L. L. Rodina

Sustainable Development in Higher Education in Russia: The Case of St. Petersburg State University.

This article focuses on attempts to introduce elements of sustainable development education into the curriculum of one of the largest Russian universities. At St. Petersburg State University, compulsory courses relevant to sustainable development have been introduced or modified in 14 faculties out of 20 during the last decade. Examples of environmentally oriented projects within and outside the university are given. The authors touch upon the state of affairs in higher education in Russia, and write about sustainable development in a wider sense, beyond the environmental context. Sustainable development in education for Russia is one of the most important pre-requisites for sustainable development in society. A model for reforming the system of national higher education is given to illustrate possible ways of achieving sustainability in education.

Sustainable development in higher education in Russia

This article focuses on attempts to introduce elements of sustainable development education into the curriculum of one of the largest Russian universities. At St Petersburg State University, compulsory courses relevant to sustainable development have been introduced or modified in 14 faculties out of 20 during the last decade. Examples of environmentally oriented projects within and outside the university are given. The authors touch upon the state of affairs in higher education in Russia, and write about sustainable development in a wider sense, beyond the environmental context. Sustainable development in education for Russia is one of the most important prerequisites for sustainable development in society. A model for reforming the system of national higher education is given to illustrate possible ways of achieving sustainability in education.

Chemistry of Diazocarbonyl Compounds: XX. Chemoselective O-Alkylation of 3(2H)-Oxoisothiazole-1,1-dioxides

Catalytic decomposition of diazoacetylacetone, ethyl diazoacetate, and diethyl diazomalonate effected by dirhodium tetraacetate in the presence of 3(2H)-oxoisothiazole-1,1-dioxides resulted in O-alkylation of amide carbonyl of the heterocycle affording the corresponding enol ethers in preparative yield. The reaction occurred chemoselectively. The 1,3-dicarbonyl derivatives of 3-hydroxyisothiazole-1,1-dioxides obtained in contrast to analogous N-alkylated products are not enolized in solutions and in crystals.

Less reactive dipoles of diazodicarbonyl compounds in reaction with cycloaliphatic thioketones - First evidence for the 1,3-oxathiole-thiocarbonyl ylide interconversion

Summary Acyclic diazodicarbonyl compounds react at room temperature with cycloaliphatic thioketones, e.g. 2,2,4,4-tetramethyl-3-thioxocyclobutanе-1-one and adamantanethione, via a cascade process in which the key step is a 1,5-electrocyclization of the intermediate thiocarbonyl ylide leading to tetrasubstituted spirocyclic 1,3-oxathioles. The most reactive diazodicarbonyl compound was diazoacetylacetone. In the case of dimethyl diazomalonate competitive 1,3-electrocyclization yielded the corresponding thiirane at elevated temperature, which after spontaneous desulfurization produced a tetrasubstituted alkene. To explain the observed temperature dependence of the main reaction product type obtained from dimethyl diazomalonate and 2,2,4,4-tetramethyl-3-thioxocyclobutanе-1-one as well as to verify reversibility of the thiocarbonyl ylide and 1,3-oxathiole interconversion, the calculations of the energy profile for the transformation of 1,3-oxathiole to alkene were performed at the DFT PBE1PBE/6-31G(d) level.

Photolysis of Regioisomeric α,α-Diphenyl-Substituted Diazotetrahydrofuranones: Primary and Secondary Photochemical Processes

The formation of C–H insertion products in the course of direct photolysis of α,α-diphenylsubstituted diazo ketones of the tetrahydrofuran series was rationalized by secondary photochemical processes which give rise to benzophenone acting as a sensitizer. Triplet excited states of diazo ketones generated by the action of benzophenone are capable of undergoing bimolecular transformations.

Modern Trends of Organic Chemistry in Russian Universities

This review is devoted to the scientific achievements of the departments of organic chemistry in higher schools of Russia within the past decade.

4-azidoquinoline N-oxide: Synthesis and photolysis

In photolysis of 4-azidoquinoline N-oxide azoxy compound was isolated as the final reaction product. This result may be ascribed to the dimerization of the intermediate nitrene to azo compound followed by oxidation of the latter with air oxygen. The initially arising nitrene is stabilized by resonance conjugation involving the aromatic system and the N-oxide group. The rate constants of 4-azidoquinoline N-oxide photolysis were measured in various solvents and the values of spin density and bond lengths in the formed nitrene were calculated.

On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation

Summary The 1,3-dipolar cycloaddition of acyclic 2-diazo-1,3-dicarbonyl compounds (DDC) and thioketones preferably occurs with Z,E-conformers and leads to the formation of transient thiocarbonyl ylides in two stages. The thermodynamically favorable further transformation of C=S ylides bearing at least one acyl group is identified as the 1,5-electrocyclization into 1,3-oxathioles. However, in the case of diazomalonates, the dominating process is 1,3-cyclization into thiiranes followed by their spontaneous desulfurization yielding the corresponding alkenes. Finally, carbocyclic diazodiketones are much less reactive under similar conditions due to the locked cyclic structure and are unfavorable for the 1,3-dipolar cycloaddition due to the Z,Z-conformation of the diazo molecule. This structure results in high, positive values of the Gibbs free energy change for the first stage of the cycloaddition process.

Thermolysis and acid-catalyzed decomposition of 4-diazotetrahydrofuran-3-ones. A new efficient synthesis of tetrasubstituted dihydrofuran-3-ones

The Wolff rearrangement is one of the most characteristic transformations of diazo ketones [1]. Diazo ketones of the tetrahydrofuran series are thus converted into oxetane derivatives. Using tetramethylsubstituted diazotetrahydrofuranone as an example, we previously showed [2] that its photolytic Wolff rearrangement was the most efficient [2]. Photoinduced reactions of aryl-substituted diazotetrahydrofuranones are characterized by lower selectivity, and they give rise to a number of products [3, 4]. The goal of the present work was to study thermal and acid-catalyzed decomposition of 2,2,5,5-tetrasubstituted 4-diazotetrahydrofuran-3-ones, compare the results with those obtained by photolysis, and estimate synthetic potential of these processes. As substrates we selected 4-diazo-2,2,5,5-tetramethyltetrahydrofuran-3one (I), 4-diazo-2,2-dimethyl-5,5-diphenyltetrahydrofuran-3-one (IIa), 4-diazo-5,5-bis(4-fluorophenyl)-2,2dimethyltetrahydrofuran-3-one (IIb), 4-diazo-5,5-dimethyl-2,2-diphenyltetrahydrofuran-3-one (IIIa), and 4-diazo-2,2-bis(4-fluorophenyl)-5,5-dimethyltetrahydrofuran-3-one (IIIb). in the absence of solvent (in melt), and the progress of reactions was monitored by TLC and H NMR.

Kinetics of 1,3-Cycloaddition of α-Diazoalkanones to Maleic Anhydride

The kinetics of 1,3-cycloaddition to maleic anhydride were studied by examples of reaction with five-, six-, and seven-membered α-diazocycloalkanones. The order of magnitude of the thermodynamic activation parameters in the reaction series investigated corresponds to a concerted mechanism of the process under consideration.