Microcellobospotia grisea中具有强抗肿瘤活性多糖重复单元中心片断的合成

通过应用三氟乙酸酯法和Koenigs-Knorr方法，对Microcellobospotia grisea中具有强抗肿瘤活性多糖重复单元中心二糖片断进行了合成研究，并经元素分析，IR，^1H，^1^3C-NMR，^1H～^1H COSY及FAB-MS确证了合成得到的二糖片断10～13的结构。     

1-芳酰基-4-菊酰基氨基硫脲类化合物的合成及生物活性

本文利用菊酰基异硫氰酸酯与芳基酰肼的加成反应合成了16个新的酰氨基硫脲类化合物，其结构经^1H NMR，IR，MS和元素分析所确证，生物活性测定表明它们具有一定杀菌活性。     

手性-3, 5-二取代-1', 2', 4'-三唑-[3', 4'-b]-2, 4-二氢间 噻二嗪的合成及 生物活性

以3-芳基-5-巯基-1,2,4-均三唑为原料,和甲醛及S-(-)-α-苯乙胺在酸催化作用下合成了6种新的化合物。研究了合成反应的条件。通过元素分析、IR、^1HNMR、和MS确证了其结构,测定了比旋光度和生物活性。结果表明,一些化合物具有一定的抗菌活性。     

5-甲基-1,3,4-噻二唑-2-硫为端基的非环冠醚的合成

本文用2-巯基-5-甲基-1,3,4-噻二唑与二溴乙烷或低聚乙二醇溴化物合成了四种新的非环冠醚. 通过元素分析,UV,IR和^1H NMR波谱鉴定.     

Coα, Coβ-二腈六甲基N-(3-咪唑基)丙基酰胺钴啉酯的合成

维生素B~1~2衍生物, 二腈六甲基钴啉酯单酸与3-咪唑基丙胺的反应, 合成了五个新的在钴呵啉环外围b, c, d, e, f-侧链酰胺类钴啉酯化合物3b-f, 产物结构经UV/VIS、CD、IR、^1H NMR、^1^3C NMR和MS-(FAB)分析确认。     

7-氮杂-3,6-二氧杂-二环[3.3.0]辛-2-酮类化合物合成的新方法

5-甲氧基-2-（5H）-呋喃酮与氮酸硅烷基酯通过1，3-偶极环加成反应可以为7-氮杂-4-甲氧基-3，6-二氧杂-二环[3.3.0]辛-2-酮类化合物提供新的合成途径。通过元素分析、IR、^1HNMR、^13CNMR、MS等波谱分析进行了结构表征。     

N-苯基-N＇-（5-苯基-2-呋喃酰基）脲的合成与生物活性

为考察脲桥变化对活性的影响，通过异氰酸苯酯和取代苯基呋喃甲酰胺反应合成了8个未见报道的N-苯基-N‘-(5-苯基-2-呋喃酰基)脲化合物，其结构均经元素分析，IR和^1H NMR确证。测定了它们的生物活性,发现所合成的化合物对蚊幼虫有明显的几丁质抑制活性。     

6,7-亚甲二氧基-9-甲基-1(2H,4H)-吖啶酮衍生物的合成

以5-芳基-1,3-环基环己二酮为原料合成了8个未见报道的吖啶酮衍生物,其结构均经元素分析,IR和^1H NMR光谱确证。其中3-呋喃基-6,7-亚甲二氧基-9-甲基-1(2H,4H)-吖啶醇对一些肿瘤细胞有抑制作用。     

N-糖基-N＇-酰氨基硫脲及其环合产物的合成

以L-α-氨基酸为起始原料，经酯化、氨基保护、肼解制得N-对甲苯磺酰基-L—α-氨基酸酰肼2，再与糖基异硫氰酸酯3～5反应，得到9种新型N-糖基-N＇-酰氨基硫脲6～8，然后在Hg（OAc）2／EtOH条件下关环，合成了一系列新的2-对甲苯磺酰氨基烃基-5-糖氨基-1，3，4-噁二唑类化合物9～11．所有新化合物的结构均经IR，^1H NMR，MS谱和元素分析确证．     

meso-四(烷氧基苯基)卟啉及其金属络合物的波谱研究

采用^1H NMR、MS、IR、UV、元素分析等分析测试表征手段确证了所合成的10个系列卟啉及其金属络合物的结构,研究了不同位置、不同链长烷氧基四苯基卟啉和不同金属离子卟啉络合物的结构与^1HNMR、IR和UV等波谱之间的关系,总结了卟啉配体及其金属络合物的^1H NMR、IR和UV判据,报道和解释了meso-四(烷氧基苯基)卟啉铜、锰络合物和meso-四(邻烷氧基苯基)卟啉钴络合物的^1H NMR研究结果,通过MS、^1H NMR、IR、UV、元素分析确证了我们所合成的铁卟啉为μ-氧桥联夹心二聚体结构,且存在两种典型构象,导致同系列络合物有四种类型^1H NMR谱图。     

1-(2-苯并呋喃酰基)愈创兰烃薁的合成

在路易斯酸作用下, 以氯乙酰氯为酰基化试剂, 对愈创兰烃薁进行了酰化反应研究, 将氯乙酰化产物与水杨醛在温和反应条件下进行缩合, 以较好的收率、高选择性地得到1-(2-苯并[b]呋喃酰基)兰烃薁类衍生物, 其结构经1H NMR, IR及元素分析等得以证实.     

A dimeric titanium-containing polyoxometalate. Synthesis, characterization, and catalysis of H2O2-based thioether oxidation

The previously unknown titanium(IV)-containing mu-hydroxo dimeric heteropolytungstate (Bu4N)7[(PTiW11O39)2-OH] (TBA salt of H1) has been synthesized, starting from H5PTiW11O40, and characterized by elemental analysis, multinuclear (31P, 17O, 183W) NMR, IR, FAB-MS, cyclic voltammetry, and potentiometric titration. 31P NMR reveals that H1 (delta -12.76) readily forms in MeCN from the Keggin monomer (POM), PTiW11O40(5-) (2, delta -13.34), upon the addition of 1.5 equiv of H+, via the protonated species, P(TiOH)W11O39(4-) (H2, delta -13.44). The ratio of H1, 2, and H2, which are present in equilibrium in MeCN solution at 25 degrees C, depends on the concentration of both H+ and H2O. The Ti-O-Ti linkage readily reacts with nucleophilic reagents, such as H2O and ROH, to yield monomeric Keggin derivatives. mu-Hydroxo dimer H1 shows higher catalytic activity than 2 for thioether oxidation by hydrogen peroxide in acetonitrile. The reaction proceeds readily at room temperature and affords the corresponding sulfoxide and sulfone in ca. quantitative yield. The addition of H2O2 to H1 or H2 results in the formation of a peroxo complex, most likely the hydroperoxo complex P(TiOOH)W11O39(4-) (I), which has 31P NMR resonance at -12.43 ppm. The rate of the formation of I is higher from H2 than from H1. When H1 is used as a catalyst precursor, the rates of the thioether oxidation and peroxo complex formation increase with increasing H2O concentration, which favors the cleavage of H1 to H2. H2O2 in MeCN slowly converts 2 to another peroxotitanium complex, P(TiO2)W11O39(5-) (II), which has 31P NMR resonance at -12.98 ppm. Peroxo complexes I and II differ in their protonation state and interconvert fast on the 31P NMR time scale. Addition of 1 equiv of H+ completely converts II to I, while 1 equiv of OH- completely converts I to II. 31P NMR confirms that I is stable under turnover conditions (thioether, H2O2, MeCN). Contrary to two-phase systems such as dichloroethane/aqueous H2O2, no products resulting from the destruction of the Keggin POM were detected in MeCN in the presence of H2O2 (a 500-fold molar excess). The reactivity of I, generated in situ from II by adding 1 equiv of H+, toward organic sulfides under stoichiometric conditions was confirmed using both 31P NMR and UV-vis spectroscopy. This is a rare demonstration of the direct stoichiometric oxidation of an organic substrate by a titanium peroxo complex.     

Synthesis and Costal Structure of 2-（N-Cyclohexyl）-imino- 1,4-sucdni Add Dihydrate

The title compound 4 was synthesized in good yield via the Michael addition of 5-methoxy-2-(5H)furanone 1 with cyclo-haxoamine 2 and subsequent oxidation of the Michael adduct 3 by H2O2 aqueous solution under mild conditions. The chemical structure and stereochemistry of the novel amino acid 4 were readily confirmed by spectrosc opicdata, such as IR, ^1H NMR, ^13C NMR,MS and X-ray crystal analysis.     

5-(S)-孟氧基-3,4-二卤-2(5H)-呋喃酮与4-硝基邻苯二胺的Michael加成―消除反应

在Et3N作为碱的温和条件下,5-(S)-孟氧基-3,4-二卤-2(5H)-呋喃酮与芳香胺4-硝基邻苯二胺发生串联的Michael加成―消除反应,生成了新的含有苯环结构的5-孟氧基-4-氨基-3-卤-2(5H)-呋喃酮类化合物。新化合物的结构通过紫外―可见光谱(UV-Vis)、红外光谱(IR)、质谱(MS)、核磁共振氢谱(1H NMR)、核磁共振碳谱(13C NMR)和元素分析等表征证实。该多环结构卤代2(5H)-呋喃酮化合物的合成,能为某些多官能团的结构复杂的2(5H)-呋喃酮化合物的合成提供新途径。     

1-三氟乙酰基-2-(4-氨基苯基)肼的合成

以对硝基苯肼和三氟乙酸酐为原料,通过酰化法合成了1-三氟乙酰基-2-(4-硝基苯基)肼,将其还原得1-三氟乙酰基-2-(4-氨基苯基)肼。其结构经^1HNMR,IR,MS和元素分析确证。研究了反应条件对收率的影响及规律,得出较佳的合成条件。     

1-{2-咪唑[1,2-a]吡啶基}愈创兰烃薁的合成

以1-氯乙酰基愈创兰烃薁和取代2-氨基吡啶为原料,一锅法合成了一系列未见文献报道的1-{2-咪唑[1,2-a]吡啶基}愈创兰烃薁衍生物,收率47%～74%,其结构经1H NMR,IR和元素分析表征。     

Investigation on the interactions between diperoxovanadate and substituted phenanthroline

Detailed investigations were carried out to explore the interaction systems of NH4VO3/H2O2/5,6-dimethyl-1,10-phenanthroline and NH4VO3/H2O2/5-methyl-1,10-phenanthroline in aqueous solution under physiological conditions by NMR spectroscopy, such as 1D 1H, 13C, 51V variable temperature, and 2D COSY, NOESY, HETCOR, COLOC techniques as well as density functional calculations. New species [OV(O2)2(5,6-dimethyl-1,10-phenanthroline)]- and [OV(O2)2(5-methyl-1,10-phenanthroline)]- including isomers were formed in a bidentate coordination fashion which were stable under the experimental conditions. The solution structures of these new species were proposed based on the direct NMR experimental information and confirmed by the theoretical calculations. All the 1H and 13C NMR peaks were assigned. The calculated 1H and 13C chemical shifts on the whole are in fair agreement with the experimental values. The methyl groups on the aromatic ring of the three new complexes were found to have a steric hindrance effect on the coordination process. Experimental results show that the order of coordination capability of phenanthroline and its derivants was: 1,10-phenanthroline>5-methyl-1,10-phenanthroline>5,6-dimethyl-1,10-phenanthroline.     

新型萜烯马来酸酐醇酸树脂的合成与结构表征

利用廉价工业松节油与顺丁烯二酸酐、多元醇。油酸等原料,合成了一种色泽浅,性能良好的萜烯马来酸酐醇酸树脂。研究了合成反应条件,用FTIR谱、^1^HNMR、TGA等手段对产物结构进行了表征,并测定了树脂的性能。     

手性3-溴-2(5H)-呋喃酮的合成及其串联的不对称Michael加成 反应的研究

研究了新的手性试剂,5-(l-孟氧基)-3-溴-呋喃酮(5a)的合成及其与亲核性醇发生的串联不对称双Michael加成/分子内亲取代反应。通过此反应,一举生成了四个新的手性中心,得到了一般方法难以合成的含有多个手性中心的丁内酯并螺－环丙烷类化合物8a～8d。详细报道了8a～8d的合成方法以及它们的[α]、IR、UV、^1^HNMR、^13^CNMR、MS、元素分析等结构分析数据。此不对称双Michael加成/分子内亲核取代反应可以为某些新的光学活性螺－环内丙烷类化合物以及某些复杂结构的分子提供合成策略。     

4-羟基偶氮苯与6-氯-5, 12-萘并萘醌反应产物的NMR分析

无水碳酸钾存在下6-氯-5, 12-萘并萘醌与4-羟基偶氮苯在干燥DMF中反应的主要产物在某些反应条件下不是6[4-(苯基偶氮基)苯氧基]-5, 12-萘并萘醌(1)。该未知反应产物2经核磁共振方法研究证实是6-(N, N-二甲氨基)5, 12-萘并萘醌。本文对化合物2的1H-和13C化学位移、偶合信息和结构作了详细归属, 并推测其反应进程, 实验结果表明, 化合物2是由化合物1与溶剂DMF反应生成。