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Full-Text Articles in Organic Chemistry

Synthesis Of Pyridine Nucleosides By Cycloaddition Reactions And Synthesis And Condensation Reactions Of 4-Aryl-2-Oxytetronimides, Glenn L. Heise Dec 1985

Synthesis Of Pyridine Nucleosides By Cycloaddition Reactions And Synthesis And Condensation Reactions Of 4-Aryl-2-Oxytetronimides, Glenn L. Heise

Master's Theses

Experiment 1: The reaction of various glutaconaldehyde salts (Na+ or K+) with glycosyl isothiocyanates has resulted in the formation of a novel class of compounds. Relatively mild conditions were utilized for the synthesis which occurs in four steps, and in good yield, starting from glucpseptentaacetate. These reactions were found to be regiospecific. The unique physical and spectral properties of the model compound 1-(2,3,4,6-tetra-0-acetyl-β-D-glycopranosyl)-2-thiono-3-pyridine carboxaldehyde are also discussed.

Experiement 2: Early synthetic methodologies have recently been utilized in the synthesis of 4-aryl-2-oxytetronimides. These compounds have been found to participate in condensation reactions with various substituted o-phenylene ...


Reaction Of Nucleophiles With Bridgehead Carbocations Derived From 1-Bromobicyclo[2.2.2]Octanes And 1-Bromobicyclo[3.3.1]Nonanes, George A. Kraus, Yung Son Hon Nov 1985

Reaction Of Nucleophiles With Bridgehead Carbocations Derived From 1-Bromobicyclo[2.2.2]Octanes And 1-Bromobicyclo[3.3.1]Nonanes, George A. Kraus, Yung Son Hon

Chemistry Publications

Both intramolecular and intermolecular reactions of bridgehead carbocations are described. The carbocations are best generated from the corresponding halide with silver triflate. The carbocations reacted effectively with allyltrimethylsilane, ethyl acetoacetate, benzene, and enol silyl ethers. Bridgehead radicals were also examined.


Synthesis Of Novel 6-Deoxyanthracyclines, George A. Kraus, Michael D. Hagen Sep 1985

Synthesis Of Novel 6-Deoxyanthracyclines, George A. Kraus, Michael D. Hagen

Chemistry Publications

An extremely direct route to the 6-deoxyanthracycline skeleton is described. The initial route to quinone 10 failed due to an unexpected complication in the Ago demethylation step. However, starting from 2-bromo- 1,4-dimethoxynaphthalene, furan 17 could be prepared in two steps. Furan 17 was then converted into anthraquinone 19 in five steps. The eight-step route proceeds in 9% overall yield.


Bridgehead Intermediates In Organic Synthesis: Two Direct Syntheses Of (.+-.)-Lycopodine, George A. Kraus, Yung Son Hon Jul 1985

Bridgehead Intermediates In Organic Synthesis: Two Direct Syntheses Of (.+-.)-Lycopodine, George A. Kraus, Yung Son Hon

Chemistry Publications

The use of carbocation-based methodologies in natural products synthesis is often complicated by undesired rearrangements and by mixtures of stereoisomers produced from the planar carbocation.


Tandem Claisen-Diels-Alder Reactions In Synthesis. A Facile Approach To Anthracyclines, George A. Kraus, Brian S. Fulton May 1985

Tandem Claisen-Diels-Alder Reactions In Synthesis. A Facile Approach To Anthracyclines, George A. Kraus, Brian S. Fulton

Chemistry Publications

Acid 8b is available in seven steps from ketone 1. Quinone 5 represents a useful intermediate for the synthesis of anthracyclines.


Reactivity Of Some Nitrogen-Containing Compounds At Supercritical Water Conditions, David M. Tiffany Apr 1985

Reactivity Of Some Nitrogen-Containing Compounds At Supercritical Water Conditions, David M. Tiffany

Master's Theses

The use of water at cuperctirical conditions to remove nitrogen from several nitrogen-containing compounds was studied with the purpose of exploring the use of supercritical water as a method of removing nitrogen from the extraction products of coal. Quinoline and isoquinolone were the primary model compounds used with benzonitrile and carbazole also being examined briefly. Reaction conditions varied in temperature (350-500°C), pressure (3500-5200 psi), and water density (0.170-.0.426g/cc). The major products formed by isoquinoline were benzene, toluene, ethylbenzene, and o-xylene as well as nonvolatile tar and char. Quinoline produced aniline and toluidine in addition to ...


Experimental And Computational Studies Of Theoretically Significiant Alkenes , Richard O. Angus Jr. Jan 1985

Experimental And Computational Studies Of Theoretically Significiant Alkenes , Richard O. Angus Jr.

Retrospective Theses and Dissertations

The concept of a novel type of homoconjugation, henceforth referred to as columnar homoconjugation, is introduced. A new class of organic molecules which is expected to exhibit such interaction is devised; for this series, the name "columnene" is coined. Molecular Orbital calculations (Huckel, MNDO, and/or ab initio) for a series of columnenes as well as cyclic allenes, cyclicbutatrienes, and trans cyclic alkenes olefins are reported. These calculations lead to the prediction that alkene moieties easily withstand slight twisting and bending destabilization. Synthetic strategies towards columnenes are developed and are categorized by two approaches: butatriene and bisallyl synthetic equivalent approaches ...


Tandem Claisen - Diels-Alder Reactions In Organic Synthesis , Brian Shane Fulton Jan 1985

Tandem Claisen - Diels-Alder Reactions In Organic Synthesis , Brian Shane Fulton

Retrospective Theses and Dissertations

The aromatic Claisen rearrangement and the Diels-Alder reaction have been widely used by synthetic chemists for the construction of natural products. A program was undertaken to explore the use of a novel sequential strategy that would incorporate the use of both the Claisen rearrangement and Diels-Alder reaction in one step. This strategy was applied towards the construction of the linear tetracyclic ring systems of the anthracycline and tetracycline antibiotics;The route was developed about the regiospecific Claisen rearrangement of 2-hydroxy-5-allyloxyacetophenone. Thermolysis of various 2-hydroxy-5-allyloxyacetophenone derivatives results in a Claisen rearrangement followed immediately by an intramolecular Diels-Alder cycloaddition to afford highly ...


Bridgehead Intermediates In Organic Synthesis: Two Direct Syntheses Of Racemic Lycopodine , Yung-Son Hon Jan 1985

Bridgehead Intermediates In Organic Synthesis: Two Direct Syntheses Of Racemic Lycopodine , Yung-Son Hon

Retrospective Theses and Dissertations

In small ring bicyclic systems such as bicyclo 2.2.2 octanes and bicyclo 3.3.1 nonanes the bridgehead carbocation does not suffer hydride shifts. Additionally, the large energy difference between the bridgehead carbocation and the analogous acyclic carbocation provides a strong driving force for bridgehead bond formation;Both intramolecular and intermolecular reactions of bridgehead carbocations derived from bicyclo 2.2.2 octanes and bicyclo 3.3.1 nonanes are described. The carbocations are best generated from the corresponding halide with silver triflate. The carbocations reacted effectively with allyltrimethylsilane, ethyl acetoacetate, benzene, silyl enol ethers, amines and acetonitrile;Both ...


Reactions Of Radicals With Nucleophiles: The Nature Of The Aryl Radical Intermediate In The Aromatic Srn1 Reaction , James Michael Tanko Jan 1985

Reactions Of Radicals With Nucleophiles: The Nature Of The Aryl Radical Intermediate In The Aromatic Srn1 Reaction , James Michael Tanko

Retrospective Theses and Dissertations

The nature of the intermediate(s) in the aromatic S(,RN)1 reaction has been studied by two approaches: The reactivity of phenyl radical, generated from an unambiguous source, has been compared to the phenyl radical intermediate in the S(,RN)1 reaction. In the second approach, an intramolecular radical rearrangement was utilized for both diagnostic and kinetic purposes;Evidence has been presented for a second kinetically significant intermediate in the aromatic S(,RN)1 reaction with which nucleophiles can react. Having the requirements that this intermediate be both paramagnetic and a precursor to free aryl radical, its identity was ...


Exploratory And Mechanistic Studies Of Cycle Allene Photochemistry , Thomas James Stierman Jan 1985

Exploratory And Mechanistic Studies Of Cycle Allene Photochemistry , Thomas James Stierman

Retrospective Theses and Dissertations

Direct solution-phase irradiation of 1,2-cyclononadiene (8) yields bicyclo 6.1.0 non-1(9)-ene (84), tricyclo 4.3.0.0('2,9) nonane (10), and cyclononyne (85) as primary photoproducts in a 94:3:3 ratio. A kinetic isotope effect of 1.30 for the formation of 84 implies that hydrogen rather than carbon is migrating. Optically active 8 is rapidly photoracemized; the relative rate of racemization to isomerization to 84 is determined to be 70. Irradiation of 8 in methanol yields 84, 10, 85, and cis-3-methoxyclononene (99) in a 90:2:3:3 ratio. Independent generation of potential ...


Studies Of The Pyrolysis Of Hydroaromatic Compounds With An Emphasis On Reactions Of Ortho-Quinodimethanes , Michael Eugene Scribner Jan 1985

Studies Of The Pyrolysis Of Hydroaromatic Compounds With An Emphasis On Reactions Of Ortho-Quinodimethanes , Michael Eugene Scribner

Retrospective Theses and Dissertations

The flash vacuum pyrolysis of 4-methylbenzocyclobutene and benzocyclobutene-1,1-d(,2) affords labeled styrenes which require the intermediacy of substituted arylcarbenes and cycloheptatetraenes. A deuterium isotope effect of 2.2 is found for the C-H insertion reac- tion of one of the intermediate carbenes. Methyl substituents on the aromatic ring of the arylcarbenes influenced the direction of the migration of the carbene towards the closest methyl substituent;The liquid phase pyrolysis of benzocyclobutene in a high pressure atmosphere of hydrogen gas produces ortho-xylene. The pyrolysis of cyclopentadiene in hydrogen gas produces cyclopentene and cyclopentane. The pyrolysis of benzocyclobutene in deuterium gas ...


A Free Radical Synthesis Of Y-Lactones Using Tri-N-Butylstannyl Iodoesters , Kevin Dean Landgrebe Jan 1985

A Free Radical Synthesis Of Y-Lactones Using Tri-N-Butylstannyl Iodoesters , Kevin Dean Landgrebe

Retrospective Theses and Dissertations

Interest in the use of free radical reactions in synthetic organic chemistry has greatly intensified in recent years. A program was undertaken to develop a free radical synthesis of (gamma)-lactones which would occur under neutral conditions. Thus, treatment of olefins with tri-n-butylstannyl iodoacetate in the presence of a catalytic amount of the free radical initiator, 2,2'-azobis(2-methylpropionitrile) (AIBN) in refluxing benzene resulted in good yields of 4-substituted-(gamma)-lactones. The products were separated from iodotri-n-butylstannane by partitioning between acetonitrile and hexanes. Further purification by column chromatography afforded the pure (gamma)-lactones;This reaction has also been extended ...


Organomercury, -Rhodium And -Palladium Intermediates In Organic Synthesis , Krishnaswamy Narayanan Jan 1985

Organomercury, -Rhodium And -Palladium Intermediates In Organic Synthesis , Krishnaswamy Narayanan

Retrospective Theses and Dissertations

Chapter I describes the synthesis of arylolefins in fair to good yield by the cross-coupling reaction of arylmercurials and vinyl halides catalyzed by 10% ClRh(PPh(,3))(,3). The reaction appears to involve initial oxidative addition of the vinyl halide to the rhodium(I) catalyst to yield a vinyl rhodium(III) species and subsequent arylation by the organomercurial to generate an aryl vinyl rhodium(III) intermediate which reductively eliminates the olefin and regenerates the catalyst;Chapter II details an improved, stereospecific synthesis of vinylmercurials from alkynes using catecholborane, followed by mercuric acetate plus sodium acetate. A vinylmercurial useful in prostaglandin ...


Mechanistic And Synthetic Aspects Of Acetylene-Alkylidenecarbene Rearrangements In The Gas Phase , Brian Laue Groh Jan 1985

Mechanistic And Synthetic Aspects Of Acetylene-Alkylidenecarbene Rearrangements In The Gas Phase , Brian Laue Groh

Retrospective Theses and Dissertations

The flash vacuum pyrolysis (FVP) of ortho-substituted trimethylsilyl(phenyl)acetylenes resulted in the formation of indene and naphthalene derivatives not possessing silicon. The loss of silicon was proposed to occur after cyclization of the starting material;Flash vacuum pyrolysis of acetylenes with a dimethylsilyl substituent beta to the acetylene group provided an unprecedented and convenient method of silacycle formation. Utilizing this new method of silacycle formation, 1,1-dimethyl-1-silaindene and 3,3-dimethyl-4-oxa-3-silacyclopentene were formed in 84% and 32% yield, respectively. Deuterium labeling studies revealed pathways competitive with alkylidenecarbene formation and trapping which led to the products;Alkylidenecarbene cyclization was also applied ...


I. Kinetic And Mechanistic Study Of The [4+4] Dimerization Of 2,3-Dimethylene-2,3-Dihydrofuran; Ii. Preparation Of 2,3-Dimethylene-2,3-Dihydrobenzo[B]Furan By The Flash Vacuum Pyrolysis Of 2-Methyl-3-Benzo[B]Furylmethyl Benzoat; Iii. Reaction Of 2,3-Dimethylene-2,3-Dihydrofuran With Triplet Oxygen , Chin-Hsing Chou Jan 1985

I. Kinetic And Mechanistic Study Of The [4+4] Dimerization Of 2,3-Dimethylene-2,3-Dihydrofuran; Ii. Preparation Of 2,3-Dimethylene-2,3-Dihydrobenzo[B]Furan By The Flash Vacuum Pyrolysis Of 2-Methyl-3-Benzo[B]Furylmethyl Benzoat; Iii. Reaction Of 2,3-Dimethylene-2,3-Dihydrofuran With Triplet Oxygen , Chin-Hsing Chou

Retrospective Theses and Dissertations

A kinetic and mechanistic study of the 4+4 dimerization of 2,3-dimethylene-2,3-dihydrofuran (1) has been carried out based on the secondary deuterium kinetic isotope effects (2(DEGREES) D KIE), substituent effects and solvent effects. The 2(DEGREES) D KIE was studied by measuring the rate constants, k(,1), k(,2), k(,3) and k(,4), respectively, for the 4+4 dimerization of 1, 2-methylene-3-dideuteriomethylene-2,3-dihydro- furan (2), 2-dideuteriomethylene-3-methylene-2,3-dihydrofuran (3) and 2,3-bis(dideuteriomethylene)-2,3-dihydrofuran (4). The relation among k(,1) - k(,4) at -30.0(DEGREES)C was found to be k(,2)/k(,1) = k ...


Nuclear Magnetic Resonance Studies Of Amorphous Silicon Hydrides: Proton Spin Dynamics , Charles Gordon Fry Jan 1985

Nuclear Magnetic Resonance Studies Of Amorphous Silicon Hydrides: Proton Spin Dynamics , Charles Gordon Fry

Retrospective Theses and Dissertations

The island size in amorphous silicon hydride has been estimated to be (TURN)75 (+OR-) 30(ANGSTROM) for an assumed three-dimensional domain, or 40 (+OR-) 20(ANGSTROM) for a two-dimensional domain. These results were obtained using spin-diffusion via the Goldman-Shen experiment;Arguments have been given to suggest that the interpretation of the Lorentzian line shape should be reexamined. Several reasons, and some calculations provide motive for interpreting the Lorentzian line shape as due to monohydrides bonded to the interstitial surfaces parallel to the growth direction, where the surface has reconstructed to give the larger than expected internuclear separations leading to ...


Formation Of Benzene By The Pyrolysis Of 4-Vinylcyclohexene Regiospecific Formation Of Anthracenes In The Pyrolysis Of Dibenzosuberones And Related Systems , Jay Leslie Tunkel Jan 1985

Formation Of Benzene By The Pyrolysis Of 4-Vinylcyclohexene Regiospecific Formation Of Anthracenes In The Pyrolysis Of Dibenzosuberones And Related Systems , Jay Leslie Tunkel

Retrospective Theses and Dissertations

The thermal rearrangement of the dimer of butadiene (32), 4-vinyl-cyclohexene (34), was investigated by flash vacuum pyrolysis (FVP). The FVP of 4-vinylcyclohexene-3,3,5,5,6,6,8,8-d(,8) (34-d(,8)) at 800(DEGREES)C gave benzene (30), which had a statistical deuterium incorporation, as a major product. From the results of the study a new mechanism for the pathway from butadiene (32) to benzene (30) is proposed;Also described is a study on dibenzocyclooctene-5,5,6,6,-d(,4) (16-d(,4)) and the isolation and characterization of the minor products produced along with anthracene (13) in the FVP ...


Regioselective Diels-Alder Reactions. A Synthesis Of The Left-Hand Portion Of Cc-1065, George A. Kraus, Stephen Yue, James Sy Jan 1985

Regioselective Diels-Alder Reactions. A Synthesis Of The Left-Hand Portion Of Cc-1065, George A. Kraus, Stephen Yue, James Sy

Chemistry Publications

Diene 2b reacted regioselectively with dienophiles. Adduct 6 was converted into the left-hand portion of CC-1065 in 10% overall yield.


The Irreversible Inhibition Of D-Amino Acid Oxidase With Trans-3-Bromoacrylic Acid And Four Others Halo-Vinylic Acids, Christopher D. Kontos Jan 1985

The Irreversible Inhibition Of D-Amino Acid Oxidase With Trans-3-Bromoacrylic Acid And Four Others Halo-Vinylic Acids, Christopher D. Kontos

Dissertations, Theses, and Masters Projects

No abstract provided.


Preparation Of Methyl-Substituted Dienols By The Hydromethylation Of Ene-Yn-Ol Substrates With Titanium Tetrachloride And Trimethylaluminum, Terry James Zitzelberger Jan 1985

Preparation Of Methyl-Substituted Dienols By The Hydromethylation Of Ene-Yn-Ol Substrates With Titanium Tetrachloride And Trimethylaluminum, Terry James Zitzelberger

Dissertations, Theses, and Masters Projects

No abstract provided.