CN117069667A - Triazolinone structure-containing compound, application thereof and herbicide - Google Patents

Triazolinone structure-containing compound, application thereof and herbicide Download PDF

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Publication number
CN117069667A
CN117069667A CN202310852089.3A CN202310852089A CN117069667A CN 117069667 A CN117069667 A CN 117069667A CN 202310852089 A CN202310852089 A CN 202310852089A CN 117069667 A CN117069667 A CN 117069667A
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compound
weeds
herbicide
formula
triazolinone
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杨光富
郑佰峰
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Wuhan Zhihui Nongyao Technology Co ltd
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Wuhan Zhihui Nongyao Technology Co ltd
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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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • 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
    • 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
    • A01P13/02—Herbicides; Algicides selective
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/34—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C07C229/36—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings with at least one amino group and one carboxyl group bound to the same carbon atom of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms
    • 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 System
    • 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
    • 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 System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond
    • 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 System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage

Abstract

The invention relates to the technical field of novel pesticide compounds, and discloses a compound containing a triazolinone structure, application thereof and a herbicide. The compound has a structure shown in a formula (I). The compound provided by the invention has high weeding activity and wide weeding spectrum, has good safety on PPO transgenic soybeans, and has important significance on creating ultra-efficient PPO inhibitor herbicides with novel structures and preventing and controlling resistant weeds.

Description

Triazolinone structure-containing compound, application thereof and herbicide
Technical Field
The invention relates to the technical field of novel pesticide compounds, in particular to a compound containing a triazolinone structure, application thereof and a herbicide.
Background
Protoporphyrinogen oxidase (PPO, EC 1.3.3.4) is an important herbicide target. It is the last co-enzyme in the step of chlorophyll and heme biosynthesis, which is widely present in various organisms and catalyzes the oxidation of protoporphyrinogen IX to protoporphyrin IX.
In plants, protoporphyrin IX is an important substance for synthesizing chlorophyll, if PPO enzyme in plants is inhibited, the protoporphyrin IX can be quickly accumulated as a substrate, and permeate out to enter cytoplasm to be oxidized to generate high-concentration protoporphyrin IX, under the action of illumination and oxygen, singlet oxygen is generated, and cell membranes are subjected to peroxidation under the action of the singlet oxygen to be destroyed, so that cell death is caused, and finally plant leaves whiten to die.
The herbicide taking PPO as a target has unique action mechanism, slow resistance generation speed, broad-spectrum weeding activity and capability of preventing and controlling various weeds and resistant weeds.
PPO inhibitor herbicides have become the most important class of grass quality at present, and are the hot spot of research by various large pesticide companies.
Up to now, there are nine major classes of 30 PPO inhibitor herbicides that have been successfully marketed.
In the wide use of PPO inhibitors for nearly fifty years, researchers find that herbicides targeting PPO have the characteristics of broad spectrum, high efficiency, low toxicity, low residue, environmental friendliness and high crop safety, and more pleasing that the herbicides have excellent control effects on various resistant weeds, and can be used for controlling weeds which have developed resistance to glyphosate and ALS inhibitor herbicides.
In 1990, WO9002120A1 disclosed a triazolinone PPO inhibitor, the structural formula of which is a representative substance which is mainly used for controlling broadleaf weeds in cereal fields and the like (trade name: carfentrazone-ethyl).
However, the substance must be used in high amounts to have a relatively good efficacy, but this results in a significant decrease in safety.
Therefore, the creation of a novel green and ultra-efficient PPO inhibitor herbicide with higher activity and better safety becomes one of the hot spots of research of various large pesticide companies and scientific research institutions.
Disclosure of Invention
The invention aims to provide a novel triazolinone compound with high herbicidal activity.
In order to achieve the above object, a first aspect of the present invention provides a triazolinone structure-containing compound having a structure represented by the formula (I) or an agrochemically acceptable salt, hydrate, solvate, or enantiomer, optically active form derivative thereof,
formula (I):
wherein in formula (I), R is selected from H, C 1-6 Alkyl, substituted or unsubstituted C 2-6 Alkenyl, substituted or unsubstituted C 2-6 Is an alkynyl group of (c).
In a second aspect the present invention provides the use of a triazolinone structure containing compound according to the first aspect described above or an agrochemically acceptable salt, hydrate, solvate or enantiomer, optically active form derivative thereof as a PPO inhibitor.
A third aspect of the present invention provides the use of a triazolinone structure containing compound according to the first aspect described above or an agrochemically acceptable salt, hydrate, solvate or enantiomer, optically active form derivative thereof for controlling weeds.
In a fourth aspect, the present invention provides a herbicide comprising an active ingredient and an adjuvant, the active ingredient comprising at least one of a compound as described in the first aspect or an agrochemically acceptable salt, hydrate, solvate thereof, or an enantiomer, optically active form derivative thereof.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The following terms are to be construed in relation to herein, and without the contrary description, the following terms are to be construed as all the same or similar terms herein are to be accorded the same interpretation.
“C 1-6 The "alkyl group" of (a) represents a straight or branched alkyl group having a total of 1 to 6 carbon atoms, for example, the number of carbon atoms may be 1, 2, 3, 4, 5, 6, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc. "C 1-4 Alkyl "has a similar definition.
“C 2-6 Alkenyl "of (a) represents a straight or branched alkenyl group having a total of 2 to 6 carbon atoms, for example, the number of carbon atoms may be 2, 3, 4, 5, 6, including but not limited to allyl, propenyl, 1-butenyl, 2-butenyl. "C 2-4 Alkenyl "of (a) has a similar definition.
“C 2-6 Alkynyl "of (a) represents a straight or branched alkynyl group having a total of 2 to 6 carbon atoms, for example, the number of carbon atoms may be 2, 3, 4, 5, 6, including but not limited to propargyl, propynyl, 1-butynyl, 2-butynyl. "C 2-4 Alkynyl "of (a) has a similar definition.
HATU is 2- (7-azabenzotriazol) -N, N' -tetramethylurea hexafluorophosphate;
HBTU is O-benzotriazol-tetramethylurea hexafluorophosphate;
EDCI is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride;
CDI is N, N' -carbonyldiimidazole;
HOBt is 1-hydroxybenzotriazole;
DCC is dicyclohexylcarbodiimide;
DIC is N, N' -diisopropylcarbodiimide;
PyBOP is benzotriazol-1-yl-oxy-tripyrrolidinylphosphine hexafluorophosphate;
POCl 3 is phosphorus oxychloride;
T 3 p is 1-propyl phosphoric acid cyclic anhydride;
DIPEA is N, N-diisopropylethylamine;
DMAP is 4-dimethylaminopyridine;
DBU is 1, 8-diazabicyclo undec-7-ene.
As described above, the first aspect of the present invention provides a triazolinone structure-containing compound having a structure represented by the formula (I) or an agrochemically acceptable salt, hydrate, solvate, or enantiomer, optically active form derivative thereof,
formula (I):
wherein in formula (I), R is selected from H, C 1-6 Alkyl, substituted or unsubstituted C 2-6 Alkenyl, substituted or unsubstituted C 2-6 Is an alkynyl group of (c).
According to a preferred embodiment, in formula (I), R is selected from H, C 1-4 Alkyl, substituted or unsubstituted C 2-4 Alkenyl, substituted or unsubstituted C 2-4 Is an alkynyl group of (c).
More preferably, the compound represented by formula (I) is selected from any one of the following:
compound 1:compound 2: />Compound 3:compound 4: />Compound 5:compound 6: />
Particularly preferably, the compound represented by the formula (I) is compound 1, compound 4 or compound 6. The inventors of the present invention have found in the study that the compound under the preferable conditions has more excellent herbicidal activity.
The present invention is not particularly limited to the process for preparing the compounds described in the foregoing first aspect and a person skilled in the art may determine suitable synthetic routes to obtain the compounds described in the first aspect of the invention based on the formulae provided herein in combination with knowledge known in the art of organic synthesis. However, in order to achieve significantly higher yields and purities, the present invention provides a preferred method for preparing the compounds described in the first aspect of the invention.
According to a preferred embodiment, the process for preparing the triazolinone structure containing compound or an agrochemically acceptable salt, hydrate, solvate, or enantiomer, optically active form derivative thereof comprises: in the presence of a solvent and a condensing agent, carrying out condensation reaction on the compound shown in the formula (II) and the compound shown in the formula (III) or the hydrochloride of the compound shown in the formula (III),
NH 2 -(CH 2 ) 2 -C(O)-O-Q 1 formula (III)
Wherein Q is 1 Selected from H, C 1-6 Is a hydrocarbon group.
According to another preferred embodiment, the process for preparing the triazolinone structure containing compound or an agrochemically acceptable salt, hydrate, solvate, or enantiomer, optically active form derivative thereof comprises: in the presence of a solvent and a condensing agent, carrying out condensation reaction on the compound 4 and a compound shown in a formula (IV),
Q 2 -OH (IV)
Wherein Q is 2 Selected from substituted or unsubstituted C 2-6 Alkenyl, substituted or unsubstituted C 2-6 Is an alkynyl group of (c).
Preferably, the condensing agent is selected from HATU, HBTU, EDCI, CDI, HOBt, DCC, DIC, pyBOP, POCl 3 、T 3 At least one of P.
Preferably, the condensation reaction is performed in the presence of a basic substance selected from at least one of triethylamine, DIPEA, DMAP, DBU, potassium carbonate, sodium carbonate, cesium carbonate and pyridine.
Preferably, the solvent is selected from at least one of dichloromethane, chloroform, dichloroethane, acetonitrile, toluene, tetrahydrofuran, and benzene.
In the preparation method of the invention, intermediates and various reagents used are commercially available and can be prepared by reactions known in the art.
The following exemplary provides a method for preparing a compound of formula (II):
specifically, the method comprises the following steps: the method comprises the steps of reacting a diazotization reaction product of a compound A-1 with pyruvic acid to obtain a compound A-2, further obtaining a cyclic triazolinone compound A-3, carrying out difluoromethylation to obtain a compound A-4, carrying out nitration reaction on the compound A-4 to obtain a nitration product A-5, carrying out nitroreduction reaction to obtain a compound A-6, carrying out diazotization on the compound A-6 to obtain a diazonium salt A-7, and then reacting the diazonium salt A-7 with acrylic acid and cuprous chloride to obtain a compound shown in a formula (II).
As previously mentioned, the second aspect of the present invention provides the use of a triazolinone structure containing compound according to the first aspect described hereinbefore or an agrochemically acceptable salt, hydrate, solvate or enantiomer, optically active form derivative thereof as a PPO inhibitor.
As previously mentioned, a third aspect of the present invention provides the use of a triazolinone structure containing compound according to the first aspect described hereinbefore or an agrochemically acceptable salt, hydrate, solvate or enantiomer, optically active form derivative thereof for the control of weeds.
The aforementioned compounds provided by the present invention have excellent herbicidal activity, and therefore, the aforementioned compounds provided by the present invention are expected to be excellent super-efficient herbicides, which can be non-cultivated wild plants or plants useless for humans for plants grown in sites harmful to human survival and activity; for example, it is possible to provide a good herbicidal effect for various wild plants in a crop planting field.
For example, can be used for controlling at least one weed in cotton field, wheat field, paddy field, corn field, soybean field and PPO transgenic soybean field.
Preferably, the weeds are selected from at least one of broadleaf weeds, grassy weeds and sedge weeds.
Preferably, the broadleaf weeds are selected from at least one of polygonum syringae, acalypha australis, strange vegetables, glossoside glomerata, myrtle, shepherd's purse, chenopodium quinoa, abutilon, galium, veronicastrum, radix et rhizoma, amaranth, acalypha australis, black nightshade, lantern grass, purslane, amaranth, feather cockscomb, calyx seu fructus physalis, carp intestines, zinnia, and annual fleabane.
Preferably, the grass weeds are selected from at least one of barnyard grass, wild millet, goosegrass, golden green bristlegrass, tiger grass, crabgrass, alopecuroide, japanese alopecuroide, festival wheat, wild oat, brome, stephania sinica, and paspalum distachum.
Preferably, the Cyperaceae is selected from at least one of crushed Cyperus rotundus, iris lactea, and Cyperus rotundus.
As previously mentioned, a fourth aspect of the present invention provides a herbicide comprising an active ingredient and an adjuvant, the active ingredient comprising at least one of a compound as described in the first aspect or an agrochemically acceptable salt, hydrate, solvate thereof, or an enantiomer, optically active form derivative thereof.
Preferably, the active ingredient is present in an amount of 1 to 99.9999% by weight. For example, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt% and the like can be mentioned.
More preferably, the active ingredient is present in an amount of 5 to 99.9999% by weight.
Particularly preferably, the active ingredient is present in an amount of 5 to 99% by weight.
The present invention is not particularly limited in the selection of the auxiliary materials, and those skilled in the art may select the auxiliary materials according to the known art, and the auxiliary materials are exemplified by at least one selected from the group consisting of surfactants, protective colloids, binders, thickeners, thixotropic agents, penetrating agents, chelating agents, colorants, and polymers. The invention is not described in detail herein, and those skilled in the art should not understand the limitation of the invention.
Preferably, the dosage form of the herbicide of the present invention is selected from at least one of emulsifiable concentrates, suspending agents, wettable powders, dusts, granules, water agents, poison baits, mother liquor and mother powders.
Preferably, the herbicide is applied by soil treatment.
The invention will be described in detail below by way of examples. In the examples below, the various starting materials used in this example were all commercially available and all had analytically pure purity grades, unless otherwise specified. The room temperature is hereinafter referred to as 25.+ -. 1 ℃.
Preparation example 1: preparation of Compound 1
(1) Synthesis of Compound A-2
100g of Compound A-1 was dissolved in 500mL of 2N aqueous HCl in a 1L three-necked flask, stirred at-5℃to give 1.5 equivalents of NaNO 2 Dissolving in 100mL of water, slowly adding into the reaction system, stirring at-5deg.C for 2 hr, and slowly adding dropwise SnCl solution containing 2 equivalents 2 After stirring for 30 minutes at-5 ℃, the mixture was moved to room temperature and stirred for 2 hours, 50mL of water was added to the reaction system, and 50mL of an aqueous solution containing 1.5 equivalents of pyruvic acid was added thereto, and stirring was continued for 30 minutes. TLC was followed until the reaction was complete, suction-filtered, and the filter cake was rinsed with a small amount of water and dried to give compound A-2 in 91% yield.
(2) Synthesis of Compound A-3
The compound A-2 prepared above was placed in a 500mL two-necked flask, 200mL of toluene was added, and 1.5 equivalents of triethylamine was added under stirring (PhO) 2 PON 3 Added into the reaction system. And heating the reaction solution to reflux, tracking the reaction process by TLC, removing toluene after the reaction is finished, recrystallizing by ethanol to obtain a solid, filtering, and drying to obtain the compound A-3, wherein the yield is 71%.
(3) Synthesis of Compound A-4
The above synthesized compound A-3 was charged into a 500mL single-necked flask, and 2 equivalents of KOH, 5 equivalents of tetrabutylammonium bromide and 200mL of tetrahydrofuran were added thereto, followed by heat refluxing. Slowly bubbling difluoro chloromethane gas until the raw materials are completely reacted, concentrating the reaction solution under reduced pressure, adding 200mL of water and extracting with 100mL of dichloromethane for 3 times, combining organic layers, drying with anhydrous sodium sulfate, and purifying by column chromatography to obtain the compound A-4 with the yield of 96%.
(4) Synthesis of Compound A-5
Placing the synthesized compound A-4 into a 500mL single-necked bottle, adding 100mL of concentrated sulfuric acid, stirring uniformly at-5 ℃, dissolving 1.5 equivalents of concentrated nitric acid into 50mL of concentrated sulfuric acid, slowly dripping into a reaction system, reacting at-5 ℃ until the raw materials react completely, slowly pouring the system into 1L of ice water, precipitating a large amount of solids, stirring to room temperature, filtering, washing with water, and drying to obtain the compound A-5, wherein the yield is 89%.
(5) Synthesis of Compound A-6
The above-prepared compound A1-5 was placed in A1L single-necked flask, and 2 equivalents of NH was added 4 Cl and 3 equivalent of reduced iron powder are added with 500mL of ethanol and 100mL of water, the reflux reaction is carried out until the raw materials completely disappear, the solution is filtered through diatomite and washed with ethanol, and the filtrate is desolventized. The obtained solid was dissolved in water, extracted with ethyl acetate, and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then desolventized to obtain Compound A-6 in a yield of 90%.
(6) Synthesis of Compound of formula (II)
Adding compound A-6 into 500mL single-necked bottle, adding 200mL of water, stirring the reaction system at-5 ℃ to obtain 1.5 equivalent of NaNO 2 Dissolving in 100mL of water, slowly dripping the solution into a reaction system, stirring at-5 ℃ for 2 hours, adding the system into 1.5 equivalents of acrylic acid, 2 equivalents of cuprous chloride and hydrochloric acid solution, stirring at room temperature until TLC monitoring reaction is finished, and carrying out suction filtration to obtain the compound shown as the formula (II) with the yield of 78%.
(7) Synthesis of Compound 1
1mmol of the compound represented by the formula (II) was added to a 50mL single-necked flask, 20mL of methylene chloride was added, 1.5mmol of CDI was added, and the mixture was stirred at room temperature for 2 hours. 1.5mmol of methyl 3-aminopropionate hydrochloride and 2mmol of DBU were added, stirred at room temperature for 30 minutes, TLC monitored the progress of the reaction, and after completion of the reaction, the reaction was acidified with 20mL of 1N HCl solution, the aqueous phase was extracted with 20mL of dichloromethane, the organic phase was dried over anhydrous sodium sulfate and concentrated, and purified by column chromatography to give compound 1 in 87% yield.
Preparation example 2: preparation of Compound 2
This preparation was carried out using a procedure similar to preparation 1, except that the methyl 3-aminopropionate hydrochloride in step (7) was replaced with an equimolar amount of isopropyl 3-aminopropionate hydrochloride;
the remainder was the same as in preparation example 1, to obtain compound 2 in a yield of 65%.
Preparation example 3: preparation of Compound 3
This preparation was carried out in a similar manner to preparation 1, except that the methyl 3-aminopropionate hydrochloride in step (7) was replaced with an equimolar amount of t-butyl 3-aminopropionate hydrochloride;
the remainder was the same as in preparation example 1, to obtain compound 3 in 73% yield.
Preparation example 4: preparation of Compound 4
This preparation was carried out using a procedure similar to that of preparation 1, except that methyl 3-aminopropionate hydrochloride in step (7) was replaced with an equimolar amount of beta-alanine;
the remainder was the same as in preparation example 1, to give compound 4 in a yield of 71%.
Preparation example 5: preparation of Compound 5
1mmol of Compound 4 was added to a 50mL single-necked flask, 20mL of methylene chloride was added, 1.5mmol of CDI was added, and the mixture was stirred at room temperature for 2 hours. 1.5mmol of allyl alcohol and 2mmol of DBU were added, stirred at room temperature for 30 minutes, TLC monitored the progress of the reaction, after completion of the reaction, acidified with 20mL of 1N HCl solution, the aqueous phase extracted with 20mL of dichloromethane, the organic phase dried over anhydrous sodium sulfate and concentrated, and purified by column chromatography to give compound 5 in 75% yield.
Preparation example 6: preparation of Compound 6
This preparation was carried out using a procedure similar to preparation 5, except that the allyl alcohol in preparation 5 was replaced with an equimolar amount of propargyl alcohol;
the remainder was the same as in preparation example 5, to obtain Compound 6 in 79% yield.
Characterization data for specific compounds of the invention are shown in table 1.
TABLE 1
Test example 1: protoporphyrinogen oxidase inhibitory Activity
Protoporphyrinogen oxidase: the protoporphyrinogen oxidase used in the experiment is prepared by tobacco PPO expression and purification. The preparation was carried out according to the method in chinese patent CN110093325 a. The enzyme activity test was carried out according to the method described in the document J.Agric.food chem.2016,64,3,552-562 "to obtain the inhibitory activity of the triazolinone structure-containing compound of the present invention and the control compound carfentrazone-ethyl against protoporphyrinogen oxidase (inhibition constant K of the inhibitor) i )。
The results are shown in Table 2.
TABLE 2
Compounds of formula (I) K i (nM, tobacco PPO)
1 3.6
3 4.2
4 4.1
5 3.2
6 3.4
Carfentrazone-ethyl 5.6
As can be seen from Table 2, the compound provided by the invention has strong inhibition activity on tobacco PPO, and is obviously better than commercial herbicide carfentrazone-ethyl.
Test example 2: experiment of common screening in greenhouse
A certain amount of crude drug is weighed by an analytical balance (0.0001 g), dissolved by N, N-Dimethylformamide (DMF) containing 1wt% of Tween-80 emulsifier to prepare 0.5-1wt% of mother solution, and then diluted by distilled water to stock solutions with different concentrations for later use.
Two treatment modes of stem and leaf spraying and soil spraying are adopted.
Post-emergence stem and leaf spray: taking paper cup with inner diameter of 7cm, loading composite soil (vegetable garden soil: seedling substrate, 1:2, v/v) to 3/4 place, directly sowing test target seeds, covering soil by 0.2cm, and growing to 3 leaf stage for later use. The comparative compound carfentrazone-ethyl and the compound provided by the invention are all applied in an automatic spray tower according to the dosage of 10g a.i./mu, and after the foliar liquid medicine is dried, the foliar liquid medicine is transferred into a greenhouse for culture (the temperature is kept at 25-28 ℃ and the humidity is kept at 70%), and the results are investigated after 20 days.
And (3) soil spraying: taking 15 cm.70 cm lunch box, loading composite soil (vegetable garden soil: seedling substrate, 1:2, v/v) to 3/4 place, directly sowing weeds, and covering soil by 0.2cm. The comparative compound carfentrazone-ethyl and the compound provided by the invention were sprayed on soil at a dose of 10g a.i./mu, and the results were investigated after 20 days.
The investigation method comprises the following steps: after 20 days of test treatment, the target victim symptom and the growth inhibition condition are visually detected, the fresh weight of the overground part is called, the fresh weight inhibition rate (%) is calculated, and the growth inhibition rate (%) is expressed by the fresh weight inhibition rate.
Fresh weight inhibition (%) = (control fresh weight-treated fresh weight)/control fresh weight×100%
The rating was specifically based on the conditions shown in Table 3, and the test results are shown in Table 4.
TABLE 3 Table 3
Level of Target victim symptoms (inhibition, deformity, albinism, etc.) Growth inhibition ratio (%)
Level 0 (same as control) Has no influence on the growth of weeds or crops and no drug effect symptoms 0
Level 1 Has slight effect on weed or crop growth and no obvious pharmacodynamic symptoms 1-19
Level 2 Has obvious effect on weed or crop growth and obvious medicinal effect symptom 20-49
3 grade Weeds or crops are severely inhibited from growing 50-79
Grade 4 Basic death of weeds or crops 80-99
Grade 5 Complete death of weeds or crops 100
TABLE 4 Table 4
The weeding activity test results show that the compound provided by the invention has excellent control effects on broadleaf weeds, grassy weeds and sedge weeds.
In particular, as can be seen from the control effect data obtained by stem and leaf treatment and soil treatment in table 4, the compounds 1, 4 and 6 provided by the invention have excellent herbicidal activity on all tested weeds, the grade is 5, and the control effect on grassy weeds such as crabgrass, barnyard grass and moleplant is extremely superior to that of carfentrazone-ethyl.
Under the same dosage, the compound 2 and the compound 3 provided by the invention have the control effect grades of 5 on amaranth, shepherd's purse, black nightshade and garcinia sedge, and have the equivalent weeding activity with the commercialized medicament carfentrazone-ethyl.
The control efficiency grade of the compound 2, the compound 3 and the compound 5 provided by the invention on crabgrass, barnyard grass and moleplant reaches 4 or 5, and the carfentrazone-ethyl under the same dosage is only 2 or 3, so that the control effect of the compound on the tested weeds is obviously better than that of the commercial carfentrazone-ethyl.
In addition, from the above results, it can be seen that the novel compounds obtained can significantly enhance the control effect on grassy weeds such as barnyard grass when active esters or amino acid/ester fragments are introduced into the molecule. This demonstrates that, for the compounds of formula (I) provided by the present invention, the active esters or amino acid/ester fragments specifically found by the present inventors have a significant promoting effect on enhancing the herbicidal activity of PPO inhibitors.
Comprehensive analysis shows that the active ester or the amino acid/ester fragment plays an important role in improving the weeding activity of the triazolinone PPO inhibitor.
Test example 3: experiment of preliminary screening in greenhouse
A certain amount of crude drug is weighed by an analytical balance (0.0001 g), dissolved by DMF containing 1wt% of Tween-80 emulsifier to prepare 0.5-1wt% of mother solution, and then diluted by distilled water to stock solutions with different concentrations for standby.
The potting method is adopted: taking a flowerpot with the inner diameter of 6cm, filling composite soil (vegetable garden soil: seedling substrate, 1:2, v/v) to 3/4 positions, directly sowing weed targets (the bud rate is more than or equal to 85%), covering soil by 0.2cm, and keeping the targets to be tested for 4-leaf period. After the comparative compound carfentrazone-ethyl and the compound provided by the invention are applied to an automatic spray tower according to the dosage shown in the following table, the weed leaf surface liquid medicine is moved into a greenhouse for cultivation after being dried, and the result is investigated after 20 days.
And (3) soil spraying: taking 15 cm.70 cm lunch box, loading composite soil (vegetable garden soil: seedling substrate, 1:2, v/v) to 3/4 place, directly sowing weeds, and covering soil by 0.2cm. Each compound was administered in an automatic spray tower at the doses shown in the following table and the results were investigated after 20 days.
The investigation method was the same as in test example 2, and the test results are shown in table 5.
TABLE 5
Note that: "/" indicates no test.
The above preliminary screening test results show that the compounds of the present invention have reduced control of the test weeds with reduced dosages. However, from the test results, when the dosage is reduced to 2.5g a.i./mu, the compound of the invention can still keep a higher level of prevention effect on weeds even if a stem and leaf treatment mode or a soil treatment mode is adopted, and the compound of the invention has a prevention effect superior to that of the commercialized medicament carfentrazone-ethyl.
In particular, at doses of 5g a.i./mu and 2.5g a.i./mu, the compounds 1, 4 and 6 provided by the invention also show extremely excellent herbicidal activity against older weeds, and especially the control effect on grassy weeds is obviously better than that of a commercial herbicide carfentrazone-ethyl.
Test example 4: PPO transgenic soybean safety field test
A certain amount of crude drug is weighed by an analytical balance (0.0001 g), dissolved by DMF containing 1wt% of Tween-80 emulsifier to prepare 0.5-1wt% of mother solution, and then diluted by distilled water to stock solutions with different concentrations for standby.
Crop testing: PPO transgenic soybean (LT 32) was tested.
The testing method comprises the following steps: at 36m 2 For one cell, each treatment was repeated three times, the target to be tested was subjected to stem and leaf spraying treatment until the target to be tested was about 3-leaf stage, and in the treatment zone, compound 1 and carfentrazone-ethyl were subjected to spraying application at dosages shown in the following table; in the control zone, spraying was performed with a reagent that did not contain the original drug, i.e. with DMF containing 1wt% Tween-80 emulsifier. The treated area and the control area were observed after 14 days of treatment and the results were investigated.
The safety of PPO transgenic soybean was counted in accordance with the same investigation method as in test example 2, and the test results are shown in table 6.
TABLE 6
The field trials of safety for PPO transgenic soybean showed that compound 1 of the present invention had very good safety for PPO transgenic soybean (LT 32) at the tested dose. Compound 1 had substantially no effect on the growth of PPO transgenic soybean (LT 32) when the test dose reached 20g a.i./mu; and the PPO transgenic soybean (LT 32) basically dies after the carfentrazone-ethyl treatment at the same dosage.
It can be seen that the safety effect of compound 1 on PPO transgenic soybean (LT 32) is significantly better than the commercial herbicide carfentrazone-ethyl. Thus, the compounds provided herein can be used to control at least one weed in a PPO transgenic soybean field.
The compound disclosed by the invention has very good application value by combining with the current experimental data, and can be used as a candidate drug molecule of PPO herbicides. The compound containing the triazolinone structural fragment provided by the invention has important significance for creating an ultra-efficient herbicide and being used for preventing and controlling weeds.
In the present invention, the active ester or amino acid/ester fragment on the one hand increases the herbicidal activity of the inhibitor molecule and on the other hand improves the crop safety of the inhibitor molecule. The subsequent development of the compound is expected to be applied to the prevention and treatment of various field weeds, and has very good economic value and social benefit.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (10)

1. A compound containing a triazolinone structure or an agrochemically acceptable salt, hydrate, solvate, or enantiomer, optically active form derivative thereof, characterized in that the compound has a structure represented by the formula (I),
formula (I):
wherein in formula (I), R is selected from H, C 1-6 Alkyl, substituted or unsubstituted C 2-6 Alkenyl, substituted or unsubstituted C 2-6 Is an alkynyl group of (c).
2. The compound according to claim 1Wherein, in formula (I), R is selected from H, C 1-4 Alkyl, substituted or unsubstituted C 2-4 Alkenyl, substituted or unsubstituted C 2-4 Is an alkynyl group of (c).
3. The compound according to claim 1 or 2, wherein the compound represented by formula (I) is selected from any one of the following:
compound 1:compound 2: />Compound 3: />Compound 4: />Compound 5:compound 6: />
4. Use of a triazolinone structure containing compound according to any one of claims 1 to 3 or an agrochemically acceptable salt, hydrate, solvate or enantiomer, optically active form derivative thereof as a PPO inhibitor.
5. Use of a compound containing a triazolinone structure according to any one of claims 1 to 3 or an agrochemically acceptable salt, hydrate, solvate or enantiomer, optically active form derivative thereof for controlling weeds.
6. The use according to claim 5, wherein the weeds are selected from at least one of broadleaf weeds, grassy weeds and sedge weeds.
7. The use according to claim 5 or 6, wherein the broadleaf weeds are selected from at least one of polygonum syringae, acalypha australis, stranguria, hedyotis diffusa, physalis pubescens, shepherdspurse, chenopodium album, galium, veronicastrum, radix et rhizoma, amaranth, acalypha australis, black nightshade, lantern grass, purslane, amaranth, feather cockscomb, calyx seu fructus, carp intestines, zinnia, and annual fleabane; and/or the number of the groups of groups,
the grass weeds are selected from at least one of barnyard grass, wild millet, wild broom corn millet, cowherb, golden green bristlegrass, tiger grass, crabgrass, alopecuroide, japanese alopecuroide, festival wheat, wild oat, brome, stephania tetrandra and double spike paspalum; and/or the number of the groups of groups,
the Cyperaceae is selected from at least one of crushed Cyperus rotundus, fructus Foeniculi, and Cyperus rotundus.
8. A herbicide comprising an active ingredient and an adjuvant, wherein the active ingredient comprises at least one of a compound of any one of claims 1 to 3 or an agrochemically acceptable salt, hydrate, solvate, or enantiomer, optically active form derivative thereof.
9. Herbicide according to claim 8, wherein the active ingredient is present in an amount of 1-99.9999% by weight, preferably 5-99.9999% by weight.
10. The herbicide according to claim 8 or 9, wherein the herbicide is in a dosage form selected from at least one of emulsifiable concentrates, suspending agents, wettable powders, dusts, granules, aqueous solutions, poison baits, mother solutions and mother powders; and/or the number of the groups of groups,
the herbicide is applied in a soil treatment mode.
CN202310852089.3A 2022-07-14 2023-07-12 Triazolinone structure-containing compound, application thereof and herbicide Pending CN117069667A (en)

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DE3936623A1 (en) * 1989-11-03 1991-05-08 Bayer Ag SULFONYLAMINOCARBONYLTRIAZOLINONE WITH SUBSTITUTES TIED ABOVE SULFUR
CA1331463C (en) * 1988-08-31 1994-08-16 Kathleen Megan Poss Herbicidal triazolinones
DE4433966A1 (en) * 1994-09-23 1996-03-28 Bayer Ag Process for the preparation of alkoxytriazolinones
CN100491338C (en) * 2003-09-29 2009-05-27 沈阳化工研究院 Substituted amide herbicides
CN106831618B (en) * 2015-12-04 2019-11-12 沈阳中化农药化工研发有限公司 A kind of quaternary ammonium compound and its application
US10897903B2 (en) * 2016-05-24 2021-01-26 Basf Se Method for controlling PPO resistant weeds
EP3281523A1 (en) * 2016-08-09 2018-02-14 Basf Se Method for controlling ppo resistant weeds
CN114213341B (en) * 2021-11-22 2023-07-04 南开大学 Oxobutyronic acid (-2-enoate) acid compound, preparation method thereof, herbicide composition, application thereof and herbicide
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