有机化学第四版课件15章有机含氮化合物.ppt

1、NOO-NOONOO-NO-O或或NO2CH3CH(CH3)2NO2NO2CH3NO2O2N2-硝基-4-异丙基甲苯2,4，6-三硝基甲苯2-硝基萘(TNT)+HNO3H2SO450 C。NO2+H2O重要中间体，常用溶剂，缓和氧化剂CH3CH3H3CCH3CH3H3CNO2HNO3CH3COOHClClNO2ClNO2ClNO2NO2HNO3,H2SO4100-110 C。HNO3,H2SO4130 C。+CH3NO2O2NC(CH3)3OCH3CH3COCH3O2NCH3NO2(CH3)3CCH3NO2O2N(CH3)3CNO2CH3葵子麝香酮麝香二甲苯麝香(1)还原还原硝基化合物被还原的

2、最终产物是胺。还原剂、介质不同时，还原产物不同。NO2NONHOHNH2硝基苯亚硝基苯N-羟基苯胺苯胺HHHHH：LiAlH4,H2/Cu,H2/Pt,Fe+HCl,SnCl2+HCl.NO2NH2H2，Cu300 C，90%o新工艺，清洁工艺苯胺重要的染料、药物中间体NH2NH2Fe+HCl+Fe3O4“铁泥”NO2NH2对硝基苯胺对苯二胺NH2NO2H2/PtNHCOCH3NHCOCH3C2H5OHCH3NO2NO2CH3NH2NH2Fe+HCl,CH3OH,75%CHONO2CHONH2SnCl2,浓HClFe(orSn)+HClNH2NO2Zn+NH4Cl+H2ONHOHN=N+O-A

3、s2O3+NaOHN=NNH-NHZn+NaOHZn+NaOHFe(orSn)+HClNH2N-羟基苯胺氧化偶氮苯偶氮苯氢化偶氮苯苯胺苯胺NO2NO2(NH4)2SNH2NO2or NH4HS (NH4)2S2 Na2S2、Fe+HClNH2NH2OHNO2NO2O2NNa2SC2H5OH,OHNH2NO2O2NOHNO2NO2OHNH2NO2Na2S,NH4Cl8085 C,64%67%oNO295 CNO2NO2发烟H N O3，浓H2SO4。Br2,Fe135-145 CNO2BrNO2。发烟H2SO4110 C。NO2NO2SO3H+PhNH2NO2NO2OCH3NO2NO2NHPh8

4、0%180 CoNO2NO2ClNO2NO2OH(2)H2O,H+o(1)Na2CO3,H2O,100 CAr-ClAr-OH水解 以上的实验表明，若卤素原子的邻、对位有硝基等强吸电子基时，以上的实验表明，若卤素原子的邻、对位有硝基等强吸电子基时，水解反应容易进行。水解反应容易进行。原因：硝基的引入有利于碱或亲核试剂的进攻。原因：硝基的引入有利于碱或亲核试剂的进攻。(见芳卤化合物见芳卤化合物)CHOHCHCH3NHCH3CH3OOCCHCH2OHHN麻黄碱阿托品CH3NH2(CH3CH2)2NH(HOCH2CH2)3NNH2甲胺二乙胺苯胺三乙醇胺CH3-CH-CH2-CH-CH2-CH3CH3

5、NH2CH3-CH-CH2-CH-N-CH2-CH3CH3CH3CH2-CH32-甲基-4-氨 基 己烷2-甲基-4-(二 乙 氨基)戊烷 NCH3HHH3CH3CNCH3键长：键角：键角：键长：CN 0.147nmC-N-C 108。CN 0.147nmNH 0.101nm。C-N-H 112.9H-N-H 105.9。甲胺三甲胺NCH3C2H5HNCH3C2H5HNCH3C2H5HNC6H5C2H5CH3CH2CH=CH2+NC6H5C2H5CH3CH2=CHCH2+RX+NH3RN+H3 X-NH3RNH2+NH4X亲核试剂烷基化剂仍有亲核性RNH2+RXR2N+H2 X-亲核试剂NH3

6、仍有亲核性R2NH+NH4XR3N+RXR4N+X-CH3 OH+H NH2Al2O3CH3NH2+H2O(NH3)2NHCH3OHAl2O3,Al2O3,CH3OH(CH3)3NCH2CNNi+H2苯乙腈苄腈 苯乙胺2-苯乙胺CH2CH2NH2NC(CH2)4CNH2/NiH2NCH2(CH2)4CH2NH2己二腈己二胺制尼龙-6 6 的 原 料LiAlH4H2ONC C H3CH3ON-CH2-CH3CH3N-甲基-N-乙 酰 苯胺N-甲基-N-乙 基 苯胺(91%)C15H31COOHC15H31CNH2OC15H31CNC15H31CH2NH2NH3,-H2O-H2OH2,NiCH3C

7、CH2CH3O+NH3H2,Ni160 C,3.95.9MPaoCH3CHCH2CH3NH2C=OCHNH2+NH3H2/Ni60 C,P。C=O其反应过程可认为如下：+H2NHC=NHCHNH2H2/NiCH3CCH3ONH2NHCH(CH3)2+H2,Ni79%（H ofmann降 解，制少一个碳的伯胺！）R-C-NH2+NaOBr+2NaOHRNH2+Na2CO3+NaBr+H2OO(NaOX)(NaX)NH2NaOH,Br290%C-NH2O(CH3)3CCNH2O(CH3)3CNH2Br2,OH-H2O,64%（G abriel合 成法，制伯胺的特殊方法）（伯胺）+RNH2CCOON

8、HKOH乙醇CCOON-K+RXCCOONR邻苯二甲酰亚胺N烷基邻苯二甲酰亚胺活泼氢COONaCOONaNaOH/H2OCOCOOCNH2COOCN-K+COOPhCH2CH2BrDMFKOHNH3CN(CH2CH2PhCOOCCOOO-O-+PhCH2CH2NH295%NaOH,H2O 此法主要用于制备芳香胺，产物为芳香族伯胺。还原剂：H2Ni(orPt)、Fe(orSn)+HCl、(NH4)2S NO2NH2NO2NH2+3H2Ni常温常压硝基萘萘胺此法不宜制 萘胺因萘硝化得不到 硝基萘Fe+HClor SnCl2+HCl(1)碱性和成盐碱性和成盐(2)烃基化烃基化(3)酰基化酰基化(4)

9、磺酰化磺酰化(5)与亚硝酸的反应与亚硝酸的反应(6)胺的氧化胺的氧化(7)芳环上亲电取代芳环上亲电取代(甲甲)卤化卤化(乙乙)硝化硝化(丙丙)磺化磺化(RNH2)RNH2+H+RN+H3RN+H3+H2O RNH2+OH-RNH2确有碱性R3N碱小稳定性小溶剂化程度小溶剂化程度大稳定性大R2NH碱性大R2N+HHR3N+-HOHHOHHOHHNH2p-共轭多电子N上带正电，苯环带负电氮原子不易给出电子NH2(I)+NH2(II)-+NH2(III)-+NH2(IV)(CH3)2NHCH3NH2(CH3)3NNH3NH(C6H5)3NNH2NH2NO2NH2OCH3SN2RNH2(过量)+RCH

10、2Cl烃基化试剂RNHCH2R伯卤烷，不易消除(过量)CH2ClNHCH2NaHCO3,90 C。+(88%)烃基化试剂NH2N-甲基苯胺N,N-二甲基苯胺对氧化剂较苯胺稳定有机合成原料N(CH3)2+2CH3OHNH2NH2+CH3OHNHCH3H2SO4orAl2O3,PH2SO4orAl2O3,P烃基化试剂OH+烃基化试剂HNZnCl2,260 C。+H2ONH2CH3-C-NHRORNH2+CH3-C-XO(ArNH2)(R)X=-Cl -OC-R -OHO(Ar)(R)(Ar2NH)R2NH+CH3-C-XOCH3-C-NR2O(Ar)R3N+CH3-C-XOxLiAlH4CH3-C

11、H2-NHRLiAlH4CH3-CH2-NR2(n-C4H9)2NH C-N(C4H9-n)2OC6H5COCl在芳胺的氮原子上引入酰基，具有重要的合成意义：在芳胺的氮原子上引入酰基，具有重要的合成意义：保护氨基或降低氨基的致活性。保护氨基或降低氨基的致活性。例如：NH2+(CH3CO)2O(orCH3COOH)NHCOCH3易三元溴代易一元溴代易氧化不易氧化引入永久性酰基。引入永久性酰基。例如：NO2ClNO2HONH2HONHCCH3HOO(1)NaOH,H2O(2)H2O,H+H2,Ni(CH3CO)2O对氨基乙酰苯胺扑热息痛(paracetamol)制备异氰酸酯。制备异氰酸酯。例如：N

12、H2COCl2-HCl-HClNHCOClN=C=O异氰酸苯酯碳酰氯二氯甲酰氯甲酰基COCl2180 C。0-5 C。COCl2CH3NH2NH2CH3N=C=ON=C=OCH3NHCOClNH2 HCl甲苯-2,4-二异氰酸酯(TDI)制备聚氨酯的原料N=C=ONH2NHC-OHONHC-ORONHC-NHROH2ORNH2ROH+CO2N-苯基氨基甲酸酯N,N-二取代脲(4)磺酰化 RNH2R3N(油状液体，可溶于酸)（可溶于NaOH）有酸性R3N(油状液体，可蒸出)H2O/H+NaOHNa+RN-SO2CH3RNHSCH3ORNH2R2NHR3NH3CSO2ClNaOH固体固体R2NSO

13、2CH3OR2NHH2O/H+R2NSO2CH3（不溶于NaOH，可滤出）3 胺。R3N+HNO2x1 胺。RNH2+HNO2N2+R+Cl-NaNO2+H2SO40 C。醇、烯、卤烃等的混合物测定-NH2的含量R2NHR2N-N=O+H2ON-亚硝基胺+中性，黄色液体分离、提纯仲胺2 胺。R2NHR2N-N=O+HClHNO21 胺。NH2+HNO2。0-5 CHClN2 Cl-+N2重氮盐可制备一系列芳香化合物微热2 胺。NHCH3+HNO2CH3N-N=O+H2ON-甲基-N-亚 硝 基苯胺3 胺。+HNO2(CH3)2N(CH3)2NN=O对亚硝基-N,N-二 甲 苯 胺苯环上有强致活

14、基，可发生亚硝化反应CH2N(CH3)2+H2O2CH2N(CH3)2 O-+90%氧化叔胺 具有一个长链烷基的氧化胺是性能优异的表面活性剂。仲胺用H2O2氧化可生成羟胺，但通常产率很低：R2NH +H2O2R2NOH +H2O羟胺久置后，空气中的氧可使苯胺由无色透明久置后，空气中的氧可使苯胺由无色透明黄黄浅棕浅棕红棕。（似苯酚）红棕。（似苯酚）NH2MnO2+H2SO4OONH2NH2ON-Ca(OCl)2（紫色）N(CH3)2 N(CH3)2 O-+H2O2或RCO3H（似苯酚）NH2+3Br2H2OBrBrBrNH2()白（似苯酚，可检验苯胺）NH2NHCOCH3BrNHCOCH3NH2

15、Br(CH3CO)2OBr2H2O/H+NH2COOHNH2COOHBrBrBrBr2,HCl,H2O40-50 C。NH2N+H3HSO4-N+H3HSO4-NO2NO2NH2H2SO4HNO3NaOH硫酸氢盐间位产物NH2NHCOCH3H2O/H+orOH-NHCOCH3NO2NH2NO2NO2NH2(CH3CO)2OHNO3，H2SO4，NHCOCH3SO3HNO2NHCOCH3SO3H混酸H2O，H+NH2NH2 H2SO4H2SO4NH3SO3-+NH2SO3H180 C烘焙。对氨基苯磺酸（内盐，不溶于水）内盐对氨基苯磺酸苯胺硫酸盐 季铵盐是氨彻底烃基化的产物：R3N+RXR4N X

16、-+季铵盐CH2-CH-CH2Cl+(CH3)3NO CH2-CH-CH2N(CH3)3 Cl-+2,3-环氧丙烷三甲基氯化铵O123淀粉O H-O-CH2-CH-CH2N(CH3)3 Cl-+淀粉OH阳离子淀粉，造纸湿强剂(CH3)3N+n-C16H31BrC16H31N(CH3)3 Br-+十六烷基三甲基溴化铵1631，一种阳离子表面活性剂(CH3CH2)4N+Br-(n-C4H9)4N+Cl-四乙基溴化铵四丁基氯化铵相转移催化剂季铵碱：CH3CH2CH2CH2N+(CH3)3 OH-CH3CH2CH=CH2+(CH3)3N+H2O氢氧化三甲基正丁铵CH3CH2CH2N+(CH2CH3)3

17、 OH-CH2=CH2+CH3CH2CH2N(CH2CH3)2+H2O氢氧化三乙基丙基铵二乙基丙基胺不能用NaOH或KOH的水溶液因为季铵碱的碱性与无机碱相当AgOH(湿Ag2O)R4N OH-+AgXR4N X-季铵碱CH3CH2-CH-CH3N(CH3)3OH-+CH3CH2CH=CH2+CH3CH=CHCH3+N(CH3)3+H2O(95%)(5%)NCH3HNCH3H3CCH3+X-NCH3H3CCH3+OH-NCH3H3CCH3NCH3H过量CH3I过量CH3ICH3NCH3H3CCH3CH3+OH-湿Ag2O湿Ag2OCH=CH2+CH2=CH2+NH(CH3)2+H2OCH2CH

18、2-N+-CH2CH3CH3CH3OH-(93%)(0.4%)酸性更强产物更稳定ClCH2CH2Cl+4NH3H2NCH2CH2NH2+2NH4Cl-+110 C。NH2H2NC-NH2H2N-COOBr2,OH-HOOC(CH2)4COOHH4NOOC(CH2)4COONH4H2NOC(CH2)4CONH2-H2O-H2ONH3H2,Ni90 C,2MPa。NC(CH2)4CNH2N(CH2)6NH2(催化加氢)+nHOOC(CH2)4COOHn H2N(CH2)6NH2HN(CH2)6NHOC(CH2)4COn-H2O减压，尼龙-66H2NCH2CH2NH2+4ClCH2COONa+2Na

19、2CO3+4NaCl+2CO2+2H2ONCH2CH2NCH2COONaNaOOCCH2CH2COONaNaOOCCH2乙二胺四乙酸钠(EDTA)H2NCH2CH2NH-H+Al2O3350 C。NHHNCH2CH2NHH2NHOCH2CH2H2CCH2O哌嗪(药物合成原料)15.3.1 重氮盐的制备重氮化反应15.3.2 重氮盐的反应及其在合成中的应用(1)失去氮的反应(a)重氮基被氢原子取代(b)重氮基被羟基取代(c)重氮基被卤素取代(d)重氮基被氰基取代(2)保留氮的反应(a)还原反应(b)偶合反应CH3-N=N-CH3OHN=NN=N偶氮苯偶氮甲烷对羟基偶氮苯4-羟基偶氮苯NN HSO

20、4-+重氮苯硫酸盐N=NNHCH3苯重氮氨基对甲苯CH3-C-N=N-C-CH3CH3CH3CNCNN N Cl-+OHN=NHO偶氮二异丁腈（自由基引发剂）氯化重氮苯重氮苯盐酸盐4,4-二羟基偶氮苯CH2-N N-+N=N-NHN=N-OH重氮甲烷苯重氮氨基苯氢氧化重氮苯（甲基化剂）+2H2O+HNO2+H2SO4NH2过量H2SO40-5 C。N+N HSO4-NaNO2+H2SO4重氮苯硫酸盐NH2+HNO2+HClN+N Cl-过量H C l0-5 C。+2H2ONaNO2+HCl重氮苯盐酸盐O2NN2 HSO4-34 C不分解。通式：N2+Cl-(HSO4-)+ZZ+N2Z-OH,-

21、H,-X,-CN+H3PO2+H2OH+N2 +H3PO3+HClN2+Cl-N2+Cl-+C2H5OHH+N2 +CH3CHO+HCl+OC2H5（少量）或：+CH3OHN2ClOCH3+N2 +HClBrBrBr由HNO2+过量H2SO4混酸0-5 CFe+HClNH2Br2/H2ONH2BrBrBr。BrBrBrH3PO2+H2OBrBrBrN2+HSO4-应用举例：N2+HSO4-+H2OH+OH+N2 +H2SO4OHN=NClBrOH从HNO2+过量H2SO405 C。混酸50 C。NO2Fe+HClNH2BrBrNO2Br2/FeBrN2+HSO4-BrOHH2OI取代N2HSO

22、4+KII+N2 +KHSO4Schiemann反应F取代+N2+BF3FN2Cl+HBF4N2 BF4Cl取代N2ClCl+CuCl+N2 +HClHClSandmeyer反应Br取代Br+N2 +HBr+CuBrN2BrHBrCH3CH3F由CH3CH3NHCOCH3.NO2.CH3NO2.CH3N2 Cl-HBF4CH3FCH3混酸Fe+HCl(CH3CO)2OCH3NO2CH3NO2+CH3NH2CH3NHCOCH3混酸CH3NHCOCH3NO2H2O/H+orOH-CH3NH2NO2HNO2+过量H2SO40-5 C。H3PO2+H2OCH3NO2HNO2+过量H C l0-5 C。

23、Fe+HClCH3NH2CH3NO2N2+HSO4-CH3FCH3N2ClHBF4CH3NH2CH3CN重氮化氰取代N2Cl+CuCN+N2 KCNCNCOOHH2O/H+Gattermann反应NH2H3CCOOHHOOCCH3NH2HNO2+过量H C l0-5 C。KCN+CuCNCH3N2ClCH3CNKMnO4H2O/H+CH3COOHCOOHCOOHCOOHCOOH氧化水解N2Cl+NaHSO3orSnCl2+HClNHNH2 HClNaOHNHNH2 N2ClZn+HCl+NH4ClNH2+HCl+OHHNaOH(pH=8-10)0-5 COHN=NN2Cl。+HCl+OHH3C

24、NaOH(pH=8-10)0-5 CN2Cl。N=NOHCH3N2ClHN(CH3)2+CH3COONa(pH=5-7)0-5 C。-N=N-N(CH3)2p-(N,N-二甲基氨基)偶氮苯（黄色）H+N+H(CH3)2N(CH3)2吸电子基，使不能进行偶联！N2ClH2N+CH3COONa(pH=5-7)0-5 C。-N=N-NH-N=N-NH2H+，重排苯重氮氨基苯对氨基偶氮苯N2Cl+CH3COONa(pH=5-7)0-5 C。-N=N-H+，重排对(N-甲基氨基)偶氮苯H-NCH3CH3-N=N-N-NHCH3在苯环上偶联N2Cl+CH3COONa(pH=5-7)0-5 C。NH2H3C

25、HNH2HH2NCH3COONa(pH=5-7)0-5 C。+N2Cl-N=N-NH2H2NH3CNH2-N=N-致活基致活基OHCH3OHNH2CH3NH2CH3COONa(pH=5-7)0-5 C。+-N=N-NH2NH2N2ClN2ClOH-N=N-OH+NaOH(pH=8-10)0-5 C。OHH2NpH=5-7pH=8-10OHNH2SO3HHO3SpH=5-7pH=8-10H-酸N(CH3)2HNaO3SN2Cl+CH3COONa0-5 C。NaO3SN=NN(CH3)2甲基橙（酸红碱黄，变色范围p H 3.1-4.4）N(CH3)2HNaO3SN2Cl+CH3COONa0-5 C

26、。NaO3SN=NN(CH3)2甲基橙（酸红碱黄，变色范围p H 3.1-4.4）NaO3SN=NNCH3CH3NaO3SN=NNCH3CH3HH+-N=N-C=C-C=C-N-OO等、-N=ONH2、NR2OH、等HO-N=N-O2N对位红（染料）刚果红（染料、指示剂）NH2SO3NaSO3NaNH2-N=N-N=N-OH NH2-N=N-SO3NaNaO3S-N=N-NO2萘酚蓝黑B(染棉毛)N=NN(CH2CH2OCOCH3)2NHCOCH2CH3O2NCl分散红玉ZGFL（染料）CH3CNCH2=CHCNNCCH2CH2CN乙腈丙烯腈1,4-丁二腈CNCH2CNO2NCH3CHCNCH

27、3异丁腈苯甲腈对硝基苯乙腈RX+NaCNRCN+NaX乙醇R-C-NH2OP2O5RC N+H2ONCCH2CH2CH2CNHOOCCH2CH2CH2COOHH2O,HCl,83%85%H2O,NaOH(CH3)2CHCH2CH2CN(CH3)2CHCH2CH2COONaCH2CNCH2CNH2OCH2COOHH2O,H2SO4100 CoH2O，HCl50 Co82%86%78%CH3CH2CN+C6H5MgBrCH3CH2C=NMgBrC6H5CH3CH2C=OC6H5H2O,H+纯醚亚胺盐，不再继续加成!CH3CNCH3C(CH2)4CH3O(1)CH3(CH2)4MgBr,THF(2)

28、H2O,H+44%CNF3CCF3CCH3O(1)CH3MgI,乙醚(2)H2O,H+，79%CNC(CH2)3CH3O(1)CH3(CH2)3Li,乙醚(2)H2O,H+RCNRCH2NH2H2/NiCH3CH2CH2CNCH3CH2CH2CH2NH2(1)LiAlH4(2)H2O,H+NC(CH2)4CN +4H2H2NCH2(CH2)4CH2NH223 MPa,97%Ni,C2H5OH,7090 CoCH2=CH-CH3+NH3+O232磷钼酸铋470 C。CH2=CH-CN+3H2OCH2=CHCN+H2OCH2=CHCNH2O酶(生物催化)20 C，常压，100%oCH2=CHCN+

29、H2OCH2=CHCNH2O铜催化剂80120 Co丙烯酰胺，生产聚丙烯酰胺的单体nCH2=CH-CNCH2-CHCNnBPO均聚聚丙烯腈（人造羊毛）CH2-CH-CH2-CH=CH-CH2CNnnCH2=CH-CN+nCH2=CH-CH=CH2BPO共聚丁腈橡胶O OBPO：PhCCPhOO过氧化苯甲酰，自由基引发剂mCH2=CHCN+nCH2=CHCH=CH2+w C6H5CH=CH2 共聚CH2CHCH2CH=CHCH2CH2CHCNC6H5mnwABS，新型热塑性树脂丙烯腈与含有活泼氢的化合物作用，生成氰乙基衍生物的反应，丙烯腈与含有活泼氢的化合物作用，生成氰乙基衍生物的反应，称为氰乙

30、基化反应。称为氰乙基化反应。腈乙基化反应是亲核加成，是腈乙基化反应是亲核加成，是Michael加成反应的一个特例。例如：加成反应的一个特例。例如：C6H5OH +CH2=CHCNPhOCH2CH2CNOH-CH3COCH2COOC2H5CH3COCHCOOC2H5CH2CH2CN+CH2=CHCNC2H5ONa60%由 ClNHCC2H5OCH3OC NHOHOHONHCCH2CH3ClClO、NHCC2H5OCH3OFe+HCl(CH3CO)2ONH2C2H5OClHNO3H2SO4NO2ClC2H5ONaNO2C2H5OP500，习题15.11。C NHOHOHONH2HOFe+HClCO

31、OHOHClHNO3H2SO4NO2ClNaOHNO2HOClNHCCH2CH3ClClOHNO3H2SO4NO2ClCl2/FeNO2ClClFe+HClNH2ClCl(CH3CH2CO)2O对甲苯胺的NMR例：CCOONHKOH乙醇CCOON-K+BrCH(COOC2H5)2NCH(COOC2H5)2CCOORH2NCH2COOH+NaOC2H5RXNCH(COOC2H5)2CCOONaOH/H2OH+COONaCOONaN-C(COOC2H5)2CCOOH+NaOH/H2OH2NCHCOOHRN-O-O+ClOH-OON+ClOH-OON+ClOH-OON+ClOH最稳定，对真实结构贡献

32、最大氮上正电荷直接分散负电荷-O-NOO-NO+-O-NO+NO-O+ClOHClOHClOHClOH氮上正电荷直接分散负电荷 最稳定，对真实结构贡献最大(CH3)2CHNCH2CH3+OH-CH3CH3CH2=CH2+(CH3)2CHN(CH3)2N(CH3)2CH3OH-CH3CH2CHCH(CH3)2+OH-N(CH3)3CH3CH=CHCH(CH3)2+N(CH3)3 CH3N(CH3)3OH-CH2+N(CH3)3 +H2ON(CH3)2CH2+H2O NH2CH3HOOCNH2Br(CH3CO)2OKMnO4NH2CH3NHCOCH3CH3NHCOCH3HOOCBr2FeNHCOCH3HOOCBrNH2HOOCBrH2OH+orOH-HOOCNHCOCH3HNO3H2SO4HOOCCH3KMnO4HOOCNO2Fe+HClBr2/H2OHOOCBrBrBrNH2HOOCNH2CH3HOOCBrBrBrNH2HOOCNH2CH3COOHNO2NH2