THE SYNTHESIS OF 1,3,2-DIOXAPHOSPHOLENES. EVIDENCE FOR AN ARYLOXYPHOSPHINIDENE INTERMEDIATE

Abstract

The reaction of 2,6-di-t-butyl-4-methylphenylphosphorodichloridite with α-diketones in the presence of magnesium metal affords modest yields of 1,3,2-dioxaphospholenes. This may be the first evidence for the existence of the monocoordinate aryloxyphosphinidene intermediate, ROP.     

含环氧基的丙烯酸酯弹性体的合成及其对聚氯乙烯改性研究

以丙烯酸丁酯（ＢＡ），甲基丙烯酸甲酯（ＭＭＡ）和甲基丙烯酸缩水甘油酯（ＧＭＡ）为原料，通过分段乳液聚合，合成了一系列具有不同组成结构的三元共聚物—Ｐ（Ｂ—Ｍ—Ｇ）弹性体，并对此弹性体改性的ＰＶＣ的抗冲击性能进行了系统研究．结果表明：改性剂组成结构的变化对改性体系的冲击性能有较大影响，改性ＰＶＣ的冲击性能最高可达７９ｋＪ／ｍ２．动态力学及ＳＥＭ实验表明，ＰＶＣ与改性体系系部分相容的共混体系，其断裂行为是明显的韧性断裂特征．本文还对改性体系的力学性能进行了研究．     

A NEW ROUTE FOR THE SYNTHESIS OF STYRYLBENZYLSULFONES,PRECURSORS OF 1-BENZYLSULFONYL-2-ARYLCYCLOPROPANES

Abstract

A novel method for the synthesis of E-styrylbenzylsulfones from E-sodium styrysulfinates and benzyl chlorides has been described. The cyclopropanation of these compounds with dimethylsulfonium methylide gave E-1-benzylsulfonyl-2-arylcyclopropanes in good yields. The corresponding Z-isomers have been obtained by the cycloaddition of benzylthiocarbenes to styrenes under phase transfer catalysis. Their geometry has been assigned based on IR and ¹H NMR spectral data.     

一些新拟除虫菊酯化合物的合成

本文采用几种不同于速灭菊酯的醇组份合成了十七个新拟除虫菊酯化合物。分别用红外光谱、核磁共振谱、质谱及元素分析等方法确定了它们的结构,并选择了家蝇、蚜虫、粘虫、拟谷(虫甲)、红蛛蜘等昆虫作了生物活性的测定。其中,醇组份为和的新拟除虫菊酯化合物具有较好的杀虫、杀螨活性。     

介孔材料B-Al-MCM-48合成的新方法

首次在两种阳离子表面活性剂存在的弱碱反应体系中加入三乙醇胺进行分子调变从而合成了具有较高稳定性和酸性的介孔材料B－Al-MCM-48,并用XRD、IR、TEM、NMR等油试手段对其进行了表征，同时阐述了其合成化学特点。结果表明，实验产品有序度高，介孔排布均匀，孔径大约介于2．0nm-3.0nm,比表面积为1200m^2/g,孔容为1．18mL/g;孔墙中引入的硼以四配位形式存在，改善了沸石酸性和稳定性。进而以轻汽油的催化加氢为探针反应考察了载Ni后介孔材料B－Al-MCM-48的催化活性，与现行X型沸石催化剂载体相比，脱氮、脱硫和芳烃转化大幅度提高。     

APPLICATION OF THE SULFONATE ESTER GROUP AS A LINKER FOR SOLID PHASE ORGANIC SYNTHESIS

A use of sulfonate ester as a linker in synthesis of w-aminoalkanols was reporte.Diols were tethered onto polystyryl sulfonyl chloride resin,yielding sulfonate resins(2).After cleaved by diethyl amine,diisopropylamine and propylamine respectively,three w-aminoalkanlos were obtained.     

APPLICATION OF THE SULFONATE ESTER GROUP AS A LINKER FOR SOLID PHASE ORGANIC SYNTHESIS

1. INTRODUCTIONIn recent years, solid phase organic synthesis (SPOS) has been increasingly used in the synthesis of small organic molecules [1]. The rapid development of SPOS brings with it the need for expanding a variety of linkers in order to accommodate new synthesis methods[2], and especially in the case of combinatorial chemistry, to allow additional diversity elements.Recently, Rueter and coworkers reported the use of a sulfonate ester as a linker in SPOS [3,4] and the compati…     

十二氢十硼双二乙基硫醚络合物新合成法的研究

本文研究了十氢十硼酸和它的各种盐类的开笼反应,找到了合成十二氢十硼双二乙基硫醚络合物[B₁₀H₁₂·(Et₂S)₂]的两个新方法.其一,以十氢十硼酸为质子源,水为配位的Lewis碱,打开稳定的B₁₀H₁₀^2-笼状骨架,随后用二乙基硫醚处理所得的混合物;其二,以硫酸为质子源,二乙基硫醚为Lewis碱打开B₁₀H₁₀^2-的笼状骨架.与文献方法比较,缩短了反应时间,提高了硼的利用率.这些反应与裂解法制备十氢十硼酸双四乙基铵相结合,完成了一条不经过高毒性的十硼烷(14),而由稳定的简单硼氢化合物制备1,2-二碳代-闭-十二硼烷(12)的新的实用路线.     

全氟烷基碘化物的脱碘亚磺化反应和合成全氟磺酸的新方法

我们在工作中发现亚硫酸钾水溶液与1的正常反应产物是2^[1],但加二氧六环于上述反应体系后发生了一个不同的反应,得到另一个产物3,即:3是熔点286℃的无色结晶,IR:1010cm^-1;¹⁹FNMR:δ_CFCl3为82.0,133.4ppm,这两个核磁共振吸收峰均为单峰并强度相等。元素分析与氧化还原滴定也符合3的结构。这一反应条件温和,产率及选择率都高达90%。因为这种反应未见文献报道,我们建议称之为“脱碘亚磺化反应”,它具有自由基反应的性质。     

新型的DIAR黄成色剂的合成

本文合成了两个新的DIAR成色剂,它们都以黄成色剂为母体,一个抑制基团是2-巯基苯骈噻唑,另一个是甲酸苯酯基苯骈三氮唑,并通过核磁、红外和质谱对结构进行了表征.     

三甲氧基蒽醌的新合成法

阿霉素(1)是目前常用的广谱抗肿瘤药物,其全合成研究引起了广泛的注意。Kende等^[1]曾自1,4,5-三甲氧基蒽醌(2)成功地合成了它的配基阿霉酮.三甲氧基蒽醌的合成,早期系以1,4,5-三氯蒽醌与甲醇钠加压反应制成^[2],但不易获得纯三氯蒽醌.Kende等系以3-甲氧基邻苯二甲酸酐与1,4-二甲氧基苯经Friedel-Crafts反应制得.最近Baldwin和Bair^[3]以间甲氧基苯甲酰苯胺,通过邻位金属化,经七步反应制得类似的1-羟基-4,5-二甲氧基蒽醌(3).     

储氢材料新合成方法的研究——置换-扩散法合成Mg2Cu

目前,国外普遍采用高温熔炼法制备Mg2Cu,这种方法的优点是工艺比较简单,缺点是产物表面性能较差,吸、放氢速度较慢,且使用前必须经过粉碎。     

A CONVENIENT MULTIGRAM PREPARATION OF FUNCTIONALIZED 2-AZIDO-2-DEOXY-D-MANNOSE AS A USEFUL ORTHOGONALLY PROTECTED BUILDING BLOCK FOR OLIGOSACCHARIDE SYNTHESIS

Multigram preparation of strategically protected 2-azido-2-deoxy mannose 5 from pentaacetyl glucose 1 is described. This manno-derivative was obtained in a straightforward manner and in high overall yield and represents a flexible building-block for complex oligosaccharide synthesis.     

THE INVESTIGATION OF MONOMER SYNTHESIS METHODS FOR POLYSULFONES AND OTHER NEW CLASSES OF SULFUR-CONTAINING POLYMERS

Abstract

Polysulfones, the new promising class of sulfur-containing polymers, are produced by aromatic nucleophilic and electrophilic substitution reactions. The first way is based on 4,4′-dichlorodiphenylsulfone (DCDPS) application as one of the basic monomers, which can be produced by three technical methods, utilizing strong sulfonating and sulfonylating agents. The reaction of hydrocarbon sulfonylation with arylsulfochlorides in the presence of small quantities of Fe chloride (kinetics, mechanism, the reactivity of initial compounds) was investigated in detail. For the first time the competitive inhibiting by initial and final products was found in this reaction, and its quantitative evaluation was given. The data obtained allowed to explain the experimentally observed anomalous reactivity of arylsulfochlorides. The chemistry of sulfonylation reaction with stabilized liquid sulfuric anhydride and dimethylsulfate was thoroughly investigated. The peculiarities and application limits of substituted diphenylsulfones synthesis methods were discussed.     

用硅烯醚型引发剂进行的基团转移聚合

本文报道了一类硅烯醚型的基团转移聚合引发剂。并以负离子和HgI_2等为催化剂,进行了甲基丙烯酸酯和丙烯酸酯的基团转移聚合。得到了实测分子量和理论分子量相近且分散性较小的浆合物。进行了甲基丙烯酸甲酯的活性聚合以及其与丙烯酸酯的A-B-A型三嵌段共聚,证实具有活性高分子的特征。探讨了该类引发剂引发基团转移聚合的机理,研究了催化剂和引发剂的配合选择性以及催化剂和引发剂的摩尔比对产物分子量和转化率的影响,发现该类引发剂引发的基团转移聚合是一恒速聚合反应。     

一种用于合成ZSM－48沸石分子筛的新体系

一种用于合成ＺＳＭ－４８沸石分子筛的新体系李建权，刘光焕，董晋湘（太原工业大学精细化工研究所，太原０３００２４）关键词捏合法，极浓体系，ＺＳＭ－４８沸石，合成，表征长期以来，沸石合成一直是在模拟天然沸石形成的条件下进行的．通常的反应体系是一过饱和状态...     

CHLOROMETHYL-DICHLOROPHOSPHANE: A USEFUL REAGENT FOR THE SYNTHESIS OF NEW HETEROCYCLES WITH DICOORDINATE PHOSPHORUS

Abstract

Only a limited number of heterophospholes are known. A general synthesis¹ involves the [4 + 1]-cyclocondensation of a reactive phosphorus(III) compound with an appropriate four-membered chain, as in the synthesis of the 2H-1,2,3-diazaphospholes.² The limiting factor in this case is the poor availability of four-membered chains with the necessary functionality at the ends.     

笼状烃金刚烷的新合成方法

笼状烃金刚烷的新合成方法米镇涛郭建维邱立勤（天津大学化工学院天津３０００７２）关键词金刚烷，沸石，催化异构金刚烷（三环［３．３．１．１［３，７］癸烷）是一种周正对称、非常稳定的笼状烃，是由１０个碳原子和１６个氢原子构成的环状四面体碳氢化合物，基本骨...     

新试剂N-苯基-N′-(氨基对苯磺酸钠)硫脲的合成及其测定微量铂(Ⅳ)的研究和应用

介绍了新试剂N 苯基 N′ (氨基对苯磺酸钠 )硫脲 (PPT)的合成 ,研究了其与铂的显色条件 ,在pH为 3.4～ 4 .2的HOAc NaOAc缓冲体系中 ,在溴化十六烷基三甲胺 (CTMAB)存在下 ,Pt(Ⅳ )与PPT形成组成比 1∶3的绿色水溶性络合物 ,其最大吸收峰位于 778.4nm ,表观摩尔吸光系数ε778.4=2 .95× 10 4 L·mol- 1·cm- 1,铂含量在 0～ 10 0 μg/ 2 5ml范围内服从比耳定律。此法线性范围宽 ,选择性好 ,4 0余种离子不干扰测定 ,用于矿石与催化剂中铂的分析 ,结果满意     

NEW APPROACHES TO THE SYNTHESIS OF ORGANOPHOSPHORUS COMPOUNDS

Abstract

The past two decades have brought us a snowballing development of organophosphorus chemistry. Indeed organophosphorus compounds have found wide practical application (in agriculture, petroleum industry, as drugs, etc.) and continue to afford promising objects for the study of theoretical matters such as tautomerism, ambiphilicity, ambidenticity, and other problems of organic chemistry. On the other hand, however impressive this progress may be, the search for new methods of synthesis, improving the known methods and forecasting new types of organophosphorus compounds remain as challenging problems as before.