Nucleophilic substitution reactions of 2,4,6-tris(trinitromethyl)-1,3,5-triazine. 2. interaction of 2,4,6-tris(trinitromethyl)-1,3,5-triazine with primary amines and hexamethyldisilazane

2-R-amino-4,6-bis (trinitromethyl)-1,3,5-triazines have been synthesized, and their structures have been established. Dynamic¹³C NMR spectroscopy has been used to measure the rotational barriers of the tertbutylamino group around the C₍₂₎-NHBu-t bond in 2-(tert-butylamino)-4,6-dichloro-1, 3, 5-triazine and 2-(tertbutylamino)-4,6-dimethoxy-1,3,5-triazine. X-ray diffraction was used to investigate the structure of 2-(tertbutylamino)-4,6-bis (trinitromethyl)-1,3,5-triazine. From the results obtained in this work it has been concluded that the bond between the NHBu-t group and the triazine ring has a partial double-bond character.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from ] Khimiya Geterotsikiicheskikh Soedinenii, No. 5, pp. 679–688 May, 1995. Original article submitted March 7, 1995.     

Crystal Structures and Packing of 2,4,6-tris(4-Fluorophenoxy)-1,3,5-triazine and 2,4,6-tris(3,4-Dimethylphenoxy)-1,3,5-triazine. New Materials for Octupolar Nonlinear Optics

The crystal structures and packing of 2,4,6-tris(4-fluorophenoxy)-1,3,5-triazine and 2,4,6-tris(3,4-dimethylphenoxy)-1,3,5-triazine are discussed. These structures have been determined as a continuation of a series of octupolar NLO materials we have been investigating. The crystal structures are characterized by C–H...F and C–H... hydrogen bonds, respectively. A characteristic of these triazine structures is the presence of dimeric Piedfort Units (PU) that are extended into more elaborate two-dimensional (2-D) networks. The structure of the fluoro derivative is compared with that of the corresponding unsubstituted and chloro/bromo-substituted derivatives. The structure of the dimethyl triazine is compared with that of the corresponding 4-methyl derivative. The noncentrosymmetric nature of the dimethyl derivative was confirmed by a powder SHG signal at 1.064 m of the order of 0.5 × KDP. Interestingly, the dimethyl derivative studied here is isostructural with the corresponding 4-methyl triazine. This H/Me isostructurality is shown to be an uncommon phenomenon by an analysis with the CSD.     

An efficient and facile one-pot synthesis of structurally unique 2,4,6-tris(arylchalcogeno)-1,3,5-triazine and 1,3,5-tris(arylchalcogeno)-2,4,6-trimethylbenzene

An efficient one-pot synthesis of a novel class of 2,4,6-tris(arylchalcogeno)-1,3,5-triazine (sulfur, selenium and tellurium) and 1,3,5-tris(arylchalcogeno)-2,4,6-trimethylbenzene (sulfur and selenium)-containing ligands has been developed based on the reaction of 2,4,6-trichloro-1,3,5-triazine and 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene with the corresponding arylchalcogenide anions generated in aqueous tetrahydrofuran.     

Thermodynamic stability of 2,4,6-tris(nitromethyl)-1,3,5-triazine: an experimental and theoretical study

The molecular geometries and electronic structures of 2,4,6-tris(nitromethyl)-1,3,5-triazine isomers were investigated by the density functional method DFT/B3LYP/6-311++G** to elucidate the structural factors responsible for the stability of these systems. It was shown that a characteristic feature of the nitromethyl tautomer (1) of 2,4,6-tris (nitromethyl)-1,3,5-triazine consists in nonvalence interactions between an oxygen atom of nitro group and a carbon atom of triazine ring, which are probably due to Coulomb attraction between them. The tautomer with the 2,4,6-tris (nitromethylene)-hexahyrdo-1,3,5-triazine structure (2) is stabilized trough direct polar conjugation between the amino and nitro groups at the double bond. Structural strain of the molecule with the 2,4,6-tris(aci-nitromethyl)-1,3,5-triazine structure (3) is the reason for its thermodynamic instability. X-ray data indicate that the compound under study exists in the triazine tautomeric form 1 and the distances between oxygen atoms of nitro group and carbon atom of the triazine ring are shortened. NMR data suggest the existence of triazine in the nitromethyl form 1 in acetonitrile and acetone and a tautomeric equilibrium between the nitromethyl and nitromethylene forms in a more polar solvent (DMSO). The results obtained suggest a Coulomb-type stabilization of the 2,4,6-tris(nitromethyl)-1,3,5-triazine molecule in the gas phase, in the crystal, and in nonpolar solvents.     

Nucleophilic substitution reactions of 2,4,6-tris(trinitromethyl)-1,3,5-triazine. 1. Interaction of 2,4,6-tris(trinitromethyl)-1,3,5-triazine with alcohols,diols, ammonia,and secondary amines

A study has been made of nucleophilic substitution reactions of 2,4,6-tris(trinitromethyl)-1,3,5-triazine with certain nucleophiles. The possibility of replacing one, two, or three trinitromethyl groups in this compound has been demonstrated.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 674–678, May, 1995. Original article submitted February 28, 1995.     

The structure of 2,4,6-tris[di(tert-butoxycarbonyl)methylidene]-hexahydro-1,3,5-triazine

The structure of 2,4,6-tris[di(tert-butoxycarbonyl)methylidene]hexahydro-1,3,5-triazine was studied by quantum chemistry, NMR and IR spectroscopy, and X-ray diffraction. This compound exists exclusively in the hexahydro-1,3,5-triazine form both in solution and in the solid phase, although due to the loss of the aromatization energy, this structure should be less stable than a 1,3,5-triazine structure. The formation of strong intramolecular hydrogen bonds confirmed by NMR and IR spectroscopy and X-ray diffraction data may be a main reason for stabilization of the hexahydro-1,3,5-triazine isomer. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1022–1026, June, 2006.     

Inclusion of tetramethylpyrazine in channels of the organic zeolite 2,4,6-tris(4-bromophenoxy)-1,3,5-triazine

2,4,6-tris(4-bromophenoxy)-1,3,5-triazine (BrPOT) features a channel size (11–12 Å) allowing the inclusion of large guest molecules such as tetramethylpyrazine (TMPZ). TMPZ forms π-stacks (d: 3.5 Å) along channels of BrPOT and shows rotational disorder for methyl positions. Co-inclusions of I₂ resulted in a doped state where I₂ molecules are oriented perpendicular to the channel axis with positional disorder as well. The particular orientation of I₂ molecules is evident from the observed dichroism.     

Trisubstituted 1,3,5-triazines. 2. Synthesis of 1,3,5-triazines from 2,4,6-tris[di(tert-butoxycarbonyl)methylene]hexahydro-1,3,5-triazine

A study was carried out on electrophilic addition and hydrolytic dissociation of 2,4,6-tris[di(tert-butoxycarbonyl)methylene]hexahydro-1,3,5-triazine. Chloro, bromo, and methyl derivatives of tris[di(tert-butoxycarbonyl)methyl]-1,3,5-triazine were synthesized for the first time as well as 2,4,6-tris-(tert-butoxycarbonylmethyl)-1,3,5-triazine. For Communication 1, see ref. [1]. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow and Institute of Chemical Physics, Russian Academy of Sciences at Chernogolovka, 142432 Chernogolovka, Moscow Oblast. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1404–1407, October, 1998.     

Trisubstituted 1,3,5-Triazines. 6. Synthesis of 2,4,6-Tris(acetonyl)-1,3,5-triazine

Acylation of 2,4,6-tris(tert-butoxycarbonylmethyl)-1,3,5-triazine with acetic anhydride in the presence of lithium hydride with subsequent removal of the tert-butoxycarbonyl groups with trifluoroacetic acid leads to 2,4,6-tris(acetonyl)-1,3,5-triazine, the cyclic analog of -cyanoacetone. The special spectral features of this compound compared with triazines obtained previously are discussed.     

Nucleophilic Substitution Reactions of 2,4,6-Tris(trinitromethyl)-1,3,5-triazine. 3. Reaction of 2,4,6-Tris(trinitromethyl)-1,3,5-triazine with Azides and Hydrazine

As a result of nucleophilic substitution of the trinitromethyl groups in 2,4,6-tris(trinitromethyl)-1,3,5-triazine, the corresponding monoazido and diazido derivatives have been synthesized. The reaction of the starting triazine with hydrazine acetate in the presence of trifluoroacetic acid leads to 1-acetyl-2,2-bis[4,6-bis(trinitromethyl)-1,3,5-triazin-2-yl]hydrazine.     

Reaction of 2,4,6-triazido-1,3,5-triazine with triphenylphosphane. syntheses and characterization of the novel 2-triphenylphosphanimino-4-azidotetrazolo[5,1-a]-[1,3,5]triazine and 2,4,6,-tris(triphenylphosphanimino)-1,3,5-triazine

2-Triphenylphosphanimino-4-azidotetrazolo[5,1-a]-[1,3,5]triazine (6) was obtained by reaction of 2,4,6-triazido-1,3,5-triazine (1) with 1 equiv of triphenylphosphane. Raman and X-ray data revealed that only one azide group formed a tetrazole ring system whereas the second azide group did not undergo ring closure. To investigate the equilibrium between the tetrazole isomer and the open-chain azide structure for these and related species, (31)P NMR studies were carried out. The obtained spectra displayed an equilibrium between the tetrazole and the open-chain azide isomers. 2,4,6-Tris(triphenylphosphanimino)-1,3,5-triazine (4) was prepared by treatment of 1 with 3 equiv of triphenylphosphane, and its X-ray structure is discussed. On the basis of PM3 semiempirical and density functional calculations, the reaction of 1 with triphenylphosphane was studied. The thermodynamics of different isomerization reactions and the activation barriers to cyclization were estimated.     

Syntheses and crystal structures of copper(II) complexes derived from 2,4,6-tris(2-pyridyl)-1,3,5-triazine

Treatment of freshly precipitated Cu(OH)₂?·?xH₂O and 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) with oxalic and malonic acids in methanol-water at room temperature gave [Cu(tptz)(C₂O₄)(H₂O)]?·?4H₂O (1) and [Cu(pma)(C₃H₂O₄)(H₂O)]?·?H₂O (2) (pma?=?2-aminocarbonylpyridine), respectively. Reaction in the absence of any acid resulted in [Cu(bpca)(tca)]?·?2H₂O (3) (bpca?=?bis(2-pyridylcarbonyl)amide anion; tca?=?2-pyridinecarboxylate anion). Complex 1 consists of [Cu(tptz)(C₂O₄)(H₂O)] and lattice H₂O molecules; the tridentate tptz ligand, bidentate oxalate dianion and an aqua ligand are bound to Cu with distorted octahedral geometry. Complex 2 is composed of [Cu(pma)(C₃H₂O₄)(H₂O)] and lattice H₂O molecules; the bidentate 2-aminocarbonylpyridine ligand, a bidentate malonate dianion and an aqua ligand are coordinated to Cu with a slightly distorted square pyramidal geometry. Complex 3 consists of [Cu(bpca)(tca)] and lattice H₂O molecules. Square pyramidally coordinated Cu atoms are surrounded by tridentate bpca with nitrogen donor atoms and a bidentate 2-pyridinecarboxylate anion.     

Trisubstituted 1,3,5-triazines 3. Synthesis of substituted 2,4,6-tris(hydroxyiminomethyl)-1,3,5-triazines

Previously undescribed substituted 2,4,6-tris(hydroxyiminomethyl)-1,3,5-triazines, including 2,4,6-(1,3,5-triazinetriyl)trinitrolic acid, have been synthesized.For Communication 2, see [1].N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 117913. Institute of Chemical Physics in Chernoglovka, Chernoglovka, Moscow Oblast, 142432, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 76–78, January, 1999.     

Coordination chemistry of 2,4,6-tri(pyridyl)-1,3,5-triazine ligands

This review covers the rich coordination chemistry of 2,4,6-tri(pyridyl)-1,3,5-triazine ligands. These polypyridyl derivatives have been coupled to transition metals and lanthanides, and the complexes obtained have been used in various fields such as luminescent materials, for the preparation of coordination polymers and networks as well as for the synthesis of discrete metalla-assemblies. The synthetic and structural aspects of the different isomers of 2,4,6-tri(pyridyl)-1,3,5-triazine are presented, and a survey of their coordination chemistry is given.     

A trinuclear copper(II) complex of 2,4,6-tris(di-2-pyridylamine)-1,3,5-triazine shows prominent DNA cleavage activity

A highly water soluble 3:2 complex of copper(II) and 2,4,6-tris(di-2-pyridylamine)-1,3,5-triazine (TDAT) has been synthesized and structurally characterized. The complex crystallized in a triclinic P1 space group with a molecular formula of [Cu3(TDAT)2Cl3]Cl3.2H2O (1), where each copper ion is coordinated by four pyridine nitrogen atoms and an apical chloride. The trinuclear complex is stable at physiological relevant conditions. It can bind to DNA through electrostatic attraction and cleave efficiently the supercoiled pBR322 DNA into its nicked and linear forms at micromolar concentrations. Active oxygen intermediates such as hydroxyl radicals and singlet oxygen generated in the presence of 1 may act as active species for the DNA scission.     

2,4,6-三(芳基氨基)-1,3,5-三嗪衍生物的合成方法和微波效应研究

用碳酸氢钠作扑酸剂,将芳香胺和氰尿酰氯在1,4-二氧六环中回流状态下反应合成了7个2,4,6-三(芳基氨基)-1,3,5-三嗪衍生物,其中6个是新化合物.与已有文献报道的方法相比,条件温和,易于操作,收率高.所合成化合物的结构通过元素分析,FAB-MS,IR确定.在二氧六环:DMF为10:3(V:V)的混合溶剂中,研究了在微波照射下和常规加热下反应速率的差异.结果表明,微波加热比常规加热下的反应速率至少高10倍以上.