理學(xué)第九十章醇酚醚PPT課件

1、CCOHCCOHOHPhenol)第1頁(yè)/共78頁(yè)CH3CHCH2OHCOHCH3CH3CH3H3CCH3CH2CH2CH2OHCH3CH2CHCH3OH第2頁(yè)/共78頁(yè)H3CCH2OHCH2CHCH2OHCCHCH2CHCH3H3CH3COHCH2CH2CH2OHOHOHOHHOOHOH第3頁(yè)/共78頁(yè)CHCH2RH2O, H+CHCH3ROH（復(fù)習(xí)，第六章）CHCH2H3CH2O, H3PO4170oC, 10MPaCHCH3H3COHCCH2H3CCH3CCH3H3CCH3OSO3HH2OCCH3H3CCH3OHH2SO4第4頁(yè)/共78頁(yè)CH2CH2X2 , H2ONaHCO3, H2O

2、ArCH3NBSArCH2BrNaOHArCH2OH(PhCOO)2CH2CH2XOHCH2CH2OHOH（復(fù)習(xí)，第五章）RXOHorH2OROH第5頁(yè)/共78頁(yè)H2CO(1)(2) H2OCH2OHR(1)(2) H2ORCROCOHRRROROHCHCH2RR(1)(2) H2ORMgXRMgXRMgX(1)(2) H2ORCOEtOCOHRRRRMgX2+EtOH第6頁(yè)/共78頁(yè)(1)(2) H2O(1)(2) H2OOEtCROCOHHRROROHCHCH2RH(1)(2) H2OLiAlH4LiAlH4RCROCOHHRH+HOEtLiAlH4 or NaBH4第7頁(yè)/共78頁(yè)CHC

3、H2RCHCH2RH2O, THFOHHg OAcCHCH3ROHHg+Hg(OAc)2NaBH4第8頁(yè)/共78頁(yè)Hydroboration-Oxidation反應(yīng)的特點(diǎn)： 產(chǎn)率較高。 區(qū)域選擇性反應(yīng)（主要為反Markovnikov規(guī)則取向）。 立體專(zhuān)一性反應(yīng)（順式加成）。 無(wú)重排產(chǎn)物生成（說(shuō)明什么？）。 第三章CHCH2RHCCH2)3B(RB2H6H2O26OHCHCH2RHOH6H2CH3HBH3H2O2OHCH3HHOH 第9頁(yè)/共78頁(yè)COHCHH H+COH2CHH 第10頁(yè)/共78頁(yè)提示：使用強(qiáng)堿時(shí)，注意羥基的保護(hù)。ROH+NaRONa+H2CH3OHCH3CH2OHCH3CHO

4、HCH3CH3COHCH3CH3ROHRMgXRONaNaNH2ROMgX+NH3+RHNaHRONa+H2第11頁(yè)/共78頁(yè) Brnsted堿 Lewis堿好離去基好離去基ROHH+ROH2ROHROHZnCl2ZnCl2NuRNu+H2OClRCl +HOZnCl第12頁(yè)/共78頁(yè)ROHRXROR+HXSN2+醚ROHH+ROHROHH2OH+RHORHRORSN2ROHRORH+H2OROH+醚第13頁(yè)/共78頁(yè)ORH+OHRORROH+ORH+ORHRHOOHRROHH+OHROR SN2第14頁(yè)/共78頁(yè)CH2H3CH3CH+ROHH+CCH3CH3CH3OHRCCH3CH3CH3O

5、RCCH3CH3CH3H2CCH3CH3H+ROH+ORCCH3CH3CH3RXROR+HXSN1ROH+第15頁(yè)/共78頁(yè)HOBrHOCH3OHHOBrH2CCH3CH3H+OBrCCH3H3CCH3Mg無(wú)無(wú)水水乙乙醚醚OMgBrCCH3H3CCH3(1) CH3CHOOCCH3H3CCH3CH3OH(2) H2OH+H2OHOCH3OH+H2CCH3CH3第16頁(yè)/共78頁(yè)ROHH+OOORH+H2OROH+OOHORTHP第17頁(yè)/共78頁(yè)OCOHRH+ROH+OCORR+H2OOCOHROHCOHRROHOHCOHRROHOHCOHRROHOHCORRH2OH+OCORRH+第18頁(yè)/

6、共78頁(yè)SO2ClH3CROH+3 HCl+ROPOCl2ROH2(RO)3POSO2ORH3C+HClPOCl3ROH+HNO2H2SO4H+RONO2RONOROSO3HH2O+HNO3第19頁(yè)/共78頁(yè)IHROHBrHor NaBr / H2SO4ClHZnCl2,RBrRIRClROHHROH2RXRH2ORXX(SN2)(SN1)H2O+X( X = Br, I)第20頁(yè)/共78頁(yè)ROHROHZnClZnCl2ClClROHZnClClRClHOZnCl(SN2)R(SN1)ClRCl+HOZnCl+第21頁(yè)/共78頁(yè)ROH+RBrPBr3RIPI3or P, I2ROHPBrBrB

7、rROHPBrBrBrRBr+HOPBr2(SN2)第22頁(yè)/共78頁(yè)反應(yīng)有兩種立體選擇性（與溶劑有關(guān)）構(gòu)型翻轉(zhuǎn)構(gòu)型保持OH +SOCl2醚為溶劑SOCl2NHRRClHRRClHRRSClClOOHHRROSClClOHHRROSClOHRR構(gòu)型翻轉(zhuǎn)第23頁(yè)/共78頁(yè)NOSClONCl SO2 N（SN2）OSClOHRRHRRCl- -OSONHRRHRRCl構(gòu)型保持OSClOHRRCHRROSClOCHRRCl+SO2SNi機(jī)理（ Substitution Nucleophlic internal, 分子內(nèi)取代機(jī)理）第24頁(yè)/共78頁(yè)OHRTsClOTsRNaCNKOAcNaICNROA

8、cRIR+OTsCH3SOOOHRRNuHRRNu+CH3SOOO（SN2）H3CSO2Cl第25頁(yè)/共78頁(yè)CCHOHH+CCH2O+Al2O3 CCHOHH+CCCCHOH2BE2H2O+HBH2OCCHBE1CC+HB第26頁(yè)/共78頁(yè)CH3CH2CCH3OHCH3H3CCH3CH3+H3CCH3CH2CH3CH2CHCH2CH3OHH2SO4, H2OCH3COHCH3CH3CHCH3H2SO4, H2OH+H3CCCCH3CH3H3C+CH3CCHCH3CH3H2COHAl2O3OHOHAl2O3 第27頁(yè)/共78頁(yè)CH2ROHCHROHRCROHRCH2R O CHRO O COO

9、HR O CROR O 堿堿性性、中中性性不不反反應(yīng)應(yīng) O CRRCHR,H2OH+ O RCOOH +CRRO酸酸性性 用常見(jiàn)的強(qiáng)氧化劑（HNO3, KMnO4 / OH，K2Cr2O7 / H2SO4）氧化致最終產(chǎn)物第28頁(yè)/共78頁(yè)CH2CH2CHHOCHCH2OHCH2CH2CHHOCHCHOHOHOOHMnO2OHOOHMnO21o醇 羧酸HOCrO3, H2SO4丙丙酮酮OCH2ROHCOOHRCrO3, H2SO4;丙丙酮酮2o醇 酮1o 醇 醛 2o 醇 酮第29頁(yè)/共78頁(yè)CrO3N2OHOCrO3NCH2OHH3C(H2C)4CrO3(C5H5N)2COH3C(H2C)4H

10、CH2Cl21o 醇 醛， 2o 醇 酮第30頁(yè)/共78頁(yè)CHROHRCROR+CH3COCH3CHH3COHCH3+AlOC(CH3)332o醇 酮，不影響雙鍵AlOC(CH3)33CHROHR+AlOC(CH3)32OCHRR+CH3COHCH3CH3AlOCRRHOCH3CCH3AlOCRRHOCH3CCH3OBu-tOBu-tOBu-tOBu-tAlOCRRHOCH3CCH3OBu-tOBu-t+第31頁(yè)/共78頁(yè)CCHOHCCHOCCHXCCHOCCCCHORCCOHHOCORCCHOTsCCHNu失失去去氫氫成成醚醚成成磺磺酸酸酯酯取取代代酯酯化化鹵鹵代代消消除除氧氧化化CCHOo

11、r：OHAlOC(CH3)33CH3COCH3O第32頁(yè)/共78頁(yè)R1CCR4R3R2稀稀冷冷 KMnO4or OsO4R3CCR4R1R2HOOHcisRCOOHH2OOHorHtransCl2, H2ONaHCO3 O R3CCR4R1R2HOOHR3CCR4R1R2OHOHH2O?cis + trans第33頁(yè)/共78頁(yè)RCOR+Mg(Hg)H2ORCCRRROH OHRCORCH3CCCH3H3CCH3OHOHH3CCOCH32Mg(Hg)H2OOMg(Hg)H2OOH OH2第34頁(yè)/共78頁(yè)HCCRHOHOHCRROHH5IO6HCCRRROO+CHOHO+CCRRHOOHH5IO

12、6CROOHCRHO+HCCRRHOHOHH5IO6( (高高碘碘酸酸) )KIO4( (偏偏高高碘碘酸酸鉀鉀) )NaIO4( (偏偏高高碘碘酸酸鈉鈉) )orHCCRRHOHOHOHHO+HCCRRHOO+H2O 2O第35頁(yè)/共78頁(yè)CH3CCCH3H3CCH3OHOHCH3CCH3CCH3CH3OH+H2OCH3CCCH3H3CCH3OHOHH+CH3CCCH3H3CCH3OHOH2CH3CCCH3H3CCH3OHH2O- -CH3CCCH3H3CCH3OH- -H+CH3CCH3CCH3CH3O CH3H2O- - CH3更穩(wěn)定的正離子第36頁(yè)/共78頁(yè)P(yáng)hCCHPhHOH OHH+

13、PhCCHPhHOPhCCPhHHO CH3CCPhPhCH3OH OHH+PhCCCH3PhCH3OPhCCPhCH3CH3O HCCHPhCH3OH OHH+HCCCH3PhHOPhCCHHCH3O 第37頁(yè)/共78頁(yè)重排有利因素：遷移基團(tuán)與離去基團(tuán)處于反式CH3OHHOH3CH+CH3OH2HOH3CCH3HOHOCH3H+CH3H2OHOCH3OH3CH3C快快慢慢H3CH3CO- - OH2- - OH2第38頁(yè)/共78頁(yè)OH OHH+OOH OHH+OOOMg(Hg)Mg(Hg)22H3CH3CCH3CH3OBF3-Et2O( (Lewis酸酸) )CCCH3H3CCH3CH3O第

14、39頁(yè)/共78頁(yè)酚-羥基與芳香環(huán)直接相連的化合物。通式：Ar-OH酚的命名可在“酚”字的前面加上芳環(huán)的名稱(chēng)，其它取代基的名稱(chēng)則寫(xiě)在芳環(huán)之前。OHOHClCH3OHOHOHOHOHCHOOHCOOH苯酚(3-甲基苯酚)間甲基苯酚-萘酚(2-萘酚)(4-羥基苯甲酸)對(duì)羥基苯甲酸(2-氯苯酚)鄰氯苯酚對(duì)苯二酚(1,4-苯二酚)間羥基苯甲醛(3-羥基苯甲醛)一、命名：第40頁(yè)/共78頁(yè)1.酚羥基的反應(yīng)酸性四、化學(xué)性質(zhì)四、化學(xué)性質(zhì)酚只能與強(qiáng)堿成鹽，而不能與NaHCO3或Na2CO3作用。酚的鈉鹽則能被碳酸所分解而成酚。OHH2CO3R-OHpka：6.371017OHNaOHONaH2O（渾濁）（澄清）

15、OHNa2HCO3CO2H2Opka=-lgkapka，酸性第41頁(yè)/共78頁(yè)取代苯酚酸性隨取代基的性質(zhì)不同而苯酚酸性強(qiáng)弱不一。一般：芳環(huán)上連接吸電子基酸性芳環(huán)上連接供電子基酸性Pka：7.154.090.25OHNOO：NO2OHNO2NO2OHNO2NO2第42頁(yè)/共78頁(yè)與三氯化鐵的反應(yīng)不同的酚所產(chǎn)生的顏色不相同：OHOHOHOHOHOHOHOHOHOH紫色紅棕色藍(lán)色藍(lán)紫色深綠色C=C OH大多數(shù)酚或具有結(jié)構(gòu)的脂肪族化合物與三氯化鐵的水溶液作用，生成有色物質(zhì)。6ArOH+FeCl3H3Fe(OAr)6+3HCl紫色絡(luò)合物第43頁(yè)/共78頁(yè)酚與醇相似，也可生成醚。但因酚羥基的C-O鍵比醇牢

16、固，所以不能直接失水成醚，而必須用間接的方法。成醚反應(yīng)ONaCH3IOCH3NaIONaOCH3CH3OSO2OCH3CH3SO4Na硫酸二甲酯第44頁(yè)/共78頁(yè)鹵代 硝化2.苯環(huán)上反應(yīng)OH3Br23HBr+H2OOHBrBrBr-（白）OHBr2OHBrOHBr+CS2或CCl405OH稀HNO3OHNO2OHNO2+2013%40%第45頁(yè)/共78頁(yè)鄰硝基苯酚和對(duì)硝基苯酚可以用水蒸氣蒸餾方法進(jìn)行分離。對(duì)硝基苯酚則只能在分子間形成氫鍵。鄰硝基苯酚可以在分子內(nèi)形成氫鍵。這就決定了它們?cè)诜悬c(diǎn)和水溶性方面的差別。在水溶液中：鄰硝基苯酚不能與水分子形成氫鍵。對(duì)硝基苯酚能與水分子形成氫鍵。O-NHOO

17、=+-ONHOONOOOH=+-NOOOHOHHOHH=-+鄰硝基苯酚（形成分子內(nèi)氫鍵容易揮發(fā)）對(duì)硝基苯酚（形成分子間氫鍵不易揮發(fā)）第46頁(yè)/共78頁(yè)OHNO2OHNO2OHNO2沸點(diǎn):100194分解水中溶解度:(g/100g水)0.21.41.7亞硝化OHOHNOOHNO27880%對(duì)亞硝基苯酚對(duì)硝基苯酚NaNO2+H2SO4稀HNO3第47頁(yè)/共78頁(yè)1).瑞穆?tīng)?蒂曼反應(yīng)（K,Reimer-F,Tiemann）歷程：OHOH+ CHCl310% NaOHCHOHOCHO+OHOH-O-:CCl2OHCClClO-CHCl2OHCCl2O-CHCl2H2OOHCHOOHCHO+第48頁(yè)/

18、共78頁(yè)ONa+ CO2125-150 C5atmOHCOONaH+OHCOOHOK+ CO2210 COHCOOKH+OHCOOHOCH3OAlCl3OOMe-Cl3AlOAlCl3+CCH3OOHCH3OOHCH3O.第49頁(yè)/共78頁(yè)4）Claisen重排反應(yīng)（苯基烯丙醚）OCH3H3COCH2CH=CH2HCH2CH=CH2HOCH3H3CCH2CH=CH2HOCH2CH=CH2H苯酚的烯丙基醚在加熱條件下，烯丙基優(yōu)先重排到鄰位碳原子上，當(dāng)鄰位被占據(jù)后，才重排到對(duì)位。第50頁(yè)/共78頁(yè)CH2CH=CHCH3OH3CCH3OH3CCH3CHCH=CH2CH3OH3CCH2CH=CHCH3

19、CH3HOHH3CCH2CH=CHCH3CH3第51頁(yè)/共78頁(yè)3.氧化反應(yīng)利用酚的易氧化性，鄰苯二酚與對(duì)苯二酚常用作照相底片的顯影劑，將氧化銀還原成金屬銀。酚比醇容易被氧化，生成苯醌。二元酚和多元酚比苯酚更容易被氧化。OHOOK2Cr2O7/H+對(duì)苯二醌（黃色）OHOHOOAg2O鄰苯二醌（紅色）+2Ag+H2O第52頁(yè)/共78頁(yè)1.磺酸鹽堿熔法該法按三步進(jìn)行：SO3HNa2SO3SO3NaSO2H2O+中和SO3NaNaOH（固）ONaNa2SO3+325350堿融ONaOHNa2SO3+SO2H2O+酸化五、酚的制備五、酚的制備第53頁(yè)/共78頁(yè)當(dāng)氯原子的鄰、對(duì)位連有吸電子基團(tuán)時(shí)，水解比

20、較容易，不需要高壓，甚至可用弱堿。ClNaOHONaCl-H+OH+35040020MPaClNO2ONaNO2OHNO2ClNO2NO2ONaNO2NO2OHNO2NO2H+H+NaOHH2ONa2CO3H2O第54頁(yè)/共78頁(yè)第55頁(yè)/共78頁(yè)RORROR（R = 烷基）CHORArOR(CH2)nOOOOOOORRROR第56頁(yè)/共78頁(yè)OCH3OCH3H3COHOCH2OHOCH3CHCH2CH2CH2CH3CH2OCH2CH3CH3COCH2CH3CH3CH3CH2CHOH3C第57頁(yè)/共78頁(yè)OH2CCH2OH2CCH CH3OCH3H3CHH123123OOOOO412365第5

21、8頁(yè)/共78頁(yè)RORRONaLR+NaL+CH3COCH2CH3CH3CH3CH3CONaCH3CH3XCH2CH3+OHCH3OTs+NaOHOCH3CCH2ClClCH2CH2OHCH2ClNaOHCCH2ClClCH2OL = X , TsO第59頁(yè)/共78頁(yè)OHR2H+ROR+H2O OOHHO+H2OH2SO4HOOH2H2SO4OO+H2O2第60頁(yè)/共78頁(yè)CH2CRRHOR+HClCH3CRRORHOBrHOHOBrH2CCH3CH3H2SO4OBrCCH3H3CCH3NaCCHOCCH3H3CCH3H+H2OHO第61頁(yè)/共78頁(yè)CHCH2RH2O, THFCHCH3ROHH

22、g+Hg(OAc)2NaBH4H2OOHHORORCHCH2RHgOAcOAcCHCH2RHgOAc H2OCHCH2RHgOAcHO- - H+CHCH2RHgOAcHOH CHCH2RHgHHOCHCH3RHOHg+NaBH4第62頁(yè)/共78頁(yè)CHCH2RROHCHCH3RORHg(OCCF3)2NaBH4OCCHRROHCCH2RORHg+NaBH4CCHRCCH2ROHHgSO4H2OCCH3RO第63頁(yè)/共78頁(yè)CORRH H+CHORRH 第64頁(yè)/共78頁(yè)CORRHHO2（空空氣氣）CORRHOOH第65頁(yè)/共78頁(yè)RORHClRORHOOBH3MgRXEtOEtEtOEtBH3

23、Cl+RORH2SO4RORH+HSO4+ Brnsted堿 Lewis堿第66頁(yè)/共78頁(yè)H+RORHNuRNu+HORRORROR NuRNu+ORSN2第67頁(yè)/共78頁(yè)H3CCHH3COCHCH3CH3H3CCHH3CIO48% HBr(過(guò)量)OHBrBrBr +H3CCHH3COH H3CCHH3CIHIHI（過(guò)量）2RORHXRXHOR+X = I, Br 第68頁(yè)/共78頁(yè)CH3CH2OCH2CH2CH3CH3CH2OHICH2CH2CH3+CH3CH2IHOCH2CH2CH3+HICH3OCH2CH2CH3HICH3IHOCH2CH2CH3+CH3OCCH3CH3HICH3OH+CH3OC