CN115124527B - Heterocyclic amide-azaindole compound, preparation method and application thereof, and herbicide - Google Patents

Heterocyclic amide-azaindole compound, preparation method and application thereof, and herbicide Download PDF

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CN115124527B
CN115124527B CN202210610735.0A CN202210610735A CN115124527B CN 115124527 B CN115124527 B CN 115124527B CN 202210610735 A CN202210610735 A CN 202210610735A CN 115124527 B CN115124527 B CN 115124527B
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formula
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weeds
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CN115124527A (en
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蔡卓梅
严耀超
董进
周少萌
叶宝琴
南甲戌
王凡
朱晓磊
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Wuhan Yuhou Technology Co ltd
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Wuhan Zhihui Nongyao Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protecting plants
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides

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  • Chemical & Material Sciences (AREA)
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  • Environmental Sciences (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to the field of novel pesticides, and discloses a heterocyclic amide-azaindole compound, a preparation method and application thereof, and a herbicide. The heterocyclic amide-azaindole compounds provided by the invention have excellent herbicidal activity.

Description

Heterocyclic amide-azaindole compound, preparation method and application thereof, and herbicide
Technical Field
The invention relates to the technical field of novel pesticide compounds, in particular to a heterocyclic amide-azaindole compound, a preparation method and application thereof, and a herbicide.
Background
The creation and application of the efficient herbicide are important technical means for guaranteeing the grain yield and maintaining the national grain safety.
In recent years, with the continuous and wide use of herbicides, the population density and the occurrence area of resistant weeds gradually increase, china is one of five countries with the most serious harm of the resistant weeds in the world, and the problem of weed drug resistance has shown an increasingly strong trend, so that the sustainable development of agricultural production is severely restricted.
Therefore, the novel efficient herbicide is created to replace the traditional herbicide, and is an urgent need for comprehensively preventing and controlling resistant weeds, realizing reduction and synergy and realizing green sustainable development of agriculture.
Disclosure of Invention
The invention aims to provide a herbicide compound with novel structure and excellent herbicidal activity.
In order to achieve the above object, a first aspect of the present invention provides a heterocyclic amide-azaindole compound having a structure represented by formula (I),
wherein, in the formula (I),
R 1 selected from substituted or unsubstituted C 1 -C 12 Alkyl, -SO of (E) 2 -C 1 -C 6 Alkyl of (a); and R is 1 Optionally present substituents from the group consisting of halogen, C 1 -C 3 Alkoxy, phenyl, substituted by at least one C 1 -C 3 Phenyl substituted by alkyl;
R 2 is H or C 1 -C 3 Alkyl of (a);
X 1 is O or-NR x -；R x Is C 1 -C 3 Alkyl of (a);
X 2 is N or-CR y -；R y Is C 1 -C 3 Is a hydrocarbon group.
A second aspect of the present invention provides a process for preparing a compound as described in the first aspect, the process comprising: contacting a compound shown in a formula (II) with a condensing agent, a compound shown in a formula (III) and an alkaline substance in the presence of a solvent to react;
wherein in the formula (II) and the formula (III), the definition of each substituent is correspondingly the same as the definition described in any one of the first aspects.
A third aspect of the invention provides the use of a compound as described in the first aspect as a herbicide for controlling weeds.
In a fourth aspect, the present invention provides a herbicide comprising a herbicidally effective amount of an active ingredient which is at least one of the compounds described in the first aspect.
A fifth aspect of the present invention provides the use of a compound as described in the first aspect or a herbicide as described in the fourth aspect for controlling weeds in a field for planting any one crop selected from corn, rice, wheat, sorghum, peanut, soybean, canola.
The heterocyclic amide-azaindole compound provided by the invention has excellent herbicidal activity and obviously excellent safety on crops.
Specifically, the heterocyclic amide-azaindoles of the present invention have a remarkable inhibitory effect on weeds including broadleaf weeds, grassy weeds and sedge weeds, and are highly safe to crops.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
“C 1 -C 12 The "alkyl group" of (a) represents an alkyl group having 1 to 12 carbon atoms, and includes a linear alkyl group, a branched alkyl group, for example, a linear alkyl group, a branched alkyl group, which may be 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms in total, and may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, methylcyclopropyl, ethylcyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl and the like. For "C 1 -C 6 Alkyl group "," C 1 -C 3 Alkyl group "and the like of (a) have similar explanations thereto except that the number of carbon atoms is different. And, if "C 1 -C 12 When the alkyl group of (2) has a substituent other than an alkyl group, the number of carbon atoms of the substituent present therein is not counted as "C 1 -C 12 Of "alkyl" in carbon number; for example, when "C 12 Methoxy-substituted C when methoxy is present as a substituent on the alkyl group "of (2) 12 The total carbon number of the alkyl groups of (2) is 13.
“-SO 2 -C 1 -C 6 The "alkyl" of (C) represents that one side of the S atom on the sulfonyl group is connected with the parent nucleus structure and the other side is connected with C 1 -C 6 Is a hydrocarbon group.
"halogen" means fluorine, chlorine, bromine, iodine.
“C 1 -C 3 Alkoxy "of (a) represents methoxy, ethoxy, n-propoxy, isopropoxy.
"by at least one C 1 -C 3 The "alkyl-substituted phenyl" of (a) means that the phenyl group is attached to the parent structure, but that there is at least one substituent on the phenyl group, and there may be 2, 3,4 or 5 substituents on the phenyl group, the substituents present on the phenyl group being selected from C 1 -C 3 Any one or more of the alkyl groups of (a).
“-NR x - "means that the N atom is a ring-forming atom and R is present on the N atom x As a substituent.
“-CR y - "means that the C atom is a ring-forming atom and R is present on the C atom y As a substituent.
As described above, the first aspect of the present invention provides a heterocyclic amide-azaindole compound having a structure represented by formula (I),
wherein, in the formula (I),
R 1 selected from substituted or unsubstituted C 1 -C 12 Alkyl, -SO of (E) 2 -C 1 -C 6 Alkyl of (a); and R is 1 Optionally present substituents from the group consisting of halogen, C 1 -C 3 Alkoxy, phenyl, substituted by at least one C 1 -C 3 Phenyl substituted by alkyl;
R 2 is H or C 1 -C 3 Alkyl of (a);
X 1 is O or-NR x -；R x Is C 1 -C 3 Alkyl of (a);
X 2 is N or-CR y -；R y Is C 1 -C 3 Is a hydrocarbon group.
Preferably, in formula (I), R 1 Selected from substituted or unsubstituted C 1 -C 8 Alkyl, -SO of (E) 2 -C 1 -C 6 Alkyl of (a); and R is 1 Optionally present substituents from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, ethoxy, n-propoxy, isopropoxy, phenyl, at least one C 1 -C 3 Phenyl substituted by alkyl; more preferably, R 1 Selected from substituted or unsubstituted C 1 -C 8 Alkyl, -SO of (E) 2 -C 1 -C 6 Alkyl of (a); and R is 1 Optionally present substituents from the group consisting of fluorine, chlorine, methoxy, ethoxy, n-propoxy, phenyl, and at least one C 1 -C 3 Phenyl substituted by alkyl.
Preferably, in formula (I), R 2 Is H, methyl, ethyl, n-propyl or isopropyl; more preferably, R 2 H.
Preferably, in formula (I)Wherein X is 1 Is O or-NR x -；R x Methyl, ethyl, n-propyl or isopropyl; more preferably X 1 Is O or-NR x -；R x Methyl, ethyl or n-propyl.
Preferably, in formula (I), X 2 Is N or-CR y -；R y Methyl, ethyl, n-propyl or isopropyl; more preferably X 2 Is N or-CR y -；R y Methyl, ethyl or n-propyl.
According to a preferred embodiment, in formula (I),
R 1 selected from substituted or unsubstituted C 1 -C 8 Alkyl, -SO of (E) 2 -C 1 -C 6 Alkyl of (a); and R is 1 Optionally present substituents from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, ethoxy, n-propoxy, isopropoxy, phenyl, at least one C 1 -C 3 Phenyl substituted by alkyl;
R 2 is H, methyl, ethyl, n-propyl or isopropyl;
X 1 is O or-NR x -；R x Methyl, ethyl, n-propyl or isopropyl;
X 2 is N or-CR y -；R y Is methyl, ethyl, n-propyl or isopropyl.
According to another preferred embodiment, in formula (I),
R 1 selected from substituted or unsubstituted C 1 -C 8 Alkyl, -SO of (E) 2 -C 1 -C 6 Alkyl of (a); and R is 1 Optionally present substituents from the group consisting of fluorine, chlorine, methoxy, ethoxy, n-propoxy, phenyl, and at least one C 1 -C 3 Phenyl substituted by alkyl;
R 2 is H;
X 1 is O or-NR x -；R x Methyl, ethyl or n-propyl;
X 2 is N or-CR y -；R y Methyl, ethyl or n-propyl.
According to a particularly preferred embodiment, the compound of the structure of formula (I) is selected from any one of the following:
compound 1:compound 2:
Compound 3:compound 4:
Compound 5:compound 6:
Compound 7:compound 8:
Compound 9:compound 10:
Compound 11:compound 12:
Compound 13:compound 14:
Compound 15:compound 16:
Compound 17:compound 18:
Compound 19:compound 20:
Compound 21:compound 22:
Compound 23:compound 24:
Compound 25:compound 26:
Compound 27:compound 28:
Compound 29:compound 30:
Compound 31:compound 32:
Compound 33:
the present invention is not particularly limited to the process for preparing the compounds described in the first aspect and a person skilled in the art may determine suitable synthetic routes to obtain the compounds described in the first aspect of the invention based on the formulae provided herein in combination with knowledge known in the art of organic synthesis. However, in order to achieve significantly higher yields and purities, the present invention provides a preferred process as described in the second aspect for the preparation of the compounds as described in the first aspect of the invention.
As previously mentioned, a second aspect of the present invention provides a process for preparing a compound as described in the first aspect, the process comprising: contacting a compound shown in a formula (II) with a condensing agent, a compound shown in a formula (III) and an alkaline substance in the presence of a solvent to react;
wherein in the formula (II) and the formula (III), the definition of each substituent is correspondingly the same as the definition described in any one of the first aspects.
Preferably, the solvent is selected from at least one of dichloromethane, chloroform, dichloroethane, acetonitrile, toluene, tetrahydrofuran, and benzene.
Preferably, the molar ratio of the compound of formula (II) to the compound of formula (III) is 1:0.8-1.5.
Preferably, the contacting conditions include: the reaction temperature is 0-120 ℃; the reaction time is 2-24h.
Preferably, the condensing agent is selected from DCC (dicyclohexylcarbodiimide), DIC (1, 3-diisopropylcarbodiimide), EDCI (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride), CDI (N, N '-carbonyldiimidazole), HATU (O- (7-azabenzotriazol-1-yl) -N, N, N', N '-tetramethyluronium hexafluorophosphate), HBTU (O- (benzotriazol-1-yl) -N, N' -tetramethyluronium hexafluorophosphate), TBTU (2- (1H-benzotrisazo L-1-yl) -1, 3-tetramethyluronium tetrafluoroborate), pyBOP (1H-benzotriazol-1-yloxytripyrrolidinyl hexafluorophosphate).
Preferably, the basic substance is at least one selected from pyridine, triethylamine, DMAP (4-dimethylaminopyridine), DIPEA (N, N-diisopropylethylamine), DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene), sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide.
The relation between the amounts of the solvent, the condensing agent and the basic substance used in the aforementioned production method is not particularly limited, and may be adjusted according to known parameters in the field of organic synthesis or may be appropriately adjusted by those skilled in the art according to examples provided hereinafter.
In addition, the synthesis method according to the second aspect of the present invention may be further subjected to some conventional post-treatments, such as filtration, solvent removal, drying, column chromatography, etc., which are well known to those skilled in the art, and the present invention is not described herein in detail, and those skilled in the art should not understand the limitation of the present invention.
As previously mentioned, a third aspect of the invention provides the use of a compound as described in the first aspect as a herbicide for controlling weeds.
Preferably, the weeds are selected from at least one of broadleaf weeds, grassy weeds and sedge weeds.
Preferably, the weeds are selected from at least one of the group consisting of descurainia sophia, shepherd's purse, chenopodium album, galium, veronicastrum, radix et rhizoma zoysiae rubrum, acalypha australis, black nightshade, lantern grass, purslane, amaranthus retroflexus, carp intestines, barnyard grass, goosegrass, green bristlegrass, crabgrass, alopecuroide, japanese alopecuroide, festival wheat, wild oat, brome, stephania, paspalum distichum, japanese rush and abnormal-shaped nutgrass.
As described above, the fourth aspect of the present invention provides a herbicide containing a herbicidally effective amount of an active ingredient which is at least one of the compounds described in the first aspect.
Preferably, in the herbicide, the content of the active ingredient is 1 to 100wt%, for example, may be 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, or the like.
Preferably, the herbicide also contains auxiliary materials.
The present invention has no special requirements on the types of the auxiliary materials, and a person skilled in the art can select the auxiliary materials according to dosage forms in combination with the types of the auxiliary materials which are known to be applied in the pesticide field, and the present invention is not repeated herein, and the person skilled in the art should not understand the limitation of the present invention.
A fifth aspect of the present invention provides the use of a compound as described in the first aspect or a herbicide as described in the fourth aspect for controlling weeds in a field for planting any one crop selected from corn, rice, wheat, sorghum, peanut, soybean, canola.
The invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, all the raw materials used were commercially available in general analytical purity.
Unless otherwise specified, room temperature or normal temperature referred to in the following examples each represents 25.+ -. 2 ℃.
Preparation example 1
Weighing 0.4mol of 7-azaindole, adding the 7-azaindole into a 2L eggplant-shaped bottle, adding 1.3L of ethyl acetate to dissolve the 7-azaindole, then slowly adding 0.6mol of m-chloroperoxybenzoic acid into the system in batches under ice bath, reacting for about 2 hours at room temperature after the addition, monitoring the reaction condition by TLC, carrying out suction filtration after the raw materials are completely reacted, and drying a filter cake to obtain an intermediate I-2, wherein the yield is 98%.
In a 2L eggplant-shaped bottle, 0.39mol of intermediate I-2 is dissolved in 1.1L of ultra-dry N, N-dimethylformamide, 0.78mol of tetramethyl ammonium bromide and 0.78mol of methylsulfonic anhydride are sequentially added under ice bath, the ice bath is removed after the addition is finished, the temperature is raised to 70 ℃ for reaction for about 2 hours, TLC monitors the reaction, the system is cooled to room temperature after the raw material point disappears, the reaction solution is poured into 3.3L of ice water, a large amount of solids are separated out, 50wt% of sodium hydroxide solution is dropwise added under stirring, the pH value of the solution is regulated to 7, suction filtration is carried out, and the obtained solids are dried to obtain intermediate I-3, and the yield is 68%.
10.2mmol of intermediate I-3 is weighed and placed in a 100mL eggplant-shaped bottle, 20mL of DMF solution is added, 20.4mmol of sodium hydride is slowly added in batches under ice bath, after the addition is finished, the ice bath is removed, 20.4mmol of methyl iodide is added after stirring for 1h at room temperature, TLC tracks the progress of the reaction, after the reaction is completed, the system is poured into 100mL of ice water, 50mL of ethyl acetate is used for extracting the reaction system for 3 times each time, the organic phase is washed twice with 40mL of saturated saline solution and then combined, anhydrous sodium sulfate is dried, and finally, the intermediate I-4 is obtained through column chromatography purification, and the yield is 85%.
8mmol of intermediate I-4, 0.24mmol of palladium acetate, 16mmol of N, N' -dicyclohexylcarbodiimide, 0.24mmol of 4, 5-bis (diphenylphosphine) -9, 9-dimethylxanthene and magneton are sequentially added into a 100mL Schlenk tube, 20mL of DMF solution is added under the protection of nitrogen, 56mmol of anhydrous formic acid and 16mmol of triethylamine are slowly added dropwise, the system is heated to 90 ℃ after the dropwise addition to react for about 2h, TLC monitors the reaction system, after the reaction is finished, the insoluble substances are cooled to room temperature to be pumped and filtered, the obtained filtrate is poured into 100mL of water, extracted for 3 times by 50mL of dichloromethane, the organic phase is collected and washed by 40mL of saturated saline, the organic phase is finally combined, and the intermediate I-5 is obtained after the anhydrous sodium sulfate is dried by column chromatography, and the yield is 90%.
2mmol of carboxylic acid intermediate I-5 is weighed and added into a 50mL eggplant-shaped bottle, the obtained product is dissolved in 15mL of acetonitrile, 2.4mmol of N, N' -carbonyldiimidazole is added, after reflux reaction is carried out for 1h, TLC monitoring is carried out, after the raw material point disappears, 2.4mmol of 1-methyl-5-aminotetrazole and 4mmol of 1, 8-diazabicyclo [5.4.0] undec-7-ene are added, the reflux reaction is continued, TLC tracks the reaction condition, acetonitrile in the system is dehydrated after the reaction is finished, then 20mL of hydrochloric acid solution with the concentration of 1mol/L is added, 20mL of dichloromethane is used for extraction for 3 times each time, the organic phases are combined, and column chromatography is carried out after drying to obtain white solid, namely the compound 1, the yield is 65%.
Preparation example 2
In a 50mL eggplant-shaped bottle, 2mmol of carboxylic acid intermediate I-5, 15mL of acetonitrile and 2.4mmol of N, N' -carbonyldiimidazole are respectively added, TLC monitoring is carried out after reflux reaction is carried out for 1h, 2.4mmol of 2-amino-5-methyl-1, 3, 4-oxadiazole and 4mmol of 1, 8-diazabicyclo [5.4.0] undec-7-ene are added after the raw material point disappears, reflux reaction is continued, TLC tracks the reaction condition, the solvent is dried after the reaction is finished, then 20mL of hydrochloric acid solution with the concentration of 1mol/L is added, 20mL of dichloromethane is used for extraction for 3 times each time, the organic phases are combined, and column chromatography is carried out after drying to obtain white solid, namely the compound 18, the yield is 63%.
Some of the compounds of the present invention were prepared by the methods described above in analogy to preparation 1 and preparation 2, the characterization data of the resulting compounds being shown in Table 1, the yields in Table 1 being the yields of the last step of the reaction.
TABLE 1
Test example 1
Enzyme level inhibition activity assay (coupling method):
enzyme level inhibitory Activity of partial Compounds against Arabidopsis HPPD (AtHPPD) was tested using the coupling method reported in the literature (Amaya, alphonso A. Et al kinetic analysis of human homogentisate, 2-dioxygenase. Industries of Biochemistry)&Biophysics2004,421, 135-142.). Weighing 2-3mg of the compound in an EP tube of 1.5mL, centrifuging on a centrifuge, and standing. And calculating the volume of 10mM of the stock solution according to the purity, relative molecular mass, mass and other information of the inhibitor, and adding DMSO with the corresponding volume for uniform mixing. The inhibitor solution was then diluted again with DMSO to 1mM for use, and finally the inhibitor was diluted with 20mM HEPES buffer to 10mM for primary screening. After the primary screening is finished, the inhibitor is diluted according to the inhibition rate obtained by the primary screening, 11 concentrations are prepared, and the inhibition rate of the inhibitor with each concentration on the enzyme is ensured to be uniformly distributed. The coupling method is used for testing under an enzyme label instrument, the test is carried out for three times in parallel, and the average value is taken as the IC of the inhibitor to the AtHPPD 50 Values, and as a control agent, the commercial inhibitor mesotrione. The results are shown in Table 2.
Table 2 evaluation of Athppd enzyme inhibitory Activity of some compounds
Numbering of compounds IC 50 (μM) Numbering of compounds IC 50 (μM)
1 0.285±0.025 15 0.451±0.001
2 0.282±0.032 16 0.484±0.001
3 0.183±0.007 17 0.536±0.008
4 0.164±0.010 20 0.413±0.031
5 0.162±0.006 21 0.430±0.022
6 0.135±0.010 22 0.390±0.023
7 0.226±0.014 23 0.597±0.015
8 0.114±0.013 24 0.721±0.037
9 0.320±0.014 25 0.309±0.018
10 0.426±0.020 26 0.477±0.016
11 0.126±0.014 28 0.474±0.046
12 0.130±0.006 29 0.577±0.005
13 0.209±0.005 30 0.455±0.003
14 0.279±0.016 Mesotrione 0.363±0.015
Test example 2
This test example is used to illustrate the herbicidal activity (expressed as growth inhibition (%)) of the compounds of the present invention.
Herbicidal activity assay (potting method): the test targets are amaranth and abutilon, and the post-emergence stem leaf spray: taking paper cup with inner diameter of 7cm, loading composite soil (vegetable garden soil: seedling substrate, 1:2, v/v) to 3/4 position, directly sowing weeds, covering soil by 0.2cm, and growing until 4-5 leaf period is reached for standby. After the compound of the invention and the comparative compound are applied in an automatic spray tower according to the dosage of 320g.ai/ha (g/ha), the plant leaf liquid is transferred into a greenhouse for cultivation (25 ℃ and 70% of humidity) after being dried, and the results are investigated after 30 days.
The growth inhibition rate evaluation method was a visual inspection method, and was specifically rated according to the conditions shown in table 3, and the test results are shown in table 4.
TABLE 3 Table 3
TABLE 4 Table 4
From the above results, it can be seen that the heterocyclic amide-azaindole compounds provided by the invention have excellent herbicidal activity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (12)

1. A heterocyclic amide-azaindole compound is characterized in that the compound has a structure shown in a formula (I),
formula (I)
Wherein, in the formula (I),
R 1 selected from-SO 2 -C 1 -C 6 Alkyl, substituted or unsubstituted C 1 -C 12 Alkyl of (a); and R is 1 Optionally present substituents from the group consisting of halogen, C 1 -C 3 Alkoxy, phenyl, substituted by at least one C 1 -C 3 Phenyl substituted by alkyl;
R 2 is H or C 1 -C 3 Alkyl of (a);
X 1 is-NR x -，X 2 Is N; r is R x Is C 1 -C 3 Alkyl of (a); or,
X 1 is O, X 2 is-CR y -；R y Is C 1 -C 3 Is a hydrocarbon group.
2. The compound according to claim 1, wherein, in formula (I),
R 1 selected from-SO 2 -C 1 -C 6 Alkyl, substituted or unsubstituted C 1 -C 8 Alkyl of (a); and R is 1 Optionally present substituents from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, ethoxy, n-propoxy, isopropoxy, phenyl, at least one C 1 -C 3 Phenyl substituted by alkyl;
R 2 is H, methyl, ethyl, n-propyl or isopropyl;
X 1 is-NR x -，X 2 Is N; r is R x Methyl, ethyl, n-propyl or isopropyl; or,
X 1 is O, X 2 is-CR y -；R y Is methyl, ethyl, n-propyl or isopropyl.
3. The compound according to claim 2, wherein, in formula (I),
R 1 selected from-SO 2 -C 1 -C 6 Alkyl, substituted or unsubstituted C 1 -C 8 Alkyl of (a); and R is 1 Optionally present substituents from the group consisting of fluorine, chlorine, methoxy, ethoxy, n-propoxy, phenyl, and at least one C 1 -C 3 Phenyl substituted by alkyl;
R 2 is H;
X 1 is-NR x -，X 2 Is N; r is R x Methyl, ethyl or n-propyl; or,
X 1 is O, X 2 is-CR y -；R y Methyl, ethyl or n-propyl.
4. A compound according to claim 3, wherein the compound of the structure of formula (I) is selected from any one of the following:
compound 1:compound 2:
Compound 3:compound 4:
Compound 5:compound 6:
Compound 7:compound 8:
Compound 9:compound 10:
Compound 11:compound 12:
Compound 13:compound 14:
Compound 15:compound 16:
Compound 17:compound 18:
Compound 19:compound 20:
Compound 21:compound 22:
Compound 23:compound 24:
Compound 25:compound 26:
Compound 27:compound 28:
Compound 29:compound 30:
Compound 31:compound 32:
Compound 33:。
5. a process for preparing a compound according to any one of claims 1 to 4, comprising: contacting a compound shown in a formula (II) with a condensing agent, a compound shown in a formula (III) and an alkaline substance in the presence of a solvent to react;
formula (II), A>Formula (III),
wherein in the formula (II) and the formula (III), the definition of each substituent is correspondingly the same as that described in any one of claims 1 to 4.
6. The method of claim 5, wherein the contacting conditions comprise: the reaction temperature is 0-120 ℃; the reaction time is 2-24h; and/or
The solvent is at least one selected from dichloromethane, chloroform, dichloroethane, acetonitrile, toluene, tetrahydrofuran and benzene; and/or
The molar ratio of the compound shown in the formula (II) to the compound shown in the formula (III) is 1:0.8-1.5.
7. The use of a compound according to any one of claims 1 to 4 as herbicide for controlling weeds.
8. The use according to claim 7, wherein the weeds are selected from at least one of broadleaf weeds and grassy weeds.
9. The use according to claim 8, wherein the weeds are selected from at least one of descurainia sophia, shepherd's purse, chenopodium, abutilon, galium, veronicastrum, radix et rhizoma halii, copperleaf, black nightshade, lantern, purslane, amaranth, barnyard grass, goosegrass, green bristlegrass, crabgrass, japanese barley, festival wheat, wild oat, brome, stephania and paspalum distichum.
10. The use according to claim 8, wherein the weeds are selected from the group consisting of alopecuroide.
11. A herbicide comprising a herbicidally effective amount of an active ingredient which is at least one of the compounds of any one of claims 1 to 4.
12. Use of a compound according to any one of claims 1 to 4 or a herbicide according to claim 11 for controlling weeds in a field where any one of crops selected from corn, rice, wheat, sorghum, peanut, soybean, canola is planted.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1137795A (en) * 1993-11-17 1996-12-11 泽尼卡有限公司 Herbicidal pyrrolopyridine compounds
CN101479253A (en) * 2006-04-28 2009-07-08 先正达参股股份有限公司 Insecticidal compounds
CN101784191A (en) * 2007-04-26 2010-07-21 先正达参股股份有限公司 4-aza indole derivatives and their use as fungicides
EP1651612B9 (en) * 2003-07-22 2012-09-05 Astex Therapeutics Limited 3,4-disubstituted 1h-pyrazole compounds and their use as cyclin dependent kinases (cdk) and glycogen synthase kinase-3 (gsk-3) modulators
CN103864785A (en) * 2014-03-11 2014-06-18 中国农业大学 Thiazoline derivatives with aza-indole framework as well as preparation method and application thereof
CN110669016A (en) * 2018-09-29 2020-01-10 山东先达农化股份有限公司 Triketone compound, preparation method and application thereof, and herbicide
CN110963973A (en) * 2018-09-29 2020-04-07 山东先达农化股份有限公司 Triketone compound containing quinazolinedione fragment, preparation method and application thereof, and herbicide
WO2020164938A1 (en) * 2019-02-12 2020-08-20 Basf Se Heterocyclic compounds for the control of invertebrate pests
BR112021012563A2 (en) * 2018-12-27 2021-09-14 Qingdao Kingagroot Chemical Compound Co., Ltd. PYRIDYLOXY CARBOXYLIC ACID OXIMA DERIVATIVE, PREPARATION METHOD, HERBICIDAL COMPOSITION AND APPLICATION THEREOF
CN116003401A (en) * 2021-10-21 2023-04-25 山东先达农化股份有限公司 Azaindole compound, preparation method and application thereof, and herbicide

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112012001943B1 (en) * 2009-07-29 2017-11-14 Bayer Intellectual Property Gmbh 4- (3-ALKYLTIBENZOYL) PYRAZOLES, HERBICIDE COMPOSITION, METHOD FOR CONTROL OF UNDESIRED PLANTS AND USE OF 4- (3-ALKYLTYBENZOYL) PYRAZOLES

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1137795A (en) * 1993-11-17 1996-12-11 泽尼卡有限公司 Herbicidal pyrrolopyridine compounds
EP1651612B9 (en) * 2003-07-22 2012-09-05 Astex Therapeutics Limited 3,4-disubstituted 1h-pyrazole compounds and their use as cyclin dependent kinases (cdk) and glycogen synthase kinase-3 (gsk-3) modulators
CN101479253A (en) * 2006-04-28 2009-07-08 先正达参股股份有限公司 Insecticidal compounds
CN101784191A (en) * 2007-04-26 2010-07-21 先正达参股股份有限公司 4-aza indole derivatives and their use as fungicides
CN103864785A (en) * 2014-03-11 2014-06-18 中国农业大学 Thiazoline derivatives with aza-indole framework as well as preparation method and application thereof
CN110669016A (en) * 2018-09-29 2020-01-10 山东先达农化股份有限公司 Triketone compound, preparation method and application thereof, and herbicide
CN110963973A (en) * 2018-09-29 2020-04-07 山东先达农化股份有限公司 Triketone compound containing quinazolinedione fragment, preparation method and application thereof, and herbicide
BR112021012563A2 (en) * 2018-12-27 2021-09-14 Qingdao Kingagroot Chemical Compound Co., Ltd. PYRIDYLOXY CARBOXYLIC ACID OXIMA DERIVATIVE, PREPARATION METHOD, HERBICIDAL COMPOSITION AND APPLICATION THEREOF
WO2020164938A1 (en) * 2019-02-12 2020-08-20 Basf Se Heterocyclic compounds for the control of invertebrate pests
CN116003401A (en) * 2021-10-21 2023-04-25 山东先达农化股份有限公司 Azaindole compound, preparation method and application thereof, and herbicide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"HPPD抑制剂的机理与应用进展";赵李霞等;《植物保护》;20081231;第34卷;第12-16页 *
"Simplification of Natural β-Carboline Alkaloids to Obtain Indole Derivatives as Potent Fungicides against Rice Sheath Blight";Jie Zeng et al.;《Molecules》;第25卷;第1189（共13）页 *

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