二烃基锡双（O，O－二硫代磷酸酯）的合成和波谱研究

合成了１５个二烃基双（Ｏ，Ｏ－二硫代磷酸酯）化合物。利用ＩＲ、（１Ｈ、１３Ｃ、１１９Ｓｎ）ＮＭＲ表征了化合物的结构。这是一类六配位变形八面体结构的二烃基锡化合物。对化合物的质谱裂解机制进行了讨论。     

三羰基环戊二烯基钼负离子与1,3—二卤丙烷的反应

三羰基环戊二烯基钼负离子与１，３－二卤丙烷在一缩二乙二醇二甲醚介质中反应，生成环卡宾配合物ＣｐＭｏＸ（ＣＯ２）ＣＯ（ＣＨ２）２ＣＨ２（Ｘ＝Ｂｒ．Ｉ）硅桥连双环戊二烯基三羰基钼负离子与１，３－二卤丙烷顺利地进行类似反应，生成相应的硅桥连双（环卡宾钼配合物）－Ｅ（Ｃ５Ｈ１ＭｏＸ（ＣＯ）２ＣＯ（ＣＨ２）２ＣＨ２）２（Ｅ＝Ｍｅ２Ｓｉ，Ｍｅ２ＳｉＳｉＭｅ２，Ｍｅ２ＳｉＯＳｉＭｅ２），化合物硅氧硅桥联二茂二钼     

含硅二硫代磷酸酯的合成及生物活性

硅基甲硫醇Ｒ＾１Ｒ＾２ＣＨ３ＳｉＣＨ２ＳＨ与Ｏ，Ｏ－二烷基二硫代磷酸酯（ＲＯ）２Ｐ（Ｓ）ＳＨ及甲醛可顺利地发生类Ｍａｎｎｉｃｈ缩合反应，利用此反应和硅基甲硫醇与Ｏ，Ｏ－二乙基－Ｓ（２－溴乙基）二硫代磷酸酯的取代反应合成了３７种新的含硅二硫代到酯化合物（ＲＯ）２Ｐ（Ｓ）Ｓ（ＣＨ２）ｎＳＣＨ２ＳｉＣＨ３Ｒ＾１Ｒ＾２（ｎ＝１，２），在初筛浓度下，该类化合物具有一定的杀虫，杀螨活性。     

柄型茂金属化合物（Ⅲ）

１,２－二（１－茚基）四甲基二硅烷相继与本基锂及ＭＣｌ４·２ＴＨＦ作用。生成四甲基二硅桥连二（１－茚基）钛和锆化合物（Ｍｅ２ＳｉＳｉＭｅ２）「Ｉｎｄ」２ＣＭｌ２「Ｍ＝（Ｔｉ（１）,Ｚｒ（２）」,对其进行催化氢化,得到相应的四氢茚基化合物（Ｍｅ２ＳｉＳｉＭｅ２）「ＩｎｄＨ４」２ＭＣｌ２「Ｍ＝Ｔｉ（３）,Ｚｒ（４）」通过元素分析,ＭＳ和ＨＮＭＲ谱表征了化合物的分子结构,并了在ＭＡＯ的助催化下,化合物３     

含硅有机锗化合物的合成

报道了一类含硅有机锗化合物的合成。从Ｍｅ３ＳｉＣｌ，ＲＸ，ＧｅＯ２出发，经过氯化、格氏反应、亲核取代等反应，制得目标化合物－－二〔烃基二甲硅基甲基〕锗的二氯化物。它们的结构经元素分析和红外表征。     

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。     

三羰基全甲基硅基环戊二烯基钼衍生物的合成与表征

通过三羰基（五甲基二硅基）环戊二烯基钼负离子盐与卤代烃（ＥｔＩ，ＰｈＣＨ２Ｃｌ，ＣｌＣＨ２ＣＯＯＥｔ，Ｉ（ＣＨ２）４Ｉ）进行基化反应合成其烷基钼化合物。用六甲基三硅二氧烷桥联双（三羰基环戊二烯基钼）负离子经冰醋酸处理，硫酸铁氧化偶联成钼－钼键双核化合物，经碘裂解后钼－钼键生成六甲基三硅二氧烷桥联双（三羰基环戊二烯基碘钼）化合物。以元素分析，ＩＲ和１ＨＮＭＲ谱表征了化合物的结构。     

1,4—双（取代苯乙炔基）苯及反,反—1,4—双（β—取代苯乙…

测定了１，４－双（取代苯乙炔基）苯（Ⅰ）和反，反－１，４－双（β－取代苯乙烯基）苯（Ⅱ）的紫外光谱、荧光光谱。用ＣＮＤＯ／Ｓ－ＣＩ和ＨＭＯ方法对苯乙炔、二苯乙炔和（Ⅰ）及苯乙烯、１，２－二苯乙烯和（Ⅱ）的激发能进行了计算和研究。讨论了化合物结构对光谱的影响。     

1,2-双(四甲基环戊二烯基)四甲基二硅烷与六羰基钼的反应

１,２－双（四甲基环戊二在）四甲基二硅烷与正丁基锂作用生成（四甲基二硅撑）双（四甲基环戊二烯基负离子盐）,后者随即与六羰基钼反应形成１,１＇－（四甲基二硅撑）双（四甲基环戊二烯基钼负离子盐）－－（Ｍｅ２ＳｉＳｉＭｅ２）〖Ｍｅ４ＣｐＭｏ（ＣＯ）３－Ｌｉ＾＋〗２（１）,１与冰醋酸作用,随即分别与ＣＣＩ４,ＮＢＳ及Ｉ２反应,生成相应的钼卤化合物（Ｍｅ２ＳＩＳｉＭｅ２）〖Ｍｅ４ＣｐＭｏ（ＣＯ）３Ｘ〗２〖Ｘ     

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.     

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%).     

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.     

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.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.