Synthesis of Aryl Ethers by Nonactivated Aromatic Nucleophilic Substitution Reactions

The results of a kinetic study of model reactions between substituted phenols and bromobenzene in the presence of potassium carbonate and the copper(I) chloride–8-hydroxyquinoline catalytic complex in N,N-dimethylformamide are presented. The reactions were found to obey a first-order rate law. Both orbital and charge interactions should be taken into account in a consideration of the effect of the structural characteristics of reactants on the rate of reaction. The kinetics of substitution of the phenoxide anion for an aromatically bound halogen atom in activated and nonactivated systems with the formation of practically valuable aryl ethers were comparatively studied. The results presented provide an opportunity to distinguish the common features and regularities of activated and nonactivated aromatic substitution in the test systems.     

Vibrational spectra and structure of 4-cyano-4′-pentalkoxybiphenyl in different physical states

The polymorphism, conformation mobility and structure of 4-cyano-4′-pentalkoxybiphenyl (5OCB) in different physical states are studied by IR spectroscopy. The spectra were measured in the frequency range 400–4000 cm⁻¹ at temperatures from 300 to 350 K. The IR spectra of 5OCB are modeled using the concept of conformational mobility of these molecules. An analysis of the experimental and theoretical spectra reveals absorption bands whose spectroscopic parameters are sensitive to variations of temperature (experiment) and conformation (theory); a relationship between these changes is established. It is concluded that the polymorphism of 5OCB is of conformation type. In the solid crystalline state, 5OCB molecules have conformations with a planar biphenyl fragment; the angle of orientation of the plane of the carbon framework of the alkyl radical relative to the biphenyl fragment decreases as the temperature increases from 35° in the solid crystalline state to 10° in the liquid crystalline and isotropic liquid states. In both of these states the biphenyl fragment becomes nonplanar. The angle between the phenyl rings is up to 30°. Saratov State University. Institute of Physics, Ukrainian Academy of Sciences. Samarkand State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 1, pp. 55–60, January–February, 1998. This work was supported by RFFR grant No. 97-03-32175a.     

A facile entry to l-aryl-4,5-dihydro[1,4]oxazepino-[5,4-a]isoindole-2,7-diones

The titled compounds were prepared by reacting N-(2-bromoethyl)phthalimide with enolates of phenylacetic acid esters. 2,3-Dihydrooxazolo[2,3-a]isoindolones are believed to be intermediates in the process. An X-ray crystallographic analysis was conducted on one of the compounds.     

Asymmetry and magnetism in bis(oximato)-bridged heterobimetallic compounds: a computational approach

A density functional study of exchange coupling was carried out for a series of heterobinuclear oximato-bridged transition metal complexes. Model calculations were used to examine the influence of the electronic configuration of the metal atoms on the coupling constants. This analysis was complemented by a study of the variation of the coupling constant with the most usual structural distortions within this family of compounds. The influence of the nature of the terminal ligands as well as that of the symmetry on the bridge were also investigated.     

Reversible temperature-induced transformations of poly(N-ethyl-4-vinylpyridinium) complexes with dodecyl sulfate in aqueous salt solutions

Supramolecular organization of complexes formed by poly(N-ethyl-4-vinylpyridinium bromide) and sodium dodecylsulfate in aqueous salt solutions was studied as a function of temperature and concentration of the complexes. It was shown that a decrease in temperature and/or concentration of complexes led to their reversible disaggregation into a molecularly dispersed (“unipolymer”) state. The ratio between the components in complex particles remained unchanged in this case. It was first found that phase separation in aqueous solutions of the complexes upon temperature elevation is accompanied by the precipitation of a nonstoichiometric complex.     

Synthesis of N-heteroaromatic onium betaines of indane-1,3-dione

Betaines are formed in good yields in the reaction of N-heteroaromatic compounds with 2-dicyanomethyleneindane-1,3-dione oxide and its 4- and 5-halo derivatives in dioxane. The corresponding oxides were obtained by oxidation of 2-dicyanomethyleneindane-1,3-dione and its 4- and 5-substituted derivatives with hydrogen peroxide in dioxane. Data from the IR spectra of the compounds are presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 889–892, July, 1978.