CN111875559B - Thiazole hydrazide derivatives and application thereof as agricultural bactericide - Google Patents
Thiazole hydrazide derivatives and application thereof as agricultural bactericide Download PDFInfo
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- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
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Abstract
The invention relates to the field of organic chemistry and agricultural pharmacy, and discloses a derivative containing a thiazole hydrazide structure and application thereof. The chemical structural general formula of the thiazole hydrazide derivative is as follows:
in the formula R 1 、R 2 Each independently selected from hydrogen, halogen, C 1‑6 Alkyl, hydroxy, amino, nitro, difluoromethyl, trifluoromethyl, C 1‑6 And C substituted by 1 to 3 halogens 1‑6 And C substituted by 1 to 3 halogens 1‑6 An alkoxy group of (2). The compound has good antibacterial activity on plant pathogenic bacteria, and can be used as an agricultural bactericide for preventing and treating plant diseases.
Description
Technical Field
The invention relates to a derivative containing a thiazole hydrazide structure and application thereof as an agricultural bactericide in prevention and treatment of crop diseases, belonging to the technical field of organic synthetic chemistry and agricultural pharmacy.
Background
Thiazole rings are important five-membered aromatic heterocycles containing nitrogen and sulfur heteroatoms, and have wide application prospects in various fields of chemistry, pharmacy, biology, material science and the like. In the field of agricultural fungicide development, thiazole structures have attracted much attention because they have good antifungal, antibacterial and antiviral activities and are low toxic to the human body, and many commercial fungicides such as Thiabendazole (Thiabendazole), fenchlorazole (chlobenzone), probenazole (Oryzemate), thiafluzamide (Thifluzamide), ethaboxam (Ethaboxam) and the like have been successfully developed. In addition to this, many antibacterial active compounds containing thiazole rings are reported every year, showing that the thiazole structure is still one of hot spots in the development of bactericides (Mishra I., mishra R., mujwar S., et al. A retrospecton antibacterial potential of thiazole scaffold [ J ]. Journal of Heterocyclic Chemistry 2020, 57, 2304-2329).
The nitrogen-containing heterocyclic compound plays an important role in the creation of novel pesticides, and the inventor designs and synthesizes a series of compounds containing a 1,2,3-triazole hydrazide structure in earlier work, wherein partial compounds have excellent control effects on rice sheath blight, sclerotinia rot of rape and wheat scab, are equivalent to positive control carbendazim and validamycin, and are novel bactericide candidate compounds (Wang X., dai Z.C., chen Y.F., et al.Synthesis of 1,2,3-triazole hydraderivative exhibitting anti-bacterial [ J ]. European Journal of Medicinal Chemistry,2017, 126, 171-182.).
Biological isostere is one of very important means in drug research and development, and the properties such as the size, the shape, the electron distribution, the polarity, the pKa (pKa), the hydrogen bond capacity and the like of molecules can be changed through electronic isostere replacement, so that the activity can be optimized, the selectivity can be increased, the physicochemical property can be improved, the metabolism can be improved, the toxic and side effects can be reduced, and the like. Based on a biological electron isostere strategy, the triazole heterocycle in the 1,2,3-triazole hydrazide compound with obvious bactericidal activity is replaced by a biological electron isostere thiazole heterocycle, and a series of thiazole hydrazide derivatives are designed and synthesized. Tests prove that part of compounds have obvious inhibitory activity on the growth of plant pathogenic bacteria and have the potential of being used as a novel agricultural bactericide for development and application.
Disclosure of Invention
The invention aims to provide a novel compound containing a thiazole hydrazide structural skeleton as an agricultural bactericide for preventing and controlling plant diseases.
The technical scheme of the invention is as follows:
a derivative containing thiazole hydrazide structure is characterized by having the following general formula:
in the formula, R 1 、R 2 Each independently selected from hydrogen, halogen, C 1-6 Alkyl, hydroxy, amino, nitro, difluoromethyl, trifluoromethyl, C 1-6 And C substituted by 1 to 3 halogens 1-6 And C substituted by 1 to 3 halogens 1-6 Alkoxy group of (2).
The preparation method of the thiazole hydrazide derivative comprises the following steps:
step A. Preparation of R 1 Different substituted 4-phenylthiazole-2-carboxylic acid ethyl esters or 2-phenylthiazole-4-carboxylic acid ethyl esters;
step B preparation of R 1 A differently substituted 4-phenylthiazole-2-carboxylic acid or 2-phenylthiazole-4-carboxylic acid;
step C, preparation ofR is prepared 1 The differently substituted 4-phenylthiazole-2-carboxylic acids or 2-phenylthiazole-4-carboxylic acids (1 eq) were dissolved in dichloromethane and R was added 2 Different substituted phenylhydrazine hydrochloride (1 eq), triethylamine (2 eq) and 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea Hexafluorophosphate (HATU) (1.2 eq) are stirred for reaction for 1 hour, and then purified by a silica gel column to obtain the 4-phenylthiazole-2-hydrazide derivative or the 2-phenylthiazole-4-hydrazide derivative.
Five agriculturally important plant pathogens are selected: the in vitro inhibitory activity of 4-phenylthiazole-2-hydrazide derivatives and 2-phenylthiazole-4-hydrazide derivatives against Fusarium graminearum (Fusarium graminearum), botrytis cinerea (Botrytis cinerea), sclerotinia sclerotiorum (sclerotiorum) and Phytophthora capsici (Phytophthora capsici) was measured at a concentration of 5 μ g/mL by a drug-containing medium method as test strains. The results show that the series of compounds generally have remarkable antibacterial activity and can be used for preparing novel agricultural bactericides.
Detailed Description
The first embodiment is as follows: preparation of 4- (2-chlorophenyl) -N' - (4-chlorophenyl) thiazole-2-hydrazide (Compound 1)
i) Adding 2-chlorobromopropiophenone (1 eq) into a reaction bottle, adding ethanol as a solvent, adding ethyl 2-amino-2-thioacetate (1.5 eq) under the condition of stirring, and heating and refluxing for reaction for 6 hours. After the reaction is finished, extracting with ethyl acetate, and purifying the crude product by a silica gel column to obtain the 4- (2-chlorphenyl) thiazole-2-carboxylic acid ethyl ester.
ii) the product (1 eq) obtained in the first step was added with sodium hydroxide (2 eq) and heated under reflux in methanol for 4 hours. After the reaction is finished, removing the methanol under reduced pressure, adding a small amount of water into the system, acidifying the system to the pH value of 2 by using dilute hydrochloric acid, performing suction filtration, and drying to obtain a white solid, namely the 4- (2-chlorphenyl) thiazole-2-carboxylic acid.
iii) The product obtained in the second step (1 eq) was dissolved in dichloromethaneTo the alkane, 4-chlorophenylhydrazine hydrochloride (1 eq), triethylamine (2 eq) and 2- (7-benzotriazol oxide) -N, N' -tetramethyluronium Hexafluorophosphate (HATU) (1.2 eq) were added and reacted for 1 hour. After the reaction, the product was purified by a silica gel column to obtain compound 1. The product was a pale yellow powder with 76% yield. m.p.153.3-153.5 ℃. 1 H NMR(400MHz，DMSO)δ10.87(s，1H)，8.48(s，1H)，8.27(s，1H)，8.11(dd，J＝7.5，1.9Hz，1H)，7.61(dd，J＝15.2，13.7Hz，2H)，7.49(dq，J＝7.5，5.7Hz，2H)，7.21(d，J＝8.8Hz，1H)，6.79(d，J＝8.8Hz，1H).m/z：364.01[M+H] + .
Example two: preparation of 4- (2-chlorophenyl) -N' - (4-fluorophenyl) thiazole-2-hydrazide (Compound 2)
In the same way as in example one, phenylhydrazine hydrochloride is changed to 4-fluorophenylhydrazine hydrochloride to obtain compound 2. The product was a yellow powder, 75% yield; m.p.139.6-140.0 ℃. 1 H NMR(400MHz，DMSO)δ10.85(s，1H)，8.47(s，1H)，8.12(dd，J＝7.5，1.9Hz，1H)，7.62(dd，J＝7.6，1.5Hz，1H)，7.48(ddd，J＝12.5，7.3，3.3Hz，2H)，7.02(dd，J＝12.3，5.5Hz，2H)，6.84-6.77(m，2H).m/z：348.0369[M+H] + .
Example three: preparation of 4- (2-chlorophenyl) -N' - (4-methylphenyl) thiazole-2-hydrazide (Compound 3)
The preparation method is the same as that in the first example, the phenylhydrazine hydrochloride is changed to 4-methylphenylhydrazine hydrochloride, and the compound 3 is obtained. The product was a yellow powder with a yield of 70%; m.p.145.2-145.8 ℃. 1 H NMR(400MHz，DMSO)δ10.71(s，1H)，8.41(s，1H)，8.09(dd，J＝7.4，2.0Hz，1H)，7.57(dd，J＝7.6，1.4Hz，1H)，7.43(ddd，J＝15.4，7.6，1.8Hz，3H)，6.94(d，J＝8.3Hz，2H)，6.66(d，J＝8.3Hz，1H)，2.15(s，3H).m/z：344.0621[M+H] + .
Example four: preparation of 4- (3-chlorophenyl) -N' - (4-chlorophenyl) thiazole-2-hydrazide (Compound 4)
The preparation method is the same as that in the first example, 2-chlorobromopropiophenone is changed to 3-chlorobromopropiophenone, and phenylhydrazine hydrochloride is changed to 4-chlorophenylhydrazine hydrochloride, so that the compound 4 is obtained. The product was a brown powder with a yield of 63%; m.p.142.3-142.6 ℃. 1 H NMR(400MHz，DMSO)δ10.86(s，1H)，8.48(s，1H)，7.99(d，J＝1.9Hz，1H)，7.73-7.70(m，1H)，7.49(dq，J＝7.5，5.7Hz，2H)，7.21(d，J＝8.8Hz，2H)，6.84-6.79(m，2H).m/z：364.0076[M+H] + .
Example five: preparation of 4- (3-chlorophenyl) -N' - (4-methylphenyl) thiazole-2-hydrazide (Compound 5)
The preparation method is the same as that in the first example, 2-chlorobromopropiophenone is changed to 3-chlorobromopropiophenone, and phenylhydrazine hydrochloride is changed to 4-methylphenylhydrazine hydrochloride, so that the compound 5 is obtained. The product was a yellow powder with a yield of 70%; m.p.136.8-137.3 ℃. 1 H NMR(400MHz，DMSO)δ9.98(s，1H)，8.58(s，1H)，7.97(d，J＝2.1Hz，1H)，7.73(d，J＝1.5Hz，1H)，7.50-7.47(m，2H)，7.11(d，J＝6.4Hz，2H)，6.88-6.83(m，2H).m/z：344.0631[M+H] + .
Example six: preparation of N', 4-bis (4-chlorophenyl) thiazole-2-hydrazide (Compound 6)
The preparation method is the same as that in the first example, 2-chlorobromopropiophenone is changed to 4-chlorobromopropiophenone, and phenylhydrazine hydrochloride is changed to 4-chlorophenylhydrazine hydrochloride, so that the compound 6 is obtained. The product is yellow powderFinally, the yield is 52%; m.p.138.9-139.7 ℃. 1 H NMR(400MHz，DMSO)δ10.81(s，1H)，8.44(s，1H)，8.04(d，J＝5.3Hz，2H)，7.54(d，J＝3.6Hz，2H)，7.25-7.19(m，2H)，6.84-6.79(m，2H).m/z：364.0070[M+H] + .
Example seven: preparation of 4- (4-chlorophenyl) -N' - (4-methylphenyl) thiazole-2-hydrazide (Compound 7)
The preparation method is the same as that in the first example, 2-chlorobromopropiophenone is changed to 4-methylbromopropiophenone, and phenylhydrazine hydrochloride is changed to 4-methylphenylhydrazine hydrochloride, so that the compound 7 is obtained. The product was a yellow powder with a yield of 70%; m.p.147.8-148.2 ℃. 1 H NMR(400MHz，DMSO)δ10.83(s，1H)，8.46(s，1H)，8.02(d，J＝3.8Hz，2H)，7.50(d，J＝5.1Hz，2H)，7.25-7.17(m，2H)，6.84-6.77(m，2H)，2.32(s，3H).m/z：344.0630[M+H] + .
Example eight: preparation of N', 2-diphenylthiazole-4-hydrazide (Compound 8)
i) Benzamide (1 eq) and Lawson's reagent (0.8 eq) were added to a reaction flask, and a small amount of toluene was added as a solvent, and reacted at 60 ℃ for 6 hours. And after the reaction is finished, purifying by a silica gel column to obtain the thiobenzamide.
ii) adding ethyl bromopyruvate (1.2 eq) into the product (1 eq) obtained in the first step, and heating and refluxing the mixture in ethanol for reaction for 8 hours. After the reaction is finished, the solvent is removed under reduced pressure, and the crude product is purified by a silica gel column to obtain the 2-phenylthiazole-4-ethyl ester.
iii) Sodium hydroxide (2 eq) was added to the product (1 eq) obtained in the second step and refluxed in methanol for 4 hours. And after the reaction is finished, removing the methanol under reduced pressure, adding a small amount of water into the system, acidifying the system to the pH value of 2 by using dilute hydrochloric acid, performing suction filtration, and drying to obtain a white solid, namely the 2-phenylthiazole-4-carboxylic acid.
iv) dissolving the product (1 eq) obtained in the third step in dichloromethane, adding 4-chlorophenylhydrazine hydrochloride (1 eq), triethylamine (2 eq) and 2- (7-benzotriazole oxide) -N, N, N ', N' -tetramethylurea Hexafluorophosphate (HATU) (1.2 eq) and reacting for 1 hour. After the reaction, the reaction mixture was purified by a silica gel column to obtain compound 8. The product was a white powder, yield 80%; m.p.159.0-160.3 ℃. 1 H NMR(600MHz，CDCl 3 )δ10.03(s，1H)，8.19(s，1H)，8.01(d，J＝2.2Hz，1H)，8.0(dd，J＝3.5，2.1Hz，2H)，7.46(d，J＝2.3Hz，3H)，7.45(d，J＝1.2，2H)，7.24-7.22(dd，J＝8.5，7.5Hz，1H)，6.85(dd，J＝8.6，1.0Hz，1H).m/z：296.28[M+H] + .
Example nine: preparation of N' - (2-fluorophenyl) -2-phenylthiazole-4-hydrazide (compound 9)
The preparation method is the same as example eight, and phenylhydrazine hydrochloride is changed to 2-fluorophenylhydrazine hydrochloride, so that the compound 9 is obtained. The product was a pale yellow powder with 59% yield. m.p.152.8-153.8 ℃. 1 H NMR(600MHz，CDCl 3 )δ9.04(s，1H)，8.18(s，1H)，8.00-7.98(m，2H)，7.51-7.49(m，3H)，7.07-7.00(m，3H)，6.88-6.85(m，1H).m/z：314.20[M+H] + .
Example ten: preparation of N' - (4-chlorophenyl) -2-phenylthiazole-4-hydrazide (Compound 10)
The preparation method is the same as example eight, and the phenylhydrazine hydrochloride is changed to 4-chlorophenylhydrazine hydrochloride to obtain the compound 10. The product was a pale yellow powder, 78% yield; m.p.166.4-167.2 ℃. 1 H NMR(600MHz，DMSO-d 6 )δ10.50(d，J＝2.2Hz，1H)，8.40(s，1H)，8.19(d，J＝2.2Hz，1H)，8.13-8.12(m，2H)，7.56-7.54(m，3H)，7.20-7.19(d，J＝8.6Hz，2H)，6.80-6.78(d，J＝8.8Hz，2H).m/z：330.46[M+H] + .
Example eleven: preparation of N' - (p-tolyl) 2-phenylthiazole-4-hydrazide (compound 11)
The preparation method is the same as example eight, and the phenylhydrazine hydrochloride is changed to 4-methylphenylhydrazine hydrochloride to obtain the compound 11. The product was a pale yellow powder in 66% yield. m.p.142.8-143.6 ℃. 1 H NMR(600MHz，Acetone-d 6 )δ9.42(s，1H)，8.27(s，1H)，8.15-8.13(m，2H)，7.55-7.54(m，3H)，7.01-7.00(d，J＝8.3Hz，2H)，6.87-6.85(d，J＝8.4Hz，2H)，2.21(s，3H).m/z：310.31[M+H] + .
Example twelve: preparation of N' - (4-nitrophenyl) -2-phenylthiazole-4-hydrazide (compound 12)
The preparation method is the same as example eight, and the phenylhydrazine hydrochloride is changed into 4-nitrophenylhydrazine hydrochloride to obtain the compound 12. The product was a yellow powder in 62% yield. m.p.167.2-167.5 ℃. 1 H NMR(600MHz，Acetone-d 6 )δ10.79(s，1H)，9.32(s，1H)，8.48(s，1H)，8.17-8.15(d，J＝9.4Hz，1H)，8.13-8.12(dd，J＝7.5，3.0Hz，2H)，8.10-8.09(d，J＝9.5Hz，1H)，7.57-7.51(m，3H)，6.85-6.83(d，J＝9.3Hz，2H).m/z：341.26[M+H] + .
Example thirteen: preparation of N' - (4-chlorophenyl) -2- (2-methylphenyl) thiazole-4-hydrazide (Compound 13)
The preparation method is the same as that in the eighth example, the benzamide is changed into the 2-methylbenzamide, and the phenylhydrazine hydrochloride is changed into the 4-chlorophenylhydrazine hydrochloride, so that the compound 13 is obtained. The product is light yellow powder, and is producedThe ratio was 67%. m.p.187.6-188.5 ℃. 1 H NMR(600MHz，DMSO-d 6 )δ9.73(s，1H)，8.37(s，1H)，7.89-7.88(d，J＝7.7Hz，1H)，7.44-7.40(m，3H)，7.37-7.35(m，1H)，7.20-7.18(m，2H)，6.95-6.94(d，J＝8.8Hz，2H)，2.67(m，3H).m/z：344.05[M+H] + .
Example fourteen: preparation of N' - (4-chlorophenyl) -2- (3-methylphenyl) thiazole-4-hydrazide (compound 14)
The preparation method is the same as that in the eighth example, the benzamide is changed to the 3-methylbenzamide, and the phenylhydrazine hydrochloride is changed to the 4-chlorophenylhydrazine hydrochloride, so that the compound 14 is obtained. The product was a pale yellow powder with 81% yield. m.p.142.5-144.5 ℃. 1 H NMR(600MHz，DMSO-d 6 )δ10.02(s，1H)，8.27(s，1H)，7.97(s，1H)，7.92-7.91(d，J＝7.8Hz，1H)，7.46-7.35(m，3H)，7.20-7.19(d，J＝8.8Hz，2H)，6.96-6.94(m，2H)，2.43-2.42(m，3H).m/z：344.05[M+H] + .
Example fifteen: preparation of N' - (4-chlorophenyl) -2- (2-chlorophenyl) thiazole-4-hydrazide (Compound 15)
In the same manner as in example eight, benzamide was changed to 2-chlorobenzamide, and phenylhydrazine hydrochloride was changed to 4-chlorophenylhydrazine hydrochloride, to obtain compound 15. The product was a pale yellow powder, 80.9% yield; m.p.146.4-146.9 ℃. 1 H NMR(600MHz，DMSO-d 6 )δ10.05(s，1H)，8.60-8.57(m，1H)，8.46(s，1H)，7.67-7.65(dd，J＝8.0，1.6Hz，1H)，7.57-7.52(m，2H)，7.20-7.19(d，J＝8.3Hz，2H)，6.97-6.94(dd，J＝9.0，2.8Hz，2H).m/z：364.02[M+H] + .
Example sixteen: preparation of N' - (4-chlorophenyl) -2- (3-chlorophenyl) thiazole-4-hydrazide (Compound 16)
The preparation method is the same as that in the eighth example, the product is that benzamide is changed into 3-chlorobenzamide, and phenylhydrazine hydrochloride is changed into 4-chlorophenylhydrazine hydrochloride, so that the compound 16 is obtained. Pale yellow powder, yield 60.1%; m.p.174.1-174.3 ℃. 1 H NMR(600MHz，DMSO-d 6 )δ10.18(s，1H)，8.35(s，1H)，8.24(s，1H)，8.02(m，1H)，7.58-7.56(m，2H)，7.48-7.46(m，1H)，7.21-7.19(d，J＝8.7Hz，2H)，6.96-6.94(dd，J＝8.9，2.7Hz，2H).m/z：364.02[M+H] + .
Example seventeen: preparation of N', 2-bis (4-chlorophenyl) thiazole-4-hydrazide (Compound 17)
The preparation method is the same as that in example eight, benzamide is changed into 4-chlorobenzamide, and phenylhydrazine hydrochloride is changed into 4-chlorophenylhydrazine hydrochloride, so that the compound 17 is obtained. The product was a pale yellow solid, 77.6% yield; m.p.251.0-252.0 ℃. 1 H NMR(600MHz，DMSO-d 6 )δ10.07(s，1H)，8.33(m，1H)，8.17-8.13(m，2H)，7.62-7.58(m，2H)，7.48-7.46(d，J＝8.8Hz，1H)，7.21-7.19(d，J＝8.8Hz，2H)，6.96-6.94(m，1H).m/z：364.02[M+H] + .
Example eighteen: determination of anti-phytopathogen activity of thiazole heterocyclic hydrazide derivative
The test strains are activated on a PDA plate by selecting wheat scab (Fusarium graminearum), botrytis cinerea (Botrytis cinerea), sclerotinia sclerotiorum (Sclerotinia sclerotiorum), rhizoctonia solani (Rhizoctonia solani) and Phytophthora capsici (Phytophtora capsicii) as test strains. Preparing PDA drug-containing plates with drug-containing concentration of 5 mug/mL by using the compounds, preparing a 5mm diameter bacterial cake of a test strain into the center of a drug-containing culture dish, culturing at a constant temperature of 25 ℃ until the test bacterial colony of a blank control dish grows to be larger than 5cm, measuring the bacterial colony diameter of each drug-containing plate by using a cross method, and calculating the inhibition rate of each compound on the growth of hyphae.
Table 1: inhibition ratio (%)% of compound 1-17 at 5. Mu.g/mL against five plant pathogenic bacteria
As can be seen from the table 1, the thiazole-2-hydrazide derivative or the thiazole-4-hydrazide derivative has a remarkable inhibition effect on the hypha growth of phytopathogens, wherein the compounds 1, 10, 13 and 15 show antibacterial activity superior to other compounds, and the thiazole hydrazide derivative is proved to have the potential of being used as a novel agricultural bactericide for development and application.
The description is given for the sole purpose of illustrating the invention concept in its implementation form and the scope of the invention should not be considered as being limited to the particular form set forth in the examples.
Claims (5)
1. A thiazole hydrazide derivative is characterized by having the following two general formulas:
in the general formula I, R 1 Selected from 2-Cl or 3-Cl, R 2 Selected from 4-F or 4-Cl; in the general formula II, R 1 Selected from H, 2-Cl, 2-CH 3 Or 3-CH 3 ，R 2 Selected from 2-F, 4-Cl or 4-CH 3 。
2. The thiazole hydrazide derivative as claimed in claim 1 for controlling agricultural plant diseases.
3. The use according to claim 2, wherein the agricultural plant diseases are rice sheath blight, gray mold, sclerotinia rot of colza, wheat scab and phytophthora capsici.
4. The use of claim 2, wherein the thiazole hydrazide derivative can be processed into emulsifiable concentrates, aqueous emulsions, microemulsions, wettable powders, water dispersible granules, suspending agents or other suitable formulations.
5. The use of the thiazole hydrazide derivative as claimed in claim 1 for controlling plant diseases, which is characterized by the use of the derivative in combination with one or more commercial bactericides for preparing compound bactericides; the commercial fungicide is selected from azoxystrobin, pyraclostrobin, prothioconazole, mancozeb, epoxiconazole, tebuconazole, prochloraz, boscalid, fluopicolide, metalaxyl, difenoconazole, propiconazole, chlorothalonil, validamycin, carbendazim and cyazoxystrobin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010823847.5A CN111875559B (en) | 2020-08-17 | 2020-08-17 | Thiazole hydrazide derivatives and application thereof as agricultural bactericide |
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| WO2010012793A1 (en) * | 2008-08-01 | 2010-02-04 | Bayer Cropscience Sa | Fungicide aminothiazole derivatives |
| KR20150052463A (en) * | 2013-11-05 | 2015-05-14 | 주식회사 대웅제약 | Novel compound, method for preparation thereof, and antifungal composition comprising the same |
| CN104926738A (en) * | 2015-06-08 | 2015-09-23 | 南京农业大学 | Application of 1,2,3-triazole-4-hydrazide derivatives to preparation of agricultural bactericide |
| CN106831615A (en) * | 2017-02-15 | 2017-06-13 | 南京农业大学 | One class 1,2,3-triazoles -5- amides compounds as disinfectant use in agriculture application |
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| WO2010012793A1 (en) * | 2008-08-01 | 2010-02-04 | Bayer Cropscience Sa | Fungicide aminothiazole derivatives |
| KR20150052463A (en) * | 2013-11-05 | 2015-05-14 | 주식회사 대웅제약 | Novel compound, method for preparation thereof, and antifungal composition comprising the same |
| CN104926738A (en) * | 2015-06-08 | 2015-09-23 | 南京农业大学 | Application of 1,2,3-triazole-4-hydrazide derivatives to preparation of agricultural bactericide |
| CN106831615A (en) * | 2017-02-15 | 2017-06-13 | 南京农业大学 | One class 1,2,3-triazoles -5- amides compounds as disinfectant use in agriculture application |
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