Propargyl sulfite compound containing trifluoromethoxy as well as preparation method and application of propargyl sulfite compound

Abstract

The invention relates to the technical field of pesticides, and particularly discloses a trifluoromethoxy-containing sulfurous acid compound, a preparation method and application thereof, an agricultural composition and a method for preventing and treating invertebrate pests. The sulfurous acid compound containing trifluoromethoxy has a structure as shown in a formula (I). The sulfurous acid compound containing the trifluoromethoxy group, provided by the invention, shows an excellent mite killing effect.

Description

Technical Field

[0001] The invention belongs to the technical field of pesticides, and particularly relates to a trifluoromethoxy-containing propargyl sulfite compound, a preparation method and application thereof. Background Art

[0002] In recent years, the control of agricultural mites has become increasingly difficult. This is primarily due to the rapid reproduction and adaptability of mites, which can quickly develop resistance to existing miticides. Consequently, the use of chemical miticides has increased significantly. Therefore, there is an urgent need to develop new, more effective miticides.

[0003] Currently, the main acaricides used in the market include pyridabenz, tebufenpyrad, azoxatin, abamectin, spirodiclofen, spiromesifen, propargyl, bifenazate, cyflumetofen, etoxazole, etoxazolidinone, and cypermethrin. However, resistance to these acaricides develops increasingly with prolonged and frequent use, and even with increasing concentrations of each agent, the acaricidal effect remains suboptimal.

[0004] However, existing acaricides still have drawbacks such as low activity against mites, severe resistance, complex production processes, high pollution levels, and high costs. Therefore, agricultural production is in urgent need of new pesticides that are highly effective, low-toxic, simple to produce, less polluting, and low-cost, and that exhibit excellent killing effects against resistant mites. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to overcome the technical problems that the existing compounds have low killing activity and serious resistance in the control of invertebrate pests (especially mites), and to provide a trifluoromethoxy-containing propargyl sulfite compound and its synthesis method and use, an agricultural composition and a method for controlling invertebrate pests.

[0006] The technical solution of the present invention is as follows: In order to achieve the above-mentioned purpose, the first aspect of the present invention provides a trifluoromethoxy-containing sulfite compound having a structure shown in formula (I):

[0007]

[0008] In formula (I),

[0009] R1, R2, R3, and R4 are each independently selected from hydrogen, halogen, cyano, nitro, amino, hydroxy, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C2-C10 alkoxycarbonyl, C2-C10 alkylcarbonyl, C1-C10 carbonyl, C2-C10 alkenyl, C2-C10 haloalkenyl, C2-C10 alkynyl, C2-C10 haloalkynyl, C1-C10 Alkylsulfonyl, C1-C10 haloalkylsulfonyl, C1-C10 alkylsulfinyl, C1-C10 haloalkylsulfinyl, C1-C10 alkylthio, C1-C10 haloalkylthio, C1-C10 alkylsilyl, C6-C10 aryl, C6-C10 aryloxy, C6-C10 arylsulfonyl, C6-C10 arylsulfinyl, C6-C10 arylthio, C3-C10 heterocycle, C3-C10 heterocycloalkyl, C3-C10 heterocycleoxy.

[0010] In some embodiments, in formula (I), R1, R2, R3, and R4 are each independently selected from hydrogen, halogen, cyano, nitro, amino, hydroxyl, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C6 carbonyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C 1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsilyl, C6-C10 aryl, C6-C10 aryloxy, C6-C10 arylsulfonyl, C6-C10 arylsulfinyl, C6-C10 arylthio, C3-C10 heterocycle, C3-C10 heterocycloalkyl, C3-C10 heterocycleoxy.

[0011] In some embodiments, in formula (I), R1, R2, R3, and R4 are each independently selected from hydrogen, halogen, cyano, nitro, amino, hydroxyl, methyl, ethyl, chloroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, allyl, propargyl, trifluoromethyl, SCF3, trifluoromethanesulfinyl, trifluoromethanesulfonyl, phenyl or halophenyl.

[0012] In some embodiments, the compound of formula I is selected from at least one of the compounds shown in the following table:

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

[0019] In some exemplary embodiments, the present invention provides the following compounds:

[0020]

[0021] A second aspect of the present invention provides a method for preparing a trifluoromethoxy-containing sulfite compound represented by formula (I), the method comprising:

[0022] (1) reacting the compound represented by formula (II) with cyclohexene oxide in the presence of a base to obtain the compound represented by formula (III);

[0023]

[0024] (2) reacting the compound represented by formula (III) with thionyl chloride to obtain the compound represented by formula (IV);

[0025]

[0026] (3) reacting the compound represented by formula (IV) with propargyl alcohol to obtain the compound represented by formula (I),

[0027]

[0028] Wherein, the definitions of R1, R2, R3 and R4 are the same as those described in the first aspect above.

[0029] In the present invention, there is no particular limitation on the type of base in step (1), as long as it can meet the requirements of the present invention, for example, it can be an organic base or an inorganic base, wherein the base can be selected from at least one of sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, triethylamine, diisopropylethylamine and pyridine.

[0030] The present invention has no particular limitation on the reaction conditions, material ratios, etc. involved in the above preparation process. Those skilled in the art can obtain appropriate reaction conditions based on common knowledge in the field of organic synthesis and the specific examples provided in the Examples of the present invention.

[0031] The third aspect of the present invention provides an agricultural composition comprising 1-99 wt % of the compound described in the first aspect.

[0032] In the present invention, the composition comprises at least one trifluoromethoxy-containing sulfite compound as described in the first aspect and at least one liquid carrier or solid carrier. The liquid carrier or solid carrier is not particularly limited, as long as it can meet the requirements of the present invention.

[0033] In the present invention, liquid carrier can be water, various aromatic hydrocarbons, aliphatic hydrocarbons, ketones, ethers etc., such as toluene, xylene, acetone, cyclohexanone, xylene, benzene, cyclohexane, isopropyl alcohol, ethylene glycol, sorbitol, methanol, ethanol, butanol, dimethylformamide, N-methylpyrrolidone, decalin, motor oil, petroleum ether, cyclohexanone, methyl oleate, methylated soybean oil etc. one or more; Solid carrier can include natural or synthetic clay and silicate, solid carrier suitable for powder can include naturally formed rock powder, chalk, quartz, clay, montmorillonite, white carbon black, diatomaceous earth, pumice, gypsum, talc, bentonite, kaolin, clay and synthetic ground mineral matter (such as micro-dispersed silicic acid or aluminum oxide). Suitable particle carrier can include crushed and graded natural rock such as calcite, marble, pumice, sepiolite and dolomite and synthetic particles made of organic and inorganic powder.

[0034] In the present invention, preferably, the composition can be applied in the form of a preparation. The compound represented by formula (I) is dissolved or dispersed in a carrier as an active ingredient, or is configured into a preparation so that it is easier to disperse when used for acaricide. For example, the composition can be prepared into a wettable powder, a water-dispersible granule, a suspension, an emulsion in water, an aqueous solution or an emulsifiable concentrate. At least one liquid or solid carrier is added to the composition, and when necessary, a suitable surfactant can also be added. The surfactant can include dodecylbenzene sulfonate, fatty alcohol sulfate, Tween, agricultural milk, sorbitol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, lignin sulfonate, alkylnaphthalene sulfonate, etc.

[0035] The inventors of the present invention have discovered that the compounds represented by formula (I) have unexpectedly high acaricidal activity. Therefore, the trifluoromethoxy-containing sulfite compounds of the present invention can also be used in agriculture or other fields to prepare acaricides. In particular, the inventors of the present invention have discovered that the compounds represented by formula (I) have high activity against the following invertebrate pests (the following list is intended to illustrate the present invention and is not intended to limit the present invention): Tetranychus (e.g., Tetranychus cinnabarinus, Panonychus citri, Tetranychus urticae, Panonychus apicale, Tetranychus kanzawa, Tetranychus viciae), Acaridae, Acaridae, and Leptocaridae.

[0036] The fourth aspect of the present invention provides a use of the compound described in the first aspect or the composition described in the third aspect in controlling invertebrate pests;

[0037] Preferably, the invertebrate pest is a pest of the family Acaridae.

[0038] In the present invention, preferably, the trifluoromethoxy-containing sulfite compound can be used to protect important crops and livestock in agriculture and horticulture from or from being harmed by harmful mites.

[0039] In the present invention, in order to obtain the desired effect, in some applications, the amount of the trifluoromethoxy-containing sulfite compound used varies depending on various factors, such as the compound used, the crop to be protected, the type of pest, the degree of infection, the application method, the application environment, the application formulation, and the like.

[0040] In the present invention, preferably, for certain applications, such as agriculture, one or more other insecticides, acaricides, fungicides, herbicides, plant growth regulators or fertilizers can be added to the agricultural composition of the present invention, thereby producing additional advantages and effects.

[0041] A fifth aspect of the present invention provides a method for controlling invertebrate pests, comprising applying an insecticidally effective amount of the trifluoromethoxy-containing sulfite compound of the first aspect or the composition of the third aspect directly or indirectly to the invertebrate pest to be controlled and / or the medium in which it grows. The invertebrate pest is an acaridae pest.

[0042] There is no particular limitation on direct or indirect methods, as long as the purpose of controlling invertebrate pests can be achieved. For example, a direct method may include directly contacting a substance containing the components of the trifluoromethoxy-containing sulfite compound with invertebrate pests (including invertebrate pests directly consuming the substance containing the components of the trifluoromethoxy-containing sulfite compound, direct contact between the body surface of invertebrate pests and the substance containing the components of the trifluoromethoxy-containing sulfite compound, etc.); an indirect method may include treating places where invertebrate pests are present (their habitats or breeding grounds or plants or soil where invertebrate pests grow) with a substance containing the components of the trifluoromethoxy-containing sulfite compound, or treating their food chain with a substance containing the components of the trifluoromethoxy-containing sulfite compound.

[0043] In the present invention, the plant is a plant of the phylum Gymnosperms and / or Angiosperms, preferably at least one of the family Rutaceae, Solanaceae, Cruciferae and Rosaceae.

[0044] Preferably, the plant can be selected from citrus, apple, pear, cotton, rose, bean, strawberry, pepper, melon, watermelon, eggplant, peanut, wheat and the like.

[0045] In the present invention, the insecticidal effective amount is not particularly limited. For example, a dosage of 30 grams to 1 kilogram of the trifluoromethoxy-containing sulfite compound per hectare can provide sufficient control. Preferably, the insecticidal effective amount can be 50 grams to 300 grams per hectare.

[0046] It should be understood that various changes and modifications can be made within the scope of the present invention as defined by the claims.

[0047] Compared with the prior art, the compound of the present invention exhibits a more excellent acaricidal effect. DETAILED DESCRIPTION

[0048] The following examples may enable those skilled in the art to more fully understand the present invention, but the present invention is not limited to the scope of the examples.

[0049] Example 1

[0050] Preparation of 2-(4-trifluoromethoxyphenoxy)cyclohexylpropyn-2-yl sulfite (Compound 1)

[0051]

[0052] (1) Cyclohexane oxide (44.2g, 1eq), p-trifluoromethoxyphenol (75g, 1eq) and 40wt% sodium hydroxide aqueous solution (5.1g) were added to a 500mL round-bottom flask in sequence, and the mixture was heated to reflux under stirring. After reacting for 10 hours, unreacted cyclohexane oxide was removed by vacuum distillation. The reaction solution was cooled to 50°C and then ethyl acetate (500mL) and water (500mL) were added for extraction and separation. After extraction and separation, the aqueous layer was extracted and separated with 500mL of ethyl acetate. After separation, the organic phases were combined, dried with anhydrous sodium sulfate, and vacuum rotary distilled to obtain 118g of a white solid (2-(4-trifluoromethoxyphenoxy)cyclohexanol) with a yield of 98.92%.

[0053]

[0054] (2) 20 mL of toluene and thionyl chloride (2.56 g, 1.2 eq) were added to a 50 mL round-bottom flask. The reaction flask was cooled in an ice bath and 2-(4-trifluoromethoxyphenoxy)cyclohexanol (4.96 g, 1 eq) was added. The reaction was continued with stirring for 5 hours. The reaction solution was then cooled to 25°C.

[0055] The reaction mixture was concentrated under reduced pressure for 20 minutes to obtain a toluene solution of a crude product of 2-(4-trifluoromethoxyphenoxy)cyclohexyl-O-sulfenyl chloride.

[0056] (3) A separate 50 mL round-bottom flask was charged with toluene (20 mL), triethylamine (3.6 g, 2 eq), and propargyl alcohol (1 g, 1 eq). The reaction flask was cooled in an ice bath and the crude toluene solution of 2-(4-trifluoromethoxyphenoxy)cyclohexyl-O-sulfinyl chloride was slowly added dropwise. After 10 min of complete addition, the mixture was stirred at room temperature for 1 hour. 100 mL of ethyl acetate, 100 mL of water, and 20 mL of saturated ammonium chloride solution were added to the reaction solution. After extraction and separation, the organic phase was dried over 5 g of anhydrous sodium sulfate. The organic phase was concentrated and purified by column chromatography to obtain 5.22 g of a nearly colorless viscous oil (Compound I-1) with a yield of 77.34%.

[0057] 1 H NMR (400MHz, CDCl3) δ7.13(d,J=8.8Hz,2H),7.00–6.86(m,2H),4.75–4.53(m,2H),4.54–4.40(m,1H),4.18(ddd,J=18.4,9.3, 4.4Hz,1H),2.54(dt,J=9.7,2.5Hz,1H),2.25–2.06(m,2H),1.88–1.64(m,2H),1.64–1.17(m,4H); MS(m / z,ESI):401.32(m+Na + ).

[0058] Other compounds of the present invention can be prepared by referring to the method disclosed in Example 1.

[0059] Formulation Examples

[0060] Preparation Example 1

[0061] Preparation of 40wt% compound emulsion

[0062] Dissolve 40 parts by weight of compound 1 in 13 parts by weight of methyl oleate, add 14 parts by weight of calcium dodecylbenzenesulfonate and 7 parts by weight of tristyrylphenol polyoxyethylene ether polyoxypropylene ether, and then add methylnaphthalene to make up to 100 parts by weight. Stir and mix thoroughly to obtain an emulsifiable concentrate containing 40% by weight of the compound.

[0063] Application Examples

[0064] Activity test of Tetranychus cinnabarinus

[0065] The test compound was dissolved in acetone and diluted to the desired concentration with a 0.1 wt % Tween 80 aqueous solution, with the acetone content not exceeding 5 wt %.

[0066] Bean seedlings grown to two true leaves were inoculated with one true leaf and then inoculated with adult Tetranychus cinnabarinus. The population was then assessed and the entire plant sprayed with a handheld sprayer. Each treatment was repeated three times (using 1 g of the preparation). After treatment, the seedlings were observed in a constant temperature observation room. After 72 hours, the number of live mites was assessed and the mortality rate was calculated. The number of mites inoculated at each inoculation was 50-150.

[0067] Among them, the mortality rate = (number of inoculated insects - number of live insects after medication) ÷ number of inoculated insects × 100%.

[0068] Among them, the mortality rates of cypermethrin and compounds on Tetranychus cinnabarinus at different concentrations are shown in Table 1:

[0069] Table 1

[0070]

[0071] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A compound represented by formula (I) or an agriculturally acceptable salt thereof, or a stereoisomer thereof, In formula (I), R1, R2, R3, and R4 are each independently selected from hydrogen, halogen, cyano, nitro, amino, hydroxy, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C2-C10 alkoxycarbonyl, C2-C10 alkylcarbonyl, C1-C10 carbonyl, C2-C10 alkenyl, C2-C10 haloalkenyl, C2-C10 alkynyl, C2-C10 haloalkynyl, C1-C10 Alkylsulfonyl, C1-C10 haloalkylsulfonyl, C1-C10 alkylsulfinyl, C1-C10 haloalkylsulfinyl, C1-C10 alkylthio, C1-C10 haloalkylthio, C1-C10 alkylsilyl, C6-C10 aryl, C6-C10 aryloxy, C6-C10 arylsulfonyl, C6-C10 arylsulfinyl, C6-C10 arylthio, C3-C10 heterocycle, C3-C10 heterocycloalkyl, C3-C10 heterocycleoxy.

2. The compound according to claim 1, characterized in that R1, R2, R3 and R4 are each independently selected from hydrogen, halogen, cyano, nitro, amino, hydroxyl, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C6 carbonyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkylsulfonyl alkyl, C1-C6 haloalkylsulfonyl, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsilyl, C6-C10 aryl, C6-C10 aryloxy, C6-C10 arylsulfonyl, C6-C10 arylsulfinyl, C6-C10 arylthio, C3-C10 heterocycle, C3-C10 heterocycloalkyl, C3-C10 heterocycleoxy.

3. The compound according to claim 1, characterized in that R1, R2, R3, and R4 are each independently selected from hydrogen, halogen, cyano, nitro, amino, hydroxy, methyl, ethyl, chloroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, allyl, propargyl, trifluoromethyl, SCF3, trifluoromethanesulfinyl, trifluoromethanesulfonyl, phenyl or halophenyl.

4. The compound according to claim 1, 2 or 3, wherein R1 is selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, trifluoromethyl, trifluoromethoxy, phenyl; R2, R3 and R4 are each independently selected from hydrogen.

5. The following compounds or their agriculturally acceptable salts, or their stereoisomers:

6. A method for preparing the compound according to claim 1, comprising: (1) reacting the compound represented by formula (II) with cyclohexene oxide in the presence of a base to obtain the compound represented by formula (III); (2) reacting the compound represented by formula (III) with thionyl chloride to obtain the compound represented by formula (IV); (3) reacting the compound represented by formula (IV) with propargyl alcohol to obtain the compound represented by formula (I), Wherein, the definitions of R1, R2, R3 and R4 are the same as those described in claim 1.

7. The preparation method according to claim 6, characterized in that The base in step (1) is selected from at least one of sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, triethylamine, diisopropylethylamine and pyridine.

8. An agricultural composition, characterized in that The composition contains 1-99 wt% of the compound according to any one of claims 1-5.

9. Use of the compound according to any one of claims 1 to 5 or the composition according to claim 8 in controlling invertebrate pests; Preferably, the invertebrate pests are Acaridae pests.

10. A method for controlling invertebrate pests, characterized in that: The method comprises: applying an insecticidal effective amount of the trifluoromethoxy-containing sulfite compound according to any one of claims 1 to 5 or the composition according to claim 8 directly or indirectly to the invertebrate pests to be controlled and / or the medium in which they grow.

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