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1、7/17/2022有机一 .Classification & Nomenclature:按环的按环的大小大小Five-membered ringSix-membered ring按杂原子的按杂原子的数目数目一个一个杂原子杂环杂原子杂环两个两个杂原子杂环杂原子杂环多个多个杂原子杂环杂原子杂环按环的拼合按环的拼合形式形式单单杂环杂环(homo-heterocycle)稠稠杂环杂环(fused-heterocycle)7/17/2022有机Classification & Nomenclature 拼合杂环的命名：拼合杂环的命名：非特定稠环非特定稠环基本环基本环附加环附加环稠合边的表示稠合边的表示呋
2、喃并呋喃并2, 3-b 噻吩噻吩吡咯并吡咯并3, 2-b 噻吩噻吩SO12345abcdHNS12345abc7/17/2022有机Classification & Nomenclature 拼合杂环的命名：拼合杂环的命名：整体稠环编号，取代基位置整体稠环编号，取代基位置NNSPh12345675-苯基咪唑并苯基咪唑并2, 1-b噻唑噻唑NNSPh12345abcNONNH123456NONNH12345abcd6H-吡唑并吡唑并4, 5-d口口恶恶 唑唑7/17/2022有机二二. Six-membered Heterocyclic compoundsPyridine 吡啶吡啶1. Stru
3、cture: C5H5N芳香性芳香性较强的碱性较强的碱性N7/17/2022有机NNNororKekules structureN1.430.841.011.010.840.87Aromaticity ? 电子云的分布电子云的分布E.S. 变难变难 N.S. 变易变易Oxidation 难难Reduction 易易BasicitySix-membered Heterocyclic compounds7/17/2022有机2. Physical properties(1) (偶极矩偶极矩) Dipole moment = 7.41 10-38 c.m 3.90 10-38 c.m IC方向一致方
4、向一致Six-membered Heterocyclic compounds(2) Solubility: 吡啶可以与水以任意比例互溶吡啶可以与水以任意比例互溶7/17/2022有机3. Chemical reactionsa. Basicity of PyridineRCH2NH2pKa4.65.199.25-10.0脂肪胺 BasicitySix-membered Heterocyclic compounds7/17/2022有机.+HCl.HClHCl-orSix-membered Heterocyclic compoundsNSO3CH2Cl2NSO3-Pyr.SO3磺化试剂磺化试剂N
5、NCOPhCl -PhCOCl酰化试剂酰化试剂NNCH3CH3II -甲基化试剂甲基化试剂7/17/2022有机b. Electrophilic Substitution:N的的-I钝化环钝化环反应条件剧烈反应条件剧烈取代反应取代反应 发生在发生在3-位（位（ ）+KNO3+H2SO4NO2300 Co+H2SO4350 CoSO3H+Br2300 CoBr(20%)(71%)(33%)N1.430.841.011.010.840.87Six-membered Heterocyclic compounds7/17/2022有机Six-membered Heterocyclic compound
6、sN+ E+2-位NEHNEHNEHNEH不稳定不稳定N+ E+3-位NHENHENHENHE取代取代2-位位取代取代3-位位Six-membered Heterocyclic compounds-Pyridine7/17/2022有机Six-membered Heterocyclic compoundsc. Nucleophilic SubstitutionNClNH3220 oCNNH290%NClNOMe95%NaOMeMeOH/NBrBrNNH2Br65%NH3160 oCNO22, 4, 6-位的影响位的影响X的取代的取代Six-membered Heterocyclic compo
7、unds-Pyridine7/17/2022有机Six-membered Heterocyclic compoundsNNaNH2NH3NNH Na+H2ONNH 2E. Chichibabin ReactionNNC6H5 C6H5Li+ LiHH-的取代的取代Six-membered Heterocyclic compounds-Pyridine7/17/2022有机Six-membered Heterocyclic compoundsN1.430.841.011.010.840.87NHZNZHNHZNZHNZHNZHNHZNHZNHZ2-位位 (6-位位)3-位位4-位位八电子氮负离子
8、八电子氮负离子八电子氮负离子八电子氮负离子Six-membered Heterocyclic compounds-Pyridine7/17/2022有机Six-membered Heterocyclic compounds-Pyridined. Reactions of side chainNCCCHHHHHH Side Chain Acidity of -HNCH3CH2CH3NaNH2NCH2CH2CH3CH3INCH2CH3CH2CH380%NCH3NCH2CH2OH +HCHOZnCl27/17/2022有机Six-membered Heterocyclic compoundsNCH2
9、NCH2NCH2NCH2NCH2NCH2NCH2NCH2NCH2NCH2NCH2NCH22-位甲基位甲基3-位甲基位甲基4-位甲基位甲基八隅体八隅体八隅体八隅体7/17/2022有机Six-membered Heterocyclic compoundse. Oxidations & ReductionsNNCH3HNO3NCOOHNH3NCNH2O侧链的氧化侧链的氧化烟碱烟碱烟酸烟酸烟酰胺烟酰胺NCH3+H2O2(30%)CH3COOH70 oC, 24hNCH3O N-氧化物氧化物 Pyridine-N-oxide3-甲基吡啶甲基吡啶N-氧化物氧化物Six-membered Heterocy
10、clic compounds-PyridinePyridine-N-oxide: Substitution / Position7/17/2022有机Six-membered Heterocyclic compounds-PyridineElectrophilicNOCH3ONaCH3OHNOOCH3NOPhMgBrH2ONOPhNucleophilicNONO2 Fuming HNO3/H2SO490 oC, 4h90%PCl3CH2Cl2NNO280%H2/Ni or Fe/H+NNH2 90%NO7/17/2022有机Six-membered Heterocyclic compounds
11、-PyridineNOHZNOHZ-attack-attack-attackNOHZNOHZNOZHNOHZNOHZ7/17/2022有机Six-membered Heterocyclic compounds-PyridineNH2/Ni25 oC, 3 atmsNHpiperidineReduction7/17/2022有机Six-membered Heterocyclic compounds-Pyrimidine嘧啶嘧啶PyrimidineNN123456sp2碱性碱性水溶性水溶性取代反应取代反应NNBr2100 oCNNBr66%NNOHH3COHHNO3HOAc, 20 o CNNHO
12、OHO2NH3C85%NNNH2NH2ClN2+Cl-NNNH2NH2NNCl7/17/2022有机NNCln-C4H9NH2NNNHC4H9-nNNCH3NaNH2130160 oCNNCH3H2NSix-membered Heterocyclic compounds-Pyrimidine2, 4, 6-positionsNNHHOONNOHOH(Uracil, U)尿嘧啶尿嘧啶NNHNH2ONNOHNH2胞嘧啶胞嘧啶 (Cytosine, C)NNHHOOH3CNNOHOHH3C胸腺嘧啶胸腺嘧啶(Thymine. T)tautomerism7/17/2022有机Six-membered H
13、eterocyclic compounds-PyrimidineNNNHNOOH3CH3CCH2CHCHCHCH2OHOHOHOHVitamin B2NNNHSNH2OOSulfadiazine SD 磺胺嘧啶NNHOOOHC2H5Ph苯巴比妥苯巴比妥 PhenobarbitalHCl H2ONNCH3ClOCH3NHNNH.Moxonidine 莫索尼定莫索尼定7/17/2022有机Six-membered Heterocyclic compounds-PyrimidineHNNHOOFAntimetabolic AgentsFluorouracil 5-FUOHNNOOFTegafurCy
14、tarabine阿糖胞苷NNONH2OHOOHHONNONH2OHO司他夫定司他夫定 StavudineNHNOH3COOHON3Zidovudine 齐多夫定齐多夫定SOHONNONH2拉米夫定拉米夫定 LamivudineAntiviral Agents7/17/2022有机Six-membered Heterocyclic compounds-Quinoline and IsoquinolineQuinoline and Isoquinoline15823467Nquinoline 喹啉12345678Niso-quinoline* 异 喹啉杂化杂化 sp2碱性碱性取代反应：取代反应：
15、E.S. N.S.位置7/17/2022有机Six-membered Heterocyclic compounds-Quinoline and IsoquinolineElectrophilic SubstitutionNHNO3/H2SO40 oC, 30 min.NNO2+NNO25852%48%NHNO3/H2SO40 oC, 30 min.NNO2+NNO25890%10%NBr2/H2SO4AgSO4NBr+58BrNNNSO3H5H2SO422 oC异环取代异环取代5-，8-位位7/17/2022有机Six-membered Heterocyclic compounds-Quino
16、line and IsoquinolineNucleophilic SubstitutionNNNH2NaNH2NC2H5MgXNC2H5150 oCNClNaOCH3CH3OH/heatNOMe发生在吡啶环上，发生在吡啶环上，2(1)、4位上位上7/17/2022有机Six-membered Heterocyclic compounds-Quinoline and IsoquinolineThe Reactions of Side ChainNCH3+COOEtCOOEtNaOEt/HOEtrt, 12hNCH2CCOOEtO90%+NCH3CH3CHOZnCl2100 oCNCHCH3CH
17、2(1), 4位侧链-H7/17/2022有机Six-membered Heterocyclic compounds-Quinoline and IsoquinolineOxidation & ReductionNCrO3 or KMnO4NCOOHCOOH氧化苯环氧化苯环NSn/HClor Na/ROHNHH2/NiNH还原吡啶环还原吡啶环7/17/2022有机Six-membered Heterocyclic compounds-PyranPyran 吡喃吡喃OOOOOOO2H-吡喃吡喃( -吡喃吡喃)4H-吡喃吡喃( -吡喃吡喃) -吡喃酮吡喃酮 -吡喃酮吡喃酮吡喃盐正离子吡喃盐正离子口口恶英嗡盐离子恶英嗡盐离子杂化杂化不饱和环醚不饱和环醚非芳香性非芳香性O芳香性芳香性 稳定性稳定性/高反应活性高反应活性7/17/2022有机Six-membered Heterocyclic compounds-PyranOOOOH+ HClCl-OO+ CH3IOOCH3I- -吡喃酮吡喃酮