2,4,6-三对氨基苯氧基-1,3,5-均三嗪的合成

以三聚氯氰和对硝基苯酚为原料,经取代、还原合成了2,4,6-三对氨基苯氧基-1,3,5-均三嗪。对Pd/C水合肼、SnCl2·2H2O-HCl及Pd/C催化加氢三种不同还原体系进行比较。采用1H-NMR、FT-IR和元素分析方法对产物进行结构表征。     

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.     

Synthesis and Characterization of S-Triazine Cored Tripodal Keto-oxime and Its Trinuclear Complexes

2,4,6-Tris(4-hydroxybenzimino)-1,3,5-triazine (II) has been synthesized by the reaction of 1 equiv. melamine (I) and 3 equiv. 4-hydroxybenzaldehyde and characterized by means of elemental analysis, ¹H NMR, Fourier transform–infrared spectroscopy, and liquid chromatography–mass spectrometry (LC-MS). 2,4,6-tris(4-(2-phenyl-2-keto-hydroxyiminoyloxy)benzimino)-1,3,5-triazine L (III) has been synthesized by the reaction of 1 equiv. II and 3 equiv. chloroisonitrozoacetophenone and characterized by means of the same methods. Four novel trinuclear Fe(III) and Cr(III) complexes involving tetradentate Schiff bases N,N′-bis(salicylidene)ethylenediamine-(salenH₂) or bis(salicylidene)-o-phenylenediamine-(salophen H₂) with L (III) have been synthesized and characterized by means of elemental analysis, Fourier transform–infrared spectroscopy, LC-MS (ESI⁺), and thermal analyses. The metal ratios of the prepared complexes have been determined using atomic absorption spectroscopy. The aim of the present study is to synthesize novel tridirectional-trinuclear systems and to present their effects on magnetic behavior of [salen or salophenFe(III)/Cr(III)] capped complexes. The complexes have also been characterized as low-spin distorted octahedral Fe(III) and as distorted octahedral Cr(III) bridged by keton-oxime group.     

Synthesis, characterization, and energetic properties of diazido heteroaromatic high-nitrogen C-N compound

The synthesis, characterization, and energetic properties of diazido heteroaromatic high-nitrogen C-N compound, 3,6-diazido-1,2,4,5-tetrazine (DiAT), are reported. Its normalized heat of formation (NDeltaHf), experimentally determined using an additive method, is shown to be the highest positive NDeltaHf compared to all other organic molecules. The unexpected azido-tetrazolo tautomerizations and irreversible tetrazolo transformation of DiAT are remarkable compared to all other polyazido heteroaromatic high-nitrogen C-N compounds, for example, 2,4,6-triazido-1,3,5-triazine; 4,4',6,6'-tetra(azido)hydrazo-1,3,5-triazine; 4,4',6,6'-tetra(azido)azo-1,3,5-triazine; and 2,5,8-tri(azido)-1,3,4,6,7,9,9b-heptaazaphenalene (heptazine).     

Porous triazine polymer: A novel catalyst for the three-component reaction

A new porous triazine-based covalent organic polymer (Triazine-COP) was prepared through the Schiff-base condensation of 2,4,6-tris(4-formyl phenoxy)-1,3,5-triazine and 4,4′-oxydianiline, under sonication. The synthesized Triazine-COP with a high surface area was stable in water and other organic solvents. In the next step, Au (III) ions were immobilized on the nitrogen-rich Triazine-COP that on the reduction with NaBH₄ produced the heterogeneous catalyst of gold clusters in nanosize (Au-NCs@Triazine-COPs). It was applied as an efficient catalyst for the A³ coupling reaction of alkynes, aldehydes with and amines. Both electron-withdrawing/releasing groups produced the corresponding propargylamines with high yields. The high activity of the Au-NCs@Triazine-COPs in this reaction was because of the nanoporous structure of the support that enables the high dispersion and an unhindered open environment for the NCs. The catalyst was reused up to 7 times without significant loss in activity.     

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.     

Analysis of explosives using differential mobility spectrometry

Characterization of ions from eight explosives (2,4,6-trinitrotoluene, pentaerythritol tetranitrate, 2,4,6-trinitrophenol, 2,4-dinitrotoluene, erythritol tetranitrate, hexamethylene triperoxide diamine, 2,4,6-trinitrophenylmethylnitramine and 1,3,5-trinitro-perhydro-1,3,5-triazine) using differential mobility spectrometry (DMS) with ⁶³Ni as an ionization source was performed. Presented results of explosive analysis have been evaluated by use of special software tool which communicates with DMS in real time. This tool was developed for visualization, identification and comparison of measured data. Each explosive provides characteristic signal at a specific compensation voltage under a fixed dispersion field. Peaks in DMS spectra for these ions were confined to a range of compensation voltages between ?1.61 to +1.71 V at RF = 1060 V. We calculated specific alpha coefficients (α₂ and α₄) to obtain a nonlinear function of explosives, based on their DMS spectra. Dependence of mobility for measured explosives ions in electric field at E/N values between 0 to 120 Td were used to inspectional graphical differentiation of explosives.     

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.     

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.     

Synthesis of Star-Shaped Macromolecular Schiff Base Complexes Having Melamine Cores and Their Magnetic and Thermal Behaviors

Abstract

We aim to study magnetic and thermal behaviors of some melamine cored macromolecular Schiff base complexes. In this context, tripodal ligands were synthesized by reacting melamine with 4-carboxybenzaldehyde or 4-hydroxybenzaldehyde. Then, 16 new trinuclear Fe(III), Cr(III), Mn(III), and Al(III) complexes were synthesized by reacting the ligands [tris-(4-carboxybenzimino)-1,3,5-triazine) or tris-(4-hydroxybenzimino)-1,3,5-triazine)] with pentadentate Schiff bases N,N′-bis(1-hydroxy-2-benzyliden)-1,7-diamino-4-azaheptane or N,N′-bis(salicylidene)pyridine-2,6-diamine. Later, ligands and complexes were characterized by means of elemental analysis, infrared spectroscopy, ¹H NMR, liquid chromatography–mass spectrometry, thermal analyses, and magnetic susceptibility measurements. Finally, metal ratios of the prepared complexes were determined by using atomic adsorption spectrometry. The complexes were also characterized as distorted octahedral high-spin d ³ (S = 3 × 1/2) Cr(III), high-spin d ⁵ (S = 5 × 1/2) Fe(III), low-spin d ⁴ (S = 2 × 1/2) Mn(III), and diamagnetic Al(III) bridged by ?OH group of COO^? or OH group of phenol.     

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.     

8-hydroxyquinoline based neutral tripodal ionophore as a copper (II) selective electrode and the effect of remote substitutents on electrode properties

New PVC membrane ion selective electrodes based on 1,3,5-Tris(8-quinolinoxymethyl)-2,4,6-trimethylbenzene (MO8HQ) are reported. The basic sensing material belongs to the group of tripodal ionophores. Also their derivatives prepared by placing suitable substitutents at fifth position of 8-oxine moiety, i.e, 1,3,5-Tris(5-chloro-8-quinolinoxymethyl)-2,4,6-trimethylbenzene (5CHQ), 1,3,5-Tris(5-benzoyl-8-quinolinoxymethyl)-2,4,6-trimethylbenzene (5BHQ) and 1,3,5-Tris[(5-phenylhydroxymethylene)-8-quinolinoxymethyl]-2,4,6-trimethylbenzene (HYD-8HQ) ionophores have also been used to make copper-selective membrane electrodes. Among all the four electrodes, MO8HQ and HYD-8HQ ionophores based electrodes show excellent response towards Cu (II) ions. The electrodes having composition 33% PVC, 4% MO8HQ and 63% dibutyl phthalate (DBP) and 33% PVC, 6% HYD-8HQ, 63% dibutyl phthalate (DBP) exhibit a good Nernstian response to Cu (II) ions in the range of 1.0 × 10⁻⁶ to 1 × 10⁻¹ M. The electrode shows a reasonably fast response time of 15 s. The effect of pH and electrode response is also reported. It shows good selectivity for Cu (II) ions in comparison to heavy metal ions, transition metal ions and for alkali and alkaline earth metal ions. The electrode response and selectivity remains unchanged for at least 5 months. The electrode can be used as an indicator electrode in the potentiometric titration of Cu (II) ions with EDTA.     

A new efficient route for the synthesis of 4,4′,6,6′-tetra(azido) azo- 1,3,5-triazine

A new method for the synthesis of 4,4′,6,6′-tetra(azido)azo-1,3,5-triazine(TAAT)is described.The key intermediate 4,4′,6,6′- tetra(azido)hydrazo-1,3,5-triazine(TAHT)was synthesized by nucleophilic substitution in the case of sodium azide as nacleophile. N-Bromosuccinide(NBS)was used as oxidant to oxidize TAHT by a tractable operation under mild reaction condition.The target compound TAAT was obtained with a facile process and high overall yield of 81%.The structures of TAAT and its intermediates were identified by spectroscopic methods.     

Study on side-chain second-order nonlinear optical polyimides based on novel chromophore-containing diamines. I. Synthesis and characterization

Side-chain second-order nonlinear optical polyimides were prepared from four novel chromophore-containing diamines and 4,4′-(hexafluoroisopropylidene) diphthalic anhydride by a traditional two-step process that included a solution polycondensation followed by a chemical imidization. The four diamines were 2,4-di-β-aminoethylamino-6-p-nitrophenylamino-1,3,5-triazine (M1), 4-nitro-4′-[N-(4,6-di-β-aminoethylamino)-1,3,5-triazin-2-yl]amino azobenzene (M2), 2,4-di-p-aminophenylamino-6-p-nitrophenylamino-1,3,5-triazine (M3), and 4-nitro-4′-[N-(4,6- di-4-aminophenylamino)-1,3,5-triazin-2-yl]amino azobenzene (M4). All the polyimides exhibited maximum ultraviolet-visible absorption peaks or shoulders of chromophores at wavelengths below 400 nm, and those based on M1 and M3 were transparent at wavelengths above 450 nm, whereas those based on M2 and M4 were transparent at wavelengths above 550 nm. The polyimides possessed high glass-transition temperatures (T_g's; 218–247 °C) and thermal decomposition temperatures. They were soluble in aprotic solvents such as N-methyl-2-pyrrolidone, N,N-dimethyl acetamide, N,N-dimethyl formamide, and dimethylsulfone. Some were even soluble in common low-boiling-point solvents such as tetrahydrofuran. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4330–4336, 1999     

Phospha-s-triazines. IV. Degradation studies of 1-diarylphospha-3,5-bis(perfluoroaliphatic)-2,4,6-triazines and 1,3,-bis(diarylphospha)-5-perfluoroaliphatic-2,4,6-triazines

Thermal and thermal oxidative stability evaluations were performed on mono- and diphospha-s-triazines at 235 and 316°C using sealed Pyrex ampoules. The specific compounds studied were: 1-diphenylphospa-3,5-bis(perfluoro-n-heptyl)-2,4,6-triazine, 1-diphenylphospha-3,5-bis(perfluoro-alkylether)-2,4,6-triazines, their respective pentafluorophenyl analogues, 1,3-bis(diphenylphospha)-5-perfluoro-n-heptyl-2,4,6-triazine and 1,3-bis(diphenylphospha)-5-perfluoroalkylether-2,4,6-triazine. All the compounds wherein phenyl groups were present on the phosphorous exhibited good thermal stability up to 316°C; the analogous pentafluorophenyl substituted materials were degraded extensively at these temperatures. The oxidative stability of both the mono- and diphospha-s-triazines was excellent at 235°C, but at 316°C some degradation was observed. This was more pronounced in compounds containing the perfluoroalkyl moiety on carbon than in the perfluoroalkylether substituted members of the series.     

Synthesis, characterization, and thermal properties of diacrylic/divinylbenzene copolymers

In this article, synthesis, characterization, and thermal properties of diacrylic/divinylbenzene copolymers based on the new aromatic tetrafunctional acrylate monomers are presented. The new monomers were generated by treatment of epoxides derived from various aromatic diols: naphthalene-2,3-diol (NAF), biphenyl-4,4′-diol (BIF), bis(4-hydroxyphenyl)methanone (BEP) or 4,4′-thiodiphenol (BES), and epichlorohydrin with acrylic acid. The addition reaction was carried out by a ratio of 0.5 mol of suitable epoxy derivative and 1 mol of acrylic acid in the presence of 0.7 wt% of triethylbenzylammonia chloride (TEBAC) as a catalyst and 0.045 wt% of hydroquinone as a polymerization inhibitor. The chemical structure of the prepared acrylate monomers was confirmed by ¹³C NMR and GC MS spectra. The emulsion–suspension polymerization of acrylate monomers with divinylbenzene (DVB) in the presence of pore-forming diluents (toluene + decan-1-ol) allowed obtaining microspheres containing pendant functional groups (hydroxyl groups). This process was carried out at constant mol ratio of acrylate monomers: DVB (1:1), and constant volume ratio of pore-forming diluents to monomers (1:1). The different concentrations of toluene in the mixture with decan-1-ol were used for qualifying the effect of the diluents on the microsphere characteristics. The influence of synthesis’s parameters on the properties of copolymer beads, e.g., pore size and surface area by BET method, the surface texture by AFM, swelling behavior in polar and non-polar solvents as well as thermal stability by differential scanning calorimetry (DSC), and thermogravimetric analysis (TG) was studied and discussed.     

Synthesis and photophysical properties of hyperbranched polyfluorenes containing 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine as the core

A series of new hyperbranched polymers containing a 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core unit and polyfluorene chain arms have been synthesized via Suzuki coupling, and characterized by NMR, IR and GPC. All the polymers exhibit good thermal stability with a high decomposition temperature. By changing the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio the UV-vis absorption and emission spectra can be partially tuned. It has been found that the polymers containing a low ratio of 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine units (P1-P3) have an absorption maximum around 385 nm, localized in the polyfluorene chain, and a shoulder around 425 nm ascribable to a charge transfer state involving the fluorene and the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core. Increasing the molar ratio of the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine unit enhances the charge transfer band which becomes dominant for P4. The LUMO level of these polymers is relatively low due to the electron affinity of the triazine group. The polymers show dual emission, with a structured band in the blue (410-440 nm), attributed to the polyfluorene, and a broad band in the red (470-500 nm) associated with the charge transfer state. All the polymers exhibit two-photon absorption activity in the range of 660 to 900 nm with the maximum two-photon absorption (TPA) cross-section red-shifted from the corresponding linear absorption. The values of the TPA cross-sections vary from 1000 to 5000 GM, following the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio.     

Aromatic polyethers with 1,3,5-triazine units as hole blocking/electron transport materials in leds

Various difluoro functionalized aromatic 1,3,5-triazine monomers were prepared. A series of poly-(1,3,5-triazine-ether)s was synthesized by polycondensation with 4,4′-(hexafluoroisopropylidene)diphenol. The polymers have excellent thermal stability and are amorphous with glass transition temperatures in the range of 190–250°C. In order to examine the potential to apply these polymers in organic electroluminescent devices, the redox properties were studied by cyclic voltammetry. It was found that the monomers have high electron affinity and reach LUMO values in the range of −2.7 to −3.1 eV. This opens the possibility to utilize 1,3,5-triazine containing materials as electron injecting/hole blocking layer in LEDs. First LED results are in accordance to these high electron affinities.     

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.     

Linear and star-shaped polynuclear Ru(II) complexes of 2-(2'-pyridyl)benzimidazolyl derivatives: syntheses, photophysical properties and red light-emitting devices

Two new star-shaped ligands with a 1,3,5-triphenylbenzene core, tmpb (1,3,5-tris[p-2-(2'-pyridyl)benzimidazolylphenyl]benzene), and a 2,4,6-tris(p-biphenyl)-1,3,5-triazine core, tmbt (2,4,6-tris[p-2-(2'-pyridyl)benzimidazolylbiphenyl]-1,3,5-triazine), have been synthesized. Their corresponding trinuclear Ru(II) complexes [Ru3(tmpb)(bpy)6](PF6)6 (3) and [Ru3(tmpt)(bpy)6](PF6)6 (4) have been obtained. Two dinuclear linear Ru(II) complexes with previously reported ligands bmb (1,4-bis[2-(2'-pyridyl)benzimidazolyl]benzene) and bmbp (4,4'-bis[2-(2'-pyridyl)benzimidazolyl]biphenyl) and formulae [Ru2(bmb)(bpy)4](PF6)4 (1) and [Ru2(bmbp)(bpy)4](PF6)4 (2) have also been synthesized. Photophysical and electrochemical properties of the new compounds have been investigated. All four compounds display a characteristic metal-to-ligand-charge transfer (MLCT) absorption band and emit a red light when excited at the maximum of the MLCT band with emission maximum at 624, 629, 623 and 625 nm, respectively in neat films at ambient temperature. The emission quantum efficiency of the four complexes in neat films was determined to be 0.15, 0.17, 0.04 and 0.05, respectively. Light emitting devices based on these four compounds were fabricated by spin-casting the compound as a neat film to an ITO substrate, followed by the deposition of an aluminium metal layer. All devices emit a deep red light and the device behavior resembles that of a light emitting electrochemical cell. The EL maximum of the devices 1, 2, 3, and 4 is at 637, 657, 678, and 655 nm, respectively. All four devices have a fast response time when a sufficiently high voltage is applied. The device based on 2 is the brightest with a maximum luminance of 133 cd m(-2) at 7 V. The performance of devices based on 1, 2, and 4 is in general much more efficient than the device based on [Ru(bpy)3](PF6)2, which was fabricated and evaluated under the same experimental conditions as for the devices based on 1-4.