From O-glucuronyl trichloroacetimidate (4) and ${\Delta}^6$-tetrahydrocannabinol (5), the C-glucuronide of ${\Delta}^6-tetrahydrocannabinol({\Delta}^6-THC)$ (7) was obtained using mild Lewis acid catalysis. The known method for the synthesis of C-glucuronide from 1-O-unprotected glucuronide provided low chemical yields. The C-glucuronide of ${\Delta}^6-THC$ was obtained through inversion of configuration at the anomeric center in O-glucuronyl trichloroacetimidate (4).

We have carried out an extended Huckel calculation to rationalize the role of $CuO_3$ chains and the size effect of the charged model clusters for the following charged model culsters : ${{Cu_6}{O_{21}}^{28-},\;{{Cu_6}{O_{22}}^{30-}\;,{{Cu_9}{O_{30}}^{39-}\;,{{Cu_9}{O_{32}}^{43-}\;,{{Cu_{12}{O_{38}}^{48-}\;,{{Cu_{15}{O_{50}}^{65-}\;,{{Cu_{18}{O_{54}}^{66-}\;,{{Cu_{18}{O_{55}}^{68-}\;,{{Cu_{24}{O_{70}}^{84-}\;and\;{{Cu_{27}{O_{78}}^{93-}$ for high-$T_c$ superconductor $YBa_2Cu_3O_7$: ${{Cu_6}{O_{18}}^{22-}\;,{{Cu_9}{O_{26}}^{31-}}\;,{{Cu_{12}{O_{32}}^{36-}\;,{{Cu_{15}{O_{42}}^{49-}\;,{{Cu_{18}{O_{46}}^{50-}\;,{{Cu_{24}{O_{60}}^{64-}\;and\;{{Cu_{27}{O_{66}}^{69-}$ for insulator $YBa_2Cu_3O_6$. The results show that the electronic structures and properties of the charged model clusters relating to high-$T_c$ superconductor are very sensitive to the size change of the clusters with various environmental effects, wherease those of the charged model clusters for insulator $YBa_2Cu_3O_6$ are monotonous to the size change. The $CuO_3$ chains along the b-direction may yield cooperative electronic coupling with the $CuO_2$ layers in determining both conducting and superconducting properties of $YBa_2Cu_3O_{7-x}$ system.

The approximate rates and stoichiometry of the reaction of excess 1,3,2-biphenyldioxaborepin [2,2'-biphenoxyborane (BPB)] with selected organic compounds containing representative functional groups under the standardized conditions (tetrahydrofuran, hydride to compound being 4 : 1, room temperature) was examined in order to define the characteristics of the reagent for selective reductions and compare its reducing power with those of other substituted boranes. The results indicate that BPB is unique and the reducing power is much stronger than that of other dialkoxyboranes, such as catecholborane and di-s-butoxyborane. BPB reduces aldehydes, ketones, quinones, lactones, tertiary amides, and sulfoxides readily. Carboxylic acids, anhydrides, esters, and nitriles are also reduced slowly. However, the reactions of acid chlorides, epoxides, primary amides, nitro compounds, and disulfides with this reagent proceed only sluggishly.

A general expression adopting a nonmultipole expansion method is derived for pseudocontact contribution to the NMR chemical shift arising from the electron orbital angular momentum and electron spin dipolar-nuclear spin angular momentum interaction of $3d^9$ system in a strong crystal field of tetragonally distorted tetrahedral symmetry. From this expression all the multipolar term are determined and the exact solution of ${\Delta}$B/B(ppm) is compared with the multipolar term. The $1/R^5$ term in the multipolar terms contributes dominantly to the NMR chemical shift but the other terms are certainly significant except that of the <111> axis. In addition, an analysis of the temperature dependence of the NMR chemical shift further illustrates that considerable care must be taken in interpeting NMR results in paramagnetic system.

Using uniform flat plate-like samples of ZSM-5 zeolites, diffusion coefficients were measured volumetrically for the diffusion of xylene, ethyltoluene and diethylbenzene by direct measurement of sorption rate. Toluene disproportionation over H(100)-, K(72)-and Cs(82)-ZSM-5 at 773 K and toluene methylation, toluene ethylation and ethylbenzene ethylation over Cs(75)-ZSM-5 at 623 K were carried out. The selective formation of para xylene during the toluene disproportionation, presumably due to the increased tortuosity over Cs-ZSM-5, could be explained by smaller diffusion coefficient in Cs-ZSM-5 than in K-and H-ZSM-5. The para selectivity increased in the order; toluene methylation < toluene ethylation < ethylbenzene ethylation. As the chain length of the alkyl substituent in dialkylbenzenes is increased, the para selectivity of the products was improved. It may be attributed to the differences in the ratios of diffusion coefficient of para products to that of ortho ones. Diffusion coefficient of m-xylene was about 1 order of magnitude smaller than that of o-xylene.

The rate constants for the formation and dissociation of nickel(II) and cobalt(II) complexes with mandelate have been determined by the pressure-jump relaxation study. The forward and reverse rate constants for the mandelate complex formation reactions were obtained to be $k_f=3.60{\times}10^4\;M^{-1}s^{-1}$ and $k_r=1.73{\times}10^2\;s^{-1}$ for the nickel(II), and $k_f=1.75{\times}10^5\;M^{-1}s{-1}$ and $2.33{\times}10^3\;s^{-1}$ for the cobalt(II) in aqueous solution of zero ionic strength ($(\mu{\to}0)\;at\;25^{\circ}C$. The results were interpreted by the use of the multistep complex formation mechanism. The rate constants evaluated for each individual steps in the multistep mechanism draw a conclusion that the rate of the reaction would be controlled by the chelate ring closure step in concert with the solvent exchange step in the nickel(II) complexation, while solely by the chelate ring closure step for the cobalt(II) complex.

3,4,5,6-Tetrahydro-7-hydroxy-2-(1,3-dithian-2-yl)- 9-alkyl-2,6-methano-2H-1-benzoxocin derivatives are readily prepared by boron trifluoride etherate-catalyzed formation of 5-alkylresorcinols with 1-thioxolanyl-2-cyclohexenol. The yieldis the highest with 5-(1,1-dimethylheptyl)resorcinol. The one with 5-pentylresorcinol is higher than with 5-methylresordnol and resorcinol apparently because of steric effects. The yields of the product increase; 3a(7%), 3b(22%), 3c(38%) and 3d(50%).

The adsorption of methanethiol on a Ag(100) surface has been studied with Extended Huckel calculation in the cluster approximation of the substrate. Since it has been known that methanethiol is chemisorbed dissociatively on silver surface by rupture of S-H bond, the methanethiolate radical is taken as adsorbate. Of the various adsorption sites, the 4-fold hollow site is preferred. The methanethiolate radical is mainly adsorbed via its 2e orbital. The charge transfer from metal to this level leads to the C-S bond weakening, which is consistent with the red shift of C-S stretching mode in surface enhanced Raman (SER) spectrum.

The approximate rates and stoichiometry of the reaction of excess lithium tris(dibutylamino)aluminum hydride (LT-DBA) with selected organic compounds containing representative functional groups under standardized conditions (tetrahydrofuran, $0^{\circ}C$) were studied in order to characterize the reducing characteristics of the reagent for selective reductions. The reducing ability of LTDBA was also compared with those of the parent lithium aluminum hydride and the alkoxy derivatives. The reagent appears to be much milder than the parent reagent, but stronger than lithium tri-t-butoxyaluminohydride in reducing strength. LTDBA shows a unique reducing characteristics. Thus, the reagent reduces aldehydes, ketones, esters, acid chlorides, epoxides, and amides readily. In addition to that, ${\alpha},{\beta}$-unsaturated aldehyde is reduced to ${\alpha},{\beta}$-unsaturated alcohol. Quinones are reduced to the corresponding diols without evolution of hydrogen. Tertiary amides and aromatic nitriles are converted to aldehydes with a limiting amount of LTDBA. Finally, disulfides and sulfoxides are readily reduced to thiols and sulfides, respectively, without hydrogen evolution.

The reaction of primary aromatic amines with 1,7-heptanediol in the presence of a catalytic amount of ruthenium complex in dioxane at $180^{\circ}C$ for 24 hours gave the corresponding 1-substituted perhydroazocines in moderate yield.

The effect of intermolecular collisions in the infrared multiphoton dissociation (IRMPD) of difluorochloromethane was investigated using He, Ar, and $N_2$ as buffer gases. The reaction probability for IRMPD of difluorochloromethane was measured as a function of laser fluence and the buffer gas pressure under unfocused beam geometry. It was observed that the reaction probability was initially enhanced with the increase of buffer gas pressure up to about 20 torr, but showed a decline at higher pressures. The reaction probability increases monotonically with the laser fluence, but the rate of increase diminishes at higher fluences. An attempt was made to simulate the experimental results by the method of energy grained master equation (EGME). From the parameters that fit the experimental data, the average energy loss per collision, $<{\Delta}E>_d$, was estimated for the He, Ar, and $N_2$ buffer gases.

The gas-phase nucleophilic substitution reaction of pentafluoroanisole with $OH^-$ and ${NH_2}^-$ nucleophiles have been studied theoretically using the AM1 method. Three reaction channels, $S_N2$, IPSO and $S_NAr$ (scheme 1), are all very exothermic so that all are accessible despite the varying central energy barriers which are much lower than the reactants level. In the IPSO and $S_NAr$ channels, the reactants form directly a stable ,${\sigma}$-anion complex which proceeds to form a proton transfer complex via a transition barrier corresponding to a loose ${\pi}$-type complex with the F-(or ${OCH_3}^-$) leaving group. Due to a greater number of probable reaction sites available for $S_NAr$ compared to the other two processes, the $S_NAr$ channel is favored as experimentally observed.

In order to prepare new chiral borohydrides (4) possessing chirality on dialkyl moieties, a series of B-alkoxydiisopinocampheylborinates (3) were synthesized by treatment of diisopinocampheylborane ($Ipc_2BH$) with alcohols (R in ROH: Me, Et, i-Pr, t-Bu) and reacted with excess of potassium hydride. Of these chiral borinic esters, only B-methoxydiisopinocampheyl borinate (3a) was converted into the corresponding dialkylmonoalkoxyborohydride (4a). For the other borinic esters, hydride uptake reactions were very slow at room temperature, accompanying disproportionation products at $65^{\circ}C$. The hydride (4a) formed is stable at $0^{\circ}C$ and can be stored over potassium hydride for few months. In the asymmetric reduction of the selected ketones, 4a provided the corresponding alcohols, such as 21% ee for 3-methyl-2-butanone, 11% ee for 2,2-dimethylcyclopentanone, 24% ee for acetophenone, 32% ee for 3-acetylpyridine, 30% for methyl benzoylformate, 31% ee for 4-phenyl-3-butyn-2-one, 39% ee for 3-butyn-2-one, and 34% ee for 3-hexyn-2-one.

The elongation of the chain length at 2'position of aminothiazolylacetamido group of cephalosporin antibiotics was achieved. The derivatives with elongated side chain at 2'position were successfully synthesis and their in vitro activities were evaluated. It is indicated that there is an optimum range of the chain length in order to exhibit higher biological activities. This result could open a possibility for the development of the cephalosporin antibiotics with higher activities by further variation of the substituents at other positions. The cephalosporin derivatives with a simple (relatively non-functionalized) side chain as well as with a linear extended side chain were also prepared. Low activities of these derivatives led to a conclusion that either simple (non-functionalized) change or linear elongation of the side chain does not enhance the antibacterial activities.

Methanolysis of a ${\beta}$-lactam ring of a cephalosporin was simulated with AM1 semiempirical quantum mechanical calculation. The tetrahedral intermediate TD1 from an O-protonated cephalosporin and a methanol transfers the proton intramolecularly to the C-4 carboxylate to generate an oxyanion, i.e., second tetrahedral intermediate TD2, which undergoes the amide bond cleavage without further protonation on the N-5. For this cleavage a low-energy barrier TS2 was located. According to the energy diagram, tetrahedral intermediates easily undergo ring cleavage even without the protonation on the amide nitrogen.

The Wittig-oxy-Cope rearrangements of deprotonated diallyl ether, I, $CH_2={\bar{C}}H-CH-O-CH_2-CH=CH_2$, have been investigated theoretically by the AM1 method. A two step mechanism forming a Wittig product ion, II, $(CH_2=CH)$ $(CH_2=CH-CH_2)$ $CHO^-$, through a radical-pair intermediate was found to provide the most favored reaction pathway in the Wittig rearrangement. The subsequent oxy-Cope rearrangement from species II also involves a two step mechanism through a biradicaloid intermediate. The intramolecular proton transfer in I (to form $CH_2=CH-CH_2-O-{\bar{C}}H-CH=CH_2$) is a higher activation energy barrier process compared to the Wittig and oxy-Cope rearrangements and is considered to be insignificant. These results are in good agreement with the condensed-phase as well as gas-phase experimental results.

Solvent dependence of the static solution properties of a polymer chain was studied by static light scattering technique for polystyrene in three good solvents, toluene, tetrahydrofuran and $CCl_4$. The molecular parameters such as radius of gyration and second virial coefficients of polystyrene are found to be clearly larger in THF than the other two solvents and they are in the order of tetrahydrofuran > toluene > $CCl_4$. The radius of gyration shows the same order while the difference is smaller. Nontheless, the penetration functions are found to have a comparable value about 0.2, which confirms the universality of the penetration function in high expansion regime over different nature of solvents.

Emission quenching of photoexcited tris(${\alpha},{\alpha} '$-diimine)-ruthenium(II) complex cations, $RuL_3^{2+}$ (L: 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine; 4,4'-diphenyl-2,2'-bipyridine; 1,10-phenanthroline; 5-methyl-1,10-phenanthroline; 5,6-dimethyl-1,10-phenanthroline or 4,7-diphenyl-1,10-phenanthroline) by $Cu^{2+}$, dimethylviologen $(MV^{2+})$, nitrobenzene (NB), and oxygen was studied in aqueous homogeneous and sodium dodecyl sulfate (SDS) micellar solutions. The apparent bimolecular quenching rate constants $k_q$ were determined from the quenching data and life-times of $^{\ast}RuL_3^{2+}$. In homogeneous media, the quenching rate was considerably slower than that for the diffusion-controlled reaction. The decreasing order of quenching activity of quenchers was $NB>O_2>MV^{2+}>Cu^{2+}$. The rate with $Cu^{2+}$ was faster as the reducing power of $^{\ast}RuL_3^{2+}$ is greater. On the other hand, the rates with NB and $O_2$ were faster as the ligand is more hydrophobic. This was attributed to the stabilization of encounter pair by van der Waals force. The presence of SDS enhanced the rate of quenching reactions with $Cu^{2+}$ and $MV^{2+}$, whereas it attenuated the quenching activity of NB and $O_2$ toward $RuL_3^{2+}$. The binding affinity of quenchers to SDS micelle and binding sites of the quenchers and $RuL_3^{2+}$ in micelle appear to be important factors controlling the micellar effect on the quenching reactions.

The reaction path Smoluchowski equation approach developed in a recent work to calculate the rate constant for a diffusive multidimensional barrier crossing process is extended to incorporate the configuration-dependent diffusion matrix. The resulting formalism is then applied to the investigation of stilbene photoisomerization dynamics. Adapting a model two-dimensional potential and a model diffusion matrix proposed by Agmon and Kosloff [J. Phys. Chem.,91 (1987) 1988], we derive an eigenvalue equlation for the relaxation rate constant of the stilbene photoisomerization. This eigenvalue equation is solved numerically by using the finite element method. The advantages and limitations of the present method are discussed.

Procedures to perform reliable relativistic self-consistent-field (RSCF) calculations are described. Using light atoms and molecules, it is demonstrated that the present method always yields correct nonrelativistic limit by employing a sufficiently large value for the speed of light in RSCF calculations. Many problems associated with analytic expansions of the Dirac equations can be computationally avoided by kinetically balancing the basis sets for large and small component spinors. Results of RSCF calculations for Ne, Kr, $H_2$, and LiH indicate very small relativistic effects for these systems as expected. Trends found is these molecules, however, may be useful in understanding relativistic effects for molecules with similar valence electronic structures and heavier atoms.

Novel polysilamethylenosilanes (PSMS) were prepared by Wurtz type co-condensation of various mixtures of 2,4,4,6-tetrachloro-2,6-dimethyl-2,4,6-trisilahept ane (TSH) and dimethyldichlorosilane (D). When TSH was incorporated more than 25 mole%, PSMS polymers were soluble in common organic solvents probably due to the polycarbosilane linkage brought from TSH. The molecular weights of the polymer were measured by gel permeation chromatography and showed higher molecular weight with high TSH content. The thermal gravimetric residues increased as TSH contents increased. These properties suggested that PSMS polymers could be useful as ceramic precursors for silicon carbide.