Metal‐Free Multicomponent Synthesis of (α‐Aminoalkyl)phosphonates Using 2,4,6‐Trichloro‐1,3,5‐triazine

(α‐Aminoalkyl)phosphonates have efficiently been synthesized by multicomponent reaction of aldehydes, amines, and triethyl phosphite in the presence of 2,4,6‐trichloro‐1,3,5‐triazine at room temperature. The products are formed in high yields (83–91%) within 0.5–1 h.     

TCT‐DMSO/[bmim]BF4: A novel promoter system for the synthesis of 3,5‐diaryl‐1,2,4‐thiadiazoles at ambient temperature

An efficient and practical procedure for direct synthesis of 3,5‐diaryl‐1,2,4‐thiadiazoles by thioamides with 2,4,6‐trichloro‐1,3,5‐triazine (TCT) and dimethylsulfoxide using 1‐butyl‐3‐methylimidazolium tetrafluoroborate as an eco‐friendly reaction medium under ambient temperature is described. This protocol can be considered as a new procedure for 3,5‐diaryl‐1,2,4‐thiadiazoles synthesis. J. Heterocyclic Chem., (2010).     

Linear π‐conjugated polymers containing 2,4,6‐tris(thiophen‐2‐yl)‐1,3,5‐triazine unit: Synthesis and optical properties

Some linear π‐conjugated polymers containing 2,4,6‐tris(thiophen‐2‐yl)‐1,3,5‐triazine unit were synthesized via Sonogashira or Suzuki reaction for the first time and characterized by IR, NMR, and GPC. Because of the introduction of 2,4,6‐tris(thiophen‐2‐yl)‐1,3,5‐triazine unit into π‐conjugated system, all polymers exhibited good thermal stability with high decomposition temperature. Their optical and electrochemical properties were investigated. Based on the 2,4,6‐tris(thiophen‐2‐yl)‐1,3,5‐triazine unit linked with different aromatic rings, the polymers showed the tunable fluorescence from blue to blue‐green emission with satisfied quantum yield. Cyclic voltammetry measurement indicated that the LUMO and HOMO levels of the polymers could be adjustable through the main‐chain structural modification. All polymers had low LUMO level (?2.86 to ?3.06 eV) due to the high‐electron affinity of triazine unit. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 702–712, 2008     

Synthesis and Catalytic Activity of a Grubbs‐Hoveyda Pre‐catalyst Having a Trimeric Resting State

A Grubbs‐Hoveyda pre‐catalyst having a trimeric resting state based on 2,4,6‐trichloro‐1,3,5‐triazine was synthesized and the complex was characterized by NMR, HRMS and elemental analysis. The activity of this complex for ring‐closing metathesis (RCM) was investigated. The catalytic system possesses high catalytic activity for many different olefin substrates.     

Preparation of a stationary phase with s‐triazine ring embedded group for reversed phase high‐performance LC

This paper describes the synthesis and chromatographic evaluation of a new polar‐embedded stationary phase, which utilized 2,4,6‐trichloro‐1,3,5‐triazine as the spacer. The resulting materials were characterized by elemental analysis, IR, and solid‐state ¹³C NMR. Empirical test mixtures were utilized to evaluate the column, and showed that it had good performance for basic compounds and high selectivity for polyaromatic hydrocarbons. Moreover, the novel stationary phase has unique property, especially in the separation of “homologous alkaloids” from natural products.     

Chitosan‐Supported Ni particles: An Efficient Nanocatalyst for Direct Amination of Phenols

A practical method for the direct amination of phenols using 2,4,6‐trichloro‐1,3,5‐triazine (TCT) as an efficient promotor for the activation of phenols in the presence of an efficient and recyclable heterogeneous catalyst prepared by immobilization of nickel particles on triazole modified chitosan is described. This heterogeneous catalyst has demonstrated a promising activity for the conversion of phenolic compounds to their corresponding amine under mild conditions. Moreover, the obtained catalyst can be reused in five consecutive runs with consistent catalytic activity.     

Synthesis,Characterization, and Energetic Properties of 6‐Amino‐tetrazolo[1,5‐b]‐1,2,4,5‐tetrazine‐7‐N‐oxide: A Nitrogen‐Rich Material with High Density

The synthesis and energetic properties of a novel N‐oxide high‐nitrogen compound, 6‐amino‐tetrazolo[1,5‐b]‐1,2,4,5‐tetrazine‐7‐N‐oxide, are described. Resulting from the N‐oxide and fused rings system, this molecule exhibits high density, excellent detonation properties, and acceptable impact and friction sensitivities, which suggests potential applications as an energetic material. Compared to known high‐nitrogen compounds, such as 3,6‐diazido‐1,2,4,5‐tetrazine (DiAT), 2,4,6‐tri(azido)‐1,3,5‐triazine (TAT), and 4,4′,6,6′‐tetra(azido)azo‐1,3,5‐triazine (TAAT), a marked performance and stability increase is seen. This supports the superior qualities of this new compound and the advantage of design strategy.     

Efficient 2,4,6‐trichloro‐1,3,5‐triazine‐catalyzed synthesis of 2‐arylbenzothiazoles and bisbenzothiazoles by condensation of 2‐aminithiophenol with aldehydes under mild conditions

2,4,6‐Trichloro‐1,3,5‐triazine efficiently catalyzed the condensation reactions between 2‐aminothiophenol and aromatic aldehydes to afford 2‐arylbenzothiazolles in good‐to‐excellent yields. Simple and mild reaction conditions, the use of a cheap catalyst and easy work up, and isolation are notable features of this method. J. Heterocyclic Chem., (2011).     

The preparation of covalent triazine‐based framework via Friedel‐Crafts reaction of 2,4,6‐trichloro‐1,3,5‐triazine with N,N′‐diphenyl‐N,N′‐di(m‐tolyl)benzidine for capturing and sensing to iodine

The covalent triazine‐based framework (TDPDB) has been prepared by Friedel‐Crafts polymerization reaction of N,N′‐diphenyl‐N,N′‐di(m‐tolyl)benzidine (DPDB) with 2,4,6‐trichloro‐1,3,5‐triazine (TCT) catalyzed by methanesulfonic acid. The yield of the reaction (94.85%) is very high. TDPDB was provided with Brunauer‐Emmett‐Teller specific surface area of 592.18 m² g^?1 and pore volume of 0.5241 cm³ g^?1. TDPDB demonstrated an excellent capacity for capturing iodine (3.93 g g^?1) and an outstanding ability to fluorescent sensing to iodine with Ksv of 5.83 × 10⁴ L mol^?1. It also showed high fluorescent sensing sensitivity to picric acid.     

Selective and Efficient Formylation of Indoles (C3) and Pyrroles (C2) Using 2,4,6‐Trichloro‐1,3,5‐Triazine/Dimethylformamide (TCT/DMF) Mixed Reagent

This study introduces an efficient method for the selective formylation of indoles and pyrroles at the positions of C(3) and C(2), respectively. The mixture of three equivalents of N ,N‐dimethylformamide and one equivalent of 2,4,6‐trichloro‐1,3,5‐triazine (cyanuric chloride) generates an easy handling formylating agent for the efficient formylation of these classes of compounds to give the corresponding aldehydes under mild reaction conditions. This procedure was highly efficient, and a range of formylated indoles and pyrroles were obtained in good to excellent yields.     

Synthesis and Investigation of Soluble Polymer-supported Dendrimers

Poly（ethylene glycol） （PEG）-supported dendrimers have been synthesized using 2.4,6-trichloro-1,3,5-triazine （TCT） as dendrons and tris（hydroxymethyl）aminomethane as tinkers with high loading capacity, excellent solubility and thermal stability by divergent method. The new synthesized PEG-supported G2.0 dendrimer has 10 times as large functional group loading capacity as commercial PEG3400 with overall yield 44.0%.     

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．     

Controlled Covalent Functionalization of Thermally Reduced Graphene Oxide To Generate Defined Bifunctional 2D Nanomaterials

A controlled, reproducible, gram‐scale method is reported for the covalent functionalization of graphene sheets by a one‐pot nitrene [2+1] cycloaddition reaction under mild conditions. The reaction between commercially available 2,4,6‐trichloro‐1,3,5‐triazine and sodium azide with thermally reduced graphene oxide (TRGO) results in defined dichlorotriazine‐functionalized sheets. The different reactivities of the chlorine substituents on the functionalized graphene allow stepwise post‐modification by manipulating the temperature. This new method provides unique access to defined bifunctional 2D nanomaterials, as exemplified by chiral surfaces and multifunctional hybrid architectures.     

Aptamer‐affinity column clean‐up coupled with ultra high performance liquid chromatography and fluorescence detection for the rapid determination of ochratoxin A in ginger powder

Aptamers are single‐stranded oligonucleotides with high affinity and specificity and are widely used in targets separation and enrichment. Here, an aptamer‐affinity column (AAC) was firstly prepared in‐house through a covalent immobilization strategy. Then, ochratoxin A (OTA) in ginger powder was absorbed and enriched using the new aptamer‐based clean‐up technology for the first time, and was further analyzed by ultra high performance liquid chromatography with fluorescence detection. After optimization, the average recoveries for blank samples spiked with OTA at 5, 15, and 45 μg/kg ranged from 85.36 to 96.83%. Furthermore, the AAC exhibited a similar accuracy as an immunoaffinity column to clean up OTA in ginger powder. Above all, it exhibited better reusability, twice that of the immunoaffinity column, had lower toxicity and cost, and took less time. Of 25 contaminated ginger powder samples, OTA contamination levels ranged from 1.51 to 4.31 μg/kg, which were lower than the European Union (EU) regulatory limits. All the positive samples were further confirmed by ultra‐fast LC with MS/MS. In conclusion, the method of clean‐up based on the AAC coupled to ultra‐HPLC with fluorescence detection was rapid, specific, and sensitive for the quantitative analysis of OTA in a complex matrix.     

Mono‐ and Bis(tetrathiafulvalene)‐1,3,5‐Triazines as Covalently Linked Donor–Acceptor Systems: Structural,Spectroscopic, and Theoretical Investigations

Reaction of 2,4,6‐trichloro‐1,3,5‐triazine with lithiated tetrathiafulvalene (TTF) in stoichiometric conditions, followed by treatment with sodium methanolate, provides mono‐ and bis(TTF)–triazines as new covalently linked (multi)donor–acceptor systems. Single‐crystal X‐ray analyses reveal planar structures for both compounds, with formation of peculiar segregated donor and acceptor stacks for the mono(TTF)–triazine compound, while mixed TTF–triazine stacks establish in the case of the bis(TTF) derivative. Cyclic voltammetry measurements show reversible oxidation of the TTF units, at rather low potential, with no splitting of the oxidation waves in the case of the dimeric TTF, whereas irreversible reduction of the triazine core is observed. Intramolecular charge transfer is experimentally evidenced through solution electronic absorption spectroscopy. Time‐dependent DFT calculations allow the assignment of the charge transfer band to singlet transitions from the HOMO of the donor(s) to the LUMO of the acceptor. Solution EPR measurements correlated with theoretical calculations were performed in order to characterize the oxidized species. In both cases the spectra show very stable radical species and contain a triplet of doublet pattern, in agreement with the coupling of the unpaired electron with the three TTF protons. The dication of the bis(TTF)–triazine is paramagnetic, but no spin–spin exchange interaction could be detected.     

Persistent Organic High‐Spin Trinitrenes

The septet ground state trinitrenes 1,3,5‐trichloro‐2,4,6‐trinitrenobenzene and 1,3,5‐tribromo‐2,4,6‐trinitrenobenzene were isolated in inert (Ar, Ne, and Xe) as well as reactive matrices (H₂, O₂, and H₂O) at cryogenic temperatures. These trinitrenes were obtained in high yields by UV photolysis of the corresponding triazides and characterized by IR and UV/Vis spectroscopy. The trinitrenes, despite bearing six unpaired electrons, are remarkably unreactive towards molecular oxygen and hydrogen and are persistent in water ice up to 160 K where the water matrix starts to sublime off.     

Theoretical studies on the formation mechanism and explosive performance of nitro‐substituted 1,3,5‐triazines

To develop new highly energetic materials, we have considered the design of molecules with high nitrogen content. Possible candidates include 1,3,5‐triazine derivatives. In this work, we studied potential synthetic routes for melamine using the MP2/6‐31+G(d,p)//B3LYP/6‐31G(d) level of theory. The mechanisms studied here are stepwise mechanism beginning with the dimerization of cyanamide and one‐step termolecular mechanism. The same type of mechanism is also applied to nitro‐substituted 1,3,5‐triazines. Values for the heat of formation in the solid phase were predicted from density functional theory calculations. Densities were estimated from a regression equation obtained by molecular surface electrostatic potentials. The Cheetah program was used to study the explosive performance of these compounds. In this study, we found that the explosive properties of 2‐amino‐4, 6‐dinitro‐1, 3,5‐triazine (ADNTA), and 2,4,6‐trinitro‐1,3,5‐triazine (TNTA) are similar to those of RDX and HMX, respectively. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

Boronate affinity monolithic column incorporated with graphene oxide for the in‐tube solid‐phase microextraction of glycoproteins

A poly(vinylphenylboronic acid–ethylene glycol dimethacrylate) monolithic material incorporated with graphene oxide was synthesized inside a poly(ether ether ketone) tube. This tube with boronate affinity monolith was coupled with a high‐performance liquid chromatography system through a six‐port valve to construct an online solid‐phase microextraction with high‐performance liquid chromatography system. The performance of this solid‐phase microextraction with high‐performance liquid chromatography system was demonstrated by standard glycoprotein in aqueous samples, namely, horseradish peroxidase. Some parameters that affect the extraction performance were investigated, including sampling rate, pH of sample solution, and sampling volume. Under the optimized conditions, the developed method showed high extraction efficiency toward horseradish peroxidase. The addition of graphene oxide greatly increased the extraction efficiency of boronate affinity monolith for horseradish peroxidase. The limit of detection of the proposed method was as low as 0.01 μg/mL by using ultraviolet detection. The recognition specificity was also evaluated by analyzing the mixture of bovine serum albumin (nonglycoprotein) and horseradish peroxidase. The results showed that this material could selectively extract horseradish peroxidase from the mixture, indicating its good specificity toward glycoproteins. The proposed method was further applied for analyzing rat plasma samples spiked with horseradish peroxidase. Good recovery and repeatability were obtained.     

The ESI CAD fragmentations of protonated 2,4,6‐tris(benzylamino)‐ and tris(benzyloxy)‐1,3,5‐triazines involve benzyl–benzyl interactions: a DFT study

The electrospray ionization collisionally activated dissociation (CAD) mass spectra of protonated 2,4,6‐tris(benzylamino)‐1,3,5‐triazine (1) and 2,4,6‐tris(benzyloxy)‐1,3,5‐triazine (6) show abundant product ion of m/z 181 (C₁₄H₁₃⁺). The likely structure for C₁₄H₁₃⁺ is α‐[2‐methylphenyl]benzyl cation, indicating that one of the benzyl groups must migrate to another prior to dissociation of the protonated molecule. The collision energy is high for the ‘N’ analog (1) but low for the ‘O’ analog (6) indicating that the fragmentation processes of 1 requires high energy. The other major fragmentations are [M + H‐toluene]⁺ and [M + H‐benzene]⁺ for compounds 1 and 6, respectively. The protonated 2,4,6‐tris(4‐methylbenzylamino)‐1,3,5‐triazine (4) exhibits competitive eliminations of p‐xylene and 3,6‐dimethylenecyclohexa‐1,4‐diene. Moreover, protonated 2,4,6‐tris(1‐phenylethylamino)‐1,3,5‐triazine (5) dissociates via three successive losses of styrene. Density functional theory (DFT) calculations indicate that an ion/neutral complex (INC) between benzyl cation and the rest of the molecule is unstable, but the protonated molecules of 1 and 6 rearrange to an intermediate by the migration of a benzyl group to the ring ‘N’. Subsequent shift of a second benzyl group generates an INC for the protonated molecule of 1 and its product ions can be explained from this intermediate. The shift of a second benzyl group to the ring carbon of the first benzyl group followed by an H‐shift from ring carbon to ‘O’ generates the key intermediate for the formation of the ion of m/z 181 from the protonated molecule of 6. The proposed mechanisms are supported by high resolution mass spectrometry data, deuterium‐labeling and CAD experiments combined with DFT calculations. Copyright © 2012 John Wiley & Sons, Ltd.     

Condensation of Aryl Aldehydes, 2‐naphthol,and Thioacetamide Catalyzed by N‐halo Reagents in Neutral Media

A new three‐component, highly efficient and solvent‐free approach for the synthesis of known and new 1‐thioamido‐alkyl‐2‐naphthol derivatives was investigated. This was achieved via a one‐pot condensation by reacting aryl aldehydes, 2‐naphthol, and thioacetamide in the presence of catalytic amount of 1,3,5‐trichloro‐1,3,5‐triazinane‐2,4,6‐trione (TCCA) and 1,3‐dichloro‐5,5‐dimethylhydantoin (DCDMH). Mechanistically, the in situ generation of Cl⁺ ion from TCCA and DCDMH is proposed to catalyse the reactions in neutral media. In the presented work, most of the products have been reported for the first time.