搜索
一、烷烃和环烷烃卤代反应：自由基反应（引发、增长、终止）氢原子的活性：叔仲伯(5:4:1)(1600:82:1);卤素活性：Cl2Br2氧化反应（完全氧化、部分氧化）;热裂解反应。氯磺酰化反应：SO2Cl2orSO2+Cl2（RSO2Cl）；硝化反应：HNO3/400oC，气相硝化（RNO2）；烷烃第3章有机化学反应环烷烃加氢加卤素加卤化氢（HBr过氧化物效应）H2Ni,80oCCH3CH2CH3Br225oCBrCH2CH2CH2BrHBrCH3CH2CH2Br加氢卤代Br2hr或高温Br加氢卤代Br2Br300oCH2Ni,300oCCH3CH2CH2CH2CH3H2Ni,200oCCH3CH2CH2CH3Cl2Clhr卤代氧化氧化140~180oC环烷酸钴+OHO90~120oCO2,60%HNO3HOOC(CH2)4COOH注意：加氢活性：小环烷烃与Br2作用，可区别于其它烷烃；小环烷烃不与KMnO4反应，可区别于烯烃。CH2Cl+HCl2.+SOCl2(C6H5COO)2Cl+HCl+SO2+Cl21.+Br23.hr+HBrBr+HBr4.CH3CH2CHCH3Br5.CH3FeBr3hrCH3BrCH2Br;亲电加成氧化反应X2HXH-OH/H2SO41.B2H62.NaOH/H2O2Hg(OAc)2/ROH、H2O、RCOOH等X-OH1.O32.Zn/H2OorR-S-R其他催化氧化（PdCl2-CuCl2、NH3）KMnO4orKCr2O7orOsO4α-H的取代、催化氢化、聚合立体专一性反式加成，溴滃离子马氏规则，反马氏（过氧化物or强吸电子基）顺式加成、区域选择性马氏规则马氏规则卤代醇进一步反应生成环氧乙烷烯烃二、烯烃RCOOOHorH2O2orAg/O2烯烃亲电加成氧化反应α-H的取代（NBS,Cl2/加热）催化氢化聚合反应（铂黑，钯粉，RaneyNi）1.CH3CH=CH2+Cl2H2OCH3CHCH2ClCl2.CF3CH=CHCl+HICF3CH2CHClI3.+Br2H2OH3COHBrH3CBrOH+4.CO3H+Na2CO3H3OOOHOH6.+B2H6CH2CH3H2O2/OHCH3COODH3CH2CBH2HHH3CH2COHHHH3CH2CODHHCH3CH2CHOH+CH3CH2CH2OHCH3OOOH3CC2H5C2H5;5.+O3CH3CH2CCHCH2CH3CH3LiAlH4orH2,Pd/C6.C2H5HCH3H+CHBrCl2(CH3)3COK(CH3)3COHCCl2C2H5HCH3H单线态卡宾于烯烃加成，烯烃为顺式构型时，加成产物也是顺式构型；烯烃为反式构型时，加成产物也是反式构型8.CH2=CHCH2CH2OH+BH3THFH2O2,NaOHH2O,THF(CH2CH2CH2CH2O)3BBH2;HOCH2CH2CH2CH2OH9.(CH3)2C=CHOC2H5+BH3O0oCH2O2,NaOHH2O(CH3)2CCOC2H5BH2;(CH3)2CCH2OC2H5OH7.C6H5CH=CH2+Hg(OAc)2CH3COOH,CH2Cl225oCNaBH4NaOH/H2OC6H5CHCH2HgOOCH2CH3OCOCH3C6H5CHCH3OCOCH3;10.NO+BH3O25oCH2O2,NaOHH2O,C2H5OHNOBH2;NOOH三、炔烃与二烯烃炔烃与烯烃相比：亲电加成反应：炔烯亲核加成反应：炔烯催化氢化反应：炔烯氧化反应：炔烯端炔：活泼氢RCCHRCCR'HCCH聚合反应氧化反应还原反应活泼氢反应与醛酮加成亲核加成过氧化物效应硼氢化反应亲电加成二聚三聚多聚①O3②H2OKMnO4/H+H2/NiNa/NH3(l)H2/Pd-BaSO4Cu2Cl2,NH4Cl反式顺式NaNH2/NH3(l)RCCNa与RX反应增长碳链Ag(NH3)2NO3Cu(NH3)2ClRCCAgRCCCu鉴别分离端炔2X22HX（马氏）H2O/Hg2+,H+（反马氏）（反马氏）HZZRC=CH2(Z=OR,CN,CH3COO)R'CR''ORCCR''OHR'酸CH2=CH-CH=CH2聚合反应双烯合成亲电加成共聚反应EZδδ（1，2-加成）（1，4-加成）CH2=CHCHOOOOCHOOOO催化剂CH2=C-CH=CH2CHCH2C6H5n环烷酸镍三异丁基铝烯丙基碘化镍CCH2CHCH2HnCCH2CHHCH2n1.CH+HBr过氧化物n-C4H9Cn-C4H9C=CH2+n-C4H9BrCCH3BrBrn-C4H9CH=CHBr+n-C4H9CH2CHBr22.CH3CCH+B2H6H2O2,OH-CH3COOHCH3CH=CHBH2,CH3CH=CHOH,CH3CH2CHO,CH3CH=CH25.H3CCCCH3+Na+NH3(l)Br2/H2OCH3HOHCH3BrHCH3BrHCH3OHHH3CHHCH3;,+8.①②O3Zn/H2OOHCOHCCHOCHO;3.HCCH+2HCHOKOHHOCH2CCCH2OH4.RCCH+HO-Br+RCCBr,H2O6.HCCHCH2CH=CH2+Br20oCHCCHCH2CHBrCH2Br+7.COOCH2CH3H3CH2COOCCOOC2H5HHCOOC2H5+9.OO四、芳烃亲电取代(定位规律)芳环氧化反应（O2/V2O5/加热）α-H的卤代单环芳烃卤代（X2/FeX3orI2/HNO3）磺化（可逆）硝化烷基化（RX/AlX3orRCH=CH2/H3PO4orROH/HF）酰基化（RCOCl/AlCl3or(RCO)2O/AlCl3orRCOOH/H2SO4）氯磺化（ClSO3H）氯甲基化（HCHO/ZnCl2/HCl）加成反应（加氢、加氯）侧链氧化有重排现象萘环还原亲电取代萘环氧化X2/Fe/PhH/(X=Cl,Br)XHNO3/H2SO4,30~60oCNO2H2SO4,165oCH2SO4,60oCSO3HSO3H165oCCH3COCl/AlCl3/CS2COCH3COCH3+75%25%COCH390%CH3COCl/AlCl3/C6H5NO2CrO3,CH3COOHV2O5,380oCNa/C2H5OH/NH3(l)H2/Ni,150oCH2/Ni,200oCOOOOO取代萘的亲电取代反应定位规律：（1）原取代基为第一类定位基并在α-位，新取代基主要进入同环α-位，也有进入原取代基邻位的。（2）原取代基为第一类定位基并在β-位，新取代基主要进入同环α-位。（3）原取代基为第一类定位基时，新取代基进入异环的α-位（5-位或8-位）。（4）注意：F-C酰化和磺化反应时有特殊现象，新取代基的导入位置与溶剂、温度有关。1.CH3+H2SO4回流NaOH(s)熔融H3OCl2/FeCH3SO3HCH3ONaCH3OHCH3OHCl;;;2.+CH3CH2COClZn-Hg浓HClBr2,hrAlCl3H2O;;;COCH2CH3CH2CH2CH3CBr2CH2CH3COCH2CH33.+CH3ClCO/HCl/AlCl3AlCl3;CH3CHOCH34.+CH3CONO2OH3ONO25.+CH3CClOAlCl3CS2COCH36.+OOOOOO9.+ClCH2CH=CH2AlCl3CH2CH=CH27.+H2SO4160oCHNO3H2SO4+SO3HSO3HNO2SO3HNO2;,8.HNO3H2SO4KMnO4/OHBr2/Fe;NO2COOHCOOHNO2COOHCOOHNO2Br;11.+CH2=CHCCH2FeCl3NH2ONCH312.NH2+CH3CH=CHCHOAs2O5NH3C13.HNO3H2SO4NO214.FRLi-LiFRLiFLiRLi;;15.FLi(Hg)-LiFBrorBuLiFLi;16.OCH3CH2COCl+CH2=CH2AlCl3H3COO（1）卤代烷；（2）卤代烯烃；（3）卤代芳烃；（4）RMgX的应用。五、卤代烃消除反应亲核取代与活泼金属RX(X=Cl,Br,I)卤代烷还原H2O/OHNaI/CH3COCH3NaHSO3RSO3NaRIROHR'COOR'COORAgNO3/EtOHAgX+RONO2活性NH3R4NXAg2O/H2OR4NOHPPh3R-PPh3XCH(COOEt)2RCH(COOEt)2LiAlH4orH2/PdorHX/ZnRHMg/Et2ORMgXLi/Et2ORLiNaR-RZn/EtOH/邻二卤消除X2，得烯烃；1，3-二卤得环丙烷衍生物。OH/EtOH/消除HX，得烯烃OH/EtOH/HCCl3消除HX，得:CCl2制高级烷烃多2个C多1个CCNRCN卤代烯特性：RCCH2XRHCXCHCH2OH/ROH/NuR'MgXAgNO3/EtOHX2/ROORHXR'2CuLiMg/THFLi/Et2OOH/ROH/的氧化、聚合反应CCHCHCH2HCRR'CH=CH2HCRONO2CH=CH2+AgXHCRNuCH=CH2+RCH=CHCH2NuNu=OH,OR,CN,NHR...X2CRCH=CH2X2CRCH3C=CH2RR'C=CH2RXMgC=CH2RLiRCCH卤代芳烃特性：不反应PhClPhCH2ClNaOH/Cu/NH3/CuO/AgNO3NaNH2/NH3EROHRNH2NH2ClEE=X,NO2R,RCO,SO3HOH/H2OPhCH2ClPhCH2OHPhCHCl2PhCHOPHCCl3PhCOOHRONaPhCH2ORCNPhCH2CNNaHSO3PhCH2SO3HRCOORCOOCH2PhAgNO3/ROHPhCH2ONO2+AgClNH3PhCH2NH2HClNR3PhCH2NR3ClMg/Et2O迅速PhCH2MgClMg/THFLi/Et2ORX/NaCu,220oCPhMgClPhLiPh-RPh-Ph夺取活泼氢多1碳RMgX的应用加成D2OOH2OROMgXROHRDR'CCHR'CCMgXCO2H3OHCHOH3OH3OR'COR''R'COOR''H3OH3OH3OH3OOR'C=NR''R'CNR'COCl/低温OOOH3OR'CH=CHCHXRCOOHRCH2OHRCOHR'R''R2CHOHR'R'CHNHR''RR'CHNHR''RRCR'ORCR'ORCCH2CH2COOHOR'CH=CHCHR多2碳制醇制酮1.RCH2X+LiEt2OCO2H2ORCH2Li;RCH2COOLi;RCH2COOH2.ClCH2CHCl2OHCH2=CCl2H2CCClHClCl3.CH3CH2CHCH3+CH3SO2ClOH/H2OOH(R)OOCH3CH2CHCH3OSO2CH3(R);CH3CH2CHCH3OH(S)Et2O4.CH3Br2/hrMgD2OCH3BrCH3MgBrCH3D;;5.CuXCH2=CHCH2BrCH2=CHCH2BrLiCH2=CHCH2Li;(CH2=CHCH2)2CuLi;CH2=CHCH2CH2CH=CH26.+NaSHH3CSOOOC2H5HCH3C2H5SHH3CH构型翻转7.HOHCH3HCH3BrKOH/C2H5OHHH3COHCH3OHCH3HCH3BrSN29.+H2OCH2BrCH2OH+OH+CH2=CHCH2CH2OHClCH2CH2SH2CH2CClClCH2CH2SH2CCH2OHClCH2CH2SCH2CH2OH芥子气8.ClCH2CH2SCH2CH2ClOH10.BrLiBrH2OCH2=CHCHCH3CH3CH=CHCH2BrCH2=CHCHCH3BrBr11.CH=CHBrCH2Cl+H2OOHCH=CHBrCH2OH12.CH3CH2LiH2OCH3CH2LiHPhCOOLiHHPhCOOHHHPhCH;CH2CH3OLiOLi;HPhCCH2CH3HO13.+B2H6CH3CClO(CH3)3COK3B;CCH3O14