This dissertation is a study involving the synthesis and chemistry of arylhaloketenes and cyclopentadiene cycloadducts, and a study of the cycloadduct isomer distribution was begun.

The objectives of this research problem was to employ alkylhaloketene-olefin isomer distributions to aid in understanding the stereochemistry and mechanism of alkylhaloketene-olefin cycloadditions.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1950. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaf 50).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1948. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves [57-58]).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1937. / Typescript. Includes abstract and vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

The objective of this research problem was to synthesize aldohaloketenes and investigate the chemistry of this new class of ketenes.

Part I describes the addition of several acid chlorides to dimethylketene. The resulting 3-ketoacid chlorides were isolated and characterized. Part II describes the cycloaddition of several aldoketenes to chloral. The ketenes were generated in situ by dehydrohalogenation and dehalogenation of appropriately substituted acyl halides.

The effect of varying substituents on structure and energies of bisketenes was studied using ab initio methods. Effect of substituents on ring closing reaction of bisketenes to the corresponding cyclobutenediones was also studied using ab initio methods. One or two of the following substituents were used to study the effect of varying substituents: BH2, CH3, NH2, OH, F, AlH2, SiH3, PH2, SH, Cl. Studies were done at the Hartree-Fock (HF), Møller-Plesset (MP2), and Density Functional Theory (B3LYP) levels of theory using the 6-31G* basis set.

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.

The objective of this investigation was to determine the electronic effects of the halogen atoms in dihaloketenes such as dichloroketene and dibromoketene.