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1.
Jing Lin 《Tetrahedron letters》2004,45(1):103-106
Bisbinaphthyl-based macrocycles are found to carry out enantioselective fluorescent recognition of α-amino acid derivatives. It is observed that one enantiomer of a N-protected phenyl glycine can increase the fluorescence intensity of the binaphthyl fluorophores by over 4-fold but the other enantiomer does not cause much fluorescence enhancement. This highly enantioselective fluorescent response makes the binaphthyl macrocycles practically useful for the enantioselective fluorescent recognition of the amino acid substrate. 相似文献
2.
Anna Finne Ann-Christine Albertsson 《Journal of polymer science. Part A, Polymer chemistry》2004,42(3):444-452
Following our continued interest in the production of bioerodible and biodegradable functional polymers for biomedical applications, we synthesized and characterized new unsaturated polyesters. The presence of functional groups in the polymer backbone provided sites for chemical modification, and through a variation in the structure, the physical properties, such as the hydrophilicity and solubility, could be affected. With 1,1-di-n-butyl-stanna-2,7-dioxacyclo-4-heptene as the initiator in the ring-opening polymerization of polyesters, a new set of functionalized polyesters was created. The polymerization of ϵ-caprolactone resulted in poly(ϵ-caprolactone) with a double bond incorporated into the structure. The polymers were obtained in a controlled manner with low molecular dispersities. The double bond was previously incorporated into L -lactide polymers, and the two reactions were compared in this study. The conversion of ϵ-caprolactone, with a degree of polymerization of 50, was completed within 140 min, whereas for L -lactide, only a 45% conversion took place in the same period of time. The dispersities were somewhat higher with ϵ-caprolactone because of the higher reaction rate and, therefore, lower selectivity. The incorporated CC double bond in the polyesters provided a variety of opportunities for further modifications. In this case, the double bond of the L -lactide macromonomers was oxidized into epoxides. Epoxidation was carried out with m-chloroperoxybenzoic acid as a chemical reagent. The conversion of the double bonds into epoxides was completed, and the obtained yields were good (>95%). As a result of the mild reaction conditions, the epoxidation of the double bond was carried out quantitatively without any side reactions. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 444–452, 2004 相似文献
3.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(1):130-137
We have shown previously that iodosylbenzene–iron(III ) porphyrin intermediates ( 2 ) are generated in the reactions of oxoiron(IV ) porphyrin π‐cation radicals ( 1 ) and iodobenzene (PhI), that 1 and 2 are at equilibrium in the presence of PhI, and that the epoxidation of olefins by 2 affords high yields of epoxide products. In the present work, we report detailed mechanistic studies on the nature of the equilibrium between 1 and 2 in the presence of iodoarenes (ArI), the determination of reactive species responsible for olefin epoxidation when two intermediates (i.e., 1 and 2 ) are present in a reaction solution, and the fast oxygen exchange between 1 and H218O in the presence of ArI. In the first part, we have provided strong evidence that 1 and 2 are indeed at equilibrium and that the equilibrium is controlled by factors such as the electronic nature of iron porphyrins, the electron richness of ArI, and the concentration of ArI. Secondly, we have demonstrated that 1 is the sole active oxidant in olefin epoxidation when 1 and 2 are present concurrently in a reaction solution. Finally, we have shown that the presence of ArI in a reaction solution containing 1 and H218O facilitates the oxygen exchange between the oxo group of 1 and H218O and that the oxygen exchange is markedly influenced by factors such as ArI incubation time, the amounts of ArI and H218O used, and the electronic nature of ArI. The latter results are rationalized by the formation of an undetectable amount of 2 from the reaction of 1 and ArI through equilibrium that leads to a fast oxygen exchange between 2 and H218O. 相似文献
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不同沉淀剂制备的Ag/TS-1催化丙烯直接气相氧化合成环氧丙烷 总被引:3,自引:0,他引:3
在423K、常压固定床石英反应器中,以丙烯直接气相氧化为探针反应,考察了催化剂制备方法、沉淀剂的种类和浓度对制备的Ag/TS-1催化剂催化性能的影响,采用TEM,XRD和UV-Vis等表征手段对Ag/TS-1催化剂进行了分析.结果表明,沉积-沉淀法是最佳的催化剂制备方法,但浸渍法也可制得具有环氧丙烷选择性的催化剂.K2CO3是一种良好的沉淀剂.以K2CO3为沉淀剂,硅钛比为64的TS-1为载体制备的Ag/TS-1催化剂上的丙烯转化率为1.72%,环氧丙烷选择性为98.2%.少量单质银的存在有利于环氧丙烷的生成,除银粒子的分散状态外,银粒子与载体TS-1间的相互作用对提高催化剂的选择性具有决定性作用. 相似文献
6.
合成了6种钨硅杂多配合物异构体α、βi-M3H2[SiW11(NbO2)O39]·H2O(M=Me4N+(TMA),Bu4N+(TBA),Et4N+(TEA);βi=β1,β2,β3)。IR光谱、UV光谱、极谱、I--S2O32-滴定证明合成的杂多配合物中有NbO2基存在, 183W NMR光谱证明其阴离子具有Keggin结构,催化实验结果表明,合成的化合物对烯烃环氧化反应具有催化活性,且过氧杂多配合物的催化活性高于非过氧杂多配合物,β异构体的催化活性高于α。 相似文献
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8.
具有C2对称轴的手性配体及其不对称催化反应 总被引:2,自引:0,他引:2
按配位原子的数目进行分类,综述了近年来研究较多的具有C2对称轴的手性配体及其相关的不对称催化反应,并对该类手性配体的设计做了分析和总结。参考文献79篇。 相似文献
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以TiCl4和SiCl4为原料,采用水解和非水水解溶胶-凝胶两种方法制备了一系列不同Ti含量的Ti-Si复氧化物载体,继而用沉积-沉淀法制得载金催化剂. 采用X射线衍射、紫外-可见漫反射光谱、 N2吸附和高分辨透射电镜对催化剂进行了表征,并考察了催化剂在氢气和氧气存在下的丙烯气相环氧化催化性能. 研究表明,钛含量在6%~14%范围内时,两种方法制得的Ti-Si复氧化物均为无定形结构,但采用非水水解溶胶-凝胶法制得的载体比表面积较高. 以非水水解溶胶-凝胶法制备的钛含量10%的Ti-Si复氧化物为载体得到的载金催化剂表现出较高的活性和选择性,反应60 min时,丙烯转化率为5.7%, 240 min后降为3.3%, 环氧丙烷的选择性稳定于95%左右. 还考察了非水水解溶胶-凝胶的陈化时间和金沉积-沉淀溶液的pH值等对反应结果的影响. 相似文献