第十一章醛和酮-3

1、CHRCROHCHRCROHBCHRCROCHRCROpKapKaHCH2CH3HCH2CHCH2HCH2HCH2C NHCH2SCH3OO 3550253429HCH2COC2H5OHCH2CCH3OHCH2COHCH2NOO201610.224CHRCROOHCHRCROOCHRCROOBRORHROR ROR B( 位位 H 有有弱酸性弱酸性)CH2NOHBCH2NOCH2NOCH2CHBCH2CNNCH2CNCH2SH3COHBCH2SH3COCH2SH3COOOOOOOpKaH2CCCH3OH2CCOC2H5OC2H5OCCHOCOC2H5OH3CCCHOCOC2H5OH3CCCHO

2、CCH3OHHHHH242012.710.79.0CH2CH3COHBCH2CH3COCH2CH3COCHCH3COHCCH3OBCHCH3COCCH3OCHCH3COCCH3OHCCH3COCCH3ONa NH2Li NCH(CH3)2CH(CH3)2(LDA)SOCH3Na CH2Na HNaOHNaOROCH3B:OCH3OCH3+CH2CH3CORB:CHCH3CORCHCH2COR+CHRCROCHRCROCHRCRO E+CHRCROCHRCROE或或ECHRCROECHRCROECHRCROHB:XXRXCODOD CHRCRODCHRCROXCHRCRORCHRCROCOH E

3、CCOR(H)D2O /DOCCOR(H)HDH2O /HOCCOODDOCCOHCCODD- - HOD+DOOCH3OD / D2O（过过量量）OCH3DDDCCOCCOHCCOXXOHXCCORHRCCORHHCCOHHH CCOHX2 ，OHX = Cl, Br, ICCOXOHCH3COR3 X2CX3CORCHX3CORO+OHCH3CH(R)OCH3CH(R)OHCH2CORHOCX3CORCOROHCX3COROHCOROCHX3+HOCH2CORXXCHCORXCX3HHOHCHCORXCHCORXXXX+CCOHX2 ，X = Cl, Br, ICCOXHCCOCCOHHH

4、- - H+CCOXCCOXHXX烯烯醇醇化化CCOHHH2OX+HXCCORHRCCORHHCCOHHH CCORHRCCORHHCCOHHH CCORCCOHCCORXCCOSi(CH3)3(1) 碱碱(2) ClSi(CH3)3强强碱碱CH3Li低低温温动动力力学学控控制制CCOH+COCCOCOHOHCCOCorH2CCHOH+H3CCHOCH2CHOCHOHH3COHCCOHHCCOHCOHCOHCCOCCH2or2HH- H2OCH3CH2CH2CHO2KOHCH3CH2CH2CHCHCHOHOC2H5C7H15CHO2NaOEtC7H15CHCCHC6H13OCH3CH3OOKO

5、HCH3OCH3OHCH3OCH3- - H2OCH3CCH3O2Ba(OH)2CH3CCH3OHCH2CCH3OI2CH3CH3CCHCCH3O 不能直接脱水不能直接脱水丙丙酮酮Ba(OH)2CCOCCOHHHCCOHCBCOOHBCCOHCHOBCCOC OHCCOCHOCCOHCCOCOHCCOHHOHCOCCOHCOHOHHOHOHHCCOCR2OR1OHR4OR3+R2OR1R3OHR4R4OR3R1OHR2R2OR1R3R4R4OR3R1R2PhC HO+H3CCCH2CH3ONaOHCCCCH2CH3OHPhHPhC HO+H3CCPhONaOHCCCPhOHPhHH2CO3+H3CCHONaOHCCHOHOH2CHOH2CHOH2CNaOHCHOCHOPrPrCHOH2OOCH3OO或CHOPrOHH+ 或 OH- -不能消除不能消除H2OOCH3HOOHH3COOH3CHOCCROHRHHCCROCRRRH2C2OCH3CCH3O2H3CCH3CCHCCH3ODowex-50 树脂H+2AlO(CH3)33OOOHOClHCl（Lewis酸催化）COHCCOHHH+CCOHHH- - H+3OCCOHH烯