CN109287638A - A kind of rice weeding composition containing metamifop - Google Patents
A kind of rice weeding composition containing metamifop Download PDFInfo
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- CN109287638A CN109287638A CN201811198804.1A CN201811198804A CN109287638A CN 109287638 A CN109287638 A CN 109287638A CN 201811198804 A CN201811198804 A CN 201811198804A CN 109287638 A CN109287638 A CN 109287638A
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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
-
- 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
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
- A01N39/04—Aryloxy-acetic acids; Derivatives thereof
-
- 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
-
- 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
-
- 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
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
Abstract
The invention discloses a kind of rice weeding composition containing metamifop, including primary activity ingredient and second order activity ingredient, the primary activity ingredient includes metamifop 5-13 mass parts, the second order activity ingredient is selected from cyhalofop-butyl 10-20 mass parts, bispyribac-sodium 4-8 mass parts, dichloro quinolinic acid 5-10 mass parts, halosulfuronmethyl 6-11 mass parts, chlorine fluorine than fluoroacetic acid 4-12 mass parts, and the second active constituent can be a kind of active matter: cyhalofop-butyl；Be also possible to two kinds of active mixtures: bispyribac-sodium and halosulfuronmethyl, cyhalofop-butyl and dichloro quinolinic acid, chlorine fluorine are than fluoroacetic acid and halosulfuronmethyl, and the present invention relates to medical compounds fields.Rice weeding composition of this kind containing metamifop, metamifop can effectively prevent and kill off paddy field main weeds, such as barnyard grass, semen euphorbiae, herba digitariae and herba eleusines indicae to rice safety, it is mainly used for transplanting and direct sowing rice field weeding, can effectively solves the problems in above-mentioned background technique.
Description
Technical field
The present invention relates to medical compounds field, specially a kind of rice weeding composition containing metamifop.
Background technique
Widely distributed weeds have 30000 kinds in the whole world, different degrees of harm are caused to crop for about 1800 kinds every year, often
Year because caused by Weed infestation crop production reduction be up to 9.7%, herbicide refers to that weeds can be made thoroughly or selectively to occur is withered
Dead medicament, also known as herbicide, to eliminate or inhibit a substance of plant growth.Common herbicide kind is to organise
Object is closed, can be widely used for the ground such as prevention and treatment farmland, orchard, floral nursery, grassland and bare place, railway line, river, reservoir, warehouse
The noxious plants such as weeds, miscellaneous filling, miscellaneous tree.Many weeds have been efficiently controlled using herbicide in the last hundred years, but chemical agent
It is a large amount of using also having caused a series of problem, the appearance, soil pollution of such as herbicide-resistant weeds plant, water quality are moved back
Change and the harm etc. to non-weeds biology are unfavorable for carrying out weeding.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of rice weeding composition containing metamifop, oxazole
Acyl grass amine can effectively prevent and kill off paddy field main weeds and be mainly used for such as barnyard grass, semen euphorbiae, herba digitariae and herba eleusines indicae to rice safety
Transplanting and direct sowing rice field weeding, can effectively solve the problems in above-mentioned background technique.
(2) technical solution
In order to achieve the above object, the present invention is achieved by the following technical programs: a kind of rice containing metamifop
Herbicidal combinations, including primary activity ingredient and second order activity ingredient, the primary activity ingredient include metamifop 5-13
Mass parts, the second order activity ingredient are selected from cyhalofop-butyl 10-20 mass parts, bispyribac-sodium 4-8 mass parts, dichloro quinolinic acid 5-10
Mass parts, halosulfuronmethyl 6-11 mass parts, chlorine fluorine are than fluoroacetic acid 4-12 mass parts.
Preferably, second active constituent can be a kind of active matter: cyhalofop-butyl；It is mixed to be also possible to two kinds of active matters
Close object: bispyribac-sodium and halosulfuronmethyl, cyhalofop-butyl and dichloro quinolinic acid, chlorine fluorine are than fluoroacetic acid and halosulfuronmethyl.
Preferably, the preparation method of the cyhalofop-butyl is 1) etherification reaction: being added and ties up into non-proton organic solvent
Then sour agent, organic base and phase transfer catalyst are added portionwise (R) -2- (4- hydroxyphenoxy) propionic acid, add 3,4- difluoro
Cyanophenyl is heated to 60~90 DEG C, insulation reaction 2~4 hours, removes solvent after reaction, be down to room temperature, be dissolved in water, and uses
Acid for adjusting pH is to 3~5, and solid is precipitated in stirring, and filtering obtains intermediate (R) -2- [4- (2- fluorine-4-nitrile)-phenoxy group]-the third
Acid；Wherein, (R) -2- (4- hydroxyphenoxy) propionic acid and 3, the molar ratio of 4- difluorobenzonilyile are 1:1~1.5；The acid binding agent
For sodium hydroxide, the polar non-solute is N-Methyl pyrrolidone.
2) dehydration esterification: by step 1) obtain intermediate (R) -2- [4- (2- fluorine-4-nitrile)-phenoxy group]-propionic acid and
Reaction vessel is added in n-butanol, dehydrated solvent and bronsted acid catalyst, is heated to reflux, water is divided to separate to anhydrous, and reaction terminates,
Reaction solution is obtained, reaction solution is washed to neutrality, removing solvent obtains cyhalofop-butyl；Wherein the dehydrated solvent refer to not with
The miscible alkanes of water or ketone non-proton organic solvent；The arene non-proton organic solvent is benzene；The alkane
Hydro carbons non-proton organic solvent is hexamethylene；The ketone non-proton organic solvent is butanone.
Preferably, the halosulfuronmethyl preparation method the following steps are included:
Step 1: by 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid ethyl ester, first hydrolysis obtains 1- methyl-under alkaline condition
5- sulfoamido -4- pyrazole carboxylic acid sodium, then acidification neutralization obtains 1- methyl -5- sulfoamido -4- pyrrole in acid condition again
Iminazole acid；
Step 2: the 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid and methylating reagent that step 1 is obtained are in methanol solvate
In, 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid methyl esters is obtained in 40 DEG C~100 DEG C of at a temperature of progress methylation reaction；
Step 3: the 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid methyl esters and chlorination reagent that step 2 is obtained are anti-in chlorination
In the presence of answering solvent and catalyst, the chloro- 1- methyl -5- sulphur of 3- is obtained in 0 DEG C~60 DEG C of at a temperature of progress chlorination reaction
Amide groups -4- pyrazole carboxylic acid methyl esters；
Step 4: the chloro- 1- methyl -5- sulfonamide of the 3- for first obtaining n-butyl isocyanate, triethylene diamine and step 3
Base -4- pyrazole carboxylic acid methyl esters is added in acylation reaction solvent, is then heated to 100 DEG C~160 DEG C addition acylating reagents and is gone forward side by side
Row back flow reaction recycles acylation reaction solvent after reaction, and condensation reaction solvent and 4,6- bis- are added directly into residue
Methoxyl group -2- pyrilamine carries out condensation reaction, obtains halosulfuronmethyl.
Preferably, the preparation method of the dichloro quinolinic acid is 450mL methanol to be first added in reaction flask, under stiring
Dichloro quinolinic acid wet product (folding hundred) 250g and 45g sodium hydroxide is added, temperature rising reflux keeps the temperature 2 hours under reflux, and decompression is steamed
It evaporates, steams methanol, when steaming 350~400ml of methanol, stop distillation, pour out material, it is small to place 24 for the crystallisation by cooling in disk
Shi Hou, drying, obtains dichloro quinolinic acid.
Beneficial effects of the present invention: metamifop can effectively prevent and kill off paddy field main weeds, such as barnyard grass to rice safety
Grass, semen euphorbiae, herba digitariae and herba eleusines indicae are mainly used for transplanting and direct sowing rice field weeding, and metamifop almost leans on cauline leaf
It absorbs, so not having requirement to water, whether there is water or not, wide adaptation range；And dichloroquinoline is added in metamifop
Acid, cyhalofop-butyl, bispyribac-sodium, halosulfuronmethyl, pyrazosulfuron or pyribenzoxim, dichloro quinolinic acid prevent and kill off barnyard grass in paddy field
Special efficacy selective herbicide belongs to hormone-type quinoline carboxylic acid herbicide, and cyhalofop-butyl can only make cauline leaf process, bud pre-treatment without
Effect, mainly prevents and kill off barnyard grass, the gramineae weeds such as semen euphorbiae, bispyribac-sodium effectively prevents and kill off barnyard grass in paddy field and other gramineae weeds, chlorine
Pyrazosulfuron can prevent and kill off part broadleaf weeds to malignant weed rhizome of nutgrass flatsedge special efficacy, and pyrazosulfuron is rapid in weeds plant body
Transfer, inhibits growth, and weeds are gradually dead；Pyribenzoxim has activity of weeding after selective ultra high efficiency bud, weeding before no bud
Activity, it is distinguished for preventing and kill off the various gramineae weeds such as barnyard grass, big fringe amur foxtail, polygonum flaccidum and miscellaneous stroke of effect of broad-leaved；It is used in mixed way,
Further improve the efficiency of weeding.
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment one
The present invention provides a kind of technical solution: a kind of rice weeding composition containing metamifop, including formula as below
Composition: metamifop and cyhalofop-butyl are mixed in a certain ratio composition, and the formula is made of raw material from the following weight:
Metamifop 5-13 mass parts, cyhalofop-butyl 10-20 mass parts.
According to the above technical scheme, the preparation method of cyhalofop-butyl is 1) etherification reaction: into non-proton organic solvent
Acid binding agent, organic base and phase transfer catalyst is added, (R) -2- (4- hydroxyphenoxy) propionic acid is then added portionwise, adds 3,
4- difluorobenzonilyile is heated to 60~90 DEG C, insulation reaction 2~4 hours, removes solvent after reaction, be down to room temperature, add water-soluble
Solution, is adjusted with acid pH to 3~5, stirs, and solid is precipitated, and filtering obtains intermediate (R) -2- [4- (2- fluorine-4-nitrile)-benzene oxygen
Base]-propionic acid；Wherein, (R) -2- (4- hydroxyphenoxy) propionic acid and 3, the molar ratio of 4- difluorobenzonilyile are 1:1~1.5；Described
Acid binding agent is sodium hydroxide, and the polar non-solute is N-Methyl pyrrolidone.
2) dehydration esterification: by step 1) obtain intermediate (R) -2- [4- (2- fluorine-4-nitrile)-phenoxy group]-propionic acid and
Reaction vessel is added in n-butanol, dehydrated solvent and bronsted acid catalyst, is heated to reflux, water is divided to separate to anhydrous, and reaction terminates,
Reaction solution is obtained, reaction solution is washed to neutrality, removing solvent obtains cyhalofop-butyl；Wherein the dehydrated solvent refer to not with
The miscible alkanes of water or ketone non-proton organic solvent；The arene non-proton organic solvent is benzene；The alkane
Hydro carbons non-proton organic solvent is hexamethylene；The ketone non-proton organic solvent is butanone.
Embodiment two
The present invention provides a kind of technical solution, a kind of rice weeding composition containing metamifop, including formula as below
Composition: metamifop, bispyribac-sodium and halosulfuronmethyl are mixed in a certain ratio composition, and the formula is by following parts by weight
Raw material is made: metamifop 5-13 mass parts, bispyribac-sodium 4-8 mass parts, halosulfuronmethyl 6-11 mass parts.
According to the above technical scheme, halosulfuronmethyl preparation method the following steps are included:
Step 1: by 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid ethyl ester, first hydrolysis obtains 1- methyl-under alkaline condition
5- sulfoamido -4- pyrazole carboxylic acid sodium, then acidification neutralization obtains 1- methyl -5- sulfoamido -4- pyrrole in acid condition again
Iminazole acid；
Step 2: the 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid and methylating reagent that step 1 is obtained are in methanol solvate
In, 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid methyl esters is obtained in 40 DEG C~100 DEG C of at a temperature of progress methylation reaction；
Step 3: the 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid methyl esters and chlorination reagent that step 2 is obtained are anti-in chlorination
In the presence of answering solvent and catalyst, the chloro- 1- methyl -5- sulphur of 3- is obtained in 0 DEG C~60 DEG C of at a temperature of progress chlorination reaction
Amide groups -4- pyrazole carboxylic acid methyl esters；
Step 4: the chloro- 1- methyl -5- sulfonamide of the 3- for first obtaining n-butyl isocyanate, triethylene diamine and step 3
Base -4- pyrazole carboxylic acid methyl esters is added in acylation reaction solvent, is then heated to 100 DEG C~160 DEG C addition acylating reagents and is gone forward side by side
Row back flow reaction recycles acylation reaction solvent after reaction, and condensation reaction solvent and 4,6- bis- are added directly into residue
Methoxyl group -2- pyrilamine carries out condensation reaction, obtains halosulfuronmethyl.
Embodiment three
The present invention provides a kind of technical solution, a kind of rice weeding composition containing metamifop, including formula as below
Composition: metamifop, cyhalofop-butyl and dichloro quinolinic acid are mixed in a certain ratio composition, and the formula is by following parts by weight
Raw material be made: metamifop 5-13 mass parts, cyhalofop-butyl 10-20 mass parts, dichloro quinolinic acid 5-10 mass parts.
According to the above technical scheme, the preparation method of cyhalofop-butyl is 1) etherification reaction: into non-proton organic solvent
Acid binding agent, organic base and phase transfer catalyst is added, (R) -2- (4- hydroxyphenoxy) propionic acid is then added portionwise, adds 3,
4- difluorobenzonilyile is heated to 60~90 DEG C, insulation reaction 2~4 hours, removes solvent after reaction, be down to room temperature, add water-soluble
Solution, is adjusted with acid pH to 3~5, stirs, and solid is precipitated, and filtering obtains intermediate (R) -2- [4- (2- fluorine-4-nitrile)-benzene oxygen
Base]-propionic acid；Wherein, (R) -2- (4- hydroxyphenoxy) propionic acid and 3, the molar ratio of 4- difluorobenzonilyile are 1:1~1.5；Described
Acid binding agent is sodium hydroxide, and the polar non-solute is N-Methyl pyrrolidone.
2) dehydration esterification: by step 1) obtain intermediate (R) -2- [4- (2- fluorine-4-nitrile)-phenoxy group]-propionic acid and
Reaction vessel is added in n-butanol, dehydrated solvent and bronsted acid catalyst, is heated to reflux, water is divided to separate to anhydrous, and reaction terminates,
Reaction solution is obtained, reaction solution is washed to neutrality, removing solvent obtains cyhalofop-butyl；Wherein the dehydrated solvent refer to not with
The miscible alkanes of water or ketone non-proton organic solvent；The arene non-proton organic solvent is benzene；The alkane
Hydro carbons non-proton organic solvent is hexamethylene；The ketone non-proton organic solvent is butanone
According to the above technical scheme, the preparation method of dichloro quinolinic acid is that 450mL methanol is first added in reaction flask,
It is added with stirring dichloro quinolinic acid wet product (folding hundred) 250g and 45g sodium hydroxide, temperature rising reflux keeps the temperature 2 hours under reflux, subtracts
Pressure distillation, steams methanol, when steaming 350~400ml of methanol, stops distillation, pours out material, and the crystallisation by cooling in disk is placed
After 24 hours, drying obtains dichloro quinolinic acid.
Example IV
The present invention provides a kind of technical solution, a kind of rice weeding composition containing metamifop, including formula as below
Composition: metamifop, chlorine fluorine are mixed in a certain ratio composition, the formula is by following heavy than fluoroacetic acid and halosulfuronmethyl
The raw material of amount part is made: metamifop 5-13 mass parts, chlorine fluorine is than fluoroacetic acid 4-12 mass parts, halosulfuronmethyl 6-11 mass
Part.
According to the above technical scheme, halosulfuronmethyl preparation method the following steps are included:
Step 1: by 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid ethyl ester, first hydrolysis obtains 1- methyl-under alkaline condition
5- sulfoamido -4- pyrazole carboxylic acid sodium, then acidification neutralization obtains 1- methyl -5- sulfoamido -4- pyrrole in acid condition again
Iminazole acid；
Step 2: the 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid and methylating reagent that step 1 is obtained are in methanol solvate
In, 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid methyl esters is obtained in 40 DEG C~100 DEG C of at a temperature of progress methylation reaction；
Step 3: the 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid methyl esters and chlorination reagent that step 2 is obtained are anti-in chlorination
In the presence of answering solvent and catalyst, the chloro- 1- methyl -5- sulphur of 3- is obtained in 0 DEG C~60 DEG C of at a temperature of progress chlorination reaction
Amide groups -4- pyrazole carboxylic acid methyl esters；
Step 4: the chloro- 1- methyl -5- sulfonamide of the 3- for first obtaining n-butyl isocyanate, triethylene diamine and step 3
Base -4- pyrazole carboxylic acid methyl esters is added in acylation reaction solvent, is then heated to 100 DEG C~160 DEG C addition acylating reagents and is gone forward side by side
Row back flow reaction recycles acylation reaction solvent after reaction, and condensation reaction solvent and 4,6- bis- are added directly into residue
Methoxyl group -2- pyrilamine carries out condensation reaction, obtains halosulfuronmethyl.
Based on above-mentioned, it is an advantage of the current invention that it is mainly miscellaneous can effectively to prevent and kill off paddy field to rice safety for metamifop
Grass is mainly used for transplanting and direct sowing rice field weeding such as barnyard grass, semen euphorbiae, herba digitariae and herba eleusines indicae.
Finally, it should be noted that being not intended to restrict the invention the foregoing is merely preferred embodiment of the invention, to the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, for those skilled in the art, still can be with
It modifies the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.It is all
Within the spirit and principles in the present invention, any modification, equivalent replacement, improvement and so on should be included in guarantor of the invention
Within the scope of shield.
Claims (5)
1. a kind of rice weeding composition containing metamifop, it is characterised in that: including primary activity ingredient and second order activity
Ingredient, the primary activity ingredient include metamifop 5-13 mass parts, and the second order activity ingredient is selected from cyhalofop-butyl 10-
20 mass parts, bispyribac-sodium 4-8 mass parts, dichloro quinolinic acid 5-10 mass parts, halosulfuronmethyl 6-11 mass parts, chlorine fluorine are than oxygen second
Sour 4-12 mass parts.
2. a kind of rice weeding composition containing metamifop according to claim 1, it is characterised in that: described second
Active constituent can be a kind of active matter: cyhalofop-butyl；It is also possible to two kinds of active mixtures: bispyribac-sodium and the phonetic sulphur of chlorine pyrrole
Grand, cyhalofop-butyl and dichloro quinolinic acid, chlorine fluorine are than fluoroacetic acid and halosulfuronmethyl.
3. a kind of rice weeding composition containing metamifop according to claim 1, it is characterised in that: the cyanogen fluorine
The preparation method of careless ester is 1) etherification reaction: acid binding agent, organic base and phase transfer catalysis (PTC) being added into non-proton organic solvent
Then agent is added portionwise (R) -2- (4- hydroxyphenoxy) propionic acid, adds 3,4- difluorobenzonilyile, be heated to 60~90 DEG C, protects
Temperature reaction 2~4 hours, removes solvent after reaction, is down to room temperature, be dissolved in water, be adjusted with acid pH to 3~5, stirs, analysis
Solid out, filtering, obtains intermediate (R) -2- [4- (2- fluorine-4-nitrile)-phenoxy group]-propionic acid；Wherein, (R) -2- (4- hydroxyl
Phenoxy group) molar ratio of propionic acid and 3,4- difluorobenzonilyile is 1:1~1.5；The acid binding agent is sodium hydroxide, and the polarity is non-
Proton solvent is N-Methyl pyrrolidone.
2) dehydration esterification: intermediate (R) -2- [4- (2- fluorine-4-nitrile)-phenoxy group]-propionic acid that step 1) is obtained and positive fourth
Reaction vessel is added in alcohol, dehydrated solvent and bronsted acid catalyst, is heated to reflux, water is divided to separate to anhydrous, reaction terminates, and obtains
Reaction solution is washed to neutrality by reaction solution, and removing solvent obtains cyhalofop-butyl；Wherein the dehydrated solvent refers to not mixed with water
Molten alkanes or ketone non-proton organic solvent；The arene non-proton organic solvent is benzene；The alkanes
Non-proton organic solvent is hexamethylene；The ketone non-proton organic solvent is butanone.
4. a kind of rice weeding composition containing metamifop according to claim 1, it is characterised in that: the chlorine pyrrole
The preparation method of Sulfometuron Methyl the following steps are included:
Step 1: by 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid ethyl ester, first hydrolysis obtains 1- methyl -5- sulphur under alkaline condition
Amide groups -4- pyrazole carboxylic acid sodium, then acidification neutralization obtains 1- methyl -5- sulfoamido -4- pyrazoles first in acid condition again
Acid；
Step 2: the 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid and methylating reagent that step 1 is obtained in methanol solvate,
1- methyl -5- sulfoamido -4- pyrazole carboxylic acid methyl esters is obtained in 40 DEG C~100 DEG C of at a temperature of progress methylation reaction；
Step 3: the 1- methyl -5- sulfoamido -4- pyrazole carboxylic acid methyl esters and chlorination reagent that step 2 is obtained are molten in chlorination reaction
In the presence of agent and catalyst, the chloro- 1- methyl -5- sulfonamide of 3- is obtained in 0 DEG C~60 DEG C of at a temperature of progress chlorination reaction
Base -4- pyrazole carboxylic acid methyl esters；
Step 4: the chloro- 1- methyl -5- sulfoamido-of the 3- for first 3. obtaining n-butyl isocyanate, triethylene diamine and step
4- pyrazole carboxylic acid methyl esters is added in acylation reaction solvent, is then heated to 100 DEG C~160 DEG C addition acylating reagents and is returned
Stream reaction, recycles acylation reaction solvent after reaction, and condensation reaction solvent and 4,6- dimethoxy are added directly into residue
Base -2- pyrilamine carries out condensation reaction, obtains halosulfuronmethyl.
5. a kind of rice weeding composition containing metamifop according to claim 1, it is characterised in that: the dichloro
The preparation method of quinolinic acid is that 450mL methanol is first added in reaction flask, and dichloro quinolinic acid wet product (folding hundred) is added under stiring
250g and 45g sodium hydroxide, temperature rising reflux keep the temperature 2 hours under reflux, and vacuum distillation steams methanol, when steaming methanol 350
When~400ml, stop distillation, pour out material, the crystallisation by cooling in disk, after placing 24 hours, drying obtains dichloro quinolinic acid.
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