北大复试等多个文件有机课件

DerivativesofCarboxylic四、结构和与性质的关系 ）O

酸酐 OO

OO

O酯

O 酰胺

O

OO

O O

O

沸(熔)点：酰卤、酸酐、酯<羧酸；羧酸<酰胺 Esters Estersgiveflowersandfruitstheirpleasantfragancesandflavors.

O

H3CNH2 O

H3COHH3CCl+- 中的和都为sp

+l-

+R - O- ''R RO OO OrbitalOverlapinCarboxylicAcidlonepairorbitalofsubstituentOrbitalOverlapinCarboxylicAcid electronpairofsubstituentleaststabilizedC=O

moststabilizedRORO R,

ROCLO

+ O+O+L慢

+R

L

L L

+ 1、羧酸衍生物的水解O Cl+

+ + +

+ OOOOOOOOR-C-Cl＞(R-C)2OR-C-OR'R-C-

+

+

0

OCHOCH3C-OBrC2H5OH-95%CHCO-3+HCCOHCC OOO RCN

R-C-OH+

D

RCN+

R-C- 反应条件：浓H2SO4/室温、NaOH/H2O2O

OCHCOOC

OH+O +

R

HRRCOO-+RCOO-+RCOOHRCOOH- + OOnRO RtransitionO Rtransitionmi'ROlEm'ROlEmr C Rer O O d+ +

O CO C C OH+OROR

+

a5H2COa5H2COC3F+N-O5+N-O5R

O+O+

快 快O

++O+OH－

- + R： V相对

RCOOC2H587.8％ROH、R：V

CH3COOR R： C2H5-

V相对

1

O+O

++

质子化慢

2 2+

质子转移

+-

O V1°>2°>3°>1°>？

+

OH+ O

C(CH

H

OC(CH

) 3

3 3H-4 H-4 HOOCO+O=+COS2H3HCOOC HOOCO+O=+COS2H3HCOOC碱催化：1°ROH2°ROH酸催化：3°ROH1°ROHO O

+R'OH O

O

+O O

+

O

+

OR''+OR-C-ClOOR-C-ClO>O>O

+ O +

OOO+OOO+OOOO+n-O+OO +C C25H51COOC2H5+ OH

3OH

3+4 43 5 3+4 43

R-C=NHR'OH

R-C=N

R-C-OH+O

O亲核加成-消除R-C-O

+

R-C-O

R-C-

+R'OH或

R-C- +O

R-C-OR''+ O

O

+

O

+

R-C-OR'+O

+

+ O+NH3 +

+

+2OO+CH3NH2OR+OOCCl+O OOOO+OO H2OCO3CO+NH3O

OCNHO

O+

O +

+O +

+

R-C-OH+O

O亲核加成-消除R-C-

+

R-C-NHR' R-C-NH2+OR-C-OR'+

脒(虚线内为脒基

2

NH2 CH3

3

C=NH

2

O

慢 LO

快 L

O

+

Nu 酯～酰胺～腈水解、醇解、氨解的实验事实证明，羧酸衍生物酰化-p -p L

O-pp-Cl-O-C--p

＜-O-R'＜-

O＞NL－愈易离去，越有利于第二步反应（消除反应酸性：HCl＞RCOOH＞ROH＞NH3 离去能力：Cl－＞－OCOR＞－OR’OR523H2O

OCH

)

2

18℃

+

+

+ + + + +

+

+

O

酯

OMgX-ROMgX

O

O O

腈 N+

O N+α-

C10H7- C10H7-O C10H7- CHOCCHCH 酯 +

CuO.CuCrO4

+

CuO.CuCrO4125℃

Na-

O

R"OH

- Na+

R-C-OR'-

R-C-H- e

O2 +4

O

2.

H2 2RCN O

H+ C O O O O

3H+O3

0------

醇醚酯 H

H3

3 H 3

ytilibts C++H

C O 2 22 H HClHClO O C CHHH ytidicai

ClaisenClaisenO O

O O

O O

OOO

HO

2 2

H

H3CCH3CC

OO

35

3+ + OO

O O

O O

OOOO+

O

O OOOO

O

O

1. 2.

2O +

CH2COOC2H5+ OC

+

+ O

O

可用于合成:OOCH2CH2CO2C2H51CH2CH2CO2C2H52O2.ΔOOOO+O OCO2C2H5+5COOC2HC5COOC2HCOC3)C73HC(H)33HC(H52iCLOCHCADFLHT5HOOC3HC3O OC9O2HOADFLHT3)H3C(COOC3HC%09CC2HCH352ClCiS3L5COOC35HOOC3HCH5CH2COrB5H2CADFLHT5HOOC2HC3HC H+ pKa=CHCCH

H+

CH3CCH2

pKa=

H H

pKa=OCH3-C-

CH

COC

dil

Δ

2CH3COOH+O

O- O

CH3COOH+O

O

RH C

H

OOOOΔOO12OO+CHCHCH3222+Δ52 5 5-2 -2

2' '22 22

' '-2' -2'2

－－

－－ －－

CH3COOH+O

OO

OOOCH CHCOC

+BrCHCHCH

H

O

O O

OO

CH3CCCH2CH2CH2BrOO OO

OOOO O

PerkinReactionRobinsonReactionStobbeReaction CHCOOC

(CH)

2

3

DarzenReactionBenzoincondensationWittigReactionMichaelReactionMannichReactionReformaskyReactionBaylis-HillmanReactionFavorskiiRearrangement H2CC +

H2CCNNa+HH2C

O

C + +

CNBr+NaBr+H

ORCOOH>H2O>RCONH2>ROH CHOC +

CNK+H OCNK+ O

OCNROO

+

2 2

N N

O

CH3(CH2)NH2+

+ O

CN- R2 2

C

33222O

HOOC3HC+2HC2HCHC=2HC0053HC2HC2HC2HCOOCCHOOC3HC+2HC2HCHC=2HC0053HC2HC2HC2HCOOCCOCCOHC OCCOHC+HO +HO

D

C6H5-CH-CH

O

顺式消除C6H

H

H

部

D

5000C

H

5000C

5D5D

500CD

H

H C2H5t-BuOK H

Br

H

OAc

CH3

SN2亲核取代

H

第一步为SN2亲核取代，构型翻转，第二步为酯的热消除，顺式消除，得到的产物与前者相同。

-HO

HOAc00 H+-+3d ad a+C+ C33+H HS HC C2RCHORCH== H2HN+a N2S-aa

0C07CS SSNCNCH CHCC CCCHC HHH HRC

CO

OCl-C-

CO+

200

+H2SO4 COCl2+OCl-C-Cl

OO

O

ONH2-C-

+Cl-C-Cl

+碳酸可以形成两种酰胺：氨基甲酸H2NCOOH和尿O

33NH2O

OO

ONOOCNHCH3OCNHCH3

)2

ONH2 NH2弱碱性： CNH2+O

CNH2.HNO3OH2NC

+NH4ClNa2CO3+NH3 NH3+

+

NH2+

COCOCOCO

+

CNH2

HC O NO N O

H2CO

H2CO

+

O

N

O

O+NaHCO3lCH2HNHllCH2HNHlCNHN2H CNHO0501H2C3HHN2H CNHO0501H2C3HCN2H

脒

+ NH2+H2O+

（H2N N2+

CNH244OS.2HNOCHN2HC2HCOlClCH.2HONCHNOCHN2HC2