7753-06-2Relevant articles and documents
METHOD FOR PRODUCING TRIAZINE COMPOUND
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Paragraph 0046; 0059-0064; 0066; 0068-0069, (2021/03/03)
To provide a method for easily and efficiently producing a triazine compound from a nitrile compound and a trihalide compound under a mild production condition using a metal catalyst.SOLUTION: There is provided a method for producing a triazine compound by reacting a nitrile compound represented by the formula (1): R1-CN (wherein, R1 is an aryl group which may be substituted with one or more substituents or a heteroaryl group which may be substituted with one or more substituents) and a trihalide compound represented by the formula (2): R2-CX3 (wherein, R2 is an aryl group which may be substituted with one or more substituents or a heteroaryl group which may be substituted with one or more substituents and X is halogen) in the presence of a catalyst containing a Group 5 metal compound and an ammonium salt and optionally a metal halide compound.SELECTED DRAWING: None
Atom-efficient synthesis of 2,4,6-trisubstituted 1,3,5-triazinesviaFe-catalyzed cyclization of aldehydes with NH4I as the sole nitrogen source
Liu, Qiang,Ren, Shuang,Xiao, Jiang
, p. 22230 - 22233 (2020/07/03)
An atom-efficient, straightforward method for the synthesis of 2,4,6-triaryl-1,3,5-triazinesviairon-catalyzed cyclization of aldehydes with NH4I as the sole nitrogen source is demonstrated. This strategy works smoothly under air atmosphere, and affords symmetrical 2,4,6-trisubstituted and unsymmetrical 1,3,5-triazines with yields from 18% to 72%. Compared to other methods, the present protocol provides a straightforward and atom-efficient approach to 2,4,6-trisubstituted 1,3,5-triazines using an inexpensive, easily available ammonium salt as the sole nitrogen source. Research into the preliminary mechanism indicates thatN-benzylidenebenzimidamides are involved in this cyclization reaction.
Method for constructing asymmetric 2,4,6-trisubstituted 1,3,5-triazine compound by mixing aromatic aldehyde and ammonium iodide
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Paragraph 0065-0109; 0146-0149, (2020/09/30)
The invention discloses a method for constructing an asymmetric 2,4,6-trisubstituted 1,3,5-triazine compound by mixing aromatic aldehyde and ammonium iodide, and belongs to the field of organic synthesis. According to the method, mixed aromatic aldehyde and ammonium iodide are subjected to a one-pot reaction under the catalytic action of iron salt, and the asymmetric 2,4,6-trisubstituted 1,3,5-triazine compound is obtained. According to the method, a micromolecular aryl aldehyde raw material and an iron salt catalyst are adopted, the cost is low, the reaction conditions are mild, the asymmetric 2,4,6-trisubstituted 1,3,5-triazine compound can be obtained, the selectivity is high, and a brand-new synthesis route is provided for construction of a triazine ring.
Mechanistic insight into the azo radical-promoted dehydrogenation of heteroarene towards N-heterocycles
Bains, Amreen K.,Adhikari, Debashis
, p. 6309 - 6318 (2020/11/03)
Borrowing hydrogenation-promoted annulations are considered to be important reactions to synthesize wide variety of N-heterocycles. In these processes, the dehydrogenation of saturated heteroarenes in the late stage is generally required to furnish the desired N-heterocycle. However, in a one-pot, multistep heterocycle synthesis, this step is not well elucidated, and the role of the catalyst is not thoroughly understood. Furthermore, the use of copious amount of base at elevated temperatures further complicates this matter and casts doubt on the involvement of the catalyst in heteroarene dehydrogenation. Herein, we report a molecularly defined nickel catalyst, which can perform two annulation reactions under mild conditions (80 °C, 8 h), towards the sustainable synthesis of triazine and pyrimidine. Mechanistically, we clearly describe the important role of the catalyst in promoting the dehydrogenation of heteroarenes. The binding of the saturated heterocycle to the metal catalyst undergoes a pre-equilibrium step (K = 238 at 80 °C), which is followed by a crucial hydrogen atom transfer. A series of kinetics experiments including Van't Hoff, Eyring analysis and interception of pyrimidinyl radical disclosed the details of the dehydrogenation process. This ligand-driven, base metal catalytic approach is significantly different from the considerably evaluated metal-ligand cooperative bond activation strategies, which may offer an alternative dehydrogenation pathway that demands less energy. This journal is
Synthesis, Spectra, and Theoretical Investigations of 1,3,5-Triazines Compounds as Ultraviolet Rays Absorber Based on Time-Dependent Density Functional Calculations and three-Dimensional Quantitative Structure-Property Relationship
Wang, Xueding,Xu, Yilian,Yang, Lu,Lu, Xiang,Zou, Hao,Yang, Weiqing,Zhang, Yuanyuan,Li, Zicheng,Ma, Menglin
, p. 707 - 723 (2018/05/05)
A series of 1,3,5-triazines were synthesized and their UV absorption properties were tested. The computational chemistry methods were used to construct quantitative structure-property relationship (QSPR), which was used to computer aided design of new 1,3,5-triazines ultraviolet rays absorber compounds. The experimental UV absorption data are in good agreement with those predicted data using the Time-dependent density functional theory (TD-DFT) [B3LYP/6–311 + G(d,p)]. A suitable forecasting model (R > 0.8, P 0.0001) was revealed. Predictive three-dimensional quantitative structure-property relationship (3D-QSPR) model was established using multifit molecular alignment rule of Sybyl program, which conclusion is consistent with the TD-DFT calculation. The exceptional photostability mechanism of such ultraviolet rays absorber compounds was studied and confirmed as principally banked upon their ability to undergo excited-state deactivation via an ultrafast excited-state proton transfer (ESIPT). The intramolecular hydrogen bond (IMHB) of 1,3,5-triazines compounds is the basis for the excited state proton transfer, which was explored by IR spectroscopy, UV spectra, structural and energetic aspects of different conformers and frontier molecular orbitals analysis.
Transition Metal-Free sp3 C–H Functionalization of Arylacetic Acids for the Synthesis of 1,3,5-Triazines
Pardeshi, Sachin D.,Sathe, Pratima A.,Pawar, Balu V.,Vadagaonkar, Kamlesh S.,Chaskar, Atul C.
, p. 2098 - 2102 (2018/05/31)
A one-pot simple, efficient and practically viable protocol for the synthesis of substituted 1,3,5-triazines has been reported from arylacetic acids and benzamidine hydrochloride. In addition, we demonstrated first transition metal-free conversion of phenylacetic acid to benzaldehyde which on condensation with two equivalents of benzamidine hydrochloride offered 2,4,6-trisubstituted 1,3,5-triazines. This protocol is environmentally benign and economically viable which makes it feasible for gram scale synthesis.
IEDDA Reaction of the Molecular Iodine-Catalyzed Synthesis of 1,3,5-Triazines via Functionalization of the sp3 C-H Bond of Acetophenones with Amidines: An Experimental Investigation and DFT Study
Tiwari, Abhishek R.,Nath, Shilpa R.,Joshi, Kaustubh A.,Bhanage, Bhalchandra M.
, p. 13239 - 13249 (2017/12/26)
The present work reports an inverse electron demand Diels-Alder (iEDDA)-type reaction to synthesize 1,3,5-trizines from acetophenones and amidines. The use of molecular iodine in a catalytic amount facilitates the functionalization of the sp3 C-H bond of acetophenones. This is a simple and efficient methodology for the synthesis of 1,3,5-triazines in good to excellent yields under transition-metal-free and peroxide-free conditions. The reaction is believed to take place via an in situ iodination-based oxidative elimination of formaldehyde. DFT calculations at the M062X/6-31+G(d,p) level were employed to investigate the reaction mechanism. Reaction barriers for the cycloaddition as well as a formaldehyde expulsion steps were computed, and a multistep mechanism starting with the nucleophilic attack by benzamidine on an in situ generated imine intermediate has been proposed. Both local and global reactivity descriptors were used to study the regioselectivity of the addition steps.
A Sequential Suzuki Coupling Approach to Unsymmetrical Aryl s-Triazines from Cyanuric Chloride
Wang, Chen,Zhang, Jiehui,Tang, Jie,Zou, Gang
, p. 2514 - 2519 (2017/07/22)
A practical approach has been developed for efficient synthesis of unsymmetrical aryl s-triazines via highly selective sequential Suzuki coupling of cyanuric chloride (2,4,6-trichlorotriazine) with aryl or vinyl boronic or diarylborinic acids catalysed by 0.1–0.5 mol% Pd(PPh3)2Cl2 under mild conditions. The second and third Suzuki couplings for unsymmetrically trisubstituted aryl s-triazines could be more practically conducted in one-pot procedure. An electron-withdrawing conjugate group at phenyl ring of arylboronic acids was unexpectedly found to completely block the coupling while steric hindrance from an ortho electron-donating substituent could be overcome. (Figure presented.).
A 1, 3, 5 - triazine derivative synthesis method
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Paragraph 0070-0072, (2018/11/03)
The invention relates to a synthesis method of 1,3,5-triazine derivatives. The synthesis method comprises the steps of mixing amidine hydrochloride, alcohol, hydrated copper acetate and sodium carbonate, adding a solvent, reacting for 12 hours-24 hours in air at the temperature of 110 DEG C-120 DEG C to obtain a product, purifying the product, extracting, drying, concentrating and separating by virtue of column chromatography to obtain the 1,3,5-triazine derivatives. The synthesis method of the 1,3,5-triazine derivatives, which is disclosed by the invention has the advantages of low cost, available raw materials, high synthesis efficiency and wide application range and is suitable for reaction of a plurality of substrates.
Polythene glycol (PEG) as a reusable solvent system for the synthesis of 1,3,5-triazines via aerobic oxidative tandem cyclization of benzylamines and N-substituted benzylamines with amidines under transition metal-free conditions
Tiwari, Abhishek R.,Bhanage, Bhalchandra M.
supporting information, p. 144 - 149 (2015/12/31)
A green and highly efficient protocol for the synthesis of 1,3,5-triazines from benzylamines and N-substituted benzylamines with amidines in PEG-600 has been developed. This protocol is transition-metal free, phosphine ligand free and uses inexpensive, easily available molecular oxygen (O2) as an oxidant. A series of 1,3,5-triazines derivatives were synthesized in good to excellent yields in a shorter reaction time. The ease of the product separation and reusability of PEG-600 makes it more environmentally benign and economically affordable for gram-scale synthesis.
