Preparation method and application of organic sulfur compound

Abstract

The invention relates to an organic sulfur compound and a preparation method and application thereof, the organic sulfur compound has a structure as shown in formula (I), and each group in the formula is as shown in the specification. The organic sulfur compound provided by the invention shows a very high prevention and treatment effect on pests and harmful mites in agriculture and gardening, can be used for preventing and treating various pests and harmful mites, and has a good application prospect. # imgabs0 #

Description

[Technical field]

[0001] The present invention relates to the field of pesticides, and in particular to organic sulfur compounds and / or their salts, and preparation methods and applications thereof. [Background technology]

[0002] In crop production in agriculture and horticulture, the losses caused by pests are still great, and pests resistant to existing drugs are emerging. From the viewpoints of the impact on environmental organisms and labor saving, it is expected that insecticides and acaricides for agriculture and horticulture will be developed that have a new mechanism of action, less impact on natural enemies and beneficial insects, and have osmotic transfer activity.

[0003] DE1803728A discloses an organic sulfur compound, which has certain effects in weed control and fungicide, but does not disclose insecticidal and acaricidal activities.

[0004]

[0005] However, due to the high speed of resistance development of pests and mites and the national requirement to reduce the use of pesticides, it is still necessary to develop new compounds with higher activity in order to achieve excellent killing effects on pests and mites at lower usage concentrations. [Summary of the invention]

[0006] The purpose of the present invention is to provide a new organic sulfur compound and its salt, which can be used as an active ingredient in insecticides and miticides, and can have a high control effect when used in a relatively low concentration.

[0007] In order to achieve the above object, the present invention provides an organic sulfur compound and / or its salt in a first aspect, wherein the organic sulfur compound has a structure shown in formula (I):

[0008]

[0009] Wherein, in formula (I),

[0010] R 1 C 1 -C 3 Alkyl or C 1 -C 3 Haloalkyl,

[0011] R 2 It is methylsulfonyl, ethylsulfonyl or phenoxycarbonyl.

[0012] In some embodiments, R 1 is methyl, ethyl or trifluoromethyl; R 2 It is ethylsulfonyl or phenoxycarbonyl.

[0013] In some embodiments, the compound of formula I is selected from at least one of the compounds shown in Table 1.

[0014] Table 1

[0015]

[0016]

[0017] The present invention provides the following compounds or agriculturally acceptable salts thereof,

[0018]

[0019] The second aspect of the present invention provides use of the organic sulfur compound and / or its salt described in the first aspect of the present invention in the preparation of insecticides and acaricides.

[0020] The third aspect of the present invention provides an insecticide and acaricide, which contains an active ingredient, and the active ingredient is selected from at least one of the organic sulfur compounds and / or their salts described in the first aspect of the present invention.

[0021] The fourth aspect of the present invention provides the use of the insecticide and acaricide according to the third aspect of the present invention in killing insects and / or acaricides in agriculture, forestry and horticulture.

[0022] Compared with the prior art, the present invention has at least the following advantages:

[0023] The organic sulfur compound or its salt provided by the present invention is used as an active ingredient as an insecticide and acaricide, and can have an excellent control effect when used at a low concentration.

[0024] Other features and advantages of the present invention will be described in detail in the following detailed description. [Specific implementation method]

[0025] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0026] In some embodiments of the present invention, preferably, the salt in the organic sulfur compound and / or its salt includes but is not limited to inorganic salts such as hydrochloride, sulfate, nitrate, phosphate; and organic salts such as acetate, fumarate, maleate, oxalate, methanesulfonate, benzenesulfonate, p-toluenesulfonate.

[0027] As mentioned above, the second aspect of the present invention provides the use of the organic sulfur compound or its salt described in the first aspect of the present invention in the preparation of insecticides and acaricides and / or parasite control agents.

[0028] Preferably, the organic sulfur compound or its salt is used as an active ingredient (ie, effective ingredient) in the insecticide acaricide and / or parasite control agent.

[0029] In some embodiments of the present invention, preferably, the insect is selected from Plutella xylostella and Spodoptera exigua; and the mite is selected from Tetranychus cinnabarinus and Tetranychus urticae.

[0030] As mentioned above, the third aspect of the present invention provides an insecticide and acaricide, which contains an active ingredient, and the active ingredient is selected from at least one of the organic sulfur compounds and / or their salts described in the first aspect of the present invention.

[0031] In some embodiments of the present invention, preferably, based on the total weight of the insecticide and acaricide, the content of the active ingredient is 1-99 weight%, for example, the content of the active ingredient is 1 weight%, 5 weight%, 10 weight%, 15 weight%, 20 weight%, 25 weight%, 30 weight%, 35 weight%, 40 weight%, 45 weight%, 50 weight%, 55 weight%, 60 weight%, 65 weight%, 70 weight%, 75 weight%, 80 weight%, 85 weight%, 90 weight%, 95 weight%, 99 weight% and any value in the range formed by any two of these point values. More preferably, based on the total weight of the insecticide and acaricide, the content of the active ingredient is 5-60 weight%.

[0032] In some embodiments of the present invention, preferably, the insecticide and acaricide further contains a carrier. Preferably, the carrier in the insecticide and acaricide is a substance acceptable in agriculture, forestry and horticulture and helpful for the application of the active ingredient. Particularly preferably, the carrier is a liquid carrier and / or a solid carrier, wherein the solid carrier is preferably selected from at least one solid substance selected from clay, natural or synthetic silicates, silicon dioxide, resins, waxes, and solid fertilizers; the liquid carrier is preferably selected from water, alcohols, ketones, petroleum fractions, aromatic hydrocarbons, chlorinated hydrocarbons, and liquefied gas.

[0033] In some embodiments of the present invention, preferably, the insecticide and acaricide may also contain surfactants, protective colloids, adhesives, thickeners, thixotropic agents, penetrants, chelating agents, colorants, polymers and other commonly used auxiliary components in the art. The present invention has no particular limitation on this, and those skilled in the art may select a reasonable composition and dosage according to actual needs.

[0034] In some embodiments of the present invention, preferably, the dosage forms of the insecticide and acaricide are each independently selected from at least one of wettable powders, soluble powders, emulsifiable concentrates, aqueous suspensions, dispersible oil suspensions, aqueous emulsions, suspoemulsions, microemulsions, aqueous solutions, granules, microcapsules and water-dispersible granules, whereby the active ingredients are more easily dissolved or dispersed so that they are easier to disperse when used as active substances of insecticides and acaricides, thereby improving the application effect.

[0035] In some embodiments of the present invention, preferably, the present invention has no particular limitation on the preparation method of the insecticide and acaricide, and those skilled in the art may refer to the methods in existing literature and standards in the field or adopt existing methods in the field to prepare the agent to obtain the desired composition and dosage form.

[0036] As mentioned above, the fourth aspect of the present invention provides the use of the insecticide and acaricide described in the third aspect of the present invention in killing insects and / or acaricides in agriculture, forestry and horticulture.

[0037] The present invention will be described in detail below by way of examples.

[0038] In the following examples, unless otherwise specified, all raw materials used are commercially available products.

[0039] In the following examples, unless otherwise specified, room temperature refers to 25±2°C.

[0040] [Example 1]

[0041] Preparation of Compound I-4

[0042]

[0043] The specific preparation process is as follows:

[0044] (1) Raw material 1 (6 g, 0.034 mol), anhydrous ethanol (18 ml, 3 vol), and purified water (6 ml, 1 vol) were added to a 100 ml three-necked flask in sequence. Potassium hydroxide (2.86 g, 0.051 mol) and carbon disulfide (3.88 g, 0.051 mol) were added under stirring. The system was heated to reflux for 10 h. TLC showed that the raw material had basically reacted. The system was cooled and quenched with water. After extraction with ethyl acetate, drying and desolvation were performed to obtain 6.9 g of a brown oil, which was directly used in the next step.

[0045] (2) Into a 100 ml three-necked flask, intermediate 2 (2 g, 0.009 mol), N,N-dimethylformamide (12 ml, 6 vol), purified water (4 ml, 2 vol), potassium carbonate (2.5 g, 0.018 mol), and 2,2,2-trifluoroiodoethane (3.78 g, 0.018 mol) were added in sequence. The system was heated to 80 °C for 5 h. TLC showed that the reaction of the raw materials was basically completed. The system was cooled and quenched with water. After extraction with 1,2-dichloroethane, drying and desolvation were performed, 2.53 g of a brown solid was obtained, which was directly used in the next step.

[0046] (3) In a 100 ml three-necked flask, intermediate 3 (1 g, 0.0033 mol) and anhydrous tetrahydrofuran (5 ml, 5 vol) were added. The mixture was cooled to <15°C in an ice bath. Sodium hydride (0.4 g, 0.0099 mol, 60%) was added in batches. Bubbles were generated. After the addition, the mixture was stirred for 0.5 h. Ethylsulfonyl chloride (0.51 g, 0.004 mol) was added dropwise. After the addition, the reaction was continued for 1 h. A small amount of raw material remained on TLC. The system was slowly poured into a saturated aqueous ammonium chloride solution to quench the mixture. The mixture was extracted with ethyl acetate, dried and desolvated. 0.17 g of a white solid was obtained by column chromatography. The purity was 95.66%, i.e., I-4. 1 H NMR (400MHz, Chloroform-d) δ7.87(s,1H),7.67(s,1H),4.09(q,J=9.6Hz,2H),3.42(q,J=7.4Hz,2H),1.29(t,J=7.4Hz,3H); MS(M+H + )=393.37 / 395.27.

[0047] [Example 2]

[0048] Preparation of Compound I-12

[0049]

[0050] The specific preparation process is as follows:

[0051] (1) Synthesis of Intermediate 2 Reference Example 1

[0052] (2) Into a 100 ml three-necked flask, intermediate 2 (2 g, 0.009 mol), N,N-dimethylformamide (12 ml, 6 vol), purified water (4 ml, 2 vol), potassium carbonate (2.5 g, 0.018 mol), and iodomethane (2.55 g, 0.018 mol) were added in sequence. The system was heated to 70 °C for 4 h. TLC showed that the raw materials had basically reacted. The system was cooled and quenched with water. After extraction with 1,2-dichloroethane, drying and desolvation were performed, 2.24 g of a brown solid was obtained, which was directly used in the next step.

[0053] (3) Add intermediate 3 (1.12 g, 0.0048 mol) and anhydrous tetrahydrofuran (5.6 ml, 5 vol) to a 100 ml three-necked flask, cool to <15°C in an ice bath, add sodium hydride (0.58 g, 0.0144 mol, 60%) in batches, and generate obvious bubbles. Stir for 0.5 h after addition, then add phenyl chloroformate (0.90 g, 0.0058 mol) dropwise, and react for 2 h after addition. TLC shows that the raw material has basically reacted. Pour the system slowly into saturated aqueous ammonium chloride solution to quench, extract with ethyl acetate, dry and desolventize, and obtain 0.26 g of white solid by column chromatography with a purity of 96.61%, i.e., I-12. 1 H NMR(400MHz,Chloroform-d)δ8.16–7.97(m,1H),7.73(s,1H),7.59–7.44(m,2H),7.35(s,3H),2.73(s,3H); MS(M+H + )=353.25 / 355.26.

[0054] [Example 3]

[0055] Preparation of Compound I-13

[0056]

[0057] The specific preparation process is as follows:

[0058] (1) Synthesis of Intermediate 2 Reference Example 1

[0059] (2) Into a 100 ml three-necked flask, intermediate 2 (2 g, 0.009 mol), N,N-dimethylformamide (12 ml, 6 vol), purified water (4 ml, 2 vol), potassium carbonate (2.5 g, 0.018 mol), and iodoethane (2.81 g, 0.018 mol) were added in sequence. The system was heated to 70 °C for 4 h. TLC showed that the raw materials had basically reacted. The system was cooled and quenched with water. After extraction with 1,2-dichloroethane, drying and desolvation were performed, 2.62 g of a brown solid was obtained, which was directly used in the next step.

[0060] (3) Add intermediate 3 (1 g, 0.004 mol) and anhydrous tetrahydrofuran (3 ml, 3 vol) to a 100 ml three-necked flask, cool to <15°C in an ice bath, add sodium hydride (0.48 g, 0.012 mol, 60%) in batches, and generate obvious bubbles. Stir for 0.5 h after addition, then add phenyl chloroformate (0.75 g, 0.0048 mol) dropwise, and react for 2 h after addition. TLC shows that the raw material has basically reacted. Pour the system slowly into saturated aqueous ammonium chloride solution to quench, extract with ethyl acetate, dry and desolventize, and obtain 0.2 g of white solid by column chromatography with a purity of 93.97%, i.e., I-13. 1H NMR(400MHz,Chloroform-d)δ8.07(s,1H),7.73(s,1H),7.50(t,J=7.9Hz,2H),7.43–7.31(m,3H),3.34(q,J=7.4Hz,2H),1.48(t,J=7.4Hz,3H), MS(M+H + )=367.35 / 369.27.

[0061] [Example 4]

[0062] Preparation of Compound I-15

[0063]

[0064] The specific preparation process is as follows:

[0065] (1) Synthesis of Intermediate 2 and Intermediate 3 Reference Example 1

[0066] (2) Add intermediate 3 (1 g, 0.0033 mol) and anhydrous tetrahydrofuran (3 ml, 3 vol) to a 100 ml three-necked flask, cool to <15°C in an ice bath, add sodium hydride (0.40 g, 0.0099 mol, 60%) in batches, and generate obvious bubbles. Stir for 0.5 h after addition, then add phenyl chloroformate (0.63 g, 0.004 mol) dropwise, and react for 2 h after addition. TLC shows that the raw material has basically reacted. Pour the system slowly into saturated aqueous ammonium chloride solution to quench, extract with ethyl acetate, dry and desolventize, and obtain 0.39 g of a white solid by column chromatography with a purity of 95.08%, i.e., I-15. 1 H NMR(400MHz,Chloroform-d)δ8.06(s,1H),7.74(s,1H),7.51(dd,J=8.6,7.2Hz,2H),7.40(t,J=7.5Hz,1H),7.37–7.31(m,2H),4.17(q,J=9.8Hz,2H); MS(M+H + )=421.24 / 423.23.

[0067]

Biological activity test

[0068] This test example tests the acaricidal activity of some compounds prepared in the present invention, specifically the acaricidal activity against Tetranychus cinnabarinus. The specific test process is as follows:

[0069] (1) Dissolving the compound to be tested in acetone and diluting it to the desired concentration with a 0.1 wt % Tween 80 aqueous solution, as shown in Test Example 1, the acetone content does not exceed 5 wt %, to prepare a drug;

[0070] (2) Remove one true leaf from the bean seedlings that have grown to two true leaves, inoculate with spider mites (the number of spider mites inoculated per bean seedling is 25-100), and investigate the number of inoculated mites 24 hours later. Use a handheld sprayer to spray the agent prepared in step (1) on the whole plant of three bean seedlings (the spray volume for each plant is 0.5 mL). After treatment, place them in a constant temperature observation room (25° C.) for observation. After 72 hours, investigate the number of live mites and calculate the mortality rate:

[0071] Mortality rate (%) = (number of inoculated mites - number of live mites after spraying) / number of inoculated mites × 100%.

[0072] [Test Example 1]

[0073] The compounds were diluted to a concentration of 100 mg / L and then tested according to the above process. In this test, compounds I-4, I-12, I-13, and I-15 showed 100% lethality to adult Tetranychus cinnabarinus mites.

[0074] According to the above test method, compounds I-4 and I-15 were selected for parallel tests with the compounds disclosed in DE1803728A to kill mites (Tetranychus cinnabarinus). The test results are shown in Table 2 below:

[0075] Table 2

[0076]

[0077] It can be seen from the above test results that the organic sulfur compounds or salts thereof provided by the present invention have good insecticidal and acaricidal effects, and the insecticidal and acaricidal activities are significantly higher than those of the control compounds.

[0078] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An organic sulfur compound as shown in formula I or an agriculturally acceptable salt thereof, characterized in that: In Formula I, R1 is C1-C3 alkyl, C1-C3 haloalkyl or phenyl C1-C3 alkyl; R2 is C1-C3 sulfonyl, phenoxycarbonyl or C1-C3 oxycarbonyl.

2. The organic sulfur compound or agriculturally acceptable salt thereof according to claim 1, characterized in that: In formula I, R1 is methyl, ethyl or trifluoromethyl; R2 is ethylsulfonyl or phenoxycarbonyl.

3. The organic sulfur compound or agriculturally acceptable salt thereof according to claim 2, characterized in that: Selected from the following structures, 4. Use of the organic sulfur compound or agriculturally acceptable salt thereof according to any one of claims 1 to 3 in the preparation of insecticides and acaricides.

5. An insecticide and acaricide, characterized in that: The insecticide and acaricide contains an active ingredient and at least one carrier, wherein the active ingredient is selected from at least one of the organic sulfur compounds or agriculturally acceptable salts thereof according to any one of claims 1 to 3.

6. The insecticide and acaricide according to claim 5, characterized in that: Based on the total weight of the insecticide and acaricide, the weight percentage of the active ingredient is 1-99%, more preferably 5-60%.

7. Use of the insecticide and acaricide according to any one of claims 5 to 6 in killing insects and / or acaricides in agriculture, forestry and gardening.

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