声化学(2013)课件.pptVIP

Sonochemical Reformatsky Reaction Using Indium BANG, K.; LEE, K.; PARK, Y. K.; LEE*, P. H.; Bull. Korean Chem. Soc. 23 (2002) 9, 1272-1276 Sonochemical Reformatsky reaction of carbonyl compounds (I) with bromoacetates such as (II) in the presence of indium metal affords the corresponding β-hydroxyesters (III) (21 examples) in good to excellent yields High-Intensity Ultrasound-Promoted Reformatsky Reactions Nathan A. Ross and Richard A. Bartsch*（J. Org. Chem. 2003, 68, 360-366） In some instances, ultrasonic irradiation can be utilized to advantage as an alternative for organic reactions ordinarily accomplished by heating. Han and Boudjouk reported that the use of a low-intensity ultrasonic (LIU) laboratory cleaning bath greatly improved the rates and yields for Reformatsky reactions of simple aldehydes and ketones with ethyl bromoacetate. However, the zinc dust still had to be “activated” using the “Cava” method, and the reported conditions called for dried, distilled dioxane as the optimal solvent. 大位阻效应，即使HIU（高强度超声波）条件下也不发生反应 Irradiation of a mixture of a phenyl ketone, an ?-bromoester, zinc dust, and iodine in dioxane with an HIU horn gave very high yields of ?-hydroxyesters in short reaction time. Only when the reactants became extremely bulky did the HIU-promoted Reformatsky reaction fail. It was not necessary to activate the zinc, and undistilled, reagent-grade dioxane was used. These factors, as well minimal purification of the crude products, make the HIU method attractive for performing Reformatsky reactions. 超声对化学体系的作用具有广阔的应用前景。对经典有机反应、金属参与的反应，纳米材料制备。此外，对高分子降解、环境有害物消除等均可获得明显的效果。 超声应用于化学反应的工作仍不广泛和深入，许多反应的真实机制和声化学的本质尚有待探究。尽管如此，超声可以促进化学反应，提高产率或改变反应条件是可以肯定的，问题是怎样选择好影响声化学反应的条件，以充分发挥超声对化学体系的作用，在这方面也需要广泛地进行实验和探索。 结 语 谢 谢 ! * * 酮的偶联反应：将TiCl4和镁粉再THF中混合后加入酮，超声数分钟至1h，反应即告完成。 如：苯乙酮的偶联，在超声辐射后，在室温下反应 10 min即得到92％收率，得到1，2－二甲基－1，2－二苯乙烯。 偶联反应 Lim等报道，在超声作用下的水溶液中，以铟为还原剂，由芳香醛还原偶合制备邻二醇得到很好的效果。 例如，以苯甲醛为底物反应８h，收率70.3% 无超声作用反应48 h，收率仅 20%。 邻