有機(jī)合成課件第2章基礎(chǔ)有機(jī)合成(完整版)
【正文】 H 2 , c a t .Examples: F e , H C l1 N i t r o p r o p a n e n p r o p y l a m i n eC H 3 C H 2 C H 2 N O 2 C H 3 C H 2 C H 2 N H 22. Reaction of halides with ammonia or amines Examples: N H 3R XNN H 2 N H NRR RR RRRRRR XR XR X R XR X m u s t b e a l k y l o r a r y l w i t h e l e c t r o n w i t h d r a w i n g s u b s t i t u e n t sN H 3N C H 3HC H 3 C H 2C H 3 C H 2 C l C H 3 C H 2 N H 2C H 3 C lE t h y l c h l o r i d e E t h y l a m i n e E t h y l m e t h y l a m i n eC H 2 N H 2N H 3B e n z y l c h l o r i d e B e n z y l a m i n e B e n z y l d i m e t h y l a m i n e2 C H 3 IC H 2 NC H 2 C lC H 3C H 3N ( C H 3 ) 2N , N d i m e t h y l a n i l i n e P h e n y l t r i m e t h y l a m m o n i u m i o d i d eC H 3 IN ( C H 3 ) 3 I2 , 4 D i n i t r o c h l o r o b e n z e n e N M e t h y l 2 , 4 d i n i t r o a n i l i n eC l N H C H3N O 2N O 2N O 2N O 2C H3N H23. Reductive amination C O N H 3R N H2R2N H2+H2, N io r N a B H3C N1oa m i n e2oa m i n e3oa m i n eC H N H2C H N R2C H N H R++H2, N io r N a B H3C NH2, N io r N a B H3C NExamples: N H 3 1 o a m i n e+H 2 , N iOH 3 CH 3 CC H N H 2H 3 CH 3 CA c e t o n e I s o p r o p y l a m i n e( C H 3 ) 2 C H C OHN H 22 o a m i n e+ NHC H 2 C H ( C H 3 ) 2I s o b u t y l a l d e h y d e A n i l i n e N I s o b u t y l a n i l i n e N a B H 3 C N3 o a m i n e+H 2 , N iC H3 CHO ( C H 3 ) 2 N H C H 3 C H 2 NC H 3C H 3A c e t a l d e h y d e D i m e t h y l e t h y l a m i n eD i m e t h y l a m i n e4. Reduction of nitriles C NR R C H 2 N H 22 H 2 , C a t .Examples: C H 2 C lB e n z y c h l o r i d e B e n z y l n i t r i l e 2 P h e n y l e t h y l a m i n eC H 2 C N C H 2 C H 2 N H 2N a C NH 2 , N i ,1 4 0 o CN a C N H 2 , N i ,C l C H 2 ( C H 2 ) 2 C H 2 C l N C ( C H 2 ) 4 C N H 2 N C H 2 ( C H 2 ) 4 C H 2 N H 21 , 4 D i c h l o r o b u t a n e A d i p o n i t r i l e H e x a m e t h y l e n e d i a m i n e( 1 , 6 D i a m i n o h e x a n e )5. Hofmann degradation of amides +R C O N H 2A r C O N H 2O B r 1 o A m i n eC O32 R N H 2A r N H 2Examples: C H 3 ( C H 2 ) 4 C O N H 2 1 o A m i n eC H 3 ( C H 2 ) 4 N H 2C a p r o a m i d e( H e x a n a m i d e )n P e n t y l a m i n eK O B r1 o A m i n eK O B rB rC O N H 2m B r o m o b e n z a m i d e m B r o m o a n i l i n eB rN H 2Reaction of Diazonium 1. Replacement of Nitrogen 2. Coupling 1. Replacement of nitrogen Reaction of Diazonium a) Replacement by Cl, Br, CN A r N 2 + Z : A r Z N 2++A r N 2 + A r X N 2+C u XExamples: C H3N H2C H3N2+C lC H3N2+H S O4C H3C 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
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