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1.以乙酰乙酸乙酯或丙二酸二乙酯为原料的合成CH3CCH2OCH3COCH2COOC2H5C4H9CHC4H9CH3COCOOH3OCH3COCH2COOC2H5C2H5ONaC4H9BrOHCH3COCHCOOC2H5C4H9CHC4H9CH3COCOOHCH2C4H9CH3COCO2+稀CH3CCH2CHCH3OCH3①以乙酸乙酯和3个碳以下的有机物为原料合成例如：CH3CHCH3ClCH2(COOC2H5)2CH2CH2COOHCH(COOC2H5)2CH2ClCH2CH2(COOC2H5)2C2H5ONaH3OOHCHCOOHCOOHCH2CH2CH2COOH+-稀②BrCH2COOC2H5CH(COOC2H5)2CH2COOC2H5CH2(COOC2H5)2C2H5ONaH3OOHCH2COOHHOOCCH2CHCH2COOHCOOHCOOH+-稀CH2(COOC2H5)2CH2COOHHOOCCH2③2NaOC2H5COOC2H5COOC2H5CH2(COOC2H5)2BrCH2CH2CH2CH2BrH3OOHCOOHCOOHCOOH+-稀CH2(COOC2H5)2COOH④2.胺类化合物的合成四、含C-N重键化合物的还原一、硝基化合物还原二、卤代烃或醇的胺解三、醛或酮的氨化还原五、酰胺降级反应六、盖布瑞尔合成法胺的合成方法CH3CH2CH2CH2OHCH3CH2CH2NH2①减少一个碳的胺的合成KMnO4H+CH3CH2CH2COOHNH3CH3CH2CH2CONH2Br/NaOHCH3CH2CH2CH2CH2NH2CH3CH2CH2CH2OHCH3CH2CH2CH2BrNaCNPBr3CH3CH2CH2CH2CNH2/Ni②增加一个碳的胺的合成③相同碳数胺的合成CH3CHCH2CH3CHCH3NH2CH3CHCH21H2OHCH3CHCH3OHCrO3NCH3CCH3O+CH3CHCH3NH2NH3CH3CCH3NHH2/NiCNCH2NH2④:CNCH2NH2CNH2/Ni+3、取代苯的合成BrBrBrCOOHNH2NH2Br21H2ONH2BrBrBrNaNO2/HClN2XBrBrBr+BrBrBrCNCuCN/KCNBrBrBrCOOH1H2O①BrBrBrNH2NH2Br21H2ONH2BrBrBrBrBrBrN2XH3PO2++NaNO2/HXN2XBrBrBr+②BrBrBrNO2Br③OHBr④HNO3H2SO4NO2Br2FeBr3NO2BrFe/HClNH2BrNaNO2/H2SO4N2HSO4Br1H2OOHBr_+OHNO2CH3INO2CH3CH3HNO3H2SO4CH3NO2(NH4)2SNaNO2/HClNO2CH3NO2NH2CH3NO2N2ClKICH3NO2I+⑤CH3CHOBrBr⑥NO2ClFNO2NNClOHN2ClO2N+ClOH重氮组分：偶合组分：4、偶氮化合物的合成重氮组分HNO3H2SO4NO2NO2(NH4)2SNO2NH2NaNO2/HClNO2N2Cl+NO2N2ClOHCl+NO2NNClOHpH=8～10+偶合组分NO2N2ClCuCl/HClNO2ClFe/HClNH2ClNaNO2/HClN2ClClH3OOHCl+++5.喹啉及其衍生物的的合成CH3NHOOCCH3NH2HOOCCH3CH=CHCHOH2SO4,C6H5NO2NHOOCCH3①CH3NNO2HOOCNH2NO2CH3CH2=CHCHOH2SO4,C6H5NO2NNO2CH3②③NH2NCH3NO2CH3COCH2CH2BrCH3COCH2CH2CHCH3OHHOCH2CH2OHH+CH3COCH2CH2BrCH3CCH2CH2BrOO+MgCH3CHOCH3CCH2CH2MgBrOOCH3CCH2CH2CHCH3OOOMgBr醚+BrMg(OH)HOCH2CH2OHH3OCH3COCH2CH2CHCH3OH++6、醛酮与格式试剂亲核加成制备醇①:用C4以下的有机物为原料合成CH3COCH2CH2CH2OHCH3COCH2CH2CCH3OHCH3②：③：CH2CH2CCH2CH2OHH由苯乙烯及其它少于两个碳的有机物合成④：CH2CH2BrMgCH2CHOCH2H++目标产物CHCH2HBrROORMgCH2CH2CH2OHHBrROORMgHCHOH+PCC7.由苯及少于三个碳的有机物合成OOCHOHCHCOOHOHCHCl3KOHH2SO4NaOHSO3HH3O+OHCHO(CH3CO)2OCH3COOKClCH2CH2CH2OHOOHCH3ClMgCH2CH2CH2OC(CH3)3CH3CHOCH3CHCH2CH2CH2OC(CH3)3OHNa2Cr2O7(CH3)2C=CH2H+ClCH2CH2CH2OC(CH3)3MgH+CH3CHCH2CH2CH2OC(CH3)3OH2SO4,H2OCH3CCH2CH2CH2OHOH+8:OHCH2CH2OHCH3CH2O9:OHOHCHC(CH3)3CHCH2CH3OHCH3CCH2CH3H+C(CH3)3OHNaOHC(CH3)3ONaClCH2CHCHC(CH3)3OCH2CHCHCH3CH3OHCHC(CH3)3CHCH2CH310:二、机理题总结1.写出下列反应的机理类型CH3COClCH3CH2OHCH3COOCH2CH3HCl++N2ClClOH+NNOHClpH=8～10+RNH2RNHCOR'(R'CO)2OR'COOH++SO2ClHSOCl2CHCH3C2H5OHCHCH3C2H5Cl+++NC6H5LiNC6H5LiH+NCH3COONO2NNO2+OO1H2OH+HOCH2CH2CH2COOH+2.写出下列反应的机理①(CH3)2CHCHCH3OHHBr？(CH3)2CHCHCH3OH(CH3)2CHCHCH3OH2H++(CH3)2CHCCH3H(CH3)2CCH2CH3++重排CCH3H(CH3)2CH+OH2_(CH3)2CHCHCH3BrBr(CH3)2CBrCH2CH3Br（主产物）②OH1H2OCNHCN++CH3COCH3CNHCNCH3COHCH3CNCN++快CNCH3COCH3CH3COCH3CN+慢CH3COCH3HCNOH+CH3COHCH3CNCH2OHCH2CH2CH2CHOHOOH+③P354CH2OHCH2CH2CH2CHOHHOCH2CH2CH2CH2COHH++HOOHHOOH+_+COCH3OHCOCHCCH3_④:P366COCH3OHCOCH2COCH2COCH3COCH2COCH2COCH31H2OCOCH2COHCH3COCHCCH31H2O___+___CH3COCH2CH2COCH2CH3OH_例如：OCH2CH3⑤酯生成机理—酰氧键断裂机理：1HRCOOHRCOOHH+++45RCOH2OHORCORORHRCOOR'+'H'+++OHRCORHOOR'OHCR++H2O'+1818控制步骤2HOR..'3RCOHOHR'OH+P406CH3CClO+H2O+CH3CClOOHHCH3COHOH+CH3CClOOHHCl_CH3COHOH_+亲核加成再消除—亲核取代CH3CClOCH3COHOHCl+H2O+⑥P411RCOOR'H+RCOOHR'OHRCOONaR'OHNaOH+++H2O⑦酯的水解碱水解机理：RCOOR'OH+RCOOR'OHRCOOHR'O+RCOOR'OH+亲核加成再消除不可逆可逆RCOOR'H+RCOOR'H++RCOOHHR'OH++酸水解机理：RCOOR'OHHH+更缺电RCOOR'OH2H+H2O..RCOOHH+_⑧酯缩合机理C6H5COOC2H5CH3COOC2H5C2H5ONaH++P415COOC2H5COOC2H5C2H5ONaC2H5OHCOOC2H5OC6H5COCH2COOC2H5三、鉴别与分离提纯练习题1.伯、仲、叔醇及邻位二醇的鉴别Lucas试剂：浓盐酸与无水氯化锌的混合物。伯醇叔醇、苄醇、烯丙醇仲醇立即出现混浊数分钟后出现混浊十分缓慢，加热才有混浊邻位二醇白色沉淀HIO4+AgNO32.酚的鉴别溴水，或三氯化铁溶液3.醛、酮的鉴别托伦试剂可氧化脂肪醛和芳香醛。斐林试剂只氧化脂肪醛。2，4-二硝基苯肼是常用的鉴别羰基的试剂4.伯、仲、叔胺的鉴别鉴别、分离伯、仲、叔胺（Hinsberg反应）RNH2R2NHR3NSO2ClCH3+对甲基苯磺酰氯NaOHSO2CH3NRNaSO2CH3NR2ClHRNH2R2NHOHOHClH--（溶）（不溶）过滤过滤不反应，固体SO2NR2CH3R3NSO2NCH3HR①如何分离苯和噻吩？②如何分离邻硝基苯酚和对硝基苯酚？③如何除去甲苯中的少量吡啶用稀盐酸洗涤，吡啶成盐溶于盐酸中，与甲苯分层得以分离分离题如何除去吡啶中少量的六氢吡啶NNHSO2ClCH3加入六氢吡啶生成磺酰胺沉淀，过滤可除去。或利用吡啶与六氢吡啶碱性的差异与酸反应除去。四、推导结构练习题：1.某化合物A,只含有C、H、O三种元素。A用浓硫酸于180℃处理时给出一个烯烃B，B氧化后生成2-甲基丁烷。A在核磁共振谱的高场处显示一个单峰（9H）,在较低场处有一个单峰（2H），在低场处还有一个单峰（1H）。试推导A和B的构造。CCH2OHCH3CH3CH3A:B:CCH3CH3CH3CCH2CH3CH3CH2C2.化合物A（C5H10O）能使高锰酸钾溶液褪色，可同乙酰氯作用生成醋酸酯B（C7H12O2）；B也能使高锰酸钾溶液褪色；进行氧化反应时，A生成酸C,C迅速失去CO2并生成丙酮。试确定A～C的构造。CCH2CH3OHCHCH2CCH2CH3OOCCH3CHCH2CCH2CH3OCOOHA:B:C:3.芳烃A（C8H10），在AlCl3存在下与乙酰氯反应，生成单一产物B（C10H12O），B能与羟胺盐酸盐反应，生成两中异构的肟C和D（C10H13NO）.将C用浓硫酸处理得到酰胺E（C10H13NO）,而D在相同条件下处理则转变为异构的酰胺F。如将F进行碱性水解，可得到2，5-二甲基苯胺。试写出A-F的结构式。ACH3CH3CH3CH3CCH3OBCH3CH3CCH3OHNNOHCH3CH3CCH3CDCH3CH3CONHCH3CH3CH3NHOCH3CEF4.化合物A能发生碘仿反应，用乙酸处理可得到乙酸酯，将A的脱水产物催化加氢，生成2，2-二甲基丁烷，试写出A的结构。CH3CH2CCH3CH3CH3CH3CHCCH3CH3CH3OH5.化合物A（C8H17N）的核磁共振谱图上无双重峰，它与2mol碘甲烷反应，再与湿的氧化银反应，热解产生中间体B（C10H21N）,B进一步甲基化转变成氢氧化物，再热解生成三甲胺、1，5-辛二烯和1，4-辛二烯的混合物。试推断A和B的结构。CH2CHCH2CH2CHCH2CH2CH3NCH3CH3NCH2CH2CH3CH2CHCH2CH2CHCHCH2CH2CH2CHCH2CH2CHCHCH2CH26.化合物E,分子式为C8H17N，E与过量碘甲烷作用得到F（C9H20IN）。F用氧化银-水处理并加热生成G（C9H19N），G再与过量碘甲烷作用，并经氧化银-水处理及加热得到H及三甲胺。H的分子式为C7H12，它经高锰酸钾氧化得到2，4-戊二酮，写出E、F、G、H的构造式。CCCCCCCH:CCCCCCCNCH3CH3G:CCCCCCCNCH3E：F：CCCCCCCNCH3CH3I_+7.化合物A（C5H9OCl）具有旋光性，A能与苯肼反应生成苯腙，能起碘仿反应。A经水解生成B（C5H10O2）,B经氧化生成C（C5H8O2）,C不能起银镜反应，但能使溴水褪色并与FeCl3溶液作用显紫色。写出A、B、C构造式。CH3COCH2CHCH3ClCH3COCH2CHCH3OHCH3COCH2COCH3ABC8.化合物A的分子式为C5H6O3，A和乙醇作用得到两个互为异构体的