CN108586444A - The ultrasound synthesis of the oxime esterification derivative of Ji Yu oxazinone pyrazol frameworks and application - Google Patents
The ultrasound synthesis of the oxime esterification derivative of Ji Yu oxazinone pyrazol frameworks and application Download PDFInfo
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- 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
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- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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Abstract
The present invention relates to technical field of organic synthesis more particularly to a kind of methods 3 oxime ester 5 oxazine ketone group pyrazole compound and synthesize the type compound using supercritical ultrasonics technology, additionally provide the application of the type compound.The present invention uses 3 oxime ester of ultrasound synthesis, 5 oxazine ketone group pyrazole compound, and synthesis material cost is relatively low, and reaction condition is mild, and easy to operate, yield is higher, and the base being prepared is in oxazinone pyrazol framework oxime esterification derivative(Ⅰ)With good bactericidal and herbicidal and insecticidal bioactivity, high activity is especially shown in terms of agricultural, gardening, flowers and health are cut weeds with the prevention and control of plant diseases, pest control, therefore there are 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 3- oximes ester -5- oxazine ketone group pyrazole compounds
And the method for using supercritical ultrasonics technology synthesizing the type compound, additionally provide the application of the type compound.
Background technology
In various heterocycle compounds, oxazine ketone compounds have extensive bioactivity and lower biology poison
Property, especially there is good effect to cutting weeds.Oxazine ketone compounds are absorbability translocated herbicide, are removed with being different from other
The mode of careless agent inhibits the growth of sensitive plant meristematic cell, low with active ingredient usage amount, suitable dispenser phase length, lasting period
The features such as length, toxic side effect are small, and drug resistance is small and highly selective.Pyrazole compound has extensive bioactivity, is in recent years
Carry out one of the primary structure of novel pesticide research.Due to efficient, less toxic and structure the diversity that pyrazole compound is shown, because
And there is boundless research and development foreground.In recent ten years, ester type compound is drawn due to its efficient bioactivity
The concern for playing pesticide circle personage becomes the hot spot of current pesticide research exploitation.In various ester type compounds, oxime ester compound
With extensive bioactivity and lower bio-toxicity, especially there is good effect to antibacterial.Oxime ester compound has
The antibacterial activity of wide spectrum can effectively inhibit and kill pathogenic microbes, the dispenser phase low with active ingredient usage amount, suitable
Long, the features such as lasting period is long, toxic side effect is small, and drug resistance is small and highly selective.According to structures to form principle, Ji Yu oxazines are studied
The oxime esterification derivative of ketone pyrazol framework has not been reported as the bioactivity of herbicide, antibacterial and insecticide;It is oriented to simultaneously
Type insecticide is current research hotspot in the ascendant, can be in plant to wound location caused by insect pest position or insect pest
It is oriented the pesticide of accumulation, research emphasis is that orientation of the pesticide in plant is translocatable, mainly with plant endogenous work
Property substance acted on by the transfer protein of homing device as homing device, after so that it is coupled with pesticide conjugates be loaded into plant
In object, and transports to pest and cause harm position through plant phloem.
Invention content
In structure of the base in the oxime esterification derivative of oxazinone pyrazol framework, pyrazole compound, oxazine ketone compound
There are the bioactivity such as good antibacterial, weeding and desinsection with oxime ester compound, and and oxazine ketone compounds have it is fine
Homing device, can be very good to make full use of pyrazole ring, the bioactivity of oxazine ketone group and oxime ester and guidance quality, obtain one
Compound of the class novelty with excellent antibacterial, weeding and insecticidal activity.
Ji Yu oxazinone pyrazol framework oxime esterification derivatives are a kind of multi-functional pesticides with antibacterial, weeding and desinsection,
Wherein there is good bacteriostatic activity , oxazinones type compound to have good effect, pyrrazole structure to cutting weeds for oxime ester base group
There is good killing activity to pest, while pyrrazole structure is light sensitive, light degradation can be carried out well, it is environmentally friendly.
Based on considerations above, applicant's design has synthesized a series of multi-functional pesticide 3- oxime esters -5- with guide function
Oxazine ketone group pyrazole compound (I).Draw into oxazine ketone group, by inhibiting the growth of sensitive plant meristematic cell, to grass family
Weeds and broad leaved weed, which have, certain prevents and kill off activity;Oxime ester base is introduced, it is early to cucumber fusarium axysporum, peanut Cercospora bacteria, tomato
Epidemic disease bacterium, fusarium graminearum, Botryosphaeria berengeriana f. sp have good bacteriostatic activity;Oxazine ketone compounds are as plant endogenous work
Property substance, there is good guiding role as homing device, by being oriented to base after the coupling of oxazine ketone group and pyrazoles type compound
Conjugates are loaded into plant by the transfer protein effect of group, and are transported to pest and caused harm position through plant phloem, are allowed to
As the pesticide of the environment-friendly high-efficiency with guide function.Due to pyrazole compound can sunlight irradiation under can slowly voluntarily
Photodissociation so that 3- oxime ester -5- oxazine ketone group pyrazole compound (I) type pesticide sprayings can delay in a natural environment after for a period of time
Slower rays solution, decomposition product environmental sound are a kind of pesticides of green low-residual.3- oxime ester -5- oxazine ketone group pyrazoles chemical combination
Object (I) type pesticide has very in prevention Orthoptera, Thysanoptera, Homoptera, Heteroptera, Lepidoptera, coleoptera, Diptera class pest
Good application, has 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;
To the universal and development of the mid-80 large power supersonic equipment, application of the ultrasonic wave in chemical industry rapidly develops, and produces
Give birth to new cross discipline --- phonochemistry.In recent years, domestic and international related acoustochemical research and academic exchange Showed Very Brisk,
With acoustochemical development, ultrasonic method be widely used in reduction reaction, addition reaction, oxidation reaction, substitution reaction,
Condensation reaction, hydrolysis etc. are almost related to the every field of organic chemistry, but so far, ultrasonic wave applies to not yet
Relevant report in oxime esterification.In addition, ultrasonic wave in organic synthesis because with reaction condition it is mild, it is easy to operate, cleaning
The advantages that pollution-free and have received widespread attention.
Ultrasonic irradiation refers in reaction vessel, using different solvents as reaction medium, by reaction vessel
Apply ultrasonic wave, so that the active function groups of reaction is more easily broken off, reduce reaction activity, to make reaction be easier into
Row.Ultrasonic irradiation has the characteristics that efficient, highly selective, mild condition, easy to operate, it can also relatively easily synthesize one
A little conventional methods are difficult to the object synthesized.As far as we know, ultrasonic technology is applied to Ji Yu oxazinone pyrazol framework oxime esters
Change the synthesis of derivative so far still without document report.
Based on the above inventive concept, of the invention first is designed to provide a kind of 3- oximes ester -5- oxazine ketone group pyrazoles
Class compound (I), shown in structural formula such as general formula (I):
In general formula (I), R1Any one in following group:The alkane such as methyl, ethyl, propyl, amyl, cyclohexyl
Base, halogenalkyl, phenyl, phenethyl, p-fluorophenyl, rubigan, p-nitrophenyl etc. replace the heterocycles such as aromatic ring, furyl.
In general formula (I), R2Selected from any one of following group:The alkyl such as methyl, ethyl, phenyl etc. replace aromatic ring.
In general formula (I), the R3Any one in following group:Hydrogen H-, halogen group, saturated alkane base, halogen
Plain alkyl, saturation cycloalkyl group, phenyl, substituted phenyl, naphthalene, substituted naphthalene, anthryl, substituted anthryl, phenanthryl, substitution
Phenanthryl, furfuryl group, substituted furfuryl group, pyrrole radicals, substituted pyrrole radicals, thienyl, substituted thienyl, pyridyl group, substituted
Pyridyl group, quinolyl, substituted quinolyl, indyl and substituted 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-、
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-、
Best, the R3Any one in following group:Hydrogen H-, methyl CH3-、
Second object of the present invention is to provide a kind of method of composite structure formula compound as shown in general formula (I), this
Method is efficient, environmentally friendly, easy, at low cost.
Second purpose to realize the present invention, the present invention designed by technical solution be:
By 3- amidoxime base -5- oxazines ketone group-pyrazole compound (II) and acyl chloridesIt is added in organic solvent, in alkali
At 15~90 DEG C under Ultrasonic Radiation (power 100-300W, preferably 150W) under the action of property reagent triethanolamine (TEA)
Reaction is prepared for 2-12 hours.
Its synthetic route is as follows:
The R1、R2、R3It is defined as described above;;
The organic solvent is selected from ethyl acetate, tetrahydrofuran, dimethyl sulfoxide and acetonitrile;
The organic solvent most preferably acetonitrile.
Preferably, reaction temperature described in reaction equation (1) is 20~65 DEG C, and the reaction time is 2-9 hours;
Best, reaction temperature described in reaction equation (1) is 20~35 DEG C, and the reaction time is 3~6 hours;
3- amidoxime -5- oxazines ketone group-pyrazole compound in the method for compound shown in the composite structure formula such as general formula (I)
(II) andMolar ratio be 1:1.
Further, the 3- amidoximes -5- oxazines ketone group-pyrazole compound (II) is synthesized by following methods:By compound
(III) after first being reacted in ethyl acetate solvent with acyl chlorides, excessive azanol and alkaline reagent TEA is added, ultrasonic wave is passed through
(constant power 150W) method is prepared, and synthetic route is as follows:
R2、R3It is defined as described above;
Reaction temperature described in reaction equation (2) is 25 DEG C, and compound (III) is first anti-in ethyl acetate solvent with acyl chlorides
It it is 6 hours between seasonable, it is 6 hours that excessive azanol, which is then added, with the reaction time after alkaline reagent TEA;
(III) the compound bibliography:Zhang Changjun, Chen Zhen, Cao Xiaoqun wait the study on the synthesis [J] of ethiproles, Shandong
Agriculture university's journal, 2009,40 (1):145-147. methods synthesize.
R2It is defined as described above;
Third object of the present invention is to provide structural formula compound answering in plant bacteriostatic agent as shown in general formula (I)
With.
Third purpose to realize the present invention, the 3- oxime ester -5- oxazine ketone group pyrazoles that the present invention is prepared
Object is closed for inhibiting cucumber fusarium axysporum, peanut Cercospora bacteria, tomato early blight bacterium, fusarium graminearum, Botryosphaeria berengeriana f. sp
There is good control effect.
Fourth object of the present invention be to provide structural formula compound as shown in general formula (I) prevent and kill off grassy weed and
Application in terms of broad leaved weed.
The 4th purpose to realize the present invention, the 3- oxime ester -5- oxazine ketone group pyrazoles that the present invention is prepared
Object is closed for preventing and kill off grassy weed and broad leaved weed, achieves preferable control effect.
Weeds described here include but are 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.
The 5th of the present invention is designed to provide structural formula compound as shown in general formula (I) in prevention harmful insect (packet
Include Orthoptera, Thysanoptera, Homoptera, Heteroptera, Lepidoptera, coleoptera and Diptera), the application in terms of mite pest.
The 5th purpose to realize the present invention, the 3- oxime ester -5- oxazine ketone group pyrazoles that the present invention is prepared
Object is closed for preventing Orthoptera, Thysanoptera, Homoptera, Heteroptera, Lepidoptera, coleoptera, Diptera harmful insect, mite class evil
Worm achieves preferable control effect.
Harmful organism described here include but are not limited to this:
Harmful insect includes:Orthoptera such as blattaria, Thysanoptera such as cotton thrips, rice thrips, melon thrips, Homoptera such as folium isatidis
Cicada, Fei Wind, aphid;Heteroptera such as harlequin bug;Lepidoptera such as wheat silkworm, prodenia litura, diamondback moth, beet armyworm, powder mosquito
Noctuid, cabbage caterpillar;Coleoptera such as rice flatworm;Diptera such as yellow-fever mosquito, culex.
Mite pest includes:Acarina such as Tetranychus cinnabarinus, Jie-Li enzyme-SQ, T.urticae Koch.
Compared with prior art, general formula (I) compound and its ultrasonic synthetic method with the advantages of application and advantageous effect
It is as follows:
1, general formula (I) compound can effectively inhibit above-mentioned germ and prevent and kill off all kinds of weeds and have preferable activity, and can have
Effect kills above-mentioned each class pest, is a kind of multi-functional low-residue green pesticide to beneficial organism low toxicity.
2, simple using ultrasonic operation, safety, yield height, time are short, and energy conservation and environmental protection reaction condition is mild, operation is simple
Just, cleanliness without any pollution;
3, the 3- oxime ester -5- oxazine ketone group pyrazole compounds (I) that the present invention synthesizes, synthesis material cost is relatively low, reaction
Mild condition, easy to operate, yield is higher, and the 3- oxime ester -5- oxazine ketone group pyrazole compounds (I) being prepared have good
Bactericidal and herbicidal and insecticidal bioactivity, the table especially in terms of agricultural, gardening, flowers and health are cut weeds with the prevention and control of plant diseases, pest control
Reveal high activity, therefore there are very big development and application values.
Description of the drawings
Fig. 1 is that the compound 1-11 that embodiment 19 is tested compares figure (expression compound to the control effect of moths attracted by lamplight larva
Code name number back target a, b indicates that processing mass concentration is 80,160mg/L respectively).
Specific implementation mode
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- amidoxime base-5- oxazine ketone group-1H- pyrazole derivatives in following example 1-11 are applicant according to invention
Method self-control described in content.
The synthesis of embodiment 1,3- second oxime ester bases -5- (3- methyl-oxazine ketone group) -1- methyl-1 H- pyrazoles (compound 1)
Generate compound 1 reaction equation be:
50mL acetonitriles, 4.50g3- amidoxime bases -5- (3- methyl-oxazine ketone group) -1- first are added in 100mL single-necked flasks
Base -1H- pyrazoles, 1gTEA add 1.60g chloroacetic chlorides, and reaction temperature is 30 DEG C, and it is (fixed that single port bottle is put into ultrasonic sink
Power 180W) in reaction, reaction time 3h.Column chromatography for separation (ethyl acetate after the completion of reaction:Petroleum ether=1:4)
5.33g compound 1.Yield:96.5%.IR(KBr,cm-1):3225(N-H),3077(CH2- H), 1725 (- C=O), 1605
(pyrazole ring skeletal vibration), 1533 and 1483 (phenyl ring skeletal vibrations), 1312 (C-F), 882 (aromatic ring C-H)1HNMR(CDCl3,
400MHz)δ:7.81 (s, 1H, Ar-H), 5.34 (s, H, N-H), 5.21 (s, H, N-H), 2.26 (q, 3H, CH2-H)。
Embodiment 2, the third oxime ester bases of 3- -5- (3- ethyls -4- methyl-oxazine ketone group) -1- ethyl -1H- pyrazoles (compound 2)
Synthesis
Generate compound 2 reaction equation be:
50mL acetonitriles, 4.50g3- amidoxime bases -5- (- 4 first base oxazine ketone group of 3- ethyls)-are added in 100mL single-necked flasks
1- ethyl -1H- pyrazoles, 1gTEA add 1.80g propionyl chlorides, and reaction temperature is 35 DEG C, and single port bottle is put into ultrasonic sink
Reaction, reaction time 4h in (constant power 200W).Column chromatography for separation (ethyl acetate after the completion of reaction:Petroleum ether=1:4)
Obtain 4.99g compounds 2.Yield:92.6%.IR(KBr,cm-1):3254 (N-H), 3080 (C-H), 1724 (- C=O), 1606
(pyrazole ring skeletal vibration), 1530 and 1399 (phenyl ring skeletal vibrations), 1314 (C-F), 884 (aromatic ring C-H)1HNMR(CDCl3,
400MHz)δ:7.81 (s, 1H, Ar-H), 5.32 (s, H, N-H), 5.19 (s, H, N-H), 2.54 (s, H, C-H), 1.23 (q, 3H,
CH2-H)。
Embodiment 3,3- fourth oxime ester bases -5- (3- ethyls -4- methyl-oxazine ketone group) -1- phenyl -1H- pyrazoles (compound 3)
Synthesis
Generate compound 3 reaction equation be:
50mL acetonitriles, 4.50g3- amidoxime bases -5- (- oxazinones of 3- ethyl -4- methyl are added in 100mL single-necked flasks
Base) -1- phenyl -1H- pyrazoles, 1gTEA, add 2.00g butyl chlorides, reaction temperature is 45 DEG C, and single port bottle is put into ultrasonic wave
Reaction, reaction time 3h in sink (constant power 250W).Column chromatography for separation (ethyl acetate after the completion of reaction:Petroleum ether=
1:4) 5.11g compounds 3 are obtained.Yield:93.1%.IR(KBr,cm-1):3231(N-H),3051(C-H),2254(-CN),1611
(pyrazole ring skeletal vibration), 1512 and 1367 (phenyl ring skeletal vibrations), 1314 (C-F), 885 (aromatic ring C-H)1HNMR(CDCl3,
400MHz)δ:7.80(s,1H,Ar-H),5.33(s,H,N-H),5.29(s,H,N-H),2.47(s,H,C-H),1.72(s,H,
C-H), 0.99 (q, 3H, CH2-H)。
Own oxime ester base-the 5- of embodiment 4,3- (3- ethyls -4- methyl-oxazine ketone group) -1- phenyl -1H- pyrazoles (compound 4)
Synthesis
Generate compound 4 reaction equation be:
50mL acetonitriles, 4.50g3- amidoxime bases -5- (- oxazinones of 3- ethyl -4- methyl are added in 100mL single-necked flasks
Base) -1- phenyl -1H- pyrazoles, 1gTEA, add 2.40g caproyl chlorides, reaction temperature is 65 DEG C, and single port bottle is put into ultrasonic wave
Reaction, reaction time 3h in sink (constant power 200W).Column chromatography for separation (ethyl acetate after the completion of reaction:Petroleum ether=
1:4) 5.37g compounds 4 are obtained.Yield:94.9%.IR(KBr,cm-1):3243 (N-H), 3066 (C-H), 1729 (- C=O),
1608 (pyrazole ring skeletal vibrations), 1532 and 1378 (phenyl ring skeletal vibrations), 1314 (C-F), 884 (aromatic ring C-H)1HNMR
(CDCl3,400MHz)δ:7.80(s,1H,Ar-H),5.32(s,H,N-H),5.29(s,H,N-H),2.49(s,H,C-H),
1.68 (s, H, C-H), 1.34 (s, H, C-H), 0.90 (q, 3H, CH2-H)。
Embodiment 5,3- hexamethylene oxime ester bases -5- (3- methylenecyclohexyls -4- cyclohexyl-oxazine ketone group) -1- methyl-1s H-
The synthesis of pyrazoles (compound 5)
Generate compound 5 reaction equation be:
50mL acetonitriles, 4.50g3- amidoxime bases -5- (3- methylenecyclohexyl -4- hexamethylenes are added in 100mL single-necked flasks
Base-oxazine ketone group) -1- methyl-1 H- pyrazoles, 1g TEA, add 2.38g Cyclohexanoyl chlorides, reaction temperature is 65 DEG C, by single port
Bottle is put into reaction, reaction time 4.5h in ultrasonic sink (constant power 160W).Column chromatography for separation (acetic acid after the completion of reaction
Ethyl ester:Petroleum ether=1:4) 5.57g compounds 5 are obtained.Yield:95.3%.IR(KBr,cm-1):3451 (N-H), 3091 (C-H),
1722 (- C=O), 1649 (pyrazole ring skeletal vibrations), 1530 and 1396 (phenyl ring skeletal vibrations), 1313 (C-F), 887 (aromatic rings
C-H).1HNMR(CDCl3, 400MHz) and δ:7.81(s,1H,Ar-H),5.27(s,H,N-H),5.20(s,H,N-H),2.55(s,
H, C-H), 1.97 (s, H, C-H), 1.80 (s, H, C-H), 1.56 (s, H, C-H), 1.30 (q, 3H, CH2-H)。
Embodiment 6,3- benzene oxime ester bases -5- (3- benzyls -4- phenyl-oxazine ketone group) -1- phenyl -1H- pyrazoles (compound 6)
Synthesis
Generate compound 6 reaction equation be:
50mL acetonitriles, 4.50g3- amidoxime bases -5- (- oxazinones of 3- benzyl -4- phenyl are added in 100mL single-necked flasks
Base) -1- phenyl -1H- pyrazoles, 1gTEA, add 2.29g chlorobenzoyl chlorides, reaction temperature is 15 DEG C, and single port bottle is put into ultrasound
Reaction, reaction time 2h in wave sink (constant power 150W).Column chromatography for separation (ethyl acetate after the completion of reaction:Petroleum ether
=1:4) 5.15g compounds 6 are obtained.Yield:91.2%.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 rings
C-H).1HNMR(CDCl3, 400MHz):8.26 (s, 1H, Ar-H), 7.66 (s, 1H, Ar-H), 7.25 (s, 1H, Ar-H), 7.05
(s, 1H, N-H), 6.78 (s, 1H, N-H).
Embodiment 7,3- are to fluorobenzene oxime ester base -5- (3- ethyls -4- methyl-oxazine ketone group) -1- phenyl -1H- pyrazoles (chemical combination
Object 7) synthesis
Generate compound 7 reaction equation be:
50mL acetonitriles, 4.50g3- amidoxime bases -5- (- oxazinones of 3- ethyl -4- methyl are added in 100mL single-necked flasks
Base) -1- phenyl -1H- pyrazoles, 1gTEA, add 2.50g to fluorobenzoyl chloride, reaction temperature is 20 DEG C, and single port bottle is put into
Reaction, reaction time 3.5h in ultrasonic sink (constant power 200W).Column chromatography for separation (ethyl acetate after the completion of reaction:
Petroleum ether=1:4) 5.14g compounds 7 are obtained.Yield:95.3%.The structural formula of the compound detects to obtain really through infrared with nuclear-magnetism
Card.
Embodiment 8,3- are to chlorobenzene oxime ester base -5- (3- ethyls -4- methyl-oxazine ketone group) -1- methyl-1 H- pyrazoles (chemical combination
Object 8) synthesis
Generate compound 8 reaction equation be:
50mL acetonitriles, 4.50g3- amidoxime bases -5- (3- ethyls -4- methyl-oxazine ketone group)-is added in 100mL single-necked flasks
1- methyl-1 H- pyrazoles, 1gTEA add 2.70g parachlorobenzoyl chlorides, and reaction temperature is 25 DEG C, and single port bottle is put into ultrasound
Reaction, reaction time 5h in wave sink (constant power 150W).Column chromatography for separation (ethyl acetate after the completion of reaction:Petroleum ether
=1:4) 6.22g compounds 8 are obtained.Yield:91.2%.The structural formula of the compound is confirmed through infrared detected with nuclear-magnetism.
Embodiment 9,3- p-nitrophenyl oxime ester bases -5- (3- ethyls -4- methyl-oxazine ketone group) -1- ethyl -1H- pyrazoles (are changed
Close object 9) synthesis
Generate compound 9 reaction equation be:
50mL acetonitriles, 4.50g3- amidoxime bases -5- (- oxazinones of 3- ethyl -4- methyl are added in 100mL single-necked flasks
Base) -1- ethyl -1H- pyrazoles, 1gTEA, add 2.66g paranitrobenzoyl chlorides, reaction temperature is 25 DEG C, and single port bottle is put
Enter reaction, reaction time 3.5h in ultrasonic sink (constant power 150W).Column chromatography for separation (acetic acid second after the completion of reaction
Ester:Petroleum ether=1:4) 5.78g compounds 9 are obtained.Yield:97.2%.The structural formula of the compound is detected through infrared with nuclear-magnetism
To confirmation.
Embodiment 10,3- benzene second oxime ester bases -5- (3- ethyls -4- methyl-oxazine ketone group) -1- phenyl -1H- pyrazoles (chemical combination
Object 10) synthesis
Generate compound 10 reaction equation be:
50mL acetonitriles, 4.50g3- amidoxime base -5- oxazine ketone group -1- phenyl -1H- pyrroles are added in 100mL single-necked flasks
Azoles, 1gTEA add 2.56g phenyllacetyl chlorides, and reaction temperature is 30 DEG C, and single port bottle is put into ultrasonic sink (constant power
Reaction, reaction time 6h in 180W).Column chromatography for separation (ethyl acetate after the completion of reaction:Petroleum ether=1:4) 5.84gization is obtained
Close object 10.Yield:94.6%.The structural formula of the compound is confirmed through infrared detected with nuclear-magnetism.
Embodiment 11,3- chaff ester groups -5- (3- methylene furfuryl group -4- furfuryl groups-oxazine ketone group) -1- methyl-1 H- pyrazoles (are changed
Close object 11) synthesis
Generate compound 11 reaction equation be:
50mL acetonitriles, 4.50g3- amidoxime bases -5- (3- methylene furfuryl group -4- furfuryl groups-Evil are added in 100mL single-necked flasks
Piperazine ketone group) -1- methyl-1 H- pyrazoles, 1gTEA, add 2.46g furoyl chlorides, reaction temperature is 15 DEG C, single port bottle is put into super
Reaction, reaction time 3h in sound wave sink (constant power 300W).Column chromatography for separation (ethyl acetate after the completion of reaction:Oil
Ether=1:4) 5.01g compounds 11 are obtained.Yield:94.8%.The structural formula of the compound is confirmed through infrared detected with nuclear-magnetism.
Comparative example 12,3- second oxime ester bases -5- (3- methyl-oxazine ketone group) -1- methyl-1 H- pyrazoles (compound 1)
Synthesis
Separately or concurrently change in embodiment 1 by 3- amidoxime bases -5- (3- methyl-oxazine ketone group) -1- methyl-1 H- pyrazoles
Prepare synthesis temperature, reaction time and the heating side of 3- second oxime ester bases -5- (3- methyl-oxazine ketone group) -1- methyl-1 H- pyrazoles
Formula, other are same as Example 1, prepare compound 1, and the result for preparing result and embodiment 1 is 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, uses ultrasound under normal pressure
Wave processing is not generally than using the yield of ultrasonication to significantly improve.
The preparation of embodiment 13,3- oxime ester -5- oxazine ketone group pyrazole compound (I) experiment pesticide
The formulations of pesticide prepared by the present embodiment are suspending agent, and alleged " gross mass " refers to " prepared suspending agent below
Gross mass ".
The surfactant naphthalenesulfonic acid-formaldehyde condensate that 11 parts account for gross mass 5% is first diluted in 11 parts respectively and accounts for total matter
It measures in 5% antifreeze glycol, and is slowly added into the water for accounting for gross mass 25% into the solution respectively, distinguish under fast stirring
The compound 1~11 for the embodiment 1-11 preparations for accounting for gross mass 25% is sequentially added into 11 groups of solution and accounts for gross mass 5%
Auxiliary agent (preservative benzoic acid, antifoaming agent organosilicon and thickener xanthans), is ground it after adding, and is eventually adding and accounts for always
The water of quality 35%.By the suspending agent being prepared add water dilution prepare respectively compound 1-11 it is a concentration of 40,80,100,
The dilute suspension agent of 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, bactericidal activity evaluation
The dilute suspension agent for using 11 groups of 100mg/L concentration of embodiment 13 respectively takes dilute suspension agent 5mL, injection training
It supports in ware, 10mL potato dextrose agars (PDA) culture medium is then added, a concentration of 50mg/L of final mass is made and contains for examination
Compound plate (drug containing tablet).Cultured beaten for examination bacterium card punch is taken into diameter 5mm bacteria cakes, is placed in drug containing tablet,
Per 3 pieces of ware.Blank control is done with not adding medicine.After temperature is to cultivate 48h in 25 ± 1 DEG C of incubators, each processing mycelia is measured
Diameter is extended, and is compared with a control.Bacteriostasis rate=[(blank bacterium solution absorbance value-sample bacterium solution absorbance value)/blank bacterium solution
Absorbance value] * 100%, 2 are shown in Table to the bactericidal activity test result of 5 kinds of phytopathogens.
The active testing of 2. 1~11 pair of germ of compound of table
Embodiment 15, 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 3.
The active testing of 3 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 3.
Embodiment 16, 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, in hot-house culture after water drenching.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%
It it is C grades, the death rate 0%~50% is D grades.Test result is shown in Table 4.
4 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 17, the biological evaluation to green leaf hopper
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 20 or more 5 ages of green leaf hopper
Worm, the wrapping of nozzle white yarn cloth are placed under room temperature, and survival and dead borer population are checked after 24 hours.Experiment is repeated 3 times.
Results are averaged.Activity in percentage, is divided into A, B, C, D level Four relative to 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 5.
5 compound 1~11 of table is when test concentrations are 100mg/L to the activity of green leaf hopper
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 18, to the biological evaluation of wheat silkworm
The dilute suspension agent of the 100mg/L concentration of each compound prepared using embodiment 13,20 3 age wheats of every group of selection
Silkworm and 11 one cun of long maize leafs are put in culture dish, and the 100mL that each compound is added dropwise in every group of culture dish respectively is above-mentioned
Suspending agent is moved into greenhouse after drying and is normally raised, statistics survival and death toll after 24 hours.Experiment is repeated 3 times, and is as a result made even
Mean value.Activity in percentage, is divided into A, B, C, D level Four, the death rate 100%~90% is A grades, dead relative to blank control
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 6.
6 compound 1~11 of table is when test concentrations are 100mg/L to the activity of wheat silkworm
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 19, to the biological evaluation of moths attracted by lamplight larva
The 80 of each compound prepared using embodiment 13, the dilute suspension agent of 160mg/L concentration is examination with Soybean Leaves
Material.20 groups of experiment point every time, every group of 50 fresh Soybean Leaves, 100 4 age moths attracted by lamplight larvas of every group of placement connect worm band leaf and carry out
Spray, experimental period are 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 1:3- oximes ester -5- oxazine ketone group pyrazoles type compounds prepared by the present invention are living to the biology of moths attracted by lamplight larva
Property have a preferable effect, and same medicament is improved with use quality concentration, is increased therewith to the death rate of moths attracted by lamplight larva
Add.Compound 2, when mass concentration is 160mg/L, moths attracted by lamplight larval mortality highest, more than 70%;And compound 5 is then by matter
The influence for measuring concentration is maximum, and when concentration doubles, the death rate increases nearly ten times.
Embodiment 20, the biological evaluation to Tetranychus cinnabarinus
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 Tetranychus cinnabarinus on slide double faced adhesive tape, rejects dead and torpescence
Individual, record 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.Its body is touched with writing brush, motionless person is death enough with mite.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 7.
7 compound 1~11 of table is when test concentrations are 500mg/L to the activity of Tetranychus cinnabarinus
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 21, to the biological evaluation of family silkworm
The 40 of each compound prepared using embodiment 13, the dilute suspension agent of 80mg/L concentration, in order to verify it to family
Whether the safety of silkworm improves, and using family silkworm as test worm, comprehensive poison of each compound to family silkworm is determined using spray-on process
Property (contact toxicity and Oral toxicity), correlated results are shown in Table 8.
48h Toxicity test results of the 8 compound 1-11 of table to family silkworm
As can be known from Table 8:Dimethoate pesticide is higher to family's silkworm toxicity, and there is 4% poisoning rate in when 40mg/L, and
Rate of being poisoned to death when 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 family silkworm, without poisoning manifestations when 40mg/L is handled, also there was only one when 80mg/L is handled
There is 1 silkworm in the experiment of group compound and shows the symptom (compound 4) being slightly poisoned.If defining poisoning rate is not higher than 3%
Processing mass concentration be safe quality concentration, then the safe quality concentration of 1~11 pair of family silkworm of compound be at least 80mg/L,
Than dimethoate pesticide (<40mg/L) at least improve 1 times.
Embodiment 22 evaluates 1,3,6,9,11 light degradation property of compound
With xenon lamp (350W) for simulated solar radiant, respectively with compound 1,3,6,9,11 for light degradation substrate, concentration
It is 1 × 10-4mol/L.In view of compound 1,3,6,9,11, solubility is relatively low in pure water, and addition acetonitrile makees cosolvent.It uses
High performance liquid chromatography measures concentration of the compound 1,3,6,9,11 after different moments degrade.Chromatographic condition is as follows:Chromatographic column is
Phenomenex C18 chromatographic columns (250nm × 4.6mm, 5 μm);Mobile phase is acetonitrile:Water volume ratio=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, is probed into
The light degradation property of compound 1,3,6,9,11.The results are shown in Table 9.
Photodegradation rate of 9 compound 1,3,6,9,11 of table in different time
Embodiment 23, phloem transport measure
By ripe castor seeds on wet absorbent cotton at 25 DEG C vernalization 48h.The seed for selecting germination, 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 untested compounds,
20mmol/L fatty acid methyl ester sulfonate, 0.25mmol/LMgCl2And 0.5mmol/LCaCl2) in, with the Rogor of same concentrations
Pesticide 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 dimethoate pesticide.It is learnt from table 10, compound 1~11 has apparent absorption peak, dimethoate pesticide to exist before 20min
Just there is absorption peak after 30min, so there is compound 1~11 preferable dredging property of bast, the bast of dimethoate pesticide to dredge
Property is poor.
The appearance time of the high performance liquid chromatography of 10 compound 1-11 of table
Compound | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | Rogor |
Appearance time/min | 5.6 | 5.4 | 6.5 | 4.5 | 6.5 | 7.5 | 7.8 | 6.9 | 7.6 | 8.8 | 8.7 | 37 |
Claims (12)
1. a kind of 3- oximes ester -5- oxazine ketone group pyrazole compounds, shown in structural formula such as general formula (I):
In general formula (I), R1Any one in following group:It is alkyl, halogenalkyl, phenyl, phenethyl, p-fluorophenyl, right
Chlorphenyl, p-nitrophenyl, furyl;
In general formula (I), R2Selected from any one of following group:Alkyl, phenyl;
In general formula (I), the R3Any one in following group:Hydrogen H-, halogen group, saturated alkane base, halogen alkane
Base, saturation cycloalkyl group, phenyl, substituted phenyl, naphthalene, substituted naphthalene, anthryl, substituted anthryl, phenanthryl, substituted phenanthrene
Base, furfuryl group, substituted furfuryl group, pyrrole radicals, substituted pyrrole radicals, thienyl, substituted thienyl, pyridyl group, substituted pyridine
Base, quinolyl, substituted quinolyl, indyl and substituted indyl.
2. 3- oximes ester -5- oxazine ketone group pyrazole compounds according to claim 1, it is characterised in that:
The R1Any one in following group:It is methyl, ethyl, propyl, amyl, phenyl, phenethyl, p-fluorophenyl, right
Chlorphenyl, p-nitrophenyl, furyl;
The R2Any one in following group:Methyl, ethyl, phenyl;
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-nitro-benzene base2,3- dichlorophenylsThe bromo- phenyl of the fluoro- 3- of 2-2,6- dimethyl benzenes
Base3,5- 3,5-dimethylphenyls2,4,6- trifluorophenyls2,3,4- trihydroxies
Phenyl2,4,5- trimethoxyphenyls1- naphthalenes2- hydroxyls-
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
3. 3- oximes ester -5- oxazine ketone group pyrazole compounds according to claim 2, it is characterised in that:
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, chloroethyl
ClCH2CH2, dichloromethyl Cl2CH-, trichloromethyl CCl3, cyclopentaCyclohexylPhenylP- methoxyl group-phenylP-nitro-benzene base2,3- dichlorophenyls1- naphthalenes2- hydroxyl -1- naphthalenesFuryl5- methyl -2-
Furyl2- pyrrole radicals3- pyrrole radicals2- thienyls2- pyridines
BaseThe bromo- 3- pyridyl groups of 2-Bis- chloro- 3- pyridyl groups of 2,6-3- quinolyls3- indyls
4. a kind of method of any 3- oxime ester -5- oxazine ketone group pyrazole compounds in synthesis claim 1-3, including
Following steps:
By 3- amidoxime base -5- oxazines ketone group-pyrazole compound and acyl chloridesIt is added in organic solvent, in triethanolamine
Under effect, reacts 2-12 hours and be prepared at 15~90 DEG C under Ultrasonic Radiation;
Its synthetic route is as follows:
5. according to the method described in claim 4, it is characterized in that:The organic solvent is selected from ethyl acetate, tetrahydrofuran, two
Any one in first sulfoxide and acetonitrile.
6. according to the method described in claim 5, it is characterized in that:The reaction temperature is 20~65 DEG C, reaction time 2-9
Hour.
7. any 3- oximes ester -5- oxazine ketone group pyrazole compounds are to prevent and kill off grass family miscellaneous in a kind of claim 1-3
Application in grass and/or broad leaved weed.
8. application according to claim 7, it is characterised in that:
The grassy weed includes:Wild oat, bromegrass, Triticum tauschii, amur foxtail, barnyard grass, annual bluegrass and/or herba setariae viridis grass;
Broad leaved weed includes:Procumbent Falsepimpernel, false loosestrife, grass dragon and/or sesbania.
9. any 3- oxime ester -5- oxazine ketone group pyrazole compounds are in plant bacteriostatic agent in a kind of claim 1-3
Application.
10. any 3- oximes ester -5- oxazine ketone group pyrazole compounds are inhibiting cucumber withered in a kind of claim 1-3
Application in germ, peanut Cercospora bacteria, tomato early blight bacterium, fusarium graminearum and/or Botryosphaeria berengeriana f. sp.
11. any 3- oximes ester -5- oxazine ketone group pyrazole compounds are in prevention harmful insect in a kind of claim 1-3
And/or the application in terms of mite pest.
12. application according to claim 11, it is characterised in that:The harmful insect includes Orthoptera, Thysanoptera, same to wing
Mesh, Heteroptera, Lepidoptera, coleoptera and/or Diptera;The mite pest includes Acarina.
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---|---|---|---|---|
CN111689943A (en) * | 2020-06-16 | 2020-09-22 | 中南民族大学 | Cyclic lactam-containing pyrazolidine oxime ester derivative and synthesis method and application thereof |
CN112390727A (en) * | 2019-08-16 | 2021-02-23 | 沈阳中化农药化工研发有限公司 | Oxime carboxylate compound and application thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105541821A (en) * | 2016-01-28 | 2016-05-04 | 中南民族大学 | Oxazine ketonization arylpyrazole compound as well as ultrasonic radiation synthesis method and application thereof |
-
2018
- 2018-04-13 CN CN201810333696.8A patent/CN108586444A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105541821A (en) * | 2016-01-28 | 2016-05-04 | 中南民族大学 | Oxazine ketonization arylpyrazole compound as well as ultrasonic radiation synthesis method and application thereof |
Non-Patent Citations (1)
Title |
---|
候孝平 等: "二氢苯骈吡喃肟及肟酯衍生物的合成", 《中国药科大学学报》 * |
Cited By (4)
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---|---|---|---|---|
CN112390727A (en) * | 2019-08-16 | 2021-02-23 | 沈阳中化农药化工研发有限公司 | Oxime carboxylate compound and application thereof |
CN112390727B (en) * | 2019-08-16 | 2021-12-07 | 沈阳中化农药化工研发有限公司 | Oxime carboxylate compound and application thereof |
CN111689943A (en) * | 2020-06-16 | 2020-09-22 | 中南民族大学 | Cyclic lactam-containing pyrazolidine oxime ester derivative and synthesis method and application thereof |
CN111689943B (en) * | 2020-06-16 | 2021-10-29 | 中南民族大学 | Cyclic lactam-containing pyrazolidine oxime ester derivative and synthesis method and application thereof |
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