Distinct chemoselectivity in the reaction of N-(thio)phosphoryl imines with diethylzinc

This report describes the reaction of N-(thio)phosphoryl imines with diethylzinc under different conditions. An interesting and distinct chemoselectivity between hydrogen-addition and ethyl-addition to imine double bond is disclosed: in weakly polar solvent, e.g. toluene, N-(thio)phosphoryl imines were exclusively reduced in excellent yields via a β-H transfer from diethylzinc to imine double bond; in polar solvents like THF, the reduction product was competitively formed as a major product together with the minor product resulting from ethyl-addition to imine double bond; in sharp contrast, in the presence of strong coordinative additive N,N,N′,N′-tetramethylethylenediamine (TMEDA), the ethylation product was formed exclusively from the reaction of N-(thio)phosphoryl imine with diethylzinc. These results are discussed and explained in terms of the coordination interactions between the imine, solvent, and additive with diethylzinc.     

胺基化树脂负载Pd(0)对Heck反应催化性能的研究

将氯球用胺化剂、乙二胺、胍进行胺化后负载氯化钯, 在乙醇溶液中用硼氢化钾还原, 制备了含胺功能基树脂负载钯(0)的催化剂; 研究了催化剂对含各种取代基碘代苯与丙烯酸的Heck芳基化反应催化性能. 结果表明, 该类催化剂具有良好的催化活性和重复使用性能, 其中用乙二胺功能化树脂负载的Pd(0)催化剂在90 ℃重复使用17次时能保持良好的催化活性. 催化剂反应前后的SEM形貌图和过滤液的活性试验表明催化剂活性组分Pd(0)在反应中有沥取(leaching)现象.     

固相力化学改性高聚物的方法研究

在固相应力作用下高聚物分子结构可被削弱或破坏,化学键可能发生畸变或断裂。固相力化学改性高聚物是研究各种高聚物因机械力影响而发生化学或物理化学变化的方法。由于该方法具有适用性广、产品纯净、操作方便、效率高、简便、节能、无污染等优点而成为高聚物改性的重要方法之一。本文系统综述了高聚物的固相剪切粉碎、固相磨盘型碾磨粉碎、高能...     

Synthesis of tetrahydrobenzoxazepine acetals with electron-withdrawing groups on the nitrogen atom. Novel scaffolds endowed with anticancer activity against breast cancer cells

Synthetic approaches that have led to (RS)-3-methoxy-N-substituded-1,2,3,5-tetrahydro-4,1-benzoxazepines with different electron-withdrawing groups, and (RS)-2-methoxy-N-trifluoroacetyl-2,3,4,5-tetrahydro-1,4-benzoxazepine are described. These novel synthons that were designed to be used as scaffolds for the preparation of new O,N-acetals as anticancer agents, unexpectedly proved to show antiproliferative activity against the MCF-7 breast cancer cell line. It has been found that substituents on the nitrogen atom have an influence on biological activity. In particular, the presence of a trifluoroacetyl moiety on the nitrogen atom leads to amides displaying interesting in vitro antitumour activities.     

Iron(III) tosylate-catalyzed deprotection of aromatic acetals in water

The deprotection of aromatic as well as conjugated acetals and ketals in water is catalyzed by iron(III) tosylate (1.0-5.0 mol %). Iron(III) tosylate is an inexpensive and readily available catalyst. The use of water, the most environmentally benign solvent, makes this procedure especially attractive for acetal deprotection.     

环氧树脂增韧改性的研究进展

概述了近年来互穿聚合物网络（IPN）、刚性粒子增韧环氧树脂的研究现状,并展望了环氧树脂增韧改性研究的前景。     

Selective cleavage of acetals with ZnBr2 in dichloromethane

A selective cleavage of acetals of 1,2- and 1,3-diols has been achieved under mild conditions using ZnBr₂ in dichloromethane at room temperature. Acetal types cleavable by this procedure include benzylidene, isopropylidene and cyclohexylidene acetals. This method is compatible with several other types of hydroxyl protecting groups such as Bn, Bz, TBDPS, TIPS and TBDMS.     

磷钨酸镧催化合成缩醛(酮)的研究

以磷钨酸镧为催化剂催化合成了苯甲醛乙二醇缩醛、苯甲醛1,2-丙二醇缩醛及环己酮乙二醇缩酮.较系统研究了反应物料配比、催化剂用量、反应时间、催化剂重复使用性能等因素对反应的影响.结果表明:在醛(酮)/二元醇(乙二醇、1,2-丙二醇)=1.0:1.5(mol/mol),催化剂用量为反应物料总质量的1.0%,环己烷为带水剂,在反应温度86～96℃条件下,反应时间2.0h,苯甲醛乙二醇缩醛收率为78.5%,苯甲醛1,2-丙二醇缩醛收率为76.1%,环己酮乙二醇缩酮收率为79.5%.     

高分子负载贵金属类催化剂及其在有机反应中的最新应用

高分子负载金属催化剂与传统的均相催化剂相比,具有较高的催化活性、立体选择性、较好的稳定性和重复使用性能,并且后处理简单,在反应完成后可方便地借助固-液分离方法将高分子催化剂与反应体系中其他组分分离、再生和重复使用,可降低成本和减少环境污染。本文综述了近五年来高分子负载贵金属类催化剂在有机反应中的最新应用,根据金属不同将其分为钌、钯、银、金四大类,并分类介绍了其在不同固相反应中的应用。本文介绍的负载贵金属类催化剂中的负载物均为不溶性聚合物,但不包括二氧化硅、可溶性聚合物和树枝状大分子等。     

Oxetane synthesis via cyclisation of aryl sulfonate esters on polystyrene and PEG polymeric supports

The addition of suitably protected pentaerythritols to polymer supported sulfonyl chloride with subsequent alkoxide formation and intramolecular cyclisation to generate oxetanes is described. This convenient method for the preparation of oxetanes has several advantages over analogous solution phase reactions and the methodology is extended to the preparation and use of a novel PEG-sulfonyl chloride.     

Acidic ionic liquid-catalyzed homologation of the polyene chain in α,β-enals (polyenals)

An efficient green-chemistry synthesis of conjugated polyenals from α,β-enals, orthoesters, and alkyl vinyl ethers promoted by acidic ionic liquid [emim][HSO₄] is described. The ionic liquid can be reused at least three times without any decrease in product yields.     

La4(Si5.2Ge2.8O18)(TeO3)4 and La2(Si6O13)(TeO3)2: Intergrowth of the lanthanum(III) tellurite layer with the XO4 (X=Si/Ge) tetrahedral layer

Two novel lanthanum(III) silicate tellurites, namely, La₄(Si_5.2Ge_2.8O₁₈)(TeO₃)₄ and La₂(Si₆O₁₃)(TeO₃)₂, have been synthesized by the solid state reactions and their structures determined by single crystal X-ray diffraction. The structure of La₄(Si_5.2Ge_2.8O₁₈)(TeO₃)₄ features a three-dimensional (3D) network composed of the [(Ge_2.82Si_5.18)O₁₈]⁴⁻ tetrahedral layers and the [La₄(TeO₃)₄]⁴⁺ layers that alternate along the b-axis. The germanate-silicate layer consists of corner-sharing XO₄ (X=Si/Ge) tetrahedra, forming four- and six-member rings. The structure of La₂(Si₆O₁₃)(TeO₃)₂ is a 3D network composed of the [Si₆O₁₃]²⁻ double layers and the [La₂(TeO₃)₂]²⁺ layers that alternate along the a-axis. The [Si₆O₁₃]²⁻ double layer is built by corner-sharing silicate tetrahedra, forming four-, five- and eight-member rings. The TeO₃²⁻ anions in both compounds are only involved in the coordination with La³⁺ ions to form a lanthanum(III) tellurite layer. La₄(Si_5.2Ge_2.8O₁₈)(TeO₃)₄ is a wide band-gap semiconductor.     

单糖和硼酸形成络合物的讨论

本文用平均络合平衡常数的测定及~(13)C NMR两种方法对一些单糖、糖苷和硼酸生成的络合物进行了研究。研究结果表明醛戊糖、醛己糖虽在溶液中主要以吡喃环存在,但当它们与硼酸络合时即由吡喃转变成呋喃。     

A Facile and Efficient Solid Supported,One‐Pot Synthesis of Functionalized Piperidine Derivatives Catalyzed by Amberlite IRA400‐Cl Resin/I2/KI via Multicomponent Reaction

A facile and efficient one‐pot, solid supported synthesis of functionalized piperidine derivatives catalyzed by Amberlite IRA400‐Cl resin/I₂/KI via a multicomponent reaction of various aldehydes, aromatic amines, and 1,3‐dicarbonyl compounds has been achieved. The reaction has been carried out in a one‐pot reaction and Amberlite resin as a solid supported catalyst at room temperature. Shorter reaction time, easy workup, yield, and mild reaction condition make the novel synthetic strategy both practical and attractive.     

Preparation of 4‐butylaniline‐bonded silica gel for the solid‐phase extraction of flavone glycosides

To extract flavone glycosides efficiently, a new extraction material based on 4‐butylaniline‐bonded silica gel was prepared using a two‐step grafting method including a ring‐opening reaction and synchronous hydrolysis. Preparation of the silica‐based material was easily achieved under mild conditions, and the material was characterized by Fourier transform infrared spectroscopy, elemental analysis, and scanning electron microscopy. The material was used in solid‐phase extraction, and the extraction can be performed in neutral conditions without regard to ionic strength. Selectivity tests of 14 compounds on the extraction cartridge showed that the material has a high affinity to flavone glycosides in contrast to octadecyl silica, and the extraction yields for four flavone glycosides were found to be >93%. Selectivity tests further reveal that the adsorption on its surface is likely attributed to multiple interactions, including hydrophobic interactions, π–π interactions, and hydrogen bonding. To explore the applicability of 4‐butylaniline‐bonded silica gel, naringin and hesperidin from Simotang oral liquid were extracted, and the extraction yields were >90%, which is distinguished from <28% on octadecyl silica cartridge.     

Mild and Efficient Chemoselective Synthesis of Acetals and Geminal Diacetates (Acylals) from Aldehydes using Lanthanum(III) Nitrate Hexahydrate

A mild and efficient chemoselective method has been developed for the preparation of acetals and gem‐diacetates in good to excellent yields through a reaction of aldehydes with ethlyleneglycol or acetic anhydride using catalytic amounts of lanthanum(III) nitrate hexahydrate as a catalyst under solvent‐free conditions.     

载溴树脂溴化酚类的研究

用简便方法制备得载溴树脂并用于酚类的溴化,当采用不同摩尔比的载溴树脂时,有选择地得到一溴、二溴及三溴代物,并有较高的产率,同时该树脂具有良好的稳定性。     

SnCl2/nano SiO2：A green and reusable heterogeneous catalyst for the synthesis of polyfunctionalized 4H-pyrans

A highly efficient and general method for the synthesis of polyfunctionalized 4H-pyrans is established through a one-pot multicomponent cyclocondensation of aromatic aldehydes with CH acids, malononitrile and ethyl acetoacetate using nano silica supported tin (Ⅱ) chloride as a catalyst. In this method SnCl2/nano SiO2 was used as green and reusable catalyst. Excellent yields, short reaction times, simple workup, and inexpensiveness and commercially availability of the catalyst are the advantages of this method.     

Pyrone derivatives and metals: From natural products to metal-based drugs

Pyrone scaffolds are often present in natural products and many derivatives therefore exhibit favorable biocompatibility and toxicity profiles. Hydroxypyrones are obtained from natural sources or can be synthesized by different well established approaches and may easily be converted into the analogous thiopyrones and hydroxypyridones. These features make them well suited to drug development and other biological applications. Herein, we summarize recent literature on the use of (thio)pyr(id)ones in bioinorganic chemistry with a focus on their metal ion chelating properties. Selected examples and different approaches using (thio)pyr(id)ones are presented and the influence of structural modifications on their chemical, physical and biological properties are discussed.