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Synthesis of Poly (thioether) s by Nucleophilic Substitution of Chromium-Arene Complex

铬芳烃配合物亲核取代合成聚硫醚

基本信息

批准号：
08651046
负责人：
KAKIMOTO Masa-aki
金额：
$ 1.41万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1997
项目状态：
已结题

项目摘要

Chromium-arene complex was prepared from p-dichlorobenzene and chromium hexacarbonyl. Stability in organic solvents and reactivity of the complex for nucleophilic aromatic substitution were investigated in detail.The complex was prepared from chromium-hexacarbonyl and p-dichlorobenzene, as reported in literature. The final purification process was changed to sublimation instead of column chromatography. Spectroscopic data and its melting point were consistent with those in literature.Stability of the complex in organic solvents is investigated by the change of absorption at 325 nm. The absorption decreased to 70% from the initial one after 1 h in non-polar solvents. The decrease is independent on the presence of water and oxygen. Exchange reaction or dissociation of ligand may exist in the solution.Nucleophilic aromatic substitutions by phenol and thiophenol were carried out in DMSO at 100ﾟC.The ratio of mono and disubstituted product was estimated from the crude product without isolation by HPLC measurements. Disubstituted product was obtained by the reaction of thiophenol. The fact indicates that second substitution by thiophenol proceeds smoothly whereas ether bond retard the second substitution by phenol. Decomplexation reaction proceeded efficiently by oxidation by I_2.Polymerization of the complex has not been investigated because the complex is not very stable in organic solvents. Rapid propagation reaction is required to use the complex as a monomer for polycondensation.

以对二氯苯和六羰基铬为原料制备铬芳烃络合物。详细研究了配合物在有机溶剂中的稳定性以及亲核芳香取代反应的反应性。据文献报道，该配合物是由六羰基铬和对二氯苯制备的。最终的纯化过程由柱色谱改为升华。光谱数据及其熔点与文献一致。通过325 nm处吸收的变化考察配合物在有机溶剂中的稳定性。在非极性溶剂中 1 小时后，吸收率从最初的吸收率降至 70%。该减少与水和氧气的存在无关。溶液中可能存在配体的交换反应或解离。苯酚和苯硫酚在DMSO中于100℃下进行亲核芳族取代。通过HPLC测量，从未经分离的粗产物中估算出单取代产物和双取代产物的比例。由苯硫酚反应得到双取代产物。事实表明，苯硫酚的二次取代顺利进行，而醚键则阻碍了苯酚的二次取代。通过I_2的氧化可以有效地进行解络反应。由于络合物在有机溶剂中不太稳定，因此尚未研究络合物的聚合反应。使用该配合物作为缩聚单体需要快速的增长反应。