Penthiediazole zinc metal complex as well as preparation method and application thereof

Abstract

The invention belongs to the field of pesticides, and particularly relates to a penthiediazole zinc metal complex and a preparation method and application thereof.The penthiediazole zinc metal complex comprises penthiediazole zinc, or a stereoisomer thereof, or a salt thereof, or a solvate thereof, the chemical structural formula of the penthiediazole zinc is shown in the formula I, and the structural formula of the penthiediazole zinc is shown in the formula II. The composition can be prepared into a suspending agent, missible oil, powder, granules, an aqueous solution, an ultra-low volume spray, microcapsules, a smoke agent and an emulsion in water. When the pesticide is used in a field, the pesticide with the concentration of 200-800 [mu] g / mL is prepared with water, and the pesticide is sprayed on plant leaf surfaces. The preparation disclosed by the invention is effective to bacteria of crops; the bactericidal composition has a good prevention and treatment effect on plant bacterial diseases such as rice bacterial leaf blight, rice bacterial leaf streak, citrus canker, citrus yellow shoot, tomato bacterial wilt, tobacco bacterial wilt, peach tree shot hole, cabbage black rot, cabbage soft rot, muskmelon bacterial angular leaf spot and watermelon bacterial fruit rot, and especially has a good prevention and treatment effect on plant bacterial diseases such as rice bacterial leaf blight, rice bacterial leaf streak, citrus canker, citrus yellow shoot, tomato bacterial wilt, tobacco bacterial wilt, peach tree shot hole.

Description

Technical Field

[0001] The invention belongs to the field of chemical industry and pesticides, and particularly relates to a thiabendazole zinc metal complex and a preparation method and application thereof. Background Art

[0002] Bacterial plant diseases are caused by bacteria infecting plants and are the third largest category of plant diseases, after fungal and viral diseases. Bacterial diseases such as rice bacterial leaf blight, rice bacterial leaf streak, citrus canker, tobacco bacterial wilt, and tomato bacterial wilt are all major global diseases. In recent years, bacterial crop diseases such as rice bacterial leaf blight, rice bacterial leaf streak, citrus canker, citrus Huanglongbing, tomato bacterial wilt, tobacco bacterial wilt, peach shooter, cabbage black rot, cabbage soft rot, melon bacterial angular leaf spot, and watermelon bacterial fruit rot have become increasingly prevalent. These diseases are characterized by rapid onset, significant damage, and widespread distribution. The long-term use of traditional fungicides has led to a degree of resistance among plant pathogens, resulting in suboptimal control. Effective chemical agents and other effective control methods are still lacking, resulting in significant losses to agricultural production.

[0003] The 1,3,4-thiadiazole fungicide, chlorothiazol, also known as thiadiazole and chlorothiazol, has a molecular formula of C5H6N6S4. It is a systemic fungicide developed and synthesized by the Sichuan Institute of Chemical Industry in my country for the prevention and control of bacterial diseases. Chlothiazol appears as white rectangular crystals or a light yellow powder. Chlothiazol's mechanism of action is that its thiadiazole can interfere with the amino acid metabolism of pathogens, thereby disrupting protein biosynthesis and inhibiting mycelial growth. Chlothiazol is not carcinogenic, teratogenic, or mutagenic, but it is susceptible to photolysis and hydrolysis, and is prone to desulfurization reactions to form dichlorothiazol. Due to its strong teratogenic and thyroid toxicity, dichlorothiazol is included in the list of pesticides explicitly prohibited by the state. To overcome these shortcomings, Zhejiang Longwan Chemical Co., Ltd. developed the highly effective, low-toxic systemic fungicide thiophanate-methyl (Longkeb) in 1998. Its active ingredient, a chemical substance called 2-amino-5-thio-1,3,4-thiadiazole copper complex, is described in Chinese Patent Publication No. CN1227224A as a fungicide for controlling bacterial and fungal diseases of crops such as rice bacterial leaf blight and rice bacterial leaf streak. It also has efficacy against various bacterial and fungal diseases of fruit and vegetable crops. However, long-term and intensive use has led to increasing resistance, the induction of spider mites, and copper poisoning. Therefore, the search for new, highly effective, low-toxic, and low-residue green fungicides is an urgent challenge in agricultural production.

[0004] Because 1,3,4-thiadiazole derivatives possess a broad spectrum of agricultural and medical bioactivities, particularly 1,3,4-thiadiazole, one of the most representative structures in the thiadiazole class. Its bioactivities primarily include antibacterial, antiviral, herbicide, insecticide, antioxidant, and anti-inflammatory properties. Therefore, molecular design, synthesis, and bioactivity research remain a hot topic in the development of green pesticides. Literature research reveals that 1,3,4-thiadiazole derivatives have been extensively studied and applied in the areas of fungicide and herbicide applications.

[0005] In 2014, Song Baoan et al. (Song Baoan, Li Pei, Yang Song, Hu Deyu, Xue Wei, Jin Linhong, Xu Weiming, He Ming, Shi Li, Yang Xia, Shi Qingcai, Wu Fang. Thiadiazole metal complexes and their applications in controlling agricultural plant diseases [P]. CN103788119A, 2014) reported a series of thiadiazole metal complexes that effectively inhibit fungal pathogens such as wheat fusarium wilt, pepper wilt, and apple rot, as well as bacterial pathogens such as rice bacterial blight and tobacco bacterial wilt. These compounds can also be used to control fungal and bacterial diseases of crops.

[0006] In 2018, Cui Zining et al. (Cui Zining, Tao Hui, Tian Hao, Xiang Xuwen, Jiang Shan, Zhang Lianhui. Application of 1,3,4-thiadiazole compounds in the prevention and control of rice bacterial blight [P]. CN107535504B, 2018.) reported the application of a series of S-(5-substituted-1,3,4-thiadiazole)-(5-substituted phenyl)-2-furanthiocarboxylate compounds in the prevention and control of rice bacterial blight. These compounds have good biological activity and can be used as inhibitors of T3SS activity of rice bacterial blight.

[0007] In 2019, Song Baoan et al. (Song Baoan, Chen Jixiang, Yang Song, Zeng Song, He Wu, Tian Pingyi, Zhou Dagui, Yi Chongfen, Li Mingwei, Wang Yanjiao, Li Xiangyang. Disulfide derivatives containing 1,3,4-oxadiazole, their preparation methods and applications [P]. CN106632129 B, 2019.) reported a series of disulfide derivatives containing 1,3,4-oxadiazole and their applications in killing nematodes and inhibiting bacterial diseases of crops.

[0008] In 2019, Song Baoan et al. (Wu, Q., Cai, H., Yuan, T., Li, SY, Gan, XH, Song, BA) designed and synthesized a series of vanillin derivatives containing a 1,3,4-thiadiazole moiety as potential antibacterial agents [J]. Bioorg. Med. Chem. Lett. 2020, 30, 127-113.) Bioactivity tests showed that most of the compounds exhibited potent antibacterial activity against X. oryzae at a concentration of 50 μg / mL. In addition, the following patents have been reported for fungicides, such as CN1292217A, CN1308070A, CN105541822A, and CN105541822A; and for herbicides, patents have been reported for herbicides, such as CN101157665A, CN109053634A, CN106212482 A, and CN107721948A. Therefore, research on novel 1,3,4-thiadiazole fungicides is of great significance.

[0009] The purpose of the present invention is to provide a new type of highly effective and low-toxic pesticide for preventing and controlling bacterial diseases of crops such as rice bacterial leaf blight, rice bacterial leaf streak, citrus canker, citrus Huanglongbing, tomato bacterial wilt, tobacco bacterial wilt, peach punchhole disease, cabbage black rot, cabbage soft rot, melon bacterial angular leaf spot and watermelon bacterial fruit rot. Summary of the Invention

[0010] One of the purposes of the present invention is to provide a pentathiabendazole zinc metal complex and a preparation method thereof.

[0011] Another object of the present invention is to provide a composition containing the above-mentioned pentithiophanate-zinc metal complex.

[0012] Another object of the present invention is to provide the use of the above-mentioned pentathiabendazim metal complex or the composition.

[0013] Another object of the present invention is to provide a method for preventing and controlling plant bacterial diseases using the above-mentioned pentithiobacillus zinc metal complex or the composition.

[0014] This is achieved specifically through the following technical solutions:

[0015] A thiophanate-zinc metal complex, comprising thiophanate-zinc, or a stereoisomer thereof, or a salt thereof, or a solvate thereof, wherein the thiophanate-zinc is also known as chloro-bis[5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclo[14.2.1.1 4,7 .1 10,13 ] Henicos-4(20),10(21),16(19)-triene-6,12,18-trithione] zinc complex, the chemical structure of which is as shown in Formula I:

[0016]

[0017] The preparation method of thiophanate-zinc comprises the following steps: using 2-amino-5-sulfanyl-1,3,4-thiadiazole as a raw material, adding water as a solvent and sodium hydroxide as an acid-binding agent, stirring and dissolving, slowly adding formaldehyde or a paraformaldehyde solution, reacting for 1-2 hours at room temperature (25±5°C), adding dilute hydrochloric acid to precipitate a solid, performing vacuum filtration after recrystallization, absorbing and drying, and drying at 50-70°C to obtain 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocyclic ring [14.2.1.1 4,7 .1 10 ,13 ] Hennicosa-4(20), 10(21), 16(19)-triene-6,12,18-trithione (abbreviated as intermediate X5); then intermediate X5 is used as raw material, water is added as solvent, sodium hydroxide is added as acid binding agent, and finally zinc chloride dissolved in water is added to the system, and the reaction is carried out at room temperature for 1-2 hours. After the reaction is completed, water is added, and the precipitated solid is filtered with a Buchner funnel. After filtration, the sample is dried to obtain a metal complex chloro-bis[5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclo[14.2.1.1 4,7 .1 10,13 ]Hexoneca-4(20),10(21),16(19)-triene-6,12,18-trithione]zinc complex, the reaction equation is as follows:

[0018]

[0019] The temperature range of the room temperature is 25±5°C.

[0020] The present invention also provides a composition containing the pentithiophanate-zinc metal complex and an agriculturally usable adjuvant or fungicide; preferably, the composition is in the form of a suspension concentrate (SC), emulsifiable concentrate (EC), powder (DP), granule (GR), aqueous solution (AS), ultra-low volume spray (ULV), microcapsule (MC), smoke spray (FU), emulsion in water (EW), and water-dispersible granule (WG).

[0021] The powders include wettable powders (WP) and soluble powders (SP).

[0022] When the penthiaxin metal complex or a composition containing the same is used in the field, water is used to prepare the drug concentration at 200-800 μg / mL and the drug is sprayed on the plant leaves. The penthiaxin metal complex or the composition containing the same is effective against bacterial diseases of crops, particularly rice bacterial leaf blight, rice bacterial leaf streak, citrus canker, citrus Huanglongbing, tomato bacterial wilt, tobacco bacterial wilt, peach shoot hole disease, cabbage black rot, cabbage soft rot, melon bacterial angular leaf spot, and watermelon bacterial fruit rot.

[0023] The use of the pentithiobacillus zinc metal complex or a composition containing the pentithiobacillus zinc metal complex in the preparation of a drug for preventing and treating plant bacterial diseases, wherein the plant bacterial diseases include rice bacterial leaf blight, rice bacterial leaf streak, citrus canker, citrus Huanglongbing, tomato bacterial wilt, tobacco bacterial wilt, peach punch hole disease, cabbage black rot, cabbage soft rot, melon bacterial angular leaf spot and watermelon bacterial fruit rot.

[0024] Compared with the prior art, the present invention has obvious antibacterial effect. From the above technical solution, it can be seen that the present invention uses 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocycle [14.2.1.1 4,7 .1 10,13 ] Hennicosa-4(20), 10(21), 16(19)-triene-6,12,18-trithione (X5) as raw materials, a new metal complex chloro-bis[5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclo[14.2.1.1 4,7 .1 10,13] Twenty-one carbon-4(20),10(21),16(19)-triene-6,12,18-trithione] zinc (pentithiobacillus zinc), the present invention can prevent and control plant bacterial diseases such as rice white leaf blight, rice bacterial leaf streak disease, citrus canker disease, citrus yellow dragon disease, tomato bacterial wilt disease, tobacco bacterial wilt disease, peach perforation disease, cabbage black rot disease, cabbage soft rot disease, melon bacterial angular leaf spot disease and watermelon bacterial fruit rot disease.

[0025] The present invention provides a chloro-bis[5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclic[14.2.1.1 4,7 .1 10,13 ] Preparation method and application of hexone carbon-4 (20), 10 (21), 16 (19)-triene-6, 12, 18-trithione] zinc (pentathiabendazole zinc) compound, the raw material X5 (5, 11, 17-trithia-1, 3, 7, 9, 13, 15, 19, 20, 21-nonane nitrogen heterocyclic [14.2.1.1 4,7 .1 10,13 ] Hennicosa-4(20), 10(21), 16(19)-triene-6,12,18-trithione) has a wide range of sources and can be prepared by self-production or purchased from the market. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for describing the embodiments or the prior art.

[0027] Figure 1 is the chemical structural formula of pentithiobacillus zinc;

[0028] Figure 2 The crystal structure and CDCC number of pentithiobacic acid zinc;

[0029] Figure 3 This is the infrared absorption spectrum of thiabendazole;

[0030] Figure 4 The intermediate 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocycle [14.2.1.1 4, 7 .1 10,13 ]HPLC of Hennicosa-4(20),10(21),16(19)-triene-6,12,18-trithione;

[0031] Figure 5 The intermediate 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocycle [14.2.1.14, 7 .1 10,13 ]H spectrum of Hennicosa-4(20),10(21),16(19)-triene-6,12,18-trithione;

[0032] Figure 6 The intermediate 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocycle [14.2.1.1 4, 7 .1 10,13 ]C spectrum of Hennicosa-4(20),10(21),16(19)-triene-6,12,18-trithione;

[0033] Figure 7 The intermediate 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocycle [14.2.1.1 4, 7 .1 10,13 ] High-resolution mass spectrum of Hennicosa-4(20),10(21),16(19)-triene-6,12,18-trithione;

[0034] Figure 8 The intermediate 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocycle [14.2.1.1 4, 7 .1 10,13 ] Crystal structure and CDCC number of Hennicosa-4(20),10(21),16(19)-triene-6,12,18-trithione;

[0035] Figure 9 This is a graph showing the protective and therapeutic activity of penthiothiazolinone at 200 μg / mL against rice bacterial blight;

[0036] Figure 10 This is a graph showing the protective and therapeutic activity of penthiazolinone at 200 μg / mL against bacterial leaf streak of rice;

[0037] Figure 11 This is a graph showing the protective activity of penthiothiazolinone zinc against rice bacterial blight at 200 μg / mL in greenhouse fields;

[0038] Figure 12 This is the particle size distribution diagram of 20% pentithiobacillus zinc suspension concentrate;

[0039] Figure 13 This is the particle size distribution table of 20% thiabendazole zinc suspension concentrate. DETAILED DESCRIPTION

[0040] The present invention will be further described below in conjunction with the embodiments:

[0041] Example 1: 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocycle [14.2.1.1 4,7 .1 10,13 Preparation of Hennicosa-4(20),10(21),16(19)-triene-6,12,18-trithione (X5)

[0042] Weigh 5 g (37.54 mmol) of 2-amino-5-thio-1,3,4-thiadiazole as a raw material, use ethanol as a solvent, stir and heat until all the raw materials are dissolved, then cool to 30°C, slowly add formaldehyde or paraformaldehyde solution, react at room temperature (25±5°C) for 1-2 hours, add dilute hydrochloric acid to the reaction system, recrystallize the precipitated solid, vacuum filter, dry it, and dry it at 50-70°C. Finally, recrystallize to obtain 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocycle [14.2.1.1 4,7 .1 10,13 ]8.73g of Hennicosa-4(20),10(21),16(19)-triene-6,12,18-trithione (X5) compound, melting point greater than 250°C, content 93-95%, yield 51.40%. 1 HNMR(400MHz,DMSO-d6)δ8.77(t,J=6.9Hz,3H),5.43(d,J=6.9Hz,6H), 13 C NMR(100MHz,DMSO-d6)δ181.42(s,2C),155.28(s,2C),57.14(s,2C).HRMS(ESI):C9H9N9S6[MH] + calcd for433.92214,found433.92340.

[0043] Single crystals of compound X5 ( Figure 3 ), select crystals of appropriate size for data collection. The results of X-ray single crystal diffraction analysis are as follows. Colorless crystals, molecular formula: C 18 H 18 C1N 18 S 12 Zn, molecular weight M = 972.08, crystal system: monoclinic system, spacegroup P21 / c, α / °=90, β / °=101.258(10)°, γ / °=90, Z=4, T=273.15K, μ(MuKα)=6.527mm -1 , Dcalc = 1.459 g / cm3, F(000) = 1392.0, final R index [all data] R = 0.1022 (4544), wR2 = 0.2997 (5056). The crystallographic data of compound X5 have been deposited in the Cambridge Crystallographic Database (CCDC: 2441750).

[0044] Example 2: Chloro-bis[5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclo[14.2.1.1 4,7 .1 10,13 Preparation of Henoneca-4(20),10(21),16(19)-Triene-6,12,18-Trithione Zinc Complex (Penthiofen-Zinc)

[0045] Weigh the 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocycle [14.2.1.1 4,7 .1 10,13 ] Hennicosa-4(20), 10(21), 16(19)-triene-6,12,18-trithione (X5) was used as raw material, water was added as solvent, sodium hydroxide was added as acid binding agent, and finally zinc chloride dissolved in water was added to the system, and the reaction was carried out at room temperature (25±5℃) for 1-2 hours. After the reaction was completed, water was added, and the precipitated solid was filtered with a Buchner funnel. After filtration, the sample was dried to obtain a metal complex chloro-bis[5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclo[14.2.1.1 4,7 .1 10,13 ]Henicosan-4(20),10(21),16(19)-triene-6,12,18-trithione] zinc (pentithiobacillus zinc), melting point greater than 250°C, content 93-98%, yield 91.78%.

[0046] By reacting compound X5 with zinc chloride solution at high temperature, single crystals of compound pentathiabendazole zinc ( Figure 2 ), select crystals of appropriate size for data collection. Single crystal data: white crystal, molecular formula: C 18 H 18 C1N 18 S 12 Zn, molecular weight M=972.02, crystal system: Triclinic system, space group P-1, α / °=96.997(1), β / °=113.896(1), γ / °=106.824(1), Z=2, T=273.15K, μ(MuKα)=7.544mm -1 , Dcalc=1.722g / cm 3 , F(000)=1276.0, final R index is [all data]R=0.0388(7553), wR2=0.1197(8734), CCDC Number:2449701.

[0047] The thiabendazole zinc compound technical drug of the present invention is white powder, and the mass percentage content of the thiabendazole zinc accounts for 1-97% of the total amount, preferably 10-80%.

[0048] The following is a comparison of the fungicide penthioxam-zinc of the present invention with thiophanate-copper and thiazole-zinc in preventing and controlling rice bacterial leaf blight and rice bacterial leaf streak to further illustrate the effect. The comparative test results are as follows:

[0049] Example 3 The original drug, clay and wetting dispersant obtained in Example 2 were ground into a 10%-20% wettable powder or a 10%-20% suspension. When used, it was prepared with water to 200-400 μg / mL and sprayed on the plant leaves.

[0050] Test Example 1: The indoor inhibition activity tests of the target compound against Xanthomonas oryzae, Xanthomonas oryzae, Xanthomonas solani, Xanthomonas aurantii, Xanthomonas syringae, Xanthomonas spp., Xanthomonas spp., Xanthomonas spp., Xanthomonas spp., Xanthomonas spp., Xanthomonas spp., Xanthomonas spp., Xanthomonas spp. and Xanthomonas spp. are shown in Tables 1 to 10.

[0051] The synthesized target compound chloro-bis[5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclo[14.2.1.1 4,7 .1 10,13 ] Twenty-one carbon-4 (20), 10 (21), 16 (19) -triene -6, 12, 18- trithione] zinc (pentathiabendazole zinc) and thiabendazole copper, thiazolidine zinc were prepared into drug-containing NB liquid culture medium with concentrations of 100 and 50 μg / mL, respectively, and 40 μL of the above-prepared pathogens containing rice bacterial leaf blight (Xoo), rice bacterial leaf streak (Xoc) and other pathogens were added to the NB liquid culture medium, and cultured in a constant temperature shaker at 28 ° C and 180 rpm for 24 to 48 hours until the growth logarithmic phase, and the OD value (OD) of the bacterial solution of each concentration was measured on a microplate reader. 595). In addition, the OD values ​​(OD 595 ), the OD value caused by the culture medium itself was corrected. The calculation formula of the corrected OD value and inhibition rate is as follows:

[0052] Corrected OD value = OD value of bacterial culture medium - OD value of sterile culture medium

[0053]

[0054] Five corresponding concentration gradients were set for the target compounds to determine their EC values ​​against bacteria such as Xanthoceras oryzae (Xoo), Xanthoceras oryzae (Xoc), Xanthoceras solani, Xanthoceras citri (Xac), Xanthoceras spp. (Peach Sclerotinia), Xanthoceras oleraceus, Xanthoceras spp. (Tobacco Bacterial Wilt), Xanthoceras rapae, Xanthoceras spp. (Pakchoy Soft Rot), Xanthoceras melanocarpa, and Xanthoceras spp. (Watermelon Bacterial Fruit Rot). 50 value.

[0055] The above method was used to determine the example chloro-bis[5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclo[14.2.1.1 4,7 .1 10,13 Antibacterial activity and EC of 21-hexone-4(20),10(21),16(19)-triene-6,12,18-trithione zinc (pentithiobacillus zinc) 50 The results are shown in Tables 1 to 10.

[0056] Table 1 Antibacterial activity of the fungicide penthiothiazolinone against bacterial blight of rice

[0057]

[0058] Note: a Average of three replicates. b Commercial antibacterial agent (20%, suspension agent).

[0059] The results in Table 1 show that the fungicides pentithiobacillus zinc, thiazole zinc and thiazole copper have certain antibacterial activity against bacterial blight of rice. 50 The concentrations of thiabendazole zinc (21.31 μg / mL) of the fungicide of the present invention are 21.31, 23.96, and 82.64 μg / mL, respectively. The fungicide penthioxam zinc (21.31 μg / mL) shows excellent antibacterial activity against rice bacterial blight pathogen, which is better than the commercial agents thiabendazole zinc (23.96 μg / mL) and thiabendazole copper (82.64 μg / mL).

[0060] Table 2 Antibacterial activity of the fungicide penthiothiazolinone against bacterial leaf streak pathogen of rice

[0061]

[0062] Note: a Average of three replicates. b Commercial antibacterial agent (20%, suspension agent).

[0063] The results in Table 2 show that the fungicides pentithiobacillus zinc, thiazole zinc and thiazole copper of the present invention have certain antibacterial activity against bacterial leaf streak pathogens. 50 The concentrations of thiabendazole zinc (34.11 μg / mL) of the fungicide of the present invention against bacterial leaf streak pathogen of rice were 34.11, 37.74 and 87.08 μg / mL, respectively. The fungicide penthioxam zinc (34.11 μg / mL) showed excellent antibacterial activity against bacterial leaf streak pathogen of rice, which was better than the commercial agents thiabendazole zinc (37.74 μg / mL) and thiabendazole copper (87.08 μg / mL).

[0064] Table 3 Antibacterial activity of the fungicide pentithiobacillus zinc against tomato bacterial wilt pathogen

[0065]

[0066] Note: a Average of three replicates. b Commercial antibacterial agent (20%, suspension agent).

[0067] The results in Table 3 show that the fungicides pentithiobacillus zinc, thiazole zinc and thiazole copper have certain antibacterial activity against tomato bacterial wilt pathogens. 50 The concentrations of thiophanate-copper in the concentration range of 38.49, 37.95 and 130.63 μg / mL were respectively. Among them, the fungicide pentithiophanate-zinc (38.49 μg / mL) of the present invention showed good antibacterial activity against tomato bacterial wilt pathogen, which was better than thiophanate-copper (130.63 μg / mL) and comparable to the commercial agent thiazole zinc (37.95 μg / mL).

[0068] Table 4 Antibacterial activity of the fungicide pentithiobacillus zinc against citrus canker

[0069]

[0070]

[0071] Note: aAverage of three replicates. b Commercial antibacterial agent (20%, suspension agent).

[0072] The results in Table 4 show that the fungicides pentithiobacillus zinc, thiazole zinc and thiazole copper of the present invention have certain antibacterial activity against citrus canker bacteria, and their EC 50 The concentrations of thiabendazole zinc (44.59 μg / mL) in the fungicide of the present invention were 44.59, 45.05 and 87.74 μg / mL, respectively. The fungicide penthioxam zinc (44.59 μg / mL) showed excellent antibacterial activity against citrus canker pathogens, which was superior to the commercial agents thiazolidine zinc (45.05 μg / mL) and thiabendazole copper (87.74 μg / mL).

[0073] Table 5 Antibacterial activity of the fungicide pentathiazolinone zinc of the present invention against peach perforator pathogen

[0074]

[0075] Note: a Average of three replicates. b Commercial antibacterial agent (20%, suspension agent).

[0076] The results in Table 5 show that the fungicides pentithiobacillus zinc, thiazole zinc and thiazole copper of the present invention have certain antibacterial activity against peach perforator pathogens. 50 The concentrations of thiabendazole zinc (37.37 μg / mL) in the fungicide of the present invention were 37.37, 39.39 and 244.76 μg / mL, respectively. The fungicide penthioxam zinc (37.37 μg / mL) showed excellent antibacterial activity against peach perforator pathogen, which was superior to the commercial agents thiazolidine zinc (39.39 μg / mL) and thiabendazole copper (244.76 μg / mL).

[0077] Table 6 Antibacterial activity of the fungicide pentithiobacillus zinc of the present invention against cabbage black rot fungi

[0078]

[0079] Note: a Average of three replicates. b Commercial antibacterial agent (20%, suspension agent).

[0080] The results in Table 6 show that the fungicides pentithiobacillus zinc, thiazole zinc and thiazole copper of the present invention have certain antibacterial activity against cabbage black rot fungi, and their EC50 The values ​​of the fungicide penthiophanate-zinc (49.19 μg / mL) of the present invention were 49.19, 84.45 and 207.51 μg / mL respectively, among which the fungicide pentithiophanate-zinc (49.19 μg / mL) had certain antibacterial activity against cabbage black rot fungus, which was better than the commercial agent thiophanate-copper (207.51 μg / mL) and the commercial agent thiazole zinc (84.45 μg / mL).

[0081] Table 7 Antibacterial activity of the fungicide pentithiobacillus zinc of the present invention against tobacco bacterial wilt pathogen

[0082]

[0083] Note: a Average of three replicates. b Commercial antibacterial agent (20%, suspension agent).

[0084] The results in Table 7 show that the fungicides pentithiobacillus zinc, thiazole zinc and thiazole copper have certain antibacterial activity against tobacco bacterial wilt pathogens. 50 The antibacterial activity of the fungicide penthioxam-zinc (86.63 μg / mL) against tobacco bacterial wilt pathogen was better than that of the commercial agent thiophanate-copper (190.44 μg / mL), and was equivalent to that of thiabendazole zinc (87.99 μg / mL).

[0085] Table 8 Antibacterial activity of the fungicide pentithiobacillus zinc of the present invention against Chinese cabbage soft rot pathogens

[0086]

[0087] Note: a Average of three replicates. b Commercial antibacterial agent (20%, suspension agent).

[0088] The results in Table 8 show that the fungicides pentithiobacillus zinc, thiazole zinc and thiazole copper of the present invention have certain antibacterial activity against the cabbage soft rot pathogen. 50 The inhibitory activity of the fungicide thiophanate-copper (38.59 μg / mL) against the soft rot pathogen of Chinese cabbage was better than that of the commercial agents thiophanate-copper (158.94 μg / mL) and thiazole zinc (39.88 μg / mL).

[0089] Table 9 Antibacterial activity of the fungicide pentithiobacillus zinc of the present invention against bacterial angular leaf spot of melon

[0090]

[0091] Note: a Average of three replicates. b Commercial antibacterial agent (20%, suspension agent).

[0092] The results in Table 9 show that the fungicides pentithiobacillus zinc, thiazole zinc and thiazole copper of the present invention have certain antibacterial activity against bacterial angular leaf spot of melon. 50 The inhibitory activity of the fungicide thiophanate-copper (24.45 μg / mL) against bacterial angular leaf spot of melon was better than that of the commercial agents thiophanate-copper (90.80 μg / mL) and thiabendazole zinc (31.57 μg / mL).

[0093] Table 10 Antibacterial activity of the fungicide pentithiobacillus zinc of the present invention against bacterial fruit rot of watermelon

[0094]

[0095] Note: a Average of three replicates. b Commercial antibacterial agent (20%, suspension agent).

[0096] The results in Table 10 show that the fungicides pentithiocarb zinc, thiazole zinc and thiazole copper of the present invention have certain antibacterial activity against watermelon bacterial fruit rot pathogens. 50 The inhibitory activity of the fungicide thiophanate-copper (38.47 μg / mL) against watermelon bacterial fruit rot was better than that of the commercial agents thiophanate-copper (107.58 μg / mL) and thiabendazole zinc (93.51 μg / mL).

[0097] Test Example 2: Using the fungicide chloro-bis[5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclo[14.2.1.1 4,7 .1 10,13The effects of pentathiabendazole zinc (pentathiabendazole zinc) on the prevention and treatment of rice bacterial leaf blight and rice bacterial leaf streak disease were compared with pentathiabendazole zinc (pentathiabendazole zinc) in the prevention and treatment of rice bacterial leaf blight and rice bacterial leaf streak disease to further illustrate their effects. The comparative test results are as follows:

[0098] 1. Test on the protective and therapeutic effects of the fungicide pentithiobacillus zinc on rice bacterial blight in living potted plants

[0099] The leaf clipping method was used to determine the protective and therapeutic effects of the fungicide penthiothiazolinone on rice bacterial blight in living pot plants at a concentration of 200 μg / mL.

[0100] 1.1 Protective activity

[0101] The fungicides penthiothiazolin, thiophanate-copper, and thiazole zinc of the present invention were each dissolved in 200 μL of DMSO and prepared with a 0.1% Tween-80 solution to a concentration of 200 μg / mL. The mixture was evenly sprayed onto rice leaves until droplets appeared. After 24 hours, the leaves were cut and inoculated with scissors containing the pathogen Bacterial Blight of Rice (Bacterial Blight of Rice). The bacterial solution was applied to the tip of the rice leaves at one-third of the surface. A control containing no fungicides was also set up with clear water. Each treatment involved 10-15 leaves, with three replicates. Fourteen days after application, the length of the lesions on the rice leaves was measured, and the control efficacy was calculated based on the lesion length.

[0102] 1.2 Therapeutic activity

[0103] Using scissors soaked in bacterial solution, the tip of a rice leaf was cut 2-3 cm from the tip. After 24 hours, the fungicides penthiothiazolin, thiabendazim zinc, and thiophanate-copper were dissolved in DMSO. A 0.1% Tween-80 solution was then added to a 200 μg / mL solution and sprayed evenly onto the rice leaves until droplets formed. A control of untreated water was also provided. Ten to 15 leaves per rice plant were treated. Fourteen days after application, the length of the lesions on the rice leaves was measured, and the control efficacy was calculated based on the lesion length.

[0104] 2. Test on the protective and therapeutic effects of the fungicide pentithiobacillus zinc on rice bacterial leaf streak in living pot plants

[0105] The protective and therapeutic effects of the fungicide penthiothiazolinone on rice bacterial leaf streak in living pot plants were tested using the pressure osmosis method at a concentration of 200 μg / mL.

[0106] 2.1 Protective activity

[0107] The fungicides penthiothiocarb, thiophanate-copper, and thiazole zinc of the present invention were each dissolved in 200 μL of DMSO. The mixture was then diluted with a 0.1% Tween-80 solution to a concentration of 200 μg / mL and sprayed evenly onto rice leaves until droplets appeared. Twenty-four hours later, the leaves were inoculated with a metered syringe containing the bacterial leaf streak pathogen of rice. The infiltration site was located between one-third and one-half of the tip of the rice leaf. A control containing no fungicides was also established using clear water. Ten to 15 leaves were treated for each treatment, with three replicates. Fourteen days after application, the length of the lesions on the rice leaves was measured, and the control efficacy was calculated based on the lesion length.

[0108] 2.2 Therapeutic activity

[0109] A quantitative syringe filled with the bacteria for bacterial leaf streak of rice was used for pressure inoculation at the 1 / 3-1 / 2 of the tip of a rice leaf. 24 hours later, the fungicides penthiothiazolinone, thiophanate-copper, and thiabendazole zinc of the present invention were dissolved in DMSO and then prepared with a 0.1% Tween-80 solution to a concentration of 200 μg / mL. The mixture was evenly sprayed onto the rice leaves until droplets appeared. A control of untreated water was also provided. 10-15 leaves per rice plant were treated. Fourteen days after application, the length of the lesions on the rice leaves was measured, and the control efficacy was calculated based on the lesion length.

[0110] Table 11 Protective effect of the fungicide pentithiobacillus zinc on rice bacterial blight

[0111]

[0112] Note 1: The fungicide pentithiobacillus-zinc of the present invention is the original drug; zinc thiazide: 20% suspension concentrate; thiophanate-copper: 20% suspension concentrate. Note 2: The control effect was observed 14 days after the application of the drug.

[0113] As can be seen from Table 11, at a concentration of 200 μg / mL, the fungicides penthiaxin, thiabendazole zinc, and thiabendazole-copper exhibited protective effects against rice bacterial blight of 80.98%, 70.83%, and 53.81%, respectively. Among them, the fungicide penthiaxin exhibited a superior protective effect against rice bacterial blight, exceeding the commercial agent thiabendazole zinc (70.83%) by more than 10 percentage points and outperforming the commercial agent thiabendazole-copper (53.81%) by more than 20 percentage points.

[0114] Table 12 The therapeutic effect of the fungicide penthiothiazolinone zinc on rice bacterial blight

[0115]

[0116] Note 1: The fungicide pentithiobacillus-zinc in this invention is the technical product; thiazole zinc: 20% suspension concentrate; thiazole copper: 20% suspension concentrate. Note 2: The control effect was observed 14 days after application.

[0117] Note 3: Different lowercase letters after the data in the same column indicate significant differences (p < 0.05).

[0118] As can be seen from Table 12, at a concentration of 200 μg / mL, the fungicides pentithiobac-zinc, thiabendazole zinc, and thiabendazole-copper exhibited therapeutic effects on rice bacterial blight of 78.34%, 69.11%, and 50.57%, respectively. The fungicide pentithiobac-zinc exhibited a good therapeutic effect (78.34%) on rice bacterial blight, outperforming the commercial agents thiabendazole zinc (69.11%) and thiabendazole-copper (50.57%).

[0119] From Table 11 and Table 12 above, it can be seen that the fungicide penthiazolinone-zinc of the present invention has good therapeutic and protective effects on rice bacterial blight, which proves that the fungicide of the present invention has a very strong fungicidal effect.

[0120] Table 13 Protective effect of the fungicide penthiothiazolinone zinc on rice bacterial leaf streak

[0121]

[0122]

[0123] Note 1: The fungicide pentithiobacillus zinc in this invention is the technical drug; zinc thiazole: 20% suspension concentrate; thiazole copper: 20% suspension concentrate

[0124] Note 2: The control effect will be observed 14 days after application.

[0125] Note 3: Different lowercase letters after the data in the same column indicate significant differences (p < 0.05).

[0126] As can be seen from Table 13, at a concentration of 200 μg / mL, the protective effects of the fungicides penthiaxin, zinc thiazolidine, and thiabendazole against bacterial leaf streak of rice were 67.00%, 56.98%, and 49.12%, respectively. Among them, the fungicide penthiaxin (67.00%) had a better protective effect against bacterial leaf streak of rice, which was superior to the commercial agents zinc thiazolidine (56.98%) and thiabendazole (49.12%).

[0127] Table 14 The therapeutic effect of the fungicide penthiothiazolinone on rice bacterial leaf streak

[0128]

[0129] Note 1: The fungicide pentithiobacillus zinc in this invention is the technical product; zinc thiazole: 20% suspension concentrate; thiazole copper: 20% suspension concentrate

[0130] Note 2: The control effect will be observed 14 days after application.

[0131] Note 3: Different lowercase letters after the data in the same column indicate significant differences (p < 0.05).

[0132] As can be seen from Table 14, the fungicides penthiaxin, thiabendazole zinc, and thiabendazole copper of the present invention have certain therapeutic effects on rice bacterial leaf streak at a concentration of 200 μg / mL, with therapeutic effects of 65.18%, 55.82%, and 47.14%, respectively. Among them, the fungicide penthiaxin (65.18%) of the present invention has a better therapeutic effect on rice bacterial leaf streak than the commercial agents thiabendazole zinc (55.82%) and thiabendazole copper (47.14%).

[0133] Test Example 3: Test on the protective effect of the fungicide pentithiobacillus zinc on rice bacterial blight in greenhouse fields

[0134] The test operation method is the same as that of determining the protective effect of the fungicide penthiothiazolinone against rice bacterial blight in living pot plants at a concentration of 200 μg / mL using the leaf clipping method.

[0135] Table 15 Greenhouse field test on the protective effect of the fungicide pentithiobacillus zinc on rice bacterial blight

[0136]

[0137]

[0138] Note 1: The fungicide pentithiobacillus-zinc of the present invention is the original drug; zinc thiazide: 20% suspension concentrate; thiophanate-copper: 20% suspension concentrate. Note 2: The control effect was observed 14 days after the application of the drug.

[0139] Note 3: Different lowercase letters after the data in the same column indicate significant differences (p < 0.05).

[0140] As shown in Table 15, the fungicides penthiaxin and thiazolinone zinc of the present invention, at a concentration of 200 μg / mL, demonstrated protective efficacy against rice bacterial blight in greenhouse field experiments, with protective efficacy rates of 73.15% and 57.92%, respectively. The fungicide penthiaxin of the present invention demonstrated excellent protective efficacy against rice bacterial blight, surpassing the commercial agent thiazolinone zinc (57.92%).

[0141] Results and Discussion: From the above data, it can be seen that the results of the in vivo pot test in the greenhouse can further confirm that, at the same concentration, the fungicide penthioxam-zinc of the present invention has a 15-20 percentage point increase in the prevention effect on rice bacterial leaf blight compared with the thiophanate-copper fungicide (Lonkebacterium) disclosed in CN1227224A, and is 10 percentage points higher than the commercial agent thiazole zinc. This shows that the fungicide penthioxam-zinc of the present invention has a good prevention and control effect on rice bacterial leaf blight and rice bacterial leaf streak.

[0142] In order to further evaluate the fungicidal activity of the fungicide penthioxam-zinc of the present invention, it is necessary to prepare penthioxam-zinc into a 20% suspension concentrate for field trial promotion, which provides data support for the pesticide registration of penthioxam-zinc.

[0143] To address the above-mentioned problems existing in the prior art, the present invention provides a formulation for preparing a 5-25% aqueous suspension concentrate of thiabendazole, comprising the active ingredient thiabendazole, a wetting and dispersing agent, a thickener, an antifreeze agent, a defoaming agent, and water, wherein the weight ratios of the components are 5-25wt%, 3-12wt%, 0.5-2.5wt%, 2-6wt%, and 0.3-0.5wt%, respectively, and water is used to make up to 100%. Preferably, the weight ratio of thiabendazole is 5-25wt%, 5-20wt%, 5-10wt%, 10-20wt%, or 10-25wt%, and most preferably 20wt%.

[0144] The wetting and dispersing agent selected in the present application is a compound of ionic or nonionic adjuvants, including a high molecular weight amphiphilic anionic nonionic surfactant complex, phosphates, lignin sulfonates, salts of phenolsulfonic acid or naphthalenesulfonic acid, salts of polyacrylic acid, sulfosuccinates, alkyl sulfonates, alkylaryl sulfonates, alkyl sulfates, lauryl ether sulfates, fatty alcohol sulfates, sulfonate formaldehyde condensates, and sulfated hexadecyl, heptadecanol and octadecanol, and sulfated fatty alcohol glycol ethers;

[0145] The defoamer is 0.3-0.5 wt% of polydimethylsiloxane in an organosilicon defoamer;

[0146] The antifreeze agent is an inorganic salt;

[0147] The thickener is one or two of magnesium aluminum silicate SF-40 and xanthan gum.

[0148] Preferably, the wetting and dispersing agent is composed of a polymer amphiphilic anionic nonionic surfactant complex SC29, sodium diphenylmethanesulfonate HAS040, naphthalenesulfonic acid sodium salt formaldehyde condensation product NNO and any one of sodium p-toluenesulfonate, sodium methanesulfinate or polynaphthalene formaldehyde sulfonic acid sodium salt in a weight ratio of 2:2:2:1.5; more preferably, the wetting and dispersing agent is composed of a polymer amphiphilic anionic nonionic surfactant complex SC29, sodium diphenylmethanesulfonate HAS040, naphthalenesulfonic acid sodium salt formaldehyde condensation product NNO and sodium p-toluenesulfonate in a weight ratio of 2:2:2:1.5.

[0149] Preferably, the thickener is a mixture of 2% magnesium aluminum silicate SF-40 or 1% magnesium aluminum silicate and 0.05% xanthan gum.

[0150] The pentathiapiprolin suspension for preventing and controlling plant bacterial diseases is prepared by taking a wetting dispersant, an antifreeze agent, and water according to the weight percentage, stirring and dissolving, adding pentathiapiprolin and a thickener according to the weight percentage, mixing evenly under the action of a shearing machine, and then pumping the mixed slurry into a sander for grinding, adding an organosilicon defoamer according to the weight percentage, and performing a particle size test every 1 hour. 90 When the particle size is approximately equal to 6.0 μm, stirring is stopped and the 20% thiabendazole zinc suspension is obtained after filtration. 90 5-8μm.

[0151] Innovation of this patent: The main significance of the developed dosage form is that through extensive screening of wetting and dispersing agents, a formulation is prepared that can effectively improve the prevention effect of the original drug in penthiaxin zinc suspension and penthiaxin zinc wettable powder on plant bacterial diseases. The penthiaxin zinc suspension prepared by the present invention has the characteristics of good dispersibility in water and storage is beneficial to the stability of the original drug.

[0152] 1. Screening of wetting and dispersing agents

[0153] The 5-25% pentithiobacillus zinc suspension prepared by compounding a high molecular weight amphiphilic anionic nonionic surfactant complex with different types of surfactants was subjected to heat storage and the water dispersibility of the original drug and the decomposition rate of the original drug after heat storage were measured. The specific results are shown in Table 16.

[0154] Table 16 Selection of wetting and dispersing agents

[0155]

[0156] As shown in Table 16, screening of different adjuvant types revealed that the addition of sulfonate adjuvants improves the stability of the technical product. The penthioxafatin suspension concentrate (SC29), a polymeric amphiphilic anionic nonionic surfactant complex, sodium diphenylmethanesulfonate HAS040, naphthalenesulfonic acid sodium salt formaldehyde condensate NNO, and sodium p-toluenesulfonate, sodium methanesulfinate, or sodium polynaphthalene formaldehyde sulfonate, exhibits excellent dispersibility, with the technical product decomposition rate after hot storage kept below 5%.

[0157] In order to screen the optimal dosage of auxiliary agents such as sodium p-toluenesulfonate, sodium polynaphthalene formaldehyde sulfonate, and sodium methanesulfinate, three contents of 0.5%, 1.5%, and 3.0% were set for screening. The specific results are shown in Table 17.

[0158] Table 17 Screening of additive dosage

[0159]

[0160]

[0161] As shown in Table 17, the decomposition rate of pentithiophanate-zinc after hot storage was less than 5% at all three different concentrations. Sodium methanesulfinate is relatively expensive and has average water dispersibility. Adding sodium polynaphthalene formaldehyde sulfonate causes the suspension concentrate to turn yellow, affecting its appearance. However, adding sodium p-toluenesulfonate not only improves the stability of the technical product but also offers a relatively lower price and a better appearance. Therefore, considering both cost and properties, the preferred wetting and dispersing agent formulation is SC29: HAS040: NNO: sodium p-toluenesulfonate = 2:2:2:1.5.

[0162] 2. Screening of thickeners

[0163] Aqueous suspension concentrates often face storage stability issues, such as particle agglomeration, sedimentation, and thickening. The aforementioned formulation is prone to sedimentation upon prolonged storage. This can be addressed by increasing viscosity to improve sedimentation stability. Excessive viscosity can make the product difficult to pour and result in significant sticking, complicating processing and use. An appropriate viscosity ensures good stability and a high suspension efficiency. Based on relevant theory and the chemical instability of thiophanate-zinc, this experiment maintained the required additives for the previously screened formulation. Instead, the viscosity was modified by adjusting the dosages of magnesium aluminum silicate and xanthan gum. However, increased viscosity can reduce the self-dispersibility of the aqueous suspension concentrate. Therefore, the water dispersibility was improved by increasing the dosage of the dispersant NNO. The results are shown in Table 18.

[0164] Table 18 Screening of thickeners

[0165]

[0166] As shown in Table 18, excessive addition of xanthan gum affected both the fluidity and water dispersibility of the formulation. Therefore, without compromising water dispersibility, 2% magnesium aluminum silicate was used as a thickener, or a combination of 1% magnesium aluminum silicate and 0.05% xanthan gum was used to improve the sedimentation stability of the suspension concentrate. Furthermore, increasing the NNO content enhanced the water dispersibility of the formulation.

[0167] 3. Selection of defoamer dosage

[0168] The wetting and dispersing agents described in this application are mostly sulfonates, which can cause a large number of bubbles during processing and affect the grinding effect. Therefore, some organosilicon defoamers such as polydimethylsiloxane are usually added to the suspending agent, but the defoamer should be added in moderation. Too much defoamer will reduce the surface tension of the system and make the stratification phenomenon more obvious. If too little is added, the defoaming effect is not obvious. In this experiment, a universal organosilicon defoamer was selected for testing, and the specific results are shown in Table 19.

[0169] Table 19 Screening of defoamer dosage

[0170]

[0171] As shown in Table 19, when the defoamer dosage is too low, it cannot effectively solve the large amount of bubbles generated during the grinding process. When the dosage is controlled at 0.3-0.5%, fewer bubbles are generated during the preparation process, which is conducive to grinding.

[0172] 4. Selection of antifreeze

[0173] Pesticide suspension concentrates using water as the dispersion medium need to maintain stability in extremely cold conditions during storage, and therefore typically require the addition of a suitable antifreeze. Using glycerol as the antifreeze increases system viscosity and poor fluidity. Using ethylene glycol as the antifreeze improves formulation stability and fluidity, but increases the decomposition rate of the technical product after hot storage. Using sodium chloride as the antifreeze, although very little precipitation will occur at the bottom of the product after cold storage, this does not increase the degree of decomposition of the technical product. Therefore, sodium chloride is the optimal antifreeze.

[0174] 5. Effect of particle size on the stability of the technical after hot storage

[0175] After determining the above-mentioned adjuvants, aqueous suspension concentrates of pentithiophanate-zinc with different particle sizes (No. 1-6) were prepared. After heat storage, the content of the technical drug was determined using the pesticide thermal stability determination method GB / T19136-2003, and the decomposition rate of the technical drug after heat storage was analyzed. The specific results are shown in Table 20.

[0176] Table 20 Effect of particle size on the stability of the original drug

[0177]

[0178]

[0179] like Figure 13 As shown in Table 20, the 20% pentithiophanate-zinc aqueous suspension prepared using the above-mentioned adjuvants met stability requirements when the particle size was between 5 and 8 μm. This indicates that, under this formulation, the formulation and particle size have a significant impact on the chemical stability of the pentithiophanate-zinc aqueous suspension. Smaller particle sizes improve the chemical stability of the technical, but too small a particle size makes industrial production difficult.

[0180] By screening the wetting and dispersing agents, the amount of the additives, the thickeners, the amount of the defoaming agents, and the antifreeze agents, the preferred formula and preparation method were determined as shown in Table 21 below.

[0181] Table 21 Preparation processing formula composition

[0182]

[0183] The above-mentioned thiophanate-zinc suspension for preventing and controlling plant bacterial diseases is prepared by taking a dispersant, a wetting agent, an antifreeze agent and water according to the weight percentage, stirring and dissolving, adding thiophanate-zinc and a thickener according to the weight percentage, mixing evenly under the action of a shearing machine, and then pumping the mixed slurry into a sander for grinding, adding an organosilicon defoamer according to the weight percentage, and performing a particle size test every 1 hour. 90 When the particle size is approximately equal to 5.0 μm, stirring is stopped and the 20% thiabendazole zinc suspension is obtained after filtration. 90 5-8μm.

[0184] 6.20% Penthiothiazolinone zinc suspension concentrate control item index specifications

[0185] The key properties of the suspension concentrates were tested in accordance with the national standard for pesticide suspension concentrates (GB / T19136-2003), as shown in Table 22. The results show that, using this formulation, the pentithiophanate-zinc aqueous suspension concentrate exhibits a milky white, uniform dispersion with good dispersibility and suspension efficiency. The technical product is relatively stable after heat storage and is also stable at low temperatures.

[0186] Table 220% Penthiothiocarb zinc aqueous suspension concentrate control item indicators

[0187]

[0188]

[0189] The present invention is further illustrated by the following examples. It should be understood that the methods described in the examples are merely illustrative of the present invention and are not intended to limit the present invention. Simple modifications to the preparation methods of the present invention, based on the concepts of the present invention, fall within the scope of the present invention. All raw materials and solvents used in the examples are commercially available products of corresponding purity.

[0190] Example 3: Preparation of 20% pentithiobacillus zinc suspension

[0191] Weigh 2.0g of sodium diphenylmethanesulfonate HAS040, 2.0g of sodium naphthalenesulfonate formaldehyde condensate NNO, 1.5g of sodium p-toluenesulfonate, 4.0g of sodium chloride and 2.0g of high molecular weight amphiphilic anionic nonionic surfactant complex SC 29 in a beaker containing 66.1g of secondary water. After stirring and dissolving, add 20.0g of thiophanate-zinc and 2.0g of magnesium aluminum silicate. After shearing and homogenization, pour it into a sand mill containing zirconium beads with a volume mass ratio of 1:1 to the suspending agent, add 0.4g of polydimethylsiloxane, and start sand milling in an ice water bath. The particle size is tested every 1h. After about 4h, the particle size is tested using a laser particle size analyzer. D 90 When the particle size is about 5 μm, stirring is stopped and the mixture is filtered to obtain a 20% pentithiophanate-zinc suspension.

[0192] Test Example 5: Field test on the control effect of the fungicide penthiothiocarb zinc of the present invention on rice bacterial blight. Test site address: Yangchang Township, Pingba District, Anshun City, Guizhou Province, National Crop Variety Monitoring Station (Guizhou) Base, longitude 106.318371, latitude 26.367751, altitude 1220 meters, flat test site, rice field.

[0193] This experiment has 5 treatments, 4 replicates, and a total of 20 plots; the plot area is 5m x 4m = 20m 2 Condition survey and result statistics

[0194] During the trial, the disease condition was investigated twice: the first time before the first treatment and the second time after the last treatment, 14 days after the last application of the drug.

[0195] Each plot was sampled at five diagonal points, with 50 plants surveyed at each point. The entire sword leaf and two leaves below the sword leaf were surveyed for each plant. Leaves were graded according to the severity of the lesions, and the total number of leaves and the number of diseased leaves at each level were recorded.

[0196] Level 0: No lesions on leaves;

[0197] Level 1: The lesion area accounts for less than 10% of the leaf area;

[0198] Level 3: The lesion area accounts for 11% to 25% of the leaf area;

[0199] Level 5: The lesion area accounts for 26% to 45% of the leaf area;

[0200] Level 7: The lesion area accounts for 46% to 65% of the leaf area;

[0201] Level 9: The lesion area accounts for more than 65% of the leaf area.

[0202] The incidence rate and disease index were calculated according to the following formula, and the difference was analyzed with SPSS software: Disease index = [Σ(number of diseased leaves at each level × relative level value) / total number of leaves surveyed × 9)] × 100

[0203] Control effect (%) = [(disease index of blank control area - disease index of treated area) / disease index of blank control area] × 100 test results

[0204] Table 23 Field control effect of the fungicide penthiothiazolinone zinc of the present invention on rice bacterial blight

[0205]

[0206] Note: Different lowercase letters after the data in the same column indicate significant differences (p < 0.05).

[0207] The test data shown in Table 23 show that the control effect of thiabendazole zinc (50-150 ml / mu) is significantly improved with the increase of dosage, the disease index decreases year by year (1.18-0.97), and the control effect reaches 64.69%-70.91%. The best control effect (70.91%) is achieved at a dosage of 150 ml / mu, which is better than the control agent 20% thiabendazole zinc (67.13%). In addition, the concentration range used in this experiment is safe for rice and no phytotoxicity occurs.

[0208] Test Example 6: Field Test of the Efficacy of the Inventive Fungicide Penthiothiocarbamate-Zinc Against Tomato Bacterial Wilt The test site is located at Guai'er Village, Jiu'an Township, Huaxi District, Guiyang City, Guizhou Province, at latitude 26.515145°, longitude 106.575132°, and an altitude of 1184.96 m. The test site is flat, with uniform fertility, and is used for tomato rotation, where bacterial wilt is common.

[0209] This experiment set up the tomato plots in natural box blocks, with a tomato plant spacing of 0.33m and a row spacing of 1m. The plot length was 5m and the width was 3m. 45 tomatoes were planted in each plot, and the plots were arranged in random blocks. This experiment had 5 treatments, 4 replicates, and a total of 20 plots. The plot area was 3.0m×5.0m=15m 2

[0210] Condition survey and result statistics

[0211] During the trial, the disease condition was investigated twice: the first time before the first treatment and the second time after the last treatment, 21 days after the last application of the drug.

[0212] Investigate all plants in each plot and record the total number of plants and the number of diseased plants

[0213] The incidence rate and disease index were calculated according to the following formula, and the difference significance was analyzed using SPSS software. Disease rate = (number of diseased plants) / total number of plants surveyed) × 100

[0214] Control effect (%) = [(blank control area disease rate - treatment area disease rate) / blank control area disease rate] × 100 test results

[0215] Table 24 Field control effect of the fungicide pentithiobacillus zinc of the present invention on tomato bacterial wilt

[0216]

[0217]

[0218] Note: Different lowercase letters after the data in the same column indicate significant differences (p < 0.05).

[0219] The test data shown in Table 24 show that the control effect of 20% pentithiophanate-zinc suspension concentrate (50-150 ml / mu) is significantly improved with increasing dosage, and the control effect against tomato bacterial wilt is best at a dosage of 150 ml / mu (69.34%), which is better than the control agent 20% thiazole zinc (68.19%). In addition, the concentration range used in this test is safe for tomatoes and no phytotoxicity occurs.

[0220] Currently, the acute toxicity test and toxicology test of penthiacin-zinc are entrusted to Xishan Zhongke Pharmaceutical Research Co., Ltd. for testing. Among them, the aquatic toxicity test is based on the acute toxicity classification standard of pesticides to fish in the National Standard of the People's Republic of China "Chemical Pesticide Environmental Safety Evaluation Test Guidelines Part 12: Fish Acute Toxicity Test" (GB / T31270.12-2014). The acute toxicity of penthiacin-zinc to zebrafish after 96 hours is "low toxicity". Through the "Daphnia Acute Activity Inhibition Test" and the test solution concentration and the average inhibition rate of Daphnia magna, the 48h-EC value of penthiacin-zinc to Daphnia magna can be calculated using DPS statistical analysis software (version 18.10). 50 The concentration of TG-025 on Daphnia magna was 3.20 mg ai / L, and its 95% confidence interval was 2.86 mg ai / L to 3.58 mg ai / L. According to the toxicity classification standard for pesticides in GB / T31270.13-2014), the acute toxicity of TG-025 on Daphnia magna for 48 hours under the conditions of this test was "poisonous". The acute toxicity was measured by the acute toxic reactions and deaths produced by oral administration of the test sample to SD rats. This test used the limit test method, with a designed dose of thiophanate-zinc of 5000 mg / kg body weight. The test results were the median lethal dose (LD50) of female and male SD rats. 50 ) were all > 5000 mg / kg, which were slightly toxic; the acute percutaneous median lethal dose (LD50) of female and male SD rats 50 ) are all greater than 2000 mg / kg, which is low toxicity; the acute inhalation toxicity test of thiabendazole zinc in rats showed that the oral and nasal exposure concentration range was 5040~5070 mg / m 3 Under the test sample aerosol environment (equivalent to the test sample inhalation dose of about 900 mg / kg), the female and male SD median lethal concentration (LC 50 )>5000mg / m 3 The sensitization rate of pentythiazolinone in Hartley guinea pigs was 0%. According to the pesticide sensitization intensity standard, the sensitization intensity was classified as weak sensitization. The acute percutaneous median lethal dose (LD50) of male and female SD rats was 0%. 50) were all > 2000 mg / kg body weight, which are low toxic; through the 24h, 48h and 72h observation time points, the average maximum score of the test sample penthiacozin zinc on the skin irritation of New Zealand white rabbits was 0. According to the pesticide skin irritation intensity grading standard: the skin irritation intensity of the test sample penthiacozin zinc on New Zealand white rabbits was graded as non-irritating; the eye irritation intensity of the test sample penthiacozin zinc on New Zealand white rabbits was graded as mild irritating (recovery after 24 hours). Genotoxicity tests revealed that the technical form of penthiafoxam zinc was non-mutagenic in all tested strains, a negative result. A micronucleus assay in mice with mammalian bone marrow polychromatophilic erythrocytes also revealed that the technical form of penthiafoxam zinc was non-mutagenic in mouse polychromatophilic erythrocytes, a negative result. A chromosome aberration assay in vitro revealed that the technical form of penthiafoxam zinc was non-mutagenic in cultured CHL mammalian cells, a negative result. Furthermore, an in vitro mammalian cell gene mutation assay revealed that the technical form of penthiafoxam zinc was negative in cultured mouse lymphoma cells (L5178YTK+ / - clone (3.7.2c), indicating that the technical form of penthiafoxam zinc did not induce mutations. Ecotoxicology and subchronic toxicity studies are ongoing. Based on these toxicological data, the toxicity of penthiafoxam zinc across all exposure routes is low, the exposure risk is manageable, and there is no significant genetic or allergenic toxicity. This meets pesticide safety requirements and demonstrates promising prospects for industrial application.

[0221] The present invention will be further described in detail below with reference to examples.

[0222] Weigh 5 g (37.54 mmol) of 2-amino-5-thio-1,3,4-thiadiazole as a raw material, use ethanol as a solvent, stir and heat until all the raw materials are dissolved, then cool to 30°C, slowly add formaldehyde or paraformaldehyde solution, react at room temperature (25±5°C) for 1-2 hours, add dilute hydrochloric acid to the reaction system, recrystallize the precipitated solid, vacuum filter, dry it, and dry it at 50-70°C. Finally, recrystallize to obtain 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocycle [14.2.1.1 4,7 .1 10,13 ]8.73g of Hennicosa-4(20),10(21),16(19)-triene-6,12,18-trithione (X5) compound, melting point greater than 250°C, content 93-95%, yield 51.40%.

[0223] Weigh the intermediate 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocycle [14.2.1.1 4,7 .1 10 ,13] 0.5 g (1.15 mmol) of Hennicosa-4 (20), 10 (21), 16 (19) -triene-6,12,18-trithione (X5) was placed in a 100 mL three-necked flask, water was added as solvent, 48.21 mg (1.21 mmol) of sodium hydroxide was added as acid binding agent, and finally 89.95 mg (0.66 mmol) of zinc chloride dissolved in water was added to the system, and the reaction was carried out at room temperature for 1-2 hours. After the reaction was completed, water was added and the precipitated solid was washed with water. The sample was filtered using a Buchner funnel or a three-necked funnel, and then dried to obtain chloro-bis[5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclo[14.2.1.14,7.110,13]hexone-4(20),10(21),16(19)-triene-6,12,18-trithione]zinc (penthioxazin) with a mass of 512 mg, a yield of 91.78%, and a melting point of greater than 250°C.

[0224] The above-obtained original drug, clay and surfactant can be ground into a 10% suspension concentrate, which can be prepared into 200-400 μg / mL with water and sprayed on plant leaves.

[0225] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Any simple modification, equivalent change and modification made to the above embodiment based on the technical essence of the present invention without departing from the content of the technical solution of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A pentathiabendazole zinc metal complex, characterized in that: The thiabendazole metal complex includes thiabendazole, or a stereoisomer thereof, or a salt thereof, or a solvate thereof. The chemical structural formula of the thiabendazole is as follows:

2. The method for preparing the pentathiabendazole zinc metal complex according to claim 1, wherein: The intermediate 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocycle [14.2.1.1 4,7 .1 10,13 ] Hennicosa-4(20), 10(21), 16(19)-triene-6,12,18-trithione (X5) is used as raw material to react to obtain penthiabendazole. The reaction equation is as follows:

3. The method for preparing the pentathiabendazole zinc metal complex according to claim 2, wherein: The method comprises the following steps: using 2-amino-5-thio-1,3,4-thiadiazole as a raw material, adding water as a solvent and sodium hydroxide as an acid-binding agent, stirring and dissolving, slowly adding formaldehyde or paraformaldehyde solution, reacting at room temperature for 1-2 hours, recrystallizing the precipitated solid, vacuum filtering, drying, and drying at 50-70° C. to obtain 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonane nitrogen heterocycle [14.2.1.1 4,7 .1 10,13 ]Hennicosa-4(20), 10(21), 16(19)-triene-6,12,18-trithione, which is intermediate X5; add intermediate X5 to sodium hydroxide aqueous solution, stir to dissolve all the raw materials, then add zinc chloride solution, react at room temperature for 1-2 hours, filter the precipitated solid with a Buchner funnel, and dry the sample at 50-80℃ after filtration.

4. A composition characterized in that The composition comprises the pentithiobacillus zinc metal complex according to claim 1, and an agriculturally applicable adjuvant or fungicide; the composition is in the form of a suspension, emulsifiable concentrate, powder, granule, aqueous solution, ultra-low volume spray, microcapsule, smoke agent, or aqueous emulsion.

5. Use of the pentithiobacillus zinc metal complex according to claim 1 in the preparation of a medicament for preventing and treating plant bacterial diseases; the plant bacterial diseases include rice bacterial leaf blight, rice bacterial leaf streak, citrus canker, citrus Huanglongbing, tomato bacterial wilt, tobacco bacterial wilt, peach shot hole disease, cabbage black rot, cabbage soft rot, melon bacterial angular leaf spot and watermelon bacterial fruit rot.

6. Use of the composition according to claim 4 in the preparation of a medicament for preventing and treating plant bacterial diseases; the plant bacterial diseases include rice bacterial leaf blight, rice bacterial leaf streak, citrus canker, citrus Huanglongbing, tomato bacterial wilt, tobacco bacterial wilt, peach shot hole disease, cabbage black rot, cabbage soft rot, melon bacterial angular leaf spot and watermelon bacterial fruit rot.

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