北大有机课件第十四章-杂环化合物.ppt

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1、2023/9/24,有机,Chapter 14 Heterocyclic Compounds（杂环化合物）,Heterocycle/Heterocyclic Compound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):,Heterocycle,Saturated Heterocycles 饱和杂环化合物,Aromatic Heterocycles 芳香杂环化合物,体现各自功能团的性质,2023/9/24,有机,一.Classification&Nomenclature:,按环的大小,Five-membered ring,Six-membered ri

2、ng,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),2023/9/24,有机,pyrrole 吡咯,thiophene 噻吩,furan呋喃,Classification&Nomenclature,Five-membered ring heterocycles,imidazole 咪唑,pyrazole 吡唑,oxazole口恶 唑,thiazole 噻唑,Isoxazole异口恶 唑,2023/9/24,有机,Six-membered ring heterocycles

3、,Classification&Nomenclature,pyridine 吡啶,pyrimidine 嘧啶,2H-pyran2H-吡喃,Pyridazine 哒嗪,Pyrazine 吡嗪,2023/9/24,有机,Fused-heterocycles,Classification&Nomenclature,quinoline 喹啉,iso-quinoline*异 喹啉,Purine*嘌呤,Indole吲哚,蝶啶pteridine,口丫啶acridine,吩嗪phenazine,carbazole 咔唑,Phenothiazine 吩噻嗪,2023/9/24,有机,Classification

4、&Nomenclature,Attention!,“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,2023/9/24,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,2023/9/24,有机,Classification&Nomenclature,互

5、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,2023/9/24,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,2023/9/24,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,2023/9/24,有机,二.Six-membered Heterocyclic compound

6、s,Pyridine 吡啶,1.Structure:,C5H5N,芳香性,较强的碱性,2023/9/24,有机,Kekules structure,Aromaticity?,电子云的分布,E.S.变难,N.S.变易,Oxidation 难,Reduction 易,Basicity,Six-membered Heterocyclic compounds,2023/9/24,有机,2.Physical properties,(1)(偶极矩)Dipole moment,=7.4110-38 c.m 3.90 10-38 c.m,I,C,方向一致,Six-membered Heterocyclic c

7、ompounds,(2)Solubility:,吡啶可以与水以任意比例互溶,2023/9/24,有机,3.Chemical reactions,a.Basicity of Pyridine,Basicity,Six-membered Heterocyclic compounds,2023/9/24,有机,Six-membered Heterocyclic compounds,Pyr.SO3,磺化试剂,酰化试剂,甲基化试剂,2023/9/24,有机,b.Electrophilic Substitution:,N的-I,钝化环,反应条件剧烈,取代反应 发生在3-位（）,Six-membered H

8、eterocyclic compounds,2023/9/24,有机,Six-membered Heterocyclic compounds,不稳定,取代2-位,取代3-位,Six-membered Heterocyclic compounds-Pyridine,2023/9/24,有机,Six-membered Heterocyclic compounds,c.Nucleophilic Substitution,2,4,6-位的影响,X的取代,Six-membered Heterocyclic compounds-Pyridine,2023/9/24,有机,Six-membered Hete

9、rocyclic compounds,E.Chichibabin Reaction,H-的取代,Six-membered Heterocyclic compounds-Pyridine,2023/9/24,有机,Six-membered Heterocyclic compounds,2-位(6-位),3-位,4-位,八电子氮负离子,八电子氮负离子,Six-membered Heterocyclic compounds-Pyridine,2023/9/24,有机,Six-membered Heterocyclic compounds-Pyridine,d.Reactions of side ch

10、ain,Side Chain,Acidity of-H,2023/9/24,有机,Six-membered Heterocyclic compounds,2-位甲基,3-位甲基,4-位甲基,八隅体,八隅体,2023/9/24,有机,Six-membered Heterocyclic compounds,e.Oxidations&Reductions,侧链的氧化,烟碱,烟酸,烟酰胺,N-氧化物 Pyridine-N-oxide,3-甲基吡啶N-氧化物,Six-membered Heterocyclic compounds-Pyridine,Pyridine-N-oxide:,Substituti

11、on/Position,2023/9/24,有机,Six-membered Heterocyclic compounds-Pyridine,Electrophilic,Nucleophilic,2023/9/24,有机,Six-membered Heterocyclic compounds-Pyridine,-attack,-attack,-attack,2023/9/24,有机,Six-membered Heterocyclic compounds-Pyridine,piperidine,Reduction,2023/9/24,有机,Six-membered Heterocyclic com

12、pounds-Pyrimidine,嘧啶Pyrimidine,sp2,碱性,水溶性,取代反应,2023/9/24,有机,Six-membered Heterocyclic compounds-Pyrimidine,2,4,6-positions,(Uracil,U)尿嘧啶,胞嘧啶(Cytosine,C),胸腺嘧啶(Thymine.T),tautomerism,2023/9/24,有机,Six-membered Heterocyclic compounds-Pyrimidine,Vitamin B2,Sulfadiazine SD 磺胺嘧啶,苯巴比妥 Phenobarbital,Moxonidi

13、ne 莫索尼定,2023/9/24,有机,Six-membered Heterocyclic compounds-Pyrimidine,Antimetabolic Agents,Fluorouracil 5-FU,Tegafur,Cytarabine阿糖胞苷,司他夫定 Stavudine,Zidovudine 齐多夫定,拉米夫定 Lamivudine,Antiviral Agents,2023/9/24,有机,Six-membered Heterocyclic compounds-Quinoline and Isoquinoline,Quinoline and Isoquinoline,qui

14、noline 喹啉,iso-quinoline*异 喹啉,杂化 sp2,碱性,取代反应：,E.S.N.S.,位置,2023/9/24,有机,Six-membered Heterocyclic compounds-Quinoline and Isoquinoline,Electrophilic Substitution,异环取代,5-，8-位,2023/9/24,有机,Six-membered Heterocyclic compounds-Quinoline and Isoquinoline,Nucleophilic Substitution,发生在吡啶环上，2(1)、4位上,2023/9/24

15、,有机,Six-membered Heterocyclic compounds-Quinoline and Isoquinoline,The Reactions of Side Chain,2(1),4位侧链,-H,2023/9/24,有机,Six-membered Heterocyclic compounds-Quinoline and Isoquinoline,Oxidation&Reduction,氧化苯环,还原吡啶环,2023/9/24,有机,Six-membered Heterocyclic compounds-Pyran,Pyran 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,2023/9/24,有机,Six-membered Heterocyclic compounds-Pyran,-吡喃酮,