Non-bipyridyl salt herbicides and their preparation methods and applications

Abstract

The present invention discloses a non-bipyridyl salt herbicide and its preparation method and application, specifically, the present invention provides a dienediamine compound having the structure of Formula I or a tricyclodienepiperazine structure shown in Formula II. The non-bipyridyl salt compound can be converted to paraquat or diquat under light irradiation and air conditions, and has the same herbicidal performance as paraquat or diquat but no obvious toxicity. Therefore, the non-bipyridyl salt compound of the present invention can be used as a non-toxic substitute for paraquat or diquat as a herbicide.

Description

[Technical Field]

[0001] The present invention relates to the field of pesticides, in particular the present invention relates to dienediamine or tricyclodienepiperazine herbicides and their preparation methods and uses. [Background technology]

[0002] Weeds pose a serious threat to the security of sustainable food production. Herbicides play an irreplaceable role in ensuring the security of global food production. Paraquat (PQ, 1,1-dimethyl-4,4-dipyridinium) dichloride is a non-selective herbicide that has rapid, efficient, and broad-spectrum herbicidal activity against weeds while retaining various characteristics such as intact root systems, rapid inactivation after contact with soil, and relatively low cost. PQ remains an indispensable product among herbicides due to its high environmental safety and high herbicidal efficacy.

[0003] However, the high toxicity of PQ to humans has become a serious social problem. The high mortality rate from PQ poisoning is due to its inherent toxicity and the lack of effective treatment. PQ has caused thousands of deaths worldwide through suicide and accidental poisoning. Data shows that PQ causes 2,000 cases of poisoning each year, with a mortality rate of 50-90%. In light of this practical problem, many countries have restricted or banned the use of PQ as a herbicide.

[0004] Several approaches have been reported to reduce the toxicity of PQ to humans and livestock and to develop antidotes for PQ. For example, mixing PQ with emetics or using PQ-encapsulated supramolecular vesicles, such as pillar[6]arenes and curubit[8]uril, have been used to develop safe PQ formulations. Due to its strong complexation ability with PQ, curubit[8]uril is also considered an effective antidote. Many antioxidants, such as naringin, lysine acetylsalicylic acid, selenium, quercetin, vitamin C, and sodium salicylate, are used as antioxidant strategies in the treatment of PQ poisoning. However, to date, these intervention strategies have not significantly reduced the mortality rate from PQ poisoning. Therefore, the development of nontoxic and effective herbicides as an alternative to PQ remains of great practical significance.

[0005] Therefore, there is an urgent need in the art for a non-toxic, practical, cost-effective and high-performance herbicide alternative to highly toxic paraquat. Summary of the Invention [Problem to be solved by the invention]

[0006] One object of the present invention is to provide a non-toxic, practical, cost-effective and high-performance herbicide as an alternative to paraquat or diquat.

[0007] Another object of the present invention is to provide a method for preparing the novel herbicides.

[0008] Another object of the present invention is to provide a method for eliminating weeds in agricultural land. [Means for solving the problem]

[0009] A first aspect of the present invention provides the use of a compound having the structure shown in Formula I or Formula II, an agronomically acceptable salt, enantiomer, diastereomer, optical isomer, tautomer, racemate, deuterated derivative, or combination thereof, for use in the preparation of a botanical herbicide, preferably a herbicide. [ka] [ka] where: R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are each independently hydrogen, halogen, cyano, C1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, -C(O)O(C1-C6) alkyl, -S(O) p is selected from the group consisting of a (C1-C6) alkyl group, a C1-C6 halogenated alkyl group, a C1-C6 halogenated alkoxy group, and -NRaRb; p is 0, 1 or 2; Ra and Rb are each independently selected from the group consisting of H, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 halogenated alkyl group, and a C1-C6 alkoxy group; R6' and R7' are each independently selected from the group consisting of H, a C1-C6 alkyl group, and a C1-C6 halogenated alkyl group. In another preferred embodiment, the compound has the structure shown in Formula I, wherein: R1, R2, R3, R4, R5, R6, R7, and R8 each independently represent hydrogen, halogen, cyano, C1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, -C(O)O(C1-C6) alkyl, -S(O) p is selected from the group consisting of a (C1-C6) alkyl group, a C1-C6 halogenated alkyl group, a C1-C6 halogenated alkoxy group, and -NRaRb; R9, R 10 are each independently selected from the group consisting of a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, and a C1-C6 halogenated alkyl group; Ra and Rb are each independently selected from the group consisting of H, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, and a C2-C6 alkynyl group.

[0010] In another preferred embodiment, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from the group consisting of hydrogen, halogen, and a cyano group; R9, R 10 are each independently selected from the group consisting of a C1-C6 alkyl group and a C3-C6 cycloalkyl group.

[0011] In another preferred example, R1, R2, R3, R4, R5, R6, R7, and R8 are all H, and R9, R 10 is a C1-C4 alkyl group.

[0012] In another preferred embodiment, the compound has the structure shown in Formula II: R1, R2, R3, R4, R5, R8, R9, R 10 are each independently selected from the group consisting of hydrogen, halogen, cyano, C1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, and C2-C6 alkynyl; R6' and R7' are each independently selected from the group consisting of H and C1-C6 alkyl groups.

[0013] In another preferred example, R1, R2, R3, R4, R5, R8, R9, R 10 , R6', and R7' are all H.

[0014] In another preferred embodiment, the compound is [ka] is selected from the group consisting of:

[0015] A second aspect of the present invention provides a method for preparing a compound as set forth in formula I or formula II below, comprising the steps of: [ka] or [ka] reacting a compound of formula Ia or a compound of formula IIa with a reducing reagent in aqueous solution to obtain a compound of formula I or a compound of formula II, wherein the reducing reagent is a borohydride or H; wherein X is selected from Cl or Br.

[0016] In another preferred example, when the reducing reagent is H2, the reaction is carried out in the presence of a hydrogenation catalyst, and preferably, the hydrogenation catalyst is selected from the group consisting of Pd and Ni.

[0017] In another preferred embodiment, the borohydride is selected from the group consisting of potassium borohydride, sodium borohydride, or a combination thereof.

[0018] In another preferred example, in the method, the molar ratio of the compound of formula Ia or IIa to the borohydride is 1:(2-5), preferably 1:(3-4).

[0019] In another preferred embodiment, the reaction temperature is 10 to 40°C, preferably 15 to 30°C, and / or

[0020] In another preferred example, the reaction time is 10 to 30 minutes, preferably 15 to 20 minutes.

[0021] In another preferred embodiment, the compound of formula Ia is 1,1-dimethyl-4,4'-dipyridinium dichloride.

[0022] In another preferred embodiment, the compound of formula IIa is 1,1'-ethylene-2,2'-dipyridinium dibromide.

[0023] In another preferred embodiment, the method further comprises the step of separating and purifying the reaction product after completion of the reaction.

[0024] A third aspect of the present invention provides an agricultural composition comprising: (a) a compound of formula I or a compound of formula II according to the first aspect of the present invention, an agronomically acceptable salt, enantiomer, diastereomer, optical isomer, tautomer, racemate, deuterated derivative, or combination thereof, as an active ingredient; and (b) an optional co-oxidizing agent, preferably selected from the group consisting of an oxidizing agent (preferably tetrachlorobenzoquinone, chloramine T, hydrogen peroxide, bleaching powder, sodium hydrosulfite, potassium peroxymonosulfate), a metal catalyst (preferably copper, iron, nickel, molybdenum, ruthenium, manganese, palladium, or platinum metal), or a combination thereof; and (c) an agronomically acceptable carrier and / or excipient, wherein preferred carriers are selected from the group consisting of water, aqueous NaCl solution, and (d) optional auxiliary agents, wherein the auxiliary agents are selected from the group consisting of molecular sieves, surfactants, protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, chelating agents, dyes, colorants, polymers, or combinations thereof. In another preferred example, the content of the active ingredient in the agricultural composition is 0.01 to 99.99 wt %.

[0025] In another preferred example, the co-oxidizing agent is [{Cu(Sal)2(MeCN)}2].

[0026] A fourth aspect of the present invention provides a method for herbicidal control, which comprises the step of applying a compound as described in formula I or formula II, or an agricultural composition as described in the third aspect of the present invention, to the surface of grass or plants in need of removal, or to the soil or environment surrounding the grass or plants, under conditions of light irradiation and the presence of oxygen gas, [ka] [ka] where: R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are each independently hydrogen, halogen, cyano, C1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, -C(O)O(C1-C6) alkyl, -S(O) p is selected from the group consisting of a (C1-C6) alkyl group, a C1-C6 halogenated alkyl group, a C1-C6 halogenated alkoxy group, and -NRaRb; p is 0, 1 or 2; Ra and Rb are each independently selected from the group consisting of H, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 halogenated alkyl group, and a C1-C6 alkoxy group; R6' and R7' are each independently selected from the group consisting of H, a C1-C6 alkyl group, and a C1-C6 halogenated alkyl group.

[0027] A fifth aspect of the present invention provides a compound as shown in formula II below: [ka] where: R1, R2, R3, R4, R5, R8, R9, R 10are each independently hydrogen, halogen, cyano, C1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, -C(O)O(C1-C6) alkyl, -S(O) p is selected from the group consisting of a (C1-C6) alkyl group, a C1-C6 halogenated alkyl group, a C1-C6 halogenated alkoxy group, and -NRaRb; p is 0, 1 or 2; Ra and Rb are each independently selected from the group consisting of H, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 halogenated alkyl group, and a C1-C6 alkoxy group; R6' and R7' are each independently selected from the group consisting of H, a C1-C6 alkyl group, and a C1-C6 halogenated alkyl group; Preferably, the compound is [ka] is.

[0028] A fifth aspect of the present invention provides a method for preparing paraquat or diquat, comprising the steps of: The method includes reacting a compound represented by Formula 2 or Formula 3 in the presence of light irradiation and oxygen gas to obtain paraquat or diquat. [ka]

[0029] In another preferred embodiment, The method includes reacting a compound represented by formula 2 or 3 in a first solvent at 60 to 100°C in the presence of an oxidizing agent and a catalyst to obtain paraquat or diquat.

[0030] In another preferred embodiment, the oxidizing agent is selected from the group consisting of tetrachlorobenzoquinone, chloramine T, hydrogen peroxide, bleaching powder, sodium hydrosulfite, potassium peroxymonosulfate, oxygen gas, air, or a combination thereof.

[0031] In another preferred example, the oxidizing agent is tetrachlorobenzoquinone.

[0032] In another preferred embodiment, the catalyst is selected from the group consisting of copper, iron, nickel, molybdenum, ruthenium, manganese, palladium, platinum, or a combination thereof.

[0033] In another preferred example, the catalyst is selected from the group consisting of [{Cu(Sal)2(MeCN)}2], a metal chloride, a metal bromide, or a combination thereof, preferably [{Cu(Sal)2(MeCN)}2].

[0034] In another preferred example, the metal chloride is selected from the group consisting of ferric chloride, copper chloride, or a combination thereof.

[0035] In another preferred example, the metal bromide is selected from the group consisting of ferric bromide, copper bromide, or a combination thereof.

[0036] In another preferred example, the amount of the oxidizing agent is 0.2 to 0.6 of the molar amount of the compound represented by formula 2 or formula 3.

[0037] In another preferred example, the amount of the catalyst is 0.01 to 0.1 of the molar amount of the compound represented by formula 2 or formula 3.

[0038] In another preferred example, the first solvent is selected from the group consisting of water, a C2-C6 nitrile solvent, a C1-C6 ketone solvent, or a combination thereof.

[0039] In another preferred example, the first solvent is selected from the group consisting of water, MeCN, acetone, or a combination thereof. [Effects of the Invention]

[0040] It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described below (e.g., in the Examples) can be combined with each other to form new or preferred technical solutions, which will not be repeated here due to space limitations. [Brief explanation of the drawings]

[0041] [Figure 1] 1 shows the trend diagram of quantitative analysis and cyclic voltammetry detection of the conversion of diene diamine compounds to PQ under light irradiation and air conditions. [Figure 2] 1 shows the herbicidal performance of dienediamine compounds against centipedegrass. [Figure 3] 1 shows the herbicidal activity of dienediamine compounds against Calamus. [Figure 4] 1 shows the herbicidal activity of dienediamine compounds against Arabidopsis thaliana. [Figure 5] The herbicidal activity of diquat and its reduced form, tricyclodienepiperazine, is shown. [Figure 6] The effects of intraperitoneal injection of dienediamine compounds and paraquat (PQ) on the survival rate and body weight of mice are shown. HR: hazard ratio. ***P<0.001, ****P<0.0001 (compared to the control group).

[0042] [Figure 7] The following shows various biochemical indexes in mice 48 hours after intraperitoneal injection of a dienediamine compound or PQ. TNF-α: tumor necrosis factor α, IL-1β: interleukin 1β, IL-6: interleukin 6, SCr: serum creatinine, BUN: urea nitrogen, UA: uric acid, AST: aspartate aminotransferase, ALT: alanine aminotransferase, SOD: superoxide dismutase, CAT: catalase. P<0.05 was considered statistically significant. 10 mice per group (n=10). [Figure 8]Figure 1 shows the damage characteristics of major organs in mice 48 hours after intraperitoneal injection of diamine compounds and PQ. Data are expressed as mean ± standard error. There were only 6 mice in each group (n = 6). P < 0.05 indicates statistical significance. Scale bar: 50 μm. [Figure 9] 1 shows the results of transmission electron microscopy of major organs in mice 48 hours after intraperitoneal injection of a dienediamine compound and PQ. [Figure 10] 1 shows the effects of dienediamine compounds and PQ on cellular activity and ROS levels in A549 cells, COS-7 cells, and Hep G2 cells. [Figure 11] 1 shows the apoptosis state of cells after direct contact of a dienediamine compound and PQ with A549 cells, COS-7 cells, and Hep G2 cells. [Figure 12] The molecular mechanisms of dienediamine compounds and PQ for Arabidopsis herbicidal control are shown. DETAILED DESCRIPTION OF THE INVENTION

[0043] After extensive and thorough research, the present inventors have discovered a non-toxic, practical, cost-effective, and highly effective dienediamine or tricyclodienepiperazine herbicide having structural formula I or structural formula II, respectively. The herbicides of the present invention do not function as electron transfer agents, and systematic evaluation in vivo and in vitro has shown that their toxicity is significantly lower than that of paraquat or diquat, and is comparable to that of a normal saline control. The herbicides of the present invention can be effectively converted into their active ingredients under natural light and air conditions, achieving highly efficient herbicidal performance. Based on this, the present inventors have completed the present invention.

[0044] term Each alkyl group moiety may be straight or branched, either alone or as part of a larger group (e.g., an alkoxy, alkylthio, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, or dialkylaminocarbonyl group, etc.) Typically, the alkyl group is, for example, a methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, t-butyl, n-pentyl, neopentyl, or n-hexyl group.

[0045] The term "alkyl group" generally refers to a C1-C6 alkyl group, a straight or branched chain alkyl group having from 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, or the like, preferably a C1-C4 alkyl group or a C1-C3 alkyl group, more preferably a C1-C2 alkyl group (e.g., a methyl group).

[0046] Alkenyl and alkynyl moieties can be straight or branched chain, and can be in either the (E)- or (Z)-configuration. Alkenyl and alkynyl moieties can contain one or more double and / or triple bonds in any combination, but preferably contain only one double bond (in the case of an alkenyl group) or only one triple bond (in the case of an alkynyl group).

[0047] The term "C2-C6 alkenyl" refers to a straight or branched chain alkenyl group having from 2 to 6 carbon atoms, such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, or the like.

[0048] The term "C2-C6 alkynyl" refers to a straight or branched chain alkynyl group having from 2 to 6 carbon atoms, such as ethynyl, propynyl, or the like.

[0049] Typically, the alkenyl or alkynyl group is a C2-C4 alkenyl or C2-C4 alkynyl group, more particularly ethenyl (vinyl), prop-2-enyl, prop-3-enyl (allyl), ethynyl, prop-3-ynyl (propargyl), or prop-1-ynyl. Preferably, the term "cycloalkyl group" refers to a cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl group.

[0050] As used herein, the term "aryl group" preferably refers to a phenyl group.

[0051] The terms "heteroaryl group" and "heteroaryl ring" (alone or as part of a larger group (e.g., heteroaryl-alkyl-)) refer to ring systems containing at least one heteroatom and may be monocyclic or bicyclic. Preferably, the monocycle contains 1, 2, or 3 heteroatoms independently selected from nitrogen, oxygen, and sulfur. Typically, as used herein, the term "heteroaryl group" includes furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, and triazinyl rings, which may be substituted or unsubstituted as described herein.

[0052] The term "halogen" refers to fluorine, chlorine, bromine, or iodine. The term "halogenated" refers to a group substituted with one or more of the same or different halogen atoms listed above, such as, for example, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoroisopropyl group, or the like.

[0053] The same applies to halogen in other definitions, such as halogenated alkyl groups or halogenated phenyl groups.

[0054] Examples of halogenated alkyl groups having 1 to 6 carbon atoms include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a 2,2,2-trifluoroethyl group, a 2-fluoroethyl group, a 2-chloroethyl group, a pentafluoroethyl group, a 1,1-difluoro-2,2,2-trichloroethyl group, a 2,2,3,3-tetrafluoroethyl group, a 2,2,2-trichloroethyl group, a heptafluoro-n-propyl group, and a perfluoro-n-hexyl group.

[0055] The term "alkoxy group" preferably has 1 to 6 carbon atoms. Typically, the alkoxy group is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, or t-butoxy, or one of the pentoxy or hexoxy isomers, preferably methoxy and ethoxy. It should be understood that two alkoxy group substituents can be present on the same carbon atom.

[0056] Typically, the term "halogenated alkoxy group" refers to, for example, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 1,1,2,2-tetrafluoroethoxy group, a 2-fluoroethoxy group, a 2-chloroethoxy group, a 2,2-difluoroethoxy group or a 2,2,2-trichloroethoxy group, preferably a difluoromethoxy group, a 2-chloroethoxy group or a trifluoromethoxy group.

[0057] Exemplary "C1-C6 alkyl-S-(alkylthio group)" include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, an s-butylthio group, or a t-butylthio group, and is preferably a methylthio group or an ethylthio group.

[0058] Exemplary "C1-C6 alkyl-S(O)-(alkylsulfinyl group)" include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, an n-butylsulfinyl group, an isobutylsulfinyl group, an s-butylsulfinyl group, or a t-butylsulfinyl group, and is preferably a methylsulfinyl group or an ethylsulfinyl group.

[0059] Exemplary "C1-C6 alkyl-S(O)2-(alkylsulfonyl group)" include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, an n-butylsulfonyl group, an isobutylsulfonyl group, an s-butylsulfonyl group, or a t-butylsulfonyl group, and is preferably a methylsulfonyl group or an ethylsulfonyl group.

[0060] The compounds of the present invention may have one or more asymmetric centers and may exist in the form of racemates, racemic compounds, single enantiomers, diastereomeric compounds, and single diastereomers. The asymmetric centers that may exist depend on the nature of the various substituents on the molecule. Each asymmetric center independently generates two optical isomers, and all possible optical and diastereomeric mixtures and pure or partially pure compounds are included within the scope of the present invention. The present invention includes all isomeric forms of the compounds.

[0061] The term "light irradiation conditions" refers to the presence of visible light irradiation in the environment, preferably under natural light conditions such as sunlight conditions.

[0062] The term "conditions in the presence of oxygen gas" refers to the presence of a sufficient amount of oxygen gas in the environment so as to convert the herbicidal composition of the present invention into the corresponding active ingredient (paraquat or diquat), and in a preferred embodiment, the oxygen gas can be present in an air environment.

[0063] The term "pesticidally acceptable salt" refers to an anion of a nematicide that is known and acceptable for forming a pharmaceutically acceptable salt. Preferably, the salt is water-soluble. Suitable acid addition salts formed by the compound of formula (I) include salts formed with inorganic acids, such as hydrochlorides, phosphates, sulfates, nitrates, etc., and salts formed with organic acids, such as acetates, benzoates, etc.

[0064] The term "weed" includes undesirable crop species, such as volunteer crops, including not only conventional crops but also volunteer crops that have been genetically modified through mutation or genetic engineering methods. For example, in a turfgrass crop, such as in a golf course environment, creeping bentgrass putting green turf may be considered "native" if found in a flat fairway area where a different type of grass is grown. Similarly, the following grasses may be considered weeds if found in an inappropriate location:

[0065] As used herein, the term "room temperature" refers to 5 to 45°C, preferably 10 to 30°C, and more preferably 25±2°C.

[0066] Unless otherwise specified, all references to paraquat (or PQ) herein refer to 1,1-dimethyl-4,4-dipyridinium or the salt formed with a halogen anion.

[0067] Non-bipyridyl herbicides The term "active ingredient" or "active substance" or "active compound" refers to a diene diamine compound having the structure of Formula I or a compound having a tricyclodiene piperazine structure as shown in Formula II, an agronomically acceptable salt, enantiomer, diastereomer, optical isomer, tautomer, racemate, deuterated derivative, or combination thereof; [ka] [ka] where: R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are each independently hydrogen, halogen, cyano, C1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, -C(O)O(C1-C6) alkyl, -S(O) p is selected from the group consisting of a (C1-C6) alkyl group, a C1-C6 halogenated alkyl group, a C1-C6 halogenated alkoxy group, and -NRaRb; p is 0, 1 or 2; Ra and Rb are each independently selected from the group consisting of H, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 halogenated alkyl group, and a C1-C6 alkoxy group; R6' and R7' are each independently selected from the group consisting of H, a C1-C6 alkyl group, and a C1-C6 halogenated alkyl group.

[0068] The dienediamine compounds or tricyclodienepiperazine compounds of the present application have herbicidal activity equivalent to that of paraquat or diquat, but their toxicity to animals is significantly lower than that of PQ or diquat. Therefore, they can be widely used in green agriculture around the world and have great potential for preventing deaths caused by PQ or diquat.

[0069] Examples of weeds that can be eliminated by the dienediamine compounds and tricyclodienepiperazine structure compounds of the present application include, but are not limited to, centipede grass, Arabidopsis thaliana, and Job's tears. After the dienediamine compounds and tricyclodienepiperazine come into contact with the surface of weeds, they produce paraquat and diquat, respectively, in sunlight and air. Both paraquat and diquat are non-selective herbicides that exhibit significant herbicidal effects on weeds and green plants, such as grasses, sedges, broadleaf weeds, Asteraceae, Polygonaceae weeds, and legumes. The dienediamine compounds or tricyclodienepiperazine compounds are mainly used for the following applications:

[0070] 1) Weed species in orchards: Siberian fox thistle (Cirsium arvense var. integrifolium), Japanese thistle (Cirsium japonicum Fisch. ex DC.), Japanese holly (Conyza japonica), Artemisia lavandulaefolia, Common earweed (Cerastium arvense L.), Cocklebur (Xanthium strumarium L.), Herb of Spanish needles, Bidens bipinnata, Artemisia hedinii Ostenf. et Pauls, Large crabgrass (Digitaria sanguinalis (L.) Scop.), Green foxtail (Setaria viridis), Common goosegrass (Eleusine indica (L.) Gaertn.), Wild oat (Avena fatua), annual peas (Vicia hirsuta), shepherd's purse (Capsella bursa-pastoris), spurge (Euphorbia helioscopia),

[0071] 2) Paddy field weeds: Monochoria vaginalis, Ammannia baccifera, Echinochloa crusgalli, Alternant weed, Ophiopogon japonicus, Chrysopogon aciculatus, Eleocharis dulcis, Paspalum paspaloides, and Sagittaria pygmaea,

[0072] 3) Weeds in wheat fields: Aster tataricus Lf, Erigeron annuus, Youngia japonica, Erigeron philadelphicus L., Cirsium arvense var. integrifolium, Gnaphalium affine D.Don, Hemistepta lyrata (Bunge) Bunge, Sowbuckthorn (Sonchus oleraceus L), Lapsana apogonoides, Alopecurus japonicus Steud., Beckmannia syzigachne, Sclerochloa dura, Polypogon fugax Nees ex Steud.), Alopecurus aequalis Sobol., Kentucky bluegrass (Poa pratensis L.), Wild oat (Avena fatua), Wheatgrass (Roegneria kamoji), Ryegrass (Lolium perenne),

[0073] 4) Weeds in cotton fields: Common goosegrass (Eleusine indica (L.) Gaertn.), Purslane (Portulaca oleracea L.), Large crabgrass (Digitaria sanguinalis (L.) Scop.), Common hawkweed (Eclipta prostrata), Quinoa (Chenopodium quinoa), Chinese hackberry (Acalypha australis), Sonchus arvensis, Echinochloa crusgalli, Cyperus rotundus, Imperata cylindrica (L.) Beauv.), Japanese hawkweed (Bolboschoenus planiculmis), Centipede grass (Cynodon dactylonlon), and Suaeda glauca (Bunge) Bunge), and Siberian fox thistle (Cirsium arvense var. integrifolium), redroot pigweed (Amaranthus retroflexus L), green foxtail (Setaria viridis), nightshade (Solanum nigrum L.), sowweed (Sonchus oleraceus L), field bindweed (Convolvulus arvensis L.), willow (Polygonum aviculare L.), ivy (Parthenocissus tricuspidata (Sieb. & Zucc.) Planch.), desert morning glory (Commelina diffusa), morning glory (Ipomoea nil (Linnaeus) Roth), thornweed (Amaranthus viridis), velvetleaf (Abutilon theophrasti Medicus), and burdock (Chloris virgata) Sw.), Amaranthus roxburghianus, Hibiscus trionum, Xanthium strumarium, Cyperus microiria, Daucus carota L., Digitaria ciliaris (Retz.) Koel.), Digitaria chrysoblephara, Eragrostis pilosa, Leptochloa chinensis (L.) Nees, Setaria glauca (L.) Beauv., Cirsium japonicum Fisch. ex DC., Artemisia canadensis, Taraxacum mongolicum Hand.-Mazz., Artemisia scoparia, Humulus scandens (Lour.) Merr., Physalis minima, and others.

[0074] 5) Weeds in corn fields: Large crabgrass (Digitaria sanguinalis (L.) Scop.), Japanese knotweed (Leptochloa chinensis (L.) Nees), common purse (Portulaca oleracea L.), goosegrass (Eleusine indica (L.) Gaertn.), etc. 6) Weeds in tobacco fields: common hackberry (Acalypha australis), giant knotweed (Polygonum lapathifolium L.), barnyard grass (Echinochloa crusgalli), cardamine hirsuta L., large crabgrass (Digitaria sanguinalis (L.) Scop.), alopecurus aequalis Sobol., Japanese holly (Mazus pumilus), etc.

[0075] Examples of weeds that can be eliminated by the dienediamine compound and tricyclodienepiperazine herbicides of the present application include centipedegrass (Cynodon dactylonlon), Arabidopsis (Arabidopsis thaliana), Job's lettuce (Acorus calamus L.), large crabgrass (Digitaria sanguinalis (L.) Scop.), goosegrass (Eleusine indica (L.) Gaertn.), hawkweed (Eragrostis cilianensis), purse (Portulaca oleracea L.), cow chickweed (Malachium aquaticum (L.) Fries.), Stellaria media (L.) Cyr, nightshade (Alternanthera sessilis (Linn.) DC.), nutsedge (Cyperus rotundus), and Japanese yew (Imperata cylindrical (L.) Beauv.), Oplismenus compositus (L.) Beauv., Phragmites australis(Cav.) Trin.ex Steud, Gallium spurium L., Fallopia convolvulus(L.) A. Love, Solanum nigrum L., Vicia gigantea Bge., Convolvulus arvensis L., Galeopsis bifida Boenn., Polygonum lapathifolium L., Polygonum bungeanum Turcz, Amaranthus retroflexus L., Commelina communis L., Elsholtzia ciliata(Thunb.) Hyland., ThlaspiarvenseL, Vicia sepium L., Descurainia Sophia (L.) Webb.ex Prantl), day bindweed (Calystegia hederacea Wall), wild oat (Avena fatua), wild crabgrass (Arrhenatherum elatius (L.) Presl), wheatgrass (Aegilops tauschii Coss.), annual foxtail (Alopecurus aequalis Sobol.), Japanese sedge (Alopecurus japonicas Steud.), Madagascar lace plant (Aponogeton madagascariensis), barnyardgrass (Echinochloa crusgalli), annual bluegrass (Poa annua L.), green foxtail (Setaria viridis (L.) Beauv.), Japanese sedge (Kyllinga brevifolia Rottb.), Cyperus difformis L.), Japanese holly (Fimbristylis miliacea (L.) Vahl), Scorpionweed (Juncellus serotinus), Cyperus iria, Japanese ragwort (Pycreus sanguinolentus), Barnyardgrass (Bulbostylis barbata (Rotth.) Kunth), Scirpus juncoides Roxb, Cyperus planiculmis (Fr.) Schmidt, Two-tone star (Ajuga nipponensis Makino), Japanese dandelion (Taraxacum mongolicum Hand.-Mazz.), Kentucky bluegrass (Poa pratensis L.), Japanese holly (Lycopodiastrum casuarinoides), Poinsettia (Euphorbia pulcherrima) Willd.et Kl.), pineapple (Ananas comosus (Linn.) Merr.), willow knotweed (Polygonum hydropiper L.), wild radish (Raphanus raphanistrum), Celastrus angulatus Maxim., cardamine hirsuta L.These include, but are not limited to, green weeds such as Echinacea purpurea (Linn.) Moench, and Inula japonica Thunb.

[0076] Agricultural composition The active substance of the present invention can be prepared into herbicidal compositions by conventional methods.These active compounds can be prepared into conventional formulations such as solutions, emulsifiable concentrates, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active substances, microcapsules in polymers, seed coating compositions, formulations used with combustion devices such as fumigation cartridges, fumigation pots and fumigation trays, and ULV cold mist and warm mist formulations.

[0077] These formulations can be produced by known methods, for example by mixing the active compound with an extender, which can be a liquid or liquefied gas or solid diluent or carrier, and optionally a surfactant, i.e., an emulsifier and / or dispersant and / or foam-forming agent. For example, when water is used as the extender, organic solvents can also be used as auxiliaries.

[0078] If necessary, active ingredients compatible with the herbicidal composition of the present invention, such as other herbicides, fungicides, plant growth regulators, antibiotics, insecticides, and fertilizers, can be added.

[0079] In a preferred embodiment, the content of the active ingredient is 1 to 99.99% by weight, preferably 5 to 95% by weight, based on the total weight of the agricultural composition, for example, the content of the active ingredient is 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight, etc.

[0080] The agronomically acceptable carriers and / or excipients may be other conventional auxiliaries that function, for example, as carriers, including, but not limited to, surfactants, protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, chelating agents, dyes, colorants, and polymers.

[0081] The term "carrier" as used herein refers to one or more organic, inorganic, natural or synthetic substances suitable for administering the active ingredient. Such carriers are generally inert and must be agriculturally acceptable, particularly to the treated plants. Carriers can be solids, such as clays, natural or synthetic silicates, silicon dioxide, resins, waxes, solid fertilizers, etc., or liquids, such as water, alcohols, ketones, petroleum fractions, aromatic or waxy hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc.

[0082] When a liquid solvent is used as a diluent or carrier, suitable diluents or carriers can include, for example: aromatic hydrocarbons such as xylene, toluene, or alkylnaphthalenes; chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride, or dichloromethane; aliphatic hydrocarbons such as cyclohexane or paraffins; mineral oil fractions; alcohols such as ethanol or ethylene glycol and their ethers and lipids; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; or less common polar solvents such as dimethylformamide and dimethyl sulfoxide; and water.

[0083] A liquefied gas diluent or carrier refers to a liquid that becomes a gas at normal temperature and pressure, such as halogenated hydrocarbons and aerosol propellants such as butane, propane, nitrogen gas, and carbon dioxide.

[0084] The solid carriers can be, for example, ground natural minerals such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatomaceous earth, and ground synthetic minerals such as highly dispersed silicic acid, alumina, and silicates. The solid carriers for granules are, for example, ground and classified natural zircon, such as calcite, marble, pumice, sepiolite, and dolomite, as well as synthetic granules of inorganic and organic coarse powders, and granules of organic materials such as sawdust, coconut shells, corn cobs, and tobacco stalks.

[0085] Adhesives include, for example, carboxymethyl cellulose, and natural and synthetic polymers (such as gum arabic, polyvinyl alcohol, and polyvinyl acetate) in powder, granule, or emulsion form.

[0086] The coloring agents include, for example, inorganic dyes such as iron oxide, cobalt oxide and Prussian blue, organic dyes such as azo dyes or metal phthalocyanine dyes, and trace nutrients such as iron, manganese, boron, copper, cobalt, aluminum and zinc salts.

[0087] The surfactant components according to the present invention include emulsifiers, dispersants or wetting agents, which may be ionic or nonionic.Examples that may be mentioned include polyacrylates, lignin sulfonates, phenolsulfonic acid or naphthalenesulfonates, polymers of ethylene oxide with aliphatic alcohols or fatty acids or aliphatic amines and substituted phenols (especially alkylphenols or arylphenols), sulfosuccinates, phosphate esters of taurine derivatives and alcohols or polyhydroxyethylated phenol phosphate esters, alkylsulfonates, alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates, fatty alcohol sulfates, sulfated hexadecanol-heptadecanol-octadecanol and sulfated fatty alcohol glycol ethers, etc., as well as condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylanisole. , ethoxylated isooctyl ether, octylphenol or nonylphenol, alkylphenyl polyethylene glycol ether, tributylphenyl polyethylene glycol ether, tristearate phenyl polyethylene glycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyethylene glycol ether acetal, sorbitol esters, lignin sulfite waste liquor, and further including proteins, modified proteins, polysaccharides, hydrophobically modified starch, polyvinyl alcohol, polycarboxylates, polyoxyalkylates, polyvinylamine, polyvinylpyrrolidone and copolymers.

[0088] Preferably, the carrier and / or excipient is at least one of an emulsifier, a dispersant, a wetting agent, a spreading agent, a stabilizer, an antifoaming agent, a synergist, a penetrating agent, an adhesive, a carrier, and a filler.

[0089] Preferably, the agricultural composition is in the form of at least one selected from wettable powders, soluble powders, emulsifiable concentrates, water suspension concentrates, oil-dispersible suspension concentrates, water emulsions, microemulsions, and water-dispersible granules.

[0090] The present invention is not particularly limited to specific methods for preparing various formulations of agricultural composition herbicides, and those skilled in the art can prepare herbicides in desired formulations by referring to the standard methods provided in "Modern Pesticide Formulation Processing Technology" (edited by Liu Guangwen, Chemical Industry Publishing House).

[0091] The components in the herbicide composition provided by the present invention can be mixed or stored separately. In a preferred embodiment, the components in the agricultural composition that form the active ingredients in the herbicide are stored alone or mixed with two or more other components and used in the form of a barrel mix.

[0092] The agricultural composition herbicide according to the present invention may be applied to crops and / or weeds by methods such as spraying, but is not limited thereto.

[0093] Process for preparing diene diamine compounds and tricyclodiene piperazines The compounds of the present invention having the structure shown in Formula I or Formula II can be prepared by the following methods, but the conditions of the methods, such as the reactants, solvent, base, amount of compound used, reaction temperature, and reaction time, are not limited to the following interpretations. The compounds of the present invention can also be easily prepared by arbitrarily combining various synthetic methods described herein or known in the art, and such combinations can be easily performed by a person skilled in the art.

[0094] Specifically, the compounds of the present invention can be prepared by the following methods. [ka] or [ka]

[0095] reacting a compound of formula Ia or a compound of formula IIa with a reducing reagent in aqueous solution to obtain a compound of formula I or a compound of formula II, wherein the reducing reagent is a borohydride or H; wherein X is selected from Cl or Br.

[0096] In one embodiment, when the reducing reagent is H2, the reaction is carried out in the presence of a hydrogenation catalyst, preferably the hydrogenation catalyst is selected from the group consisting of Pd and Ni.

[0097] In another preferred embodiment, the borohydride is selected from the group consisting of potassium borohydride, sodium borohydride, or a combination thereof. In another embodiment, in the method, the molar ratio of the compound of formula Ia or IIa to the borohydride is 1:(2-5), preferably 1:(3-4).

[0098] In another embodiment, the reaction temperature is 10 to 40°C, preferably 15 to 30°C, and / or

[0099] In another embodiment, the reaction time is 10 to 30 minutes, preferably 15 to 20 minutes.

[0100] In another embodiment, the compound of formula Ia is 1,1-dimethyl-4,4'-dipyridinium dichloride.

[0101] In another embodiment, the compound of formula IIa is 1,1'-ethylene-2,2'-dipyridinium dibromide.

[0102] In another embodiment, the method further comprises the step of separating and purifying the reaction product after the reaction is completed.

[0103] Compared with the prior art, the main advantages of the present invention are as follows: (1) When used as herbicides, the diene diamine compounds and tricyclodiene piperazine structures of the present invention have herbicidal activity equivalent to that of paraquat or diquat, but their toxicity to animals is equivalent to that of physiological saline in the control group, making them virtually non-toxic, and therefore they can be used as substitutes for paraquat or diquat. (2) The dienediamine compound and tricyclodienepiperazine structure of the present invention exhibit herbicidal activity under natural light irradiation and atmospheric conditions.

[0104] Hereinafter, the present invention will be further described in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and do not limit the scope of the present invention. In the following examples, experimental methods without specific conditions are usually in accordance with conventional conditions or conditions suggested by manufacturers. Unless otherwise specified, percentages and parts are calculated by weight.

[0105] Example 1. Preparation of Dienediamine Compound 2 [ka] 1,1-Dimethyl-4,4'-dipyridinium dichloride (100 g, 0.39 mol, 1.0 equiv.) was dissolved in 400 mL of distilled water, and potassium borohydride (98.4 g, 1.17 mol, 3.0 equiv.) was added and stirred at room temperature for 15 minutes. The mixture was extracted three times with dichloromethane (200 mL), dried over anhydrous sodium sulfate, and evaporated to give a white solid (73.5 g, 96% yield). 1 H NMR (500MHz, D2O). δ 5.62(t,1H),2.87(s,2H),2.45(t,2H),2.17(t,2H),2.12(s,3H). 13 C NMR(126MHz,D2O) δ 133.5,119.5,53.4,50.6,43.8,24.8.HRMS(ESI) m / z calcd for C 12 H 21 N2[(M+H)+ ]:193.1626,found:193.1703.

[0106] The above process of the present invention can be used to prepare the diene diamine compounds in a large scale preparation that is gentler and less costly than existing small scale preparation methods.

[0107] Example 2. Preparation of tricyclodienepiperazine (compound of formula 3) [ka] Dissolve 1,1'-ethylene-2,2'-dipyridinium dibromide (100 g, 0.35 mol, 1.0 equiv.) in 400 mL of distilled water and add potassium borohydride (56.7 g, 1.05 mol, 3.0 equiv.). Stir at room temperature for 15 minutes. Extract with dichloromethane (200 mL) three times, dry with sodium sulfate, and evaporate to give a black solid (47.1 g, 70% yield). 1 H NMR(500MHz,CDCl3) δ5.6-5.5(m 4H),3.1(m 2H),2.8-2.7(m 2H),2.6(m 2H),2.4-2.3(m 2H),2.0(m 2H),1.9(m 2H),1.8(m 2H); 13 C NMR (126MHz, CDCl3) δ 124.0,123.8,61.9,54.0,53.98,29.0.

[0108] Example 3. Conversion of the compound of formula 2 by the action of tetrachlorobenzoquinone [ka] 1,1'-Dimethyl-1,1',2,2',3,3',6,6'-octahydro-4,4'-bipyridine (100 mg, 0.52 mmol, 1.0 equiv.), tetrachlorobenzoquinone (63.9 mg, 0.26 mmol, 0.5 equiv.), and [{Cu(Sal)(NCMe)}] (19.7 mg, 0.03 mmol, 0.05 equiv.) were added to 5 mL of acetone, heated to 40 °C, and reacted for 8 h. The mixture was washed twice with 20 mL of dichloromethane and filtered to give a black solid, which was washed twice with 20 mL of methanol. The methanol was dried over sodium sulfate and evaporated to give yellow 1,1-dimethyl-4,4'-dipyridinium dichloride (128 mg, 96%). 1 H NMR(500MHz,D2O) δ 8.91(d,J=5.7Hz,1H),8.39(d,J=4.8Hz,1H),4.37(s,2H). 13 C NMR(126MHz,D2O) δ 149.8,146.2,126.6,48.3.HRMS(ESI) m / z calcd for C 12 H 14 N2[(M+2H) / 2]: 93.0572, found: 93.0573. The product was confirmed to be paraquat, indicating that the compound of formula 2 can be reconverted to paraquat under oxidizing conditions.

[0109] Example 4. Conversion of compounds of formula 2 under native conditions [ka] 1,1'-Dimethyl-1,1',2,2',3,3',6,6'-octahydro-4,4'-bipyridine (50 mg, 0.26 mmol, 1.0 equiv.) can be added to 5 mL of saline and left under natural light for 24 hours to give a yellow solid (40 mg, 63% yield). 1 H NMR(500MHz,D2O) δ 8.91(d,J=5.7Hz,1H),8.39(d,J=4.8Hz,1H),4.37(s,2H). 13C NMR(126MHz,D2O) δ 149.8,146.2,126.6,48.3.HRMS(ESI) m / z calcd for C 12 H 14 N2[(M+2H) / 2]: 93.0572, found: 93.0573, the product is confirmed to be paraquat.

[0110] Example 5. Conversion of compounds of formula 3 under native conditions [ka] 50 mg (50 mg, 0.26 mmol, 1.0 equiv.) of 1,4,6,7,9,12,12a,12b octahydrodipyridine[1,2-a:2',1'-c]pyrazine can be added to 5 mL of saline and left under natural light for 24 hours to obtain a yellow solid. 1 H NMR (500MHz, D2O) δ9.1 (dd, 2H), 8.8 (dd, 2H), 8.7 (m, 2H), 8.3-8.2 (m, 2H), 5.2 (d, 4H). 13 C NMR (126 MHz, DO) δ = 148.26, 147.0, 130.6, 128.3, 52.3, confirming that the product is the compound of formula 5.

[0111] Example 6. Conversion of compounds of formula 2 The present invention further examines the quantitative analysis of the conversion of diene diamine compounds to PQ. The present invention provides two conversion methods, all of which can achieve such conversion. Method I (small-scale conversion): Under the action of a catalyst and an oxidizing agent, the compound of formula 2 can achieve different degrees of conversion in different solvents under high temperature conditions. In particular, at 80 °C, using water as the catalyst, [{Cu(Sal)2(NCMe)}2] (5%) as the catalyst, and tetrachlorobenzoquinone as the oxidizing agent, the conversion rate can reach up to 92%. [ka]

[0112] [Table 1]

[0113] Method II (large-scale conversion): Under light irradiation and air conditions, using saline as a solvent, the compound of formula 2 is converted to PQ. As shown in Figure 1, the compound of formula 2 is converted to PQ under dark conditions at 25 ° C and light irradiation conditions at 25 ° C and 40 ° C, respectively. The results show that the diene diamine compound is hardly converted to PQ under dark conditions, but is converted to PQ under light irradiation, and the conversion efficiency increases with increasing temperature. After 24 hours of exposure under natural light irradiation at 40 ° C, the conversion rate of the diene diamine compound to PQ is about 63%, and after 24 hours of exposure under natural light irradiation at 25 ° C, the conversion rate is about 30%, indicating that the conversion of the compound of formula 2 is light-dependent and may be used as a sustained-release herbicide. [ka]

[0114] [Table 2]

[0115] Example 7. Evaluation of the herbicidal properties of compounds of formula 2 As is well known, centipede grass, Arabidopsis thaliana, and Jojoba are naturalized green weeds and invasive grasses in most regions of the world. Photosynthesis occurs in their leaves and entire leaf bundles. The compounds of the present application exhibit excellent control effects on green weeds by disrupting photosynthesis. Therefore, centipede grass, Jojoba, and Arabidopsis thaliana are selected as plant models for evaluating the herbicidal activity of the compounds of the present application.

[0116] Under air and sunlight, the compounds of formula 2 of the present application are sprayed on the leaves at concentrations of 1, 2, 4 and 8 times the PQ equivalent, respectively, and paraquat herbicide is used as a positive control, while saline spray is used as a blank control. The diameter of the observation area is 8 cm.

[0117] As shown in Figures 2, 3, and 4, 24 hours after spraying PQ and various concentrations of dienediamine, centipedegrass, J. japonica, and Arabidopsis leaves began to wilt. The herbicidal effect also increased with increasing concentration. At the same time, the herbicidal effect was slightly delayed in the groups treated with the same or double doses of the compound of Formula 2. When the dose concentration of the compound of Formula 2 was more than twice that of PQ, the herbicidal activity of the compound of Formula 2 was equivalent to that of PQ at any time point after application. This delayed herbicidal effect of the compound of Formula 2 is likely due to the efficiency and yield of the compound of Formula 2's conversion to PQ under air and sunlight. However, regardless of the dose concentration, 120 hours after application, the grass in all groups sprayed with the herbicide was completely withered and dried. These data demonstrate the herbicidal activity of the dienediamine compound of Formula 2.

[0118] Example 8. Evaluation of the herbicidal properties of the compound of formula 3 In the air and sunlight, the compound of formula 3 of the present application is sprayed on the leaves, and diquat herbicide is used as a positive control. The diameter of the observation area is 10 cm. As can be seen from Figure 5, three days after spraying the compound of formula 3, tricyclodienepiperazine (concentration not shown), centipede grass begins to wilt. After five days, the centipede grass completely wilts. The compound of formula 3 exhibits a herbicidal effect equivalent to that of diquat. This indicates that the compounds of the present application have herbicidal activity equivalent to that of diquat.

[0119] Example 9. In vivo safety evaluation of compounds of formula 2 First, we determined the optimal dose and time for lethality in mice by administering PQ at single intraperitoneal injection doses of 20, 30, 40, 50, and 60 mg / kg. All mice survived for more than 168 hours at 20 and 30 mg / kg doses, but died within 27 to 113 hours at 50 or 60 mg / kg doses, with their body weight significantly reduced on the first day. Furthermore, a significant increase in lung injury score was observed 24 hours after PQ administration, with the highest lung injury score at 48 hours compared to other time points. Therefore, 50 mg / kg was selected as the optimal dose. Tissue samples were collected from mice 48 hours after PQ administration.

[0120] To evaluate the in vivo safety of the compound of formula 2 of the present invention, acute toxicity tests were conducted on mice. First, the LD50 of diene diamine in mice was measured. As shown in Table 1, after intraperitoneal injection of 300 and 600 mg / kg diene diamine into mice on the third day after administration, all mice survived; after administration of 900 and 1050 mg / kg, three mice died, respectively; and after administration of 1200 mg / kg, eight mice died. By calculation, the LD50 on the seventh day after diene diamine intoxication was 1003.67 mg / kg (95% CI: 879.34, 1111.89). This indicates that diene diamine is less toxic to mice and is highly safe.

[0121] Table 1. Deaths and LD50 determinations of acute paraquat poisoning in mice after intraperitoneal injection of different concentrations of paraquat. [Table 3]

[0122] As shown in Figure 6, 100% of the mice administered PQ (0.19 mmol / kg) died within 112 hours after PQ administration. Meanwhile, all mice in the Formula 2 compound group survived 168 hours after administration of Formula 2 compound (0.19 mmol / kg). The weight of the mice in the PQ group continued to decrease (P<0.01), while the weight of the mice in the control group and the Formula 2 compound dienediamine group continued to increase steadily.

[0123] As shown in Figure 7, compared to the control group, the lung, liver, and kidney indices of mice intraperitoneally injected with 50 mg / kg paraquat for 48 hours all significantly increased, whereas the lung, liver, and kidney indices of mice administered dienediamine were not statistically significantly different from the control group. Cardiac indices were also not statistically different among the three groups. In the paraquat-intoxicated group, serum inflammatory indicators TNF-α, IL-β, and IL-6, liver function indicators AST and ALT, and kidney function indicators SCr, BUN, and uric acid levels significantly increased at 48 hours, whereas lung tissue SOD and CAT significantly decreased (P<0.05). There were no significant changes in these indices in mice administered the same dose of dienediamine (compound of Formula 2) intraperitoneally. This causes systemic inflammation and significant functional damage to the lungs, liver, and kidneys 48 hours after 50 mg / kg paraquat poisoning, but no significant differences in these biochemical indices were detected after intraperitoneal injection of the same molar concentration of the compound of formula 2, dienediamine.

[0124] As shown in Figure 8, after 48 hours of PQ administration, mice exhibited numerous organic lesions accompanied by obvious inflammation, including pulmonary hemorrhage, extensive thickening of alveolar septa, hemorrhage near the central vein in the liver, renal interstitial edema, degeneration of renal tubular epithelial cells, and multifocal myocardial cell necrosis accompanied by inflammatory cell infiltration. In contrast, no obvious pathological damage was observed in these major tissues in the dienediamine and control groups. At the same time, the tissue damage scores of major organs in the PQ group were significantly higher than those in the control and dienediamine groups.

[0125] Forty-eight hours after intraperitoneal injection of 0.19 mmol / kg of paraquat or the compound of Formula 2, transmission electron micrographs of the lungs, liver, kidneys, and heart were taken. The black arrows indicate mitochondrial damage. The scale bar for the heart group is 200 nm, while the scale bar for the other groups is 100 nm. As shown in Figure 9, the transmission electron microscopy results indicated mitochondrial damage, such as swelling, vacuolization, blurring, or rupture of mitochondrial cristae, in the lungs, liver, kidney, and heart tissues of mice in the PQ group. No obvious mitochondrial structural damage was detected in either the dienediamine group or the control group.

[0126] Once PQ enters the human body, it is rapidly absorbed and distributed to the lungs, kidneys, liver, and muscles. Death due to PQ ingestion is usually caused by multiple organ failure, including pulmonary edema, renal failure, and hepatic failure. Therefore, lung cells (A549 cells), kidney cells (COS-7), and liver cells (Hep G2) were selected to evaluate the direct cytotoxicity of dienediamine.

[0127] After 24 hours of co-incubation with PQ, PQ exhibited a direct cytotoxic effect on A549, Hep G2, and COS-7 cell lines in a dose-dependent manner. Meanwhile, after 24 hours of co-incubation with the compound of formula 2 at the same concentration gradient, no significant change in cell viability was detected in the above cells. The half maximal inhibitory concentration (IC50) was calculated to represent the cytotoxicity of the compound of formula 2. The results are shown in Table 2.

[0128] Table 2. Toxic effects of dienediamines and paraquat on three cell types [Table 4]

[0129] The results show that the IC of the compound group of formula 2 in the above three types of cells 50 The IC value was significantly higher than that of the PQ-treated group. 50 The values ​​showed an increase of several tens of times, which indicates a significant improvement in the safety of dienediamine to living organisms.

[0130] The above three types of cells were exposed to 100 μM PQ (100) and 100 μM compound of formula 2, respectively, and incubated for 18 hours. The intracellular reactive oxygen species (ROS) levels were quantified by flow cytometry, and the intracellular ROS levels (n=6) were measured by DCF fluorometry. As shown in Figure 10, ROS production in the PQ group was significantly increased compared to the compound of formula 2 group and the control group.

[0131] Furthermore, after 24 hours of incubation, Annexin V-FITC and propidium iodide (PI) staining (n=6) was performed as shown in Figure 11. Data are mean ± SEM. *p<0.05, **p<0.01, ***p<0.001, ****p<0.0001.

[0132] The results show that the cell apoptosis rate of the compound of formula 2 group is significantly reduced compared to the PQ group. This result is consistent with the ROS level, which is not significantly different.

[0133] Example 10. Herbicidal mechanism of compounds of formula 2 LC-MS was used to detect paraquat (PQ) in Arabidopsis plants treated with compound (Formula 2) under natural light and air conditions. After treatment with compound (Formula 2), the diamine was converted to PQ in a time-dependent manner (Figure 12C). Concomitantly, chlorophyll content (Figure 4C), maximum fluorescence quantum yield of photosynthetic system II (PSII), maximum photochemical efficiency (Fv / Fm), and leaf photosynthetic pigment content (SPAD) were significantly reduced (Figures 12A, C, and D). Electron microscopy revealed that treatment with compound (Formula 2) for 8 hours resulted in chloroplast cytoplasm lysis, swelling of thylakoids and mitochondrial cristae, and rupture of mesophyll nuclei, mitochondria, and chloroplast walls after 24 hours, accelerating plant death (Figure 12B). These results demonstrate that when sprayed on Arabidopsis thaliana, the compound of formula 2 is converted to PQ, which interferes with the photosynthetic electron transport mechanism of chloroplasts, causing the withering of the green plant.

[0134] overview The present inventors have discovered for the first time that the compound of formula 2 is not converted to PQ under air and dark conditions, but is directly converted to PQ under air and sunlight conditions. Furthermore, its herbicidal activity is equivalent to that of PQ under natural light and air. All of this evidence indicates that the conversion of the compound of formula 2 to PQ in plants is an important mechanism for its high herbicidal activity.

[0135] The present invention has demonstrated through in vivo and in vitro experiments that the toxicity of the compound of formula 2 to animals is significantly lower than that of PQ, and its toxicity level is equivalent to that of a normal control group using physiological saline, indicating that the dienediamine compound of formula 2 is a non-toxic herbicide.

[0136] The bipyridine structure is the basis of PQ as an electron transfer catalyst, which generates a large amount of free radicals, causing cell damage. PQ causes a decrease in SOD and CAT in lung tissue and an increase in ROS in lung, kidney, and liver cells. In contrast, in the dienediamine-treated group, there was no significant change in SOD and CAT levels in lung tissue and ROS production in cell lines.

[0137] In summary, the present invention uniquely uses diene diamine 2 to prepare a herbicidal composition, which can be converted into PQ under natural light and air conditions. Diene diamine not only has the same herbicidal activity as PQ, but is also non-toxic. Therefore, diene diamine has great potential and can be widely used in green agriculture around the world, preventing deaths caused by PQ.

[0138] All documents mentioned in this application are incorporated by reference in this application as if each document were incorporated by reference individually. Furthermore, after reading the above teachings of the present invention, those skilled in the art will be able to make various changes or modifications to the present invention, and these equivalents will also fall within the scope defined by the appended claims of this application.

Claims

1. 1. Use of a compound having the structure shown in Formula I or Formula II, its agriculturally acceptable salt, enantiomer, diastereomer, optical isomer, tautomer, racemate, deuterated derivative, or combination thereof, in Used in the preparation of botanical herbicides, 【Chemistry 1】 【Chemistry 2】 where: R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ are each independently hydrogen, halogen, a cyano group, C １ -C ６ Alkyl group, C ３ -C ６ Cycloalkyl group, C ２ -C ６ Alkenyl group, C ２ -C ６ Alkynyl group, C １ -C ６ Alkoxy group, —C(O)O(C １ -C ６ ) alkyl group, —S(O) ｐ (C １ -C ６ ) alkyl group, C １ -C ６ Halogenated alkyl group, C １ -C ６ is selected from the group consisting of a halogenated alkoxy group, and —NRaRb; p is 0, 1 or 2; Ra and Rb each independently represent H or C. １ -C ６ Alkyl group, C ３ -C ６ Cycloalkyl group, C ２ -C ６ Alkenyl group, C ２ -C ６ Alkynyl group, C １ -C ６ Halogenated alkyl group, C １ -C ６ alkoxy groups; R ６ ', R ７ ' are each independently H, C １ -C ６ Alkyl group, C １ -C ６ 1. Use of a compound having the structure shown in Formula I or Formula II, an agronomically acceptable salt, enantiomer, diastereomer, optical isomer, tautomer, racemate, deuterated derivative, or combination thereof, characterized in that the compound is selected from the group consisting of halogenated alkyl groups.

2. The compound has the structure shown in Formula I, wherein: R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ are each independently hydrogen, halogen, a cyano group, C １ -C ６ Alkyl group, C ３ -C ６ Cycloalkyl group, C ２ -C ６ Alkenyl group, C ２ -C ６ Alkynyl group, C １ -C ６ Alkoxy group, —C(O)O(C １ -C ６ ) alkyl group, —S(O) ｐ (C １ -C ６ ) alkyl group, C １ -C ６ Halogenated alkyl group, C １ -C ６ is selected from the group consisting of a halogenated alkoxy group, and —NRaRb; R ９ , R １０ are each independently C １ -C ６ Alkyl group, C ３ -C ６ Cycloalkyl group, C ２ -C ６ Alkenyl group, C ２ -C ６ Alkynyl group, C １ -C ６ selected from the group consisting of halogenated alkyl groups; Ra and Rb each independently represent H or C. １ -C ６ Alkyl group, C ３ -C ６ Cycloalkyl group, C ２ -C ６ Alkenyl group, C ２ -C ６ alkynyl groups, 2. The use according to claim 1.

3. R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ are each independently selected from the group consisting of hydrogen, halogen, and a cyano group; R ９ , R １０ are each independently C １ -C ６ Alkyl group, C ３ -C ６ cycloalkyl groups selected from the group consisting of 3. The use according to claim 2.

4. R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ are all H and R ９ , R １０ is C １ -C4 alkyl group 3. The use according to claim 2.

5. The compound has the structure shown in Formula II: R １ , R ２ , R ３ , R ４ , R ５ , R ８ , R ９ , R １０ are each independently hydrogen, halogen, a cyano group, C １ -C ６ Alkyl group, C ３ -C ６ Cycloalkyl group, C ２ -C ６ Alkenyl group, C ２ -C ６ alkynyl groups, R ６ ', R ７ ' are each independently H, C １ -C ６ alkyl groups selected from the group consisting of 2. The use according to claim 1.

6. R １ , R ２ , R ３ , R ４ , R ５ , R ８ , R ９ , R １０ , R ６ ', R ７ ' are all H's 6. The use according to claim 5.

7. The compound is 【Transformation 3】 characterized in that the compound is selected from the group consisting of 2. The use according to claim 1.

8. A process for preparing a compound as described in formula I or formula II below, comprising: It includes the following steps: 【Chemistry 4】 or 【Transformation 5】 Reacting a compound of formula Ia or a compound of formula IIa with a reducing reagent in aqueous solution to obtain a compound of formula I or a compound of formula II, wherein the reducing reagent is a borohydride or H ２ and A method for preparing a compound as described in the following formula I or II, characterized in that X is selected from Cl or Br.

9. 1. An agricultural composition comprising: (a) a compound of formula I or a compound of formula II as defined in claim 1, its agronomically acceptable salt, enantiomer, diastereomer, optical isomer, tautomer, racemate, deuterated derivative, or combination thereof, as an active ingredient; and (b) an optional co-oxidizing agent, preferably selected from the group consisting of an oxidizing agent (preferably tetrachlorobenzoquinone, chloramine T, hydrogen peroxide, bleaching powder, sodium hydrosulfite, potassium peroxymonosulfate), a metal catalyst (preferably copper, iron, nickel, molybdenum, ruthenium, manganese, palladium, or platinum metal), or a combination thereof; and (c) an agronomically acceptable carrier and / or excipient, wherein preferred carriers are selected from the group consisting of water, aqueous NaCl solution, and and (d) an optional auxiliary agent, wherein the auxiliary agent is selected from the group consisting of a molecular sieve, a surfactant, a protective colloid, an adhesive, a thickener, a thixotropic agent, a penetrating agent, a chelating agent, a dye, a colorant, a polymer, or a combination thereof.

10. A weed control method comprising:

10. The method of claim 9, wherein the compound as defined in formula I or formula II or the agricultural composition as defined in claim 9 is applied to the surface of grass or plants requiring removal, or to the soil or environment surrounding the grass or plants, under conditions of light irradiation and the presence of oxygen gas, 【Transformation 6】 【Transformation 7】 where: R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ are each independently hydrogen, halogen, a cyano group, C １ -C ６ Alkyl group, C ３ -C ６ Cycloalkyl group, C ２ -C ６ Alkenyl group, C ２ -C ６ Alkynyl group, C １ -C ６ Alkoxy group, —C(O)O(C １ -C ６ ) alkyl group, —S(O) ｐ (C １ -C ６ ) alkyl group, C １ -C ６ Halogenated alkyl group, C １ -C ６ is selected from the group consisting of a halogenated alkoxy group, and —NRaRb; p is 0, 1 or 2; Ra and Rb each independently represent H or C. １ -C ６ Alkyl group, C ３ -C ６ Cycloalkyl group, C ２ -C ６ Alkenyl group, C ２ -C ６ Alkynyl group, C １ -C ６ Halogenated alkyl group, C １ -C ６ alkoxy groups; R ６ ', R ７ ' are each independently H, C １ -C ６ Alkyl group, C １ -C ６ The herbicidal method as described above, wherein the herbicidal agent is selected from the group consisting of halogenated alkyl groups.

11. A compound as shown in formula II below: 【Transformation 8】 where: R １ , R ２ , R ３ , R ４ , R ５ , R ８ , R ９ , R １０ are each independently hydrogen, halogen, a cyano group, C １ -C ６ Alkyl group, C ３ -C ６ Cycloalkyl group, C ２ -C ６ Alkenyl group, C ２ -C ６ Alkynyl group, C １ -C ６ Alkoxy group, —C(O)O(C １ -C ６ ) alkyl group, —S(O) ｐ (C １ -C ６ ) alkyl group, C １ -C ６ Halogenated alkyl group, C １ -C ６ is selected from the group consisting of a halogenated alkoxy group, and —NRaRb; p is 0, 1 or 2; Ra and Rb each independently represent H or C. １ -C ６ Alkyl group, C ３ -C ６ Cycloalkyl group, C ２ -C ６ Alkenyl group, C ２ -C ６ Alkynyl group, C １ -C ６ Halogenated alkyl group, C １ -C ６ alkoxy groups; R ６ ', R ７ ' are each independently H, C １ -C ６ Alkyl group, C １ -C ６ selected from the group consisting of halogenated alkyl groups; Preferably, the compound is 【Chemistry 9】 A compound as shown in the following formula II, characterized in that:

12. 1. A method for preparing paraquat or diquat, comprising: The method, comprising the step of reacting a compound represented by Formula 2 or Formula 3 in the presence of light irradiation and oxygen gas to obtain paraquat or diquat. 【Chemistry 10】

13. The method comprises reacting a compound represented by Formula 2 or Formula 3 in a first solvent at 60 to 100°C in the presence of an oxidizing agent and a catalyst to obtain paraquat or diquat. The method of claim 12.

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