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Articles 1 - 21 of 21

Full-Text Articles in Organic Chemistry

Micellar Catalyzed Hydrolysis Of Hydroxamic Acids By Perfluorooctanoic Acid, Mohammad Hashem Akhavan Tafti Dec 1988

Micellar Catalyzed Hydrolysis Of Hydroxamic Acids By Perfluorooctanoic Acid, Mohammad Hashem Akhavan Tafti

Master's Theses

The work reported herein demonstrated that a perfluorocarboxylic acid does indeed behave as a reactive counterion surfactant exhibiting micellar catalysis, this conclusion was further verified by subsequent experimentation.

Rates of acidic hydrolysis of octano-, phenylaceto-, and 4-bromo phenylacetohydroxamic acid have been determined in aqueous perfluorooctanoic acid--a reactive counterion surfactant system. Typical micellar catalysis was observed for the hydrolysis of octanohydroxamic acid but not for the arylacetohydroxamic acids.

Further investigation into finding a more water soluble surfactant which has reactive counter ions is suggested in order to test the theoretical equation (based on the pseudo phase model) appropriate for this surfactant ...


Gas-Phase And Computational Studies Of Pentacoordinate Silicon, Robert Damrauer, Larry W. Burggraf, Larry P. Davis, Mark S. Gordon Sep 1988

Gas-Phase And Computational Studies Of Pentacoordinate Silicon, Robert Damrauer, Larry W. Burggraf, Larry P. Davis, Mark S. Gordon

Mark S. Gordon

We have demonstrated that a wide variety of pentacoordinate silicon anions (siliconates) should be stable and can be prepared by combining the predictive powers of MNDO and ab initio computational methods and the flowing afterglow (FA) experimental technique. MNDO has been used to compute the anion affinities of 91 siliconates; all but five of these are predicted to be stable with respect to the loss of an anion. Twenty-four siliconates, most of them previously unreported, have been prepared and studied in the FA. The MNDO predictions were, in general, consistent with the experimental results and with trends previously reported by ...


Cycloaddition Reactions Of Bridgehead Enones, George A. Kraus, Yung Son Hon, James Sy, Jeff Raggon Apr 1988

Cycloaddition Reactions Of Bridgehead Enones, George A. Kraus, Yung Son Hon, James Sy, Jeff Raggon

Chemistry Publications

The cycloaddition reactions of bridgehead enones derived in situ from ketones 8,9, and 10 with various dienes at 0 "C afford good yields of adducta. Even 1,1,3-trisubstituted dienes work well. The exclusive exo stereochemistry can be rationalized in terms of a stepwise mechanism involving ionic intermediates.


Synthesis Of 7,7,8-Trideuteriated Trichothecenes, George A. Kraus, P.J. Thomas Apr 1988

Synthesis Of 7,7,8-Trideuteriated Trichothecenes, George A. Kraus, P.J. Thomas

Chemistry Publications

Trideuteriated trichothecenes can be generated from diacetoxyscirpenol by a reaction sequence involving acetylation, epoxide deoxygenation, allylic oxidation, deuterium exchange, epoxidation, and reduction.


Synthesis And Reactions Of A-Diketones And Preparation Of Some New Benzimidazoles, Mohamad Reza Agharahimi Apr 1988

Synthesis And Reactions Of A-Diketones And Preparation Of Some New Benzimidazoles, Mohamad Reza Agharahimi

Master's Theses

This report will discuss the synthesis of 2,5-dl-(p-chlorophenyl)-3,4-dioxoadiponitrile and its reactions. This compound exists in the form of 4,4'- dichloropulvinic nitrile which is a precursor to 4,4'-dichk>rovulpinic acid. These compounds have been shown to have antiinflammatory activity in rats.

The benzimidazole and pyridazine derivatives of 4,4'-dichioropulvinic nitrile and the benzimidazole derivative of 4,4'-dichk>rovuipinic acid are another group of compounds that are also believed to have useful biological activities. The Pinner synthesis of imidates is used to make the intermediate to the benzimidazole derivative of 4,4 ...


A Synthetic Approach To Novel Heterocyclic Herbicides, Paul Antony Pathadan Apr 1988

A Synthetic Approach To Novel Heterocyclic Herbicides, Paul Antony Pathadan

Master's Theses

The purpose of this research study was to prepare novel heterocyclic herbicides. The first phase of the project was to synthesize 1-(nitromethyl)-4-phthalazone.

In the second phase 1 - (nitromethyl)-4-phthalazone was treated with 1,3-propane-dithio-di-p-toluene sulfonate in presence of sodium hydride to get the target compound 4-(1'-nitro-l,3-dithiane)phthalazone.

It is believed that this compound might block the electron transport system of aerobic cells1 . So further investigation of this compound may lead to novel herbicides.


Synthesis And Study Of Novel Quinoxaline Di-N-Oxide And 3-Acyl-2-Methylquinoxaline Di-N-Oxides, Cyprian Okwara Ogbu Apr 1988

Synthesis And Study Of Novel Quinoxaline Di-N-Oxide And 3-Acyl-2-Methylquinoxaline Di-N-Oxides, Cyprian Okwara Ogbu

Master's Theses

This research project consists of two parts. The first involved the synthesis of a novel quininoxaline di-N-oxide via benzofuroxan. The second part was the use of this compound as a synthetic precursor.

It was assumed that 3,4-dimethylaniline would be successfully converted to 5,6-dimethybenzofurazan 1-oxide (5,6-dimethybenzofuroxan) through a sequence of reaction steps. Fortunately, this assumption was correct as the desired compound was produced. This compound was utilized in synthesizing the novel 3-acetyl-2,6,7-trimethylquinoxaline 1,4-dioxide. From the structure of this adduct, it is believed that it will take part in condensation reactions associated with methyl ketones without ...


A Direct Synthesis Of C-Glycosyl Compounds, George A. Kraus, Maria T. Molina Feb 1988

A Direct Synthesis Of C-Glycosyl Compounds, George A. Kraus, Maria T. Molina

Chemistry Publications

Lactone 4 (R = Bn) can be converted into C-glycosyl compounds by reaction with an organometallic reagent followed by reduction with Et,SiH and BF3.Et20.


Preparation And Utilization Of Organopalladium Intermediates , Hanchul Song Jan 1988

Preparation And Utilization Of Organopalladium Intermediates , Hanchul Song

Retrospective Theses and Dissertations

[pi]-Allylpalladium compounds have been prepared from alkenylcycloalkanes bearing 3- and 4-membered rings by reaction with organomercurials and dilithium tetrachloropalladate through a novel palladium-promoted ring-opening process. In the second part of the thesis, [pi]-allylpalladium compounds prepared in situ from various acetoxy-substituted dienes and functionally substituted organomercurials react with base to provide a new route to dihydrobenzofurans and lactones. In the part three of the thesis, cyclic alkenes bearing vinylic halides have been shown to undergo facile, palladium catalyzed cyclization to afford a wide variety of bicyclic cycloalkenes. This methodology allows one to close a 5- or 6-membered ring onto ...


The Transition State Of The Cyclopropylidene To Allene Ring Opening , Robert Jude Sutherland Jan 1988

The Transition State Of The Cyclopropylidene To Allene Ring Opening , Robert Jude Sutherland

Retrospective Theses and Dissertations

As part of an effort to understand the chemistry of cyclopropylidenes in solution, the effects of substituents on the relative rates of cyclopropylidene ring opening versus intermolecular insertion in methanol have been examined via correlation analysis;The trans-2,3-diarylcyclopropylidenes were generated via the base induced decomposition of ethyl N-nitroso N-(trans-2,3-diarylcyclopropyl)carbamates, in various concentrations of methanol, using toluene as the cosolvent. The partitioning of the disubstituted cyclopropylidenes in methanol solution at room temperature was found to be a linear function of the alcohol concentration;The relative cyclopropylidene to allene ring opening rate was found to increase when electron ...


Novel Ring Forming Reactions For Organic Synthesis , Jeffrey J. Thurston Jan 1988

Novel Ring Forming Reactions For Organic Synthesis , Jeffrey J. Thurston

Retrospective Theses and Dissertations

Almost all biologically important molecules contain a ring in their structure. The first two sections of this manuscript deal with general methodology which will facilitate the construction of certain rings. The last part of this manuscript deals with the total synthesis of a natural product containing a tricyclic structure;Part I deals with the preparation of cyclic 1,2-aminoalcohols. Many important natural products contain this substructure. Several recent synthetic methods have been reported for the synthesis of 1,2-aminoalcohols, attesting to the high interest in this area and also to the need for additional methods. Part I deals with the ...


I. Asymmetric Organic Photochemistry; Ii. Palladium-Catalyzed Allylic Arylation Of Cyclic Alkenes , Bruce Edward Baker Jan 1988

I. Asymmetric Organic Photochemistry; Ii. Palladium-Catalyzed Allylic Arylation Of Cyclic Alkenes , Bruce Edward Baker

Retrospective Theses and Dissertations

This dissertation is divided into two sections. The research in each section is of an entirely different nature. The focus of the first section will be different approaches to asymmetric organic photochemistry. The focus of the second section will be palladium-catalyzed allylic arylation of cyclic alkenes;The first section will discuss three different sets of experiments, aimed at exploring different aspects of asymmetric organic photochemistry. A model system involving the concept of chiral electron-transfer sensitizers is explored first. The latter two studies involve photochemically-induced [pi] bond rotation in allenes. The photoracemization of optically active 1,3-diphenylallene is observed and the ...


Synthetic Approaches To Anthracycline Antibiotics , Tim On Man Jan 1988

Synthetic Approaches To Anthracycline Antibiotics , Tim On Man

Retrospective Theses and Dissertations

Nogalamycin is an anthracycline antibiotic that exhibits inhibitory activity against both gram-positive microorganisms and several types of cancer. Several analogs have been tested and were found to be more active than the parent compound. 7-Con-O-methylnogarol was one of the most active analogs;Research was undertaken to develop an enantiospecific synthesis of 7-con-O-methylnogarol and other analogs. The investigation involved: (1) preparation of a ketosugar with three contiguous stereogenic centers from D-arabinose; (2) synthesis of a tetracyclic moiety which could be transformed into ABCD ring system of the synthetic target; and (3) a stereoselective coupling reaction between the ketosugar and the tetracyclic ...


Synthesis Of Fused And Bridged Ring Systems , James Nicolas Ong Sy Jan 1988

Synthesis Of Fused And Bridged Ring Systems , James Nicolas Ong Sy

Retrospective Theses and Dissertations

The efficient construction of fused and bridged carbocyclic ring systems has always been a challenge for the organic chemist. We describe the following advances: (1) An effective method for making cis-fused cyclopentanoids using samarium diiodide has been achieved. The resulting tricyclic fused systems were utilized in two concise approaches to rocaglamide, a compound that exhibits significant antileukemic activity. (2) A novel way of constructing bridged ring systems involving a reactive enone intermediate and 1,1,3-trisubstituted dienes has been effected. The unusual preference for the exo mode of cycloaddition is explained.


Free Radical Chain Reactions Involving An Electron Transfer Process , Woonphil Baik Jan 1988

Free Radical Chain Reactions Involving An Electron Transfer Process , Woonphil Baik

Retrospective Theses and Dissertations

Photostimulated reactions of 2-substituted-2-nitropropanes with 1°-alkoxide ions in alcohol solution afford 2,2-dialkoxypropanes in reasonable yields. The reactions are inhibited by O[subscript]2 and m-dinitrobenzene and do not occur in the dark. Furthermore, the reactions are retarded for a discrete period of time by a small amount of di-tert-butyl nitroxide. The evidence supports a free radical chain process involving the trapping of Me[subscript]2CNO[subscript]2[superscript]· by 1°-RO[superscript]-, the decomposition of ROCMe[subscript]2NO[subscript]2[superscript]-· to ROCMe[subscript]2[superscript]· and the oxidation of ROCM[subscript]2[superscript]· to ROCMe[subscript]2 ...


Catalytic Dehydrogenation Condensation Of Silyl Hydrides And Amines: Thermal Decomposition Of Silazanes And Polysilazanes , Kermit K. Kinsley Jan 1988

Catalytic Dehydrogenation Condensation Of Silyl Hydrides And Amines: Thermal Decomposition Of Silazanes And Polysilazanes , Kermit K. Kinsley

Retrospective Theses and Dissertations

The synthesis of silazanes by the condensation of silyl hydrides and amines or ammonia has been shown to be catalyzed by palladium chloride or ruthenium dodecacarbonyl. The synthesis of diaminosilanes can also be catalyzed by the same catalysts. Attempts to prepare disilazanes from rtriethylsilane and butylamine were not successful;The synthesis of polysilazanes was shown to be possible at room temperature when palladium chloride was used as the catalyst. Ruthenium dodecacarbonyl was not useful under these conditions. The molecular weight of the polysilazane is dependent upon the rate of ammonia addition to the silane solution. When trihydrosilanes were condensed with ...


Free Radical Processes Involving Electron Transfer Or Producing [Gamma]-Lactones , Steven J. Herron Jan 1988

Free Radical Processes Involving Electron Transfer Or Producing [Gamma]-Lactones , Steven J. Herron

Retrospective Theses and Dissertations

The formation constants of isopropyldichloromercurate and isopropyldiiodomercurate have been calculated to be 8.0 x 10[superscript]-2 and 8.6 dm[superscript]3/mole, respectively, using the variation of [superscript]1H NMR shift as a function of halide ion concentration. The reaction of an equilibrium solution containing approximately 55% isopropyldichlorormercurate with bromotrichloromethane was studied. Evidence is presented that supports the conclusion that the reaction is a free radical chain mechanism of considerable length (initial kinetic chain length > 38,000). The chain propagating step appears to be the reduction of the trichloromethyl radical by the isopropylmercurate. Though dialkylmercurials do not ...


Kinetic And Mechanistic Aspects Of The Thermal Decomposition Of Silyketenes, -Thioketenes And -Ketenimines , Gitendra Chandra Paul Jan 1988

Kinetic And Mechanistic Aspects Of The Thermal Decomposition Of Silyketenes, -Thioketenes And -Ketenimines , Gitendra Chandra Paul

Retrospective Theses and Dissertations

The flash vacuum pyrolysis (FVP) of bis(trimethylsilyl)ketene led to 1-trimethylsilylpropyne and a trace of cyclotrisiloxane. The products were accounted for by postulating a retro-Wolff process. The decomposition kinetics of dimethylsilyl(trimethylsilyl)ketene were followed in a stirred-flow reactor (SFR) and the activation parameters (Ea = 51.7 Kcal/mol, log A = 12.97) were obtained. FVP of several alkyl(trimethylsilyl)ketenes were also examined. These ketenes have been observed to decompose by three different routes viz., a retro-Wolff process, a homolytic cleavage process and a retro-ene process. When the alkyl group was t-butyl, the retro-Wolff product was not observed ...


Cyclic Ether Synthesis Via Lewis Acid Promoted Carbon-Carbon Bond Forming Cyclization Reactions Of Unsaturated And Saturated Symmetric Acetals, Elizabeth Gonda Jan 1988

Cyclic Ether Synthesis Via Lewis Acid Promoted Carbon-Carbon Bond Forming Cyclization Reactions Of Unsaturated And Saturated Symmetric Acetals, Elizabeth Gonda

Dissertations, Theses, and Masters Projects

No abstract provided.


The Synthesis Of Quinone-Capped Cyclodextrins, Michael Vernie Cossette Jan 1988

The Synthesis Of Quinone-Capped Cyclodextrins, Michael Vernie Cossette

Dissertations, Theses, and Masters Projects

No abstract provided.


Linked Beta-Cyclodextrins, Richard Desider Nemeth Jan 1988

Linked Beta-Cyclodextrins, Richard Desider Nemeth

Dissertations, Theses, and Masters Projects

No abstract provided.