Five-Membered Heterocycles with One Heteroatom
Five-membered aromatic heterocycles with one heteroatom; pyrrole 2, furan 3 and thiophene 4, are considered to be derived from cyclopentadienyl anion 1 by replacing CH group by NH, O and S, respectively (scheme-1). These five-membered heterocycles are, th
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FIVE-MEMBERED HETEROCYCLES WITH ONE HETEROATOM
CONTENTS GENERAL 1.1 Structure and Stability 1.2 Aromaticity 1.2.1 Aromaticity Order 1.3 Reactivity of Five-Membered Heterocycles 1.3.1 Comparison with Acyclic Analogs 1.3.2 Comparison with Benzene 1.3.3 Reactivity Order in Five-Membered Heterocycles 1.3.4 Reactivity Comparison with Benzene 1.3.5 Effect of Aromaticity on Reactivity 1.3.6 Electrophilic Substitution Reactions 1.3.6.1 Directing Effect of Ring Heteroatom 1.3.6.2 Directing Effects of Substituents in Monosubstituted Heterocycles 1.3.6.3 Directing Effects of Substituents in Disubstituted Heterocycles 1.3.7 Nucleophilic Substitution Reactions 1.3.8 Reduction 1.3.9 Addition Reactions 1.3.10 Cycloaddition Reactions 1.3.11 Reactions with Free Radicals 1.3.12 Reactions with Electron-Deficient Species R. R. Gupta et al., Heterocyclic Chemistry © Springer-Verlag Berlin Heidelberg 1999
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Heterocyclic Chemistry
2 PYRROLFS 2.1 General 2.1.1 Extraction 2.1.2 Ehrlich Test 2.2 Synthesis 2.2.1 Cyclization Reactions 2.2.1.1 (3 + 2) Cyclization Reactions 2.2.1.1.1 Reaction of a-Amino Ketones or a-Amino P-Keto Esters with P-Diketones or P-Keto Esters (Knorr Pyrrole Synthesis) 2.2.1.1.2 Reaction of a-Amino Ketones with Alkynes 2.2.1.1.3 Reaction of P-Amino-a,p-unsaturated Esters with Nitroalkenes 2.2.1.1.4 Reaction of a-Diketones with Amines 2.2.1.2 (2 + 2 + 1) Cyclization Reactions 2.2.1.2.1 Reaction of P-Keto Esters with a-Halo Ketones (Hantzsch Pyrrole Synthesis) 2.2.1.2.2 Reaction of Aldehydes or Ketones with Hydrazine (Piloty-Robinson Pyrrole Synthesis) 2.2.1.2.3 Reaction of Benzoin with Benzyl Aryl Ketones 2.2.1.2.4 Reaction of Aldehydes with Alkyl Isocyanoacetates 2.2.1.3 (4 + 1) Cyclization Reactions 2.2.1.3.1 Reaction of 1,4-Diketones with Ammonia or Ammonia Derivatives (Paal-Knorr Synthesis) 2.2.1.3.2 Reaction of 1,4-Dienes or Diynes with Amines 2.2.2 Ring Expansion Reactions 2.2.3 Extrusion Reactions 2.3 Structure 2.4 Basicity 2.5 Reactions 2.5.1 Protonation 2.5.2 Proton Exchange 2.5.3 Electrophilic Substitution Reactions 2.5.3.1 Orientation 2.5.3.2 Nitration 2.5.3.3 Halogenation 2.5.3.3.1 Chlorination 2.5.3.3.2 Bromination 2.5.3.3.3 Iodination 2.5.3.4 Sulfonation
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Five-Membered Heterocycles with One Heteroatom
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2.5.5 2.5.6
2.5.7
2.5.8 2.5.9 2.5.10
2.5.3.5 Acylation 2.5.3.5.1 Houben-Hoesch Reaction 2.5.3.5.2 Gattermann Formylation 2.5.3.5.3 Vilsmeier-Haack Reaction 2.5.3.5.4 Friedel-Crafts Acylation 2.5.3.6 Alkylation 2.5.3.7 Hydroxymethylation (Mannich Reaction) 2.5.3.8 Reactions with Aldehydes and Ketones 2.5.3.9 Diazo Coupling Reactions on Carbon and Nitrogen Anionic Species 2.5.4.1 Alkylation 2.5.4.2 Acylation Nucleophjlic Substitution Reactions Oxidation 2.5.6.1 Autoxidation 2.5.6.2 Photo-oxidation 2.5.6.3 Oxidation with Chromium Trioxide 2.5.6.4 Oxidation with Hydrogen Peroxide Reduction 2.5.7.1 Catalytic Hydrogenation 2.5.7.2 Re
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