1-Nucleosides of 5-substituted 4-chloro-1,2,3-triazoles

1-Nucleosides of 5-substituted 4-chloro-1,2,3-triazoles were produced by glycosylation of the corresponding triazoles by the method of fusion with tetra-0-acyl-D-ribofuranose in the presence of bis-p-nitrophenyl phosphate. The structure of the compounds obtained and their conformational peculiarities were studied by the methods of mass spectrometry and NMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1556–1564, November, 1984.     

Synthesis of [(4-chloro-5H-1,2,3-dithiazol-5-ylidene)amino]azines

The reactions of 2-, 3- and 4-aminopyridines with 4,5-dichloro-1,2,3-dithiazolium chloride (Appel salt) 4 to give N-(4-chloro-5H-1,2,3-dithiazol-5-ylidene)pyridin-X-amines 1a (X = 2), 1g (X = 3) and 1k (X = 4) were optimized with respect to base, temperature and reaction time. Based on these conditions a total of thirteen [(dithiazolylidene)amino]azines 1a-m were prepared and fully characterized.     

The 5-chloro-1-alkoxy-1,2,3-benzotriazole system

The 5-chloro-1-alkoxy-1,2,3-benzotriazole system has been synthesized and characterized via its physical and chemical properties. HMO calculations predict the most reactive sites on the molecule.     

Synthesis of 5-amino-4-hetaryl-2,3-dihydro-1h-3-pyrrolones

2-Hetaryl-3-oxo-4-phthalimidobutyronitriles (and pentanonitriles) were obtained with high yields by C-acylation of hetarylacetonitriles with N-phthaloylglycine and -alanine chlorides respectively under the conditions of base catalysis. Hydrazinolysis of the phthaloyl protection in these compounds leads to the formation of 5-amino-4-hetaryl-2,3-dihydro-1H-3-pyrrolones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1783–1790, December, 2004.     

Direction of glycosylation of 5-substituted 4-chloro-1,2,3-triazoles

The structures of previously obtained nucleosides of 5-substituted 4-chloro-1, 2,3-triazoles were refined by means of high-resolution mass spectrometry and ¹³C NMR spectroscopy. It is shown that fusion of 5-substituted 4-chloro,1,2,3-triazoles with tetra-0-acylribofuranoses in the presence of di(p-nitrophenyl) phosphate leads to the formation of 2-nucleosides of the corresponding triazoles. The signals of the carbon atoms in the ¹³C NMR spectra of the 4,5-di-substituted triazoles and their nucleosides were assigned.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 937–940, July, 1987.     

Synthesis of substituted 2-amino-5,6-dihydro-4h-1, 3-oxazines

4,4,6-Trimethyl-2-alkyl(aryl)amino-5,6-dihydro-4H-1,3-oxazines were synthesized via two methods: amination of 4,4,6-trimetiiyl-2-methylthio-5,6-dihydro-4H-1,3-oxazine and cyclization of N-aryl-N-(2-methyl-4-hydroxy-2-amyl)-S-methylisothiourea.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1037–1040, August, 1972.     

Synthesis of 4-chloro-7-dialkylaminocoumarins

A series of 4-chloro-7-dialkylaminocoumarins has been synthesized by heating m-diethylaminophenol, m-N-piperidinophenol, m-N-morpholinophenol, and 8-hydroxyjulolidine, respectively, with malonic acids in the presence of excess phosphorus oxychloride. The feasibility of preparing other 4-substituted 7-aminocoumarins from these 4-chloro derivatives has been demonstrated using as an example the reactions of 4-chloro-7-diethylaminocoumarins with sodium ethoxide, hydrazine, and dibutylamine. The spectral and luminescence characteristics of these newly synthesized compounds have been investigated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 830–835, June, 1990.     

4-Halogeno-3-oxides and sulfides of the 3,4-dihydro-2h-1,2,3-diazaphosphole system

4-Bromodiazaphosphole-3-oxides or sulfides can be obtained by reaction of the corresponding unsubstituted derivative with appropriate reagents. PTAB was demonstrated to be very regio- and stereoselective, allowing bromination exclusively at the 4-position of the ring with prevalent or exclusive formation of one of the two possible isomers. However, when regioselectivity is not required, cheaper and more available bromine or NBS can be used conveniently. 4-Chlorodiazaphosphole-3-oxides can be obtained by reaction of the corresponding unsubstituted derivative with NCS. 4-Bromodiazaphosphole-3-oxides undergo stereoselective methanolysis as well as parent unsubstituted oxides.     

Synthesis of 1-alkyl-4(5)-hydroxymethyl-1,2,3-triazoles

An in situ method for the synthesis of 1-alkyl-4(5)-hydroxymethyl-1,2,3-triazoles by the action of acetylenic alcohols with alkyl azides as the latter are formed from sodium azide and alkyl halides in dimethylformamide is proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1688–1689, December, 1980.     

Synthesis of 4-Arylselanyl-1H-1,2,3-triazoles from Selenium-Containing Carbinols

In this work, we present a simple way to achieve 4-arylselanyl-1H-1,2,3-triazoles from selenium-containing carbinols in a one-pot strategy. The selenium-containing carbinols were used as starting materials to produce a range of selanyl-triazoles in moderate to good yields, including a quinoline and Zidovudine derivatives. One-pot protocols are crucial to the current concerns about waste production and solvent consumption, avoiding the isolation and purification steps of the reactive terminal selanylalkynes. We could also isolate an interesting and unprecedented by-product with one alkynylselenium moiety connected to the triazole.     

N-alkylation of 4-chloro-5-cyano-1,2,3-triazole with orthoformic acid derivatives

The N-alkylation of 4-chloro-5-cyano-1,2,3-triazole with methyl and ethyl orthoformate, and the dimethyl, diethyl and ethylene acetals of DMF has been examined. Methylation gives all three N-methyl isomers, whereas ethylation and hydroxyethylation gives the 2-N-alkyl derivatives only. It has been shown for the first time that it is possible to use DMF ethylene acetal to obtain N-hydroxyethylazoles. The structures of the products were established by¹³C NMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 920–924, July, 1988.     

1-取代-1H-1,2,3-三唑-4-甲酰胺类化合物的设计合成与生物活性

以吡唑酰胺类杀菌剂为模板,应用"生物等排原理"设计了1,2,3-三唑甲酰胺类具有等排结构的化合物,从丙炔酸出发合成内炔酰胺后,利用Cu(I)催化的1,3-偶极环加成反应,使其与叠氮化合物反应,快速合成了17个结构新颖的1-取代-1H-1,2,3-三唑-4-甲酰胺类化合物.当使用Cu/C催化时,中间体N-(3,4-二甲氧基苯基乙基)丙炔酰胺(4a)与2,2,2-三氟乙基叠氮(14)在三乙胺作添加剂的条件下,可以获得中等收率的偶联的1,2,3-三唑化合物17.所有目标化合物都通过核磁共振氢谱,元素分析或高分辨质谱的确认,并测试了其生物活性.结果表明,该类化合物虽无明显的杀菌活性,但在100μg/mL测试浓度下,化合物6a,6e,6k和61均表现出较好的除草活性.     

Synthesis and Characterization of 2-Arylseleno-2-chloro-1,2,3-triorgano-1,3,2λ5-diazaphosphetidin-4-ones

The reactions of N,N′-dimethyl-N,N′-bis(trimethylsilyl)urea 8 and N-methyl-N′-phenyl-N,N′-bis(trimethylsilyl)urea 9 with phenylselenenyl chloride 6 and p-chlorophenylselenenyl chloride 7 furnished the N-arylseleno-N,N′-diorgano-N′-(trimethylsilyl)ureas 10–13 . The reactions of 10–13 with MePCl₂ and PhPCl₂ resulted in the formation of a new class of compounds, the 2-arylseleno-2-chloro-1,2,3-triorgano-1,3,2λ⁵-diazaphosphetidin-4-ones 14–19 . The new selenophosphoranes 20 and 21 were obtained in the reaction of 15 and 17 with p-nitrophenol in the presence of triethylamine. The identity and structure of the new compounds were established by ¹H- and ¹³C-NMR spectroscopy, elemental analysis, ³¹P- and ⁷⁷Se-NMR spectroscopy in the case of the selenophosphoranes 14–21 , and mass spectrometry in the case of 11 and 13 . A possible mechanism of the reaction leading to the selenophosphoranes is discussed. Single-crystal X-ray structure analyses of the selenophosphoranes 19 and 20 were conducted. Both display distorted trigonal bipyramidal geometry at phosphorus, the major distortions being imposed by the four-membered rings.     

The preparation and characterization of 5-substituted-4-chloro-1,2,3-dithiazolium salts and their conversion into 4-substituted-3-chloro-1,2,5-thiadiazoles

A series of monosubstituted acetonitriles were treated with disulfur dichloride at room temperature in CH2Cl2 to afford 5-substituted-4-chloro-1,2,3-dithiazolium chlorides 1.Where the 5-substituent was not a good leaving group the chloride salts were converted into the corresponding perchlorate salts 2 which were sufficiently stable and soluble to provide both (1)H- and (13)C-NMR and cyclic voltammetry data. Several of the dithiazolium chlorides were converted into their corresponding 4-substituted-3-chloro-1,2,5-thiadiazoles 13 on treatment with aqueous ammonia. Mechanisms for all reactions are proposed.     

Conformational analysis of 1-chloro-4-iodobutane and 1-chloro-5-iodopentane

Infrared spectra were obtained for Cl(CH₂)₄I and Cl(CH₂)₅I in the liquid and solid states. Zero-order normal coordinate calculations were made for the five conformers of each compound that have all the carbon atoms coplanar. Comparison of the observed and calculated wavenumbers led to the conclusion that all five conformers of Cl(CH₂)₄I are present in the liquid and solid states. For Cl(CH₂)₅I, the TT, TG and GT conformers are present in the liquid state. No evidence was obtained that indicated either the presence or absence of the GG and GG' conformers. Only the TT conformer is present in the solid. Vibrational assignments were made for both compounds.