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Dissertations / Theses on the topic 'Benzyl ethers'
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1
Fruteau, de Laclos Anne-Marie F. (Anne-Marie François). "Cleavage of benzyl aryl ethers by chlorine." Thesis, McGill University, 1991. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=70291.
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In order to extend application of the gel-degradation mechanism of delignification, model compounds of the general structure (3,4-dimethoxyphenyl)-CH(OR)R$ sp prime$ were treated at room temperature with increasing charges of molecular Cl$ sb2$ in glacial HOAc.<br>Catalytic amounts of Cl$ sb2$ cleaved benzyl aryl ether bonds (OR=2-methoxy-4-methylphenoxy) before any ring chlorination occurred. Yields of cleavage decreased in the order: R$ sp prime$=H; R$ sp prime$=$-$CH$ sb2$-2-methoxyphenoxy; R$ sp prime$=$-$CH(CH$ sb2$OH)-2-methoxyphenoxy. These results support the concept that the delignification of wood pulp by chlorine results from benzyl aryl ether cleavage. The conditions of the reaction, as well as control reactions with hydrochloric acid, suggest that the cleavage is due to conventional acid hydrolysis induced by chlorine. The experimental evidence does not rule out another possible mechanism in which the cleavage is initiated by molecular chlorine.<br>Benzyl ether links were generally stable in models of the benzyl alkyl type, whose primary reactions were ring chlorination. A large excess of chlorine caused side-chain displacement, hitherto considered the primary reaction in the solubilization of lignin.
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Greenhalgh, Richard P. "Diasteroselective Wittig rearrangements." Thesis, University of Kent, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.359407.
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Sandrin, Franco. "Lewis acid catalyzed reactions of 1-benzyl-2, 5-bis (trimethylsiloxy) pyrrole." Thesis, McGill University, 1985. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=66047.
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Hughes, Samantha Jayne. "A computational and synthetic study of poly(benzyl phenyl ether) dendrimers." Master's thesis, University of Cape Town, 1998. http://hdl.handle.net/11427/17221.
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Includes bibliographies.<br>Organic and organochromium poly(benzyl phenyl ether) dendrimers have been investigated by synthetic · and computational methods. The first generation organic benzyl alcohol and bromide wedges have been prepared, and a first generation organic dendrimer was synthesised. The preparation of novel organochromium dendrimers has been investigated. Several chromium arene complexes were prepared by different routes, and the halogenation methodology was thoroughly explored with various reagents. The target compound, a chromium complexed first generation dendritic wedge, was not accessible by any of the methods investigated. The novel compound (dibenzyl ether)bis[tricarbonylchromium(O)] has been prepared by two routes and the crystal structure of this complex was determined. Several other chromium arene complexes were synthesised, and the crystal structure of one of these, (benzyl methyl ether)tricarbonylchromium(O), was determined. The structure and properties of the organic and organochromium dendrimers have been investigated by molecular mechanics and molecular dynamics techniques. The existing CHARMm polymer force field was extended to include parameters for the tricarbonylchromium moiety. The two crystal structures solved as part of the synthetic effort, were used in this regard. The accuracy of the new parameters was assessed by simulation of the crystal structure of ( dibenzyl ether)bis[tricarbonylchromium(O)]. The important ether linkage torsion angle parameter, which plays a significant role in the topology of the dendrimer, was singled out for refinement. The torsion angle was parameterised with the model compound benzyl phenyl ether, by fitting the CHARMm results for rotation about the dihedral, to ab initio torsional data. Molecular dynamics simulations have been performed on generations one through five of the organic and organochromium dendrimers. The radius of gyration and RMS variation were investigated as a function of generation for both dendrimer series. The radius of gyration was found to increase exponentially with generation, whereas the relationship of RMS variation to generation was not as well defined. Density distributions were calculated for all five generations of the organic and organometallic dendrimers. In addition, the distribution of the monomers from each generation within the dendrimer was analysed. In the later generation dendrimers, the monomers belonging to the earlier generations are extended, while the terminal groups are mobile and found in all regions of the dendrimer. The solvent accessible surface was calculated for the organochromium dendrimers. It was concluded from these results that although the terminal groups are mobile, the majority of these monomers remain on the periphery of the dendrimer, or in solvent accessible areas.
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Deora, Nipa. "Computational Studies of Protonated Cyclic Ethers and Benzylic Organolithium Compounds." Diss., Virginia Tech, 2010. http://hdl.handle.net/10919/27800.
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Protonated epoxides feature prominently in organic chemistry as reactive intermediates. Gas-phase calculations studying the structure and ring-opening energetics of protonated ethylene oxide, propylene oxide and 2-methyl-1,2-epoxypropane were performed at the B3LYP and MP2 levels (both with the 6-311++G** basis set). Structural analyses were performed for 10 protonated epoxides using B3LYP, MP2, and CCSD/6-311++G** calculations. Protonated 2-methyl-1,2-epoxypropane was the most problematic species studied, where relative to CCSD, B3LYP consistently overestimates the C2-O bond length. The difficulty for DFT methods in modeling the protonated isobutylene oxide is due to the weakness of this C2-O bond. Protonated epoxides featuring more symmetrical charge distribution and cyclic homologues featuring less ring strain are treated with greater accuracy by B3LYP.
Ion-pair separation (IPS) of THF-solvated fluorenyl, diphenylmethyl, and trityl lithium was studied computationally. Minimum-energy equilibrium geometries of explicit mono, bis and tris-solvated contact ion pairs (CIPs) and tetrakis-sovlated solvent separated ion pair (SSIPs) were modeled at B3LYP/6-31G*. Associative transition structures linking the tris-solvated CIPs and tetrakis-solvated SIPs were also located. In vacuum, B3LYP/6-31G* ΠHIPS values are 6-8 kcal/mol less exothermic than the experimentally-determined values in THF solution. Incorporation of secondary solvation in the form of Onsager and PCM single-point calculations showed an increase in exothermicity of IPS. Application of a continuum solvation model (Onsager) during optimization at the B3LYP/6-31G* level of theory produced significant changes in the Cα-Li contact distances in the SSIPs. An increase in of ion pair separation exothermicity was observed upon using both PCM and Onsager solvation models, highlighting the importance of both explicit and implicit solvation in modeling of ion pair separation.<br>Ph. D.
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Bronk, John M. "Synthesis and characterization of poly (butyl vinyl ether) homopolymers and copolymers utilizing the aluminum hydrogen sulfate catalyst system." Thesis, This resource online, 1991. http://scholar.lib.vt.edu/theses/available/etd-08182009-040347/.
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Yigitsoy, Basak. "Benzyl Functionalized Benzotriazole Containing Conjugated Polymers: Effect Of Substituent Position On Electrochromic Properties And Synthesis Of Crown Ether Functionalized Electrochromic Polymers." Phd thesis, METU, 2011. http://etd.lib.metu.edu.tr/upload/12613309/index.pdf.
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A new class of &pi<br>-conjugated monomers was synthesized with combination of electron donating and electron-withdrawing heterocyclics to understand the effects of structural differences on electrochemical and optoelectronic properties of the resulting polymers. Electron deficient benzotriazole, substititued with benzyl from two available sites, coupled with stannylated electron donating groups, ethylenedioxythiophene (EDOT) and thiophene (Th), to yield four different monomers<br>1-benzyl-4,7-di(thiophen-2-yl))-2H-benzo[d][1,2,3] triazole (BBTA), 2-benzyl-4,7-di(thiophen-2-yl))-2H-benzo[d][1,2,3] triazole (BBTS), 1-benzyl-4,7-bis(2,3-dihydrothieno[3,4-b]dioxin-5-yl)-2H-benzo [d][1,2,3]triazole (BBTEA), 2-benzyl-4,7-bis(2,3-dihydrothieno[3,4-b]dioxin-5-yl)-2H-benzo [d][1,2,3]triazole (BBTES).
Furthermore, EDOT and thiophene terminated napthalene-2,3-crown ether containing monomers, 14,19-di(thiophen-2-yl)-naphtho[2,3-b][1,4,7,10,13] pentaoxacyclo pentadecane (TNCT), 14,19-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-naphtho[2,3-b][1,4,7,10,13]pentaoxacyclopenta decane (ENCE), were synthesized to observe the effect crown ether moiety on the final electrochemical and optoelectronic properties of resultant polymers.
Cyclic voltammetry, UV-Vis-NIR spectroscopy and colorimetry techniques were employed to examine electrochemical and optoelectronic properties of all monomers and polymers. Experimental results showed that alteration of substituent, substitution position and donor groups&rsquo<br>strength lead to obtain polymers with different redox behaviors, optical band gaps and different number of achievable colored states.
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Adnani, Driss. "Réactivité en cycloaddition [4+2] et [3+2] du tétrafluoroborate de 2-benzoyl-1, 2-dihyfroisoquinoléine - 1 carbonitrile (composé de Reissert dérivé de l'isoquinoléine) avec quelques énones et ethers d'enol. : Étude de la régio- et de la stéréochimie des cycloadduits." Besançon, 1995. http://www.theses.fr/1995BESA2022.
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Les réactions étudiées ont mis en évidence la réactivité des cétones Alpha, Beta éthyléniques vis-à-vis du tétrafluoroborate de 2-benzoyl-1, 2-dihydroisoquinoléines-1 -carbonitrile : on observe généralement une réaction de cycloaddition [4+2] qui conduit à des dérivés substitués de pyrrole. Dans le cas de deux de ces cétones, nous avons pu mettre en évidence la réaction concurrente de cycloaddition dipolaire 1,3 qui conduit à un dérivé de la pyrrolo(2,1 -a)isoquiléine. Ceci indique que l'on a doncà faire à deux réactions concurrentes même dans le cas des alcènes alors que McEwen indiquait que tous les alcènes donnaient lieu à une réaction de cycloaddition de type [4+2]. Lorsque l'énone mise en oeuvre comporte deux faces diastéréospécifiques comme c'est le cas avec les arylidéneindanones et -tétralones que nous avons utilisées, on observe une approche diastéréosélective des réactants. Notre étude a mis en évidence le rôle décisif des facteurs conformationnels pour rendre compte de la diastéréochimie observée. Les spirocomposés obtenus avec ces dernières énones peuvent s'ouvrir en milieu acide pour donner des dérivés tétrasubstitués de pyrrole. Enfin, les quelques réactions effectuées avec des éthers d'énol ont montré que pour les plus simples d'entre eux, c'est la réaction de cycloaddition dipolaire-1,3 qui intervient : ces ethers d'énol se comportent comme des alcynes masqués vis à vis du tétrafluoroborate de 2-benzoyl-1,2 dihydroisoquinoléine-1-carbonitrite au sens de McEwen. Nous avons proposé un mécanisme qui rend compte de la réactivité de ces alcènes particuliers.
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Souabi, Salah. "Etude de l'adsorption de tensioactifs cationiques sur charbon actif influence de coadsorbats /." Grenoble 2 : ANRT, 1988. http://catalogue.bnf.fr/ark:/12148/cb376186543.
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Hennequin, Laurent. "Nouvelle méthode de préparation de composés dicarbonylés-1,5 : application à la synthèse de substances naturelles." Rouen, 1986. http://www.theses.fr/1986ROUES026.
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On met au point une méthode générale de synthèse de composés delta-dicarbonylés et delta-dicarbonylés α -halogénés par action respectivement d'un éther d'énol silyle ou d'un éther d'énol silyle β-halogéné sur des carbocations fonctionnels. En milieu basique, les composés delta-dicarbonylés sont transformés en cyclohexénones, tandis que leurs anologues halogénés conduisent, selon la structure du composé de départ, à des cyclopropanes disubstitués trans ou à des spiranes hétérocycliques. Ces méthodes ont été appliquées à la synthèse d'alpha -cypérones. On a également préparé des synthons de bis-annélation et obtenu ainsi la homo-D deshydrotestostérone
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Bennis, Khalil. "Etude de l'adsorption et de la reduction electrochimique sur electrode de mercure de quelques cetones en presence de tensio-actifs en milieu aqueux." Clermont-Ferrand 2, 1988. http://www.theses.fr/1988CLF2E406.
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Etude de la reduction electrochimique de l'acetophenone, l'oxyde de mesityle et l'ethylideneacetone en milieu aqueux en presence d'agents de surface anioniques (laurylsulfate de sodium), d'agents de surface cationiques (bromure de benzyltrimethylammonium et bromure de cetyltrimethylammonium) et d'agents de surface non ioniques (brij 35 et poly(oxyethylene))
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ZHAO, CHENG-LONG, and 趙澄龍. "The study of iodide and bromide effect on the synthesis of benzyl ethers with tertiary amine as catalyst." Thesis, 1989. http://ndltd.ncl.edu.tw/handle/70812034395120293749.
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Ramanathan, Mani, and 馬瑞門. "Synthetic studies towards the antimalarial fungal polyketide Codinaeopsin via an intramolecular Diels-Alder reaction and Efficient deprotection of benzyl ethers and aryl acetals using triphenylphosphine hydrobromide." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/pbp37w.
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博士<br>國立中央大學<br>化學學系<br>101<br>Codinaeopsin (1) a new tryptophan derived polyketide was isolated in 2008 from an endophytic fungus collected in Costa Rica (Fig.1).1 The unique chemical structure of this target includes a densely substituted trans decalin carbocycle which is connected to an indole fragment through an unusual heterocyclic unit. Among the natural products found in this family, Codinaeopsin has the most substituted decalin unit with four methyl and a 1-methyl-propenyl groups attached to it. The unusual α-acyl-γ-hydroxy lactam (modified tetramic acid cores) with oxidized Cα position of tryptophan are often present in natural products from fungal sources. Codinaeopsin is having promising activity against plasmodium falciparum, the causative agent of most lethal form of malaria (IC50=2.33μg/mL) or 4.7μM. The structural complexity, together with the extraordinary biological profile, prompted us to choose this natural product as an ideal synthetic target. The synthetic plan relied on a late stage Lewis acid mediated intramolecular Diels-Alder (IMDA) reaction of E,E,E-triene with a suitable dienophile to yield the appropriately decorated decalin skeleton.The synthetic approach described here shares a number of key features, including rhodium catalyzed hydrogenation of commercially available mesitol, E-selective Horner-Wittig olefination protocol to construct the trisubstituted alkene and one pot TPAP oxidation/Wittig olefination of the sensitive polyene substrate. Syntheses of racemic exo and endo decalin cores of Codinaeopsin are accomplished via intramolecular Diels-Alder reaction under thermal and Lewis acidic conditions. The relative stereochemistry of these IMDA adducts were confirmed by NOE and single crystal X-ray techniques.
In chapter 2, Triphenylphosphine hydrobromide is reported to cleave the benzyl ethers derived from 1o, 2o, alkyl and aryl alcohols to the corresponding alcohols and benzyltriphenylphosphonium bromide in good yields. The reaction is optimized both under microwave and conventional heating conditions using stoichiometric amount of triphenylphosphine hydrobromide. The mechanism of this reaction is also discussed.
In chapter 3, Triphenylphosphine hydrobromide is reported to deprotect the aryl acetals and ketals to give the corresponding carbonyl compounds and alkyl phosphonium salts under convenient conditions (50 oC, microwave, 5 min. yields up to 90%). The reaction is compatible with acid sensitive functional groups and the mechanism is discussed through the substrates surveyed.
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Ramakrishna, T. "Synthesis, Metal Complexation And Catalytic Studies Of Poly(Ether Imine) And Poly(Benzyl Aryl Ether) Dendrimers." Thesis, 2004. https://etd.iisc.ac.in/handle/2005/1311.
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Ramakrishna, T. "Synthesis, Metal Complexation And Catalytic Studies Of Poly(Ether Imine) And Poly(Benzyl Aryl Ether) Dendrimers." Thesis, 2004. http://etd.iisc.ernet.in/handle/2005/1311.
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"Generation-independent dimerization behavior of quadruple hydrogen bond-containing oligo(benzyl ether) dendrons." 2006. http://library.cuhk.edu.hk/record=b5892931.
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Wong Chun Ho.<br>Thesis (M.Phil.)--Chinese University of Hong Kong, 2006.<br>Includes bibliographical references (leaves 72-77).<br>Abstracts in English and Chinese.<br>Contents --- p.i<br>Acknowledgments --- p.iii<br>Abstract --- p.iv<br>Abbreviations and acronyms --- p.vi<br>Publications originated from the work of this thesis --- p.viii<br>Chapter Chapter 1 - --- Dendritic Macromolecules and Dendronized Polymers<br>Chapter 1.1 --- Introduction to Dendrimers and Dendronized Polymers --- p.1<br>Chapter 1.2 --- Overview of the Synthesis of Dendronized Polymers --- p.4<br>Chapter 1.2.1 --- Graft-from Approach --- p.4<br>Chapter 1.2.2 --- Graft-to Approach --- p.5<br>Chapter 1.2.3 --- Macromonomer Approach --- p.6<br>Chapter 1.2.3.1 --- Step Growth Polymerization --- p.6<br>Chapter 1.2.3.2 --- Chain Growth Polymerization --- p.8<br>Chapter 1.2.3.3 --- Supramolecular Polymerization --- p.9<br>Chapter Chapter 2 - --- En Route to Hydrogen Bond-Mediated. Supramolecular Dendronized Polymers<br>Chapter 2.1 --- Design of Supramolecular Dendronized Polymers --- p.15<br>Chapter 2.1.1 --- Binding Modes in Supramolecular Polymers --- p.15<br>Chapter 2.1.1.1 --- Hetero-Complementary Polymerization --- p.16<br>Chapter 2.1.1.2 --- Self-Complementary Polymerization --- p.17<br>Chapter 2.1.2 --- The Effect of Binding Constant on the Degrees of Polymerization --- p.18<br>Chapter 2.1.3 --- The Effect of Dimerization Constant on the Molecular Weight Distribution --- p.21<br>Chapter 2.1.4 --- The Dendritic Effect on the UPy Binding Behavior --- p.21<br>Chapter 2.2 --- Summary --- p.24<br>Chapter Chapter 3 - --- "Design, Synthesis, and Structural Characterization of Dendronized Dimers"<br>Chapter 3.1 --- Design of Dendronized Dimers --- p.25<br>Chapter 3.1.1 --- The Nature of R and R on the Dimerization Behavior --- p.25<br>Chapter 3.1.2 --- Selection of Dendrons --- p.26<br>Chapter 3.1.3 --- Positioning of Dendrons and the Synthetic Feasibility --- p.27<br>Chapter 3.2 --- Synthesis of Dendronized Dimers --- p.28<br>Chapter 3.3 --- Characterizations of the Intermediates and Target Dimers --- p.31<br>Chapter 3.3.1 --- 1H NMR Spectroscopy --- p.31<br>Chapter 3.3.2 --- 13C NMR Spectroscopy --- p.38<br>Chapter 3.3.3 --- Mass Spectrometry --- p.41<br>Chapter 3.3.4 --- Vapor Pressure Osmometry --- p.43<br>Chapter 3.3.5 --- Infrared Spectroscopy --- p.43<br>Chapter 3.3.6 --- Gel Permeation Chromatography --- p.44<br>Chapter 3.4 --- Conclusions --- p.46<br>Chapter Chapter 4 - --- Determination of Dimerization Constants<br>Chapter 4.1 --- Overview of the Self-Assembling Process in UPy System --- p.47<br>Chapter 4.2 --- Determination of the Dimerization Constants (Kdim*) --- p.49<br>Chapter 4.2.1 --- Dimerization Constants in CDCl3 at 25 °C --- p.50<br>Chapter 4.2.2 --- Dimerization Constants in 10% (v/v) DMSO-d6/CDCl3 at 25 °C --- p.53<br>Chapter 4.2.3 --- Dimerization Constants in CDCl3 at 50 °C --- p.56<br>Chapter 4.3 --- Heterodimerization Experiment --- p.56<br>Chapter 4.4 --- Conclusions --- p.57<br>Chapter Chapter 5 - --- Experimental Procedures<br>Chapter 5.1 --- General Information --- p.60<br>Chapter 5.2 --- General Synthetic Procedures --- p.61<br>Chapter 5.3 --- Experimental Procedures --- p.62<br>References --- p.72<br>Appendix<br>NMR Spectra --- p.78<br>GPC results --- p.119
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Kang, Ting-Cih, and 康庭慈. "Liquid-phase hydrogenolysis of lignin model compound (benzyl phenyl ether) using a Ni/Carbon catalyst." Thesis, 2017. http://ndltd.ncl.edu.tw/handle/zj5qn2.
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碩士<br>國立臺灣大學<br>化學工程學研究所<br>105<br>Hydrogenolysis is a promising process to produce value-added products from lignin, which has received great attention in recent years. However, drastic conditions (i.e. high pressure and temperature) are required for selective generation of desired compounds from hydrogenolysis of lignin. In this thesis, we propose a liquid-phase hydrogenolysis system for selective cleavage of a lignin model compound (i.e. Benzyl phenyl ether (BPE)) under mild conditions. BPE is an α-O-4 model compound of lignin and has been used as a reactant to study the catalytic efficiency of lignin hydrogenolysis. In my system, various solvents over carbon black supported nickel (denoted as Ni/CB) catalyst with the presence of NaBH4 (i.e. the liquid hydrogen source) were investigated. We found that solvents play a vital role in our liquid-phase hydrogenolysis system, and the ethanol/water co-solvent with a ratio of 3/7 can dramatically enhance the conversion of BPE. With optimized reaction conditions, the maximum conversion of BPE was achieved at 99.2% and the yield of toluene and phenol was 46.3% and 45.1%, respectively. The kinetic study of BPE hydrogenolysis reveals that the activation energy in our system was less (i.e. 41.8 kJ·mol-1) than that of previous reports in literatures (i.e. 72 kJ·mol-1), which indicates the enhanced catalytic performance in our system.
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Wang, Yen-Jhung, and 汪彥璋. "1.Application of Halogenated Benzyl Ether in Carbohydrate Chemistry2.Iron-Catalyzed Cross-Coupling Reaction of Formamides with Thiols." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/88670261212170566024.
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碩士<br>國立中興大學<br>化學系所<br>101<br>The first part of this thesis, we introduce the halogenated benzyl ether as a new protecting group carbohydrate chemistry. First, the combination of palladium acetate (1.0 mol%) and Josiphos (1.0 mol%) can be used as a powerful catalytic system to form C-S bond between halogenated benzyl ethers with thiols. Interestingly, the resulting thioether-containging benzyl group can be selectively removed and afforded the corresponding alcohols.
In the second part of this thesis, we report that iron dichloride can be used as a catalyst for the coupling reaction of thiols with formamides in the presence of TBHP as an oxidant.
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ZHANG, QIONG-FEN, and 張瓊芬. "Synthesis and characterization of side-chain liquid crystalline polymethacrylates and polyacrylates containing benzyl ether based mesogenic side group." Thesis, 1990. http://ndltd.ncl.edu.tw/handle/67575592479810954997.
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Chou, Hua-Cheng, and 周華晟. "Designed to Synthetic Benzyl Ether-Linked Glucuronide Derivative of Benzo[de]quinoline camptothecin(BQC) for Selective Anticancer Therapy." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/17913684817324924372.
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碩士<br>嘉南藥理科技大學<br>藥學系<br>101<br>5, 6-Dihydro-4H-benzo[de]quinolone camptothecin (BQC), a derivative of camptothecin, has been identified as a potential anti-tumor drug. Additionally, BQC could be conjugated with a methyl glucuronate to improve its tumor specificity and also its water solubility. Dr. Masamichi. firstly synthesized compound 6 from compound 1 through nitrification, oxidation and reduction. Compound 6 then was conjugated with compound 7 to give BQC. However, when the start material is compound 1, the nitrification step would produce a 6-nitro and 6, 8-dinitro byproduct, thus it requires purification of the 8-nitro main product. The yield of nitrification and oxidation is 13.0% and 77.4%, respectively, the total yield is just 10%. In our study, in order to increase the total yield, we modified the synthesis process. We obtained compound 5 by using the same starting material (compound 1) but with different orders, which are oxidation and nitrification. The yield of oxidation and nitrification is 42.7% and 69%, respectively. The total yield is 33%. It is 3-folds better than the original process.
In order to improve the practicality of clinical applications by increased the tumor targeting, we were according to the strategy of prodrug. We have been designed and synthesized a BQCG -ester type compound.
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MAO, Yung-jen, and 毛勇仁. "Phase Behavior and Miscibility in a Ternary Blend System Comprising Polycaprolactone, Poly(benzyl methacrylate) and Poly(vinyl methyl ether)." Thesis, 2000. http://ndltd.ncl.edu.tw/handle/15644801075846606593.
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碩士<br>國立成功大學<br>化學工程學系<br>88<br>Phase behavior and miscibility of a ternary polymer blend comprising polycaprolactone (PCL), poly(benzyl methacrylate) (PBzMA) and poly(vinyl methyl ether) (PVME) was investigated by polarizing optical microscopy (POM), scanning electron microscopy (SEM), differential scanning calorimeter (DSC) and Fourier-transform infrared spectroscopy (FTIR). Each composition of the ternary mixture forms a miscible blend with a homogeneous phase structure. The ternary blend system exhibits lower critical solution temperature (LCST) behavior through optical observation for phase separation on heating. The existence of a single Tg in each blend also indicates that the ternary blend system is miscible according to the conventional standard of glass transition. Nevertheless, widening of the thermal transition breadth was obvious and contingent upon blend composition suggesting that miscellaneous scales of molecular aggregation. The FTIR result shows that the intermolecular interactions were weak and not specific
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GUO, YU-CHENG, and 郭昱成. "(Thiolan-2-yl)diphenylmethanol Benzyl Ether-catalyzed Asymmetric Cyclopropanation of Chalcones with Cinnamyl Bromide & Development of New Chiral Furan Compound." Thesis, 2017. http://ndltd.ncl.edu.tw/handle/3ed5t3.
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碩士<br>國立中正大學<br>化學暨生物化學研究所<br>106<br>This work describles catalytic and asymmetric cyclopropanation by using (Thiolan-2-yl)diarylmethanol benzyl ether as an organocatalyst. We optimized the reaction condition by screening solvents, bases, additives, temperatures and catalysts. The most important factors are solvent and temperature, which affect the diastereoselectivity and enantioselectivity. Under the optimized reaction conditions, cinnamyl bromide reacted with trans-chalcones via the CoreyChaykovsky reaction to give major cis-vinylcyclopropanes with up to 95% ee.
Besides, we synthesized a chiral furan compound. It was synthesized from -valerolactone through six steps in 61% total yield. The key step is using asymmetric Sharpless dihydroxylation reaction to build the stereogenetic center of the furan ligand with 99% ee.
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Cusson, Jean-Philippe. "Étude de la cyclisation de lactones à 9 membres par réaction de métathèse et formation catalytique de liens benzyliques asymétriques." Thèse, 2017. http://hdl.handle.net/1866/19342.
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Préalablement, une synthèse de l’aliskiren, un inhibiteur de la rénine développé pour le traitement de l’hypertension, a été réalisée auprès du groupe Hanessian. Durant cette synthèse, une réaction clé de cyclisation par métathèse, menant à la formation de lactone à neuf membres, a été réalisée. Durant cette réaction, nous avons observé une différence de réactivité entre les diastéréomères, menant à la formation de monolactones et de dilactones, générant ainsi de l’intérêt pour l’étude des facteurs en cause. Le présent mémoire rapporte et détaille les résultats de cette analyse quant à la formation de monomères versus celle de dimères par cyclisation à l’aide de catalyseurs de Grubbs et l’impact de différentes conditions réactionnelles et la diastéréochimie relative sur la réaction.
Un intérêt pour la formation de liens benzyliques nous a incité à approfondir notre compréhension d’une méthodologie de substitution nucléophile diastéréosélective catalysée par des acides. Le rationnel mit de l’avant par les groupes Bach et Olah a procuré une compréhension du mécanisme réactionnel sur lequel nous avons basé nos observations subséquentes. Nous avons porté notre attention sur l’alkylation d’arènes, de phénols et de sulfonamides. Diverses régiosélectivités et diastéréosélectivités ont pu être observées en présence de substrats dérivés de la synthèse de l’aliskiren, de nitroalcools ainsi que de azidoalcools en utilisant plusieurs acides de Lewis et de Brønsted.<br>Previously, a synthesis of aliskiren, a renin inhibitor developed for the treatment of hypertension, was developed in the Hanessian group. As part of that synthesis, they used a ring-closing metathesis which led to the formation of a nine-membered lactone, a key intermediate of the synthesis. During the reaction, we observed a difference in reactivity between the various diastereoisomers leading to the formation of mono- and dilactones, inciting us to study the various factors involved. The present master’s thesis reports and details the results of the study of monomers versus dimers formation by cyclization using Grubbs’s catalysts and the effect of various reaction conditions and relative configuration on the reaction.
An interest for the formation of benzylic bonds drove us to deepen our comprehension of a methodology of diastereselective nucleophilic substitution catalysed by acids. The rational brought forth by the Bach and Olah groups served as a basis for our understanding of the mechanism involved upon which we based our following observations. We focused our attention on the alkylation of arenes, phenols and sulfonamides. Various regioselectivities and diastereoselectivities were observed on substrates derived from the aliskiren’s synthesis, nitroaocohols and azidoalcohols while using various Lewis and Brønsted acids.