Unconventional nucleotide analogues—XVII: Ring-transformations of uracil dihalocarbene adducts

Halocarbene adducts of 1,3-disubstituted uracil (3a, b, d) undergo ring-enlargement to yield 1,3-diazepine derivatives (4a–d). The ring-opening of the cyclopropane system is controlled by the stereochemical configuration of the halogen atom, which can be eliminated as a halide ion. Reduction of the adducts with n-Bu₃SnH leads to a variety of 1,3-diazepines. Details of the mechanism of formation of the diazepines and their further transformations are discussed.     

Ultrasound mediated alkaline hydrolysis of methyl benzoate--reinvestigation with crucial parameters

In the present work hydrolysis of methyl benzoate was carried out using aqueous sodium hydroxide solution at room temperature in the presence of ultrasound since otherwise the same reaction takes place at relatively high temperature. Also, the above hydrolysis reaction was investigated at a relatively larger scale with the variation in parameters influencing the emulsification process and hence the reaction rates. It has been observed that the position of ultrasound source on the liquid-liquid interface is a crucial parameter affecting the two-phase emulsification rates. The poor bulk mixing occurring in the presence of ultrasound alone with an increase in the volume of the reaction mixture and its consequent effect on the reaction kinetics has been conclusively established. These studies have shown that the use of ultrasound with mechanical stirring can result in substantial reduction in the overall power consumption, especially for reaction systems like hydrolysis that do not require very high temperatures and pressures generated by cavitation.     

Correlations to predict droplet size in ultrasonic atomisation.

In conventional two fluid nozzles, the high velocity air imparts its energy to the liquid and disrupts the liquid sheet into droplets. If the energy for liquid sheet fragmentation can be supplied by the use of ultrasonic energy, finer droplets with high sphericity and uniform size distribution can be achieved. The other advantage of ultrasound induced atomisation process is the lower momentum associated with ejected droplets compared to the momentum carried by the droplets formed using conventional nozzles. This has advantage in coating and granulation processes. An ultrasonic probe sonicator was designed with a facility for liquid feed arrangement and was used to atomise the liquid into droplets. An ingenious method of droplet measurement was attempted by capturing the droplets on a filter paper (size variation with regard to wicking was uniform in all cases) and these are subjected to image analysis to obtain the droplet sizes. This procedure was evaluated by high-speed photography of droplets ejected at one particular experimental condition and these were image analysed. The correlations proposed in the literature to predict droplet sizes using ultrasound do not take into account all the relevant parameters. In this work, a truly universal correlation is proposed which accounts for the effects of physico-chemical properties of the liquid (flow rate, viscosity, density and surface tension), and ultrasonic properties like amplitude, frequency and the area of vibrating surface. The significant contribution of this work is to define dimensionless numbers incorporating ultrasonic parameters, taking cue from the conventional numbers that define the significance of different forces involved in droplet formation. The universal correlations proposed are robust and can be used for designing ultrasonic atomisers for different applications. Among the correlations proposed here, those ones that are based on the dimensionless numbers and Davies approach predict droplet sizes within acceptable limits of deviation. Also, an empirical correlation from experimental data has been proposed in this work.     

Ultrasound and deep eutectic solvent (DES): A novel blend of techniques for rapid and energy efficient synthesis of oxazoles

The present work deals with the synthesis of novel oxazole compounds by using effective combination of ultrasound (US) and deep eutectic solvent (DES). The reaction was also conducted by thermal method (NUS) and the comparative studies are provided. It was observed that applying ultrasound not only improved yields and reduced reaction times but also saved more than 85% energy as shown by energy consumption calculations. The advantages of using DES as reaction medium is highlighted from the fact that it is bio-degradable, non-toxic, recyclable and could be easily prepared using inexpensive raw materials. The recyclability for DES was studied wherein it was found that ultrasound has no negative effects on DES even up to four runs. In addition, the present work is the first report on the combinative use of DES and US in organic synthesis.     

Geosphere laminations in free groups

We construct geosphere laminations for free groups, which are codimension one analogues of geodesic laminations on surfaces. Other analogues that have been constructed by several authors are dimension-one instead of codimension-one. Our main result is that the space of such laminations is compact. This in turn is based on the result that crossing, in the sense of Scott-Swarup, is an open condition. Our construction is based on Hatcher??s normal form for spheres in the model manifold.     

Simple bilevel programming and extensions

Mathematical Programming - In this paper we discuss the simple bilevel programming problem (SBP) and its extension, the simple mathematical programming problem under equilibrium constraints...