鄭州大學(xué)有機(jī)化學(xué)10醇醚

1、If, as an organic chemist, you were allowed to choose the ten aliphatic compounds with which to be stranded on a desert island, you would almost certainly pick alcohols. You would use your alcohols not only as raw materials, but frequently as the solvents. Finally, hot and tired after a long day in

2、the laboratory, you could perhaps relax over an alcoholic drink! Chapter 10 Alcohols and Ethers10.1 Nomenclature, Classification and Structure10.1.1 NomenclatureOH5,6,6-三甲基三甲基-5-乙基乙基-2-庚醇庚醇5-ethyl-5,6,6-trimethyl-2-heptanolOHHHOH(2R,5S)-7-甲基甲基-2,5-辛二醇辛二醇(2R,5S)-7-methyl-2,5-octanediolOH(E)-6,7-二甲基二甲

3、基-6-壬烯壬烯-1-醇醇(E)-6,7-dimethyl-6-nonen-1-olH3COH1-甲基環(huán)戊醇甲基環(huán)戊醇 1-methylcyclopentanolHOCH3(1S,2S)-2-甲基環(huán)己醇甲基環(huán)己醇(1S,2S)-2-methylcyclohexanolOHHO(1R,4R)-2-環(huán)己烯環(huán)己烯-1,4-二醇二醇(1R,4R)-cyclohex-2-ene-1,4-diolCH2OH環(huán)戊基甲醇環(huán)戊基甲醇cyclopentylmethanolCH2OH苯甲醇苯甲醇 芐醇芐醇phenylmethanolCOHCH3CH32-苯基苯基-2-丙醇丙醇2-phenyl-2-propanolH

4、OOHHO4-羥甲基羥甲基-1,8-辛二醇辛二醇4-hydroxymethyl-1,8-octanediolprimary alcohols (伯醇伯醇, 1醇醇)secondary alcohols (仲醇仲醇, 2醇醇)tertiary alcohols (叔醇叔醇, 3醇醇) 10.1.2 ClassificationCOHROHHOHR+ H2OCOHROHRORR+ H2OCOHROHOHOOHR+ H2O10.1.3 StructureCH3OHCH3CH2OHHHHOHHH一元醇一元醇多元醇多元醇脂肪醇脂肪醇脂環(huán)醇脂環(huán)醇芳香醇芳香醇CH3CH2CH2OHCH3HHOHHHHOCH

5、2CH2OHOHHHOHHHHOHOHHHHHOCH2CH2ClHClHOHHHHOCH2CH2OCH3HOHOHHCH3HOHOHHOOHOOHHX10.2 Spectroscopy (光譜學(xué)光譜學(xué))IR(紅外紅外)醇醇OH伸縮振動(dòng)伸縮振動(dòng): 游離游離羥基羥基3650 3610(尖峰尖峰, 強(qiáng)度不定強(qiáng)度不定), 締合締合羥基羥基35003300 (寬峰寬峰) (形形成成氫鍵氫鍵后基團(tuán)的伸縮頻率都會(huì)后基團(tuán)的伸縮頻率都會(huì)下降下降，譜帶，譜帶變寬變寬)醇醇C-O伸縮振動(dòng)伸縮振動(dòng)126010001-己醇己醇CH3CH2CH2CH2CH2CH2OH順順-1,2-環(huán)戊二醇在低頻區(qū)有紅外吸收，既使稀釋該吸

6、收峰也不消失；反環(huán)戊二醇在低頻區(qū)有紅外吸收，既使稀釋該吸收峰也不消失；反-1,2-環(huán)戊二醇無(wú)環(huán)戊二醇無(wú)此吸收，為什么？此吸收，為什么？NMR(核磁共振氫譜核磁共振氫譜)HO-CH2-CH3羥基質(zhì)子羥基質(zhì)子 = 0.55.5 ppm氫鍵氫鍵使使羥基質(zhì)子羥基質(zhì)子共振信號(hào)共振信號(hào)移向低場(chǎng)移向低場(chǎng), 常是一個(gè)較寬的單峰常是一個(gè)較寬的單峰分子內(nèi)氫鍵分子內(nèi)氫鍵, 其化學(xué)位移變化與溶液濃度無(wú)關(guān)其化學(xué)位移變化與溶液濃度無(wú)關(guān)加入幾滴加入幾滴重水重水(D2O), 再測(cè)定圖譜，再測(cè)定圖譜，會(huì)使會(huì)使羥基羥基質(zhì)子信號(hào)消失質(zhì)子信號(hào)消失MS(質(zhì)譜質(zhì)譜)醇醇的的分子離子峰分子離子峰M+經(jīng)常經(jīng)常較弱較弱, 甚至看不到甚至看不到

7、, M-18或或M-15或或M-29峰峰豐度較高豐度較高CHCH2CH3OH+ H2O+ CH2CH3CHCH2CH3OHm/z = 136CH=CHCH3m/z = 118CHOHm/z = 10710.3 ReactionsCOH + +Acidity and basic / nucleophilic -OH is a leaving group (very poor)SN2 or SN1E1 or E2Formation of esters(酯酯) and sulfonates(磺酸酯磺酸酯)Oxidation10.3.1 Acidity and Basic / Nucleophilic

8、 ROHAlkoxide ion(stablized by solution)OHH+ROOHH+H+-AcidityAcidity: 1 2 3 共軛堿的堿性？共軛堿的堿性？Acidity:RSO3H RCOOH ArOH H2O ROH RCCH H2 NH3 RHOHOHOHOHOHOHOHO2NO2NClClCH3OCH3ORONa + H2OROH + NaOHRONa + RCCHROH + RCCNaNH3 + RCCNaNaNH2 + RCCHROH + NaNH2RONa + NH3ROH + RMgXRH + MgX(OH)Reaction with active meta

9、ls (與活潑金屬反應(yīng)與活潑金屬反應(yīng))K Na Mg AlROH + NaRONa + H2ROH + NaHRONa + H2(CH3)2CHOH + Al(CH3)2CHO3Al(CH3)3COH + K(CH3)3COK大體積強(qiáng)堿大體積強(qiáng)堿親核性較弱親核性較弱Basic / NucleophilicCO H + HACO HH+ A-+質(zhì)子化醇質(zhì)子化醇ROH + HIROH2 I-Good leaving group(CH3)3CBr + C2H5OH(CH3)3COC2H5 +72%CCH2H3CCH328%55叔鹵代烷的溶劑解叔鹵代烷的溶劑解(SN1), 醇的親核性弱醇的親核性弱鹽1

10、0.3.2 Formation of esters and sulfonatesRCOOH, (RCO)2O or RCOClROHRCOOR羧酸酯羧酸酯酰化反應(yīng)?；磻?yīng)ROH + HONO2RONO2ROH + HONORONO硝酸酯硝酸酯亞硝酸酯亞硝酸酯RNO2硝基化合物硝基化合物 CH2ONO2CHONO2CH2ONO2The 1998 Nobel Prize in Medicine was awarded to the scientists (R. F. Furchgott, L. J. Ignarro, and F. Murad) who discovered that NO is

11、an important signaling molecule (chemical messenger).ROHPOOHHOOH+POOHROOHPOOHROORROHPOORROORROH三硝酸甘油酯三硝酸甘油酯磷酸酯磷酸酯ROSOHOOROH + HOSOHOOROHROSOROOSulfates(硫酸酯硫酸酯)Me2SO4硫酸二甲酯硫酸二甲酯是個(gè)很好的甲基化試劑是個(gè)很好的甲基化試劑CH3OSOCH3OOCH3CH2OH +baseCH3CH2OCH3SN2Sulfonates(磺酸酯磺酸酯)ROHRSO2ClRSO2ORbase+OCH2CH3HbaseSOCH3ClOSOCH3OCH2

12、CH3OMsCl+OCH2CH3HbaseSOOCH2CH3OCH3SOClOCH3TsCl磺酸酯磺酸酯是個(gè)很好的烷基化試劑是個(gè)很好的烷基化試劑SOOORCH2R- Nu+SOO-ORRCH2Nu +SN2常用親核試劑常用親核試劑: 烷氧基負(fù)離子烷氧基負(fù)離子, 鹵素負(fù)離子等鹵素負(fù)離子等CH3OSO2C2H5ONaC2H5OCH3CRRHOH + ClTsretention-HClCRRHOTsROSOROOROHROHbaseRORSulfates (硫酸酯硫酸酯)Sulfonates (磺酸酯磺酸酯)baseROHRSO2ClRSO2ORbaseNu-RNuO O H HT Ts sC Cl

13、 lO O T Ts sH HC Cl l( (S S) )- -2 2- -O O c ct ta an no ol l( (S S) )- -2 2- -O O c ct ty yl l t to os sy yl la at te e+ +p py yr ri id di in ne e+ +T To os sy yl lc ch hl lo or ri id de eO O- -N N a a+ +O OO O T Ts sO OO ON N a a+ +O O T Ts s- -( (S S) )- -2 2- -O O c ct ty yl l t to os sy yl la a

14、t te e+ +S So od di iu um ma ac ce et ta at te ee et th ha an no ol lS SN N2 2+ +( (R R) )- -2 2- -O O c ct ty yl l a ac ce et ta at te eOOOODue to its suitable properties and the low cost, DEHP (鄰苯二甲酸二鄰苯二甲酸二(2-乙基乙基)己酯己酯) is widely used as a plasticizer in manufacturing of articles made of PVC. Plas

15、tics may contain 1% to 40% of DEHP. 10.3.3 Nucleophilic Substitution(親核取代親核取代)ROHRNuNu-OH is a leaving group (very poor)10.3.3.1 Reaction with HXROHHXRXReactivity of HX HI HBr HClReactivity of ROHBenzyl, allyl, 3 2 1CCH3OHCH3H3C+ HCl (concd)25 oC+ H2O94%CCH3ClCH3H3CCH3CH2CH2CH2OH+refluxCH3CH2CH2CH2B

16、rHBr (concd)(95%)用用Lucas試劑（鹽酸試劑（鹽酸+氯化鋅）鑒別各類醇氯化鋅）鑒別各類醇CHHROHH+RCH2OHH+Mechanism1alcohols and methanolSN2X+CHHRCHHROHH+X -OHH+ORHORHZnCl2-+ZnCl2ORHZnCl2-+Cl -ClR+Zn(OH)Cl2-2, 3, allylic, and benzylic alcoholsSN1+ HfastCCH3CH3H3COHHCCH3OCH3H3CH+slowCCH3CH3H3COHHOHH+H3CCCH3CH3+fastCCH3CH3H3CClCl -H3CCCH

17、3CH3+外消旋化、重排外消旋化、重排與與HBr反應(yīng)速度反應(yīng)速度CH3OCH=CHCH2OH CH3CH=CHCH2OH ClCH=CHCH2OH NCCH=CHCH2OHOHHBrBrBr+64%36%HOHBrBrBr+Neighboring-group Participation(鄰基參與鄰基參與)CH3BrHCH3HOHHBrCH3BrHCH3HBrCH3HBrCH3BrH+蘇式蘇式蘇式外消旋體蘇式外消旋體BrOHH3CCH3HHH+BrOH2H3CCH3HHBrH3CCH3HHBr-BrBrH3CCH3HHBrBrCH3H3CHH+CH3HBrCH3HOHHBrCH3HBrCH3HB

18、r赤式赤式赤式內(nèi)消旋體赤式內(nèi)消旋體10.3.3.2 Reaction with Other ReagentsPX3或或PX5+ PBr3+C2H5OHRBrH3PO3C2H5OH + PCl5RCl+ HClPOCl3C2H5OHPI2RI1and 2alcohols seldom rearrange (SN2)RCH2OHBrPBrBr+BrRCH2OPBr2H+-RCH2BrA good leaving groupBr -RCH2OPBr2H+ HOPBr2+PBr3-10 to 0 oC4 h(55-60%)(CH3)2CHCH2OH(CH3)2CHCH2BrSOCl2 (亞硫酰氯亞硫酰

19、氯 氯化亞砜氯化亞砜)reflux+ SOCl2+ROHRClHCl + SO2緊密離子對(duì)緊密離子對(duì)SNiretention of configurationA 3amine is added to promote the reaction inversion of configuration (SN2) + SOCl2pyridine(91%)CH2OHH3COCH2ClH3COMechanismheat+CCH2OCCHOHHAR OSOOCH3Nu-RNuROHTsCl10.3.3.3 Reactions via Sulfonates or Sulfates (通過(guò)磺酸酯或硫酸酯反應(yīng)通過(guò)

20、磺酸酯或硫酸酯反應(yīng))CN-I- / 丙酮丙酮RO-構(gòu)型保持構(gòu)型保持 構(gòu)型翻轉(zhuǎn)構(gòu)型翻轉(zhuǎn)10.3.4 EliminationIntermolecular Dehydration of Alcohols (消除反應(yīng)消除反應(yīng)醇的分醇的分子內(nèi)脫水子內(nèi)脫水) E1OHH+t-BuOKHOTsClTsORCH2OHRCOHRCOOHOO10.3.5 Oxidation(氧化氧化)RCHOHRCORRO10.3.5.1 KMnO4 and MnO2RCH2OHH3O+RCO2HOH +KMnO4RCO2 K+H2Oheat MnO2OHKMnO4COOH74%伯醇分子中如有烯鍵，亦可被氧化伯醇分子中如有烯鍵，

21、亦可被氧化仲醇叔醇用仲醇叔醇用酸性酸性高錳酸鉀氧化易使碳鏈斷裂高錳酸鉀氧化易使碳鏈斷裂新制新制MnO2KMnO4 + MnSO4 + NaOHMnO2 + K2SO4 + Na2SO4 + H2OC COHC CCH OHMnO2MnO2C CC HOC CCO其他羥基以及烯鍵不受影響其他羥基以及烯鍵不受影響MnO2HOHOOHOHOOH10.3.5.2 Chromic acid (鉻酸鉻酸) Na2Cr2O7/H2SO4, CrO3/HOAc, CrO3.Py.HCl/CH2Cl2, CrO3 / H2SO4acetone (Jones試劑試劑) pyridinium chlorochrom

22、ate(氯鉻酸吡啶嗡鹽氯鉻酸吡啶嗡鹽) PCC (Sarrett試劑試劑)如果醛的沸點(diǎn)低，可蒸出避免進(jìn)一步氧化如果醛的沸點(diǎn)低，可蒸出避免進(jìn)一步氧化Na2Cr2O7/H2SO4RCH2OHRCO2HRCHONa2Cr2O7/H2SO4Na2Cr2O7/H2SO4CH3CH2CH2OHNa2Cr2O7/H2SO4CH3CH2CHO50%Na2Cr2O7/H2SO4OHO85%OHH2CrO4AcetoneO35oCPCC +NCrO3Cl-CrO3+ HClNH+(C2H5)2C CH2OHCH3PCC(C2H5)2CCHCH3O25oC+CH2Cl294%80%OHPCCCH2Cl2O84%PC

23、CCH2Cl2OHHO10.3.5.3 Nitric acid(硝酸硝酸) 10.3.5.4 Oppenauer OxidationCH OH +CH3CCH3O(i-PrO)3AlC OCH3CHCH3OH+可逆反應(yīng)可逆反應(yīng)+CH3CCH3O(i-PrO)3AlCH3CHCH3OH+OHO+CH3CCH3O(t-BuO)3AlCH3CHCH3OH+CH2OHCHO10.3.5.5 Pfizner-Moffatt OxidationCH3SCH3ODCCN C NN,N-dicyclohexylcarbodiimide (N,N-二環(huán)己基碳二亞胺二環(huán)己基碳二亞胺)脫水劑脫水劑CH3SCH3OD

24、CCO2NCH2OHO2NCHO10.4 Reactions of Glycols (鄰二醇的反應(yīng)鄰二醇的反應(yīng))10.4.1 Oxidative Cleavage(氧化斷裂氧化斷裂)Periodic acid (高碘酸高碘酸)OHOHH5IO6OHCCHO高碘酸高碘酸或或醋酸鉛醋酸鉛C OHC OHIOHHOHOOHOO+IOHOOOHOOCCMechanism鄰二醇鄰二醇( -二醇二醇), -羥基醛羥基醛/酮酮/酸酸, -氨基醛氨基醛/酮酮/酸酸, 1,2-二酮二酮(-二酮二酮), 1-氨基氨基-2-羥基化合物羥基化合物均可被高碘酸分解均可被高碘酸分解OHOHt-BuOHOH很慢很慢Bu-t

25、OHOHLead acetate (醋酸鉛醋酸鉛)：Pb(OAc)410.4.2 Pinacol Rearrangement (頻哪醇重排頻哪醇重排)CH3CCH3OHCH3CCH3OHH+CH3COCH3CCH3CH3CH3CCH3OHCH3CCH3OHH+CH3CCH3OHCH3CCH3OH2CH3CCH3OHCH3CCH3-H2OCH3COHCH3CCH3CH3HCPhOHCPhCH3OHH+1) 形成最穩(wěn)定的碳正離子形成最穩(wěn)定的碳正離子HCPhOHCPhCH3Mechanism2) 提供電子的基團(tuán)發(fā)生遷移提供電子的基團(tuán)發(fā)生遷移HCPhOHCPhCH3HCOCPhPhCH33) 遷移基團(tuán)

26、與離去基團(tuán)應(yīng)處于反位遷移基團(tuán)與離去基團(tuán)應(yīng)處于反位H3COH2CH3HOOH3CCH3H3COHOHH3C10.5 Preparation of AlcoholsAlkenesAlkyl HalidesCarbonyl CompoundsAlcoholsGrignard SynthesisCH3OHCH3HOCH3OH2CH3HOH+- H2OHO10.5.1 Via Hydrolysis of Alkyl Halides(通過(guò)鹵代烴的水解通過(guò)鹵代烴的水解)It is rarely used for the synthesis of alcohols, since alkyl halides a

27、re normally prepared from alcohols.很少用鹵代烴的水解來(lái)制備醇，因?yàn)槎鄶?shù)情況下鹵代烴比醇貴重，常用醇來(lái)制備鹵很少用鹵代烴的水解來(lái)制備醇，因?yàn)槎鄶?shù)情況下鹵代烴比醇貴重，常用醇來(lái)制備鹵代烴。代烴。CH3Br + HO- CH3OH + Br- (CH3)3CBr + H2O (CH3)3COH + HBr H3CCH3CH3CH2ClH2O, Ca(OH)2H3CCH3CH3CH2OH(78%)RX + HO- ROH + X-10.5.2 Via Reactiontion of Alkenes (通過(guò)烯烴反應(yīng)通過(guò)烯烴反應(yīng))H2SO4H+H2OH C C OSO3

28、HH2OH C C OH1) BH32) H2O2/OH-H C C OHH C C OHCCCCOOsOOOH2OCCOH OH+OsOOOOH2O, H+ or OH-HOOHRCO3HNa2CO3OCXCOHX2 / OH-Oxymercuration-demercuration of alkenes(烯烴的羥汞化烯烴的羥汞化-去汞化去汞化)CHgOAcCOHH2OHg(OAc)2NaBH4CHCOHThe reactions take place very rapidly at room temperature;The overall reaction gives alcohols i

29、n very high yields, usually greater than 90%; Rearrangements of the carbon skeleton seldom occur.* Mercury compounds are extremely hazardous!Markovnikov additionanti addition(反式加成反式加成)Mechanism(機(jī)理機(jī)理)H2OHg(OAc)2NaBH4OHCH=CH2CCH3H3CH2OHg(OAc)2NaBH4CH3CHCCH3H3CCH3CH3OHCH3(CH2)2CHCH2Hg(OAc)2CH3(CH2)2CHC

30、H2HgOAcNaBH4OH(93%)THF-H2OOH-(1 h)CH3(CH2)2CHCH2HOH(15s)10.5.3 Via Reduction of Carbonyl Compounds or Derivatives of Carboxylic Compounds (通過(guò)羰基化合物或羧酸衍生物還原通過(guò)羰基化合物或羧酸衍生物還原) H RCHORCH2OH H RCRORCHROH H RCOHORCH2OH+ H RCORORCH2OHROHHydrogenation (H2 with Raney nickel): Also reduces any C=C bondsSodium i

31、n alcohol Lithium aluminum hydride (LiAlH4): reduces acids, esters, aldehydes, and ketonesSodium borohydride (NaBH4): reduces only aldehydes and ketones10.5.4 Grignard Synthesis(格氏試劑合成法格氏試劑合成法)RMgX+CO1. ether2. H3O+X -CROH+MgX21) Grignard Reagents React with Formaldehyde to Give a 1 Alcohol.2) Grign

32、ard Reagents React with All Other Aldehydes to Give 2 Alcohols.3) Grignard Reagents React with Ketones to Give 3 Alcohols.+H3O+ RMgXHCHOOCHHROHCHHRMgX+H3O+ RMgXRCHOOCRHROHCRHRMgX+H3O+ RMgXRCROOCRRROHCRRRMgX+H3O+C6H5MgBrHCHOOMgBrC6H5CH2Et2OC6H5CH2OH90%+H3O+CH3CH2MgBrH3CCHOEt2OCH3CH2CHOHOMgXCH3CH2CCH3

33、HCH380%+NH4ClCH3CH2CH2CH2MgBrH3CCH3COEt2OOMgXCH3CH2CH2CH2CCH3CH3OHCH3CH2CH2CH2CCH3CH3H2O92%+H3O+RMgXRCROOOCRORMgXOHCRRRRInitial product (unstable)-ROMgXspontaneouslyRCRORMgXOMgXCRRR4) Esters React with Two Molar Equivalents of a Grignard Reagent to Form 3 Alcohols+H3CCC2H5OOOMgBrCCH3OCH2CH3CH3CH2OHC

34、H3CH2CCH3CH2CH3H3CCCH3CH2OCH3CH2MgBrOMgXCH3CH2CCH3CH2CH3CH3CH2MgBr-C2H5OMgBrNH4ClH2O67%如用如用甲酸酯甲酸酯，則得，則得仲醇仲醇+CH3CH2CH2CH2MgBr85%HCOOC2H5(CH3CH2CH2CH2)2CHOH也可使用也可使用碳酸酯碳酸酯+CH3CH2MgBr85%COOCH3CH3OCCH2CH3HOCH2CH3CH2CH3CH2H2CO+H+ RMgXRCH2CH2O -Mg2+X-RCH2CH2OHSN2CH2H2CO+H+C6H5MgBrC6H5CH2CH2OMgBrEt2OC6H5CH2

35、CH2OH5) Reactions of Grignard Reagents with EpoxidesCHH2CO+C6H5MgBrCH3H+C6H5CH2CHOMgBrEt2OC6H5CH2CHOHCH3CH3+H3O+ + RLiCOOCROHCRLi6) 其他類似試劑其他類似試劑+H2C CHLiC6H5CHOCH2=CHCHC6H5OH NaCH3 CCH3 O+H3CCCH3CCCCCH3CH3ONa H3O+H3CCCCCH3CH3OH炔醇炔醇CMgBrC2H5CHOCCHC2H5OH+C6H5CC6H5CC6H5MgBrCH2CH3COCH3CH2+1. Et2O2. NH4C

36、lCH2CH3CC6H5OHCH3CH2H2OCH3CH2MgBr+C6H5CCH3CH2O1. Et2O2. NH4ClH2OCH2CH3CC6H5OHCH3CH21. Et2O2. NH4ClH2OCH2CH3CC6H5OHCH3CH2+CH3CH2MgBr2C6H5OCH3CORetrosynthetic Analysis (逆合成分析逆合成分析)CH2CH3CC6H5OHCH3CH2Ethers (醚醚)C2H5OC2H5 diethyl ether (乙醚乙醚) First general anestheticCauses nausea and vomiting, and is hi

37、ghly flammableCH3OC(CH3)3 Methyl tert-butyl ether (MTBE 甲基叔丁基醚甲基叔丁基醚) Additive to improve gasoline performance as an antiknock agent and to reduce emission of CO in automotive exhaust gas Sulfide(硫醚硫醚) RSRROR10.6 Structure, Classification and Nomenclature10.6.1 StructureC CH H3 3- -O O - -C CH H3 3C

38、 CH H3 3C CH H2 2- -O O - -C CH H2 2C CH H3 3D D i im m e et th hy yl l e et th he er rD D i ie et th hy yl l e et th he er rsp3111.710.6.2 ClassificationR-O-R simple ether(單醚單醚), symmetrical ether(對(duì)稱醚對(duì)稱醚)R-O-R complex ether(混醚混醚), unsymmetrical ether(不對(duì)稱醚不對(duì)稱醚)aliphatic ether(脂肪醚脂肪醚)aromatic ether(芳

39、香醚芳香醚)OCH3OOsp2p- 共軛共軛Ocyclic ether(環(huán)醚環(huán)醚)OOOOOEpoxide, oxirane(環(huán)氧化合物環(huán)氧化合物, 環(huán)氧乙烷環(huán)氧乙烷)Crown ether(冠醚冠醚)OOOOOOOOOOOO10.6.3 NomenclatureCommon NamesCH3-O-CH3甲醚甲醚dimethyl ethermethyl etherO二乙烯基醚二乙烯基醚C6H5OC6H5二苯基醚二苯基醚CH3-O-CH2CH3甲乙醚甲乙醚CH3CH2-O-CH2Cl乙基氯甲基醚乙基氯甲基醚O甲基叔丁基醚甲基叔丁基醚O異丁基仲丁基醚異丁基仲丁基醚OO烯丙基乙炔基醚烯丙基乙炔基醚甲

40、基環(huán)己基醚甲基環(huán)己基醚O苯乙醚苯乙醚IUPAC NamesROalkoxy groupO2-甲基甲基-2-甲氧基丙烷甲氧基丙烷2-methoxy-2-methylpropaneCH3-O-CH2CH2CH31-甲氧基丙烷甲氧基丙烷O2-異丁氧基丁烷異丁氧基丁烷 2-(2-甲基丙氧基甲基丙氧基)丁烷丁烷2-isobutoxybutaneEpoxide, oxirane (環(huán)氧化合物環(huán)氧化合物, 環(huán)氧乙烷環(huán)氧乙烷)O環(huán)氧乙烷環(huán)氧乙烷氧化乙烯氧化乙烯123O2,2-二甲基環(huán)氧乙烷二甲基環(huán)氧乙烷氧化異丁烯氧化異丁烯O(S)-2,2-二甲基二甲基-3-異丙基環(huán)氧乙烷異丙基環(huán)氧乙烷O甲基環(huán)氧乙烷甲基環(huán)氧乙

41、烷1,2-環(huán)氧丙烷環(huán)氧丙烷O1,3-環(huán)氧丙烷環(huán)氧丙烷O2-甲基甲基-1,2-環(huán)氧丙烷環(huán)氧丙烷O2,4-二甲基二甲基-2,3-環(huán)氧戊烷環(huán)氧戊烷O2,3,4-三甲基三甲基-3,4-環(huán)氧環(huán)氧-1-戊烯戊烯O1,2-環(huán)氧環(huán)己烷環(huán)氧環(huán)己烷氧化環(huán)己烯氧化環(huán)己烯OOOOOOOOOOOO18-冠冠-610.7 SpectroscopyIR醚醚COC伸縮振動(dòng)伸縮振動(dòng)12751020cm-1(強(qiáng)吸收強(qiáng)吸收)NMR1H-C-O = 3.54 ppmCH3CH2CH2OCH2CH2CH3MS醚醚的的分子離子峰分子離子峰M+常常較弱較弱CH3CH2CH2CH2OCH2CH2CH2CH3M=130m/z=57m/z=87

42、 分子離子失去分子離子失去C3H7.分子離子失去分子離子失去C4H9O.10.8 Reactions10.8.1 Autoxidation(自動(dòng)氧化自動(dòng)氧化)10.8.2 BasidityROR+H+RORHROR+BF3RORBF3-形成形成钅羊钅羊鹽和絡(luò)合物的能力鹽和絡(luò)合物的能力: ROR ROAr ArOArThe 1987 Nobel Prize in Chemistry was awarded to Charles J. Pedersen, Donald J. Cram, and Jean-Marie Lehn for their work on crown ethers and r

43、elated compounds (host-guest chemisty). CH3OCH3HBrCH3OCH3H_Br_+10.8.4 Acid-Catalyed CleavageReactivity: HI HBr HClRORHXRX + ROHHXRXEthers with 1 alkyl groups react by an SN2Br_+CH3OCH3HBr CH3+HOCH3RCH2OCH3HI+CH3IRCH2OHHIRCH2ICH2CH3OCH3CHOCH3CHHICH3CH2CH3HI,H2OCH3+SN2OHIOHI+OHI+OCH2CH3HBr, H2ORefluxO

44、HCH3CH2Br+Phenol cannot react further to become halideAllylic, benzylic, and 3o ethers cleave via E1/SN1CH3CH3CH3CCH2CH2CH3OCH3CH3CH3CBrHOCH2CH2CH3HBr+OHBrOH- Br-CH3OHCH3H3CCH3+混醚混醚C-O斷裂次序斷裂次序:Allyl, benzyl, 3烷基烷基2烷基烷基, 1烷基烷基, CH3芳基芳基ArOAr在在HI作用下醚鍵不斷裂作用下醚鍵不斷裂C CH2C6H5H3COH3O+C6H5COCH3CH3OH10.8.5 Hyd

45、rogenolysis of Benzyl Ethers (芐基醚的氫解芐基醚的氫解)CH2O RH2 / Pd-CCH3ROH+This Reaction is useful for protection of -OHOHOHOHOCH3OCH3OOHPhCH2Clpyridine1) BH3 / THF2) H2O2 / OH-OOHOCH3OCH3OCH3OH2, Pd/COHOHBrBrOHHBrBrBr10.8.6 Ring Opening of Epoxide (環(huán)氧乙烷的開環(huán)環(huán)氧乙烷的開環(huán))ORNu- anionic nucleophileUnder conditions of acid catalysisRing Opening in BaseORNaOHRONaNH3NaCNNaN3C6H5LiRC CNaRMgXLiAlH4RHOOHRHOORRHOCNRHON3RHOC6H5RHOC CRRHORRHOHRHONH2OC2H5ONa / C2H5OHOC2H5OH() OCH3H3CHC6H5NH3C6H5H3CHONH2CH3Hetc.nH2CCH2OH3COCH2CH2