[材料科学与工程][有机化学][第11章 芳香烃的化学性质][孙芳]

1、芳环难以氧化、加成，芳环难以氧化、加成，易于发生亲电取代反应。易于发生亲电取代反应。 C6H6Br2Br2FeBr3KMnO4H+CCl4不反应C6H5Br不反应芳烃侧链反应芳烃侧链反应HXNO2SO3HRCROHalogenationNitrationSulfonationAlkylationAcylation+ E+E+HE+-H+Esp2sp3sp2HE+HE+HE+1. 亲电取代反应历程亲电取代反应历程加成，慢加成，慢消除，快消除，快-络合物络合物-络合物的共振结构式络合物的共振结构式亲电取代反应历程亲电取代反应历程+ 浓HNO3浓H2SO455oCNO2+ H2OHONO2+ 2H2

2、SO4NO2+ + H3O+ + 2HSO4-硝化历程硝化历程慢HNO2HNO2HNO2HNO2快NO2+H2NO2H+甲苯比苯容易硝化甲苯比苯容易硝化,邻对位产物为主？邻对位产物为主？硝基苯继续硝化困难硝基苯继续硝化困难,间位产物为主间位产物为主?CH3HNO3(浓） NO2CH30+ H2O+30C+CH3NO2 NO2+ 发烟HNO3浓硫酸0NO2NO2+H2OC100CH3HNO3(浓） NO2CH30+30CCH3NO20 混酸50CCH3O2NNO20 混酸50CCH3O2NNO20 混酸50C1 NO2CH3O2NNO22,4,6- 三硝基甲苯（TNT)+ Br2FeBr3Br+

3、 HBr+ X2QickXXFeX3XXFeX3+-SlowHX+FeX4-X+ HX+ FeX3卤化历程卤化历程 CH3+ HNO3CH3O2NNO2NO255oC 80oC 110oC+ H2SO4ClFeCl3Cl Cl Cl Cl Cl2CH3+ HNO3CH3O2NNO2NO255oC 80oC 110oC+ H2SO4CH3+ HNO3CH3O2NNO2NO255oC 80oC 110oC+ H2SO4OH+ Br2H2OOHBrBrBrNH2+ Br2H2ONH2BrBrBr氯苯比苯氯代困难氯苯比苯氯代困难邻对位产物为主？邻对位产物为主？+ H2SO4 (10%SO3)SO3H+

4、 H2OSO3H稀 H2SO4100170oC+ H2SO4可利用此反应保护苯环上的某个位置可利用此反应保护苯环上的某个位置+ CH3CH2ClAlCl305oCCH2CH3+ HClCH3CH2Cl + AlCl3CH3CH2+ + AlCl4-CH3CH2+ +CH2CH3H+CH2CH3H+AlCl4-+CH2CH3+ HCl + AlCl31）烷基化历程）烷基化历程 +H3PO4+H3PO4H+H+OHH+O+H2H2O-+甲基迁移1.+H+ 产物-H+(1)CH2CH2CHC(CH3)3OHH+(2)CH3CHCH2CHCHCH3H+CH2CH3(3) CCH2CH3H+C6H6+C

5、H3CHCH2ClCH3AlCl3?+CH3CHCH2ClCH3AlCl3?+H3PO4+CH3CHCH2ClCH3AlCl3?C(CH3)3+CH3CHCH2ClCH3AlCl3?CH3+CH2CH2CH3+ CH3CH2CH2ClAlCl3 (30%)+H3PO4CH(CH3)230%70%+RX无水AlCl3R+RR+ CH3CClOAlCl3 (1mol)C-CH3O+ HClC-CH3O+ CH3COCCH3OOAlCl3 (2mol)+ CH3COOHCH2CH2CH2COCl无水AlCl3O+HClCH3CIO CH3CBrO CH3CClOCH3CFOO+ OOAlCl3 CC

6、H2CH2COOHOAlCl3 + CH3CH2CClOCCH2CH3OZn-HgHClCH2CH2CH3+ HCHO + HCl无水 ZnCl2CH2Cl+ HCHO + HCl无水 ZnCl2CH3CH3CH2ClNH3KCNCH3CH2CNCH3CH2NH2CH3KMnO4COOHC H2C H3K M n O4C O O HC H2C H3C H3K M n O4C O O HC H3+ O2V2O5400CCHCHCOOCO+CO2+H2O0+3H2NiNaNH3,CH3CH2OH液1,4-环己二烯CH2CH3Br2CH-CH3Br(100%)Br2hv2BrBr+CHCH3CH2C

7、H3Br2CHCH3Br. . . . . .自由基反应历程自由基反应历程 CH3+ HNO3CH3O2NNO2NO255oC 80oC 110oC+ H2SO4CH3+ HNO3CH3O2NNO2NO255oC 80oC 110oC+ H2SO4CHOOHCH3NO2CHOOHCH3NO2CHOOHCH3NO2NO2CH3甲苯比苯容易硝化甲苯比苯容易硝化邻对位产物为主邻对位产物为主硝基苯继续硝化困难硝基苯继续硝化困难间位产物为主间位产物为主浓浓HNO3浓浓H2SO4发烟发烟HNO3发烟发烟H2SO4NO2 CH3+ HNO3CH3O2NNO2NO255oC 80oC 110oC+ H2SO4

8、CH3+ HNO3CH3O2NNO2NO255oC 80oC 110oC+ H2SO4CH3CH3+ HNO3CH3O2NNO2NO255oC 80oC 110oC+ H2SO4ClFeCl3Cl Cl Cl Cl Cl2CH3+ HNO3CH3O2NNO2NO255oC 80oC 110oC+ H2SO4CH3+ HNO3CH3O2NNO2NO255oC 80oC 110oC+ H2SO4氯苯比苯氯代困难氯苯比苯氯代困难邻对位产物为主邻对位产物为主待解问题待解问题CH3HE+CH3HE+CH3HE较稳定CH3HECH3HECH3HECH3HE+CH3HE较稳定CH3HE+O-P-M-CHHH

9、CH3HE+CH3HE+CH3HE较稳定CH3HECH3HECH3HECH3HE+CH3HE较稳定CH3HE+O-P-M-CH3HE+CH3HE+CH3HE较稳定CH3HECH3HECH3HECH3HE+CH3HE较稳定CH3HE+O-P-M-较稳定较稳定较稳定较稳定+HE+HE特别不稳定HEHEHEHE+HEHE+O-P-M-特别不稳定HENO2NO2NO2NO2NO2NO2NO2NO2NO2NOO-+HE+HE特别不稳定HEHEHEHE+HEHE+O-P-M-特别不稳定HENO2NO2NO2NO2NO2NO2NO2NO2NO2+HE+HE特别不稳定HEHEHEHE+HEHE+O-P-M-特

10、别不稳定HENO2NO2NO2NO2NO2NO2NO2NO2NO2特别不稳定特别不稳定特别不稳定特别不稳定+HECl+ClHE特别稳定HEClHEHEHE+HEHE+O-P-M-ClHE+HECl+特别稳定HEClClClClClCl+HECl+ClHE特别稳定HEClHEHEHE+HEHE+O-P-M-ClHE+HECl+特别稳定HEClClClClClCl+HECl+ClHE特别稳定HEClHEHEHE+HEHE+O-P-M-ClHE+HECl+特别稳定HEClClClClClCl特别稳定特别稳定特别稳定特别稳定 -NR2 _NHR _NH2 _OH; _NHCOR _OCOR; _R _

11、Ar; _X_+NR3 _NO2 _CF3 _CCl3 _CN _SO3H _CHO _CR _COOH _COORO -NR2 _NHR _NH2 _OH; _NHCOR _OCOR; _R _Ar; _X烷基苯硝化烷基苯硝化CH3+ HNO3CH3O2NNO2NO255oC 80oC 110oC+ H2SO4 RRCH3+ HNO3CH3O2NNO2NO255oC 80oC 110oC+ H2SO4NO2HNO3H2SO4空间立体效应空间立体效应CH3+ HNO3CH3O2NNO2NO255oC 80oC 110oC+ H2SO4甲苯烷基化甲苯烷基化+ RClRCH3+ HNO3CH3O2

12、NNO2NO255oC 80oC 110oC+ H2SO4取代基的体积和进攻试剂的体积越大，邻位异构体越少。取代基的体积和进攻试剂的体积越大，邻位异构体越少。 CH3NO2(99%)COOHSO3HCOOHBr100%80%20%OHNO2OHNO2NO2NO2CH3NO2NO2ClBr不进入该位置CHOOHCH3NO2OHCH3（100%）CH3NHCOCH3CH3NO2(99%)COOHSO3HCOOHBr100%80%20%CH2CH3CH3Cl19%17%43%20%CH3H2SO4CH3SO3HHNO3H2SO4CH3NO2SO3HH+CH3NO2KMnO4NO2COOHKMnO4C

13、OOHHNO3H2SO4COOHNO2ClNO2Cl2FeClH2SO4ClSO3HHNO3ClSO3HNO2H2SO4H+ClNO2CH3H2SO4CH3SO3HHNO3H2SO4CH3NO2SO3HH+CH3NO2KMnO4NO2COOHKMnO4COOHHNO3H2SO4COOHNO2CH3H2SO4CH3SO3HHNO3H2SO4CH3NO2SO3HH+CH3NO2KMnO4NO2COOHKMnO4COOHHNO3H2SO4COOHNO2CH3H2SO4CH3SO3HHNO3H2SO4CH3NO2SO3HH+CH3NO2KMnO4NO2COOHKMnO4COOHHNO3H2SO4COO

14、HNO2NH2NH2NO2CH3COClNHCOCH3浓H2SO4NHCOCH3SO3HHNO3NHCOCH3SO3HNO2H3+O讨论讨论 CH3COOHBrNO2选择：选择：(a) 1.硝化硝化 2.氧化氧化 3.溴代溴代 (b) 1.氧化氧化 2.硝化硝化 3.溴代溴代 (c) 1.氧化氧化 2.溴代溴代 3.硝化硝化+ Br2CH3COOHBr(75%)+ HNO3H2SO4NO2(95%)卤化硝化H2SO4SO3HSO3HH2SO41600C动力学控制热力学控制H2SO4SO3HSO3HH2SO41600C动力学控制热力学控制H2SO4SO3HSO3HH2SO41600C动力学控制热

15、力学控制H2SO4SO3HSO3HH2SO41600C动力学控制热力学控制G(act.)G(act.)G(deact.)G(deact.)G(act.)G(act.)G(deact.)G(deact.)CH3ClSO3HCH3SO3HCCl4 ,OoCH2SO4SO3HSO3HH2SO41600C动力学控制热力学控制NO2NO2NO2NO2NO2HNO3H2SO4,0oC+H2SO4SO3HSO3HH2SO41600C动力学控制热力学控制H2SO4SO3HSO3HH2SO41600C动力学控制热力学控制NO2NO2NO2NO2NO2HNO3H2SO4,0oC+NO2NO2NO2NO2NO2HN

16、O3H2SO4,0oC+H2SO4SO3HSO3HH2SO41600C动力学控制热力学控制NO2NO2NO2NO2NO2HNO3H2SO4,0oC+H2SO4SO3HSO3HH2SO41600C动力学控制热力学控制NO2NO2NO2NO2NO2HNO3H2SO4,0oC+NO2NO2NO2NO2NO2HNO3H2SO4,0oC+NO2NO2NO2NO2NO2HNO3H2SO4,0oC+NO2(deact.)OCOOHCOOHNO2NH2(act.)OCOOHCOOH(1) (2)HH(3) (4)(5) (6)(7)(8) (9)HH(10)Na+CH3(11)(12)(1) (2)HH(3)

17、 (4)(5) (6)(7)(8) (9)HH(10)N a+C H3(11)(12)(1) (2)HH(3) (4)(5) (6)(7)(8) (9)HH(10)Na+CH3(11)(12)(1) (2)HH(3) (4)(5) (6)(7)(8) (9)HH(10)Na+CH3(11)(12)(1) (2)HH(3) (4)(5) (6)(7)(8) (9)HH(10)Na+CH3(11)(12)(1) (2)HH(3) (4)(5) (6)(7)(8) (9)HH(10)Na+CH3(11)(12)(1) (2)HH(3) (4)(5) (6)(7)(8) (9)HH(10)Na+CH3

18、(11)(12)(1) (2)HH(3) (4)(5) (6)(7)(8) (9)HH(10)Na+CH3(11)(12)(1) (2)HH(3) (4)(5) (6)(7)(8) (9)HH(10)Na+CH3(11)(12)(1) (2)HH(3) (4)(5) (6)(7)(8) (9)HH(10)Na+CH3(11)(12)Na+(1) (2)HH(3) (4)(5) (6)(7)(8) (9)HH(10)N a+C H3(11)(12)+芳香族化合物的加成芳香族化合物的加成Na醇四氢化萘H2Pt十氢化萘+3H2Ni+3Cl2日 光 或 紫 外 光ClClClClClCl六 六 六芳香族化合物的芳香族化合物的O2V2O5460C0COOCO+ O2V2O5400CCHCHCOOCO+CO2+H2O