Synthesis and structural study of 4,6-diazido-2-(2,2,2-trinitroethylamino)-1,3,5-triazine

Russian Chemical Bulletin - A method for synthesis of 2-(2,2,2-trinitroethylamino)-4,6-diazido-1,3,5-triazine from 2-amino-4,6-diazido-1,3,5-triazine was elaborated. The molecular and crystal...     

New polynitrogen hyperbranched polymers

A method for the preparation of new representatives of polynitrogen hyperbranched polymers of heterocyclic series was developed involving polymerization of monomeric 2,4-diazido-6-propynyloxy-1,3,5-triazine by 1,3-dipolar cycloaddition. Kinetics of polymerization of diazidoacetylene monomer was compared with the kinetic data of polymerization of its closest analog, 2-azido-4,6-bis(propynyloxy)-1,3,5-triazine monomer. Properties of hyperbranched poly(1,2,3-triazole-1,3,5-triazine)s with terminal azide groups and terminal triple bonds were compared, as well.     

Nitrene-carbene rearrangement during photolysis of 2-azido-1,3,5-triazines in argon matrices

It was shown using IR spectroscopy and ESR spectroscopy that UV irradiation of 2-azido-4,6-dichloro-1,3,5-triazine isolated in solid argon resulted in triplet 4,6-dichloro-1,3,5-tri-azinyl-2-nitrene (D = 1.384 cm^?1, E = 0.004 cm^?1), whose further photochemical transformation included the consecutive formation of 3-didehydro-1,2,4,6-tetraazepine, 2-chloro-1-diazochloromethyl-2-isocyanocarboimide, and presumably triplet 2-chloro-1-chloromethyl-idene-2-isocyanocarboimide and isocyanodichloroacetonitrile. The photolysis of 2-azido-4,6-dimethoxy-1,3,5-triazine and 2-azido-4,6-di(dimethylamino)-1,3,5-triazine affords photo-chemically stable triplet 4,6-dimethoxy-1,3,5-triazinyl-2-nitrene (D = 1.436 cm^?1, E = 0.0044 cm^?1) and 4,6-bis(dimethylamino)-1,3,5-triazinyl-2-nitrene (D = 1.468 cm^?1, E = 0.0042 cm^?1) as the final products.     

Acylhydroperoxide oxidations of the anticancer agent hexamethylmelamine

The clinically effective anticancer agent hexamethylmelamine undergoes an unusual acylhydroperoxide oxidative transformation to give the novel product 2,4-bis(dimethylamino)-6-[(dimethylamino)oxy]-1,3,5-triazine.     

Condensed Tetrazolo-1,3,5-triazines. 1. Synthesis of 5-Polynitromethyltetrazolo[1,5-<Emphasis Type="Italic">a</Emphasis>]-1,3,5-triazin-7-one Salts

The aziridation of 2-R-4,6-bis(trinitromethyl)-1,3,5-triazines containing electron-donor substituents has been studied. It was found that the corresponding 4-azido-2-dialkylamino-6-trinitromethyl-1,3,5-triazines are formed when R = NMe₂, NEt₂. When R = O^–NMe₄ ⁺ a novel reaction route was discovered leading to the tetramethylammonium salt of 5-polynitromethyltetrazolo[1,5-a]-1,3,5-triazin-7-one which is formed as a result of azido-tetrazole and lactim-lactam tautomeric conversion. Denitration of this salt at the trinitromethyl group occurs with retention of the tetrazolo-1,3,5-triazine structure. An X-ray analysis was carried out for the denitration product which was the dipotassium salt of 5-dinitromethyltetrazolo[1,5-a]-1,3,5-triazin-7-one.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 259–266, February, 2005.     

Herbizide,VI [1] kernfluorierte 2,4-dianilino-6-(dihexylamino)-1,3,5-triazine

The nucleophilic substitution of the chlorine atoms in 2,4-dichloro- 6-(dihexylamino)-1,3,5-triazine by aniline leads to 2,4-dianilino-6-(dihexylamino)- 1,3,5-triazine and by fluorinated amines to (dihexylamino)- 1,3,5-triazines bearing groupings as follows: (2-fluoroanilino)-, (3-fluoroanilino)-, (4-fluoroanilino)-, (2,4-difluoroanilino)-, (2,5-difluoroanilino)-, and (2,6-difluoroanilino)-. The new compounds are characterized by IR, ¹-NMR, and mass spectroscopy. 2,4-Bis-(2,4-difluoroanilino)- 6-(dihexylamino)-1,3,5-triazine in particular shows herbicidal and anti- diabetic activity.     

Hyperbranched Poly([1,2,3]-triazole-[1,3,5]-triazine)s: An Unusual High Degree of Branching as an Effect of a Polyaddition Kinetics

The results of the kinetic study of melt and solution polymerization at the 1,3-dipolar cycloaddition reaction of the AB₂ monomer – 2-azido-4,6-bis(prop-2-yn-1-yloxy)-[1,3,5]-triazine (ABPOT) are presented in this work as well as the results of the ¹³C-NMR characterization of the obtained hyperbranched poly([1,2,3]-triazole-[1,3,5]-triazine)s. It is established, that the first-shell substitution effect during polyaddition process and unusual high degree of branching (up to 0.9) of polymers synthesized in melt are held.     

Trisubstituted 1,3,5-Triazines. 5. Reaction of 2,4,6-Tris[di(tert-butoxycarbonyl)nitromethyl]-1,3,5-triazine with Nucleophiles

The reaction of 2,4,6-tris[di(tert-butoxycarbonyl)nitromethyl]-1,3,5-triazine with ammonia, amines, and hydrazine has been studied. It was possible to substitute one of the di(tert-butoxycarbonyl)nitromethyl groups in this compound in the presence of ammonia, primary aliphatic amines, dimethylamine, and morpholine. The reaction with hydrazine leads to both mono- and disubstituted products. A double dealkoxylation occurs in the presence of diethylamine to give the bis(dimethylammonium) salt of 2,4-bis(tert-butoxycarbonylnitromethyl)-6-[di(tert-butoxycarbonyl)nitromethyl]-1,3,5-triazine.     

Hydrogen-bonded supramolecular poly(ether ketone)s

The preparation of 2,4-diamino-1,3,5-triazine telechelic poly(ether ketone)s (triazine PEKs) and the formation of supramolecular polymers with dodecyl-(α-ω)-bis(5-methyl-1,3-pyrimidine-2,4-dione) were investigated. Both structures interacted by complementing hydrogen-bonding units present at their respective chain ends, this being reminiscent of triple hydrogen bonding in DNA. The preparation of the triazine PEKs started from hydroxyl-terminated poly(ether ketone)s by a nucleophilic displacement reaction with 2,4-diamino-6-(4-fluorophenyl)-1,3,5-triazine. With this method and molecular weight control via the Carothers equation, a series of triazine PEKs with a complete degree of end-group functionalization were prepared. The structure of the polymers was proven by ¹³C NMR spectroscopy and matrix-assisted laser desorption/ionization spectroscopy. When mixed as a 1:1 complex in solution with dodecyl-(α-ω)-bis(5-methyl-1,3-pyrimidine-2,4-dione), short triazine PEKs (molecular weight = 5700 or 10,000) showed a temperature-dependent association behavior visible via dynamic NMR spectroscopy. Additional proof of the formation of a supramolecular, hydrogen-bonded network was derived from solid-state NMR spectroscopy, differential scanning calorimetry, and rheological investigations. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 661–674, 2004     

New hyperbranched poly([1,2,3]-triazole-[1,3,5]-triazines)

New hyperbranched polymers have been synthesized through the 1,3-dipolar polycycloaddition of the AB₂ monomer—2-azido-4,6-bis(propynyloxy)-[1,3,5]-triazine. The polymers contain conjugated heteroaromatic triazine and triazole cycles and terminal acetylene groups. The products have been characterized by exclusion liquid chromatography and IR and ¹H NMR studies.     

Condensed tetrazolo-1,3,5-triazines. 4. Synthesis of salts of 5-aminotetrazolo[1,5-a]-1,3,5-triazin-7-one

2-Amino-4-azido-1,3,5-triazin-6(1H)-ones were synthesized by successive substitution of the trinitromethyl groups in 2-amino-4,6-bis(trinitromethyl)-1,3,5-triazines under the influence of azide and nitrite ions. Interaction of 2-amino-4-azido-1,3,5-triazin-6(1H)-ones with bases led to the azido-tetrazole tautomeric conversion give salts of 5-aminotetrazolo[1,5-a]-1,3,5-triazin-7-one. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1211–1219, August, 2006.     

Synthesis of 3 or 3,3′-substituted BINOL ligands and their application in the asymmetric addition of diethylzinc to aromatic aldehydes

Three new substituted BINOL ligands (R)-3-[4,6-bis(dimethylamino)-1,3,5-triazin-2-yl]-1,1′-bi-2-naphthol (R)-1, (R)-3,3′-bis[4,6-bis(dimethylamino)-1,3,5-triazin-2-yl]-1,1′-bi-2-naphthol (R)-2 and 2,4-bis(2,2′-dihydroxy-1,1′-binaphthalen-3-yl)-6-(p-tolyl)-1,3,5-triazine (R,R)-3 have been obtained by directed ortho-lithiation or Suzuki cross-coupling process. Ligand (R)-1 shows improved catalytic properties for the asymmetric diethylzinc addition to aromatic aldehydes.     

Structural isomerism in CuSCN coordination polymers

CuSCN reacts with the angular ligand 2,4-bis(4-pyridyl)-1,3,5-triazine (dpt) to afford rare examples of coordination polymer structural isomers including a non-centrosymmetric three-dimensional framework with Cd(SO4) topology constructed from tetrahedral metal cations.     

Increased sensitivity of an enzyme immunoassay (ELISA) for the determination of triazine herbicides by variation of tracer incubation time

Immunoassays for triazine herbicides were tested for their reaction to the variation of the tracer incubation time. By application of a sequential technique the measuring range of atrazine could be expanded to five decades and the total duration of the test could be reduced to about 30 min. In an optimized version a lower detection limit of 9 pmol/l (2 ng/l) was achieved. The detection limit of a sensitive immunoassay for terbuthylazine is also below the concentration limit demanded of the German drinking water regulation (100 ng/l) and reaches 130 pmol/l (30 ng/l). Short tracer incubation times did not lead to increased cross-reactivities in contrast to theoretical models [1, 2]. Different mechanisms, which could cause a shift of the center point of the calibration curve, are discussed, including kinetic considerations.Nomenclature ametryn 2-(ethylamino)-4-(isopropylamino)-6-(methylthio)-1,3,5-triazine - atrazine 2-(chloro)-4-(ethylamino)-6-(isopropylamino)-1,3,5-triazine - deethylatrazine 2-(amino)-4-(chloro)-6-(isopropylamino)-1,3,5-triazine - DMSO dimethylsulfoxide - DOC dissolved organic carbon - ELISA enzyme-linked immunosorbent assay - glyme 1,2-dimethoxyethane - hydroxyatrazine 2-(ethylamino)-4-(hydroxy)-6-(isopropylamino)-1,3,5-triazine - PBS phosphate buffered saline - propazine 2-(chloro)-4,6-bis(isopropylamino)-1,3,5-triazine - simazine 2-(chloro)-4,6-bis(ethylamino)-1,3,5-triazine - terbuthylazine 2-(tert-butylamino)-4-(chloro)-6-(ethylamino)-1,3,5-triazine - TLC thin-layer chromatography - TMB 3,3,5,5-tetramethylbenzidine - tracer enzyme (peroxidase) labeled hapten     

2,4-双(三氯甲基)-6-(4-甲氧基-1-苯乙烯基)-s-三嗪光引发剂的合成与聚合动力学研究

本研究以4-甲氧基苯甲醛和2,4-双(三氯甲基)-6-甲-基1,3,5-三嗪为原料合成了一种引发剂2,4-双(三氯甲基)-6-(4-甲氧基-1-苯乙烯基)-s-三嗪(BMT),并利用红外光谱、紫外光谱、核磁共振等手段对其结构进行表征.利用实时红外光谱研究其光聚合动力学性能,结果表明,不同引发剂浓度,不同单体和不同光强对单体双键转化率都有一定的影响.     

Non-Glycosidic Azides of D-Altro- and D-Gulopyranose

ABSTRACT

Starting with methyl 2-O-cyclohexylcarbamoyl-3,4-O-(2,2,2-trichloroethylidene)-α-D-altropyranoside (1), methyl 4-O-cyclohexylcarbamoyl-2,3-O-(2,2,2-trichloroethylidene)-β-D-gulopyranoside (12), and methyl 6-O-cyclohexylcarbamoyl-2,3-O-(2,2,2-trichloroethylidene)-β-D-gulopyranoside (21), the 6-azido-6-deoxyaltroses 4, 6, 11, the 6-azido-6-deoxy-D-gulose 14, the 4-azido-4,6-dideoxy-D-gulose 20, and the 4-azido-4-deoxy-D-gulose 26 were synthesised via iodinated or tosylated precursors. Additionally, two gluco-configured azides, the 3-azido-3,6-dideoxy-D-glucose (19) and the 3-azido-3-deoxy-D-glucose (25), were obtained besides the desired 4-azido-4-deoxy-D-gulosides 20 and 26, when methyl 6-deoxy-4-O-tosyl-β-D-gulopyranoside (18) and methyl 6-O-cyclohexylcarbamoyl-4-O-tosyl-β-D-gulopyranoside, respectively, were reacted with sodium azide. An X-ray analysis is presented for methyl 2,4-di-O-acetyl-3-azido-3,6-dideoxy-zl-D-glucose (19).     

A new method for the synthesis of 2,4-diazido-6-trinitromethyl-1,3,5-triazine

A new method for the synthesis of 2,4-diazido-6-trinitromethyl-1,3,5-triazine was elaborated. The method makes it possible to exclude the work with unstable 2,4,6-tris(trinitromethyl)-1,3,5-triazine.     

2,4-diamino-6-(acetohydrazidomethylsulfinylmethyl)-1,3,5-triazine. State in solution, acid-base and complexing properties

Solutions of a new drug, 2,4-diamino-6-(acetylhydrazidomethylsulfonylmethyl)-1,3,5-triazine, exhibiting tuberculocidal activity were studied using the methods of pH-metry, spectrophotometry, mathematical simulation of equilibria (CPESSP software), and molecular mechanics. Protolytic properties of the compound in the medium of aqueous dimethylsulfoxide (40 vol % of DMSO) were characterized. The composition of the copper(II) complex of this compound was determined and its stability constants were calculated. Based on the absorption spectra in the UV and visible regions the complexing ability of 2,4-diamino-6-(acetylhydrazidomethylsulfonylmethyl)-1,3,5-triazine toward nickel(II) and cobalt(II) were characterized in comparison with copper(II) under the same conditions.     

The Oxidation of Hexahydrotriazines

Summary. N-Alkyl-2,4-dioxohexahydro-1,3,5-triazines oxidize readily with oxygen to the corresponding cyanuric acid derivates. The oxidation of 1,3,5-trimethyl-2,4-dioxohexahydro-1,3,5-triazine resulted in a stable form of hydroperoxide. During the oxidation of 1,3,5-trimethyl- 6-phenyl-2,4-dioxohexahydro-1,3,5-triazine this hydroperoxide could not be identified, however, the result was the stable reaction product bis-[6-phenyl-1,3,5-trimethyl-2,4-dioxohexahydro-1,3,5-triazin]peroxide.     

Synthesis and nitration of 3-R-4-(2,2,2-trinitroethyl)aminofuroxans

Simple methods for the synthesis of 3-R-4-(2,2,2-trinitroethyl)aminofuroxans were developed based on the Mannich reaction of N,N′-bis(3-R-furoxan-4-yl)methylenediamines with trinitromethane or 3-R-4-aminofuroxans with trinitroethanol or with CH₂O and trinitromethane. The Mannich bases obtained were studied in the nitration reaction, which showed their ability to form nitramines depending on substituents on the furoxan ring.