columbia大学有机化学课件 （十五）.pptVIP

4.15Halogenation of Alkanes Energetics RH + X2 ? RX + HX explosive for F2 exothermic for Cl2 and Br2 endothermic for I2 4.16Chlorination of Methane Chlorination of Methane carried out at high temperature (400 °C) CH4 + Cl2 ? CH3Cl + HCl CH3Cl + Cl2 ? CH2Cl2 + HCl CH2Cl2 + Cl2 ? CHCl3 + HCl CHCl3 + Cl2 ? CCl4 + HCl 4.17Structure and Stability of Free Radicals Free Radicals contain unpaired electrons Alkyl Radicals Most free radicals in which carbon bearsthe unpaired electron are too unstable to beisolated. Alkyl radicals are classified as primary,secondary, or tertiary in the same way thatcarbocations are. Figure 4.15 Structure of methyl radical. Methyl radical is planar, which suggests that carbon is sp2 hybridized and that the unpaired electron is in a p orbital. Alkyl Radicals The order of stability of free radicals is the same as for carbocations. Alkyl Radicals Alkyl Radicals Alkyl Radicals Alkyl Radicals The order of stability of free radicals can be determined by measuring bond strengths.  By bond strength we mean the energy required to break a covalent bond. A chemical bond can be broken in two different ways—heterolytically or homolytically. In a homolytic bond cleavage, the two electrons inthe bond are divided equally between the two atoms.One electron goes with one atom, the second with the other atom. In a heterolytic cleavage, one atom retains bothelectrons. The species formed by a homolytic bond cleavageof a neutral molecule are free radicals. Therefore, measure energy cost of homolytic bond cleavage to gain information about stability of free radicals. The more stable the free-radical products, the weakerthe bond, and the lower the bond-dissociation energy. Measures of Free Radical Stability Bond-dissociation energy measurements tell us that isopropyl radical is 13 kJ/mol more stable than propyl. Measures of Free Radical Stability Bond-dissociation energy