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【正文】 K M n O 4 , HC H 3 C C H + C H 3 C O O H + C O 2 + H 2 OC H 3 C = C H 2 +C H 3K M n O 4 , HC H 3 C C H 3O+C O 2 + H 2 O( 1)與 KMnO4的反應(yīng) ( 2)與 O3的反應(yīng) +C H 3C H 3 C H = C C H 2 C H 3 O 3 C COOOC H 3C H 3C H 2 C H 3HOH2 O + Z n C H 3 C H O + C H 3 C C H 2 C H 3+C H 3 C C C H 2 C H 3 O 3H 2 O + Z n1 )2 ) C H 3 C O O H C H 3 C H 2 C O O H5. 烯烴 α H 的鹵代(烯丙位鹵代) C H 3 C H = C H 2 + C l 2 ℃5 0 0 ~ 6 0 0 C l C H 2 C H = C H 2H 2 CH 2 CCOCON B r+B rH 2 CH 2 CCOCON H+C C l 4(N溴代丁二酰亞胺 , NBS) 6. 末端炔烴的特殊性 ( 1)炔 H的弱酸性 H C C H + N a N H 2 H C C N a +H N H 2 +φpKa =25 φpKa =35H C C H+ H C C N a + +H O H N a O H酸性: H 2 O R O H H C C H N H 3 R H( 2)金屬炔化物的生成 R C C H+[ C u ( N H 3 ) 2 ] C l[ A g ( N H 3 ) 2 ] N O 3R C C A gR C C C uN H 3 + N H 4 N O 3+ N H 3 + N H 4 N O 3(白) (磚紅) 四、二烯烴( diene ) 1. 二烯烴的分類與結(jié)構(gòu) ( 1)隔離二烯烴: C = C H ( C H2 ) n C H = C ( n = 1 , 2 , 3 . . . )( 2)累積二烯烴: C = C = C C C C HHHHsp2 sp2sp(3)共軛二烯烴: C = C H C H = CC = C C H 3C H 3HHHHC = C (2Z,4Z)2,4己二烯 C = CC H 3C H 3HHHC = CB r(2Z,4E)2溴 2,4己二烯 H 2 C = C H C H = C H 21 2 3 4H B rC H = C H 2C H 3 C HB r1,2加成 C H 3 C H = C H C H 2B r1,4加成 歷程如下: H 2 C = C H C H = C H 21234 H ++ C H 2 C H C H C H 3+δ+δH 2 C = C H C H 3C HB rC H 3C H = C HC H 2B r1234C H 2 C H C H C H3+δ+δB r+1,2加成 1,4加成 C H = C H 2C H 2 C HB rC H = C HC H 2B r+H 2 C = C H C H = C H 2B rB r 2C H 2B r4 0 ℃20% 80% C H = C H 2C H 2 C HB r B rC H = C HC H 2B rC H 2B r 8 0 ℃C H 3C = C HC H 2HH 2 C = C C H = C H 2 H B rC H 2B rC H = C H 2C H 2 CH B r+C H 3C H 380% 20% 1,2加成 1,4加成 (主) 3. 狄爾斯 阿德爾 (DielsAlder)反應(yīng): C H O+ 1 0 0 ℃苯C H O雙烯體 親雙烯體 + OOO OO
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