Dissertations / Theses on the topic 'Dioxin derivates'

La plupart des procédés thermiques conduisent à la formation de dioxine (PCDD/F) à l'état de traces. Leur toxicité et leur faible biodégradabilité nécessitent de minimiser ces rejets par tous les moyens disponibles (modification du procédé, traitement des émissions, etc. ). Dans le cas des incinérateurs, notre étude bibliographique révèle que la zone de refroidissement des fumées joue un rôle particulièrement important sur la formation des PCDD/F. Des études approfondies effectuées sur des micropilotes ont permis d'identifier trois voies indépendantes conduisant à la formation de ces produits : une formation en phase gazeuse vers 600°C, une formation catalytique en présence de poussières de 300°C à 500°C et finalement la réaction de-novo par gazéification des poussières à 300°C. Nous en avons conclu que seule une amélioration de la combustion permettait de réduire la quantité de PCDD/F émis mais également celle d'autres produits imbrulés indésirables. Nos résultats expérimentaux sur l'oxydation du dibenzofurane en phase gazeuse et à des températures relativement élevées (> 900°C) prouvent que la teneur en oxygène ainsi que le régime d'écoulement sont les paramètres primordiaux et qu'une richesse d'environ 0,8 conduit à une combustion totale des imbrulés. Enfin, nous avons construit un mécanisme détaillé appliqué à l'oxydation du dibenzofurane qui permet d'expliquer qualitativement nos observations expérimentales et qui semble être en bon accord avec les hypothèses faites par d'autres équipes de recherche sur l'oxydation des produits aromatiques à haute température

The structure and synthesis of N,N'-disubstituted thiourea-S,S-dioxides were investigated experimentally and computationally. Hydrogen peroxide oxidation of acyclic and cyclic N,N'-dialkylthioureas furnished S,S-dioxides in agreement with computational predictions. Some s,S,S-trioxides were also isolated. An X-ray crystallographic study of N,N'-diisopropylthiourea dioxide, fIrst synthesised in this work, verilled computational models. The prediction of a stable N,N'-diarylthiourea dioxide derivative was supported by successful isolation of the dioxide. The application of N,N'-diisopropylthiourea dioxide as a reducing agent was investigated. Removal of tosyl groups from N-tosylaziridines, deprotection of CBz-amines and reduction of nitriles could not be realised. However, aldehydes and ketones were successfully reduced to the respective alcohols in yields comparable with that of thiourea dioxide. Disulfides and N-tosylsulfIIDides were reduced to a higher degree with N,N'· diisopropylthiourea dioxide than thiourea dioxide under simple, mild conditions. The mechanism of decomposition of N,N'-diisopropylthiourea dioxide to give radical anions was investigated with N-tosylsulfIIDides and a cyclopropylketone. The study revealed that at high pH, heterolysis of the C-S bond in N,N'-diisopropylthiourea dioxide led to the formation of a sulfmate dianion sol. The dianion was thought to rapidly oxidise to a powerful reducing species, the radical anion SO;- and subsequently effect reduction via a single-electron transfer pathway. A full mechanism of decomposition and reduction is proposed. An investigation into the role of thiourea dioxides as N-heterocyclic carbene (NHC) synthons was carried out. It was thought that decomposition of ethylenethiourea dioxides, via the elimination of sulfur dioxide, would provide an alternative approach to metal NHC complex synthesis. Oxaziridine oxidation of acyclic thioureas, successfully established in this work, was applied to the preparation of ethylenethiourea dioxides. A short study revealed considerable potential for thiourea dioxides as NRC precursors.

Electrocatalytic reduction and oxidation of nitrite using cobalt phthalocyanine derivatives was studied. The detection limit of 1 x 10⁻¹° mol dm⁻³ was achieved when these molecules were employed as catalysts for nitrite detection. The mechanisms for nitrite catalysis were proposed. The position of the peripheral substituents on cobalt porphyrazines (related to cobalt phthalocyanines) affected the catalytic activity of these complexes. The highest activity for nitrite reduction was observed on the cobalt(II) 2,3-tetramethyltetrapyridinoporphyrazine ([CoTm-2,3-tppa]⁴⁺), with cobalt phthalocyanine showing the lowest activity, and the cobalt(II) 3,4- tetramethyltetrapyridinoporphyrazine ([CoTm-3,4-tppa]⁴⁺), showing intermediate behaviour. A mixture of a negatively charged cobalt(II) tetrasulfophthalocyanine ([Co¹¹TSPc]⁴⁻) and a positively charged [CoTm-3,4-tppa]⁴⁺ showed better activity for nitrite reduction than did the individual components. Cobalt porphyrazines lowered the potentials for nitrite reduction in that peaking was observed, as opposed to cobalt phthalocyanine, where only the increase in currents was observed without peaking. Using the cobalt phthalocyanine derivatives, nitrite can be reduced to ammonia with high current efficiency. A glassy carbon electrode modified with [Co¹¹TSPc]⁴⁻ was employed for the determination of nitrite. Nitrate had an insignificant effect on nitrite oxidation on these modified electrodes. Electrocatalytic determination of S0₂ was studied as a function of pH at a glassy carbon electrode modified with iron(II) tetrasulfophthalocaynine. It was found that depending on pH, S0₂.xH₂0, HS0₃⁻ and/or SO₃²⁻ are the main compounds in solution and that these compounds behave differently at the electrode surface. Detection limits ranging from 4.0 ± 0.1 x 10⁻⁵ to 7.5 ± 0.1 x 10⁻⁵ mol dm⁻³ depending on pH were observed. Similar results were obtained when cobalt(II) tetrasulfophthalocaynine was employed for S0₂ catalysis under the same experimental conditions. Cysteine and histidine determination using oxidation currents was performed on glassy carbon electrodes modified with [CoTm-3,4-tppa]⁴⁺ (represented as [CoTm-3,4-tppa]⁴⁺-GCE) in pH 7 Tris buffer. The detection limit of 1.0 x 10⁻⁵ mol dm⁻³ for cysteine and 2.24 x 10⁻⁷ mol dm⁻³ for histidine were obtained. Cyanide can be detected down to 1 x 10⁻¹¹ mol dm⁻³ using [CoTm-3,4-tppa]⁴⁺-GCE in pH 10.8 buffer. Cyanide and S0₂ coordinate to the [CoTSPc]⁴⁻ species. The coordination is accompanied by oxidation of the central Co(II) metal, forming a [Co¹¹¹CoTSPc]³⁻ species. The rate constants for cyanide coordination to the [Co¹¹TSPc]⁴⁻ complex are larger than those reported for the coordination of cyanide to FePc and RuPc complexes in non-aqueous media. Autoreduction of [Co¹¹Tmtppa]⁴⁺ occurred in the presence of either histidine or cysteine, with the formation of metal reduced species, [Co¹Tmtppa(-2)]³⁺. Nitric oxide and nitrite coordinate to the [Co¹¹Tmtppa]⁴⁺ species, without auto-reduction of this species, which was observed for cysteine or histidine. The use of [Co¹¹TSPc]⁴ resulted in improved rate of interaction with nitrite when compared to the [Co¹¹Tmtppa]⁴⁺ species.

Ein vielversprechendes Design für organische lichtemittierende Dioden (OLEDs) verwendet eine Wirt-Gast-Strategie durch Dispergieren einer kleinen Menge eines hocheffizienten Emitters (der Gast) in eine passende Transportmatrix (der Wirt). Die Aufgabe des Wirts ist den Exzitonentranport zum Emitter sicherzustellen und den Zerfall von Triplet-Exzitonen zu verhindern, und damit eine hohe Bauteilperformance zu erreichen. Die vorliegende Arbeit konzentriert sich auf die Beziehung zwischen Molekülstruktur und optoelektrischer Eigenschaften von Carbazol/Dibenzothiophen-Derivaten. Die Untersuchung umfasst sieben dieser Derivate für den Wirt, bei denen die Carbazoleinheit als Donator und die Dibenzothiopheneinheit als Akzeptor fungiert, wobei beide durch einen oder mehrere Phenylabstandshalter verbunden sind. Diese Wahl der Wirtsmaterialien erlaubt es den Einfluss der erweiterten Phenylabstandshalter und der unterschiedlichen molaren Verhältnisse von Akzeptor zu Donator zu untersuchen. Es ergab sich, dass eine kürzere Phenylabstandshalterlänge die Bauteilperformance durch eine größere Löcher- und Elektronendichte in der Emitterschicht verbessert; und ein 1:1 Carbazol-zu-Dibenzothiophen-Verhältnis der Bauteilperformance zuträglich ist, da es zu einem Ladungsträgergleichgewicht in der Emitterschicht führt. Diese Arbeit zeigt, unter Verwendung dieser Wirtsmaterialien, blaue FIrpic-basierte phosphoreszierende OLEDs (PhOLEDs) und grüne 4CzIPN-basierte thermisch aktivierte verzögerte Phosphoreszenz (TADF) OLEDs. Die blauen PhOLEDs und grünen TADF OLEDs mit mDCP zeigten Effizienzen von 43 cd/A (18.6%) beziehungsweise 66 cd/A (21%).
A particularly interesting organic light-emitting diodes (OLEDs) design adopts a host-guest strategy by dispersing a small amount of highly efficient emitter (the guest) into an appropriate transport matrix (the host). The host is utilized to transfer excitons to the emitter and to prevent triplet exciton quenching, thus high device performance can be achieved. The present thesis focuses on the relationship between the molecular structure and opto-electrical properties of carbazole/dibenzothiophene derivatives. The investigation encompasses seven of these derivatives for the host, in which the carbazole unit acts as a donor and the dibenzothiophene as an acceptor while they are linked through phenyl spacer(s). This choice of host materials enables to assess the impact of extended phenyl spacers and different acceptor to donor molar ratios. It was found that decreasing the phenyl spacer length enhances the device performance due to the larger both hole and electron densities in the emitting layer; and a 1:1 carbazole to dibenzothiophene ratio is favorable for device performance, since it balances the charge carriers in the emitting layer. Using these host materials, the work presented in this thesis demonstrates high-performance blue FIrpic-based phosphorescent OLEDs (PhOLEDs) and green 4CzIPN-based thermally activated delayed fluorescence (TADF) OLEDs. The blue PhOLEDs and green TADF OLEDs with mDCP showed efficiencies of 43 cd/A (18.6%) and 66 cd/A (21%), respectively.

The synthesis of high molecular weight copolymer of carbon disulphide (CS2) and propylene oxide (PO) has not reported in literature. In the present work, zinc isopropyl xanthate (Zn(Xt)2) was used as catalyst for the copolymerisation of PO and CS2 into high copolymer. However, the product can be fractionated into high and low molecular weight components. High molecular weight copolymer was rubbery products, but low molecular weight copolymers were oily products containing cyclic dithiocarbonates. Copolymers were characterized by elemental, end group analysis, DSC, TGA, GPC, Light Scattering, UV, IR, NMR spectroscopy, polarized microscopy and refractometry. Copolymerization process was zeroth order with respect to monomers, and its non-terminated but suffered from several types of transfer reactions. As a result of transfer reactions S-(C=S)-S, O-(C=S)-O, O-(C=O)-O groups in the backbone of copolymer and SH groups at the chain terminals and cyclic dithiocarbonates are formed. Apart from SH groups, OH and double bonds were found and their amounts were determined at the chain terminals. Copolymers with high mole fractions of PO units (F1) in the copolymer are crystallized in the shape of Malta&
#8217
s Cross. Melting points of products were obtained from DSC. The F1 values are calculated from elemental analysis as well as zeroth order rate constants and from melting point of the crystals. All three results were in close agreement and changed between 0.9 &
#8211
0.7. However, these ratios depend on reaction conditions (temperature, catalyst and monomer concentrations, time and dielectric constant of reaction medium). A mechanism for coordination-copolymerization on the basis of above observation was proposed.

Gegenstand der vorliegenden Arbeit ist die Untersuchung makrocyclischer Strukturen, welche über eine Sequenz von zwei Diels-Alder-Reaktionen synthetisiert wurden. Dabei wurden leichtzugängliche Sorbinsäure- und Sorbyl-Abkömmlinge mit aliphatisch-verknüpften Bis-(1,2,4-triazolin-3,5-dionen) kombiniert. Infolge der Prochiralität der eingesetzten Bisdiene können stereochemisch-differenzierte Reaktionsprodukte auftreten. Besonderes Augenmerk lag auf der stereochemischen Zuordnung, welche in vielen Fällen mittels NMR-Spektroskopie oder Einkristall-Röntgenstrukturanalyse gelang.

Ce travail vise à obtenir un matériau possédant des propriétés de complexation grâce aux cyclodextrines (CyD) et à démontrer la faisabilité de la synthèse en milieu CO2 supercritique (scCO2). L'adaptation en scCO2 de la polyaddition directe entre une α-CyD et un diisocyanate n’a montré qu’une faible conversion après 7 heures de réaction (presque totale en 4 heure en milieu liquide), en raison de la complexation possible du diisocyanate par la CyD, de l’insolubilité de la CyD dans le scCO2 ou d’une diminution de la vitesse de réaction nécessitant un temps supérieure pour atteindre une conversion plus élevée. Des études supplémentaires sont nécessaires pour confirmer ses hypothèses. La conception d’un monomère original pouvant être scCO2-soluble, par acétylation des hydroxyles de la CyD, fonctionnalisé par 3 isocyanates a montré, par polyaddition avec une alkyldiamine, en milieu solvant, une forte dépendance de la masse molaire avec la concentration (jusqu’à 16,89 kg/mol à 50 %pds en monomères). En milieu scCO2, la conversion du monomère original a été totale, avec des masses molaires atteintes supérieures à celles en milieu liquide à concentration identique, démontrant l’intérêt d’un tel milieu en remplacement de solvants organiques dans le cas d’une conception bien adaptée. L’extension de la gamme de concentrations et des conditions opératoires (température, pression) reste à réaliser pour conclure à l’intérêt du scCO2 par rapport à ce monomère original à base de CyD
This work aims at obtaining a polymeric material possessing complexation abilities thanks to cyclodextrins (CyD) within its framework and demonstrating the feasibility of the synthesis in supercritical CO2 medium (scCO2). Contrary to liquid medium, the polymerization of α-CyD and a diisocyanate in scCO2 shows only low conversion after 7 hours due to the possible complexation of the diisocyanate by the CyD, the insolubility of the CyD in scCO2 medium or insufficient time to achieve high conversion due to diminution of the reaction rate. New studies have to be done in order to confirm these hypothesis. The design of an original monomer which could be soluble in scCO2 thanks to acetyl groups fixed on the CyD and functionalized by 3 isocyanates, leads to a strong dependency of the molar mass with the concentration of monomers (up to 16.89 kg/mol at 50 %w of monomers) when reacted with a diaminoalkyle chain extender in solvent medium. In scCO2 medium, full conversion of this monomer is achieved, with higher molar masses obtained than in liquid medium at the same concentration. This demonstrates the potential of such a synthesis medium instead of organic solvents when design is well adapted. However, more experiments are needed to study the influence of concentration, temperature and pressure on larger scales to conclude in the interest of scCO2

Higher carbon chain sugars have gained increased interest recently; they are important building blocks of natural and unnatural products with biological properties. The synthesis of these higher sugar skeletons is commonly known to be achieved with the Wittig methodology which exploits phosphorus ylide chemistry. This method has been successfully used for the synthesis of the higher carbon sugars. The aim of this project was to synthesise ß,ß'-dioxo sugar-derived phosphorus ylides, a new class of ylides, as versatile intermediates to valuable higher carbon sugar derivatives and carbohydrate mimics. Model reactions were initially conducted; tetrahydro-2-furoic acid and tetrahydro-2H-pyran-4-carboxylic acid, compounds which are structurally similar to the precursor sugars, were identified as suitable model compounds. These compounds were converted to acyl chlorides and then converted to ß,ß'-dioxo phosphorus ylides precursors by acylation. The methodology proved successful and 8 examples were isolated. However, low yields were obtained due to the inevitable formation of triphenylphosphine oxide. The method was then extended to sugar derivatives, prepared using standard protecting group chemistry. It was found that acylation could be achieved using the simple acyl chloride route or peptide coupling methodology for sugar derivatives which were acid sensitive. ß,ß'-dioxo sugar-derived phosphorus ylides (16 examples) were successfully isolated in low yields. The oxidation and thermal reactivity of the ß,ß'-dioxo ylides were studied. Oxidation resulted in the successful synthesis of vicinal tricarbonyls, isolated as a mixture with the gem-diols (hydrates). The thermal decomposition of the ylides gave alkynes in moderate yields.

Ce travail est consacré à la recherche et au développement de nouvelles molécules à viséepharmacologique en série naphtoquinonique en utilisant des réactions par transfert monoélectroniquede type SRN1 et des cyclisations radicalaires oxydatives induites par l'acétate de manganèse(III). Lapremière partie décrit l’étude de la réactivité SRN1 de la 2-(chlorométhyl)-3-méthoxynaphtoquinoneavec divers anions nitronates conduisant à la formation de produits de C-alkylation avec de bonsrendements. Ces derniers ont fait l’objet d’une réaction de réduction-cyclisation permettant la synthèsede nouveaux dérivés benzo[g]indol-5(3H)-ones. Dans la seconde partie, une nouvelle réactiond’oxydation initiée par l’acétate de manganèse(III) a été développée sur la 2-hydroxy-3-méthylnaphtoquinone dans des conditions opératoires douces. En effet, la réactivité originale de la 2-hydroxy-3-méthylnaphtoquinone avec divers alcènes aromatiques en présence de Mn(OAc)3 et dedioxygène, a permis pour la première fois en série naphtoquinonique, l’obtention de nouveaux dérivésoriginaux dihydronaphto[2,3-c][1,2]dioxine-5,10(3H,10aH)-diones sous forme d’un mélange dediastéréoisomères à potentialités antipaludiques. Un mécanisme réactionnel original a été proposé pourla formation de ces produits
This work is focused on the research and development of new pharmacologicalmolecules in naphthoquinonic series, synthesized by single electron transfer reaction SRN1 ormanganese(III) acetate catalyzed oxidative radical cyclization. The first part describes the SRN1reactivity of 2-(chloromethyl)-3-methoxynaphthoquinone with various nitronate anions leading to theC-alkylation products. The reduction-cyclization reaction of the latter derivatives allowed us to obtainnew benzo[g]indol-5(3H)-one derivatives. In the second part, a new reaction initiated by Mn(OAc)3 on2-hydroxy-3-methylnaphthoquinone was developed under mild conditions. Indeed, the original reaction of2-hydroxy-3-methylnaphthoquinone with various aromatic alkenes in presence of dioxygen led to newdihydronaphtho[2,3-c][1,2]dioxine-5,10(3H,10aH)-dione derivatives as a mixture of diastereoisomerswith antimalarial potential. An original mechanism was proposed in order to explain the formation ofthese products

Ce travail s’inscrit dans la recherche et le développement de nouvelles méthodologies pour la synthèse de molécules portant un groupement sélénocyané ou arylsélanyle. Dans une première partie, le trisélénodicyanure (TSD) généré à partir du malononitrile et du dioxyde de sélénium a été utilisé pour la substitution électrophile d’hétérocycles riches en électrons tels que les imidazohétérocycles, les chromèn-4-ones et également pour l’ipso-sélénocyanation d’acides arylboroniques sans l’utilisation de métaux. Cette sélénocyanation permet d’accéder rapidement et de façon fiable aux dimères diséléniés correspondants, très utilisés en tant que réactifs de départ. Dans une seconde partie, une première bischalcogénation sélective d’imidazo[1,2-a]pyrimidines a été mise au point sur les positions 3 et 6 à partir de dimères dichalcogénés en présence d’iode et d’acide phosphorique dans le DMSO. Une C3-arylsulfénation d’imidazo[1,2-a]pyrimidines à partir d’arylsulfinates de sodium sans utiliser de réducteur a également été décrite. Dans une dernière partie, s’appuyant sur les propriétés redox intéressantes du sélénium, les composés sélénocyanés ont été testés sur la leishmaniose. En séries imidazo[1,2-a]pyridine ou imidazo[2,1-b]thiazole, trois molécules ont présenté une bonne activité leishmanicide de l’ordre du micromolaire ainsi qu’une faible cytotoxicité engendrant un indice de sélectivité supérieur à celui de l’amphotéricine B, molécule de référence
This work focuses on the research and development of new methodologies for the synthesis of selenocyanate and arylselanyl molecules. In first part, triselenodicya-nide (TSD) generated from malononitrile and selenium dioxide was applied to the electrophilic substitution of electro-enriched heterocycles such as imidazoheterocycles, chromen-4-ones and ipso-selenation of arylboronic acids without the use of metals. This selenocyanation provides fast and reliable access to the corresponding diselenated dimers widely used as starting reagents. In a second part, a first selective bischalcogenation of imidazo[1,2-a]pyrimidines was developed at positions 3 and 6 from dichalcogenated dimers in the presence of iodine and phosphoric acid in DMSO. This work also allowed us to develop a C3-arylsulfenation of imidazo[1,2-a]pyrimidines from sodium arylsulfinates without the use of a reducer. In a final section, based on the interesting redox properties of selenium, the selenocyanates were tested on leishmaniasis. In imidazo[1,2-a]pyridine or imidazo[2,1-b]thiazole series, three molecules showed good leishmanicidal activity in the micromolar range as well as low cytotoxicity resulting in a higher selectivity index than amphotericin B, a drug used as a reference

1,2-Dioxines are a specific class of cyclic peroxide that are both prevalent in nature and important synthetic building blocks. To date, much of the chemistry involving 1,2-dioxines is concerned with cleavage of the weak peroxide bond, providing a convenient method for the incorporation of 1,4-oxygen functionality into molecules. Comparatively little attention has been directed towards transformations of the alkene unit contained within 1,2-dioxines, which is the focus of this thesis. The synthesis of a broad range of diversely functionalised 1,2-dioxines from commonly available starting materials is presented. Subsequently, the osmium catalysed dihydroxylation of 3,6-disubstituted 1,2-dioxines was investigated, furnishing novel peroxy diols in high yield and with excellent diastereoselectivity. The peroxy diols were then reduced, affording stereospecific tetraols and higher polyols, including the rare sugar allitol. In addition, homolytic ring-opening of the 1,2-dioxanes was examined, providing a new route to polyhydroxylated furanoses, highlighted by the synthesis of the natural keto-sugar psicose. Several 4-substituted 1,2-dioxines were also dihydroxylated, followed by reduction of the peroxide bond, providing a convenient route to branched erythritol derivatives, including the important plant sugar 2-C-methyl-erythritol. The cobalt catalysed ring-opening of the peroxy diols produced novel erythrose derivatives in high yield. In addition, the triphenylphosphine induced ring contraction of the peroxy diols is presented, which allowed for the synthesis of novel dihydroxylated tetrahydrofurans in excellent yield. Asymmetric dihydroxylation of the achiral 4-substituted 1,2-dioxines was explored, furnishing optically enriched peroxy diols with varying enantioselectivity depending on the substrate. The synthesis of novel alkyl and aryl branched erythrono-γ-lactones via oxidation of lactols derived from the acetonide protected peroxy diols is also documented. The utility of this sequence is illustrated by the preparation of potassium 2,3,4-trihydroxy-2-methylbutanoate, a leaf-closing substance of Leucaena leucocephalam. Additionally, γ-lactones were prepared from epoxy hydroxy ketones derived from epoxy-1,2-dioxanes, facilitated by a Baeyer-Villiger lactonisation protocol. The requirements and limitations of this procedure are discussed. The proposed and attempted synthesis of other lactones from 1,2-dioxines was also examined. Finally, several other general alkene transformations were investigated on 1,2- dioxines including: halo-hydrin formation, phenylselenyl chloride addition, aminohydroxylation, cyclopropanation, and aziridination, allowing for the preparation of several new classes of functionalised 1,2-dioxines. In summary, the work presented in this thesis establishes clear and efficient methodology towards several interesting and useful sugar-type core structures from modified 1,2-dioxines.
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Thesis (Ph.D) -- University of Adelaide, School of Chemistry and Physics, 2008

My thesis work revolves around the ability to modify the 1,4,8,11-tetraazacyclotetradecane (cyclam) framework in order tune the electronic properties of resulting metal complexes towards real life applications. A huge direction for science and engineering is the pursuit of Moore’s Law, to constantly miniaturize electronic processes while improving their performance. With the physical limits of copper wiring being reached on nanoscale levels, alternative resources must be utilized. Naturally, the absolute limit of wiring would be on the single molecular scale. It is this idea that Chapters 1-3 are founded upon. Moving forward, I deemed three key concepts are important for success of this project: (1) the ability for modification of the molecule to be incorporated into existing technologies, (2) redox stability of the molecular complexes to allow multiple charges to pass through without losing integrity, and (3) the ability to function as a wire and allow current to pass through. Requirement (1) has been proven possible in previous work on cyclam, however (2) and (3) were yet to be shown for any cobalt tetraazamacrocyclic complex until this work.

Chapter 1 covers my first successful exploration into modification of the cylcam ligand in order to obtain favorable electronic properties. Cobalt complexes utilizing the MPC ligand (5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradecane) show stability upon reduction, whereas the cyclam analogues did not. In fact, [Co(MPC)(C₂Ph)₂]⁺ was the first cobalt based tetraazamacrocyclic alkynyl complex to show such redox stability without the use of heavily electron withdrawing axial ligands. It was found that this improvement of redox stability is a result of the weakened equatorial ligand field caused by the steric bulk of the phenyl substituents of the cyclam framework. This in turn led to improved axial ligand bonding and hence greater stability. This work shows the Co^III(MPC) framework can satisfy requirement (2).

Based on the results of Chapter 1, Chapter 2 realizes the idea that with improved axial ligand bond strengths in Co^III(MPC) complexes, the possibility for electronic delocalization between cobalt and the axial ligand performing as the wire is opened. A series of dinuclear Co^III(MPC) complexes, with cobalt centers linked through a butadiyndiyl bridge, were prepared. With each cobalt being identical, theoretically each should behave electrochemically similar and reduction of the complex should be a single two electron event. It is however shown that this two electron event was, in fact, split into two single electron events. The source of this result is the delocalization of the first added electron between both cobalt centers, effectively making two half-reduced metals. Therefore, the ability for Co^III(MPC) complexes to satisfy requirement (3) has been proven.

Chapter 3 expands on the results shown in Chapters 1 and 2. Where Chapter 2 showed delocalization of an electron between cobalt centers, Chapter 3 shows delocalization of a hole through cobalt between ethynylferrocene ligands. With this, all three requirements are met and the ability as Co(MPC) to function as a wire has been proven for both oxidation and reduction, both between cobalt and through cobalt.

Chapter 4 takes a new direction, however applies the same basic principle as the previous three in modifying the cyclam ligand to achieve desired properties. Where application in electronic devices are made stable by use of the bulky MPC ligand, application towards catalysis requires an open catalytic site and weak enough axial coordination to allow the substrate to leave once reduced. Through the alkyl substitution of the cyclam ligand in Ni^II(CTMC) (5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradecane) in place of the MPC ligand, electronically donating properties of the macrocycle were maintained while opening the axial catalytic site. In this work, it was shown that reduction in steric bulk of the ligand from phenyl to ethyl to methyl, while maintaining electron donating properties, improved catalytic efficiency and all complexes were superior to Ni^II(cyclam).

To screen amine solvents for application in CO2 capture from coal-fired power plants, the equilibrium CO2 partial pressure and liquid film mass transfer coefficient were characterized for CO2-loaded and highly concentrated aqueous amines at 40 – 100 °C over a range of CO2 loading with a Wetted Wall Column (WWC). The acyclic amines tested were ethylenediamine, 1,2-diaminopropane, diglycolamine®, methyldiethanolamine (MDEA)/Piperazine (PZ), 3-(methylamino)propylamine, 2-amino-2-methyl-1-propanol and 2-amino-2-methyl-1-propanol/PZ. The cyclic amines tested were piperazine derivatives including proline, 2-piperidineethanol, N-(2-hydroxyethyl)piperazine, 1-(2-aminoethyl)piperazine, N-methylpiperazine (NMPZ), 2-methylpiperazine (2MPZ), 2,5-trans-dimethylpiperazine, 2MPZ/PZ, and PZ/NMPZ/1,4-dimethylpiperazine (1,4-DMPZ). The cyclic CO2 capacity and heat of CO2 absorption were estimated with a semi-empirical vapor-liquid-equilibrium model. 5 m MDEA/5 m PZ, 8 m 2MPZ, 4 m 2MPZ/4 m PZ and 3.75 m PZ/3.75 m NMPZ/0.5 m 1,4-DMPZ were identified as promising solvent candidates for their large CO2 capacity, fast mass transfer rate and moderately high heat of absorption. The speciation in 8 m 2MPZ and 4 m 2MPZ / 4 m PZ at 40 °C at varied CO2 loading was investigated using quantitative 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. In 8 m 2MPZ at 40 °C over the CO2 loading range of 0 – 0.37 mol CO2/mol alkalinity, more than 75% of the dissolved CO2 exists in the form of unhindered 2MPZ monocarbamate, and the rest is in the form of bicarbonate and dicarbamate; 19% - 56% of 2MPZ is converted to 2MPZ carbamate at 0.1 - 0.37 mol CO2/mol alkalinity. A rigorous thermodynamic model was developed for 8 m 2MPZ in the framework of the Electrolyte Nonrandom Two-Liquid (ENRTL) model. At 40 °C, the reaction stoichiometry for 2MPZ and CO2 is around 2 at lean loading but diminishes to 0 at rich loading. Bicarbonate becomes the major product at CO2 loading greater than 0.35 mol/mol alkalinity. The predicted heat of CO2 absorption is 75 kJ/mol at 140 °C and decreases with temperature when CO2 loading is above 0.25. The mass transfer rate data for 8 m 2MPZ was represented with a rate-based WWC model created in Aspen Plus®. The reaction rate was described with termolecular mechanism on an activity basis. With minor CO2 loading adjustment and regression of pre-exponential kinetic constants and diffusion activation energy, a majority of the measured CO2 fluxes in the WWC experiments were fitted by the model within ±20% over 40 – 100 °C and 0.1 – 0.37 mol CO2/mol alkalinity. The diffusion activation energy for 8 m 2MPZ at the rich loading is about 28 kJ/mol. The activity-based reaction rate constant at 40 °C for 2MPZ carbamate formation catalyzed by 2MPZ is 1.94×1010 kmol/m3•s. The calculated liquid film mass transfer coefficients are in close agreement with the experimental values. The liquid film mass transfer rate is dependent on the diffusion coefficients of amine and CO2 to the same extent at lean loading and 40 °C. The sum of the powers for the two diffusivities is approximately equal to 0.5 over the loading range of 0 – 0.4 mol CO2/mol alkalinity. The sum of the powers for the dependence of the liquid film mass transfer coefficient on the carbamate formation rate constants (k2MPZ-2MPZ and k2MPZCOO--2MPZ) approaches 0.5 at very lean loading at low temperature, but it decreases as CO2 loading and temperature is increased. At 100 °C, the physical liquid film mass transfer coefficient is the most important factor that determines the liquid mass transfer rate. The pseudo-first order region shifts to higher range of physical liquid film transfer coefficient as temperature increases.
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Dissertação de mestrado em Química Medicinal
Over time, the interest in studying molecular systems using computational methods has increased. These methods allowed to interpret and organize experimental results in order to solve or suggest new procedures to respond to a certain problem. Synthesis of polyhydroxylated sugar-like compounds is difficult for organic chemists due to the necessary stereo- and regio- selectivity in the reactions. Monosaccharides are commonly employed as starting materials, but a multistep protection/deprotection manipulations are big disadvantage issues. The D-erythrose has been known for a long time but the poor chiral induction offered by this template prevent its large use in these types of reaction. Recently it was possible to obtain, a derivative of D-erythrose, the D-erythrosyl δ-lactone, that showed total facial selectivity in 1,3-dipolar cycloadditions and nucleophilic additions. Two types of sugar-like scaffolds (five- and six-membered lactones ring) are readily accessed from nucleophilic attack to D-erythrosyl δ-lactone template. Both templates are obtained through a stereo- and regio-selective synthetic route and from which five- and six-membered lactones are obtained. Theoretical and computational means revealed that the reactions leading to both lactones share a common pathway but diverge after the second nucleophilic attack that is also the rate-limiting step in one of the reactions. The synthesis of five-membered lactone requires the presence of hardnucleophiles and the full pathway requires 4 steps. The six-membered lactones require the presence of soft-nucleophiles and full catalytic process requires only 1 step. The origin of the stereo-selectivity is justified by an intrinsic characteristic of D-erythrosyl dlactone that forces the nucleophilic attack to occur only at one face of the lactone. The regio-selectivity is dependent on the nature of the attacking molecule, i.e, if hard or soft nucleophiles are used in the reactions. The inhibitory activity of D-erythrose derivatives (five- and six-membered lactones) were tested against α-glucosidase, β-glucosidase, α-galactosidase and β-galactosidase. The biological assay revealed that some of the tested compounds present high specificity for some of these enzymes, an important feature in the development of new drugs targeting glycosidases. Molecular docking studies with human-enzymes were also carried out to study the origin of the specificity of some of these compounds to these enzymes. The results indicate that the factor that plays a major role in the inhibitory activity of the Derythrose derivatives is the position of the sugar-like moiety inside the binding pocket. When an efficient interaction is obtained with this part of the molecule and the active site of the enzyme, the compounds present satisfactory inhibitory activity otherwise, they are inactive. In α-glucosidase and β-galactosidase, this sort of interaction is possible with some of the tested compounds and these are the only ones that present inhibitory activity. In β-glucosidase and α-galactosidase all the compounds are inactive because the active site is located at the bottom of the binding pocket and none of the compounds can interact with it with sugar-like moiety.
Ao longo do tempo, o interesse em estudar sistemas moleculares usando métodos computacionais aumentou. Estes métodos permitiram interpretar e organizar resultados experimentais para resolver ou sugerir novos procedimentos para responder a um determinado problema. A síntese de compostos semelhantes a açúcares polihidroxilados é difícil para os químicos orgânicos devido à necessária estereo- e regio-seletividade das reações envolvidas. Os monossacarídeos são comumente empregados como materiais de partida, mas os múltiplos passos de proteção/desproteção necessários são uma grande desvantagem apontada a estes métodos. A D-eritrose é conhecida há muito tempo, mas a baixa indução quiral oferecida por este modelo impede o seu uso em maior escala. Recentemente, foi possível obter um derivado de D-eritrose, a D-eritrosil δ-lactona, que mostrou total seletividade facial em ciclo-adições 1,3-dipolares e adições nucleofílicas. Dois tipos de esqueletos semelhantes a açúcar (anel de lactona de cinco ou seis membros) são facilmente obtidos através do ataque nucleofílico ao modelo de Deritrosil δ-lactona. Ambos os modelos são obtidos através de um método sintético estereo- e regio-seletivo, mas o mecanismo envolvido não era conhecido. Os resultados obtidos por métodos teóricos e computacionais revelaram que ambas as lactonas partilham a mesma via mecanística, mas divergem no segundo ataque nucleofílico que é o passo limitante numa das reações. A síntese do anel de lactona de cinco membros requer a presença de nucleófilos hard e exige 4 passos. As lactonas de seis membros requerem a presença de nucleófilos soft e a reação fica completa em apenas 1 passo. A origem da estereo-seletividade é justificada por uma característica intrínseca da Deritrosil δ-lactona que força o ataque nucleofílico a ocorrer apenas por uma das faces. A regio-seletividade depende da natureza do nucleófilo, isto é, se são utilizados nucleófilos hard ou soft nas reações. A actividade inibidora dos derivados de D-eritrose (lactonas de cinco e seis membros) foi testada contra α-glucosidase, β-glucosidase, α-galactosidase e β-galactosidase. Os ensaios biológicos revelaram que alguns dos compostos testados apresentam alta especificidade para algumas dessas enzimas, uma característica importante no desenvolvimento de novos fármacos com glicosidases como alvo. Estudos de Docking Molecular com enzimas humanas foram realizados para avaliar e perceber a especificidade que alguns desses compostos apresentaram para algumas dessas enzimas. Os resultados indicam que o fator que desempenha um papel importante na atividade inibitória dos derivados de D-eritrose é a posição do anel que mimetiza o açúcar dentro da bolsa de ligação. Quando uma interação eficiente é obtida com esta parte da molécula e o centro ativo da enzima, os compostos apresentam atividade inibitória satisfatória, caso contrário eles são inativos. Nas α-glucosidase e β-galactosidase, esse tipo de interação é possível com alguns dos compostos testados e estes são os únicos que apresentam atividade inibitória. Na β-glucosidase e α-galactosidase todos os compostos são inativos porque o centro ativo está localizado na parte inferior da bolsa de ligação e nenhum dos compostos consegue interagir de forma eficiente.

碩士
國立臺灣大學
藥學研究所
88
This study is aimed to synthesize two series of compounds, namely, substituted arylpiperazinyl benzothiazinone 1,1-dioxide (A) and substituted arylpiperazinyl quinazolinone (B) derivatives for evaluation of α1A adrenoceptor selectivity and are considered to be potential for treatment of benign prostatic hyperplasia (BPH). The synthesis of compounds in A series started from esterification of 3,4-dimethoxyphenyl acetic acid (25) in methanol with a catalytic amount of concentrated sulfuric acid to give 3,4-dimethoxy-1-(carbomethoxymethyl)benzene (26). Then 26 underwent chloro-sulfonation with chlorosulfonic acid to afford 4,5-dimethoxy-2-carbomethoxymethylbenzenesulfonyl chloride (27). Compound 27 was treated with (2-methoxyphenyl)piperazinylalkyl amines (23a-c) and (2-pyrimidinyl)piperazinylalkyl amines (24a-c) to give N-((4-(2-methoxyphenyl)piperazinyl)alkyl)-4,5-dimethoxy-2-carbomethoxymethyl benzenesulfonamides (28a-c) and N-((4-(2-pyrimidinyl)piperazinyl) alkyl)-4,5-dimethoxy-2-carbomethoxymethylbenzenesulfonamides (31a-c), respectively. The hydrolysis of 28a-c and 31a-c with methanolic NaOH afforded N-((4-(2-methoxyphenyl)piperazinyl)alkyl)-4,5-dimethoxy-2-carboxymethylbenzenesulfonamides (29a-c) and N-((4-(2-pyrimidinyl)piperazinyl)alkyl)-4,5-dimethoxy-2-carboxymethylbenzene sulfonamides (32a-c), respectively. Compounds 29a-c and 32a-c were then treated with phosphorus oxychloride to provide N-((4-(2-methoxyphenyl)piperazinyl)alkyl)-6,7-dimethoxy-2H-1,2-benzothiazin-(4H)-3-one 1,1-dioxide (30a-c) and N-((4-(2-pyrimidinyl)piperazinyl)-alkyl)-6,7-dimethoxy-2H-1,2-benzothiazin-(4H)-3-one 1,1-dioxide (33a-c), respectively. For the synthesis of compounds in series B, 2-aminobenzophenone (36) and urea underwent condensation at 195 ℃ afford 4-phenyl quinazolin-2-one (37). The reaction of 37 reacted with p-methoxybenzyl chloride (38) gave 1-(p-methoxybenzyl)-4-phenyl- quinazolin-2-one (39) which was then treated with sodium cyanoborohydride to provide 1-(p-methoxy benzyl)-4-phenyl-3,4-dihydroquinazolin-2-one (40). 30a-c and 33c were subjected to different receptor binding assays. The preliminary results revealed that designed target compound 30a-c and 33c possess affinity toward α1A、α1B、 D1、 D2S、 D2L and 5-HT1A receptors. The different carbon chain length between the heterocycle moiety and arylpiperazine also affect the affinity and selectivity among different receptors. Among these compounds, compound 30b possess high affinity toward α1A receptors with IC50 = 107.2 pM and the selectivity ratio for α1B 、5-HT1A 、D1 、 D2S and D2L receptors is 118 、 12 、 6640 、 1538 and 6006, respectively.

碩士
國立臺灣科技大學
化學工程研究所
84
A semi-flow type apparatus was employed in this study to measure the vapor-liquid equilibria (VLE) , for three binary composed of carbon dioxide with a close-boiling compound 1,2- dimethoxybenzene,2-methoxyphenol or p-cresol at temperatures from 323.15 K to 423.15 K and pressures up to 200 bar or near the critical pressures of the mixtures. The solubility of carbon the liquid phase, as evidenced by the experimental results , with increasing temperature and increases with increasing As the equilibrium pressures are higher than the critical carbon dioxide, the saturated composition of heavy compound in vapor phase increases dramatically. Retrograde behavior was in each binary system. Moreover, p-cresol is obviously less than 1,2-dimethoxybenzene and 2-methoxyphenol in carbon dioxide under experimental conditions . The volatility of 1,2- dimethoxybenzene is lower than that of 2-methoxyphenol at subcritical pressures of carbon dioxide but becomes greater at supercritical pressures of carbon dioxide. An empirical equation correlates well the saturated vapor compositions of the heavy components in terms of the density of carbon dioxide. The new VLE data were employed to determine the Henry' s constants and the second virial cross coefficients. new VLE data were also used to test the validity of three representative cubic equations of state with various mixing was shown that the Soave equation of state with the two-parameter van der Waals one-fluid mixing rules yielded the best results.

博士
臺灣大學
藥學研究所
98
While chronic inflammation is widely believed to be a predisposing factor for cancer, the exact mechanisms linking these conditions have remained elusive. CX9051, a benzo[1.3.2]dithiazolium ylide 1,1-dioxide derivative identified as a COX-2 and 5-LOX dual inhibitor in our laboratory, exhibited anti-inflammatory activity and anti-proliferation effects. Our results demonstrated that CX9051 suppressed the LPS-induced PGE2 production and TNF-α generation and attenuated the protein expression of COX-2, iNOS, Akt, and NF-κB as well as NF-κB translocation. Furthermore, CX9051 could inhibit the proliferation and induced apoptosis of prostate cancer cell lines. The effect has been shown to be mediated via the regulation of NF-κB, the induction of TRAIL and the activation of extrinsic apoptotic signaling, which cross-react the activation of mitochondria mediated intrinsic pathways, leading to the apoptosis of cancer cells. The anti-proliferation and anti-inflammatory activities of CX9051 revealed in this thesis provided a propelling evidence for CX9051 serving as a promising lead compound to provide anti- inflammatory and chemopreventive benefits. In addition, a scaffold modification approach has been employed to design a novel class of Top I inhibitor in this thesis. The most effective Top I inhibitor 26, a 3-substituted quinolin-4(1H)-one derivative, elicited its cytotoxic effects of Top I poison through Top I down-regulation, which paralleled the induction of DNA single-strand breaks and followed with curative anti-tumor activity against the colon carcinoma xenograft tumor model. According to the impressive Top I inhibitory activity, pro-apoptotic activity in HT-29 cells and in vivo xenograft inhibition activity exhibited by 26, this investigation has provided an alternative lead compound for the development of novel Top I inhibitor for the treatment of cancer. In conclusion, the results in this thesis suggested that benzo[1.3.2]dithiazolium ylide 1,1-dioxide and 3-substituted quinolin-4(1H)-one derivatives were promising leads for the development of anti-inflammatory drugs and anticancer agents, respectively.

碩士
國立臺灣大學
藥學研究所
90
This thesis is aimed in (i) the design and synthesis of 6-oxo-indolo[1,2-b]benzo[1,2,4]thiadiazine 12,12-dioxide derivatives, analogues of tryptanthrin, as potential novel anticancer drugs; (ii) tryptanthrin containing polyamine side chain, by enhancing the binding ability with DNA to act as stabilizing agent of triplex DNA. Due to the results of satisfactory inhibitory activities of tryptanthrin derivatives against various cancer cell lines, 6-oxo-indolo[1,2-b]benzo[1,2,4]thiadiazine 12,12-dioxide (23) and its derivatives were designed and synthesized on the basis of bioisosterism concept. This structurally new planar skeleton ring system has never been reported previously. It is not only a new series of heterocycles worthwhile to develop but also expected to have potential in anticancer activity due to the presence of benzenesulfonamide moiety. The result from molecular modeling demonstrated that this four-ring system contained the planar structure and conjugated effect to the same extent with tryptanthrin. Appropriate isatins were chlorinated by phosphorus pentachloride and then underwent coupling reaction with 2-aminobenzenesulfonyl fluoride (46) to afford target compounds 23 and its derivatives 8-methyl- (53a), 10-bromo- (53b) and 8,9-difluoro-6-oxo-indolo[1,2-b]benzo[1,2,4]thiadiazine 12,12-dioxide (53c). In preparing DNA stabilizing agent, the nucleophilic substitution of monoprotected {3-[(3-aminopropyl)methylamino]propyl}carbamic acid t-butyl ester (64) and 5,6-difluoroisatin (48c) gave surprising result. It is the product from the middle tertiary amine, shorter side chain 6-[N-(t-butyloxycarbonylamino-propyl)-N-methylamino]-5-fluoroisatin (66), not the expected long chain product of 6-{[(t-butyloxycarbonylaminopropyl)amino]propyl}amino-5-fluoroisatin (65). The same result was obtained even though different reaction conditions were employed. The isatin 66 was then coupled with isatoic anhydride in pyridine to afford trytanthrin derivative 67, which was then deprotected by TFA to give the final product, the TFA salt of 9-[N-(3-aminopropyl)-N-methylamino]-8-fluoroindolo[2,1-b]quinazolin-6,12-dione (68).

碩士
國立中興大學
化學系所
106
Ten di-nuclear nickel complexes based on Salen-type derivatives containing bezothiazole and benzotriazole functionalities have been synthesized and structurally characterized by X-ray, elementary analysis and LC-MS. First, di-nuclear nickel complexes (1)-(4) were synthesized from a series of BiIBThP with different substituted functional group and were performed as one-component catalyst for copolymerization of carbon dioxide and cyclohexene oxide (CHO). The best catalytic activity (TOF=51 h-1) with high copolymerization selectivity and controlled molecular weight (Mn=35,000 g/mol) as well as high content carbonate linkages were obtained by using di-Ni complex (1), which functional group is substituted by methoxy group. For a given BiIBThP with the methoxy functionality, di-nuclear nickel complexed (1), (5)-(9) with different co-ligands were also prepared. Without co-catalyst, all of them have good activity for copolymerization with CO2/CHO. Among them, the complex (7) has the best activity (TOF= 65 h-1) within 6 h. CO2/CHO copolymerization catalyzed by complex (5) in the presence of excess PCHC polyol with small molecular weight can be produced. A unimodal molecular weight distribution was observed by GPC, and the resulting polymer microstructure, which were further identified by MALDI-TOF, NMR and LC-MS.

碩士
國立中興大學
化學系所
107
Novel structurally well-defined di-nuclear nickel complexes, ([(OMe3CHDiBThP)Ni2(OAc)2(H2O)] (1), [(Me3CHDiBThP)Ni2(OAc)2(H2O)] (2), [(Cl3CHDiBThP)Ni2(OAc)2(H2O)] (3), [(OMe3CHDiBThP)Ni2(DNP)2(MeOH)] (4), [(Me3CHDiBThP)Ni2(DNP)2(H2O)] (5), [(Cl3CHDiBThP)Ni2(DNP)2(MeOH)](6), [(OMe3CHDiBThP)Ni2(O2CCF3)(H2O)][ClO4](7), [(OMe3CHDiBThP)Ni2(O2C7F5)2] (8) , [(Me3CHDiBThP)Ni2(O2C7F5)(MeOH)2][ClO4](9), [(Cl3CHDiBThP)Ni2(O2C7F5)(MeOH)(H2O)][ClO4](10), [(OMe3CHDiBThP)Ni2(Cl)2(MeOH)2](11), [(Me3CHDiBThP)Ni2(OAc)2(HOAc)] (12) coordinated by the benzothiazole containing Salan-type ligand with ancillary nitrophenolate or carboxylic acid derivatives have been synthesized for polymerization catalysis. All of nickel complexes have been fully characterized by X-ray craystallography, elementary analysis and ESI-MS. Experimental results revealed that air-stable complexes 1-12 were shown to effectively catalyze copolymerization of epoxide with carbon dioxide (CO2). Among them, complex 3 incorporating chloro and acetato groups showed the best catalytic performance (TOF = 83 h-1) and narrow polydispersity index (PDI) (＜1.25) with a good copolymer selectivity during copolymerization of cyclohexene oxide(CHO) and CO2. In addition, the molecular weights of PCHC polymers catalyzed by complex 3 was in a controllable character with a range from 20600–27000 g mol−1. On the other hand, the structural information of the PCHC from MALDI-TOF experiment showed that the series of peaks could be divided into an interval of about 142 Da which indicates a repeated unit of PCHC chains and these peaks also suggest that the chain propagation of copolymerization was initiated by acetate group as an initiator. The result have successfully verified that di-nickel complex 3 was a new high potential catalyst for copolymerization of CHO with CO2.

碩士
國立交通大學
應用化學系
88
Synthesis of Dioxa- and Trioxa- Cage Compounds 12 and 16 as Probes to Determine the Stereochemistry of the Redution Products of 2,3-Diacylnorbornene Derivatives 6 and 7. Ozonolysis of diols 6a-c,followed by addition of n-butylamine or isopropylamine, gave dioxamonoaza-cages 19 and 20. Reaction of 16 with Lawesson's Reagent in dichloromethane gave the transformation product 29. Reaction of 16 with three equivalents of triethylsilane(at -78℃),in dichloromethane in the presence of TiCl4 gave the double nucleophilic substitution products 32.

博士
中原大學
化學研究所
101
Several novel metal complexes bearing BTP ligands (BTP = N,O-bidentate benzotriazole phenoxide), [{(-C1BTP)AlMe2}2] (1), [(C1BTP)2AlMe] (2), [(C1BTP)3Al] (3), [(C1BTP)2Al(OAn)] (4), [{(C1BTP)2Al}2(-O)] (5), [{(C1BTP)2Al(-OH)}2] (6), [(C1BTP)Al2Me5] (7), [(CMe2PhBTP)AlMe2] (8), [(t-BuBTP)AlMe2] (9), [(CMe2PhBTP)2AlMe] (10), [{(CMe2PhBTP)2Al}2(-O)] (11), [(TMClBTP)2Mg(THF)2] (12), [(CMe2PhBTP)2Al(NMe2)] (13), [(t-BuBTP)2Al(NMe2)] (14), [(TMClBTP)2Al(NMe2)] (15), [{(t-BuBTP)2Al}2(-O)] (16), [{(TMClBTP)2Al}2(-O)] (17), [(-C8BTP)Ti(OiPr)3]2 (18), [(C8BTP)2Ti(OiPr)2] (19), [(t-BuBTP)2Ti(OiPr)2] (20), [(TMClBTP)2Ti(OiPr)2] (21) and trimetallic complexes incorporated by amine-bis(benzotriazole phenolate) ligands, [(C1NNBiBTP)2Mg3(OBn)2] (22), [(C1PPBiBTP)2Mg3(OBn)2] (23), [(C1NNBiBTP)2Zn3(OAc)2] (24), [(C1NNBiBTP)2Co3(OAc)2] (25) and [(C1NNBiBTP)2Ni3(OAc)2(H2O)2] (26) were synthesized and structurally characterized. Their optical properties and catalytic activities in ring-opening polymerization (ROP) of lactone and carbon dioxide/epoxides coupling and copolymerization were systematic studied. Luminescent properties of complexes 1-3 and 5-7 in solution were studied, and it was found that the maxima emission wavelength (max) of 1-3 and 5-7 is in the range 492 to 500 nm and the quantum yield is 0.020-0.118, depending on the BTP ligands coordinating to the metal center. Experimental results demonstrated that complexes 4, 11/(9-anthracenemethanol (9-AnOH)), 12/9-AnOH, 15, 18 and 19 efficiently catalyze the ring-opening polymerization of -caprolactone (-CL) or/and L-lactide (L-LA) in a controlled fashion, yielding polymer with the expected molecular weights and narrow polydispersity indices (PDIs). Single-site Al amide 15 is an efficient initiator for the LA polymerizations with a living character, and the polymerization displays a first-order dependence on the L-LA concentration. Kinetic studies of ε-CL polymerization initiated by 18 were investigated using in situ 1H NMR spectroscopy; the polymerization exhibited first-order dependence on both complex 18 and ε-CL concentrations. Additionally, bimetallic BTP-ligated alumoxane 17 is an active catalyst (TOF: 120 h-1) for the coupling of CO2 with PO in the presence of n-Bu4NBr to give propylene carbonate under mild conditions. New trimetallic magnesium complexes bearing amine-bis (benzotriazole phenolate) were synthesized for bifunctional catalysis. Complex 22 catalysed -CL polymerizations in not only a ‘living’ manner but also in an ‘immortal’ fashion. Additionally, tri-Mg 22 was active for the coupling of CO2 with cyclohexene oxide (CHO) on addition of n-Bu4NBr co-catalysts to give cis-cyclohexene carbonate under mild conditions. A novel tri-Co 25 catalyst for the copolymerization of CHO and CO2 in controlled manner, yielding poly(cyclohexene carbonate) with the highly molecular weights and narrow PDIs (Mn = 10100, PDI = 1.39). The 25/n-Bu4NCl catalytic system shows good productivity (TON: 990) and activity (TOF: 495 h-1) under optimal conditions.