Chemistry of 1,2,3-Thiadiazoles, Volume 62

Vasiliy A. Bakulev, Department of Technology for Organic Synthesis, The Urals State Technical University, Russia.Wim Dehaen, Department of Chemistry, University of Leuven, Belgium.

• 1 Synthesis of 1,2,3-thiadiazoles 11.1 Cyclization of Hydrazones with Thionyl Chloride (Hurd–Mori Synthesis) 11.1.1 Scope and Limitations 21.1.2 Mechanism of the Hurd–Mori Reaction 41.1.3 Application of the Hurd–Mori Reaction in Organic Synthesis 51.2 Cycloaddition of Diazoalkanes onto a C=S bond (Pechmann Synthesis) 171.3 Heterocyclization of α-diazo Thiocarbonyl Compounds (Wolff Synthesis) 221.3.1 Introduction of a Diazo Function into Compounds Containing a C=S Bond 231.3.2 Introduction of a C=S Bond in the α-position to a Diazo Group 271.3.3 Simultaneous Introduction of Diazo and Thiocarbonyl Functions 291.4 Transformations of other Sulfur-containing Heterocyclic Compounds 301.5 Elaboration of Preformed 1,2,3-Thiadiazoles 331.5.1 Carboxylic Acids 331.5.2 Functional Derivatives of Carboxylic Acids 351.5.3 Aldehydes 361.5.4 Amino-1,2,3-Thiadiazoles 371.5.5 Halo Derivatives 391.5.6 5-Hydrazino-, 5-Mercapto-1,2,3-Thiadiazoles and 5-Sulfide Derivatives 401.5.7 2-(1,2,3-Thiadiazol-5-yl)acetic Acid Derivatives 411.5.8 Alkenyl-1,2,3-Thiadiazoles 421.5.9 5-Hydroxyiminomethyl- and 5-Diazomethyl-1,2,3-Thiadiazoles 421.5.10 4-Hydroxymethyl-1,2,3-Thiadiazoles 431.6 Tables 441.7 Selected Procedures 791.7.1 1,2,3-Thiadiazole-4-Carbaldehyde 791.7.2 4-Phenyl-1,2,3-Thiadiazole 801.7.3 4-Phenyl-1,2,3-Thiadiazole-5-Carbaldehyde 811.7.4 4-Phenyl-5-Oxyiminomethyl-1,2,3-Thiadiazole 821.7.5 5-Phenyl-1,2,3-Thiadiazole-4-Carbaldehyde 821.7.6 5-Chloro-1,2,3-Thiadiazole-4-Carbaldehyde 831.7.7 Ethyl 5-amino-1,2,3-Thiadiazole-4-Carboxylate 841.7.7.1 Pechmann Method 841.7.7.2 Wolff Method 851.7.8 Ethyl 5-chloro-1,2,3-Thiadiazole-4-Carboxylate 861.7.9 4-Phenyl-2-(2,4,6-Trichlorophenyl)-1,2,3-Thiadiazolium Chloride 861.7.10 5-Amino-4-ethoxycarbonyl-2-phenyl-1,2,3-thiadiazolium bromide 872 Structure of 1,2,3-Thiadiazoles 932.1 Theoretical Methods 932.2 Experimental Structural Methods 972.2.1 X-ray Analysis 972.2.2 Nuclear Magnetic Resonance Spectroscopy 1032.2.2.1 Proton NMR Spectroscopy 1032.2.2.2 Carbon-13 NMR Spectroscopy 1032.2.2.3 Nitrogen-14 NMR Spectroscopy 1062.2.2.4 Nitrogen-15 NMR Spectroscopy 1062.2.3 Mass Spectrometry 1072.2.4 Other Spectroscopic Data 1103 Chemical Properties of 1,2,3-Thiadiazoles 1133.1 Reactions due to the Reactivity of Ring Atoms 1133.1.1 Reactions with Electrophiles 1133.1.1.1 Protonation 1133.1.1.2 Complexation 1143.1.1.3 Alkylation 1153.1.1.4 Acylation 1163.1.1.5 Oxidation 1163.1.1.6 Electrophilic Substitution of Hydrogen 1173.1.2 Reactions with Nucleophiles 1173.1.2.1 Attack at the Sulfur Atom 1173.1.2.2 Attack at the C5 Atom 1183.1.2.3 Attacks at H4 and H5 1203.1.2.4 Cycloaddition Reactions 1213.2 Reactions of Substituents 1223.2.1 5-Alkyl-1,2,3-thiadiazoles 1223.2.2 1,2,3-Thiadiazole-4-carbaldehyde 1233.2.3 5-Amino-1,2,3-thiadiazole-4-carbothioamide 1243.2.4 Mercapto-1,2,3-thiadiazoles 1243.3 Rearrangements 1243.3.1 Dimroth-type Rearrangements 1253.3.2 Cornforth-type Rearrangements 1293.3.2.1 Rearrangements of 4-(iminomethyl)- substituted-1,2,3-Thiadiazoles 1293.3.2.2 Degenerate Rearrangements of 4-Thiocarbamoyl-1,2,3-Thiadiazoles 1333.3.2.3 Rearrangements of 1,2,3-Thiadiazoles Bearing Diazo, Azido and Hydrazono Groups in the 5-'Position 1333.3.2.4 Tandem Rearrangements 1363.4 Ring Cleavage of 1,2,3-Thiadiazoles 1373.4.1 Thermal Decomposition 1373.4.2 Photochemical Decomposition 1413.4.3 Base-catalyzed Decomposition 1433.4.4 Oxidative and Reductive Processes 1493.4.5 Other Processes for Ring Cleavage 1514 Fused 1,2,3-Thiadiazoles 1554.1 1,2,3-Thiadiazoles Fused with Five-Membered Rings 1554.1.1 Cyclopenteno-1,2,3-thiadiazoles 1554.1.2 Pyrrolo[2,3-d][1,2,3]thiadiazoles 1584.1.3 Pyrrolo[3,2-d][1,2,3]thiadiazoles 1584.1.4 Pyrrolo[3,4-d][1,2,3]thiadiazoles 1584.1.5 4,6-Dihydrofurano[3,4-d][1,2,3]thiadiazoles 1594.1.6 Thieno[2,3-d][1,2,3]thiadiazoles 1594.1.7 Thieno[3,2-d][1,2,3]thiadiazoles 1604.1.8 Thieno[3,4-d][1,2,3]thiadiazoles 1624.1.9 Selenopheno[3,4-d][1,2,3]thiadiazole 1624.1.10 Benzoselenopheno[3,2-d][1,2,3]thiadiazole 1634.2 1,2,3-Thiadiazoles Fused with Six-Membered Rings 1634.2.1 Cyclohexeno-1,2,3-thiadiazoles 1634.2.2 Benzo-1,2,3-thiadiazoles 1664.2.3 Piperidino[3,4-d][1,2,3]thiadiazoles 1734.2.4 1,2,3-Thiadiazolo[4,5-b]pyridines 1744.2.5 1,2,3-Thiadiazolo[4,5-c]pyridines 1744.2.6 1,2,3-Thiadiazolo[5,4-c]pyridines 1764.2.7 1,2,3-Thiadiazolo[5,4-d]pyrimidines 1764.2.8 1,2,3-Thiadiazolo[4,5-d]pyrimidines 1784.2.9 Pyrano[3,4-d][1,2,3]thiadiazole 1794.2.10 Thiopyrano[4,3-d][1,2,3]thiadiazoles 1794.2.11 Thiopyrano[2,1-d][1,2,3]thiadiazole 1804.2.12 Selenopyrano[4,3-d][1,2,3]thiadiazoles 1814.3 1,2,3-Thiadiazoles Fused with Seven-Membered Rings 1814.3.1 Benzooxepino- and Benzothiepino[3,4-d][1,2,3]thiadiazoles 1814.3.2 Thiadiazolo[5,4-d]benzazepines 1824.3.3 1,2,3-Thiadiazolo[5,4-b][1,5]benzodiazepine 1824.4 Bicyclic 1,2,3-Thiadiazoles of Azathiapentalenic Structure 1835 Synthesis and Properties of 1,2,3-Selenadiazoles 1935.1 Synthesis of 1,2,3-Selenadiazoles 1935.1.1 Oxidative Cyclization of Hydrazones by Se-containing Reagents 1935.1.2 Cycloaddition Reactions of Diazoalkanes with Compounds Containing C=Se Bonds 1975.1.3 Elaboration of Preformed 1,2,3-Selenadiazoles 1975.1.4 Miscellaneous Syntheses 2015.2 Structural Data of 1,2,3-Selenadiazoles 2015.2.1 Mass Spectrometry 2015.2.2 Proton NMR Spectroscopy 2015.2.3 Carbon-13 NMR Spectroscopy 2025.2.4 Nitrogen-15 NMR Spectroscopy 2025.2.5 Selenium-77 NMR Spectroscopy 2035.2.6 X-ray Crystallography 2035.2.7 Miscellaneous 2045.3 Reactivity of 1,2,3-Selenadiazoles 2045.3.1 Ring Cleavage 2045.3.1.1 Thermal Reactions 2045.3.1.2 Photochemical Reactions 2105.3.1.3 Base-catalyzed Reactions 2115.3.1.4 Radical-catalyzed Reactions 2145.3.1.5 Reaction with Metal Complexes 2155.3.1.6 Miscellaneous Ring Cleavage Reactions 2175.3.2 Formation of Salts and Ylides 2185.4 Fused 1,2,3-Selenadiazoles 2205.4.1 Bicyclic 1,2,3-Selenadiazoles 2205.4.2 Tricyclic 1,2,3-Selenadiazoles 2215.4.3 Tetra- and Pentacyclic 1,2,3-Selenadiazoles 2225.5 Applications of 1,2,3-Selenadiazoles 2226 1,2,3-Thiadiazoles in Medicine and Agriculture 2296.1 Medicine 2296.2 Agriculture 2316.2.1 Thidiazuron 2326.2.2 Bion 233References 236Index 239