Alteration of Organic Synthetic Processes Using Organic Zeolites in Water

在水中使用有机沸石改变有机合成工艺

基本信息

批准号：
13555220
负责人：
AOYAMA Yasuhiro
金额：
$ 8.64万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

We investigated the microporocity, guest-binding properties, and catalytic behaviors of "organic zeolites" based on anthracene-bisresorcinol derivatives. The major achievements are as follows.(1) Lanthanum-containing organic zeolites catalyze various reactions of carbonyl substrates which proceed via enolate intermediates. This is, however, not the case for such reactions as carbonylation of ketones with CO_2 and isomerization of sugars, in which the chelate-type products show strong affinity to the metallic center to prohibit turnover of the catalysts.(2) Lanthanum complexes of triphenylphosphine was used to network various, heavy metals such as Pd(II), Ru(II), Rh(II), and Pt(II) to give microporous materials. They are capable of promoting, characteristic reactions of these metals such as. coupling but only in a stoichiometric manner ; this is because reoxidation of reduced, metal centers is still a problem.(3) Acridine-bisresorcinol derivatives serve as a "self-complementary" building blocks in which the nitrogen acts as a kind of "guest" for the resorcinol moiety to give coordinatively saturated and robust microporous material. Benzene as a guest can be removed without changing the crystal structure significantly.(4) Anthracene-bis(isophtalic acid) gives rise to a remarkably robust H-bonded network capable to reversible adsorption-desorption of methane. The crystal structure of genuine microporopus crystal structure was revealed.(5) Attempts were also made to utilize glycoclusters as a source of organic zeolites stable in water. The calix[4]resorcarene-based macrocyclic glycoclusters encapsulate plasmid DNA in a size-and number-controlled manner to give artificial "glycovirus" of a size of 50 nm.

我们研究了基于蒽-双间苯二酚衍生物的“有机沸石”的微孔性、客体结合特性和催化行为。主要成果如下：(1)含镧有机沸石催化羰基底物通过烯醇化物中间体进行的各种反应。然而，酮与CO_2的羰基化和糖的异构化等反应却并非如此，其中螯合型产物对金属中心表现出很强的亲和力，从而阻止催化剂的周转。(2)三苯基膦的镧配合物用于网络化各种重金属，例如 Pd(II)、Ru(II)、Rh(II) 和 Pt(II)，以得到微孔材料。它们能够促进这些金属的特征反应，例如。耦合，但仅以化学计量方式；这是因为还原的金属中心的再氧化仍然是一个问题。（3）吖啶-双间苯二酚衍生物作为“自互补”结构单元，其中氮充当间苯二酚部分的一种“客体”以进行配位饱和且坚固的微孔材料。苯作为客体可以在不显着改变晶体结构的情况下被去除。(4)蒽-双(间苯二甲酸)产生非常坚固的氢键网络，能够可逆地吸附-解吸甲烷。揭示了真正的微孔菌晶体结构。(5)还尝试利用糖簇作为水中稳定的有机沸石来源。基于杯[4]间苯二酚的大环糖簇以大小和数量控制的方式封装质粒DNA，产生大小为50 nm的人工“糖病毒”。

项目成果

期刊论文数量（70）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

O.Hayashida, K.Mizuki, K.Akagi, A.Matsuo T.Kanamori, T.Nakai, S.Sando, Y.Aoyama: "Macrocyclic Glycoclusters. Self-Aggregation and Phosphate-Induced Agglutination Behaviors of Calix[4]resorcarene-Based Quadruple-Chain Amphiphiles with a Huge Oligosaccharid

O.Hayashida、K.Mizuki、K.Akagi、A.Matsuo T.Kanamori、T.Nakai、S.Sando、Y.Aoyama：“大环糖簇。Calix[4]间苯二酚的自聚集和磷酸盐诱导的凝集行为

DOI：
发表时间：
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0
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T.Tanaka, K.Endo, Y.Aoyama: "Stacked Porphyrin Arrays from Hydrogen-Bonded Porphyrin-Resorcinol 1D Chains"Bull.Chem.Soc.Jpn.. 74. 907-916 (2001)

T.Tanaka、K.Endo、Y.Aoyama：“氢键卟啉-间苯二酚 1D 链的堆叠卟啉阵列”Bull.Chem.Soc.Jpn.. 74. 907-916 (2001)

DOI：
发表时间：
期刊：
影响因子：
0
作者：
通讯作者：

Osamu Hayashida, Keiji Mizuki, Kazuyuki Akagi, Aki Matsuo, Takuya Kanamori, Takuya Nakai, Shinsuke Sando, Yasuhiro Aoyama: "Macrocyclic Glycoclusters. Self-Aggregation and Phosphate-Induced Agglutination Behaviors of Calix[4]resorcarene-Based Quadruple-Ch

Osamu Hayashida、Keiji Mizuki、Kazuyuki Akagi、Aki Matsuo、Takuya Kanamori、Takuya Nakai、Shinsuke Sando、Yasuhiro Aoyama：“大环糖簇。Calix[4]基于间苯二酚的四联体的自聚集和磷酸盐诱导的凝集行为