北大有机课件第十四章杂环化合物

2022/11/26有机Chapter14HeterocyclicCompounds（杂环化合物）Heterocycle/HeterocyclicCompound构成环系的原子除C外，还有其它杂原子。O,S,N.Hetero-atom(杂原子):HeterocycleSaturatedHeterocycles

饱和杂环化合物AromaticHeterocycles

芳香杂环化合物体现各自功能团的性质2022/11/26有机Chapter14Heteroc2022/11/26有机一.Classification&Nomenclature:按环的大小Five-memberedringSix-memberedring按杂原子的数目一个杂原子杂环两个杂原子杂环多个杂原子杂环按环的拼合形式单杂环(homo-heterocycle)稠杂环(fused-heterocycle)2022/11/26有机一.Classification2022/11/26有机pyrrole

吡咯thiophene

噻吩furan呋喃Classification&NomenclatureFive-memberedringheterocyclesimidazole

咪唑pyrazole

吡唑oxazole口恶唑thiazole

噻唑Isoxazole异口恶唑2022/11/26有机pyrrolethiophenefu2022/11/26有机Six-memberedringheterocyclesClassification&Nomenclaturepyridine

吡啶pyrimidine

嘧啶2H-pyran2H-吡喃Pyridazine

哒嗪Pyrazine

吡嗪2022/11/26有机Six-memberedrin2022/11/26有机Fused-heterocyclesClassification&Nomenclaturequinoline

喹啉iso-quinoline*

异喹啉Purine*

嘌呤Indole吲哚

蝶啶pteridine口丫啶acridine

吩嗪phenazinecarbazole

咔唑Phenothiazine

吩噻嗪2022/11/26有机Fused-heterocycl2022/11/26有机Classification&NomenclatureAttention!“指示氢”

or“标氢”—最多的非累积双键外的饱和氢没有达到最多的非累积双键，“外加氢”的标注2022/11/26有机Classification&N2022/11/26有机Classification&Nomenclature取代杂环的命名：编号原则：单杂环、稠杂环；最小编号和优先顺序法则iso-quinoline*

异喹啉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-羟基喹啉-5-磺酸2022/11/26有机Classification&N2022/11/26有机Classification&Nomenclature互变异构的存在，编号及名称的改变7H-嘌呤9H-嘌呤2,4-二羟基嘧啶嘧啶-2,4-二酮5-甲基吡唑3-甲基吡唑2022/11/26有机Classification&N2022/11/26有机Classification&Nomenclature拼合杂环的命名：非特定稠环基本环附加环稠合边的表示呋喃并[2,3-b]噻吩吡咯并[3,2-b]噻吩2022/11/26有机Classification&N2022/11/26有机Classification&Nomenclature拼合杂环的命名：整体稠环编号，取代基位置5-苯基咪唑并[2,1-b]噻唑6H-吡唑并[4,5-d]口恶唑2022/11/26有机Classification&N2022/11/26有机二.Six-memberedHeterocycliccompoundsPyridine吡啶1.Structure:

C5H5N芳香性较强的碱性2022/11/26有机二.Six-memberedHe2022/11/26有机Kekule’sstructureAromaticity?电子云的分布E.S.变难N.S.变易Oxidation难Reduction易BasicitySix-memberedHeterocycliccompounds2022/11/26有机Kekule’sstructure2022/11/26有机2.Physicalproperties(1)(偶极矩)Dipolemoment=7.4110-38c.m3.9010-38c.mIC方向一致Six-memberedHeterocycliccompounds(2)Solubility:吡啶可以与水以任意比例互溶2022/11/26有机2.Physicalproper2022/11/26有机3.Chemicalreactionsa.BasicityofPyridineBasicitySix-memberedHeterocycliccompounds2022/11/26有机3.Chemicalreacti2022/11/26有机Six-memberedHeterocycliccompoundsPyr.SO3磺化试剂酰化试剂甲基化试剂2022/11/26有机Six-memberedHeter2022/11/26有机b.ElectrophilicSubstitution:N的-I钝化环反应条件剧烈取代反应发生在3-位（）Six-memberedHeterocycliccompounds2022/11/26有机b.ElectrophilicS2022/11/26有机Six-memberedHeterocycliccompounds不稳定取代2-位取代3-位Six-memberedHeterocycliccompounds-Pyridine2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompoundsc.NucleophilicSubstitution2,4,6-位的影响—X的取代Six-memberedHeterocycliccompounds-Pyridine2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompoundsE.ChichibabinReactionH-的取代Six-memberedHeterocycliccompounds-Pyridine2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds2-位(6-位)3-位4-位八电子氮负离子八电子氮负离子Six-memberedHeterocycliccompounds-Pyridine2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-Pyridined.ReactionsofsidechainSideChainAcidityof-H2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds2-位甲基3-位甲基4-位甲基八隅体八隅体2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompoundse.Oxidations&Reductions侧链的氧化烟碱烟酸烟酰胺N-氧化物Pyridine-N-oxide3-甲基吡啶N-氧化物Six-memberedHeterocycliccompounds-PyridinePyridine-N-oxide:Substitution/Position2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-PyridineElectrophilicNucleophilic2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-Pyridine-attack-attack-attack2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-PyridinepiperidineReduction2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-Pyrimidine嘧啶Pyrimidinesp2碱性水溶性取代反应2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-Pyrimidine2,4,6-positions(Uracil,U)尿嘧啶胞嘧啶(Cytosine,C)胸腺嘧啶(Thymine.T)tautomerism2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-PyrimidineVitaminB2SulfadiazineSD磺胺嘧啶苯巴比妥PhenobarbitalMoxonidine莫索尼定2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-PyrimidineAntimetabolicAgentsFluorouracil5-FUTegafurCytarabine阿糖胞苷司他夫定StavudineZidovudine齐多夫定拉米夫定LamivudineAntiviralAgents2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-QuinolineandIsoquinolineQuinolineandIsoquinolinequinoline

喹啉iso-quinoline*

异喹啉杂化sp2碱性取代反应：E.S.N.S.位置2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-QuinolineandIsoquinolineElectrophilicSubstitution异环取代5-，8-位2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-QuinolineandIsoquinolineNucleophilicSubstitution发生在吡啶环上，2(1)、4位上2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-QuinolineandIsoquinolineTheReactionsofSideChain2(1),4位侧链-H2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-QuinolineandIsoquinolineOxidation&Reduction氧化苯环还原吡啶环2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-PyranPyran吡喃2H-吡喃(-吡喃)4H-吡喃(-吡喃)-吡喃酮-吡喃酮吡喃盐正离子口恶英嗡盐离子杂化不饱和环醚——非芳香性芳香性稳定性/高反应活性2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-Pyran-吡喃酮2022/11/26有机Six-memberedHeter38可编辑感谢下载38可编辑感谢下载2022/11/26有机Chapter14HeterocyclicCompounds（杂环化合物）Heterocycle/HeterocyclicCompound构成环系的原子除C外，还有其它杂原子。O,S,N.Hetero-atom(杂原子):HeterocycleSaturatedHeterocycles

饱和杂环化合物AromaticHeterocycles

芳香杂环化合物体现各自功能团的性质2022/11/26有机Chapter14Heteroc2022/11/26有机一.Classification&Nomenclature:按环的大小Five-memberedringSix-memberedring按杂原子的数目一个杂原子杂环两个杂原子杂环多个杂原子杂环按环的拼合形式单杂环(homo-heterocycle)稠杂环(fused-heterocycle)2022/11/26有机一.Classification2022/11/26有机pyrrole

吡咯thiophene

噻吩furan呋喃Classification&NomenclatureFive-memberedringheterocyclesimidazole

咪唑pyrazole

吡唑oxazole口恶唑thiazole

噻唑Isoxazole异口恶唑2022/11/26有机pyrrolethiophenefu2022/11/26有机Six-memberedringheterocyclesClassification&Nomenclaturepyridine

吡啶pyrimidine

嘧啶2H-pyran2H-吡喃Pyridazine

哒嗪Pyrazine

吡嗪2022/11/26有机Six-memberedrin2022/11/26有机Fused-heterocyclesClassification&Nomenclaturequinoline

喹啉iso-quinoline*

异喹啉Purine*

嘌呤Indole吲哚

蝶啶pteridine口丫啶acridine

吩嗪phenazinecarbazole

咔唑Phenothiazine

吩噻嗪2022/11/26有机Fused-heterocycl2022/11/26有机Classification&NomenclatureAttention!“指示氢”

or“标氢”—最多的非累积双键外的饱和氢没有达到最多的非累积双键，“外加氢”的标注2022/11/26有机Classification&N2022/11/26有机Classification&Nomenclature取代杂环的命名：编号原则：单杂环、稠杂环；最小编号和优先顺序法则iso-quinoline*

异喹啉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-羟基喹啉-5-磺酸2022/11/26有机Classification&N2022/11/26有机Classification&Nomenclature互变异构的存在，编号及名称的改变7H-嘌呤9H-嘌呤2,4-二羟基嘧啶嘧啶-2,4-二酮5-甲基吡唑3-甲基吡唑2022/11/26有机Classification&N2022/11/26有机Classification&Nomenclature拼合杂环的命名：非特定稠环基本环附加环稠合边的表示呋喃并[2,3-b]噻吩吡咯并[3,2-b]噻吩2022/11/26有机Classification&N2022/11/26有机Classification&Nomenclature拼合杂环的命名：整体稠环编号，取代基位置5-苯基咪唑并[2,1-b]噻唑6H-吡唑并[4,5-d]口恶唑2022/11/26有机Classification&N2022/11/26有机二.Six-memberedHeterocycliccompoundsPyridine吡啶1.Structure:

C5H5N芳香性较强的碱性2022/11/26有机二.Six-memberedHe2022/11/26有机Kekule’sstructureAromaticity?电子云的分布E.S.变难N.S.变易Oxidation难Reduction易BasicitySix-memberedHeterocycliccompounds2022/11/26有机Kekule’sstructure2022/11/26有机2.Physicalproperties(1)(偶极矩)Dipolemoment=7.4110-38c.m3.9010-38c.mIC方向一致Six-memberedHeterocycliccompounds(2)Solubility:吡啶可以与水以任意比例互溶2022/11/26有机2.Physicalproper2022/11/26有机3.Chemicalreactionsa.BasicityofPyridineBasicitySix-memberedHeterocycliccompounds2022/11/26有机3.Chemicalreacti2022/11/26有机Six-memberedHeterocycliccompoundsPyr.SO3磺化试剂酰化试剂甲基化试剂2022/11/26有机Six-memberedHeter2022/11/26有机b.ElectrophilicSubstitution:N的-I钝化环反应条件剧烈取代反应发生在3-位（）Six-memberedHeterocycliccompounds2022/11/26有机b.ElectrophilicS2022/11/26有机Six-memberedHeterocycliccompounds不稳定取代2-位取代3-位Six-memberedHeterocycliccompounds-Pyridine2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompoundsc.NucleophilicSubstitution2,4,6-位的影响—X的取代Six-memberedHeterocycliccompounds-Pyridine2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompoundsE.ChichibabinReactionH-的取代Six-memberedHeterocycliccompounds-Pyridine2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds2-位(6-位)3-位4-位八电子氮负离子八电子氮负离子Six-memberedHeterocycliccompounds-Pyridine2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-Pyridined.ReactionsofsidechainSideChainAcidityof-H2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds2-位甲基3-位甲基4-位甲基八隅体八隅体2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompoundse.Oxidations&Reductions侧链的氧化烟碱烟酸烟酰胺N-氧化物Pyridine-N-oxide3-甲基吡啶N-氧化物Six-memberedHeterocycliccompounds-PyridinePyridine-N-oxide:Substitution/Position2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-PyridineElectrophilicNucleophilic2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-Pyridine-attack-attack-attack2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-PyridinepiperidineReduction2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-Pyrimidine嘧啶Pyrimidinesp2碱性水溶性取代反应2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-Pyrimidine2,4,6-positions(Uracil,U)尿嘧啶胞嘧啶(Cytosine,C)胸腺嘧啶(Thymine.T)tautomerism2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-PyrimidineVitaminB2SulfadiazineSD磺胺嘧啶苯巴比妥PhenobarbitalMoxonidine莫索尼定2022/11/26有机Six-memberedHeter2022/11/26有机Six-memberedHeterocycliccompounds-PyrimidineAntimetabolicAgentsFluorouracil5