大學(xué)有機(jī)化學(xué)第11章醛和酮

1、12COCOOOOOHCOHRCOHRCOR3COHCH3CH2CH2CH3CHCH2CHOCH3COHCH3COCH2CH3CO4CH3CH2CH2CHCH2CHCH2CHOCH3C2H5CH3CH2CCHCH2CH3OCH35CH3CHCHCHOCH2CHCHCHCHOCH3CH3CH3CHCHCHCH3CCH3OCHOCOCH2CH36CH3OH3CCHOCOCC78COHH116.5121.7121.7COCOCO9CH3CH2OHCu280CH3CHO + H2CH3CHCH2+ CO + H2Co(CO)6P(nC C4H9)32160，6 MPaCH3CH2CH2CHO + CH

2、3CHCHOCH310CH3+ O2V2O5360CHO + H2OCH2CH3+ O2硬硬脂脂酸酸鈷鈷130CCH3O(CH3)3CCH2OHK2Cr2O7H2SO4(CH3)3CCHO11RCH2OH+CH3CCH3OAl(OCHCH3)3CH3RCHO+CH3CHCH3OH苯/RCH2CHCHCHROHCH3COCH3(CH3)2CHO3AlRCH2CHCHCROCOClCH3OCH3 LiAl(OBuC t)3H,乙乙醚醚，-78 H3O+CHOCH3OCH3CrO3/吡啶；CH2Cl2/25。C或CrO3/H2SO4/H2O/丙酮RCHORCH2OH12RCOOR DIBACH，己己

3、烷烷，-78 H3O+RCOHCH3CH2CH2COCl + H2PdC BaSO4硫硫C 喹喹啉啉CH3CH2CH2COH+ HClAl(CH3)2CHCH2CH2CH(CH3)2H13+COClAlCl3CO+ HCl+ CO + HClAlCl3CuClCH3CH3CHO室室溫溫HCOCl14CH3CH2CH2CH3CH3OCH2CH3CH3CH2CHOCH3COCH3CH3CH2CH2OH沸沸點(diǎn)點(diǎn)/ /-0.5 8 49沸沸點(diǎn)點(diǎn)/ /56 97CH2CH3CHOCH2OHOHCH3沸沸點(diǎn)點(diǎn)/ /136.1 179.0 205.2 201.815COCOH(CH3)2CHCH2COCH3

4、O (CH3)2CCHCOCH3COHCOHCH3COCH2CO16COHCO17CCH3OCO18CH3CH2COCO1920OCR (H)CH21NuH慢NuC O+快NuC OH +-+HC O+C OHHRHArHCH3CH3C OC OC OC ORCH3RRArArC OC OC OO22CH3O2NCHOCHOCHONuC ORR23COR(CH3)H+SOHOO NaCR(CH3)HO NaSO3HCR(CH3)HSO3 NaOH(CH3)(CH3)R C SO3NaOHHOR C HNaHSO3HCl/Na2CO3NaClSO2H2OCO2H2O+Na2SO324CH3CH2

5、CCH3CH3CH2CCH2CH3NaHSO3不反應(yīng)Na2CO3OOCH3CH2C SO3NaOHCH3CHOCCH3O+NaHSO3CHSO3NaOHNa2CO3CHO(固體)不反應(yīng)R C H (CH3)(CH3)(CH3)+R C SO3HONaHONaHSO3NaCNR C CNOHH25R COHROH / H+CROROHHROH / H+CRORORH+ H2OCOH + 2CH3CH2OHHClCHOCH2CH3OCH2CH3+ H2OR C H+HOCH2HOCH2H+/RHCOCH2OCH2+H2OO(R)(R)26R COROR+H2OH+R C HO+2ROHH(R)(R

6、)由 CH3CHCH2CHO 合成 CH3CCH2CHOOHO+2C2H5OHH+無水CH3CHCH2CH(OC2H5)2CH3CHCH2CHOOHOHKMnO4/H+CH3CCH2CH(OC2H5)2H2O/H+CH3CCH2CHOOO27BrCH2CHO+HOCH2CH2OH無水HClBrCH2CHOCH2OCH2Mg/醚BrMgCH2CHOCH2OCH2CH3CHO醚CH3CHCH2CHOCH2OCH2OMgBrH2OH+CH3CHCH2CHOOHH2OCH3CH=CHCHO/28HOCH2CH2CH2COHH2CH2CCH2OCHOHH2CH2CCH2CHOOH+CORHOHRH快快C

7、ORHH+ ORH慢慢CRHORHOHORHCRHOROH+OHRH29CRHOROHORHHCRHOROHHH2OCORHRCORHRORHCRHORHORORHCRHOROR +OHRHCR(R)HOROR+ H2OH+CR(R)HO+ 2 ROH30縮醛或縮酮的生成可用于保護(hù)羰基：縮醛或縮酮的生成可用于保護(hù)羰基：O +HOCH2CH2HOTsOHOOCH2CH2+ H2OCH2OHOCOOOC2H5COOOC2H5H+HOCH2CH2OHOO LiAlH4 /乙醚 H3O+CH2OHOOCOOC2H5H+H2OOCH2OH31R C H+HCNOHR C OH(CH3)(CH3)OCNH

8、HCNOHH+CNH+R C H+HCNR C OH(CH3)(CH3)OCNCNR C OH(CH3)HCN32R C H(CH3)OR C OH(CH3)HCNKCN/H2OH2SO4R C H+(CH3)OR C OH(CH3)HCNNaHSO3R CH(CH3)SO3NaOHNaCNH2O33RCH2C H(CH3)ONaHSO3NaCNH2O12/RCH2C COOHH(CH3)OHRCH=C COOHH(CH3)RCH=C COOCH3H(CH3)RCH2C CH2NH2H(CH3)OHRCH2C CNOHH(CH3)H2OHCl濃H2SO4H2SO4CH3OH/H 34CH3CH

9、2COCH3HCNCH3CH2COHCNCH3濃濃H2SO4CH3CHCCH3COOHCOCH3CH3HCNCOHCNCH3CH3(75%)CH3OH, H2SO4CH2CCH3COOCH3甲基丙烯酸甲酯甲基丙烯酸甲酯(90%)有機(jī)玻璃：有機(jī)玻璃：CH2CCOOCH3CH3n聚甲基丙烯酸甲酯聚甲基丙烯酸甲酯(5) 與金屬有機(jī)試劑的加成與金屬有機(jī)試劑的加成Grignard試劑試劑 有機(jī)鋰試劑有機(jī)鋰試劑 炔鈉炔鈉 加成加成 水解水解 醇醇35CORCH2OHHHCORHCORRCOHRRRRMCHOHRRR Mg X +CORCO Mg XH3O+RCOHR Li+CORCO LiH3O+RCOH

10、+COCO NaH3O+RCCOHRCC NaRCCC36MgBr +COHH乙乙醚醚CH2OMgBrH3O+CH2OH(CH3)3CCC(CH3)3O+ (CH3)3CLi醚醚/ /- -7 70 0 H3O+(CH3)3C3COHOHCC Na, ,液液NH3, -33 H3O+, 70%OHCCH37H2OH+CH2COOC2H5OHH(R)H2O/H+ H2OH2SO4/CHCOOHH(R)R CR C=CH2COOHH(R)OHR CRC HO+BrCH2C OC2H5OZn甲苯CH2COOC2H5OZnBrH(R)(R)R C38H3O+COHCCO2RBrCCO2RZnBrZn:

11、CCO2RCOCBrZnOCCO2RCOHCCO2RH2O, H+CCCO2H39O + BrCH2COOC2H5 Zn, 甲甲苯苯 H3O+,OHCH2COOC2H5(70%)R Li RMgX RC CNa BrZnCH2COOC2H5(C6H5)3PCRR(C6H5)3PCRR40CRRO +(C6H5)3P CRRCRRCRR+ (C6H5)3P ORHC=O+(C6H5)3P CRR0。R C C RRP(C6H5)3HO-+C(R)(R)（R）R COHC RP(C6H5)3RRC=CRR+P(C6H5)3O=H(R)41(C6H5)3P+RRCHX(C6H5)3PCH XRR(C

12、6H5)3PRRCH + PhLiX(C6H5)3PRRC+ C6H6 + LiX423C6H5MgBr + PCl3(C6H5)3P + 3MgClBrCH3Cl(C6H5)3P nC BuLiPh3PCH2OCH2CH2O + CH3ClCl HCHO+43CHP(C6H5)3+ OHCOCCH3O(C6H5)3POOCCH3OOH44H2CO + NH3H2CNH聚聚合合NNN3HCHONH3NNNNHHHCOH+COHCOHH2N YCN YOHHH2OCN YH+CN YOH2HHH+CN YYNHH+COCNY + H2O45CO + H2NOHCNOH + H2OCO + H2N

13、NH2CNNH2+ H2OCO + H2NNHC6H5HNO2O2NCNNHC6H5HNO2O2N+ H2OO + H2NNHCNH2ONNHCNH2O+ H2O46H2N NH=N NHNO2NO2NO2NO2CH3CH3O+H+bp.169。Cmp155。CH2N NH=N NHNO2NO2NO2NO2CH3CH3O+H+bp.169。Cmp130。C47CNC6H5HOHCNC6H5HOH+ H2OCO +H2NRH+COHNHRH+CNRCHO+ CH3NH2CNCH3H+ H2O48+ H2ORCH2CRO+ R2NHRCH2CROHNR2RCHCRNR2O+NH苯苯N+ H2ONN

14、49ONHH3O+NBrCH2COOC2H5NCH2COOC2H5H2OCH2COOC2H5OCORCH3H+CORCH250CORCH2CORCH2CORCH2COCHHHBr2, AlCl3乙乙醚醚，0 0COCHHBrCH3COCH3+ OH-H2OCH3COCH2CH3COCH2慢慢CH3COCH2+ BrBr快快CH3COCH2Br51快快CH3COCH3+ H+CH3COHCH2-H+HCH3COHCH2CH3COHCH2+BrBr快快CH3COHCH2BrCH3COHCH2Br+ BrCH3COHCH2BrCH3COCH2Br + H+快快CH3CO52PhCCH3ONaOHOP

15、hCCH2XNaOHOPhCCHX2NaOHOPhCCX3X2X2X2PhCOCX3+OHPhCOCX3OHPhCOOH+PhCOO+ CHX3CX3CH3COCH3CHOH,53R C CH3R C ONaOO+3NaOX( X2+NaOH )+HCX3+NaOH2OOOC CH33I2NaOHC CI3NaOHC ONa+HCI3OOCH=CH C CH33KOBrCH=CHC OKH+CH=CHCOOHCH CH3OHO+CH CH3OHRI2NaOH C CH3I2/NaOHCOOHCI3RRNa(H)(H)(H)542 CH3CHO10% NaOH5 CH3CHCH2CHOOHOCH

16、3CHCH2CHCH3CH=CHCHOH2O/或 H+OH55OOOCH3CH2CHCH3CH2CHH2O/或 H+OHCH3CH2C H+CH3CH2C H10%NaOH5 C。CH3CH3CHCH=CCHOOO+CH3CH2C HCH3CHCHHOH2O+H2OCH3CH2CHCH3OHCHCHOOHOOCH3CH2C H+CH3CHCHCH3CH2CH CH3OCHCHO56-OHCH3CHO+CH3CH2CHO四種產(chǎn)物2CH3CH=CHCHOOHCH3CH=CHCHOCH3CH=CHCHCH2CH=CHCH=CHCH=CHCHOOHCH2O+CH3CH2CHO稀OHCH2=C CHOC

17、H3+CH3CH2CH=C CHOCH3572CH3CCH3OBa(OH)2CH3COHCH3CH2CCH3OH2OCH3CCH3=CHCCH3O3 HCHO+CHHHCHOCa(OH)255HOCH2CCHOCH2OHCH2OH58OONa2CO3, H2O回回流流OOHOOOCH2CH2CCH3OHH2OOHOO CHO+ CH3CHONaOHCOHHCHHCHOH2OCHCHOCH59CHOCH3CH2COOOCH3CH2C+CH3CH2COONa135, 30h CHCCOOH + CH3CH2COOHCH370%CH3COCH3+ H COH+ R NHHCH3COCH2 CH2NH

18、R+ H2O60RCHO+ 2 Ag(NH3)2OHRCONH4O+ 2Ag+ H2O + 3NH3CH3CHCHCHOAg(NH3)2OHH3O+CH3CHCHCOOH61+Cu(OH)2NaOH+CHOAg(NH3)2OHCH3CH2CHOCH3CH2COOHRCH=CHCHOAg(NH3)2OHRCH=CHCOOHRCHO+2Cu (OH)2NaOHRCOONa+Cu2O+3H2O+O50% HNO3V2O5CH2CH2COOHCH2CH2COOHKMnO4、 CrO362RC H(R)+H2Ni或Pt或PdP.a.RCH H(R)OHO/C=C、C C、CN、NO2、COOR、COX、

19、X等CH2CH=CHCHOCH3CH2CH2CH2OHH2/NiP.a./Br63O2NCH=CHCHOO2NCH=CHCH2OHNa/C2H5OHC=C、C C、CN、COOH、COOR、COX、NO2、X、等64C=C、C C、CN、COOH、COOR、COX、NO2、X、等O2NCH=CHCHOO2NCH=CHCH2OHNaBH4/C2H5OH或NaBH4/H2O/OHBHHHHNa+NaBH4/C2H5OHNaBH4/H2O/OH65Li+AlHHHHC 、CN、COOH、COOR、 C O C 、COX、NO2OOOO2NCH=CHCH=CHOLiAlH4/1412醚H2O/H+H2

20、NCH2CH2OHCCHBrBrC=C、C C、X66CORHAlH3LiHCORHHAlH3Li3RCHO(RCH2O)4AlLi稀 HCl4 RCH2OH+ AlCl3 + LiClAl OCH(CH3)2 3/(CH3)2CHOHC OR(R)H+ (CH3)2CHOH(CH3)2CHO3AlCHOHR(R)H+ CH3COCH367OOCOOH、COOR、 C O C 、COX CH2CH2C OHOO CH2CH2C OHOZn Hg/HCl(濃)苯或甲苯/CCH2CH3CH=CHCH3CH=CHZn Hg/HCl(濃)苯或甲苯/CHOCH368COR(R)HH2NNH2CNNH2R

21、(R)HNaOC2H5C2H5OH高高溫溫、高高壓壓CH2R(R)H+ N2OOCOOH、COOR、 C O C 、COXCH3OCH2CH3OCH3OCH2CH2CH3CH2N NH2/NaOH(HOCH2CH2)2O/180。C692 HCHO + NaOHHCOONa + CH3O HArCHO + OHArCOHOHCArHOArCOOH+ ArCOHHArCOO-+ ArCOHHHH+ArCOOH+ ArCOHHH70HOCH2CCH2OHCH2OHCHO + HCHOCa(OH)260HOCH2CCH2OHCH2OHCH2OH+ 1 / 2 (HCOO)2Ca71CCCOCH2CHCOH + HClClCH2CH2CHOCCCOCCCOCCCO72CH2CHCOHH+CH2CHCOH