CN1948328B

CN1948328B - Methyl amine abamectin acylate and its preparation method and application

Info

Publication number: CN1948328B
Application number: CN200610123017A
Authority: CN
Inventors: 徐汉虹; 胡林; 梁明龙; 万水娥; 夏坚; 金亚旭
Original assignee: South China Agricultural University
Current assignee: South China Agricultural University
Priority date: 2006-10-26
Filing date: 2006-10-26
Publication date: 2010-05-12
Anticipated expiration: 2026-10-26
Also published as: CN1948328A

Abstract

The present invention discloses a kind of methylaminoabamectin organic acid salt, its preparation method and application. Said invention also provides its chemical structure formula. As compared withabamectin and emamectin benzoate the ratio of its polar group in the compound can be greatly raised, and its solubility in the water also is obviously raised, so that it can greatly raise effect for controlling plant pests.

Description

Methylamino avermectin organic acid salt and preparation method and application thereof

Technical Field

The invention belongs to the field of pesticides, and particularly relates to methylamino abamectin organic acid salts, and a preparation method and application thereof.

Background

In 1975, researchers at northern research institute of japan separated a Streptomyces avermitilis MA-4680(NRRL8165) from soil samples from Jinggang county, and subsequently Merck, usa extracted a group of mixed natural products consisting of 8 structurally similar homologues from fermented mycelia of the Streptomyces avermitilis, and named avermectins (avermectins, AVM for short). In 1981, the company realizes the industrialization of abamectin and gradually applies to the aspects of agriculture and animal husbandry and sanitation. At the end of the 80 s, abamectin strains are introduced in China, and the research on strain separation, mutation breeding, fermentation process, extraction and refining and the like is carried out by units such as Shanghai pesticide research institute, Chinese agriculture university and the like, so that the production and use of abamectin in China are promoted. The compound has strong repelling and killing effect on nematode and arthropod parasitized in animal body, can reduce the dosage from mg/kg level to mu g/kg level, and has the features of unique action mechanism, high safety, etc. the medicine is first used as one kind of parasite resisting medicine for preventing and treating parasite in animal body. The drug is found to have good control effect on a plurality of pests and mites on crops, so that the drug is used as an insecticide and acaricide to control agricultural pests. According to Bloom reports of researchers of the U.S. Food and Drug Administration (FDA) in 1993, AVM not only is tightly combined with soil in a natural environment and is not easily washed and infiltrated, but also is rapidly degraded into an inactive compound under a light condition or under the action of soil microorganisms, and molecular fragments of the AVM are finally decomposed and utilized by plants and microorganisms as a carbon source without any residual toxicity. Abamectin is an important antibiotic and has become an efficient biological source pesticide for agriculture and veterinary use. To date, some of the deficiencies have been gradually revealed by the use of avermectins. The test proves that: it is inactive against eggs of many pests, is not systemic, and has developed resistance to certain pests. Therefore, except that the yield of the strain is improved by a biotechnology means, and the activity of the strain is improved by improving a production process and a preparation technology, the derivative modification is carried out on a parent structure to overcome certain defects of the original parent abamectin, and the application of the compound in the aspects of control range, insecticidal activity, human and animal toxicity, environmental toxicity and the like is expanded.

In 1984, Merk corporation started to perform derivatization research on the hydroxyl group on 4 '- (alpha-L-oleanolic group) alpha-L-oleanolic group of abamectin, and developed 4' -deoxy-4 abamectin B1 a/B1B. In 1989, the company develops 4 '-epi-methylamino-4' deoxyabamectin, and finds that the deoxyabamectin has strong insecticidal effect on lepidoptera pests. Later, to solve the stability problem of 4 '-epi-methylamino-4' deoxyabamectin, Merk company in 1994 started to research the stability of various organic acid salts thereof and finally screened out 4 '-epi-methylamino-4' deoxyabamectin benzoate as a development object, and the compound is the emamectin benzoate which is increasingly widely applied in agricultural pest control at present. The success of the development of emamectin benzoate greatly improves the application of abamectin in the prevention and treatment of pests such as lepidoptera pests, pine wood nematodes and the like, but because the solubility of the emamectin benzoate in water is very low, the emamectin benzoate has weak systemic delivery conductivity in plant bodies, and in addition, the emamectin benzoate has the defects of too narrow insecticidal spectrum, low activity on other important pests and the like, the application of the abamectin in the pests in agriculture and forestry is greatly restricted. Researches show that in the processing process of emamectin benzoate, after the screening range of organic acid is enlarged, certain salts obtained far exceed emamectin benzoate in the aspects of water solubility, systemic infusion conductivity in plant bodies and bioactivity, and the application range of the medicines in the prevention and treatment of plant diseases and insect pests is greatly widened.

Disclosure of Invention

The invention aims to overcome the defects of the existing emamectin benzoate in pest control and provides a methylamino abamectin organic acid salt which has good pest control effect, wide pest control range and easy degradation.

The invention also aims to provide a preparation method of the methylamino abamectin organic acid salt.

The invention further aims to provide the application of the methylamino abamectin organic acid salt in preparing the pesticide.

The invention relates to a methylamino abamectin organic acid salt, which has the structural formula as follows:

wherein:

x represents CH₃Or CH₂CH₃

R^-And represents acid radical anion of formic acid, acetic acid, acrylic acid, sorbic acid, malic acid, oxalic acid or succinic acid:

HCOO^- CH₃COO^-

CH₂＝CHCOO^-

CH₃CH＝CHCH＝CHCOO^-

the above methylamino abamectin organic acid salt is methylamino abamectin formate, methylamino abamectin acetate, methylamino abamectin acrylate, methylamino abamectin sorbate, methylamino abamectin malate, methylamino abamectin oxalate or methylamino abamectin succinate. The organic acid salt of methylamino avermectin may be methylamino avermectin B_1aOrganic acid salt, which can be methylamino abamectin B_1bThe organic acid salt may be a mixture of the two.

The methylamino abamectin organic acid salt can be synthesized by the following ways: dissolving methylamino abamectin benzoate in acetone, placing the dissolved methylamino abamectin benzoate in a beaker, under the ice bath condition, slowly dropwise adding 1mol/L NaOH solution into the acetone solution under the stirring condition until the pH value of the solution is neutral, stirring for 20min, adding water, continuously stirring for 20min, ventilating in a fume hood, naturally volatilizing the acetone, carrying out column chromatography on the obtained substance, recrystallizing, carrying out freeze drying to obtain methylamino abamectin, weighing the methylamino abamectin, dissolving the methylamino abamectin in acetone, dropwise adding an organic acid acetone solution containing the organic acid until the pH value of the mixed solution is neutral, stirring for 5min, drying in the fume hood, transferring the mixed solution to a vacuum drier, and drying to obtain the methylamino abamectin organic acid salt, wherein different organic acid acetone solutions are adopted to obtain the unused methylamino abamectin organic acid salt, and the separation and purification methods used in the synthesis method are all conventional methods, for example, selective crystallization is carried out by using a proper solvent, or column separation is carried out by using silica gel and alumina, and the concentration of the obtained emamectin after purification in the reaction process is more than 95 percent.

The methylamino abamectin organic acid salt has good insecticidal effect, and is particularly suitable for killing various agricultural and forestry pests. Agricultural pests: such as cabbage moth (Plutella xylostella L.), cotton bollworm (Helicoverpa armigera), beet armyworm (Spodoptera exigua), tobacco budworm (Heliothis assitaguene), alfalfa thrips (Frankliniella acilitalis), armyworm (Leucanthia Separata Walker), Spodoptera litura (Prodenia litura Fabricius), cabbage caterpillar (Pierilis rapae Linnaeus), Epinephelus exigua (Sidemia debiva), red brown rice moth (Polia illobila Butler), cabbage caterpillar (Mam estra brasiliensis Linnaeus), alfalfa caterpillar (Heliothis virilis Htibnanogana), Spirothistle (Pyrria brueckea), tobacco budworm (Heliothis virescens), tobacco budworm (Oscilaria), tobacco budworm (Ostertagia punctata), tobacco budworm (Ostertagia japonica, etc.), cabbage caterpillar (Helicoverpa virescens), tobacco budworm (Ostertagia litura), tobacco budworm (Ostreta), tobacco budworm (apple moth, etc. Forestry pests: such as pine wood nematodes (Bursaphelenchus xylophilus), hyphantria cunea (Hypopharia cunea Drary), Trichosporon chrysis (Elerusia lcptalina), and Liriomyza sativa Blancard.

In pest control, the methylamino abamectin organic acid salt may be compounded into various kinds of conventional preparation formsUse is made, for example, of microemulsions, emulsifiable concentrates, aqueous emulsions, pastes, trunk injections, granules, powders, suspensions, aerosols and microcapsules. The preparation can be prepared by conventional method, such as microemulsion, which can be prepared by using one or more of alcohols, ketones, esters and aromatic hydrocarbons as solvent, and alkyl benzene sulfonate calcium salt, magnesium alkyl benzene sulfonate, aluminum alkyl benzene sulfonate, sodium alkyl benzene sulfonate, barium alkyl benzene sulfonate, C₈-C₂₀The anti-freezing agent is prepared by using one or more of sodium alkyl sulfate, styrene polyoxyethylene ether ammonium sulfate, benzyl diphenol polyoxyethylene ether, phenethylphenol polyoxyethylene (N15-30) ether, phenethylphenol polyoxyethylene polyoxypropylene, nonylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether methyl condensate, diphenol polyoxyethylene ether, domestic agricultural milk No. 700 and No. 300 as an emulsifier, using one or more of 3-chloro-1, 2-epoxypropane, butyl glycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, polyethylene glycol diglycidyl ether and sodium sorbate as a stabilizer, and using one or more of ethylene glycol, glycerol, propylene glycol, polyethylene glycol and sorbitol as an anti-freezing agent.

The synthesized methylamino abamectin organic acid salt may be used alone, or in combination of two or more kinds, or may be mixed with known germicide, miticide, pesticide or nematicide, herbicide and growth regulator. The active substances can be employed in the form of their formulations, such as solutions, suspensions, wettable powders, pastes, soluble powders, dusting formulations and granules, by customary methods, for example by pouring, spraying, dusting, foaming, injecting, brushing or the like. The concentration of active substance used in the treatment of the plant parts can vary within a relatively wide range, generally in the range from 1 to 0.0001% by weight, preferably from 0.5 to 0.001% by weight. When used as an injection for tree trunks, the injection dose is usually in the range of 2 to 50g/m³Preferably in the range of 5 to 20g/m³。

Compared with the prior art, the methylamino abamectin organic acid salt has the following beneficial effects:

1. compared with abamectin, the proportion of polar groups in the compound is increased, the oil-water distribution coefficient of the compound is changed, so that the modified new substance can penetrate through the plant epidermis more easily and enter the plant body, and the new substance is transported and diffused to all parts of the organism from the pesticide application position to achieve the control effect.

2. Compared with methylamino abamectin benzoate, the solubility of the compound in water is improved by dozens to hundreds of times, taking methylamino abamectin acetate as an example, the solubility of the compound in water is up to 1.242g, which is several orders of magnitude higher than abamectin (1 mu g/100mL water) and widely applied methylamino abamectin benzoate (2.4mg/100mL water); the systemic transport capacity in the plant body is greatly enhanced, and the implementation test shows that the same dose of methylamino abamectin benzoate and methylamino abamectin acetate is injected into the trunk, and the systemic quantity of the latter in the trunk is far higher than that of the former.

3. The control range of emamectin benzoate is expanded, the activity on controlling a plurality of pests is greatly increased, and experiments prove that the stomach toxicity activity of the emamectin benzoate to 3 rd larvae of diamondback moth is 4.52 times that of the emamectin benzoate, 15.73 times that of the abamectin, 335.81 times that of profenofos and 364.26 times that of cyfluthrin respectively; the stomach toxicity activity of the emamectin benzoate to the third-instar cotton bollworm is 4.29 times that of emamectin benzoate, 34.93 times that of abamectin, 205.21 times that of cypermethrin and 115.82 times that of chlorfenapyr respectively; the activity of the emamectin benzoate acrylate on the stomach toxicity of phyllotreta striolata adults is respectively 2.10 times of that of emamectin benzoate, 5.07 times of that of abamectin, 2.25 times of fipronil, 5.44 times of phoxim and 200 times of that of deltamethrin; the stomach toxicity activity of the emamectin benzoate to striped rice borers is 5.5 times of that of emamectin benzoate, 44.75 times of that of abamectin, 2580 times of fenitrothion and 5387.5 times of that of chlorpyrifos; the activity of the emamectin benzoate sorbate to the 3 rd larva of the armyworm is 1.95 times that of emamectin benzoate, 328.29 times that of abamectin, 80.66 times that of beta-cypermethrin and 8.99 times that of phoxim respectively; the emamectin succinate has high control effect on the liriomyza sativae, and the control effect after being diluted by 10000 times and sprayed is still 96.65 percent after 15 days and is far higher than that of other medicaments; the reproduction inhibition activity of the emamectin benzoate malate on the pine wood nematodes is 1.15 times that of emamectin benzoate, 2.24 times that of abamectin and 176.61 times that of cadusafos respectively.

4. Compared with the prior avermectin drugs, the avermectin drug has higher polarity, is easier to degrade in natural environment and is safer to ecological environment.

Drawings

FIG. 1 is a graph showing the control effect of 4 kinds of agents on the pine wilt disease of potted seedlings.

Detailed Description

Example 1:

accurately weighing 10g of distilled water in a 10ml graduated test tube by using an electronic analytical balance, and placing the graduated test tube in a water bath kettle at 25 ℃. Then, each compound was added thereto with shaking until it could not be dissolved. Repeat 3 times. After drying, the material was weighed and the solubility in water was calculated and the results are shown in table 1. From table 1, we can see that the solubility of emamectin benzoate organic acid salt in water is improved by about tens to hundreds times compared with emamectin benzoate.

TABLE 1 solubility of emamectin benzoate in Water

Example 2:

treating 3-year-old diamondback moth larvae by adopting a leaf dipping method under indoor conditions, and performing LC (liquid chromatography) on diamondback moths by using various medicaments at 48h₅₀The values are shown in Table 2. As can be seen from Table 2, the emamectin benzoate has much higher activity on diamond back moths than other control medicaments, which are respectively 4.52 times of emamectin benzoate, 15.73 times of abamectin, 335.81 times of profenofos and 364.26 times of cyfluthrin, and shows extremely strong insecticidal activity.

TABLE 2 toxicity test results (48h) of agents such as methylamino avermectin acetate against 3 rd instar larvae of plutella xylostella

Example 3:

treating 3-year-old bollworm larvae by using a leaf dipping method under indoor conditions, and performing LC (liquid chromatography) of various medicaments on the bollworms in 48 hours₅₀The values are shown in Table 3. As can be seen from Table 3, the emamectin benzoate has much higher activity to cotton bollworm than other control agents, which are respectively 4.29 times of emamectin benzoate, 34.93 times of abamectin, 205.21 times of cypermethrin and 115.82 times of chlorfenapyr, and shows extremely strong insecticidal activity.

TABLE 3 toxicity test results of emamectin benzoate and other agents on 3 rd instar cotton bollworm larvae (48h)

Example 4:

treating phyllotreta striolata adults by adopting a leaf dipping method under indoor conditions, and performing LC (liquid chromatography) of various medicaments on phyllotreta striolata adults within 48 hours₅₀The values are shown in Table 4. As can be seen from Table 4, the activity of emamectin benzoate acrylate on phyllotreta striolata adults is much higher than that of other control agents, and the emamectin benzoate acrylate is 2.10 times that of emamectin benzoate, 5.07 times that of abamectin, 2.25 times that of fipronil and 5.44 times that of phoxim respectively, and the emamectin benzoate acrylate shows extremely strong insecticidal activity.

TABLE 4 indoor toxicity test results (48h) of Mebamido avermectin acrylate and other agents on Phyllotreta striolata adults

Example 5:

under indoor conditions, the rice sprout immersion method is adopted to treat the striped flea beetle imagoes, and LC of various medicaments to Chilo suppressalis Ant borer is carried out in 48 hours₅₀The values are shown in Table 5. As can be seen from Table 5, the activity of emamectin benzoate to striped rice borer is much higher than that of other control medicaments, which are respectively 5.5 times of emamectin benzoate, 44.75 times of abamectin, 2580 times of fenitrothion and 5387.5 times of chlorpyrifos, and the emamectin benzoate shows extremely strong insecticidal activity.

TABLE 5 results of indoor toxicity test of drugs such as emamectin benzoate to Chilo suppressalis Ant borer (48h)

Example 6:

under indoor conditions, the leaf soaking method is adopted to treat mythimna separata larvae of 3 th instar, and LC of various medicaments for striped rice borer and Antenorhabditis borer is adopted at 48h₅₀The values are shown in Table 6. From Table 6, it can be seenThe activity of emamectin benzoate sorbate on 3 rd larva of armyworm is much higher than that of other contrast agents, namely 1.95 times of emamectin benzoate, 328.29 times of abamectin, 80.66 times of beta-cypermethrin and 8.99 times of phoxim, and the emamectin benzoate sorbate has extremely strong insecticidal activity.

TABLE 6 indoor toxicity test results (48h) of methylamino avermectin sorbate for armyworm 3 rd instar larvae

Example 7:

under the lower concentration, the control effect of the methylamino abamectin succinate on the liriomyza sativae is far better than the control effects of emamectin benzoate, abamectin, cyromazine, dimehypo and other medicaments, and the specific implementation test results are as follows: test agents: 3% methylamino avermectin succinate microemulsion (self-prepared in laboratory) is diluted by 10000 times; diluting 3% emamectin benzoate microemulsion by 8000 times; 0.9 percent of abamectin emulsifiable solution is diluted by 2000 times; 75% cyromazine wettable powder, diluted 5000 times; diluting 18% bisultap water solution by 300 times;

selecting a test field by adopting a ridge and ridge planting mode, randomly arranging the test field in blocks, repeating the treatment for three times, and treating the test field with the specified liquid medicine of 60kg/667m³And (3) comparing with clear water, measuring 7d (about the peak time of the low-age larvae) after the peak time of the adult larvae by using a yellow plate induction method, taking 5 random points of sampling in each cell by adopting a tag mark in the first day before the drug, checking 20 leaves in each point, checking 100 leaves in total, performing population base number investigation before the drug, investigating the number of the live larvae on the leaves marked by the pre-drug investigation at 5d, 10d and 15d after the drug, calculating the corrected death rate of the larvae, and referring to a table 7.

TABLE 7 corrected mortality of larvae of liriomyza sativae, medicaments such as emamectin succinate

Example 8:

under indoor conditions, the growth and reproduction inhibiting activity of the emamectin benzoate on the pine wood nematodes is obviously higher than that of the organophosphorus pesticide and the emamectin benzoate, and the good inhibiting effect is shown. Adopting culture dish fungus bioassay method, and using methylamino abamectin malate, emamectin benzoate, abamectin and clomiphos to treat pine wood nematode IC₉₅The values are 0.1786 mug/ml, 0.2049 mug/ml, 0.3999 mug/ml and 31.5430 mug/ml respectively, wherein the inhibiting activity of the emamectin malate is 1.15 times, 2.24 times and 176.61 times of the latter respectively. See table 8.

TABLE 8 Activity of Emamectin malate on Bursaphelenchus Xyla

Example 9:

the same dose of methylamino abamectin benzoate and methylamino abamectin organic acid salt (in this embodiment, methylamino abamectin acetate is taken as a representative) is injected into the trunk, and the systemic amount of the latter in the trunk is far higher than that of the former. As can be seen from table 9: injecting the same dose of 10g/m into the trunk³The systemic amount of the methylamino abamectin benzoate and the methylamino abamectin acetate in the trunk is far higher than that of the methylamino abamectin benzoate and the methylamino abamectin acetate. Wherein the presence of the agent is detectable at a height of 7m from the tree on day 3 after the emamectin benzoate injection. While the presence of emamectin benzoate was not detected at this position all the time. 20 days after injection, the content of the emamectin benzoate is detected to be 1.71 mu g/g at the position 4m higher than the tree, and the content of the emamectin acetate at the position can reach 20.13 mu g/g.

TABLE 9 dynamic state of delivery of two agents in Pinus massoniana

Example 10:

the comparative experiment of the prevention effect of the methylamino abamectin acetate, the clomiphos, the abamectin and the methylamino abamectin benzoate on the sick pine seedlings is carried out under the same injection dosage;

test materials: in 4 months in 2005, 4-year-old masson pine bagged seedlings with consistent sizes are selected in a nursery garden of a forest academy of sciences in Guangdong province, the height of the seedlings is 80-100cm, the diameter of the base of a trunk is 1.4-1.8cm, and each pine seedling is required to have 1-2 lateral branches. After 2 months, the plants with normal growth were taken for testing. 95% Kyoho crude (Zhejiang Yifan chemical Co., Ltd.); 95.5% of abamectin (provided by Guangxi Guilin Jiqi Co., Ltd.); 91% EB crude drug (Zhejiang Haizheng pharmaceutical Co., Ltd.); the content of the methylamino abamectin acetate technical product (synthesized by pesticide of southern China university of agriculture and key laboratory of chemical and biological education department) is not lower than 90 percent;

the test method comprises the following steps: the test adopts the treatment of trunk injection. During treatment, the seedlings are drilled at the position 5cm higher than the ground, the angle is 45 degrees with the seedlings, the aperture is 3mm, and the depth is 10 mm. Then, a large pipette tip is selected, the tip is cut off, and the tip is inserted into the hole. Then the medicine is injected into the gun hole, and the medicine hole is sealed by adhesive plaster. The nematode inoculation adopts a lopping casing method. Selecting one lateral branch of the in-vitro pine branch, cutting off the treetop at a position about 5cm away from the main branch to enable the cross section to be upward, winding a little absorbent cotton at the base part of the cross section, sleeving a latex tube with the length of about 8cm, fastening the base part of the latex tube by using a string, and injecting nematode suspension liquid from a gate, wherein the inoculation amount is 10000 per branch. The nozzle was then plugged with wet degreased cotton to maintain the humidity in the latex tube for nematode penetration. Each agent is provided with 1, 5, 10 and 20g/m³4 concentrations, 10 shoots were selected for each concentration. In addition, 10 seedlings were selected to inject 1ml of acetone without inoculatingThe worms were used as control I, 10 seedlings were inoculated with 1ml acetone as control II. And (5) inoculating 15 days after the injection. The disease grading standard adopts the method of Xufuyuan et al, and the needle leaves are classified into 5 grades according to the degrees of chlorosis, withered and yellow and reddening: level 0 (representative value 0), normal; grade I (representative value 1), chlorosis, part of the needles (below 1/4) turned yellow; in class II (typical value 2), 2/4-3/4 needles turned yellow, and needles below 1/4 turned red; grade III (typical value 3), the color of needle leaves turns red from about 1/4 to 3/4; grade IV (representative value 4), above 3/4, turns red and dies. And calculating the infection index of the test seedlings and the prevention and treatment effect of the medicament after 60 days of inoculation by taking the test seedlings as a standard. And (3) shearing quantitative test seedling main stems for plants with the disease progression of more than I, carrying out nematode separation by a Beemann funnel method in a laboratory, and carrying out microscope examination and counting under a dissecting mirror. Wherein,

disease index ═ Σ (damage degree representative value:numberof disease strains at this stage)/(number of total strains at the highest stage representative value)

The control effect is [ (control susceptibility index-treatment susceptibility index)/control susceptibility index ]. 100%

The volume calculation formula of the sapling is as follows:

V(m³)＝1/3×π〔d(m)/2〕²×h(m)×2，

d is the diameter of the base of the tree trunk, h is the height of the seedling

The preparation of the medicament comprises: 1g of the medicament is weighed and dissolved in 10ml of acetone solution, and the injection dosage is calculated according to the test concentration and the volume of the sapling.

And (3) test results: the method comprises the steps of treating pine seedlings by adopting a medicament injection method and then inoculating nematodes, wherein the control effect of 4 medicaments such as methylamino abamectin acetate and the like on pine wood nematode diseases under different concentrations is shown in figure 1 after 2 months, in order to reflect the systemic dispersion and dispersion of the medicaments in the pine seedlings and the control effect of the nematodes, no emulsifier is added in the preparation process of the experimental medicament, and as is obvious from figure 1, when the medicament injection dosage is 1g/m³In the process, 4 medicaments have no control effect on the pine wood nematodes, and the content of the methylamino abamectin acetate is the highest and is only 7.5 percent. Prevention of pine wilt disease by 4 medicaments with increasing injection dosageThe effect is obviously improved. When the injection dosage is 20g/m³In the process, the control effect of the methylamino avermectin acetate reaches 95 percent and is obviously higher than that of AVM (45 percent), EB (60 percent) and cadusafos (77.5 percent). The methylamino abamectin acetate is one kind of systemic medicine with water solubility up to 2150mg/L and is transported to effective concentration in pine seedling after being injected into tree to reach preventing and treating effect. Although the growth and reproduction inhibiting effect of the AVM and the EB on the pine wood nematodes under indoor conditions is far higher than that of clomiphos, the control effect on the pine wood nematode disease of the masson pine is lower than that of the other pine wood nematode disease under the same concentration. This is because: the solubility of AVM and EB in water is 0.01mg/L and 24mg/L respectively, when injected into the pine body, it is difficult to dredge upwards in a short time and reach effective dose in the tree body, and the clorophos is a two-way dredging systemic medicament, the solubility in water is 700mg/L, and after injected, it can be quickly transported to effective concentration in the pine body to obtain the effect of prevention and cure. Therefore, under the same injection dosage, the prevention effect of the emamectin benzoate on the sick pine seedlings is higher than that of the clomiphos, the abamectin and the emamectin benzoate.

Example 11: composition of 0.3% methylamino abamectin acetate microemulsion and preparation method thereof

The main agent of the embodiment comprises the following effective components in percentage by weight (%): methylamino abamectin acetate 3;

the auxiliary agent comprises the following components in percentage by weight: solvent: 10 parts of methanol; emulsifier: ethylene oxide 11, calcium dodecylbenzenesulfonate 8: 78, water;

the raw materials with the weight ratio are mixed and then are prepared into the microemulsion by a microemulsion processing method.

Example 12: preparation of methylamino abamectin organic acid salt

Preparing methylamino abamectin acetate: dissolving 19g of 91% methylamino abamectin benzoate in 200ml of acetone, placing the mixture in a 1000ml big beaker, slowly and dropwise adding 20ml of 1mol/L NaOH into an acetone solution under the stirring condition under the ice-dissolving condition until phenolphthalein turns red, stirring for 20min, adding 200ml of water, continuing stirring for 20min, ventilating in a ventilation cabinet, wherein the door is slightly higher than the mouth of the beaker, and naturally volatilizing the acetone. And carrying out column chromatography, recrystallization and freeze drying on the obtained substance to obtain the compound I. Weighing 8.80g of the compound I, dissolving the compound I by using 100ml of acetone, dropwise adding 2ml of acetic acid acetone solution containing 0.6g of glacial acetic acid into the solution, stirring for 5min, drying in a fume hood, and then transferring to a vacuum drier for drying to obtain the product of the methylamino abamectin acetate with the concentration of more than 90%. By adopting the same preparation method, acetic acid is replaced by formic acid, acrylic acid, sorbic acid, malic acid, oxalic acid and succinic acid to obtain methylamino abamectin formate, methylamino abamectin acrylate, methylamino abamectin sorbate, methylamino abamectin malate, methylamino abamectin oxalate and methylamino abamectin succinate.

Claims

1. The structure of the methylamino abamectin organic acid salt is as the formula (I):

wherein:

x represents CH₃Or CH₂CH₃

R-is acid radical anion of formic acid, acetic acid, acrylic acid, sorbic acid, malic acid, oxalic acid or succinic acid, and is shown as follows:

2. the preparation method of the emamectin benzoate as claimed in claim 1, which is characterized by comprising the following steps: dissolving methylamino abamectin benzoate in acetone, and slowly and dropwise adding a NaOH solution under an ice bath condition until the pH value of the solution is neutral; adding water after full stirring, continuously stirring, ventilating in a fume hood, and naturally volatilizing acetone; performing column chromatography on the obtained substance, recrystallizing, and freeze-drying to obtain methylamino abamectin; dissolving methylamino abamectin in acetone, adding organic acid acetone solution containing organic acid drop by drop until the pH value of the mixed solution is neutral, stirring, drying in a fume hood, transferring to a vacuum drier, and drying to obtain the methylamino abamectin organic acid salt.

3. The use of the emamectin benzoate organic acid salt of claim 1 in the preparation of a pesticide for pine wood nematodes.