有机化学第十四PPT课件

1、RN=OORN=OO+或RN=OO+RNOO+=实验实验；CH3NO2 N-O键等长，键等长，0.122 nmRN=OOOORN：或RNOO+1212RNOO+第1页/共96页CH3CHCH3NO2O2NNO2CH3NO2第2页/共96页第3页/共96页NO2R CHNHOO第4页/共96页溶于NaOH溶液 or H2/NiR-NO2Fe+HClR-NH2 + H2OR CH N=OOR CH NOO=+R CH N=OO+R CH2N=OO+H+R CH NOOH+=H+NaOHR CH NOO=Na+第5页/共96页CH3(CH2)7CHCH2NO2OHCH3(CH2)7CHOCH3NO2

2、NaOH, EtOHCHCH2NO2OHCHO+ CH3NO2OHCH=CHNO2C6H5COOEt + CH3NO2EtOC6H5COCH2NO2+ EtOH第6页/共96页酸性碱性NH2RNHRNHRNO2RM, HClZn, NaOHM=Fe,Sn,Zn第7页/共96页ArNO22HArNO2HArNHOH2HArNH2ArNArH2NOArNArHNOHArNArN2HArNHArNH- -H2O第8页/共96页+Fe, 55oCBr2BrNO2+Fe, 140oCBr2NO2Br第9页/共96页b b）亲核取代反应ClNO2H+NaHCO3, H2O130 COHNO2ClNO2NO

3、2O2NH+NaHCO3, H2O35 CClNaOHH2O,ClOH高温,高压NaOHH+OHNO2NO2O2N第10页/共96页ClNO2CH3ONaCH3OHClOCH3NO2ClXWNu+NuWX+W:NR3NO2CF3CRCNCOOHO第11页/共96页ClNO2NO2SHNO2NO2OCH3NO2NO2NHCH3NO2NO2NHNH2NO2NO2NaSHNaOCH3NH2CH3NH2NH2ClNO2NO2SHNO2NO2OCH3NO2NO2NHCH3NO2NO2NHNH2NO2NO2NaSHNaOCH3NH2CH3NH2NH2ClNO2NO2SHNO2NO2OCH3NO2NO2NH

4、CH3NO2NO2NHNH2NO2NO2NaSHNaOCH3NH2CH3NH2NH2第12页/共96页iii）硝基对酚、芳酸的酸性影响pKa 9.89 8.28 7.16 4.00 0.38pKa 4.17 3.49 3.40 1.43OHNO2OHNO2NO2OHNO2NO2O2NOHNO2OHCO2HNO2NO2CO2HNO2CO2HCO2HNO2第13页/共96页氨 季铵盐NH3R1NR4R3R2X第14页/共96页C2H5NH2C2H5NC2H5C2H5NMeEtNH2NCH3CH3NH CH3H3C第15页/共96页NH2NH2CH2CH2NH2H2NCH3CHCH2CHCH3CH3

5、NH22 2）结构复杂的胺: : 氨基作取代基CH3NH CH(CH2)3CH3CH3第16页/共96页3 3）季铵化合物CH3CH2 N CH2CH3 Cl+CH2CH3CH2CH3 NH4Cl CH3 N CH3 OH+CH3CH3NH4OH 作为铵的衍生物命名第17页/共96页 物理性质和光谱性质 (1) 物理性质 低分子量胺有氨味，较高级胺有鱼腥味 芳胺有特殊气味，毒性较大。沸点：水溶性：低级胺溶于水，高级胺不溶于水。比同碳的醇低。同碳异构体：伯胺仲胺叔胺第18页/共96页(2) 光谱性质 NH 35003300 cm- -1，伯胺两个峰，仲胺为一个峰。第19页/共96页第20页/共9

6、6页 胺的立体化学 NR3R2R1 NR3R2R1 不能分离，快速翻转第21页/共96页季铵盐，对映体能分离 CH3C2H5CH2CH CH2C6H5N+CH2 CHCH2CH3C2H5C6H5N+苯胺中的NH2，棱锥形结构，但键角偏离109，NH2为114 ，趋向于120的 sp2杂化。NHH114 N 第22页/共96页 化学性质 NNHHNRRRRRHR第23页/共96页(1) 碱性 弱碱性：RNH2+ HClRNH3 Cl+ 碱性比较：脂肪胺 NH3 芳香胺 脂肪胺 RNH2 R3N (） (CH3)2NH2 (CH3)3N芳香胺 ArNH2 Ar2NH Ar3N D-ArNH2 Ar

7、NH2 W-ArNH2第24页/共96页NO2NH2NH2OCH3NH2ClNH2+ CII+ CI 、 Cpkb8.719.3810.5413.02NO2NH2NH2OCH3NH2ClNH2 2. C2H5NH2 NH3 C6H5NH2 C6H5CONH2 溶于水 不溶于水 应用： 分离提纯RNH2NaOHRNH3 Cl+RNH2HCl不溶于水 第25页/共96页(2) 酸性（很弱） CH3NH2+ NaCH3N Na+H+H212R2NHR2N-+ H+pKa=35(H3C)2HCNH(H3C)2HCn-BuLiCHNLiCH+ n-BuHH3CH3CH3CH3C第26页/共96页(3)

8、烷基化反应（SN2）NH3RXRNH2+NH4XR3NRX+NH4XR4N+XRXR2NH2NH4XRX+NH3RXRNH2+NH4XR2NH2NH4XRX+R3NRX+NH4XR4N+XRX第27页/共96页(4) 酰基化反应 RCLORNH2+R2NHR3NRCONHR+HLNo ReactionRCONR2NH2NO2NH2CH3COClHNO3H2SO4NHCOCH3NO2H2O , H+NHCOCH3第28页/共96页磺酰化：Hinsberg反应 用于类胺的分离或鉴别。 RNH2R2NHR3NPhSO2Cl1o 胺2o 胺3o 胺PhSO2NHR不溶PhSO2NR2不溶PhSO2Cl

9、 + R3N不溶NaOHNaOHPhSO2NR Na溶解PhSO2NR2不溶H+R3NH溶解PhSO2NHR不溶H+H+PhSO2NR2不溶第29页/共96页油状物油状物溶于水溶于水RNH2HNO2R2NHHNO2R3NHNO2ROHH2O+N2R2N NOR3NH3NO2第30页/共96页NH2NaNO2, HCl0 5oCXN2OHN2+H2ONHRHNO2NNORNR2HNO2NR2ON第31页/共96页RNH2ORNHOHRNORNO2+R3NH2O2R3NOR3NO第32页/共96页CHCH2R+ (CH3)2NOH150oCRCHCH2-N(CH3)2H OCHNCH3CH3OCH

10、2CH3CHHH CHCH2CH3CHH+CHCHH3CCH2H 规则第33页/共96页顺式共平面)N(CH3)2HDH3CH3COH DH3CH3CC CHN(CH3)2O+CH3HC6H5CH3C CCH3HCH3C6H5(CH3)2N OH+C CHN(CH3)2O+CH3HC6H5CH3+ (CH3)2NOH第34页/共96页HCH2N(CH3)2 HCH2N(CH3)2O+H2O2CH2+ HCH2N(CH3)2O+(CH3)2NOH160HCH2N(CH3)2 HCH2N(CH3)2O+H2O2第35页/共96页4 4）芳香胺易氧化 NH2MnO2H2SO4 , 10OO芳胺的盐对

11、氧化剂不敏感，有时将芳胺变成盐后储存。 NH2H3CNH2HOOC 芳胺：无色芳胺：无色 黄色黄色 红棕色红棕色 褐色 黑色 NH2MnO2H2SO4 , 10OO第36页/共96页NH2+ 3Br2+ 3 HBrH2O NH2BrBrBr(白色)1 1）卤代反应NH2NH2BrNH2NH2BrNH2+ 3Br2+ 3 HBrH2O NH2BrBrBr(白色)第37页/共96页(CH3CO)2ONH2NHCOCH3NHCOCH3BrBr2CH3COOHNH2BrH+ , H2OH2SO4NH2Br2NH2Br HSONH34+ HSOBrNH34HO(CH3CO)2ONH2NHCOCH3NHC

12、OCH3BrBr2CH3COOHNH2BrH+ , H2O(CH3CO)2ONH2NHCOCH3NHCOCH3BrBr2CH3COOHNH2BrH+ , H2O(CH3CO)2ONH2NHCOCH3NHCOCH3BrBr2CH3COOHNH2BrH+ , H2OH2SO4NH2Br2NH2Br HSONH34+ HSOBrNH34HOH2SO4NH2Br2NH2Br HSONH34+ HSOBrNH34HOH2SO4NH2Br2NH2Br HSONH34+ HSOBrNH34HO第38页/共96页H2SO4NH2NHSO3HNH2SO3HH2ONH3 HSO4+180(CH3CO)2ONH2N

13、HCOCH3HNO3CH3CO2HNHCOCH3NO2OH-, H2ONH2O2NH2SO4NH2NHSO3HNH2SO3HH2ONH3 HSO4+180H2SO4NH2NHSO3HNH2SO3HH2ONH3 HSO4+180H2SO4NH2NHSO3HNH2SO3HH2ONH3 HSO4+180NH2O2NNH2?HNO3第39页/共96页R4NXAg2OH2OR4NOH + AgX第40页/共96页NCH2H3CCH3CH3CRCH2CH R +H H2OOHNH3CCH3CH3H+ CH2CHH3CCH CH2N(CH3)3 OH HH CH2CH3CCH CH298%HCH2CHH3C

14、CH CH22%+HNCH2H3CCH3CH3CRCH2CH R +H H2OOHNH3CCH3CH3H+ 第41页/共96页(H3C)3NCCHOH(H3C)3NCCHOH CC OHRCHCHCH2N(CH3)3HH 第42页/共96页 CH2N(CH3)3 OHHH PhCH2CH2NCH2CH3CH3CH3OH +NCH2CH3H3CH3CCHCH2Ph93%CH2CH2+0.4%CH2CH2+99%1%HH第43页/共96页NCH3HNCH3CH3CH3IAg2ONCH3CH3CH3OHNCH2CH3CH3彻底甲基化彻底甲基化Ag2O CH3I2 CH3I R3NCCHHOHCC第4

15、4页/共96页NCH3CH3CH3OHNCH3HNH3CCH3OHNHNCH2CH3CH3Ag2O CH3I 过量C5H11NC7H16IN(A)(B)C7H17NO(C)第45页/共96页RXNH3RNH2+NH4X+Ag2ONCH3CH3CH32 CH3I ?Ag2OCH3I CH2CH NCH3CH3CH3OH H3CPhCO第46页/共96页XNH3NH2NH2NH2XHX慢步骤X消除NH2NH2加成NH2HNH2H+ NH2第47页/共96页第48页/共96页 BrNH2NH3NH2 NH2 NH2+50%50%BrNH2NH3H3COCH3第49页/共96页NH2ClF3CNH2F

16、3CNH2F3CNH2ClHF3CNH2F3CNH2F3CClF3CF3CNH2NH2F3CHabbaNH2第50页/共96页(3) 含氮化合物的还原1）硝基化合物RNO2HRNH2ArNO2HArNH2第51页/共96页RCNH2, Nior LiAlH4RCH2NH2RCRN OHH2, NiRCHRNH2or LiAH4LiAlH4RCONH2RCH2NH2Cl(CH2)4Cl2 NaCNNC(CH2)4CNH2N(CH2)6NH2H2, NiRCRN OHH2, NiRCHRNH2or LiAH4第52页/共96页RCRNHRCHRNH2RCROH2 / NiNH3RCHRNH2RCR

17、OH2, NiNH3RCHRNH2RCHRRCHRNHRCRORCHRNRCRH2 / NiRCRNHRCHRNH2RCROH2 / NiNH3第53页/共96页NOOKNOOROH-, H2ONH2RCOO-COO-CHONH3H2,NiCH2NH2NHOOKOHR X第54页/共96页RCNH2OBr2 / NaOHRNH2+CO2CNH2OH3COBr2/OH-NH2H3CONHOOKOHR-CHCOOEtClOH-H2OR-CHCOOHNH2COO-COO-RCNH2OBr2 / NaOHRNH2+CO2第55页/共96页氨基直接和双键相连的化合物由醛或酮与仲胺缩合得到 CCHO+HR

18、HNR2+CCNR2RH2OCRO+ HNR2HHRCCOHR2NHH2OCCNR2R： HNR2 =NHNHNHO第56页/共96页CCNR2RCCNR2RCCORCCORE+CCNR2REE+CCORE+H2O第57页/共96页 CCNR2RRO1.2.H2O / H+CCORRCCCORORROCORCCR2NRR X1.2. H2O / H+R-C-Cl1.2.H2O / H+O第58页/共96页ONHH+N(1)Br(2) H3O+(1) CH3COCl(2) H3O+OOCH3OOOOCH3ONHH+OCH3O(1)(2) HOAc, H2O第59页/共96页1 1）偶氮化合物 N

19、 Nazobenzene 偶氮某烃，英文名词头azo- RN NR两个氮原子以双键相连， 同时各自与一个烃基相连azomethane N NCH3CH3N NCH3CCCH3CH3CNCH3CN偶氮二异丁腈 第60页/共96页 N N CHCOOC2H5重氮乙酸乙酯 ethyl diazoacetate N NOH氢氧化重氮苯 diazobenzene hydroxide N N Cl+ 氯化重氮苯 diazobenzene chloride 第61页/共96页ArNH2+ 2HCl +NaNO2NaCl2H2O+0 5 ArN2+ Cl在较低温度0 5； 酸性溶液中进行+NNsp杂化N N

20、Cl+ 第62页/共96页 芳香族重氮盐的性质 (1) 取代反应 NGN好的离去基团取代反应叁键的还原弱亲电试剂，偶联反应ArXArHArCNArOHArN2 XArN2 X第63页/共96页重重氮氮盐盐ArN2 X CuCl, HClArCl CuBr, HBrArBrKI ArI ArFH2O / H CuCN,KCNH3PO2HCHO, NaOHArOHArCNArHArHNaBF4ArN2BF4第64页/共96页合成一些用一般方法得不到的芳香族化合物；在芳环上引入羟基、氰基、卤素原子。H3CH3CBrOHH3CBrSO3HH3CBrOH1. NaOH/300oC2. H+H3COHBr

21、2?第65页/共96页H3CBrOHH3CBrN2 SO4HH3CBrNH2H3CBrNO2H3CNO2H3CH3CNO2H3CHNO3H2SO4H3CBrNO2Br2FeFeHBrH3CBrNH2NaNO2H2SO4H3CBrN2 SO4HH3CBrOHH3O+ 第66页/共96页BrBrBrBr2FeBrBr2FeBrBrBrBr+BrBrBrBrBrBrNH2NH2BrBrBrBrBrBrNH2NH2第67页/共96页HNO3H2SO4FeHClNH2Br2（过过量量）H2OBrBrBrNH2NaNO2 / HCl0-5oCBrBrBrN2 ClBrBrBrH3PO2第68页/共96页C

22、H3CH3BrCH3CH3BrCH3BrNH2CH3NHCOCH3CH3NO2CH3BrNHCOCH3CH3BrN2Cl第69页/共96页N2ClNHNH2Na2SO3or SnCl2 , HClArNHNH2N2ClNHNH2Na2SO3or SnCl2 , HClAr N N ClH NaHSO3, Na2SO3, SnCl2/HCl, Sn/HClH =第70页/共96页活化的芳环活化的芳环1）重氮盐与酚、芳香叔胺偶联，生成）重氮盐与酚、芳香叔胺偶联，生成偶氮苯衍生物弱亲电试剂弱亲电试剂偶联到对位，若对位被占则邻位偶联到对位，若对位被占则邻位OHpH = 810ArN2 X+OHNNAr

23、OHRpH = 810OHN N ArRArN2 X+NR2pH =57NR2NNArNR2RpH =57NR2NNArR第71页/共96页NNaO3SpH =57N(CH3)2NX-NHO3SN(CH3)2NNN第72页/共96页NNOHNNOHSO3NaOH NH2NNNNNaO3SSO3NaNO2第73页/共96页 CH2 N NCH2 N N+CH2 N N+CH2 N N+ CH2 N N+ 碳原子既有亲核性又有亲电性CH2 N N+ CH2 N N+ CNNHHCH2 N N+ CH2 N N+ 线型分子1 1）和酸性化合物反应（甲基化试剂）R COOH + CH2N2R COOC

24、H3+ N2sp杂化sp2杂化R COOH + CH2N2R COOCH3+ N2第74页/共96页OH+ CH2N2OCH3CH3CCH2OCOOC2H5 CH2N2CH3CCHOCH3COOC2H5OH+ CH2N2OCH3CH3CCH2OCOOC2H5 CH2N2CH3CCHOCH3COOC2H5CH3COOH+CH2N2CH3COOCH3+N2RCOOHH2CNNRCOOH3C+NNRCOOCH3+ N2第75页/共96页H2OROHCH2COOCH3PhCOOHPhRCClO+H2CNNRCCHONNN2Ag2ORCCHOCCORHRCH2COORRCH2COOH第76页/共96页分

25、解生成碳烯 CH2 （3）与不饱和化合物的反应CH2CCH3COOC2H5COOC2H5CH3+ CH2N2+ N2CH2N2hvorCH2.N2 +CH2CCH3COOC2H5COOC2H5CH3+ CH2N2+ N2第77页/共96页在试剂或热等的作用下，取代基从一个原子上迁移到另一个原子上的反应。 CRCCCRCRXCXRCRCCCR驱动力：形成更稳定的物种第78页/共96页1,2-迁移 XRCXCRX=C, N, O(1) 重排到缺电子的碳原子 CH3CCCH3H3CCH3OH OHH+CH3CCH3CCH3CH3O+H2O结构对称的邻位二醇第79页/共96页CH3CCCH3H3CCH

26、3OH OHH+Pinacol重排重排机理：机理：CH3CCCH3H3CCH3OH OH2CH3CCCH3H3CCH3OHH2O CH3CCCH3H3CCH3OHCH3 H+CH3CCH3CCH3CH3OOMg(Hg)2OHOHH+O第80页/共96页PhCCHPhHOH OHH+结构不对称的邻位二醇CH3CCPhPhCH3OH OHH+哪个羟基优先离去？富电子基团优先迁移：芳基 烷基PhCCHPhHOPhCCCH3PhCH3O能生成更稳定碳正离子的羟基优先离去哪个基团优先迁移？第81页/共96页迁移基团与离去基团处于反式迁移基团与离去基团处于反式CH3OHHOH3CH+快CH3OH2HOH3

27、COH3CH3C- H2O- H+CH3HOHOCH3H+慢CH3H2OHOCH3H3CH3CO- H2O- H+发生迁移的是离去基团反式位置上的基团 ！第82页/共96页类似片呐醇的重排反应CH3CCH2C6H5OH+CH3 C CH2C6H5OH IAgNO3CH3 C CH2C6H5OH+HNO2CH3 C C CH3CH3OHCH3NH2+CH3 C C CH3CH3OHCH3N2CH3 C C CH3CH3CH3OH+第83页/共96页2）Wagner-Meerwein重排 CH3COHCH3CH3CHCH3H+ CHCH2CHClCH3H3CHH3CCCCH3CH3H3C+CH3C

28、CHCH3CH3H2CCH CH2CCH3H3CHHClCH CH2CCH3H3CClHH+i)ii)第84页/共96页ClCHCH2CCH3H3CHH ClCHCH2CCH3H3CHCH CH2CCH3H3CHHClHCH CH2CCH3H3CHHCH CH2CCH3H3CClHHCl HCH3COHCH3CH3CHCH3H+CH3COH2CH3CH3CHCH3- H2OCH3CCH3CH3CHCH3H3CCCCH3CH3H3C+CCH3CCH3CH3HH2CH+CH3CCHCH3CH3H2Ci)第85页/共96页(2) 重排到缺电子的氮原子1）Beckmann重排： ONOHNH2OHHHNOH2SO4NH(CH2)6COnRCRNOHHRCRNHO第86页/共96页H3CC NHOEtt-BuHRCRNOHHRCRNOHHRCRNHORCRNHOCH3CNOHHEtt-BuH第87页/共9