Polarographic results for the reduction of a number of aromatic compounds in anhydrous acetic acid were obtained. The compounds studied included: o-, m- and p-nitroanilines and nitro-phenols; o-nitrobenzoic acid; 2,4-dinitro substituted phenol, benzoic acid and toluene; 3,5-dinitro substituted phenol and benzoic acid; 2,4,6-trinitro substituted phenol, benzoic acid and toluene. It has been shown that activating substituents on the benzene nucleus hinder the reduction of nitro groups on the ring, the effect being most pronounced for the o- and p- positions. Hydrogen bonding has been shown to occur to a lesser extent in acetic acid than in aqueous solution. Deactivating groups have been shown to cause nitro substituents to be more easily reduced, the effect decreasing in the order o<m<p. The polarographic reduction of a nitro group has been postulated to proceed with the same mechanism as in aqueous solvents. This reduction has been assumed to be a four or six electron irreversible reaction to the hydroxylamino or amino group repectively. Acetic acid, although limited in the potential range available, has been determined to be a suitable solvent for polarographic studies of organic compounds. / Science, Faculty of / Chemistry, Department of / Graduate

The transfer of energy from one species of hydrocarbon to another has been observed. The conditions under which such transfer occurs indicate that one aromatic hydrocarbon may be absorbed onto crystals of the other forming a surface complex with a binding energy of a few hundred calories. Transfer of energy occurs readily between the components of this complex but not between molecules of different hydrocarbons when both are in solution. However, evidence for resonance transfer of energy between pairs of molecules of the same substance when both are in solid solution has been found. Studies of a large number of hydrocarbons have failed to reveal any single electronic property of the molecule which determines its ability to form complexes of the type found. The techniques developed were applied to a preliminary study of the rate of disappearance of carcinogenic hydrocarbons applied to the skin of mice. Also included are literature surveys on the known interactions of polycyclic hydrocarbons, the mode of reaction of carcinogenic hydrocarbons with living cells, and the spectral properties of chlorophyll. / Science, Faculty of / Chemistry, Department of / Graduate

The infrared spectra of single crystals of naphthalene-d₈, anthracene-h₁₀ and anthracene-d₁₀ are reported with the plane of the incident radiation parallel to all three principal optical directions of the crystals. The polarized measurements extend down to 50 cm⁻¹and all low-energy infrared-active molecular vibrations and many lattice vibrations have been assigned. The laser-excited Raman spectra of single crystals of naphthalene-d₈ and anthracene-d₁₀ also are reported and this data was supplemented by depolarization ratio measurements from solution and from the melt. With the new information available from these studies a re-evaluation of the assignments of the molecular fundamentals of these three molecules has been made. When the list of fundamentals was as complete as possible, attention was directed to the force fields. The out-of-plane field of benzene was reconsidered, and the assumption that interaction constants should be as small as possible was completely supported. Transfer of these force constants to naphthalene was successful; however, it proved to be impossible to fit all the observed non-planar frequencies of anthracene with the force constants developed for benzene. An in-plane modified valence force field designed for benzene was extended to naphthalene and anthracene and refined to fit simultaneously the observed frequencies of all three molecules and their three perdeuterated analogues. The results were compared with the results of a similar calculation carried out by Neto, Scrocco and Califano and presented elsewhere, and certain differences were noted, particularly in the anthracene-h₁₀ and -d₁₀ B₂[subscript u] ring modes. In order to find out how well force fields developed for these molecules would transfer to related but less similar molecules, the vibrations of pyrene and acenaphthene were considered. The infrared spectra of single crystals of pyrene-h₁₀, pyrene-d₁₀ and acenaphthene were measured, with emphasis on the low-frequency regions not previously studied. The data obtained were supplemented by Raman measurements carried out by others in this laboratory and fairly complete assignments of the normal vibrations were possible. The fundamental frequencies of these molecules were calculated with force fields synthesized from the two planar fields mentioned earlier and from the out-of-plane fields of benzene and (for acenaphthene) cyclopentane. Comparison of the observed and calculated frequencies showed that although some fairly large discrepancies did arise, they were few in number and located only in the region of the ring stretching vibrations (above about 1200 cm⁻¹) . The fit to the fundamentals below that energy was most encouraging, and indicated that the transfer of force constants from one molecule to another in order to calculate approximate frequencies was certainly possible. / Science, Faculty of / Chemistry, Department of / Graduate

acase@tulane.edu / The syntheses and structural characterization of 3-arylimino steroids, tribenzodecacyclene, hexabenzodecacyclene, and a new class of twisted chiral polycyclic aromatic compounds, the “hairpin furans” are described. In the hope of generating a new class of materials with large optical rotations, various arylamines were condensed with cholest-4-ene-3,6-dione (14) to give 3-arylimino steroids. These compounds possess moderately high specific rotations ([α]D ~ 300-800) and strong circular dichroism. One such derivative, 3-(4-methoxyphenylimino)cholest-4- en-6-one (15), crystallizes as the (E)-imine and upon dissolution undergoes mutarotation to an equilibrium mixture of (E)- and (Z)-isomers with a half-life of approximately 1 h at room temperature, as judged by both NMR spectroscopy and polarimetry. High-temperature, TiCl4-catalyzed, triple aldol condensations of aceanthrenone 26 and acenaphthacenone 27 gave tribenzodecacyclene 18 and hexabenzodecacyclene 19, respectively, in yields of 16% and 0.8%, respectively. Compound 18 is a red, crystalline solid that is stable under ordinary conditions; its X-ray structure reveals it to be a strongly pitched, C3-symmetric, molecular propeller. In contrast, the more highly strained compound 19 is a blue-black solid whose solutions are unstable to air and light. Its simple NMR spectra, as well as HDFT calculations, indicated that it is a D3-symmetric molecular propeller. The thermal reaction of two cyclopentadienones with 5,5’-binaphthoquinone or 6,6’-dimethoxy-5,5’-binaphthoquinone in refluxing nitrobenzene (210 °C) gives, in a single synthetic step that includes two Diels-Alder additions, two decarbonylations, and two dehydrogenations, giant biaryl bisquinones (compounds 42, 50, 52, 53 and 62). However, when two cyclopentadienones react with 6,6’-dimethoxy-5,5’- binaphthoquinone in nitrobenzene at higher temperatures (250-260 °C), the resulting products are molecular ribbons composed of two twisted aromatic systems fused to a heteropentahelicene (49, 51, and 54). These molecules are representatives of a new class of chiral polycyclic aromatic compounds, the “hairpin furans”. Interestingly, reheating a dimethoxy-substituted giant biaryl (e.g., 52) in nitrobenzene at 260 °C does not yield the corresponding hairpin furan, and the mechanistic studies indicate that some intermediate or byproduct of the synthesis of the giant biaryls is a reagent or catalyst necessary for the conversion of the dimethoxybiaryl to the furan. / 1 / Xin Geng

Claisen first synthesized Chalcone in 1881 by condensing acetophenone with benzaldehyde using sodium methoxide as a condensing agent. Chalcone and its derivatives have been prepared primarily as intermediates for the synthesis of anthocyanins and other related pigments. In recent years extensive preparation and study of chalcones has been carried out utilizing chalcones for their biological effects in medical and pharmaceutical fields. It has been shown that certain highly substituted compounds present in the flower pigments as additives to adhesive absorb ultraviolet radiation. Carboxylic acid chalcones have become known for their therapeutic action in the treatment of chronic kidney diseases, diseases of the eye, and rheumatoid diseases, such as bursitis and osteoarthritis. Treatment of chalcones with sulfuric acids to obtain α-ketosulfones, used as chemotherapeutic agents, has been under investigation and useful results have been obtained. Many of these α-ketosulfones are used to identify small amounts of sulfuric acid obtained from the cleavage and rearrangement of certain sulfones. In the research of genetic factors which regulate the formation of flavonoids factors in organisms, a suitable method for determining these compounds in small amounts in plant tissues is of very great importance and chalcones have been under investigation to serve this purpose. The observation of insecticidal bacteriostatic and tuberculostatic activities in chalcones has led to extensive investigation of chalcones.

This document only includes an excerpt of the corresponding thesis or dissertation. To request a digital scan of the full text, please contact the Ruth Lilly Medical Library's Interlibrary Loan Department (rlmlill@iu.edu).

No description available.

No description available.

No description available.

This report discusses research which was conducted in two areas: the study of aromatic nucleophilic fluoroalkoxylation assisted via cationic phase transfer catalysis and the study of unsymmetrical vinamidinium salts and their reactions with organometallic reagents. Sodium alkoxides have been successfully used to fluoroalkoxylate activated halo- aryl and heteroaryl substrates under phase transfer catalysis conditions. Optimum reaction conditions incorporated tetra-n-butyl-phosphonium bromide as the catalyst and refluxing toluene as the solvent medium. Different quarternary phosphonium and arrmonium salts have been evaluated as catalysts: also, the effects of activating groups, leaving groups, and nucleophiles have been reported. The reaction of 3-dimethylamino-3-phenyl-prop-2-en-l-ylidendimethyliminium perchlorate with organolithium and Grignard reagents has also been studied in an effort to define the reaction in terms of which electrophilic site of the salt is susceptible to nucleophilic attack to the greatest extent. The results reported reveal that the reaction occurs at the 1-position in all cases producing the α, β-unsaturated ketone after acid hydrolysis. Finally, this report reveals the experimental procedures used as well as the spectral and physical data of all new compounds synthesized. Explanations of the data are offered and recommendations for future research in both areas are given.