E. A. Krasnokutskaya

Unusually Stable, Versatile, and Pure Arenediazonium Tosylates: Their Preparation, Structures, and Synthetic Applicability

A new, simple, and effective method for the diazotization of a wide range of arylamines has been developed by using a polymer-supported diazotization agent in the presence of p-toluenesulfonic acid. Various pure arenediazonium tosylates with unusual stabilities can be easily prepared by this method. As a result, these salts are useful and versatile substrates for subsequent transformations, such as halogenation and Heck-type reactions. The unusual stabilities of arenediazonium tosylates are also preliminarily discussed with their X-ray structures.

DFT investigation of the thermodynamics and mechanism of electrophilic chlorination and iodination of arenes

Quantum chemical calculations at the B3LYP/6-311G* level have been carried out in order to investigate the reaction mechanisms of the iodination of benzene and its monosubstituted derivatives with ICl, I+, I3+ and reagents containing N–I and O–I bonds as the iodinating agents. The results are compared with those obtained for chlorination by Cl+ and Cl2, both in the gas phase and in methanol solution using the PCM solvent model. We have also used the MP2/DGDZVP level of theory and the IEFPCM model to perform comparisons in a few cases. The thermodynamic parameters for the reactions have been calculated, the structures of the intermediate products (π- and σ-complexes) and transition states have been optimized, and the profiles of the free energy surfaces have been constructed.

Solvent‐Free Iodination of Arenes using Iodine–Silver Nitrate Combination

Abstract A simple and environmentally safe general method of iodination of aromatic substrates under sovent‐free conditions using the I2/AgNO3 combination in a solid state is reported. Both activated and deactivated aromatic compounds afford the respective aryl iodides in generally high yields (80–90%).

Generation of electrophilic iodine from iodine monochloride in neutral media. Iodination and protodeiodination of carbazole

In reaction of iodine monochloride with CF3COOAg, CH3COONa or (CH3COO)2Pb in acetonitrile and acetic acid the chloride is bonded by metal cations, and electrophilic iodine is generated able to easily iodinate anthracene and carbazole. However at the iodination of anthracene in the presence of oxygen the prevailing process is anthracene oxidation to anthraquinone. In the presence of sulfuric acid protodeiodination of 3-iodocarbazole was found to occur resulting in rearranged products.

A simple and efficient procedure for diazotization-iodination of aromatic amines in aqueous pastes by the action of sodium nitrite and sodium hydrogen sulfate

One of the most widely used methods of synthesis of aromatic iodides is based on diazotization–iodina-tion of aromatic amines. The diazotization is generally carried out using accessible sodium nitrite in strongly acidic medium at reduced temperature [1–5]. Alter-native procedures involve more expensive alkyl nitrites as diazotizing agents in the presence of diiodomethane or other sources of iodine [6, 7]. We previously pro-posed simple procedures for diazotization–iodination with sodium nitrite at room temperature in weakly acidic media created by

Organic chemistry. History and mutual relations of universities of Russia

The review describes the history of development of organic chemistry in higher schools of Russia over a period of 170 years, since the emergence of organic chemistry in our country till now.

Modern Trends of Organic Chemistry in Russian Universities

This review is devoted to the scientific achievements of the departments of organic chemistry in higher schools of Russia within the past decade.

Latent ruthenium carbene complexes with six-membered N- and S-chelate rings

New ruthenium carbene complexes with chelating N- and S-benzylidene ligands were synthesized by the reactions of second- and third-generation Grubbs catalysts with ortho-vinylbenzyl-substituted amines or sulfides. These complexes were shown to exhibit catalytic activity in ring-opening metathesis polymerization and ring-closing metathesis.

Pyridinyl trifluoromethanesulfonates: preparation methods and use in organic synthesis

The methods for the synthesis of pyridinyl trifluoromethanesulfonates are reviewed. Examples of their use in organic synthesis for the production of valuable products are presented.

N-chelate ruthenium carbene complexes in olefin metathesis and isomerization

The catalytic activity of N-chelate ruthenium carbene complexes in the metathesis of hex-1-ene has been studied in comparison to the second generation Grubbs catalyst.