药学院药物合成反应习题

第一章 卤化反应

1，写出下列反应的主要产物（或试剂）

①

BrCH3OC6H4CHCHHBr2CCl42~5℃C6H4OH3CHHHBr

②

OOBrBrOCH3BrOOCCl4ref 5fH3CCH3H3CCH3CH3O

③

C8H17C8H17O2CF3CI2, CF3COOAgI

④

OOSiMe3MeNBSTHF00BrMe

⑤

(C6H5)3PI2C6H6 refHOHHI

⑥

BrBrOBrBrEt2O,HCLOOOAc

⑦

AgFICH2COOMeFCH2COOMe

⑧

OAcCOCBrBr,NaOHCOCH3CH2O diox,100HO

COOHHClH2OHO

⑨

B2H6BHCHCH3CHCH32H3CHBCH3I2NaOCH3CH3OHCH3CH2CHICH3

2,写出下列反应可能产物

HBr 100℃①

(CH3)3CCH2OH封管(CH3)2CCHCH3+(CH3)2CHCH3CH3+(CH3)3CCH2Br

②

HCH3CCCH3COOCH3NBS,(C6H5CO)2O2CCl4refHCCCOOCH3CH3HCH3CCCOOCH3CH2BrBrH2C

③

CH2COCH2CH2CH3BrCH3CCH2CH2CH3OBr2 KClO3,H2O40~45℃CH3COCH2 CH2CH3Br

④

ClCHClCHCH3CHCC2H5HH3CCl2,CH3COOH25℃C2H5H3C+HOCOCH3CCClC2H5H3C+HHClCCC2H5HOCOCH33，写出下列反

应的主要试剂及条件

①

PBr3/170~180℃C(CH2OH)4C(CH2Br)4

②

HOOC(CHSOCl2/Ref2)4COOHClCO(CH2)4COCl

③

PhCH2COCH3SOClor,Cl2/RefPhCHCOCH2/加热3Cl

OCOOHorIHgO/I2/LTA/CCl4/ref2/加热orAgNO3I④KOH 2加热第二章 烃化反应

4，完成下列反应

①

COOCH3OHCH3INaOHOH②

OCOOCH3OHOCH3

OHOCH3OHMe2SO4K2CO3OHOCH3OCH3

③

H2CH3CH2COCH2CH3OH,H2SO4H3CCH2OH CH3OH,CH3ONaH3COCH3H2CCH2OHOH

④

Me2SO4(H2C)5CONH(H2C)5CONCH3

⑤

O2NClPhNH295℃O2NNHPhNO2NO2

⑥

CH3C6H4SO2ClH3CC6H4SO2OHHOHCH2(COOC2H5)2C2H5ONaC2H5OH(EtO2C)2HCH

⑦

NH2CH2OHNHCH2Raney-Ni,加热

⑧

OH3COLiH3CLDA/CH3OCH2CH2OCH3-40~0℃ 2,完成下列反应过程

①

OCNCOCH(COOC2H5)2OCNaNC(COOC2H5)2C2H5ONaC2H5OHCOCH2COOC2H5OCNCOClCH2COOC2H5150~160℃C(COOC2H5)2HCl H2OCH3COOHH2NCH2COOHCHCOOH

②

CHOCH2NHCH3+CH3NH2H2/Raney-NiOCH2NCH3CH2CH2OH

③

OC6H5CH2NH2(C2H5O)2PHOC6H5CH2NHP(OC2H5)2OH2CCHCH2Br/50%NaOH(n-C4Hg)4NHSO4C6H5CH2NP(OC2H5)2CH2CHCH2HClHClC6H5CH2NCH2CHCH2

④

NH2(H3C)3CO(H3C)3CNC6H6 ref带水CH3CH3C2H5MgBrrefOCH3(H3C)3CNMgBrCH3CH3H2CCCH2ClCH2C=CH2(H3C)3COrefOCH3

第三章 酰化反应

①

CH3+CH3COClH3COOCH3OCH3AlCl3COH3COOCH3OCH3

②

HO2NCOHNHCOCHCl2CHCH2OH+CH3(CH2)16COClN/C6H6HO2NCOHNHCOCHCl2CHCH2OOC(CH2)16CH3

③

SH2NNOOCCNNNH2CSNNNCH3NH2CSNNNCH3CCOOHClCH2CONHS+NOCH3DCCTHFSClCH2CONHSNOCH3O

④

CH3CH3(CH2)5COClAlCl3ClCH2CH2ClCH3CH3O

⑤

OCH3H3COOCH3H3COCHOH3COZn(CN)2/HCl①DMF/POCl3②H2OH3COH3COH3CO

⑥

CHOCH3+C6H5NCHOPOCl390~95℃ACONaH2O

⑦

CH3COCH2COOC2H5+140℃4~5小时H3CCOCH2COOHO

2，完成下列合成路线

①

OHEt2SO4,NaOH或C2H5X,NaOHOC2H5DMFPOCl3CHOCOClOC2H5Cl2OC2H5H2NSCH3CH3OCNHSOC2H5CH3CH3COONaNOCOONaNO

②以苯和丁二酸为起始原料合成四氢萘

OO+OAlCl3CH2CH2COOHOZn-HgHClCH2CH2CHOOHHFCH3H2OZn HgHClO

第四章 缩合

①

COCH3+HCHO+CH3NHCH3COCH2CH2N

CH3COCH2CH2NCH3NHCOCH3+HCHO+HN(CH3)2COCH2CH2N(CH3)2

②

HCH3Ph3PHCHCH3+CHOHCH3+HH③

CH3CH2CH2COCH3+CH3COOC2H5碱CH3CH2CH2COCH2COCH3④

CHO+BrCH2COOC2H5H①Zn+C6H6(C2H5)2O②H2OCCHCOOC2H5

2，完成下列反应式

①

OCH3H3COHCNO2+O2NH2OCHOOH

②

OO2Ph3PCHCH3H3CHCCHCH3

③

OHOH2COCH2OHCH2OH+CH2O(过量)Ca(OH)2H2OHOH2C

④

C6H5CHO①(C2H5CH2CO)2O,C3H7COOK②NaOHCOOHCHCC2H5

⑤

OClCH2COOCH3CH3ONaOCOOCH3H2OOHCOOHOHCHO

⑥

O(EtO)2C=O+C6H5CH2CNC2H5ONaC6H5HCCNCOC2H5

(C6H5)3PCH2CH=CH2NaNH2液NH3C6H6回流(C6H5)3PCHCH=CH2⑦

Cl

H3COCH2CH2CHOH3COCH2CH2CH=CHCH=CH2C6H625%

⑧

CH3CO2CH3O+BrCH2CO2CH3ZnC6H6 (C2H5)2OCH3CO2HH2OCH3CO2CH3CHCOOCH3

3,完成下列合成反应

①从甲苯→

COOEtCC2H5COOEt

CH2BrCNCH2CNCOOC2H5HCOCOOC2H5CH3Br2/hvNaCNCOOC2H5H+加热COOEtCHCOOEtCHCOOEtEtOHHCOOEtEtONaC2H5BrCOOEtCC2H5COOEt

②

HCCH3CH3H2CCHOCH3CH3

CH3①CrO2Cl2 CCl4②H2OH3CCH3H2CHCCH3CHOCHOCH3CH2CHOC2H5ONaH3CCHCCHOCH3Pd-CH2 125℃CH3

4，填写下列各部产物

①

HCHO/OHα甲基丙醛A(C5H10O2)DBH3CHCNH3OB(C6H12O4)+H2OC(C6H10O3)NH2CH2CH2COOCH2PhAH3CCH2OHCCH3CHOH3O+E(C9H17NO5)+PhCH2OHCH2OHCCH3CHCNCOHH3CH2CCCH3OOCHOHOHNCH2CH2COOHDH3CECH2OHCCH3HCOHOHNCH2CH2COOCH2PhH3CCH2OHCCH3HCOH

②

COCH3COCH3CH3OCH2CH2COCH3O(C2H5)2NCH2CH2COCH3CH3ONa,CH3OH,C6H6CH3KOHCH3OH H2OH3O+O

③

OHC①ZnBrCH2COOEt②CH3ONa,CH3OH,C6H6CHCHCOOEtLAHCH2CH2CH2OH①HBr②KCNCH2CH2CH2CNH3OCOOH①SOCl2②AlCl3O

第五章 氧化反应

1，完成下列反应式

①

CH3CHOCrO3/Ac2OH2SO4NO2NO2

②

CH3COOHNO2CrO/H2O高温 高压

③

CH3CH3CH3COCH3CH3COClAlCl3①Br2 NaOH②H+COOHCH3CH3CH3

④

RRMnO2CHCl3HOOHHOO

⑤

OcAOAcKMnO4, KIO4,H2OBaOH, K2CO3 35℃OOOOH ⑥

CH3CH3NO2CrO2Cl2CS2 25℃NO2OCH3OCH3

⑦

CH2OH(C5H5N)2 CrO3CH2Cl2HOHOCHO

⑧

0.5MSeO2C2H5OH回流OH

⑨

OHHOHOODMSO-DCC H3PO4RTH3COH3CO ⑩

CH3OCOOCH3CH2O2 NaOHRORO

⑾

ClCOOOHH3CHH(C2H5)2O 25℃H3CHOH

⑿

C6H5COOOHCHCl3COCH3HOCOCH3H

2,试以化学表示实现下列变化的各步反应

①

COOHCHO稀NaOHC2H5CONH2CHOAg2OC2H5①SOCl2②NH3C2H5RCO3HOC2H5CONH2

②

HO(CH2)6CH3H3CH3CSO2ClSO2O(CH2)6CH3DMSOOHC(CH2)5CH3

③

OHOH①H2SO4②KMnO4稀NaOHCHOOHPb(OAc)4CHOCHO

④

OOOOH①CrO3 H2SO4 H2O②SeO2Bu-t①KOH②HCl,加热Bu-tBu-t

第六章 还原反应

1，完成下列反应

①

CH3CH=CHCHO0.25MNaBH4CH3CH=CHCH2OH

②

NO2NH2NH2 H2OPd-C/C2H2OHNH2

③

OOH0.25MNaBH4or 0.25MLiAlH4or M PV

④

OCH3OC(CH2)3OCH3OC(CH2)3OCH3OCH3Zn-Hg HClBrBr

⑤

B2H6THF 25℃2BHH2O2 NaOHHOHCH3H

⑥

CH3OH3COClCH3OPb-BaSO4 H2Q-SH3COH

⑦

2PHCH2CH=CH2+Pd/C2PHCH2CH2CH3+

⑧

OOH2/(Ph3O)3RhCl

⑨

OH2/Pd-CAcOH,HClO4OPhHOCH2CH2OCH2CH2Ph

CH=CH2CH=CH2OCHOHCAl(OCH(CH3)2)3H3CO(CH3)2CHOHNH3CO⑩

N

2,改错

①

HOOCCOOEtLAHC2H6HOH2CCOOEtLAHHOH2CCH2OH

②

Zn-Hg HClCH3COCOOEtCH3CHOHCOOEt

③

CH3OH3CH3CCH3HCH3HOCH3HHCH3CH3LAHH3CH3C

3，完成下列合成题

H2CC=OCH21，试由环己醇、氯乙酸、乙醇合成(H2C)7

OHCl(CH2)6ClClCH2COOH2CH2(COOC2H5)2CH2(COOC2H5)2+Cl(CH2)6ClC2H5ONa(C2H5OOC)2CH(CH2)6CH(COOC2H5)2Na C6H4(CH3)2ref①H2O NaOH②EtOH H+C=OCHOHC2H5OOC(CH2)8COOC2H5H2C(H2C)7C=OCH2H2C(H2C)7Zn/HClHOAc

O2，试由

OCH3 合成O

OOHOH0.25MNaBH4OCH3H2OH+OCH3OH+O

HCOOEtOO3，试由

HHCH2CH2COOH 制备

COOEtHCH2OHNaC2H5OHHCH2CH2COOHHOOCH2CH2COONaH+

1，完成下列反应式

第七章 重排反应

①

OHOHO稀H2SO4

②

CONH2HHOHHOHHOHOHCH2OHCONH2HOHHOHOHCH2OHNaOCl/H2OHOHH

③

CH2C6H4OCH3NCH3C2H5C6H5LiEt2OPH2COCH2C6H9NCH3+C2H5NCH3CH2C6H5OCH3PC2H5

④

-ClNPhLi/PhH加热N ⑤

CH2N(CH3)3NCH3NaNH2/NH3NCH3CH2N(CH3)2

⑥

CH3OHOHCH3H+-H2OCOCH3CH3

⑦

OCH3OCH3OCH3NaOCl/NaOHOCH3CONH2NH2

⑧

NCHNHCEtOOC180℃EtOOC

⑨

CH3OCH3OHPhNEt2ref 2HOCH3OCH3

⑩

CH2NH2HOONaNO2/H+CH3H3C

⑾

CH3C(OEt)3142~147℃8 daysHOCH2COOEt

⑿

CO2MeMeMeCO2Me①HCl-HOAc-Ac2O②H3O+CHMe2HOMe2NH2CHMe2

二，完成下列合成过程

①

2KCNCHOOOHCOHCOOHNO3COOOOCO①KOH②H+OOHCOOH

②

CH3+OCHOOC2H5OCHOOH加热OOOOHCCHO加热OOCH3

③

OHCHEtCH3+2H5OH/TolHH2,4-O2NC62C3COOC100℃ 8hrEtOCH3CH3Etclaisen重排OCH3OCOOCHH3EtCH3NaBHEtCH3H42COCH3CH3OHCOOCH3OCH3EtOHCH3COOCH3claisen重排OEtEtEtCH3COOCH3EtOEtCH3COOCH3CH3COOCH3NaBH4CH3OH