Thesis (Ph. D.)--Ohio state University, 1923. / Autobiography.

Selective oxidations are important for the functionalization of compounds in organic synthesis and chemical industry. Using O2 as a terminal e- acceptor would be ideal because it is cheap and environmentally friendly, but aerobic oxidations are often prone to unselective free radical autoxidation. Recently developed palladium catalysts use O2 as a selective multi-electron oxidant for various organic transformations. Although these methods are powerful and sophisticated, the lower cost of base metals makes them attractive as potential alternatives. The challenge is to develop methods for effecting multi-electron transformations at metals that typically prefer one electron changes. To this end, the development of manganese(III) complexes containing redox-active ligands as catalysts for selective oxidase-type oxidation of organic substrates was pursued. Bis(tetrabromocatecholato) manganese(III) complexes were shown to aerobically oxidize catechols to form quinones and H2O2. This reactivity was extended to other alcohol and amine substrates. In these reactions, the non-innocent tetrabromocatecholate ligands may impart a multi-electron character to the metal. To directly probe the intermediacy of ligand-centered radicals in catalytic turnover, a series of structurally similar manganese(III) complexes with aminophenol-derived ligands were prepared and characterized. The capacity of these ligands to undergo low-energy redox changes, allowed for isolation of an electron transfer series spanning two redox states without a change in oxidation state at the metal center. The ligand-centered redox events were a key feature in aerobic homocoupling of Grignard reagents.

Flame based synthesis is a major manufacturing process of commercially valuable nanoparticles for large-scale production. However, this important industrial process has been advanced mostly by trial-and-error based evolutionary studies owing to the fact that it involves tightly coupled multiphysics flow phenomena. For large scale synthesis of nanoparticles, different physical and chemical processes exist, including turbulence, fuel combustion, precursor oxidation, and nanoparticle dynamics exist. A reliable and predictive computational model based on fundamental physics and chemistry can provide tremendous insight. Development of such comprehensive computational models faces challenges as they must provide accurate descriptions not only of the individual physical processes but also of the strongly coupled, nonlinear interactions among them. In this work, a multiscale computational model for flame synthesis of TiO2 nanoparticles in a turbulent flame reactor is presented. The model is based on the large-eddy simulation (LES) methodology and incorporates detailed gas phase combustion and precursor oxidation chemistry as well as a comprehensive nanoparticle evolution model. A flamelet-based model is used to model turbulence-chemistry interactions. In particular, the transformation of TiCl4 to the solid primary nucleating TiO2 nanoparticles is represented us- ing an unsteady kinetic model considering 30 species and 70 reactions in order to accurately describe the critical nanoparticle nucleation process. The evolution of the TiO2 number density function is tracked using the quadrature method of moments (QMOM) for univariate particle number density function and conditional quadrature method of moments (CQMOM) for bivariate density distribution function. For validation purposes, the detailed computational model is compared against experimental data obtained from a canonical flame- based titania synthesis configuration, and reasonable agreement is obtained. / text

Neste trabalho realizou-se triagem para oxidação de sulfetos a sulfóxidos utilizandose fungos Basidiomicetos, os quais são denominados fungos da podridão branca, uma vez que decompõem a lignina presente na madeira, causando o apodrecimento e em lguns casos, a morte da planta. A triagem foi realizada utilizando-se quatro sulfetos aromáticos (Fig.1) e 6 fungos Basidiomicetos: Pycnoporus sanguineos CCB 501, Trametes versicolor CCB 202, Trametes rigida CCB 285, Trichaptum byssogenum CCB 203, Trametes villosa CCB 291, Irpex lacteus CCB 196. Na Tabela 1 são mostrados alguns resultados obtidos na oxidação com os microrgamsmos: (Ver PDF) Na segunda parte deste trabalho, com a finalidade de aplicar a biocatálise em moléculas mais complexas, realizou-se a síntese de 8 compostos bi-funcionalizados com grupos selênio, sulfeto e carbonila (cetona) (Esquema 1), as quais reagiram quimiosseletivamente frente às enzimas. (Ver PDF) Na última parte deste trabalho foi desenvolvido um novo método de síntese de biciclos [3.2.1] (32) (Esquema 2) (Ver PDF). / In the first part of this dissertation, we reported the screening of Basidiomycetes fungus for the oxidation of the sulfides into sulfoxides. The Basidiomycetes fungs are known as white rot fungus, because promote the degrade of lignin in wood, causing the death of the plant. The screening was reported with four aromatic sulfides (Table I) and six Basidiomycetes fungus: Pycnoporus sanguineos CCB 501, Trametes versicolor CCB 202, Trametes rigida CCB 285, Trichaptum byssogenum CCB 203, Trametes villosa CCB 291, Irpex lacteus CCB 196. Table 1. Oxidation of aromatic sulfides by whole fungal cells. (See PDF) In the second part of this dissertation, we synthesized eight bi-funcionalizated compounds with sulfide, selenide and ketone groups (Scheme 1). Theses compounds were submitted to the action of enzymatic system ofBasidiomycetes fungi. (See PDF) In the last part of this dissertation it is reported a new method for the synthesis of bicycle [3.2.1] (32) (Scheme 2). (See PDF)

Esta dissertação apresenta estudos visando à síntese de indanos oticamente ativos, através da contração de anel de 3-alquenóis promovida por tálio(III). Dois novos sais de tálio(III) foram preparados - o (S)-(-)-triacetoxipropionato de tálio (TTAP) e o tripropionato de tálio (TTP) - a partir do triacetato de tálio (TTA) e dos ácidos (S)-(-)-2-acetoxipropiônico e propiônico, respectivamente. A ciclização do isopulegol foi realizada com TTAP e com TTP, em rendimentos similares aos obtidos com TTA e com trinitrato de tálio (TTN). O rearranjo oxidativo do 2-(3,4-diidronaftalen-1-il)-etanol, que é um 3-alquenol, também pôde ser efetuado com o TTAP e com o TTP, embora rendimentos inferiores aos obtidos com TTN, com TTA, ou com trifluoroacetato de tálio (TTFA) tenham sido alcançados. Nestas contrações de anel, fica evidente que a ordem de reatividade segue a força elétron atraente dos ânions ligados ao tálio. Além disso, as melhores condições reacionais obtidas foram as que utilizam como solvente uma mistura de água e do ácido correspondente ao ligante do sal de tálio(III). Finalmente, na reação de contração de anel com o sal de tálio(III) quiral TTAP, o produto de contração de anel foi obtido como uma mistura racêmica. Os testes preliminares de resolução enzimática do 3-hidroxi-1-indan-1-il-propan-1-ona realizados com lipases mostraram-se promissores, abrindo novas perspectivas para a obtenção de indanos oticamente ativos com bom excesso enantiomérico. / This dissertation presents a study toward the synthesis of optically active indans by the thallium(III) promoted ring contraction of 3-alkenols. Two new thallium(III) salts were prepared - thalllium (S)-(-)-triacetoxypropionate (TTAP) and thallium tripropionate (TTP) - from thallium triacetate (TIA) and (S)-(-)-2-acetoxypropionic acid and propionic acid, respectively. The cyclization of isopulegol was performed using TTAP or TTP. The isolated yields for these reactions are similar to that obtained with TTA or with thallium trinitrate (TTN) The oxidative rearrangement of the 2-(3,4-dihydro-naphthalen-1-yl)-ethanol, which is a 3alkenol, could also be performed by TTAP or by TTP, although the isolated yields were lower from that in a similar reaction with TTN, TTA or thallium trifluoroacetate (TTFA). In these ring contractions, the reactivity c1early depends on the eletron-withdrawing ability of the anion bonded to the thallium atom. In addition, the best reaction conditions are those where the solvent is a mixture of H2O and the acid corresponding to the ligand of the thallium(III) salt. Finally, in the reaction using the chiral non-racemic TTAP, the ring contraction product was obtained as a racemic mixture. The preliminary results on the enzymatic resolution of 3-hydroxy-1-indan-1-yl-propan-1-one using lipases show that optically active indan might be obtained in good e.e. using this approach.

Neste trabalho realizou-se triagem para oxidação de sulfetos a sulfóxidos utilizandose fungos Basidiomicetos, os quais são denominados fungos da podridão branca, uma vez que decompõem a lignina presente na madeira, causando o apodrecimento e em lguns casos, a morte da planta. A triagem foi realizada utilizando-se quatro sulfetos aromáticos (Fig.1) e 6 fungos Basidiomicetos: Pycnoporus sanguineos CCB 501, Trametes versicolor CCB 202, Trametes rigida CCB 285, Trichaptum byssogenum CCB 203, Trametes villosa CCB 291, Irpex lacteus CCB 196. Na Tabela 1 são mostrados alguns resultados obtidos na oxidação com os microrgamsmos: (Ver PDF) Na segunda parte deste trabalho, com a finalidade de aplicar a biocatálise em moléculas mais complexas, realizou-se a síntese de 8 compostos bi-funcionalizados com grupos selênio, sulfeto e carbonila (cetona) (Esquema 1), as quais reagiram quimiosseletivamente frente às enzimas. (Ver PDF) Na última parte deste trabalho foi desenvolvido um novo método de síntese de biciclos [3.2.1] (32) (Esquema 2) (Ver PDF). / In the first part of this dissertation, we reported the screening of Basidiomycetes fungus for the oxidation of the sulfides into sulfoxides. The Basidiomycetes fungs are known as white rot fungus, because promote the degrade of lignin in wood, causing the death of the plant. The screening was reported with four aromatic sulfides (Table I) and six Basidiomycetes fungus: Pycnoporus sanguineos CCB 501, Trametes versicolor CCB 202, Trametes rigida CCB 285, Trichaptum byssogenum CCB 203, Trametes villosa CCB 291, Irpex lacteus CCB 196. Table 1. Oxidation of aromatic sulfides by whole fungal cells. (See PDF) In the second part of this dissertation, we synthesized eight bi-funcionalizated compounds with sulfide, selenide and ketone groups (Scheme 1). Theses compounds were submitted to the action of enzymatic system ofBasidiomycetes fungi. (See PDF) In the last part of this dissertation it is reported a new method for the synthesis of bicycle [3.2.1] (32) (Scheme 2). (See PDF)

Esta dissertação apresenta estudos visando à síntese de indanos oticamente ativos, através da contração de anel de 3-alquenóis promovida por tálio(III). Dois novos sais de tálio(III) foram preparados - o (S)-(-)-triacetoxipropionato de tálio (TTAP) e o tripropionato de tálio (TTP) - a partir do triacetato de tálio (TTA) e dos ácidos (S)-(-)-2-acetoxipropiônico e propiônico, respectivamente. A ciclização do isopulegol foi realizada com TTAP e com TTP, em rendimentos similares aos obtidos com TTA e com trinitrato de tálio (TTN). O rearranjo oxidativo do 2-(3,4-diidronaftalen-1-il)-etanol, que é um 3-alquenol, também pôde ser efetuado com o TTAP e com o TTP, embora rendimentos inferiores aos obtidos com TTN, com TTA, ou com trifluoroacetato de tálio (TTFA) tenham sido alcançados. Nestas contrações de anel, fica evidente que a ordem de reatividade segue a força elétron atraente dos ânions ligados ao tálio. Além disso, as melhores condições reacionais obtidas foram as que utilizam como solvente uma mistura de água e do ácido correspondente ao ligante do sal de tálio(III). Finalmente, na reação de contração de anel com o sal de tálio(III) quiral TTAP, o produto de contração de anel foi obtido como uma mistura racêmica. Os testes preliminares de resolução enzimática do 3-hidroxi-1-indan-1-il-propan-1-ona realizados com lipases mostraram-se promissores, abrindo novas perspectivas para a obtenção de indanos oticamente ativos com bom excesso enantiomérico. / This dissertation presents a study toward the synthesis of optically active indans by the thallium(III) promoted ring contraction of 3-alkenols. Two new thallium(III) salts were prepared - thalllium (S)-(-)-triacetoxypropionate (TTAP) and thallium tripropionate (TTP) - from thallium triacetate (TIA) and (S)-(-)-2-acetoxypropionic acid and propionic acid, respectively. The cyclization of isopulegol was performed using TTAP or TTP. The isolated yields for these reactions are similar to that obtained with TTA or with thallium trinitrate (TTN) The oxidative rearrangement of the 2-(3,4-dihydro-naphthalen-1-yl)-ethanol, which is a 3alkenol, could also be performed by TTAP or by TTP, although the isolated yields were lower from that in a similar reaction with TTN, TTA or thallium trifluoroacetate (TTFA). In these ring contractions, the reactivity c1early depends on the eletron-withdrawing ability of the anion bonded to the thallium atom. In addition, the best reaction conditions are those where the solvent is a mixture of H2O and the acid corresponding to the ligand of the thallium(III) salt. Finally, in the reaction using the chiral non-racemic TTAP, the ring contraction product was obtained as a racemic mixture. The preliminary results on the enzymatic resolution of 3-hydroxy-1-indan-1-yl-propan-1-one using lipases show that optically active indan might be obtained in good e.e. using this approach.