研究有机反应机理的方法.ppt

有机反应机理 有机反应机理的研究方法 动力学同位素效应 有机反应中间体 3. 同位素效应 研究证明, C-H 键断裂所需活化能比C-D键断裂所需活化能要小, 因此, C-H键的反应速率比C-D键反应速率要大, 动态同位素效应就是根据这一差别而定义的. 动态同位素效应kH/kD D2O; CDCl3, CD3SOCD3 醇的氧化反应 * * 第一章 有机反应机理及研究方法 高分子工程室 张所波 第一章 有机反应机理的研究方法 1.有机反应机理 (Proposing Reaction Mechanism) Let’s work out a reasonable mechanism for a simple reaction: one you probably haven’t seen before. Since the overall result of the reaction is to replace an ethoxy group by a cyanide group, it may be tempting to propose an SN2 mechanism. However, an essential requirement for any SN2 reaction is that the group being displaced by the nucleophile must be a good leaving group. Only a small group of anions, all the conjugated bases of strong acids, can act as leaving groups in typical SN2 reactions. That group includes chloride, bromides, and iodide anions, as well as derivatives of sulfate anions, such as benzenesulfonate anions. Neutral molecules, such as water and alcohols, can act as leaving groups in SN2 and E2 reactions under acidic or basic conditions. Proposing a reasonable Reaction Mechanism. How can you select a reasonable mechanism for the reaction described above? Don’t start out by trying to arrive at the products of the reaction. Instead, focus on the starting materials, and select the reaction they are most likely to undergo under the reaction conditions. Then, do the same with the products of the reaction you’ve proposed and, if necessary, with the products of the second reaction and later reactions. It is surprising how often a sequence of the most likely steps will lead to the actual reaction products. The staring organic compound is an alcohol, which will be partially converted to its anion by reaction with cyanide ions or other bases. Ignore the fact that this reaction may not seem to be leading to the desired product, and consider what can happen to the new anion. It can, of course, pick up a proton to give back the starting alcohol, but obviously, that leads nowhere. The only other reacti