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12有机化合物的合成解好有机合成题的基础是将有机反应按官能团转化、增长碳链、减少碳链、重组碳架、环扩大、环缩小、开环、关环等进行归纳、熟记、灵活应用。解合成题通常分两步进行：1.运用逆合成法对目标分子进行剖析，最终确定合成所需的起始原料。这就要求掌握各类化合物的拆分方法。2.以剖析为依据，写出合成方案。3RORR-XR-RRCCRRCH2-CH2RRCH=CHRRCH2-CH2R有机化学合成总结1.饱和脂肪烃（1）．偶联反应(2)．醛、酮还原(3)．烯烃、炔烃还原4CH=CH2RRCH2-CH2-OHR-CH2CH2XR-CH=CH22.不饱和脂肪烃一、烯烃合成(1)．醇脱水(2)．卤代烷脱卤化氢(3)．邻二卤化合物脱卤化氢(4)．炔的还原R-CC-RH2H2NaNH3或Li,C=CHRRHHHRC=CRLindlar触媒(5)．Wittig反应CCR1R2RHCOR1R2R-CH=P(Ph)3+5R-CC-R1R-CR1X+CHR-CCR1R-C-C-R1XHHX二、炔烃合成（1）从其它炔烃（2）通过二卤消除反应6RXRHX2+R-CH-CH2XR-CH=CH2R-CH=CH2R-CHCH2XXX2+RXROHX-G+RClNaIRI+3.卤代烃(1)烷烃的卤代(2)不饱和烃和卤化氢或卤素加成(3)从醇制备(4)卤素的置换7C-CH2OHHRHR-CH=CH2OH2+R-CH2CH2OHR-CH=CH2(BH3)2C-CH2OHHRHR-CH=CH2+R-CH2OHRCHOR-COOHRCOOR1RRORROHR-CH2-OHRMgXCH2O+RHR1ORMgXR1CHOR1MgXRCHO++RR2R1ORMgXR1R2COR1MgXRR2COR2MgXRR1CO+++R-CH2OHR-CH2XOH+-4.醇(1)烯烃水合(2)硼氢化-氧化(3)．醛,酮,羧酸及其酯还原(4)从格利雅试剂(5)卤烃水解89CHCHCH2CH2+CH2CH2COOCH3COOCH3+200oC150oCCH2CH2CH2CH2CHCH简写为高压常用反应：10CCCH3CH3HHH2,Pd/PbO,CaCO3CH3CCCH3CH3CH2CC(CH2)3CH3Na,液NH3,-78℃,97%CH3CH2CHC(CH2)3CH3HCHC2H5CC2H5CCNaC2H5CCNaC3H7IC3H7CCC2H5+NaINaNH2++NH3+11CH3CHCH2+CH3COOHOCH3CHCH2O+CH3COOH过氧乙酸环氧丙烷12CCHRR1R2+KMnO4(浓）RCOOH+OCR1R2KMnO4(酸性）+CHCH2RRCOOH+CO2+H2OKMnO4(浓）+HOOC-CH2CH2-COOH+KMnO4(浓）CH3COOHCH3O13OHH2SO4OHSO3HFeBr3Br2OHSO3HBrOH2OHBr△CH3Br2FeBr3BrCH3KMnO4BrCOOHBrCOOHNO2HNO3H2SO4+定位规则在有机合成上的应用14醛酮甲醛HHCOR1HCOR1R2CO1)RMgX2)H3O+HHCOHR伯醇R1HCOHR仲醇R1R2COHR叔醇R-X+MgR-MgX绝对乙醚15O+RMgX1.Et2O2.H3O+RCH2CH2OH+RMgXCH3COOEtH3COHRR16应用——保护羰基BrCH2CH2CHO+HOCH2CH2OHOBrCH2CH2CHOHCl(g)CH3CH2CCLiOCH2CH2CHOCH3CH2CCH3O+CH2CH2CHOCH3CH2CC保护基17NH2NHAc(AcO)2OAcONaNHAcBrHH2ONH2BrBr2,H2O18CH3ONaOClCO2HCH3CCHCOCH3CH3KOClCH3CCHCO2HCH388%53%19RCONH2NaOH,Br2RNCOH2ORNH220CH3COC2H5O21.EtONa/EtOH2.H3+OCH3CCH2COC2H5OOCO2C2H5CO2C2H5CO2C2H5O1.C2H5ONa2.H3+OPhCOOCH3+CH3CH2COOC2H51)NaOH2)H+PhCCHOCH3COOC2H5C6H5CCH3+C6H5COC2H5OO1.C2H5ONa2.H3+OC6H5CCH2CC6H5OOCH2(CO2Et)2+CH3COCHCH2CH3COCH2CH2CH(CO2Et)2KOHEtOH21•由乙酰乙酸乙酯为原料合成甲基酮的一种重要方法，称为乙酰乙酸乙酯合成法OOEtOCH3CHROOHOCH3CHR1.NaOH,H2O2.H3O+-CO2CH3CCH2RO22•丙二酸酯的烷基化CH2(CO2Et)21.EtONa2.RXRCH(CO2Et)21.OH-2.H3O+,RCH2CO2H1.EtONa2.R'XRR'C(CO2Et)21.OH-2.H3O+,RR'CHCO2H23RCONH2NaOH,Br2RNCOH2ORNH2N2ClNaClOH2NH2NaNO2++2+HCl2+5℃BrNH21.H2SO4,H2O,NaNO22.BrOH66%CH3NH2NaNO2,H2OH2SO4CH3NNHSO4CuBrCH3Br70%CuCNKCNCH3CN67%241．完成下列转化分析：目标分子一方面是一个甲基酮,另一方面又是一个增加两个碳原子的伯醇。CH3COCH2CH2CH2CH2OHCH3COCH2CH2MgX+OCHCCH2CH2Br合成时应保护羰基合成：CHCCH2CH2BrH2OHg2+,H+CH3C=OCH2CH2BrHOCH2CH2OHH+CH3COCH2CH2BrO(1)O(2)H3O+CH3COCH2CH2CH2CH2OH(1)CHCCH2CH2BrCH3COCH2CH2CH2CH2OH25分析：这是增加一个碳原子的反应,且由环状化合物转化成开链化合物。CH3C=O(CH2)4CHOCH3CH3OH=OOH合成：OHK2Cr2O7/H+=O(1)CH3MgBr(2)H3O+CH3OHH+,H2OCH3(1)O3(2)Zn/H2OCH3C=O(CH2)4CHO(2)OHCH3C=O(CH2)4CHO26(3)C2H5OHH2NCH2CH2CH2CH2NH2分析：这是一个增加两个碳原子的反应,目标分子为胺。C2H5OHH2NCH2CH2CH2CH2NH2NCCH2CH2CNBrCH2CH2BrCH2=CH2合成：CH3CH2OHH+CH2=CH2Br2/CCl4BrCH2CH2BrNaCNNCCH2CH2CNH2/NiH2NCH2CH2CH2CH2NH227(2)C=OCH3CH3ONO2CH3分析：C=OCH3CH3ONO2CH3CH3O+COClNO2合成：CH3H2SO4100℃Na2CO3NaOH300℃CH3ONaCH3ICH3CH3O28CH3HNO3H2SO4KMnO4/H+SOCl2COClNO2C=OCH3CH3ONO2COClNO2AlCl3CH3CH3O+29【练习】以指定原料合成(其它试剂任选)：COOHCH3(1)O=C=OOHCH3(2)CH3ClBrBrCH3和30(1)O=(1)CH3MgBr(2)H3O+PBr3吡啶BrCH3Mg/醚(1)CO2(2)H3O+COOHCH3O=(1)CH3MgBr(2)H3O+H+,H2OCH3HBrROORMg/醚(1)CO2(2)H3O+CH3BrCH3COOH31(2)CH3ClBrBrCH3HNO3H2SO4Fe+HClBr2CH3NH2BrBrNaNO2+HCl0~5℃CuClHCl32FFBrBrCH3O和COOH1233HCCHH3CH2CCH2CH3HHOOCH3CH2CH3OH和OOCH3