酚和醚都是烃的含氧衍生物

第八章醇酚醚(Alcohols、Ethers)乙醇乙醚苯酚CH3CH2OHCH3CH2OCH2CH3OH第一节醇醇、酚和醚都是烃的含氧衍生物，羟基与脂肪烃基直接相连的叫醇，羟基与芳香烃基直接相连的叫酚，两烃基与氧直接相连的叫醚。例：OHCH3OHCH2OH饱和脂环醇例如：2-甲基环己醇脂环醇不饱和脂环醇例如：2-环己烯醇芳香醇例如：苯甲一：分类：醇饱和脂肪醇CH3CH2CH2OH丙醇；脂肪醇不饱和脂肪醇CH2=CHCH2OH2-丙烯醇一元醇CH3CH2OH乙醇醇二元醇HOCH2CH2OH乙二醇（按羟基的数目）CH2CH2CH2多元醇|||丙三醇OHOHOH按所连碳原子的种类不同:伯醇CH3CH2CH2CH2OH丁醇仲醇CH3CHCH3异丙醇醇|OH叔醇（CH3）3COH叔丁醇优势构象优势构象二：醇的结构CHOHHH1090OHRSP3OHHHHOHHHHClOHHH试写出FCH2CH2OH与BrCH2CH2OH的优势构象(用Newman投影式表示）三.物理性质(分子间氢键缔合)为什么醇具有较高的沸点？醇分子中烃基对氢键缔合有阻碍作用。多元醇，分子中两个以上位置可形成氢键。乙醇乙二醇丙三醇78.5oC197oC290oCOHRORHOHRHOR低级醇与水互溶。醇在强酸中的溶解度比在水中大。ROHHOHHORHOHROH+HXROHX-H+CH3CH2CH2CH2OH水浓HCl8%互溶醇和物CaCl24C2H5OH四.醇的化学性质ROHROHROH1.醇的酸碱性RCH2OH+HXRCH2OH2X-+RCH2OH+NaRCH2ONa+1/2H2(CH3)3COH+K(CH3)3COK+1/2H2作碱性试剂或亲核试剂作消除反应试剂酸性：ROHH2O;碱性：RONaNaOHRONa+H2OROH+NaOH液态醇的酸性强弱顺序：1o醇2o醇3o醇[分析]烷氧负离子的稳定性2.取代反应（生成卤代烷）1)与氢卤酸反应ROH+HXRX+H2O醇活性顺序：3o2o1oCH3OHHX活性：HIHBrHCl酸催化使羟基质子化，减弱C-O键，然后以水的形式离去。SN1机制：（多数2o3o醇）δ-δ+X-CCH3CH3CH3OH+HXCH3CCH3CH3OH2+CH3C+CH3CH3CH3CCH3CH3XSN2机制：（多数1o醇）ROHH+ROH2+ROH2]XR+H2OX[X-下面的反应能否顺利进行CH3CH2CH2CH2OH+NaBrCH3CH2CH2CH2Br•鉴别不同类型醇（六个碳以下的醇）？3o醇、烯丙醇、苄醇室温下反应液立即混浊、分层；2o醇2~5min.反应液混浊、分层；1o醇加热，反应液混浊、分层；反应按SN1历程，有碳正离子重排。CH3C-CHCH3CH3OHHHClCH3C-CHCH3CH3OH2H+-H2OCH3C-CHCH3CH3H+重排CH3C-CH2CH3CH3+Cl-Cl-CH3C-CH2CH3ClCH3CH3C-CHCH3CH3HClLucas试剂：浓HCl—无水ZnCl2ROH+HClRCl+H2O2）与PX3、SOCl2反应3(CH3)2CHCH2OHPBr33(CH3)2CHCH2Br+H3PO3RCH2OH+BrPBr2RCH2OPBr2+HBrBr-+RCH2OPBr2SN2RCH2Br+-OPBr2CH3CH2CH2CH2OH+SOCl2-HClCH3CH2CH2CH2OSClO-SO2CH3CH2CH2CH2Cl反应不发生重排。ROH+SOCl2RCl+SO2+HCl+3HONO2+3H2O甘油三硝酸酯CH2OHCHOHCH2OHCH2ONO2CHONO2CH2ONO2CH3OH+H2SO4CH3OSOHOO硫酸氢甲酯CH3OH硫酸二甲酯CH3OSOCH3OOROH-H2O烷基磷酸酯三烷基磷酸酯二烷基磷酸酯ROH+HOPOHOOH-H2OROPOHOOHROPOHOORROH-H2OROPOROOR3.成酯反应腺苷-O-P-O~P-O~P-O-OOOO-O-O-ATP“~P”“高能键”烷基二磷酸酯、烷基三磷酸酯在生物化学中非常重要。试写出烷基三磷酸酯的结构式并写出其释放能量的水解反应式。•与磺酰氯作用生成磺酸酯CH3SClOO对甲苯磺酰氯+CH3OH吡啶-HCl对甲苯磺酸甲酯CH3S-OCH3OOR’OOSORCH2Nu:-+NuCH2R+R’OOS-O好的离去基团4.脱水反应1)生成烯烃（分子内脱水）OHHCCH+OH2HCC+-H2OHCC+-H+CC醇脱水成烯的反应速率：3o醇2o醇1o醇消除取向——Saytzeff规则E1机理氢从含氢较少的-C碳上脱去，生成双键碳上取代基较多的稳定的烯烃。CH3CH2CCH3CH3OH48%H2SO490oCCH3CH=C(CH3)2+CH3CH2C=CH2CH384%[讨论]CH2OHH+170oC?CH2OHH+CH2OH2+CH2-H2O+重排H+-H+•氧化铝催化加热脱水（不发生重排）Al2O3350oCCH2OHCH22)生成醚（分子间脱水）CH3CHOHCH3H+CH3CHOH2CH3+-H2OCH3CH+CH3CH3CHOHCH3CH3CHOCHCH3CH3CH3H+-H+CH3CHOCHCH3CH3CH3制简单醚（两个烃基相同的1o或2o醇）制混合醚（3o与1o醇）H++(CH3)3COH(CH3)3COH2-H2O(CH3)3C+CH3CH2OH+(CH3)3COCH2CH3H-H+(CH3)3COCH2CH35.氧化1).KMnO4(H+orOH-)、Na2Cr2O7-H2SO4、HNO31o醇RCH2OH[O]RCHO[O]RCOOH2o醇RCHOHR'[O]RC=OR'3o醇RCOHR'R[O]不易被氧化2）选择性氧化剂a.MnO2-C为不饱和键的1o、2o醇。双键保留。产物：醛或酮。C=C-CH2OHMnO2C=C-CHOC=C-CHOHRMnO2C=C-C=ORHOCH2CH2CH=CHCH2OHMnO2HOCH2CH2CH=CHCHOCH3CHCH2CH2OHCH3OHMnO2CH3CHCH2CH2OHCH3Ob.CrO3—吡啶、CrO3—H2SO4(稀)分子中双键、三键保留。CH2OHCHOCrO32C5H5NOOOHCrO32C5H5NOOO1o醇2o醇3o醇CrO3-H2SO4无反应（3o醇）橙色变为蓝绿色（1o、2o醇）c.DCC-DMSOHODCC-DMSOH3PO4（少量）ODCC:二环己基碳二亚胺N=C=N(Dicyclohexylcarbodimide)(Dimethylsulfoxide)DMSO3）欧芬脑尔氧化法（2o醇氧化成酮，不饱和键保留）R2CHOH+CH3CCH3OAl[OCH(CH3)2]3orAl[OC(CH3)3]3RCR+CH3CHCH3OOHCH3CHCH2CH2CH=CCH=CH2OHCH3Al[OC(CH3)3]3丙酮—苯CH3CCH2CH2CH=CCH=CH2CH3ORCROHCROHIO-4RRCROCRORIO-OOHOH2R2C=O+IO3-+H2OR-C-CH-CHOOHO2HIO4RCHO+HCOOH+HCOOHHR-CH-C-CH2OHHOO2HIO4RCHO+CO2+HCHO6.二醇的特有反应CH2CHCHCH2OHOHOHOH3HIO42HCHO+2HCOOH反应定量进行，经环状高碘酸酯进行：1）高碘酸或四醋酸铅氧化-羟基酸、1,2-二酮、-氨基酮及邻氨基醇等有类似反应。CH2CH2NH2OHHIO42HCHOCH3CCCH3OOHIO42CH3COOH试写出下列化合物用高碘酸氧化的产物及消耗的试剂用量。2）邻二醇的重排反应——频哪醇(pinacol)重排H2CHOH2CHOHHHOHHHOCH3CCCH3H3CCH3HOOHH2SO4CH3CCCH3CH3H3CO四甲基乙二醇(pinacol)频哪酮(pinacolone)CHOHCHOHOCH2CH2HCOOH+产物：试剂用量：2molCH3CCCH3H3CCH3HOOHH+CH3CCCH3H3CCH3HO+OH2-H2OCH3CCCH3H3CCH3+OH重排CH3CCCH3CH3HOCH3+-H+CH3CCCH3CH3OCH3不对称的邻二醇，重排如何进行？优先生成较稳定的碳正离子决定基团迁移及反应的产物。CCCH3HOOHCH3H+-H2OCCCH3CH3OH+重排-H+CCCH3H3CO•提供较多电子的基团优先迁移迁移能力：芳基烷基或HCCHOOHCH3H+-H2O+H3CCCCH3H3COH重排-H+OCH3CH3CC[讨论]C6H5H5C6KMnO4（冷）OH-H+ABBAphphHOHOphphO四.醇的制备1）卤代烷水解2）以烯烃为原料a.烯烃的硼氢化氧化b.烯烃的水合c.烯烃的羟汞化-脱汞化RCH=CH2Hg(OCOCH3)2H2O,25oCRCHCH2OHHgOCOCH3NaBH4RCHCH2OHHHg(OCOCH3)2H2ONaBH4CH3CCH=CH2CH3CH3CH3CCH3CH3CHOHCH2H马氏加成，不发生重排3）羰基化合物还原CONaBH4EtOHCHOH4）羧酸、羧酸酯的还原C2H5COOHLiAlH4H2OC2H5CH2OH(C2H5COOCH3)(C2H5CH2OH)5）格氏试剂与羰基化合物等反应RMgX+C=O无水乙醚R-C-OH+MgOHXR-C-OMgXH+H2Oa.RMgX+H-C-HO无水乙醚R-C-OMgXHHH2OH+RCH2OH(1)制1o醇MgCl+HCHO无水乙醚H2OH+CH2OH在格氏试剂烃基上增加一个碳原子CH3CH2CH2MgBr+1)无水Et2O2)H3O+CH3CH2CH2CH2CH2OHb.O在格氏试剂烃基上一次增加两个碳原子。CH2MgCl+CH3CHO无水乙醚H2OH+CH2CHOHCH3(2)制2o醇a.RMgX+R'-C-HO无水乙醚R-CH-OMgXH2OH+RCHOHR'R'b.甲酸酯与格氏试剂反应CH3CHMgBrCH3+HCOC2H5O无水乙醚CH3CHCHOCH3OMgBrCH3CHCHCH3OC2H5对称2o醇CH3CHCHOCH3(CH3)2CHMgBrCH3CHCHCHCH3CH3OMgBrCH3H+H2OCH3CHCHCHCH3CH3CH3OH醛活性大于酯。原料用量：甲酸酯∶格氏试剂=1∶2（mol)c.一取代环氧乙烷与格氏试剂反应MgBr+CH3CHCH2OEt2OCH2CHCH3OMgBrH+H2OCH2CHCH3OHC-CH3O+CH3CH2MgBr1)Et2O2)H3O+C-CH2CH3CH3OH(3)制3o醇a.格氏试剂与酮反应b.格氏试剂与羧酸酯反应H3CMgBr+COC2H5O[]CH3COC2H5OMgBrCCH3O1)H3CMgBr2)H3O+CCH3CH3HO酮的活性大于酯原料用量：酯∶格氏试剂=1∶2(mol)逆合成法表示步骤方法是用一个空心箭头目标分子前体由目标分子指向前体————————————————————[设计合成路线]CH3CH2CCH2CH3C6H5OH方法一：CH3CH2CCH2CH3C6H5OHCH3CH2CCH2CH3O+C6H5MgBr方法二：CH3CH2CCH2CH3OHC6H5CH3CH2CC6H5O+CH3CH2MgBr方法三：CH3CH2CCH2CH3OHC6H52CH3CH2MgBr+C6H5-C-OCH3O•二醇的制备1）烯烃的氧化2）水解RCHCHROHXOH-RCHCHROHOHH+H2ORCHCHROHOHORCHCHRRCHCHRXXOH-RCHCHROHOH1)RCO3HKMnO4（冷）OHOHHHHOOHHH2)H3O+一.结构、命名与物性p-共轭①苯环上电子云密度增加；②酚羟基氢的离解能力增强。OHCH3COOHClOHO2NCHCH2OHOHCH35-甲基-2-萘酚5-硝基-3-羟基-