[60]富勒烯与氮杂芳烃叶立德的反应

[60]富勒烯与乙氧羰基甲基氮杂芳烃叶立德发生1,3-偶极环加成反应,生成[60]富勒烯并吡咯烷衍生物。反应温度对反应有一定的影响。     

C60-N-甲基吡咯烷衍生物直接进样电喷雾离子阱质谱表征

通过直接进样方式,采用电喷雾电离质谱技术分析了8个合成的富勒烯-N-甲基吡咯烷衍生物,详细研究了其在电喷雾条件下的质谱行为。由结果可知,该类化合物在电喷雾电离过程中易得到电子而负离子化;当衍生物结构中有相对易质子化基团或有活泼氢时,则可获得质子化和去质子的正负离子谱图;衍生物在负离子模式下容易失去吡咯环产生富勒烯负离子,且在合适能量碰撞下易发生衍生化基团内部的逆环加成反应,通过失去1个中性小分子物质CH2‖N—CH3,产生新的一取代亚甲基富勒烯衍生物。基于电喷雾电离源技术联合离子阱分析器建立的质谱分析方法,不但能提供准确的分子量信息,还能通过获得高分辨同位素谱峰和丰富的二级碎片离子峰,进一步确认化合物的分子结构,是一种先进、快速的富勒烯吡咯烷衍生物定性分析方法。     

新型富勒烯α-氨基酸的合成及其纳米颗粒水悬液的制备

通过1,3-偶极环加成反应合成中间体N-取代的3,4-富勒烯吡咯烷, 利用α-氨基与α-羧基均被保护的天冬氨酸或谷氨酸的非α-羧基与中间体N-取代的3,4-富勒烯吡咯烷衍生物的活化羟基进行缩合反应, 产物脱保护后得到了2种新的α-富勒烯氨基酸: 富勒烯天冬氨酸和富勒烯谷氨酸. 采用MALDI-TOF质谱、红外光谱、紫外-可见光谱和1H NMR 等方法对它们进行了结构表征. 采用有机溶剂交换法, 制备富勒烯氨基酸纳米颗粒水悬液, 并进行了电镜和表面zeta-电位分析, 结果表明, 此水悬液体系稳定, 颗粒形态大小均一, 在生物医学领域中具有潜在的应用前景.     

醋酸锰作用下二烯丙基叔胺与[60]富勒烯的自由基环加成反应

二烯丙基叔胺与[60]富勒烯在醋酸锰作用下发生自由基环加成反应,生成[60]富勒烯并吡咯烷衍生物.醋酸锰的用量和反应温度等因素对反应有一定影响.反应可能先由Mn(Ⅲ)与烯丙胺经单电子氧化产生自由基,再与[60]富勒烯加成并进一步环化.研究中得到的各产物的结构均通过波谱学方法表征.     

新型富勒烯衍生物的激光质谱结构表征

对3种电化学方法合成的新型结构富勒烯衍生物进行了激光质谱表征,确认了1,2加成以及[5,6]开环富勒烯衍生物结构.质谱结果发现了富勒烯以及富勒烯衍生物与氧的结合峰,核磁共振结果进一步证明了富勒烯衍生物的结构,为含有C60结构衍生物的研究提供了有力的表征手段.     

2',5'-二氢-1'H-吡咯骈[3',4':1,2][60]富勒烯衍生物的合成

以甘氨酸乙酯盐酸盐与取代的苯甲醛为原料,制得了一系列亚胺,然后用亚胺与C60反应,得到带有不同取代基的吡咯烷骈[60]富勒烯衍生物.经1H NMR,13C NMB,FT-IR,UV-vis以及TOF-SIMS等方法对所得化合物结构进行了表征,并进行了产物的生物活性测试.     

低成本富勒烯衍生物电子传输层在钙钛矿太阳能电池的应用（英文）

有机无机杂化钙钛矿太阳能电池(PSCs)近几年吸引了众多的关注。目前,在反式平板异质结钙钛矿太阳能电池中,最普遍使用的电子传输层材料是富勒烯衍生物PCBM,但是由于其价格昂贵,将会影响钙钛矿太阳能电池的最终产业化。本文开发出一种新的低成本富勒烯衍生物N-甲基-2-戊基[60]富勒烯吡咯烷(NMPFP)来取代PCBM,用于反式钙钛矿太阳能电池的电子传输层。和PCBM电子传输层相比,NMPFP具有更快的电子传输速率。用NMPFP制作的钙钛矿太阳能电池几乎没有迟滞现象,取得了13.83%的光电转换效率,和PCBM电池性能相当。而且,由于NMPFP更强的疏水性,其电池的稳定性优于PCBM电池。本研究表明NMPFP是一种非常有前景的电子传输材料,用于反式平板钙钛矿太阳能电池,可以有效的取代PCBM。     

2',5'-二氢-1'H-吡咯骈[3',4':1,2][60]富勒烯衍生物的合成

以甘氨酸乙酯盐酸与取代的苯甲醛为原料,制得了一系列亚胺,然后用亚胺与C~6~0反应,得到带有不同取代基的吡咯烷骈[60]富勒烯衍生物.经^1HNMR,^1^3CNMR,FT-IR,UV-vis以及TOF-SMS等方法对所得化合物结构进行了表征,并进行了产物的生物活性测试。     

η2-C70[RhCl(CO)(PPh3)2]n配合物的合成和表征

从１９８５年Ｋroto等^[1]发现Ｃ６０等富烯至１９９６年富勒烯发现者获诺贝尔化学奖期间,在化学、物理、材料等领域掀起了富勒烯研究热潮^[2~8],此后,化学工作者致力于富勒烯的化学修饰,探索富勒烯各类衍生物的结构与性能之间的依赖关系,并在此基础上合成出具有独特结构与笥能的富勒烯衍生物,以期望在富勒烯及其衍生物的开发利用方面取得突破性进展。     

有机富勒烯化合物的逆环加成反应

逆环加成反应是富勒烯衍生物的一种重要反应。在还原、氧化或加热条件下,许多富勒烯衍生物的加成基团会从富勒烯骨架上断开,得到富勒烯母体,是富勒烯环加成反应的逆反应。该反应与富勒烯环加成反应结合,已被应用于富勒烯化学中保护/去保护基团方法,对于选择性制备富勒烯及其衍生物具有重要意义。然而由于逆环加成反应的存在,引起了有机富勒烯化合物的不稳定,从而可能影响其在实际中的应用。最近,我们研究了一系列含有亚胺酯杂原子环结构的富勒烯噁唑衍生物在电化学还原下的稳定性,结果表明加成基团之间存在的分子内C-H…X（X = N,O）氢键对化合物的稳定性可能起着较为关键的作用。在此,我们将结合我们的工作对有机富勒烯化合物的逆环加成反应进行综述。     

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%.     

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.     

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.     

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.     

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.     

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.     

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.