Ground-state dynamics of α-methylstyrene. I. Thermally induced oligomerization in bulk

α-Methylstyrene (α-Me-St) in bulk undergoes a variety of thermally induced processes which we investigated in detail by product-distribution analysis. The oligomeric products, shown by GC–MS coupling techniques and independent syntheses, consisted of nine dimers and nine trimers with no detectable higher oligomers or polymers. Two isomeric cyclobutanes and one of the open-chain unsaturated dimers were formed by a conventional two-step cycloaddition; a Flory-type diradical was the common intermediate. In contrast to these 2π + 2π products, the majority of the remaining oligomers could not be interpreted on the basis of π-electron interaction between closed shell molecules. Their structures, however, were compatible with a free radical process in which cumyl(MH·) and 1,4-dimethyl-1-phenyl-tetrahydronaphthalene-yl(THN·), which are consecutive products of 4π + 2π and 2π + 2π interactions, respectively, were involved in addition and transfer reactions. Because of the small rate of initiation and the obvious lack of free radical recombination products, a mechanism was suggested in which MH· and THN· radicals react predominantly in a closed sequence of elementary processes and to a rather small extent only by bimolecular free radical termination. Two sorts of stabilization steps, hydrogen transfer to monomer (R_nH· + M → R_n + MH·) and hydrogen abstraction from a hypothetical 4π + 2π intermediate I (R_nH· + I → R_nH₂ + THN·), are attributed to the high rates of unsaturated and saturated oligomer formation.     

Study of the thermal stages of the photoinitiated cyclization of diarylamines with polyhalogenated methanes

On the basis of a study of the kinetics of the dark stages of the photoinitiated formation of acridines from substituted diphenylamines and bromoform the ionic nature of these stages was confirmed. Quantum chemical calculations confirmed the assumption of the dependence of the efficiency of cyclization on the charge state of the reacting molecules.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 564–569, March, 1991.     

Molecular and crystal structure of 1,3,10,12-tetraoxa-6,7,15,16-tetrathiacyclooctadecane recovered from a polysulfide oligomer

Conclusions The geometric parameters of the molecules of the main cyclic-fraction component contained in a polysulfide oligomer synthesized from 2,2-dichlorodiethylformal were determined. The cyclic structure assigned to this compound according to mass spectrometric data was confirmed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 338–340, February, 1988.The authors thank A. Kh. Plyamovatyi for-useful discussion of the present paper.     

Dynamic thermal decomposition of linear polymers and its study by thermo analytical methods

Kinetic schemes allowing to interprete the results of high-temperature gravimetric analysis of linear polymers are proposed. A thermoanalytical method has been developed in which the time for establishing constant temperature in the sample is reduced by 1–2 s. The method can be used to determine to what temperature the polymer can be overheated.     

Reductive coupling of polyfunctionalized organobismuth and organolead arylating reagents in the synthesis of benzopyran derivatives

Benzopyran derivatives were synthesized in good yields by the reactions of tris[2-(chloromethyl)phenyl]bismuth diacetate and 2-(halomethyl)aryllead triacetates with phenols and naturally occurring 4-hydroxycoumarins in the presence of bases according to a three-step one-pot procedure. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2520–2529, November, 2005.