Polyesterification of aromatic dicarboxylic acids and bisphenols with tosyl chloride/dimethylformamide/pyridine promoted by the improvement of the difficult solubility of the activated diacids with lithium chloride

The solution polyesterification of dicarboxylic acids in pyridine, the activated intermediates of which were difficult to dissolve in tosyl chloride/dimethylformamide/pyridine, was investigated in the presence of lithium chloride. The solubility of the activated dicarboxylic acids was largely improved by the presence of the salt, and the polycondensation with bisphenols was greatly facilitated. The salt was more effectively added to a pyridine solution of dicarboxylic acids than to the activated dicarboxylic acids in pyridine. The favorable additive effect on the improved solubility was attributed to a lowered degree of association of the activated dicarboxylic acids, which led to distributions of the resulting oligomers from bisphenols at an earlier stage closer to the theoretical ones and yielded better polycondensation results. The reaction, which proceeded through favorable distributions of the co‐oligomers, produced copolymers of higher inherent viscosities and slightly block sequence distributions determined by NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2725–2733, 2004     

Novel UV‐induced photografting process for preparing poly(tetrafluoroethylene)‐based proton‐conducting membranes

A novel process comprising the UV‐induced photografting of styrene into poly(tetrafluoroethylene) (PTFE) films and subsequent sulfonation has been developed for preparing proton‐conducting membranes. Although under UV irradiation the initial radicals were mainly generated on the surface of the PTFE films by the action of photosensitizers such as xanthone and benzoyl peroxide, the graft chains were readily propagated into the PTFE films. The sulfonation of the grafted films was performed in a chlorosulfonic acid solution. Fourier transform infrared and scanning electron microscopy were used to characterize the grafted and sulfonated membranes. With a view to use in fuel cells, the proton conductivity, water uptake, and mechanical properties of the prepared membranes were measured. Even through the degree of grafting was lower than 10%, the proton conductivity in the thickness direction of the newly prepared membranes could reach a value similar to that of a Nafion membrane. In comparison with γ‐ray radiation grafting, UV‐induced photografting is very simple and safe and is less damaging to the membranes because significant degradation of the PTFE main chains can be avoided. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2624–2637, 2007     

Tangent circle bundles admit positive open book decompositions along arbitrary links

In the present paper we generalize the divide lying in the unit disk, introduced by A'Campo, to compact, oriented, smooth surfaces, and prove a fibration theorem for generalized divides. As a consequence, we will show that, for any link L in the tangent circle bundle Y to the compact surface, there exists an additional knot K such that the link L∪K is the binding of a “positive” open book decomposition of Y.     

Likelihood estimation of soft-core interaction potentials for Gibbsian point patterns

The likelihood method is developed for the analysis of socalled regular point patterns. Approximating the normalizing factor of Gibbs canonical distribution, we simultaneously estimate two parameters, one for the scale and the other which measures the softness (or hardness), of repulsive interactions between points. The approximations are useful up to a considerably high density. Some real data are analyzed to illustrate the utility of the parameters for characterizing the regular point pattern.     

2-alkoxy and 2,2-dialkoxy nitriles from acetals and orthoesters — exchange of alkoxy into cyano group by means of cyanotrimethylsilane

Title transformation is accomplished by the catalytic action of SnCl₂ or BF₃·OEt₂ Lithio derivative of 2,2-dimethoxyacetonitrile is used as synthetic equivalent of methyl lithioformate.     

Transition metal salts-catalyzed aza-Michael reactions of enones with carbamates

Several transition metal salts were found to catalyze aza-Michael reactions of enones with carbamates efficiently. The catalytic activity was strongly dependent on the nature of the metal salts. While conventional Lewis acids such as BF(3).OEt(2), AlCl(3), or TiCl(4) showed lower activity, group 7-11 transition metal salts in higher oxidation states such as ReCl(5), Fe(ClO(4))(3).9H(2)O, RuCl(3).nH(2)O, OsCl(3).3H(2)O, RhCl(3).nH(2)O, PtCl(4).5H(2)O, or AuCl(3).H(2)O exhibited higher catalytic activity. [reaction: see text]     

A novel measurement method of Donnan potential at an interface between a charged membrane and mixed salt solution

We developed a novel measurement method of the Donnan potential difference at a charged membrane/salt solution interface. The method can measure the potential under the condition that the membrane charge density is much lower than the KCl concentration of the salt bridge. This method is very useful for obtaining the effective charge density of each layer of a bipolar membrane. The present experiments in a system of a negatively charged poly(vinyl alcohol) membrane and a single salt solution of KCl, NaCl, LiCl, CaCl₂ and LaC₃ revealed that the membrane effective charged density has the same value for all the ions. The experiments in mixed KCl and CaCl₂ solution revealed that the potential in the system is governed mainly by the concentration of the counterion having the highest valence in the system.     

alpha-Aminoallylation of aldehydes with ammonia: stereoselective synthesis of homoallylic primary amines

Three-component reactions of aldehydes, ammonia, and allylboronates were found to provide homoallylic primary amines in high yields with high chemo- and stereoselectivities. A two-step, one-pot, stereoselective synthesis of an uncommon alpha-amino acid, alloisoleucine, was achieved utilizing this reaction.     

Indium triflate-catalyzed vinylation of beta-ketoesters with acetylene gas

[reaction: see text]. An In(OTf)(3)-catalyzed addition of a beta-ketoester to acetylene in the presence of molecular sieves produces a alpha-vinylated ketoester in good to excellent yield. The vinylation reaction proceeds without any loss of elements in starting molecules under solvent-free conditions and allows the use of welding-grade acetylene, providing a practical method for synthetic utilization of acetylene gas.