Design of neutral, mono- or di-cationic water-soluble trihydrazidophosphoradamantanes

The versatile behavior of a trihydrazidophosphoradamantane allowing the synthesis of a variety of neutral, mono- or di-cationic water-soluble molecules of potential interest for biphasic catalysis is reported.     

Remote stereocontrol by the sulfinyl group: Mukaiyama aldol reactions of (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde in the asymmetric synthesis of β-hydroxyacids and 1,3-diols

(S)-2-[2-(p-Tolylsulfinyl)phenyl]acetaldehyde reacts with different O-silylated ketenethioacetals in the presence of Yb(OTf)₃ yielding β-hydroxythioesters in high yields and diastereoselectivities. The obtained compounds were readily transformed into β-hydroxyacids and their corresponding diols. These Mukaiyama aldol reactions are a direct evidence of the ability of the sulfinyl group to control 1,5- and 1,6-asymmetric induction processes.     

Regular population monotonic allocation schemes

The paper introduces a refinement of the notion of population monotonic allocation scheme, called regular population monotonic allocation scheme (regularpmas). This refinement is based on economic situations in which players may have to select new partners from a set of potential players and in which there exist certain capacity constraints. A sufficient condition for the existence of a regularpmas is given. For the class of games with regularpmas, we prove that the core coincides with the Davis and Maschler and the Mas-Colell bargaining sets.     

Preparation of rhodium–phyllosilicate catalysts without leaching in liquid-phase 1-hexene hydrogenation

Rhodium catalysts have been prepared on palygorskite and montmorillonite (clay) supports by reduction with hydrogen (1 atmosphere) at room temperature of a cationic organometallic rhodium compound anchored to the support. The activity of these catalysts for the hydrogenation of liquid-phase 1-hexene remains constant with increase of prehydrogenation time and with re-use for several runs. No rhodium leaching is observed.     

Elimination of man-made radionuclides from natural waters by applying a standard coagulation-flocculation process

We studied the effectiveness of potable water treatment processes that consist of the stages of coagulation-flocculation-decantation, using iron-based coagulants, in eliminating gamma-emitting man-made radioisotopes of cesium, strontium, and americium from two natural waters with different degrees of mineralization. The resulting decontamination was found to depend on the chemical behavior of each of the radionuclides considered, on the pH at which the process of coagulation is carried out, and on the concentration of the other stable cations present. This revised version was published online in July 2006 with corrections to the Cover Date.     

A nucleophilic substitution reaction in microemulsions based on either an alcohol ethoxylate or a sugar surfactant

A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.

¹²⁷I NMR studies, as well as quadrupole splitting experiments performed by ²H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.

The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles.     

Luttinger liquid with asymmetric dispersion

We present an extension of the Tomonaga-Luttinger model in which left and right-moving particles have different Fermi velocities. We derive expressions for one-particle Green's functions, momentum-distributions, density of states, charge compressibility and conductivity as functions of both the velocity difference ε and the strength of the interaction β. This allows us to identify a novel restricted region in the parameter space in which the system keeps the main features of a Luttinger liquid but with an unusual behavior of the density of states and the static charge compressibility κ. In particular κ diverges on the boundary of the restricted region, indicating the occurrence of a phase transition. Received 20 May 2002 / Received in final form 23 August 2002 Published online 19 November 2002     

Olefin terpolymerizations. II. 4-vinylcyclohexene and cyclooctadiene

4-Vinylcyclohexene (VCH) and cyclooctadiene (COD) were investigated as termonomers in EPDM (ethylene/propylene/diene) synthesis by using rac-ethylenebis (1-η⁵-indenyl) zir-conium dichloride ( 1 ) as a catalyst precursor. Homopolymerizations of VCH, vinylcycloh-exane and cyclohexene were compared. The parameter K_πκ_p, which is the apparent rate constant for Ziegler-Natta polymerization, is about the same for VCH and vinylcyclohexanebut is 10 times smaller for cyclohexene. Therefore, the linear olefinic double bond is more active than the cyclic internal double bond. VCH reduces ethylene polymerization rate but not propylene polymerization rate in copolymerizations. In terpolymerizations, VCH tends to suppress ethylene incorporation especially at elevated polymerization temperature and Lowers the polymer MW by about two-fold. COD has very low activity as a termonomer. © 1995 John Wiley & Sons, Inc.