Dynamic Reaction Monitoring as Enabling Technology for Developing New Selective Catalytic Syntheses in the Fine Chemical Industry

在这个项目中，我们将使用先进的FlowNMR光谱加上其他互补技术，如紫外-可见光谱，质谱和高效液相色谱，实时研究分子溶液相变，特别是过渡金属配合物的催化作用。目的是得到动力学和机理信息，使我们能够改进现有的工艺，并带来与工业精细化学合成相关的新反应性。示例工作包包括：1)Ru-和v -催化烷烃的Meyer-Schuster重排反应。在初步联合工作的基础上，建立对流动中这些空气敏感转换的监测，利用选择性激励脉冲序列，异核磁共振和二维技术来量化催化剂中间体。除了建立可靠的定量实时监测该反应的方法外，主要的重点是了解和防止催化剂失活以提高生产率。2) Ru/Rh/ ir催化选择性加氢反应。将装置扩展到在二氢作为还原剂的压力下工作，并建立对氢和氘化技术，目的是增加对机制的理解，从而提高选择性。3)酸催化碳链延伸反应。开发先进的13C FlowNMR方法和反应工程解决方案，包括质谱采样，以便在高温高压下跟踪C3和C4延伸反应，目的是了解反应途径。4)铜催化酚类有氧氧化生成醌。探索在流动中利用顺磁核磁共振波谱的可能性，目的是建立一种方法来研究通过开壳物质进行的氧化反应。这项工作将在巴斯大学的动态反应监测设施进行，由Ulrich hintermaair博士监督。帝斯曼以获取研发材料、前景知识产权和安置机会的形式提供战略建议和项目支持。同意每3个月通过电子邮件或电话进行项目更新，每6个月面对面或通过Skype进行项目会议，每12个月进行书面报告。

In this project, we will use advanced FlowNMR spectroscopy coupled with other complementary techniques such as UV-vis spectroscopy, mass spectrometry and high-performance liquid chromatography for real-time investigations of molecular solution phase transformations, catalysis with transition metal complexes in particular, with the aim of deriving kinetic and mechanistic information that will allow us to improve existing processes and bring about new reactivity of relevance to industrial fine chemical synthesis.Example work packages include:1) Ru- and V-catalysed Meyer-Schuster rearrangement reactions of alkinols. Building on preliminary joint work, establish monitoring of these air-sensitive transformations in flow, utilising selective excitation pulse sequences, hetero-nuclear NMR and two-dimensional techniques to quantify catalyst intermediates. Main focus besides establishing reliable methods for quantitative real-time monitoring of this reaction is understanding and preventing catalyst deactivation to improve productivities.2) Ru/Rh/Ir-catalysed selective hydrogenation reactions. Extend setup to work under pressures of dihydrogen as reductant, and establish para-hydrogen and deuteration techniques with the aim of increased mechanistic understanding allowing to improve selectivities.3) Acid-catalysed carbon chain elongation reactions. Develop advanced 13C FlowNMR methods and reaction engineering solutions including mass spectrometry sampling to allow tracking C3 and C4 extension reactions at high temperature and pressure with the aim of understanding the reaction pathway.4) Cu-catalysed aerobic oxidations of phenols to quinones. Explore the possibility of utilizing paramagnetic NMR spectroscopy in flow with the aim of establishing a method for investigating oxidation reactions proceeding through open-shell species.The work will be carried out in Bath's Dynamic Reaction Monitoring Facility, supervised by Dr Ulrich Hintermair. DSM offer strategic advice and project support in form of access to R&D materials and foreground IP as well as placement opportunities. Project updates by email or telephone were agreed to occur every 3 months, project meetings in person or via Skype every 6 months, and written reports every 12 months.