第2章重要有机化学反应

1、第二章第二章重要有机反应重要有机反应2CH3COCH3Mg,C6H6H3O+(CH3)2C C(CH3)2 OH OHMg,C6H6CH3C OCH3_ -CH3C OCH3_-CH3C=OCH32CH3C OCH3_ -CH3C OCH3_-Mg2+H3O+(CH3)2C C(CH3)2OH OHCH3 C C CH3CH3CH3OH OH_H3OCH3 C C CH3CH3CH3_O+CH3 C C CH3CH3CH3OH OH_H3O+CH3 C C CH3CH3CH3OH OH2_+CH3 C C CH3CH3CH3OH_+H2OCH3 C C CH3CH3CH3OH_+CH3 C C

2、 CH3CH3CH3OH_+-H+CH3 C C CH3CH3CH3_O RCH2COOH + Br2BrPRCHCOOH BrRCHCOOH OHNH3CN_RCHCOOH RCHCOOH RCHCOOH OHNH2CNKolbe-Schmidt反应用来制备水杨酸反应用来制备水杨酸(酚酸酚酸)ONaH3O+CO2heatOHCOONaCOOHOHOheatOCOONaCOONaOH-O=C=OH2 CH3CO2Et1.EtONa.EtOH2.H3+OCH3-C-CH2-C-O-EtOO.酯分子中酯分子中 -H有微弱酸性，在醇钠作用下，生有微弱酸性，在醇钠作用下，生成碳负离子（烯醇盐），并作为

3、亲核试剂进攻另成碳负离子（烯醇盐），并作为亲核试剂进攻另一分子的酯羰基一分子的酯羰基 ，生成缩合产物。，生成缩合产物。EtONaCH3-C-O-EtOCH2-C-O-Et-O.CH2=C-O-EtO-.CH3-C-O-EtO+CH2-C-O-Et-O.CH3-C-OEtO-CH2-CO2Et.-EtO-HAcH2OCH3-C-CH2-CO2EtO.EtONaCH3-C-CH2-CO2EtO-Na +CH3-C-CH-CO2EtO.CH3-C=CH-CO2EtONa.Me2CH-CO2EtEtONa EtOHMe2C-CO2Et-.Me2CH-C-OEtOMe2CH-C-OEtO-Me2C-CO

4、2Et.Me2CH-C-C-CO2EtOMeMe.C-OEtO+ CH3-C-OEtO1.EtONa.EtOH2.H3+OC-CH2-C-OEtOO.CH3-C-OEt + H-C-OEtOO1.EtONa.EtOH2.H3+OC-CH2-C-OEtOOH.OC-OEtCO2Et2. H3+O1. EtONa , EtOHCO2EtO.CO2EtC-OEtO.EtONaC-OEtOCO2Et-.COOEtCO2Et-.OCO2Et.EtONaOCO2Et-.H3+OOCO2Et.=O + CH3-C-O1. EtONa , EtOH2. H3+OCH2-C-O-OC-C-OEtO-.+OH-C

5、H3-C-CH2-C-CH3OOCH3-C-CH3OCH3-C-OEtO.-CHO+(CH3CO)2OheatNaAc-CH=CH-COOH.BrRCHCOOEtOHZnOCH3C HH2OCH3CH-CHCOOEtRCH3CO2Et +(Me2CH)2NLi+-CH2=CH-OEt-OLi+ (Me2CH)2NHOH.+LiO-CH2=CH-OEtOCH3C HCH3 IOCH3CHCH3CH2CO2EtCH2CO2EtLiH2OCH2CO2EtCH3CHOHCH2CO2Et1.=O + CH2-CO2EtOBrZn_C-H(R)C-ORC NNO2O_O_CH2=CHCH2=CHCH2=C

6、HCH2=CH.CH3-C-CH2-C-OEtOOEtONa.OOCH3-C-CH-C-OEt-CH2=CH-C=OHCH3-C-CH-CO2EtOCH2-CH2-CHO.CH3-C-CH2-CH2-CH2CHOOH3+O.51CH2(CO2Et)2EtONa.CH(CO2Et)2-CH3-CH=CH-C=OOEtCH3-CH-CH2-CO2EtCH(CO2Et)2.H3+OCHCH3-CH2COOHCH2COOH.15Beckmann重排重排例例 Birch还原还原H2O2(CH3CO3H)+O_N_(CH3)2_N(CH3)2CCPhCH3CH3H 115_O+NCH3CH3HHC(CH3

7、)2CPhPhC(CH3)2CHHCH3N+_ 115HCCPhCH3HHPhC(CH3)2CHHCH3N+O_ 115HCCPhCH3HHO(CH3)2HN+_+(CH3)3N_CH2-CH2-HOH-(CH3)4NClAg2O(CH3)4NOH+H2O-+CH3OH(CH3)3N +(CH3)3N_CH3OH-H2O+ CH2CH2+(CH3)3N+ CH3CH2CH2CH_CH3N(CH3)3OH_+CH3CH2CHCH_CH3CH3CH2CH2CHCH298%2%_CH3CH2R_CHR2_H+N(CH3)3HHOH_H2O+(CH3)3NPh CH2 CH2 N CH2 CH3 OH

8、+CH3 _ _CH3-4%96%+ CH2CH2CHPh_CH2CH32INHN+CH3CH3I_N+CH3CH3_HOH_Ag2OICH3Ag2O+ (CH3)3N_+CH3CH2 N C CH3 OH_CH3CH3CH3CH3CH3_CCH2CH3+CH2CH293%PhHCH3PhH+N(CH3)3OH_PhPhHHCH3+N(CH3)3OH_RSRSPhHHCH3CH3O_+N(CH3)2PhCH3HCH3HO_N(CH3)2+SSSSPhCCCH3HPhPhCCCH3HCH3R-C-NH2O OH -R-C-NH O-Br-BrR-C-NHBr O. OH -R-C-N-Br O-

9、._Br -R-C-N OO=C=N-R. OH -R-N=C-O- OH R-N-C-OO.-H-R-NH-C-OOR-NH2+ CO2(CO3 -2).Hofmann重排（降解）重排（降解）CNO.CH2HCH3DDCH3HCH2NNaOHBr2+-R-C-ClOR-C-N-ON NNaN3N2-R-C-NOR-N=C=OR-NH2H2OCO2-R-C-OHHN3O+H2SO4R-C-N3OR-N=C=OR-NH2-N2H2ORCOOHNaN3+ H2SO4H2ORNH2CO2N2+ Lossen反应反应 CH2-C-CH2C6H5ClEtONaOC6H5CH2CH2-CO2Et EtON

10、aCH2 CHC6H5Cl-OCCH2-C-CH2C6H5ClOOCCH2 CHC6H5EtONa-CH2 CHC6H5COOEtC6H5CH2CH2-CO2Et RCOOAg + Br2 heatR-C-O-BrO+AgBrOR-C-O-BrOOCR.+Br.RCOO_CO2R.BrRBrRCOOAg + Br2 heatRBr + CO2 + AgBrH2O heatRBr + CO2 + +R COOHHgOBr2+HgBr2H2O heatOR-C-O-BrOOCR.+Br.RCOO_CO2R.Br+RBrR COOHHgOBr2+Hg(RCOO)2Hg(RCOO)2Hg+R-C-O-

11、BrOBr2COOHEtOOC2科尔伯反应科尔伯反应(Kolbe)COOH2CH3CH3CH3.COO_CO2.2CH3CO2_.COOCH3-eCH3CH3CH3CH3.CH3+CH3EtOOC (CH2)4COOEt. + NH3COH2NiNH2CH_NH2C+NCOR_NH2C_RH2NiHC_NHRR2NH+COH2NiH_N_RRCEdvhweiler-Clarke反应反应例例 Mannich反应反应CH3-C-O-CH2CH2CH3O500 C0CH3-C-OH + CH3-CH=CH2O.C6H5_CH2O-C-CH3CH_O_C6H5HHC6H5C6H5HOC=OCH3HHC

12、6H5C6H5NH2NHNR2OH2O+NHNTsOH_SO3HCH3_TsOH =H+OH+OHNNH+HON+H2O_H2OHN+H_+NNN+-HNNNOHHTsOHHNONBr-CH2CO2EtICH3OH_CH3CH3_CO_ClCH2CH CN_H2OCH3N+H2OOCH3N+CH2CH2CNH2OOCH2CH2CNN+CO_CH3H2OOCO_CH3OCH2CO2EtOCH3TsOHHNNCH3+85%15%CH3NOCH2CH2CN_+O_CH2CNCH2_O_CO2EtCO2EtH+-CH3_+NOOCH2-_NOO-+NOOHCH2=- + 例例R-C-O-HO+ CH2

13、-N N+-+R-C-O O-CH3-N N+RCOOCH3N2+HXRSO3HArOHCH2N2CH3-C-CH=C-CH3OHOH+CH3XRSO3CH3ArOCH3CH3-C-CH=C-CH3OOCH3+ N2R-C-RO-CH2-N N+R C RCH2 N N+O-R-C-CH2-ROR C CH2 N RO-N+ N2R RCCOH2=O +CH2-N N+-O-+CH2-N N=O + N2CH2N2CH2C=CCCCH2C=CRHRHCCH2CRRHHCH2I2Cu(Zn)Et2OC=CRRHH+ CHCl3Me3COKMe3COHCl2CCCRRHH+ CHCl3HB +B-

14、CCl3-CCl3-+CCl2Cl-CHCH3C6H5HCOC2H5MgBrRHCH3C6H5HCOC2H5MgBrC2H5MgBrHCH3C6H5HC2H5MgBrCOHHCH3C6H5HC2H5COH3O+CHCH3HCOC2H5MgBrHOSHHCH3HCOOC2H5MgBrHCH3HC2H5COHOMgBrHCH3HC2H5COHOHH3O+-NH2NaNO2/HCl00C-N2Cl+-N2Cl+-H2O-OH-I-Cl-Br-CN-HKIr.t.CuClCuBrCuCNH3PO250%NH2HBF400CNaNO2N2BF4-+F/H2OCuNaNO2NO2Br-BrBrHNO3H2

15、SO4NO2FeHClNH2 Br2H2OBr-BrBrNH2NaNO2HCl 00CH3PO2TM+-N2Cl+-OHNaOHpH 7-9-N=N-OH+-N2Cl+-NMe2NaAc/H2OPH 5-7-N=N-NMe2 + HCHO + HCl-CH2ClZnCl2Reimer-Tiemann反应反应 Rosenmund还原还原C CH H2 2- -C CH H- -C CH H2 2O OH HO OH H O OH HN NH H2 2N NH H2 2S SO O4 4p ph h- -N NO O2 2heat+C CH H2 2= =C CH H- -C CH HO OH H2 2S SO O4 4C CH H2 2- -C CH H- -C CH H2 2O OH HO OH H O OH H+CHCH2 2CHCHC CO OH HNHNH2 2NHNHCHCH2 2CHCHC CO OH HH HH HH H2 2O ON NH HN Np ph h- -N NO O2 2