第十八届国际化学奥林匹克简讯

1986.7.6—7.15第十八届国际化学奥林匹克在荷兰来顿举行。22个国家86名中学生参加了竞赛。我国派遣王夔、吴国庆作为观察员出席,为下届参赛作了准备。竞赛分理论试题和化学实验两项,分别为五小时和五个半小时。理论试题共七题,其中无机化学两题、有机化学两题、生物化学一题、结构化学一题、化学工程一题。实验试题为无机合成与容量分析。竞赛结果11人获金质奖,15人获银质奖,25人获铜质奖,此外还向各题最高得分手发了单项奖。荷兰选手成绩最佳,获金质奖、银质奖的各两名。亚洲国家仅科威特参赛,未获奖。据悉,第十九届国际化学奥林匹克将于1987年7月在匈牙利举行。我国已决定组团参赛。从全图选拔选手的工作正在紧张筹备。     

高考全国理综卷Ⅰ第28．（7）小题的不同解答

2005年高考理综试卷（全国卷Ⅰ）第28题的最后一小题：“（7）还可以用其他实验方法测定试样中纯碱的质量分数。请简述一种不同的实验方法”，很好地体现了作答的开放性。虽然知识和能力的起点和落点都不为高，但是突出了化学的学科特点，重点考查的是运用基础知识，设计基本化学实验的能力。     

晶粒取向度与烧结钕铁硼磁体的矫顽力

实验发现，烧结钕铁硼永磁合金的矫顽力随磁体内晶粒取向程度的提高（取向系数ａ的减小）而下降。根据不同矫顽力理论对各种取向程度磁体矫顽力的计算值与实验结果对比表明：成核机制与钉钆机制和实验结果偏离较大，用反磁化核长大的发动场理论很好地解释了矫顽力的晶粒取向度关系。     

第三主族金属簇合物

金属簇合物化学是在金属有机化学与无机配合物化学基础上发展起来的一门新兴学科。第ⅢA族元素由于其缺电子特性而备受关注,大量以前认为不存在的、具有双键或叁键的第三主族金属簇合物分子相继被合成,并且通过X射线衍射和光谱学分析得到了它们的结构和性质。本文介绍了第ⅢA族金属簇合物的实验及理论研究进展,同时也提出了一些需要深入解决的新问题。     

科学家发现第Ⅲ号元素

国际理论和应用化学联合会不久前认定,德国达姆施塔特重离子研究所的科学家发现了第111号元素。 据德国“科学”网站报道,科学家西古德·霍夫曼与同事早在1994年就利用镍元素和铋元素进行对撞实验,观测     

温度对光学纤维自发喇曼光谱强度的影响

测量了不同温度下ＣＣｌ４液芯光纤喇曼光谱强度，实验结果表明，光谱强度随着温度的变化存在着一个极大值，对影响光纤喇曼光谱强度的几个主要因素进行了估算，理论与实验结果符合较好。     

分光光度法与激光热透镜光谱分析法测定高散射物质光吸收的比较

通过理论和实验比较了分光光度法与激光热透镜光谱分析法在高散射背景下测量物质光吸收的差异。研究了在不同含量纳米TiO2的散射背景下，散射对分光光度法和热透镜光谱分析法测定耐尔蓝溶液含量的影响。结果表明，分光光度法对具有光散射性质试样的测定存在较大误差，而激光热透镜光谱分析法能较好的避免散射影响，测定结果准确。实验结果与理论分析相一致。     

国际奥林匹克化学竞赛——第十八届国际化学奥林匹克

1986.7.6-7.15第18届国际化学奥林匹克在荷兰来顿举行。22国86名中学生参赛。我国派王夔教授、吴国庆副教授作为观察员出席。竞赛分理论试题和实验两项,分别为五小时和五个半小时。理论试题共七题:无机化学两题、有机化学两题、生物化学一题、物理化学一题、工业化学一题。实验为无机合成及其组成分析。     

Zeeman原子吸收光谱分析法中谱线轮廓的研究Ⅴ.Ag328.1nm的分析性能

从理论和实验两方面研究和讨论了在ＺＡＡＳ法中，不同调制方式及磁感应强度对Ａｇ３２８．１ｎｍ的分析性能的影响，并取得一致的结果     

从化学实验竞赛探讨高校化学实验教学的改革和创新*——第11届全国大学生化学实验邀请赛理论试题的解析与思考

从命题思路、试题内容及特点和结果分析等3个方面对第11届全国大学生化学实验邀请赛的理论试题进行讨论分析和总结,同时对化学实验教学的改革提出几点思考和建议,以期促进高校化学实验教学的改革和创新。     

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.     

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%).     

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.     

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.