北大有機(jī) 雜環(huán)化合物

2022/12/31Chapter14HeterocyclicCompounds（雜環(huán)化合物）Heterocycle/HeterocyclicCompound構(gòu)成環(huán)系的原子除C外，還有其它雜原子。O,S,N.Hetero-atom(雜原子):HeterocycleSaturatedHeterocycles

飽和雜環(huán)化合物AromaticHeterocycles

芳香雜環(huán)化合物體現(xiàn)各自功能團(tuán)的性質(zhì)2022/12/31一.Classification&Nomenclature:按環(huán)的大小Five-memberedringSix-memberedring按雜原子的數(shù)目一個雜原子雜環(huán)兩個雜原子雜環(huán)多個雜原子雜環(huán)按環(huán)的拼合形式單雜環(huán)(homo-heterocycle)稠雜環(huán)(fused-heterocycle)2022/12/31pyrrole

吡咯thiophene

噻吩furan呋喃Classification&NomenclatureFive-memberedringheterocyclesimidazole

咪唑pyrazole

吡唑oxazole口惡唑thiazole

噻唑Isoxazole異口惡唑2022/12/31

Six-memberedringheterocyclesClassification&Nomenclaturepyridine

吡啶pyrimidine

嘧啶2H-pyran2H-吡喃Pyridazine

噠嗪Pyrazine

吡嗪2022/12/31

Fused-heterocyclesClassification&Nomenclaturequinoline

喹啉iso-quinoline*

異喹啉Purine*

嘌呤Indole吲哚

蝶啶pteridine口丫啶acridine

吩嗪phenazinecarbazole

咔唑Phenothiazine

吩噻嗪2022/12/31Classification&NomenclatureAttention!“指示氫”

or“標(biāo)氫”—最多的非累積雙鍵外的飽和氫沒有達(dá)到最多的非累積雙鍵，“外加氫”的標(biāo)注2022/12/31Classification&Nomenclature取代雜環(huán)的命名：編號原則：單雜環(huán)、稠雜環(huán)；最小編號和優(yōu)先順序法則iso-quinoline*

異喹啉Purine*

嘌呤5-硝基-2-呋喃甲醛4-氨基嘧啶N,N-二乙基-3-吡啶甲酰胺1,3,7-三甲基嘌呤-2,6-二酮3-甲基-5-氯喹啉7-碘-8-羥基喹啉-5-磺酸2022/12/31Classification&Nomenclature互變異構(gòu)的存在，編號及名稱的改變7H-嘌呤9H-嘌呤2,4-二羥基嘧啶嘧啶-2,4-二酮5-甲基吡唑3-甲基吡唑2022/12/31Classification&Nomenclature拼合雜環(huán)的命名：非特定稠環(huán)基本環(huán)附加環(huán)稠合邊的表示呋喃并[2,3-b]噻吩吡咯并[3,2-b]噻吩2022/12/31Classification&Nomenclature拼合雜環(huán)的命名：整體稠環(huán)編號，取代基位置5-苯基咪唑并[2,1-b]噻唑6H-吡唑并[4,5-d]口惡唑2022/12/31二.Six-memberedHeterocycliccompoundsPyridine吡啶1.Structure:

C5H5N芳香性較強(qiáng)的堿性2022/12/31Kekule’sstructureAromaticity?電子云的分布E.S.變難N.S.變易Oxidation難Reduction易BasicitySix-memberedHeterocycliccompounds2022/12/312.Physicalproperties(1)(偶極矩)Dipolemoment=7.4110-38c.m3.9010-38c.mIC方向一致Six-memberedHeterocycliccompounds(2)Solubility:

吡啶可以與水以任意比例互溶2022/12/313.Chemicalreactionsa.BasicityofPyridineBasicitySix-memberedHeterocycliccompounds2022/12/31Six-memberedHeterocycliccompoundsPyr.SO3磺化試劑?；噭┘谆噭?022/12/31b.ElectrophilicSubstitution:N的-I鈍化環(huán)反應(yīng)條件劇烈取代反應(yīng)

發(fā)生在3-位（）Six-memberedHeterocycliccompounds2022/12/31Six-memberedHeterocycliccompounds不穩(wěn)定取代2-位取代3-位Six-memberedHeterocycliccompounds-Pyridine2022/12/31Six-memberedHeterocycliccompoundsc.NucleophilicSubstitution2,4,6-位的影響—X的取代Six-memberedHeterocycliccompounds-Pyridine2022/12/31Six-memberedHeterocycliccompoundsE.ChichibabinReactionH-的取代Six-memberedHeterocycliccompounds-Pyridine2022/12/31Six-memberedHeterocycliccompounds2-位(6-位)3-位4-位八電子氮負(fù)離子八電子氮負(fù)離子Six-memberedHeterocycliccompounds-Pyridine2022/12/31Six-memberedHeterocycliccompounds-Pyridined.ReactionsofsidechainSideChainAcidityof-H2022/12/31Six-memberedHeterocycliccompounds2-位甲基3-位甲基4-位甲基八隅體八隅體2022/12/31Six-memberedHeterocycliccompoundse.Oxidations&Reductions側(cè)鏈的氧化煙堿煙酸煙酰胺N-氧化物Pyridine-N-oxide3-甲基吡啶N-氧化物Six-memberedHeterocycliccompounds-PyridinePyridine-N-oxide:Substitution/Position2022/12/31Six-memberedHeterocycliccompounds-PyridineElectrophilicNucleophilic2022/12/31Six-memberedHeterocycliccompounds-Pyridine-attack-attack-attack2022/12/31Six-memberedHeterocycliccompounds-PyridinepiperidineReduction2022/12/31Six-memberedHeterocycliccompounds-Pyrimidine嘧啶Pyrimidinesp2堿性水溶性取代反應(yīng)2022/12/31Six-memberedHeterocycliccompounds-Pyrimidine2,4,6-positions(Uracil,U)尿嘧啶胞嘧啶(Cytosine,C)胸腺嘧啶(Thymine.T)tautomerism2022/12/31Six-memberedHeterocycliccompounds-PyrimidineVitaminB2SulfadiazineSD磺胺嘧啶苯巴比妥PhenobarbitalMoxonidine莫索尼定2022/12/31Six-memberedHeterocycliccompounds-PyrimidineAntimetabolicAgentsFluorouracil5-FUTegafurCytarabine阿糖胞苷司他夫定StavudineZidovudine齊多夫定拉米夫定LamivudineAntiviralAgents2022/12/31Six-memberedHeterocycliccompounds-QuinolineandIsoquinolineQuinolineandIsoquinolinequinoline

喹啉iso-quinoline*

異喹啉雜化sp2堿性取代反應(yīng)：E.S.N.S.位置2022/12/31Six-memberedHeterocycliccompounds-QuinolineandIsoquinolineElectrophilicSubstitution異環(huán)取代5-，8-位2022/12/31Six-memberedHeterocycliccompounds-QuinolineandIsoquinolineNucleophilicSubstitution發(fā)生在吡啶環(huán)上，2(1)、4位上2022/12/31Six-memberedHeterocycliccompounds-QuinolineandIsoquinolineTheReactionsofSideChain2(1),4位側(cè)鏈-H2022/12/31Six-memberedHeterocycliccompounds-QuinolineandIsoquinolineOxidatio