醚和環(huán)氧課件

1、醚和環(huán)氧課件醚和環(huán)氧課件OCHCHOCH3CH3環(huán)醚環(huán)氧化合物三元的環(huán)醚氧原子與二價烴基兩端相連CH3OCH3CH3OCH2CH3單(純)醚混(合)醚R=RR=R醚和環(huán)氧課件單純醚：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）醚和環(huán)氧課件 CH3CH2CHCH2CH3OCH3CH3OCH2CH2OCH3CH3OCH=CH CH33-甲氧基戊烷1,2-二甲氧基乙烷(乙二醇二甲醚)對甲氧基丙烯基苯醚和環(huán)氧課件CH2CH2OOOOCH2CHOCH3CH2CHOCH2Cl1,4-

2、二氧六環(huán)(或二 惡 烷)1,4-環(huán)氧丁烷(或四氫呋喃)口環(huán)氧乙烷(或氧化乙烯、氧雜環(huán)丙烷)1,2-環(huán)氧丙烷3-氯-1,2-環(huán)氧丙烷(簡稱為環(huán)氧氯丙烷)醚和環(huán)氧課件： OCH3CH30.142nm112o不等性sp3雜化CH2CH2O61.559.20.147nm0.144nmoo醚和環(huán)氧課件醚和環(huán)氧課件 2CH3CH2OHCH3CH2OCH2CH3濃H2SO4CH2=CH2 + O212Ag300 o C , 12MpaCH2CH2O醚和環(huán)氧課件CH3CH2BrCH3CCH3CH3ONa+CH3CH2OCCH3CH3CH3乙基叔丁基醚RONa + RXR-O-R + NaXO NaOCH2CH

3、3+ Br CH2CH3醚和環(huán)氧課件CH3-C-BrCH3CH3+ CH3CH2ONaCH3C=CH2 + CH3CH2OH + NaBrCH3OHCH3CH2OHO-CH3CH2OTsO(1) NaH/CH2Cl2(2) TsCl/CH2Cl2- OTs-90% OCH3+ CH3OH + CO2OH CH3OCOCH3O+碳酸二甲酯無毒，可代替有毒的硫酸二甲酯( 傳統(tǒng)的甲基化試劑)CH3OSOCH3OO可循環(huán)使用醚和環(huán)氧課件(CH2)nOHCH2X(CH2)nO-CH2X(CH2)n+1OOH- X-醚和環(huán)氧課件(3) CCBrOHHHCH3H3COH - H2OCCBrHHCH3H3CO

4、- Br-CCOHHCH3H3CCCBrOHCH3HHH3COH - H2OCCBrCH3HHH3CO- Br-CCOCH3HHH3C蘇式赤式順式反式進攻試劑與離去基團反式共平面!醚和環(huán)氧課件CH3CCH2CH3+ ROH濃H2SO4ROCCH3CH3CH3RO CCH3CH3CH3HCH3C CH2CH3ROH-H+H+CH3C CH3CH3RO CCH3CH3CH3醚和環(huán)氧課件CH3CCH2CH3BrCH2CH2CH2O CCH3CH3CH3BrCH2CH2CH2OHH2SO4Mg純醚+DCH2CH2CH2O CCH3CH3CH3DCH2CH2CH2OHH2SO4D2OCH3CCH2CH3

5、+醚和環(huán)氧課件CHCH + CH3OHCH2=CHOCH320% KOH水溶液, PCHCH + C2H5OHCH2=CHOC2H5NaOH160180 oC醚和環(huán)氧課件(3) (CH3)3CCH=CH2(CH3)3CCHCH3OCH3(1) Hg(OAc)2,CH3OH(2) NaBH4,OH -OC(CH3)3OC(CH3)3HgOOCCF3(CF3COO)2Hg(CH3)3COHNaBH4OH -醚和環(huán)氧課件RROH OH ORR醚和環(huán)氧課件醚和環(huán)氧課件10.6 醚和環(huán)氧課件醚和環(huán)氧課件 RRORRO+ 濃H Cl (或濃H2SO4）H+Cl-(HSO4-)堿酸鹽羊金醚和環(huán)氧課件RRO+

6、BF3AlCl3MgRXBF3RROAlCl3RRORROMgRX酸lewis堿lewis醚和環(huán)氧課件 -OCH3子中（定量進行）CH3OCH2CH3 + HICH3I + CH3CH2OHAgNO3AgI根據(jù)AgI的重量可推算出原來分 的含量。（Zeisel法）CH3CH2CH2OCH3SN2CH3CH2CH2OCH3HCH3CH2CH2OH + CH3IHIH+I -SN2小小CH3CH2CH2I 醚和環(huán)氧課件H+-HOCH3CH3CH3CH3-C+CH3-C-O-CH3CH3CH3+HCH3CH3CH3-C O-CH3Br-CH3CH3CH3-C-Br-H+C=CH2CH3CH3BrCH

7、2CH2CH2OH + CH3-C=CH2CH3BrCH2CH2CH2O-C-CH3CH3CH3D-CH2CH2CH2O-C-CH3CH3CH3H2SO4H2SO4Mg干醚D2O DCH2CH2CH2OH + CH3-C=CH2CH3 醚和環(huán)氧課件HOCH2CH2OHHOCH2CH2OC2H5HOCH2CH2Br乙二醇乙二醇單乙醚溴乙醇2-CH2 CH2OHOH2+-H+-H+CH2 CH2OH2OC2H5OHHBr+H+CH2 CH2OHOC2H5H+CCHOCH3CH3CH3CH3CHCCH3CH3OCH3OHCH3OHH2SO4 醚和環(huán)氧課件CCHOCH3CH3CH3CCHOCH3CH3

8、CH3HCH3CHCCH3CH3OHH2SO4CH3CHCCH3CH3OCH3OHCH3CHCCH3CH3OCH3OH HCH3OH-H+3 o C+CH3CHCCH3CH3OH2 o C+x 醚和環(huán)氧課件 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劑-OP烷基酚OH乙二醇烷基酚醚CH2 CH2OOH-HORRCH2CH2OOOH-RHOCH2CH2OCH2CH2OHO(CH2CH2O) CH2CH2ORnOOH-n-1 醚和環(huán)氧課件(似S 2)NCH

9、 CH2OCH3-Nu空間障礙： C1C2Nu更容易從背面進攻C1CH3 CH CH2NuO-，CCHOH3CH3CCH3CHCH3CCH3H3COH OCH3CH3OHCHCH3CCH3H3COOCH3CH3O-CH3ONa，CH3OH 醚和環(huán)氧課件O+ R-MgXRCH2CH2OMgXRCH2CH2OH干醚H2O/H+多2 個 C 的伯 醇n- C6H13MgBr +OH2OH+純醚n- C6H13CH2CH2OH+OH2OH+純醚CH2=CHCH2CH2CH2OHCH2=CHCH2MgBr+OCH3H2OH+純醚CH2CHCH3OHMgBr醚和環(huán)氧課件 OOHO六元環(huán)狀過渡態(tài)OHCH2-

10、CH=CH-R(H)O-CH-CH=CH2R(H)abccba例：bcCH2-CH=CH2R-C-CH-RaOcbaR-C=CH-RO-CH2-CH=CH2醚和環(huán)氧課件O-CH2-CH=14CH2CH3H3COHCH3CH2CH=14CH2H3C經(jīng)兩次六元狀過渡態(tài)醚和環(huán)氧課件H，易發(fā)生自由基氧化CH3CH2OCH2CH3 + O2CH3CH2OCHCH3O-OH過氧化乙醚來自空氣，受熱易爆炸K4Fe(SCN)6K3Fe(SCN)6過氧化物無色血紅色KI淀粉過氧化物I2淀粉蘭色無色醚和環(huán)氧課件醚和環(huán)氧課件OOOOOOK+OOOOLi+OOOOO OOOOOO18-冠-612-冠-4OOOO15-

11、冠-5醚和環(huán)氧課件CH2-CH2-COOHCH2-CH2-COOH+ KMnO418-冠-6苯、水OOOOOO親水層親油層OOOOOOHOOOHOClOOClKOH+醚和環(huán)氧課件醚和環(huán)氧課件醚的制法及化學(xué)性質(zhì)小結(jié)醚的制法及化學(xué)性質(zhì)小結(jié)(環(huán)醚)RI + H2O制制法法性性質(zhì)質(zhì)2、醚鏈斷裂3、生成過氧化物1、醇分子間脫水2、Williamson合成法3、烷氧汞化-脫汞反應(yīng)ROH + R I濃H2SO4CHOROOHHO(CH2)nCH2XOH -(CH2)n+1OHI1、生成 鹽钅 羊HIO2RORHBF3RORBF32 ROH1o or 2oH2SO4RO - + R X1oROR( or R)RCH=CH2(CH3COO)2HgR OHNaBH4OH -RCHCH3OR醚和環(huán)氧課件環(huán)氧化合物的制法及性質(zhì)小結(jié)環(huán)氧化合物的制法及性質(zhì)小結(jié)制制法法性性質(zhì)質(zhì)2、烯烴環(huán)氧化3、鹵代醇脫鹵化氫 (鄰基參與)1、環(huán)氧乙烷的工業(yè)制法1