化学化工专业英语解剖.ppt

Oxidation Reaction of C—H Bond Alcohols may be considered to be the first product of oxidation of the alkanes in the oxidation scheme, which eventually produces carbon dioxide and water. Alcohols might be expected to be subject to further oxidation .This has been found to be the case as long as a hydrogen atom (α-hydrogen) remains bonded to the carbon atom which has already been partially oxidized. The following equations illustrate the structural changes which occur; it should be emphasized that they do not illustrate the mechanistic steps of the reactions [(1) and (2)]. 1. C-H键的氧化反应 醇可以被认为是烷烃氧化过程中的氧化初产品。这个过程将最终生产CO2和H2O。醇曾被认为可被进一步氧化。已经发现，只要部分氧化的碳原子上仍有氢原子（α-H），就有进一步氧化的可能。下面的方程列出了所发生的结构变化，需要强调的是这些方程并不能真正反映反应（1）和（2）的机理。 (1) l0alcohol unstable intermediate aldehyde carboxylic acid (2) 20alcohol unstable intermediate ketone The above reaction involve the C—H bond. Since 30 alcohol have no α-hydrogen atom bonded to the partially oxidized carbon atom, they are resistant to further oxidation. 上述反应均有C-H键的参与。由于3级醇部分氧化的碳原子上没有α-H的存在。因此，它不易被进一步的氧化。 2. Reaction of O—H Bond The proton bonded to oxygen of an alcohol is much more acidic than protons bonded to carbon. This difference can be readily accounted for on the greater electronegativity of oxygen, which polarizes the O—H bond. The hydrogen on oxygen is replaceable by sodium for example (3). (3) 2RCH2OH + 2Na → 2RCH2O-Na+ + H2 2. O-H键的反应 醇中氧原子所键合的质子要比碳原子所键合的质子酸性要强。这种差别很容易用氧的电负性较大，因而它极化了O-H键而进行解释。例如氧原子上的氢容易被钠所取代。 This reaction is analogous to the liberation of hydrogen by reaction of an acid and a metal. The order of reactivity of alcohols in this reaction is:l0＞20＞30. The reason for this order of reactivity is believed to be the result of the inductive effects of alkyl groups. Utilizing the relative electronegativity value of 2.1 for hydrogen and 2.5 for carbon, the H—C may be represented as follows: Hδ+→Cδ- . 这个反应与金属置换酸中的氢的反应很相似。在这个反应中，醇的反应活性顺序是1＞2＞3。这个反应顺序的原