CN115806512A - Fluorine-containing acaricide and preparation method thereof - Google Patents
Fluorine-containing acaricide and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of new pesticides containing one sulfur-oxygen double bond, and particularly relates to a fluorine-containing acaricide, a preparation method and a field test experiment thereof, wherein all raw materials are commercial industrial products, the reaction condition is mild, the control is easy, the content of the prepared fluorine-containing acaricide is more than 90%, the total molar yield is more than or equal to 92% in terms of p-tert-butylphenol, the field activity test effect of the novel fluorine-containing acaricide is very good, and the novel fluorine-containing acaricide has better acaricidal property and low phytotoxicity compared with propargite.
Description
Technical Field
The invention belongs to the technical field of new pesticides containing one sulfur-oxygen double bond, and particularly relates to a fluorine-containing acaricide and a preparation method thereof.
Background
Propargite (also called propargite) is used as a sulfite acaricide, has the characteristics of high efficiency, low toxicity, broad spectrum, long lasting period, no harm to natural enemies, difficult generation of drug resistance and the like, is introduced since 1964, and is widely used for preventing and controlling various agricultural and forestry pest mites.
The literature (Zhong Liangkun, kong Xiaoyan, ni Yun, etc. the synthesis and biological activity research of novel sulfite compounds containing substituted isoxazole rings [ J ] Proc. Agro-pharmacy, 2015,17 (6): 651-659) indicates that propargite temperature sensitive acaricide has poor efficacy when the temperature is lower than 22 ℃ and can cause drug damage to citrus. Toxicological studies find that propargite has long-term high risk to mammals, secondary toxicity risk to birds and high risk to aquatic organisms.
The literature (Li Weinan, xue Zhaomin. Studies on the synthesis of propargite [ J ] proceedings of the Shandong academy of education 2009, no. 5: 77-79) reports the synthetic route of propargite as follows: reacting p-tert-butylphenol with epoxy cyclohexane under the action of base catalysis, and removing excessive epoxy cyclohexane to obtain 2- (4-tert-butylphenoxy) cyclohexanol; then reacting with thionyl chloride and removing excessive thionyl chloride to obtain 2- (4-tert-butylphenoxy) cyclohexyl chlorosulfite; and finally, reacting with propiolic alcohol under the condition of excessive acid-binding agent, and removing the solvent in the system to obtain the propargite crude oil.
The novel fluorine-containing acaricide seeks for higher activity acaricidal action and low phytotoxicity, and can provide wider application space.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a novel fluorine-containing acaricide and a preparation method thereof.
The invention is realized by the following technical scheme: a fluorine-containing acaricide has a molecular formula of,
wherein R is 1 、R 2 、R 3 At least one of which is F.
A preparation method of fluorine-containing acaricide comprises the following steps,
step one, preparing p-tert-butyl benzene epoxy cyclohexanol, wherein p-tert-butyl phenol, 1,2-epoxy cyclohexane and toluene are mixed according to a molar ratio of 1:1.1:3, mixing, reacting for 10 hours at the temperature of 115-120 ℃, washing for three times by using hot water with washing quantity, and removing excessive cyclohexene oxide and toluene by reduced pressure distillation to prepare p-tert-butyl benzene epoxy cyclohexanol for later use;
step two, preparing 2- (4-tert-butyl phenoxy) cyclohexyl chlorosulfite, dissolving p-tert-butyl phenoxy cyclohexanol in toluene, cooling to 0-10 ℃, and then dropwise adding thionyl chloride, wherein the molar ratio of the p-tert-butyl phenoxy cyclohexanol to the thionyl chloride is 1:1.0 to 1.4, keeping the temperature at 0 to 10 ℃ in the dropping process, raising the temperature to 25 to 30 ℃ after the dropping is finished, preserving the temperature for 15 to 20 hours, and removing the solvent and thionyl chloride by reduced pressure evaporation to obtain 2- (4-tert-butyl) cyclohexyl chlorosulfite as an oily matter;
and step three, mixing toluene, fluorine-containing ethanol and an acid-binding agent in a molar ratio of 3.
Further, in the third step, the acid is selected from one of formic acid, acetic acid, propionic acid, hydrochloric acid and sulfuric acid.
Further, in the third step, the fluorine-containing ethanol is one of 2-fluoroethanol, 2,2-difluoroethanol and 2,2,2-trifluoroethanol.
Further, in the third step, the acid-binding agent is one of triethylamine, pyridine and N, N-diisopropylethylamine
A method of testing a fluorine-containing miticide according to claim 1, comprising the steps of,
a, selecting an experimental object, an experimental medicament and an experimental site, wherein the experimental object is red spider, the experimental medicament is 45% bifenazate-etoxazole suspending agent, 30% ethacrylonitrile suspending agent, 73% propargite missible oil and 40% fluorine acaricide microemulsion, and the experimental site is a field;
b, dividing sixteen small areas in the field, wherein 45% bifenazate-etoxazole suspending agent, 30% ethacrylonitrile suspending agent, 73% propargite missible oil and 40% fluacaricide microemulsion respectively correspond to the four small areas, and the application amount is respectively 45% bifenazate-etoxazole suspending agent 33.5ga.i./hm 2 33.5g a.i./hm of 30% ethazole mite nitrile suspending agent 2 40% of fluorine acaricide microemulsion 45ga.i./hm 2 73% propargite emulsifiable concentrate 55ga.i./hm 2 ；
C, randomly hanging the cards and marking 10 plant strips in each cell, investigating the total number of eggs and adults on 10 cells before pesticide application, investigating the number of remaining insects on the branches 1d, 3d, 15d and 30d after pesticide application, recording and analyzing.
The invention has the beneficial effects that: according to the synthetic method of the fluorine-containing acaricide, all raw materials are commercial industrial products, the reaction conditions are mild and easy to control, the content of the prepared fluorine-containing acaricide is more than 90%, the total molar yield is more than or equal to 92% in terms of p-tert-butylphenol, the field activity test effect of the novel fluorine-containing acaricide is very good, and the novel fluorine-containing acaricide has better acaricidal property and low phytotoxicity compared with propargite.
Drawings
FIG. 1 is a graphic synthesis scheme of a fluorine-containing acaricide;
FIG. 2 is a nuclear magnetic spectrum of the bulk fluorine-containing acaricide prepared in example 1;
FIG. 3 is a nuclear magnetic spectrum of the fluuorinated acaricide prepared in example 2;
FIG. 4 is a nuclear magnetic spectrum of the fluuorinated acaricide prepared in example 3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A fluorine-containing acaricide has a molecular formula of,
the preparation method comprises the following steps:
step one, preparing p-tert-butylphenoxy cyclohexanol, putting 50 g of p-tert-butylphenol, 52.3 g of cyclohexene oxide, 3.73 g of potassium hydroxide and 106 ml of toluene into a 250 ml three-necked bottle, heating to reflux, keeping the reflux for 10 hours, and washing with hot water at the temperature of more than 80 ℃ for three times, wherein each time is 150 ml; removing excessive cyclohexene oxide and toluene by reduced pressure distillation to obtain 82.4 g of white p-tert-butylphenoxy cyclohexanol with the yield of 99.7 percent;
step two, preparing 2- (4-tert-butylphenoxy) cyclohexyl chlorosulfite, adding 15.1 g of thionyl chloride and 60 ml of toluene into a 250 ml three-neck flask, replacing with nitrogen for three times, cooling to 0 ℃, adding 30 g of p-tert-butylphenoxy cyclohexanol solid in batches, keeping the temperature for reaction for 12 hours after the addition is finished, adding 60 ml of dichloromethane, concentrating under reduced pressure, repeatedly adding dichloromethane for 3 times, and evaporating to dryness to obtain 40g of oily matter with the yield of 100%.
Step three, preparing 2- (4-tert-butylphenoxy) cyclohexyl sulfurous acid-2-fluoroethanol ester, putting 8.31 g of 2-fluoroethanol, 20 ml of toluene and 21.6 ml of triethylamine into a 250 ml three-necked bottle, replacing the mixture with nitrogen for three times, cooling to 0 ℃, dropwise adding 39 g of 2- (4-tert-butylphenoxy) cyclohexyl chlorosulfite/25 ml of toluene mixed solution, controlling the temperature to be below 10 ℃, continuing to react for 2 to 3 hours after the dropwise adding is finished, dropwise adding acetic acid to adjust the pH value to be neutral, washing once with 100 ml of 10% sodium chloride aqueous solution, washing twice with pure water, and obtaining 36 g of golden yellow oily liquid which is evaporated under reduced pressure by organic phase, wherein the yield is 85% of the fluorine-containing acaricide.
The nuclear magnetic spectrum of the fluidextract raw pesticide obtained in the example is shown in figure 2.
Example 2
A fluorine-containing acaricide has a molecular formula of,
the preparation method comprises the following steps:
step one, preparing p-tert-butylphenol epoxy cyclohexanol, putting 50 g of p-tert-butylphenol, 52.3 g of epoxy cyclohexane, 3.73 g of potassium hydroxide and 106 ml of toluene into a 250 ml three-necked bottle, heating to reflux, keeping the reflux for 10 hours, washing three times with hot water at the temperature of more than 80 ℃, removing excessive epoxy cyclohexane and toluene by reduced pressure distillation, and obtaining 82.4 g of white p-tert-butylphenol epoxy cyclohexanol with the yield of 99.7 percent, wherein 150 ml of hot water is used for each time;
step two, preparing 2- (4-tert-butylphenoxy) cyclohexyl chlorosulfite, adding 15.1 g of thionyl chloride and 60 ml of toluene into a 250 ml three-necked bottle, replacing the thionyl chloride with nitrogen for three times, cooling to 0 ℃, adding 30 g of p-tert-butylphenoxy cyclohexanol solid in batches, after the addition is finished, carrying out heat preservation reaction for 12 hours, after the heat preservation is finished, adding 60 ml of dichloromethane, carrying out reduced pressure concentration, repeatedly adding dichloromethane for 3 times, and evaporating to dryness to obtain 40g of oily matter which is 2- (4-tert-butyl) cyclohexyl chlorosulfite, wherein the yield is 100%.
Step three, preparing 2- (4-tert-butylphenoxy) cyclohexyl sulfurous acid-2,2-difluoroethanol ester: 250. 10.7 g of 2,2-difluoroethanol, 20 ml of toluene and 21.6 ml of triethylamine are put into a ml three-mouth bottle and replaced by nitrogen for three times, the temperature is reduced to 0 ℃, 39 g of 2- (4-tert-butylphenoxy) cyclohexyl chlorosulfite/25 ml of toluene mixed solution is dripped, the temperature is controlled to be below 10 ℃, the reaction is continued for 2 to 3 hours after the dripping is finished, acetic acid is dripped to adjust the PH value to be neutral, 100 ml of 10% sodium chloride aqueous solution is washed once, and the pure water is washed twice, each time is 100 ml, thus obtaining 40g of golden yellow oily liquid which is evaporated by pressure and dried by organic phase, and is the original drug of the fluorine-containing acaricide, and the yield is 90%.
The nuclear magnetic spectrum of the fluidextract raw pesticide obtained in the example is shown in figure 3.
Example 3
A fluorine-containing acaricide has a molecular formula of,
the preparation method comprises the following steps:
step one, preparing p-tert-butyl benzene epoxy cyclohexanol: 50 g of p-tert-butylphenol, 52.3 g of cyclohexene oxide, 3.73 g of potassium hydroxide and 106 ml of toluene are put into a 250 ml three-neck flask, the temperature is raised to reflux, the reflux is kept for 10 hours, the mixture is washed three times with hot water of more than 80 ℃ and 150 ml of toluene each time, the excessive cyclohexene oxide and toluene are removed by reduced pressure distillation, 82.4 g of white p-tert-butylphenoxy cyclohexanol is obtained, and the yield is 99.7%;
step two, the preparation of 2- (4-tert-butylphenoxy) cyclohexyl chlorosulfite: 15.1 g of thionyl chloride and 60 ml of toluene are put into a 250 ml three-neck flask, replaced by nitrogen for three times, cooled to 0 ℃, and added with 30 g of p-tert-butyl phenoxy cyclohexanol solid in batches. After the addition, the reaction is carried out for 12 hours under the condition of heat preservation, 60 ml of dichloromethane is added for decompression and concentration after the heat preservation is finished, the dichloromethane is repeatedly added for 3 times, and evaporation is carried out to obtain 40g of oily matter which is 2- (4-tert-butyl) cyclohexyl chlorosulfite with the yield of 100 percent;
step three, preparing 2- (4-tert-butylphenoxy) cyclohexyl sulfurous acid-2,2,2-trifluoroethyl alcohol ester: 13.0 g of 2,2,2-trifluoroethanol, 20 ml of toluene and 21.6 ml of triethylamine are put into a 250 ml three-mouth bottle, nitrogen is substituted for three times, the temperature is reduced to 0 ℃, 39 g of 2- (4-tert-butylphenoxy) cyclohexyl chlorosulfite/25 ml of toluene mixed solution is dripped, the temperature is controlled to be below 10 ℃, after dripping is finished, the reaction is continued for 2 to 3 hours, acetic acid is dripped to adjust the pH value to be neutral, 100 ml of 10% sodium chloride aqueous solution is washed once, pure water is washed twice, 100 ml of each time, the organic phase is evaporated to dryness under reduced pressure, and 43 g of golden yellow oily liquid is obtained, which is the fluorine-containing acaricide raw drug, and the yield is 93%.
The nuclear magnetic spectrum of the fluidextract raw pesticide obtained in the example is shown in figure 4.
The fluorine-containing acaricide is obtained by modifying the drug group in the field to achieve the technical effects of reducing the toxic and side effects of the existing drug, improving the drug effect and the like, and the introduced group has an unfixed using effect on the product, and the technical effect is unpredictable.
The activity was measured as follows:
the control effect for the red spider is detected,
screening safe and efficient pesticide for preventing and treating red spider.
In 2020 and 2021, field efficacy tests are carried out, and 4 novel insecticides, namely 40% fluorine mite first microemulsion, 45% bifenazate-etoxazole suspending agent, 30% ethiazole mite nitrile suspending agent and 73% propargite missible oil are adopted, wherein the insecticide with better control effect on red spiders is 40% fluorine mite first microemulsion, the dead insect rate of 3d mites after the insecticide is more than 97%, the dead insect rate of 14d eggs after the insecticide is more than 97%, the lasting period reaches about 30d, fluorine mites are the fluorine-containing acaricide provided in the embodiment 1 firstly, and the molecular formula is as follows:
the result is that the 40% fluorine mite first microemulsion can be popularized and applied in production as a high-efficiency medicament, wherein the 40% fluorine mite first microemulsion is the diluent of the fluacrid acaricide obtained by the invention to the weight content of 40%.
Specifically, the red spider is an animal belonging to the family Tetranychidae of the order Acarina. It is mainly distributed in China, japan, thailand, philippines, etc. The male red spiders are 0.42-0.52 mm long, have large body color change, are generally red and pear-shaped, and have black long spots on both sides of the back of the body; the female red spider mite is deep red, and has black spots on two sides and elliptic shape. It belongs to high temperature active animal, and has the advantages of strong fecundity, fast development, short period, strong adaptability, wide spreading mode, wide distribution and miscellaneous feeding. Mainly harms various fruit trees and vegetable crops of citrus trees, apple trees, solanaceae, cucurbitaceae, leguminosae, liliaceae and the like and ornamental plants of rosaceous.
At present, the prevention and treatment of red spiders are mainly based on chemical prevention and treatment, and the conventional common pesticides comprise 110g/L etoxazole suspending agent, 43% bifenazate suspending agent, 30% ethiprole suspending agent, 73% propargite missible oil and 340g/L spirodiclofen suspending agent. Because the long-term use of the insecticides causes drug resistance of pests and obviously reduces the control effect, the problem of drug resistance of red spiders needs to be solved by replacing insecticides. In order to safely and efficiently prevent and treat red spiders, field pesticide effect tests are carried out in Jinning district of Kunming city in Yunnan province, sanmen county in Taizhou city in Zhejiang province, indocalamus transverse town in Wenling city in Taizhou city in Zhejiang province and Delist Temple town in Wakuan city in Dalian city in Liaoning province, 4 novel pesticides are researched, wherein the pesticide comprises 40% of fluorine mite microemulsion 45g a.i./hm 2 45% BifenazateEtoxazole suspending agent 33.5g a.i./hm 2 33.5g a.i./hm of 30% ethazole mite nitrile suspending agent 2 73% propargite missible oil 55g a.i./hm 2 The prevention and treatment effect on the red spiders is expected to be popularized and applied in production, and the quality of crops is improved.
Materials and methods of experiment:
test site and conditions
The tests were carried out on 4 different crops, 4 places respectively,
(1) The ornamental plant plantation of the south Rosaceae of Kunyang street in Jinning area of Kunming, yunnan province is a luxuriant growing period and the variety is super;
(2) The method is carried out at cherry planting houses in the Templezhen town of Wakuan shop, dalian city, liaoning province, and the variety is dates;
(3) The method is carried out at orange growers in Sanmen county in Taizhou city of Zhejiang province, and the varieties are red beauty in the germination growth period;
(4) The cultivation of the watermelon in the transverse region of Indocalamus in Taizhou, zhejiang province is carried out, the first batch of the watermelon is finished, and the next batch of the watermelon grows for 8424.
Reagent for testing
45% bifenazate etoxazole suspending agent 33.5g a.i./hm 2 Ruidefeng biotechnology, inc., dongguan; 30% ethazoxazole nitrile suspending agent 33.5g a.i./hm 2 Shenyang Kechui Chemicals, inc.; 73% propargite missible oil 55g a.i./hm 2 Aisida biochemicals, inc.; 45g a.i./hm of 40% fluacrid first microemulsion 2 The biotechnology research center for small insects in Henan province.
Design of experiments
45% bifenazate and etoxazole suspending agent 33.5g a.i./hm 2 33.5g a.i./hm of 30% ethazole mite nitrile suspending agent 2 45g a.i./hm of 40% fluacrid microemulsion 2 73% propargite missible oil 55g a.i./hm 2 The total amount of the treatment is 4, and the dosages of the treatment are all effective component dosages. Each treatment is provided with 4 times of repetition, 16 cells are totally formed, and the area of each cell is 30m 2 And each cell adopts random arrangement.
Application time and method
The tests are respectively carried out in 7 months and 5 months in 2021 in 2020, no other pesticide is applied before and during the tests, and the tests adopt a 3WBD-16L type knapsack sprayer to carry out whole plant spraying, so that the front and back sides of the leaf are uniformly coated with pesticide, and preferably water drops downwards.
Investigation and statistical method
Randomly hanging the cards in each cell and marking 10 plant strips, investigating the total number of eggs and adults on 10 cells before pesticide application, and investigating the number of the remaining insects on the branches 1d, 3d, 15d and 30d after pesticide application. And calculating the prevention and treatment effect by using EXCEL office software, and counting the difference significance of the prevention and treatment effects among treatments by using a DPS data processing system.
Results and analysis
The results of the field test in 2020 and 7 months are shown in tables 1-1 and 1-2. The control effect of the novel insecticide fluorine mite is better than that of 2-fluorine mite and 3-fluorine mite at 1d after the insecticide is applied, and the control effect of the fluorine mite on red spider eggs and imagoes is respectively 98.35 percent and 98.95 percent after the insecticide is applied at 15d, so that the control effect of the fluorine mite is obviously better than that of the 2-fluorine mite and that of the 3-fluorine mite at first; from the table 1-2, the test of different dilution times is carried out on the fluorine mites, the 1d and 1000-time liquid dilution after the pesticide is superior to that of the fluorine mites diluted by 1500-time liquid and 2000-time liquid, the control effects of the 3d and 1000-time liquid dilution after the pesticide and 1500-time liquid dilution are close to that of the fluorine mites diluted by 2000-time liquid, and the control effects are superior to that of the 2000-time liquid dilution; the death rate of fluorine mites diluted by 15d and 1000 times to eggs and imagoes after the pesticide is 98.32 percent and 98.25 percent, the death rate of fluorine mites diluted by l500 times to eggs and imagoes is 97.05 percent and 97.75 percent, and the control effect of fluorine mites diluted by 1000 times is close to that of fluorine mites.
TABLE 1-1% Dermatophagoides pteronyssinus ME for red spider field efficacy test of Rosaceae ornamental flower (2020 Zhejiang Taizhou)
Note: (1) the data in Table 1-1 are all 4-time repeat averages;
(2) The experimenter did not continue to observe during the 30 day time return trip;
TABLE 1-2% Dermatophagoides pteronyssinus ME for red spider field efficacy test of Rosaceae ornamental flower (2020 Zhejiang Taizhou)
Note: (1) the data in tables 1-2 are all 4-time repeat averages;
(2) The experimenter did not continue to observe during the 30 day time return trip;
the results of the test of the new 4 kinds of pesticides on the prevention of red spider are shown in tables 2-1, 2-2, 2-3 and 2-4 after 5 months 2021. After-drug 3d,40% Dermatophagoides pteronyssinus first microemulsion 45g a.i./hm 2 The dead rate of the imago reaches more than 97 percent, and is obviously superior to the 45 percent bifenazate-etoxazole suspending agent 33.5g a.i./hm 2 And 30% ethazoxazonitrile suspending agent 33.5g a.i./hm 2 15d,40% Dermatophagoides pteronyssinus first microemulsion 45g a.i./hm after drug administration 2 The dead rate of the suspension on eggs reaches more than 98 percent, and is obviously superior to 45 percent of bifenazate-etoxazole suspension agent 33.5g a.i./hm 2 And 30% ethazoxazonitrile suspending agent 33.5g a.i./hm 2 The effective period is 30 days.
TABLE 2-1% Fluoroacarid ME for the test of the efficacy of red spider, a rosebush ornamental flower, in the field (Yunnan Kunming 2020)
Note: (1) the data in Table 2-1 are all 4-time repeat averages;
(2) The experimenter did not continue to observe during the 30-day time return trip;
(3) The 73% propargite emulsifiable solution has obvious symptoms of regional blackening of the front surface of the leaf blade and black spot on the back surface in 48 hours, and the plant leaf blade has the symptoms of yellowing and drying in 6 days, and is identified as a more obvious symptom of phytotoxicity. The plants in the area where the 40% of the fluorine mites are applied in the microemulsion agent firstly grow normally and have no phytotoxicity symptom.
TABLE 2-2% Fluoroacarid ME to cherry spider field test (Yunnan Kunming 2020)
Note: (1) the data in Table 2-2 are all 4-time repeat averages;
(2) The experimenter did not continue to observe during the 30 day time return trip;
(3) The 73% propargite emulsifiable solution has obvious regional blackening symptom of the front surface of leaves in 48 hours, has more obvious burning phenomenon at the red bud part of the growing point of branches, has the symptoms of dry leaves and yellowing in 6 days, has the phenomenon of dry-out at the red bud part of the growing point of branches, and is identified as more obvious phytotoxicity symptom, and plants in the 40% fluacrid first microemulsion using area grow normally without phytotoxicity symptom expression.
TABLE 2-3% Fluoroacarid ME to Red spider of orange tree field test (Yunnan Kunming 2020)
Note: (1) the data in tables 2-3 are all 4-time repeat averages;
(2) The experimenter did not continue to observe during the 30 day time return trip;
(3) The 73% propargite emulsifiable solution has obvious regional yellowing symptoms of the front surface of leaves, blackening of the stem parts of branches and obvious burning phenomenon on petals of a citrus tree in 48 hours, has dry and yellow symptoms of the leaves in 6 days and obvious burning phenomenon of the petal parts, and is identified as a more obvious phytotoxicity symptom. The 40% fluorine mite microemulsion is used in the area where the plants grow normally and has no phytotoxicity symptom.
TABLE 2-4% Dermatophagoides pteronyssinus ME for test of pesticide effect of watermelon red spider in field (2020 Liaoning Dalian)
Note: (1) the data in tables 2-4 are all 4-time repeat averages;
(2) The experimenter did not continue to observe during the 30 day time return trip;
(3) The 73% propargite emulsifiable solution has obvious symptoms of curling and yellowing of leaves within 48 hours, has a more obvious burning phenomenon at the growing point of branches, has the symptoms of withering and blackening of curled leaves on the 6 th day, has the phenomenon of withering at the growing point of branches, and is identified as a more obvious phytotoxicity symptom. The 40% fluacrypyrim microemulsion is firstly used for the plants in the medicine application area to normally grow and has no symptom of phytotoxicity.
Summary and discussion
The 40% fluorine mite first microemulsion is a novel pesticide with a brand new structure and action mechanism, has the characteristics of environmental friendliness, long lasting period and the like, is a brand new type pesticide, has the characteristics of quick effect, long lasting period, environmental friendliness and the like, has very low toxicity to bees and other pollinating insects, is a novel broad-spectrum pesticide, has the characteristics of high efficiency, low toxicity, no interactive resistance with other chemical pesticides and the like, and is proved by experiments that the 40% fluorine mite first microemulsion has better control effect on red spiders, is remarkably superior to a conventional pesticide in quick effect and lasting effect, can reach about 30 days, is safe and free of phytotoxicity, and is an ideal pesticide substitute for controlling the red spiders.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (6)
1. A fluorine-containing acaricide is characterized in that the molecular formula is,
wherein R is 1 、R 2 、R 3 At least one of which is F.
2. A method for producing the fluorine-containing acaricide according to claim 1, characterized by comprising the steps of,
step one, preparing p-tert-butyl benzene epoxy cyclohexanol, wherein p-tert-butyl phenol, 1,2-epoxy cyclohexane and toluene are mixed according to a molar ratio of 1:1.1:3, mixing, reacting for 10 hours at the temperature of 115-120 ℃, washing for three times by using hot water with washing quantity, and removing excessive cyclohexene oxide and toluene by reduced pressure distillation to prepare p-tert-butyl benzene epoxy cyclohexanol for later use;
step two, preparing 2- (4-tert-butyl phenoxy) cyclohexyl chlorosulfite, dissolving p-tert-butyl phenoxy cyclohexanol in toluene, cooling to 0-10 ℃, and then dropwise adding thionyl chloride, wherein the molar ratio of the p-tert-butyl phenoxy cyclohexanol to the thionyl chloride is 1:1.0-1.4, keeping the temperature at 0-10 ℃ in the dropping process, raising the temperature to 25-30 ℃ after dropping, preserving the temperature for 15-20 hours, and removing the solvent and thionyl chloride by reduced pressure distillation to obtain an oily matter 2- (4-tert-butyl) cyclohexyl chlorosulfite;
and step three, mixing toluene, fluorine-containing ethanol and an acid-binding agent in a molar ratio of 3.
3. The method for producing a fluorine-containing acaricide according to claim 2, wherein in step three, the acid is one selected from formic acid, acetic acid, propionic acid, hydrochloric acid and sulfuric acid.
4. The method for preparing fluorine-containing acaricide according to claim 2, characterized in that in the third step, the fluorine-containing ethanol is selected from one of 2-fluoroethanol, 2,2-difluoroethanol, 2,2,2-trifluoroethanol.
5. The method for preparing fluorine-containing acaricide according to claim 2, wherein in the third step, the acid-binding agent is one of triethylamine, pyridine and N, N-diisopropylethylamine.
6. The method for assaying fluorine-containing acaricide according to claim 1, which comprises the steps of,
a, selecting an experimental object, an experimental medicament and an experimental site, wherein the experimental object is red spider, the experimental medicament is 45% bifenazate, etoxazole suspending agent, 30% ethiazole-chlorfenapyr suspending agent, 73% propargite missible oil and 40% fluorine-containing acaricide microemulsion, and the experimental site is a field;
b, sixteen small areas are divided in the field, 45% bifenazate, etoxazole suspending agent, 30% ethacrylonitrile suspending agent, 73% propargite missible oil and 40% flutolaccide microemulsion respectively correspond to the four small areas, and the application amounts of the four small areas are 45% bifenazate, 33.5ga.i./hm of etoxazole suspending agent and 33.5g a.i./hm of 30% acetazonitrile suspending agent, 45ga.i./hm of 40% flutolaccide microemulsion and 55ga.i./hm of 73% propargite missible oil;
c, randomly hanging the cards and marking 10 plant strips in each cell, investigating the total number of eggs and adults on 10 cells before pesticide application, investigating the number of remaining insects on the branches 1d, 3d, 15d and 30d after pesticide application, recording and analyzing.
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| CN114315671A (en) * | 2020-09-28 | 2022-04-12 | 山东康乔生物科技有限公司 | Organic sulfur compound and preparation method and application thereof |
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| US3272854A (en) * | 1963-07-18 | 1966-09-13 | Us Rubber Co | Cycloaliphatic sulfite esters |
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| CN114315671A (en) * | 2020-09-28 | 2022-04-12 | 山东康乔生物科技有限公司 | Organic sulfur compound and preparation method and application thereof |
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