Organic chemistry 10Word下载.docx

Organic chemistry 10Word下载.docx

《Organic chemistry 10Word下载.docx》由会员分享，可在线阅读，更多相关《Organic chemistry 10Word下载.docx（19页珍藏版）》请在冰豆网上搜索。

-OR（Ar）ester

-NH2、-NHR、-NR2amide

2.NamingCarboxylicAcidsandDerivatives

CarboxylicAcids:

RCO2H

Simpleopen-chaincarboxylicacidsarenamedbyreplacingtheterminal–eofthealkanenamewith-oicacid.The–CO2Hcarbon（thecarboxylgroupcarbon）isalwaysnumberedC1.

Alternativelycompoundsthathavea–CO2Hgroupbondedtoaringarenamedbyusingthesuffix-carboxylicacid.Inthisalternativesystem,thecarboxylicacidcarbonisattachedtoC1ontheringbutisnotitselfnumbered.

3-Bromocyclohexanecarboxylicacid

1-Cyclopentenecarboxylicacid

Commonnames

PopularnameIUPACname（-oicacid）

HCOOHformicacidmethanoicacid

CH3COOHaceticacidethanoicacid

HOOC-COOHoxalicacidethanedioicacid

HOOC（CH2）2COOHsuccinicacid

C17H35COOHstearicacidoctadecanoicacid

C15H31COOHpalmiticacidhexadecanoicacid

Benzoicacid

Nomenclature-oic→oyl

acetylbenzoylpropanoyl

AcidHalides:

RCOX

Acidhalidesarenamedbyidentifyingfirsttheacylgroupandthenthehalide.

Theacylgroupnameisderivedfromtheacidnamebyreplacingthe-icacidendingwith-yl,orthe-carboxylicacidendingwith-carbonyl.Forexample.

AcidAnhydrides:

RCO2COR’

Anhydridesfromsimplecarboxylicacidsandcyclicanhydridesfromdicarboxylicacidsarenamedbyreplacingthewordacidwithanhydride:

AceticanhydrideBenzoicanhydrideSuccinicanhydride

aceticpropanoicanhydride

Amides:

RCONH2

Amideswithanunsubstituted–NH2grouparenamedbyreplacingthe-oicacidor-icacidendingwith-amideorbyreplacingthe-carboxylicacidendingwith–carboxamide.

Ifthenitrogenatomissubstituted,theamideisnamedbyfirstidentifyingthesubstituentgroupandthentheparent.ThesubstituentsareprecededbytheletterNtoidentifythemasbeingdirectlyattachedtonitrogen.

N,N-dimethylacetamide

N,2-dimethylpropanamide

N-phenylacetamide（acetylaniline）

Esters:

RCO2R

Systematicnamesforestersarederivedbyfirstgivingthenameofthealkylgroupattachedtooxygenandthenidentifyingthecarboxylicacid.Insodoing,the-icacidendingisreplacedby-ate:

Nitriles:

R-C≡N

Compoundscontainingthe–C≡Nfunctionalgrouparecallednitriles.Simpleacyclicnitrilesarenamedbyadding-nitrileasasuffixtothealkanename,withthenitrilecarbonnumberedC1.

Morecomplexnitrilesarenamedasderivativesofcarboxylicacidsbyreplacingthe-icacidor-oicacidendingwith-onitrile,orbyreplacingthe-carboxylicacidendingwith-carbonitrile.Inthissystem,thenitrilecarbonatomisattachedtoC1butisnotitselfnumbered:

Acetonitrile（fromaceticacid）Benzonitrile（frombenzoicacid）

2,2-Dimethylcyclohexanecarbonitrile（from2,2-dimethylcyclohexanecarboxylicacid）

3.OccurrenceandPropertiesofCarboxylicAcids

Themostobviouspropertyofcarboxylicacidsisimpliedbytheirname-theiracidity.Carboxylicacidsaremuchstrongeracidsthanalcohols.

Aceticacid:

Ka=1.76×

10-5（pKa=4.75）Ethanol:

Ka=10-16（pKa=16）.

carboxylicacidsreactwithbasessuchasNaOHtogivewater-solublemetalcarboxylates,RCO2-Na+.

•

RCOOH>

H2CO3>

ArOH

酸性大小的判断：

1．吸电子能力越高基团的取代烃基上的H则酸性越强

2．吸电子基团越多，酸性越强

3．吸电子基团离羰基越近，则酸性越强

4．斥电子基团越多，越大，则酸性越小

4.NucleophilicAcylSubstitutionReactions

Carboxylicacidsandtheirderivativesalsoreactwithnucleophiles,buttheultimateproductisdifferentfromthatofthealdehyde/ketonereaction.

Incomparingthereactivityofdifferentacylderivatives,themoreelectron-poortheC=Ocarbon,themorereadilythecompoundreactswithnucleophiles.

Aconsequenceofthesereactivitydifferencesisthatit'

susuallypossibletoconvertamorereactiveacidderivativeintoalessreactiveone.Acidchlorides,forexample,canbeconvertedintoestersandamides,butamidesandesterscan'

tbeconvertedintoacidchlorides.

5.ReactionsofCarboxylicAcids.

ConversionofAcidsintoAlcoholsbyReduction（RCO2H→RCH2OH）

carboxylicacidsarereducedbylithiumaluminumhydride（LiAlH4）toyieldprimaryalcohols.

Formationofcarboxylicacidderivatives

acylAcetyl（-ic→-yl）

ConversionofAcidsintoAcidChlorides（RCO2H→RCOCl）

Carboxylicacidsareconvertedintoacidchloridesbytreatmentwiththionylchloride,SOCl2.Theneteffectissubstitutionofthe-OHgroupby-Cl.Forexample:

acylhalideoracidhalide

ConversionofAcidsintoEsters（RCO2H–RCO2R'

）

Perhapsthemostusefulreactionofcarboxylicacidsistheirconversionintoestersbyreactionwithanalcohol-thesubstitutionof-OHby-OR.CalledtheFischeresterificationreaction,thesimplestmethodinvolvesheatingthecarboxylicacidwithanacidcatalystinanalcoholsolvent.

ester（esterification）

Alcohols:

CH3OH>

10>

20>

30

Carboxylicacid:

HCOOH>

CH3COOH>

RCH2COOH>

R2CHCOOH>

R3CCOOH

acidanhydride

Cyclicacidanhydride

amide

6.ChemistryofAcidHalides

ConversionofAcidChloridesintoAcids（RCOCl→RCO2H）

Acidchloridesreactwithwatertoyieldcarboxylicacids（hydrolysisreaction）.

ConversionofAcidChloridesIntoEsters（RCOCl→RCO2R'

Acidchloridesreactwithalcoholstoyieldestersinareactionanalogoustotheirreactionwithwatertoyieldacids:

ConversionofAcidChloridesintoAmides（RCOCl→RCONH2）

Acidchloridesreactrapidlywithammoniaandwithaminestogiveamides.

7.ChemistryofAcidAnhydrides

Thebestmethodforpreparingacidanhydridesisbyanucleophilicacylsubstitutionreactionofanacidchloridewithacarboxylicacidanion.

Aceticanhydrideisoftenusedtoprepareacetateestersofcomplexalcoholsandtopreparesubstitutedacetamidesfromamines.

Thechemistryofacidanhydridesissimilartothatofacidchlorides.

8.ChemistryofEsters

ConversionofEstersintoAcids（RCO2R'

→RCO2H）

Estersarehydrolyzedeitherbyaqueousbaseorbyaqueousacidtoyieldacarboxylicacidplusanalcohol:

Hydrolysisinbasicsolutioniscalledsaponification.

soapismadebythebase-inducedesterhydrolysisofanimalfat

ConversionofEstersintoAlcoholsbyReduction（RCO2R'

→RCH2OH）

EstersarereducedbytreatmentwithLiAlH4toyieldprimaryalcohol.

ConversionofEstersintoAlcoholsbyReactionwithGrignardReagents.

Grignardreagentsreactwithesterstoyieldtertiaryalcoholsinwhichtwoofthesubstituentsonthehydroxyl-bearingcarbonareidentical.

9.Chemistryofamides

ConversionofAmidesIntoAcids（RCONH2→RCO2H）

Amidesundergohydrolysistoyieldcarboxylicacidsplusamineonheatingineitheraqueousacidorbase.

ConversionofAmidesintoAminesbyReduction（RCONH2→RCH2NH2）

Likeothercarboxylicacidderivatives,amidesarereducedbyLiAlH4.Theproductofthisreduction,however,isanamineratherthananalcohol:

Thiskindofreactionisspecificforamidesanddoesnotoccurwithothercarboxylicacidderivatives.

Summary

chemicalproperties

nucleophilicsubstitution

HNu:

reaction

H2Ohydrolysis

ROHalcoholysis

NH3（H2NR）ammonolysis

1）hydrolysis

2）alcoholysis

3）Ammonolysis（NH3、H2NR、HNR2）