聚苯乙烯磺酰氯树脂的制备及其在含氮碱性树脂合成中的应用

本文报道一种制备聚苯乙烯磺酰氯的新方法。首先将商品磺酸阳离子交换树脂在乙醇中用吡啶处理转化为磺酸吡啶盐树脂,然后与亚硫酰氯回流得到具有单一磺酰氯基团的树脂.这种树脂分别与乙烯多胺、α-氨基吡啶、1,2,4-三氮唑和2-氨基噻唑反应制得了一系列含氯碱性树脂。     

2—聚苯乙烯磺酰基乙醇树脂的合成及其在海因和脲固相合成中的应用

合成了一种新型的聚合物载体－－2－聚苯乙烯磺酰基乙醇，并研究其在固相有机合成中的应用。聚苯乙烯亚磺酸钠树脂（1）在相转移催化剂Bu4NI和助催化剂KI的作用下，与氯乙醇进行砜化反应，得到含羟基功能基的2－聚苯乙烯磺酰基乙醇树脂2。树脂2用Boc保护的氨基酸酯化，封闭树脂上未反应的羟基，用酸脱保护并用三乙胺中和，再与异（硫）氰酸苯酯反应生成聚合物支载的脲树脂6。树脂6用酸解脱得到了海因和硫代海因化合物。用碱处理树脂6时得到取代的脲和硫脲。优化了合成反应的全过程，探讨了树脂在酸性条件下的解脱方法。结果表明，2－聚苯乙烯磺酸基乙醇树脂易与羧工形成含酯键的连接桥，连接桥在强酸性和碱性条件下均可解脱得到产物。     

聚苯乙烯基N-甲基-N-酰基磺酰胺树脂的制备及其作为酰基转移试剂在酰胺合成中的应用

聚苯乙烯基磺酰氯树脂(树脂1)与甲胺水溶液在吡啶的催化作用下反应，制备了N—甲基磺酰胺树脂(树脂2)．用酰氯在吡啶中与树脂2反应，得到N—酰基—N—甲基磺酰胺树脂(树脂3)．树脂3作为胺底物的酰基转移试剂，用来制备N—取代的酰胺，收率14～81％．树脂3可以有选择性地酰化乙醇胺中的氨基而不会使羟基酰化。     

2-聚苯乙烯磺酰基乙醇树脂的合成及其在海因和脲固相成中的应用

合成了一种新型的聚合物载体—2-聚苯乙烯磺酰基乙醇，并研究其在固相有机合成中应用，聚苯乙烯亚磺酸钠树脂（1）在相转移催化剂BU4NI和助催化KI的作用下，与氯乙进行砜化反应，得到含羟基功能基的2-聚苯乙烯磺酰基乙醇树脂2。树脂2用Boc保护的氨基酯化，封闭树脂上未反应的羟基，用酸脱保护并用三乙胺中和，再与异（硫）氰酸苯酯反应生成聚合生物支载的脲树脂6树脂6用酸解脱得到海因和硫代海因化合物，用碱处理树脂6是得到取代的脲和硫脲，优化了合成反应的全过程，探讨了树脂在酸性和碱性条件下的解脱方法，结果表明，2-聚苯乙烯磺酰基乙醇树脂易与羧基形成含酯键的连接桥，连接桥在强酸性和碱性条件下均可解脱得到产物。     

聚苯乙烯—吡啶树脂的合成及催化水解反应

在氢氧化钠作用下，氯甲基化聚苯乙烯与吡啶反应制成聚苯乙烯－吡啶树脂，测定了其化学组成和红外光谱，并考察了在酯水解反应中的催化活性。     

聚苯乙烯基N,O-二酰基磺酰羟胺树脂: 一种双酰基转移试剂在合成酰胺库中的应用

用聚苯乙烯基磺酰羟胺树脂1与酰氯2反应合成了聚苯乙烯基N,O-二酰基磺酰羟胺树脂3. 树脂3作为一种新的双酰基转移试剂可与胺4发生酰基转移反应, 合成了含有24个结构类似的酰胺化合物库. 改变酰氯的种类, 结果发现双对硝基苯甲酰树脂3a的活性较高. 双酰基树脂3胺解结果表明, 由脂肪族胺得到的酰胺收率较芳香族胺高. 当解脱试剂同时含有羟基和氨基时, 双酰基树脂3能选择性地在氨基端发生酰基转移, 而羟基端不受影响.     

3—聚苯乙烯磺酰基环氧丙烷作为活性中间体制备聚合物试剂

本文讨论了聚苯乙烯亚磺酸钠树脂（１）在相转移催化剂存在下与环氧氯丙烷反应制备含环氧功能基的树脂（２），后者进一步与含氨基的化合物在碱性条件下通过亲核反应制备了数种含胺功能基的树脂（３）。     

N-烷基-N-酰基磺酰胺聚苯乙烯基微球作为固相酰化剂的研究

一种可循环使用的固相试剂：N-烷基-N-酰基磺酰胺聚苯乙烯基微球(5), 通过对聚苯乙烯磺酰氯微球树脂进行两步功能基化的修饰反应来制备. 制备过程如下：聚苯磺酰氯树脂(1)与伯胺(2)反应得到聚苯乙烯基N-烷基磺酰胺树脂(3), 树脂3用酰氯(4)或酸酐酰化得到N-烷基-N-酰基磺酰胺聚苯乙烯基树脂(5). 酰化的树脂5作为酰基转移试剂与亲核试剂胺反应得到二级酰胺. 根据5上取代基对酰胺生成的程度的影响结果表明, 烷基R¹和酰基(R²CO)对酰基转移反应活性的大小依次分别为：苯基＞苄基＞甲基＞正丁基＞＞H和对硝基苯甲酰基(苯甲酰基＞乙酰基. 胺的亲核能力对酰胺的收率也有一定的影响. N-苯基-N-苯甲酰基磺酰胺树脂重复使用3次没有发现活性降低.     

聚苯乙烯磺酰氯和聚苯乙烯亚磺酸盐的合成及其应用

本文以36篇文献，包括作者近年的工作，综述了聚苯乙烯磺酰氯和聚苯乙烯亚磺酸盐的合成方法和这些功能基化聚合物在有机合成及其他方面的应用。     

3-聚苯乙烯磺酰基丙醇的制备及其在固相有机合成中的应用

本文采用聚苯乙烯亚磺酸钠树脂1与3-氯丙醇在碘化四正丁胺和碘化钾的存在下反应制备了3-聚苯乙烯磺酰基丙醇树脂2.以该树脂为载体固载了Boc保护的L-丙氨酸,再经封羟基、脱保护、中和,与异氰酸苯酯反应制得聚合物支载的脲6.脲树脂6在酸性或强碱条件下解脱得到取代的海因化合物,在弱碱条件下解脱得到取代的脲化合物.     

SOLID PHASE SYNTHESIS OF ISOXAZOLINES

1. INTRODUCTION A solid phase organic synthesis (SPOS) has increasingly attracted chemist抯 attention over the past decades [1~3]. It was found that the compounds with biological activity are mostly derived from heterocycle structures. It is therefore no…     

SOLID PHASE SYNTHESIS OF ISOXAZOLINES

The solid-phase synthesis of isoxazolines on 2-polystyrylsulfonamidoethanol resin isreported. 2-Polystyrylsuifonamidoethanol resin 1 was reacted with acryloyl chloride to afford2-polystyrylsulfonylamidoethyl acrylate resin 2, which was further reacted with brominatedaldoximes by [3+2] cycioaddition to give isoxazoline resin 4. Resin 4 was treated with aqueous 6mol/L HCI solution to obtain isoxazolines in good yield and purity.     

THE STUDIES OF THE CURING OF AN EPOXY RESIN ON COPPER WIRE BY FTIR EXTERNAL REFLECTION SPECTROSCOPY

The epoxy coating on copper wire has been studied by a modified sampling technique using Fourier transform infrared (FTIR) diffuse reflectance attachment. As the wire axis was parallel to the incident plane, a reflection spectrum of thin layer coating on a copper wire can be obtained. The study found that imidszole, especially the acetic acid treated imidazole, can be used as an effective curing catalyst of the epoxy resin on copper. This is the first report about the IR study of coatings on metal wires.     

Solid-phase synthesis of amine-bridged cyclic enkephalin analogues via on-resin cyclization utilizing the Fukuyama-Mitsunobu reaction

An efficient solid-phase synthetic route is described for the preparation of 13-membered amine-bridged cyclic enkephalin analogues (ABEs) 1a and 1c-1j (Figure 1) resulting from a sulfonamide-containing peptide whose backbone is bound to a resin. The Fukuyama-Mitsunobu reaction of the 2-nitrobenzenesulfonyl-protected amine bound to the solid support with protected aminoethanol in the presence of triphenylphosphine and diisopropyl azodicarboxylate (DIAD) is utilized to prepare a resin-bound sulfonamide-protected secondary amine. After peptide cyclization, this protected amine functionality becomes the "amine bridge" of the target molecule. In addition, the reagent DIAD was found to be a superior reagent compared to diethyl azodicarboxylate (DEAD) in the solid-phase Fukuyama-Mitsunobu reaction.     

Synthesis and characterization of new nano-particles as blue ceramic pigment

The synthesis of a new nano-blue ceramic pigment CoxMg1-xAl2O4 (0 < or = x < or = 0.1) using the combination between co-precipitation and combustion synthesis (CS) method. The structure of pigments is assigned based on thermogravimetric and differential thermogravimetric analysis (TG-DTGA), X-ray diffractions (XRD), and UV-vis spectroscopy. Also, diffuse reflectance spectroscopy (DRS) using CIE L*a*b* parameter measurement method, infrared spectroscopy (IR) and transmission electron microscopy (TEM) is used. The result revealed that the nano-size particle pigment was obtained in range 24-35 nm by using 3-methyl-pyrozole-5-one (3MP5O) as a fuel at 400 degrees C in open furnace. Also, results show the varying colors and particles' size as a result of different calcination temperatures from 500 to 1200 degrees C for 2h.     

Resacetophenone oxime–formaldehyde resin and its metal chelates. III

In this paper the synthesis and properties of resacetophenone oxime–formaldehyde resin are described. The number-average molecular weights of the resin determined by vapor-pressure osmometry and nonaqueous conductometric titration are 2200 ± 10% and 2500 g/mol, respectively. Cu(II), Ni(II), and Co(II) chelates of the resin were prepared. Elemental analysis of the chelates indicates a metal to ligand ratio of 1:2. The diffuse reflectance spectra and magnetic moments of Ni(II) and Co(II) chelates show tetrahedral structure, whereas Cu(II) chelate shows a square planar structure. Infrared spectral studies show that the metals are coordinated through the nitrogen of the oximino group and oxygen of the phenolic group. The presence of methylene bridges is also indicated by IR spectral studies. The thermal behavior of the resin and its metal chelates are also discussed.     

A new route to semirigid poly(amide-ester)s with ordered structure

Four novel semirigid poly(amide-ester)s having the same ordered amide-amide-ester-ester (-AAEE-) and the same or the different phenyl structure were synthesized from the various combination of active acylamide of benzotriazole (HBT) such as 1,1′-(isophthaloyl)bisbenzotriazole (IPBBT) and 1,1′-(terephthaloyl)bisbenzotriazole (PBBT) with diols such as N,N'-bis(2-hydroxyethyl)isophthamide (HEIPA) and N,N'-bis(2-hydroxyethyl)terephthamide (HEPTA) which prepared from the selective N-acylation of IPBBT or PBBT with aminoethanol in excellent yield at room temperature. Before the preparation of diol monomers, a model reaction of selective N-acylation was also completed from active monoacylamide of benzotriazole, 1-benzoylbenzotriazole with aminoethanol. The ordered structure of poly(amideester)s were characterized by infrared (IR) and NMR spectra. On the bases of different reactivity between selective N-acylation and O-acylation of active acylamide of benzotriazole, poly(amide-ester)s having the ordered AAEE and the same phenyl structure were also readily synthesized from the IPBBT or PBBT with aminoethanol under mild conditions by one-bath process.     

Dehydrogenation of ethylbenzene with nitrous oxide in the presence of mesoporous silica materials modified with transition metal oxides

The novel mesoporous templated silicas (MCM-48, SBA-15, MCF, and MSU) were used as supports for transition metal (Cu, Cr, or Fe) oxides. The catalysts were synthesized using the incipient wetness impregnation, and characterized by low-temperature N2 sorption, DRIFT, photoacoustic IR spectroscopy, UV-vis diffuse reflectance spectroscopy, and temperature-programmed desorption of ammonia. It was shown that the preparation method used results in different distributions and dimensions of the transition metal oxide clusters on the inert support surface. The prepared catalysts were tested in the reaction of oxidative dehydrogenation of ethylbenzene in the presence of nitrous oxide. The iron-containing catalysts showed the highest catalytic activity. The presence of isolated Fe3+ was found to be the most important factor influencing the ethylbenzene conversion. The undesirable effect of the increase in selectivity toward CO2 was observed for the samples with the highest concentrations of acidic surface sites.     

Polystyrene-bound electron-deficient tin(IV) porphyrin: A new, highly efficient, robust and reusable catalyst for acetylation of alcohols and phenols with acetic anhydride

In the present work, tetrakis(p-aminophenyl)porphyrinatotin(IV) trifluoromethanesulfonate, [Sn^IV(TNH₂PP)(OTf)₂], supported on chloromethylated polystyrene was prepared and characterized by elemental analysis, FT IR and diffuse reflectance UV-Vis spectroscopic methods. This new heterogenized catalyst was used for acetylation of alcohols and phenols with acetic anhydride in short reaction times and high yields. The catalyst is of high reusability and stability in the acetylation reactions and was recovered several times without loss of its initial activity and catalyst leaching.     

电荷转移盐(C3H5N2)3[PMo12O40]的合成与热分解及光致变色动力学

用磷钼酸与咪唑合成一种新的杂多酸-有机电荷转移盐(C3H5N2)3[PMo12O40]。通过元素分析、红外光谱、固体漫反射光谱、电子自旋共振及热分析等测试技术对其进行了表征,用单扫描法(Achar法和Coats-Redfern法)对合成化合物的TG分析结果进行了非等温热分解动力学研究。推断结果表明,合成化合物的第1步热分解为球对称的三维扩散机理(n=2),其动力学方程为dα/dt=1.58×108[1-(1-α)1/3]-1(1-α)2/3exp(-40 931.0/T),求得分解反应的表观活化能E=340.30 kJ/mol,指前因子A=1.05×108 s-1。 标题化合物对紫外光具有光致变色性质,用固体漫反射光谱研究了其光致变色反应动力学。 结果显示,其光致变色反应表现为一级或准一级动力学,速率常数k=9.80×10-5 s-1。