CN104910093B - The contraposition of 4 phenyl contains alcohol oxime ether structure oxazoline compounds and its preparation and the application in terms of worm mite Juncao is prevented and treated - Google Patents
The contraposition of 4 phenyl contains alcohol oxime ether structure oxazoline compounds and its preparation and the application in terms of worm mite Juncao is prevented and treated Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
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Abstract
The present invention relates to as led to 4 phenyl oxazoline compounds of the contraposition containing alcohol oxime ether structure and its preparation and the application on agricultural chemicals shown in formula (I), such compound represents a kind of Insecticiding-miticiding sterilization herbicide structure type of novel succinct, broad-spectrum high efficacy.The contraposition of 4 phenyl is used as new type disinsection killing acarus and bacteria herbicide containing alcohol oxime ether structure oxazoline compounds, and oriental armyworm, bollworm, corn borer, diamondback moth, beet armyworm, mosquito larvae can be prevented and treated well；Tetranychus cinnabarinus can be prevented and treated well；Following ten kinds of pathogens can be suppressed well：Cucumber is withered, peanut foxiness, apple wheel line, tomato early epidemic, gibberella saubinetii, potato late blight, rape sclerotium, cucumber grey mold, rice banded sclerotial blight, Phytophthora capsici；Following weeds can be prevented and kill off：Rape, three-coloured amaranth, barnyard grass and lady's-grass.(wherein R meaning is shown in specification)
Description
Technical field
The present invention relates to a class Novel 4-phenyl contraposition containing alcohol oxime ether structure oxazoline compounds and its prepare and
Application in terms of preventing and treating worm, mite, bacterium, grass, belongs to technical field of pesticide.
Background technology
It is well known that chemical pesticide occupies an important position always in disease pest and weed Synthetical control system, and inciting somebody to action
One period come will continue to be method very valuable during disease pest and weed is prevented and treated, and in human health care, ensure crops
Indelible effect has been played in terms of high yield.But person poultry poisoning, environmental pollution, " three R " produced by chemical pesticide is asked
Topic i.e. residual (Residue), resistance (Resistance) and pest resurgence (Resurgence) is increasingly serious
(Pestic.Sci.1998,54,300~322.；Agricultural chemicals, 2009,48 (9), 625~628.), give the non-target life such as mammal
Thing brings serious harm, pollutes environment or even destroy the ecological balance, and this requires that the direction of current plant protection is
Regulation and control to harmful organism, not " are killed (- cide) " simply.
Benzoylurea derivertives as a class " insect growth regulator, IGR (Insect Growth Regulators,
Abbreviation IGRs) ", by the development of interference insect, cast off a skin, the distinctive physiology course such as breed and control insect, started the 3rd
For the history of insecticide；Emphasize to be controlled pest population and adjust, optionally effective pest control, to people, animal, insect
Natural enemy and ecological environment security, meet requirement and the target of current green pesticide
(Pestic.Biochem.Physiol.1979,12,10~22.；J.Agric.Food Chem.1973,21 (3), 348~
354.).Etoxazole (Etoxazole, structural formula one), 2,4- diphenyl -1,3- oxazoline class chitins of currently the only commercialization
Matter biosynthesis inhibitor, not only with the incomparable acaricidal activity of other chitin synthesis inhibitors, but also with very
Good insecticidal activity.Oxime ether structure is the important active fragment of a class, is widely used in many pesticide molecules, example
Such as, flucycloxuron, fenpyroximate, orysastrobin, Enestroburin, commercialization medicament all active groups containing oxime ether structure such as fluxofenim
Group.Wherein, flucycloxuron (Flucycloxuron, structure one) be Holland Phillips Duphar companies initiative contain alcohol oxime
The benzoyl area kind chitin synthesis inhibitor of ether structure, with extraordinary insecticidal activity.Document report 2 in 2006,4- bis-
Phenyl -1,3- oxazoline compounds have closely similar structure-activity relationship with benzoyl urea compound
(J.Pestic.Sci.2006,31 (4), 409~416.).
During new, green, efficient pesticide-miticide is formulated, we are in combination with flucycloxuron and the structure of etoxazole
Effect relation, and etoxazole initiative longitude and latitude, design synthesized 4- phenyl contraposition derivative Z-1~Z- containing alcohol oxime ether structure
3 (structural formulas one), synthetic method is as shown in Scheme1.Bioactivity research finds compound Z-1~Z-3 only to diamondback moth, sweet tea
Dish noctuid and the young mite of Tetranychus cinnabarinus and mite ovum show pesticide and miticide actility (table 1).
The compound Z-1 of table 1.~Z-3 pesticide and miticide actility test results
Note：- represent undetermined
The content of the invention
Present invention aims at provide class Novel 4-phenyl contraposition containing alcohol oxime ether structure oxazoline compounds and
It is prepared and the application in terms of disease pest and weed preventing and treating.The present invention has found the 4- benzene of 2,4- diphenyl -1,3- oxazolines in early stage
Base contraposition is connected with the basis of the derivative of alcohol oxime ether structure Z-1~Z-3 has and kill diamondback moth, beet armyworm and Tetranychus cinnabarinus,
Tradition limitation is broken through, skeleton innovation is carried out, preferably goes out a collection of structural behaviour stabilization, kills diamondback moth, beet armyworm and Tetranychus cinnabarinus
Effect be better than Z-1~Z-3 compound, and find first to 4- phenyl contraposition containing alcohol oxime ether structure oxazoline class chemical combination
Thing also has kills bollworm, corn borer, aphid, mosquito larvae and sterilization, activity of weeding well.The present invention is new, wide to formulate
Spectrum, efficient agricultural disease pest and weed pesticide control are laid a good foundation, and possess good creativeness.
Novel 4-phenyl contraposition of the present invention is that general structure is shown in (I) containing alcohol oxime ether structure oxazoline compounds
The compound of structure：
In formula, OR represents cycloalkanone oxime, benzaldoxime, Substituted benzaldoxime etc..
4- phenyl contraposition of the present invention is following structure containing alcohol oxime ether structure oxazoline compounds (formula I)
Structure 1-11 shown in formula two is the compound of representative.
The compound of the logical formula (I) of the present invention can be prepared by the method shown in Scheme2.F is added to dichloromethane
In, KBr, potassium bromate and water are added, hydrochloric acid is added dropwise at 0 DEG C, is reacted 25 hours, organic phase sodium carbonate liquor, bicarbonate
Sodium solution is washed till colourless, then uses dichloromethane aqueous phase extracted, merges organic phase and washed with sodium chloride solution, then with nothing
Water magnesium sulfate is dried, and suction filtration is spin-dried for obtaining white solid, intermediate g is recrystallized to obtain with toluene and petroleum ether.Then, by sodium hydride
Dimethylformamide is added to, ketoxime is added, reacted 40 minutes, reacts and finishes under addition intermediate g, ice bath, supervised with TLC
Survey, add ethyl acetate, with a large amount of saturated common salt water washings, aqueous phase, which merges, to be extracted with ethyl acetate, merge organic phase with anhydrous
Magnesium sulfate is dried, and suction filtration is spin-dried for, and making eluant, eluent silica gel column chromatography with petrol ether/ethyl acetate=10/1 (v/v) separates, and must produce
Product I.
The compound of the logical formula (I) of the present invention, which has, excellent kills Tetranychus cinnabarinus activity.To the young mite of Tetranychus cinnabarinus, compound 9,
10th, 11 active effects are optimal, are 10 in test concentrations-4During mg/L, the death rate is 100%, and etoxazole is 10-3Mg/L concentration
Under the death rate be 40%, higher than known compound Z-1~Z-3；To Tetranychus cinnabarinus mite ovum, compound 9,10 active effects be
Test concentrations are 10-4During mg/L, the death rate is 100%, is better than etoxazole 10-3The death rate under mg/L concentration is 30%, right
Young mite activity is higher than known compound Z-1~Z-3；Compound 1-10 is higher than etoxazole to young mite and mite ovum activity.
The compound of the logical formula (I) of the present invention can also prevent and treat bollworm, corn borer, diamondback moth, beet armyworm, aphid well
Worm, mosquito larvae；Wherein compound 8 shows 83.3% fatal rate to bollworm, is in concentration when concentration is 600mg/L
During 600mg/L, compound 7 shows 80% fatal rate to bollworm, and etoxazole is when concentration is 600mg/L, to cotton boll
Worm shows 50% fatal rate；Compound 1,6,7,8,9,10 is showed diamondback moth respectively when test concentrations are 100mg/L
Go out 49%, 70%, 50%, 85%, 60%, 70% fatal rate, higher than known compound Z-1~Z-3, compound 4 exists
Diamondback moth is shown during 600mg/L 100% fatal rate, higher than known compound Z-1 and Z-2.Compound 10 is testing dense
When spending for 5mg/L, 80% fatal rate is shown respectively to mosquito larvae, with insecticidal effect phase of the etoxazole under 5mg/L concentration
When.Compound 11 shows 60% fatal rate to mythimna separata when test concentrations are 25mg/L, and etoxazole is in test concentrations
During 100mg/L, 40% fatal rate is shown to mythimna separata.
The compound of the logical formula (I) of the present invention can suppress following ten kinds of pathogens well：Cucumber is withered, peanut foxiness, apple
Fruit wheel line, tomato early epidemic, gibberella saubinetii, potato late blight, rape sclerotium, cucumber grey mold, rice banded sclerotial blight, Phytophthora capsici, wheat
White powder, rod spore tikka.
The compound of the logical formula (I) of the present invention has certain inhibition to rape, barnyard grass, three-coloured amaranth etc..
The compound of the logical formula (I) of the present invention can be used directly as Insecticiding-miticiding bactericide, can also be plus agriculturally
The carrier of receiving is used, can also be with other Insecticiding-miticiding bactericide such as emamectin-benzoate, tebufenpyrad, bromine worm
Nitrile, etoxazole, fenpyroximate etc. are applied in combination, the performance synergistic effect that these compositions have, some performance summation actions.
The 4- phenyl contraposition of the present invention contains the more existing agricultural entomogenous fungi used of alcohol oxime ether structure oxazoline compounds
Careless control agent, with very big advantage：Chemical constitution is simple, and chemical property is stable, and biological spectrum is wide, Insecticiding-miticiding sterilization activity
Significantly；Toxicity is low, and environment compatibility is good, to non-target organism safety.The present invention is the new, wide spectrum of initiative, efficient agricultural disease
Cordyceps sinensis evil control agent is laid a good foundation, and possesses good creativeness.
Embodiment
The present invention is described in further detail by the following examples, but the invention is not restricted to these embodiments.
Embodiment 1：The synthesis of compound 1：
5.0g (16.1mmol) compounds f, 40mL dichloromethane, 40mL water, 1.9g are sequentially added in 250mL single port bottles
(16.1mmol) KBr and 1.33g (8.05mmol) potassium bromate.0 DEG C of ice-water bath temperature control, is added dropwise the solution of the 6.1mL containing concentrated hydrochloric acid
20mL, is reacted 25 hours, and TLC monitoring reactions are finished, and point liquid, organic phase is washed with sodium carbonate liquor, sodium bicarbonate solution successively
To close to colourless, then dichloromethane aqueous phase extracted is used, merging organic phase is washed with sodium chloride solution, anhydrous MgSO4Dry, take out
Filter, is spin-dried for obtaining white solid, product g, common 3.5g, yield 55.9% is recrystallized to obtain with toluene and petroleum ether.Fusing point：127-128
℃。1H NMR (400MHz, CDCl3) δ 7.45-7.36 (m, 5H), 6.97 (t, J=8.0Hz, 2H), 6.62 (d, J=7.6Hz,
1H), 5.61-5.57 (m, 1H), 4.49 (s, 2H), 4.04-3.91 (m, 2H)
0.49g (20.59mmol) sodium hydride, 50mL dimethylformamides and 0.51g are added in 100mL single port bottles
(5.15mmol) cyclopentanone oxime, reacts 40 minutes, adds and is reacted under 1.0g (2.57mmol) intermediate g, condition of ice bath to TLC prisons
Survey reaction to finish, add ethyl acetate, with a large amount of saturated common salt water washings, aqueous phase, which merges, to be extracted with ethyl acetate, and is merged organic
Dried with anhydrous magnesium sulfate, suction filtration, screw out solvent and obtain rufous liquid, with the column chromatography of petrol ether/ethyl acetate=10/1, obtain
Yellow oil 0.65g.Yield 68.8%.1H NMR (400MHz, CDCl3) δ 7.49-7.31 (m, 1H, H-13), 7.38 (d, J
=8.0Hz, 2H, H-7, H-8), 7.32 (d, J=8.0Hz, 2H, H-6, H-9), 7.00 (t, J=8.0Hz, 2H, H-12, H-
14), 5.47 (dd, J=10.0,8.4Hz, 1H, H-11), 5.07 (s, 2H, H-5), 4.81 (dd, J=10.0,8.4Hz, 1H, H-
10), 4.30 (t, J=8.4Hz, 1H, H-10), 2.44 (t, J=6.8Hz, 2H, H-1), 2.36 (t, J=6.8Hz, 2H, H-4),
1.77-1.71 (m, 4H, H-2, H-3)13C NMR (100MHz, CDCl3) 6167.4,167.2,162.54,162.48,160.0,
159.9,157.5,141.1,138.0,132.5,132.4,132.3,128.4,126.6,112.1,111.8,75.1,74.8,
70.1,31.0,30.9,28.0,27.1,25.2,25.2,24.7,24.6.HRMS (MALDI)：Calcd.for C21H20F2N2O2
[M+H]+371.1566；found371.1570.
Embodiment 2：The synthesis of compound 2~11：
Compound 2~11 is synthesized using method shown in embodiment 1.
Compound 2
Yellow thick liquid, yield is 40%.1H NMR (400M, CDCl3) 7.46-7.41 (m, 1H), 7.36 (d, J=
8.0Hz, 2H), 7.32 (d, J=8.0Hz, 2H), 7.00 (t, J=8.4Hz, 2H), 5.52-5.42 (m, 1H), 5.05 (s, 2H),
4.85-4.78 (m, 1H), 4.32-4.28 (m, 1H), 2.50 (t, J=6.2,2H), 2.24-2.15 (m, 2H), 1.64-1.66
(m, 4H), 1.59-1.61 (m, 2H) .HRMS (ESI)：Calcd.for C22H22F2N2O2H[M+H]+385.1722；
found385.1722.
Compound 3
Light yellow liquid, yield is 46.4%.1H NMR (400MHz, CDCl3) δ 7.46-7.41 (m, 1H), 7.37 (d, J
=8.0Hz, 2H), 7.32 (d, J=8.0Hz, 2H), 7.00 (t, J=8.0Hz, 2H), 5.47 (dd, J=10.4,8.0Hz,
1H), 5.06 (s, 2H), 4.81 (dd, J=10.4,8.4Hz, 1H), 4.30 (t, J=8.4Hz, 1H), 2.59-2.54 (m,
2H), 2.38-2.34 (m, 2H), 1.73-1.56 (m, 8H) .HRMS (MALDI)：Calcd.for C21H20F2N2O2[M+H]+
399.1879；found399.1875.
Compound 4
Yellow thick liquid, yield is 68%.1H NMR (400M, CDCl3) 8.13 (s, 1H), 7.64-7.54 (m, 2H),
7.45-7.41 (m, 3H), 7.41-7.30 (m, 5H), 7.00 (t, J=8.4Hz, 2H), 5.53-5.42 (m, 1H), 5.21 (s,
2H), 4.88-4.76 (m, 1H), 4.27-4.31 (m, 1H) .HRMS (ESI)：Calcd.for C23H18F2N2O2H[M+H]+
398.1409；found398.1408.
Compound 5
Light yellow liquid, yield is 61.2%.1H NMR (300MHz, CDCl3) δ 8.38 (s, 1H), 7.81 (t, J=
6.6Hz, 1H), 7.45-7.32 (m, 6H), 7.15-6.96 (m, 4H), 5.48 (dd, J=10.2,8.1Hz, 1H), 5.22 (s,
2H), 4.82 (dd, J=10.2,8.4Hz, 1H), 4.31 (t, J=8.1Hz, 1H)13C NMR (100MHz, CDCl3) δ 164.1,
162.6,162.5,161.7,160.0,157.6,147.93,147.90,141.6,136.8,134.5,134.4,132.5,
132.4,132.33,130.28,130.2,129.0,126.8,123.2,123.2,116.9,116.7,113.4,113.2,
112.1,112.1,111.8,76.3,74.8,70.1.HRMS (MALDI)：Calcd.for C23H17F3N2O2[M+H]+
411.1315；found411.1307.
Compound 6
Yellow thick liquid, yield is 32.0%.1H NMR (300MHz, CDCl3) δ 8.08 (s, 1H), 7.47-7.26 (m,
8H), 7.09-6.93 (m, 3H), 5.47 (dd, J=10.2,8.1Hz, 1H), 5.20 (s, 2H), 4.80 (dd, J=10.2,
8.4Hz, 1H), 4.28 (t, J=8.1Hz, 1H)13C NMR (100MHz, CDCl3) δ 164.1,162.6,162.5,161.7,
160.0,157.6,147.93,147.90,141.6,136.8,134.5,134.4,132.5,132.4,132.33,130.28,
130.2,129.0,126.8,123.25,123.22,116.9,116.7,113.4,113.2,112.1,112.1,111.8,
76.3,74.8,70.1.HRMS (MALDI)：Calcd.for C23H17F3N2O2[M+H]+411.1315；found411.1315.
Compound 7
Light yellow solid, 85-87 DEG C of fusing point, yield is 33.3%.1H NMR (400MHz, CDCl3) δ 8.10 (s, 1H),
7.60-7.52 (m, 2H), 7.47-7.39 (m, 3H), 7.35 (d, J=8.0Hz, 2H), 7.07-6.98 (m, 4H), 5.48 (dd, J
=10.4,8.0Hz, 1H), 5.19 (s, 2H), 4.82 (dd, J=10.4,8.4Hz, 1H), 4.29 (t, J=8.0Hz, 1H)13C
NMR (100MHz, CDCl3) δ 147.9,141.6,137.0,132.5,132.4,132.3,128.9,126.8,115.9,
115.7,112.1,111.8,76.1,74.8,70.1.HRMS (MALDI)：Calcd.for C23H17F3N2O2[M+H]+
411.1315；found411.1313.
Compound 8
Yellow thick liquid, yield is 32.0%.1H NMR (400MHz, CDCl3) δ 8.11 (s, 1H), 7.50 (d, J=
8.0Hz, 2H), 7.43-7.36 (m, 5H), 7.33 (d, J=7.6Hz, 2H), 6.97 (t, J=8.4Hz, 2H), 5.45 (t, J=
9.2Hz, 1H), 5.19 (s, 2H), 4.79 (t, J=9.2Hz, 1H), 4.27 (t, J=8.2Hz, 1H), 1.31 (s, 9H)13C
NMR (100MHz, CDCl3) δ 162.6,162.5,160.02,159.96,157.6,153.2,149.0,141.5,137.2,
132.5,132.4,132.3,129.4,128.9,126.9,126.7,125.7,112.1,111.8,107.5,107.3,
107.1,75.9,74.8,70.1,34.8,31.2.HRMS (MALDI)：Calcd.for C27H26F2N2O2[M+H]+449.2035；
found449.2032.
Compound 9
Light yellow liquid, yield is 70.4%.1H NMR (400MHz, CDCl3) δ 8.51 (d, J=2.0Hz, 1H), 8.02
(d, J=7.6Hz, 1H), 7.61 (d, J=7.6Hz, 1H), 7.50-7.31 (m, 7H), 6.94 (t, J=8.4Hz, 2H), 5.46
(dd, J=10.0,8.0Hz, 1H), 5.23 (s, 2H), 4.78 (dd, J=10.0,8.4Hz, 1H), 4.26 (t, J=8.4Hz,
1H).13C NMR (100MHz, CDCl3) δ 164.1,162.6,162.5,161.7,160.0,157.6,147.93,147.90,
141.6,136.8,134.5,134.4,132.5,132.4,132.33,130.28,130.2,129.0,126.8,123.25,
123.22,116.9,116.7,113.4,113.2,112.1,112.1,111.8,76.3,74.8,70.1.HRMS (MALDI)：
Calcd.for C24H17F5N2O2[M+H]+461.1283；found461.1287.
Compound 10
Yellow thick liquid, yield is 53.9%.1H NMR (400MHz, CDCl3) δ 8.15 (s, 1H), 7.84 (s, 1H),
7.74 (d, J=7.6Hz, 1H), 7.61 (d, J=7.6Hz, 1H), 7.51-7.39 (m, 4H), 7.36 (d, J=8.0Hz, 2H),
7.00 (t, J=8.0Hz, 2H), 5.48 (dd, J=10.0,8.4Hz, 1H), 5.23 (s, 2H), 4.82 (dd, J=10.0,
8.4Hz, 1H), 4.30 (t, J=8.4Hz, 1H)13C NMR (100MHz, CDCl3) δ 164.1,162.6,162.5,161.7,
160.0,157.6,147.93,147.90,141.6,136.8,134.5,134.4,132.5,132.4,132.33,130.28,
130.2,129.0,126.8,123.25,123.22,116.9,116.7,113.4,113.2,112.1,112.1,111.8,
76.3,74.8,70.1.HRMS (MALDI)：Calcd.for C24H17F5N2O2[M+H]+461.1283；found461.1282.
Compound 11
Yellow thick liquid, yield 52.6%.1H NMR (400M, CDCl3) 8.15 (s, 1H), 7.69 (d, J=8.0Hz,
2H), 7.61 (d, J=8.0Hz, 2H), 7.44-7.42 (m, 3H), 7.36 (d, J=8.0Hz, 2H), 7.00 (t, J=8.0Hz,
2H), 5.52-5.44 (m, 1H), 5.23 (s, 2H), 4.87-4.78 (m, 1H), 4.27-4.32 (m, 1H) .HRMS (ESI)：
calcd.for C24H17F5N2O2[M+H]+461.1283；found461.1285.
Embodiment 3：The contraposition of 4- phenyl is containing alcohol oxime ether structure oxazoline compounds 1-11 to mythimna separata
(M.separate), northern house (C.pipiens's), bollworm (H.armigera) and corn borer (P.nubilalis) kills
Worm activity：
Mensuration program is as follows：
The active testing of oriental armyworm
The experimental method of oriental armyworm：After leaf dipping method, concentration needed for being configured to, the blade for being about 5-6cm diameter immerses
5-6 seconds in decoction, take out, be placed on blotting paper and dry, be placed in the culture dish specified, access 10 first 3 instar larvaes, it is put into 27 ±
Inspection result after being observed 3-4 days in 1 DEG C of insectary.
The active testing of mosquito larvae
The experimental method of mosquito larvae：Culex pipiens pallens, the normal population of indoor feeding.Weigh test compound about
5mg is in penicillin medicine bottle, plus 5mL acetone (or suitable solvent), vibration dissolving, as 1000mg/kg mother liquors.Pipette
0.5mL mother liquors, add in the 100mL beakers for filling 89.5mL water, larvae at the beginning of 10 first 4 ages are chosen, together with 10mL feeding liquids
Pour into the lump in beaker, the concentration of its decoction is 5mg/kg.It is put into standard process chamber, 24h inspection results.With containing
The aqueous solution of 0.5mL test solvents is blank control.
The active testing of bollworm
The experimental method of bollworm：Feed mixes medicine method, and the firm configuration that 3mL adds about 27g is pipetted from the solution configured
In good feed, so as to obtain the required concentration of ten times of dilution.Medicament is equably poured into 24 clean orifice plates after mixing, and dries in the air cool
24 first 3 age bollworms are accessed afterwards, inspection result after observing 3-4 days.
The active testing of corn borer
The test method of corn borer：It is about 5-6cm blades immersion decoction diameter after leaf dipping method, concentration needed for being configured to
It is middle 5-6 seconds, take out, be placed on blotting paper and dry, be placed in the culture dish specified, access 10 first 3 instar larvaes, be put into 27 ± 1 DEG C
Insectary in observation 3-4 days after inspection result.
The compound of table 2 to oriental armyworm, mosquito larvae, bollworm, corn borer determination of activity
(note：ET is etoxazole)
Using broad spectrum insecticide acaricide etoxazole as control, carry out to oriental armyworm, northern house, bollworm and corn
Snout moth's larva active testing, test result shows that part of compounds shows greater activity, part of compounds higher than etoxazole effect or
Person is suitable.Compound 11 shows higher mythimna separate, significantly larger than etoxazole mythimna separate, part of compounds performance
Go out and necessarily kill bollworm and corn borer activity.
Embodiment 4：The contraposition of 4- phenyl containing the young mite of 1~11 pair of Tetranychus cinnabarinus of alcohol oxime ether structure oxazoline compounds,
Mite ovum, diamondback moth, the mite killing insecticidal activity of beet armyworm：
Mensuration program is as follows：
The active testing of Tetranychus cinnabarinus children mite
Selection to young mite
First have to obtain egg-laying season consistent ovum, (can be laid eggs with the ovum produced in 24 hours before egg hatching under the conditions of 25 DEG C
Afterwards the 5th day) ovum blade has been removed, it is cut into small pieces and is placed on above the blade of tool two panels true leaf, in greenhouse under solar radiation, one
The young mite newly hatched after it can be transferred on young leaves.The young mite stage of development can be selected to carry out chemicals treatment, often according to test requirements document
The worm amount of individual tested plant should be no less than 60.
Test method：Infusion process
The pea seedling leaf of the young mite of inoculated Tetranychus cinnabarinus is put into the decoction prepared with straight peen ophthalmology tweezers, it is ensured that complete
Portion contaminates, and time 2-3 second, gets rid of extraction raffinate.One plant every time, every plant of 2 blades.After decoction is dry, the markd diameter of tool is put into
In the culture dish of 10cm length, each compound of inspection result is repeated 3 times within 96 hours.Control only into distilled water add emulsifying agent and
Solvent, stirs.
The active testing of Tetranychus cinnabarinus mite ovum
Selection to ovum
Tetranychus cinnabarinus is seeded on the blade with two panels true leaf bean seedlings into female mite with fine, soft fur pen, every plant connect 14 into
Mite, i.e., each blade connects 7, is placed in 25 DEG C of thermostatic chambers.Spawning removes into mite after 24 hours, can typically produce 100 ovum left sides
It is right.Continue that after placing 24 hours chemicals treatment can be carried out under similarity condition.
Test method：Infusion process
The pea seedling leaf of inoculated Tetranychus cinnabarinus ovum is put into the decoction prepared with straight peen ophthalmology tweezers, it is ensured that all
Contaminate, time 2-3 second, get rid of extraction raffinate.One plant every time, every plant of 2 blades.After decoction is dry, the markd diameter of tool is put into
In 10cm culture dish, inspection result after 96 hours.
Diamondback moth and the active testing of beet armyworm
Diamondback moth (Plutella xylostella) is that the insect for surveying the long-term manually feed raising in room gives birth in Nankai University.
Rearing conditions：T, 24~26 DEG C；RH, 70%~80%；L/D, 14h/10h.Individual Size and physiological status one are chosen during experiment
The second instar larvae of cause is for examination.
Beet armyworm (Spodoptera exigua) is that the insect for surveying the long-term manually feed raising in room gives birth in Nankai University.
Rearing conditions：T, 27 ± 1 DEG C；RH, 50%~75%；L/D, 14h/10h.Individual Size is chosen during experiment consistent with physiological status
Three age instar larvaes for examination.
The leaf dipping method proposed using international resistance Action Committee (IRAC).Weighed on assay balance 2mg medicines sample in
In 10mL small beakers, plus 50uL dimethylformamides (analysis is pure) dissolve, plus 200mg/kg decoctions are made in 10mL water.With straight peen eye
Section's tweezers dipping cabbage leaves, 2~3 seconds time, get rid of extraction raffinate.1 tablet once, totally 3, each sample.By sample flag sequence according to
It is secondary to be placed on processing paper.After decoction is dry, it is put into the straight type pipe for having markd 10cm length, accesses 2 age diamondback moth larvaes, uses
Gauze covers the mouth of pipe.Test process is placed in standard process chamber, inspection result after 96h.Each compound is repeated 3 times.Control
Emulsifying agent and solvent are only added into distilled water, is stirred.
The compound of table 3 is to the young mite of Tetranychus cinnabarinus, mite ovum, diamondback moth and beet armyworm determination of activity (concentration mg/L)
(note：- represent not test, ET is etoxazole)
Using broad spectrum insecticide acaricide etoxazole as control, survey the activity for killing the young mite of Tetranychus cinnabarinus and mite ovum
Examination, as a result shows that the contraposition of 4- phenyl kills cinnabar leaf containing what alcohol oxime ether structure oxazoline compounds 1~11 were all done well
Mite children mite and mite ovum activity, and all show to kill the young mite of Tetranychus cinnabarinus and mite ovum activity, compound 5- far above etoxazole
11 pairs of young mite activity all show 100% fatal rate, compound 5,9,10 work pair mite ovum under 0.0001mg/L concentration
Property under 0.0001mg/L concentration be all 100%, and compound 5,8,9 is significantly larger than compound Z-1~Z-1 and kills young mite
With mite ovum activity；Carry out to diamondback moth and beet armyworm active testing, test result is shown, the contraposition of 4- phenyl contains alcohol oxime ether
Jie Gou 1~11 pair of diamondback moth of oxazoline compounds has certain bioactivity, and the wherein activity of compound 1,5,6,8,9 is remote
It is the fatal rate that 100mg/L still shows more than 45% in test concentrations far above compound Z-1~Z-1.Part of compounds table
Reveal killing beet noctuids activity.
Embodiment 5：Part 4- phenyl contraposition contains alcohol oxime ether structure oxazoline compounds bactericidal activities：
Mensuration program is as follows：
A. in vitro sterilization test, biomass growth rate determination method (Plating)：
Precise testing compound, aseptically, dimethyl sulfoxide, N, N- diformazans is selected according to the property of compound
Base imines, the dissolving of acetone equal solvent, and it is standby to be diluted with water to series concentration.Draw the culture dish that 1mL decoctions are transferred to 9cm
In, the culture medium for then adding 9mL shakes up and is allowed to be well mixed with decoction, is positioned to containing flat board, and will contain 1mL sterilized waters with
The flat board of 9mL culture mediums is used as control treatment group.Bacterium disk is taken to be transferred on culture medium flat plate using a diameter of 4mm card punch.
Each processing is repeated 3 times, and it is that each bacterium disk extension is investigated after 24 ± 1,72 hours to be placed on temperature setting in constant incubator
Diameter, bactericidal activity inhibiting rate is tried to achieve as follows：
I=(D1-D2)/D1*100%
I is bacteriostasis rate, and D1 represents that blank control group extends the diameter of bacterium disk, and D2 is that chemicals treatment group extends the straight of bacterium disk
Footpath.
B. live body sterilization test：
Gray mold：Botrytis cinerea is gone on PDA plate first and activated 3 days, is returned again in PD liquid mediums, every bottle of transfer
5 pieces, it is necessary to cultivate 6 days, are beaten mycelia, measure light transmittance (light transmittance：9.8%) spray inoculation, then moisturizing culture is extremely fallen ill.
Rape sclerotium：Sclerotinia sclerotiorum is gone to first after being activated 3 days on PDA plate, then gone in PD liquid mediums,
Every bottle of transferase 45 block, need to be cultivated 6 days, beat mycelia, measure light transmittance (light transmittance：1.1%) spray inoculation, then moisturizing culture is extremely
Morbidity.
Wheat white powder：The Powdery Mildew Fresh spores that 24h is produced on morbidity wheat leaf blade are collected first, then by fresh spore
Son is uniformly inoculated on the potted plant wheat seedling of 2-3 leaf phases.
Situation about being fallen ill according to blank control, carries out classification investigation to inoculation leaves infected situation, adopts with the following method：Nothing
Scab is 0 grade；It is 1 grade below 5% that the area of scab, which accounts for whole leaf area,；Lesion area accounts for whole below leaf area 6%-10%
For 3 grades；Spot area accounts for whole below leaf area 11%-25% for 5 grades；Lesion area accounts for whole below leaf area 26%-50%
For 7 grades；Lesion area accounts for whole leaf area more than 50% for 9 grades；
The computational methods of disease index and prevention effect are：
Disease index=[∑ (the typical value number of the sick numbers of blade at different levels × relative series) ÷ (total leaf numbers × highest series
Typical value)] × 100；
Preventive effect=[(the average disease index of the average disease index-processing of control group) the average disease index of ÷ control groups] ×
100。
Phytophthora capsici disease：P. capsici is gone into PDA plate first to activate 3 days, the training of oat flat board is then transferred into
Illumination cultivation 7d or so on base is supported, finally brush hyposporangium suspension, continues 1 hour standby under conditions of being stored in 4 DEG C.Make
The decoction 1mL prepared is drawn with liquid-transfering gun and is inoculated in seedling rhizome 1cm or so place；Bacterium is connect using root-pouring method, spore concentration
It is formulated as 1 and is made as 5/ml of root, is inoculated with liquid-transfering gun seedling rhizome 1cm or so place, moisturizing 12h.The classification mark of pouring root inocalation method
Standard is：
It is set to 0 grade without any symptom of catching an illness；The slightly blackening of seedling rhizome position, and not wilting or restorability occurs in blade
Wilting is set to 1 grade；The position blackening of seedling rhizome is up to 1~2cm, and irrecoverability wilting, the blade of plant bottom occurs in blade
Occasionally have to come off and be set to 2 grades；There is blackening more than 1~2cm in seedling rhizome portion, and blade, which occurs substantially to wilt or fall leaves, more is set to 3
Level；Blackening, shrinkage occur for seedling rhizome portion, and generation leaf in growing point outside is come off or whole strain is wilted and is set to 4 grades；Plant is completely withered
It is set to 5 grades.
The computational methods of disease index and prevention effect are：
Disease index (DI)=[∑ (strain number of the sick value of series × sick level disease) × 100] ÷ (peak × tune of sick level
Look into strain number)；
Preventive effect=[(the average disease index of the average disease index-processing of control) ÷ compares average disease index] ×
100。
The in vitro bactericidal activity measurement result of table 4
(note：- represent not test, ET is etoxazole)
The part of compounds live body bacteriostatic activity test result of table 5
(note：- represent not test, ET is etoxazole, and X represents Fluoxastrobin, and * represents dimethomorph under 12.5mg/L concentration
Inhibiting rate.)
Using etoxazole and commercialization bactericide Fluoxastrobin, dimethomorph as control, mutual-through type for I compound carried out from
Body and the test of live body bactericidal activity, as a result show that the part of compounds that formula is I is withered to cucumber under the μ g/mL of concentration 50, spend
Raw foxiness, apple wheel line, tomato early epidemic, gibberella saubinetii, potato late blight, rape sclerotium, cucumber grey mold, rice banded sclerotial blight, capsicum
Phytophthora has in vitro bactericidal activity very well, wherein to apple wheel line and rape sclerotium effect substantially, part of compounds is to apple wheel line
Inhibitory activity reach more than 89%；Under the μ g/mL of concentration 200, formula is I part of compounds to rape sclerotium, paddy rice line
Withered, wheat white powder, cucumber rod spore tikka, phytophthora live body, cucumber grey mold have fine live body bactericidal activity.
Embodiment 6：Part 4- phenyl contraposition contains alcohol oxime ether structure oxazoline compounds activity of weeding：
Mensuration program is as follows：
A. isolated activity is determined：
Rape Plating, completes a diameter of 5.6cm original shape filter paper, in culture dish in a diameter of 6cm culture dish
The testing compound solution of 2ml aimed concns is added on filter paper, rape seed is soaked seed before experiment starts 6 hours, Mei Gechong
15 rape seeds are placed again, are then placed within conditions of dark and are maintained at after 30 ± 1 DEG C, 66 hours that to measure rape radicle long
Degree, growth inhibition ratio is tried to achieve with blank control contrast.
Barnyard grass small-radius curve track, first adds one layer of bead in bottom in 50mL beaker, conjunction is then spread on bead
The filter paper of suitable size, 5mL testing compound solutions are pipetted with pipettor, in experiment by barnyard grass presprouting of seeds to showing money or valuables one carries unintentionally, each
Beaker sow 10 barnyard grasses, be then placed within Continuous irradiation 72 hours under growth lamp, be maintained at 28 ± 1 DEG C, by with blank pair
The activity of weeding of testing compound is evaluated according to the growing state that group barnyard grass compares.
B. pot experiment
Proper amount of Nutrition Soil is put into a diameter of 7cm dixie cup, a certain amount of water is then added, by seed before sowing
Vernalization, after planting covers certain thickness soil, is cultivated in condition of culture room, notes keeping moisture, illumination and proper temperature
Plant growth.Processing is divided into soil treatment and cauline leaf process, and testing compound is sprayed at into soil after planting during soil treatment
The processing mode on surface, cauline leaf process is in germination and grown possess the examination material of certain growth cauline leaf before treatment, selection
In the same size, growth phase is synchronous, and general to grassy weed in 1.5 leaf phases, broad leaved weed is handled in the 2-3 leaf phases.
The in vitro Herbicidal result of table 6
(note：- represent not test, ET is etoxazole)
The pot experiment Herbicidal result of table 6
(note：- represent not test, ET is etoxazole, the albefaction of * leaf margins part)
Using etoxazole as control, mutual-through type has carried out in vitro rape Plating, barnyard grass small-radius curve track and live body for I compound
Pot experiment, as a result shows that the compound that formula is I has fine inhibitory activity under the μ g/mL of concentration 100 to rape and barnyard grass, its
The middle effect of compound 6 is obvious；Under 100 grams/acre of concentration, formula is I part of compounds to rape, three-coloured amaranth, barnyard grass and lady's-grass
Soil treatment and cauline leaf process have all shown certain activity of weeding and whitening action.
Claims (4)
1.4- phenyl is aligned containing alcohol oxime ether structure oxazoline compounds I,
It is characterized in that the compound shown in formula I is：
2. the 4- phenyl contraposition described in claim 1 is killing cinnabar leaf containing alcohol oxime ether structure oxazoline compounds 5~11
Application in mite children mite and mite ovum.
3. the 4- phenyl contraposition described in claim 1 is following in preventing and treating containing alcohol oxime ether structure oxazoline compounds 1~11
Ten kinds of pathogens：Cucumber is withered, peanut foxiness, apple wheel line, tomato early epidemic, gibberella saubinetii, potato late blight, rape sclerotium,
Application in cucumber grey mold, rice banded sclerotial blight, Phytophthora capsici.
4. described in claim 1 4- phenyl contraposition containing alcohol oxime ether structure oxazoline compounds 1~11 prevent and kill off it is following
Weeds：Application in rape, three-coloured amaranth, barnyard grass and lady's-grass.
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| WO2021057852A1 (en) * | 2019-09-24 | 2021-04-01 | 南开大学 | Oxazoline compound, synthesis method therefor and application thereof |
| CN112624995B (en) * | 2019-09-24 | 2022-11-11 | 南开大学 | Synthesis method of 2, 4-diphenyl-4, 5-dihydrooxazoline compound |
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| CN1173172A (en) * | 1995-01-20 | 1998-02-11 | 纳幕尔杜邦公司 | Insecticidal and acaricidal oxaxolines and thiazolines |
| CN1498213A (en) * | 2001-03-23 | 2004-05-19 | �Ϻ���ͨ��ѧ | Arylisoxazoline derivaties, method for production and use there of as pesticides |
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| CN1498213A (en) * | 2001-03-23 | 2004-05-19 | �Ϻ���ͨ��ѧ | Arylisoxazoline derivaties, method for production and use there of as pesticides |
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