Alkanes - City University of New York：烷烃-纽约城市大学.pptVIP

* * * * * * * * * * * * * * * * * * * * * * * * * * * * The life of the chain depends on the ongoing presence of the highly reactive Cl atoms and alkyl radicals. Eliminating these species ends chains. 4. 2 Cl. Cl – Cl 5. 2 R. R – R 6. R. + Cl. R - Cl Heat or light Chain Reaction Mechanism 1. Cl – Cl 2 Cl. 2. R – H + Cl. R. + H - Cl 3. R. + Cl – Cl R – Cl + Cl. Repeat 2, 3, 2, 3,…. Chain steps. Chlorine atom. Highly reactive, only seven electrons in valence shell Weak Cl-Cl bond may be broken by heat or light. Hydrogen to be abstracted. Trade bonds: R-H for H-Cl Alkyl radical, only seven electrons around the C, highly reactive alkyl radical. Trade bonds: weak Cl-Cl for a stronger C-Cl Regenerates the Cl atom used in step 2 Termination steps. Initiation Energetics of the Chain Steps Chlorination of ethane Step 2, abstraction of the H, controls the regioselectivity of the reaction. Isothermic or slightly exothermic for Cl; endothermic for Br. Step 3, attachment of the halogen, controls the stereochemistry, which side the halogen attaches. Exothermic Step 2 and Bond Dissociation Energies, breaking bonds… More highly substituted radicals are easier to make. This gives rise to regioselectivity = non-random replacement. Now bromination. Compare chlorination and bromination of 2-methyl propane. Bromination is more Regioselective. Examine Step 2 only for regioselectivity. BDE, reflecting different radical stabilities Slightly exothermic Endothermic H-Cl is a more stable bond than H-Br. Step 2 is exothermic for chlorination. Endothermic for Br First chlorination. Two kinds of H. Step 2 Transition State Energetics, Cl vs Br chlorination Exothermic, tertiary radical more stable Early transition states, little difference in energies of activation, rates of abstraction and regioselectivity bromination Endothermic, but tertiary radical still more stable by same amount. Late transi