A novel and expeditious approach to unusual spirolactam building blocks

A rapid access to 7-azaspiro[4.5]decan-6-ones 1 involving three regio- and chemoselective reactions starting from tetrabromonorbornyl derivatives is described. The alkaline H(2)O(2) cleavage reaction of monosubstituted alpha-diketones 9 furnished the potential bridged bicyclic lactones 10in a highly regio- and stereoselective manner. The radical-mediated, intermolecular bridgehead C-C bond formation of the versatile bridged lactones 10 with acrylonitrile followed by LAH reduction of the adduct 13 intriguingly leads to the formation of novel spirolactam building blocks 1.     

Physico-chemical properties of the sodium salts of some fatty acids in formamide solution in the temperature range 15–45°C

The thermal stability of some boracites, CuB₇O₁₃Cl, NiB₇O₁₃Br and FeB₇O₁₃I, was investigated using thermogravimetry in air up to 1000°, DTA in air to 1200° and evolved gas analysis in vacuum to 1200°C. Only the FeI compound showed weight loss below 1000°C. The endothermic peaks associated with melting were CuCl (1025°C), NiBr (1150°C) and FeI) (965°C). Evolved gas analysis indicated major differences in the decomposition products of the three materials.     

Kinetic studies of nonaqueous polymerization of methyl methacrylate initiated by ferric laurate–n-hexyl amine system

The polymerization of methyl methacrylate was studied in carbon tetrachloride medium with ferric laurate, a metal soap, in combination with n-hexyl amine as the initiator system at 60°C. The rate of polymerization was found to be linear with the monomer concentration and proportional to the square root of both ferric ion and amine concentration. A reaction scheme involving initial complex formation between ferric ion and amine and subsequent reaction of the complex with the solvent molecule to produce free radicals responsible for initiation of polymerization has been postulated to account for the observed results.     

The coupled-cluster method with a multiconfiguration reference state

The coupled-cluster approach to obtaining the bond-state wave functions of many-electron systems is extended, with a set of physically reasonable approximations, to admit a multiconfiguration reference state. This extension permits electronic structure calculations to be performed on correlated closed- or open-shell systems with potentially uniform precision for all molecular geometries. Explicit coupled cluster working equations are derived using a multiconfiguration reference state for the case in which the so-called cluster operator is approximated by its one- and two-particle components. The evaluation of the requisite matrix elements is facilitated by use of the unitary group generators which have recently received wide attention and use in the quantum chemistry community.     

Thermodynamics of silver—silver halide electrodes and thermodynamic solubility products of silver halides in glycerol + water mixtures at different temperatures

The standard potentials of silver—silver bromide and silver—silver iodide electrodes in glycerol+water mixtures containing 5, 10, 20 and 30 wt% glycerol were determined from electromotive force measurements of the cell Ag(s), AgX(s), KX(c)//KCl(c), AgCl(s), Ag(s), where X is Br or I, at seven different temperatures in the range 5–35°C. The standard potentials in each solvent are represented as a function of temperature. The standard thermodynamic functions for the electrode reactions, the primary medium effects of various solvents upon X⁻, and the standard thermodynamic quantities for the transfer of 1 g-ion of X⁻ from water to the respective glycerol + water media are evaluated and discussed in the light of ion—solvent interactions as well as the structural changes of the solvents. From the values of the Ag/Ag⁺ and Ag/AgX, X⁻ electrodes, the thermodynamic solubility product constants of silver chloride, silver bromide and silver iodide have been determined in glycerol + water solvent mixtures at different temperatures.     

Divisibility of certain $$\ell $$ -regular partitions by 2

The Ramanujan Journal - For a positive integer $$\ell $$ , let $$b_{\ell }(n)$$ denote the number of $$\ell $$ -regular partitions of a nonnegative integer n. Motivated by some recent conjectures...     

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.     

Effect of gamma irradiation on the thermal decomposition of zinc bromate by dynamic thermogravimetry

The thermal decoposition of -irradiated zinc bromate has been studied by dynamic thermogravimetry. The reaction order, activation energy, frequency factor and entropy of activation were computed using the Coats-Redfern, Freeman-Carroll and Horowitz-Metzger methods and were compared with those of the unirradiated salt. Irradiation enhances the decomposition and the effect increases with the irradiation dose. The activation energy decreases on irradiation. The mechanism for the decomposition of unirradiated and irradiated zinc bromate follows the Avrami model equation, 1-(1-)^1/3=kt, and the rate-controlling process is a phase boundary reaction assuming spherical symmetry.     

Kinetics and mechanism of the anation of (αβ)-hydroxo(tetraethylenepentamine)cobalt(III) by thiosulfate, the base hydrolysis of the (sulfur-bonded) thiosulfato(tetraethylenepentamine)-cobalt(III) and photochemistry of oxygen and sulfur-bonded thiosulfato complexes

Summary The reaction of ()-(tetren)CoOH²⁺ with S₂O ₃ ^2- in the 7.25–8.28 pH range at 20–40 °C yielded S- (yellow) and O- (purple) bonded thiosulfato(tetren)cobalt(III) complexes, the former in larger quantities. The rate determining step is preceded by diffusion-controlled ion-pair [(tetren)CoOH²⁺,S₂O ₃ ^2- ] formation. Replacement of coordinated OH^- by S₂O ₃ ^2- is interpreted in terms of an internal conjugate base mechanism: (tetren)CoOH²⁺ (tetren-H)CoOH ₂ ²⁺ , the reactive amido conjugate base being generated by intramolecular proton transfer from the coordinated NH site.In acid medium the S-bonded (tetren)Co(S₂O₃)⁺ is highly stable to redox decomposition, in contrast to its pentaammine analogue. The complex however, undergoes base hydrolysis yielding the corresponding hydroxo complex. The rate and activation parameters for the base hydrolysis have been reported. Photolysis of O- and S-bonded isomers of [(tetren)CoS₂O₃]⁺ in acidic medium at 254 and 313 nm, respectively, yielded aquation products accompanied by some decomposition of S₂O ₃ ^2- .