CN114380815B - Plant protection camalexin derivative and preparation method and application thereof - Google Patents

Plant protection camalexin derivative and preparation method and application thereof Download PDF

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CN114380815B
CN114380815B CN202210065421.7A CN202210065421A CN114380815B CN 114380815 B CN114380815 B CN 114380815B CN 202210065421 A CN202210065421 A CN 202210065421A CN 114380815 B CN114380815 B CN 114380815B
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camalexin
bromo
thiazole
derivative
carbohydrazide
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CN114380815A (en
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卢爱党
李林
王兹稳
廖安财
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Hebei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

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Abstract

The invention relates to a plant protection element camalexin derivative, a preparation method and application thereof. The structural general formula of the plant protection element camalexin derivative is shown as I, a new substituent group is introduced into the derivative based on alkaloid camalexin, a bromine atom is introduced into the 5-position of a core skeleton indole structural unit of a natural product camalexin, and a hydrazone functional group is introduced into the 4-position of a thiazole structural unit, so that a series camalexin derivative is generated. The alkaloid plant protection element camalexin derivative has good anti-plant virus activity and broad-spectrum plant pathogen killing activity.

Description

Plant protection camalexin derivative and preparation method and application thereof
Technical Field
The invention belongs to the technical field of fine chemicals, and particularly relates to a plant protection element camalexin derivative, a preparation method thereof and an application of the plant protection element camalexin derivative serving as a biocide in agriculture.
Background
Camalexin (3-thiazol-2' -yl-indole, as shown in structural formula one) is a plant protection agent specific to crucifers, also known as camelina, which is a sulfur-containing indole alkaloid, and representative phytoalexins or plant protection agents produced by crucifers after external stimuli can be induced by a variety of pathogens (e.g., bacteria, fungi, viruses, oomycetes, etc. [ GLAWISCHNIG, e.camalexin. Phytochem.2007,68 (4), 401-406 ].
From 1991 Browne et al [ Browne L.M; conn, K.L; ayer, W.A; tewari, j.p. tetrahedron 1991,47 (24), 3909-3914, ] since phytoalexins camalexin were first isolated from leaves of camellia japonica, phytoalexins camalexin and derivatives thereof have not only a protective effect on crops in agricultural production, but also bioactive [Yamashita,N.;Taga,C.;Ozawa,M.;Sanada,N.;Kizu,R.J.Nat.Med.2022,76,110–118;Mezencev,R.;Mojzis,J.;Pilatova,M.;Kutschy,P.Neoplasma 2003,50,239–245;Pilatova,M.;Ivanova,L.;Kutschy,P.;Varinska,L.;Saxunova,L.;Repovska,M.;Sarissky,M.;Seliga,R.;Mirossay,L.;Mojzis,J.Toxicol.Vitr.2013,27,939–944;Mezencev,R.;Updegrove,T.;Kutschy,P.;Repovska,M.;Mcdonald,J.F.J.Nat.Med.2011,65,488–499;Mezencev,R.;Galizzi,M.;Kutschy,P.;Docampo,R.Exp Parasitol.2009,122,66–69;Pedras,M.S.C.;Ahiahonu,P.W.K.Bioorgan.Med.Chem.2002,10,3307–3312.]. documents [ Ayer, W.A; craw, p.a; ma, Y.T; miao, S.C. tetrahedron 1992,48 (14), 2919-2924.) uses the corresponding indole and 2-bromothiazole as raw materials, and the alkaloid camalexin and the derivative (shown as a reaction formula I) are obtained through Grignard reaction, so that the compound has a certain bactericidal activity on the amycolatopsis (Cladosporium sp.) and a very inflammable reagent methyl magnesium iodide is needed in the reaction process.
Literature [ Pedras, m.s.c.; minic, z.; sarma-MAMILLAPALLE, V.K.J.Agric.food chem.2009,57,2429-2435 ] synthesized a series of derivatives containing the core structure of camalexin (as structural formula two) and examined their inhibitory activity against Brassinin oxidase (a fungal detoxification enzyme capable of overcoming the action of plant defenses), found that the synthesized series of compounds had a certain inhibitory activity against Rhizoctonia solani (Leptosphaeria maculans), but camalexin derivative 2f had no inhibitory effect against Brassinin oxidase; the application of the anti-plant pathogenic bacteria is limited to the black spot of rape.
Literature [ Pedras, m.s.c.; abdoli, a. Bioorg. Med. Chem.2013,21 4541-4549 ] in order to explore the bioconversion process of phytol camalexin, phytol camalexin and derivatives 2b, 2f were synthesized using reported methods, and compounds 2 g-2 j were prepared by introducing other substituents into the thiazole structure as in equation two; studies of the biological activity of alternaria brassicae (ALTE RNARIA brassicicola) showed that: at a dosage of 0.2mM, camalexin and compound 2b, and 2 g-2 h had 100% inhibition of Alternaria brassicae, but 2f had 71% inhibition of Alternaria brassicae, and 2 i-2 j had 38% and 41% inhibition of Alternaria brassicae, respectively; meanwhile, the thiazole structural unit substituent has a remarkable influence on the inhibition activity of the Alternaria brassicae, but unfortunately, due to the limitation of halogenated species, specific functional groups (such as methyl, carboxylic acid and hydroxymethyl) can only be introduced into the thiazole structural unit, and the biological activity and the compound property of the thiazole structural unit can not be regulated.
The application of nortopsentin alkaloid derivatives containing bisindole and thiazole structural units in the system in the control of plant diseases and insect pests is reported in literature [Guo,J.;Hao,Y.;Ji,X.;Wang,Z.;Liu,Y.;Ma,D.;Li,Y.;Pang,H.;Ni,J.;Wang,Q.J.Agric.Food Chem.2019,67,10018-10031.] and patent [ CN109418267B ], the synthetic method is shown in a reaction formula II, and the research on biological activity shows that: most of nortopsentin alkaloid derivatives containing bisindole and thiazole structural units have better inhibition rate on tobacco mosaic virus than commercial variety ribavirin, and have certain bactericidal activity on 14 common plant pathogenic bacteria (tomato early blight, wheat gibberella, rice blast, phytophthora capsici, rape sclerotium, rice sheath blight, cucumber ash mold, cucumber wilt, peanut brown spot, apple ring spot, wheat sheath blight, corn small spot, watermelon anthrax and rice bakanae). Although nortopsentin alkaloid derivatives containing bisindole and thiazole structural units have good tobacco mosaic virus resistance and bactericidal activity, 2-bromo-1- (1H-indol-3-yl) ethyl-1-ketone used in the reaction process cannot be directly purchased and at least 3 steps of reactions are needed for synthesis, so that when an indole group is introduced into the thiazole 4-position, the influence of substituents on the biological activity is limited, and the biological activity and the compound property of the thiazole are relatively weak.
Disclosure of Invention
The invention aims to provide a plant protection element camalexin derivative, a preparation method and application thereof, aiming at the problems that the plant protection element camalexin derivative has various activities, good environmental compatibility and the like and has relatively low activity. The derivative introduces a new substituent group based on alkaloid camalexin, introduces a bromine atom at the 5-position in a core skeleton indole structural unit of a natural product camalexin, and introduces a hydrazide hydrazone functional group at the 4-position in a thiazole structural unit to generate a series camalexin derivative. The alkaloid plant protection element camalexin derivative has good anti-plant virus activity and broad-spectrum plant pathogen killing activity.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a derivative of plant protection element camalexin, the structural general formula of the derivative of plant protection element camalexin is shown as I,
Wherein, R is phenyl, 2-fluorophenyl, 3, 4-difluorophenyl, 2, 6-difluorophenyl, 2, 4-difluorophenyl, 2, 3-difluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3, 4-dichlorophenyl, 2, 6-dichlorophenyl, 2, 4-dichlorophenyl, 2, 3-dichlorophenyl, 2, 5-dichlorophenyl, 4-chlorophenyl, 5-chloro-2-fluorophenyl, 2-bromophenyl, 3-bromophenyl, 4-iodophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-methylphenyl 3-methylphenyl, 4-methylphenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 3, 5-bis (trifluoromethyl) phenyl, 3-methoxyphenyl, 3,4, 5-tris (methoxy) phenyl, 4-methoxyphenyl, 2-thienyl, 2-furyl, 2-pyridyl, 4-pyridyl, 1-naphthyl, 4-quinolyl, cyclohexyl, cyclopentyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or benzyl.
The plant protection element camalexin derivative is preferably:
Wherein the compound shown in the chemical structural formula I-1 is (E) -N ' -benzylidene-2- (5-bromo-1H-indol-3-yl) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-2 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' - (4-methoxybenzylidene) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-3 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' - (3, 4, 5-trimethoxybenzylidene) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-4 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' - (4-trifluoromethylbenzylidene) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-5 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' - (4-fluorobenzoylidene-4-carbohydrazide, the compound shown in the chemical structural formula I-6 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' - (2-bromobenzylidene) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-7 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' - (4-nitrobenzylidene) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-8 is 2- (5-bromo-1H-indol-3-yl) -N ' - (naphthalen-1-ylmethylene) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-9 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' - (pyridin-4-ylmethylene) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-10 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' - (quinolin-4-ylmethylene) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-11 is 2- (5-bromo-1H-indol-3-yl) -N ' - (furan-2-ylmethylene) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-12 is E) -2- (5-bromo-1H-indol-3-yl) -N ' - (cyclohexylmethylene) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-13 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' - (2-methylpropylene) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-14 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' -butylideylthiazole-4-carbohydrazide, and the compound shown in the chemical structural formula Ia-15 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' -octylidene thiazole-4-carbohydrazide.
The preparation method of the plant protection element camalexin derivative comprises the following steps:
(1) Taking 5-bromo-1H-indole-3-thioformamide (3 e) as a raw material, and carrying out heating reflux reaction on the raw material and 3-bromopyruvate ethyl ester in an ethanol solvent to obtain a compound 5;
Wherein the molar ratio is that 5-bromo-1H-indole-3-thioformamide: 3-bromopyruvate ethyl ester=1: 1 to 1.5, 5 to 20mL of ethanol is added per millimole of 5-bromo-1H-indole-3-thiocarboxamide, the reaction time is 1 to 4 hours, and the temperature range is 75 to 85 ℃;
(2) Taking a compound 5 and 80% hydrazine hydrate as raw materials, and heating and refluxing the raw materials in an ethanol solvent to react to obtain a compound 6;
wherein, the molar ratio is that, compound 5: hydrazine hydrate = 1: 3-10, adding 15-30 mL of ethanol per millimole of compound 5, wherein the reaction time is 1-4 h, and the temperature range is 75-85 ℃;
(3) The preparation method of the compounds I-1 to I-15 comprises the following steps:
Heating and refluxing the raw materials of the compound 6 and aldehyde compounds in an ethanol solvent to react to obtain compounds I-1 to I-15;
wherein, the molar ratio is that, compound 6: aldehyde compound = 1: 1-2, adding 15-30 mL of ethanol per millimole of compound 6, wherein the reaction time is 1-4 h, and the temperature range is 75-85 ℃;
The aldehyde compound is specifically benzaldehyde, 2-fluorobenzaldehyde, 3, 4-difluorobenzaldehyde, 2, 6-difluorobenzaldehyde, 2, 4-difluorobenzaldehyde, 2, 3-difluorobenzaldehyde, 4-fluorobenzaldehyde, 2-chlorobenzaldehyde, 3, 4-dichlorobenzaldehyde, 2, 6-dichlorobenzaldehyde, 2, 4-dichlorobenzaldehyde, 2, 3-dichlorobenzaldehyde, 2, 5-dichlorobenzaldehyde, 4-chlorobenzaldehyde, 5-chloro-2-fluorobenzaldehyde, 2-bromobenzaldehyde, 3-bromobenzaldehyde, 4-iodobenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 3-nitrobenzaldehyde, and the like 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2-trifluoromethylbenzaldehyde, 3-trifluoromethylbenzaldehyde, 4-trifluoromethylbenzaldehyde, 3, 5-bis (trifluoromethyl) benzaldehyde, 3-methoxybenzaldehyde, 3,4, 5-tris (methoxy) benzaldehyde, 4-methoxybenzaldehyde, 2-thiophenaldehyde, 2-furaldehyde, 2-pyridylaldehyde, 4-pyridylaldehyde, 1-naphthylaldehyde, 4-quinolinylaldehyde, cyclohexylcyclohexanecarboxyaldehyde, cyclopentylcyclohexanal, n-propionaldehyde, n-butyl, isobutyl, n-valeraldehyde, n-hexanal, n-heptanal, n-octanal, n-nonanal or phenylacetaldehyde.
The application of the plant protection element camalexin derivative is used as an anti-plant virus agent, wherein the plant protection element camalexin derivative is a compound shown in the following chemical structural formulas I-1 to I-15:
The plant protection element camalexin derivative I-1-I-15 is used as an anti-plant virus agent, wherein the plant virus is tobacco mosaic virus, pepper virus, rice virus, tomato virus, sweet potato virus, melon virus or maize dwarf mosaic virus. Wherein, the compound has excellent activity of resisting tobacco mosaic virus, most of the compound has activity obviously better than commercial variety ribavirin, and the activities of the compounds I-1 to I-2, I-4 to I-13 and I-15 are obviously better than those of plant protection element camalexin.
The application of the plant protection element camalexin derivatives I-1-I-15 in the aspect of resisting plant pathogenic bacteria, specifically, the plant pathogenic bacteria are tomato early blight, wheat gibberella, rice blast, phytophthora capsici, rape sclerotium, rice sheath blight, cucumber gray mold, cucumber wilt, peanut brown spot, apple sheath blight, wheat sheath blight, corn small spot, watermelon anthracnose or rice bakanae; the plant pathogen resisting activity is shown to be broad, the biological activity spectrum is different from that of the plant protection element camalexin, and unexpected effects and breakthrough progress are achieved.
Compared with the prior art, the invention has the outstanding substantial characteristics and remarkable progress as follows:
(1) The first discovery that the plant protection element camalexin derivative has good anti-plant virus activity, under the same test condition, when the dosage is 500 mug/mL, I-1 to I-2, I-4 to I-13 and I-15 are all superior to commercial variety ribavirin, and the compounds I-6 and I-8 show anti-TMV activity equivalent to or higher than that of Ningnanmycin at 500 mug/mL; in addition, the plant protection element camalexin derivative has broad-spectrum inhibition activity on 14 common agricultural pathogens, for example, the inhibition rate of the compounds I-1 and I-13 against phytophthora capsici, rhizoctonia solani and Sclerotinia sclerotiorum is obviously better than camalexin, the inhibition rate of the compound I-12 against rice blast fungus and cucumber gray mold is obviously better than camalexin, and unexpected effects and breakthrough progress are obtained; the invention expands the application range of the plant protection element camalexin derivative as biological pesticide.
(2) The important intermediate 2- (5-bromo-1H-indole 3-yl) thiazole-4-carbohydrazide (6) is obtained in the preparation process of the plant protection element camalexin derivative, and the compound can be heated and refluxed with various different types of aldehyde compounds in ethanol solution to obtain different substituted camalexin derivatives, so that the guarantee is provided for the systematic exploration of structure-activity relationship, the regulation of biological activity, the regulation of compound solubility and stability and the like.
Detailed Description
The preparation method of the plant protection element camalexin derivative comprises the following specific steps of:
Taking 5-bromo-1H-indole-3-thiocarboxamide shown in a chemical structural formula 3e as a raw material, and carrying out heating reflux reaction on the raw material and 3-bromopyruvate ethyl ester in an ethanol solvent to generate a 2- (5-bromo-1H-indole-3-yl) thiazole-4-ethyl formate intermediate product shown in the chemical structural formula 5; dissolving the intermediate product in ethanol, adding 80% hydrazine hydrate to generate hydrazinolysis reaction under heating condition to obtain an important intermediate 2- (5-bromo-1H-indole 3-yl) thiazole-4-carbohydrazide shown in a chemical structural formula 6; finally, reacting the 2- (5-bromo-1H-indole 3-yl) thiazole-4-carbohydrazide with different substituted aldehyde compounds to prepare the 2- (5-bromo-1H-indole-3-yl) -N' -methylene thiazole-4-carbohydrazide shown in the chemical structural formula I.
The preparation of the compounds I-1 to I-5 comprises the following steps:
Example 1
The preparation method of the (E) -N' -benzylidene-2- (5-bromo-1H-indol-3-yl) thiazole-4-carbohydrazide shown in the chemical formula I-1 comprises the following steps:
in the first step, chlorosulfonic acid isocyanate (12 mmol) is added dropwise to a DMF (10 mL) solution of 5-bromoindole (10 mmol) at-50 ℃ under nitrogen protection, and the temperature is raised to room temperature after the dropwise addition is completed to continue the reaction for 1.5 hours. After TLC detection reaction is finished, pouring the reaction system into ice water, stirring for 30 minutes, and suction-filtering to obtain yellow solid 5-bromo-1H-indole-3-carbonitrile, wherein the yield is 99%; melting point 185–186℃;1H NMR(400MHz,CDCl3)δ9.18(s,1H),7.93(s,1H),7.76(s,1H),7.45(d,J＝8.7Hz,1H),7.39(d,J＝8.7Hz,1H);13C NMR(100MHz,DMSO-d6)δ135.9,134.0,128.4,126.1,120.7,115.6,115.0,114.4,84.0, determines that the product is 5-bromo-1H-indole-3-carbonitrile.
Second, 5-bromo-1H-indole-3-carbonitrile (8 mmol) was added to a mixture of 70% sodium hydrosulfide solution (24 mmol) and magnesium chloride hexahydrate (8 mmol) in 10mL of DMF and stirred at 40℃for 12 hours, then the mixture was poured into 200 mL of water, after which the filter cake was added to 1M HCl solution after suction filtration, stirred for 20 minutes and filtered, and then the filter cake was washed with water to give 5-bromo-1H-indole-3-thiocarboxamide as a white solid, yield 89%, melting point 145–147℃;1H NMR(400MHz,DMSO-d6)δ12.00(s,1H),9.05(s,1H),8.95(s,1H),8.91(s,1H),8.15(s,1H),7.43(d,J＝8.5Hz,1H),7.30(d,J＝8.5Hz,1H);13C NMR(100MHz,DMSO-d6)δ193.5,136.0,129.2,128.5,125.1,124.6,116.0,114.5,114.2, determined to be 5-bromo-1H-indole-3-thiocarboxamide; wherein the first and second step references [Guo,J.C.;Hao,Y.N.;Ji,X.F.;Wang,Z.W.;Liu,Y.X.;Ma,D.J.;Li,Y.Q.;Pang,H.L.;Ni,J.P.;Wang,Q.M.J.Agric.Food Chem.2019,67,10018-10031.] are prepared.
Thirdly, adding 5-bromo-1H-indole-3-thioformamide (2 mmol) into ethanol (20 mL) solution of 3-bromopyruvate ethyl ester (2 mmol), heating at 80 ℃ for 2 hours, and filtering to obtain yellow solid ethyl 2- (5-bromo-1H-indol-3-yl) thiazole-4-carboxylate with the yield of 98%; melting point 202–203℃;1H NMR(400MHz,DMSO-d6)δ12.07(s,1H),8.42(d,J＝1.8Hz,1H),8.38(s,1H),8.27(d,J＝2.9Hz,1H),7.49(d,J＝8.6Hz,1H),7.37(d,J＝8.6Hz,1H),4.35(q,J＝7.1Hz,2H),1.35(t,J＝7.1Hz,3H);13C NMR(100MHz,DMSO-d6)δ162.9,160.8,146.0,135.3,128.9,125.8,125.2,122.6,114.3,113.5,109.4,60.7,14.2.C14H12BrN2O2S[M+H]+350.9797,found(ESI+)350.9794, determines that the product is ethyl 2- (5-bromo-1H-indol-3-yl) thiazole-4-carboxylate.
Fourth, compound 2- (5-bromo-1H-indol-3-yl) thiazole-4-carboxylic acid ethyl ester (1 mmol,1.0 equiv.) and hydrazine hydrate (80%, 0.2mL,5mmol,5 equiv.) are dissolved in ethanol (20 mL), the temperature is controlled to 80 ℃ and heated for 2 hours, and after cooling to room temperature, the yellow solid 2- (5-bromo-1H-indol-3-yl) thiazole-4-carbohydrazide is obtained by suction filtration, and the yield is 69%; melting point 295–296℃;1H NMR(400MHz,DMSO-d6)δ11.98(s,1H),9.85(s,1H),8.63(d,J＝1.4Hz,1H),8.23(s,1H),8.07(s,1H),7.45(d,J＝8.6Hz,1H),7.35(d,J＝8.6Hz,1H),4.61(s,2H);13C NMR(100MHz,DMSO-d6)δ163.3,160.7,149.6,135.8,129.4,126.1,125.8,123.7,120.4,114.5,114.2,110.3.C12H10BrN4OS[M+H]+336.9753,found(ESI+)336.9757, determines that the product is 2- (5-bromo-1H-indol-3-yl) thiazole-4-carbohydrazide.
Fifth, 2- (5-bromo-1H-indol-3-yl) thiazole-4-carbohydrazide (1 mmol,1.0 equiv.) and benzaldehyde (1.05 mmol,1.05 equiv.) are dissolved in ethanol (20 mL) and heated at 80deg.C for 2 hours, cooled to room temperature and suction filtered to give (E) -N '-benzylidene-2- (5-bromo-1H-indol-3-yl) thiazole-4-carbohydrazide as a white solid with a yield of 41% and a melting point of 214–215℃;1H NMR(400MHz,DMSO-d6)δ12.07(s,1H),11.82(s,1H),8.66(s,1H),8.54(s,1H),8.30(d,J＝5.9Hz,2H),7.78(s,1H),7.76(s,1H),7.49(d,J＝8.5Hz,4H),7.38(dd,J＝8.6,1.4Hz,1H);13C NMR(100MHz,DMSO-d6)δ163.4,157.8,149.3,149.2,135.8,134.9,130.6,129.5,129.4,127.7,126.2,125.8,123.3,122.8,114.7,114.3,110.1;C19H14BrN4OS[M+H]+425.0066,found(ESI+)425.0064,, which determines that the product is (E) -N' -benzylidene-2- (5-bromo-1H-indol-3-yl) thiazole-4-carbohydrazide.
Example 2
The preparation method of the (E) -2- (5-bromo-1H-indol-3-yl) -N' - (4-methoxybenzylidene) thiazole-4-carbohydrazide shown in the chemical formula I-2 comprises the following steps:
The product was obtained as (E) -2- (5-bromo-1H-indol-3-yl) -N' - (4-methoxybenzylidene) thiazole-4-carbohydrazide in the same manner as in example 1, white solid, yield 56% and melting point >300℃;1H NMR(400MHz,DMSO-d6)δ12.08(s,1H),11.71(s,1H),8.59(s,1H),8.54(s,1H),8.30(s,1H),8.29(s,1H),7.72(d,J＝8.7Hz,2H),7.49(d,J＝8.6Hz,1H),7.39(d,J＝8.6Hz,1H),7.06(d,J＝8.7Hz,2H),3.83(s,3H);13C NMR(100MHz,DMSO-d6)δ163.4,161.4,157.7,149.3,149.2,135.8,129.5,129.3,127.3,126.1,125.8,123.2,122.6,114.9,114.7,114.3,110.1,55.8;C20H16BrN4O2S[M+H]+455.0172,found(ESI+)455.0173,, except that the benzaldehyde was replaced with 4-methoxybenzaldehyde in the fifth step.
Example 3
The preparation method of the (E) -2- (5-bromo-1H-indol-3-yl) -N' - (3, 4, 5-trimethoxybenzylidene) thiazole-4-carbohydrazide shown in the chemical structural formula I-3 comprises the following steps:
The product was obtained as (E) -2- (5-bromo-1H-indol-3-yl) -N' - (3, 4, 5-trimethoxybenzylidene) thiazole-4-carbohydrazide in the same manner as in example 1, in 42% yield and at a melting point 241–242℃;1H NMR(400MHz,DMSO-d6)δ12.07(s,1H),11.83(s,1H),8.60(s,1H),8.55(s,1H),8.30(s,2H),7.49(d,J＝8.8Hz,1H),7.38(d,J＝8.8Hz,1H),7.06(s,2H),3.87(s,6H),3.73(s,3H);13C NMR(100MHz,DMSO-d6)δ163.5,157.8,153.7,149.3,139.8,135.8,130.3,129.5,126.1,125.8,123.3,122.8,114.7,114.3,110.1,104.8,60.6,56.4;C22H20BrN4O4S[M+H]+515.0383,found(ESI+)515.0387,, except that 3,4, 5-trimethoxybenzaldehyde was used instead of benzaldehyde.
Example 4
The preparation method of the (E) -2- (5-bromo-1H-indol-3-yl) -N' - (4-trifluoromethyl benzylidene) thiazole-4-carbohydrazide shown in the chemical formula I-4 comprises the following steps:
The product was obtained as (E) -2- (5-bromo-1H-indol-3-yl) -N' - (4-trifluoromethylbenzylidene) thiazole-4-carbohydrazide in the same manner as in example 1, but with a white solid, yield 57%, and melting point >300℃;1H NMR(400MHz,DMSO-d6)δ12.08(s,1H),11.86(s,1H),8.66(s,1H),8.54(s,1H),8.31(d,J＝6.1Hz,2H),7.85(s,1H),7.81(s,1H),7.49(d,J＝8.6Hz,1H),7.38(d,J＝8.4Hz,1H),7.32(d,J＝8.5Hz,2H);13C NMR(100MHz,DMSO-d6)δ164.9,163.5,162.4,157.9,149.2,148.1,135.8,131.4,129.9,129.5,126.1,125.8,123.2,122.9,116.5,116.3,114.7,114.3,110.1,79.6;C20H13BrF3N4OS[M+H]+492.9940,found(ESI+)492.9946,, as described in the fifth step 4-trifluoromethylbenzaldehyde instead of benzaldehyde.
Example 5
The preparation method of the (E) -2- (5-bromo-1H-indol-3-yl) -N' - (4-fluorobenzylidene) thiazole-4-carbohydrazide shown in the chemical formula I-5 comprises the following steps:
The product was obtained as (E) -2- (5-bromo-1H-indol-3-yl) -N' - (4-fluorobenzylidene) thiazole-4-carbohydrazide in the same manner as in example 1, white solid, yield 41% and melting point >300℃;1H NMR(400MHz,DMSO-d6)δ12.08(s,1H),12.04(s,1H),8.74(s,1H),8.56(s,1H),8.35(s,1H),8.30(s,1H),7.99(d,J＝8.0Hz,2H),7.85(d,J＝8.2Hz,2H),7.49(d,J＝8.6Hz,1H),7.39(d,J＝8.6Hz,1H);13C NMR(100MHz,DMSO-d6)δ163.04(s),157.5,148.6,146.9,138.3,135.3,129.1,127.7,125.8,125.7,125.6,125.5,125.3,122.8,114.2,113.8,109.6;C19H13BrFN4OS[M+H]+442.9972,found(ESI+)442.9979,, except that the benzaldehyde was replaced with 4-fluorobenzaldehyde in the fifth step.
Example 6
The preparation method of the (E) -2- (5-bromo-1H-indol-3-yl) -N' - (2-bromobenzylidene) thiazole-4-carbohydrazide shown in the chemical structural formula I-6 comprises the following steps:
The product was determined to be (E) -2- (5-bromo-1H-indol-3-yl) -N' - (2-bromobenzylidene) thiazole-4-carbohydrazide in yield 82％,mp>300℃;1H NMR(400MHz,DMSO-d6)δ12.18(s,1H),12.07(s,1H),9.01(s,1H),8.54(s,1H),8.34(s,1H),8.30(s,1H),8.05(d,J＝7.5Hz,1H),7.72(d,J＝7.9Hz,1H),7.55–7.44(m,2H),7.38(d,J＝8.4Hz,2H);13C NMR(100MHz,DMSO-d6)δ163.4,158.0,149.1,147.3,135.8,133.7,133.7,132.2,129.5,128.6,127.9,126.2,125.8,124.1,123.3,123.2,114.7,114.3,110.1;C19H13Br2N4OS[M+H]+502.9171,found(ESI+)502.9173, as in example 1, white solid, except that 2-bromobenzaldehyde was used instead of benzaldehyde in the fifth step.
Example 7
The preparation method of the (E) -2- (5-bromo-1H-indol-3-yl) -N' - (4-nitrobenzylidene) thiazole-4-carbohydrazide shown in the chemical formula I-7 comprises the following steps:
The product was identified as (E) -2- (5-bromo-1H-indol-3-yl) -N' - (4-nitrobenzylidene) thiazole-4-carbohydrazide in 97% yield and melting point >300℃;1H NMR(400MHz,DMSO-d6)δ12.15(s,1H),12.09(s,1H),8.77(s,1H),8.55(s,1H),8.37(s,1H),8.34(s,1H),8.31(d,J＝5.9Hz,2H),8.03(d,J＝8.4Hz,2H),7.49(d,J＝8.6Hz,1H),7.39(d,J＝8.4Hz,1H);13C NMR(100MHz,DMSO-d6)δ163.6,158.0,149.0,148.4,146.6,141.2,135.8,129.6,128.6,126.1,125.8,124.6,123.5,123.3,114.7,114.3,110.1;C19H13BrN5O3S[M+H]+469.9917,found(ESI+)469.9911, as in example 1, except that 4-nitrobenzaldehyde was used instead of benzaldehyde in the fifth step.
Example 8
The preparation method of the 2- (5-bromo-1H-indol-3-yl) -N' - (naphthalen-1-ylmethylene) thiazole-4-carbohydrazide shown in the chemical structural formula I-8 comprises the following steps:
the product was found to be 2- (5-bromo-1H-indol-3-yl) -N' - (naphthalen-1-ylmethylene) thiazol-4-carbohydrazide in 97% yield and melting point >300℃;E:Z＝8:3;1H NMR(400MHz,DMSO-d6)δ12.11(for E isomer,s,0.8H),11.99(for Z isomer,s,0.3H),11.93(for E isomer,s,0.8H),9.85(for Z isomer,s,0.3H),9.36(for E isomer,s,0.8H),8.88(for E isomer,d,J＝8.5Hz,0.8H),8.63(for Z isomer,s,0.3H),8.56(for E isomer,d,J＝1.6Hz,0.8H),8.36(s,1H),8.33(s,1H),8.23(for Z isomer,s,0.3H),8.09–7.98(m,3H),7.73–7.61(m,2H),7.52–7.34(m,3H),4.61(for Z isomer,s,0.5H);13C NMR(100MHz,DMSO-d6)δ163.0,157.3,148.7,148.4,135.3,133.5,130.6,130.4,129.6,129.3,128.8,127.4,127.3,126.3,125.6,125.3,124.1,123.1,122.7,122.4,120.0,114.3,114.0,113.8,113.7,109.8,109.6;C23H16BrN4OS[M+H]+475.0223,found(ESI+)475.0225, as determined in example 1 as a white solid except that the benzaldehyde was replaced with 1-naphthaldehyde in the fifth step.
Example 9
The preparation method of the (E) -2- (5-bromo-1H-indol-3-yl) -N' - (pyridine-4-ylmethylene) thiazole-4-carbohydrazide shown in the chemical structural formula I-9 comprises the following steps:
The product was obtained as (E) -2- (5-bromo-1H-indol-3-yl) -N' - (pyridin-4-ylmethylene) thiazol-4-carbohydrazide in the same manner as in example 1, white solid, yield 54% and melting point >300℃;1H NMR(400MHz,DMSO-d6)δ12.13(s,1H),12.09(s,1H),8.69(s,1H),8.67(d,J＝4.2Hz,2H),8.55(s,1H),8.37(s,1H),8.31(s,1H),7.71(d,J＝5.6Hz,2H),7.49(d,J＝8.6Hz,1H),7.39(d,J＝8.6Hz,1H);13C NMR(100MHz,DMSO-d6)δ163.1,157.5,150.3,148.5,146.2,141.5,135.3,129.1,125.6,125.3,123.0,122.8,121.,114.2,113.8,109.6;C18H13BrN5OS[M+H]+426.0019,found(ESI+)426.0023,, except that benzaldehyde was used instead of benzaldehyde in the fifth step.
Example 10
The preparation method of the (E) -2- (5-bromo-1H-indol-3-yl) -N' - (quinolin-4-ylmethylene) thiazole-4-carbohydrazide shown in the chemical formula I-10 comprises the following steps:
The product was obtained as (E) -2- (5-bromo-1H-indol-3-yl) -N' - (quinolin-4-ylmethylene) thiazol-4-carbohydrazide in 80% yield and at a melting point >300℃;1H NMR(400MHz,DMSO-d6)δ12.18(s,1H),12.12(s,1H),9.38(s,1H),9.03(d,J＝4.4Hz,1H),8.78(d,J＝8.4Hz,1H),8.56(s,1H),8.41(s,1H),8.33(s,1H),8.13(d,J＝8.4Hz,1H),7.91(d,J＝4.5Hz,1H),7.87(t,J＝7.6Hz,1H),7.78(t,J＝7.6Hz,1H),7.50(d,J＝8.6Hz,1H),7.40(d,J＝10.1Hz,1H);13C NMR(100MHz,DMSO-d6)δ150.8,148.9,146.1,138.0,135.8,130.3,130.1,129.4,128.0,126.1,125.8,125.4,124.7,123.5,123.2,120.0,114.7,114.3,110.1;C26H15BrN5OS[M+H]+476.0175,found(ESI+)476.0177, as determined in example 1 as a white solid except that the benzaldehyde was replaced with 4-quinolinecarboxaldehyde in the fifth step.
Example 11
The preparation method of the 2- (5-bromo-1H-indol-3-yl) -N' - (furan-2-ylmethylene) thiazole-4-carbohydrazide shown in the chemical structural formula I-11 comprises the following steps:
The product was found to be 2- (5-bromo-1H-indol-3-yl) -N' - (furan-2-ylmethylene) thiazole-4-carbohydrazide in 67% yield and melting point 251–252℃;E:Z＝3:1;1H NMR(400MHz,DMSO-d6)δ12.10(for E isomer,s,1H),11.99(for Zisomer,s,0.2H),11.84(for E isomer,s,0.6H),9.85(for Z isomer,s,0.2H),8.63(for Z isomer,s,0.2H),8.56(d,J＝5.9Hz,1H),8.39(for E isomer,d,J＝3.3Hz,0.5H),8.32(d,J＝9.2Hz,1.5H),8.23(for Z isomer,s,0.2H),8.06(for Z isomer,s,0.2H),7.95(for Z isomer,d,J＝1.3Hz,0.2H),7.89(for E isomer,s,0.6H),7.62(for Z isomer,s,0.2H),7.48(d,J＝8.6Hz,1H),7.38(d,J＝8.6Hz,1H),7.17(for Z isomer,d,J＝3.5Hz,0.2H),6.99(for E isomer,d,J＝3.3Hz,0.6H),6.83(for Z isomer,d,J＝3.5Hz,0.2H),6.67(for E isomer,d,J＝1.5Hz,0.6H);13C NMR(100MHz,DMSO-d6)δ163.0,157.3,149.5,148.6,145.3,138.4,135.3,129.0,125.6,125.3,122.8,122.4,114.2,113.8,113.7,112.3,109.6;C17H12BrN4O2S[M+H]+414.9859,found(ESI+)41 4.9863, as compared to example 1, except that 2-furaldehyde was used instead of benzaldehyde in the fifth step.
Example 12
The preparation method of the (E) -2- (5-bromo-1H-indol-3-yl) -N' - (cyclohexylmethylene) thiazole-4-carbohydrazide shown in the chemical formula I-12 comprises the following steps:
The product was identified as (E) -2- (5-bromo-1H-indol-3-yl) -N' - (cyclohexylmethylene) thiazole-4-carbohydrazide in the same manner as example 1 in 62% yield as the white solid and melting point 286–287℃;1H NMR(400MHz,DMSO-d6)δ12.07(s,1H),11.37(s,1H),8.51(s,1H),8.28(s,1H),8.23(s,1H),7.83(s,1H),7.48(d,J＝8.6Hz,1H),7.37(d,J＝8.6Hz,1H),2.30(s,1H),1.87–1.59(m,5H),1.39–1.14(m,5H);13C NMR(100MHz,DMSO-d6)δ162.8,157.1,156.8,148.9,135.3,128.9,125.6,125.3,122.7,121.8,114.2,113.7,109.6,79.1,29.7,25.5,25.0;C19H20BrN4OS[M+H]+431.0536,found(ESI+)431.0533,, except that cyclohexylformaldehyde was used instead of benzaldehyde in the fifth step.
Example 13
The preparation method of the (E) -2- (5-bromo-1H-indol-3-yl) -N' - (2-methylpropylene) thiazole-4-carbohydrazide shown in the chemical structural formula I-13 comprises the following steps:
The product was obtained as (E) -2- (5-bromo-1H-indol-3-yl) -N' - (2-methylpropylene) thiazole-4-carbohydrazide in the same manner as in example 1, white solid, yield 48％,mp 258–259℃;1H NMR(400MHz,DMSO-d6)δ12.06(s,1H),11.37(s,1H),8.50(s,1H),8.27(s,1H),8.22(s,1H),7.85(s,1H),7.47(d,J＝8.6Hz,1H),7.37(d,J＝8.6Hz,1H),1.11(d,J＝6.8Hz,7H);13C NMR(100MHz,DMSO-d6)δ162.8,158.0,157.1,148.8,135.3,128.9,125.6,125.3,122.7,121.9,114.2,113.7,109.6,47.9,31.15,19.61;C16H16BrN4OS[M+H]+391.0223,found(ESI+)391.0225,, except that isobutyraldehyde was used instead of benzaldehyde in the fifth step.
Example 14
The preparation method of the (E) -2- (5-bromo-1H-indol-3-yl) -N' -butylidene thiazole-4-carbohydrazide shown in the chemical structural formula I-14 comprises the following steps:
The product was determined to be (E) -2- (5-bromo-1H-indol-3-yl) -N' -butylideothiazole-4-carbohydrazide in yield 65％,mp 272–273℃;1H NMR(400MHz,DMSO-d6)δ7.39(s,1H),7.15(s,1H),7.04(s,1H),6.78(d,J＝3.9Hz,1H),6.38(d,J＝6.3Hz,1H),6.32(d,J＝6.4Hz,1H),1.45–1.25(m,2H),0.74–0.53(m,3H),0.25(s,4H);13C NMR(100MHz,DMSO-d6)δ162.8,157.0,153.2,149.0,135.3,129.0,125.6,125.3,122.8,121.8,114.2,113.7,109.6,34.0,19.5,13.7;C16H16BrN4OS[M+H]+391.0223,found(ESI+)391.0227, as in example 1, white solid, except that N-butyraldehyde was used instead of benzaldehyde in the fifth step.
Example 15
The preparation method of the (E) -2- (5-bromo-1H-indol-3-yl) -N' -octylidene thiazole-4-carbohydrazide shown in the chemical structural formula I-15 comprises the following steps: the product was determined to be (E) -2- (5-bromo-1H-indol-3-yl) -N' -octylidene thiazole-4-carbohydrazide in the same manner as in example 1, white solid, 66% yield and 223–224℃;1H NMR(400MHz,DMSO-d6)δ7.63(s,1H),7.39(s,1H),7.29(s,1H),7.01(s,1H),6.62(d,J＝8.6Hz,1H),6.57(d,J＝8.6Hz,1H),1.61(m,2H),0.83(m,3H),0.52(m,12H);13C NMR(100MHz,DMSO-d6)δ163.3,157.5,153.8,149.5,135.8,129.5,126.1,125.8,123.3,122.3,114.7,114.2,110.1,32.6,31.7,29.1,29.0,26.6,22.6,14.4;C20H24BrN4OS[M+H]+447.0849,found(ESI+)447.0855,% melting point, except that N-octanal was used instead of benzaldehyde in the fifth step.
Example 16
The activity of individual compounds shown in the plant protection element camalexin derivatives I-1 to I-15 against tobacco mosaic virus is measured by the following procedures:
firstly, tobacco mosaic virus purification and concentration determination:
Tobacco mosaic virus purification and concentration determination are carried out according to SOP specification of tobacco mosaic virus prepared by a measuring room of southern university element, virus crude extract is subjected to polyethylene glycol centrifugation for 2 times, the concentration is determined to be 20 mug/mL, and the obtained product is refrigerated at 4 ℃ for later use;
Secondly, preparing individual compound medicament solutions shown in the plant protection element camalexin derivatives I-1 to I-15:
weighing 40mg of individual compounds shown as plant protection element camalexin derivatives I-1 to I-15 as raw materials, adding 0.4mL of DMF (dimethyl formamide) into each raw material for dissolution to prepare 1X 10 5 mug/mL mother liquor, and diluting with Tween 80 aqueous solution with mass percent concentration of 1%o to test concentration of 500 mug/mL or 100 mug/mL to prepare individual compound medicament solutions shown as plant protection element camalexin derivatives I-1 to I-15, and directly diluting ribavirin or Ningnanmycin preparation with water to prepare a contrast substance;
thirdly, living body protection:
Respectively selecting ten parts of 3-5 She Qishan Xiyan cigarettes with uniform growth vigor, spraying the individual compound medicament solutions shown in the second step of the plant protection element camalexin derivatives I-1-I-15, repeating each treatment for 3 times, setting tween 80 water solution with the mass percent concentration of 1%o for comparison, spreading 500 meshes of silicon carbide on the leaf surface after 24 hours, dipping a virus solution by using a writing brush, lightly wiping the whole leaf surface for 2 times along the pulse supporting direction, supporting the lower part of the leaf by using palm, flushing the leaf with flowing water after inoculation, repeating each 3 leaves for 1 time, repeating for 3 times, recording the number of lesions after 3 days, and calculating the prevention effect;
Fourth step, living body treatment effect:
respectively selecting ten parts of 3-5 She Qishan Western cigarettes with uniform growth vigor, inoculating viruses with writing brush whole leaves, wherein the virus concentration is 10 mug/mL, flushing with running water after inoculation, collecting and drying leaf surfaces, spraying the individual compound medicament solution shown by the plant protection element camalexin derivatives I-1 to I-15 and prepared in the second step on the whole plant, repeating for 3 times, setting tween 80 water solution with the mass percent concentration of 1 per mill for comparison, recording the number of lesions after 3 days, and calculating the control effect;
Fifth step, living body passivation:
Respectively selecting ten parts of 3-5 She Qishan Xiyan cigarettes with uniform growth vigor, respectively mixing the individual compound medicament solution shown in the plant protection element camalexin derivative I-1-I-15 prepared in the second step with an equal volume of virus juice, passivating for 30min, performing friction inoculation, wherein the virus concentration is 20 mug/mL, washing with running water after inoculation, repeating for 3 times, setting a Tween 80 aqueous solution with the mass percent concentration of 1 per mill for comparison, counting the number of lesions after 3 days, and calculating the result;
The results of the measurement of the tobacco mosaic virus resistance of individual compounds shown in the derivatives I-1 to I-15 of the above-mentioned plant protection element camalexin are shown in Table 1.
Table 1. Results of anti-TMV Activity test of individual compounds shown as derivatives I-1 to I-15 of plant protection element camalexin:
the plant protection element camalexin derivative shown in table 1 has good anti-plant virus activity, most of the anti-plant virus activity is better than commercial variety ribavirin when the dosage is 500 mug/mL under the same test condition, and the compounds I-6 and I-8 show the anti-TMV activity which is equal to or higher than that of Ningnanmycin at 500 mug/mL, thus having development value.
Example 17
The antibacterial activity test, in vitro sterilization test, and the measurement procedure of the individual compounds in the plant protection element camalexin derivatives I-1 to I-15 are as follows:
Cell growth rate assay, plate method: 3mg of the individual compounds in the plant protection element camalexin derivatives I-1 to I-15 are respectively dissolved in 0.03mL of acetone, then the mixture is diluted to a test concentration of 50mg/kg by using an aqueous solution containing 200 mug/mL of Tween 80, then 1mL of liquid medicine is respectively absorbed and injected into a corresponding culture dish, 9mL of culture medium is respectively added, a 50 mug/mL medicine-containing flat plate is prepared after shaking uniformly, 1mL of sterilized purified water is added as a blank contrast, a puncher with the diameter of 4mm is used for cutting a fungus disk along the outer edge of hypha, the fungus disk is moved onto the medicine-containing flat plate, each treatment is repeated three times, the culture dish is placed in a constant temperature incubator at 24+/-1 ℃ for culture, the expansion diameter of each fungus disk is investigated after 48 hours, the average value is calculated, and the relative bacteriostasis rate is compared with the blank contrast.
The results of the in vitro fungicidal activity of the individual compounds of the abovementioned derivatives I-1 to I-15 of phytosanitary camalexin are shown in Table 2.
TABLE 2 results of in vitro bactericidal Activity test of individual Compounds in the derivatives I-1 to I-15 of phytosanitary camalexin
Table 2 shows that the derivatives of the plant protection element camalexin have broad-spectrum inhibition activity on 14 common agricultural pathogens, and under the same test conditions, the inhibition rate of the compounds I-1 and I-13 against phytophthora capsici, rhizoctonia cerealis and Sclerotinia sclerotiorum is obviously superior to camalexin, and the compounds I-1 to I-11 show moderate to good bactericidal activity on the Rhizoctonia apple.
The percentages in the above examples are mass percentages.
The materials and reagents involved in the above examples are all commercially available and the chemical reaction process is well within the skill of the art.
The invention is not a matter of the known technology.

Claims (1)

1. A use of a derivative of phytoncide camalexin as an anti-plant virus agent,
The plant virus is tobacco mosaic virus;
The structural formula of the plant protection element camalexin derivative is as follows:
Wherein the compound shown in the chemical structural formula I-1 is (E) -N ' -benzylidene-2- (5-bromo-1H-indol-3-yl) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-6 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' - (2-bromobenzylidene) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-8 is 2- (5-bromo-1H-indol-3-yl) -N ' - (naphthalen-1-ylmethylene) thiazole-4-carbohydrazide, the compound shown in the chemical structural formula I-10 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' - (quinolin-4-ylmethylene) thiazole-4-carbohydrazide, and the compound shown in the chemical structural formula I-13 is (E) -2- (5-bromo-1H-indol-3-yl) -N ' - (2-methylpropylene) thiazole-4-carbohydrazide.
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