稀土化合物催化合成磷(膦)酸酯和磷杂环戊烷的分析-analysis of rare earth compounds for catalytic synthesis of phosphorus ( phosphine ) esters and phosphorus heterocyclic cyclopentane.docx

目录前言·····························································································1第一章硅氨基稀土化合物催化phospha-aldol-Brook重排反应的研究···············2第一节文献综述··································································2第二节结果与讨论································································10参考文献···················································································28第二章稀土化合物催化亚磷酸二乙酯与α,β-不饱和酮的加成错误!未定义书签。第一节文献综述·································································30第二节结果与讨论······························································35参考文献···················································································53第三章实验部分·············································································56第一节原料及试剂······························································56第二节分析与测试······························································69第三节硅氨基稀土化合物催化phospha-aldol-Brook重排反应的研究·70第四节稀土化合物催化亚磷酸二乙酯与α,β-不饱和酮的加成··········71参考文献···················································································72附录····························································································73攻读学位期间发表的论文··································································109致谢··························································································110前言稀土金属在过渡金属领域占有重要地位，其催化的有机反应是当今有机合成方法学和绿色化学研究领域的热点。我国是世界上稀土资源最丰富的国家之一，因此，对于我国稀土化学工作者来说，在基础理论和实际应用方面更好地研究对稀土资源的开发利用责无旁贷。近年来，稀土化合物在有机合成中的应用有了突飞猛进的发展。利用稀土金属离子的强Lewis酸性和高配位数的性质，稀土化合物可以催化多种类型的有机反应。尽管稀土化合物在催化有机反应的领域中已产生了很多极有价值的结果，但这方面的研究还有很大的开发空间。比如对于含不同碱基配体的稀土化合物，如何通过碱基的调控实现有机反应的选择性；如何通过底物的设计及反应条件的调整，发展高活性的新颖的合成路线，等等，这些都是极有意义的研究内容。有机磷化合物由于其性质的多样性而在诸如医药、农药、表面活性剂、金属防腐剂、高分子材料和精细化工的多个领域被广泛应用。如α-酰基磷酸酯是一种很有价值的有机合成中间体，可转化成为多种重要有机分子；γ-氧代膦酸酯的生理活性及其在药物学方面的潜在的和实际的应用性已多有报道；2-氧杂磷杂环戊烷类化合物具有潜在的生物活性和一些独特的性质，如可以用作塑料和树脂的热保护剂等。但通过调研文献我们发现，α-酰基磷酸酯的合成大多需要比较苛刻的反应条件，γ-氧代膦酸酯与2-氧杂磷杂环戊烷虽有可能由同样的原料通过不同程度的反应得到，但有效的选择性的合成方法却未见报道。因此，发展这些化合物的高效合成方法是很有意义的。在我们实验室原先工作的基础上，我们希望利用硅氨基稀土化合物和芳氧基稀土化合物的独