CN116283822A - Thiazole and imidazo [1,2-a ] pyridine acylhydrazone compounds and application thereof - Google Patents

Thiazole and imidazo [1,2-a ] pyridine acylhydrazone compounds and application thereof Download PDF

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CN116283822A
CN116283822A CN202310073525.7A CN202310073525A CN116283822A CN 116283822 A CN116283822 A CN 116283822A CN 202310073525 A CN202310073525 A CN 202310073525A CN 116283822 A CN116283822 A CN 116283822A
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carbohydrazide
pyridine
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thiazole
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李定
张蓉蓉
姚晓芳
刘志刚
高锦明
胡兆农
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Northwest A&F University
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    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • 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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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract

The invention discloses thiazole and imidazo [1,2-a ]]Pyridine acylhydrazone compounds and application thereof, and the compounds have the following characteristics

Description

Thiazole and imidazo [1,2-a ] pyridine acylhydrazone compounds and application thereof
Technical Field
The invention belongs to the field of pesticide chemistry, and in particular relates to thiazole and imidazo [1,2-a ] pyridine acyl hydrazone compounds and application thereof, which can effectively inhibit plant pathogenic fungi, oriental armyworms and aphids, and application of the compounds in preventing and treating agricultural pathogenic fungi infection and common insect pests.
Background
The plant mycosis is a disease caused by plant pathogenic fungi and mainly comprises rice blast fungus, gray mold fungus, rust fungus, fusarium graminearum, fusarium oxysporum, powdery mildew, anthrax, corn black powder and the like. Several, even tens of fungal diseases can be found on crops. Crop diseases and insect pests are also one of main agricultural disasters, and common diseases and insect pests of crops in China are Oriental armyworms, corn borers, cotton bollworms, cotton aphids, wheat red spiders, locust and the like. Plant mycoses and crop pests have seriously affected agricultural production in China.
In recent years, condensed heterocyclic compounds have gradually developed into flash points in the development of new drugs. Acylhydrazones are a class of compounds containing amide and imine functional structures. The N-acylhydrazone structure has peptidomimetic properties and can be recognized by a variety of different receptors. The hydrazone nitrogen and oxygen atoms have extremely strong coordination capability, so that the hydrazone nitrogen and oxygen atoms are favorable for forming complexes with a plurality of metal ions. Through modifying the chemical structure, more high-activity heterocyclic substituted acylhydrazone compounds can be obtained, and the heterocyclic substituted acylhydrazone compounds are widely applied to various fields of agriculture, medicine, industry and the like. In agriculture, acylhydrazone compounds are widely used as herbicides, bactericides, pesticides and the like. In the aspect of medicine, the heterocyclic substituted acylhydrazone compound has various physiological activities, and the acylhydrazone and the metal complex thereof have been widely used in the fields of medicine, analysis, functional materials and the like. The acylhydrazone compounds have antibacterial, antiparasitic, antitumor and enzyme inhibiting activities. In industry, acylhydrazone compounds are used in fluorescence analysis of biological materials, luminescent materials, dyes, fluorescent probe materials, and the like.
The bactericides which are widely used in China at present comprise pyraclostrobin, chlorothalonil, thifluzamide, diethofencarb and the like. Spirodiclofen, tebufenozide, chlorfluazuron and the like are pesticides with better activity on the market. However, with the development of society, drug resistance is a common problem of the existing bactericidal insecticide, and irregular use of the bactericidal insecticide is a main cause of reduced pesticide effectiveness. Therefore, the design and development of novel heterocyclic acylhydrazone compounds have important significance for the development of human life health and food safety industry.
Disclosure of Invention
The invention aims to explore a novel efficient heterocyclic acylhydrazone bactericidal insecticide and provide a heterocyclic acylhydrazone derivative with plant pathogen resistance and insecticidal activity.
The technical scheme of the invention is as follows:
thiazole and imidazo [1,2-a ] pyridine acylhydrazones, said compounds comprising:
a compound of formula I or a pharmaceutically acceptable salt thereof:
Figure BDA0004065402620000021
r in formula I 1 Selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 2 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 3 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, haloalkoxy, haloalkyl, alkenylalkoxy, and haloalkenylalkoxy;
R 4 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 5 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
and/or a compound of formula ii:
Figure BDA0004065402620000022
r in II 1 Selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 2 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 3 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, haloalkoxy, haloalkyl, alkenylalkoxy, and haloalkenylalkoxy;
R 4 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 5 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R' 1 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R' 2 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R' 3 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl.
Alternatively, the alkyl group is a straight or branched saturated hydrocarbon group having 1 to 6 carbon atoms; or a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms; or a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms which is a straight or branched saturated hydrocarbon group having 1 to 6 carbon atoms attached;
the haloalkyl is a straight-chain or branched-chain saturated hydrocarbon group with 1-6 carbon atoms, or a cyclic saturated hydrocarbon group with 3-6 carbon atoms connected with the straight-chain or branched-chain saturated hydrocarbon group with 1-6 carbon atoms; wherein one or more carbon atoms are substituted with one or more halogen atoms;
the alkoxy is straight-chain or branched-chain saturated hydrocarbon with 1-6 carbon atoms; or a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms; or a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms which is a straight or branched saturated hydrocarbon group having 1 to 6 carbon atoms attached; wherein each carbon atom is optionally substituted with oxygen;
the alkenyl and alkynyl are straight-chain or branched-chain unsaturated hydrocarbon groups containing double bonds or triple bonds and having 1-6 carbon atoms;
the halogen is selected from the group consisting of fluorine, chlorine, bromine and iodine;
the halogenated unsaturated hydrocarbon group is alkenyl or alkynyl, wherein one or more carbon atoms in the alkenyl or alkynyl are substituted by one or more halogen atoms;
the haloalkyl is alkyl as defined above connected with halogen;
the haloalkoxy is that the alkoxy is as defined above is connected with halogen;
the alkenylalkoxy is an unsaturated hydrocarbylalkoxy linkage as defined above;
the haloalkylalkoxy is a haloalkylalkoxy linkage as defined above.
Optionally, R in formula I 1 Selected from hydrogen, fluorine, chlorine, bromine and hydroxyl;
R 2 selected from hydrogen, fluorine, chlorine and bromine;
R 3 selected from the group consisting of hydrogen, fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy and allyloxy;
R 4 selected from hydrogen, fluorine, chlorine, bromine and trifluoromethyl;
R 5 selected from hydrogen, fluorine, chlorine and bromine.
Alternatively, R in formula II 1 Selected from hydrogen, fluorine, chlorine, bromine and hydroxyl;
R 2 selected from hydrogen, fluorine, chlorine and bromine;
R 3 selected from the group consisting of hydrogen, fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy and allyloxy;
R 4 selected from hydrogen, fluorine, chlorine, bromine and trifluoromethyl;
R 5 selected from hydrogen, fluorine, chlorine and bromine;
R' 1 selected from hydrogen, chlorine, bromine and benzyloxy;
R' 2 selected from hydrogen, chlorine and bromine;
R' 3 selected from hydrogen, chlorine and bromine.
Alternatively, the compounds of formula I are preferably compounds of the following structure:
(E) -N' - (4- (trifluoromethoxy) benzylidene) thiazole-4-carbohydrazide (I-1);
(E) -N' - (5-chloro-2-fluorobenzylidene) thiazole-4-carbohydrazide (I-2);
(E) -N' - (2, 4-dichlorobenzylidene) thiazole-4-carbohydrazide (I-3);
(E) -N' - (3, 5-dichlorobenzylidene) thiazole-4-carbohydrazide (I-4);
(E) -N' - (4- (allyloxy) benzylidene) thiazole-4-carbohydrazide (I-5);
(E) -N' - (3-chlorobenzyl) thiazole-4-carbohydrazide (I-6);
(E) -N' - (2, 6-chlorobenzyl) thiazole-4-carbohydrazide (I-7);
(E) -N' - (3, 5-dichloro-2-hydroxybenzylidene) thiazole-4-carbohydrazide (I-8);
(E) -N' - (2-fluoro-4- (trifluoromethyl) benzylidene) thiazole-4-carbohydrazide (I-9);
(E) -N' - (2-fluoro-5- (trifluoromethyl) benzylidene) thiazole-4-carbohydrazide (I-10).
Alternatively, the compounds of formula II are preferably of the following structure:
(E) -N' - (2-fluoro-5- (trifluoromethyl) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-1);
(E) -N' - (3-chlorobenzyl) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-2);
(E) -N' - (5-chloro-2-fluorobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-3);
(E) -N' - (2, 6-dichlorobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-4);
(E) -N' - (3, 5-dichlorobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-5);
(E) -N' - (4- (allyloxy) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-6);
(E) -N' - (2-bromobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-7);
(E) -N' - (2-fluoro-4- (trifluoromethyl) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-8);
(E) -N' - (4- (trifluoromethoxy) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (II-9).
The thiazole and imidazo [1,2-a ] pyridine acyl hydrazone compounds are used for preparing plant bactericides.
Optionally, the bactericide is used for preventing and treating gray mold of tomatoes, dry rot of potatoes, anthracnose of apples, rot of apples, rice blast and/or wheat scab.
The thiazole and imidazo [1,2-a ] pyridine acyl hydrazone compounds are used for preparing plant pesticides.
Optionally, the insecticide is used for controlling insects including myxoplasma and/or aphids.
The compound activity test results of the invention show that the compounds shown in the general formulas I and II have excellent inhibitory activities on potato dry rot germs (Fusarium solani), botrytis cinerea (Botrytis cinerea), wheat red fungus germs (Fusarium graminearum), apple rot germs (Cytospora sp.), apple anthracnose germs (Colletotrichum gloeosporioides) and rice blast germs (Magnaporthe grisea), and can be used for preparing plant bactericides.
The activity test results show that the compounds of the general formulas I and II have excellent inhibitory activity on Oriental myxoma and can be used for preparing botanical pesticides.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The two general formulas of the thiazole and imidazo [1,2-a ] pyridine acylhydrazone compounds of the present invention include:
a compound of formula I or a pharmaceutically acceptable salt thereof:
Figure BDA0004065402620000051
r in formula I 1 Selected from hydrogen, alkylHalogen and hydroxy;
R 2 selected from hydrogen, alkyl, halogen and hydroxy;
R 3 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, haloalkoxy, haloalkyl, and alkoxyalkenyl;
R 4 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 5 selected from hydrogen, alkyl, halogen and hydroxy;
and/or a compound of formula ii:
Figure BDA0004065402620000052
r in II 1 Selected from hydrogen, alkyl, halogen and hydroxy;
R 2 selected from hydrogen, alkyl, halogen and hydroxy;
R 3 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, haloalkoxy, haloalkyl, alkenylalkoxy, and haloalkenylalkoxy;
R 4 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 5 selected from hydrogen, alkyl, halogen and hydroxy;
R' 1 selected from the group consisting of hydrogen, alkyl, halogen, and alkoxy;
R' 2 selected from the group consisting of hydrogen, alkyl, halogen, and alkoxy;
R' 3 selected from the group consisting of hydrogen, alkyl, halogen, and alkoxy.
Alkyl is a straight or branched saturated hydrocarbon group having 1 to 6 carbon atoms; or a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms; or a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms which is a straight or branched saturated hydrocarbon group having 1 to 6 carbon atoms attached;
haloalkyl is a straight or branched saturated hydrocarbon group having 1 to 6 carbon atoms, or a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms linked to a straight or branched saturated hydrocarbon group having 1 to 6 carbon atoms; wherein one or more carbon atoms are substituted with one or more halogen atoms;
alkoxy is a straight or branched saturated hydrocarbon radical having 1 to 6 carbon atoms; or a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms; or a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms which is a straight or branched saturated hydrocarbon group having 1 to 6 carbon atoms attached; wherein each carbon atom is optionally substituted with oxygen;
alkenyl and alkynyl are straight-chain or branched unsaturated hydrocarbon groups containing double bonds or triple bonds and having 1 to 6 carbon atoms;
halogen is selected from the group consisting essentially of substitution of fluorine, chlorine, bromine, and iodine;
halo-unsaturated hydrocarbyl is alkenyl or alkynyl as defined above wherein one or more carbon atoms are replaced with one or more halogen atoms;
haloalkyl is alkyl as defined above attached to halogen;
haloalkoxy is alkoxy as defined above linked to halogen;
alkenyl alkoxy is an unsaturated alkyl alkoxy linkage as defined above;
haloalkylalkoxy is a haloalkylalkoxy linkage as defined above.
The invention has the preferable scheme that:
r in formula I 1 Selected from hydrogen, fluorine, chlorine, bromine and hydroxyl;
R 2 selected from hydrogen, fluorine, chlorine and bromine;
R 3 selected from the group consisting of hydrogen, fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy and allyloxy;
R 4 selected from hydrogen, fluorine, chlorine, bromine and trifluoromethyl;
R 5 selected from hydrogen, fluorine, chlorine and bromine;
r in II 1 Selected from hydrogen, fluorine, chlorine, bromine and hydroxyl;
R 2 selected from hydrogen, fluorine, chlorine and bromine;
R 3 selected from the group consisting of hydrogen, fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy and allyloxy;
R 4 selected from hydrogen, fluorine, chlorine, bromine and trifluoromethyl;
R 5 selected from hydrogen, fluorine, chlorine and bromine;
R' 1 selected from hydrogen, chlorine, bromine and benzyloxy;
R' 2 selected from hydrogen, chlorine and bromine;
R' 3 selected from hydrogen, chlorine and bromine.
The compounds of the general formula I are preferably compounds of the following structure:
(E) -N' - (4- (trifluoromethoxy) benzylidene) thiazole-4-carbohydrazide (I-1);
(E) -N' - (5-chloro-2-fluorobenzylidene) thiazole-4-carbohydrazide (I-2);
(E) -N' - (2, 4-dichlorobenzylidene) thiazole-4-carbohydrazide (I-3);
(E) -N' - (3, 5-dichlorobenzylidene) thiazole-4-carbohydrazide (I-4);
(E) -N' - (4- (allyloxy) benzylidene) thiazole-4-carbohydrazide (I-5);
(E) -N' - (3-chlorobenzyl) thiazole-4-carbohydrazide (I-6);
(E) -N' - (2, 6-chlorobenzyl) thiazole-4-carbohydrazide (I-7);
(E) -N' - (3, 5-dichloro-2-hydroxybenzylidene) thiazole-4-carbohydrazide (I-8);
(E) -N' - (2-fluoro-4- (trifluoromethyl) benzylidene) thiazole-4-carbohydrazide (I-9);
(E) -N' - (2-fluoro-5- (trifluoromethyl) benzylidene) thiazole-4-carbohydrazide (I-10).
The compounds of the general formula II are preferably compounds of the following structure:
(E) -N' - (2-fluoro-5- (trifluoromethyl) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-1); (E) -N' - (3-chlorobenzyl) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-2);
(E) -N' - (5-chloro-2-fluorobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-3);
(E) -N' - (2, 6-dichlorobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-4);
(E) -N' - (3, 5-dichlorobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-5);
(E) -N' - (4- (allyloxy) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-6);
(E) -N' - (2-bromobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-7);
(E) -N' - (2-fluoro-4- (trifluoromethyl) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-8); (E) -N' - (4- (trifluoromethoxy) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (II-9). The preparation method of the compound of the invention comprises the following steps:
Figure BDA0004065402620000081
a method for synthesizing a Scheme1 heterocyclic acylhydrazone compound I. (1) a heterocyclic ester starting material; (2) synthesizing an intermediate; (3) aldehyde raw materials; (4) acylhydrazone derivatives;
Figure BDA0004065402620000082
a method for synthesizing a Scheme2 heterocyclic acylhydrazone compound II. (1) pyridine raw materials; (2, 3) synthesizing an intermediate; (4) aldehyde raw materials; (5) acylhydrazone derivatives;
in the scheme of the invention, the mentioned proportion or percentage are calculated by mass unless otherwise specified.
General preparation method of class I compounds:
(I) A10 mL eggplant-shaped bottle was charged with thiazole-4-carboxylic acid ethyl ester (100 mg,0.64 mmol) in dry EtOH (6.4 mL) and NH was added 2 -NH 2 ·H 2 O (0.2 ml,10-15 eq) was stirred at room temperature and reacted overnight. Concentrated in vacuo and the silica gel column purified DCM: meOH (50:1-10:1) to afford intermediate compound 2 (thiazole-4-carboxamide) as a white solid.
(II) 2 (thiazole-4-carboxylic acid hydrazide) and 3 in methanol (5 ml) were added to a 25ml eggplant-shaped bottle, 2 drops of glacial acetic acid were added, and the reaction mixture was stirred at room temperature overnight. Concentrated in vacuo and purified by silica gel chromatography with DCM: meOH (50:1-10:1) to afford the title compound.
General preparation method of class II compounds:
(I) Pyridine starting material 1 (500 mg,5.31 mmol) and anhydrous EtOH (10 mL) were added to a 25mL eggplant-shaped bottle, stirred in an ice bath, ethyl 3-bromopyruvate (1.55 g,7.97 mmol) was added, and refluxed for 24h; after cooling, concentrated in vacuo and purified by silica gel chromatography in DCM: meOH (100:1-50:1) to give intermediate compound 2 as a pale yellow solid.
In a 10mL eggplant-shaped bottle, intermediate compound 2 (50 mg,0.26 mmol) was added, and NH was added 2 -NH 2 ·H 2 O (0.5 ml, excess) was stirred well and refluxed at 69℃for 2h. Concentrated in vacuo, purified by silica gel chromatography, DCM: meOH (50:1-10:1) to afford intermediate compound 3 as a white solid.
(II) A25 ml eggplant-shaped bottle was charged with a methanol solution (5 ml) of intermediate compound 3 and aldehyde starting material 4, 2 drops of glacial acetic acid were added thereto, and the mixture was stirred at room temperature overnight. Concentrated in vacuo and purified by silica gel chromatography with DCM: meOH (50:1-10:1) to afford the title compound.
Example 1:
(E) -N' - (4- (trifluoromethoxy) benzylidene) thiazole-4-carbohydrazide (I-1);
Figure BDA0004065402620000091
the preparation method of the general formula I is used for preparing the target compound I-1 by using thiazole-4-formylhydrazine and 4-trifluoromethoxybenzaldehyde to obtain a yellow solid with the yield of 88.63%. 1 H NMR(400MHz,DMSO-d 6 )δ12.06(s,1H),9.27(d,J＝2.0Hz,1H),8.61(s,1H),8.54(d,J＝2.0Hz,1H),7.85–7.82(m,2H),7.47–7.44(m,2H). 13 CNMR(100MHz,DMSO-d 6 )δ157.14,155.33,149.51,149.33,147.08,133.65,129.05,126.16,121.37.
Example 2:
(E) -N' - (5-chloro-2-fluorobenzylidene) thiazole-4-carbohydrazide (I-2);
Figure BDA0004065402620000092
the preparation method of the general formula I is to prepare the target compound I-2 by thiazole-4-formylhydrazine and 5-chloro-2-fluorobenzaldehyde,obtained as a yellow solid in 96.39% yield. 1 NMR(400MHz,DMSO-d 6 )δ12.32(s,1H),9.28(d,J＝2.0Hz,1H),8.80(s,1H),8.57(d,J＝2.0Hz,1H),7.89(dd,J＝6.2,2.8Hz,1H),7.55(ddd,J＝8.9,4.5,2.8Hz,1H),7.38(dd,J＝10.1,8.9Hz,1H). 13 C NMR(100MHz,DMSO-d 6 )δ159.75(d,J＝323Hz),157.24,155.37,149.27,139.91(d,J＝4.0Hz),131.45(d,J＝9.0Hz),129.00,126.50,125.39(d,J＝3.0Hz),123.88(d,J＝12.0Hz),118.24(d,J＝23.0Hz).
Example 3:
(E) -N' - (2, 4-dichlorobenzylidene) thiazole-4-carbohydrazide (I-3);
Figure BDA0004065402620000101
the preparation method of the general formula I is used for preparing the target compound I-3 by thiazole-4-formylhydrazine and 2, 4-dichlorobenzaldehyde to obtain a white solid with the yield of 78.39%. 1 H NMR(400MHz,DMSO-d 6 )δ12.37(s,1H),9.28(d,J＝2.0Hz,1H),8.99(s,1H),8.56(d,J＝2.0Hz,1H),8.02(d,J＝8.5Hz,1H),7.72(d,J＝2.1Hz,1H),7.54–7.49(m,1H). 13 C NMR(100MHz,DMSO-d 6 )δ157.25,155.31,149.38,143.61,135.12,134.03,130.91,129.40,128.18,128.02,126.38.
Example 4:
(E) -N' - (3, 5-dichlorobenzylidene) thiazole-4-carbohydrazide (I-4);
Figure BDA0004065402620000102
the preparation method of the general formula I is used for preparing the target compound I-4 by thiazole-4-formylhydrazine and 3, 5-dichlorobenzaldehyde to obtain yellow solid with the yield of 96.98%. 1 H NMR(400MHz,DMSO-d 6 )δ12.24(s,1H),9.28(d,J＝2.0Hz,1H),8.56(d,J＝2.0Hz,1H),8.54(s,1H),7.73(d,J＝1.9Hz,2H),7.68(t,J＝1.9Hz,1H). 13 C NMR(100MHz,DMSO-d 6 )δ157.27,155.36,149.30,145.50,138.09,134.66,129.12,126.45,125.36.
Example 5:
(E) -N' - (4- (allyloxy) benzylidene) thiazole-4-carbohydrazide (I-5);
Figure BDA0004065402620000111
the preparation of the target compound I-5 from thiazole-4-formylhydrazine and 4-allyloxybenzaldehyde gave a yellow solid in 88.33%. 1 H NMR(400MHz,DMSO-d 6 )δ11.82(s,1H),9.26(d,J＝2.0Hz,1H),8.52(s,1H),8.50(d,J＝2.0Hz,1H),7.68–7.61(m,2H),7.06–7.00(m,2H),6.05(s,1H),5.41(dq,J＝17.3,1.7Hz,1H),5.28(dq,J＝10.5,1.5Hz,1H),4.62(dt,J＝5.3,1.6Hz,2H). 13 C NMR(100MHz,DMSO-d 6 )δ159.80,156.85,155.15,149.77,148.49,133.42,128.76,127.03,125.61,117.67,115.03,68.30.
Example 6:
(E) -N' - (3-chlorobenzyl) thiazole-4-carbohydrazide (I-6);
Figure BDA0004065402620000112
the preparation method of the general formula I is used for preparing the target compound I-6 by thiazole-4-formylhydrazine and 3-chlorobenzaldehyde to obtain a white solid with the yield of 95.64 percent. 1 H NMR(400MHz,DMSO-d 6 )δ12.10(s,1H),9.28(d,J＝2.0Hz,1H),8.57(s,1H),8.55(d,J＝2.0Hz,1H),7.75(d,J＝2.0Hz,1H),7.66(ddd,J＝4.7,3.3,1.5Hz,1H),7.50(dd,J＝4.0,2.3Hz,2H). 13 C NMR(100MHz,DMSO-d 6 )δ157.16,155.30,149.45,146.98,136.60,133.68,130.81,129.78,126.24,126.20,125.96.
Example 7:
(E) -N' - (2, 6-dichlorobenzylidene) thiazole-4-carbohydrazide (I-7);
Figure BDA0004065402620000113
in the preparation method of the general formula I, thiazole-4-formylhydrazine and 2, 6-dichlorobenzeneThe aldehyde gave the target compound I-7 as a yellow solid in 89.58% yield. 1 H NMR(400MHz,DMSO-d 6 )δ12.72(s,1H),12.53(s,1H),9.30(d,J＝2.0Hz,1H),8.73(s,1H),8.61(d,J＝2.0Hz,1H),7.60(dd,J＝19.0,2.5Hz,2H). 13 CNMR(100MHz,DMSO-d 6 )δ157.22,155.34,149.36,144.04,133.94,131.26,130.82,129.06,126.43.
Example 8:
(E) -N' - (3, 5-dichloro-2-hydroxybenzylidene) thiazole-4-carbohydrazide (I-8);
Figure BDA0004065402620000121
the preparation method of the general formula I is used for preparing the target compound I-8 by using thiazole-4-formylhydrazine and 3, 5-dichloro-2-hydroxybenzaldehyde, and the yield is 91.15 percent. 1 H NMR(400MHz,DMSO-d 6 )δ12.34(s,1H),9.29(d,J＝2.0Hz,1H),8.79(s,1H),8.55(d,J＝2.0Hz,1H),7.58(d,J＝0.9Hz,1H),7.56(s,1H),7.47–7.43(m,1H). 13 C NMR(100MHz,DMSO-d 6 )δ157.16,155.63,152.34,148.64,148.04,130.36,128.49,127.05,122.97,121.54,120.81.
Example 9:
(E) -N' - (2-fluoro-4- (trifluoromethyl) benzylidene) thiazole-4-carbohydrazide (I-9);
Figure BDA0004065402620000122
the preparation of the target compound I-9 by the preparation method of the general formula I, thiazole-4-formylhydrazine and 2-fluoro-4-trifluoromethyl benzaldehyde, gave a yellow solid with a yield of 93.48%. 1 H NMR(400MHz,DMSO-d 6 )δ12.38(s,1H),9.29(d,J＝2.0Hz,1H),8.88(s,1H),8.58(d,J＝2.0Hz,1H),8.16(t,J＝7.7Hz,1H),7.79(dd,J＝10.6,1.8Hz,1H),7.68(dd,J＝8.2,1.7Hz,1H). 13 C NMR(100MHz,DMSO-d 6 )δ160.50(dd,J＝297Hz),157.28,155.34,149.25,139.86(d,J＝5.0Hz),131.34(dd,J＝33.0,8.5Hz),127.64(d,J＝3.0Hz),126.53,126.17(d,J＝10.0Hz),123.23(q,J＝269Hz),121.70(t,J＝4Hz),113.71(dd,J＝24.0,4.0Hz).
Example 10:
(E) -N' - (2-fluoro-5- (trifluoromethyl) benzylidene) thiazole-4-carbohydrazide (I-10);
Figure BDA0004065402620000131
the preparation of the target compound I-10 was carried out using thiazole-4-carboxylic acid hydrazide and 2-fluoro-5- (trifluoromethyl) benzaldehyde in the general formula I to give a yellow solid in 92.96% yield. 1 H NMR(400MHz,DMSO-d 6 )δ12.38(s,1H),9.29(d,J＝2.0Hz,1H),8.88(s,1H),8.58(d,J＝2.0Hz,1H),8.21(dd,J＝6.6,2.4Hz,1H),7.89(td,J＝5.0,4.5,2.3Hz,1H),7.57(t,J＝9.4Hz,1H). 13 C NMR(100MHz,DMSO-d 6 )δ162.43(d,J＝248.0Hz),157.29,155.39,149.20,139.78(d,J＝3.0Hz),128.83(d,J＝5.0Hz),126.55,125.87(dd,J＝32.0,3.0Hz),124.09(t,J＝190Hz),123.54–123.25(m),122.32,117.71(d,J＝22.0Hz).
Example 11:
(E) -N' - (2-fluoro-5- (trifluoromethyl) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-1);
Figure BDA0004065402620000132
by a process for the preparation of the general formula II by imidazo [1,2-a ]]The pyridine-2-formylhydrazine and 2-fluoro-5-trifluoromethylbenzaldehyde produce the target compound II-1 as a yellow solid in 98.31% yield. 1 H NMR(400MHz,DMSO-d 6 )δ12.40(s,1H),8.89(s,1H),8.62(d,J＝6.8Hz,1H),8.59(s,1H),8.21(dd,J＝6.5,2.5Hz,1H),7.90–7.85(m,1H),7.65(d,J＝9.2Hz,1H),7.56(t,J＝9.4Hz,1H),7.40(ddd,J＝8.9,6.8,1.3Hz,1H),7.03(t,J＝6.7Hz,1H). 13 C NMR(100MHz,DMSO-d 6 )δ162.32(d,J＝233.0Hz),158.95,144.05,139.03(d,J＝4.0Hz),138.14,129.66,129.16–128.53(m),127.79,126.83,125.86(dd,J＝33.0,3.0Hz),123.55–123.18(m),122.37(d,J＝270.0Hz),117.71(d,J＝23.0Hz),117.35,116.30,113.54.
Example 12:
(E) -N' - (3-chlorobenzyl) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-2);
Figure BDA0004065402620000141
by a process for the preparation of the general formula II by imidazo [1,2-a ]]The pyridine-2-formylhydrazine and 3-chlorobenzaldehyde to prepare the target compound II-2 as a white solid in 89.86% yield. 1 H NMR(400MHz,DMSO-d 6 )δ12.08(s,1H),8.62(dt,J＝6.9,1.2Hz,1H),8.57(d,J＝11.0Hz,2H),7.75(q,J＝1.5Hz,1H),7.68–7.61(m,2H),7.54–7.45(m,2H),7.39(ddd,J＝9.2,6.7,1.3Hz,1H),7.03(td,J＝6.8,1.1Hz,1H). 13 CNMR(100MHz,DMSO-d 6 )δ158.77,146.34,144.03,138.36,136.80,133.70,130.85,129.67,127.80,126.80,126.16,125.93,117.35,116.09,113.51.
Example 13:
(E) -N' - (5-chloro-2-fluorobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-3);
Figure BDA0004065402620000142
by a process for the preparation of the general formula II by imidazo [1,2-a ]]The pyridine-2-formylhydrazine and 5-chloro-2-fluorobenzaldehyde gave the objective compound II-3 as a white solid in 91.39% yield. 1 H NMR(400MHz,DMSO-d 6 )δ12.33(s,1H),8.81(s,1H),8.62(dt,J＝6.9,1.2Hz,1H),8.57(s,1H),7.90(dd,J＝6.1,2.8Hz,1H),7.65(dq,J＝9.3,1.0Hz,1H),7.56–7.52(m,1H),7.42–7.35(m,2H),7.03(td,J＝6.8,1.2Hz,1H). 13 CNMR(100MHz,DMSO-d 6 )δ159.45(d,J＝270.0Hz),158.91,144.05,139.22(d,J＝4.0Hz),138.20,131.30(d,J＝8.0Hz),129.00(d,J＝3.0Hz),127.80,126.83,125.36(d,J＝2.0Hz),124.08(d,J＝12.0Hz),118.25(d,J＝23.0Hz),117.36,116.25,113.54.
Example 14:
(E) -N' - (2, 6-dichlorobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-4);
Figure BDA0004065402620000143
by a process for the preparation of the general formula II by imidazo [1,2-a ]]The pyridine-2-formylhydrazine and 2, 6-dichlorobenzaldehyde gave the target compound II-4 as a white solid in 95.18% yield. 1 H NMR(400MHz,DMSO-d 6 )δ12.32(s,1H),8.80(s,1H),8.65–8.61(m,1H),8.56–8.54(m,1H),7.65(dd,J＝9.2,1.2Hz,1H),7.59–7.56(m,2H),7.47–7.44(m,1H),7.40(ddd,J＝9.2,6.7,1.3Hz,1H),7.03(td,J＝6.8,1.2Hz,1H). 13 C NMR(100MHz,DMSO-d 6 )δ158.84,144.05,143.43,138.30,133.97,131.21,130.98,129.08,127.82,126.81,117.38,116.19,113.53.
Example 15:
(E) -N' - (3, 5-dichlorobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-5);
Figure BDA0004065402620000151
by a process for the preparation of the general formula II by imidazo [1,2-a ]]The pyridine-2-formylhydrazine and 3, 5-dichlorobenzaldehyde gave the target compound II-5 as a white solid in 91.22% yield. 1 H NMR(400MHz,DMSO-d 6 )δ12.22(s,1H),8.62(dt,J＝6.9,1.3Hz,1H),8.56(d,J＝5.3Hz,2H),7.72(d,J＝2.0Hz,2H),7.68(t,J＝1.9Hz,1H),7.64(dt,J＝9.1,1.1Hz,1H),7.39(ddd,J＝9.2,6.7,1.3Hz,1H),7.03(td,J＝6.7,1.2Hz,1H). 13 C NMR(100MHz,DMSO-d 6 )δ158.89,144.85,144.03,138.28,138.21,134.68,129.00,127.80,126.83,125.29,117.36,116.21,113.54.
Example 16:
(E) -N' - (4- (allyloxy) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-6);
Figure BDA0004065402620000152
of the general formula IIPreparation method using imidazo [1,2-a ]]The pyridine-2-formylhydrazine and 4-allyloxybenzaldehyde gave the target compound II-6 as a white solid in 98.04% yield. 1 H NMR(400MHz,DMSO-d 6 )δ11.79(s,1H),8.61(dd,J＝6.9,1.3Hz,1H),8.54–8.52(m,2H),7.65–7.62(m,3H),7.40–7.36(m,1H),7.05–7.01(m,3H),6.06(m,1H),5.41(dq,J＝17.3,1.7Hz,1H),5.28(dq,J＝10.5,1.5Hz,1H),4.62(dt,J＝5.3,1.6Hz,2H). 13 C NMR(100MHz,DMSO-d 6 )δ159.72,158.41,147.84,143.97,138.70,133.47,128.68,127.75,127.21,126.66,117.71,117.30,115.77,115.05,113.39,68.31.
Example 17:
(E) -N' - (2-bromobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-7);
Figure BDA0004065402620000161
by a process for the preparation of the general formula II by imidazo [1,2-a ]]The pyridine-2-formylhydrazine and 2-bromobenzaldehyde produce the target compound II-7 as a white solid in 82.14% yield. 1 H NMR(400MHz,DMSO-d 6 )δ12.35(s,1H),8.99(s,1H),8.62(d,J＝6.6Hz,1H),8.56(s,1H),8.01(dd,J＝7.9,1.8Hz,1H),7.73–7.59(m,2H),7.47(t,J＝7.6Hz,1H),7.43–7.32(m,2H). 13 C NMR(100MHz,DMSO-d 6 )δ158.91,146.48,144.04,138.44,133.49,133.21,131.67,128.11,127.79,127.37,126.77,123.63,117.37,116.12,113.50.
Example 18:
(E) -N' - (2-fluoro-4- (trifluoromethyl) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-8);
Figure BDA0004065402620000162
by a process for the preparation of the general formula II by imidazo [1,2-a ]]The pyridine-2-formylhydrazine and 2-fluoro-4-trifluoromethylbenzaldehyde give the target compound II-8 as a yellow solid in 93.28% yield. 1 H NMR(400MHz,DMSO-d 6 )δ12.40(s,1H),8.89(s,1H),8.62(d,J＝6.9Hz,1H),8.58(s,1H),8.16(t,J＝7.7Hz,1H),7.81–7.76(m,1H),7.69–7.64(m,2H),7.42–7.37(m,1H),7.03(t,J＝6.7Hz,1H). 13 C NMR(100MHz,DMSO-d 6 )δ160.24(d,J＝251.0Hz),158.96,144.06,139.16(d,J＝4.0Hz),138.17,133.19,127.82,127.59(d,J＝3.0Hz),126.86,126.39(d,J＝11.0Hz),121.75(d,J＝5.0Hz),117.38,116.31,114.08–113.60(m),113.57.
Example 19:
(E) -N' - (4- (trifluoromethoxy) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-9);
Figure BDA0004065402620000171
by a process for the preparation of the general formula II by imidazo [1,2-a ]]The pyridine-2-formylhydrazine and 4-trifluoromethoxybenzaldehyde gave the objective compound II-9 as a yellow solid in 98.14% yield. 1 H NMR(400MHz,DMSO-d 6 )δ12.04(s,1H),8.62(d,J＝7.3Hz,2H),8.55(s,1H),7.83(d,J＝8.5Hz,2H),7.64(d,J＝9.2Hz,1H),7.45(d,J＝8.3Hz,2H),7.39(dd,J＝9.2,6.5Hz,1H),7.02(t,J＝6.8Hz,1H). 13 C NMR(100MHz,DMSO-d 6 )δ158.75,149.25,146.43,144.04,138.43,133.84,128.97,127.81,126.81,122.40(q,J＝126Hz),121.40,117.36,116.05,113.51.
The compounds of the invention can be prepared by the method or the method similar to the method, and corresponding raw materials are selected according to different substituents and different substituent positions.
(I) The activity test results show that the compounds of the general formulas I and II have excellent inhibitory activity against potato dry rot pathogen (Fusarium solani), botrytis cinerea (Botrytis cinerea), wheat red mildew pathogen (Fusarium graminearum), apple rot pathogen (Cytospora sp.), apple anthracis (Colletotrichum gloeosporioides) and rice blast fungus (Magnaporthe grisea).
The following are the results of partial activity evaluation experiments
All the compounds are tested for inhibition activity on different plant source fungi by using a hypha growth rate method, and compared with a positive control drug, the compounds with good activity are screened.
The specific method comprises the following steps: the compound to be screened was prepared as a mother liquor of 10mg/m L, 75. Mu.L (50 ppm, the same applies hereinafter) was added to 20mL of the solid medium and rapidly and uniformly mixed. The strain to be tested needs to be activated in advance, and a puncher with the inner diameter of 5mm is used for preparing a sufficient number of bacterial cakes for standby. The bacterial cake is placed on the solidified culture medium by a sterile inoculating needle, the mycelium-containing surface faces downwards, the bacterial cake is tightly contacted with the culture medium by lightly pressing, and three bacterial cakes of the same pathogenic fungi are placed in each culture dish. The culture dish after inoculation is placed into a constant temperature incubator at 26-28 ℃ for dark culture, and the radial length of the fungus colony is measured by a ruler after 48-96 hours (cross method, average value is obtained).
The corresponding DMSO solvent system was used as a blank control and carbendazim as a positive control. Inhibition ratio (%) = (C-T)/(C-5 mm) ×100%, C is colony diameter (mm) of the blank control group, and T is colony diameter (mm) of the treatment group or the positive control group. LC (liquid Crystal) device 50 The values were determined from the inhibition ratios of the different concentration gradients and the fit plots were calculated as IBM SPSS Statistics.
TABLE 1 determination of toxicity of partial Compounds against Botrytis cinerea, fusarium solani and Ammoniae anthracis
Figure BDA0004065402620000181
TABLE 2 determination of toxicity of partial Compound against apple rot pathogen, rice blast pathogen and wheat scab pathogen
Figure BDA0004065402620000191
The results of the activity test (II) show that the compounds of the general formulas I and II have excellent inhibitory activity against Oriental armyworm.
All the compounds were tested for inhibitory activity against 3-year old Oriental myxoplasma by leaf dipping, and compared with the blank group and the negative group, the compounds with good activity were screened out.
The specific method comprises the following steps: selecting 3-year-old Oriental armyworm with symmetrical size and good health condition, placing in 24-hole plate, preparing compound to be screened into mother liquor of 1mg/m L, taking appropriate amount of fresh and clean leaves, and cutting into square with 0.5mm for use. The leaf blade is immersed in the solution of the medicament to be detected, taken out after 10s, placed in a culture dish for airing, and placed in a 24-well plate containing Oriental armyworm in equal quantity. After 24h and 48h the results were observed and recorded.
The following are the partial activity evaluation experiments and results:
insecticidal Activity of the compounds of Table 3 against Oriental Clausena of three ages at a concentration of 1.0mg/mL
Figure BDA0004065402620000201
a Mortality of Oriental myxomyxoma with Celastrin V (CV) at 10.0mg/mL
TABLE 4 LD of partial Compound against Oriental Clay (3 years old) after 48 hours of treatment 50 Value of
Figure BDA0004065402620000202
The results of the activity test of (III) show that the compounds of the general formulas I and II have excellent aphid inhibition activity.
All compounds were tested for their inhibitory activity against the aphids of wing-free peas and compared with the blank and negative groups, compounds with good activity were screened out.
The specific method comprises the following steps: randomly selecting 20-30 wingless pea grown aphids with good health status, placing the grown aphids on pea leaves, dissolving 0.1mg of a compound to be screened by using 200 mu L of acetone, diluting a medicament by using 0.1% tween 80% aqueous solution to prepare 100mg/L mother liquor, placing the leaves in the liquid medicine for 10s, detecting death conditions of the test insects after 24h, and recording the results.
The following are the partial activity evaluation experiments and results:
TABLE 5 LD of partial compounds against Aphis finelegans after 24 hours of treatment 50 Value of
Figure BDA0004065402620000211
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.

Claims (10)

1. Thiazole and imidazo [1,2-a ] pyridine acylhydrazones, characterized in that said compounds comprise:
a compound of formula I or a pharmaceutically acceptable salt thereof:
Figure FDA0004065402610000011
r in formula I 1 Selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 2 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 3 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, haloalkoxy, haloalkyl, alkenylalkoxy, and haloalkenylalkoxy;
R 4 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 5 selected from hydrogen, alkyl, halogenHydroxyl and haloalkyl;
and/or a compound of formula ii:
Figure FDA0004065402610000012
r in II 1 Selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 2 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 3 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, haloalkoxy, haloalkyl, alkenylalkoxy, and haloalkenylalkoxy;
R 4 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R 5 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R' 1 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R' 2 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl;
R' 3 selected from the group consisting of hydrogen, alkyl, halogen, hydroxy, and haloalkyl.
2. The thiazoles and imidazo [1,2-a ] pyridine acylhydrazones according to claim 1, wherein said alkyl group is a straight or branched saturated hydrocarbon group having 1 to 6 carbon atoms; or a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms; or a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms which is a straight or branched saturated hydrocarbon group having 1 to 6 carbon atoms attached;
the haloalkyl is a straight-chain or branched-chain saturated hydrocarbon group with 1-6 carbon atoms, or a cyclic saturated hydrocarbon group with 3-6 carbon atoms connected with the straight-chain or branched-chain saturated hydrocarbon group with 1-6 carbon atoms; wherein one or more carbon atoms are substituted with one or more halogen atoms;
the alkoxy is straight-chain or branched-chain saturated hydrocarbon with 1-6 carbon atoms; or a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms; or a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms which is a straight or branched saturated hydrocarbon group having 1 to 6 carbon atoms attached; wherein each carbon atom is optionally substituted with oxygen;
the alkenyl and alkynyl are straight-chain or branched-chain unsaturated hydrocarbon groups containing double bonds or triple bonds and having 1-6 carbon atoms;
the halogen is selected from the group consisting of fluorine, chlorine, bromine and iodine;
the halogenated unsaturated hydrocarbon group is alkenyl or alkynyl, wherein one or more carbon atoms in the alkenyl or alkynyl are substituted by one or more halogen atoms;
the haloalkyl is alkyl as defined above connected with halogen;
the haloalkoxy is that the alkoxy is as defined above is connected with halogen;
the alkenylalkoxy is an unsaturated hydrocarbylalkoxy linkage as defined above;
the haloalkylalkoxy is a haloalkylalkoxy linkage as defined above.
3. Thiazole and imidazo [1,2-a ] according to claim 1]Pyridine acylhydrazone compound, characterized in that R in formula I 1 Selected from hydrogen, fluorine, chlorine, bromine and hydroxyl;
R 2 selected from hydrogen, fluorine, chlorine and bromine;
R 3 selected from the group consisting of hydrogen, fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy and allyloxy;
R 4 selected from hydrogen, fluorine, chlorine, bromine and trifluoromethyl;
R 5 selected from hydrogen, fluorine, chlorine and bromine.
4. Thiazole and imidazo [1,2-a ] according to claim 1]Pyridine acylhydrazone compound, characterized in that R in formula II 1 Selected from hydrogen, fluorine, chlorine, bromine and hydroxyl;
R 2 selected from hydrogen, fluorine, chlorine and bromine;
R 3 selected from the group consisting of hydrogen, fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy and allyloxy;
R 4 selected from hydrogen, fluorine, chlorine, bromine and trifluoromethyl;
R 5 selected from hydrogen, fluorine, chlorine and bromine;
R' 1 selected from hydrogen, chlorine, bromine and benzyloxy;
R' 2 selected from hydrogen, chlorine and bromine;
R' 3 selected from hydrogen, chlorine and bromine.
5. The thiazole and imidazo [1,2-a ] pyridine acylhydrazone compounds according to claim 1, characterized in that,
the compounds of the general formula I are preferably compounds of the following structure:
(E) -N' - (4- (trifluoromethoxy) benzylidene) thiazole-4-carbohydrazide (I-1);
(E) -N' - (5-chloro-2-fluorobenzylidene) thiazole-4-carbohydrazide (I-2);
(E) -N' - (2, 4-dichlorobenzylidene) thiazole-4-carbohydrazide (I-3);
(E) -N' - (3, 5-dichlorobenzylidene) thiazole-4-carbohydrazide (I-4);
(E) -N' - (4- (allyloxy) benzylidene) thiazole-4-carbohydrazide (I-5);
(E) -N' - (3-chlorobenzyl) thiazole-4-carbohydrazide (I-6);
(E) -N' - (2, 6-chlorobenzyl) thiazole-4-carbohydrazide (I-7);
(E) -N' - (3, 5-dichloro-2-hydroxybenzylidene) thiazole-4-carbohydrazide (I-8);
(E) -N' - (2-fluoro-4- (trifluoromethyl) benzylidene) thiazole-4-carbohydrazide (I-9);
(E) -N' - (2-fluoro-5- (trifluoromethyl) benzylidene) thiazole-4-carbohydrazide (I-10).
6. Thiazole and imidazo [1,2-a ] pyridine acylhydrazones according to claim 1, characterized in that the compounds of general formula ii are preferably of the following structure:
(E) -N' - (2-fluoro-5- (trifluoromethyl) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-1);
(E) -N' - (3-chlorobenzyl) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-2);
(E) -N' - (5-chloro-2-fluorobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-3);
(E) -N' - (2, 6-dichlorobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-4);
(E) -N' - (3, 5-dichlorobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-5);
(E) -N' - (4- (allyloxy) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-6);
(E) -N' - (2-bromobenzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-7);
(E) -N' - (2-fluoro-4- (trifluoromethyl) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (ii-8);
(E) -N' - (4- (trifluoromethoxy) benzylidene) imidazo [1,2-a ] pyridine-2-carbohydrazide (II-9).
7. Use of thiazoles and imidazo [1,2-a ] pyridine acylhydrazones according to any one of claims 1-6 for the preparation of plant bactericides.
8. The use according to claim 7, wherein the fungicide is used for controlling plant diseases including tomato gray mold, potato dry rot, apple anthracnose, apple rot, rice blast and/or wheat scab.
9. Use of thiazoles and imidazo [1,2-a ] pyridine acylhydrazones according to any one of claims 1 to 6 for the preparation of botanical pesticides.
10. The use according to claim 9, wherein the insecticide is for controlling insects including myxons and/or aphids.
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