Benzothiazole phosphorus compound as well as synthesis method and application thereof

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a benzothiazole phosphorus compound and a synthesis method and application thereof.The synthesis method of the benzothiazole phosphorus compound specifically comprises the steps that a benzothiazole compound and an organic phosphorus compound are placed in a solvent and react in a nitrogen atmosphere under the action of illumination and an oxidizing agent, and the benzothiazole phosphorus compound is obtained. And the benzothiazole phosphorus compound is obtained. The molar ratio of the benzothiazole compound to the organic phosphorus compound is (1: 1)-(1: 5.5), and the oxidizing agent is persulfate. The preparation method comprises the following steps: adding a certain amount of water into a reaction kettle, reacting for 24-30 hours, dissolving solids in a reaction solution, adding ethyl acetate for extraction for three times, collecting the ethyl acetate, spin-drying, separating by a chromatographic column, and purifying to obtain a series of benzothiazole phosphorus compounds. The synthesis method disclosed by the invention is simple and convenient to operate and high in product yield.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a benzothiazole phosphorus compound and a synthesis method and application thereof. Background Art

[0002] Thiazole compounds are a class of heterocyclic compounds containing nitrogen and sulfur. Studies have found that this type of compound has multiple biological activities such as insecticide, antibacterial, anticancer and plant growth regulation. A variety of thiazole drugs have been announced one after another, such as thiofluanid, which can be used to prevent and control viruses caused by the nucleus of the fungus mycelium; thiothiocyanate, which can prevent and treat fungal or bacterial diseases transmitted by soil and seeds; and allylthiazole, which has a good effect in preventing and controlling rice blast. In addition, other thiazole drugs such as the antibacterial agent thiothiocyanate, the insecticide thiamethoxam and the anti-inflammatory drug meloxicam have been developed and put on the market. The chemical molecular structures of these drugs are as follows: Figure 5 shown.

[0003] Similarly, organophosphorus compounds are also an important class of organic compounds. Organophosphorus compounds have been widely used in organic synthesis, medicinal chemistry, pesticides, materials chemistry, natural products, catalysis and coordination chemistry. For example, chiral phosphine ligands represented by BINAP (1,1-binaphthyl-2,2'-bisdiphenylphosphine) have been developed and applied in the field of asymmetric catalysis. In addition, there are important organophosphorus ligands such as CAMP (cyclic adenosine-3',5'-monophosphate), SEGPHOS (5,5-bis(diphenylphosphine)-4,4-di-1,3-piperazine), and BPE (1,2-bis(2,5-diphenylphosphino)ethane). The chemical molecular structures of these organophosphorus ligands are as follows: Figure 6 As shown. In terms of drugs, some organophosphorus compounds have received widespread attention due to their unique biochemical activity. For example, Cidofovir can be used as a new drug against cytomegalovirus (CMV). This compound significantly improves the activity while reducing the development of viral resistance; Fosinopril can be used to treat hypertension or as an adjuvant therapy; Remdesivir can be used to fight Ebola virus and pneumonia virus because of its broad-spectrum antiviral activity. The chemical molecular structures of the above-mentioned organophosphorus compounds used in ligands and drugs are shown in Figure 6 shown.

[0004] There are also many methods for synthesizing benzothiazole phosphine compounds disclosed at present. Some of these methods are complicated to operate, some raw materials are not easy to obtain, some have low yields, and some have high costs. For example, the Chinese patent application with publication number CN118908997A discloses a preparation method and application of α-phosphonyl imine compounds, which can synthesize α-diphenylphosphonylbenzo[d]thiazole, i.e. 2-diphenylphosphineoxybenzothiazole compounds. The preparation method of the Chinese patent application with publication number CN118908997A is: 0.2mmol benzothiazole, 0.2mmol diphenylphosphine oxide, and 0.01mmol photocatalyst 4CzIPN are placed in a photoreaction tube containing a stirrer, 2mL dichloromethane solvent is added, and the reaction is carried out for 24 hours at room temperature. After completion, dichloromethane was used for extraction (4 mL*3), the organic phases were combined, washed with saturated brine (5 mL*3), dried with anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and then separated and purified by silica gel column chromatography to finally obtain 74 mg of a white solid compound with a yield of 87%. This preparation method uses a photocatalyst to promote the reaction. The photocatalyst is relatively expensive, has a complex molecular structure, and the catalytic effect is easily affected by light conditions and is not stable enough.

[0005] In view of this, it is of positive significance to study new methods for synthesizing benzothiazole phosphine compounds. Summary of the invention

[0006] The purpose of the present invention is to provide a benzothiazole phosphorus compound and a synthesis method and application thereof.

[0007] The present invention provides a method for synthesizing a benzothiazole phosphorus compound, comprising the following steps: The benzothiazole compound represented by formula II and the organophosphorus compound represented by formula III are placed in a solvent and reacted in a nitrogen atmosphere by light and an oxidant to obtain the benzothiazole phosphorus compound; , In the formula, R1 and R2 are independently selected from hydrogen, C1-C18 alkyl, C1-C18 alkoxy, halogen, trifluoromethyl or nitro; The molar ratio of the benzothiazole compound to the organic phosphorus compound is 1:1 to 1:5.5, and the oxidant is persulfate.

[0008] In the above synthesis method, the benzothiazole compound represented by Formula II has a structure represented by any one of the following Formula II-1 to Formula II-24: ; The organic phosphorus compound represented by Formula III is a diphenylphosphine oxide compound, and the diphenylphosphine oxide compound has a structure represented by any one of the following Formulas III-1 to III-12: .

[0009] In the above synthesis method, the solvent is acetonitrile (CH3CN), and the amount of acetonitrile used is 1.5-2.5 ml.

[0010] In the above synthesis method, the reaction temperature is room temperature, specifically 20°C to 30°C, and the reaction time is 24 h to 30 h.

[0011] In the above synthesis method, the preferred range of the molar ratio of the benzothiazole compound to the organic phosphorus compound (i.e., diphenylphosphine oxide compound) is 1:3.5~1:5; the optimal ratio of the molar ratio of the benzothiazole compound to the organic phosphorus compound (i.e., diphenylphosphine oxide compound) is 1:5.

[0012] In the above synthesis method, the molar ratio between the oxidant and the benzothiazole compound is 1.5:1 to 3:1, and the optimal ratio is 2:1.

[0013] In the above synthesis method, the persulfate is potassium persulfate (K2S2O8), sodium persulfate (Na2S2O8) or ammonium persulfate [(NH4)2S2O8].

[0014] In the above synthesis method, the optimal illumination condition is blue light with a power of 24 W to 40 W.

[0015] The benzothiazole phosphorus compound prepared by the present invention has a structure shown in Formula I: , In the formula, R1 and R2 are independently selected from one of hydrogen, C1-C18 alkyl, C1-C18 alkoxy, halogen, trifluoromethyl and nitro.

[0016] Preferably, R1 and R2 are independently selected from one of hydrogen, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, fluorine, chlorine, bromine, iodine, nitro and trifluoromethyl.

[0017] Preferably, R1 is independently selected from one of methyl, methoxy, nitro, fluorine, chlorine and bromine, and R2 is independently selected from one of hydrogen, methyl, methoxy, trifluoromethyl, chlorine and bromine.

[0018] In some preferred embodiments, the benzothiazole phosphorus compound has a structure shown in any one of the following Formulas I-1 to I-34: .

[0019] The present invention provides an application of the benzothiazole phosphorus compound in inhibiting tomato gray mold. The benzothiazole phosphorus compound has good inhibitory activity against tomato gray mold.

[0020] The beneficial effects of the present invention are as follows: The present invention utilizes the more friendly method of light, using diphenylphosphine oxide compounds as a phosphorus source, and directly constructs a "CP" bond at the 2nd position of the benzothiazole compound. The method of the present invention has mild reaction conditions, no photocatalyst is required, the substrate does not need to be activated, the operation is simple, the preparation steps are few, the cost is low, the product yield is high, and it conforms to the concept of green development. In addition, the benzothiazole phosphorus compound prepared by the present invention has good inhibitory activity against tomato gray mold fungus, and can be used as a bactericide to inhibit tomato gray mold fungus. The prior art patent application with publication number CN118908997A uses a photocatalyst for catalysis, while the present invention uses an oxidant for reaction. The two synthesis methods have their own characteristics, but the reaction mechanisms of the two synthesis methods are different; and the yield of the prior art synthesis method is up to 87%, and the yield of the synthesis method of the present invention can reach up to 97%, which is 10% higher than the yield of the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The specific implementation modes of the present invention are further described in detail below with reference to the accompanying drawings.

[0022] Figure 1 This is the hydrogen spectrum of the product 2-diphenylphosphinothiazole in Example 1 of the present invention.

[0023] Figure 2 This is the carbon spectrum of the product 2-diphenylphosphinothiazole in Example 1 of the present invention.

[0024] Figure 3 This is the phosphorus spectrum of the product 2-diphenylphosphinothiazole in Example 1 of the present invention.

[0025] Figure 4 The figure is a reaction mechanism diagram of the synthesis method of the benzothiazole phosphorus compound of the present invention.

[0026] Figure 5 The figure is a diagram of the chemical molecular structure of some thiazole compounds in the prior art.

[0027] Figure 6 The diagram shows the chemical molecular structures of some organophosphorus compounds used in ligands and drugs in the prior art. DETAILED DESCRIPTION

[0028] In order to more clearly understand the above-mentioned purpose, features and advantages of the present invention, the present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments. In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention can also be implemented in other ways different from those described herein, and therefore, the present invention is not limited to the limitations of the specific embodiments disclosed below.

[0029] Example 1: Synthesis of 2-diphenylphosphinothiazole

[0030] 0.2 mmol of benzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were added to a dry photoreaction tube equipped with a magnetron. Then the photoreaction tube was evacuated and filled with nitrogen. Under a nitrogen atmosphere, 2 ml of CH3CN was injected into the photoreaction tube through a syringe and sealed. Subsequently, the sealed photoreaction tube was placed under blue light at room temperature (i.e., 20 ℃ ~ 30 ℃) and stirred for 24 h under this condition. After 24 h of reaction, a certain amount of water was added to the photoreaction tube to completely dissolve the solid in the reaction solution, and then ethyl acetate was added for extraction, extracted 3 times in total, ethyl acetate was collected, the solvent was evaporated under reduced pressure, separated and purified by chromatographic column, and finally 65.06 mg of the target product 2-diphenylphosphine oxybenzothiazole was obtained with a yield of 97%. The molecular formula structure corresponding to the product in this example is Ⅰ-1.

[0031] The product was identified as 2-diphenylphosphinothiazole by hydrogen spectrum, carbon spectrum and phosphorus spectrum of nuclear magnetic resonance. Figure 1 , carbon spectrum see Figure 2 , phosphorus spectrum see Figure 3 , the structural characterization data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 8.2 Hz, 1H), 7.99 (dt, J =15.7, 5.6 Hz, 5H), 7.61 – 7.44 (m, 8H). 13 C NMR (100 MHz, CDCl3) δ 167.6, 166.3, 155.5 (d, J = 22.0 Hz), 136.9, 132.8 (d, J = 22.0 Hz), 132.1 (d, J = 10.0 Hz), 130.6 128.8 (d, J =13.0 Hz), 126.8 (d, J = 5.0 Hz), 124.9, 122.2. 31P NMR (162 MHz, CDCl3) δ 19.95.

[0032] Example 2: Synthesis of 2-diphenylphosphinothiazole

[0033] 0.2 mmol of benzothiazole, 0.7 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were added to a dry photoreaction tube equipped with a magnetron. Then the photoreaction tube was evacuated and filled with nitrogen. In a nitrogen atmosphere, 2 ml of CH3CN was injected into the photoreaction tube through a syringe and sealed. Subsequently, the sealed photoreaction tube was placed under blue light at room temperature and stirred for 24 h under this condition. After 24 h of reaction, a certain amount of water was added to the photoreaction tube to completely dissolve the solid in the reaction solution, and then ethyl acetate was added for extraction. The extraction was performed 3 times in total, and ethyl acetate was collected. The solvent was evaporated under reduced pressure, separated and purified by chromatographic column, and finally 60.36 mg of the target product 2-diphenylphosphine oxybenzothiazole was obtained, with a yield of 90%. The molecular formula structure corresponding to the product in this example is Ⅰ-1. This example shows that changing the amount of diphenylphosphine has a certain effect on the yield. After screening the reaction conditions, it was found that the optimal dosage ratio of diphenylphosphine to benzothiazole is the molar ratio used in Example 1.

[0034] Example 3: Synthesis of 2-diphenylphosphinothiazole

[0035] 0.2 mmol of benzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of ammonium persulfate were added to a dry photoreaction tube equipped with a magnetron. Then the photoreaction tube was evacuated and filled with nitrogen. In a nitrogen atmosphere, 2 ml of CH3CN was injected into the photoreaction tube through a syringe and sealed. Subsequently, the sealed photoreaction tube was placed under blue light at room temperature and stirred for 24 h under this condition. After 24 h of reaction, a certain amount of water was added to the photoreaction tube to completely dissolve the solid in the reaction solution, and then ethyl acetate was added for extraction. The extraction was performed 3 times in total, and ethyl acetate was collected. The solvent was evaporated under reduced pressure, separated and purified by chromatographic column, and finally 59.02 mg of the target product 2-diphenylphosphine oxybenzothiazole was obtained, with a yield of 88%. The molecular formula structure corresponding to the product in this example is Ⅰ-1. This example shows that changing the oxidant has a certain effect. After screening the reaction conditions, it was found that the best oxidant was potassium persulfate.

[0036] Example 4: Synthesis of 2-diphenylphosphinothiazole

[0037] 0.2 mmol of benzothiazole, 0.7 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were added to a dry photoreaction tube equipped with a magnetron. Then the photoreaction tube was evacuated and filled with nitrogen. Under a nitrogen atmosphere, 2 ml of CH3CN was injected into the photoreaction tube through a syringe and sealed. Subsequently, the sealed photoreaction tube was placed in a black box and stirred for 24 h at room temperature. After 24 h of reaction, a certain amount of water was added to the photoreaction tube to completely dissolve the solid in the reaction solution, and then ethyl acetate was added for extraction. The extraction was performed 3 times in total, ethyl acetate was collected, the solvent was evaporated under reduced pressure, and the chromatographic column was separated and purified. Finally, only 5.37 mg of the target product 2-diphenylphosphine oxybenzothiazole was obtained, and the yield was only 8%. This example is used as a comparative example to illustrate that the illumination conditions play a key role in the reaction. The molecular formula structure corresponding to the product in this example is Ⅰ-1.

[0038] Example 5: Synthesis of 4-methyl-2-diphenylphosphinoylbenzothiazole

[0039] Based on the synthesis method of Example 1, 0.2 mmol of 4-methylbenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 47.52 mg of the target product 4-methyl-2-diphenylphosphineoxybenzothiazole with a yield of 68%. The molecular formula structure of the product in this example is Ⅰ-2.

[0040] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ8.06−7.94 (m, 4H), 7.82 (d, J = 7.9 Hz, 1H), 7.56 (dd, J = 10.4, 4.3Hz, 2H), 7.49 (td, J = 7.4, 3.2 Hz, 4H), 7.36 (dt, J =14.8, 7.3 Hz, 2H),2.78 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 164.7 (d, J = 129.0 Hz), 154.8 (d, J = 21.1Hz), 136.5, 134.7, 132.4 (d, J = 2.8 Hz), 131.8 (d, J = 10.1 Hz), 130.6,128.4 (d, J = 12.8 Hz), 126.9, 126.5, 119.3, 18.3. 31P NMR (162 MHz, CDCl3) δ 19.4.

[0041] Example 6: Synthesis of 5-methyl-2-diphenylphosphinoylbenzothiazole

[0042] 0.2 mmol of 5-methylbenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were added to a dry photoreaction tube equipped with a magnetron. Then the photoreaction tube was evacuated and filled with nitrogen. In a nitrogen atmosphere, 2 ml of CH3CN was injected into the photoreaction tube through a syringe and sealed. Subsequently, the sealed photoreaction tube was placed under blue light at room temperature and stirred for 24 h under this condition. After 24 h of reaction, a certain amount of water was added to the photoreaction tube to completely dissolve the solid in the reaction solution, and then ethyl acetate was added for extraction, and extracted 3 times in total. The ethyl acetate was collected, the solvent was evaporated under reduced pressure, and the chromatographic column was separated and purified to finally obtain 58.70 mg of the target product 5-methyl-2-diphenylphosphine oxybenzothiazole with a yield of 84%. The molecular formula structure corresponding to the product in this example is Ⅰ-3.

[0043] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.02 – 7.92(m, 5H), 7.86 (d, J = 8.2 Hz, 1H), 7.55 (td, J = 7.2, 1.6 Hz, 2H), 7.52 –7.44 (m, 4H), 7.30 (dd, J = 8.3, 1.6 Hz, 1H), 2.50 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ166.7 (d, J =127.0 Hz), 156.0 (d, J =22.0Hz), 137.0, 134.0,132.7 (d, J =2.0 Hz), 131.0 (d, J =10.0 Hz),131.8, 130.7,128.7 (d, J =12.0 Hz), 124.6, 121.6, 21.5. 31 P NMR (162 MHz, CDCl3) δ 19.97.

[0044] Example 7: Synthesis of 6-methyl-2-diphenylphosphinoylbenzothiazole

[0045] Based on the synthesis method of Example 1, 0.2 mmol of 6-methylbenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 56.60 mg of the target product 6-methyl-2-diphenylphosphineoxybenzothiazole with a yield of 81%. The molecular formula structure of the product in this example is Ⅰ-4.

[0046] The structural characterization data of the product in this example are as follows: 1 H NMR (400MHz, CDCl3) δ 8.06 (d, J = 8.6 Hz, 1H), 8.01−7.91 (m, 4H), 7.79 (s,1H), 7.60−7.53 (m, 2H), 7.52−7.45 (m, 4H), 7.35 (d, J = 8.6 Hz,1H),2.55 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 165.4 (d, J =128.3 Hz), 153.7 (d, J = 21.8Hz), 137.2, 132.6 (d, J = 2.8 Hz), 132.0 (d, J = 10.2 Hz), 131.3 (d, J = 108.7Hz), 128.7 (d, J = 12.8 Hz), 128.6, 124.3, 121.7, 21.7. 31 P NMR (162 MHz, CDCl3) δ 19.9.

[0047] Example 8: Synthesis of 7-methyl-2-diphenylphosphinoylbenzothiazole

[0048] Based on the synthesis method of Example 1, 0.2 mmol of 7-methylbenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 43.32 mg of the target product 7-methyl-2-diphenylphosphineoxybenzothiazole with a yield of 62%. The molecular formula structure of the product in this example is Ⅰ-5.

[0049] The structural characterization data of the product in this example are as follows: 1H NMR (400 MHz, CDCl3) δ8.09−7.97 (m, 4H), 7.85 (d, J = 7.9 Hz, 1H), 7.59 (dd, J = 10.4, 4.3Hz, 2H), 7.52 (td, J = 7.4, 3.2 Hz, 4H), 7.39 (dt, J =14.8, 7.3 Hz, 2H),2.86 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 165.4 (d, J = 129.0 Hz), 155.5 (d, J = 21.1Hz), 137.0, 135.4, 132.9 (d, J = 2.8 Hz), 132.3 (d, J = 10.1 Hz), 131.2,128.9 (d, J = 12.8 Hz), 127.5, 127.1, 119.7, 18.8. 31 P NMR (162 MHz, CDCl3) δ 19.7.

[0050] Example 9: Synthesis of 4-chloro-2-diphenylphosphinoylbenzothiazole

[0051] Based on the synthesis method of Example 1, 0.2 mmol of 4-chlorobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 48.07 mg of the target product 4-chloro-2-diphenylphosphineoxybenzothiazole with a yield of 65%. The molecular formula structure of the product in this example is Ⅰ-6.

[0052] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.92 (s, 1H), 8.05 (td, J = 12.9, 8.1 Hz, 4H), 7.58~7.66 (m, ,8H). 13C NMR (100 MHz, CDCl3) δ 167.8 (d, J = 124.9 Hz), 154.0 (d, J = 21.6Hz), 138.1, 133.0, 132.8 (d, J = 2.8 Hz), 132.0 (d, J = 10.3 Hz), 130.8 (d, J = 108.7 Hz), 128.8 (d, J = 13.0 Hz), 127.8, 125.5, 121.7.

[0053] Example 10: Synthesis of 4-bromo-2-diphenylphosphinoylbenzothiazole

[0054] Based on the synthesis method of Example 1, 0.2 mmol of 4-bromobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 48.05 mg of the target product 4-bromo-2-diphenylphosphineoxybenzothiazole with a yield of 58%. The molecular formula structure of the product in this example is Ⅰ-7.

[0055] The structural characterization data of the product in this example are as follows: 1 H NMR (400MHz, CDCl3) δ 8.18 (d, J = 1.5 Hz, 1H), 8.06 (d, J = 8.8Hz, 1H), 8.03−7.95 (m, 4H), 7.66 (dd, J = 8.8, 1.5 Hz, 1H), 7.64−7.58 (m,2H),7.57−7.4 (m, 4H). 13 C NMR (100 MHz, CDCl3) δ 167.8(d, J = 124.8 Hz), 154.2 (d, J = 21.5Hz), 138.5, 132.9 (d, J = 2.8Hz), 132.0 (d, J = 10.4 Hz), 130.7 (d, J = 109.3Hz), 130.4, 128.8(d, J = 13.0 Hz), 125.8, 124.7, 120.9.

[0056] Example 11: Synthesis of 4-fluoro-2-diphenylphosphinoylbenzothiazole

[0057] Based on the synthesis method of Example 1, 0.2 mmol of 4-fluorobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 44.52 mg of the target product 4-fluoro-2-diphenylphosphineoxybenzothiazole with a yield of 63%. The molecular formula structure of the product in this example is Ⅰ-8.

[0058] The structural characterization data of the product in this example are as follows: 1 H NMR (400MHz, CDCl3) δ 8.08 (dd, J = 9.0, 4.6 Hz, 1H), 7.91−7.82 (m,4H), 7.69−7.45 (m, 7H), 7.21 (td, J = 8.8, 2.4 Hz, 1H). 13 C NMR (100 MHz, CDCl3)δ 166.7 (dd, J = 126.3, 3.5 Hz), 161.1 (d, J =249.1 Hz), 151.8 (d, J =22.3 Hz), 137.8 (d, J = 11.5 Hz), 132.5 (d, J = 2.8Hz), 131.6 (d, J =10.3 Hz), 130.4 (d, J = 109.1 Hz), 128.8 (d, J = 12.9 Hz), 125.6 (d, J =9.7 Hz), 115.4 (d, J = 25.3 Hz), 107.7 (d, J = 26.6 Hz).

[0059] Example 12: Synthesis of 4-methoxy-2-diphenylphosphinothiazole

[0060] Based on the synthesis method of Example 1, 0.2 mmol of 4-methoxybenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 46.04 mg of the target product 4-methoxy-2-diphenylphosphineoxybenzothiazole, with a yield of 63%. The molecular formula structure corresponding to the product in this example is Ⅰ-9.

[0061] The structural characterization data of the product in this example are as follows: 1H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 8.7 Hz, 1H), 7.77−7.70 (m, 4H), 7.54−7.49 (m, 2H), 7.46−7.41 (m, 4 H), 7.35 (d, J = 2.2 Hz, 1H), 7.18 (dd, J =8.7, 2.3 Hz, 1H), 3.93 (s, 3H). 13 C NMR (100MHz, CDCl3) δ 156.2 (d, J = 129.8 Hz), 150.3, 146.6 (d, J= 21.9 Hz), 134.2, 133.1 (d, J = 2.5 Hz), 132.3 (d, J = 9.3 Hz), 128.8 (d, J= 107.6 Hz), 121.8 (d, J = 12.7 Hz), 114.1, 108.2, 54.8.

[0062] Example 13: Synthesis of 5-methoxy-2-diphenylphosphinothiazole

[0063] Based on the synthesis method of Example 1, 0.2 mmol of 5-methylbenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 52.61 mg of the target product 5-methoxy-2-diphenylphosphineoxybenzothiazole, with a yield of 72%. The molecular formula structure corresponding to the product in this example is Ⅰ-10.

[0064] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 9.1 Hz, 1H), 8.00−7.90 (m,4H), 7.59−7.53 (m, 2H), 7.52−7.45 (m, 4 H), 7.40 (d, J = 2.5 Hz,1H), 7.14 (dd, J =9.1, 2.5 Hz, 1H), 3.87 (s, 3H). 13C NMR (100MHz, CDCl3) δ 163.3 (d, J = 129.8 Hz), 158.8, 150.1 (d, J= 21.9 Hz), 138.6, 132.5 (d, J = 2.7 Hz), 131.8 (d, J = 10.3 Hz), 131.2 (d, J = 109.6 Hz), 128.6 (d, J = 12.7 Hz), 125.2, 117.1, 103.4,55.8.

[0065] Example 14: Synthesis of 6-methoxy-2-diphenylphosphinothiazole

[0066] Based on the synthesis method of Example 1, 0.2 mmol of 6-methoxybenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 53.34 mg of the target product 6-methoxy-2-diphenylphosphineoxybenzothiazole with a yield of 73%. The molecular formula structure of the product in this example is Ⅰ-11.

[0067] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.85−7.69 (m,4H), 7.62−7.52 (m, 2H), 7.48−7.40 (m, 6 H), 7.06 (dd, J = 9.1, 2.5 Hz, 1H), 3.82 (s, 3H). 13 C NMR (100MHz, CDCl3) δ 156.7 (d, J = 127.8 Hz), 156.0, 145.6 (d, J= 21.0 Hz), 136.1, 134.2 (d, J = 2.7 Hz), 132.3 (d, J = 9.9 Hz), 128.8 (d, J= 108.6 Hz), 122.6 (d, J = 12.7 Hz), 114.6, 104.9, 55.5.

[0068] Example 15: Synthesis of 7-methoxy-2-diphenylphosphinothiazole

[0069] Based on the synthesis method of Example 1, 0.2 mmol of 7-methoxybenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 37.40 mg of the target product 7-methoxy-2-diphenylphosphineoxybenzothiazole with a yield of 52%. The molecular formula structure of the product in this example is Ⅰ-12.

[0070] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 8.7 Hz, 1H), 7.97−7.88 (m,4H), 7.56-7.51 (m, 2H), 7.52−7.48 (m, 5H), 7.04 (dd, J = 9.1, 2.5 Hz, 1H), 3.83(s, 3H). 13 C NMR (100MHz, CDCl3) δ 156.2, 154.5, 153,9, 134.2(d, J = 2.7 Hz), 133.1 (d, J = 2.2 Hz), 132.3 (d, J = 9.3 Hz), 128.8(d, J = 108.6 Hz), 126.3,120.7,113.9, 55.2.

[0071] Example 16: Synthesis of 5-chloro-2-diphenylphosphinoylbenzothiazole

[0072] 0.2 mmol of 5-chlorobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were added to a dry photoreaction tube equipped with a magnetron. Then the photoreaction tube was evacuated and filled with nitrogen. In a nitrogen atmosphere, 2 ml of CH3CN was injected into the photoreaction tube through a syringe and sealed. Subsequently, the sealed photoreaction tube was placed under blue light at room temperature and stirred for 24 h under this condition. After 24 h of reaction, a certain amount of water was added to the photoreaction tube to completely dissolve the solid in the reaction solution, and then ethyl acetate was added for extraction, and extracted 3 times in total. The ethyl acetate was collected, the solvent was evaporated under reduced pressure, and the chromatographic column was separated and purified to finally obtain 59.91 mg of the target product 5-chloro-2-diphenylphosphine oxybenzothiazole with a yield of 81%. The molecular formula structure corresponding to the product in this example is Ⅰ-13.

[0073] The structural characterization data of the product in this example are as follows: 1H NMR (400 MHz, CDCl3) δ 8.18 (s, 1H), 7.95 (td, J = 12.9, 8.1 Hz, 5H), 7.58 (t, J = 7.4 Hz, 2H), 7.49 (ddd, J = 21.1, 10.5, 5.9 Hz, 5H). 13 C NMR (100 MHz, CDCl3) δ 169.4 (d, J =124.0 Hz), 156.3 (d, J =22.0Hz), 135.2, 132.9 (d, J =10.0 Hz), 132.0 (d, J = 11.0 Hz), 131.4, 130.3,128.9 (d, J =13.0 Hz), 127.4, 124.5, 123.0. 31 P NMR (162 MHz, CDCl3) δ 19.79.

[0074] Example 17: Synthesis of 5-bromo-2-diphenylphosphinoylbenzothiazole

[0075] 0.2 mmol of 5-bromobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were added to a dry photoreaction tube equipped with a magnetron. Then the photoreaction tube was evacuated and filled with nitrogen. In a nitrogen atmosphere, 2 ml of CH3CN was injected into the photoreaction tube through a syringe and sealed. Subsequently, the sealed photoreaction tube was placed under blue light at room temperature and stirred for 24 h under this condition. After 24 h of reaction, a certain amount of water was added to the photoreaction tube to completely dissolve the solid in the reaction solution, and then ethyl acetate was added for extraction, and the extraction was performed 3 times in total. The ethyl acetate was collected, the solvent was evaporated under reduced pressure, and the chromatographic column was separated and purified to finally obtain 74.57 mg of the target product 5-bromo-2-diphenylphosphine oxybenzothiazole, with a yield of 90%. The molecular formula structure corresponding to the product in this example is Ⅰ-14.

[0076] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.35 (s, 1H), 7.96 (dd, J = 12.8, 7.6 Hz,4H), 7.86 (d, J = 8.6 Hz, 1H), 7.64 – 7.55 (m, 3H), 7.50 (td, J = 7.7, 3.1Hz, 4H). 13 C NMR (100 MHz, CDCl3) δ 169.2 (d, J = 123.0 Hz), 156.6 (d, J = 21.0Hz), 135.7, 132.9 (d, J = 3.0 Hz), 132.0 (d, J = 11.0 Hz), 131.3, 130.1 (d, J = 30.0 Hz), 128.9 (d, J = 18.0 Hz), 127.7, 123.3, 120.6. 31 P NMR (162 MHz, CDCl3) δ 19.78.

[0077] Example 18: Synthesis of 5-fluoro-2-diphenylphosphinoylbenzothiazole

[0078] Based on the synthesis method of Example 1, 0.2 mmol of 5-fluorobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 55.83 mg of the target product 5-fluoro-2-diphenylphosphineoxybenzothiazole, with a yield of 79%. The molecular formula structure of the product in this example is Ⅰ-15.

[0079] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ7.94 (dd, J = 4.8, 9.2 Hz, 1 H), 7.92 (dd, J= 2.3, 7.9 Hz, 1 H), 7.75-7.83 (m, 4 H), 7.64 (td, J = 1.1, 7.3 Hz, 2 H), 7.58 (td, J = 3.2, 7.6 Hz, 4 H), 7.26 (td, J = 2.4, 8.9 Hz, 1 H). 13C NMR (100 MHz, CDCl3) δ 165.3 (d, J = 126.3, 3.3 Hz), 161.2 (d, J =249.0 Hz), 152.0 (d, J = 21.7 Hz), 136.8 (d, J = 11.3 Hz), 131.6 (d, J = 2.6Hz), 131.3 (d, J = 10.3 Hz), 130.8 (d, J = 109.2 Hz), 128.6 (d, J = 12.8 Hz), 125.8, 115.8 (d, J = 25.3 Hz), 108.8 (d, J = 26.7 Hz).

[0080] Example 19: Synthesis of 5-nitro-2-diphenylphosphinoylbenzothiazole

[0081] Based on the synthesis method of Example 1, 0.2 mmol of 5-nitrobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 59.33 mg of the target product 5-nitro-2-diphenylphosphineoxybenzothiazole with a yield of 78%. The molecular formula structure of the product in this example is Ⅰ-16.

[0082] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.32 (d, J = 2.2 Hz, 1H), 8.45 (dd, J = 9.1,2.2 Hz, 1H), 8.37 (d, J = 9.1 Hz, 1H), 8.09- 7.88 (m, 4H), 7.63 (td, J = 7.3,1.4 Hz, 2H), 7.59−7.48 (m,4H). 13 C NMR (100 MHz, CDCl3) δ 158.4(d, J = 20.8 Hz), 155.7 (d, J = 108.5Hz), )145.8, 137.0, 133.0 (d, J = 2.9 Hz), 131.9 (d, J = 10.3Hz), 130.0 (d, J= 109.5 Hz), 128.8 (d, J = 13.0 Hz), 123.2, 121.7,119.1.

[0083] Example 20: Synthesis of 6-chloro-2-diphenylphosphinoylbenzothiazole

[0084] Based on the synthesis method of Example 1, 0.2 mmol of 6-chlorobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 59.90 mg of the target product 6-chloro-2-diphenylphosphineoxybenzothiazole with a yield of 81%. The molecular formula structure of the product in this example is Ⅰ-17.

[0085] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.12 (d, J = 8.8 Hz, 1H), 8.04−7.94 (m, 5H), 7.65−7.58 (m, 2H), 7.58−7.49 (m, 5H). 13 C NMR (100 MHz, CDCl3) δ 168.1 (d, J = 124.9 Hz), 154.2 (d, J = 21.6Hz), 138.4,133.3, 133.1 (d, J = 2.8 Hz), 132.3 (d, J = 10.3 Hz), 131.1 (d, J=108.7 Hz), 129.1 (d, J = 13.0 Hz), 128.0, 125.8, 121.9.

[0086] Example 21: Synthesis of 6-bromo-2-diphenylphosphinoylbenzothiazole

[0087] Based on the synthesis method of Example 1, 0.2 mmol of 6-bromobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 62.14 mg of the target product 6-bromo-2-diphenylphosphineoxybenzothiazole with a yield of 75%. The molecular formula structure of the product in this example is Ⅰ-18.

[0088] The structural characterization data of the product in this example are as follows: 1 H NMR (400MHz, CDCl3) δ 8.17 (d, J = 1.5 Hz, 1H), 8.05 (d, J = 8.8Hz, 1H), 8.02−7.94 (m, 4H), 7.65 (dd, J = 8.8, 1.5 Hz, 1H), 7.63−7.57 (m,2H), 7.56−7.48 (m, 4H). 13 C NMR (100 MHz, CDCl3) δ 168.1 (d, J = 124.8 Hz), 154.5 (d, J = 21.5Hz), 138.8, 133.2 (d, J = 2.8 Hz), 132.2 (d, J = 10.4 Hz), 130.9 (d, J =109.3 Hz), 130.6, 129.1 (d, J = 13.0 Hz), 126.0, 124.9, 121.1.

[0089] Example 22: Synthesis of 6-fluoro-2-diphenylphosphinoylbenzothiazole

[0090] Based on the synthesis method of Example 1, 0.2 mmol of 6-fluorobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 50.88 mg of the target product 6-fluoro-2-diphenylphosphineoxybenzothiazole with a yield of 72%. The molecular formula structure of the product in this example is Ⅰ-19.

[0091] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.15 (dd, J = 4.8, 9.2 Hz, 1 H), 7.95-8.05(m, 4 H), 7.70 (dd, J = 2.3, 7.9 Hz, 1 H), 7.60 (td, J = 1.1, 7.3 Hz, 2 H), 7.53 (td, J = 3.2, 7.6 Hz, 4 H), 7.31 (td, J = 2.4, 8.9 Hz, 1 H). 13 C NMR (100 MHz, CDCl3) δ 166.9 (d, J = 126.3, 3.3 Hz), 161.5 (d, J =249.0 Hz), 152.3 (d, J = 21.7 Hz), 138.3 (d, J = 11.3 Hz), 132.9 (d, J = 2.6Hz), 132.1 (d, J = 10.3 Hz), 131.1 (d, J = 109.2 Hz), 128.9 (d, J = 12.8 Hz), 126.1, 116.1 (d, J = 25.3 Hz), 108.2 (d, J = 26.7 Hz).

[0092] Example 23: Synthesis of 6-nitro-2-diphenylphosphinoylbenzothiazole

[0093] Based on the synthesis method of Example 1, 0.2 mmol of 6-nitrobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 58.57 mg of the target product 6-nitro-2-diphenylphosphineoxybenzothiazole with a yield of 77%. The molecular formula structure of the product in this example is Ⅰ-20.

[0094] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.99(d, J = 2.2 Hz, 1H), 8.44 (dd, J = 9.1,2.2 Hz, 1H), 8.32 (d, J = 9.1 Hz,1H), 8.11- 7.90 (m, 4H), 7.65 (td, J = 7.3,1.4 Hz, 2H), 7.61−7.50 (m,4H). 13 C NMR (100 MHz, CDCl3) δ 174.7 (d, J = 119.5 Hz), 158.9 (d, J = 20.8Hz), 146.3, 137.5, 133.5 (d, J = 2.9 Hz), 132.4 (d, J = 10.3Hz), 130.5 (d, J= 109.5 Hz), 129.1 (d, J = 13.0 Hz), 125.7, 122.4,119.3.

[0095] Example 24: Synthesis of 7-fluoro-2-diphenylphosphinoylbenzothiazole

[0096] Based on the synthesis method of Example 1, 0.2 mmol of 7-fluorobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 39.58 mg of the target product 7-fluoro-2-diphenylphosphineoxybenzothiazole with a yield of 56%. The molecular formula structure of the product in this example is Ⅰ-21.

[0097] The structural characterization data of the product in this example are as follows: 1H NMR (400MHz, CDCl3) δ 7.97 (d, J = 9.0, 1H), 7.95−7.89 (m, 4H), 7.70−7.63 (m, 2H), 7.58−7.49 (m,5H), 7.28 (td, J = 8.6, 2.4 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 156.9 (dd, J = 126.3, 3.5 Hz), 151.4 (d, J= 249.1 Hz), 148.3, 134.2 (d, J = 11.5 Hz), 133.3 (d, J = 2.8 Hz), 132.0 (d, J =10.3 Hz), 128.9 (d, J = 107.1 Hz), 127.4, 123.1, 119.0, 105.1.

[0098] Example 25: Synthesis of 7-chloro-2-diphenylphosphinoylbenzothiazole

[0099] Based on the synthesis method of Example 1, 0.2 mmol of 7-chlorobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 39.20 mg of the target product 7-chloro-2-diphenylphosphineoxybenzothiazole with a yield of 53%. The molecular formula structure of the product in this example is Ⅰ-22.

[0100] The structural characterization data of the product in this example are as follows: 1 H NMR (400MHz, CDCl3) δ 8.08 (d, J = 8.2 Hz, 1H), 7.92−7.87 (m, 4H), 7.65−7.58 (dd, J = 15.9, 7.1 Hz 3H), 7.56−7.48 (m,4H), 7.38 (td, J = 8.6, 2.4Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 166.9 (dd, J = 126.3, 3.5 Hz), 161.4,158.3, 144.2 (d, J = 11.5 Hz), 143.3 (d, J = 2.8 Hz), 142.0 (d, J =10.3 Hz),138.9 (d, J = 107.1 Hz), 137.4, 133.1, 129.0, 125.5.

[0101] Example 26: Synthesis of 7-bromo-2-diphenylphosphinoylbenzothiazole

[0102] 0.2 mmol of 7-bromobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were added to a dry photoreaction tube equipped with a magnetron. Then the photoreaction tube was evacuated and filled with nitrogen. In a nitrogen atmosphere, 2 ml of CH3CN was injected into the photoreaction tube through a syringe and sealed. Subsequently, the sealed photoreaction tube was placed under blue light at room temperature and stirred for 24 h under this condition. After 24 h of reaction, a certain amount of water was added to the photoreaction tube to completely dissolve the solid in the reaction solution, and then ethyl acetate was added for extraction, and the extraction was performed 3 times in total. The ethyl acetate was collected, the solvent was evaporated under reduced pressure, and the chromatographic column was separated and purified to finally obtain 64.62 mg of the target product 7-bromo-2-diphenylphosphine oxybenzothiazole with a yield of 78%. The molecular formula structure corresponding to the product in this example is Ⅰ-23.

[0103] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.12 (d, J = 8.2 Hz, 1H), 7.96 (dd, J =12.8, 7.6 Hz, 4H), 7.60 (dd, J = 15.9, 7.1 Hz, 3H), 7.52 (d, J = 10.5 Hz, 4H), 7.42 (t, J = 8.0 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 168.34(dd, J = 126.3, 3.5 Hz), 167.11(dd, J= 126.3, 3.5 Hz), 154.98, 154.76, 139.92(d, J = 11.5 Hz), 132.77, 132.74,131.98, 131.88, 131.14, 130.05, 129.30, 128.76, 128.64, 127.84, 123.58,119.37. 31 P NMR (162 MHz, CDCl3) δ 19.87.

[0104] Example 27: Synthesis of 7-nitro-2-diphenylphosphinoylbenzothiazole

[0105] Based on the synthesis method of Example 1, 0.2 mmol of 7-nitrobenzothiazole, 1.0 mmol of diphenylphosphine and 0.4 mmol of potassium persulfate were used to react to obtain 32.71 mg of the target product 7-nitro-2-diphenylphosphineoxybenzothiazole with a yield of 43%. The molecular formula structure of the product in this example is Ⅰ-24.

[0106] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.89 (d, J = 1.8 Hz, 1H), 8.39 (dd, J = 9.1,2.2 Hz, 1H), 8.28 (d, J = 8.5 Hz,1H), 8.09- 7.88 (m, 4H), 7.63 (td, J = 7.3,1.4 Hz, 2H), 7.59−7.48 (m,4H). 13 C NMR (100 MHz, CDCl3) δ 158.4(d, J = 20.8 Hz), 145.8, 137.0, 133.0(d, J = 2.9 Hz), 131.9 (d, J = 10.3Hz), 130.0 (d, J = 109.5 Hz), 129.6, 128.8(d, J = 13.0 Hz), 125.2, 121.9, 118.8.

[0107] Example 28: Synthesis of 2-bis(4-methylphenyl)phosphinothiazole

[0108] Based on the synthesis method of Example 1, 0.2 mmol of benzothiazole, 1.0 mmol of di-(4-methylphenyl)phosphine and 0.4 mmol of potassium persulfate were used to react to obtain 55.24 mg of the target product 2-di-(4-methylphenyl)phosphine oxybenzothiazole with a yield of 76%. The molecular formula structure of the product in this example is Ⅰ-25.

[0109] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.20 (d, J = 8.0 Hz, 1H), 8.02 (d, J = 7.6Hz, 1H), 7.91−7.79 (m, 4H), 7.55 (t, J = 7.4 Hz, 1H), 7.49 (t, J = 7.4 Hz,1H), 7.35−7.28 (m, 4H), 2.41 (s,6H). 13 C NMR (100 MHz, CDCl3) δ 167.9 (d, J = 126.3 Hz), 155.8 (d, J = 21.4Hz), 143.7 (d, J = 2.6 Hz), 137.4 (s), 132.5 (d, J =10.5 Hz), 129.5 (d, J =13.2 Hz), 128.3 (d, J = 111.6 Hz), 127.1, 126,9, 125.2, 122.5, 22.2.

[0110] Example 29: Synthesis of 7-methyl-2-di(4-methylphenyl)phosphinothiazole

[0111] Based on the synthesis method of Example 1, 0.2 mmol of 7-methylbenzothiazole, 1.0 mmol of di-(4-methylphenyl)phosphine and 0.4 mmol of potassium persulfate were used to react to obtain 39.25 mg of the target product 7-methyl-2-di(4-methylphenyl)phosphineoxybenzothiazole with a yield of 52%. The molecular formula structure of the product in this example is Ⅰ-26.

[0112] The structural characterization data of the product in this example are as follows: 1H NMR (400 MHz, CDCl3) δ 8.15 (d, J = 8.0 Hz, 1H), 7.91−7.79 (m, 4H), 7.55 (t, J = 7.4 Hz, 1H), 7.49 (t, J = 7.4 Hz, 1H), 7.35−7.28 (m, 4H), 2.41(s, 6H), 2.37(s, 3H). 13 C NMR (100 MHz, CDCl3) δ 167.9 (d, J = 126.3 Hz), 155.6 (d, J = 21.4Hz), 143.5 (d, J = 2.6 Hz), 141.6, 139.5, 137.4, 129.5 (d, J = 13.2 Hz),128.3 (d, J = 111.6 Hz), 127.1, 126,9, 125.2, 122.5, 22.2, 19.8.

[0113] Example 30: Synthesis of 4-chloro-2-di(4-methylphenyl)phosphinothiazole

[0114] Based on the synthesis method of Example 1, 0.2 mmol of 4-chlorobenzothiazole, 1.0 mmol of di-(4-methylphenyl)phosphine and 0.4 mmol of potassium persulfate were used to react to obtain 50.92 mg of the target product 4-chloro-2-di(4-methylphenyl)phosphineoxybenzothiazole with a yield of 64%. The molecular formula structure of the product in this example is Ⅰ-27.

[0115] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 7.6 Hz, 1H), 7.91−7.79 (m, 4H), 7.55 (t, J = 7.4 Hz, 1H), 7.49 (t, J = 7.4 Hz, 1H), 7.35−7.28 (m, 4H), 2.41(s,6H). 13C NMR (100 MHz, CDCl3) δ 167.9 (d, J = 126.3 Hz), 155.8 (d, J = 21.4Hz), 143.7 (d, J = 2.6 Hz), 137.4 (s), 132.5 (d, J =10.5 Hz), 129.5 (d, J =13.2 Hz), 128.3 (d, J = 111.6 Hz), 127.1, 126,9, 125.2, 121.7, 22.2.

[0116] Example 31: Synthesis of 4-bromo-2-di(4-methylphenyl)phosphinothiazole

[0117] Based on the synthesis method of Example 1, 0.2 mmol of 4-bromobenzothiazole, 1.0 mmol of di-(4-methylphenyl)phosphine and 0.4 mmol of potassium persulfate were used to react to obtain 53.96 mg of the target product 4-bromo-2-di(4-methylphenyl)phosphineoxybenzothiazole with a yield of 61%. The molecular formula structure of the product in this example is Ⅰ-28.

[0118] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.08 (d, J = 7.2 Hz, 1H), 8.00−7.91 (m, 4H), 7.71 (t, J = 7.4 Hz, 1H), 7.49 (t, J = 7.4 Hz, 1H), 7.35−7.28 (m, 4H), 2.41(s,6H). 13 C NMR (100 MHz, CDCl3) δ 168.7 (d, J = 126.3 Hz), 157.8 (d, J = 21.4Hz), 145.7 (d, J = 2.6 Hz), 137.4 (s), 132.5 (d, J =10.5 Hz), 129.5 (d, J =13.2 Hz), 128.3 (d, J = 111.6 Hz), 127.1, 126,9, 125.2, 121.7, 22.2.

[0119] Example 32: Synthesis of 4-fluoro-2-di(4-methylphenyl)phosphinothiazole

[0120] Based on the synthesis method of Example 1, 0.2 mmol of 4-fluorobenzothiazole, 1.0 mmol of di-(4-methylphenyl)phosphine and 0.4 mmol of potassium persulfate were used to react to obtain 41.19 mg of the target product 4-fluoro-2-di(4-methylphenyl)phosphineoxybenzothiazole with a yield of 54%. The molecular formula structure corresponding to the product in this example is Ⅰ-29.

[0121] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.00 (s, 1H), 7.79−7.68 (m, 4H), 7.87 (t, J= 6.8 Hz, 1H), 7.42 (t, J = 7.4 Hz, 1H), 7.35−7.28 (m, 4H), 2.41 (s,6H). 13 C NMR (100 MHz, CDCl3) δ 175.6 (d, J = 116.5 Hz), 165.8 (d, J = 22.1Hz), 153.7 (d, J = 2.8 Hz), 147.4, 142.5 (d, J =9.5 Hz), 139.5 (d, J = 13.2Hz), 134.3 (d, J = 101.6 Hz), 129.1, 127,9, 125.2, 123.6, 22.8.

[0122] Example 33: Synthesis of 7-bromo-2-di(4-methylphenyl)phosphinothiazole

[0123] Based on the synthesis method of Example 1, 0.2 mmol of 7-bromobenzothiazole, 1.0 mmol of di-(4-methylphenyl)phosphine and 0.4 mmol of potassium persulfate were used to react to obtain 34.50 mg of the target product 7-bromo-2-di(4-methylphenyl)phosphineoxybenzothiazole with a yield of 39%. The molecular formula structure of the product in this example is Ⅰ-30.

[0124] The structural characterization data of the product in this example are as follows: 1H NMR (400 MHz, CDCl3) δ 8.13 (d, J = 7.2 Hz, 1H), 8.00−7.91 (m, 4H), 7.82 (t, J = 7.4 Hz, 1H), 7.49 (t, J = 7.4 Hz, 1H), 7.35−7.28 (m, 4H), 2.41(s,6H). 13 C NMR (100 MHz, CDCl3) δ 163.4 (d, J = 124.2 Hz), 152.8 (d, J = 20.4Hz), 141.6 (d, J = 2.6 Hz), 137.4, 128.5 (d, J =9.5 Hz), 127.3 (d, J = 13.2Hz), 126.9 (d, J = 111.6 Hz), 126.1, 125,6, 124.8, 121.4, 21.5.

[0125] Example 34: Synthesis of 7-methyl-2-bis(4-chlorophenyl)phosphinothiazole

[0126] Based on the synthesis method of Example 1, 0.2 mmol of 7-methylbenzothiazole, 1.0 mmol of di-(4-chlorophenyl)phosphine and 0.4 mmol of potassium persulfate were used to react to obtain 37.64 mg of the target product 7-methyl-2-di(4-chlorophenyl)phosphineoxybenzothiazole with a yield of 45%. The molecular formula structure of the product in this example is Ⅰ-31.

[0127] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.18 (d, J= 7.8 Hz, 1H), 8.01 –7.95 (m, 4H), 7.60–7.49 (m, 6H). 2.38 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 166.0 (d, J= 129.6 Hz), 155.6 (d, J= 21.2Hz), 140.0 (d, J= 3.6 Hz), 137.1, 133.6 (d, J= 10.8 Hz), 130.1, 129.5 (d, J=13.5 Hz), 129.0, 127.3, 125.2, 122.6, 19.8.

[0128] Example 35: Synthesis of 4-chloro-2-di-(4-trifluoromethylbenzene)phosphinothiazole

[0129] Based on the synthesis method of Example 1, 0.2 mmol of 4-chlorobenzothiazole, 1.0 mmol of di-(4-trifluoromethylbenzene)phosphine and 0.4 mmol of potassium persulfate were used to react to obtain 33.34 mg of the target product 4-chloro-2-di-(4-trifluoromethylbenzene)phosphineoxybenzothiazole with a yield of 38%. The molecular formula structure corresponding to the product in this example is Ⅰ-32.

[0130] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.32 (d, J =49.4 Hz 1H), 8.05 (td, J = 12.9, 8.1 Hz, 4H), 7.95~7.76 (m, ,8H). 13 C NMR (100 MHz, CDCl3) δ 167.9 (d, J = 126.3 Hz), 155.8 (d, J = 21.4Hz), 143.7 (d, J = 2.6 Hz), 137.4, 135.9 (d, J = 98.9 Hz), 134.7 (m), 133.4(d, J = 11.7 Hz), 129.3 (m), 128.8 (d, J =265.6 Hz), 127.1, 126,9, 125.2,121.7.

[0131] Example 36: Synthesis of 4-bromo-2-bis(4-methoxyphenyl)phosphinothiazole

[0132] Based on the synthesis method of Example 1, 0.2 mmol of 4-bromobenzothiazole, 1.0 mmol of di(4-methoxyphenyl)phosphine and 0.4 mmol of potassium persulfate were used to react to obtain 32.67 mg of the target product 4-bromo-2-di(4-methoxyphenyl)phosphine oxybenzothiazole with a yield of 28%. The molecular formula structure of the product in this example is Ⅰ-33.

[0133] The structural characterization data of the product in this example are as follows: 1H NMR (400 MHz, CDCl3) δ 8.01 (d, J= 7.9 Hz, 1H), 7.82 (dd, J= 12.0,8.8 Hz, 4H), 7.46 -7.56 (m, 2H), 7.00 –7.02 (m, 4H), 3.84 (s, 6H). 13 C NMR (100 MHz, CDCl3) δ 167.8(d, J= 126.9 Hz), 163.0(d, J= 2.9 Hz), 155.3(d, J= 21.4 Hz), 136.8, 133.9(d, J= 11.7 Hz), 126.5(d, J= 9.8 Hz), 124.6(s), 123.5, 122.8, 122.0, 121.7, 55.3. 31 P NMR (162 MHz, CDCl3) δ 20.55 (s).

[0134] Example 37: Synthesis of 4-fluoro-2-bis(4-bromophenyl)phosphinothiazole

[0135] Based on the synthesis method of Example 1, 0.2 mmol of 4-fluorobenzothiazole, 1.0 mmol of di-(4-bromophenyl)phosphine and 0.4 mmol of potassium persulfate were used to react to obtain 52.14 mg of the target product 4-fluoro-2-di-(4-bromophenyl)phosphine oxybenzothiazole, with a yield of 51%. The molecular formula structure corresponding to the product in this example is Ⅰ-34.

[0136] The structural characterization data of the product in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 8.0Hz, 1H), 7.89−7.80 (m, 4H), 7.71−7.64 (m, 4H), 7.60 (t, J = 7.2 Hz,1H), 7.54 (t, J = 7.4 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 165.3 (d, J = 130.5 Hz), 159.9, 155.1 (d, J = 21.6 Hz), 136.5, 133.1 (d, J =10.7 Hz), 131.9 (d, J = 13.3 Hz), 129.4 (d, J = 108.4 Hz), 128.1 (d, J =3.5 Hz), 126.8, 122.0.

[0137] The reaction mechanism of the preparation method in the prior art patent application with publication number CN118908997A is: first, under the action of light and photocatalyst, diphenylphosphine oxide free radicals are generated, and then the diphenylphosphine oxide free radicals are added to the unsaturated bond "C=N", and finally the corresponding products are generated. The reaction mechanism of the synthesis method of the present invention includes two reaction paths, and the yield of the target product of the present invention is obtained by the superposition effect of the two reaction paths. Among them, reaction path a is: under the action of light, persulfate combines with benzothiazole compounds to form EDA complex, and then the EDA complex decomposes to generate SO4 ·- With benzothiazole compounds, followed by SO4 ·- Reacts with diphenylphosphine oxide to generate SO4 2- and diphenylphosphine oxide free radical, and then diphenylphosphine oxide free radical adds to the unsaturated bond "C=N" to finally generate the corresponding product. Reaction path b is: persulfate directly generates part of SO4 under light ·- , followed by SO4 ·- Reacts with diphenylphosphine oxide to generate diphenylphosphine oxide free radicals, SO4 2- and H + Then, the diphenylphosphine oxide free radical is added to the unsaturated bond "C=N" to finally generate the corresponding product. The specific reaction mechanism of the present invention can be found in Figure 4 .

[0138] Example 38: Bactericidal activity test

[0139] The mycelium growth rate method was used to select some compounds for the determination of fungicidal activity against tomato gray mold. The commercialized fungicide: thiophanate-methyl (2,4,5,6-tetrachloro-1,3-benzonitrile) was used as a comparison compound. The general screening concentration was 50 ug / ml. The fungicidal test results are shown in Table 1.

[0140] Table 1 Test results of fungicidal activity of the benzothiazole phosphine compound of the present invention and existing fungicides:

[0141] The test results show that the effect of the compound prepared by the present invention in inhibiting tomato gray mold can reach the level of existing fungicides with good fungicidal effects.

[0142] Obviously, the above embodiments are merely examples for illustrating the implementation methods of the present invention and are not intended to limit the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the scope of protection of the present invention.

Claims

1. A method for synthesizing a benzothiazole phosphorus compound, characterized in that: The following steps are involved: The benzothiazole compound represented by formula II and the organophosphorus compound represented by formula III are placed in a solvent and reacted in a nitrogen atmosphere by light and an oxidant to obtain the benzothiazole phosphorus compound; ， In the formula, R1 and R2 are independently selected from hydrogen, C1-C18 alkyl, C1-C18 alkoxy, halogen, trifluoromethyl or nitro; The molar ratio of the benzothiazole compound to the organic phosphorus compound is 1:1 to 1:5.5, and the oxidant is persulfate.

2. The method for synthesizing a benzothiazole phosphorus compound according to claim 1, characterized in that: The benzothiazole compound represented by formula II has a structure represented by any of the following formulae: ； The organic phosphorus compound represented by formula III is a diphenylphosphine oxide compound, and the diphenylphosphine oxide compound has a structure represented by any of the following formulas: 。 3. The method for synthesizing a benzothiazole phosphorus compound according to claim 1, characterized in that: The solvent is acetonitrile.

4. The method for synthesizing a benzothiazole phosphorus compound according to claim 1, characterized in that: The reaction temperature is 20°C to 30°C, and the reaction time is 24 h to 30 h.

5. The method for synthesizing a benzothiazole phosphorus compound according to claim 1, characterized in that: The molar ratio of the benzothiazole compound to the organic phosphorus compound is 1:

5.

6. The method for synthesizing a benzothiazole phosphorus compound according to claim 1, characterized in that: The molar ratio between the oxidant and the benzothiazole compound is 1.5:1 to 3:

1.

7. The method for synthesizing a benzothiazole phosphorus compound according to claim 1, characterized in that: The persulfate is potassium persulfate, sodium persulfate or ammonium persulfate.

8. A benzothiazole phosphorus compound, prepared according to the synthesis method of the benzothiazole phosphorus compound according to any one of claims 1 to 7, characterized in that: The benzothiazole phosphorus compound has a structure shown in Formula I: ， In the formula, R1 is independently selected from one of methyl, methoxy, nitro, fluorine, chlorine and bromine, and R2 is independently selected from one of hydrogen, methyl, methoxy, trifluoromethyl, chlorine and bromine.

9. The benzothiazole phosphorus compound according to claim 8, characterized in that The benzothiazole phosphorus compound has a structure shown in any of the following formulae: 。 10. Use of the benzothiazole phosphorus compound according to claim 8 in inhibiting tomato gray mold.

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