Organic synthesis based on cathodic deprotonation of acids

The results of studies on electrosynthesis involving carb- and heteroanions generated by cathodic deprotonation of acids (CDA), carried out in the laboratory headed by the author, are surveyed. These studies resulted in the elaboration of efficient electrochemical versions of the known Michaelis-Becker, Wittig-Horner, and Perkin reactions; electrochemical analogs of homolytic aromatic substitution, alkylation, heterocyclization,etc. were developed. Based on CDA, convenient and promising methods for preparing variousN-, O-, P-, S-, andC-alkylated and arylated substances have been developed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1411–1422, August, 1995.The author is grateful to Professor V. A. Dorokhov, Professor V. P. Litvinov, and researchers from the laboratories of N. D. Zelinsky Institute of Organic Chemistry headed by them, who participated in joint studies.The work was carried out with financial support from the International Science Foundation (Grant No. MHYOO).     

On the dynamical Casimir effect in a one-dimensional contracting cavity

The dynamical Casimir effect is analyzed in the framework of the S-matrix formulation for a one-dimensional cavity that exhibits contraction at a constant rate over a finite time interval. The exact solution to the problem is presented. It is demonstrated that the efficiency of the creation of pairs nonmonotonically depends on the contraction time. This is due to the fact that the particles are only created at the moments corresponding to the acceleration and stopping of the moving boundary, so that the contributions of these processes on the number of the created particles interfere with each other. The parameters that correspond to the optimal creation of pairs and the stability of a vacuum are presented. The effect of the finiteness of the cavity-boundary acceleration on the results obtained is studied.     

Subgame Consistent Cooperative Solutions in Stochastic Differential Games

Subgame consistency is a fundamental element in the solution of cooperative stochastic differential games. In particular, it ensures that: (i) the extension of the solution policy to a later starting time and to any possible state brought about by the prior optimal behavior of the players would remain optimal; (ii) all players do not have incentive to deviate from the initial plan. In this paper, we develop a mechanism for the derivation of the payoff distribution procedures of subgame consistent solutions in stochastic differential games with transferable payoffs. The payoff distribution procedure of the subgame consistent solution can be identified analytically under different optimality principles. Demonstration of the use of the technique for specific optimality principles is shown with an explicitly solvable game. For the first time, analytically tractable solutions of cooperative stochastic differential games with subgame consistency are derived.     

Synthesis on the basis of electrogenerated carbenes

A series ofS _N2 reactions with halomethanes as substrates and the corresponding anions as nucleophiles were studied by the semiempirical MNDO and AM1 methods, taking into account solvent effects. Analysis of the kinetics, structures of reagents, intermediates and products, and charge distribution in them allows one to draw the conclusion that the retardation ofS _N2 reactions is stronger in solvents than in the gas phase, and the rates of reactions involving anions with a lower number of halogen atoms are higher.For Part 8 see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2148–2154, November, 1995.This work was partially financially supported by the International Science Foundation (Grant No. MHYOO).     

Mass-spectrometric study of the cyclization of diazo ketones. 2. Cyclization of 1-diazo-4-sulfonylaminobutan-2-ones to N-sulfonylpyrrolidin-3-ones

A comparison of the mass spectra of 1-diazo-4-sulfonylamino-butan-2-ones and N-sulfonylpyrrolidin-3-ones makes it possible to conclude that under the conditions of electron impact and chemical ionization the molecular ions of the investigated diazo ketones lose a molecule of nitrogen and undergo partial cyclization to the corresponding pyrrolidinones without undergoing the Wolff rearrangement.See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 919–925, July, 1982.     

Dimerization of Sodium Enolates of Malonic Ester and Acetylacetone Effected by the Action of 4-Methyl-3,4-dibromotetrahydropyran

Russian Journal of Organic Chemistry -