A method for synthesizing β-ketophosphorus oxide

Abstract

The present application discloses a method for synthesizing β-ketophosphorus oxide, and relates to the technical field of organic synthesis. The method comprises the following steps: sodium trifluoromethanesulfinate, an aryl phosphorus oxide compound, an aromatic alkyne compound, and a solvent are placed in a reaction vessel and mixed; the mixture is reacted for 12 to 30 hours under air atmosphere, room temperature, and 30-watt blue light irradiation with continuous stirring, and after the reaction is completed, the mixture is washed with water, extracted with ethyl acetate, dried, and concentrated by reduced pressure distillation to remove the solvent to obtain a crude product; the crude product is separated by column chromatography to obtain a target product. The synthesis method provided by the present application has the characteristics of cheap and readily available raw materials, a simple catalytic system, easy separation of the target product, high stereo and position selectivity, simple reaction operation, safety and reliability, and green environmental protection, which are advantages that other methods cannot have at the same time.

Description

Technical Field

[0001] The present application relates to the technical field of organic synthesis, and in particular to a method for synthesizing β-ketophosphorus oxide. Background Art

[0002] β-Ketophosphorus oxide is an important organophosphorus compound with a wide range of biological activities and excellent metal complexing ability. Therefore, it can be used for liquid-liquid extraction of metal ions. In addition, β-ketophosphonates can also be used as useful precursors for the synthesis of chiral β-amino and β-hydroxyphosphonic acids, both of which have good biological properties. On the other hand, β-ketophosphorus oxide is also a very useful synthetic intermediate that can be prepared into other functional molecules through a variety of transformations, such as the preparation of α,β-unsaturated carbonyl compounds using the Horner-Wadsworth-Emmons reaction.

[0003] Generally, β-ketophosphorus oxides can be prepared by the reaction of α-haloketones with trialkylphosphites at high temperature (Arbuzov reaction) or the acylation reaction of alkylphosphonates with carboxylic acid derivatives, but both methods have limitations, such as low atom economy, difficult to obtain materials, cumbersome procedures, relatively harsh reaction conditions, and the need for excessive amounts of toxic organometallic reagents. Secondly, the hydrolysis of alkynylphosphine compounds can be achieved using expensive metal palladium or gold catalysts to obtain β-ketophosphorus oxides, but this method requires the preparation of the original alkynylphosphine compound material in advance, which increases the synthesis steps. Therefore, it is necessary to continue to develop convenient and efficient methods to obtain β-ketophosphorus oxides.

[0004] The simplest and most atom-economical strategy to synthesize β-ketophosphorus oxides is to directly utilize the oxidation-phosphorylation of alkynes and phosphine oxyhydrides with oxygen. In 2015, Zhao reported that in the presence of AgNO3 / CuSO4 catalyst and K2S2O8, oxygen in the air was used to achieve a one-pot reaction of alkynes with phosphine oxyhydrides to prepare a variety of β-ketophosphorus oxides. Almost at the same time, He and Song used Cu / Fe copper / iron catalytic system and oxygen at high temperature to achieve oxygen-phosphorylation of alkynes and synthesize a series of β-ketophosphorus oxides. The participation of metals and the addition of additional oxidants or high temperatures also restrict the application of these three methods to a certain extent. Photocatalytic methodology is a powerful technical means that has developed rapidly in the organic field in the past decade. It has attracted widespread attention from researchers for its low energy consumption, low pollution and good atom economy, injecting new vitality into synthetic chemistry. In 2016, Cai used the dye Rhodamine B as a photosensitizer and achieved the oxygen-phosphonylation of alkynes and phosphine compounds with oxygen to prepare β-ketophosphorus oxides at room temperature and under 12W white light irradiation. Although this method has made some progress compared with the previously reported methods, the use of the dye Rhodamine B will cause environmental pollution to a certain extent, especially in the post-processing process. Therefore, it is still of great significance to continue to develop simple, green and environmentally friendly catalytic systems to achieve the oxygen-phosphonylation of alkynes to synthesize β-ketophosphorus oxides.[Reference: A. Bakht iary, MRP Heravi, A Hassanpour, I. Amini and E. Vessa lly, RSC Adv.,2021,11,470–483; AKBhattacharyaandG.Thyagarajan,Chem.Rev.,1981,81,415–430; l., 2012, 354, 2427–2432; L. Xie, R. Yuan, R. Wang, Z. Peng, J. Xiang and W. He, Eur. andJ.Y.Chung,J.Org.Chem.,2009,74,7574–7576;RRMi l burn,K.McRae,J.Chan,J.Tedrow,R.Larsen and M.Fau l,Tetrahedron Lett.,2009,50,870–872; H.-T.Wu,ChemComm,2015,51,3846–3849;N.Yi,R.Wang,H.Zou,W.He,W.Fu and W. He, J. Org. Chem., 2015, 80, 5023–5029; M. Zhou, M. Chen, Y. Zhou, K. Yang, J. Su, J. Du and Q. Song, Org. Lett., 2015, 17, 1786–1789; V. Gut i ​​errez, E. Mascar′o, F. Al onso, Y. Mog li eand G.Rad ivoy,RSC Adv.,2015,5,65739–65744; M.-j.Bu,G.-p.Lu andC.Cai,Cata l.Sci.Technol.,2016,6,413–416.]. Summary of the invention

[0005] The purpose of the present application is to provide a method for synthesizing β-ketophosphorus oxide to solve at least one of the above technical problems.

[0006] In order to achieve the above-mentioned object of the invention, the present application provides a method for synthesizing β-ketophosphorus oxide, comprising the following steps:

[0007] Sodium trifluoromethanesulfinate, an arylphosphorus oxide compound, an aromatic alkyne compound and a solvent are placed in a reaction container and mixed;

[0008] In an air atmosphere, at room temperature, under blue light irradiation, the reaction is continued with stirring for 12 to 30 hours. After the reaction is completed, the mixture is washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent to obtain a crude product.

[0009] The crude product is separated by column chromatography to obtain the target product.

[0010] Preferably, the target product has one or more of structural formula I, structural formula II, and structural formula III, and the structural formula I, structural formula II, and structural formula III are shown below:

[0011]

[0012] Preferably, in the structural formula I, R 1 is one of hydrogen, methyl, ethyl, tert-butyl, methoxy, fluorine, chlorine, bromine, cyano, trifluoromethyl, nitro, methyl ester, and phenyl; R 2 It is one of hydrogen, chlorine, methyl, and methoxy.

[0013] Preferably, the aromatic phosphorus oxide compound is selected from one of diphenylphosphine oxide, bis(p-methylphenyl)phosphine oxide, bis(3,5-dimethylphenyl)phosphine oxide, bis(4-chlorophenyl)phosphine oxide and bis(p-methoxyphenyl)phosphine oxide.

[0014] Preferably, the aromatic alkyne compound is selected from one of phenylacetylene, 4-methylphenylacetylene, 4-ethylphenylacetylene, 4-tert-butylphenylacetylene, 4-methoxyphenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 4-bromophenylacetylene, 4-phenylphenylacetylene, 3-thiopheneacetylene, and 6-ethynyl-4,4-dimethyldihydrobenzothiopyran.

[0015] Preferably, the solvent is selected from one of dichloromethane, isopropanol, methanol and tert-butanol.

[0016] Preferably, the molar ratio of the sodium trifluoromethanesulfinate, the aryl phosphorus oxide compound and the aromatic alkyne compound is [0.1-0.3]:[1.5-2.0]:1.

[0017] Preferably, the concentration of the reaction system is 1-2M.

[0018] Preferably, the blue light irradiation power is 30 watts.

[0019] Preferably, the wavelength of the blue light is 400-460 nm.

[0020] Preferably, the synthetic reaction formula of the target product is as follows:

[0021]

[0022] According to experimental research, the present invention provides a method for preparing β-ketophosphorus oxide by oxidative phosphonylation of aromatic alkynes and aromatic phosphorus oxides with high selectivity and high conversion rate. Compared with the prior art, the method has the characteristics of cheap and readily available raw materials, simple and mild reaction system, good regional chemical selectivity, simple reaction operation, wide substrate range, and green environmental protection. The method mainly solves the shortcomings of other β-ketophosphorus oxides, such as the need for pre-prepared raw materials, high temperature, and easy environmental pollution caused by dye catalysts. The characteristics of the method are specifically manifested as follows:

[0023] (1) The catalytic system is simple, requiring only commercial sodium trifluoromethanesulfinate, which is easy to store, stable in nature, cheap and readily available;

[0024] (2) It only needs to react under room temperature and air conditions, using oxygen in the air as an oxidant and oxygen source, without the need for additional high-purity oxygen;

[0025] (3) Compared with the traditional photocatalytic synthesis method, the synthesis method provided by the present application uses green and pollution-free raw materials, and is also more environmentally friendly during the post-processing process;

[0026] (4) The target product obtained is easy to separate and has high stereo and position selectivity. With appropriate reaction conditions, such as controlling the wavelength of blue light, adding the components in a suitable ratio, and controlling the power of blue light irradiation, the yield of the product is guaranteed to be suitable for industrial production applications and have commercial value. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is the reaction formula for preparing β-ketophosphorus oxide. DETAILED DESCRIPTION

[0028] The technical scheme of the present application is further described in detail below in conjunction with specific embodiments and comparative examples. The specific materials, contents, data and other conditions and details provided in the embodiments and comparative examples are all used to explain the present application, and the protection scope of the present application is not limited by the embodiments. Any simple modifications, equivalent changes and modifications made according to the essence of the present application all belong to the scope of the claims of the present application.

[0029] Unless otherwise indicated, all percentages, parts, ratios, etc. herein are by weight.

[0030] The singular forms "a", "an" and "the" include plural referents unless otherwise indicated.

[0031] When a quantity or other value is expressed in the form of a range, a preferred range, or an upper preferred numerical limit and a lower preferred numerical limit, it should be understood that any range combined with any pair of upper or lower range limits is specifically interpreted as being equivalent to being specifically interpreted, regardless of whether the range is specifically disclosed.

[0032] The present application discloses a method for synthesizing β-ketophosphorus oxide, comprising the following steps:

[0033] Sodium trifluoromethanesulfinate, an arylphosphorus oxide compound, an aromatic alkyne compound and a solvent are placed in a reaction container and mixed;

[0034] In an air atmosphere, at room temperature, under blue light irradiation, the reaction is continued with stirring for 12 to 30 hours. After the reaction is completed, the mixture is washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent to obtain a crude product.

[0035] The crude product is separated by column chromatography to obtain the target product.

[0036] Specifically, the target product has one or more of structural formula I, structural formula II, and structural formula III, and structural formula I, structural formula II, and structural formula III are shown below:

[0037]

[0038] In some embodiments, in Structural Formula I, R 1 is one of hydrogen, methyl, ethyl, tert-butyl, methoxy, fluorine, chlorine, bromine, cyano, trifluoromethyl, nitro, methyl ester, and phenyl; R 2 It is one of hydrogen, chlorine, methyl, and methoxy.

[0039] In some embodiments, the arylphosphine oxide is selected from one of diphenylphosphine oxide, bis(p-methylphenyl)phosphine oxide, bis(3,5-dimethylphenyl)phosphine oxide, bis(4-chlorophenyl)phosphine oxide, and bis(p-methoxyphenyl)phosphine oxide.

[0040] In some embodiments, the aromatic alkyne compound is selected from one of phenylacetylene, 4-methylphenylacetylene, 4-ethylphenylacetylene, 4-tert-butylphenylacetylene, 4-methoxyphenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 4-bromophenylacetylene, 4-phenylphenylacetylene, 3-thiopheneacetylene, and 6-ethynyl-4,4-dimethyldihydrobenzothiopyran.

[0041] In some embodiments, the solvent is selected from one of dichloromethane, isopropanol, methanol, and tert-butanol.

[0042] In some embodiments, the molar ratio of the sodium trifluoromethanesulfinate, the aryl phosphorus oxide compound, and the aromatic alkyne compound is [0.1-0.3]:[1.5-2.0]:1.

[0043] Furthermore, the concentration of the reaction system is 1-2M.

[0044] Furthermore, the blue light irradiation power is 30 watts.

[0045] Furthermore, the wavelength of blue light is 400-460 nm.

[0046] Specifically, the synthesis reaction formula of the target product is as follows:

[0047]

[0048] Under light, sodium trifluoromethanesulfinate and oxygen can form an active intermediate 1 (the actual catalytic species of the reaction). Intermediate 1 is excited by light to form an excited state 2, which then undergoes a single electron transfer with oxygen to form a free radical species 3. At the same time, the generated free radical 3 grabs H in the aromatic phosphorus oxide to generate compound 4 and aromatic phosphorus radical 5. The phosphorus radical 5 undergoes an addition reaction with alkynes to obtain alkenyl phosphorus radical 6, which then reacts with oxygen O2 radical anions and H+ to generate peroxide compound 7, and then a series of transformations occur to obtain the target product β-ketophosphorus oxide TM.

[0049] This reaction may be achieved through the following pathways:

[0050]

[0051] The following is a specific synthesis example:

[0052] Synthesis example 1

[0053] Synthesis of β-(Diphenylphosphoryl)-1-phenylethan-1-one

[0054] 0.2mmol phenylacetylene, 0.05mmol sodium trifluoromethanesulfinate, 0.4mmol diphenylphosphine oxide, 1.0mL isopropanol were added to the reactor. In an air atmosphere, at room temperature, under irradiation of 30 watts of blue light with a wavelength of 400-410nm, the reaction was stirred for 20 hours. After the reaction, the mixture was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product with a yield of 80%. 1 H NMR (400MHz, CDCl3): δ7.94(d,J=7.6Hz,2H),7.80–7.75(m,4H),7.50–7.45(m,3H),7.43–7.34(m,6H),4.12(d,J=15.2Hz,2H). 13C NMR(101MHz, CDCl3): δ192.6(d,J C-P =5.7Hz),136.7,133.4,132.0(d,J C-P =2.5Hz),131.7(d,J C-P =104Hz),130.9(d,J C-P =9.8Hz),129.0,128.4(d,J C-P =12.3Hz),128.3,43.0(d,J C-P =58.3Hz). 31 P NMR (162 MHz, CDCl3): δ 27.11.

[0055] Synthesis example 2

[0056] Synthesis of β-(diphenylphosphoryl)-1-(4-methylphenyl)ethan-1-one

[0057] 0.2mmol 4-methylphenylacetylene, 0.05mmol sodium trifluoromethanesulfinate, 0.4mmol diphenylphosphine oxide, 1.0mL isopropanol were added to the reactor. In an air atmosphere, at room temperature, under irradiation of 30 watts of blue light with a wavelength of 400-410nm, the reaction was stirred for 20 hours. After the reaction was completed, it was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product with a yield of 82%. 1 H NMR (400MHz, CDCl3): δ7.85 (d, J = 6.8 Hz, 2H), 7.79–7.74 (m, 4H), 7.47–7.37 (m, 6H), 7.15 (d, J = 7.6 Hz, 2H), 4.08 (d, J = 15.2 Hz, 2H), 2.31 (s, 3H). 13 C NMR (101MHz, CDCl3): δ192.1(d,J C-P =5.7Hz),144.3,134.3,131.9(d,J C-P =2.0Hz),131.8(d,J C-P =103.1Hz),130.8(d,J C-P =9.8Hz),129.1,129.0,128.3(d,J C-P =12.3Hz),42.8(d,J C-P =58.4Hz),21.4. 31 P NMR (162 MHz, CDCl3): δ 27.18.

[0058] Synthesis example 3

[0059] Synthesis of β-(diphenylphosphoryl)-1-(4-methoxyphenyl)ethan-1-one

[0060] 0.2mmol 4-methoxyphenylacetylene, 0.05mmol sodium trifluoromethanesulfinate, 0.4mmol diphenylphosphine oxide, 1.0mL isopropanol were added to the reactor. In an air atmosphere, at room temperature, irradiated with 30 watts of blue light with a wavelength of 400-410nm, the reaction was stirred for 20 hours. After the reaction, the mixture was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product with a yield of 70%. 1 H NMR (400MHz, CDCl3): δ7.97–7.94(m,2H),7.81–7.75(m,4H),7.51–7.41(m,6H),6.87(d,J=6.8Hz,2H),4.07(d,J=15.3Hz,2H),3.81(s,3H). 13 C NMR (101MHz, CDCl3): δ191.0(d,J C-P =5.6Hz),163.9,132.1(d,J C-P =2.6Hz),131.8(d,J C-P =103.2Hz),131.7,131.0(d,J C-P =9.8Hz),130.0,128.5(d,J C-P =12.3Hz),113.6,55.4,43.0(d,J C-P =58.2Hz). 31 P NMR (162 MHz, CDCl3): δ 27.28.

[0061] Synthesis example 4

[0062] Synthesis of β-(diphenylphosphoryl)-1-(4-chlorophenyl)ethan-1-one

[0063] 0.2mmol 4-chlorophenylacetylene, 0.05mmol sodium trifluoromethanesulfinate, 0.4mmol diphenylphosphine oxide, 1.0mL isopropanol were added to the reactor. In an air atmosphere, at room temperature, irradiated with 30 watts of blue light with a wavelength of 400-410nm, the reaction was stirred for 20 hours. After the reaction was completed, it was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product with a yield of 75%. 1H NMR (400MHz, CDCl3): δ7.90–7.88(m,2H),7.77–7.72(m,4H),7.47–7.38(m,6H),7.32–7.29(m,2H),4.07(d,J=15.1Hz,2H). 13 C NMR (101MHz, CDCl3): δ191.4(d,J C-P =5.6Hz),139.9,135.0,132.0(d,J C-P =2.2Hz),131.4(d,J C-P =103.7Hz),130.7(d,J C-P =9.8Hz),130.5,128.5(d,J C-P =4.6Hz),128.4,43.1(d,J C-P =57.3Hz). 31 P NMR (162 MHz, CDCl3): δ 26.85.

[0064] Synthesis example 5

[0065] Synthesis of β-(diphenylphosphoryl)-1-(4-nitrophenyl)ethan-1-one

[0066] 0.2mmol 4-nitrobenzeneacetylene, 0.05mmol sodium trifluoromethanesulfinate, 0.4mmol diphenylphosphine oxide, 1.0mL isopropanol were added to the reactor. In an air atmosphere, at room temperature, under irradiation of 30 watts of blue light with a wavelength of 400-410nm, the reaction was stirred for 30 hours. After the reaction was completed, it was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product with a yield of 45%. 1 H NMR (400MHz, CDCl3): δ8.18–8.12(m,4H),7.77–7.72(m,4H),7.51–7.42(m,6H),4.17(d,J=14.9Hz,2H). 13 C NMR (101MHz, CDCl3): δ191.4(d,J C-P =5.6Hz),150.1,141.0,132.3,130.7(d,J C-P =9.8Hz),131.1(d,J C-P =103.7Hz),130.2,128.6(d,J C-P =12.4Hz),123.4,43.8(d,J C-P =53.1Hz). 31P NMR (162 MHz, CDCl3): δ 26.64.

[0067] Synthesis example 6

[0068] Synthesis of β-(diphenylphosphoryl)-1-(thiophen-3-yl)ethan-1-one

[0069] 0.2mmol 3-thiopheneacetylene, 0.05mmol sodium trifluoromethanesulfinate, 0.4mmol diphenylphosphine oxide, 1.0mL isopropanol were added to the reactor. In an air atmosphere, at room temperature, irradiated with 30 watts of blue light with a wavelength of 400-410nm, the reaction was stirred for 24 hours. After the reaction was completed, the mixture was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product with a yield of 60%. 1 H NMR (400MHz, CDCl3): δ8.26–8.25(m,1H),7.78–7.72(m,4H),7.46–7.37(m,7H),7.17–7.14(m,1H),3.99(d,J=15.3Hz,2H). 13 C NMR (101MHz, CDCl3): δ186.2(d,J C-P =5.2Hz),142.1,135.2,132.0,131.5(d,J C-P =103.2Hz),130.8(d,J C-P =9.9Hz),128.4(d,J C-P =12.4Hz),126.9,126.0,44.6(d,J C-P =58.1Hz). 31 P NMR (162MHz,CDCl3):δ26.89.

[0070] Synthesis Example 7

[0071] Synthesis of 1-(4,4-dimethylthiochroman-6-yl)-β-(diphenylphosphoryl)ethan-1-one

[0072] 0.2mmol 6-ethynyl-4,4-dimethylthiobenzopyran, 0.05mmol sodium trifluoromethanesulfinate, 0.4mmol diphenylphosphine oxide, 1.0mL isopropanol were added to the reactor. In an air atmosphere, at room temperature, irradiated with 30 watts of blue light with a wavelength of 400-410nm, the reaction was stirred for 24 hours. After the reaction was completed, it was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product with a yield of 62%. 1H NMR (400MHz, CDCl3): δ7.95 (s, 1H), 7.78–7.73 (m, 4H), 7.58 (d, J = 8.1Hz, 1H), 7.45–7.35 (m, 6H), 7.0 2(d,J=8.3Hz,1H),4.04(d,J=15.3Hz,2H),2.94(t,J=6.4Hz,2H),1.83(t,J=6.0Hz,2H),1.24(s,6H). 13 C NMR (101MHz, CDCl3): δ191.4(d,J C-P =5.5Hz),141.5,140.4,132.5,131.81(d,J C-P =2.3Hz),131.80(d,J C-P =103.0Hz),130.8(d,J C-P =9.8Hz),128.3(d,J C-P =12.3Hz),126.8,126.5,126.0,42.6(d,J C-P =58.3Hz),36.4,32.7,29.4,23.0. 31 P NMR (162 MHz, CDCl3): δ 27.27.

[0073] Synthesis example 8

[0074] Synthesis of β-[Bis(3,5-dimethylphenyl)phosphoryl]-1-phenylethan-1-one

[0075] 0.2mmol phenylacetylene, 0.05mmol sodium trifluoromethanesulfinate, 0.4mmol bis(3,5-dimethylphenyl)phosphine oxide, and 1.0mL isopropanol were added to the reactor. The mixture was stirred and reacted for 24 hours at room temperature and irradiated with 30 watts of blue light with a wavelength of 400-410nm under air atmosphere. After the reaction, the mixture was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent. The crude product was separated by column chromatography to obtain the target product with a yield of 65%. 1 H NMR (400MHz, CDCl3): δ7.96 (d, J = 7.3Hz, 2H), 7.49 (t, J = 7.4Hz, 1H), 7.39–7.35 (m, 6H), 7.09 (s, 2H), 4.08 (d, J = 15.3Hz, 2H), 2.29 (s, 12H). 13 C NMR (101MHz, CDCl3): δ192.8(d,J C-P =5.5Hz),138.1(d,J C-P=12.9Hz),136.9,133.7(d,J C-P =2.5Hz),133.2,131.5(d,J C-P =102.4Hz),129.0,128.4(d,J C-P =9.8Hz),128.2,43.1(d,J C-P =57.3Hz),21.1. 31 P NMR (162 MHz, CDCl3): δ 27.70.

[0076] It should be noted that, in each of the above embodiments, there is not necessarily a certain order between the above steps. A person skilled in the art can understand, based on the description of the embodiments of the present invention, that in different embodiments, the above steps may have different execution orders, that is, they may be executed in parallel, may be executed interchangeably, and so on.

[0077] The above contents are further detailed descriptions of the present invention in combination with specific preferred embodiments, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions. It is obvious that various modifications can be easily made to these embodiments by those skilled in the art to which the present invention belongs. Therefore, several simple deductions or substitutions made without departing from the concept and spirit of the present invention should be regarded as belonging to the protection scope of the present invention.

Claims

1. A method for synthesizing β-ketophosphorus oxide, characterized in that: The following steps are involved: Sodium trifluoromethanesulfinate, an arylphosphorus oxide compound, an aromatic alkyne compound and a solvent are placed in a reaction container and mixed; In an air atmosphere, at room temperature, under blue light irradiation, the reaction was continued with stirring for 12 to 30 hours. After the reaction was completed, the mixture was washed with water, extracted with ethyl acetate, dried, and concentrated by vacuum distillation to remove the solvent to obtain a crude product. The crude product is separated by column chromatography to obtain the target product; The synthetic reaction formula of the target product is as follows: ； The target product has one or more of structural formula I, structural formula II, and structural formula III, wherein the structural formula I, structural formula II, and structural formula III are shown below: ； In the structural formula I, R 1 is one of hydrogen, methyl, ethyl, tert-butyl, methoxy, fluorine, chlorine, bromine, cyano, trifluoromethyl, nitro, methyl ester, and phenyl; R 2 It is one of hydrogen, chlorine, methyl, and methoxy; The solvent is selected from one of dichloromethane, isopropanol, methanol and tert-butanol; The molar ratio of the sodium trifluoromethanesulfinate, the aryl phosphorus oxide compound and the aromatic alkyne compound is [0.1-0.3]:[1.5-2.0]:1; The blue light irradiation power is 30 watts; The wavelength of the blue light is 400-460nm.

2. The method for synthesizing β-ketophosphorus oxide according to claim 1, characterized in that: The aromatic phosphorus oxide compound is selected from one of diphenylphosphine oxide, bis(p-methylphenyl)phosphine oxide, bis(4-chlorophenyl)phosphine oxide and bis(p-methoxyphenyl)phosphine oxide.

3. The method for synthesizing β-ketophosphorus oxide according to claim 1, characterized in that: The aromatic alkyne compound is selected from one of phenylacetylene, 4-methylphenylacetylene, 4-ethylphenylacetylene, 4-tert-butylphenylacetylene, 4-methoxyphenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 4-bromophenylacetylene, 4-phenylphenylacetylene, 3-thiopheneacetylene, and 6-ethynyl-4,4-dimethyldihydrobenzothiopyran.

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