钌(Ⅱ)表面活性剂配合物的合成、表征及其液晶和发光性质

合成了一个新钌(Ⅱ)表面活性剂配合物[Ru(bpy)₂(d19-phen)]Cl₂(bpy=2,2′-联吡啶,d19-phen=4,7-二正十九烷基-1,10-邻菲咯啉),用元素分析、核磁共振谱和质谱对配合物的组成和结构进行了表征.该配合物具有优良的发光性能和较高的量子效率,其与水的混合体系展示良好的溶致液晶行为.     

A General and Efficient CuBr2‐Catalyzed N‐Arylation of Secondary Acyclic Amides

A general and efficient Cu(II)‐catalyzed cross‐coupling method is reported for the preparation of acyclic tertiary amides. Generally moderate to excellent yields and functional group tolerance were obtained with secondary acyclic amides and aryl halides as substrates in toluene.     

加碘食盐中微量碘的离子选择性电极测定

在加碘食盐中加入还原剂将KIO3中的IO3^-还原为I^-,使用碘离子选择性电极技术,采用标准曲线法直接测定了溶液中的I-量.并引入表面活性剂作为增敏剂,降低了检测下限,提高了检测的灵敏度.实际测定3种食盐样品,取得了较好的效果.     

Synthesis of α- and/or γ-benzoyloxy-α,β-enones from α-halo-α,β-enones

Sodium benzoate reacts with α-halo-α,β-enones in the presence of tetrabutylammonium hydrogensulfate or 18-Crown-6 to afford α- and/or γ-benzoyloxy-α,β-enones in good yield. The α/γ and γ/γ′ selectivities are dependent on the substrate and reagent.     

Epoxide as precatalyst for metal-free catalytic transesterification

Transesterification of methyl esters was accelerated by an in situ-generated metal-free catalyst comprising a quaternary alkylammonium salt and an epoxide. The combination of a quaternary alkylammonium acetate and glycidol is optimal, and various esters were synthesized from methyl esters with alcohols in good to excellent yield. Analysis of the catalyst solution revealed that basic species are generated by the ring-opening reaction of epoxide.     

Synthesis and Molecular Structure of New Macro Acyclic Mannich Derivatives: Symmetrical and Unsymmetrical 2-[(E)-(Benzylideneamino)(aryl)methyl]cyclododecanone

Abstract

In an effort to provide a green synthetic route for heterocyclic scaffolds, new macro analogs of acyclic Mannich derivatives have been synthesized in good yields in a one-pot, efficient fashion. The acyclic symmetrical and unsymmetrical 2-[(E)-(benzylideneamino)(aryl)methyl]cyclododecanones have been synthesized by condensation of cyclododecanone, aromatic aldehyde, and ammonium acetate in ethanolic media. By infrared, NMR, and mass spectral analyses, their structures were determined. Examination of crystal structure of a p-Cl and o-Br analogs reveals the minimum energy [3333] square conformation of cyclododecanone ring. In the crystal, molecules aggregate in dimeric subunits formed by C-Cl … π and C-H..π interactions. The reported one-pot, multichain reaction of macrocycles is the first synthetic attempt of acyclic compounds in this type of Mannich reaction involving ketones containing active methylene groups.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

The effect of selected surfactants on the structure of a bicellar system (DMPC/DHPC) studied by SAXS

The stabilizing or disturbing effect of different surfactants on the bicellar phase of phospholipids significantly depends on their type. The effect of different surfactants on the bicellar structure made of a mixture of phospholipids 1,2-dimyristoyl-sn-glycero-3-phosphocholine and 1,2-dihexanoyl-sn-glycero-3-phospho-choline (DMPC/DHPC) has been studied by the small angle scattering of synchrotron radiation. The study has been performed for three surfactants: dodecyldimethyl-(hexyloxymethyl)ammonium chloride, n-undecylammonium chloride and t-octylphenoxypolyethoxyethanol (Triton X-100) introduced into a bicellar solution of DMPC/DHPC (2.8:1). The bicellar phase has been disturbed in the shortest time in the presence of dodecyldimethyl-(hexyloxymethyl)ammonium chloride in this system a transition from the bicellar to lamellar structure has been directly visible. The changes have been less pronounced in the presence of undecylammonium chloride and practically not noted in the presence of Triton X-100.     

镍—亚硝基红盐—氯化癸基吡啶体系的络合物吸附波研究及应用

在0.020mol/硼砂-0.0030％亚硝基红盐-0.0040％氯化癸基吡啶体系中,镍有一灵敏的络合物吸附波,峰电位-0.55V(υs. Ag/AgCl),线性范围0.2～1600ng/ml,可用于水样和发样的测定。镍与亚硝基红盐形成1:3的二元络合物。络合物在滴汞电极上的吸附,低浓度符合Langmuir吸附等温线,高浓度符合Frumkin吸附等温线。     

碳酸氢铵制纯碱的研究

本文对“中间盐”复分解制碱法进行了研究。“中间盐”的加入不能使两个三盐共饱和点在干盐图上发生明显的移动,但能使三盐介稳平衡点的介稳期延长,从而使得用碳酸氢铵和食盐通过复分解制碱成为可能。     

Remarkable enhancement effect of potassium tert-butoxide/THF solution in base-induced Sommelet-Hauser rearrangements

A solution of potassium tert-butoxide in THF was shown to remarkably enhance the base-induced Sommelet-Hauser rearrangement of N-benzylic amino acid-derived ammonium ylides.     

Enantioselective Synthesis of Acyclic Orthogonally Functionalized Compounds Bearing a Quaternary Stereocenter Using Chiral Ammonium Salt Catalysis

We herein report an asymmetric protocol to access a series of orthogonally functionalized acyclic chiral target molecules containing a quaternary stereogenic center by carrying out the enantioselective α-alkylation of novel orthogonally functionalized dioxolane-containing cyanoacetates under chiral ammonium salt catalysis. By using just 1 mol % of Maruoka's spirocyclic ammonium salt catalysts enantioselectivities up to e.r.=97.5 : 2.5 could be achieved and further functional group manipulations of the products were carried out as well.     

Oxoammonium salt-mediated oxidative nitriles synthesis from aldehydes with ammonium acetate

An efficient and scalable route for the synthesis of nitriles was developed by oxoammonium salt (4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) mediated oxidative conversion of aldehydes with NH₄OAc. A variety of aliphatic aldehydes as well as benzaldehydes were converted into the corresponding nitriles in high yields. The nitroxyl radical which is the reduced species of the used oxoammonium salt was recovered by simple acid-base extraction for the recycling.     

One-pot synthesis of α-diazo-β-hydroxyesters under phase-transfer catalysis and application to the catalytic asymmetric aldol reaction

The one-pot (three steps) synthesis of α-diazo-β-hydroxyesters from tosyl chloride under phase-transfer catalysis is described. The catalytic asymmetric aldol reaction between a diazoester and aldehydes was also investigated and gave moderate to good enantioselectivity.     

Dimerization of Acetylenic Amides

Summary.  Dimers of substituted acetylenic amides were obtained when triethylamine was used as refluxing solvent and acid acceptor instead of pyridine in the reaction of substituted acetylenic amides with triphosgene. Unsubstituted acetylenic amides resulted in the corresponding quinazolinone. Received October 22, 2001. Accepted (revised) November 22, 2001     

Stereocontrolled Synthesis of Adjacent Acyclic Quaternary‐Tertiary Motifs: Application to a Concise Total Synthesis of (−)‐Filiformin

Lithiation/borylation methodology has been developed for the synthesis of acyclic quaternary‐tertiary motifs with full control of relative and absolute stereochemistry, thus leading to all four possible isomers of a stereodiad. A novel intramolecular Zweifel‐type olefination enabled acyclic stereocontrol to be transformed into cyclic stereocontrol. These key steps have been applied to the shortest enantioselective synthesis of (?)‐filiformin to date (9 steps) with full stereocontrol.     

The effect of shear on ordered block copolymer solutions

Block copolymers are extensively used in solution, especially aqueous solution, because of their amphiphilic character. This leads to the formation of lyotropic mesophases under given conditions of concentration and temperature. In many applications, block copolymer solutions are subjected to shear during processing (for example in drug delivery or when washing in detergent solutions) and thus it is of considerable interest to understand how shear affects the mesophase structure. Recent research has focussed on probing shear-induced structural transformations in lamellar, hexagonal and cubic-packed micellar phases using small-angle X-ray and neutron scattering.     

Na2CrO4-(NH4)2CrO4-H2O体系的相图

铬盐工业是无机盐工业的一个主要分支,其主要产品有重铬酸钠、铬酸酐、铬酸铵、氧化铬等,广泛用于合金材料、电镀、制革、印染、橡胶等部门,是国民经济中重要的基础化工原料工业．铬盐生产系先将铬铁矿制成铬酸钠及重铬酸钠,然后再进一步加工制成其它铬盐产品．在铬盐...