1997年全国高中学生化学竞赛(初赛)试题与试题分析

今年的全国高中学生化学竞赛的初赛刚刚结束。我们认为这次竞赛的试题较好地体现了今年5月全国高中学生化学竞赛工作会议上再次肯定的试题的水平要求:原理水平大致与人民教育出版社的《化学读本》相当,基本上不涉及更高一级的,即大学化学的原理,但考虑到冬令营的优胜选手以及参加国际竞赛的选拔,需要补充一定量的静态立体化学的知识(包括立体异构),当然试题涉及的具体化学内容本身对中学生是陌生的,但用竞赛学生的已有知识以及适当增加的知识为基础是可以理解的。为进一步考察试题的难易,我们对试题作如下的分析。     

姜黄素衍生物与类似物的构效关系研究进展

根据目前对姜黄素衍生物与类似物的结构与药理作用的关系的研究现状,论述了姜黄素衍生物与类似物的结构与其抗氧化、抗炎和抗肿瘤的药理作用的关系,包括对姜黄素及其衍生物与类似物的结构修饰与其活性之间的关系的论述。大量的实验结果显示姜黄素衍生物与类似物的药理作用与其结构中所具有的官能团有着密切的关系,这为新药开发提供了一个很好的方向。     

泽林斯基学派底发展道路(二)

二、烃的互相转变泽林斯基及其学派在烃的互相转变方面的研究,也有不可比拟的巨大成就。石油工业在国民经济中是相当庞大的、最重要的工业部门之一,天然气和石油是烃的最重要的来源。全世界石油年产量达三亿吨以上(不包括苏联在内),它的产量仅次于煤炭工业。但是几乎所有产品都用来做内燃机的燃料、润滑油等,仅有少数的作为化学工业的原料,然而利用石油作化学工业原料的需要是与日俱增的。对于石油的产品用为内燃机燃料及润滑油的要求,在今后会变得更为严格,这就是说:在不同用途的产品中烃类的化学组成不是完全没有关系的,仅一定类型的烃类在现代的航空、汽车及拖拉机发     

在化学教学中对学生的科学—无神论教育

在对学生的科学-无神论的教育中,化学教师的任务取决于我们苏维埃学校的总任务。苏维埃的学校是“教育出能够彻底建成共产主义一代”的工具。共产主义与宗教是不相容的。共产主义者“不能够也不应该对表现在宗教信仰形式中的无知、愚昧、和黑暗势力熟视无睹。”“因为党是拥护科学的,而宗教偏见是反对科学的”。在培养极积的、自觉的共产主义建议者的事业中,对学生的科学-无神论教育是化学教师的一项极其重要的任务。在共产党和苏联政府的领导下,总的来讲我们的学校卓有成效地担起了自己的教育-教养的任务。她培养了掌握科学基础的、思想健全的、体魄     

定性分析教学中的一些问题

在当前的分析化学教学中,定性分析仍占有相当重要的地位。它的主要作用,是使学生在系统地学习元素周期律的基础上,进一步掌握常见离子的基本性质,为定量分析及今后的工作打下坚实的基础。但是,从最近几年来的实际教学情况来看,定性分析部分的教学工作一直存在一些问题。造成这种情况的原因是多方面的：如在编写教材过程中,对有些问题未能进一步进行研究;不同的参考书的提法不尽相同;硫代乙酰胺的引入带来了许多新的实验现象而目前得不到很好的解释;实验条件的改变导致许多离子的反应出现异常情况等。     

改进的微乳液聚合制备的聚甲基丙烯酸甲酯的力学和光学性能研究

研究了改进的微乳液聚合方法制备的聚甲基丙烯酸甲酯(PMMA)的力学和光学性能, 并与本体聚合制备的PMMA相比较. 研究结果表明, 由改进的微乳液聚合制备的PMMA具有较高的Tg和富间规度, 在较宽的温度范围内具有较高的力学模量. 此外, 它的拉伸强度、拉伸模量及断裂伸长率均比本体聚合制备的PMMA样品高. PMMA的折光率与制备方法关系不大, 但由改进的微乳液聚合制备的PMMA样品消光系数更小, 更加透明. 这说明由改进的微乳液聚合方法制备的PMMA具有更广泛的应用前景.     

Mn助剂对CuFeZrO2低碳醇合成催化剂的修饰作用

利用程序升温还原和原位漫反射红外光谱技术研究了Mn修饰的CuFeZrO2催化剂的结构特性,并测试了催化剂的CO加氢合成低碳醇的反应性能.研究表明，适量添加锰助剂有利于提高催化剂的反应活性,提高产物中C2＋醇的含量,抑制甲烷的生成,但随锰含量的增加催化剂的活性和选择性呈现先增加后下降的趋势.程序升温还原的测试表明,锰助剂通过与铜的相互作用使铜的还原变得困难,影响铜在催化剂上的状态,随锰的加入量的增加这种作用得到加强.铜分散度的测定表明锰促进了铜的分散,利用探针分子CO在催化剂上吸附的漫反射红外光谱研究发现,锰助剂可以提高组分间的相互作用,影响铜的电子性质,从而增加了CO在铜上的吸附.     

如何教给同学系统的，巩固的化学基础知识

在中学化学教学大纲上指示,中学化学教学的基本任务:“第一就是使学生获得一定的系统的和巩固的化学基本知识……。”我觉得这样的要求是非常恰当的。系统的鞏固的化学基本知识,就不是零碎的、片面的、散乱的一堆化学材料,而是系统的、科学的、自然界物质变化的规律;不是无用的、累赘的、死板的知识,而是学了化学之後,能获得合乎高等学校要求的化学基础,或是直接为国家的生产建设服务。因而在正确的进行系统的、鞏固的基本化学知识的讲授     

伴有辅酶再生的生物催化过程

很多生物催化的氧化还原反应需要昂贵辅酶的参与,本文详细介绍了伴有辅酶再生的生物催化过程中,辅酶的使用、辅酶的酶反应再生、电化学再生及载体再生的特点,并对各种再生方法的优缺点进行了比较,同时介绍了辅酶的固定化及化学改性方法的研究进展.简单综述了伴有辅酶再生的基于细胞、游离酶和固定化酶的生物催化系统的研究和应用,并展望了辅酶的研究前景及辅酶再生研究的发展方向和亟待解决的问题.     

我国古代人民制造陶器的化学工艺

我们伟大的祖国有极其悠久的文化史,这不是一句空洞的自豪的话,而是有许许多多的事实可以证明的。除了古代文献的纪载以外,我们在最近三十多年来,由於考古学家的努力,在地下发掘出很多文字所未曾记录的史前遗物,从这些遗物里,我们可以确切地认识到我们古代的文化,古代人民丰富的发明和创造。现在所已知的史前遗物可以说还仅仅是埋藏在地下的极小的一部分,将来继续不断的发掘可以有更大的收获,而已经得到的古物也尚有待於更深入的和广泛详细的研究。可是即就现有的资料和研究结果来说,已足以充分说明我国古代文化的悠久与可爱了。     

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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

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.     

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.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.