浙江大学 英文 有机化学ppt课件

1、NH4+NCO-heatH2NCONH2Ammonium cyanateUreaCnH2nCnH2n+2CC+HHPt, Pd or NiSolvent,PressureCCHHCC+Solvent,PressureCCHHHH2H2PtCCH2+ C2H5OH(25oC, 50 atm)CCH2HCH3H3CH3CCH3HNiH2+ C2H5OH(25oC, 1 atm)PdH2+ethyl acetate2 H2OO5-CyclononyoneCyclonoanonePdRXZn, HX(-ZnX2)RHR-Zn2+X-2CH3CH2CHCH3BrZnHBr2CH3CH2CHCH3H+Zn

2、Br22CH3CHCH2CH2BrZnHBr+ZnBr2CH3CH32CH3CHCH2CH3CCRHNaNH2CC - Na+R+RXCCRRterminal alkynesodium amidealkynide anionR must be methyl or 1o and unbranced at the second carbonCCHHNaNH2CC - Na+H+H3CBrCCHCH384%H3CCHCCHNaNH2H3CBrH3CH3CCHCC-Na+H3CH3CCHCCH3CCH3H2/PtCH3CHCH2CH2CH3CH3Nu:-+R:X:.Nu:R+:X:-.Leaving

3、groupNucleophileNu:-+ R:X:.Nu:R+ :X:-.Nu:-R:X:-.Nu:-+R :X:.Nu:R:X:-.Or does the carbon-halogen bond break first?R+And thenR+HO-+CH3ClCH3OH+Cl-H:O:-.CCl:HHH+.-O.H-CHHHCl:.-+O.HCHHH+:Cl:.-Transition stateH3CHCl:H+:OH -.SN2H3CHHOH+Cl-cis-1-Chloro-3-methylcyclopentanetrans-3-methylcyclopentanolHO:-CBrH3

4、CHC6H13HOCCH3HC6H13+Br-(R)-(-)-2-Bromooctane(S)-(-)-octanol(CH3)3CCl+ 2 H2O(CH3)3COH+H3O+Cl-CClCH3H3CCH3SlowH2OC+CH3H3CCH3+Cl-C+CH3H3CCH3+:OHH.fastCO+CH3H3CCH3HH.+:OHH.fastCO+CH3H3CCH3HH.CO:CH3H3CCH3H.+O+HH.HCH3CH2CH2CBrH3CCH3CH2- Br-SlowCH3CH2CH2C+H3CCH3CH2:OH2.H2O:.front sideattackCH3CH2CH2COHH3CC

5、H3CH2CH3CH2CH2CCH3CH3CH2HOback sideattackTrigonal planar structureRXR = Me, 1o, or 2o(X = Cl, Br, or I)CN -RCNRS-RSRSH -RSHRO-ROROH -ROHRCC -CCRRCO-OROCROR3NRNR3+N3-RN3RCCYZelimination(-YZ)CCCH3CHCH3BrCH2H5ONaC2H5OH, 55oCH2CCHCH3+NaBr+C2H5OH79%BrCH2H5ONaC2H5OH, 55oCH2CCCH3+NaBr+C2H5OH91%CH3CH3CCH3CH

6、3C2H5O-+CH3CHBrCH3H2CCHCH3+CH2CH5OH + Br-CCCH3HHHHBrC2H5O:-.CCCH3HHHHBrC2H5O.-+Transition stateCCHHHCH3+C2H5OH+Br-(CH3)3CCl+H2OH2CC(CH3)2+ H3O+ + Cl-H3CCCH3CH3ClslowH2OH3CC+CH3CH3+Cl-HCHHC+CH3CH3+HO:H.HO+H.H+CCHHCH3CH3CH3CH2ONa + CH3CH2BrC2H5OH55oCCH3CH2OCH2CH3 +H2CCH290%10%CH3CH2ONa + CH3CHCH3C2H5O

7、H55oCH2CCHCH3E2 79%BrOC2H5SN221%+CH3CHCH3CH3CH2ONa + CH3CCH3C2H5OH25oCH2CCCH3E2 91%BrOC2H5SN19%+CH3CH3CH3CHCH3C2H5OH65oCCH3O-+CH3(CH2)15CH2CH2BrE2+SN21%99%(CH3)COH40oC+CH3(CH2)15CH2CH2BrE2+SN285%15%CH3O-H3CCH3CO-OH3C+CH3CHCH3BrSN2100%H3CCOOCHCH3CH3CCHHHHHXBaseHHHH-HXCCHHHHHOHH+, heatHHHH-HOHCCBrHHHH

8、BrZn, CH3CO2HHHHH-ZnBr2CH3CHCHBrCH2HCH3B:-ababCH3CHCCH3CH3CH3CH2CCH2CH3Zaitsevs rulemore stable alkenekinetic controlHofmann ruleB: CH3CH2O-: major product is aB: (CH3)3CO-: major product is bCCHLB:-Anti periplanartransition state(preferred)CCHB:-LSyn periplanartransition state(only with certain rig

9、id molecules)HCH(CH3)2HClHHH3C(a)CH(CH3)2H3C1-Menthene(78%)(more stable alkene)(b)CH(CH3)2H3C2-Menthene(22%)(Less stable alkene)EtO-(a)EtO-(b)CH(CH3)2ClH3CCH(CH3)2ClH3CNeomentyl chlorideMenthyl chlorideHCH(CH3)2ClHHHH3CMenthyl chloride(more stable conformation)HCH(CH3)2ClHHHCH3EtO-H3CCH(CH3)2Less st

10、able conformationElimination is impossible2-Menthene (100%)CCOHHAheat+H2OCRRROHCRRHOHCHRHOHCCROHRHH+AfastCCRO+HRHHCCRO+HRHHslowCC+RHRCC+RHRA-+fastCCRR+HACCHOHHHH+AfastCCHO+HHHHCCHHHA-+slowCCHH+HA+A-O+HHCHCCH3H3CCH3CH3OHCCCH3H3CCH3CH385%H3PO4heat+CCHCH3H2CCH3CH3majorminorCHCCH3H3CCH3CH3OH+HO+HHCHCCH3

11、H3CCH3CH3+OH2CHCCH3H3CCH3CH3+OH2CCHCH3H3CCH3CH3+CCHCH3H3CCH3CH3+2o Carbocation less stableCCH2CH3CCH3CH3+transition state1, 2 shiftCCHCH3H3CCH3CH3+3ocarbocationmore stableCCCH3CH2CH3CH3+A:-HHabCCCH3H3CCH3CH3+CCHCH3H2CCH3CH3majorminorCH3CH3OHH+ heat-H2OHCCH3CH3+C+CH3CH3+CH3CH3H+- H+CH3CH3CCBrBr+2 NaI

12、+I2CCBrBr+ZnBr2acetonCH3CO2HZnCCHRHRBrBr+RCCR+2 NH3+ 2 Br-2 NH2-H2CCHCH2CH3Br2CCl4CH2BrCHBrCH2CH3NaNH2mineral oil110-160oCHCCCH2CH3OCH3ClCH3ClPCl51. NaNH22. H+CHH3CCCCH3PtH2H3CHCCHCH3PtH2CH3CH2CH2CH3H3CH2CCCCH2CH3H2/Ni2B(P-2)(Syn additon)CCCH2CH3H3CH2CHHCCH2, Pd/CaCO3Lindlars Cat.(Syn additon)CCRRHH

13、RRCC(1) Li, C2H5NH2, -78oC(2) NH4Cl(anti additon)CCHRHRRRCC+ABadditionCCABCCCCHXHXH OSO3HCCHOSO3HHOHCCHOHXXCCXXH2CCHCH3H2CCHCH3HBr+HBrMarkovnikov addition productH2CCHCH3HBrCH3CH2CH2+Br-CH3CH2CH2Br(little formed)1o2oCH3CHCH3+Br-CH3CHCH3BrCCH2H3CH3C+IClCHCH2H3CH3CI+Cl-CCH2H3CH3CIClH2CCHCH3HBrCH3CH2CH

14、2Br+ROORradical mechanismCH2HCC2H5HXC2H5CCH2H+H+X-C2H5XHCH3(S)-C2H5HCH3H50%(R)-50%racmic formHBr2(b)HBr+Br-(a)HBrHBrBrHBrH(b)(a)CCH2H3CH3CBr2CCH2CH3H3CBr+OH2CCH2BrCH3H3CO+H2H+CCH2BrCH3H3COH73%CCHRRH+:CCl2CCHRRHCClClThe addition of canbenes is sterospecificCH2N2KOC(CH3)3/CHCl3CH2I2/Zn(Cu):CH2:CCl2:CH

15、2+MnO4-HHOOMnO-OH2OOH-coldHHOHOHCis-+OsO4HHOOOsOONaHSO3H2O25oCHHOHOHCis-pyridineH3CHCCHCH3KMnO4, OH-, H2Oheat2 CH3COOHH3CH2CHCCH2CH3KMnO4, OH-, H2OheatH3CH2CHCOCH3C+OO+H2OCH3KMnO4, OH-, H2OheatCH3CCH2CH2CH2CH2COOOH(1) O3, CH2Cl2, -78oCRRRH(2) Zn/HOAcRRO+RHOCCRRX2 ( 1 equiv.)anti additionCCRRXXX2RCX2

16、CX2RHX ( 1 equiv.)anti additionCCRRHXHXRCH2CX2R(1) O3 (2)HOAc or(1) KMnO4, OH- (2) H+RCOOH + RCOOHCH4+Cl2heator lightCH3Cl+MechanishCl2Cl.+Cl.Cl.heator light+CHHH:HHCl+CHHH.CHHH.+Cl2CH3Cl+Cl.ReactionHClR OO RH3CHCCH2+HBrCH3CH2CH2BrR OO RR O.heatR O.+HBrR OH+Br.Br.+H3CHCCH2H3CHCCHBr.H3CHCCHBr.+H : Br

17、2o RadicalCH3CH2CH2Br+Br.CCHCH3H3CCH3CH2(1) Hg(OAc)2(2) NaBH4, OH-THF-H2OCHCCH3H3CCH3CH3OHCCHCH3H3CCH3CH2Hg(OAc)2HgOAc+OAc-+HgOAc+CHCCH3H3CCH3CH2HgOAc+CHCCH3H3CCH3CH2HgOAc+H2OCCHCH3H3CCH3CH2HgOAc+OH2CCHCH3H3CCH3CH2HgOAc+OH2-H2OCCHCH3H3CCH3CH2HgOAcOHCCHCH3H3CCH3CH2HgOAcOHNaBH4/OH-CCHCH3H3CCH3CH3OHCCH

18、3CHHHBH3+CCH3CHHHHBHH+four-centertransition stateboron adds to to the less hindered carbon atomCCH3CHHHHBHHsyn additionCH3(1) THF: BH3(2) H2O2, OH-CH3HHOHH2O2/OH-CH3CO2HCCH3CHHHHOHCCH3CHHHHHheatSOOClH3C+CH3CH2OHSOOOCH2CH3H3CSOOClH3C+CH3CH2OHSOOH3COCH2CH3S ROOORH2CNu:-+NuCH2RRCHROH+ClTsretention-HClR

19、CHROTsRCHROTsNu:-+inversionSN2RCHRNu+TsO-ROHHClHBrPBrSOCl2RClRBrRBrRClCH3CHCHCH3CH3OHHBrCH3CHCH2CH3CH3Brsole product, Why?RO-Na+RLRORCH3CH2CH2OH+SN2NaHCH3CH2CH2ONaCH3CH2ICH3CH2OCH2CH2CH3H3CH3CHH+RCOOHOOCH3HCH3HH3CHHCH3+RCOOHOOCH3HHCH3+OCH3HHCH3cis-2-butenetrans-2-buteneEnantiomeric transSyn-Syn-OCH3

20、CH2O-+CH3CH2OCH2CHCH3OHBaseSN2OCH3OH+1-likeHACCH3H3COCH3CH2OHSNH3CH3CHH+RCOOHOcis-2-buteneSyn-OHHH3CH3CH2O, HAOHHHH3CH3C+H2OaHHCH3H3CHOOH(2R, 3R)HHH3CCH3OHHO(2S, 3S)H3-BH+RORRO-RHHOHROHRHHydride transferAlkoxide ionAlcoholRORNaBH4ROHRNaBH4LiAlH4COHRAldehydesCOHHRHCOHHRHKetonesCORRCOHRRHCOHRRHEstersC

21、OORRCOHHRH+HORCarboxylic AcidesCOOHRCHOHRHH2CrO4COHRCOHHRHCORRCOHRRHCOHRRRReactantPCCN+H CrO3Cl-KMnO4COOHRCOOHRCORRCORRRX+2 LiRLi+LiXRX+MgRMgXRM( M = Li or MgBr )HARH+MAOCCRCCOHCOHRCOHRRRCORRCOHRRRCOORRCOHRRR+HORRLiCuIR2CuLiRXRR+RCu+an alkyllithiumLithium dialkylcuprateRXLiEt2ORXLiXHX(low concentrat

22、ion)high temperatureXH2C CHCH3+ Cl2 400oCgas phaseH2C CHCH2Cl +HCl( X = Cl2, Br2 )HBrH2C CHCH3+NBSperoxides or lightNOOBrlight or ROORCCl4H2C CHCHBr +NOOHCCCCHBrCCCCBrHCCCC HBr1, 2 addition1,4 additionKinetic control(low temperature)Thermodynamic control(hith temperature)MajorMiniorMiniorMajorH2C CH

23、CHCH2+HBr- 80oC40oCH3CHC CHCH2Br+H3C CHCHH2C Br80%20%H3CHC CHCH2Br+H3C CHCHH2C Br20%80%+DieneDienophileAdduct+OH30oCOH+OCH3OOAlCl3Et2O25oCOHOHOOOHOHOCH3+COCH3COCH3HHOOHHCOCH3COCH3OO+COCH3HH3COCHOHHCOCH3COCH3OOOs-cis Conformations-trans conformation+ORORHightly strainedRHR is exoHRR is endoX2,FeX3XHO

24、NO2H2SO4NO2SO3H2SO4SO3HHCl, AlCl3( R can rearrange )RF-C AlkylationRCOCl, AlCl3CORF-C AcylationCORZn(Hg)HCl, refluxCH2R+OOOAlCl3CCH2CH2COHOOZn(Hg), HClrefluxCCH2CH2COHOSOCl2CH2CH2CH2CClOAlCl3, CS2OCH3NBS, LightCl2heat/lightCH2BrCH2ClCCl3CH31, KMnO4,OH-, heat2, H3O+COOHR1, KMnO4,OH-, heat2, H3O+COOHR

25、:HCCHCH3;CCCH3;COCH2CH3NH2CH3COClbaseNHCOCH3HNO3H2SO4NHCOCH3+NHCOCH3NO2NO290%trace1. H2O, H2SO42. OH-NH2NO2NH2CH3COClbaseNHCOCH3concdH2SO4NHCOCH3SO3HNHCOCH3SO3HHNO3NO21. H2O, H2SO42. OH-NH2NO2NaNH3, EtOHCH3CH2MgBr+CH3CHO1. Et2O2. H3O+CH3CH2CHCH3OHCH3CHCH2CHO+CCO2CH2CH31. Zn2. H3O+CH3CHCH2CHCCO2CH2CH

26、3CH3CH3BrCH3CH3OHCH3CH3COH:-+CO-HH3O+COHHO+LiAlH41. Et2OH3O+2.OHHCH3CCH2CH2CH3O+ NaBH4CH3CHCH2CH2CH3OHCH3OHOH-RRO1.NaCN2. HARROHCNHCl/H2OheatRROHCOOHRROHCH2NH2LiAlH4OAr3P+C -+CAr3POC+Ar3POO+Ar3P+CH2-CH2C2H5OH + CH3CHOC2H5OCOC2H5HCH3OOOC2H5OOC2H5OHCH2CH2OHOO(1) LiAlH4Et2O(2)H2OOHOOH3O+H2OOHOCO+H2NRCN

27、RCO+H2NHNRCNNHRCCH2CH3O+NH2NH2NaOHheatCH2CH2CH3C6H5CCH3ORCOOHOC6H5CCH3OORCHOAg(NH3)2+H2ORCOOH+AgRCAg(NH3)2+H2OOR,no reactionCCOH+X2acidor BaseCCOXC6H5CCH3O+X2acidor BaseC6H5CO-O+CHX3RCH2CHOOH-H2ORCH2CHCHCHOHROAn aldolNaBH4RCH2CHCHCH2OHOHRHA-H2ORH2CHCCCHORH2/NiRCH2CH2CHCH2OHRLiAlH4RH2CHCCCH2OHRH2, Pd

28、-CRCH2CH2CHCH2OHRC6H5CHO+CH3CCH3OOH-C6H5CHCHCCH3OC6H5CHO+CH3NO2OH-C6H5CHCHNO2H2/NiC6H5CHCH2NH2C6H5CHO+C6H5CH2CNEtO-C6H5CHCEtOHCNC6H5CH3CCH2CH2CH2CH2CHOOOH-CCH3OOH3CHHHB:-O-H3CO-H3CHHKinetic enolateThermodynamic enolateLess stablemore stableOH3CHHHO-Li+H3CDMELi+-N(i-C3H7)2OH3CO-Li+H3CDMELi+-N(i-C3H7)

29、2CH3IOH3CCH3C6H5CHCHCC6H5O+CN-C6H5CHCH2CC6H5CNOCH3CHCHCCH3O+CH3CuCH3CH CH2CCH3CH3OOOCH3+H2CCHCCH3OOH-OOCH3OconjugateadditionOH-aldol condensationOCH3ORH2CCOOHP + Br2( PBr3)RHCCOOHBrOH-RHCCOOHOHNH3RHCCOO-NH3+CH2CCOOHORheatCCH3OR+CO2CCCOOHOHORRheatCCOOHRRH+CO2CNRH3O+, heatRCOOH(i-Bu)2AlHH2ORCHOR-MM =

30、MgBr or LiRCORCH3OH3C+ CH2O+ (C2H5)2NHCH3CCH2OH2CN(C2H5)2N+BrCH2COC2H5ON+CH2COC2H5OH2OOCH2COC2H5OCCH2COOEtOH3C1. NaOEt2. RBrCCHCOOEtOH3CROH-, heat1.2.H3O+3. heatCH2COH3CR1. KOC(CH3)32. RBrCCHCOOEtOH3CROH-, heat1.2.H3O+3. heatCCHOH3CRCCCOOEtOH3CRRRArNH2HONO0-5oCArN+2Cu2O, Cu2+, H2OArOHCuClArClCuBrArB

31、rCuCNArCNKIArI(1) HBF4heatArFH3PO2, H2OArHCH3CH2CHCH3OH-+N(CH3)3150oCH3CHCCHCH3CH3CH2CH+CH2+(CH3)3N:+H2O5%95%CHCH2N+RCH3CH3-OHsyn-CHCH2R+NCH3CH3HOOHNaOHONaRCH2XOCH2ROOH Keto-enoltauomerizationHOOOHXCCCCHXCHCXHOSO2OHCCOSO2OHH2OCCHOHH2OCCHOHX2HXCH2HBrROORCH2BrB2H6H2O2OHOHHClClClClClCH3CHCHCH2ClHICH3CH

32、CH2CH2ClICH3OCHCH2HICH3OCHCH3I(CH3CH2)3CCHCH2HI(CH3CH2)2CCHCH3I CH2CH3RCCHH2OHgSO4H2SO4OCCH3RRCCR(H)B2H63CCHOOHRRHHB2H6H2O2OHOCHRHOHNOOONHOOHCOOCH2CH3H3CH2COOCHHCO2C2H5CO2C2H5HOOCH3C2H5ONaH2CCHCOCH3OOCH3CH2CH2COCH3NaOH-H2OOOCH3OHHOOCH3CONuCONuH-NuCHNuOHRCHOHCNRCHCNOHH3ORCHCOOHOHCHROHCOHORHROHCOROROO

33、HOHOHOHOHCH3OHHClOOHOHOHOHOCH3OCHOCH3COCH3OO(CH3)3CBrCH2OOHCOHOHH3CBrH3CH2CHCH3HOBrH3CH2CHHOCH3CH2CH3HNNaNH2NH3H2ONNH2NHNO3浓H2SO4NNO3SBr2, HOAc, SBrNCH3CH2INC2H5IClClNO2O2NNaOHClOHNO2O2NClCH2CH(CH3)CH2CH3C2H5NHCOCH3CH3COClAlCl3NHCOCH3COCH3SO3HSO3HNO2NO2浓H2SO4浓H2SO4浓HNO3H3OCH3CH2OCH2CHCH2HICH3CH2OHIC

34、H2CHCH2SN1CH3OCH(CH3)2HICH3I(CH3)2CHOHSN2CHCXCHCNuCCHLNuCCHNuLHCH3ClDHCH3KOH,EtOHClHCH3HDCH3ClHCH3HDCH3DCH3H3CHH2CCHC6H5(CH3CH2)3NCH2CH2C6H5OH(CH3)2CHCHCH2CH3N(CH3)3OH(CH3)2CHCHCHCH3NHCH3IAg2ONCH3CCH2CH3KMnO4CCH2OHOHH3CCH3KMnO4,H2OOHCH3C(CH2)2CCH(CH3)2OOHOOCCOOHRRRHO3OOORRRHPd/H2LiAlH4RCROHRCHOHZn,H

35、2ORROHROCH3CH2CHCH2O3Zn,H2OCH3CH2CHOHCHOO3LiAlH4HOCH2(CH2)4CHCH3OHO3Pd/C, H2HOCH2(CH2)3CH2OHORCOOHOOHOHOHCH3H2OOHH3COHOHCH2OHKMnO4, H2OCOOHHOOHCrO3, H2SO4H2O, CH2Cl2OOH3CHCCCH3CHCH3OHMnO2H3CHCCCCH3CH3OH3CHCCHCH2OHAl OCH(CH3)23CH3COCH3H3CHCCHCHOCH2OH(C5H5N)2.CrO3CH2Cl2CHORHCHCROHOHHIO4CHORCHOROHOHPb(

36、Ac)4OOCCH2OHOPb(Ac)4COOHHCOHKMnO4, HCOOHHOOCOCHCHCHOCrO3, HOCHCHCOOHCHOAg2O / H2OTHFCOOHOHNO3V2O5H2CH2CCOOHH2CH2CCOOHC(CH2)3CH3OZn-HgHCl(CH2)4CH3ONH2NH2, NaOH(HOCH2CH2)2O,COCH3H2NiCHCH3OHC6H5CHCHCHOAl OCH(CH3)23(CH3)2CHOHC6H5CHCHCH2OHCH3CHCHCH2CH2CHOLiAlH4H3OCH3CHCHCH2CH2CH2OHOMgH3OOHOHCH3CHO3HCHO稀O

37、HHOH2CCCH2OHCH2OHCHOHCHOOHC(CH2OH)4COOH(1) LiAlH4, Et2O(2) H3OCH2OHCH3CCH2CH2COOHONaBH4CH3CHCH2CH2COONaOHHOOH3CHOOCH2CCClOB2H6H2OHOH2CH2CCClOCH3CH2CCH2COOC2H5CH3OHLiAlH4CH3CH2CCH2CH2OHCH3OHH3CHCCHCH2CONHCH3LiAlH4Et2O,H3CHCCHCH2CH2NHCH3CH3CH2COCH2CH2CONH2NaBH4CH3CH2CCH2CH2CONH2OHHC2H5OC(CH2)2COOClPd

38、/ BaSO4C2H5OC(CH2)2COOHNKMnO4H2PtNCOOHCOOHNHOCHONaOHOCH2OHOCOOHMgClHCHOCH2OH(CH3)2COCH3MgIH2OH(CH3)3COHCH3CH2CHCH3OHHBrMgCO2H2OHCH3CH2CHCH3COOHCH3(CH2)3MgBrOH2OHCH3(CH2)4CH2OHCH3CCH2BrOOH OHHCH3CCH2BrOOMgOH2OHCH3CCH2CH2CH2OHOMgOH2OHBrCH2CH2OHMgH2OHHBrHCO2CH2CH2COHOOCHCHCOC2H5O2CH3MgIH2OHOCHCHC（CH3）2

39、OHHCOOC2H52CH3CH2MgClC2H5OC2H5H3OHCOH(C2H5)2CH3CH2CHCOOCH2CH3BrOZn, THFHH2OCH3CH2CHCOOCH2CH3HO2CH3CH2CH2CHONaOH, H2O80100CNaOH, H2O 68CCHCH2CH2CHCCH2OHCH2CH3CH3CH2CH2CHCHCH2OHCH2CH3OHO2NCH2OHCH3CH2ONaOHO2NCHCHCHOCHOCH3NO2NaOHCHCHNO2BrCHOOCH3NaOHBrCHOCH3OCHOCH3CCH2CH3OHOCHCCH3CCH3OCOOC2H5COCH3(1)C2H5

40、ONa(2)H3OCCH2COOCH3COC2H5OLDACH3CH2CClOH2OCH3CH2CCH2COC2H5OOCH3CH2CH2COC2H5OLDACH3IH2OCH3CH2CHCOC2H5OCH3H2OHSOCl2CH3CH2CHCClOCH3H2CCCOOC2H5OLiH2OCH3CH2CHCCH2COC2H5OCH3OC6H5CH2CCH3OBr, NaOH过量C6H5CH2CONaOCHBr3H3CCOBr2HOAcH3CCOBrArCHO(RCH2CO)2OCH3COOKArHCCCOOHRCHOCH3NO2OHH2OCHCHNO2NO2NO2O2NCH3CHOOHNO2N

41、O2O2NHCCHCH3CCH2ORCH3CCH2COC2H5OORX稀NaOHEtONaCH3CCH2CH2CCH3OOCH3CCH2COC2H5OO(1)EtONa(2)CH3COCH2Cl稀NaOHHCH2CH2COOC2H5CH2CH2COOC2H5(1)EtONa(2) HOCOOC2H5(1)EtONa(2)C2H5BrOCOOC2H5C2H5稀NaOHHOC2H5CH3CCH2COC2H5OOH2CCHCCH3OEtONaC2H5OHCH3CCH2OCH2CH2CCH3OCH3CCH2COC2H5OOC2H5ONaPhHCCHCOPhCH3COCHCHCH2CPhCOOC2H5P

42、hOC2H5ONaOC2H5OOCPhPhH2CCO2C2H5CO2C2H5(1)C2H5ONa(2)RX(1)OH / H2O(2)H /RCH2COOHH2CCO2C2H5CO2C2H5(1)C2H5ONa(2)BrCH2CH2CH2Br(COOEt)2LiAlH4OHOHP / Br2BrBrEtONa,H2CCO2C2H5CO2C2H5(1)OH / H2O(2)H /COOEtCOOEtCOOHOCCHC6H5HCC6H5CH2(COOEt)2C2H5ONaC2H5OHOCH2CC6H5HCC6H5CH2COOHPhCHOH2CCO2C2H5CO2C2H5C2H5ONaPhCHCH(

43、COOEt)2OHH2CCO2C2H5CO2C2H5(1)C2H5ONa(2)EtBrHCCO2C2H5CO2C2H5Et(1)C2H5ONa(2)PhCH2BrH3OPhCH2CHCOOHC2H5H2CCO2C2H5CO2C2H5C2H5ONaHCCCH2BrHCCO2C2H5CO2C2H5CH2CCHHgSO4H2SO4, H2OCH3CCH2CH2COOHOH2CCO2C2H5CO2C2H5C2H5ONaH2CCHCH2BrH2CCHCH2CH(COOC2H5)2(1)OH / H2O(2)H /H2CCHCH2CH2COOHLiALH4H2OH2CCHCH2CH2CH2OHOHOHHO

44、HOHOHOCH3H3COCH3COOOCH3OCHCHCHCH3C2H5OHHCCH3CHCC2H5HOCH2CHH3CCH3CHROHH3CCH3CH2CHCHRH2CCHOCH2CHCH2H2CCHCH2CH2CHOOCOC2H5C2H5H3CAlCl3H3CC2H5OHCOC2H5AlCl3OCHCHCH2CH3OCOCH3OCOCH3OHH2CCHCCH3HAlCl3OCOC6H5COHORCRNOHHRCNHROHH3CNOHNHH3CONH2HNO2N2-HH2OOHCH2CH3CH3CH2OHNH2CH3NO2CH3N2ClCH3FeHClHNO2HClN2ClCH3CuCNC

45、NCH3N2ClCH3H2OOHCH3NH2Br2H2ONH2BrBrBrNaNO2H2SO4H3PO4H2OBrBrBrH3CN2ClHOCH3H3CNNHOCH3HOH2CH2COHCH3CH2BrNaOHHOH2CH2COCH2CH3ClCH2CH2CH2CH2OHNaOHOH3CHCCHCH2CH2OHHOCH3(CH3)3CBrCH3CH2CH2ONa(CH3)2CCH2OH2OH2SO4HOCH2CH2OHOHHOCH2CH2OCH2CH2OCH2CH2OHClCH2CH2OCH2CH2ClOOHOHOClOClKOHTHF-H2OOOOOOHOCH2CH2OCH2CH2OH2SO

46、Cl2OHCOCH2CH3Zn-Hg浓HClCH2CH2CH3CCH2CHOClAlCl3CH3CH2CH2ClAlCl3CH2CH2CH3CH(CH3)2HFAlCl3H2COCH2H2OCH2CH2OH(C6H5)3PCH3CH2CH2Br(C6H5)3PCH2CH2CH3BrC6H5CHOC6H5CHCHCH2CH3H3CHCCHCHO(C6H5)3PCHC6H5H3CHCCHCHCHC6H5CHO(H5C2O)2POHCCOOCH3COOCH3CH3CH2CCH3OClCH2COOC2H5NaNH2CH3CH2CCHCOOC2H5CH3OHCH3H2CHCH3CHOCH3CClOAlC

47、l3CCH3OClCHCOOOC2H5CH3NaNH2CCCOOC2H5OCH3CH3HCHCCH3CH3ONH2CHONCHONHNRCClONCROH2OOCRONOOCH3C2H5HNH2NH2H2NClCH3CH2CH3HClCH3CH2CH3NKOODMFNNaOOPhCH2ClOHPhCH2NH2H3CNOHHNHH3COCCH3OOHCONH4CHCH3NH2OHCHO(CH3)2NH.HClOH2CNCH3CH3CH3COCH3HCHO, (CH3)2NH.HClCH3COCH2CH2N(CH3)2H3CHCCOOHCOOHCH3CH2COOHCO2n(H2C)COOHCOOH

48、(CH3CO)2On(H2C)COCOOH2OH2CCH2CH2COOHCH2CH2COOHBa(OH)2OH2OCO2OHCHCl3(1)NaOH / H2O(2)HOHCHOOHCHOArCHO2KCNArCHCOOHAr目标（母体）结构子系合成子子系试剂OHOHHC2H5CH3CHOC2H5MgBrOHOOHOHOLiCH3CHOOOHSSHOOOCOOHOOHOCHOFGIORORSSNHOOHCNHFGACHOCHOCOORFGR(不适用)CHOOHOHSSNHOOHCNHCHOCHOCOOHCHOOHCHOHCHOOHCOOHOO(1)(2)(1)(2)ClOOBrOOEtOOCC

49、OOEtO(1)(2)FGAEtOOCCOOEtOOEtOOCOClCOOEtOEtOOCOOHOOOEtOH(2)EtOOCOEtOOCH3CCH2CH2CH2CH2NOCH3CH3BrCH2CH2CH2CH2NH22 CH2O少量 HCOOHBrCH2CH2CH2CH2NCH3CH3Mg无水醚BrMgCH2CH2CH2CH2NCH3CH3CH3CClOH2OCH3CCH2CH2CH2CH2NOCH3CH3CH3CCHOCH2CH3CNNaHCH3CCH2CH2CH2CNOLiAlH4CH3CCH2CH2CH2CH2NH2OO(1) CH2O(2) H2 / Ni(1) CH2O(2) H2

50、 / NiCH3CCH2CH2CH2CH2NOOCH3CH3H3OCH3CCH2CH2CH2CH2NOCH3CH3HOOHTsOH,苯CH3CCH2CH2CH2CNOOCH3COHO2C2H5OH2HCH3COC2H5O2EtONaCH3CCH2COC2H5OOEtONaEtOHH2C CHCNCH3CCHCH2CH2CNOCOOC2H5OHHCH3CCH2CH2CH2CNOH2 / NiCH3CHCH2CH2CH2CH2NH2OH2CH2OHCOOH(过量)CH3CHCH2CH2CH2CH2NOHCH3CH3CH3CCH2CH2CH2CH2NCH3CH3OCrO3NCH3CHOHCHOHNC

51、H3CH3HClHCCH2CH2NCH3CH3ONaBH4HOCH2CH2CH2NCH3CH3SO2Cl2ClCH2CH2CH2NCH3CH3C2H5OCH3CCHCOC2H5OOClCH2CH2CH2NCH3CH3CH3CCHCH2CH2CH2NOCOOC2H5CH3CH3OHHCH3CCH2CH2CH2CH2NOCH3CH3CH3COOH22 C2H5OHHCH3COOC2H52BrH3CC2H5ONaC2H5OHCH3(1)B2H6(2)H2O2, OHCH3OHCH3Br2hvCH3Br2hvBrH3CC2H5ONaC2H5OHCH3HH2OH3COHH2CCH2AgO2H2COCH2

52、H2CCH2H2OHCH3CH2OHSOCl2CH3CH2ClMg无水醚CH3CH2MgClH2COCH2H2OHCH3CH2CH2CH2OHHBrHCH3CH2CH2CH2BrNaOHC2H5OHCH3CH2CHOCH3CH2MgCl无水醚H2OHCH3CH2CHCH2CH3OHCH3CH2CH2CH2OHH3CH2CHCCH2O3ZnH2OH2CCCHCH2CH3H3CCCHH3CCOHCHCH3CH2Al2O3H3CCOHCCH3CHPd / PbO, CaCO3H2CH3CCO3OHC CHKOHHgSO4, H2SO4H2OHCCH液NH3NaNH2CH3CH2CH2CCHB2H6H

53、2O2OHHCCNaCH3CH2CH2BrCH3CH2CH2CH2CHOH2NCOCH3H3COCHNCOCH3HH2OH3COCHNCH3COClAlCl3H2NCH3COClO2NZn / HCl硝化H3COH3COCOCH2CH2COOHOOOAlCl3H2OCH3CH2CCH2CH2CH3OHCH2CH3CH3CH2CCH2CH2CH3OCH3CH2MgBrH2OHCH3CH2CHCH2CH2CH3OHK2Cr2O7HCrO3NCH3CH2CH2OHCH3CH2CHOCH3CH2CH2MgBrH2OHOCH3CH2CH2CH2CHCH3OHOHH2SO4H2CCHCH2CHCH3OHB

54、2H6H2O2OHH2CCHCH2MgBr无水醚H2OHCH3CHO3H2Ni, 压力Br2hvBrNaOHOBr2AlBr3BrMg无水醚MgBrOMgBr无水醚H2OHOHHH3CCOHClAlCl3, CuClH3CCHOMgBr无水醚H2OHH3CHCOHHBrH3CHCBrMg无水醚HCHOH2OHH3CHCCH2OHHCHO, HClZnCl2,CH2ClKCNH2OHCH2COOHSOCl2CH2CClOH2 / PdBaSO4CH2CHOCH3CCH2BrOOHOHHCH3(CH2)4CH2OHMg无水醚OH2OHCH3CCH2CH2CH2OHOH2CCHCHOOHOHHOHC

55、HCOH2CH2O2OsO4H2CHCCHOOOHOHH, H2OH2CHCCHOOHOHCO + HClAlCl3, CuCl,CHOBr2FeBrCHOZn(Hg)HClBrCH3CO + HClAlCl3, CuCl,CHOBr2FeBr3BrCHOZn(Hg)HClBrCH3Mg无水醚HCHOH2OHCH2OHCH3Ni, H2CH3CH32(CH3)2COBa(OH)2I2(CH3)2CCHCCH3OCH3LiH2OH(H3C)2CCHCCH3OHCH3CH3CH2OHHBrHCH3CH2BrMg无水醚CH3CH2MgBrCH3CHOH2OHCH3CH2CHCH3OHK2Cr2O7HCH3CH2CCH3OHSCH2CH2SHHH3CH2CCH3CSSCH2CH2BrCH2CH2CHOC2H5OHHCl气BrCH2CH2CH(OC2H5)2Mg醚BrMgCH2CH2CH(OC2H5)2CH3CH2CHOH2ONH4Cl醚CH3CH2CHCH2CH2CH(OC2H5)2OHCrO3NCH3CH2CCH2CH2CH(OC2H5)2OH2OHCH3CH2CCH2CH2CHOOH3CBr2FeH3CBrMg无水醚H3CMgBrO无水醚H2OHH3CCH2CH2OHCrO3HH3CCH2COOHCH3