含多个(R)-1,1''''-联萘手性高分子合成与结构表征

单体（R）．3，3＇-二碘-2，2＇-二正丁氧基-1，1＇-联萘（（R）-M-1），（R）-6，6＇-二溴-2，2＇-二正丁氧基-1，1’-联萘（（R）-M-2）分别与1，4-二乙烯基-2，3-二丁氧基萘（M-3），在钯催化下，通过Heck交叉耦合反应合成手性高分子P-1与P-2．单体和高分子进行了^1H—NMR、^13C-NMR、FT-IR、旋光度、GPC、UV、热分析、荧光光谱和CD等测试分析．高分子侧链上引入丁氧基后使得手性高分子溶解性增强并具有良好的成膜性，手性高分子P-1和P-2都能发射较强的蓝绿色荧光，荧光量子效率分别为0．42和0．48．     

含多个(R)-1,1′-联萘手性高分子合成与结构表征

单体(R)-3,3′-二碘-2,2′-二正丁氧基-1,1′-联萘((R)-M-1),(R)-6,6′-二溴-2,2′-二正丁氧基-1,1′-联萘((R)-M-2)分别与1,4-二乙烯基-2,3-二丁氧基萘(M-3),在钯催化下,通过Heck交叉耦合反应合成手性高分子P-1与P-2.单体和高分子进行了1H-NMR1、3C-NMR、FT-IR、旋光度、GPC、UV、热分析、荧光光谱和CD等测试分析.高分子侧链上引入丁氧基后使得手性高分子溶解性增强并具有良好的成膜性,手性高分子P-1和P-2都能发射较强的蓝绿色荧光,荧光量子效率分别为0.42和0.48.     

Asymmetric oxidation of sulfides catalyzed by (R)-6,6'-dibromo-BINOL derived titanium complex

Abstract

An efficient asymmetric oxidation of sulfides was achieved using (R)-6,6'-dibromo-BINOL as chiral ligand in combination with Ti(OⁱPr)₄ using 70% aqueous tertiary butyl hydroperoxide as oxidant. The resulting sulfoxides had high enantiopurities and good yields. A range of aryl alkyl and aryl benzyl sulfides were oxidized to the corresponding sulfoxides with 78–95% ee in 72–80% yields.     

（2R,3S）—2甲基—3—羟基戊酸甲酯的手性合成

１引言烟草甲ＬａｊｓｔｏｄｅｒｍａｓｅｒｒｉｃｏｒｎｅＦａｂｒ。ｉｎｓ是一种主要危害烟草、香烟、干燥植物以及谷物、面粉的农业害虫。这种害虫在我国主要分布在淮河以南地区以及世界各地的温暖地带［‘］。（２,３Ｓ）－２一甲基一３一羟基成酸甲酯是我们设计的合成烟草甲性信息素的一个重要中间体。我们以丙快醇为基本原料合成了该化合物。丙炔醇参照文献ｌ’］方法制得２一戊炔一ｌ一醇２,催化还原条件下,炔键可被部分加氢得到（Ｑ－２一戊烯一卜醇３。在四异丙氧基钛、Ｄ－（）一酒石酸＄［Ｊ４Ａ分于筛催化条件下,顺式烯丙醇…     

SYNTHESIS OF POLYBINAPHTHYLS INCORPORATING CHIRAL(R)-1,1''''-BI-2,2''''-NAPHTHOL ENTITIES WITH p-DIVINYLBENZENE BY Pd-CATALYZED HECK REACTION

INTRODUCTION(R) or (S) 2,2'-binaphthnol (BINOL) have often been used as the starting materials for obtaining chiral binaphthylcompounds. The 2,2'-hydroxyl groups of BINOL can be easily converted into other functional groups and the3,3'-and 6,6'-positions of naphthyl skeletal structure of BINOL can be selectively functionalized, leading to avariety of binaphthyl derivatives which can exhibit remarkably stable chiral configuration as well as high chiralinduction in many asymmetric proc…     

A NEW OPTICALLY ACTIVE POLYURETHANE DERIVED FROM CHIRAL(2R, 3R)(+)-DIETHYL L-TARTRATE AND DIISOCYANATE*

Optically active polyurethane was synthesized by the polyaddition of (2R, 3R)-(+)-diethyl L-tartrate (DET), 4,4'-diphenylmethane diisocyanate (MDI) and polyethylene glycol (PEG) with variousmolecular weights at 60℃in DMSO. The polymers were characterized by specific rotation, DSC and ~1HNMR spectra.     

（R）—N—乙酰四氢噻唑—2—硫酮—4—羧酸与醇的反应

（Ｒ）－Ｎ－乙酰四氢噻唑－２－硫酮－４－羧酸与醇反应，在ＳＯＣｌ２存在下得到乙酸酯及四氢噻唑－２－硫酮－４－羧酸酯；在碳酸钾存在下得到乙酸酯及四氢噻唑－２－硫酮－４－羧酸；在二环己基碳二亚胺（ＤＣＣ）存在下得到缩水产物Ｎ－乙酰四氢噻唑－２－硫酮－４－羧酸酯。     

Synthesis and Crystal Structure of 5（R）-（1R,2S,5R）-Menthoxy-4（R）- N-cyclohexylaminobutyrolactone

1INTRODUCTION Substitutedγ-butyrolactones are a group of impor-tant compounds containing unique carbon skeleton of butyrolactone which is widely present in many natural products and have received considerable interest because of their biological and medicinal properties[1～4].Therefore,much attention has been paid to the new asymmetric methods for synthesi-zing these interesting compounds[5～11].The prece-ding results led us to explore the possibility of using cyclohexylamine to convert5(…     

(R)-N-酰基四氢噻唑-2-硫酮-4-羧酸在DCC存在下与胺的反应

由Ｎ－乙酰四氢噻唑－２－硫酮－４－羧酸（［α］２０Ｄ－１０９．８３°），及Ｎ－苯甲酰四氢噻唑－２－硫酮－４－羧酸（［α］２０Ｄ－１１２．２２°），在Ｎ，Ｎ′－二环己基二亚胺（ＤＣＣ）存在下分别与环己胺、苯胺反应得到光学活性产物（Ｒ）－Ｎ－乙酰四氢噻唑－２－硫酮－４－甲酰环己胺（［α］１７Ｄ－７４．５°），及（Ｒ）－Ｎ－苯甲酰四氢噻唑－２－硫酮－４－甲酰苯胺（［α］１９Ｄ－７．０４°）。用量子化学ＰＭ３方法研究了反应物和产物的电子结构。     

(R)-2-硫代四氢噻唑-4-羧酸及其酯的合成

L-半胱氨酸盐酸盐与二硫化碳, 氢氧化钠在硝酸铅存在下进行成环反应得到(R)-四氢噻唑-2-硫酮-4-羧酸产率76% , 后者与 醇在硫酸铁水合物催化下反应得到(R)-四氢噻唑-2-硫酮-4-羧酸酯, 产率40～82% .     

Study on Bicoordination Chiral Inducement Catalysis of （R）-4-Thiazolidinecarboxylic Acid

The bicoordination chiral inducement catalysis of (R)-4-thiazolidinecarboxylic acid in the enantioselective borane reduction of prochiral ketones has been studied. The fact that the absolute configuration of the main product can be changed by simply using different operation methods was firstly verified. And the reason of bicoordination chiral inducement was discussed.     

Spektralphotometrische Bestimmung von Eisen(III) und Chrom(VI) mit Helasolviolett 4R

Ohne Zusammenfassung

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Spectrophotometric determination of iron(III) and chromium(VI) by means of helasol violet 4R

     

IMMOBILIZATION OF Saccharomyces Cerevisiae USING POLY(ACRYLAMIDE)GEL FOR ASYMMETRIC SYNTHESIS OF R(-)-MANDELIC ACID

1. INTRODUCTIONPoly(acrylamide) hydrogel (PAAm gel), which is able to swell, but cannot be dissolved in the aqueous environment, is a three-dimension network with repeating hydrophilic units -CONH2. Since PAAm gel has a good biocompatibility as well as a high mechanical strength, and can be easily separated from reaction medium, PAAm gel has often been employed to immobilize enzymes and cells so as to catalyze various of chemical and biochemical reactions [1,2]. So far, biosynthesis …     

SYNTHESIS AND STRUCTURE OF Pd(II) COMPLEXES OF 1,2,3-TRIPHENYLGUANIDINE

Abstract

The formation of two complexes by reaction of [PdCl₄]^2- with 1,2,3-triphenylguanidine (PhNH)₂C=NPh under different metal/ligand ratios has been observed and the structure of the complex [(1,2,3-triphenylguanidine)₂PdCl₂] has been determined by X-ray diffraction methods. The ligands are coordinated as neutral monodentate molecules to the metal centre through their imine nitrogen atoms. The second Pd(II) complex is [Pd(1,2,3-triphenylguanidine)₄]²⁺ and was isolated by precipitation with ClO^? ₄.     

Synthesis and Crystal Structure of （R）-4-Hydroxymethyl-2-thioxo Thiazolidine and Its Asymmetric Catalysis

(R)-4-Hydroxymethyl-2-thioxo thiazolidine as a new chiral catalyst in the asymmetric addition of diethyl-zinc to benzaldehyde was synthesized from (R)-4-hydroxymethyl-2-thioxo thiazolidine carboxylic acid and its crystal structure was determined by X-ray diffraction method. The compound was crystallized in the orthorhombic system, space group P212121 with unit cell dimensions a=0.67253(12) nm; b=0.89164(17) rim; c=1.06146(19) nm, volume 0.6365(2) nm3; Z=4, calculated denisity 1.557 Mg/m3; absorption coefficient 0.733 mm-1; F(000)=312. The X-ray crystal structure analysis reveals that the compound has a thione group.     

Mn(OH)_2空气氧化反应实验与产物表征

锰属于ⅦＢ族元素 ,其价电子构型为 3ｄ54ｓ2 ,具有ｄ区元素多种氧化态的特征 ,它的氧化态表现有 + 2、+ 3、+ 4、+ 6、+ 7,锰系化合物的化学性质也是多种多样的。关于Ｍｎ(Ⅱ )的还原性已多见报道[1～ 3 ] ,在酸性介质中Ｍｎ2 + 比较稳定 ,需要强氧化剂才能将其氧化 ,而在碱性介质中Ｍｎ2 + 沉淀为Ｍｎ(ＯＨ)2 ,易被氧化 ,即使与空气接触也能被氧化成棕色的ＭｎＯ(ＯＨ)2 。2Ｍｎ(ＯＨ) 2 +Ｏ2 =2ＭｎＯ(ＯＨ) 2 ( 1 )作出上述结论的依据是Ｍｎ的标准电极电势图[3 ] :由标准电极电势图可见 ,在碱性条件下Ｏ2 有将Ｍｎ(ＯＨ) 2 氧化成ＭｎＯ…     

（R）—四氢噻唑—2—硫酮—4—羧酸的合成及其晶体结构

由Ｌ－半胱氨酸盐酸盐与二硫化碳在ＮａＯＨ及ＣｕＳＯ４．Ｈ２Ｏ存在下反应得到（Ｒ）－四氢噻唑－２－硫酮－４－羧酸，「α」＾２０Ｄ－８７．５°，产率６６％。用Ｘ射线衍射法测得其晶体结构，属正交晶系，Ｐｚ１ｚ１ｚ１空间群，晶体学参数：α＝０．５０２９（２）ｎｍ，ｂ＝０．７７４９９（５）ｎｍ，ｃ＝１．６３００（５）ｎｍ，Ｖ＝０．６３５０（５）ｎｍ＾３，Ｚ＝４。用分子轨道方法研究了该化合物的电子结构，得到其     

REACTION OF (2-BENZOTHIAZOLYL)-SULFENAMIDES WITH P-CONTAINING REAGENTS

Abstract

The title reaction was investigated to find that only substitution reaction on amino group occurred when (2-benzothiazolyl)sulfenamides 1 reacted with P(NR₂,)₃, whereas the treatment of 1 with (RO)P(NR₂,)₂, gave derivatives of phosphorodiarnidothioic acid together with 2-alkylthiobenzothiazole and its isomer in addition to substitution products, and no substitution products obtained when N-substituted analogues of 1 were treated similarly.     

CRYSTAL STRUCTURE,SPECTRAL AND MAGNETIC BEHAVIOR OF COPPER(II)(5-CHLOROSALICYLATO)2 (AQUA)2

Abstract

The synthesis and characterization of Cu(5-Clsal)₂(H₂O)₂ (5-Clsal = 5-chlorosalicylate) are reported. Characterization of the compound was based on elemental analysis, electronic and EPR spectra, and magnetic susceptibility measurement over a temperature range 93–239 K.

An X-ray analysis of Cu(5-Clsal)₂(H₂O)₂ was carried out, showing a polymeric chain of copper(II) atoms bridged by pairs of water molecules with Cu-O(bridge) bond lengths of 1.970(2) and 2.718(2)Å. The coordination sphere about each copper(II) atom is completed (on the X-axis) by a trans-pair of unidentate 5-chlorosalicylate anions. The bridging oxygen atoms arrange a planar Cu₂O₂ rhombus. The relationship between degree of distortion and g-values from EPR spectra is also discussed.