高等有机课件Chapter 6 Aromatic Substitution, Electrophilic.pptVIP

Chapter 6 Aromatic Substitution, Electrophilic Hongjun Zhu Most substitutions at an aliphatic carbon are by nucleophiles. In aromatic systems the situation is reversed, because the high electron density at the aromatic ring leads to its reactivity as a Lewis base or a Bronsted–Lowry base, depending on the positive species. In electrophilic substitutions, a positive ion or the positive end of a dipole or induced dipole is attacked by the aromatic ring. The leaving group (the electrofuge) must necessarily depart without its electron pair. In electrophilic substitutions the most important leaving groups are those that can best exist without the pair of electrons necessary to fill the outer shell, that is, the weakest Lewis acids. 6.1 MECHANISMS ORIENTATION AND REACTIVITY Quantitative Treatments of Reactivity in the Substrate Hammet t 方程是L. P. Hammet t 在1935 年考查一系列间位和对位取代的苯衍生物在侧键上的反应关系后建立的。他发现, 间位或对位取代苯甲酸的电离常数(Ka) 和苯甲酸的电离常数(K oa) 之比的对数值是一个常数: σ和ρ的意义 取代基常数σ的意义 σ表示电子效应的大小,即取代基接受电子或给出电子能力的大小;或者是取代基在反应中,相当于H的极性效应的相对度量. 吸电子基σ为正,给电子基σ为负. σ取代基常数,决定于取代基的结构和在苯环中的位置.不依赖于反应常数,即与反应类型无关. 这种电子效应同时包括了诱导效应和共轭效应,是二者的综合结果. 反应常数ρ的意义 反应常数ρ是某一类反应对取代基电子效应的敏感性的尺度. 从化合物结构分析,ρ为正值时,表示反应物的反应中心在决定速度步骤的过渡态或中间体比起始态有更多的负电荷,或者正电荷有所减少; ρ为负值,则相反.如芳环的亲电取代反应等. The Effect of the Leaving Group In the vast majority of aromatic electrophilic substitutions, the leaving groupvis Ht as indicated above, and very little work has been done on the relative electrofugal ability of other leaving groups. However, the following orders of leaving-group ability have been suggested: (1) for leaving groups that depart without assistance (SN1 process with respect to the leaving group), NO2+ iPr+ SO3 t-Bu + ArN2 + ArCHOH + NO+ CO2; (2) for leaving groups that depart with assistance from an outside nucleophile (SN2 process), Me + Cl + Br + D +~ RCO + H +~ I + Me3Si +. We can use this kind of list to help predict which group, X or Y, will cleave from an arenium ion once it has been formed, and so obtain an idea