高等有机化学(第13至第14章)2008.pptVIP

CHAPTER 13Aromatic Nucleophilic Substitution It must pointed out that nucleophilic substitutions proceed so slowly at an aromatic carbon that the reactions of Chapter 8 are not feasible for aromatic substrates. There are, however, exceptions to this statement, and it is these exceptions that form the subject of this chapter. MECHANISMS 1. The SNAr Mechanism Evidence for The SNAr Mechanism The break of the Ar-X was not the rate-determining step Element effect of leaving group The SN1 Mechanism The evidence for the SN1 mechanism The Benzyne Mechanism Mechanism Other evidence The SRN1 Mechanism Explaining Evidence for SRN1 mechanism REACTIVITY The Effect of Substrate Structure SNAr Mechanism Benzyne Mechanism The Effect of the Leaving Group The Effect of the Attacking Nucleophile Examples of Reaction Chapter 14 Addition to Carbon–Carbon Multiple Bonds MECHANISMS 1. Electrophilic Addition Stereochemistry for the additon of molecule ABC=CBA Cyclic intermediate Open Carbocation Intermediates Stereochemistry of AdE3 mechanism Nucleophilic Addition 2. Alkali Fusion of Sulfonate Salts 3. Replacement by SH or SR 4. Replacement by NH2, NHR, or NR2 5. Replacement of a Hydroxy Group by an Amino Group(Bucherer reaction) 6. Homo-Coupling of Aryl Halides: The Ullmann Reaction 7. Aryl–Alkyne Coupling Reactions 8. Conversion of Aryl Substrates to Carboxylic Acids, Their Derivatives,Aldehydes, and Ketones 9. The von Richter Rearrangement There are four fundamental ways in addition to a double or triple bond. Three of these are two-step processes: Initial attack by a nucleophile, or an electrophile or a free radical. The second step consists of combination of the resulting intermediate with Respectively, a positive species, a negative species, or a neutral entity. The fourth type of mechanism: Attack at the two carbon atoms of the double or triple bond is simultaneous (concerted). Which of the four mechanisms is operating in any given case is determined by:the nature of the sub