课件有机上下册老师11醛和酮

1、6OOCRCHORCR'Carbonyl羰基Aldehyde醛Ketone酮§1 命名一、醛Rule: 选主链, 定母体；编号；排序烷醛ane-alOOOCH3CHCH2CHCHHCHH3CCHCH3CH2CH3甲醛 methanal formaldehyde乙醛 ethanal acetaldehyde4-甲基-2-乙基戊醛2-ethyl-4-methylpetanalgbaCH3CH2CHCH2CHO CH3b-甲基戊醛或 3-甲基戊醛b -methylpetanalH3CCHOCHO3-甲基环己基甲醛3-methylcyclohexanecarbaldyhyde苯甲醛b

2、enzenecarbaldehydebenzaldehydeO2NCHOp-甲醛p-nitrobenzenecarbaldehyde654321CH3CH=CHCHCH2CHOCH33-甲基-4-己烯醛3-methyl-4-hexenal名二、酮Rule: 选主链, 定母体；编号；排序烷酮ane-anoneOH3CCCH3O CH3CH2CCH562CHCH35-甲基-3-己酮5-methyl-3-hexanonepropanone acetone123 4OCH3H3CO4- 甲基环己酮CCH2CH3OO1-苯基-1-1-phenyl-1-propanone2,4-己二酮4-methylcy

3、clohexanoneO CH3CHCHCH2CCH365432 1CH3CCH2CCH2CH312 34 564-己烯-2-酮4-hexen-2-one2,4-hexanedioneCH2O n多聚甲醛H+ CH2OH+OOO三聚甲醛化合物普通命名法IUPAC命名法熔点/沸点/溶解度g/100 g H2O甲醛HCHOformaldehydeformaldehyde-9221易溶乙醛CH3CHOacetaldehydeacetaldehyde-1212116丙醛CH3CH2CHOpropionaldehydepropanal-81497丁醛CH3(CH2)2CHOn-butyraldehyde

4、butanal-9976戊醛CH3(CH2)3CHOn-valeraldehydepentanal-92103苯甲醛PhCHObenzaldehydebenzaldehyde-261780.3CH3COCH3acetonepropanone-9556丁酮CH3CH2COCH3ethyl methyl ketone2-butanone-8680262-戊酮CH3(CH2)2COCH3methyl propyl ketone2-pentanone-781026.33-戊酮C2H5COC2H5dimethyl ketone3-pentanone-401025环己酮Ocyclohexanonecycl

5、ohexanone-451552.4苯乙酮PhCOCH3methyl phenyl ketone1-phenyl-1-ethanone21202不溶苯PhCOCH2CH3ethyl phenyl ketone1-phenyl-1- propanone21218不溶二苯酮PhCOPhdiphenyl ketoneDiphenyl methanone48306不溶§2 醛酮的物质性质§3 醛酮的化学性质一、羰基的结构与反应特征ddCOC O亲核加成反应dOO-OHCHACd CNu:-NuNusp2杂化，平面结构sp3杂化，四面体二、羰基的亲核加成反应1. 加HCNH3O+OH

6、C O+HCNCCNOHCCOOHa-羟基酸(1) LiAlH4(2) H2OOHCCH2NH2a-氨基醇OHOHCHOH2SO4CCNH O+CCOOH+NaCNH 3HEnzymePhCHO + HCN7MechanismHCNH+CN-O-OHHCN9ddC OCN-slowCCNCCN实验证据：加少量碱反应的进行相对活性：Problems:H C O>HR C O H>R C O R'比较如下化合物与HCN反应的活性大小(1)R CO H> Ar C O H(2)R C O >R'R C OAr芳环与羰基p-p共轭，减弱羰基碳正性O(3)(CH3

7、)3CCC(CH3)3<OCCH3(4) 将如下化合物与HCN反应的活性大小排序CH3OOCH3CHOCH3CHCHOClCH2CHOCH3CC2H5CH3CCH3ABCDEC>A>B>E>D脂肪族醛酮与HCN反应活性，主要受空间因素影响(5) 将如下化合物与HCN反应的活性大小排序O2NOOOCHCH3OCHCH叔丁基的位阻，妨碍亲核试剂接近羰基碳ABCA>C>B芳香族醛酮与HCN反应活性，主要受效应的影响反应范围RCHO RCOCH3 8碳以下的环酮2. 与饱和NaHSO3溶液反应10ddOOH亲核中心为S，不是OC OHOSONaCSO3Na反应

8、范围： RCHO RCOCH3 8碳以下的环酮H3O+OHCSO3NaOH-/H2OOHC O+Na+SO2+H2O C O+Na2SO3+NaHCO3OHCSO3Na+NaCNCCN+Na2SO33. 与ROH加成RH+R OHR'OHR OR'COH OR'HC OR'H+HC OR'HMechanism半缩醛缩醛H+R C OH HR C OH HH OR'R OR'C OHH-H+R OR'C OHHR半缩醛COHH酸的作用活化羰基，增大羰基的碳正性H+ROR' OR'R+HOR'OR'HH

9、R C-H2OR OR'COH2COR'H-H+C OR' HH缩醛OR'RCH1171OH+H3COC2H5CH3CCH3+2 CH3CH2OHH C C+H2OO+CH2OHH+ CH2OH3OC2H5缩酮O+H2OO回流管waterCH2OHH+ORCHO+CH2OHRCHO+H2O分水器缩醛(酮)的分解缩醛R R'(H)OR"COR"R3H O+COR'(H)+2 R"OH分水器缩醛(酮)在碱性条件下是的，但对酸敏感保护羰基O CH3CCH2CH2XH+CH2OHCH2OHO+MgCH3CCH2CH2MgXH

10、3COC CH2CH2XMgOH3COC CH2CH2MgX OOH3COC CH2CH2CH2CH2OMgXCH3CCH2CH2CH2CH2OHH3O+OO4. 与RSH（硫醇）加成H+C O+2 RSHC SR SR+H2O硫代缩醛（酮）33H CO+SHH C SHSR-NiH3CSH2Hg2+/H2O+NiSCH2SHH+SRCHOH3CO+CH2SHRCHS+H2On-BuLiRS CLiSR'XRS CR'SHg2+/H2O RC OR'Problem?OHCOH3COSHH+SH1 molS SOR-Ni H2H3COCH3CH2MgBrSOMgBrSCH

11、2CH3(1) H3O+(2) Hg2+OHCOH C2H55. 与H2O加成C O+H2OK平衡OHC OHK平衡的大小取决于羰基上的取代基H C O HK平衡O+H2HOH C OHHK = 2 x 10399.9%Cl3CC OH+H2OCl3COHC OH H6. 与金属有机试剂RM加成RM: RMgBr, RLi, RC=CNaddRH3O+RCORMgBrCOMgBrCOHRMgBr与RLi的区别各种醇的O(CH )CHLiOLiH O+OH(CH3)3CCC(CH3)33 2(CH3)3CCC(CH3)33CH(CH3)2(CH3)3CCC(CH3)3CH(CH3)2O+HCCN

12、aONaCCHH3O+OHCCHH2O/Hg2+/H+OH COCH37. 与氨的衍生物加成NH3NH2Y反应通式：NH2R胺NH2OH羟胺NH2NH2肼NH2NHPh 苯肼O NH2NHCNH2 氨基脲RO+NH2Y可逆RRO-OHR'(H)R'(H)NH2YR'(H) NHY-H2ORNYR'(H)RO+R'(H)NH2R胺NH2OH羟胺NH2NH2肼RR'(H)RR'(H)RH+弱酸R'(H) RNRN OHNNH2亚胺碱Schiff Base肟腙NH2NHPh 苯肼OR'(H)RNNHPh苯腙NH2NHCNH2氨基

13、脲R'(H)NNHCONH2半腙缩胺脲R R'(H)O+H+ ROHR'(H)ROHR'(H)活化羰基NH2Y +H+RNH3YNH2失活ROR'(H)R+NH2NH O2N羰基试剂H+NO2RNNHR'(H)O2N2,4-二腙NO2黄色R'(H)NY+H2OR'(H)O+H2NY水解HOCC三、涉及羰基a-H的反应1. a-H的酸性及烯醇平衡HCCHHCC-+H+pKa = 25OH3CCO2CH3H3CCCH -+H+pKa = 20OCC HOCC-H+HH+OCCOCCO-CC烯醇平衡O-CC+H+OH CC2. a-卤代

14、及卤仿反应A. 酸催化下的卤代反应O+OCC+X2HCCHXOCH3CO2HOCCH3+Br2CCH2Br动力学实验：反应速度与羰基化合物以及酸的浓度相关， 但与卤素的浓度无关结论：反应的决速步骤在卤素参与反应之前MechanismOOHCH3CO -OH+CCH3HH2CCH2slowCCH2ddfast酸催化烯醇化O-H+BrBrfastOHCCH2BrfastCCH2BrO+Cl2OCl+HCl自动催化反应B. 碱催化下的卤代反应OOH3CCMechanismCH3+X2NaOHH3CCCH2XOH3CCCH3OH-slowO2H3CCCH -O-ddOH3CCCH2XXfastH3CC

15、CH2XOOH-OO-ddH3CCCH2XH3CCCHXHCCCHXXXOOH3CCCHX2H3CC3CX3OH3CCO CH3+X2NaOHH3CCCX3OH-CH3CO2H+CX3O-H3CCCX3OH23CH3CO -+CHX卤仿OH3CCO CH3+I2NaOHH3CCOH+CHI3黄色碘仿反应碘仿反应的应用鉴别有机分子中是否具有OH3CCOHH3CC H结构单元OHOH-OI /OH-H3CC HCH2CH3+I2H3CCCH2CH3 2CH3CH2CO2H+CHI33223HCO2HCHI3CH CH OH+I /OH-CH CHO I2/OH-反应的方向OCH3Br/CH CO

16、HOCH3 232BrOHCH3<OHCH3性酸性条件：卤代反应发生在取代的a碳上OI /OH-碱性条件：卤代反应发CH3CCH2CH32CH3CH2CO2H+CHI3生在取代基少的a碳上：决速步骤中碱夺取a-H形成烯醇负离子，取代少的a-C上H的酸性强，位阻小3. 羟醛缩合(Aldol)反应A. 碱催化下的羟醛缩合反应稀NaOHba2 CH3CHOCH3CH=CHCHOa,b-不饱和醛MechanismOOOCH CHO-OOHOOH-3CHCHCH CHH2OCHCHCH CHCH3CHfastCH2CH32slow32-H2OO- H2CCHCH3CH=CHCHOCH CHCHOO

17、H-OHCH33CH3CHCHCCHO羟酮缩合CH3CH3CH33PhCOCHOH-PhC=CHCOPhCH3OOAlOC(CH3)33B. 酸催化下的羟醛缩合反应332 CH CHOH+CH CH=CHCHOH+CH3CH=CHCHO-H2OH2CCHOHCH3CH=OO-OH CH3CHCH2CHOHO CH3CHCH2CHC. 分子内的羟醛缩合反应OOH-OOH3COHC CH2CH2CH2CHCHOCH3OH-CHOD. 交叉羟醛缩合反应CH3CHO+CH3CH2CHOOH-四种产物交叉羟醛缩合反应a, b-不饱和醛酮的3CHO+CHCHOOH-CCHCHO H提供羰基提供a-HCHO

18、 +OH3CCOH-OCCCHH2OCHO+CH3CHCHOOH-OHCCHOCCH3不对称的酮Aldol反应的取向OH+O PhCH=CCCH3CHPhCHO+CH3CCH CH323OOOH-O PhCH=CHCCH2CH3OOLiH3CLDA-78H3CLiCH3CHOH3CCHCH3H2OLDA: (CH3)2CH2NLi(CH3)2CH2NH +n-BuLiOOHH3CCHCH3四、氧化反应1. 强氧化剂：KMnO4/H+, K2Cr2O7/H+, HNO3RCHO4KMnO /H+RCOOHCH2CHOKMnO4/H+CO2HOH2KMnO4浓HNO3CH2CO2HH3CCCCH3

19、CH3CO2H+CH3CH2CO2H+HCO2HO浓HNO3CO2H CO2HCO2+H2O2. 弱氧化剂：Tollens试剂 AgNO3/NH3.H2O Ag(NH3)2+OH- Fehling试剂 CuSO4/OH- + 酒石酸钾钠HOCO2HOCO2NaCuHOCO2HOCO2K2RCHO+Ag(NH3)2OHRCO -+Ag22RCHO+Cu2+ OH- RCO -+Cu OO(1) Ag(NH3)2OHRCHCHCH+(2) H3ORCHC HCO2HCH2CHO Ag(NH3)2OHCH2CO2H3.维立格氧化(Baeyer-Villiger)OOORC RCH3CO3HORC O

20、RCH3CO3HOMechanismRR OHO-RCO-OHORORO OC R2ROR反应方向H O OCRO RCOR-H+OHROROOORCO HRR'3 ROR' +R?OR'R迁移能力：Ar>3o>2o>1o>CH3H3C>> XOCCH3OCF3CO3HOCCH3OCF3CO3HH3COCOH3COOCRCHO RCO3HRCOH氢优先迁移2五、还原反应1. 还原为醇A. 催化氢化ROR'(H)RH2/NiOHR'(H)选择性差O H2CCHCH2CCH3H2/NiOH H3CCH2CH2CHCH3OH

21、2/NiRCHCHCCH3ORCH2CH2CCH3条件催化氢化活性：CHO > C=C > RCORB. 化学还原LiAlH4, NaBH4R R'(H)OLiAlH4or NaBH4ROHR'(H)选择性好CH CH=CHCHO(1) LiAlH4/THF32CH CH=CHCH OH3(2) HO3O+OH+LiAlH4LiAlH4: 可还原COR, CO2H, CN, NO2NaBH4:只能还原醛酮羰基C.外因彭R还原(Meerwein-Ponndorf)(CH3)2CHO3AlROH+CHCOCHR'(H)O+(CH3)2CHOH可逆33R'

22、(H)MechanismRAlOCH(CH3)22OAlOCH(CH3)22 OOCCH3RCHR'(H)HCH3(H)R'负氢转移R R'(H)OH +(CH3)2CHOH(CH3)2CHO3Al脑氧化(Oppenauer)R R'(H)OH+CH3COCH3(CH3)2CHO3Al可逆R R'(H)O+(CH3)2CHOHMechanismRRO AlOCH(CH3)22+(CH3)2CHOHR'(H)OH +(CH3)2CHO3AlR'(H)HO醇交换OHH3C(CH3)2CHO3AlH3CCH3RO+R'(H)O(CH3)

23、2CHO3AlPhCHCHCPh H+O H3CPhCHCHCPh+(CH3)2CHOHD. 金属还原单分子还原： Na/C2H5OH; Fe/CH3CO2HMechanismR R'(H)Na/C2H5OHOROHR'(H)RR'(H)ONaROR'(H)C2H5OHROHR'(H)NaROHR'(H)负离子基C2H5OHROHR'(H)双分子还原： Mg, Mg-Hg齐/非质子性溶剂RMgObenzeneH3O+R'R'RCCR还原偶联R'MechanismROMgR'R'RCO Mg.OH O

24、HROR'R'R'RCCR O MgOR'R'RCC RH3O+R'R'RCC ROH OHO MgO2. 还原为烃A. Clemmensen还原RZn-Hg/HCl OR'RCH2R'PhCOCH3Zn-Hg/HClPhCH2CH3B. Wolff-Kischer还原RO+NH2NH2R'改进KOHR CHpressureR'2RO+NH2NH2R'NaOH(HOCH2CH2)2ORCH2R'MechanismR+NH NHRNHNHB-RNHNHRN=NHO222R'R'

25、R'R'RR-N2RBHB-RCH2BHCH R'R'CH N=N R'CH N=NHR'C. 硫代缩酮的还原SHH+O +SHSH2/R-Ni S+NiS3. 歧化反应Cannizzaro反应OCH2OR3CHOPhCHOCHO无a-H2 PhCHO 浓NaOHPhCONa+PhCH OH222浓NaOH+ OCHOOCO2NaOCH2OHMechanismOO-ArCHOArCH-ArCHOH-亲核加成OH负氢转移ArCO2H +ArCH2O-ArCO2+ArCH2OH2 CH3CHO 浓NaOHCH3CH=CHCHO交叉歧化反应PhCHO

26、+浓NaOHOCHO四种反应方式PhCHO +CH2O浓NaOHPhCH2OH +HCO2H+OCHOCH2O浓NaOH+OCH2OHHCO2H甲醛羰基活性高，优先受到OH-的进攻六、其它重要反应1. Wittig反应O +Ph3PR RR'R'R+Ph3P=OA. Wittig试剂的Ph3PWittig试剂磷(Yilde)R'Ph P+RCH2X SN2Ph3PCH2R X-n-BuLiPhPCHR3Ph3P+CH3Br季鏻盐Ph3PCH3 Br-n-BuLi3Ph3P=CH2Ph3P+CH2=CHCH2ClPh3PCH2CH=CH2 Cl-n-BuLiPh3P=CH

27、CH=CH2B. Wittig反应的机理RO-PPh3OPh3PR'CRR'R-Ph3P=O R'OPPh3 CRR'C. Wittig反应的应用CH2CH3 OHCHCHOH3CHCH3CH2CH3OCHCH3+Ph3PCHCH3CH2Ph3POCH2+OBrO+Br22. 安息香缩合反应CN-HOOOOO2 PhCHOPhCHCPh MechanismO-OHPhhHCN-H O-OHPhCOPhCOHPhCCN2HPhCHCNOHPhCCN失去质子决速步骤OH O-PhhO-OHPhh-CN-OOHPhhCN HCN HHO2NCHOCN-No React

28、ionCN-CH3OCHONo ReactionH决速步OHPhC OOH O-PhhPhC CNCN H：吸取代基减弱碳负离子的亲核性给取代基减弱羰基碳的碳正性-CN-OOHO2NCHO+反应中提供羰基碳，其碳正性大CH3OCHO反应中提供碳负离子，亲核性大CH3OCCNO2H3.重排(Beckman)-反酮肟重排RO +NH2OHRROHH+ NRor PCl5ORCNHRMechanism酮肟酰胺ROH+R NHRRN OH2-H2ORCNRH2OOH2RCNRH+特点：分子内的反式重排PhPhORCNHROHRCNRH H3CCCNH3CH+CHOHH3CONCCH3手性碳构型保持H七

29、、羰基加成反应的R'O +HNuR'化学R'OH*R'NuR = R'产生一个新的手性中心潜手性碳CNR'O-R'ONu-R'a R'b R'O-R'CNR,R中不含手性碳，则得到外消旋体PhHHCCPhCN+HCN? HCCHH3COH3COHCram规则: 不对称醛酮与亲核试剂加成时，亲核试剂优先从醛酮优势构象中空间位阻较小的一边，既较小基团一边进攻羰基优势构象：手性碳原子上最大基团与羰基处于反式共平面 时，其构象最LRLNuSCC MOHNuRSCCMOHLRLRNuSHNuOMMSOHOH CH3H

30、3COHCH3LiH2OH CH3ONaBH4OH H八、a,b-不饱和醛酮的反应CC O1. 亲核加成43NuCCC OH1,2-加成214321CCCO+HNuH4341,4-加成CCC OHCCC ONu21Nu 32143CC O2143CC O213,4-产物醛羰基活性高，倾向于1,2-加成；酮倾向于1,4-加成A. 与HCN加成OHPhCH=CHCHO+HCNPhCHCHCHCNOPhCHCHCB. 与RMgX加成Ph+HCNPhCHCH2COPhNCO PhCHCHCCH3PhMgBrH3O+OHPhCHCHCPhOPhCHCHCPhCH3PhMgBrH3O+PhCHCH2COP

31、hPhRMgX与加成a,b-不饱和醛酮作用，1,2-加成倾向大，但如羰基上有较大位阻取代基，则倾向于1,4-加成C. 与RLi加成OPhCHCHCPhOHPhLiH3O+PhCHCHCPhPhRLi试剂活性高，倾向于1,2-加成D. 与R2CuLi加成OR2CuLi倾向于1,4-加成(CH2=CH)2CuLiH3O+HCH3CHCHCOCH3H2C=CHOCCH2COCH3 CH3(CH3)2CuLiCH3H3O+H3CCH3CH3CHCH2COCH3 H3CCH3MgBrCuIO CH3CHCHCCH3CH3MgBrH3O+OHCH3CHCHCCHCH332. 亲电加成ClOCH3CHCHC

32、CH3HClCH3CHCH2COCH3OO HBrBr与HX加成，一般为1,4-加成OBr2/CCl4Br BrPhCHCHCCH3Br2褪色PhCCHCOCH3H§4 醛酮的一、醛的1.炔水合，胞二卤代物水解Hg2+/H+HCCH +H2OCH3CHORCCH2B2H6H2O2/OH-RCH CHORHH O/OH-RH22HHOH3 BRCH2CHOCH3Cl/hnCHCl2H O+CHO 232.芳烃氧化CH3新制MnO2CHOCH3CrO3/CH3CO2HCH(OCOCH3)2H2OCHO(CH3CO)2OBrBrBr3.伯醇氧化CH3CH2CH2CH2OHCH3CH=CHC

33、H2OHCrO3/PyridineCrO3/PyridineCH3CH2CH2CHOCH3CH=CHCHO4. Reimer-Tiemer反应OH+CHCl3OH-OHCHO5. 酰氯的部分还原A. Rosenmund还原RCOCl +H2Lindlar催化剂 RCHOCOCl+H2Lindlar催化剂CHOClClB. 化学还原LiAlH(OC(CH3)33LiAlH4+3 (CH3)3COHLiAlHOC(CH3)33RCOClLiAlHOC(CH3)33RCHOO2NCOClLiAlHOC(CH3)33O2NCHO二、酮的1. 甲基酮的RCOCH323RCCH +H O Hg2+/H+R

34、COCH2.的氧化OH RCHRCrO3/H2SO4ORCR3. 芳香酮的+RCOClAlCl3COR4. 酰氯与有机铜化合物的反应RCOCl+R'2CuLiRCOR'H3CO(CH CH CH CH ) CuLiH3COCH CCl3222 2H C CH CCH2CH2CH2CH3H3C3H3COCCH2CH2CH3H3CH3CCuLi2Li+CH3CH2CH2COCl H3CBrO2NCOCH3O2NCOCl+(CH3)2CuLiO2NCOOHO2NCH3Key Reactions1. Reaction with Grignard ReagentsTreatment of

35、 formaldehyde with a Grignard reagent followed by hydrolysis gives a primary alcohol. Similar treatment of any other aldehyde gives a secondary alcohol. Treatment of a ketone gives a tertiary alcohol.O1. PhMgBrOHH3CCCH32. H3O+H3CCCH32. Reaction with Organolithium ReagentsReactions of aldehydes ane k

36、etones with organolithium reagents are similar to those with Grignars reagents.PhOH3CCC(CH3)31. PhLi2. H3O+H3COHCC(CH3)33Reactions with Anions of Terminal AlkynesTreatment of an aldehyde or ketone with the alkali metal salt of a terminal alkyne followed by hydrolysis gives an a-alkynyalchol.PhO 1. H

37、C CNa2. H3O+OHC CH4. Reaction with HCN to form CyanohydrinsFor aldehydes and most sterically unhindered aliphatic ketones, equilibrium favors formation of the cyanohydrin. For aryl ketones, equilibrium favors starting materials, and little cyanohydrin is obtained.H2SO4OHPhCHO + NaCNPhC CN H5. The Wi

38、ttig ReactionTreatment of an aldehyde or ketone with a triphenylphosphonium ylide gives an oxaphosphetane intermediate, which fragments to give triphenylphosphine oxide and an alkene.O+Ph3PCH2CH2 + Ph3PO6. HydrationThe degree of hydration is greater for aldehydes than for ketones.OHCH+ H2O OHHCH(> 99%)OH7. Addition of Alcohols to Form HemiacetalsHemiacetals are only minor components of an equilibrium mixture of aldehyde or ketone and alcohol, except where the OH and the C=O are parts