Thermodynamic and lfer studies for the oxidation of anilines by the periodate ion

The various thermodynamic parameters for the periodate oxidation of six anilines, viz. aniline, p-chloroaniline, p-ethoxyaniline, o- and p-methoxyanilines and p-methylaniline have been reported and discussed. The validity of the isokinetic relationship and various linear free energy relationships (LFERs) have been tested and discussed. An attempt has been made to correlate these findings with the mechanism operative in these reactions.     

Ceric ammonium nitrate on silica gel for efficient and selective removal of trityl and silyl groups

Silica gel-supported ceric ammonium nitrate (CAN-SiO2) was found effective for rapid and selective cleavage of trityl (Tr), monomethoxytrityl (MMTr), and dimethoxytrityl (DMTr) groups from protected nucleosides and nucleotides under mild conditions. Efficiency of deprotections depended upon the stability of the resultant carbocationic species: DMTr+ > MMTr+ > Tr+. Use of a catalytic amount of this solid-supported reagent can also efficiently and selectively remove the tert-butyldimethylsilyl or the triisopropylsilyl group from a primary hydroxyl functionality in di- or trisilyl ethers of ribonucleosides. A comparative study of deprotection reactions by utilization of CAN alone or CAN-SiO2 indicates a remarkable increase in the rate of the reactions involving a solid support. The mechanism of electron-transfer processes is proposed for the use of CAN-SiO2 in the removal of these protective groups from organic molecules.     

Investigation of the reactions of fluorinated isatins and N-acetylisatins with thiocarbohydrazide: Synthesis of a novel spiro system: 2-oxo-1′,2′,4′,5′-tetrahydrospiro[3H-indole-3,3′-1,2,4,5-tetrazine]-6′-thione

A novel system 2-oxo-1′,2′,4′,5′-tetrahydrospiro[3H-indole-3,3′-1,2,4,5-tetrazine]-6′-thione has been synthesized by the treatment of fluorinated isatins with thiocarbohydrazide in aqueous ethanolic medium. Under exactly similar conditions, N-acetylisatin gave exclusively thiocarbohydrazone. The spiro product, on treatment with acetic acid, gave fluorinated isoindigo. Characterization of these products have been done by elemental analyses, ir, pmr and mass spectral studies.     

Polarographische Untersuchungen von aus Cadmium(II) und Propylendiamin in wäßrigem Dimethylformamid entstandenen Komplexen

The reduction of Cd(II) in propylenediamine was found to be reversible and diffusion controlled. The complexes of Cd(II) with propylenediamine in 25%, 50%, and 75% dimethylformamide have been studied polarographically using theDeFord andHume's treatment as extended byIrving. Increase in the stability constants was observed with increase in dimethylformamide percentage. The percentage composition of the various complexed and uncomplexed species in 25% and 50% dimethylformamide are presented.     

A theoretical study of solvation energies of FCH2COO−, FCH2COOH,and F2CHCOO−

A continuum and a discrete-continuum models are used to determine the solvation energies of FCH₂COO^?, FCH₂COOH, and F₂CHCOO^?. For the anions, the continuum model provides results closer to the experiment, while for the acid, the addition of one water molecule improves the continuum-only energy.     

Universal consequences of the presence of excluded volume interactions in dilute polymer solutions undergoing shear flow

The role of solvent quality in determining the universal material properties of dilute polymer solutions undergoing steady simple shear flow is examined. A bead-spring chain representation of the polymer molecule is used, and the influence of solvent molecules on polymer conformations is modelled by a narrow Gaussian excluded volume potential that acts pairwise between the beads of the chain. Brownian dynamics simulations data, acquired for chains of finite length, and extrapolated to the limit of infinite chain length, are shown to be model independent. This feature of the narrow Gaussian potential, which leads to results identical to a delta-function repulsive potential, enables the prediction of both universal crossover scaling functions and asymptotic behavior in the excluded volume limit. Universal viscometric functions, obtained by this procedure, are found to exhibit increased shear thinning with increasing solvent quality. In the excluded volume limit, they are found to obey power law scaling with the characteristic shear rate beta, in close agreement with previously obtained renormalization group results. The presence of excluded volume interactions is also shown to lead to a weakening of the alignment of the polymer chain with the flow direction.     

Enantioselective synthesis of (8S,13S,14R)-7-oxa-estra-4,9-diene-3,17-dione

The first enantioselective synthesis of (8S,13S,14R)-7-oxa-estra-4,9-diene-3,17-dione with the trans-C/D ring junction is described. Key features of the synthesis include Ag₂O-mediated C-O bond formation, thermodynamically controlled axial-equatorial inversion, one-pot of halogen exchange and Co/Cr-mediated C-C bond formation, and intramolecular aldol condensations.     

Reaction of nitriles under acidic conditions. Part VII. Study on the reaction of o-aminonitriles with cyanamides to synthesize 2,4-diaminothieno[2,3-d]pyrimidines

The reaction of N-arylcyanamides with thiophene o-aminonitriles under the influence of dry hydrogen chloride gas yields a mixture of two products. The major product has been identified as 2-amino-3-aryl-4-iminothieno[2,3-d]pyrimidine and the minor as 2-amino-3-arylthieno[2,3-H]pyrimidin-4(3H)-one.     

Thermal ignition studies on metallized fuel-oxidizer systems

The thermal ignition behaviour of various mixtures of organic fuels, magnesium and ammonium nitrate (AN) has been examined by differential thermal analysis technique. It has been observed that the thermal decomposition/ignition of organic fuel-AN mixtures is modified significantly in the presence of magnesium metal. The decomposition characteristics of the binary mixtures of AN with various metals indicate the specific action of magnesium and zinc in lowering the decomposition temperature. A possible explanation for the low temperature decomposition is given in terms of the solid state reaction causing the fusion of AN which further reacts with the metal resulting in a highly exothermic reaction.

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Zusammenfassung Mittels DTA wurde das thermische Initiierungsverhalten verschiedener Gemische aus organischen Brennstoffen, Magnesium und Ammoniumnitrat (AN) untersucht. Es wurde festgestellt, daß die thermische Zersetzung/Initiierung von Gemischen aus organischen Brennstoffen und AN durch die Gegenwart von metallischem Magnesium bedeutsam beeinflußt wird. Die Zersetzungscharakteristiken binären Gemische aus AN und verschiedener Metalle zeigen eine spezielle Wirkung von Magnesium und Zink bei der Herabsetzung der Zersetzungstemperatur. Eine mögliche Erklärung für die Zersetzung bei niedrigerer Temperatur kann in Bezug auf die Festkörperreaktion gesehen werden, die das Schmelzen von AN verursacht, welches dann mit dem Metall stark exotherm reagiert.

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An approximate max-flow min-cut relation for undirected multicommodity flow,with applications

In this paper, we prove the first approximate max-flow min-cut theorem for undirected multicommodity flow. We show that for a feasible flow to exist in a multicommodity problem, it is sufficient that every cut's capacity exceeds its demand by a factor ofO(logClogD), whereC is the sum of all finite capacities andD is the sum of demands. Moreover, our theorem yields an algorithm for finding a cut that is approximately minimumrelative to the flow that must cross it. We use this result to obtain an approximation algorithm for T. C. Hu's generalization of the multiway-cut problem. This algorithm can in turn be applied to obtain approximation algorithms for minimum deletion of clauses of a 2-CNF formula, via minimization, and other problems. We also generalize the theorem to hypergraph networks; using this generalization, we can handle CNF clauses with an arbitrary number of literals per clause.Most of the results in this paper were presented in preliminary form in Approximation through multicommodity flow,Proceedings, 31th Annual Symposium on Foundations of Computer Science (1990), pp. 726–737.Research supported by the National Science Foundation under NSF grant CDA 8722809, by the Office of Naval and the Defense Advanced Research Projects Agency under contract N00014-83-K-0146, and ARPA Order No. 6320, Amendament 1.Research supported by NSF grant CCR-9012357 and by an NSF Presidential Young Investigator Award.