1，3－双－（介晶基）－1，1，3，3－四甲基二硅氧烷的合成和相变研究

合成了１６种１，３－双－（介晶基）－１，１，３．３－四甲基二硅氧烷（Ⅱ_（ａ，ｂ），Ⅲ_（ａ─ｇ），Ⅲ_ｊ，Ⅳ_（ａ─ｆ）．其化学结构用￣１ＮＭＲ、ＩＲ、ＵＶ和元素分析表征。通过ＤＳＣ和偏光显微镜研究了它们的相行为，除Ⅱ_（ａ，ｂ）、Ⅲ_ｄ和Ⅳ_ｄ外，其余都呈现液晶相变。用Ｘ衍射分析研究了１，３－双－（４－甲基偶氮苯氧甲基）－１，１，３，３－四甲基二硅氧烷（Ⅱ_ａ）的晶体结构。讨论了这些新型硅氧烷化合物的比学结构对液晶相变行为的影响。     

含固氮酶钼微环境结构单元O_3MoS_3的Mo－S，Mo－Fe－S化合物的研究

研究了含固氮酶钼微环境Ｏ_３ＭｏＳ_３结构单元四个系列化合物［Ｍｏ（Ｓ，Ｏ－Ｃ_６Ｈ_４－１，２］~－（Ｍ）［Ｍｏ_２（ＣＯ）_３（Ｓ，Ｏ－Ｃ_６Ｈ_４－１，２）_３］~（２－）（Ｄ），［Ｍｏ_３（ＣＯ）_７（Ｓ，Ｏ－Ｃ_６Ｈ_４－１，２）_３］~（２－）（Ｔ），和［Ｍｏ_２Ｆｅ（ＣＯ）_４（Ｓ，Ｏ－Ｃ_６Ｈ_４－１，２）_３Ｃｌ_２］~（２－）（Ｔ_ｆ）的合成化学与结构化学，并通过Ｘ－射线光电子能谱，红外光谱和电化学环伏安研究，深入探讨了它们的混合价，电子迁移和电化学行为，也讨论了有趣的Ｏ_３ＭｏＳ_３结构单元。     

含L－氨基酸结构的手性液晶化合物的合成及其相变行为

合成了９种具Ｌ－氨基酸衍生物结构的介晶化合物（Ｉ－Ⅲ，Ⅳａｂ，Ⅴａ，ｂ，Ⅵａ，ｂ）、４种氨基酸衍生物（Ａ１－４）和６种介晶化合物（Ｍ１－６）．新化合物（Ⅰ－Ⅲ，Ⅳａ，ｂ，Ⅴａ，ｂ，Ⅵａ，ｂ，Ａ４，Ｍ３－６）的化学结构通过ＩＲ、１ＨＮＭＲ和元素分析证实；并用偏光显微观察和ＤＳＣ分析研究了其相变行为，结果表明有８种化合物（Ｍ３－６，Ⅵａ，ｂ，Ⅴｂ，Ⅵｂ）呈现液晶相变。测定了它们的比旋光度。通过Ｘ射线衍射研究了化合物Ⅵｈ１２０～１３０℃和Ⅵｂ１７０～１８０℃的近晶结构，Ⅵｂ显，Ⅵｂ呈。测定了化合物Ⅳｂ的电滞回线，证明其具铁电性。     

柄型金属有机化合物（Ⅱ）：硅氧硅桥联二（1—茚基及四氢茚基…

１，３－二（１－茚基）四甲基二硅氧烷相继与丁基锂及ＺｒＣｌ４．２ＴＨＦ作用，生成硅氧桥联二（１－茚基）二氯化锆（Ｍｅ２ＳｉＯＳｉＭｅ２）（Ｉｎｄ）２ＺｒＣｌ２（１）。对其进行催化氢化得到相应的四氢茚基化合物（Ｍｅ２ＳｉＯＳｉＭｅ２）ＩｎｄＨ４）２ＺｒＣｌ２（２）．１和２均含有顺式和反式二种异构体（１和１以及２和２），通过重结晶得到纯的单一异构体，１，２和２，１和２的晶体结构经Ｘ射线衍射测定，二者均     

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。     

6-羟基富烯及环戊二烯并[d][1,2]嗪的合成

由６，６－二烷基富烯与烯丙基格氏试剂加成所得到的取代环戊二烯基负离子与芳酰氯反应，合成了５个未见文献报道的６－羟基富烯化合物（１～５）。用此类化合物与羟胺反应，合成了５个新的环戊二烯并［ｄ］口恶嗪化合物（６～１０），其结构经ＩＲ，１ＨＮＭＲ和元素分析证实。     

6—羟基富烯及环戊二烯并[d][1,2]恶嗪的合成

由６，６－二烷基富烯与烯丙基格氏试剂加成所得到的取代环戊二烯基负离子与芳酰氯反应，合成了５个未见文献报道的６－羟基富烯化合物（１￣５）。用此类化合物与羟胺反应，合成了５个新的环戊二烯并［ｄ］恶嗪化合物（６￣１０），其结构经ＩＲ，＾１Ｈ ＮＭＲ和元素分析证实。     

6-硫杂-13-氧杂二环[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进行了结构鉴定。     

2,2′-二取代-1,1′-联萘化合物的NMR研究

用二维核磁共振谱（ＣＯＳＹ、ＨＭＱＣ、ＨＭＢＣ、ＦＧ＿ＨＭＢＣ）进一步研究了２，２′－二羟基－１，１′－联萘（１）、２，２′－二甲氧基－１，１′－联萘（２）、２，２′－亚甲二氧基－１，１′－联萘（３）、２，２′－亚乙二氧基－１，１′－联萘（４）、２－羟基－２′－甲氧基－１，１′－联萘（５）、２－羟基－２′－乙氧基－１，１′－联萘（６）、２－羟基－２′－异丙氧基－１，１′－联萘（７）、２－羟基－２′－丁氧基－１，１′－联萘（８）和２－羟基－２′－氧乙酸基－１，１′－联萘（９）等９个２，２′－二取代－１，１′－联萘化合物，确定了它们的氢谱和碳谱谱峰的归属，指出联萘化合物的立体结构、萘环的磁各向异性对质子谱有明显的影响，特别是Ｈ８（Ｈ８′）；而其对环碳的影响可以忽略。     

含磷稠杂环的合成及其生物活性

研究了氯代膦酰异氰酸酯与５－氨基－３－苄硫基－１，２，４－三唑及其类似物的成环反应，合成了１２个，７－芳基（烷氧基）－２－苄硫基－５，７－二氧代－４，５，６，７－四氢－７－磷杂－１，２，４－三唑（１，５ａ）三嗪，利用ＨＮＭＲ，ＰＮＭＲ确定其为Ｚ型，生物活性测定结果表明，部分化合物具有一定的除草活性。     

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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.