Motion of a helium atom through a comparable-diameter channel in the Frenkel-Kontorova model

The motion of a helium atom through a channel with a diameter comparable to the diameter of this atom is investigated. Such channels are observed in materials of the quartz type. The inclusion of the local law of momentum conservation in the analysis of the interaction between the He atom and the atoms forming the channel wall makes it possible to reduce the problem to one-dimensional motion similar to the motion of a dislocation in the Frenkel-Kontorova model. In the model proposed here, the activation energy of the complex formed by the He atom and the displacements of atoms of the channel wall is calculated. The obtained energy is expressed in terms of the shear modulus of the material forming the channel and the helium atom polarizability, which depends on the state of the helium atom.     

Heterocyclic nitro compounds XIX. Kinetics of the methylation of 3(5)-nitro-1,2,4-triazoles with dimethyl sulfate

The effect of a substituent in the triazole ring and of the composition of the solvent on the reaction rate was established as a result of a study of the kinetics of methylation of sodium salts of 3(5)-nitro-1,2,4-triazoles in water and water-dioxane mixtures. The relationships found are due to the different degree of dissociation of intimate ion pairs of anions of nitrotriazoles with sodium and the specific character of the solvation of the anions by water.     

Electrode transformations of carbanions and heteroanions

Conclusions The electrolytic oxidation of the 3-nitro-1,2,4-triazole anion is realized through an intermediate radical, which splits out an H atom on reaction with the medium and reacts with benzene to give N-substituted phenyl-3-nitro-1,2,4-triazoles.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1643–1646, July, 1988.     

Copper(II) Chelate Complex with N′-(2,4-Dichlorophenoxy)acetyl-N,N-Dimethylhydrazine: Crystal and Molecular Structure

X-ray diffraction analysis of the copper(II) chelate complex CuL₂ (where L is the deprotonated imid-ol form of N,N-dimethyl-2,4-dichlorophenoxyacetohydrazide (HL)) was performed (3826 reflections, R = 0.039, wR = 0.043). Crystals are monoclinic, a = 8.365(7) Å, b = 23.090(7)Å, c = 12.713(3) Å, = 95.12(6)°, space group P2₁/c, Z = 4. The slightly distorted square environment of the copper cation is composed of two N atoms of the dimethylamino groups and two O atoms of the deprotonated imidol groups. Both N and O atoms are located in trans-positions relative to each other. Additional coordination of electron-donor atoms is prevented by methyl groups, in which the C atoms are at a distance of 2.837 to 2.918 Å from the central ion.     

Dipole moments of nitro derivatives of indazole

The dipole moments of indazole and a number of its nitro derivatives in dioxane solution were measured. The directions of the vectors of the dipole moments of indazole in the tautomeric 1-H and 2-H forms were determined to solve the problems associated with the tautomerism and the position of the substituents in the molecules. The experimental values of the dipole moments, of the investigated compounds were compared with the values calculated via a vector additive scheme. As a result it was shown that the mononitro and dinitro derivatives of indazole exist primarily in the 1-H tautomeric form, whereas the trinitro and tetranitroindazoles exist in the 2-H tautomeric form. The ratios of the isomers were calculated for compounds that have dipole moments intermediate between the 1-H and 2-H forms. A deviation between the experimental and calculated dipole moments of compounds containing two nitro groups in the ortho position was established; this may be explained by disruption of the coplanarity of the molecules or by deviation from additivity because of the introduction of strong electron-acceptor substituents.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1669–1671, December, 1977.     

2-(1-Chloroalkyl)furans in the reaction with sodium diethyl phosphite

2-(1-Chloroethyl) and 2-(1-chloro-2-methylpropyl)furans react with sodium diethyl phosphite to give two products, 2-(1-diethoxyphosphorylmethyl)furan and 2-alkyl-5-(diethoxyphosphoryloxy)furan. The fraction of the latter product increases with increasing size of the alkyl radical. 2-Methyl substitution in the substrate completely suppresses phosphate formation. 2-(1-Chloroethyl)-5-(2-methylpropyl)furan under the action of sodium diethyl phosphite eliminates hydrogen chloride to give the corresponding alkene.     

Synthesis of 3,4-Disubstituted Phosphorus-containing Furans with Free 2 and 5 Positions

A synthetic approach to -(chloromethyl)furans with free 2, 5 positions is developed. It isshown that these compounds enter the Michaelis-Becker reaction to form usual phosphorylation products.With 3,4-bis(diethoxyphosphorylmethyl)furan, two conformers with different chemical shifts of phosphorus nuclei and PCH₂ protons were detected.     

Synthesis of Halomethyl Derivatives of 3- and 4-(Dialkoxyphosphorylmethyl)-5-tert-butylfuran-2-carboxylic Acid and Their Reactions with Nucleophilic Agents

5-tert-Butyl-4-chloromethyl-, 5-tert-butyl-4-(diethoxyphosphorylmethyl)-3-methylfuran-2-carboxylates are effectively brominated with N-bromosuccinimide by the 3-methyl group. The bis(halomethyl)derivative is phosphorylated under conditions of the Arbuzov reaction to give the corresponding chloromethylphosphonate. The obtained organophosphorus derivatives of bromomethyl- and chloromethylfuran-2-carboxylic acid react with secondary amines and sodium butanethiolate to form the corresponding substitution products. Alkyl 5-tert-butyl-4-chloromethyl-3-(diethoxyphosphorylmethyl)-furan-2-carboxylate reacts with sodium acetate in acetic acid to give a 4-acetoxymethyl derivative. It is the first example of a facile reaction with O-nucleophiles of halomethyl derivatives of phosphonomethylated furans.     

α-Oxides in reactions with nh acids of the heterocyclic series

Alkylation of 3,5-dinitro-1,2,4-triazole with -epoxides in aprotic media gave a number of 1-(2-hydroxyalkyl)-3,5-dinitro-1,2,4-triazoles, which readily undergo intramolecular cyclization with elimination of HNO₂ to give 5,6-dihydrooxazolo[3,2-b]-1,2,4-triazole derivatives.See [1] for communication I.Translated from Khimiya Geterotsiklicheskih Soedinenii, No. 5, pp. 705–707, May, 1975.