Researches on 1, 2, 4-triazoles

Determination of the acidity constants of 1-aryltetrazolinethiones-5, 4-aryl-1, 2, 4-triazolinethiones-3, 1-aryltetrazolinones-5, 4-aryl-1, 2, 4-triazolinones-3 shows that carbonyl compounds are 10^–1–10^–2 times less acid than compounds with a thione group. Acidities are found to increase considerably, 10³–10⁴ times, on passing from triazole compounds to tetrazole ones. 4-Aryl-1, 2, 4-triazolinones-3 and 1-aryl-tetrazolinones-5 are aminomethylated and cyanoethylated and the reactions found to take place at the amide nitrogen atom.For Part VI see [1].     

Research on 1, 2, 4-triazoles

The stability of sulfides and sulfones of 1-aryltetrazoles and 4-aryl-1, 2, 4-triazoles depends on the acceptor character of the heterocyclic ring. Unlike tetrazole sulfides, triazole sulfides do not undergo hydrolysis, Tetrazole sulfones are more readily hydrolyzed than triazole ones. When an electron-donor substituent is introduced into the p-position of the phenyl ring, the rate of hydrolysis is cut. Neither triazole nor tetrazole sulfides and sulfones, not arylated at a nitrogen atom, are hydrolyzed by alkali, because of a partial decrease in positive charge at the carbon atom of the sulfoazomethine group through formation of an anion with a sextet of -electrons in the ring. Hydrolysis of sulfides and sulfones can conveniently be used to prepared 1-aryltetrazolinones-5 and 4-aryl-1, 2, 4-triazolinones-3.For Part V see [8].     

Ring-degenerate rearrangement of 5-amino-4-iminomethyl-1, 2, 3-triazoles

5-Amino-4-(substituted)iminomethyl-1-phenyl-1, 2, 3-triazoles 5 rearrange thermally to 4-amidino-substituted triazoles 6 instead of undergoing the Dimroth rearrangement to 5-anilinotriazoles 3 .     

On the lead tetraacetate oxidation of 4-amino-1,2,4-triazoles, 1-amino- and 2-amino-1,2,3-triazoles

Lead tetraacetate oxidation of 4-amino-1,2,4-triazoles, 1-amino- and 2-amino-1,2,3-triazoles affords mainly fragmentation to nitriles or acetylenes, even in the presence of intramolecularly attached double bonds.

---

Über die Bleitetraacetatoxidation von 4-Amino-1,2,4-triazolen, 1-Amino- und 2-Amino-1,2,3-triazolen (Kurze Mitteilung)

Zusammenfassung Bei der Oxidation von 4-Amino-1,2,4-triazolen, 1-Amino- und 2-Amino-1,2,3-triazolen mit Bleitetraacetat entstanden hauptsächlich Nitrile bzw. Acetylene durch Fragmentierung — trotz der Gegenwart von intramolekularen Doppelbindungen.

     

Conversion of 2, 5-diphenyl-1, 3,4-oxadiazole to 3, 5-diphenyl-4-aryl-1, 2, 4-triazoles

2, 5-Diphenyl-1, 3, 4-oxadiazoles are shown to react with aromatic amines on heating, to give 2, 5-diphenyl-4-aryl-1, 2, 4-triazoles.     

Conversion of 2, 5-diphenyl-1, 3,4-oxadiazole to 3, 5-diphenyl-4-aryl-1, 2, 4-triazoles

2, 5-Diphenyl-1, 3, 4-oxadiazoles are shown to react with aromatic amines on heating, to give 2, 5-diphenyl-4-aryl-1, 2, 4-triazoles.     

3—芳基—5—巯基—1,2,4—均三唑的双—Mannich反应研究

研究了在氯化氢－乙醇溶液中，３－芳基－５－巯基－１，２，４－均三唑与甲醛和伯胺（芳胺或脂肪胺）的双Ｍａｎｎｉｃｈ反应，合成了１３的的稠杂环化合物３，５－二取代０四氢均三唑并「３，４－ｂ」「１，３，５」噻二嗪，经元素分析、Ｉ手ＭＳ确定了结构，初步测定了该类化合物的生物活性。     

Synthesis of 5-amino-1-(aminothioformyl)-1, 2, 4-triazoles

By the reaction of 5-amino-1, 2, 4-triazoles with benzoyl isothiocyanate we have synthesized 5-amino-1-(benzoylaminothioformyl)-1, 2, 4-triazoles, which form 5-amino-1-(aminothioformyl)-1, 2, 4-triazoles on alkaline hydrolysis.     

Synthesis of some nitro and amino derivatives of 1, 2, 4-triazole-5-thiones and 1, 2, 4-triazoles

Isomeric 3-(nitrophenyl)-1, 2, 4-triazole-5-thiones are synthesized by cyclizing 1-nitrobenzoylthiosemicarbazides. 1-(4-Nitrophenyl)-1, 2, 4-triazole-3-thione is prepared by condensing 4-(4-nitrophenyl) thiosemicarbazide with formic acid. Oxidation converts the triazolethiones to nitrophenyltriazoles, and the latter are reduced to aminophenyltriazoles.     

Synthesis,characterization and self-assembly of novel fluorescent alkoxy-substituted 1, 4-diarylated 1, 2, 3-triazoles organogelators

Novel organogelators based on fluorescent alkoxy-substituted 1,4-diarylated 1, 2, 3-triazoles are reported. The findings monitored in the current study promoted the development of inventive compacted supramolecular architectures generated by self-assembly of the prepared triazole-based organogelators. The synthesis, characterization and gelation properties of the current novel alkoxy-substituted 1,4-diarylated 1, 2, 3-triazole arms were described. The synthesis procedures were accomplished by using Cu-catalyzed azide-alkyne cycloaddition (CuAAC) of alkoxy-substituted aryl azide with aryl bearing terminal alkyne subtituents and alkoxy chains of different lengths. The alkoxy-substituted of 1, 4-diarylated 1, 2, 3-triazole derivatives bearing different alkoxy chains were characterized by FTIR, ¹H/¹³C NMR, and elemental analysis. The 1, 4-diarylated 1, 2, 3-triazoles with longer alkoxy terminal groups demonstrated improved gelation properties compared to those with shorter alkoxy terminals. The morphologies of the self-assembled alkoxy-substituted 1, 4-diarylated 1, 2, 3-triazoles were investigated using scanning electron microscopy (SEM), which demonstrated arrangements of highly ordered nanofibers, forced by π-stacks and van der Waals interactions. The antibacterial activity and cytotoxicity of the newly synthesized triazoles was investigated to verify the potential use of the present triazole gelators for a variety of applications, such as drug delivery.     

1-取代芳基-4-乙氧羰基-5-酰胺基-1, 2, 3-三唑的合成及 抗菌性能的研究

报道了1-取代芳基-4-乙氧羰基-5-氨基-1,2,3-三唑同各种酰氯的反应,制得23种新型衍生物1-芳基-4-乙氧羰基-5-酰胺基-1,2,3-三唑。讨论了产物的收率与所用酰化试剂的关系,新化合物的结构经IR,^1HNMR,MS及元素分析确证,并评价了这些化合物的抗菌性能。     

Synthesis of 1-aryl-5-methyl-4-substituted-l,2,3-triazoles

As 1-aryl-5-methyl-4-substituted-1,2,3-triazoles often exhibit broad spectrum biological actions, we have synthesized many heterocyclic and condensed heterocyclic compounds which contained 1-aryl-5-methyl-1,2,3-triazol-4-yl functional groups and screened their antibacterical activities^[1,2]. Our further work testified that it was necessary to go on studying such kind of compounds. In order to improve the soluble of these compounds, we chose aniline and p-toluidime as starting materials to synthesize 1-aryl-5-methyl-4-substituted-1,2,3-triazoles 1a-b, 2a-b, 3a-b, 4a-b, 5a, These new compounds all have active reaction groups such as SH, NH₂ as well as OH. So they might react with ω-substituted-ω-bromo-acetophenone and 6a-b, 7a-b, 8a-b, 9a were obtained. They are all soluble in hot alcohol. Under similar conditions it is difficult to let 4a-b react completely with ω-substituted-ω-bromo-acetophenone. We only observed a little new compounds by TLC. By Mannich reaction, 1a-b also could react with formaldelyde and p-toluidime and l0a-b were isolated. The evaluation of the biological activity is in progress.     

Researches on 2, 1, 3-thia- and selenadiazole

Depending on the reaction conditions, benzo-2, 1, 3-selenadiazole (I), dichlorodimethyl ether and aluminum chloride react to give a complex IV, or else 4-chloromethyl-(V) or 4, 7-di(chloromethyl) benzo-2, 1, 3-selenadiazole (VI). 5-(II) and 4-methylbenzo-2,l,3-selenadiazole(III) are chloromethylated by dichlorodimethyl ether in the presence of chlorosulfonic acid. Compound II is converted mainly into 5-methyl-4-chloromethylbenzo-2, 1, 3-selenadiazole(VII) or a mixture of three possible isomers VII, VIII, and IX, depending on the amount of base or pseudo-base in the reaction mixture. Ill gives mainly 4-methyl-7-chlorornethylbenzo-2, 1, 3-selenadiazole(X), independent of the presence of base. The structures of the chloromethylation products are shown by reductive splitting to o-diamides, and chromatography of the latter in the presence of reference spots. The high reactivity of the chlorine in the chloromethyl group made it possible to obtain new derivatives by replacing it with a hydroxyl, cyano, or thiocyano group.For Part XL see [1].     

Researches on 2, 1, 3-thia- and selenadiazole

4-Hydroxy-, 4-hydroxy-5-methyl-, 4-hydroxy-7-methylbenzo-2,1,3-thiadiazoles are polymorphous.4-Hydroxybenzo-2,1,3-thiadiazole (I), 4-hydroxy-5-methyl- and 4-hydroxy-7-methylbenzo-2, 1, 3-thiadiazoles (II and III) melt at 114–115°, 110–112°, 100–102° C, respectively, after recrystallization from water [2–4], but after recrystallization from petrol ether [5] they melt at 128–129°, 124–125°, and 119–120° C [5]. In this connection we recrystallized these phenols repeatedly from petrol ether after recrystallizing them from water, and their melting points rose as expected [5]. On the other hand, the compounds with melting points 128–129°, 124–125°, 119–120° C (ex petrol ether), after repeated crystallization from water melted at 114–115°, 110–112°, 100–102° C, respectively.For Part XXXVIII see [1].     

One-pot synthesis of 1-monosubstituted-1, 2, 3-triazoles from 2-methyl-3-butyn-2-ol

An efficient method for the synthesis of 1-monosubstituted-1, 2, 3-triazoles from 2-methyl-3-butyn-2-ol under copper catalyst conditions has been developed through a one-step one-pot sequence. This method provides a concise and efficient pathway to synthesize 1-monosubstituted-1, 2, 3-triazole derivatives in good to excellent yields.     

1-Nucleosides of 5-substituted 4-chloro-1,2,3-triazoles

1-Nucleosides of 5-substituted 4-chloro-1,2,3-triazoles were produced by glycosylation of the corresponding triazoles by the method of fusion with tetra-0-acyl-D-ribofuranose in the presence of bis-p-nitrophenyl phosphate. The structure of the compounds obtained and their conformational peculiarities were studied by the methods of mass spectrometry and NMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1556–1564, November, 1984.     

Synthesis of 1-alkyl-4(5)-hydroxymethyl-1,2,3-triazoles

An in situ method for the synthesis of 1-alkyl-4(5)-hydroxymethyl-1,2,3-triazoles by the action of acetylenic alcohols with alkyl azides as the latter are formed from sodium azide and alkyl halides in dimethylformamide is proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1688–1689, December, 1980.     

Synthesis of 4-Arylselanyl-1H-1,2,3-triazoles from Selenium-Containing Carbinols

In this work, we present a simple way to achieve 4-arylselanyl-1H-1,2,3-triazoles from selenium-containing carbinols in a one-pot strategy. The selenium-containing carbinols were used as starting materials to produce a range of selanyl-triazoles in moderate to good yields, including a quinoline and Zidovudine derivatives. One-pot protocols are crucial to the current concerns about waste production and solvent consumption, avoiding the isolation and purification steps of the reactive terminal selanylalkynes. We could also isolate an interesting and unprecedented by-product with one alkynylselenium moiety connected to the triazole.     

Synthesis of 3,5-Diaryl-4-benzylideneamino-1,2,4-triazoles and 4-Amino-3,5-diaryl-1,2,4-triazoles

A one-pot reaction leading to 3,5-diaryl-4-benzylideneamino-1,2,4-triazoles is described, the key step of which is the reaction of arenecarbohydrazonoyl chloride with benzylidenehydrazide. Compounds obtained in this way were hydrolyzed to 4-amino-3,5-diaryl-1,2,4-triazoles.     

Efficient,mild synthesis of N-unsubstituted 1,2,3-triazoles from methanolysis of 1-sulfonyl-1,2,3-triazoles

A small library of diverse N-unsubstituted 1,2,3-triazoles was prepared from the corresponding 1-sulfonyl-1,2,3-triazoles, which were treated only with MeOH at reflux temperature. This process was carried out in good yields showing high efficiency and good functional group tolerance.