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。     

Friedel-Crafts酰基化法制备聚苯乙烯型阴离子交换树脂

提出了一种合成聚苯乙烯型阴离子交换树脂的新方法：通过Ｆｒｉｅｄｅｌ－Ｃｒａｆｔｓ酰基化反应在交联聚苯乙烯上引入乙酰基，然后经溴化、胺化反应制备阴离子交换树脂。该方法避免了使用氯甲醚等致癌物质，并消除了二次交联等副反应。讨论了溶剂，催化剂，试剂和反应温度及时间等因素对各步反应的影响。测定了产物的基本性能并对所得结果进行了讨论。     

应用阴离子交换树脂有效合成3—芳氨基—4—氰基—5—氨基吡唑

研究了不活泼芳胺（杂环胺）与α，α－二氰基二硫缩醛的加成－消除反应，报道了一种应用阴离子交换树脂有效合成３－芳氨基－４－氰基－５－氨基吡唑的一锅煮方法。     

聚苯乙烯—三乙醇胺树脂催化合成α—丁基苯乙腈

研究了聚苯乙烯－三乙醇胺树脂催化苯乙腈的α－丁基化作用,考察了反应温度,催化剂用量和反应时间对产品收率的影响及催化剂的回收,套用性能,在本实验最佳条件下,收率可达６８％,催化剂回收套用５次后,活生未降低,重量未损失。     

2,5—取代—1,3,4—恶二唑化合物库的固相合成

本文使用组合化学方法以聚苯乙烯亚磺酸钠树脂为载体合成了２，５－取代－１，３，４－恶二唑化合物库。树脂１首先与溴代乙酸乙酯反应聚合物支载的乙酸酯。肼解后所得的肼树脂进一步与取代的苄氯反应得双酰肼树脂。树脂４与三氯氧磷回流得聚合物支载的２，５－取代－１，３，４－恶二唑。     

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。     

交联聚苯乙烯强—弱碱树脂的合成及脱色性能研究

交联聚苯乙烯氯甲基化后，分别与甲胺（或二甲胺）、三甲胺（或α－甲基吡啶、二甲基乙醇胺）混合胺化试剂进行亲核取代反应，合成了一系列同时带有强－弱碱功能基的交联聚苯乙烯树，并表征了这些树脂的结构，测定了树脂对甜菊甙的脱色性能，结果表明，这些树酯功能基碱性适中，脱色容量较高，甜菊甙损失较少，再生效率高。     

交联聚苯乙烯强－弱碱树脂的合成及脱色性能研究

交联聚苯乙烯氯甲基化后，分别与甲胺（或二甲胺）、三甲胺（或α－甲基吡啶、二甲基乙醇胺）混合胺化试剂进行亲核取代反应，合成了一系列同时带有强－弱碱功能基的交联聚苯乙烯树脂，并表征了这些树脂的结构，测定了树脂对甜菊甙的脱色性能，结果表明，这些树脂功能基碱性适中，脱色容量较高，甜菊甙损失较少，再生效率高。     

应用漫反射红外光谱技术优化2-聚苯乙烯磺酰胺基乙醇树脂的合成

本文采用漫反射红外光谱法优化一种新的固相合成载体2－江西 乙烯磺酰胺基乙醇树脂的合成。聚苯乙烯磺酰氯树脂在有或没有溶剂和／或催化剂存在下与乙醇铵反应得到2－聚苯乙烯磺酰胺基乙醇树脂。漫反射红外光谱跟踪整个反应过程。结果表明，漫反射红外光谱技术是优化制备新的功能基化聚合物条件的有力工具。2－聚苯乙烯磺酰胺基乙醇树脂的优化制备条件是：聚苯乙烯磺酰氯，乙醇胺在60℃反应30min。     

席夫碱型聚苯乙烯多胺树脂的合成及性能研究

以乙酰化聚苯乙烯树脂为母体,与二乙烯三胺缩合制备了席夫碱型聚苯乙烯多胺树脂,分别研究了溶剂、催化剂、物料比、反应温度和反应时间等对反应的影响,并对树脂进行了结构表征,初步探索了树脂对Cu~(2+)的吸附行为。结果表明,在偏三甲苯中,以对甲苯磺酸为催化剂,160℃下反应16h,所得多胺树脂的全交换容量为3.99mmol/g,对Cu~(2+)的吸附量为63.5mg/g。     

Thermal behavior of typical weak basic ion exchange resin

Thermal behaviors of typical weak basic ion exchange resins (301 and 315) were studied with thermogravimetry, elemental analysis, and Fourier transform infrared spectrometer in this study. Results indicated that there were three stages for 301 resin mass loss, the first stage and the second stage were mainly related to the decomposition of functional group, and the third stage was the decomposition of main chain. Whereas there were two stages for 315 resin mass loss, the first stage was elimination of moisture, and the second stage was the decompositions of functional group and main chain. Moreover, the decomposition of tertiary amine had three stages, the polyamine was a continuous mass loss process, and the thermostability of tertiary amine was weaker than that of polyamine.     

聚氯乙烯多乙烯多胺树脂的相转移催化作用

聚氯乙烯多乙烯多胺树脂可作为酯水解、氧取代(醚和酯的合成)、卤素取代(丁基碘和硫氰酸卞酯的合成)和缩合反应(卞叉丙酮的合成)的催化剂,效果良好。它是一种新型的高分子相转移催化剂。     

Versatile procedure for asymmetric and orthogonal protection of symmetric polyamines and its advantages for solid phase synthesis

To date, many polyamine syntheses are carried out on solid phase to allow the generation of biologically active polyamine conjugates and libraries of natural product analogs. The synthesis of compounds and libraries, which derive from a symmetric polyamine building block such as spermine requires asymmetric and orthogonal protection of the symmetric polyamine. For this purpose we have established a novel Aloc- and Nosyl-protection group strategy, which displays several advantages. Solution phase synthesis and an easy workup reveals high yield of the asymmetrically and orthogonally protected polyamine. Asymmetric protection prevents cross-linking of the resin, and sequential deprotection can occur on highly acid and base labile resins without cleavage of the linker. Finally, it tolerates the elongation and modification of the symmetric polyamine backbone with several functional groups by conventional Fukuyama-alkylation. The suitability of this protection group strategy was shown by the first solid phase synthesis of the philanthotoxin-analog HO359b.     

The effect of epoxy resin and polyamine hardener on the photo-fading of 2-piperidinoanthraquinone in solution: A flash photolysis study

The triplet state of 2-piperidinoanthraquinone has been generated in toluene solutions using nanosecond laser flash photolysis. The effect of epoxy resin and polyamine hardener on the yield and lifetimes of the dye triplet state and the dye semiquinone species has been studied. For both resin and hardener, dye semiquinone species are produced which subsequently disproportionate to yield the hydroquinone and so cause photo-fading. The mechanisms by which these free radicals are formed and their relevance to the photo-fading of dyed epoxy resin are discussed in detail.     

自乳化水性环氧树脂乳液的研制

利用化学改性的方法制备自乳化型水性环氧树脂乳液。采用二乙醇胺部分开环环氧树脂,并采用聚醚多胺进行扩链,制备可自分散的阳离子水性环氧树脂乳液。本文研究了乳液研制时共溶剂丙二醇甲醚、环氧树脂分子量、二乙醇胺用量、不同的聚醚多胺、聚醚多胺D-230用量、HAC用量对乳液稳定性的影响。并对乳液性能进行测试,结果表明,该乳液具有良好的贮存稳定性,VOC含量低,涂膜综合性能优良等特点,该乳液为环保型产品。     

聚合物负载手性季铵盐的合成与表征

以金鸡纳生物碱中的辛可宁为原料,氯甲基化聚苯乙烯-聚乙二醇、一缩二乙二醇、二缩三乙二醇、乙二醇等为载体合成了几种聚合物负载的手性季铵盐,并对它们的结构用红外光谱、元素分析、扫描电镜和X射线光电子能谱等测试手段进行了表征。     

The combined solid/solution-phase synthesis of nitrosamines: the evolution of the "libraries from libraries" concept

The generation of diverse chemical libraries using the "libraries from libraries" concept by combining solid-phase and solution-phase methods is described. The central features of the approaches presented are the use of solid-phase synthesis methods for the generation of a combinatorial polyamine library. Following cleavage from the resin with HF, the polyamine library was reacted with ethyl nitrite in the solution phase to yield the desired nitrosamine library in good yield and purity. The approaches described enable the efficient syntheses of individual nitrosamines as well as mixture-based nitrosamine libraries.     

Synthesis and high performance liquid chromatography/electrospray mass spectrometry single-bead decoding of split-pool structural libraries of polyamines supported on polystyrene and polystyrene/ethylene glycol resins

Natural polyamines are ubiquitous biomolecules present in all living cells. These cationic compounds play essential roles in both cell growth and differentiation and are known to interact in complex ways with polyanionic biomolecules. Consequently, there is significant interest in expanding nature's polyamine diversity using combinatorial synthesis and screening strategies. This article describes an efficient split-pool solid-phase synthetic strategy toward the generation of encoded libraries of polyamines via the exhaustive borane-promoted reduction of trityl-linked, resin-bound polyamides. Model structural libraries of tetra- and pentaamines were designed from a set of geometrically diverse amino acid building blocks. To encode the libraries, a partial termination synthesis approach was employed at the polyamide stage, allowing each library to be analyzed from single beads by HPLC/ESMS under two sets of conditions featuring both pH extremes. Determination of the sequence of polyamine residues was simply achieved by the mass differences observed between the full oligomers and the terminated ones. Both polystyrene- and TentaGel-supported libraries, including a library of 4913 pentaamines, were prepared and successfully decoded. For the TentaGel-supported libraries, suitable for on-bead aqueous screening of biomolecules, a novel trityl-derivatized resin was prepared in which the trityl group is anchored to the poly(ethylene glycol) chains via a methylene group. The resulting resin is much more resistant than other commercially available polystyrene-poly(ethylene glycol) trityl resins to the harsh borane reduction conditions required. Two workup conditions for the cleavage of the resultant borane-amine adducts were evaluated on the TentaGel bound polyamide 14. Although the two methods showed a comparable efficiency when using the polystyrene support, with 14 it was found that the piperidine-exchange method afforded polyamines of higher purity than the iodine-based oxidative method previously developed in our laboratory.     

渗透型改性环氧灌浆材料

以环氧树脂为主剂、脂肪族多胺为固化剂,以糠酮树脂、活性稀释剂糠醛丙酮、硅烷、Mannich型酚醛胺为主要改性材料的改性环氧灌浆材料,具有优异的渗透性,结合适当的施工工艺,可获得固化时间可调、固化物强度符合实际工程的渗透型改性环氧灌浆材料,并可用作多种用途。     

Electrospray ionization mass spectra of monoimidazole/polyamine conjugates

Imidazole/polyamine amides are biologically important molecules due to their specific DNA binding activity, and much attention has been attracted to the synthesis of their derivatives or analogues. In the present studies, the fragmentation of a series of synthetic monoimidazole/polyamine amides was investigated using electrospray ionization mass spectrometry (ESI-MS) combined with tandem mass spectrometry (ESI-MS/MS). All of the monoimidazole/polyamine amides produced the fragment ion m/z 183 except for the monoimidazole/ethyldiamine amide. The diamine amides produced this ion after the elimination of an alkene, the triamine amides produced it via their corresponding diamine amide fragments, and the tetraamine amide via its triamine and then diamine amide fragments. The characterization of the mass spectra for the different polyamine amides allowed identification of a specific product from the N-acylation of spermidine, and should assist further study of the polyamine amides in DNA binding action.