness of cotton fabric, cleaning power and biodegradable to reduce environmental pollution. The structure of these surfactants has been confirmed by EA, FTIR and 1H-NMR while the surface activities were evaluated by surface tension, contact angel and foaming properties. These surfactants exhibit excellent functional properties of surface activities. In application on cotton bleaching procedures, these surfactants increase the wetting power of the fibers of grey fabrics and also increase the whiteness of bleached cotton. Biodegradable modified surfactants possess hydrophilic groups and hydrophobic groups, exhibiting specific structure and surface activities better than traditional surfactants. Part 2 contains the preparation of multi-anionic modified surfactants were prepared by reacting anionic with nonionic polyoxyethylenated stearyl ether. For multi-anionic and nonionic hydrophilic surfactant, possess the function properties including surface tension, foam properties and wetting, can use dye auxiliary to determine interaction of dye and surfactant, dyeability and dyeing mechanism. The dyeing properties on cotton-direct dye systems were studied via the spectrophotometric method. The aggregation of direct dyes in dye-surfactant systems was found to influence the rate of cotton dyeing. The disaggregations of direct dyes in the presence of surfactants increase the dye uptake of cotton. On the other hand, the formations of dye-surfactant complex retard the speed of dye uptake at leveling fabric dyeing.

碩士
東海大學
化學工程與材料工程學系
107
In this study, two hetergeneous catalysts (MNP-DMAP and P2O5/Al2O3) were prepared for catalyzing two acylation reactions (the reactions of 2,6-dimethylphenol and polyphenylene ether with methacrylic anhydride) in a batch reactor. 2,6-dimethylphenol (2,6-DMP) is the monomer of polyphenylene ether. 2,6-DMP acylation was used to study effects of following conditions on catalyst performances: TEOS amount, reaction time, reaction temperature, catalyst weight, and catalyst reuseability. The maximum 2,6-xylyl methacrylate yields obtained were 93% and 62.35% for MNP-DMAP and P2O5/Al2O3, respectively. Kinetic studies indicated that 2,6-DMP acylation reaction was second order, with the activation energies of 33.63 KJ/mole, 38 KJ/mole, and 40KJ/mole for 4-DMAP, MNP-DMAP and P2O5/Al2O3, respectively. The second reaction was the acylation of lower molecular weight modified polyphenylene ether (MX-90). CN1280337C patent disclosed a method of producing allyl-containing polyphenylene ether using homogeneous 4-DMAP catalyst. Allyl-containing polyphenylene ether can be transformed to thermoset polymer. We studied the effects of reaction time and reaction temperature on catalyst performances, and found that product yields reached 100% for both MNP-DMAP and P2O5/Al2O3 catalysts. Kinetic studies indicated that modified polyphenylene ether acylation reaction was second order, with activation energies of 51.38 KJ/mole for MNP-DMAP. Gas Chromatography(GC), Fourier transform infrared spectroscopy (FTIR), Nuclear Magnetic Resonance(NMR), X-ray Diffraction(XRD), Thermal Field-Emission Scanning Electron Microscope(FE-SEM), High Resolution Transmission Electron Microscope(HR-TEM), Vibrating Sample Magnetometer (VSM), Inductively coupled plasma atomic emission spectroscopy (ICP-AES), High Resolution Surface Area and Porosimetry Analyzer(BET) were used to analyze the products and catalysts.

碩士
東海大學
化學工程學系
92
The objective of this dissertation is to synthesize the alkyl sulfide ether in an organic solvent/aqueous solution two-phase medium by phase transfer catalysis. Thioethers can be used as perfume and inverse phase transfer catalyst. The primary purpose of this dissertation is to study the phase transfer catalytic reaction of thioether compounds, reaction mechanism, kinetics, and parameters in order to obtain the optimum reaction conditions. The experimental results prove the actuality of the reaction mechanism and confirm following the pseudo first-order rate law. Several rigid results were obtained from the expertmental work. A. Using phase transfer catalyst to synthesize unsymmetrical sulfide ether could improve the reaction rate, increase higher yield and elevate the conversion in mild reaction conditions. B. The hypothesis of the reaction mechanism, which is identified by the experimental results is correct. Using pseudo first-order rate law and pseudo steady-state hypothesis(PSSH) could be used to describe the reaction model successfully. C. Based on the experimental data, it is known that the reaction is enhanced with the increase in temperature, amount of catalyst and symmetric form of the catalyst. In addition, the rection is also affected by the amount of water, organic solvent and the molar ratio of the two reactants.

碩士
國立成功大學
化學工程學系碩博士班
90
Two phase transfer catalysis techniques were employed in this study, one is tri-liquid-liquid-phase catalysis technique in which soluble tetra-ammonium salt (tetra-n-propylammonium bromide Pr4NBr and tetra-n-butylammonium bromide Bu4NBr) were used as the phase transter catalysts, the other is liquid-liquid-solid (i.e. triphase) catalysis technique in which insoluble polymer-supported catalyst was utilized. In the preparation of the polymer-supported catalyst (triphase catalyst) tributylamine was immobilized on chloromethylated polystyrene polymer. With organic product allyl phenyl ether (ROPh) as solvent, we made use of allyl bromide (the organic reactant, RBr) and sodium phenolate (the aqueous reactant, NaOPh) to synthesize allyl phenyl ether. By this way, we can get the pure allyl phenyl ether without separation and purification if all the allyl bromide is converted. Thus, we can save the operation cost, and need not to dispose the waste solvent. It will correspond with the ‘green chemistry’. At the end of this study, the feasibilities and two catalysis techniques were evaluated and compared by operating in continuous-flow stirred vessel reactor (CFSVR). 　　This thesis is composed of three parts. In the first part, the feasibilities of using Pr4NBr and Bu4NBr as the phase transfer catalysts for the tri-liquid-phase reaction in a continuous-flow reactor were evaluated basing on whether a third liquid phase will be formed or not. Then, using Pr4NBr as the catalyst, the tri-liquid-phase catalytic reaction was carried out under different operating conditions by means of a continuous-flow stirred vessel reactor. The performance of prepared polymer-supported catalyst was evaluated by using it as a triphase catalyst repeatedly in a batch reactor under different operating conditions in the second part. The tri-liquid-phase and liquid-liquid-solid catalytic systems were compared in the last part. 　　In the first part, the etherification reaction was carried out with the tri-liquid-phase method, the effects of operating variables, including the most suitable volume of allyl phenyl ether for helping the tri-liquid-phase and mole fraction of Pr4NBr on the conversion of RBr, and the repeated batch operations on the distribution of Pr4NBr or Bu4NBr in various phase were investigated first. After that we investigate the effects of agitation speed, inlet flow rate, reaction temperature, inlet molar ratio of reactant, the number of stages in the extractor and the kinds of catalysts on the performance of CFSVR. Experiment results show that the tri-liquid-phase catalytic system that was formed by the using Pr4NBr as a catalyst and equal amount of allyl phenyl ether and pure water was suitable for being operated in a continuous-flow reactor. When the mole fraction of Pr4NBr was 0.5, most of the catalysts concentrate on the third-liquid phase. Although the catalytic activity of Pr4NBr is lower than Bu4NBr, however, its loss rate is lower when both were used as the catalysts in repeated batch operations. When total volume of inlet fluid is larger than the volume of reactor, the system can reach a steady state. The interfacial mass transfer resistance can be neglected when the agitation speed is beyond 600 rpm. A higher conversion of RBr can be obtained when the inlet flow rate is 1 ml/min. The higher the temperature is, the higher the conversion gets and the more stable more stable the third-liquid phase is. In order to prevent the loss of that the third-liquid phase resulting from agitation, we installed a packed bed or baffles under the continuous-flow reactor, and observed individual. The result shows that the reactor with a packed bed can keep the catalyst loss rate of aqueous being lower. However, the droplet of the third-liquid phase easily stayed under the packed bed rather than go back to the reaction area. Therefore, the reaction is more appropriately carried out in the continuous-flow reactor that has baffles. The more stages the extractor has, the better the effect of extraction is. The effect of extraction will be similar if there is little amount of Pr4N+ among organic phase outlet. Feeding with equal organic-to-aqueous reactant molar ratio can keep the catalyst loss rate lower than unequal reactant molar ratio inlet. Because of lower lipophilicity, Pr4NBr was more suitable to be used as the phase transfer catalyst to run this tri-liquid-phase catalytic reaction than Bu4NBr. 　　In the second part, the etherification reaction was carried out with the liquid-liquid-solid method. Several factors which influence the conversion of RBr is discussed. The factors include agitation speed, volumetric ratio of organic solvent and water, reaction temperature, amount of catalysts, amount of aqueous and organic reactants, amount of salts, amount of tri-n-butylamines and stability of catalyst. Experimental results show that the interfacial mass transfer resistance can be neglected when the agitation speed is beyond 200 rpm. High conversion of RBr will be obtained when the volume of organic solvent and water are equal. Raising the temperature can promote the conversion. But RBr will vaporize and the catalyst will be worsened when the temperature is too high. As a result, the appropriate temperature is 50℃. An amount of 5.4 meq catalyst is economic and cost-effective. When using more NaoPh than RBr, the reaction is pseudo-first-order irreversible reaction. As this time, a higher conversion of RBr comes into effect. Existence of salts restrains the activity of catalyst. The extent of inhibition depends on the amount of salts. Two reasons will cause the decrease of catalyst activity. One is that the activity site on the polymeric support will fall down because of Hofmann elimination reaction. The other is that the force of agitation will destroy the structure of catalyst. The tri-n-butylamine which falls from support can react with organic reactant and form the tetra-alkylamine salt. The tri-n-butylamine salt has catalytic activity but is lower than the form that the tri-n-butylamine fixes on the support. 　　The performances of the tri-phase system and liquid-liquid-solid system are compared in the last part. The comparison is based on four items, namely, catalytic effect, stability of catalysts, the operation of continuous-flow reactor and the procedure of preparing catalysts. Because of the high dispersion and bigger interfacial area, the tri-liquid phase catalyst has better catalytic effect. On the other hand, the tri-liquid phase catalyst is cheaper than the triphase catalyst hence it is more cost-effective. Although the tri-liquid phase catalyst will dissolve in organic and aqueous phase and flow away with outlet, the stability of catalyst is still better than triphase catalyst. The operation of continuous-flow reactor with liquid-liquid-solid catalyst is simpler due to the fact that we don’t have to extract the catalyst from the organic phase. The procedure of preparing polymer-supported catalysts is complicated and the reproducibility is not as well as the formation of a third liquid phase in the tri-liquid phase system.

碩士
國立成功大學
化學工程學系碩博士班
101
Poly(N-vinylpyrrolidone) ( PVP ) form complexes with poly(methacrylic acid) ( PMA ) by hydrogen bonding. The main purpose of the study is the influence of nonionic surfactant Tergitol 15-S-9 and Tergitol 15-S-30 on the complexes of PMA and PVP. This investigation is classified according to surfactant. The first section is Tergitol 15-S-9 system, and the second section is Tergitol 15-S-30 system. The interaction between surfactant and PVP, PMA in different pH respectively, and PMA/PVP complexes in different pH were investigated by fluorescence, transmittance, pH measurements and aggregation number. In Tergitol 15-S-30 system, its EO chain length is longer than Tergitol 15-S-9, so the number of hydrogen bonding formed with PMA increases, that the influence of hydrogen bond on PMA and PMA/PVP complexes is more marked than Tergitol 15-S-9 system. Hydrogen bonding affects the solution properties obviously in acidic solution.

碩士
國立中興大學
化學工程學系所
99
In this study, allyl phenyl ether was synthesized by ultrasound-assisted liquid-liquid phase-transfer catalysis in capillary micro-reactor. In general, we use micro-reactor can be increased specific surface between organic phase and aqueous phase, and increased reaction rate. In this study, we compared the difference in performance between batch reactor and micro-reactor. The operating parameters including reactor length, types of catalyst, amount of catalyst, types of solvent, reaction temperature, space time, ultrasonic frequency and power, were all performed to find the optimal reaction conditions. The yield of allyl phenyl ether increased with the space time, so the flow rates of aqueous phase and organic phase were both controlled at 0.03 ml/min. Increasing reaction temperature can increase the reaction rate. The lower ultrasonic frequency made the yield of product higher. For improved productivity, in the conditions of 0.25 M of sodium phenoxide trihdrate, 0.0625 M of tetra-n-butylammonium bromide, 0.125 M of allyl bromide, 60 cm3 of de-ionized water, 60 cm3 of methyl isobutyl ketone, aqueous phase flow rate was 0.03 cm3/min, organic phase flow rate was 0.03 cm3/min, reactor length is 107 cm, ultrasonic frequency at 28 kHz and power 300 W, and the reaction temperature at 60 °C, the product was 91.2 %. The apparent activation energy can be obtained as 19.27 kcal/mol in the range of 45~60 °C. When reaction with ultrasound assisted, the reaction activity can be increased. The yield of product was 62.6 % without ultrasound assisted, but when reaction with ultrasound assisted, the yield of product was 91.2 %. Compared the reaction with and without ultrasound assisted, the product yield can be raised to 45.7 %. Comparison of the reactor, at the same space time, the yield of product in micro-reactor was higher than the yield of product in batch reactor. When the space time was 7.2 minutes, the yield of product in micro-reactor was 91.2 % and the yield of product in batch reactor was 70 %. The reaction constant in Micro-reactor was higher than that in batch reactor, so we used the micro-reactor to get the better reaction efficiency.

碩士
國立成功大學
化學工程學系碩博士班
91
In this study, several kinds of trialkylamines were immobilized on chloromethylated polystyrene polymer, silica gel and alumina to prepare triphase catalysts. These catalysts were then employed for catalyzing the etherification reaction of allyl bromide (the organic reactant) and sodium phenolate (the aqueous reactant). In the experiments, phenetole has a configuration similar to the organic product, allyl phenyl ether, was used as an organic solvent for the purpose of simulating a reaction system with the organic product as a solvent. An optimal catalyst was selected basing on the activity, selectivity and stability. Subsequently, for preventing the catalysts from the destruction by the stirrer, ultrasonic vibration was imposed on the reactor. The effect of ultrasonic vibration on the performance of catalyst was investigated. Finally, the etherification reaction was carried out in a batch reactor and a continuous-flow stirred vessel reactor in which the organic product was used as a solvent, and the ultrasonic vibration was imposed in addition to a slow mechanical stirring. By this study, an optiomal catalyst and a proper way of stirring were found. This thesis is composed of four parts. In the first part, several kinds of trialkylamines were immobilized on the polymeric support and used as the catalysts for catalyzing the etherification reaction. Experiment results show that the immobilization of trialkylamine is influenced by the length of the alkyl group in the trialkylamine molecules. The amount of trialkylamine immobilized is less when the length of alkyl group is longer. For catalyzing the reaction between allyl bromide and sodium phenolate, the catalyst immobilizing tri-n-propylamine is the best, tri-n-butylamine the second, triethylamine the next, and tri-n-pentylamine the worst. When the amount of sodium phenolate is larger than that of allyl bromide, the conversion of allyl bromide will be higher, and the reaction is of the pseudo-first order. In the second part, the inorganic compounds (silica and alumina) were functionalized first and then used as the supports for immobilizing the trialkylamines. The inorganic supported catalyst has a high mechanical strength, can sustain even at high temperatures and can not be easily destroyed at a high stirring speed. Its stability is higher than the polymeric supported catalyst. The experimental result shows that it is true. The shortcoming of inorganic supported catalyst is its low activity and selectivity. In addition, the rate of catalyzing allyl bromide will be slow down in the later period of the reaction. These shortcomings can not be improved by changing the operation conditions. So comparing to the polymeric supported catalyst, the inorganic supported catalyst is a worse choice. In order to mitigate the decay of catalyst due to the destruction by the mechanical stirrer and to improve the contacting pattern between the catalyst particles and the organic and aqueous phases for increasing the reaction rate, three mixing modes were compared in the third part of this study, namely, mechanical stirring, mechanical stirring with the imposition of ultrasonic vibration, and stirring with a magnetic bar. The experimental results show that the decay of the catalyst is indeed mitigated when the ultrasonic vibration is imposed on the reaction mixture which is agitated by a mechanical stirrer at a slow speed. The result also reveals the activity and the stability of the catalyst become the worst when the magnetic bar is employed for stirring. In the last part, the etherification reaction was carried out in a batch reactor and in a continuous-flow stirred vessel reactor (CFSVR) with the organic product, allyl phenyl ether, as the solvent. The catalysts and the operation conditions were selected and determined by referring the results obtained in the preceding parts. The polymeric supported tri-n-propylamine was used as the catalyst while the SiO2-supported tri-n-butylamine catalyst was tested for comparison. The mechanical stirring at a low agitation speed with the imposition of ultrasonic vibration was adopted for agitating the reacting mixture. The results reveal that the activity of polymeric supported catalyst is higher than that of SiO2-supported catalyst, and the conversion of allyl bromide declines only slightly during a long-period operation.

碩士
國立成功大學
化學工程學系碩博士班
100
The major idea of the research is the influence of noionic surfactant Tergtitol 15-S-9 and 15-S-30 on the polymer complexes of poly(N-vinylpyrrolidone) ( PVP ) and poly(acrylic acid) ( PAA ). The PVP/PAA hydrophobic complexes form due to the hydrogen bond between the pyrrolidone belong to PVP and the carboxylic acid belong to PAA. When adding surfactant to PVP/PAA system, the hydrophobic interaction between PVP and PAA decrease, because the interaction between surfactant and polymer reduce the hydrogen bonding between PVP and PAA. There are hydrophobic interaction between alkyl groups in surfactant , PVP and PAA, and hydrogen bonding interaction in a portion of PAA system with the ethylene oxide ( EO ) chains of “Tergitol 15-S-n” surfactant. The investigation divide into two sections. The first section is Tergitol 15-S-9 system, and the second section is Tergitol 15-S-30 system. The interaction between (1) PVP and surfactant (2) PAA in different pH and surfactant (3) PVP/PAA complexes in different pH and surfactant were characterized by Fluorescent, specific viscosity, pH and aggregation number in both systems. After unscramble the result of the investigation, discovering the interaction between PAA and surfactant was week in the Tergitol 15-S-9 system, and when the EO chain of surfactant become longer the interaction between surfactant and PAA or PVP/PAA complexes increase.

碩士
國立成功大學
化學工程學系
89
In this study, the feasibilities of using tri-liquid-phase and liquid-liquid-solid phase transfer catalysis techniques for synthesizing allyl phenyl ether by etherification of allyl bromide (the organic reactant) and sodium phenolate (the aqueous reactant) were evaluted and compared. Tetrabutylammonium bromide, a soluble catalyst, was used in the tri-liquid-phase catalysis while the supported tributylamine, which was immobilized on the chloromethylated styrene-DVB copolymer, was employed as the triphase catalyst. Both catalytic reactions were carried out in a continuous-flow stirred vessel reactor (CFSVR). This dissertation consists of four parts. In the first part, the experimental results of the tri-liquid phase catalysis in a CFSVR were explained and discussed. The second part deals with the liquid-liquid-solid phase transfer catalysis in a batch reactor, while the third part presents the results of the liquid-liquid-solid phase transfer catalysis in a CFSVR, which was operated under the conditions determined by referring to the results obtained in the second part. The performances of these two techniques, tri-liquid and liquid-liquid-solid phase transfer catalysis, were compared in the fourth part. In the first part, the effects of operating variables including mole fraction of QBr, inlet reactant mole ratio, agitation speed, operating temperature, reactant volumetric flow rate, stability of catalysts and the installation of baffles in the bottom of reactor on the performance of the tri-liquid phase catalytic system were investigated. Experimental results indicate that increasing the amount of salts and utilizing non-polar organic solvent will enhance the formation of third-liquid phase. To concentrate catalysts in the third-liquid phase and to save the dosage of catalysts, appropriate mole fraction of QBr should be between 0.3 and 0.5. Feed with equal organic-to-aqueous reactant molar ratio will reduce the catalyst loss rate. The interfacial mass transfer resistance can be neglected when the agitation speed is beyond 300 rpm. However, catalyst loss rate would rise up when the agitation speed exceeded 800 rpm. Therefore, agitation speed was fixed at 800 rpm in this study. The installation of baffles improves the separation of third-liquid phase and aqueous phase, hence reduce catalysts loss rate effectively. High temperatures will lower catalyst loss rate, while low temperatures reduces stability of third-liquid phase. Therefore, a high temperature is preferred, the reasonable operating temperature is 50℃. For finding proper operating conditions for the continuous operation of the liquid-liquid-solid system, in the second part, the effects of the operating variables, including agitation speed, volumetric ratio of organic solvent and water, kinds of organic solvents, amount of catalysts, operating temperature, kinds and amounts of salts, on the performance of a batch reactor were studied first. The experimental results show that: The interfacial mass transfer resistance can be neglected when the agitation speed is fixed at 600 rpm. Higher conversion of allyl bromide and fraction yield of allyl phenyl ether will be obtained when the volumes of organic solvent and water are equal. Kinds of organic solvent have little effect on the fraction yield of main product when no catalyst is used. However, organic solvent of higher polarity increases not only the conversion of allyl bromide but also the fraction yield of allyl phenyl ether when 3g of catalysts are employed. A high temperature will induce more side-reactions while a low temperature results in water solvation, appropriate temperature is 40℃. Existence of salts restrains the activity and selectivity of catalysts. The extent of inhibition depends on the amount of salts added but is nearly independent on the kinds of salts. The third part presents the results of the reaction carried out in a CFSVR under the conditions determined by referring to the results obtained in the second part. The variables investigated include agitation speed, amount of catalysts, reactant volumetric flow rate, operating temperature and catalysts deactivation. Experimental results reveal that catalyst decays obviously under high temperatures. To prevent evaporation, the proper temperature is 40℃. Increasing the amount of catalyst will give a higher reaction rate, however, excess catalysts will cause coagulation and the catalyst particles would not be well scattered in agitation. Because etherification reaction in this experiment is irreversible pseudo-first-order, increasing the inlet aqueous or organic reactant concentration will have little effect on the conversion of allyl bromide. As to the stability, catalyst obviously loses its activity during a long-time operation. The inlet dispersion phase can not mix well immediately with another dispersion phase primarily existing in the CFSVR, therefore, the observed outlet concentration of allyl bromide is higher than the predicted value. In turn, both the reaction rate and the conversion are higher than the value predicted from the model for the batch reactor. The performances of the tri-liquid-phase and liquid-liquid-solid systems are compared in the final part. The comparison is based on five items namely, activity, selectivity, stability, the operation of continuous-flow reactor and the procedure of preparing catalysts. (1). Because of the hydrophobic property of polymer-supported catalysts, the aqueous reactant is hard to diffuse into the active sites inside the catalysts, the reaction of liquid-liquid-solid catalytic system only proceeds on the external surface of catalyst particles. Therefore, the catalytic activity in the tri-liquid phase catalysis is much better than that in the liquid-liquid-solid phase transfer catalysis under the same amount of catalysts. (2). The third-liquid phase is more stable than the polymer-supported catalyst, but the third-liquid phase might be dissolved slightly in the water. (3). The fraction yield of main product obtained by the tri-liquid phase transfer catalysis is higher than that with the liquid-liquid-solid phase transfer catalysis. Oxygen-allylation is the main reaction in the tri-liquid phase catalysis. However, side-reactions may take place in carbon-allylation pathway within liquid-liquid-solid phase transfer catalysis. (4). Both of tri-liquid and liquid-liquid-solid phase transfer catalysis can recover catalysts easily but excessive concentration of salts in the tri-liquid phase catalytic system may result in the formation of salt crystals and the loss of catalysts. (5). The procedure of preparing polymer-supported catalysts is complicated and the reproducibility is not as well as the formation of a third liquid phase in the tri-liquid phase system. 1-1 傳統的兩液相反應系統---------------------------------------------------1 1-2 相間轉移觸媒的種類------------------------------------------------------2 1-3 液-液-固三相催化反應----------------------------------------------------4 1-3-1 液-液-固三相觸媒-------------------------------------------------4 1-3-2 續流式液-液-固三相催化反應----------------------------------6 1-4 三液相催化反應------------------------------------------------------------7 1-4-1 三液相催化反應系統---------------------------------------------7 1-4-2 第三液相觸媒的重複使用性------------------------------------8 1-5丙烯基苯基醚的合成-------------------------------------------------------8 1-6本論文的研究內容--------------------------------------------------------10 第二章 實驗--------------------------------------------------------------------------12 2-1 實驗藥品-------------------------------------------------------------------12 2-2 實驗方法-------------------------------------------------------------------13 2-3 分析方法-------------------------------------------------------------------16 2-3-1 固體觸媒中氯離子含量（活性基）之分析---------------------16 2-3-2 四正丁基銨離子濃度的分析------------------------------------18 2-3-3 氣相層析法（G.C.）分析-------------------------------------------18 2-4 校正曲線-------------------------------------------------------------------19 2-5 反應物轉化率與主產物生成分率的定義----------------------------20 第三章 續流式三液相反應--------------------------------------------------------25 3-1 形成第三液相之適當條件--------------------------------------27 3-2 適當操作條件之分析-------------------------------------------29 3-3 不同流率下反應器所需穩定時間-------------------------------29 3-4擋板效應對轉化率與觸媒流失率的影響-----------------------30 3-5 攪拌速率的效應--------------------------------------------------------30 3-6反應溫度與進料流率的效應------------------------------------------31 3-7 不同莫耳比進料的效應-------------------------------------------32 3-8 三液相觸媒的穩定性-------------------------------------------------33 第四章 批式液-液-固三相反應---------------------------------------------------44 4-1攪拌速率對反應的影響--------------------------------------------------46 4-2 油、水體積比對反應的影響---------------------------------------------47 4-3 有機溶劑種類對反應的影響-------------------------------------------48 4-4 觸媒添加量對反應的影響----------------------------------------------49 4-5 溫度對反應的影響-------------------------------------------------------50 4-6 丙烯基溴添加量對反應的影響----------------------------------------51 4-7 酚化鈉添加量對反應的影響-------------------------------------------51 4-8鹽類種類與添加量對反應的影響--------------------------------------52 4-9 觸媒重複使用次數對反應的影響-------------------------------------53 4-10 機械攪拌力對觸媒活性的影響---------------------------------------53 4-11 反應速率式的推導-----------------------------------------------------54 第五章 續流式液-液-固三相反應------------------------------------------------75 5-1不同流率下反應器所需穩定時間--------------------------------------75 5-2 攪拌速率的效應----------------------------------------------------------76 5-3 觸媒添加量的效應-------------------------------------------------------76 5-4 反應溫度與進料流率的效應-------------------------------------------77 5-5 三相觸媒的穩定性-------------------------------------------------------77 5-6 酚化鈉濃度效應----------------------------------------------------------78 5-7 丙烯基溴濃度效應-------------------------------------------------------78 5-8 由續流攪拌式反應器推測反應速率式-------------------------------78 5-9續流攪拌式反應器與批式反應器的比較-----------------------------79 第六章 結論與未來研究方向-----------------------------------------------------91 6-1 三液相系統與液-液-固系統之綜合比較-----------------------------91 6-1-1催化活性------------------------------------------------------------91 6-1-2觸媒穩定性---------------------------------------------------------91 6-1-3反應選擇性---------------------------------------------------------92 6-1-4續流式操作的難易度---------------------------------------------93 6-1-5觸媒製備程序------------------------------------------------------93 6-2 結論-------------------------------------------------------------------------93 6-3 對未來研究方向建議----------------------------------------------------97 參考文獻-----------------------------------------------------------------------------100 自述-----------------------------------------------------------------------------------104