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Photoinduced Iodine Catalyzed Atherton-Todd Reaction Synthesis of Organophosphorus Compounds

A compound and light-induced technology, applied in the direction of organic chemistry, chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, etc., can solve problems such as limited development, environmental damage, single catalytic substrate, etc., and achieve high yield High, good universality, short response time effect

Active Publication Date: 2020-11-03
HENAN UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although this method does not add alkaline reagents, it uses equivalent-level toxic halogenated reagents, and the catalytic substrate is single, so the applicability is not high
[0003] It can be seen that the current Atherton-Todd reaction still needs to be reacted in the environment of toxic halogenated reagents, metals, high temperature and strong alkali (and the amount of catalyst used is generally equivalent), heavy metals, heating and strong The alkaline environment is not suitable for the synthesis and preparation of some drugs, and it will cause some damage to the environment, which greatly limits the development of the reaction

Method used

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  • Photoinduced Iodine Catalyzed Atherton-Todd Reaction Synthesis of Organophosphorus Compounds
  • Photoinduced Iodine Catalyzed Atherton-Todd Reaction Synthesis of Organophosphorus Compounds
  • Photoinduced Iodine Catalyzed Atherton-Todd Reaction Synthesis of Organophosphorus Compounds

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] The preparation of embodiment one propyl diphenylphosphonate

[0020] Diphenylphosphine oxide (0.5mmol, 101mg), n-propanol (2.5mmol, 187ml), iodine (0.075mmol, 19mg), dichloromethane (3ml) were reacted under light at room temperature for 24h in an oxygen atmosphere, and 0.5ml was added Saturated sodium thiosulfate solution washes off iodine molecules, and after 2eq Na 2 SO 4 After drying, filtering, the organic phase was separated by column chromatography, and purified to obtain 104 mg of a white solid product with a yield of 80%. The reaction equation is as follows:

[0021]

[0022] The NMR characterization of propyl diphenylphosphonate is as follows: 1 H NMR (400MHz, CDCl 3 )δ7.85–7.77(m,4H),7.53–7.48(m,2H),7.47–7.41(m,4H),3.98(m,2H),1.75(m,J=14.1,7.1Hz,2H) , 0.97 (t, J=7.4Hz, 3H).

Embodiment 2

[0023] The preparation of embodiment two diphenyl phosphonic acid octyl esters

[0024] Diphenylphosphine oxide (0.5mmol, 101mg), n-octanol (2.5mmol, 392ml), iodine (0.075mmol, 19mg), dichloromethane (3ml) were reacted under light at room temperature for 24h in an oxygen atmosphere, and 0.5ml was added Saturated sodium thiosulfate solution washes off iodine molecules, and after 2eq Na 2 SO 4 After drying, filtering, the organic phase was separated by column chromatography, and purified to obtain 126 mg of light yellow oily liquid with a yield of 76%. The reaction equation is as follows:

[0025]

[0026] The NMR characterization of octyl diphenylphosphonate is as follows: 1 H NMR (400MHz, DMSO) δ7.80–7.70(m,4H),7.62–7.47(m,6H),3.97–3.86(m,2H),1.69–1.56(m,2H),1.27(d,J =46.0Hz, 10H), 0.86–0.79(m, 3H).

Embodiment 3

[0027] The preparation of embodiment three diphenylphosphonic acid cyclohexyl esters

[0028] Diphenylphosphine oxide (0.5mmol, 101mg), cyclohexanol (2.5mmol, 260ml), iodine (0.075mmol, 19mg), dichloromethane (3ml), light reaction for 24h in an oxygen atmosphere at room temperature, add 0.5ml Saturated sodium thiosulfate solution washes off iodine molecules, and after 2eq Na 2 SO 4 Drying, filtration, column separation of the organic phase, and purification gave 98 mg of a white solid product with a yield of 65%. The reaction equation is as follows:

[0029]

[0030] The NMR characterization of cyclohexyl diphenylphosphonate is as follows: 1 H NMR (400MHz, CDCl 3 )δ7.78–7.70(m,4H),7.45–7.39(m,2H),7.38–7.32(m,4H),4.40–4.29(m,1H),1.82(d,J=10.3Hz,2H) ,1.71–1.63(m,2H),1.58–1.48(m,2H),1.43–1.36(m,1H),1.23–1.15(m,3H).

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Abstract

The invention belongs to the technical field of organic synthesis, discloses a method for synthesis of organophosphorus compound by photo-induced iodine catalyzed Atherton-Todd reaction. The method comprises the following steps: a compound shown as formula II and a nucleophilic reagent are subjected to reaction for 24 hours in a dichloromethane solvent, an oxygen atmosphere, under irradiation condition of room temperature and the action of a halogenated reagent I2, then the organophosphorus compound shown as the formula II is obtained through washing, drying, separating and purifying. According to the the method provided by the invention, compared with traditional Atherton-Todd reaction, no catalysis of metal is needed,no addition of alkali is needed, reaction environment such as metal, high temperature and strong base is replaced, a series of organophosphorus compounds can be synthesized by catalyzing a variety of substrates under the irradiation condition of room temperature, and hasthe advantages of good universality, short reaction time and higher yield.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to a method for synthesizing organophosphorus compounds by light-induced iodine catalyzing Atherton-Todd reaction. Background technique [0002] Organophosphorus compounds, such as organophosphine (phosphorus) esters and organophosphine (phosphorus) amides, are widely used in biology, medicine, pesticides and materials. The Atherton-Todd reaction is an important synthetic method of organophosphorus compounds. . The classic Atherton-Todd reaction uses a dialkyl phosphonate, under the action of an equivalent base and excess carbon tetrachloride, first generates a phosphonyl halide, and then forms a dialkyl phosphonamide with an amine compound or an alcohol compound Or dialkyl phosphonate reaction. Weisheng Tian team established with 6eq C 4 f 9 SO 2 F / Et 3 N catalyst system to catalyze the reaction of different alcohols with diphenylphosphine oxide, all of which can obta...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/32C07F9/30C07F9/36C07F9/40C07F9/6574C07F9/6571C07F9/11C07F9/572C07F9/6533
CPCC07F9/11C07F9/304C07F9/3229C07F9/36C07F9/4021C07F9/5728C07F9/6533C07F9/657181
Inventor 徐元清杨鹏坤许静徐浩孟献瑞张文凯刘保英任艳蓉房晓敏丁涛
Owner HENAN UNIVERSITY
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