WO2020063981A1 - 三酮类化合物及其制备方法和应用以及一种除草剂 - Google Patents

三酮类化合物及其制备方法和应用以及一种除草剂 Download PDF

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WO2020063981A1
WO2020063981A1 PCT/CN2019/109175 CN2019109175W WO2020063981A1 WO 2020063981 A1 WO2020063981 A1 WO 2020063981A1 CN 2019109175 W CN2019109175 W CN 2019109175W WO 2020063981 A1 WO2020063981 A1 WO 2020063981A1
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Prior art keywords
formula
compound
structure represented
weeds
reaction
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PCT/CN2019/109175
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English (en)
French (fr)
Inventor
杨光富
曲仁渝
王现全
陈恩昌
张天柱
杜晨
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山东先达农化股份有限公司
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Priority to EP19865076.4A priority Critical patent/EP3858818A4/en
Priority to AU2019345827A priority patent/AU2019345827B2/en
Publication of WO2020063981A1 publication Critical patent/WO2020063981A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • C07D239/72—Quinazolines; Hydrogenated quinazolines
    • C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4
    • C07D239/96—Two oxygen atoms
    • 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
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines

Definitions

  • the invention relates to the field of pesticide herbicides, in particular to a triketone compound, a preparation method and application thereof, and a herbicide containing the triketone compound.
  • HPPD p-hydroxyphenylpyruvate dioxygenase
  • HPPD inhibitory herbicides entered the market later than AHAS-, PPO-, and ACCase-inhibitory herbicides. Although they started late, they did not prevent the "star molecules" from occupying the market quickly. It is a trione herbicide-mesotrione (also known as mesotrione) developed by Syngenta. It has occupied the top five herbicide sales for many years. In corn fields with frequent weed resistance, mesotrione has gradually replaced other types of herbicides as the most widely used and effective corn field herbicides.
  • mesotrione still has some shortcomings. For example, it is not safe for other bulk crops and cash crops such as wheat, rice, peanuts, soybeans, and rape. At the same time, mesotrione is not safe for many grasses. Weeds (such as common weeds, foxtail and golden foxtail, etc.) have poor control effects. There are also reports in the literature that weeds tend to turn green after using mesotrione. Recently, ciclopirox, created by Qingyuan Nongguan, became the first HPPD herbicide in wheat field in China (as disclosed in CN105218449A), which can effectively control resistance and multi-resistance.
  • ciclopirox is not ideal for controlling weeds such as brome, wild oats, and knotty wheat, which are harmful to wheat growth.
  • specific structure of ciclopirox is as follows:
  • One of the objectives of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide an HPPD herbicide that can be used in wheat and / or peanut crops.
  • the second object of the present invention is to provide a gramineous weed and a part of broad-leaved weeds that are harmful to the growth of wheat and / or peanuts, such as yarrow, tang, foxtail, brome, wild oats, and knot wheat. Triketones with good control.
  • a first aspect of the present invention provides a triketone compound having a structure represented by formula (I),
  • R 1 is n-propyl or cyclopentyl
  • R 2 is selected from H, C 1-6 alkyl, C 1-3 alkyl substituted with 1-6 halogen atoms, C 2-6 alkynyl, C 5- substituted with trimethylsilyl 8 alkynyl group, C 2-6 alkenyl by 1-6 halogen atoms of the C 2-6 alkenyl group;
  • X is selected from hydroxy, halogen, C 1-3 alkylthio, phenylthio, C 1-3 alkylsulfone, phenylsulfone;
  • R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from H and C 1-3 alkyl.
  • triketone compounds having the general structure represented by formula (I) have high crop (such as wheat and peanut) safety, and are safe for brome, wild oats, knot wheat, etc.
  • a variety of gramineous weeds and some broad-leaved weeds that harm wheat and / or peanut growth have significantly better control effects than the compounds of the prior art.
  • a method for preparing the aforementioned triketone compound includes:
  • the method further comprises one, two or three of the following steps in sequence:
  • X 1 in the compound of the structure represented by the formula (II-5) is halogen
  • X 2 is selected from a C 1-3 alkyl group, benzene base
  • a third aspect of the present invention provides the use of the triketone compound according to the first aspect in controlling weeds.
  • a fourth aspect of the present invention provides a herbicide, which is composed of an active ingredient and an excipient, and the active ingredient includes at least one of the triketone compounds according to the first aspect of the present invention.
  • the triketone compound provided by the present invention can be used as an HPPD herbicide for wheat and / or peanut crops, and the triketone compound provided by the present invention is Various grass weeds and some broad-leaved weeds that are harmful to the growth of wheat and / or peanuts, such as knot wheat, have good control effects and high safety to crops.
  • the first aspect of the present invention provides a triketone compound having a structure represented by formula (I),
  • R 1 is n-propyl or cyclopentyl
  • R 2 is selected from H, C 1-6 alkyl, C 1-3 alkyl substituted with 1-6 halogen atoms, C 2-6 alkynyl, C 5- substituted with trimethylsilyl 8 alkynyl group, C 2-6 alkenyl by 1-6 halogen atoms of the C 2-6 alkenyl group;
  • X is selected from hydroxy, halogen, C 1-3 alkylthio, phenylthio, C 1-3 alkylsulfone, phenylsulfone;
  • R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from H and C 1-3 alkyl.
  • C 1-6 alkyl means an alkyl group having a total of 1-6 carbon atoms, and includes a linear alkyl group, a branched alkyl group, and a cycloalkyl group. For example, it may be 1, 2, 3, or 4 carbon atoms.
  • straight-chain alkyl branched-chain alkyl and cycloalkyl, which may be, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl Group, cyclobutyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl and the like.
  • C 1-3 alkyl group means an alkyl group having a total number of 1-3 carbon atoms, and includes a linear alkyl group, a branched alkyl group, and a cycloalkyl group.
  • Alkyl, branched alkyl, and cycloalkyl may be, for example, methyl, ethyl, n-propyl, isopropyl, or cyclopropyl.
  • C 1-3 alkyl group substituted by 1-6 halogen atoms means an alkyl group having a total number of 1-3 carbon atoms, and includes a linear alkyl group, a branched alkyl group, and a cycloalkyl group, and may be, for example, a carbon atom.
  • a total of 1, 2 or 3 straight-chain alkyl, branched-chain and cycloalkyl groups, and 1-6 H on the alkyl group are replaced by halogen atoms, for example, there may be 1, 2, 3, 4, 5, or Six H are substituted with at least one halogen atom selected from fluorine, chlorine, bromine, and iodine.
  • C 2-6 alkynyl group means an alkynyl group having 2 to 6 carbon atoms in total, and examples thereof include ethynyl, propynyl, and butynyl.
  • C 5-8 alkynyl substituted with trimethylsilyl means an alkynyl having 5-8 carbon atoms in total, and at least one H of the alkynyl is substituted with trimethylsilyl.
  • C 2-6 alkenyl group means an alkenyl group having 2 to 6 carbon atoms in total, and examples thereof include vinyl, propenyl, and butenyl.
  • Definitions "by the 1-6 halogen atoms substituted C 2-6 alkenyl group” defined “C 2-6 alkenyl” is similar, except that, “consisting of 1-6 halogen atoms C 2 H of 1-6 -6 alkenyl group "is substituted with a halogen atom, for example, there may be 5 or 6 H from at least one halogen selected from fluorine, chlorine, bromine, iodine atom To replace.
  • C 1-3 alkylthio group means an alkyl group having a sulfur atom connected to the mother core at one end and a C 1-3 at the other end.
  • Phhenylthio means that one end of the sulfur atom is connected to the mother core and the other end is connected to the phenyl group.
  • C 1-3 alkylsulfone means that the sulfone group is attached to the mother core and the C 1-3 alkyl group, respectively.
  • Phenylsulfone means that the sulfone group is attached to the mother core and the phenyl group, respectively.
  • R 1 is n-propyl or cyclopentyl
  • R 2 is selected from H, C 1-3 alkyl, substituted with 1-3 halogen atoms, C 1-3 alkyl and the C 3-6 alkynyl group, a trimethylsilyl-substituted C 6- 8 alkynyl group, C 3-6 alkenyl, substituted with 1-3 halogen atoms, a C 3-6 alkenyl group;
  • X is selected from hydroxy, halogen, C 1-3 alkylthio, phenylthio, C 1-3 alkylsulfone, phenylsulfone;
  • R 3 , R 4 , R 5 , R 6 are each independently selected from H and C 1-3 alkyl;
  • R 7 is H.
  • R 1 is n-propyl or cyclopentyl
  • R 2 is selected from H, methyl, ethyl, monofluoromethyl, difluoromethyl, monofluoroethyl, difluoroethyl, trifluoromethyl, trifluoroethyl,
  • X is selected from -OH, -F, -Cl, -Br, CH 3 -S-, CH 3 CH 2 -S-, CH 3 CH 2 CH 2 -S-,
  • R 3 , R 4 , R 5 , and R 6 are each independently selected from H, methyl, ethyl, n-propyl, and isopropyl;
  • R 7 is H.
  • the compound represented by formula (I) is selected from at least one of the following:
  • the triketone compounds provided by the present invention can be used as HPPD herbicides in crops such as wheat and / or peanuts.
  • the triketone compounds provided by the present invention are yarrow, tang, foxtail, brome, wild oat, Various gramineous weeds and some broad-leaved weeds that are harmful to the growth of wheat, such as barley wheat, have good control effects, and show excellent crop safety to wheat and peanut.
  • the present invention does not specifically limit the specific method for obtaining the triketone compound, and those skilled in the art can obtain a suitable triketone compound according to the specific structure of the triketone compound provided by the present invention in combination with the synthetic method in the field of organic synthesis. Methods.
  • the second aspect of the present invention provides a method for preparing the triketone compound described in the first aspect, the method comprising:
  • the method further comprises one, two or three of the following steps in sequence:
  • X 1 in the compound of the structure represented by the formula (II-5) is halogen
  • X 2 is selected from a C 1-3 alkyl group, benzene base
  • the molar ratio of the compound of the structure represented by formula (II-3) to the catalyst and the base is 1: (0.01-1): (0.5-4); more preferably, the structure represented by formula (II-3)
  • the molar ratio of the compound to the catalyst and the base is 1: (0.05-1): (1-3).
  • the conditions of the contact include: a reaction temperature of 0-100 ° C; a reaction time of 0.5-36h; more preferably, in the step (2), the conditions of the contact include : Reaction temperature is 20-40 ° C; reaction time is 5-30h.
  • the method according to the present invention may further include a step of purifying the obtained product.
  • a step of purifying the obtained product There is no special requirement for the purification method, and various purification methods conventionally used by those skilled in the art may be adopted, such as You can use an extractant to extract, dry the desiccant, and remove impurities by column chromatography and other methods.
  • the compound having the structure represented by the formula (II-1) can be prepared by a conventional reaction in the art.
  • the compound of the structure represented by the formula (II-1) can be prepared by using the synthetic route shown below:
  • the compound represented by the formula A is reacted with iodine chloride to obtain the compound represented by the formula B, and further reacted with the compound represented by the formula C to obtain the compound represented by the formula D, and then the compound represented by the formula D is halogenated in the presence of a base.
  • Compound (R 2 I or R 2 Br) is reacted to obtain a compound represented by formula E, and further reacted with cuprous cyanide to obtain a compound represented by formula F, and further hydrolyzed under acidic conditions to obtain a structure represented by formula (II-1) compound of.
  • the catalyst is selected from the group consisting of sodium cyanide, potassium cyanide, acetone cyanohydrin, trimethylcyanosilane, 1,2,4-triazole and benzo 1, 2, 3 At least one of 4-triazole.
  • the base is selected from at least one of potassium carbonate, sodium carbonate, cesium carbonate, triethylamine, and pyridine.
  • the solvent is selected from at least one of methylene chloride, chloroform, dichloroethane, acetonitrile, toluene, tetrahydrofuran, and benzene.
  • the third aspect of the present invention provides the use of the triketone compound according to the first aspect in controlling weeds.
  • the weed according to the present invention is a plant growing on a site harmful to human survival and activities, and may be a non-cultivated wild plant or a plant that is useless to humans. For example, various wild plants can be planted in the field.
  • the weed may be a broadleaf weed and / or a grass weed.
  • the weeds are wheat field weeds and / or peanut field weeds.
  • the weeds are yarrow, foxtail, tangs, amaranth, amaranth, ramie, knot wheat, wild oats, bromberry, Mai Mai Niang, Japanese Mai Mai Niang, hard grass , At least one of the grass root, the barnyard grass, and the pig burdock, the cattle stellate, the mother-in-law, the crushed rice qi, the sorrel leaf sedge, the queen's grass, the broccoli.
  • the amount of the triketone compound is 10-400 g / ha.
  • the triketone compound is used after being dissolved and diluted with a solvent, and the concentration after being dissolved and diluted with a solvent is preferably 0.05-0.4 g / L.
  • the solvent for dissolving the triketone compound may include N, N-dimethylformamide, dimethylsulfoxide, and the like, and the reagent for dilution may be water containing common additives and the like.
  • one or more of additives commonly used in the field of herbicides, such as surfactants and emulsifiers may also be added to the solution in which the triketone compound is dissolved.
  • the diluted triketone compounds of the present invention can be sprayed onto the stems and / or leaves of plants by conventional methods in the art.
  • the fourth aspect of the present invention provides a herbicide, which is composed of an active ingredient and an adjuvant, and the active ingredient includes at least one of the triketone compounds according to the first aspect of the present invention. Species.
  • the content of the active ingredient is 1-99.9% by weight.
  • auxiliary materials of the present invention are various additives commonly used in various dosage forms for preparing herbicides in the art.
  • the dosage form of the herbicide of the present invention is at least one selected from the group consisting of emulsifiable concentrate, suspending agent, wettable powder, powder, granule, aqueous solution, mother liquor and mother powder.
  • room temperature means 25 ° C ⁇ 3 ° C.
  • intermediate B 8.31 g of intermediate B was added to a 200 mL two-necked flask, 80 mL of pyridine was added, and 2.55 g of N-n-propyl isocyanate shown by C-1 was slowly added to the system with stirring. The reaction solution was heated to 100 ° C. and reacted overnight. After the reaction was completed, pyridine was distilled off under reduced pressure. The obtained solid was dissolved in acetone, stirred and passed through the column to obtain intermediate D-1. Yield: 78%; melting point: 295-296 ° C.
  • intermediate D-1 7.91 g of intermediate D-1 was added to a 200 mL single-necked flask, 50 mL of DMF was added, and 14.95 g of Cs 2 CO 3 was added with stirring to continue the reaction for about 30 min. 6.49 g of CH 3 I was slowly added dropwise to the reaction system. After the dropwise addition was completed, the reaction was stirred at room temperature overnight. After the reaction was completed, the system was poured into 200 mL of water, and a large amount of solid was precipitated to obtain intermediate E-1. Yield: 95%; melting point: 208-210 ° C.
  • the aqueous layers were combined, and the aqueous layers were acidified with concentrated hydrochloric acid to a pH of about 1, and left to precipitate.
  • intermediate B 8.31 g of intermediate B was added to a 200 mL two-necked flask, 80 mL of pyridine was added, and 3.33 g of cyclopentyl isocyanate represented by C-2 was slowly added to the system with stirring. The reaction solution was heated to 100 ° C. for overnight reaction. After the reaction was completed, pyridine was distilled off under reduced pressure. The obtained solid was dissolved in acetone, stirred and passed through the column to obtain intermediate D-2. Yield: 80%; melting point: 307-308 ° C.
  • intermediate D-2 8.88 g of intermediate D-2 was added to a 200 mL single-necked flask, 50 mL of DMF was added, and 15.6 g of Cs 2 CO 3 was added with stirring to continue the reaction for about 30 min. 6.77 g of CH 3 I was slowly added dropwise to the reaction system. After the dropwise addition was completed, the reaction was stirred at room temperature overnight. After the reaction was completed, the system was poured into 200 mL of water, and a large amount of solid was precipitated to obtain intermediate E-2. Yield: 95%; melting point: 220-221 ° C.
  • intermediate E-2 8.755 g of intermediate E-2 and 4.06 g of CuCN were added to a 200 mL double-necked flask, and 100 mL of dried DMF was added. The reaction was refluxed for 12 hours. After the reaction was completed, DMF was distilled off under reduced pressure. After cooling, 100 mL of acetone was added to the reaction flask and stirred vigorously for 20 min. The unreacted CuCN was removed by filtration. The filtrate was dried to give intermediate F-2. Yield: 86%; melting point: 232-233 ° C.
  • the aqueous layers were combined, and the aqueous layers were acidified with concentrated hydrochloric acid to a pH of about 1, and left to precipitate.
  • This test example is used to illustrate the herbicidal activity inhibition rate (%) of some specific compounds and compounds of the structure represented by formula (I) and comparative compound D1, where comparative compound D1 (the comparative compound D1 is a specific compound disclosed in CN104557739A, And CN104557739A is the same as the main inventor of the present invention)
  • the structural formula is:
  • Initial screening test (potted method): The test targets are yarrow, ragtail, mathang, amaranth, quinoa, and ramie.
  • Spraying of stems and leaves after seedling Take a 7cm inner diameter paper cup and install compound soil (vegetable garden soil: seedling substrate, 1: 2, v / v) to 3/4, directly sowing weeds, covering the soil with 0.2cm, until the 4-5 leaf stage is ready for use.
  • compound soil vegetable garden soil: seedling substrate, 1: 2, v / v
  • the compound of the present invention and the above-mentioned comparative compound D1 were applied at a dose of 150 g.ai/ha (g / ha) in an automatic spray tower, and after the foliar medicinal solution of the crop was dried, it was moved to a greenhouse for cultivation (70% humidity), and after 30 days Findings.
  • the method of evaluating the growth inhibition rate is visual inspection, and the ratings are specifically based on the conditions shown in Table 2.
  • the test results are shown in Table 3.
  • Test Example 1 The same method as in Test Example 1 was used to reduce the dose of some compounds for rescreening. The test results are shown in Table 4.
  • the compound of the present invention has a herbicidal activity equivalent to or better than D1 against three weeds, such as yarrow, foxtail, and tang, and it is better for grass weeds, wheat, and wild oats. , Brome, Kanmai Niang, and Kanmai Niang, etc.
  • compounds 10, 11, 12, 14, 31, 32 still maintain good herbicidal activity against the above weeds under the three application methods, while the control The agent D1 showed almost no herbicidal activity against the main grass weeds in the above-mentioned wheat field.
  • the compound of the present invention can be used as a broad-spectrum herbicide for controlling grass weeds.
  • Test Example 1 The same method as in Test Example 1 was used to determine crop safety for some compounds. The test results are shown in Table 5.
  • Compound 11 had only a slight inhibitory effect on wheat at three application concentrations, but did not affect wheat growth, and had excellent crop safety. Compounds 12 and 14 also have high safety to wheat at low concentrations.
  • Compound 31 showed almost no inhibitory effect on wheat under the three application methods, and compound 32 also only slightly inhibited wheat under the three application methods, but did not affect normal wheat growth.
  • the compound of the present invention is obviously suitable for application as a herbicide in wheat fields, and has great commercial value.
  • the compounds 11, 12, 31 and 32 in the present invention are also very safe for peanuts, so they can also be used in peanut fields to control grasses and some broad-leaved weeds, but currently they have not been used to control peanut field weeds.
  • HPPD inhibitory herbicide HPPD inhibitory herbicide.

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Abstract

公开了三酮类化合物及其制备方法和应用以及一种除草剂，该化合物具有式（I）所示的结构。上述三酮类化合物能够用作防除禾本科杂草以及阔叶杂草的HPPD除草剂。上述三酮类化合物对多种危害小麦和/或花生生长的禾本科杂草和部分阔叶杂草具有良好防效。

Description

三酮类化合物及其制备方法和应用以及一种除草剂 技术领域
本发明涉及农药除草剂领域，具体涉及一种三酮类化合物及其制备方法和应用，以及一种含有该三酮类化合物的除草剂。
背景技术
杂草抗药性的爆发性增长已经成为现代农业可持续发展所面临的一个关键挑战，而创制新型超高效除草剂是解决这一挑战的根本途径。
截至目前，我国正式报道的抗性杂草种类超过40种，是世界上抗性杂草危害最为严重的五个国家之一。特别是在我国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。例如，小麦田中的播娘蒿、荠菜、看麦娘、日本看麦娘、雀麦、节节麦、野燕麦等主要杂草的抗性种群已经发展成为优势杂草，导致部分省市区域的麦田除草剂用量不断加大，不仅增加了防治成本，而且导致药害事件频发、农药残留超标。
因此，在当前国家大力提倡“减量增效、绿色发展”的大背景下，创制出作用机制新颖的超高效除草剂以替代传统除草剂，是防治抗性杂草、实现减量增效和绿色发展的根本途径。
靶向对羟苯基丙酮酸双加氧酶(HPPD)的除草剂因其高效、低毒、环境友好以及抗性风险低等特点被广泛使用。
截止目前，靶向HPPD所开发成功的除草剂多达数十种，以结构分类大致可以归为三大类：1、以硝磺草酮(Mesotrione)为代表的三酮类；2、以苯唑草酮(Topramezone)为代表的吡唑类；3、以异噁氯草酮(Isoxachlortole)为代表的异噁唑类。
经过农药市场销售额调查，HPPD抑制类除草剂进入市场时间较AHAS-、PPO-以及ACCase-抑制类除草剂相比起步虽晚，但不妨碍其中的“明星分子”对市场的迅速占领，特别是由先正达公司研发的三酮类除草剂-硝磺草酮(又名：甲基磺草酮)，连续多年占领除草剂销售额前五。在抗性杂草多发的玉米田中，硝磺草酮已经逐渐代替了其他类型的除草剂成为使用最广和最为有效的玉米田除草剂。
然而，硝磺草酮仍然存在着一些自身不足，例如其对其它的一些大宗作物和经济作物如小麦、水稻、花生、大豆和油菜等安全性较差，同时硝磺草酮对多种禾本科杂草(如普发性杂草狗尾草和金狗尾草等)防效较差，也有文献报道使用硝磺草酮后杂草易出现返青现象等。最近由清原农冠公司创制的环吡氟草酮成为了我国首个麦田HPPD除草剂(如CN105218449A中所公开)，其可以有效防除抗性及多抗性的看麦娘、日本看麦娘等禾本科杂草及部分阔叶杂草，为小麦田的除草剂使用提供了更多选择。然而，环吡氟草酮对雀麦、野燕麦、节节麦等多种危害小麦生长的禾本科杂草防效却并不理想。另外，环吡氟草酮的具体结构如下：
Figure PCTCN2019109175-appb-000001
鉴于我国农业生产实际中还没有兼备广谱性和超高效除草活性且用于小麦田的HPPD除草剂，尤其是对雀麦、野燕麦、节节麦等多种危害小麦生长的禾本科杂草具有优异防效的除草剂。此外，针对经济作物花生，目前仍然缺乏可使用的HPPD抑制型除草剂用于防治花生田例如稗草、马唐、狗尾草等禾本科杂 草。因此，为满足我国农业生产中的现实需求，创制出对小麦和花生安全的新型超高效HPPD除草剂具有十分重要的意义。
发明内容
本发明的目的之一是为了克服现有技术存在的上述缺陷，提供一种能够用于小麦和/或花生作物的HPPD除草剂。
本发明的目的之二是为了提供一种对稗草、马唐、狗尾草、雀麦、野燕麦、节节麦等多种危害小麦和/或花生生长的禾本科杂草和部分阔叶杂草具有良好防效的三酮类化合物。
为了实现上述目的，本发明的第一方面提供一种三酮类化合物，该化合物具有式(I)所示的结构，
Figure PCTCN2019109175-appb-000002
其中，在式(I)中，
R 1为正丙基或环戊基；
R 2选自H、C 1-6的烷基、由1-6个卤原子取代的C 1-3的烷基、C 2-6的炔基、由三甲基硅基取代的C 5-8的炔基、C 2-6的烯基、由1-6个卤原子取代的C 2-6的烯基；
X选自羟基、卤素、C 1-3的烷基硫基、苯基硫基、C 1-3的烷基砜基、苯基砜基；
R 3、R 4、R 5、R 6和R 7各种独立地选自H和C 1-3的烷基。
本发明的发明人在研究中发现，具有式(I)所示通式结构的三酮类化合物具有高的作物(例如小麦和花生)安全性，且对雀麦、野燕麦、节节麦等多种危害小麦和/或花生生长的禾本科杂草和部分阔叶杂草具有明显比现有技术的化合物更好的防效。
本发明的第二方面提供一种制备前述三酮类化合物的方法，该方法包括：
(1)将式(II-1)所示结构的化合物依次与氯化亚砜和式(II-2)所示结构的化合物反应，得到式(II-3)所示结构的化合物；
(2)在重排反应条件下，将式(II-3)所示结构的化合物与催化剂在碱和溶剂存在下进行接触，得到式(II-4)所示结构的化合物；
任选该方法还依次包括以下步骤中的1个、2个或3个步骤：
(a)将式(II-4)所示结构的化合物进行卤化反应，得到式(II-5)所示结构的化合物；
(b)将式(II-5)所示结构的化合物与式(II-6)所示结构的硫醇钠反应，得到式(II-7)所示结构的化合物；
(c)在式(II-8)所示结构的过氧化物存在下，将式(II-7)所示结构的化合物进行氧化反应，得到式(II-9)所示结构的化合物；
Figure PCTCN2019109175-appb-000003
Figure PCTCN2019109175-appb-000004
Figure PCTCN2019109175-appb-000005
X 2-SNa式(II-6)，
Figure PCTCN2019109175-appb-000006
其中，
式(II-5)所示结构的化合物中的X 1为卤素；
式(II-6)所示结构的化合物、式(II-7)所示结构的化合物和式(II-9)所示结构的化合物中的X 2选自C 1-3的烷基、苯基；
并且，式(II-1)、式(II-2)、式(II-3)、式(II-4)、式(II-5)、式(II-7)和式(II-9)中涉及的其余取代基与本发明前述的化合物的取代基对应相同。
本发明的第三方面提供第一方面所述的三酮类化合物在防治杂草中的应用。
本发明的第四方面提供一种除草剂，该除草剂中由活性成分和辅料组成，所述活性成分包括本发明第一方面所述的三酮类化合物中的至少一种。
本发明提供的上述三酮类化合物能够用作小麦和/或花生作物的HPPD除草剂，并且，本发明提供的上述三酮类化合物对稗草、马唐、狗尾草、雀麦、野燕麦、节节麦等多种危害小麦和/或花生生长的禾本科杂草和部分阔叶杂草具有良好防效，且对作物具有高安全性。
具体实施方式
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。
如前所述，本发明的第一方面提供了一种三酮类化合物，该化合物具有式(I)所示的结构，
Figure PCTCN2019109175-appb-000007
其中，在式(I)中，
R 1为正丙基或环戊基；
R 2选自H、C 1-6的烷基、由1-6个卤原子取代的C 1-3的烷基、C 2-6的炔基、由三甲基硅基取代的C 5-8的炔基、C 2-6的烯基、由1-6个卤原子取代的C 2-6的烯基；
X选自羟基、卤素、C 1-3的烷基硫基、苯基硫基、C 1-3的烷基砜基、苯基砜基；
R 3、R 4、R 5、R 6和R 7各种独立地选自H和C 1-3的烷基。
“C 1-6的烷基”表示碳原子总数为1-6的烷基，包括直链烷基、支链烷基和环烷基，例如可以为碳原子总数为1、2、3、4、5或6的直链烷基、支链烷基和环烷基，例如可以为甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、叔丁基、环丁基、正戊基、异戊基、环戊基、正己基、环己基等。
“C 1-3的烷基”表示碳原子总数为1-3的烷基，包括直链烷基、支链烷基和环烷基，例如可以为碳原子总数为1、2、3的直链烷基、支链烷基和环烷基，例如可以为甲基、乙基、正丙基、异丙基、环丙基。
“由1-6个卤原子取代的C 1-3的烷基”表示碳原子总数为1-3的烷基，包括直链烷基、支链烷基和环烷基，例如可以为碳原子总数为1、2或3的直链烷基、支链烷基和环烷基，并且烷基上的1-6个H被卤素原子取代，例如可以有1、2、3、4、5或6个H由选自氟、氯、溴、碘的至少一种卤素原子取代。
“C 2-6的炔基”表示碳原子总数为2-6的炔基，例如可以为乙炔基、丙炔基、丁炔基等。
“由三甲基硅基取代的C 5-8的炔基”表示碳原子总数为5-8的炔基，且该炔基的至少一个H由三甲基硅基取代。
“C 2-6的烯基”表示碳原子总数为2-6的烯基，例如可以为乙烯基、丙烯基、丁烯基等。“由1-6个卤原子取代的C 2-6的烯基”的定义与“C 2-6的烯基”的定义相似，不同的是，“由1-6个卤原子取代的C 2-6的烯基”上的1-6个H被卤素原子取代，例如可以有1、2、3、4、5或6个H由选自氟、氯、溴、碘的至少一种卤素原子取代。
“C 1-3的烷基硫基”表示硫原子的一端连接母核，另一端连接C 1-3的烷基。“苯基硫基”表示硫原子的一端连接母核，另一端连接苯基。“C 1-3的烷基砜基”表示砜基分别与母核和C 1-3的烷基连接。“苯基砜基”表示砜基分别与母核和苯基连接。
根据一种优选的具体实施方式，在式(I)中，
R 1为正丙基或环戊基；
R 2选自H、C 1-3的烷基、由1-3个卤原子取代的C 1-3的烷基、C 3-6的炔基、由三甲基硅基取代的C 6-8的炔基、C 3-6的烯基、由1-3个卤原子取代的C 3-6的烯基；
X选自羟基、卤素、C 1-3的烷基硫基、苯基硫基、C 1-3的烷基砜基、苯基砜基；
R 3、R 4、R 5、R 6各种独立地选自H和C 1-3的烷基；
R 7为H。
根据另一种优选的具体实施方式，在式(I)中，
R 1为正丙基或环戊基；
R 2选自H、甲基、乙基、一氟甲基、二氟甲基、一氟乙基、二氟乙基、三氟甲基、三氟乙基、
Figure PCTCN2019109175-appb-000008
X选自-OH、-F、-Cl、-Br、CH 3-S-、CH 3CH 2-S-、CH 3CH 2CH 2-S-、
Figure PCTCN2019109175-appb-000009
Figure PCTCN2019109175-appb-000010
R 3、R 4、R 5、R 6各种独立地选自H、甲基、乙基、正丙基和异丙基；
R 7为H。
根据一种特别优选的具体实施方式，式(I)所示的化合物选自以下中的至少一种：
Figure PCTCN2019109175-appb-000011
Figure PCTCN2019109175-appb-000012
Figure PCTCN2019109175-appb-000013
本发明提供的上述三酮类化合物能够用作小麦和/或花生等作物的HPPD除草剂，并且，本发明提供的上述三酮类化合物对稗草、马唐、狗尾草、雀麦、野燕麦、节节麦等多种危害小麦生长的禾本科杂草以及部分阔叶杂草具有良好防效，且对小麦和花生表现出优异的作物安全性。
本发明对获得上述三酮类化合物的具体方法没有特别的限定，本领域技术人员可以根据本发明提供的三酮类化合物的具体结构，结合有机合成领域的合成方法获得适合的制备三酮类化合物的方法。
但是，为了提高获得的三酮类化合物的收率，如前所述，本发明的第二方面提供了一种制备第一方面所述的三酮类化合物的方法，该方法包括：
(1)将式(II-1)所示结构的化合物依次与氯化亚砜和式(II-2)所示结构的化合物反应，得到式(II-3)所示结构的化合物；
(2)在重排反应条件下，将式(II-3)所示结构的化合物与催化剂在碱和溶剂存在下进行接触，得到式(II-4)所示结构的化合物；
任选该方法还依次包括以下步骤中的1个、2个或3个步骤：
(a)将式(II-4)所示结构的化合物进行卤化反应，得到式(II-5)所示结构的化合物；
(b)将式(II-5)所示结构的化合物与式(II-6)所示结构的硫醇钠反应，得到式(II-7)所示结构的化合物；
(c)在式(II-8)所示结构的过氧化物存在下，将式(II-7)所示结构的化合物进行氧化反应，得到式(II-9)所示结构的化合物；
Figure PCTCN2019109175-appb-000014
Figure PCTCN2019109175-appb-000015
X 2-SNa式(II-6)，
Figure PCTCN2019109175-appb-000016
其中，
式(II-5)所示结构的化合物中的X 1为卤素；
式(II-6)所示结构的化合物、式(II-7)所示结构的化合物和式(II-9)所示结构的化合物中的X 2选自C 1-3的烷基、苯基；
并且，式(II-1)、式(II-2)、式(II-3)、式(II-4)、式(II-5)、式(II-7)和式(II-9)中涉及的其余取代基与本发明前述第一方面中所述的化合物的取代基对应相同。
根据本发明所述的制备式(I)所示结构的三酮类化合物的方法，本领域技术人员可以根据重排反应的常规条件及操作将式(II-3)所示结构的化合物与催化剂在碱和溶剂存在下进行接触。
优选情况下，式(II-3)所示结构的化合物与催化剂和碱的摩尔比为1：(0.01-1)：(0.5-4)；更优选地，式(II-3)所示结构的化合物与催化剂和碱的摩尔比为1：(0.05-1)：(1-3)。
优选情况下，在步骤(2)中，所述接触的条件包括：反应温度为0-100℃；反应时间为0.5-36h；更优选地，在步骤(2)中，所述接触的条件包括：反应温度为20-40℃；反应时间为5-30h。
本领域技术人员应该理解的是，本发明所述的方法还可以包括对所得产物进行提纯的步骤，对于提纯的方法没有特别的要求，可以采用本领域技术人员常规使用的各种提纯方法，例如，可以采用萃取剂萃取，干燥剂干燥，并通过柱层析等方法除杂。
在本发明所述的制备方法中，式(II-1)所示结构的化合物可以采用本领域内的常规反应制备得到。
示例性地，式(II-1)所示结构的化合物可以采用如下所示的合成路线制备获得：
Figure PCTCN2019109175-appb-000017
具体地，将式A所示化合物与氯化碘反应得到式B所示化合物，并进一步与式C所示化合物反应得到式D所示化合物，然后在碱存在下将式D所示化合物与卤化物(R 2I或R 2Br)进行反应得到式E所示化 合物，并进一步与氰化亚铜反应得到式F所示化合物，进一步在酸性条件下水解得到式(II-1)所示结构的化合物。
在上述合成路线中，在没有特别说明的情况下，涉及的取代基的定义均与前文中的相应定义对应相同。
本发明的实例部分示例性地列举了上述合成路线中的具体的操作条件，本领域技术人员不应理解为对本发明的限制。
优选情况下，在步骤(2)中，所述催化剂选自氰化钠、氰化钾、丙酮氰醇、三甲基氰硅烷、1,2,4-三氮唑和苯并1,2,4-三氮唑中的至少一种。
优选地，在步骤(2)中，所述碱选自碳酸钾、碳酸钠、碳酸铯、三乙胺和吡啶中的至少一种。
优选地，在步骤(2)中，所述溶剂选自二氯甲烷、三氯甲烷、二氯乙烷、乙腈、甲苯、四氢呋喃和苯中的至少一种。
如前所述，本发明的第三方面提供了第一方面所述的三酮类化合物在防治杂草中的应用。
本发明所述的杂草为生长在有害于人类生存和活动的场地的植物，可以为非栽培的野生植物或对人类无用的植物。例如，可以为农作物种植地里的各种野生植物。
在本发明的前述应用中，所述杂草可以为阔叶杂草和/或禾本科杂草。
优选地，所述杂草为小麦田杂草和/或花生田杂草。
根据一种优选的具体实施方式，所述杂草为稗草、狗尾草、马唐、苋菜、黎、苘麻、节节麦、野燕麦、雀麦、看麦娘、日本看麦娘、硬草、棒头草、菵草中以及猪殃殃、牛繁缕、婆婆纳、碎米齐、酸模叶蓼、雀舌草、大巢菜的至少一种。
优选地，在本发明的前述应用中，所述三酮类化合物的用量为10-400克/公顷。
在本发明提供的如上所述的三酮类化合物的应用中，所述三酮类化合物用溶剂溶解并稀释后使用，用溶剂溶解并稀释后的浓度优选为0.05-0.4g/L。所述溶解三酮类化合物的溶剂可以包括N,N-二甲基甲酰胺、二甲亚砜等，所述稀释用的试剂可以为含有常用添加剂的水等。优选情况下，还可以向溶解有所述三酮类化合物的溶液中添加本领域内除草剂中常用的添加剂，如表面活性剂、乳化剂等中的一种或多种。经稀释后的本发明所述的三酮类化合物可以通过本领域内常规的方法喷洒至植物的茎和/或叶。
如前所述，本发明的第四方面提供了一种除草剂，该除草剂中由活性成分和辅料组成，所述活性成分包括本发明第一方面所述的三酮类化合物中的至少一种。
优选地，所述活性成分的含量为1-99.9重量％。
本发明的所述辅料为本领域制备除草剂的各种剂型中常用的各种添加剂。
优选地，本发明的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。
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，本实例中所用的各种原料均来自商购，其纯度级别均为分析纯。
在没有特别说明的情况下，以下室温均表示25℃±3℃。
制备例1：化合物31的制备
Figure PCTCN2019109175-appb-000018
室温下将75.5g的A所示的化合物加入到1L反应瓶中，搅拌下加入300mL冰乙酸，再将81g的ICl溶解到200mL冰乙酸中，搅拌下于30min内滴加到上述反应体系中，滴加完毕后，继续搅拌反应约2.5h。反应完毕后，将反应液减压抽滤，所得固体分别用乙腈200mL和冰乙酸200mL洗涤，干燥后得中间体B，收率95％；熔点：186-188℃。 1H NMR(600MHz,DMSO-d 6)：δ8.97(brs,3H),7.72(d,J＝8.4Hz,1H),6.75(d,J＝7.8Hz,1H),2.40(s,3H)。
将8.31g的中间体B加入到200mL两颈瓶中，加入80mL吡啶，搅拌下将2.55g的C-1所示的N-正丙基异氰酸酯缓慢加入到体系中。将反应液加热到100℃反应过夜，反应完毕后，减压蒸馏除去吡啶，所得固体用丙酮溶解，拌样、过柱，得中间体D-1。产率78％；熔点：295-296℃。 1H NMR(600MHz,CDCl 3)δ9.67(s,1H),8.14(d,J＝7.8Hz,1H),7.40(d,J＝7.8Hz,1H),3.45(t,J＝7.2Hz,2H),2.34(s,3H),1.72–1.32(m,2H),0.85(t,J＝7.2Hz,3H).
将7.91g的中间体D-1加入到200mL单颈瓶中，加入50mL的DMF，搅拌下加入14.95g的Cs 2CO 3继续搅拌反应约30min。将6.49g的CH 3I缓慢滴加到反应体系中，滴加完毕后室温搅拌反应过夜。反应完毕后，将体系倒入200mL水中，大量固体析出得中间体E-1。产率95％；熔点：208-210℃。 1H NMR(600MHz,CDCl 3)δ8.14(d,J＝7.8Hz,1H),7.40(d,J＝7.8Hz,1H),3.89(s,3H),3.45(t,J＝7.8Hz,2H),2.34(s,3H),1.54(dd,J＝14.4,7.8Hz,2H),0.85(t,J＝6.6Hz,3H).
将7.82g的中间体E-1，3.89g的CuCN加入到200mL双颈瓶中，加入100mL干燥的DMF。回流反应12h，反应完毕后减压蒸馏除去DMF，冷却后向反应瓶中加入100mL丙酮剧烈搅拌20min，过滤除去未反应完的CuCN。滤液脱干得中间体F-1。收率88％，熔点：210-211℃。 1H NMR(600MHz,CDCl 3)δ7.91(d,J＝7.8Hz,1H),7.36(d,J＝7.8Hz,1H),3.92(s,3H),3.48(t,J＝7.8Hz,2H),2.38(s,3H),1.64(dd,J＝14.4,7.8Hz,2H),0.95(t,J＝6.6Hz,3H).
将4.88g的中间体F-1加入到200mL反应瓶中，搅拌下加入30mL冰乙酸，30mL水，30mL浓硫酸。升温到120℃反应12h，反应完毕后冷却到室温，将反应体系倒入200mL冰水的烧杯中，向烧杯中加入100mL乙酸乙酯，萃取分出有机层，水层再用100mL乙酸乙酯萃取2次，萃取完毕后有机层合并，有机层再用50重量％的氢氧化钠溶液每次30mL萃取3次，合并水层，将水层用浓盐酸酸化到pH值为1左右，静置析出大量固体(即为中间体II-1-1)，抽滤，烘干固体直接投入下一步反应。
将1.38g的中间体II-1-1加入到100mL单颈瓶中，加入20mL干燥的THF，室温下缓慢滴加1.18g 的SOCl 2，滴加完毕后75℃回流反应约1.5h，TLC跟踪反应进程，反应结束后脱干溶剂。加入20mL干燥的CHCl 3，1.12g的式II-2-1所示的化合物，1.01g的Et 3N，反应约0.5h，TLC跟踪至酰氯消失。反应完毕后用100mL水洗一次，每次用30mL的1摩尔/升的HCl洗2次，每次用30mL的饱和NaHCO 3洗2次，无水Na 2SO 4干燥，过柱，得中间体II-3-1。产率80％；熔点：177-178℃。 1H NMR(600MHz,CDCl 3)δ8.25(d,J＝9.0Hz,1H),7.82(d,J＝9.0Hz,1H),5.87(t,J＝1.8Hz,1H),3.89(s,3H),3.45(t,J＝7.2Hz,2H),3.16(t,J＝7.2Hz,2H),2.48(td,J＝6.6,1.8Hz,2H),2.34(s,3H),1.74–1.31(m,4H),0.85(t,J＝6.6Hz,3H).
将1.48g的中间体II-3-1加入到50mL两颈瓶中，加入20mL无水乙腈，N 2保护下加入0.81g的Et 3N，34mg的丙酮氰醇。室温下反应8h，TLC跟踪至反应原料消失。反应完毕后脱干乙腈，加入约30mL的CHCl 3。每次用10mL的1摩尔/升的盐酸洗三次，饱和氯化钠每次10mL洗3次，有机层用无水硫酸钠干燥。减压脱去溶剂得浅黄色油状物，所得油状物用20mL甲醇重结晶得化合物31(白色固体)。
制备例2：化合物2的制备
Figure PCTCN2019109175-appb-000019
将0.925g的化合物31加入到50mL两颈瓶中，加入15mL无水二氯甲烷中，缓慢向体系中加入0.945g草酰氯。室温下反应15h，TLC跟踪至反应原料消失。反应完毕后用饱和碳酸氢钠将有机相洗涤三次，合并有机层，并用无水硫酸钠干燥。减压脱去溶剂得白色固体，即为化合物2。
制备例3：化合物3的制备
Figure PCTCN2019109175-appb-000020
将0.31g的化合物2加入到50mL两颈瓶中，加入15mL无水二氯甲烷中，和0.112g甲硫醇钠。室温下反应30h，TLC跟踪至反应原料消失。反应完毕后用直接拌样、柱层析即可得化合物3。
制备例4：化合物7的制备
Figure PCTCN2019109175-appb-000021
将0.2g的化合物3加入到50mL两颈瓶中，加入15mL无水二氯甲烷中，和0.171g间氯过氧苯甲酸(m-CPBA)。室温下反应10h，TLC跟踪至反应原料消失。反应完毕后用直接拌样、柱层析即可得化合物7。
制备例5：化合物32的制备
Figure PCTCN2019109175-appb-000022
将8.31g的中间体B加入到200mL两颈瓶中，加入80mL吡啶，搅拌下将3.33g的C-2所示的环戊基异氰酸酯缓慢加入到体系中。将反应液加热到100℃反应过夜，反应完毕后，减压蒸馏除去吡啶，所得固体用丙酮溶解，拌样、过柱，得中间体D-2。产率80％；熔点：307-308℃。 1H NMR(600MHz,CDCl 3)δ9.63(s,1H),8.09(d,J＝8.4Hz,1H),7.36(d,J＝8.4Hz,1H),5.96–5.71(m,1H),2.33(s,3H),2.06–1.83(m,2H),1.81–1.50(m,6H).
将8.88g的中间体D-2加入到200mL单颈瓶中，加入50mL的DMF，搅拌下加入15.6g的Cs 2CO 3继续搅拌反应约30min。将6.77g的CH 3I缓慢滴加到反应体系中，滴加完毕后室温搅拌反应过夜。反应完毕后，将体系倒入200mL水中，大量固体析出得中间体E-2。产率95％；熔点：220-221℃。 1H NMR(600MHz,CDCl 3)δ8.12(d,J＝7.8Hz,1H),7.38(d,J＝7.8Hz,1H),4.12–4.08(m,1H),3.89(s,3H),2.34(s,3H),2.09–1.83(m,2H),1.87–1.43(m,6H).
将8.755g的中间体E-2，4.06g的CuCN加入到200mL双颈瓶中，加入100mL干燥的DMF。回流反应12h，反应完毕后减压蒸馏除去DMF，冷却后向反应瓶中加入100mL丙酮剧烈搅拌20min，过滤除去未反应完的CuCN。滤液脱干得中间体F-2。产率86％；熔点：232-233℃。 1H NMR(600MHz,CDCl 3)δ7.92(d,J＝7.8Hz,1H),7.37(d,J＝7.8Hz,1H),4.20–4.12(m,1H),3.92(s,3H),2.42(s,3H),2.15–1.99(m,2H),1.90–1.46(m,6H).
将5.54g的中间体F-2加入到200mL反应瓶中，搅拌下加入30mL冰乙酸，30mL水，30mL浓硫酸。升温到120℃反应12h，反应完毕后冷却到室温，将反应体系倒入200mL冰水的烧杯中，向烧杯中加入100mL乙酸乙酯，萃取分出有机层，水层再用100mL乙酸乙酯萃取2次，萃取完毕后有机层合并，有机层再用50重量％的氢氧化钠溶液每次30mL萃取3次，合并水层，将水层用浓盐酸酸化到pH值为约1，静置析出大量固体(即为中间体II-1-2)，抽滤，烘干固体直接投入下一步反应。
将1.51g的中间体II-1-2加入到100mL单颈瓶中，加入25mL干燥的THF，室温下缓慢滴加1.18g的SOCl 2，滴加完毕后75℃回流反应约1.5h，TLC跟踪反应进程，反应结束后脱干溶剂。加入20mL干燥的CHCl 3，1.12g的式II-2-1所示的化合物，1.01g的Et 3N，反应约0.5h，TLC跟踪至酰氯消失。反应完毕后用100mL水洗一次，每次用30mL的1摩尔/升的HCl洗2次，每次用30mL的饱和NaHCO 3洗2次，无水Na 2SO 4干燥，过柱，得中间体II-3-2。产率70％；熔点：180-181℃。 1H NMR(600MHz,CDCl 3)δ8.25(d,J＝8.4Hz,1H),7.82(d,J＝8.4Hz,1H),5.85(s,1H),4.31–4.05(m,1H),3.89(s,3H),3.16(t,J＝7.8Hz, 2H),2.51(td,J＝6.6,1.8Hz,2H),2.34(s,3H),2.02–1.87(m,2H),1.83–1.60(m,6H),1.54(p,J＝6.6Hz,2H).
将1.38g的中间体II-3-2加入到50mL两颈瓶中，加入25mL无水乙腈，N 2保护下加入0.71g的Et 3N，30mg的丙酮氰醇。室温下反应10h，TLC跟踪至反应原料消失。反应完毕后脱干乙腈，加入约30mL的CHCl 3。每次用10mL的1摩尔/升的盐酸洗三次，饱和氯化钠每次10mL洗3次，有机层用无水硫酸钠干燥。减压脱去溶剂得浅黄色油状物，所得油状物用20mL甲醇重结晶得化合物32(白色固体)。
本发明的其余化合物的制备方法参照前述制备例1-5。其中，将本发明的通式结构中的部分具体化合物的表征数据列于表1中：
表1
Figure PCTCN2019109175-appb-000023
Figure PCTCN2019109175-appb-000024
Figure PCTCN2019109175-appb-000025
Figure PCTCN2019109175-appb-000026
Figure PCTCN2019109175-appb-000027
Figure PCTCN2019109175-appb-000028
测试例1
本测试例用于说明式(I)所示结构的化合物中的部分具体化合物以及对比化合物D1的除草活性抑制率(％)，其中对比化合物D1(该对比化合物D1为CN104557739A中公开的具体化合物，且CN104557739A与本发明的主要发明人相同)的结构式为：
Figure PCTCN2019109175-appb-000029
初筛试验(盆栽法)：供试靶标为稗草、狗尾草、马唐、苋菜、藜和苘麻，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。本发明的化合物和前述对比化合物D1按照150g.a.i/ha(克/公顷)的剂量在自动喷雾塔施药后，待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。
生长抑制率评价方法为目测法，具体根据表2所示的情况进行评级，测试结果如表3中所示。
表2
生长抑制率/％ 评价(抑制、畸形、白化等) 级别
0 对杂草或作物生长无影响，无药效症状。 0级(与空白对照相同)
1-19 对杂草或作物生长轻微影响，无明显药效症状。 1级
20-49 对杂草或作物长有影响，有明显药效症状。 2级
50-79 杂草或作物受到严重生长抑制。 3级
80-99 杂草或作物基本死亡。 4级
100 杂草或作物完全死亡。 5级
表3
Figure PCTCN2019109175-appb-000030
Figure PCTCN2019109175-appb-000031
测试例2
采用与测试例1相同的方法对部分化合物降低剂量进行复筛测定，测试结果见表4所示。
表4
Figure PCTCN2019109175-appb-000032
从上述所示的结果可以看出：
在初筛除草活性实验中，本发明的大多数化合物对稗草、狗尾草、马唐、苋菜、藜、苘麻6种常见的禾本科和阔叶杂草表现出十分优异的除草防效，与化合物D1具有相当或明显更优的活性。
进一步在降低浓度的复筛实验中，本发明的化合物对稗草、狗尾草以及马唐等3种杂草的除草活性仍 与D1相当甚至更优，而对于禾本科杂草节节麦、野燕麦、雀麦、看麦娘和日本看麦娘等，本发明中化合物10、11、12、14、31、32在三种施药方式下仍然对上述杂草保持较好的除草活性，而对照药剂D1对这上述的小麦田中主要禾本科杂草几乎没有表现出除草活性。
由此看出，本发明的化合物能够作为防除禾本科杂草的广谱性除草剂而使用。
测试例3
采用与测试例1相同的方法对部分化合物进行作物安全性的测定，测试结果见表5所示。
表5
Figure PCTCN2019109175-appb-000033
从上述所示的结果可以看出：
化合物11在三种施药浓度下对小麦仅有轻微的抑制作用，但不影响小麦的生长，具有优异的作物安全性。而化合物12和14也在低浓度下对小麦也具有较高的安全性。
化合物31在三种施药方式下对小麦几乎没有表现出抑制作用，化合物32在上述三种施药方式下也仅对小麦有轻微抑制，但不影响小麦正常生长。
结合上述的对小麦田难防治禾本科杂草的良好除草活性，本发明的化合物明显适合作为小麦田除草剂进行施用，具有巨大的商业价值。
此外，本发明中的化合物11、12、31和32对花生也十分安全，因此也能够用于花生田防除禾本科和部分阔叶杂草，而目前市面上还没有用于防治花生田杂草的HPPD抑制型除草剂。
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。

Claims (10)

  1. 一种三酮类化合物，该化合物具有式(I)所示的结构，
    Figure PCTCN2019109175-appb-100001
    其中，在式(I)中，
    R 1为正丙基或环戊基；
    R 2选自H、C 1-6的烷基、由1-6个卤原子取代的C 1-3的烷基、C 2-6的炔基、由三甲基硅基取代的C 5-8的炔基、C 2-6的烯基、由1-6个卤原子取代的C 2-6的烯基；
    X选自羟基、卤素、C 1-3的烷基硫基、苯基硫基、C 1-3的烷基砜基、苯基砜基；
    R 3、R 4、R 5、R 6和R 7各种独立地选自H和C 1-3的烷基。
  2. 根据权利要求1所述的化合物，其中，在式(I)中，
    R 1为正丙基或环戊基；
    R 2选自H、C 1-3的烷基、由1-3个卤原子取代的C 1-3的烷基、C 3-6的炔基、由三甲基硅基取代的C 6-8的炔基、C 3-6的烯基、由1-3个卤原子取代的C 3-6的烯基；
    X选自羟基、卤素、C 1-3的烷基硫基、苯基硫基、C 1-3的烷基砜基、苯基砜基；
    R 3、R 4、R 5、R 6各种独立地选自H和C 1-3的烷基；
    R 7为H；
    优选地，在式(I)中，
    R 1为正丙基或环戊基；
    R 2选自H、甲基、乙基、一氟甲基、二氟甲基、一氟乙基、二氟乙基、三氟甲基、三氟乙基、
    Figure PCTCN2019109175-appb-100002
    X选自-OH、-F、-Cl、-Br、CH 3-S-、CH 3CH 2-S-、CH 3CH 2CH 2-S-、
    Figure PCTCN2019109175-appb-100003
    Figure PCTCN2019109175-appb-100004
    R 3、R 4、R 5、R 6各种独立地选自H、甲基、乙基、正丙基和异丙基；
    R 7为H。
  3. 根据权利要求1所述的化合物，其中，式(I)所示的化合物选自以下中的至少一种：
    Figure PCTCN2019109175-appb-100005
    Figure PCTCN2019109175-appb-100006
  4. 一种制备权利要求1-3中任意一项所述的三酮类化合物的方法，该方法包括：
    (1)将式(II-1)所示结构的化合物依次与氯化亚砜和式(II-2)所示结构的化合物反应，得到式(II-3)所示结构的化合物；
    (2)在重排反应条件下，将式(II-3)所示结构的化合物与催化剂在碱和溶剂存在下进行接触，得到式(II-4)所示结构的化合物；
    任选该方法还依次包括以下步骤中的1个、2个或3个步骤：
    (a)将式(II-4)所示结构的化合物进行卤化反应，得到式(II-5)所示结构的化合物；
    (b)将式(II-5)所示结构的化合物与式(II-6)所示结构的硫醇钠反应，得到式(II-7)所示结构的化合物；
    (c)在式(II-8)所示结构的过氧化物存在下，将式(II-7)所示结构的化合物进行氧化反应，得到 式(II-9)所示结构的化合物；
    Figure PCTCN2019109175-appb-100007
    其中，
    式(II-5)所示结构的化合物中的X 1为卤素；
    式(II-6)所示结构的化合物、式(II-7)所示结构的化合物和式(II-9)所示结构的化合物中的X 2选自C 1-3的烷基、苯基；
    并且，式(II-1)、式(II-2)、式(II-3)、式(II-4)、式(II-5)、式(II-7)和式(II-9)中涉及的其余取代基与权利要求1-3中任意一项所述的化合物的取代基对应相同。
  5. 根据权利要求4所述的方法，其中，在步骤(2)中，所述接触的条件包括：反应温度为0-100℃；反应时间为0.5-36h。
  6. 根据权利要求4或5所述的方法，其中，在步骤(2)中，所述催化剂选自氰化钠、氰化钾、丙酮氰醇、三甲基氰硅烷、1,2,4-三氮唑和苯并1,2,4-三氮唑中的至少一种；
    优选地，所述碱选自碳酸钾、碳酸钠、碳酸铯、三乙胺和吡啶中的至少一种；
    优选地，所述溶剂选自二氯甲烷、三氯甲烷、二氯乙烷、乙腈、甲苯、四氢呋喃和苯中的至少一种。
  7. 权利要求1-3中任意一项所述的三酮类化合物在防治杂草中的应用；
    优选地，所述杂草为小麦田杂草和/或花生田杂草；
    优选地，所述杂草为稗草、狗尾草、马唐、苋菜、黎、苘麻、节节麦、野燕麦、雀麦、看麦娘、日本看麦娘、硬草、棒头草、菵草中以及猪殃殃、牛繁缕、婆婆纳、碎米齐、酸模叶蓼、雀舌草、大巢菜的至少一种。
  8. 根据权利要求7所述的应用，其中，所述三酮类化合物的用量为10-400克/公顷。
  9. 一种除草剂，该除草剂中由活性成分和辅料组成，所述活性成分包括权利要求1-3中任意一项所述的三酮类化合物中的至少一种；
    优选地，所述活性成分的含量为1-99.9重量％。
  10. 根据权利要求9所述的除草剂，其中，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。
PCT/CN2019/109175 2018-09-29 2019-09-29 三酮类化合物及其制备方法和应用以及一种除草剂 WO2020063981A1 (zh)

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CN113249343B (zh) * 2020-02-07 2024-04-26 山东舜丰生物科技有限公司 具有抗除草剂特性的多肽、核酸及其应用
CN113439750A (zh) * 2020-03-27 2021-09-28 辽宁先达农业科学有限公司 一种除草剂组合物及其应用和除草剂
CN114573565B (zh) * 2020-11-30 2023-08-08 山东先达农化股份有限公司 一种吡唑-喹唑啉酮类化合物及其制备方法和应用、一种除草剂
CN115124527B (zh) * 2022-05-31 2024-03-12 武汉智汇农耀科技有限公司 一种杂环酰胺-氮杂吲哚类化合物及其制备方法和应用、一种除草剂

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