Thermal decomposition of transition metal carboxylates

Thermal solid-phase decomposition of anhydrous copper(ii) formate has been studied at 120–180 ° The rate of gas evolution during the decomposition depends on the depth of conversion and can be presented as the sum of first-order reaction rates and the rate of the autocatalytic process (a second-order reaction). The evolution of the solid phase during thermolysis has been observed by optical microscopy. The decomposition of copper formate is a complex topochemical process, a combination of homogeneous and heterogeneous transformations and dispersion of large crystals.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. l, pp. 72–76, January, 1996.     

Reaction of 2,6-dibenzylidenecyclohexanone with phosphorus pentachloride: Triple functionalization of the isosemiquinoid system

The reaction of 2,6-dibenzylidenecyclohexanone with PCl₅ occursvia the sequential stages of desoxychlorination and substitutional phosphorylation to form (after oxidation, methoxylation, and hydrolysis on the surface of the chromatographic SiO₂ adsorbent) organophosphorus products of the 1-(a-chloro-, a-hydroxy-, or -alkoxy)benzyl-2-chloro-3-(-(dimethylphosphoryl)benzylidene)cyclobex-1-ene series.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 441–443, February, 1996.     

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).     

Preparation and reactivity of metal-containing monomers

The thermal decomposition of iron (III) acrylate, [Fe₃O(CH₂=CHCOO)₆ · 3H₂O]OH (FeAcr), a monomer with a complex cluster cation, has been studied at 200–370 °C. Thermal transformations of FeAcr occur in two temperature regions. The rates of gas evolution in the low temperature region (200–300 °C) and the high temperature region (300–370 °C) are described by first-order equations withk=4.2 · 10²¹exp[−59000/(RT)] s⁻¹ andk=1.3 · 10⁶exp[−30500/(RT)] s⁻¹, respectively. A study of the qualitative and quantitative composition of the products of FeAcr thermolysis was carried out. The thermal transformation of FeAcr is a complex process of dehydration, degradation, and polymerization in the solid phase followed by decarboxylation of the metal-carboxyl groups of the polymer. for part 33 see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1743–1750, October, 1993.     

Epoxy-amine multimethacrylic prepolymers,kinetic and structural studies

Epoxy-amine methacrylated prepolymers are prepared in a 1-step synthesis by the reaction of Bisphenol A diglycidyl ether, glycidyl methacrylate, and different diamines. The adaptation of these reactions to production processes with a reduced reaction time requires a kinetic control and the use of efficient catalysts. The comparative kinetic treatment of the epoxy-amine reaction in the frame of Horie's and Rozenberg's kinetic schemes have been made. Cases where an efficient acid catalyst is used are also examined. Structural studies of these reactions established the occurrence of a Michael amine/double bond addition, when some amines are used. © 1995 John Wiley & Sons, Inc.     

Synthesis of novel mono- and diaryl-substituted [2.2]paracyclophanes

The cross-coupling reactions of 4-bromo[2.2]paracyclophane withp-tolylmagnesium bromide in the presence of various palladium and nickel complexes have been studied. It was found that [1,1 -bis(diphenylphosphinoferrocene)]palladium dichloride (PdCl₂ · dppf) shows the highest catalitic activity in this reaction. A series of new mono- and diaryl [2.2]paracyclophane derivatives with various substituents in the arene ring have been synthesized using this catalyst. It was shown that it is possible to cross-couple organozinc [2.2]paracyclophane derivatives with aromatic bromides. The composition and structure of the compounds obtained have been established on the basis of elemental analysis and spectral data. Some correlations between the structure and spectral parameters of mono- and diarylsubstituted [2.2]paracyclophanes have been found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1081–1085, June, 1994.The present work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-5246).The authors wish to express their gratitude to Prof. N. A. Bumagin for his scientific interest and helpful discussions.