Organic Chemistry Commons^™

Efforts Toward Difunctionalization Of (Hetero)Arenes Enabled By Visible Light, Eric Allen

Master's Theses (2009 -)

Functionalized arenes and heteroarenes are ubiquitous motifs in natural products, pharmaceuticals, and functional materials. As such, methods to place multiple functionalities on (hetero)arenes in one synthetic step create molecular complexity quickly and are highly valued. The vast majority of current strategies are metal-mediated, although others such as utilizing aryne intermediates and cycloadditions have also been reported. The premier challenge in this research area is the difficulty in controlling regioselectivity. Strategies of controlling regioselectivity have included tuning the electronic nature of the substrate, the use of directing groups (DGs), steric influences, ligand control, and photochemically initiated methods. Certain strategies tend to …

The Photodynamic And Structural Analyses Of Advanced Materials For Solar Fuel Conversion, Brian Pattengale

Dissertations (1934 -)

Mitigating the current and future climate and pollution issues that have been brought on by the combustion of fossil fuels is of utmost importance and will rely on, in part, the availability of renewable fuel sources. Of the possible sources of energy, solar is abundant, but must be harnessed efficiently and stored as a solar fuel to overcome the current storage issues that limit photovoltaic cells. One such fuel, H2(g), represents a carbon-neutral source of energy if it can be efficiently liberated from water via the water splitting reaction. Thus, much attention is focused on designing materials to perform the …

Design, Synthesis And Study Of Redox And Optoelectronic Properties Of Aromatic Oxidants And Polycyclic Aromatic Hydrocarbons, Mohammad Mosharraf Hossain

Dissertations (1934 -)

Organic materials play a significant role for the next generation photovoltaic devices that convert solar energy into usable forms of energy. In this regard, polycyclic aromatic hydrocarbons (PAHs) are fundamental tools in the developing area of molecular electronics and photovoltaics as they show excellent optical/electronic properties and are well-suited for applications in such developing areas as flexible display devices, field effect transistors and solar cell panels. Design and synthesis of novel materials for photovoltaics applications would require the proper understanding the mechanism of charge transport and identification of the structural features necessary in a particular molecular wire or PAH. To …

Photoremovable Protecting Groups Based On Electrocyclization With Leaving Group Expulsion Via A Proposed Zwitterion, Gilbert Ndzeidze

Dissertations (1934 -)

The triplet excited state of thioxanthone produced by photolysis undergoes reversible triplet energy transfer with a trimethylene - linked benzothiophene-2-carboxanilide ring system. The ensuing electrocyclic ring closure of the anilide moiety produces a putative zwitterionic intermediate that is capable of expelling leaving groups (LG-) from the C-3 position of the benzothiophene ring. Stern-Volmer quenching studies with cyclohexadiene as quencher furnish the rate constants for the triplet excitation transfer in the forward and reverse directions, which can be expressed as an equilibrium constant K = 0.058. Overall, the rate of triplet excited state reaction becomes K x kr = 5.7 x …

Functional And Structural Studies Of Cytochromes P450 By Resonance Raman Spectroscopy, Yilin Liu

Dissertations (1934 -)

Cytochrome P450 is a broad class of heme monooxygenase enzymes which catalyze various oxidative transformations. There are two main kinds of mammalian P450s: steroidogenic and drug metabolizing P450s. The first project involves a steroidogenic P450, CYP17A1, occupying a central role in the biosynthesis of steroid hormones. It catalyzes hydroxylation reaction on pregnenolone and progesterone, generating 17OH-pregnenolone and 17OH-progesterone, presumably utilizing a “Compound I” species. However, these hydroxylated products can be further processed in a second oxidative cycle to cleave the C17–C20 bond to form dehydroepiandrosterone or androstenedione, respectively, a crucial step in androgen production. Interestingly, it is well known that …

Ruthenium-Catalyzed Dehydrogenative And Dehydrative C-H Coupling Reactions Of Arenes With Alcohols And Carbonyl Compounds, Hanbin Lee

Dissertations (1934 -)

Despite their outstanding achievements, the requirement of preformed functional groups and wasteful byproduct formation are inherent disadvantages associated with the transition metal catalyzed cross-coupling methods. Inspired by the needs for green and sustainable chemistry, transition metal catalyzed dehydrogenative and dehydrative coupling methods have been recognized as environmentally sustainable and atom economical synthetic routes for the new C-C bond formation. The catalytic activation of C-H and C-O bonds allows the formation of coupling products from ubiquitous hydrocarbon substrates by releasing hydrogen or water byproduct. However, these novel protocols require relatively harsh conditions due to their low reactivity of C-H and C-O …

Synthesis And Study Of The Electrochemical And Optoelectronic Properties Of Π-Conjugated Poly-P-Phenylene-Based Molecular Wires, Anitha Boddeda

Dissertations (1934 -)

Organic photovoltaics will play an important role in supplementing the energy needs of the twenty first century in a most cost-effective way to convert the solar energy into usable forms of energy. One of the bottlenecks in promoting widespread use of photovoltaic devices for solar energy storage is the inefficiency of the devices, which in part arises due to the inefficient charge separation and long-range charge transport. Design and synthesis of efficient charge-transfer materials would require one to first identify and establish the structural features necessary in a given molecular wire, which may promote effective charge transfer to long distances. …

Computational Modeling Of S-Thiolation Reaction: Toward Discovering The Enzymatic Mechanisms Of Endogenous Hno Formation, Elena Ivanova

Dissertations (1934 -)

S-nitrosothiols (RSNOs) have long been proposed as potential sources of the elusive endogenous nitroxyl (HNO) via S-thiolation reaction with thiols. It is however not clear how S-thiolation can compete with the trans-S-nitrosation pathway commonly observed in vitro. Based on the insights into the highly unusual, antagonistic chemical nature of RSNO molecules, we hypothesize that, while difficult in vitro, S-thiolation could easily lend itself to enzymatic catalysis. To explore this possibility, we adopted a bottom-up computational approach that aims to identify possible catalytic mechanisms able to steer the RSNO + thiol reaction toward HNO production. Inspired by recent discovery of small …

Photochemical Electrocyclic Ring Closure And Elimination Reactions Of N-(Oxothioxanthenyl)Naphthothiophene Carboxamides, Himali Devika Jayasekara

Dissertations (1934 -)

Photochemical cleavage reactions have found a widespread used in biological applications that require the photorelease of biologically active molecules such as proteins, peptides, neurotransmitters, and nucleotide phosphates. This research focuses on the design of photoremovable protecting groups which can be utilized to release these biomolecules by photolysis. These biomolecules are attached to the photoremovable protecting group at the sites of functional groups that are present within these substrates. Such functional groups are carboxylates, phosphates, thiolates, or phenolates, which upon exposure to light, are released as anions of varying basicities. The photochemical reaction involved is an electrocyclic ring closure between aromatic …

Investigation Of The Use Of A Plasticizer-Polymer Sensor Coating With Improved Long-Term Stability In The Liquid Phase, Laura Jeanne Alderson

Master's Theses (2009 -)

Benzene is one of the volatile organic compounds present in crude oil and gasoline. Leakage from underground storage tanks or hazardous waste sites can introduce benzene contamination into nearby groundwater. Benzene is a known carcinogen and its exposure is limited by the Environmental Protection Agency to 5 parts per billion (ppb) in drinking water. Early, accurate detection of the presence of benzene contamination in groundwater supplies is extremely important. Shear horizontal surface acoustic wave (SH-SAW) devices with a chemically sensitive coating can be used for the detection of volatile organic compounds in liquid, such as BTEX (benzene, toluene, ethylbenzene and …

Toward Electronic Materials Based On Metal Pincer-Type Complexes, Jeewantha Sampath Hewage

Master's Theses (2009 -)

There is currently a lot of interest in developing electrically conducting or semiconducting metal-organic frameworks (MOF's), highly porous materials constructed by organic ligands bridging metal centers. Typically MOF's are non-conducting and, moreover, they are susceptible to hydrolytic degradation. If hydrolytically stable and electrically conducting MOFs could be realized, then revolutionary new technologies could be envisioned. Currently, organic dicarboxylates are used as bridging organic ligands and one simple strategy to obtain the desired materials is to explore other ligand systems. Pincer ligands are organic compounds that are uninegative and bind metals in a tridentate, meridional fashion with two five-member chelate rings. …

Photochemical Elimination Reactions That Proceed Via Triplet Excited State Electrocyclic Ring Closures, Himali Devika Jayasekara

Master's Theses (2009 -)

Cage compounds have become an important tool for the study of biological processes. The research focuses on new cage compounds that can unmask functional groups present in biologically important molecules such as proteins, peptides, and oligonucleosides. The project focuses on certain functional groups that are often difficult to release photochemically. These are the thiolate groups present in cysteine residues of proteins and peptides. Thiolate groups are fairly basic leaving groups, unlike the more labile groups such as the carboxylates that are present in proteins and peptides, or the phosphate groups present in nucleosides. The research takes advantage of the ability …

Spectral Data For "Probing The Human Estrogen Receptor-Alpha Binding Requirements For Phenolic Mono- And Do-Hydroxyl Compounds: A Combined Synthesis, Binding And Docking Study", Christopher Mccullough, Terrence S. Neumann, Jayapal Reddy Gone, Zhengjie He, Julie Lukesh, Rajesh K. Pandey, William A. Donaldson, Daniel S. Sem

Natural Products Synthesis via Organoiron Methodology

Spectral data used in the course of researching "Probing the human estrogen receptor-alpha binding requirements for phenolic mono- and do-hydroxyl compounds: A combined synthesis, binding and docking study".

Various estrogen analogs were synthesized and tested for binding to human ERα using a fluorescence polarization displacement assay. Binding affinity and orientation were also predicted using docking calculations. Docking was able to accurately predict relative binding affinity and orientation for estradiol, but only if a tightly bound water molecule bridging Arg394/Glu353 is present. Di-hydroxyl compounds sometimes bind in two orientations, which are flipped in terms of relative positioning of their hydroxyl groups. …

Probing The Human Estrogen Receptor-Α Binding Requirements For Phenolic Mono- And Di-Hydroxyl Compounds: A Combined Synthesis, Binding And Docking Study, Christopher Mccullough, Terrence S. Neumann, Jayapal Reddy Gone, Zhengjie He, Christian Herrild, Julie Lukesh, Rajesh K. Pandey, William A. Donaldson, Daniel S. Sem

Chemistry Faculty Research and Publications

Various estrogen analogs were synthesized and tested for binding to human ERα using a fluorescence polarization displacement assay. Binding affinity and orientation were also predicted using docking calculations. Docking was able to accurately predict relative binding affinity and orientation for estradiol, but only if a tightly bound water molecule bridging Arg394/Glu353 is present. Di-hydroxyl compounds sometimes bind in two orientations, which are flipped in terms of relative positioning of their hydroxyl groups. Di-hydroxyl compounds were predicted to bind with their aliphatic hydroxyl group interacting with His524 in ERα. One nonsteroid-based dihdroxyl compound was 1000-fold specific for ERβ over ERα, and …

Expulsion Of Leaving Groups From Zwitterionic Intermediates Generated Via Photochemical Electrocyclic Ring Closure Reactions And An Investigation On Tpe Oligomers, Tasnuva Shahrin

Dissertations (1934 -)

Photochemical cleavage reactions have been found widespread use in biological applications that require intracellular photochemical release of biologically active substrates such as peptides, proteins, neurotransmitters, or nucleotide phosphates. The research is to devise photoremovable protecting groups (cage compounds) that can be used to deprotect those biological substrates by irradiation. A number of photocleavage reactions have been developed in recent years which release chlorides, hydroxides, carboxylates, thiolates, and phenolates leaving groups for use in such applications. Nevertheless, photochemical elimination reactions that expel such leaving group anions remain quite uncommon. The cleavage of cage compounds via photolysis requires heterolysis of a bond …

Spectral Data For "Generation Of Molecular Complexity From Cyclooctatetraene: Preparation Of Optically Active Protected Aminocycloheptitols And Bicyclo[4.4.1]Undecatriene", Mohamed F. El-Mansy, Anobick Sar, Sergey V. Lindeman, William A. Donaldson

Natural Products Synthesis via Organoiron Methodology

Spectral data created in the course of the research project. Supports specific findings in "Generation of Molecular Complexity from Cyclooctatetraene: Preparation of Optically Active Protected Aminocycloheptitols and Bicyclo[4.4.1]undecatriene".

The racemic (6-cyclo-heptadienyl)Fe(CO)₃⁺ cation ((±)-7), prepared from cyclooctatetraene, was treated with a variety of carbon and heteroatom nucleophiles. Attack took place at the less hindered C¹ dienyl carbon and decomplexation of the (cycloheptadiene)Fe(CO)₃ complexes gave products rich in functionality for further synthetic manipulation. In particular, a seven-step route was developed from racemic (6-styryl-2,4-cycloheptadien-1-yl)phthalimide ((±)-9 d) to afford the optically active aminocycloheptitols (−)-20 and …

Spectral Data For "Reactivity Of Acyclic (Pentadienyl)Iron(1+) Cations: Synthetic Studies Directed Toward The Frondosins", Do W. Lee, Rajesh K. Pandey, Sergey V. Lindeman, William A. Donaldson

Natural Products Synthesis via Organoiron Methodology

Spectral data created in the course of the research project. Supports specific findings in "Reactivity of acyclic (pentadienyl)iron(1+) cations: Synthetic studies directed toward the frondosins".

A short, 4-step route to the scaffold of frondosin A and B is reported. The [1-methoxycarbonyl-5-(2′,5′-dimethoxyphenyl)pentadienyl]Fe(CO)₃⁺ cation was prepared in two steps from (methyl 6-oxo-2,4-hexadienoate)Fe(CO)₃. Reaction of this cation with isopropenyl Grignard or cyclohexenyllithium reagents affords (2-alkenyl-5-aryl-1-methoxycarbonyl-3-pentene-1,5-diyl)Fe(CO)₃ along with other addition products. Oxidative decomplexation of these (pentenediyl)iron complexes, utilizing CuCl₂, affords 6-aryl-3-methoxycarbonyl-1,4-cycloheptadienes via the presumed intermediacy of a cis-divinylcyclopropane.

Sprectral Data For "Generation Of Molecular Complexity From Cyclooctatetraene Using Dienyliron And Olefin Metathesis", Mohamed F. El-Mansy, Anobick Sar, Subhabrata Chaudhury, Nathaniel J. Wallock, William A. Donaldson

Natural Products Synthesis via Organoiron Methodology

Spectral data used in the course of researching "Generation of molecular complexity from cyclooctatetraene using dienyliron and olefin metathesis methodology".

Transformation of the simple hydrocarbon cyclooctatetraene into a variety of polycyclic skeletons was achieved by sequential coordination to iron, reaction with electrophiles followed by allylated nucleophiles, decomplexation and olefin metathesis.

Generation Of Molecular Complexity From Cyclooctatetraene Using Dienyliron And Olefin Metathesis Methodology, Mohamed F. El-Mansy, Anobick Sar, Subhabrata Chaudhury, Nathaniel J. Wallock, William A. Donaldson

Chemistry Faculty Research and Publications

Transformation of the simple hydrocarbon cyclooctatetraene into a variety of polycyclic skeletons was achieved by sequential coordination to iron, reaction with electrophiles followed by allylated nucleophiles, decomplexation and olefin metathesis.

Design, Synthesis And Study Of Polycyclic Aromatic Hydrocarbons And Their Cation Radicals, Tushar Navale

Dissertations (1934 -)

The unifying theme of most of optoelectronic devices revolves around the charge carrier mobility of the organic materials used in the conductive layers, which is a measure of how easily the electron/hole moves in a particular pi conjugated organic material. When pi conjugated materials are incorporated in these devices, molecules are generally layered in random orientation. Consequently, the efficiency of charge transport in the conducting layers of these devices is governed not only by the intramolecular electron/hole transport through the backbone of the molecule but also by the intermolecular electron/hole transport between the molecules and hence packing of these molecules …

Design And Synthesis Of Polycyclic Aromatic Hydrocarbons For Emission And Through-Space Charge Delocalization Studies, Vijay Vyas

Dissertations (1934 -)

Over the past decades, a variety of pi-conjugated organic materials have been explored as potential charge transport materials in conducting layers of photovoltaic devices. The performance of these devices critically depend on the efficiency with which the charge carriers (electrons and/or holes) move within the pi-conjugated materials present in their hole and electron conducting layers before their collection at the electrode. Hence, a large amount of research effort is devoted not only to the preparation of new pi-conjugated organic molecules for charge transport applications but also in understanding the nature of charge transport along the molecule (intra-chain) as well as …

Reactivity Of Acyclic (Pentadienyl)Iron(1+) Cations: Synthetic Studies Directed Toward The Frondosins, Do W. Lee, Rajesh K. Pandey, Sergey V. Lindeman, William A. Donaldson

Chemistry Faculty Research and Publications

A short, 4-step route to the scaffold of frondosin A and B is reported. The [1-methoxycarbonyl-5-(2′,5′-dimethoxyphenyl)pentadienyl]Fe(CO)₃⁺ cation was prepared in two steps from (methyl 6-oxo-2,4-hexadienoate)Fe(CO)₃. Reaction of this cation with isopropenyl Grignard or cyclohexenyllithium reagents affords (2-alkenyl-5-aryl-1-methoxycarbonyl-3-pentene-1,5-diyl)Fe(CO)₃ along with other addition products. Oxidative decomplexation of these (pentenediyl)iron complexes, utilizing CuCl₂, affords 6-aryl-3-methoxycarbonyl-1,4-cycloheptadienes via the presumed intermediacy of a cis-divinylcyclopropane.

Synthesis Of Hydroxy- And Polyhydroxy-Substituted 1,3-Diaminocyclohexanes, Anobick Sar, Sergey V. Lindeman, William A. Donaldson

Chemistry Faculty Research and Publications

The synthesis of hydroxy-trans-1,3-diaminocyclo­hexanes based on nitroso-Diels-Alder cycloaddition of (cyclohexadienyl)phthalimide is reported.

Design, Synthesis And Study Of The Bridged And Cofacially-Arrayed Poly-P-Phenylene Molecular Wires, Matthew J. Modjewski

Master's Theses (2009 -)

Two novel series of bridged and cofacially-arrayed poly-p-phenylenes have been designed synthesized and studied. The bridged poly-p-phenylenes have been synthesized from a readily available diacetylenic precursor utilizing three high yielding steps, and their structures were determined by 1H/13C NMR spectroscopy as well as X-ray crystallography. The racemization barrier between the two atropoisomers was found to be ~12 Kcal mol-1; the versatility of the synthesis employed was extended to synthesis a triply bridged tetra-p-phenylene and a quadruply bridged penta-p-phenylene.

The cofacially-arrayed poly-p-phenylenes have shown that the X-ray crystal structures of the neutral compounds are largely dominated by C-H--π-interactions interactions while the …

Spectral Data For "Synthesis Of Cyclopropanes Via Organoiron Methodology: Stereoselective Preparation Of Bi(Cyclopropyl)S", Rajesh K. Pandey, Sergey V. Lindeman, William A. Donaldson

Natural Products Synthesis via Organoiron Methodology

Spectral data created in the course of the research project. Supports specific findings in "Synthesis of Cyclopropanes via Organoiron Methodology: Stereoselective Preparation of Bi(cyclopropyl)s".

Cyclopropanation of [2-(alkenyl)pentenediyl]Fe(CO)₃ complexes (4) proceeds in a diastereoselective fashion to afford [2-(cyclopropyl)pentenediyl]Fe(CO)₃. The relative stereochemistry of the products was established by X-ray crystallography. The diastereoselectivity is rationalized on approach of the cyclopropanation reagent on the sterically more exposed face of 4. Oxidatively induced reductive elimination afforded stereodefined bi(cyclopropyl)s.

A Study Of The Chelation Of Copper (Ii) With Various Indicators And Chelating Agents In A Non-Aqueous Solvent, Marian Rauch

Bachelors’ Theses

The chelation of Copper II in nonaqueous solvent systems has been under investigation, however, its application is generally limited to extraction methods. In recent years, considerable work has been done at Marquette to investigate spectrophotometric titrations of metals with various chelating agents in nonaque6us solvent systems to determine stability constants and as an important contribution to the field of direct analytical methods. The purpose of this work was to study the adsorption effects and the titration of various types of indicators when applied to the Copper II - Dibenzyldithiocarbamic Acid Zinc Salt Chelate and the Copper II-a -Benzoinoxime Chelate in …

Preparation And Infrared Spectrum Of Dimethyl Pinate In An Attempt To Determine The Configuration Of Pinic Acid, Margaret Schormuller

Bachelors’ Theses

The esters if pinic acid are in increasing demand for low temperature lubricants, and certain esters are also useful as plasticizers. In spite of the vast amount of work that has been done with pinic acid and its esters, its geometrical configuration has not yet been satisfactorily established. Stereoisomers may result from both geometrical and optical isomerism. If the cis configuration is assumed to be the dd-enantiomorph, a total of four enantiomorphs are possible.

Benzoylation Studies With A Compound Reported To Be Benzoyl Acid Sulfate And Analytical Studies On The Sample, Robert J. Peanasky

Bachelors’ Theses

A very valuable reagent in organic characterization work is benzoyl chloride. By interacting benzoyl chloride with any one of the general classes of compounds termed phenols, alcohols, and amines, solid and very satisfactory derivatives are usually produced. However, the action of this compound occurs rather slowly and the operator, unless especially careful, suffers from the lachrimatory effects of the reagent, benzoyl chloride. A sample was submitted to my major professor, Dr. C. R. Haymaker, by Gene LaFave who claimed that it was benzoyl acid sulfate. This compound was a solid not difficult to manipulate in contradistinction to the lachrimatory liquid …

Determination Of Saponification Rate By Change In Hydrogen Ion Concentration Measured With Quinhydrone And Glass Electrodes, Richard Porter

Bachelors’ Theses

The measurement or hydrogen ion concentration is becoming more important in all the fields of chemistry since the states or many chemical systems can to some extent be defined by their hydrogen ion concentration. If the hydrogen ion concentration or a particular solution can be measured accurately, in many cases other important relations and quantities may be determined. Methods or measurement are therefore important instruments or investigation.

When an ester is saponified by an alkali, the hydrogen ion concentration increases as the reaction proceeds. Thus, it the hydrogen ion concentration can be calculated at different intervals of time, some knowledge …

Deamination Of Certain Toluidines Through Diazotization And Decomposition Of The Diazonium Salt With Alcohol In The Presence Of Copper, Ralph E. Schaeffer

Bachelors’ Theses

Historically credit is given to Johann Peter Griess tor the discovery or diazo compounds in 1858 (8). Six years later, Griess reported that diazonium salts of benzene yield benzene when boiled with alcohol (31). At first it was thought that only hydrocarbons were formed when diazonium salts of benzene were boiled with alcohol. However, in 1870 ethyl ethers were found to be products or the reaction between diazotized chlorotoluidines and ethyl alcohol (31). Since that time much attention has been given to the factors influencing the formation of hydrocarbons or ethers as a result or the reaction between diazonium salts …