Thesis (Ph. D.)--University of Wisconsin--Madison, 1965. / Vita. Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1958. / Typescript. Abstracted in Dissertation abstracts, v. 19 (1958) no. 6, p. 1318-1319. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 270-274).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1935. / Typescript. With this is bound 5 reprints from Journal of the American Chemical Society: The haloform reaction : IV. The influence of ortho methoxy groups / By Reynold C. Fuson, Mark W. Farlow and Carlyle J. Stehman. Vol. 53 (1931), p. 4097-4103 -- Ring-chain conjugation in the quinoline series / By Arnold Hoffman, Mark W. Farlow and Reynold C. Fuson. Vol. 55 (1933), p. 2000-2004 -- The action of zinc on 1,4-dibromo-1,4-dibenzoylbutane : an intramolecular Reformatsky reaction / By Reynold C. Fuson, Mark W. Farlow. Vol. 56 (1934), p. 1593-1595 -- Hydrogenation of derivatives of pyridine / By Homer Adkins, Leo F. Kuick, Mark Farlow and Bruno Wojcik. Vol. 56 (1934), p. 2425-2428 -- The structure of C₇H₁₂O₂ from the hydrogenation of furylacrolein / By Mark Farlow, Harold E. Burdick and Homer Adkins. Vol. 56 (1934), p. 2498. Includes bibliographical references (leaves 37-39).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1951. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1959. / Typescript. Abstracted in Dissertation abstracts, v. 19 (1959) no. 12, p. 3261. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 228-233).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1968. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 181-199).

Thesis (Ph. D.)--University of Washington, 1987. / Vita. Includes bibliographical references (leaves [73]-75).

ChapterI contains a review of phosphoniteisn asymmetric catalysis and recent developments in asymmetric hydrogenation and a symmetric hydroformylation catalysis. Chapter2 is concerned with new phosphonite ligands f r asymmetric catalysis. A new three-steps ynthesiso f 9,9'-biphenanthryl-10,10'-dio(lb iphenanthrol') in 36% yield from phenanthrene is reported. The ligands PhP(OR)2, PhP(OR')2, (RO)2PCH2CH2P(OR)2a nd Ph2PCH2CH2P(OR)2 derived from 'biphenanthrol' (HOR)2 and dimethyl-1,1'-binaphthyl-2,2'-dihydroxy-3,3'-dicarboxylate( HOR')2 have been synthesised and their Pt(O,I I) and R h(I) chemistry is discussed The crystal structures of two complexes of the type [PtC12(phosphonite)h2a] ve been determined. The monoPhosphonite, diphosphonite and phosphinophosphonite complexes [Rh(cod)P2]BF4 derived from (S)-'biphenanthroal'r e described. In Chapter 3, the chemistry of some new diphosphites is described. The diastereomeric mixture of (RO)2P(ORRO)P(OR)2( 'biphenanthrite') is formed by reacting (±)-'biphenanthrol' with PC13- Optically pure (R, R, R)-'biphenanthrite' is similarly prepared from (R)-biphenanthrol'.The side-products and intermediates in this reaction are identified by their independent syntheses C: IP(OR)2,H (O)P(OR)2, (RO)2POP(OR)a2n d (HORRO)P(OR)2 Dehydration of 'biphenanthrola' lso occurs to give a furan, which was characterisedb y X-ray crystallography. Two equivalents of (R)-CIP(OR)2 react with (R)- or (S)-'binaphthol' (HOR")2 to give (R, R, R)- and (R, S, R)-(RO)2P(OR"R"O)P(OR)2 ('pnp'). The disodium salt of (±)-'biphenanthrol' reacts with two equivalents of (±)-CIP(OR)2 to yield the single ((R, SR) / (SR, S))- diastereomeor f 'biphenanthriteT. he Pt(II), Pd(11aI)n dR h(I) coordinationc hemistry of these new diphosphitesis reported. The complexes[ MC12(diphosphite)a] re fluxional due to the conformational flexibility of the nine-memberech delate ring and the crystal structures of (R,R ,R )- and (SR,S )-[PtC12('biphenanthrite)s]h ow very different ring conformations T.he hydroformylation of styrenes catalysed by rhodium(I) complexes of (R, R, R)-'biphenanthrite', (R, S, R)-'pnp' and (R, R, R)-pnp' is reported. The 'biphenanthritec' complex gives 50% branched aldehyde and no asymmetric induction. The complex of (R, SR)-'pnp' gives 91-96% branched aldehyde and up to 72% ee. The differences in the catalytic properties of the diastereomer is discussed. In Chapter4 , the asymmetric hydrogenation of oc-enamides with rhodium(I) complexes of the new phosphonites and diphosphitesa s catalysts is discussed The diphosphonite complex shows low activity and a modest ee (up to 41%) but the analogousp hosphinophosphonitceo mplex is highly active and gives high ee's (up to 88%).T his is the first phosphinophosphonittoe be used in asymmetric hydrogenation. The monophosphonitceo mplexi s very activea ndt he ee's of up to 92% aret he highest obtained with a monodentatleig and in asymmetric cc-enamide hydrogenation. Chapter5 gives the experimental details for the chemistry reported in this thesis.

Orientadores: Elizabete Jordão, Wagner Alves Carvalho / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-14T20:39:31Z (GMT). No. of bitstreams: 1 Vignado_Carolina_M.pdf: 9451299 bytes, checksum: d456e8a7b568704dea2a9de758422b89 (MD5) Previous issue date: 2009 / Resumo: A hidrogenação catalítica de ácidos dicarboxilicos e seus ésteres e uma reação química de grande interesse industrial e acadêmico devido a formação de uma variedade de produtos químicos e farmacêuticos. A seletividade da reação depende do local onde ocorre a quebra da ligação podendo haver a formação de muitos produtos. Em geral, esse tipo de reação e catalisada por metais do grupo VIII suportados, como o rutênio, porem, catalisadores monometálicos tem se mostrado pouco eficazes em relação ao ataque da carbonila. O presente trabalho faz um estudo da hidrogenação do adipato de dimetila por catalisadores de rutênio suportado em titânia e promovidos por Fe, Sn, Ni e Ge. A adição desses outros metais teve como objetivo aumentar a seletividade ao ataque da carbonila e, conseqüentemente, levar a maiores formações do 1,6-hexanodiol, que e utilizado na produção de poliésteres, elastomeros poliuretanos, adesivos e plastificantes poliméricos. Os catalisadores foram preparados pelo método de impregnação de modo a obter um catalisador com teor nominal de 2% em massa de Ru e 4,7% em massa do promotor. Os suportes utilizados foram uma titânia apenas com fase anatase e outra com fase rutilo verificando-se a influencia dessas fases no desempenho dos catalisadores. Todas as amostras foram calcinadas e reduzidas a 400°C, temperatura na qual ocorre o efeito SMSI (forte interação metal-suporte) que tem sido benéfico para esse tipo de reação por resultar na formação de espécies TiOx que ativam a carbonila. As principais técnicas utilizadas para a caracterização foram microscopia eletrônica de varredura (MEV), difração de raios-x (DRX), adsorção de N2 (método de B.E.T.) e redução a temperatura programada (TPR). As reações foram conduzidas em fase liquida empregando-se o 1,4-dioxano como solvente a 250°C e 50 atm de H2 sob rotação constante de 1500 rpm em um reator Parr de alta pressão. Os resultados obtidos demonstram que a distribuição dos produtos e alterada nos sistemas cujos promotores foram o Fe e o Sn. Alem disso, observou-se um aumento na atividade catalítica. Os catalisadores promovidos por Sn apresentaram melhores seletividades na formacao do diol, enquanto que o sistema catalisado por RuNi/TiO2 apresentou alta seletividade na formação do EMM. Os catalisadores suportados em anatase apresentaram melhores resultados de atividade e seletividade. / Abstract: The catalytic hydrogenation of dicarboxylic acids and their esters is a reaction of great interest from the academic and industrial point of view due to the formation of different precursor for chemicals and pharmaceuticals industry. The selectivity depends on the place where the hydrogenolisys occurs, with potencial formation of many products. In general this reaction is catalyzed by supported VIII metal group as ruthenium. However, monometallic catalysts has been described as ineffective to attack the carbonyl group. This work studies the hydrogenation of dimethyl adipate by ruthenium catalysts supported on titania and promoted by Fe, Sn, Ni and Ge. The aim of these metals was to increase the selectivity to the attack of the carbonyl and thus leading to higher formation of 1,6-hexanediol, which is used in the production of polyester, polyurethane elastomers, adhesives and polymeric plasticizers. The catalysts were prepared by wet impregnation using aqueous suspensions in order to obtain catalysts with 2 wt% in ruthenium and 4.7 wt% in promoter. It was used anatase and rutilo supports to evaluate the influence of these phases in the performance of catalysts. These samples were subjected to calcination and reduction at 400°C, to guarantee the SMSI effect leading to the formation of species TiOx responsible for activation of the carbonyl. The techniques used for characterization were scanning electron microscopy (SEM), X-ray diffraction (XRD), N2 adsorption (BET method) and temperature programmed reduction (TPR). The reactions were performed in a liquid phase with 1,4-dioxane as solvent, at 255°C and 50 atm of H2, under mechanical stirring at 1500 rpm. Quantification of the reaction products was done by gas chromatography. The addition of Sn and Fe clearly changed the distribution of the products and an increase in the catalytic activity. Catalysts promoted by Sn showed better selectivity to the formation of diol. However the performance of RuNi/TiO2 showed high selectivity to MME as well as the monometallic systems. The catalysts supported on anatase had better results of activity and selectivity. / Mestrado / Sistemas de Processos Quimicos e Informatica / Mestre em Engenharia Química

The hydrogenation of ethylene reaction was studied over small catalyst beds of powdered nickel, nickel spheres, alumina supported nickel, powdered copper, and platinum wire. The reactor was positioned between the pole faces of an electromagnet, so that a magnetic field of strengths up to 10⁴ gauss could be applied across the catalyst bed. The reaction was studied at conditions of constant flow over the temperature range of 25° C to 550°C. The reaction rate was measured by means of a gas chromatograph, which had the sampling port installed in the system. Two magneto-catalytic effects were studied in this work: (i) the change in catalytic activity of a ferromagnetic catalyst as it is heated through its Curie temperature (internal magneto-catalytic effect); (ii) the change in catalytic activity of either a ferromagnetic or non-ferromagnetic catalyst, due to the presence of an external magnetic field (external magneto-catalytic effect). A clearly observable internal magneto-catalytic effect was found for the runs done on the ferromagnetic catalyst, nickel, which has an approximate Curie temperature of 360°C. In order to confirm this effect, runs were done over the temperature range of 300°C to 500°C on the non-ferromagnetic catalysts, copper and platinum. No change in reaction rate was found near 360°C, as was found using a nickel catalyst. No external magneto-catalytic effect was observed at any temperature. The hydrogenation of ethylene was found to be a rapidly self-poisoning reaction at temperatures above 100°C. Published literature indicates that at moderately high temperatures, desorption of reacting ethylene complexes off the catalyst surface causes the decrease in reaction rate. In this work a significant mole fraction of methane was detected in the reactor effluent gas, at temperatures above 300°C, and an accompanying carbon deposit was observed to form on the catalyst surface. The rapid decrease in catalytic activity at high temperatures was believed to be due to this carbon deposit. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate