公开(公告)号：US20120232257A1

公开(公告)日：2012-09-13

申请号：US13390311

申请日：2010-10-04

Applicant: Nikolas Pietrzik

Inventor： Nikolas Pietrzik

IPC: C07C201/02 ,  C07H5/04 ,  C07H1/00 ,  C07C203/04 ,  C07D251/06 ,  C08B5/02 ,  C07H7/02

CPC classification number: C07B43/02 ,  C07C313/36 ,  C07D251/06 ,  C07H9/04

Abstract: The invention relates to a nitration method having the following principles: a phosgene species is converted with two equivalent silver nitrates into a double-mixed anhydride of carbonic acid and nitric acid, known here as carbonic acid dinitrate (I). Said operation is carried out in situ, and the formed dinitrate decomposes spontaneously. In addition to carbon dioxide, nitrate ions and nitronium ions are formed, said ions comprising electrophiles which are necessary for nitration. The solution which is used is acetonitrile, and is insignificant if the alcohol species is dissolved or suspended. The necessary equivalent silver nitrates are introduced into the system and optionally heated or cooled to the desired temperature. Subsequently, the acid chloride is introduced slowly, drop by drop or slowly little by little. Phosgene, diphosgene, triphosgene and chloroformic acid ester can be used as carbonic acid dichloride and monochloride, and their thiocarbonic acid analogues. A brown colouration and precipitated silver chloride display the formation of the carbonic acid reactants, said brown colouration rapidly discolouring due to an immediate reaction of the nitronium ions with the substrate with is to be nitrated. Towards the end of the addition of phosgene, the brown colouration remains for longer and longer until it no longer disappears. Then, it is stirred for another hour at room temperature. In the event of high acid-sensitive educts, non-nucleophilic nitrogen bases such as DBU can be added to the system in order to intercept the formation of nitric acid.

Abstract translation: 本发明涉及一种具有以下原理的硝化方法：将光气物质用两当量的硝酸银转化成碳酸和硝酸的双重混合酸酐，这里称为硝酸二苯酯（I）。 所述操作在原位进行，形成的硝酸酯自发分解。 除了二氧化碳之外，还形成硝酸根离子和硝鎓离子，所述离子包含硝化所必需的亲电体。 使用的溶液是乙腈，如果醇类物质溶解或悬浮，则不重要。 将必需的相当的硝酸银引入体系中，并任选地加热或冷却至所需温度。 随后，缓慢逐滴引入酰氯，或逐渐缓缓地引入。 光气，双光气，三光气和氯甲酸酯可用作二氯化碳和一氯化碳及其硫代碳酸类似物。 棕色着色和沉淀的氯化银显示碳酸反应物的形成，棕色着色由于硝基离子与底物立即反应而迅速变色将被硝化。 在加入光气结束时，棕色着色会持续更长时间，直至不再消失。 然后在室温下再搅拌1小时。 在酸敏感性离析物高的情况下，可以向体系中加入非亲核性氮碱如DBU，以拦截硝酸的形成。