有機(jī)合成課件第2章基礎(chǔ)有機(jī)合成(編輯修改稿)
2025-02-16 07:06 本頁(yè)面
【文章內(nèi)容簡(jiǎn)介】 C lC H3B rC H3C No T o l u i d i n eo M e t h y l a n i l i n eo A m i n o t o l u e n eo T o l u e n e d i a z o n i u mc h l o r i d eo C h l o r o t o l u e n eo B r o m o t o l u e n eo t o l u n i t r i l eo C y a n o t o l u e n eN a N O2H C lH2S O4C u C lC u B rC u C NC H3N2+C lN a N O2H C lN a N O2b) Replacement by I Example: A r N 2 + A r I N 2+K Ic) Replacement by F K IN H 2H 2 S O 4N a N O 2A n i l i n e I o d o b e n z e n eN 2 + H S O 4 IA r N 2 + B F 4 A r F N 2 B F 3+ +h e a tExamples: N 2H C lN a N O 2B F 3+ +h e a tN H 2 N 2 + B F 4 FN 2 + C l H B F 4b e n z e n e d i a z o n i u m c h l o r i d eb e n z e n e d i a z o n i u m f l u o r o b o r a t eF l u o r o b e n z e n ed) Replacement by OH A r N 2 + A r O H N 2+ H 2 O H + +N H 2C H 3O HC H 3N 2 + H S O 4 C H 3o T o l u i d i n e o C r e s o lH 2 O , H +H 2 S O 4N a N O 2h e a tExample: e) Replacement by H A r N 2 + A r O H N 2+ H 3 P O 2 H 2 O + H 3 P O 3 +Example: C lN H 2H 2 S O 4H N O H 3 P O 3C l2 , 4 D i c h l o r o a n i l i n e m D i c h l o r o b e n z e n eC lN 2 + H S O 4 C lC lC l2. Coupling A r N 2 + X + G GNA r NG m u s t b e s t r o n g l y e l e c t r o n r e l e a s i n gg r o u p : O H , N R 2 , N H 2 , N H 2Example: + O HNNO HN 2 + C l B e n z e n e d i a z o n i u m c h l o r i d ep H y d r o x y a z a b e n z e n ep ( p h e n y l a z o ) p h e n o lPreparation of Aldehyde amp。 Ketone Aldehyde 1. Oxidation of Primary Alcohols 2. Oxidation of Methylbenzene 3. Reduction of Acid chloride Ketone 1. Oxidation of Secondary Alcohols 2. FriedelCrafts Acylation Preparation of Aldehyde amp。 Ketone 1. Oxidation of primary alcohols Example: P y r i d i n i u m c h l o r o c h r o m a t eC OHC H 3 C H 2 C H 2C H 3 C H 2 C H 2 C H 2 O Hn B u t y l a l c o h o l1 B u t a n o ln B u t y l a l d e h y d eB u t a n a l2. Oxidation of methylbenzene C l 2 , h e a tC r O 3 / A c 2 OA r C H C l 2A r C H ( O O C C H 3 ) 2A r C H OA r C H 3 H 2 OExamples: H 2 OB rC H 3B rC H C l 2B rC H OC l 2 , h e a t , h vp B r o m o t o l u e n e p B r o m o b e n z a l d e h y d eC r O 3 / A c 2 O H2 ON O 2C H ON O 2C H 3N O 2C H ( O A c ) 2p N i t r o t o l u e n e p N i t r o b e n z a l d e h y d e3. Reduction of acid chloride R C O C l o r A r C O C l L i H ( O B u n ) 3 R C H O o r A r C H OExample: N O 2C O C lL i H ( O B u n ) 3N O 2C H O1. Oxidation of secondary alcohols 2 o a l c o h o l K e t o n eR C H R 39。O HCOR 39。RC r O 3 o r K 2 C r 2 O 7Example: C H 3HO HC HH 3 C C H 3K 2 C r 2 O 7 H 2 S O 4C H 3C HH 3 C C H 3O2. FriedelCrafts acylation +R C O C l R C O A rL e w i s a c i dA r HExamples: +n C 5 H 1 1 C O C l n C 5 H 1 1 C OC a p r o y l c h l o r i d e n p e n t y l p h e n y l k e t o n eA l C l 3+ A l C l 3C O C l C OB e n z o y l c h l o r i d e B e n z o p h e n o n e( D i p h e n y l k e t o n e )Reactions of Aldehyde amp。 Ketone 1. Oxidation 2. Reduction 3. Addition of Cyanide 4. Addition Derivatives of ammonia 5. Addition of Alcohols 6. Cannizzaro Reaction 7. Addition of Grignard Reagent Reactions of Aldehyde amp。 Ketone 1. Oxidation a) Aldehydes R C H Oo rA r C H OR C O O Ho rA r C O O HU s e d c h i e f l yf o r d e t e c t i o no f a l d e h y d eK M n O 4K 2 C r 2 O 7A g ( N H 3 ) 2 +Example: + 2 A g ( N H 3 ) 2 +C
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