Explosive materials have always been attracting the attention of scientists. Various explosives either in pure bulk form or as admixtures are synthesized and investigated from different points of view. However, because of dangerous character of these materials, their syntheses and properties have to be forecasted by theoretical studies. The new research trends of explosive materials generally include the designs of novel derivatives of well&ndash / known explosives to improve their detonation performances (heats of explosion, detonation velocities and detonation pressures) and thermal stabilities and decrease their sensitivities towards friction, electric spark, shock and impact either experimentally or theoretically. NTO (5&ndash / nitro&ndash / 2,4&ndash / dihydro&ndash / 3H&ndash / 1,2,4&ndash / triazol&ndash / 3&ndash / one) and PATO (3&ndash / picrylamino&ndash / 1,2,4&ndash / triazole) are very important secondary explosives that take place in the literature for many years in terms of their explosive properties. In this thesis study, new species of these explosives have been designed to enhance their detonation performances (ballistic properties) and to lower their sensitivities and reactivities computationally. Additionally, aromatic nitration reactions and their mechanisms for unprotonated and protonated PATO species have been analyzed. The ab initio quantum chemistry methods, Hartree&ndash / Fock (HF) and Density Functional Theory (DFT), have been used in the calculations with Pople basis sets. Novel NTO and PATO tautomeric species have been designed and investigated to enlighten the effects of tautomerism on their quantum chemical properties and detonation performances in the gas phase. Various aromatic nitration mechanisms (carbon and nitrogen mono&ndash / nitration mechanisms) of unprotonated tautomeric PATO species as well as PATO have been designed in gas phase and the reaction states (pre&ndash / transition states, transition states, intermediates and nitration products) have been detected belonging to these mechanisms. Nitrations in solution phase have also been analyzed. The reaction states have been detected for carbon and nitrogen mono&ndash / nitrations of protonated PATO species in the gas phase. The detonation performances of unnitrated and nitrated PATO products have been presented.

Submitted by MARCOS HENRIQUE PEREIRA WONDRACEK null (marcoswondracek@ufgd.edu.br) on 2017-10-29T05:42:20Z No. of bitstreams: 1 TESE - versão final.pdf: 3488966 bytes, checksum: 44030b3422f6b77b9ba441eb0905cb23 (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-11-09T13:58:32Z (GMT) No. of bitstreams: 1 wondracek_mhp_dr_araiq.pdf: 3488966 bytes, checksum: 44030b3422f6b77b9ba441eb0905cb23 (MD5) / Made available in DSpace on 2017-11-09T13:58:32Z (GMT). No. of bitstreams: 1 wondracek_mhp_dr_araiq.pdf: 3488966 bytes, checksum: 44030b3422f6b77b9ba441eb0905cb23 (MD5) Previous issue date: 2017-10-05 / Item merged in doublecheck by Monique Sasaki (sayumi_sasaki@hotmail.com) on 2017-12-07T17:59:08Z Item was identical to item(s): 153113, 153193 at handle(s): http://hdl.handle.net/11449/152063, http://hdl.handle.net/11449/152164 / Este trabalho relata o desenvolvido de métodos analíticos que visa à determinação de algumas espécies tóxicas e potencialmente tóxicas de metais e metalóides em níveis ultra-traço em amostra de água naturais, utilizando uma técnica analítica menos sensível, como a espectrometria de absorção atômica em chama (FAAS). Essa técnica foi escolhida por ser relativamente simples e possuir baixo custo operacional. A técnica de extração em fase sólida (EFS), utilizando um novo material sorvente, foi utilizada para separar e pré-concentrar os analitos. Este estudo demonstra o procedimento de uma nova rota sintética via co-condensação visando à produção de uma sílica mesoporosa organofuncionalizada com o ligante 4-amino-3-hidrazino-5-mercapto-1,2,4-triazole e, sua utilização como sorvente para pré-concentração/análise de especiação de íons metálicos em amostras de água. O material produzido foi caracterizado por espectroscopia na região do infravermelho (FTIR), BET, ressonância magnética nuclear (RMN) de 29Si e 13C, dentre outras. As características adsortivas desse material foram estabelecidas em estudos de batelada, onde se estudou o efeito do pH, cinética de adsorção e capacidade máxima de adsorção. A otimização multivariada foi utilizada para obtenção das melhores condições químicas e de fluxo no sistema de pré-concentração, permitindo avaliar as interações principais e secundárias entre os fatores. Por meio da análise dos espectros obtidos por FTIR foi possível observar bandas de estiramento C–H, C–Cl e (NH2) oriundos da fração orgânica do material. A área superficial foi de 369,84 m2 g-1com diâmetro médio de poros em 7,1 nm, relacionados a materiais mesoporosos. Os resultados obtidos por RMN de 29Si comprovam a formação do material híbrido, sintetizado por co-condensação, e o RMN de 13C confirma o ancoramento do ligante na matriz. O pH que favorece a adsorção dos íons foi 5,0 para Cu(II) e 3,0 para Cd(II) e As(V). O modelo cinético de pseudo segunda ordem apresentou melhor ajuste aos dados experimentais, indicando adsorção química. Os dados de sorção desses íons metálicos mostraram bom ajuste ao modelo de Langmuir, com capacidade máxima de adsorção próxima aos valores obtidos experimentalmente, 0,057, 0,018 e 0,060 mmol g-1 para Cu(II), Cd(II) e As(V), respectivamente, indicando que a sorção ocorre em monocamada. Os parâmetros analíticos encontrados para o Cu(II) foram: fator de pré-concentração de 18,1; intervalo linear de 10,0 – 200,0 µg L-1 (R = 0,999) e LD de 1,45 µg L-1. Para o Cd(II): fator de pré-concentração de 15,8; intervalo linear de 2,0 – 100,0 µg L-1 (R = 0,999) e LD de 0,38 µg L-1. Para o As(V): fator de pré-concentração de 5,0; intervalo linear de 0,25 – 2,5 µg L-1 (R = 0,999) e LD de 0,039 µg L-1. A exatidão foi checada pelo método de adição e recuperação e/ou método comparativo com GFAAS ou ICP OES. As recuperações variaram de 97 – 106% (Cu), 100 – 105% (Cd), 88 – 103% (As(V)) e 96 – 106% (As(total)). Os resultados para Cu(II) determinados com os métodos propostos foram concordantes com os obtidos com o método comparativo. Conclui-se que o material produzido apresenta bom potencial para ser aplicado na extração/pré-concentração de cobre, cádmio e análise de especiação inorgânica de arsênio. Provou-se também que baixos limites de detecção e quantificação podem ser obtidos mesmo utilizando uma técnica menos sensível como a FAAS. / This paper reports on the development of analytical methods for the determination of some toxic and potentially toxic species in ultra - trace levels in natural water samples using a less sensitive analytical technique such as flame atomic absorpti on spectrometry (FAAS). This technique was chosen because it is relatively simple and has a low operating cost. The solid phase extraction technique (SPE) using a new sorbent material was used to separate and preconcentrate the analyte. This study demonstr ates the procedure of a new synthetic route using the technique of the co - condensation for the production of a mesoporous organo - functionalised silica with the 4 - amino - 3 - hydrazino - 5 - mercapto - 1,2,4 - triazole ligant and its use as a sorbent for preconcentrati on/ analysis of metal ion s speciation in water samples. The material produced was characterized by infra - red spectroscopy (FTIR), BET, 29 Si and 13 C nuclear magnetic resonance (NMR), among others. The adsorptive characteristics of this material were establis hed in batch studies, where the effect of pH, adsorption kinetics and maximum adsorption capacity were studied. Multivariate optimization was used to obtain the best chemical and flow conditions in the preconcentration system, allowing the evaluation of th e main and secondary interactions among the factors. By means of the analysis of the spectra obtained by FTIR, it was possible to observe C - H, C - Cl and (NH 2 ) stretch bands from the organic fraction of the material. The surface area was 369.84 m 2 g - 1 with a verage pore diameter at 7.1 nm related to mesoporous materials. The results obtained by 29 Si NMR prove the formation of the hybrid material, synthesized by co - condensation, and the 13 C NMR confirms the anchoring of the ligan t in the matrix. The pH 5.0 it w as favors the adsorption of the ions Cu (II), the pH 3.0 it was favors the adsorption of the Cd (II) and As (V). The kinetic model of pseudo second order showed better adjustment to the experimental data, indicating chemical adsorption. The adsorption data of Cu (II), Cd (II), and As (V) were similar to those of the Langmuir model, with a maximum adsorption capacity of 0.057, 0.018 and 0.060 mmol g - 1 for Cu (II), Cd(III) and As(V) , respectively, indicating that the sorption occurs in monolayer. The analyt ical parameters for Cu (II) were: preconcentration factor of 18.1; linear range of 10.0 - 200.0 μg L - 1 (R = 0.999) and LD of 1.45 μg L - 1 . For Cd (II): preconcentration factor of 15.8; linear range of 2.0 - 100.0 μg L - 1 (R = 0.999) and LD of 0.38 μg L - 1 . Fo r As (V): preconcentration factor of 5.0; linear range of 0.25 - 2.5 μg L - 1 (R = 0.999) and LD of 0.039 μg L - 1 . Accuracy was checked by addi tion and recovery method of the standard and/ or comparative method with GFAAS or ICP OES. The recovery ranged from 97 - 106% Cu(II), 100 - 105% Cd (II), 88 - 103% As (V) and 96 - 106% As (total)). The results for Cu (II) determined with the proposed methods were concordant with those obtained with the comparative. It is concluded that the material produced can be successfully applied in the extraction / preconcentration of copper, cadmium and analysis of inorganic speciation of arsenic and low limits of detection and quantification can be obtained even using a less sensitive technique such as FAAS.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This thesis reports the synthesis of various series of trifluoromethyl substituted nitrogenated heterocycles, such as pyrroles, pyrazoles, pyrimidines and 1,2,3-triazoles, exploiting the synthetic versatility of 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one in reactions with nitrogenated nucleophiles. In this way, synthesis of a novel series of 4-amino-3-trifluoromethyl-1H-N-substituted pyrroles was performed through two reaction steps. In the first stage is an addition reaction of primary or secondary amine in the 4-position of 5-bromo-1,1,1-trifluoro-4-methoxy-3-penten-2-one furnishing 4-amino-5-bromo-1,1,1-trifluoropent-3-en-2-one. The second stage is a nucleophilic substitution of the bromine by a primary amine followed by an intramolecular cyclocondensation reaction resulting in the formation of pyrroles with yields from 50 to 98%. Through the reaction of 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one with sodium azide, 5-azido-1,1,1-trifluoro-4-methoxypent-3-en-2-one was obtained. This compound was subjected to cycloaddition reaction [3 + 2] with terminal alkynes, allowing the synthesis of a novel series of 1,1,1-trifluoro-4-methoxy-5-(4-alkyl/aryl-1H-1,2,3-triazol-1-yl)-pent-3-en-2-one (I) in good yields (74-90%). Through this reaction a wide range of bi-heterocycle compounds was obtained. For example, the reaction of compound I with 2-methylisothiourea sulfate gave a series of 4-(1H-1,2,3-triazol-1-yl)-methyl-6-trifluoromethyl pyrimidine (72-79%). In a second step, the SCH3 group of these pyrimidines was oxidized to SO2CH3 and subsequently substituted by primary and secondary amines to give a series of 2-aminopyrimidines derivatives in yields of 70-93%. Furthermore, the reaction with N1-substituted 2-methylisothiourea sulphates furnished two products: a 4-pyrimidinone and 1,4-dihydropyrimidine derivatives, depending on the reaction conditions employed. From the reaction of compound I with hydrazines and hydrazides a series of 4-[(4-alkyl/aryl-1H-1,2,3-triazol-1-yl)methyl]-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-pyrazole, in yields of 77-90%, was obtained. The products obtained in this study were characterized by 1H- and 13C- NMR, mass spectrometry, high resolution mass spectrometry, elemental analysis, and X-ray diffraction. Keywords: 5-bromo-1,1,1-trifluoro-4-methoxypent-3-en-2-one, 5-bromo-4-enaminoketone, 4-amino-3-trifluoromethyl-1H-pyrroles N-substituted, 1,2,3-triazole, pyrimidine, pyrazolines, bi-heterocycles. / Esta tese apresenta a síntese de várias séries de heterociclos nitrogenados trifluormetil substituidos, tais como pirróis, pirazóis, pirimidinas e 1,2,3-triazóis, explorando-se a versatilidade sintética de 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona em reações com nucleófilos nitrogenados. Dessa forma, a síntese de uma série inédita de 4-amino-3-trifluormetil-1H-pirróis N-substituídos foi realizada através de duas etapas reacionais. Na primeira etapa ocorre uma reação de adição de amina primária ou secundária na posição-4 da 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona para a formação de 4-amino-5-bromo-1,1,1-trifluorpent-3-en-2-ona. Na segunda etapa ocorre a substituição nucleofílica do bromo por uma amina primária e consequente ciclocondensação intramolecular para a formação dos pirróis com rendimentos entre 50 a 98%. Através da reação da 5-bromo-1,1,1-trifluor-4-metoxipent-3-en-2-ona com azida de sódio, obteve-se a 5-azido-1,1,1-trifluor-4-metoxipent-3-en-2-ona, a qual, pela reação de cicloadição [3+2] com alcinos terminais possibilitou a síntese de uma série inédita de 1,1,1-trifluor-4-metóxi-5-(4-alquil/aril-1H-1,2,3-triazol-1-il)-pent-3-en-2-ona (I), com bons rendimentos (74-90%). Por intermédio destes compostos foi obtida uma vasta gama de bi-heterociclos. Por exemplo, a reação do composto I com sulfato de 2-metilisotioureias possibilitou a obtenção da série de 4-(1H-1,2,3-triazol-1-il)metil-6-trifluormetil pirimidinas (72-79%). Em uma segunda etapa, o grupamento SCH3 destas pirimidinas foi oxidado a SO2CH3 e, posteriormente substituído por aminas primárias e secundárias, obtendo-se, assim, uma série de 2-aminopirimidinas derivadas com rendimentos de 70-93%. Além disso, a reação com os sulfatos de 2-metilisotioureia N1-substituídos levou a obtenção de dois produtos: uma 4-pirimidinona e uma 1,4-diidropirimidina, dependendo da condição reacional empregada. A partir da reação do composto I com hidrazinas e hidrazidas proporcionou a obtenção de uma série de 4-[(4-alquil/aril-1H-1,2,3-triazol-1-il)metil]-5-hidróxi-5-trifluormetil-4,5-diidro-1H-pirazol com rendimentos de 77-90%. Os produtos obtidos neste trabalho foram caracterizados por Ressonância Magnética Nuclear de Hidrogênio e Carbono-13, Espectrometria de Massas, Espectrometria de Massas de Alta Resolução, Análise Elementar e Difratometria de Raio-X.