有機(jī)化學(xué)課件chpt伯胺一級(jí)胺仲胺二級(jí)叔胺

Chapter20ORGANIC Departmentof XiamenORGANIC Aminesareclassifiedasprimary(RNH2),secondary(R2NH),ortertiary(R3N),dependingonthenumberoforganicsubstituents tonitrogen.伯胺(一級(jí)胺仲胺二級(jí)胺叔胺(三級(jí)胺Departmentof XiamenORGANIC Whenwespeakofatertiaryalcoholorhalide,werefertothedegreeofsubstitutionatthealkylcarbonatom.Whenwespeakofatertiaryamine,however,werefertothedegreeofsubstitutionatthenitrogenatom.

tert-Butylalcohol

Departmentof XiamenORGANIC NomenclatureofCommonnomenclature:alkylamines(the-amineisaddedtothenameofthealkylSystematicnomenclature:thenameoftheparentcompound –e→-amineDepartmentof XiamenORGANIC Primary

(ethanamine)(2-methyl-1-propanamine)(2-methyl-2- 2-甲基-2-丙2 2

14-Departmentof XiamenORGANIC SecondaryandTertiaryCommonnomenclature:symmetricalsecondaryandtertiaryaminesarenamedbyaddingtheprefixdi-ortri-tothealkylgroup.Systematicnomenclature:namedasN-substitutedprimaryamines.Thelargestalkylgroupischosenastheparentname,andtheotheralkylgroupareconsideredN-substituentsontheparent(Nsincethey’reattachedtoDepartmentof XiamenORGANIC

N-甲基乙 N-乙基乙 N,N-二乙基乙

N,N-二甲基-1-丙 N-甲基-N-乙基環(huán)己Departmentof XiamenORGANIC An–NH2group,whennottheprincipalgroup,isnamedbytheprefixamino-.2-Aminobutanoic2-氨基丁O

2,6-Diaminobenzoic2,6-二氨基苯甲4-氨基-2丁

2-2-氨基乙Departmentof XiamenORGANIC A

Benzenamine1-Naphthalenamine1,3- Departmentof XiamenORGANIC Threecommonarylamineshavethefollowing

benzenamine)Departmentof XiamenORGANIC BHeterocyclicTheimportantheterocyclicaminesallhavecommonInsystematicrecementnomenclaturetheprefixesaza-,diaza-,andtriaza-areusedtoindicatethatnitrogenatomshaverecedcarbonatomsinthecorrespondinghydrocarbon.

N Pyrrole(1-

Pyrazole

Imidazole)Departmentof XiamenORGANIC

SOxazole噁(1,3-氧氮雜-2,4-環(huán)戊二烯

Thiazole噻(1,3-硫氮雜-2,4-環(huán)戊二烯 5 吡咯烷，四氫吡

Indole吲(1-(1-氮雜茚Departmentof XiamenORGANIC 4 4 Pyridine吡啶Pyridazine噠

嘧

吡(azabenzene)(1,2-diazabenzene)(1,3-diazabenzene)(1,3- 8N 8N Piperidine哌啶Quinoline喹

Isoquinoline異喹

Departmentof XiamenORGANIC PhysicalPropertiesandStructureofAminesDepartmentof XiamenORGANIC APhysicalBoilingpoints:alcohol>amine>alkaneFormstronghydrogenbondstoeachother(1°and2°)Formhydrogenbondstowaterorotherhydroxylicsolvents.Verywatersoluble(lowmolecularweightDepartmentof XiamenORGANIC BStructureofsp3sp3N3NRNRInterconversionofamine R

RQuaternaryammoniumsaltssuchasthesecanberesolvedDepartmentof XiamenORGANIC BasicityofAmines:AmineDepartmentof XiamenORGANIC RR+HRH+Inthegasphase:3°>2°>1°>Inaqueoussolution:2°>1°>3°>Departmentof XiamenORGANIC ABasicityofArylamines

DelocalizationoftheelectronpairstabilizesArylgroupsareelectron-withdrawingDepartmentof XiamenORGANIC BAminesversusBasicity:nonaromaticamines>arylamines>amides.ThepKaoftheconjugateacidofatypicalamideisabout

O

O

O

N-Protonated

ProtonatedontheoxygenDepartmentof XiamenORGANIC 20.3CAminiumSaltsandQuaternaryAmmoniumSalts(銨鹽與季銨鹽)When1°,2°,and3°aminesactasbasesandreactwithacids,theyformcompoundscalledaminiumsalts.Aminiumsalt—N+attachedtoatleastone

CH3CH2NH3(CHCH)

(CHCH) 2

2 (CHCH)

(CHCH) 2

2 Departmentof XiamenORGANIC WhenN+isnotattachedtoaH.thecompoundiscalledaquaternaryammoniumsalt.(CH(CH3CH2CH2CH2)4NTetrabutylammoniumbromide(TBAB)(aquaternaryammoniumsalt)Quaternaryammoniumhydroxides(季銨堿)arestrongbasesasstrongasNaOHorKOH.(CH(CH3)4N+(CH3)4N+Departmentof XiamenORGANIC 20.3DSolubilityofAminesinAqueousAlmostallalkylaminiumchlorides,bromides,iodidesandsulfatesaresolubleinwater.DistinguishingaminesfromnonbasiccompoundsSeparatingaminesfromnonbasiccompounds (orH2SO4)

(oraminiumsaltWater-insolubleamidesdonotdissolveindiluteaqueousacidsolution.Departmentof XiamenORGANIC 20.3EAminesasResolvingEnantiomericallypureaminesareoftenusedtoresolveracemicformofacidiccompounds.Naturallyoccurringopticallyactiveaminessuchas(–)-quinine,(–)-strychnine,and(–)-brucineareoftenemployedasresolvingagentsforracemicacids. N H

N H Departmentof XiamenORGANIC 20.4SomeBiologicallyImportantDepartmentof XiamenORGANIC 2-

R=CH3,AdrenalineR=H,Noradrenaline

Departmentof XiamenORGANIC

HNHNN3H3

HCNHCNRCH3Codeine

Departmentof XiamenORGANIC VitaminsandAn