Chemistry Commons^™

Kinetics And Mechanism Of Acylation Of Amines With 2-Naphthoyl Azide, Abraham L. Faburada

Dissertations

The reaction of 2-naphthoyl azide with primary and secondary amines in protic and aprotic solvents follows second-order kinetics. The effect of increasing solvent polarity is shown to increase the rate of reaction. For amines of similar basicity, the rate of reaction decreases with increasing steric hindrance on the amine. The changes in free energy and entropy of activation for n-butylamine and cyclohexylamine are in accord with steric requirements of amines. For amines of similar steric hindrance, the rate of reaction increases with increasing amine basicity. The mechanism of addition-elimination involving the formation of a tetrahedral intermediate is consistent with the …

Micellarly Catalyzed Reaction Of Substituted Benzohydroxamic Acids, Nop Utrapiromsuk

Dissertations

The rate constants for hydrolysis of ten derivatives of benzohydroxamic acid, namely, p-H, p-CH(,3), m-CH(,3), p-CH(,3)CH(,2), p-OCH(,3), p-NO(,2), p-Cl, and m-Cl, in 0.160 and 0.158 M HCl at 67.9-68.2(DEGREES)C without and with sodium 1-dodecanesulfonate were determined. There is a good linear correlation between log k(,w) and the Hammett substituent constants, (sigma), for all para and meta derivatives where k(,w) is the rate constant in the bulk aqeous phase. In the presence of micelles all the compounds, except the meta-nitro derivative, followed the standard pseudophase model of micellar catalysis. However, correlations of log k(,m) or log K/N, where k(,m) is the …

Analysis Of Organic N-Chloramines In Chlorinated Drinking Water, John Po Wen Yang

Chemistry & Biochemistry Theses & Dissertations

This thesis describes the development of a sensitive method for the separation and quantitation of organic N-chloramines in chlorinated tap water. 5-Dimethylaminonaphthalene- l-sulfinic acid has been synthesized and characterized. It yields highly fluorescent dansyl derivatives on reaction with N-chloramines. Conditions of the derivatization were optimized for the detection of N-chloropiperidine at concentrations in aqueous solution of 10^-7 M. The technique gives a quantity of derivative which is proportional to the concentration of chloramine present over the range examined (10^-7 M to 10^-4 M). High pressure liquid chromatographic separation of dansyl derivatives of amines and amino acids has …

The Regioselective 3-Alkylation Of Piperidine, Richard Dunn Todd

Chemistry & Biochemistry Theses & Dissertations

The compounds: 3-allylpiperidine, 3-ethylpiperidine and 3-n-butylpiperidine have been synthesized by regioselectively alkylating the three position of piperidine. Piperidine was converted to N-chloropiperidine and then dehydrohalogenated to produce Δ¹-piperideine. The enamide anion was generated by adding solutions of Δ¹-piperideine to ethylmagnesium bromide or lithium diisopropylamide. Addition of alkylhalides produced 3-alkyl- Δ¹-piperideine which could be reduced or alkyllithiated to give 3-alkylpiperidines or 2,3-dialkylpiperidines respectively.

The yields of products were low and the reaction generated a continuum of mono- and di-alkylpiperidines and there was evidence that several dimeric piperideines were formed. The low yields were discussed in …

Synthesis Of Dihydroisoquinolines And Tetrahydroisoquinolines, John J. Schlager

Chemistry & Biochemistry Theses & Dissertations

Dihydroisoquinolines and tetrahydroisoquinolines are compounds which possess a variety of pharmacological activities. New easier methods of synthetic manipulations of these structures is of constant interest in the pharmaceutical industry.

This paper describes a new three step method of preparing 1-alkyl- and 1-aryl-tetrahydroisoquinolines from a tetrahydroisoquinoline. The synthesis involves the N-chlorination of tetrahydroisoquinoline followed by dehydrohalogenation with potassium superoxide. The reaction products are the dihydroisoquinolines. Overall yields range from 85-96%. The unsubstituted, 1-methyl-, and 1-phenyl-J,4-dihydroisoquinolines have been formed. Organometallation of the unsubstituted dihydroisoquinoline provides the 1-substituted tetrahydroisoquinoline. The 1-benzyl-, 1-n-butyl-, 1-ethyl-, 1-methyl-, and 1-phenyl-1,2,J,4-tetrahydroisoquinolines were prepared. The use of Grignard and …

A Technique For The Isolation And Identification Of Aliphatic Amines In Water, Peter Alan Drew

Chemistry & Biochemistry Theses & Dissertations

Small, aliphatic amines added to a basic, aqueous solution (16.2 L) at a concentration of 100 parts per billion were isolated by sorption on a small column of macroreticular resin. The amines were eluted with diethyl ether; the eluate concentrated, and the compounds separated and identified by gas chromatography. The efficiency of the recovery of a-nines ranged from 5 to 28%.

A protocol for derivatizing pyrrolidine and n-pentylamine in ether with fluorinated acylating agents was developed. The method was found to be adequate for the detection of approximately 13 micrograms of &-nines in concentrated ether extract.

Environmental water samples …

Method For Direct Preparation For 1,2,4-Triazole From Hydrazine And Formamide, Harris E. Petree, Joseph R. Pociask, John T. Gupton

Chemistry Faculty Publications

Process for the preparation of 1,2,4-triazole comprises contacting hydrazine or its aqueous solutions with at least about 2.5 moles of formamide at a temperature of 140° to 210° C. and then recovering the resultant 1,2,4- triazole in yields of 92-98% with 94-98% purity. The formamide is maintained in an excess over about the 2.5 molar amount consumed in the reaction with the hydrazine. Recovery steps for isolating the 1,2,4-triazole are disclosed.

A Study Of The Photolysis Of O-Methyl Podocarpinitrile Oxide, Dianne Marie Hunter

Dissertations and Theses

The photolytic reaction of 0-methyl podocarpinitrile oxide to yield the δ-lactam (shown below) was studied under various conditions such as: solvent (hexane, methanol), mercury lamp wattage (lOOW, 450W), filter (Pyrex, Corex, Vycor), and additives (dichloromethane, hexafluorobenzene). The reactions were analyzed with IR, NMR and HPLC. Preparative medium pressure liquid chromatography and TLC were used in the δ-lactam isolation. The conditions resulting in the optimum yield of δ-lactam were determined. The photolytic stability of the δ-lactam under the conditions in which it was formed indicated that it was relatively stable only in hexane.

Transport Of Ozone Across An Air/Water Interface Coupled With Aqueous Decomposition, Ahmad Ali Mehrabzadeh

Dissertations and Theses

Photoacoustic spectroscopy was used to analyze the transport of ozone through the air/water interface. Experimental results showed that the ozone transport rate is similar to rates measured for other gases of low solubility and low reactivity. The transport rate increases with increasing pH. The decomposition rate of ozone was studied in solutions. The decomposition rate also depends on the pH of the solution, and in high pHs both the deposition velocity and the decomposition rate constant of ozone have larger values. The value of the deposition velocity (Kd) is 3.7 ± .9 x 10^-3 cm/sec and the decomposition rate …

Preparation And Properties Of Benzotropones And Benzohomotropones, Robert E. Suder

Dissertations

No abstract provided.

The Concentration And Speciation Of Sugars In Natural Waters, Minoo Shakerin Sweet

Dissertations and Theses

Due to the importance of carbohydrates in biological systems, many efforts have been made to develop a quantitative method for analysis of carbohydrates in natural waters. The low concentrations of dissolved sugars in natural waters require a sensitive analytical method. In this study, gas chromatography of alditol acetate derivatives of sugars was investigated for quantitative and qualitative analysis of individual dissolved sugars in natural waters. The alditol acetate derivatives of sugars give only one derivative for each sugar, yielding qualitative and quantitative results.

The detection limit was 25 nM for each sugar. Because of this very low detection limit, only …

Bulletin 3992 - Nitrogenous Fertilisers For Cereal Production, M. G. Mason

Bulletins - 3000 - 3999

Because fertiliser prices continue to rise, it is becoming increasingly important to understand what affects the response to fertilisers by crops.

Among the many factors influencing crop response to nitrogen applications, the most important are the season, soil type, paddock history, time of application and source of nitrogen. Before deciding whether to use nitrogen on a cereal crop, which source to use and at what rate, the farmer needs some understanding of how these factors work.

A Process For The Production Of 2-Alkyl Or 2-Cycloalkyl-4-Methyl-6-Hydroxypyrimidines, Joseph T. Blackwell Iii, John T. Gupton, Teruko U. Miyazaki, James B. Nabors, Joseph R. Pociask

Chemistry Faculty Publications

Production of 2-alkyl- or cycloalkyl-4-methyl-6- hydroxypyrimidines by first neutralizing an alkyl imidate ester hydrochloride with a base in the presence of a water-immiscible solvent for the alkyl imidate ester to be freed thereby; condensing the alkyl imidate ester with diketene to form an oxazinone intermediate, which is then reacted in organic solution with gaseous ammonia and recovering the desired substituted 6-hydroxypyrimidine.

The Unexpected Preferential Formation Of 1-Alkyl-1-Phenyl-2–Propanones On Monoalkylation Of The 1-Phenyl-2-Propanone Dianion, Jack M. Hinkley

Masters Theses

No abstract provided.

The Effects Of Electron-Donating And Electron-Withdrawing Groups On The Alkylation Sites Of Para-Substituted Phenylacetones, Abraham L. Faburada

Masters Theses

The dianions of phenylacetone and its para-substituted derivatives were generated using potassium hydride and n-butyl lithium in tetrahydrofuran. Methyl, ethyl, and n-butyl iodides were used to alkylate the dianions. The results of alkulation indicated that C₁ is preferentially attacked by the less active ethyl and n-butyl iodides. The results further show that terminal alkylation is enhanced by electron-donating groups at the para-position of the phenyl ring. The results are rationalized in terms of the difference in electron density at C₁ and at C₃ in the dianion, on the basis of resonance theory. The regio-selectivity of alkylation as …

Determination Of The Rate Of Formation Of Hcn, Mitchell Hull

Honors Theses

Nitric oxide is a major air pollutant arising from fossil fuel combustion, yet the fuel contribution to its formulation is uncertain. Since, in combustion, fossil fuels undergo disintegration before oxidation takes place, the study of the pyrolsis of a model constituent of fossil fuels can shed light on NO formation. The rate of inert pyrolytic disappearance of pyridine and the rate of formation of the principal Nitrogen-containing pyrolytic product, HCN, was studied in an inert atmosphere. The rate constant for the formation of HCN and its temperature dependence were determined.

The Preparation And Study Of Some Bridged Tropones, Sultan T. Abu-Orabi

Masters Theses

No abstract provided.

Proximity Effects. Kinetics, Mechanisms And Reactivity Correlations For The Acidic And Alkaline Hydrolysis Of Ortho-Substituted-N-Methylbenzohydroxamic Acids, Irl E. Ward

Dissertations

No abstract provided.

Comparisons Between Oriented Film And Solution Tertiary Structure Of Various Nucleic Acids, Douglas R. C. Priore

Chemistry and Chemical Biology ETDs

It was desired to help establish whether or not the tertiary structure of a biomolecule is the same in a cry­stal (or an oriented film) as it is in solution. Generally it is accepted that the structures in these diverse environ­ments are similar, if not identical. By comparing the extinction coefficients obtained from oriented film data to those obtained from solution data it was hoped that this question might further be resolved. To this end an electric dichroism instrument built in our lab was used to measure the dichroic signal so as to calculate, with the help of the ultraviolet …

Studies Toward The Total Synthesis Of A Colchicine Analog, Jacob Shya Tou

Masters Theses

No abstract provided.

Side-Chain Metalations Of Certain Dimethylpyridines By Means Of Organoalkali Metal Reagents, Stephen Bendzunas

Masters Theses

No abstract provided.

Unusual Alkylations Of The 1,1-Diphenyl-2-Propanone Dianion, Ruth E. Tenbrink

Masters Theses

No abstract provided.

The Synthesis And Study Of The Enolate Monoanion Of 2, 4-Di-P-Anisylbicyclo(3.2.1)Oct-6-En-3-One, Phillip D. Reynhout

Masters Theses

No abstract provided.

The Synthesis And Physical Properties Of Some 1-Methyl And 2-Methyl Bridged Cycloheptapyrazolones, Gary R. Larson

Masters Theses

No abstract provided.

Kinetics And Stoichiometry Of The Aquation Reaction Of Pentaaquodihalomethyl Chromium(Iii) Ions, Mohammad Javaid Akhtar

University of the Pacific Theses and Dissertations

This study was designed to provide information about the mechanisms of pentaaquodihalomethyl chromium(III) ions (halo chloro, bromo and iodo).

...

Mechanisms based on carbonium ion, carbeno and carbenoid type intermediates are proposed. A mechanism based on the nucleophillic attack (S_N2) of water on the carbon center leading to a metal-formyl type intermediate is suggested as best fitting all the criteria observed in these studies.

(see PDF file for additional Abstract as it includes formulas)

Process For The Production Of 2-Alkyl Or 2-Cycloalkyl-4-Methyl-6-Hydroxypyrimidines, John T. Gupton, Alex M. Jelenevsky, Teruko U. Miyazaki, Harris E. Petree

Chemistry Faculty Publications

Production of 2-alkyl or 2-cycloalkyl-4-methyl-6-hydroxy pyrimidines by first reacting diketene and lower alkanoic or cycloalkanoic acid amides in the presence of catalytic amounts of Lewis bases or Lewis or Bronsted acids, followed by treating the N-acetoacetyl (lower) alkanoic or cycloalkanoic acid amide intermediates with ammonia in the presence of acid catalysts.

Process For The Production Of 2-Alkyl Or 2-Cycloalkyl-4-Methyl-6-Hydroxypyrimidines, J. Thomas Blackwell, John T. Gupton, Jim B. Narbors

Chemistry Faculty Publications

Production of 2-alkyl or 2-cycloalkyl-4-methyl-6-hydroxy pyrimidines by sequentially reacting without isolation of any intermediates in an organic solvent (1) diketene and ammonia to produce .beta.-aminocrotonamide and (2) .beta.-aminocrotonamide, after water removal therefrom, a lower alkanoic or cycloalkanoic acid ester and an alkali metal alkoxide.

The Effect Of Stabilizing Groups On The Extent Of Long-Range Π Electron Participation And The Effect Of The Negative Charge On The Chemical Shift Of Neighboring Protons In Carbanions, Atilla Tuncay

Dissertations

No abstract provided.

A Stereochemical Study Of Some 2,2'-Bridged Biphenyls, Alan J. Quarfoot

Dissertations

No abstract provided.

3,3-Diphenyl-2-Morpholinone Derivatives Of 2-Amino-2-Deoxy-D-Allose., Ram Babu

University of the Pacific Theses and Dissertations

A new cyclic protective group has been fused to the cis amino alcohol group of benzyl 2-amino-3,5-o-benzylidene-2-deoxyβ-D-Allopyranoside, by way of a unique rearrangements mechanism. To establish the 2-morpholinone structure, chemical studies, such as reduction and acetylation were conducted.

Comparative spectroscopic studies using ir, pmr, and C-13 nmr confirmed the assigned structures.

The 2-morpholinone ring was cleaved by mild alkaline hydrolysis and could be closed again with acetic anhydride in pyridine. An oxazolidinone derivation of benzyl 2-amino-4,6-o-benzylidene-2-deoxyβ-D-allopyranoside was prepared in a quantitative yield by a modification of a known method.

Protective group properties of the oxazolidinone were studied prior to the …