Michail Vasil'evič Lomonosov

This paper is dedicated to the 300^th anniversary of Michail Vasil'evič Lomonosov, Russiás first world‐renowned scholar. He was educated in Russia and Germany and founded the first chemical laboratory in the Academy of St. Petersburg. There he carried out many quantitative experiments especially in the field of melting glasses. He argued in favor of a corpuscular structure of matter and explained physical and chemical phenomena on the basis of his theory. He also contributed to the humanities by writing numerous papers about the history of the Russian nation and the grammar and the poetics of the Russian language. In his personal life he also wrote himself poems and odes.     

Development of the catalytic synthesis of compounds of the quinoline series (the N. S. Kozlov reaction) (Review)*

This article is dedicated to the 80^th anniversary of the Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus (in 1929-1959 the Institute of Chemistry, Academy of Sciences of the BSSR). It contains a review of the advances in the synthesis and properties of condensed heterocyclic systems containing a quinoline fragment – derivatives of quinaldine, benzo[f]quinoline, indeno- and indoloquinoline, benzo[a]phenanthridine, benzoacridine, tetrahydroquinoline, 1,7- and 4,7-phen-anthroline. The reactions forming the basis of the synthesis of the heterocycles are described – catalytic reaction of amines with acetylene, catalytic condensation of azomethines with methyl and α-methylene ketones, triple-component condensation of arylamines, carbonyl compounds, and CH acids.     

Pyridazines,LIV: On the synthesis of pyridazine-fused S-heterocycles: Thieno[2,3-c]pyridazine,pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine,and pyridazino[3,4-b][1,4]benzothiazine

Summary Starting from 3-chloro-4-pyridazinecarbonitrile (1), the thienopyridazine derivatives2 and3 were prepared. Condensation of3 with triethyl orthoformate afforded the novel tricyclic system4. Reaction of1 with 2-aminothiophenol, followed by treatment with NaH/DMSO was found to give the diaza-phenothiazine6 instead of the expected condensed thiazepine.Dedicated with best wishes to Prof. Dr. G. Zigeuner on the occasion of his 70^th anniversary     

Study of alkaloids of the Siberian and Altai flora

Lappaconitine and N-deacetyllappaconitine derivatives containing bromine and iodine atoms in the aromatic moiety were synthesized. The Heck cross-coupling of these halides with ethyl acrylate or 2-methyl-5-vinylpyridine afforded new olefinated lappaconitine derivatives. Dedicated to the memory of Academician V. A. Koptyug on the occasion of the 75th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1038–1044, June, 2006.     

Temperature dependence of EPR spectrum of 2-trifluoromethylnitrobenzene radical anion in acetonitrile

Temperature dependence of the EPR spectrum of 2-trifluoromethylnitrobenzene radical anion in anhydrous acetonitrile in the temperature range 217 K ≤ T ≤ 296 K was studied and simulated. Temperature-dependent dynamic modulation of the fluorine isotropic hyperfine structure is caused by slow hindered rotation of CF₃ group with an activation energy of E _F* = 36.5±0.5 kJ mol⁻¹, which is the highest value for motions in π-type free radicals studied to date. Dedicated to the memory of Academician V. A. Koptyug on the occasion of the 75th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 926–931, June, 2006.     

Catalytic oxidation of α-pinene with tert-butyl hydroperoxide in the presence of Fe-pillared montmorillonite

The reaction of α-pinene with tert-butyl hydroperoxide can proceed via allylic oxidation or α-pinene isomerization, depending on the structural features of the catalysts based on Fe-pillared montmorillonite. Dedicated to the memory of Academician V. A. Koptyug on the occasion of the 75th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 956–961, June, 2006.     

On the odour shift from bitter almond odour to cinnamic-floral notes

Summary The structural differences between bitter almond odour substances and molecules with cinnamic or floral odour notes were investigated by comparison of a number of compounds with various synthetic modifications. An attempt was made to find a systematic principle for the change of the odour notes.Dedicated to Prof. Dr. K. Schlögl on the occasion of his 70^th anniversary     

Improved synthesis of the enantiomers of propafenone using chiral building blocks

Summary A short and efficient synthesis of the enantiomers of the antiarrhythmic drug propafenone (1) is described using both (R)-isopropylideneglycerol tosylate and (S)-glycidyl tosylate as chiral building blocks. The key step of the high yield synthesis is the acetalization of the carbonyl group in 1-(2-hydroxyphenyl)-3-phenyl-1-propanone (2) which allows application of mild reaction conditions in the subsequent alkylation of the phenolic hydroxy group.With our best wishes dedicated to Prof. Dr.H. Achenbach on the occasion of his 65^th birthday     

2-(10-Diazo-10H-anthracen-9-ylidene)-malonodinitrile: A convenient precursor of 9,10-disubstituted anthracenes

Summary The acid promoted decomposition of 2-(10-diazo-10H-anthracen-9-ylidene)-malonodinitrile in the presence of water, methanol, ethanol, acetic and propionic acid, ethyl thioglycolate,p-thiocresole, and acetyl acetone yielding 9,10-disubstituted 9,10-dihydroanthracenes was investigated. Treatment of the reaction products with tri-ethyl amine followed by hydrochloric acid caused their tautomerization to the corresponding 9,10-disubstituted anthracenes. A mechanism for this reaction is proposed. The first example of an intermolecular C-C-bond formation during the protic acid promoted decomposition of a diazo compound in the presence of CH-acids was found. An improved procedure for the preparation of the starting diazo compound, which may serve as a convenient precursor of 9,10-disubstituted anthracenes, is described.Cordially dedicated to Prof. Dr.K. Winsauer on the occasion of his 70^th birthday     

Analysis of phase diagrams employing Bayesian excess parameter estimation

Summary Bayesian estimation of thermodynamic excess quantities was applied to liquidus data of the systems cyclohexane — benzene and potassium chloride — sodium chloride as well as data on the austenite ferrite equilibrium of the iron — zinc system. Theoretical considerations (KCl-NaCl) and results from calorimetric or partial pressure studies (Fe-Zn) were used as independenta priori information. The recalculated phase diagrams coincide perfectly with those given in the literature. In each case the thermodynamic significance of the experimental data is discussed.Dedicated to Professor Erich Schwarz-Bergkampf on occasion of the 85^th anniversary of his birthday     

Solubility Behavior in Ternary Water-Salt Systems under Sub- and Supercritical Conditions

Summary.  Two main types of binary systems with distinctive solubility behavior under sub- and supercritical conditions were used to subdivide ternary water-salt systems into three classes. Characteristic features of solubility behavior and phase equilibria in ternary water-salt systems of each class at temperatures above 200°C are discussed on the basis of available experimental data and some conclusions obtained as a result of theoretical derivation of fluid and complete phase diagrams. Corresponding author. E-mail: Valyashko@IGIC.RAS.RU Received September 25, 2002; accepted (revised) November 28, 2002 Published online April 24, 2003 RID="a" ID="a" Dedicated to Prof. Dr. H. Gamsjaeger on the occasion of his 70^th birthday anniversary     

Synthesis of 2-thio derivatives of 4-phenyl-9H-pyrimido[4,5-b]indole

The reaction of 3-benzylidene-2-ethoxyindolenine tetrafluoroborate with thiourea gives a mixture of 4-phenylpyrimido[4,5-b]indole-2(1H)-thione, its 3,4-dihydro derivative, and the corresponding disulfide, the product ratio depending on the reaction conditions. A number of transformations of the resulting compounds, in particular, those giving 2-alkylthio pyrimidoindole derivatives are described. Dedicated to the memory of Academician V. A. Koptyug on the occasion of the 75th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1032–1037, June, 2006.     

Reaction of Z isomers of alkylaromatic 1,2-hydroxylamino oximes with 1,2-diketones

The reactions of Z isomers of alkylaromatic 1,2-hydroxylamino oximes containing the hydroxylamino group at the primary or secondary carbon atom with diacetyl afford 6-acetyl-5,6-dihydro-4H-1,2,5-oxadiazines. The reactions of these compounds with alkylaromatic 1,2-diketones produce N-substituted α-aroylnitrones or 6-aroyl-5,6-dihydro-4H-1,2,5-oxadiazines or, alternatively, their tautomeric mixtures. Dedicated to the memory of Academician V. A. Koptyug on the occasion of the 75th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1008–1013, June, 2006.     

Electrochemical reduction of 3,3′-bi(2-R-5,5-dimethyl-4-oxopyrrolinylidene)-1,1′-dioxides in water and its binary mixtures with acetonitrile

It has been shown by cyclic voltammetry for the first time for nitrons that the first step of electrochemical reduction of 3,3′-bi(2-R-5,5-dimethyl-4-oxopyrrolinylidene)-1,1′-dioxides in water and its binary mixtures with acetonitrile is a reversible one-electron process. The potentials of the first one-electron reduction peaks shift toward less negative values with an increase in the water content in the binary mixture, being in water equal to −0.14, −0.09, −0.08, and +0.19 V vs. saturated calomel electrode for dinitrons with R = Me, Ph, Bu^t, and CF₃, respectively. Such very low reduction potentials allow one to use derivatives of these dinitrons as redox-active labels in applied bioorganic electrochemistry. Dedicated to the memory of Academician N. N. Vorozhtsov on the 100th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1227–1229, June, 2007.     

Thermodynamic dissociation constants of salicylic and monochloroacetic acids in mixed solvent systems from conductance measurements at 25°C

The molar conductances of dilute solutions of salicylic and monochloroacetic acids in binary mixtures of methanol, ethanol, 1-propanol, N,N-dimethylformamide, acetone, acetonitrile, tetrahydrofuran and dioxane with water have been measured at 25°C. The Lee-Wheaton conductance equation was fitted to the data in order to derive thermodynamic dissociation constants and limiting molar conductances. The results were compared with those in the literature pertaining to analogous media, mostly derived potentiometrically. The findings are interpreted in terms of a solvent effect on the ionization of these acids in mixed solvent systems.This paper is dedicated to the late Professor Raymond M. Fuoss on his 3^rd anniversary.     

HPLC in photokinetics: Determination of reaction mechanism and photochemical quantum yields of (E)-1-phenylpropene

Summary A combined method of high-performance liquid chromatography and UV-absorption spectroscopy is described for use in dynamic systems. It provides a way of obtaining detailed mechanistic information as well as quantitative data (rate constants, quantum yields), even though neither mechanism nor photoproducts are known. The kinetic treatment of the photoreaction of (E)-1-phenylpropene was successful, showing a photo-isomerization and a parallel step. Information on this additional step is obtained by using HPLC to observe the changes in the concentrations of the reactants' selectivity. The necessity of process control is demonstrated.Dedicated to Prof. Ernst Bayer on the occasion of his 60^th anniversary.     

Incubation period in the 2,2,4,4‐tetramethyl‐1‐piperidinyloxy‐mediated thermal autopolymerization of styrene: Kinetics and simulations

Mechanisms and simulations of the induction period and the initial polymerization stages in the nitroxide‐mediated autopolymerization of styrene are discussed. At 120–125 °C and moderate 2,2,4,4‐tetramethyl‐1‐piperidinyloxy (TEMPO) concentrations (0.02–0.08 M), the main source of radicals is the hydrogen abstraction of the Mayo dimer by TEMPO [with the kinetic constant of hydrogen abstraction (k_h)]. At higher TEMPO concentrations ([N?] > 0.1 M), this reaction is still dominant, but radical generation by the direct attack against styrene by TEMPO, with kinetic constant of addition k_ad, also becomes relevant. From previous experimental data and simulations, initial estimates of k_h ≈ 1 and k_ad ≈ 6 × 10^?7 L mol^?1 s^?1 are obtained at 125 °C. From the induction period to the polymerization regime, there is an abrupt change in the dominant mechanism generating radicals because of the sudden decrease in the nitroxide radicals. Under induction‐period conditions, the simulations confirm the validity of the quasi‐steady‐state assumption (QSSA) for the Mayo dimer in this regime; however, after the induction period, the QSSA for the dimer is not valid, and this brings into question the scientific basis of the well‐known expression k_th[M]³ (where [M] is the monomer concentration and k_th is the kinetic constant of autoinitiation) for the autoinitiation rate in styrene polymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6962‐6979, 2006     

Preface

A small number of publications are collected in this Special Chapter of the J. Therm. Anal. Cal. All these publications of the Special Chapter are related to scientific areas, which are presented and discussed at our International Conferences on Pharmacy and Applied Physical Chemistry. Of course, the publications collected here are only some typical highlights compared with the scientific program of the PhandTA 8, Monte Verità, 2004 with 50 oral contributions and 25 poster presentations. A rather complete overview of the scientific program was presented in J. Therm. Anal. Cal., 57, 1999. The latter volume represents a considerable part of the contributions given at the PhandTA 3, held in 1997 at the Centro Stefano Fanscini at Monte Verità, Ascona, Switzerland. The scientific program is the essential part of our Conferences, however, the conference site at Monte Verità is by its history, by the site on top of a hill situated in a wonderful park, overlooking Ascona and the Lago Maggiore a rather ideal place for the conferences of our anticipated quality. The PhandTA conferences were three times held at Monte Verità. The next one, the PhandTA 9 will be held on September 10 to 13, 2006 at the “Institut für Pharmazeutische Technology und Biopharmazie”, University of Düsseldorf, Germany. The 10^th anniversary, namely the PhandTA 10, will be held from Sunday 21^st to Wednesday 24^th of October, 2007. This anniversary meeting will also express our activities over a period of 15 years since the foundation of the European Society for Applied Physical Chemistry in 1992. With both of these Conferences we plan to create a Special Chapter in the JTAC. I extend on behave of the members of the board of eurostar-science an invitation to the members of our society and to our scientific friends to participate in the two forthcoming PhandTA’s. Additionally, all possible participants should consider a publication of the presented scientific work in cooperation with the members of the board and the editors of this journal. Cordially, Erwin E. Marti President of the European Society for Applied Physical Chemistry     

Cryptic functions of enzymes in chemical catalysis

Using a number of examples, this article demonstrates how the functional groups responsible for the catalytic activity of an enzyme must be studied within the context of the enzyme-substrate complex. Very often a substrate will actively cooperate with the enzyme to bring about its own transformation. The so-called cryptic functions of enzymes are considered in the case of seryl proteases which, according to the type of substrate or structural modification introduced in the enzyme, may exhibit esterase, amidase, protease, racemase or dehydratase activity. The cryptic functions may possess a physiological significance which reflects the evolutionary history of the protein. Alternatively they may offer a simple way of exploiting the enzymes as catalysts capable of taking part in the chemical reactions of biotechnological interest but little physiological importance.This work is dedicated to Prof.E. Wünsch (München) at the occasion of his 60^th birthday.     

M. S. Tswett and the discovery of chromatography I: Early work (1899–1903)

Summary On the occasion of the 90th anniversary of the Warsaw lecture of M. S. Tswett representing the first report on the chromatographic technique, this two-part article outlines the evolution of the method. This part deals with Tswett's early work in 1899–1901 and his research in 1901–1903 leading to the lecture at Warsaw. The second part will deal with the fundamental twin papers of 1906, with his book of 1910, summarizing all his activities related to the investigation of plant pigments and to the development of chromatography, and with a few special questions related to Tswett's scientific activities in this field.Part II of this article will be published in the next month's issue ofChromatographia.