2－（3，4，5－三甲氧基）苯基－4，9－二氢环庚并吡喃－4，9－二酮的一步合成

２－（３，４，５－三甲氧基）苯基－４，９－二氢环庚并吡喃－４，９－二酮的一步合成高文涛（锦州师范学院化学系锦州１２１００３）关键词缩杂环酮化合物，３，４，５－三甲氧基，苯甲醛，成环缩合，合成自然界中某些抗菌素和毒菌的基本组成中含有酮结构单元，具有抗癌...     

1，2－二氢－3H－吲哚－3－酮类化合物的光化学合成

１，２－二氢－３Ｈ－吲哚－３－酮类化合物的光化学合成凌可庆（淮北煤炭师范学院化学系，淮北，２３５０００）关键词吲哚衍生物，单重态氧反应，１，２－二氢－３Ｈ－吲哚－３－酮衍生物，光合成１，２－二氢－３Ｈ－吲哚－３－酮是重要的有机合成中间体，广泛用于多种...     

4－芳氧基－4－氧代－1，3，4－二氮磷杂环戊－2－硫酮类化合物的合成及其除草活性

４－芳氧基－４－氧代－１，３，４－二氮磷杂环戊－２－硫酮类化合物的合成及其除草活性陈茹玉，张成祥，冯克胜，程慕如（南开大学元素有机化学研究所天津３０００７１）关键词二氮磷杂环戊硫酮，酚类化合物，除草活性前文［１，２］曾报道含膦脲五员环类化合物的合成，...     

1－对甲苯磺酰基－2－氧代－2－苯氧基－3－芳基－1，4，2－二氮磷杂环戊－5－硫酮的合成及其除草活性

通过１－苯基－３－对甲苯磺酰基硫脲（１）与亚磷酸三苯酯和取代苯甲醛在甲苯中进行的类Ｍａｎｎｉｃｈ反应合成１－对甲苯磺酰基－２－氧代－２－苯氧基－３－芳基－１，４，２－二氮磷杂环戊－５－硫酮（２）．本文对合成过程中所涉及到的副反应进行了初步探讨，初步的生物活性测定结果表明，化合物２具有一定的除草活性。     

1－对甲苯磺酰基－3－芳基－4－苯基－1，4，2－二氮磷杂环戊－5－酮的合成及除草活性

通过１－苯基－３－对甲苯磺酰基脲与亚磷酸三苯酯和取代苯甲醛在甲苯中进行的类Ｍａｎ－ｎｉｃｈ反应合成１－对甲苯磺酰基－２－苯氧基－２－氧代－３－芳基－４－苯基－１，４，２－二氮磷杂环戊－５－酮．化合物的结构经元素分析、ＮＭＲ、ＭＳ及部分化合物的红外光谱所证实，对合成过程中所涉及到的副反应进行了初步探讨，生物测定实验表明，某些产物具有良好的选择性除草活性。     

3，4－二硫方酸的从头算研究

在６－３１Ｇ水平上对３，４－二硫方酸（３，４－二巯基－３－环丁烯－１，２－二酮）的３种平面构象异构体进行ＳＣＦ计算．结果表明，ＺＺ型异构体最稳定，ＺＥ型次之，从等键反应能量分析３，４－二硫方酸的稳定性，与苯作比较探讨其芳香性．并在６－３１Ｇ水平上计算了３种构象的振动频率．     

1，3，4，6－四硫代戊搭烯－2，5－二酮制备含硫取代基的四硫富瓦烯的研究

以１，３，４，６－四硫代戊搭烯－２，５－二酮为原料，经偶联、醇解、烃化或醇解、烃化、偶联等步骤，制得四甲硫基四硫富瓦烯、四乙硫基四硫富瓦烃、二喹喔啉硫醚、４－甲硫基－５－甲氧甲酰硫基－１，３－二硫环戊烯－２－酮、四甲硫基乙烯和４，４＇－二甲硫基－５，５＇－二甲氧甲酰硫基四硫富瓦烯及它的异构体混合物．提出了１，３，４，６－四硫代戊搭烯－２，５－二酮醇解机理．讨论了未得到某些预期产物的原因．报道了３种四硫富瓦烯衍生物的循环伏安图及电化学性质．     

2，5－二取代－1，3，4－噁二唑和N，N′－二酰基肼化合物的合成与生物活性

合成了１８种新的对称与不对称的２，５－二取代－１，３．４－　二唑及Ｎ，Ｎ′－二酰基肼化合物，用元素分析、红外光谱、核磁氢谱和质谱确定了其结构，并对它们的杀虫、抗菌活性进行了测试，发现了数个具有效强生物活性的化合物。     

α－羰基烯酮环二硫代缩醛化学（ⅩⅤ）──β，β－1，3－亚丙二硫基－α，β－不饱和芳酮与2－甲基烯丙基Grignard试剂加成物的酸催化取代－环合芳构化反应

α－羰基烯酮环二硫代缩醛化学（ⅩⅤ）──β，β－１，３－亚丙二硫基－α，β－不饱和芳酮与２－甲基烯丙基Ｇｒｉｇｎａｒｄ试剂加成物的酸催化取代－环合芳构化反应杨智蕴，王子苓，刘群，胡玉兰（东北师范大学化学系，长春，１３００２４）关键词β，β－１，３－亚...     

β－二酮或β－三酮对铈（Ⅳ）盐引发烯类单体聚合的影响

研究了β－二酮或β－三酮（如：３－苄基乙酰丙酮、苯甲酰基丙酮、二苯甲酰基甲烷及３－苯甲酰基乙酰丙酮）对铈（Ⅳ）盐引发丙烯酰胺聚合的促进作用，测定了聚合反应速度及表现活化能，表明铈（Ⅳ）盐／β－二酮或β－三酮可组成活性很高的氧化还原体系；采用自旋捕捉技术及ＥＳＲ谱研究了体系的初级自由基结构；通过ＦＴＩＲ光谱端基分析检测到这类体系引发丙烯腈所得聚合物端基有β－二酮结构。以此为基础，提出了这类体系引发烯类单体聚合的机理。     

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%.     

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.     

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.     

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.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

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.     

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.