有機(jī)化學(xué)課件--第五章 鹵代烴

1、RX （ X = F, Cl, Br, I）RClRBrRI,RFRCH2XCHXRRCXRRRCXRRXCXRRCRXRCRRCRXXCH3CH2CH2CH2Br正正溴溴丁丁烷烷CH3CH2CHBrCH3仲仲溴溴丁丁烷烷CH3CBrCH3叔叔溴溴丁丁烷烷CH3正正丁丁基基溴溴仲仲丁丁基基溴溴叔叔丁丁基基溴溴CH3CHCH2BrCH3異異丁丁基基溴溴異異溴溴丁丁烷烷三三氯氯甲甲烷烷氯氯仿仿, , chloroformn-butyl bromidesec-butyl bromidetert-butyl bromideisobutyl bromideCHCl3選取選取含鹵素的最長碳鏈含鹵素的最長碳

2、鏈為主鏈為主鏈CH3CH2CHCH2CH3CH2Br2 乙乙基基 1 溴溴丁丁烷烷CH2CH2CCH2CH3CH3HBr(S) 3 甲甲基基 1 溴溴戊戊烷烷CH2ClCl反反 1 氯氯甲甲基基 4 氯氯環(huán)環(huán)己己烷烷CH3ClCHCH3CH2CH3(R) 2,3 二二甲甲基基 3 氯氯戊戊烷烷CH3HCNOFClBrISP2.12.53.03.54.02.12.53.02.82.5CX CF3CCl3 ,（強(qiáng)強(qiáng)）吸吸電電子子基基團(tuán)團(tuán)(electron withdrawinggroup)CRC Cl CRCClClCl CXCX+CXCX+Nu Nu( SNNucleophilic Substi

3、tution Reaction)CHRWW: 吸吸電電子子基基（electron withdrawing group）有有弱弱酸酸性性B（堿堿）CRW+HB CHRCH X BCRCH +X+HB消消除除 H成成烯烯烴烴Elimination Reaction) ）NuRX+XRNu+NuRX+XRHNu+H底物底物 (substrate)親核試劑：親核試劑： 至少含有一至少含有一對未共用電子對對未共用電子對OHORSHSROHRORRSHRSRR醇醇醚醚硫硫醇醇硫硫醚醚OCOROCORR酯酯NuR+XRNuCNCCR炔炔基基負(fù)負(fù)離離子子CNRCCRR腈腈高高級級炔炔丙丙二二酸酸酯酯負(fù)負(fù)離離子

4、子CH(CO2Et)2R烷烷基基丙丙二二酸酸酯酯IIRCH(CO2Et)2NuR+XRNu碘碘代代烷烷HOHHORHNH2HNHRHNR2NR3(水)(醇)(氨)(伯胺)(仲胺)(叔胺)ROH醇醇ORR醚醚RNH2伯伯胺胺RNHR仲仲胺胺RNR2叔叔胺胺RNR3 X季季銨銨鹽鹽NuR+XRHNu RX為重要有機(jī)中間體為重要有機(jī)中間體（intermediates）RXORRSHRSRROCORRCNRCC RRCH(CO2Et)2RIRNaOH or H2ONaOR or HORNaSH or NaSRNHR2(H)CCRNaCCRXMgorNaCH(CO2Et)2NaCNNaIRCOONa酯酯

5、腈腈高高級級炔炔烷烷基基丙丙二二酸酸酯酯醇醇醚醚伯伯胺胺仲仲胺胺叔叔胺胺硫硫醇醇( (硫硫醚醚) )OHRNH2RNHRRNR2R碘碘代代物物NuXRNuRXNuRX+過過渡渡態(tài)態(tài)NuRX+NuRXNuXR+勢勢能能反反應(yīng)應(yīng)進(jìn)進(jìn)程程 XRRNuNuR勢勢能能反反應(yīng)應(yīng)進(jìn)進(jìn)程程XRXRRX+NuRX+慢慢快快 動力學(xué)證據(jù)動力學(xué)證據(jù)反應(yīng)速率反應(yīng)速率立體化學(xué)證據(jù)立體化學(xué)證據(jù)對手性底物，對手性底物，產(chǎn)物的立體化學(xué)產(chǎn)物的立體化學(xué)重排重排現(xiàn)象現(xiàn)象反應(yīng)類型反應(yīng)類型I I RXNu構(gòu)型翻轉(zhuǎn)構(gòu)型翻轉(zhuǎn)無無雙分子機(jī)理雙分子機(jī)理bimolecular mechanismIIII RX消旋化消旋化有有單分子機(jī)理單分子機(jī)理

6、unimolecular mechanismNuRX+XR+NuC6H13H3CBrH+NaOHC6H13CH3HOH+NaBr構(gòu)構(gòu)型型發(fā)發(fā)生生轉(zhuǎn)轉(zhuǎn)換換與與 SN2 機(jī)機(jī)理理吻吻合合C6H13H3CBrHOHC6H13CCH3BrHHO C6H13CH3HOH+Br仲仲鹵鹵代代烷烷R1R2XR3Nu+R1R2NuR3R1R2NuR3+叔叔鹵鹵代代烷烷與與 SN1 機(jī)機(jī)理理吻吻合合R1R2XR3R1R2R3 XNuR1CR2NuR3()鹵代烷親核取代的兩種機(jī)理：鹵代烷親核取代的兩種機(jī)理： SN2 和和 SN1 機(jī)理機(jī)理(CH3)3CF+(CH3)3CSbF6可可通通過過核核磁磁共共振振觀觀察察到

7、到SbF5超超酸酸R2CHR3C1o2o3oCH3sp2 雜雜化化平平面面型型RCH2RHRH+RR+e 鍵鍵離離解解能能 電電離離能能RHRH+e 3o2o1oCH33o2o1oCH3,PhCH2CH2=CHCH2 H (KJ/mol)13161130100010719701040CHRCH2RRCCH pCHRORCHRORCHXRCHXRppppCHCHHH2CH pCHHH p（誘導(dǎo)）吸（誘導(dǎo)）吸CCF3CCCl3CCOCNO2CCH2HHH3CH2CCCH2H3CH2CHHHCCH2HH3CH2C HCCH2CH3HH3CH2CCCH2H3CH2CCH3H HCCHCH3CH3CH3

8、H3C CH3CCHCH3CH3CH3H3CCH3CH2Br+NaOHCH3CH2OHNaBr+CH3CH2BrOHCH3CH2OH+Br 希望通過這些例子，學(xué)習(xí)并基本掌握反希望通過這些例子，學(xué)習(xí)并基本掌握反應(yīng)機(jī)理的表達(dá)方法應(yīng)機(jī)理的表達(dá)方法CH3CBrCH3CH3+H2O乙乙醇醇CH3COHCH3CH3HBr+CH3CBrCH3CH3CH3CCH3CH3H2OBrCH3COHCH3CH3CH3COHCH3CH3+HBrHBrCCH2BrCH3CH3H3CCCH2OC2H5CH3CH3H3CC2H5OHCCH2CH3CH3OC2H5H3C+AgNO3 CH3CCH2CH3CH3H3CBrCCH2

9、CH3CH3H3C AgBrCCH2CH3CH3H3CC2H5OHCCH2CH3CH3H3CC2H5ONO3CCH2CH3CH3OC2H5H3C HNO3HAgNO3 絕對的按絕對的按 SN2 或或 SN1 機(jī)理的例機(jī)理的例子不多，一般情況下兩種機(jī)理并存，子不多，一般情況下兩種機(jī)理并存，并依反應(yīng)條件而改變。并依反應(yīng)條件而改變。NuRX+XR+Nu溶溶劑劑l R的結(jié)構(gòu)的結(jié)構(gòu)l CX鍵鍵強(qiáng)度強(qiáng)度l 體積體積l 濃度濃度l 親核能力親核能力 l 濃度濃度l 對親核試劑的影響對親核試劑的影響l 對反應(yīng)的影響對反應(yīng)的影響l 穩(wěn)定性穩(wěn)定性XRRNuNuRX慢慢快快NuXR NuRX+CX鍵強(qiáng)度：鍵強(qiáng)度：

10、F Cl Br ICX鍵易解離鍵易解離CX鍵易解離鍵易解離相對相對速率速率相對相對速率速率空間位阻效應(yīng)空間位阻效應(yīng) 電子效應(yīng)電子效應(yīng)BrROHRBr+OH80%乙醇水溶液55oCCH3CHH3CBrCH3CH3CCH3BrCH2H3CBr1000.220BrH3C7.99BrRIRNaBr+NaIAcetone（丙丙酮酮）CH3CHH3CBrCH3CH3CCH3BrCH2H3CBr1500.010.001BrH3C1相對相對速率速率BrROC2H5RBr+OC2H5無無水水乙乙醇醇55oCCH2H3CBrCH2CH2BrCH2CHBrCH2CBrH3CH3CH3CCH3H3CCH3100283

11、 0主要原因：主要原因：空間位阻效應(yīng)空間位阻效應(yīng)相對相對速率速率相對相對速率速率正碳離子穩(wěn)定性正碳離子穩(wěn)定性空助效應(yīng)（消除空助效應(yīng)（消除X減少基團(tuán)擁擠）減少基團(tuán)擁擠）BrROHRHBr+H2O80%乙乙醇醇- -水水55oCCH2H3CBrCH3CHH3CBrCH3CH3CCH3Br1000.0230.0140BrH3CBrROHRHBr+H2OHCOOHCH2H3CBrCH3CHH3CBrCH3CH3CCH3Br108451.71.0BrH3CHOC2H5OC2H5RClRIRNaCl+NaIAcetoneCH3CHH3CClCH2CH2ClH3CCH2H3CClCH2CHClH2CCH3C

12、lCH2Cl1.03393930.00760.37l 芐基與烯丙基芐基與烯丙基鹵代烴鹵代烴易發(fā)生易發(fā)生SN2相對相對速率速率l 相對相對速率速率ClROHRHCl+H2O80%乙乙醇醇- -水水HOC2H5OC2H5RCH3CHH3CClCH2H3CClCH2CHClH2CCH2Cl1.0CH3CH3CCH3ClHORNH2NH3FH2OR3CR2NHFRONH2ROROIBrClRSROHSHO,質(zhì)子性溶劑中質(zhì)子性溶劑中OSH3CCH3OCHNCH3CH3CH3CNOCH3CCH3DMFDMSO(Dimethyl Sulfoxide)(N, N Dimethylformamide)二二甲甲亞

13、亞砜砜N, N 二二甲甲基基甲甲酰酰胺胺ROH H2O RCOOHH2OHCOOHCH3OHC2H5OHCH3COOH805933246DMSODMFCH3CN49373621CH3CCH3OFClBrIRSROHSHOFHOHHOHHHOHHOCXNu 正離子被溶劑化了，正離子被溶劑化了，負(fù)離子完全釋放出來。負(fù)離子完全釋放出來。負(fù)負(fù)電荷密度大者親核性較強(qiáng)電荷密度大者親核性較強(qiáng)（與堿性順序一致）。（與堿性順序一致）。如：如： MX 在在 DMSO 中中OSH3CCH3MOSCH3H3COSCH3CH3OSH3CH3CXFClBrI強(qiáng)強(qiáng)弱弱free大體積大體積弱親核弱親核性強(qiáng)堿性強(qiáng)堿大體積大體積

14、堿強(qiáng)堿堿強(qiáng)堿強(qiáng)強(qiáng)弱弱強(qiáng)強(qiáng)弱弱親核性親核性試劑的體積作用試劑的體積作用烷基給電子作用烷基給電子作用堿堿 性性O(shè)CCH3CH3H3COCHCH3H3COCH2H3COH3CLDA (Lithium Diisopropyl Amide)NCHCH3H3CCHH3CCH3LiDIEA堿堿性性親親核核性性(CH3)2CH2NC2H5(C2H5)3N弱弱強(qiáng)強(qiáng)強(qiáng)強(qiáng)弱弱NuXRNuRX NuRX+XRRXXR X+極性大：極性大：對極性大（電荷密度集中）體系有利。對極性大（電荷密度集中）體系有利。極性?。簶O性?。簩O性?。姾擅芏确稚ⅲw系有利。對極性?。姾擅芏确稚ⅲw系有利。SN2 機(jī)理機(jī)理SN1 機(jī)理機(jī)

15、理電荷密度集中電荷密度集中（極性大）（極性大）電荷密度分散電荷密度分散（極性減?。O性減?。O性較小極性較小極性增加極性增加低極性溶劑對穩(wěn)低極性溶劑對穩(wěn)定過渡態(tài)有利定過渡態(tài)有利極性溶劑對穩(wěn)定極性溶劑對穩(wěn)定過渡態(tài)有利過渡態(tài)有利XR：1o ， 2oNu：強(qiáng)強(qiáng)親親核核性性， 大大濃濃度度溶溶劑劑：非非質(zhì)質(zhì)子子性性， 低低極極性性XR：3o, 烯烯丙丙型型, , 芐芐基基型型Nu：弱弱親親核核性性（避避免免SN2）溶溶劑劑：大大極極性性對對SN2有有利的因素利的因素對對SN1有有利的因素利的因素典型的典型的SN2典型的典型的SN1L = F, Cl, Br, INuRL+LR+Nu強(qiáng)強(qiáng)弱弱10-2

16、1 50 150FClBrI溶于丙酮溶于丙酮碘離子的碘離子的高親核高親核性性和和好離去性好離去性ClRNu, NaIIRNuR NaINu溶解性能的差別溶解性能的差別Cl ( Br)RNaI丙丙酮酮IR+NaCl (NaBr)不溶于丙酮不溶于丙酮SN2C6H13H3CIHNa I*丙丙酮酮消消旋旋化化光光學(xué)學(xué)純純a. 消旋化速率取決于消旋化速率取決于RI和和I b. 消旋化速度比同位素交換快一倍消旋化速度比同位素交換快一倍2. 試解釋下列實驗現(xiàn)象試解釋下列實驗現(xiàn)象（Hughes，1935）1. 由丙烯制備烯丙基碘由丙烯制備烯丙基碘H2CCHCH3H2CCHCH2I醇的羥基難取代醇的羥基難取代R

17、OHNuRNu+OHROC2H5RNH2RCN均難被取代均難被取代例：醇的溴代例：醇的溴代SN2 or SN1金屬的絡(luò)合物金屬的絡(luò)合物SN2 or SN1ROHHBrROH2BrRBr+H2OROHHClRHOZnCl2ClRCl +HOZnCl2ZnCl2SN2H3CSOOClH3CSOOORH3CSOOOROTsTsClOTs穩(wěn)定的負(fù)離子，弱堿穩(wěn)定的負(fù)離子，弱堿ROHTsClROTsNuRNuOTs+ HCl試寫出合理的機(jī)理解釋試寫出合理的機(jī)理解釋CH3HPhOHTsClCH3HPhOTsC2H5OKCH3HPhC2H5OCH3HPhOHKCH3HPhOKC2H5OTsCH3HPhOC2H

18、5 一般情況下，消除一般情況下，消除與親核取代反應(yīng)同時與親核取代反應(yīng)同時存在（競爭）存在（競爭） Elimination Reaction)取代反應(yīng)，取代反應(yīng)，SN2 or SN1X+Nu CHRCH X BCRCH +X+HBCHRCHNu 弱堿弱堿強(qiáng)堿強(qiáng)堿注意：注意：主要產(chǎn)物的結(jié)構(gòu)主要產(chǎn)物的結(jié)構(gòu) 有何特點？有何特點？CH3CH2CH2CH2ClCH3CH2CHCH2CH3CH2CHCH3ClCH3CH2CHCH2CH3CHCHCH3+主主要要次次要要CH3CH2CCH3BrCH3CH2CCH2CH3CHCCH3+主主要要次次要要CH3CH3CH3 EtOHKOHEtOHKOHEtOHKOH

19、EtOH注意：注意：消除為立消除為立 體專一性體專一性PhH3CHBrHPh PhCH3HBrHPh orKOEtEtOHCCH3CPhHPhPhH3CHBrHPh PhCH3HBrHPh or1R, 2R1S, 2S1S, 2R1R, 2SKOEtEtOHCCH3CPhHPh動力學(xué)證據(jù)動力學(xué)證據(jù)反應(yīng)速率反應(yīng)速率反應(yīng)的立體化學(xué)反應(yīng)的立體化學(xué)重排重排現(xiàn)象現(xiàn)象反應(yīng)類型反應(yīng)類型I I RXB:立體專一性立體專一性無無雙分子機(jī)理雙分子機(jī)理IIII RX無選擇性無選擇性有有單分子機(jī)理單分子機(jī)理 CHRCH X BCRCH +X+HB+ CCHXBCC+BHCCHXB + X五中心過渡態(tài)五中心過渡態(tài)勢勢能

20、能反反應(yīng)應(yīng)進(jìn)進(jìn)程程SPTCCHXCCH XB CC+BH慢慢快快SPT1T2M勢勢能能反反應(yīng)應(yīng)進(jìn)進(jìn)程程 CCHXBCC+BHCCHXB + XCCHXCCH XB CC+BH慢慢快快CCHX CH3CH2CHCH3ClCH3CH2CHCH2CH3CHCHCH3+主主要要次次要要 EtOHKOHCHClCH2CH3CHHHOHabCH3CHCHCH3CH3CH2CHCH2ab+H2O+Cl+H2O+ClCH3CH2CCH3BrCH3 CCH2CH3CHHHCH3 BrBrabaCH3CHCCH3CH3bCH3CH2CCH2CH3+HBrHBr+CH3CH2CCH3BrCH3CH2CCH2CH3C

21、HCCH3+主主要要次次要要CH3CH3CH3 EtOHKOHCH3CH2CCH3BrCH3CH2CCH2CH3CHCCH3+主主要要次次要要CH3CH3CH3 EtOHCCH3CHCH3BrCH3H3CEtOHCCCH3CH3H3CCH3+CCHCH3CH3H2CCH3CH3CCHCH3BrCH3H3C BrCCH3CHCH3CH3H3C CH3(CH3 遷遷移移)CCCH3CH3H2CCH3H BrCCCH3CH3H3CCH3H BrCCHCH3CH3H2CCH3abba CH3CH2CCH3BrCH3CH2CCH2CH3CHCCH3+主主要要次次要要CH3CH3CH3EtOHCH3CH2

22、CHCH3ClCH3CH2CHCH2CH3CH+主主要要次次要要EtOHKOHCHCH3E2 機(jī)理機(jī)理E1 機(jī)理機(jī)理為什么？為什么？CCRRRRCCRRHRCCRHHRCCRRHHCCRHHH CCHHHHCCRHHRCCRHHR有有 van der waals 排斥力排斥力CC+催催化化劑劑CCHH H = 氫氫化化熱熱（放熱）H2+ H2+ H2+ H2CH3CH2CHCH3ClCH3CH2CHCH2CH3CH+主主要要次次要要EtOHKOHCHCH3E2 反應(yīng)反應(yīng)CHClCH2CH3CHHHOHabCH3CHCHCH3CH3CH2CCH2abCH3CHCHCH3ClHHO ClHOH C

23、H3CH2CHCH2E1 反應(yīng)反應(yīng)CH3CH2CCH3BrCH3CH2CCH2CH3CHCCH3+主主要要次次要要CH3CH3CH3EtOHCH3CH2CCH3BrCH3 CCH2CH3CHHHCH3 BrBrabaCH3CHCCH3CH3bCH3CH2CCHCH3CH3CHCCH3CH3HBr HBr CH3CH2CCH2CH3CH3(CH2)3CHCH3ClCH3(CH2)3CHCH2CH3(CH2)2CHCHCH3+CH3OCH3CH3CCH3O67%9%33%91%ROZaitsev 取向取向Hofmann 取向取向H3CCCH2CCH3BrCH3CH3CH3H3CCCH2CCH2CH

24、3CH3CH3H3CCCHCCH3CH3CH3CH3+C2H5OCH3CH3CCH3O98%86%14%2%RO CCHXBCCHXB CCHXB HXB sp3 sp2CCHXBCCHXB CCB HXB HX重疊式構(gòu)象，重疊式構(gòu)象，較不穩(wěn)定。較不穩(wěn)定。負(fù)電荷相距較近，負(fù)電荷相距較近，有排斥作用有排斥作用PhH3CHBrHPh PhH3CHBrHPhEtOCCH3CPhHPhHPhCH3HPhBrEtOPhH3CHBrHPh PhCH3HBrHPh orKOEtEtOHCCH3CPhHPh(H3C)2HCClCH3C2H5O(H3C)2HCCH3(H3C)2HCClCH3C2H5O(H3C)

25、2HCCH3(H3C)2HCCH3+75%25%唯唯一一產(chǎn)產(chǎn)物物III消除速率消除速率I : II = 200 : 1(H3C)2HCClCH3(H3C)2HCClCH3HHHC2H5O(H3C)2HCCH3Hab(H3C)2HCCH3baIOC2H5(H3C)2HCClCH3(H3C)2HCClCH3HHH(H3C)2HCClCH3HHHC2H5O(H3C)2HCCH3HIICCXHNuB1o2o3oRXCH3CHCHCH3CH3BrNaI丙丙酮酮CH3CHCHCH3CH3ICH3CCHCH3CH3CH3CHCHCH3CH2CH3CHCHCH3CH3BrCH3COONa丙丙酮酮CH3CHCH

26、CH3CH3OCOCH3CH3CCHCH3CH3CH3CH CHCH3CH2CH3CCH3CH3Cl80% C2H5OH20% H2OCH3CCH3CH3OHCH3CCH3CH3OC2H5H2CCCH3CH3+CH3CCH3CH3BrCH3CCH3CH3OC2H5H2CCCH3CH3+C2H5ONaC2H5OH分析分析：醚類化合物可：醚類化合物可由親核取代制得由親核取代制得Williamson 醚合成法醚合成法切斷切斷(disconnection)CH3CCH3CH3OCH3RX+O RROR親親核核取取代代(Retrosynthetic analysis)RORRX+O RCH3CCH3CH

27、3OCH3abaCH3CCH3CH3X+OCH3bCH3CCH3CH3OXCH3+有兩種切斷方式有兩種切斷方式哪一種更有合成意義？哪一種更有合成意義？CH3CCH3CH3XHOCH3NaNaOCH3H2CCCH3CH3CH3CCH3CH3OICH3CH3CCH3CH3OHNaCH3CCH3CH3OCH3Hofmann取向取向 CCHFBCC+BHFCCF 慢慢快快機(jī)理：經(jīng)過碳負(fù)離子中間體機(jī)理：經(jīng)過碳負(fù)離子中間體CH3CH2CH2CH2CHCH3FCH3ONaCH3OHCH3CH2CH2CH2CHCH2CH3CH2CH2CHCHCH3+70%30%C F鍵較強(qiáng)鍵較強(qiáng)不易斷開不易斷開CH3CH2C

28、H2CHFCH3CH2CH2CHCHCH2FHHCH3OOCH3abCH3CH2CH2CH2CHFabCHCH3CH2CH3CH2CH2CH2CHCH2CH3CH2CH2CHCHCH3 F F較穩(wěn)定較穩(wěn)定較不穩(wěn)定較不穩(wěn)定Hofmann取向的解釋取向的解釋2o1oCCFOC2H5DCCHFOC2H5CCDFCCHFDOC2H5CCDFOC2H5 /機(jī)理機(jī)理RXLiAlH4NaBH4（還還原原 2o or 3o RX）Zn / HClNa / NH3 (液液)H2 / PdRHXR還還原原劑劑CH3R 合成上合成上若涉及還原若涉及還原反應(yīng)，應(yīng)注反應(yīng)，應(yīng)注意底物中是意底物中是否有鹵素。否有鹵素。RX

29、+Mg醚醚RMgXXMgXMgOR2RRR2ORXMgORRORR單單體體( (稀稀溶溶液液) )二二聚聚體體( (濃濃溶溶液液) )烷基鹵化鎂烷基鹵化鎂Grignard試劑試劑（溶解于醚）（溶解于醚）RX+2 Li醚醚或或烷烷烴烴RLi+LiX烷基鋰烷基鋰R XLi+R XLi+R XRX+R+LiR Li有機(jī)金屬化合有機(jī)金屬化合物物金屬與金屬與碳直接成鍵碳直接成鍵常用醚：常用醚：乙醚乙醚四氫呋喃四氫呋喃（THF）O RMgXR2CdR2CuLiRLi烷基鋰烷基鋰烷基鹵化鎂（烷基鹵化鎂（Grignard試劑，格氏試劑，格林雅試劑）試劑，格氏試劑，格林雅試劑）二烷基銅鋰二烷基銅鋰烷基鎘烷基鎘R

30、M （M = 金金屬屬，metal）金屬金屬電負(fù)性電負(fù)性Li1.0Mg1.2Cd1.7Cu1.9較活潑金屬可與較活潑金屬可與 RX 直接反應(yīng)直接反應(yīng)RX+2 Li醚醚或或烷烷烴烴RLi+LiXRX+Mg醚醚RMgX2 RLi+CuIR2CuLi+LiI2 RMgCl+CdCl2R2Cd+2 MgCl2較不活潑金屬，用交換法較不活潑金屬，用交換法反應(yīng)活性：反應(yīng)活性：RI RBr RCl脂肪族脂肪族鹵代物鹵代物 芳香族芳香族鹵代物和鹵代物和烯基烯基鹵代物鹵代物Victor Grignard(1871 1935)諾貝爾化學(xué)獎諾貝爾化學(xué)獎（1912）RX+Mg醚醚RMgX現(xiàn)制現(xiàn)用現(xiàn)制現(xiàn)用RMgX R RMgX+2ROMgX2O2H2OROH化合物化合物pKa共軛堿共軛堿化合物化合物pKa共軛堿共軛堿(CH3)3C H71(CH3)3CH2N H36H2NCH3CH2 H62CH3CH2