A classification of stationary liquids by infrared spectroscopy to evaluate the polarity was made using the solvent effect technique. The infrared C-Cl absorption frequency shift was measured for solutions of 1-chlorohexane dissolved in each stationary phase. These frequency shifts were correlated to the relative retention times of 1-octene/n-octane, trans-2-octene/n-octane and...
The ethyl acetate extract of the culture filtrate of the marine Ascomycete,
Leptosphaeria oraemaris (Linder) yielded a novel metabolite
designated by the common name leptosphaerin. An x-ray crystallographic
structure analysis was disproved by the synthesis of 3-acetoxy-S-(1,2-dihydroxyethyl)-
3-pyrrolin-2-one 1, starting with N,N-dibenzylhydroxylamine
47 and D-mannitol 44. Oxidation of 47 followed...
This thesis describes a study of the synthesis, stereochemistry,
and reactivity of cobalt(III) cysteinato (CyS) and related thiolato complexes.
The preparation of [Co(en)₂CyS]⁺ resulted in a product solution
containing a mixture of diastereomers in the ratio 2.3:1 (Δ:A). The isomers were separated by ion exchange chromatography, and
their absolute configurations...
Eleven hand specimen whole rock (WR) samples (25-200 g each) and
33 fragments (0.5-0.8 g each) from a single basaltic flow at Picture
Gorge, Oregon were analyzed via instrumental neutron activation
analysis (INAA) for 12 elements (Na, Fe, Cr, Sc, Co, La, Sm, Eu, Yb,
Lu, Hf and Ta). Standard...
Intramolecular cyclization of organometallic compounds represents
a promising tool for synthesis. The reaction involves exothermic
consumption of intramolecular double bonds via insertion
into a carbon metal sigma bond. This represents an intramolecular
example of the reaction type responsible for metal catalyzed polymerization
of olefins.
Organolithium reagents were found to cyclize...
This research emphasized fundamental physical and electrochemical
studies of systems based on the room temperature fused salt, triethyl-ammonium
dichlorocuprate(I). Such systems, which must be maintained
under a protective atmosphere, were also used in some preliminary
battery studies.
Spectra of dark green solutions of copper (II) chloride in
triethylammonium dichlorocuprate(I) obey...
Intramolecular cyclization of organometallic compounds represents
a promising tool for synthesis in general. The use of strategically-
placed heteroatoms in the cyclizing molecule can influence
the stereochemistry and/or efficiency of an organometallic cyclization
while providing for functionality in the cyclic product.
The work described herein first concerns cyclizations of organolithiums....
The photochemistry of aldicarb and two related compounds,
0-(methylcarbamoyl) isobutyraldehyde oxime and 0-(methylcarbamoyl)
trimethylacetaldehyde oxime was explored under laboratory
conditions. Upon irradiation aldicarb decomposed rapidly to
methylamine, dimethylamine, tetramethylsuccinonitrile, and
1-methylthio-2, 3-dicyano-2, 3-dimethylbutane. The other two
compounds decomposed only after a long period of irradiation. The
difference in reactivity was...
Lamellar x-ray diffraction was studied from thin films of L-α-1,2-dipalmitoyl lecithin (DPL) and a 1:1 mixture (BrDPL) of L-α-l-palmitoyl-2-(9- bromopaimitoyl) lecithin and its 10-bromo analog. The specimens had high lamellar order, with an upper bound on the mosaicity of 6 mrad (0.4°) for DPL and BrDPL. With various water contents,...
As part of the continuing investigation of the thermal cis- 1, 3, 5-hexatriene to 1,3-cyclohexadiene rearrangement, four new trienes and a cross-conjugated pentaene have been prepared and their thermal reactions studied. A new route to the synthesis of highly substituted trienes has been developed. The synthesis of three of these...
The Diels-Alder reaction represents a promising tool for use in
asymmetric synthesis. The reaction involves a rigid transition state
that facilitates the formation of one diastereomeric transition state
and is reversible. This satisfies two necessary criteria for
asymmetric synthesis.
The Diels-Alder reactions of 1,l-dialkylspiro[2.4]-4,6- heptadienes
with maleic anhydride and p-benzoquinone...
Hydrated cobalt(II) and nickel(II) trifluoromethanesulfonates have
been prepared by a previously reported procedure, and have been
characterized for the first time as [ Co(H₂O)₆] (CF₃SO₃)₂H₂O and [Ni(H₂O)₆] (CF₃SO₃)₂. These formulations are based on analyses,
near-infrared spectra, and on measurements of the ligand field
electronic spectra and the magnetic susceptibilities. The...
Several approaches to the synthesis of methymycin were
investigated. Segment A (39), containing functionality corresponding
to C-9, 10, and 11 of methynolide was made in
six steps from propionaldehyde in an overall yield of 37%.
Oxidation of 34 with silver nitrate gave 35 which, upon hydroxylation
with hydrogen peroxide, gave...
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 atmospheric trace element abundances associated with "indoor"
and '"outdoor" air particulate have been measured for university chemistry
laboratories, typical homes, modern office buildings, hospital and
automobile repair garages in a rural setting (Corvallis, Oregon) and
modern office buildings in an urban setting (Portland, Oregon). Samples
of atmospheric particulate matter...
Gas-solid chromatography often has asymmetrical elution
peaks. This is attributed to nonlinear isotherms, multi-energy
adsorption sites, and slow processes. This study utilized a stopflow
gas chromatograph with various NaOH and NaCl modified
aluminas as adsorbents and methane as adsorbate to determine the
influence of surface area and pore volume distribution...
This thesis describes a Mossbauer effect and electron
paramagnetic resonance study of iron (III) tetraphenylporphyrinatobenzenethiolate
benzene thiol, an analog compound
for bacterial cytochrome P-450. The compound is unusual in
that it provides a model for the two ferric reaction states
of cytochrome P-450. The iron in the model compound exhibits...
The tosylhydrazones of exo-3-deuteriocamphor and 2- deuterio-2,4-dimethy1-3-pentanone were treated with Nbromosuccinimide (NBS) and pyruvic acid to regenerate the parent ketones. The ketones from the pyruvic acid cleavage show a significant loss of deuterium. The ketones from the NBS cleavage show no loss of deuterium, indicating that stereochemical integrity at. C[subscript...
Studies of anisotropic and isotropic Raman line shape yield information about the rotational motion (rotational correlation function) and non-reorientational (vibrational) lifetimes. The rotational motion of carbon disulfide has been studied previously by the techniques of Raman spectroscopy (6, 43), Rayleigh scattering (43, 46) and direct measurement (47). This work was...
A multielement spectrometer has been developed for the simultaneous determination of four elements by atomic absorption (AA) or atomic fluorescence (AF). The spectrometer is based on a multiple exit slit monochromator and uses a mirrored funnel to direct light from the various exit slits to a single photomultiplier. There are...
The application of lucigenin chemiluminescence for the determination
of trace concentrations of Co(II) is described. This method
is based on the enhancing effect that Co(II) has on the reaction of
lucigenin and hydrogen peroxide in a basic solution. The chemiluminescence
signal from a Co(II) enhanced lucigenin reaction, which is in...
A procedure for evaluating the precision of atomic absorption
measurements is presented and applied to 21 elements under varying
instrumental conditions. The experimental relative standard deviations
(RSD's) in absorbance obtained from repetitive measurements made
with a high resolution voltmeter and on-line computer, are compared
to those predicted by a recently...
A total synthesis of the fungal hormones, trisporic acids A and B, is described, starting from a -methyltetronic acid 34. A Robinson annelation of 34 with ethyl vinyl ketone affords the lactone 33. Treatment of 33 with N-bromosuccinimide gave 97, which was hydrolyzed to the lactol 103. The reaction of...
The satellite structure ("shake-up") present in the X-ray
photoelectron spectra of several planar molecules containing
double bonds has been investigated in the gas phase.
This set consists of three five-membered heterocyclic
molecules, ethylene and two of its fluorinated analogs, and
benzene with three of its fluorinated analogs. In addition,
core...
The potassium salts of a series of 1-vinylcycloalk-3-en-l-ols were found to undergo ring expanding [1, 3]-sigmatropic shifts at 25° when dissolved in hexamethylphosphoramide (HMPA) or 1, 2-dimethoxyethane (DME) with 18-crown-6. The yields and reaction rates were compared with those of the corresponding Siloxy-Cope ring expansions. These anionic cases showed about...
Several approaches to the synthesis of penicillin from 2-iminothioazolidine
50, from 2-thiothiazolidine 66 and by photocyclization of
77 and 78 were investigated. 2-Iminothiazolidine 50 was prepared
from dibromoester 45 by the action of benzylamine followed by treatment
of aziridine 46 with potassium or ammonium thiocyanate. Attempted
introduction of a two-carbon...
A new x-ray source capable of operating at up to 80
watts has been designed and developed, and put to use with
the Oregon State University Cylindrical Electrostatic
Analyzer. The new source produces over four times the
photoelectron intensity of its predecessor, from gaseous
samples, and accommodates a wider selection...
Diffusion of short chain n-alkanes was found to be faster in the
polydimethylsilicone elastomer SE-30 than in the polydimethylsilicone
oil SF-96-2000. The opposite was true for the longer chain n-alkanes
suggesting that choice of stationary phase for gas chromatography
would depend on the chain length of sample components. The dependence...
Investigations of plasma production by a pulsed dye laser
microprobe were made. Comparisons between a Q- switched and a
pulsed dye laser system were made on the intensity of the continuum
produced by atmospheric breakdown. The dye laser system was
foundtominimize the production of the continuum which in turn
allowed...
The retro-ene reaction of 2-vinylcyclohexanols occurs readily
in the vapor phase at 400-450° producing unsaturated carbonyl
compounds in good yields. The starting- materials were prepared in
general by the carbenoid addition reaction of ethyl diazoacetate,
appropriately substituted cyclohexene, and copper catalyst to
produce bicyclic esters which were reduced to the...