北大有機(jī)有機(jī)含氮化合物2

2023/9/2有機(jī)Chapter13OrganicCompoundsContainingNitrogen有機(jī)含氮化合物硝基化合物酰胺腈肟胺重氮和偶氮化合物

2023/9/2有機(jī)含氮有機(jī)物硝基化合物NitroCompunds酰胺Amides腈Nitriles肟Oximes胺Amines重氮和偶氮化合物DiazoniumSalts&Azocompounds2023/9/2有機(jī)Amine(胺)NH3

胺(Amine)

銨銨鹽(AmmoniumSalt)

氨(Ammonia)

季胺鹽(QuaternaryAmmoniumSalt)2023/9/2有機(jī)根據(jù)N上所連烴基的種類(lèi)脂肪胺芳香胺芳脂胺CH3NH2一.Classification&Naming:2023/9/2有機(jī)根據(jù)N上所連烴基的數(shù)目RNH2R2NHR3NR4N+1°胺（伯胺）PrimaryAmines2°胺（仲胺）SecondaryAmines3°胺（叔胺）TertiaryAmines4°胺（季銨鹽)QuaternaryAmmoniumSaltClassification&Naming2023/9/2有機(jī)根據(jù)分子中胺基的數(shù)目一元胺多元胺胺的分級(jí)與鹵代烴、醇不同！(CH3)3C-OH3°醇(CH3)3C-NH21°胺Classification&Naming3o鹵代烴2023/9/2有機(jī)(CH3)2NHdimethylamineaniline苯胺N-methylanilineCH3-NH2methylamine

甲（基）胺CH3CH2NH2ethylamine乙胺Classification&Naming2023/9/2有機(jī)3-胺甲基-2-N,N-二甲胺基己烷C6H5NH3+Cl-氯化苯銨Classification&Naming3-(N-乙胺基)庚烷2-氨基乙醇-(N-甲胺基)丙酸對(duì)氨基苯磺酸氯化四甲銨硫酸乙銨2023/9/2有機(jī)二.Structure&Isomerism:SP32023/9/2有機(jī)SP3SP3“SP2”Structure&Isomerism2023/9/2有機(jī)胺的對(duì)映體的轉(zhuǎn)變構(gòu)型翻轉(zhuǎn)，能壘較低，翻轉(zhuǎn)速度較快N上不同的取代手性氮對(duì)映異構(gòu)體？—自動(dòng)外消旋化，不可拆分Structure&Isomerism2023/9/2有機(jī)

氮在環(huán)內(nèi)，翻轉(zhuǎn)受阻

季銨鹽不能進(jìn)行氮的翻轉(zhuǎn)

可分離出穩(wěn)定的旋光異構(gòu)體胺的對(duì)映體的轉(zhuǎn)變Structure&IsomerismTroger堿S-R-

形成N氧化物，不能翻轉(zhuǎn)

2023/9/2有機(jī)三.PreparationofAamines

PreparationbyNucleolicSubstitution1、胺的烷基化1°胺2°胺3°胺4°胺反應(yīng)產(chǎn)物復(fù)雜如何控制產(chǎn)物在1°胺？采用該法合成胺，哪一種鹵代烷不適用？芳香胺2023/9/2有機(jī)PreparationofAamines3、Gabriel合成法制備1°胺2、芳香鹵代烴的胺解2023/9/2有機(jī)PreparationofAamines

PreparationbyReduction1.硝基化合物1°胺2.腈3.酰胺4.肟5.AlkylAzide疊氮物2023/9/2有機(jī)PreparationofAamines6、羰基化合物的還原胺化(ReductiveAmination)NH31°胺1°胺2°胺2°胺3°胺1°胺的二甲基化2023/9/2有機(jī)PreparationofAamines

PreparationbyRearrangements1、HofmannRearrangements（Hofmann重排，降解）異氰酸酯機(jī)理2023/9/2有機(jī)PreparationofAaminesR-2-甲基丁酰胺R-2-甲基丁胺三元環(huán)過(guò)渡態(tài)構(gòu)型保持SN2Stereochemistry2023/9/2有機(jī)PreparationofAamines2、Curtius&SchmidtRearrangements酰疊氮化合物CurtiusSchmidt2023/9/2有機(jī)

PreparationbyMannichreactionPreparationofAamines-胺基酮-H酮甲醛胺鹽酸性水、醇溶液胺甲基化反應(yīng)2023/9/2有機(jī)機(jī)理PreparationofAaminesMannichBase2023/9/2有機(jī)四.ReactionSP3LongelectronpairBasicity堿性，成鹽Nucleophlicity親核性，烷基化ResonanceActivitiontotheAromaticringElectophilicSubstitution芳香環(huán)的親電取代反應(yīng)2023/9/2有機(jī)(一)BasicityandFormationofAmmoniumSalts：氮上的孤對(duì)電子不溶溶解LewisBasepKb=-lgKb實(shí)驗(yàn)測(cè)定接受質(zhì)子或提供電子2023/9/2有機(jī)試驗(yàn)測(cè)定的胺的pKbBasicityandFormationofAmmoniumSalts2023/9/2有機(jī)

脂肪胺氨苯胺

脂肪胺:2°胺1°胺3°胺

芳香胺：對(duì)甲氧基苯胺>苯胺>對(duì)硝基苯胺BasicityandFormationofAmmoniumSalts2023/9/2有機(jī)

脂肪胺的堿性2o>1o>3o脂肪胺的堿性都大于氨；烷基相同，仲胺堿性最強(qiáng)，伯、叔胺次之電子(誘導(dǎo)、共軛）效應(yīng)溶劑化效應(yīng)位阻效應(yīng)3o>2o>1o1o>2o>3o1o>2o>3o胺的堿性強(qiáng)度決定于氮上電子云密度增高N上電子云密度降低N上電子云密度BasicityandFormationofAmmoniumSaltspKb3.01pKb2.732023/9/2有機(jī)

芳香胺的堿性苯胺的結(jié)構(gòu)p-

共軛N上電子云密度下降芳香胺堿性比氨弱

芳香胺氮上氫被推電子基團(tuán)取代

芳香胺氮上氫被吸電子基團(tuán)取代

芳香胺苯環(huán)上氫被基團(tuán)取代，對(duì)堿性影響

----取代基的結(jié)構(gòu)與位置致活基團(tuán)(-NH2,-OCH3,-CH3)致鈍基團(tuán)(-NO2,-SO3H,-CO2H,-X,-NH3+)BasicityandFormationofAmmoniumSalts誘導(dǎo)與共軛2023/9/2有機(jī)

季胺堿離子化合物

堿性順序：季胺堿>脂肪氨>氨>芳香胺>酰胺>磺酰胺

酰亞胺BasicityandFormationofAmmoniumSalts2023/9/2有機(jī)胺的成鹽反應(yīng)RNH2+H+RNH3+R2NH+H+R2NH2+R3N+H+R3NH+BasicityandFormationofAmmoniumSalts水溶性銨鹽：無(wú)臭，不揮發(fā)的固體，溶于水，但不溶于有機(jī)溶劑。

分離，純化——植物中生物堿的提取

利于吸收和保存鹽酸普魯卡因?yàn)躅^堿/附子2023/9/2有機(jī)手性羧酸的拆分BasicityandFormationofAmmoniumSalts非對(duì)映異構(gòu)體番木鱉堿(strychnine)馬錢(qián)子堿(brucine)辛可寧(cinchonine)奎寧(quinine)2023/9/2有機(jī)(二)AlkylationandQuaternaryAmmoniumSaltsAlkylation堿性親核性烷基化

季銨堿QuaternaryAmmoniumBase2023/9/2有機(jī)AlkylationandQuaternaryAmmoniumSaltsQuaternaryAmmoniumCompounds膽堿(choline)溴化乙酰膽堿(acetylcholinebromide)乙酰膽堿(acetylcholine,ACh)磷脂2023/9/2有機(jī)QuaternaryAmmoniumSalts兩溶性

相轉(zhuǎn)移催化劑(Phase-transferCatalyst)2023/9/2有機(jī)Phase-transferCatalyst2023/9/2有機(jī)(三)MethylationandHofmannEliminationHofmannElimination

E2elinminationMechanismoftheHofmannelimination2023/9/2有機(jī)MethylationandHofmannEliminationHofmann’srule:Thelesssubstitutedalkeneispreferredminormajor2023/9/2有機(jī)MethylationandHofmannEliminationStereochemistryofHofmanneliminationE2Transelimination2023/9/2有機(jī)MethylationandHofmannElimination2023/9/2有機(jī)MethylationandHofmannEliminationApplication胺結(jié)構(gòu)的分析完全甲基化Hofmann消除

第一次完全甲基化生成的季銨鹽甲基增加個(gè)數(shù)胺的級(jí)別

消除的次數(shù),產(chǎn)生烯烴及胺的結(jié)構(gòu)原胺的結(jié)構(gòu)有幾個(gè)含

-H的烴基2023/9/2有機(jī)(四)AcylationandSulfonylationReactionor縛酸劑除酸劑苯磺酰氯苯磺酰胺AcylationSulfonylation2023/9/2有機(jī)

AcylationandSulfonylationApplications

藥物合成中的應(yīng)用撲熱息痛(paraspen)非那西丁(phenacetin)磺胺藥(抗菌劑，利尿藥，降糖藥)2023/9/2有機(jī)

AcylationandSulfonylation

2023/9/2有機(jī)

氨基的保護(hù)芳胺的易氧化性乙酰氨基的定位規(guī)律

胺的分離、鑒定HinsbergReaction溶解不溶不反應(yīng)

AcylationandSulfonylation2023/9/2有機(jī)(五)ReactionwithNitrousAcidHNO2,亞硝酸NaNO2/HCl,NaNO2/H2SO4芳香伯胺氯化重氮苯DiazoniumSalt重氮鹽重氮化反應(yīng)DiazotizationMechanism2023/9/2有機(jī)脂肪伯胺e.g.ReactionwithNitrousAcid2023/9/2有機(jī)仲胺N-亞硝基胺黃色油狀物，難溶于水和稀酸ReactionwithNitrousAcid2023/9/2有機(jī)脂肪叔胺芳香叔胺成鹽苯環(huán)上取代ReactionwithNitrousAcid2023/9/2有機(jī)(六)Schiff’sbase&Enamine(Schiff堿和烯醇)Schiff’sBaseImineSchiff’sbaseImine&EnamineImineEnamine2023/9/2有機(jī)Enamine(烯胺)Formation酸催化除水環(huán)狀仲胺2023/9/2有機(jī)Enamine(烯胺)Reactions親核能力弱;活潑鹵代烴、酰氯反應(yīng)2023/9/2有機(jī)Enamine(烯胺)Question:2023/9/2有機(jī)(七)ElectrophilicaromaticsubstitutionAstronglyactivitinggroup

Ortho-&Para-position2023/9/2有機(jī)ElectrophilicaromaticsubstitutionNitrated硝化Sulfonated磺化2023/9/2有機(jī)(八)Diazotization&DiazoniumSalts重氮化反應(yīng)和重氮鹽取代基對(duì)穩(wěn)定性的影響2023/9/2有機(jī)Diazotization&DiazoniumSaltsArN2+X-易分解----取代反應(yīng)重氮正離子----親電試劑-----偶聯(lián)反應(yīng)

性質(zhì):離子型化合物,水溶性好,穩(wěn)定性差(光、熱、振動(dòng))

中性或堿性不穩(wěn)定2023/9/2有機(jī)

Substitution&Applications

被鹵素和氰基取代SandmeyerReactionDiazotizatio