第十章 醚和環(huán)氧化合物.

1、第十章第十章醚和環(huán)氧化合物醚和環(huán)氧化合物C2H5OC2H5CH3OC2H5CH2CH2OO CH3 單醚單醚 混醚混醚 環(huán)醚環(huán)醚 芳醚芳醚單純醚：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） CH3CH2CH2CHCH2CH3OCH3CH3OCH CHCH2CH3CH3OCH2CH2OCH2CH2OCH3H OCH2CH31-1-甲氧基甲氧基-1-1-丁烯丁烯,- -二甲氧基乙醚二甲氧基乙醚3-3-甲氧基己烷甲氧基己烷（二甘醇二甲醚）（二甘醇二甲醚）乙氧基環(huán)己烷乙氧基環(huán)己

2、烷CH2CH2OOOOCH2CHOCH3CH2CHOCH2Cl1,4-二氧六環(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)P368習題習題10.1 OCH3CH30.142nm112o不等性sp3雜化甲醚甲醚乙醚乙醚CH2CH2O61.559.20.147nm0.144nmoo 2CH3CH2OHCH3CH2OCH2CH3濃H2SO4CH2=CH2 + O212Ag300 o C , 12MpaCH2CH2OCH3CH2BrCH3CCH3CH3ONa+CH3CH2OCCH3CH3CH3乙基叔丁基醚

3、RONa + RXR-O-R + NaXO NaOCH2CH3+ Br CH2CH3CH3-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)使用綠色綠色化學化學(CH2)nOHCH2X(CH2)nO-CH2X(CH2)n+1OOH- X-(3) CCBrOHHHCH3H3CO

4、H - H2OCCBrHHCH3H3CO- 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!CH3CCH2CH3+ ROH濃H2SO4ROCCH3CH3CH3RO C CH3CH3CH3HCH3C CH2CH3ROH-H+H+CH3C CH3CH3RO C CH3CH3CH3CH3CCH2CH3BrCH2CH2CH2O CCH3CH3CH3BrCH2CH2CH2OHH2SO4Mg純醚+DCH2CH2CH2O CCH3CH3CH3DCH2CH2CH2OHH2SO4D2O

5、CH3CCH2CH3+CHCH + CH3OHCH2=CHOCH320% KOH水溶液, PCHCH + C2H5OHCH2=CHOC2H5NaOH160180 oC(3) (CH3)3CCH=CH2(CH3)3CCHCH3OCH3(1) Hg(OAc)2,CH3OH(2) NaBH4,OH -OC(CH3)3OC(CH3)3HgOOCCF3(CF3COO)2Hg(CH3)3COHNaBH4OH -P368習題習題10.2RROH OH ORRP370習題習題10.3 RRORRO+ 濃H Cl (或濃H2SO4）H+Cl-(HSO4-)堿酸鹽羊金RRO+BF3AlCl3MgRXBF3RROA

6、lCl3RRORROMgRX酸lewis堿lewis -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CH3CH2CH2IH+-HOCH3CH3CH3CH3-C+CH3-C-O-CH3CH3CH3+HCH3CH3CH3-C O-CH3Br-CH3CH3CH3-C-Br-H+C=CH2CH3CH3BrCH2CH2CH2OH + CH3-C=CH2CH3BrCH2CH2

7、CH2O-C-CH3CH3CH3D-CH2CH2CH2O-C-CH3CH3CH3H2SO4H2SO4Mg干醚D2O DCH2CH2CH2OH + CH3-C=CH2CH3HOCH2CH2OHHOCH2CH2OC2H5HOCH2CH2Br乙二醇乙二醇單乙醚溴乙醇2-CH2 CH2OHOH2+-H+-H+CH2 CH2OH2OC2H5OHHBr+H+CH2 CH2OHOC2H5H+CCHOCH3CH3CH3CH3CHCCH3CH3OCH3OHCH3OHH2SO4CCHOCH3CH3CH3CCHOCH3CH3CH3HCH3CHCCH3CH3OHH2SO4CH3CHCCH3CH3OCH3OHCH3CH

8、CCH3CH3OCH3OH 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劑-OP烷基酚OH乙二醇烷基酚醚CH2 CH2OOH-HORRCH2CH2OOOH-RHOCH2CH2OCH2CH2OHO(CH2CH2O) CH2CH2ORnOOH-n-1(似S 2)NCH CH2OCH3-Nu空間障礙： C1C2Nu更容易從背面進攻C1CH3 CH CH2NuO-，CCHOH3CH3CCH

9、3CHCH3CCH3H3COH OCH3CH3OHCHCH3CCH3H3COOCH3CH3O-CH3ONa，CH3OHO+ R-MgXRCH2CH2OMgXRCH2CH2OH干醚H2O/H+多2 個 C 的伯 醇+OH2OH+純醚CH2=CHCH2CH2CH2OHCH2=CHCH2MgBr+OCH3H2OH+純醚CH2CHCH3OHMgBr OOHO六元環(huán)狀過渡態(tài)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經(jīng)兩次六元狀過渡態(tài)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P374習題習題10.410.6OOOOOOK+OOOOLi+OOOOO OOOOOO18-冠