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New contributions of this work are as follows:(1). Preparation of Spherical MgCl_2-Supported Late-Transition Metal Catalysts for Ethylene PolymerizationFacile and effective immobilization of late-transition metal catalysts. 2,3-bis-(2,6-diisopropylphenyl) butane diimine nickel dibromide (1) and 2,6-bis-[1-(2,4,6-trimethylphenylimino)ethyl]pyridine iron dichloride (2), for ethylene polymerization has been achieved, using spherical MgCl_2 supports obtained by thermal dealcoholization of MgCl_2·2.56C_2H_5OH, and the effects of dealcoholization temperature on supported late-transition metal catalysts and the properties of resultant polymers were studied, the results indicated that:1.Supports with appropriate mechanical strength, high surface area and high porosity could be prepared by thermal dealcoholization of spherical MgCl_2·2.56C_2H_5OH supports; 2.BET, XRD, IR, SEM, GPC and DSC analyses indicate that the activities of the supported late-transition metal catalysts and the properties of resultant polymers are strongly dependent on the dealcoholization temperature.

本工作的新贡献如下:(1)、球形氯化镁负载后过渡金属催化荆催化乙烯聚合本文将配合物2,3-双(2,6-二异丙基苯亚胺)丁烷二溴化镍(1)和配合物2,6-二[1-(2,4,6-三甲基苯亚胺)乙基]吡啶二氯化铁(2)分别直接负载于经不同热脱醇温度处理的球形氯化镁载体上,研究了氯化镁载体的脱醇温度对负载化后过渡金属催化剂及其聚合物的影响,研究表明:1、通过对球形MgCl_2·2.56C_2H_5OH载体进行热脱醇处理,可以获得合适机械强度、较高比表面积和较高孔隙度的球形氯化镁载体;2、BET,XRD,IR,SEM,GPC和DSC研究表明,脱醇温度极大地影响负载后过渡金属催化剂的活性和聚合物的性能。

Whenpyridine was used as reductive decomposing agent, the expecting cholest-4-en-3,6-dione-22-al was obtained. However, when Zn/HOAc was used to decomposethe ozonide, C-4,5 double bond was further reduced to give cholest-3,6-dione-22-al as main product. 2 For the side-chain construction of compound (1), the solid-liquid phase-transfer Wittig reaction was used. When (3-methyl-2-oxobutyl)-triphenylarsonium bromide was used as reagent, the reaction can be carried out inmild reaction condition and the yield is higher than that when phosphorane wasused.

但使用Zn/HOAc作为分解剂时,却得到其氢化产物胆甾-3, 6-二酮-22-醛;2在甾体支链引入过程中,采用固-液相转移Wittig反应的方法,用(3-甲基)-2-氧丁基三苯基溴化胂作为试剂,反应在非常温和的条件下便可完成,而且产率比传统采用膦烷的方法更高;3在对某些甾酮化合物的选择性还原反应研究时,发现在〓还原体系中,当加入某些金属离子后,反应有更好的区域选择性和立体选择性。

Sodium fatty alcohlo ether sulfate, S-80, fatty alcohol-polyoxyethylene ether and S-60 resulted in slow photodecomposition of rotenone in aqueous solution revealing a photo-extinction effect, sodium dodecylberzenesulfonate, tween-60, hexadecyl trimethyl ammonium bromide and poyl vinyl pyrrolidone made the photolysis of rotenone in aqueous solution fast showing an obvious photosensitized effect.

室内条件下研究了鱼藤酮水溶液存在不同表面活性剂时,鱼藤酮的紫外光降解,结果表明:脂肪醇聚氧乙烯醚硫酸钠、司本-80、长链脂肪醇聚氧乙烯醚和司本-60对鱼藤酮在水溶液中的光解速率表现出显著的光猝灭降解效应;十二烷基苯磺酸钠、吐温-60、十六烷基三甲基溴化铵和聚乙烯吡咯烷酮对鱼藤酮在水溶液中的降解表现出一定程度的光敏化作用。

Two-dimensional multilayered complex of Octabenzenesulphonate Polyhedral Oligomeric Silsesquioxane modified by alkyltrimethylammonium bromide C_nH_(2n+1N(CH_3)_3Br, CnTAB, where n denotes the carbon number in the alkyl chain via ion-exchange reaction.

一方面,使用多电荷阴离子的八磺酸根POSS和十六烷基三甲基溴化铵表面活性剂在水溶液体系里面进行离子交换反应,利用有机-无机不同的相似相容性质通过自组装的手段,得到具有规整的二维层状结构的杂化材料。

In addition,α-alkenoyl ketene--acetals mainly used as the synthons of 3C and 5C, theα-functionalized reactions of which just limited on some simple reactions, as bromination, nitration, acetylation. However, the understanding of the forming of C-C bond atα-position is far from enough.

另外,对于α-烯酰基二硫缩烯酮的研究则主要集中在其作为3C或5C合成子的研究上,其α-位的官能化研究只是停留在溴化、硝化、脱羧等简单的反应之上,而对α-位C-C键的形成还缺乏足够的认识。

After the click reaction of the SCL micelles and azide-terminus PNIPAM homopolymer, the novel PNIPAM-functionalized SCL micelles with pH-responsive cores and outer thermosensitive coronas were prepared, which was investigated act as excellent candidate of nanosized drug delivery vehicles. Finally, two types of novel shell cross-linked micelles in aqueous solution were prepared from these remarkable PMEO_2MA-b-P(DMA-co-QDMA)-b-PDEA triblock copolymers by cross-linking the inner P(DMA-co-QDMA) shell of micelles upon the addition of diazide tetra derivative in the presence of copper catalyst using click chemistry.

另外,还可以使用溴丙炔对ATRP聚合出的PMEO_2MA-b-PDMA-b-PDEA三嵌段的中间PDMA嵌段进行部分季胺化,这样可以利用两端叠氮化的四甘醇来交联由PMEO_2MA-b-PDMA-b-PDEA在不同条件下形成的两种分别以PMEO_2MA或PDEA为核的胶束,从而实现了从同一个聚合物直接在水溶液中得到两种内核不同敏感的壳交联胶束。

For the first time, enantiomers of C2-symmetric 1,1 -spirobiindane-7,7'-diol were resolved with crude menthyl chloroformate by phase-transfer catalysis in the presence of tetrabutylammonium bromide. The reaction was carried out at 0℃-rt. The diastereomers of SPINOL bis-menthyl carbonate can be separated by simple crystallization using alcohol. The hydrolysis of the diastereomers was carried out via aqueous NaOH/EtOH solution.

首次通过相转移催化的方法对螺双二氢茚二酚进行了有效的拆分,用L--氯甲酸薄荷醇酯做拆分剂,以四丁基溴化铵为催化剂在0℃-室温下进行酯化反应生成非对映体衍生物,以乙醇作溶剂,通过重结晶的方法分离衍生物,在水-乙醇混合溶剂条件下,用强碱NaOH或KOH分别水解,制得相应的光学纯度大于99%ee的两个异构体SPINOL,其中总收率:--SPINOL,78.2%;--SPINOL,80.6%。

First, the geometry optimization for 1-phenyldibenzophosphole and triphenylphosphine were carried out using quantum chemical AM1 method.

用量子化学AM1方法优化了1-苯基二苯并膦和三苯基膦的几何构型,比较了两种化合物的电子结构和空间结构,发现PDBP作为羰基合成铑膦催化剂的配体要优于三苯基膦;系统研究了PDBP的合成方法,其最佳合成条件为:在无水无氧的条件下,采用二乙胺锂与溴化四苯基膦摩尔比为3,反应温度为22 ℃,反应5 h,反应后酸化, pH值为1~2,产物收率可达到85%~88%。

After the click reaction of the SCL micelles and azide-terminus PNIPAM homopolymer, the novel PNIPAM-functionalized SCL micelles with pH-responsive cores and outer thermosensitive coronas were prepared, which was investigated act as excellent candidate of nanosized drug delivery vehicles.

另外,还可以使用溴丙炔对ATRP聚合出的PMEO_2MA-b-PDMA-b-PDEA三嵌段的中间PDMA嵌段进行部分季胺化,这样可以利用两端叠氮化的四甘醇来交联由PMEO_2MA-b-PDMA-b-PDEA在不同条件下形成的两种分别以PMEO_2MA或PDEA为核的胶束,从而实现了从同一个聚合物直接在水溶液中得到两种内核不同敏感的壳交联胶束。

A novel chiral diallylic diamine has been synthesized through double addition of allyl zinc bromide to chiral imines in this contribution.

通过烯丙基溴化锌对手性亚胺的两次不对称加成,合成了光活性的双烯丙基化的新型手性二胺。

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