第七章醚与环氧化合物课件.ppt

1、OOOH3CH3Csp3杂化sp3杂化轨道上的孤对电子OC2H5C2H5l根据两个烃基是否相同，分为单醚和混醚l按烃基种类，分为脂肪醚和芳香醚l如果氧原子与烃基连成环则为环醚l分子中含有多个氧原子的大环醚，因为结构象皇冠而被称为冠醚。OC2H5CH3O CH3OOOOOOOOOOC2H5C2H5 CH2=CH-O-CH=CH2O（二）乙醚 二乙烯基醚 二苯醚 CH3O C2H5O CH3CH3CH-CHCH3CH3OCH3CH3OCH3C2H5OCH2CH2OH甲乙醚 苯甲醚 l结构复杂的醚2-甲基-3-甲氧基丁烷 对-甲氧基甲苯 2-乙氧基乙醇 OOOOCH3OO环氧乙烷1.4-二氧六环四氢

2、呋喃（二噁烷）氧化乙烯氧化丙烯 其衍生物的系统命名，方法有二：O11233O1122334O122331421,2-环氧丙烷 1,2-环氧丁烷 2，3-环氧丁烷 OOOOOO18-冠-6 钅 羊CH3CH2-O-CH2CH3H+Cl-CH3CH2OCH2CH3+H+-Cl-(浓)该性质可用于醚的纯化，用于和烷烃、卤代烃等的区别。CH3CH2-O-CH2CH3H3O+Cl-H2O+C2H5OC2H5HI+C2H5IC2H5OH+HIH2O+C2H5IC2H5OH+醚与浓强酸（如HX）共热，醚键断裂生成卤代烃和醇如果HX过量，生成的醇可进一步反应生成卤代烃氢卤酸的反应活性:HIHBrHClCH3C

3、H2HI+CH3O？R1OR2HXR1X+R2OH(R2R1)RArHXRX+ArOHOHXR2XR O R.+H XRORH+X-亲核试剂质子化醚+X-R1O R2H1。R1XSN2R2R1+R2OH若 和 都 是 烃基R1R2R1O R2HSN1若 和 是 或 烃基R22。R13。R2+R1OHX-R2XCH3CH2OCH2CH3CH3CH2-O-CH-CH3O-O-HO2课后自学并回答：为什么蒸馏乙醚时要避免蒸干？如何检查并除去醚中的过氧化物？CH2CH2OH2OH+HO-CH2-CH2-OHCH3OHH+HO-CH2-CH2-OCH3NH3HO-CH2-CH2-NH2l 4.环氧化合物

4、的开环反应 4.1 环氧乙烷的开环反应HXHO-CH2-CH2-XRMgBrXMgO-CH2-CH2-RHO-CH2-CH2-RH2O/H+制备比试剂本身多两个碳的伯制备比试剂本身多两个碳的伯醇，是延长碳链的方法之一。醇，是延长碳链的方法之一。CH2CH2O+H+H2OCH2CH2OHOH2+CH2CH2OHOH+H+CH2CH2OH-OH-OCH2CH2OH-OCH2CH2OHCH2CH2O+H-H+弱亲核试剂 质子化环氧乙烷+H-OCH2CH2O-O-OCH2CH2OH强亲核试剂CH2CH2O非质子化环氧乙烷+CCH2O+CH3CH3CH3OHC2H5ONaCCH3CH2OCH3OHCH3

5、CH3OCCHHCH3CH3OCCHHCH3CH3OCH3OCCHHCH3CH3OCH3OCH3OHCCHHCH3CH3OHCH3OCCH2O+CH3CH3CH3OHH+CCH3CH2OHOCH3CH3CCHHCH3CH3OH+CCHHCH3CH4OHHOCH3CH3OHSN2机制CCHHCH3CH3OHCCHHCH3CH4OHCCHCH3CH3OHHOCH3HOCH3H+CCHCH3CH3OHHOOOOO15-冠-5OOOOOOOOOOOOK+K+18-冠-6+KMnO418-冠-6CH2CH2COOHCH2CH2COOH100%钅 羊CH3CH2-O-CH2CH3H+Cl-CH3CH2-O

6、-CH2CH3+H+-Cl-(浓)该性质可用于醚的纯化，用于和烷烃、卤代烃等的区别。R1OR2HXR1X+R2OHRArHXRX+ArOH(R2R1)OHXR2XR O R.+H XRORH+X-R1O R2HSN1若 和 是 或 烃基R22。R13。R2+R1OHX-R2X亲核试剂质子化醚+X-R1O R2H1。R1XSN2R2R1+R2OH若 和 都 是 烃基R1R2CH3CH2OCH2CH3CH3CH2-O-CH-CH3O-O-HO2CH2CH2OH2OH+HO-CH2-CH2-OHCH3OHH+HO-CH2-CH2-OCH3NH3HO-CH2-CH2-NH2HXHO-CH2-CH2-X

7、RMgBrXMgO-CH2-CH2-RHO-CH2-CH2-RH2O/H+l 7.4 环氧化合物的开环反应7.4.1 环氧乙烷的开环反应CH2CH2O+H+H2OCH2CH2OHOH2+CH2CH2OHOH+H+CH2CH2OH-OH-OCH2CH2OH-OCH2CH2OHCH2CH2O+H-H+弱亲核试剂质子化环氧乙烷+H-OCH2CH2O-O-OCH2CH2OH强亲核试剂CH2CH2O非质子化环氧乙烷+C CH2O+CH3CH3CH3OHC2H5ONaCCH3CH2OCH3OHCH3CH3OCCHHCH3CH3OCCHHCH3CH3OCH3OCCHHCH3CH3OCH3OCH3OHCCHHCH3CH3OHCH3OCCH2O+CH3CH3CH3OHH+CCH3CH2OHOCH3CH3CH3OCCHHCH3CH3OCCHHCH3CH3OHCH3OH+CCHHCH3CH3OHSN1机制CCHHCH3CH3OHCCHHCH3CH3OHOCH3CH3OHCCHCH3CH3OHH+CCHHCH3CH4OHSN2机制HOCH3CCHHCH3CH3OHCCHHCH3CH4OHHOCH3H+CCHCH3CH3OHH