Novel refreshable N‐halamine polymeric biocides containing imidazolidin‐4‐one derivatives

A novel cyclic‐amine monomer, 1‐acryloyl‐2,2,5,5‐tetramethylimidazolidin‐4‐one (ACTMIO), was synthesized in a good yield through the reaction of acryloyl chloride with 2,2,5,5‐tetramethylimidazolidin‐4‐one and was fully characterized with Fourier transform infrared and ¹H NMR studies. ACTMIO was copolymerized with several widely used acrylic and vinyl monomers under ordinary conditions. In the presence of triallyl‐1,3,5‐triazine‐2,4,6(1H,3H,5H)‐trione, ACTMIO was easily grafted onto most textile fabrics. After regular chlorine bleach treatment, N‐halamine derivatives of the corresponding polymeric materials exhibited antibacterial properties against Escherichia coli, and these properties were durable and refreshable with chlorine bleaching. The relationship between the structures and antibacterial properties of the samples is further discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3073–3084, 2001     

Preparation of antibacterial cellulose with a monochloro‐s‐triazine‐based N‐halamine biocide

A novel monochloro‐s‐triazine‐based N‐halamine precursor, 4‐(4‐(5,5‐dimethylhydantoin‐3‐ethylamino)‐6‐chloro‐1,3,5‐triazinylamino)‐benzenesulfonate (HB), was synthesized and characterized by proton nuclear magnetic resonance. The reactive dyes dyeing method was applied to bond HB onto cotton fabrics, and the treated fabrics were confirmed by Fourier transform infrared spectrometer and scanning electron microscope. The chlorinated HB‐treated fabrics showed excellent antibacterial efficacies against Staphylococcus aureus and Escherichia coli O157:H7 and inactivated all inoculated bacteria within 1 min of contact. Interestingly, it was found that the finishing process and following chlorination caused smaller tensile strength loss of cotton fabrics than the traditional pad‐dry‐cure method. Furthermore, the antimicrobial cotton fabrics exhibited good stability and regenerability. Copyright © 2015 John Wiley & Sons, Ltd.     

Tris(2‐cyanoethyl) isocyanurate

The title compound, 1,3,5‐tris(2‐cyano­ethyl)‐1,3,5‐triazine‐2,4,6(1H,3H,5H)‐trione, C₁₂H₁₂N₆O₃, forms a layered structure stabilized by C—H?O and C—H?N hydrogen bonds.     

Silicon‐based mercaptans: High‐performance monomers for thiol‐ene photopolymerization

Ester‐free silane and siloxane‐based thiol monomers were successfully synthesized and evaluated for application in thiol‐ene resins. Polymerization reaction rates, conversion, network properties as well as degradation experiments of those thiol monomers in combination with triallyl‐1,3,5‐triazine‐2,4,6(1H,3H,5H)‐trione (TATT) as ene component were performed and compared with formulations containing the commercially available mercaptopropionic ester‐based thiol pentaerythritol tetra‐3‐mercaptopropionate. Kinetic analysis revealed appropriate reaction rates and conversions reaching 90% and higher. Importantly, storage stability tests of those formulations clearly indicate the superiority of the synthesized mercaptans compared with pentaerythritol tetra‐3‐mercaptopropionate/TATT resins. Moreover, photocured samples containing silane‐based mercaptans provide higher glass transition temperatures and withstand water storage without a significant loss in their network properties. This behavior together with the observed excellent degradation resistance of photocured silane‐based thiol/TATT formulations make these multifunctional mercaptans interesting candidates for high‐performance applications, such as dental restoratives and automotive resins. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 418–424     

Composite Particles From Pickering‐Stabilized Radical Mediated Thiol‐Ene Suspension Polymerizations

Pickering stabilization is a facile method to create composite colloidal particles. Inorganic colloidal SiO₂ nanoparticles are often used as the stabilizer for particles instead of the more common amphiphilic surfactants. Here the use of this approach in radical‐mediated thiol‐ene suspension polymerizations using monomers 1,3,5‐triallyl‐1,3,5‐triazine‐2,4,6(1H,3H,5H)‐trione (TTT) and pentaerythritol tetrakis (3‐mercaptopropionate) (PETMP) is described. The resulting micron‐sized crosslinked poly(thioether) colloidal particles are coated with 80 nm silica nanoparticles. The addition of a small amount of various costabilizers is examined (hexadecane, cetyl alcohol and toluene), and while all yielded particles, cetyl alcohol provide more consistent results. Scanning electron microscopy and thermal analysis of the composite particles demonstrate morphologies that are consistent with a raspberry‐like structure. No significant changes to the glass transition temperature are observed, which is consistent with the silica nanoparticles being located at the surface of the polymer particles.     

An Efficient Synthesis of New Dispiropyrrolidine Derivatives via Three‐Component 1,3‐Dipolar Cycloaddition Reaction

A series of new dispiropyrrolidine derivatives were synthesized via the three‐component 1,3‐dipolar cycloaddition reaction of azomethine ylides generated in situ by the decarboxylative condensation of acenaphthenequinone and sarcosine or l ‐thioproline with 5‐benzylidene‐1,3‐dimethylpyrimidine‐2,4,6‐trione. The structures of the products were identified by IR, ¹H‐NMR, and HRMS spectra.     

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.     

Synthesis of novel fused tricyclic quinolones: 4a,5‐Dihydro‐1H‐[1;2,4]triazino[1,6‐a]quinoline‐2,4,6(3H)‐triones

A versatile methodology to build the 1H‐[1,2,4]triazino[1,6‐a]quinoline‐2,4,6(3H)‐trione structure from methyl 6‐fluoro4‐oxo‐1,4‐dihydro‐2‐quinolinecarboxylate was developed. The method involves an N‐ami‐nation followed by condensation of an aroyl isocyanate to form an alpha semicarbazidocarboxylate that readily cyclizes to the fused [1,2,4]triazino ring under ammonia/ethanol condition. Also, the reactivity of the [1,2,4]triazino ring thus obtained was studied.     

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.     

An Efficient One‐pot Synthesis of Novel Spiro Cyclic 2‐Oxindole Derivatives of Pyrimido[4,5‐b]Quinoline,Pyrido[2,3‐d:6,5‐d′]Dipyrimidine and Indeno[2′,1′:5,6]Pyrido [2,3‐d]Pyrimidine in Water

A novel and facile one‐pot synthesis of spiro cyclic 2‐oxindole derivatives of pyrimido[4,5‐b]quinoline‐4,6‐dione, pyrido[2,3‐d:6,5‐d′]dipyrimidine‐2,4,6‐trione, and indeno[2′,1′:5,6]pyrido [2,3‐d]pyrimidine employing 6‐aminothiouracil (or 6‐aminouracil), isatin, and cyclic 1,3‐diketone (e.g. 1,3‐indanedione, dimedone, or barbituric acid) has been developed.     

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.     

The Synthesis and Characterization of s‐Triazine‐Cored Tripodal Structure and Its Salen/Salophen‐Bridged Fe/Cr(III) Capped Complexes

A novel Schiff base compound was synthesized, and its complexation properties with Fe(III) and Cr(III) were investigated. Tripodal ligand was synthesized by the reaction of s‐triazine and 4‐hydroxybenzaldehyde. Then a Schiff base involving 8‐hydroxyquinoline was synthesized by the reaction of 5‐aminomethyl‐8‐hydroxyquinoline ( QN ) and 2,4,6‐tris(p‐formylphenoxy)‐1,3,5‐triazine ( TRIPOD ) in methanol/chloroform media. The obtained Schiff base ( QN-TRIPOD ) was then reacted with four trinuclear Fe(III) and Cr(III) complexes including tetradentate Schiff bases N ,N ′‐bis(salicylidene)ethylenediamine (salenH₂)/bis(salicylidene)‐o‐phenylenediamine (SalophenH₂). The synthesized ligand and complexes were characterized by means of elemental analysis carrying out ¹H NMR, FTIR spectroscopy, thermal analyses, and magnetic susceptibility measurements. Finally, metal ratios of the prepared complexes were determined by using atomic adsorption spectrometry.     

Synthesis and characterization of a novel phosphorus–nitrogen‐containing flame retardant and its application for textile

The economic and environmentally friendly flame‐retardant compound, tetramethyl (6‐chloro‐1,3,5‐triazine‐2,4‐diyl)bis(oxy)bis(methylene) diphosphonate ( CN‐1 ), was synthesized by a simple two‐step procedure from dimethyl phosphate, and its chemical structure was characterized by ¹H, ¹³C, and ³¹P nuclear magnetic resonance and gas chromatography mass spectroscopy. Using the traditional pad–dry–cure method, we obtained several different add‐ons (wt%) by treating cotton twill fabric with flame retardant ( CN‐1 ). Thermogravimetric analysis, in an air and nitrogen atmosphere, of the modified cotton showed that decomposition occurred ~230°C with 16% residue weight char yield at 600°C, indicating high thermal stability for all treated levels. Limiting oxygen index (LOI) and the vertical flammability test were employed to determine the effectiveness of the flame‐retardant treatments on the fabrics. LOI values increased from ~18 vol% oxygen in nitrogen for untreated fabric to maximum of 34 vol% for the highest treatment level. Fabrics with higher levels of flame retardant also easily passed the vertical flammability test. Furthermore, Fourier transform infrared and scanning electron microscopy were utilized to characterize the chemical structure as well as the surface morphology of the flame‐retardant treated twill fabrics, including char area and the edge between unburned fabric and char area. Copyright © 2011 John Wiley & Sons, Ltd.     

15N NMR spectra and reactivity of 2,4,6‐triazidopyridines, 2,4,6‐triazidopyrimidine and 2,4,6‐triazido‐s‐triazine

2,4,6‐Triazido‐s‐triazine, 2,4,6‐triazidopyrimidine and six different 2,4,6‐triazidopyridines were studied by ¹⁵N NMR spectroscopy. The assignment of signals in the spectra was performed using the gauge‐independent atomic orbital (GIAO)–Tao‐Perdew‐Staroverov‐Scuseria exchange‐correlation functional (TPSS)h/6‐311+G(d,p) calculations on the M06‐2X/6‐311+G(d,p) optimized molecular geometries. The Truhlar and coworkers' continuum solvation model called SMD was applied to treat solvent effects. With this approach, the root mean square error in estimations of the ¹⁵N chemical shifts for the azido groups was just 1.9 ppm. It was shown that the different reactivity of the α‐ and γ‐azido groups in pyridines correlates well with the chemical shifts of the N_α signals of these groups. Of two nonequivalent azido groups of azines, the azido group with the most shielded N_α signal is the most electron‐deficient and reactive toward electron‐rich reagents. By contrast, the azido group of azines with the most deshielded N_α signal is the most reactive toward electron‐poor reagents. Copyright © 2013 John Wiley & Sons, Ltd.     

One‐pot New Barbituric Acid Derivatives Derived from the Reaction of Barbituric Acids with BrCN and Ketones

Reaction of cyclic β‐dicarbonyl compounds such as pyrimidine‐(1H,3H,5H)‐2,4,6‐trione (BA), 1,3‐dimethyl pyrimidine‐(1H,3H,5H)‐2,4,6‐trione (DMBA) and 2‐thioxo‐pyrimidine‐(1H,3H,5H)‐4,6‐dione (TBA) with cyanogen bromide in acetone and 2‐butanone in the presence of triethylamine afforded a new class of stable heterocyclic spiro[furo[2,3‐d]pyrimidine‐6,5′‐pyrimidine]2,2′,4,4′,6′(3H,3′H,5H)‐pentaones (dimeric forms of barbiturate) at 0 °C and ambient temperature. Structure elucidation was carried out by X‐ray crystallographic, ¹H NMR, ¹³C NMR, two dimensional NMR, FT‐IR spectra, mass spectrometry and elemental analysis. The mechanism of product formation is discussed. The reaction of DMBA with cyanogen bromide in the presence of triethylamine also afforded trimeric form of barbiturate of uracil derivatives in good yield. The reaction of selected acyclic β‐dicarbonyl compounds with cyanogen bromide in the presence of triethylamine in acetone and/or diethyl ether has also been investigated under the same condition. Diethyl malonate and ethyl cyanoacetate brominated and also ethyl acetocetate both brominated and cyanated on active methylene via cyanogen bromide.     

Triazine‐Cored Lanthanide‐Based Metal–Organic Frameworks Featuring Unique Water Chains and Strong Characteristic Emissions

A new triazine‐cored tricarboxylic acid, N,N′,N“‐1,3,5‐triazine‐2,4,6‐triyltris(cis‐4‐aminocyclohexane‐carboxylic acid) (H₃L), has been prepared by replacing the chlorine atoms of cyanuric chloride with cis‐4‐aminocyclohexane‐carboxylic acid, which has been used for the construction of a series of triazine‐cored lanthanide‐based metal–organic frameworks (MOFs). All these MOFs were structurally authenticated, revealing that they are isostructural and exist as two‐dimensional (2D) coordination networks with the general formula [Ln(L)(H₂O)₂]?5.5 H₂O (Ln= 1?Gd , 2?Tb , 3?Eu ). A unique one‐dimensional water chain, composed of primary tetrameric cyclic rings and dodecameric cyclic rings, has been found entrapped in the lattice. Moreover, all these compounds display bright characteristic photoluminescence. Particularly, for 1 , apart from the strong blue emission peak (Φ_f=20.6 %) corresponding to the intraligand transition under near‐UV excitation, the characteristic emissions of Gd³⁺ cation (Φ_f=5.0 %) were unexpectedly observed upon excitation at 273 nm.     

Direct Synthesis of a Covalent Triazine‐Based Framework from Aromatic Amides

There have been extensive efforts to synthesize crystalline covalent triazine‐based frameworks (CTFs) for practical applications and to realize their potential. The phosphorus pentoxide (P₂O₅)‐catalyzed direct condensation of aromatic amide instead of aromatic nitrile to form triazine rings. P₂O₅‐catalyzed condensation was applied on terephthalamide to construct a covalent triazine‐based framework (pCTF‐1). This approach yielded highly crystalline pCTF‐1 with high specific surface area (2034.1 m² g^?1). At low pressure, the pCTF‐1 showed high CO₂ (21.9 wt % at 273 K) and H₂ (1.75 wt % at 77 K) uptake capacities. The direct formation of a triazine‐based COF was also confirmed by model reactions, with the P₂O₅‐catalyzed condensation reaction of both benzamide and benzonitrile to form 1,3,5‐triphenyl‐2,4,6‐triazine in high yield.     

Double Pancake Versus Long Chalcogen–Chalcogen Bonds in Six‐Membered C,N,S‐Heterocycles

The double “pancake” bonding in the dimers of the six‐membered heterocycles 1,3‐dithia‐2,4,6‐triazine ( 4 ) and 1,3‐dithia‐2,4‐diazine ( 16 ) were investigated by means of high‐level quantum chemical calculations (B3LYP and CCSD(T)). It was found that the S–S dimers, 20 a and 27 , are not the most stable isomers, but the dimers showing short S?N ( 21 a ) and S?C ( 25 , 28 ) bonds. An investigation of the 5‐phenyl‐1,3‐dithia‐2,4,6‐triazine ( 4 b ) yields that the syn dimer with two S?S bonds (2.57 Å) is the most stable one. In this dimer, the phenyl groups are placed on top of each other. The additional dispersion energy of the phenyl rings causes a stabilization of the syn‐S–S (C_2v‐like) isomer. As a result, two weak albeit relevant single S?S bonds (2.57 Å) are predicted. These findings contradict the recently published concept of double “pancake” bonding in the dimer 4 b ₂.     

Vinylene‐Linked Covalent Organic Frameworks by Base‐Catalyzed Aldol Condensation

Two 2D covalent organic frameworks (COFs) linked by vinylene (?CH=CH?) groups (V‐COF‐1 and V‐COF‐2) are synthesized by exploiting the electron deficient nature of the aromatic s‐triazine unit of C₃‐symmetric 2,4,6‐trimethyl‐s‐triazine (TMT). The acidic terminal methyl hydrogens of TMT can easily be abstracted by a base, resulting in a stabilized carbanion, which further undergoes aldol condensation with multitopic aryl aldehydes to be reticulated into extended crystalline frameworks (V‐COFs). Both V‐COF‐1 (with terepthalaldehyde (TA)) and V‐COF‐2 (with 1,3,5‐tris(p‐formylphenyl)benzene (TFPB)) are polycrystalline and exhibit permanent porosity and BET surface areas of 1341 m² g^?1 and 627 m² g^?1, respectively. Owing to the close proximity (3.52 Å) of the pre‐organized vinylene linkages within adjacent 2D layers stacked in eclipsed fashion, [2+2] photo‐cycloadditon in V‐COF‐1 formed covalent crosslinks between the COF layers.     

Bis(1,3,5‐triazine‐2,4,6‐triamine‐κN1)silver(I) nitrate

The title compound, [Ag(C₃H₆N₆)₂]NO₃, has an alternating two‐dimensional bilayer structure supported by extensive hydrogen bonds. The [Ag(melamine)₂]⁺ cationic monomers (melamine is 1,3,5‐triazine‐2,4,6‐triamine) are connected via N—H...N hydrogen bonds to form two‐dimensional sheets. Nitrate groups are sandwiched between two sheets through N—H...O hydrogen bonds. An almost perfectly linear coordination geometry is found for the Ag^I ions. The triazine ligands are slightly distorted due to π–π interactions.