Hyperpolarizabilities of Chelidamic Acid Complexes M_m(C_7H_3O_5N)_n (M=Cu, Ag): Theoretical Analysis

The frequency‐dependent hyperpolarizabilities of chelidamic acid complexes M_m(C₇H₃O₅N)_n (M?Cu, Ag) were investigated under the time dependent density functional theory (TDDFT) combined with the sum‐over‐states method (SOS). The relationship between molecular orbitals and nonlinear optical (NLO) properties has been explored. The results show that the charge transitions of π‐π* and 3d_M‐π* are very important to the second‐order polarizabilities, and the largest component of dynamic β is 3.84×10^?25 cm⁵·esu^?1 at 0.74 eV for Ag₂Cu₂(C₇H₃O₅N)₄. The charge transition between π‐π* is also highly crucial to the third‐order polarizabilities, and the largest component of dynamic γ is ?4.46×10^?29 esu at 0.50 eV for Ag₂Cu₂(C₇H₃O₅N)₄. The central Cu ion, as electron bridge, extends the range of delocalization and leads to an interesting phenomenon of spiroconjugation.     

On the shepherding of Uranian epsilon ring

To explain the long-term existence of Uranian narrow rings, we study the dynamical evolution of Uranian epsilon ring under the influence of its two shepherding satellites: Cordelia and Ophelia. The model of planar-elliptic restricted three-body problem is employed, in which the three bodies are Uranus, a satellite and a test particle. Dissipations due to interparticle collisions are also taken into consideration. A mapping system has been obtained based on the differential equation system. Numerical results show that only those particles originally lying in the libration region of the resonance can be shepherded. The size of the libration region depends mainly on the orbital eccentricity and mass of the shepherd satellite. For the outer shepherd Ophelia with larger orbital eccentricity, if its mass is a third of the nominal mass 2.5 × 10¹⁹ g, most of the orbits are regular and the outer edge of the ring can be shepherded, but more fuzzy than the inner edge. Thus we infer that Ophelia has a smaller mass.     

明胶接枝磺化缩聚物油井水泥分散剂的合成与性能

以动物明胶为原料,通过与甲醛、丙酮和焦亚硫酸钠发生磺化接枝反应,合成了一种新型的明胶接枝磺化缩聚物油井水泥分散剂.利用红外光谱分析测试技术证明了在明胶分子侧链上引入了磺化缩聚物.测试结果表明,当合成分散剂加入质量分数为1%时,水泥浆的流性指数、稠度系数和稠化时间比值(与未加水泥浆)分别为1.124、O.014和1.02,抗压强度比值均大于1.0,在18%NaCl、37%NaCl和2%CaCl,盐水水泥浆的流性指数分别为1.021、1.087和0.914、稠度系数分别为0.035、0.025和0.063.结果证明.明胶接枝磺化缩聚物的分散性能优异、耐盐性强并且无缓凝副作用,性能与常用的磺化醛酮缩聚物分散剂接近.是一种新型的预期可生物降解的油井水泥分散剂.     

Two Novel Poly-Oxygen Bipyridine Alkaloids from Speranskia tuberculata

In a previous paper' we reported two optically active pyridine-2, 6 (l H. 3H)-dionealkatoids speranskalines A and B from SPeranskia luberculala (Bge.) (Euphorbiaceae)We report here the isolation and structural elucidation of two novel poly-oxygenbipyridine alkaloids named speranculatines A (l) and B (2) from this plant.The acetone (or methanol) extract of the air-dried whole plants of .q. IllhelT.lllaluwas subjected to column chromatography on St gel to afford a fraction. whichdemonstrate…     

Practical synthesis of new functionalized tetraphenylenes

The practical synthesis procedure of substituted tetraphenylene derivatives involving the synthesis of a precursor for 4, 7-dunethoxyisobenzofuran and Diets-Alder addition of 4, 7-dimethoxyisobenzofuran generated in situ to 5, 6, 11,12-te-tradehydrodibenzo[a,e]cyclooctene, followed by a low valent titanium mediated deoxygenation to give 1,4, 11, 14-tetra-methoxy-dibenzo[b, n] tetraphenylene, which can be further demethyiated to the corresponding phenolic compound, which was acetylated to afford 1,4,11,14-tetraacetoxy-dibenzo-[ b, n] tetraphenylene.     

1,1''-双(四甲基环戊二烯基)二茂铁与五羰基铁和三乙腈三羰基钼的反应

配体1,1-双(四甲基环戊二烯基)二茂铁1,1-Fc(Me4Cp)2(Ⅰ)与五羰基铁在二甲苯中回流反应, 得二茂铁桥连双(四甲基环戊二烯基)四羰基二铁1,1-Fc[(Me4Cp)Fe(CO)(μ-CO)]2(1). 化合物1在氯仿中与单质碘反应, Fe_Fe键断裂, 生成二茂铁桥连双铁碘化合物1,1-Fc[(Me4Cp)Fe(CO)2I]2(2). 配体Ⅰ与正丁基锂作用生成二茂铁桥连双(四甲基环戊二烯基负离子盐), 后者随即与三乙腈三羰基钼反应形成1,1-二茂铁双(四甲基环戊二烯基负离子盐)1,1-Fc[(Me4Cp)Mo(CO)3-Li+]2(Ⅱ). 钼负离子Ⅱ与CH3I作用在钼原子上发生甲基化, 得到产物1,1-Fc[(Me4Cp)Mo(CO)3Me]2(3). Ⅱ与BrCH2CH2Br反应, 未得到预期的Mo_Mo键化合物, 相反却得到少量亲核取代-消除的双钼-溴化合物1,1-Fc[(Me4Cp)Mo(CO)3Br]2(4). 经元素分析、 IR及1H NMR表征化合物1-4的结构, 并用X射线衍射测定了化合物1的晶体结构.     

Electron Transfer Reaction between M-C_6H_6 and M~ -C_6H_6 Complexes in the Gas Phase: Density Functional Theory Study

Significant progress has been made in understanding the nature of the transition state andthe paths for electron transfer, especially the influences of environmental factors and themolecular properties on the electron transfer rate. These classical and semi-classical, aswell as quantum-mechanical theory, have been very successful in rationalizing severalstructure-reactivity relationships and in predicting novel features of reactivity. Thesemodels established some links between the electron tra…     

2-苄硫基-5,7-二甲氧基-1,2,4-三唑并[1,5-a]嘧啶的合成研究

2-苄硫基-5，7-二甲氧基-1，2，4-三唑并[1，5-a]嘧啶（Ⅲ）是磺草唑胺（metosulam）及1，2，4-三唑[1，5-a]嘧啶醚类超高效除草剂的重要中间体．由5-氨基-3-苄硫基-1，2，4-三唑（Ⅰ）为起始原料，经环合、氯代一步反应制得2-苄硫基-5，7-二氯-1，2，4-三唑并[1，5-a]嘧啶（Ⅱ）．优化试验发现90℃、丙二酸与（Ⅰ）摩尔比为1．1：1、反应20h时收率达85％以上．（Ⅱ）与甲醇钠进行置换反应制得（Ⅲ），对反应温度和物料配比进行了优化试验，发现25℃、甲醇钠与（Ⅱ）的摩尔比为5：1时收率达到90％以上．中间体（Ⅱ）、（Ⅲ）的结构经^1H-NMR、MS、IR确证．该方法原料易得、操作简便，总收率较高．     

Synthesis and Structure of E-2-(2,4,6-tri tert butylphenylphosphinyl)-2-〔N-(tert-butyldimethylsilyl)-N-(p-chrolophenyl)〕amino-1-(2,4,6-tri tert-butyl-phenyl)phosphacthylene

1　INTRODUCTIONItwaswellknown thatelementsofthesecondary and higherrow are in generaldifficulty to form multiplebondsin which apπ hybridized stateisinvolved〔1〕.Thus,simple compounds containing multiple phosphorus carbon bonds,such as methyl dynephosphine( HC≡P) 〔2 - 3〕 and methylenephosphine( H2 C=PH〔4〕,are notstableat room temperature.Three methods to stabilize compounds containing double ormultiple bond involving phosphorusatom in the pπ hybridized state are often used.The f…     

Synthesis and Isolation of Diastereomers of Optically Active Cyclomercurated Ferrocenylimines

IntroductionOrganomercurials have been used extensively in organic synthesis and synthesis of other organometallics due to their ability to accommodate practically all the important organic functional groups and their ease in undergoing transmetallation for syntheses of transition metal organometallics which are very useful in organic synthesis. Recently, we reported the synthesis of optically active 1,2-disubstituted cyclomercurated ferrocenylimines by transmetallation reaction of planar chir…