199Hg and13C NMR spectra of bromine-substituted benzyl derivatives of mercury

Conclusions ¹⁹⁹Hg chemical shifts indicate that in dibenzyl derivatives of mercury and in benzylmercury bromides, there is, conjugation of the C-Hg bond with the orbitals of the aromatic ring, and also intramolecular coordination of the Hg atom with the Br atoms located in the o-position relative to the CH₂HgBr group, leading to the formation of a five-membered chelate ring. Such coordination interaction does not have an appreciable effect on the¹³C chemical shifts or the J_C-Hg constants.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 793–799, April, 1985.     

Electrochemically induced formation of organomercury compounds

A procedure for the alkylation of metallic mercury by (dimethylglyoximato)butylcobalt(III) electrochemically generated in the presence of butyl bromide is proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 309–312, February, 1994.     

A new method for the generation of stable phenoxyl radicals by the reaction of [(Me3Si)2N]2E (E = Ge,Sn) with sterically hindered phenols

An unusual reaction of diaminogermylene and diaminostannylene with sterically hindered phenols which leads to the formation of stable phenoxyl radicals in high concentrations was found. The reaction mechanism was proposed. Amides [(Me₃Si)₂N]₂E (E = Ge, Sn) were investigated electrochemically.     

Synthesis and Steric Structure of Aroxypropynyl Alcohols of the Tetrahydropyran and Tetrahydrothiopyran Series

Optimal conditions have been developed for the synthesis and isolation of phenoxy- and benzyloxypropynyl alcohols of the tetrahydropyran and tetrahydrothiopyran series. The structures of individual isomers have been established on the basis of the ¹H and ^13C NMR spectra. The stereochemical results of the reaction depend on the initial ketone structure.     

Reactivity of some “ladder” type complexes under conditions of metallation

The behavior of binuclear “ladder” type complexes FpL, where Fp=Cp(CO)₂Fe, L=p-MeC₆H₄Cr(CO)₃ (4), CH₂C₆H₅Cr(CO)₃ (5), andp-FpC₆H₄Cr(CO)₃ (6), under conditions of metallation was studied. Unlike compounds5 and6, the σ-bound ligand L in compound4 migrates from the iron atom to the cyclopentadienyl ring to give complexes Me(CO)₂FeC₅H₄−C₆H₄(p-Me)Cr(CO)₃. The electrochemical reduction potentials of the complexes4–6 and the rearrangement products were measured. The migration activity of L is determined by the ease of reductive cleavage of the Fe−L bond and the susceptibility of the system to undergo intramolecular electron transfer from the Cp ligand to the aromatic ring. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1832–1835, September, 1998.     

Synthesis and steric structure of aryloxypropynyl alcohols of the phosphinane series

Phenoxy-and benzyloxypropynyl alcohols of the phosphinane series are synthesized. The steric structure of individual isomers is established by means of ¹H and ¹³C NMR spectroscopy. Stereodirection of the ethynylation of trans- and cis-2,5-dimethyl-1-phenyl-2-thioxo-λ⁵-phosphinane-4-ones is studied.     

Polyfunctional macroheterocycles. 7. Synthetic enzyme analogs. synthesis of 16- and 22-membered nitrogen and sulfur crown compounds containing exocyclic histamine and histidine fragments and carboxyl groups

The acid hydrolysis of 9,14-bis(2-methoxycarbonylethyl)-11-12-benzo-3,4-(4,5-dimethylbenzo)-10,13-dioxo-1,6-dithia-9,14-diazacyclohexadeca-3,11-diene leads to the corresponding 9,14-biscarboxy derivative. The reaction of 4,9,15,20-tetrakis-(2-methoxycarbonylethyl)-6,7,17,18-dibenzo-5,8,16,19-tetraoxo-1,12-dithia-4,9,15,20-tetraazacyclodocosa-6,17-diene with hydrazine hydrate and subsequent treatment with NaNO₂ gave the corresponding tetraazide. The reaction of this tetraazide with histamine and histidine leads to macroheterocycles, containing exocyclic histamine and histidine fragments.For Communication 6, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 130–133, January, 1993.     

Electrochemical study of some bromo-substituted [2.2]paracyclophanes

The potentials of electrochemical oxidation ( ) and reduction ( ) of monobromo- and isomeric di- and tribromo[2.2]paracyclophanes as well as of mono-, di-, and tribromobenzenes were measured in acetonitrile. The similarity between the properties ofpseudo-para-disubstituted cyclophanes andmeta-disubstituted benzenes, on the one hand, andpseudo-meta-disubstituted cyclophanes andpara-disubstituted benzenes, on the other hand, was confirmed by the existence of a linear relationship between of bromo-substituted [2.2]paracyclophanes and of the corresponding bromo-substituted benzenes. The results were explained in terms of the qualitative theory of molecular orbitals, taking into account a through space interaction between the -systems of the benzene rings.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 839–845, May, 1994.The authors wish to express their gratitude to Professor R. Hoffmann (Cornell University, USA) for a useful discussion and criticisms of the text of this paper.This work was financially supported by the Russian Foundation for Basic Research (Project 93-03-5246).     

Alkylation of cobalt and lutetium tetra(3,5-di-tert-butyl-4-hydroxyphenyl)dodecachlorophthalocyanine complexes initiated with current

Electrochemical properties of tetra(3,5-di-tert-butyl-4-hydroxyphenyl)dodecachlorophthalocyanine complexes of cobalt(II) and lutetium(III) in DMF solutions have been studied. It was suggested that in the presence ofn-butyl bromide, the electrochemically generated monoanionic complexes undergo alkylation at the metal atom. The geometries of the neutral and anionic complexes were calculated by the ZINDO/I semiempirical method. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 289–293, February, 1998.     

Polyfuryl(aryl)alkanes and their derivatives 18. Photochemical transformation of 2-nitroaryldifurylmethanes

During UV irradiation or storage in light, solutions of 2-nitroaryldifurylmethanes in THF are converted into derivatives of 4,9-dihydrofuro[3,2-b]quinoline.For communication 17 see [1].Kubansk State Technological University, Krasnodar 350072, Russia. Severo-Osetinsk State University, Vladikavkaz 362040, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1250–1252, September, 1998.