高等有機化學 第五章 芳環(huán)

1、2022-4-812022-4-82CCCCCCHHHHHH2022-4-832022-4-842022-4-852022-4-862022-4-872022-4-88L+YY+X2022-4-89Y+slowlyLYLYLYLYYfast123L+2022-4-8102022-4-811+Z-YZLY+-L2022-4-8122022-4-813+MeMeMeH+HFSbF5SO2(liquid)-78MeMeMeHHSbF6-2022-4-814YHY+Y+Y+ H+產物絡合物也稱傳荷絡合物絡合物+2022-4-8152022-4-8162022-4-817+Y+Y+H+2022-4-81

2、8Z2022-4-8192022-4-8202022-4-821Z2022-4-822ZYHZYHZYHZYHZYHZYHZYHZYH+對位間位67891011+HYZHYZHYZ543+HYZ鄰位2022-4-8232022-4-8242022-4-8252022-4-8262022-4-827Z2022-4-828可以形成與 Y+Z絡合物以下2022-4-8292022-4-8302022-4-8312022-4-8322022-4-8332022-4-834（2）Ortho/Pare Ratio2022-4-835HH0.250.250.10.10.32022-4-836BrHNO3Br

3、NO2BrNO2+90% 以上2022-4-837（3）Orientation in Benzene Rings with More than One SubstituentCH3CH3COOHCl2022-4-838NHCOCH3OCH3四種產物大致相等2022-4-839NO2Cl2022-4-840e.g的位置最好進攻因此動力學控制產物是 位而熱力學控制產物是 位2022-4-841CH3e.g2022-4-8422022-4-843NN2022-4-844 分速度因數(shù)與選擇性分速度因數(shù)與選擇性2022-4-8452022-4-846fokPhH/6kPhZ/2異構體o100kPhZ/2

4、kPhH/6異構體m100fmfp異構體p100kPhH/6kPhZ/12022-4-8472022-4-848fo(6)(2)(23)(1)(0.63)43.5fm(6)(2)(23)(1)(0.03)2.1fp(6)(1)(23)(1)(0.34)46.92022-4-849Cl0.0290.00090.137OCH30.252.31045.54102022-4-8502022-4-851lgkXkH()x2022-4-852lgkXkHx2022-4-8532022-4-854Ar HHNO3 / H2SO4Ar NO22022-4-8552022-4-856e.g HNO3 + H2S

5、O4NO2+H3O +HSO4-+222022-4-857NR2HNO2NR2NO2022-4-858ArH+ArN2+Ar-NN-ArNaO3SN2+NMe2NaO3SNNMe2N2022-4-8592022-4-860N N NHNH2N2+N NNH2-+C6H5NH3Cl2022-4-861Ar HH2SO4Ar SO2OHH2SO4OHOHSO3HOHSO3H+2022-4-862ClSO2OHRSOClR2022-4-863+ArHSCl2Friedel-CraftsArSAr催化劑+SOAlCl3OS2022-4-864NH2SNaClNaOHS2Cl2NH2Cl2022-4-8

6、65R+ X2FeX3RX+ HX2022-4-866R+ R,ClorBrAlCl3RR,2022-4-8672022-4-8683AlCl3+CHCl3CHCH3CHCH2CH2CHCH3ClCl+CH3CH3AlCl32022-4-8692022-4-870+RCClOAlCl3COR2022-4-871ArH+RCORH2SO4RCORCROHRArCRArRAr，ArHCCl3C HO+2ClClCCl3CHCl2022-4-872OHCH2CH2CH2OHOHCH2CH2CH2OHCH2CH2酚醛樹脂 2022-4-873（5）Rearrangement ReactionO C R

7、OAlCl3OHROOHCRO+2022-4-8742022-4-8752022-4-8762022-4-8772022-4-8782022-4-8792022-4-8801. reactions activated by electron-withdrawing groups ortho and para to the leaving group;2. reactions catalyzed by very strong bases and proceeding through aryne intermediates; 3. reactions initiated by electron d

8、onors; 4. reactions in which the nitrogen of a diazonium salt is replaced by a nucleophile. Reactions that are successful at an aromatic substrate are largely of four kinds:It is noted that solvent effects can be important2022-4-8812022-4-8822022-4-8832022-4-8842022-4-8852022-4-8862022-4-887 2022-4-8882022-4-8892022-4-890 2022-4-8912022-4-8922022-4-8932022-4-8942022-4-8952022-4-8962022-4-8972022-4-8982022-4-8992022-4-8100MeMeMeMeMeMeMeMeMeNH2-+IH2NH2NMeMeMeIMeMeMeMeMeMeNH2-+H2NH2N2022-4-81012022-4-81022022-4-8103ArIelectr