发展光气及替代品的特异性有机反应及其传感应用

Phosgene and its substitutes, diphosgene and triphosgene, have widely been used in organic synthesis as a synthetic auxiliary in the preparation of many important classes of organic compounds. More and more investigations have been revealing that triphosgene is not an equivalent of phosgene, even different products were obtained in the presence of different bases as catalytes. Their mechanisms remain to be clarified. Furthermore, as highly toxic substances, phosgene and diphosgene were used as chemical weapon agents (CWAs) during World War I, World War II and the Iran-Iraq war. In contrast to nevre agents, whose production is strictly controlled and prohibited by laws, phosgene and diphosgene are widely used industrial materials. For this reason, phosgene and its substitutes become a serious threat to public health safety for both its potential use by terrorists and its unexpected release during industrial accidents. Therefore, it is urgent to develop facile, sensitive and selective methods for detecting phosgene, such as by using fluorescent molecular sensors. In this project, we will study kinetics of organic reactions promoted by phosgene and its substitutes with alcohols or amines, and establish the linear relationship of the reactivity and the structure. Specific organic reactants will be constructed for reactions with phosgene or its substitutes meticulous molecular design, and their mechanisms will be clarified. Next, with the specific reactions as the sensing sites, effective chemosensors will be designed and synthesized to achieve highly sensitive and highly selective detection of phosgene and its substitutes. Meanwhile, in view of similar electrophilicity with phosgene and its substitutes, new organic sensing reactions caused by nerve agents will also be developed.

光气及其替代品（二光气、三光气）在有机合成中有着广泛的应用，是合成多种有机物的重要砌块。光气替代品因计量、操作方便而取代了光气。越来越多的研究表明，光气替代品与光气并非等价物，且不同碱存在时反应结果迥异，其机理问题有待阐明。同时，剧毒的光气、二光气作为化学战剂用于一、二战和两伊战争。这样，广泛使用的光气替代品对公共安全构成了巨大的威胁。应对这一威胁，迫切需要建立一种准确识别、快速检出光气及替代品的方法。因此，本项目拟开展涉及光气及替代品的有机反应的动力学研究，建立反应活性与结构之间的线性关系，阐明反应机理；通过精心的分子设计，发展光气及其替代品参与的特异性的有机反应。进一步，以特异性有机反应为传感位点，选择合适的荧光团，构建高效特异性的化学传感器，实现高灵敏、高选择性地探测光气及替代品，能够从性质相似的干扰物（包括神经毒剂模拟物）中准确检出，同时，探索新的神经毒剂的有机传感反应。

光气及其替代品（二光气、三光气）在有机合成中有着广泛的应用，是合成多种有机物的重要试剂。三光气因计量、操作方便及容易转化为光气而取代光气。同时，剧毒的光气、二光气作为化学战剂用于一、二战和两伊战争。目前，广泛使用的光气及替代品对公共安全构成了重大威胁，为此，迫切需要建立一种准确识别、快速检出光气及替代品的方法。本项目致力于开发涉及光气及替代品的特异性有机反应，建立反应活性与结构之间的关系，并阐明反应机理。在发展的涉及三光气的有机反应中，二类是新的有机反应：由酰化联胺构建噁二唑酮衍生物、由2-甲基喹啉/吡啶N-氧化物一锅制备2-氯甲基喹啉/吡啶，并论证了反应机理。这二类反应条件温和，底物范围宽，反应快速，产率高。在光气及其替代品传感应用方面，通过精心的分子设计，以特异性有机反应为传感位点，选择萘二酰亚胺、香豆素、BODIPY和喹啉等荧光团，构建了七款特异性的化学传感器，可实现快速(<1s）、高灵敏（0.05nM）及高选择性地探测分析。同时，探索了神经毒剂模拟物、芥子气及类似物的新的有机传感反应，分别设计合成了二款相应的荧光探针。本项目研制的三类化学毒剂的检测试剂及试纸，与其他检测方式相比，它们费用低，携带方便、操作简单，适用于公安应对化学恐怖袭击和化学突发事件，对可疑物进行现场点测、快速筛查化学毒剂。