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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.

Microcosm studies were conducted beginning with three xylene isomers: ortho-xylene, meta-xylene and para-xylene; and continued with the four mononitroxylene (MNX) isomers, culminating with testing ten dinitroxylene (DNX) isomers. Soil samples were obtained from a historically contaminated site with high levels of dinitrotoluene (DNT), trinitrotoluene (TNT) and dinitroxylene (DNX) and used as the inoculum for microcosm tests. The microcosm method of different isomers was based on the previous work on biodegradation of nitrotoluene. As it was demonstrated previously that 2,4-DNT degrading bacteria were present at the site, it was hypothesized that these may be capable of transforming or cometabolizing some of DNX isomers. Thus, DNX cometabolism studies were conducted in the presence of 2,4-DNT degrading bacteria. The presence of xylene and 2,4-DNT degrading was confirmed in this thesis. Meanwhile, several MNX and DNX isomers showed degradability in microcosm studies. Cometabolism studies showed that four DNX isomers could be cometabolized by 2,4-DNT enrichment.

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Thesis (Ph.D.)--University of Tulsa, 1995. / Includes bibliographical references (leaves 197-214).

The fluorescence spectrum of many polycyclic aromatic compounds (PACs) depends upon solvent polarity. The emission spectrum of PAC monomers consists of several major vibronic bands labeled I, II, etc., in progressive order. Emission intensity enhancement of select bands is observed in polar solvents.

The process of C. K. Bradsher for preparing mesosubstituted anthracene and 1,2-benzanthracene derivatives has been widely extended. The purpose of this research was to extend this process to the thiophene series, in addition to continuing some work on the 9-(dimethyl)- phenylanthracene series and some newly developed l,2-dimethyl-10-phenyl)-anthracene series. 2'-Thienyl-2-benzylbenzophenone was prepared and cyclized to 9-(2-thienyl)-anthracene by the conventional methods in good yields. 3'-Thienyl-2-benzylbenzophenone was prepared in a different way, indirect and tedious. Thiophene was iodinated to tetraiodothiophene and tetraiodothiophene was reduced with aluminum-amalgam to 3-iodothiophene. 3-Thienylmagnesiumiodide was prepared by the entrainment technique and condensed with 2-cyanodiphenylmethane to 3'-thienyl-2-benzylbenzophenone. This ketone was cyclized to 9-(3'-thienyl)-anthracene by the standard acid mixture. 2-(1-Naphthylmethyl)-phenyl-2-thienylketimine formed from the condensation between 2-(1'-naphthylmethyl)- benzonitrile and 2-thienylmagnesiumbromide resisted hydrolysis to the corresponding ketone but cyclized quantitatively to 10-(2-thienyl)-l,2-benzanthracene. Following the classical Bradsher process, the reaction between 2-thienylmagnesiumbromide and o-chlorobenzaldehyde was unsuccessful because the hydrol formed was so reactive that it polymerized rapidly and ended up with tars. A cross-condensation reaction between 2-ethynylmagnesium bromide and o-chlorobenzylchloride was utilized to give the expected 2-(2'-chlorobenzyl)- thiophene in one step. This new procedure has been widely extended to the other series. It is preferred to. the conventional Bradsher process and the Friedel-Crafts method in terms of time, chemicals, and unequivocal products formed. 2-(2'-Chlorobenzyl)-thiophene so formed by the new procedure was converted by von Braun reaction to the corresponding nitrile and the nitrile was allowed to react with phenylmagnesiumbromide to give 2-(2-thienylmethyl)-benzophenone. The above ketone was cyclized almost quantitatively to 4-phenyl-thiophanthrene. The thiophene-containing ketones prepared in this research are very viscous oils. In order to have crystalline derivatives for identification purposes these ketones were oxidized to the corresponding diketones. 2-Thienyl-2-benzylbenzophenone and 2-(2'-thienylmethyl)- benzophenone gave the identical diketone, 2-benzoyl-2'- thienyl-benzophenone. 3 1 -Thienyl-2-benzylbenzophenone was oxidized to anthraquinone by using 25% sulfuric .acid, acetic acid and sodium dichromate. The formation of anthraquinone indicates that the monoketone cyclized first and then split off the thiophene ring. Apparently, the 3-thienyl group is more susceptible to oxidation than the 2’-thienyl group. A study of the oxidation of anthracene derivatives for structure proof was made using 9-phenylanthracene as a model compound. It was oxidized to 10-phenyl-10-hydroxyanthrone which resisted further oxidation to anthraquinone. It is obvious that the tertiary alcohol system stabilized the phenyl ring. In continuing the work on the 9-(dimethyl)-phenylanthracene series, the yields of three ketimine salts and one ketone were improved. Satisfactory analytical data was obtained for 2’,6’-dimethyl-2-benzylbenzophenone. In an attempt to overcome the steric effects offered by 2,6-ortho groups, 2-(2',3'-dimethylbenzyl)-benzonitrile was prepared. The starting material for this series, l-bromo-2,3-dimethylbenzene has been prepared in 47% yield by diazotization in comparison with the previous yield of 30%. / Doctor of Philosophy

LD2668 .T4 1966 T458 / Master of Science

published_or_final_version / Chemistry / Master / Master of Science

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