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Zeotropic mixtures exhibit a temperature glide between the dew and bubble points during condensation. This glide has the potential to increase system efficiency when matched to the thermal sink in power generation, chemical processing, and heating and cooling systems. To understand the coupled heat and mass transfer mechanisms during phase change of high-glide zeotropic mixtures, a comprehensive investigation of the condensation of ammonia and ammonia/water mixtures in small diameter channels was performed. Condensation heat transfer and pressure drop experiments were conducted with ammonia and ammonia/water mixtures. Experiments on ammonia were conducted for varying tube diameters (0.98 < D < 2.16 mm), mass fluxes (75 < G < 225 kg m⁻² s⁻¹) and saturation conditions (30 < Tsat < 60°C). Zeotropic ammonia/water experiments were conducted for multiple tube diameters (0.98 < D < 2.16 mm), mass fluxes (50 < G < 200 kgm⁻² s⁻¹) and bulk ammonia mass fraction (xbulk = 0.8, 0.9, and > 0.96). An experimental methodology and data analysis procedure for evaluating the local condensation heat duty (for incremental ∆q), condensation transfer coefficient (for pure ammonia), apparent heat transfer coefficient (for zeotropic ammonia/water mixtures), and frictional pressure gradient with low uncertainties was developed. A new heat transfer model for condensation of ammonia in mini/microchannels was developed. Using the insights derived from the pure ammonia work, an improved zeotropic condenser design method for high-temperature-glide mixtures in small diameter channels, based on the non-equilibrium film theory, was introduced. The key features of the improved model were the consideration of annular and non-annular flow effects on liquid film transport, including condensate and vapor sensible cooling contributions, and accounting for mini/microchannel effects through the new liquid film correlation. By understanding the behavior of these mixtures in microchannel geometries, highly efficient, compact thermal conversion devices can be developed.

Isoxazoles and isoxazolines have been shown in the literature to be an important scaffold for pharmaceuticals and insecticides, as well as a source of synthetic versatility important to many syntheses. As a substitute for other aromatic rings, isoxazoles are known to change the efficacy of a given compound. Isoxazolines can be used as a precursor to many other functional moieties that may be effected during earlier synthetic steps. There are many routes to the heterocyclic moiety, allowing for their insertion in a wide range of molecules. Our group has previously reported a condensation of arylaldehydes with hydroxylamine to first make an aryloxime which can, after generating the nitrile oxide, then cyclize with an alkene or alkyne in situ and create the isoxazoline or isoxazole, respectively. The Knoevenagel Condensation reaction is identified as the addition of an activated methylene complex, malononitrile or cyanoacetamide, with a carbonyl followed by dehydration.. Our group has previously reported a facile, one-pot reductive alkylation of benzyl malononitriles. These compounds have been noted as having many insecticidal uses, as well as being potent pharmacophores. The scope of this project is to further explore and optimize the condensation of aryl aldehydes and methylene complexes. The condensed and reduced methylene complex will then be alkylated to join the heterocyclic moiety to reach the final disubstituted methylene product. A second approach will also be explored in which the monosubstituted malononitrile will first be alkylated with allyl or propargyl bromide, which can then undergo a 1,3-dipolar cycloaddition with a nitrile oxide. The library of compounds generated will be sent to collaborators to test the biological activity of the molecules. / Introduction and background literature -- Reactions of methylene complexes -- Synthesis of disubstituted methylene complexes. / Department of Chemistry

The quinoline-5,8-diones are an important class of compounds with a wide spectrum of biological activites such as antibacterial, antiasthmatic, antifungal, antitumour and antiparasitic agents. Over the past three decades many variously substituted derivatives of quinoline-5,8-diones have been synthesized and reported. The majority of them dealt with the chemistry of C-6 and/or C-7 substituted quinolinediones and were related to Lavendamycin. Our lab has developed several procedures for the condensation (Knoevenagel) and reduction of aldehydes and ketones with malononitrile. When this reductive alkylation procedure was attempted with quinoline-2-carboxaldehyde, a crude product was observed by NMR spectroscopy. This product rearranged upon attempted purification via recrystallization or column chromatography. The nucleophilic attack of the quinoline N on the C of the nitrile followed by a proton transfer and a tautomerization resulted in the creation of indolizine. We will study the reductive alkylation of a series of quinoline-5,8-diones with carboxaldehydes at the C-2 position with malononitrile. This reaction is carried out in 95% ethanol with no catalysts present. This reaction mixture is then diluted with additional 95% ethanol and then cooled in an ice/water bath before the addition of sodium borohydride (NaBH4) to afford the desired monosubstituted malononitrile. We have also carried out the reactions with a range of other substituted quinoline compounds. In these cases the indolizines were not observed. It is assumed that the indolizine product does not form due to the presence of substituents on the C-8 position. Additional studies will focus on unsubstituted C-8 quinoline rings to prepare other novel indolizines. Otherwise, various reactions are performed to force the formation of indolizine. / Introduction/background -- Preparation of quinoline derivatives and their respective carboxaldehydes -- Preparation of monosubstituted malononitriles and indolizines. / Department of Chemistry

In 2006, an amphoteric molecule containing both an aldehyde and an unprotected amine was reported in the Yudin group by Dr. Ryan Hili. The unprotected aziridine aldehyde exists as homochiral dimers. Furthermore, due to the reversibility of the hemiacetal formation, the free aldehyde is available to undergo a wide array of reactions including an Ugi multicomponent reaction to give the final peptide macrocycle. Thus far, the mechanistic pathway involved in the Ugi reaction between S-trans aziridine aldehyde dimer and L-amino acids in the presence of tert-butyl isocyanide has given high diastereoselectivity whereas low diastereoselectivity is observed if the aziridine dimer is of the opposite stereochemistry. Herein, preliminary results show that a S-cis aziridine aldehyde with either a D or L-secondary amino acid gives high diastereoselectivity showing that the reaction is under Felkin-Ahn control.

In 2006, an amphoteric molecule containing both an aldehyde and an unprotected amine was reported in the Yudin group by Dr. Ryan Hili. The unprotected aziridine aldehyde exists as homochiral dimers. Furthermore, due to the reversibility of the hemiacetal formation, the free aldehyde is available to undergo a wide array of reactions including an Ugi multicomponent reaction to give the final peptide macrocycle. Thus far, the mechanistic pathway involved in the Ugi reaction between S-trans aziridine aldehyde dimer and L-amino acids in the presence of tert-butyl isocyanide has given high diastereoselectivity whereas low diastereoselectivity is observed if the aziridine dimer is of the opposite stereochemistry. Herein, preliminary results show that a S-cis aziridine aldehyde with either a D or L-secondary amino acid gives high diastereoselectivity showing that the reaction is under Felkin-Ahn control.

Typescript. / Theses (Ph. D.)--University of Hawaii at Manoa, 1978. / Bibliography: leaves 85-89. / Microfiche. / viii, 89 leaves ill

Thesis (Ph.D.)--York University, 2006. Graduate Programme in Earth and Space Science. / Typescript. Includes bibliographical references (leaves 188-201). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&res_dat=xri:pqdiss&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&rft_dat=xri:pqdiss:NR19810

Thesis (M.S.)--Oregon State University, 2008. / Printout. Includes bibliographical references (leaves 84-85). Also available on the World Wide Web.

Thesis (BSc. (Hons))--Australian National University, 2002. / Available via the Australian National University Library Electronic Pre and Post Print Repository. Title from title screen (viewed Feb. 18, 2003). "A thesis submitted as partial fulfillment of the requirements for the degree of Bachelor of Science with Honours in theoretical physics at the Australian National University" Includes bibliographical references.