专业英语 6 Methods of Making Carbon-Nitrogen Bonds.ppt

1、6 Methods of Making Carbon-Nitrogen Bonds6.1 Electrophilic methods of making C-Nbonds6.2 Nucleophilic methods of making C-Nbonds6.3 Rearrangement methods6.4 The synthesis of amino acids6.5 The synthesis of nitrogen heterocycles6.1 Electrophilic Methods of Making C-N Bonds Nitrogen-containing electro

2、phile react with electron-rich species such as alkenes and arenes1.Concentrated nitric acid+concentrated sulfuric acid2.Concentrated nitric acid+acetic acid and/or acetic anhydrideThe generation of nitronium ion(NO2+)3.Nitric acid+Lewis acid(boron trifluoride,lanthanide();trifluoromethanesulfonates

3、or a zeolite沸石.)5.Some metal nitrates:copper()nitrate,vanadium()oxytrinitrate4.Nitroniumtetrafluoroborate(NO2+BF4-)useful reagent for acid-sensitive aromatic compounds with nitrile group.1.The aromatic nitration products (orth/para or meta)is determined by the substituents on the aromatic ring.2.Zeo

4、lite catalyst facilitate the para isomer because the limited space of the pores.3.Kyodai(N2O5)nitration can generate ortho isomers.para or ortho productNitrosation Nitrosation of phenols with nitrous acidNitrosation of alkenes with Nitrosyl chloride1.Alkyl halides react with ammonia 6.3 Nucleophilic

5、 Methods of Forming C-N Bonds2.Gabriel method(phthalimide)for making primary aminen3 Treat trifluoroacetamide with carbonium ion4 Treat sulfonamide with carbonium ionn5 Reduction of azide n6 Treating nitrosation products of a dialkylaniline with alkali n7 Reduction of amides,imines and oximes肟n 8 Th

6、e reductive amination of ketones by the LeuckartLeuckart method methodn9 Reduction of nitriles n10 Reduction of nitro group nPropose a synthesis of tropinone 托品酮(1).n-amino ketone suggest Mannich reaction,which involves the condensation of an enolate with an iminium salt.6.4 Rearrangement Methods to

7、 make carbon-nitrogen bondBeckmann rearrangement Oximes are converted to amides in the presence of a strong protic acid.nHofmann degradation of amides.Prepare the following compoundnCurtius rearrangement of acid azides 1 The Strecker method6.5 The Synthesis of Amino AcidsSynthesize the following com

8、poundnErlenmeyer azlactone method nUsing diethyl bromomalonate and phthalimide NOOK+CHCO2EtCO2EtBrNOOCHCO2EtCO2EtNaHRI1)2)NOOCCO2EtCO2EtR1)OH2)HCCO2EtNH2RHnUsing oximinomalonat methodnThe compounds have two sites of reactivity.n Some typical bidentate(二 齿)nucleophilesn 6.6 Synthesis of Nitrogen Hete

9、rocyclesSynthesize the following compoundHantzsch synthesis of dihydropyridinesUsing Hantzsch way to synthesizeThe Hantzsch synthesis of pyrroles.Knorr synthesis of pyrrolesSynthesis of quinolines喹啉IsoquinolinesGive a suggestion to problem 1eQuinoxxaline 喹喔啉Benzimidazole 苯并咪唑Anthranilic acid(邻氨基苯甲酸）in hetero ring synthesis Benzoxazine 苯并噁嗪nFischer indole（吲哚）synthesis