WO2023066372A1 - Azaindole compound and preparation method therefor and use thereof, and herbicide - Google Patents

Azaindole compound and preparation method therefor and use thereof, and herbicide Download PDF

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WO2023066372A1
WO2023066372A1 PCT/CN2022/126676 CN2022126676W WO2023066372A1 WO 2023066372 A1 WO2023066372 A1 WO 2023066372A1 CN 2022126676 W CN2022126676 W CN 2022126676W WO 2023066372 A1 WO2023066372 A1 WO 2023066372A1
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alkyl
alkylene
formula
group
phenyl
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PCT/CN2022/126676
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French (fr)
Chinese (zh)
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杨光富
周少萌
赵静
蔡卓梅
王现全
陈恩昌
张天柱
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山东先达农化股份有限公司
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Publication of WO2023066372A1 publication Critical patent/WO2023066372A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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

Definitions

  • the invention relates to the field of pesticide compounds, in particular to an azaindole compound, a preparation method and application thereof, and a herbicide.
  • p-Hydroxyphenylpyruvate dioxygenase is an important member of the 2-histidine-1-carboxylate triad structure oxidase family, which can convert para- Hydroxyphenylpyruvate is catalyzed into homogentisic acid, which is further converted into plastoquinone and tocopherol.
  • Plastid quinone and tocopherol in plants are key cofactors for the synthesis of phytoene dehydrogenase (PDS), and PDS can further promote the synthesis of carotenoids in plants, which can protect plants from Damage from singlet oxygen.
  • PDS phytoene dehydrogenase
  • the object of the present invention is to provide a novel ultra-efficient HPPD-inhibiting herbicidal compound that is safe for crops.
  • the first aspect of the present invention provides an azaindole compound, which has a structure shown in formula (I):
  • R is a group shown in formula (R-1) or formula (R-2),
  • R X is selected from H, halogen, C 1 -C 3 alkyl, C 1 -C 3 alkyl substituted by 1-6 halogens, C 2 -C 4 ester, cyano, phenyl, nitrate base;
  • R Y is selected from C 1 -C 10 alkyl, C 1 -C 10 alkyl substituted by 1-9 halogens, -C 1 -C 6 alkylene -OC 1 -C 6 alkyl, -C 1 -C 6 alkylene -SC 1 -C 6 alkyl, -C 1 -C 5 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 6 alkylene group-CN, -C 1 -C 6 alkylene group-Si-C 1 -C 6 alkyl group, C 2 -C 12 alkenyl group, C 2 -C 12 alkynyl group, -C 1 -C 6 alkylene-C ⁇ C-Si-C 1 -C 6 alkyl, -SO 2 -C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, containing at least one C 2 -C 7 saturated or unsaturated heterocyclo
  • the combination A is composed of C 1 -C 6 alkyl, halogen, and C 1 -C 6 alkyl substituted by 1-6 halogens;
  • R 3 and R 4 are each independently selected from H, C 1 -C 3 alkyl
  • R 5 is selected from C 1 -C 3 alkyl
  • R 6 is selected from H, C 1 -C 3 alkyl, C 3 -C 6 saturated cycloalkyl
  • R 7 selected from H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -CO-N(C 1 -C 3 alkyl) 2 , -C 1 -C 6 alkylene-O-CO-OC 1 -C 6 alkyl, -CO-C 1 -C 6 alkyl, -C 1 -C 6 alkylene-CO-phenyl, - CS-N(C 1 -C 3 alkyl) 2 , -CO-pyrazolyl substituted by at least one group in combination A, -SO 2 -C 1 -C 6 alkyl, C 2 - C 6 ester group, -C 1 -C 6 alkylene-phenyl group.
  • the second aspect of the present invention provides a method for preparing the compound described in the aforementioned first aspect, the method comprising: performing a rearrangement reaction on a compound represented by formula (II-1) or a compound represented by formula (II-2), to obtain The product shown in formula (I-1) or the product shown in formula (I-2);
  • the method also includes: performing a substitution reaction between the product represented by the formula (I-2) and the compound represented by the formula (II-3), to obtain the product represented by the formula (I-2);
  • the third aspect of the present invention provides the use of the compound described in the aforementioned first aspect as a herbicide.
  • the fourth aspect of the present invention provides a herbicide, which contains an adjuvant and a herbicidally effective amount of the compound described in the first aspect.
  • the azaindole compound provided by the present invention has excellent HPPD inhibitory effect, has significant inhibitory effect on weeds including broad-leaved weeds, grass weeds and sedge weeds, and has a significant inhibitory effect on corn, rice , wheat, sorghum, peanuts, soybeans, rapeseed and other crops have high safety.
  • the halogen in the present invention includes fluorine, chlorine, bromine and iodine.
  • the C 1 -C 3 alkyl group in the present invention includes methyl, ethyl, n-propyl and isopropyl.
  • the C 1 -C 3 alkyl substituted by 1-6 halogens in the present invention means any 1-6 H in any group selected from methyl, ethyl, n-propyl, and isopropyl (eg 1, 2, 3, 4, 5, 6 H) are substituted by halogen.
  • the C 2 -C 4 ester group in the present invention represents a structure represented by -COOR 1 , and R 1 is selected from any group among methyl, ethyl, n-propyl, and isopropyl.
  • the C 1 -C 10 alkyl group in the present invention means a straight chain alkyl group or a branched group with a total of 1-10 carbon atoms (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10). Alkanes.
  • C 1 -C 6 alkyl has a similar definition, differing only in the total number of carbon atoms.
  • the C 1 -C 10 alkyl group substituted by 1-9 halogens represents the C 1 -C 10 1-9 H on the alkyl group are replaced by halogen.
  • the C 1 -C 6 alkylene group in the present invention means an alkylene group with a total of 1-6 carbon atoms (such as 1, 2, 3, 4, 5, 6), which can be branched or branched chain alkylene base.
  • a C 1 -C 5 alkylene group has a similar definition, differing only in the total number of carbon atoms.
  • the C 2 -C 12 alkenyl group in the present invention means an alkenyl group with a total of 2-12 carbon atoms (such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12), which can be Branched alkenyl or branched alkenyl containing at least one double bond.
  • the C 2 -C 12 alkynyl group in the present invention means an alkynyl group with a total of 2-12 carbon atoms (such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12), which can be Straight-chain or branched-chain alkynyl containing at least one triple bond.
  • the C 3 -C 8 cycloalkyl group in the present invention refers to a cycloalkyl group with a total of 3-8 carbon atoms, and the number of ring carbon atoms is any one of 3-8, such as 3, 4, 5, 6, 7 ,8.
  • the first aspect of the present invention provides an azaindole compound.
  • R is a group represented by formula (R-1), R X is selected from H, halogen, C 1 -C 3 alkyl, consisting of 1-6 Halogen substituted C 1 -C 3 alkyl, C 2 -C 4 ester, cyano, phenyl, nitro; RY is selected from C 1 -C 8 alkyl, substituted by 1-6 halogens C 1 -C 8 alkyl, -C 1 -C 4 alkylene -OC 1 -C 6 alkyl, -C 1 -C 4 alkylene -SC 1 -C 6 alkyl, -C 1 -C 3 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 4 alkylene -CN, -C 1 -C 4 alkylene -Si -C 1 -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkyn
  • Preferred embodiment 2 On the basis of the aforementioned preferred embodiment 1, more preferably, the combination A is composed of C 1 -C 4 alkyl, halogen, C 1 - Alkyl composition of C4 .
  • R is a group shown in formula (R-1), and the compound shown in formula (I) is selected from any one of the following table 1:
  • R is a group represented by formula (R-2), R X is selected from H, halogen, C 1 -C 3 alkyl, consisting of 1-6 Halogen substituted C 1 -C 3 alkyl, C 2 -C 4 ester, cyano, phenyl, nitro; RY is selected from C 1 -C 8 alkyl, substituted by 1-6 halogens C 1 -C 8 alkyl, -C 1 -C 4 alkylene -OC 1 -C 6 alkyl, -C 1 -C 4 alkylene -SC 1 -C 6 alkyl, -C 1 -C 3 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 4 alkylene -CN, -C 1 -C 4 alkylene -Si -C 1 -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkyn
  • R is a group represented by formula (R-2), R X is selected from H, halogen, C 1 -C 3 alkyl, consisting of 1-6 Halogen substituted C 1 -C 3 alkyl, C 2 -C 4 ester, cyano, phenyl, nitro; RY is selected from C 1 -C 6 alkyl, substituted by 1-6 halogens C 1 -C 6 alkyl, -C 1 -C 4 alkylene -OC 1 -C 6 alkyl, -C 1 -C 4 alkylene -SC 1 -C 6 alkyl, -C 1 -C 3 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 4 alkylene -CN, -C 1 -C 4 alkylene -Si -C 1 -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkyn
  • R is a group shown in formula (R-2), and the compound shown in formula (I) is selected from any one of the following table 2:
  • R is a group represented by formula (R-1) or formula (R-2), and R X is selected from H, halogen, C 1 -C 3 alkane C 1 -C 3 alkyl group, C 2 -C 4 ester group, cyano group, phenyl group, nitro group; RY is selected from C 1 -C 8 alkyl group, C 1 -C 8 alkyl, -C 1 -C 4 alkylene -OC 1 -C 6 alkyl, -C 1 -C 4 alkylene -SC 1 substituted by 1-6 halogens -C 6 alkylene, -C 1 -C 3 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 4 alkylene -CN, -C 1 -C 4 Alkylene-Si-C 1 -C 6 Alkyl, C 2 -C 8 Alkenyl, C 2 -C 8 Alkyl
  • Preferred embodiment 8 On the basis of the aforementioned preferred embodiment 7, more preferably, the combination A is composed of C 1 -C 4 alkyl, halogen, C 1 - Alkyl composition of C4 .
  • R is a group shown in formula (R-1) or formula (R-2), and the compound shown in formula (I) is selected from the aforementioned Table 1 and Any one of the aforementioned Table 2.
  • the present invention has no special requirements on the specific method for preparing the compound described in the first aspect. Those skilled in the art can determine a suitable preparation route according to the structural formula disclosed in the present invention and in combination with known knowledge in the field of organic pesticide synthesis to obtain the first compound. However, in order to obtain compounds with better yield and purity, the present invention provides the preferred method described in the second aspect to prepare the compound described in the first aspect.
  • the second aspect of the present invention provides a method for preparing the compound described in the first aspect.
  • the present invention has no special limitations on the conditions and specific operating parameters involved in the aforementioned preparation method. Those skilled in the art can select according to the knowledge known in the art, or according to the following aspects of the present invention. The parameters and conditions provided in the examples listed herein are selected, and the present invention will not be described in detail here, and those skilled in the art should not understand it as a limitation of the present invention.
  • the third aspect of the present invention provides the use of the compound described in the aforementioned first aspect in herbicides.
  • the herbicides described in the present invention are directed against the group consisting of Artemisia solanum, shepherd's purse, quinoa, velvetleum, pig's weed, mother-in-law, chickweed, amaranth, solanum nigrum, lantern plant, purslane, retrovertica Amaranth, carp sausage, barnyardgrass, goosegrass, golden foxtail, foxtail, crabgrass, kanmai, Japanese kanmai, festival wheat, wild oats, brome, daughter of gold, paspalum bispinus, firefly rush, At least one of the weeds in the heterosedge is controlled by an effective herbicide.
  • the fourth aspect of the present invention provides a herbicide, which contains an adjuvant and a herbicidally effective amount of the compound described in the first aspect.
  • the content of the compound is 0.1-99.99wt%.
  • the content of the compound is 1wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%.
  • the dosage form of the herbicide is selected from at least one of emulsifiable concentrate, suspension concentrate, wettable powder, powder, granule, aqueous solution, mother liquor and mother powder.
  • the compound of the present invention has high safety to crops such as corn, rice, wheat, sorghum, peanut, soybean and rapeseed.
  • room temperature or normal temperature involved in the following examples all represent 25 ⁇ 2°C.
  • the insoluble matter was suction-filtered, and the organic phase was poured into 200mL of water, and then the aqueous phase was extracted with 50mL of dichloromethane for 3 times, the organic phase was combined, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain the intermediate 1-3, the yield is 85%.
  • the insoluble matter was suction-filtered, and the organic phase was poured into 100 mL of water, then the aqueous phase was extracted with 30 mL of dichloromethane for 3 times, the organic phases were combined, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain the intermediate 1-11, the yield was 85%.
  • the insoluble matter was suction-filtered, and the organic phase was poured into 200mL of water, and then the aqueous phase was extracted with 50mL of dichloromethane for 3 times, the organic phase was combined, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain the intermediate 1-14, the yield is 85%.
  • the organic phase was washed 3 times with 10 mL of 1 mol/L hydrochloric acid, and then washed 2 times with 30 mL of saturated NaHCO 3 solution, the organic phase was collected, dried over anhydrous Na 2 SO 4 , and purified by column chromatography to obtain the enol ester intermediate Body 1-17, the yield is 90%.
  • the preparation methods of the remaining compounds of the present invention refer to the aforementioned preparation examples, and the characterization data of some specific compounds of the present invention are shown in Table 3.
  • the yields in Table 3 are calculated based on the main raw materials in the last step of the chemical reaction to obtain the compound.
  • Preliminary screening test (pot planting method): the test target and the test crops are as shown in the following table, and the stems and leaves are sprayed after emergence: take a paper cup with an inner diameter of 7cm and fill it with compound soil (vegetable garden soil: seedling substrate, 1:2, v/v ) to 3/4, sow weeds directly, cover with soil 0.2cm, and wait for the 4-5 leaf stage to be used for later use.
  • the test compound was sprayed in the automatic spray tower according to the dose shown in the following table, the weed or crop foliage liquid was dried and then moved into the greenhouse for cultivation (humidity 70%), and the results were investigated after 30 days.
  • the evaluation method of the growth inhibition rate is the visual method, and the rating is specifically performed according to the conditions shown in Table 4, and the test results are shown in Table 5-Table 18.
  • Enzyme-level inhibitory activity test (coupling method): The enzyme-level inhibitory activity of some compounds on Arabidopsis thaliana HPPD (AtHPPD) was tested using the coupling method reported in the literature (Amaya, Alphonso A. et al. Kinetic analysis of Human homogentisate 1,2-dioxygenase. Archives of Biochemistry & Biophysics 2004, 421, 135-142.).
  • Compound number IC50 ( ⁇ M) Compound number IC50 ( ⁇ M) 1 0.039 ⁇ 0.004 185 0.126 ⁇ 0.006 2 0.113 ⁇ 0.005 192 0.056 ⁇ 0.003 3 0.078 ⁇ 0.002 245 0.099 ⁇ 0.005 62 0.187 ⁇ 0.004 281 0.111 ⁇ 0.002 Mesotrione 0.289 ⁇ 0.012 / /
  • the compound provided by the invention has a good effect on tested barnyard grass, foxtail, crabgrass, amaranth, quinoa, velvetleaf 6 common broad-leaved weeds and grasses. Undergraduate weeds have a significant inhibitory effect.
  • some compounds of the present invention showed 100% herbicidal control effect on 6 weeds tested at the application rate of 320 g.a.i/ha.
  • compound 1 of the present invention shows 100% herbicidal control effect on tested barnyardgrass, foxtail, crabgrass, wild oats, brome, kangaroo, and Japanese kanko .
  • the comparative compound mesotrione has excellent herbicidal effects on barnyardgrass and crabgrass, it has almost no inhibitory effect on the growth of foxtail.
  • the azaindole compounds provided by the present invention have very high herbicidal activity to broad-leaved weeds, grass weeds and Cyperaceae weeds, such as broad-leaved weeds: Artemisia sobanifolia, shepherd's purse , quinoa, velvetleaf, pig scorpion, mother-in-law, cow chickweed, iron amaranth, nightshade, lantern grass, purslane, retroverted amaranth, carp sausage; Gramineae weeds: barnyardgrass, goosegrass, goldenseal Setaria, Setaria, Crabgrass, Kan Mai Niang, Japanese Kan Mai Niang, Festival Barley, Wild Oats, Brome, Qianjinzi, Paspalum bitachy;
  • the compound of the present invention has high safety to crops, and is obviously suitable for application as a herbicide in grain crop fields, especially wheat fields. It has strong development and commercialization prospects.

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Abstract

Disclosed are an azaindole compound and a preparation method therefor and a use thereof, and an herbicide. The compound has a structure represented by formula (I). The compound has excellent herbicidal activity.

Description

一种氮杂吲哚类化合物及其制备方法和应用、一种除草剂Azaindole compound, preparation method and application thereof, and herbicide
相关申请的交叉引用Cross References to Related Applications
本申请要求2021年10月21日提交的中国专利申请202111226714.0的权益，该申请的内容通过引用被合并于本文。This application claims the benefit of Chinese Patent Application 202111226714.0 filed on October 21, 2021, the contents of which are incorporated herein by reference.
技术领域technical field
本发明涉及农药化合物领域，具体涉及一种氮杂吲哚类化合物及其制备方法和应用、一种除草剂。The invention relates to the field of pesticide compounds, in particular to an azaindole compound, a preparation method and application thereof, and a herbicide.
背景技术Background technique
高效除草剂的创制与应用是保障粮食产量、维护国家粮食安全的重要技术手段。The creation and application of high-efficiency herbicides is an important technical means to ensure grain production and maintain national food security.
我国受抗性杂草危害严重，目前正式报道的抗性杂草种类超过40种，特别是在几类重要的农作物田中，杂草抗药性的问题已经呈现出愈演愈烈的趋势，导致除草剂的使用量不断攀升，严重地影响了农业生产的可持续发展。my country is seriously endangered by resistant weeds. At present, more than 40 kinds of resistant weeds have been officially reported. Especially in several important crop fields, the problem of weed resistance has shown an intensifying trend, leading to the use of herbicides The increasing amount has seriously affected the sustainable development of agricultural production.
近年来通过研究和实际田间应用表明，以对羟苯基丙酮酸双加氧酶(EC 1.13.11.27,HPPD)为靶标的除草剂具有高效、低毒、环境友好等特点，更为重要的是，相较于AHAS、PSII、ACCase抑制类除草剂所面临的极为严重的杂草抗性问题，HPPD抑制类除草剂抗性发展极为缓慢，且与其他类型除草剂之间没有交互抗性，并特异性地对多种抗性杂草具有显著的防治效果。In recent years, studies and practical field applications have shown that herbicides targeting p-hydroxyphenylpyruvate dioxygenase (EC 1.13.11.27, HPPD) have the characteristics of high efficiency, low toxicity, and environmental friendliness. More importantly, Compared with the extremely serious weed resistance problems faced by AHAS, PSII, and ACCase-inhibiting herbicides, the development of resistance to HPPD-inhibiting herbicides is extremely slow, and there is no cross-resistance with other types of herbicides, and It has a significant control effect on a variety of resistant weeds specifically.
因此，开发新型HPPD抑制型除草剂具有十分重要的现实意义。Therefore, the development of new HPPD-inhibiting herbicides has very important practical significance.
对羟苯基丙酮酸双加氧酶属于2-组氨酸-1-羧酸盐面三联体结构氧化酶家族中的重要一员，它能够将植物体内酪氨酸代谢过程中所产生的对羟基苯丙酮酸催化转化成为尿黑酸，尿黑酸会被进一步转化成质体醌和生育酚。p-Hydroxyphenylpyruvate dioxygenase is an important member of the 2-histidine-1-carboxylate triad structure oxidase family, which can convert para- Hydroxyphenylpyruvate is catalyzed into homogentisic acid, which is further converted into plastoquinone and tocopherol.
植物体内质体醌和生育酚是合成八氢番茄红素脱氢酶(PDS)的关键辅助因子，而PDS能进一步促进植物体类胡萝卜素的合成，其能够在光照的条件下保护植物免受单线态氧的损害。Plastid quinone and tocopherol in plants are key cofactors for the synthesis of phytoene dehydrogenase (PDS), and PDS can further promote the synthesis of carotenoids in plants, which can protect plants from Damage from singlet oxygen.
若对植物体内的HPPD进行抑制，则会使酪氨酸正常代谢过程受阻，导致类胡萝卜素在植物体内缺乏，进而影响植物光合作用，使植物出现白化症状而最终死亡。If HPPD in plants is inhibited, the normal metabolic process of tyrosine will be blocked, resulting in the lack of carotenoids in plants, which will affect the photosynthesis of plants, causing albinism symptoms and eventually death of plants.
截止目前，靶向HPPD的商品化除草剂已有十余种，然而绝大多数HPPD抑制型除草剂品种局限于应用在玉米田中，对其他作物安全性差。Up to now, there are more than ten kinds of commercial herbicides targeting HPPD. However, most HPPD-inhibiting herbicides are limited to the application in corn fields and are not safe for other crops.
因此，为满足我国农业生产中的现实需求，创制可以广泛防治普发性杂草和多发性抗性杂草，且对农作物安全的新型超高效HPPD抑制型除草剂具有巨大的市场价值。Therefore, in order to meet the actual needs of my country's agricultural production, it is of great market value to create new ultra-efficient HPPD-inhibiting herbicides that can widely control common weeds and multiple resistant weeds, and are safe for crops.
发明内容Contents of the invention
本发明的目的是为了提供对农作物安全的新型超高效HPPD抑制型除草化合物。The object of the present invention is to provide a novel ultra-efficient HPPD-inhibiting herbicidal compound that is safe for crops.
为了实现上述目的，本发明的第一方面提供一种氮杂吲哚类化合物，该化合物具有式(I)所示的结构：In order to achieve the above object, the first aspect of the present invention provides an azaindole compound, which has a structure shown in formula (I):
Figure PCTCN2022126676-appb-000001
Figure PCTCN2022126676-appb-000001
其中，在式(I)中，Wherein, in formula (I),
R为式(R-1)或式(R-2)所示的基团，R is a group shown in formula (R-1) or formula (R-2),
R X选自H、卤素、C 1-C 3的烷基、由1-6个卤素取代的C 1-C 3的烷基、C 2-C 4的酯基、氰基、苯基、硝基； R X is selected from H, halogen, C 1 -C 3 alkyl, C 1 -C 3 alkyl substituted by 1-6 halogens, C 2 -C 4 ester, cyano, phenyl, nitrate base;
R Y选自C 1-C 10的烷基、由1-9个卤素取代的C 1-C 10的烷基、-C 1-C 6的亚烷基-O-C 1-C 6的烷基、-C 1-C 6的亚烷基-S-C 1-C 6的烷基、-C 1-C 5的亚烷基-CH-(O-C 1-C 6的烷基) 2、-C 1-C 6的亚烷基-CN、-C 1-C 6的亚烷基-Si-C 1-C 6的烷基、C 2-C 12的烯基、C 2-C 12的炔基、-C 1-C 6的亚烷基-C≡C-Si-C 1-C 6的烷基、-SO 2-C 1-C 6的烷基、C 3-C 8的环烷基、含有至少一个O的C 2-C 7的饱和或不饱和杂环烷基、-C 1-C 6的亚烷基-C 3-C 8的环烷基、-C 1-C 6的亚烷基-含有至少一个O的C 2-C 7的饱和或不饱和杂环烷基、-C 1-C 6的亚烷基-含有至少一个S的C 2-C 7的饱和或不饱和杂环烷基、苯基、由组合A中的至少一种基团取代的苯基、-C 1-C 6的亚烷基-苯基、-C 1-C 6的亚烷基-由组合A中的至少一种基团取代的苯基； R Y is selected from C 1 -C 10 alkyl, C 1 -C 10 alkyl substituted by 1-9 halogens, -C 1 -C 6 alkylene -OC 1 -C 6 alkyl, -C 1 -C 6 alkylene -SC 1 -C 6 alkyl, -C 1 -C 5 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 6 alkylene group-CN, -C 1 -C 6 alkylene group-Si-C 1 -C 6 alkyl group, C 2 -C 12 alkenyl group, C 2 -C 12 alkynyl group, -C 1 -C 6 alkylene-C≡C-Si-C 1 -C 6 alkyl, -SO 2 -C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, containing at least one C 2 -C 7 saturated or unsaturated heterocycloalkyl of O, -C 1 -C 6 alkylene -C 3 -C 8 cycloalkyl, -C 1 -C 6 alkylene - containing C 2 -C 7 saturated or unsaturated heterocycloalkyl with at least one O, -C 1 -C 6 alkylene -C 2 -C 7 saturated or unsaturated heterocycloalkyl with at least one S, Phenyl, phenyl substituted by at least one group in combination A, -C 1 -C 6 alkylene-phenyl, -C 1 -C 6 alkylene - by at least one of combination A A phenyl substituted by a group;
所述组合A由C 1-C 6的烷基、卤素、由1-6个卤素取代的C 1-C 6的烷基组成； The combination A is composed of C 1 -C 6 alkyl, halogen, and C 1 -C 6 alkyl substituted by 1-6 halogens;
在式(R-1)中，R 3和R 4各自独立地选自H、C 1-C 3的烷基； In formula (R-1), R 3 and R 4 are each independently selected from H, C 1 -C 3 alkyl;
在式(R-2)中，R 5选自C 1-C 3的烷基；R 6选自H、C 1-C 3的烷基、C 3-C 6的饱和环烷基；R 7选自H、C 1-C 6的烷基、C 2-C 6的烯基、C 2-C 6的炔基、-CO-N(C 1-C 3的烷基) 2、-C 1-C 6的亚烷基-O-CO-O-C 1-C 6的烷基、-CO-C 1-C 6的烷基、-C 1-C 6的亚烷基-CO-苯基、-CS-N(C 1-C 3的烷基) 2、-CO-由组合A中的至少一种基团取代的吡唑基、-SO 2-C 1-C 6的烷基、C 2-C 6的酯基、-C 1-C 6的亚烷基-苯基。 In formula (R-2), R 5 is selected from C 1 -C 3 alkyl; R 6 is selected from H, C 1 -C 3 alkyl, C 3 -C 6 saturated cycloalkyl; R 7 selected from H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -CO-N(C 1 -C 3 alkyl) 2 , -C 1 -C 6 alkylene-O-CO-OC 1 -C 6 alkyl, -CO-C 1 -C 6 alkyl, -C 1 -C 6 alkylene-CO-phenyl, - CS-N(C 1 -C 3 alkyl) 2 , -CO-pyrazolyl substituted by at least one group in combination A, -SO 2 -C 1 -C 6 alkyl, C 2 - C 6 ester group, -C 1 -C 6 alkylene-phenyl group.
本发明的第二方面提供制备前述第一方面中所述的化合物的方法，该方法包括：将式(II-1)所示化合物或式(II-2)所示化合物进行重排反应，得到式(I-1)所示的产物或式(I-2)所示的产物；任选地，The second aspect of the present invention provides a method for preparing the compound described in the aforementioned first aspect, the method comprising: performing a rearrangement reaction on a compound represented by formula (II-1) or a compound represented by formula (II-2), to obtain The product shown in formula (I-1) or the product shown in formula (I-2); Optionally,
该方法还包括：将所述式(I-2)所示的产物与式(II-3)所示的化合物进行取代反应，得到式(I-2)所示的产物；The method also includes: performing a substitution reaction between the product represented by the formula (I-2) and the compound represented by the formula (II-3), to obtain the product represented by the formula (I-2);
Figure PCTCN2022126676-appb-000002
Figure PCTCN2022126676-appb-000002
式中各取代基的定义与第一方面中所述对应相同，但式(II-3)和式(I-3)中的R 7不为H。 The definition of each substituent in the formula is the same as that described in the first aspect, but R 7 in formula (II-3) and formula (I-3) is not H.
本发明的第三方面提供前述第一方面中所述的化合物在除草剂中的应用。The third aspect of the present invention provides the use of the compound described in the aforementioned first aspect as a herbicide.
本发明的第四方面提供一种除草剂，该除草剂中含有辅料和除草有效量的第一方面中所述的化合物。The fourth aspect of the present invention provides a herbicide, which contains an adjuvant and a herbicidally effective amount of the compound described in the first aspect.
本发明提供的氮杂吲哚类化合物具有优异的HPPD抑制作用，对包括阔叶杂草、禾本科杂草和莎草科杂草在内的杂草具有显著的抑制效果，并且对玉米、水稻、小麦、高粱、花生、大豆、油菜等作物的安全性高。The azaindole compound provided by the present invention has excellent HPPD inhibitory effect, has significant inhibitory effect on weeds including broad-leaved weeds, grass weeds and sedge weeds, and has a significant inhibitory effect on corn, rice , wheat, sorghum, peanuts, soybeans, rapeseed and other crops have high safety.
具体实施方式Detailed ways
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.
本发明所述卤素包括氟、氯、溴、碘。The halogen in the present invention includes fluorine, chlorine, bromine and iodine.
本发明所述C 1-C 3的烷基包括甲基、乙基、正丙基、异丙基。 The C 1 -C 3 alkyl group in the present invention includes methyl, ethyl, n-propyl and isopropyl.
本发明所述由1-6个卤素取代的C 1-C 3的烷基，表示选自甲基、乙基、正丙基、异丙基中的任意基团中的任意1-6个H(例如1、2、3、4、5、6个H)由卤素取代。 The C 1 -C 3 alkyl substituted by 1-6 halogens in the present invention means any 1-6 H in any group selected from methyl, ethyl, n-propyl, and isopropyl (eg 1, 2, 3, 4, 5, 6 H) are substituted by halogen.
本发明所述C 2-C 4的酯基表示-COOR 1所示的结构，且R 1选自甲基、乙基、正丙基、异丙基中的任意基团。 The C 2 -C 4 ester group in the present invention represents a structure represented by -COOR 1 , and R 1 is selected from any group among methyl, ethyl, n-propyl, and isopropyl.
本发明所述C 1-C 10的烷基表示碳原子总数为1-10(例如1、2、3、4、5、6、7、8、9、10个)的直链烷基或者支链烷基。C 1-C 6的烷基具有与此类似的定义，仅仅是碳原子总数不同。 The C 1 -C 10 alkyl group in the present invention means a straight chain alkyl group or a branched group with a total of 1-10 carbon atoms (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10). Alkanes. C 1 -C 6 alkyl has a similar definition, differing only in the total number of carbon atoms.
本发明所述由1-9个卤素(例如1、2、3、4、5、6、7、8、9个)取代的C 1-C 10的烷基表示所述C 1-C 10的烷基上的1-9个H由卤素取代。 The C 1 -C 10 alkyl group substituted by 1-9 halogens (such as 1, 2, 3, 4, 5, 6, 7, 8, 9 ) in the present invention represents the C 1 -C 10 1-9 H on the alkyl group are replaced by halogen.
本发明所述C 1-C 6的亚烷基表示碳原子总数为1-6(例如1、2、3、4、5、6)的亚烷基，可以为支链或者支链的亚烷基。C 1-C 5的亚烷基具有与此类似的定义，仅仅是碳原子总数不同。 The C 1 -C 6 alkylene group in the present invention means an alkylene group with a total of 1-6 carbon atoms (such as 1, 2, 3, 4, 5, 6), which can be branched or branched chain alkylene base. A C 1 -C 5 alkylene group has a similar definition, differing only in the total number of carbon atoms.
本发明所述C 2-C 12的烯基表示碳原子总数为2-12(例如2、3、4、5、6、7、8、9、10、11、12)的烯基，可以为支链烯基或者支链烯基，其中含有至少一个双键。 The C 2 -C 12 alkenyl group in the present invention means an alkenyl group with a total of 2-12 carbon atoms (such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12), which can be Branched alkenyl or branched alkenyl containing at least one double bond.
本发明所述C 2-C 12的炔基表示碳原子总数为2-12(例如2、3、4、5、6、7、8、9、10、11、12)的炔基，可以为直链炔基或者支链炔基，其中含有至少一个三键。 The C 2 -C 12 alkynyl group in the present invention means an alkynyl group with a total of 2-12 carbon atoms (such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12), which can be Straight-chain or branched-chain alkynyl containing at least one triple bond.
本发明所述C 3-C 8的环烷基表示碳原子总数为3-8的环烷基，成环碳原子数为3-8中的任意一个，例如3、4、5、6、7、8。 The C 3 -C 8 cycloalkyl group in the present invention refers to a cycloalkyl group with a total of 3-8 carbon atoms, and the number of ring carbon atoms is any one of 3-8, such as 3, 4, 5, 6, 7 ,8.
针对其余取代基，具有与上文类似的定义。For the remaining substituents, there are analogous definitions as above.
如前所述，本发明的第一方面提供了一种氮杂吲哚类化合物。As mentioned above, the first aspect of the present invention provides an azaindole compound.
以下针对本发明所述的式(I)所示结构的化合物提供几种优选的具体实施方式。The following provides several preferred specific embodiments for the compound represented by the formula (I) in the present invention.
优选的具体实施方式1：在式(I)中，R为式(R-1)所示的基团，R X选自H、卤素、C 1-C 3的烷基、由1-6个卤素取代的C 1-C 3的烷基、C 2-C 4的酯基、氰基、苯基、硝基；R Y选自C 1-C 8的烷基、由1-6个卤素取代的C 1-C 8的烷基、-C 1-C 4的亚烷基-O-C 1-C 6的烷基、-C 1-C 4的亚烷基-S-C 1-C 6的烷基、-C 1-C 3的亚烷基-CH-(O-C 1-C 6的烷基) 2、-C 1-C 4的亚烷基-CN、-C 1-C 4的亚烷基-Si-C 1-C 6的烷基、C 2-C 8的烯基、C 2-C 8的炔基、-C 1-C 4的亚烷基-C≡C-Si-C 1-C 6的烷基、-SO 2-C 1-C 6的烷基、C 3-C 6的环烷基、含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-C 3-C 6的环烷基、-C 1-C 4的亚烷基-含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-含有至少一个S的C 2-C 5的饱和或不饱和杂环烷基、苯基、由组合A中的至少一种基团取代的苯基、-C 1-C 4的亚烷基-苯基、-C 1-C 4的亚烷基-由组合A中的至少一种基团取代的苯基；所述组合A由C 1-C 6的烷基、卤素、由1-6个卤素取代的C 1-C 6的烷基组成；在式(R-1)中，R 3和R 4各自独立地选自H、C 1-C 3的烷基。 Preferred embodiment 1: In formula (I), R is a group represented by formula (R-1), R X is selected from H, halogen, C 1 -C 3 alkyl, consisting of 1-6 Halogen substituted C 1 -C 3 alkyl, C 2 -C 4 ester, cyano, phenyl, nitro; RY is selected from C 1 -C 8 alkyl, substituted by 1-6 halogens C 1 -C 8 alkyl, -C 1 -C 4 alkylene -OC 1 -C 6 alkyl, -C 1 -C 4 alkylene -SC 1 -C 6 alkyl, -C 1 -C 3 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 4 alkylene -CN, -C 1 -C 4 alkylene -Si -C 1 -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, -C 1 -C 4 alkylene -C≡C-Si-C 1 -C 6 Alkyl, -SO 2 -C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 5 saturated or unsaturated heterocycloalkyl containing at least one O, -C 1 -C 4 alkylene -C 3 -C 6 cycloalkyl, -C 1 -C 4 alkylene -C 2 -C 5 saturated or unsaturated heterocycloalkyl containing at least one O, - C 1 -C 4 alkylene group - C 2 -C 5 saturated or unsaturated heterocycloalkyl group containing at least one S, phenyl, phenyl substituted by at least one group in combination A, -C 1 -C 4 alkylene-phenyl, -C 1 -C 4 alkylene-phenyl substituted by at least one group in combination A; said combination A is composed of C 1 -C 6 alkylene group, halogen, C 1 -C 6 alkyl group substituted by 1-6 halogens; in formula (R-1), R 3 and R 4 are each independently selected from H, C 1 -C 3 alkane base.
优选的具体实施方式2：在前述优选的具体实施方式1的基础上，更优选地，所述组合A由C 1-C 4的烷基、卤素、由1-6个卤素取代的C 1-C 4的烷基组成。 Preferred embodiment 2: On the basis of the aforementioned preferred embodiment 1, more preferably, the combination A is composed of C 1 -C 4 alkyl, halogen, C 1 - Alkyl composition of C4 .
优选的具体实施方式3：在式(I)中，R为式(R-1)所示的基团，且式(I)所示的化合物选自以下表1中的任意一种： Preferred embodiment 3: In formula (I), R is a group shown in formula (R-1), and the compound shown in formula (I) is selected from any one of the following table 1:
表1Table 1
Figure PCTCN2022126676-appb-000003
Figure PCTCN2022126676-appb-000003
Figure PCTCN2022126676-appb-000004
Figure PCTCN2022126676-appb-000004
Figure PCTCN2022126676-appb-000005
Figure PCTCN2022126676-appb-000005
Figure PCTCN2022126676-appb-000006
Figure PCTCN2022126676-appb-000006
Figure PCTCN2022126676-appb-000007
Figure PCTCN2022126676-appb-000007
Figure PCTCN2022126676-appb-000008
Figure PCTCN2022126676-appb-000008
优选的具体实施方式4：在式(I)中，R为式(R-2)所示的基团，R X选自H、卤素、C 1-C 3的烷基、由1-6个卤素取代的C 1-C 3的烷基、C 2-C 4的酯基、氰基、苯基、硝基；R Y选自C 1-C 8的烷基、由1-6个卤素取代的C 1-C 8的烷基、-C 1-C 4的亚烷基-O-C 1-C 6的烷基、-C 1-C 4的亚烷基-S-C 1-C 6的烷基、-C 1-C 3的亚烷基-CH-(O-C 1-C 6的烷基) 2、-C 1-C 4的亚烷基-CN、-C 1-C 4的亚烷基-Si-C 1-C 6的烷基、C 2-C 8的烯基、C 2-C 8的炔基、-C 1-C 4的亚烷基-C≡C-Si-C 1-C 6的烷基、-SO 2-C 1-C 6的烷基、C 3-C 6的环烷基、含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-C 3-C 6的环烷基、-C 1-C 4的亚烷基-含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-含有至少一个S的C 2-C 5的饱和或不饱和杂环烷基、苯基、由组合A中的至少一种基团取代的苯基、-C 1-C 4的亚烷基-苯基、-C 1-C 4的亚烷基-由组合A中的至少一种基团取代的苯基；所述组合A由C 1-C 6的烷基、卤素、由1-6个卤素取代的C 1-C 6的烷基组成；在式(R-2)中，R 5选自C 1-C 3的烷基；R 6选自H、C 1-C 3的烷基、C 3-C 6的饱和环烷基；R 7选自H、C 1-C 6的烷基、C 2-C 6的烯基、C 2-C 6的炔基、-CO-N(C 1-C 3的烷基) 2、-C 1-C 4的亚烷基-O-CO-O-C 1-C 6的烷基、-CO-C 1-C 6的烷基、-C 1-C 4的亚烷基-CO-苯基、-CS-N(C 1-C 3的烷基) 2、-CO-由组合A中的至少一种基团取代的吡唑基、-SO 2-C 1-C 6的烷基、C 2-C 6的酯基、-C 1-C 4的亚烷基-苯基。 Preferred embodiment 4: In formula (I), R is a group represented by formula (R-2), R X is selected from H, halogen, C 1 -C 3 alkyl, consisting of 1-6 Halogen substituted C 1 -C 3 alkyl, C 2 -C 4 ester, cyano, phenyl, nitro; RY is selected from C 1 -C 8 alkyl, substituted by 1-6 halogens C 1 -C 8 alkyl, -C 1 -C 4 alkylene -OC 1 -C 6 alkyl, -C 1 -C 4 alkylene -SC 1 -C 6 alkyl, -C 1 -C 3 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 4 alkylene -CN, -C 1 -C 4 alkylene -Si -C 1 -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, -C 1 -C 4 alkylene -C≡C-Si-C 1 -C 6 Alkyl, -SO 2 -C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 5 saturated or unsaturated heterocycloalkyl containing at least one O, -C 1 -C 4 alkylene -C 3 -C 6 cycloalkyl, -C 1 -C 4 alkylene -C 2 -C 5 saturated or unsaturated heterocycloalkyl containing at least one O, - C 1 -C 4 alkylene group - C 2 -C 5 saturated or unsaturated heterocycloalkyl group containing at least one S, phenyl, phenyl substituted by at least one group in combination A, -C 1 -C 4 alkylene-phenyl, -C 1 -C 4 alkylene-phenyl substituted by at least one group in combination A; said combination A is composed of C 1 -C 6 alkylene group, halogen, C 1 -C 6 alkyl group substituted by 1-6 halogens; in formula (R-2), R 5 is selected from C 1 -C 3 alkyl group; R 6 is selected from H, C 1 -C 3 alkyl, C 3 -C 6 saturated cycloalkyl; R 7 is selected from H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Alkynyl, -CO-N(C 1 -C 3 alkyl) 2 , -C 1 -C 4 alkylene -O-CO-OC 1 -C 6 alkyl, -CO-C 1 -C 6 alkyl, -C 1 -C 4 alkylene -CO-phenyl, -CS-N(C 1 -C 3 alkyl) 2 , -CO-at least one group in combination A Substituted pyrazolyl, -SO 2 -C 1 -C 6 alkyl, C 2 -C 6 ester, -C 1 -C 4 alkylene-phenyl.
优选的具体实施方式5：在式(I)中，R为式(R-2)所示的基团，R X选自H、卤素、C 1-C 3的烷基、由1-6个卤素取代的C 1-C 3的烷基、C 2-C 4的酯基、氰基、苯基、硝基；R Y选自C 1-C 6的烷基、由1-6个卤素取代的C 1-C 6的烷基、-C 1-C 4的亚烷基-O-C 1-C 6的烷基、-C 1-C 4的亚烷基-S-C 1-C 6的烷基、-C 1-C 3的亚烷基-CH-(O-C 1-C 6的烷基) 2、-C 1-C 4的亚烷基-CN、-C 1-C 4的亚烷基-Si-C 1-C 6的烷基、C 2-C 8的烯基、C 2-C 8的炔基、-C 1-C 4的亚烷基-C≡C-Si-C 1-C 6的烷基、-SO 2-C 1-C 6的烷基、C 3-C 6的环烷基、含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、 -C 1-C 4的亚烷基-C 3-C 6的环烷基、-C 1-C 4的亚烷基-含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-含有至少一个S的C 2-C 5的饱和或不饱和杂环烷基、苯基、由组合A中的至少一种基团取代的苯基、-C 1-C 4的亚烷基-苯基、-C 1-C 4的亚烷基-由组合A中的至少一种基团取代的苯基；所述组合A由C 1-C 4的烷基、卤素、由1-6个卤素取代的C 1-C 4的烷基组成；在式(R-2)中，R 5选自甲基、乙基、正丙基、异丙基；R 6选自H、甲基、乙基、正丙基、异丙基、环丙基、环丁基；R 7选自H、C 1-C 6的烷基、C 2-C 6的烯基、C 2-C 6的炔基、-CO-N(C 1-C 3的烷基) 2、-C 1-C 4的亚烷基-O-CO-O-C 1-C 6的烷基、-CO-C 1-C 6的烷基、-C 1-C 4的亚烷基-CO-苯基、-CS-N(C 1-C 3的烷基) 2、-CO-由组合A中的至少一种基团取代的吡唑基、-SO 2-C 1-C 6的烷基、C 2-C 6的酯基、-C 1-C 4的亚烷基-苯基。 Preferred embodiment 5: In formula (I), R is a group represented by formula (R-2), R X is selected from H, halogen, C 1 -C 3 alkyl, consisting of 1-6 Halogen substituted C 1 -C 3 alkyl, C 2 -C 4 ester, cyano, phenyl, nitro; RY is selected from C 1 -C 6 alkyl, substituted by 1-6 halogens C 1 -C 6 alkyl, -C 1 -C 4 alkylene -OC 1 -C 6 alkyl, -C 1 -C 4 alkylene -SC 1 -C 6 alkyl, -C 1 -C 3 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 4 alkylene -CN, -C 1 -C 4 alkylene -Si -C 1 -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, -C 1 -C 4 alkylene -C≡C-Si-C 1 -C 6 Alkyl, -SO 2 -C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 5 saturated or unsaturated heterocycloalkyl containing at least one O, -C 1 -C 4 alkylene -C 3 -C 6 cycloalkyl, -C 1 -C 4 alkylene -C 2 -C 5 saturated or unsaturated heterocycloalkyl containing at least one O, - C 1 -C 4 alkylene group - C 2 -C 5 saturated or unsaturated heterocycloalkyl group containing at least one S, phenyl, phenyl substituted by at least one group in combination A, -C 1 -C 4 alkylene-phenyl, -C 1 -C 4 alkylene-phenyl substituted by at least one group in combination A; said combination A is composed of C 1 -C 4 alkylene Base, halogen, composed of C 1 -C 4 alkyl substituted by 1-6 halogens; in formula (R-2), R 5 is selected from methyl, ethyl, n-propyl, isopropyl; R 6 is selected from H, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl; R 7 is selected from H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl , C 2 -C 6 alkynyl, -CO-N(C 1 -C 3 alkyl) 2 , -C 1 -C 4 alkylene -O-CO-OC 1 -C 6 alkyl, -CO-C 1 -C 6 alkyl, -C 1 -C 4 alkylene-CO-phenyl, -CS-N(C 1 -C 3 alkyl) 2 , -CO-by combination A Pyrazolyl substituted by at least one of the groups, -SO 2 -C 1 -C 6 alkyl, C 2 -C 6 ester group, -C 1 -C 4 alkylene-phenyl.
优选的具体实施方式6：在式(I)中，R为式(R-2)所示的基团，且式(I)所示的化合物选自以下表2中的任意一种： Preferred embodiment 6: In formula (I), R is a group shown in formula (R-2), and the compound shown in formula (I) is selected from any one of the following table 2:
表2Table 2
Figure PCTCN2022126676-appb-000009
Figure PCTCN2022126676-appb-000009
Figure PCTCN2022126676-appb-000010
Figure PCTCN2022126676-appb-000010
Figure PCTCN2022126676-appb-000011
Figure PCTCN2022126676-appb-000011
Figure PCTCN2022126676-appb-000012
Figure PCTCN2022126676-appb-000012
Figure PCTCN2022126676-appb-000013
Figure PCTCN2022126676-appb-000013
Figure PCTCN2022126676-appb-000014
Figure PCTCN2022126676-appb-000014
Figure PCTCN2022126676-appb-000015
Figure PCTCN2022126676-appb-000015
Figure PCTCN2022126676-appb-000016
Figure PCTCN2022126676-appb-000016
Figure PCTCN2022126676-appb-000017
Figure PCTCN2022126676-appb-000017
Figure PCTCN2022126676-appb-000018
Figure PCTCN2022126676-appb-000018
Figure PCTCN2022126676-appb-000019
Figure PCTCN2022126676-appb-000019
Figure PCTCN2022126676-appb-000020
Figure PCTCN2022126676-appb-000020
Figure PCTCN2022126676-appb-000021
Figure PCTCN2022126676-appb-000021
Figure PCTCN2022126676-appb-000022
Figure PCTCN2022126676-appb-000022
优选的具体实施方式7：在式(I)中，R为式(R-1)或式(R-2)所示的基团，R X选自H、卤素、C 1-C 3的烷基、由1-6个卤素取代的C 1-C 3的烷基、C 2-C 4的酯基、氰基、苯基、硝基；R Y选自C 1-C 8的烷基、由1-6个卤素取代的C 1-C 8的烷基、-C 1-C 4的亚烷基-O-C 1-C 6的烷基、-C 1-C 4的亚烷基-S-C 1-C 6的烷基、-C 1-C 3的亚烷基-CH-(O-C 1-C 6的烷基) 2、-C 1-C 4的亚烷基-CN、-C 1-C 4的亚烷基-Si-C 1-C 6的烷基、C 2-C 8的烯基、C 2-C 8的炔基、-C 1-C 4的亚烷基-C≡C-Si-C 1-C 6的烷基、-SO 2-C 1-C 6的烷基、C 3-C 6的环烷基、含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-C 3-C 6的环烷基、-C 1-C 4的亚烷基-含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-含有至少一个S的C 2-C 5的饱和或不饱和杂环烷基、苯基、由组合A中的至少一种基团取代的苯基、-C 1-C 4的亚烷基-苯基、-C 1-C 4的亚烷基-由组合A中的至少一种基团取代的苯基；所述组合A由C 1-C 6的烷基、卤素、由1-6个卤素取代的C 1-C 6的烷基组成；在式(R-1)中，R 3和R 4各自独立地选自H、C 1-C 3的烷基；在式(R-2)中，R 5选自C 1-C 3的烷基；R 6选自H、C 1-C 3的烷基、C 3-C 6的饱和环烷基；R 7选自H、C 1-C 6的烷基、C 2-C 6的烯基、C 2-C 6的炔基、-CO-N(C 1-C 3的烷基) 2、-C 1-C 4的亚烷基-O-CO-O-C 1-C 6的烷基、-CO-C 1-C 6的烷基、-C 1-C 4的亚烷基-CO-苯基、-CS-N(C 1-C 3的烷基) 2、-CO-由组合A中的至少一种基团取代的吡唑基、-SO 2-C 1-C 6的烷基、C 2-C 6的酯基、-C 1-C 4的亚烷基-苯基。 Preferred embodiment 7: In formula (I), R is a group represented by formula (R-1) or formula (R-2), and R X is selected from H, halogen, C 1 -C 3 alkane C 1 -C 3 alkyl group, C 2 -C 4 ester group, cyano group, phenyl group, nitro group; RY is selected from C 1 -C 8 alkyl group, C 1 -C 8 alkyl, -C 1 -C 4 alkylene -OC 1 -C 6 alkyl, -C 1 -C 4 alkylene -SC 1 substituted by 1-6 halogens -C 6 alkylene, -C 1 -C 3 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 4 alkylene -CN, -C 1 -C 4 Alkylene-Si-C 1 -C 6 Alkyl, C 2 -C 8 Alkenyl, C 2 -C 8 Alkynyl, -C 1 -C 4 Alkylene -C≡C- Si-C 1 -C 6 alkyl, -SO 2 -C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 5 saturated or unsaturated hetero Cycloalkyl, -C 1 -C 4 alkylene -C 3 -C 6 cycloalkyl, -C 1 -C 4 alkylene -C 2 -C 5 saturated or not containing at least one O Saturated heterocycloalkyl, -C 1 -C 4 alkylene - C 2 -C 5 saturated or unsaturated heterocycloalkyl containing at least one S, phenyl, at least one group from the combination A Substituted phenyl, -C 1 -C 4 alkylene-phenyl, -C 1 -C 4 alkylene - phenyl substituted by at least one group in combination A; said combination A consists of C 1 -C 6 alkyl, halogen, C 1 -C 6 alkyl substituted by 1-6 halogens; in formula (R-1), R 3 and R 4 are each independently selected from H, C 1 -C 3 alkyl; in formula (R-2), R 5 is selected from C 1 -C 3 alkyl; R 6 is selected from H, C 1 -C 3 alkyl, C 3 -C 6 saturated cycloalkyl; R 7 is selected from H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -CO-N(C 1 -C 3 Alkyl) 2 , -C 1 -C 4 Alkylene -O-CO-OC 1 -C 6 Alkyl, -CO-C 1 -C 6 Alkyl, -C 1 -C 4 Alkylene Alkyl-CO-phenyl, -CS-N(C 1 -C 3 alkyl) 2 , -CO-pyrazolyl substituted by at least one group in combination A, -SO 2 -C 1 - C 6 alkyl group, C 2 -C 6 ester group, -C 1 -C 4 alkylene-phenyl group.
优选的具体实施方式8：在前述优选的具体实施方式7的基础上，更优选地，所述组合A由C 1-C 4的烷基、 卤素、由1-6个卤素取代的C 1-C 4的烷基组成。 Preferred embodiment 8: On the basis of the aforementioned preferred embodiment 7, more preferably, the combination A is composed of C 1 -C 4 alkyl, halogen, C 1 - Alkyl composition of C4 .
优选的具体实施方式9：在式(I)中，R为式(R-1)或式(R-2)所示的基团，且式(I)所示的化合物选自前述表1和前述表2中的任意一种。 Preferred embodiment 9: In formula (I), R is a group shown in formula (R-1) or formula (R-2), and the compound shown in formula (I) is selected from the aforementioned Table 1 and Any one of the aforementioned Table 2.
本发明对制备第一方面中所述的化合物的具体方法没有特别的要求，本领域技术人员可以根据本发明公开的结构式，结合农药有机合成领域内的已知知识确定合适的制备路线获得第一方面所述的化合物，但是，为了获得收率和纯度更好的化合物，本发明提供第二方面中所述的优选方法制备第一方面中所述的化合物。The present invention has no special requirements on the specific method for preparing the compound described in the first aspect. Those skilled in the art can determine a suitable preparation route according to the structural formula disclosed in the present invention and in combination with known knowledge in the field of organic pesticide synthesis to obtain the first compound. However, in order to obtain compounds with better yield and purity, the present invention provides the preferred method described in the second aspect to prepare the compound described in the first aspect.
如前所述，本发明的第二方面中提供了一种制备第一方面中所述的化合物的方法。As mentioned above, the second aspect of the present invention provides a method for preparing the compound described in the first aspect.
在没有特别说明的情况下，本发明对前述制备方法中涉及的条件和具体操作参数没有特别的限定，本领域技术人员可以根据本领域内已知的知识进行选择，也可以根据本发明的后文中列举的实例中提供的参数和条件进行选择，本发明在此不再赘述，本领域技术人员不应理解为对本发明的限制。In the absence of special instructions, the present invention has no special limitations on the conditions and specific operating parameters involved in the aforementioned preparation method. Those skilled in the art can select according to the knowledge known in the art, or according to the following aspects of the present invention. The parameters and conditions provided in the examples listed herein are selected, and the present invention will not be described in detail here, and those skilled in the art should not understand it as a limitation of the present invention.
如前所述，本发明的第三方面中提供了前述第一方面中所述的化合物在除草剂中的应用。As mentioned above, the third aspect of the present invention provides the use of the compound described in the aforementioned first aspect in herbicides.
优选地，本发明所述除草剂为针对选自播娘蒿，荠菜，藜，苘麻，猪殃殃，婆婆纳，牛繁缕，铁苋菜，龙葵，灯笼草，马齿苋，反枝苋，鲤肠，稗草，牛筋草，金狗尾草，狗尾草，马唐，看麦娘，日本看麦娘，节节麦、野燕麦、雀麦，千金子，双穗雀稗，萤蔺，异型莎草中的至少一种杂草具有防效的除草剂。Preferably, the herbicides described in the present invention are directed against the group consisting of Artemisia solanum, shepherd's purse, quinoa, velvetleum, pig's weed, mother-in-law, chickweed, amaranth, solanum nigrum, lantern plant, purslane, retrovertica Amaranth, carp sausage, barnyardgrass, goosegrass, golden foxtail, foxtail, crabgrass, kanmai, Japanese kanmai, festival wheat, wild oats, brome, daughter of gold, paspalum bispinus, firefly rush, At least one of the weeds in the heterosedge is controlled by an effective herbicide.
如前所述，本发明的第四方面提供了一种除草剂，该除草剂中含有辅料和除草有效量的第一方面中所述的化合物。As mentioned above, the fourth aspect of the present invention provides a herbicide, which contains an adjuvant and a herbicidally effective amount of the compound described in the first aspect.
更优选地，在所述除草剂中，所述化合物的含量为0.1-99.99wt％。示例性地，在所述除草剂中，所述化合物的含量为1wt％、5wt％、10wt％、15wt％、20wt％、25wt％、30wt％、35wt％、40wt％、45wt％、50wt％、55wt％、60wt％、65wt％、70wt％、75wt％、80wt％、85wt％、90wt％、95wt％。More preferably, in the herbicide, the content of the compound is 0.1-99.99wt%. Exemplarily, in the herbicide, the content of the compound is 1wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%.
优选地，该除草剂的剂型选自乳油、悬浮剂、可湿性粉剂、粉剂、粒剂、水剂、母液和母粉中的至少一种。Preferably, the dosage form of the herbicide is selected from at least one of emulsifiable concentrate, suspension concentrate, wettable powder, powder, granule, aqueous solution, mother liquor and mother powder.
本发明所述的化合物对玉米、水稻、小麦、高粱、花生、大豆、油菜等作物的安全性高。The compound of the present invention has high safety to crops such as corn, rice, wheat, sorghum, peanut, soybean and rapeseed.
以下将通过实例对本发明进行详细描述。以下实例中在没有特别说明的情况下，使用的原料均为普通的市售品。The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, the raw materials used are common commercial products.
在没有特别说明的情况下，以下实例中涉及的室温或者常温均表示25±2℃。Unless otherwise specified, the room temperature or normal temperature involved in the following examples all represent 25±2°C.
制备例1：化合物1的制备Preparation Example 1: Preparation of Compound 1
Figure PCTCN2022126676-appb-000023
Figure PCTCN2022126676-appb-000023
将20mmol的1-1所示化合物加入到100mL烧瓶中，加入30mL的N,N-二甲基甲酰胺，室温下搅拌溶解，依次加入24mmol碳酸铯、22mmol碘甲烷。搅拌反应1h。TLC监测反应完毕后，将反应液抽滤，有机相倒入200mL水中，随后用50mL二氯甲烷萃取水相3次，合并有机相，无水硫酸钠干燥，柱层析纯化得到中间体1-2，收率为97％。Add 20mmol of the compound shown in 1-1 into a 100mL flask, add 30mL of N,N-dimethylformamide, stir and dissolve at room temperature, then add 24mmol of cesium carbonate and 22mmol of methyl iodide in sequence. The reaction was stirred for 1 h. After the reaction was monitored by TLC, the reaction solution was suction filtered, the organic phase was poured into 200 mL of water, and the aqueous phase was extracted 3 times with 50 mL of dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain intermediate 1- 2. The yield is 97%.
将18mmol中间体1-2，36mmol的N,N-二环己基碳酰亚胺,0.9mmol乙酸钯，1.8mmol三苯基膦以及磁子加入到100mL史莱克管中。N 2保护下再加入30mL干燥的N,N-二甲基甲酰胺，60mmol的甲酸，32mmol的三乙胺，随后将反应体系升温至80℃进行反应。TLC监测反应完毕后将不溶物进行抽滤，并将有机相倒入 200mL水中，随后用50mL二氯甲烷萃取水相3次，合并有机相，无水硫酸钠干燥，柱层析纯化得到中间体1-3，收率为85％。 Add 18mmol of intermediate 1-2, 36mmol of N,N-dicyclohexylcarboimide, 0.9mmol of palladium acetate, 1.8mmol of triphenylphosphine and magnetons into a 100mL Shrek tube. Under the protection of N 2 , 30 mL of dry N,N-dimethylformamide, 60 mmol of formic acid, and 32 mmol of triethylamine were added, and then the temperature of the reaction system was raised to 80° C. for the reaction. After the reaction was monitored by TLC, the insoluble matter was suction-filtered, and the organic phase was poured into 200mL of water, and then the aqueous phase was extracted with 50mL of dichloromethane for 3 times, the organic phase was combined, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain the intermediate 1-3, the yield is 85%.
将12mmol中间体1-3加入到100mL烧瓶中，加入30mL的N,N-二甲基甲酰胺室温下搅拌溶解，依次加入24mmol碳酸铯、22mmol碘甲烷。搅拌反应1h。TLC监测反应完毕后，将反应液抽滤，有机相倒入200mL水中，随后用50mL二氯甲烷萃取水相3次，合并有机相，无水硫酸钠干燥，柱层析纯化得到中间体1-4，收率为95％。Add 12mmol of intermediate 1-3 into a 100mL flask, add 30mL of N,N-dimethylformamide and stir to dissolve at room temperature, then add 24mmol of cesium carbonate and 22mmol of methyl iodide in sequence. The reaction was stirred for 1 h. After the reaction was monitored by TLC, the reaction solution was suction filtered, the organic phase was poured into 200 mL of water, and the aqueous phase was extracted 3 times with 50 mL of dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain intermediate 1- 4. The yield is 95%.
将10mmol中间体1-4加入到100mL烧瓶中，加入30mL的N,N-二甲基甲酰胺室温下搅拌溶解，加入10.5mmol的N-氯代丁二酰亚胺。搅拌反应5h。TLC监测反应完毕后，将反应液倒入200mL水中，随后用50mL二氯甲烷萃取水相3次，合并有机相，无水硫酸钠干燥，柱层析纯化得到中间体1-5，收率为90％。Add 10mmol of intermediate 1-4 into a 100mL flask, add 30mL of N,N-dimethylformamide and stir to dissolve at room temperature, and add 10.5mmol of N-chlorosuccinimide. The reaction was stirred for 5h. After TLC monitors that the reaction is complete, the reaction solution is poured into 200mL water, then the aqueous phase is extracted 3 times with 50mL dichloromethane, the organic phases are combined, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain intermediate 1-5. The yield is 90%.
将9mmol中间体1-5加入到100mL烧瓶中，加入15mL四氢呋喃和15mL水室温下搅拌溶解，加入18mmol的氢氧化钠。室温反应2h。TLC监测反应完毕后，将反应液倒入200mL的1mol/L的盐酸溶液中，析出大量固体，抽滤得到中间体1-6，收率为90％。Add 9mmol of intermediate 1-5 into a 100mL flask, add 15mL of tetrahydrofuran and 15mL of water and stir to dissolve at room temperature, and add 18mmol of sodium hydroxide. Reaction at room temperature for 2h. After the reaction was monitored by TLC, the reaction solution was poured into 200 mL of 1 mol/L hydrochloric acid solution, a large amount of solid was precipitated, and intermediate 1-6 was obtained by suction filtration with a yield of 90%.
将6mmol中间体1-6加入到100mL单颈瓶中，加入30mL干燥的四氢呋喃，室温下缓慢滴加12mmol氯化亚砜，滴加完毕后将体系加热至80℃继续反应1.5h，TLC监测反应完毕后脱干溶剂。然后加入20mL干燥的二氯甲烷，9mmol的环己二酮，9mmol的三乙胺，反应0.5h。待反应完毕后，用100mL的1mol/L的盐酸洗涤有机相3次，再用100mL饱和碳酸氢钠溶液洗涤2次，收集有机相，无水硫酸钠干燥，柱层析纯化，得到烯醇酯中间体1-7，收率为80％。Add 6mmol of intermediate 1-6 into a 100mL single-necked bottle, add 30mL of dry tetrahydrofuran, and slowly add 12mmol of thionyl chloride dropwise at room temperature. After the dropwise addition, heat the system to 80°C to continue the reaction for 1.5h, and monitor the reaction by TLC The solvent was removed after completion. Then 20 mL of dry dichloromethane, 9 mmol of cyclohexanedione, and 9 mmol of triethylamine were added and reacted for 0.5 h. After the reaction is complete, wash the organic phase with 100 mL of 1 mol/L hydrochloric acid for 3 times, then wash with 100 mL of saturated sodium bicarbonate solution for 2 times, collect the organic phase, dry over anhydrous sodium sulfate, and purify by column chromatography to obtain the enol ester Intermediate 1-7, the yield is 80%.
将4mmol烯醇酯中间体1-7加入到100mL两颈瓶中，加入20mL无水乙腈，N 2保护下加入8mmol的三乙胺，0.4mmol的丙酮氰醇。室温下搅拌反应10h，TLC监测反应至原料完全消失。脱干乙腈，加入20mL的二氯甲烷。用100mL 1mol/L的盐酸洗涤有机相3次，后用100mL饱和氯化钠溶液洗涤3次，收集有机层，无水硫酸钠干燥。浓缩得油状物，用10mL乙醚重结晶，得化合物1。 Add 4mmol of enol ester intermediate 1-7 into a 100mL two-neck flask, add 20mL of anhydrous acetonitrile, and add 8mmol of triethylamine and 0.4mmol of acetone cyanohydrin under the protection of N2 . The reaction was stirred at room temperature for 10 h, and the reaction was monitored by TLC until the raw material disappeared completely. Dry the acetonitrile and add 20 mL of dichloromethane. The organic phase was washed 3 times with 100 mL of 1 mol/L hydrochloric acid, and then washed 3 times with 100 mL of saturated sodium chloride solution, and the organic layer was collected and dried over anhydrous sodium sulfate. Concentrate to obtain an oil, which is recrystallized with 10 mL of ether to obtain compound 1.
制备例2：化合物67的制备Preparation Example 2: Preparation of Compound 67
Figure PCTCN2022126676-appb-000024
Figure PCTCN2022126676-appb-000024
将6mmol中间体1-3加入到100mL单颈瓶中，加入30mL干燥的四氢呋喃，室温下缓慢滴加12mmol氯化亚砜，滴加完毕后将体系加热至80℃继续反应1.5h，TLC监测反应完毕后脱干溶剂。然后加入20mL干燥的二氯甲烷，9mmol的环己二酮，9mmol的三乙胺，反应0.5h。待反应完毕后，用100mL的1mol/L的盐酸洗涤有机相3次，再用100mL饱和碳酸氢钠溶液洗涤2次，收集有机相，无水硫酸钠干燥，柱层析纯化，得到烯醇酯中间体1-8，收率为80％。Add 6mmol of intermediate 1-3 into a 100mL single-necked bottle, add 30mL of dry tetrahydrofuran, and slowly add 12mmol of thionyl chloride dropwise at room temperature. After the dropwise addition, heat the system to 80°C to continue the reaction for 1.5h, and monitor the reaction by TLC The solvent was removed after completion. Then 20 mL of dry dichloromethane, 9 mmol of cyclohexanedione, and 9 mmol of triethylamine were added and reacted for 0.5 h. After the reaction is complete, wash the organic phase with 100 mL of 1 mol/L hydrochloric acid for 3 times, then wash with 100 mL of saturated sodium bicarbonate solution for 2 times, collect the organic phase, dry over anhydrous sodium sulfate, and purify by column chromatography to obtain the enol ester Intermediate 1-8, the yield is 80%.
将4mmol烯醇酯中间体1-8加入到100mL两颈瓶中，加入20mL无水乙腈，N 2保护下加入8mmol的三乙胺，0.4mmol的丙酮氰醇。室温下搅拌反应10h，TLC监测反应至原料完全消失。脱干乙腈，加入20mL的二氯甲烷。用100mL的1mol/L的盐酸洗涤有机相3次，后用100mL饱和氯化钠溶液洗涤3次，收集有机层，无水硫酸钠干燥。浓缩得油状物，用10mL乙醚重结晶，得化合物67。 Add 4mmol of enol ester intermediate 1-8 into a 100mL two-neck flask, add 20mL of anhydrous acetonitrile, and add 8mmol of triethylamine and 0.4mmol of acetone cyanohydrin under the protection of N2 . The reaction was stirred at room temperature for 10 h, and the reaction was monitored by TLC until the raw material disappeared completely. Dry the acetonitrile and add 20 mL of dichloromethane. Wash the organic phase 3 times with 100 mL of 1 mol/L hydrochloric acid, then wash 3 times with 100 mL of saturated sodium chloride solution, collect the organic layer, and dry over anhydrous sodium sulfate. Concentrate to obtain an oil, which is recrystallized from 10 mL of ether to obtain compound 67.
制备例3：化合物80的制备Preparation Example 3: Preparation of Compound 80
Figure PCTCN2022126676-appb-000025
Figure PCTCN2022126676-appb-000025
Figure PCTCN2022126676-appb-000026
Figure PCTCN2022126676-appb-000026
将18mmol中间体1-2，27mmol乌洛托品，20ml乙酸，40ml水加入250ml茄形瓶中，150℃回流过夜，TLC监测反应完毕之后，冷却至室温，有固体析出，水洗，抽滤得到中间体1-9，产率为30％。Add 18mmol of intermediate 1-2, 27mmol of urotropine, 20ml of acetic acid, and 40ml of water into a 250ml eggplant-shaped bottle, and reflux overnight at 150°C. After the reaction is monitored by TLC, cool to room temperature, and solids are precipitated, washed with water, and filtered with suction to obtain Intermediate 1-9, yield 30%.
将5.4mmol中间体1-9，21.6mmol的NaBH 4，80ml乙醚作溶剂，反应2h后，滴加CF 3COOH回流过夜,TLC监测反应,柱层析纯化，得到中间体1-10，收率为80％。 5.4mmol of intermediate 1-9, 21.6mmol of NaBH 4 , and 80ml of ether were used as solvents. After reacting for 2 hours, CF 3 COOH was added dropwise and refluxed overnight. The reaction was monitored by TLC and purified by column chromatography to obtain intermediate 1-10. The yield was 80%.
将4mmol中间体1-10，8mmol的N,N-二环己基碳酰亚胺,0.2mmol乙酸钯，0.4mmol三苯基膦以及磁子加入到50mL史莱克管中。N 2保护下再加入10mL干燥的N,N-二甲基甲酰胺，13mmol的甲酸，7mmol的三乙胺，随后将反应体系升温至80℃进行反应。TLC监测反应完毕后将不溶物进行抽滤，并将有机相倒入100mL水中，随后用30mL二氯甲烷萃取水相3次，合并有机相，无水硫酸钠干燥，柱层析纯化得到中间体1-11，收率为85％。 Add 4mmol of intermediate 1-10, 8mmol of N,N-dicyclohexylcarboimide, 0.2mmol of palladium acetate, 0.4mmol of triphenylphosphine and magnetons into a 50mL Shrek tube. Under the protection of N 2 , 10 mL of dry N,N-dimethylformamide, 13 mmol of formic acid, and 7 mmol of triethylamine were added, and then the temperature of the reaction system was raised to 80° C. for the reaction. After the reaction was monitored by TLC, the insoluble matter was suction-filtered, and the organic phase was poured into 100 mL of water, then the aqueous phase was extracted with 30 mL of dichloromethane for 3 times, the organic phases were combined, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain the intermediate 1-11, the yield was 85%.
将3.4mmol中间体1-11加入到100mL单颈瓶中，加入30mL干燥的四氢呋喃，室温下缓慢滴加6.8mmol氯化亚砜，滴加完毕后将体系加热至80℃继续反应1.5h，TLC监测反应完毕后脱干溶剂。然后加入20mL干燥的二氯甲烷，5.1mmol的环己二酮，5.1mmol的三乙胺，反应0.5h。待反应完毕后，用100mL的1mol/L的盐酸洗涤有机相3次，再用100mL饱和碳酸氢钠溶液洗涤2次，收集有机相，无水硫酸钠干燥，柱层析纯化，得到烯醇酯中间体1-12，收率为80％。Add 3.4mmol of intermediate 1-11 into a 100mL single-necked bottle, add 30mL of dry tetrahydrofuran, and slowly add 6.8mmol of thionyl chloride dropwise at room temperature. After the dropwise addition, heat the system to 80°C to continue the reaction for 1.5h, TLC After monitoring the completion of the reaction, the solvent was removed. Then add 20 mL of dry dichloromethane, 5.1 mmol of cyclohexanedione, and 5.1 mmol of triethylamine, and react for 0.5 h. After the reaction is complete, wash the organic phase with 100 mL of 1 mol/L hydrochloric acid for 3 times, then wash with 100 mL of saturated sodium bicarbonate solution for 2 times, collect the organic phase, dry over anhydrous sodium sulfate, and purify by column chromatography to obtain the enol ester Intermediate 1-12, the yield is 80%.
将2.72mmol烯醇酯中间体1-12加入到50mL两颈瓶中，加入10mL无水乙腈，N 2保护下加入5.44mmol的三乙胺，0.2mmol的丙酮氰醇。室温下搅拌反应10h，TLC监测反应至原料完全消失。脱干乙腈，加入20mL的二氯甲烷。用100mL的1mol/L的盐酸洗涤有机相3次，后用100mL饱和氯化钠溶液洗涤3次，收集有机层，无水硫酸钠干燥。浓缩得油状物，用10mL乙醚重结晶得化合物80。 Add 2.72mmol of enol ester intermediate 1-12 into a 50mL two-neck flask, add 10mL of anhydrous acetonitrile, and add 5.44mmol of triethylamine and 0.2mmol of acetone cyanohydrin under the protection of N2 . The reaction was stirred at room temperature for 10 h, and the reaction was monitored by TLC until the raw material disappeared completely. Dry the acetonitrile and add 20 mL of dichloromethane. Wash the organic phase 3 times with 100 mL of 1 mol/L hydrochloric acid, then wash 3 times with 100 mL of saturated sodium chloride solution, collect the organic layer, and dry over anhydrous sodium sulfate. Concentrate to obtain an oil, and recrystallize from 10 mL of diethyl ether to obtain compound 80.
制备例4：化合物93的制备Preparation Example 4: Preparation of Compound 93
Figure PCTCN2022126676-appb-000027
Figure PCTCN2022126676-appb-000027
将10mmol中间体1-4加入到100mL烧瓶中，加入30mL的N,N-二甲基甲酰胺室温下搅拌溶解，加入10.5mmol的N-碘代丁二酰亚胺。搅拌反应5h。TLC监测反应完毕后，将反应液倒入200mL水中，随后用50mL二氯甲烷萃取水相3次，合并有机相，无水硫酸钠干燥，柱层析纯化得到中间体1-13，收率为92％。Add 10mmol of intermediate 1-4 into a 100mL flask, add 30mL of N,N-dimethylformamide and stir to dissolve at room temperature, and add 10.5mmol of N-iodosuccinimide. The reaction was stirred for 5h. After TLC monitors that the reaction is complete, the reaction solution is poured into 200mL water, then the aqueous phase is extracted 3 times with 50mL dichloromethane, the organic phases are combined, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain intermediate 1-13. The yield is 92%.
在250ml两颈瓶中，加入27mmol碘化亚铜，27mmol氟化钾，在氮气的保护下加入20ml的N,N-二甲基甲酰胺和20ml的N-甲基吡咯烷酮室温搅拌，然后加入27mmol的TMSCF 3，将体系升温至60℃活化1h，将9mmol中间体1-13溶解到25ml的N,N-二甲基甲酰胺和10ml的N-甲基吡咯烷酮中，再添加至活化后的体系中，升温至100℃，过夜反应。TLC监测反应完毕后将不溶物进行抽滤，并将有机相倒入200mL水中，随后用50mL二氯甲烷萃取水相3次，合并有机相，无水硫酸钠干燥，柱层析纯化得到中间体1-14，收率为85％。 In a 250ml two-necked bottle, add 27mmol cuprous iodide, 27mmol potassium fluoride, add 20ml of N,N-dimethylformamide and 20ml of N-methylpyrrolidone under the protection of nitrogen and stir at room temperature, then add 27mmol TMSCF 3 , the system was heated to 60°C for 1h activation, 9mmol of intermediate 1-13 was dissolved in 25ml of N,N-dimethylformamide and 10ml of N-methylpyrrolidone, and then added to the activated system , heated to 100°C and reacted overnight. After the reaction was monitored by TLC, the insoluble matter was suction-filtered, and the organic phase was poured into 200mL of water, and then the aqueous phase was extracted with 50mL of dichloromethane for 3 times, the organic phase was combined, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain the intermediate 1-14, the yield is 85%.
将7mmol中间体1-14加入到100mL烧瓶中，加入15mL四氢呋喃和15mL水室温下搅拌溶解，加入14 mmol的氢氧化钠。室温反应2h。TLC监测反应完毕后，将反应液倒入200mL的1mol/L的盐酸溶液中，析出大量固体，抽滤得到中间体1-15，收率为90％。Add 7 mmol of intermediate 1-14 into a 100 mL flask, add 15 mL of tetrahydrofuran and 15 mL of water and stir to dissolve at room temperature, and add 14 mmol of sodium hydroxide. Reaction at room temperature for 2h. After the reaction was monitored by TLC, the reaction solution was poured into 200 mL of 1 mol/L hydrochloric acid solution, a large amount of solid was precipitated, and intermediate 1-15 was obtained by suction filtration with a yield of 90%.
将5mmol中间体1-15加入到100mL单颈瓶中，加入30mL干燥的四氢呋喃，室温下缓慢滴加10mmol氯化亚砜，滴加完毕后将体系加热至80℃继续反应1.5h，TLC监测反应完毕后脱干溶剂。然后加入20mL干燥的二氯甲烷，7.5mmol的环己二酮，7.5mmol的三乙胺，反应0.5h。待反应完毕后，用100mL的1mol/L的盐酸洗涤有机相3次，再用100mL饱和碳酸氢钠溶液洗涤2次，收集有机相，无水硫酸钠干燥，柱层析纯化，得到烯醇酯中间体1-16，收率为80％。Add 5mmol of intermediate 1-15 into a 100mL single-necked bottle, add 30mL of dry tetrahydrofuran, and slowly add 10mmol of thionyl chloride dropwise at room temperature. After the dropwise addition, heat the system to 80°C to continue the reaction for 1.5h, and monitor the reaction by TLC The solvent was removed after completion. Then 20 mL of dry dichloromethane, 7.5 mmol of cyclohexanedione, and 7.5 mmol of triethylamine were added and reacted for 0.5 h. After the reaction is complete, wash the organic phase with 100 mL of 1 mol/L hydrochloric acid for 3 times, then wash with 100 mL of saturated sodium bicarbonate solution for 2 times, collect the organic phase, dry over anhydrous sodium sulfate, and purify by column chromatography to obtain the enol ester Intermediate 1-16, yield 80%.
将3mmol烯醇酯中间体1-16加入到100mL两颈瓶中，加入20mL无水乙腈，N 2保护下加入8mmol的三乙胺，0.3mmol的丙酮氰醇。室温下搅拌反应10h，TLC监测反应至原料完全消失。脱干乙腈，加入20mL的二氯甲烷。用100mL的1mol/L的盐酸洗涤有机相3次，后用100mL饱和氯化钠溶液洗涤3次，收集有机层，无水硫酸钠干燥。浓缩得油状物，用10mL乙醚重结晶得化合物93。 Add 3mmol of enol ester intermediate 1-16 into a 100mL two-neck flask, add 20mL of anhydrous acetonitrile, and add 8mmol of triethylamine and 0.3mmol of acetone cyanohydrin under the protection of N2 . The reaction was stirred at room temperature for 10 h, and the reaction was monitored by TLC until the raw material disappeared completely. Dry the acetonitrile and add 20 mL of dichloromethane. Wash the organic phase 3 times with 100 mL of 1 mol/L hydrochloric acid, then wash 3 times with 100 mL of saturated sodium chloride solution, collect the organic layer, and dry over anhydrous sodium sulfate. Concentrate to obtain an oil, and recrystallize from 10 mL of diethyl ether to obtain compound 93.
制备例5：化合物184的制备Preparation Example 5: Preparation of Compound 184
Figure PCTCN2022126676-appb-000028
Figure PCTCN2022126676-appb-000028
将6mmol中间体1-6加入到100mL单颈瓶中，加入30mL干燥的THF，室温下缓慢滴加12mmol SOCl 2，滴加完毕后将体系加热至80℃回流反应约1.5h，TLC监测反应，待反应完毕后脱干溶剂。然后加入20mL干燥的CH 2Cl 2，3.6mmol吡唑酮，6mmol的Et 3N，反应约0.5h。反应完毕后，用10mL的1mol/L的盐酸洗涤有机相3次，再用30mL饱和NaHCO 3溶液洗涤2次，收集有机相，无水Na 2SO 4干燥，柱层析纯化得到烯醇酯中间体1-17，收率为90％。 Add 6mmol of intermediate 1-6 into a 100mL single-necked bottle, add 30mL of dry THF, and slowly add 12mmol of SOCl 2 dropwise at room temperature. After the dropwise addition, the system is heated to 80°C and refluxed for about 1.5h. The reaction is monitored by TLC. After the reaction was completed, the solvent was removed. Then 20 mL of dry CH 2 Cl 2 , 3.6 mmol of pyrazolone, and 6 mmol of Et 3 N were added, and the reaction was carried out for about 0.5 h. After the reaction was completed, the organic phase was washed 3 times with 10 mL of 1 mol/L hydrochloric acid, and then washed 2 times with 30 mL of saturated NaHCO 3 solution, the organic phase was collected, dried over anhydrous Na 2 SO 4 , and purified by column chromatography to obtain the enol ester intermediate Body 1-17, the yield is 90%.
将5.4mmol烯醇酯中间体1-17加入到100mL两颈瓶中，加入30mL无水乙腈，在N 2保护下加入10.8mmol的Et 3N，0.54mmol丙酮氰醇。室温下搅拌反应14h，TLC监测反应至原料完全消失。脱干乙腈，加入约30mL的CH 2Cl 2。用20mL的1mol/L的盐酸洗涤有机相3次，后用20mL饱和NaCl溶液洗涤3次，收集有机层，无水Na 2SO 4干燥。浓缩得油状物，用10mL乙醚重结晶得化合物184。 Add 5.4mmol of enol ester intermediate 1-17 into a 100mL two-neck flask, add 30mL of anhydrous acetonitrile, and add 10.8mmol of Et 3 N and 0.54mmol of acetone cyanohydrin under the protection of N 2 . The reaction was stirred at room temperature for 14 h, and the reaction was monitored by TLC until the raw material disappeared completely. The acetonitrile was dried, and about 30 mL of CH 2 Cl 2 was added. The organic phase was washed 3 times with 20 mL of 1 mol/L hydrochloric acid, and then washed 3 times with 20 mL of saturated NaCl solution, and the organic layer was collected and dried over anhydrous Na 2 SO 4 . Concentrate to obtain an oil, and recrystallize from 10 mL of diethyl ether to obtain compound 184.
制备例6：化合物313的制备Preparation Example 6: Preparation of Compound 313
Figure PCTCN2022126676-appb-000029
Figure PCTCN2022126676-appb-000029
将2mmol化合物184，3mmol的Cs 2CO 3加入到50mL茄形瓶中，加入10mL乙腈，再逐滴加入2.6mmol烯丙基溴，随后将反应体系升温至70℃继续反应4h。反应完毕后，柱层析纯化得到化合物313。 Add 2mmol of compound 184 and 3mmol of Cs 2 CO 3 into a 50mL eggplant-shaped flask, add 10mL of acetonitrile, and then add 2.6mmol of allyl bromide dropwise, then raise the temperature of the reaction system to 70°C and continue the reaction for 4h. After the reaction was completed, compound 313 was obtained by column chromatography purification.
制备例7：化合物365的制备Preparation Example 7: Preparation of Compound 365
Figure PCTCN2022126676-appb-000030
Figure PCTCN2022126676-appb-000030
将2mmol化合物184加入到50mL茄形瓶中，加入10mL二氯甲烷溶解，依次加入8mmol的N,N-二乙基氯甲酰胺，4mmol三乙胺，2mmol的DMAP，随后将反应体系升温至70℃继续反应4h。反应完毕后，柱层析纯化得到化合物365。Add 2mmol of compound 184 into a 50mL eggplant-shaped flask, add 10mL of dichloromethane to dissolve, add 8mmol of N,N-diethylchloroformamide, 4mmol of triethylamine, and 2mmol of DMAP in sequence, and then raise the temperature of the reaction system to 70 ° C to continue the reaction for 4h. After the reaction was completed, compound 365 was obtained by column chromatography purification.
本发明的其余化合物的制备方法参照前述制备例，本发明部分具体化合物的表征数据如表3所示。表3中的收率均以获得该化合物的最后一步化学反应中主要原料为基准计算获得。The preparation methods of the remaining compounds of the present invention refer to the aforementioned preparation examples, and the characterization data of some specific compounds of the present invention are shown in Table 3. The yields in Table 3 are calculated based on the main raw materials in the last step of the chemical reaction to obtain the compound.
表3table 3
Figure PCTCN2022126676-appb-000031
Figure PCTCN2022126676-appb-000031
Figure PCTCN2022126676-appb-000032
Figure PCTCN2022126676-appb-000032
Figure PCTCN2022126676-appb-000033
Figure PCTCN2022126676-appb-000033
Figure PCTCN2022126676-appb-000034
Figure PCTCN2022126676-appb-000034
Figure PCTCN2022126676-appb-000035
Figure PCTCN2022126676-appb-000035
测试例1test case 1
初筛试验(盆栽法)：供试靶和供试作物如以下表格中所示，苗后茎叶喷雾：取内径7cm纸杯，装复合土(菜园土：育苗基质，1：2，v/v)至3/4处，直接播种杂草，覆土0.2cm，待长至4-5叶期备用。供试化合物按照如以下表格中所示的剂量在自动喷雾塔施药后，待杂草或作物叶面药液晾干后移入温室培养(湿度70％)，30天后调查结果。Preliminary screening test (pot planting method): the test target and the test crops are as shown in the following table, and the stems and leaves are sprayed after emergence: take a paper cup with an inner diameter of 7cm and fill it with compound soil (vegetable garden soil: seedling substrate, 1:2, v/v ) to 3/4, sow weeds directly, cover with soil 0.2cm, and wait for the 4-5 leaf stage to be used for later use. After the test compound was sprayed in the automatic spray tower according to the dose shown in the following table, the weed or crop foliage liquid was dried and then moved into the greenhouse for cultivation (humidity 70%), and the results were investigated after 30 days.
并且，对于部分化合物进行了进一步降低施药量复筛。In addition, some compounds were further screened with reduced dosage.
生长抑制率评价方法为目测法，具体根据表4所示的情况进行评级，测试结果如表5-表18中所示。The evaluation method of the growth inhibition rate is the visual method, and the rating is specifically performed according to the conditions shown in Table 4, and the test results are shown in Table 5-Table 18.
对比化合物结构式(即为硝磺草酮)：
Figure PCTCN2022126676-appb-000036
Comparative compound structural formula (namely mesotrione):
Figure PCTCN2022126676-appb-000036
表4Table 4
(％)(%) 评价(抑制、畸形、白化等)Evaluation (suppression, malformation, albinism, etc.) 生长抑制率级别growth inhibition level
0-50-5 对杂草或作物生长无影响，无药效症状。It has no effect on weeds or crop growth, and has no medicinal symptoms. 00
5-295-29 对杂草或作物生长有轻微影响，无明显药效症状Slightly affect the growth of weeds or crops, no obvious symptoms of efficacy 11
30-4930-49 对杂草或作物生长有抑制，无明显药效症状。It can inhibit the growth of weeds or crops, and has no obvious efficacy symptoms. 22
50-6950-69 对杂草或作物长有影响，有明显药效症状。It has an effect on the growth of weeds or crops, and has obvious efficacy symptoms. 33
70-8970-89 杂草或作物受到严重生长抑制。Severe growth inhibition of weeds or crops. 44
80-10080-100 杂草或作物死亡。Weed or crop death. 55
表5table 5
Figure PCTCN2022126676-appb-000037
Figure PCTCN2022126676-appb-000037
Figure PCTCN2022126676-appb-000038
Figure PCTCN2022126676-appb-000038
Figure PCTCN2022126676-appb-000039
Figure PCTCN2022126676-appb-000039
表6Table 6
Figure PCTCN2022126676-appb-000040
Figure PCTCN2022126676-appb-000040
Figure PCTCN2022126676-appb-000041
Figure PCTCN2022126676-appb-000041
表7Table 7
Figure PCTCN2022126676-appb-000042
Figure PCTCN2022126676-appb-000042
Figure PCTCN2022126676-appb-000043
Figure PCTCN2022126676-appb-000043
Figure PCTCN2022126676-appb-000044
Figure PCTCN2022126676-appb-000044
表8Table 8
Figure PCTCN2022126676-appb-000045
Figure PCTCN2022126676-appb-000045
Figure PCTCN2022126676-appb-000046
Figure PCTCN2022126676-appb-000046
表9Table 9
Figure PCTCN2022126676-appb-000047
Figure PCTCN2022126676-appb-000047
Figure PCTCN2022126676-appb-000048
Figure PCTCN2022126676-appb-000048
Figure PCTCN2022126676-appb-000049
Figure PCTCN2022126676-appb-000049
表10Table 10
Figure PCTCN2022126676-appb-000050
Figure PCTCN2022126676-appb-000050
Figure PCTCN2022126676-appb-000051
Figure PCTCN2022126676-appb-000051
Figure PCTCN2022126676-appb-000052
Figure PCTCN2022126676-appb-000052
表11Table 11
Figure PCTCN2022126676-appb-000053
Figure PCTCN2022126676-appb-000053
表12Table 12
Figure PCTCN2022126676-appb-000054
Figure PCTCN2022126676-appb-000054
Figure PCTCN2022126676-appb-000055
Figure PCTCN2022126676-appb-000055
表13Table 13
Figure PCTCN2022126676-appb-000056
Figure PCTCN2022126676-appb-000056
Figure PCTCN2022126676-appb-000057
Figure PCTCN2022126676-appb-000057
表14Table 14
Figure PCTCN2022126676-appb-000058
Figure PCTCN2022126676-appb-000058
表15Table 15
Figure PCTCN2022126676-appb-000059
Figure PCTCN2022126676-appb-000059
表16Table 16
Figure PCTCN2022126676-appb-000060
Figure PCTCN2022126676-appb-000060
Figure PCTCN2022126676-appb-000061
Figure PCTCN2022126676-appb-000061
表17Table 17
化合物编号Compound number 剂量/g.a.i/haDose/g.a.i/ha 籼稻Indica 粳稻Japonica rice 小麦wheat
11 120120 00 11 00
33 120120 00 00 00
185185 120120 11 00 00
192192 120120 00 11 00
281281 120120 00 00 00
硝磺草酮Mesotrione 120120 44 44 44
表18Table 18
化合物编号Compound number 剂量/g.a.i/haDose/g.a.i/ha 玉米corn
11 120120 11
33 120120 00
185185 120120 11
281281 120120 00
测试例2test case 2
酶水平抑制活性测试(偶联法)：利用文献所报道的偶联法对部分化合物对拟南芥HPPD(AtHPPD)的酶水平抑制活性进行了测试(Amaya,Alphonso A.et al.Kinetic analysis of human homogentisate 1,2-dioxygenase.Archives of Biochemistry&Biophysics 2004,421,135-142.)。Enzyme-level inhibitory activity test (coupling method): The enzyme-level inhibitory activity of some compounds on Arabidopsis thaliana HPPD (AtHPPD) was tested using the coupling method reported in the literature (Amaya, Alphonso A. et al. Kinetic analysis of Human homogentisate 1,2-dioxygenase. Archives of Biochemistry & Biophysics 2004, 421, 135-142.).
称取2mg化合物于1.5mL的EP管中，离心机上离心后待用。根据抑制剂的纯度、相对分子质量和质量等信息计算出储液10mM的体积量，加入相应体积的DMSO混合均匀。随后再次用DMSO将10mM的抑制剂溶液稀释成1mM待用，最后用20mM的HEPES缓冲液将抑制剂稀释成10μM用于初筛。做完初筛之后，按照初筛得到的抑制率对抑制剂进行浓度稀释，配制11个浓度，确保每个浓度的抑制剂对酶的抑制率有一个均匀分布。利用偶联法在酶标仪下进行测试，平行测试三次，取其平均值为抑制剂对AtHPPD的IC 50值，并且用商品化抑制剂硝磺草酮作为对照药剂，结果如表19所示。 Weigh 2mg of the compound into a 1.5mL EP tube, centrifuge on a centrifuge and set aside. Calculate the volume of 10 mM stock solution according to the information such as the purity, relative molecular mass and mass of the inhibitor, add the corresponding volume of DMSO and mix well. Subsequently, the 10 mM inhibitor solution was diluted to 1 mM with DMSO again for use, and finally the inhibitor was diluted to 10 μM with 20 mM HEPES buffer for preliminary screening. After the preliminary screening, the concentration of the inhibitor was diluted according to the inhibition rate obtained from the preliminary screening, and 11 concentrations were prepared to ensure that the inhibitor of each concentration had a uniform distribution of the inhibitory rate of the enzyme. Utilize the coupling method to test under the microplate reader, test in parallel three times, take the average value as the IC50 value of the inhibitor to AtHPPD, and use the commercial inhibitor mesotrione as the control agent, the results are shown in Table 19 .
表19：部分化合物对AtHPPD酶抑制活性评价Table 19: Evaluation of AtHPPD enzyme inhibitory activity of some compounds
化合物编号Compound number IC 50(μM) IC50 (μM) 化合物编号Compound number IC 50(μM) IC50 (μM)
11 0.039±0.0040.039±0.004 185185 0.126±0.0060.126±0.006
22 0.113±0.0050.113±0.005 192192 0.056±0.0030.056±0.003
33 0.078±0.0020.078±0.002 245245 0.099±0.0050.099±0.005
6262 0.187±0.0040.187±0.004 281281 0.111±0.0020.111±0.002
硝磺草酮Mesotrione 0.289±0.0120.289±0.012 // //
从上述结果可知，在320g.a.i/ha的施药量下，本发明提供的化合物对所测试的稗草、狗尾草、马唐、苋菜、藜、苘麻6种常见的阔叶杂草和禾本科杂草具有显著的抑制效果。From the above results, it can be seen that under the application rate of 320g.a.i/ha, the compound provided by the invention has a good effect on tested barnyard grass, foxtail, crabgrass, amaranth, quinoa, velvetleaf 6 common broad-leaved weeds and grasses. Undergraduate weeds have a significant inhibitory effect.
进一步地，本发明中部分化合物在320g.a.i/ha的施药量下对所测试的6种杂草表现出100％的除草防效。Further, some compounds of the present invention showed 100% herbicidal control effect on 6 weeds tested at the application rate of 320 g.a.i/ha.
当降低剂量为120g.a.i/ha时，本发明中化合物1对所测试的稗草、狗尾草、马唐、野燕麦、雀麦、看麦娘、日本看麦娘表现出100％的除草防效。对比化合物硝磺草酮虽然对稗草、马唐具有优异的除草防效，但是其对狗尾草的生长几乎不具有抑制作用。When the reduced dose is 120g.a.i/ha, compound 1 of the present invention shows 100% herbicidal control effect on tested barnyardgrass, foxtail, crabgrass, wild oats, brome, kangaroo, and Japanese kanko . Although the comparative compound mesotrione has excellent herbicidal effects on barnyardgrass and crabgrass, it has almost no inhibitory effect on the growth of foxtail.
在120g.a.i/ha剂量下，化合物1、3、185、192、281等对籼稻、粳稻、小麦均展现出了优异的作物安全性，而对比化合物硝磺草酮对籼稻、粳稻、小麦的生长具有严重的抑制作用，作物安全性极差。At a dose of 120g.a.i/ha, compounds 1, 3, 185, 192, 281, etc. showed excellent crop safety to indica rice, japonica rice, and wheat, while the comparative compound mesotrione showed excellent crop safety to indica rice, japonica rice, and wheat. Growth is severely inhibited and crop safety is extremely poor.
在120g.a.i/ha剂量下，化合物1、3、185、281等对玉米展现出了优异的作物安全性。Compounds 1, 3, 185, 281, etc. exhibited excellent crop safety to maize at a dose of 120 g.a.i/ha.
在酶水平活性测试中，化合物1、2、3、62、185、192、245、281等均对AtHPPD的抑制活性优于对照药剂硝磺草酮。In the enzyme level activity test, the inhibitory activity of compounds 1, 2, 3, 62, 185, 192, 245, 281, etc. on AtHPPD was better than that of the control drug mesotrione.
由前述结果可知，本发明提供的氮杂吲哚类化合物对阔叶杂草、禾本科杂草和莎草科杂草均具有很高的除草活性，例如阔叶杂草：播娘蒿，荠菜，藜，苘麻，猪殃殃，婆婆纳，牛繁缕，铁苋菜，龙葵，灯笼草，马齿苋，反枝苋，鲤肠；禾本科杂草：稗草，牛筋草，金狗尾草，狗尾草，马唐，看麦娘，日本看麦娘，节节麦、野燕麦、雀麦，千金子，双穗雀稗；莎草科：萤蔺、异型莎草。As can be seen from the aforementioned results, the azaindole compounds provided by the present invention have very high herbicidal activity to broad-leaved weeds, grass weeds and Cyperaceae weeds, such as broad-leaved weeds: Artemisia sobanifolia, shepherd's purse , quinoa, velvetleaf, pig scorpion, mother-in-law, cow chickweed, iron amaranth, nightshade, lantern grass, purslane, retroverted amaranth, carp sausage; Gramineae weeds: barnyardgrass, goosegrass, goldenseal Setaria, Setaria, Crabgrass, Kan Mai Niang, Japanese Kan Mai Niang, Festival Barley, Wild Oats, Brome, Qianjinzi, Paspalum bitachy;
并且，本发明的化合物对作物的安全性高，明显适合作为粮食型作物田特别是小麦田除草剂进行施用。具有很强的开发和商业化前景。Moreover, the compound of the present invention has high safety to crops, and is obviously suitable for application as a herbicide in grain crop fields, especially wheat fields. It has strong development and commercialization prospects.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.

Claims (12)

  1. 一种氮杂吲哚类化合物，其特征在于，该化合物具有式(I)所示的结构：A kind of azaindole compound, it is characterized in that, this compound has the structure shown in formula (I):
    Figure PCTCN2022126676-appb-100001
    Figure PCTCN2022126676-appb-100001
    其中，在式(I)中，Wherein, in formula (I),
    R为式(R-1)或式(R-2)所示的基团，R is a group shown in formula (R-1) or formula (R-2),
    R X选自H、卤素、C 1-C 3的烷基、由1-6个卤素取代的C 1-C 3的烷基、C 2-C 4的酯基、氰基、苯基、硝基； R X is selected from H, halogen, C 1 -C 3 alkyl, C 1 -C 3 alkyl substituted by 1-6 halogens, C 2 -C 4 ester, cyano, phenyl, nitrate base;
    R Y选自C 1-C 10的烷基、由1-9个卤素取代的C 1-C 10的烷基、-C 1-C 6的亚烷基-O-C 1-C 6的烷基、-C 1-C 6的亚烷基-S-C 1-C 6的烷基、-C 1-C 5的亚烷基-CH-(O-C 1-C 6的烷基) 2、-C 1-C 6的亚烷基-CN、-C 1-C 6的亚烷基-Si-C 1-C 6的烷基、C 2-C 12的烯基、C 2-C 12的炔基、-C 1-C 6的亚烷基-C≡C-Si-C 1-C 6的烷基、-SO 2-C 1-C 6的烷基、C 3-C 8的环烷基、含有至少一个O的C 2-C 7的饱和或不饱和杂环烷基、-C 1-C 6的亚烷基-C 3-C 8的环烷基、-C 1-C 6的亚烷基-含有至少一个O的C 2-C 7的饱和或不饱和杂环烷基、-C 1-C 6的亚烷基-含有至少一个S的C 2-C 7的饱和或不饱和杂环烷基、苯基、由组合A中的至少一种基团取代的苯基、-C 1-C 6的亚烷基-苯基、-C 1-C 6的亚烷基-由组合A中的至少一种基团取代的苯基； R Y is selected from C 1 -C 10 alkyl, C 1 -C 10 alkyl substituted by 1-9 halogens, -C 1 -C 6 alkylene -OC 1 -C 6 alkyl, -C 1 -C 6 alkylene -SC 1 -C 6 alkyl, -C 1 -C 5 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 6 alkylene group-CN, -C 1 -C 6 alkylene group-Si-C 1 -C 6 alkyl group, C 2 -C 12 alkenyl group, C 2 -C 12 alkynyl group, -C 1 -C 6 alkylene-C≡C-Si-C 1 -C 6 alkyl, -SO 2 -C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, containing at least one C 2 -C 7 saturated or unsaturated heterocycloalkyl of O, -C 1 -C 6 alkylene -C 3 -C 8 cycloalkyl, -C 1 -C 6 alkylene - containing C 2 -C 7 saturated or unsaturated heterocycloalkyl with at least one O, -C 1 -C 6 alkylene -C 2 -C 7 saturated or unsaturated heterocycloalkyl with at least one S, Phenyl, phenyl substituted by at least one group in combination A, -C 1 -C 6 alkylene-phenyl, -C 1 -C 6 alkylene - by at least one of combination A A phenyl substituted by a group;
    所述组合A由C 1-C 6的烷基、卤素、由1-6个卤素取代的C 1-C 6的烷基组成； The combination A is composed of C 1 -C 6 alkyl, halogen, and C 1 -C 6 alkyl substituted by 1-6 halogens;
    在式(R-1)中，R 3和R 4各自独立地选自H、C 1-C 3的烷基； In formula (R-1), R 3 and R 4 are each independently selected from H, C 1 -C 3 alkyl;
    在式(R-2)中，R 5选自C 1-C 3的烷基；R 6选自H、C 1-C 3的烷基、C 3-C 6的饱和环烷基；R 7选自H、C 1-C 6的烷基、C 2-C 6的烯基、C 2-C 6的炔基、-CO-N(C 1-C 3的烷基) 2、-C 1-C 6的亚烷基-O-CO-O-C 1-C 6的烷基、-CO-C 1-C 6的烷基、-C 1-C 6的亚烷基-CO-苯基、-CS-N(C 1-C 3的烷基) 2、-CO-由组合A中的至少一种基团取代的吡唑基、-SO 2-C 1-C 6的烷基、C 2-C 6的酯基、-C 1-C 6的亚烷基-苯基。 In formula (R-2), R 5 is selected from C 1 -C 3 alkyl; R 6 is selected from H, C 1 -C 3 alkyl, C 3 -C 6 saturated cycloalkyl; R 7 selected from H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -CO-N(C 1 -C 3 alkyl) 2 , -C 1 -C 6 alkylene-O-CO-OC 1 -C 6 alkyl, -CO-C 1 -C 6 alkyl, -C 1 -C 6 alkylene-CO-phenyl, - CS-N(C 1 -C 3 alkyl) 2 , -CO-pyrazolyl substituted by at least one group in combination A, -SO 2 -C 1 -C 6 alkyl, C 2 - C 6 ester group, -C 1 -C 6 alkylene-phenyl group.
  2. 根据权利要求1所述的化合物，其中，在式(I)中，The compound according to claim 1, wherein, in formula (I),
    R为式(R-1)所示的基团，R is a group shown in formula (R-1),
    R X选自H、卤素、C 1-C 3的烷基、由1-6个卤素取代的C 1-C 3的烷基、C 2-C 4的酯基、氰基、苯基、硝基； R X is selected from H, halogen, C 1 -C 3 alkyl, C 1 -C 3 alkyl substituted by 1-6 halogens, C 2 -C 4 ester, cyano, phenyl, nitrate base;
    R Y选自C 1-C 8的烷基、由1-6个卤素取代的C 1-C 8的烷基、-C 1-C 4的亚烷基-O-C 1-C 6的烷基、-C 1-C 4的亚烷基-S-C 1-C 6的烷基、-C 1-C 3的亚烷基-CH-(O-C 1-C 6的烷基) 2、-C 1-C 4的亚烷基-CN、-C 1-C 4的亚烷基-Si-C 1-C 6的烷基、C 2-C 8的烯基、C 2-C 8的炔基、-C 1-C 4的亚烷基-C≡C-Si-C 1-C 6的烷基、-SO 2-C 1-C 6的烷基、C 3-C 6的环烷基、含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-C 3-C 6的环烷基、-C 1-C 4的亚烷基-含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-含有至少一个S的C 2-C 5的饱和或不饱和杂环烷基、苯基、由组合A中的至少一种基团取代的苯基、-C 1-C 4的亚烷基-苯基、-C 1-C 4的亚烷基-由组合A中的至少一种基团取代的苯基； R Y is selected from C 1 -C 8 alkyl, C 1 -C 8 alkyl substituted by 1-6 halogens, -C 1 -C 4 alkylene -OC 1 -C 6 alkyl, -C 1 -C 4 alkylene -SC 1 -C 6 alkyl, -C 1 -C 3 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 4 alkylene-CN, -C 1 -C 4 alkylene -Si-C 1 -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, -C 1 -C 4 alkylene-C≡C-Si-C 1 -C 6 alkyl, -SO 2 -C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, containing at least one C 2 -C 5 saturated or unsaturated heterocycloalkyl of O, -C 1 -C 4 alkylene -C 3 -C 6 cycloalkyl, -C 1 -C 4 alkylene - containing C 2 -C 5 saturated or unsaturated heterocycloalkyl with at least one O, -C 1 -C 4 alkylene -C 2 -C 5 saturated or unsaturated heterocycloalkyl with at least one S, Phenyl, phenyl substituted by at least one group in combination A, -C 1 -C 4 alkylene-phenyl, -C 1 -C 4 alkylene - by at least one of combination A A phenyl substituted by a group;
    所述组合A由C 1-C 6的烷基、卤素、由1-6个卤素取代的C 1-C 6的烷基组成； The combination A is composed of C 1 -C 6 alkyl, halogen, and C 1 -C 6 alkyl substituted by 1-6 halogens;
    在式(R-1)中，R 3和R 4各自独立地选自H、C 1-C 3的烷基； In formula (R-1), R 3 and R 4 are each independently selected from H, C 1 -C 3 alkyl;
    优选地，所述组合A由C 1-C 4的烷基、卤素、由1-6个卤素取代的C 1-C 4的烷基组成。 Preferably, the combination A consists of C 1 -C 4 alkyl, halogen, and C 1 -C 4 alkyl substituted by 1-6 halogens.
  3. 根据权利要求2所述的化合物，其中，在式(I)中，R为式(R-1)所示的基团，且式(I)所示的化合物选自以下中的任意一种：The compound according to claim 2, wherein, in formula (I), R is a group shown in formula (R-1), and the compound shown in formula (I) is selected from any one of the following:
    Figure PCTCN2022126676-appb-100002
    Figure PCTCN2022126676-appb-100002
    Figure PCTCN2022126676-appb-100003
    Figure PCTCN2022126676-appb-100003
    Figure PCTCN2022126676-appb-100004
    Figure PCTCN2022126676-appb-100004
    Figure PCTCN2022126676-appb-100005
    Figure PCTCN2022126676-appb-100005
    Figure PCTCN2022126676-appb-100006
    Figure PCTCN2022126676-appb-100006
  4. 根据权利要求1所述的化合物，其中，在式(I)中，The compound according to claim 1, wherein, in formula (I),
    R为式(R-2)所示的基团，R is a group shown in formula (R-2),
    R X选自H、卤素、C 1-C 3的烷基、由1-6个卤素取代的C 1-C 3的烷基、C 2-C 4的酯基、氰基、苯基、硝基； R X is selected from H, halogen, C 1 -C 3 alkyl, C 1 -C 3 alkyl substituted by 1-6 halogens, C 2 -C 4 ester, cyano, phenyl, nitrate base;
    R Y选自C 1-C 8的烷基、由1-6个卤素取代的C 1-C 8的烷基、-C 1-C 4的亚烷基-O-C 1-C 6的烷基、-C 1-C 4的亚烷基-S-C 1-C 6的烷基、-C 1-C 3的亚烷基-CH-(O-C 1-C 6的烷基) 2、-C 1-C 4的亚烷基-CN、-C 1-C 4的亚烷基-Si-C 1-C 6的烷基、C 2-C 8的烯基、C 2-C 8的炔基、-C 1-C 4的亚烷基-C≡C-Si-C 1-C 6的烷基、-SO 2-C 1-C 6的烷基、C 3-C 6的环烷基、含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-C 3-C 6的环烷基、-C 1-C 4的亚烷基-含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-含有至少一个S的C 2-C 5的饱和或不饱和杂环烷基、 苯基、由组合A中的至少一种基团取代的苯基、-C 1-C 4的亚烷基-苯基、-C 1-C 4的亚烷基-由组合A中的至少一种基团取代的苯基； R Y is selected from C 1 -C 8 alkyl, C 1 -C 8 alkyl substituted by 1-6 halogens, -C 1 -C 4 alkylene -OC 1 -C 6 alkyl, -C 1 -C 4 alkylene -SC 1 -C 6 alkyl, -C 1 -C 3 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 4 alkylene-CN, -C 1 -C 4 alkylene -Si-C 1 -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, -C 1 -C 4 alkylene-C≡C-Si-C 1 -C 6 alkyl, -SO 2 -C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, containing at least one C 2 -C 5 saturated or unsaturated heterocycloalkyl of O, -C 1 -C 4 alkylene -C 3 -C 6 cycloalkyl, -C 1 -C 4 alkylene - containing C 2 -C 5 saturated or unsaturated heterocycloalkyl with at least one O, -C 1 -C 4 alkylene -C 2 -C 5 saturated or unsaturated heterocycloalkyl with at least one S, Phenyl, phenyl substituted by at least one group in combination A, -C 1 -C 4 alkylene-phenyl, -C 1 -C 4 alkylene - by at least one of combination A A phenyl substituted by a group;
    所述组合A由C 1-C 6的烷基、卤素、由1-6个卤素取代的C 1-C 6的烷基组成； The combination A is composed of C 1 -C 6 alkyl, halogen, and C 1 -C 6 alkyl substituted by 1-6 halogens;
    在式(R-2)中，In formula (R-2),
    R 5选自C 1-C 3的烷基； R 5 is selected from C 1 -C 3 alkyl groups;
    R 6选自H、C 1-C 3的烷基、C 3-C 6的饱和环烷基； R 6 is selected from H, C 1 -C 3 alkyl, C 3 -C 6 saturated cycloalkyl;
    R 7选自H、C 1-C 6的烷基、C 2-C 6的烯基、C 2-C 6的炔基、-CO-N(C 1-C 3的烷基) 2、-C 1-C 4的亚烷基-O-CO-O-C 1-C 6的烷基、-CO-C 1-C 6的烷基、-C 1-C 4的亚烷基-CO-苯基、-CS-N(C 1-C 3的烷基) 2、-CO-由组合A中的至少一种基团取代的吡唑基、-SO 2-C 1-C 6的烷基、C 2-C 6的酯基、-C 1-C 4的亚烷基-苯基。 R 7 is selected from H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -CO-N(C 1 -C 3 alkyl) 2 , - C 1 -C 4 alkylene-O-CO-OC 1 -C 6 alkyl, -CO-C 1 -C 6 alkyl, -C 1 -C 4 alkylene-CO-phenyl , -CS-N(C 1 -C 3 alkyl) 2 , -CO-pyrazolyl substituted by at least one group in combination A, -SO 2 -C 1 -C 6 alkyl, C 2 -C 6 ester group, -C 1 -C 4 alkylene-phenyl group.
  5. 根据权利要求4所述的化合物，其中，在式(I)中，The compound according to claim 4, wherein, in formula (I),
    R为式(R-2)所示的基团，R is a group shown in formula (R-2),
    R X选自H、卤素、C 1-C 3的烷基、由1-6个卤素取代的C 1-C 3的烷基、C 2-C 4的酯基、氰基、苯基、硝基； R X is selected from H, halogen, C 1 -C 3 alkyl, C 1 -C 3 alkyl substituted by 1-6 halogens, C 2 -C 4 ester, cyano, phenyl, nitrate base;
    R Y选自C 1-C 6的烷基、由1-6个卤素取代的C 1-C 6的烷基、-C 1-C 4的亚烷基-O-C 1-C 6的烷基、-C 1-C 4的亚烷基-S-C 1-C 6的烷基、-C 1-C 3的亚烷基-CH-(O-C 1-C 6的烷基) 2、-C 1-C 4的亚烷基-CN、-C 1-C 4的亚烷基-Si-C 1-C 6的烷基、C 2-C 8的烯基、C 2-C 8的炔基、-C 1-C 4的亚烷基-C≡C-Si-C 1-C 6的烷基、-SO 2-C 1-C 6的烷基、C 3-C 6的环烷基、含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-C 3-C 6的环烷基、-C 1-C 4的亚烷基-含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-含有至少一个S的C 2-C 5的饱和或不饱和杂环烷基、苯基、由组合A中的至少一种基团取代的苯基、-C 1-C 4的亚烷基-苯基、-C 1-C 4的亚烷基-由组合A中的至少一种基团取代的苯基； R Y is selected from C 1 -C 6 alkyl, C 1 -C 6 alkyl substituted by 1-6 halogens, -C 1 -C 4 alkylene -OC 1 -C 6 alkyl, -C 1 -C 4 alkylene -SC 1 -C 6 alkyl, -C 1 -C 3 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 4 alkylene-CN, -C 1 -C 4 alkylene -Si-C 1 -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, -C 1 -C 4 alkylene-C≡C-Si-C 1 -C 6 alkyl, -SO 2 -C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, containing at least one C 2 -C 5 saturated or unsaturated heterocycloalkyl of O, -C 1 -C 4 alkylene -C 3 -C 6 cycloalkyl, -C 1 -C 4 alkylene - containing C 2 -C 5 saturated or unsaturated heterocycloalkyl with at least one O, -C 1 -C 4 alkylene -C 2 -C 5 saturated or unsaturated heterocycloalkyl with at least one S, Phenyl, phenyl substituted by at least one group in combination A, -C 1 -C 4 alkylene-phenyl, -C 1 -C 4 alkylene - by at least one of combination A A phenyl substituted by a group;
    所述组合A由C 1-C 4的烷基、卤素、由1-6个卤素取代的C 1-C 4的烷基组成； The combination A is composed of C 1 -C 4 alkyl, halogen, and C 1 -C 4 alkyl substituted by 1-6 halogens;
    在式(R-2)中，In formula (R-2),
    R 5选自甲基、乙基、正丙基、异丙基； R is selected from methyl, ethyl, n-propyl, isopropyl;
    R 6选自H、甲基、乙基、正丙基、异丙基、环丙基、环丁基； R is selected from H, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl;
    R 7选自H、C 1-C 6的烷基、C 2-C 6的烯基、C 2-C 6的炔基、-CO-N(C 1-C 3的烷基) 2、-C 1-C 4的亚烷基-O-CO-O-C 1-C 6的烷基、-CO-C 1-C 6的烷基、-C 1-C 4的亚烷基-CO-苯基、-CS-N(C 1-C 3的烷基) 2、-CO-由组合A中的至少一种基团取代的吡唑基、-SO 2-C 1-C 6的烷基、C 2-C 6的酯基、-C 1-C 4的亚烷基-苯基。 R 7 is selected from H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -CO-N(C 1 -C 3 alkyl) 2 , - C 1 -C 4 alkylene-O-CO-OC 1 -C 6 alkyl, -CO-C 1 -C 6 alkyl, -C 1 -C 4 alkylene-CO-phenyl , -CS-N(C 1 -C 3 alkyl) 2 , -CO-pyrazolyl substituted by at least one group in combination A, -SO 2 -C 1 -C 6 alkyl, C 2 -C 6 ester group, -C 1 -C 4 alkylene-phenyl group.
  6. 根据权利要求5所述的化合物，其中，在式(I)中，R为式(R-2)所示的基团，且式(I)所示的化合物选自以下中的任意一种：The compound according to claim 5, wherein, in formula (I), R is a group shown in formula (R-2), and the compound shown in formula (I) is selected from any one of the following:
    Figure PCTCN2022126676-appb-100007
    Figure PCTCN2022126676-appb-100007
    Figure PCTCN2022126676-appb-100008
    Figure PCTCN2022126676-appb-100008
    Figure PCTCN2022126676-appb-100009
    Figure PCTCN2022126676-appb-100009
    Figure PCTCN2022126676-appb-100010
    Figure PCTCN2022126676-appb-100010
    Figure PCTCN2022126676-appb-100011
    Figure PCTCN2022126676-appb-100011
    Figure PCTCN2022126676-appb-100012
    Figure PCTCN2022126676-appb-100012
    Figure PCTCN2022126676-appb-100013
    Figure PCTCN2022126676-appb-100013
    Figure PCTCN2022126676-appb-100014
    Figure PCTCN2022126676-appb-100014
    Figure PCTCN2022126676-appb-100015
    Figure PCTCN2022126676-appb-100015
    Figure PCTCN2022126676-appb-100016
    Figure PCTCN2022126676-appb-100016
    Figure PCTCN2022126676-appb-100017
    Figure PCTCN2022126676-appb-100017
    Figure PCTCN2022126676-appb-100018
    Figure PCTCN2022126676-appb-100018
    Figure PCTCN2022126676-appb-100019
    Figure PCTCN2022126676-appb-100019
    Figure PCTCN2022126676-appb-100020
    Figure PCTCN2022126676-appb-100020
    Figure PCTCN2022126676-appb-100021
    Figure PCTCN2022126676-appb-100021
    Figure PCTCN2022126676-appb-100022
    Figure PCTCN2022126676-appb-100022
  7. 根据权利要求1所述的化合物，其中，在式(I)中，The compound according to claim 1, wherein, in formula (I),
    R为式(R-1)或式(R-2)所示的基团，R is a group shown in formula (R-1) or formula (R-2),
    R X选自H、卤素、C 1-C 3的烷基、由1-6个卤素取代的C 1-C 3的烷基、C 2-C 4的酯基、氰基、苯基、硝基； R X is selected from H, halogen, C 1 -C 3 alkyl, C 1 -C 3 alkyl substituted by 1-6 halogens, C 2 -C 4 ester, cyano, phenyl, nitrate base;
    R Y选自C 1-C 8的烷基、由1-6个卤素取代的C 1-C 8的烷基、-C 1-C 4的亚烷基-O-C 1-C 6的烷基、-C 1-C 4的亚烷基-S-C 1-C 6的烷基、-C 1-C 3的亚烷基-CH-(O-C 1-C 6的烷基) 2、-C 1-C 4的亚烷基-CN、-C 1-C 4的亚烷基-Si-C 1-C 6的烷基、C 2-C 8的烯基、C 2-C 8的炔基、-C 1-C 4的亚烷基-C≡C-Si-C 1-C 6的烷基、-SO 2-C 1-C 6的烷基、C 3-C 6的环烷基、含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-C 3-C 6的环烷基、-C 1-C 4的亚烷基-含有至少一个O的C 2-C 5的饱和或不饱和杂环烷基、-C 1-C 4的亚烷基-含有至少一个S的C 2-C 5的饱和或不饱和杂环烷基、苯基、由组合A中的至少一种基团取代的苯基、-C 1-C 4的亚烷基-苯基、-C 1-C 4的亚烷基-由组合A中的至少一种基团取代的苯基； R Y is selected from C 1 -C 8 alkyl, C 1 -C 8 alkyl substituted by 1-6 halogens, -C 1 -C 4 alkylene -OC 1 -C 6 alkyl, -C 1 -C 4 alkylene -SC 1 -C 6 alkyl, -C 1 -C 3 alkylene -CH-(OC 1 -C 6 alkyl) 2 , -C 1 -C 4 alkylene-CN, -C 1 -C 4 alkylene -Si-C 1 -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, -C 1 -C 4 alkylene-C≡C-Si-C 1 -C 6 alkyl, -SO 2 -C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, containing at least one C 2 -C 5 saturated or unsaturated heterocycloalkyl of O, -C 1 -C 4 alkylene -C 3 -C 6 cycloalkyl, -C 1 -C 4 alkylene - containing C 2 -C 5 saturated or unsaturated heterocycloalkyl with at least one O, -C 1 -C 4 alkylene -C 2 -C 5 saturated or unsaturated heterocycloalkyl with at least one S, Phenyl, phenyl substituted by at least one group in combination A, -C 1 -C 4 alkylene-phenyl, -C 1 -C 4 alkylene - by at least one of combination A A phenyl substituted by a group;
    所述组合A由C 1-C 6的烷基、卤素、由1-6个卤素取代的C 1-C 6的烷基组成； The combination A is composed of C 1 -C 6 alkyl, halogen, and C 1 -C 6 alkyl substituted by 1-6 halogens;
    在式(R-1)中，R 3和R 4各自独立地选自H、C 1-C 3的烷基； In formula (R-1), R 3 and R 4 are each independently selected from H, C 1 -C 3 alkyl;
    在式(R-2)中，R 5选自C 1-C 3的烷基；R 6选自H、C 1-C 3的烷基、C 3-C 6的饱和环烷基；R 7选自H、C 1-C 6的烷基、C 2-C 6的烯基、C 2-C 6的炔基、-CO-N(C 1-C 3的烷基) 2、-C 1-C 4的亚烷基-O-CO-O-C 1-C 6的烷基、-CO-C 1-C 6的烷基、-C 1-C 4的亚烷基-CO-苯基、-CS-N(C 1-C 3的烷基) 2、-CO-由组合A中的至少一种基团取代的吡唑基、-SO 2-C 1-C 6的烷基、C 2-C 6的酯基、-C 1-C 4的亚烷基-苯基； In formula (R-2), R 5 is selected from C 1 -C 3 alkyl; R 6 is selected from H, C 1 -C 3 alkyl, C 3 -C 6 saturated cycloalkyl; R 7 selected from H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -CO-N(C 1 -C 3 alkyl) 2 , -C 1 -C 4 alkylene-O-CO-OC 1 -C 6 alkyl, -CO-C 1 -C 6 alkyl, -C 1 -C 4 alkylene-CO-phenyl, - CS-N(C 1 -C 3 alkyl) 2 , -CO-pyrazolyl substituted by at least one group in combination A, -SO 2 -C 1 -C 6 alkyl, C 2 - C 6 ester group, -C 1 -C 4 alkylene-phenyl group;
    优选地，所述组合A由C 1-C 4的烷基、卤素、由1-6个卤素取代的C 1-C 4的烷基组成。 Preferably, the combination A consists of C 1 -C 4 alkyl, halogen, and C 1 -C 4 alkyl substituted by 1-6 halogens.
  8. 根据权利要求7所述的化合物，其中，在式(I)中，The compound according to claim 7, wherein, in formula (I),
    R为式(R-1)或式(R-2)所示的基团，R is a group shown in formula (R-1) or formula (R-2),
    且式(I)所示的化合物选自权利要求3中所示的化合物1-化合物183和权利要求6中所示的化合物184-化合物578中的任意一种。And the compound shown in formula (I) is selected from any one of compound 1-compound 183 shown in claim 3 and compound 184-compound 578 shown in claim 6.
  9. 一种制备权利要求1-8中任意一项所述的化合物的方法，其特征在于，该方法包括：将式(II-1)所示化合物或式(II-2)所示化合物进行重排反应，得到式(I-1)所示的产物或式(I-2)所示的产物；任选地，A method for preparing the compound described in any one of claims 1-8, characterized in that the method comprises: rearranging the compound shown in formula (II-1) or the compound shown in formula (II-2) Reaction, obtain the product shown in formula (I-1) or the product shown in formula (I-2); Optionally,
    该方法还包括：将所述式(I-2)所示的产物与式(II-3)所示的化合物进行取代反应，得到式(I-2)所示的产物；The method also includes: performing a substitution reaction between the product represented by the formula (I-2) and the compound represented by the formula (II-3), to obtain the product represented by the formula (I-2);
    Figure PCTCN2022126676-appb-100023
    Figure PCTCN2022126676-appb-100023
    在式(II-1)、式(II-2)、式(I-1)、式(I-2)和式(I-3)中的R X和R Y的定义与权利要求1-8中任意一项所述的定义相同； The definition of R X and R Y in formula (II-1), formula (II-2), formula (I-1), formula (I-2) and formula (I-3) and claims 1-8 have the same definition as any of the above;
    在式(II-1)、式(I-1)中的R 3和R 4的定义与权利要求1-8中任意一项所述的定义相同； In formula (II-1), formula (I-1), the definition of R 3 and R 4 is the same as the definition described in any one of claims 1-8;
    式(II-2)、式(I-2)和式(I-3)中的R 5和R 6的定义与权利要求1-8中任意一项所述的定义相同； The definition of R in formula (II-2), formula (I-2) and formula (I-3) and R 6 is the same as the definition described in any one of claims 1-8;
    式(II-3)和式(I-3)中的R 7的定义与权利要求1-8中任意一项所述的定义相同，但不为H。 R 7 in formula (II-3) and formula (I-3) has the same definition as that described in any one of claims 1-8, but is not H.
  10. 权利要求1-8中任意一项所述的化合物在除草剂中的应用。Use of the compound described in any one of claims 1-8 in herbicides.
  11. 根据权利要求10所述的应用，其中，所述除草剂为针对选自播娘蒿，荠菜，藜，苘麻，猪殃殃，婆婆纳，牛繁缕，铁苋菜，龙葵，灯笼草，马齿苋，反枝苋，鲤肠，稗草，牛筋草，金狗尾草，狗尾草，马唐，看麦娘，日本看麦娘，节节麦、野燕麦、雀麦，千金子，双穗雀稗，萤蔺，异型莎草中的至少一种杂草具有防效的除草剂。The application according to claim 10, wherein, the herbicide is selected from the group consisting of Artemisia solani, shepherd's purse, goosefoot, velvetleum, pig's weed, mother-in-law, cow chickweed, amaranth, solanum nigrum, lantern plant, Purslane, Amaranthus retroflexus, carp intestine, barnyardgrass, goosegrass, golden foxtail, foxtail, crabgrass, kanmai, Japanese kanmai, barley, wild oats, brome, daughter of a thousand golds, double spikes Herbicides that control at least one of the weeds of paspalum, firefly rush, and exotic sedges.
  12. 一种除草剂，其特征在于，该除草剂中含有辅料和除草有效量的权利要求1-8中任意一项所述的化合物；A herbicide, characterized in that the herbicide contains the compound described in any one of claims 1-8 in an adjuvant and a herbicidally effective amount;
    优选地，在所述除草剂中，所述化合物的含量为0.1-99.99wt％；Preferably, in the herbicide, the content of the compound is 0.1-99.99wt%;
    优选地，该除草剂的剂型选自乳油、悬浮剂、可湿性粉剂、粉剂、粒剂、水剂、母液和母粉中的至少一种。Preferably, the dosage form of the herbicide is selected from at least one of emulsifiable concentrate, suspension concentrate, wettable powder, powder, granule, aqueous solution, mother liquor and mother powder.
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WO2000003993A1 (en) * 1998-07-16 2000-01-27 Ishihara Sangyo Kaisha Ltd. Pyrazole-type compounds, process for producing the same and herbicides containing the same
CN110317185A (en) * 2019-07-18 2019-10-11 中国药科大学 Benzo five-membered heterocyclic HPPD enzyme inhibitor or its salt, herbicidal composition, preparation method and purposes

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