This thesis examines the reactions of hydrocarbons exposed to chlorosulfonic acid in order to establish the reaction rate and associated molecular structure of each compound.

In order to explore the N-H stretching region of aliphatic amines, we performed a study of the Raman spectrum of n-propylamine at various concentrations in cyclohexane. Statistical analysis provided evidence of a second symmetric stretching vibration, which we were able to assign to nonhydrogen bonded NH2 groups. To obtain additional evidence on the existence of monomers in n-propylamine and to further study hydrogen bonding and Fermi resonance in aliphatic amines, we extended the investigation to the analysis of the Raman spectrum of this compound over an extended range of temperature in the neat liquid phase. This study corroborated our finding that the peak previously assigned to the symmetric stretching mode of hydrogen bonded amines is actually composed of two bands. Furthermore, trends in both the resolved band parameters and the Fermi resonance analysis were tabulated, allowing one to monitor the change in the N-H valence region with concentration and temperature.

Various modern spectroscopies have been utilized with considerable success in recent years to probe the dynamics of vibrational and reorientational relaxation of molecules in condensed phases. We have studied the temperature dependence of the polarized and depolarized Raman spectra of various modes in the following dihalomethanes: dibromomethane, dichloromethane, dichloromethane-d2, and bromochloromethane. Among other observed trends, we have found the following: Vibrational dephasing times calculated from the bend) and (C-Br stretch) lineshapes are of the same magnitude in CI^B^. The vibrational dephasing time of [C-D(H) stretch] is twice as long in CD2Cl2 as in CH-^C^, and the relaxation time of (C-Cl stretch) is greater in CI^C^ than in CD2CI2. Isotropic relaxation times for all three stretching vibrations are significantly shorter in C^BrCl than in CI^C^ or CI^B^. Application of the Kubo model revealed that derived modulation times are close to equal for equivalent vibrations in the various dihalomethanes. Thus, the more efficient relaxation of the A^ modes in CE^BrCl can be attributed almost entirely to the broader mean squared frequency perturbation of the vibrations in this molecule.

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.

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 body of information concerning carbon-carbon spin-spin coupling constants now includes a large number of coupling constants, the establishment of a dihedral angular dependence on 3JCC, and the application of 3JCC to conformational analysis. This study adds another dimension to the growing wealth of information associated with 13 C-NMR: the influence of some non-bonded interactions on 3JCC Four types of non-bonded interactions that could influence vicinal carbon-carbon NMR coupling constants were investigated. To facilitate the NMR studies, a variety of 13C-labeled compounds were synthesized.