有機(jī)化學(xué)上冊(cè)課件朱衛(wèi)民7芳香烴

OnJune1,2007,abouttenthousandOnJune1,2007,abouttenthousandcitizensparaded()beforethemunicipal(市政的buildingin()againstthislargestchemicalindustrialprojectinthehistoryofChapter7AromaticAliphatic~(脂肪烴)Hydrocarbons(烴)Alicyclic~(脂環(huán)烴)Aromatic~,arenes(芳香烴Aliphatic:fatty Aliphatic:open-chainAromatic:fragrant Aromatic:benzene(苯) Aromaticity(芳香性cyclicandfullyconjugated4n+2πelectronsinthesystemtheentiresystemisnarspecialchemicalstabilitysubstitutionreactionsinsteadofadditionMonocyclicMonocyclicarenes(單環(huán)芳香烴)(聯(lián)苯類 Multiphenylaliphatic(多苯代脂肪烴 Fused-ring(稠環(huán)芳香烴 Nonbenzenoid Heterocyclic(非苯體系 (雜環(huán)化合物 N 7.1Structureofbenzene(苯的結(jié)構(gòu) Kekulésuggestedthattwoisomericstructurescouldexistbutinterconvertedtoorapidlytobeseparated.(互變異構(gòu))Butbenzenebehavesunlikeansp 7.27.2Nomenclatureofderivativesofbenzene(名 苯作為甲(基) 異丙氯(代)1,2-二甲苯1-甲基-3-乙基苯鄰二甲苯間甲乙苯o-二甲苯m-苯苯作為取代CH-Ph- 2,3-二甲基-4-苯基己 苯乙 苯甲 2-苯基丙 α-苯基丙 鄰苯二甲(酸) 苯 對(duì)苯二 間苯二 1-苯基乙醇苯磺基團(tuán)基團(tuán)的重要-COOH>-SOH>-COOR>-COX>-CONH>-OCOR>-CN>-CHO>-COR-OH>-NH>-OR>-R>-X>-NO>- 對(duì)硝基氯 鄰羥基苯甲 鄰乙酰氧基苯甲水楊 乙酰水楊酸(阿司匹林苯乙 鄰乙?；郊姿峒?.3Physicalpropertiesofbenzene(苯的物理性質(zhì)7.4ReactionsofbenzeneElectrophilicsubstitution(苯的化學(xué)反應(yīng)親電取代Electrophilicsubstitution(親電取代)Addition(加成)Reduction(還原):Birchreduction(還原),catalyhydrogenation(催化氫化)Oxidation(氧化)Electrophilicsubstitution(親電取代π絡(luò)合一級(jí)同位素效應(yīng)Hσ絡(luò)合EHEHEHEHE H7.4.17.4.1Nitration(硝化OH 3,25 ONOHNO+HSO+NO+HNitroniumNO -H1.H/Pd-2.1)FeorSnorZn/HCl3.1)SnCl/HCl7.4.2Halogenation(鹵化+ClFe+△X2+X++XH-XReactivityofhalogens(鹵素的活性F>Cl>Br>Otheragents(其它試劑IClRCOOXHOX7.4.37.4.3Sulfonation(磺化concentratedorfuming OSO+ClSOH氯磺O苯磺酰H--HOSulfonationisDesulfonationcanbe plishedbyusingdilutesulfuricacid,orbypassingthroughthereaction.conc.conc.H + 100℃SO7.4.4Friedel-Crafsalkylation(傅-克烷基化CharlesFriedel+AlClorJamesMasonCraftsR-+ X×X AlCl×RF>RCl>RBr>+ Otheralkylationagents(其它烷基化試劑alkenes(烯)alcohol(醇)epoxides(環(huán)氧化合物+CHCH=CHCH+ CHCHCHCH+ HSO+ ActivityActivityofsubstrates(底物的活性YY=NO,N+Me,COH,COR,CF,SOH,NH,NHR,NR×Carbocationrearrangementsoccur(碳正離子發(fā)生重排Polyalkylationscanoccur(會(huì)發(fā)生多烷基化+CHCl+ 100℃F-Calkylationisreversible(傅-克烷基化是可逆反應(yīng)+AlCl++ + ++ClCHCH CH 7.4.5Friedel-Crafsacylation(傅-克?；?ClemmensenReduction:Zn(Hg)/HCl,Wolff-KishnerReduction:HNNH/OH-,O +HCO++ OOActivityofreagents(試劑的活性RCOCl>(RCO)O>F-Cacylationisirreversible(傅-克酰基化是不可逆反應(yīng)Rearrangementorpolysubstitutiondoesnotoccurwithacylation(?；话l(fā)生重排或多酰基化)Activityofsubstrates(底物的活性Y=NO,N+Me,COH,COR,CF,YNH,NHR, CCHCHC OZn/ CHdoesn’t-7.4.67.4.6Blancchloromethylation氯甲基化 +HCHO+CHCl氯化芐基 一苯一氯甲 HH-H HCHOH H 其它引入氯甲基的方法 +HCHO+ CHCl +HCHO+ CH H+/H CHNH CO+-HC+H-RCN/HCl-ZnCl,甲?；?7.4.7Gattermann-Kochformylation(H-C≡N+HCl→H-C=NH Gattermannacylation適用于烷基苯，酚，酚醚混混 ++Activator(活化基Deactivator(鈍化基o,p-Director(鄰對(duì)位定位基m-Director(間位定位基混 ++7.57.5Directingeffectsofsubstituents(取代基的定位效應(yīng)ClassificationofSubstituentsinElectrophilicAromaticSubstitutionStrong-O-,-NR,-NHR,-NH,-OH,-Ortho&Moderate-NHCOR,-Weak-R,-CH,-Weak-F,-Cl,-Br,-I,-CHX,-CH=CHCOOH,-Moderate-CHO,-COR,-COR,-COH,-Strong-CN,-SOH,-NO,-CF,-CCl,-Allactivatingsubstituentsareortho,paraHalogensubstituentsareslightlydeactivatingbutareortho,para-Stronglydeactivatingsubstituentsaremeta分析各基團(tuán)的電子效應(yīng)EE？Multiplesubstituenteffects(多取代基效應(yīng)1)取代基的定位效應(yīng)一致時(shí)，它們的作用相互加強(qiáng)取代取代基的定位效應(yīng)時(shí),考慮活化基或鄰對(duì)位定位基或弱鈍化不同類型的取代基相互處于間位時(shí)，第三個(gè)取代基主要進(jìn)入間位定位基的鄰位4)取代基定位能力相近時(shí),得混合Caution(注意傅-克烷基化，磺化是可逆反活性較低(低于鹵苯)的芳烴不起傅-克反應(yīng)-NH,-NHR,-NR取代的芳烴不起傅-克反乙烯型鹵,芳基鹵不能作為傅-克烷基化的試 甲?；磻?yīng),不能用烷基苯,酚,酚醚作底物,帶有強(qiáng)鈍化基的化合物強(qiáng)活化的苯環(huán)會(huì)發(fā)生多鹵代反應(yīng)△D7.67.6 BrNO +7.7Otherreactionsofbenzene(苯的其它反應(yīng)7.7.1AdditionofbenzenewithCl2(苯與氯的加成+Cl7.7.2Halogenationofthebenzylicposition(芐基位的鹵化radical Br2,7.7.37.7.3Oxidation(氧化OOVO,OR須含α PhBu- No (CH)PhCF[O]3 NaCrO/O7.7.4Reduction還原7.7.4.1Catalytichydrogenation(催化氫化+37.7.4.27.7.4.2Birchreduction(還原Na/NH(l)OCHH/HOONa/ Na/ Na/ 7.8Polycyclicarenes(多環(huán)芳烴7.8.1Multiphenylaliphatichydrocarbons(多苯代脂烴Ph2CH2Cl122,2-二(4-氯苯基)-1,1,1-PhCH+C碳正離子的穩(wěn)定PhC+>PhCH+>RC+>PhCH+≈RCH+≈CH=CHCH+>RCH+>CH>CH=CH+≈自由基的穩(wěn)定PhC?>PhCH?>PhCH?≈CH=CHCH?>RC?>RCH?>RCH?>CH=CH?≈7.8.2Biphenyls(聯(lián)苯類命3’1’242,4’-二氯聯(lián)4-(3-氨基苯基)-2-氯苯5’62-氯-4’-硝基聯(lián)II7.8.3Fused-ringarenes(稠環(huán)芳烴76 1α 436 4 6 32命HOS 1-硝基 5-甲基-2-萘磺 1,6-萘二α-硝基 苯并[a] AportionAportionofaAGraphene(石墨烯)isaone-atom-thicknarsheetofsp-bondedcarbonatomsthataredenselypackedina bcrystallattice.Itcanbevisualizedasanatomic-scalechickenwiremadeofcarbonatomsandtheirbonds.Grapheneisthebasicstructuralelementofsomecarbonallotropes(同素異形體)includinggraphite,carbonnanotubesandfullerenes.Itcanalsobeconsideredasaninfiniylargearomaticmolecule.TheNobelPrizeinPhysicsfor2010wasawardedtoAndreGeimandKonstantinNovoselov“forgroundbreakingexperimentsregardingthetwo-dimensionalmaterialOCrO/O加成反 + +PhH Br/ CHCOCl/CS,- CHCOCl/PhNO, 親電試劑被溶劑定位規(guī)+AlCl/+O萘發(fā)生親電取代時(shí)，環(huán)上的活化基使取代多發(fā)生在活化基在1位時(shí)，取代多發(fā)生在4活化基在2位時(shí)，取代多發(fā)生在1位，也可能發(fā)生在6位(在異環(huán)鈍化基使取代多發(fā)生在鹵化，硝化多發(fā)生在α位(同時(shí)考慮位阻效應(yīng)磺化，?；喟l(fā)生在β蒽作為二烯體與親二烯體發(fā)生D-AO+ O合成合成-Haworth反應(yīng)萘及其衍生物的合OO OZn-Hg/OOZn-Hg/SeorPd/ O OZn-Hg/GOZn-Hg/HClSeorPd/GG=-R,-OR,-+OOR'OH, PPAZn-Hg/HClSeorH+,ROMgX R/GSeorRRH+,/G蒽及其衍生物的合O菲及其衍生物的合 Zn-Hg/ PPAZn-Hg/HClSeorPd/蔻及其衍生物的合成（AreallAreallfully-conjugated,cyclicsystems(calledannulenes輪烯)√?√7.9Hückel’sRuleandAromaticity(休克爾規(guī)則與芳香性7.9.1Hückel’sAmoleculeisaromaticifIscyclicandIscompleyContains4n+2πAromaticity芳香性)(4n+2π電子)Antiaromaticity反芳香性)(4nπ電子)Nonaromaticity非芳香性)Anaromaticcompoundismorestablethanasimilaracyclic Anantiaromaticcompoundislessst