In an effort to determine if there is a specific conformational structure which is most effective at the appropriate active physiological site, the synthesis of a group of sterically restricted analogs was undertaken. A portion of the polymethylene carbon skeleton of glutaric acid was replaced by selected aromatic carbons in benzenedicarboxylic acids to produce a series of ridged conformers, and the relative plant growth regulating properties of these derivatives were determined.

In these studies several different types of antimetabolites were synthesized, and their biological effects were examined in various assay systems. More extensive investigations were done in microbial systems in which many of the compounds proved to be inhibitory to growth, and attempts were made to determine the mode of biochemical action by adding supplements of the appropriate natural metabolite.

The site of initial metal-carbonyl bond-breaking during ligand-exchange reactions in a series of octahedral metal carbonyls of the type (L2)M(CO)4 (M = Cr, Mo, W; L2 = diphos, phen, dipy) has been determined employing infrared spectroscopy and Fourier transform nuclear magnetic resonance spectroscopy. The results of this study reveal, for all metal carbonyl complexes of the type mentioned above, that loss of CO occurs exclusively at an axial position (cis to the bidentate ligand, I^)• The dynamic nature of the five-coordinate intermediates, such as (diphos)Mo(CO)3, (phen)M(CO)3 (M = Cr, Mo, W), and (dipy)Cr(CO)3, which are generated in solution upon CO dissociation, is reported and discussed. The results of this investigation confirm that these intermediates are fluxional on the time scale of CO-exchange process. A mechanism which describes the site of initial metal-carbonyl bond-breaking and the fluxionality of the five-coordinate intermediate during ligand-exchange reactions in the complexes (L2)M(CO)4 is proposed. A kinetic study of reactions of W(CO)6 with pseudo-halide anions (NCS-, NCO-, CN-) has been initiated. The results indicate that these reactions proceed via a bimolecular path, which involves initial attack of the pseudo-halide anion at a carbonyl carbon of W(CO)6,

The kinetics and mechanism of the reactions of (tmpa)W-(CO)^ and (tmen)W(CO)^ (tmpa = N,N,N',N'-tetramethy1-1,3-diaminopropane and tmen = N,N,N1,N1-tetramethylethylenediamine) with four phosphorus donor ligands (triisopropyl phosphite, triphenyl phosphite, triphenylphosphine and "constrained phosphite", 4-methyl-2,6,7-trioxa-l-phosphabicylo[2.2.2]octane) in xylene have been investigated in detail. These reactions were found to take place by the ring-opening of the bidentate ligand in a reversible step which leads to the formation of a five-coordinate intermediate of the type [(h^-tmpa)W(CO)or [(h^-tmen)W(CO). The intermediate then reacts with one molecule of phosphorus ligand, L, to form a six-coordinate intermediate, which can either expel the bidentate ligand and react with another molecule of L leading to the formation of a new disubstituted tungsten tetracarbonyl or go through a ring-reclosure step to form a seven-coordinate activated com-2 2plex or intermediate of the type [(h -tmpa)W(CO)^(L)] or [(h - tmen)W(CO)^(L)] which then regenerates the substrate through the expulstion of the L molecule. This mechanism is consistent with the observed rate behavior in these systems. For the reaction of (tmpa)W(CO)^ with the "constrained phosphite", an intermediate of the type [(h1-tmpa)W(CO)4P(OCH2)3CCH3] was isolated and identified.

A kinetic study of the reactions of Group VI-B hexacarbonyls with primary amine and halide ligands was undertaken in order to determine the possible mechanisms of these reactions. As well as the expected dissociative pathway, the reactions with the primary amines were seen to proceed by a concurrent pathway which was dependent upon the ligand concentration. Since nitrogen donor ligands are expected to be poor donor ligands, the mechanism proposed was a "dissociative interchange" mechanism which should not be too dependent upon the nucleophilicity of the ligand. Comparison of the rate constants for the amines studied as well as those of the previously investigated Lewis base ligands indicated all such reactions may proceed through the same mechanism. The similarity in rate constants for the ligand-independent and ligand-dependent pathways supports this mechanism. The rate of formation of the final product was seen to be dependent upon the square of the mercuric halide concentration. Therefore, the conversion of Fe(CO)4(HgX)2 to the final product was proposed to proceed by the successive abstraction by each HgX group of two molecules of mercuric halide. These oxidative elimination reactions are related to a chemical model for the intermediate step in the reduction of dinitrogen to ammonia …

The purpose of this investigation is to study the Birch reduction products of [2.2lparacyclophane and of [2.2]paracyclophane- 2-carboxylic acid. The tetrahydro Birch reduction product of [2.2]paracyclophane is shown to be dl stereoisomer, with the olefins of the upper deck only partially overlapping with the olefins of the lower deck. This stereochemical elucidation is accomplished by means of a complete proton nmr analysis of the tetraepoxide derivative. A proposed mechanism supported by VB (valence bond) and MO (molecular orbital) theories for this Birch reduction process is presented.

The levels of total nicotinamide adenine dinucleotide (NAD) and nicotinamide adenine dinucleotide phosphate (NADP), and their redox states were determined as the function of growth in S. cerevisiae. Cells growing in a medium containing 0.8% glucose exhibit two phases of exponential growth, utilizing glucose and ethanol, respectively. The NAD pool is 50% reduced during both stages of growth while the NADP pool is 67% reduced in glucose growth and 48% reduced in ethanol growth. The NAD/NADP ratio is constant during growth on glucose and a two-fold increase in the NAD/NADP ratio occurs upon exhaustion of glucose. The increased ratio is maintained during growth on ethanol. This alteration in the regulation of the relative levels of NAD and NADP may be due to a change in the regulation of NAD kinase and/or NADP phosphatase activities. These changes may be related to the redox state of the NADP pool.

To gain better understanding of the nature of the carbonmetal bonding in 3-neopentylallyl alkali metal (5,5-dimethyl- 2-hexenyl alkali metal) systems, an investigation is extended to 3-neopentylallylpotassium. In addition, pertinent data on the 3-neopentylallyl systems are re-examined in an attempt to understand the trends in the bonding habits, as affected by the solvent, the cation and the temperature.

Many of the bands in the vapor-phase far-ultraviolet absorption spectra of simple molecules can often be fit to mathematical progressions referred to as molecular Rydberg series. The name Rydberg arises from the similarity between the Rydberg formula for the atomic hydrogen spectrum and the formulae for the progressions found in molecular spectra. The theories of molecular Rydberg transitions and states are discussed in terms of the inferences that have been made in the past from the available spectral data. The dipole moment changes (ca. 0.4 Debye units) from the ground state to all of the Rydberg states studied were found to be smaller than changes typically found in transitions of charge-transfer nature (ca. 1 Debye unit). The implication is that the Rydberg transitions are fairly localized. The changes in polarizability are on the order of 6 x 10⁻²⁴ cm³ and are assumed to be increases over those of the ground state.

The central nature of nicotinamide in metabolic processes as a part of the NAD and NADP coenzyme systems prompted the synthesis of a series of N-nicotinyl- and N-isonicotinyl-N'- (substituted)ureas as potential metabolite antagonists of the vitamin. The compounds which were synthesized may be represented by the following general structure, where R = hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, cyclohexyl, phenyl and a-naphthyl. The observed toxicity of the N-nicotinyl-N'-(substituted)urea analogs may be attributed to the formation of a non-functional N-nicotinyl-N'-(substituted)urea-NAD analog through an exchange reaction catalyzed by NAD-ases in the cell. Support for this view was obtained by an in vitro enzymic synthesis of Nnicotinyl- N'-ethylurea-NAD analog employing N-nicotinyl-7- 1 4CN'- ethylurea. The labeled derivative was characterized through spectral, chromatographic, and chemical reaction studies.

The development of an analytical method for the determination of total organic-bound chlorine (TOCl) produced during the chlorination of municipal wastewater effluents is presented. Sewage effluent from the Denton, Texas municipal treatment plant was chlorinated at high chlorine doses (1000 - 4000 ppm), as well as typical treatment levels. Chlororganics present in the wastewater, before and after chlorination, were concentrated by adsorption on Amberlite XAD-2 macroreticular resin, followed by elution with diethyl ether. After concentration, the extracts were analyzed for TOC1 by microcoulometry. Analysis of wastewater extracts revealed the production of substantial amounts of new chlorinated organics when effluents were treated with chlorine. The method shows good precision and estimated accuracy is favorable.

In model reaction systems to test amino acids in chlorinated waste effluents, several amino acids were chlorinated at high chlorine doses. (2000-4000 mg/1). Amino acids present in municipal waste effluents before and after chlorination were concentrated and purified using cation exchange and Chelex resins. After concentration and cleanup of the samples, the amino acids were derivatized by esterification of the acid functional groups and acylation of the amine groups. Identification and quantification of the amino acids and chlorination products was carried out by gas chromatography/mass spectrometry, using a digital computer data system. Analysis of the waste products revealed the presence of new carbon-chlorine bonded derivatives of the amino acid tyrosine when the effluents were treated with heavy doses of chlorine.

A series of oxovanadium(IV) complexes of Schiff bases derived from substituted salicylaldehyde and aminoalcohols has been prepared and characterized. The Schiff bases coordinate through 0, N, and 0 as tridentate bivalent ligands. The primary purpose of the investigation is to describe the structure and bonding in these complexes. The subnormal magnetic properties of the complexes provide much information about both the structure and the bonding in the complexes.

The research described herein is concerned with the synthesis of certain organic compounds which have the amino-oxy grouping and are related in structure to the naturally occurring amines, putrescine, spermidine and spermine.

In an effort to study the spectral, magnetic, and stereochemical properties of vanadyl complexes, both a new series of vanadyl complexes derived from type (VII) ligands with subnormal magnetic moment and from type (VIII) ligands with normal magnetic moment are synthesized and characterized.

The purpose of the investigation described herein was to investigate the degree of delocalization of the unpaired electron in ion radicals formed in the oxidation process of compounds with aromatic rings connected by means of various groups and atoms not entering the ring; then, to establish the relationship of coupling constants in radical cations with substituent σ values. The parent cation radical, in which the co-planar ion was derived from N,N-dimethylaniline, was selected in order to maximize the substituent effects on coupling constants and to obtain couplings at several positions (specifically, CH3, N, and ring protons).

This investigation involved the synthesis of 1-amino-2-hydroxycyclopentanecarboxylic acid, a potential structural analog of the natural amino acids, serine and threonine. The title compound also includes the structural features present in an established antitumor agent, cycloleucine.

Four isosteric series of plant growth-regulating compounds were prepared. Using an Avena sativa coleptile assay system, derivatives in series I and IV inhibited segment elongation to a greater degree than did comparable derivatives in series II and III.

The principle objective of this study is to conduct a definitive investigation into the cycloaddition of allenes and ketenes, with particular emphasis on halogenated ketenes.

The objective of this research problem was to synthesize aldohaloketenes and investigate the chemistry of this new class of ketenes.

The objectives of this investigation were: 1. To establish calorimetrically the transition temperature for the orthorhombic to cubic transition exhibited by PbF₂ and to determine the enthalpy of this transition. 2. To determine if the solid-solid phase transitions claimed in the literature for PbCl₂, PbF₂, PbBr₂, and PbI₂ were of thermodynamic importance, and if so, to determine the enthalpies of transition. 3. To determine if the discontinuous thermal expansions reported by Hsu for the lead halides were of thermodynamic importance. 4. To obtain reliable heat content data for the lead halides in both the solid and liquid states.

It was proposed to study the cycloaddition of ketenes and carbodiimides in some detail. The first objective was to investigate the general applicability of the reaction as a tool for the synthetic organic chemist in the preparation of a new class of substituted β-lactams; i.e., imino-β-lactams. It was proposed for this part of the research problem to look for the intermediate, either directly or indirectly, by trapping experiments. It was further proposed to study substituent effects in the ketene and carbodiimide and also Investigate the effect of solvent polarity on the reaction rate. From these data, it was hoped that the mechanism of the cycloaddition reaction could be elucidated.

With three different proposals for the bonding in metal carbonyls, it was decided to look into the situation more thoroughly in order to see what other evidence was available to support or refute any of these ideas. It became obvious that a definite contradiction existed between the kinetic evidence of various metal carbonyls, and the concept of MC bond strengths as predicted by Cotton's theory.

The majority of interest in organolithium and organoaluminum compounds has centered around their potency as polymerization catalysts.