Hydrogen bonds in carbonylated 1,4-dihydropyridines

For H bonds stabilized by π-conjugation in carbonylated 1,4-dihydropyridines, an analysis of the structural data of the Cambridge Structural Databank showed that the hydrogen bond was an essential condition for π-conjugation. It was found that π-delocalization possibly correlated with the bioactivity of drugs that were calcium antagonists. In the presence of two carbonyl groups, hydrogen bonds in crystal are predominantly formed by the carbonyl group that is anti-periplanar to the 1,4-dihydropyridine ring.     

Volumetric and refractive properties of binary mixtures containing 1,4-dioxane and chloroalkanes

Refractive index deviations, excess volumes, and molar refractions of binary mixtures containing 1,4-dioxane and 1-chloropropane or isomeric chlorobutanes have been calculated from experimental data of refractive indices and densities at temperatures of 298.15 K and 313.15 K. Results obtained have been discussed in terms of intermolecular interactions and a comprehensive discussion has been provided. Excess volumes have been also correlated using Peng–Robinson–Stryjek–Vera cubic equation of state and the relation between parameter b (covolume) from the equation of state and molar refraction has been verified. Refractive indices were compared with those predicted using the equation of state and several mixing rules.     

Hydrogen peroxide and ammonia on protonated ice clusters

A temperature controlled source for protonated water clusters has been combined with high-resolution mass spectroscopy to study the stability pattern of ice clusters and compounds with ammonia and hydrogen peroxide depending on temperature. The stability pattern of pure protonated ice shows the two well known peaks at 21 and 28 molecules and also less pronounced structure up to n=55. Ammonia and hydrogen peroxide do not destroy this pattern but shift it by a number of water molecules. The additives are therefore integrated in the persisting crystalline structure of the pure protonated ice. Based on this structural information, density functional theory calculations reveal that hydrogen peroxide and ammonia occupy surface positions on a dodecahedral 21-molecule cluster and are not caged in the center.     

Hydrogen bonds in gas-phase clusters between halide ions and olefins

Gas-phase clustering reactions of halide ions (X- = F-, Cl-, Br-, and I-) with ethylene (C2H4) and propylene (C3H6) were studied with a pulsed electron beam mass spectrometer. Bonding energies of all cluster ions were found to be less than 10 kcal/mol, i.e., no anion-initiated polymerization of C2H4 and C3H6 took place. For the cluster F-(C2H4)n, a small gap in the binding energy is observed between n = 4 and 5 suggesting that the first shell is completed with n = 4. For larger halide ions, the bond energies for the clusters X-(C2H4)n were found to be nearly n independent. For Cl-(C3H6)n a steep decrease in binding energies was observed between n = 2 and 3 and n = 3 and 4. The structure of the cluster ions was investigated by ab initio calculations. X-(C2H4)n complexes were calculated to have hydrogen-bond geometries regardless of the identity of the halide ions, and bidentate (chelate) type geometries of X-(C3H6)1 were found.     

1,4-二氧六环和氨分子氢键团簇的从头算

在不同基组水平上,对１,４－二氧六环和氨分子氢键团簇体系进行了从头算分子转道法研究,优化得到中性团簇,离子团簇和碎片离子（质子化团簇离子和非质子化团簇离子）平衡几何构型,研究结果表明：中性团簇最稳定构型为Ｒ－ＨＮ２－ＨＮＮ２（Ｒ：１,４－二氧六环）,离子团簇由于发生质子转移,其构型与中 团簇有较大的淡同,两类碎片离子Ｒ（ＮＨ３）＋和Ｒ（ＮＨ３）Ｈ＾＋与中性团簇Ｒ（ＮＨ３）的结构也有所不同     

Nitration of phenol in 1,4-dioxane

The nitration of phenol with excess nitric acid in aqueous dioxane, in contrast to the nitration in aqueous ethanol, yields exclusively 2,4-dintrophenol, whereas at equimolar ratio of phenol and nitric acid the major reaction products are mononitrophenols (99%), among which the p-isomer prevails.     

Molecular beam multiphoton-ionization studies on ammonia—water binary clusters

Two-photon ionization mass spectra are obtained for NH₃H₂O binary clusters both with a nozzle beam and an ArF excimer laser. The detected major ions are H⁺(NH₃)_n(H₂O)_m(1 <m + n < 9). The results suggest that ammonia molecules constitute an inner shell which is surrounted by water molecules.     

Unsaturated benzo-1,4-dioxane derivatives

Reaction of 6-chloromethylbenzo-1,4-dioxane with triethyl phosphite gives a phosphonate, the condensation of which with aldehyde gives unsaturated compounds containing a benzo-1,4-dioxane ring.     

Gas-phase oxidation of 1,4-dioxane

An experimental investigation in a conventional static apparatus of the oxidation of equimolecular mixtures 1,4-dioxane-O₂ has shown that 1,4-dioxane reacts with oxygen more readily than most hydrocarbons. Cool flames and ignitions were observed above 200°C in a pressure range up to 300 torr. The products of the slow reaction and cool flame were analyzed by gas chromatography and GC-MS; the slow reaction gives only CO, CO₂, H₂CO, H₂, C₂H₄, and H₂O. A radical chain mechanism is suggested and discussed by using an evaluation of the rate constants of the possible elementary steps by the methods of thermochemical kinetics.     

Thermal polymerization of N-tert-butylacrylamide in 1,4-dioxane

The kinetics of the thermal polymerization of N-tert-butylacrylamide were investigated in 1,4-dioxane as solvent, in the 65–80°C temperature range. It was found that the overall rate of polymerization which was determined by a gravimetric method is proportional to the 1.9 power of monomer concentration at 70°C. The rate of initiation was determined by ESR spectroscopy using DPPH as an inhibitor, and it was found that the order of initiation rate is 1.8 with respect to monomer concentration at 70°C. The overall activation energy for the thermal polymerization of N-tert-butylacrylamide was found to be 64 ± 9 kJ mol^?1 in the 65–80°C temperature range. The activation energy for the rate of initiation was also determined and it was found to be 90 ± 23 kJ mol^-1.     

Homolytic amination of benzo-1,4-dioxane

When 5,6-benzo-1,4-dioxane was reacted with N,N-dialkylchloramines in the presence of FeSO₄ at 10–20C in a solution of acetic and sulfuric acids, 6-(N,N-dialkylamino)benzo-1,4-dioxanes and 6-chloro- and 6,7-dichloro-benzo-1,4-dioxanes were obtained. Under the conditions used in the study mainly chlorination products were synthesized. Reaction of 5,6-benzo-1,4-dipxane with the system (NH₃OH)₂SO₄-TiCl₃ resulted in the formation of 6-aminobenzo-1,4-dioxane.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 316–318, March, 1989.     

Synthesis of acetylenic derivatives of 1,4-dioxane

Cyclic ketals — 2,5-dimethyl-2,5-bis(4-penten-2-ynyloxy)-1,4-dioxane and 2,5-dimethyl-2,5-bis(3-phenyl-2-propynyloxy)-1,4-dioxane — were isolated in the reaction of propargyl alcohol with vinyl- and phenylethynylcarbinols in the presence of HgO-BF₃.O(C₂H₅)₂ catalytic system.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1029–1030, August, 1986.     

Hydrogen bonds in carbohydrates

We propose a method of hydrogen-bond effective quasi-harmonic potential matching for taking into account changes in the torsional energy of CCOH groups involving H bonds. Knowledge of the perturbation potential has enabled analytical calculation of changes in the torsion force constants of these groups explicitly taking into account their dependences on the structure of the hydrogen bridge and the crystal as a whole. It is also shown that the application of the matched potential for determining the torsion angle (CCOH group energy minimization in the cluster) leads to a better agreement with the experimental geometrical data.     

Kinetics of chloromethylation of benzo-1,4-dioxane

The chloromethylation of benzo-1,4-dioxane in acetic acid in presence of SnCl₄, SbCl₃, ZnCl₂, and SbCl₅ catalysts was investigated. The activation energy of the process was found to be 19.6 kcal/mole. The reaction is zero order in chloride ion and first order in the Hammett acidity function. In excess HCl the reaction is described by a second-order equation. The relative activities of the methyl chlorides in the chloromethylation of benzo-1,4-dioxane were determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 459–462, April, 1981.     

Homolytic alkylation of benzimidazole by 1,4-dioxane

The homolytic alkylation of benzimidazoles by 1,4-dioxane has been studied. Introduction of an ethyl group at position 1 and a sulfonic group at position 2 of the heterocycle lowers the yield of products of substitution of hydrogen or the sulfonic group at position 2 by a dioxanyl radical.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 791–792, June, 1988.     

1,4-dioxane as a solvent in spectroscopy and photochemistry

Commercially available 1,4-dioxane, even of spectroscopic grade, contains various impurities that arise mostly from reaction of the solvent with oxygen. Aspects relevant to the spectroscopy and photochemistry of the dioxane/oxygen system are discussed. Methods of purification and storage of the solvent are presented.