胺重氮和偶氮化合物

胺重氮和偶氮化合物演示文稿2023/3/301當前1頁，總共78頁。2023/3/302（優(yōu)選）胺重氮和偶氮化合物當前2頁，總共78頁。10.1NomenclatureandStructureofAmines

CommonNames：乙胺二乙胺苯胺甲（基）乙（基）丙胺ethanaminediethylamineanilineNethylmethylpropanamine當前3頁，總共78頁。選擇含氮的最長碳鏈為母體，稱為“某胺”，氮上的其它烴基則作為取代基，在其前面加上N-，以明確取代基的位置。系統(tǒng)命名法：N,N-二甲基-4-甲氧基苯胺3-甲基-N-乙基戊胺結構比較復雜的胺和含有多官能團的化合物，也可以把烴或其它官能團作為母體，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-戊醇當前4頁，總共78頁。當前5頁，總共78頁。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當前6頁，總共78頁。當前7頁，總共78頁。當前8頁，總共78頁。當前9頁，總共78頁。(+)-Tr?gerbase(-)-Tr?gerbase

特勒格爾當前10頁，總共78頁。（S)(R)當前11頁，總共78頁。10.2BoilingPointandWaterSolubility

CompoundCH3CH3CH3OHCH3NH2CH3CH2CH3CH3CH2OHCH3CH2NH2Mol.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當前12頁，總共78頁。11.3BasicityofAmines

：

當前13頁，總共78頁。氣相中測定的堿性強弱次序為：

(C2H5)3N

(C2H5)2NH

C2H5NH2

NH3，

水溶液中測定的堿性強弱次序為：

(C2H5)2NH

(C2H5)3N

C2H5NH2

NH3，

烷基給電子和氫鍵的共同作用結果當前14頁，總共78頁。烷基的給電子作用氫鍵的作用

氫鍵的生成使銨離子更加穩(wěn)定，從而使堿性增強。

當前15頁，總共78頁。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-C6H4NH29.344.601.204.40-0.262.471.00當前16頁，總共78頁。Strongbaseshaveweakconjugateacids,andweakbaseshavestrongconjugateacids.當前17頁，總共78頁。4.582.471.00當前18頁，總共78頁。pKa=13.6Here,resonancestabilizationofthebaseissmall,duetochargeseparation,whiletheconjugateacidisstabilizedstronglybychargedelocalization.Consequently,aqueoussolutionsofguanidinearenearlyasbasicasaresolutionsofsodiumhydroxide.當前19頁，總共78頁。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當前20頁，總共78頁。問題11-8DBN和DBU比一般胺的堿性強得多，是有機合成中廣泛使用的有機堿，試指出DBN和DBU分子中哪一個氮原子最容易被質子化，并解釋它們比簡單胺堿性增強的原因。當前21頁，總共78頁。11.4AcidityofAminespKa~36氨基離子當前22頁，總共78頁。Compound

C6H5SO2NH2

pKa33271915109.6當前23頁，總共78頁。11.5PreparationofAmines

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-NH2當前24頁，總共78頁。當前25頁，總共78頁。當前26頁，總共78頁。Gabriel合成法——

當前27頁，總共78頁。當前28頁，總共78頁。硝基的還原——ReductionofNitroGroups

常用的還原劑：錫、鐵、鋅、氯化亞錫等

當前29頁，總共78頁。當前30頁，總共78頁。肟的還原——當前31頁，總共78頁。當前32頁，總共78頁。HofmannRearrangementandCurtiusReaction

缺電子，空軌道N當前33頁，總共78頁。在Hofmann重排反應中，如果發(fā)生遷移的烴基碳原子為手性碳，遷移時其構型保持。當前34頁，總共78頁。CurtiusReaction?；┊斍?5頁，總共78頁。當前36頁，總共78頁。當前37頁，總共78頁。(i)Alkylationofthesulfonamidederivativeofa1o-amine.Gives2o-amines.

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

(iii)Reductionofamidederivativesof1o&2o-amines.Gives2o&3o-amines合成2級和3級胺當前38頁，總共78頁。當前39頁，總共78頁。ReductiveAmination當前40頁，總共78頁。完成下列轉變當前41頁，總共78頁。TheLeuckartReaction

Ausefulvariantofthereductiveaminationmethodusesformicacidorformatesaltsasreductants.當前42頁，總共78頁。MannichReaction當前43頁，總共78頁。當前44頁，總共78頁。11.6胺的反應（ReactionsofAmines）11.6.1烷基化反應（AlkylationofAmines）當前45頁，總共78頁。11.6.2胺的?；ˋcylationofAmines）Aza-MichaelAddition：當前46頁，總共78頁。ReactionwithBenzenesulfonylchloride(磺酰化，Hinsbergtest)⑴可用于鑒別：與對甲基苯磺酰氯作用產物可溶于強堿的為伯胺；有固體析出的為仲胺；不反應，出現分層現象的為叔胺。⑵可用于分離伯、仲、叔胺。在混合物中加入對甲苯磺酰氯，進行作用，然后:蒸出叔胺；過濾得到仲胺的磺酰胺，濾液為伯胺的磺酰胺鈉鹽。產物經過水解得到原來的胺。當前47頁，總共78頁。10.6.3胺的氧化和Cope消除CopeElimination——occurswhen3o-amineoxidesareheatedattemperaturesof150to200oC當前48頁，總共78頁。消除機理：E2syn-Eliminations有兩個消除位點時：1）Hofmann產物為主；2）如有順反，反式為主當前49頁，總共78頁。當前50頁，總共78頁。11.6.4與亞硝酸的反應（ReactionofAmineswithNitrousAcid）

Nitrousacid:HNO2orHONO1°-Amines+HONO(coldacidicsolution)

NitrogenGasEvolutionfromaClearSolution2°-Amines+HONO(coldacidicsolution)

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

AClearSolution(AmmoniumSaltFormation)(1)AliphaticAmines當前51頁，總共78頁。Undertheacidicconditionsofthisreaction,allaminesundergoreversiblesaltformation:Thishappenswith3o-amines,andthesaltsareusuallysolubleinwater.Thereactionsofnitrousacidwith1°-and2°-aliphaticaminesmaybeexplainedbyconsideringtheirbehaviorwiththenitrosoniumcation(NO+),anelectrophilicspeciespresentinacidicnitrousacidsolutions.亞硝酰正離子nitrosoniumcation當前52頁，總共78頁。PrimaryAmines

脂肪族伯胺生成的烷基重氮鹽在低溫下也會放出氮氣生成碳正離子，并按碳正離子的機理繼續(xù)反應。

當前53頁，總共78頁。N-亞硝基胺SecondaryAmines

當前54頁，總共78頁。(2)ArylAmines

1o-ArylAmines

芳香族伯胺與亞硝酸反應生成的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的合成中。

當前55頁，總共78頁。2o-ArylAmines

3o-ArylAmines

當前56頁，總共78頁。11.6.5芳胺的親電取代（ElectrophilicSubstitutionofArylAmines）當前57頁，總共78頁。當前58頁，總共78頁。11.7季銨鹽的消除反應（EliminationReactionsof

4o-AmmoniumSalts）當前59頁，總共78頁。HofmannElimination

——含有-氫的季銨堿，在受熱時則分解為烯烴、叔胺和水。

當前60頁，總共78頁。HofmannRule

——ThetendencyofHofmanneliminationstogivetheless-substituteddoublebondisomer.Thiscontrastss