Perdeutero-spiropentane (C₅D₈) has been synthesized and infrared and Raman spectra are reported for the first time. Wavenumber assignments are made for most of the fundamental vibrational modes. Gas phase infrared spectra were recorded at a resolution (0.002 cm⁻¹) sufficient to resolve individual rovibrational lines and show evidence of strong Coriolis...
I. Lithium alkyl and aryl monosubstituted cyclooctatetraenide
dianions (Li₂ C₈H₇-R; R = methyl, n- butyl, sec- butyl, tert- butyl,
phenyl and benzyl) were synthesized by the reaction of the appropriate
organolithium reagent with cyclooctatetraene in diethyl ether or
tetrahydrofuran. The reaction occurred cleanly and with good yield
of lithium monosubstituted...
Studies toward the total syntheses of highly potent cytotoxic alkaloids
including the bromopyrrole alkaloids and indole alkaloids were conducted and are
described. Studies carried out in the course of this dissertation consist of five total syntheses of natural products that include bromopyrrole alkaloids nagelamide A, D and agelastatin D as...
Pelargonium graveolens Ait., rose geranium, contains several oxygenated monoterpenes, most of which are related to each other structurally. In this work, the metabolism and interconversions of these terpenes was investigated. A chromatographic analysis of geranium oil was performed initially for the purposes of identifying the terpenes and determining which chromatographic...
Sulfide is an important species to measure in environmental water samples. The
spectrophotometric detection method for reduced sulfur species (sulfide) based on
generation of methylene blue was adapted to work in an apparatus utilizing microfluidic
PDMS mixing and observation cells with flow channels in the 100 μm range. The
benefits...
A method for the control of absolute stereochemistry in
morphine syntheses has been demonstrated by the resolution
and efficient racemization of the advanced morphine precursor , 9-methoxy-3-methyl-5,6-dihydro-3H-benzofuro[3,2-e]isoquinoline-
7(7aH)-one, I. This was accomplished by the facile coversion of optically resolved I to its ring opened
form, 5,6,7,8-tetrahydro-10-methoxy-3-methyl-7-oxo[1]benzoxonino[
6,7-c]pyridinium tosylate, II, (Equation...
A tracer method utilizing stable activable tracers (involving rare earth nuclides with short-lived t[subscript 1/2] < 1 day} activation products) for tracing fluid bound substances in fresh water is explored. Simulated laboratory studies showed these tracers (Dy and in) when chelated with diethylenetriamine2entaacetic acid a7i1W to be stable ( <20%)...
The high resolution stimulated Raman spectrometer at OSU was
modified to improve its sensitivity and to extend its range of
applications to low Raman shifts and to the spectroscopy of solids and
liquids. As part of the characterization of the spectrometer, optical
Stark effects on rotational and vibrational transitions of...
A new experimental apparatus was built at Oregon State University to perform high resolution stimulated Raman spectroscopy in a pulsed molecular jet at state densities of the order of 10¹¹ cm⁻³. The technique uses a stimulated Raman step to first populate a vibrational/rotational level and then a resonantly enhanced multiphoton...
Many D2d-symmetric 2,2',6,6'-tetrasubstituted biphenyls are
readily prepared via net oxidative dimerization of appropriate
1,3-disubstituted benzenes. Conversion of such proprochiral
compounds to useful C2-symmetric chiral biphenyls requires
formal replacement of two substituents on opposing aryl ring
units with alternate groups. This under exploited
desymmetrization tactic has been demonstrated for the
generation...
An automated multielement flame atomic fluorescence (AF) spectrometer based on microcomputer control was constructed to determine four elements simultaneously. The instrument employs a multiple exit slit monochromator where the light from various exit slits is directed to a single detector with a mirrored funnel. Each element is excited to fluoresce...
Studies towards the total synthesis of (+)-Phomactin A (1), D (6), and G (9), fungal metabolites with unique molecular architecture and pronounced biological activity, are described. These studies resulted in the synthesis of advanced intermediates 354 and 356, which contain all of the carbon atoms of 1, 6 and 9....
The enantioselective total synthesis of quinolizidine-containing natural product cermizine D and formal syntheses of senepodine G and cermizine C has been achieved. These natural products are members of the lycopodium alkaloids, which have attracted significant attention due to their exciting biological activities and the diverse structural scaffolds. Key steps in...
The analysis of 64 rock samples from Saudi Arabia and three
samples from the axial trough of the Red Sea has been done.
Instrumental neutron activation analysis (INAA) was the analytical
tool used for the analysis of at least 18 and as many as 24 elements
in these 67 rock...
An automated instrument based on a single-board microcomputer
was developed for use in voltammetric analyses. Operator input of
numerous experiment parameters allows any type of voltammetric
analysis to be implemented and multiple scans to be run unattended.
A three operational amplifier potentiostat is used to control
the cell voltage and...
7,7'-Dihydroxy-8,8'-biquinolyl (azaBINOL) was prepared from 7-hydroxyquinoline via N,N-dimethyl O-quinol-7-yl carbamate by directed ortho-metallation followed by FeCl₃-mediated oxidative coupling of the 8-lithioquinoline intermediate. Saponification of the resulting dicarbamate provided crystalline (±)-azaBINOL in 56% overall yield. 6,6'-Bis(dimethylaminocarbonyl)-7,7'-dihydroxy-8,8´-biquinolyl was prepared from the same dicarbamate by a double anionic-Fries rearrangement in 43% yield. 7,7'-Bis(diethylamino-carbonyloxy)-6,6'-diiodo-8,8´-biquinolyl...
Interesting rovibrational characteristics of two D_(3h) oblate symmetric top molecules were studied. Hamiltonian models for the fine rovibrational level structure of [1.1.1]propellane (propellane) were obtained for many low-lying modes. Ground state parameters (GSP) that are not exclusively K^(2n) dependent were obtained. Initially, the GSP were used in conjunction with density...
A sensitive technique for the determination of As(III) and As{V)
at μ/L and sub-μg/L concentrations from a single sample aliquot
has been developed. This technique is based on the hydride
generation atomic absorption (HGAA) spectrophotometry. The hydrides
of the arsenic species are generated in a reaction vessel by mixing
the...
Early studies on the biosynthesis of the quinoline quinone portion of
streptonigrin, 1, had suggested the intermediacy of novel aromatic amino
acids. In order to test this hypothesis, a series of compounds was synthesized
and tested for potential incorporation. [4-¹⁵N] 4-Aminoanthranilic acid,
4 5 a , [4-² H] 7-aminoquinaldinic acid,...
The design and construction of two new sample injection systems or nozzles, for use with the Oregon State electron diffraction apparatus are discussed. One of these nozzles was intended for use with volatile samples the vapors of which were to be heated or cooled over the range -196 to 540°C;...
Two nonlinear optical experiments are presented in which the third-order electronic susceptibility of molecules is used to generate Raman signals. The first one uses a single 532 nm beam from a Nd:YAG laser to produce Stimulated Raman Scattering in benzene and deuterated benzene. With a simple experimental set-up, stimulated emission...
This thesis describes the development of a new enantioselective synthetic method employing chiral cis-2,5-diaminobicyclo[2.2.2]octane-based organometallic catalysts. The significance of this new method to organic synthesis is illustrated with preparation of enantioenriched products that are transformed to important pharmaceutical agents. Chapter 1 provides a brief historical overview of asymmetric catalysis, especially...
The design and construction of a chemiluminescence
photometer is described. The design is based on a discrete
sample system which has a number of advantages over
the previously described flow cell system and centrifugal
analyzer. The advantages include simple and inexpensive
equipment, small sample size, versatile electronic readout
system, and...
The first asymmetric synthesis of (-)-7-epicylindrospermopsin via intramolecular nitrone cycloaddition is described. The synthesis utilized a convergent approach to prepare the cycloaddition precursor 176, which was assembled by condensation of hydroxylamine 175 with aldehyde 145. Hydroxylamine 175 was synthesized from ethylene glycol (166) in seven steps. Aldehyde 145 was completed...
The development and optimization of a single-phase derivatization
technique for small ring aromatics in water are presented. Also
described are the design, optimization and application of a remote
reaction chamber for fiber optic sensing.
Aqueous solutions of the major aromatic compounds in gasoline are
derivatized to o-nitrosophenol-Cu complexes with a...
¹³⁰ Sn and ¹²⁸Sn were separated from mixed fission products.
The decay of these isotopes were studied with Ge(Li),
LEPS, and plastic scintillator detector systems in single
and two parameter coincidence modes. The decay scheme constructed
for ¹²⁸Sn decay has levels at 0.0 (5+), 45.7 (4+),
77.8 (3+), 152.9 (2+),...
Four strategies which involve synthetic elaboration of
the shikimate nucleus are discussed. Methyl shikimate was
differentially protected as the 3,4-0-cyclopentylidene ketal
and as the 5- 0- tert- butyldiphenylsilyl ether. The methyl
ester was then reduced with diisobutylaluminum hydride and
the resulting allylic alcohol was oxidized to aldehyde 47
with pyridinium...
This thesis is concerned with the development and use of routine
analysis techniques based on chemiluminescence (CL) detection for: 1)
ethanol in gin down to the 0.3% (v/v) level; 2) the antioxidants propyl
gallate and BHA in lard to levels as low as 0.3 and 0.2 mg/L, respectively; 3) pyrogallol...