杂环化学省公共课一等奖全国赛课获奖课件.pptx
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1、6 Six-membered Heterocycles芳香六元杂环化合物第1页芳香六元杂环化合物类型芳香六元杂环化合物类型第2页芳香六元杂环化合物类型芳香六元杂环化合物类型第3页6.1 PyridinePyridine is the simplest heterocycle of the azine type.It is derived from benzene by replacement of a CH group by an N-atom.The pyridinium ion is isoelectronic with benzene.Methylpyridines are known
2、as picolines,dimethylpyridines as lutidines and 2,4,6-trimethylpyridine as collidine.第4页6.1 PyridineElectrophilic reactions on nitrogen第5页6.1 Pyridine Electrophilic substitution reactions第6页6.1 Pyridine-NitrationElectrophilic substitution reactionsNitration of pyridine with HNO3/H2SO4 occurs under d
3、rastic conditions(ca.300C),but yields only ca.15%of 3-nitropyridine.N2O5,however,gives rise to good yields of 3-nitropyridine(ca.70%)when reacted in CH3NO2 or SO2.第7页6.1 Pyridine-SulfonationElectrophilic substitution reactionsSulfonation of pyridine with oleum at 250C with Hg(II)catalysis yields the
4、 pyridine-3-sulfonic acid in 70%yield第8页6.1 Pyridine-HalogenationElectrophilic substitution reactionsHalogenation of pyridine occurs with elemental chlorine or bromine at high temperature.3-Halo-and 3,5-dihalopyridines are formed at ca.300C as a result of an ionic SEAr process.At higher than 300C,2-
5、halo-and 2,6-dihalopyridines are produced,probably by a radical mechanism.第9页6.1 Pyridine Nucleophilic substitution reactions and metalationAs expected,N-,O-,S-and C-nucleophiles attack the ring C-atoms of pyridine.Addition of the nucleophile and elimination of a pyridine substituent as leaving grou
6、p occur in a two-step process.第10页6.1 Pyridine Nucleophilic substitution reactions and metalation第11页6.1 Pyridine Nucleophilic substitution reactions and metalation第12页6.1 Pyridine Nucleophilic substitution reactions and metalationPyridine shows complex behaviour towards GRIGNARD reagents.第13页6.1 Py
7、ridine Additions of nucleophiles to pyridinium ionsN-Alkylpyridinium ions add hydroxide ions reversibly and exclusively in the 2-position,forming 2-hydroxy-l,2-dihydro-N-alkylpyridines which can be oxidized by mild oxidizing agents to N-alkyl-2-pyridones第14页6.1 Pyridine Side-chain reactivity of pyri
8、dineAlkylpyridines undergo reactions analogous to benzene such as side-chain halogenation and oxidative functionalization.第15页6.1 Pyridine Side-chain reactivity of pyridine第16页6.1 Pyridine Side-chain reactivity of pyridine第17页6.1 Pyridine Side-chain reactivity of pyridine第18页6.1 Pyridine Reactions o
9、f pyridine N-oxidesN-Oxidation of pyridine is carried out with peroxy acids and deoxygenation back to pyridine is brought about by a redox reaction with phosphorus(III)compounds such as PCl3,PPh3 or P(OC2H5)3第19页6.1 Pyridine Reactions of pyridine N-oxidesPyridine-1-oxide undergoes electrophilic and
10、nucleophilic substitution reactions at the 2-and 4-positions,as predicted from its resonance description第20页6.1 Pyridine Reactions of pyridine N-oxides第21页6.1 Pyridine Reactions of pyridine N-oxidesPyridine-N-oxides undergo alkylation and acylation at oxygen.O-Alkylation occurs most readily with ben
11、zyl halides under mild conditions and leads to 1-benzyloxypyridinium ions which in a basic medium,e.g.aqueous alkali,undergo disproportionate into arylaldehydes and pyridine第22页6.1 Pyridine OxidationThe pyridine ring is remarkably stable towards oxidation.Therefore,pyridine serves as a solvent for o
12、xidation reactions in the Collins oxidation with CrO3.Aqueous KMnO4,preferably in a basic medium,oxidizes pyridine to CO2;peroxy acids bring about N-oxidation to pyridine-1-oxide.第23页6.1 Pyridine Reduction第24页6.1 Synthesis of PyridinePyridine synthesis by cyclocondensation第25页6.1 Synthesis of Pyridi
13、nePyridine synthesis by cycloaddition第26页6.1 Synthesis of PyridineHetero-Diels-Alder reaction第27页6.1 Synthesis of PyridinePyridine synthesis via ring transformations第28页6.2 QuinolineQuinoline is derived from naphthalene by replacement of one of its a-CH groups by nitrogen.2-and 3-Methylquinoline(qui
14、naldine and lepidine),2-quinolone(carbostyril),4-quinolone and the quinolinium ion are important derivatives of quinoline.第29页6.2 QuinolineElectrophilic substitution reactionsNitration第30页6.2 QuinolineElectrophilic substitution reactions第31页6.2 QuinolineElectrophilic substitution reactions第32页6.2 Qu
15、inolineNucleophilic substitution reactions第33页6.2 QuinolineNucleophilic substitution reactions第34页6.2 QuinolineSide-chain reactivity第35页6.2 Quinoline Oxidation第36页6.2 Quinoline Reductions第37页6.2 Quinoline Reductions第38页6.2 Synthesis of Quinoline第39页6.2 Synthesis of Quinoline第40页6.2 Synthesis of Quin
16、oline第41页6.2 Synthesis of Quinoline第42页6.2 Synthesis of Quinoline第43页6.2 Synthesis of Quinoline第44页6.2 Synthesis of Quinoline第45页6.2 Synthesis of Quinoline第46页6.2 Synthesis of Quinoline第47页6.2 Synthesis of QuinolineMeth-Cohn synthesis第48页6.2 Synthesis of Quinoline第49页6.2 Synthesis of Quinoline第50页6.
17、2 Synthesis of QuinolineQuinolines are accessible by ring transformation of other heterocyclic systems.第51页6.2 Synthesis of Quinoline第52页6.3 Isoquinoline 异喹啉异喹啉Isoquinoline is derived from naphthalene by replacement of a-CH group by nitrogen.The isoquinolinium ion and 1-isoquinolone isoquinolin-1(2H
18、)-one,isocarbostyril are important derivatives of isoquinolines.第53页Electrophilic substitution reactions第54页Nucleophilic substitution reactions第55页Nucleophilic substitution reactions第56页Nucleophilic substitution reactions第57页Side-chain reactivity第58页Oxidation第59页Reduction第60页Synthesis of isoquinolin
19、e第61页Synthesis of isoquinoline第62页Synthesis of isoquinoline第63页Synthesis of isoquinoline第64页Synthesis of isoquinolinePomeranz-Fritsch synthesis第65页Pictet-Spengler synthesis第66页Synthesis of isoquinoline第67页Synthesis of isoquinoline第68页6.4 Dibenzopyridines吖啶菲啶第69页Reactions of dibenzopyridines第70页React
20、ions of dibenzopyridines第71页Reactions of dibenzopyridines第72页Reactions of dibenzopyridines第73页Reactions of dibenzopyridinesPhenanthridine is oxidized to 6-phenanthridone and quinoline-3,4-dicarboxylic acid by the action of ozone,followed by treatment with alkaline H2O2 solution:第74页Synthesis of acri
21、dines and phenanthridinesUllmann synthesis第75页Synthesis of acridines and phenanthridinesBernthsen synthesis第76页Synthesis of acridines and phenanthridines第77页Synthesis of acridines and phenanthridines第78页Synthesis of acridines and phenanthridines第79页6 Six-membered Heterocycles芳香六元杂环化合物(2)第80页6.5 磷杂苯磷
22、杂苯 Phosphabenzene第81页6.5 磷杂苯磷杂苯 Phosphabenzene第82页6.5 磷杂苯磷杂苯 Phosphabenzene第83页Synthesis of phosphabenzenes第84页6.6 哒嗪哒嗪 Pyridazine第85页6.6 哒嗪哒嗪 PyridazineReactions of pyridazine also show analogies to pyridine.Electrophiles attack the ring N-atoms,for instance in protonation,alkylation or N-oxidation
23、.SEAr reactions at the ring C-atoms are difficult to carry out,even in the presence of activating substituents due to the deactivation by the additional N-atom.However,N-oxidation facilitates the substitution in some cases.第86页6.6 哒嗪哒嗪 Pyridazine3-Substituted pyridazine-1-oxides react with cyanide b
24、y analogy to a REISSERT reaction functionalizing the C-6 position。第87页Synthesis of pyridazines第88页Synthesis of pyridazinesSchmidt-Druey synthesis第89页Synthesis of pyridazines第90页6.7 嘧啶嘧啶 PyrimidineIn its reactions,pyrimidine behaves as a deactivated heteroarene.Its reactivity is comparable to that of
25、 1,3-dinitrobenzene or 3-nitropyridine.Electrophiles attack on nitrogen in protonating and alkylating reactions.Electrophilic substitutions at carbon are not observed in the parent compound.Electron-donating substituents(OH,NH2)increase the SEAr reactivity in the pyridmidine system(two substituents
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