第四章芳香烃( 4 学时)

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第四章芳香烃( 4 学时)

AromaticHydrocarbons)


( Aromatic Hydrocarbons )( Simple aromatic hydrocarbons)(Fusedpolycyclic aromatic hydrocarbons )( Non-benzenoidaromatic hydrocarbons )


( Simple aromatic hydrocarbons)


( Structure of benzene )1Kekule1825 C 6 H 6Kekul’e


13CCH 2Ni+ 119.6kJ·mol 13H 2Ni+ 207.4kJ·mol 1119.63207.4=151.4 kJ·mol 1


26C6H6XXXX


HHCHCCCCHCHH


HHHHHH


CH 3methylbenzeneCH 3CH 3CH 3CH 3 CH 3CH 312—o-dimethylbenzene13—m-dimethylbenzene14—p-dimethylbenzene


CH 3CH 3CH 3CH 3CH 3CH 3 CH 3 CHCH 331, 2, 3—victrimethylbenzene1, 3, 5—symtrimethylbenzene1, 2, 4—unsymtrimethylbenzene


(nomenclature) CH—CH 2 —CH 3CH 2 —CH 2 —CH 3CHCH 233 - phenylhexanephenyl ethylene


C 2 H 5CH 3CHC 2 H 35CH(CH 3 ) 2252


( Priority order of functional group )— COOH —SO 3 H — COOR —COX — CONH 2 — CHO — CN — OH —NH 2 —R — NO 2 —X HO COOHHO NO 2CH 3SO 3 H


H ArArCH 2 — CH 3 — (Ph) 4—


1. (Substitution reaction)(1)Hologenation H+ Br 2FeBr 355~60Br+ HBrBrBr 2 , FeBr 3BrBr+BrBr


(Hologenation)CH 3 Cl 2,FeCl 3CH 3Cl+ClCH 3CH 3 Cl2 CH 2 ClCl 2 CHCl 2^^^^^^^^


() (Nitration)HH 2SO 4+ HO-NO 250~60NO 2+ H 2 ONO 2HONO 2 + 90H 2 SO 4NO 2+ H 2 ONO 2CH 3H 2SO 4 CH+ HO-NO 3CH2 +330 NO 2 O 2 N


() (Sulfonation)H+HOSO3 H 70~80SO 3 H+ H 2 OSO 3 HH 2SO 4200~245SO 3 HSO 3 HH 2SOCH 4 SO 3 H3+CH 3HO 3 SCH 3


() (Alkylation)AlCl3 + RCl AlCl 3R+ HCl


1C 3 + CH 3 CH 2 CH 2 ClAlCl 3CH(CH 3 ) 2 (CH 2 ) 2 CH 3+2 FeCl 3 , SnCl 4 , HF, H 2 SO 4 ………


CH(CH 3 ) 2+ CH 3 CH=CH 2AlCl 3CH(CH 3 ) 2+ CH3 CH 2 CH 2 OH AlCl 34NO2 CNSO3 H—CO—


1 01 0


(Acylation)AlCl3 + AlCl 3+ HCl


1NO2 CNSO3 H—CO—234


Electrophilic substitution reactionH+ Br 2H• •Br : Br + FeBr 3FeBr 3Br55~60Br + +H H• C C•C • • CC CH HHBr +Br+ HBrBr +Br ++ [FeBr 4 ]


Electrophilic substitution reactionHH • H•+ BrC CC • • C•• C C HH H


Electrophilic substitution reactionH• •H H• C C•C • • CC CH HBrH +H ++ [FeBr 4 ] HBr + FeBr 3


Electrophilic substitution reaction_ +HNO 3 +2H 2 SO 4 2HSO 4 + H 3+ O + NO 2RCl + AlCl 3R + + [AlCl 4 ] _R C O Cl+AlCl 3R CO+ [AlCl 4 ]


2. (Oxidation )H 3 C C(CH 3 ) 3KMnO 4HOOC C(CH 3 ) 3H +V 2 O 5 H C C O + O 2 O + CO400~500+ 2 H 2 OH CCO1H2COOH


3. ( Addition )H 2NiCl 2 C 6 H 6 Cl 6


orthoortho/paradirectors meta directors


1 NR 2 NH 2 OH OCH 3 NHCOCH 3 RX


+N(CH 3 ) 3 , NO 2 , CN, SO 3 H, CHO ,COOH, COOR, CONH 2


2. CH 3CH 3 1.0170.999 + I + C1.011()


+ + + C p- + I


NO 2 O N = O NO 20.7050.800 I C 0.720


3. ClCOOHCH 3COOHCH 3SO 3 HH 3 CO CH 3


ClCH 3NO 2COOHNO 2BrNO 2Br


1.CH 3COOHBrNO 2•√


2COOHCl•√


3CH 3CH 2 ClClAB•√


4ClNO 2•√


5ClNO 2SO 3 HA) B) C) D) •√


6CH 3CH


7CH 3O 2 NCOOHNO 2


(Hückelrule):4n+2 ( n = 0123……0 ……) (Key notes)1. 2. C sp 2 3. = 4n+24


41 + 2 = 642 + 2 = 1043 + 2 = 14= 4= 8


= 6= 2= 2= 6[18]-= 18

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