A Facile and Rapid Method for Preparation of Thiazine and Thiadiazine Derivatives by Sonication Technique

Ultrasound accelerated synthesis of 2,3-(substituted)benzo-1,4-thiazino[5,6-b]-4H-9H-7- methyl-10-oxoquinolines (4), 7-substituted-2,2-dimethyl-2,3-dihydro-1H,10H-phenothiazin- 4-one (5), 4-substituted-3,9, 10-trihydro-11-oxo-quinolino[2,3-b]-1,3,4-thiadiazino[2,3-d]- 1,2,4-triazole (6), and 7,7-dimethyl-7,8-dihydro-3H,5H,6H-1,2,4-triazolo[3,4-b][1,3,4] benzothiadiazin-9-one (7) from carbostyril and dimedone using sulfur powder and iodine as a catalyst in THF is reported. The structures of the compounds have been elucidated on the basis of spectral and elemental analysis.     

Helicenoid-based bis-1,2,3-triazole tweezer: Synthesis and selective iodide sensing

Abstract

Novel helicenoid based 1,2,3-triazole tweezer 4 was synthesized using a multistep synthetic protocol with high yields from 2,7-Dihydroxynaphtlene 3 as a precursor. This helicenoid-based bis-1,2,3-triazole tweezer 4 selectively causes non-covalent interaction with iodide anion. The UV-vis absorption exhibited enhancement while fluorescence spectra exhibited significant quenching. ¹H NMR titration showed shift of 1,2,3-triazole C-H signal with an increase in iodide concentration. Association constant of 3.818?×?10⁴ M^?1 was recorded for the host interaction with iodide ions. This value of association constant for iodide sensing using 1,2,3-triazole is the best reported so far for hosts with 1,2,3-triazole moiety and suggests that the helicenoid geometry is responsible for this remarkable behavior.     

1-(4-取代苯基)-4-苯基-5-(2-羟基苄基)氨基-1,2,3-三唑类衍生物的合成及抑菌活性

将邻羟苯基引入1,2,3-三唑结构中, 设计合成了10个1-(4-取代苯基)-4-苯基-5-取代-1,2,3-三唑类衍生物. 首先, 以对位取代的芳胺为原料, 经重氮化、叠氮化、闭环和缩合反应制得1-(4-取代苯基)-4-苯基-5-水杨醛亚胺-1,2,3-三唑类衍生物(3a~3e), 再用硼氢化钠还原制得1-(4-取代苯基)-4-苯基-5-(2-羟基苄基)氨基-1,2,3-三唑类衍生物(4a~4e). 目标化合物的结构经核磁、IR及元素分析确认. 抑菌活性测试表明, 当质量浓度为0.1 mg/L时, 除化合物3e和4e外, 所有化合物对白色念球菌的抑菌率均达95%以上, 对大肠杆菌的抑菌率达85%以上, 具有强抑菌活性, 表明该类化合物在抗菌药物开发方面有重要应用价值.     

Selenium heterocycles. XXXV . Synthesis and pyrrolysis of aryloxy-, arylthio-, and arylseleno-1,2,3-selenadiazoles

A series of 4-substituted-5-arylthio-1,2,3-selenadiazoles, 4-substituted-5-arylseleno-1,2,3-selenadiazoles and 4-aryloxymethyl-1,2,3-selenadiazoles were synthesized. Pyrrolysis of these compounds afforded the corresponding acetylenes XI, XIII (X = S, Se) and XII, respectively. Oxidation of 4-substituted-5-arylthio-1,2,3-selenadiazoles (XIV) with m-chloroperbenzoic acid gave 4-substituted-5-arylsulfinyl-1,2,3-selenadiazoles (XV) and 4-substituted-5-arylsulfonyl-1,2,3-selenadiazoles (XVI).     

A convenient synthesis and crystal structure of disubstituted 1,2,3-triazoles having ether functionality

Abstract

A series of 27 ether-linked 1,4-disubstituted 1,2,3-triazoles (8a–8z₁) has been synthesized by 1,3 dipolar cycloaddition of 1-substituted-4-(prop-2-yn-1-yloxy)benzene (3a–3c) and aromatic azides (5a–5c, 7a–7f). The synthesized compounds were explicated by FTIR, ¹H NMR, ¹³C NMR and HRMS techniques. The structures of synthesized triazoles 8c (CCDC 1840219) and 8f (CCDC 1840220) were also confirmed by X-ray crystallography.     

Studies on Condensed Heterocyclic Compounds XVII. Synthesis of 6-(1-Aryl-5-methyl-1,2,3-triazol-4-yl)-3-phenyl-s-triazolo[3,4-b]-1,3,4-thiadiazoles

Treatment of 4-amino-5-mercapto-3-phenyl-1,2,4-triazole 2 with 1-aryl-4-carboxy-5-methyl-1,2,3-triazoles 1a-1j in a one-step reaction yielded several 6-(1-aryl-5-methyl-1,2,3-triazol-4-yl)-3-phenyl-s-triazolo[3,4-b]-1,3,4-thiadiazoles 3a-3j . The structures of all the products were established on the basis of elemental analyses and spectral data. The fragmentation of the mass spectra of 3a-3j under electron impact was discussed.     

Synthesis of 1,2,3-triazole nucleosides via the acid-catalyzed fusion procedure

The acid-catalyzed fusion of methyl 1,2,3-triazole-4-carboxylate, 4-cyano-1,2,3-triazole, and 4-nitro-1,2,3-triazole with an acylated ribofuranose provided the corresponding 2-β-D-ribo-furanosyl-4-substituted-1,2,3-triazoles along with the isomeric 1-β-D-ribofuranosyl-4-substituted-1,2,3-triazoles. The structures of these nucleosides were assigned on the basis of their nmr spectra. The synthesis of 2-β-D-ribofuranosyl-1,2,3-triazole-4-carboxamide from both the corresponding methyl ester and cyano nucleosides is described. The cyano nucleosides were utilized to prepare 2-β-D-ribofuranosyl-1,2,3-triazole-4-thiocarboxa?ide and 1-β-D-ribofuranosyl-1,2,3-triazole-4-thiocarboxamide. Reduction of the 4-nitro-1,2,3-triazole nucleosides provided 4-amino-2-β-D-ribofuranosyl-1,2,3-triazole and the isomeric 4-amino-1-β-D-ribofuranosyl-1,2,3-triazole. The acid-catalyzed fusion procedure with 1,2,3-triazole afforded 1-β-D-ribofuranosyl-1,2,3-triazole and 2-β-D-ribofuranosyl-1,2,3-triazole.     

3-巯基-5-芳香基-4-芳基亚甲胺基-4H-1,2,4-三唑的合成及波谱研究

5-取代-4-氨基-3-巯基-1,2,4-三唑与芳香醛在弱酸性乙醇溶液中反应, 合成了一系列3-巯基-5-芳香基-4-芳基亚甲胺基-4H-1,2,4-三唑(3a～3d)及水溶性的3-巯基-5-(D-葡萄糖-1-基)-4-(4-氯代苯基)亚甲胺基-4H-1,2,4-三唑(3e)新化合物. 以元素分析, IR, NMR, MS实验技术对其结构进行了表征, 并研究其NMR波谱特征.     

Pyrazoles as building blocks in heterocyclic synthesis: Synthesis of pyrazolo [3,4-d]pyrimidine, pyrazolo[3,4-e][1,4]diazepine, pyrazolo [3,4-d][1,2,3]triazine and pyrolo [4,3-e][1,2,4]triazolo[1,5-c]pyrimidine derivatives

Several new pyrazolo[3,4-d]pyrimidine, pyrazolo[3,4-e][1,4]diazepine, pyrazolo[3,4-d][1,2,3]triazine and pyrolo[4,3-e][1,2,4]triazolo[1,5-c]pyrimidine derivatives were prepared by the reaction of the corresponding 5-amino-pyrazole-4-carbonitrile derivative with different organic reagents under different reaction conditions. Using IR, ¹H NMR, and mass spectra we have characterized all new compounds.     

Convenient and efficient Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions catalyzed by 1,3,4-trisubstituted-1,2,3-triazolium iodide and palladium salt systems

A series of 1,3,4-trisubstituted-1,2,3-triazolium iodide salts (4a–c) were synthesized via a three-step reaction sequence. Corresponding anilines (1a–c) were converted to azides (2a–c) which were then treated with phenylacetylene with “Click” chemistry to access 1,4-disubstituted-1,2,3-triazoles (3a–c). Subsequent methylation of 1,4-disubstituted-1,2,3-triazoles (3a–c) yielded 1,3,4-trisubstituted-1,2,3-triazoliumiodide salts (4a–c) in appreciable yields. All the synthesized compounds were characterized by ¹H and ¹³C NMR, ATR–IR spectroscopic techniques and elemental analyses. Additionally, the structure of 1-(4-chlorophenyl)-4-phenyl-1,2,3-triazole (3b) was confirmed by single crystal X-ray diffraction analysis. The catalytic activity of 4a–c in a catalytic system consisting of 1,3,4-trisubstituted-1,2,3-triazoliumiodide salt/palladium(II) acetate/base were investigated toward Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions. The Suzuki–Miyaura cross-coupling reactions were carried out under mild reaction conditions with good to excellent yields, whereas Heck–Mizoroki cross-coupling reactions were performed at elevated temperature with moderate yields. Further, in situ method skips the synthetic procedure of preparing the palladium(II) complexes and hence is more economical and less tedious.     

Theoretical studies on a series of 1,2,3-triazoles derivatives as potential high energy density compounds

Based on the full-optimized molecular geometric structures at B3LYP/6-31G* and B3P86/6-31G* levels, the densities (ρ), detonation velocities (D), and pressures (P) for a series of 1,2,3-triazole derivatives, as well as their thermal stabilities, were investigated to look for high energy density compounds (HEDCs). The heats of formation (HOFs) are also calculated via designed isodesmic reactions. The calculations on the bond dissociation energies (BDEs) indicate that the BDEs of the initial scission step are between 53 and 70 kcal/mol, and 4-nitro-1,2,3-triazole is the most reactive compound, while 1-(2′,4′-dinitrophenyl)-5-nitro-1,2,3-triazole is the least reactive compound for 1,2,3-triazole derivatives studied. The condensed phase heats of formation are also calculated for the title compounds. These results would provide basic information for the further studies of HEDCs. The detonation data of 1-(3′,4′-dinitrophenyl)-4-nitro-1,2,3-triazole and 1-(2′,4′-dinitrophenyl)-4-nitro-1,2,3-triazole show that they meet the requirement for HEDCs.     

1,2,3-Triazolo[4,5-d]-1,2,4-triazolo[4,3-b]pyridazines

Some new 1,2,3-triazolo[4,5-d]-1,2,4-triazolo[4,3-b]pyridazines were prepared starting from the corresponding 1,2,3-triazolo[4,5-d]pyridazines via the formation of the 1,2,4-triazole ring, by condensation of an appropriate monocarbon fragment with the 4-hydrazino substituent and the nitrogen atom in the 5 position of the heterocycle. Condensation of 4-phenylhydrazino substituted derivatives with formic acid gave zwitterionic compounds.     

Synthesis and Antitubercular Evaluation of New Bis-1,2,3-Triazoles Derived from D-Mannitol

Five new bis-1,2,3-triazole derivatives from D-mannitol, namely 2,3,4,5-tetra-O-acetyl-1,6-dideoxy-1,6-bis-(4-substituted-1H-1,2,3-triazol-1-yl)-D-mannitol (4), have been synthesized from 2,3,4,5-tetra-O-acetyl-1,6-diazido-1,6-dideoxy-D-mannitol (3) and alkynes, employing copper (I)-catalyzed azide-alkyne cycloaddition (CuAAC) methodology. Evaluation of their in vitro antitubercular activity against Mycobacterium tuberculosis H₃₇Rv using the Alamar Blue susceptibility test indicated poor activities. However, this study has provided information about the SAR of D-mannitol derivatives in the search for new anti-TB drugs based on this carbohydrate.     

Efficient method for the synthesis of 1,2,3-triazole functionalized isoxazolidine derivatives by 1,3-dipolar cycloaddition of nitrones with terminal olefins

1-Phenyl-1,2,3-triazole-4-carbaldehyde 1 was treated with different N-alkyl hydroxylamine hydrochlorides 2 using NaHCO₃ to obtain 1,2,3-triazole substituted N-alkyl nitrones 3a–c. The nitrones 3a–c were further reacted with different substituted olefins and furnished 2-alkyl-3-(1-phenyl-1H-1,2,3-triazol-4-yl)-5-(substituted)isoxazolidine derivatives 4a–p in high yields via 1,3-dipolar cycloaddition reaction.     

N-糖基-N'-(6-取代色酮-3-基-亚甲氨基)硫脲类化合物的合成

糖基异硫氰酸酯(1a～1c)与无水肼反应, 生成糖基氨基硫脲2a～2c, 再与6-取代-3-甲酰基色酮3a～3d反应, 得到一系列新的N-糖基-N-(6-取代色酮-3-基-亚甲氨基)硫脲类化合物4a～4d, 5a～5d, 6a～6d. 所有新化合物的结构均经IR, ¹H NMR, MS谱和元素分析证实. 所得糖的衍生物构型保持不变, 均为β-型.     

1,4‐Diaryl and Schiff's base [1,2,3]‐triazole derivative liquid crystalline compounds

Regioselective synthesis of [1,2,3]‐triazoles based on the ‘click‐reaction’, involving the Cu(I)‐catalysed 1,3‐dipolar cycloaddition of aryl azide to terminal arylacetylenes, was successfully employed in the preparation of two series of non‐linear mesogens, based on 1,4‐diaryl‐[1,2,3]‐triazole (Ia–e) and with Schiff's base units (IIa–c). Their mesophases were characterized by polarizing optical microscopy and differential scanning calorimetry. All final compounds exhibited preferentially the SmC phase. In addition, compounds of series I showed weak blue fluorescence in solution (λ_{max. em.} = 380–386 nm) with poor quantum yields and a Stokes shift of around 90 nm.     

Synthesis of Isomeric Dimers of Deoxycholic Acid Derivatives Linked by 1,2,3-Triazole

Steroidal propargylic ester 6 and the propiolic ester 7 were prepared in a few steps from the deoxycholic acid. The Huisgen cycloaddition reaction of alkynes 6 and 7 as dipolarophiles with a 1,3-dipolar compound, the azide 5, afforded the dimeric compounds 8 and 9, respectively, in good yield. The dimers of deoxycholic acid derivatives linked by 1,4-disubstituted 1,2,3-triazole were characterized by spectroscopic methods.     

Synthesis of 2(5H)-Furanone Derivatives with Symmetrical and Unsymmetrical Bis-1,2,3-triazole Structure

The interesting bioactivities of 2(5H)-furanone, 1,2,3-triazole, and amino acid derivatives have promoted their combination into one multifunctional molecule. The symmetrical bis-1,2,3-triazoles and mono-1,2,3-triazoles with one free azide group are synthesized respectively by controlling the molar ratio of reactants, N-[5-alkoxy-2(5H)-furanonyl] amino acid propargyl ester and 1,4-diazidobutane. The unsymmetrical bis-1,2,3-triazoles are afforded by the subsequent reaction of mono-1,2,3-triazoles with other terminal alkynes with good to excellent yields in a short time under the same mild “click” reaction conditions. The 32 new compounds obtained in the reactions are characterized by Fourier transform infrared, ¹H NMR, ¹³C NMR, mass spectrometry, and elemental analysis. Because of the diversity of four or five basic units in molecule, this methodology provides easy access to different chiral 2(5H)-furanone compounds with polyheterocyclic structure, especially with unsymmetrical bis-1,2,3-triazole moiety. Importantly, a simple approach is provided for the synthesis of unsymmetrical bis-1,2,3-triazoles using common diazides.     

Oxide der 1,2,3-thiadiazole—III : Darstellung und eigenschaften der cycloalkeno-1,2,3-thiadiazole und ihrer mono- und trioxide

Cycloalkeno-1,2,3-thiadiazoles (3a–d) can be prepared from cycloalkanone-tosylhydrazones (2a–d) by treatment with SOCl₂. Oxidation of 3a–d with peracetic acid yields 1,2,3-thiadiazole-2-oxides (4a–d) and 1,2,3-thiadiazole-1,1,2-trioxides (5a–c). A characterisation of these three classes of compounds is performed by discussion of their UV, IR, NMR and mass spectra.     

Selenium heterocycles XXIII. Synthesis of 4,5-dihydrophenanthro[1,3-d]-1,2,3-selenadiazoles and 10,11 -dihydrophenanthro[1,2-d]-1,2,3-selenadiazoles

The selenium dioxide oxidation of a series of 1,2,3,4-tetrahydrophenanthrone and 1,2,3,4-tetrahydrophenanthren-4-one semicarbazones afforded 4,5-dihydrophenanthro[4,3-d]-1,2,3-selenadiazoles and 10,11-dihydrophenanthro[1,2-d]-1,2,3-selenadiazoles. The latter series which represent a new type of selenaazasteroidal compounds were pyrolyzed and gave the corresponding 1,4-deselenine derivatives.