醇和酚小结

一、物理性质1.沸点：较高(氢键）OHRORHOHRHOR烃基对氢键缔合有阻碍。例（CH3)3COH，b.p.82.5℃，m.p.26℃。乙醇乙二醇丙三醇78.5oC197oC290oC第十章醇和酚Ⅰ醇2.溶解性低级醇与水互溶。在强酸中的溶解度比在水中大。ROHHOHHORHOHCH3CH2CH2CH2OH水浓HCl8%互溶HROH+HXROHX3.波谱（1）IR特征峰vO-H游离：～3600cm-1尖缔合：～3400cm-1宽分子内：～3500cm-1尖vC-O1200~1100cm-1,宽，较强二.醇的反应（1）酸性,（2）碱性,（3）OH被取代。1.酸碱性（1）酸性RO－HRO+H酸性排序CH3OH＞RCH2OH＞R2CHOH＞R3COH烷基体积增加，醇的酸性降低。ClCH3CH2CH2OHCH3CHCH2OHCH2CH2CH2OHCl＞＞ROH＋NaRONa＋H2CH3CH2OH＋Mg(EtO)2Mg＋H2干燥醇OHRδδδ拉电子基使酸性增强（3）碱性质子化EtOH+BF3HEtO－BF3EtOH+CaCl2CaCl2.4EtOH络合物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：HIHBrHCln-BuOH+HI(conc.)n-BuI+H2On-BuOH+HBrH2SO4n-BuBr+H2OH2SO4n-BuBr+H2On-BuOH+NaBrn-BuOH+HCl(conc.)ZnCl2n-BuCl+H2OROH＋HROH2SN1机制:（2o,3o及β-取代较多的醇）X-CCH3CH3CH3OH+HXCH3CCH3CH3OH2+CH3C+CH3CH3CH3CCH3CH3XSN2机制:（1o醇）t-BuOH+HCl(conc.)t-BuCl+H2O反应机理HROHROH2XXROH2RX+H2OZnCl2催化机理δHROHZnCl2R－OZnCl2HClROZnCl2ClδRCl+H2O+ZnCl2H有碳正离子重排。鉴别不同类型醇（六个碳以下的醇）Lucas试剂：浓HCl—无水ZnCl23o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；2）与PX3、SOCl2反应3ROH+PX33RX+H3PO310，20醇反应机理ROH+PX3ROPX2＋HXRX＋O－PX2SN2反应（无重排）ROH+SOCl2RCl+SO2+HClCH3CH2CH2CH2OH+SOCl2-HClCH3CH2CH2CH2OSClO-SO2CH3CH2CH2CH2ClOHSOCl2CH3CH2CH3HClCH3CH2CH3H构型保留XR－O－PX23.成酯反应ROH＋RCOOHHRCOOR＋H2O无机酸酯+3HONO2+3H2O甘油三硝酸酯CH2OHCHOHCH2OHCH2ONO2CHONO2CH2ONO2构型转化PyOHSOCl2CH3CH2CH3HClCH3CH2CH3HPyorDMFOHCH3CH2CH3HSOCl2OSOClCH3CH2CH3HClOO－SC2H5CH3HN－SO2ClC2H5CH3H硫酸氢甲酯NaOHROH+H2SO4ROSO3HROSO3NaR为长链烷基时，其钠盐作为洗涤剂.ROSO3H溶于浓硫酸，可用于提纯分离.提纯方法粗产物浓硫酸上层下层硫酸层产物水洗碱洗干燥蒸馏纯品CH3OH＋H2SO4CH3OSO2OH(CH3O)2SO2+H2SO42CH3OSO2OHΔ硫酸二甲酯,甲基化试剂;类似物硫酸二乙酯(C2H5O)2SO2.例如ZnCl2OHCH3(CH2)5CHCH3HClClCH3(CH2)5CHCH34.脱水反应1)生成烯烃（分子内脱水）E1机理醇脱水成烯的反应速率：3o醇2o醇1o醇消除取向——Saytzeff规则: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%OHHCCH+OH2HCC+-H2OHCC+-H+CCCH2OHH+CH2OH2+CH2-H2O+重排H+-H+重排现象CH2OHH+170oC?2)生成醚制简单醚（两个烃基相同的1o或2o醇）CH3CHOHCH3H+CH3CHOH2CH3+-H2OCH3CH+CH3CH3CHOHCH3CH3CHOCHCH3CH3CH3H+-H+CH3CHOCHCH3CH3CH35.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CH2CH2CH2CH2OHNaCr2O7H2SO4CH2CH2CH2CHOb.p.118℃75℃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。HOCH2CH2CH=CHCH2OHMnO2HOCH2CH2CH=CHCHOCH3CHCH2CH2OHCH3OHMnO2CH3CHCH2CH2OHCH3Ob.CrO3—吡啶络合物氯铬酸吡啶（PCC）CH2CH2CH2CH2OHPCCCH2Cl2CH2CH2CH2CHOCH2OHCHOCrO32C5H5N分子中双键、三键保留。C5H5N+CrO3+HClC5H5NH.ClCrO3沙瑞特试剂N+CrO32CrO3.2C5H5N3）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=CH2CH3O4）CrO3—H2SO4(稀)1o醇2o醇3o醇CrO3-H2SO4无反应（3o醇）橙色变为蓝绿色（1o、2o醇）分子中双键、三键保留。四.醇的制备1）羰基化合物还原CONaBH4EtOHCHOH①醛酮还原剂：NaBH4Al(OPr-i)3LiAlH4溶剂：甲（乙）醇异丙醇乙醚，THFRCHORCOR'RCOOR'RCOOH反应活性逐渐降低Ph－C－PhONaBH4alcoholPh－CH－PhOHC－HONaBH4alcoholNO2CH2OHNO2注:异丙醇铝还原伯醇的产率较低，副产物多.氢化铝锂还原性强、价格高，硼氢化钠还原性弱、价廉，②羧酸和酯伯醇Al(OPr-i)3RCH＝CHCR＋CH3CHCH3OHORCH＝CHCHR＋CH3CCH3OHOalcoholOCH3OCCH2CH2CHONaBH4LiAlH4etherOCH3OCCH2CH2CH2OHHOCH2CH2CH2CH2OH＋CH3OH选择性强Ocat.RCR＋H2OHRCHR催化氢化价廉、污染小ORCOHLiAlH4RCH2OHORCOC2H5LiAlH4RCH2OH伯沃－布兰反应ORCOC2H5NaRCH2OHalcohol2）格式反应RMgX+C=O无水乙醚R-C-OH+MgOHXR-C-OMgXH+H2O(1)制1o醇a.RMgX+H-C-HO无水乙醚R-C-OMgXHHH2OH+RCH2OHMgCl+HCHO无水乙醚H2OH+CH2OH在格氏试剂烃基上增加1个碳原子CH3CH2CH2MgBr+1)无水Et2O2)H3O+CH3CH2CH2CH2CH2OHb.O在格氏试剂烃基上增加2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CH3CHCHOCH3OMgBrCH3CHCHCH3OC2H5CH3CHCHOCH3(CH3)2CHMgBrCH3CHCHCHCH3CH3OMgBrCH3H+H2OCH3CHCHCHCH3CH3CH3OH对称2o醇原料用量：甲酸酯∶格氏试剂=1∶2（mol)(3)制3o醇c.一取代环氧乙烷与格氏试剂反应MgBr+CH3CHCH2OEt2OCH2CHCH3OMgBrH+H2OCH2CHCH3OHa.格氏试剂与酮反应C-CH3O+CH3CH2MgBr1)Et2O2)H3O+C-CH2CH3CH3OHb.格氏试剂与羧酸酯反应OPhMgBr+PhCOC2H5COPhCOC2H5MgBrPhPhPhOCH3OPhPhOPhMgBr①②CPhPhOHPh酯∶格氏试剂=1∶2（mol)五.有机合成设计[设计合成路线]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CH3CH2CCH2CH3C6H5OH方法二：CH3CH2CCH2CH3OHC6H5CH3CH2CC6H5O+CH3CH2MgBr方法一：CH3CH2CCH2CH3C6H5OHCH3CH2CCH2CH3O+C6H5MgBr方法三：CH3CH2CCH2CH3OHC6H52CH3CH2MgBr+C6H5-C-OCH3OClCH2CH2OH五、二元醇1.物性：沸点、粘度、味道2.特有反应1）高碘酸或四醋酸铅氧化反应定量进行，经环状高碘酸酯进行：RCROHCROHIO-4RRCROCRORIO-OOHOH2R2C=O+IO3-+H2OCH3CH－C(CH3)2OHCH3CHO+(CH3)2COH5IO6OHCH3CH－CH－C(CH3)2OHH5IO6OHOHCH3CHO+HCOOH+(CH3)2CO四乙酸铅的氧化产物同上2）邻二醇的重排反应——频哪醇(pinacol)重排CH3CCCH3H3CCH3HOOHH2SO4CH3CCCH3CH3H3CO四甲基乙二醇(pinacol)频哪酮(pinacolone)CH3CCCH3H3CCH3HOOHH+CH3CCCH3H3CCH3HO+OH2-H2OCH3CCCH3H3CCH3+OH重排CH3CCCH3CH3HOCH3+-H+CH3CCCH3CH3OCH3•富电子的基团优先迁移不对称的邻二醇，优先生成较稳定的碳正离子:CCCH3HOOHCH3H+-H2OCCCH3CH3OH+重排-H+CCCH3H3COCCHOOHCH3H+-H2O+H3CCCCH3H3COH重排-H+OCH3CH3CC迁移能力：芳基烷基HCH3OC6H4＞CH3C6H4C6H5ClC6H4＞＞3）脱水一缩二甘醇1,4-二氧六环四氢呋喃tetrahydrofuran(THF)3.制备1）烯烃的氧化1)RCO3HKMnO4（冷）OHOHHHHOOHHH2)H3O+2）水解HHOOHOHOHOHOOHOHOOHOHOHRCH－CH2ClOHRCH－CH2OHOHORCH－CH2OHRCH－CH2OH酸性比较：RCOOHH2CO3PhOHH2OROH＞＞＞＞PhOH+NaOHPhONa+H2O三、化学性质1.酸性OH+H2OO+H3O易溶水Ⅱ酚（phenol)OH1.6Dsp2..氧原子sp2杂化，p-π共轭，(1)苯环电子密度高,(2)酸性该性质用于分离提纯苯酚和苯甲醇混合物的分离蒸馏纯品H＋苯酚OHONaHorCO2混合物NaOH水溶液上层下层上层下层苯甲醇酚钠水溶液酸性与结构的关系OHG酸性比较OHO2NClCH3CH3OOHOHOH苦味酸，强酸性OHNO2NO2O2N试比较下列各组化合物的相对酸性：1)HOClHOHOClabcOHOHNO2OHNO2OHNO2abcd2)1)c＞b＞a2)c＞b＞d＞a2.亲电取代（1）卤化在水中易进行亲电取代原因OH＋Br2CS2OHBr弱极性溶剂OHBr酸性溶液OH＋Br2H2OHBrOH＋Br2白色H2OOBrBrBrBrBrOHBrBrNaHSO3水溶液鉴别酚OH+H2OO+H3O溴代酚酸性强，较苯酚易进行亲电取代.（2）硝化＋Br2OHOBrOHBr＋Br2OHBrBrBr2OHBrBrBrOB