公开(公告)号：EP2598509A1

公开(公告)日：2013-06-05

申请号：EP11781995.3

申请日：2011-07-27

申请人： Ustav Organicke Chemie a Biochemie Akademie Ved Ceske Republiky, V.V.I.

发明人： JANSA, Petr ,  HOLY, Antonín ,  CESNEK, Michal

IPC分类号： C07F9/40

CPC分类号： C07F9/4006

摘要： The invention deals with the method of the synthesis of dialkyl haloalkylphosphonates and dialkyl haloalkyloxyalkylphosphonates via a microwave-heated Michaelis-Arbuzov reaction of trialkylphosphites with dihaloalkanes or bis(haloalkyl)ethers in a closed vessel, during which the reaction mixture, containing a dihaloalkane or bis(haloalkyl)ether and a trialkylphosphite, is heated with microwave radiation with the standard frequency (2.45 GHz) to reach a reaction temperature which is specific for each individual halogen. In the subsequent reaction of the first dihaloalkane or bis(haloalkyl)ether halogen atom with trialkyl phosphite, the desired dialkyl haloalkylphosphonate or dialkyl haloalkyloxyalkylphosphonate is formed, but the reaction of its halogen atom with the so-far present trialkylphosphite, leading to the creation of the relevant bisphosphonate, no longer takes place. In the case of an inhomogeneous reaction mixture, also the desired product in the amount of 0.1-5 molar % is added to the reaction mixture for its homogenization, which homogenizes it and thus precludes its uncontrollable overheating. The entire process of synthesis is more effective, faster, less expensive and more environmentally friendly than the methods described so far in the literature. The possibility of performing the described procedure also in a continuous-flow microwave reactor allows industrial production with minimal demands on an optimization of the reaction conditions for larger quantities, eliminates some security risks, dramatically reduces the spatial demands in production and reduces the need for the usage of large-tonnage industrial reactors.

摘要翻译： 本发明涉及通过在密闭容器中通过三烷基亚磷酸酯与二卤代烷烃或双（卤代烷基）醚的微波加热的迈克尔斯 - 阿布佐夫反应合成卤代烷基膦酸二烷基酯和二烷基卤代烷氧基烷基膦酸酯的方法，其中含有二卤代烷或二 （卤代烷基）醚和三烷基亚磷酸酯，以标准频率（2.45GHz）的微波辐射加热，达到对于各个卤素特异的反应温度。 在第一个二卤代烷烃或双（卤代烷基）醚卤素原子与亚磷酸三烷基酯的反应中，形成了所需的卤代烷基膦酸二烷基酯或卤代烷基氧基烷基膦酸二烷基酯，但其卤素原子与目前为止存在的亚磷酸三烷基酯反应，导致产生 相关的二膦酸盐，不再发生。 在不均匀的反应混合物的情况下，将均匀化均匀化的反应混合物中所需的0.1-5摩尔％的量也加入其中，从而排除其不可控制的过热。 整个合成过程比文献中迄今描述的方法更有效，更快，更便宜，更环保。 在连续流微波反应器中执行所描述的过程的可能性允许工业生产对较大量的反应条件的优化的需求最小化，消除一些安全风险，大大降低了生产中的空间需求，并且减少了对 大吨位工业反应堆的使用。