Study on 1,3,5‐Triazine Chemistry in Dehydrocondensation: Gauche Effect on the Generation of Active Triazinylammonium Species

The reaction of 2‐chloro‐4,6‐dimethoxy‐1,3,5‐triazine (CDMT) with various nitrogen‐containing compounds, particularly tertiary amines (tert‐amines), has been studied for the preparation of 2‐(4,6‐dimethoxy‐1,3,5‐triazinyl)trialkylammonium salts [DMT‐Am(s)]. DMT‐Ams derived from aliphatic tert‐amines exhibited activity for the dehydrocondensation between a carboxylic acid and an amine to form an amide in a model reaction. Based on a conformational analysis of DMT‐Ams and tert‐amines by NMR and X‐ray diffraction methods, we concluded that a β‐alkyl group maintained in a gauche relationship with the nitrogen lone pair of tert‐amines significantly hinders the approach of CDMT to the nitrogen. Thus, trimethylamine and quinuclidine without such alkyl groups readily react with CDMT whereas triethylamine, possessing two or three such gauche β‐alkyl groups in the stable conformations, does not react at all. The theory of “gauche β‐alkyl group effect” proposed here provides useful guidelines for the preparation of DMT‐Ams possessing various tertiary amine moieties. An investigation of the dehydrocondensation activity of tert‐amines in a CDMT/tert‐amine system that involves in situ generation of DMT‐Am, showed that the gauche effect of the β‐alkyl group becomes quite pronounced; the yield of the amide decreases significantly with tert‐amines possessing an unavoidable gauche β‐alkyl group. Thus, the tert‐amine/CDMT systems are useful for judging whether tert‐amines can readily react with CDMT without isolation of DMT‐Ams.     

Constructing connected bicritical graphs with edge-connectivity 2

A graph $G$ is said to be bicritical if the removal of any pair of vertices decreases the domination number of $G$. For a bicritical graph $G$ with the domination number $t$, we say that $G$ is $t$-bicritical. Let $\lambda \left(G\right)$ denote the edge-connectivity of $G$. In [2], Brigham et al. (2005) posed the following question: If $G$ is a connected bicritical graph, is it true that $\lambda \left(G\right)\ge 3?$In this paper, we give a negative answer toward this question; namely, we give a construction of infinitely many connected $t$-bicritical graphs with edge-connectivity $2$ for every integer $t\ge 5$. Furthermore, we give some sufficient conditions for a connected $5$-bicritical graph to have $\lambda \left(G\right)\ge 3$.     

Blockade of inflammatory responses by a small-molecule inhibitor of the Rac activator DOCK2

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Highlights? CPYPP binds to DOCK2 DHR-2 domain and inhibits its catalytic activity ? CPYPP inhibits DOCK2-mediated Rac activation in cells ? The structural features of CPYPP required for its inhibitory effect were revealed ? CPYPP inhibits lymphocyte migration and activation in vitro and in vivo     

Single Crystal of a Prussian Blue Analogue Based on Rubidium Manganese Hexacyanoferrate.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.     

Estimation of the Refractive Index Change in Glass Induced by Femtosecond Laser Pulses

It is known that local refractive index change occurs when femtosecond laser pulses with extremely high peak power are launched into glass. We focused 130-femtosecond laser pulses of 800 nm into the bulk of glass and examined the shape of the induced refractive index change. We found that the length of the spot of the refractive index change along the optical axis reached about 30 μm despite the diameter being about 2 μm. To estimate the distribution of induced refractive index change, we fabricated Bragg grating by scanning the focused spot and calculated the amount of the change by applying Kogelnik’s coupled mode theory to the measured diffraction efficiencies of the higher order diffracted beams.     

A chiral chelating diene as a new type of chiral ligand for transition metal catalysts: its preparation and use for the rhodium-catalyzed asymmetric 1,4-addition

As a new type of chiral ligand, a C2-symmetric norbornadiene derivative (1R,4R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene (1) was prepared and used for the rhodium-catalyzed asymmetric addition of organoboron and -tin reagents to alpha,beta-unsaturated ketones, which gave high yields of the 1,4-addition products with up to 99% enantioselectivity.     

Some Regularity Criteria for Affine Semilocal Rings

The purpose of this article is to study an existence of p-bases and mainly to give some regularity criteria for semilocal rings essentially of finite type over fields.     

Selective tungsten deposition into ordered nanohole arrays of anodic porous alumina by electron-beam-induced deposition

The selective deposition of a metal (tungsten) into ordered nanohole arrays of an anodic porous alumina membrane was performed using an electron-beam-induced deposition process. After deposition, the membrane was observed and analyzed using electron microscopy and energy-dispersive X-ray spectroscopy. It is shown that the deposition was preferentially conducted in the holes in the irradiated area of the electron beam. A calculation of the electron-beam intensity explains the reason for the preferential deposition in the holes. PACS 81.07.-b; 81.16.Rf; 61.46.+w