Collaborative Industrial/Academic Research on Alternate Phosgene Chemistry for Environmentally Benign Chemical Synthesis and Processing

在与工业界学术联络的资助机会（GOALI）倡议下，有机合成项目和数学与物理科学理事会多学科活动办公室支持罗切斯特大学化学系威廉·琼斯教授的研究。琼斯教授与伊士曼柯达公司合作，通过在合成硫代氨基甲酸酯、尿素和异氰酸酯中间体中取代光气作为酰基来源，并通过在酰胺合成中取代酰基氯化物，为摄影化学品的生产开发更环保的合成和加工化学。新发现的过渡金属催化剂允许用一氧化碳代替光气，这种催化剂激活一氧化碳向亲核试剂的顺序加成，允许从简单和相对安全的前体形成硫代氨基甲酸酯和相关的官能团。催化系统的机理研究为改进催化剂设计提供了见解，并将导致催化范围的扩展，以允许其他杂基和碳基亲核试剂的偶联。光气是合成化学工业中必不可少的试剂，但这种高毒性气体对人类生命和环境的危害是巨大的。在工业界学术联络资助计划（GOALI）的支持下，琼斯教授探索了一氧化碳作为相对安全的光气替代品的使用。虽然一氧化碳本身不具有反应性，但可以通过使用含金属的催化剂来诱导一氧化碳形成与用其他方法从光气制备的产物相同的产物。这些研究可能会导致伊士曼柯达公司大规模生产感光化学品时光气的使用显著减少，该公司是GOALI合作研究计划的参与者之一，而且这些研究的长期影响远远超出了感光化学品领域。参与该项目的学生和博士后学者将花费大量时间在柯达实验室学习和研究工艺开发化学，从而将这种在学术环境中通常不会遇到的广泛经验带回罗切斯特大学。

Under the Grant Opportunities for Academic Liaisons with Industry (GOALI) initiative, the Organic Synthesis Program and the Office of Multidisciplinary Activities of the Directorate for Mathematical and Physical Sciences support the studies of Professor William Jones of the Department of Chemistry at the University of Rochester. Professor Jones, in collaboration with Eastman Kodak Company, develops environmentally more benign synthesis and processing chemistry for photographic chemicals production through the replacement of phosgene as an acyl source in the synthesis of thiocarbamate, urea, and isocyanate intermediates and through the replacement of acyl chlorides in amide syntheses. Replacement of phosgene with carbon monoxide is permitted by newly-discovered transition-metal based catalysts which activate carbon monoxide toward the sequential addition of nucleophiles, allowing the formation of thiocarbamates and related functional groups from simple and comparatively safe precursors. Mechanistic studies of the catalytic systems offer insights into improved catalyst design and will lead to the extension of the scope of the catalysis to permit the coupling of other hetero- and carbon-based nucleophiles. Phosgene is an essential reagent in the synthetic chemicals industry, but the hazards of this highly toxic gas to both human life and to the environment are significant. With support under the Grant Opportunities for Academic Liaisons with Industry (GOALI) initiative, Professor Jones explores the use of carbon monoxide as a comparatively safe substitute for phosgene. Although rather unreactive by itself, carbon monoxide may be enticed through the use of metal-containing catalysts to form the same products as are otherwise prepared from phosgene. These studies may lead to significant reductions in the use of phosgene in the large-scale production of photographic chemicals at Eastman Kodak Company, a coparticipant in this collaborative GOALI research program, and the long-range implications of the studies go well beyond the photographic chemicals arena. Students and postdoctoral scholars involved in the project will spend significant periods of time learning about and working on process development chemistry in Kodak's laboratories, thereby bringing this breadth of experience, not ordinarily encountered in the academic environment, back to the University of Rochester.