V. D. Filimonov

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.

Surface modification of biomaterials based on high-molecular polylactic acid and their effect on inflammatory reactions of primary human monocyte-derived macrophages: Perspective for personalized therapy

Polylactic acid (PLA) based implants can cause inflammatory complications. Macrophages are key innate immune cells that control inflammation. To provide higher biocompatibility of PLA-based implants with local innate immune cells their surface properties have to be improved. In our study surface modification technique for high-molecular PLA (MW=1,646,600g/mol) based biomaterials was originally developed and successfully applied. Optimal modification conditions were determined. Treatment of PLA films with toluene/ethanol=3/7 mixture for 10min with subsequent exposure in 0.001M brilliant green dye (BGD) solution allows to entrap approximately 10(-9)mol/cm(2) model biomolecules. The modified PLA film surface was characterized by optical microscopy, SERS, FT-IR, UV and TG/DTA/DSC analysis. Tensile strain of modified films was determined as well. The effect of PLA films modified with BGD on the inflammatory reactions of primary human monocyte-derived macrophages was investigated. We developed in vitro test-system by differentiating primary monocyte-derived macrophages on a coating material. Type 1 and type 2 inflammatory cytokines (TNFα, CCL18) secretion and histological biomarkers (CD206, stabilin-1) expression were analyzed by ELISA and confocal microscopy respectively. BGD-modified materials have improved thermal stability and good mechanical properties. However, BGD modifications induced additional donor-specific inflammatory reactions and suppressed tolerogenic phenotype of macrophages. Therefore, our test-system successfully demonstrated specific immunomodulatory effects of original and modified PLA-based biomaterials, and can be further applied for the examination of improved coatings for implants and identification of patient-specific reactions to implants.

2,4,6,8-Tetraiodoglycoluril in sulfuric acid as a new powerful reagent for iodination of deactivated arenes

Abstract Deactivated arenes are iodinated readily at 0°C by the action of 2,4,6,8-tetraiodoglycoluril in sulfuric acid to give the iodoarenes in generally good yields.

1,3-Diiodo-5,5-dimethylhydantoin—An efficient reagent for iodination of aromatic compounds

Abstract1,3-Diiodo-5,5-dimethylhydantoin in organic solvents successfully iodinates alkylbenzenes, aromatic amines, and phenyl ethers. The reactivity of electrophilic iodine is controlled by acidity of the medium. Superelectrophilic iodine generated upon dissolution of 1,3-diiodo-5,5-dimethylhydantoin in sulfuric acid readily reacts with electron-deficient arenes at 0 to 20°C with formation of the corresponding iodo derivatives in good yields. The structure of electrophilic iodine species generated from 1,3-diiodo-5,5-dimethylhydantoin in sulfuric acid is discussed.

A Facile Synthesis of α -Iodo- β -nitroalkenes from Alkynes Using I2/NO3 − or KI/NO3 −

Abstract A covenient method with I2/NO3 − or KI/NO3 − has been developed for the synthesis of α -iodo- β -nitroalkenes from alkynes.

Matsuda–Heck reaction with arenediazonium tosylates in water

Summary An environmentally friendly Matsuda–Heck reaction with arenediazonium tosylates has been developed for the first time. A range of alkenes was arylated in good to quantitative yields in water. The reaction is significantly accelerated when carried out under microwave heating. The arylation of haloalkylacrylates with diazonium salts has been implemented for the first time.

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.

(Dichloroiodo)benzene—An Easily Available Reagent for Chloro‐ and Iodoalkoxylation, Iodohydroxylation, and Iodochlorination of Alkenes

Abstract A convenient synthesis of vicinal methoxychlorides, methoxyiodides, iodhydrines and iodocloride from alkenes using PhICl2/CH3OH, I2/PhICl2/CH3OH, I2/PhICl2/CH3CN/H2O and I2/PhICl2/CH2Cl2 is described.

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