Thermodynamic properties of water/organic systems with small contents of water 1. Limiting partial molal volumes of D2O and H2O in methanol and 2-propanol at various temperatures

Limiting partial molal volumes of D₂O and H₂O in methanol and 2-propanol have been measured in the temperature interval 278–318 K. A hypothesis is advanced regarding the formation of water-alcohol aggregates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 317–320, February, 1991.     

Aromatic substitution

It is demonstrated that a previously developed topological expression for the total π-electron energy of aromatic molecules provides a good qualitative account of localization energies. The logarithm of the ratio of the algebraic structure counts for the ground state and the localized reaction intermediate is the principle energy determining factor. This expression fails for hydrocarbons with unusually small HOMO-LUMO separations. An alternative topological expression that includes a correction for this situation provides an excellent non-empirical explanation for the successful empirical use of Dewar reactivity numbers in correlating exact localization energies. The present analysis provides an explanation for the success of the traditional resonance structure counting technique in predicting relative rates of aromatic substitution. The analysis develop applied only to alternant hydrocarbons.     

Infrared spectra and rotational isomerism of epifluorohydrin and other propene oxide derivatives

The infrared spectrum for the vapour, liquid and solid states of epifluorohydrin has been studied, and evidence has been obtained for the presence of rotational isomers. The dominant conformer in all phases corresponds to a gauche structure, which was the only form identified in the vapour by microwave spectroscopy [1]. Similar evidence for conformational equilibria has been found for the chloro, bromo and iodo derivatives, and the enthalpy differences between the rotational isomers of these compounds were measured respectively as 4580 ± 970, 3950 ± 400, and 2350 ± 170 J mol^?1 respectively. At low temperatures, epiiodohydrin was found to crystallize in one of two possible crystalline phases. These two phases correspond to the two rotational isomeric conformations of the molecule.     

Reaction of Organoelement Hydrides R<Subscript>3</Subscript>EH (E = Si,Ge) with Metal <Emphasis Type="Italic">tert</Emphasis>-Butylate (M = Al,Ti)-<Emphasis Type="Italic">tert</Emphasis>-Butyl Hydroperoxide Oxidative Systems

Trialkyl(aryl)silanes and -germanes effectively react with metal (Al, Ti) tert-butylate-tert-butyl-hydroperoxide under mild conditions (room temperature, benzene or tetrachloromethane) mainly by the element-hydrogen bond. The character of the products depends on the nature of the element, the structure of the radical bound to it, and the solvent. The process is radical in nature. It includes the stages of formation of element-centered radicals and their reaction with the oxygen generated by the system. The intermediate organometallic peroxides can also acts as oxidants for the element (Si, Ge)-hydrogen bonds.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 7, 2005, pp. 1161–1170.Original Russian Text Copyright © 2005 by Stepovik, Gulenova, Martynova, Skvortsov, Cherkasov.     

Functional derivatives of thiophene

A method is proposed for the synthesis of isatin analogs — 4,5-dioxothieno[2,3-b] pyrroles and 5,6-dioxothieno[3,2-b]pyrroles — by reaction of oxalyl chloride with amino-substituted α-amino- and Β-aminothiophene. The thiosemicarbazones of 4-ary1-5,6-dioxothieno[3,2-b]pyrroles were synthesized. n]mis|See [1] for communication X.     

Reactions of 1-Allenylpyrazole and 1-Allenyl-1,2,4-triazole with Hydrogen Chloride and Metal Chlorides

1-Allenylpyrazole and 1-allenyl-1,2,4-triazole react with hydrogen chloride via proton addition at the pyridine-like nitrogen atom (N² and N⁴, respectively). In the reaction with 1-allenylpyrazole, 1-[(E)-3-chloro-1-propenyl]pyrazole is also formed via regio- and stereoselective addition of hydrogen chloride to the propadienyl group. 1-Allenylpyrazole and 1-allenyl-1,2,4-triazole act as unidentate ligands with respect to Co, Ni, Cu, Zn, Cd, Pd, and Sn, the donor centers being N² and N⁴, respectively. Apart from mononuclear coordination compounds, 1-allenylpyrazole gives rise to polymeric complexes which contain units and blocks formed by the free ligand.     

Interaction of Nitromethane with Modified Paramagnetic Defects on a Thermochemically Activated Silica Surface

It was found that the interaction of the modified paramagnetic defects SiO(CH₂) _n H₂ (n = 0.1) with nitromethane on a thermochemically activated silica surface at 300 K results in the formation of the following nitroxyl radicals: SiO(CH₂) _n CH₂ON( )CH₃ and SiO(CH₂) _n CH₂N( )CH₃. It was suggested that these radicals are the products of two different reactions of the modified paramagnetic defects: the first results from a reaction with free nitromethane; the second, from a reaction with nitromethane bound as complexes with diamagnetic surface defects.     

Elimination of bremsstrahlung in activation analysis by the deflection of β-particles in a magnetic field

The structureless background at X-ray and low energy -ray region, resulting from bremsstrahlung due to the stopping of -radiations, causes serious problems in nuclear spectroscopy. In this study, in order to reduce the background and therefore to increase the sensitivity of the nuclear analytical technique and the number of elements observable, a methodology is developed to deflect the -particles by a magnetic field. The experimental setup consists of a permanent magnet /1 kG/, Ge/Li/ solid-state detector, and multichannel analyzer.     

Kinetic CH-acidity of benzenetricarbonylchromium and its derivatives

Kinetic acidities of aryl and benzyl CH-bonds for complexes of benzene and its methoxy and alkyl derivatives with tricarbonylchromium are determined in a solution of lithium tert-butoxide in N,N-dimethylacetamide. Complexation of alkyl-aromatic compounds to the Cr(CO)3 group increases the lability of the aryl CH-bond by 107–109 times and that of the benzyl bond by 5·10⁴–5·10⁵ times. The Cr(CO)₃ group in arene complexes neutralizes the effect of other substituents regardless of their nature and position in the molecule.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2458–2461, November, 1989.     

Benzindoles. 23. 2-formyl- and 3-formyl-4,5-benzindoles

It is shown that, in addition to the usually formed 3-formyl-4,5-benzindole, 2-formyl-4,5-benzindole can be obtained via the Vilsmeier reaction. The IR, PMR, and UV spectra of the 2- and 3-formyl isomers are compared, and their possible conformations are discussed.See [1] for Communication 22.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 343–345, March, 1984.