习题15(含氮)(DOC)

习题15.1完成下列转变：(P486)(1)ClOHNO2NO2O2N解：ClOHNO2NO2O2NClNO2NO2O2NH2O/OH-HNO3/H2SO4(2)NH2COCH3解：NH2COCH3CH3COClAlCl3or(CH3CO)2OCOCH3NO2COCH3HNO3/H2SO4SnCl2,浓HCl(3)NO2NO2O2NCH3解：NO2NO2O2NCH3CH3NO2NO2O2NCOOHKMnO4HNO3/H2SO4NO2NO2O2N-CO2(4)CH3OHCH3OCH3NO2C(CH3)3O2N(葵子麝香)解：CH3OHCH3OCH3C(CH3)3CH3OCH3(CH3)2C=CH2H+CH3INaOHCH3OCH3NO2C(CH3)3O2NHNO3/H2SO4习题15.2试将下列下列化合物按酸性大小排列：(1)(A)OH(B)OHNO2(C)OHBr(D)OHCH3(2)(A)COOHCl(B)COOH(C)COOHClCl(D)COOHCLClCl解：(1)酸性：B＞C＞A＞D(2)酸性：D＞C＞A＞B习题15.3分别指出下列化合物是芳胺还是脂肪胺，并用1°、2°、3°表示出其属于伯、仲、叔胺哪一类。(P488)(1)NCH3脂环族叔胺，3°胺(2)CHCH3NH2脂肪族伯胺，1°胺(3)NHCH3脂肪族仲胺，2°胺(4)NH2芳香族伯胺，1°胺习题15.4命名下列化合物：(P489)(1)CH3(CH2)4CH2N(CH3)3I-碘化三甲基己基铵(2)HNNHN,N’-二(β-萘基)对苯二胺(3)NHCH3CH33-甲基-N-甲基苯胺(4)CH3CH2CH2CHN(CH3)2CH32-(二甲基氨基)戊烷，二甲基(1-甲基丁基)胺？(5)H3CNHCH34,4’-二甲基二苯胺(6)CH3CH2CH2CHCH3N(CH3)3OH-氢氧化三甲基(1-甲基丁基)铵习题15.5完成下列转变：(P493)(1)(1)NH3,(2)NaOBrCOOHNH2(2)COCOONH2COOH(1)NH3,(2)NaOBr(3)CH2=CHCH=CH2H2N(CH2)6NH2解：2NaCNCl2(1mol)CH2=CHCH=CH2ClCH2CH=CHCH2ClH2/NiH2N(CH2)6NH2NCCH2CH=CHCH2CN(4)CH2NH2HCH3NaOBrCH2CONH2HCH3(5)(1)Cl2/FeNO2NH2ClClNH(2)H2/NiOH2/Ni(6)CH2ClCH2CH2NH2(1)NaCN(2)H2/Ni习题15.6下列化合物是天然橡胶、乳胶的通用防老化剂。试用对苯二胺与合适的酚合成之。(P493)（1）NHNH解：NH2H2N2HO+orAl2O3,H2SO4,220CoNHNH（2）NHNH解：orAl2O3,H2SO4,220CoNH2H2N+2HONHNH习题15.7下列(I)商品名称为抗老剂3C；(II)是比(I)性能更为优良的橡胶抗老化剂。试由相应的胺和醛(或酮)合成之。(P493)NHNHCH(CH3)2NHNHCHCH2CH(CH3)2CH3(I)(II)解：NHNH2(CH3)2C=OH2,Ni+(I)NHNHCH(CH3)2H2,Ni+NHNH2CH3CCH2CH(CH3)2ONHNHCHCH2CH(CH3)2CH3(II)习题15.8根据化合物C9H13N的红外光谱和核磁共振谱，写出该化合物的构造式。(P497)解：C9H13N的构造式为CH2NHCH2CH3dcab氮原子上的氢为活泼氢，其吸收峰经重水交换实验后消失。习题15.9把下列每组化合物的碱性由大至小排列成序：(P499)(1)(A)NH(B)NH3(C)NH2(D)NH脂肪族仲胺无机氨一个苯环分散孤对电子二个苯环分散孤对电子解：碱性：A＞B＞C＞D(2)(A)NH2OCH3(B)NH2(C)NH2NO2(D)NH2NO2CH3O－有+INO2－有-INO2－有-I、-C解：碱性：A＞B＞C＞D习题15.10一种混合物中有NH2CH3，CCH3NH2O和OHCH3三种物质。请予以分离提纯之。(P499)解：NH2CH3CCH3NH2OOHCH3碱层酸层(1)5%NaOH(2)分液有机层有机层(1)5%HCl(2)分液OH-H+OHCH3NH2CH3习题15.11C2H5ONHCCH3O又称非那西汀(phenacetin)，是解热镇痛药物APC中的一种主要成分；COHOHNHO又称osalmid，是一种利胆药物；NHCCH2CH3ClClO又称敌稗，是一种除草剂。试以氯苯为原料合成上述化合物(其它试剂任选)。(P500)解：①phenacetin的合成：Fe+HClClHNO3H2SO4ClNO2C2H5ONaC2H5ONO2C2H5OH(CH3CO)2OC2H5ONHCCH3OC2H5ONH2②osalmid的合成：Fe+HClClHNO3H2SO4ClNO2H2O/OH-OHNO2OHNH2COHOHNHOOHCOCl③敌稗的合成：ClHNO3H2SO4ClNO2Cl2/FeClNO2ClClNH2ClFe+HClNHCCH2CH3ClClO(CH3CH2CO)2O习题15.12下列异氰酸酯是除TDI外较常用的聚氨酯原料，试由指定原料合成之。(P502)(1)由CH2合成CH2O=C=NN=C=O(MDI)解：CH2HNO3H2SO4H2,NiCH2NO2O2NCOCl2CH2NH2H2NCH2O=C=NN=C=O(2)由合成N=C=ONO=C=(NDI)解：HNO3H2SO4COCl2H2,NiNO2NO2NH2NH2N=C=ONO=C=习题15.123,4-二氯苯基氨基甲酸甲酯又称灭草灵，是高效、低毒、低残留的稻田除草剂之一。试由氯苯合成之。(P502)解：ClClNO2Cl2/FeClNH2ClHNO3H2SO4Fe+HClClNO2ClCOCl2CH3OHClN=C=OClClNHClCOCH3O习题15.14完成下列转变：(P506)(1)NH2CH3HOOCNH2Br解：(CH3CO)2OKMnO4NH2CH3NHCOCH3CH3NHCOCH3HOOCBr2FeNHCOCH3HOOCBrNH2HOOCBrH2OH+orOH-(2)CH3HOOCBrBrBrNH2解：HNO3H2SO4HOOCCH3KMnO4HOOCNO2Fe+HClBr2/H2OHOOCBrBrBrNH2HOOCNH2习题15.15写出下列季铵碱受热分解时，生成的主要烯烃的结构：(P509)(1)[(CH3)2CHNCH2CH3]+OH-CH3CH3CH2=CH2+(CH3)2CHN(CH3)2(2)N(CH3)2CH3OH-+H2ON(CH3)2CH2(3)[CH3CH2CHCH(CH3)2]+OH-N(CH3)3CH3CH=CHCH(CH3)2+N(CH3)3(4)CH3N(CH3)3OH-CH2+N(CH3)3+H2O习题15.16完成下列转变：(P509)(1)NCH3H(1)过量CH3I(2)湿Ag2ONCH3H3CH3COH-NCH3H3CH3C+H2O(1)CH3I(2)湿Ag2OOH-N(CH3)3H3CH2CCH2=CHCH=CHCH3(2)NH2(1)过量CH3I(2)湿Ag2ON(CH3)3OH-+N(CH3)3+H2O习题15.17用三甲胺与合适的原料制备下列化合物：(P510)(1)[(CH3)3NCH2CH2OH]+OH-(胆碱)解：(CH3)3NO+H2O[(CH3)3NCH2CH2OH]OH-(2)[(CH3)3NCH2CH2Cl]+Cl-(矮壮素)解：[(CH3)3NCH2CH2Cl]+Cl-(CH3)3N+ClCH2CH2Cl11mol(3)[(CH3)3NCH2CH2OCCH3]+OH-O(乙酰胆碱)解：(CH3)3NO+H2OOH-[(CH3)3NCH2CH2OH](CH3CO)2OOH-[(CH3)3NCH2CH2OCCH3]O(4)氯化胆碱[(CH3)3NCH2CH2OHCl-]解：(CH3)3N+ClCH2CH2OH[(CH3)3NCH2CH2OH]Cl-或者：[(CH3)3NCH2CH2OH]Cl-[(CH3)3NCH2CH2OH]OH-HCl习题15.18由指定原料合成下列化合物：(P512)(1)由丙烯酸、乙二胺和环氧乙烷合成胍血生NNCCH2CH2BrOH。解：O+H2NCH2CH2NH2NHNHAl2O3-2H2OCH2=CHCOOHBrCH2CH2COOHHBrSOCl2BrCH2CH2COClNNCCH2CH2BrOHBrCH2CH2COClNHNH+-HCl(2)由1,3-丁二烯合成尼龙-66。解：NCCH2CH=CHCH2CN2NaCN(A)CH2=CHCH=CH2Cl2(1mol)ClCH2CH=CHCH2ClH2NCH2CH2CH2CH2CH2CH2NH2HOOCCH2CH2CH2CH2COOHH2NiH2OH+(B)H2NiHOOCCH2CH=CHCH2COOH(C)(A)(B)(C)+C(CH2)4CNH(CH2)6NHOO缩聚(尼龙-66)习题15.19写出下列芳胺重氮化产物的构造式：(P514)(1)4-甲基苯胺NaNO2,HCl0~5Co解：NaNO2,HCl0~5CoH3CNH2H3CNNCl-(2)邻氨基苯乙醚NaNO2,H2SO40~5Co解：NaNO2,H2SO40~5CoOC2H5NH2OC2H5NNHSO4-(3)5-硝基-2-萘胺0CoNaNO2,HCl解：0CoNaNO2,HClNH2NO2N2Cl-NO2(4)2,4-二氯苯胺0CoNaNO2,HCl解：0CoNaNO2,HClNH2ClClN2Cl-ClCl习题15.20由指定原料合成下列化合物(其它试剂任选)：(P515)(1)由甲苯合成3,5-二溴甲苯解：NHO3H2SO4H2,NiCH3CH3BrBrNH2CH3NO2CH3NH2Br2/H2ONaNO2,H2SO40~5CoCH3BrBrN2HSO4-CH3BrBrH3PO2+H2O(2)由苯甲酸合成2,4,6-三溴苯甲酸解：COOHCOOHNH2H2SO4,HNO3COOHNO2Fe+HClorH2/NiBr2/H2OCOOHBrBrBrNH2NaNO2,H2SO40~5CoCOOHBrBrBrCOOHBrBrBrN2HSO4-H3PO2+H2O(3)由甲苯合成间硝基甲苯解：NHO3H2SO4CH3CH3NHCOCH3CH3NO2CH3NH2CH3NHCOCH3NO2NHO3H2SO4Fe+HCl(CH3CO)2OorH2/NiCH3NO2CH3NH2NO2CH3N2HSO4-NO2H2OOH-NaNO2,H2SO40~5CoH3PO2+H2O(4)由苯合成3,5-二溴苯胺解：NO2NHO3H2SO4Fe+HClorH2/NiBr2Fe,NO2BrBrNH2BrBr习题15.21完成下列转变：(P517)(1)NO2NH2NO2OH解：NO2NH2NO2OHH2O/H+NO2N2HSO4-NaNO2,H2SO40~5Co(2)NO2CH3OHCOOH解：KMnO4NO2CH3NO2COOHNH2COOHNaNO2,H2SO40~5CoFe+HClorH2,NiOHCOOHH2O/H+N2HSO4-COOH(3)ClNO2OCH3OH解：ClNO2OCH3NO2OCH3NH2CH3ONaCH3OHFe+HClorH2,NiOCH3OHH2O/H+OCH3N2HSO4-NaNO2,H2SO40~5Co(4)H3COHHOOC解：NHO3H2SO4H3CH3CNO2KMnO4HOOCNO2HOOCNH2HOOCN2HSO4-NaNO2,H2SO40~5CoFe+HClorH2,NiH2O/H+HOOCOH习题15.22完成下列各反应式：(P519)(1)间溴苯胺HNO2,HClH2