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The Vacuum Ultraviolet Spectra of Cyclohexane, Cyclohexene, 1,4-Cyclohexadiene, Isotetralin, and Several Methyl Substituted Analogs

Description: A paucity of literature exists on the Independent System analysis of adjacent, parallel transition dipoles. Applying this theory and certain spectral information semiemperical calculations were made to predict absorption profiles and band intensities. To aid in the assignment of the 7*+7 absorption bands it was necessary to obtain the vacuum ultraviolet spectra of cyclohexane and cyclohexene. Because the spectra of these molecules contained sharp, atomic-like absorption bands a Rydberg series could be fitted to certain absorptions, thus the determination of their ionization potentials. Using Independent System analysis profiles and intensities of 7*+q-- absorption bands ins 'several methyl substituted 1,4- cyclohexadienes and isotetralin were predicted where general agreement was found with observed experimental spectra.
Date: December 1974
Creator: Tidwell, Edgar Rhea
Partner: UNT Libraries

ESR Studies of Group IV Substituted Anilines

Description: The purpose of the investigation described herein was to investigate the degree of delocalization of the unpaired electron in ion radicals formed in the oxidation process of compounds with aromatic rings connected by means of various groups and atoms not entering the ring; then, to establish the relationship of coupling constants in radical cations with substituent σ values. The parent cation radical, in which the co-planar ion was derived from N,N-dimethylaniline, was selected in order to maximize the substituent effects on coupling constants and to obtain couplings at several positions (specifically, CH3, N, and ring protons).
Date: June 1970
Creator: Wong, Pui-Suen
Partner: UNT Libraries

Synthesis of trimethylsilyl-substituted pentacyclo(²,⁶.0³,¹º.0⁵,⁹)undecanes and chloro-substituted pentacyclo(²,⁶.0³,¹º.0⁵,⁹)undecane

Description: As part of a continuing study of the synthesis and chemistry of new, substituted pentacyclo(²,⁶.0³,¹º.0⁵,⁹)undecanes, the following compounds have been synthesized: 1: X=O, Y=SiMe_3; 2: X=CH_2, Y=SiMe_3; 3: X=O, Y=Cl; 6: X=OAc, Y=H; 8: X=OC(O)Ph, Y=H; 9: X=OSO_2Ph, Y=H; 11: X=OH, Y=H; 12: X=OMe, Y=H; 14: X=CHSiMe_3, Y=SiMe_3; 15: X=OH, Y=Cl; 16: X=OAc, Y=Cl; 17: X=OMe, Y=Cl. An important objective of this work is to prepare new polycyclic cage compounds which can be utilized as intermediates for the synthesis of new, substituted tricyclopentanoid natural products (triquinanes) and related systems. Compounds 1-4 were identified as target molecules in this connection.
Date: August 1984
Creator: Huang, Chunmin
Partner: UNT Libraries

A Carbon-13 and Lithium-6 NMR Study of Alkyllithium Compounds

Description: A variable temperature 13C and 6Li NMR study has been conducted for 6Li-enriched ethyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-, t-butyl--, isopentyl-, 2-ethylbutyl-, and n-hexyllithium in cyclopentane. Significant differences in the 13C NMR parameters are observed as a function of the alkyl group and temperature. These changes are compared to the 6Li spectra and explained in terms of the aggregates present. 13C-6Li coupling is readily observed in both the 13 6 C and Li spectra of compounds which contain branching at either the alpha or beta carbons of the alkyl group. This coupling has been used to identify the aggregates present in solution and to identify the fluxional behavior of these aggregates.
Date: December 1983
Creator: Jensen, Randy M.
Partner: UNT Libraries

Optimization of High Performance Liquid Chromatographic Separations

Description: This study had a twofold purpose. First, the usefulness of the simplex algorithm as a short method of optimization in high performance liquid chromatographic separations was investigated. The second was to test a modified simplex method. The volume fractions of mobile phase components were chosen as the variable factors in the optimization process. Four test cases were performed which included separation of cholesterol esters, naphthalene and its derivatives, polycyclic aromatic compounds, and the thiane compounds. The standard for accepting an optimum was based on the baseline separation of two adjacent peaks and the analysis time. In addition to successful separations, the correlation between the separation and the chemical characteristics of mobile phase compositions was calculated and this could then be used for further modification of simplex search strategy.
Date: August 1983
Creator: Nguyen, Khanh Thi
Partner: UNT Libraries

Mass Spectral Study of Trimethylsilylmethyl Substituted Chlorosilanes

Description: The mass spectra of the compounds [Me 3 SiCH2 nSiCl 4 n (n=1-3) were studied in detail. MIKES and CID spectra were used in conjunction with the observance of metastable processes to develop consistent fragmentation schemes. Particular attention is drawn to the formation of charged and neutral species containing the silicon-carbon double bond, including 2-silaallene, under conditions of electron impact.
Date: December 1982
Creator: Pope, Keith Randal
Partner: UNT Libraries

The Synthesis and Reactivity of Bis(silyl)acetylenes

Description: Six bis(silyl)acetylenes with the following varied silicon substituents were prepared: I (Me, Me); II (H, H); III (Cl, H); IV (Cl, Cl); V (OMe, H); VI (OMe, OMe). While I and II may be prepared by the reaction of dilithio- or bis(bromomagnesium)-acetylide with appropriate chlorosilane, similar reactions designed to give III - VI give oligomers, YMe_2Si(C≡C-SiMe_2)_nY, VII, Y = Cl, OMe, as the major products indicating that the acetylenic functionality on silicon activates the chlorosilane toward nucleophilic substitution. Compounds III and IV were prepared by free radical chlorination of II. Methanolysis of III and IV gave quantitative yields of V and VI, respectively. In the presence of mineral acid, VI readily cyclized to give high yields of the cyclic siloxane octamethyl-4,9-dioxa-3,5,8,10-tetrasila-cyclodeca-1,6-diyne, VIII, and the analogous triyne, IX. It was determined that V and VI could be prepared directly from II in high yield by methanolysis with palladium catalyst. Vaska's complex also accomplished the conversion. I attempted to prepare bis(ethoxydimethylsilyl)acetylene by using of Wilkinson 's catalyst for hydrosilylation with acetaldehyde. The principal product of this reaction was 1-(dimethylsilyl)-3,5,5-trimethyl-4-oxa-3-silacyclopent-1-ene, XI.
Date: May 1987
Creator: Albanesi, Todd E. (Todd Edward)
Partner: UNT Libraries

Photochemical Silene Syntheses

Description: We report the attempted syntheses of two photochemical dimethylsilene precursors, both of which are derived from polyphenyl silanorbornadiene skeletons. Possible synthetic schemes and our results are reported herein. Photolysis of 1,2-divinyl-1,1,2,2-tetramethyl-1,2-disilane at room temperature in a cyclohexane solution of 1,3-butadiene produces 1,1-dimethyl-2-(vinyldimethylsilylmethyl) silene which is trapped in high yields to afford the E- and Z-1,1-dimethyl-2-(vinyldimethylsilylmethyl)-3-vinyl-1-silacyclobutanes in 42 and 29% yields, respectively, along with minor amounts of 1,1-dimethyl-2-(vinyldimethylsilylmethyl)-1-silacyclohex-3-ene, 9%. Low Pressure Flow Pyrolysis at 450º C of either the E- or Z-isomer provides a relatively mild thermal source of the silene in the gas phase. Two products, 1,1,3,3-tetramethyldisilacyclohex-3-ene and 2,2,5,5-tetramethyl-2,5-disilabicyclo[2.2.1]hexane, are formed from an intramolecular rearrangement of the silene. Other reactions of the 3-vinylsilacyclobutanes include geometric isomerization, ring expansion to the silacyclohex-3-ene, and a homodienyl-1,5-hydrogen shift to 3,3,6,6-tetramethyl-3,6-disiladeca-1,4,8-triene. Synthetic schemes, successful and unsuccessful, for hydrido silene, acylpolysilene, and fluorine substituted silene precursors are discussed in the final chapter.
Date: August 1987
Creator: Bobbitt, Kevin L. (Kevin Lee)
Partner: UNT Libraries

Investigation of Substituent Effects of 2-Substituted Silaethylenes

Description: This investigation is concerned with determining whether a carbon substituent or a silicon substituent on the carbon terminus of a silicon-carbon double bond has a more stabilizing effect. Two different 2-substituted silaethylenes were generated at the same time by pyrolyzing 1, 1-dimethyl-2-neopentyl-4- (dimethylalkoxysilyl) silacyclobutanes in a nitrogen flow system. The results of these pyrolyses, both neat and in the presence of a trapping reagent, show that the silaethylene with a silicon substituent on the carbon terminus was favored approximately two to one over the silaethylene with a carbon substituent. This datum, along with other observations and hypotheses discussed, leads to the suggestion that the silicon substituenton the carbon terminus of the silaethylene bond has a more stabilizing effect than the carbon substituent.
Date: December 1980
Creator: Snyder, Walter David
Partner: UNT Libraries