Regioselectivity of olefin oxidation by iodosobenzene catalyzed by metalloporphyrins : control by the catalyst

The regioselectivity of the oxidation of three monosubstituted olefins, 6-phenoxyhex-1-ene, hex-1-ene and styrene, by iodosobenzene in the presence of various Fe-, Mn- or Cr-tetraaryl-porphyrins, was studied. It was found that, besides epoxides, known products from such systems, allylic alcohols and aldehydes were formed, the latter not being derived from the corresponding epoxides. The relative importance of these reactions greatly depends upon both the metal and porphyrin constituents of the catalyst. More particularly, the competition between epoxidation and allylic hydroxylation can be efficiently controlled by non-bonded interactions between the olefin and porphyrin substituents. No hydroxylation of the aromatic rings and no oxidative dealkylation of the ether function was detected.     

Desymmetrization of Dicationic Diboranes by Isomerization Catalyzed by a Nucleophile

Cationic monoboranes exhibit a rich chemistry. By constrast, only a few cationic diboranes are known, that all are symmetrically substituted. In this work, the first unsymmetrically substituted dicationic diboranes, featuring sp²–sp²‐hybridized boron atoms, are reported. The compounds are formed by intramolecular rearrangement from preceding isomeric symmetrically substituted dicationic diboranes, a process that is catalyzed by nucleophiles. From the temperature‐dependence of the isomerization rate, activation parameters for this unprecedented rearrangement are derived. The difference in fluoride ion affinity between the two boron atoms and the bonding situation in these unique unsymmetrical dicationic diboranes are evaluated.     

Oxidation of 1,4-dimethylcyclohexane by perchloric acid catalyzed by polyphenylferrosiloxane

The reaction of oxidation of 1,4-dimethylcyclohexane (DMCH) by perchloric acid at ～20 °C catalyzed by polyphenylferrosiloxane has been found. The chromatographic analysis has revealed the formation of several products, including the tertiary alcohol with 100% retention of the configuration of the initial configuration. The specific feature of the process is the following: along with the high stereospecific formation of the tertiary alcohol,cis-trans isomerization in the starting 1,4-DMCH is observed. The data obtained are discussed on the basis of the mechanism, including the formation of a ferryl intermediate with the subsequent transfer of the oxygen atom to the tertiary C?H bond of 1,4-DMCH through the intermediate complex with the five-coordinated carbon.     

Production of Enzymes by Plant Cells Immobilized by Sol-Gel Silica

Ajuga reptans cells are cultivated and used for production of invertase. These plant cells are immobilized by a sol-gel SiO₂ membrane, which is built up directly on the cell surface by exposure to a gaseous flow of silicon alcoxide precursors. The immobilization modifies the metabolic activity of cells, resulting in a 40-fold increase in invertase production with respect of free cells. Results concerning total release of proteins, cell growth and produced invertase activity are discussed, considering the absence of breeding, induced by SiO₂ immobilization, the prominent factor promoting the observed exceptional increase in invertase productivity.     

Synthesis of arylaliphatic chlorosilanes by alkylation of aromatic compounds by alkenylchlorosilanes

Conclusions In combination with HCl or H₂O, EtAlCl₂ is an active catalyst for alkylation of aromatic compounds by alkenylchlorosilanes, and compounds of boron, titanium, and tin are inactive in this reaction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1639–1641, July, 1985.     

Optimal acidity of complexes by solution of polynomials and by iteration

The methods for optimal acidity of complexes M(x)L(y)(OH)(m)H(n) based on direct iteration or solution of polynomials are described and discussed. Then, by a direct straightforward method of computation (that does not require any iteration) the complexes M(x)L(OH)(m)H(n) and ML(y)(OH)(m)H(n) are treated (where 1 x 3 and 1 y 3). Finally, the conditions leading to formation of polynuclear complexes are shown and discussed. The importance of study of polynuclear complexes for solving of biochemical problems is pointed out. Practical examples are given for each method.     

Monoalkylation of acetonitrile by primary alcohols catalyzed by iridium complexes

The monoalkylation of acetonitrile by primary alcohols was achieved in a one-pot sequence in the presence of iridium catalysts. A diversity of nitriles has been obtained from aryl- and alkyl-methanols in excellent yield.     

Ring opening of aziridines by aromatic thiols followed by amino-substitution

Ring opening of 2-aziridinecarboxylic acid methyl ester by a number of aromatic thiols under solvent-free and non-catalytic conditions resulted in bis-arylsulfanyl propanoic acid esters.     

Hydroalumination of cycloolefins by diisobutylaluminum hydride catalyzed by zirconium compounds

Conclusions Zirconium chloroalkoxides are effective catalysts for the hydroalumination of cycloolefins by diisobutylaluminum hydride.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 669–673, March, 1982.     

Kinetics of chalcone oxidation by peroxide anion catalysed by poly-l-leucine

An insight into the kinetics, mechanism and optimum reaction conditions of the Julia-Colonna epoxidation has been gained using a soluble polyleucine catalyst.     

十六烷基三甲基溴化铵改进Hummers法制备石墨烯的研究

将阳离子表面活性剂（十六烷基三甲基溴化铵,CTAB）作为絮凝剂,利用其与氧化石墨烯（GO）产生静电吸引的原理,实现中间产物CTAB-GO复合物的快速分离和纯化,并利用水合肼还原制得还原氧化石墨烯（RGO）。采用UV-Vis、 SEM、 TEM、 AAS和XPS对石墨烯的形貌、纯度、制备过程及机理进行了分析表征。结果显示,CTAB能通过静电力吸附在GO表面,形成CTAB-GO复合物的絮凝沉淀。当CTAB和GO的质量比为1:2时,可以达到最佳的絮凝效果。该絮凝沉淀仅通过低压过滤或低速离心（3 000 rpm, 3 min）便能实现快速分离和纯化,得到CTAB-GO复合物。AAS和XPS证实CTAB-GO复合物中不存在杂质离子。此外,CTAB-GO复合物经过水合肼还原后,CTAB能快速完全脱除,从而得到高纯度RGO。     

The Reduction of Benzofuroxans by Ferrous Salts and by Thiophenol

Treatment of benzofuroxan derivatives with ferrous sulphate in DMSO/water solution affords in high yield o-nitroanilines. o-Nitroaniline was also obtained by reduction of benzofuroxan with thiophenol in presence of catalytic amount of Fe²⁺ or Fe³⁺ salts.     

Nanoporous carbons obtained by carbonization of copolymers impregnated by salts

This paper demonstrates the results of research on influence of types of polymer and kinds of salts used for impregnation of the polymer on porous structure formation in the final carbonaceous product. The studies were performed in two stages. In the first stage, the role of polymer structure were mainly studied. To achieve the aim, three different porous copolymers (polyimide and two types of polyester) were impregnated with the same salts (NiSO₄, and the mixture of AgNO₃ and Gd(NO₃)₃). In the second part of the study, only one polymer (polyimide) was impregnated by three mixtures of salts (chlorides, nitrates and sulphates of K, Cu(II) and Fe(III)). This approach allowed to evaluate the impact of the mixture of salts on porosity of the carbons, which were to be prepared. The obtained results revealed that when the impregnation was applied as a method for activation and moulding of porosity of carbonaceous materials prepared from polymers, several factors should be taken into account. First of all, initial decomposition temperatures of the polymers and the salts should be compared to find out if carbonization and activation processes proceed simultaneously or not. If the copolymer was carbonized and gases were released from decomposing salts, they reacted each other and synergic effect of polymer and salts properties were observed. Such conditions favored the development of microporous structure of the obtained carbon. On the contrary, if the processes were separated in time because of high temperature of melting point of the salts more mesopores were retained.