1,2,4-三嗪类化合物的研究XXI.3-甲硫基-5-氧代-2.5-二氧-1,2,4-三嗪的取代苯磺铣化反应及6- 碳的亲电特性

3-甲硫基-5-氧代-2.5-二氧-1,2,4-三嗪(Ic)与取代的苯磺铣氯反应,在无水吡啶中生成N-[6-(3-甲硫基-5-负氧基)-1,2,4-三嗪基]吡啶内嗡盐(4);在NaOH-H~2O-Ch~3COCH~3中生成3-甲硫基-4-(取代苯磺铣基)-5-氧化-6-羟基-1,4,5,6-四氢- 12,4-(6);资Naoh-Ch~3O中则生成1-(对甲苯磺铣基)-3-甲硫基-6-甲氧基-1,4,5,6-四氢-三嗪(7)显示了其6-C具有不寻常的亲电特性.     

Reaction of 4-Amino-3-methylthio-5-oxo-6-R-4,5-dihydro-1,2,4-triazines with Sulfonylacetic Acid Nitriles

The reactions of 4-amino-3-methylthio-5-oxo-6-R-4,5-dihydro-1,2,4-triazines with arylsulfonylacetonitriles and with dinitriles of sulfonyldiacetic acid and methylenebis(sulfonylacetic) acid have been studied. 7-Amino-3-R-8-(R'-sulfonyl)-1,4-dihydropyrazolo[5,1-c][1,2,4]triazin-4-ones have been synthesized and these are the first representatives of geminal sulfones in which the heterocyclic ring is bound directly to the sulfur atoms of the sulfonyl groups.     

1,2,4-triazines and condensed derivatives—XVI : 1-oxo-1,2-dihydro- and 1-oxo-1,2,6,7-tetrahydro[1,2,4]triazino[1,6-c]-quinazolin-5-ium salts. Synthesis and some reactions

Methylation of the type 1 and 2 triazinoquinazoliumolates yields the oxotriazinoquinazolinium salts of types 7 and 8, respectively. 4a similarly furnishes 9. Acid induced degradations and NaBH₄ reductions of compounds 7–9, their conversions into the corresponding pseudobases (10, 11) as well as methods of synthesis of the novel oxotriazinoquinazoliniumolates (16) are described.     

Coordination compounds of hydrazine derivatives with transition metals. Part 27. Coordination chemistry of 4-amino-3-alkyl-5-thio-1,2,4-triazolines and 4-amino-5-oxo-3-thioxo-6-alkyl-2,3,4,5-tetrahydro-1,2,4-triazines

Summary Mono-, bis- and tris-ligand nickel(II) and cobalt(II) complexes with 4 amino-3-alkyl-5-thio-1,2,4-triazolines (HRL) (R=H, Me, or Et) and 4-amino-5-oxo-3-thioxo-6-methyl-2,3,4,5-tetrahydro-1,2,4-triazine (HL') have been prepared and characterized. In these complexes both HRL and HL' are in the neutral thione form. Nickel(II) and cobalt(II) complexes with mononegative thiolate ligands have been also isolated.The reaction of HL' with copper(II) salts in a molar ration of 11 results in the formation of [Cu(HL')X] (X=Cl or Br) and Cu(L')X (X=NO₃ or CH₃COO). However, in the presence of a large excess of HL' the reaction proceeds with partial reduction of Cu^II and both [Cu(HL')X₂] and [Cu(HL')₂]X have been isolated and characterized. The mechanism of copper(II) reduction by HL' is discussed.     

1,2,4-triazines. III. A convenient synthesis of 1,2,4-triazines and their covalent hydration

A general synthesis of 1,2,4-triazines, from 3-methylthiotriazines is described. It has been shown that 1,2,4-triazines undergo covalent hydration across the N₄-C₅ bond.     

1,2,4-Triazines. XII. Syntheses of 5-carboxarnido-1,2,4-triazines via an addition-oxidation reaction

5-Unsubstituted 1,2,4-triazines, when treated with potassium cyanide suspended in moist dioxane afford 5-carhoxamido as well as 5,5′ -bi-1,2,4-triazinyl derivatives. A probable reaction sequence is described.     

Stable aziridinium salts of oxalic and 2,5-dihydro-4,5,5-trimethyl-2-oxo-5-furancarboxylic acids

Conclusions Stable salts of aziridine, 2-methylaziridine, and 2,2-dimethylaziridine with the oxalic and 2,5-dihydro-4,5,5~trimethyl-2-oxo-5-furancarboxylic acids were obtained.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 192–194, January, 1983.     

Reactions of the derivatives of 5,6-diaryl-2,5-dihydro-1,2,4-triazines with dimethyl acetylenedicarboxylate—structural reassignments of the products and further observations

The structures of the dihydro derivatives of 5,6-diaryl-1,2,4-triazines and of the products from the title reactions have been reassigned as 5,6-diaryl-2,5-dihydro-1,2,4-triazines ($\text{5}$a-g) and 2,6-diaryl-4-methyl-5-substituted-1,8-bis-methoxycarbonyl-3,4,7-triaza-bicyclo[3.3.0]octa-2,7-dienes ($\text{7}$a-g), respectively.     

Recyclization of 2,3-Disubstituted 5-Arylamino-2,5-dihydro-1,2,4-thiadiazoles and Related Salts into Benzothiazole Derivatives

Russian Journal of General Chemistry -     

Recyclization of 3-oxazoliopropanesulfonates into 2,5-dihydro-1,2,4-triazinio-4-propanesulfonates

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1425–1426, October, 1989.     

Synthesis and Structure of 5-Indolyl-6-thienyl-1,2,4-triazines

Acylation of indole and 2,5-dimethylthiophene with 2-(3-indolyl)-2-oxoacetyl chloride afforded the corresponding diketones. 1-(2,5-Dimethyl-3-thienyl)-2-(3-indolyl)ethanedione reacted with thiosemicarbazide under atmosperic and elevated pressure to give 6-(2,5-dimethyl-3-thienyl)-5-(3-indolyl)-2,3-dihydro-1,2,4-triazine-3-thione whose structure was studied in detail by the X-ray diffraction method. Reactions of 6-(2,5-dimethyl-3-thienyl)-5-(3-indolyl)-2,3-dihydro-1,2,4-triazine-3-thione with amines and hydrazine resulted in formation of fused triazolo- and tetrazolotriazines.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 895–902.Original Russian Text Copyright © 2005 by Krayushkin, Yarovenko, Sedishev, Zavarzin, Vorontsova, Starikova.Dedicated to Full Member of the Russian Academy of Sciences V.I. Minkin on his Jubilee     

Synthesis and transformations of 3-azido-5-amino-1,2,4-triazines

The reaction of the tetrazolediazonium ion with malonic acid dinitrile and nitroacetonitrile leads to the formation of 3-azido-5-amino-1,2,4-triazine derivatives. According to the mass-spectrometric data and the results of X-ray diffraction analysis, the crystalline compounds exist in the amino form. The facile hydrolysis of the amino and azido groups to azauracils is an argument in favor of the existence of the imino form in solution.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 557–561, April, 1984.     

Synthesis and structure of 6-tert-butyl-5-triphenylgermyl-1,2,4-triazines

Russian Chemical Bulletin - 3-tert-Butyl-8-methyl-4-triphenylgermyl-1,4-dihydropyrazolo[5,1-c][1,2,4]triazine and...     

A regioselective approach to 5-substituted-3-amino-1,2,4-triazines

Nucleophilic displacement of readily available alpha,alpha-dibromoketones with excess morpholine gave the corresponding ketoaminals, which upon condensation with aminoguanidine in MeOH in the presence of AcOH afforded 5-substituted-3-amino-1,2,4-triazines in >95% regioselectivity and 45-76% isolated yield. [reaction: see text]     

An unusual transformation of 5-acyl-1,2,4-triazines into 3-pyridyl-1,2,4-triazines via tandem Stille cross-coupling/aza Diels-Alder reaction

A new route to 3-heteroaryl-1,2,4-triazines possessing a keto substituent at C-5 of the 1,2,4-triazine core using a Stille cross-coupling procedure and their unexpected ring transformation into pyridyltriazines as a result of enolization of an acyl group catalyzed by metal ions, are reported.     

Regioselectivity of cyclization of 1-(6-methyl-5-oxo-2,5-dihydro-1,2,4-triazin-3-yl)-4-arylthiosemicarbazides by treating with methyl iodide and dicyclohexylcarbodiimide

1-(6-Methyl-5-oxo-2,5-dihydro-1,2,4-triazin-3-yl)-4-arylthiosemicarbazides treated with methyl iodide in the presence of sodium acetate in ethanol convert into 6-methyl-3-arylamino[1,2,4]-triazolo[4,3-b][1,2,4]triazin-7(1H)-ones. In reaction with dicyclohexylcarbodiimide 6-methyl-3-arylamino[1,2,4]triazolo[3,4-c][1,2,4]triazin-5(1H)-ones were obtained which at heating in alcohol solution in the presence of sodium acetate or at 262–272°C underwent the Dimroth rearrangement to give 3-methyl-7-arylamino[1,2,4]triazolo[5,1-c][1,2,4]-triazin-4(8H)-ones.     

Nitroazines. 19. Prototropic tautomerism in 6-nitro-7-oxo-4,7-dihydro-1,2,4-triazolo[5,1-c][1,2,4]triazines

Prototropic reactions of 6-nitro-7-oxo-4,7-dihydro-1,2,4-triazolo[5,1-c][1,2,4]triazines is tautomeric as established from photoionization results. The ratios of the tautomers in the gas phase and in solution have been determined by mass and ¹³C NMR spectroscopy.For Communication 18 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1555–1559, November, 1992.     

Synthesis of Dialkyl 4-Ethoxy-2,5-dihydro-1-(9,10-dihydro-9,10-dioxoanthracen-1-yl)-5-oxo-1H-pyrrole2,3-dicarboxylates

Abstract

The reaction of ethyl 9,10-dihydro-9,10-dioxoanthracen-1-yl-carbamoyl-formate with dialkyl acetylenedicarboxylates in the presence of triphenylphosphine leads to dialkyl 4-ethoxy-2,5-dihydro-1-(9,10-dihydro-9,10-dioxoanthracen-1-yl)-5-oxo-1H-pyrrole-2,3-dicarboxylates in fairly good yields. A dynamic NMR effect is observed as a result of restricted rotation around the single bond linking the anthraquinone moiety and the heterocyclic ring system, which is attributed to the interaction between the pyrrole residue and the peri C═O group.