復(fù)旦有機(jī)化學(xué)課件16-22芳香含氮、酚醌雜環(huán)與生物有機(jī)物

一．堿性條件下酚類芳環(huán)上的取代反應(yīng)苯氧基負(fù)離子活化的芳環(huán)（易親電取代）苯氧基負(fù)離子的結(jié)構(gòu)分析氧負(fù)離子（作為親核試劑）烯醇負(fù)離子片斷（作為親核試劑）OOHBOHH2C

OOHOHCH2OHCH2OHOHCH2OH＋H2C

OOHOHOHCH2+HOOHCH2+

HOOHCH2H2C

OOHOHCH2OHOHOH1.

堿性條件下的酚醛縮合聚合產(chǎn)物與酸性條件下的縮合類似酚醛樹(shù)脂OOOHOCH2OCH2HOHOOCH2OHCH2

OH

－OH－H2OOHOHCH2聚合機(jī)理縮合機(jī)理OHOHOH2C

OOCH2OHOCH2OHOCH2OHCH2OHOCH2OHCH2OHOHH2C

OCH2OHCH2OH類似Aldol縮合Michael加成2.

Kolbe-Sitt反應(yīng)乙酰水楊酸(Aspirin)OHNaOHOHCO2

HOHCO2H加壓120-140oCCO2Ac2OOAcCO2H反應(yīng)機(jī)理

O

C

OOOOCO2CO2HOHOHCO2H2H對(duì)氨基水楊酸（抗結(jié)核病藥物）例：OHHONaOHCO2,

135oC1.2.OH2H

NNaOHCO2,

120oC1.2.OHHOOHH2NCOOHCOOHHH生成對(duì)羥基苯甲酸酸OHK2CO3OHCO2200300oCOHH+OHCOOH240oCCO2KOHCO2KK2CO3CO2HOHCO2HH+鉀鹽，高溫有利于生成對(duì)位產(chǎn)物OHOHCHOCHCl3CH3CH3OHCH3OHCH3OHCH3CHOOCH3CHCl2OHCHCl3OHC少量＋＋3.

Reimer-Tiemann反應(yīng)例：OHOHOHOHCHO+OHCHOCHCl3OHOHOCHCl3OHCCl3

ClCCl2OHCCl2OCHCl22OHOCHOH+OHCHOCCl2OCH(OH)2H2OReimer-Tiemann反應(yīng)機(jī)理（卡賓機(jī)理）二氯卡賓（親電性）二．酚類化合物的氧化易氧化的酚類弱氧化劑間位苯酚氧化不生成醌OHOOOHorOHNH2Ag2OOHOHOOAg2OOH

O[O]醌類化合物O對(duì)位苯醌（1,4-苯醌）鄰位苯醌（1,2-苯醌）酚類的氧化——基過(guò)程HO[O]OOOOHOOH+基偶合OOOHOH+O[O]OOHOH+中加入微量對(duì)苯二酚抗氧劑BHT食品、飼料、動(dòng)植物油、肥皂的抗氧劑橡膠、塑料的防老劑OHC(CH3)3(H3C)3CRHOCH3(H3C)3CC(CH3)3+RCH3BHT(Butylated

hydroxytoluene)穩(wěn)定的氧基酚類作為抗氧化劑例:

?在新處理苯三．芳基醚的反應(yīng)及在

中應(yīng)用1.

芳基烷基醚的水解（用Williamson醚法）總是生成苯酚和碘代烷，為什么？復(fù)習(xí):

芳基醚的OHNaOHONaR

X

orO

RR

OTsor

NaHO

RH

IOH+

R

IH

IAr

O

Ar'二芳基醚不分解，為什么？OHO

CH3(1)

NaH(2)

(CH3O)2SO2or

CH3IOR

C

ClAlCl3OCH3CORH

IOHCOR芳基烷基醚的水解在上的應(yīng)用——保護(hù)酚羥基例：AlCl3用量較大，產(chǎn)率不高溫度過(guò)高時(shí)醚被分解OHOR

C

ClAlCl3COR先轉(zhuǎn)變成甲基醚（保護(hù)羥基），再?；疧H

OH+COR（上次課內(nèi)容）溫度不能過(guò)高OAlCl2AlCl3CH3Cl+將酚轉(zhuǎn)變?yōu)榉蓟S基醚氫化脫芐基芐基與雜原子相連，催化氫化時(shí)易脫去常用于氨基的保護(hù)和脫保護(hù)OHO

CH2Ph(1)

NaH(2)

X

CH2PhOR

C

ClAlCl3O

CH2PhH2

/

Pd-C+OR

C

OHCH3PhOR

CN

CH2PhRRH2

/

Pd-CRRN

H+

CH3PhRRON

C

O

CH2PhH2

/

Pd-CRRN

H

+

CO2

+CH3Ph2.

芳基醚的Birch還原及水解成環(huán)己烯酮復(fù)習(xí)：Birch

還原（給電子基）（吸電子基）Li,

NH3

(l)EtOH取代基對(duì)反應(yīng)的影響OR

Li,NH3

(l)EtOHORLi,

NH3

(l)EtOHCOOHCOOH(上冊(cè)，p268,

第7.8節(jié))(下冊(cè)，p779,

第17.11節(jié))R,

OR,COOH,OH,COOR,NH2(R),CONR2COR以下基團(tuán)反應(yīng)時(shí)不受影響以下基團(tuán)反應(yīng)時(shí)可被破壞X,

NO2,

CHO,H3COOCH3Li

/

NH3EtOH3H

COOCH3OOCH3H2OH+Li,

NH3

(l)OCH3

OCH3EtOH烯醇醚，易水解HCl/H2OOHCl/H2O

/O或H2O/OHBirch還原應(yīng)用：通過(guò)Birch

還原環(huán)己烯酮例:問(wèn)題：為什么還原不發(fā)生在另一個(gè)環(huán)上？請(qǐng)寫(xiě)出后兩步反應(yīng)得機(jī)理OCH3OHCH3OH3CCH3OHH3CCH3RR3.

烯丙基芳基醚的Claisen重排及[3,

3]

遷移注意烯丙基與苯環(huán)的連接位置190~200oCClaisen重排O

OHOH+主要產(chǎn)物CH3OCH3OCH3H1231'O2'3'11'OH2'233'

CH31231'2'3'CH3O

HOCH3HOHCH3HCH312O

H1'32'3'1231'

H2'3'121'2'3'3重排過(guò)程（協(xié)同機(jī)理，六員環(huán)過(guò)渡態(tài)）[3,

3]

遷移六員環(huán)過(guò)渡態(tài)六員環(huán)過(guò)渡態(tài)互變異構(gòu)互變異構(gòu)第一次重排第二次重排鄰位產(chǎn)物對(duì)位產(chǎn)物乙烯基烯丙基醚的[3,

3]

遷移（屬于Claisen重排）1'O2'H1'O2'21

11'O2'33'233'3'123OH3CCO2EtOH3CCO2EtOC2H5200oC200oCOC2H5H1231'O2'3'2312'

1'CHO3'Cope重排——1,5-己二烯的[3,

3]

遷移（p858,

第18.20節(jié)）Cope重排可逆Claisen重排與Cope重排131'R2'

3'

RRR12

231'2'3'X=O,

Claisen重排X=CH2,Cope重排121'X3

R3'

R2'RR231X1'2'3'HCH3CH3HCH3HCH3CH3HCH3HHHHCH3HCH3CH3CH3化學(xué)——機(jī)理：HHCH3CH3Cope重排的H專一性反應(yīng)Z型225oCCH3CH3E型椅式構(gòu)象過(guò)渡態(tài)不可逆的Cope重排1231'2'

3'1231'2'3'HOHOOHOHHOO

互變異構(gòu)擴(kuò)環(huán)四．芳基酯的Fries重排Fries重排特點(diǎn)產(chǎn)率較高。環(huán)上有間位定為基時(shí)不發(fā)生。

低溫對(duì)位產(chǎn)物多，高溫鄰位產(chǎn)物多。例：其它催化劑：BF3,ZnCl2,FeCl3,

TiCl4OAlCl3OHROCC

ROOHCRO+OAlCl3H3COCC

CH3OOHCCH3OHOCH3AlCl3CH3165oC25oCCH3Fries重排機(jī)理（分子間重排，芳環(huán)上的親電取代）OAlCl3OC

ROAlCl3OC

ROO

CRO

COOOCRAlCl3RHOAlCl2OC

ROCROH2OHOC

ROOOHHHOCROOCROHCO

ROHH2O+酯的水解+CROR

C

OHHHClOCH3重排發(fā)生在分子間的實(shí)驗(yàn)證明OCCH3ClOCPhOCH3+AlCl3OHH3COCCH3ClOHCPhOCH3OHPh

COCH3OH3CH

COCH3Cl+++Fries重排的其它可能機(jī)理OAlCl3OH3C

CCH3COO

AlCl3OH3C

CO

AlCl3+H3C

C

OO

AlCl3H或鄰位ClCCH3OO

AlCl3H2OOHCCH3O本次課小結(jié)：通過(guò)苯氧基負(fù)離子進(jìn)行的反應(yīng)（堿性酚醛縮合,

Kol