最新四川大学有机化学第八章ppt课件.ppt

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1、LIYING2022-7-6一、醇的结构、分类和命名醇（ROH）:RH的H被OH取代后的产物 HOH中的H被R取代的产物C、O: sp3杂化化学反应:容易断裂 CO和OH键 与金属作用（OH，断裂，酸性） 亲核取代反应(OH被取代) 消除反应(消除OH和-H)LIYINGLIYINGLIYINGLIYINGLIYINGLIYINGLIYING2022-7-61、沸点: 比同碳原子的烷烃、卤代烃高。化合物 乙醇 乙烷 丙烷 氯乙烷沸点78.5-98-4212乙醇乙烷丙烷氯乙烷-100-50050100沸点沸点LIYING2022-7-6ROHHORHOR氢键20kJ/mol醇与水分子间也能形成氢

2、键LIYING2022-7-6 低级醇溶于水，甲醇、乙醇、丙醇与水混溶。随分子量增大，水溶性降低。ROHHOH亲水基亲脂基（疏水基）LIYING2022-7-6 低级醇能和一些无机盐类（MgCl2、CaCl2、CuSO4）形成结晶状分子化合物（结晶醇），如MgCl2.6C2H5OH、CaCl2.4C2H5OH、CaCl2.4CH3OH。 结晶醇不溶于有机溶剂而溶于水。利用此来除去少量低级醇。LIYING2022-7-6CORCHHH亲核取代(如与HX、PX3、PX5作用）消除（脱水）酸性（与活泼金属作用）作亲核试剂（酯化反应）氧化、脱氢LIYING2022-7-6 ROH + Na RONa

3、+ H2 RONa + H2OROH + NaOHLIYING2022-7-6 25(CH3)3COH 18CH3CH2OH 16HOH 15.74CH3OH 15.54CF3CH2OH 12.43 化合物 pKaH HC C C CH H酸性增强LIYING2022-7-6 CH3OH + NaHCH3ONa + H2OCH2CH2OH + NaNH2CH3CH2ONa + NH3CH3CHCH3OH+ CH3LiCH3CHCH3OLi+ CH4OH+ CH3MgClOMgCl + CH4LIYING2022-7-6 6 CH3CCH3OH+ 2 AlHgCl2or AlCl3(CH3)2C

4、HO3Al2+ 3H2CH3CH2OH + Mg I2(CH3CH2O)2Mg + H2(CH3CH2O)2Mg + H2O CH3CH2OH + Mg(OH)2用于制备绝对无水乙醇。LIYING2022-7-61）与氢卤酸反应R OH + HX R X + H2O LIYING2022-7-6 C H3 CCH3CH3OHConc. HClr.t C H3 CCH3CH3ClCH3CH2CH2CH2OH47% HI48% HBrH2SO4Conc. HClZnCl2CH3CH2CH2CH2I CH3CH2CH2CH2Br CH3CH2CH2CH2ClLIYING2022-7-6(CH3)3C

5、OH 放热、立即混浊 几分钟后，浑浊CH3CH2CH OHCH3CH3(CH2)3OH 室温无变化；加热后变浑浊ZnCl2/HClr.tLIYING2022-7-61）SN2 （伯醇与HX）：ROH + H+快R O H H（质子化醇）X R O H HR O H HX RX + H2OLIYING2022-7-6R3COH + H+R3COH2R3C + H2OR3C + XR3CX快 慢快LIYING2022-7-6CH3 C COH CH3HHCH3 HClCH3 C CCl CH3HHCH3 HBr+ CH3 C CH CH3HClCH3 (重排产物）CH3 CCH3 CH3 CH2B

6、r CH3 CCH3 Br CH2CH3+(重排产物）CH3 CCH3 CH3 CH2OH LIYING2022-7-6 CH3 C COH CH3HHCH3 CH3 C CCl CH3HHCH3 + CH3 C CH CH3HClCH3 (重排产物）CH3 C COH2 CH3HHCH3 CH3 C C CH3HHCH3 (二级碳正离子）H+CH3 C CH CH3HCH3 Cl重排Cl（三级碳正离子）LIYING2022-7-61、用反应机理解释以下反应。CCH3 OHCH3HClCCH3 ClCH3+ CH3 CH3ClLIYING2022-7-6 与卤化磷反应的特点：1）不发生重排。

7、2）副反应：成酯。 副反应：ROH + PCl3(RO)3P + HCl亚磷酸酯ROH + PCl5(RO)3PO + HCl磷酸酯LIYING2022-7-6反应历程：SN2CCH3CH2 H CH3OH+ SOCl2乙醚吡啶CCH3CH2 H CH3ClCCH2CH3H CH3Cl SN2分子内SN2构型保持 构型翻转紧密离子对吡啶：NLIYING2022-7-6 能与无机酸（H2SO4、HNO3、H3PO4等）和 有机酸（以后讨论）成酯。CH3CH2OH + HOSO2OH CH3CH2OSO2OH + H2OCH2 CH2+ HOSO2OH硫酸氢乙酯CH3OSO2 OH+ HOSO2

8、OCH3CH3OSO2OCH4 + H2SO4减压蒸馏or （CH3)2SO4硫酸二甲酯剧毒LIYING2022-7-6 nC12H25OH + H2SO44455 Cn-C12H25OSO3HNaOHor Na2CO3n-C12H25OSO3Na十二烷基磺酸钠 乳化剂LIYING2022-7-6CH2OHCHOHCH2OH+ 3 HNO3浓硫酸CH2ONO2CHONO2CH2ONO2+ H2O烈性炸药治疗心绞痛和胆绞痛3 n-C4H9OH + HO PHO HO O(n-C4H9O)3PO磷酸三丁酯LIYING2022-7-6 常用催化剂：H2SO4、H3PO4、AlCl3 两种方式：分子内

9、脱水（消除）、分子间脱水（亲核取代）。1) 分子内脱水RCHCH2OHHH+RCH CH2 + H2OCH3CH2OH98%H2SO4170 CCH2 CH2 + H2OLIYING2022-7-6 CH3CH2CH CHCH3HOH75%H2SO4100 CC CHCH3CH3CH2H(主要）CH3CH2C(CH3)2OH47%H2SO487 CCH3CH C(CH3)2CH3CH2C CH2CH3(主）（次）LIYING2022-7-6R3COHR2CHOHRCH2OH 叔醇的脱水较常用，有时也用仲醇，伯醇少用。CH3CH2CH2CH2OHAl2O3CH3CH3CH CH2+ H2OLIY

10、ING2022-7-6 CH3CH2OH + H2SO4CH3CH2OH2 + HSO4CH3CH2 OH2CH3CH2 + H2OCH2 CH2HCH2 CH2+ H+快慢快E1历程（碳正离子中间体），往往会有重排LIYING2022-7-6 CH3 CCH3CH3 CHCH3OHH2SO4(CH3)2C C(CH3)2历程：CH3C CHCH3CH3OHCH3 H+CH3C CHCH3CH3OH2CH3 H2OCH3C CHCH3CH3CH3 CH3C CHCH3CH3CH3 重排H+CH3CCH3 CCH3CH3LIYING2022-7-6 2 ROH H+ROR + H2O醚 CH3C

11、H2OHH2SO4C2H5OC2H5 + H2O乙醚140 CLIYING2022-7-6 SN2:CH3CH2 OHH+CH3CH2 OH2CH3CH2OHCH3CH2OCH2CH3HC2H5OC2H5 + H+LIYING2022-7-61）氧化剂氧化：RCH2OHR2CHOHR3COH氧化剂RCHO (醛）ORCOOH(羧酸）R2CO(酮)无反应。剧烈条件下，发生键断裂生成低级羧酸氧化剂：KMnO4、H2CrO4、K2Cr2O7/H2SO4、 Na2Cr2O7/H2SO4、CrO3/H2SO4LIYING2022-7-6 CH3(CH2)8CH2OHCrO3/H2SO4H2O, 丙酮CH

12、3(CH2)8COOH93% CH2OH PhCrO3/H2SO4H2O, 丙酮 COOH Ph85% OHCrO3/H2SO4H2O, 丙酮 O96%LIYING2022-7-6 CrO3 + HCl + NN H CrO3ClPCCPyridine CH2OHPCCCH2Cl2 CHO82%LIYING2022-7-6 RCH2OHRCHO + H2Cu, 325 CR2CHOHCu, 325 CRCOR + H2醛酮CH3CH2OHCu or Ag550 CCH3CHO + H2O+ O2LIYING2022-7-61) 酸性及螯合物的形成 多元醇的酸性比一元醇的酸性强ROH + NaO

13、HRONa + H2OCH2OHCH OHCH2OH+ Cu(OH)2CH2OCH OCH2OHCu深蓝色溶液 H2OCH2CH2OHOH+ Cu(OH)2 H2O CH2O CuO CH2绛蓝色溶液LIYING2022-7-6 CC OH OHHIO4 O O+ + HIO3AgNO3AgIO3 + HNO3C COROHRRHIO4RCOOH + RCORLIYING2022-7-6 CH3CHCH2HOOHHIO4CH3CHO + HCHO + HIO3CH2CHCH2OH OHOHHIO42 HCHO + CO2 + H2O +HIO3CH2CHCH2OHOHHIO4LIYING202

14、2-7-6 C C CH3CH3CH3CH3 OHOHC C CH3OCH3CH3 CH372%H2SO4片呐醇 片呐酮OHHOH2SO4OLIYING2022-7-6l由烯烃制备水合、氧化、硼氢化氧化、羟汞化脱汞、羰基合成反应l由羰基化合物制备Grignard反应、与炔化物反应、还原l卤代烃水解LIYING2022-7-6C C+ B2H6硼氢化C CH3B氧化C C OH硼氢化氧化反应：特点：1.氢加到含氢较少的双键碳原子上；2.顺式加成(指H和OH加在同一边），选择性好；3.产率高；4.反应条件温和。LIYING2022-7-6 CH3OHHCH3OHH解：CH3OHH2SO4 CH3B

15、2H6HCH3BH2H顺式加成H2O2, OHHCH3OHHLIYING2022-7-6 RCH CH2Hg(OAc)2 RCH CH2OHHgOAcNaBH4RCHCH3OHH2O4）羰基合成法H2C CH2+ CO +H2Co(CO)8, 加压CH3CH2CH2OHLIYING2022-7-6 1）醛、酮与格氏试剂作用HCHORCHORCOR1, RMgX2, H2O, H+ RCH2OH 伯醇 仲醇 CH ROHR C OHRR叔醇C O + RMgXCR OMgXH2ORCOHLIYING2022-7-6 O RMgBrRCH2CH2OMgBrH3ORCHCH2OH制备增加2个碳的伯醇

16、的好方法问题： CH2CH2CH2CH2OHLIYING2022-7-6 CH3CCH3HC CNaOCH3CC CHONaCH3H2OCH3CC CHCH3OHHCHO+ NaC CNaH2OHOCH2C CCH2OH3)醛、酮的还原R CO R还原R CHOH R还原剂：C2H5OH + Na、LiAlH4、 NaBH4、H2 + catalystLIYING2022-7-61）烯烃氧化氧化冷、稀KMnO4OHHOHHOH顺-1,2-环己二醇或OsO4LIYING2022-7-6（2）醛、酮的还原CO 2CH3 CH3Mg, H2OC COHCH3OCCH3CH3H3H2,3-二甲基-2,

17、3-丁二醇（片呐醇）CH3CH CH2+ Cl2500 CCH2CH CH2ClHOClCH2CH CH2ClClOHCa(OH)28090 CCH2CH CH2ClONa2CO3100150 CCH2CH CH2HOOH OH2022-7-6第二节第二节 消除反应消除反应卤代烃的卤代烃的E2、E1消去反应消去反应醇的醇的E2、E1、E1CB反应反应其它消去反应其它消去反应LIYING2022-7-6消除反应：消除反应： 从从一个一个化合物中化合物中消除消除两个原子两个原子 或原子团的反应。或原子团的反应。消除消除:相邻的两个碳原子上的原子或基团相邻的两个碳原子上的原子或基团被消除，形成双键或

18、叁键。被消除，形成双键或叁键。C CNu ECCNu E+消除消除:从同碳原子上消除两个原子或基团，从同碳原子上消除两个原子或基团，形成卡宾：形成卡宾：C NuEC+ NuE1,1消除消除LIYING2022-7-6CF3COONaCF2CO2NaF+1，3消除：消除：CC CNuECCC+ NuERCH2CH2OH +HXRCH2CH2X+H2ORCH CH2+H2OHX亲核取代反应时，常伴随消除反应亲核取代反应时，常伴随消除反应LIYING2022-7-6l3种消除机制种消除机制- E1, E2, and E1CBLGHHLG- LG- H- H- H- LG- LGLIYING2022-

19、7-6l1、E2反应反应-消除消除lMechanism with deprotonation by base, the C-LG bond is broken at the same time. H+ and LG - are lost at the same time through a concerted, bimolecular, rate-determination step.LGHCC+ LG+ H : Base: BaseLIYING2022-7-6lRegiochemistry（区域选择性）区域选择性）lZaitsevs Rule CH3CHCH2CH3Br- OCH3CH3CH

20、=CHCH3CH2=CHCH2CH3+CH3CHCH2CH2CH3Cl- OHCH3CH=CHCH2CH3CH2=CHCH2CH2CH3+80%20%67%33%CH3CCH2CH3ClCH3- OHCH2=CCH2CH3CH3CH3C=CHCH3CH3+70%30%LIYING2022-7-6 H3CHC CHCH3BrHOCH32-bromobutane + CH3O -H2C CHCH2CH31-butene + CH3OH2-butene + CH3OHBrHProgress of the reactionOCH3more stableless stableLIYING2022-7-6

21、lRelative reactivities - 30 20 10 CH3CH2CCH3CH3CH2CHCH3CH3CH2CH2CH2BrBrBrCH3CH3CH=CCH3CH3CH=CHCH3CH3CH2CH=CH2CH3302010 three alkyl substituents two alkyl substituents one alkyl substituentsLIYING2022-7-6BrCH3CH3CH3CH3CH3CH3CH3CH-CCH3+ RO -CH3C=CCH3BaseCH3CHC=CH2+More substituted productLess substitu

22、ted productCH3CH2O - (CH3)3CO -CH3CH2(CH3)2CO -19%81%(CH3CH2)3CO -8% 92%79%21%73%27%LIYING2022-7-6l2) 离去基团离去基团CH3O -Leaving group Conjugate acidpKaX = IX = BrX = ClX = FHIHBrHClHF-10 -9 -73.281%72%67%30%19%28%33%70%X+ABBALIYING2022-7-6l2) 离去基团离去基团似似E1CB的负离子特征（而碳负离子的稳的负离子特征（而碳负离子的稳定性是定性是 30 20 10 30

23、allylic 20 benzylic 20 allylic 30 10 benzylic = 10 allylic = 20 10 +CH3 vinylLIYING2022-7-6CCH3CH3CHCH3ClCH3OHCCH3CH3CHCH31,2-methyl shiftCCH3CHCH3CH3- H +CCH3CCH3CH320 carbocation30 benzylic cationLIYING2022-7-6lPlease try to propose a mechanism for the following reactionCH2H3CCH3 H +CH3CH3CH3LIYIN

24、G2022-7-6lStereochemistryC CH2CH3CH3ClCH3CHCH2CH3CH3H3CCH3CH2CHCH3CHCH2CH3H3CE1CH3CH2CHCH3CH2CHminormajorLIYING2022-7-6lE1 reactions from Cyclic Compounds HCH3ClCH3HCH3CH3- H +CH3CH3MeOHE1LIYING2022-7-6HCH3HCH3MeOHE1BrHHCH3HCH3HHCH3CH3HH1,2-hydride shift2030- H +CH3CH3LIYING2022-7-6l1) 底物结构底物结构(Stru

25、ctures of Substrates)lRX: 10,20, E2; 30 E1lPrimary and secondary alkyl halides react primarily by an E2 machanism under basic conditions; tertiary alkyl halides undergoes E1 elimination because of the greater stability of the tertiary cation intermediateLIYING2022-7-6lROH: 10 E2; 20, 30 E1lDehydrati

26、on of secondary and tertiary alcohols proceeds via an E1 mechanism because the nation of the leaving group requires that the reaction be carried out under acidic conditions, which are unfavorable for the E2 pathwayLIYING2022-7-6l2) 离去基团离去基团(Leaving Groups)lIn both E1 and E2 mechanisms, the C-LG bond

27、 is broken in the rate-determination step. Clearly, the weaker the C-LG bond, the easier is its cleavage, because less energy is needed to reach the transition state in which this bond substantially brokenLIYING2022-7-6lReactivity: R-I R-Br R-Cl R-F lIt has little effect on whether the elimination r

28、eaction proceeds via the E1 or the E2 mechanism. LIYING2022-7-6l1) SN2/E2竞争竞争l卤代烃的反应活性卤代烃的反应活性: SN2 10 20 30l E2 30 20 10l10卤代烃易于取代，较少消去卤代烃易于取代，较少消去l如进攻试剂体积大或卤代烃的如进攻试剂体积大或卤代烃的碳上取碳上取代基多，则消去比率大大增加代基多，则消去比率大大增加LIYING2022-7-6CH3CH2CH2BrCH3O -CH3OHCH3CH2CH2OCH3 + CH3CH=CH290%10%when the primary alkyl hal

29、ide is sterically hinderedCH3CHCH2BrCH3O -CH3OHCH3CHCH2OCH3 + CH3C=CH240%60%CH3CH3CH3when the nucleophile is sterically hinderedCH3CH2CH2CH2CH2Brt-BuO -t-BuOHCH3CH2CH2CH2CH2OC(CH3)3 + CH3CH2CH2CH=CH215%85%LIYING2022-7-6l1）SN2/E2竞争竞争l对于对于20 卤代烃卤代烃l进攻试剂碱性越强，体积越大，则发生进攻试剂碱性越强，体积越大，则发生消去反应的几率越大消去反应的几率越大l

30、而而30卤代烃则以消去反应为主卤代烃则以消去反应为主CH3CHCH3EtO -EtOHCH3CHCH3 + CH3CH=CH225%75%ClOEtCH3CHCH3AcO -AcOHCH3CHCH3 100%ClOOCCH3CH3CCH3EtO -EtOH CH3C=CH2CH3CH3BrLIYING2022-7-6l2) SN1/E1竞争竞争l卤代烃在卤代烃在SN1和和E1反应中的活性顺序一致：反应中的活性顺序一致： 30 20 10 ; RI RBr RCll反应温度高有利于反应温度高有利于E1l极性溶剂和弱碱性亲核试剂有利于极性溶剂和弱碱性亲核试剂有利于SN1LIYING2022-7-6

31、l机制：机制：E1，E2，E1CBl醇的醇的E1，E2机制与卤代烃不同之处在于，机制与卤代烃不同之处在于，醇需要首先质子化，再发生实质的碳醇需要首先质子化，再发生实质的碳-氧氧键断裂键断裂LIYING2022-7-6l1-丁醇失水得到丁醇失水得到 1-丁烯和丁烯和 2-丁烯丁烯CH3CH=CHCH3 + CH3CH2CH=CH2CH3CH2CH2CH2OHH2SO4E2How can we explain the forming of 2-butene? CH3CH2CH=CH2CH3CH2CH2CH2OHH2SO4H + CH3CH2+CHCH3- H +CH3CH=CHCH3LIYING2

32、022-7-6l醇的醇的E1CB机制机制l1）beta-碳原子上连有强的吸电子基，从而碳原子上连有强的吸电子基，从而 beta-氢具有较强的酸性，且碳负离子得以稳氢具有较强的酸性，且碳负离子得以稳定；定；l2）离去基团难离去）离去基团难离去OHHOH: OH OHOH- OH -OHHLIYING2022-7-6l例：例：l1、氟代烃发生、氟代烃发生 似似E1CB反应，得到反反应，得到反Zaitsev规则为主的烯烃规则为主的烯烃l2、季铵碱的、季铵碱的Hofmann消去反应，也似消去反应，也似E1CB历程，得到反历程，得到反Zaitsev规则为主的烯烃规则为主的烯烃l这种选择性被称为这种选择性

33、被称为Hofmann定位定位(Hofmann Orientation)LIYING2022-7-6l1、消除、消除X2的反应的反应l2、卤代乙烯消除、卤代乙烯消除HX的反应的反应l3、卤代芳烃消除、卤代芳烃消除HX的反应的反应l4、生物体系中的消除反应、生物体系中的消除反应l5、 -消除反应消除反应LIYING2022-7-6l1、消除、消除X2的反应的反应 lin the present of Zn, Mg, I - - anti periplanarCCXXZnCCXZnXCC+ ZnX2CCXXMgCCXMgXCC+ MgX2CCBrBrCCI -LIYING2022-7-6lPleas

34、e try to give the correct configuration of the reactant ZnCCPhHPhH?LIYING2022-7-6lThe elimination of HX from a vinyl halide produces an alkyne very strong bases, such as sodium amide, NaNH2, are generally employed for this purposes. lThe elimination options of mechanismsCCRRHXCCRRHXCCRRXCCRRHA vinyl

35、 cationA vinly anion: BaseCCRRE1E2E1cBLIYING2022-7-6lBecause the product alkyne has no stereochemical features, it is difficult to find experimental details to verify which mechanism is actually followed. lHowever, the E1 route is unlikely because the vinyl cation is so unstable, the energetic consi

36、derations favor the concerted E2 and the E1CB elimination mechanisms. LIYING2022-7-6CCvacant p-orbitalA vinyl cationC: sp-hybridizedcC sp2- hybrid orbitalA vinyl anionC: sp2-hybridizedonly 6 electrons8 electronsLIYING2022-7-6 Please suggest a mechanism for transformation and give reasons for the obs

37、erved regiochemistryBrNaNH2HLIYING2022-7-6H-H2CBrNH2HH2CBrCHH2CBrH2CCCHCH3HCCCHCH3HNH2- BrLIYING2022-7-6l- Formation of BenzynelThe possible pathway are E1, E2, and E1CB. BrHBrHBrHBr: Base: Base- H-Base- Brphenyl cationE 2Benzynephenyl anionLIYING2022-7-6lStructure of BenzyneLIYING2022-7-6lBiologica

38、l DehydrationO C CH2-CH-COCOOmalatefumaraseenolaseCHHCOOOO+ H2OfumarateCH2-CHOH OPO3 2-COOCH2=CCOOOPO3 2-+ H2OLIYING2022-7-6-消除： C X YXY C卡宾（碳烯）光、热分解：CH2N2hCH2 +N2重氮甲烷LIYING2022-7-6Cl CClCl HBCl CClClClCl CCl二氯卡宾B：强碱 NaOH、醇钠LIYING2022-7-6两种情况：单线态卡宾接近sp2 三线态卡宾spCHH103HH136单线态卡宾 三线态卡宾能量较高能量较低LIYING202

39、2-7-6 C C CH3 HCH3 H + CH2( )CH3HCH3HCH3HHCH3C C H CH3CH3 H + CH2( )单 顺线 式态 加卡 成宾LIYING2022-7-6C C CH3 HCH3 H + CH2( )CH3HCH3HCH3HHCH3C C H CH3CH3 H 三 无线 立态 体卡 选宾 择 性+ CHCl3NaOHPTCPTC: Phase Transfer CatalystCCl2LIYING2022-7-6酚：OH直接与芳环相连，简写为ArOHOHCH2OHOHOHOHOH苯酚 苯甲醇（苄醇） 邻苯二酚萘酚 萘酚 LIYING2022-7-61.结构

40、O Hsp2 sp3 C O Hsp3 sp3p共轭（C）极性更大，易于离解弱酸性、OH不易被取代OH基是致活基，苯环上更易亲电取代LIYING2022-7-6一般以苯酚为母体命名。OHOCH3OHClClClClOHNO2O2NNO2Cl2-甲氧基苯酚 五氯苯酚 2,4,6-三硝基苯酚 （苦味酸） LIYING2022-7-6l大多数酚是结晶性固体，少数酚是高沸点液体。l具有特殊气味l能形成分子间氢键，沸点较高，在水中有一定溶解度l具有腐蚀性和杀菌能力LIYING2022-7-6比苯更容易酸性比醇强，比碳酸弱亲核性比醇弱O H苯环上的亲电取代羟基上的反应: 酸性、作亲核试剂LIYING202

41、2-7-61）酸性OHpKa=10O+ H+OOOOOLIYING2022-7-6 OHGG: NH2、CH3、CH3O、H、Cl、 Br、 I、 NO2pKa：10.46;10.26; 10.21;10;9.38;9.35;9.30;7.16酸性增强LIYING2022-7-6 OH NO2NO2: m- o- P-pKa: 8.36 7.21 7.16 解释： I中等，NO2 I大，NO2 I小，NO2 与OH距离中等 OH距离近 与OH距离远 无C，不共轭 C C似乎酸性最小 酸性最大 酸性中等但 分子内氢键 分子间氢键OHONOON OO HOHNOO 邻硝基苯酚 对硝基苯酚分子内氢键

42、 分子间氢键LIYING2022-7-6OHNO2NO2OHNO2NO2O2NpKa 4.O5 0.25OO G G吸电子基 给电子基负离子稳定性 负离子稳定性 提高 降低LIYING2022-7-66C6H5OH + FeCl3H3Fe(OC6H5)6 + 3HCl苯酚 六苯氧根络铁酸 蓝紫色 凡具有烯醇式结构的化合物都有这一显色反应OHC C OHLIYING2022-7-6各类酚与三氯化铁反应所显颜色 酚 苯酚 对甲苯酚 间甲苯酚 对苯二酚 邻苯二酚 间苯二酚 连苯三酚 -萘酚 -萘酚 与FeCl3显色 蓝紫色 蓝色 蓝紫色 暗绿色结晶 深绿色 蓝紫色 淡棕红色 紫红色沉淀 绿色沉淀 对

43、苯二酚则被氧化成醌：OHOHFeCl3OOOHOHOHOHOO对苯二酚 苯醌 醌氢醌（氢醌）暗绿色 结晶LIYING2022-7-6上章学过：R XRC CR + NaXR X CH2OR CH2ONa + RC CNa + 醚苯甲醇钠把醇钠换成酚钠ONa+ R XOR+ NaX苯甲醚亲核性：O CH2OLIYING2022-7-6OHOH, (CH3)2SO4OCH3+ CH3OSO3举例：OHOH，C2H5BrOC2H5OHH2C CHCH2ClOCH2CH CH2LIYING2022-7-6 OHOH:邻对位定位基 O O是比OH更强的定位基LIYING2022-7-6OH+ 3Br2H

44、2OOHBrBrBr白色沉淀OHSO3H+ 3Br2H2OOHSO3HBrBr白色沉淀LIYING2022-7-6OH+ Br2CS25 COHBr+ OHBr+ HBrHOAc回流OH20%HNO325 COHNO2OHNO215% 3040%浓HNO3OHNO2O2NNO2LIYING2022-7-6OH98%H2SO410-25 COHSO3HOHSO3H100 C98%H2SO4, 100 COHHO3SSO3H4-羟基-1,3-苯二磺酸LIYING2022-7-6 OHNaNO2, H2SO478 COHNO稀HNO3OHNO280%问题：1、试比较三种硝基苯酚异构体在沸点， 水溶性

45、方面的差异，并说明理由。2、如何合成纯邻硝基苯酚和纯对硝基 苯酚LIYING2022-7-6l不能用AlCl3作催化剂OH+ AlCl3OAlCl2+ HClOHCH3(CH3)2C CH2H2SO4,OHCH3C(CH3)3(CH3)3COH+ CH3COOHH3PO4OHCOCH3LIYING2022-7-6OH+ CH3COCH3H2SO4CCH3CH3HOOH双酚ACCH3CH3HOOHOCH2ClCCH3CH3HOOCH2OOCH2ClCCH3CH3OOCH2OOCH2环氧树脂LIYING2022-7-6l易于氧化(即使在空气中放置过久，也会氧化而呈深红色)。OHOHOHNa2Cr2

46、O7/H2SO4OO对苯醌LIYING2022-7-6 OHOHAgO2OOOHNa2Cr2O7/H2SO4OOOH3H2,Raney NiOHLIYING2022-7-61、磺酸盐碱熔法H2SO4SO3SO3HNaOHSO3NaNaOH(s)300 CONaH+OHLIYING2022-7-6间苯二酚的制备：H2SO4SO3SO3HSO3HNaOHSO3NaSO3NaNaOH(s)ONaONaHOHOHLIYING2022-7-6Cl是乙烯式卤代烃，难以亲核取代ClNaOH,360 C20MPaONa+H+OHNO2NO2ClNaOH95100 COHNO2NO2LIYING2022-7-6

47、CH3CH CH2H2SO4CH(CH3)2异丙苯O2,R2O2110120 C0.4MPaC(CH3)2OHO稀硫酸8090 COH+ CH3CCH3O 苯酚 丙酮LIYING2022-7-6CH(CH3)2ROOR ROC(CH3)2O2C(CH3)2OOCH(CH3)2C(CH3)2OHO+ C(CH3)2 2ROLIYING2022-7-6C(CH3)2OHOH+C(CH3)2OH2OH2OC(CH3)2OOC(CH3)2H2OO C(CH3)2OH2H+O C(CH3)2OHO CH3CCH3OHOH+ CH3CCH3OLIYING2022-7-6l一、醚的结构、分类和命名COC11

48、0。醚键1.18DRORRORROAr简单醚 混合醚 芳醚（对称醚） （不对称醚） ArOArLIYING2022-7-6l1、开链醚 根据烃基结构分为：饱和醚、不饱和醚和芳醚。 普通命名法：两个烃基名醚。两个烃基名中文按次序规则，英文按字母顺序。CH3 OC2H5CH3OC(CH3)3甲基乙基醚 甲基叔丁基醚 LIYING2022-7-6 OCH3CH3CH2OCH CH2CH3OCH3C2H5OCH2CH2OC2H5 CH3OCH2CH2OH苯甲醚（茴香醚） 乙基乙烯基醚 二甲醚（甲醚）乙二醇二乙醚 乙二醇一甲醚OC2H5OC2H5二苯醚（苯醚） 二乙醚（乙醚）LIYING2022-7-6

49、 把醚看成是烃的烷氧衍生物，取较长的烃基作母体。烷氧基：ROC2H5OCH2CH2CH2CH2CH3CH32-乙氧基己烷 1,2-二甲氧基乙烷CH3OCH2CH2OCH3C2H5OCH2CH2OH OCH3CH3O2-乙氧基乙醇 1,4-二甲氧基苯OC(CH3)34-叔丁氧基-1-环己烯 1-苯氧基-2-4-甲基苯氧基乙烷OCH2CH2OCH3LIYING2022-7-6环 醚环 氧 化 合 物大 环 多 醚环氧化合物OCH2H2CCH2OH2CCH2OCHCHClH2C环氧乙烷 3-氯-1,2-环氧丙烷 1,3-环氧丙烷OOO四氢呋喃 1,4-二氧六环 THF （二噁烷）LIYING2022

50、-7-6 (OCH2CH2)n 冠醚（Crown ether）OOOOOO18-冠-6(18-Crown-6)OOOOOO二苯并-18-冠-6LIYING2022-7-6lb.p.比同数碳原子的醇低得多。l水中溶解度小（环醚除外）。CH3OCH3 C2H5OC2H5b.p. 24.9 34.6C2H5OH CH3CH2CH2CH2OHb.p. 78.4 117.8LIYING2022-7-6l性质稳定，常作溶剂。COC键在苛刻条件下可以断裂。l1、形成yang盐：ROR+ H+ROR HLIYING2022-7-6ROR + BF3R2O BF3ROR + AlCl3R2O AlCl32ROR