金属富勒烯La＠C_（2n）的合成、提取及其ESR和MS表征

采用对掺入Ｌａ_２Ｏ_３的石墨棒原位活化并结合交换电极回放方法制备了产率较高的金属富勒烯，并用甲苯高温热提取的方法有效地提取出Ｌａ＠Ｃ_（２ｎ），其中Ｌａ＠Ｃ_（７４）为可溶性金属富勒烯增加了新成员．同时，首次采用解吸电子轰击质谱对提取物进行了表征，讨论了提取物的ＥＳＲ谱．     

用于富勒烯分离的高效液相色谱固定相

用于富勒烯分离的高效液相色谱固定相陈德朴，郁鉴源，廖沐真，黄贺生，刘凤英，刘梦林（清华大学化学系，北京，１０００８４）（清华大学现代应用物理系）关键词Ｃ_（６０）、Ｃ_（７０）分离，固定相，高效液相色谱目前有关富勒烯的研究是国际上一个非常活跃的研究领域...     

1，3，6，11，13，18，28，31－八溴富勒烯－C_（60）LB膜特性及导电性的研究

１，３，６，１１，１３，１８，２８，３１－八溴富勒烯－Ｃ_（６０）ＬＢ膜特性及导电性的研究叶玉汉，肖玉方（宁波师范学院化学系，宁波，３１５０２０）（中国科学院兰州化学物理研究所）关键词１，３，６，１１，１３，１８，２８，３１－八溴富勒烯，Ｃ_（６０）Ｌ...     

高富勒烯的提取,分离和分析

采用二硫化碳重结晶富勒烯混合物或二硫化碳二次抽提烟灰以提取高富勒烯（ｈｉｇｈｅｒｆｕｌｅｒｅｎｅｓ，Ｃｎ，ｎ＞７０）。产物经高效液相色谱分析，高富勒烯的含量从１％分别提高到４％和６％；经激光飞行时间质谱证明，产物中除含主要成分Ｃ６０和Ｃ７０以外，还含有Ｃ７６、Ｃ７８、Ｃ８２、Ｃ８４以及更高碳原子的富勒烯。     

C_（60）化学修饰的PNVC材料的UV－VIS谱研究

本实验采用金属有机化学方法成功地将富勒烯分子引入到ＰＮＶＣ侧链形成ＣＢＰ（ＣｈａｒｍＢｒａｃｅｌｅｔＰｏｌｙｍｅｒ）型共聚功能材料，研究了其ＵＶ－ＶＩｓ谱行为。结果表明，Ｃ_（６０）或Ｃ_（６０）／Ｃ_（７０）混合物化学修饰的产物其紫外可见谱明显向长波方向移动，谱峰范围由２８０ｎｍ扩展至８７０ｎｍ。Ｃ_（６０）含量增加，红移程度增大，在可见区域的吸收程度亦增加。产物主要存在５个特征峰，分别位于２１５ｎｍ、２６５ｎｍ、２９８ｎｍ、３３５ｎｍ、３４５ｎｍ处，其中２１５ｎｍ峰为Ｃ_（６０）仅存的特征峰。最后讨论了不同合成条件与产物硝化处理对其ＵＶ－ＶＩＳ谱行为的影响。     

同时测定食用植物油中抗氧剂叔丁基对羟基茴香醚和2，6－二叔丁基对甲酚的方法

报道了用高效液用色谱法同时测定食用植物油中的抗氧剂叔丁基对羟基茴香醚（ＢＨＡ）和２，６－二叔丁基对甲酚（ＢＨＴ）的实验方法。采用ＺｏｒｂａｘＯＤＳＣ_（１８）色谱住，甲醇：水（９０：１０，Ｖ／Ｖ）作流动相，检测波长为２４５ｎｍ，流速为１ｍＬ／ｍｉｎ。检测下限分别为１５ｎｇ（ＢＨＡ），９０ｎｇ（ＢＨＴ），回收率分别是９６．８％±９．８％（ＢＨＡ），９９．０％±３．２％（ＢＨＴ）。方法快速、准确，灵敏度高。     

一种新的稳定的C60衍生物

一种新的稳定的Ｃ_（６０）衍生物德国化学家Ｋ．Ｍｕｌｌｅｎ等人用下述方法合成了一种新的Ｃ（６０）衍生物：这一反应具有选择性，且生成物有很好的稳定性，因此对富勒烯的制备化学很有意义。目前，Ｋ．Ｍｕｌｌｅｎ等人正试图利用这一反应来制备适合聚合的Ｃ（６０）?..     

金属富勒烯的价π轨道成键,杜瓦结构和无π轨道自由基结构

对富勒烯的价π轨道成键和无π轨道自由基进行了理论研究，得到内接和外接一种和多种金属富勒烯的各种可能对称性和结构，除了Ｃ６０（Ｉｈ），Ｃ３４（Ｃ３ｖ）和Ｃ２８（Ｔｄ）外，我们还研究了Ｃ３３（Ｃ３），Ｃ５６（Ｔｄ）和Ｃ６８（Ｔｄ）。这样的价键观点将为分子轨道计算以及分子构件配置的相反观点提供新的见解。     

C_（60）与n－Bu_3SnH的自由基反应研究

Ｃ_（６０）与ｎ－Ｂｕ_３ＳｎＨ的自由基反应研究余益民，郭兴华，刘子阳，刘淑莹，傅芳信，钱明星（中国科学院长春应用化学研究所，长春，１３００２２）（东北师范大学化学系）关键词自由基反应，富勒烯，三丁基锡氢化物，自由基海绵自Ｋｒａｔｓｃｈｍｅｒ等［１］实...     

链状三核异金属簇阴离子［Cl_2FeS_2M＇（PPh_3）_2］~－（M＝Mo

在５５０～９０ｃｍ~（－１）波数范围内，测量簇阴离子［Ｃｌ_２ＦｅＳ_２ＭＳ_２Ｍ′（ＰＰｈ_３）_２］~－（Ｍ＝Ｍｏ，Ｍ′＝Ａｇ；Ｍ＝Ｗ，Ｍ′＝Ｃｕ，Ａｇ）的付里叶变换红外光谱，并对标题簇阴离子［Ｃｌ_２ＦｅＳ_２ＷＳ_２Ｃｕ（ＰＰｈ_３）_２］~－，［Ｃｌ_２ＦｅＳ_２ＭｏＳ_２Ａｇ（ＰＰｈ_３）_２］~－和［Ｃｌ_２ＦｅＳ_２ＷＳ_２Ａｇ（ＰＰｈ_３）_２］~－骨架的振动光谱给予经验指认。同时采用＂诱导自洽方法计算振动力常数＂程序，对簇骨架［Ｃｌ_２ＦｅＳ_２ＭＳ_２Ｍ~′Ｐ_２］进行简正坐标分析。振动频率的计算值与观测值符合良好，两者平均偏差小于１．０％，计算结果支持了振动谱带的归属并表明计算力常数的合理性。文中还讨论了主要价键振动频率的变化规律。     

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.