The synthesis and insecticidal activity of certain alcohols (hydroxymethyldibenzofurans, hydroxymethyldibenzothiophenes and some of their ⍺-cyano derivatives), esterified with trans-chrysanthemic acid, were investigated. The preparation of these planar alcohol moieties was undertaken to study conformation-activity effects in insecticides of the pyrethroid type. The synthesis of final ester products employed two methods. One was the direct condensation of the appropriate alcohol with chrysanthemic acid chloride in the presence of pyridine. The other involved the in situ formation of the cyanohydrin from the appropriate aldehyde and subsequent condensation with chrysanthemic acid chloride in the presence of a phase transfer reagent. Insecticidal activity is to be tested at rates of 0.001, 0.01, 0.1, 10, 100, and 1000 ppm. Fenvalerate is used as the standard against Diabrotica undecimpuntata (spotted cucumber beetles).

(1). An improved method for synthesizing bicyclo (2,2,1) hepta-2,5-diene-7-spiro-1'-cyclopentane (5) has been developed. Thermal reaction of compound (5) with neat iron pentacarbonyl under nitrogen atmosphere affords the corresponding cage dimer (6). Some aspects of the syntheses, spectra, and chemistry of compound (5) and (6) are discussed. (2). A structure isomer of decamethyldodecahedrane (C₃₀H₄₀), molecule (11), is expected to be synthesized via thermal reaction of iron carbonyl complexes with compound (10). An intermediate in this synthesis, 2,2- tetramethylene-1,4-dibromobutane (9) was efficiently synthesized starting from cyclopentanone. Some aspects of the syntheses, spectra, and chemistry of compound (1) to (9) will be discussed.

Lecithin:cholesterol acyltransferase (LCAT) was purified 30,000-fold from hog plasma in a homogeneous state as indicated by polyacrylamide gel electrophoresis. The purified enzyme had an apparent molecular weight of 66,000 and was found to contain about 21.4 percent (w/w) carbohydrate. The properties of hog LCAT including amino acid composition were compared with human LCAT. High density lipoprotein (HDL) was isolated from the hog plasma by an immunoaffinity column chromatography. The isolated HDL showed nearly identical lipid-protein composition although it contained additional protein components when it was compared to HDL isolated by a traditional method involving ultracentrifugation.

As part of a continuing study of the synthesis and chemistry of new, substituted pentacyclo(5.4.0.0²，⁶.0³，¹º.0⁵，⁹)undecanes, the following compounds have been synthesized: 1: X=O, Y=SiMe_3; 2: X=CH_2, Y=SiMe_3; 3: X=O, Y=Cl; 6: X=OAc, Y=H; 8: X=OC(O)Ph, Y=H; 9: X=OSO_2Ph, Y=H; 11: X=OH, Y=H; 12: X=OMe, Y=H; 14: X=CHSiMe_3, Y=SiMe_3; 15: X=OH, Y=Cl; 16: X=OAc, Y=Cl; 17: X=OMe, Y=Cl. An important objective of this work is to prepare new polycyclic cage compounds which can be utilized as intermediates for the synthesis of new, substituted tricyclopentanoid natural products (triquinanes) and related systems. Compounds 1-4 were identified as target molecules in this connection.

In order to explore the N-H stretching region of aliphatic amines, we performed a study of the Raman spectrum of n-propylamine at various concentrations in cyclohexane. Statistical analysis provided evidence of a second symmetric stretching vibration, which we were able to assign to nonhydrogen bonded NH2 groups. To obtain additional evidence on the existence of monomers in n-propylamine and to further study hydrogen bonding and Fermi resonance in aliphatic amines, we extended the investigation to the analysis of the Raman spectrum of this compound over an extended range of temperature in the neat liquid phase. This study corroborated our finding that the peak previously assigned to the symmetric stretching mode of hydrogen bonded amines is actually composed of two bands. Furthermore, trends in both the resolved band parameters and the Fermi resonance analysis were tabulated, allowing one to monitor the change in the N-H valence region with concentration and temperature.

The physico-chemical properties of lecithin:cholesterol acyltransferase were investigated. The amino acid composition analysis showed a relatively high content of glutamic acid, aspartic acid, glycine and leucine. The spectrophotometric titration of phenolic groups in the enzyme showed a large increase in absorbance at 295 nm with an apparent pK of about 12.0. The largest change in molar ellipticity at 222 nm was also observed above pH 11. Circular dichroism studies revealed that human lecithin:cholesterol acyltransferase has a relatively high content of β-pleated sheet structure (48%) with 20% α-helix, and 32% remaining structure. Human lecithin:cholesterol acyltransferase has a high extinction coefficient at neutral pH. Microsequencing of the amino terminal residues of the enzyme revealed a hydrophobic character. Inactivation of lecithin:cholesterol acyltransferase activity was observed using diisopropylfluorophosphate with a stoichiometry of 1 mole of diisopropylphosphate incorporated per mole of enzyme. This suggests the involvement of a serine residue in the active site of the enzyme, possibly for the formation of an acyl-intermediate. A new quicker assay method for lecithin:cholesterol acyltransferase was developed. This assay involved coupling reaction with acyl CoA synthetase, ΡΡᵢ-dependent phosphofructokinase, aldolase, triosephosphate isomerase and α-glycerol-3-phosphate dehydrogenase monitoring a change in the absorbance or fluorescence intensity due to the oxidation of …

The reaction of tert-butyllithium with chloromethylphenylvinylsilane at low temperatures in hexane gave a 48% yield of a mixture of the five isomers of 1,3-dimethyl-1,3-diphenyl-2,4-dineopentyl-1,3-disilacyclobutane, formed by the head-to-tail dimerization of both E- and Z-1-methyl-1-phenyl-2-neopentylsilenes, along with an acyclic dimer. These were separated and their stereochemistry was established by ('1)H- and ('13)C-NMR spectroscopy. The E- and Z-silenes were also trapped as their {4 + 2} cycloadducts with cyclopentadiene, 2,3-dimethyl-1,3-butadiene and anthracene, which also were separated and stereochemically characterized. A consistent mole ratio of 70:30 for the E- and Z-silene adducts is interpreted as evidence for stereochemical induction in the silene generation reaction. It is also suggested that the dimerization of the silenes to give the 1,3-disilacyclobutanes occurs by a nonstereospecific stepwise pathway. When E- or Z-1-methyl-1-phenyl-2-neopentylsilene was generated by the retro-Diels-Alder flow vacuum thermolysis of its corresponding cyclopentadiene or anthracene adduct at temperatures between 400 and 600(DEGREES)C and then trapped with 2,3-dimethyl-1,3-butadiene, the stereochemical distribution of the products is independent of the stereochemistry of the silene precursor, indicating that the silene is not configurationally stable towards cis-trans isomerization at these temperatures. Evidence that the intermolecular ene reaction and the {4 + 2} cycloaddition which occur with 2,3-dimethyl-1,3-butadiene are concerted is presented. …

The objective of this study was to develop new synthetical routes to natural and industrial products utilizing ketene cycioaddition reactions. The cycioaddition of diphenylketene with α,β-unsaturated imines yields (2+2) cycioaddition products, g-lactams. However, electron donating groups, such as dimethylamine, in the 4-position of the α,β-unsaturated imines result in (4+2) cycloaddition products, ∂-lactams. Dichloroketene reacted with α,β-unsaturated imines to yield (4+2) cycloaddition products, g-lactams. Large substituents in the 4-position of a, ^-unsaturated imines resulted in a (2+2) cycioaddition product, β-lactam. The ∂-lactams derived from dichloroketene are easily dehydrochlorinated to the corresponding 2-pyridornes.

A series of dihydroxy bridged copper(II) complexes of the type [(L)Cu(OH)₂Cu(L)]x₂ * nH₂0, where L is 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine or 1,10-phenanthroline, x is a counter ion, and n is the number of water molecules, was synthesized. In the case of monohydroxy bridged copper(II) complexes, we have found a new method of synthesis for [ (L)₂Cu(OH)Cu(L)₂ ] (ClO₄)₃, where L is 2,2'-bipyridine or 1,10-phenanthroline. We have synthesized five new monohydroxy bridged copper(II) complexes, thus increasing the number of monohydroxy bridged copper(II) complexes to nine. All complexes have been characterized by infrared spectroscopy, UV-visible spectroscopy, magnetic moments, and elemental analysis. The electron spin resonance results establish that the fulvic acids contain organic free radicals as an internal part of their molecular structure. The concentration of unpaired electrons will increase by increasing the pH. The unpaired electron in fulvic acid interacts with the unpaired electron on copper(II) through the Π system, and this will decrease the spin concentration of fulvic acid complexed with copper(II). The displacement of titration curve from a free ligand (fructose-1,6-diphosphate, ribulose-1,5-diphosphate, phospherine, phosphothreonine, and 3-phosphoglyceric acid, to a ligand plus copper(II) (1:1 ratio) shows there is a strong interaction between copper(II) and the corresponding ligand. All complexes absorb UV-visible at …

The hydration behavior of the calcium aluminates as a function of the glass content, the curing temperature, and the water-solid ratio was investigated. In order to keep them from influencing the results, the free-lime content and the surface area of all samples were kept constant, whenever possible. Samples were hydrated with a water-solid ratio of 10/1 for periods of 1 to 90 days. Three curing temperatures were studied; 2°C, 25°C, and 50°C. Samples were hydrated in tightly sealed polyethylene containers to prevent reactions with atmospheric carbon dioxide. The hydration was followed by X-ray diffraction and thermal analysis. Only two samples, Hexacalcium Tetra-alumino Magnesium Silicate and Tricalcium Magnesium Dialuminate, were successfully prepared in an amorphous form. These compounds were used to investigate the effect of glass content on the hydration behavior. Results indicate that when the glass content is increased a corresponding increase is found in the percent combined water. Samples hydrated at 25°C were influenced by changes in the glass content to a greater degree than were those hydrated at either 2°C or 50°C. The effect of the water-solid ratio on the hydration behavior of the calcium aluminates was studied using the compounds; Hexacalcium Tetra-Alumino Magnesium Silicate/ and Dodecacalcium Hepta-Aluminate. …