中國(guó)農(nóng)業(yè)大學(xué)有機(jī)化學(xué)課件第十章 醇酚醚

Chapter10.

Alcohols,PhenolsandEthers10.1.1Classificationandnomenclature10.1AlcoholsGeneralformulaR—OHNumbersofOHgroupsAlcoholDiolsPolyalcoholsKindsofhydrocarbonylAromaticAlkalicCyclicSaturatedUnsaturatedenolketoneAldehyde10.1.2Nomenclatureofalcohol

n-Butanoliso-Propanolt-ButanolTriphenylMethanol10.1.2.1CommonNomenclature10.1.2.2SystemicNomenclature2,4-dimethyl-2-pentanol2-chloroethanol3-buten-2-ol5-methyl-2-ethyl-1,3,5-heptanetriolcis-1,2-cyclohexanediol練習(xí)、用系統(tǒng)命名法給以下化合物命名Crystalalcohol：低級(jí)醇與無(wú)機(jī)鹽形成的分子化合物10.1.3PhysicalPropertiesofAlcoholsboilingpointofalcohols10.1.4ChemicalpropertiesofalcoholsReactivecenters:10.1.4.1Reactionwithactivemetals(similartowater)reactivityofalcohols：CH3OH>1°>2°>3°Manufactureofsodiumethoxide：Othermetalalcoxides:異丙醇鋁四乙醇鈦〔鈦酸乙酯〕叔丁醇鋁10.1.4.2DisplacementofOHbyhalogenatom

(1)reactionwithhydrogenhalidesReactivityofhydrogenhalides：HI>HBr>HClReactivityofalcohols：allylandbenzyl>3°>2°>1°>CH3OHAllylandtertiaryalcoholsr.t.DelaminationimmediatelySecondaryalcoholsr.t.DelaminationafterstandingforafewminutesPrimaryalcoholsr.t.NoreactiontakeplaceReactionphenomenaofdifferentalcoholswithLucas’reagentLucas’reagentZnCl2+HClAllyl,tertiaryandsecondaryalcohols〔SN1〕Reactionmechanism：Primaryalcohols〔SN2〕Thedifferencesofnucleophilicsubstitutionbetweenalcoholsandalkylhalides：◆catalystisnecessaryforalcohols

refractiveindexofC—ObondandC—Xbond(Rn)(cm3/mol)3.766.579.4714.51◆notsimplefirstorsecondorderreactions，thereactionrateisalsocorrelatedtotheconcentrationofacidSN1:v=k[ROH][H+]SN2:v=k[ROH][H+][X-]Sidereaction—molecularrearrangement(2)reactionwithphosphorushalidesmechanism：mechanism：(3)ReactionwithsulfinylchlorideSNi(SubstitutionNucleophilicinternal)mechanism：10.1.4.3DehydrateSaytzeffalkenes(1)intramolecule〔elimination〕Reactivity:

tertiary>secondary>primarymechanism〔E1〕Sidereaction：molecularrearrangement(2)intermolecules〔nucleophilicsubstitution〕SN2Synthesisofmixedethers10.1.4.4Formationofesters

(1)reactionwithmineralacids(2)Reactionwithorganicacids硝化甘油硫酸二甲酯10.1.4.5OxidationanddehydrogenationHemiacetalesterSidereactionConceptsofoxidationandreductioninorganicchemistryOxidation=addedoxygenorshuckoffhydrogenReduction=addedhydrogenorshuckoffoxygen101.4.6Reactionsof1,2-diolsGeneralproperties：(1)OxidationbyHIO4mechanism：Similarreactions：(2)Dehydrating片吶醇片吶酮R=CH3,Yield72%10.1.5Preparationofalcoholsinlaboratory10.1.5.1alkeneasthestartingmaterials

(1)hydroboration-oxidation(2)oxymercuration-reduction10.1.5.2Carbonylcompoundsasthestartingmaterials(1)reductionofcarbonylcompoundsa.catalytichydrogenation25℃reactivityb.reductionwithmetalhydridesmetalhydridesincommonuse：NaBH4,KBH4,LiBH4,LiAlH4,AlH3c.reductionbyborane(2)additionwithGrignardreagent10.1.6Representatives10.1.6.1Methanol(木醇、木精)300°CIndustrialmanufacture:10.1.6.2Ethanol〔酒精〕Brewageofwine糖化階段酒化階段10.1.6.31,2,3-Propanetriol(glycerol)10.1.6.5phenylmethanol〔benzylalcohol〕10.1.6.41,2,3,4,5,6-cyclohexanehexol〔inositol〕10.2EliminationAreactionwhichasmallmoleculeisshuckedofffromthemothermolecule1,3-elimination(-elimination)1,1-elimination(-elimination)Classification：1,2-elimination(-elimination)10.2.1—elimination10.2.1.1mechanism(1)doublemoleculeselimination〔E2〕◆mechanismCCH3CH2OH

+

CH3CHCH2+

BrH3CH2O-

+

HCHCH2BrCH3CH3CH2OHCHCH2BrCH3Include:primaryhalides,quaternaryammoniumsaltsreactwithstrongalkaliDynamicequation：

v=k[CH3CH2CH2Br][CH3CH2Oˉ]

Dynamicequation：v=k[HCR2-CR2–L](2)singlemoleculeelimination〔E1〕慢mechanism：Include:departureofhydrogenhalideintertiaryhalides,dehydrationofalcoholsunderacidcatalyzingSidereactions：rearrangementandnucleophilicsubstitutionE1cbreaction(conjugatedbase)SimilartoE1cbSimilartoE2E1cbTypicalE2TypicalE1ThepossibilityofC-HbonddisconnectionincreasedChangeabletransitionstatetheory10.2.1.2Orientationofelimination(regioselectivity):E2：〔1〕dependonthestabilityofproduct(alkene)e.g.Thestabilityalsodecidesthereactivityofalkylhalides(2)bulkoftheleavinggroupL2-戊烯（%）1-戊烯（%）Br6931I7030OSO2R5248S+(CH3)21387N+(CH3)3298離去基團(tuán)L(在中)的體積對(duì)E2方向的影響(3)BulkofalkaliC2H5Oˉ7030(CH3)3COˉ27.572.5C2H5(CH3)2COˉ22.577.5(C2H5)3COˉ11.588.5試劑2-甲基-2-丁烯（%）2-甲基-1-丁烯（%）不同堿對(duì)的E2方向的影響(4)Blockof-H化合物產(chǎn)物1-烯（%）2-烯（%）19818614-H的空間位阻對(duì)E2方向的影響〔試劑C2H5Oˉ〕E1：Undergeneralconditions,thepredominantproductisSaytzeffalkenewhichdeterminedbystabilityofalkene.ButHofmannalkenewillbethepredominantproductif-Hsarehinderedbylargergroups.e.g.10.2.1.3Thecompetitionofeliminationandnucleophilicsubstitution

(1)structuralfactors(2)Strengthofthealkaliusedstrengthofalkalisincommonuse：NH2ˉ>ROˉ>HOˉ>CH3COOˉ>Iˉ(3)Polarityofthesolventused：極性大不利于電荷分散，因此不利于消除反應(yīng)物溫度/°C無(wú)水乙醇%含20%水的乙醇%歷程(CH3)3C-Br2519.612.6E1(CH3)2CH-Br557159E2(4)TemperatureHighertemperatureisinfavorofelimination10.2.1.4StereochemistryofeliminationE1：nostereoselectivityE2：anti-elimination10.2.1.5Hotelimination200～500°CmechanismAttestations：10.2.2-eliminationcarbenedichlorocarbenedifluorocarbene10.2.2.1Electronicstructuresofcarbene°°10.2.2.2Reactionsofcarbene80%10%10%++問(wèn)題、用溴處理(Z)-3-己烯，然后在KOH-C2H5OH中反響，可得(Z)-3-溴-3-己烯；但用相同試劑及順序處理環(huán)己烯，卻不能得到1-溴環(huán)己烯。用立體結(jié)構(gòu)表示這兩種烯烴的反響過(guò)程及反響產(chǎn)物。問(wèn)題、預(yù)測(cè)以下兩個(gè)化合物在乙醇中與乙醇鈉反響的主產(chǎn)物，如將堿換成三乙基甲醇鈉情況又如何？10.3Phenols10.3.1Structureandnomenclatureofphenolseg.鄰甲苯酚

2-甲苯酚鄰苯二酚

1,2-苯二酚鄰羥基苯甲醛

2-羥基苯甲醛-萘酚鄰甲氧基苯酚

2-甲氧基苯酚2,4,6-三硝基苯酚

〔苦味酸〕練習(xí)、用系統(tǒng)命名法命名以下化合物10.3.2Physicalproperties10.3.3Chemicalproperties10.3.3.1ReactionsonO-Hbondi.acidityⅱ.reactionswithFeCl3紫色ⅲ.formationofaryletherseg.10.3.3.2reactionsonbenzenering⑴halogenation0℃白色黃色⑵nitration20℃40%13%IntramolecularhydrogenbondIntermolecularhydrogenbond苦味酸〔pKa=1.6×10-1〕⑶nitrition⑷condensation7～8℃10.3.3.3oxidationp-benzoquinoneo-benzoquinone10.3.4Representatives10.3.4.1phenol無(wú)色針狀結(jié)晶，mp43℃,有特殊氣味。

manufacture：①Throughsulfonation320-350℃200℃②Throughchlorobenzene425℃③Throughoxidationofiso-propylbenzene110-120℃80-90℃10.3.4.2HydroquinonePrincipleofdevelopment

manufacture10.3.4.3a–naphtholandb-naphthol-naphthol-naphthol

manufacture:200℃,1.4MPa-naphthol-naphthol10.4Ethers10.4.1structureandnomenclature通式R–O–R′〔R=R′單醚；RR′混合醚〕′110℃nomenclature：Commonnomenclature(usuallyusedforsimpleethers)eg.甲醚苯醚異丙醚甲基叔丁基醚苯甲醚IUPACname〔forperplexingethers〕eg.2-甲氧基-3-乙基己烷4-羥基-3-甲氧基苯甲醛(香蘭素)

nameofcyclicethers:環(huán)氧乙烷四氫呋喃

1,4-環(huán)氧丁烷二噁烷

1,4-二氧六環(huán)

nameofpolyethers：乙二醇甲乙醚二縮二醇單甲醚10.4.2Physicalpropertiesofethers10.4.3Chemicalproperties10.4.3.1FormationofprotonatedethersFormationofcomplexeswithLewisacid：CatalystusedinFridel-Craftssubstitution10.4.3.2