CN106632122B - Benzoxazoles benzene oxycarboxylic acid amides compound and preparation method thereof - Google Patents
Benzoxazoles benzene oxycarboxylic acid amides compound and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 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
- A01N43/74—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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
The invention discloses a kind of benzoxazoles benzene oxycarboxylic acid amides compounds and preparation method thereof.Wherein compound is the compound or its pharmaceutically acceptable salt of structure shown in formula (E).In terms of the compound of the present invention or its pharmaceutically acceptable salt can be applicable to crops weeding, especially apply in terms of preventing and kill off gramineae weed, broadleaved herb or nutgrass flatsedge.The compound of the present invention, without any adverse effect, is not required to that safener is added, dosage is small, and herbicidal spectrum is wide, and herbicidal effect is good, is more advantageous in agricultural production and uses to the normal growth of rice class crops.
Description
Technical field
The invention belongs to pesticide fields, and in particular to a kind of benzoxazoles benzene oxycarboxylic acid amides compound and its preparation side
Method.
Background technique
Herbicide (herbicide), which refers to, can make weeds that withered medicament, also known as herbicide thoroughly or selectively occur,
To eliminate or inhibit a substance of plant growth.World Herbicide development is gradually steady, and main development is efficient, less toxic, wide
Spectrum, the kind of low dosage, the small disposable treatment agent of environmental pollution are increasingly becoming mainstream.Common kind is organic compound
It is miscellaneous to 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 for object
The noxious plants such as grass, miscellaneous filling, miscellaneous tree.At present the common herbicide of paddy field have metamifop, cyhalofop-butyl, pyrazosulfuron,
Oxadiazon etc..
Metamifop (metamifop) belongs to aromatic oxygen-phenoxy group propionates class herbicide.Its mechanism of action is to inhibit second
Acyl coenzyme A carboxylase, effective ingredient, which needs to reach target in plant, can play herbicide effect.Solvent and surfactant will
It each serves as softening blade face wax layer and opens the effect of plant stomata, enter effective ingredient in plant and play a role.With
There is blade face and move back green in susceptible weeds in several days after medicine, inhibit growth, some weeds dry up for 2 weeks after administration, or even death.
Actual pesticide experience have shown that, repeat and it is single-minded apply a kind of reactive compound and carry out controlling weeds will lead in many cases
Cause the fast selective of weeds.
As other existing classes of herbicides, the herbicide for paddy field such as metamifop have dosage big, for a long time
Using being also easy to produce drug resistance, and it is easy to produce pesticide residue, part herbicide has phytotoxicity, needs using safener or other are auxiliary
The disadvantages of material, is unfavorable for a large amount of long-time services of herbicide, it is therefore necessary to the further more excellent herbicide of research and development effect.
Summary of the invention
The purpose of the present invention is on the basis of existing technology, provide a kind of structure novel to have crops herbicide effect
Benzoxazoles benzene oxycarboxylic acid amides compound.
It is a further object of the present invention to provide a kind of preparation methods of above-mentioned benzoxazoles benzene oxycarboxylic acid amides compound.
The third object of the present invention is to provide a kind of above-mentioned benzoxazoles benzene oxycarboxylic acid amides compound and removes in crops
The purposes of careless aspect.
The purpose of the present invention can be achieved by the following measures:
A kind of benzoxazoles benzene oxycarboxylic acid amides compound, i.e., the compound of structure shown in formula (E) or its pharmaceutically may be used
The salt of receiving,
Wherein,
R1Selected from hydrogen or C1~4Alkyl；
R2Selected from hydrogen, C1~4Alkyl or following group:
X1、X2、X3Or X4It is independently hydrogen or halogen.
In a preferred embodiment, R1Selected from hydrogen, methyl or ethyl.
In a preferred embodiment, R2Selected from hydrogen, methyl, ethyl, formula (I) group or formula (II) group, X1、X2、X3Or X4
It is independently hydrogen, Cl, F or Br.
In a kind of more preferable scheme, the compound of the present invention or its pharmaceutically acceptable salt, wherein compound is selected from:
The present invention provides a kind of preparation method of the compound of structure shown in formula (E), reaction routes are as follows:
In a preferred embodiment, the preparation method of the compound of structure shown in formula (E) includes the following steps:
Step 1: compound A is added catalyst with compound B under alkaline condition and is reacted to obtain etherate；
Step 2: compound C is reacted to obtain acyl chlorides with acylating reagent；
Step 3: compound D is reacted to obtain compound E with amine under alkaline condition.
Each step is described in further details below:
Step 1: catalyst is added in etherification reaction, the synthesis of compound C, compound A and compound B under alkaline condition
It is reacted to obtain etherate.
The molar ratio of compound A and B can be 1:1~1:1.5, preferably 1:1.1；Alkali may is that sodium carbonate, carbonic acid
Potassium；Catalyst is intended to transfer catalyst, comprising: tetrabutylammonium bromide, benzyltriethylammoinium chloride；Reaction dissolvent can be DMF,
Dichloroethanes, toluene；Reaction temperature can be 45~90 DEG C, preferably at 55~60 DEG C.
Step 2: acyl chlorides synthesis, the synthesis of compound D, compound C are reacted to obtain acyl chlorides with acylating reagent.
The molar ratio of compound C and acylating reagent can be 1:1~1:1.5, preferably 1:1.2；Acylating reagent can be with
It is: thionyl chloride, oxalyl chloride.Reaction dissolvent can be methylene chloride, dichloroethanes, toluene；Reaction temperature can be 40~80
DEG C, preferably at 45~55 DEG C.
Step 3: amide synthesis, compound D are reacted to obtain compound E with amine under alkaline condition.
The molar ratio of compound D and amine can be 1:1~1:2；Amine can be ammonia, monomethyl amine, dimethylamine, formula (III) change
Close object or formula (IV) compound；；Alkali can be sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, preferably sodium bicarbonate；Reaction
Solvent can be water；Reaction temperature can be -5 DEG C~15 DEG C, preferably 0~5 DEG C；A small amount of triethylamine conduct can be added in reaction
Catalyst, to improve reaction efficiency.
Each group is as defined above in preparation method.
Invention includes a kind of Herbicidal combinations, it is with the compound or its pharmaceutically acceptable salt of structure shown in formula (E)
For active constituent or main active, it is aided with auxiliary agent pesticide-acceptable.
Dosage form pesticide-acceptable can be made by effective component and insecticides adjuvant in composition of the invention jointly.
The mass content of effective component can be 2~95%, preferably 5~80% in composition of the invention.
Suitable auxiliary agent can be solid or liquid, they are usually common substance during formulation, such as day
Right or regenerated minerals, solvent, dispersing agent, wetting agent, adhesive, thickener, adhesive or fertilizer.
The method of administration of the present composition includes the aerial part that composition of the invention is used for plant growth, especially
It is leaf portion or blade face.The frequency and amount of application of application depend on the biology and weather life condition of pathogen.It can be by plant
Growth place, such as rice field is soaked with the liquid preparation of composition, or composition is applied in soil in solid form,
As in granular form (soil application), composition can enter in plant (systemic action) through plant root by soil.
These compositions can only include that active constituent (also known as effective component) is administered, can also with additive or
Auxiliary agent mixes together, therefore composition of the invention can be prepared into various dosage forms, for example, wettable powder, suspending agent,
Dispersible oil-suspending agent, aqueous emulsion, missible oil, water dispersible granules etc..According to the property of these compositions and application composition institute
Purpose to be achieved and ambient conditions can choose composition to be sprayed, atomizing, dust, broadcast sowing or sprinkle the side poured or the like
Method application.
Composition of the invention can be prepared into various dosage forms by known method, such as can by effective component with help
Agent can uniformly mix together with surfactant when needing, grind, be prepared into required agent such as solvent, solid carrier
Type.
Above-mentioned solvent can be selected from aromatic hydrocarbon, preferably contain 8-12 carbon atom, such as xylene mixture or substituted benzene, phthalein
Esters of gallic acid, such as two octanoic acid of Dibutyl phthalate or phthalandione, fat hydrocarbon, such as thiacyclohexane or paraffin, the ether of pure and mild ethylene glycol and they
And ester, such as ethyl alcohol, ethylene glycol, ethylene glycol monomethyl；Ketone, such as cyclohexanone, highly polar solvent, such as N- methyl -2- pyrrolidines
Ketone, dimethyl sulfoxide or dimethylformamide and vegetable oil or vegetable oil, such as soybean oil.
Above-mentioned solid carrier, such as usually natural mineral fillers, such as talcum, kaolinite for pulvis and dispersible agent
Soil, montmorillonite or atlapulgite.In order to manage the physical property of composition, polymolecularity silicic acid or polymolecularity can also be added
Adsorpting polymerization object carrier, such as granulated adsorptive carriers or non-adsorbed carrier, suitable granulated adsorptive carriers are porous types, it is such as floating
Stone, bentonite or bentonite；Suitable non-adsorbed carrier such as calcite or sand.Further, it is possible to use a large amount of inorganic in nature or having
The prefabricated material to granulate of machine property is as carrier, especially dolomite.
The chemical property of effective component in composition according to the present invention, suitable surfactant are sulfomethylated lignin
Acid, naphthalene sulfonic acids, phenolsulfonic acid, alkali salt or amine salt, alkylaryl sulfonates, alkyl sulfate, alkylsulfonate, fat
Alcohol sulfate, fatty acid and sulphated fatty alcohol glycol ether, there are also the condensation product of sulfonated naphthalene and naphthalene derivatives and formaldehyde, naphthalene or
The condensation product of naphthalene sulfonic acids and phenol and formaldehyde, NONIN HS 240, ethoxylated isooctyl-phenol, octyl phenol, nonyl phenol,
Alkylaryl polyglycol ether, tributyl benzene polyglycol ether, three stearyl phenyl polyglycol ethers, alkyl aryl polyether alcohol,
Ethoxylated castor oil, polyoxyethylene alkyl ether, ethylene oxide condensation product, ethoxylation polyoxypropylene, laurel acid polyethylene glycol
Ether acetal, sorbitol ester, lignin sulfite waste liquor and methylcellulose.
C in the present invention1~4Alkyl refers to the linear or branched saturated hydrocarbon base containing 1~4 carbon atom, specific optional
From methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl.
Halogen in the present invention refers to fluorine, chlorine, bromine or iodine.
Pharmaceutically acceptable salt in the present invention indicates to retain those of biological effectiveness and property of parent compound
Salt.This kind of salt includes:
(1) it is obtained by the free alkali of parent compound with inorganic acid or reacting for organic acid, inorganic acid packet with acid at salt
Include hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, metaphosphoric acid, sulfuric acid, sulfurous acid and perchloric acid etc., organic acid include acetic acid, trifluoroacetic acid,
Propionic acid, acrylic acid, caproic acid, pentamethylene propionic acid, glycolic acid, pyruvic acid, oxalic acid, (D) or (L) malic acid, fumaric acid, maleic acid,
Benzoic acid, hydroxybenzoic acid, gamma-hydroxybutyric acid, methoxy benzoic acid, phthalic acid, methanesulfonic acid, ethanesulfonic acid, naphthalene -1- sulphur
Acid, naphthalene-2-sulfonic acid, p-methyl benzenesulfonic acid, salicylic acid, tartaric acid, citric acid, lactic acid, cinnamic acid, dodecyl sulphate, gluconic acid,
Glutamic acid, aspartic acid, stearic acid, mandelic acid, succinic acid or malonic acid etc..
(2) acid proton being present in parent compound is replaced or given birth to organic base ligand compound by metal ion
At salt, metal ion such as alkali metal ion, alkaline-earth metal ions or aluminium ion, organic bases for example ethanol amine, diethanol amine,
Triethanolamine, tromethamine, N-METHYL-ALPHA-L-GLUCOSAMINE, quinine etc..
Pharmaceutical composition in the present invention refer to by one or more of compound in the present invention or its pharmaceutically may be used
Salt, solvate, hydrate or the prodrug of receiving and other chemical component, such as pharmaceutically acceptable carrier, mixing.Drug
The purpose of composition is to promote administration to the process of animal.
In terms of the compound of the present invention or its pharmaceutically acceptable salt can be applicable to crops weeding, especially apply
In terms of preventing and kill off gramineae weed, broadleaved herb or nutgrass flatsedge.The compound of the present invention is to the normal growth of rice class crops without any
Adverse effect is not required to that safener is added, and dosage is small, and herbicidal spectrum is wide, and herbicidal effect is good, is more advantageous in agricultural production and uses.
Specific embodiment
The invention will be further described with reference to embodiments.But the scope of the invention is not limited to following embodiments.
The compound that embodiment 1-12 synthesizes is as shown in the table.
Embodiment 1: the synthesis of compound 1
500gDMF, investment 100g compound A, 113.6g potassium carbonate and the 5g tetrabutyl are added into 1000mL four-hole boiling flask
Ammonium bromide is warming up to 60 DEG C, and mixed solution of the 113.5g compound B in 50gDMF is added dropwise, controls 55~60 DEG C of temperature, is added dropwise
Terminating, reacts about 2 hours, reaction terminates, and adds in 1000g water, it with salt acid for adjusting pH to 7~8, stirs 1 hour, filtering, Gu
Body is etherate, drying.
500g dichloroethanes is added into 1000ml four-hole bottle, 100g compound C is added, is warming up to 50 DEG C, 42.8g is added dropwise
Thionyl chloride controls 50~55 DEG C of temperature, and completion of dropwise addition is reacted 1 hour, and reaction terminates, and acyl chloride reaction liquid is spare.To 1000ml
Addition 75g water, 24.48g25% ammonium hydroxide, 38.16g sodium carbonate, 5g triethylamine are cooled to 0~5 DEG C, and acyl chloride reaction liquid, control is added dropwise
5~10 DEG C of temperature processed, completion of dropwise addition is reacted 1 hour, and reaction terminates, layering, and organic phase precipitation obtains crude product, and 200g first is added
Alcohol is warming up to 50 DEG C of dissolutions, is cooled to 5 DEG C, and solid is precipitated, and is obtained by filtration product, white solid, yield: 72%, content:
95%.
Embodiment 2: the synthesis of compound 2
Acyl chloride reaction liquid is the same as embodiment 1.
75g water is added to 1000ml, 27.95g40% monomethylamine aqueous solution, 38.16g sodium carbonate, 5g triethylamine is cooled to
0~5 DEG C, acyl chloride reaction liquid is added dropwise, controls 5~10 DEG C of temperature, completion of dropwise addition is reacted 1 hour, and reaction terminates, layering, organic phase
Precipitation obtains crude product, and 200g methanol is added and is warming up to 50 DEG C of dissolutions, is cooled to 5 DEG C, solid is precipitated, product is obtained by filtration, white
Solid, yield: 71%, content: 95%.
Embodiment 3: the synthesis of compound 3
Acyl chloride reaction liquid is the same as embodiment 1.
75g water is added to 1000ml, 40.57g40% dimethylamine agueous solution, 38.16g sodium carbonate, 5g triethylamine is cooled to
0~5 DEG C, acyl chloride reaction liquid is added dropwise, controls 5~10 DEG C of temperature, completion of dropwise addition is reacted 1 hour, and reaction terminates, layering, organic phase
Precipitation obtains crude product, and 200g methanol is added and is warming up to 50 DEG C of dissolutions, is cooled to 5 DEG C, solid is precipitated, product is obtained by filtration, white
Solid, yield: 71%, content: 95%.
Embodiment 4: the synthesis of compound 4
Acyl chloride reaction liquid is the same as embodiment 1.
75g water is added to 1000ml, the chloro- 2-aminopyridine of 51.33g3-, 38.16g sodium carbonate, 5g triethylamine is cooled to 0
~5 DEG C, acyl chloride reaction liquid is added dropwise, controls 5~10 DEG C of temperature, completion of dropwise addition is reacted 1 hour, and reaction terminates, layering, organic phase
Precipitation obtains crude product, and 200g methanol is added and is warming up to 50 DEG C of dissolutions, is cooled to 5 DEG C, solid is precipitated, product is obtained by filtration, white
Solid, yield: 73%, content: 95%.
Embodiment 5: the synthesis of compound 5
Acyl chloride reaction liquid is the same as embodiment 1.
75g water is added to 1000ml, and 83.95g pyrazole amine, 38.16g sodium carbonate, 5g triethylamine is cooled to 0~5 DEG C, drop
Add acyl chloride reaction liquid, control 5~10 DEG C of temperature, completion of dropwise addition is reacted 1 hour, and reaction terminates, and layering, organic phase precipitation obtains
Crude product is added 200g methanol and is warming up to 50 DEG C of dissolutions, be cooled to 5 DEG C, solid is precipitated, and product is obtained by filtration, and white solid is received
Rate: 73%, content: 95%.
Embodiment 6: the synthesis of compound 6
Acyl chloride reaction liquid is the same as embodiment 1.
75g water is added to 1000ml, the fluoro- 2-aminopyridine of 40.36g3-, 38.16g sodium carbonate, 5g triethylamine is cooled to 0
~5 DEG C, acyl chloride reaction liquid is added dropwise, controls 5~10 DEG C of temperature, completion of dropwise addition is reacted 1 hour, and reaction terminates, layering, organic phase
Precipitation obtains crude product, and 200g methanol is added and is warming up to 50 DEG C of dissolutions, is cooled to 5 DEG C, solid is precipitated, product is obtained by filtration, white
Solid, yield: 75%, content: 95%.
Embodiment 7: the synthesis of compound 7
Acyl chloride reaction liquid is the same as embodiment 1.
To 1000ml be added 75g water, the fluoro- 2- methylamino pyridine of 51.88g3,5- bis-, 38.16g sodium carbonate, 5g triethylamine,
It is cooled to 0~5 DEG C, acyl chloride reaction liquid is added dropwise, controls 5~10 DEG C of temperature, completion of dropwise addition is reacted 1 hour, and reaction terminates, layering,
Organic phase precipitation obtains crude product, and 200g methanol is added and is warming up to 50 DEG C of dissolutions, is cooled to 5 DEG C, solid is precipitated, production is obtained by filtration
Product, white solid, yield: 71%, content: 95%.
Embodiment 8: the synthesis of compound 8
Acyl chloride reaction liquid is the same as embodiment 1.
To 1000ml be added 75g water, the chloro- 2- methylamino pyridine of the fluoro- 5- of 57.81g3-, 38.16g sodium carbonate, 5g triethylamine,
It is cooled to 0~5 DEG C, acyl chloride reaction liquid is added dropwise, controls 5~10 DEG C of temperature, completion of dropwise addition is reacted 1 hour, and reaction terminates, layering,
Organic phase precipitation obtains crude product, and 200g methanol is added and is warming up to 50 DEG C of dissolutions, is cooled to 5 DEG C, solid is precipitated, production is obtained by filtration
Product, white solid, yield: 72%, content: 95%.
Embodiment 9: the synthesis of compound 9
Acyl chloride reaction liquid is the same as embodiment 1.
75g water, the fluoro- 2- methylamino pyridine of 45.41g3-, 38.16g sodium carbonate, 5g triethylamine, cooling is added to 1000ml
To 0~5 DEG C, acyl chloride reaction liquid is added dropwise, controls 5~10 DEG C of temperature, completion of dropwise addition is reacted 1 hour, and reaction terminates, and layering is organic
Phase precipitation obtains crude product, and 200g methanol is added and is warming up to 50 DEG C of dissolutions, is cooled to 5 DEG C, solid is precipitated, product is obtained by filtration, white
Color solid, yield: 74%, content: 95%.
Embodiment 10: the synthesis of compound 10
Acyl chloride reaction liquid is the same as embodiment 1.
75g water, the chloro- 2-aminopyridine of 58.68g3,5- bis-, 38.16g sodium carbonate, 5g triethylamine, drop is added to 1000ml
Acyl chloride reaction liquid is added dropwise to 0~5 DEG C in temperature, controls 5~10 DEG C of temperature, and completion of dropwise addition is reacted 1 hour, and reaction terminates, and layering has
Machine phase precipitation obtains crude product, and 200g methanol is added and is warming up to 50 DEG C of dissolutions, is cooled to 5 DEG C, solid is precipitated, product is obtained by filtration,
White solid, yield: 73%, content: 95%.
Embodiment 11: the synthesis of compound 11
Acyl chloride reaction liquid is the same as embodiment 1.
To 1000ml be added 75g water, the chloro- 2- methylamino pyridine of 63.73g3,5- bis-, 38.16g sodium carbonate, 5g triethylamine,
It is cooled to 0~5 DEG C, acyl chloride reaction liquid is added dropwise, controls 5~10 DEG C of temperature, completion of dropwise addition is reacted 1 hour, and reaction terminates, layering,
Organic phase precipitation obtains crude product, and 200g methanol is added and is warming up to 50 DEG C of dissolutions, is cooled to 5 DEG C, solid is precipitated, production is obtained by filtration
Product, white solid, yield: 74%, content: 95%.
Embodiment 12: the synthesis of compound 12
Acyl chloride reaction liquid is the same as embodiment 1.
75g water is added to 1000ml, the chloro- 2-aminopyridine of 46.78g3-, 38.16g sodium carbonate, 5g triethylamine is cooled to 0
~5 DEG C, acyl chloride reaction liquid is added dropwise, controls 5~10 DEG C of temperature, completion of dropwise addition is reacted 1 hour, and reaction terminates, layering, organic phase
Precipitation obtains crude product, and 200g methanol is added and is warming up to 50 DEG C of dissolutions, is cooled to 5 DEG C, solid is precipitated, product is obtained by filtration, white
Solid, yield: 76%, content: 95%.
Embodiment 13-24:15% wettable powder
Compound 1 15%, sodium lignin sulfonate 6%, alkylsulfonate 5%, white carbon black 8%, kaolin complements to
100%.
Active constituent and various auxiliary agents and filler etc. are sufficiently mixed in proportion, is made and implements after ultra-fine pulverizer disintegrating
The wettable powder of example 13.
Respectively with the compound 1 in compound 2-12 replacement wettable powder, embodiment 14-24 can be respectively obtained.
Embodiment 25-36:35% wettable powder
Compound 1 35%, bentonite 3%, alkylsulfonate 3%, white carbon black 5%, diatomite complements to 100%.
Active constituent and various auxiliary agents and filler etc. are sufficiently mixed in proportion, is made and implements after ultra-fine pulverizer disintegrating
The wettable powder of example 25.
Respectively with the compound 1 in compound 2-12 replacement wettable powder, embodiment 26-36 can be respectively obtained.
Embodiment 37-48:65% wettable powder
Compound 1 65%, aliphatic alcohol sulfate 6%, calcite 3%, kaolin 7%, precipitated calcium carbonate complements to
100%.
Active constituent and various auxiliary agents and filler etc. are sufficiently mixed in proportion, is made and implements after ultra-fine pulverizer disintegrating
The wettable powder of example 37.
Respectively with the compound 1 in compound 2-12 replacement wettable powder, embodiment 38-48 can be respectively obtained.
Embodiment 49-60:20% water dispersible granules
Compound 1 20%, sodium benzoate 5%, alkyl polyoxyethanyl ether sulfonate 5%, fatty mercaptan acid ammonium 4%, kaolinite
Soil complements to 100%.
Active constituent, auxiliary agent and filler are mixed according to the formula uniformly, through air-flow crushing at wettable powder, then plus
Enter a certain amount of water mixing extrusion granulation, the water dispersible granules product of embodiment 49 is made after dry screening.
Respectively with the compound 1 in compound 2-12 replacement water dispersible granules, embodiment 50-60 can be respectively obtained.
Embodiment 61-72:10% missible oil
Compound 1 10%, propylene glycol 15%, alkylaryl polyglycol ether 10%, toluene complements to 100%.
Respectively with the compound 1 in compound 2-12 replacement missible oil, embodiment 62-72 can be respectively obtained.
Embodiment 73: drug effect verification test
It is respectively 10% metamifop EC (Korea Spro of 10% missible oil and reference substance of the embodiment of the present application 61-72 for agent of having a try
Autumn is good).Each processing is as follows:
Every processing is repeated 2 times, totally 52 cells.Every plot area 20m2, random alignment.
In direct sowing of rice Tanaka, sprayer cauline leaf is used to the rice field of the barnyard grass containing different leaf ages, semen euphorbiae and herba digitariae
It is spraying, and temporally record preventive effect.Weeding result see the table below.
For the application leaf age of barnyard grass 2-4 leaf, processing 3,5,7,9,11,13,15,17,19,21,23 is in dosage 50g
a.i./hm2Under, after medicine 10d to the preventive effect of barnyard grass, semen euphorbiae and herba digitariae after 93% or more, medicine 20d to barnyard grass, a thousand pieces of gold
The preventive effect of son and herba digitariae is 95% or more；Processing 4,6,8,10,12,14,16,18,20,22,24 dosage 90g a.i./
hm2Under, after medicine 10d to the preventive effect of barnyard grass, semen euphorbiae and herba digitariae after 95% or more, medicine 20d to barnyard grass, semen euphorbiae and horse
The preventive effect of Tang is 97% or more.
Above each processing has obvious exception during being showed no paddy growth relative to blank control.
Claims (11)
1. compound or its pharmaceutically acceptable salt, wherein compound is selected from:
2. a kind of preparation method of compound described in claim 1, it is characterised in that its reaction route are as follows:
Wherein the compound of structure shown in formula E is compound described in claim 1.
3. preparation method according to claim 2, it is characterised in that this method comprises the following steps:
Step 1: compound A is added catalyst with compound B under alkaline condition and is reacted to obtain etherate；
Step 2: compound C is reacted to obtain acyl chlorides with acylating reagent；
Step 3: compound D is reacted to obtain compound E with amine under alkaline condition.
4. preparation method according to claim 3, it is characterised in that in step 1, the molar ratio of compound A and B are 1:
1~1:1.5, the alkali of alkaline condition are sodium carbonate or potassium carbonate, and the catalyst is tetrabutylammonium bromide or benzyl triethyl ammonium chlorine
Change ammonium, reaction dissolvent is DMF, dichloroethanes or toluene, and reaction temperature is 45~90 DEG C；In step 2, compound C and acylation
The molar ratio of reagent is 1:1~1:1.5, and the acylating reagent is thionyl chloride or oxalyl chloride, and reaction dissolvent is methylene chloride, two
Chloroethanes or toluene, reaction temperature are 40~80 DEG C.
5. the preparation method according to claim 4, it is characterised in that in step 1, reaction temperature is 55~60 DEG C；?
In step 2, reaction temperature is 45~55 DEG C.
6. the preparation method according to claim 4, it is characterised in that in step 3, the molar ratio of compound D and amine is
1:1~1:2；The amine is selected from ammonium hydroxide, monomethyl amine, dimethylamine or formula (IV) compound；The alkali of alkaline condition is sodium carbonate, carbonic acid
Potassium, sodium bicarbonate or triethylamine, reaction dissolvent are water；Reaction temperature is -5 DEG C~15 DEG C；
Wherein, X1、X2、X3Or X4It is independently hydrogen or halogen.
7. preparation method according to claim 6, it is characterised in that in step 3, reaction temperature is 0~5 DEG C.
8. preparation method according to claim 6, it is characterised in that in step 3, triethylamine is further added in reaction
As catalyst.
9. a kind of Herbicidal combinations, it is characterised in that it is with compound described in claim 1 or its pharmaceutically acceptable salt
For active constituent or main active, it is aided with auxiliary agent pesticide-acceptable.
10. the purposes of compound described in claim 1 or its pharmaceutically acceptable salt in terms of crops weeding.
11. compound described in claim 1 or its pharmaceutically acceptable salt are in terms of crops prevent and kill off gramineae weed
Purposes.
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| CN107382896B (en) * | 2017-08-02 | 2019-07-09 | 张建华 | Benzoxazoles -2- oxygroup phenoxy group propionyl imine compound and its synthetic method and application |
| EP4209486A1 (en) * | 2022-01-07 | 2023-07-12 | Adama Agan Ltd. | Process for the preparation of aryloxyphenoxypropionic acid derivatives in a non polar solvent with a tertiary amine catalyst |
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| CN101743219A (en) * | 2007-07-03 | 2010-06-16 | 株式会社庆农 | Optically active (R)-aryloxypropionic acid amides and herbicidal composition comprising same |
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| JPH0217187A (en) * | 1988-07-06 | 1990-01-22 | Kumiai Chem Ind Co Ltd | Phenoxypropionamide derivative and herbicide |
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| US4130413A (en) * | 1976-09-10 | 1978-12-19 | Hoechst Aktiengesellschaft | Heterocyclic phenyl ethers and herbicides containing same |
| CN101743219A (en) * | 2007-07-03 | 2010-06-16 | 株式会社庆农 | Optically active (R)-aryloxypropionic acid amides and herbicidal composition comprising same |
| CN103086995B (en) * | 2013-02-01 | 2014-08-13 | 湖南大学 | 2-[4-(benzoxazole-2-oxygroup) phenoxy] alkylamide and application thereof |
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