3·{6-[（1R，2R，4S）-2-羟基-1，3，3-三甲基二环[2．2．1]庚烷-2-基]-吡啶-2-基}．2’-特戊酰基-1，1’-（R）-联萘-2，2＇-酚合钼（Ⅵ）的合成、单晶结构及应用

化合物3-{6-（1R,2R,4S）-2-羟基-1,3,3-三甲基二环[2．2．1]庚烷-2-基]-吡啶-2-基}-1,1’-（R）-联萘-2,2’-酚（1）与特戊酰氯反应,得到单个羟基封端的化合物3-{6-[（1R,2R,4S）-2．羟基-1,3,3-三甲基二环[2．2．1]庚烷-2-基]-吡啶-2-基}-2’-特戊酰基-1,1’-（R）-联萘-2,2’-酚（2）。化合物2与MoO2（acac）2进行配位得到金属配合物3-{6-[（1R,2R,4S）-2-羟基-1,3,3-三甲基二环[2．2．1]庚烷-2-基]-吡啶-2-基}-2’-特戊酰基-1,1’-（R）-联萘-2,2’-酚合钼（酰）[Mo（Ⅵ）-2],通过核磁共振氢谱、红外光谱和质谱测试技术对其结构进行了表征,用X射线单晶衍射测定了化合物的晶体结构。结果表明,化合物晶体属单斜晶系,空间群为P21,晶胞参数α=1．17934（10）nm,b=2．3045（2）nm．c=1．51888（13）nm,α=90°,β=112．84°,γ=90°．V=3．8042（6）nm^3,Z=4,μ=0．392mm^-1,De=1．298Mg／m^3,F（000）=1544,R^1=0．0775,wR^2=0．1934,GOF=1．122。在配合物中,钼原子处于六配位的八面体配位环境,配位原子分别来自1个分子水中的O原子、配体分子中1个酚羟基的O,毗啶环中的O,醇羟基中的O形成ONO三齿配合物。配合物Mo（Ⅵ）-2在萘乙烯的不对称环氧化反应中,得到中等活性和较低的对映选择性。     

1，2-萘醌-4-磺酸钠分光光度法测定链霉素的研究

链霉素(streptomycin,STR)是一种对结核分枝杆菌有强大抗菌作用的氨基糖苷类抗生素,它通过作用于细胞的核糖体抑制细菌蛋白质的生物合成而呈现杀菌作用[1].目前所报道检测链霉素含量的方法主要有高效液相色谱法[2] 、鲁米诺的流动注射化学发光法[3] 、微生物学检测法[4、5] 、荧光法[6]、免疫法[7]以及紫外分光度度法[8]等,但以可见光度法测定链霉素的研究还很少有报道.本文基于1,2-萘醌-4-磺酸钠(NQS)能与含有胺基类药物分子结构中的胺基发生亲核缩合或取代作用 [9-13],建立了以NQS作为显色剂在可见光度法测定STR的新方法.研究表明,控制溶液pH12.00,STR与NQS发生缩合反应生成摩尔比为1: 2红褐色产物,最大吸收波长λ max =470 nm,STR浓度在2.91μg/mL～145.7μg/mL范围内与吸光度成良好线性关系.与文献中所报道的其他方法相比,该方法不仅具有简便、快速、不需昂贵的仪器设备等特点,具有重要的应用价值.     

含1，3，5-三-((4-吡啶)-1，2-乙烯基)苯的配位聚合物的合成、结构及性质

用三烯烃三吡啶配体1,3,5三-((4-吡啶)-1,2-乙烯基)苯(tpeb)和M(NO_3)_2(M=Co,Ni,Zn,Cd)以及4种不同的有机羧酸(3,5-二溴苯甲酸(3,5-HDBB)、2,5-噻吩二羧酸(2,5-H_2TDC)、2,5-呋喃二羧酸(2,5-H_2FDC)、2,5-二溴对苯二甲酸(2,5-H_2DBTP))进行溶剂热反应,得到了[Zn(tpeb)(3,5-DBB)_2]_n(1)、[Co_2(tpeb)_2(2,5-TDC)_2]_n(2)、[Co_2(tpeb)_2(2,5-FDC)_2]_n(3)、[Co(tpeb)(2,5-DBTP)]_n(4)、[Ni(tpeb)(2,5-DBTP)]_n(5)、[Cd(tpeb)_(0.5)(2,5-DBTP)]_n(6)六个配位聚合物。对配合物1～6分别进行了单晶X射线衍射、粉末X射线衍射、红外、元素分析、热重、荧光等结构表征。配合物1～6结构独特且多样。配合物1是由[Zn(3,5-DBB)_2]单元通过配体tpeb桥联构筑的一维zigzag链状结构;配合物2和3是由一维梯状[Co(tpeb)]_n链分别与2种不同的五元杂环二取代羧酸桥联构筑而成的二维双层结构;配合物4和5均是由一维[M(2,5-DBTP)]_n(M=Co,Ni)链通过tpeb交叉连接而成的三维网络结构;配合物6则是由二维的[Cd(2,5-DBTP)]_n层状结构通过tpeb连接而成的三维互穿拓扑网络结构。配合物1～6的热稳定性较好,它们在固态时表现出不同的荧光性质。     

双环[2，2，1]庚-5-烯-2-甲酰基芳香醛腙的合成和生物活性

合成了七个未见文献报道的双环[2，2，1]庚-5-烯-2-甲酰基芳香醛腙席夫碱 类化合物。用核磁共振氢谱、红外光谱和元素分析对新化合物进行了表征，考察了 它们的生物活性。结果表明某些化合物具有除草作用、抗菌作用和植物生长调节作 用。     

3-(3′-吡啶基)-6-芳基-1，2，4-三唑并[3，4-b]-1，3，4-噻二唑衍生物基态和激发态性质

用密度泛函B3LYP方法对3-(3'-吡啶基)-6-芳基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑衍生物(芳基为苯基、3-吡啶基和苯乙烯基)进行基态几何构型全优化,计算分子的电离势I_p和电子亲和势E_A等相关能量,并用Zerner间略微分重叠(ZINDO)和含时密度泛函(TDDFT)方法计算吸收光谱,用单组态相互作用方法(CIS)优化三种化合物分子的S_1激发态结构,分析其能量与发射光谱的关系,计算溶剂中分子的吸收和发射光谱,并与实验结果对照.计算结果表明,从3-(3'-吡啶基)-6-苯基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑分子(化合物A)到3-(3'-吡啶基)-6-(3'-吡啶基)-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑分子(化合物B)以及3-(3'-吡啶基)-6-对乙烯苯基-1,2,4-三唑并[3,4-b]- 1,3,4-噻二唑分子(化合物C)的电子亲和势依次增大,愈来愈容易接受电子,吸收光谱和发射光谱红移.     

7-氯-[1，2，3，4]-四氢吩嗪-[2，3]-并富勒烯[60]的合成

60富勒烯及其衍生物因其结构的特殊性,在有机超导、分子磁性、有机发光材料、分子器件、非线性光学活性、能量代谢和生物活性等[1]方面表现出独特的性能和潜在的应用前景,是非常活跃的研究领域之一.     

金属调控的2，4，6-三(2-吡啶基)-1，3，5-三嗪基配合物的光致变色性能

在溶剂热条件下,将2,4,6?三(2?吡啶基)?1,3,5?三嗪(2?TPT)、2,5?呋喃二羧酸(2,5?H₂FCA)分别与不同类型的金属硝酸盐(Zn、Cd和Mn)进行组装,得到了3个2?TPT基配合物:[Zn(2?TPT)(2,5?FCA)](1)、[Cd(2?TPT)(2,5?FCA)]·1.5H₂O(2)和[Mn(2?TPT)(2,5?FCA)](3)。通过单晶X射线衍射、粉末X射线衍射、FT?IR、UV?Vis、差热-热重、电子顺磁共振和X射线光电子能谱对1~3的结构和光致变色性能进行了表征,并详细地探究了其光致变色机理。配合物1~3表现出明显差异的光诱导分子间电子转移和光致变色性能,主要体现在光响应速率和颜色对比度2个方面。其中,1的光致变色性能明显优于2,而3不具有光致变色行为。这种明显差异的光致变色行为,主要归因于不同类型的金属及其配位模式的差异所引起的不同晶体堆积模式和电子给体-受体间相对位置关系(界面关系),体现出了金属对于光致变色性能的调控作用。     

2-(1H-1，2，4-三氮唑)乙酸-稀土配合物的合成与结构

利用柔性含氮配体羧酸2-(1H-1,2,4-三氮唑)乙酸(HL)与稀土氧化物在水热条件下反应得到了2个稀土配位聚合物 [Gd(L)₃H₂O]_n(1)和[Nd(L)₃H₂O]_n(2)。利用元素分析、红外光谱、X射线单晶衍射结构分析等方法对其进行了表征。晶体结构表明2个配合物晶体同属三斜晶系,空间群P1,具有一维链状结构。     

(2R，3R)-和(2S，3S)-2-(4-羟基-3-甲氧基)-3-羟甲基-1，4-苯并二氧六环-6-醛的对映选择性合成

1,4-苯并二氧六环木脂素类天然产物多数具有增加胆碱乙酰化酶和抗肝毒等活性 ,其活性主要源于 1 ,4-苯并二氧六环官能团 [1] . 1 ,4-苯并二氧六环木脂素的消旋全合成已有报道 [2 ] ,但其不对称合成还是空白[3] .我们发展了一条对映选择性合成 1 ,4-苯并二氧六环木脂素的简捷有效的路线 .基于前面的工作 [4 ] ,我们发现 1 ,4-苯并二氧六环醛类衍生物是合成此类天然产物的关键中间体 ,选择 2 - (4-羟基- 3-甲氧基 ) - 3-羟甲基 - 1 ,4-苯并二氧六环 - 6-醛 (1 )作为目标分子 ,其合成路线如下 :Reagents and conditions:( ) Me OH,H2 SO4,9…     

刚性配体1，3，5-三(1-咪唑基)苯与1，2，4-苯三甲酸构筑的金属配合物：水热合成及晶体结构

由水热法合成了2个配合物[Co(1,2,4-HBTC)(tib)](1)和[Ni4(1,2,4-BTC)2(tib)4(H2O)2]·(1,2,4-HBTC).9H2O(2)(1,2,4-H3BTC=1,2,4-苯三甲酸,tib=1,3,5-三(1-咪唑基)苯),并用元素分析、红外光谱、X-射线单晶衍射及热重分析等对其进行了表征。晶体结构分析结果表明:配合物1是由Co(Ⅱ)和tib连接形成的二维层状结构,1,2,4-HBTC2-作为端基配体与Co(Ⅱ)配位,而配合物2是通过1,2,4-BTC3-连接[Ni(tib)]2+二维网形成最终的二维多层结构,这2个化合物最终均被氢键连接形成三维超分子结构。     

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.     

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.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.     

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%).