Research in the field of functionally substituted azines. Syntheses of imidazolidinyl-sym-triazines

New approaches have been developed for the application of cyanamino-sym-triazines in the synthesis of imidazolidinyl-sym-triazines.     

Synthesis and thermal decomposition of haloalkoxy-sym-triazines. 7. Thermal decomposition of 2-dialkylamino-4-(2-chloroethoxy)-6-methoxyamino-sym-triazines

Two 2-dialkylamino-4-(2-chloroethoxy)-6-methoxyamino-sym-triazines were synthesized. It was established that when they are heated at 120° C, the 2-chloroethoxy group undergoes rearrangement with cyclization to give 2-dialkylamino-4-oxo-8-methoxy-6, 7-dihydroimidazo [1,2-a]-sym-triazines, the structure of which was confirmed by data from the IR, PMR, and mass spectra.See [6] for Communication 6.Translated from Khimiya Geterotsilicheskikh Soedinenii, No. 8, pp. 1122–1124, August, 1981.     

Some Conversions of Thiazoline Carboxylic Acid Esters

We have carried out solvolysis of the previously described ethyl esters of 3-methyl(aryl)-4-methyl-2-thioxothiazoline-5-carboxylic acids, leading to the corresponding acids without breaking down the heterocycle. We synthesized a series of novel esters from the latter by treatment with dimethyl sulfate or reactive halides. Of these, only in the case of the ethyl ester of 3,4-dimethyl-2-thioxothiazoline-5-carboxylic acid did we obtain the hydrazinolysis product (the hydrazide), from which we synthesized novel hydrazones by treatment with aldehydes and ketones.     

Investigations into functionally substituted azines.

Reaction of 2-N-potassiocyanamino-4,6-bisisopropyl(dimethylamino)-sym-triazines with acid 1,2,2,2-tetrachloroethylamides leads to the formation of 2-N-cyano-N-(1-acylamino-2,2,2-trichloroethyl)amino-4,6-bisisopropyl(dimethylamino)-sym-triazines. Reaction with 1-hydroxy(methoxy)-2,2,2-trichloroethylamides of chloroacetic acid leads to 2-(2-imino-4-oxooxazolidin-1-yl)-4,6-bis(dimethylamino)-sym-triazine and its 1-methoxy-2,2,2-trichloroethyl derivative substituted at the position 3 of the oxazolidine ring.     

Synthesis and thermal decomposition of haloalkoxy-sym-triazines. 8. Synthesis and thermal decomposition of 2-methoxy(methylthio)-4-(2-chloroethylthio)-6-dialkylamino-sym-triazines

New 2-chloroethylthio derivatives of sym-triazine were obtained by the reaction of mercapto-sym-triazines and dichloroethane. It was established that these chlorides undergo cyclization to give 2-dialkylamino-4-oxo(thioxo)-4,5,6,7-tetrahydrothiazolo [1,2-a]-sym-triazines, the structure of which was confirmed by PMR and mass-spectral data, at moderate temperatures.See [7] for Communication 7.Translated f rom Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1275–1278, September, 1981.     

Mass-spectrometric behavior of some cyano-substituted 4-(β-chloroethylmercapto)-sym-triazines

Intense [M-Cl]⁺ and [M-CT₂=CCNCl]⁺ ion peaks are characteristic for the mass spectra of 4-(-chloro--cyanoethylmercapto)-sym-triazines. The introduction of monoalkylamino groups into the 2 and 6 positions of the heteroring does not lead to the development of [M-HCl]⁺ ion peaks in the mass spectra or to a change in the characteristic fragmentation pathways.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1268–1270, September, 1982.     

Synthesis and thermal decomposition of haloalkoxy-sym-triazines 5. Thermal decomposition of 2-methoxy(methylthio)-4-[1,3-dichloropropoxy(3-chloro-1-propoxy)]-6-dimethylamino-sym-triazines

2-Methoxy (methylthio)-4-(1, 3-dichloropropoxy)-and 2-methoxy (methylthio)-4-(3-chloro-1-propoxy)-6-dimethylamino-sym-triazines were synthesized and subjected to thermolysis, as a result of which chloromethyltetrahydrooxazolo-, N-2, 3-di-chloropropyl-sym-triazines and tetrahydrooxazino-and tetrahydrothiazino-sym-triazines, respectively, were obtained. The thermolysis of haloalkoxy-sym-triazines proceeds via a concerted mechanism. See [4] for communication 4. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 411–415, March, 1980.     

Studies on Functionally-substituted Azines. 8. Synthesis and Transformations of 1-Arylsulfonylamido-4-methoxy-6-methylpyrimidines

The action of arylsulfonyl chlorides on 2-amino-4-methoxy-6-methylpyrimidine in pyridine gave 2-arylsulfonylamido-4-methoxy-6-methylpyrimidines, which were alkylated at the amide fragment, while the action of hydrazine hydrate led to nucleophilic replacement of the methoxy group. The resultant hydrazinopyrimidines were converted into azidopyrimidines and N-pyrimidinyldithiocarbazinates. Potassium salt of 2-p-toluenesulfonylamido-4-methoxy-6-methylpyrimidine dithiocarbazinate reacted with dimethyl sulfate to give the S-methyl derivative, while the reaction with chloroacetonitrile gave thiazolidinylaminopyrimidine. The chlorination using N-chlorosuccinimide yielded only 5-chloropyrimidines.     

Effect of Different Substituents on Amine-imine Tautomerism of 2-Amino-4-methylthiazole Derivatives

We have used ¹H NMR to study the amine-imine tautomerism of some esters and amides of 2-N-labeled 4-methylthiazole-5-carboxylic acids and 5-carbamic acids. We have shown that the nature of the substituents of the 2-NHR¹, 5-COR², or 5-NHCOR² groups affects that position of the tautomeric equilibrium. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1240–1243, August, 2005.     

Synthesis of N-cyano-N-alkoxycarbonylalkylamino-symm-triazines and their solvolysis

The action of potassium salts of cyanoamino-symm-triazines on esters of chloroacetic and bromomalonic acids gave carbonylalkylamino-symm-triazines. The solvolysis of these esters proceeds with heterocyclilzation, leading to the formation of hydantoin derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1114–1116, August, 1993.