CN105541821B - Oxazine assimilation arylpyrazole type compound and its Ultrasonic Radiation synthetic method and application - Google Patents
Oxazine assimilation arylpyrazole type compound and its Ultrasonic Radiation synthetic method and application Download PDFInfo
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- CN105541821B CN105541821B CN201610058200.1A CN201610058200A CN105541821B CN 105541821 B CN105541821 B CN 105541821B CN 201610058200 A CN201610058200 A CN 201610058200A CN 105541821 B CN105541821 B CN 105541821B
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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
- C07D413/04—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 directly linked by a ring-member-to-ring-member 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
- 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
- A01N43/86—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 one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
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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
- 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
- A01N47/02—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 no bond to a nitrogen atom
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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
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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Abstract
The invention belongs to technical field of organic synthesis, specifically disclose one kind 1 (2,6 dichloro-4,4s (trifluoromethyl) phenyl) 5 oxazine ketone group 3 cyano 1H pyrazoles type compounds and method that the type compound is synthesized using ultrasonic irradiation, additionally provide the application of the type compound.The present invention synthesizes 1 (2,6 dichloro-4,4s (trifluoromethyl) phenyl) 5 oxazine ketone group, 3 cyano 1H pyrazoles type compounds using ultrasonic irradiation, and synthesis material cost is relatively low, and reaction condition is mild, and easy to operate, yield is higher；1 (2 be prepared, 6 dichloro-4,4s (trifluoromethyl) phenyl) 5 oxazine ketone group 3 cyano 1H pyrazoles types compound have good bioactivity, high activity is particularly shown in terms of the prevention of agricultural, gardening, flowers and sanitary insect pest, therefore with very big development and application values.
Description
Technical field
The present invention relates to technical field of organic synthesis more particularly to a kind of 1- (2,6- bis- chloro- 4- (trifluoromethyl) phenyl)-
5- oxazines ketone group -3- cyano -1H- pyrazoles type compounds and the method that the type compound is synthesized using ultrasonic irradiation, also
Provide the application of the type compound.
Background technology
In recent ten years, heterocyclic compound causes the concern of pesticide circle personage due to its efficient bioactivity, becomes
The hot spot of current pesticide research exploitation.In various heterocycle compounds, oxazine ketone compounds have extensive bioactivity
With relatively low bio-toxicity, especially there is good effect to cutting weeds.Oxazine ketone compounds are absorbability translocated herbicide,
Inhibit the growth of sensitive plant meristematic cell in a manner of being different from other herbicides, it is low, suitable with active ingredient usage amount
The features such as dispenser phase is long, the lasting period is long, toxic side effect is small, and drug resistance is small and highly selective.Arylpyrazoles compound has wide
General bioactivity is one of primary structure of novel pesticide research in recent years.The height shown due to arylpyrazoles compound
The diversity of effect, low toxicity and structure, thus with boundless research and development prospect.Arylpyrazoles pesticide is a kind of
The chloride channel adjusted by γ-aminobutyric acid disturbs the access of chlorion, destroys the activity of pest normal central nervous system, and
Cause being overexcited for insect nerves and muscles in the case of sufficient dosage, insect is caused to be fainted from fear, dead novel pesticide.
Due to the interaction special with GABA receptor, arylpyrazole type compound plays an important role of unique machine to pest
System, can effectively prevent the pest resistant to common insecticides.Guidance type insecticide is research hotspot in the ascendant at present, i.e.,
The pesticide of accumulation can be oriented to wound location caused by insect pest position or insect pest in plant, research emphasis is pesticide
It is translocatable in the in vivo orientation of plant, mainly using plant endogenous active material as homing device, after it is made to be coupled with pesticide
It is acted on by the transfer protein of homing device and conjugates is loaded into plant, and transported to pest and cause harm through plant phloem
Position.
The content of the invention
By having good effect to cutting weeds in oxazinone type compound, arylpyrazole type compound has pest
Unique mechanism of action, oxazine ketone groups is combined with arylpyrazole type compound, making one kind can cut weeds
The multi-functional pesticide of energy desinsection again.
Based on considerations above, applicant's design has synthesized a series of multi-functional pesticide 1- (2,6- bis- with guide function
Chloro- 4- (trifluoromethyl) phenyl) -5- oxazine ketone group -3- cyano -1H- pyrazoles type compounds (II).Draw into oxazine ketone group, pass through
Inhibit the growth of sensitive plant meristematic cell, have to grassy weed and broad leaved weed and certain prevent and kill off activity.Oxazine class chemical combination
Object has good guiding role, oxazine ketone group and arylpyrazole type as plant endogenous active material as homing device
Conjugates are loaded into plant by the transfer protein effect of homing device after closing object coupling, and are transported through plant phloem
Cause harm position to pest, make the pesticide of the environment-friendly high-efficiency with guide function.You Yu oxazine compounds can be in the sun
It can slowly voluntarily photodissociation under light irradiation so that 1- (2,6- bis- chloro- 4- (trifluoromethyl) phenyl) -5- oxazinone -3- cyano -
1H- pyrazoles type compound (II) types pesticide spraying for a period of time after can the slow photodissociation under natural environment, decomposition product is to environment
It is harmless, it is a kind of pesticide of green low-residual.1- (2,6- bis- chloro- 4- (trifluoromethyl) phenyl) -5- oxazinone -3- cyano -1H-
Pyrazoles type compound (II) type pesticide is in prevention Orthoptera, Thysanoptera, Homoptera, Heteroptera, Lepidoptera, coleoptera, Diptera
There is good application in class pest, there are very big development and application values in agricultural, gardening, flowers and health etc..
The twenties in last century, American scientist Richard and Loomis have found that ultrasonic wave can accelerate to chemically react first,
But fail the attention for causing chemists for a long time.Until the popularization and development of the mid-80 large power supersonic equipment, surpass
Application of the sound wave in chemical industry rapidly develops, and generates new cross discipline --- phonochemistry.In recent years, have both at home and abroad
Acoustochemical research and academic exchange Showed Very Brisk are closed, with acoustochemical development, ultrasonic wave has been widely used in aoxidizing
Reaction, reduction reaction, addition reaction, substitution reaction, condensation reaction, hydrolysis etc. are almost related to each neck of organic chemistry
Domain.In addition, ultrasonic wave is subject in organic synthesis when having many advantages, such as mild reaction condition, easy to operate, cleanliness without any pollution
Extensive concern.
Ultrasonic irradiation refers to answering in container, using different solvents as reaction medium, by being applied to reaction vessel
Add ultrasonic wave, the active function groups of reaction are more easily broken off, reduce reaction activity, so that reaction is easier to make for.
Ultrasonic irradiation has the characteristics that efficient, highly selective, mild condition, easy to operate, it can also relatively easily be synthesized
Conventional method is difficult to the object synthesized.As far as we know, ultrasonic technology should be in oxazine assimilation arylpyrazole type compound
Synthesis so far still without document report.
More than inventive concept is based on, of the invention first is designed to provide a kind of 1- (2,6- bis- chloro- 4- (fluoroforms
Base) phenyl) -5- oxazinone -3- cyano -1H- pyrazoles type compounds (II), shown in structural formula such as general formula (II)：
In general formula (II), R1Any one in following group：- H ,-G (G represents Cl, Br or I), And-S-CnH2n+1(n=1,2,3 or 4)；
Preferably, the R1Any one in following group：- H ,-G (G represents Cl, Br or I),And
Optimal, the R1For
In general formula (II), R2Selected from any one of following group：PhenylP- methoxyl group-phenylP-nitro-benzene base2,3- dichlorophenylsThe fluoro- 3- of 2-
Bromo- phenyl2,6- 3,5-dimethylphenyls3,5- 3,5-dimethylphenyls
Optimal, R2For phenyl；
In general formula (II), the R3Any one in following a few class groups：Halogen group, saturated alkane base are satisfied
With cycloalkyl group, substituted or unsubstituted phenyl, naphthalene, anthryl, phenanthryl, furfuryl group, pyrrole radicals, thienyl, pyridyl group, quinolyl
And indyl；
Specifically, the R3Any one in following group：Hydrogen H-, fluorine F-, chlorine Cl-, bromine Br-, iodine I-, methyl
CH3-, ethyl CH3CH2-, propyl CH3CH2CH2-, butyl CH3CH2CH2CH2-, amyl CH3CH2CH2CH2CH2-, chloromethyl
ClCH2-, chloroethyl ClCH2CH2-, dichloromethyl Cl2CH-, trichloromethyl CCl3-, cyclopropylCyclopentaCyclohexylPhenylP- methoxyl group-phenylP- nitre
Base-phenyl2,3- dichlorophenylsThe bromo- phenyl of the fluoro- 3- of 2-2,6-
3,5-dimethylphenyl3,5- 3,5-dimethylphenyls2,4,6- trifluorophenyls2,
3,4- trihydroxy phenyl2,4,5- trimethoxyphenyls1- naphthalenes2- hydroxyl -1- naphthalenesFuryl5- methyl -2- furyls2- pyrrole radicals3- pyrrole radicals2- thienyls2- pyridyl groupsThe bromo- 3- pyridyl groups of 2-Bis- chloro- 3- pyridyl groups of 2,6-3- quinolyls3- indyls
Preferably, the R3Any one in following group：Hydrogen H-, fluorine F-, chlorine Cl-, bromine Br-, methyl CH3-、
Ethyl CH3CH2-, propyl CH3CH2CH2-, butyl CH3CH2CH2CH2-, amyl CH3CH2CH2CH2CH2-, chloromethyl ClCH2-, chlorine
Ethyl ClCH2CH2-, dichloromethyl Cl2CH-, trichloromethyl CCl3-, amylCyclohexylBenzene
BaseP- methoxyl group-phenylP-nitro-benzene base2,3- dichloro-benzenes
Base1- naphthalenes2- hydroxyl -1- naphthalenesFuryl5- first
Base -2- furyls2- pyrrole radicals3- pyrrole radicals2- thienyls
2- pyridyl groupsThe bromo- 3- pyridyl groups of 2-Bis- chloro- 3- pyridyl groups of 2,6-3-
Quinolyl3- indyls
Optimal, the R3Any one in following group：Hydrogen H-, chlorine Cl-, methyl CH3-, trichloromethyl
CCl3-, cyclohexylPhenylP- methoxyl group-phenylFuryl
Second object of the present invention is the method for providing a kind of composite structure formula compound as shown in general formula (II), this
Method is efficient, environmentally friendly, easy, at low cost.
Second purpose to realize the present invention, the technical solution designed by the present invention are：
A kind of method of composite structure formula compound as shown in general formula (II)：By 3- cyano -5- imino groups -1- (2,6- bis-
Chloro- 4- trifluoromethyls) -1H- pyrazoles type compounds and carboxylic acid halidesIt is added in organic solvent, in ultrasonic amplitude
It penetrates under (constant power 150W) and is prepared when 15~90 DEG C of reaction 0.5-10 are small.
Its synthetic route is as follows：
The compoundMiddle X be Cl, Br or I, R1、R2、R3It is defined as described above；
The organic solvent is selected from cyclic ethers class, arene, chain ethers, amine solvent and esters；
Wherein, cyclic ether solvents include tetrahydrofuran, dioxane；
Aromatic hydrocarbon solvent includes toluene, dimethylbenzene, mesitylene, chlorobenzene, bromobenzene；
Chain ethers solvent includes ethylene glycol diethyl ether, butyl glycol ether, diethylene glycol monomethyl ether, diethylene glycol diformazan
Ether, propylene glycol monomethyl ether, dihydroxypropane single-ether；
Amine solvent includes N,N-dimethylformamide, DMAC N,N' dimethyl acetamide；
Esters solvent includes ethyl acetate, ethyl acetoacetate, ethyl propionate.
The organic solvent is preferably any one in toluene, tetrahydrofuran, ethylene glycol diethyl ether；
The organic solvent most preferably tetrahydrofuran.
Preferably, the reaction temperature is 40~70 DEG C, when the reaction time is 1-9 small；
Optimal, the reaction temperature is 50~60 DEG C, when the reaction time is 5~6 small；
3- cyano -5- imino groups -1- (2,6- bis- in composite structure formula method of compound as shown in general formula (II)
Chloro- 4- trifluoromethyls) -1H- pyrazoles type compounds andThe molar ratio of reactant is 1:2.
3- cyano -5- imino groups -1- (2,6- dichlor-4-trifluoromethyls the phenyl) -1H- pyrazoles type compounds are by following
Method synthesizes：(I) it is prepared by formula (III) compound and formula (IV) compound in toluene solvant by being heated to reflux；
R1、R2It is defined as described above；
Third object of the present invention is that providing structural formula compound as shown in general formula (II) is preventing and kill off grassy weed
With the application in terms of broad leaved weed.
The 3rd purpose to realize the present invention, 1- (2,6- bis- chloro- 4- (trifluoromethyl) benzene that the present invention is prepared
Base) -5- oxazine ketone group -3- cyano -1H- pyrazoles types compound for preventing and kill off grassy weed and broad leaved weed, achieves preferably
Control effect.
Weeds described here include but not limited to this：
Grassy weed includes：Wild oat, bromegrass, Triticum tauschii, amur foxtail, barnyard grass, annual bluegrass, herba setariae viridis grass.
Broad leaved weed includes：Procumbent Falsepimpernel, false loosestrife, grass dragon, sesbania.
Fourth object of the present invention is that provide structural formula compound as shown in general formula (II) (wraps in prevention harmful insect
Include Orthoptera, Thysanoptera, Homoptera, Heteroptera, Lepidoptera, coleoptera and Diptera), the application in terms of mite pest.
The 4th purpose to realize the present invention, 1- (2,6- bis- chloro- 4- (trifluoromethyl) benzene that the present invention is prepared
Base) -5- oxazine ketone group -3- cyano -1H- pyrazoles types compound is for preventing Orthoptera, Thysanoptera, Homoptera, Heteroptera, squama wing
Mesh, coleoptera, Diptera harmful insect, mite pest, achieve preferable control effect.
Harmful organism described here include but not limited to this：
Harmful insect includes：Orthoptera such as blattaria, Thysanoptera such as cotton thrips, rice thrips, melon thrips, Homoptera such as black tail leaf
Cicada, Fei Wind, aphid；Heteroptera such as harlequin bug；Lepidoptera for example oriental armyworm, prodenia litura, diamondback moth, beet armyworm,
Mosquito powder exigua, cabbage caterpillar；Coleoptera such as rice flatworm；Diptera such as yellow-fever mosquito, culex.
Mite pest includes：Acarina such as cotton spider mites, Jie-Li enzyme-SQ, T.urticae Koch.
Compared with prior art, general formula (II) compound and its Ultrasonic Radiation synthetic method with it is the advantages of application and beneficial
Effect is as follows：
1st, general formula (II) compound, which not only has above-mentioned all kinds of weeds, preferably prevents and kill off activity, and can effectively kill above-mentioned
Each class pest is a kind of multi-functional low-residue green pesticide to beneficial organism low toxicity.
2nd, using Ultrasonic Radiation method is easy to operate, safety, yield are high, the time is short, energy conservation and environmental protection reaction condition is mild,
Easy to operate, cleanliness without any pollution；
3rd, 1- (2,6- bis- chloro- 4- (trifluoromethyl) phenyl) -5- oxazine ketone group -3- cyano -1H- pyrazoles that the present invention synthesizes
Type compound (II), synthesis material cost is relatively low, and reaction condition is mild, and easy to operate, yield is higher, the 1- that is prepared (2,
6- bis- chloro- 4- (trifluoromethyl) phenyl) -5- oxazine ketone group -3- cyano -1H- pyrazoles type compounds (II) have good removal of impurities
Grass and insecticidal bioactivity, particularly show high work in terms of agricultural, gardening, flowers and health are cut weeds with the prevention and control of plant diseases, pest control
Property, therefore with very big development and application values.
Description of the drawings
Fig. 1 is that the compound 1-11 that embodiment 18 is tested compares the control effect of moths attracted by lamplight larva figure (expression compound
Target a, b represents processing mass concentration for 80,160mg/L respectively behind code name number).
Specific embodiment
The product and its synthetic method of the present invention and application are further described below by specific embodiment, but this
A little specific embodiments are not in any way limit the scope of the present invention.
Raw material used in following embodiment is known compound, is commercially available or can be with known in the art
Method synthesizes.
3- cyano -5- phenyliminos -1- (2,6- dichlor-4-trifluoromethyls phenyl) -1H- in example 1 below -11
Pyrazoles type compound is that applicant makes by oneself according to the method described in the content of the invention.
Embodiment 1,1- (2,6- dichlor-4-trifluoromethyls-phenyl) -5- (6- methyl -2- phenyl -4- ketone -4H-1,3- Evil
Piperazine base) -3- cyano -4- trifluoromethyl sulphinyl base -1H- pyrazoles (compound 1) synthesis
Generation compound 1 reaction equation be：
50mL THF, 4.50g3- cyano -4- trifluoromethyl sulphinyl base -5- phenyl imido are added in 100mL single port bottles
Base -1- (2,6- dichlor-4-trifluoromethyl phenyl) -1H- pyrazoles, 1g molecular sieves, add 1.60g chloroacetic chlorides, reaction temperature is
50-60 DEG C, single port bottle is put into reaction, reaction time 6h in ultrasonic sink (constant power 150W).Rear pillar is completed in reaction
Chromatography (ethyl acetate：Petroleum ether=1：4) 5.33g compounds 1 are obtained.Yield：87.5%.mp:185.5~188.0 DEG C of .IR
(KBr,cm-1):3228(N-H),3080(CH2- H), 2249 (- CN), 1723 (- C=O), 1606 (pyrazole ring skeletal vibrations),
1534 and 1486 (phenyl ring skeletal vibrations), 1312 (C-F), 882 (aromatic ring C-H)1HNMR(CDCl3,400MHz)δ:7.90(s,
1H, Ar-H), 7.80 (s, 1H, Ar-H), 7.76 (s, 1H, Ar-H), 7.74 (s, 1H, Ar-H), 7.70 (s, 1H, Ar-H), 7.60
(s, 1H, Ar-H), 7.67 (s, 1H, Ar-H), 5.32 (s, H, C-H), 3.32 (s, H, C-H), 1.10 (q, 3H, CH2-H)。
Embodiment 2,1- (2,6- dichlor-4-trifluoromethyls-phenyl) -5- (6- methyl -2- phenyl -4- ketone -4H-1,3- Evil
Piperazine base) -3- cyano -1H- pyrazoles (compound 2) synthesis
Generation compound 2 reaction equation be：
50mL toluene, 4.50g3- cyano -5- phenyliminos -1- (bis- chloro- 4- tri- of 2,6- are added in 100mL single port bottles
Trifluoromethylphenyl) -1H- pyrazoles, 1g molecular sieves, add 1.60g chloroacetic chlorides, reaction temperature is 30-40 DEG C, and single port bottle is put into
Reaction, reaction time 6h in ultrasonic sink (constant power 150W).Column chromatography for separation (ethyl acetate after the completion of reaction：Stone
Oily ether=1：4) 4.89g compounds 2 are obtained.Yield：80.2%.mp:150.6~154.1 DEG C of .IR (KBr, cm-1):3254(N-H),
3080 (C-H), 2252 (- CN), 1724 (- C=O), 1606 (pyrazole ring skeletal vibrations), 1530 and 1399 (phenyl ring skeleton shakes
It is dynamic), 1314 (C-F), 884 (aromatic ring C-H)1HNMR(CDCl3,400MHz)δ:7.90(s,1H,Ar-H),7.80(s,1H,Ar-
H), 7.76 (s, 1H, Ar-H), 7.74 (s, 1H, Ar-H), 7.70 (s, 1H, Ar-H), 7.60 (s, 1H, Ar-H), 7.67 (s, 1H,
Ar-H), 5.32 (s, H, C-H), 3.32 (s, H, C-H), 1.10 (q, 3H, CH2-H)。
Embodiment 3,1- (2,6- dichlor-4-trifluoromethyls-phenyl) -5- (6- methyl -2- phenyl -4- ketone -4H-1,3- Evil
Piperazine base) the bromo- 1H- pyrazoles (compound 3) of -3- cyano -4- synthesis
Generation compound 3 reaction equation be：
20mL ethylene glycol diethyl ethers, the bromo- 5- phenyliminos -1- of 4.40g3- cyano -4- are added in 100mL single port bottles
(2,6- dichlor-4-trifluoromethyl phenyl) -1H- pyrazoles, 1g molecular sieves, add 1.60g chloroacetic chlorides, reaction temperature 50-60
DEG C, single port bottle is put into reaction, reaction time 6h in ultrasonic sink (constant power 150W).Column chromatography point after the completion of reaction
From (ethyl acetate：Petroleum ether=1：4) 4.99g compounds 3 are obtained.Yield：83.2%.mp:205.6~208.1 DEG C of .IR (KBr,
cm-1):3231 (N-H), 3051 (C-H), 2254 (- CN), 1736 (- C=O), 1611 (pyrazole ring skeletal vibrations), 1512 Hes
1367 (phenyl ring skeletal vibrations), 1314 (C-F), 885 (aromatic ring C-H)1HNMR(CDCl3,400MHz)δ:7.90(s,1H,Ar-
H), 7.80 (s, 1H, Ar-H), 7.76 (s, 1H, Ar-H), 7.74 (s, 1H, Ar-H), 7.70 (s, 1H, Ar-H), 7.60 (s, 1H,
Ar-H), 7.67 (s, 1H, Ar-H), 5.32 (s, H, C-H), 3.32 (s, H, C-H), 1.10 (q, 3H, CH2-H)。
Embodiment 4,1- (2,6- dichlor-4-trifluoromethyls-phenyl) -5- (6- methyl -2- phenyl -4- ketone -4H-1,3- Evil
Piperazine base) -3- cyano -4- ethylsulfinyl -1H- pyrazoles (compound 4) synthesis
Generation compound 4 reaction equation be：
In 100mL single port bottles add in 20mL THF, 4.60g3- cyano -4- ethylsulfinyl -5- phenyliminos -
1- (2,6- dichlor-4-trifluoromethyl phenyl) -1H- pyrazoles, 1g molecular sieves, add 1.60g chloroacetic chlorides, reaction temperature 80-
90 DEG C, single port bottle is put into reaction, reaction time 6h in ultrasonic sink (constant power 150W).Column chromatography after the completion of reaction
Separate (ethyl acetate：Petroleum ether=1：4) 4.97g compounds 4 are obtained.Yield：80.2%.mp:172.6~174.1 DEG C of .IR
(KBr,cm-1):3243 (N-H), 3066 (C-H), 2253 (- CN), 1729 (- C=O), 1608 (pyrazole ring skeletal vibrations), 1532
With 1378 (phenyl ring skeletal vibrations), 1314 (C-F), 884 (aromatic ring C-H)1HNMR(CDCl3,400MHz)δ:7.90(s,1H,Ar-
H), 7.80 (s, 1H, Ar-H), 7.76 (s, 1H, Ar-H), 7.74 (s, 1H, Ar-H), 7.70 (s, 1H, Ar-H), 7.60 (s, 1H,
Ar-H), 7.67 (s, 1H, Ar-H), 5.32 (s, H, C-H), 3.32 (s, H, C-H), 1.10 (q, 3H, CH2-H)。
Embodiment 5,1- (2,6- dichlor-4-trifluoromethyls-phenyl) -5- (5- methyl -6- ethyl -2- phenyl -4- ketone -4H-
1,3- oxazinyls) -3- cyano -4- trifluoromethyl sulphinyl base -1H- pyrazoles (compound 5) synthesis
Generation compound 5 reaction equation be：
50mL THF, 4.50g3- cyano -4- trifluoromethyl sulphinyl base -5- phenyl imido are added in 100mL single port bottles
Base -1- (2,6- dichlor-4-trifluoromethyl phenyl) -1H- pyrazoles, 1g molecular sieves, add 2.20g propionyl chlorides, reaction temperature is
15-25 DEG C, single port bottle is put into reaction, reaction time 10h in ultrasonic sink (constant power 150W).Rear pillar is completed in reaction
Chromatography (ethyl acetate：Petroleum ether=1：4) 5.64g compounds 5 are obtained.Yield：84.3%.mp:195.7~198.6 DEG C of .IR
(KBr,cm-1):3451 (N-H), 3091 (C-H), 2253 (- CN), 1722 (- C=O), 1649 (pyrazole ring skeletal vibrations), 1530
With 1396 (phenyl ring skeletal vibrations), 1313 (C-F), 887 (aromatic ring C-H)1HNMR(CDCl3, 400MHz) and δ:7.90(s,1H,Ar-
H), 7.80 (s, 1H, Ar-H), 7.76 (s, 1H, Ar-H), 7.74 (s, 1H, Ar-H), 7.70 (s, 1H, Ar-H), 7.60 (s, 1H,
Ar-H), 7.67 (s, 1H, Ar-H), 5.32 (s, H, C-H), 3.32 (s, H, C-H), 1.10 (q, 3H, CH2-H)。
Embodiment 6,1- (2,6- dichlor-4-trifluoromethyls-phenyl) -5- (the chloro- 6- chloromethyls -2- phenyl -4- ketone -4H- of 5-
1,3- oxazinyls) -3- cyano -4- trifluoromethyl sulphinyl base -1H- pyrazoles (compound 6) synthesis
Generation compound 6 reaction equation be：
50mL THF, 4.50g3- cyano -4- trifluoromethyl sulphinyl base -5- phenyl imido are added in 100mL single port bottles
Base -1- (2,6- dichlor-4-trifluoromethyl phenyl) -1H- pyrazoles, 1g molecular sieves, add 2.20g chloracetyl chlorides, reaction temperature
For 50-60 DEG C, single port bottle is put into reaction, reaction time 6h in ultrasonic sink (constant power 150W).After the completion of reaction
Column chromatography for separation (ethyl acetate：Petroleum ether=1：4) 5.44g compounds 6 are obtained.Yield：71.2%.mp:181.2~183.6 DEG C
.IR(KBr,cm-1):3451 (N-H), 3082 (C-H), 2256 (- CN), 1736 (- C=O), 1628 (pyrazole ring skeletal vibrations),
1531 and 1378 (phenyl ring skeletal vibrations), 1314 (C-F), 856 (aromatic ring C-H)1HNMR(CDCl3, 400MHz):7.90(s,1H,
Ar-H), 7.80 (s, 1H, Ar-H), 7.76 (s, 1H, Ar-H), 7.74 (s, 1H, Ar-H), 7.70 (s, 1H, Ar-H), 7.60 (s,
1H, Ar-H), 7.67 (s, 1H, Ar-H), 5.32 (s, H, C-H), 3.32 (s, H, C-H), 1.10 (q, 3H, CH2-H)。
Embodiment 7,1- (2,6- dichlor-4-trifluoromethyls-phenyl) -5- (5- trichloromethyl -6- trichloroethyl -2- phenyl -
4- ketone -4H-1,3- oxazinyls) -3- cyano -4- trifluoromethyl sulphinyl base -1H- pyrazoles (compound 7) synthesis
Generation compound 7 reaction equation be：
50mL THF, 4.50g3- cyano -4- trifluoromethyl sulphinyl base -5- phenyl imido are added in 100mL single port bottles
Base -1- (2,6- dichlor-4-trifluoromethyl phenyl) -1H- pyrazoles, 1g molecular sieves add tri- chlorpromazine chlorides of 3.00g, reaction temperature
It spends for 50-60 DEG C, single port bottle is put into reaction, reaction time 6h in ultrasonic sink (constant power 150W).Reaction is completed
Column chromatography for separation (ethyl acetate afterwards：Petroleum ether=1：4) 5.64g compounds 7 are obtained.Yield：75.2%.mp:255.2~257.6
The structural formula of DEG C compound is confirmed through infrared detected with nuclear-magnetism.
Embodiment 8,1- (2,6- dichlor-4-trifluoromethyls-phenyl) -5- (5- cyclohexyl -6- first cyclohexyl -2- phenyl 4-
Ketone -4H-1,3- oxazinyls) -3- cyano -4- trifluoromethyl sulphinyl base -1H- pyrazoles (compound 8) synthesis
Generation compound 8 reaction equation be：
50mL THF, 4.50g3- cyano -4- trifluoromethyl sulphinyl base -5- phenyl imido are added in 100mL single port bottles
Base -1- (2,6- dichlor-4-trifluoromethyl phenyl) -1H- pyrazoles, 1g molecular sieves, add 2.80g2- cyclohexyl chloroacetic chlorides, instead
Temperature is answered as 50-60 DEG C, single port bottle is put into reaction, reaction time 6h in ultrasonic sink (constant power 150W).Reaction
Column chromatography for separation (ethyl acetate after finishing：Petroleum ether=1：4) 5.92g compounds 8 are obtained.Yield：81.2%.mp:191.6~
The structural formula of 193.7 DEG C of compounds is confirmed through infrared detected with nuclear-magnetism.
Embodiment 9,1- (2,6- dichlor-4-trifluoromethyls-phenyl) -5- (5- phenyl -6- tolyl -2- phenyl -4- ketone -
4H-1,3- oxazinyls) -3- cyano -4- trifluoromethyl sulphinyl base -1H- pyrazoles (compound 9) synthesis
Generation compound 9 reaction equation be：
50mL THF, 4.50g3- cyano -4- trifluoromethyl sulphinyl base -5- phenyl imido are added in 100mL single port bottles
Base -1- (2,6- dichlor-4-trifluoromethyl phenyl) -1H- pyrazoles, 1g molecular sieves, add 2.60g phenyllacetyl chlorides, reaction temperature
For 50-60 DEG C, single port bottle is put into reaction, reaction time 6h in ultrasonic sink (constant power 150W).After the completion of reaction
Column chromatography for separation (ethyl acetate：Petroleum ether=1：4) 5.48g compounds 9 are obtained.Yield：77.2%.mp:171.2~173.6 DEG C of
The structural formula of the compound is confirmed through infrared detected with nuclear-magnetism.
Embodiment 10, (5- p-methoxyphenyl -6- first is to methoxyl group by 1- (2,6- dichlor-4-trifluoromethyls-phenyl) -5-
Phenyl -2- phenyl -4- ketone -4H-1,3- oxazinyls) -3- cyano -4- trifluoromethyl sulphinyl base -1H- pyrazoles (compound 10)
Synthesis
Generation compound 10 reaction equation be：
50mL THF, 4.50g3- cyano -4- trifluoromethyl sulphinyl base -5- phenyl imido are added in 100mL single port bottles
Base -1- (2,6- dichlor-4-trifluoromethyl phenyl) -1H- pyrazoles, 1g molecular sieves, add 3.00g acetanisole chlorine,
Reaction temperature is 50-60 DEG C, and single port bottle is put into reaction, reaction time 6h in ultrasonic sink (constant power 150W).Instead
Column chromatography for separation (ethyl acetate after the completion of answering：Petroleum ether=1：4) 6.34g compounds 10 are obtained.Yield：84.6%.mp:192.3
The structural formula of~194.6 DEG C of compounds is confirmed through infrared detected with nuclear-magnetism.
Embodiment 11,1- (2,6- dichlor-4-trifluoromethyls-phenyl) -5- (5- furyl -6- first furyl -2- phenyl -
4- ketone -4H-1,3- oxazinyls) -3- cyano -4- trifluoromethyl sulphinyl base -1H- pyrazoles (compound 11) synthesis
Generation compound 11 reaction equation be：
50mL THF, 4.50g3- cyano -4- trifluoromethyl sulphinyl base -5- phenyl imido are added in 100mL single port bottles
Base -1- (2,6- dichlor-4-trifluoromethyl phenyl) -1H- pyrazoles, 1g molecular sieves add 2.50g furans chloroacetic chlorides, reaction temperature
It spends for 50-60 DEG C, single port bottle is put into reaction, reaction time 6h in ultrasonic sink (constant power 150W).Reaction is completed
Column chromatography for separation (ethyl acetate afterwards：Petroleum ether=1：4) 5.23g compounds 11 are obtained.Yield：74.8%.mp:154.2~157.6
The structural formula of DEG C compound is confirmed through infrared detected with nuclear-magnetism.
Comparative example 12,1- (2,6- dichlor-4-trifluoromethyls-phenyl) -5- (6- methyl -4- ketone -4H-1,3- oxazines
Base) -3- cyano -4- trifluoromethyl sulphinyl base -1H- pyrazoles (compound 1) synthesis
Separately or concurrently change temperature, reaction time and the mode of heating of embodiment 1, other are same as Example 1, prepare
Compound 1, the result for preparing result and embodiment 1 are listed in the table below in 1 simultaneously：
The synthesis of compound 1 and yield under 1. different condition of table
From comparative example 1~3 three group, comparative example, which can be seen that temperature and time, influences yield, under normal pressure using ultrasound
Yield of the ripple processing generally than not using ultrasonication significantly improves.
Embodiment 13,1- (2,6- bis- chloro- 4- (trifluoromethyl) phenyl) -5- oxazinone -3- cyano -1H- pyrazoles type chemical combination
The preparation of object experiment pesticide
The formulations of pesticide prepared by the present embodiment are suspending agent, and alleged below " gross mass " refers to " prepared suspending agent
Gross mass ".
The surfactant naphthalenesulfonic acid-formaldehyde condensate for first accounting for gross mass 5% by 11 parts is diluted in 11 parts and accounts for total matter respectively
It measures in 5% suitable antifreeze glycol or glycerine, and is slowly added into the water for accounting for gross mass 25% into the solution respectively,
Sequentially added respectively into 11 groups of solution under quick stirring account for compound 1~11 prepared by the embodiment 1-11 of gross mass 25% and
The auxiliary agent (preservative benzoic acid, antifoaming agent organosilicon and thickener xanthans) of gross mass 5% is accounted for, it is ground after adding
Mill, is eventually adding the water for accounting for gross mass 35%.The suspending agent being prepared is added water into dilution and prepares compound 1-11 respectively
Concentration is the dilute suspension agent of 40,80,100,160 and 500mg/L.That is 11 compound groups, every group of 5 concentration gradients.
Prepared dilute suspension agent is ready for use on following embodiment.
Embodiment 14, the biological evaluation to barnyard grass
Using the dilute suspension agent of the 100mg/L concentration of embodiment 13, rice soil 1kg is filled in culture tank, water is added to protect
It is wet.30, the sowing barnyard grass seed per tank, depth 5mm grows several days at room temperature, when growing into for 2 leaf phase, is added dropwise respectively per tank
The dilute suspension agent of the 100mg/L concentration of 10~15 drop compounds 1~11, by observing the death rate two days later, experiment repeats 3
Secondary, results are averaged.Correlated results is shown in Table 6.
The active testing of 2 1~11 pair of barnyard grass of compound of table
| Compound | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
| The death rate (%) | 93.3 | 90.0 | 83.3 | 86.3 | 93.3 | 86.3 | 90.0 | 93.3 | 96.6 | 93.3 | 90.0 |
1~11 barnyard grass of compound has preferable herbicidal efficacy as can be known from Table 2.
Embodiment 15, the biological evaluation to Procumbent Falsepimpernel
Using the dilute suspension agent of the 100mg/L concentration of embodiment 13, in area 10m2Small-scale test Tanaka sow footpath between fields
It serves seed, each 100, experimental plot sowing Procumbent Falsepimpernel seed is embedded in the soil layer of 0.5cm depths, water drenching is after hot-house culture.It is raw
When growing to for 4 leaf phase, the dilute suspension of the 100mg/L concentration of 500mL compounds 1~11 is uniformly sprayed in each small-scale test field respectively
Agent, by observing the death rate two days later, experiment is repeated 3 times, and results are averaged.The opposite blank control of activity in percentage,
It is divided into A, B, C, D level Four, the death rate 100%~90% is A grades, and the death rate 90%~70% is B grades, the death rate 70%~50%
For C grades, the death rate 0%~50% is D grades.Test result is shown in Table 3.
3 compound 1~11 of table is when test concentrations are 100mg/L to the activity of Procumbent Falsepimpernel
| Compound | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
| Active rank | A | B | B | B | B | A | A | A | A | A | A |
Embodiment 16, the biological evaluation to rice green leafhopper
The dilute suspension agent of the 100mg/L concentration of each compound prepared using embodiment 13 is chosen two core rice seedlings and immersed
It takes out and dries in liquid, after 5 seconds, be placed in Boiling tube, often 20 plants of pipe, if then introducing 5 age of rice green leafhopper of 20 or more
Worm, the wrapping of nozzle white yarn cloth are placed under room temperature, 24 it is small when after check survival and dead borer population.Experiment is repeated 3 times.
Results are averaged.Activity in percentage, is divided into A, B, C, D level Four compared with blank control, and the death rate 100%~90% is
A grades, the death rate 90%~70% is B grades, and the death rate 70%~50% is C grades, and the death rate 0%~50% is D grades.Test result
It is shown in Table 4.
4 compound 1~11 of table is when test concentrations are 100mg/L to the activity of rice green leafhopper
| Compound | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
| Active rank | B | A | A | B | B | A | A | B | B | A | A |
Embodiment 17, the biological evaluation to oriental armyworm
The dilute suspension agent of the 100mg/L concentration of each compound prepared using embodiment 13, every group of 20 first 3 age of selection east
Square mythimna separata and 11 one cun of long maize leafs are put in culture dish, and the 100mL of each compound is added dropwise in every group of culture dish respectively
Above-mentioned suspending agent, after drying move into greenhouse in normally raise, 24 it is small when after statistics survival and death toll.Experiment is repeated 3 times, as a result
It is averaged.Activity in percentage, is divided into A, B, C, D level Four compared with blank control, and the death rate 100%~90% is A grades,
The death rate 90%~70% is B grades, and the death rate 70%~50% is C grades, and the death rate 0%~50% is D grades.Test result is shown in Table
5。
5 compound 1~11 of table is when test concentrations are 100mg/L to the activity of oriental armyworm
| Compound | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
| Active rank | B | A | A | A | B | A | B | A | A | A | A |
Embodiment 18, the biological evaluation to moths attracted by lamplight larva
The 80 of each compound prepared using embodiment 13, the dilute suspension agent of 160mg/L concentration, using Soybean Leaves as examination
Material.20 groups of experiment point every time, every group of 50 fresh Soybean Leaves, every group of 100 first 4 age moths attracted by lamplight larva of placement connect worm band leaf and carry out
Spray, experimental period is for 24 hours.If 3 repetitions are tested, results are averaged, separately sets blank control, to investigate larval mortality.
Using 4 age moths attracted by lamplight larvas as test worm, the 80 of compound 1-11,160mg/L mass concentrations are respectively adopted and carry out to 4 age lamps
The biological activity test of moth larvae, the test result for arranging gained are shown in Fig. 1.
As can be seen from Figure 1：1- (2,6- bis- chloro- 4- (trifluoromethyl) phenyl) -5- oxazinone -3- cyano prepared by the present invention -
1H- pyrazoles type compounds have the bioactivity of moths attracted by lamplight larva a preferable effect, and same medicament with use quality it is dense
Degree improves, and the death rate of moths attracted by lamplight larva is increased therewith.Compound 2, when mass concentration is 160mg/L, moths attracted by lamplight larva is dead
Rate highest is died, more than 70%；And compound 5 is then influenced maximum by mass concentration, when concentration doubles, the death rate increases near
Ten times.
Embodiment 19, the biological evaluation to cotton spider mites
The dilute suspension agent of the 500mg/L concentration of each compound prepared using embodiment 13, is existed using slide infusion process
2h is placed under the indoor environment of 25 ± 1 DEG C of temperature for examination cotton spider mites on slide double faced adhesive tape, is rejected dead and inactive
Individual records mite number living.One end with mite is immersed to the dilute suspension agent of the 500mg/L concentration of each compound prepared in advance
In, it is taken out after 5s, blots mite body and its liquid extra around with blotting paper rapidly.25 ± 1 DEG C of temperature, illumination (L: D=16h:
3d is cultivated under 8h), per 1 result of inspection for 24 hours.Touch its body with writing brush, using mite enough motionless person as death.Each compound
Dilute suspension agent experiment is repeated 3 times, and results are averaged.The opposite blank control of activity in percentage, is divided into A, B, C, D tetra-
Grade, the death rate 100%~90% are A grades, and the death rate 90%~70% is B grades, and the death rate 70%~50% is C grades, the death rate
0%~50% is D grades.Test result is shown in Table 6.
6 compound 1~11 of table is when test concentrations are 500mg/L to the activity of cotton spider mites
| Compound | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
| Active rank | B | A | A | A | A | B | A | A | A | A | A |
Embodiment 20, the biological evaluation to apis cerana
The 40 of each compound prepared using embodiment 13, the dilute suspension agent of 80mg/L concentration, in order to verify its centering
Whether the security of magnificent honeybee improves, and using worker bee as test worm, synthesis of each compound to apis cerana is determined using spray-on process
Toxicity (contact toxicity and Oral toxicity), correlated results is shown in Table 7.
7 compound 1-11 of table is to the 48h Toxicity test results of apis cerana
As can be known from Table 7：Ethiprole is higher to Chinese Bee Venom, and there is 4% poisoning rate in when 40mg/L, and
Rate of being poisoned to death during 80mg/L reaches 46% close to half；It is mainly shown as the weak and limp landing of body or death.Compound 1~
11 relatively low to the comprehensive toxicity of apis cerana, without poisoning manifestations when 40mg/L is handled, also only has when 80mg/L is handled
Occur 1 silkworm in the experiment of one group of compound and show the symptom being slightly poisoned (compound 4).If it defines poisoning rate to be not higher than
3% processing mass concentration is safe quality concentration, then the safe quality concentration of 1~11 pair of apis cerana of compound is at least
80mg/L, than ethiprole (<40mg/L) at least improve 1 times.
Embodiment 21 evaluates 1,2,3,6,10 light degradation property of compound
With xenon lamp (350W) for simulated solar radiant, respectively with compound 1,2,3,6,10 for light degradation substrate, concentration
It is 1 × 10-4mol/L.In view of the solubility in pure water of compound 1,2,3,6,10 is relatively low, addition acetonitrile makees cosolvent.It uses
High performance liquid chromatography measures concentration of the compound 1,2,3,6,10 after degrading at different moments.Chromatographic condition is as follows：Chromatographic column is
Phenomenex C18 chromatographic columns (250nm × 4.6mm, 5 μm)；Mobile phase is acetonitrile:Water=62:38；Flow velocity is 1.0mL/
min；Detection wavelength is 250nm；20 μ L of sample size.Experiment is repeated 3 times, and results are averaged.Degradation rate is calculated, probes into compound
1st, 2,3,6,10 light degradation property.The results are shown in Table 8.
8 compound 1,2,3,6,10 of table is in the photodegradation rate of different time
Embodiment 22, phloem transport measure
By ripe castor seeds on wet absorbent cotton at 25 DEG C vernalization 48h.The seed of germination is selected, is placed in artificial climate
Sand base culture is used in incubator.25 DEG C ± 1 DEG C of incubator temperature, relative humidity 75% ± 5%, daylight 14h, night close
It closes.To cultivate the castor-oil plant seedling of 6d as material to be tested.Castor-oil plant seedling is carefully peelled off into endosperm, is sure not to fold or stave cotyledon.
Its leaf is soaked in respectively in 11 groups of buffer solutions containing compound 1~11 (in each buffer solution containing 100 μm of ol/L testing compounds,
20mmol/L fatty acid methyl ester sulfonate, 0.25mmol/L MgCl2And 0.5mmol/L CaCl2) in, with the fluorine of same concentrations
Worm nitrile buffer solution is control.After cultivating 2h in each group buffer solution, cut off careful at seedling cotyledon to hypocotyl crotch 1cm,
The bast liquid that incision is oozed out in 3h is collected, 0.22 μm of organic phase miillpore filter is crossed after centrifugation, filtrate is dilute with pure water
It is to be measured after releasing 4 times.Experiment is repeated 5 times, and is averaged.Use compound 1 in high effective liquid chromatography for measuring bast diffusate
~11, the content of ethiprole.It is learnt from testing result, compound 1~11 has apparent absworption peak, and ethiprole does not have absworption peak,
So compound 1~11 has preferable dredging property of bast, ethiprole does not possess dredging property of bast.
Claims (8)
1. a kind of 1- (2,6- bis- chloro- 4- (trifluoromethyl) phenyl) -5- oxazinone -3- cyano -1H- pyrazoles type compounds, knot
Shown in structure formula such as general formula (II)：
In the general formula (II), R1Any one in following group：-H、-G、And
The G represents Cl, Br or I；
In the general formula (II), R2For phenyl；
In the general formula (II), R3Any one in following group：Hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, fourth
Base, amyl, chloromethyl, chloroethyl, dichloromethyl, trichloromethyl, cyclopropyl, cyclopenta, cyclohexyl, phenyl, p- methoxyl group-
Phenyl, furyl.
2. 1- (2,6- bis- chloro- 4- (trifluoromethyl) phenyl) -5- oxazinone -3- cyano -1H- pyrroles according to claim 1
Azoles type compound, it is characterised in that：
The R1For
The R3Any one in following group：Hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, amyl, chloromethane
Base, chloroethyl, dichloromethyl, trichloromethyl, cyclohexyl, phenyl, p- methoxyl group-phenyl, furyl.
3. 1- (2,6- bis- chloro- 4- (trifluoromethyl) phenyl) -5- oxazinone -3- cyano -1H- pyrroles according to claim 2
Azoles type compound, it is characterised in that：
The R3Any one in following group：Hydrogen, chlorine, methyl, trichloromethyl, cyclohexyl, phenyl, p- methoxyl group-
Phenyl and furyl.
4. it is a kind of synthesize any described 1- (2,6- bis- chloro- 4- (trifluoromethyl) phenyl)-5- oxazinones in claim 1-3-
The method of 3- cyano -1H- pyrazoles type compounds：
By 3- cyano -5- imino groups -1- (2,6- dichlor-4-trifluoromethyls phenyl) -1H- pyrazoles type compounds and carboxylic acid halidesIt is added in organic solvent, is prepared under Ultrasonic Radiation when 15~90 DEG C of reaction 0.5-10 are small,
Its synthetic route is as follows：
The compoundMiddle X is Cl, Br or I；
The R1、R2、R3As any one of claim 1-3 is defined.
5. according to the method described in claim 4, it is characterized in that：The organic solvent is selected from cyclic ethers class, arene, chain
Any one in ethers, amine solvent and esters；
Wherein, cyclic ether solvents are tetrahydrofuran or dioxane；
Aromatic hydrocarbon solvent is toluene, dimethylbenzene, mesitylene, chlorobenzene or bromobenzene；
Chain ethers solvent is ethylene glycol diethyl ether, butyl glycol ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, the third two
Alcohol methyl ether or dihydroxypropane single-ether；
Amine solvent is N,N-dimethylformamide or DMAC N,N' dimethyl acetamide；
Esters solvent is ethyl acetate, ethyl acetoacetate or ethyl propionate.
6. according to the method described in claim 5, it is characterized in that：The organic solvent is toluene, tetrahydrofuran, ethylene glycol two
Any one in ether；
The reaction temperature is 40~70 DEG C, when the reaction time is 1-9 small.
7. a kind of any described 1- (2,6- bis- chloro- 4- (trifluoromethyl) phenyl) -5- oxazinone -3- cyanogen in claim 1-3
Application of the base -1H- pyrazoles type compounds in grassy weed and/or broad leaved weed is prevented and kill off.
8. application according to claim 7, it is characterised in that：
The grassy weed is wild oat, bromegrass, Triticum tauschii, amur foxtail, barnyard grass, annual bluegrass and/or herba setariae viridis grass；
The broad leaved weed is Procumbent Falsepimpernel, false loosestrife, grass dragon and/or sesbania.
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| EP0352944A1 (en) * | 1988-07-15 | 1990-01-31 | Rhone-Poulenc Agriculture Limited | Derivatives of N-phenylpyrazoles |
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| CN1239953A (en) * | 1996-12-04 | 1999-12-29 | 拜尔公司 | 3-thiocarbamoylpyrazole derivatives as pesticides |
| WO2006000313A1 (en) * | 2004-06-26 | 2006-01-05 | Merial Ltd. | N-phenylpyrazole derivatives as pesticides |
| WO2006138147A1 (en) * | 2005-06-13 | 2006-12-28 | Bayer Cropscience Ag | Pesticidal 5-di-(substituted)aminopyrazole derivatives |
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|---|---|---|---|---|
| EP0352944A1 (en) * | 1988-07-15 | 1990-01-31 | Rhone-Poulenc Agriculture Limited | Derivatives of N-phenylpyrazoles |
| CN1192735A (en) * | 1995-08-11 | 1998-09-09 | 辉瑞大药厂 | Parasiticidal compound |
| CN1239953A (en) * | 1996-12-04 | 1999-12-29 | 拜尔公司 | 3-thiocarbamoylpyrazole derivatives as pesticides |
| WO2006000313A1 (en) * | 2004-06-26 | 2006-01-05 | Merial Ltd. | N-phenylpyrazole derivatives as pesticides |
| CN101175729A (en) * | 2004-12-07 | 2008-05-07 | 梅瑞尔有限公司 | 1-phenyl-3-piperazine-pyrazoles and pesticidal compositions of matter thereof |
| WO2006138147A1 (en) * | 2005-06-13 | 2006-12-28 | Bayer Cropscience Ag | Pesticidal 5-di-(substituted)aminopyrazole derivatives |
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