The reaction of chlorodimethylvinylsilane with tertbutyllithium was investigated in the presence of several conjugated dienes. In all cases except with 2,5-dimethylfuran, [2+4] cycloadducts of a silene intermediate are obtained in hydrocarbon solvents. The presence of THF in the reaction mixture suppresses the formation of cycloadducts in favor of 1,3-disilacyclobutanes. In the reaction of dimethylethoxyvinylsilane or dimethylmethoxyvinylsilane with tert-butyllithium the main product is the 1,1-dimethyl2-neopentyl-4-(dimethylalkoxysilyl)silacyclobutane. It is concluded that lithium chloride elimination to give silene intermediates occurs in hydrocarbon solvents. In the presence of strong Lewis bases or when the leaving group on silicon is an alkoxy group, the addition reaction giving a-lithiosilanes occurs and products arising from their coupling reactions are obtained.

The first objective of this investigation was to conduct a systematic study into the reactions of chloroketenes with ketene acetals. The second objective was to explore the synthetic utility of these reaction products and offer a rational explanation for these reaction products.

This dissertation reports the preparation of several types of anthraquinones structurally related to adriamycin. It describes the synthesis of two types of 2-aminoquinizarin compounds. It also presents two new syntheses of a heterocyclic tetracyclic ring system, similar to the aglicone ring system of adriamycin. A series of 2-aminoquinizarins was prepared by adding several primary amines to quinizarin. Quinizarin was shown to be essentially inert toward secondary amines. Several secondary amine adducts with quinizarin have been prepared, however, by treating the bis-boroacetate ester of quinizarin with the amines. Both types of 2-aminoquinizarin compounds exhibit outstanding potential for possessing antineoplastic activity, and several have been submitted to the National Cancer Institute for testing in their screening program for antineoplastic agents.

Since the development of the understanding that the electron distribution within a molecule is chiefly responsible for its properties and behavior, factors influencing this charge distribution have been of interest to scientists. The chemical reactivity of a molecule, the physical properties, and to a large extent, structure and geometry, are all functions of the electron distribution. This study examines the issue of electronic structure from two points of view, each of them focussing on a specific component within the molecules studied. In the present work, the effects of the highly polar carbonyl group on spectroscopic parameters and physical behavior are investigated. An additional area of study is the effect of fluorine substitution on the energy levels of some halogenated ethylenes. The specific parameters examined are the ionization potentials, the absorption frequencies, and the energies of a class of excited states known as molecular Rydberg states. It was during the study of these halogenated ethylenes that the observations leading to the carbonyl compound investigations were made, so that the two areas examined are connected both experimentally and chemically.

This paper describes a new technique for analyzing fire debris using nuclear magnetic resonance (NMR) spectroscopy. Petroleum distillates, which are commonly used accelerants, were weathered, burned, and steamdistilled. These, as well as virgin samples of the accelerants, were analyzed by gas chromatography and nuclear magnetic resonance spectroscopy. In addition, solvent studies and detectibility limit studies were conducted. The use of NMR is described as a valuable adjunct to the existing methods of analysis.

The laser Raman spectra of tetrachlorocyclopropene in the liquid and solid phases have been recorded and vibrational assignments are presented. These results along with root mean squared vibrational amplitudes from electron diffraction data have been employed in a normal coordinate analysis in which a 19 parameter potential function is refined. This potential function, originally expressed in terms of compliance constants, is then used to derive the corresponding conventional and relaxed force constants.

Trihalomethanes such as chloroform, dichlorobromomethane, dibromochloromethane, and bromoform are formed when natural water is chlorinated in water treatment. This investigation explores the use of ozone to remove organic precursors from natural water, thus decreasing trihalomethane formation potential. The data suggest a mechanism involving formation of secondary precursors after prolonged contact with ozone, suggesting that trihalomethane precursors may be minimized by using low doses of ozone and short contact time.

A series of picosecond excite-probe experiments was performed on various concentrations of aqueous and ethanolic solutions of rhodamine B in order to determine the existence of dimerization in those solutions. The goals of the research presented in this dissertation were twofold. Initially, various techniques of time-resolved spectroscopy were to be employed to further characterize the ground and excited-state molecular properties of the aqueous RB dimer. The information obtained, and the techniques developed in that study would then be utilized in an effort to secure evidence which would support or refute the claims of rhodamine B dimerization in an ethanolic solution.

Rules which correlate structure and insecticidal activity of pyrethroids have evolved over the last thirty years from the results obtained in the testing of various synthetic pyrethroids. The major portion of these rules have dealt either with the development of new alcohol moieties or variations in the unsaturated side chain of the cyclopropane ring. There has been very little work done concerning modifications of the cyclopropane ring. This study was initiated to discover the affect of substituting an aziridin ring for the cyclopropane ring found in pyrethroids.

This study consists of four major areas of research. First, the relationship between and was extended to Lrl nil homoallylic couplings and was used to determine the relative degree of puckering in a series of dihydroaromatic carboxylic acids. Second, the effect of coupling contributions transmitted through space were examined by theoretical calculations of the intermediate neglect of differential overlap finite perturbation theory type (INDO-FPT) including selective overlap reduction experiments to determine the sign and magnitude of the major through-space contributions and the effect of the orientation of the substituent upon the vicinal carbon3 carbon coupling. Third, the dependence of the J upon substituent orientation in norbornanes was empirically investigated by the synthesis of a series of lactones and cyclic ethers whose conformation was rigid and known. Fourth, a large number of norbornanes substituted with methyls in the 1, 3, and 7 position and a carbon-13 labeled substituent in the 2 position were synthesized and studied in order to obtain a variety of vicinal C-C couplings; all the NMR parameters for this series of compounds were determined while the carbon13 labeled substituent was varied from methyl to methylene to carbinol to aldehyde and to carboxylic acid.

The physiological role of LCAT has been the subject of a number of recent articles (Glomset, 1979; Nilsson-Ehle et al., 1980). According to most current theories, the enzyme functions in combination with high-density lipoproteins in the reverse cholesterol transport pathway which presumably returns peripheral cholesterol to the liver where cholesterol catabolism takes place. Despite the exciting potential for studies on the catalytic function and the nature of the enzyme-substrate complex, the mechanism of action of LCAT remains largely unexplored. The relatively slow progress in the elucidation of the LCAT reaction mechanism is likely to be due to the difficulties in the isolation of the enzyme in sufficient quantities. Consequently, considerably less is known about the physical and chemical properties of the enzyme. Therefore, the first objective of this investigation was to isolate and purify sufficient amount of enzyme for subsequent characterization studies. The second objective of this investigation was to characterize the physical properties of the enzyme by techniques including analytical ultracentrifugation, ultraviolet spectroscopy, and circular dichroism and fluorescence spectroscopy. The third objective of this investigation was to characterize the chemical properties of the enzyme which deals with the amino acid and carbohydrate composition and with some basic structural features …