CuZSM—5分子筛上苯酚羟化制苯二酚

在Ｎａ２Ｏ－ＳｉＯ２－ＣｕＯ－Ｈ２Ｏ体系中以１５％ＴＰＡＢｒ－８５％ＨＭＤＡ为模板剂合成了ＣｕＺＳＭ－５分子筛，并用ＸＲＤ，ＩＲ及ＳＥＭ等方法进行了表征，考察了ＣｕＺＳＭ－５分子筛催化苯酚与过氧化氢的羟化活性，研究了催化剂用量，反应温度，反应时间及ｎ（ＰｂＯＨ）／ｎ（Ｈ２Ｏ２）等对羟化活性的影响。     

（四甲基二硅撑）双（3—三甲硅基环戊二烯基）—四羰基二铁…

标题化合物（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）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、ＰｈＣＨ２Ｃｌ、ＣｌＣＨ２ＣＯＯＣ２Ｈ５和Ｐｈ３ＳｎＣｌ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（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）Ｆｅ（ＣＯ）２Ｒ〕２（Ｒ：Ｍ     

导电高聚物聚2，5－二甲基苯胺的化学合成与特性

报道了聚２，５－二甲基苯胺（ＰＤＭｅＡｎ）的化学合成，并用标准四探针方法测定其电导率，以ＦＴＩＲ、ＵＶ－Ｖｉｓ吸收光谱、元素分析和ＣＶ法对其性质进行了研究，ＰＤＭｅＡｎ的结构与聚苯胺和聚２，５－二甲氧基苯胺的结构类似，是由其单元通过氮原子（Ｎ）在对位上键合而成，本征态的ＰＤＭｅＡｎ能溶于多种有机溶剂，如ＣＨ２Ｃｌ２、ＣＨＣｌ３、ＤＭＳＯ、ＤＭＦ等。     

UNUSUAL FORMATION OF ORGANO－NEODYMIUM AND －SAMARIUM CATIOHS AND X－RAY STRUCTURE OF［（MeOCH_2CH_2C_5H_4）_2Sm（thf）］［Co（CO）_4］

ＵＮＵＳＵＡＬ　ＦＯＲＭＡＴＩＯＮ　ＯＦ　ＯＲＧＡＮＯ－ＮＥＯＤＹＭＩＵＭ　ＡＮＤ　－ＳＡＭＡＲＩＵＭ　ＣＡＴＩＯＨＳ　ＡＮＤ　Ｘ－ＲＡＹ　ＳＴＲＵＣＴＵＲＥ　ＯＦ［（ＭｅＯＣＨ_２ＣＨ_２Ｃ_５Ｈ_４）_２Ｓｍ（ｔｈｆ）］［Ｃｏ（ＣＯ）_４］ＵＮＵＳＵＡ...     

二苯基锡不饱和烃基膦酸酯的合成及其结构表征

以二苯基二氯化锡和炔（烯）基膦酸盐为原料,在乙醇中反应,合成了８种新的二苯基锡不饱和烃基膦酸酯Ｐｈ２ＳｎＯ２Ｐ（Ｏ）Ｒ（Ｒ＝Ｃ－－－ＣＣ３Ｈ７－ｎ,Ｃ－－－ＣＣ４Ｈ９－ｎ,Ｃ－－－ＣＣ５Ｈ１１－ｎ,Ｃ－－－ＣＣ５Ｈ１３－ｎ,Ｃ－－－ＣＣＨ２ＯＣＨ３,Ｃ－－－ＣＣＨ２ＯＣ２Ｈ５,Ｃ－－－ＣＰｈ,ＣＨ－－－ＣＣｌＰｈ）,利用元素分析、ＩＲ,＾１ＨＮＭＲ和ＴＧ－ＤＡＴ对其组成的结构进行了表征。     

Molecular Structure of Organolanthanide Complex ［（η~5－CH_3C_5H_4）_2Tb（μ－Cl）（THF）］_2

ＭｏｌｅｃｕｌａｒＳｔｒｕｃｔｕｒｅｏｆＯｒｇａｎｏｌａｎｔｈａｎｉｄｅＣｏｍｐｌｅｘ［（η~５－ＣＨ_３Ｃ_５Ｈ_４）_２Ｔｂ（μ－Ｃｌ）（ＴＨＦ）］_２ＷＵＺｈｏｎｇ－Ｚｈｉ；ＨＵＡＮＧＺｕ－Ｅｎ；ＣＡＩＲｕｉ－Ｆａｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅ...     

（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。     

微乳液的增敏作用研究：Ni（Ⅱ）—5—Br—PADAP的分光光度法测定

以含水量８０％的阴离了了型ＳＤＳ／ｎ－Ｃ５Ｈ１１ＯＨ／ｎ－Ｃ７Ｈ１６／Ｈ２Ｏ微乳液为介质，进行了Ｎｉ（Ⅱ）－５－Ｂｒ－ＰＡＤＡＰ分光光度研究，其表观摩尔吸光系数为１．１３×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，与相应含水量的ＳＤＳ胶束介质比较，测定灵敏度显著提高，样品分析令人满意。     

金属键有机化合物的研究──非对称型η~5－取代环戊二烯基三羰基钼（钨）金属单键化合物的合成及表征

通过η５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ（Ｍ＝Ｍｏ，Ｗ）以及η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭｏＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＷＮａ在Ｆｅ＿２（ＳＯ＿４）＿３醋酸水溶液作用下的交叉氧化偶联反应，合成了７个新的非对称型金属单键化合物η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）－３Ｍｏ─Ｍｏ（ＣＯ）＿３Ｃ＿５Ｈ＿４Ｒ~２－η~５（Ｒ~１，Ｒ~２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ），η５－Ｒ１Ｃ５Ｎ４（ＣＯ）３Ｗ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ；Ｈ，ＣＯ２Ｅｔ）和η５－Ｒ１Ｃ５Ｈ４（ＣＯ）３Ｍｏ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，Ｈ；Ｅｔ，Ｃ（Ｏ）Ｍｅ；Ｃ（Ｏ）Ｍｅ，ｎ－Ｂｕ；ＣＯ２Ｍｅ，ｎ－Ｂｕ）．用Ｃ／Ｎ分析、ＩＲ、１ＨＮＭＲ和ＭＳ表征了它们的结构，并对该氧化偶联反应的特点进行了讨论．     

二（三）苄基锡不饱和烃基膦酸酯的合成

合成了１０种二（三）苄基锡不饱和烃基膦酸酯［（ＰｈＣＨ２）ｎＳｎ］ｎ－１Ｏ２Ｐ（Ｏ）Ｒ（ｎ＝２，３；Ｒ＝—Ｃ≡ＣＰｈ，—Ｃ≡ＣＣ５Ｈ１１－ｎ，—Ｃ≡ＣＣＨ２ＯＣＨ３，—Ｃ≡ＣＣＨ２ＯＣ２Ｈ５，—ＣＨ＝ＣＣｌＰｈ），利用元素分析、核磁共振氢谱和ＴＧ－ＤＴＡ对其组成和结构进行了表征．初步生物活性测试表明，有些化合物具有较强的杀螨和杀菌活性     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

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.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.