《有機(jī)化學(xué)》(胡宏紋版)第十四章 羧酸衍生物

1、C=ORR(H)R被G取代C=OGR(H)COGRG= XO-C-ROORNH2 (NHR，NR2)R-C=N-H2O酰鹵酸酐酯酰胺腈 R-C-GONu-R-C-GONu-G-R-C-NuOn注意能夠生成注意能夠生成酮酮的反應(yīng)的反應(yīng)A. RLi和和RMgX OR-C-XR-CR-COOO或RMgXOR-C-R通過(guò)降低溫度來(lái)控制反應(yīng)停留在生成酮這一步。OCH3-C-ClCH3CH2CH2CH2MgCl(C2H5)2O / FeCl3-700CO72%CH3CH2CH2CH2MgCl(C2H5)2O / FeCl3室溫OCH3-C-ClOHOClCH3MgI-150COCH3CH3CH3OR-C-

2、OR2 RMgXH3+OOHR-C-RRORO-C-OR3 RMgXH3+OOHR-C-RROH-C-OR2 RMgXH3+OOHR-CH-RSNOSOMgBr21. 2. H3+OOHSNSBrOCH3MgOMgBrOCH3NCOOCH3CH3OOCNOHHOCH3OCH3OOCH3OCH3OHC-OC2H51. 2 C4H9MgBr2. H3+OOHOC2H5O-C-OC2H51. 3 C2H5MgBr2. H3+O(C2H5)3COH2. H3+OOOOO1. 2 CH3LiOOOHH3+OOHO1. CH3Li2. H3+OC-COOC2H5CH3CH3C CCH3CH3CH3O70%

3、R-C-NH2ORMgXR-C-NHMgXO-RHRMgXR-C-NHMgXOMgXRH3+OR-C-ROR-C NRMgXR-C NMgXRH3+OR-C-ROCH3-C-CH2-C-NH2CH3CH3O1. 2 C6H5MgBr2. H3+OCH3-C-CH2-C-C6H5CH3CH3O1. C6H5MgBr2. H3+OOCH2CNCH2-C-CH3-C-CH2-C-ClCH3OCH3-C=CH2CH32CuLi+-50CCH3-C-CH2-C-CH2=C-CH3CH3OCH3C2H5O-C-(CH2)8-C-ClOO(C2H5)2CdC2H5O-C-(CH2)8-C-C2H5OOR-C

4、-NH2OR-C-OHO2 RMgX(2 RLi)2 RLiR-C NR-C-ClOR-C-XOR-C-HORMgX(RLi)R2CuLiR2CdRCORCH3-C-ClOH2OCH3-C-OHO+ HCl(CH3CO)2OH2OCH3-C-OHO2R-C-OC2H5OH2OR-C-OHO+ C2H5OHNaOH 250CR=相對(duì)速率CH3 ClCH2 Cl2CH CH3CO Cl3C 1 290 6130 7200 23150吸電子基團(tuán)對(duì)酯的水解有利CH3-C-OROH2OCH3-C-OHO+ ROHHCl 250C空間阻礙小對(duì)酯的水解有利 R-C-OROH+R-C-OROHH2OR-C-O

5、ROHOH2R-C OROHOHH-ROHR-C-OHOH-H+R-C-OHOOH-R-C-OROR-C-OROOH+ ROR-C-OHO強(qiáng)堿弱酸酸堿中和+ ROHR-C-OO H2ONaOHCH3-C-OC2H5OCH3-C-ONaO+ C2H5OHCH2OOCC17H35CH2OOCC17H35CH-OOCC17H35NaOHCH2OHCH2OHCH-OHC17H35C-ONaO3+R-C-NH2OR-C-NHROR-C-NR2OH2OH+或OH-R-C-OHO+ NH3RNH2 R2NHC-CH3OH3+O乙酰苯胺NH-CH3C-OHONH2+苯乙酰胺CH2C-NH2OH3+OCH2C-

6、OH + NH3O R-C=NH+R-C=NHH2OR-C=NHOH2-H+R-C=NHOHR-C-NH2OR-C-OHOH3+OR-C=NOH-R-C=NOH-OH-R-C=NHOHH2OR-C-NH2OR-C-OOH2OOH-R-C-GOROHH+或OH-R-C-ORO+ HGCH3-C-ClOCH3-C-OHCH3CH3+CH3-C-OO-C-CH3CH3CH3N(CH3)2NH(CH3)2Cl6368%+ONOOONCNCCNCNONOOOHOOCHOOCCOOHCOOHC2H5OH / H2OKOH回流 5 天C-ClO+ HONH3C-OO+ NH4ClHO(CH3CO)2OCH3

7、COOOOOC2H5OHBF3 (C2H5)2O，室溫SOCl2OClOOOOOn-C4H9OHCOOHOC4H9On-C4H9OHH2SO4OC4H9OOOC4H9ROHH+R-C-ORO+ ROHR-C-ORO低沸點(diǎn)醇高沸點(diǎn)醇CH3OCHOCH2CH2OHOCOCH3O+Zn(OAc)2Sb2S3COCH2CH2OOCOn滌綸CH2OHCH2OHCH3OHKOHCH2OOCCH3CH2OOCCH3+ CH3COOCH3OCH3OCH3OOAcH2O2, NaHSO4CH3OH, 室溫OOCH3OCH3OOAcHOOCH3OCH3OAcCH2=CH-C-NH2O+ C2H5OHOH-CH2=

8、CH-C-OC2H5O+ NH3C-NHCH3OCH3OHH+C-OCH3O+ CH3NH2R-C=NH+R-C=NHROHR-C=NHHORR-C=NH2ORH3+OR-C-OROR-C=NROR-C=NORR-C=NHORROH-RO-H2OR-C-OROOH-C-HOHCNCHCNOHC2H5OHH+CHCOOC2H5OHBrCH2CH2CH2CH2Br2 NaCNNC(CH2)4CNC2H5OHH+C2H5OOC(CH2)4COOC2H5R-C-OROR-C-OHO+ ROHH+直接酯化R-C-XO(RCO)2O+ ROHR-C-ORO親核加成-消除R-C-NH2ORCN+ ROHH+

9、或OH-R-C-ORO容易進(jìn)行不易進(jìn)行R-C-ORO+ ROHH+或OH-R-C-ORO+ ROH酯交換R-C-OO+ RXR-C-ORO+ X-親核取代R-C-RORCOOOHR-C-ORO+ RCOOH(容納電子能力RR)酮的過(guò)酸氧化OOO2 NH3OONH2O NH4H+OONH2OH3000CNHOONH33000C形成酰胺與脫水同時(shí)進(jìn)行，得到鄰苯二甲酰亞胺。OHNH2Cl-C-OC2H5OOHNH-C-OC2H5OOClCH2Cl(CH3)3CNHNH2ONHNHC(CH3)3CH2ClOOOH2NCOOHHRR = -CH(CH3)2；-CH2+NOOCOOHHRDMFN2, 10

10、00CONOOOSNNH2NHZn(OAc)2NNOOONSOCOOC2H5NH2NH2 H2OOCONHNH2C2H5OOCCH2NH2 HClH-C-OCH3O(C2H5)3NH-C-NHCH2COOC2H5ONH2NH2 H2ONNNNCH3CH3SCH2COOC2H5NNNNCH3CH3SCH2CONHNH2NHHOOCCOOCH3NH2+(COCl)2CH2Cl2HNNHOCOOCH3CH3-C-NH2OCH3-C-NHC2H5O+ NH3+ C2H5NH2H+H2N-C-NH2O+ 2 RNH2H+RNH-C-NHROCH3NH2NHONHONH2R-C-NHROR-C-OHO+

11、RNH2H+直接酰胺化R-C-XO(RCO)2O+ RNH2R-C-NHRO親核加成-消除R-C-NH2OH+或OH-R-C-NHRO容易進(jìn)行R-C-ORO+ RNH2H+或OH-R-C-NHRO酰胺交換+ RNH2R-C-RH+R-C-NHRO(-OH與反式的R對(duì)調(diào)后再轉(zhuǎn)化為酮式)Beckmann重排NOHNH3R-C=NR-C=NNH3R-C=NHNH2脒 (虛線內(nèi)為脒基)NC C N=N C CNCH3CH3CH3CH3偶氮異丁腈(AIBN)脂溶性自由基引發(fā)劑1. 2 NH3HN=C C N=N C C=NHCH3CH3CH3CH3NH2NH22,2-偶氮雙(2-脒基丙烷)鹽酸鹽(AAP

12、H) 2HCl2. 2 HCl水溶性自由基引發(fā)劑(CH3)2N-C N + (C2H5)2NH(C2H5)2NH HCl(CH3)2N- C - N(C2H5)2NH虛線內(nèi)的結(jié)構(gòu)稱(chēng)為胍，是一種強(qiáng)堿。R-C-GOR-C-OHO+R-C-OHOR-C-GO+OClHOClOOHONOOO - C - CF3OOClHOClOOONOOCH2-C=OHCH3-C-OHOOHCH3-C-CH3OCH2-C=OHCH3BrCH2-C-BrOCH2-C=OBrBr7000C7000CZnCH2=C=OCH2=C=OCH2=C=O+ H2O+ CH4+ ZnBr2活性中間體：烯酮CH2=C=ONuCH2-C

13、=ONuH-Nu-NuCH3-C=ONuCH3-C-NuOR-C-OHOR-C-XOR-C-NH2OR-C-OROR-C-O-C-ROOPX3或SOCl2P2O5/ ROH/H+NH3/H+P2O5RCNH2OH2OH2O/OH-H2O/H+或OH-H2O/H+或OH-RCOONaROHROHROHROHROHNH3NH3NH3NH3R-C-NH2NHRNH2R-C-XOR-C-NH2OR-C-OROR-C-O-C-ROORCNH2/PtRCH2OHRCH2OHRCH2OHRCH2NH2RCH2NH2含氧類(lèi)羧酸衍生物被還原為醇。含氮類(lèi)羧酸衍生物被還原為胺。C2H5O-C-CH2CH2C-ClO

14、OPd/BaSO4+ H2喹啉/SC2H5O-C-CH2CH2C-HOOCH3-C-CH2-C-ClCH3CH3OPd/BaSO4+ H2喹啉/SCH3-C-CH2-C-HCH3CH3OR-C-ORONaCH3R-C-CHRO OHHOOCCNH2PtHOOCCH2NH2FeC-C2H5O1. HCN2. (CH3)3SiClFeC-C2H5OSi(CH3)3CN2 LiAlH4(C2H5)2OFeC-C2H5OHCH2NH2NOOH210 % Pd/CNHOO R-C-ORONaNa+ + eR-C-ORO Na雙自由基耦合R-C C-RO NaO NaOROR-ORR-C-C-ROO2Na

15、R-C-ONaR-C-ONaH2OR-C-CHROOH類(lèi)似酮的雙分子還原OOHCOOCH3COOCH3Na甲苯CH2-O-C-(CH2)kCH=CH(CH2)7CH3CH-O-C-(CH2)mCH=CH(CH2)7CH3CH2-O-C-(CH2)nCH=CH(CH2)7CH3OOO蒜頭果油1. O32. O2O3氧化切斷C=CCH2-O-C-(CH2)kCOOHCH-O-C-(CH2)mCOOHCH2-O-C-(CH2)nCOOHOOOCH3OH酯交換得到二酸酯CH3OOC(CH2)lCOOCH3Na二甲苯酯的雙分子還原成環(huán)l-1HOOZnHCll-1O此方法可以以47%的轉(zhuǎn)化率得到環(huán)十五酮R

16、-C-ORONaROHRCH2OHR-C-ORONaNa+ + eR-C-ORO NaeR-C-ORONaROH-RO-R-C-HONaOR-RO-R-C-HOeR-C-HONaeR-C-HONaRCH2OHROH-RO-R-C-HONaHROH-RO-COOCH3COOCH3NaCH3OHOHOHCOOCH3COOCH3NaCH3OHOHOHSOCl2ClClOCH3OCH3BrONaCH3OH, 室溫OHCH3OCH3BrCNCH3OSnCl2HClCHOCH3O芳香腈還原為芳香醛 金屬還原劑金屬還原劑LiAlH4LiBH4NaBH4B2H6LiAlH(t-BuO)3RCOClRCH2OH

17、RCH2OHRCH2OH RCHO(RCO)2ORCH2OHRCH2OHRCH2OHRCH2OH RCOORRCH2OHRCH2OH RCH2OH RCONH2RCH2NH2 RCH2NH2 RCNRCH2NH2 (R=CH3(CH2)11)COOCH3ROORORLiAlH4(R=CH3(CH2)11)CH2OHROOROROFeCOOCH3(CH2)4NH(CH2)2CH3LiAlH4FeCH2OH(CH2)4NH(CH2)2CH3(C2H5OOC)2CHCH2CH2COOCH3LiAlH4OHOHOOHOOOCH3OphCH2OOLiAlH4O-150COHOOCH3OphCH2OClO

18、NH2LiAlH4THF, 600CClNH2R-C-NH2OR-C-NHO+ H+R-C=NHO一般情況下的酸性順序：RCOOH H2O RCONH2 ROH RC CH NH3NHOOK2CO3NKOO+ KHCO3pKa=6.35R-C-NH2O+R-C-ClO(RCO)2OR-COR-CONHHClRCOOH+CH3-C C-NH2OCH3CH3HNO2H2OCH3-C C-OHOCH3CH3R-C-NH2O+ Br2 + NaOHRNH2 + NaBr + Na2CO3R-C-NH2OR-C-NHBrO+Br2+NaOHNaOBr+ HBrC=O和Br兩個(gè)吸電子基團(tuán)使N上H的酸性更強(qiáng)OH-R-C N BrO同步進(jìn)行C=N形成Br-脫去R-遷移-Br-O=C=N-R異腈酸酯H2ORNH2 + CO2CH3-C C-NH2OCH3CH3Br2Na