Computational studies on the structures and energies of the tautomers of 1-amino-3-nitrotriazol-5-one-2-oxide

Molecular orbital calculations at the DFT-B3LYP/aug-cc-pVDZ level were performed for the possible tautomers of 1-amino-3-nitro-1,2,4-triazol-5-one-2-oxide. We have examined the substitution effects of amino and nitro groups by comparing calculated geometries, relative energies, and electrostatic potentials of model molecules. The optimized structures, vibrational frequencies, and thermodynamic values for triazol-5-one-N-oxides were obtained in their ground state. The results show 1H, 4H tautomers to be most stable. Detonation velocity and detonation pressure were evaluated by the Kamlet and Jacob equations based on the predicted density and the calculated heat of explosion. Explosive properties appear to be promising compared with those of 1,3,5-trinitro-1,3,5-triazine (D = 8.75 km/s, P = 34.7 Gpa) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (D = 8.96 km/s, P = 35.96 Gpa), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (D = 9.20 km/s, P = 42.0 Gpa) and octanitrocubane (D = 9.90 km/s, P = 48.45 GPa). The designed triazol-5-one-N-oxides satisfy the criteria of high energy density materials.     

Synthesis of 1-(2,4,6-trichlorophenyl)-2-(1,2,4-triazol-4-yl)-diazene-1-oxide

By reaction of 4-amino-1,2,4-triazole with 1-nitroso-2,4,6-trichlorobenzene in the presence of excess dibromoisocyanurate the title compound was obtained.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 362–364, February, 1992.     

Synthesis and structure elucidation of 3-methoxy-1-methyl-1H-1,2,4,-triazol-5-amine and 5-methoxy-1-methyl-1H-1,2,4,-triazol-3-amine

Previously it was shown that condensation of dimethyl N-cyanodithioimidocarbonate ( 1a ) with methylhydrazine gave predominantly 1-methyl-5-methylthio-1H-,2,4-triazol-3-amine ( 2 ), which was initially identified erroneously as the regioisomer l-methyl-3-methylthio-1H-1,2,4-triazol-5-amine ( 3 ). We have found that reaction of dimethyl N-cyanoimidocarbonate ( 1b ) with methyl hydrazine affords a high yield of 3-methoxy-1-methyl-1H-1,2,4-triazol-5-amine ( 4 ) rather than the regioisomer 5-methoxy-1-methyl-1H-1,2,4-triazol-3-amine ( 5 ). The structure assignment of 4 was confirmed by X-ray crystallographic analysis of the benzenesulfonyl isocyanate adduct 7 . Triazole 5 was obtained after reacting dimethyl N-cyanothioimidocarbonate ( 1c ) with methylhydrazine.     

Optimization of the synthesis of 5-amino-1,2,4-triazol-3-ylacetic acid and bis(5-amino-1,2,4-triazol-3-yl)methane

The influence of the molar ratio and concentration of the reactants and of the temperature and time of the synthesis on the yield of malonic acid guanylhydrazides in the reaction of aminoguanidine with malonic acid in acidic aqueous solutions was examined, and improved procedures for preparing 5-amino-1,2,4-triazol-3-ylacetic acid and bis(5-amino-1,2,4-triazol-3-yl)methane were suggested.     

Adamantylazoles: VIII. Acid-catalyzed adamantylation of 1,2,4-triazol-5-ones

3-R-1,2,4-Triazol-5-ones are adamantylated in sulfuric acid. The reaction involves the N¹ atom of the ring. 4-Adamantyl-1-methyl-, 1-adamantyl-4-methyl-, and 1,4-diadamantyl-1,2,4-triazol-5-ones were also prepared. Therewith, it was found that N¹ exhibits a higher reactivity than N⁴.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1377–1382.Original Russian Text Copyright © 2004 by Amandurdyeva, Saraev, Kuzmina, Golod.For communication VII, see [1].This revised version was published online in April 2005 with a corrected cover date.     

New derivatives of N-vinyltriazoles: 1,3-diaryl-3-(1H-1,2,4-triazol-1-yl)-2-propen-1-ones

We have synthesized previously unknown N-vinyltriazoles:1,3-diaryl-3-(1H-1,2,4-triazol-1-yl)-2 propen-1-ones. We discuss a hypothesis for a probable reaction mechanism. Institute of Chemistry, Academy of Sciences of the Moldavian Republic, Kishinev 277028. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 910–914, July, 1995. Original article submitted March 24, 1995.     

Lanthanide perchlorate complexes of 4-nitroquinoline-1-oxide and 5-nitroisoquinoline-2-oxide

Novel complexes of lanthanide perchlorates with 4-nitroquinoline-1-oxide (NQNO) and 5-nitroisoquinoline-2-oxide (NIQNO) have been prepared and characterized. The complexes have the general formulaeLn(NQNO)₈(ClO₄)₃ (whereLn=La-Nd), Ln(NQNO)₇(ClO₄)₃ (whereLn=Gd-Yb),Ln(NIQNO)₉(ClO₄)₃ (whereLn=La-Nd), andLn(NIQNO)₇(ClO₄)₃ (whereLn=Gd-Yb). The IR, proton NMR spectral data indicate the coordination of the N—O group of the ligands to he lanthanide ions.de|Es wurden neue Komplexe von Lanthanidperchloraten mit 4-Nitrochinolin-1-oxid (NQNO) und 5-Nitroisochinolin-2-oxid (NIQNO) dargestellt und charakterisiert. Die Komplexe haben die allgemeinen FormelnLn(NQNO)₈(ClO₄)₃ (mitLn=La-Nd),Ln(NQNO)₇(ClO₄)₃ (mitLn=Gd-Yb),Ln(NIQNO)₉(ClO₄)₃ (mitLn=La-Nd) undLn(NIQNO)₇(ClO₄)₃ (mitLn=Gd-Yb). Die IR- und NMR-Daten zeigen die Koordination der N—O-Gruppe der Liganden zum Lanthanidenion an.

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Lanthanid-Perchlorat-Komplexe von 4-Nitrochinolin-1-oxid und 5-Nitroisochinolin-2-oxid

     

二茂铁亚甲基三氮唑配合物的合成、晶体结构及性能研究

以二茂铁亚甲基三氮唑为配体,通过与金属离子的自组装得到了两个新的二茂铁基功能配合物：[Cd(tmf)2(SCN)2]n (1) 和 [Ni(tmf)4(SCN)2] (2) (tmf =二茂铁亚甲基三氮唑)。其中,配合物1呈一维链状结构;配合物2是一个通过氢键作用而形成的二维超分子。三阶非线性光学性质测试结果表明,配合物1（n2 = 2.11 × 10-11 esu）和2（n2 = 1.92 × 10-11 esu）的三阶非线性光学折射效应与配体tmf（n2 = 2.49 ×10-11 esu）接近,说明配合物1和2的三阶非线性光学性质主要受配体控制。循环伏安法(CV)测试结果显示,这两个配合物在电极上的氧化还原过程是受扩散控制的。计时电流法(CA)和计时电量法(CC)测得配合物1的扩散系数比配合物2的扩散系数小。     

Reaction of 1-tert-butyl-3,4-diphenyl-1,2,4-triazol-5-ylidenes with a malonic ester

Four stable carbenes, 1-tert-butyl-3,4-diaryl-1,2,4-triazol-5-ylidenes 1a-d, including new fluorine-containing compounds 1c,d, react with a malonic ester to afford heterocyclic zwitterionic compounds 5a-d. The reactions with more acidic compounds (ethyl acetoacetate, malononitrile and 1,3-dimethylbarbituric acid) proceed with substrate deprotonation to form the respective azolium salts 6a-c. The X-ray crystal structure of 5a was also determined.     

A new method for the synthesis of novel 1-aryl-3-quinoxalinyl-1,2,4-triazol-5-ones

The reactions of 3-methoxycarbonylmethylene-2-oxo-1,2,3,4-tetrahydroquinoxaline 1 with aryl diazonium salts gave 3-(α-aryldiazenylmethoxycarbonylmethylene)-2-oxo-1,2,3,4-tetrahydroquinoxalines 2a-c , whose reactions with hydrazine hydrate afforded 3-(α-aryldiazenylhydrazinocarbonylmethylene)-2-oxo-1,2,3,4-tetrahydroquinoxalines 3a-c . The reactions of 3a-c with nitrous acid resulted in the Curtius rearrangement to provide the 1-aryl-3-quinoxalinyl-1,2,4-triazol-5-ones 4a-c.     

Structure and Synthesis of a New Library of N,N-Bis-[1,2,4]triazol-1-ylmethyl-amino Compounds

New N,N-bis(triazol-1-ylmethyl)amines have been prepared in one step by condensation of 1-(hydroxymethyl)triazole with a series of primary substituted aromatic amines. These reactions were carried out in refluxed CH₃CN for 4 h. The products were recuperated with excellent and good yields (75–90.5%). The x-ray crystallography structure of one of them has been studied.     

Lithiation of 1-alkyl-1H-1,2,4-triazol-5-yl phosphonic acid esters: Novel anion-mediated carbon-to-carbon phosphonate migrations

The lithiation chemistry of 1-alkyl-1H-1,2,4-triazol-5-yl phosphonic acid esters 3 has been investigated. Lithiation occurs exclusively on the 1-alkyl group, α to nitrogen, to give carbanionic intermediates 10 . No evidence was found for any lithiation at the 3-position of the triazole ring. On warming, intermediates 10 undergo an unusual anion-mediated phosphonate migration, giving rise to 1H-1,2,4-triazol-1-yl-methylphos-phonates 14 .     

Preparation and Structure Characterization of 4-Amino-1,2,4-triazol-5-one Hydrate

4-Amino-1,2,4-triazol-5-one hydrate (ATO·H₂O) was prepared and its structure was analyzed by four-circle diffraction measurement. The obtained results show that the crystal belongs to the triclinic crystal system, space group P 1 with crystal parameters a = 6.432(1), b = 6.551(1), c = 6.740(1) ; = 68.04(1), = 82.18(1), = 81.90(1)°, V = 259.7(7) ³; Z = 2; Dc = 1.510 g/cm³; = 0.131 mm^-1; F(000) = 124. ATO·H₂O was characterized by FT-IR analysis, X-ray diffraction analysis, and single crystal diffraction analysis.     

Synthesis and Biological Activities Evaluation of New 4-(2,4-Difluorophenyl)-N-aryl-5-(1H-1,2,4-triazol-1-yl)thiazol-2-amine

Fifteen new thiazol-2-amine derivatives containing the 2,4-difluorophenyl unit and 1H-1,2,4-triazole moiety were synthesized. Their structures of all these new compounds have been confirmed by ¹H NMR spectra and elemental analysis. The antifungal and plant-growth-regulatory activities of the title compounds are discussed.