Electrochemical reduction of 1,1-dihalo-2,2-disubstituted cyclopropanes

The electrochemical reduction of 1,1-dihalo-2-R-2-methylcyclopropanes was studied by polarography and preparative electrolysis. A mixture of stereoisomeric monoboro- and monochlorocyclopropanes was obtained with preparative yield of 60–70% in preparative electroreduction in methanol against a background of 0.1 M LiClO₄. In the case of bromine derivatives of cyclopropanes (except when R = CN) an effect was found on the part of the current density on the ratio of cis and trans isomers, which was interpreted as a change, in dependence on current density, of the contributions of the reactions of reduction of the starting compounds (S_N2 mechanism) and ionic pairs (S_N1 mechanism). The effect of the solvent (CHCl₃, DMF, DMSO, MeOH) and background salt (LiClO₄, Et₄NBr) on the ratio of stereoisomers is in agreement with this interpretation.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2023–2032, September, 1992.     

On the function of action on a manifold of ground state solutions

The functions of action and energy are introduced on a manifold of ground states of the Euclidian scalar field functional of action. The differential identity connecting these two functions is proved.Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 105, No. 3, pp. 438–449, December, 1995.     

Spin-spin coupling of77Se and31P nuclei in cyclic organophosphorous compounds

We have established that direct phosphorus-selenium spin-spin coupling constants in cyclic compounds with P=Se exocyclic and P-C endocyclic bonds are found in the range¹J_PSe=–708 to –859 Hz; in this case, it is greater for the axial orientation of P=Se than for the equatorial orientation.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 776–780, April, 1990.     

Condensation of methyl 2-chloro-3-(3-nitrophenyl)-2,3-epoxypropionate with 1,2-phenylene diamine

It is established that the -chloroepoxide methyl 2-chloro-3-(3-nitrophenyl)-2, 3-epoxypropionate, in contrast to its a-chloroketone isomer methyl 3-(3-nitrophenyl-3-chloro-2-oxopropionate, forms 2-(3-nitrophenyl-3methoxycarbonylquinoxaline in reaction with 1,2-phenylene diamine, whereas the condensation of the achloroketone with 1,2 phenylene diamine gives 3-(-chloro-3-nitrophenyl)-2-oxo-1,2-dihydroquinoxaline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1105-1108, August, 1994.     

Synthetic analogs of active centers of iron-sulfur proteins: Reactions with phosphates

The interaction of synthetic analogs of active centers of iron-sulfur proteins with phosphates of different structures was studied. It was shown that the process involves ligand exchange and obeys the first-order reaction kinetic equation. The most rapid exchange occurred with the most acidic compound diphenyl phosphate.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2301–2305, October, 1992.     

ESR study of NiIII complexes with nitrosonaphthols and dithio acids

Mixed-ligand Ni^III complexes with -nitroso--naphthol, -nitroso--naphthol,o-ethylxanthate, andN,N-diethyldithiocarbamate as ligands have been studied by ESR in liquid and frozen solutions. The degrees of symmetry distortion for the first coordination sphere of these complexes have been determined. It is shown that the transition from planar square Ni^IIL₂ complexes to more stable octahedral Ni^IIIL₂L and Ni^IIILL₂ complexes occursvia the radical addition mechanism. A method for trapping short-lived radicals is suggested on the basis of the complex formation scheme.Translted fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1513–1515, August, 1995.The work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-5050)     

Synthesis of some new derivatives of dithiene-and oxathienecarboxylic acids

Substituted anilides of 1,4-dithiene- and oxathienecarboxylic acids were synthesized. It was shown that the reaction of 3-phenyl-1,4-dithi-2-ene-2-carboxyl chloride with 2-aminopyridines, depending on the base used and the reaction conditions, leads to the formation of N-[3-phenyl-2-(1,4-dithi-2-en)ylcarbonyl]2-amino-pyridine and/or N,N-bis[3-phenyl-2-(1,4-dithi-2-en)-ylcarbonyl]pyridonimine. The data of IR, UV, and PME spectroscopy were used to confirm the structure of the synthesized compounds.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Science Center, Russian Academy of Sciences. Kazan 420083. Translated fro, Khimiya Geterotskiklicheskikh Soedinenii, No. 9, pp. 1191–1196, September, 1994. Original article submitted May 10, 1994.