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1、 Chapter 17 醛酮醛酮 Chapter 18 烯醇，烯酮，烯胺烯醇，烯酮，烯胺 Chapter 19 羧酸羧酸 Chapter 20 羧酸衍生物羧酸衍生物 Chapter 22 胺胺 Chapter 23 含氮芳香化合物含氮芳香化合物以及前面各章Ozonolysis of Alkenes（不推薦在合成中使用）（不推薦在合成中使用）CCO3COOCHydration of AlkynesCCH2OH+H g+CCHO HCCHOH醛酮的制備：Chapter 17 醛酮醛酮 O R COCO HCO HO O R RCOClAlCl3COROH醇的氧化醇的氧化Friedel-Crafts

2、 ?；；疪CO HR R O R N o reacti on思考：無(wú)思考：無(wú)AlCl3 生成什么？生成什么？Gattermann-Koch 反應(yīng)反應(yīng):+CO +HClAlCl3,CuClCHO+HClCH3CH3 MnO2H2SO4CH3CHO芳烴的氧化：芳烴的氧化：Fehling Test:Tollens Test:(Red)R RC C H HO O +C C u u +N Na aO OH H +H H2 2O OR RC C O OO O N Na a +H H +C C u u2 2O O2 2+R R C C H H O O +2 2 A A g g(N N H H3 3)2

3、 2 O O H HR RC C O OO O N NH H4 4 +N N H H3 3 +H H2 2O O +A Ag gN uCOR1R2HCOR1R2HN uCOHHCOR1HCOR1R2被進(jìn)攻的羰碳的反應(yīng)活性被進(jìn)攻的羰碳的反應(yīng)活性:原因：原因：1.位阻位阻 2.取代基的給電子效應(yīng)取代基的給電子效應(yīng)醛酮參與的反應(yīng)：醛酮參與的反應(yīng)：常見(jiàn)親核加成的親核試劑：常見(jiàn)親核加成的親核試劑：含碳含碳 HCN,RM,MCCH（格氏試劑，炔鈉）（格氏試劑，炔鈉）含氮含氮 NH3,RNH2,R2NH,H2N-Y 含氧含氧 H2O,ROH（醛酮的水解，羰基的保護(hù)）（醛酮的水解，羰基的保護(hù)）含硫含硫 RSH

4、,NaHSO3（鑒別醛酮類化合物）（鑒別醛酮類化合物）CORHCRHO N aSO3H某醛亞硫酸氫鈉加成物SOH OO N aCRHO HSO3N aHCN+RCOR CN CR O HR加熱氰基才變?yōu)轸然訜崆杌抛優(yōu)轸然鵆H3CH2CCH3NaCN HClCH3CH2CCH3H2SO4CH3CH2CCH3COOHCCH3H3CH2COOHCNOHCOOHAldehyde or Triphenylphosphonium Triphenylphosphine Ketone ylide(磷葉立德)oxideReaction type:Nucleophilic Addition then Elim

5、ination Ph3PCH2O +DMSOCH2RCOR+RNH2RCNRRPrimary amineImineCH +CH3NH2OCHNCH3NH3RNH2NH2NH2NH2OHNH2NHCNH2ONH2NHArAmmoniaPriary amineHydroxylamineHydrazineSemicarbazideArylhdrazine與一級(jí)胺反應(yīng)R RC CH H2 2C CR R +R R 2 2N NH HR RC CH H2 2C CR R R RC CH HC CR R N NR R 2 2O OO OH HN NR R2 2 O O+H HN NC C6 6H H6 6

6、C CH H3 3H HO O3 3S SN N烯胺的烷基化和?；┌返耐榛王；疦R-XR-C-XONNRROH2OHRROOO與二級(jí)胺反應(yīng)O OC CH H3 3C CH HO O1 1.3 30 0%N N a aO O H H,C C H H3 3O O H H2 2.H H3 3O OO OC CH H3 3C CH H2 2O OH H+H HC CO O O OH H+C CH H2 2O OC Cl lC CH HO O1 1.5 50 0%N N a aO O H H2 2.H H3 3O OC Cl lC CH H2 2O OH HC CO OO OH HC Cl l

7、+RCOR RCOO O H+RCOOR +R C O O H原子插在位阻大的一邊。R RC CH H (R R )O O H H R RC CH H2 2H H (R R )lClemmensen Reduction(acidic conditions)Zn(Hg)in HCl reduces the C=O into-CH2-lWolff-Kishner Reduction(basic conditions)NH2NH2/KOH/ethylene glycol(a high boiling solvent)reduces the C=O into-CH2-以上方法不還原以上方法不還原C=C

8、,C C 或-COOHCHHOHCHHO HCR HOR CHHO HCR R OR CR HO H+Li A l H4N aB H4C CH HO OO OC CH H3 3H HO O1 1.A Ag g2 2O O,N N a aO OH H,H H2 2O O2 2.H HC Cl lC CO OO OH HO OC CH H3 3H HO O酸催化的機(jī)理R R C C H H2 2C C R R O OH HO OH HH HF Fa as st t+R R C C H H2 2C C R R +O OH HO OH HH HO OH HH HR RC CH HC CR R H HO

9、 OH H+S Sl lo ow wR RC CH HC CR R +O OH HH HO OH HH HR RC CH HC CR R H HO OO OH H+S Sl lo ow wR RC CH HC CR R +H HO O H HO ORC HC RORC HC ROR RC CH HC CR R O OO OH HH H+F Fa as st tR RC CH HC CR R +H H O OO O H HC H3C C H2C C H3K =4C H3CC H C C H3O HOOOC H2C C H2C C H3O HO不穩(wěn)定不穩(wěn)定-Diketones（對(duì)稱）H2CC C

10、H2C H3O HC H3C C H2C H3OC H3CC H C H3O H(不對(duì)稱)多取代熱力學(xué)穩(wěn)定多取代熱力學(xué)穩(wěn)定少取代動(dòng)力學(xué)不穩(wěn)定少取代動(dòng)力學(xué)不穩(wěn)定R RC CC CO OR R +X X2 2R RH HR RC CC CO OR R +H H X XR RH Hx xCOC HRR COC H2RCOC H3RCOCHR R X2O H-RCOCXR R HO H+X-+醛酮的醛酮的 鹵代鹵代C CO OC C H HC CO OC C H H 2 2 C CO OC C H H3 3 Haloform 反應(yīng)（鑒別甲基酮）反應(yīng)（鑒別甲基酮）RCOCHHH3 I24 OH-RCOO

11、HOH+CHI3+3IRCH2CHONaOHRCHCHORCH2CHOHCOCHCHROHCH2RDehydrtionHCOCCHRCH2R(heat)O OH HH HC CH HO OH HC CH H +H H2 2O OO OR RR RH HH HC CH HO OR RH HC CH H2 2O OR RH HC CO OR RC CH H2 2R RO OH HH HH HC CO OR RC CH H2 2R RO OH HH HH HO OH H-O OH HH HC CO OR RC CH H2 2R RO OH HH HH H O OH HH HC CO OR RC CH

12、 H2 2R RO OH HH HH HF Fa as st tH HC CO OR RC CH H2 2R R +O OH HH HH H2 2O O機(jī)理（分子內(nèi)同理）機(jī)理（分子內(nèi)同理）H HC CO OR RC CH H2 2R RO OH HH HS Sl lo ow wH HC CO OR RH HC CC CH H2 2R R+O OH HH H3 3C CC CC CH H3 3O OC CH HO O+N Na aO OH HO OH C H +O(C H3)2C H C H2CHO K2C O3H2O-Et2O(C H3)2C H C HC H2O HCOH何時(shí)脫水？（1）產(chǎn)物

13、在羰基和羥基間要有一個(gè) -H（2）共軛（3）加熱（4）無(wú)水環(huán)境 a,b 不飽和羰基化合物不飽和羰基化合物C CC CC CO OC CC CC CO OC CC CC CO O34OHNuOHNuDirect or1,2-AdditionOHNuConjugate or1,4-Addition12快 稍慢 弱堿：RSH，CN-，R2CuLi，烯醇強(qiáng)堿：RLi,RMgX,LiAlH4CH2CHCORH2CCHCORRSHRSH1.R2CuLi2.H3O+KCNH2CCHCORNCHH2CCHCORRHRCOCRRH2CCHCORCHCRRORMichael AdditionOC H3O+C H2

14、C HCC H3O K O HC H3O HOC H3OC H2C H2C C H3OOO+N aO HO+H2ORobinson 成環(huán)成環(huán)OC H3OC H2C H2C C H3OA lO C(C H3)33 C6H6,H eatOC H3O HON ot isolated2-M ethyl-2-(3-oxo-b utyl)-cycloh exane-1,3-d ione-H2OOC H3O8a-M eth yl-3,4,8,8a-tetrahyd ro-2H,7H-nap h thalene-1,6-d io neO OC CH H3 3+L Li iA Al lH H4 41 1.E E

15、t t2 2O O2 2.H H2 2O OO OH HC CH H3 3O OC CH H3 3+H H2 2O OH HC CH H3 3P Pd d-C C3 3-M M e et th hy yl l-c cy yc cl l o oh he ex xa an no ol l3 3-M M e et th hy yl l-c cy yc cl l o oh he ex x-2 2-e en no on ne eH H3 3C CO O1 1.L Li i,N NH H3 3(l l)2 2.H H2 2O OH H3 3C CO O羧酸的制備羧酸的制備RCOXRRCOCORCOO R

16、RCON H2OH2ORCOO HBrNaCNCNH+H2OCOOH腈的水解（制備增加一個(gè)腈的水解（制備增加一個(gè)C的羧酸）的羧酸）格氏試劑和格氏試劑和CO2 反應(yīng)反應(yīng)RC O O H O O =C r2O7-2 or M nO4-2/H2SO4/H eat烴基取代的苯的氧化烴基取代的苯的氧化羧酸生成羧酸衍生物H H O O C C H H2 2C C H H2 2C C H H2 2C C O O H HO OO OO OR C O O H +Li A l H4CO HR +H2OHHR R C C H H2 2C C O O H H +X X2 2O OP PX X3 3R R C C H

17、H C C O O H H +H H X XX XO OCH3CH2CH2CH2COOHBr2PBr3CH3CH2CH2CHCOOH K2CO3H2O,HeatCH3CH2CH2CHCOOHBrOH羧酸的還原羧酸的還原羧酸的羧酸的鹵代鹵代CHCOOHCOOHCH2COOH+CO2二羧酸的脫羧二羧酸的脫羧RClOROOR1OROOR1ROHORNH2OROO=親核試劑進(jìn)攻時(shí)，羰基的活性：比如水解RCOXRRCOCORCOO R RCON H ROH2ORCOO HR O HRCOO HR N H2RRCOCORCOO R RCON H ROH2OR O HRCOO HR N H2NOOOO Et

18、OOO HO EtOOC lO EtOOC lB rEtO2CC O2EtB rEtO HSO C l2B r2EtO HRCOO R RCON H RH2OR O HRCOO HR N H2RCOO R B aseR R C C O O R R +H H2 2O OO OR R C C O O O O H H +R R O O H HH HR RC CO O R R O OH HO OH HH HR RC CO O R R +H H2 2O OO OH HR RC CO O H HO O R R R RC CO O H HO O R R R RC CO OO O R R H H酯的水解（機(jī)理

19、）酯的水解（機(jī)理）R RC CO O R R O OH HO OH HH HR RC CO O R R O OH HO OH HH HR RC CO O R R O O H HO OH HH HR RC CO O R R O O H HO OH HH HO O H H+H H3 3O OR RC CO O R R O O H HO O H HO OH HH HH HR RC CO O R R O O H HO O H H H H+H H2 2O OR RC CO O R R O O H HO O H H H HR RC CO O H HO O H H+R R O O H HO OH HH HR

20、 RC CO O H HO O+H H3 3O OH HR RC CO O H HO OC H3COO C(C H3)3C H3CO HO C(C H3)3C H3CO HOC H3CO HO C(C H3)3+C(C H3)3(C H3)3CO H2(C H3)3CO HH+H2OH+RCOORN a無(wú) 水 E tO HR C H2O H +R O H酯的雙分子還原酯的雙分子還原RCOORRCOOR二甲苯RCONaRCONaRCORCOHAcyloin condensation偶姻縮合NaH2O2R Li2R M gXR COO R R CO HRR2.H3OOO1.2C2H5MgBr/TH

21、FOHEtEtOHCCC6H5C6H5HHC6H5C HC H2C6H5OCOC H3CCC6H5HHC6H5+(主)5 0 0CH3CHOCH2CH2CH3COCH3500CH2CHCH2CH2CH3CH3CHCHCH2CH357%43%趨向于消除酸性較強(qiáng)，空間位阻較小的 HRCOOH+HOH+RNH2heatRCONHRacidRCOOCOR+RCOOHR2NHRCONR2+acid anhydride RCOOR+ROHRNH2RCONHR+esterRCONH2RCN+H2OH+or OH-nitrile=acid chlorideR2NH2+Cl-+RCONR2R2NH+2RCOCl

22、RCOOH+RNH2RCONHRRCH2NHR(1)(2)H2OLiAlH4H2OH+or-OHBr-,OH-RNH2+CO2POCl3(or P2O5)RCN(NaOBr)酰胺參與的反應(yīng)酰胺參與的反應(yīng)RCONH2RCNPOCl31 amideRCN+RXNaCNNa+X-alkyl halide+ArNN+CuCNArCNN2diazonium salt RCORHCNKCNRCRHOCNaldehyde or ketonecyanohydrin=RCONH2RCH2NH2(1)(2)LiAlH4H2OH+or-OHRCNH+or-OHH2ORCOOHH2ORMgXRCNRMgXH3O+RC

23、ORNCH3CH3CH3s p3 h y b rid iz e d親核性親核性和和堿性堿性（N上連有給電子基可以增加堿性）上連有給電子基可以增加堿性）NH2NH2NH2NH2ONO2 RNO2RNH2RCNRCH2NH2RCNH2ORCH2NH2RCONHRRCH2NHRRCONR2RCH2NR2RCRNHRCRHNH2RCRNRRCRHNHRCCHNR2CHCH2NR2RCRONH3orRCRORNH2H2/Pt or LiAlH 4H2/Pt or LiAlH 4LiAlH 4LiAlH 4LiAlH 4H2/PtLiAlH 4orH2/PtLiAlH 4H2/Pt or LiAlH 4H

24、2/PtH2/Ptor Sn/H+Hofmann 消除消除芳香胺芳香胺親電芳環(huán)取代親電芳環(huán)取代氧化氧化對(duì)二氨基聯(lián)苯重排對(duì)二氨基聯(lián)苯重排重氮化重氮化NH2Br2H2ONH2BrBrBrAniline2,4,6-TribromoanilineNH2(CH3CO)2OPyridineNH COCH3NH COCH3Br2BrH2OHClNH2Br+CH3CO2HNH2I2NaHCO3NH2INH2(CH3CO)2OPyridineNHCOCH3NHCOCH3COC6H5AlCl3C6H5COClNH2室溫發(fā)煙 H2SO4NH2SO3HNHCOCH380NHCOCH3SO2Cl(1)RNH2NH2SO2NHR(2)HClClSO3HNHNHNH2H2NH2NH2NH+70%30%COOHCH3HHO1.(CH3CH2)2O2.H3O機(jī)理要按步驟寫(xiě)機(jī)理要按步驟寫(xiě)D-A反應(yīng)，醚的水解作業(yè)的合成題！