New tin templates for the synthesis of macrocyclic polythiaether-polythiaester ligands

The preparation of new tin templates, stannathianes 1-3 is described. New templates have been successfully applied to the synthesis of macrocyclic polythialactones 4-9 by cyclization of corresponding stannathianes 1-3 with pimeloyl dichloride.     

Lipophilicity Evaluation of the Products Obtained in the Reaction of N3-Substituted Amidrazones with cis-1,2-Cyclohexanedicarboxylic Anhydride

The lipophilicity of the novel 12 products of the reaction of N³-substituted amidrazones with cis-1,2-cyclohexanedicarboxylic anhydride (4 linear, 4 triazole-like and 4 isoindole ones) with potential pharmacologic activity was evaluated by thin layer and liquid chromatography. Using organic-aqueous eluent systems (with methanol or acetonitrile) on RP18 plates and C18 column, a linear relationship between the volume fraction of modifiers and the retention indices was obtained. The retention values, log k or R _M were extrapolated to zero organic modifier content to obtain the log k _w or R _MW values. 12 compounds with known literature lipophilicity were used as a calibration dataset. The results were compared in a multivariate way with in silico methods (ALOGPs, AC_logP, AB/LogP, COSMOFrag, miLogP, ALOGP, MLOGP, KOWWIN, XLOGP3).

     

On natural homomorphisms of Witt rings

We prove that the kernel of the ring homomorphism between the Witt ring of any order of a global field and the Witt ring of the field is a nilideal.

     

Reducing Cognitive Effort in Scoring Negotiation Space Using the Fuzzy Clustering Model

Negotiation scoring systems are fundamental tools used in negotiation support to facilitate parties searching for negotiation agreement and analyzing its efficiency and fairness. Such a scoring system is obtained in prenegotiation by implementing selected multiple criteria decision-aiding methods to elicit the negotiator’s preferences precisely and ensure that the support is reliable. However, the methods classically used in the preference elicitation require much cognitive effort from the negotiators, and hence, do not prevent them from using heuristics and making simple errors that result in inaccurate scoring systems. This paper aims to develop an alternative tool that allows scoring the negotiation offers by implementing a sorting approach and the reference set of limiting profiles defined individually by the negotiators in the form of complete packages. These limiting profiles are evaluated holistically and verbally by the negotiator. Then the fuzzy decision model is built that uses the notion of increasing the preference granularity by introducing a series of limiting sub-profiles for corresponding sub-categories of offers. This process is performed automatically by the support algorithm and does not require any additional preferential information from the negotiator. A new method of generating reference fuzzy scores to allow a detailed assignment of any negotiation offer from feasible negotiation space to clusters and sub-clusters is proposed. Finally, the efficient frontier and Nash’s fair division are used to identify the recommended packages for negotiation in the bargaining phase. This new approach allows negotiators to obtain economically efficient, fair, balanced, and reciprocated agreements while minimizing information needs and effort.     

Hydrolysis and retro‐aldol cleavage of ethyl threo‐2‐(1‐adamantyl)‐3‐hydroxybutyrate: competing reactions

The hydrolysis of ethyl threo‐2‐(1‐adamantyl)‐3‐hydroxybutyrate ( 1 ) and the parent ester ethyl 3‐hydroxybutyrate ( 4 ) has been studied experimentally and computationally. In the hydrolysis of threo‐ester 1 with 2 M NaOH, predominantly retro‐aldol product was observed, whereas the hydrolyzed product was present in a minor amount. When the reaction is carried out under the same conditions with the parent ester ethyl 3‐hydroxybutyrate ( 4 ), hydrolyzed product is exclusively observed. The competitive pathways, namely hydrolysis and the retro‐aldol reaction for 1 and 4 were investigated using DFT calculations in the both gas and solvent phase. The calculated results in the solvent phase at B3LYP/6–31 + G* level revealed that the formation of retro‐aldol products is kinetically preferred over the hydrolysis of threo‐ester 1 in the presence of a base. However, the parent ester 4 showed that the retro‐aldol process is less favored than the hydrolysis process under similar conditions. The steric effect imposed by the bulky adamantyl group to enhance the activation barriers for the hydrolysis of the ethyl threo‐2‐(1‐adamantyl)‐3‐hydroxybutyrate ( 1 ) was further supported by the calculations performed with tert‐butyl group at the α‐carbon atom of ethyl 3‐hydroxybutyrate ( 7 ). Copyright © 2010 John Wiley & Sons, Ltd.     

Vanadium complex with tetradentate [O,N,N,O] ligand supported on magnesium type carrier for ethylene homopolymerization and copolymerization

Immobilization of 1,2‐cyclohexylenebis(5‐chlorosalicylideneiminato)vanadium dichloride on the magnesium support obtained in the reaction of MgCl₂·3.4EtOH with Et₂AlCl gives a highly active precursor for ethylene homopolymerization and its copolymerization with 1‐octene. This catalyst exhibits the highest activity in conjunction with MAO, but it is also highly active with AlMe₃ as a cocatalyst. On the other hand, when combined with chlorinated alkylaluminum compounds, Et₂AlCl and EtAlCl₂, it gives traces of polyethylene. Moreover, its catalytic activity is strongly affected by the reaction temperature: it increased with rising polymerization temperature from 20 °C to 60 °C. The kinetic curves obtained for the supported vanadium catalyst, in contrast to its titanium analogue, are of decay type, yet the reduction in the polymerization rate is rather moderate in the early stages of polymerization, and then it is relatively very slow. The vanadium catalyst gives copolymers at a lower yield than the titanium one does, but with the significantly higher 1‐octene content. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 471–478, 2010