另一个-第十一章醛和酮

Chapter

11Aldehydes

&Ketones11.1

Classification

and

NomenclatureCH3CH2CH2CHO正丁醛ClassificationNomenclatureCommon

NomenclatureOCH苯BrCH2CH2CHO溴丙醛OCCH2Cl氯代苯乙酮OCH3CCH2CH3甲乙酮OC环己基苯基酮OCH3CCHO对乙酰基苯(2) Systemic

NomenclatureCH3CH3CH2CHCHO2-甲基丁醛CH3CHO2-甲基环己OCH3CH2CH2CCH32-戊酮OCH3CH33,3-二甲基环己酮Precedence

order

of

functional

groups

asprinciple

part

in

nomenclatureAldehyde>Ketone>Alcohol>Alkene

and

Alkyneeg.OCH3CCH2CH2CHO4

氧代戊醛练习：用系统命名法和普通命名法命名下列化合物1.O2.CH

CHCHO3.

HOCH2CH2CHO4.

O11.2

Physical

PropertiesbpCH3CH

CH2-47.4℃CH3CH

O20.8℃CH3CH2OH78.3℃u2.7DOCCH3CH30.4DCH2CCH3

CH31.7DOHCCH3CH3bp-6.9℃56.5℃82.3℃u0.5D2.7D1.6D11.3 Chemical

PropertiesC

CHReactive

centers

of

aldehyde

and

ketone-

↑reactionsonα-HO

←

attacked

by

electrophilic

reagent←attacked

by

nucleophilic

reagentR(H)↖Reactions

of

aldehyde11.3.1

Nucleophilic

AdditionRC

OR'HCNR

OHCR'

CNCNOHOHHCNRC

OR'RCR'CNOHCNOHCNCN

H2OR

CNC

R'

ORCR'CN11.3.1.1 Reaction

with

hydrogen

cyanide11.3.1.2 addition

with

sodium

bisulfite

(NaHSO3)C6H13CHOnR

CHSO3Na11.3.1.3 addition

with

Grignard’s

reagentRMgX+HCHOH+RCH2OHR'CHOH+RR'CHOHR'COR''RR'R''COHH11.3.1.4 addition

with

H2OHOH

+

C

OHO

C

OH偕二醇11.3.1.5 addition

with

alcoholORCR'

+

2CH3OH酸OCH3RCR'OCH3缩醛（酮）mechanism：OHRCR'OCH3H+OH2R

C

R'OCH3SN1R

C

R'OCH3R

C

R'OCH3CH3OHHOCH3R

C

R'OCH3CH3OHOCH3R

C

R'

+

CH3OH2OCH3ORCR'

+

CH3OHOCH311.3.1.6 addition

with

amines①

reaction

with

pri

mine——Schiff

base3RCHO

+

3NH3HNNHNHRR3RCH

NH不稳定6HCHO

+

4NH3+

6H2ON乌洛托品NNN②

reaction

with

secondary

amine——enamineCHO

+

CH3N

PhHCH3Ph+

H2OCH

N烯胺87%O+ONH酸ON+

H2ONOO+

RCClNOOCRCl2H

OOOCR+ONHHCl11.3.1.7

Wittig’s

reactionC

CHR

+

O=PPh3C

O

+

CH

PPh3RWittig

试剂Ph3PCH3Br+

PhLiPh3PCH2

+

C6H6+

LiBrPhPhC O

+

CH2PPh3O-Ph2C

CH2

PPh3Ph2C

CH2+

O

PPh3Ph3P+

RCHXR'+Ph3PCHRR'X-+COORPh3PCH2Br-RONa

Ph3P

OCHOCOORLiAlH4CH2OH维生素A11.3.1.8 Reaction

with

Schiff’s

reagentH2NH2NCH3NH

.HClSO2NHSO2HH2NH2NCH3SO3HCH3OHRCHOSOHNRCHORCHOSOHNOHNH

.HCl无色红色或紫色11.3.1.9 reaction

with

aryl

hydrocarbons①

halomethylation+

HCHO

+HCl

ZnCl2

CH2Cl

+

H2O79%mechanism：HCHO

+

H3OCH2

OHCH2

OH +

H2O+

CH2OHCH2OHHOH2CH2OH+

H3OCH2OH

+

HClCH2Cl

+

H2O②

other

reactionsOH+OCH3HClHOAcOHHOCH370%+

H2O2OHCl

+

Cl3CC

HOHClCHCCl3Cl

+

2H2O245~50%

DDT11.3.2

oxidative

and

reductive

reactionsreduction

of

carbonyl

compoundsto

alcohol①

metal

hydridsCH3CHO4+

4CH3OH

+

NaBH4CH3OH4CH2OHCH3+

NaOCH3

+

B(OCH3)396%O4+

LiAlH4乙醚H2O4HOH+

LiOH

+

Al(OH)390%CRRO

+

AMeerwein-Poundorf

反应②

catalytic

hydrogenation3CH

OOH2

,

PtO2HOHCH3O97%25oC,1atm,

Fe3+O+

H2Pd/C,

HOAc,

HCl4atmHOHOHH+20%73%11.3.2.1.2 to

methyleneOPhCCH2CH3

+

H2NNH2KOH,

,1h三甘醇PhCH2CH2CH3

+

N2

+

H2O82%①Wolff-Kishner’s

reactionOHHH2NNH222

5+

N

+ C

H

OHHHC2H5ONa200oC,加压mechanism：RRC

O

+

H2NNH2H2ORRC

NNH2OH-RRC

NNHRRC

N

NHH2ORRCH

N

NHOH-RRCH

N

N慢CH

+

N2RR2CH

+

OH-H2O

RR②

Clemmensen’s

reductionCH3OZn/Hg,C2H5OHHCl,24h+

H2OCH3

93%CH3(CH2)5CH

OZn/Hg25%HClCH3(CH2)5CH387%③

desulfur

of

thioacetalor

thioketal3BF

乙醚溶液HSCH2CH2SHRaney

NiC2H5OH,

,40hO(CH2)6OC(CH2)6

(CH2)6CCO2

6SCSCS

(CH

)

SS

SC(CH2)6

(CH2)6CH2(CH2)6CH2(CH2)6CH2(CH2)611.3.2.2

OxidationRCHO

+

AgRCHO

+

Cu(1)

aldehydeTollens

试剂：AgNO3的氨溶液Fehling

试剂：CuSO4

+NaOH+酒石酸钠钾Benediet

试剂：CuSO4

+NaCO3

+柠檬酸钠CHOCH3CH2CH2CH2CHC2H5H2O,NaOHKMnO4

H3OCH3CH2CH2CH2CHCOOHC2H578%OCHOK2Cr2O7/H2SO4COOHO75%(2)

ketoneOC+

PhCOOOHOCO+OCOH82%Baeyer-Villiger

反应OR

C

RPhCOOOHOHR

C

ROOCPhOOHC

R

+

PhCOOOR-HO

C

ORRmechanism:CPhHCH3CCH3OPhCO3HCPhHCH3OO

CCH3迁移基团的规律：H>苯基>三级烷基>二级烷基>苄基>一级烷基>甲基如果迁移基团是手性碳，迁移后构型保持。eg.11.3.2.3 Cannizzaro

reaction2

ClCHO50%NaOHH3OClCH2OH

+

ClCOOH93%88%mechanism：ORC H

+

OH-快O-

OR

C H

+

C

ROH

H慢O-R

C

HOHO

O-R

C

+

H

C

ROH

H快2RCOO-

+ RCH

OHRCOO-

+

H3ORCOOH

+

H2OCrossed

Cannizzaro

reaction：CH3OCHO

+

HCHONaOHCH3OCH2OH

+

HCOONa(HOCH2)3CCHO

+

HCHONaOHC(CH2OH)4

+

HCOONa11.3.3

reactions

onα-HpKa

~20OC

CHOC

COC

C+

H烯醇式enolizationEnolization

could

be

catalyzedby

both

acid

and

base：OCH3C

CH2

HHOHCH3C

CH2

HOCH3C

CH2

H

+

BOBH

+

CH3CCH2

OHCH3

C

CH2

+

HOCH3C

CH211.3.3.1 Halogenation

of

α-H①

Base-catalyzed

halogenationO(CH3)3CCCH3

+ 3

Br2NaOH2O(CH3)3CCCBr3OH-H3O(CH3)3CCOOH

+

CHBr371.74%H

O/二噁烷，0oCmechanism：-ORCCH3

+

OH-ORCCH2

+

Br—BrOORCCH2-

+

H2OORCCBr3RCCH2Br

+

Br-ORCCH2BrORCCBr3OH-O-RC

CBr3OHROCOH

+

-CBr3RCOO-

+

HCBr3②

Acid-catalyzed

halogenationBr3CCH

+

Br2OBr2CCH

Br

+

HBrOO+

Cl2H3OOCl+

HClHOAc25oC69-72%61-66%mechanism：R

CCH3OH3O2OHRC

CHBr-Br2OHRC CH

Br2-HOR

CCH2

Br+OHR

C CH

Br③

Free

radical

halogenation3h,25℃83～85%O+OON

BrCCl4过氧化物BrO+NHOOCCl4OCH3HO+

ClSClOCH3ClO+

HCl

+

SO211.3.3.2 Aldol

condensation2

CH3CH

ONaOHH2OCH3CHCH2CH

OOH50%①

Base-catalyzed

aldol

condensationmechanism：HO-

+

HCH2

CHO-CH2CHOO-CH2

CH +

H2OOCH3CH +-CH2CHOO-CH3CHCH2CHOH2OOH

CH3CHCH2CHO +

OH-②

Acid-catalyzed

aldol

condensation2

CH3CCH3O酸Dowex-50CH3CH332C

CH

CCH

+ H

OOmechanism：OHCH3CCH3OHCH3CCH3+

H2OOCH3CH3

+

H3OOH

CH3

C

CH2HO

C

CH3CH3CH3OHCH3C

CH2H3C

C

OHCH3

OHCH3C

CH2H3C

C

OHH2O32O33CH

CCH

C

CH +

H

OCH3OH3OCH

CCH

CCH3CH32+

H

O③

Crossed

aldol

condensation影响产物的因素：a.

-H

的活泼性b.羰基的活泼性eg.O

+(CH3)2CHC

OOH-OH(CH3)2CHCHO-H2O(CH3)2CH

CHHOO+

CH3CHOOH-OHCH2CHO-H2OCHCHO分子内的羟醛缩合：CH2CH2CCH3OOTosOHO+

H2O90%Claisen-S缩合：3PhCHO

+

CH

CHO碱2PhCHCH

CHOOH-H2OPhCH

CHCHO肉桂醛11.4 Mechanism

of

NucleophilicAdditionSimple

additionmechanismNu

+C

ORR

慢O-R

C

NuRH2O快-O-R

C

Nu

+

OHR11.4.1.2 Factors

affecting

the

addition①

stereo

factors②

electric

factors③

Nucleophility

of

reagent练习：判断下列各组化合物中哪个化合物进行亲核加成反应时活性更强，为什么？4-溴丁酮和溴代2,3-丁二酮和丁酮对和对甲氧基苯环戊酮和环11.4.2

Complexed

AdditionRRC

O

+

H快RRC

OHCH2N-B,慢

RROHNH2B快CRROH2NHB快

RRC

NHB--H,快RRC

NB11.4.3

Stereochemistry

of

Nucleophilic

AdditionCORSMNuLLSOHNuRM+MLRSNuOHCram

规则：稳定构象优势产物劣势产物CH3C

H6

11HCH3OAlH3-HC

CC

C6

11CH3HC

H

HCH3OH+6

11CH3HC

CCH3C

H

OHHeg.From

HydrocarbonsOxidation

of

side

chain

of

substituted

arylhydrocarbonsOzonolysis-reduction

of

alkeneHydration

of

alkynesFormylation

of

alkenesFriedel—Crafts

acylation

of

arylhydrocarbons11.5 Preparation

of

Aldehyde

andKetone11.5.2

Oxidation

or

dehydrogenation

ofalcoholCH3(CH2)5CH2OHCH3(CH2)5CHOCH2

CHCH2OH新制MnO2CH2

CHCHO25℃CrO3

(C5H5N)2CH2Cl2,

25℃CHOH

+

Al

OC(CH3)33RRCHOAlOC(CH3)32+

(CH3)COHRRCHOAlOC(CH

)3

3

23+

CH

CCH3RROCH3CH3OCCHRAl OC(CH

)OR3

3

2CH3CH3CHO

Al

OC(CH3)32O+

RCRCH3CH3CHOAl

OC(CH3)32+

(CH3)3COHAl

OC(CH3)33+

CH3CHCH3OHOppenauer氧化法：11.5.3

From

carboxylic

acidOCClH2Pd-BaSO4CHO+

HClCH3CH3CH3ONHCH+POCl3H2OCH374-81%Rosenmund

还原法CHOCH3NH2

+

HCl

+

H3PO4+CH375%

Vilsmeier-Haack反应2

CH3COOHMnO2OCH3CCH3+

H2O

+

CO2300℃11.5.4

Extracted

from

animal

or

plant

bodyCH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C

OCH3麝香酮CH3CH3CH3O樟脑(1)Formaldehyde11.6

Representatives聚

树脂氨基树脂甲酚

树脂醛树脂酚醛树脂间苯二酚树脂脲醛缩合物羟甲基脲素羟甲基脲素树脂化肥控制剂乙二醇脱除雕白粉橡胶促进剂蛋白质硬化剂三聚和多聚乌洛托品（熏蒸剂，酚醛树脂熟化剂剂，杀菌剂，防水剂，）季戊四醇三羟甲基丙烷1，4丁二醇新戊二醇异戊二烯橡胶吡啶-甲基吡啶11.6.2

Acetaldehyde2CHOCN-OHCHCO安息香11.6.3

Benzaldehyde安息香缩合反应：mechanism：OPhCH

+

CN-O-PhCHCNOHPhC-CNOH

OPhC-

+

CCN

HPhOHO-PhC

C

PhCN

HO-OHPhC

C

PhCN

HPh

+

CN-O

OHPhC

CH11.6.4

Acetone11.6.5

cyclohexone甲基丙烯酸甲基丙烯酸甲酯有机玻璃甲基丙烯酸高级酯涂料、润滑油双酚A聚碳酸酯环氧树脂溶剂二

醇甲基异丁基甲酮（醇）异佛尔酮氯双烯酮甲基乙烯基酮乙烯酮片呐酮2-甲基

-2-丁醇双

丙烯酰胺

吸水性树脂，

感光树脂2-鸢尾酮香料溴仿、碘仿缩氨脲乙酰偶氮二异丁腈剂、原料杀鼠灵

灭鼠药异丙胺

，如扑草净橡胶防老化剂乙氧基喹啉食品、饲料抗氧化剂有机制药11.7

Unsaturated

carbonyl

compound11.7.1

enoneCH2C

OH

OHCH2C

OH

CH3AlPO4CH2

C O

+

H2OCH2

C O

+

CH43

CO

+

H2ZnOCH2

CO

+

CO22CH2

C

O2CH2

C

OCH

C

O双烯酮700oC700-800oCo200-300