四种(3,4),(8,9)-双环氧-三环[5.2.1.02,6]癸烷的合成和构型

以内式及外式-三环[5.2.1.0^2,6]癸二烯-3,8为原料进行部分环氧化反应,先制得在[2.2.1]庚烷环上具有环氧基的单氧化物.然后分别以过醋酸环氧化,或进行次氯酸酯加成,继而脱去氯化氢而环氧化,制得四种立体构型不同的(3,4),(8,9)-双环氧-三环[5.2.1.0^2,6]癸烷.对它们的构型进行了讨论.     

三环羧酸酯的α－羟基化反应研究

三环羧酸酯（Ⅱ）在强碱ＬＤＡ作用下经过烯醇中间体，由空气氧对其进行氧化，在羰基α－位引入一个过氧键，尔后用亚硫酸钠还原得到三环羟基羧酸酯（Ⅲ）。用量子化学ＡＭ１计算结果分析了Ⅲｂ分子中形成分子内氢键的原因及其与Ⅲａ和Ⅲｃ之间的区别。     

三环羧酸酯的α—羟基化反应研究

三环羧酸酯（ＩＩ）在强碱ＬＤＡ作用下经过烯醇中间体，由空气氧对其进行氧化，在羰基α－位引入一个过氧键，尔后用亚硫酸钠还原得到了三环羟基羧酸酯（Ⅲ）。用量子化学ＡＭ１计算结果分析了Ⅲｂ分子中形成分子内氢键的原因及其与Ⅲａ和Ⅲｃ之间的区别。     

新的苯并二氮卓类三环化合物：1H，10H4，9－二氢－环戊并［1，2－b］［1，5］苯并二氮卓－10－酮及其3－甲基衍生物的合成

通过邻苯二胺与环戊酮的β－羧酸酯缩合及催化氢化，合成了由环戊基与苯并二氮并环形成的新的苯并二氮类三环化合物。     

新的苯并二氮Zuo类三环化合物：1H,10H—4,9—二氢—环戊并（1,2—b）（1,5）苯并二

通过邻苯二胺与环戊酮的β－羧酸酯缩合及催化氢化，合成了由环戊基与苯并二氮Ｚｕｏ并环形成的新的苯并二氮Ｚｕｏ类三环化合物。     

有机锡4-(4-吡啶基甲基硫代)苯甲酸酯的合成、结构与生物活性研究(英文)

通过4-(4-吡啶基甲基硫代)苯甲酸与三苯基氧化锡以及三环己基氢氧化锡反应,合成了三苯基锡4-(4-吡啶基甲基硫代)苯甲酸酯(1)及三环己基锡4-(4-吡啶基甲基硫代)苯甲酸酯(2)。它们的结构通过红外,核磁以及X-射线单晶衍射分析得到确证。化合物1表现为一维链状结构,而化合物2通过分子间的O-H…O和O-H…N氢键形成二维网状结构。生物活性测试表明,这2个化合物具有较高的抗肿瘤活性。     

杂氮硅三环侧链上基团转换反应的研究

2,8,9-三氧杂-5-氮杂-1-硅双环[3,3,3]十一碳烷(简称杂氮硅三环)是一类具有五配位键的有机硅化合物。有关它的合成方法和其物理化学性质,文献中已报道甚多。但有关硅三环上与硅侧链相连接的有机基团的转换反应或其它反应研究的还很不够。我们认为进行这方面工作是很有意义的,因为一般硅三环都是从相应的三烷氧基硅烷与三乙醇胺反应制得。如果能从一种硅三环开始进行基团转換来得到一系列其它基团的硅三环,这就为这一类化合物的合成提供新路线。与此同时,还可研究硅三环在各种合成条件     

有机锡4-(4-吡啶基甲基硫代)苯甲酸酯的合成、结构与生物活性研究

通过4-（4-吡啶基甲基硫代）苯甲酸与三苯基氧化锡以及三环己基氢氧化锡反应,合成了三苯基锡4-（4-吡啶基甲基硫代）苯甲酸酯（1）及三环己基锡4-（4-吡啶基甲基硫代）苯甲酸酯（2）。它们的结构通过红外,核磁以及X-射线单晶衍射分析得到确证。化合物1表现为一维链状结构,而化合物2通过分子间的O-H…O和O-H…N氢键形成二维网状结构。生物活性测试表明,这2个化合物具有较高的抗肿瘤活性。     

主链含杂氮硅三环的聚醚的合成及其抗肿瘤活性研究

通过乙二醇或多缩乙二醇双缩水甘油醚与氨基乙醇开环聚合,然后与γ-氨基丙基三乙氧基硅烷反应,合成了四种主链含γ-氨基丙基杂氮硅三环的聚醚聚合物。将这四种聚醚聚合物与芳香醛反应,合成了十二种主链含有γ-芳亚甲氨基丙基杂氮硅三环的聚醚聚合物。用IR、UV、~1HNMR和元素分析对它们的结构进行了验证。用体外细胞培养法测定了这些聚合物的抗肿瘤活性。     

三环己基锡芳氧乙酸盐的合成及其结构表征

三环己基锡衍生物(Cy_3SnX,Cy=环己基,X=配体或取代基)是一类具有较强生物活性的有机锡化合物,它们广泛用作杀螨剂,杀菌剂和海洋防污剂。有关三环己基锡芳氧乙酸盐的合成至今报道很少。Bubblitz 合成了两个三环已基锡芳氧乙酸盐,此后,Matsuda 等人制备了三环已基锡-2,4-二氯苯氧乙酸盐,它们都具有良好的杀螨、杀菌活性,后者还可应用于海洋     

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%.     

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.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

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.     

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.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.