It is one purpose of this dissertation to introduce a facile method for the preparation of β glycosides of D-glucose and D-allose. It is the second purpose of this dissertation to investigate the preparation of 2-oxazolidinones forming a bridge between C2 and C3 of allopyranose. This preparation, along with the facile preparation of β-benzyl glycosides of D-glucosamine and D-allosamine, should lead to compounds which, in a few steps, can conceivably be used for coupling at positions 1 and 4.

Three chapters of this dissertation, therefore,are devoted to describing the synthesis of 1,3,5,7-s-hydrinda-centetrone using the three starting materials, pyromellitic dianhydride by means of the four above described reactions. 1,3,5,7-s-Hydrindacentetrone, itself, and its properties are described in Chapter three when first prepared. An entire chapter is devoted to the preparation of the dinitroso and dinitro derivatives; both because of the complexity of their reactions and because of their relative importance. An additional chapter is devoted to other miscellaneous derivatives. Conclusions have been drawn as to the appropriateness of each method of synthesis and are presented at the end of their respective chapters. In addition, a summary of all results is presented at the end of this paper.

The present work consists of two parts. The first part contains the synthesis of 3,4,6-tri-o-benzoyl-D-glucopyranosido-[1,2:41,51]-21-oxazolidone (III) and the study of its chemistry in order to determine whether it could be used as a simultaneous protecting group for C1 and C2 in the preparation of new aminosugars. The second part covers the synthesis and de-o-benzoylation of β-D-glucosaminides. The products thus obtained can be used to prepare new disaccharides. In addition new aminosugar derivatives have been prepared.

This research is primarily interested in investigating the reactions of benzyl 2-amino-4,6-0-benzylidene-2- deoxy-D-glucopyranoside (I) with various esters. The advantage offered by this sugar is that an alcohol and an amine group are in close proximity, allowing studies of intermolecular vs. intramolecular reactions and observation on anchimeric assistance in intramolecular reactions.

This investigation was undertaken in an attempt to form strained cyclic allenes and to study their chemistry. The method chosen for the attempted formation of strained cyclic allenes was the determination of the corresponding 2,3-dibromocycloalkene. 2,3-Dibromocyclononene was synthesized during the course of this investigation so that its debromination to the 1,2-cyclononadiene, which is the smallest stable, 1,2-cycloalkadiene, could be studies as model for the debromination of smaller 2,3-dibromocycloalkenes was initiated. The formation of 1,2-cyclohexadiene was attempted by the debromination of the 2,3-dibromocyclohexene. Evidence for the presence of this unstable intermediate was sought via the use of trapping agents.

A great variety of amino sugars has been found in antibiotics among these D-gulosamine in the striptomyces group. In the same group, .an N-methylated amino-sugar, N-methyl-L~ glucosamine has been isolated. Although N-methyl-0-gulosamine .has not been found in nature until now, its ultimate discovery would not be surprising in this context. In the present work this amino-sugar and some important derivatives are prepared for the first time, starting from D-glucosamine, a pure benzyl· 3-0-acetyl-2-benzyloxycarbonylamido-2-deoxy-~-D-glucopyranoside (X) was obtained by a series of kno~n processes. Benzyl 3-0-acetyl~-methylsulfonyl-2-deoxy-~-D-glucopyranoside (XIII) and some of its derivatives were obtaine.d from (X). An attempt was made to obtain benzyl-~-D~gulopyranoside (2'3':4,5)oxazolidone- 2 (XVII), by a route different from that of Gross et al. Since the yield of the starting material (XIII) to be use~for the preparation of the oxazolidone (XVII) was not high enough, the oxazolidone (XVII), which was the starting material for this investigation, was synthesized in the original manner. When positions 4 and 6 of the oxazolidone (XVII) were blocked by the benzylidene group, methylation occurred only at the nitrogen. Mono-N-methyl-gulosamine (XXV) and some of its derivatives were synthesized in this way. when only the 6-posi tion of the oxazolidone (XVII) was blocked, the hydroxyl group in the 4-position was also methylated. In this way, the 4-0-methyl ether of N-methyl-0-gulosamine (XXXI) could be synthesized. The 4,6-0-methyl ether of N-methyl-D-gulosamine (XXXVI) was synthesized by direct methylation of the oxazolidone (XVII) and subsequent cleavage of the blocking groups.

Much information has been obtained on the orientation of unsymmetrical reagents about substituted allenes. Although hydrogen halide addition to 1,2-propadiene yields 2-halopropenes,20,31 it has been ample demonstrated, at least in the case of halogenation and oxymercuration of the 1,2-alkyl substituted allenes, that the attacking electrophile ends up in the product attached to the central carbon of the original allenic system. 20,22,31,34,38,39,40 Using optically active 1,3-dimethylallene(15) it has been shown that the bromination and oxymercuration of 15 is stereospecific. 22,39Knowledge of the absolute configurations of the optically active addition products have made it possible to propose a plausible mechanism for the reactions (eq 1). 1,2-cyclononadiene(1) was brominated in methanol and a 40:60 mixture of two products corresponding to isomeric bromomrthoxycyclonenes was obtained. Preliminary, chemical, and spectral evidence indicated that the isomeric mixture definitely did not consist of cis-trans geometric isomers. The primary objective of the research then became the identification of the isomeric bromination products of 1,2-cyclononadiene(1) in various reactive solvents. The results are discussed with reference to the intermediates that may be involved in these reactions.

Itaconic acid (IA) has many versatile applications in science and medicine. Engineering Escherichia coli can provide a reliable route for IA production, where cis -aconitate decarboxylase (CAD) is one essential enzyme in the process. The synthetic cad gene has been cloned into various vectors to improve the expression rate and folding activities. The strain bearing plasmid pTrc99a- cad displays a significant amount of IA production, while the CAD protein expressed from the same plasmid displays the highest enzymatic activity in vitro. To improve the reliability of forming the cis -aconitate intermediate, the aconitase genes from Aspergillus terreus have been cloned into the pTrc99a vector. The expression of aconitate hydratase leads to a peak at 10.3 min in the HPLC spectra after 4 hours incubation. The peak will be analyzed to determine whether it is cis -aconitate. The obtained data will provide data on possible metabolic pathways of IA production in Aspergillus terreus.

Herbig-Haro objects are the nebulous emission regions arising from shocks associated with the bipolar outflows of young stellar objects. Observations of the emission lines of HH objects can reveal properties of these stellar jets, which are associated with star formation, and one tool to study stellar jets and HH objects is computer modeling. AstroBEAR is a 3D magnetohydrodynamic code with adaptive mesh refinement and parallelization capabilities. The goals of this research were (1) to improve the cooling in AstroBEAR and add the ability to create valid emission-line maps for HH objects, and (2) to model a jet overrunning and shocking clumps, and to explore a parameter space that may lead to morphologies like those of HH 29. The results generate emission-line maps with the correct spatial morphology in Hα and [SII], and begin to map out the regimes (shock velocities, resolution, physical scales) in which the code remains valid.

One proven solution for improving the reliability of a wireless channel is to use relays. We analyze the three-node relay network, focusing on the estimate-and-forward (EF) relay protocol, where the relay node estimates the source symbol and then forwards it to the destination. For an uncoded system in a path-loss model for the cooperative three-node wireless network, we show that EF with minimum mean square error (MMSE) estimate outperforms other common relay protocols such as amplify-and-forward (AF) and detect-and-forward (DF). Since the probability density function required by the optimal maximum a posteriori (MAP) detector at the destination does not have an analytical form, we provide a solution to bypass its numerical approximation. We show that EF with a piecewise linear approximation of the MMSE estimate provides an analytical form of the detector at the destination and its performance is similar to the case when a MMSE estimate is used.