Allyl sulfonyl fluoride compound and application thereof in killing pine wood nematode activity

Abstract

The invention provides an allyl sulfonyl fluoride compound and application thereof in killing pine wood nematodes, and belongs to the field of forestry plant protection. The allylsulfonyl fluoride compound is subjected to pine wood nematode killing activity test and nematode killing toxicity determination, and the biological activity test result shows that the allylsulfonyl fluoride compound has good nematode killing activity, can efficiently kill pine wood nematodes, has a good prevention and treatment effect on pine wood nematode diseases, and has a good application prospect. The plant nematicide is a plant nematicide with wide application prospect and research potential.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of forestry plant protection, and particularly relates to an allyl sulfonyl fluoride compound and application thereof in preventing and treating plant diseases and killing nematodes. BACKGROUND

[0002] Sulfonyl fluoride has a very important application in drug design, development and modification. Compared with sulfonyl chloride, sulfonyl fluoride group is more stable and has better biocompatibility. Hexavalent sulfur fluoride warhead can highly selectively react with specific amino acid residues in target protein to form a stable covalent complex, so the compound containing SuFEx warhead has great potential in the development of covalent drugs. The introduction of sulfonyl fluoride group can multiply the efficacy of the original drug, and plays an important role in chemical biology and drug discovery and design. Sulfonyl fluoride compounds have rich biological activities, and previous researches are mainly on antibacterial activity, and less on the activity of killing pine wood nematodes.

[0003] Forestry development is of great significance to China. In terms of ecology, forestry development plays an indispensable role in soil and water conservation, water conservation, climate regulation and biodiversity conservation. Meanwhile, in terms of economic development, it provides timber and forest products, and helps China's forestry economy and employment. In terms of social and cultural aspects, it not only provides leisure places for people, but also carries the function of cultural heritage. However, the problem of pests and diseases has always been the main factor affecting the health of forests. Since pine wood nematode disease was first discovered in Nanjing, China in 1982, it has shown a rapid spreading trend. At present, pine wood nematode disease has spread to 708 county-level administrative areas in 19 provinces (regions and cities) of Jiangsu, Jiangxi, Anhui, Zhejiang, Liaoning, Shandong and Fujian, with an affected area covering more than 122.27 million hm 2 According to statistics, under natural conditions, pine wood nematode can harm up to 45 species of Pinus, has strong pathogenicity, spreads rapidly, is difficult to control, and causes rapid death of the host. Pine wood nematode has become the most serious harmful organism to China's forests, and poses a major threat to ecological environment construction. Therefore, it is of great significance to develop a new pine wood nematode control drug. SUMMARY

[0004] The purpose of the present application is to provide an allyl sulfonyl fluoride compound, and to study the nematocidal effect thereof, so as to develop a new nematocide for preventing and treating plant diseases.

[0005] To achieve the above-mentioned purpose, the present application provides an allyl sulfonyl fluoride compound having nematocidal performance, and the structure formula of the allyl sulfonyl fluoride compound is as shown in formula I.

[0006]

[0007] In formula I, R 1one of halogen, naphthalene ring, benzyl, alkyl, ester, cycloalkane, cyclohexanone, substituted aryl (wherein the substituents include but are not limited to halogen, nitro, cyano, alkyl, methoxy, phenyl, trifluoromethylsulfonic acid group); R 2 one of H, methyl.

[0008] Further, the allyl sulfonyl fluoride compound can effectively inhibit pine wood nematode disease.

[0009] Another object of the present application is to provide a nematocide prepared by using the above-mentioned allyl sulfonyl fluoride compound for inhibiting pine wood nematode disease, wherein a pharmaceutically acceptable carrier can be added to the preparation of the drug to form a common pharmaceutical preparation such as tablets, powders, liquids, suspensions, injections, etc., and a liquid or solid filler or diluent, etc. common pharmaceutical adjuvants can also be added to the preparation.

[0010] The "plant disease" referred to herein is pine wood nematode disease. However, the use of the compounds described herein is by no means limited to these genera or species, but extends in the same way to other fungi and pests.

[0011] Compared with the prior art, the present application has the following beneficial effects:

[0012] The target compound (I) obtained by the present application has an inhibitory insecticidal effect on pine wood nematodes and the like, and can be applied to a novel plant nematocide; BRIEF DESCRIPTION OF DRAWINGS

[0013] Figure 1 is the structural formula of the allyl sulfonyl fluoride compound of the present application.

[0014] Figure 2 is the hydrogen spectrum of the compound 3c described in the examples of the present application.

[0015] Figure 3 is the carbon spectrum of the compound 3c described in the examples of the present application.

[0016] Figure 4 is the fluorine spectrum of the compound 3c described in the examples of the present application. DETAILED DESCRIPTION

[0017] In order to make the above-mentioned objects, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application will be described in detail below in conjunction with the description of the examples.

[0018] In the following description, many specific details are set forth in order to provide a thorough understanding of the present application, but the present application can also be implemented in other ways different from those described herein, and those skilled in the art can make similar generalizations without departing from the scope of the present application, therefore the present application is not limited to the specific examples disclosed below.

[0019] Second, the term "one embodiment" or "an embodiment" as may appear in various places in the specification are not necessarily all referring to the same embodiment, nor are they necessarily mutually exclusive or alternative embodiments.

[0020] The allyl sulfonyl fluoride compound of the present application is shown as Figure 1

[0021] Example 1

[0022] Into a 25 mL three-necked reaction flask equipped with a rotor, allyl bromide (0.2 mmol, 1.0 equiv), lithium triflate (1 mmol, 5.0 equiv), and diethyl ether (10 mL, 0.02 M) were added, respectively. The flask was equipped with a graphite felt electrode (20 mm x 10 mm x 1 mm) as an anode and a zinc electrode (20 mm x 10 mm x 1 mm) as a cathode. After the mixture was stirred uniformly, the fluorosulfonyl chloride reagent (0.4 mmol, 2.0 equiv, 1 M in PhCF3) was added and electrolyzed at a constant voltage of 8 V for 6 h at room temperature. Thin layer chromatography showed that the starting material was completely converted. The reaction was quenched by adding water (10 mL) in a fume hood, and the mixture was extracted with ethyl acetate three times. The organic phase was collected and dried over anhydrous sodium sulfate. After the solvent was removed using a rotary evaporator, the allyl sulfonyl fluoride compound (30.1 mg, 64%) was purified by silica gel column chromatography. The reaction process is as follows:

[0023]

[0024] Example 2

[0025] To detect the effect of the allyl sulfonyl fluoride compound on Bursaphelenchus xylophilus, the nematode was verified by the Forest Pathology Laboratory of Nanjing Forestry University. The results are shown in Table 5.

[0026] Preparation of nematode culture solution: Bursaphelenchus xylophilus was fed on Botrytis cinerea grown well on PDA medium, and the feeding conditions were constant temperature feeding at 25°C in the dark. The preparation of PDA medium and fungal culture was carried out according to the conventional method.

[0027] Preparation of solvent: 2 mL of DMF and 1000 mL of 2.5 wt% OP10 / H2O solution were mixed in proportion to prepare the solvent for standby.

[0028] Preparation of mixed sample solution: 0.2 mg of the allyl sulfonyl fluoride compound prepared in Example 1 was mixed with 1 mL of the above solvent for standby.

[0029] ​Take 100 μL mixed sample solution and 100 μL nematode culture solution, stand for 24 h, and observe the mortality rate of nematodes; nematode mortality rate = number of dead nematodes / number of test nematodes * 100%.

[0030] Take 100 μL mixed sample solution and 100 μL nematode culture solution, stand for 24 h, and observe the mortality rate of nematodes; nematode mortality rate = number of dead nematodes / number of test nematodes * 100%.

[0031] Mortality rate = number of dead nematodes / total number of nematodes * 100%

[0032] Corrected mortality rate = (treatment group mortality rate-blank group mortality rate) / (1-blank group mortality rate) * 100%

[0033] The results are shown in Table 1.

[0034] Number Compound Number Corrected Mortality (%, mean ± SD) 1 3a 93.1±3.0 2 3b 92.4±2.1 3 3c 100 4 3d 84.4±5.3 5 3e 87.4±3.1 6 3f 88.9±1.3 7 3g 100 8 3i 79.6±6.2 9 3j 66.7±2.2 10 3l 82.2±6.3 11 3n 100 12 3o 94.2±3.3 13 3p 91.7±3.7 14 3q 36.0±5.3 15 3t 45.2±5.3

[0035] Table 1

[0036] The experimental results show that the allyl sulfonyl fluoride compound can inhibit the growth of nematodes, and has obvious inhibitory effect on pine wood nematode disease, thereby laying a solid foundation for the development of new nematode-killing agents.

[0037] Example 3

[0038] Gradient concentration toxicity tests were conducted on representative allyl sulfonyl fluoride compounds, and the experimental results showed that the compound concentration was positively correlated with the mortality rate of pine wood nematodes.

[0039] By testing the mortality rate of nematodes under different concentrations, a dose-effect experiment was set up with five gradient concentrations (20, 40, 60, 80 and 100 mg / L), and a complete virulence regression equation was established.

[0040] The results are shown in Table 2.

[0041] Number Compound Number Regression Equation Correlation coefficient (R 2 ) LC 50 ]] 1 3c y = 1.4864x - 33.779 0.9733 49.6 mg / L 2 3n y = 1.0836x - 25.321 0.9772 69.5 mg / L

[0042] Table 2

[0043] The experimental results show that the allyl sulfonyl fluoride compound has good toxic effect on pine wood nematodes, thereby laying a solid foundation for the development of new nematode-killing agents.

[0044] It should be noted that the above examples are only used to illustrate the technical solutions of the present application and are not limiting. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the spirit and scope of the present application, and all should be covered in the scope of the claims of the present application.

Claims

1. An allyl sulfonyl fluoride compound for use in the inhibition of pine wood nematode activity, characterized by: The structure of the compound is shown in formula I: In formula I, R 1 is one of halogen, naphthalene ring, benzyl, alkyl, ester, cycloalkane, cyclohexanone, substituted aryl (wherein the substituents include but are not limited to halogen, nitro, cyano, alkyl, methoxy, phenyl, trifluoromethanesulfonic acid group); R 2 is one of H, methyl.

2. A compound preparation, characterized by, The allyl sulfonyl fluoride compound of claim 1, and a carrier.

3. The allyl sulfonyl fluoride compound according to claims 1-2, characterized by: The dosage form of the allyl sulfonyl fluoride compound used as a fungicide is a pesticide-acceptable dosage form, including any one of emulsifiable concentrate, dry flowable, wettable powder, microemulsion, aqueous emulsion, suspension, dispersible oil suspension, and preferably suspension.

4. Use of the allylsulfonyl fluoride compounds according to claims 1-3 in agriculture, forestry, horticulture, characterized in that: The compound is used for preventing and treating pine wood nematode disease.

5. Use according to claim 4, characterized in that, The plant disease is pine wood nematode disease.

6. Use according to claim 4, characterized in that: The allyl sulfonyl fluoride compound has obvious inhibitory effect on pine wood nematode disease.

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