1-芳基-3，5-二甲基吡唑-4-羧酸有机锡酯的合成、结构及杀菌活性研究

由1-芳基-3,5-二甲基吡唑-4-羧酸与适当的有机锡反应,合成表征了一系列的1-芳基-3,5-二甲基吡唑-4-羧酸有机锡酯(1～14),并通过单晶衍射确定了1-苯基-3,5-二甲基吡唑-4-羧酸三乙基锡酯(7)的结构。该化合物与一分子水共同结晶,通过分子间O-H…O及O-H…N氢键形成二维网状结构。杀菌活性筛选表明新合成的化合物对于番茄早疫菌、花生褐斑菌、小麦赤霉菌、苹果轮纹菌及灰霉菌全部具有良好的生长抑制作用。1-苯基-3,5-二甲基吡唑-4-羧酸三乙基锡酯及1-(2-吡啶基)-3,5-二甲基吡唑-4-羧酸三乙基锡酯在50μg.mL-1浓度下的体外实验中表现出很高的生长抑制率。对于高活性的三取代锡羧酸酯进行了EC50值的测定,结果表明1-(2-吡啶基)-3,5-二甲基吡唑-4-羧酸三乙基锡酯对苹果轮纹菌的EC50值为0.06μg.mL-1,对小麦赤霉菌的EC50值为0.14μg.mL-1。     

ω-9-蒽多亚甲基羧酸-甲基取代香豆素酯的合成及其光性能研究

合成了9个新的双荧光团化合物ω-9-蒽多亚甲基羧酸-甲基取代香豆素酯和3个模型化合物,讨论了这些化合物的结构与光性能之间的关系。     

混合三烃基锡衍生物的研究——Ⅵ.二环已基-甲基锡羧酸酯的结构及生物活性

本文合成了未见文献报道的二环己基-甲基锡氧化物及其二十个羧酸酯衍生物,经红外、核磁及X射线衍射分析确定了化合物的结构.结果表明,所合成的二环己基-甲基锡脂肪酸酯为分子间氧桥相连的五配位聚合结构,而取代苯甲酸酯则为单分子变形四面体结构.化合物的生物活性测定结果表明,这是一类具有高效杀螨、杀菌及除草活性的有机锡化合物.     

一种新型α-甲氧基甲基吡咯的合成

以乙酰乙酸苄酯(4)为原料,经Knorr缩合制备了2,4-二甲基-3-丙酸甲酯基-5-羧酸苄酯基-1-氢吡咯(2)和2,4-二甲基-3-羧酸甲酯基-5-羧酸苄酯基-1-氢吡咯(3)。乙醚介质中,溴水氧化条件下,吡咯(2)发生自身缩合生成二吡咯甲烷(7),吡咯(3)无反应发生。在Pb(OAC)4氧化条件下,当其浓度为吡咯(3)浓度的2倍时,在80℃,吡咯(3)完全转化,所得产物经HCl甲醇溶液回流,以82%的产率制备了新型2-甲氧基甲基-3-羧酸甲酯基-4-甲基-5-羧酸苄酯基-1-氢吡咯(1)。吡咯(1)、(2)、(3)及二吡咯(7)的结构用核磁、元素分析、质谱和红外测试技术进行了表征。吡咯(1)的构建对进一步研究吡咯构效关系具有一定参考价值。     

混合三烃基锡衍生物的研究 Ⅵ. 二环己基-甲基锡羧酸酯的结构及生物活性

本文合成了未见文献报道的二环己基-甲基锡氧化物及其二十个羧酸酯衍生物, 经红外、核磁及X射线衍射分析确定了化合物的结构。结果表明, 所合成的二环己基-甲基锡酯肪酸酯为分子间氧桥相连的五配位聚合结构, 而取代苯甲酸酯则为单分子变形四面体结构。化合物的生物活性测定结果表明, 这是一类具有高效杀螨、杀菌及除草活性的有机锡化合物。     

混合三烃基锡衍生物的研究 Ⅵ. 二环己基-甲基锡羧酸酯的结构及生物活性

本文合成了未见文献报道的二环己基-甲基锡氧化物及其二十个羧酸酯衍生物, 经红外、核磁及X射线衍射分析确定了化合物的结构。结果表明, 所合成的二环己基-甲基锡酯肪酸酯为分子间氧桥相连的五配位聚合结构, 而取代苯甲酸酯则为单分子变形四面体结构。化合物的生物活性测定结果表明, 这是一类具有高效杀螨、杀菌及除草活性的有机锡化合物。     

有机锡2-(3-吡啶甲基硫代)苯甲酸酯与2-吡啶硫代乙酸酯的合成、结构与抗真菌活性

通过二乙基氧化锡、二丁基氧化锡以及三苯基氧化锡与2-(3-吡啶甲基硫代)苯甲酸和2-吡啶硫代乙酸的反应,3个四核有机锡羧酸酯以及2个单核三苯基锡羧酸酯被合成。它们的结构通过X-射线单晶衍射结构分析得到确证。生物活性测试表明,四核二丁基锡2-吡啶硫代乙酸酯以及单核三苯基锡2-(3-吡啶甲基硫代)苯甲酸酯对西瓜炭疽病菌、花生褐斑以及苹果轮纹菌等具有高的抑制活性。     

三(硅烃基亚甲基)锡吡啶羧酸酯的研究

大多数三烃基锡化合物具有一定的生物活性,有一些已在农业生产中被用来作为杀虫剂、杀菌剂和杀螨剂使用.由于在它们的使用中出现较大的毒副作用,为此,人们合成了一系列含硅三烃基锡化合物,并对它们的生物活性进行了广泛的研究[1-3],结果表明,三[(三甲硅基)亚甲基]锡羧酸酯及其类似物具有较强的杀螨活性和广泛的生物活性谱,并且毒性有所减小.为了系统地研究含硅三烃基锡化合物,进一步探讨这类化合物的结构与生物活性之间的关系,本文用双[三(硅烃基亚甲基)锡]氧化物分别与三种不同的吡啶甲酸反应,合成了9个新的化合物三(硅烃基亚甲基)锡吡啶羧酸酯.反应方程式如下:     

双羟甲基-18-冠-6及其衍生物的合成

报道了双羟甲基-18-冠-6及其正丁基、烯丙基、酯基、羧酸基衍生物的合成。所合成的八种新冠醚化合物的结构已经IR、MS、NMR、元素分析证实。     

嘧啶的研究:胺及肼對2-甲硫基-4-甲基-嘧啶-5-羧酸乙酯的作用

1.乙氧基亚甲基乙酰乙酸乙酯与S-甲基假硫脲硫酸盐在乙醇钠的存在下於乙醇中缩合形成2-甲硫基-4-甲基嘧啶-5-羧酸乙酯。此嘧啶酯用氢氧化钾乙醇溶液水解,成为相应的嘧啶-5-羧酸。此嘧啶羧酸又变为银盐,再用碘代乙烷与之作用,又生成上述的嘧啶酯。 2.2-甲硫基-4-甲基嘧啶-5-羧酸乙酯与肼、氨、甲胺、乙胺、正丁胺、苯甲胺及环己胺在乙醇中作用,生成相应的2-肼基一、氨基一、烷氨基—、芳烷氨基-及环烷氨基衍生物。     

三苄基和三[(甲基二苯硅基)亚甲基]锡二硫代磷酸酯的研究

本文合成了七个三苄基锡二硫代磷酸酯和八个三[(甲基二苯硅基)亚甲基]锡二硫代磷酸酯, 测定了它们的IR, 1H, 119Sn和31P NMR, 119Sn NMR的化学位移与磷酸酯基的芳环对位取代基Hammett常数呈线性关系。表明该两类化合物均为四价锡的单分子有机锡化合物。     

三丁基锡羧酸酯的结构表征及其生物活性研究

合成了三十个三丁基锡羧酸酯Bu3SnO2CR(R=烷基、芳基、芳氧甲基和呋喃基)。通过对它们的红外光谱、核磁共振谱(^1^3C, ^1^1^9Sn)的研究, 表明羰基红外吸收频率与锡原子的配位数有密切关系, 同样分子上的微小变化明显地表现在δ119Sn上, 对位取代基苯甲酸酯的δ119Sn与苯环上取代基的Hammett常数(σ)之间存在良好的线性关系:δ119Sn=19.11σ+110.612 n=7, γ=0.9955着重研究了部分化合物在经济作物上的抗病原菌能力, 结果表明, 这是一类具有广谱性的有机锡化合物, 抗菌活性优于对比药剂朴海因, 接近或相当于多菌灵, 它们同时具有较强的除草活性。     

三[(苯基二甲硅基)亚甲基]锡 O,O-二芳基二硫代磷酸酯的研究

本文合成了十五个新的[苯基二甲硅基]锡O,O-二芳基二硫代磷酸酯。测定了它们的IR, ^1H, ^1^3C, ^1^1^9Sn NMR及MS, ^1^1^9Sn NMR的化学位移δ和芳环对位取代基的Hammett常数σ之间存在良好的线性关系。     

A study of trialkyltin β-aryl-β-triphenylgermyl propionates

Twenty new compounds of the form Ph₃GeCHArCH₂COOSnR₃ (R = n-Bu, cyclohexyl; Ar = substituted phenyl) have been synthesized. Their structures were characterized by IR and ¹¹⁹Sn and ¹H NMR spectroscopy. The compounds are five-coordinated carboxylate bridged polymers when R = n– Bu; when R = cyclohexyl (Cy) they are four-coordinate. ¹¹⁹Sn NMR measurements of chemical shift for the two series of compounds have shown that there is a good linear relationship for the chemical shift of ¹¹⁹Sn NMR between the tributyltin and tricyclohexyltin propionates, viz. δ¹¹⁹Sn(Bu₃Sn) = 1.0474 δ ¹¹⁹Sn(Cy₃Sn) + 95.8076, n = 5, r = 0.993. The structure of one compound was determined by X-ray diffraction. It exists as a monomeric four-coordinated species in a distorted tetrahedronal geometry.     

Zinn(IV)-Komplexe mit dreizähnigen diaciden Liganden — 119Sn-NMR und 119mSn-Mössbauer-spektroskopische Untersuchungen

Tin(IV) Complexes with Tridentate Diacidic Ligands — ¹¹⁹Sn NMR and ^119mSn Mössbauer Studies The tin(IV) chelates of tridentate diacidic azomethines of acetylacetone resp. salicylaldehyde with benzoylhydrazine, thiobenzoylhydrazine, 2-hydroxyaniline and 2-mercaptoaniline as well as with the ligands 2-(2′-hydroxy-4-methylphenyl)-6-(2″-hydroxyphenyl)pyridine, 2-(2′-hydroxyphenyl)-8-quinolinol and 2.6-diphenacylpyridine were synthesized. The compounds were characterized by IR-, UV/VIS-, MS-, ¹¹⁹Sn NMR and ^119mSn Mössbauer spectroscopy. They exist as a mixture of geometrical isomers.     

三(2-甲基-2-苯基丙基)锡芳氧乙酸酯的合成

三（２－甲基－２－苯基丙基）锡芳氧乙酸酯的合成刘宝殿,宁志刚,朱东升,包明（东北师范大学化学系,长春,１３００２４）关键词三（２－甲基－２－苯基丙基）锡芳氧乙酸酯,三（２－甲基－２－苯基丙基）氢氧化锡,芳氧乙酸,杀螨活性１９６６年Ｒｅｉｃｈｌｅ［１］...     

Solid-state and high-resolution liquid 119Sn NMR spectroscopy of some monomeric, two-coordinate low-valent tin compounds: very large chemical shift anisotropies

High-resolution liquid- and solid-state 119Sn NMR spectroscopy was used to study the bonding environment in the series of monomeric, two-coordinate Sn(II) compounds of formula Sn(X)C6H3-2,6-Trip2 (X = Cl, Cr(eta 5-C5H5)(CO)3, t-Bu, Sn(Me)2C6H3-2,6-Trip2; Trip = C6H2-2,4,6-i-Pr3). The trends in the principal components of the chemical shift tensor extracted from the solid-state NMR data were consistent with the structures determined by X-ray crystallography. Furthermore, the spectra for the first three compounds displayed the largest 119Sn NMR chemical shift anisotropies (up to 3798 ppm) of any tin compound for which data are currently available. Relaxation time based calculations for the dimetallic compound 2,6-Trip2H3C6Sn-Sn(Me)2C6H3-2,6-Trip2 suggests that the chemical shift anisotropy for the two-coordinate tin center may be as much as ca. 7098 ppm, which is as broad as the 1 MHz bandwidth of the NMR spectrometer.     

Synthesis and spectroscopic and X-ray structural characterization of R2Sn(IV)-oxydiacetate and -iminodiacetate complexes

Seven novel R2Sn(IV)-oxydiacetate (oda) and -iminodiacetate (ida) compounds of the form [R2Sn(oda)(H2O)]2 (R = Me, nBu, and Ph) (1-3), [(R2SnCl)2(oda)(H2O)2]n (R = Et, iBu, and tBu) (4-6), and [Me2Sn(ida)(MeOH)]2 (7) have been synthesized and characterized by IR, 1H, 13C, and 119Sn NMR (solution), solid-state 119Sn CPMAS NMR, and (119m)Sn M?ssbauer spectroscopy. The crystal structure of [Me2Sn(oda)(H2O)]2, 1, shows it to be dinuclear (centrosymmetric), with two seven-coordinated tin atoms, bridged by one arm of the carboxylate group from each oda. By contrast, the crystal structure of [(Et2SnCl)2(oda)(H2O)2]n, 4, comprises a zigzag polymeric assembly containing a pair of different alternating subunits, {Et2SnCl(H2O)} and {Et2SnCl(H2O)(oda)}, which are connected by way of bridging oda carboxylates, thus giving seven-coordinate tin centers in both components. Finally, the structure of [Me2Sn(ida)(MeOH)]2, 7, also centrosymmetric dinuclear, is comprised of a pair of mononuclear units with seven-coordinate tin. The 119Sn solid-state CPMAS NMR and (119m)Sn Mossbauer suggest the presence of seven-coordinate Sn metal atoms in some derivatives and the existence of two different tin sites in the [(R2SnCl)2(oda)(H2O)2]n compounds.     

Synthese et etude par RMN 119Sn de nouveaux composes benzyliques organostanniques

Preparations of new benzylic organotin compounds are presented. ¹¹⁹Sn NMR studies show long range coupling constants ¹¹⁹Sn¹¹⁹Sn and intramolecular coordination of tin.     

Fine-tuned characterization at the solid/solution interface of organotin compounds grafted onto cross-linked polystyrene by using high-resolution MAS NMR spectroscopy

The structural characterization of organotin compounds that are grafted onto insoluble cross-linked polymers has necessarily been limited to elemental analysis, infrared spectroscopy, and in a few instances, solid-state NMR spectroscopy. This important bottleneck in the development of such grafted systems has been addressed by using high-resolution magic angle spinning (hr-MAS) NMR spectroscopy. The great potential of this technique is demonstrated through the structural characterization of diphenylbutyl-(3,4) and dichlorobutylstannanes (5,6), grafted onto divinylbenzene cross-linked polystyrene by means of a suitable linker (1, 2). First, conditions suitable for the application of hr-MAS NMR spectroscopy were identified by characterizing the (1)H resonance line widths of the grafted organotin moiety following swelling of the functionalized beads in eight representative solvents. The presence of clearly identifiable tin coupling patterns in both the 1D (13)C and 2D (1)H-(13)C HSQC spectra, and the incorporation of (119)Sn chemical shift and connectivity information from hr-MAS 1D (119)Sn and 2D (1)H-(119)Sn HMQC spectra, provide an unprecedented level of characterization of grafted organotins directly at the solid/liquid interface. In addition, the use of hr-MAS (119)Sn NMR for reaction monitoring, impurity detection, and quantification and assessment of the extent of coordination reveals its promise as a novel tool for the investigation of polymer-grafted organotin compounds. The approach described here should be sufficiently general for extension to a variety of other nuclei of interest in polymer-supported organometallic chemistry.