版權(quán)說明:本文檔由用戶提供并上傳,收益歸屬內(nèi)容提供方,若內(nèi)容存在侵權(quán),請進(jìn)行舉報(bào)或認(rèn)領(lǐng)
文檔簡介
ChapterThecarbon-carbonChapterThecarbon-carbondoublebond(C=C)isthefunctionalgroupofalkenes.Generalformula:UnsaturatedAlkenescontainlessthanthemaximumofStructureofStructureofTheC=Cbondenergyis605kJ/mol(144.5kcal/mol)inethyleneversus368kJ/mol(88kcal/mol)fortheC-Cbondinethane.Sobondisweakerthe§6-CarbonPosition§6-CarbonPositionofthedoublebondGeometricisomerismacgeometrica≠band acgeometrica≠band a=bornogeometricbdGeometricisomershavedifferentphysicalH CCHHHcis-2-trans-2-GeometricisomershavedifferentphysicalH CCHHHcis-2-trans-2-Relativedensity(at-010-DipoleTheirchemicalpropertiesaresimilarbutnotidentical;theyreactwiththesamereagents,butatdifferentrates(especiallyinbiologicalsystems).HHOOHHOOSelectastheparentstructurethelongestcontinuouschainthatcontainstheC=Cbond.Indicatebyanumberthepositionofthedoublebondintheparentchain.Indicatebynumbersthepositionsofthealkylgroupsattachedtotheparentchain.EachnameisderivedbychangingtheendingofthecorrespondingalkanenametoWhenageometricisomeristobespecified,aprefixisadded:cis-ortrans-,or(Z)-or(E)-.1-(cis-ortrans-)CCHC2-3,3-Dimethyl-1-(cis-ortrans-)2-乙基-1-4-甲基-2-1-(cis-ortrans-)CCHC2-3,3-Dimethyl-1-(cis-ortrans-)2-乙基-1-4-甲基-2-丙基-1-3-甲基-4-HCC(Z)-3-乙基-2-(E)-2,4-二甲基-3-乙基-3-(Z)-1,2-二氯溴乙trans-1,2-二氯溴乙Physical§Physical§6-??????SimilarwiththephysicalpropertiesofInsolubleinwater,butquitesolubleinnon-polarsolvents.Lessdensethanwater.Boilingpoint(b.p.)Meltingpoint(m.p.)Dipolemoment:verysmall,butlargerthan~ofAmethylgroupisanelectron-donatingsubstituentonthedoubleHHHHHHHμ=Amethylgroupisanelectron-donatingsubstituentonthedoubleHHHHHHHμ=HHHb.p.b.p.μ=0.35μ=0.37m.p.-m.p.-ChemicalTheChemicalThefunctionalgroupdeterminesthecharacteristicreactionsoforganiccompound.ofalkenesareoftwo Reactionsthattakeplaceatthedoublebonditselfanddestroyit——additionandoxidation. Reactionsthattakeplaceatcertainpositionshavingspecialrelationshipstothedoublebond——Additionreaction:Areactioninwhichtwomoleculestoyieldasinglemoleculeof+CYCZCCfreeradicalssourceAdditionreaction:Areactioninwhichtwomoleculestoyieldasinglemoleculeof+CYCZCCfreeradicalssourceofelectonsfree-radicalSubstitutionCCCHCCCX(X=Cl,I.CatalyticPt,Pd,or?H=heatofCI.CatalyticPt,Pd,or?H=heatofCC+CHCH1.Heterogeneoushydrogenationandhomogeneousor2.HeatHeatofhydrogenationandstabilityofThetransThetransisomeristhemorestablethanthecisisomer.ThegreaterthenumberofalkylgroupsattachedtothedoublybondedcarbonatomsthemoretheD2,MajorDDD2,+ DDD( D2,MajorDDD2,+ DDD( II.ElectrophilicII.ElectrophilicAdditionofElectrophilicElectrophilicIKI+88-IKI+88-Theregioselectivityofaddition——Theregioselectivityofaddition——Markovnikov’sIntheadditionofanacidtothecarbon-carbondoublebondofanalkene,thehydrogenoftheacidattachesitselftothecarbonthatalreadyholdsthegreaternumberofhydrogens.Stabilityofcarbocations:3o>2o>1o>+3HHActualCHHHMarkovnikov’sElectrophilicadditiontoacarbon-carbondoublebondinvolvestheintermediateformationofthemorestablecarbocation.HHActualCHHHMarkovnikov’sElectrophilicadditiontoacarbon-carbondoublebondinvolvestheintermediateformationofthemorestablecarbocation.Therelativereactivitiesof(CHTherelativereactivitiesof(CH3)2C=CH2>CH3CH2CH=CH2>CH2=CH2>Additionisaccompaniedbyrearrangements.2.Addition2.AdditionofsulfuricTheadditionofsulfuricacidfollowsMarkovnikov’s98%98%CH3CH2OH+3.Addition3.Additionofwater——4.AdditionofBr2/4.AdditionofBr2/ Br2/BrBr2/+Br2/+++++ThisreactionThisreactionisuseful??PreparationofvicinalHCHHHHCCCCH333HCHCHHH HH+CCHStereoselectivereaction:ReactioninwhichasinglestartingmaterialhastheHCHHHHCCCCH333HCHCHHH HH+CCHStereoselectivereaction:Reactioninwhichasinglestartingmaterialhasthecapacitytoformtwoormorestereoisomericproductsbutformsoneofthemingreateramountsthananyofitsstereoisomers.TermssuchasadditiontothelesshinderedsidedescribeStereospecificreaction:Reactioninwhichstereoisomericmaterialsgivestereoisomericproducts.Termssuchassynaddition,antiAnti--III.Free-radicaladditionofnoIII.Free-radicaladditionofnonoMarkovnikovPeroxidePeroxide>Stabilityoffree3o>>Stabilityoffree3o>2o>1o>ThepresenceorabsenceofperoxideshasnoeffectonorientationofadditionofHCl,HI,H2SO4,H2O,IV.Hydroboration-H2O2,CHC+HBCHCBCC BHRH=H,HB+IV.Hydroboration-H2O2,CHC+HBCHCBCC BHRH=H,HB++(1)B2H6,(2)HO, No++δδH-- δ HH HHTransitionstateforAnti-(1)B2H6,HH+(2)H2O++δδH-- δ HH HHTransitionstateforAnti-(1)B2H6,HH+(2)H2O2,OxidationcoldalkalineCCCCCCOO OOK1,2-diolRRC+COOCCHHO KMnO4,CH3CH2COOHOxidationcoldalkalineCCCCCCOO OOK1,2-diolRRC+COOCCHHO KMnO4,CH3CH2COOHKMnO4,O+KMnO4,+Thisreactionisuseful??DeduceKMnO4,O+KMnO4,+Thisreactionisuseful??DeducethestructureofOOCCNaO23OOOCCCCOPhase-transferˉ4Phase-transferˉ4permanganate?2.Ozonolysishas2.Ozonolysishasbothsyntheticandanalyticalapplicationsinorganic3.3.OCH3 H H3H+CC3HOCH3OHHH3++CC HO3Ring-openingpreparationofanti-1,2-OCH3 H H3H+CC3HOCH3OHHH3++CC HO3Ring-openingpreparationofanti-1,2-VI.AllylicHCCC+XCCCX2=Cl2,Stabilityoffreeradicals:CHCH2>3o>2o>1o>>VI.AllylicHCCC+XCCCX2=Cl2,Stabilityoffreeradicals:CHCH2>3o>2o>1o>>lowCH3280-gasOO++ON-O82-VII.MonomerO2nn1×108-1.5×108TiCl4/n VII.MonomerO2nn1×108-1.5×108TiCl4/n n1×105-1×106 CHn22nChemicalpropertiesofChemicalpropertiesofCatalyticElectrophilicaddition(HX,H2SO4,H2O,X2,HOX)AdditionoffreeradicalsSynadditionthatfollowsanti-MarkovnikovAllylicsubstitution2005年Nobel化學(xué)獎(jiǎng)——烯烴復(fù)分解反應(yīng) XXXnR+RXXnR1++n2005年Nobel化學(xué)獎(jiǎng)——烯烴復(fù)分解反應(yīng) XXXnR+RXXnR1++n烯烴復(fù)分解催化劑的發(fā)展概R R R++RRR121Chauvin催化機(jī)理 NO1O FSchrock,3F3C Ph332烯烴復(fù)分解催化劑的發(fā)展概R R R++RRR121Chauvin催化機(jī)理 NO1O FSchrock,3F3C Ph332Grubbs,Grubbs,4Grubbs,PreparationofI.ReductionofRRHHCLindlarPreparationofI.ReductionofRRHHCLindlarRCCNaorliq.II.DehydrationofII.DehydrationofEaseofdehydrationof3o>2o>III.DehalogenationofvicinalCXCX+CCZn/+BrCIII.DehalogenationofvicinalCXCX+CCZn/+BrC2H5O-/IV.DehydrohalogenationofalkylCHCX++ >2o>ReactivityofRXtowardSaytzeff’srule:indehydrohalogenation,themorestablethealkene,thefasteritisformed.StereochemistryoftheE2-IV.DehydrohalogenationofalkylCHCX++ >2o>ReactivityofRXtowardSaytzeff’srule:indehydrohalogenation,themore
溫馨提示
- 1. 本站所有資源如無特殊說明,都需要本地電腦安裝OFFICE2007和PDF閱讀器。圖紙軟件為CAD,CAXA,PROE,UG,SolidWorks等.壓縮文件請下載最新的WinRAR軟件解壓。
- 2. 本站的文檔不包含任何第三方提供的附件圖紙等,如果需要附件,請聯(lián)系上傳者。文件的所有權(quán)益歸上傳用戶所有。
- 3. 本站RAR壓縮包中若帶圖紙,網(wǎng)頁內(nèi)容里面會(huì)有圖紙預(yù)覽,若沒有圖紙預(yù)覽就沒有圖紙。
- 4. 未經(jīng)權(quán)益所有人同意不得將文件中的內(nèi)容挪作商業(yè)或盈利用途。
- 5. 人人文庫網(wǎng)僅提供信息存儲空間,僅對用戶上傳內(nèi)容的表現(xiàn)方式做保護(hù)處理,對用戶上傳分享的文檔內(nèi)容本身不做任何修改或編輯,并不能對任何下載內(nèi)容負(fù)責(zé)。
- 6. 下載文件中如有侵權(quán)或不適當(dāng)內(nèi)容,請與我們聯(lián)系,我們立即糾正。
- 7. 本站不保證下載資源的準(zhǔn)確性、安全性和完整性, 同時(shí)也不承擔(dān)用戶因使用這些下載資源對自己和他人造成任何形式的傷害或損失。
最新文檔
- 2024年汽車銷售合同擔(dān)保服務(wù)模板附車輛改裝服務(wù)3篇
- 2024年短期公租房租賃合同
- 崗位職責(zé)表課程設(shè)計(jì)
- 2024幼兒園發(fā)展規(guī)劃(35篇)
- 基于機(jī)器學(xué)習(xí)的古代繪畫修復(fù)與復(fù)原技術(shù)研究
- 2024年?duì)I銷工作計(jì)劃(59篇)
- 沼氣池儲氣罐課程設(shè)計(jì)
- 線描西蘭花課程設(shè)計(jì)
- 英漢互譯系統(tǒng)的課程設(shè)計(jì)
- 物流行業(yè)運(yùn)輸司機(jī)工作總結(jié)
- (八省聯(lián)考)河南省2025年高考綜合改革適應(yīng)性演練 生物試卷(含答案)
- 人工智能銷售工作總結(jié)
- 2025年中小學(xué)春節(jié)安全教育主題班會(huì)課件
- 工商注冊租房合同范例
- 2023-2024學(xué)年廣東省深圳市羅湖區(qū)八年級上學(xué)期期末生物試題
- 【9物(北師)期末】阜陽市臨泉縣2023-2024學(xué)年九年級上學(xué)期期末考試物理試題
- 2025年醫(yī)院保衛(wèi)科工作總結(jié)及2025年工作計(jì)劃
- 班會(huì)課件高中
- 部編版一年級上冊語文第一單元-作業(yè)設(shè)計(jì)
- 安全生產(chǎn)泄漏課件
- 陜西省西安市高新第一中學(xué)2023-2024學(xué)年八年級上學(xué)期期末歷史試題
評論
0/150
提交評論