The pyrolysis of sec-butyllithium in solution was studied in an attempt to understand the loss of stereo-specificity and the atypical kinetics that have been reported. Additionally, the effect of added lithium alkoxides was studied to determine their effects on the highly reactive sec-butyllithium substrate.
This study is concerned with the nature of the relatively unusual bonding which occurs in organolithium compounds as a direct result of the oligomerization and possible explanations for that bonding.
In this work, the principal concern will be with the coupling reaction and it is anticipated that the other reactions referred to above will be considered further when products of the RX-R'Li reactions are discussed.
An investigation of the cycloaddition behavior of dichloroketene with various types of olefins seemed in order to determine if dichloroketene behaved similarly to dialkylketenes. It was anticipated that a study of this type would indicate the reactivity of dichloroketene to various types of olefinic compounds and thus establish if the ease of cycloaddition with dichloroketene parallels the nucleophilicity of the olefin as it does in dialkylketenes.
The object of this thesis is to establish the diffusion coefficient of Na ion in PbCl2-NaCl mixtures and to compare its relationship to the other species.
Since 1955 research has been conducted at North Texas State College on diffusion in molten salts. The object of this work was a continuation of the diffusion studies, specifically the diffusion of Pb210 and Cl36 in molten PbCl2-NaCl mixtures.
This paper is an attempt to appraise the usefulness of the dropping gallium electrode (DGE) in fused LiNO3-KNO3, to compare it with the dropping mercury electrode (DME), and to study the DGE in fused LiCl-KCl.
Gases at satisfactory pressures fluoresce in the presence of radio frequency radiation (6). Such fluorescent gases have been used to probe fields of radio frequency oscillation and their emission spectra have been recorded and studied. Ions with multiple charges also exist in these gases, (6). In 1941 Oliver (12) observed the fluorescence of an isobutane- isobutene gaseous mix flowing to a pump through a glass tube which was wrapped by a spiral antenna of a sevenmegacycle transmitter. A white deposit was noticed at a bend in the tubing on the pump side of the fluorescing section of the gas (12, p. 8). In 1957 Blacknall (3) studied the fluorescence and reaction products of propylene in the antenna region of sevenmega- cycle radiation, The oscillator employed by Blacknall was an ARC-5/T-22 military surplus transmitter of range 7.00 to 9.10 megacycles, which he operated at 7.00 megacycles. Blacknall observed a drop in pressure and the formation of a brown deposit in the region of the coil. Blacknall did not report an analysis of this product. In 1959 Armstrong (1) repeated Blacknall's experiments and modified Blacknall's apparatus into an improved design. He also performed an analysis on Blacknall's product. Blacknall used a vertical open-end mercurial manometer with which to measure pressure in his system and as a result introduced mercury vapor into his system. Armstrong tried to minimize the amount of mercury introduced by covering his manometric mercury with a layer of octyl sebacate, "octoil". Armstrong used a spiral-would antenna wrapped around his reaction vessel and reported the formation of spiral brown rings coincident with the copper wire of the antenna. There was a white product deposited in a spiral interlaced with the spiral of dark brown material. No definite identification was reported by Armstrong other than reporting, his solid material as isotactic …
The objective of this investigation was to determine the electronic effects of the halogen atoms in dihaloketenes such as dichloroketene and dibromoketene.
As long ago as 1881, it was realized that a functional group of atoms in a molecule would cause an absorption band to appear at a particular frequency in the infrared spectrum of the molecule. In more recent years, the concept of characteristic group frequencies has become firmly established and has resulted in the present widespread use of infrared spectroscopy. There appear to have been relatively few studies of infrared absorption of organic acids as compared with their salts.
The present work is a part of a systematic investigation of the frequency shifts in infrared absorption produced by changing to the anions carbonyl containing acidic compounds.
There is no available information in the literature on interaction between carboxyl hydrogen and ω-phenyl groups. Consequently, it was of interest to seek such interactions. Some form of interaction is evident from the study of the spectra of some phenylalkanoic acids and benzoyalkanoic acids.
The study of some acylurea derivatives of 2-amino-3-alkylamino- and -3-arylamino-1,4-naphthoquinones was undertaken to determine the course of reaction under conditions similar to those used by J. R. Hoover and A. R. Day to prepare 2-alkyl-1H-naphth[2,3-d] imidazole-4.9-diones from 2-acylamino-3-amino-1,4-naphthoquinones.
The work reported by D. Bryce-Smith and G. F. Cox, along with several recent publications describing experimental results designed to elucidate the long disputed question of the structure of the Grignard reagent in ether stimulated the work reported here, in an effort to obtain additional evidence of the structure of the organomagnesium complex in benzene solvent. Since the primary objective of this work was to prepare organoberyllium compounds using the organomagnesium complexes in hydrocarbon solvents, it seemed an insight into the structure of these complexes would be beneficial in this work. The techniques used and experimental evidence obtained from the structure elucidation of the ethereal Grignard reagent have been most helpful in organization of the methods used to study the structure of organomagnesium halide complexes in benzene solvent. It seemed that an insight into the structure of these organomagnesium halide complexes in hydrocarbon solvents would be beneficial in accomplishing the second objective of this work. This objective was to prepare organoberyllium compounds using the organomagnesium halide complexes prepared in hydrocarbon solvents.
The procedure of Takimoto, Denault, and Hotta was followed in order to prepare 4-amino-3-hydrazino-5-methyl-s-triazole hydrochloride (II) and its precursor, triamino-guanidine hydrochloride (I).
In many series of compounds, intensity of biological activity and chemical reactivity are proportional. Generally whenever a alkyl group replaces a reactive hydrogen atom, as would be the case for an N-substituted hydroxylamine as compared to hydroxylamine, the over-all biological activity of the resulting compound is lower than that of its nonalkylated analogue. Since toxicity and physiological activity are not proportional, this comparison can only suggest possible types of derivatives to prepare and test.
A series of compounds were prepared by condensing 2,3-dimethyl-4,9-dioxo-1-(2-propyl)-naphth[2,3-d] imidazolium iodide with various aromatic aldehydes.
In the course of attempting to prepare 3,6-bis(hydroxy-methyl)-s-tetrazine via the reduction of 3,6-bis(carboxy)-s-tetrazine with lithium aluminum hydride, it became apparent that the tetrazine ring was cleaved.
An experiment was designed to study in the same animal any preferential absorption of a free fatty acid in the presence of a triglyceride of the same fatty acid. Rats were administered a mixture of free fatty acid and its triglyceride labeled with carbon-13 and carbon-14 respectively. Each isotope in the fed lipid and in the lipid recovered from the gastrointestinal tract was measured. The isotope effect, if any, was studied by administering a mixture of palmitic acid-1-C13 and palmitic acid-1-C14.
The specific goal of the investigation was the measurement, as a function of temperature, of the self-diffusion coefficients of Pb210 and Cl36 in PbCl2-KCl compositions in the region of the first compound, and to calculate from these data the activation energy necessary for the diffusion of these ions.
The study herein described involved the detection of pyridine N-oxide reductase activity in cell-free extracts of E. coli 9723, the determination of co-factors necessary for the enzymatic process, a study of the optimum conditions for enzyme catalysis, and a general characterization of the enzyme.
The study reported herein concerns itself with the isolation of melaninless mutants of S. antibioticus, ATCC, 3723, and with the demonstration that at least one of the sites of mutation involves that of the enzyme, tyrosinase.
Since only one example of an asymmetric synthesis which involved an intermediate containing an optically active ligand has been reported, two questions immediately arise: "Is this type of asymmetric synthesis an isolated example, or is it a stepping stone toward a generalized trend for Co (III) which may be extended to include levo rotatory, as well as dextro rotatory molecules?" In addition, asymmetric synthesis affords a new avenue for synthesizing resolved neutral complexes.
The purpose of this investigation is two-fold. Some new complex compounds, where one of the bidentate molecules is an optically active amino acid, were prepared, and attempts to separate those complex isomers by different methods were made. The replacement of the amino acids by optically inactive ligands was studied.
A number of N-substituted-3-hydroxy-3-phenylphthal-imidines and some of the isomeric amides have been prepared in order to study changes in the infrared spectra of these compounds due to structural changes in the molecule, particularly with reference to a hydroxyl band at 3.0µ and a carbonyl band at 5.75µ.
This study reported herein involves the synthesis and determination of certain biological activities of 4,5-dihydroxy-2-pyridinealanine and the synthesis of 3-pyridine-N-methylalanine.
At the time this work was begun, there was some confusion about the technique necessary for the successful synthesis of organomagnesium compounds in hydrocarbon solvents and without solvents. It was decided to repeat the work of Bryce-Smith and Zakharkin. Thus began the study of the synthesis of organomagnesium compounds without solvents; the study of the reaction products of these organomagnesium compounds in hydrocarbons plus 2-butanone compared to the reaction products of the corresponding etheral Grignard reagent plus 2-butanone; and a preliminary study of the nature of these organomagnesium compounds in hydrocarbon solvents.
Part one of this thesis concerns the polymerizability of some α,β-unsaturated monaldehydes and also relates the synthesis of some new polyaldehydes which have not been reported in the literature. Part two concerns the polymerization of glyoxal, the simplest dialdehyde, and the structure elucidation of this new polymer.
Since Djerassi and Scholz found that 2-(aryloxy-methyl)imidazolines and their hydrochloride salts exhibit vasoconstrictive properties, the 1,2-(I) 1,3-(II) and 1,4-bis-(2-imidazolinylmethoxy) benzene (III) analogs (Fig. 1, p.2) were chosen for synthesis in order to test them for their effective vasoconstrictive characteristics and for whatever other physiological properties they might exhibit.
This thesis is concerned with the thermal decomposition of a series of alkyllithium compounds in the pure state in an attempt to determine the relative stability of alkyllithium compounds and to examine the mechanism of the elimination reaction.
The turbidimetric method for the determination of lead ion developed in this work is not intended as a replacement for standard analytical procedures, but is presented solely as a laboratory exercise for courses in elementary instructional analysis.
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