胺重氮和偶氮化合物10、1NomenclatureandStructureofAmines

monNames:乙胺二乙胺苯胺甲(基)乙(基)丙胺ethanaminediethylamineanilineNethylmethylpropanamine選擇含氮得最長碳鏈為母體,稱為“某胺”,氮上得其它烴基則作為取代基,在其前面加上N-,以明確取代基得位置。系統(tǒng)命名法:N,N-二甲基-4-甲氧基苯胺3-甲基-N-乙基戊胺結(jié)構(gòu)比較復(fù)雜得胺與含有多官能團(tuán)得化合物,也可以把烴或其它官能團(tuán)作為母體,氨基作為取代基來命名。4-(N,N-二甲氨基)苯甲酸3-甲基-5-氨基-1-戊醇胺類化合物形成銨鹽或季銨鹽后,命名如下例:甲胺鹽酸鹽苯胺硫酸鹽溴化四乙銨MethylammoniumAnilinesulfateTetraethylammoniumchloridebromideN-甲基-N-乙基環(huán)戊烷基銨鹽酸鹽溴化三乙基芐基銨N-Ethyl-N-methylcyclopentylammoniumBenzyltriethylammoniumchloridebromide(+)-Tr?gerbase(-)-Tr?gerbase

特勒格爾(S)(R)10、2BoilingPointandWaterSolubility

poundCH3CH3CH3OHCH3NH2CH3CH2CH3CH3CH2OHCH3CH2NH2Mol、Wt、303231444645Boiling

PointoC-88、6o65o-6、0o-42o78、5o16、6oCCH3(CH2)2CH3CH3(CH2)2OHCH3(CH2)2NH2CH3CH2NHCH3(CH3)3CH(CH3)2CHOH(CH3)2CHNH2(CH3)3NMw、5860595958605959Bp-0、5o97o48o37o-12o82o34o3o大家有疑問的，可以詢問和交流可以互相討論下，但要小聲點(diǎn)11、3BasicityofAmines

:

氣相中測定得堿性強(qiáng)弱次序?yàn)?

(C2H5)3N

(C2H5)2NH

C2H5NH2

NH3,

水溶液中測定得堿性強(qiáng)弱次序?yàn)?

(C2H5)2NH

(C2H5)3N

C2H5NH2

NH3,

烷基給電子與氫鍵得共同作用結(jié)果烷基得給電子作用氫鍵得作用

氫鍵得生成使銨離子更加穩(wěn)定,從而使堿性增強(qiáng)。

胺pKa（25oC,H2O）胺pKa（25oC,H2O）NH3CH3NH2(CH3)2NH(CH3)3NCH3CH2NH2(CH3CH2)2NH(CH3CH2)3N9.2410.6210.739.7910.6410.9410.75C6H5CH2NH2C6H5NH2(C6H5)2NHC6H5NHCH3o-NO2-C6H4NH2m-NO2-C6H4NH2p-NO2-C6H4NH29.344.601.204.40-0.262.471.00Strongbaseshaveweakconjugateacids,andweakbaseshavestrongconjugateacids、4、582、471、00pKa=13、6Here,resonancestabilizationofthebaseissmall,duetochargeseparation,whiletheconjugateacidisstabilizedstronglybychargedelocalization、Consequently,aqueoussolutionsofguanidinearenearlyasbasicasaresolutionsofsodiumhydroxide、BaseNamePyridineTriethyl

AmineHünig'sBaseDBUBarton's

BasePotassium

t-ButoxideSodiumHMDSLDAFormula

(C2H5)3N

(CH3)3CO(–)K(+)[(CH3)3Si]2N(–)Na(+)

[(CH3)2CH]2N(–)Li(+)pKa5、310、711、41214192635、7ImportantReagentBasespKa8、8pKa12pKa6、79pKa12、3問題11-8DBN與DBU比一般胺得堿性強(qiáng)得多,就是有機(jī)合成中廣泛使用得有機(jī)堿,試指出DBN與DBU分子中哪一個氮原子最容易被質(zhì)子化,并解釋它們比簡單胺堿性增強(qiáng)得原因。11、4AcidityofAminespKa~36氨基離子pound

C6H5SO2NH2

pKa33271915109、611、5PreparationofAmines

Preparationof1o-AminesExampleNitrogen

ReactantCarbon

Reactant1stReaction

TypeInitialProduct2ndReaction

Conditions2ndReaction

TypeFinalProduct1、N3(–)RCH2-Xor

R2CH-XSN2RCH2-N3or

R2CH-N3LiAlH4or

4H2&PdHydrogenolysisRCH2-NH2or

R2CH-NH22、C6H5SO2NH(–)RCH2-Xor

R2CH-XSN2RCH2-NHSO2C6H5or

R2CH-NHSO2C6H5NainNH3(liq)HydrogenolysisRCH2-NH2or

R2CH-NH23、CN(–)RCH2-Xor

R2CH-XSN2RCH2-CNor

R2CH-CNLiAlH4

ReductionRCH2-CH2NH2or

R2CH-CH2NH24、NH3RCH=Oor

R2C=OAddition/

EliminationRCH=NHor

R2C=NHH2&Ni

orNaBH3CNReductionRCH2-NH2or

R2CH-NH25、NH3RCOXAddition/

EliminationRCO-NH2LiAlH4ReductionRCH2-NH26、NH2CONH2

(urea)R3C(+)SN1R3C-NHCONH2NaOHsoln、HydrolysisR3C-NH2Gabriel合成法——

硝基得還原——ReductionofNitroGroups

常用得還原劑:錫、鐵、鋅、氯化亞錫等

肟得還原——HofmannRearrangementandCurtiusReaction

缺電子,空軌道N在Hofmann重排反應(yīng)中,如果發(fā)生遷移得烴基碳原子為手性碳,遷移時其構(gòu)型保持。CurtiusReaction?；?i)Alkylationofthesulfonamidederivativeofa1o-amine、Gives2o-amines、

(ii)Reductionofalkyliminesanddialkyliminiumsalts、Gives2o&3o-amines、

(iii)Reductionofamidederivativesof1o&2o-amines、Gives2o&3o-amines合成2級與3級胺ReductiveAmination完成下列轉(zhuǎn)變TheLeuckartReaction

Ausefulvariantofthereductiveaminationmethodusesformicacidorformatesaltsasreductants、MannichReaction11、6胺得反應(yīng)(ReactionsofAmines)11、6、1烷基化反應(yīng)(AlkylationofAmines)11、6、2胺得?；?AcylationofAmines)Aza-MichaelAddition:ReactionwithBenzenesulfonylchloride(磺酰化,Hinsbergtest)⑴可用于鑒別:與對甲基苯磺酰氯作用產(chǎn)物可溶于強(qiáng)堿得為伯胺;有固體析出得為仲胺;不反應(yīng),出現(xiàn)分層現(xiàn)象得為叔胺。⑵可用于分離伯、仲、叔胺。在混合物中加入對甲苯磺酰氯,進(jìn)行作用,然后:蒸出叔胺;過濾得到仲胺得磺酰胺,濾液為伯胺得磺酰胺鈉鹽。產(chǎn)物經(jīng)過水解得到原來得胺。10、6、3胺得氧化與Cope消除CopeElimination——occurswhen3o-amineoxidesareheatedattemperaturesof150to200oC消除機(jī)理:E2syn-Eliminations有兩個消除位點(diǎn)時:1)Hofmann產(chǎn)物為主;2)如有順反,反式為主11、6、4與亞硝酸得反應(yīng)(ReactionofAmineswithNitrousAcid)

Nitrousacid:HNO2orHONO1°-Amines+HONO(coldacidicsolution)

NitrogenGasEvolutionfromaClearSolution2°-Amines+HONO(coldacidicsolution)

AnInsolubleOil(N-Nitrosoamine)3°-Amines+HONO(coldacidicsolution)

AClearSolution(AmmoniumSaltFormation)(1)AliphaticAminesUndertheacidicconditionsofthisreaction,allaminesundergoreversiblesaltformation:Thishappenswith3o-amines,andthesaltsareusuallysolubleinwater、Thereactionsofnitrousacidwith1°-and2°-aliphaticaminesmaybeexplainedbyconsideringtheirbehaviorwiththenitrosoniumcation(NO+),anelectrophilicspeciespresentinacidicnitrousacidsolutions、亞硝酰正離子nitrosoniumcationPrimaryAmines

脂肪族伯胺生成得烷基重氮鹽在低溫下也會放出氮?dú)馍商颊x子,并按碳正離子得機(jī)理繼續(xù)反應(yīng)。

N-亞硝基胺SecondaryAmines

(2)ArylAmines

1o-ArylAmines

芳香族伯胺與亞硝酸反應(yīng)生成得芳香重氮鹽比烷基重氮鹽穩(wěn)定得多,可在水溶液中,0~10oC下保存一段時間,并用于多種芳香族化合物得合成中。

2o-ArylAmines

3o-ArylAmines

11、6、5芳胺得親電取代(ElectrophilicSubstitutionofArylAmines)11、7季銨鹽得消除反應(yīng)(EliminationReactionsof

4o-AmmoniumSalts)HofmannElimination