【正文】 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 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。Chapter 2 Basic of Organic Synthesis Preparation of Alkane of Alkenes 2. Reduction of Alkyl Halides 3. Coupling of Alkyl Halides with Organometalic Compounds R M g X H 2 O R HR X + M gPreparation of Alkane 1. Hydrogenation of alkene C n H 2 n H 2 + P t , P d , N i C n H 2 n + 2A l k e n e A l k e n e of alkyl halides a) Hydrolysis of Grignard reagent. Example: C H 3 C H 2 C H C H 3B rC H 3 C H 2 C H C H 3M g B rC H 3 C H 2 C H C H 3HM g H 2 On B u t a n es e c B u t y l m a g n e s i u m b r o m i d es e c B u t y l b r o m i d eb) Reduction by metal and acid. R X + Z n + H + R H + Z n 2 + + X Example: C H 3 C H 2 C H C H 3B rC H 3 C H 2 C H C H 3Hn B u t a