Alkylation of ethylenethiourea with alcohols: a convenient synthesis of S-alkyl-isothioureas without toxic alkylating agents

The alkylation of ethylenethiourea with alcohols and aqueous acids (HCl, HBr, and HI) allows the synthesis of the respective S-alkyl-isothioureas in high yield and purity. Consistently high yields (91-98%) were obtained with 56% HI, the yields for 48% HBr (48-93%) and 37% HCl (36-85%) were lower and varied with the type of alcohol. The method is a convenient low-cost alternative to the use of alkyl iodides and an easy access to the S-tert-butyl isothiourea.     

D,L-1,2,2-三甲基环戊烷-1,3-二胺硝酸镍配合物的合成、结构及其和手性D-(+)-1,2,2-三甲基环戊烷-1,3-二胺氯化镍配合物的对比分析(英)

A nickel(Ⅱ) complex [Ni(La)₂](NO₃)₂ (1) with bidentate racemic 1,2,2-trimethylcyclopentane-1,3-diamine ligand has been synthesized and characterized by IR, EA, ES-MS, and its X-ray diffraction study reveals that the nickel(Ⅱ) center is tetra-coordinated by one D- and one L- diamine ligands, and a three-dimensional hydrogen-bond-sustained network is formed in the solid state by means of the eight-membered N-H…O hydrogen bond cycle. This compound also supplies a good comparison to the chiral complex [Ni(L_b)₂]Cl₂·2H₂O (2) (L_b=D-(+)-1,2,2-trimethylcyclopentane-1,3-diamine). CCDC: 218122.     

High-performance liquid chromatography of amino acids, peptides and proteins CXXV. Molecular dynamics simulation of n-butyl chains chemically bonded to silica-based reversed-phase high-performance liquid chromatography sorbents

The molecular dynamics method has been applied to investigate the conformations of n-butyl ligands immobilised onto an amorphous silica surface analogous to those utilised with silica-based RP-HPLC sorbents. Three systems were constructed which corresponded to ligand densities of 1.64, 2.67 and 3.69 μmol/m². A number of parameters related to the structure of the sorbent materials were derived in order to characterise the molecular properties of each system. These parameters included the hydrocarbon layer thickness, the frequency of gauche conformations, the distance distribution for carbon atoms and the diffusion coefficients of individual atoms in the n-butyl ligands. From these properties, the positions of chains with respect to the surface as well as their mobility were estimated. It was found that at higher densities, the n-butyl chains are predominantly perpendicular to the surface while at low density they are highly tilted or lying almost parallel to the surface. The degree of ligand flexibility decreased with increasing surface density. Mobility of individual carbon atoms as well as chain disorder increased with distance from the surface for all ligand densities. The simulated properties of n-butyl chains immobilised to a silica surface correlated well with results obtained by Fourier transform IR and ¹³C-cross polarisation magic angle spinning NMR experimental methods and statistical predictions of the behaviour of immobilised chains.     

对称三唑Schif碱和氯化铜配合物的研究

本文介绍水杨配合与４－氨基－３，５－二乙基－１，２，４－三唑缩合而成对称三唑Ｓｃｈｉｆ碱（ＳＡＥＴＺ）与氯化铜（ＣｕＣｌ２）形成一种新的配合物Ｃｕ（ＳＡＥＴＺ）２（ＳＡＥＴＺ＝４－（邻羟苯基亚甲基）－亚胺－３，５－二乙基－１，２，４－三唑）。配合物的晶体结构表明，分子中两个偶氮甲碱的Ｎ原子及两个酚氧原子与中心Ｃｕ原子形成规则的平面配位结构。晶体属单斜晶系，空间群Ｐ２１／ｎ，ａ＝８．６８８（２），ｂ＝９．３１４（１），ｃ＝１６．５１５（４），β＝９４．３４（２）。，Ｖ＝１３３２．５（７）３，Ｚ＝２。     

过渡金属乙酰丙酮螯合物的体积排除色谱研究

用定量体积排除色谱方法研究了过渡金属Fe(Ⅲ)、Co(Ⅲ)、Cu(Ⅱ)、Ni(Ⅱ)的乙酰丙酮螯合物在四氢呋喃溶液中的加合和缔合行为。在溶液中乙酰丙酮钴(Ⅲ)以单个螯合物分子的形式存在,乙酰丙酮铜(Ⅱ)和乙酰丙酮铁(Ⅲ)与溶剂加合生成加合物,乙酰丙酮铁(Ⅲ)除加合物外还存在缔合度为2-10的多分散缔合物,乙酰丙酮镍(Ⅱ)水合物在四氢呋喃中产生了加合交换作用,同时存在缔合度为6左右的缔合物。色谱数据给出了螯合物、加合物及缔合物     

甲烷氧化偶联催化反应的特征

应用程序升温反应（ＴＰＲ）及质谱分析表征了ＣａＯ，Ｓｍ２Ｏ３，０．５－１０％Ｓｍ／ＣａＯ催化剂上的甲烷氧化偶联反应特性。谱图分析表明，在４００－１０００℃范围内，甲烷氧化偶联反应产物的变化呈现三个反应温度区域：（１）完全氧化区，反应主要为ＣＨ３·在催化剂表面完全氧化形成ＣＯｘ和Ｈ２：（２）偶联区，主要为ＣＨ３·的氧化和偶联竞争反应，Ｈ２谱线出现明显的低温峰；（３）氧耗尽区，反应为高温气相反应，产物     

Electron transfer initiated Diels-Alder reaction with allenes as dienophiles

The first examples of using aryl allenes as dienophiles in the electron transfer induced Diels-Alder reaction are described. According to mechanistic tests the reaction proceeds via a cycloaddition of the diene^+· to the allene.     

Reaction of N-(2-hydroxyethyl) ethylenediamine over zeolite and chromite catalysts

N-(2-hydroxyethyl) ethylenediamine reaction was observed over zeolite catalysts giving rise to only dehydrocyclization and over chromite catalysts showing dehydrocyclization together with dehydrogenation. The major product changes from the cyclized compound piperazine to pyrazine when the reactant is switched from zeolite to chromite catalyst. This process stands as a model reaction for characterizing lone acid sites and adjacent acid-base sites over zeolite and chromite catalysts, respectively.IICT Communication No. 3175     

YPxV1—xO4（0≤x≤1）：Dy^3＋的合成及其光谱性质的研究

本文报道了不同组成的ＹＰｘＶ１－ｘＯ４（０≤ｘ≤１）：Ｄｙ＾３＋的合成和结构。ＹＰｘＶ１－ｘＯ４（０≤ｘ≤１）为四方晶系，晶胞参数随ｘ的增大呈线性减小。基质的Ｓｔｏｋｅｓ位移随ｘ的增大逐渐变大，而激发光谱峰值则向短波方向移动。在ＹＰｘＶ１－ｘＯ４：０．００６Ｄｙ＾３＋体系中，ｘ＞０．４时出现的基质发射是由ＰＯ＾３－４引起的。基质及Ｄｙ＾３＋的发光效率和Ｄｙ＾３＋的发光强度的黄蓝比均与ｘ有关。同时探     

Notes on Kuhn's ω″ molecular orbital method

(1) It is shown that, contrary to statements sometimes made, it is perfectly possible to obtain consistent sets of charges in Kuhn's ω″ molecular-orbital method, whatever the values of the parameters ω, ω′, ω″.

(2) Particular applications are made to the benzyl cation, and to the non-alternants fulvene, heptafulvene and azulene. It appears that including the ω-terms decreases the magnitude of the largest of the net atomic charges as calculated by the simple Hückel method, and results in an overall smoothing-out process. Further inclusion of the ω′-terms continues this smoothing-out process, but inclusion of the ω″-terms may sometimes slightly reverse this process.

(3) The charge distributions obtained for fulvene and azulene in (1) and (2) lead to molecular dipole moments which are still much too large.

In view of (3) it is not clear that the additional work involved in the inclusion of ω′ and ω″ is justified by the greater accuracy thus obtained.