Method for preparing six fluorine phosphonic acid ester base fe organism derivatives

A technology of diethyl difluoromethylphosphonate and diethyl bromodifluoromethylphosphonate is applied in the fields of organic chemical industry and fine chemical industry, and can solve the problems of toxic and unstable free radical initiators, and achieve high application Value, convenient separation and purification, and the effect of less waste discharge

Inactive Publication Date: 2015-08-19
LUOYANG NORMAL UNIV
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Problems solved by technology

[0004] Aiming at the synthesis method of the above-mentioned existing difluorophosphonate compounds, expensive phosphorus ligands need to be used, the reaction is carried out at a relatively high temperature, and defects such as toxic and unstable free radical initiator AIBN need to be used, the present invention A mild and efficient method for preparing 6-difluorophosphonate-phenanthridine derivatives is provided

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  • Method for preparing six fluorine phosphonic acid ester base fe organism derivatives
  • Method for preparing six fluorine phosphonic acid ester base fe organism derivatives
  • Method for preparing six fluorine phosphonic acid ester base fe organism derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Synthesis of diethyl difluoro(phenanthridin-6-yl)methylphosphonate (2a)

[0027] Weigh 2-phenylbenzene isocyanide 1a (1mmol), ethyl bromodifluorophosphonate (4.0mmol), three (2-phenylpyridine) iridium (0.05mmol) and sodium bicarbonate (2.0mmol), and Add it to a 25mL Schlenk reaction flask in turn, then add acetonitrile (10.0mL) and place it under a 20W LED lamp to react for 40h. After the reaction is over, remove the solvent under reduced pressure and use petroleum ether / ethyl acetate as the eluent , separated on a silica gel column, the yield of the product diethyl difluoro(phenanthridin-6-yl)methylphosphonate was 78%.

[0028] 1 H NMR (400 MHz, CDCl 3 ): δ = 8.66 (d, J = 7.6 Hz, 1H), 8.59 (d, J = 7.6 Hz, 2H), 8.23 ​​(d, J = 7.2 Hz, 1H), 7.87 (t, J = 7.2 Hz, 1H), 7.69-7.79 (m, 3H), 4.45-4.62 (m, 4H),1.42 (t, J = 7.2 Hz, 6H); 13 C NMR (125 MHz, CDCl 3 ): δ = 150.5 (td, J 1 = 25.4, J 2 = 13.3 Hz), 141.7, 133.9, 131.1, 130.5, 129.0, 128.9, 127.7, 126.8,...

Embodiment 2

[0030] Synthesis of diethyl difluoro(8-methylphenanthridin-6-yl)methylphosphonate (2b)

[0031] Weigh 2-p-tolylbenzonitrile 1b (0.5mmol), ethyl bromodifluorophosphonate (1.0mmol), tris(2-phenylpyridine) iridium (0.02mmol) and sodium carbonate (1.0mmol), And sequentially added in the 25mL Schlenk reaction bottle, then, add dichloromethane (5.0mL), and place to react 48h under the blue LED lamp of 5 watts, after the reaction finishes, remove solvent under reduced pressure, use sherwood oil / ethyl acetate as The eluent was separated on a silica gel column, and the yield of the product diethyl difluoro(8-methylphenanthridin-6-yl)methylphosphonate was 76%.

[0032] 1H NMR (400 MHz, CDCl 3 ): δ = 8.54 (d, J = 8.0 Hz, 2H), 8.20 (d, J = 8.0 Hz, 1H), 8.36(s, 1H), 7.68-7.76 (m, 3H), 4.51-4.59 (m, 4H),2.61 (s, 3H), 1.42 (t, J = 7.2 Hz, 6H); 13 C NMR (125MHz, CDCl 3 ): δ = 150.2 (td, J 1 = 26.0, J 2 = 14.2 Hz), 141.4, 137.8, 132.9, 131.8, 130.4, 128.8, 128.5, 127.4, 126.0,...

Embodiment 3

[0034] Synthesis of diethyl (8-ethylphenanthridin-6-yl)difluoromethylphosphonate (2c)

[0035] Weigh 2-p-ethylphenylisocyanate 1c (0.5mmol), ethyl bromodifluorophosphonate (2.0mmol), [4,4'-di-tert-butyl-2,2'-bipyridine] di [2-2-Phenylpyridine] Iridium hexafluorophosphate (0.01mmol) and triethylamine (2.0mmol) were added successively to a 25mL Schlenk reaction flask, then tetrahydrofuran (5.0mL) was added, and placed React under a 40-watt LED lamp for 36 hours. After the reaction, remove the solvent under reduced pressure, use petroleum ether / ethyl acetate as the eluent, and separate on a silica gel column to obtain the yield of the product diethyl (8-ethylphenanthridin-6-yl) difluoromethylphosphonate was 72%.

[0036] 1 H NMR (400 MHz, CDCl 3 ): δ = 8.51-8.59 (m, 2H), 8.39 (s, 1H), 8.21(d, J = 8.0 Hz, 1H), 7.67-7.78 (m, 3H), 4.50-4.59 (m, 4H),2.91 (q, J = 7.6 Hz, 2H), 1.42 (t, J = 7.2 Hz, 6H), 1.37 (t, J = 7.6 Hz, 3H); 13 C NMR (125MHz, CDCl 3 ): δ = 150.3 (td, ...

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Abstract

The invention relates to a soft and effective method for preparing six fluorine phosphonic acid ester base fe organism derivatives. 2 - aryl aromatic nitrile and br two fluorine methyl phosphonic acid diethyl ester are applied as raw materials. A series of six fluorine phosphonic acid ester base fe organism derivatives is prepared under the function of photo-catalyst. The using of free radical reagent of high toxicity is not used in the method, and thus the method is environment friendly and economic. The exposure of visible light is used and the reaction under high temperature is avoided, and the reaction condition is mild. The invention has the advantages taht the separation and purification is convenient, the waste is little, special demand to the bottom reaction materials is not necessary, the application is wide, and the application value is high.

Description

technical field [0001] The invention relates to the fields of organic chemical industry and fine chemical industry, in particular to a method for synthesizing 6-difluoromethylphosphonic acid diethylcarboxyphenanthridine derivatives. Background technique [0002] Due to the small size, high electronegativity and high electron cloud density of fluorine atoms, introducing them into organic molecules can change the physical, chemical and biological properties of the parent compound, so fluorine-containing compounds have many application specificities, such as fluorine-containing polymers The material has high chemical resistance and thermal stability, and the introduction of fluorine atoms or fluorine-containing groups significantly enhances the mimicry, permeability, electronic effect, and barrier effect of organic compounds, so that fluoride is widely used in medicine, pesticides, etc. Therefore, organic fluorine chemistry has now penetrated into various fields of organic ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/576
Inventor 朱梅付维军
Owner LUOYANG NORMAL UNIV
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