The present.study was an investigation of the formation and kinetic stability of store complexes contain.ir)ing a chromium-carbon bond in an aqueous medium. An orange-brown pentaaquotrifluoromethylchromium(III) ion was obtained by the reduction of trifluororrethyl iodide with Cr(II) and is the most inert of any organochrotnium(III) complex known. The initial aquation rates of trifluoromethylchromium(III) ion were described by the differential rate law -dln [(H2O)5CrCF32+]/dt = ko + k1(H+) The products of the initial reaction were hexaaquochromium (III), carbon monoxide and HF. The values of ko and k1 at 45° were 5.21 x 10-1 and 9.38 x 10M-1sec-1 respectively. The activation parameters for the acid independent and acid dependent pathways were: ΔH+ = 19.7 kcal/more, ΔS+ = -27.4 cal-deg-1mole-1; and ΔHǂ1 = 23.4 kcal/mole and ΔSǂ1 = -12.7 cal-deg-1mole-1. The acceleration in the aquation with time was observed indicating autocatalysis by a product of the reaction. An intermediate, (Cr( OH2)4FCrCF31+ ), was separated from the aquation reaction solution; this same ion was also formed immediately when fluoride ion was added to the (H2)5CrCF32+ ion in 0.05M perchloric acid. The added fluoride ion also increased the rate of aquation. Rapid formation of (Cr(OH2)4FCrCF31+) ion was attributed to the strong stabilizing effect of the trifluoromethyl ligand on water molecules in the inner coordination sphere of chromium( III). A solvent-assisted mechanism for the aquation of pentaaquotrifluoromethyl-chromium(III) ion was proposed in which an activated complex was formed which dissociated in a concerted manner to give the products. Also, a reaction sequence was proposed for the complete aquation reaction which was consistent with the rate laws, the effect of added fluoride ion and the activation parameters. Pink organochromium(III) species of 2+ charge was isolated in the reduction of carbon tetrachloride and carbon tetrabromide with chromium( II). he pink species have ·chromium:carbon:halide ratios of 1:1:1 and their uv-visible spectra showed unusually high absorbance values in the 500 nm region. The pink organochromium(III) reacted very rapidly with oxygen. The products of dissociation were carbon monoxide, formic acid, formaldehyde, bexaaquochromium(III), chromium( II) halide ions. The kinetics of aquation were studied, and initial rate coefficients and activation parameters were obtained. The identity dt these organochromium(III) species was not established but most possible structures were proposed.

The decision to attempt the synthesis of furo [3, 2-b] furan was based on four considerations. Firstly, there are an abundance of synthetic and naturally occurring compounds, especially carbohydrate derivatives, containing this ring system in a partially or fully saturated state. Secondly, some of these compounds are physiologically active and others are important industrially. Thirdly, no compound, synthetic or naturally occuring, containing the fully unsaturated nucleus has been reported. Yet this molecule has an uninterrupted chain of six carbon atoms and may conceivably be formed from certain hexose derivatives. By analogy with compounds containing the saturated ring, furo[3,2-b] furan may be physiologically active. Lastly, there is only one synthetic 3-alkoxyfuran, 3·-methoxyfuran. Any intermediate successes toward the stated goal as well as achievement of the final objective will expand knowledge in the difficult area of 3-substituted furan synthesis especially in the presently unexamined area of 3-alkoxyfuran synthesis.

Ten N('8)-acetylspermidine analogues were synthesized. These compounds were used as active site directed agents to investigate the catalytic mechanism of N('8)-acetylspermidine deacetylase. This enzyme is present in the cytosolic fraction of rat liver homogenate. The Ki values for all the compounds were determined from Dixon plots. The results of this study show that these compounds act as competitive inhibitors of N('8)-acetylspermidine deacetylase. The Ki values of these compounds range from 29.2 to 0.00018 mM. The size of the active site was investigated by substitution of the acetyl group of N-acetyl-1,6-diaminohexane and N-acetyl-1,8-diaminooctane with larger groups. These modifications resulted in a decrease in the inhibitory activity. Compounds were made in which the length of the carbon chain between two terminal amino groups was varied. It was found that a six carbon separation is needed for optimal activity. Bioisosteric replacement of N('4) of N('8)-acetylspermidine with a -CH(,2)- group resulted in a decrease in the potency of the compound compared with N-acetyl-1,6-diaminohexane. On the other hand, bioisosteric replacement of the N('8) of N('8)-acetylspermidine with a -CH(,2)- group resulted in a large increase in the inhibitory activity. The Ki value for this compound (Ki = 0.00018 mM) is lower than the Km of the enzyme (Km = 0.01m mM). Results obtained from this project and other results obtained in our laboratory were used to draw a hypothetical model for the active site of N('8)-acetylspermidine deacetylase.

Cis and trans isomers of 3-(mono- or dialkylamino)-7-(methoxy or hydroxy)-1-phenyl-1,2,3,4-tetrahydronapthalenes were synthesized. Compounds HC- 11 (cis) and HT- 11 (trans) with 3- (dimethylamino) and 7-methoxy substituents and compounds HC- 13 and HT- 13 with 3- ((cyclopropylmethyl)methylamino) and 7-methoxy substituents were synthesized from their corresponding 3-(methylamino) and 7-methoxy derivatives (HC- 10 and HT- 10). HC- 10 and HT- 10 were previously prepared by reductive amination of the 3-tetralone and separated by fractional recrystallization. HC- 10 was obtained predominantly in a 9:1 ratio. Analysis of proton NMR spectral data supports the fact that both the phenyl group at C-1 and nitrogen substituents at C-3 of the tetralin ring are placed pseudoequatorially in the preferred conformation for the cis and trans isomers. Compounds HC- 10 - 12 and HT- 10 and 11 and also HC- and HT- 13 and 14 were tested for their opioid-related agonist and/or mixed agonist-antagonist properties in the guinea pig ileum (GPI) longitudinal muscle assay as described by Kosterlitz.$\sp{64}$ These tests show that compounds HC- 10 and HC- 11 have agonist activity approaching that for a full agonist but at a higher dose level (approximately $60 \times)$ that for Normorphine (NM). Compounds HC- 13 and HT- 10 were of intermediate potency ranging in activity from 1/300 to 1/700 the potency of NM. Their activities are classified as those of partial agonist. The 0-demethylated compounds HC- 12, HC- 14 and HT- 14 were weak in potencies as agonist. Compounds HT- 11 and HT- 13 were inactive. Agonist activity in these compounds resides predominantly in the cis isomers as revealed by the superior potencies of HC- 10, HC- 11, HC- 13 and HC- 14 over their trans counterparts. This observation is in agreement with those reported earlier$\sp{6}$ for the nonphenolic congeners 2C and 2T. Naloxone (Nx) only partially blocks the activity of these compounds, thus the activity seen on the GPI may not be totally opioid in nature. Antagonism of NM activity by HC- 14 and HT- 14, with pA$\sb 2$ values of 4.9 and 4.63 respectively, shows that these compounds possess little mu receptor antagonist activity. ftn$\sp{6,64}$Please see dissertation for references.

In this study, two, three, four, five, and six rare earths were separated by reversed-phase thin layer chromatography. Selected sample spots were removed from the plate and determined by emission spectroscopy. Di-(2-ethylhexyl)phosphoric acid was used as the stationary phase. This roganic substituted inorganic acid is retained on the adsorbent through hydrogen bonding and is essentially hydrophobic, so that the aqueous mobile phase can pass over it without serious interaction between the two acids.

A technique has been developed for determining the effect of very low energy electrons (3.0 to 8.0 eV) on molecules adsorbed on metal surfaces. The electron source is a thoria coated iridium filament operated at low filament current to minimize the thermal distribution of the energies of emitted electrons (0.0 to 0.4 eV). The system is kept at 10('-3) to 10('-4) torr by allowing the gas studied to pass through the reaction vessel while the system is being evacuated by Vac Ion pumps. Analysis is performed via computer controlled quadrupole mass spectrometry. Carbon monoxide gas has been studied on gold, nickel, palladium, molybdenum and tungsten surfaces produced by vacuum sublimation of the metals. Observations fit the following series of reactions: CO(ads) + e('-) (--->) CO('*)(ads) + e('-) CO('*)(ads) + CO(ads) (--->) C(,2)O(,2)(ads) C(,2)O(,2)(ads) (--->) CO(,2)(ads) + C(ads) C(ads) + CO(ads) (--->) C(,2)O(ads) C(,2)O(ads) + CO(ads) (--->) C(,3)O(,2)(ads) Since desorption occurs along with these reactions, the mass levels of 44 (CO(,2)), 56 (C(,2)O(,2)) and 68 (C(,3)O(,2)) were monitored as a function of electron energy. Threshold potentials (ie. the potential at which the mass spectrometer ion current begins to increase for a given mass level) were determined for the surfaces studied. Good agreement has been obtained for the threshold potentials (E(,th)) determined at the three mass levels for a given metal surface. Average values are: E(,th)(gold) = 6.0 eV; E(,th)(nickel) = 6.1 eV; E(,th)(palladium) = 4.8 eV; E(,th)(molybdenum) = 4.1 eV; E(,th)(tungsten) = 3.0 eV. A relationship between these threshold potentials and the heats of adsorption for CO adsorbed on the surfaces has been proposed. The heat of adsorption is believed to be primarily a function of d(pi)(--->)p(pi)* back bonding from the metal to the surface bound carbonyl. This stabilizes the (pi)* orbital relative to the gas phase and lowers the excitation energy of CO by the heat of adsorption.

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