郑州大学 有机化学8卤代烃 金属有机化合物复习课程.ppt

8 * 8.9 Organozinc Reagents (有机锌试剂) Simmons-Smith reaction stereospecific 8.10 Organosodium Reagents (有机钠试剂) Würtz反应 an antifungal(抗真菌的) compound isolated from lily plants 3-甲基-1,5-二甲氧基-2,4-二氯苯 2,4-dichloro-1,5-dimethoxy-3-methylbenzene Chlortetracycline 氯四环素 Thyroxine 甲状腺素 Aryl Halides(芳基卤，卤代芳烃) 8.11 Structure 8.12 Preparation Halogenation of arenes(芳烃的卤化) Halogenation of aryl diazonium salts (重氮盐的卤化) SN1 CuCl CuBr KI NaBF4 8.13 Reactions 8.13.2 Formation of Organometallic Reagents (有机金属试剂) 8.13.1 Electrophilic aromatic substitution(芳香族亲电取代) Würtz-Fittig反应 Ullmann反应 Würtz反应 Fittig反应 8.13.3 Nucleophilic Aromatic Substitution (芳香族亲核取代反应) SN2 is not reasonable because the aromatic ring blocks backside approach of the nucleophile. Inversion is not possible. SN1 is also unlikely because: 1)C—Cl bond is strong; therefore, ionization to a carbocation is a high-energy process 2)Aryl cations are highly unstable Nucleophilic aromatic substitution by Addition-Elimination: the SNAr Mechanism Successful nucleophilic substitution: 1) a good nucleophile, such as RSH, HO-, NC-, R2NH, etc; 2) a good leaving group, such as halides; 3) an electron-withdrawing group ortho or para to the leaving group. SNAr Mechanism ：Addition-Elimination Starting from benzene, how to synthesize 4-nitrobenzonic acid (对硝基苯甲酸) and 4-nitrobenzonitrile (对硝基苯甲腈)? Reaction rate: X = I Br Cl F Reaction rate: X = F Cl ~ Br I 尽管芳基卤不易发生SN2与SN1，但在强碱作用下可以发生亲核取 8.13.4 Nucleophilic aromatic substitution through an Elimination-Addition mechanism: the Benzyne mechanism (芳香族亲核取代反应的消去-加成机理—苯炔机理 the π orbitals of benzyne (苯炔) normal π bond two p orbitals inside the ring abnormal π bond two sp2 orbitals outside the ring Evidence for benzyne as an intermediate: Regioslectivity (区域选择性) 取代基(CF3, OMe)即使有孤对电子，也不可能与苯环负离子上的负电共轭（因为p轨道不可能共平面），故只考虑诱导效应。 Typical Benzyne Reactions (苯炔的典型反应) Summary Reactions of alkyl halides SN1 SN2 E1 E2 Reduction Organometallics Grignard Reagents Organocopper Reagents Aryl nuc