【正文】 C H 2 C H 3Use of Protecting and Blocking Groups N H2C H3C O C lb a s eN H C O C H3H N O3H2S O4N H C O C H3+N H C O C H3N O2N O29 0 %t r a c e1 . H2O , H2S O42 . O HN H2N O2Use of Protecting and Blocking Groups N H2C H3C O C lb a s eN H C O C H3c o n c dH2S O4N H C O C H3S O3HN H C O C H3S O3HH N O3N O21 . H2O , H2S O42 . O HN H2N O2The Birch Reduction N aN H 3 , E t O HAddition Reaction of Aldehydes and ketones Grignard Reaction: Reformatsky Reaction: C H 3 C H 2 M g B r + C H 3 C H O1 . E t 2 O2 . H 3 O + C H 3 C H 2 C H C H 3O HC H 3 C H C H 2 C H O + C C O 2 C H 2 C H 31 . Z n2 . H 3 O +C H 3 C H C H 2 C H C C O 2 C H 2 C H 3C H 3C H 3B rC H 3 C H 3O H C H 3C H 3Addition of Hydride ion General Reaction: C OH : + C O H H 3 O+C O HHO + L i A l H 41 . E t 2 OH 3 O+2 .O HHC H 3 C C H 2 C H 2 C H 3O+ N a B H4 C H 3 C H C H 2 C H 2 C H 3O HC H 3 O HO HAddition of Hydrogen Cyanide RR 39。O1 . N a C N2 . H ARR 39。O HC NH C l / H2Oh e a tRR 39。O HC O O HRR 39。O HC H2N H2L i A l H4Eg Addition of Yields OA r 3 P+C +CA r 3 P OC + A r3 P OO + A r3 P+C H 2C H 2Addition of Alcohols C 2 H 5 O H + C H 3 C H O C 2 H 5 O C O C 2 H 5HC H 3OOO C 2 H 5OO C 2 H 5O H C H2C H2O HOO( 1 ) L i A l H4E t2O( 2 ) H2OO HOOH3O+H2OO HOAddition of Derivative of ammonia C O + H 2 N R C NRC O + H 2 N H N R C N N HRThe WolffKishner Reduction C C H 2 C H 3O+ N H 2 N H 2N a O Hh e a tC H 2 C H 2 C H 3The BaeyerVilliger Oxidation of Aldehydes and Ketones Migratory aptitude: Pay attention to the mechanism C 6 H 5 C C H 3OR C O O HOC 6 H 5 C C H 3OOTollen’s Test(silver Mirror Test) R C H OA g ( N H3)2+H2OR C O O H + A gR CA g ( N H3)2+H 2 OOR , n o r e a c t i o nReactions via Enoles and Enolate Anions Halogenation of ketones The haloform reaction C COH+ X 2a c i do r B a s e C COXC 6 H 5 C C H 3O+ X 2 a c i do r B a s e C 6 H 5 C O O+ C H X 3The aldol reaction: The addition of Enolate anions to aldehydes and ketones R C H2C HOO HH2OR C H2C H C H C HO HROA n a l d o lN a B H4R C H2C H C H C H2O HO HRH A H 2 OR H2C H C C C H ORH 2 / N iR C H2C H2C H C H2O HRL i A l H 4R H2C H C C C H2O HRH2, P d CR C H2C H2C H C H2O HRClaisenSchmidt reaction C 6 H 5 C HO+ C H 3 C C H 3OO H C 6 H 5 C H C H C C H 3OCondensations with nitroalkanes and Nitriles C 6 H 5 C HO+ C H 3 N O 2O HC6H5C H C H N O2H 2 / N iC6H5C H C H2N H2C 6 H 5 C HO+ C 6 H 5 C H 2 C NE t OC6H5C H CE t O HC NC 6 H 5Cyclizations via aldol condensation C H 3 C C H 2 C H 2 C H 2 C H 2 C HO O O H C C H 3OLithium Enolates OH 3 CH HHB :OH 3 COH3CHHK i n e t i c e n o l a t e T h e r m o d y n a m i c e n o l a t eL e s s s t a b l e m o r e s t a b l eOH 3 CH HHO L i +H 3 CD M EL i + N ( i C 3 H 7 ) 2Direct Alkylation of ketones via Lithium Enolates OH 3 CO L i +H 3 CD M EL i + N ( i C 3 H 7 ) 2 C H 3 IOH 3 C C H 3Conjugate addition Organocopper reagents add almost exclusively in the conjugate manner C 6 H 5 C H C H C C6 H 5O+ C NC 6 H 5 C H C H2 C C 6 H 5C NOC H 3 C H C H C C H3O+ C H 3 C u C H3 C H C H 2 C C H 3C H 3OMichael additions OOC H3+ H 2 C C H C C H 3OO HOOC H3Oc o n j u g a t ea d d i t i o nO Ha l d o l c o n d e n s a t i o nOC H3OCarboxylic acids and their derivatives ahalo acids RH2C COO HP + B r2( P B r3)RHC COO HB rO HRHC COO HO HN H3RHC COON H3+Decarboxylation of carboxylic acids CH2C COO HORh e a tC C H3OR+ C O 2C C COO HOH ORRh e a tC COO HRRH + C O 2Reactions of Nitriles C NRH3O+, h e a tR C O O H( i B u )2A l HH2OR C H OR 39。 MM = M g B r o r L iR C O R 39。The Mannich Reaction C H 3OH 3 C+ C H 2 O + ( C 2 H 5 ) 2 N H C H 3 C C H 2O H2C N ( C 2 H 5 ) 2Synthesis of Enamines: Stork Enamine Reactions N+ B r C H2C O C2H5O N+C H2C O C2H5OH2OOC H2C O C2H5OAcetoacetic ester synthesis C C H 2 COO E tOH 3 C1 . N a O E t2 . R B rC C H COO E tOH 3 CRO H, h e a t1 .2 . H 3 O+3 . h e a tCH 2COH 3 C R1 . K O C ( C H 3 ) 32 . R 39。 B rC C H COO E tOH 3 CRO H, h e a t1 .2 . H 3 O+3 . h e a tC C HOH 3 C RC C COO E tOH 3 CRR 39。R 39。Amines: Diazotizatoin of primary Arylamines A r N H2H O N O0 5oCA r N+2C u2O , C u2+ , H2OA r O HC u C lA r C lC u B rA r B rC u C NA r C NK IA r I( 1 ) H B F 4h e a tA r FH 3 P O 2 , H 2 OA r HThe Hofmann Elimination Hofmann rule: Yield mainly the least substituted alkene. C H 3 C H 2 C H C H 3 O H + N ( C H3 ) 31 5 0 o CH 3 C H C C H C H 3 C H 3 C H 2 C H+ C H 2+ ( C H 3 ) 3 N : + H 2 O5 % 9 5 %The Cope Elimination The Cope elimination is a syn elimination: C H C H 2N +RC H 3C H 3 OHs y n CHC H 2R + NC H 3C H 3H OPhenols and Aryl halides Williamson synthesis O HN a O HO N aR C H2