具有好的溶解性和高的热稳定性的富勒烯-苝化合物的合成

在氩气保护下,利用N-(正丁基)-N’(4-甲酰基苯氧戊基)-1．6,7,12-四-(4-叔丁基苯氧基)-3,4,9,10-苝酰亚胺和N-甲基甘氨酸产生的亚胺叶立德与富勒烯反应,合成了含富勒烯的苝化合物,用NMR、FT—IR、UV-Vis及TGA等方法对其结构和性能进行了表征和测试。研究结果表明此类化合物具有好的溶解性和高的热稳定性。     

酯的水解实验的改进

该文对现行的高中化学 (试验修订本 )第二册中关于乙酸乙酯水解实验的不足之处进行了分析,并提出了改进的方法,对其实验内容和实验效果进行了讨论。     

基于压力的速率方程的应用

通过具体实例说明对于气相反应,使用基于压力的速率方程解题比使用基于浓度的速率方程更直接﹑更简便。总结了具有简单级数的反应的基于压力的速率方程及其特征。     

地球的内部可能是湿润的

在地球的低层地幔下 ,可能存在着比现在的海洋还要多 4倍的水 ,这是日本工业大学的Ｍ .Ｍｕｒａｋａｍｉ和他的同事们最近估测出来的。日本地球科学家们利用了一种多功能钻探仪 ,通过对 3种据信包含低层地幔中在高温高压下生成的主要矿物组成的分析后 ,得到了这个结论。这 3种矿物是 :Ｍｇ ｐｅｒｏｖｓｋｉｔｅ ,Ｃａ ｐｅｒｏｖｓｋｉｔｅ和Ｍａｇｎｅｓｉｏｗ櫣ｓｔｉｔｅ。再利用ＳＩＭＳ对矿物中溶解的氢的含量进行测量 ,矿物学家认为氢是水的标记。发现这3种矿物的含水量都相当可观 ,大约在 0 .2 %至 0 .4 %(重量比率 )之间。用红外…     

基于环糊精的农药吸附剂的研究进展

农药的研发与使用极大地提高了农作物的产量,为解决人类温饱、改善人类生活品质做出了贡献。但是,农药广泛残留于农副产品以及土壤和水体中,造成的污染日趋严重。残留的农药通常具有微量致毒、难生物降解、生物累积等特性,对生物健康与生态系统造成了巨大威胁。高效检测微量农药、减小污染危害是亟待解决的问题。吸附法具有成本低、操作简单、稳定性强、可重复性强的特点,在农药分离预富集领域得到了广泛关注。作为一种常用的农药吸附剂材料,环糊精是一类具有空腔的超分子化合物,能够作为主体通过主客体作用形成包合物;另外,可以通过醚化、酯化、氧化等化学反应对环糊精进行后修饰以提高其吸附性能。疏水作用、静电作用、范德华力、氢键作用、立体效应协同促进对农药的吸附。环糊精在农药吸附领域已经取得了一定进展,但是目前还没有基于环糊精的农药吸附剂的综述。该文针对杀菌剂、杀虫剂、除草剂、植物生长调节剂这4类农药,系统性地评述了基于环糊精的农药吸附剂的制备、吸附机理及应用,目前存在个别吸附剂吸附容量不高、降解机理不明确、降解产物对环境不友好、容易造成二次污染的问题,研发高吸附容量、易回收、易分离、易再生的基于环糊精的农药吸附剂是未来的主要研究方向。     

铁的吸氧腐蚀实验的改进

正1问题的提出化学实验是化学教学的生命线,在课堂教学中发挥着重要的认识论功能、方法论功能和教学论功能[1]。笔者在利用教科书中铁的吸氧腐蚀实验[2]进行教学时,如图1,发现该实验仅能让学生体会吸氧腐蚀的吸氧过程,而更核心的电化学过程却无法感受到。通过查阅近年文献,发现同仁们对该实验的研究更多关注如何缩短实验所用时间[3-6]。即便     

糖基修饰的氨基酸类化合物的合成

通过对5种氨基酸酯化和氨基保护得到苄氧羰基氨基酸甲酯, 经肼解制备苄氧羰基氨基酸酰肼, 然后分别与3种不同的糖基异硫氰酸酯反应, 制备了相应的目标化合物15个, 且产率均在60%以上. 所有新化合物均经元素分析, IR, MS和¹H NMR确证. 同时探索了苄氧羰基氨基酸甲酯肼解的最佳反应条件.     

基于Matlab的二元共聚合反应的竞聚率的求解

以直线交叉法为依据,根据最小二乘原理,采用Matlab GUI工具设计了一款用于计算二元共聚合反应竞聚率的图形用户程序。与传统的求解竞聚率方法相比,该图形用户程序具有设计原理简单、计算快捷的特点;同时程序提供界面简洁、交互友好的数据输入平台,实用性强。实际应用表明:采用该款图形用户程序所测得的数据与微机动态搜索法、Tidwell-Mortimer法相近,而比采用斜率截距法计算竞聚率的最小差方和更小,并且也避免了采用斜率截距法由于所用方程的非对称性造成的计算结果的不一致性。     

基于环糊精的新材料的研究进展

从纳米粒子、水凝胶、纤维材料和环糊精高分子等方面介绍了近年来以环糊精为基础研制的新材料的研究进展。目前以环糊精为基础的纳米粒子材料有核壳结构的纳米粒子、环糊精的化学接枝与共聚、环糊精与无机非金属材料的复合和含环糊精的囊泡材料;以环糊精为基础的凝胶材料有水凝胶和有机凝胶两种材料;此外还有以环糊精为基础的纤维材料、环糊精高...     

某些助剂对明胶的凝胶强度的影响的研究

众所周知,物理力学性能是照相明胶的一种很重要的属性。在各种彩色及黑白胶片都面向高温快速加工发展的今天,这种属性就显得更为重要。提高胶片的物理力学性能,一方面要从提高明胶本身的胶冻强度着手,例如减少明胶中溶胶组份(分子量小、冷水中溶解度高),提高明胶中的α和β组份的相对含量,减少分子量过大的组份等等。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.