北師有機化學上第8酚醚

第八章醇、酚、醚第八章醇、酚、醚第一節(jié)第一節(jié)第二節(jié)醇酚第三節(jié)醚第一節(jié)醇—醇的分類和命名二醇的三醇的性質(zhì)(一)(一)分類：酚叔醇叔醇伯醇伯醇仲醇(二 為主鏈。 最小。

巰基硫醇酚羥 –R（?。┩榛?烷氧基醚 苯基苯

醇羥 酰 甲酰 –R（大）烷基烷 烯基

磺酸基磺酸 氨基

羧 1-Methylpentyl1-Methylpentyl1,1-二甲基丁醇1,1-Dimethylbutyl2-己醇2-甲基-2-戊醇6-甲基-3-6-甲基-3-2-甲基-5

H

H

氯甲基-

（R）-3 11276345 11276345OH

8

bicyclicringtakesprecedenceoverthelocationof-OHcis-3-Methylcyclohexanol Bicyclo[4.4.0]decan-3-CompoundsCompoundscontainingmorethanone-OHgrouparenameddiols,triols,etc.CH2OHOH

CH3CHCH2 OH

CH2CHCH2HOHO OH二制(一由烯烴來(二格氏合成法(三)(四由鹵代烴來(五還原反應(一)由烯烴 烯烴 作烯烴與濃硫酸作用,水解烯烴 化作烯烴與次鹵酸作用烯烴 作B2H6,H2O2,

特點:如1-丁烯 立體專一性強,順式加成.2.H2.H2O2,例1.1.HHH（反）-2產(chǎn)率 唯一產(chǎn)HB H2O2, 相比：操作更簡便；選擇性更高9-BBN22.

C

+

CH3C

?存在重排產(chǎn)物?反應需在酸催化下，與水的加成；?反應遵守馬氏規(guī)則;?存在重排產(chǎn)物OH特點:??反應遵守馬氏規(guī)則;?存在重排產(chǎn)物3.4烯烴羥4烯烴羥HCCC特點:遵守馬氏規(guī)則;特點:遵守馬氏規(guī)則;不發(fā)生重排 條件溫和，產(chǎn)率高HHCCCOH 5.5.C8+H3CC此反應遵循馬氏規(guī)則反式加成CCCCCCCCOOOO6.特點:特點:順式加成;產(chǎn)物為鄰二醇羥基.PreparationPreparationof1,2-TheThetwosyntheticroutesto1,2-glycolsleadtodifferentstereochemistries.例例OsO4叔丁醇NaBH4NaBH4或7)臭氧化(OzonolysisofCC+CC+COOCOC+C臭氧化物在鋅作用下，生成相應醛酮；在臭氧化物在鋅作用下，生成相應醛酮；在NaBH4,LiAlH412341234RRRO1.例例+OAdditionAdditiontoEthylene

2.2.RRR RCRCformaldehydetogiveprimaryalcoholsaldehydestogivesecondaryalcoholsketonestogivetertiaryalcoholsesterstogivetertiaryalcohols3.8–8–O?RC???例例8–8–HHO?HRCHO???HRCHOH例例COH例例++O4.4.8–8–O?RCO???RCOH ysisofCH3C—

TherearetwootherCanyousee

OC—OCOCMg2.2.C2CH3MgBr

TwooftheTwoofthegroupsattachedtothetertiarycarboncomefromtheGrignardreagent.MechanismMechanismfortheReactionanEsterwithaGrignard++O CH2CH2MethodstoProtectAnAnexampleofTMS-alcoholprotectionina(三(三)1金屬鋰試劑與醛作用Formation1金屬鋰試劑與醛作用FormationofOrganolithium++RR=1°,2°,some3°,vinylandaryl(phenyl)rate:X=I>Br>Cl(bromineispreferred)solvents:ethers,pentane,benzene

+

+Br+

++OO+1.1.乙醚,2.+1.+1.2.OC2.(四(四由鹵代烴來醇+++HCHCRCORCO酮(五)RCORCOH醛RHCHRHRHC11

Pt醛HH酮O +O+2OOOO例HH2(100atm)Ni,125°C2.2.RR HHTheseThesereagentsaresourcesofhydrideion,H:ˉ,averypowerfulnucleophile.H+H–H+H– HHH– H硼氫化鈉Sodiumnotsensitiveto氫化鋰鋁Lithiumaluminummorepowerful,veryreactivewithH2OOneOnemoleofNaBH4reducesfourmolesofaldehydeorOHONa+H-B-H+R-C-H

OBH3Na+R-C-R'H

H2

R-C-fromthehydridereducingagentR-C-HExamples:Sodium O醛酮OHRCH=CHCR'O

NaH2

OHRCH=CHCHR'O

RCH2CH2XXLithiumLithiumaluminum需用乙醚或四氫呋喃需用乙醚或四氫呋喃(THF)O醛

O(CH)

(CH) 5酮

5

1.LiAlH1.LiAlH42.H無論是無論是NaBH4或O33.用LiAlH4只有只有LiAlH4可作為還原劑NaBH4則很難RCORCORHCH

LiAlH4，乙醚MechanismforthereactionofacarboxylicacidwithLiAlH4例OO+ReductionofEstersGivesPrimaryMechanismMechanismforthereactionofanN-substitutedamidewithLiAlH4MechanismMechanismforthereactionofanN,N-disubstitutedamidewithLiAlH4一一物理性質(zhì)(二化學性質(zhì)(一)物理性質(zhì) H O l=1.7沸點瞬間偶極沸點瞬間偶極,0 所有液態(tài)的醇密度約0.844）C—O1025-1200cm–1(C—O1025-1200cm–1(寬O—H3200-3650cm–1(寬 InfraredInfraredSpectrumof1H

o0.5-5 Ho3.3-4 ((o,?醇的分子離子峰很??；?醇的分子離子峰很??；?基峰為(M主峰常為失去烷基的含RR+ProtonatedProtonatedbystrongacidstooxoniumions,ROH2+醇的酸性與水相似，是弱酸醇的酸性與水相似，是弱酸；它們的共軛堿是強堿；水是比醇更強的酸, 醇共軛堿的堿性較水的共軛堿強氨是非常弱的酸，它們的共軛堿是非常強的堿.酸1.8x10-–RCH28OH(二)11.與活潑金屬作用2.洋鹽的形成3.與酸的作用4.取代反應5.脫水反應6.氧化反應7.多元醇的特殊反應Reactionsof ++++醇的活性：1o2o>+常見的活潑金屬有：常見的活潑金屬有：NaKMgStericeffectsareStericallyaccessible;lesshinderedandmoreeasilysolvated.

Stericallylessaccessible;morehinderedandlesseasilysolvated.Electron-withdrawinggroupsstabilizealkoxideandlowerpElectron-withdrawinggroupsstabilizealkoxideandlowerpKa.+HOSO2HH H水可使Yang O+OO+O+3aa）例例OO+O+bb）與酸酐 +OO+OO+O例例 +OO++++常見的無機酸有：常見的無機酸有：–O與HONO2

CH

CH3OSO CH3OSO2OH+H2O+++44醇的取代反應與與HX++R3COH>R2CHOH>RCH2OH>三級 二級 一級 甲HX的活性：HIHBr>性差的不適用；羥基易重排。OO:+HH+O:+..Htert-butyloxonium的離去基團,需要在酸的幫助下,生成水合正離子.Step+H+HStepHHtert-ButylH洋鹽C-O鍵的正離子.C親電試劑C親電試劑....l++..:.lStepterttert-Butyl(Lewis堿(Lewis堿) (Lewis酸(Lewis酸)OHH

(CH)3HOH

盧卡斯盧卡斯（Lucas）

叔醇立即混濁（反應按SN叔醇立即混濁（反應按SN1）；仲醇放置3-5伯醇加熱后冷卻混濁（反應按

(CH)CCl+(CH)CCl+H32Step Yang

O:+H+O:H..

Step2:Step2:氧離子與鹵負離子作用+:.

H

– .

H

OH StepStepO:+HH+O:+..H+HHStepStep2:氧離子與溴離子作用H..++H NaBrH2SO4

++Br++亞硫酰氯?亞硫酰氯

SOCl2+ RCl+HCl+OSOSCl

K23(常用吡啶代替三溴化磷PBr3+ 常加吡啶、K2常加吡啶、K2CO3堿性試劑，除去反應中生成的55+CH2RLowtempandbelow,favorsetherHightempandabove,favorsalkene +StepStepO:+O:+H HHH++HH+Step機HH+O:HHHStepStepC機HH+CH+H+H+HH10901090TheZaitsev++TheTheZaitsev消去反應發(fā)生在

twoprotonsonthis?carbonthreeprotonsonthis?carbononlyoneprotononthisTheZaitsevTheZaitsevRRRRCCCHCRonlyoneprotononthis例例++++機機C+ H3H3PO4 ++HH+重 +HHHH+HHH+H例例HH2SO4,機機Step??Step??CHCH3HOSO2H H+–OSO2機機StepStepHHCH32H+H??CHH3HHHH機StepStep++H?–OSO2O?O?OHHO?HDehydrateDehydratewithconc.H2SO4,thenaddCH

alcohol

alkene

alkaneTosylate,Tosylate,thenreducewith

6氧化反應Ofrom6氧化反應OfromORRROO1）1）一般氧化劑H2OHH2OHCHCOHCOOOOCCO H2Cr

acetone

Cr32-Isopropyl-5-methyl-cyclohexanol(Menthol)

2-Isopropyl-5-methyl-cyclohexanone(Menthone)2）2）NitricacidO硝酸是強氧化劑硝酸是強氧化劑,斯試劑CollinsCrO3吡啶（CrO3in瓊斯試劑Jones鉻酸 （chromicacidinPDC氧化劑:PCC氧化劑吡啶的氯鉻酸鹽活性MnO2二甲亞砜類氧化劑斯試劑CollinsreagentCrO3/OCrO3吡啶

2

CrO3吡啶 CH

于分子中含有對酸敏感的基團,如縮醛或碳碳雙鍵的瓊斯試劑瓊斯試劑Jonesreagent CrO3

,H

2特點:OOHH+H–特點:氧化伯醇或仲醇為醛或酮的同時，不氧化碳碳PDCPDC吡啶的重鉻酸鹽OOH OH特點:氧化伯醇或仲醇為醛或酮的同時，不氧化碳碳雙鍵、三鍵以及硝基?；鶠槿┩?不氧化不飽和鍵、一般醇。O◆AlbrightGoldman(二甲亞砜和乙酐)Moffatt(二甲亞砜和二環(huán)已基碳酰二亞胺◆AlbrightGoldman(二甲亞砜和乙酐)Moffatt(二甲亞砜和二環(huán)已基碳酰二亞胺）歐芬腦爾Oppenauer氧化劑RHRHCRO+C RCORRCOR+ （甲乙酮，環(huán)己酮）氧化成酮， 一反應稱為歐芬腦爾(Oppenauer,R.V)氧化法，其逆反應稱為麥爾外因-彭道夫(Meerwein-Ponndorf)R2CHOH

R2C=O

CHCHCH 麥爾外因-彭道夫還原：異丙醇大大過量,邊反應,邊將 反應只在醇和酮之間發(fā)生HOOOOCCCCCO+OCO+OPeriodicPeriodicCleavageofSameproductsformedasfromozonolysisofthecorrespondingalkene.

HC

H OC

頻哪重排Pinacol頻哪重排PinacolThiolsThiols硫醇是含有巰基（mercaptogroup，SH）的一類化合物 TheTheflavorofgarlic,leeksandonionsisduetheextrusionofvolatilesulfurcompoundsuponhavehavepKasofaboutcandeprotonatedinaqueous+++(pKa=10)(pKa=15.7)

+

SSN2usingthioureaassource nucleophilicsulfur.HydrolysisinbaseHydrolysisinbaseconvertstheisothiouroniumsalttothedesiredthiol

.+.

第二節(jié)二、酚

酚C—O鍵距136pm,比甲醇稍短CH3OH142椅式構(gòu)象無芳香性酸性極微弱有芳香性麝香草酚

CO

2對羥基苯甲 5-5-氯-2-

巰基硫醇酚羥 –R（小）烷基烷 烷氧基醚 苯基苯

醇羥 酰 甲酰 –R（大）烷基烷 烯基

磺酸基磺酸 氨基 2-羥基-1-7-氯-8-2-羥基-1-7-氯-8-硝基-2-1-甲基-2-12

360oC，加壓

熔融SO2熔融SO2,制備 + COCO+CO+CO+OC+CO機理

H2O,

((一物理性質(zhì)((二化學性質(zhì)(一物理性質(zhì)

(g/100

O—HO—H3600cm- ；C—O1200-1250cm- 11H o4-12204204256210270235287m/zm/z(二11水水?OHKa=?OHKa=10-+ CHCHCH?? 3HKa=10- +CH–3 體體

O –

?O? ??

O?? O??OHHH?? H

H

H H

?– 酚不能與酚不能與NaHCO3+++ 1x10-5x10-6x10-1x10-4x10-7x10-6x10-4x10-7x10-7x10-1x10-4x10-SubstitutedSubstituted––HHHHON+??O????HHHHN+??O?2酚分子中的C—O由羥基間脫水 ，一般采用Williamson合成法++WilliamsonWilliamsonONaONa++ +++F+F++例 + 例

OH+OH+O6所有的酚類及脂肪族烯醇式醇類化合物均可與FeCl3紫色紫色顏色對甲苯酚紫色綠色紫色OOK2Cr2OOK2Cr2O7,4Na2Cr2O7,

OO5.5.羥基是強的鄰對位定位基，活化苯環(huán)，反應比苯容易鹵化Halogenation硝化亞硝化Nitrosation磺化 柯爾貝Kolbe++鹵化+F+FF鹵化硝化

+

硝化硝化?

H2SOH2SO4,H2O亞硝化H24柯爾貝6OOOOOOO+O+OAlCl3催化使芳香酯該反應稱為Fries重排

(CH) 2 第三節(jié)醚（Ethers）一、醚的結(jié)構(gòu)介紹介紹ThediscoverythatinhalingThediscoverythatinhalingetherscouldmakeapatientinsensitivetopainrevolutionizedthepracticeofmedicine. OHOHHOHOOO CH3CHCH3CH2OCH21-氯-3- ethylmethyl CHCH CH3CH2OCH2diethyl

chloropropylethyl3-名CH3CH名CH3CH2SCH2（硫代甲基）烷基作取代基，ethylmethyl

CH3CH2SCH2diethyl

cyclopentylmethyl名O (Ethylene

氧雜環(huán)戊烷O

氧雜環(huán)己烷

1,4名O OSSSSSSSS硫雜己環(huán)1酸催化脫水H2SO4, +

+CH3CH2CH2CH2OCH2CH3+2Williamson醚合成法SN2親核取代反應伯鹵代烷有如下事實有如下事實甲基和1o鹵代烷產(chǎn)率高2o鹵代烷產(chǎn)率低(competing歸elimination)3o鹵代烷發(fā)生歸消除是唯一的產(chǎn)物.CH3

O-Na+ 2-Bromo-2-methylpropane

Sodiummethoxide

CH3C= CH3OH2-Methylpropene

Na+Br-++例

++E2E2消除機理33醇與烯加成+CH2=烯烯烴的溶劑化作用：

+

NaBH4OHˉ

O(一)boilingboiling水中的溶解度(g/100O水中的溶解度(g/100O99C—O10701150cm-1

WaveWavenumber,cm-1H1H83.3-4.0880.881.480.8CH3CH2CH2OCH2CH283.2 ChemicalChemicalshift(8,m/zm/z +

m/z

m/z(二醚的化學性質(zhì)的溶劑；醚在空氣中易被氧化成過氧化物，過氧化物不穩(wěn)定，加熱或蒸餾易分解。CHCHCHCHCHCH3222O3+OHYang2Yang對能接受質(zhì)子，生成Yang醚可與缺電子試劑，如：BF醚可與缺電子試劑，如：BF3，RMgX等形成Yang鹽(絡(luò)合物)．BF3，RMgX均以此形式保存于乙醚中R?OR?OR+RO?R3.3.OODoDonotdistilltoStoreStoreinfullbottleswithtight 醚蒸干，易分解，發(fā) 檢查是否有過氧化物存在淀粉碘化鉀紫 血紅色44CH3CHCH2CH3CH3醚和濃的醚和濃的HIHBr作用時，醚鍵斷裂；一般來講，3o按SN1歷程進行，1o按SN2歷程進行；醚鍵的斷裂先小后大，芳基不變；可用于保護酚羥基。3o3oandbenzylicethersareparticularlysensitivetocleavagebyHX.tert-ButylethersarecleavedbyHClatroomO-CCH3

OH+ Cl-C-CH3 InInthiscase,protonationoftheetheroxygenfollowedbyC-Ocleavagetogivethetert-butyl?H3H??+O3H機?I?HOHO+++??RBr??++R?? HRR??OH++CH3CH2—加熱+生成烷基鹵代物和苯酚OO例例例4OH機OH機OClaisenOOheatOOAllylphenylether

TransitionstateOOHAcyclohexadienoneintermediate

keto-enoltautomerism

o-ABenzylhexylCHO(CH)BenzylhexylCHO(CH)223CH3+BenzylicBenzylicethersarecleavedunderconditionscatalyticBenzylToTocarryouthydroboration/oxidationofalkene,thephenolic-OHmustfirstbeprotected;itisacidicenoughtoreactwithBH3anddestroythereagent.HHProtectthephenolic-OH,carryoutthehydroboration/oxidation,andthenremovethebenzylprotectinggroupbyhydrogenolysis.Protectthephenolic-OH,carryoutthehydroboration/oxidation,andthenremovethebenzylprotectinggroupbyhydrogenolysis.

BH3?H2O2/

Pd/2-(3-EthersEthers-ProtectingSupposeSupposeyouwishtocarryoutthisHCCCH2CH2CH2OH

TreatingTreatingthecompoundwithonemoleofNaNH2willgivethealkoxideanionratherthantheacetylide.HCCCH2CH2CH2OH+Na+NH2 4-Pentyn-1-HCCCH2CH2CH2O-Na+ +NH3TheunprotectedalkyneTheunprotectedalkyneisformedbyformedbytreatmentofanalcoholwith2-methylpropeneinthepresenceofanacidcatalystThetert-butylprotectinggroupisbytreatmentwithaqueousEthersEthers-ProtectingTrimethylsilylTrimethylsilyl(TMS)Treatthealcoholwithchlorotrimethylsilaneinpresenceofa3oamine,suchasThefunctionofthe3oamineistocatalyzethereactionandtoneutralizetheHCl.

Cl-Si-CH3Chlorotri-

(CH3CH2)3

RCH2O-Si-CH3Atrimethylsilymethylsilane etherTheTMSgroupisremovedbytreatmentwithaqueousacidorwithFˉintheformoftetrabutylammoniumfluoride. 1 O ????OHHOHHHHHHO例HHHHORRRO2.例例+O+ORRCHO例例O

機機 O– ––??

?

H

O?H例例O乙醇-水HHHHOHHCCHORRHS HRROHH H2H3OH親核試劑從背面進攻SN2++O OLiAlH4LiAlH4,乙醚H2SO4,OHHRROH

CH

HHOH H O 生成生成BrCH2C