CN112568223B - Herbicidal composition, application thereof and herbicide - Google Patents
Herbicidal composition, application thereof and herbicide Download PDFInfo
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- CN112568223B CN112568223B CN202011631196.6A CN202011631196A CN112568223B CN 112568223 B CN112568223 B CN 112568223B CN 202011631196 A CN202011631196 A CN 202011631196A CN 112568223 B CN112568223 B CN 112568223B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
- A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- Wood Science & Technology (AREA)
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Abstract
The invention relates to the field of pesticides, and discloses a weeding composition and application thereof, and a herbicide, wherein the weeding composition comprises the following components in percentage by weight: (0.01-100) a component A and a component B, wherein the component A is a compound 168 shown in a formula (1), and the component B is oxazachlor shown in a formula (2); optionally, the composition further comprises a component C shown in a formula (3). The weeding composition and the herbicide provided by the invention can overcome the defect of low safety of the medicament provided by the prior art in preventing and controlling weeds in paddy fields, and simultaneously improve the stability of weeding effect and the weed death speed.
Description
Technical Field
The invention relates to the field of pesticides, in particular to a weeding composition, application of the weeding composition in preventing and controlling paddy field weeds and a herbicide.
Background
Grass weeds in paddy fields become a main factor threatening the yield of paddy rice, and even in areas with strong drug resistance of barnyard grass and moleplant seeds, the phenomenon of absolute yield occurs.
At present, methods for controlling weeds in paddy fields are divided into sealing treatment and stem and leaf spraying treatment, and stem and leaf spraying is used as a main means for controlling the weeds. However, these weeds have developed a certain resistance to conventional agents such as quinclorac, penoxsulam, oxazoxamide, etc., and the difficulty of control increases, and the cost of control increases.
Compound 168 (english name (R) -2- (1- (2- (4-chlorophenyloxy) proppoxyimino) -butyl) -5- (2- (ethylhio) propyl) -3-hydroxyyclohex-2-enone) is also a cyclohexenone herbicide having the structural formula:
compound 168 is an ACCase inhibitor. Is mainly used for preventing and controlling gramineous weeds in paddy fields.
The compound 168 has a poor control effect in preventing and killing barnyard grass, semen Euphorbiae, crabgrass and golden green bristlegrass in paddy fields, and the improvement of the dosage can increase the stability of the drug effect, but is easy to cause phytotoxicity to paddy.
Disclosure of Invention
The invention aims to overcome the defect of low safety of the medicament provided by the prior art in preventing and controlling paddy field weeds.
The invention further aims to overcome the defects of unstable weeding effect and low weed death speed of the cyclohexenone herbicide compound 168. At present, no herbicide has good prevention effect on weeds in various families in a broad spectrum, and the occurrence condition of local weeds can be solved only by mixing different herbicides, but the occurrence of herbicide cross resistance of the weeds is brought along with the occurrence of the local weeds, and the mixed herbicide antagonizes to reduce the activity and generate a plurality of problems of heavier phytotoxicity on rice and the like.
The inventor of the present invention found in the study that the compound 168, when mixed with a specific amount of oxazamate, can significantly increase the control effect on grassy weeds such as barnyard grass, crabgrass, etc., and can also improve the safety to rice. Accordingly, the inventors of the present invention completed the technical scheme of the present invention.
In order to achieve the above object, a first aspect of the present invention provides a herbicidal composition comprising a herbicidally effective amount of a component a and a component B in a weight ratio of 1: (0.01-100), wherein the component A is a compound 168 shown in a formula (1), and the component B is oxazoxamide shown in a formula (2); optionally, the composition also contains a component C shown in a formula (3);
in a second aspect, the present invention provides the use of the aforementioned herbicidal composition for controlling weeds in paddy fields.
In a third aspect the present invention provides a herbicide consisting of an active ingredient and an adjuvant, the active ingredient comprising the herbicidal composition of the first aspect.
The weeding composition and the herbicide provided by the invention can overcome the defect that the medicament provided by the prior art has obvious resistance in preventing and controlling weeds in paddy fields, and have good preventing and controlling effect on resistant weeds in paddy fields. Moreover, the weeding composition and the herbicide provided by the invention can overcome the defect that the cyclohexenone herbicide compound 168 can generate serious phytotoxicity to crops such as rice, have good control effect on grassy weeds common to paddy fields, and have high safety to rice.
Particularly, the weeding composition and the herbicide provided by the invention can obviously increase the control effect on grassy weeds such as barnyard grass, moleplant seed and the like, and can improve the safety and the weed death speed of rice.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a herbicidal composition comprising a herbicidally effective amount of a component a and a component B in a weight ratio of 1: (0.01-100), wherein the component A is a compound 168 shown in a formula (1), and the component B is oxazoxamide shown in a formula (2); optionally, the composition also contains a component C shown in a formula (3);
the components in the pesticide composition provided by the invention can be stored in a mixed mode or can be stored independently, and the pesticide composition provided by the invention comprises the components which form the pesticide composition are stored separately and are mixed in a barrel mixing mode for use.
Preferably, in the herbicidal composition, the weight ratio of the component a to the component B is 1: (0.05-50); more preferably 1: (0.1-30); particularly preferably 1: (0.3-10).
The inventors of the present invention found that, in particular, a composition comprising, by weight, 1: the weeding composition of the component A and the component B, which are (0.3-10), can prevent and control weeds in paddy fields, and the formed weeding composition can realize 100% prevention effect on grassy weeds in paddy fields such as barnyard grass, moleplant seed and the like, and has high safety on crops.
Preferably, in the herbicidal composition, the weight ratio of the component a to the component C is 1: (0-0.5).
In fact, the component C in the herbicidal composition of the present invention does not have a good control effect on weeds, but, due to the existing process limitations, the purity of the component A obtained in the prior art is difficult to reach 100% under the control of costs, and substantially a certain amount of component C is contained, and therefore, the herbicidal composition of the present invention optionally contains component C, and the inventors of the present invention found that when the weight ratio of component C to component A is not higher than 0.5:1, the herbicidal composition of the present invention has excellent weed control effects and high safety to crops.
As previously mentioned, a second aspect of the present invention provides the use of the aforementioned herbicidal composition for controlling paddy field weeds.
Preferably, the weeds are one or more than two grassy weeds.
More preferably, the weeds are one or more than two of grassy weeds such as barnyard grass, moleplant seed, golden green bristlegrass, crabgrass, paspalum distachum, rice Lespedeza and the like.
As described above, the third aspect of the present invention provides a herbicide comprising an active ingredient and an adjuvant, the active ingredient comprising the herbicidal composition of the first aspect.
Preferably, the content of the active ingredient is 1 to 95% by weight based on the total weight of the herbicide; more preferably 1 to 80% by weight.
Preferably, the auxiliary materials are at least one of emulsifying agent, dispersing agent, wetting agent, spreading agent, stabilizing agent, defoaming agent, synergistic agent, penetrating agent, adhesive, safener, carrier and filler.
Preferably, the dosage form of the herbicide of the present invention is at least one selected from the group consisting of wettable powders, soluble powders, emulsifiable concentrates, aqueous suspensions, dispersible oil suspensions, aqueous emulsions, microemulsions and water dispersible granules.
The method of how to form the dosage forms of wettable powder, soluble powder, emulsifiable concentrate, aqueous suspension, dispersible oil suspension, aqueous emulsion, microemulsion, water dispersible granule and the like is not particularly limited, and the person skilled in the art can refer to the method provided in the modern pesticide dosage form processing technology (Liu Anwen, chemical industry Press) to form various dosage forms provided by the invention.
The component B of the present invention may be in other active forms of the aforementioned substances, for example, in the form of esters or salts thereof, etc.
Preferably, the herbicide of the present invention is stored separately from the components of the pesticidal composition forming the active ingredient and is ready to be used in tank mix form.
The present invention will be described in detail by examples. In the following examples, all the raw materials used are commercially available products unless otherwise specified.
The preparation method of (R) -2- (4-chlorine-phenoxy) -propoxyamine comprises the following steps:
parachlorophenol (0.515 mol), potassium carbonate (0.5 mol) and petroleum ether (500 ml) are added into a reaction bottle for reflux water separation, after reaction for 30min, (S) -methyl chloropropionate (0.5 mol) is added dropwise, after the dripping is finished, water separation is continued for 12h under the condition of 65 ℃, water (100 ml) is added after HPLC (high performance liquid chromatography) detects that the methyl chloropropionate is basically unchanged, the mixture is stirred and then stands for layering, an organic phase is washed twice by water, petroleum ether is removed under reduced pressure, and 2-parachlorophenoxy methyl propionate is obtained.
Sodium borohydride (1 mol), anhydrous calcium chloride (0.05 mol), toluene (500 ml) and ethanol (500 ml) are added into a reaction bottle, after being uniformly mixed, the prepared methyl 2-p-chlorophenoxy propionate (0.5 mol) is continuously added dropwise, after the dripping is finished, the reaction is carried out for 4 hours under the condition of 30 ℃, after the content of the methyl 2-p-chlorophenoxy propionate is detected to be less than 1wt percent by HPLC, 20wt percent ammonium chloride aqueous solution (calculated as pure substance, 1 mol) is added for hydrolysis reaction, the hydrolysis temperature is 30 ℃ and the hydrolysis time is 1 hour, after the reaction is finished, standing and layering are carried out, toluene is used for extracting twice, organic phases are combined, and the (R) 2- (4-chlorophenoxy) -propanol is obtained after the solvent is removed by cleaning.
2- (4-chloro-phenoxy) -propanol (0.5 mol), triethylamine (0.585 mol) and toluene (500 ml) were added to a reaction flask, methanesulfonyl chloride (0.6 mol) was added dropwise thereto, the mixture was reacted at 30℃for 3 hours, after HPLC detection, the content of 2- (4-chloro-phenoxy) -propanol was less than 1% by weight, and then water was added and stirred for delamination, and toluene was removed from the organic phase to give [2- (4-chloro-phenoxy) -propyl ] methanesulfonate.
Methanesulfonic acid [2- (4-chloro-phenoxy) -propyl ] ester (0.5 mol), acetohydroxamic acid (0.85 mol) and DMSO (600 ml) are added into a reaction bottle, sodium hydroxide (2 mol) is added after stirring and dissolution, reaction is carried out for 10 hours at 60 ℃, after HPLC detection of no change of methanesulfonic acid [2- (4-chloro-phenoxy) -propyl ] ester, DMSO is distilled off, organic phase water remained in the bottle is dissolved, and the mixture is extracted three times by using dichloromethane, and dichloromethane is removed, thus N- [2- (4-chloro-phenoxy) -propoxy ] acetamide is obtained.
N- [2- (4-chloro-phenoxy) -propoxy ] acetamide (0.5 mol) and ethanol (100 ml) are added into a reaction bottle, 30wt% hydrochloric acid (1 mol based on hydrogen ions) is added dropwise, the reaction is carried out for 5 hours at 30 ℃, after the content of N- [2- (4-chloro-phenoxy) -propoxy ] acetamide is detected to be less than 1wt% by HPLC, ethanol in the system is removed, 30wt% NaOH is added to adjust the pH value to 14, dichloromethane is used for extraction twice, and dichloromethane is removed to obtain (R) -2- (4-chloro-phenoxy) -propoxy amine, and the optical purity is more than or equal to 95%.
The preparation method of the (S) -2- (4-chlorine-phenoxy) -propoxyamine comprises the following steps:
similar to the preparation of (R) -2- (4-chloro-phenoxy) -propoxyamine, the difference is: and (S) -methyl chloropropionate is replaced by (R) -methyl chloropropionate, so that the (S) -2- (4-chloro-phenoxy) -propoxyamine is prepared, and the optical purity is more than or equal to 95%.
2- (1-butyryl) -5- (2-ethylmercaptopropyl) -1, 3-cyclohexanedione: purchased from Shandong first reach Agrochemical Co., ltd.
Mass spectrometer: icpms-2030 Shimadzu production.
400M nuclear magnetism: bruker.
Automatic polarimeter: WZZ-2S, shanghai electric production.
The raw materials used in the following examples are specifically as follows:
component A:
compound 168, synthesized in the laboratory, was synthesized as follows:
the specific synthesis method comprises the following steps: to the reaction flask were added 5.5g of (R) -2- (4-chloro-phenoxy) -propoxyamine, 7.3g of 2- (1-butyryl) -5- (2-ethylmercaptopropyl) -1, 3-cyclohexanedione and 100.0ml of petroleum ether, the temperature was kept constant at 35℃for 6 hours, 100.0ml of saturated saline was added to the system, and the aqueous phase was adjusted to pH=1 with 20% by weight of hydrochloric acid, and after stirring sufficiently, the layers were separated, the organic phase was washed to neutrality with saline, and the solvent was stripped off to give a yellow viscous liquid, which was determined by mass spectrometry, 400M nuclear magnetism and automatic polarimeter as component A having an optical purity of more than 95%.
Component B:
oxazoxamide is synthesized in a laboratory, and the synthesis route is as follows:
specific synthetic methods are published in the "synthesis of several excellent herbicides" by the journal of the world pesticides ", 2012, volume 34, phase 1, pages 1-2, with reference to Cheng Zhiming.
Component C: laboratory synthesis, the synthetic route is as follows:
the specific synthesis method comprises the following steps: to the reaction flask were added 5.5g of (S) -2- (4-chloro-phenoxy) -propoxyamine, 7.3g of 2- (1-butyryl) -5- (2-ethylmercaptopropyl) -1, 3-cyclohexanedione and 100.0ml of petroleum ether, the temperature was kept constant at 35 ℃ for 6 hours, 100.0ml of saturated saline was added to the system, and the aqueous phase was adjusted to ph=1 with 20wt% hydrochloric acid, and after stirring sufficiently, the layers were separated, the organic phase was washed with saline to neutrality, and the solvent was stripped off to give a yellow viscous liquid, which was determined by mass spectrometry, 400M nuclear magnetism and automatic polarimeter as component C having an optical purity of more than 95%.
Cyclohexanone: purchased from atanan shipping and university limited.
Anhydrous sodium sulphate: purchased from Shandong Tian Du chemical Co.
Sodium dodecyl sulfonate: purchased from atanan Hengrun textile Co.
Calcium dodecylbenzenesulfonate: purchased from Shandong Tiandao bioengineering Co.
Castor oil polyoxyethylene ether: brand EL-20, available from Shandong Tiandao bioengineering Co.
150# solvent oil: purchased from Jiangsu Huaren chemical Co.
Nonylphenol polyoxyethylene ether: trade mark NP-7, available from Nanjing chemical Co., ltd
White carbon black: purchased from the sea white carbon company.
Organic bentonite: purchased from the new mineral materials limited of the Hui-throwing of the state of Suzhou.
Methyl oleate: purchased from Jiangsu Fengshtime biotechnology Co.
Nonylphenol polyether-10 phosphate: the brand NP-10P was purchased from Shandong Tiandao bioengineering Co.
Dioctyl sodium sulfosuccinate: purchased from Shandong Yongyan health products technology Co.
Naphthalene sulfonic acid sodium salt formaldehyde condensate: the brand GY-D10 is purchased from Beijing Guangdong Yinong chemical Co.
Styrene acrylic acid copolymer sodium salt: brand GY-D800, available from Beijing Guangdong Yinong chemical Co.
Composition of EO-PO block copolymer: brand D800, available from Nanjing Gutian chemical Co.
Kaolin: purchased from shanxi Xinjingtai technologies.
Xanthan gum: purchased from qiao Feng chemical Co., ltd.
Ethylene glycol: purchased from jinan Xin Weida chemical industry Co.
Silicone defoamer: purchased from Qingdao Jiusheng chemical technology Co.
The amounts of the raw materials in the examples below are in weight percent unless otherwise specified.
Example 1: emulsifiable concentrate
The formula comprises the following components: 2% of component A+5% of component B+7% of calcium dodecyl benzene sulfonate+8% of castor oil polyoxyethylene ether+5% of cyclohexanone and 150# solvent oil.
The processing process comprises the following steps: mixing the above materials, stirring, and dissolving completely.
Example 2: emulsifiable concentrate
The formula comprises the following components: 2.5% of component A+2.5% of component B+8% of calcium dodecyl benzene sulfonate+7% of castor oil polyoxyethylene ether+5% of cyclohexanone+150# solvent oil.
The processing process comprises the following steps: mixing the above materials, stirring, and dissolving completely.
Example 3: dispersible oil suspension agent
The formula comprises the following components: 3% of component A+5% of component B+8% of calcium dodecyl benzene sulfonate+7.5% of nonylphenol polyoxyethylene ether+2.5% of castor oil polyoxyethylene ether+1% of white carbon black+2% of organic bentonite and methyl oleate.
The processing process comprises the following steps: and (3) putting the materials into a mixing kettle, stirring and mixing, then, passing through a colloid mill, then, entering a sand mill for three-stage sanding, and finally, shearing uniformly in a shearing machine to obtain a finished product.
Example 4: dispersible oil suspension agent
The formula comprises the following components: the composition comprises 4% of component A, 5% of component B, 7% of calcium dodecyl benzene sulfonate, 8% of nonylphenol polyoxyethylene ether, 3% of castor oil polyoxyethylene ether, 1% of white carbon black, 2% of organic bentonite and methyl oleate.
The processing process comprises the following steps: and (3) putting the materials into a mixing kettle, stirring and mixing, then, passing through a colloid mill, then, entering a sand mill for three-stage sanding, and finally, shearing uniformly in a shearing machine to obtain a finished product.
Example 5: water dispersible granule
The formula comprises the following components: 5% of component A+1.5% of component B+3.2% of anhydrous sodium sulphate+2.0% of sodium dodecyl sulfate+7% of naphthalene sulfonate sodium salt formaldehyde condensate+3% of styrene acrylic acid copolymer sodium salt+10% of white carbon black and filler kaolin are supplemented.
The processing process comprises the following steps: firstly, absorbing the component A by using white carbon black, uniformly mixing the materials, carrying out air flow crushing, adding water for kneading, granulating, drying, and finally screening to obtain a finished product.
Example 6: water dispersible granule
The formula comprises the following components: 1% of component A+10% of component B+3.2% of anhydrous sodium sulfate+2.0% of sodium dodecyl sulfate+6.5% of naphthalene sulfonic acid sodium salt formaldehyde condensate+3.5% of styrene acrylic acid copolymer sodium salt+5% of white carbon black+filler kaolin are filled.
The processing process comprises the following steps: firstly, absorbing the component A by using white carbon black, uniformly mixing the materials, carrying out air flow crushing, adding water for kneading, granulating, drying, and finally screening to obtain a finished product.
Example 7: aqueous emulsion
The formula comprises the following components: composition of 5% component a+5% component b+8% EO-PO block copolymer+4% calcium dodecylbenzenesulfonate+10% 150# solvent oil+5% cyclohexanone+2% xanthan gum+4% ethylene glycol+0.1% silicone defoamer+water.
The processing process comprises the following steps: and (3) putting the oil phase materials into a shearing kettle, stirring and mixing uniformly, putting the oil phase materials into a mixing kettle, stirring and mixing uniformly, and then slowly adding the water phase materials into the oil phase materials for shearing.
Example 8: aqueous emulsion
The formula comprises the following components: 4% of component A+10% of component B+8% of EO-PO block copolymer composition+4% of calcium dodecylbenzenesulfonate+10% of 150# solvent oil+5% of cyclohexanone+2% of xanthan gum+4% of ethylene glycol+0.1% of silicone defoamer+water.
The processing process comprises the following steps: and (3) putting the oil phase materials into a shearing kettle, stirring and mixing uniformly, putting the oil phase materials into a mixing kettle, stirring and mixing uniformly, and then slowly adding the water phase materials into the oil phase materials for shearing.
Example 9: dispersible oil suspension agent
The formula comprises the following components: 3% of component A+5% of component B+1% of component C+4% of calcium dodecyl benzene sulfonate+11% of nonylphenol polyether-10 phosphate ester+5% of dioctyl sodium succinate+2% of organic bentonite and methyl oleate.
The processing process comprises the following steps: and (3) putting the materials into a mixing kettle, stirring and mixing, then, passing through a colloid mill, then, entering a sand mill for three-stage sanding, and finally, shearing uniformly in a shearing machine to obtain a finished product.
Example 10: dispersible oil suspension agent
The formula comprises the following components: 2% of component A+5% of component B+1% of component C+4% of calcium dodecyl benzene sulfonate+11% of nonylphenol polyether-10 phosphate ester+5% of dioctyl sodium succinate+2% of organic bentonite and methyl oleate.
The processing process comprises the following steps: and (3) putting the materials into a mixing kettle, stirring and mixing, then, passing through a colloid mill, then, entering a sand mill for three-stage sanding, and finally, shearing uniformly in a shearing machine to obtain a finished product.
Test case
Test target: barnyard grass (Echinochloa crus-galli (L.) P.Beauv.), crabgrass (Digitaria sanguinalis (L.) Scop.).
The weeding activity test method comprises the following steps: 15-20 seeds of the weeds to be tested are uniformly sown on the soil surface of a pot bowl by adopting a stem and leaf spraying method (NY/T1155.4-2006), quantitative soil is filled in the pot bowl with the height of 11cm and the diameter of 9cm to 3/4 of the pot bowl, and the pot bowl is covered with fine soil with the height of about 1cm and then placed in a greenhouse (the temperature is 22-28 ℃ and the humidity is 97%, and the same applies below) for cultivation. And (3) carrying out stem and leaf spraying treatment when the target weeds to be tested grow to 3-5 leaf stages, spraying 1mL of liquid medicine into each pot, repeating for 4 times, placing the treated target weeds to be tested in a greenhouse for culture, and periodically observing the growth condition of the target weeds to be tested.
The investigation method comprises the following steps: after 30 days of test treatment, the victim symptoms and growth inhibition conditions of the target weeds to be tested are visually detected, and the fresh weight of the overground parts of the target weeds to be tested is weighed, so that the fresh weight inhibition rate (%) is calculated.
Fresh weight inhibition (%) = (control fresh weight-treated fresh weight)/control fresh weight x 100.
Combined action evaluation method: the mode of action of the herbicide combination was evaluated according to the Gowing method (NY/T1155.7-2006) and the formula is: e (E) 0 =x+y× (100-X)/100, where X is the fresh weight inhibition of the target weed for single use of agent a compound 168; y is the fresh weight inhibition rate of the target weeds when the B medicament is used singly; e (E) 0 The agent A and the agent B are the theoretical control effects of targets in the mixing process; e is the actual control of the targets of the A medicament and the B medicament when mixed, and the results are shown in table 1.
Evaluation criteria: when E-E 0 >Expressed as synergy at 10%, when E-E 0 Between 10% and E-E 0 <-10% expressed as antagonism.
Table 1: indoor fresh weight control effect of compound 168 and oxazachlor on weeds
And (3) field efficacy test:
test crop: direct seeding rice
The administration period is as follows: 15 days after sowing, 3 leaves of rice 1 heart, 3-4 leaf period of weeds
Test treatment: the herbicide composition provided in the example was used for field verification, and the field verification test was mainly performed in three places of Hainan, jilin Changchun, jiangsu Huaian, and Hubei Jingzhou. The four-land rice varieties are early rice 27, general japonica 89, guangliangyou 297 and Huanghua.
Selecting land with serious weed occurrence and complex and various weed phases of 20m 2 For one district, each treatment is repeated for 3 times, stem and leaf spraying treatment is carried out 15 days after direct seeding, water is added 48 hours after pesticide application treatment, and water is kept for 5-7 days.
And (3) observing the treatment area and the control area 30 days after treatment, counting the number of weeds in the treatment area and the control area, and calculating the plant prevention effect of the weeds in the treatment area.
Plant control (%) = (control weed number-treated weed number)/control weed number×100.
The control effect of the agents of each example on weeds and the safety results on rice are shown in table 2, and the crop safety evaluation criteria are shown in table 3. And EC in table 2 represents: emulsifiable concentrates.
Table 2: the pesticide has average prevention effect on weeds in different areas and safety on rice
Through field experiments, it is obvious that the compound 168 and the metamifop have synergistic or additive effects, the average prevention effect of field weeding can be obviously improved, and the phytotoxicity of the compound 168 to rice can be reduced by mixing.
Table 3: crop safety evaluation standard table
| Growth inhibition ratio (%) | Evaluation (inhibition, deformity, albinism, etc.) |
| 0 | Has no influence on the growth of crops and is safe. |
| 0-10 | Slightly affects the growth of crops, and has no obvious phytotoxicity. |
| 10-30 | Has influence on the growth of crops and is slightly phytotoxic. |
| 30-50 | To doThe growth of the plant is greatly influenced and moderately harmed. |
| 50-100 | Has great influence on the growth of crops and serious phytotoxicity. |
| 100 | The crop died completely. |
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A herbicidal composition comprising a herbicidally effective amount of a component a and a component B in a weight ratio of 1: (0.3-10), wherein the component A is a compound 168 shown in a formula (1), and the component B is oxazoxamide shown in a formula (2); optionally, the composition also contains a component C shown in a formula (3);
2. the herbicidal composition of claim 1, wherein the weight ratio of component a to component C is 1: (0-0.5).
3. Use of the herbicidal composition according to claim 1 or 2 for controlling weeds in paddy fields.
4. The use according to claim 3, wherein the weeds are one or more of grassy weeds.
5. A herbicide consisting of an active ingredient and an adjuvant, the active ingredient comprising the herbicidal composition according to claim 1 or 2.
6. The herbicide according to claim 5, wherein the active ingredient is contained in an amount of 1 to 95% by weight, based on the total weight of the herbicide.
7. The herbicide according to claim 5, wherein the active ingredient is contained in an amount of 1 to 80% by weight, based on the total weight of the herbicide.
8. The herbicide of any one of claims 5-7, wherein the adjuvant is at least one of an emulsifier, a dispersant, a wetting agent, a spreader, a stabilizer, a defoamer, a synergist, a penetrant, an adhesive, a safener, a carrier, and a filler.
9. The herbicide according to any one of claims 5-7, wherein the herbicide is in a dosage form selected from at least one of wettable powder, soluble powder, emulsifiable concentrate, aqueous suspension, dispersible oil suspension, aqueous emulsion, microemulsion and water dispersible granule.
10. The herbicide according to any one of claims 5-7, wherein the herbicide is stored separately from the components of the pesticidal composition forming the active ingredient and is ready-to-use in a tank mix.
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| CN106857561A (en) * | 2017-04-07 | 2017-06-20 | 安徽蓝田农业开发有限公司 | Herbicidal composition and its application of a kind of Han oxaziclomefones He metamifop |
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| CN104756998A (en) * | 2015-04-20 | 2015-07-08 | 济南科赛基农化工有限公司 | Metamifop.benzobicylon compound preparation and application thereof |
| CN106857561A (en) * | 2017-04-07 | 2017-06-20 | 安徽蓝田农业开发有限公司 | Herbicidal composition and its application of a kind of Han oxaziclomefones He metamifop |
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