Novel Strategies for Heterocyclic Constructions via 1, 4-Dipolar Intermediates

In the thesis entitled " Novel Strategies for Heterocyclic Constructions via 1 ,4-Dipolar Intermediates"Synthesis of a complex organic molecules essentially involves the formation of carbon-carbon and carbon-heteroatom bonds. Various synthetic methods are available for these processes involving ionic, pericyclic and radical reactions. Among the pericyclic reactions, dipolar cycloaddition reactions, introduced by Huisgen, have emerged as a very powerful tool for heterocyclic construction. Heterocyclic compounds remain an important class of organic molecules due to their natural abundance and remarkable biological activity, thus constituting an intergral part of pharmaceutical industry. In this respect, developing newer synthetic methodology for heterocyclic construction has been an area of immense interest. In recent years, 1,3-dipolar cycloaddition reactions proved to be efficient routes to a wide variety of five membered heterocycles, as attested by their application in the total synthesis of various complex organic molecules. However, the potential application of similar 1,4- dipolar cycloaddition reactions for the construction of six memebered heterocycles remained underexploited. In this context, a systematic investigation of the reactivity of 1,4-dipoles generated from nitrogen heterocycles (pyridine and its analogues) and dimethyl acetylenedicarboxy!ate (DMAD) towards various dipolarophiles has been carried out and the results are embodied.

Strategies for Inverse Profiling of Two Dimensional Dielectric Scatterers Using Electromagnetic Illumination

Electromagnetic tomography has been applied to problems in nondestructive evolution, ground-penetrating radar, synthetic aperture radar, target identification, electrical well logging, medical imaging etc. The problem of electromagnetic tomography involves the estimation of cross sectional distribution dielectric permittivity, conductivity etc based on measurement of the scattered fields. The inverse scattering problem of electromagnetic imaging is highly non linear and ill posed, and is liable to get trapped in local minima. The iterative solution techniques employed for computing the inverse scattering problem of electromagnetic imaging are highly computation intensive. Thus the solution to electromagnetic imaging problem is beset with convergence and computational issues. The attempt of this thesis is to develop methods suitable for improving the convergence and reduce the total computations for tomographic imaging of two dimensional dielectric cylinders illuminated by TM polarized waves, where the scattering problem is defmed using scalar equations. A multi resolution frequency hopping approach was proposed as opposed to the conventional frequency hopping approach employed to image large inhomogeneous scatterers. The strategy was tested on both synthetic and experimental data and gave results that were better localized and also accelerated the iterative procedure employed for the imaging. A Degree of Symmetry formulation was introduced to locate the scatterer in the investigation domain when the scatterer cross section was circular. The investigation domain could thus be reduced which reduced the degrees of freedom of the inverse scattering process. Thus the entire measured scattered data was available for the optimization of fewer numbers of pixels. This resulted in better and more robust reconstructions of the scatterer cross sectional profile. The Degree of Symmetry formulation could also be applied to the practical problem of limited angle tomography, as in the case of a buried pipeline, where the ill posedness is much larger. The formulation was also tested using experimental data generated from an experimental setup that was designed. The experimental results confirmed the practical applicability of the formulation.

2(3H)-Furanones and related substrates: Synthetic strategies and selectivity profile in their reactivity

The synthesis and reactions of simple derivatives of 2(3H)- and 3(2H)furanones have attracted considerable attention in recent years, primarily in connection with development of routes to antitumor agents that contain this ring as central structural unit. They also serve as useful synthetic building blocks for lactones and furans and are the precursors of a wide variety of biologically important heterocyclic systems. Although a number of syntheses of furanones were known they were in many cases limited to specific substitution pattems. The development of altemative strategies for the preparation of these heterocycles is therefore of considerable importance or continues to be a challenge.We propose to develop new and general approaches to the synthesis of furanone ring systems from simple and readily available starting materials since we were interested in examining their rich photochemistry. The photochemical reactivity of Beta,gama-unsaturated lactams and lactones is a subject of current interest. Some of the prominent photoreaction pathways of unsaturated lactones include decarbonylation, solvent addition to double bonds, decarboxylation, migration of aryl substituents and dimerisation. lt was reported earlier that the critical requirement for clean photochemical cleavage of the acyl-oxygen bond is the presence ofa double bond adjacent to the ether oxygen and 2(3H)-furanones possessing this structural requirement undergo facile decarbonylation. But related phenanthrofuranones are isolated as photostable end products upon irradiation. Hence we propose to synthesis a few phenanthro-2(3H)-furanones to study the effect of a radical stabilising group at 3-position of furanone ring on photolysis. To explore the tripletmediated transformations of 2(3H)-furanones in polar and nonpolar solvents a few 3,3-bis(4-chlorophenyl)-5-aryl-3H-furan-2-ones and 3,3-di(p-tolyl)-5-aryl- 3H-furan-2-ones were synthesised from the corresponding dibenzoylstyrene precursors by neat thermolysis. Our aim was to study the nature of intermediates involved in these transformations.We also explored the possibility of developing a new and general approach to the synthesis of 3(2H)-furanones from simple and readily available starting materials since such general procedures are not available. The protocol developed by us employs readily available phenanthrenequinone and various 4-substituted acetophenones as starting materials and provides easy access to the required 3(2H)-furanone targets. These furanone derivatives have immense potential for further investigations .We also aimed the synthesis of a few dibenzoylalkene-type systems such as acenaphthenone-2—ylidene ketones and phenanthrenone-9-ylidene ketones. These systems were expected to undergo thermal rearrangement to give furanones and spirofuranones. Also these systems can be categorised as quinonemethides which are valuable synthetic intermediates.

CACHE REPLACEMENT STRATEGIES FOR MOBILE DATA CACHING.

Data caching is an important technique in mobile computing environments for improving data availability and access latencies particularly because these computing environments are characterized by narrow bandwidth wireless links and frequent disconnections. Cache replacement policy plays a vital role to improve the performance in a cached mobile environment, since the amount of data stored in a client cache is small. In this paper we reviewed some of the well known cache replacement policies proposed for mobile data caches. We made a comparison between these policies after classifying them based on the criteria used for evicting documents. In addition, this paper suggests some alternative techniques for cache replacement

Median computation in graphs using consensus strategies

Following the Majority Strategy in graphs, other consensus strategies, namely Plurality Strategy, Hill Climbing and Steepest Ascent Hill Climbing strategies on graphs are discussed as methods for the computation of median sets of pro¯les. A review of algorithms for median computation on median graphs is discussed and their time complexities are compared. Implementation of the consensus strategies on median computation in arbitrary graphs is discussed

Consensus strategies for signed profiles on graphs

The median problem is a classical problem in Location Theory: one searches for a location that minimizes the average distance to the sites of the clients. This is for desired facilities as a distribution center for a set of warehouses. More recently, for obnoxious facilities, the antimedian was studied. Here one maximizes the average distance to the clients. In this paper the mixed case is studied. Clients are represented by a profile, which is a sequence of vertices with repetitions allowed. In a signed profile each element is provided with a sign from f+; g. Thus one can take into account whether the client prefers the facility (with a + sign) or rejects it (with a sign). The graphs for which all median sets, or all antimedian sets, are connected are characterized. Various consensus strategies for signed profiles are studied, amongst which Majority, Plurality and Scarcity. Hypercubes are the only graphs on which Majority produces the median set for all signed profiles. Finally, the antimedian sets are found by the Scarcity Strategy on e.g. Hamming graphs, Johnson graphs and halfcubes

A Study on Futures Trading in Commodities With Special Reference to Rubber

Futures trading in Commodities has three specific economic functions viz. price discovery, hedging and reduction in volatility. Natural rubber possesses all the specifications required for futures trading. Commodity futures trading in India attained momentum after the starting of national level commodity exchanges in 2003. The success of futures trading depends upon effective price risk management, price discovery and reduced volatility which in turn depends upon the volume of trading. In the case of rubber futures market, the volume of trading depends upon the extent of participation by market players like growers, dealers, manufacturers, rubber marketing co-operative societies and Rubber Producer’s Societies (RPS). The extent of participation by market players has a direct bearing on their awareness level and their perception about futures trading. In the light of the above facts and the review of literature available on rubber futures market, it is felt that a study on rubber futures market is necessary to fill the research gap, with specific focus on (1) the awareness and perception of rubber futures market participants viz. (i) rubber growers, (ii) dealers, (iii) rubber product manufacturers, (iv) rubber marketing co-operative societies and Rubber Producer’s Societies (RPS) about futures trading and (2) whether the rubber futures market is fulfilling the economic functions of futures market viz. hedging, reduction in volatility and price discovery or not. The study is confined to growers, dealers, rubber goods manufacturers, rubber marketing co-operative societies and RPS in Kerala. In order to achieve the stated objectives, the study utilized secondary data for the period from 2003 to 2013 from different published sources like bulletins, newsletters, circulars from NMCE, Reserve Bank of India (RBI), Warehousing Corporation and traders. The primary data required for this study were collected from rubber growers, rubber dealers, RPS & Rubber Marketing Co-operative Societies and rubber goods manufacturers in Kerala. Data pertaining to the awareness and perception of futures trading, participation in the futures trading, use of spot and futures prices and source of price information by dealers, farmers, manufacturers and cooperative societies also were collected. Statistical tools used for analysis include percentage, standard deviation, Chi-square test, Mann – Whitney U test, Kruskal Wallis test, Augmented Dickey – Fuller test statistic, t- statistic, Granger causality test, F- statistic, Johansen co – integration test, Trace statistic and Max –Eigen statistic. The study found that 71.5 per cent of the total hedges are effective and 28.5 per cent are ineffective for the period under study. It implies that futures market in rubber reduced the impact of price risks by approximately 71.5 per cent. Further, it is observed that, on 54.4 per cent occasions, the futures market exercised a stabilizing effect on the spot market, and on 45.6 per cent occasions futures trading exercised a destabilizing effect on the spot market. It implies that elasticity of expectation of futures market in rubber has a predominant stabilizing effect on spot prices. The market, as a whole, exhibits a bias in favour of long hedges. Spot price volatility of rubber during futures suspension period is more than that of the pre suspension period and post suspension period. There is a bi-directional association-ship or bi-directional causality or pair- wise causality between spot price and futures price of rubber. From the results of the hedging efficiency, spot price volatility, and price discovery, it can be concluded that rubber futures market fulfils all the economic functions expected from a commodity futures market. Thus in India, the future of rubber futures is Bright…!!!