Chemical Spectroscopy photochemical organic reactions in micro reactors

光化学是生产重要和有价值的化学品的重要方法，特别是用于医疗应用（例如抗癌药物）。然而，目前通常用于合成这些化合物的方法（在搅拌反应器中批量合成）是有限的，它不允许有效地扩大生产规模，也不允许开发独特的反应途径，其中需要仔细控制反应时间和暴露于光下。为了应对这些挑战，该项目提出了一种协调的方法，将化学、工艺工程和现场分析技术的专业知识结合起来，以前所未有的实时洞察反应过程和条件来探索连续流动光化学。在流动微反应器中，利用利用反应/产物混合物的可变红外吸收的原位浓度传感器，利用基于法布里-珀罗过滤器的新型检测器，探索吲哚和茚唑的光氧化催化酰化，以及氧化环化到酰基吲哚。这些过滤器将扩展提案第一阶段的初步发现，其中多层布拉格反射镜之间的阶梯间隔的静态过滤器被开发并被证明有效地监测2,1-苯并恶隆酮合成的进展。一个主要的发展将是扩大这些传感器的能力，用液晶弹性体取代静态分离器，其尺寸可以通过加热改变。这将使传感器能够独立地调谐到不同的目标红外波长，并使它们适应一系列不同的化学物质。这些先进的传感器将在许多独立的反应器中实现，用于观察目标化学中的不同反应步骤，特别侧重于在微反应器流动光化学条件下获得不同反应步骤的有用反应动力学参数。在项目的最后一部分，将不同的贡献汇集在一起，将允许传感器部署在多个反应器、分离器和其他连续流、多步骤系统中的过程单元中，将一个控制系统充分利用红外传感器提供的实时成分数据。为了补充这一强大的实验工作，将进行并行建模活动，其中将进行微流体流道中光化学的分析和数值模型。模型结果将与得到的实验结果进行比较，为流动光化学系统提供额外的见解，特别是为设计未来的流动光反应器提供有用的指导。

Photochemistry is an important method for the production of important and valuable chemicals, especially for medical applications (for example, anti-cancer drugs). However the current methods often used to synthesise these compounds (batch synthesis in stirred reactors) is limited, it does not allow for effective up-scaling of the production, nor does it allow for the exploitation of unique reaction pathways where careful control of reaction time and exposure to light is required. To address these challenges, this project proposes a coordinated approach bringing together expertise in chemistry, process engineering and in situ analytic technqiues, to explore continuous flow photochemistry with an unprecendented level of real-time insight into reaction progress and conditions. The photoredox-catalysed acylation of indoles and indazoles, as well as the oxidative cyclization to acylindoles will be explored in flow micro reactors, utilizing in situ concentration sensors exploiting the variable IR absorption of the reaction/product mixtures, which will be detected using novel detectors based on Fabry-Perot filters. These filters will expand on initial discoveries in Phase 1 of the proposal, where static filters with stepped spacings between the multi-layer Bragg mirrors, were developed and proven effective in monitoring the progress of 2,1- Benzoxalonone synthesis. A major development will be to expand the capability of these sensors be replacing the static separators with liquid crystal elastomers, whose dimensions can be changed by heating. This will enable the sensors to be independently tuned to different target IR wavelengths, and making them adaptable to a range of different chemistries. These advanced sensors will be implemented in a number of standalone reactors looking at different reaction steps in the target chemistry, with a particular focus on obtaining useful reaction kinetic parameters for the separate reaction steps, under micro reactor flow photochemistry conditions. In the final part of the project, bringing together the different contributions will allow for the sensors to be deployed in multiple reactors, separators and other process units in a continuous flow, multi-step system, will a control system making full use of the real-time composition data provided by the IR sensors. Complementing this robust experimental work, will be a parallel modeling activity, where both analytical and numerical models of photochemistry in a microfluidic flow channel will be carried out. The model results will be compared to the obtained experimental results, providing additional insight into the flow photochemistry system and especially providing useful guidance in designing future flow photo reactors.