药物合成反应习题及答案Word文档格式.docx

1、CH BuLi等价试剂a合成子：氧化性或亲电性的离子合成子Me2C-OHCH2COCH3CH2-CH-COORMe2C=OBrCH2COCH3CH2=CH-COOR5，协同反应协同反应：在反应过程中，若有两个或两个以上的化学键破裂和形成时，都必须相互协调地在同一步骤中完成。6,非均相催化氢化:催化剂、反应物、试剂和氢供体在两项或多项中反应，催化剂自成一相，称为非均相催化氢化。催化剂自成一相称为非均相催化剂如Pd/C为催化剂，氢气为氢供体，在反应液中还原双键的反应。1）DMAP2）DMF3）DCC4）TBAF1）AromaticElectrophilicSubstitution; 芳香亲电取代2

2、）Phase-transfercatalyst;相转移催化剂3）Carbocations;碳负离子4）trifluoroaceticanhydride.三氟乙酸酐RyojiNoyoriwasawardedtheNobelPrizein2001,Whatdidhediscover?RyojiNoyori日本名古屋大学的野伊良治因在手性催化氢化反应方面做出了突出贡献而被授予2001年Nobel化学奖。例：R（S）-BINAP-Rh+COOR1NHCOR2H2SSharplesswasawardedtheNobelPrizein2001,Whatdidhediscover?Sharpless因在手性

3、催化环氧化反应方面做出了开创性和突出贡献而被授予2001年Nobel化学奖。t-BuOOHOH OHBuO BuOTi（OPr-i）4/（+）DET O二、写出下列反应产物1 ，Cl2/NaOH/H2OOH+HgCl2Cl2，CH2OAcCOHONBS/dioxaneOH2OBrBr2/cat.PCl3C4H9CCHOOH5,C4H9CH2COOHPh3P/Br26,CH3PCl37,NClNMeOOMeBBr3CH3Br8,NH2N2O2NNO2NaNO/HClCuCl/HClNO29,2HBF4/NaNO2N2BF4F10,CuClheatOBnPhCH2Br/K2CO3BnO11,DMF

4、PhCH2Br/NaH12,O AlCl313, +CHO14,+CH3CH2COCH2CH3AlCl315,2H2CCH2NaH16,CHO+（C2H5O）2P-CHCOOEtNaOEtCH2CH2OHE式COOEtNEt217, +COOEt heat18,COOEtheatClCH2COOEt19,O NaOBr20, NH2O OH2O2/C6H5CN21,KHCO3/MeOH22, CH3COOOHO COOEtH3COsO423,PyCHMCPBAOCH324325,O2NCCNO2Rh（Ph3P）3ClH26,PhCCCOOEtPhCCOOEtHHN=CHCH3NHCH2CH3C

5、H3CHO27H2/RaneyNi28 MeONC2930O2N3132LiAlH4COOEt MeO CH2OHFe/NH4ClSnCl2/EtOHCOOEt H2N COOEtZn/HClRaneyNiOSO2CH333COOCH3Pd-C/H2H2N34Pd/CH235三、写出下列反应条件PhCH2Br1,K2CO3/DMFPd/C/H2Me2SO4/K2CO32,acetone3,4,5,OTBSNHBnO OTBSTBSCl OBnHNn-Bu4N+F-NBu-n+n-BuNH2COOHDCC/DMAPICH2COOHTsOH/C6H6refluxCH3OHCOOMeconcentr

6、atedH2SO4COClNHBoc11,PhNHAcAc2O/PyBr2NaOHBr BrHOOC ClOC13,14, CHCOOEtH3C15,CHCOOEtPh3CNa H3CH3C OCHCClH3Ci-Pr2NLiO CH3CCCOOEtCH3H3C O CH3CH C C COOEtH3C CH3OZn/BrCH2COOEtCH2COOEtH+COOEtLiAlH4CH2OH（i-Pr-O）3AlCH3COCH3COOEt LiAlH4 CH2OHOHOHSnCl417,Pb（AcO）4OCH3NaOCH3AcOHCH3O20,JonesOCOOHHCrO4/H2SO4/acet

7、oneO2NCH2OHPDC硝酸铈铵CANH2C（NH4）2Ce（NO3）622,Pb（OAc）4OMEMH3COSeO2H3CO24,OMEMCH3E25,Zn-Hg/HCl26NaBH4CH2Cl28CCHOAl（C2H5O）3CCH2OH29H3CAl（OPr-i）3i-PrOHH3CCH3四、写出系列反应机理或历程1，LiAlH4还原酯机理Ot-BuOCl/CHCl350C+H2CCCCH3O H O H2O+ CH3NH2 + ONCH3 O 颠茄酮H2SO4NaNH2O O O-H2OO OOHNaOH H+NCH3 OheatHC五、用简单化合物为原料（或给出的化合物为原料）合成下列目的物NHCOCH2BrBrCH2COBrZnCl2CCH2ClClCH2COCl（CH2）N43，CH3COClO-HClOAgNO3CBrCH2N2Ag2OCHN2