A density functional theory study of the gas-phase elimination reactions of 4-arylideneimino-1,2,4-triazol-3(2H )-ones and their 3(2H )-thione analogues

Theoretical studies on the thermolysis in the gas phase of 4-arylideneimino-1,2,4-triazol-3(2H)-ones and 4-arylideneimino-1,2,4-triazol-3(2H)-thiones were carried out using density functional theory methods, at the B3LYP/6-31G(d) and B3LYP/6-311+G(2d,p) levels of theory. The proposed reaction mechanism occurs in one step, leading to the formation of 3-hydroxy-(2H)-1,2,4-triazole or 3-mercapto-(2H)-1,2,4-triazole and a 4-substituted benzonitrile, via a six-membered cyclic transition state. The progress of the reactions was followed by means of the Wiberg bond indices. The results indicate that the transition states have character intermediate between reactants and products, and the calculated synchronicities show that the reactions are slightly asynchronous, in the case of triazolones, and show a higher asynchronicity in the case of triazolthiones. The bond-breaking processes are slightly more advanced than the bond-forming ones, indicating a small bond deficiency in the transition states. Kinetic and activation parameters for the reactions studied have been calculated and compared with available experimental data.From the Proceedings of the 28th Congreso deQuímicos Teóricos de Expresión Latina (QUITEL 2002)     

富烯碳原子簇的石墨层间闭合形成机理

本文提出了富烯碳原子簇的石墨层间闭合形成机理，由该机理推出的许多结果与实验事实符合很好。我们认为碳原子簇自由基的快速淬灭及其淬灭速度是富烯碳原子簇形成及其丰度的决定因素。由此得出富烯碳原子簇在给定实验条件下产生的必然性，并预言不同大小的富烯碳原子簇可以通过优化实验条件选择性地合成。     

动力学体系二维数据的秩分析及其应用

详细论证了动力学体系中存在的多种共线性情况,以及在此情况下二维数据阵的秩与独立反应数及组分数的关系.分析了通过增秩这一方式来判断体系组分数的条件.讨论了反应间存在物质交换对数据阵秩的影响.建立起一套通过秩分析判断未知动力学体系中存在的反应组分数、独立反应数以及可能反应机理的方法.将秩分析技术应用到聚苯胺与质子酸反应,初步分析了该体系存在的多种吸光性结构及结构变化.确定了[H＋]=0.01～0.1 mol•L－1范围内,聚苯胺与质子酸反应存在一个三结构两步互变过程.     

Theoretical Study on the Dark Oxidation Reaction Mechanism of Ethers

1 INTRODUCTION Ethers are a kind of organic compounds that are easily oxidized under the conditions of lacking light and any additional excitement. According to dif- ferent mechanisms, the oxidation reactions could be classified into two types: photooxidation reaction and dark oxidation reaction. The former is the reaction with excited state oxygen molecule (singlet state), while the latter is the reaction with ground state oxygen molecule (triple state) without illuminance or any exciter…     

Thick Silicate Film by an Interfacial Polymerization

A thick silica gel film, corresponding to the glass film of 10–20 micron in thickness, has been formed at the interface between two immiscible liquids, hexane and water, using E-40, a partially polymerized silicon alkoxide, as the precursor. The film formation was possible using both acid- and base-catalyzed water, but was greatly dependent on the type of catalyst. Only the trace of a film was observed for the system catalyzed with a strong electrolyte such as HCl, HNO₃ or NaOH, while a gel film, corresponding to the glass film of several to 10 micron in thickness was formed with a weak electrolyte such as ammonia, organic acid like acetic acid, citric acid, etc., of similar pH value. The direct introduction of organic base catalyst like triethylamine in hexane was much more effective than the use of ammonia water, suggesting that the polymerization of E-40 to form a gel film takes place in the organic phase, where water molecules, as well as undissociated ammonia or organic acids, can diffuse in.     

N-TiO2/ZnO复合纳米管阵列的掺杂机理及其光催化活性

以ZnO纳米柱阵列为模板, 采用溶胶-凝胶法制备出TiO2/ZnO和N掺杂TiO2/ZnO的复合纳米管阵列. 扫描电镜(SEM)、X射线光电子能谱(XPS)和紫外-可见漫反射吸收光谱(UV-Vis)的结果表明: 两种阵列的纳米管均为六角形结构, 直径约为100 nm, 壁厚约为20 nm; 在N-TiO2/ZnO复合纳米管阵列中, 掺入的N离子主要是以N-Ox、N-C和N-N的形式化学吸附在纳米管表面, 仅有少量的N离子以取代式掺杂的方式占据TiO2晶格O的位置; 表面N物种形成的表面态能级和取代式掺杂导致带隙的窄化, 增强了纳米管阵列的光吸收效率, 促进了光生载流子的分离. 光催化实验结果表明, N离子的掺杂有利于N-TiO2/ZnO复合纳米管阵列光催化活性的提高.     

Anomalous hydroalumination of methyl nopol ether with a LiAlH4-3AlBr3 system

Hydroalumination of methyl nopol ether with a LiAlH₄-3AlBr₃ system is accompanied by a skeleton rearrangement and gives 6-dibromoalumo-7-methoxymethyl-2-menthene. Further hydroalumination affords a mixture of 2,6- and 2,5-bis(dibromoalumo)-7-(methoxymethyl)menthanes in 8020 ratio. Hydrolysis and oxidation of these organoaluminum compounds were carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 506–510, March, 1994.     

Salt effects in the mercuration of unsaturated compounds. Kinetic evidence for the formation of ion pairs and a solvated ion

The kinetics of mercuration of bornylene and cyclohexene in different solvents in the presence of NaOAc and LiClO₄ has been investigated. Addition of NaOAc sharply decreases the rate of addition reactions of mercuric acetate to bornylene and cyclohexene in alcohols; the main direction of the mercuration of bornylene is the formation of acetoxy-adducts, and the yield of solvo-adducts decreases from 76 % in the absence of NaOAc, to 19 % in the presence of the salt (4·10^–3 mol L^–1). A reaction scheme involving the participation of intermediate ion pairs and a solvated mercurinium ion is suggested and confirmed by a steady-state concentration method. The influence of NaOAc on the rate of the reaction and on product formation is realized through the common ion effect.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 819–826, May, 1994.     

Synthesis of 2,2’-Biflavanones from Flavone via Electroreduction and Photolysis

Biflavonoids, widely distributed in natural plants, had strong biological activities including spasmolysis, peripheral vasodilatation, antibradykinin activity and antispasmogenic action against prostaglandin PGE1, inhibition of cyclic GMP and cyclic AMP phosphodiesterase and inhibition of hepatoma cells. Recently, some biflavonoids were demonstrated to enhance suppersion of lymphocyte proliferation, inhibition of phospholipaseCr1, anti-inflammatory activity, anti-HIV activity, anticompleme…     

A radical mechanism of the reaction of molybdenum carbonyl complexes with bis(triethylgermyl)mercury

The reaction of [Cp(CO)₃Mo]₂ with (Et₃Ge)₂Hg occurs in toluene and THF by a radical mechanism. The interaction between [Cp(CO)₃Mo]₂Hg and (Et₃Ge)₂Hg has a radical character only in THF. The formation of Cp(CO)₃MoH at the first stage of these reactions substantially affects the further course of the process.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1648–1650, September, 1993.