Алкилирование 5-фенил-6r-2н-1,2,4-триазин-3-тиона и гетероциклизация 1-(4-бромфенил)-2-(5-фенил-6r-1,2,4-триазин-3-илсульфанил)этанонов

A. V. Rybakova; D. G. Kim; O. A. Khaybullina; V. G. Sobolevskaya

Authors

A. V. Rybakova South Ural State University, Chelyabinsk, Russian Federation
D. G. Kim South Ural State University, Chelyabinsk, Russian Federation
O. A. Khaybullina South Ural State University, Chelyabinsk, Russian Federation
V. G. Sobolevskaya South Ural State University, Chelyabinsk, Russian Federation

Keywords:

5, 6-diphenyl-1, 2, 4-triazine-3-thione, 5-phenyl-2, 3-dihydro-1, alkylation, heterocyclization, 1-(4-bromophenyl)-2-(5-phenyl-1, 4-triazine-3-ylsulfanyl)ethanone, 1-(4-bromophenyl)-2-(5

Abstract

5,6-Diphenyl-1,2,4-triazine-3-thione and 5-phenyl-2,3-dihydro-1,2,4-triazine-3-thione were obtained by condensation of dibenzoyl (benzyl) and phenylglyoxal, respectively, with thiosemicarbazide (or its hydrochloride). Alkylation of 5,6-diphenyl-1,2,4-triazine-3-thione and 5-phenyl-2,3-dihydro-1,2,4-triazine-3-thione with p-bromophenacyl bromide in acetonitrile (acetone) in the presence of triethylamine proceeded to give 1-(4-bromophenyl)-2-(5-phenyl-(5,6-diphenyl-)- 1,2,4-triazine-3-ylsulfanyl)ethanones. 5,6‑Diphenyl-1,2,4-triazine-3-thione was also alkylated by monochloroacetic acid and its methyl ester. It should be noted that the product of the abovementioned alkylation reaction was obtained in a higher yield with the use of the K₂CO₃–H₂O–DMF system. The ¹H NMR spectra of S-derivatives of 5-phenyl-(5,6-diphenyl-)- 1,2,4-triazine-3-thiones contained signals of the SCH₂ protons in the range of δ 4.04–5.01 ppm as well as aromatic protons of the phenyl rings manifested as a multiplet at δ 7.23–7.50 ppm. The aromatic protons of the p-bromophenacyl group were observed as two signals shifted downfield at δ 7.77–7.83 and δ 8.02–8.06 ppm. The IR spectra of S-derivatives of 5-phenyl-6R-1,2,4-triazine-3-thiones contained intense bands of the С=О group at 1700, 1681, 1680, 1740 cm^–1. The action of concentrated sulfuric acid on 1-(4-bromophenyl)-2-(5,6-diphenyl-1,2,4-triazine-3-ylsulfanyl)ethanone led to an intramolecular addition to the carbonyl group followed by dehydration and formation of 3-(4-bromophenyl)-6,7-diphenyl-8а-Н-[1,3]thiazolo[3,2-b][1,2,4]triazine-8-ol, as evidenced by the ¹H NMR data. The ¹H NMR spectrum of the latter compound revealed no signals of the SCH₂ protons, and the H-2 proton appeared as the signal shifted downfield (δ 6.78 ppm). 3-(4-Bromophenyl)-7-phenyl[1,3]thiazolo[3`,2`;2,3][1,2,4]triazinium hydrosulfate was synthesized by the intramolecular heterocyclization of 1-(4-bromophenyl)-2-(5-phenyl-1,2,4-triazine-3-ylsulfanyl)-ethanone under the action of concentrated sulfuric acid. The ¹H NMR spectrum of 3-(4-bromophenyl)-7-phenyl[1,3]thiazolo[3`,2`;2,3][1,2,4]triazinium hydrosulfate contained the characteristic signal at δ 8.96 ppm attributed to the aromatic H-2 proton of the thiazole cycle. In addition, the cyclization reaction was evidenced by the shift of the H-6 proton signal to a weaker field (δ 10.29 ppm) compared with the corresponding proton signal of the starting compound, which could be caused by the appearance of a positively charged nitrogen atom in the structure. It is also pertinent to note that the IR spectra of the heterocyclization products revealed no absorption band of the carbonyl group, in contrast to the IR spectra of the initial
1-bromophenyl-2-(1,2,4-triazine-3-ylsulfanyl)ethanones.5,6-diphenyl-1,2,4-triazine-3-thione, 5-phenyl-2,3-dihydro-1,2,4-triazine-3-thione, alkylation, heterocyclization, 1-(4-bromophenyl)-2-(5-phenyl-1,2,4-triazine-3-ylsulfanyl)ethanone, 1-(4-bromophenyl)-2-(5,6-diphenyl-1,2,4-triazine-3-ylsulfanyl)ethanone, 3-(4-bromophenyl)-6,7-diphenyl-8а-Н-[1,3]thiazolo[3,2-b][1,2,4]triazine-8-ol, 3-(4-bromo-phenyl)-7-phenyl[1,3]thiazolo[3`,2`;2,3][1,2,4]triazinium hydrogen sulfate

Author Biographies

A. V. Rybakova, South Ural State University, Chelyabinsk, Russian Federation

кандидат химических наук, доцент кафедры теоретической и прикладной химии

D. G. Kim, South Ural State University, Chelyabinsk, Russian Federation

доктор химических наук, профессор, кафедра прикладной и теоретической химии, химический факультет, институт естественных и точных наук

O. A. Khaybullina, South Ural State University, Chelyabinsk, Russian Federation

студент

V. G. Sobolevskaya, South Ural State University, Chelyabinsk, Russian Federation

магистрант

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