有机化学-常用于有机合成的反应.pdf

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1、一.碳链增长的反应1.乙酰乙酸乙酯的的烷基化反应OOOOO1.NaOH,H2O-CO2CH3CHOEt+CH3CHOHCH3CCH2R2.H3ORROOOOOO1.EtONa1.EtONaCH3CHOEt2.RXCH3COEtCH3CH2OEt2.RX2RR'ROOO1.NaOH,H2O-CO2R2.H3O+CH3COHCH3CCHRR'R'合成CHCOCHRR型的酮3OOMeOHOOOC2H5ONa-BrCH2CH2CH2CH2BrCH3CCH2COOC2H5CH3CCHCOOC2H5OOC2H5ONa-BrCH2CH2CH2CH2CHCCH3BrCH2CH2CH2CH2CC

2、CH3COOC2H5COOC2H5COOC2H5-+O1)OH2)HCCH3COCH33)6/20/20165:22PM32.丙二酸酯的烷基化1.EtONa-CH(COEt)RCH(COEt)1.OHRCH2CO2H2222.RX22+2.H3O,1.EtONa2.R'X-RR'C(COEt)1.OHRR'CHCO2H22+2.H3O,合成增加两个碳的酸6/20/20165:22PM4HOMeO2CCO2MeO3.醛、酮、酰卤、酯、酸酐与金属试剂（格氏试剂、锂、试剂等）OMgXOO+R'MgXRCClRCClRCR'R'OH1.R'MgXRCR'+2.H3OR'-+OOMgXOR

3、'MgX-ROMgXR'MgXRCORRCORRCR'R'OMgXOHH+/H2ORCR'RCR'制备醇R'R'RHO+R'RR'R'3CO+XMgRC-+COH(R")H(R")HOMgX(R")HEt2O(CH3)3CCOCl+(CH3)2CuLi(CH3)3CCOCH3-78oC60%6/20/20165:22PM7Reformatsky反应——RZn,EtOR1R3+R1R312H3OCO+R3CHCO2EtR2CCHCO2EtR2CCHCO2EtR2O-+ZnBrOHBrHOOBr1.Zn,Et2OCO2Et+CO2Et2.HO+34.酯缩合反应(克莱

4、森缩合反应,迪克曼缩合,交叉酯缩合,酮与酯)，贝金反应,迈克尔反应，OOO1.EtONa/EtOH2CH3COC2H5+CH3CCH2COC2H52.H3O-酮酸酯OOOO1.C2H5ONaHCOC2H5+CH3COC2H5HCCH2COC2H52.H+3OOOOO1.C2H5ONaC6H5CCH3+C6H5COC2H52.H+OC6H5CCH2CC6H53AcONaC6H5CHO+(CH3CO)2OC6H5CHCHCO2Ho175C合成，-不饱和羧酸6/20/20165:22PM10Michael加成反应OOOKOEt,EtOH+Et2OO64%OOOEt3N+CNt-B

5、uOHOCN77%5.羟醛缩合反应增长碳链，主链增加2个碳，碳原子数成倍增加OHI5%NaOH2CH3CHOCH3CHCH2CHOCH3CHCHCHO有‐氢的醛‐羟基醛,‐不饱和醛OH-I2[H]CHOOHCHOCHOOH-H2OCHCHCHOCH3CHOOOCHOOCHCHCCH3C6H5CHOCHCHCCHCHC6H5NaOHCH3CCH3NaOH,H2O,H2O,78%94%OOCHCHCC6H5CCH386%CHOOMeMeMeMeNaOEtNaOH+草酸Michael羟醛缩合OOOOO加成54%OH86%——Robinson并环反应6.‐烷基化反应-OOONa

6、NHCH3ICH32EtO-I-27.末端炔在碱作用下与卤代烃或醛酮反应O1.HCC-Na+液氨2.HO+OH365%~75%OHOHHOHO8.偶联反应9.Friedel-Crafts烃基化和酰基化反应O1)AlCl33)Zn(Hg)+O2)HCl(aq)HClO10.增加1个碳[H]222酰胺胺+3羧酸腈+酯2+3Mannich反应三.环状化合物的合成1.Diels‐Alder反应——232332333外消旋的产物232332333外消旋的产物2.Robinson并环反应OMeMeMeMeNaOEtNaOH草酸+Michael羟醛缩合OOOOO加成54%OH86%3.迪克曼缩

7、合反应CO2C2H5CO2C2H51.C2H5ONa+2.H3OCO2C2H5OCO2C2H51.C2H5ONaCO2C2H5+CO2C2H52.H3OOCHCH33OO4.二卤代烃与乙酰乙酸乙酯或丙二酸乙酯的烷基化反应OOC2H5ONa-BrCH2CH2CH2CH2BrCH3CCH2COOC2H5CH3CCHCOOC2H5OOC2H5ONa-BrCH2CH2CH2CH2CHCCH3BrCH2CH2CH2CH2CCCH3COOC2H5COOC2H5COOC2H5-+O1)OH2)