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.     

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.     

Mixed-metal ethylenediaminetetraacetates of neodymium and alkaline earths

Conclusions In solution, the complexes M^II(NdA)₂ do not have a polynuclear structure. In the conditions studied, hydroxo polynuclear complexes including EDTA and M^II and Nd³⁺ ions are also not formed. Our results are not inconsistent with the hypothesis that the solid complex Ca(NdA)₂·17H₂O has a polynuclear structure and that the polynuclear character is successively weakened as Ca²⁺ is replaced by Sr²⁺ and Ba²⁺.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1235–1239, June, 1977.     

Stereochemistry of the synthesis of 1,2,3,4-tetrahydrocinnolines from aryldiazenium salts and olefins

It follows from the PMR spectra that the reaction of 1-methyl-, 1-phenyl-, 1-ethyl-,1-phenyl-, and 1,1-diphenyldiazenium salts with cis- and trans-d-styrenes, which leads to the corresponding 3-d-4-phenyl-1,2,3,4-tetrahydrocinnolines, takes place with retention of the configuration in the starting styrenes. It is therefore proposed that this reaction be regarded as a special case of [4⁺_s + 2_s]-cycloaddition.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1658–1661, December, 1977.