Synthesis of tailor-made 1-aryl-2-arylamino-4-imino-1,4,5,6-tetrahydro-1,3,5-triazine-6-thiones

Reaction of 1-amidino-3-arylthioureas (1) with aryl isothiocyanates yielded 1-aryl-2-arylamino-4-imino-1,4,5,6-tetrahydro-1,3,5-triazine-6-thiones (3) which contained the more electron releasing aryl substituent at the ring nitrogen. The reaction of the S-benzyl derivatives of (1) with aryl isothiocyanates could be directed to give the same type of triazinethione derivatives but with the desired aryl substituent at the ring nitrogen.     

Synthesis of 2-trifluoromethyl-4,6-diphenyl-1,3,5-triazine

Conclusions Methods have been developed for the preparation of the simplest fluorine-containing phenyltriazine, viz., 2-trifluororaethyl-4,6-diphenyl-1,3,5-triazine, in virtually quantitative yield.Translated from Izvestiva Akademii Nauk SSSR, Seriya Khimieheskaya, No. 4, pp. 919–920, April, 1986.     

Trisubstituted 1,3,5-triazines. 4. Synthesis of 2-nitroamino-4,6-bis(trinitromethyl)-1,3,5-triazine

The nitration, at the amino group, of 2-amino-4,6-bis(trinitromethyl)-1,3,5-triazine and its derivatives has been studied.For Communication 3, see [1].n. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 117913. Institute of Chemical Physics in Chernoglovka, Chernoglovka, Moscow Oblast, 142432, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 79–81, January, 1999.     

Reaction of 4-aryl-1,2,4-triazines with hydrazine

The action of hydrazine on 3,5-dioxo-4-aryl-2,3,4,5-tetrahydro-1,2,4-triazines gave 4-amino-3,5-dixo-2,3,4,5-tetrahydro-1,2,4-triazines. The intermediates of this reaction were isolated and shown to be α-ketoacidhydra-zide 4-arylsemicarbazones and not the α-ketoanilidecarbohydrazones. The realtive rates of cyclization of the latter isomeric derivatives provide a support for a proposed intermediates which were not isolated in the reaction of 3-mercapto and 3-methylmercapto-4-aryl-5-oxo-4,5-dihydro-1,2,4-triazines with hydrazine.     

Reaction of 2-imino-3-aryl-4-oxothiazolidines with phenyl isothiocyanate

2-Phenylthiocarbamoylimino-3-aryl-4-oxothiazolidines, which are hydrolyzed at the C=N and N₃=C₄ bonds of the thiazolidine ring to give 3-arylthiazolidine-2,4-diones, N-phenylthiocarbamoylarylpseudothiohydantoic acids, and 3-phenylthiocarbamoylthiazolidine-2,4-dione, were synthesized by reaction of 2-imino-3-aryl-4-oxothiazolidines with phenyl isothiocyanate.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 903–905, July. 1976.     

Synthesis of substituted 2-amino-4,6-bis(nonafluoro-tert-butyl)-1,3,5-triazines

A procedure was developed for the synthesis of substituted 2-amino-4,6-bis(nonafluoro-tert-butyl)-1,3,5-triazines from 2-chloro-4,6-bis(nonafluoro-tert-butyl)-1,3,5-triazine and aliphatic and aromatic amines. The data of¹⁹F NMR spectroscopy are indicative of the presence of a barrier to internal rotation. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1568–1572, August, 1999.     

Reaction of N1-acylacetamidrazones with trifluoroacetylvinyl ethers. Synthesis of new 4-trifluoromethyl- and 6-trifluoromethylpyridines

The reaction between N¹-acylacetamidrazones 1 and enol ether 2 is described. Depending on the reaction conditions and on the substitution pattern of amidrazones 2-acylhydrazino-4-methyl-6-trifluoro-methylpyridines 3 and/or 2-acylhydrazino-6-methyl-4-trifluoromethylpyridines 4 were obtained.     

Synthesis and molecular structure of 2-methoxy-4-amino-6-dinitromethyl-1,3,5-triazines zwitterionic salts

Zwitterionic salts of 2-methoxy-4-amino-6-dinitromethyl-1,3,5-triazines were synthesized. The structure of the compounds and the site of nitrogen protonation in the 1,3,5-triazine ring were established based on IR and ¹H NMR spectra and on the data of X-ray diffraction analysis.     

Synthesis of 4-alkylthio-2-(o-hydroxyphenyl)-1,3,5-triazines by recyclization of 4-oxo-1,3-benzoxazine perchlorates

A method has been developed for synthesis of 4-alkylthio-2-(o-hydroxyphenyl)-1,3,5-triazines by treatment of 4-oxo-1,3-benzoxazine perchlorates with S-methyl, benzyl, and allyl-isothioureas.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1658–1661, December, 1989.     

Synthesis of Chiral 2,4-Chiral 2,4-Dichloro-6-menthoxy-1,3,5-triazines and 2-Chloro-4, 6-Dimenthoxy-1,3,5-triazines as Enantiodifferentiating Coupling Reagents. An X-ray Study on 2,4,6-Trimenthoxy-1,3,5-triazine

Chiral mono-di-and trimenthoxy-1,3,5-triazines ware obtained from natural menthol and cyanuric chloride and applied as enantioselective coupling reagents in the synthesis of dipeptides.     

Introduction of a triflate group into sterically-hindered positions in 1-aryl-4,6-diamino-1,3,5-triazines and their dimroth rearrangement products

Decomposition of 1-(azidophenyl)-4,6-diamino-1,3,5-triazines 11–13 and their 4-amino-6-(azidoanilino)-1,3,5-triazine isomers 31–33 in trifluoromethanesulphonic acid at 0° led to the introduction of the triflate group (OSO₂CF₃) into the aryl group. This method can be employed to introduce a bulky substituent into the hindered position ortho to the triazinyl substituent. Dimroth rearrangement of 1-(aryl)-4,6-diamino-1,3,5-triazines is best effected in refluxing ethanolic pyridine.     

Azoles and azines: CXXVIII. Reaction of 2-aryl-4-hydroxy-6H-1,3-thiazin-6-ones with 6-bromo-4-oxo-4H-chromene-3-carbaldehyde

Russian Journal of General Chemistry -     

Mass spectrometric decomposition of 2-dimethylamino-4-methoxy-6-polynitromethyl-1,3,5-triazines

Fragmentation of 6-fluoro(chloro, bromo)dinitromethyl-, 6-trinitromethyl-, 6-(1,1-dinitroethyl)-, and 6-(2-hydroxy-1,1-dinitroethyl)-2-dimethylamino-4-methoxy-1,3,5-triazines under electron impact was studied. The stability of the molecular ions and main fragmentation pathways are discussed.     

First synthesis of 4-oxo-6-trifluoromethyl-4H-thiopyran-2-carboxylic acid and its derivatives

Treatment of 6-trifluoromethylcomanic acid with sodium hydrosulfide afforded for the first time 4-oxo-6-trifluoromethyl-4H-thiopyran-2-carboxylic acid (6-trifluoromethylthiocomanic acid). When heated or treated with H₂SO₄, this acid easily underwent decarboxylation leading to 2-trifluoromethyl-4H-thiopyran-4-one. Because of this, both ethyl and methyl 6-tri-fluoromethylthiocomanates were obtained in low yields (15–23%). Decarboxylation of 6-tri-(di)fluoromethylcomanic acids gave 2-tri(di)fluoromethyl-4H-pyran-4-ones in 77–80% yields.     

Trisubstituted 1,3,5-triazines. 2. Synthesis of 1,3,5-triazines from 2,4,6-tris[di(tert-butoxycarbonyl)methylene]hexahydro-1,3,5-triazine

A study was carried out on electrophilic addition and hydrolytic dissociation of 2,4,6-tris[di(tert-butoxycarbonyl)methylene]hexahydro-1,3,5-triazine. Chloro, bromo, and methyl derivatives of tris[di(tert-butoxycarbonyl)methyl]-1,3,5-triazine were synthesized for the first time as well as 2,4,6-tris-(tert-butoxycarbonylmethyl)-1,3,5-triazine. For Communication 1, see ref. [1]. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow and Institute of Chemical Physics, Russian Academy of Sciences at Chernogolovka, 142432 Chernogolovka, Moscow Oblast. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1404–1407, October, 1998.     

Synthesis of diethyl 6-aryl-2-oxo-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylates

Reaction of diethyl oxalylacetate sodium salt with aromatic aldehydes and urea led to the formation of diethyl 6-aryl-2-oxo-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylates.     

Synthesis, structural determination and dynamic behavior of 2-chloro-4,6-bis(pyrazolylamino)-1,3,5-triazines

A series of 2-chloro-4,6-bis(pyrazolylamino)-1,3,5-triazines with applications in crystal engineering have been prepared. At low temperature, the presence of two or three isomers has been detected and these assigned to 4,6-diamino-1,3,5-triazine structures on the basis of comparison with model compounds. 2D-Exchange spectroscopy studies in various solvents and at different temperatures have been used to determine the equilibrium constants and the activation free energies of the restricted rotation about the amino-triazine bond. A plot of the activation free energy versus temperature showed a good linear correlation and confirmed that the same process is present in all of the compounds under investigation. Comparison with model compounds also confirmed both the occurrence of the restricted rotation and the 4,6-diamino-1,3,5-triazine tautomerism for triazines 1-4 in solution. The structure of compound 1 has been determined in the solid state by X-ray crystallography and consists ofa 4,6-diamino- 1,3,5-triazine structure stabilized by intra and intermolecular hydrogen bonds.     

Reaction of enaminonitriles with isocyanates. Synthesis of new 2-oxo- and 6-oxopyrimidines

The reaction of enaminonitriles 1 with aryl or benzyl isocyanates afforded C- 3–5 or N-adducts 6–8 or a mixture of both depending on the substitution pattern of the considered enaminonitrile. The one-step synthesis of 6-oxopyrimidines 9–11 and 2-oxopyrimidines 12–14 by cyclization of compounds 3–5 and 6–8 respectively is also described.