Organic Chemistry Commons^™

Perfluoroalkyl (Aryl) Sulfonimide Zwitterions, Hua Mei

All Dissertations

This research focuses on superacid perfluoroalkyl(aryl) sulfonimides and their derivatives as a source of stable zwitterionic salts. The strong resonance stabilization of sulfonimides imparts unexpected stability to the zwitterions.
Two types of zwitterions were investigated. The first are symmetrical diaryliodonium zwitterions (DZs) as potential photo acid generators (PAGs) for microlithography. Driven by the demand for smaller feature sizes in the microelectronics industry, microlithography using shorter wavelength light has evolved and new PAGs are of interest. New DZs are potentially useful because they have good thermal stability and may be structurally modified to alter their spectral absorption characteristics. As an extension …

Bis(1,2-Dihydroxy­Benzene) Hexa­Methyl­Ene­Tetra­Mine, Philias Daka, Kraig A. Wheeler

Faculty Research and Creative Activity

The title binary complex, 2C6H6O2·C6H12N4, is constructed from hexa­methyl­ene­tetra­mine, positioned about a twofold symmetry operator, and 1,2-dihydroxy­benzene. Each of the four tertiary amine N atoms participates in O—H⋯N contacts that produce mol­ecular strands that propagate along the c axis.

(Acetonitrile-Κn){2-[Bis­(2-Pyridylethyl)­Amino]Ethanol-Κ4n,N′,N′′,O}Zinc(Ii) Bis­(Perchlorate) Monohydrate, Hong-Chang Liang, Marcel M. Hetu, Kraig A. Wheeler, Lev N. Zakharov, Arnold L. Rheingold

Faculty Research and Creative Activity

In the title compound, [Zn(C2H3N)(C16H21N3O)](ClO4)2·H2O, the ZnII ion is coordinated by two pyridyl N atoms, one amine N atom, and an ethanol O atom from the N,N′,N′′,O-tetra­dentate 2-[bis­(2-pyridylethyl)amino]­ethanol donor ligand. The fifth coordination site is filled by an acetonitrile N atom, and there is one solvent water mol­ecule in the asymmetric unit. The 2+ charge of the cationic portion of the complex is balanced by two perchlorate counter-anions.

(E,E)-1,3-Bis[9,10-Dihydro-9-Nitro-10-(Trinitro­Meth­Yl)-9-Anthr­Yl]Propane, Mustafa Arslan, Erol Asker, John Masnovi, Ronald J. Baker

Chemistry Faculty Publications

The title compound, C₃₃H₂₄N₈O₁₆, was obtained as a product of the photoreaction between 1,3-di-9-anthrylpropane and tetra­nitro­methane. The mol­ecule occupies a special position on a twofold axis. The trinitro­methyl and nitro substituents on the 9,10-dihydro­acridine system are E oriented.

A 2:1 Complex Of 1,3-Bis­(9h-Carbazol-9-Yl)Propane And Tetra­Chloro-P-Benzoquinone (P-Chloranil), Mustafa Arslan, Randolph B. Krafcik, John Masnovi, Ronald J. Baker

Chemistry Faculty Publications

In the title electron donor–acceptor complex, C₂₇H₂₂N₂·0.5C₆Cl₄O₂, the p-chloranil mol­ecule lies on a crystallographic inversion center, which is located at the center of the benzene ring. In the crystal structure, one p-chloranil mol­ecule lies above and below the central rings of each donor group of two neighboring 1,3-bis­(9H-carbazol-9-yl)propane mol­ecules, with a ring-centroid separation of 3.444 (1) Å. The angle between the planes of the stacking rings of the carbazole and p-chloranil mol­ecules is 3.4 (2)°.

N-(2-Aminobenzyl)-N,N-Bis(Quinolin- 2-Ylmethyl)Amine, Abhijit Mitra, Pamela J. Seaton, Kraig A. Wheeler

Faculty Research and Creative Activity

The title new diquinaldine derivative, C27H24N4, forms mol­ecular assemblies organized by inter­molecular quinoline π–π stacking [3.356 (3) and 3.440 (3) Å] and both inter- and intra­molecular N—H⋯N hydrogen bonds [3.039 (3)–3.104 (3) Å and 129 (2)–172 (2)°]. The combination of such inter­actions provides readily definable contacts that propagate along each crystallographic axis.

Strychninium (S)-2-(2-Bromo­Phen­Oxy)Propanoate 1.4-Hydrate, Kraig A. Wheeler, Aaron M. Lineberry

Faculty Research and Creative Activity

In the title mol­ecular salt, C21H23N2O2+·C9H8BrO3−·1.4H2O, the components are linked by inter­molecular C—O−⋯H—+N and OW—H⋯O inter­actions.

10,10′-Dinitro-10,10′-(Butane-1,4-Di­Yl)Dianthracen-9(10h)-One, Mustafa Arslan, Erol Asker, John Masnovi, Ronald J. Baker

Chemistry Faculty Publications

The title compound, C₃₂H₂₄N₂O₆, was obtained as the decomposition product of (E,E)-1,4-bis­[9,10-dihydro-9-nitro-10-(trinitro­meth­yl)-9-anthr­yl]butane, which was synthesized via a photochemical reaction of 1,4-bis­(9-anthr­yl)butane with tetra­nitro­methane. The asymmetric unit contains one half-mol­ecule; the complete mol­ecule is generated by a center of inversion. The crystal packing is determined mainly by inter­molecular C—H⋯O inter­actions.

10,10′-Dinitro-10,10′-(Propane-1,3-Di­Yl)Di-10h-Anthracen-9-One, Mustafa Arslan, Erol Asker, John Masnovi, Ronald J. Baker

Chemistry Faculty Publications

The title compound, C₃₁H₂₂N₂O₆, was obtained as the decomposition product of (E,E)-1,3-bis­[9,10-dihydro-9-nitro-10-(trinitro­meth­yl)-9-anthr­yl]propane, which was synthesized via a photochemical reaction of 1,3-di-9-anthrylpropane with tetra­nitro­methane. Inter­molecular C—H⋯O inter­actions are the most prominent features of the crystal packing; no indications of any inter­molecular π–π stacking were found.

Toward Synthesizing A Selective Dopamine Binding Magnetic Resonance Contrast Agent, Judy Lau

Senior Honors Projects

Magnetic resonance imaging (MRI) is a non-invasive diagnostic methodology used to provide a two-dimensional view of an internal organ or structure, especially the brain and spinal cord. Magnetic resonance contrast agents are usually injected into necessary parts of the body prior to imaging to increase the differences between different tissues or between normal and abnormal tissue, making it easier for a radiologist or doctor to interpret the image that is taken. The development of new and more efficient, effective, and selective contrast agents for various biological processes or chemicals is a growing field of research and study. My project allowed …

Secondary N-Nitrosocarbamate Anions: Structure And Alkylation Reactions. A Dft Study, Vladimir Benin

Chemistry Faculty Publications

The current article reports theoretical studies (DFT: B3LYP/6-31+G(d)) on the structure and alkylation reactions of the anions of some secondary N-nitrosocarbamates, a class of ambident nucleophiles whose chemistry has been little explored. Several anions (1–4), with an increasing size of the carbamate alkyl (aryl) group were investigated, in an attempt to establish the influence of the size of that group on the thermal stability and regioselectivity of alkylation of the title anions. The conclusion is that thermal stability and the mode of reaction are affected significantly only in the presence of very large and branched carbamate groups. The thermal …

9-Ethyl-3-(9h-9-Ethyl­Carbazol-3-Yl)-4-Nitro­-9h-Carbazole, Erol Asker, John Masnovi

Chemistry Faculty Publications

In the mol­ecule of the title compound, C₂₈H₂₃N₃O₂, the nitro group is almost perpendicular to the carbazole ring to which it is attached. The crystal packing is determined by C—H⋯O and π–π inter­actions, where the nitrated carbazole ring of one mol­ecule associates in a shifted parallel planar orientation with the centrosymmetrically related non-nitrated carbazole ring of a neighbouring mol­ecule.

Bis(9-Ethyl­Carbazol-3-Yl)Ethane, Erol Asker, John Masnovi

Chemistry Faculty Publications

In the title compound, C₃₀H₂₈N₂, each carbazole skeleton is essentially planar. The planes of the two carbazole ring systems are nearly parallel, with a dihedral angle of 2.33 (19)°. The crystal packing is stabilized only by van der Waals forces and weak C—H⋯π inter­actions.

Composition Ot Glvceride Esters Of Lauric Acid Bv Ftir Band Shape Analysis, Deniz P. Wong, Modesto Tan Chua, Erwin P. Enriquez

Chemistry Faculty Publications

Synthesis of glyceride esters of a fatty acid produces a mixture of isomers that are difficult to separate and analyze, requiring high temperature GC in most cases particularly for long-chain esters. In this paper, we present a fast estimation of the composition of the glyceride esters of lauric acid and glycerol (monolaurin, dilaurin, and trilaurin) by FTIR band shape analysis. The method uses the fact that the carbonyl stretching regions of the pure glycerides have differentband shapes, which implies any composite band of a mixture of glycerides may be resolved into the component peaks due to each glyceride. The carbonyl …

Synthesis Of Aspernigrin A, Erica Joerger

Undergraduate Theses and Capstone Projects

Aspernigrin A is a compound correlated with inhibiting the growth of cancer cells in the colon. A five-step synthesis was designed for aspernigrin A, projected to yield four intermediates and the final product. The intermediates were analyzed by high field 1HNMR and FT-IR spectroscopy before proceeding to the next step. A model pyridone ring system was successfully prepared from a commercially available pyrone precursor in two steps. These results provide a proof of concept that the synthetic scheme should successfully yield the natural product.

9,9′-Diethyl-3,3′-Di-9h-Carbazol­Yl, Erol Asker, John Masnovi

Chemistry Faculty Publications

In the title compound, C₂₈H₂₄N₂, the carbazole ring systems are essentially planar to within 0.076 (3) Å. The dihedral angle between the planes of the ring systems is 40.38 (4)°. The contribution of inter­molecular π–π inter­actions to the mol­ecular stacking is observed.

Bis(9-Ethyl­Carbazol-3-Yl)Methane, Erol Asker, John Masnovi

Chemistry Faculty Publications

In the title compound, C₂₉H₂₆N₂, the carbazole ring systems are essentially planar. There is no indication of π–π interactions in the crystal structure, adjacent carbazole groups being non-parallel.

Scanning Probe Microscopy And Oxidation Of Silicon At Breakdown Voltages, Thabo Gcwabaza

Theses, Dissertations and Capstones

The growing importance of Scanning Probe Microscopy (SPM) as a tool for nanofabrication is opening many avenues in lithography nano-science. One type of Scanning Probe Lithography involves electrochemistry at the tip/substrate interface. Atomic Force Microscopy (AFM) with conductive tips and substrates was used in our study to both pattern and image those patterns on silicon substrates. Our long-term objective is to design and fabricate micron-scale patterns of nanometer sized spots on silicon chips that can serve as attachment sites for DNA based nano-arrays. In order to fabricate such substrates a study of the underlying electrochemistry was required. A most promising …

Design And Implementation Strategies For Peer-Led Team Learning In Organic Chemistry, Stephen K. Manu

Capstone Research Projects

Peer-Led Team Learning (PLTL), which initially began as an effort to improve undergraduate chemistry education, has shown the potential to improve learning among college students in all disciplines. The model applies the desired qualities of teamwork to learning. This project is aimed at designing and setting up a PLTL Workshop at Southern Adventist University (SAU). Nine students currently taking organic chemistry at SAU volunteered to participate in the project. In order to determine the effectiveness of the project, test scores were collected and analyzed for any apparent trends, and an end-of-semester survey was conducted. The results indicate that the program …

A Molecular Salt Of Tricyanomethanide Anion And A N,N9- Dianisylphenazinium Dication: Cooperative Affects Of Methoxy…Methoxy And Cmn…N+ Intermolecular Contacts, Scott E. Mckay, Kraig A. Wheeler, Silas C. Blackstock

Faculty Research and Creative Activity

A molecular salt of tricyanomethanide anion and a N,N9- dianisylphenazinium dication forms extended supramolecular assemblies that consist of unusual methoxy…methoxy and CMN…N+ intermolecular contacts.

Projects That Assist With Content In A Traditional Organic Chemistry Course, John J. Esteb, John R. Magers, Luanne Mcnulty, Anne M. Wilson

Scholarship and Professional Work - LAS

Projects that engage undergraduate students in content-based courses, such as organic chemistry, must relate to the material and provide useful tools for the divergent needs of the students. There are few examples of these types of projects in the literature. Herein, we describe two projects, the reaction notebook and the end-of-semester synthesis activity. Each project is designed to stimulate student ownership of the material and leads to engagement with the content of the course.

Nanodot-Based Organic Memory Devices, Zhengchun Liu

Doctoral Dissertations

In this study, resistor-type, diode-type, and transistor-type organic memory devices were investigated, aiming at the low-cost plastic integrated circuit applications. A series of solution-processing techniques including spin-coating, inkjet printing, and self-assembly were employed to fabricate these devices.

The organic resistive memory device is based on a novel molecular complex film composed of tetracyanoquinodimethane (TCNQ) and a soluble methanofullerene derivative [6,6]-phenyl C61-butyric acid methyl ester (PCBM). It has an Al/molecules/Al sandwich structure. The molecular layer was formed by spin-coating technique instead of expensive vacuum deposition method. The current-voltage characteristics show that the device switches from the initial 'low' conduction state to …

Spirobicyclic Diamines 2: Synthesis Of Homochiral Diastereoisomeric Proline Derived [4,4]-Spirolactams, Fintan Kelleher, Sinead Kelly

Articles

L-Proline derived diastereoisomeric [4.4]-spirolactams have been prepared by a reductive-amination reaction of (R)- or (S)-alanine methyl ester followed by thermal cyclisation of the resulting amine onto the proline ester group in refluxing toluene. Under similar conditions (R)- or (S)-phenylalanine methyl ester gave no cyclisation products, while R- or S-a-methylbenzylamine required treatment with NaNH₂ in refluxing toluene to induce cyclisation giving diastereoisomeric [4.4]-spirolactams

Development Of A Calix[4]Arene Sensor For Soft Metals Based On Nitrile Functionality, Benjamin Schazmann, Dermot Diamond

Articles

The current work is amongst the first to examine the potential usefulness of the nitrile functional group in potentiometric analytical sensors for soft metals. Nitrile functionality has hereby been incorporated into a calix[4]arene skeleton to give a series of new cation selective hosts. The analytical sensing behaviour of these hosts was examined by Ion Selective Electrode (ISE) based potentiometry. In all cases a preference for soft metals was observed, explained primarily in terms of soft–soft compatibility between calix[4]arene nitrile hosts and metal guests in combination with a classical ‘lock and key’ best fit mechanism. Hosts 2, 3 and 4 showed …

Solubilisation, Purification And Processing Of Single Walled Carbon Nanotubes Using Organic Molecules, Theresa Hedderman

Doctoral

The aims of this research are seven fold; • To enhance the solubility of SWNTs in organic solvents. • To purify an untreated sample of SWNTs that contains many side products. • To gain a greater understanding of the interaction between the polycyclic aromatic hydrocarbons and SWNTs. • To debundle and disperse SWNTs. • To select SWNTs of a specific structure based on the structures of the polycyclic aromatic hydrocarbons used. • To observe and compare the interaction of polycyclic aromatic hydrocarbons with SWNTs produced by different methods. • To elucidate factors which contribute to different degrees of interaction between …

Preparation Of Some Substituted Terephthalic Acids, Susanna Branion, Vladimir Benin

Chemistry Faculty Publications

We report in detail the preparation of two substituted terephthalic acids: 2‐sulfomethylterephthalic acid (1) and 2‐phosphonoterephthalic acid (2). Efficient, short syntheses have been developed for both compounds. They are potentially useful monomers for construction of acid‐pendant polymer chains.

Preparation, Characterization And Dft Studies Of Some New N-Nitrosocarbamates And N-Nitrosoureas, Ragavan Narayanan, Helene Hedian, Eric Shamo, Vladimir Benin

Chemistry Faculty Publications

We are presenting the preparation, characterization and density functional theory (DFT) studies {B3LYP/6-31+G(d)) of several reiated classes of N-nitrosocarbamates and N-nitrosoureas. The iong-range goal is the design and preparation of compounds, which would undergo photochemical or hydrolytic decomposition, to yield stabilized cyclic cations that can serve as alkylating agents at various nucleophilic centers, including DNA bases.

Density Functional Studies Of The Structure And Bonding In Piano Stool Carbene Complexes, John P. Graham, Robbie Davis

Journal of the Arkansas Academy of Science

No abstract provided.

Synthesis Of Glycosylamides And Carbohydrate Fused Heterocycles, Michael De Castro

Seton Hall University Dissertations and Theses (ETDs)

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A Chloride Selective Calix[4]Arene Optical Sensor Combining Urea Functionality With Pyrene Excimer Transduction, Benjamin Schazmann, Dermot Diamond

Articles

A neutral 2-site chloride selective compound has been developed (3), based on a 1,3- alternate tetrasubstituted calix[4]arene providing a preorganised supramolecular scaffold. The resultant supramolecular cavity is amongst the first to combine urea functional groups bridged with single methylene spacers to pyrene moieties. It combines a naturally and synthetically proven H-bonding system with the elegant ratiometric fluorescent signalling properties of an intramolecular pyrene excimer system, triggered by conformational changes upon anion coordination. The excimer emission of 3 is quenched, with a simultaneous rise in the monomer emission solely by the chloride anion amongst a wide variety of anions tested. 3 …