具有生物活性有机硅化合笺的研究（Ⅵ）：含硅四配位双（单）硫…

共合成了１３个含硅四配位二硫代磷酸酯和２个含硅四配位单硫代磷酸酯的新化合物，经元素分析，ＩＲ，＾１ＨＮＭＲ，ＭＳ确定了新化合物结构。对部分化合物进行了生物活性的测定，结果表明个别化合物有较好的生物活性。     

用层析法分离磷酸酯基化学修饰的二核苷酸的非对映异构体

本文报道用高效液相色谱法和高效薄层色谱法分离磷酸醌基化学修饰的二核苷酸二尿苷硼烷磷酸酯，二胸苷硫代磷酸酯，二（２＇－脱氧－２＇－氟）尿苷及胞苷硫代磷酸酯的非对映异构体，所得到的非对映异构体的ＲＦ值和＾３１Ｐ－ＮＭＲ化学移植之间的关系符合一般规律，即移动快的异构体有较高的位移植，移动慢的异构体有较的化学位移植。     

硫代磷酸酯萃取铊(Ⅰ)的研究

近年来,硫代磷酸酯萃取分离金属的研究日益增多^[1,2],人们较多地注意其萃取机理和萃合物组成,而以量子化学计算说明硫代磷酸酯结构与铊(Ⅰ)萃取关系的研究甚少。本文比较了二(2-乙基己基)单硫代磷酸(D₂EHMTPA)、二(2-乙基已基)二硫代磷酸(D₂EHDT-PA)]和二(2-乙基已基)磷酸(D₂EHPA)从硫酸介质中对铊(Ⅰ)的萃取行为,并通过EHMO法计算结果,对硫代磷酸醋结构与铭(Ⅰ)萃取能力的关系进行了研究。     

烯丙氧基硫代磷酸酯的合成

硫代磷酸酯是合成有机磷农药的重要中间体 ,许多硫代磷酸酯本身就具有良好的杀虫活性。具有对称型的烯丙氧基硫代磷酸酯有明显的杀虫活性[1～ 3] ;不饱和脂肪烃基不对称硫代磷酸酰胺酯也有良好的杀虫活性[4～ 6] 。本文将具有生物活性的硫代磷酸酯活性结构单元甲氧基 (或乙氧基 )、芳氧基、烯丙氧基设计合成了 8个未见报道的新型不对称硫代磷酸酯 ,所有的化合物经光谱表征及杀虫活性实验。合成路线如下 :PSCl3　1ROH ROPSCl2　2CH2 CHCH2 ONa PROClSOCH2 CHCH2　3XC6 H4 ONa PROXC6H4OSOCH2 CHCH2　4试剂和仪器 :柱层…     

混合三烃基锡衍生物的研究：X.甲基二环己基锡二硫代磷酸酯的合成及生…

合成了１０种甲基二环己基锡－Ｏ，Ｏ－二烃基二硫代磷酸酯，利用ＩＲ，ＮＭＲ，ＭＳ及元素分析确证了化合物的结构，生物活性测试结果表明，这类化合物具有较高的杀螨和除草活性。     

气液色谱法研究双-(O,0′-二正辛基二硫代磷酸酯)合镍(Ⅱ)与酮类加合反应的热力学性质

二烷基二硫代磷酸酯及其过渡金属配合物具有强杀菌性能及抑制酶水解作用,可以用作石油添加剂和高聚物防老剂,又是一类优良的萃取剂,用于钴镍、钴锰等的萃取分离^[1-2]。二硫代磷酸酯的金属盐与含氮、含氧的有机碱形成的加合物在液-液萃取中起着重要作用^[3],因此这类配物合的加合作用受到了广泛的注意。     

O—烷基苯基硫代磷酰取代硫脲的合成（Ⅲ）：含P—C键化合物的…

利用Ｏ－烷基苯基硫代磷酸酸异硫氰基酯与胺与胺的加成反应，合成了两系列Ｏ－烷基苯基硫代磷酰取代硫脲化合物，经元素分析、ＩＲ和＾１ＨＮＭＲ确定了它们的结构，并进行了除草活性的测试。     

含硅不对称硫代磷酸酯及其磷类似物的合成与杀虫活性

合成了两个系列的含硅不对称硫代磷酸酯新化合物，研究了其杀虫活性，并合成了第２系列含硅化合物的碳类似物，对其＾１Ｈ，＾３１ＰＮＭＲ及杀虫活性进行了比较。     

二烃基锡双（O，O－二硫代磷酸酯）的合成和波谱研究

合成了１５个二烃基双（Ｏ，Ｏ－二硫代磷酸酯）化合物。利用ＩＲ、（１Ｈ、１３Ｃ、１１９Ｓｎ）ＮＭＲ表征了化合物的结构。这是一类六配位变形八面体结构的二烃基锡化合物。对化合物的质谱裂解机制进行了讨论。     

双-[O,O''-(2,2''-联苯基)二硫代磷酸酯]合镍(II)的晶体结构

二硫代磷酸酯及其过渡金属螯合物是一类颇具重要性的化合物,本文报道了双-[O, O'-(2,2'-联苯基)二硫代磷酸酯]合镍的晶体结构。     

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.     

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.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.