1,4,5,6-Tetrahydro-1,2,4-triazin-6-ones and 3-amino-1-imidazolin-4-ones from 2-aminoacylhydrazines

The 2-aminoacylhydrazines form 1,4,5,6-tetrahydro-1,2,4-triazin-6-ones with orthoesters and iminoesters. Benzylidene and isopropylidene derivatives of the 2-aminoacylhydrazines give the corresponding derivatives of 3-amino-1-imidazolin-4-ones with the same reagents.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1388–1391, October, 1991.     

A Convenient Synthesis of 1,2,4-Triazolo-1,3,5-triazin-4-ones and 1,2,4-Triazolo-1,3,5-triazin-4-thiones

The imidates derived from 3-aminotriazole 1 react with isocyanates and isothiocyanates to give corresponding 1,2,4-triazolo-1,3,5-triazin-4-ones and 1,2,4-triazolo-1,3,5-triazin-4-thiones in a 60–75% overall yield. If the condensation is realized at r.t., then the intermediate 2 can be isolated.     

Synthesis of 4-alkyl-6-amino-3,5-dicyano-2(1H)-pyridinethiones

Condensation of aliphatic aldehydes with cyanothioacetamide has given 4-alkyl-6-amino-3,5-dicyano-2(1H)-pyridinethiones, which have also been synthesized by recyclization of 4-alkyl-2,6-diamino-4H-thiopyrans. Substituted 2-alkylthiopyridines and thieno[2,3-b]pyridines have been prepared from the pyridinethiones. 2,6-Diamino-4-isopropyl-3,5-dicyano-4H-thiopyran and 6-amino-4-isobutyl-2-methylthio-3,5-dicyanopyridine have been studied by x-ray crystallography.T. G. Shevchenko State Teaching Institute, Lugansk 348011. A. N. Nesmeyanov Institute of Organoelemental Compounds, Moscow 117813. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1655–1663, December, 1997.     

Thermal Decomposition of Triazine Herbicides. I. 1,2-(4-chloro-6-ethylamino-1,3,5-triazin-2-ylamino)-2-methylpropionitrile (cyanazine)

Cyanazine was taken as an example for investigations under the influence of different conditions on thermal decomposition of triazine herbicides. DSC measurements were carried out under atmospheric pressure and hermetically closed, under pressure 1.3 kPa. The influence of the pressure on the constant reaction rate of decomposition of cyanazine was discussed. It was also proved that the predicted reaction constant rates from isothermal and non-isothermal measurements are consistent. This revised version was published online in August 2006 with corrections to the Cover Date.     

2-芳基-2,3-二氢4(1H)-喹唑啉酮类化合物的合成

在NaHSO4催化下,以苯甲醛和邻氨基苯甲酰胺为底物,在室温下合成了一系列2-芳基-2,3-二氢-4(1H)-喹唑啉酮类化合物,该反应产率高、操作简单、并且避免使用有毒的金属催化剂.     

Synthesis of N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea with a radioactive label

Methods for the introduction of a radioactive ¹³C label into N-(2-chlorophenyl-sulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, which has herbicidal activity, are described.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 654–656, May, 1989.     

Synthesis and transformations of 6-amino-3,5-dicyano-4ethylpyridine-2(1H)-thione

The condensation of propionaldehyde with cyanothioacetamide gives 6-amino-3,5-dicyano-4-ethylpyridine-2(1H)-thione, which was used to obtain substituted 2-alkylthiopyridines, 2-ethylthio-6- ethylaminopyridine, and pyrazolo[3,4-b]pyridine.T. G. Shevchenko Lugansk State Pedagogical Institute, 348011 Lugansk. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Science, 117913 Moscow. Translated from Khimiya Geterotsklicheskikh Soedinenii, No. 8, pp. 1094–1098, August, 1996. Original article submitted March 4, 1996; revision submitted July 1, 1996.     

Synthesis of 4-Alkynyl-substituted 3,4-Dihydropyrimidin-2(1H)-ones

4-Alkynyl-3,4-dihydropyrimidin-2-(1H)-ones were synthesized by a one-pot reaction of propynals, ethyl acetoacetate, and urea. The yields of acetylenic dihydropyrimidinones depend significantly upon the propynal structure and catalyst type. A comparative study of the catalysts revealed an important advantage of polyphosphate ester in tetrahydrofuran in comparison with hydrochloric acid in methanol or trimethylchlorosilane in dimethylformamide, allowing the preparation of target compounds in good or moderate yields.     

Synthesis and structure of 6-amino-3,5-dicyano-4-heptylpyridine-2(1H)-thione

Condensation of caprylic aldehyde with cyanothioacetamide taken in a ratio of 1:2 affords 6-amino-3,5-dicyano-4-heptylpyridine-2(1H)-thione. The structure of the thione was studied by X-ray structural analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 196–198, January, 1997.     

Synthesis of 6-nitro-8-chloro-2,3-dieydro-4(1H)-quinolone

6-Nitro-8-chloro-2,3-dihydro-4(1H)-quinolone and its dehydrogenation product-6-nitro-8-chloro-4-hydroxyquinoline — were isolated in the cyclization of N-(2-chloro-4-nitrophenyl--alanine in polyphosphoric acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 954–956, July, 1978.     

Synthesis and structure of dihydro-1,2,4-triazin-6(1H) ones

Reactions of the iminoesters 3a-c with hydrazine or 1,2-dimethylhydrazine gave 4,5-dihydro- 4a-c or 2,5-dihydro-1,2,4-triazin-6(1H) ones 7a-c , respectively. When methylhydrazine was employed, 1-methyl-4, 5-dihydro- 5a-c and 2-methyl-2,5-dihydro-1,2,4-triazin-6(1H) ones 6a-c were obtained. Compounds 6a-c exist as zwitterions in the solid state and in polar aprotic solvents.     

Synthesis of 2,3-Dihydroquinazoline-4(1H)-ones

An efficient, inexpensive, and heterogeneous catalyst, [Al(H₂PO₄)₃], was applied in a three-component, one-pot cyclocondensation reaction of isatoic anhydride with primary amines (or ammonium salts) and aldehydes to afford the corresponding quinazolinone derivatives in excellent yields. Reactions occurred under thermal solvent-free conditions. It was found that this solid acidic catalyst could be easily recovered and reused for at least three cycles without any loss of activity.     

Synthesis of 4-(2-acetoxyethoxymethyl)-6-methyl-1,2,4-triazin-3(4H)-one 1-oxide as thymidine analogue

Alkylation of the sodium salt and the trimethyl silylated derivatives of 6-methyl-1,2,4-triazin-3(4H)-one 1-oxide with chloromethoxyethyl acetate, n-hexyl chloride and benzyl bromide gave the 4-substituted products. However, attempts to achieve the ring closure of N⁴-(2-acetoxyethoxymethyl)thiosemicarbazide with bicarbonyl compounds to the corresponding as-triazines under different reaction conditions was not possible without disruption of the acetoxyethoxymethyl moiety. Although the as-triazine nucleoside analog II did not show antileukemic activity, this and other 4-alkylated as-triazine 1-oxides revealed good growth inhibitory effects against a representative spectrum of microorganisms.     

Approaches to the construction of substituted 4-amino-1H-pyrrol-2(5H)-ones

Fully substituted 4-aminopyrrolones are easily accessed via simple routes starting from imines, ketones, or α-bromophenyl acetonitriles. Imines were reacted with KCN/NH(4)Cl in aqueous ethanol to produce α-arylamino benzyl cyanides. On the other hand, ketones were transformed to the desired α-amino nitriles using a modified Strecker reaction. Then, α-amino nitrile precursors were allowed to react with a suitable acyl halide to produce the corresponding amides. Further treatment of these amides with ethanolic KOH converted them to highly substituted 4-amino-1H-pyrrol-2(5H)-one derivatives in moderate to excellent yields.     

Synthesis of 2-amino-4-hydroxy-1,3,5-triazanaphthalenes

The synthesis of 2-amino-4-hydroxy-6-amyl-1,3,5-triazanaphthalene (8) is described as a model sequence pertinent to preparation of 8-deazafolic acid and its analogs. Condensation of 2-acet-amido-4-hydroxy-6-pyrimidinealdehyde (3) with dimethyl 2-oxoheptylphosphonate afforded 1-(2′-acetamido-4′-hydroxy-6′-pyrimidinyl)-1-octene-3-one (4) as a key intermediate. Conversion of 4 to 1-(2′-amino-4′-hydroxy-5′ -phenylazo-6′ pyrimidinyl)-3-octanone (7) followed by reductive cyclization yielded 8 or its tetrahydro derivative (9) .     

4-(9-蒽基)-6-十六烷氧基-2-氨基-1,3,5-三嗪的合成及光谱行为的研究

从三氯均三嗪出发通过三步反应合成了4-(9-蒽基)-6-十六烷氧基-2-氨基-1,3,5-三嗪(AHTA),并通过红外、核磁、质谱、高分辨质谱对目标产物进行了表征.研究表明AHTA分子在基态下分子的蒽环与三嗪环不共平面,激发态下表现为ICT的荧光发射.由于分子间氢键作用的存在,AHTA在自组装膜和LB膜中均形成H-聚集体.