Electrocatalytic reactions: anion radical cyclobutanation reactions and electrogenerated base reactions

Intermolecular anion radical [2+2] cyclobutanation reactions have been observed between vinyl sulfones and vinyl/propenyl ketones. The products are novel and formed electrocatalytically, although yields are at best modest (11-45%). Competing mechanisms are discussed. Additionally, the electrochemical reduction of vinyl alkyl sulfones in acetonitrile leads to near quantitative formation of cyanomethylation product cyano-sulfones. The single step approach has electrocatalytic factors in excess of thirty.     

Electroprotic reactions

Reactions involving the coupled transfer of electrons and protons are called electroprotic reactions. In this article we briefly describe some of our experiences with electroprotic reaction as a tool for executing interesting chemical transformations.     

Carbonylation reactions

Conclusions From the UV spectra it follows that the chain reaction for the carbonylation of piperidine, initiated by CuCl₂, proceeds via the Intermediate formation of charge-transfer complexes, in which the Cu²⁺ ion undergoes oxidation-reduction reaction with the free electron pair of the amine.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2705–2708, December, 1973.     

Topochemical reactions

A survey of topochemical reactions is given and the theory of their kinetics is discussed. The first part of this study [1] deal with the autolocalization, now the factors leading the autolocalization are under consideration.     

Topochemical reactions

A survey of topochemical reactions is given and the theory of their kinetics is discussed.

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Zusammenfassung Eine Übersicht über die topochemische Reaktion wird gegeben und die Theorie ihrer Kinetik erörtert.

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Résumé On présente une étude d'ensemble sur les réactions topochimiques en discutant la théorie de la cinétique.

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This paper was written from a series of lectures read by the author at the First All-Union School on the Chemistry of Solids (Novotsherkask, September 1972).     

Carbonylation reactions

Conclusions 1-Propanol and 1-butanol are carbonylated with CO in the presence of CuCl₂ to give dialkyl carbonates at <100° and alkyl formates at >100°; at >100° the carbonylation is accompanied by dehydration and hydrochlorination reactions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 804–806, April, 1973.     

Pseudo-zero-order reactions

Reactions at the very first instant of their life, i.e., short after their start, follow a pseudo-zero-order kinetics. The initial rate method studying the very first instants of a reaction, which, i.e., can last hours, if k is in days, when it is applied to the integrated rate laws, allows to approximate any kinetics with a pseudo-zero-order. This kind of kinetics allows, nevertheless to derive valuable information about the characteristics of a reaction, which can be obtained by running the reaction at different initial concentrations. This could spare a lot of time required normally for collecting kinetic data over three or more half-lives.     

Amplification reactions

Amplification methods were first used over 100 years ago but the term only came into general usage during the development of microanalytical techniques. There has been a revived interest in amplification methods during the last few years, for it has been realized that by their application to trace analysis, it is often possible to obtain unusally precise results. The amplification methods available for various cations and anions are reviewed.