有机化学学习笔记：第十五章负碳离子反应ppt课件

1、 -碳的卤代及烷碳的卤代及烷(酰酰)基化反响基化反响 醛醛(酮酮)及酯的缩合反响及酯的缩合反响 生成碳碳双键的反响生成碳碳双键的反响成环的反响成环的反响 其他类型的负碳离子反响其他类型的负碳离子反响 C OR(H)R-CH2碱性条件 OH-直接与 -H酸碱中和生成CC OR(H)CRHC OR(H)CRH烯醇化酮式负碳离子稳定自身的方式负碳离子参与反应的形式C OR(H)R-CH2酸性条件 H+与C=O中氧原子结合C OHR(H)CRHH烯醇化C OHR(H)CRH-H+C OHR(H)CRH酮式CH3-CH2-C-CH3OH+CH3-CH-C-CH2OHHHabHa和Hb均有脱去的可能，形成

2、两种烯醇式。aCH3-CH2-C=CH2OH取代少的烯烃不稳定(次产物)bCH3-CH=C-CH3OH取代多的烯烃稳定(主产物)Br-Br-H+CH3-CH-C-CH3OBrCH3-CH2-C-CH3OOH-CH3-CH-C-CH2OHHabHa和Hb均有可反应，形成两种负碳离子。abCH3-CH2-C-CH2O远离推电子基团(易生成，且稳定)CH3-CH-C-CH3O离推电子基团近(不易生成，不稳定)Br-BrCH3-CH2-C-CH2BrOCH3-CH2-C-CH2BrOOH-CH3-CH2-C-CHBrOBr-Br-Br-CH3-CH2-C-CHBr2OOH-Br-Br-Br-CH3-C

3、H2-C-CBr2OCH3-CH2-C-CBr3O第二步溴代比第一步容易，第三步比第二步更容易。OH-CH3-CH2-C-CBr3OCH3-CH2-C-CBr3OOHCH3-CH2-C-OHO+ CBr3 酸碱中和CH3-CH2-C-OO+ CHBr3 OC-CH3BrNaOHBr2OC-OHBr+ CHBr3OC-CH3BrCH3COOHBr2OC-CH2BrBrCH3-C-CH3O(CH3)2C C(CH3)2OHOH-OH(CH3)3C-C-CH3OH+Br2Mg(CH3)3C-C-OHONH3(CH3)3C-C-NH2OOH-Br2(CH3)3CNH2卤仿反应Hoffmann降解反应条

4、件相同OBr2NH2OH HClOHNBrNHOBrPPAONHNNR-XNRXH3+OORONaOCH3OOR-X-X-ORNRONHRNRNRNRR-XNRRXH3+OORRNaOCH3ROOORROROR R-X-X-ORRCH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5R-XCH3COCHCOOC2H5RH+CH3COCHCOOC2H5R稀NaOHCH3COCHCOOHRCH3-C-CH2-RO+ CO2H+CH3COCHCOOC2H5R-C=O稀NaOHCH3COCHCOOHCH3-C-CH2-C-RO+ CO2R-C=OOCH3COCH2COOC2H5NaO

5、C2H5CH3COCHCOOC2H5CH3-C=OCH3COClNaOC2H5C2H5BrCH3COCCOOC2H5CH3-C=OC2H5H+稀NaOHCH3COCHCOCH3C2H5CH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5Br2. H+1.稀NaOHCOCH3CH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5X(CH2)nX(CH2)nXCH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5(CH2)nCH3COCHCOOC2H52. H+1.稀NaOHCH3C(CH2)nCCH3OO使用不同长度CH2的卤代烃得到不同的

6、甲基二酮CH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5I2CH3COCHCOOC2H522. H+1.稀NaOHCH3C(CH2)2CCH3OOCH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5X(CH2)nX(CH2)nXNaOC2H5CH3COCHCOOC2H5(CH2)n2. H+1.稀NaOHCHCOCH3(CH2)nCH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5Br(CH2)3Br(CH2)3BrNaOC2H52. H+1.稀NaOHCOOC2H5CH3COC-CH3OCH3CCH2CH2CphOOP2O5OC

7、H3phph-C-CH3OBr2CH3COOHph-C-CH2BrOOH OHH+OOphCH2BrCH3COCH2COOC2H5NaOC2H5OOphCH2CHCOOC2H5COCH31. OH-2. H3+OCH3COCH2COOC2H5NaOC2H5Br(CH2)3BrOCOOC2H5CH3CH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5Br-(CH2)3BrCH3CCHCOOC2H5(CH2)3BrONaOC2H5CH3C-C-COOC2H5(CH2)3BrOCH3C=C-COOC2H5(CH2)3-BrOOCOOC2H5CH3CH3 C CH-C-OC2H5R

8、浓OH-OOCH3 C CH-C-OC2H5ROOOHOH-OC2H5CH3 C CH=C-OHROOOHRCH-COOHRCH2COOHCH3COO-CH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5Br2. H+1.浓NaOHCH2COOHCH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5I2CH3COCHCOOC2H52NaOC2H5CH3I2. H+1.浓NaOHCH3COCHCOOC2H5CH3COCCOOC2H5CH3HOOCCHCH2COOHCH3B. CH2(COOC2H5)2CH2(COOC2H5)2NaOC2H5CH(COOC2H

9、5)2R-XR-CH(COOC2H5)2或RCOXRCOCH(COOC2H5)2稀NaOHR-CHCOOHCOOHRCOCH(COOH)2H+RCH2COOHRCOCH2COOHCH2(COOC2H5)2NaOC2H5CH3CH2COClCH3CH2COCH(COOC2H5)2NaOC2H5CH3BrCH3CH2COC(COOC2H5)2CH31.稀NaOH2. H+CH3CH2COCHCOOHCH3CH2(COOC2H5)2NaOC2H5BrCH(COOC2H5)21.稀NaOH2. H+CH2COOHCH2(COOC2H5)2NaOC2H5X(CH2)nXX(CH2)nCH(COOC2H5

10、)2NaOC2H5CH2(COOC2H5)2(C2H5OOC)2CH(CH2)nCH(COOC2H5)21.稀NaOH2. H+HOOCCH2(CH2)nCH2COOHCH2(COOC2H5)2NaOC2H5I22CH(COOC2H5)2CH(COOC2H5)21.稀NaOH2. H+CH2COOHCH2COOHCH2(COOC2H5)2NaOC2H5X(CH2)nXX(CH2)nCH(COOC2H5)2NaOC2H5C(COOC2H5)2(CH2)n1.稀NaOH2. H+CHCOOH(CH2)nCOOH1.稀NaOH2. H+COOC2H5COOC2H5CH2ClCH2ClNaOC2H5C

11、H2(COOC2H5)2CH2OHCH2OHSOCl2COOC2H5COOC2H5NaC2H5OHCH2(COOC2H5)2NaOC2H5Br(CH2)3BrBr(CH2)3CH(COOC2H5)2NaOC2H5CH3-C-HOCH3-C-HO+10%NaOH45 hoursCH3-CH-CH2-C-HOHO50%CH3-C-HOH+CH2-C-HOHH-H+CH2=C-HOHCH3-C-HOCH3-CH-CH2-C-HOOH由烯醇式生成负碳离子是决定反应速率的步骤。CH3-CH-CH2-C-HOHOCH3-C-HOOH-CH2-C-HO-H+CH2=C-HO生成负碳离子是决定反应速率的步骤。

12、CH3-C-HOCH3-CH-CH2-C-HOOCH3-CH-CH2-C-HOHOH2O-OH-CH3CH2CH2C-HO1M NaOH801000C3 hoursCH3CH2CH2CH=CCH2CH3CHO86%ORR = o-F; p-F; p-CF3OH2NCl+CH3COOHH2SO4ORH2NClNRClCH3OCH2OCH3OCH2OOHOCH3HOOCH2OCH3OCH2OCH3OCH3+KOHC2H5OH/H2OCH3OCH2OCH3OCH2OOHOOCH2OCH3OCH2OCH3OCH3O2NOOOHO+NaOCH3CH3OHO2NOOOCH3OOHOArCHOC2H5OH

13、/ KOHCH3OOHOArAr = CH3OCH3OCH3OOCH3OOHBrOCH3OCH3OCHOCH3OH / KOH室温，36 hOOHBrOCH3OOCH3OOBOHNO(R,S)-1Cat.* =ArHOO+30 mol% Cat.*05oC, 50 hoursArOHO ee%99Ar =OCH3CH3OOCH3O2NClClORCHOR = H; o-, m-, p-NO2; o-, p-Cl; p-Br+5 mol % NHCOOHn-C12H25O室温，24小时ROHO产率 6587 %ee % 6070 O+NHCOOHCH3COCH3，室温产率 80 %ee % 65

14、76 %OOOOOOH OCH3-CH-CH2-C-CH3OHOCH3-C-CH3OCH3Ba(OH)22单程产率 88%ee% 90ONaOCH3OCH2=CHCCH3OMichael加成OCH2CH2CCH3ONaOCH3羟醛缩合OCH2CH2CCH2OOO-OH-O12312ONaOCH3OCH2=CHCCH3OMichael加成OCH2CH2CCH3OCH3NaOCH3羟醛缩合OCH2CH2CCH2OCH3OO-OH-ONHNOCH2=CHCCH3OH3+OMichael加成OCH2CH2CCH3OCH3NaOCH3羟醛缩合OCH2CH2CCH2OCH3OO-OH-OCH3OO+ CH

15、3CH2CCH=CH2 OKOHCH3OOOCOOC2H5+ CH3CCH=CHCH3 ONaOCH3C2H5OOCOO+ CH3CCH=CH2 ONaOC2H5OO+ CH3CCH=CH-ONaOC2H5OO(CH3)2C=CHCCH3O+NaOCH3O(CH3)2C=CHCCH3O+NH OOt-BuOO+NaOCH3t-BuOOOC2H5OOC1. OH-2. H+CCH2CHOCH2COCHCOOC2H5CCH=CHOCH3COCH2COOC2H5NaOC2H5C-CH3O+ H-COOH-OOOOCH3COCH=CH2NaOCH3OOCH3INaOCH3NaOCH3OOOOOCH3O

16、OOCH3OOOCH3OOCH3OO OOCH3OO-CH3OOCH3CCH2COOC2H5OCH3CH=CCCH3O+NaOC2H5CH3CH3COOC2H5COOC2H5COOC2H5CH3CCH2COOC2H5ONaOC2H5CH3CCHCOOC2H5OCH3CH=C CCH3OCOOC2H5Michael加成CH3CH-C=CCH3OC2H5OOCCH3CCHCOOC2H5OC2H5OH-C2H5O-CH3CH-C=CCH3OHC2H5OOCCH3CCHCOOC2H5OCH3CHC2H5OOCOCHCCH3OCHCCH3C2H5OOCNaOC2H5CH3CHC2H5OOCOCHCCH3

17、OCHCCH2C2H5OOC羟醛缩合C2H5OOCC2H5OOCCH3OOCH3-OH-OCH3CH3COOC2H5COOC2H5CH2(COOC2H5)2NaOC2H5CH(COOC2H5)2CH3CCH=CH2OMichael加成CH3CCH2CH2CH(COOC2H5)2ONaOC2H5羟醛缩合CH2CCH2CH2CHOCOOC2H5COC2H5OOOC2H5OOCOC2H5-C2H5O-OOCOOC2H5来自CH2(COOC2H5)2此处亚甲基是羟醛缩合反应位置其余部分来自不饱和酮OO1. OH-2. H+CH3CCH3O2Ba(OH)2H+CH3CCH=C(CH3)2OCH2(COO

18、C2H5)2NaOC2H5OOCH3CCH3OCHOOH-CH=CHCCH3OCH2(COOC2H5)2NaOC2H5OOOOOOC2H5OOC1. OH-2. H+CH-C-CH3OCH2(COOC2H5)2NaOC2H5OCH3COCH2COOC2H5NaOC2H5COOC2H5COCH31. OH-2. H+C-CHO +浓OH-R1R2R3C-CHOR1R2R3C-CH2OH +R1R2R3C-COOR1R2R3C C-HOH-R1R2R3OC C-HR1R2R3OOHC C-HR1R2R3OH 对C=O的亲核加成C C-OHR1R2R3OC C-HR1R2R3OH+酸碱中和C-COO

19、R1R2R3C-CH2OH+ R1R2R3OH-R-C-C-ROOR-C-C-ROOOH-R迁移R-C-COOOHRR-C C-OOOHROCHO1. 30% NaOH2. H3+OOCH2OH+OCOOHC COO1. 30% KOH2. H3+OC COOHOHC CHOHOC HOCN-安息香C HOCN-C HOCNH交换C OHCNH COC COH OCN HH交换C COHOCN HC CHOHO-CN-HNO3C CO OC OHCNGC HOGG是吸电子基团，使CHO中C的正电性上升，有利于亲核加成；但使形成的亲核试剂负碳离子的负电荷分散到苯环上，亲核性下降，不利于反应。对反

20、应不利C OHCNGC HOGG是推电子基团，使CHO中C的正电性下降，不利于亲核加成；但使形成的亲核试剂负碳离子的负电荷更加集中，亲核性升高，有利于反应。对反应不利G2G1C CHOHO含吸电子基团一侧被亲核加成含推电子基团一侧作为亲核试剂CN-CHON(CH3)2CHONO2+(CH3)2NC CHOHONO2NNCH3NH2NSCH3CH2CH2OHCH2ClHVB1-H+NSCH3CH2CH2OHRH-CO亲核加成NSCH3CH2CH2OHRH-CO负氢迁移NSCH3CH2CH2OHRCOHNSCH3CH2CH2OHRCOHC-HONSCH3CH2CH2OHRCHOC-HONSCH3C

21、H2CH2OHRCOHC-HONSCH3CH2CH2OHRC CHOOH-CHOSVB1NaOHOSSOHO2EDTA-Fe(III)OSSOR-C-HOR1CCH2R2OR3NHR4+H+R1CCH-CH-NOR2RR3R4+ H2OR-C-HOR3NHR4+亲核加成R-CHNOHR3R4H+R-CHNOH2R3R4-H2OR-CH-NR3R4R1CCH2R2OH+R1CCH2R2OHR1C=CHR2OHR-CH-NR3R4R-CH=NR3R4R1CCH-CH-NOHR2RR3R4R1CCH-CH-NOR2RR3R4-H+CH3CCH3O+ HCHO + (CH3)2NH微量HClCH3CC

22、H2CH2N(CH3)2OCH3ICH3CCH2CH2N(CH3)3 IOAg2OCH3CCH2CH2N(CH3)3 OHOCH3CCH=CH2O-C-CH3O+ HCHO + (CH3)2NH微量HCl-CCH2CH2N(CH3)2O85%CH3NH2CH2CHOCH2CHO+CH2COOHCH2COOHC=OpH=5CH2CH CHCOOHCH2CH CHCOOHNCH3C=O-CO2CH2CH CH2CH2CH CH2NCH3C=ONO颠茄酮CCH2CCH3OO+ (CH3)2NCH2N(CH3)2 少量(CH3)2NH HClC2H5OHCCHCCH3OOCH2N(CH3)2CCH3O1. C2H5OH/HCl 5250COCHONO2+NH22. 10% NaHCO3NO2NH76%CHONO2+CH3SO2NH2H-P(OC2H5)2OCH3COClCH3SO2NHCH-P(OC2H5)2NO2O79%O+ HCHO + (CH3)2NHH2ONOANOB+产率 59%(A:B=7:3) OHNCH3HCHOONCH3NCH3C=CH + HCHO + NHCH3C=CCH2NOOHHCHONHOOHNH2/PdOOH87%NH+ HCHO + (CH3)2NHH2OCH3COOHNNH95%草绿碱CH3OHN2COO