8-hydroxyquinoline stannous, preparation method thereof and application of 8-hydroxyquinoline stannous in prevention and treatment of plant diseases and insect pests

Abstract

The invention relates to 8-hydroxyquinoline stannous, a preparation method thereof and application of the compound in prevention and treatment of plant diseases and insect pests. The preparation method is mild in process condition and simple to operate, adopts water as a reaction medium, does not use an organic solvent, and can reduce the cost, reduce the process steps and improve the yield and the content of a finished product. The 8-hydroxyquinoline stannous can be used for preventing and treating crop mites, and also has a good prevention effect on bacterial diseases and fungal diseases of citrus.

Description

Technical Field

[0001] The invention relates to 8-hydroxyquinoline stannous compound and a preparation method thereof, as well as application of the compound in preventing and controlling plant diseases and insect pests. Background Art

[0002] The molecular formula of 8-hydroxyquinoline stannous is C 18 H 12 N2O2Sn, with a molecular weight of 407.02, is easily soluble in acid, insoluble in water, and slightly soluble in organic solvents such as methanol and acetonitrile. Its structural formula is:

[0003]

[0004] The prior art method for preparing 8-hydroxyquinoline stannous uses an organic solvent, which is costly and has complicated process steps. Moreover, 8-hydroxyquinoline stannous is not usually used as a pesticide. Summary of the invention

[0005] The purpose of the present invention is to provide 8-hydroxyquinoline stannous compound and its preparation method, as well as the application of the above compound in preventing and controlling plant diseases and insect pests. 8-hydroxyquinoline stannous compound is made into corresponding pesticide preparations to prevent and control crop pest mites, and at the same time prevent and control bacterial diseases and fungal diseases of citrus.

[0006] The preparation method of 8-hydroxyquinoline stannous is as follows:

[0007] (1) adding a water-soluble stannous salt to water and stirring to dissolve it;

[0008] (2) adding 8-hydroxyquinoline and stirring the reaction for 0.1-2 hours;

[0009] (3) adding a catalyst to adjust the pH to 3.0-9.0, then heating to 70-100° C. and reacting for 0.5-3 hours;

[0010] (4) Cool to room temperature, filter, wash with water, filter again, and then dry at 80-120°C.

[0011] The molar ratio of the water-soluble stannous salt to 8-hydroxyquinoline is 1.0-1.5:2.0-2.8.

[0012] Wherein, the catalyst is one or more of ammonia water, sodium hydroxide, potassium hydroxide and ammonium bicarbonate.

[0013] 8-Hydroxyquinoline stannous can be made into a suspension, which comprises the following components by mass percentage: 8-hydroxyquinoline stannous 15-40%, a wetting agent 0.5-2.0%, a dispersant 1-4%, an organosilicon defoamer 0.3-0.6%, a preservative 0.1-0.3%, a thickener xanthan gum 1.0-2.0%, and water supplemented to 100%.

[0014] A 30% suspension concentrate of 8-hydroxyquinoline stannous acid has excellent control effects on citrus red spider mites and citrus rust mites, and also has good control effects on bacterial diseases such as citrus canker and fungal diseases such as citrus anthracnose.

[0015] By adopting the above technical solution, the present invention has the following beneficial effects:

[0016] (1) The method for preparing stannous 8-hydroxyquinoline has mild process conditions and simple operation. Water is used as the reaction medium without using an organic solvent, which can reduce costs, reduce process steps, and improve yield and finished product content.

[0017] (2) 8-Hydroxyquinoline stannous acid can be used to control crop pests and mites, and it also has good preventive effects on bacterial and fungal diseases of citrus. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the specific implementation of the present invention or the technical solution in the prior art, the following briefly introduces the drawings required for use in the specific implementation or the prior art description. Obviously, the drawings described below are some implementations of the present invention, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0019] Figure 1-1 Infrared spectrum of 8-hydroxyquinoline standard

[0020] Figure 1-2 Infrared spectrum of sample 8-hydroxyquinoline stannous

[0021] Figure 1-3 Infrared comparison of the sample 8-hydroxyquinoline stannous and the standard 8-hydroxyquinoline Figure 2-1 Sample 8-hydroxyquinoline stannous 1 H-NMR spectrum

[0022] Figure 2-2 8-Hydroxyquinoline Standard 1 H-NMR spectrum

[0023] Figure 2-3 Sample 8-hydroxyquinoline stannous deuterated chloroform phase 13 C-NMR spectrum

[0024] Figure 2-4 8-Hydroxyquinoline Standard in Deuterated Chloroform 13 C-NMR spectrum DETAILED DESCRIPTION

[0025] The technical solution of the present invention will be described clearly and completely below in conjunction with the accompanying drawings and embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] Example 1: Preparation and chemical structure confirmation of 8-hydroxyquinoline stannous

[0027] The preparation method of stannous 8-hydroxyquinoline comprises the following steps:

[0028] (1) Add 107.4 g of 99% pure stannous sulfate into a closed reactor, add water, and stir to dissolve;

[0029] (2) adding 145.2 g of 8-hydroxyquinoline with a purity of 99% and stirring continuously for 2 hours;

[0030] (3) adding sodium hydroxide as a catalyst and adjusting the pH to 5.0, then raising the temperature to 80° C. for reaction for 3 hours;

[0031] (4) After the reaction is completed, the mixture is cooled to room temperature, filtered, washed with water, filtered again, and dried at 90° C. to obtain 8-hydroxyquinoline stannous acid, with a content of 98.5% and a yield of 99%.

[0032] The 8-hydroxyquinoline stannous acid and 8-hydroxyquinoline standard were determined by infrared and nuclear magnetic resonance methods. See the attached figure for the spectrum.

[0033] According to the Technical Guidelines for the Preparation and Structural Confirmation of Chemical Drug APIs, Guiding Principle No.: [H] GPH2-1, Chapter II, Technical Guidelines for the Structural Confirmation of Chemical Drug APIs, Section III, Basic Contents of the Structural Confirmation of Drug APIs, Article 1.4: Analysis of Metal Salts and Complexes, on the basis of the general required tests, consider using appropriate means to reflect the type, form and content of metal elements in the drug; for items that are not suitable or cannot test the metal salts themselves, consider using the corresponding test results of the acid molecules or ligands before salt formation for support. The structural confirmation of 8-hydroxyquinoline stannous acid complies with this principle, using appropriate means to conduct confirmation tests, and supporting the corresponding test results of the acid molecules or ligands of the salt formation.

[0034] The compound obtained in this embodiment has the structural formula (I):

[0035]

[0036] The compound obtained in this example was tested by ICP, and the mass fraction of tin element Sn was measured to be 29.2% (wt%), which is consistent with the tin content (wt%) of 29.17% in the chemical formula of 8-hydroxyquinoline stannous tin. The content of 8-hydroxyquinoline was calculated based on the mass fraction of tin element.

[0037] The compounds obtained in this example and the 8-hydroxyquinoline standard product were 1 HNMR and 13 CNMR and FT IR tests confirmed that the obtained compound was the target compound. The key peak values ​​shown in the spectrum are as follows:

[0038] according to Figure 1-1 The FT IR spectrum of the 8-hydroxyquinoline standard shows that 3050cm-1 shows a broad peak, which is the VAr-H stretching vibration peak of the benzene ring H and the stretching vibration peak of Var-OH. 1578cm-1 and 1498cm-1 are the VC=C stretching vibration peaks of the benzene ring skeleton, and 1578cm-1 shows a strong peak, indicating that the aromatic ring is conjugated with a double bond or a group with a lone pair of electrons. Combined with the molecular formula of 8-hydroxyquinoline, the N element on the quinoline aromatic ring contains a lone pair of electrons, which is consistent with the performance of this wave number. 1498cm-1 shows a strong peak, indicating that there are hydroxyl groups on the aromatic ring, causing the aromatic ring skeleton vibration to bend symmetrically with CH2. 1225cm-1-950cm-1 shows a weak and sharp peak with a high intensity, indicating that there are polar substituents on the aromatic ring. Combined with the structural formula of 8-hydroxyquinoline, this peak is consistent with the infrared characteristics of 8-hydroxyquinoline. 816cm-1 and 778cm-1 show two strong and sharp absorption peaks, indicating that the compound has meta-disubstitution, and 739cm-1 shows a strong absorption peak, indicating that the compound has ortho-disubstitution. Since the strong absorption peaks of 816cm-1-739cm-1 overlap with the absorption of monosubstituted benzene, this overtone peak can be inferred to be the absorption peak of a condensed ring compound. Combined with the structural formula of 8-hydroxyquinoline, with the hydroxybenzene ring as the core, the nitrogen-containing aromatic ring and the hydroxyl group are both substituents of the hydroxybenzene ring, and the nitrogen-containing aromatic ring and the hydroxybenzene ring as substituents, the overtone peak meets the fingerprint characteristics of each substituent group of 8-hydroxyquinoline. Therefore Figure 1-1 The FT IR spectrum shown is consistent with the infrared characteristic spectrum of 8-hydroxyquinoline.

[0039] same, Figure 1-2The FT IR spectrum of the compound shown shows that 3056cm-1 exhibits a broad peak, which is the VAr-H stretching vibration peak of the benzene ring H and the stretching vibration peak of Var-OH, 1601cm-1, 1572cm-1, 1495cm-1 are the VC=C stretching vibration peaks of the benzene ring skeleton, and 1578cm-1 exhibits a strong peak, indicating that the aromatic ring is conjugated with a double bond or a group with a lone pair of electrons, and 1457cm-1 is a strong absorption peak, indicating that the presence of hydroxyl groups on the aromatic ring causes the aromatic ring skeleton vibration to bend symmetrically with CH2. 1225cm-1 1 -950cm-1 1 It is shown as a sharp strong absorption peak, indicating that there are polar substituents such as -OH groups on the aromatic ring of the compound, 819cm-1 1 -729cm-1 shows 4 strong and sharp absorption peaks, indicating that the compound has meta-disubstituted, 729cm-1 shows a strong absorption peak, indicating that the compound has ortho-disubstituted. 1 -729cm-1 These strong absorption peaks overlap with the absorption of monosubstituted benzene, so this overtone peak can be inferred to be the absorption peak of condensed ring compounds. Figure 1-3 The infrared spectra of the 8-hydroxyquinoline standard and the compound described in this example are compared, and the positions of the absorption peaks of the spectra are consistent, so it can be judged that the ligand of the compound described in this example is consistent with 8-hydroxyquinoline. The infrared absorption peak of the compound described in this example is sharper and stronger than the infrared absorption peak of 8-hydroxyquinoline, because the molar ratio of 8-hydroxyquinoline to tin element in the compound of this example is 2:1, and the signal displayed by the functional group in the infrared spectrum is stronger than that of 8-hydroxyquinoline.

[0040] FT IR instrument parameters

[0041] Instrument Model Thermo Fisher iS5 Sample scan times 16 Background scan times 16 Resolution 4.00 Sampling Gain 1.0 Mirror speed 0.4747 Grating 100.00 Detector DTGS KBr Beam Splitter KBr light source IR

[0042] right Figure 2-1 and Figure 2-2 After analysis, the nuclear magnetic resonance hydrogen spectra of 8-hydroxyquinoline stannous and 8-hydroxyquinoline are basically consistent. 1 H-NMR (Bruker model: 400MHz AVANCE II IHD, solvent: CDC 1 3) 8-Hydroxyquinoline stannous δ8.8, 1H; δ8.2, 1H; δ7.47, 1H; δ7.39, 1H; δ7.02, 1H; δ6.93, 1H. 8-Hydroxyquinoline δ8.8, 1H; δ8.1, 1H; δ7.43, 1H; δ7.38, 1H; δ7.29, 1H; δ7.20, 1H. Comparison Figure 2-1 and Figure 2-2 8-Hydroxyquinoline Stannous has two 8-hydroxyquinoline oxygen anions in one molecule. 1H-NMR shows two groups of H shift peaks with equal intensity between δ7.2 and δ7.5, while 8-hydroxyquinoline alone shows a single group of H shift peaks.

[0043] This indicates that the compound obtained in this example and 8-hydroxyquinoline are substances with different structures.

[0044]

[0045] 8-Hydroxyquinoline stannous NMR H spectrum

[0046] H Chemical shift value H quantity 1,19 δ7.37 1 2,20 δ6.93 1 6,18 δ7.02 1 8,12 δ8.8 1 9,13 δ7.47 1 10,14 δ8.2 1

[0047] right Figure 2-3 and Figure 2-4 After analysis, the NMR carbon spectra of 8-hydroxyquinoline stannous and 8-hydroxyquinoline were obviously different. 13 C-NMR (Bruker model: 400MHz AVANCE II IHD, solvent: CDC l 3) 8-hydroxyquinoline stannous δ130.26, 1, 4, 5, 10, 15, 18, 19 C positions, δ113.06, 2 C positions, δ121.43, 6, 14, 20 C positions, δ139.45, 8 C positions, δ113.76, 9, 13 C positions, δ143.852, 12 C positions, δ131.00, 16 C positions. 8-Hydroxyquinoline standard δ121.84 δ110.39 δ148.02 δ138.39 δ128.67 δ136.26 δ152.44 δ118.00 δ127.81. Figure 2-3 and Figure 2-4 The analysis of the C1 nuclear magnetic resonance spectrum showed that the compound obtained in this example and 8-hydroxyquinoline were different substances.

[0048] 8-Hydroxyquinoline stannous NMR C spectrum

[0049] C-Number Chemical shift value 1,4,5,10,15,18,19 δ130.26 2 δ113.06 3，21 Not Detected 6,14,20 δ121.43 8 δ139.45 9,13 δ113.76 12 δ143.85 16 δ131.00

[0050]

[0051] 8-Hydroxyquinoline standard H NMR spectrum

[0052]

[0053]

[0054] 8-Hydroxyquinoline standard NMR C spectrum

[0055] C-Number Chemical shift value 1 δ121.84 2 δ110.39 3 δ148.02 4 δ138.39 5 δ128.67 6 δ136.26 8 δ152.44 9 δ118.00 10 δ127.81

[0056] Example 2: Preparation

[0057] (1) The preparation of 30% suspension concentrate is as follows, calculated by mass percentage:

[0058] 8-Hydroxyquinoline stannous acid 30%, wetting agent fatty alcohol polyoxyethylene ether 1.5%, dispersant castor oil polyoxyethylene ether 3%, silicone defoaming agent 0.5%, preservative BIT 0.2%, thickener xanthan gum 1.5%, water to make up 100%.

[0059] The preparation method is as follows:

[0060] Mix water, dispersant and wetting agent evenly according to the formula ratio, add defoamer and preservative under stirring, mix evenly through high-speed shearing, then add 8-hydroxyquinoline stannous technical, continue shearing and mixing, then put into a horizontal sand mill for primary sand milling and secondary sand milling to make the particle size of the material all below 5μm, then add thickener, shear evenly to obtain.

[0061] (2) The preparation of 30% water dispersible granules is as follows, calculated by mass percentage:

[0062] 8-Hydroxyquinoline stannous acid 30%, dispersant sodium lignin sulfonate 12%, wetting agent phenethylphenol polyoxyethylene ether condensate 8%, disintegrant polyvinyl pyrrolidone 10%, binder soluble starch 3%, silicone defoamer 0.3%, kaolin makes up 100%.

[0063] The preparation method is as follows:

[0064] After the active ingredients and the remaining auxiliary ingredients except the binder are mixed uniformly according to the formula ratio, they are crushed by a jet mill and mixed uniformly again. Then, the binder aqueous solution is sprayed into the mixture according to the formula, granulated by extrusion, dried and sieved, so as to obtain water-dispersible granules.

[0065] (3) The preparation of 30% wettable powder, calculated by mass percentage, is as follows:

[0066] 8-Hydroxyquinoline stannous acid 30%, dispersant sodium lignin sulfonate 12%, wetting agent phenethylphenol polyoxyethylene ether condensate 8%, disintegrant polyvinyl pyrrolidone 10%, silicone defoamer 0.3%, kaolin makes up 100%.

[0067] The preparation method is as follows:

[0068] After the active ingredient and the remaining auxiliary ingredients are uniformly mixed according to the formula ratio, they are crushed by a jet mill until D90 is ≤35μm to obtain a wettable powder.

[0069] Example 3: Experiment on the control of citrus rust tick and red spider

[0070] Test method: Apply pesticides in citrus orchards when rust mites or red spiders are infesting, set up clear water controls, 2-4 trees per plot, and set up interval protection zones between plots. Investigate the insect population base before spraying, use the five-point sampling method, investigate 2 citrus trees at each sampling point, mark tender shoots of each tree in the east, west, south, north, and center, and investigate the number of active mites on a total of 25 leaves. Use a backpack electric sprayer to spray evenly, and spray each plot evenly at a water volume of 100L / mu for each pesticide treatment. No other pesticides are used during the test. Investigate the insect population of red spiders 1, 3, 7, 15, 20, and 25 days after spraying, and investigate the insect population of rust mites 1 and 3 days after spraying, and calculate the insect population reduction rate and corrected control effect.

[0071] Insect population reduction rate (%) = (insect population base before treatment - number of surviving insects after treatment) × 100 / insect population base before treatment;

[0072] Control effect (%) = (insect population reduction rate in the treated area - insect population reduction rate in the control area) × 100 / (100 - insect population reduction rate in the control area).

[0073] Table 1 Field efficacy test data on citrus red spider mites Test time: March 27, 2023, weather: cloudy, temperature: 10-14℃, location: orchard in the eastern suburbs of Guilin

[0074]

[0075] Table 1

[0076]

[0077] Note: The number of live insects is the total number of insects in 3 repetitions, and the reduction rate (%) and control efficacy are the average values ​​of 3 repetitions.

[0078] Table 2 Field efficacy test data on citrus rust mites Spraying date: July 24, 2024, temperature: 29-38℃, weather: sunny, test location: eastern suburbs of Guilin

[0079]

[0080] Note: The number of live insects is the total number of 10 repetitions, and the reduction rate and control efficacy are the average numbers of 10 repetitions.

[0081] Example 4: Experiment on the prevention and control of citrus canker and citrus anthracnose

[0082] The specific experimental methods are as follows:

[0083] Spray pesticides in citrus orchards when canker and anthracnose begin to appear in April and May. Each treatment was repeated 4 times, with a clean water control, 2-4 trees in each plot, and interval protection zones between plots. A five-point sampling method was used, with 2 citrus trees surveyed at each sampling point. Each tree was sampled at 5 points in the east, south, west, north, and center, and 2 leaves or branches were surveyed at each point. A backpack electric sprayer was used for uniform spraying. Each plot was evenly sprayed at a water volume of 100L / mu for each pesticide treatment. No other pesticides were used during the test. Surveys were conducted before spraying, 10 days after the first spraying, 10 days after the second spraying, and 10 days after the third spraying.

[0084] Citrus canker lesion grading standards:

[0085] Leaf (fruit) grading method:

[0086] Level 0: no disease;

[0087] Level 1: There are 1 to 5 lesions on each leaf (fruit);

[0088] Level 3: There are 6 to 10 lesions on each leaf (fruit);

[0089] Level 5: There are 11 to 15 lesions on each leaf (fruit);

[0090] Level 7: There are 16 to 20 lesions on each leaf (fruit);

[0091] Level 9: There are more than 21 spots on each leaf (fruit).

[0092] Citrus Anthracnose Disease Grading Standards:

[0093] Level 0: branches and shoots are not infected;

[0094] Level 1: The diameter of the infected branches is less than 5 cm;

[0095] Level 2: 5 cm < branch and tip diseased diameter < 10 cm;

[0096] Level 3: 10 cm < branch and tip diseased diameter < 20 cm;

[0097] Level 4: 20 cm < branch and tip disease diameter < 30 cm;

[0098] Level 5: The diseased diameter of branches and tips is >30 cm.

[0099] Calculation method of drug efficacy:

[0100]

[0101]

[0102] Table 2 Field efficacy of the agent against citrus canker and citrus anthracnose The first application test time: May 8, 2023, weather: cloudy, temperature: 18-25℃, location: orchard in the eastern suburbs of Guilin

[0103]

[0104] It can be seen from the above experimental data that the technical solution of the present invention truly prepares 8-hydroxyquinoline stannous and its suspension, which can be used to control citrus red spiders and rust mites, and also has good preventive effects on bacterial diseases and fungal diseases of citrus. If the above-mentioned pests and diseases occur at similar times, the application period can be appropriately adjusted to prevent and control them at the same time, avoiding repeated application of the pesticides, thereby reducing production costs.

[0105] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. Use of 8-hydroxyquinoline stannous acid in preventing and controlling plant diseases and insect pests.

2. The use according to claim 1, characterized in that: The plant pests are crop mites.

3. The use according to claim 2, characterized in that: Pest mites for crops include citrus rust tick and citrus red spider.

4. The use according to claim 1, characterized in that: The plant diseases include plant fungal diseases and plant bacterial diseases.

5. The use according to claim 4, characterized in that: The plant fungal diseases include citrus anthracnose and citrus scab, and the plant bacterial diseases include citrus canker.

6. Use of 8-hydroxyquinoline stannous acid in the preparation of agents for preventing and controlling plant diseases and insect pests.

7. The use according to claim 6, characterized in that The agent is an 8-hydroxyquinoline stannous suspension, which comprises the following components by mass percentage: 8-hydroxyquinoline stannous 15-40%, a wetting agent 0.5-2.0%, a dispersant 1-4%, an organosilicon defoamer 0.3-0.6%, a preservative 0.1-0.3%, a thickener xanthan gum 1.0-2.0%, and water supplemented to 100%.

8. The method for preparing 8-hydroxyquinoline stannous used in claims 1-7, characterized in that: The following steps are involved: (1) adding a water-soluble stannous salt to water and stirring to dissolve it; (2) adding 8-hydroxyquinoline and stirring the reaction for 0.1-2 hours; (3) adding a catalyst to adjust the pH to 3.0-9.0, then heating to 70-100° C. and reacting for 0.5-3 hours; (4) Cool to room temperature, filter, wash with water, filter again, and then dry at 80-120°C.

9. The preparation method according to claim 8, characterized in that: The molar ratio of the water-soluble stannous salt to 8-hydroxyquinoline is 1.0-1.5:2.0-2.

8.

10. The preparation method according to claim 9, characterized in that: The catalyst is one or more of ammonia water, sodium hydroxide, potassium hydroxide and ammonium bicarbonate.

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