Long-acting volatile electric heating mosquito-repellent incense liquid and preparation method thereof

Abstract

The invention discloses long-acting volatile electric heating mosquito-repellent incense liquid and a preparation method thereof. The long-acting volatile electric heating mosquito-repellent incense liquid comprises the following components in percentage by weight: 0.4%-3% of a component A, 7%-99.5% of a component B, 0.01%-90% of a component C and 0.01%-3% of other auxiliaries, the component A is a compound as shown in a formula (I); the component B is a solvent; and the component C is a core rod dredging agent. The electric heating mosquito-repellent incense liquid can be continuously and stably volatilized when different contents are prepared, a core rod cannot be blocked, and the requirement for long-acting volatilization time is met. The active ingredients are low in toxicity and high in safety to people; # imgabs0 #

Description

[0001] This application is a divisional application of a Chinese invention patent application. The original application date was August 10, 2022, the application number was 202210953603.8, the invention title was "A long-acting volatile electric mosquito-repellent liquid and its preparation method", and the publication number was CN117617240A; the applicant filed a divisional application. Technical Field

[0002] The present invention relates to a long-acting volatile electric mosquito-repellent liquid and its preparation method, which can be used to prepare liquid mosquito-repellent with different contents, still ensure the continuous and stable volatilization of the original drug, will not block the core rod, avoid the loss of the medicament, and meet the requirement of the long-acting volatilization duration. Background Art

[0003] The pyrethroid compound shown in Formula I is a novel hygienic insecticide and has good basic activity for controlling hygienic pests; the pyrethroid compound shown in Formula I can be prepared according to the following reaction route:

[0004]

[0005] Wherein R is methyl or ethyl, M is sodium or potassium, and R1 is hydrogen.

[0006] For example, using methyl 3-formyl-2,2-dimethylcyclopropanecarboxylate (CAS No. 62138-41-4) as the starting material, reacting with acetonitrile at 60 °C under the action of sodium ethoxide for 4 hours, adding dilute hydrochloric acid to neutralize the pH to 8, adding ethyl acetate and water for liquid separation, and stripping the oil layer to obtain the intermediate methyl 3-(2-cyano-1-ethenyl)-2,2-dimethylcyclopropanecarboxylate.

[0007] Adding 2,3,5,6-tetrafluorobenzyl alcohol (CAS No. 4084-38-2), a catalytic amount of tetra-isopropyl titanate and toluene solvent to the obtained methyl 3-(2-cyano-1-ethenyl)-2,2-dimethylcyclopropanecarboxylate, slowly heating to reflux to distill out the by-product methanol, controlling in gas phase, after the raw materials are completely converted, cooling to 0-5 °C, dropping a small amount of water, separating the liquid, and stripping to obtain the pyrethroid compound of Formula I.

[0008] Starting from cyclopropanecarboxylates with different single configurations, pyrethroid compounds of formula I with corresponding configurations can be obtained. For example, when starting from methyl (1R,3R)-3-formyl-2,2-dimethylcyclopropanecarboxylate (CAS No. 27335-33-7), the product with 1R, 3R in the chrysanthemic acid part is obtained. Then, by fractional crystallization and separation of the double bond CN group Z,E isomers, a single 2,3,5,6-tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate or 2,3,5,6-tetrafluorobenzyl-(1R,3R)-3-[(1E)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate can be obtained. Starting from methyl (1R,3S)-3-formyl-2,2-dimethylcyclopropanecarboxylate (CAS No. 55701-02-5), 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-(-2-cyano-1-ethenyl)-2,2-dimethylcyclopropanecarboxylate or 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate or 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1E)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate can be obtained.

[0009] Currently, the usage duration of electric heating mosquito-repellent liquid in the market is limited. To prepare for a long usage duration, the content of the active ingredient in the liquid medicine needs to be increased, but increasing the content of the active ingredient will bring a series of problems, such as uneven volatilization of the active ingredient, causing problems such as core rod blockage and relatively high residual content of the active ingredient in the later stage, thus affecting the efficacy. To solve the above problems, the present invention optimizes the solvent and adds a core rod dredging agent that can assist the volatilization of the active ingredient to ensure that the high-content electric heating mosquito-repellent liquid can still volatilize continuously and evenly without the risk of blocking the core rod, thereby providing the possibility for the development of liquid mosquito-repellent products with different usage durations. On the other hand, people's requirements for the quality of life are getting higher and higher, and concepts such as low toxicity, environmental protection, and non-irritation are deeply rooted in people's hearts. By developing a long-acting volatilizing electric heating mosquito-repellent liquid, the same volume of liquid medicine can be used for a longer time, meeting the development concept of low-carbon environmental protection. The compound shown in formula (I) of the present invention has a slightly toxic acute oral toxicity rating and higher usage safety. Developing liquid mosquito-repellent products formulated with such safer active ingredients meets the needs of social development. Summary of the Invention

[0010] The technical problem to be solved by the present invention is to provide a long-acting volatilizing electric heating mosquito-repellent liquid and its preparation method, which can stably and continuously volatilize evenly, will not block the core rod, avoid loss of the medicament, and meet the requirement of long-acting volatilization duration, aiming at the deficiencies in the prior art.

[0011] To achieve the above object, the present invention adopts the following technical solutions:

[0012] A long-acting volatile electric heating mosquito-repellent liquid, by weight, contains 0.4%-3% of component A, 7%-99.5% of component B, 0.01%-90% of component C and 0.01%-3% of other auxiliaries;

[0013] The component A is the compound shown in formula (I), that is, 2,3,5,6-tetrafluorobenzyl-3-[-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate;

[0014] The component B is a solvent;

[0015] The component C is a core rod dredging agent;

[0016]

[0017] In the above technical solution, the component A shown is preferably selected from any one or a mixture of two or more of 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate, 2,3,5,6-tetrafluorobenzyl-(1S,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate, 2,3,5,6-tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate, 2,3,5,6-tetrafluorobenzyl-(1S,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate in any proportion.

[0018] In the above technical solution, the component A is further preferably 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate.

[0019] In the above technical solution, the component B is selected from any one or a mixture of two or more of amide solvents, monocarboxylic acid ester solvents, dicarboxylic acid ester solvents, tricarboxylic acid ester solvents, C8-20 alkane solvents, water, dodecylbenzene, decylbenzene, C2-8 alcohol solvents in any proportion.

[0020] In the above technical solution, the amide solvent is selected from N,N-dimethyldecanamide.

[0021] In the above technical solution, the monocarboxylic acid ester solvent is selected from any one or a mixture of two or more of methyl oleate, isopropyl tridecanoate, isopropyl myristate, isopropyl palmitate, isopropyl phenylacetate, ethyl phenylacetate, n-butyl myristate in any proportion.

[0022] In the above technical solution, the dicarboxylic acid ester solvent is selected from any one or a mixture of two or more of diisopropyl glutarate, diisopropyl adipate, and diisobutyl adipate in any proportion.

[0023] In the above technical solution, the tricarboxylic acid ester solvent is selected from any one or a mixture of two or more of tributyl citrate and acetyl tributyl citrate in any proportion.

[0024] In the above technical solution, the alcohol ether solvent is selected from any one or a mixture of two or more of triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and propylene glycol methyl ether in any proportion.

[0025] In the above technical solution, the C8-18 alkane solvent is selected from any one, two or more of D60 (ExxonMobil Chemical Company), D80 (ExxonMobil Chemical Company), D100 (ExxonMobil Chemical Company), D110 (ExxonMobil Chemical Company), D130 (ExxonMobil Chemical Company), Isopar-E (ExxonMobil Chemical Company), Isopar-G (ExxonMobil Chemical Company), Isopar-H (ExxonMobil Chemical Company), Isopar-L (ExxonMobil Chemical Company), Isopar-M (ExxonMobil Chemical Company), octane, nonane, quane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane in any proportion.

[0026] In the above technical solution, the C2-8 alcohol solvent is selected from any one, two or more of ethanol, isopropanol, n-propanol, n-butanol, sec-butanol, tert-butanol, n-pentanol and its isomers, n-hexanol and its isomers, n-heptanol and its isomers, n-octanol and its isomers in any proportion.

[0027] In the above technical solution, the component C is selected from any one or a mixture of two or more of propylene carbonate, butylene carbonate, glyceryl trioctanoate, sorbitan monooleate, fatty alcohol and ethylene oxide condensate, γ-butyrolactone, ethyl alkyl ethoxy ester, dipropylene glycol methyl ether acetate, the compound shown in formula (II), the compound shown in formula (III), and the compound shown in formula (IV) in any proportion;

[0028]

[0029] wherein R 1 , R 2 and R 3 are all C1-C10 alkyl groups.

[0030] In the above technical solution, the other auxiliary agents include any one of antioxidants, preservatives, and anti-ultraviolet agents, or a mixture of two or more of them in any proportion.

[0031] In the above technical scheme, the antioxidant is selected from any one of 2,6-di-tert-butyl-4-methylphenol, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, butylated hydroxyanisole, and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, or a mixture of two or more of them in any proportion.

[0032] In the above technical solution, the preservative is selected from sodium benzoate, sodium dehydroacetate, potassium sorbate, methyl paraben or kasone.

[0033] In the above technical solution, the anti-ultraviolet agent is 2-hydroxy-4-n-octyloxybenzophenone or 3,5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester.

[0034] The present invention also provides a method for preparing the long-lasting volatile electrothermal mosquito-repellent liquid, comprising the following steps:

[0035] Components A, B, C and other additives in the stated proportions are mixed at room temperature (or heated to below the boiling point of the solvent) until clarified, stirred evenly and then filled into packaging bottles, a drainage and volatilization core rod is inserted, and an outer cap is tightened to obtain a finished product.

[0036] Compared with the prior art, the electric mosquito-repellent liquid prepared by the present invention can achieve the purpose of driving away and killing sanitary pests. The electric mosquito-repellent liquid can volatilize the effective ingredients into the air through the liquid mosquito-repellent heater, and the volatilization time can be up to 960 hours. DETAILED DESCRIPTION

[0037] The specific implementation of the technical solution of the present invention is described in detail below, but the present invention is not limited to the following description:

[0038] The preparation method of the electric mosquito-repellent liquid in each embodiment of the present invention is as follows: components A, B, C and other additives in the stated proportions are mixed at room temperature (or heated to below the boiling point of the solvent) until clarified, stirred evenly and then filled into a packaging bottle, a drainage and volatilization core rod is inserted, and the outer cover is tightened to obtain the finished product.

[0039] The present invention will be described below in conjunction with specific embodiments:

[0040] Preparation Example 1: 0.4% 2,3,5,6-tetrafluorobenzyl-3-[(1Z)-2-cyano-1-vinyl]-2,2-dimethylcyclopropylcarboxylate electric mosquito-repellent liquid

[0041] 0.4 g of 2,3,5,6-tetrafluorobenzyl 3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate (each of the four isomers (1R,3S), (1S,3R), (1R,3R), and (1S,3S) accounts for 25%), 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 0.3 g of 2-hydroxy-4-n-octyloxybenzophenone, 5 g of glyceryl trioctanoate, 19.1 g of diisopropyl adipate, 40 g of D100, and 35 g of D110. The electric heating mosquito-repellent liquid was prepared according to the above method.

[0042] Formulation Example 2: 0.6% 2,3,5,6-tetrafluorobenzyl (1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate electric heating mosquito-repellent liquid

[0043] 0.6 g of 2,3,5,6-tetrafluorobenzyl (1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 5 g of glyceryl trioctanoate, 19.2 g of diisopropyl adipate, 40 g of D100, and 35 g of D110. The electric heating mosquito-repellent liquid was prepared according to the above method.

[0044] Formulation Example 3: 0.6% 2,3,5,6-tetrafluorobenzyl (1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate electric heating mosquito-repellent liquid

[0045] 0.6 g of 2,3,5,6-tetrafluorobenzyl (1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 5 g of glyceryl trioctanoate, 14.2 g of isopropyl myristate, 50 g of D100, and 30 g of D110. The electric heating mosquito-repellent liquid was prepared according to the above method.

[0046] Formulation Example 4: 0.75% 2,3,5,6-tetrafluorobenzyl (1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate electric heating mosquito-repellent liquid

[0047] 0.75 g of 2,3,5,6-tetrafluorobenzyl (1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate, 0.25 g of 2,6-di-tert-butyl-4-methylphenol, 5 g of propylene carbonate, 19 g of diisopropyl glutarate, 45 g of D100, and 30 g of D110. The electric heating mosquito-repellent liquid was prepared according to the above method.

[0048] Formulation Example 5: 0.9% 2,3,5,6-tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate Electric Mosquito Repellent Liquid

[0049] 0.9 g of 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 5 g of propylene carbonate, 23.9 g of isopropyl myristate, 34 g of D100, 36 g of D110, and the electric mosquito repellent liquid was prepared according to the above method.

[0050] Formulation Example 6: 1.2% 2,3,5,6-tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate Electric Mosquito Repellent Liquid

[0051] 1.2 g of 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 8 g of glyceryl trioctanoate, 20.6 g of diisopropyl glutarate, 32 g of D100, 38 g of D110, and the electric mosquito repellent liquid was prepared according to the above method.

[0052] Formulation Example 7: 1.2% 2,3,5,6-tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate Electric Mosquito Repellent Liquid

[0053] 1.2 g of 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 5 g of ethyl ethoxyester, 23.6 g of isopropyl myristate, 30 g of D100, 40 g of D110, and the electric mosquito repellent liquid was prepared according to the above method.

[0054] Formulation Example 8: 1.5% 2,3,5,6-tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate Electric Mosquito Repellent Liquid

[0055] 1.5 g of 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 8 g of propylene carbonate, 30.3 g of diisopropyl glutarate, 30 g of D110, 30 g of D130, and the electric mosquito repellent liquid was prepared according to the above method.

[0056] Formulation Example 9: 1.5% 2,3,5,6-tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate electric heating mosquito repellent liquid

[0057] 1.5 g of 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 8 g of ethyl ethoxyester, 30.3 g of diisopropyl adipate, 40 g of D110, 20 g of D130, and the electric heating mosquito repellent liquid was prepared according to the above method.

[0058] Formulation Example 10: 1.5% 2,3,5,6-tetrafluorobenzyl-3-[-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate electric heating mosquito repellent liquid

[0059] 1.5 g of 2,3,5,6-tetrafluorobenzyl-3-[-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 8 g of ethyl ethoxyester, 30.3 g of diisopropyl adipate, 40 g of D110, 20 g of D130, and the electric heating mosquito repellent liquid was prepared according to the above method.

[0060] Formulation Example 11: 1.8% 2,3,5,6-tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate electric heating mosquito repellent liquid

[0061] 1.8 g of 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 6 g of the compound shown in formula (II), 32 g of diisopropyl adipate, 30 g of D110, 30 g of D130, and the electric heating mosquito repellent liquid was prepared according to the above method.

[0062] Formulation Example 12: 1.8% 2,3,5,6-tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate electric heating mosquito repellent liquid

[0063] 1.8 g of 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 5 g of the compound shown in formula (IV), 32 g of diisopropyl adipate, 30 g of D110, 31 g of D130, and the electric heating mosquito repellent liquid was prepared according to the above method.

[0064] Formulation Example 13: 1.8% 2,3,5,6-Tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate Electric Heating Mosquito Repellent Liquid

[0065] 1.8 g of 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 5 g of the compound shown in formula (IV), 34 g of tributyl citrate, 25 g of D110, and 34 g of D130 were used to prepare the electric heating mosquito repellent liquid according to the above method.

[0066] Formulation Example 14: 2.1% 2,3,5,6-Tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate Electric Heating Mosquito Repellent Liquid

[0067] 2.1 g of 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 6 g of the compound shown in formula (IV), 36.7 g of diisopropyl adipate, 25 g of D110, and 30 g of D130 were used to prepare the electric heating mosquito repellent liquid according to the above method.

[0068] Formulation Example 15: 2.1% 2,3,5,6-Tetrafluorobenzyl-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate Electric Heating Mosquito Repellent Liquid

[0069] 2.1 g of 2,3,5,6-tetrafluorobenzyl-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate (each of the four isomers (1R,3S), (1S,3R), (1R,3R), and (1S,3S) accounts for 25%), 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 6 g of the compound shown in formula (IV), 36.7 g of diisopropyl adipate, 22 g of D110, and 33 g of D130 were used to prepare the electric heating mosquito repellent liquid according to the above method.

[0070] Formulation Example 16: 2.4% 2,3,5,6-Tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropanecarboxylate Electric Heating Mosquito Repellent Liquid

[0071] 2.4 g of 2,3,5,6 - tetrafluorobenzyl - (1R,3S) - 3 - [(1Z) - 2 - cyano - 1 - vinyl] - 2,2 - dimethylcyclopropyl carboxylate, 0.2 g of 2,6 - di - tert - butyl - 4 - methylphenol, 0.4 g of 2 - hydroxy - 4 - n - octyloxybenzophenone, 32 g of diisopropyl glutarate, 15 g of sorbitan monooleate, 20 g of D110, 30 g of D130, and the electric heating mosquito repellent liquid is prepared according to the above method.

[0072] Formulation Example 17: 2.7% of 2,3,5,6 - tetrafluorobenzyl - (1R,3R) - 3 - [(1Z) - 2 - cyano - 1 - vinyl] - 2,2 - dimethylcyclopropyl carboxylate electric heating mosquito repellent liquid

[0073] 2.7 g of 2,3,5,6 - tetrafluorobenzyl - (1R,3S) - 3 - [(1Z) - 2 - cyano - 1 - vinyl] - 2,2 - dimethylcyclopropyl carboxylate, 0.2 g of 2,6 - di - tert - butyl - 4 - methylphenol, 8 g of glyceryl trioctanoate, 34.1 g of diisopropyl adipate, 22 g of D110, 33 g of D130, and the electric heating mosquito repellent liquid is prepared according to the above method.

[0074] Formulation Example 18: 3% of 2,3,5,6 - tetrafluorobenzyl - (1R,3R) - 3 - [(1Z) - 2 - cyano - 1 - vinyl] - 2,2 - dimethylcyclopropyl carboxylate electric heating mosquito repellent liquid

[0075] 3 g of 2,3,5,6 - tetrafluorobenzyl - (1R,3S) - 3 - [(1Z) - 2 - cyano - 1 - vinyl] - 2,2 - dimethylcyclopropyl carboxylate, 0.2 g of 2,6 - di - tert - butyl - 4 - methylphenol, 0.4 g of 2 - hydroxy - 4 - n - octyloxybenzophenone, 8 g of glyceryl trioctanoate, 38.4 g of isopropyl myristate, 11 g of D110, 39 g of D130, and the electric heating mosquito repellent liquid is prepared according to the above method.

[0076] Formulation Example 19: 3% of 2,3,5,6 - tetrafluorobenzyl - (1R,3R) - 3 - [(1Z) - 2 - cyano - 1 - vinyl] - 2,2 - dimethylcyclopropyl carboxylate electric heating mosquito repellent liquid

[0077] 3 g of 2,3,5,6 - tetrafluorobenzyl - (1R,3S) - 3 - [(1Z) - 2 - cyano - 1 - vinyl] - 2,2 - dimethylcyclopropyl carboxylate, 0.2 g of 2,6 - di - tert - butyl - 4 - methylphenol, 0.4 g of 2 - hydroxy - 4 - n - octyloxybenzophenone, 37.4 g of diisopropyl adipate, 9 g of propylene carbonate, 12 g of D110, 38 g of D130, and the electric heating mosquito repellent liquid is prepared according to the above method.

[0078] Formulation Example 20: 3% 2,3,5,6-Tetrafluorobenzyl 3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate Electric Heating Mosquito Repellent Liquid

[0079] 3 g of 2,3,5,6-tetrafluorobenzyl 3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate (each of the four isomers (1R,3S), (1S,3R), (1R,3R), and (1S,3S) accounts for 25%), 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 0.4 g of 2-hydroxy-4-n-octyloxybenzophenone, 37.4 g of diisopropyl adipate, 7 g of the compound shown in formula (IV), 12 g of D110, and 40 g of D130 were used to prepare the electric heating mosquito repellent liquid according to the above method.

[0080] Comparative Example 1: 0.62% Tetrafluoromethylether Electric Heating Mosquito Repellent Liquid

[0081] 0.62 g of tetrafluoromethylether, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 0.4 g of 2-hydroxy-4-n-octyloxybenzophenone, 55.78 g of D80, and 43 g of D100.

[0082] Comparative Example 2: 3% 2,3,5,6-Tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate Electric Heating Mosquito Repellent Liquid

[0083] 3 g of 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate, 0.2 g of 2,6-di-tert-butyl-4-methylphenol, 0.4 g of 2-hydroxy-4-n-octyloxybenzophenone, 40.4 g of diisopropyl adipate, 16 g of D110, and 40 g of D130 were used to prepare the electric heating mosquito repellent liquid according to the above method.

[0084] Test Example 1:

[0085] Test method: Refer to "GB / T 13917.6-2009 Hygienic Insecticides for Pesticide Registration - Indoor Efficacy Tests and Evaluations - Part 6: Electric Heating Mosquito Repellent Liquids" to conduct efficacy tests at 240 h, 480 h, 720 h, and 960 h after spotting. Use a cylinder device: Each time, 30 test mosquitoes were sucked and placed through the central round hole of the round plate (F), and the rubber stopper (H) was tightly plugged. After the test insects resumed normal activities, the heater carrying the electric heating mosquito repellent liquid to be tested was continuously powered on to the corresponding time period and placed under the central empty area of the round plate (F), close to the central hole, and fumigated for 1 min. Immediately plug the rubber stopper (H) and start timing. The number of knocked-down test insects was recorded at regular intervals. The observation time was 20 min. The test should be repeated three times or more. After each test, the test device should be cleaned. The test results are shown in Table 1.

[0086] Table 1 Results of the Cylinder Potency Test of Electric Heating Mosquito Repellent Liquid with Different Samples

[0087]

[0088] The test results show that after adding Component C, it can ensure that the electric heating mosquito repellent liquid with a high content can still volatilize continuously and evenly, and the efficacy is more stable during the overall duration, without affecting the efficacy in the later stage of sample application.

[0089] Test Example 2:

[0090] Formulation Example 4, Formulation Example 8, and Formulation Example 18 were tested according to the method of Test Example 1, and the results are shown in Table 2.

[0091] Table 2 Results of the Cylinder Potency Test of Electric Heating Mosquito Repellent Liquid with Different Samples

[0092]

[0093] The test results show that different combinations of Component B of the present invention can control the liquid volatilization time, so that samples with different durations can be formulated.

[0094] Test Example 3:

[0095] Referring to GB / T 13917.10-2009, the efficacy test was carried out in the simulation room at the penultimate time point and evaluated according to the standard. The evaluation standard is that the knockdown rate of Culex pipiens pallens in 1 hour ≥ 90% is Class A activity, and the knockdown rate ≥ 70% is Class B activity. The test results are shown in Table 3.

[0096] Table 3 Results of the Simulation Room Potency Test of Electric Heating Mosquito Repellent Liquid with Different Samples

[0097]

[0098] The above examples are only to illustrate the technical concept and technical characteristics of the present invention, and should not be used to limit the protection scope of the present invention. Any equivalent transformation or modification made according to the essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. A long-acting volatile electric mosquito-repellent liquid, which is characterized in that: by weight, it contains 0.4%-3% of component A, 7%-99.5% of component B, 0.01%-90% of component C and 0.01%-3% of other auxiliaries; the component A is a compound shown in formula (I), namely 2,3,5,6-tetrafluorobenzyl-3-[-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate; the component B is a solvent; the component C is a core rod dredging agent; 2. The long-acting volatile electric mosquito-repellent liquid according to claim 1, which is characterized in that: the component A shown is selected from any one or a mixture of two or more of 2,3,5,6-tetrafluorobenzyl-(1R,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate, 2,3,5,6-tetrafluorobenzyl-(1S,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate, 2,3,5,6-tetrafluorobenzyl-(1R,3R)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate, 2,3,5,6-tetrafluorobenzyl-(1S,3S)-3-[(1Z)-2-cyano-1-ethenyl]-2,2-dimethylcyclopropyl carboxylate in any proportion.

3. The long-acting volatile electric mosquito-repellent liquid according to claim 1, which is characterized in that: the component B is selected from any one or a mixture of two or more of amide solvents, monocarboxylic acid ester solvents, dicarboxylic acid ester solvents, tricarboxylic acid ester solvents, C8-20 alkane solvents, dodecylbenzene, and decylbenzene in any proportion.

4. The long-acting volatile electric mosquito-repellent liquid according to claim 1, which is characterized in that: the component C is selected from any one or a mixture of two or more of propylene carbonate, butylene carbonate, glyceryl trioctanoate, sorbitan monooleate, fatty alcohol and ethylene oxide condensate, γ-butyrolactone, ethyl ethoxy ester, dipropylene glycol methyl ether acetate, the compound shown in formula (II), the compound shown in formula (III), and the compound shown in formula (IV) in any proportion; wherein R 1 , R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms.

5. The long-acting volatile electric mosquito-repellent liquid according to claim 1, which is characterized in that: the other auxiliaries include any one or a mixture of two or more of antioxidants, preservatives, and anti-ultraviolet agents in any proportion.

6. The long-acting volatile electric mosquito-repellent liquid according to claim 5, which is characterized in that: The antioxidant is selected from any one of 2,6-di-tert-butyl-4-methylphenol, isooctyl β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, butylated hydroxyanisole, n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, a mixture of two or more of them in any proportion; the preservative is selected from sodium benzoate, sodium dehydroacetate, potassium sorbate, methyl paraben or Kathon; the ultraviolet absorber is 2-hydroxy-4-n-octyloxybenzophenone or n-hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.

7. A method for preparing the long-acting volatile electric mosquito-repellent liquid according to claim 1, characterized in that: it comprises the following steps: Mix the components A, B, C and other auxiliaries in the stated proportions at room temperature (or heated to below the boiling point of the solvent) until clear, stir evenly, then fill into a packaging bottle, insert a drainage and volatilization core rod, and tighten the outer cap to obtain the finished product.

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