Novel Synthetic Methodology Utilizing Fluorous Phases as a Liquid Screen

利用氟相作为液体筛选的新型合成方法

基本信息

批准号：
15550095
负责人：
MATSUBARA Hiroshi
金额：
$ 2.43万
依托单位：
Osaka Prefecture University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

项目摘要

In this project, we studied "the Phase-Vanishing(PV) Method". This novel method that we developed recently utilizes unique properties of the fluorous phase. The PV method, which capitalizes on the diffusion of reagents through the fluorous phase, is very simple methodology, and does not need any dropping funnels, heating/cooling baths, and thermometers. Inspection of suitable solvent for the PV method reveals that FC-72(perfluorohexanes) is an outstanding fluorous solvent. Firstly we examined bromination of olefins with Br2 ; this reaction finished in 2 days with standing to afford corresponding dibromide in 68-97% yields, while gentle stirring of the bromine layer, taking care not to mix the three layers, the reaction completed in 4 hours giving similar yields (88-91%). We also carried out various organic reactions including demethylations of aryl methyl ethers with BBr_3, bromination of alcohols with PBr_3 or SOBr_3, and the Friedel-Crafts acylations of aromatic compounds with SnCl_4 using the PV method, and showed that the method gave corresponding products in good yields. A parallel synthesis of the PV method in the Friedel-Crafts acylations using a very simple multi-fingered glass apparatus is also performed successfully, providing four types of aromatic keteones in high yield (64-85%) at once. During this project with FC-72 we have found that the solvent has weak points. Namely, the recovery of FC-72 is invaluably incomplete due to its high volatility, and in the parallel synthesis we sometimes faced contamination of products. In order to overcome these problems, we searched again more suitable fluorous solvents for the PV method than FC-72, and found that perfluoropolyethers (Galden) are a superior solvent.

在这个项目中，我们研究了“相变（PV）方法”。我们最近开发的这种新颖方法利用了易流相的独特特性。 PV方法将试剂通过透明阶段扩散而利用，这是非常简单的方法，并且不需要任何掉落的漏斗，加热/冷却浴和温度计。对PV方法的合适溶剂检查表明，FC-72（Perfluorohexanes）是一种出色的荧光溶剂。首先，我们检查了用BR2对烯烃的溴化。该反应在2天内完成，站立可提供68-97％的收益率，而溴层的温和搅拌，注意不要混合三层，该反应在4小时内完成了相似的收率（88-91％）。我们还进行了各种有机反应，包括用BBR_3的芳基甲基醚的脱甲基化，具有PBR_3或SOBR_3的醇的溴化以及使用PV方法的芳族化合物的Friedel-Crafts酰基化，并使用PV方法表明该方法具有良好的收益率。还可以成功地执行使用非常简单的多指玻璃设备在Friedel-Crafts酰基中的PV方法的平行合成，同时提供了高产量（64-85％）的四种类型的芳族酮酮。在使用FC-72的项目中，我们发现溶剂具有弱点。也就是说，由于FC-72的恢复，由于其高波动性，因此不完全是不完整的，在平行的合成中，我们有时会面临产品的污染。为了克服这些问题，我们再次搜索了与FC-72相比，PV方法更合适的荧光溶剂，并发现全氟去剂（Galden）是一种优越的溶剂。