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Preparation method of 2,4-di-substituted-1,3,5-triazine

A disubstituted, formamidine hydrochloride technology, applied in the direction of organic chemistry, can solve the problems of unfriendly demethylation by-products, limited range of substrates, and insufficient mild conditions, and achieve low-cost, low-toxic metal residues and environmental protection. Friendly, no metal residue effect

Active Publication Date: 2018-03-06
ZHENGZHOU UNIVERSITY OF LIGHT INDUSTRY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although the substrate range is wide and the yield is acceptable, metal copper is used in the reaction and environmentally unfriendly demethylation by-products such as N-methylformamide or methyl mercaptan are generated
Therefore, combining the previous synthetic methods, we found that these methods have disadvantages such as insufficient mild conditions, limited range of substrates, low yield, and insufficient economical greenness.

Method used

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  • Preparation method of 2,4-di-substituted-1,3,5-triazine
  • Preparation method of 2,4-di-substituted-1,3,5-triazine
  • Preparation method of 2,4-di-substituted-1,3,5-triazine

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0014]

[0015] Add 1a (4mmol, 624mg), potassium iodide (0.8mmol, 133mg), potassium tert-butoxide (4mmol, 449mg), tert-butyl hydroperoxide (8mmol, 70% aqueous solution, 1.2mL) and methyl tert-butyl to the reaction flask base ether (10 mL), and then heated at 100° C. for 12 hours. After the reaction is completed, it is first quenched with saturated sodium thiosulfate solution, then extracted with ethyl acetate, the organic phases are combined, dried with anhydrous sodium sulfate, concentrated, and then subjected to column chromatography with a mixed solvent of petroleum ether and ethyl acetate to obtain Product 3a, yield 85%. White solid, Mp: 74-75℃; 1 H NMR (600MHz, CDCl 3 ):δ9.25(s,1H),8.65-8.63(m,4H),7.62-7.58(m,2H),7.56-7.53(m,4H); 13 C NMR (150MHz, CDCl 3 ): δ171.3, 166.7, 135.5, 132.8, 128.9, 128.7.

Embodiment 2

[0017]

[0018] Add 1b (4mmol, 698mg), potassium iodide (0.8mmol, 133mg), potassium tert-butoxide (4mmol, 449mg), tert-butyl hydroperoxide (8mmol, 70% aqueous solution, 1.2mL) and methyl tert-butyl to the reaction flask base ether (10 mL), and then heated at 100° C. for 18 hours. After the reaction is completed, it is first quenched with saturated sodium thiosulfate solution, then extracted with ethyl acetate, the organic phases are combined, dried with anhydrous sodium sulfate, concentrated, and then subjected to column chromatography with a mixed solvent of petroleum ether and ethyl acetate to obtain Product 3b, yield 69%. White solid, Mp: 155-156°C; 1 H NMR (600MHz, CDCl 3 ):δ9.20(s,1H),8.67-8.62(m,4H),7.25-7.20(m,4H); 13 C NMR (150MHz, CDCl 3 ): δ 170.3, 166.6, 166.0 (d, J=252.6Hz), 131.6 (d, J=3.0Hz), 131.3 (d, J=9.4Hz), 115.9 (d, J=21.5Hz).

Embodiment 3

[0020]

[0021] Add 1c (4mmol, 764mg), potassium iodide (0.8mmol, 133mg), potassium tert-butoxide (4mmol, 449mg), tert-butyl hydroperoxide (8mmol, 70% aqueous solution, 1.2mL) and methyl tert-butyl to the reaction flask base ether (10 mL), and then heated at 100° C. for 12 hours. After the reaction is completed, it is first quenched with saturated sodium thiosulfate solution, then extracted with ethyl acetate, the organic phases are combined, dried with anhydrous sodium sulfate, concentrated, and then subjected to column chromatography with a mixed solvent of petroleum ether and ethyl acetate to obtain Product 3c, yield 81%. White solid, Mp: 191-192°C; 1 H NMR (600MHz, CDCl 3 ):δ9.23(s,1H),8.58-8.55(m,4H),7.53-7.50(m,4H); 13 C NMR (150MHz, CDCl 3 ): δ170.5, 166.7, 139.4, 133.8, 130.2, 129.1.

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Abstract

The invention discloses a method for preparing 2,4-di-substituted-1,3,5-triazine. The method comprises the specific step: with substituted formamidine hydrochloride as a reaction substrate an iodine-containing compound as a catalyst, tert-butyl hydroperoxide as an oxidant, inorganic base as an acid binding agent and aliphatic ether as an organic solvent (also used as a carbon source), carrying outcarbon-hydrogen and carbon-oxygen bond deletion, nucleophilic addition, deaminizing condensation and oxidative aromatization reaction to obtain a 2,4-di-substituted-1,3,5-triazine compound, wherein achemical structural general formula of the substituted formamidine hydrochloride is shown in the description; the iodine-containing compound is selected from one of potassium iodide (KI), tetrabutylammonium iodide (TBAI), elemental iodine (I2) and N-iodosuccinimide (NIS); the inorganic base is selected from one of anhydrous potassium carbonate, anhydrous sodium carbonate, cesium carbonate, potassium hydroxide and potassium tert-butoxide; and the aliphatic ether is selected from one of methyl tert-butyl ether, ethyl ether and ethylene glycol dimethyl ether. The preparation method disclosed bythe invention has the characteristics of easily-obtained raw materials, low price and low toxicity of a catalyst, wide range of the substrate, simplicity and convenience in operation, greenness, environmental protection and the like.

Description

technical field [0001] The invention relates to a preparation method of 2,4-disubstituted-1,3,5-triazine. Background technique [0002] 1,3,5-Triazine is a class of nitrogen-containing heterocyclic compounds that are very important in natural products and medicinal chemistry. In particular, 2,4-disubstituted-1,3,5-triazines exhibit very excellent biological activity. In addition, 2,4-disubstituted-1,3,5-triazines can be used as polydentate nitrogen ligands for transition metal-catalyzed organic synthesis reactions or the preparation of organometallic materials. [0003] The traditional method generally all is to synthesize 2,4-diphenyl-1,3,5-triazine (Angew.Chem.1960,72,956; Chem.Ber.1963,96,3265; Monatsh.Chem.1995,126,99; Zhurnal Organiccheskoi Khimii,1987,23,2443), however, the substrate range is narrow, the yield is generally low and the reaction conditions are harsh. In recent years, Xu et al. have synthesized 2,4-disubstituted-1, 3,5-Triazine (M.-N.Zhao, R.-R.Hui, Z...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D251/24C07D401/14
CPCC07D251/24C07D401/14
Inventor 闫溢哲牛斌贺远李政崔畅刘延奇史苗苗周亚萍刘华玲
Owner ZHENGZHOU UNIVERSITY OF LIGHT INDUSTRY
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