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Photosensitive COFs catalyst and method for catalytic synthesis of thiophosphate derivatives

A technology for synthesizing thiophosphoric acid and thiol derivatives, applied in chemical instruments and methods, catalysts for physical/chemical processes, compounds of elements of Group 5/15 of the periodic table, etc. Affecting industrial applications and other issues, achieving the effect of strong industrial application prospects, wide substrate applicability, and fewer by-products

Active Publication Date: 2021-11-30
ZHONGYUAN ENGINEERING COLLEGE
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The invention proposes a photosensitive COFs catalyst and a method for catalyzing and synthesizing phosphorothioate derivatives, which solves the problem that the existing method for synthesizing phosphorothioate derivatives is only carried out in a homogeneous catalytic system, and the catalyst or accelerator cannot be repeated. use, technical issues affecting industrial applications, etc.

Method used

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  • Photosensitive COFs catalyst and method for catalytic synthesis of thiophosphate derivatives
  • Photosensitive COFs catalyst and method for catalytic synthesis of thiophosphate derivatives
  • Photosensitive COFs catalyst and method for catalytic synthesis of thiophosphate derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] (1) Synthesis of photosensitive COF-1 catalyst

[0030]Synthesis of photosensitive COFs-1: 1,3,6,8-tetrakis-(4-formylphenyl)-pyrene (0.08mmol, 49.5mg), 1,1'-[1,4-phenylenebis (Methylene)]bis(1-pyridinium) dichloride (0.16mmol, 53.1mg), 6M potassium tert-butoxide aqueous solution (150uL) and o-dichlorobenzene / n-butanol (volume ratio 2:1) were mixed Add 1.5mL of solvent to a 10mL ampoule. Immerse the ampoule in liquid nitrogen to freeze for 5 minutes, connect the vacuum pump to pump air for 5 minutes under freezing conditions, stop pumping, and place the ampoule at room temperature until the liquid in the bottle melts. The above-mentioned "freezing-pumping-thawing" operation was performed twice again. The ampoule is frozen, and the neck of the ampoule is heated and sealed under pumping. The sealed ampoule was placed at room temperature to completely melt the liquid, and the ampoule was placed in an oven previously heated to 150° C., and left to react for 72 hours. Aft...

Embodiment 2

[0038] The photosensitive COF-1 catalyst was synthesized as in Example 1.

[0039] Synthesis of target compound 2: 202 mg of diphenylphosphine oxide, 320 mg of 2-thionaphthol, 5 mg of photosensitive COF-1 catalyst, and 5 g of DMF were weighed in a 100 ml flask. A stir bar was added thereto, and then stirred for 6 h at 25° C. under an air atmosphere under ultraviolet light irradiation. After the reaction was finished, the catalyst was removed by filtration, the filtrate solvent was removed by a rotary evaporator, and then 2292 mg of phosphorothioate derivatives were obtained by column chromatography separation, with a yield of 81%.

[0040]

[0041] NMR data of target compound 2: 1 H NMR (600MHz, CDCl 3 )δ7.99(s,1H),7.91-7.85(m,4H),7.75-7.67(m,3H),7.52-7.41(m,9H); 13 C NMR (150MHz, CDCl 3 )δ135.3(d, J=5.0Hz), 133.5(d, J=1.6Hz), 132.9(d, J=1.2Hz), 132.5(d, J=107.0Hz), 132.3(d, J=3.0 Hz), 131.6(d, J=10.3Hz), 131.5(d, J=3.3Hz), 128.6(d, J=1.1Hz), 128.5(d, J=13.2Hz), 127.8,...

Embodiment 3

[0044] The photosensitive COF-1 catalyst was synthesized as in Example 1.

[0045] Synthesis of target compound 3:

[0046] In a 100ml flask, 708mg of bis(4-phenylphenyl)phosphine oxide, 500mg of p-methylthiophenol, 8mg of photosensitive COF-1 catalyst, 7g of acetonitrile, and 7g of water were weighed. A stirrer bar was added thereto, and then stirred for 12 h at 25° C. in an air atmosphere under the irradiation of a blue LED light. After the reaction was completed, the catalyst was removed by filtration, the filtrate solvent was removed by a rotary evaporator, and then 743 mg of phosphorothioate derivative 3 was obtained by column chromatography separation, with a yield of 78%.

[0047]

[0048] NMR data of target compound 3: 1 H NMR (400MHz, CDCl 3 )δ7.98-7.92(m,4H),7.70-7.67(m,4H),7.62-7.60(m,4H),7.49-7.45(m,4H),7.42-7.38(m,4H),7.04( d,J=8.1Hz,2H),2.27(s,3H); 13 C NMR (100MHz, CDCl 3 )δ145.0(d, J=3.0Hz), 139.8, 139.2(d, J=2.3Hz), 135.4(d, J=3.7Hz), 132.2(d, J=10.6H...

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Abstract

The invention provides a photosensitive COFs catalyst and a method for catalytic synthesis of thiophosphate derivatives. The photosensitive COFs catalyst takes 1,3,6,8-tetra(4-formylphenyl)pyrene and 1,1'-[1,4-phenylene bis(methylene)] bis(1-azacyclonium)salt as raw materials, and the photosensitive COFs catalyst is synthesized through a solvothermal method under the action of alkali. The preparation method comprises the following steps: by taking photosensitive COFs as a catalyst and taking a substituted phosphine oxide derivative and a thiol derivative as reactants, conducting reacting for 1-30 hours in an air or oxygen environment under the conditions of room temperature, existence of a solvent and illumination, removing the reaction solvent after the reaction is finished, and then obtaining the thiophosphate derivative by a column chromatography separation method or a recrystallization method. The reaction belongs to a heterogeneous catalytic reaction, the catalyst is good in stability, high in catalytic activity, high in reaction efficiency, capable of being recycled for multiple times, simple in synthesis process, high in product selectivity, few in by-product and environmentally friendly, and has a relatively strong industrial application prospect.

Description

technical field [0001] The invention relates to the technical field of synthesis of phosphorothioate derivatives, in particular to a photosensitive COFs catalyst and a method for catalytically synthesizing phosphorothioate derivatives. Background technique [0002] Thiophosphonate derivatives with S-P(O) bonds play an important and constructive role in the fields of organic synthesis, medicinal chemistry, materials science, agrochemical and biological sciences due to their unique structures and diverse biological properties. Some of them have been widely used as important precursors for a series of functional products such as insecticides, antibacterial agents, and enzyme inhibitors. However, these classical methods for phosphorothioate usually contain harsh reaction conditions (e.g., moisture sensitivity, toxic solvents, strong bases, etc.), or are limited by multi-step reaction steps and functional group tolerance, etc. In recent years, in Pd(J.Am.Chem.Soc.,2016,138,5825)...

Claims

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Application Information

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IPC IPC(8): B01J31/06B01J35/10C07F9/32C07F9/6553C07F9/58C07F9/6574C07F9/6541C07F9/18C08G12/26
CPCB01J31/063C07F9/3229C07F9/3205C07F9/3276C07F9/3282C07F9/3288C07F9/655345C07F9/58C07F9/6541C07F9/65744C07F9/18C08G12/26B01J2231/49B01J35/39B01J35/613B01J35/633Y02P20/584
Inventor 乔辉杰杨利婷董昊博王嘉琳孙武轩贾军米立伟
Owner ZHONGYUAN ENGINEERING COLLEGE
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