1、醛醛 和和 酮酮aldehydes and ketonesCOCH3CH2CHOCORCHORCORCHORCOCH3CHCCH3CH3OCCH3O酮酮 HCHOCH3CHOCH2CHOCH3CCH2CH3OCH2CCH2CH3OCHCCH3CH2O CH3CHCH2CHOCH3OHCHORRsp2CO羰基碳：羰基碳：sp2雜化；雜化；羰基為平面型。羰基為平面型。羰基是極性基團(tuán)羰基是極性基團(tuán)羰基羰基 C=O: : 一個(gè)一個(gè) 鍵、鍵、 一個(gè)一個(gè) 鍵鍵 CO+CHCOCO + HCNCOHCNH2OH+orOH-COHCOOHHCNH+ + CN-B-+ HCNBH + CN-COCNCOCNCO

2、HCNCNSlowHCN+CONaHSO3COHSO3Na+COCOHSO3NaH or OHH2 O+CH3CH2CCCH3H3OHg2+CH3CH2COCH2CH3CH3CH2CH2COCH3+CCH3CH3ONaHSO3CCH3CH3OHSO3NaNaCNCCH3CH3OHCN+CORORRH+ H2OH+CRHO + 2ROHCOHORCOHORdry HCl(q)or OHROHdry HClCOROR+CH3CH2CH2CHO + CH3CH2OH（干）HClCH3CH2CH2CHOCH2CH3OHCH3CH2OHH+CH3CH2CH2CHOCH2CH3OCH2CH3COHCOHC

3、OH+COHROHCOHHORHCOHOR+ROHCORHORHCORORCOH2ORH2 OCOR+CH3CH2CHO + CH2-CH2OH OHH+ CH3CH2OCOHHOCH2CH2CH2CHOOOHHCOHHSCH2HSCH2SS+OHCHOCH3OHH+OOMeCH2OHOHCH3CHOHOHCOHOHCH3CH3100%56%很少CCl3CHOHOHCOH2 OCOHOHCH3COCH3CH3CH2MgBrdry Et2OH3OCCH3CH3OHCH2CH3+1) 2)+OHOH+H3OCOCOMgXRRMgXCOHR無(wú)水 乙 醚+Br2FeBr3BrMgEt2OMgBrOHK

4、MnO4OMgBrOEt2OH3OTM(1)(2)+CH2CH3OHOHCH2CH2+C2H5BrC2H5NBSOHH BrCH2CH2BrCHCH3BrCHCH2ROORMgOTMH3OEt2OCH2CH2MgBr+(CH3)2CHCCH(CH3)2CH3CH2CH2MgBrdry Et2OH3OO(CH3)2CHCCH(CH3)2OHCH2CH2CH3+1) 2)+30%(CH3)3CCC(CH3)3(CH3)3CLidry Et2OH3OO(CH3)3CCC(CH3)3OHC(CH3)3+1) 2)+81%OHCCNaOHCCH+H3OHgOHCOCH3+2+NH2GNH2NH2NH2N

5、HOHNH2CRRORNH2CRRNHR+COCNH2GNG+烯醇式轉(zhuǎn)化COHNR2COHNR2+?HCOHNR2COHNR2CHHC+CCNR2COH2NRCOHNHRH2 OCNR+H2N-OH （羥胺） C=N-OH （肟）H2N-NH2 （肼） C=N-NH2 （腙）H2N-NHNO2O2NC=N-NHNO2O2NH2N-NH-C-NH2OC=N-NH-C-NH2（縮氨脲）O（氨基脲）（2，4-二硝基苯肼）（2，4-二硝基苯腙）CO +COCH3H2NNHCNNHCH3+CH3C HO+ CH2HCHONaOHH2OCH3CHOHCH2CHOCH3CHOHCH2CHO-H2OCH3CH

6、=CHCHO , -不飽和醛不飽和醛 -羥基醛羥基醛CH2CHOH-OH-CH2CHOCH2=CHO-CH3COHCH3CH=CH CHOOH-, H2OCH3CHO-CH2CHOH2OCH3CH CH CHOOHHCH3CH2CCH3CH2CHOOHCH3CH2CHOHOCHCHOCH3H+酮縮合酮縮合 相對(duì)較難相對(duì)較難：HCH + CH3CHCHOOCH3dil. Na2CO340oCCH3CCH3CHOCH2OHCH3OOOOHCH3CCH2CH2CCH3OOOHOCH3COCH3Ba(OH)2CH2CCH3OCH3OCH3CH2CHO + CH3CHOdil. OH-?CH=CHCHO

7、肉桂醛HCHOCH3CHOOHHOCH2CH2CHOHCHOHCHOOHOHHOCH2CCHOCH2OHCH2OH+OCH3NO2C2H5ONaOHCH2NO2+CHCOX2CXCO酸 或堿+溴仿溴仿C CXOXX+ OH-C CXXXO-C OHO+ CX3HO-COO- + HCX3(Haloform)RCOCH3Br2NaOHRCOCBr3OHCHBr3RCOO+COCXHH CH3CO 、CH3CHOHC CH3OCl2NaOHH+C OHO+ CHCl3I2NaOHNaOICHI3CH3CCCH3CH3CH3CH3CCOOHCH3CH3CH3CCOOHCH3CH3CH3CCOCH3C

8、H3CH3I2/NaOHCH3CCCH3CH3CH3HKMnO4/OHCH3CCCH3CH3CH3OH OH+稀 、冷OHNO3CH2CH2COOHCH2CH2COOH50%RCHOKMnO4/HRCOOH+ CH3CH=CHCHOAg(NH3)2OHCH3CH=CHCOOAg+Ag(NH3)2OH+RCHOTollens reagentFehlings reagentRCOORCOOAgCu2O+H2/NiCH3CH2CH2CH2OHCH3CHCHCHOCOCHOHCH2CH3CH=CHCHO1) LiAlH4 乙醚2）H+，H2OCH3CH=CHCH2OH（90%） CHCHOCHAlOC

9、H(CH3)23(CH3)2CHOHCHCH2OHCHAlOCH(CH3)23CH3COCH32 CH3CCH3OMg苯H3O+CH3CCH3OHCCH3CH3OHCH3ONa/EtOHCH3OHHOMgC6H6OHOHH+H2OOCH3CCOOHCH3CH3CH3CCH3O2 CH3CCH3OMg苯H3O+CH3CCH3OHCCH3CH3OHHCH3CCOOHCH3CH3CH3CCOCH3CH3CH3I2/NaOH+HCH3CCCH3CH3CH3OH OHC6H5CHOCH3COCH3C6H5CHCHCOC(CH3)3CH3COC(CH3)3OHMg/C6H6+2C6H5CHOCH3COCH

10、3C6H5CHCHCOC(CH3)3and(CH3)3CCH2OHHCl/ZnCl2CH2CHCH2CH3OHH2SO4CH2CHOCH2CHCH21.( )2.( )3.( )HOCH2CH2CH2CH2ClOH4.( )OH OHHO+CH2CHCH3CH3CH2CH2OCH2CHCH2 COZnHgHCl CH2Zn-Hg齊：齊： Zn粉或粉或Zn粒用粒用5-10%HgCl2 處理。處理。 堿性條件堿性條件COCH2NH2NH2/C2H5OHC2H5ONaCCH2CH3OCH2CH2CH3NH2NH2 / KOH(HOCH2CH2O)285%(CH3)3C(CH3)3CClAlCl3CH

11、3CH2CH2COClAlCl3(CH3)3CCOCH2CH2CH3Zn-Hg/con. HCl(CH3)3CCH2CH2CH2CH3(CH3)3CCH2CH2CH2CH3濃OH-CHOCOONa+CH2OH2CHOOCH3+ HCHO濃-OH- H+CH2OHOCH3+ HCOOHHCHONaOHHCOONaCH3OH2濃HOCH2CCH2OHCH2OHCH2OH？HOCH2CCHOCH2OHCH2OH3HCHO + CH3CHOHCHO稀OH-濃OH-HOCH2CCH2OH + HCOO-CH2OHCH2OHRRRRC(C6H5)3PC(C6H5)3P+_(C6H5)3PCH3CH2BrC

12、6H6(C6H5)3P CH2CH3Br+_(C6H5)3P=CHCH3C6H5Li or C2H5ONa強(qiáng) 堿脫氫R1R2CRROC(C6H5)3P+RRR1R2CC(C6H5)3PO+CH3NO2CrO3H2SO4NO2CHO醋酸低溫CHOCH3MnO2/H2SO4少 量 分批 CH3Cl2CHCl2H3OCHOCHOHOH+光CCl4AlCl3CClClCOH3O2+ COH ClCHOAlCl3/ CuCl+35-50度CH3CH3CHOCO/HClAlCl3/CuCl 25度OHCHCl3NaOH/ H2OOHCHOOHCHO+3745%811%OHOCH3CHCH3OHCH3CHC

13、CH3OHCH3CH3CH3CHOOOCH3CH3OO第二節(jié)第二節(jié) 不飽和醛酮不飽和醛酮CCCOCCCO-+4 3 21CCCO.一、一、 , -不飽和醛酮不飽和醛酮CH2=CHCHOCH3CH=CHCHOCH=CHCHOCH2=C=OC6H5CH=CHCCH3OC6H5MgXC6H5CHCCH3C6H5OMgBrCH1234H3OC6H5CHCCH3C6H5OHCH+1234C6H5CHCH2CCH3C6H5O烯醇互變C6H5CH=CHCCH3O) C6H5MgX) H3OC6H5CH=CHCCH3OHC6H512+C6H5CHCH2CCH3C6H5O+CCCO4 3 2 1+ Nu-1,2

14、-1,4-(共軛加成)CCCO-NuH+CCCOHNuCCCO-NuH+CCCOHNuCCCOHNu互變異構(gòu)KCNCH3COOHCH=CH-COCH-CH2-COCNCH3CH=CH-C-CH3OCH3LiH2OCH3CH=CH-C-CH3OHCH3C6H5CH=CHCC6H5O) C6H5MgX) H3OC6H5CH=CHCC6H5OHC6H5C6H5CHCH2CC6H5C6H5O12+6%94%+CH2=CHCHOHClCH2CHCOHHClCH2CH2CHClO1,4-加成 , -不飽和共軛化合物（醛、酮、酯、腈等）不飽和共軛化合物（醛、酮、酯、腈等）與能形成碳負(fù)離子的化合物發(fā)生的與能形

15、成碳負(fù)離子的化合物發(fā)生的1,4- -親核加親核加成反應(yīng)成反應(yīng) -不飽和醛酮與鹵素、次鹵酸等的加成不飽和醛酮與鹵素、次鹵酸等的加成主要發(fā)生在碳碳雙鍵上。主要發(fā)生在碳碳雙鍵上。CH2=CHCCH3O+ CH2(COOC2H5)2C2H5ONaC2H5OHCH2CH2CCH3OCH(COOC2H5)2CH3COCH2COOC2H5CNCH2COOC2H5RNO2COCH2COCCCOCCCOOC2H5ONaOCH3O+ CH2=CHCCH3OOOCH3CH2CH2CCH3O共軛加成羥醛縮合C2H5ONaOCH3OCH2=CHCCH3OCH2(COOC2H5)2C2H5O-CH(COOC2H5)2-C

16、H2CH=CO-CH3CH(COOC2H5)2C2H5OHCH2CH2CH(COOC2H5)2CCH3O氧化：氧化： Tollens reagent還原：還原： 催化氫化（控制條件優(yōu)先還原催化氫化（控制條件優(yōu)先還原C=C） 金屬氫化物金屬氫化物 Meerwein-ponndorf reduction (異丙醇異丙醇- -異丙醇鋁異丙醇鋁、oppenauer oxidation) 立體專一性的順式加成反應(yīng)，親雙烯體在反應(yīng)過立體專一性的順式加成反應(yīng)，親雙烯體在反應(yīng)過程中構(gòu)型保持；反應(yīng)所得產(chǎn)物主要為程中構(gòu)型保持；反應(yīng)所得產(chǎn)物主要為內(nèi)型內(nèi)型的。的。+OOOOOOHHHHOOO+主要產(chǎn)物次要產(chǎn)物COOC

17、2H5HH5C2OOCHCOOC2H5COOC2H5COOC2H5COOC2H5+COOC2H5HHCOOC2H5COOC2H5COOC2H5+（六）插烯規(guī)律（六）插烯規(guī)律可視為乙醛分子中甲基和醛基之間插入乙烯基；可視為乙醛分子中甲基和醛基之間插入乙烯基；像這樣兩個(gè)基團(tuán)由于插入一個(gè)或一個(gè)以上乙烯基像這樣兩個(gè)基團(tuán)由于插入一個(gè)或一個(gè)以上乙烯基后相互影響不變的性質(zhì)稱為后相互影響不變的性質(zhì)稱為插烯作用插烯作用，又稱，又稱插烯插烯規(guī)律規(guī)律（vinylogy）。 CH3CHCHCHO2OH-CH3CHCHCHCH2CHCHCHOOHCH3CHCHCHCHCHCHCHO_ H2O二、乙烯酮二、乙烯酮CH3COCH3700CH2CO+CH4CH3CO2H700800CH2CO+H2O乙烯酮很容易聚合成雙乙烯酮，雙乙烯酮是具有刺激乙烯酮很容易聚合成雙乙烯酮，雙乙烯酮是具有刺激性的液體，具有內(nèi)酯結(jié)構(gòu)，在強(qiáng)熱（性的液體，具有內(nèi)酯結(jié)構(gòu)，在強(qiáng)熱（550600）時(shí)）時(shí)可解聚為乙烯酮。可解聚為乙烯酮。 2CH2COCH2COCCH2O雙乙烯酮雙乙烯酮CCH2OH2 OROHNH3H ClRCOOHCH2=CCH3OHCOHOHCH2COHORCH2CO