合工大高鸿宾有机化学第四版课件10章醚和环氧.ppt

1、OCHCHOCH3CH3环醚环氧化合物三元的环醚氧原子与二价烃基两端相连CH3OCH3CH3OCH2CH3单(纯)醚混(合)醚R=RR=R单纯醚：O(二)苯 醚CH3CH2OCH2CH3(二)乙 醚混合醚：甲乙醚甲叔丁醚苯甲醚CH3OCH2CH3(CH3)3COCH3OCH3（小的R命在前面）（芳基命在前面）CH3CH2CHCH2CH3OCH3CH3OCH2CH2OCH3CH3OCH=CH CH33-甲氧基戊烷1,2-二甲氧基乙烷(乙二醇二甲醚)对甲氧基丙烯基苯CH2CH2OOOOCH2CHOCH3CH2CHOCH2Cl1,4-二氧六环(或二 恶 烷)1,4-环氧丁烷(或四氢呋喃)口环氧乙烷(

2、或氧化乙烯、氧杂环丙烷)1,2-环氧丙烷3-氯-1,2-环氧丙烷(简称为环氧氯丙烷)：OCH3CH30.142nm112o不等性sp3杂化CH2CH2O61.559.20.147nm0.144nmoo 2CH3CH2OHCH3CH2OCH2CH3浓H2SO4CH2=CH2 +O212Ag300 o C,12MpaCH2CH2OCH3CH2BrCH3CCH3CH3ONa+CH3CH2OCCH3CH3CH3乙基叔丁基醚RONa+RXR-O-R+NaXO NaOCH2CH3+Br CH2CH3CH3-C-BrCH3CH3+CH3CH2ONaCH3C=CH2+CH3CH2OH+NaBrCH3OHCH3

3、CH2OHO-CH3CH2OTsO(1)NaH/CH2Cl2(2)TsCl/CH2Cl2-OTs-90%OCH3+CH3OH +CO2OH CH3OCOCH3O+碳酸二甲酯无毒，可代替有毒的硫酸二甲酯(传统的甲基化试剂)CH3OSOCH3OO可循环使用(CH2)nOHCH2X(CH2)nO-CH2X(CH2)n+1OOH-X-(3)CCBrOHHHCH3H3COH-H2OCCBrHHCH3H3CO-Br-CCOHHCH3H3CCCBrOHCH3HHH3COH-H2OCCBrCH3HHH3CO-Br-CCOCH3HHH3C苏式赤式顺式反式进攻试剂与离去基团反式共平面!CH3CCH2CH3+ROH

4、浓H2SO4ROCCH3CH3CH3RO C CH3CH3CH3HCH3C CH2CH3ROH-H+H+CH3C CH3CH3RO C CH3CH3CH3CH3CCH2CH3BrCH2CH2CH2O CCH3CH3CH3BrCH2CH2CH2OHH2SO4Mg纯醚+DCH2CH2CH2O CCH3CH3CH3DCH2CH2CH2OHH2SO4D2OCH3CCH2CH3+CHCH +CH3OHCH2=CHOCH320%KOH水溶液,PCHCH +C2H5OHCH2=CHOC2H5NaOH160180 oC(3)(CH3)3CCH=CH2(CH3)3CCHCH3OCH3(1)Hg(OAc)2,CH

5、3OH(2)NaBH4,OH-OC(CH3)3OC(CH3)3HgOOCCF3(CF3COO)2Hg(CH3)3COHNaBH4OH-RROH OH ORR10.6 RRORRO+浓H Cl(或浓H2SO4）H+Cl-(HSO4-)碱酸盐羊金RRO+BF3AlCl3MgRXBF3RROAlCl3RRORROMgRX酸lewis碱lewis -OCH3子中（定量进行）CH3OCH2CH3+HICH3I+CH3CH2OHAgNO3AgI根据AgI的重量可推算出原来分 的含量。（Zeisel法）CH3CH2CH2OCH3SN2CH3CH2CH2OCH3HCH3CH2CH2OH +CH3IHIH+I-

6、SN2小小CH3CH2CH2I H+-HOCH3CH3CH3CH3-C+CH3-C-O-CH3CH3CH3+HCH3CH3CH3-C O-CH3Br-CH3CH3CH3-C-Br-H+C=CH2CH3CH3BrCH2CH2CH2OH+CH3-C=CH2CH3BrCH2CH2CH2O-C-CH3CH3CH3D-CH2CH2CH2O-C-CH3CH3CH3H2SO4H2SO4Mg干醚D2O DCH2CH2CH2OH+CH3-C=CH2CH3 HOCH2CH2OHHOCH2CH2OC2H5HOCH2CH2Br乙二醇乙二醇单乙醚溴乙醇2-CH2 CH2OHOH2+-H+-H+CH2 CH2OH2OC2

7、H5OHHBr+H+CH2 CH2OHOC2H5H+CCHOCH3CH3CH3CH3CHCCH3CH3OCH3OHCH3OHH2SO4 CCHOCH3CH3CH3CCHOCH3CH3CH3HCH3CHCCH3CH3OHH2SO4CH3CHCCH3CH3OCH3OHCH3CHCCH3CH3OCH3OH HCH3OH-H+3 o C+CH3CHCCH3CH3OH2 o C+x HOCH2CH2NH2NH3CH2 CH2O+OH-乙醇胺OOH-HOCH2CH2NHCH2CH2OH二乙醇胺OOH-(HOCH2CH2)3N三乙醇胺二乙二醇烷基酚醚聚乙二醇烷基酚醚乳化剂-OP烷基酚OH乙二醇烷基酚醚CH2

8、 CH2OOH-HORRCH2CH2OOOH-RHOCH2CH2OCH2CH2OHO(CH2CH2O)CH2CH2ORnOOH-n-1 (似S 2)NCH CH2OCH3-Nu空间障碍：C1C2Nu更容易从背面进攻C1CH3 CH CH2NuO-，CCHOH3CH3CCH3CHCH3CCH3H3COH OCH3CH3OHCHCH3CCH3H3COOCH3CH3O-CH3ONa，CH3OH O+R-MgXRCH2CH2OMgXRCH2CH2OH干醚H2O/H+多2 个 C 的伯 醇n-C6H13MgBr+OH2OH+纯醚n-C6H13CH2CH2OH+OH2OH+纯醚CH2=CHCH2CH2CH

9、2OHCH2=CHCH2MgBr+OCH3H2OH+纯醚CH2CHCH3OHMgBr OOHO六元环状过渡态OHCH2-CH=CH-R(H)O-CH-CH=CH2R(H)abccba例：bcCH2-CH=CH2R-C-CH-RaOcbaR-C=CH-RO-CH2-CH=CH2O-CH2-CH=14CH2CH3H3COHCH3CH2CH=14CH2H3C经两次六元状过渡态H，易发生自由基氧化CH3CH2OCH2CH3+O2CH3CH2OCHCH3O-OH过氧化乙醚来自空气，受热易爆炸K4Fe(SCN)6K3Fe(SCN)6过氧化物无色血红色KI淀粉过氧化物I2淀粉兰色无色OOOOOOK+OOOO

10、Li+OOOOO OOOOOO18-冠-612-冠-4OOOO15-冠-5CH2-CH2-COOHCH2-CH2-COOH+KMnO418-冠-6苯、水OOOOOO亲水层亲油层OOOOOOHOOOHOClOOClKOH+醚的制法及化学性质小结醚的制法及化学性质小结(环醚)RI +H2O制制法法性性质质2、醚链断裂3、生成过氧化物1、醇分子间脱水2、Williamson合成法3、烷氧汞化-脱汞反应ROH +R I浓H2SO4CHOROOHHO(CH2)nCH2XOH-(CH2)n+1OHI1、生成 盐钅 羊HIO2RORHBF3RORBF32 ROH1o or 2oH2SO4RO-+R X1oROR(or R)RCH=CH2(CH3COO)2HgR OHNaBH4OH-RCHCH3OR环氧化合物的制法及性质小结环氧化合物的制法及性质小结制制法法性性质质2、烯烃环氧化3、卤代醇脱卤化氢 (邻基参与)1、环氧乙烷的工业制法1、酸催化开环 (似SN1)2、碱催化开环 (似SN2)3、与格氏试剂反应 (似SN2)C=CRRCO3HCCRBrO-CCRBrOHOH-ORCH2=CH2O2Ag,ORO-OCRCOR(1)RMgX(2)H2O/H+HOCRCRROCRCOHArOCRCOHXCRCOHROHH+ArOHH+HXH2OH+HOCRCOH