第十二章-醛和酮课件.ppt

1、2023-1-101第十二章第十二章 醛醛 和和 酮酮2023-1-102教学目的教学目的 2023-1-103本 章 内 容n第一节 醛和酮的分类和命名 n第二节 醛和酮的化学性质 n第三节 醛和酮的制备方法习题答案课堂设问2023-1-104第一节 醛和酮的分类和命名n一.分 类 n二.命 名 2023-1-105一、分 类 醛和酮分子中都含有羰基（），统称羰基化合物。羰基是醛和酮的官能团。分子组成相同的醛和酮是构造异构体。例如：它们的分子式均为C3H6O，只是构造不同，它们属于官能团异构。醛和酮可根据分子中烃基的不同，分为脂肪（族）醛和酮、脂环（族）醛和酮、芳香（族）醛和酮。例如：丙醛

2、丙酮CH3CH2COHCH3CCH3O2023-1-106脂肪醛和酮脂肪醛和酮 脂环醛和酮脂环醛和酮CH3CH2COCH3CH3CHOCH2CH CHOCH2CH COCH3CHOOCHOC CH3OCO芳香醛和酮芳香醛和酮2023-1-109 月桂醛 巴豆醛 肉桂醛 甲基乙基甲酮 甲基烯丙基甲酮 二苯基甲酮（甲乙酮)(甲烯丙酮)(二苯酮）CH CHCHOCH3(CH2)10CHOCH3CH=CHCHOCH3CH2COCH3CH3COCH2CH CH2CO2023-1-1010（2）系统命名法 CH3CH CH2CHOCH3CH3CCH CHOCH3CHCCHOCH3C CH2CH3OCH3C

3、H2CH CH2C CH2CH3OCH3CH3C CH2COCH2CH33-甲基丁醛 3-甲基-2-丁烯醛 2-丙炔醛丁酮 5-甲基-3-庚酮 4-甲基-4-戊烯-2-酮2023-1-1011 CH3CH CH2CH2CHOCH3CH3CH C CHCH3O CH3CH35 4 3 2 15 4 3 2 1 ,4-甲基戊醛 2,4-二甲基-3-戊酮(-甲基戊醛)(,-二甲基-3-戊酮)2023-1-1012 苯基乙酮 二苯甲酮 二苯乙酮苯甲醛 苯乙醛 3苯基丙醛CHOCH2CHOCH2CH2CHOCOC CH3OC CH2OCH2CHOC CH3OBrCH3CHO苯乙醛 对甲基苯乙醛 对溴苯乙

4、酮2023-1-1013 CH3CC CH2CH3OOCH3CCH2C CH3OO2,3-戊二酮 2,4-戊二酮（-戊二酮）（-戊二酮）问题1、22023-1-1014第二节 醛和酮的化学性质 n一.羰基的结构 n二.醛和酮的物理性质 n三.醛和酮的化学性质 2023-1-1015一、羰基的结构2023-1-1016COHHCOCH3HCOCH3CH32.27D2.72D2.85D2023-1-1017二、醛和酮的物理性质CH3(CH2)6CHOCH3(CH2)10CHOCH3(CH2)14CHOCHOCH2CHOCH3(CH2)16CHOCH CH CHOCHOOHOC2H52023-1-1

5、018CH2CH2C(CH2)12OCH2CHC(CH2)12OCH3CH CH COCH3CH3CH CH3CH3OCH3C(CH2)8CH3OCH2C(CH2)4CH3OCH32023-1-10192023-1-1020R2CR1CH(R)OH BR2CR1CH(R)OHR2CR1CH(R)O 三、醛和酮的化学性质2023-1-10212023-1-10221.羰基的加成反应 2023-1-1023 OC+O-2023-1-1024慢CRR1O(H)+E-Nu-E+CRR1O-Nu(H)CRR1OENuE+(H)2023-1-1025NuNuHR RMgBr,RLiR CCR CCMgBr

6、,R CCNaHLiAlH4,NaBH4CNHO3SNaHSO3NaCNH2NR,HNR2HORH2O2023-1-1026CONuCONuCOHNuRMgBr,RLi,R CCMgBrR CCNaLiAlH4,NaBH4H2ONu,CONuCONuCOHNuNaHSO3NaCN,H2ONu2023-1-1027 2023-1-1028CH3COHCH3CCH3OHCOHCOHCH3COHHCOHCOHCH3CCH3OCOCH3COCH3CH2CH2CHOCH3CHCH CHOCH3C CHCH2OCH3C CH2CH3O2023-1-1029 COHO2NCOHCOHCH32023-1-10

7、30 C O+HCNCOHCN2023-1-1031HCNOH+CN+H2OCOCNCOCNHCOHCNCN+CN苯甲醛氰醇丙酮氰醇CHOCCNOHH+HCNOH-CH3C CH3O+HCNOH-CH3C CH3OHCN与氢氰酸亲核加成历程：2023-1-1032影响醛、酮与HCN的加成反应的因素：HCN +OH-CN-+H2O2023-1-1033 与HCN加成反应的活性顺序：HCHOR-CHOR-CO-RR-CO-C6H52023-1-1034在合成上的应用：CH3CCH3OCH3CH3COHCNCH2CCCH3OO CH3CH3CCCH3OOHOHH2O/H+HCNCH2=C CNCH3

8、-H2OCH3CCH2CH3NH2OHH2/NiH2SO4CH3OH有机玻璃的单体有机玻璃的单体2023-1-1035CNH2CNCNH2COOHCONaCNNH4ClH2O/H+or OHCOHCOHNH3COHNH3NH2COH2NH2CCNNH2CCNNH3CNH2COOHH2O/H+or OH2023-1-1036反应可逆反应可逆HOSOOHOSOOCOCSO3HONaNaHSO3CSO3NaOHH+2023-1-10372023-1-1038RCSO3NaOHHNa2CO3 H2OHClH2OR-CHO +Na2SO3 +CO2 +H2OR-CHO +NaCl +SO2 +H2O20

9、23-1-1039应用实例：应用实例：2023-1-1040优点：可避免使用挥发性的剧毒HCN。c.c.间接制备间接制备问题3:试用化学方法分离下列混合物：（l）环己醇和环己酮 （2）苯酚和苯甲醛 问题32023-1-1041COCOHORCORORROH/干HClROH/干HCl H2O+2023-1-1042 间 硝 基 苯 甲 醛 间 硝 基 苯 甲 醛 缩 二 甲 醇 乙 醛 乙 醇 乙 醛 缩 二 乙 醇 CH3CHO+2C2H5OHCaCl2CH3CHOC2H5OC2H5+2H2OCHONO2+2CH3OHH2SO4CHNO2OCH3OCH3+2H2O2023-1-1043 OCH

10、2CH2OHOH+OOCH2CH2+H2O对甲苯磺酸苯2023-1-1044 2023-1-1045CHOHClOCH3OCH3OHOOHTsOHOO H2O+H2O+2 CH3OH2023-1-1046CHOCH2OHOHHHHOOHHOHHOHHOHOHHHHOCH2OHHOHOHHHOHOHHHHOCH2OHHOAg(NH3)2+OOHHOHOHHHHOCH2OHHOH+AgROOHRRHOOR2023-1-1047HCOHCOCOHROHHHCOHORHHCOH2ORCORHHCORORHCORORHORHORH2O亲电性增强亲电性增强2023-1-1048RCROHCOOCH3H+R

11、CRH3COOCH3H+RCREtOOEtCH3CH3CEtOOEtOCH3CHOCH3OCH3CH3CH3CORCRO蒸馏除去蒸馏除去2023-1-1049（分两步）（分两步）H+CH3CH3CEtOOEtCH3CH3CEtOOEtHCH3CH3COEtH2OEtOCH3CH3COH2EtOHEtOHCH3CH3COHEtOHCH3CH3COHCH3CH3COH+来自下步反应来自下步反应2023-1-1050RCROHEtOHRCROHEtOHRCROHRCROEtOEtEtORCROH2EtORCR H2OEtOHH HRCROEtOEt来自上步反应来自上步反应2023-1-1051RCR

12、EtOOEtHRCREtOOHEtRCROEt HOEtHOOHRCREtOHOOHRCROOOHHEt HOEtRCREtOOEtH+HOOHRCROO2 HOEt2023-1-1052OOCH3OHHOOCH3O(干干)HClRCROOHRCROOHRCROO H2023-1-1053H3CC(CH2)2OCH3CCH3OHH3CC(CH2)2OMgBr+H3CCCH3O分子内羰基将参与分子内羰基将参与反应，应先保护。反应，应先保护。H3CC(CH2)2OBrH3CC(CH2)2OCH3CCH3OH2023-1-1054H+MgOHOH(1)(2)H2OH2OH+RC(CH2)2CH3CC

13、H3OHOOH3CC(CH2)2OBrH3CC(CH2)2OOBrH3CC(CH2)2OOMgBrH3CCCH3OH3CC(CH2)2OCH3CCH3OH无无水水乙乙醚醚+OHOH醚键，碱性醚键，碱性条件下稳定条件下稳定缩酮水解，除去保护缩酮水解，除去保护2023-1-1055OBrONaOHNaOHCOONaOBrH+OHOHOBrBrOONaOHOOH2OH+O2023-1-1056BrCH2CH2CHOC2H5OHH+Br CH2CH2CHOOC2H5C2H5OH-CH2CHCHOOC2H5C2H5OH3+CH2CHCHO 3-溴 丙 醛 3-溴 丙 醛 缩 二 乙 醇 丙 烯 醛 缩

14、二 乙 醇 丙 烯 醛 2023-1-1057MeOOEtOHOOHMeOEtOOOH2NEtOOOHNH3LiAlH4H2NEtOO1.H2.OHHNEtOH3NEtOH2O保护羰基保护羰基去除保护去除保护2023-1-1058OHHOOHOHOORCClOEt3N(碱)OCROCH3CCH3OHClH2OH+OOOCROHOOHRCClO2023-1-1059RCRORCR干HCl H2O+HSSH+SSRCRSSRaney NiRCRHHH2RCROHSSH干HCl2023-1-10602023-1-1061问题4OCOOC2H5HOCH2CH2OH H+OCH2CH2OCOOC2H5O

15、CH2CH2OCOOC2H5OCH2OH LiAlH4(C2H5)2O H+H2O又 如：2023-1-1062COCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORR2023-1-1063Br CH2CH2CH2CCH3OCCH2CH2CH2OHCH360%MgTHFCH2CH2CH2CH2CCH3OBrCH3OH MgTHF 2023-1-10642023-1-1065CCOHCCRCOHCCRCCOHCCH3OCCH3OCHHCR=HH2Lindlar催催化化剂剂H2O/Hg+Na/NH3炔基醇HHCOH

16、CCRHHH+COHCOCCR(H)MCCR(H)H2OM=Na,K,MgX等等问题52023-1-1066C O+NH3COHNH2C NH-H2O2023-1-1067+苯CH3NH2CHOCH3CHN+H3CCCH3O+CH3CH2CH2NH2HClH3CCH3CNCH2CH2CH3+H2OH2OHCO+H2OCNR+H2NR亚胺中若有共轭亚胺中若有共轭体系的才稳定体系的才稳定2023-1-1068HCOHCOHCOHNH2RCOHNHRHCNHRCOH2NHRCNRH2OHH2NR2023-1-1069O+NHOTsOH甲甲 苯苯NHNOCHO+N+H2O+H2OK2CO3烯胺是有机合

17、成中的重要中间体+H2OCR(H)ORR(H)NR+HNR2RRH 位位有氢有氢2023-1-1070HCH2RCOHCH2RCOHNHR2H2OHNR2CH2RCOHCH2RCOHNR2CH2RCOH2NR2HCHRCNR2HHCH2RCNR22023-1-1071CNOHH2NOHCNH2NHN C NH2ONH C NH2OCO+CNNHRH2NNHRCNNHH2NHNO2NNO2O2NNO2HHHH+H2O+H2O+H2O+H2O2023-1-1072CH3(CH2)5CHO +NH2OHCH3(CH2)5CH=NOH +H2OCO+H2N-NH2CNNH2+H2OC CH3O+H2N

18、NHC6H5CCH3N NHC6H5+H2OCH3CH2C CH3ONH2NH C NH2O+CH3COONaC2H5OH/H2OCH3CH2CCH3N NHC NH2O81-93%73%87-91%93%2023-1-1073C HOCH3C CH3ONH2NH C NH2O+CH3CH2CHN NHC NH2O+NH2OHCH3C CH3N OHO+NH2OHN OHCH3CHONO2O2NNHNH2+NO2O2NNHNCHCH3丙酮肟环己酮肟乙醛-2,4-二硝基苯腙苯甲醛缩氨脲2023-1-1074C=O+NH2-ZCNZHOHC=N-Z 2023-1-1075CN OHH2/NiCH

19、NH2或 LiAH4CN NH2H2/NiCN RH2/NiCH NH RCOH2N OHH2N NH2RNH22023-1-1076CNRRLiH2OCNHRRor RMgXCH2RCHNR2OH+CHRCNRRH2Pd/CCH2RCNRRH2023-1-1077 问题6HCHO CH3CHOCHOCH3C CH3OOC CH3OCO2023-1-1078G.Wittig（18971987）1979年诺贝尔化学奖2023-1-1079RCH2X +Ph3P Ph3P+-CH2RX-Ph3P=CHR Ph3P+-CHRB-CH3X +Ph3P Ph3P+-CH3X-Ph3P=CH2B-R2CH

20、X +Ph3P Ph3P+-CHR2X-Ph3P=CR2B-2023-1-10802023-1-1081C=O+Ph3P=C C=C2023-1-1082O+Ph3P=CHCH3CH CH3OCH2Ph3P=CH2+CHO(H3C)2N+Ph3P=CCl2CH(H3C)2NCCl2CO+Ph3P=CH2CCH2CHCH CHO+Ph3P=CHR CHCH CH CH R问题72023-1-1083 无色(紫红色醛SO3NaNHSO2NaNHSO2NaCNaO2SHNNHSO2NaNHSO2NaCNH2023-1-10842023-1-10852.-氢原子的活泼性2023-1-10862023-

21、1-1087pKapKaHC H2C H3HC H2C H C H2HC H2HC H2C NHC H2S C H3OO 3550253429HCH2COC2H5OHCH2CCH3OHCH2COHCH2NOO201610.2242023-1-1088pKaH2CCCH3OH2CCOC2H5OC2H5OCCHOCOC2H5OH3CCCHOCOC2H5OH3CCCHOCCH3OHHHHH242012.710.79.02023-1-1089烯醇负离子烯醇负离子 CHRCROHBCHRCROCHRCRO2023-1-1090R C CH2R1OR CCH R1OHR C CH R1O-H+-H+H+H

22、+2023-1-10912023-1-1092 丙酮丙酮环己酮环己酮CH3CHOCH2CH OHCH3CCH3OCH2CCH3OHOOH(1.5*10-4%)(1.2%)乙醛乙醛酮式酮式 (很少)2023-1-1093CH3CCH2CCH3OOCH3CCH CCH3OHO(76%)(24%)酮式酮式2023-1-10942023-1-1095 CH3CHOCH2CHOH+5%NaOHCH3CHCH2CHOOH2023-1-1096CCOHHCCOHCOHCOHCCOCCH2or2HH-H2O2023-1-1097CH3CHOCH2CHOH+5%NaOHCH3CHCH2CHOOHCH3CH2CH

23、OCH3CH CHOH+5%NaOHCH3CH2CH CH CHOOHCH32023-1-1098-羟基醛羟基醛 CH3CHCH2CHOOHCH3CHCH CHOOH-CH3CHO +OH-CH2CHO +H2O+-CH2CHOCH3CHCH2CHOO-CH3CHCH2CHOOHH2OCH3CHO2023-1-1099 CH3CH2CH2CHOCH2CHCH CHOCH2CH3OHCH2CH3CH2CHCCHOCH2CH3CH2CH3NaOH/H2O80-100oCKOH/H2O 6-8oC286%75%2023-1-10100CH3CCH3O2Ba(OH)2CH3CCH3OHCH2CCH3O

24、I2CH3CH3CCHCCH3O 不能直接脱水不能直接脱水丙丙酮酮Ba(OH)22023-1-10101+CH3C CH2CH3OCH3C CH2CH3OCH3CCH2CH3OHCH2C CH2CH3OBa(OH)2CH3CCH2CH3CH C CH2CH3OBa(OH)22023-1-10102 CH3CHO CH3CH2CHO+CH3CH CH2COHOHCH3CH2CH CH2COHOHCH3CH CH COHOH CH3CH3CH2CH CHCOHOHCH3 2023-1-10103R2OR1OHR4OR3+R2OR1R3OHR4R4OR3R1OHR2R2OR1R3R4R4OR3R1R

25、22023-1-10104 68%64%CHO+CH3CH2CHO OH-10oCCH C CHOCH3HCHO +CH3CH CHOCH3Na2CO3 40oCCH3CCHOCH3CH2OH2023-1-10105柠檬醛A 假紫罗兰酮 OH-100oC OH-20oCCH CH COCH3CHO+CH3COCH3CHOCOCH3+CH CH CO70%85%CHOCH3CH3CH3CHCH3CH3CH3CHCCH3O+CH3COCH3 C2H5ONaC2H5OH/-5oC49%OH-3HCHO +CCHOHHHCCHOCH2OHCH2OHHOH2CCCH2OHCH2OHCH2OHHOH2C

26、HCHO OH-三羟甲基乙醛 季戊四醇2023-1-10106NaOHCHOCHOPrPrCHOH2OOCH3OO或CHOPrOHH+或 OH-不能消除不能消除H2OOCH3HOOHH3COOH3CHO2023-1-10107（3）克莱森-施密特反应 肉桂醛78%32%CHO+CH3CHOCH CH CHOCH3C CH3O10%NaOH/C2H5OH 25oC/5hCHO+10%NaOH 70oC/2hCH CH C CH3O2023-1-10108（4）柏金反应 问题862%CHO+CH3COOCCH3OCH3COOK160-180oCCH CH COOH肉桂酸2023-1-10109（5

27、）卤化和卤仿反应 醛和酮分子中的醛和酮分子中的-氢原子可被卤原子（氢原子可被卤原子（ClCl、BrBr、I I）取代，生成取代，生成-卤代醛或酮。卤代醛或酮。2023-1-10110CCOHX2，X=Cl,Br,ICCOXHCCORHRCCORHHCCOHHH 2023-1-10111CHOH+Br2CHOBrCHCl3+HBrO+Cl2H2OOCl+HClCH3CCH3O+Br2CH3COOHCH3CCH2OBr+HBr80%61-66%2023-1-10112CCOCCOHHH-H+CCOXCCOXHXX烯烯醇醇化化CCOHHH2OX+HX 2023-1-10113OHCH3COR3 X2

28、CX3CORCHX3CORO+OHCCORHRCCORHHCCOHHH 2023-1-10114CHCCH3OCH3CH3+Br2CH3OHCHCCH2OCH3CH3BrR CCH3O+3NaOXR CCX3O+3NaOHCH3CHOCH2CHOXCHCHOXXCCHOXXX X2H2OX2X2R CCX3OOH-RCOO-+CHX3R CCH3O NaOXor X2+OH-R CCX3OOH-RCOO-+CHX32023-1-10115OHCH3COR3 X2CHX3CORO+CCOCCOHCCOXXOHXCCOHX2，OHX=Cl,Br,ICCOX 2023-1-10116CH2CORHO

29、CX3CORCOROHCX3COROHCOROCHX3+HOCH2CORXXCHCORXCX3HHOH+H有有弱酸性弱酸性烯醇负离子烯醇负离子亲核加成亲核加成消除消除2023-1-10117CHCCH3OCH3CH3R CCH3OCH3CHO NaOIor I2+OH-HCOONa +CHI3 NaOIor I2+OH-RCOO-+CHI3 NaOIor I2+OH-CHCOONaCH3CH3+CHI3COCH3 NaOIor I2+OH-COONa+CHI32023-1-10118COCH3 NaOIor I2+OH-H+H2OCOOH(CH3)3CCOCH3 NaOIor I2+OH-H+

30、H2O(CH3)3C-COOH+CHI3+CHI32023-1-10119问题9问题10习题7CH3COOHCHCH3HCOOH +CHI3NaOINaOICH3CH2OHCH3CHOCH CH3OHNaOINaOICOOH+CHI32023-1-10120（6）外消旋化 H5C6CCH C2H5OCH3H5C6CCC2H5O-CH3OH-H5C6CCH C2H5OCH3+OH-H2O()1-苯基-2-甲基-1-丁酮()1-苯基-2-甲基-1-丁酮2023-1-10121 CH3CH2CHCH2C CH3OCH3CH3CH2CHCH C CH3OHCH3*2023-1-101223.氧化和还原

31、反应 2023-1-10123RCOHOORCHO2023-1-10124RCHORCONH4O2 Ag(NH3)2OH+2 AgRCONaO+Cu2OCu(OH)2/NaOH 2023-1-10125RCHORCOOHOO2RCOHO2RCHO2023-1-10126产物复杂，合成应用意义不大产物复杂，合成应用意义不大R1COHOR1CH2CCH2R2OCCH2R2OHOR1CH2COOHCR2OHO强强氧氧化化剂剂+O浓浓 HNO3COOHCOOH有合成意义有合成意义习题52023-1-10127Baeyer-Villiger反应反应R1CR2ORCOOHOR1COR2OR1OCR2OCO

32、OHOH3CCOOHOF3CCOOHOCOOHO(MCPBA)Cl2023-1-10128R1CR2ORCOOHOH+R1CR2OHHOR1CR2OHO CROH+OR1CR2OHOCRO R1OR1CR2OHOCROH H+OCOHR1OCR2OHH+R1OCR2O（来来自自过过氧氧酸酸）R迁迁移移2023-1-101292023-1-10130R CHOH2/Ni/PR CH2OHRCR1OH2/Ni/PRCH R1OHOH2/Ni/POHCH3CHCH CH2CHOH2/Ni/P250oCCH3CH2CH2CH2CH2OHCHO H25%Pd-CCHO81%2023-1-10131H2(

33、0.3MPa)PtCROR(H)CHROHR(H)NOH3CNiH2NOHH3CHNOHH3CH2023-1-101322023-1-10133CH CH CHONaBH4H+CH CH CH2OH2023-1-10134COHCOHHCOHAlAlH2OLiAlH4H2OCH2OHRRCHOCHROHRCRORor NaBH4LiAlH4or NaBH4H2O2023-1-10135LiAlH4H2ONaBH4OCOOMeCOOMeOHHCH2OHOHHH2O1.1.2.2.2023-1-10136OOHHOHH86%14%+OOHHOHH86%14%+H3CCH3CH3H3CCH3CH3H

34、3CCH3CH31.NaBH4 or LiAlH41.H2O2.H2O2.NaBH4:LiAlH4:89%11%NaBH4:LiAlH4:NaBH4 or LiAlH48%92%2023-1-10137R1CR2OCH3CH CH3OH+AlOCH(CH3)23R1CH R2OH+CH3CCH3O习题62023-1-101382023-1-10139（1 1）单分子还原（2 2）还原偶合R1CR2O(H)Na or LiR1CHR2OH(H)R1CR2O2Mg(Hg)R1CCR1OH OHR2R22023-1-101402023-1-10141适用于对酸适用于对酸稳定的体系稳定的体系RCR(H

35、)ORCH2R(H)Zn(Hg)HCl2023-1-10142COCH2CH2CH3Zn-Hg /HClCH2CH2CH2CH3Ar HCClROAlCl3ArCROZn(Hg)HClArCH2R2023-1-10143适用于对碱适用于对碱稳定的体系稳定的体系NH2-NH2,NaOH(HOCH2CH2)2O,RCRORCH2RN2+2023-1-10144COCH2CH3CH2CH2CH3 NH2-NH2/NaOH(HOCH2CH2)2O/O NH2-NH2/NaOH(HOCH2CH2)2O/CH3COCH3NiH2SSCH3CH3CH3CH2CH3HS(CH2)3SHCH3CH2CHOSSC

36、H2HCH3HS(CH2)3SHNiH2CH3CH2CH32023-1-10145 RCH浓浓 OHORCOORCH2OH+H+RCOOH+RCHO2023-1-10146CHO2CH2OHCOOHOHOCHOOCH2OHOCOOH2OH2HCHOCH3OH +HCOONa50%NaOH 25oC/1h50%KOH100oC/1hCHOBrCH2OHBrCOONaBr+45%48%22023-1-10147RCOHOHRCOHOHRCOHRCOHOHRCOH+HRCOO+HRCOHH负负H迁迁移移2023-1-10148产物复杂，一般无合成意义产物复杂，一般无合成意义R1CH浓OHOR1COO

37、R2CH2OHR2CHO+R2COOR1CH2OH+R CH浓OHOHCOORCH2OHCH2O+2023-1-10149R CHOHCOORCH2OHCH2O+OH+HCHO+HCOONaCHOCH2OH50%NaOH 问题11问题12习题102023-1-10150第三节 醛、酮的制法CHOOCHOCH2CCH(CH2)12CH3O柠檬醛a 柠檬醛b 樟脑 麝香酮2023-1-10151醛、酮的制法一、氧化或脱氢法二、羧酸及其衍生物还原法三、偕二卤代物水解法四、FriedelCrafts酰化法五、甲酰化法六、炔烃水合2023-1-10152一、氧化或脱氢法 CH3MnO2+H2SO4CHO

38、CHO(CH3CO)2OCH(OCOCH3)2CHO+2CH3COOHH2O2023-1-10153CH2CH3Mn(OCOCH3)2 130oC+O2COCH3+H2OCu O FeHOH Ci2500oCCH3CH2ClCHCl2CHO2023-1-10154 吡啶Cr2O3CH3CCH2CH3CH3CCH2CH3CH3CCH2CH3+CH3COCH3 CH3COCHOSeO2CHCHCCOOSeO22023-1-10155R1R2R1R2OOOCCH2R1R2CR1R2O+KMnO4CO2CCR1R2R3HOCR3HCR1R2O+(1)O3(2)Zn/H2OOCR3OHCR1R2O+KM

39、nO42023-1-10156RCH2OHRCHCrO3PyridineORCHROHRCROAlOC(CH3)33 /CH3CCH3OCrO3/H2SO4CrO3Pyridine2023-1-10157 CH3(CH2)5CH CH3OHCH3(CH2)5C CH3OK2Cr2O7/H2SO4 100oC/H2O96%CH3CH2OH CH3COOHK2Cr2O7/H2SO4 O2023-1-10158 制备醛时若采用三氧化铬和吡啶的络合物为氧化剂，则醛的产率很好。CH3(CH2)5CH2OHCH3(CH2)5CH2CHO CrO3(C5H5N)2CH2Cl2/25oC/1hR1CR2OCH

40、3CH CH3OH+AlOCH(CH3)23R1CH R2OH+CH3CCH3O2023-1-10159 催化剂10MPaOHCH2CH2+O+CH3CH32023-1-10160 CH3CH2OH CH3CHO +H2 Cu300oCR1CHR2OHR1CR2O Cu200-300oC+H2R1CCR3OH OHR2H HIO4or Pb(OAc)4R1CHO +R2COR32023-1-10161二、羧酸及其衍生物还原法 RCOCl RCHO+HClPd-BaSO4 H2 2023-1-10162RCOCl RCHO LiAlH(t-BuO)3C N(CH3)2OCHN(CH3)2OLiL

41、iAlH(EtO)3CHOH3O+LiAlH(EtO)3CHOH3O+CN2023-1-10163 R1-MgBr +CdCl2Et2O0oCR1-CdCl +MgCl2R1-CO-R2 +CdCl2R2COCl /C6H6/35oC2023-1-10164 H3CO CH2CN+MgBrEt2OCCH2OCH3N MgBrCCH2OCH3NHCCH2OCH3OH3O+H3O+2023-1-10165三、偕二卤代物水解法 光R1CRXX(H)H+or OH-H2OR1CRO(H)2Cl2OH-H2OCH2CH3C CH3ClClC CH3O2023-1-10166ArCH3ArCHO X2/h

42、v or ArCHX2H2OHOor NBSArCH2ArCOCXXHOArArAr HCCl4/AlCl3Friedle-Crafts反反应应2or HArAr X2/hv or or NBSH2OAr=Ar2023-1-10167四、FriedelCrafts酰化法 上述从羧酸及其衍生物合成醛，酮是一般的合成上述从羧酸及其衍生物合成醛，酮是一般的合成方法，如果要合成芳酮，则通常不必用金属有机物而方法，如果要合成芳酮，则通常不必用金属有机物而最常用的重要方法是芳烃最常用的重要方法是芳烃FriedelFriedelCtaftsCtafts酰化法，酰化法，其通式是：其通式是：AlCl3C RO+

43、RCOCl2023-1-10168 AlCl3OOO+OOOHOOHZn-Hg HClOH3PO4(CH2)15COClAlBr3 CS2CH2(CH2)14CO2023-1-10169五、甲酰化法 H+CO +HClAlCl3CHOCO +HClCHOCl2023-1-10170 +CO +H2CH3CHCH2Co(CO)42CH3CH2CH2CHOCH3CH CHOCH3+2023-1-10171六、炔烃水合习题11RCCHH2OHg+RCOCH3CCHHCCHM（M=Na,MgX 等等）RXCCRHCH3CROCCRRH2OHg+H2OHg+CH2RCRORCRORCROHCCHH2OH

44、g+RCROHCCH3O(1)(2)H2O2023-1-10172小 结 现将醛和酮的主要反应以及前面各章中涉及到的醛和酮的制法汇总如下:（一）醛的特殊反应 ArCH2Cl2ArCH3Ag H2ONaOHCrO3ArCHORCHOCu2OArCHOCH3CORAr-CH=CH-CORAr-CH=CH-COOH Ac2ORONa ArCOOH +ArCH2OH(R)(R)40%NaOH洋红色洋红色土伦试剂土伦试剂品红试剂品红试剂费林溶液费林溶液2023-1-10173（二）醛和酮（二）醛和酮 2023-1-10174 例例 题题（）试用化学方法鉴别下列化合物：解：题中五个化合物分属三类，首先用羰

45、基试剂将（A、（B）、（C）与（D）、（E）分开。在（A）、（B）、（C）中利用芳醛的特征反应将（A）与（B）、（C）分开；（B）和（C）虽均是酮，但可利用二者构造上的差别，采用特性反应将两者区别开。（D）和（E）属于不同类型化合物，可利用某一类反应的共性将两者区别开。例如，可采用下列程序进行鉴别：2023-1-10175（二）以乙烯为主要原料合成3-己酮。解：对比原料与产物的构造式：通过对比可以看出，此是增碳反应、且是成倍增长。可将3-己酮分解为乙基和“丁醛”，而丁醛可由两分子乙醛经羟醛缩合而得，乙酸可由乙烯得到。丁醛若与溴化乙基镁反应，可增加两个碳原子，且是直链。通过上述分析，由乙烯合成3

46、-己酮可用反应式表示如下：（1）由乙烯合成丁醛：2023-1-10176（2）溴化乙基镁的制备：（3）3-己酮的合成：2023-1-10177课堂设问2 21 18 87 79 91010111112123 34 45 56 62023-1-10178问题12-l 命名下列各代合物：3-甲基-2-乙基戊醛 5-甲基-4-己烯醛2,2-二甲基-3-戊酮 4-己烯-3-酮2,2-二甲基环己酮 1-苯基-2-丙酮2023-1-10179问题12-2 写出下列化合物的构造式：CH3CHCH2CHOCH3（1）异戊醛 （2）三氯乙醛Cl3C-CHO（3）,-不饱和成醛 （4）-氯-溴丁酮CH3CH2CH

47、=CHCHOBrCH2CH2CCH2ClO（5）乙基环已基甲酮 （6）-苯基丙酮CCH2CH3OCH2CCH3O2023-1-10180问题12-3 试用化学方法分离下列混合物：（1）环己醇和环己酮（2）苯酚和苯甲醛2023-1-10181问题12-4 完成下列反应式：CH3CH2CH2CHO +2CH3OH CH3CH2CH2CH(OCH3)2OBrOOCH2CH2OOOCH2CH2BrHOCH2CH2OH H+NaOHC2H5OHH2O H+2023-1-10182问题12-5 完成下列反应式：MgCl+HCHOCH2OMgClCH2OHH2O H+(1)BrCl+MgClMgBrClCH

48、OMgBrCH3ClCHCH3OHI2CH3CHO H2ONH4Cl(2)CH3MgBr +(CH3)2CHCCH(CH3)2(CH3)2CHCCH(CH3)2(CH3)2CHCCH(CH3)2CH3CH3OHOMgBrH2O H+(3)2023-1-10183问题12-6 完成下列反应式：2023-1-10184问题12-7 完成下列反应式：2023-1-10185问题12-8 完成下列反应式：2023-1-10186问题12-9 下列化合物中哪些可以发生碘仿反应？答：（2）和（3）可以发生碘仿反应。2023-1-10187问题12-10 完成下列反应式：2023-1-10188问题12-1

49、1 用化学方法鉴别下列各组化合物：（2）苯乙酮、苯甲醛、苄醇（1）1-丙醇、丙醛、丙酮2023-1-10189问题12-12 完成下列反应式：2023-1-10190习题答案 p299-3021 16 611111515121214147 78 89 910102 23 34 45 52023-1-101911命名下列各化合物：3-甲基戊醛 2-甲基-3-戊酮甲基环戊基甲酮 3-甲氧基苯甲醛3,7-二甲基-6-辛烯醛 -溴代苯乙酮2023-1-101921-戊烯-3-酮 丙醛缩二乙醇环己酮肟 2,4-戊二酮丙酮-2,4-二硝基苯腙2023-1-101932写出下列化合物的构造式：（1）2-丁烯

50、醛 （2）二苯甲酮CH3CH=CHCHOCO（3）2,2-二甲基环戊酮 （4）3-（间羟基苯基）丙醛OCH3CH3OHCH2CH2CHO（5）甲醛苯腙 （6）丙酮缩氨脲HNN=CH2C=N NHC NH2CH3CH3O2023-1-10194（7）苄基丙酮 （8）-溴代丙醛CH2COCH2CH2CH3CH3CHCOHBr（9）三聚甲醛 （l0）邻羟基苯甲醛OHCHOOCH2CH2OOCH22023-1-10195 3写出分子式为C5H10O的醛和酮的同分异构体，并命名。CH3CH2CH2CH2COHCH3CH CH2COHCH3CH3CH2CHCOHCH3CH3CCOHCH3CH3CH3CCH