北大复试等多个文件考研有机第十章

(Carboxylicacidsandsubstitutedcarboxylicacids)1羧酸(carboxylic acid)的官能团是羧基(carboxyl)(-COOH)，除甲酸外，它们都可OOC2

*

O O

4(二 formic

benzoic

palmitic cannamic

stearic

ic5

C

Cb－bromobutanoic

butandioic

cis-2-butendioic命名含脂环和芳环的羧酸时，脂环和芳环做取代基，脂

CHCHCOOH22benzoic

67C1－C3 8OH-OH-O。打开氢键时所需能量：甲酸30.1KJ/mol(b.p101乙醇乙醇25.1KJ/mol(b.p789OOCOOCCOOHRCRRRCRRC+O•HHH••

••

••α－HROCOH

_O

R(Ar)CO-氢原子酸性增加，羧酸具 O羧酸根负离子的p-p

RCOO-中负电荷均O

1- O2-

OO

X射线衍射证实，在甲酸钠分子中，两个碳氧双键均为5RCOOH+NaHCRCOOH+NaHC3 RCOONa+C2+RCOONa+ RCOOH+

CHCO

+

CH +-CH2-

2S--+ +CH3-N 2S--

2NN2NN缺点：贵、毒、易3NH3酸性酸性：COOH＞fieldHH HOCO HO OδOXHOeffectissmallunlessXiselectronegative;effectislargestOXHOHHF

②CarboxylicAcids-HydridizationofSubstituentsEffectsonAciditysp2-hybridizedcarbonismoreelectron-withdrawingthansp3,andspismoreelectron-withdrawingwithdrawingthan羧酸衍生物的生成(羰基的反应O

-Y- +++b.p107 b.p107

+

OH+

1OORCOS1OORCOS

+

+内返 COOCOCOOCO在脱水剂（如P2O5）P 2

CH3＋

O180

2 + (RCO)2O 2b.pO OO--O+OOO+OCOOCO2223222223224222252 39 树脂-SO3H，CaSO4CH3COOH+ + OCH3---

+O OH+ R

+ O+

O

4

5

+ C*

C*

O

CH3C-OC(CH3)3+C+=OH

+ H

O+ H 3 H3C+ CH3OH(4酰胺的生成 CHCHCOOH+HNC

662。1906C6H5COO-CHCONHC66+H2N

2-2

4 4 - 3H+H2

B2H ofdilof

(selectivereductionofcarboxylgroupinpreferencetocarbonyl 2422 2 32232

CC

H

,O

酯

CH-COOH+

红PCHCOOH

Cl-

Cl-C-

CHCHCOOH+Br红P

CH3C-

2P+3RCH2COOH+ RCH2COX+X2 RCHXCOX+

3RCH2COX+H3PO3RCHXCOX+HXRCHXCOOH+RCH2COXH2O/OH- NH3/ 脱羧反应Cl3-Cl3-CHCl3+OOCH3C-CH2-C-OOCH3C-CH2-H+OCOOHCH3

OCH3 CHCH3COOHCOOHCHCH-COOH32+2C

+

H

RCO

CristolST（ 脱）——直接用羧酸与氧化、 +HgO+

n-C17H35Br+HgBr2+CO2+H2O ++RCI+CO2+Pb(OAc)2CH3COOH+Pb(OAc)4+ +

R+2CO2+H2+ 2 2KOC(CH 2

-阳极：2

-2

22

2.+22RCOOK+ R-R++

2

+2

.2O+2 2KOH+. 芳香羧酸、a，β2 HOOC-

HCOOH+CO2（脱羧HOOC-CH2-

CH3COOHCO2（脱羧

O

+HO（脱水CH2-

OH

H

O

CH2-CH2-CH-CH-CH2-CH2-CH-CH-CO+2+H222

CO+CO2+

CCOCOORCH2CH2R' RCOOH+

CH=CHCH+

[O]R-

[O]

[O]KMnO4、

O

COOH+3

3 ++CH2=CHCOOH+ ++2++2+2++222-2--222 2OO+OH2O

OC-

+

2低

O

2MgBr+CO2

C-OMgBr

+

150-160

OH +

180-250

取代羧酸（substitutedcarboxylic22

3CH 3

lacticacid

malicacid

ic citricacid

COOH isocitricacid salicylicacid

protocatechuicacid

gallicacid O

- O+H+O

+H

CH

O

OOH --OH

RCH=CH-- a-OR-CH-CH2CH2-C-OO+H2OOR-CH-CH2CH2CH2-C-O-H2R-O+H2OHO(CH2HO(CH2)nD OOOOOO O

RCHO+ RCOO-+ aa–

P

H

稀OH-

H

3 3

NeighboringgroupparticipationLbaCC +LbaCC +CCab ab 浓CO2

OO+

OBaeyer-Villiger氧 ReformatskyR +

O酸 O

O

O酸(pyruvic

COCOOH>CO>