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

Abstract

The invention relates to the technical field of weeding, in particular to application of hydroxyproline and derivatives thereof, a biological herbicide, a broad-spectrum herbicide and a weed control method, and hydroxyproline has a structure as shown in a formula (I). The hydroxyproline and the derivative thereof provided by the invention have good herbicidal activity. Through verification, the hydroxyproline or the derivative thereof disclosed by the invention can be independently applied to a field or compounded with other medicaments to achieve a good weeding effect, and the application cost can be effectively reduced; the weeding spectrum is wide, and the weeding composition has a good control effect on most of broadleaf weeds, grassy weeds and cyperaceae weeds; in addition, hydroxyproline and derivatives are safe and harmless to the environment and human health, and powerful guarantee is provided for guaranteeing healthy growth of crops and reducing planting cost. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of weed control, and specifically relates to the applications of hydroxyproline and its derivatives, biological herbicides, broad-spectrum herbicides, and methods for controlling weeds. Background Art

[0002] Farmland weeds directly affect crop yields and also have an indirect impact on the quality of crops. Herbicides can effectively reduce weed damage and are currently the most economical and effective weed control means. However, the long-term and large-scale use of single herbicides has accelerated the evolution of weed communities, resulting in an increasingly serious problem of weed resistance; at the same time, the problems of food safety and farmland ecological environment safety caused by herbicide residues have also become increasingly severe. It has become particularly urgent to develop highly efficient, low-toxic (or non-toxic), and environmentally friendly herbicides.

[0003] The active ingredients of organic herbicides mainly include substances such as amino acids, fatty acids, benzene, alcohols, and organic amines. Since 1996, amino acid herbicides have always ranked first among 23 types of herbicides; the most widely promoted variety of this type of herbicide is glyphosate, which is composed of a glycine backbone and a phosphate group; although glyphosate has low cost and excellent efficacy, its safety still has concerns. On the other hand, some studies have found that the herbicide compositions containing fatty acids can be quickly decomposed into relatively non-toxic residues after application, and their safety is relatively high; however, the recommended application doses of these herbicides are relatively high, usually requiring an application amount of more than 10000 g / ha. For example, a literature (Qian Zhenguan, Shen Guohui, Li Tao, Chai Xiaoling, Wen Guangyue. Research on the herbicidal activity and application technology of plant-derived herbicide nonanoic acid [J]. Acta Agriculturae Shanghai, 2010, 26(02): 1-4.) reported that at least 11000 g - 22500 g / ha of application amount is required to promote herbicidal activity, which poses an economic obstacle to its popularization. Summary of the Invention

[0004] The purpose of the present invention is to overcome the deficiencies of the prior art, and while taking into account safety, efficacy, and economy, broaden the weed control spectrum and improve the control efficiency of weeds.

[0005] To achieve the above-mentioned invention purpose, in the first aspect of the present invention, there is provided the application of hydroxyproline and its derivatives in controlling weeds. The hydroxyproline has the structure shown in formula (I), and the derivatives are selected from at least one of agriculturally chemically acceptable salts, hydrates, solvates of hydroxyproline, or derivatives of its enantiomers and optically active forms;

[0006]

[0007] Among them, in formula (I),

[0008] R1 is selected from H, -COOR 1, Fmoc, Gly; R 1 selected from unsubstituted or C substituted by at least one phenyl 1-12 alkyl;

[0009] R2 is selected from -OR 21 , -NR 21 R 22 or -C(O)-NH 2 ;

[0010] R 21 and R 22 are each independently selected from H, Na ion, ammonium ion, unsubstituted or C substituted by at least one group in combination A 1-12 alkyl, unsubstituted or phenyl substituted by R 23 , C 3-8 cycloalkyl, quinolinyl; or, R 21 and R 22 together cyclize to form a 5-6 membered saturated or unsaturated ring; R 23 is selected from C 1-6 alkyl, amino-substituted phenyl;

[0011] The combination A contains phenyl, hydroxyl, -NH 2 and -N(R 24 )(R 25 ); R 24 and R 25 are each independently selected from unsubstituted or C substituted by at least one hydroxyl 1-6 alkyl;

[0012] R3 and R4 are each independently selected from H and hydroxyl, and R3 and R4 are not both H.

[0013] The second aspect of the present invention provides a biological herbicide, and 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.

[0014] The active ingredients mentioned in the second aspect of the present invention include 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 biology or artificially synthesized.

[0015] The third aspect of the present invention provides a broad-spectrum herbicide, and the active ingredient of the herbicide includes a first component and a second component;

[0016] The first component is at least one of the hydroxyproline and its derivatives described in the first aspect;

[0017] The second component includes at least one of 5-enolpyruvylshikimate-3-phosphate synthase inhibitor, acetolactate synthase inhibitor, acetyl-CoA carboxylase inhibitor, p-hydroxyphenylpyruvate dioxygenase inhibitor, protoporphyrinogen oxidase inhibitor, photosystem II inhibitor, phytoene desaturase inhibitor, very long chain fatty acid inhibitor, deoxy-D-fructose phosphate synthase inhibitor, glutamine synthetase inhibitor, cellulose synthase inhibitor, pyruvate dehydrogenase inhibitor, dihydropteroate DHP synthase inhibitor, carotenoid synthesis inhibitor, fat synthesis inhibitor, synthetic hormone inhibitor, cell division inhibitor, tubulin inhibitor, and photosystem I electron transfer inhibitor.

[0018] The fourth aspect of the present invention provides a method for controlling field weeds, spraying at least one of the hydroxyproline and its derivatives described in the application of 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.

[0019] The present invention provides the application of hydroxyproline and its derivatives, especially L-hydroxyproline and its derivatives, in weeding. The pyrrolidine ring of the hydroxyproline and its derivatives provided by the present invention contains at least one hydroxyl group and has good herbicidal activity.

[0020] Verified by examples of the present invention, applying 2250 - 4500 g / ha of L-hydroxyproline or its derivatives to the field can achieve good weeding effects. Moreover, the herbicide provided by the present invention has a broad herbicidal spectrum and has good control effects on most broadleaf weeds, gramineous weeds, and cyperaceae weeds. In addition, L-hydroxyproline is derived from organisms, and using L-hydroxyproline alone or derivatives created with it as the backbone is safer for the environment and human health, providing a strong guarantee for the healthy growth of crops and reducing planting costs.

[0021] In a preferred embodiment of the present invention, using hydroxyproline or its derivative as the first component and mixing it with the second component results in a herbicide with a broader herbicidal spectrum, which has good control effects on most broadleaf weeds, gramineous weeds, and cyperaceae weeds. In particular, when the second component includes one or more of 5-enolpyruvylshikimate-3-phosphate synthase inhibitors, acetolactate synthase inhibitors, acetyl-CoA carboxylase inhibitors, 4-hydroxyphenylpyruvate dioxygenase inhibitors, protoporphyrinogen oxidase inhibitors, photosystem II inhibitors, phytoene desaturase inhibitors, very-long-chain fatty acid inhibitors, deoxy-D-fructose phosphate synthase inhibitors, glutamine synthetase inhibitors, cellulose synthase inhibitors, pyruvate dehydrogenase inhibitors, dihydropteroate synthase inhibitors, carotenoid synthesis inhibitors, lipid synthesis inhibitors, synthetic hormone inhibitors, cell division inhibitors, tubulin inhibitors, and photosystem I electron transfer inhibitors, the herbicide provided by the present invention has excellent herbicidal effects.

[0022] The hydroxyproline and its derivatives provided by the present invention have good herbicidal activity.

[0023] Furthermore, verified by examples, compared with the existing biological herbicides (such as nonanoic acid) that require an application amount of more than 11,250 g / ha, the hydroxyproline or its derivative provided by the present invention can achieve good herbicidal effects at an application amount of 2,250 - 4,500 g / ha. That is, compared with the existing biological herbicides, when the hydroxyproline or its derivative provided by the present invention is used as a herbicide, the application amount for single application in the field can be significantly reduced (the reduction rate is as high as 60wt% - 80%); in addition, the hydroxyproline or its derivative provided by the present invention can be compounded with the first component such as glyphosate. Exemplarily, when the hydroxyproline or its derivative of the present invention is compounded with glyphosate, compared with the single application of glyphosate (2,250 g / ha), in the compound application of the present invention, only 112.5 g / ha of glyphosate and 2,250 g / ha of the hydroxyproline or its derivative provided by the present invention need to be compounded to achieve an effect equivalent to or even better than the single application of glyphosate. This shows 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 the sustainable development of agriculture.

[0024] In a particularly preferred case, when the first component and the second component in the broad-spectrum herbicide provided by the present invention are compounded and used, a synergistic effect can be produced, and the application cost of the broad-spectrum herbicide provided by the present invention is lower, which is conducive to popularization and application.

[0025] Verified by examples, applying 2250 - 4500 g / ha of hydroxyproline or its derivatives of the present invention to the field can achieve good herbicidal effects, effectively reducing the cost of applying pesticides; and it has a broad herbicidal spectrum and has good control effects on most broad-leaved weeds, gramineous weeds and cyperaceae 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 the planting cost. Detailed Description of the Invention

[0026] The endpoints and any values disclosed in this text for a range are not limited to the exact range or value. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this text.

[0027] The agriculturally acceptable salts of hydroxyproline include but are not limited to sodium salts, ammonium salts, hydrochloride salts, etc.

[0028] The term "alkyl" used alone or in a compound word (such as "C 1-12 alkyl") includes straight-chain or branched-chain alkyls. Non-limiting examples of alkyls 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 alkyl represents an alkyl with a total of 1 - 12 carbon atoms, and the total number of carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12.

[0029] "C 3-8 cycloalkyl" represents a cycloalkyl with a total of 3 - 8 carbon atoms, and all ring-forming atoms are C atoms. For example, it can be a cycloalkyl with a total of 3, 4, 5, 6, 7, 8 ring-forming carbon atoms, and any position on the "C 3～8 cycloalkyl" is directly connected to the parent nucleus. For example, cyclopropyl, cyclobutyl, cyclopentyl, etc. "C 3～6"Naphthenyl" and the like have similar definitions, differing only in the total number of carbon atoms.

[0030] As described above, the first aspect of the present invention provides the use of hydroxyproline and its derivatives in weed control. The hydroxyproline has the structure shown in formula (I), and the derivatives are selected from at least one of agriculturally chemically acceptable salts, hydrates, solvates of hydroxyproline, or their enantiomers and derivatives of optically active forms;

[0031]

[0032] Wherein, in formula (I),

[0033] R1 is selected from H, -COOR 1 , fluorenylmethoxycarbonyl, glycyl; R 1 is selected from C 1-12 alkyl which is unsubstituted or substituted by at least one phenyl;

[0034] R2 is selected from -OR 21 , -NR 21 R 22 or -C(O)-NH 2 ;

[0035] R 21 and R 22 are each independently selected from H, Na ion, ammonium ion, C 1-12 alkyl which is unsubstituted or substituted by at least one group in combination A, phenyl which is unsubstituted or substituted by R 23 , C 3-8 naphthenyl, quinolinyl; or, R 21 and R 22 together cyclize to form a 5-6 membered saturated or unsaturated ring; R 23 is selected from C 1-6 alkyl, phenyl substituted by amino;

[0036] The combination A contains phenyl, hydroxyl, -NH 2 and -N(R 24 )(R 25 ); R 24 and R 25 are each independently selected from C 1-6 alkyl which is unsubstituted or substituted by at least one hydroxyl;

[0037] R3 and R4 are each independently selected from H and hydroxyl, and R3 and R4 are not both H at the same time.

[0038] Preferably, in the application of the present invention, the hydroxyproline has the structure shown in formula (I-1):

[0039]

[0040] The definitions of the substituents in formula (I-1) are correspondingly the same as those of the substituents in the structure shown in 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 which is unsubstituted or substituted by at least one phenyl group;

[0043] R2 is selected from -OR 21 , -NR 21 R 22 or -C(O)-NH 2 ;

[0044] R 21 and R 22 are each independently selected from H, Na ion, ammonium ion, C 1-10 alkyl which is unsubstituted or substituted by at least one group in combination A, phenyl which is unsubstituted or substituted by R 23 , C 4-6 cycloalkyl, quinolinyl; or, R 21 and R 22 together cyclize to form a 5- to 6-membered saturated or unsaturated ring; R 23 is selected from C 1-3 alkyl, phenyl substituted by amino group;

[0045] The combination A contains phenyl, hydroxyl, -NH 2 and -N(R 24 )(R 25 ); R 24 and R 25 are each independently selected from C 1-6 alkyl which is unsubstituted or substituted by at least one hydroxyl group;

[0046] R3 and R4 are each independently selected from H and hydroxyl, and R3 and R4 are not both 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)-NH 2 ;

[0050] R 21 and R 22 are each independently selected from H, Na ion, ammonium ion, C 1-6 alkyl, C 1-10 alkyl substituted by at least one group in combination A, phenyl unsubstituted or substituted by R 23 , C 5-6 cycloalkyl, quinolinyl; or, R 21 and R 22 together cyclize to form pyridyl; R 23 is selected from C 1-3 alkyl, phenyl substituted by amino;

[0051] Combination A contains phenyl, hydroxyl, -NH 2 and -N(R 24 )(R 25 ); R 24 and R 25 are each independently selected from C 1-6 alkyl unsubstituted or substituted by at least one hydroxyl;

[0052] R3 and R4 are each independently selected from H and hydroxyl, and R3 and R4 are not both 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 as any one of Formula I-A, Formula II-A and Formula III-A:

[0054]

[0055] Wherein, R1 is hydrogen, tert-butoxycarbonyl, benzyloxycarbonyl or fluorenylmethoxycarbonyl, glycyl; R2 is hydrogen group, methyl ester hydrochloride, ethyl ester hydrochloride, sodium ion, ammonium ion or methyl carboxylate.

[0056] Particularly preferably, the structure of the L-hydroxyproline is shown as Formula I-A.

[0057] 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, which is the structure represented by formula II-A; 23161-63-9, 95341-65-4 and 95341-64-3), salts of trans-4-hydroxy-L-proline, salts of cis-4-hydroxy-L-proline, 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), or at least one of them.

[0058] 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.

[0059] 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.

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

[0061] Preferably, the structure represented by formula (I-1) is 4R-4-hydroxy-L-proline hydrochloride.

[0062] Preferably, the structure represented by formula (I-1) is BOC-L-hydroxyproline, wherein, in the structure represented by formula (I-1), R1 is tert-butoxycarbonyl, R2 is hydrogen, R3 is OH, and R4 is H.

[0063] Preferably, the structure represented by formula (I-1) is N-Cbz-L-hydroxyproline methyl ester.

[0064] Preferably, the structure represented by formula (I-1) is Fmoc-L-hydroxyproline. In the structure represented by formula (I-1), R1 is fluorenylmethyloxycarbonyl, R2 is hydrogen, R3 is OH, and R4 is H.

[0065] Preferably, the structure represented by formula (I-1) is L-glycyl-L-hydroxyproline. In the structure represented by formula (I-1), R1 is glycyl, R2 is hydrogen, R3 is OH, and R4 is H.

[0066] The inventors found that the L-hydroxyproline and its derivatives of the present invention have good herbicidal activity.

[0067] Preferably, the types of weeds include at least one of broadleaf weeds, gramineous weeds, and cyperaceous weeds.

[0068] In a particularly preferred case, the types of weeds include at least one of annual broadleaf weeds, annual gramineous weeds, and annual cyperaceous weeds.

[0069] Particularly preferably, in the present invention, the annual broadleaf weeds are preferably Erigeron annuus and / or Alternanthera philoxeroides, the gramineous weeds are preferably one or more of Echinochloa crusgalli, Digitaria sanguinalis, and Leptochloa chinensis, and the cyperaceous weeds are preferably Cyperus iria.

[0070] The present invention does not particularly limit the specific methods for preparing the structures represented by the foregoing formula (I) and their derivatives, and the structures represented by formula (I-1) and their derivatives. Those skilled in the art can, on the premise of understanding the structures of the present invention, combine the existing technologies in the synthesis field and the known technical means in this field to obtain suitable preparation routes for synthesizing the structures represented by the foregoing formula (I) and their derivatives, and the structures represented by formula (I-1) and their derivatives. Several specific preparation methods of the structures represented by the foregoing formula (I) and their derivatives, and the structures represented by formula (I-1) and their derivatives are exemplarily provided in the following text of the present invention, and those skilled in the art should not understand this as a limitation of the present invention.

[0071] As described above, the second aspect of the present invention provides a broad-spectrum herbicide, and the active ingredient of the herbicide includes a first component; the first component is at least one of the hydroxyproline and its derivatives in the application described in the first aspect.

[0072] Preferably, the first component is L-hydroxyproline or its derivative as described in the application in the first aspect. More 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 or sodium salt of trans-4-hydroxy-L-proline, ammonium or sodium salt of cis-4-hydroxy-L-proline, ammonium or sodium salt of trans-3-hydroxy-L-proline, ammonium 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.

[0073] Preferably, the active ingredient of the herbicide further comprises a second component; the second component comprises at least one of 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitor, acetolactate synthase (ALS) inhibitor, acetyl-CoA carboxylase (ACCase) inhibitor, 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor, protoporphyrinogen oxidase (PPO) inhibitor, photosystem II (PSII) inhibitor, phytoene desaturase (PDS) inhibitor, very long chain fatty acid (VLCFA) inhibitor, deoxy-D-fructose phosphate synthase (DOXP) inhibitor, glutamine synthetase inhibitor, cellulose synthase inhibitor, pyruvate dehydrogenase (PDH) inhibitor, dihydropteroate DHP synthase (DHPS) inhibitor, carotenoid synthesis inhibitor, fat synthesis inhibitor, synthetic hormone inhibitor, cell division inhibitor, tubulin inhibitor, and photosystem I electron transfer inhibitor. The inventors found that the combination of the first component and the second component in the present invention can produce a synergistic effect, further reducing the application cost of the broad-spectrum herbicide and facilitating its popularization and application.

[0074] Preferably, the second component is selected from at least one of glyphosate, glufosinate, flumioxazin, mesotrione, 2,4-D butyl ester, bispyribac-sodium, cyhalofop-butyl, penoxsulam, quinclorac, bentazone, oxaziclomefone, quizalofop-p-ethyl, fomesafen, quizalofop-p-tefuryl, nicosulfuron, atrazine, sodium 2-methyl-4-chlorophenoxyacetate, fluroxypyr, carfentrazone-ethyl, diflufenican, bensulfuron-methyl, sulfosulfuron, clodinafop-propargyl, mesosulfuron-methyl, flucarbazone-sodium, tribenuron-methyl, florasulam, pinoxaden, glufosinate-ammonium, imazapyr, glufosinate-ammonium, triazosulfuron, benzobicyclon, cypropyrazone, and bispyrazone.

[0075] According to a particularly preferred specific 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; the second component is preferably one or more of glyphosate, glufosinate, flumioxazin, mesotrione, and 2,4-D butyl ester. The mass ratio of the first component to the second component in the present invention is 160:1 to 4:1.

[0076] According to a preferred specific embodiment, in the broad-spectrum herbicide, the first component is trans-4-hydroxy-L-proline, and the application rate per mu of the trans-4-hydroxy-L-proline is 150 - 300 g; according to another preferred specific embodiment, in the broad-spectrum herbicide, the first component is cis-4-hydroxy-L-proline, and the application rate per mu of the cis-4-hydroxy-L-proline is 150 - 200 g.

[0077] According to another preferred specific 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 content of the first component to the second component is 8:1 to 40:1.

[0078] According to another preferred specific 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 content of the first component to the second component is 2:1 to 160:1.

[0079] As mentioned above, the third aspect of the present invention provides a method for controlling field weeds, spraying at least one of the hydroxyproline and its derivatives described in the application of the first aspect in the field and / or spraying the broad-spectrum herbicide described in the second aspect in the field.

[0080] 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 / ha. More preferably, it is 4500 g / ha.

[0081] In order to further illustrate the present invention, the following examples are used to describe in detail the application of hydroxyproline and its derivatives provided by the present invention in weed control, but they should not be construed as limiting the protection scope of the present invention.

[0082] Example 1

[0083] (1) Using water or ethanol as solvents, 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%, Guangdong Boxin Chemical Reagent Co., Ltd.), cis-4-hydroxy-L-proline (CAS No. 618-27-9, purity ≥ 98.0%, Guangzhou Jinyuan Chemical Co., Ltd.), trans-3-hydroxy-L-proline (CAS No. 4298-08-2, purity ≥ 98.0%, Shanghai Aladdin Biochemical Technology Co., Ltd.), cis-3-hydroxy-L-proline (CAS No. 4298-08-2, purity ≥ 95.0%, Shanghai Yuanye Bio-Technology Co., Ltd.), trans-3,4-dihydroxy-L-proline (CAS No. 259140-15-3, purity ≥ 95.0%, Shanghai Yuanye Bio-Technology Co., Ltd.), and cis-3,4-dihydroxy-L-proline (CAS No. 95341-65-4, purity ≥ 95.0%, Shanghai Yuanye Bio-Technology Co., Ltd.) were each diluted to concentrations of 0.50 g / 100 mL, 0.75 g / 100 mL, and 1.0 g / 100 mL. Referring to the "Guidelines for Indoor Bioassay of Pesticides - Herbicides - Part 4: Activity Determination Test - Stem and Leaf Spray Method" (NY / T 1155.4-2006), the herbicidal activities of L-proline and trans-4-hydroxy-L-proline were determined:

[0084] The germinated seeds of barnyard grass were evenly sown in plastic pots with a diameter of 15 cm, 20 seeds per pot, and covered with 0.3 - 0.4 cm of soil. They were cultured in an artificial climate chamber with a daytime temperature of 34 °C under light for 12 h and a nighttime temperature of 28 °C in the dark for 12 h, keeping the soil moist; when the seedlings grew to the three-leaf stage, thinning was carried out, and 15 seedlings with consistent growth were left in each pot.

[0085] Three-leaf stage barnyard grass seedlings were used to conduct the above-mentioned stem and leaf spray herbicidal tests for the 7 agents. Four treatment concentrations (0 g / 100 mL, 0.5 g / 100 mL, 0.75 g / 100 mL, and 1.0 g / 100 mL) were set for each agent, and 5 replicates were set for each treatment concentration. The spraying amount was 50 mL (i.e., 10 ml / pot), and the untreated group (0 g / 100 mL) in each group was used as the control. On the 14th day after spraying, the fresh weight of the above-ground parts of the weeds was weighed, the data measured from the 5 replicates were averaged, and the fresh weight control effect was calculated according to the following formula.

[0086] E(%) = (C - T) / C × 100;

[0087] Where: E(%) represents the fresh weight control effect; C represents the average fresh weight of the above-ground parts of the weeds in the untreated group (g); T represents the average fresh weight of the above-ground parts of the weeds 14 days after spraying (g); the results are shown in Table 1.

[0088] Table 1: Determination of Herbicidal Activity of Hydroxy-L-proline

[0089]

[0090] As can be seen from Table 1, L-proline at three concentrations has no herbicidal effect on barnyard grass, while when the concentration of 6 different configurations of L-hydroxyproline reaches or exceeds 0.5 g / 100 mL, it has an obvious herbicidal effect on weeds. In addition, it can also be seen from Table 1 that the herbicidal activity of the cis structure of hydroxy-L-proline is stronger than that of the trans structure.

[0091] (2) Dilute 19 substances including trans-4-hydroxy-L-proline, sodium trans-4-hydroxy-L-prolinate (Compound a), cis-4-hydroxy-L-proline, sodium cis-3-hydroxy-L-prolinate (Compound b), trans-3-hydroxy-L-proline, ammonium trans-3-hydroxy-L-prolinate (Compound c), cis-3-hydroxy-L-proline, ammonium cis-3-hydroxy-L-prolinate (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, and Compounds e - h to a concentration of 1.0 g / 100 mL. Prepare barnyard grass seedlings in the manner described in (1), spray clear water and the agents respectively, and calculate the control effect on the fresh weight of barnyard grass.

[0092] Exemplarily, the preparation methods of several substances are as follows:

[0093] Compound a: Mix 1 mol / L trans-4-hydroxy-L-proline with 1 mol / L sodium hydroxide in a molar ratio of 1:1.2, place it on a magnetic stirrer at 25 °C and stir for 24 h, then vacuum dry to constant weight to obtain sodium trans-4-hydroxy-L-prolinate;

[0094] Compound b: Mix 1 mol / L cis-4-hydroxy-L-proline with 1 mol / L sodium hydroxide in a molar ratio of 1:1.2, place it on a magnetic stirrer at 25 °C and stir for 24 h, then vacuum dry to constant weight to obtain sodium cis-4-hydroxy-L-prolinate;

[0095] Compound e: Mix 1 mol / L cis-4-hydroxy-L-proline with 1 mol / L hexanol in a molar ratio of 1:1.2, add concentrated sulfuric acid as a catalyst, and reflux for 8 hours. After the reaction is completed, cool to room temperature, and perform post-treatments such as neutralization, extraction, and drying to obtain cis-4-hydroxy-L-proline hexyl ester.

[0096] Compound f: 1 mol / L of cis-4-hydroxy-L-proline and 1 mol / L of phenol were mixed in 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, it was cooled, and the excess acid was neutralized with saturated sodium carbonate solution. Then the product was extracted with ethyl acetate, washed and dried to obtain cis-4-hydroxy-L-proline phenyl ester.

[0097] Compound g: 1 mol / L of cis-4-hydroxy-L-proline and 1 mol / L of urea were mixed in a molar ratio of 1:1, and 1.2 mol of condensing agent DCC was added. The mixture was stirred at room temperature for 8 hours, and then the by-product dicyclohexylurea (DCU) was filtered off. Then, the filtrate was concentrated and purified to obtain cis-4-hydroxy-L-proline urea amide.

[0098] Compound h: 1 mol / L of cis-4-hydroxy-L-proline and 1 mol of butylamine were mixed in a molar ratio of 1:1, and 1.2 mol / L of condensing agent EDCI (dichloromethane as the reaction solvent) was added. The mixture was stirred at room temperature for 8 hours. After the reaction, the by-product was filtered off. Then, the solvent was removed by vacuum distillation and the product was purified by column chromatography etc. to obtain cis-4-hydroxy-L-proline butyl amide.

[0099] Table 2: Herbicidal activity analysis of L-hydroxyproline and its derivatives

[0100]

[0101]

[0102] As can be seen from Table 2, L-hydroxyproline derivatives all have relatively high herbicidal activity at 1 g / 100 mL.

[0103] Example 2

[0104] A herbicide was prepared with the concentration of trans-4-hydroxy-L-proline being 1.0 g / 100 mL and the volume concentration of the adjuvant being 0.05%. The adjuvant was agricultural organosilicon surfactant IOTA 2000 (produced by Anhui Aiyota Silicone Oil Co., Ltd., containing polyether modified heptamethyltrisiloxane);

[0105] The experiment was carried out according to the methods and basic requirements of the field efficacy plot test of 《GB / T 17980.42-2000 Pesticide field efficacy test guidelines (I) Herbicides for controlling weeds in maize fields》:

[0106] On the dry land with regular plots and uniform soil fertility, ridges were made, and maize was planted according to the specification of plant spacing 30 cm × 60 cm. Three rectangular plots were randomly set, and the area of each plot was 20 m 2When the corn grows to the 3-leaf stage and the 5-leaf stage, the weeds in the plots are respectively treated with trans-4-hydroxy-L-proline by foliar spraying at 2250 g / ha and 4500 g / ha. The control effect of weeds 20 days after spraying the medicine was investigated, and the results are shown in Table 3.

[0107] Plant control effect = number of dead plants / total number of plants × 100%.

[0108] Table 3: Weed plant control effect (%) of different dosages of trans-4-hydroxy-L-proline

[0109]

[0110]

[0111] As can be seen from Table 3, when the dosage of trans-4-hydroxy-L-proline is 2250 g / ha, it has a good control effect on weeds. When the dosage is increased to 4500 g / ha, it has excellent control effects on different types of weeds.

[0112] Example 3

[0113] Test the plant control effects of the compounding of hydroxy-L-proline with other chemical herbicides on barnyard grass, crabgrass, green foxtail, nutgrass flatsedge, creeping woodsorrel, broadleaf polygala, purslane, monochoria vaginalis, redroot amaranth, bedstraw, slender amaranth, monochoria korsakowii, goosegrass, arrowhead, Alopecurus aequalis, wild oat, shepherd's purse, field bindweed, speedwell, fleabane, perennial ryegrass, water hyacinth, Spartina alterniflora in the open air.

[0114] 1. Application scenarios. Select to carry out tests 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 odoratum fields (40 cm × 15 cm), free-range ponds, coastal tidal flats and other places.

[0115] 2. Plot setting and compounding treatment. Select areas with relatively concentrated distribution of target weeds in the above scenarios to set plots and test the foliar spraying treatment effects of compound pesticides. Each plot in corn fields, cotton fields, spring wheat fields, lily fields, and coastal tidal flats is 20 m 2 , each plot in direct-seeded rice fields and transplanted rice fields is 25 m 2 , each plot in four-year-old tea gardens, lily fields, and polygonatum odoratum fields is 9 m 2 , each plot in ponds is 5 m 2The medicament treatment components are set as a compound group, a control group 1, and a control group 2, each group containing 3 plots; the control group 1 is treated with trans-4-hydroxy-L-proline or cis-4-hydroxy-L-proline alone, and the control group 2 is treated with a chemical herbicide alone. The medicine is applied during the weed seedling stage to compare the plant control effects of the compound group and the control groups.

[0116] The chemical herbicide formulations used and their manufacturers are as follows: 41 wt% glyphosate isopropylammonium aqueous solution, Monsanto Company; 10 wt% cyhalofop-butyl emulsifiable concentrate, Jiangsu Huifeng Bio-Agriculture Co., Ltd.; 15 wt% mesotrione suspension concentrate, Shandong Binong Technology Co., Ltd.; 200 g / L glufosinate-ammonium aqueous solution, Yongnong Bioscience Co., Ltd.; 72 wt% 2,4-D butylate emulsifiable concentrate, Shandong QiaoChang Modern Agriculture Co., Ltd.; 100 g / L bispyribac-sodium suspension concentrate, Jiangsu Futian Agrochemical Co., Ltd.; 25 g / L penoxsulam dispersible oil suspension, Anhui Jiuyi Agricultural Co., Ltd.; 50 wt% quinclorac wettable powder, Zhejiang Zhongshan Chemical Industry Group Co., Ltd.; 480 g / L bentazone aqueous solution, Jiangsu Zhongqi Science & Technology Co., Ltd.; 10 wt% metamifop emulsifiable concentrate, Jiangsu Ruibang Agrochemical Co., Ltd.; 6 wt% triazosulfuron dispersible oil suspension, Jiangsu Agricultural Means of Production Group Agrochemical Co., Ltd.; 250 g / L fomesafen aqueous solution, Jinan Tianbang Chemical Co., Ltd.; 10 wt% quizalofop-P-ethyl emulsifiable concentrate, Hebei Rongwei Biopharmaceutical Co., Ltd.; 10 wt% acifluorfen-ethyl emulsifiable concentrate, Shandong Xianda Agrochemical Co., Ltd.; 40 g / L nicosulfuron dispersible oil suspension, Qingdao Qingyuan Nongguan Resistance Weed Control Co., Ltd.; 38 wt% atrazine suspension concentrate, Shandong Lubang Chemical Industry Co., Ltd.; 30 wt% tembotrione suspension concentrate, BASF Europe Company; 56 wt% MCPA-Na soluble powder, Jiangsu Institute of Hormones Co., Ltd.; 200 g / L fluroxypyr emulsifiable concentrate, Sichuan Lier Crop Science Co., Ltd.; 5 wt% diflufenican suspension concentrate, Qingdao Qingyuan Nongguan Resistance Weed Control Co., Ltd.; 10 wt% bensulfuron-methyl wettable powder, Zhejiang Tianfeng Bioscience Co., Ltd.; 75 g / L sulcotrione suspension concentrate, Bayer CropScience; 69 g / L clodinafop-propargyl emulsion in water, Bayer CropScience (China) Co., Ltd.; 15 wt% clodinafop-propargyl wettable powder, Syngenta Crop Protection AG; 30 g / L mesosulfuron-methyl dispersible oil suspension, Bayer CropScience (China) Co., Ltd.; 70% flucarbazone-sodium water dispersible granules, Jiangsu Kelsi Group Co., Ltd.; 75 wt% tribenuron-methyl water dispersible granules, Shandong Lubang Chemical Industry Co., Ltd.; 50 g / L florasulam suspension concentrate, Dow AgroSciences (China) Co., Ltd.; 5 wt% pinoxaden emulsifiable concentrate, Syngenta Crop Protection AG; 10 wt% quinmerac suspension concentrate, manufacturer: Shandong Xianda Agrochemical Co., Ltd.; 6 wt% pyraflufen-ethyl dispersible oil suspension, Jiangsu Qingyuan Nongguan Weed Control Co., Ltd.; 6 wt% cypropyrazone dispersible oil suspension, Jiangsu Qingyuan Nongguan Weed Control Co., Ltd.; 10 wt% bicyclopyrone dispersible oil suspension, Qingdao Qingyuan Crop Science Co., Ltd.; 20 wt% glufosinate-ammonium ammonium salt soluble concentrate, Yongnong Bioscience Co., Ltd.; 240 g / L imazapyr aqueous solution, Zhejiang Xin'an Chemical Industry Group Co., Ltd.

[0117] 3. Control efficacy of compound treatment. The application rates of herbicides and weed control efficacies in each group of tests are shown in Table 4, where the plant control efficacy is shown in Table 4, and the control efficacy (%) = number of dead plants / total number of plants × 100%. The compound ratio in Table 4 represents the compound mass ratio.

[0118] Table 4: Weed control efficacy of the first component compounded with the second component

[0119]

[0120]

[0121]

[0122]

[0123]

[0124] As can be seen from the above embodiments, the hydroxyproline and its derivatives provided by the present invention have a broad herbicidal spectrum and have good control effects on most broad-leaved weeds, gramineous weeds and cyperaceae weeds.

[0125] The first component and the second component in the broad-spectrum herbicide provided by the present invention are compounded to produce a synergistic effect, further reducing the application cost and being beneficial to popularization and application.

[0126] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the technical concept scope of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope 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.

Images