三核铁配合物[Fe~3(μ~3-O)(μ-O~2CH)~6(H~2O)~2(O~2CH)].2H~2O的合成、结构和性能的研究

本文合成了含μ~3-O的三核铁甲酸配合物[Fe~3(μ~3-O)(μ-O~2CH)~6(H~2O)~2(O~2CH)].2H~2O进行了元素分析、红外与Raman光谱、核磁与顺磁共振波谱分析和磁化率测定, 并作了配合物的X射线单晶结构分析。比较了同系物的结构, 且讨论了波谱及其它性能的研究结果。     

二硅烷表面活性剂的合成与表面性能测定

合成了一种新型有机硅表面活性剂--聚醚改性二硅烷。 首先以(CH3)3SiCl和(CH3)2HSiCl为原料,金属钠作还原偶合剂,二甲苯作溶剂,用Wurtz偶合法合成了含氢二硅烷,对其结构进行了红外光谱、紫外吸收光谱和气相色谱表征,并确定了合成最佳反应条件：n((CH3)3SiCl)∶n((CH3)2HSiCl)=1.2∶1,反应物浓度为1.8 mol/L,助剂15-冠醚-5用量为总反应原料质量的2%,反应温度为80 ℃,反应时间为11 h。 再以合成的含氢二硅烷和甲基封端烯丙基聚醚（Mr=400）为原料,在Karstedt铂催化剂作用下进行硅氢加成反应,合成了聚醚改性二硅烷表面活性剂,确定的合成反应最佳温度为95 ℃,时间为4 h;该表面活性剂的表面张力为22.49 mN/m,临界胶束浓度为0.9 g/L,在pH值为6.94和4.12的水溶液中,具有良好的水解稳定性。     

一种新型磷系阻燃剂的合成

以甲基丙烯酸羟乙酯(1),三氯氧磷(2)和甲醇为原料,合成了一种新型磷系阻燃剂--甲基丙烯酰氧乙基二甲基磷酸酯(3),其结构经1H NMR和IR表征.合成3的较适宜反应条件为:1 0.5 mol,n(1):n(2)=1.0:1.3,于0℃反应6 h.     

半夹芯16电子化合物CpCo(S2C2B10H10)中B(3,6)位的选择性分步取代反应

16e半夹芯化合物CpCo(S2C2B10H10)(Cp:cyclopentadienyl)(1)与炔烃HC≡CC(O)Fc(Fc:ferrocenyl)在物质的量之比为1∶1时反应生成化合物CpCo(S2C2B10H9)(CH=CHC(O)Fc)(2)。在化合物2中,一分子HC≡CC(O)Fc偶合到原料化合物1的碳硼烷笼子的B(3)位点,导致B(3)位的氢原子迁移到炔烃的内部碳原子上形成烯烃取代基。2能继续与另外一分子HC≡CC(O)Fc反应,生成B-双取代产物CpCo(S2C2B10H8)(CH=CHC(O)Fc)2(3)。3仍然是1个16e化合物,并且在B(3,6)位点有2个反式烯烃取代基CH=CHC(O)Fc。在过量炔烃存在情况下,该反应生成化合物3及炔烃环三聚产物1,3,5-{HC=CC(O)Fc}3(4)。化合物2、3、4用红外,核磁,元素分析,质谱和单晶X-射线衍射分析等方法进行了表征。     

溶胶凝胶法合成LiCuVO4及其电化学性能研究

以CH3COOLi.2H2O、Cu(NO3)2.3H2O、V2O5和双氧水(30%)为原料,采用溶胶凝胶法合成了LiCuVO4,其结构、组成和形貌经XRD和SEM确认。结果表明,本文所合成的LiCuVO4具有隧道结构的形貌,颗粒粒径为0.2～6μm。将LiCuVO4作为锂离子电池正极材料,首次循环的放电比容量达到160mAh/g;而作为负极材料,其最大放电比容量达到481mAh/g。在两种电化学测试中,LiCuVO4都显示了良好的循环性能。     

[NH3(CH2)5NH3][Fe2{O3PC(CH3)(OH)(PO3H)}2]@2H2O:一个新的二膦酸亚铁化合物的合成、结构与性质研究（英文）

通过水热合成得到一个新的有机二膦酸亚铁化合物[NH3(CH2)5NH3][Fe2Ⅱ(O3PC(CH3)(OH)(PO3H)}2]·2H2O,该化合物包含阴离子型共价双链[Fe2Ⅱ{O3PC(CH3)(OH)PO3H}2]n2n-,质子化的戊二胺和结晶水,双链之间通过强氢键构成一个开放型的骨架结构.另外,观察到亚铁离子之间存在弱铁磁性相互作用.     

磺酸型水溶性膦配体的合成

以季鳞盐[Ph2P(CH2OH)2]^ Cl^-与含磺酸根的胺的曼尼希反应合成了水溶性更大的含Ph2PCH2N配位基团的磺酸型膦配体[(Et3NH)2][Ph2PCH2N(CH2CH2SO3)2(2a)和[(Et3NH)2][O3SCH2CH2N(CH2PPh2)CH2CH2N(CH2PPh2)CH2CH2SO3](2b),用NMR、MS、IR等对该膦配体的结构进行了表征。25℃时膦配体2a在水中的溶解度为0．21g／mL,在乙醇中为0．29g／mL。膦配体2b的SO3H与Ph2P的摩尔比较低,在水中溶解度为0．11g/mL,在乙醇中为0．15g／mL。     

主（脱铝Y分子筛纳米腔）-客（Co，Mn和Cox/Mnx三核金属簇合物）纳米复合物催化剂高效催化环己烯环氧化反应

采用模板合成法制备了在脱铝Y分子筛纳米腔中含有Co, Mn,和Co/Mn混合物的三核金属簇合物的复合物催化剂,包括[Mn3(O)(CH3COO)6-(py)3]-Y,[Co3(O)(CH3COO)6-(py)3],[Co2Mn(O)(CH3COO)6-(py)3]-Y和[CoMn2(O)(CH3COO)6-(py)3]-Y],并运用傅里叶变换红外光谱、紫外-可见光光谱、前场扫描电镜、X射线衍射和原子吸收光谱对其进行了表征.包裹的金属簇合物在环己烯环氧化反应中表现出较高的催化活性,反应以H2O2/O2为氧化剂,在加热机械搅拌下进行,所得环氧化物产率在82.5%?90.7%.在该催化体系中, NaBr用作氧化助剂可以提高反应性能.在所制多相催化体系中,含单核的金属簇合物催化活性更高,其中以Mn3(O)-DAZY化合物的效率最高.各催化剂活性顺序为Mn3(O)-DAZY> Co3(O)-DAZY> Mn2Co(O)-DAZY> MnCo2(O)-DAZY.     

主(脱铝Y分子筛纳米腔)-客(Co,Mn和Co_x/Mn_x三核金属簇合物)纳米复合物催化剂高效催化环己烯环氧化反应（英文）

采用模板合成法制备了在脱铝Y分子筛纳米腔中含有Co,Mn,和Co/Mn混合物的三核金属簇合物的复合物催化剂,包括[Mn3(O)(CH3COO)6-(py)3]-Y,[Co3(O)(CH3COO)6-(py)3],[Co2Mn(O)(CH3COO)6-(py)3]-Y和[CoM n2(O)(CH3COO)6-(py)3]-Y],并运用傅里叶变换红外光谱、紫外-可见光光谱、前场扫描电镜、X射线衍射和原子吸收光谱对其进行了表征.包裹的金属簇合物在环己烯环氧化反应中表现出较高的催化活性,反应以H2O2/O2为氧化剂,在加热机械搅拌下进行,所得环氧化物产率在82.5%-90.7%.在该催化体系中,Na Br用作氧化助剂可以提高反应性能.在所制多相催化体系中,含单核的金属簇合物催化活性更高,其中以Mn3(O)-DAZY化合物的效率最高.各催化剂活性顺序为Mn3(O)-DAZY?Co3(O)-DAZY?Mn2Co(O)-DAZY?MnC o2(O)-DAZY.     

L-天门冬氨酸二肽的结构与甜味的一些关系

本文报导了一系列L-天门冬氨酸二肽衍生物,NH_2CH(CH_2COOH)CONHCH(COOCH_3)-(COX)(X为烷氧基,烷氨基,邻位取代苯胺基及N-甲基苯胺基)的合成和它们的甜度。这些二肽尾部的电性能、憎水性、以及整个分子的链长(在满足一定立体要求的条件下)都影响着二肽的甜度。     

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%.     

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.     

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.     

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.     

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.     

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.     

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.     

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.