内式及外式-5,5-二取代-3-氧代-4-氧杂三环[5,2,1,02,6]-8-癸烯类化合物的合成

由于许多降冰片烷衍生物及内酯类化合物都是很好的香原料,可用于调制化妆品或食用香精。为了探讨结构与香气的关系,并寻找新型的香原料,我们将上述两部分骨架-降冰片烷环系及内酯环系结合在一起,合成了具有如下结构的化合物16个。     

五元氮杂糖衍生物的实用有效合成方法

以D-葡萄糖为原料, 经具有降冰片烷结构的双环缩醛中间体, 合成了部分羟基保护的1-脱氧-D-氮杂阿拉伯糖衍生物, 提供了一种合成五元氮杂糖衍生物的简便有效方法.     

大位阻α-二亚胺钯配合物催化降冰片烯与5-降冰片烯-2-乙酸酯的共聚研究

采用大位阻9,10-二氢-9,10-乙醇蒽~(-1)1,12-二亚胺钯配合物为主催化剂,三五氟苯基硼B(C6F5)3为助催化剂,在甲苯中对降冰片烯与极性降冰片烯衍生物5-降冰片烯-2-乙酸酯进行加成共聚合研究,呈现出高催化活性(1.1×10~4~1.6×10~6g_(polymer)/molPd·h)。当5-降冰片烯-2-乙酸酯加入摩尔比为10~50%时,其插入率为5.53~8.45%。聚合反应产率随着5-降冰片烯-2-乙酸酯加入摩尔比的增大而减小。共聚物的热分解温度T_d、玻璃化转变温度T_g和分子量Mw分别为332.4~432.5℃、259.9~306.6℃和2.3×104~8.6×104g·mol~(-1)。     

手性降冰片烯衍生物的制备及应用

手性降冰片烯类衍生物是C5主馏分之一的(双)环戊二烯中一类重要的高附加值衍生产品,主要由环戊二烯和非对称的亲双烯体通过Diels-Alder反应制得。本文从合成手性降冰片烯衍生物的机理出发,重点介绍了在有/无催化剂条件下制备手性降冰片烯酯类、醛类、酮类和酰基口恶唑烷酮类衍生物时的收率和立体选择性等。由手性二醇、二酚或口恶唑啉与配位较强的铝、硼、铜、钛或镧系金属络合物等配位而成的手性催化剂有利于提高手性降冰片烯衍生物合成速度及其立体选择性。同时,本文针对近年来手性降冰片烯衍生物在光致变色的光学材料和阴离子、阳离子及复合离子交换膜领域中的应用进行了简要概述。最后,对其研究方向和应用前景进行了展望。     

多羟基吡咯烷衍生物的立体选择性合成

以D-木糖及D-葡萄糖为原料, 经具有降冰片结构的双环缩醛中间体, 合成了适当羟基保护的五元环氮杂糖衍生物及其氟代衍生物, 进一步探讨了含氮杂糖结构的双糖衍生物的合成.     

8-苯胺-1-萘磺酸钛配合物的合成及催化乙烯与降冰片烯共聚合反应

合成了新型催化剂8-苯胺-1-萘磺酸钛配合物, 并应用于乙烯与降冰片烯的共聚合反应中. 分别考察了助催化剂种类[甲基铝氧烷(MAO)和三乙基铝(TEA)]、 降冰片烯浓度、 Al/Ti摩尔比、 聚合温度和聚合压力对催化活性与共聚性能的影响. 通过核磁共振、示差扫描量热和凝胶渗透色谱等对所制备的共聚物进行了表征. 结果表明, 在相同条件下, 以MAO为助催化剂时, 共聚催化活性更高, 催化剂为单活性中心, 可得到分子量分布较窄(PDI≈3)的共聚产物, 其共聚反应机理为加成聚合. 另外, 随着降冰片烯浓度的升高, 共聚物中降冰片烯单元的摩尔比呈线性上升趋势, 所得共聚物的熔点随之降低.     

2-羟基-5,6,7,8-四氢-5,8-亚甲基喹啉-3-羧酸的合成

5,6,7,8-四氢喹啉及衍生物是医药和农药的重要中间体。2-羟基-5,6,7,8-四氢-5,8-亚甲基喹啉-3-羧酸是合成HIF脯氨酰羟化酶抑制剂的重要中间体,其合成方法目前无文献报道。本文以降冰片烯为起始原料,经水合、氧化、缩合、环合和水解5步反应合成目标产物,总收率43.09%,结构经¹H NMR、 ¹³C NMR和MS确证。该路线具有原料廉价易得、操作简单、后处理方便且收率较高等优点,适合工业化生产。     

7-羟甲基-7-羟基双环[3,3,1]壬烷-3-酮的合成并转换成1-羟基-4-原金刚烷酮（英文）

３,７－二取代双环［３,３,１］壬烷衍生物具有许多有趣的反应特异性,可合成各种官能性金刚烷衍生物。本文以１－金刚烷醇为原料经二步反应合成７－亚甲基双环［３,３,１］壬烷－３－酮。再用催化量四氧化锇进行氧化几乎定量地得到７－羟甲基－７－羟基双环［３,３,１］壬烷－３－酮（９）。９用对甲苯磺酰氯处理得１１,然后转换成１－羟基－４－原金刚烷酮（８）。根据光谱数据分析,（９）有一互变异构体（１０）,研究表明１０的存在对合成８没有影响。预计８可以作为合成各种三取代金刚烷的原料。     

顺-5-降冰片烷-外-2,3-二甲酰亚胺的合成

以顺-5-降冰片烯-外-2,3-二甲酸酐（2）为原料,氨气为氨源,经氨化反应制得顺-5-降冰片烯-外-2,3-二甲酰亚胺（3）; 3经钯炭催化氢化合成了盐酸鲁拉西酮关键中间体顺-5-降冰片烷-外-2,3-二甲酰亚胺（1）,其结构经¹ H NMR和MS（ESI）确证。研究了2与氨气的投料比[r=n（2）/n（氨气）]、反应时间、析晶时间对3外观和收率的影响,以及氢化反应温度和反应时间对1外观和收率的影响。结果表明：合成3的最佳反应条件为：r=1.0/2.5,反应时间25~30 h,析晶时间6~8 h, 3收率93.2%。合成1的最佳反应条件为：氢化反应温度20~30 ℃,反应时间6~10 h, 1收率98.2%。 1的中试极限条件为：于40~50 ℃浓缩6 h,湿品于45~55 ℃干燥8 h,总收率91.5%。     

5-丁氧基亚甲基-2-降冰片烯的合成及其加成聚合反应

采用降冰片烯-5-甲醇和溴丁烷在氢化钠作用下合成了5-丁氧基亚甲基-2-降冰片烯,双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3催化体系使之聚合。 考察了聚合时间对其均聚合的影响以及5-丁氧基亚甲基-2-降冰片烯和降冰片烯不同摩尔投料比对其共聚行为的影响。 采用1H NMR、FTIR和TGA测试技术对所得的聚合物进行了结构表征和性能测试。 结果表明,双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3催化体系对5-丁氧基亚甲基-2-降冰片烯均聚和共聚具有较高的催化活性。 得到的均聚物和共聚物为加成型聚合物,料液中5-丁氧基亚甲基-2-降冰片烯的摩尔分数为10%~90%时,其在共聚物中的插入率为22.1%~76.9%,所得聚合物具有较好的热稳定性（Td＞360 ℃）,在THF和CHCl3等许多普通溶剂中有很好的溶解性能。     

ClO与ClO自由基反应机理及电子密度拓扑分析

利用密度泛函理论对ClO与ClO自由基反应机理进行了深入理论探讨,在B3LYP/6-311＋＋G（3df）水平上对该反应体系的反应物、中间体、过渡态及产物进行了几何构型优化,对反应通道进行了IRC(内禀反应坐标）路径解析,计算了沿各反应通道的能垒和离解能,并进行了零点能校正.从量子拓扑学的角度,对反应通道IRC途径上一些重要点进行了电子密度拓扑分析,讨论了反应过程中化学键的断裂、生成以及键的变化规律,找到了反应途径的能量过渡态和结构过渡态.     

飞行时间二次离子质谱(TOF-SIMS)结合化学衍生法分析杂环新化合物的结构

飞行时间二次离子质谱(TOF-SIMS)分析了难挥发的杂环新化合物咪唑啉硫氰酸盐及其三种衍生物, 确认出很强的氢离化及银离化准分子离子峰, 通过对各种衍生物谱图的对照分析, 确认出较强的含有结构特征的碎片离子峰, 并对该化合物在离子轰击下的裂解规律作了分析, 支持了对该新化合物结构的鉴定。     

Pt/HM、Pd/HM催化剂上CO氧化反应活性和动力学研究

研究了Pt/HM、Pd/HM催化剂上CO氧化反应的活性,求出了各种催化剂的CO氧化反应动力学方程。考察了不同气氛下CO氧化活性的演变规律和V⁴⁺、Co²⁺离子对Pt、Pd的助催化作用,并用催化剂集团结构适应模型对以上结果作出了解释。     

Facile synthesis methodology and characterization studies of silica-decorated hybridized anisotropic nanotubes and nanosheets

Carbonaceous nanomaterials and their derivatives have been inspired tremendous enthusiasm in the scientific community. They have been excogitated as the encouraging attributes and the qualified dispersed phase to develop multi-functional composites. Particularly, graphene and carbon nanotube (anisotropic fillers) have gained substantial research interest owing to their promising characteristics. This highlights an innovative technique to synthesize hybridized nanotube and nanosheet. Initially, parent materials have been synthesized: The pristine CNT has been modified by acid mixture solution, and reduced graphene oxide has been prepared by chemical reduction method. Henceforth, the self-assembly in situ sol–gel technique has been endorsed here. The synthesized nanohybrids have been characterized by different spectroscopic techniques: FTIR, Raman, UV, and XPS to confirm the attachment of multifunctionalities; meanwhile, the composition and stability have been investigated from XRD and TGA plots. The magnitude of surface charge and particle size distribution have been evaluated for the parent and hybridized products; further, morphology of all the samples has been authenticated from FESEM and TEM.     

快原子轰击质谱及其在金属有机配合物研究中的应用

本文介绍FAB质谱的原理、功能和优点。综述了FAB机理,讨论了影响FAB谱的因素。归纳了FAB法在金属有机配合物研究中的应用。     

Theoretical Study of the AICI Disproportionation Reaction Mechanism on the Al(100) Surface

The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum (100) surfaces has been investigated by the plane-wave density functional theory (DFT).Three kinds of possible reaction mechanism of AlCl disproportionation reaction on the aluminum (100)surfaces have been taken into account. The structures of reactants and products have been optimized, transition states have been confirmed and activation energies have been calculated. The adsorption energy of reactants and desorption energy of products have been determined. All of these have been employed to confirm the reaction mechanism and the rate determining step of AlCl disproportionation reaction on the aluminum (100) surfaces.     

Phase structure of silanol-modified ethylene-vinyl acetate copolymers

For (ethylene-vinyl acetate copolymer)-tetraethoxysilane and (ethylene-vinyl acetate copolymer)-polydimethylsiloxane systems, the solubility of components has been studied in a wide range of temperatures and compositions. Phase diagrams have been constructed, pair interaction parameters have been calculated, and diffusion coefficients and activation energies of diffusion have been estimated. The temperature and concentration ranges of a change in solubility related to chemical interactions between the components have been revealed, and the structure of the modified copolymers has been studied. On the basis of the kinetic data on the movement of isoconcentration planes in diffusion zones of component mixing, time intervals corresponding to the onset of the chemical reaction between the components have been determined and the apparent activation energies of the process have been computed. Complex-shaped binodal and boundary curves have been interpreted within the framework of the classical Flory-Huggins theory.     

3-芳氧基-6-取代哒嗪的合成及其除草活性

合成了系列3-芳氧基-6-取代哒嗪类化合物.化合物结构经¹HNMR、元素分析、IR和MS确证.生物活性测试结果表明,该类化合物具有很好的除草活性,讨论了其结构与除草活性的关系.     

侧链液晶高分子的非线性光学特征及其应用

阐述了侧链高分子液晶非线性光学的基本原理,着重讨论了影响非线性光学特征的几个基本因素,说明了双折射与外场强度、双折射与序参数之间的定量关系,展望了侧链高分子液晶非线性光学特征在一些领域中的应用前景。     

Overpressured thin-layer chromatography

The properties, apparatus and applications of overpressured thin-layer chromatography (OPTLC) have been reviewed. In the Introduction planar chromatography has been briefly characterized, with particular attention to TLC. The general properties of OPTLC and methods of development of chromatograms in this technique have been then given. The construction of chambers and equipment for OPTLC has been described, paying attention to two-dimensional columns. The properties of chambers for OPTLC have been characterized considering the flow of eluent, sorbent-eluent interactions and the efficiency of various systems. OPTLC, TLC and HPTLC have been compared and also a comparison between OPTLC with a constant (linear) eluent flow-rate and with a decreasing eluent flow-rate has been made. Analytical applications of OPTLC have been described and examples of separations of mixtures have been given.