4—CH3SC6H4NH2对α—磷酸锆的插层特性

制备了４－ＣＨ３ＳＣ６Ｈ４ＮＨ２（ＭＭＡ）插层的α－Ｚｒ９ＨＰＯ４）２．Ｈ２Ｏ，研究了不同实验条件下ＭＭＡ的插层特性，发现插层反应与ＭＭＡ和α－ＺｒＰ摩尔比Ｒ有关；（１）当Ｒ〉２时，有插层产物相产生，但是即使在ＭＭＡ大大过量的条件下，仍然有部分α－ＺｒＰ颗粒大小等有关；插层产物的层间距约为２．３６ｎｍ，，层间距的大小不随反应物浓度，温度等条件变化。     

一些多层夹心配合物的电子结构和成键

本文采用Ｆｅｎｓｋｅ－Ｈａｌｌ方法研究了三层和四层夹心配合物的电子结构和成键。结果拽出，三层夹心配合物的稳定电子组态为３０－３４价电子（ＶＥ），但是当金属－金属间距缩短时，由两个过渡金属的ｄｘ＾２，ｄｘ＾２－ｙ＾２，和ｄｘｙ组成的三个ＭＯ能级上升且定位在前线轨道区域，因此预料２６－２８ＶＥ也是稳定电子组态。基于ＭＯ分析，４２Ｖ遥四层夹心配合物是稳定电子组态，然而由于ＨＯＭＯ（ｄｘ＾２）与ＬＵＭＯ（     

THE TRANSPORT PROPERTY OF HYDROGEN THROUGH PALLADIUM IMPREGNATED γ－Al_2O_3 MEMBRANE

ＴＨＥＴＲＡＮＳＰＯＲＴＰＲＯＰＥＲＴＹＯＦＨＹＤＲＯＧＥＮＴＨＲＯＵＧＨＰＡＬＬＡＤＩＵＭＩＭＰＲＥＧＮＡＴＥＤγ┐Ａｌ２Ｏ３ＭＥＭＢＲＡＮＥＺｈａｏＨｏｎｇｂｉｎ，ＬｉＡｎｗｕ，ＧｕＪｉｎｇｈｕａ，ＸｉｏｎｇＧｕｏｘｉｎｇ＊（ＳｔａｔｅＫｅｙＬａ...     

SYNTHESIS OF Mg-Al LAYERED DOUBLE HYDROXIDES PILLARED WITH POLYOXOMETALATES

ＳＹＮＴＨＥＳＩＳＯＦＭｇ－ＡｌＬＡＹＥＲＥＤＤＯＵＢＬＥＨＹＤＲＯＸＩＤＥＳＰＩＬＬＡＲＥＤＷＩＴＨＰＯＬＹＯＸＯＭＥＴＡＬＡＴＥＳＳＹＮＴＨＥＳＩＳＯＦＭｇ－ＡｌＬＡＹＥＲＥＤＤＯＵＢＬＥＨＹＤＲＯＸＩＤＥＳＰＩＬＬＡＲＥＤＷＩＴＨＰＯＬＹＯＸＯ...     

烷基磷（膦）酸萃取剂钠盐与非离子表面活性剂AEO9混合体系胶团的…

本文研究了烷基磷（膦）酸萃取剂钠盐ＮａＥＨＥＨＰ，ＮａＤＴＭＰＰ，Ｎａ２（ＭＥＨＰ）与非离子表面活性剂ＡＥＯ９以不同比例复配后水溶液胶团的形成及分子间的相互作用结果表明混合胶团的形成使ＣＭＣ大大降低，分子间在胶团中的相互中弱为，Ｎａ２（ＭＥＨＰ）体系〉ＮａＤＴＭＰＰ体系〉ＮａＥＨＥＨＰ体系，分子间在表面层的作用小于同体系分子间在胶团中的相互作用，这一结果有利于混合胶团的形成。     

烷基磷（膦）酸萃取剂钠盐与非离子表面活性剂AEO_9混合体系胶团的形成和分子间的相互作用

本文研究了烷基磷（膦）酸萃取剂钠盐ＮａＥＨＥＨＰ，ＮａＤＴＭＰＰ，Ｎａ_２（ＭＥＨＰ）与非离子表面活性剂ＡＥＯ_９以不同比例复配后水溶液胶团的形成及分子间的相互作用，结果表明混合胶团的形成使ＣＭＣ大大降低。分子间在胶团中的相互作用强弱为：Ｎａ_２（ＭＥＨＰ）体系＞ＮａＤＴＭＰＰ体系＞ＮａＥＨＥＨＰ体系，分子间在表面层的吸引作用小于同体系分子间在胶团中的相互作用，这一结果有利于混合胶团的形成。     

VOHPO4.0.5H2O的制备及活化和催化性能

用正戊醇和仲醇还原ＶＯＰＯ４．２Ｈ２Ｏ，以制备正丁烷氧化顺酐的Ｖ－Ｐ－Ｏ催化剂前驱物ＶＯＨＰＯ４．０．５Ｈ２Ｏ，并用ＸＲＤ，ＴＧ，ＳＥＭ对共进行了表征。结果表明，由正戊醇还原ＶＯＰＯ４．２Ｈ２Ｏ合成的前驱物ＶＯＨＰＯ４．０．５Ｈ２Ｏ的ＸＲＤ，在（２２）晶面衍射强度较强；而由仲戊醇合成的前驱物ＶＯＨＰＯ４．０．５Ｈ２Ｏ的ＸＤ，在（００１）晶面衍射强度较强。正戊醇还原ＶＯＰＯ４．２ＨＯ２合成的前驱物Ｖ     

具有抗HIV病毒活性的杂多酸HPA-23与谷胱甘肽的作用

以谷胱甘肽作为病毒包络蛋白的模拟物，用ＮＭＲ方法研究了与具有抗爱滋病病毒活性杂多酸ＨＰＡ－２３的作用。对不同配比的ＨＰＡ－２３和谷胱甘肽混合物的＾１Ｈ和＾１＾８＾３ＷＮＭＲ谱研究结果表明，还原型和氧化型谷胱甘肽均以Ｃ末端ＣＯＯ＾－与ＨＰＡ－２３骨架的钨原子配位，还原型谷胱甘肽侧链上的巯基（ＳＨ）也参加配位。ＣＯＳＹ谱证明了ＳＨ配位为慢交换反应。早在七十年代初，人们就发现杂多酸具有抗病毒活性。最近报     

RUTHENIUM COORDINATION COMPOUNDS WITH POLYPYRIDINES V．DNA－BINDING STUDIES OF Ru（Ⅱ）COORDINATION COMPOUNDS WITH（2－PHENYL－）IMIDAZO［f］1，10－PHENANTHROLINE

ＲＵＴＨＥＮＩＵＭＣＯＯＲＤＩＮＡＴＩＯＮＣＯＭＰＯＵＮＤＳＷＩＴＨＰＯＬＹＰＹＲＩＤＩＮＥＳＶ．ＤＮＡ－ＢＩＮＤＩＮＧＳＴＵＤＩＥＳＯＦＲｕ（Ⅱ）ＣＯＯＲＤＩＮＡＴＩＯＮＣＯＭＰＯＵＮＤＳＷＩＴＨ（２－ＰＨＥＮＹＬ－）ＩＭＩＤＡＺＯ［ｆ］１，１０－...     

RUTHENIUM COORDINATION COMPOUBNDS WITH POLYPYRIDINES Ⅳ SYNTHESIS AND CHARACTERIZATION OF （2－PHENYL）IMIDAZO［f］ 1， 10－PHENANTHROLINE AND THEIR Ru（Ⅱ） COORDINATION COMPOUNDS

ＲＵＴＨＥＮＩＵＭＣＯＯＲＤＩＮＡＴＩＯＮＣＯＭＰＯＵＢＮＤＳＷＩＴＨＰＯＬＹＰＹＲＩＤＩＮＥＳⅣＳＹＮＴＨＥＳＩＳＡＮＤＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦ（２－ＰＨＥＮＹＬ）ＩＭＩＤＡＺＯ［ｆ］１，１０－ＰＨＥＮＡＮＴＨＲＯＬＩＮＥＡＮＤＴＨＥＩ...     

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.     

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.     

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.     

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.