7.5多环芳烃 Polycyclic Aromatic Hydrocarbons
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 7.5 多环芳烃 Polycyclic Aromatic Hydrocarbons
751联苯( Biphenyl) 1.联苯的结构 32H 213 4 56 H
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 7.5.1 联苯 ( Biphenyl) 1. 联苯的结构 45° H H H H 1 1' 2 2' 3 3' 4 4' 5 6 6' 5
2.联苯的制备 g联苯胺重排 NH-NH- HN一 NH2 NaNo2+ H3PO2 2 HCI ①D ⑨D
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 2. 联苯的制备 NH NH H + H 2 N NH 2 NaNO 2 HCl N 2 N 2 H 3PO 2 联苯胺重排
Wurtz-Fittig reaction 2 C 5% Ulmann reaction Cu 2 230 82
Organic Chemistry Organic Chemistry Xiamen Xiamen University University Cl Na 2 5% Wu rt z − F ittig R eactio n I Cu 2 82% Ul m a n n Re a c t i o n 230
23.联苯的反应 Fe +B_△ -Br 2·B包助 AlC ANO2 少C-CH2CH2CO2H 70~90%
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 3. 联苯的反应 + Br 2 Fe Br Br Br 2 , F e Br + O O O Al C l 3 NO 2 C C H 2CH 2CO 2 H O 70 ~ 90%
Br Br2 NH2 H2O nH2 Br HNO SO3H H2SO4△ O2N- SO3H
Organic Chemistry Organic Chemistry Xiamen Xiamen University University NH 2 Br 2 H 2 O NH 2 Br Br SO 3 H H 2SO 4 O 2 N SO 3 H HNO 3
HNO No HOAc Ka~23 p Br2 -Br Fe Br Br2 2 h 芴( Fluorene) Na, Cro 芴酮 ①D HOAc Fluorenone H K ⑨D KOH 芴钾
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 1 2 6 5 4 3 7 8 9 HNO 3 HOA c NO 2 Br Br Br 2 Br 2 Fe hv 芴 ( Flu o rene) O Na 2Cr 2 O 7 HOA c H K KOH pKa ~ 23 芴酮 F luorenone 芴钾
7.52稠环芳烃 1.萘( Naphthalene)) I a 1424A1.365A 2B 1.404A 4 o1.393A 苯的碳碳键1.397A 稳定化能250kJ/mol
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 7.5.2 稠环芳烃 1. 萘 (Naphthalene) 1.424 A 1.365 A 1.404 A 1.393 A 苯的碳碳键1.397 A 1 2 3 5 4 6 7 8 9 10 α β 稳定 化 能 250 kJ/mol
三萘衍生物的合成 D CH AlCl3 Zn(Hg) CH HO2C HCI CH HOC hf or Ppa Hg Se,△ 三orH2SO4CH HCI CH3 or ①D D CH
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 萘衍生物的合成 CH 3 O O O + Al C l 3 CH 3 HO 2 C O Zn( Hg) HCl CH 3 HO 2 C HF or PPA or H 2SO 4 CH 3 O Zn( Hg) HCl CH 3 Se , or S , CH 3
RMgX H,O CH Et,O CH3 Hcu人 ROMgⅩ R OH H Se,△ △CH or s △CH: R R 荼的反应—亲电取代反应 ①D NO hNO2 /HOAC-Ac,O NO ⑨D 50~70 101
Organic Chemistry Organic Chemistry Xiamen Xiamen University University CH 3 O RMg X Et 2 O CH 3 R OMgX H 2 O H + CH 3 R OH H + CH 3 R Se , or S , CH 3 R 萘的反应——亲电取代反应 50 ~70 HNO 3 /HOA c - A c 2 O NO 2 NO 2 + 10 1