Mandelonitrile and isothiocyanate compound insecticidal composition, preparation and application of mandelonitrile and isothiocyanate compound insecticidal composition

Abstract

The invention provides a mandelonitrile and isothiocyanate compound insecticidal composition, a preparation and application of the mandelonitrile and isothiocyanate compound insecticidal composition and the preparation. The isothiocyanate is at least one selected from the group consisting of allyl isothiocyanate, ethyl isothiocyanate, n-propyl isothiocyanate, phenyl isothiocyanate, benzyl isothiocyanate, 1-phenyl ethyl isothiocyanate and 2-phenyl ethyl isothiocyanate; the mass ratio of the mandelonitrile to the isothiocyanate is (1-16): (100-1). The composition disclosed by the invention is used for preparing a fumigant for preventing and treating warehouse pests, root-knot nematodes in soil and pine wood nematodes on pine trees, has an obvious fumigating effect on pests such as grain pests, soil nematodes and pine wood nematodes, has an obvious synergistic effect and is relatively small in dosage.

Description

Technical Field

[0001] The invention belongs to the technical field of pesticides and relates to a compound insecticide composition of mandelonitrile and isothiocyanate, a preparation and application thereof. Background Art

[0002] Almond nitrile can be extracted from some plants of the Rosaceae and Aspergillus family. Isothiocyanates are widely present in the Cruciferae family, especially in the Brassica and Horseradish genera, where the output is considerable.

[0003] Garlic fruit (M.oleifera), also known as mountain tung fruit and monkey fruit, is a plant of a single genus unique to my country. The volatile oil from fresh branches and leaves and peel and pulp of garlic fruit is a light yellow liquid with a strong bitter almond aroma. Almond nitrile can be extracted from the volatile oil from branches and leaves and the volatile oil from peel and pulp.

[0004] There are a few studies that have shown that mandelonitrile has the ability to kill or inhibit bacteria, such as controlling Gram-positive and Gram-negative bacteria.

[0005] Horseradish (Armoracia rusticana (Lam)), also known as Western horseradish, horseradish, and horse radish, is a traditional Chinese medicinal material with anti-cancer, bactericidal, diuretic, and nerve-stimulating effects. Horseradish essential oil is usually a light yellow liquid with a pungent and stimulating smell similar to mustard.

[0006] Glucosinolates exist in horseradish and Brassica plants. When completely dried, glucosinolates and their hydrolases are distributed in different compartments in the cells and isolated from each other. When the plant tissue is broken, the cell structure is destroyed, and glucosinolates are fully in contact with the hydrolases. Under the action of the hydrolases, enzymatic hydrolysis occurs, thus producing isothiocyanate compounds with spicy taste.

[0007] The isothiocyanate compounds contained in horseradish mainly include allyl isothiocyanate (AITC), ethyl isothiocyanate (EITC), 4-pentenyl isothiocyanate, 5-hexenyl isothiocyanate, 3-butenyl isothiocyanate, phenyl isothiocyanate, benzyl isothiocyanate, 5-methylthiopentyl isothiocyanate, 6-methylthiohexyl isothiocyanate, and 7-methylthioheptyl isothiocyanate. Among them, the content of allyl isothiocyanate is the highest.

[0008] A large number of studies have shown that allyl isothiocyanate has significant anti-cancer potential, and it can induce apoptosis of cancer cells through various pathways. At the same time, allyl isothiocyanate has an inhibitory effect on a variety of bacteria and fungi. It has a certain inhibitory activity against common food spoilage bacteria and pathogens such as Escherichia coli, Staphylococcus aureus, yeast, and mold, and can be used in food preservation and medicine.

[0009] US7195788B2 discloses a composition containing mandelonitrile and its use, which contains mandelonitrile, benzaldehyde and hydrogen cyanide, and is mainly used for post-harvest commodities such as fruits, vegetables, roots, grains and nuts to prevent certain fungi and insects.

[0010] US20170223969A1 discloses an antibacterial composition extracted from Prunus plants, the main components of which are benzaldehyde, mandelonitrile and hydrogen cyanide, which can act alone or synergistically to control Gram-positive and Gram-negative bacteria.

[0011] The inventor's CN101133739 proposed several product formulations with allyl isothiocyanate as the main active ingredient for use in soil, food, textiles and tobacco warehouses, and provided a fumigation method that is very convenient for users. It also specified the specific use objects and dosages of allyl isothiocyanate as a pesticide product.

[0012] In summary, it is currently reported that the composition containing mandelonitrile has insecticidal biological activity, but its effective ingredients, specific pests that can be prevented and controlled, and usage scenarios are not clearly stated. The inventors screened and compounded the biological activities of mandelonitrile and isothiocyanate compounds and found that the compound combination can produce a synergistic effect. There is no public report on the use of the compound preparation between the two compounds as a fumigant for granaries, warehouses, and soil, and there is no report or patent application on the compound between the two compounds for treating pests. Summary of the invention

[0013] The purpose of the present invention is to provide an insecticidal composition of mandelonitrile and isothiocyanate with synergistic effect and good insecticidal effect.

[0014] Another object of the present invention is to provide an insecticidal composition of mandelonitrile and isothiocyanate for use in preparing an insecticidal preparation for controlling warehouse pests, root-knot nematodes in the soil and pine wood nematodes on pine trees.

[0015] The present invention is achieved through the following technical solutions:

[0016] An insecticide composition containing mandelonitrile and isothiocyanate, wherein the composition comprises mandelonitrile and isothiocyanate, and the isothiocyanate is selected from at least one of allyl isothiocyanate, ethyl isothiocyanate, n-propyl isothiocyanate, phenyl isothiocyanate, benzyl isothiocyanate, 1-phenylethyl isothiocyanate and 2-phenylethyl isothiocyanate;

[0017] The mass ratio of mandelonitrile to isothiocyanate is (1-17):(100-1).

[0018] Optionally, the specific insecticidal composition is:

[0019] The weight ratio of mandelonitrile to allyl isothiocyanate is (1-16):(2-1);

[0020] The weight ratio of mandelonitrile to ethyl isothiocyanate is (1-9):5;

[0021] The weight ratio of mandelonitrile to n-propyl isothiocyanate is (3-8):(100-13);

[0022] The weight ratio of mandelonitrile to phenyl isothiocyanate is (2-3):(50-2);

[0023] The weight ratio of mandelonitrile to benzyl isothiocyanate is (1-3): (100-13);

[0024] The weight ratio of mandelonitrile to 1-phenylethyl isothiocyanate is (1-11):(25-7);

[0025] The weight ratio of mandelonitrile to 2-phenylethyl isothiocyanate is (2-17):(13-12).

[0026] The use of any insecticidal composition containing mandelonitrile and isothiocyanate described in the present invention for preparing agricultural insecticides.

[0027] Optionally, the pesticide is in the form of an oil, a microemulsion, a soluble liquid, a fumigation tablet or a dry injection;

[0028] Calculated by mass percentage, the content of mandelonitrile in the agricultural insecticide is 1% to 30%, and the content of isothiocyanate is 1% to 60%.

[0029] A preferred solution is a pesticidal composition preparation containing mandelonitrile and isothiocyanate, wherein the preparation is an oil preparation, and the components and weight percentages are as follows:

[0030] Mandelonitrile 1% to 20%, isothiocyanate 1% to 60%, antioxidant 0.1% to 2%, solvent 10% to 80%, vegetable oil to 100%;

[0031] The antioxidant is propyl gallate, ascorbic acid or tocopherol;

[0032] The solvent is at least one of furfural, 5-methylfurfural, ethyl acetate and cyclohexanone;

[0033] The vegetable oil is soybean oil, rapeseed oil or cottonseed oil.

[0034] A preferred embodiment is an insecticide composition preparation containing mandelonitrile and isothiocyanate, wherein the preparation is a microemulsion, and the components and weight percentages are:

[0035] Mandelonitrile 1% to 10%, isothiocyanate 1% to 20%, emulsifier 12% to 28%, co-surfactant 5% to 15%, solvent 5% to 15%, water to 100%;

[0036] Wherein, the emulsifier is at least one of TX-10, Well201, Well202, Well205, Nongru 500, Nongru 601, and OP-10;

[0037] The co-surfactant is cyclohexanone or n-butanol;

[0038] The solvent is at least one of cyclohexanone, furfural, 5-methylfurfural, ethanol and ethyl acetate.

[0039] A preferred solution is a pesticidal composition preparation containing mandelonitrile and isothiocyanate, wherein the preparation is a soluble liquid, and the components and weight percentages are:

[0040] Mandelonitrile 1% to 30%, isothiocyanate 1% to 40%, emulsifier 1% to 10%, and solvent to 100%;

[0041] The emulsifier is at least one of TX-10, Well201, Well202, Well205, Nongru 500, Nongru 600, Nongru BY, Nongru EL and OP-10;

[0042] The solvent is at least one of ethanol, ethyl acetate, sec-butyl acetate, furfural and 5-methylfurfural.

[0043] A preferred solution is an insecticide composition preparation containing mandelonitrile and isothiocyanate, wherein the preparation is a fumigation tablet, and the components and weight percentages are: mandelonitrile 1% to 25%, isothiocyanate 1% to 30%, antioxidant 0.5% to 2.0%, carrier 60% to 92%,

[0044] The antioxidant is ascorbic acid or propyl gallate;

[0045] The carrier is at least one of starch, talc, diatomaceous earth, lignin and cellulose.

[0046] A preferred solution is an insecticide composition preparation containing mandelonitrile and isothiocyanate, wherein the preparation is a dry injection preparation, and the components and weight percentages are: mandelonitrile 1% to 25%, isothiocyanate 1% to 30%, emulsifier 1% to 30%, penetrant 1% to 10%, and solvent is made up to 100%;

[0047] The emulsifier is at least one of calcium dodecylbenzene sulfonate, sodium succinate sulfonate, polyethylene glycol monostearate and sorbitan sesquioleate;

[0048] The penetrant is polyether-modified trisiloxane or fatty alcohol polyoxyethylene ether;

[0049] The solvent is at least one of ethanol, isopropanol, propylene glycol, n-butanol, cyclohexanone and acetophenone.

[0050] Technical effects of the present invention:

[0051] The insecticidal composition of mandelonitrile and isothiocyanate of the present invention has obvious synergistic effect, high insecticidal activity, relatively small dosage, obvious fumigation effect on harmful organisms in scenes such as granaries, warehouses, and soil, and can be used to replace the banned fumigant-methyl bromide.

[0052] The insecticidal composition of mandelonitrile and isothiocyanate of the present invention is used for preparing a pesticide preparation for preventing and controlling warehouse pests, root-knot nematodes in the soil and pine wood nematodes on pine trees.

[0053] The invention uses mandelonitrile and isothiocyanate as active ingredients and is suitable for fumigation in different occasions such as granaries, warehouses, containers, soil, etc.; it has insecticidal activity and can fumigate and kill corn weevils, red flour beetles, book lice and other common warehouse pests, root-knot nematodes in the soil, pine wood nematodes on pine trees, etc. DETAILED DESCRIPTION

[0054] The present invention is further described below in conjunction with embodiments, but the present invention is not limited thereto.

[0055] The present invention uses mandelonitrile and isothiocyanate compounds to screen the fumigation activity of common warehouse pests, soil nematodes and pine wood nematodes. Through the screening of single-dose and compound preparations, it is found that the fumigation effect of the combination is better than that of the single-dose use. This invention can reduce the dosage, delay the resistance of pests, and provide a new method for preventing and controlling warehouse pests, root-knot nematodes in the soil, and pine wood nematodes on pine trees.

[0056] An insecticide composition containing mandelonitrile and isothiocyanate, comprising active ingredient A and active ingredient B, wherein the weight ratio of active ingredient A to active ingredient B is (1-17):(100-1), active ingredient A is selected from mandelonitrile, active ingredient B is isothiocyanate, and isothiocyanate is selected from any one of the following compounds: allyl isothiocyanate, ethyl isothiocyanate, n-propyl isothiocyanate, phenyl isothiocyanate, benzyl isothiocyanate, 1-phenylethyl isothiocyanate and 2-phenylethyl isothiocyanate;

[0057] Preferably, the weight ratio of mandelonitrile to allyl isothiocyanate is (1-16): (2-1);

[0058] The weight ratio of mandelonitrile to ethyl isothiocyanate is (1-9):5;

[0059] The weight ratio of mandelonitrile to n-propyl isothiocyanate is (3-8):(100-13);

[0060] The weight ratio of mandelonitrile to phenyl isothiocyanate is (2-3):(50-2);

[0061] The weight ratio of mandelonitrile to benzyl isothiocyanate is (1-3): (100-13);

[0062] The weight ratio of mandelonitrile to 1-phenylethyl isothiocyanate is (1-11):(25-7);

[0063] The weight ratio of mandelonitrile to 2-phenylethyl isothiocyanate is (2-17):(13-12).

[0064] The insecticide composition of mandelonitrile and isothiocyanate of the present invention can be made into pesticide preparations well known in the art, such as oil preparations, microemulsions, soluble liquid preparations or tablet preparations, and can be made into different dosage forms according to different application occasions.

[0065] When the compound is made into an oil, the components and weight percentage of the oil are: 1% to 10% of mandelonitrile, 5% to 50% of allyl isothiocyanate, 0.1% to 2% of antioxidant, 10% to 80% of solvent, and 100% of vegetable oil. The antioxidant is propyl gallate or tocopherol. The solvent is furfural, 5-methylfurfural, ethyl acetate or cyclohexanone. The vegetable oil is soybean oil, cotton oil or rapeseed oil.

[0066] The preparation process is as follows: first, the antioxidant is added into the mixed mother liquor of mandelonitrile and allyl isothiocyanate weighed in a certain amount and mixed thoroughly. Then, the vegetable oil and solvent weighed in a certain amount are mixed thoroughly. Finally, the above two solutions are mixed in a preparation tank and stirred continuously for 1 to 3 hours. The prepared oil is filtered through a filter, and the filtered oil is transferred to a brown glass bottle or a metal container with a liner, etc., because these materials can better block light and oxygen, which is conducive to the long-term storage of the oil. The oil is generally suitable for preventing and controlling pests in grain in warehouses.

[0067] When the microemulsion is prepared, the components and weight percentage of the microemulsion are: 1% to 20% of mandelonitrile, 4% to 50% of ethyl isothiocyanate, 12% to 28% of emulsifier, 5% to 15% of co-surfactant, 10% to 30% of solvent, and water is used to make up to 100%. The emulsifier is one or more of TX-10, Well201, Well202, Well205, Nongru 500, Nongru 601, OP-10, etc. The co-surfactant is cyclohexanone or n-butanol. The solvent is one or more of cyclohexanone, furfural, 5-methylfurfural, ethanol, and ethyl acetate.

[0068] The preparation process is as follows: first, accurately weigh mandelonitrile and ethyl isothiocyanate and place them in dry and clean containers respectively. Add a small amount of solvent for dissolution pretreatment to ensure that they can be fully dispersed. Next, add the selected emulsifier to a container containing a certain amount of water (or other solvents as the continuous phase), use a stirrer to stir at an appropriate speed, so that the emulsifier is evenly dispersed in the aqueous phase to form an emulsifier solution. Then, slowly add the dissolved active ingredient solution dropwise to the emulsifier solution, while constantly stirring to fully mix the active ingredient and the emulsifier. Afterwards, add a co-surfactant, which can further reduce the interfacial tension and promote the formation of a microemulsion. Finally, the prepared microemulsion is quality tested, and the qualified products are divided into double-barrier glass bottles or aluminum bottles with inner barrier layers, and sealed for storage. The microemulsion is generally used to prevent and control warehouse pests, root-knot nematodes in the soil, and pine wood nematodes on pine trees.

[0069] When the compound is made into a soluble liquid, the components and weight percentage of the soluble liquid are: 1% to 5% of mandelonitrile, 10% to 40% of benzyl isothiocyanate, 1% to 20% of emulsifier, and the solvent is made up to 100%. The emulsifier is one or more of TX-10, Well201, Well202, Well205, Nongru 500, Nongru 600, Nongru BY, Nongru EL, OP-10, etc. The solvent is one or more of ethanol, ethyl acetate, sec-butyl acetate, furfural, 5-methylfurfural, etc.

[0070] The preparation process is as follows: accurately weighed mandelonitrile and benzyl isothiocyanate are placed in a dry, clean beaker, and stirred at a low speed with a glass rod to fully mix them to form an active ingredient mixture. The pre-mixed active ingredient mixture is slowly added to the solvent, and stirred continuously until the active ingredient is completely dissolved to form a uniform transparent solution. Then, the emulsifier is slowly added to the solution in which the active ingredient is completely dissolved, and the addition process is continuously stirred to make it evenly dispersed. After the emulsifier is added, the stirring speed is gradually increased to high speed and the emulsification operation is performed for 15-30 minutes. A stable emulsified system is formed by high-speed stirring, and the active ingredient is evenly dispersed in the solvent to obtain a soluble liquid with good stability and fluidity. Subsequently, the prepared soluble liquid is subjected to quality inspection, and the soluble liquid that has passed the quality inspection is filtered through filter paper, filter screen or filter membrane to remove impurities, insoluble matter or insufficiently emulsified particles, so that it is more clear and transparent, and then promptly packaged with materials such as plastic bottles and glass bottles with good sealing and strong corrosion resistance, and the product name, effective ingredients, content, usage, precautions and other relevant information are marked on the packaging for easy storage, transportation and use. The soluble liquid is generally used to prevent and control warehouse pests, root-knot nematodes in the soil and pine wood nematodes on pine trees.

[0071] When the compound is made into fumigation tablets, the components and weight percentages of the tablets are: 1% to 20% of mandelonitrile, 3% to 30% of phenyl isothiocyanate, 0.5% to 2.0% of antioxidant, and 40% to 90% of carrier. The antioxidant is ascorbic acid or propyl gallate. The carrier is one of starch, talcum powder, diatomaceous earth, lignin or cellulose.

[0072] The preparation process is as follows: weighed mandelonitrile, phenyl isothiocyanate and antioxidant are placed in a suitable mixing device, such as a three-dimensional motion mixer or a V-type mixer. The mixing device is turned on and preliminary mixing is performed at an appropriate speed for about 10 to 30 minutes, so that the components can be evenly distributed before the carrier is added, and the carrier is slowly added to the mixed raw materials, stirring while adding. After the carrier is added, the speed of the mixing device is increased and the mixing is continued for 30 to 60 minutes to ensure that the components are fully mixed and uniform. The mixed material is transferred to the hopper of the tablet press. Adjust the parameters such as the pressure of the tablet press, the thickness and diameter of the tablet. Start the tablet press and press the mixed material into tablets. During the pressing process, pay attention to the tablet molding. If there are cracks, loose tablets, etc., the parameters of the tablet press need to be adjusted in time. The tablets with qualified quality are packaged with suitable packaging materials, such as aluminum foil bags or plastic bottles. The fumigation tablets are generally used to fumigate pests in grain warehouses.

[0073] When the compound is made into a dry injection agent, the components and weight percentage of the dry injection agent are: 1% to 40% of mandelonitrile, 3% to 30% of allyl isothiocyanate, 1% to 30% of emulsifier, 0% to 10% of penetrant, and the solvent is made up to 100%. The emulsifier is one or more of calcium dodecylbenzene sulfonate, sodium succinate sulfonate, polyethylene glycol monostearate or sorbitan sesquioleate. The penetrant is polyether-modified trisiloxane or fatty alcohol polyoxyethylene ether. The solvent is one or more of ethanol, isopropanol, propylene glycol, n-butanol, cyclohexanone, and acetophenone.

[0074] The preparation process is as follows: according to the formula, a certain amount of mandelonitrile, allyl isothiocyanate, emulsifier, penetrant and solvent are accurately weighed and put into a V-type mixer. Turn on the mixing equipment and mix at an appropriate speed. After mixing, use a filtering device (such as filter paper, filter membrane, etc.) to filter the solution to remove possible impurities, undissolved particles, etc., to obtain a clear and transparent injection agent solution. The injection agent with qualified quality after filtration is put into a plastic bottle or glass bottle, and the product name, ingredients, usage, shelf life and other information are marked on the packaging. The injection agent is generally used to prevent and control pine wood nematodes on pine trees.

[0075] The above production processes are all completed by machines under closed conditions. Workers should avoid direct contact with liquid medicine and uncut tablets. Production workers should have complete protective measures.

[0076] Bioassay research:

[0077] Determination of the activity of a single compound against several important warehouse pests: refer to the method of (Jiang Zhili, 2002), the specific method is to inoculate 30 test insects in a triangular flask (V = 250mL), then fix a filter paper strip (3cm × 1cm) on the rubber stopper, let the filter paper strip hang in the bottle (do not touch the bottle wall), and use a microinjector to drop a certain dose of monomer compound on the filter paper strip, quickly plug the rubber stopper, and seal the bottle mouth with sealing film and transparent sealing tape, and let the filter paper strip hang just at 1 / 3 of the center of the bottle, and place it in an intelligent incubator (L:D = 12:12, T = 27 ± 1℃, RH = 70 ± 5%) for fumigation treatment, set a blank control, set 3 replicates for each treatment, and test 30 insects for each replicate. After fumigation for 72 hours, remove the rubber stopper and let it diffuse for 1 hour, check the fumigation status of each bottle, and record the number of dead insects. The death standard is to move the insect body with a small brush, and the insect body is dead if there is no reaction. The mortality rate and the corrected mortality rate were calculated, and the fumigation results of each group were compared, and the monomer compound with good fumigation effect was selected. The test results are shown in Tables 1 to 9.

[0078] ① The fumigation activity of mandelonitrile and isothiocyanate compounds against warehouse pests was determined. The results are shown in Table 1.

[0079] Table 1 Results of the fumigation activity of compounds at different concentrations against three important storage pests

[0080]

[0081] The results in the above table show that when the concentration of the eight compounds is 20 μL / L, they all have good fumigation activity against red flour beetle, corn weevil, grain borer, etc. Therefore, the toxicity of the eight compounds was compared, and the results are shown in Table 2.

[0082] Table 2 Results of fumigation toxicity test of mandelonitrile and seven isothiocyanate compounds against three types of storage pests (72h)

[0083]

[0084]

[0085] Table 2 shows that mandelonitrile, ethyl isothiocyanate and allyl isothiocyanate have better control effects on the three pests.

[0086] ② Determination of the toxicity of different ratios of mandelonitrile and allyl isothiocyanate to Tribolium castaneum

[0087] First, the toxicity ratio of two pesticides mixed in a certain ratio is determined through indoor toxicity determination. When the toxicity ratio is less than 1, it is an antagonistic effect, when the toxicity ratio is greater than 1.1, it is a synergistic effect, and when the toxicity ratio is around 1 (±0.1), it is an additive effect. The one with the highest toxicity ratio is the best ratio. On this basis, granary and field tests are carried out.

[0088] Table 3 Toxicity test of different ratios of mandelonitrile and allyl isothiocyanate to Tribolium castaneum (72h)

[0089]

[0090] Note: The ratio of the above two drugs is the LC of the two drugs 50 Compare.

[0091] As shown in Table 3, when the LC 50 When the ratio is 1:4-9:1, that is, when the mass ratio of the active ingredients is 1:2-16:1, the toxicity ratio is greater than 1, and the combination within this range has a synergistic effect.

[0092] ③ Toxicity determination of different ratios of mandelonitrile and ethyl isothiocyanate to corn weevil

[0093] Table 4 Toxicity test of different ratios of mandelonitrile and ethyl isothiocyanate to corn weevils (72h)

[0094]

[0095] As shown in Table 4, when the LC 50 When the ratio is 3:7-4:1, that is, when the mass ratio of the active ingredients is 1:5-9:5, the toxicity ratio is greater than 1, and the combination within this range has a synergistic effect.

[0096] ④ Toxicity determination of different ratios of mandelonitrile and n-propyl isothiocyanate to the grain borer

[0097] Table 5 Toxicity test of different ratios of mandelonitrile and n-propyl isothiocyanate to rice borer (72h)

[0098]

[0099] Table 5 shows that when mandelonitrile and n-propyl isothiocyanate have LC 50 When the ratio is 1:9-7:3, that is, when the mass ratio of the active ingredients is 3:100-8:13, the toxicity ratio is greater than 1, and the combination within this range has a synergistic effect.

[0100] ⑤ Toxicity determination of different ratios of mandelonitrile and phenyl isothiocyanate against red castanea:

[0101] Table 6 Toxicity test of different ratios of mandelonitrile and phenyl isothiocyanate on Tribolium castaneum (72h)

[0102]

[0103] Table 6 shows that when mandelonitrile and phenyl isothiocyanate have LC 50 When the ratio is 1:9 to 4:1, that is, the mass ratio of the active ingredients is 2:50 to 3:2, the toxicity ratio is greater than 1, and the compounding within this range has a synergistic effect.

[0104] ⑥ Toxicity test of different ratios of mandelonitrile and benzyl isothiocyanate to corn weevils:

[0105] Table 7 Toxicity test of different ratios of mandelonitrile and benzyl isothiocyanate to corn weevils (72h)

[0106]

[0107] Table 7 shows that when the ratio of mandelonitrile to benzyl isothiocyanate is 1:9 to 7:3, that is, when the mass ratio of the active ingredients is 1:100 to 3:13, the toxicity ratio is greater than 1, and the combination within this range has a synergistic effect.

[0108] ⑦ Toxicity determination of different ratios of mandelonitrile and 1-phenylethyl isothiocyanate to the grain borer

[0109] Table 8 Toxicity determination of different ratios of mandelonitrile and 1-phenylethyl isothiocyanate to rice borer (72h)

[0110]

[0111] As shown in Table 8, when mandelonitrile and 1-phenylethyl isothiocyanate have a LC 50 When the ratio is 1:4 to 9:1, that is, when the mass ratio of the active ingredients is 1:25 to 11:7, the toxicity ratio is greater than 1, and the combination within this range has a synergistic effect.

[0112] ⑧ Toxicity test of different ratios of mandelonitrile and 2-phenylethyl isothiocyanate against Tribolium castaneum:

[0113] Table 9 Toxicity determination of different ratios of mandelonitrile and 2-phenylethyl isothiocyanate on Tribolium castaneum (72h)

[0114]

[0115]

[0116] As shown in Table 9, when the LC 50When the ratio is 1:4 to 7:3, that is, when the mass ratio of the active ingredients is 2:13 to 17:12, the toxicity ratio is greater than 1, and the combination within this range has a synergistic effect.

[0117] Embodiment 1:

[0118] First, 10 kg of propyl gallate is added into a mixed mother liquor of about 51.5 kg of 97% mandelonitrile technical drug and 210.5 kg of 95% allyl isothiocyanate technical drug accurately weighed and fully mixed. Then, 350 kg of soybean oil and 378 kg of furfural accurately weighed and fully mixed. Finally, the above two solutions are mixed in a preparation tank and stirred continuously for 1 to 3 hours. The prepared oil is filtered through a filter, and the filtered oil is transferred to a brown glass bottle or a metal container with a liner, etc., to prepare an oil product of 1 ton of mandelonitrile and allyl isothiocyanate insecticide composition.

[0119] Sampling analysis showed that the content of mandelonitrile was 5% and the content of allyl isothiocyanate was 20%. The product was divided into aluminum cans coated with barrier materials, each can weighing 5 kg, for a total of 200 cans. The cans were sealed and labeled to obtain the insecticide composition oil product with a content of 25%.

[0120] Embodiment 2:

[0121] The preparation process is the same as that of Example 1, except that 1 ton of the composition oil contains 206.2 kg of 97% mandelonitrile technical drug, 210.5 kg of 95% ethyl isothiocyanate technical drug, 20 kg of tocopherol, 200 kg of 5-methylfurfural, and 363.3 kg of rapeseed oil. Analysis shows that the content of mandelonitrile and ethyl isothiocyanate insecticide composition is 40%.

[0122] Embodiment 3:

[0123] The preparation process is the same as that in Example 1, the difference is that 1 ton of the composition oil contains 206.2 kg of 97% mandelonitrile technical drug, 526.3 kg of 95% n-propyl isothiocyanate technical drug, 20 kg of propyl gallate, 100 kg of ethyl acetate, and 147.5 kg of cottonseed oil. Analysis shows that the content of the mandelonitrile and n-propyl isothiocyanate composition is 70%.

[0124] Embodiment 4:

[0125] The preparation process is the same as that of Example 1, except that, in 1 ton of the composition oil, there are 103.1 kg of 97% mandelonitrile technical drug, 52.6 kg of 95% phenyl isothiocyanate technical drug, 10 kg of tocopherol, 300 kg of cyclohexanone, and 534.3 kg of soybean oil. Analysis shows that the content of the mandelonitrile and phenyl isothiocyanate composition is 15%.

[0126] Embodiment 5:

[0127] Production of 2% mandelonitrile and 14% benzyl isothiocyanate insecticide composition microemulsion

[0128] First, accurately weigh 41.23 kg of 97% mandelonitrile technical drug and 294.7 kg of 95% benzyl isothiocyanate technical drug, and place them in dry and clean containers. Add 200 kg of cyclohexanone for dissolution pretreatment to ensure that it can be fully dispersed. Next, add 240 kg of TX-10 to a container of 1124.07 kg of deionized water, and use a stirrer to stir at an appropriate speed to evenly disperse the emulsifier in the aqueous phase to form an emulsifier solution. Then, slowly add the dissolved active ingredient solution to the emulsifier solution, while constantly stirring to fully mix the active ingredient and the emulsifier. After that, add 100 kg of cyclohexanone to promote the formation of microemulsion. The amount of mandelonitrile in the sampled product is 2%, and the content of benzyl isothiocyanate is 14%. Finally, 2 tons of products with a total content of 16% of active components are obtained. The product is packaged in a 500mL double-barrier glass bottle with a sealed bottle mouth.

[0129] Embodiment 6:

[0130] The preparation process is the same as that in Example 5, the difference is that in 1 ton of the microemulsion composition, 154.6 kg of 97% mandelonitrile technical drug, 473.7 kg of 95% 2-phenylethyl isothiocyanate technical drug, 100 kg of solvent furfural, 130 kg of emulsifier Well201, 50 kg of co-surfactant cyclohexanone, and 91.7 kg of deionized water are added. The content of mandelonitrile and 2-phenylethyl isothiocyanate composition is 60%.

[0131] Embodiment 7:

[0132] The preparation process is the same as that in Example 5, the difference is that in 1 ton of the composition microemulsion, 51.5 kg of 97% mandelonitrile technical drug, 157.9 kg of 95% allyl isothiocyanate technical drug, 140 kg of solvent 5-methylfurfural, 200 kg of emulsifier agricultural milk 500, 50 kg of co-surfactant n-butanol, and 400.6 kg of deionized water are added, and the content of mandelonitrile and allyl isothiocyanate composition is analyzed to be 20%.

[0133] Embodiment 8:

[0134] The preparation process is the same as that in Example 5, the difference is that in 1 ton of the microemulsion composition, 154.6 kg of 97% mandelonitrile technical drug, 315.8 kg of 95% ethyl isothiocyanate technical drug, 140 kg of solvent ethanol, 220 kg of emulsifier OP-10, 70 kg of co-surfactant cyclohexanone, and 99.6 kg of deionized water are added. The content of mandelonitrile and ethyl isothiocyanate composition is 45%.

[0135] Embodiment 9:

[0136] Production of soluble liquid preparation of 6% mandelonitrile and 36% 1-phenylethyl isothiocyanate

[0137] 61.6 kg of 97% mandelonitrile technical and 378.9 kg of 95% 1-phenylethyl isothiocyanate technical were accurately weighed into a dry and clean beaker, and stirred at a low speed with a glass rod to fully mix and form an active ingredient mixture. The pre-mixed active ingredient mixture was slowly added to 300 kg of ethanol solvent, and stirred continuously until the active ingredient was completely dissolved to form a uniform transparent solution. Then 259.5 kg of TX-10 emulsifier was slowly added to the solution in which the active ingredient was completely dissolved, and the addition process was continued to stir to make it evenly dispersed. After the emulsifier was added, the stirring speed was gradually increased to high speed and the emulsification operation was performed for 15-30 minutes. A stable emulsified system was formed by high-speed stirring, and the active ingredient was evenly dispersed in the solvent to obtain a soluble liquid with good stability and fluidity. Subsequently, the prepared soluble liquid is subjected to quality inspection, and the soluble liquid that passes the quality inspection is filtered through filter paper, filter screen or filter membrane to remove impurities, insoluble matter or inadequately emulsified particles, making it clearer and more transparent. It is then promptly packaged with sealing and corrosion-resistant materials such as plastic bottles and glass bottles, and the product name, active ingredients, content, usage, precautions and other relevant information are marked on the packaging for easy storage, transportation and use.

[0138] The sampled product contained 6% mandelonitrile and 36% 1-phenylethyl isothiocyanate, and finally 1 ton of product with a total content of effective components of 42% was obtained. The product was packaged in a 500mL double-barrier glass bottle with a sealed bottle mouth.

[0139] Embodiment 10:

[0140] The preparation process is the same as that of Example 9, except that 1 ton of the soluble liquid composition contains 51.5 kg of 97% mandelonitrile technical drug, 157.9 kg of 95% phenyl isothiocyanate technical drug, 200 kg of emulsifier Well 201, and 590.6 kg of solvent ethyl acetate. Analysis shows that the content of the mandelonitrile and phenyl isothiocyanate combination is 20%.

[0141] Embodiment 11:

[0142] The preparation process is the same as that of Example 9, except that, in 1 ton of the soluble liquid of the composition, 30.9 kg of 97% mandelonitrile technical drug, 221 kg of 95% benzyl isothiocyanate technical drug, 150 kg of emulsifier Nongru 500, and 598.1 kg of solvent ethyl acetate are added. Analysis shows that the content of the mandelonitrile and benzyl isothiocyanate composition is 24%.

[0143] Embodiment 12:

[0144] The preparation process is the same as that of Example 9, except that 1 ton of the soluble liquid composition contains 309 kg of 97% mandelonitrile technical drug, 210.5 kg of 95% 2-phenylethyl isothiocyanate technical drug, 200 kg of emulsifier Nongru EL, and 280.5 kg of solvent sec-butyl acetate. Analysis shows that the content of the mandelonitrile and 2-phenylethyl isothiocyanate composition is 50%.

[0145] Embodiment 13:

[0146] Production of 5% mandelonitrile and 15% allyl isothiocyanate composition tablets

[0147] Put 52 kg of 97% mandelonitrile technical drug, 157.9 kg of 95% allyl isothiocyanate technical drug and 33.1 kg of propyl gallate into the V-type mixer. Turn on the mixing equipment and perform preliminary mixing at 10-30 rpm for about 10-30 minutes to ensure that the ingredients are evenly distributed before the starch is added. Slowly add 757 kg of starch to the above mixed raw materials, stirring while adding. After the carrier is added, increase the speed of the mixing equipment and continue mixing for 30-60 minutes to ensure that the ingredients are fully mixed. Transfer the mixed material to the hopper of the tablet press. Adjust the parameters of the tablet press, set the pressure to 10kN, the tablet thickness and diameter to 5mm, and the diameter to 10mm. Start the tablet press and press the mixed material into tablets.

[0148] The content of mandelonitrile in the sampled tablets was 5%, the content of allyl isothiocyanate was 14.9%, and the total content of effective components in the product was 20%. Each tablet was sealed with an aluminum foil bag or a plastic bottle.

[0149] The results of the test on the biological activity of the composition tablets of Example 13 against warehouse pests in simulated granaries:

[0150] Take 270 adults of red flour beetle, 270 adults of corn weevil, and 270 adults of grain borer collected from the granary, put 30 adults of red flour beetle into breathable mesh bags respectively, and put them into 9 bags in total, then put 30 adults of corn weevil into breathable mesh bags respectively, and put them into 9 bags in total; then put 30 adults of grain borer into breathable mesh bags respectively, and put them into 9 bags in total; put a certain amount of wheat in each bag, and then put 5 kg of wheat into a 10L glass desiccator.

[0151] Three bags of red flour beetle, three bags of corn weevil and three bags of grain borer were placed in each of the three layers, upper, middle and lower, of the wheat pile. Five tablets of the 5% mandelonitrile and 15% allyl isothiocyanate composition produced in Example 13 were placed on the upper layer of the wheat pile, and then vaseline was applied to the ground edge of the lid of the dryer, and the lid was closed tightly. The test results were checked after 24 and 48 hours.

[0152] Table 10 Test results of the biological activity of the composition tablets of Example 13 against warehouse pests in simulated granaries

[0153]

[0154] As can be seen from Table 10, after 24 hours, all the red flour beetles and grain borers in the upper layer of the wheat pile died, and at the same time, all the corn weevils in the upper, middle and lower layers died. After 48 hours, the test results showed that all the pests were dead.

[0155] Embodiment 14:

[0156] The preparation process is the same as that of Example 13, except that 1 ton of the composition tablets contains 92.8 kg of 97% mandelonitrile technical drug, 208.4 kg of 95% ethyl isothiocyanate technical drug, 20 kg of ascorbic acid, and 678.8 kg of talc. The content of the mandelonitrile and ethyl isothiocyanate combination is 29%.

[0157] Embodiment 15:

[0158] The preparation process is the same as that of Example 13, except that 1 ton of the composition tablets contains 165 kg of 97% mandelonitrile technical drug, 273.7 kg of 95% n-propyl isothiocyanate technical drug, 20 kg of propyl gallate, and 541.3 kg of diatomaceous earth. Analysis shows that the content of the mandelonitrile and n-propyl isothiocyanate composition is 42%.

[0159] Embodiment 16:

[0160] The preparation process is the same as that of Example 13, except that 1 ton of the composition tablets contains 309 kg of 97% mandelonitrile technical drug, 210.5 kg of 95% phenyl isothiocyanate technical drug, 40 kg of ascorbic acid, and 440.5 kg of lignin. Analysis shows that the content of the mandelonitrile and phenyl isothiocyanate combination is 50%.

[0161] Example 1-16: Test on the efficacy of compounding mandelonitrile and isothiocyanate to control warehouse pests in granaries:

[0162] Prepare a grain test warehouse, 6 meters long, 4 meters wide, and 5 meters high, put 30 tons of wheat in it, and pile it up in the test warehouse (without sacks). Take 900 adults of red flour beetles, 900 adults of corn weevils, and 900 adults of grain borers collected from the grain warehouse, and put 100 adults of red flour beetles, 100 adults of corn weevils, and 100 adults of grain borers into breathable mesh bags, for a total of 27 bags, and put a certain amount of wheat in them. Check the number of pest deaths in each mesh bag after 7 days, 14 days, and 21 days, and calculate the control effect.

[0163] Table 11 The efficacy test of mandelonitrile and isothiocyanate combination in controlling warehouse pests in granaries

[0164]

[0165]

[0166] It can be seen from Table 11 that the combination of mandelonitrile and isothiocyanate can effectively control the three warehouse pests, and the control effect is better than that of a single agent, and the control period is long.

[0167] Example 7-16 Field test of compounding mandelonitrile and isothiocyanate to control southern root-knot nematode

[0168] This experiment was arranged to be carried out in the southern root-knot nematode-prone area of ​​Yangling District, Shaanxi Province (morbidity index above level 5). Due to the long-term planting of a single crop, the root-knot nematode population is difficult to control. The previous crop planted on the plot was cucumber. One year before the experiment, no nematicides were used on the plot. The plot was planted in single ridges and double rows. Normal land preparation and management were carried out before the experiment. Before transplanting the test cucumber seedlings, the soil was treated with different almond nitriles and isothiocyanate insecticide compositions, and the ridges were sealed with polyethylene plastic film after treatment. After sealing for 7 days, the field was opened for 4 days and the cucumber seedlings were transplanted. The control effect of each agent was calculated 7 days, 14 days, and 21 days after the application of the drug.

[0169] Table 12 Field efficacy of mandelonitrile and isothiocyanate combination against southern root-knot nematode

[0170]

[0171] It can be seen from Table 12 that the combination of mandelonitrile and isothiocyanate can effectively control root-knot nematodes, and the control effect is better than that of a single agent, and the control period is long.

[0172] Embodiment 17:

[0173] Production of 10% mandelonitrile and 15% allyl isothiocyanate composite dry injection agent

[0174] 103.1 kg of 97% mandelonitrile technical drug, 157.9 kg of 95% allyl isothiocyanate technical drug, 100 kg of emulsifier calcium dodecylbenzene sulfonate, 50 kg of penetrant polyether modified trisiloxane and 589 kg of ethanol are weighed and put into a V-type mixer. Turn on the mixing equipment. After mixing, use a filtering device (such as filter paper, filter membrane, etc.) to filter the solution to remove possible impurities, undissolved particles, etc., to obtain a clear and transparent injection agent solution. The injection agent with qualified quality after filtration is put into a plastic bottle or a glass bottle, and the product name, ingredients, usage, shelf life and other information are marked on the package. The injection agent is generally used to prevent and control pine wood nematodes on pine trees.

[0175] Embodiment 18:

[0176] The preparation process is the same as that of Example 17, except that one ton of the composition injection dry agent contains 412.4 kg of 97% mandelonitrile technical drug, 210.5 kg of 95% ethyl isothiocyanate technical drug, 150 kg of emulsifier sodium succinate sulfonate, 110 kg of penetrant fatty alcohol polyoxyethylene ether, and 117.1 kg of solvent isopropanol. Analysis shows that the content of the mandelonitrile and ethyl isothiocyanate composition is 60%.

[0177] Embodiment 19:

[0178] The preparation process is the same as that of Example 17, except that 1 ton of the composition injection dry agent contains 61.9 kg of 97% mandelonitrile technical drug, 252.6 kg of 95% n-propyl isothiocyanate technical drug, 120 kg of emulsifier polyethylene glycol monostearate, 70 kg of penetrant polyether modified trisiloxane, and 495.5 kg of solvent propylene glycol. Analysis shows that the content of the mandelonitrile and n-propyl isothiocyanate composition is 30%.

[0179] Embodiment 20:

[0180] The preparation process is the same as that of Example 17, except that, in 1 ton of the composition injection dry agent, there are 103.1 kg of 97% mandelonitrile technical drug, 210.5 kg of 95% phenyl isothiocyanate technical drug, 100 kg of emulsifier sorbitan sesquioleate, 80 kg of penetrant fatty alcohol polyoxyethylene ether, and 506.4 kg of solvent cyclohexanone. Analysis shows that the content of mandelonitrile and phenyl isothiocyanate composition is 30%.

[0181] Example 17-20 Determination of biological activity of mandelonitrile and isothiocyanate mixture against pine wood nematode

[0182] In the pine forest of the test site, five areas severely infested by pine wood nematodes were selected, each with 100 pine trees with a breast diameter of about 25 cm. On the trunks of these pine trees, red paint was used to clearly mark them, and holes were punched 30 cm above the base of the trunk at an angle of 45°. Then, the four examples of the pharmaceutical agents were slowly inserted into the holes, and the time was ensured to be the same day. The left and right sides of each pine tree were punched, and two bottles of the pharmaceutical agent were injected on each side.

[0183] Table 13 Control rate of pine wood nematode disease in forests by trunk injection of a compound of mandelonitrile and isothiocyanate

[0184]

[0185] It can be seen from Table 13 that the combination of mandelonitrile and isothiocyanate can effectively control pine wood nematodes and effectively reduce the proportion of diseased and dead pine trees. The control effect is better than that of a single agent, and the dosage is reduced.

[0186] Although the present invention has been described in detail above with general descriptions and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements may be made thereto based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. An insecticidal composition containing mandelonitrile and isothiocyanate, characterized in that: The composition comprises mandelonitrile and isothiocyanate, and the isothiocyanate is selected from at least one of allyl isothiocyanate, ethyl isothiocyanate, n-propyl isothiocyanate, phenyl isothiocyanate, benzyl isothiocyanate, 1-phenylethyl isothiocyanate and 2-phenylethyl isothiocyanate; The mass ratio of mandelonitrile to isothiocyanate is (1-17):(100-1).

2. The insecticidal composition containing mandelonitrile and isothiocyanate according to claim 1, characterized in that: The specific insecticidal composition is: The weight ratio of mandelonitrile to allyl isothiocyanate is (1-16):(2-1); The weight ratio of mandelonitrile to ethyl isothiocyanate is (1-9):5; The weight ratio of mandelonitrile to n-propyl isothiocyanate is (3-8):(100-13); The weight ratio of mandelonitrile to phenyl isothiocyanate is (2-3):(50-2); The weight ratio of mandelonitrile to benzyl isothiocyanate is (1-3): (100-13); The weight ratio of mandelonitrile to 1-phenylethyl isothiocyanate is (1-11):(25-7); The weight ratio of mandelonitrile to 2-phenylethyl isothiocyanate is (2-17):(13-12).

3. Use of the insecticide composition containing mandelonitrile and isothiocyanate according to any one of claims 1 to 2 for preparing agricultural insecticides.

4. The use according to claim 3, characterized in that: The pesticide is in the form of an oil, a microemulsion, a soluble liquid, a fumigation tablet or a dry injection; Calculated by mass percentage, the content of mandelonitrile in the agricultural insecticide is 1% to 30%, and the content of isothiocyanate is 1% to 60%.

5. An insecticide composition preparation containing mandelonitrile and isothiocyanate, characterized in that: The preparation is an oil, and the components and weight percentages are: Mandelonitrile 1% to 20%, isothiocyanate 1% to 60%, antioxidant 0.1% to 2%, solvent 10% to 80%, vegetable oil to 100%; The antioxidant is propyl gallate, ascorbic acid or tocopherol; The solvent is at least one of furfural, 5-methylfurfural, ethyl acetate and cyclohexanone; The vegetable oil is soybean oil, rapeseed oil or cottonseed oil.

6. An insecticide composition preparation containing mandelonitrile and isothiocyanate, characterized in that: The preparation is a microemulsion, and the components and weight percentages are: Mandelonitrile 1% to 10%, isothiocyanate 1% to 20%, emulsifier 12% to 28%, co-surfactant 5% to 15%, solvent 5% to 15%, water to 100%; Wherein, the emulsifier is at least one of TX-10, Well201, Well202, Well205, Nongru 500, Nongru 601, and OP-10; The co-surfactant is cyclohexanone or n-butanol; The solvent is at least one of cyclohexanone, furfural, 5-methylfurfural, ethanol and ethyl acetate.

7. An insecticide composition preparation containing mandelonitrile and isothiocyanate, characterized in that: The preparation is a soluble liquid, and the components and weight percentages are: Mandelonitrile 1% to 30%, isothiocyanate 1% to 40%, emulsifier 1% to 10%, and solvent to 100%; The emulsifier is at least one of TX-10, Well201, Well202, Well205, Nongru 500, Nongru 600, Nongru BY, Nongru EL and OP-10; The solvent is at least one of ethanol, ethyl acetate, sec-butyl acetate, furfural and 5-methylfurfural.

8. An insecticide composition preparation containing mandelonitrile and isothiocyanate, characterized in that: The preparation is a fumigation tablet, and the components and weight percentages are: mandelonitrile 1% to 25%, isothiocyanate 1% to 30%, antioxidant 0.5% to 2.0%, carrier 60% to 92%, The antioxidant is ascorbic acid or propyl gallate; The carrier is at least one of starch, talc, diatomaceous earth, lignin and cellulose.

9. An insecticide composition preparation containing mandelonitrile and isothiocyanate, characterized in that: The preparation is a dry injection preparation, and the components and weight percentages are: 1% to 25% of mandelonitrile, 1% to 30% of isothiocyanate, 1% to 30% of emulsifier, 1% to 10% of penetrant, and the solvent is made up to 100%; The emulsifier is at least one of calcium dodecylbenzene sulfonate, sodium succinate sulfonate, polyethylene glycol monostearate and sorbitan sesquioleate; The penetrant is polyether-modified trisiloxane or fatty alcohol polyoxyethylene ether; The solvent is at least one of ethanol, isopropanol, propylene glycol, n-butanol, cyclohexanone and acetophenone.

Images