大學有機化學 羧酸及其衍生物

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1、會計學1大學有機化學大學有機化學 羧酸及其衍生物羧酸及其衍生物2022/5/29HCOOHformic acidmethanoic acidCH3COOHacetic acidethanoic acidOOHpropynoic acidOHOOOH2-octenedioic acidOOHOHO2-butenedioic acid第1頁/共118頁2022/5/29COOHO2Np-nitrobenzoic acidOOH3-vinyl-4-hexynoic acidCOOHO4-oxocyclohexanecarboxylic acidCOOHCOOHphthalic acidCOOH3-p

2、henyl propenoic acid3-phenyl-acrylic acid第2頁/共118頁2022/5/29CH3COOHCH3COOHH-bondH-bondCH3COHO+ H2OCH3COO+ H3O第3頁/共118頁2022/5/29 RCOOH + RCOCl+NRCOCROO+NH+Cl-RCOCROORCOO-Na+ + RCOClRCOOH2P2O5 RCOOCOR+ H2O第4頁/共118頁2022/5/29RCOClRCOOCRO RCOORRCONH2COLR+ NuHCONuH+LR-CONuHLR+-CONuR+ HL第5頁/共118頁2022/5/29CH

3、2CH2COOHCOOH300oCOOO+ H2OCCOOOHOH230oCO + H2OOOsuccinic acid succinic anhydride phthalic acid phthalic anhydride(100%)第6頁/共118頁2022/5/29RCOOH + SOCl2RCOCl + SO2 + HCl3RCOOH + PCl33RCOCl RCOOH + PCl5RCOCl + H3PO3+ POCl3 + HCl第7頁/共118頁2022/5/29RCOOH +SOClClRCOOHSClClO+-RCOOHSOCl+Cl-RCClOOHSOCl+_RCOCl+

4、OSOClHHCl + SO2第8頁/共118頁2022/5/29OCH3COH + SOCl280oCOCH3CCl+ SO2 +HCl(8090%)COHO+ PCl5CCl + POCl3 + HClO第9頁/共118頁2022/5/29CH3COOH + CH3CH2OHHACH3COOC2H5 + H2OC6H5COOH + CH3OHHAC6H5COOCH3 + H2O第10頁/共118頁2022/5/29CC6H5OOHCC6H5OOHHOHHH+HOCH3+-HOCH3C6H5COOOHHCH3H+C6H5COOOHCH3HH+CC6H5OCH3OH+HOH- H3O+ H3O

5、+CC6H5OCH3O第11頁/共118頁2022/5/29第12頁/共118頁2022/5/29OOHRNaOHRIOORR第13頁/共118頁2022/5/29OOHROOCH3RCH2N2+ N2第14頁/共118頁2022/5/29RCOOHRCOO-NH4+ NH3第15頁/共118頁2022/5/29RCONH2RCOO-NH4+(solid)heat+ H2O第16頁/共118頁2022/5/29H3OLiAlH4RCH2OHCYROY=OH , Cl , OCOR , OR.CH3CH2CH2CHONaBH4H2ONaBH4H2OCH3CH2CH2CH2OHCH3CH2CCH3

6、OCH3CH2CHCH3OH(85%)(87%)第17頁/共118頁2022/5/29CH3COOH + Cl2h ClCH2COOHor Ph Cl2CHCOOHh Cl3CCOOHor Por PRCHCOOHXOHNH3CNRCHCOOHOHRCHCOOHNH2RCHCOOHCNH3ORCHCOOHCOOH第18頁/共118頁2022/5/29COOHCOOHBr2 / FeBr3Br第19頁/共118頁2022/5/29HOOCCOOH HCOOH CO2+位有羰基的羧酸受熱易脫羧或鄰位連有強吸電基團時，易脫羧HOOCCH2COOHCCH2COOHCl3CCOOHCH3OCCH3CH3

7、OCH3COOH + CO2+ CO2CHCl3 + CO2 第20頁/共118頁2022/5/29HOOCCOOH O + H2OOOHOOCCOOH O + H2OOOHOOCCOOHBa(OH)2 O+ CO2 + H2OHOOCCOOHBa(OH)2 O + CO2 + H2O第21頁/共118頁2022/5/29吸電子誘導效應(yīng): NO2 CN F Cl Br I OCH3 OH C6H5 HC CHCHCH2CH2CCOHOOO場效應(yīng)誘導效應(yīng)第22頁/共118頁2022/5/29COOOHCOOOHCOOOH ClCl CHOOClHHClCOHOpKa 6.07pKa 5.69第2

8、3頁/共118頁2022/5/29四、制備四、制備（一）氧化法（一）氧化法 1、烯烴的氧化、烯烴的氧化 CH3CHCHCH3(1) KMnO4,OH-, H2O(2) H3O+heat(1) KMnO4,OH-, H2O(2) H3O+heat2CH3COOHCH3CH2C=CH2CH3CH3CH2C=OCH3+ CO2 + H2ORCHCHR(1) O3(2) H2O2RCOOH + RCOOH第24頁/共118頁2022/5/29RCHOKMnO4, OH-RCOO-H3O+RCOOHRCHOAg2O, OH-RCOO-H3O+RCOOHRCOH(1) Ag(NH3)2+, H2O(3)

9、H3O+RCOOHRCH2OH + KMnO4OH-H2OheatRCOO-K+ + MnO2H3O+RCOOH第25頁/共118頁2022/5/29CH3(1) KMnO4, OH-, heat(2) H3O+COOHbenzoic acid(100%)RC6H5(1) O3, CH3COOH(2) H2O2RCOOH3、烷基苯的氧化4、苯環(huán)的氧化第26頁/共118頁2022/5/29OCCH3CH2CH3HCNCH3CH2COHCH3CNHClH2OheatCH3CH2COHCH3COOH95%H2SO4heatCH3CHCCOOHCH3 -hydroxy acid,unsaturated

10、 acidHOCH2CH2ClNaCN(80%)HOCH2CH2CN(1) OH-, H2O(2) H3O+(7580%)HOCH2CH2COOHBrCH2CH2CH2BrNaCN(7780%)NCCH2CH2CH2CNH3O+HOOCCH2CH2CH2COOH第27頁/共118頁2022/5/29RX + MgEt2ORMgXCO2RCOOMgXH3O+RCOOHArX + MgEt2OArMgXCO2ArCOOMgXH3O+ArCOOHEtOOEtOO(1) NaOC2H5(2) BrEtOOEtOO(1) 50% KOH,reflux(2) dilute H2SO4, reflux (-

11、CO2) diethyl butylmalonate(80-90%)OHOhexanoic acid (75%)第28頁/共118頁2022/5/29EtOOEtOO(1) NaOC2H5(2) IEtOOEtOO(1) KOC(CH3)3(2)IEtOOEtOO(1) OH-, H2O(2) H3O+HOOHOOHOOOOH180oC-CO2OHOdiethyl ethylmalonatediethyl ethylpropylmalonateethylpropylmalonic acid2-ethylpentanoic acid第29頁/共118頁2022/5/29CH2I2 + 2Na+O

12、EtOEtOO-EtOOEtEtOOEtO OOO(1) aq. HCl(2) evaporation, heatHOOHOO+ 2CO2 + 4EtOHglutaric acid(80% from tetraester)第30頁/共118頁2022/5/29 Na+OEtOEtOO-BrBr+(-NaBr)EtOEtOBrOOC2H5ONaEtOEtOBrOO-OOOEtOEthydrolysis anddecarboxylationOOH第31頁/共118頁2022/5/29ArCCH3O(1) X2/NaOH(2) H3O+ArCOOH + CHX3第32頁/共118頁2022/5/29

13、ArCHO+(RCH2CO)2ORCH2COOKArCHCCOOHRRCH2COOH+反應(yīng)以反式產(chǎn)物為主+ (CH3CO)2OCH3COONaOOCHCHCOOHCHO第33頁/共118頁2022/5/29+CH2(COOC2H5)2CHO哌啶/吡啶 CHC(COOC2H5)2(1) OH /H2O(2) H / CHCHCOOHCH3(CH2)5CHO+CH2(COOH)2吡啶 CH3(CH2)5CHCHCOOH第34頁/共118頁2022/5/29CH3COCH3+CH2CNCOOC2H5CH3COONH4CH3CCH3CCNCOOC2H5(1) OH /H2O(2) H / CH3CCH

14、COOHCH3第35頁/共118頁2022/5/29CH33Cl2CCl3NaOHH2OCOONaHCOOH 第36頁/共118頁2022/5/29第37頁/共118頁2022/5/29H3COClethanoyl chlorideacetyl chlorideONH2benzoamideONN-methyl-N-ethyl benzoamideOOOphthalic anhydrideOOethyl ethanoateethyl acetateOH3COCH3benzyl 3-methylbutanoateOOOmethyl 4-acetylbenzoate第38頁/共118頁2022/5/

15、29AORONuRRANuO+ Nu+ AA= OH , X , OR , RCOO ,NH2 ; Nu= X ,OR , OH ,RCOO , NH3 .第39頁/共118頁2022/5/29OClROOORROO RRONH2R+H OHOOHR+HClOOHROHRNH3(皂化)(HCl , NaOH)第40頁/共118頁2022/5/29OClROOORROORR+HClOOHROHROHROORRRCN第41頁/共118頁2022/5/29OClROOORROO RR+NH4ClOONH4ROHRONH2RNH2H第42頁/共118頁2022/5/29R MgXR LiRCOORCO

16、ROHRCOCl1.CO22.H2O1.1.RCHO1.RCOROR COOHR CH2OHR CH2CH2OHR CR CRR CHR CRR CHROHOHROOO羧酸1 醇1 醇2 醇3 醇醛酮酮RMgXRMgXRMgXRCHOHRR CR COHRROHRR3 醇3 醇2 醇2.H3O2.H3O2.H3O2.H3O1.HCHO1. RCN2.H3O酮R CRORClOO(CH3)2CuLi第43頁/共118頁2022/5/29LiAlH4H3ORCH2OHCYROY=OH , Cl , OCOR , OR.RCNLiAlH4H3ORCH2NH2RCNNiRCH2NH2+H2120oC,

17、 壓力LiAlH4H3ORCH2NR2CNR2RO第44頁/共118頁2022/5/29LiAlHOC(CH3)33H3OCClH3COCHH3COAlHCH2CH(CH3)22COEtH3COH3OCClH3COCHH3COH2Pd/BaSO4二甲苯羅森孟德反應(yīng)CH3CHCHCH2COOC2H5Na + EtOHCH3CHCHCH2CH2OH鮑維特-勃朗克還原SnCl2/HClRCN(RCHNHHCl)2SnCl4H2ORCHO斯蒂芬反應(yīng)第45頁/共118頁2022/5/292CH3COC2H5NaOC2H5CH3CCHCOC2H5OOO-Na+ C2H5OHHClCH3CCH2COC2H5

18、OOsodioacetoacetic ester(removed bydistillation)ethyl acetoacetate(76%)第46頁/共118頁2022/5/29RCHCOC2H5OH+OC2H5-RCHCOC2H5O-RCHCOC2H5O-+ C2H5OHCOC2H5ORCH2+CHCOC2H5RO-RCH2CCHCOC2H5OC2H5ORO-+ C2H5O- RCH2CCHCOC2H5OORRCH2CCRCOC2H5OOHRCH2CCRCOC2H5OO-+ C2H5OHRCH2CCRCOC2H5OO-H3O+(rapid)RCH2CCOHRCOOC2H5keto form

19、enol form第47頁/共118頁2022/5/29C2H5OC(CH2)4COC2H5OO(1) NaOC2H5(2) H3O+OCOC2H5Odiethyl hexanedioate(diethyl adipate)ethyl 2-oxocyclopentanecarboxylate(74-81%)OEtOCHOOEtH+ -OEtOEtOCHOOEt-EtOO-HOOEtOHOOEt+ -OEtOOOEt-+ EtOHHOH2+OOOEt第48頁/共118頁2022/5/29NHOONKOO+ KOHNHOONBrOO+ NaOH+Br2+ NaOH+Br2CNH2RONH2R霍夫曼

20、降解或叫霍夫曼重排第49頁/共118頁2022/5/29CRONHH-:OH.RCONH-+ H2OBrBrRCONHBr+ Br-RCONHBr-:OH.RCONBr-+ H2O(- Br-)RNCOamideN-bromo amidebase-promoted N-bromination of the amide occurs.N-bromo amideisocyanateBase removes a proton from the nitrogen to give a bromoamide anionThe R- group migrates to the nitrogenas a br

21、omide ion departs. This producesan isocyanate.RNCO-:OH.RNCOOH-RNCOHO-HOHRNCOOHRNH2 + CO2 + OH-HCO3-isocyanatecarbamate ionamineThe isocyanate undergoes hydrolysis and decarboxylation to produce the amine.第50頁/共118頁2022/5/29SOCl2ONH2CH3H2OCH3CN RCONH2P4O10 or (CH3CO)2O heat (-H2O)RCN: + H3PO3 or CH3C

22、OOH 第51頁/共118頁2022/5/29RCOOH + SOCl2RCOCl + SO2 + HCl3RCOOH + PCl33RCOCl RCOOH + PCl5RCOCl + H3PO3+ POCl3 + HCl第52頁/共118頁2022/5/29 RCOOH + RCOCl+NRCOCROO+NH+Cl-RCOCROORCOO-Na+ + RCOCl CH2CH2COOHCOOH300oCOOO+ H2OCCOOOHOH230oCO + H2OOOsuccinic acid succinic anhydride phthalic acid phthalic anhydride(1

23、00%)第53頁/共118頁2022/5/29CH3COOH + CH3CH2OHHACH3COOC2H5 + H2OC6H5COOH + CH3OHHAC6H5COOCH3 + H2OC6H5CClO+ CH3CH2OH+NC6H5COCH2CH3 +ONH+Cl-(80%)（3） 由酰氯和醇的反應(yīng)由酰氯和醇的反應(yīng) OOHROOCH3RCH2N2+ N2第54頁/共118頁2022/5/29CH3COCCH3 + C6H5CH2OHOOCH3COCH2C6H5 + CH3COOHOO + CH3CHCH2CH3OOOHCOOHCOOCHCH2CH3CH3(97%) RCORO+ROHHA,

24、heatRCORO+ROHhigh boilingesterhigh boilingalcohol higher boilingesterlower boilingalcohol CH2CHCOCH3O+ CH3CH2CH2CH2OHHACH2CHCOCH2CH2CH2CH3 + CH3OHOmethyl acrylate butyl alcohol butyl acrylate methanol (94%) 第55頁/共118頁2022/5/29RCHCH2CH2CH2COHOOHAHORHOOHH+OROOHHH+OROH+OHH+O + H3O+ + A-ROa -lactone第56頁

25、/共118頁2022/5/29OOC6H5OH-/H2O HA, slight excessC6H5CHCH2CH2CO-OOH0oCHA, exactly one equivalentC6H5CHCH2CH2COHOOH第57頁/共118頁2022/5/29RCOCl:NHRRRCOClNHRR-+RCNORRH+Cl-:NHRRCRNORR + RRNH2+Cl-第58頁/共118頁2022/5/29RCOCl+ R3NRCONR3Cl-+H2ORCOOH+ HNR3Cl-+第59頁/共118頁2022/5/29RCOCROO+ 2RNHRRCNRRO+ RCOO-RRNH2+CCOOO+

26、 2NH3H2OwarmCCOONH2O-NH4+H3O+(-NH4+)CCOONH2OHphthalicanhydrideammoniumphthalamate(94%)phthalamicacid(81%)第60頁/共118頁2022/5/29CCOONH2OHphthalamic acid150160oCCCOONH + H2Ophthalimide(100%)第61頁/共118頁2022/5/29RCOOR+HNRRRCONRR+ ROHClCH2COOC2CH5+ NH3 (aq.)05oCClCH2CONH2+ C2H5OHethyl chloroacetatechloroacet

27、amide(6287%)第62頁/共118頁2022/5/29RCOOHRCOO-NH4+ NH3RCONH2RCOO-NH4+(solid)heat+ H2O第63頁/共118頁2022/5/29第64頁/共118頁2022/5/29RCOOH+C6H11NCNC6H11COROHCNC6H11NC6H11+-COROHCNC6H11NC6H11+-proton transferCOROCNC6H11NHC6H11reactive intermediateRNH2RCO-ONH2RCNHC6H11NC6H11+RCONHR+OCNHC6H11NHC6H11an amideN,N-dicycl

28、ohexylurea第65頁/共118頁2022/5/29RCN(1) concd. H2SO4(2) H2ORCONH2NHOa -lactam-lactam-lactamNHOaNHOa第66頁/共118頁2022/5/29SNCOOHCH3CH3NORHOC6H5CH2R=Penicillin GR= C6H5CHCH3AmpicillinR= C6H5OCH2Penicillin V第67頁/共118頁2022/5/29SNCOOHCH3CH3NORHOEEactive enzymea penicillinSNNHROCH3CH3COOHEO-HNSCH3CH3COOHNOROHina

29、ctive enzymeinactive enzyme第68頁/共118頁2022/5/29CNRROHHCNHRROC(R)CCH3C6H5HCH3N(E)OHH2SO4C(R)NHCH3C6H5HCH3CO構(gòu)型保持第69頁/共118頁2022/5/29CH3(CH2)6CH2Cl (in decane)R4N+Br-aqueous NaCN, 105oC,less than 2hCH3(CH2)6CN95% yieldRCONH2P4O10 or (CH3CO)2O heat (-H2O)RCN: + H3PO3 or CH3COOH 第70頁/共118頁2022/5/29COCl2 +

30、H2OCO2 + 2HClCOCl2ROHClCOORROHROCOORCOCl2+ 2NH3H2NCONH2 + 2HClH2NCNH2NH胍RCOHOH原酸OH 3C2H5ONa原甲酸三乙酯HCCl3+HC(OC2H5)3第71頁/共118頁2022/5/29CClClO+ 2CH3CH2OHCH3CH2OCOCH2CH3 + 2HClOcarbonyldichloridediethyl carbonateCClClO+ 4NH3H2NCNH2 + 2NH4ClOcarbonyldichlorideurea第72頁/共118頁2022/5/29ClCOCH3OClCOCCl3OClCClO

31、CH3OH- HCl3 Cl2- 3HClCl3COCOCCl3O第73頁/共118頁2022/5/29C6H5CH2OH + CClClOCC6H5CH2OClO+ HClbenzyl chloroformateCROClO+ RNH2ROCNHROOH-a carbamate(or urethane)第74頁/共118頁2022/5/29CC6H5CH2OClO+ H2NRCC6H5CH2ONHOROH-CC6H5CH2ONHORH2, PdHBr, CH3COOHRNH2 + CO2 + C6H5CH3RNH3 + CO2 + C6H5CH2Br+第75頁/共118頁2022/5/29R

32、OH +C6H5NCOROCNHC6H5Ophenyl isocyanate第76頁/共118頁2022/5/29CH3NCO+OHOCCH3NHOmethyl isocyanate 1-naphthol Sevin 第77頁/共118頁2022/5/29CHOClOHCl + CO2CROOHOROH+ CO2CHONH2ONH3 + CO2chloroformic acidunstablean alkyl hydrogen carbonateunstablecarbamic acidunstable第78頁/共118頁2022/5/29CROHOdecarboxylationRH + CO

33、2CRCCH2OHOO100150oCCRCH3O+ CO2第79頁/共118頁2022/5/29CRCH2OCOOH-CO2RCCH2OHCRCH3O -keto acidenolketoneRCOCH2COO-CO2RCOCH2-RCCH2O-HARCOCH3resonance-stabilizedanion第80頁/共118頁2022/5/29100150oCHOCCCOHRROOHCRRCOHO+ CO2第81頁/共118頁2022/5/29第82頁/共118頁2022/5/29CH2CH2CCOOOCH3OCH3A (C4H6O4) CH2CH2COCOOB (C4H4O3)H2SO

34、4excess CH3OHCH2CH2CH2OHCH2OHC (C4H10O4)CH2CH2CCOOOHOHD (C4H10O2)LiAlH4excess CH3OH第83頁/共118頁2022/5/29第84頁/共118頁2022/5/29FCH2COOHCH2CHCH2COOHNCCH2COOHClCH2COOH(CH3)2CHCH2COOH(A)(B)(C)(D)(E)HCCCOOHFCOOHCH3OCOOH(CH3)2NCOOHClCOOH(A)(B)(C)(D)(E)1)2)第85頁/共118頁2022/5/293)4)CH3OCOOHO2NCOOHFCOOHClCOOHCCOOHN

35、(A)(B)(C)(D)(E)NCCH2COOHO2NCH2COOHCH3CH2CH2COOHHCCCH2COOH(A)(B)(C)(D)第86頁/共118頁2022/5/29COOHCOOHCOOHCOOHNO2NO2NO2COOHCOOHCOOHClClCl5)(A) (B) (C) (D)(A) (B) (C) (D)6)COOH第87頁/共118頁2022/5/29COOHCOOHCOOHOHOHOHCOOH7)COOHCOOHCOOHOCH3OCH3OCH3COOHCOOHCOOHCH3CH3CH3pKa 4.20 pKa 2.98 pKa 4.08 pKa 4.57pKa 3.91

36、 pKa 4.27 pKa 4.38pKa 4.09 pKa 4.09 pKa 4.47第88頁/共118頁2022/5/291) CH3CH2CHO , CH3COCH3 , CH3CH2COCl , (CH3CO)2O , CH3CH2CO2CH3 , CH3CH2CO2H(1) (2) (3)(4) (5) (6),(1) (2)CH3CHCO2C2H5C2H5CH3CHCO2C2H5COCH3CH3CHCO2C2H5CO2C2H5CH3CH2CO2C2H52)(3) (4)第89頁/共118頁2022/5/29CHCOOHCH3CH3(CH2)42）由苯及4個碳以下化合物合成CO3）由

37、己二酸及苯甲腈合成由合成CH2COOH4)第90頁/共118頁2022/5/29CH3CHCH2CH3COCl6) 由乙醇合成COBrCl7）由環(huán)己酮和鄰氯苯甲酸通過格氏反應(yīng)合成第91頁/共118頁2022/5/29(1)2CH3CCH=CH2OOO+t-BuOKTHF(2)ONaOH(CH3)2C=CHCCH=C(CH3)2OH3CH3CCH3第92頁/共118頁2022/5/29OCOOC2H5OCH3COOC2H5O+OCH3COOC2H5O第93頁/共118頁2022/5/29CH3(2) CH3COCH2CH2COOH(3) CH3CH2CH2COCH2COCH3(4) CH3COC

38、H2CH2CH2BrCH3CH2CHCOOH(1)第94頁/共118頁2022/5/29(1)(2)CH2C2H5OCH2C2H5OCOOC2H5第95頁/共118頁2022/5/29FCH2COOHCH2CHCH2COOHNCCH2COOHClCH2COOH(CH3)2CHCH2COOH(A)(B)(C)(D)(E)HCCCOOHFCOOHCH3OCOOH(CH3)2NCOOHClCOOH(A)(B)(C)(D)(E)1) C A D B E2) B E A C D第96頁/共118頁2022/5/29CH3OCOOHO2NCOOHFCOOHClCOOHCCOOHN(A)(B)(C)(D)(

39、E)NCCH2COOHO2NCH2COOHCH3CH2CH2COOHHCCCH2COOH(A)(B)(C)(D)3) C D B A E4) B A D C第97頁/共118頁2022/5/29COOHCOOHCOOHCOOHNO2NO2NO2COOHCOOHCOOHClClCl5) B D C A(A) (B) (C) (D)(A) (B) (C) (D)pKa 4.20 pKa 2.18 pKa 3.46 pKa 3.44pKa 4.20 pKa 2.96 pKa 3.83 pKa 3.976) B C D ACOOH第98頁/共118頁2022/5/29COOHCOOHCOOHOHOHO

40、HCOOH7)COOHCOOHCOOHOCH3OCH3OCH3COOHCOOHCOOHCH3CH3CH3pKa 4.20 pKa 2.98 pKa 4.08 pKa 4.57pKa 3.91 pKa 4.27 pKa 4.38pKa 4.09 pKa 4.09 pKa 4.47第99頁/共118頁2022/5/291) (3) (4) (1) (2) (5) (6)CH3CH2CHO , CH3COCH3 , CH3CH2COCl , (CH3CO)2O , CH3CH2CO2CH3 , CH3CH2CO2H(1) (2) (3)(4) (5) (6),(1) (2)CH3CHCO2C2H5C

41、2H5CH3CHCO2C2H5COCH3CH3CHCO2C2H5CO2C2H5CH3CH2CO2C2H52) (2) (3) (4) (1)(3) (4)第100頁/共118頁2022/5/29Br2FeBr3BrMg / Et2OMgBrOH2SO4 HOKMnO4, OH-H3O+COCH2CH2CH2CH2COOHZn-Hg, HClCH2CH2CH2CH2CH2COOH第101頁/共118頁2022/5/292）由苯及4個碳以下化合物合成CH3COClFeCl3CCH3OH2 / PdCH3CHOHH+ CH2CH過過氧氧酸酸Mg / Et2OO OCH3CH2CH2BrCH3CH2C

42、H2MgBrCH3CH2CH2MgBrH+ CH3CH2CH2CH2CHOMgBrCH3CH2CH2CHCHH2 / PdCH3(CH2)4CH3COClFeCl3CH3(CH2)4CHH2 / PdCH3(CH2)4CCH3OCOOHCH3CH3(CH2)4CHCH3ClCH3(CH2)4CHCH3OHSOCl2NaCNCH3(CH2)4CHCNCH3H+ / H2OCH3(CH2)4CHCOOHCH3第102頁/共118頁2022/5/293）由己二酸及苯甲腈合成COCOHOOC(CH2)4COOHSOCl2EtOHClC(CH2)4CClOOEtOC(CH2)4COEtOOEtONaON

43、aOH / H2O H3O+O LiAlH4H3O+ HBrBrMg / Et2OBrMgCNCNMgBrH3O+COEtO第103頁/共118頁2022/5/29由合成4)CH2COOHNBSBrCH2(COOEt)2CH3CH2ONaHCCOOEtCOOEtBrCCOHHOOOCCOEtEtOOONaOH / H2O H3O+ CH2COOH第104頁/共118頁2022/5/29CH3CH2BrMg / Et2OOCH3CH2CH2CH2OMgH3O+CH3CH2CH2CH2OHHBrCH3CH2CH2CH2BrNH3CH3CH2CH2CH2NH2HCCHNH4Cl-CuClH2CCHC

44、CHHgSO4 / H2SO4H2OH2CCHCCH3O(CH3)2CuLiCl2H2O, HOAcCH3CH2CH2CCH3OCH3CH2CHCClCH3ONaOHCH3CHCHCCH3O(CH3)2CuLiCH3CHCH2CH3CCH3OCH3CHCH2CH3CONaOCH3CHCH2CH3CClONaOH, I2CH3CHCH2CH3CNHCH2CH2CH2CH3OCH3CHCH2CH3COHOH3O+SOCl2CH3CH2CH2CH2NH2第105頁/共118頁2022/5/29HCCHNH4Cl-CuClH2CCHCCHH2CCHCCH3OCH3CHCH2CH3COCl6) 由乙醇合

45、成CH3CH2OHconcd. H2SO4180 CCH2CH2Br2CH2CH2BrBrCH3CH2ONaHCCHOCOCH3CHCH2CH3CH2CCH3OOHCC-Na+HCCHNaNH2HCC-Na+CH3CH2CCH3OHgSO4 / H2SO4H2OHOCH2CH2OH, HClH2, PdH3O+第106頁/共118頁2022/5/29HgSO4 / H2SO4H2OHOCH2CH2OH, HClH2, PdH3O+CH3CHCCH3CCH3CH2CCH3HCAl2O3 CH3CH2CCH3OHCCHCH3CH3CHCCH3CCHCH3CH3CHCCH3COCH3OOCH3CH2

46、CCH3HCOCH3OOCH3CH2CCH3HCOONaI2, NaOHH3O+SOCl2CH3CH2CCH3HCOOHCH3CH2CCH3HCOCl第107頁/共118頁2022/5/29H2, Pd7）由環(huán)己酮和鄰氯苯甲酸通過格氏反應(yīng)合成CBrClOHOOC(CH2)4COOHSOCl2EtOHClC(CH2)4CClOOEtOC(CH2)4COEtOOEtONaONaOH / H2O H3O+O LiAlH4H3O+ COEtOOOHH2SO4KMnO4第108頁/共118頁2022/5/29Mg / Et2OH2, Pd / BaSO4HBrMgBrCClHOOSOCl2CClClOC

47、ClHOBrMgBrCOCOHHH2OKMnO4, OH-COBr2, HOAcBrClClCl第109頁/共118頁2022/5/29(1)2CH3CCH=CH2O+t-BuOKTHF(2)ONaOH(CH3)2C=CHCCH=C(CH3)2OOOOCH2CH2CH2CCH3OCH2CCH3OOCH3CH3CH3OCHCCHCCH2CH3CH3CH3NaOHOCHCCHCCH3CH3CH3CH3OCH3CH3CH3Michael addition第110頁/共118頁2022/5/29OCOOC2H5OCH3COOC2H5O+OCH3COOC2H5OOCOOC2H5+OOCOOC2H5C2H

48、5ONaCOOC2H5CH3OCOOC2H5CH3OC2H5ONaOOCOOC2H5CH3OCOOC2H5OHCH3O 第111頁/共118頁2022/5/29(2) CH3COCH2CH2COOHC2H5ONaNaOH, H2O H3O+ OC2H5OOOC2H5OOOOC2H5OOONaOKOKMnO4, OH-H3O+OHOOHOOO第112頁/共118頁2022/5/29C2H5ONaCH3CH3CH2CHCOOH(1)CH2(COOC2H5)2C2H5OOC2H5OOC2H5ONaC2H5OOC2H5OOCH3CH2BrC2H5OOC2H5OOCH3INaOH, H2O H3O+ C

49、H3CH3CH2CHCOOH第113頁/共118頁2022/5/29C2H5ONaNaOH, H2O H3O+ OC2H5OOOC2H5OO(3) CH3CH2CH2COCH2COCH3ClOOOOOOC2H5O第114頁/共118頁2022/5/29C2H5ONaNaOH, H2O H3O+ OC2H5OOOC2H5OOOOC2H5OOONaBrO(4) CH3COCH2CH2CH2BrPBr3OHO第115頁/共118頁2022/5/29(1)OCH2C2H5HOOC(CH2)4COOHSOCl2EtOHClC(CH2)4CClOOEtOC(CH2)4COEtOOEtONaONaOH / H2O H3O+ COEtOOHH2SO4KMnO4OCOEtOEtONaCH3CH2CH2BrOCOEtOCH2CH2CH3OCH2C2H5第116頁/共118頁2022/5/29(2)CH2C2H5OCOOC2H5HOOC(CH2)4COOHSOCl2EtOHClC(CH2)4CClOOEtOC(CH2)4COEtOO H3O+COEtOOHH2SO4KMnO4OCOEtOEtONaCH3CH2CH2BrOCOEtONHNCOEtONCH2CH2CH3CH2HCH2CH3第117頁/共118頁