Reaction of Olefins with Anodically Generated Radical Cations of Trialkyl Phosphites and Dialkyl Trimethylsilyl Phosphites

Electrochemical oxidation of trialkyl phosphites and dialkyl trimethylsilyl phosphites in the presence of olefins yields mixtures of isomeric dialkyl alkenyl(cycloalkenyl)phosphonates with predominating [alken(cycloalken)-2-yl]phosphonates. A scheme of the process was proposed, which involves attack of the alkene double bond by anodically generated radical cations of phosphites, followed by a second electron transfer, deprotonation, and elimination of cationic species: alkyl cation in the case of trialkyl phosphites and trimethylsilyl cation in the case trimethylsilyl phosphites

Finely dispersed minerals in destruction zones of deep horizons – catalyzers of geofluid transformation

© SGEM2015. Based on experimental simulation implementation of catalytic mechanism of generating hydrocarbon systems containing gas and liquid phases from methane is revealed in destruction zones of the crystalline basement of Eastern Russian Plate. Catalytic activity of finely dispersed clay minerals of destruction zones is studied in the presence of reservoir water. Simulation experiments showed possibility of generating gaseous and liquid petroleum hydrocarbons in destruction zones of the crystalline basement of paleo platforms. Generation process is carried out under the catalytic activity of natural finely dispersed clay associates in the presence of promoting additives in reservoir water. Hydrocarbon content is determined by the ratio of intermediate compounds formed as a result of partly implemented steam reforming, their conversion by Fischer-Tropsch mechanism into different sealing products. Such zones of the crystalline basement in deep horizons can act as a “chemical reactor” for generating hydrocarbon systems, the total yield of which is defined by duration of initial components contact

Free-Radical Phosphorylation of Olefins Initiated by Anodic Oxidation

Electrochemical oxidation of lithium and sodium dialkyl phosphites generates dialkyl phosphonyl radicals, which initiate chain free-radical addition of dialkyl phosphites across the alkene multiple bond to form alkyl(cycloalkyl)phosphonates. Alkyl(cycloalkyl)phosphonates are formed simultaneously owing to anodic oxidation of adsorbed primary radical adducts of phosphonyl radical and alkene molecule to give the carbenium cation, followed by deprotonation of the latter

Elite opinion and foreign policy in post-communist Russia

Russian elite opinion on matters of foreign policy may be classified as ‘Liberal Westerniser’, ‘Pragmatic Nationalist’ and ‘Fundamentalist Nationalist’, terms that reflect longstanding debates about the country’s relationship with the outside world. An analysis of press statements and election manifestoes together with a programme of elite interviews between 2004 and 2006 suggests a clustering of opinion on a series of strategic issues. Liberal Westernisers seek the closest possible relationship with Europe, and favour eventual membership of the EU and NATO. Pragmatic Nationalists are more inclined to favour practical co-operation, and do not assume an identity of values or interests with the Western countries. Fundamentalist Nationalists place more emphasis on the other former Soviet republics, and on Asia as much as Europe, and see the West as a threat to Russian values as well as to its state interests. Each of these positions, in turn, draws on an identifiable set of domestic constituencies: Liberal Westernisers on the promarket political parties, Pragmatic Nationalists on the presidential administration and defence and security ministries, and Fundamentalist Nationalists on the Orthodox Church and Communists

Oil generation potential of the Permian deposits of Tatarstan based on the content, structure and thermal stability of organic matter in rocks

© SGEM2016.With the use of thermal analysis and Rock-Eval, as well as on the basis of changes in the content and features of the group and the hydrocarbon composition of organic matter in samples of oil and bitumen-containing rocks of Permian deposits in Tatarstan, according to their mineral composition, evaluated the types of hydrocarbon fluids and oil generation potential of the rocks

The influence of transition metals–Fe, Co, Cu on transformation of organic matters from Domanic rocks in hydrothermal catalytic system

© 2018, © 2018 Taylor & Francis Group, LLC. Character of conversion of organic matter from Domanic rocks of Pervomaiskoye field (Tatarstan) of Semiluki horizon of upper Devonian deposits in the hydrothermal-catalytic system at temperature of 300 °C in carbon dioxide medium was studied with the application of complex of oil-soluble precursors of catalysts containing Fe, Co, and Cu. In presence of catalysts complex, content of organic extract increases, in which content of hydrocarbon fractions, saturated and aromatic hydrocarbons, increases 1.5 times, while resins content decreases by two times. As result of kerogen destruction in products of experiments, the content of asphaltenes and carbonaceous substances such as carbenes and carboides increase

Conversion of Heavy Oil with Different Chemical Compositions under Catalytic Aquathermolysis with an Amphiphilic Fe-Co-Cu Catalyst and Kaolin

© 2018 American Chemical Society. The physical simulation of heavy oil catalytic aquathermolysis with different chemical compositions from deposits located in the Tatarstan Republic, Russia (Ekaterinovsky oil, B2 type, and Olimpiadovsky oil, A1 type), was designed. The catalytic aquathermolysis processes were conducted at a temperature of 300 °C in the presence of a rock-forming additive - kaolin (the content of montmorillonite was 44%), and catalysts composed of transition metal (Fe, Co, and Cu) carboxylates. The environment of the processes was a mixture of carbon dioxide and water vapor. The distinctive features of hydrothermal-catalytic conversion of various oil types are evaluated by fractional, structural-group, microelement compositions, and H:C ratio changes. These variations are due to initial properties of crude oils and the activation degree of destruction reactions on C-C, C-N, C-O, and C-S bonds leading to different levels of increase of saturated fractions content and decrease of resins and asphaltenes content in the products of experiments. By the thermal analysis method, the assessment of potential content of the oil on a solid sorbent before and after experiments was carried out. The high-molecular-weight components of the naphthene-aromatic B2 type oil revealed greater adsorption capacity to the rocks, in comparison with the oil of the A1 type. Therefore, the adsorption of catalyst components on rocks is also greater

Electrochemically induced phosphorylation of alkenes

The processes of electrochemical phosphorylation of alkenes were investigated. It was found that anodically generated radical-cations of trialkyl phosphites, dialkyl trimethylsilyl phosphites, mono-and diamidophosphites were added to olefin molecules to give unsaturated alkenephosphonates. The anodic oxidation of tetraalkyl pyrophosphites proceeds with disintegration of initial radical-cations and leads to mixture alkane-and alkenephosphonates. Greater amounts of alkanephosphonates were formed during anodic oxidation of sodium (or lithium) dialkyl phosphites in the presence of alkenes. © 1997 Published by Elsevier Science Ltd

Безопасное тестирование симуляции систем с отказами и разрушением

The paper deals with conformance testing based on formal specications. The con- cept of safe testing was earlier proposed by the authors for trace based conformance. This concept is propagated on the case of (weak) simulation based on a relation between specication and implementation states. The theory of safe simulation of systems with refusals and destructions is proposed. The problems of complete testing and sucient conditions for the existense of complete test suite are discussed. The practical algo- rithm of complete testing for restricted classes of specications and implementations is described.Статья посвящена тестированию соответствия (конформности) реализации требованиям спецификации. Идея безопасного тестирования предложена авторами для конформности, основанной на трассах наблюдений. Эта идея распространяется на случай (слабой) симуляции, основанной на соответствии состояний реализации и спецификации. Предлагается теория безопасной симуляции для систем с отказами и разрушением. Обсуждаются вопросы полноты тестирования и достаточные условия существования полного набора тестов. Предлагается алгоритм полного тестирования для практического применения, опирающийся на некоторые ограничения на реализацию и спецификацию

Generation of Hydrocarbons by Hydrothermal Transformation of Organic Matter of Domanik Rocks

© 2016, Springer Science+Business Media New York.The distinctive properties of products of hydrothermal transformations of organic matter of bituminous rocks from Upper Devonian Domanik carbonate-argillaceous deposits of the Romashkino field, which were formed due to generation of bituminous components present in the rock in free state as well as of hydrocarbons and high-molecular heteroatomic compounds in the insoluble kerogen degradation process, are determined. It is shown that, among the n-alkanes, homologs with even number of carbon atoms dominate in the kerogen degradation products and that the asphaltenes contain two solid disperse phases differing in aromaticity, heteroatom, microelement and vanadium porphyry complex contents, free radical concentration, and solubility in organic solvents. The sequence of leaching out of hydrocarbons, heteroatomic compounds, resins, and asphaltenes from the rock by vapor-gas mixture is studied. The migration and adsorption capacity of n-alkanes with even and odd numbers of carbon atoms is shown to be diverse. Changes in the microstructure of Domanik rocks upon hydrothermal transformations are studied