1、會(huì)計(jì)學(xué)1醛酮的親核加成醛酮的親核加成OC HROCROC醛酮的官能團(tuán)ROCROCROCROCROCORCHCH(R)H羰基親核加成反應(yīng)-H的反應(yīng)氧化(以醛為主)與還原反應(yīng)飽和醛酮不飽和醛酮脂肪族醛酮脂環(huán)族醛酮芳香族醛酮根據(jù)烴基分類CH3CH=CH-CHOCCH3OCHOO根據(jù)官能團(tuán)分類OCH3CCH2CCH3OCH3CCH3OCH3CHOCH2CCH3O加成試劑：HCN；NaHSO3；ROH；NH2Y；RMgX； Ph3P=CRR（一）羰基的親核加成反應(yīng)COCOCO影響因素電子效應(yīng)供電基團(tuán)，不利于反應(yīng)?？臻g效應(yīng)基團(tuán)越大，越不利于反應(yīng)。試劑親核能力不同試劑反應(yīng)范圍不同。反應(yīng)活性：醛酮；甲基酮非甲

2、基酮；脂肪族芳香族C=OCH3CH3C=ORCH3C=OHHC=ORHC=OArHC=OArCH3C=ORRC=OArAr重點(diǎn)一：反應(yīng)形式和產(chǎn)物結(jié)構(gòu)重點(diǎn)二：在合成上的應(yīng)用1、加H-CNC=O + HCN反應(yīng)范圍：醛、脂肪族甲基酮、8個(gè)C以下脂環(huán)酮反應(yīng)條件：堿性，pH8.0，有利于CN-離解。應(yīng)用：OHCH3CH3CCOOHCH3CH2=CCOOHCH3CH2=CCOOCH3CH3CCH3O+ HCNCH3CCNOHCH3COHCN2、加亞硫酸氫鈉(NaHSO3)C=O + NaSO3H反應(yīng)范圍：醛、脂肪族甲基酮、8個(gè)C以下脂環(huán)酮應(yīng)用：鑒別；分離SO3HCONaSO3NaCOH練習(xí)1：鑒別(分離

3、)環(huán)己酮和3-己酮OCH3CH2CCH2CH2CH3ONaHSO3(飽和)HOSO3NaNaCl + SO2 + H2ONa2SO3 + CO2 + H2OO3、加醇ROHC=O + HORORCOR + H2OOHCORC=OC=OH+OHCOROHCORH+很活潑，不穩(wěn)定反應(yīng)條件：條件催化C=O +CH3HHOC2H5HOC2H5結(jié)構(gòu)似醚，穩(wěn)定CCH3HOC2H5OC2H5HOCH2HOCH2CCH3HOCH2OCH2C=O +CH3H反應(yīng)范圍：醛。酮較難、-羥基醛發(fā)生分子內(nèi)縮醛化反應(yīng)，可得到5、6圓環(huán)狀穩(wěn)定的半縮醛。CH2CH2CH2CHOOHCH2CH2OCH2CHOHCH2CH2O-

4、HCH2CHOOOO+ HOCH2CH2OH+ H2OCH2=CHCHOC2H5OC2H5CH2=CHCHOCH2CHCHOOHOHCH2CHCHOC2H5OC2H5OHOH應(yīng)用：保護(hù)醛基練習(xí)2：CH3CH2CHOC2H5OC2H5CH3CH2CHO4、與氨的衍生物加成縮合C=O + HNH-YOHCNYHCNYC=O + H2NYCNYH2NOHH2NNH2H2NNHPhH2NNHNO2NO2H2NNHCNH2OCNNHCNH2OCNNHNO2NO2CNNHPhCNNH2CNOH練習(xí)3：分析下列物質(zhì)，是由哪些醛酮轉(zhuǎn)變得到的CH3CH2CSO3NaOHCH3CHNOHNNHCONH2OOHHC

5、H2CH2CH2CH2CHOOHCH3CH2CCH3 + NaHSO3OCHOH2NNOHOH2NNHCNH2O5、與RMgX加成C=O + RMgXOMgXCROHCROHCRHHHOHCRROHCRRRC=OHHC=ORHC=ORRMgCl+C=OHHCH2OHMgCl+C=OCH3CH3COHCH3CH3練習(xí)4：P38214(3)用不多于四個(gè)C的醇和鹵代烴合成CH3CHCH2CCH2CH3CH3OHCH3RCH2CH2OHR2CHOHR1R2COHR3R1原料分析：RMgX +CCORCH2MgX + HCHOR2CHOR1MgX + R2MgX + R1CHOOR2CR3R1MgX +

6、 CH3CHCH2MgXCH3OCH3CCH2CH3OR1CR3R2MgX + OR1CR2R3MgX + ？練習(xí)5：分析下列各醇用什么原料合成CH3CH2CH2CH2OHOHCCH3CH3CHCH2CH3OHCH3CCH3O+MgXCCH3O+CH3MgXCHO+ CH3CH2MgXMgXCH3CH2CHO +HCHO + CH3CH2CH2MgX+ CH3CH2MgXCH2CH2OCCCCCCCOHCC=CCCCC練習(xí)6： 2-甲基-1-丙醇、異丙醇2,4-二甲基-2-戊烯HOCCCCOHCCCCCCMgXCOCCC練習(xí)7：苯、乙烯、丙烯3-甲基-1-苯基-2-丁烯CC=CCCCCMgXO

7、CCCCCCCCOHCCOHMgXCH2CH2OCCCCCCCOHCCCCCOH？以羰基化合物和鹵代烴為原料，通過(guò)，制備結(jié)構(gòu)較復(fù)雜的烯烴。6、魏悌希(Witting)反應(yīng)(C6H5)3P+ CH3X(C6H5)3PCH3X(C6H5)3PCH2(C6H5)3PCH2磷葉立德(ylide)鄰位兩性離子CH2O +(C6H5)3PCH2C=O +Ph3P=C(C6H5)3PCH2R4NClNH4ClC=O +Ph3P=CRRCCRRPh3PCHXRRPh3P=CRRPh3P + CHXRR練習(xí)8：P3795(2)用魏悌希試劑合成(CH3)2CCHC6H5 (CH3)2CO + Ph3PCHC6H5

8、C6H5CHO + Ph3PC(CH3)2Ph3P + CH3CHCH3BrPh3P + C6H5CH2Br練習(xí)7：苯、乙烯、丙烯3-甲基-1-苯基-2-丁烯CCC=CCCCCC=CCC練習(xí)6： 2-甲基-1-丙醇、異丙醇2,4-二甲基-2-戊烯HOCCCCOHCCCCCCHOC+ PPh3C(CH3)2CCHO+ PPh3C(CH3)2MgXCH2CH2O+BrCCC+ Ph3PBrCCC+ Ph3PCCOHCCCPPh3C+ OC(CH3)2CCPPh3+ OC(CH3)21、加NaHSO3鑒別醛、脂肪族甲基酮、小環(huán)酮2、加ROH用于保護(hù)醛基 保護(hù)的含義：轉(zhuǎn)化；復(fù)原3、加RMgX制備伯仲叔

9、醇 重點(diǎn)：原料分析4、加魏悌希試劑制備烯 用其他方法不易得到的烯，如：環(huán)外烯1、由格利雅試劑制備醇-C-CH3 C3H7OH-CH2CH2OHOH2、由魏悌希試劑制備烯烴CH=CHCH3=CHCH2CH3一、分析可能的原料組合C2H5OHOHC2H51、用乙烯、丁二烯合成-CH2CHCH2-OH二、合成2、用乙烯、甲苯、環(huán)戊烷合成ORCHCH(R)H羰基親核加成反應(yīng)-H的反應(yīng)氧化(以醛為主)與還原反應(yīng)飽和醛酮不飽和醛酮脂肪族醛酮脂環(huán)族醛酮芳香族醛酮根據(jù)烴基分類CH3CH=CH-CHOCCH3OCHOO根據(jù)官能團(tuán)分類OCH3CCH2CCH3OCH3CCH3OCH3CHOCH2CCH3O加成試劑：HCN；NaHSO3；ROH；NH2Y；RMgX； Ph3P=CRR（一）羰基的親核加成反應(yīng)COCOCO影響因素電