Use of hydroxyproline and derivative thereof, biological herbicide, broad-spectrum herbicide, and weed control method

Abstract

The present invention relates to the technical field of weeding, in particular to a use of hydroxyproline and a derivative thereof, a biological herbicide, a broad-spectrum herbicide, and a weed control method. The hydroxyproline has a structure as shown in formula (I). The hydroxyproline and the derivative thereof provided by the present invention have good herbicidal activity. Upon verification, the hydroxyproline or the derivative thereof of the present invention can be independently applied to a field or compounded with other agents, so as to achieve a good weeding effect, and the herbicide application cost can be effectively reduced. Moreover, a broad spectrum of weed control is achieved, and a good control effect on most broadleaf weeds, gramineous weeds and cyperaceae weeds is achieved. Additionally, the hydroxyproline and the derivative are safe and harmless to the environment and human health, and a powerful guarantee is provided for ensuring the healthy growth of crops and reducing the planting cost.

Description

Application of hydroxyproline and its derivatives, biological herbicides, broad-spectrum herbicides, and weed control methods

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Chinese patent application 202311698802.X filed on December 11, 2023, the contents of which are incorporated herein by reference. Technical Field

[0003] The invention belongs to the technical field of weed control, and in particular relates to applications of hydroxyproline and its derivatives, biological herbicides, broad-spectrum herbicides, and weed control methods. Background Art

[0004] Weeds in farmland directly affect crop yield and indirectly impact crop quality. Herbicides effectively reduce weed damage and are currently the most cost-effective weed control method. However, the long-term and extensive use of a single herbicide accelerates the evolution of weed communities, leading to the growing problem of weed resistance. Furthermore, herbicide residues pose increasing risks to food safety and the ecological and environmental safety of farmland. The development of highly effective, low-toxic (or non-toxic), and environmentally friendly herbicides is urgently needed.

[0005] The active ingredients of organic herbicides mainly include amino acids, fatty acids, benzene, alcohols, organic amines and other substances.

[0006] Since 1996, amino acid herbicides have been ranked first among the 23 herbicide categories. The most widely used herbicide in this category is glyphosate, which consists of a glycine skeleton and a phosphate group. Although glyphosate is inexpensive and has excellent efficacy, its safety remains a concern. On the other hand, studies have found that herbicide compositions containing fatty acids can quickly decompose into relatively non-toxic residues after application, and their safety is relatively high. However, the recommended dosage of this type of herbicide is relatively high, usually requiring an application of more than 10,000 g / hectare. For example, a document (Qian Zhenguan, Shen Guohui, Li Tao, Chai Xiaoling, Wen Guangyue. Study on the herbicidal activity and application technology of the botanical herbicide nonanoic acid [J]. Journal of Shanghai Agriculture, 2010, 26(02): 1-4.) reports that a dosage of at least 11,000 g to 22,500 g / hectare is required to promote herbicidal activity, which poses an economic barrier to its promotion. Summary of the Invention

[0007] The purpose of the present invention is to overcome the shortcomings of the prior art, broaden the weed control spectrum and improve the weed control efficiency while taking into account safety, efficacy and economy.

[0008] In order to achieve the above-mentioned object of the invention, the first aspect of the present invention provides the use of hydroxyproline and its derivatives in weed control, wherein the hydroxyproline has a structure represented by formula (I), and the derivative is selected from at least one of an agrochemically acceptable salt, hydrate, solvate, or enantiomer or optically active form of hydroxyproline;

[0009] Wherein, in formula (I),

[0010] R1 is selected from H, -COOR 1 , fluorenylmethoxycarbonyl, glycyl; R 1 is selected from C 1-12 alkyl;

[0011] R2 is selected from -OR 21 、-NR 21 R 22 or -C(O)-NH2;

[0012] R 21 and R 22 Each independently selected from H, Na ion, ammonium ion, C unsubstituted or substituted by at least one group in combination A 1-12 Alkyl, unsubstituted or R 23 Substituted phenyl, C 3-8 Cycloalkyl, quinolinyl; or, R 21 and R 22 Together they form a 5-6 membered saturated or unsaturated ring; R 23 Selected from C 1-6 Alkyl, amino substituted phenyl;

[0013] The combination A contains phenyl, hydroxyl, -NH2 and -N(R 24 )(R 25 );R 24 and R 25 Each independently selected from C 1-6 alkyl;

[0014] R3 and R4 are each independently selected from H and hydroxyl, and R3 and R4 are not H at the same time.

[0015] A second aspect of the present invention provides a biological herbicide, the active ingredient of which is at least one of trans-4-hydroxy-L-proline, cis-4-hydroxy-L-proline, trans-3-hydroxy-L-proline, and cis-3-hydroxy-L-proline.

[0016] The active ingredient mentioned in the second aspect of the present invention includes at least one of trans-4-hydroxy-L-proline, cis-4-hydroxy-L-proline, trans-3-hydroxy-L-proline, and cis-3-hydroxy-L-proline derived from biological or artificial sources.

[0017] A third aspect of the present invention provides a broad-spectrum herbicide, wherein the active ingredients of the herbicide include a first component and a second component;

[0018] The first component is at least one of the hydroxyproline and its derivatives described in the first aspect;

[0019] The second component includes at least one of a 5-enolpyruvylshikimate-3-phosphate synthase inhibitor, an acetolactate synthase inhibitor, an acetyl-CoA carboxylase inhibitor, a p-hydroxyphenylpyruvate dioxygenase inhibitor, a protoporphyrinogen oxidase inhibitor, a photosystem II inhibitor, a phytoene desaturase inhibitor, a very long chain fatty acid inhibitor, a deoxy-D-fructose phosphate synthase inhibitor, a glutamine synthetase inhibitor, a cellulose synthase inhibitor, a pyruvate dehydrogenase inhibitor, a dihydropteroate DHP synthase inhibitor, a carotenoid synthesis inhibitor, a fat synthesis inhibitor, a synthetic hormone inhibitor, a cell division inhibitor, a microtubule inhibitor, and a photosystem I electron transfer inhibitor.

[0020] The fourth aspect of the present invention provides a method for controlling weeds in a field, comprising spraying at least one of the hydroxyproline and its derivatives described in the application described in the first aspect in the field, spraying the biological herbicide described in the second aspect in the field, and spraying the broad-spectrum herbicide described in the third aspect in the field.

[0021] The present invention provides hydroxyproline and its derivatives, in particular L-hydroxyproline and its derivatives for use in weed control. The hydroxyproline and its derivatives provided by the present invention contain at least one hydroxyl group on the pyrrolidine ring and have good weed control activity.

[0022] The present invention has been verified through practical examples, demonstrating that applying 2250-4500 g / hectare of L-hydroxyproline or its derivatives to fields can achieve excellent weed control. Furthermore, the herbicide provided by the present invention has a broad spectrum of weed control, effectively controlling most broadleaf weeds, grass weeds, and sedge weeds. Furthermore, since L-hydroxyproline is derived from organisms, using it alone or as a derivative based on it is safer for the environment and human health, providing a strong guarantee for the healthy growth of crops and reducing planting costs.

[0023] In a preferred embodiment of the present invention, hydroxyproline or a derivative thereof is used as the first component and mixed with the second component to obtain a broad-spectrum herbicide with a wider weed control spectrum, and has good control effects on most broad-leaved weeds, grass weeds, and sedge weeds. In particular, when the second component includes one or more of a 5-enolpyruvylshikimate-3-phosphate synthase inhibitor, an acetolactate synthase inhibitor, an acetyl-CoA carboxylase inhibitor, a p-hydroxyphenylpyruvate dioxygenase inhibitor, a protoporphyrinogen oxidase inhibitor, a photosystem II inhibitor, a phytoene desaturase inhibitor, a very long chain fatty acid inhibitor, a deoxy-D-fructose phosphate synthase inhibitor, a glutamine synthetase inhibitor, a cellulose synthase inhibitor, a pyruvate dehydrogenase inhibitor, a dihydropteroate DHP synthase inhibitor, a carotenoid synthesis inhibitor, a fat synthesis inhibitor, a synthetic hormone inhibitor, a cell division inhibitor, a microtubule inhibitor, and a photosystem I electron transfer inhibitor, the herbicide provided by the present invention has excellent weed control effects.

[0024] The hydroxyproline and its derivatives provided by the invention have good herbicidal activity.

[0025] Furthermore, it has been verified by the examples that, compared with the existing biological herbicides (such as nonanoic acid) that require the application of more than 11250 g / hectare, the hydroxyproline or its derivatives provided by the present invention can achieve a good weed control effect at a usage amount of 2250-4500 g / hectare. That is, compared with the existing biological herbicides, the hydroxyproline or its derivatives provided by the present invention, when used as herbicides, can significantly reduce the amount of its single application to the field (reduction of up to 60 wt%-80 wt%); in addition, the hydroxyproline or co-derivatives provided by the present invention can be applied in combination with a first component such as glyphosate. For example, when the hydroxyproline or its derivatives of the present invention are applied in combination with glyphosate, compared with the application of glyphosate alone (2250 g / hectare), the combined application of the present invention only requires the application of 112.5 g / hectare of glyphosate and 2250 g / hectare of the hydroxyproline or its derivatives provided by the present invention to achieve an effect comparable to or even better than the application of glyphosate alone. It is shown that the herbicide provided by the present invention has a beneficial effect on reducing environmental pollution and ecological damage caused by chemical substances, improving the quality and safety of agricultural products and people's health and safety, and promoting sustainable agricultural development.

[0026] In a particularly preferred embodiment, the first component and the second component of the broad-spectrum herbicide provided by the present invention are used in combination to produce a synergistic effect. The broad-spectrum herbicide provided by the present invention has a lower application cost and is conducive to promotion and application.

[0027] The present invention has been verified by the examples to achieve a good weed control effect by applying 2250-4500 g / hectare of hydroxyproline or its derivatives to the field, which can effectively reduce the cost of pesticide application. The invention also has a wide weed control spectrum, and has a good control effect on most broadleaf weeds, grass weeds, and sedge weeds. In addition, hydroxyproline and its derivatives are harmless to the environment and human health, providing a strong guarantee for ensuring the healthy growth of crops and reducing planting costs. DETAILED DESCRIPTION

[0028] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0029] Agrochemically acceptable salts of hydroxyproline include, but are not limited to, sodium salt, ammonium salt, hydrochloride, and the like.

[0030] Used alone or in compound words (e.g. "C 1-12 The term "alkyl" as used herein includes straight or branched chain alkyl groups, and non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl or different isomers. In particular, C 1-12 The alkyl group represents an alkyl group having a total number of carbon atoms of 1 to 12, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

[0031] “C 3-8 "Cycloalkyl" means a cycloalkyl group with a total of 3 to 8 carbon atoms, and the ring atoms are all C atoms, for example, it can be a cycloalkyl group with a total of 3, 4, 5, 6, 7, or 8 ring carbon atoms, and the "C 3～8 Any position on the cycloalkyl group is directly connected to the parent nucleus. For example, cyclopropyl, cyclobutyl, cyclopentyl, etc. 3～6"Cycloalkyl" and the like have similar definitions except for the total number of carbon atoms.

[0032] As mentioned above, the first aspect of the present invention provides the use of hydroxyproline and its derivatives in weed control, wherein the hydroxyproline has a structure represented by formula (I), and the derivative is selected from at least one of an agrochemically acceptable salt, hydrate, solvate, or enantiomer or optically active form of hydroxyproline;

[0033] Wherein, in formula (I),

[0034] R1 is selected from H, -COOR 1 , fluorenylmethoxycarbonyl, glycyl; R 1 is selected from C 1-12 alkyl;

[0035] R2 is selected from -OR 21 、-NR 21 R 22 or -C(O)-NH2;

[0036] R 21 and R 22 Each independently selected from H, Na ion, ammonium ion, C unsubstituted or substituted by at least one group in combination A 1-12 Alkyl, unsubstituted or R 23 Substituted phenyl, C 3-8 Cycloalkyl, quinolinyl; or, R 21 and R 22 Together they form a 5-6 membered saturated or unsaturated ring; R 23 Selected from C 1-6 Alkyl, amino substituted phenyl;

[0037] The combination A contains phenyl, hydroxyl, -NH2 and -N(R 24 )(R 25 );R 24 and R 25 Each independently selected from C 1-6 alkyl;

[0038] R3 and R4 are each independently selected from H and hydroxyl, and R3 and R4 are not H at the same time.

[0039] Preferably, in the application of the present invention, the hydroxyproline has a structure shown in formula (I-1):

[0040] The definitions of the substituents in formula (I-1) are the same as those of the substituents in the structure represented by formula (I) described above.

[0041] According to a preferred embodiment, in formula (I) and formula (I-1),

[0042] R1 is selected from H, -COOR 1 , fluorenylmethoxycarbonyl, glycyl; R 1 is selected from C 1-10 alkyl;

[0043] R2 is selected from -OR 21 、-NR 21 R 22 or -C(O)-NH2;

[0044] R 21 and R 22 Each independently selected from H, Na ion, ammonium ion, C unsubstituted or substituted by at least one group in combination A 1-10 Alkyl, unsubstituted or R 23 Substituted phenyl, C 4-6 Cycloalkyl, quinolinyl; or, R 21 and R 22 Together they form a 5-6 membered saturated or unsaturated ring; R 23 Selected from C 1-3 Alkyl, amino substituted phenyl;

[0045] The combination A contains phenyl, hydroxyl, -NH2 and -N(R 24 )(R 25 );R 24 and R 25 Each independently selected from C 1-6 alkyl;

[0046] R3 and R4 are each independently selected from H and hydroxyl, and R3 and R4 are not H at the same time.

[0047] According to another preferred embodiment, in formula (I) and formula (I-1),

[0048] R1 is H;

[0049] R2 is selected from -OR 21 、-NR 21 R 22 or -C(O)-NH2;

[0050] R 21 and R 22 Each independently selected from H, Na ion, ammonium ion, C 1-6 Alkyl, C substituted by at least one group in combination A 1-10Alkyl, unsubstituted or R 23 Substituted phenyl, C 5-6 Cycloalkyl, quinolinyl; or, R 21 and R 22 Cyclize together to form a pyridinyl group; R 23 Selected from C 1-3 Alkyl, amino substituted phenyl;

[0051] The combination A contains phenyl, hydroxyl, -NH2 and -N(R 24 )(R 25 );R 24 and R 25 Each independently selected from C 1-6 alkyl;

[0052] R3 and R4 are each independently selected from H and hydroxyl, and R3 and R4 are not H at the same time.

[0053] According to a particularly preferred embodiment, the hydroxyproline is L-hydroxyproline, and the structure of the L-hydroxyproline is shown in any one of Formula IA, Formula II-A and Formula III-A:

[0054] Among them, R1 is hydrogen, tert-butyloxycarbonyl, benzyloxycarbonyl or fluorenylmethyloxycarbonyl, glycyl; R2 is hydrogen, methyl hydrochloride, ethyl hydrochloride, sodium ion, ammonium ion or methyl carboxylate.

[0055] Particularly preferably, the structure of the L-hydroxyproline is as shown in Formula IA.

[0056] Preferably, the structure represented by formula (I) includes trans-4-hydroxy-L-proline (CAS No. 51-35-4), cis-4-hydroxy-L-proline (CAS No. 618-27-9), trans-3-hydroxy-L-proline (CAS No. 4298-08-2), cis-3-hydroxy-L-proline (CAS No. 4298-08-2), 3,4-dihydroxy-L-proline (CAS No. 259140-15-3, i.e., the structure represented by formula II-A; 23161-63-9, 95341-65-4 and 95341-64-3), trans-4-hydroxy -L-proline salt, cis-4-hydroxy-L-proline salt, trans-4-hydroxy-L-proline methyl ester hydrochloride (CAS No. 40216-83-9), 4R-4-hydroxy-L-proline hydrochloride (CAS No. 33996-30-4), BOC-L-hydroxyproline (CAS No. 13726-69-7), N-Cbz-L-hydroxyproline methyl ester (CAS No. 64187-48-0) or Fmoc-L-hydroxyproline (CAS No. 88050-17-3), L-glycyl-L-hydroxyproline (CAS No. 24587-32-4).

[0057] Preferably, the structure represented by formula (I-1) is trans-4-hydroxy-L-proline or cis-4-hydroxy-L-proline, wherein, in the structure represented by formula (I-1), R1 is hydrogen, R2 is hydrogen, R3 is OH, and R4 is H.

[0058] Preferably, the structure represented by formula (I-1) is a salt of trans-4-hydroxy-L-proline or a salt of cis-4-hydroxy-L-proline, wherein, in the structure represented by formula (I-1), R1 is hydrogen, R2 is a sodium ion or an ammonium ion, R3 is OH, and R4 is H.

[0059] Preferably, the structure represented by formula (I-1) is trans-4-hydroxy-L-proline methyl ester hydrochloride.

[0060] Preferably, the structure represented by formula (I-1) is 4R-4-hydroxy-L-proline hydrochloride.

[0061] Preferably, the structure represented by formula (I-1) is BOC-L-hydroxyproline, wherein, in the structure represented by formula (I-1), R1 is tert-butyloxycarbonyl, R2 is hydrogen, R3 is OH, and R4 is H.

[0062] Preferably, the structure represented by formula (I-1) is N-Cbz-L-hydroxyproline methyl ester.

[0063] Preferably, the structure represented by formula (I-1) is Fmoc-L-hydroxyproline, wherein, in the structure represented by formula (I-1), R1 is fluorenylmethyloxycarbonyl, R2 is hydrogen, R3 is OH, and R4 is H.

[0064] Preferably, the structure represented by formula (I-1) is L-glycyl-L-hydroxyproline, wherein, in the structure represented by formula (I-1), R1 is a glycyl group, R2 is hydrogen, R3 is OH, and R4 is H.

[0065] The inventors have found that the L-hydroxyproline and its derivatives described in the present invention have good herbicidal activity.

[0066] Preferably, the types of weeds include at least one of broadleaf weeds, grass weeds and sedge weeds.

[0067] Particularly preferably, the types of weeds include at least one of annual broadleaf weeds, annual grass weeds and annual sedge weeds.

[0068] Particularly preferably, in the present invention, the annual broadleaf weeds are preferably Juniperus tatarinowii and / or Alternanthera philoxeroides, the Poaceae weeds are preferably one or more of Echinochloa crus-galli, Digitaria sanguinalis and Leptochloa chinensis, and the Cyperus weeds are preferably Cyperus annuus.

[0069] The present invention does not particularly limit the specific method for preparing the structure represented by the aforementioned formula (I) and its derivatives, and the structure represented by the formula (I-1) and its derivatives. Those skilled in the art, on the premise of understanding the structure of the present invention, can combine the existing technology in the field of synthesis and the known technical means in the art to obtain a suitable preparation route to synthesize the structure represented by the aforementioned formula (I) and its derivatives, and the structure represented by the formula (I-1) and its derivatives. The present invention hereinafter exemplifies several specific preparation methods for the structure represented by the aforementioned formula (I) and its derivatives, and the structure represented by the formula (I-1) and its derivatives, which should not be understood by those skilled in the art as limiting the present invention.

[0070] As mentioned above, the second aspect of the present invention provides a broad-spectrum herbicide, the active ingredient of which includes a first component; the first component is at least one of the hydroxyproline and its derivatives described in the application described in the first aspect.

[0071] Preferably, the first component is L-hydroxyproline or a derivative thereof as described in the application described in the first aspect. Further preferably, the first component is at least one of trans-4-hydroxy-L-proline, cis-4-hydroxy-L-proline, trans-3-hydroxy-L-proline, cis-3-hydroxy-L-proline, (3r,4r)-(9ci)-3,4-dihydroxy-L-proline, ammonium salt or sodium salt of trans-4-hydroxy-L-proline, ammonium salt or sodium salt of cis-4-hydroxy-L-proline, ammonium salt or sodium salt of trans-3-hydroxy-L-proline, ammonium salt or sodium salt of trans-3-hydroxy-L-proline, trans-4-hydroxy-L-proline methyl ester hydrochloride, 4R-4-hydroxy-L-proline hydrochloride, BOC-L-hydroxyproline, N-Cbz-L-hydroxyproline methyl ester, Fmoc-L-hydroxyproline and L-glycyl-L-hydroxyproline.

[0072] Preferably, the active ingredient of the herbicide further comprises a second component; the second component comprises at least one of a 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitor, an acetolactate synthase (ALS) inhibitor, an acetyl-CoA carboxylase (ACCase) inhibitor, a p-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor, a protoporphyrinogen oxidase (PPO) inhibitor, a photosystem II (PSII) inhibitor, a phytoene desaturase (PDS) inhibitor, a very long chain fatty acid (VLCFA) inhibitor and a deoxy-D-fructose phosphate synthase (DOXP) inhibitor, a glutamine synthetase inhibitor, a cellulose synthase inhibitor, a pyruvate dehydrogenase (PDH) inhibitor, a dihydropteroate DHP synthase (DHPS) inhibitor, a carotenoid synthesis inhibitor, a fat synthesis inhibitor, a synthetic hormone inhibitor, a cell division inhibitor, a microtubule inhibitor, and a photosystem I electron transfer inhibitor. The inventors have discovered that the compounding of the first component and the second component of the present invention can produce a synergistic effect, thereby further reducing the application cost of the broad-spectrum herbicide and facilitating its promotion and application.

[0073] Preferably, the second component is selected from at least one of glyphosate, glufosinate, fluazifop-butyl, mesotrione, 2,4-D butyl, bispyribac-butyl, cyhalofop-butyl, penoxsulam, dichloroquinoline, bentazone, oxadiazol, quinclorac, quinoline, fluazifop-butyl, fluazifop-butyl, quinoxaline, nicosulfuron, atrazine, 2-Methyl-4-chloro sodium salt, cloflupyr, mesotrione, bispyribac-butyl, benzylsulfuron-methyl, cyclamates, oxadiazol-butyl, clodinafop-butyl, methyldisulfuron-methyl, fluazifop-butyl, bensulfuron-methyl, cyclamates, oxadiazol-butyl, clodinafop-butyl, methyldisulfuron-methyl, fluazifop-butyl, bensulfuron-methyl, bispyribac-butyl, pinoxafil, glufosinate, imamipyr, glufosinate ammonium salt, triazosulfuron, benzylpyrazone, cyclamates, and mesotrione.

[0074] According to a particularly preferred embodiment, in the present invention, the first component of the broad-spectrum herbicide is preferably trans-4-hydroxy-L-proline or cis-4-hydroxy-L-proline; and the second component is preferably one or more of glyphosate, glufosinate, fluazifop-butyl, mesotrione, and 2,4-D butyl ester. The mass ratio of the first component to the second component is 160:1 to 4:1.

[0075] According to a preferred embodiment, in the broad-spectrum herbicide, the first component is trans-4-hydroxy-L-proline, and the trans-4-hydroxy-L-proline is used in an amount of 150-300 g per mu. According to another preferred embodiment, in the broad-spectrum herbicide, the first component is cis-4-hydroxy-L-proline, and the cis-4-hydroxy-L-proline is used in an amount of 150-200 g per mu.

[0076] According to another preferred embodiment, the broad-spectrum herbicide contains a first component and a second component, the first component is trans-4-hydroxy-L-proline, and the mass ratio of the first component to the second component is 8:1 to 40:1.

[0077] According to another preferred embodiment, the broad-spectrum herbicide contains a first component and a second component, the first component is cis-4-hydroxy-L-proline, and the mass ratio of the first component to the second component is 2:1 to 160:1.

[0078] As mentioned above, the third aspect of the present invention provides a method for controlling weeds in a field, comprising spraying at least one of the hydroxyproline and its derivatives described in the application of the first aspect and / or spraying the broad-spectrum herbicide described in the second aspect in the field.

[0079] Preferably, the spraying rate of the broad-spectrum herbicide is 2250 to 4500 g / hectare, based on the mass of the first component in the broad-spectrum herbicide, and more preferably 4500 g / hectare.

[0080] To further illustrate the present invention, the application of hydroxyproline and its derivatives provided by the present invention in weed control is described in detail below with reference to examples, but these examples should not be construed as limiting the scope of protection of the present invention.

[0081] Example 1

[0082] (1) Using water or ethanol solvent, L-proline (CAS No. 147-85-3, purity ≥99.0%, produced by Guangdong Wenglong Chemical Reagent Co., Ltd.), trans-4-hydroxy-L-proline (CAS No. 51-35-4, purity ≥99.0%, produced by Guangdong Boxing Chemical Reagent Co., Ltd.), cis-4-hydroxy-L-proline (CAS No. 618-27-9, purity ≥98.0%, produced by Guangzhou Jinyuan Chemical Co., Ltd.), trans-3-hydroxy-L-proline (CAS No. 4298-08-2, purity ≥98.0%, produced by Shanghai Jizhi Biochemical Technology ... cis-4-hydroxy-L-proline (CAS No. 618-27-9, purity ≥98.0%, produced by Guangzhou Jinyuan Chemical Co., Ltd.), cis-4-hydroxy-L-proline (CAS No. 618-27-9, purity ≥98.0%, produced by Guangzhou Jinyuan Chemical Co., Ltd.), cis-4-hydroxy-L-proline (CAS No. 618-27-9, purity ≥98.0%, produced by Guangzhou Jinyuan Chemical Co., Ltd.), cis-4-hydroxy-L-proline (CAS No. 618-27-9, purity ≥98.0%, produced by Guangzhou Jinyuan Chemical Co., 3-Hydroxy-L-proline (CAS No. 4298-08-2, purity ≥95.0%, Shanghai Yuanye Biotechnology Co., Ltd.), trans-3,4-dihydroxy-L-proline (CAS No. 259140-15-3, purity ≥95.0%, Shanghai Yuanye Biotechnology Co., Ltd.), and cis-3,4-dihydroxy-L-proline (CAS No. 95341-65-4, purity ≥95.0%, Shanghai Yuanye Biotechnology Co., Ltd.) were diluted to concentrations of 0.50 g / 100 mL, 0.75 g / 100 mL, and 1.0 g / 100 mL, respectively. The herbicidal activity of L-proline and trans-4-hydroxy-L-proline was determined with reference to "NY / T 1155.4-2006 Guidelines for Indoor Bioassay Tests of Pesticides—Herbicides—Part 4: Activity Determination Test—Stem-Leaf Spray Method":

[0083] Evenly sow germinated barnyard grass seeds in 15cm-diameter plastic pots, 20 seeds per pot, and cover with 0.3-0.4cm of soil. Cultivate in an artificial climate chamber with 34°C light for 12 hours during the day and 28°C darkness for 12 hours at night, keeping the soil moist. Thin out seedlings when they reach the three-leaf stage, leaving 15 uniformly growing seedlings per pot.

[0084] Three-leaf barnyardgrass seedlings were subjected to a foliar spray test using the seven pesticides described above. Four treatment concentrations (0 g / 100 mL, 0.5 g / 100 mL, 0.75 g / 100 mL, and 1.0 g / 100 mL) were used for each pesticide, with five replicates per treatment. The spray volume was 50 mL (i.e., 10 ml / pot). An untreated control (0 g / 100 mL) was used in each treatment. The fresh weight of the aboveground portion of the weeds was weighed 14 days after application. The average of the five replicates was calculated, and the fresh weight efficacy was calculated using the following formula.

[0085] E(%)=(CT) / C×100;

[0086] Wherein: E (%) represents the fresh weight control effect; C represents the average fresh weight of the aboveground part of the weeds in the untreated group (g); T represents the average fresh weight of the aboveground part of the weeds 14 days after application (g); the results are shown in Table 1.

[0087] Table 1: Determination of herbicidal activity of hydroxy-L-proline

[0088] As shown in Table 1, none of the three concentrations of L-proline had any effect on barnyardgrass. However, when the concentration of the six different L-hydroxyproline structures reached or exceeded 0.5g / 100mL, they showed significant weed control. Furthermore, Table 1 also shows that the cis-form of hydroxy-L-proline exhibited stronger herbicidal activity than the trans-form.

[0089] (2) Trans-4-hydroxy-L-proline, sodium trans-4-hydroxy-L-proline (compound a), cis-4-hydroxy-L-proline, sodium cis-3-hydroxy-L-proline (compound b), trans-3-hydroxy-L-proline, trans-3-hydroxy-L-proline ammonium (compound c), cis-3-hydroxy-L-proline, cis-3-hydroxy-L-proline ammonium (compound d), 3,4-dihydroxy-L-proline, trans-4-hydroxy-L-proline methyl ester hydrochloride, 4R-4-hydroxy-L-proline hydrochloride, BOC-L-hydroxyproline, N-Cbz-L-hydroxyproline methyl ester, Fmoc-L-hydroxyproline, L-glycyl-L-hydroxyproline, compounds e to h, a total of 19 substances, were diluted to a concentration of 1.0 g / 100 mL. Echinochloa crusgalli seedlings were prepared as described in (1), sprayed with water and the pesticide, and the control efficacy of fresh weight of Echinochloa crusgalli was calculated.

[0090] The following are some examples of the preparation of several substances:

[0091] Compound a: 1 mol / L trans-4-hydroxy-L-proline and 1 mol / L sodium hydroxide were mixed at a molar ratio of 1:1.2, stirred on a magnetic stirrer at 25°C for 24 hours, and then vacuum dried to constant weight to obtain sodium trans-4-hydroxy-L-proline;

[0092] Compound b: 1 mol / L cis-4-hydroxy-L-proline and 1 mol / L sodium hydroxide were mixed at a molar ratio of 1:1.2, stirred on a magnetic stirrer at 25°C for 24 h, and then vacuum dried to constant weight to obtain sodium cis-4-hydroxy-L-proline;

[0093] Compound e: 1 mol / L cis-4-hydroxy-L-proline and 1 mol / L hexanol were mixed at a molar ratio of 1:1.2, and concentrated sulfuric acid was added as a catalyst. The mixture was refluxed for 8 hours. After completion of the reaction, the mixture was cooled to room temperature and subjected to post-treatment including neutralization, extraction, and drying to obtain cis-4-hydroxy-L-proline hexyl ester.

[0094] Compound f: 1 mol / L cis-4-hydroxy-L-proline and 1 mol / L phenol were mixed at a molar ratio of 1:1.2, and a small amount of concentrated sulfuric acid was added as a catalyst. The mixture was stirred at 80°C for 6 hours. After the reaction, the mixture was cooled, and the excess acid was neutralized with saturated sodium carbonate solution. The product was then extracted with ethyl acetate, washed, and dried to obtain cis-4-hydroxy-L-proline phenyl ester.

[0095] Compound g: 1 mol / L cis-4-hydroxy-L-proline and 1 mol / L urea were mixed at a molar ratio of 1:1, and 1.2 mol of a condensing agent, DCC, was added. After stirring at room temperature for 8 hours, the byproduct, dicyclohexylurea (DCU), was removed by filtration. The filtrate was then concentrated and purified to obtain cis-4-hydroxy-L-proline uramide.

[0096] Compound h: 1 mol / L cis-4-hydroxy-L-proline and 1 mol butylamine were mixed at a 1:1 molar ratio, and 1.2 mol / L EDCI (dichloromethane was used as the reaction solvent) was added. The mixture was stirred at room temperature for 8 hours. After completion of the reaction, the byproducts were removed by filtration. The solvent was then removed by vacuum distillation, and the product was purified by column chromatography or other methods to obtain cis-4-hydroxy-L-proline butyramide.

[0097] Table 2: Analysis of herbicidal activity of L-hydroxyproline and its derivatives

[0098] As can be seen from Table 2, the L-hydroxyproline derivatives all have high herbicidal activity at 1 g / 100 mL.

[0099] Example 2

[0100] The herbicide was prepared with a trans-4-hydroxy-L-proline concentration of 1.0 g / 100 mL and an adjuvant concentration of 0.05% by volume. The adjuvant was the agricultural silicone surfactant IOTA 2000 (produced by Anhui Aiyota Silicone Oil Co., Ltd., containing polyether-modified heptamethyltrisiloxane);

[0101] Conduct the test with reference to the methods and basic requirements for field efficacy plot tests in GB / T 17980.42-2000 Guidelines for Field Efficacy Tests of Pesticides (I) Herbicides for Control of Weeds in Corn Fields:

[0102] In dry land with uniform soil fertility, ridges were made and corn was planted with a row spacing of 30 cm × 60 cm. Three rectangular plots were randomly set up, each with an area of ​​20 m 2When the corn reached the three-leaf and five-leaf stages, weeds in the plots were sprayed with 2250 g / ha and 4500 g / ha of trans-4-hydroxy-L-proline, respectively. The weed control efficacy was investigated 20 days after the application, and the results are shown in Table 3.

[0103] Plant protection effect = number of lethal plants / total number of plants × 100%.

[0104] Table 3: Weed control effect of different dosages of trans-4-hydroxy-L-proline (%)

[0105] As shown in Table 3, when the dosage of trans-4-hydroxy-L-proline is 2250 g / hectare, it has a good control effect on weeds. When the dosage is increased to 4500 g / hectare, it has excellent control effects on different types of weeds.

[0106] Example 3

[0107] The test was conducted to investigate the control effect of hydroxy-L-proline in combination with other chemical herbicides on outdoor barnyard grass, crabgrass, foxtail grass, cyperus rotundus, oxalis, broadleaf floribunda, purslane, duckweed, Amaranthus retroflexus, cleaver, chinensis, rainweed, goosegrass, wild arrowhead, alopecuroides, wild oats, sophisticate, shepherd's purse, field bindweed, speedwell, fleabane, multiflora ryegrass, water hyacinth, and Spartina alterniflora.

[0108] 1. Application Scenarios. The experiments were conducted in corn fields (plant spacing 30 cm × 60 cm), four-year-old tea gardens (plant spacing 0.8 m × 1.8 m), cotton fields (plant spacing 120 cm × 40 cm), spring wheat fields (seeding rate 25 kg / mu), direct-seeded rice fields (seeding rate 6 kg / mu), transplanted rice fields (plant spacing 25 cm × 14 cm), lily fields (plant spacing 40 cm × 30 cm), Polygonatum fields (40 cm × 15 cm), free-range ponds, and coastal mudflats.

[0109] 2. Plot setting and compound treatment. Set up plots in the relatively concentrated areas of target weeds in the above scenario to test the effect of stem and leaf spray treatment with compound pesticides. Each plot is 20m 2 , 25m per plot for direct-seeding rice fields and transplanted rice fields 2 , four-year-old tea garden, lily field, and Polygonatum field, each plot is 9m 2 , 5m for each pond 2 The treatment groups included a combination group, control group 1, and control group 2, each containing three plots. Control group 1 received either trans-4-hydroxy-L-proline or cis-4-hydroxy-L-proline alone, while control group 2 received a single chemical herbicide. Applications were made at the weed seedling stage, and the control efficacy of the combination and control groups was compared.

[0110] The chemical herbicide formulations used and their manufacturers are: 41wt% glyphosate isopropylamine salt solution, Monsanto Company; 10wt% cyhalofop-butyl emulsifiable concentrate, Jiangsu Huifeng Bio-Agriculture Co., Ltd.; 15wt% mesotrione suspension concentrate, Shandong Binnong Technology Co., Ltd.; 200g / L glufosinate aqueous solution, Yongnong Bioscience Co., Ltd.; 72wt% 2,4-D butyl ester emulsifiable concentrate, Shandong Qiaochang Modern Agriculture Co., Ltd.; 100g / L bispyribac-sodium suspension concentrate, Jiangsu Futian Agrochemical Co., Ltd.; 25g / L penoxsulam dispersible oil suspension concentrate, Anhui Jiuyi Agriculture Co., Ltd.; 50wt% quinclorac wettable powder, Zhejiang Zhongshan Chemical Group Co., Ltd.; 480g / L methotrexate aqueous solution, Jiangsu Zhongqi Technology Co., Ltd. Co., Ltd.; 10wt% oxadiazine emulsifiable concentrate, Jiangsu Ruibang Agrochemical Co., Ltd.; 6wt% triazosulfuron dispersible oil suspension, Jiangsu Agricultural Production Materials Group Agrochemical Co., Ltd.; 250g / L fomesafen aqueous solution, Jinan Tianbang Chemical Co., Ltd.; 10wt% quizalofop-p-ethyl emulsifiable concentrate, Hebei Rongwei Biopharmaceutical Co., Ltd.; 10wt% fluazifop-butyl emulsifiable concentrate, Shandong Xianda Agrochemical Co., Ltd.; 40g / L nicosulfuron dispersible oil suspension, Qingdao Qingyuan Agro-Crown Resistant Weed Control Co., Ltd.; 38wt% atrazine suspension, Shandong Luba Chemical Co., Ltd.; 30wt% benzylpyrazone suspension, BASF SE; 56wt% 2-Methyl-4-chloro-1-sodium salt soluble powder, Jiangsu Hormone Research Institute Institute Co., Ltd.; 200 g / L clofopyralid emulsifiable concentrate, Sichuan Lier Crop Science Co., Ltd.; 5wt% bifenazolin suspension concentrate, Qingdao Qingyuan Agro-Crown Resistant Weed Control Co., Ltd.; 10wt% bensulfuron-methyl wettable powder, Zhejiang Tianfeng Bioscience Co., Ltd.; 75 g / L tembotrione suspension concentrate, Bayer CropScience; 69 g / L fenoxaprop-ethyl emulsifiable concentrate in water, Bayer CropScience (China) Co., Ltd.; 15wt% clodinafop-butyl wettable powder, Syngenta Crop Protection Co., Ltd., Switzerland; 30 g / L mesosulfuron-methyl dispersible oil suspension concentrate, Bayer CropScience (China) Co., Ltd.; 70% fluazifop-methyl water dispersible granules, Jiangsu Kesheng Group Co., Ltd.; 75wt% bensulfuron-methyl water dispersible granules, Shandong Luba Chemical Co., Ltd.; 50g / L florasulam suspension concentrate, Dow AgroSciences (China) Co., Ltd.; 5wt% pinoxasulfobutyl emulsifiable concentrate, Syngenta Crop Protection GmbH, Switzerland; 10wt% quinclorac suspension concentrate, produced by Shandong Xinda Agrochemical Co., Ltd.; 6wt% pyraclostrobin dispersible oil suspension concentrate, Jiangsu Qingyuan Agroguan Weed Control Co., Ltd.; 6wt% cypermethrin dispersible oil suspension concentrate, Jiangsu Qingyuan Agroguan Weed Control Co., Ltd.; 10wt% bispyribac dispersible oil suspension concentrate, Qingdao Qingyuan Crop Science Co., Ltd.; 20wt% glufosinate ammonium soluble concentrate, Yongnong Bioscience Co., Ltd.; 240g / L imidacloprid aqueous solution, Zhejiang Xin'an Chemical Group Co., Ltd.

[0111] 3. Control efficacy of compound treatments. The herbicide application rates and weed control efficacy for each group of experiments are shown in Table 4, where the control efficacy per plant is expressed as: control efficacy (%) = number of lethal plants / total number of plants × 100%. The compound ratios in Table 4 represent the compound mass ratios.

[0112] Table 4: Weed control effect of the first component combined with the second component

[0113] It can be seen from the above examples that the hydroxyproline and its derivatives provided by the present invention have a broad weed control spectrum and have good control effects on most broadleaf weeds, grass weeds and sedge weeds.

[0114] The first component and the second component of the broad-spectrum herbicide provided by the present invention are compounded to produce a synergistic effect, further reduce the application cost, and facilitate promotion and application.

[0115] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. Application of hydroxyproline and its derivatives in weed control, characterized in that: The hydroxyproline has a structure represented by formula (I), and the derivative is selected from at least one of an agrochemically acceptable salt, hydrate, solvate, or enantiomer or optically active derivative of hydroxyproline; Wherein, in formula (I), R1 is selected from H, -COOR 1 , fluorenylmethoxycarbonyl, glycyl; R 1 is selected from C 1-12 alkyl; R2 is selected from -OR 21 、-NR 21 R 22 or -C(O)-NH2; R 21 and R 22 Each independently selected from H, Na ion, ammonium ion, unsubstituted or substituted by at least one group in combination A C 1-12 Alkyl, unsubstituted or R 23 Substituted phenyl, C 3-8 Cycloalkyl, quinolyl; or, R 21 and R 22 Together they form a 5-6 membered saturated or unsaturated ring; R 23 Selected from C 1-6 Alkyl, amino substituted phenyl; The combination A contains phenyl, hydroxyl, -NH2 and -N(R 24 )(R 25 );R 24 and R 25 Each independently selected from C 1-6 alkyl; R3 and R4 are each independently selected from H and hydroxyl, and R3 and R4 are not H at the same time.

2. The use according to claim 1, characterized in that: The hydroxyproline has a structure shown in formula (I-1): The definitions of the substituents in formula (I-1) are the same as those in claim 1.

3. The use according to claim 1 or 2, characterized in that: In formula (I) and formula (I-1), R1 is selected from H, -COOR 1 , fluorenylmethoxycarbonyl, glycyl; R 1 is selected from C 1-10 alkyl; R2 is selected from -OR 21 、-NR 21 R 22 or -C(O)-NH2; R 21 and R 22 Each independently selected from H, Na ion, ammonium ion, unsubstituted or substituted by at least one group in combination A C 1-10 Alkyl, unsubstituted or R 23 Substituted phenyl, C 4-6 Cycloalkyl, quinolyl; or, R 21 and R 22 Together they form a 5-6 membered saturated or unsaturated ring; R 23 Selected from C 1-3 Alkyl, amino substituted phenyl; The combination A contains phenyl, hydroxyl, -NH2 and -N(R 24 )(R 25 );R 24 and R 25 Each independently selected from C 1-6 alkyl; R3 and R4 are each independently selected from H and hydroxyl, and R3 and R4 are not H at the same time; Preferably, in formula (I) and formula (I-1), R1 is H; R2 is selected from -OR 21 、-NR 21 R 22 or -C(O)-NH2; R 21 and R 22 Each independently selected from H, Na ion, ammonium ion, C 1-6 Alkyl, C substituted by at least one group in combination A 1-10 Alkyl, unsubstituted or R 23 Substituted phenyl, C 5-6 Cycloalkyl, quinolyl; or, R 21 and R 22 Cycling together to form a pyridinyl group; R 23 Selected from C 1-3 Alkyl, amino substituted phenyl; The combination A contains phenyl, hydroxyl, -NH2 and -N(R 24 )(R 25 );R 24 and R 25 Each independently selected from C 1-6 alkyl; R3 and R4 are each independently selected from H and hydroxyl, and R3 and R4 are not H at the same time.

4. The use according to claim 1, characterized in that: The hydroxyproline is L-hydroxyproline, and the structure of the L-hydroxyproline is shown in any one of Formula IA, Formula II-A and Formula III-A: Wherein, R1 is hydrogen, tert-butyloxycarbonyl, benzyloxycarbonyl or methyloxycarbonyl, glycyl; R2 is hydrogen, methyl hydrochloride, ethyl hydrochloride, sodium ion, ammonium ion or methyl carboxylate; Preferably, the structure of the L-hydroxyproline is as shown in Formula IA.

5. The use according to claim 4, characterized in that: The structure shown in formula (I) includes at least one of trans-4-hydroxy-L-proline, cis-4-hydroxy-L-proline, trans-3-hydroxy-L-proline, cis-3-hydroxy-L-proline, dihydroxy-L-proline, a salt of trans-4-hydroxy-L-proline, a salt of cis-4-hydroxy-L-proline, trans-4-hydroxy-L-proline methyl ester hydrochloride, 4R-4-hydroxy-L-proline hydrochloride, BOC-L-hydroxyproline, N-Cbz-L-hydroxyproline methyl ester or Fmoc-L-hydroxyproline, and L-glycyl-L-hydroxyproline.

6. The use according to any one of claims 1 to 5, characterized in that: The weed type includes at least one of broadleaf weeds, grass weeds and sedge weeds; Preferably, the weed types include at least one of annual broadleaf weeds, annual grass weeds and annual sedge weeds.

7. A biological herbicide, characterized in that: The active ingredient of the herbicide is at least one of trans-4-hydroxy-L-proline, cis-4-hydroxy-L-proline, trans-3-hydroxy-L-proline, and cis-3-hydroxy-L-proline; Preferably, the active ingredient of the herbicide is trans-4-hydroxy-L-proline or cis-4-hydroxy-L-proline.

8. A broad-spectrum herbicide, characterized in that: The active ingredient of the herbicide includes a first component; the first component is at least one of hydroxyproline and its derivatives described in the application according to any one of claims 1 to 5; Preferably, the active ingredient of the herbicide further comprises a second component; the second component comprises at least one of a 5-enolpyruvylshikimate-3-phosphate synthase inhibitor, an acetolactate synthase inhibitor, an acetyl-CoA carboxylase inhibitor, a p-hydroxyphenylpyruvate dioxygenase inhibitor, a protoporphyrinogen oxidase inhibitor, a photosystem II inhibitor, a phytoene desaturase inhibitor, a very long chain fatty acid inhibitor, a deoxy-D-fructose phosphate synthase inhibitor, a glutamine synthetase inhibitor, a cellulose synthase inhibitor, a pyruvate dehydrogenase inhibitor, a dihydropteroate DHP synthase inhibitor, a carotenoid synthesis inhibitor, a fat synthesis inhibitor, a synthetic hormone inhibitor, a cell division inhibitor, a microtubule protein inhibitor, and a photosystem I electron transfer inhibitor; Preferably, the first component is selected from at least one of trans-4-hydroxy-L-proline, cis-4-hydroxy-L-proline, trans-3-hydroxy-L-proline, cis-3-hydroxy-L-proline, (3r,4r)-(9ci)-3,4-dihydroxy-L-proline, ammonium salt or sodium salt of trans-4-hydroxy-L-proline, ammonium salt or sodium salt of cis-4-hydroxy-L-proline, ammonium salt or sodium salt of trans-3-hydroxy-L-proline, ammonium salt or sodium salt of trans-3-hydroxy-L-proline, trans-4-hydroxy-L-proline methyl ester hydrochloride, 4R-4-hydroxy-L-proline hydrochloride, BOC-L-hydroxyproline, N-Cbz-L-hydroxyproline methyl ester, Fmoc-L-hydroxyproline and L-glycyl-L-hydroxyproline; Preferably, the second component is selected from at least one of glyphosate, glufosinate, fluazifop-butyl, mesotrione, 2,4-D butyl, bispyribac-butyl, cyhalofop-butyl, penoxsulam, dichloroquinoline, bentazone, oxadiazine, quinoline, quinclorac, fluazifop-butyl, fomesulfuron, quizalofop-ethyl, fluazifop-butyl, nicosulfuron, atrazine, 2-Methyl-4-chloro-sodium salt, clofopyralid, mesotrione, bispyribac-butyl, benzylsulfuron-methyl, cyclamoxadone, oxadiazine, clofosinate-butyl, 2,4-D butyl, bispyribac-butyl, cyhalofop-butyl, benzylsulfuron-methyl, cyclamoxadone, cyhalofop-butyl, cyhalofop-butyl, methyldisulfuron, fluazifop-butyl, bensulfuron-methyl, bispyribac-butyl, pinoxafil, glufosinate, imamipyr, glufosinate ammonium salt, triazosulfuron, benzylpyrazone, cyproconazole, and bispyribac.

9. The broad-spectrum herbicide according to claim 8, characterized in that: In the broad-spectrum herbicide, the content of the first component is less than 5000 g / hectare; preferably 2250-4500 g / hectare; Preferably, the mass ratio of the first component to the second component is 5:1 to 160:

1.

10. A method for controlling weeds in a field, characterized in that: Spraying at least one of the hydroxyproline and its derivatives described in any one of claims 1 to 5 in the field, spraying the biological herbicide described in claim 7 in the field, spraying the broad-spectrum herbicide described in any one of claims 8 to 9 in the field; Preferably, based on the mass of the first component in the broad-spectrum herbicide, the spraying amount of the broad-spectrum herbicide is 2250-4500 g / hectare.

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