CN110551117A - Phenazine compound containing oxazole ring and application of phenazine compound as agricultural bactericide - Google Patents

Phenazine compound containing oxazole ring and application of phenazine compound as agricultural bactericide Download PDF

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CN110551117A
CN110551117A CN201910956284.4A CN201910956284A CN110551117A CN 110551117 A CN110551117 A CN 110551117A CN 201910956284 A CN201910956284 A CN 201910956284A CN 110551117 A CN110551117 A CN 110551117A
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phenazine
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oxazole
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CN110551117B (en
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叶永浩
陈议亮
严威
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Nanjing Agricultural University
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

The invention relates to phenazine compounds containing oxazole rings and application of the compounds as agricultural bactericides, wherein the compounds have the following general formula of

Description

Phenazine compound containing oxazole ring and application of phenazine compound as agricultural bactericide
Technical Field
The invention relates to a phenazine compound containing an oxazole ring and application thereof as a bactericide in plant disease control, belonging to the technical field of agricultural pharmacy.
Background
The natural phenazine compound is a secondary metabolite widely existing in microorganisms such as pseudomonas and streptomyces, and has different physical and chemical properties and multiple biological activities such as antibiosis, nematode resistance, antimalarial resistance, antioxidation, hypertension resistance, cell proliferation inhibition and the like due to different types and positions of functional groups on a phenazine ring. In the agricultural field, the agricultural antibiotic-shenqinmycin which is independently researched and developed in China is a phenazine compound generated by the metabolism of pseudomonas, has been registered as a pesticide at present, and is applied to the control of plant diseases such as gummy stem blight, root rot and the like.
Oxazole ring is a functional group having important biological activity, and various commercial pesticide varieties contain oxazole rings, such as famoxadone (famoxadone), metamifop (metamifop), chlozolinate (chlozolinate) vinclozolin (vinclozolin), and the like, and have been widely used. Thus, the oxazole ring has important value for the research and development of new pesticides.
Based on an active substructure splicing strategy, the invention introduces an oxazole functional group into a phenazine mother nucleus structure for the first time, and adopts a simple, convenient and economic synthesis method to efficiently synthesize a series of phenazine compounds containing oxazole rings with novel structures. Through determination, the compounds have remarkable antibacterial activity 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 synthesis method of a novel phenazine compound containing an oxazole ring and application of the phenazine compound in plant disease control.
The phenazine compound containing oxazole ring provided by the invention has the following structural general formula:
Wherein R is selected from: hydrogen, halogen, methyl, hydroxyl, amino, phenyl, phenoxy, difluoromethyl, trifluoromethyl, 1-6 carbon alkoxy, and 2-4 substituents represented by R. Wherein, the phenyl substituent group comprises phenyl and phenyl substituted by halogen, hydroxyl, amino and 1-6 carbon alkoxy.
The compound related to the invention can be synthesized by the following route and method, and is characterized by comprising the following four steps:
Step 1: adding aniline compound A and 2-bromo-3-nitrobenzoic acid into 2, 3-butanediol, adding CuCl, Cu powder and N-ethylmorpholine, heating at 70 deg.C, stirring for 15 hr, washing the obtained solution with 0.1M ammonia water, and filtering. The resulting solution was slowly poured into 2M HCl to prepare intermediate B.
Step 2: intermediate B and NaBH4Adding into 2M NaOAnd (4) heating and refluxing the solution in the H for 5H, cooling in an ice bath after the reaction is finished to obtain a sodium salt of the phenazine acid, and acidifying with dilute hydrochloric acid to obtain a phenazine-1-carboxylic acid intermediate C.
And step 3: and under the ice bath condition, dissolving the intermediate C in dichloromethane, dropwise adding oxalyl chloride and N, N-dimethylformamide under the protection of nitrogen, stirring at room temperature for 16h, removing volatile matters in vacuum, dissolving in dichloromethane, cooling to 0 ℃, dropwise adding ammonia water, stirring for half an hour, filtering the reaction product to obtain a solid, drying, and recrystallizing with ethyl acetate to obtain the phenazine-1-formamide intermediate D.
And 4, step 4: heating the mixture of the intermediate D and 1, 3-dichloroacetone at 130 ℃ for 1h, cooling to room temperature, adding water for quenching, extracting the mixture with dichloromethane, drying an organic phase with sodium sulfate, filtering, concentrating under reduced pressure, and carrying out column chromatography to obtain the target compound.
The synthesis of the phenazine compound containing the oxazole ring provided by the invention has the characteristics of simple steps, high yield and easiness in operation.
The invention relates to a phenazine compound containing an oxazole ring, which preferably has the following structure:
The activity of the phenazine compound containing the oxazole ring on plant pathogenic fungi provided by the invention comprises Rhizoctonia solani (Rhizoctonia solani), rice blast (Magnaporthe grisea), wheat gibberellic disease (Fusarium graminearum), wheat holomyces graminis (Gaeumannomyces graminis), wheat Rhizoctonia cerealis (Rhizoctonia cerealis), Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), tomato early blight (Alternaria solani), tomato gray mold (Botryis cinerea), cucumber colletotrichum (Colletochlorum lagenarium), potato late blight (Phytophthora infestans) and pepper mold (Phytophora capsici).
Detailed Description
The process of the present invention will be described below with reference to specific examples, but the present invention is not limited thereto. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials may be prepared commercially or by conventional methods, unless otherwise specified.
The first embodiment is as follows: preparation of 2- (1-phenazine) -4-chloromethyl oxazole (Compound 1)
Respectively adding aniline and 2-bromo-3-nitrobenzoic acid into 2, 3-butanediol, adding CuCl, Cu powder and N-ethylmorpholine, heating and stirring at 70 ℃ for 15h, washing with 0.1M ammonia water, filtering, and slowly pouring the obtained solution into 2M HCl to obtain an intermediate 3-nitro-2-phenylaminobenzoic acid; adding the phenazine and NaBH4 into a solution in 2M NaOH, refluxing for 5h, cooling in an ice bath, and acidifying with dilute hydrochloric acid to obtain phenazine-1-carboxylic acid; under the ice bath condition, dissolving phenazine-1-carboxylic acid in dichloromethane, dropwise adding oxalyl chloride and N, N-dimethylformamide under the protection of nitrogen, stirring at room temperature for 16h, removing volatile matters in vacuum, cooling to 0 ℃, dropwise adding ammonia water, stirring for half an hour, filtering the reactant to obtain a solid, drying, and recrystallizing with ethyl acetate to obtain phenazine-1-formamide; heating the mixture of the 2- (1-phenazine) -4-chloromethyl oxazole with 1, 3-dichloroacetone at 130 ℃ for 1h, cooling to room temperature, adding water for quenching, extracting the mixture with dichloromethane, drying an organic phase with sodium sulfate, filtering, concentrating under reduced pressure, and carrying out column chromatography to obtain the 2- (1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 68%.1H NMR(400MHz，CDCl3)δ8.53(dd，J＝7.0，1.4Hz，1H)，8.47(dd，J＝8.8，1.4Hz，1H)，8.38-8.35(m，1H)，8.34-8.31(m，1H)，8.00(s，1H)，7.96(dd，J＝8.7，7.0Hz，1H)，7.91(ddt，J＝9.1，6.6，3.3Hz，2H)，4.73(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：296.0591；found：296.0594。
Example two: preparation of 2- (9-fluoro-1-phenazine) -4-chloromethyl oxazole (compound 2)
The preparation method is the same as the first embodiment. 2, 6-difluoroaniline is used for replacing aniline to obtain 2- (9-fluoro-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 65%.1H NMR(400MHz，CDCl3)δ8.63(d，J＝7.1Hz，1H)，8.49(d，J＝2.4Hz，1H)，8.16(dt，J＝8.5，1.7Hz，2H)，8.04(d，J＝4.8Hz，1H)，7.91-7.87(m，1H)，7.64-7.58(m，1H)，4.74(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：314.0496；found：314.0499。
Example three: preparation of 2- (8-fluoro-1-phenazine) -4-chloromethyl oxazole (compound 3)
The preparation method is the same as the first embodiment. 2, 5-difluoroaniline is used for replacing aniline to obtain 2- (8-fluoro-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, 73% yield.1H NMR(400MHz，CDCl3)δ8.54(dd，J＝7.1，1.4Hz，1H)，8.43-8.37(m，2H)，8.23(d，J＝9.3Hz，1H)，8.03-7.93(m，2H)，7.84(dd，J＝9.3，2.1Hz，1H)，4.74(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：314.0496；found：314.0506。
Example four: preparation of 2- (7-fluoro-1-phenazine) -4-chloromethyl oxazole (compound 4)
The preparation method is the same as the first embodiment. And 4-fluoroaniline is used for replacing aniline to obtain 2- (7-fluoro-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 68%.1H NMR(400MHz，CDCl3)δ8.51(d，J＝7.1Hz，1H)，8.40(q，J＝7.7，6.6Hz，2H)，8.08-7.93(m，2H)，7.89(dd，J＝9.2，2.6Hz，1H)，7.72(t，J＝8.9Hz，1H)，4.74(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：314.0496；found：314.0499。
Example five: preparation of 2- (9-chloro-1-phenazine) -4-chloromethyl oxazole (compound 5)
the preparation method is the same as the first embodiment. 2-chloroaniline is used for replacing aniline to obtain 2- (9-chloro-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, 73% yield.1H NMR(400MHz，CDCl3)δ8.54(dd，J＝7.8，4.3Hz，2H)，8.31(d，J＝8.9Hz，1H)，8.18(s，1H)，8.01(s，1H)，7.97(dd，J＝8.7，7.1Hz，1H)，7.81(d，J＝8.9Hz，1H)，4.75(s，2H)，2.71(s，3H)。HRMS[ESI]m/z：calcd for([M+H]+)：330.0201；found：330.0197。
Example six: preparation of 2- (8-chloro-1-phenazine) -4-chloromethyl oxazole (compound 6)
The preparation method is the same as the first embodiment. 2-fluoro-5-chloroaniline is used for replacing aniline to obtain 2- (8-chloro-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, 73% yield.1H NMR(400MHz，CDCl3)δ9.48(s，1H)，8.28(dd，J＝7.8，1.7Hz，1H)，8.17(dd，J＝8.2，1.7Hz，1H)，7.11-7.04(m，2H)，6.99(ddd，J＝8.8，4.2，2.5Hz，1H)，6.90(dd，J＝7.1，2.5Hz，1H)，5.07(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：330.0201；found：330.0201。
Example seven: preparation of 2- (7-chloro-1-phenazine) -4-chloromethyl oxazole (Compound 7)
The preparation method is the same as the first embodiment. 4-chloroaniline is used for replacing aniline to obtain 2- (7-chloro-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 62%.1H NMR(400MHz，CDCl3)δ8.51(dd，J＝7.1，1.4Hz，1H)，8.38(dd，J＝8.7，1.4Hz，1H)，8.34-8.26(m，2H)，7.98(s，1H)，7.95(dd，J＝8.7，7.0Hz，1H)，7.81(dd，J＝9.2，2.3Hz，1H)，4.72(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：330.0201；found：330.0197。
Example eight: preparation of 2- (9-bromo-1-phenazine) -4-chloromethyl oxazole (compound 8)
The preparation method is the same as the first embodiment. 2-bromoaniline is used to replace aniline to obtain 2- (9-bromo-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 74%.1H NMR(400MHz，CDCl3)δ8.53(d，J＝7.0Hz，1H)，8.43(dd，J＝8.8，5.3Hz，1H)，8.40-8.34(m，1H)，8.31(q，J＝5.7Hz，1H)，8.01(s，1H)，7.96-7.88(m，2H)，4.74(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：373.9696；found：373.9692。
Example nine: preparation of 2- (8-bromo-1-phenazine) -4-chloromethyl oxazole (compound 9)
The preparation method is the same as the first embodiment. 2-fluoro-5-bromoaniline is used to replace aniline to obtain 2- (8-bromo-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 57%.1H NMR(400MHz，CDCl3)δ8.54(dd，J＝7.1，1.4Hz，1H)，8.43-8.37(m，2H)，8.23(d，J＝9.2Hz，1H)，8.04-7.93(m，2H)，7.84(dd，J＝9.3，2.2Hz，1H)，4.74(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：373.9696；found：373.9695。
experimental example ten: preparation of 2- (7-bromo-1-phenazine) -4-chloromethyl oxazole (compound 10)
the preparation method is the same as the first embodiment. 4-bromoaniline is used to replace aniline to obtain 2- (7-bromo-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, 73% yield.1H NMR(400MHz，CDCl3)δ8.56-8.50(m，2H)，8.50-8.46(m，1H)，8.23(dd，J＝9.3，5.2Hz，1H)，7.99(d，J＝5.8Hz，2H)，7.97(s，1H)，4.74(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：373.9696；found：373.9693。
Example eleven: preparation of 2- (9-iodo-1-phenazine) -4-chloromethyloxazole (Compound 11)
The preparation method is the same as the first embodiment. 2-iodoaniline is used for replacing aniline to obtain 2- (9-iodine-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 65%.1H NMR(400MHz，CDCl3)δ8.53(d，J＝7.0Hz，1H)，8.46(d，J＝8.8Hz，1H)，8.35(dq，J＝18.0，4.8，3.4Hz，3H)，7.96(dd，J＝9.0，6.5Hz，2H)，4.75(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：421.9557；found：421.9548。
Example twelve: preparation of 2- (8-iodo-1-phenazine) -4-chloromethyloxazole (Compound 12)
The preparation method is the same as the first embodiment. 2-fluoro-3-iodoaniline is used to replace aniline to obtain 2- (8-iodo-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 75%.1H NMR(400MHz，CDCl3)δ9.48(s，1H)，8.28(dd，J＝7.8，1.7Hz，1H)，8.17(dd，J＝8.2，1.7Hz，1H)，7.11-7.03(m，2H)，6.99(ddd，J＝8.8，4.2，2.5Hz，1H)，6.90(dd，J＝7.1，2.5Hz，1H)，5.07(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：421.9557；found：421.9556。
example thirteen: preparation of 2- (7-iodo-1-phenazine) -4-chloromethyloxazole (Compound 13)
the preparation method is the same as the first embodiment. Substituting aniline with 4-iodoaniline to obtain 2- (7-iodo-1-phenazine)4-chloromethyl oxazole. Yellow liquid, yield 62%.1H NMR(400MHz，CDCl3)δ8.53(d，J＝5.9Hz，1H)，8.41(d，J＝10.3Hz，1H)，8.31(t，J＝6.1Hz，1H)，8.09(d，J＝5.3Hz，1H)，7.99(d，J＝10.3Hz，2H)，4.74(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：421.9557；found：421.9552。
Example fourteen: preparation of 2- (9-methyl-1-phenazine) -4-chloromethyl oxazole (compound 14)
The preparation method is the same as the first embodiment. 2-methylaniline is used for replacing aniline to obtain 2- (9-methyl-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 72%.1H NMR(400MHz，CDCl3)δ8.50-8.46(m，1H)，8.42(d，J＝8.7Hz，1H)，8.24(d，J＝8.9Hz，1H)，8.05(s，1H)，7.99(d，J＝1.1Hz，1H)，7.93(dd，J＝8.5，7.2Hz，1H)，7.73(dd，J＝9.0，1.8Hz，1H)，4.72(s，2H)，2.68(s，3H)。HRMS[ESI]m/z：calcd for([M+H]+)：310.0747；found：310.0748。
Example fifteen: preparation of 2- (8-methyl-1-phenazine) -4-chloromethyl oxazole (compound 15)
The preparation method is the same as the first embodiment. 2-fluoro-5-methylaniline is used for replacing aniline to obtain 2- (9-methyl-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 82%.1H NMR(400MHz，CDCl3)δ8.54(dd，J＝7.8，4.3Hz，2H)，8.31(d，J＝8.9Hz，1H)，8.18(s，1H)，8.03-7.94(m，2H)，7.81(d，J＝8.9Hz，1H)，4.75(s，2H)，2.71(s，3H)。HRMS[ESI]m/z：calcd for([M+H]+)：310.0747；found：310.0748。
Example sixteen: preparation of 2- (7-methyl-1-phenazine) -4-chloromethyl oxazole (compound 16)
The preparation method is the same as the first embodiment. The 4-methylaniline is used for replacing aniline to obtain 2- (7-methyl-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 76%.1H NMR(400MHz，CDCl3)δ8.48(dd，J＝6.8，1.2Hz，1H)，8.42(d，J＝8.7Hz，1H)，8.24(d，J＝8.9Hz，1H)，8.05(s，1H)，7.99(s，1H)，7.93(dd，J＝8.5，7.2Hz，1H)，7.73(dd，J＝9.0，1.8Hz，1H)，4.72(s，2H)，2.68(s，3H)。HRMS[ESI]m/z：calcd for([M+H]+)：310.0747；found：310.0747。
example seventeen: preparation of 2- (9-methoxy-1-phenazine) -4-chloromethyl oxazole (compound 17)
The preparation method is the same as the first embodiment. 2-methoxyaniline is used for replacing aniline to obtain 2- (9-methoxy-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 75%.1H NMR(400MHz，CDCl3)δ8.98(d，J＝7.1Hz，1H)，8.46(d，J＝8.8Hz，1H)，8.28(d，J＝9.5Hz，1H)，8.01(t，J＝7.9Hz，1H)，7.70-7.61(m，1H)，7.54(d，J＝2.8Hz，1H)，5.32(s，1H)，4.97(s，2H)，4.10(s，3H)。HRMS[ESI]m/z：calcd for([M+H]+)：326.0696；found：326.0692。
Example eighteen: preparation of 2- (8-methoxy-1-phenazine) -4-chloromethyl oxazole (compound 18)
The preparation method is the same as the first embodiment. 2-fluoro-5-methoxyaniline is used for replacing aniline to obtain 2- (8-methoxy-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 62%.1H NMR(400MHz，CDCl3)δ8.54(d，J＝7.0Hz，1H)，8.46-8.40(m，1H)，8.32(s，2H)，8.02-7.96(m，2H)，7.84(d，J＝8.9Hz，1H)，4.75(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：326.0696；found：326.0693。
Example nineteenth: preparation of 2- (7-methoxy-1-phenazine) -4-chloromethyl oxazole (compound 19)
The preparation method is the same as the first embodiment. 4-methoxyaniline is used for replacing aniline to obtain 2- (7-methoxy-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 70%.1H NMR(400MHz，CDCl3)δ8.98(d，J＝7.1Hz，1H)，8.46(d，J＝8.8Hz，1H)，8.28(d，J＝9.5Hz，1H)，8.01(t，J＝7.9Hz，1H)，7.68-7.63(m，1H)，7.54(s，1H)，6.04(s，1H)，4.97(s，2H)，4.10(s，3H)。HRMS[ESI]m/z：calcd for([M+H]+)：326.0696；found：326.0697。
Example twenty: preparation of 2- (7-phenyl-1-phenazine) -4-chloromethyl oxazole (compound 20)
The preparation method is the same as the first embodiment. Substituting 4-benzidine for aniline to obtain 2- (7-phenyl-1-phenazine) -4-chloromethyl oxazole. Yellow liquid, yield 85%.1H NMR(400MHz，CDCl3)δ8.28-8.16(m，2H)，7.62-7.52(m，4H)，7.49-7.41(m，2H)，7.40-7.32(m，1H)，7.13-7.05(m，2H)，7.02(t，J＝8.0Hz，1H)，4.94(s，2H)。HRMS[ESI]m/z：calcd for([M+H]+)：372.0904；found：372.0899。
Example twenty one: determination of antibacterial activity of phenazine compound containing oxazole ring
The in vitro antibacterial activity evaluation is carried out by adopting a plate hypha growth rate inhibition method, and test strains are selected to be activated on a PDA plate, wherein the test strains comprise Rhizoctonia solani (Rhizoctonia solani), rice blast fungus (Magnaporthegrisea), wheat gibberellic disease (Fusarium graminearum), wheat holomyces graminis (Gaeumanomy graminis), wheat Rhizoctonia cerealis (Rhizoctonia cerealis), sclerotinia sclerotiorum (Sclerotinia sclerotiorum), tomato early blight (Alternaria solani), tomato gray mold (Botryis cinerea), cucumber Colletotrichum lagenarium (Colletotrichum laxatum), potato late blight (Phytophthora infestans) and capsicum (Phytophthora capsici).
Preparing the compound into a PDA drug-containing flat plate with the concentration of 20 mu g/mL, preparing a bacterial cake with the diameter of 5mm from a test strain, placing the bacterial cake in the center of a drug-containing culture dish, culturing at the constant temperature of 25 ℃ until the test strain in a blank control dish grows to be close to the edge of the culture dish, measuring the colony diameter of each drug-containing flat plate by using a cross method, repeating for 3 times, calculating the average value, and comparing with the blank control to calculate the relative bacteriostasis rate. The inhibition rate of the disease is calculated according to the following formula:
Further preparing the compound into PDA drug-containing flat plate with gradient concentration, obtaining the bacteriostatic rate by the same method, and calculating the concentration of the compound when the inhibitory rate is 50%, namely EC by using SPSS 20.0 statistical software50The value is obtained. Phenazine-1-carboxylic acid (shenqinmycin), Phenamacril (Phenamacril) and Carbendazim (Carbendazim) were used as positive controls.
TABLE 1 inhibitory ratio (%)% of phenazine compound containing oxazole ring at 20. mu.g/mL concentration to phytopathogen
TABLE 2 EC of oxazacyclo-containing phenazine compounds against phytopathogens50Value of
As can be seen from tables 1 and 2, the phenazine compounds containing oxazole ring have certain inhibition effect on the growth of three plant pathogenic fungiCompared with the commercial pesticide phenazine-1-carboxylic acid (shenqinmycin), the bacteriostatic activity is obviously improved. Wherein the inhibition medium concentration of the compounds 4, 14 and 17 to sclerotinia sclerotiorum is less than 1.0 mu g/mL, and is close to positive control carbendazim (EC)50Equal to 0.33 mug/mL) and better than another positive control phenamacril (EC)507.83 μ g/mL). Therefore, the compounds have the potential of further development and application as novel agricultural bactericides.
The use of the phenazine compounds containing an oxazole ring as agricultural fungicides of the present invention has been described by way of specific examples, and those skilled in the art can refer to the present invention and appropriately modify the raw materials, process conditions, etc. to achieve other objects without departing from the present invention, and all such substitutions and modifications will be obvious to those skilled in the art and are intended to be included within the scope of the present invention.

Claims (6)

1. A kind of cyclic phenazine compound containing oxazole, its characteristic is that it has the following general formula:
Wherein R is selected from: hydrogen, halogen, methyl, hydroxyl, amino, phenyl, phenoxy, difluoromethyl, trifluoromethyl, 1-6 carbon alkoxy, and 2-4 substituents represented by R.
2. The compound of formula (la) of claim 1, comprising the following compounds:
3. The use of the phenazine compounds containing an oxazole ring as claimed in claim 1 for controlling agricultural plant diseases.
4. the use as claimed in claim 3, characterized in that the agricultural diseases are rice sheath blight, sclerotinia rot of colza, wheat scab.
5. According to the use of the compounds 3 and 4, the compounds can be processed into missible oil, aqueous emulsion, microemulsion, wettable powder, water dispersible granule, suspending agent and other suitable formulations.
6. The application of the phenazine compound containing oxazole ring in preventing and treating plant diseases as claimed in claim 1 and 2, which is characterized in that the phenazine compound is combined with one or more of commercial bactericides to prepare compound bactericides; the commercial fungicide is selected from azoxystrobin, pyraclostrobin, prothioconazole, mancozeb, epoxiconazole, tebuconazole, prochloraz, boscalid, fluopicolide, metalaxyl, difenoconazole, propiconazole, chlorothalonil, validamycin, carbendazim and cyhalonil.
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Citations (3)

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CN107188858A (en) * 2017-06-12 2017-09-22 长江大学 The formyl piperazine compound of azophenlyene 1 and its application
CN107382988A (en) * 2017-07-10 2017-11-24 长江大学 A kind of furodiazole compound of 2 substituted Thio 5 (1 phenazinyl) 1,3,4 and its application
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WO2018118781A1 (en) * 2016-12-20 2018-06-28 Fmc Corporation Fungicidal oxadiazoles
CN107188858A (en) * 2017-06-12 2017-09-22 长江大学 The formyl piperazine compound of azophenlyene 1 and its application
CN107382988A (en) * 2017-07-10 2017-11-24 长江大学 A kind of furodiazole compound of 2 substituted Thio 5 (1 phenazinyl) 1,3,4 and its application

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