6—硫杂—13—氮杂二环（9.3.0）—3,8—二炔十四烷的合成及核磁共振鉴定

以３，４－二（４′－甲磺酰氧－２′－丁炔基）四氢呋喃或６－硫杂－３，８－二炔－１，１１－二羟甲基环十一烷为原料合成了二环化合物６－硫杂－１３－氧杂二环（９．３．０）－３，８－二炔十四烷，通过＾１ＨＮＭＲ＾１３ＣＮＭＲ，ＩＲ及ＭＳ进行结构鉴定。     

1-酰氧(胺)-2,8,9-三氧杂-5-氮杂-1-锡杂三环[3.3.3.01.5]十一烷的合成和结构研究

合成了１４个新化合物：１－酰氧（胺）基－２，８，９－三氧杂－５－氮杂－１－锡杂三环［３．３．３．０１．５］十一烷．由ＩＲ、１ＨＮＭＲ、１３ＣＮＭＲ和１１９ＳｎＮＭＲ及元素分析确定其结构．该类化合物在ＣＤＣｌ３中可能形成六配位化合物，而在ＤＭＳＯ中，溶剂分子参与Ｓｎ原子配位，聚合体解聚为六配位化合物．     

1—酰氧（胺）—2,8,9—三氧杂—5—氮杂—1—锡杂三环（3.3.3.0^1. …

合成了１４个新化合物，１－酰氧（胺）基－２，８，９－三氧杂－５－氮杂－１－锡杂三环（３．３．３．０＾１．５）十一烷，由ＩＲ，＾１ＨＮＭＲ，＾１３ＣＮＭＲ和＾１１９ＳｎＮＭＲ及元素分析确定其结构，该类化合物在ＣＤＣｌ３中可能形成六配位化合物，而在ＤＭＳＯ中，溶剂分子参与Ｓｎ原子配位，聚合体解聚为六配位化合物。     

磷杂螺环化合物的合成──3，9－二氢－3，9－二硫代－2，4，8，10－四氧杂－3，9－二磷杂螺环［5，5］十一烷的合成及其与α－芳基－β－硝基烯的加成反应

本文合成了３，９－二氢－３，９－二硫代－２，４，８，１０－四氧杂－３，９－二磷杂螺环－［５，５］十一烷２，研究了２在Ｎ，Ｎ－二甲基乙酰胺介质中，在氢化钠作用下与α－芳基－β－硝基烯的加成反应，得到５个新的加成产物３_（ａ－ｅ），对２及加成物３_（ａ－ｅ）的~１ＨＮＭＲ谱进行了归属，并得到元素分析和ＩＲ的证实。     

“烯—二炔”模型化合物前体—6—硫杂—13—氧杂双环［9.3.0 …

以顺－１,２,３,６－四氢邻苯二甲酸酐为原料,经还原、环化、臭氧化、Ｗｉｔｔｉｇ羰基烯化、酯化、二醇化和硫化等８步反应,合成了新型抗癌抗菌素“烯－二炔”的双环前体：６－硫杂－１３－氧杂双环［９．３．０］－３,８－十四二炔。该合成路线步骤少,收率高,反应条件温和。６个新化合物４－９的结构均经元素分析、核磁共振、红外光谱和质谱确证。     

两个环己烷螺含氮杂环化合物的合成和晶体结构

环己酮与硫代碳酰肼在不同介质中的反应，合成出两个不同的环己烷螺含氮杂环化合物。经Ｘ－射线结构分析确定它们分别为１，２，４，５－四氮螺［５，５］十一烷－３－硫酮，Ｃ＿７Ｈ＿（１４）Ｎ＿４Ｓ（Ⅰ）和１，２，４，－三氮螺［４，５］癸－１－烯－４－氨基－３－硫酮。Ｃ＿７Ｈ＿（１２）Ｎ＿４Ｓ＿ｘ（Ｓ＿ｘ＝０．８Ｓ＋０．２Ｏ）（Ⅱ）。晶体学参数分别为（Ⅰ）：Ｐ２＿１／ｃ，ａ＝１２．０２６（４），ｂ＝２６．８１７（６），ｃ＝１２．０４２（３），β＝１１５．９４（２）°，Ｚ＝４，Ｖ＝９３３．４（１０），Ｍ＿ｒ＝１８６．２８；（Ⅱ）：Ｐ２＿１／ｍ，ａ＝６．５９５（７），ｂ＝６．８１７（６），ｃ＝１０．５７２（６），β＝１０６．３（１）°，Ｖ＝４５６（１），Ｚ＝２，Ｍ＿ｒ＝１８１．０５。最终一致因子分别为Ｒ＝０．０５４，Ｒ＿ｗ＝０．０６５和Ｒ＝０．０８９，Ｒ＿ｗ＝０．０９６。两个化合物中，环己烷都为椅式构型，它与其螺联的６员氮杂环，５员氮杂环的最小二乘平面间的夹角分别为６８．９４和９０°。并对合成反应途径作了初步讨论。     

磷杂螺环化合物的合成——3,9—二氢—3,9—二硫代—2,4,8,10—…

本文合成了３，９－二氢－３，９－二硫代－２，４，８，１０－四氧杂－３，９－二磷杂螺环－［５，５）十一烷２，研究了２在Ｎ，Ｎ－二甲基乙酰胺介质中，在氢化钠作用下与α－芳基－β－硝基烯的加成反应，得到５个新的加成产物３ａ－ｅ，对２及加成物３ａ－ｅ的＾１ＨＮＭＲ谱进行了归属，并得到元素分析和ＩＲ的证实。     

不对称1,3,2—苯并二氧碳杂环己烷非对映消旋体的合成及生 …

通过相转移催化关环反应合成了新的６－取代－２－硫－２－烷（芳）氧－４（２，４－二氯苯基）－４－氢－１，３，２－苯并二氧磷杂环己烷（３ａ－３ｇ），用结晶法分离得到了７对非对映消旋体，其结构经ＨＮＭＲ、＾３１ＰＮＭＲ和元素分析确证，化合物３ａ－Ａ单晶Ｘ射线分析表明其构型为（２Ｒ，４Ｓ；２Ｓ，４Ｒ），生物活性测定结果表明，化合物３ｃ有良好的杀虫活性，非对映消旋体Ａ和Ｂ具有协同杀虫作用。     

具有生物活性的有机硅化合物的研究（ⅩⅢ）──1－（O，O－二烷基－二硫代磷酸酯）亚甲基－2，8，9－三氧杂－5－氮－1－硅杂三环［3，3，3，0~（1，5）］十一烷的合成

合成了９种１－（Ｏ，Ｏ－二烷基－二硫代磷酸酯）亚甲基－２，８，９－三氧杂－５－氮杂－１－硅杂三环［３，３，３，０~（１，５）］十一烷。合成方法简便，易于后处理，经元素分析、ＩＲ、１ＨＮＭＲ、ＭＳ确定了新化合物的结构，并对其进行了生物活性的研究。     

2,4,6—三氧—1,3,5,2—三氮磷杂环己烷衍生物的合成及其生物活性

利用Ｎ，Ｎ－二（２－氯乙基）氨基磷酰二异氰酸酯和胺的加成反应，合成了２，４，６－三氧－１，３，５，２－三氮磷杂环己烷衍生物，它们的结构经１ＨＮＭＲ，ＩＲ，ＭＳ和元素分析所证实．初步生测结果表明，部分化合物具有一定的抗肿瘤活性．     

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.