有機合成課件第2章基礎(chǔ)有機合成(參考版)
2025-01-23 07:06本頁面
【正文】 C C C O R 39。RP h 3 P OExample: + +P h 3 P C H 2 P h 3 P OO C H 2M e t h y l e n e t r i p h e n y l p h o s p h o r a n e M e t h y l e n e c y c l o h e x a n e3. Nucleophilic acyl substitution a) Claisen condensation OC O R 39。1o2o3oReaction of Carbanion 1. Halogenation of ketones 2. Nucleophilic Additon to Carbonyl Compounds 3. Nucleophilic Acyl Substitution 1. Halogenation of ketones Reaction of Carbanion C COHK e t o n e a H a l o k e t o n eX 2 = C l 2 , B r 2 , I 2X 2H + o r O H C COX+Examples: ++C y c l o h e x a n o n e 2 B r o m o c y c l o h e x a n o n eB r 2 H B rH +HOB rOH 3 C C COC H 3C H 3C H 3H 3 C C COC I 3C H 3C H 3H 3 C C COC O O C H 3C H 3I 2 , O H t e r t B u t y l m e t h y l k e t o n e T r i m e t h y l a c e t a t e i r o nO H 2. Nucleophilic addition to carbonyl pounds a) Aldol condensation C C OHb a s e o r a c i dC C C OHO HA l d o lCO+Examples: C H 3 C OHC H 2 C OHHC H 2 C OHC H 3 CHO HC H 3 C CHC OH H+ H+ N a H S O4h e a tA c e t a l d e h y d e 3 H y d r o x y b u t a n a l 2 B u t e n a lC H 3 C OC H 3C H 2 C OC H 3HC H 2 C OC H 3C H 3 CHO HC H 3 C CC H 3C OH C H 3+ H+ N a H S O4h e a tA c e t o n e 4 H y d r o x y 4 m e t h y l 2 p e n t a n o n e 4 M e t h y l 3 p e n t e n 2 o n eC H 2 C C H 3O+C OHH C C H C C H 3HOB e n z a l a c e t o n eb) Wittig reaction + +COP h 3 P CR 39。 39。C OHHC OHR 39。 39。 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 H 3 C H O 3 O H C H 3 C O O 2 A g 4 N H 4 2 H 2 OT o l l e n s t e s t+ ++ +b) Methyl ketones Examples: COC H 3C C HC H 3C H 3COO HC C HC H 3C H 34 M e t h y l 3 p e n t e n 2 o n e 3 M e t h y l 2 b u t e n o i c a c i dK O C l H 2 S O 4COC H 3RO X COC H 3A rCOC X 3RCOC X 3A rCOO RCOO A rH 2 O H a l o f o r mr e a c t i o n+ + +COC H 3C 2 H 5 COO C 2 H 53 O I C H I 3 2 O H I o d o f o r m2. Reduction a) Reduction to alcohols H 2 / N i , P t , P dL i A l H 4 o r N a B H 4 , t h e n H +C O C O HHExamples: O H O HH 2 , N iC y c l o p e n t a n o n e C y c l o p e n t a n o lC C H 3OL i A l H 4A c e t o p h e n o n e a p h e n y l e t h y l a l c o h o lC C H 3O HHb) Reduction to hydrocarbons C O C HHZ n ( H g ) , c o n c . H C lN 2 H 4 , B a s eC l e m m e n s e n r e d u c t i o nf o r c o m p o u n d s s e n s i t i v e t o b a s eW o l f f K i s h n e r r e d u c t i o nf o r c o m p o u n d s s e n s i t i v e t o a c i dN 2 H 4 , B a s eOH HC y c l o p e n t a n o n e C y c l o p e n t a n eExamples: C C H 2 C H 2 C H 3On B u t y r o p h e n o n eC H 3 C H 2 C H 2 C O C ln B u t y l b e n z e n eZ n ( H g ) , c o n c . H C lC H 2 C H 2 C H 2 C H 3A l C l 33. Addition of cyanide +C O C C NH C N C y a n o h y d r i nExamples: C COHO HC N CHO HC O O HB e n z a l d e h y d e M a n d e l o n i t r i l e M a n d e l i c a c i dN a C NN a H S O 4H 2 OH 2 S O 4HC H 3 CC H 3 COC H 3O HC N C H 3 CC H 3O HC O O HN a C NN a H S O 4H 2 OH 2 S O 4C H 3a c e t o n ec y a n o h y d r i nM e t h a c r y l i c a c i dC H 2 CC H 3C O O H4. Addition derivatives of ammonia +C O H 2 N G C N G U s e d f o r
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