有机课件-第10章

2第三节羧酸衍生物O

O

OR

C

X

R

C O

C酰卤

酸酐O

OR

R

C

O

R

R

C

NH2(R)

R

C

N酯

酰胺

腈—羧酸衍生物的结构与命名1羧酸衍生物的结构sp2OR

C L

（X、O、N）碳-杂原子键具有某些双键性质OR

C

LO-R

C

L

R+O-C

L+C

N:OH

C

NH2

CH3

NH2137.6

147.4ppm133.4OH

C

OCH3

CH3

OHC

O:

143.0ppm32.羧酸衍生物

名1)

酰氯和酰胺是根据分子中所含的酰基来命名OCH3CH2C

Cl丙酰氯Propanoyl

chlorideCH3

OCH3CHCH2CH2C

ClOHCH3HCNOCH3CH3OC

ClN-甲基乙酰胺N-Methyl

acetamideN,N-二甲基甲酰胺N,N-Dimethyl

formamide(DMF)苯甲酰氯Benzoyl

chlorideOCH3C

NH2乙酰胺Acetamide4-甲基戊酰氯4-Methylpentanoyl

chlorideOCH3CH2CHCBrBrHOOCOCCl4-(氯甲酰)苯甲酸2-溴丁酰溴CH3

OHCH3COOHNHCOCH3N-甲基-3-甲基戊酰胺4-乙酰氨基-1-萘甲酸OR-C-NHNOSCH3CH3COOHR=C6H5CH2-(penicillin

G)青霉素(penicillin)452>

酸酐

名:羧酸的名称后加”酐”O

OCH3C

O

C

CH2CH3O

OCH3C

O

CCH3OOOO乙酸酐(乙酐或醋酐)Acetic

anhydrideOO邻苯二甲酸酐Phthalic

anhydrideO乙丙(酸)酐Acetic

propionic

anhydrideOO丁二酸酐Succinic

anhydride顺丁烯二酸酐Maleic

anhydride6OOOH3COHH3CH2CH3CHOHCH3OHCH3OCH3

OCH3OHCH3N(CH3)2CH3O

OCH3HOOErythromycin

A

(红霉素)AOOOHHO

HCHOH2COHVitamin

C3>酯是根据水解后所得的羧酸和醇来命名甲基丙烯酸甲酯methyl

methacrylate(methyl

ethylpropoinate)“x酸

x酯”

羧酸

醇OCH3COCH2CH3乙酸乙酯ethyl

acetateCCH3

OH2C

COCH34>晴根据水解所得的酸命名CH3C

NEthanenitrile7二.羧酸衍生物的物理性质低级的酰氯和酸酐为具有刺鼻气味的液体.酰氯和酸酐不溶于水,但极易水解.羧酸衍生物都能溶于

,其中DMF,EA,

是良好的

.891.IR.

P331

表10-4C=O:

1630-1850cm-12.NMR※1H

NMR

α

-C上质子1.1-2.4ppm之间酯中烷氧基上质子:3.7-4.1酰胺中氮原子上的质子为5-8,

不能出现

的峰.※13C

NMRC=O:170

117.4C

N2250cm-1三.羧酸衍生物的光谱性质C

N四. 羧酸衍生物中主要反应基团性能的比较1.

的活泼性H+CH2

CH+O-CH2

C

Cl

+O-OCH3

C

Cl

OCH3

C

OCH3OCH3

CN(CH3)2CH2

C

N(CH3)2

+H+OCH3

+O-pka1625302.

羰基氧的碱性酯或酰胺酸催化时,H+加到羰基氧上还是加到烷氧基氧上或氨基氮上？11OR

C

ORH+H+OR

C

N(CH3)2+OHR

C

OR+OHR

C

N(CH3)2H+OR

C

CH2CH2OR'

OR

C

CH2CH2OR'H+p-共轭电荷转移。羰基氧具有一定的碱性，易接受质子。质子化发生在羰基氧上羰基与烷氧基不发生p-共轭,质子化发生在哪个原子上？12ORRC

ORRsp3碱性较强sp2碱性较弱3.羧酸衍生物的亲核取代—消去反应Carbonyl:R

R1OC+

NuNuRC

OR1NuRC

OHR1H

NuAcyl:NuRC

OLRCLO

+NuHHNuRC

OLHNuRC

O亲核取代反应活性O

O

O影响反应活性的因素：羰基的活性与羰基相连基团(Y)的离去能力离去基团的离去能力：RO-

>H2N-X-

>

RCOO-~

RCNRCX

>

RCOCR

>RCOORRCOOHORCNH2活性低的衍生物可由活性高的衍生物13五.酰氯1.羧酸与SOCl2,PCl5,PCl32.酰氯的化学性质1)水解－生成羧酸OR

C

Cl+H2OOR

C

OH

+

HCl2)醇解－生成酯OR

C

Cl+

HOR1OR

C

OR1+HCl3)氨(胺)解－生成酰胺OR

C

Cl+HNR1R2OR

C

NR1R2

+HCl4>还原成醛条件：LiAl(OBu-t)3

或H2/Pd-BaSO4145)与有机金属化合物反应：Grignard:O6)傅－克酰基化芳酮CH3CCl

+

CH3(CH2)3MgCl Et

O,FeCl3

2-70oCOCH3CCH2CH2CH2CH3

CH3(CH2)3MgClOHC(CH2CH2CH2CH3)2CH3铜锂试剂：OR

CCl

+

R2'CuLiEt2OR

C

R'O1516六.酸酐1.酸酐的1）由乙烯酮CH3COOHCH2=C=O

+

CH3COOHCH3C

OCH2=C=O

+

H2OOOCCH32）由乙酐3）由羧酸盐与酰氯COOH(CH3CO)2OH3PO4OOC

O

COOC O

CCH3CH3CH2CH3COONa

+

CH3CH2COCl4）羧酸脱水—二元羧酸脱水得5、6元环COOHCOOH200oCOOOCOOHCOOHOOO2.酸酐的反应1）水解

O

OR

C

O

C

R+H2ORCOOH2）醇解O

OR

C

O

C

R+HOR'RCOOR'

+

RCOOHCOOHCOOCH2CH2CH2CH3OOO+CH3CH2CH2CH2OH回流COOHCOOCH2CH2CH2CH3CH3CH2CH2CH2OHH2SO4COOCH2CH2CH2CH3COOCH2CH2CH2CH3173）氨（胺）解O

OR

C

O

C

R+2

HNR'R''OR

C

NR'R''OR

C O-

HNR'R''+OOO+2NH3300oCNHOOBr2OON

BrCOO-NH4CONH2OOO

+

2NH3COOHCONH23H

O+300oCNHOO酰亚胺18（4）Perkin(珀金)反应CHOO

O+

CH3COCCH

33CH

COONa170oCCH=CHCOOHOHCHO+

CH3COCCH3O

OCH3COONaOO（香豆素）19七.酰胺酰氯、酯、酸酐的氨（胺）解1.-R

COO

NH4_H2ORCONH2RCN

+

H2OH3O+RCONH22.酰胺的反应1）水解20机理21酸催化机理：碱催化机理：2）脱水反应R

COO-NH4_H2ORCONH2RCOOH

NH3H3O++

H2O_H2O+

H2ORCN3）还原反应OR

CN

R'R''1)

LiAlH4,

Et2ON

R'R''R

CH22)

H2O22（Hofmann）降解: 酰胺与次卤酸钠的碱溶液作用，脱去羧基生成比原料少一个碳的伯胺的反应4）降解OR

C

NH2

+

NaOXOHR-NH2

+

Na2CO3

+

NaX

+

H2O(CH3)3CCH2CONH2Br2NaOH(CH3)3CCH2NH2Br2NaOHO

+

2NH3OOOCH2

C

NH2CH2

COONH4H2NCH2CH2COO-23机理:24八.酯酯的直接酯化酰

解酸酐醇解酯交换酸酸盐与卤代烃作用腈与醇作用3

2+

CH

CH

OHHClCH3COCH2CH3NH2+

Cl-H3O+CH3COCH2CH3O+

CH3CH2OHH2SO4CH2COOC2H5252.酯的反应RCOOR'+

H2ORCOOH

+R'OH水解酯化RCOOR'+

NaOHRCOONa

+

R'OH可逆反应皂化反应H+1）水解键的断裂发生在酰氧键还是烷氧键？O

OR

C

OR'

R

C

O

R'大多数2o和1o醇的羧酸酯水解发生酰氧键断裂；3o醇的羧酸酯水解发生烷氧键断裂。26OR

C

OR'H++OHR

C

OR'2H

OOHR

C

OR'+OH2R

C

R'OHOH:

OH++OH-R'OHR

C

OH-H+RCOOH酸催化：碱催化：OR

COR'

+

OH-O-R

C

OR'OHOR

COH

+

-OR'RCOO-

+

R'OHRCOC(CH

)3

3OH+RC

O C(CH

)3

3+

OHOH+RC O

+

C(CH3)+C(CH3)3

+

H2O

H2OC(CH3)3+27-H+(CH3)3COH3o醇的羧酸酯水解：SN1机制（2）醇解（酯交换反应）CH2=CHCOOCH3

+

CH3(CH2)2CH2OHSO3HH3CCH2=CHCOO(CH2)3CH3

+

CH3OH通式：OR

C

OR1+

R2OHH+

or

R2O-OR

C

OR2b.p.较高+

R1OHb.p.较低（3）氨解（氨或胺本身亲核性较强）O+OR

C

OR1

NH3

R

CNH2

+

R1OH++eg.

NCCH

COOC

H

NH

2

2

53NCCH2CONH22

3CH

CH

OH+

C6