大学课程-有机化学反应总结

烷烃CH3CH=CH2CH2BrCH=CH2hor500oC1、烷基的卤代Br21.2.CH3CHCHCCH+H2Pd-CaCO33.CH3CH2CCH2CH3+HOBrPb(OAc)24.+NBS光照CCl45.C(CH3)3KMnO4H+6.CH3CCHCH3(1)O3(2)H2O/Zn7.8.9.10.稀冷KMnO4/OH-11.12.I2/NaOH+CH3H3CCH3CHCH2CH(CH3)2OH浓硫酸(CH3CH2)2CHOCH3+HI(1mol)H3O++CH3CHO稀OH-+OC2H5COC2H5H3CC2H55℃CH2CH3HBr+13.H2O/NaOHCHCH3ClCl14.CH3CH2CCH2CH3(过量)B2H6NaOHH2O2CH3CH2CCH+H2OHgSO4H2SO4CH3CH2CH2ClAlCl3BrNaOH/醇COClNH3NaOHBr215.1.2.3.CH3CH2CCH2CH3Br4.5.C(CH3)3CH3CCH3O7.8.+9.10.11.12.+CH3CH=CHCH(CH3)2+CH3CHO6.CH3CHCH2CHOOH,CH3CH=CHCHOCH3OHOHCH3CH2COOHCHI3(CH3CH2)2CHOHCH3ICH3CH2CCH3OCH2CH3CH3CCH(CH3)2CH3BrCH3CH=CH-CH=CH2BrOHCH(CH3)2C(CH3)3COOHCH3CH3CH2OHCH3CH2CCH3OClCHCH313.OH[CH3CH2CH(CH3)CH2]3B14.CH3CH2CH(CH3)CH2OH,15.CONH2NH2,有苯甲位、烯丙位时，优先反应；没有时，级数高的H反应。烯烃CH3CH3CH3CH3CH3CH3HHHHH2,Pt0.1MPa酯酸86%14%醋酸H2，Pd/C1、顺式加氢3oCBr2/CCl4BrHHBrBrHHBr+73-86%2、反式加溴3、马氏规则：H+主要加到含氢多的碳上。CH3CH2CH=CH2CH3CH2CHCH3CH3CH2CH2CH2HBr醋酸BrBr80%20%+CH3CH=CH2+Br2(H2O)CH3-CH-CH2||HOBr过氧化物或光照CH3CH=CH2+HBrCH3CH2CH2Br4、反马氏加HBr5、间接水合H2OCH3CH=CH2+H2SO4(80%)CH3CH__CH2CH3CH__CH2HO3SOHHHO异丙醇∆6、硼烷——反马氏加水CH3CH2CH2OHCH3CH=CH2B2H6H2O2，HO-H2ORC≡CH1)B2H62)H2O2/OH－RCH2CHOCCl4溶液500~6000ClCH3CHCH2CH2CH=CH2+HClCH3CH=CH2+Cl2室温ClCl7、烯丙位卤代CCl4溶液500~6000ClCH3CHCH2CH2CH=CH2+HClCH3CH=CH2+Cl2室温ClCl7、烯丙位卤代CH3CH3HHCH3CO3HCH3CH3HHCCO8、烯烃环氧化9、烯烃被KMnO4氧化CH3C2H5HCH3HCH3OHHOCH3C2H5冷稀，中性或碱性KMnO4KMnO4CH3CCH2CH3O+CH3COOH10、烯烃臭氧化(CH3)2C=CH2O3H2OZn(CH3)2C=O+CH2O炔烃HCCH+NaHCCNa+H2110°HCCH+NaNaCCNa+H2190°1、炔钠与碳链增长HCCH+NaNH2HCCNa+NH3液氨CH3C≡CNa+C2H5Br→CH3C≡CC2H5+NaBrCCRR'Pd,PtorNiCH2CH2RR'2H2R-CC-R’R'HRHCCLindlar催化剂顺式加成2、催化氢化Lindlar催化剂：Pd-CaCO3/PbAc2、Pd-BaSO4/喹啉R-CC-R’R'HRHCCNa,NH3(l)反式加成3、与卤素加成HCCHCl2Cl2FeCl3FeCl3CHCl2-CHCl2HHCCClClCH2=CH-CH2-CCHCH2BrCHBr-CH2-CCHBr2(1mol)CCHRHXCCH2RXCCH3RXXHX马氏规则4、与HX加成CH3(CH2)5CCH+H2OCH3(CH2)5CCH3O91%Hg2+5、与H2O加成CHCH+HOCH3CH2=CHOCH3KOH加热，加压6、与甲醇加成7．氧化反应R-CC-R'RCOOH+R’COOHKMnO4二烯烃1、加成反应CHCHH2CCH2BrHCHCHH2CCH2HBrCHCHH2CCH2HBr（无过氧化物）+1,2－加成1,4－加成－80oC1,2－加成是主要产物40oC1,4－加成是主要产物（烯的取代基多，稳定）2、狄尔斯-阿尔德反应+脂环烃小环环烷烃(n=3，4)活泼，易开环1、催化加氢时，氢总是从不含取代基的一端加入，如：H2/Ni常压CH2CHCH3CH3CH3CH3+HBrCH3CHCH2CH3Br2、与HX/X2加成时，在含氢最多与含氢最少的位置断键CH3+HBrCH3CHCH2CH3BrBr2CH3CHBrCH2CH2BrH＋总是加在含氢多的碳原子上（马氏规则）3、取代反应Cl2/hvCl4、环烷烃常温下与不与高锰酸钾、臭氧反应。BrBr2CCl4NBSBrBrCH3CH3CH3OHCCH-CH2CH2-C-CH3O(1)O3(2)Zn-H2O5、环烯烃反应（等同于烯烃的反应）苯环1、苯环卤代、硝化Cl+Cl2+HClFeCl325°CSO3H+H2SO4稀H2SO4100-170oC∆2、占位反应+H2SO4(浓)110oCSO3H+H2O3、傅-克烷基化反应CH2CH3+CH3CH2BrAlCl3+HBrC6H6+CH2=CH2AlCl3C6H5CH2CH3C6H6+CH3CH2OHC6H5CH2CH3H2SO4+CH3CH2CH2ClAlCl34、傅-克酰基化反应CH3OCH3COCl+AlCl3+HCl乙酰氯苯乙酮97%CH3CCH3COOO+AlCl3+CH3COOH乙酸酐85%CH3O+CH3CH2CH2ClAlCl3CH(CH3)2CH2CH2CH3+主()次()+CH3CH2COClAlCl3COCH2CH3Zn-HgHClCH2CH2CH35、合成直链烷基苯6、氯甲基化反应CH2ClHCHO，HCl(浓)ZnCl260oC7、侧链烃基的氧化CH3CH3KMnO4H+COOHCOOHCOOHCOOH多环芳烃X2萘的亲电取代反应SO3HSO3H60℃165℃165℃XNO2HNO3,H2SO4X21、取代反应2、取代反应3、氧化1,4-萘醌CH3CH3OOCrO3/CH3COOH室温所以：不能用侧链氧化的方法制萘甲酸卤代烃1、取代RCH2-XNaOHRCH2OHNaX++水R-X+NH3R-NH2+NH4X（过量）RX+NaIRI+NaX丙酮【X＝Cl，Br】CH2－CH＝CHClClNaOH/H2O△CH2－CH＝CHClOH例：CH2ClKCNClCH2CNCl醇解R-X+RONaR-OR+NaX''醚R-X为一级卤代烃（仲、叔卤代烷主要发生消除反应生成烯烃）腈解R-X+NaCN→R-CN醇例1：关于CH3CH2—O—C(CH3)3合成路线的选择CH3CH2Br+NaOC(CH3)3CH3CH2OC(CH3)3CH3CH2ONa+BrC(CH3)3×叔卤代烷主要发生消除ONa+CH3—IO—CH3CH3ONa+Cl(为什麽?)例2：关于苯甲醚合成路线的选择卤苯中C-Cl很稳定CH2－CH＝CHClClNaOH/H2O△CH2－CH＝CHClOH例：CH2ClKCNClCH2CNCl与AgNO3—醇溶液反应R-X+AgNO3R-ONO2+AgX醇硝酸酯2、消去反应CH3CH2-CH-CH3CH3CH=CHCH3+CH3CH2CH=CH281%19%BrKOHC2H5OH一般来说，H从含H少的碳原子上脱去：反式消除优先得共轭烯烃-CH2-CH-CH-CH3CH3Br-CH=CH-CH-CH3CH3-CH2-CH=C-CH3CH3KOHC2H5OH´R-CCHHXKOHC2H5OHHXR-CCHHXHXRCCH邻二、偕二卤代烷得到炔烃-CH2-CH-CH-CH3CH3Br-CH=CH-CH-CH3CH3-CH2-CH=C-CH3CH3KOHC2H5OH´CH3CH－CH＝CH2ClKOH/乙醇△CH2＝CH－CH＝CH23、与金属钠反应RX+2NaRNa+NaXRNa+RXRR+NaX2RX+2NaRR+2NaX对称烷烃，碳原子增加1倍CH3(CH2)3I+LiCH3(CH2)6CH3+LiI2Na2醇、醚、酚1.醇与卤化磷、氯化亚砜反应3ROH+PBr33RBr+H3PO4ROH+PX5RX+HX+POX32CH3OH+2HOSO2OH(硫酸)2CH3OSO2OHCH3OSO2OCH3硫酸二甲酯减压蒸餾-H2SO42、硫酸二甲酯CH3CH2CCCH3OHCH3CH=CCCH346%H2SO487ºCCH2-CH-CH3OHCH=CH-CH3稀H2SO43、消去反应CH3CH2CH2CH2OH360ºC170ºCCH3CH=CHCH3CH3CH2CH=CH2H2SO4Al2O375%H2SO4用氧化铝作脱水时，一般不发生重排。360OC140OC4、PCC氧化CH3CHCHCH2CH2CH2OHPCCCH2Cl2CH3CHCHCH2CH2CHO氯铬酸吡啶5、环氧乙烷环氧乙烷是张力很大的环,因此化学性质较活泼。发生开环反应。H2COCH2H2O/H+ROH/H+HXHCNRMgXHOCH2CH2OHROCH2CH2OHXCH2CH2OHHOCH2CH2CNRCH2CH2OH6.卤代OH+Br2H2OOHBrBrBr(白色)+3HBrOH+Br2CS20℃OHBr+OHBr(67%)(33%)7、酚与酸酐或酰氯反应或者用：CH3COClOH+OH+(CH3)3COHH2SO4C(CH3)3OHCH3=CH2H2SO4OHCH3C(CH3)3(CH3)3C2(CH3)2C酚比芳烃容易进行傅-克反应。且以对位产物为主。8、烷基化和酰基化反应8.酚的氧化反应OHOHOHNa2Cr2O7/H2SO4OO对苯醌醛、酮1.加HCNCH3COH+HCNα-羟基腈CH3COHCNH2、与炔化钠加成OCCH3O1.HC2.H3O+OHCCHCNaCCHH+-H2O+H2O/HgSO43、与氨及其衍生物加成+H—NH—GC=OC——N—GHOH-H2OC=N—G亚胺4醛酮的α-H卤代单卤代Br2H2ORCH2CHOBr2/OH-也可写成：NaOX完全卤代CH3CHOHCCl3+HCOONaCl2/NaOH卤仿反应Br2/NaOHOH3C—C—HOH3C—C—HHOCH2—C—HHOCH2—C—HHOCH2—C—H+OHCH3CHCH2CHO5、羟醛缩合反应CH3CH=CHCHO-H2Oα,β-不饱和醛βαOC—HCH2CHOOHCH-CH2CHOOC—HOC—HOC—HCH2CHOCH2CHOOHCH-CH2CHOOHCH-CH2CHOH2OCH=CH-CHOCinnaldehyde肉桂醛H2OCH=CH-CHOCH=CH-CHOCinnaldehyde肉桂醛C6H5CHO+C6H5CH2CNEtONaEtOH△H2OC6H5CH=CCNC6H56、还原成醇RCHC=O(R')H①NaBH4或LiAlH4②H3O+=CHRCHC(R')H=CHOHH7.还原成亚甲基-CH2-NH2-NH2,NaOH(HOCH2CH2)2O8.歧化反应不含α-H的醛在浓碱下歧化2HCHO浓OHHCOO+CH3OHCOH+HCHOCH2OH+HCOO－浓碱甲醛总是被氧化羧酸及其衍生物+PCl3+H3PO33CH3COOH3CH3COCl+PCl5+POCl3COOHCOCl+HCl1、酰卤的生成NO2COOH+SOCl2NO2COCl+SO