C60[RuHCl（CO）（PPh3）]3配合物的合成和表征

富勒烯配合物的制备及其性质的研究是目前富勒烯化学最为活跃的研究领域之一［１］,人们正致力于探索富勒烯各类衍生物的结构与性质之间的依赖关系,以期合成出具有特殊性能的富勒烯配合物,为富勒烯的实际开发应用奠定基础。本文首次合成Ｃ６０［ＲｕＨＣｌ（ＣＯ）（ＰＰｈ３）］３配合物,采用元素分析、红外光谱、电子光谱进行鉴定和表征,并推测了其结构。１　实验部分１．１　Ｃ６０［ＲｕＨＣｌ（ＣＯ）（ＰＰｈ３）］３的合成合成按下列反应进行：ＲｕＣｌ３＋３ＰＰｈ３＋ＨＣＨＯ→ＲｕＨＣｌ（ＣＯ）（ＰＰｈ３）３ＲｕＨＣｌ（…     

分子C_(60)CH_2(C_(2V))气相热力学性质的理论研究

自从富勒烯被发现并能常量制备以来,人们就开始了对Ｃ６０衍生物的研究．Ｃ６０ＣＨ２是Ｃ６０最简单的衍生物之一,Ｃ６０ＣＨ２有２种异构体,根据所属点群的对称性划分一种是属Ｃ２Ｖ群的Ｃ６０ＣＨ２（Ｃ２Ｖ）,另一种是属ＣＳ群的Ｃ６０ＣＨ２（ＣＳ）．文献［１］...     

含镧金属富勒烯不同溶剂的高温高压提取

将金属原子或离子置于以Ｃ６０、Ｃ８２为代表的富勒烯笼内形成金属富勒烯包合物是目前富勒烯研究的热点课题［１～３］．合成的金属富勒烯常伴随生成较难分离的空心富勒烯,传统的索氏提取法效率又较低,使得金属富勒烯的深入研究受到限制［１,２］．本文采用改进的高温...     

C60睛胺类衍生物的合成及三阶非线性光学性质

Ｃ６０的三阶非线性光学性质的研究是近年来富勒烯物理化学性质的研究热点之一［１］．研究显示,尽管Ｃ６０具有三维共轭的π电子体系,其本身并不具有大的三阶非线性系数［２,３］．但由于Ｃ６０分子具有较低的三重简并ＬＵＭＯ能级,显示出较强的电负性,能够与适当的?..     

C60接枝聚(N-乙烯基咔唑)的合成、表征及光电导性能

自从Ｃ６０被发现和被制备出来以后,其特殊的结构和独特的物理和化学性质受到各研究领域学者的广泛青睐．聚（Ｎ－乙烯基咔唑）（ＰＶＫ）体系经 Ｃ６０掺杂后光电导性能有很大幅度提高．但掺杂体系不稳定,因而限制了对该类材料的应用．为了克服这种缺点,我们尝试用各种简单的方法把Ｃ６０化学键合到高分子链中,制备具有光电导性能的Ｃ６０高分子衍生物． 最近,唐本忠［１］和 Ｐａｔｉｌ［２］等分别用常规的自由基聚合方法,将Ｃ６０接枝到聚合物分子主链上,我们已研究了不含导电高分子的Ｃ６０共聚物的光电导性能［３］,本文采用…     

用原子转移自由基聚合法合成末端含碳笼烯-60的窄分子量分布聚苯乙烯

Ｃ６０是碳笼烯一族的代表,其独特的球笼形空间结构和电子结构决定了其有许多奇异的性质［１］．关于Ｃ６０的化学反应性的研究方兴未艾［２］,其中Ｃ６０的高分子衍生物的合成也是关注所在．迄今关于含Ｃ６０的高聚物的合成已有许多报道［３,４］,而关于窄分布的含Ｃ６０高聚物的合成的研究尚少．Ｆｒｅｙ等［５］将阴离子聚合所得的聚苯乙烯链的末端转变为氨基,再与过量的Ｃ６０发生单电子转移加成反应制得窄分布的以Ｃ６０封端的聚苯乙烯．Ａｓｔｒｕｓ等［６］将活性阳离子聚合所得的六臂星形聚苯乙烯的末端转化为氨基,得到Ｃ６０…     

富勒烯功能高分子材料的制备与性能研究

对富勒烯功能高分子材料的制备、表征及其性能研究已成为光前国际上的前沿领域之一。从合成角度考虑,以不同的方法对Ｃ６０进行高分子修饰可得到结构、性质各异的富勒烯高分子衍生物,对于研究如何更好地控制Ｃ６０高分子衍生物的结构,探讨了有Ｃ６０参与的聚合反应的机理以及Ｃ６０在高分子衍生物中的作用无疑是很有帮助的。从应用角度考虑,Ｃ６０引入高分子中必将导致新型聚合物的产生。这些新型聚合物表现出许多独特而极具应用     

富勒烯的金属配合物及其催化性能

富勒烯的金属配合物及其催化性能１）刘英陈远荫２）盛蓉生（武汉大学化学系武汉４３００７２）关键词富勒烯金属配合物催化分类号Ｏ６４３．３２碳元素的第三种存在形式富勒烯正以其独特的结构和性能以及诱人的应用前景引起人们日益浓厚的兴趣．其中又以Ｃ６０的研究为主...     

C_(60)RuH_2(CO)(PPh_3)配合物的合成和氧化还原性能研究

自从１９８５年Ｋｒｏｔｏ等人１发现Ｃ６０等碳原子簇以来在化学、物理以及材料科学掀起了富勒烯的研究热潮２。目前富勒烯配合物的制备及其性质的研究是富勒烯化学最为活跃的研究领域之一３～５人们正致力于探索富勒烯各类衍生物的结构与性质之间的依赖关系以期合成出具有特殊性能的富勒烯配合物为富勒烯的实际开发应用奠定基础。本文合成表征了Ｃ６０ＲｕＨ２ＣＯＰＰｈ３配合物研究了其氧化还原特性。１实验部分１．１Ｃ６０ＲｕＨ２ＣＯＰＰｈ３的合成合成按下列反应进行ＲｕＣｌ３＋３ＰＰｈ３＋ＨＣＨＯＲｕＨ２ＣＯＰＰｈ３３ＲｕＨ…     

高富勒烯的提取新方法

高富勒烯的提取新方法刘咏梅盛蓉生朱绫李俊（武汉大学分析测试中心４３００７２）１９９０年，Ｋｒａｔｓｃｈｍｅｒ和Ｈｕｆｍａｎ等［１］发明了克量级生产Ｃ６０的方法，使富勒烯成为９０年代研究的热门课题。Ｃ７０［２］的单柱克量级分离也有报道，高富勒烯Ｃｎ（ｎ...     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

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.