Novel1, 3-Dipolar Cycloaddition Reactions of Acyclic Carbonyl Ylides and Related Chemistry

The thesis entitled novel 1,3-dipolar cycloaddition reactions of acyclic carbonyl ylides and related chemistry embodies the results of the investigations carried out to explore the reactivity of acyclic carbonyl ylides,generated by the reaction of dicarbomethoxy carbine and aldehydes towards dipolarophiles such as activated styrenes,1,2-and 1,4-quinones. In conclusion ,we have explored the reactivity pattern of acyclic carbonyl ylides derived from dicarbomethoxycarbene and aldehyde towards activated styrenes with a view to develop a stereoselective synthesis of highly substituted tetrahydrofuran derivatives. It was also found that the ylide could be trapped by various 1,2-and 1,4-diones to form dioxolane derivatives. It is noteworthy that the cycloaddition is highly region- and stereoselective. With isatins the ylide preferentially adds to the more electrone deficient carbonyl group making it regiospecific. Hetrocyclic compounds are of pivotal importance in organic chemistry, and enormous efforts have been devoted to develop new methodologies for their synthesis. It is noteworthy in this context that, 1,3-dipolar cycloaddition reaction,otherwise called Huisgen reaction, constitutes one of the most efficient methods for the synthesis of five membered heterocycles. Among the various dipoles, carbonyl ylides have received substiancial attention in recent years largely due to their utility in the synthesis of a wide range of oxygen hetrocycles, which are often found as structural subunits of many bioactive natural products.

Studies on the histological and biochemical changes during spermatogenesis in MUGIL CEPHALUS linnaeus and related species

Several studies on the biology and fisheries of mullets, particularly of M cephalus are now available. Different aspects of breeding, larval rearing, seed production, field culture and ecophysiology have also been investigated. However, information on the spermatogenesis in M cephalus as well as L parsia is scanty. Since an understanding of the reproductive strategies is an essential pre-requisite for evolving successful breeding programmes through artificial fertilization and gametic preservation, investigations on spermatogenesis in these species were taken up and the results are presented in this thesis. The thesis is presented in 9 chapters

Nucleophilic addition of Nitrones to Electron deficient acetylenes and related studies

Nitrones or azomethine-N-oxides are important precursors for the synthesis of several heterocyclic systems. They belong to the allyl anion type 1,3-dipoles and possess unique structural features which make them extraordinarily useful synthons. They behave as 1,3-dipoles in 1,3-dipolar cycloaddition reactions and as electrophiles in reactions with organometallic reagents. These are the two basic reactions given by nitrones. Nitrones also act as ‘spin traps’ in which they react with short-lived radicals to furnish stable nitroxide radicals which can be detected and identified by electron paramagnetic resonance (EPR) spectroscopy. Recently SmI2 catalysed reductive cross-coupling reactions of nitrones have gained significant interest in which the reactions are initiated by single electron transfer (SET) to nitrones. Apart from these reactions, nitrones are also known to participate in reactions which are initiated by the nucleophilic attack of nitrone-oxygen. In our group, we have also explored the nucleophilic character of nitrones through various reactions. The results obtained enabled us to develop a novel two-step one-pot strategy for quinolines and indoles - the heterocycles renowned for their pharmacological applications, from nitrones and electron deficient acetylenes. Using dibenzoylacetylene and phenylbenzoylacetylene as dipolarophiles, we could introduce a desired functional group at a predetermined position of the quinolines or indoles to be synthesised. In this context, the thesis entitled “NUCLEOPHILIC ADDITION OF NITRONES TO ELECTRON DEFICIENT ACETYLENES AND RELATED STUDIES” portrays our attempt to expand the scope of our x novel synthetic protocol using ester functionalised acetylenes: dimethyl acetylenedicarboxylate (DMAD) and methyl propiolate. The thesis is organised in to five chapters. The first chapter briefly describes the different classes of reactions that nitrone functionality can tolerate. The research problem is defined at the end of this chapter. The second chapter describes the synthesis of different nitrones used for the present study. The optimisation and expansion of scope of the novel strategy towards quinoline synthesis is discussed in the third chapter. The fourth chapter portrays the synthesis of indole-3-carboxylates using the novel strategy. In the fifth chapter, the reaction of N-(2,6-dimethylphenyl) and N-(2,4,6-trimethylphenyl)nitrones are discussed. Here we also discuss the mechanistic reinvestigation of Baldwin’s proposal in the isoxazoline-oxazoline rearrangement. The major outcome of the work is given at the end of the thesis. The structural formulae, schemes, tables and figures are numbered chapter-wise since each chapter of the thesis is organized as an independent unit. All new compounds (except two compounds reported in fourth chapter) are fully characterised on the basis of spectral and analytical data and single crystal X-ray analysis on representative examples. Relevant references are included at the end of individual chapters.

Novel Hetrocyclic Constructions Mediated by Nucleophilic Carbenes and Related Chemistry

The thesis entitled novel heterocyclic constructions mediated by nucleophilic carbenes and related chemistry, embodies the results of the investigations carried out to explore the reactivity patterns of the 1:1 zwitterions, generated in situ from various nucleophilic carbenes and DiMethyl AcetyleneDicarboxylate(DMAD) towards aldehydes and ketones. The traditional synthesis of complex organic molecules employs stepwise formation of bonds and involves multiple steps. Besides the sequential synthesis, in several instances, the desired product can also be obtained in one pot reactions of three or more starting compounds. Such reactions in which more than two starting materials react to form a product in such a way that the majority of the atoms of the starting materials can be found in the products are called multicomponent reactions(MCRs). The results of our investigations on the application of N-heterocyclic carbenes in multicomponent reaction with DMAD and aromatic aldehydes leading to the one pot synthesis of 2-oxy-maleate and furanone derivatives. It is interesting to note that dihydrofuran and lactone motifs are present in a number of biologically active natural products and other heterocyclic compounds. It is conceivable that the novel multicomponent reactions described herein will find application in the synthesis of a variety of heterocyclic compounds, and in natural product synthesis.

Fuzzy Absolutes and Related Topics

The study on the fuzzy absolutes and related topics. The different kinds of extensions especially compactification formed a major area of study in topology. Perfect continuous mappings always preserve certain topological properties. The concept of Fuzzy sets introduced by the American Cyberneticist L. A Zadeh started a revolution in every branch of knowledge and in particular in every branch of mathematics. Fuzziness is a kind of uncertainty and uncertainty of a symbol lies in the lack of well-defined boundaries of the set of objects to which this symbol belongs. Introduce an s-continuous mapping from a topological space to a fuzzy topological space and prove that the image of an H-closed space under an s-continuous mapping is f-H closed. Here also proved that the arbitrary product fi and sum of  fi of the s-continuous maps fi are also s-continuous. The original motivation behind the study of absolutes was the problem of characterizing the projective objects in the category of compact spaces and continuous functions.

Fuzzy Topological Games and Related Topics

The main purpose of study is to extend the concept of the topological game G(K, X) and some other kinds of games into fuzzy topological games and to obtain some results regarding them. Owing to the fact that topological games have plenty of applications in covering properties, it made an attempt to explore some inter relations of games and covering properties in fuzzy topological spaces. Even though the main focus is on fuzzy para-meta compact spaces and closure preserving shading families, some brief sketches regarding fuzzy P-spaces and Shading Dimension is also provided. In a topological game players choose some objects related to the topological structure of a space such as points, closed subsets, open covers etc. More over the condition on a play to be winning for a player may also include topological notions such as closure, convergence, etc. It turns out that topological games are related to the Baire property, Baire spaces, Completeness properties, Convergence properties, Separation properties, Covering and Base properties, Continuous images, Suslin sets, Singular spaces etc.

Box Products in Fuzzy Topological Spaces and Related Topics

The topology as the product set with a base chosen as all products of open sets in the individual spaces. This topology is known as box topology. The main objective of this study is to extend the concept of box products to fuzzy box products and to obtain some results regarding them. Owing to the fact that box products have plenty of applications in uniform and covering properties, here made an attempt to explore some inter relations of fuzzy uniform properties and fuzzy covering properties in fuzzy box products. Even though the main focus is on fuzzy box products, some brief sketches regarding hereditarily fuzzy normal spaces and fuzzy nabla product is also provided. The main results obtained include characterization of fuzzy Hausdroffness and fuzzy regularity of box products of fuzzy topological spaces. The investigation of the completeness of fuzzy uniformities in fuzzy box products proved that a fuzzy box product of spaces is fuzzy topologically complete if each co-ordinate space is fuzzy topologically complete. The thesis also prove that the fuzzy box product of a family of fuzzy α-paracompact spaces is fuzzy topologically complete. In Fuzzy box product of hereditarily fuzzy normal spaces, the main result obtained is that if a fuzzy box product of spaces is hereditarily fuzzy normal ,then every countable subset of it is fuzzy closed. It also deals with the notion of fuzzy nabla product of spaces which is a quotient of fuzzy box product. Here the study deals the relation connecting fuzzy box product and fuzzy nabla product