Heterocyclic compounds

A method for the synthesis of 9-arylamino--quinindanes from anilides of cyclopentylideneanthranilic acid has been devised. A number of previously undescribed compounds have been obtained, and their properties have been examined.For Parts I and II, see [1].The name -quinindanes has been suggested for 2, 3-trimethylenequinolines [2].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1242–1243, September, 1970.     

Heterocyclic nitro compounds

Reaction of 1-methyl-3,5-dinitro-1,2,4-triazole with alcohols or phenols in the presence of bases (tertiary amines) leads to replacement of the nitro group in the 5-position by an alkoxy or phenoxy group.For part IV, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 5, pp. 702–704, May, 1970.     

Heterocyclic nitro compounds

A number of triazolylpropanones were synthesized by oxidation of 1-(2-hydroxypropyl)-3-nitro-5-R-1,2,4-triazoles obtained by condensation of 3-nitro-5-R-1,2,4-triazoles with propylene oxide. Similar triazolylbutanones were obtained by reaction of 3-nitro-5-R-1,2,4-triazoles with methyl vinyl ketone.See [1] for communication XIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 991–994, July, 1976.     

Heterocyclic nitro compounds

The reaction of 3(5)-nitro-1,2,4-triazole with hydrogen halides (HCl and HBr) leads to replacement of the nitro group by chlorine and bromine. In 1-methyl-3,5-dinitro-1,2,4-triazole the nitro group in the 5 position is replaced. Nucleophilic substitution of halogen in 1-methyl-3-nitro-5-halotriazoles leads to the formation of the corresponding 1-methyl-3-nitro-5-substituted 1,2,4-triazoles.See [1] for Communication VI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1701–1703, December, 1970.     

Heterocyclic diazo compounds

Benzothiazole-2-diazonium tetrafluoroborate and its 6-bromo, 6-methyl, and 6-methoxy derivatives are relatively stable and have high electrophilicities. They are rapidly converted in weakly alkaline media to the corresponding anti-diazotates, from which primary nitrosoamines can be obtained by acidification.     

Heterocyclic nitro compounds

Depending on the conditions and nature of the hydrazine derivative, the reaction of 1-methyl-3,5-dinitro-1,2,4-triazole (I) with hydrazine leads either to the replacement of one of the nitro groups by a hydrazine residue or to its reduction to an amino (hydroxylamino) group. In both cases, the reaction takes place in position 5 of the triazole ring. The reaction of I with acetylhydrazine gives 5-azido-1-methyl-3-nitro-1,2,4-triazole.For Communication V, see [11].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 7, pp. 997–1000, July, 1970.     

Heterocyclic nitro compounds

Reaction of 1-methyl-3, 5-dinitro-1, 2, 4-triazole with aliphatic amines results in the replacement of the nitro group in the 5-position of the triazole ring by the amino group. Some reactions of the compounds obtained have been investigated.For part II, see [1].     

Heterocyclic nitro compounds

The kinetics of the reaction of 1-methyl-3-nitro-5-chloro-1,2,4-triazoles and 1-methyl-3-nitro-5-bromo-1,2,4-triazoles with hydroxide ions were studied. The reaction leads to replacement of the halogen or nitro group, and the ratio of the rates of substitution is 301. The mutual influence of the halogen and nitro group on the rate of substitution as a function of their position in the ring was examined.See [1] for communication XIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 848–851, June, 1972.     

Heterocyclic nitro compounds

1,2,4-Triazole, 3(5)-R-1,2,4-triazoles (R=CH₃, CL, Br, NO₂), and their N-trimethylsilyl derivatives were nitrated with nitronium salts. The products were N-nitro-1,2,4-triazoles, which split out the nitro group under the influence of acids and undergo rearrangement to 3-nitrotriazoles when they are heated in inert solvents. When R=NO₂, a dinitrotriazole is not formed, and the starting 3-nitro-1,2,4-triazole is recovered.See [1] for communication 21.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 550–554, April, 1979.     

Heterocyclic nitro compounds

The MO LCAO method with the Hückel approximation was used to calculate the -electron densities, the bond orders, and the energies of the -electron interaction of a number of 1,2,4-triazole derivatives. The results obtained agree satisfactorily with the chemical and physicochemical properties of the triazoles.See [1] for communication IX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 409–413, March, 1971.     

Heterocyclic nitro compounds

The dipole moments of some 3(5)-nitro-1,2,4-triazoles in dioxane were measured. Hydrogen is attached to the N₁ heteroatom in nitrogen-unsubstituted 3-nitrotriazoles. The dipole moments of the triazoles in chloroform are lower than in dioxane.See [1] for communication VIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 275–278, February, 1971.     

Heterocyclic nitro compounds

Ketones of the 3-nitro-5-R-1,2,4-triazole series react with hydrazoic acid in concentrated sulfuric acid to give triazolyl-substituted acetamides. Acid hydrolysis of the latter leads to 1-aminoalkyl-3-nitro-5-R-1,2,4-triazoles. Intramolecular cyclization with the elimination of HNO₂ and the formation of 2-nitro-5,6-dihydro-1H-imidazo[2,3-b]-1,2,4-triazole was noted in the case of 1-(2-aminoethyl)-3,5-dinitro-1,2,4-triazole.See [1] for communication XX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1271–1273, September, 1977.     

Heterocyclic nitro compounds

The IR and Raman spectra of a number of anions of the nitro derivatives of 1,2,4-triazole were investigated. On the basis of the position of the absorption maxima of the asymmetric and symmetric t vibrations of the nitro group, it is assumed that the nitro groups in the 3 and 5 positions of the triazole ring are coplanar, which should lead to an increase in the participation of the nitro group in the de localization of the negative charge of the anion. Shifts of the frequencies as a function of the nature of the cation (NH₄, Na, K, Cs) were not detected in the IR spectra of the crystalline salts. In addition, the IR spectra of the crystalline salts are similar (with respect to the frequencies) to the spectra of aqueous solutions of the salts, which may serve as proof of the identical structure of the anions in crystals and aqueous solutions.See [1] for communication XII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 120–123, January, 1972.     

Heterocyclic nitro compounds

The acidity of a number of nitro derivatives of 1,2,4-triazole has been determined. The acidity indices correlate well with Hammett's _I and _meta constants and somewhat less well with the _para constants. The high values of show the great sensitivity of the system to the influence of substituents. The acidities of the conjugate acids of 3-nitro-1,2,4-triazole and its C- and N-methyl derivatives have also been determined. Hammett's postulate is not observed for these compounds, and the amide scale of acidity, H_A, is more suitable for calculating their acidity indices than H_O.For part III, see [1].     

Heterocyclic nitro compounds

The kinetics of the substitution of a nitro group by a hydroxyl group in 1-methyl-3-nitro-,1-methyl-5-nitro-, and 3-nitro-4-methyl-1,2,4-triazoles as well as in a series of 1-methyl-3-R-5-nitro-1,2,4-triazoles were studied. The activation parameters of the reaction were determined. There is a linear correlation dependence between log k and the _m substituent constants in the investigated series.See [1] for communication XIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 568–571, April, 1972.     

Heterocyclic nitrogen compounds in whisky and beer

Summary Differences in the composition of the heterocyclic nitrogen compounds in whisky and beer were studied using capillary gas chromatography. The raw materials common to both whisky and beer lead to similar N-heterocycles being detected in both beverages. Pyridines, pyrazines, and thiazoles could be identified in both beverages. In addition, pyrroles were detected in beer and quinolines in whisky. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Heterocyclic compounds based on maleic acid monoureide

The products of the bromination in water of maleic acid monoureide and its methyl ester have the 2-imino-5-bromocarboxy(carbomethoxy)methyl-4-oxazolidone structure. 2-Imino-5-bromocarboxymethyl-4-oxazolidone undergoes dehydrobromination in aprotic polar solvents to give 2-imino-5-carboxymethylidene-4-oxazolidone. In the presence of dry hydrogen chloride in dimethylacetamide the oxazole ring undergoes dehydrobromination and isomerization to an imidazole ring with the formation of 5-carboxymethylidenehydantoin. Methyl -bromofumarate monoureide is formed when the oxazole ring of 2-imino-5-bromocarbomethoxymethyl-4-oxazolidone is opened with alkali.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 972–975, July, 1979.The authors thank S.I. Zav'yalov, I. Ya. Shternberg, and I. P. Sekatsis for their participation in the discussion of this research.