二茂钛含氟有机酸衍生物的质谱研究

本文研究了二茂钛含氟长链有机酸衍生物(1～3)和具有环状结构的新型二茂钛全氟有机酸(4～7)的电子轰击质谱(EIMS)和负离子化学电离质谱(NICIMS)。在EI谱中出现弱的或不出现M~+,1～7均以CpTiF_2离子为基峰。高质量区的主要特征碎片离子有[M-·cp]~+、[M-R]~+(1～3)和氟重排离子。在低质量区出现一系列二茂钛及茂钛氟重排离子。 1、4～7的NICI(CH_4)质谱中,4、5出现强的M~-离子峰,1出现[M-1]-离子峰,有两个钛的环状结构化合物6和7出现双电荷M~=离子峰,而不出现M~-。     

Use of α‐diketones as visible photoinitiators for the photocrosslinking of waterborne latex paints

The efficiency of several α‐diketones as visible light photoinitiators for the crosslinking of waterborne latex dispersions in the presence of acrylic monomers was evaluated. Among the eight α‐diketones studied, camphorquinone allows the fastest curing speed, and the curing of the acrylic waterborne coating is not affected by the presence of oxygen. The properties of the sunlight‐cured volatile organic compound (VOC)‐free pigmented paints prepared from the waterborne latex are as good or better than the equivalent conventional paint containing VOCs. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3171–3181, 2002     

Can the presence of chemically inert species modify the face selectivity in asymmetric induction by cyclodextrins?

Reduction of-cyclodextrin (-CD) aromatic ketone (acetophenone and acetonaphthones) inclusion compounds were carried out in the presence of a large number of chemically inert species as potential co-guests. In several cases, it was observed that stoichiometric molar ratios of these compounds to ketone significantly modify the chiral induction yielding the inverted alcohol enantiomer and increasing the face selectivity. The results were found to depend strongly on the respective structure and shape of both the ketone and the additive, and on the molar ratio of-CD:ketone:third compound. These observations suggest the formation of a three-component inclusion complex in which the geometry of binding of the substrate and its mobility are changed with respect to the binary system.     

正交试验法研制多烷基二氢化茚

双环苯型麝香化合物对香料工业具有重要意义。如粉檀麝香是合成麝香料。而1,1,2,3,3,5-六甲基-2.3-二氢化茚(HMI)则是制备粉檀麝香的母体化合物, 其经酰化后即可得到粉檀麝香。本文以对甲基异丙苯和2-甲基-丁烯-[2]为原料, 合成了HMI。     

固体Hp[EuA_4]配合物异构体的研究

合成了化学式为Hp[EuA_4]的配合物(A=对甲氧基苯甲酰苯甲酰甲烷;Hp=六氢吡啶),用X-射线粉末衍射法,荧光光谱及热谱等方法研究了它们的性质,并发现由于合成条件(反应物的摩尔投量比,反应温度,所用溶剂)不同,在固体Hp[EuA_4]配合物中配体空间的排布不同,而有不同的异构体存在。     

锗钨酸分子间化合物的合成和结构研究

以锗钨酸和4-甲基吡啶为原料合成了分子间化合物H₄GeW₁₂O₄₀·5C₆H₇N·CH₃CN。单晶X-射线分析表明，属正交晶系，空间群P2₁2₁2₁, 晶胞参数a=13.533(5),b=20.835(5), c=21.859(7)?，V=6164(3)?³。Dc=3.650 Mg/m³, Z=4。对3934个可观察到的衍射点进行全矩阵最小二乘法修正后，可靠性因子R=0.0534。     

沙蚕毒系化合物的结构与生物活性关系

用ＭＮＤＯ－ＰＭ３方法对沙蚕毒系化合物二氢沙蚕毒，硫氰酸酯，巴丹，杀虫单及其异构件的几何构型进行了全自由度优化，并计算了其电子结构，讨论了生物活性与几何构型和电了结构的关系。     

Inclusion by a fluorenyl diol host with substituted pyridines

The structures of the inclusion compounds formed by the host 9,9’-(ethyne-1,2-diyl)bis(fluoren-9-01) with pyridine and picolines are similar and display tubular topology. The host discriminates poorly between these guests. The kinetics of desorption of the pyridine compound is governed by the Avrami-Erofe’ev equation A2, with an activation energy of 111(7) kJ mol⁻¹.     

十八元环多钒硼酸盐的水热合成及其氧化还原性质研究

在水热条件下合成了[Ni(en)2]6[(VO)12O6B18O39(OH)3].6H2O多钒硼酸盐,X射线衍射分析表明,该晶体属三方晶系,R-3空间群.测试了晶体的IR光谱和TG曲线,用循环伏安法详细研究了合成化合物的氧化还原性质及电子转移机理,结果表明该化合物具有两对氧化还原峰,其电子转移数分别为单电子和三电子.     

反相毛细管电色谱中中性化合物的保留及有机改性剂对其保留值的影响

以硫脲作为电渗流标记物测定的死时间和以苯同系物线性回归方法测定的死时间为基础，将液相色谱中溶质保留值方程应用到电色谱中，得到了容量因子与二元流动相体系中有机改性剂含量之间的关系曲线；通过实验数据说明了一些极性的电中性化合物在电场作用下也会发生迁移而引起保留值的变化，且这种变化还受有机改性剂含量的影响。