三缺位杂多化合物K_8［P_2W_（18）Mo_2Co_2（H_2O）_2O_（68）］·MoO_6·15H_2O的合成、结构及催化H_2O_2分解研究

合成了杂多化合物Ｋ８［Ｐ２Ｗ（１８）Ｍｏ２Ｃｏ２（Ｈ_２Ｏ）２Ｏ（６８）］·ＭｏＯ６·１５Ｈ２Ｏ，依据ＸＲＤ、ＩＲ、ＵＶ－Ｖｉｓ及ＸＰＳ确定了其晶体结构和配位原子价态，考察了该化合物催化Ｈ２Ｏ２分解的动力学行为。     

硅源及晶化时间对SAPO-5分子筛结构及性质的影响

分别以硅凝胶和正硅酸乙酯为硅源，通过改变晶化时间合成了系列ＳＡＰＯ５分子筛．用ＸＲＤ，ＭＡＳＮＭＲ和ＳＥＭ对分子筛的结构和形貌进行了表征．结果表明，以硅凝胶为硅源时，凝胶中的铝有３种面体配位状态．加热晶化很容易使凝胶转化为ＳＡＰＯ５分子筛，合成物的晶形更加规则．在４８ｈ内，延长晶化时间有助于硅进入分子筛骨架，使残余的Ａｌ２Ｏ３·Ｈ２Ｏ进一步反应，使骨架硅和铝的面体配位环境更加对称；超过４８ｈ后，硅开始游离出分子筛骨架，并使部分ＳＡＰＯ５转化为ＳＡＰＯ３４．以正硅酸乙酯为硅源时，硅和铝的反应活性均较低，凝胶中ＡｌＰＯ４及Ａｌ２Ｏ３·Ｈ２Ｏ的量均比四面体配位铝的量大．只有当晶化时间超过４８ｈ时，反应物中Ａｌ２Ｏ３·Ｈ２Ｏ才能完全转化．在此反应体系中，延长晶化时间有助于ＳＡＰＯ５的生成，使分子筛骨架硅的取代量更大，晶形更加规则，骨架铝的对称性更好．     

α－一铌二钼十五钨磷杂多酸盐的合成和性质研究

合成了通式为α－Ｍ＿（７－ｘ）Ｈ＿ｘ［Ｐ＿２Ｗ＿（１５）Ｍｏ＿２ＮｂＯ＿（６２）］·ｘＨ＿２Ｏ［Ｍ＝Ｋ~＋，（ＣＨ＿３）＿４Ｎ~＋，（Ｃ＿２Ｈ＿５）＿４Ｎ~＋，（Ｃ＿４Ｈ＿９）＿４Ｎ~＋］的４种盐．用ＩＲ、ＵＶ吸收光谱、极谱、~（１８３）ＷＮＭＲ、ＸＰＳ和ＸＲＤ等方法对其进行了表征，确认三取代的位置是在Ｄａｗｓｏｎ结构的同一“极位”．研究了取代Ｗ原子数目对~（１８３）ＷＮＭＲ化学位移的影响，发现“极位”Ｗ原子的~（１８３）ＷＮＭＲ化学位移平均值与取代原子数目呈线性关系．     

K_3Sb_3P_2O_（14）·5H_2O的水热合成与表征

利用水热晶化法合成了磷锑酸钾Ｋ３Ｓｂ３Ｐ２Ｏ１４·５Ｈ２Ｏ，并通过ＸＲＤ、３１ＰＭＡＳＮＭＲ、ＩＲ、ＤＴＡ－ＴＧ及组成分析等多种手段对其进行了表征。该化合物属六方晶系，晶胞参数为：ａ＝０．７１３７７ｎｍ，ｂ＝０．７１３７７ｎｍ，ｃ＝３．０８０４７ｎｍ，α＝９０°，β＝９０°，γ＝１２０°，具有层状结构，钾离子具有可交换性。     

STEREOCHEMISTRY OF CYCLIC ORGANOPHOSPHORUS COMPOUNDS－ⅡMETHANOLYSIS OF 2－CHLORO－4－PHENYL－5，5－DIMETHYL－1，3，2－DIOXAPHOSPHORINAN－2－THIONE：RETENTION OF CONFIGURATION AS WELL AS WELL AS RING OPENING ISOMERIZATION

ＳＴＥＲＥＯＣＨＥＭＩＳＴＲＹ　ＯＦ　ＣＹＣＬＩＣ　ＯＲＧＡＮＯＰＨＯＳＰＨＯＲＵＳ　ＣＯＭＰＯＵＮＤＳ－ⅡＭＥＴＨＡＮＯＬＹＳＩＳ　ＯＦ　２－ＣＨＬＯＲＯ－４－ＰＨＥＮＹＬ－５，５－ＤＩＭＥＴＨＹＬ－１，３，２－ＤＩＯＸＡＰＨＯＳＰＨＯＲＩＮＡＮ－...     

四元交互体系Li~＋，Mg~（2＋）／Cl~－，SO_4~（2－）－H_2O

本文采用等温溶解平衡法研究了四元交互体系Ｌｉ＋，Ｍｇ２＋／ＣＩ－，ＳＯ－Ｈ２Ｏ２５℃的机关系和平衡液相的物化性质（密度、粘度、电导率、折光率和ｐＨ）．该体系２５℃有七个相区Ｌｉ２ＳＯ４·Ｈ２Ｏ，ＭｇＳＯ４·７Ｈ２Ｏ．ＭｇＳＯ４·６Ｈ２Ｏ．ＭｇＳＯ４·５Ｈ２Ｏ，ＭｇＣ１２，６Ｈ２Ｏ，ＬｉＣＩ．ＭｇＣｌ２．７Ｈ２Ｏ，ＬｉＣＩ·Ｈ２Ｏ，十一条单变量线，五个共饱点．其中ＬｉＣＩ·Ｈ２Ｏ＋ＬｉＣＩ·ＭｇＣｌ２·７Ｈ２Ｏ＋Ｌｉ２ＳＯ４·Ｈ２Ｏ为一致零变量点．与文献中的研究结果比较，我们得到两个新相区ＭｇＳＯ４·６Ｈ２Ｏ和ＭｇＳＯ４·５Ｈ２Ｏ．用经验和半经验公式计算了平衡液相的密度、折光率．由实验测定的溶解度数据求得了高锂浓度下的Ｐｉｔｚｅｒ参数．对该体系２５℃溶解度进行了理论计算复证．     

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     

Bi4PMo(12)O(49)催化剂的性质及其在丙烷选择氧化中的活性

从钼磷酸出发制备了Ｂｉ４ＰＭｏ１２Ｏ４９催化剂，ＩＲ及ＸＲＤ分析结果表明，高温焙烧后其基本组成为α－Ｂｉ２Ｍｏ３Ｏ１２／ＭｏＯ３，考察了该催化剂对丙烷的选择氧化生，ＥＳＲ及ＸＰＳ测定结果表明，反应后催化剂中Ｍｏ＾５＋的含量明显增加，这暗示着反应物种吸附在Ｍｏ＾６＋上，而Ｂｉ则为气相氧的入口。     

α—一铌二钼十五钨磷杂多酸盐的合成和性质研究

合成了通式为α－Ｍ７－ｘＨｘ［Ｐ２Ｗ１５Ｍｏ２ＮｂＯ６２］．ｘＨ２Ｏ］Ｍ＝Ｋ＾＋，（ＣＨ３）４Ｎ＾＋，（Ｃ２Ｈ５）４Ｎ＾＋，（Ｃ４Ｎ９）４Ｎ＾＋］的４种盐。用ＩＲ，ＵＶ吸收光谱，极谱，１８３ＷＮＭＲ，ＸＰＳ和ＸＲＤ等方法对其进行了表征，确认三取代的位置在Ｄａｗｓｏｎ结构的同一“极位”。研究了取代Ｗ原子数目对１８３ＷＮＭＲ化学位移的影响，发现“极位”Ｗ原子的１８３ＷＮＭＲ化学位移平衡值与取代原子数目     

（四甲基二硅撑）双（3－三甲硅基环戊二烯基）－四羰基二铁的反应性

标题化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２／（μ－ＣＯ）_２（Ａ）分子中的Ｆｅ－Ｆｅ键被钠汞齐还原断裂，生成相应的双铁负离子，分别与ＭｅＣＯＣｌ、ＰｈＣＯＣｌ、ＰｈＣＨ_２Ｃｌ、ＣｌＣＨ_２ＣＯＯＣ_２Ｈ_５和Ｐｈ_３ＳｎＣｌ进行亲核取代反应，生成在铁原子上引入相应取代基的产物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２Ｒ］_２（Ｒ：ＭｅＣＯ（１），ＰｈＣＯ（２），ＰｈＣＨ_２（３），ＣＨ_２ＣＯＯＣ_２Ｈ_５（４），Ｐｈ_３Ｓｎ（５），Ｉ（６））。Ａ在氯仿中与碘反应，得到Ｆｅ－Ｆｅ断裂的双铁碘化物，但在苯中与过量碘反应，则得到Ｆｅ－Ｉ－Ｆｅ桥联的离子型化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２Ｉ·Ｉ（７）。化合物６的晶体和分子结构经Ｘ射线衍射测定，６属单斜晶系，Ｐ２１／ｃ空间群，ａ＝１．７２１７（４）ｎｍ，ｂ＝０．７７５３（２）ｎｍ，Ｃ＝１．３６２９（７）ｎｍ，β＝１０３．８０（３）°，Ｖ＝１．７６７（２）ｎｍ３，Ｚ＝４，Ｄｃ＝１．６２９９·ｃｍ－１，最终偏差因子Ｒ＝０．０５４。     

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.