Specially prepared 2-arylquinolin-4(1H)-ones and their 2-aryl-1-methyl-4-quinolone derivatives were converted in high yield and purity to the corresponding C-3 brominated products using pyridinium tribromide in acetic acid at room temperature. The 2-arylquinolin-4(1H)-ones were reacted with iodine and Na2CO3 mixture in THF at room temperature to produce the 3-iodo-2-arylquinolin-4(1H)-one derivatives. The latter were, in turn, N-methylated using NaH-MeI mixture in dry THF to afford the corresponding 2-aryl-3-iodo-1-methyl-4-quinolone derivatives. The 3-iodo-2-arylquinolin-4(1H)-one and 2-aryl-3-iodo-1-methyl-4-quinolones were converted to 2,3-diarylquinolin-4(1H)-one and 2,3-diaryl-1-methyl-4-quinolones following Suzuki cross-coupling reaction method, respectively. The 2-aryl-3-bromoquinolin-4(1H)-ones, on the other hand, were converted to 2-aryl-3-bromo-4-chloroquinoline derivatives using phosphorus oxychloride under reflux. The 2-aryl-3-bromo-4-chloroquinoline were then transformed to the corresponding 2-aryl-3-bromo-4-N-(4'-chloroaryl)-4-aminoquinolines derivatives using 4-chloroaniline in ethanol under reflux. The products synthesized in this investigation were characterised using a combination of 1H NMR, 13C NMR, IR and mass spectroscopic techniques. / Chemistry / Chemistry / MSC (CHEMISTRY) / MSC (Chemistry)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This study was carried out in three parts: At first, three methods for the bromination of 6-alkylsubstituted 2-phenyl-3H-pyrimidin-4-ones was developed for the synthesis of: (i) a new series of 6-alkylsubstituted 5-bromo-2-phenyl-3H-pyrimidin-4-ones, (ii) a new series of 6-(1-bromoalkyl)-2-phenyl-3H-pyrimidin-4-ones, and (iii) e new series of 5-bromo-6-(1-bromoalkyl)-2-phenyl-3H-pyrimidin-4-ones. On the second part, the brominated pyrimidines obtained, were used to synthesize new 6-methylsubstituted 2-phenyl-3Hpyrimidin-4-ones from the reaction of the brominated pyrimidinones with primary and secondary amines, pyridine and sodium azide. On the third part, a new series of 5- e 6-substituted 4-trifluoromethyl-2-ureido pyrimidines was prepared, in good yields, from the cyclocondensation reaction of β- alkoxyvinyl-trifluoromethylketones substituted and dicyanodiamide. The products synthesized in this study were obtained in good yields and were characterized by GC-MS and 1H e 13C RMN spectroscopy. The purity of the products was assured by elemental analysis. Some compounds such as 5-bromo-2-phenyl-6-propyl-3H-pyrimidin-4-one, 5-bromo-6-(1- bromopropyl)-2-phenyl-3H-pyrimidin-4-one, 5-bromo-6-(1-bromobutyl)-2-phenyl-3H-pyrimidin-4-one, 6-(1-azidoethyl)-5-bromo-2-phenyl-3H-pyrimidin-4-one, 6-(1-azidopropyl)-5-bromo-2-phenyl-3H-pyrimidin-4-one, and 6-(1-azidobutyl)-5-bromo-2-phenyl-3H-pyrimidin-4-one, exhibited significant antimicrobial activity against some microorganisms, such as Candida albicans, Saccharomyces cerevisiae, Staphylococcus aureus, Salmonela, Klebsiela pneumonie among others. / Este trabalho foi realizado em três etapas. Na primeira, foram desenvolvidos três métodos de bromação de 2-fenil-3H-pirimidin-4-onas 6-alquilsubstituídas para a obtenção de: (i) uma série inédita de 5-bromo-2-fenil-3H-pirimidin-4-onas 6-alquilsubstituídas, (ii) uma série inédita de 6-(1- bromoalquil)-2-fenil-3H-pirimidin-4-onas e (iii) uma série inédita de 5-bromo-6-(1-bromoalquil)-2-fenil-3H-pirimidin-4-onas. Na segunda etapa, as pirimidinas bromadas, obtidas na etapa anterior, foram utilizadas para sintetizar novas 2-fenil-3H-pirimidin-4-onas 6-metilsubstituídas através de reações das pirimidinonas bromadas com aminas primárias e secundárias, piridina e azida de sódio. Na terceira etapa, foi sintetizada uma nova série de 4-trifluormetil-2-ureído pirimidinas 5- e 6-substituídas a partir de reações de ciclocondensação entre -alcoxivinil-fluormetilcetonas substituídas e dicianodiamida. Os produtos sintetizados neste trabalho foram obtidos em bons rendimentos e foram caracterizados por CG-EM e RMN de 1H e 13C. A pureza dos produtos foi comprovada por análise elementar. Alguns compostos como 5-bromo-2-fenil-6-propil-3H-pirimidin-4-ona, 5-bromo-6-(1-bromopropil)-2-fenil-3H-pirimidin-4-ona, 5-bromo-6-(1-bromobutil)-2-fenil-3Hpirimidin-4-ona, 6-(1-azidoetil)-5-bromo-2-fenil-3H-pirimidin-4-ona, 6-(1- azidopropil)-5-bromo-2-fenil-3H-pirimidin-4-ona e 6-(1-azidobutil)-5-bromo-2-fenil-3H-pirimidin-4-ona, apresentaram atividade antimicrobiana significativa contra alguns microorganismos como Candida albicans, Saccharomyces cerevisiae, Staphylococcus aureus, Salmonela, Klebsiela pneumonie e outras.

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京都大学 / 新制・課程博士 / 博士(工学) / 甲第24625号 / 工博第5131号 / 新制||工||1981(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 松原 誠二郎, 教授 中尾 佳亮, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2018-11-29T18:26:31Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Cibeli May.pdf: 3927669 bytes, checksum: 83b271f172e7367bd94016252ee517c4 (MD5) / Made available in DSpace on 2018-11-29T18:26:31Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Cibeli May.pdf: 3927669 bytes, checksum: 83b271f172e7367bd94016252ee517c4 (MD5) Previous issue date: 2018-04-13 / O texto deste trabalho esta dividido em três capítulos. No Capítulo 1 tem-se a revisão bibliográfica onde é apresentada a aplicação dos compostos orgânicos bromados, a principal forma de síntese destes e as mudanças que vêm ocorrendo devido o uso de solventes prejudiciais à camada de ozônio. Serão descritos métodos alternativos de sínteses, sendo que o mais abordado é o método eletroquímico usado, portanto neste trabalho, por meio do qual é possível realizar a bromação de anéis aromáticos e bromação de aromáticos na posição benzílica. Também serão apresentadas as aplicações dos compostos sintetizados: α, α α’, α’-tetrabromo-pxileno e α, α, α’, α’-tetrabromo-2,5-diciano-p-xileno. No Capítulo 2 são apresentados os estudos experimentais e teóricos, onde se buscou uma explicação para as diferenças observadas na reação química tradicional de tetrabromação benzílica no 2,5-diciano-p-xileno em comparação ao p-xileno. Para isso se realizou para cada composto a reação de Wohl-Ziegler por 10 horas, recolhendo-se amostras em cada tempo determinado, estas amostras formam analisadas por Ressonância Magnética Nuclear de Hidrogênio (RMN de H1) e Cromatografia Gasosa acoplada a Espectrometria de Massas (CG-MS). Também foi realizado um estudo teórico de carga a partir de simulação computacional. O que se observa é que o composto contendo o substituinte nitrila apresenta uma reação de bromação mais lenta com a formação de quatro compostos intermediários, enquanto que para o composto sem substituinte a reação é mais rápida e apenas dois compostos intermediários são observados. No Capítulo 3 é descrito um método alternativo de síntese para a tetrabromação benzílica do 2,5-diciano-p-xileno e do p-xileno. A obtenção destes compostos ocorre usando-se reações eletroquímicas, onde não é necessário o uso de solventes de venda proibida (CCl4). Também se realizou um acompanhamento cinético, analisando-se as amostras coletadas por RMN de H1 e CG-MS, para fazer a comparação de síntese pelo método tradicional e eletroquímico. Sendo que a principal diferença observada é que no método eletroquímico as reações são mais lentas, também com este método é possível continuar adicionando bromos na posição benzílica ao composto p-xileno, obtendo-se este composto pentabromado e hexabromado. / The text of this paper is divided into three chapters. In Chapter 1 there is a bibliographic review where the application of brominated organic compounds is presented, the main form of synthesis of these and the changes that have been occurring due to the use of solvents harmful to the ozone layer. It will be described alternative methods of synthesis, and the most approached is the electrochemical method used, therefore in this work, through which it is possible to perform the bromination of aromatic rings and bromination of aromatics in the benzylic position. The applications of the synthesized compounds: α, α, α', α'-tetrabromo-p-xylene and α, α, α ', α'-tetrabromo-2,5-dicyano-p-xylene will also be presented. In Chapter 2 we present experimental and theoretical studies, where an explanation was sought for the differences observed in the traditional chemical reaction of benzylic tetrabromination in 2,5-dicyano-p-xylene compared to p-xylene. In order to do this, the reactions of Wohl-Ziegler were carried out for 10 hours. Samples were collected at each determined time. These samples were analyzed by Hydrogen Nuclear Magnetic Resonance (H1 NMR) and Gas Chromatography Coupled to Mass Spectrometry (CG-MS). A theoretical load study was also carried out from a computer simulation. What is observed is that the compound containing the nitrile substituent has a slower bromination reaction with the formation of four intermediate compounds, whereas for the compound without substituent the reaction is faster and only two intermediate compounds are observed. In Chapter 3 an alternative method of synthesis for the benzylic tetra-bromination of 2,5-dicyano-p-xylene and p-xylene is described. The production of these compounds occurs using electrochemical reactions, where it is not necessary to use solvents of prohibited sale (CCl4). Also, a kinetic monitoring was performed, analyzing the samples collected by H1 NMR and CG-MS, to make the comparison of synthesis by the traditional and electrochemical method. As the main difference observed is that in the electrochemical method the reactions are slower, also with this method it is possible to continue adding bromines in the benzylic position to the compound p-xylene, obtaining this compound pentabromado and hexabromado.

Electrophilic Aromatic Substitution (EAS) is one of the most frequently used aryl substitution methods. Aside from the fact that most EAS reactions require an acid and an oxidizer to proceed, the reactions involving activated aryls typically produce a mixture of ortho- and para- products as well as an ortho-/para- disubstituted product. Regiospecificity in aromatic substitution is key in the production of many compounds in a variety of disciplines. Since EAS is one of the most often used substitution methods, it is extremely important to develop an efficient method for regiospecific substitutions. Previous research developed a method of ortho-substitution by using hydrocarbon media, a less hazardous, greener medium, which was modified to develop a method of p-iodination (bromination), but with extensive time periods. The research presented here not only reveals an expedient, rapid method for regiospecific p-bromination, but also does so without the need for an acid or an oxidizer. The conditions for p-bromination involve the use of acetone (sometimes with cyclohexane) and NBS resulting in GC yields of p-brominated product approaching 100% in a cost and time efficient manner without the concerns of hazardous materials or byproducts like Br2 or HBr. The reaction mechanism is briefly examined as well.

Bromoarenes are important aromatic building blocks that are commonly used to synthesize various functional compounds in pharmaceutical, agrochemical and related industries.1,2 This great demand for bromoarenes makes their preparation a widely studied area of synthetic organic chemistry. However, further understanding of the reactivity and regiochemistry of aromatic functionalization reactions is still necessary, as much about the secondary substitution and solvent effects remain unknown. Resonance Theory is a widely used theoretical model to predict the regiospecifity and reactivity of the bromination of various aromatic compounds.3 The reactivity and regiospecificity of many substituted aromatic compounds is well explained using resonance theory.4 However, kinetic understanding of the p-bromination of halosubstituted aromatic compounds has not been investigated to the best of our knowledge.5,6In this thesis, the reactivity and regiospecifity of the p-bromination of activated secondary substituted aromatic compounds as well as media effects on the process will be discussed. Synthesizing bromoarenes has been accomplished using many different experimental setups.7-11 N-bromosuccinimide is the most highly utilized electrophilic aromatic brominating agent. Many of the NBS- based aromatic bromination reactions have been reported using strong acids, strong bases, halogenated solvents, nonpolar solvents and polar solvents alike.12 The bromination reactions reported herein were performed using two different solvents, acetonitrile and acetone, to investigate the effects of solvent polarity on p-bromination. Although acetonitrile is one of the most commonly used solvents in the p-bromination of aromatic compounds, acetone has not been investigated.

Methane activation with bromine followed by the condensation of the methyl bromide into higher hydrocarbons or oxygenates is a novel route. However, the selective production of monobrominated methane (CH3Br) at high conversions is a crucial prerequisite. A reaction model was developed according to the kinetic data available in the literature and thoroughly studied to investigate the optimum reactor conditions for selective methane bromination in gas phase. It was concluded that at high methane (&gt / 90%) conversions dibromomethane synthesis was favored at high selectivity (~90%) under the following conditions: T=330 &deg / C, Br:CH4 = 3. Sulfated zirconia included SBA-15 catalysts were prepared and characterized for the catalytic methane activation via bromination. The SBA-15 sol-gel preparation technique was followed and the zirconium was added during the preparation in the form of ZrOCl2&middot / 8H2O with 5-30 mol % ZrO2 with respect to the SiO2 content simultaneously with the silicon source (TEOS). The catalysts were sulfated in 0.25 M H2SO4 solution. The zirconium contents of the catalysts were determined by elemental analysis and 15 wt. % Zr was determined as the highest amount. XRD analysis showed the crystalline zirconia peaks only for high zirconia loadings (&gt / 25 mol % ZrO2) indicating the good distribution of Zr in silica framework at lower loadings. BET surface areas of the sulfated catalysts are in the range of 313-246 m2/g. The porous structures of the catalysts were determined by TEM pictures, which revealed that the increase in Zr content decreased the long range order of pore structure of SBA-15 in agreement with XRD results. The acidities of the catalysts were determined by 1H MAS NMR experiments. Br&oslash / nsted acidity was identified by a sharp 1H MAS NMR line at 10.6 ppm. The highest acidity was observed at 5.2 wt. % Zr loading according to 1H MAS NMR experiments. 29Si MAS NMR analysis showed the formation of Si-O-X linkages (X=H, Zr). Further characterization of Br&oslash / nsted acidity was performed by FT-IR spectroscopy of adsorbed CO at 82 K. The analysis revealed that the Br&oslash / nsted acidity of sulfated catalysts were similar to the acid strength of the conventional sulfated zirconia. In TPD experiments, the basic molecule isopropylamine (IPAm) was adsorbed and decomposition temperature of IPAm was monitored. The temperature decreased from 340 &deg / C to 310 &deg / C in sulfated catalysts, indicating the acidic character of these samples. Catalytic methane bromination reaction tests were performed in a quartz tubular reactor. The results showed that 69% methane conversion was attainable over SZr(25)SBA-15 catalyst at 340 &deg / C. The liquid 1H NMR measurements of the products revealed that &gt / 99% methyl bromide selectivity was achieved.

Intramolecular ring closing metathesis in the presence of Grubbs' catalyst has been used as an efficient approach to synthesize bridged resorcinarenes. Octaallyl cavitands may undergo conformational changes; however bridge formation by RCM of the allyl groups gives a rigid, enforced, concave cavity capable of holding neutral molecules. This is the first report describing tandem formation of the four bridges on the upper rim of resorcinarenes. Structures of bridged resorcinarenes are confirmed by spectral analysis data.This report also describes the synthesis of polyhydroxy resorcinarenes, which have been used as metal complexing agents, sensors, receptors, molecular reaction vessels and catalytic chambers. They are able to encapsulate small neutral molecules, drug molecules inside the cavity. Such cavitands offer unique molecular platforms for host--guest chemistries, as well as new polymers and self-assembled systems.