CN104910093A - 4-phenyl para-alcohol oxime ether-containing oxazoline compound and preparation and application in controlling insects, mites, bacteria and weeds - Google Patents
4-phenyl para-alcohol oxime ether-containing oxazoline compound and preparation and application in controlling insects, mites, bacteria and weeds Download PDFInfo
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- CN104910093A CN104910093A CN201410091120.7A CN201410091120A CN104910093A CN 104910093 A CN104910093 A CN 104910093A CN 201410091120 A CN201410091120 A CN 201410091120A CN 104910093 A CN104910093 A CN 104910093A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—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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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
Abstract
The invention relates to a 4-phenyl para-alcohol oxime ether-containing oxazoline compound as shown in the general formula (I), preparation of the compound and an application of the compound in pesticides. The compound represents a novel concise, wide-spectral and high-efficiency insecticidal anti-mite bactericidal herbicide structure type. When used as a novel insecticidal anti-mite bactericidal herbicide, the 4-phenyl para-alcohol oxime ether-containing oxazoline compound can greatly control oriental armyworm, cotton bollworm, corn borer, plutella xylostella, beet armyworm and mosquito larvae, can greatly control Tetrangychus cinnabarinus, can greatly inhibit ten pathogenic bacteria including cucumber fusarium wilt, Cercospora arachidicola, Physalospora piricola Nose, Alternaria solani, Fusarium graminearumt, late blight of potato, sclerotinia sclerotioru, Botrytis cinerea, rice sheath blight and phytophthora capsici, and can control and eliminate weeds including rape, amaranth, barnyard grass and crab grass, wherein the meaning of R is as shown in the specification.
Description
Technical field
The present invention relates to a class Novel 4-phenyl contraposition contain alcohol oxime ether structure oxazoline compounds and preparation thereof and control worm, mite, bacterium, careless in application, belong to technical field of pesticide.
Background technology
As everyone knows, chemical pesticide occupies an important position in disease pest and weed Synthetical control system always, and will continue to be method very valuable in disease pest and weed control in one period in the future, in human health care, guarantee farm crop high yield etc., play indelible effect.But the person poultry poisoning produced by chemical pesticide, environmental pollution, the day by day serious (Pestic.Sci.1998 of " three R " problem i.e. residual (Residue), resistance (Resistance) and pest resurgence (Resurgence), 54,300 ~ 322.; Agricultural chemicals; 2009; 48 (9); 625 ~ 628.); bring serious harm to non-target organisms such as Mammalss, pollute environment and even destroy the eubiosis; this just requires that the direction of current plant protection is the regulation and control to harmful organism, not " kills (-cide) " simply.
Benzoylurea derivertives is as a class " insect growth regulator(IGR) (Insect Growth Regulators; be called for short IGRs) ", by the growth of interference insect, cast off a skin, the distinctive physiological process such as breeding carrys out Control pests, started the history of third generation sterilant; Emphasize to control pest population and regulate, optionally effective pest control, to people, animal, pest natural enemy and ecological environment security, meet requirement and target (Pestic.Biochem.Physiol.1979,12,10 ~ 22. of current green pesticide; J.Agric.Food Chem.1973,21 (3), 348 ~ 354.).Second mite azoles (Etoxazole, structural formula one), 2 of current Unique Product, 4-phenylbenzene-1,3-oxazoline class benzoylurea derivertives, not only has the acaricidal activity that other chitin synthesis inhibitors are incomparable, but also has good insecticidal activity.Oxime ether structure is the important active fragments of a class, and be widely used in many pesticide molecules, such as, flucycloxuron, fenpyroximate, orysastrobin, enostroburin, the commercialization medicaments such as fluxofenim all contain the active group of oxime ether structure.Wherein, flucycloxuron (Flucycloxuron, structure one) is the benzoyl area kind chitin synthesis inhibitor containing alcohol oxime ether structure of the Phillips Duphar company initiative of Holland, has extraordinary insecticidal activity.Bibliographical information 2,4-phenylbenzene-1,3-oxazoline compounds in 2006 and benzoyl urea compound have closely similar structure activity relationship (J.Pestic.Sci.2006,31 (4), 409 ~ 416.).
In the process of novel, green, the efficient pesticide-miticide of initiative, we are simultaneously in conjunction with the structure activity relationship of flucycloxuron and second mite azoles, and the initiative longitude and latitude of second mite azoles, design and synthesis 4-phenyl contraposition contains the derivative Z-1 ~ Z-3 (structural formula one) of alcohol oxime ether structure, and synthetic method is as shown in Scheme1.Bioactivity research finds that compound Z-1 ~ Z-3 only shows pesticide and miticide actility (table 1) to small cabbage moth, beet armyworm and carmine spider mite children mite and mite ovum.
Table 1. compound Z-1 ~ Z-3 pesticide and miticide actility test result
Note :-represent undetermined
Summary of the invention
The object of the invention is to provide a class Novel 4-phenyl contraposition to contain alcohol oxime ether structure oxazoline compounds and preparation thereof and the application in disease pest and weed is prevented and treated.The present invention finds 2 in early stage, 4-phenylbenzene-1, derivative Z-1 ~ Z-3 that the 4-phenyl contraposition of 3-oxazoline is connected with alcohol oxime ether structure have kill small cabbage moth, beet armyworm and carmine spider mite basis on, break through tradition limitation, carry out skeleton innovation, optimize a collection of structure properties to stablize, kill small cabbage moth, compound that the effect of beet armyworm and carmine spider mite is better than Z-1 ~ Z-3, and Late Cambrian contains alcohol oxime ether structure oxazoline compounds to the contraposition of 4-phenyl also has and well kill bollworm, Pyrausta nubilalis (Hubern)., aphid, mosquito larvae and sterilization, weeding activity.The present invention is for initiative is novel, wide spectrum, efficient agricultural disease pest and weed pesticide control are laid a good foundation, and possess good creativeness.
The compound of structure shown in be general structure be (I) that Novel 4-phenyl contraposition of the present invention contains alcohol oxime ether structure oxazoline compounds:
In formula, OR represents cycloalkanone oxime, benzaldoxime, Substituted benzaldoxime etc.
It is that shown in following structural formula two, structure 1-11 is the compound of representative that 4-phenyl of the present invention contraposition contains alcohol oxime ether structure oxazoline compounds (general formula I).
The compound of general formula of the present invention (I) can by the method preparation shown in Scheme2.F is joined in methylene dichloride, add Potassium Bromide again, potassium bromate and water, drip hydrochloric acid at 0 DEG C, react 25 hours, organic phase sodium carbonate solution, sodium hydrogen carbonate solution are washed till colourless, then use dichloromethane extraction aqueous phase, merge organic phase sodium chloride solution and wash, then anhydrous magnesium sulfate drying is used, suction filtration, is spin-dried for obtain white solid, obtains intermediate g with toluene and sherwood oil recrystallization.Then, sodium hydride is joined dimethyl formamide, then add ketoxime, react 40 minutes, react complete under adding intermediate g, ice bath, monitor with TLC, add ethyl acetate, with a large amount of saturated common salt water washing, aqueous phase merging is extracted with ethyl acetate, and merges organic phase anhydrous magnesium sulfate drying, suction filtration, be spin-dried for, make eluent silica gel column chromatography with petrol ether/ethyl acetate=10/1 (v/v) and be separated, obtain product I.
The compound of general formula of the present invention (I) has excellence and kills carmine spider mite activity.To carmine spider mite children mite, compound 9,10,11 active effect is best, is 10 in test concentrations
-4during mg/L, mortality ratio is 100%, and second mite azoles is 10
-3mortality ratio under mg/L concentration is 40%, higher than known compound Z-1 ~ Z-3; To carmine spider mite mite ovum, compound 9,10 active effect is for being 10 in test concentrations
-4during mg/L, mortality ratio is 100%, is better than second mite azoles 10
-3mortality ratio under mg/L concentration is 30%, active in known compound Z-1 ~ Z-3 to young mite; Compound 1-10 to young mite and mite ovum activity all higher than second mite azoles.
The compound of general formula of the present invention (I) can also prevent and treat bollworm, Pyrausta nubilalis (Hubern)., small cabbage moth, beet armyworm, aphid, mosquito larvae well; Wherein compound 8 is when concentration is 600mg/L, bollworm is shown to the lethality rate of 83.3%, when concentration is 600mg/L, compound 7 pairs of bollworms show the lethality rate of 80%, and second mite azoles is when concentration is 600mg/L, bollworm is shown to the lethality rate of 50%; Compound 1,6,7,8,9,10 is when test concentrations is 100mg/L, respectively 49% is shown to small cabbage moth, 70%, 50%, 85%, 60%, the lethality rate of 70%, higher than known compound Z-1 ~ Z-3, compound 4 shows the lethality rate of 100% to small cabbage moth when 600mg/L, higher than known compound Z-1 and Z-2.Compound 10, when test concentrations is 5mg/L, shows the lethality rate of 80% respectively to mosquito larvae, suitable with the insecticidal effect of second mite azoles under 5mg/L concentration.Compound 11, when test concentrations is 25mg/L, shows the lethality rate of 60% to mythimna separata, second mite azoles, when test concentrations is 100mg/L, shows the lethality rate of 40% to mythimna separata.
The compound of general formula of the present invention (I) can suppress following ten kinds of pathogenic bacterias well: cucumber is withered, peanut foxiness, apple take turns line, tomato early epidemic, gibberella saubinetii, potato late blight, rape sclerotium, cucumber grey mold, rice banded sclerotial blight, Phytophthora capsici, wheat white powder, excellent spore tikka.
The compound of general formula of the present invention (I) has certain inhibition to rape, barnyard grass, three-coloured amaranth etc.
The compound of general formula of the present invention (I) can directly use as Insecticiding-miticiding sterilant, also can add that the carrier agriculturally accepted uses, also can with other Insecticiding-miticiding sterilant as emamectin-benzoate, tebufenpyrad, bromothalonil, second mite azoles, fenpyroximate etc. combinationally use, the performance synergism that these compositions have, some performance summation actions.
4-phenyl of the present invention contraposition contains the agricultural entomogenous fungi grass control agent of the more existing use of oxazoline compounds of alcohol oxime ether structure, has very large advantage: chemical structure is simple, stable chemical nature, biological spectrum is wide, Insecticiding-miticiding sterilization is significantly active; Toxicity is low, and environment compatibility is good, to non-target organism safety.The present invention is for initiative is novel, wide spectrum, efficient agricultural disease pest and weed control agent are laid a good foundation, and possess 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) compound f, 40mL methylene dichloride, 40mL water, 1.9g (16.1mmol) Potassium Bromide and 1.33g (8.05mmol) potassium bromate is added successively in 250mL single port bottle.Ice-water bath temperature control 0 DEG C, drip the solution 20mL containing concentrated hydrochloric acid 6.1mL, react 25 hours, TLC monitoring reaction is complete, separatory, organic phase extremely close to colourless, then uses dichloromethane extraction aqueous phase with sodium carbonate solution, sodium hydrogen carbonate solution washing successively, merge organic phase sodium chloride solution to wash, anhydrous MgSO
4drying, suction filtration, is spin-dried for obtain white solid, obtains product g with toluene and sherwood oil recrystallization, altogether 3.5g, yield 55.9%.Fusing point: 127-128 DEG C.
1H NMR(400MHz，CDCl
3)δ7.45-7.36(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 is added in 100mL single port bottle, 50mL dimethyl formamide and 0.51g (5.15mmol) cyclopentanone oxime, react 40 minutes, add 1.0g (2.57mmol) intermediate g, react complete to TLC monitoring reaction under condition of ice bath, add ethyl acetate, with a large amount of saturated common salt water washing, aqueous phase merging is extracted with ethyl acetate, merge organic phase anhydrous magnesium sulfate drying, suction filtration, screw out solvent and obtain reddish-brown liquid, with petrol ether/ethyl acetate=10/1 column chromatography, obtain yellow oil 0.65g.Yield 68.8%.
1H NMR(400MHz，CDCl
3)δ7.49-7.31(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，CDCl
3)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 C
21H
20F
2N
2O
2[M+H]
+371.1566；found371.1570.
Embodiment 2: the synthesis of compound 2 ~ 11:
Adopt method synthetic compound 2 ~ 11 shown in embodiment 1.
Compound 2
Yellow thick liquid, yield is 40%.
1H NMR(400M，CDCl
3)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 C
22H
22F
2N
2O
2H[M+H]
+385.1722；found385.1722.
Compound 3
Light yellow liquid, yield is 46.4%.
1H NMR(400MHz，CDCl
3)δ7.46-7.41(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 C
21H
20F
2N
2O
2[M+H]
+399.1879；found399.1875.
Compound 4
Yellow thick liquid, yield is 68%.
1H NMR(400M，CDCl
3)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 C
23H
18F
2N
2O
2H[M+H]
+398.1409；found398.1408.
Compound 5
Light yellow liquid, yield is 61.2%.
1H NMR(300MHz，CDCl
3)δ8.38(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，CDCl
3)δ164.1，162.6，162.5，161.7，160.0，157.6，147.93，147.90，141.6，136.8，134.5，134.4，132.5，132.4，132.33，130.28，130.2，129.0，126.8，123.2，123.2，116.9，116.7，113.4，113.2，112.1，112.1，111.8，76.3，74.8，70.1.HRMS(MALDI)：Calcd.for C
23H
17F
3N
2O
2[M+H]
+411.1315；found411.1307.
Compound 6
Yellow thick liquid, yield is 32.0%.
1H NMR(300MHz，CDCl
3)δ8.08(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，CDCl
3)δ164.1，162.6，162.5，161.7，160.0，157.6，147.93，147.90，141.6，136.8，134.5，134.4，132.5，132.4，132.33，130.28，130.2，129.0，126.8，123.25，123.22，116.9，116.7，113.4，113.2，112.1，112.1，111.8，76.3，74.8，70.1.HRMS(MALDI)：Calcd.for C
23H
17F
3N
2O
2[M+H]
+411.1315；found411.1315.
Compound 7
Light yellow solid, fusing point 85-87 DEG C, yield is 33.3%.
1H NMR(400MHz，CDCl
3)δ8.10(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，CDCl
3)δ147.9，141.6，137.0，132.5，132.4，132.3，128.9，126.8，115.9，115.7，112.1，111.8，76.1，74.8，70.1.HRMS(MALDI)：Calcd.for C
23H
17F
3N
2O
2[M+H]
+411.1315；found411.1313.
Compound 8
Yellow thick liquid, yield is 32.0%.
1H NMR(400MHz，CDCl
3)δ8.11(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，CDCl
3)δ162.6，162.5，160.02，159.96，157.6，153.2，149.0，141.5，137.2，132.5，132.4，132.3，129.4，128.9，126.9，126.7，125.7，112.1，111.8，107.5，107.3，107.1，75.9，74.8，70.1，34.8，31.2.HRMS(MALDI)：Calcd.for C
27H
26F
2N
2O
2[M+H]
+449.2035；found449.2032.
Compound 9
Light yellow liquid, yield is 70.4%.
1H NMR(400MHz，CDCl
3)δ8.51(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，CDCl
3)δ164.1，162.6，162.5，161.7，160.0，157.6，147.93，147.90，141.6，136.8，134.5，134.4，132.5，132.4，132.33，130.28，130.2，129.0，126.8，123.25，123.22，116.9，116.7，113.4，113.2，112.1，112.1，111.8，76.3，74.8，70.1.HRMS(MALDI)：Calcd.for C
24H
17F
5N
2O
2[M+H]
+461.1283；found461.1287.
Compound 10
Yellow thick liquid, yield is 53.9%.
1H NMR(400MHz，CDCl
3)δ8.15(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，CDCl
3)δ164.1，162.6，162.5，161.7，160.0，157.6，147.93，147.90，141.6，136.8，134.5，134.4，132.5，132.4，132.33，130.28，130.2，129.0，126.8，123.25，123.22，116.9，116.7，113.4，113.2，112.1，112.1，111.8，76.3，74.8，70.1.HRMS(MALDI)：Calcd.for C
24H
17F
5N
2O
2[M+H]
+461.1283；found461.1282.
Compound 11
Yellow thick liquid, yield 52.6%.
1H NMR(400M，CDCl
3)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 C
24H
17F
5N
2O
2[M+H]
+461.1283；found461.1285.
The contraposition of embodiment 3:4-phenyl contains alcohol oxime ether structure oxazoline compounds 1-11 to mythimna separata (M.separate), northern house (C.pipiens), the insecticidal activity of bollworm (H.armigera) and Pyrausta nubilalis (Hubern). (P.nubilalis):
Mensuration program is as follows:
The active testing of oriental armyworm
The experimental technique of oriental armyworm: leaf dipping method, after being configured to desired concn, the blade that diameter is about 5-6cm is soaked into the liquid 5-6 second, take out, be placed on thieving paper and dry, be placed in the culture dish of specifying, access 10 3 instar larvaes, check result after 3-4 days is observed in the insectary putting into 27 ± 1 DEG C.
The active testing of mosquito larvae
The experimental technique of mosquito larvae: culex pipiens pallens, the normal population of indoor feeding.Take test compound and be about 5mg in penicillin medicine bottle, add 5mL acetone (or suitable solvent), vibration is dissolved, and is 1000mg/kg mother liquor.Pipette 0.5mL mother liquor, add and fill in the 100mL beaker of 89.5mL water, choose larvae at the beginning of 10 4 ages, pour in the lump in beaker together with 10mL feeding liquid, the concentration of its liquid is 5mg/kg.Put into standard treatment chamber, 24h check result.With the aqueous solution containing 0.5mL test solvent for blank.
The active testing of bollworm
The experimental technique of bollworm: feed mixes medicine method, pipettes 3mL and adds in the feed just configured of about 27g from the solution configured, thus obtains the desired concn of dilution ten times.Pour into equably in 24 clean orifice plates after medicament mixing, cool rear access 24 3 bollworm in age of drying in the air, observes check result after 3-4 days.
The active testing of Pyrausta nubilalis (Hubern).
The test method of Pyrausta nubilalis (Hubern).: leaf dipping method, after being configured to desired concn, being about 5-6cm blade diameter and soaking into the liquid 5-6 second, take out, be placed on thieving paper and dry, be placed in the culture dish of specifying, access 10 3 instar larvaes, check result after 3-4 days is observed in the insectary putting into 27 ± 1 DEG C.
Table 2 compound is to the determination of activity of oriental armyworm, mosquito larvae, bollworm, Pyrausta nubilalis (Hubern).
(note: ET is second mite azoles)
With broad spectrum insecticide miticide second mite azoles for contrast, carried out oriental armyworm, northern house, bollworm and corn borer activity test, test result shows that part of compounds shows greater activity, and part of compounds is higher than the effect or quite of second mite azoles.Compound 11 shows higher mythimna separate, and far away higher than second mite azoles mythimna separate, part of compounds shows necessarily kills bollworm and corn borer activity.
The contraposition of embodiment 4:4-phenyl contain alcohol oxime ether structure oxazoline compounds 1 ~ 11 pair of carmine spider mite children mite, mite ovum, small cabbage moth, beet armyworm kill mite insecticidal activity:
Mensuration program is as follows:
The active testing of carmine spider mite children mite
To the selection of young mite
First spawning time consistent ovum will be obtained, the ovum produced in available 24 hours, before egg hatching, (the 5th day after laying eggs under 25 DEG C of conditions) has taken off ovum blade, be cut into small pieces be placed on tool two panels true leaf blade above, in greenhouse under sun exposure, the young mite newly hatched afterwards for a day can be transferred on young leaves.Can according to test requirements document, select the young mite etap to carry out chemicals treatment, the worm amount of each tested plant should be no less than 60.
Test method: pickling process
With straight peen ophthalmology tweezers, the pea seedlings blade of inoculated carmine spider mite children mite is put into the liquid prepared, guarantee whole dip-dye, time 2-3 second, get rid of remaining liquid.Each strain, every strain 2 blades.After liquid is dry, put into the culture dish that the markd diameter 10cm of tool is long, within 96 hours, each compound of check result repeats 3 times.Contrast only adds emulsifying agent and solvent in distilled water, stirs.
The active testing of carmine spider mite mite ovum
To the selection of ovum
On the blade becoming female mite to be seeded in carmine spider mite to have two panels true leaf bean seedlings with fine, soft fur pen, every strain connects 14 and becomes mites, and namely each blade connects 7, is placed in 25 DEG C of thermostatic chambers.Mite is removed into, about generally can producing 100 ovum after laying eggs 24 hours.Under similarity condition, continue placement can carry out chemicals treatment after 24 hours.
Test method: pickling process
With straight peen ophthalmology tweezers, the pea seedlings blade of inoculated carmine spider mite ovum is put into the liquid prepared, guarantee whole dip-dye, time 2-3 second, get rid of remaining liquid.Each strain, every strain 2 blades.After liquid is dry, put into the culture dish of the markd diameter 10cm of tool, check result after 96 hours.
The active testing of small cabbage moth and beet armyworm
Small cabbage moth (Plutella xylostella) surveys for Nankai University is raw the insect that room uses artificial diet for a long time.Rearing conditions: T, 24 ~ 26 DEG C; RH, 70% ~ 80%; L/D, 14h/10h.The Individual Size second instar larvae consistent with physiological status is chosen for examination during test.
Beet armyworm (Spodoptera exigua) surveys for Nankai University is raw the insect that room uses artificial diet for a long time.Rearing conditions: T, 27 ± 1 DEG C; RH, 50% ~ 75%; L/D, 14h/10h.The instar larvae confession examination in three ages that Individual Size is consistent with physiological status is chosen during test.
Adopt the leaf dipping method that international resistance Action Committee (IRAC) proposes.Analytical balance takes 2mg medicine sample in 10mL small beaker, add 50uL dimethyl formamide (analytical pure) and dissolve, add 10mL water and make 200mg/kg liquid.With straight peen ophthalmology tweezers dipping cabbage leaves, 2 ~ 3 seconds time, get rid of remaining liquid.Each 1, totally 3, each sample.Be successively placed in treatment paper by sample flag sequence.After liquid is dry, put into the straight type pipe that the markd 10cm of tool is long, access 2 age diamondback moth larvae, build the mouth of pipe with gauze.Test process is placed in standard treatment chamber, check result after 96h.Each compound repeats 3 times.Contrast only adds emulsifying agent and solvent in distilled water, stirs.
Table 3 compound is to carmine spider mite children mite, mite ovum, small cabbage moth and beet armyworm determination of activity (concentration mg/L)
(note :-represent and do not test, ET is second mite azoles)
With broad spectrum insecticide miticide second mite azoles for contrast, carry out the active testing to killing carmine spider mite children mite and mite ovum, what result showed that the contraposition of 4-phenyl contains that alcohol oxime ether structure oxazoline compounds 1 ~ 11 all does well kill carmine spider mite children mite and mite ovum is active, and all show far above second mite azoles kill carmine spider mite children mite and mite ovum active, compound 5-11 shows the lethality rate of 100% to young mite activity under the concentration of 0.0001mg/L, compound 5, 9, the activity of 10 pairs of mite ovum is all 100% under the concentration of 0.0001mg/L, and compound 5, 8, 9 far away higher than compound Z-1 ~ Z-1 to kill young mite and mite ovum active, carry out small cabbage moth and beet armyworm active testing, test result shows, the contraposition of 4-phenyl contains alcohol oxime ether structure oxazoline compounds 1 ~ 11 pair of small cabbage moth and has certain biological activity, wherein compound 1,5,6,8,9 activity is far away higher than compound Z-1 ~ Z-1, is the lethality rate that 100mg/L still shows more than 45% in test concentrations.Part of compounds shows killing beet noctuids activity.
Embodiment 5: the contraposition of part 4-phenyl contains alcohol oxime ether structure oxazoline compounds fungicidal activity:
Mensuration program is as follows:
A. in vitro sterilization test, biomass growth rate assay method (Plating):
Precise testing compound, aseptically, select methyl-sulphoxide, N, N-dimethylimino, acetone equal solvent to dissolve, and it is for subsequent use to be diluted with water to series concentration according to the character of compound.Drawing 1mL liquid transfers in the culture dish of 9cm, and the substratum then adding 9mL shakes up and makes it to mix with liquid, is placed to containing dull and stereotyped, and by the flat board treatment group in contrast containing 1mL sterilized water and 9mL substratum.The punch tool that use diameter is 4mm is got bacterium dish and is transferred on culture medium flat plate.Each process repetition 3 times, is placed on temperature in constant incubator and is set to 24 ± 1, and within 72 hours, with the diameter of " Invest, Then Investigate " each bacterium dish expansion, fungicidal activity inhibiting rate is tried to achieve by following formula:
I＝(D1-D2)/D1*100％
I is bacteriostasis rate, and D1 represents the diameter of blank group expansion bacterium dish, and D2 is the diameter of chemicals treatment group expansion bacterium dish.
B. live body sterilization test:
Gray mold: first botrytis cinerea to be gone on PDA flat board activation 3 days, then forward in PD liquid medium, every bottle of transferase 45 block, needs cultivation 6 days, beat mycelia, (transmittance: 9.8%) spray inoculation, then moisturizing is cultured to morbidity to measure transmittance.
Rape sclerotium: first Sclerotinia sclerotiorum to be gone on PDA flat board activation after 3 days, then go in PD liquid medium, every bottle of transferase 45 block, 6 days need be cultivated, beat mycelia, (transmittance: 1.1%) spray inoculation, then moisturizing is cultured to morbidity to measure transmittance.
Wheat white powder: first collect the Powdery Mildew Fresh spores that on morbidity wheat leaf blade, 24h produces, then Fresh spores is evenly inoculated on the potted plant stem and leaf of Wheat of 2-3 leaf phase.
According to the situation of blank morbidity, classification investigation is carried out to inoculation leaves infected situation, adopts with the following method: be 0 grade without scab; It is 1 grade that the area of scab accounts for whole leaf area less than 5%; It is 3 grades that lesion area accounts for whole below leaf area 6%-10%; It is 5 grades that spot area accounts for whole below leaf area 11%-25%; It is 7 grades that lesion area accounts for whole below leaf area 26%-50%; It is 9 grades that lesion area accounts for whole leaf area more than 50%;
The method of calculation of disease index and prevention effect are:
Disease index=[∑ (the typical value number of the sick number of blade at different levels × relative progression) ÷ (typical value of total leaf number × highest number)] × 100;
Preventive effect=[(the average disease index of control group-process average disease index) the average disease index of ÷ control group] × 100.
Phytophthora capsici is sick: first P. capsici is gone to PDA flat board activation 3 days, then transfer to about illumination cultivation 7d on oat plate culture medium, finally brush hyposporangium suspension, continue under leaving the condition of 4 DEG C in 1 hour for subsequent use.Use liquid-transfering gun to draw the liquid 1mL prepared to be inoculated in seedling rhizome about 1cm and to locate; Adopt root-pouring method to connect bacterium, spore concentration is formulated as 1 and is made as root 5/ml, locate inoculation with liquid-transfering gun seedling rhizome about 1cm, moisturizing 12h.The grade scale of filling with root inoculation method is:
0 grade is decided to be without any symptom of catching an illness; The slightly blackening of seedling rhizome position, and blade appearance is not wilted or restorability wilting is decided to be 1 grade; The position blackening of seedling rhizome reaches 1 ~ 2cm, and blade occurs that irrecoverability is wilted, and the blade of plant bottom is even to be had to come off and be decided to be 2 grades; Seedling rhizome portion occurs that blackening is more than 1 ~ 2cm, and blade occurs obviously to wilt or fall leaves morely to be decided to be 3 grades; There is blackening, shrinkage in seedling rhizome portion, generation leaf in vegetative point outside comes off or whole strain is wilted is decided to be 4 grades; Plant is completely withered is decided to be 5 grades.
The method of calculation of disease index and prevention effect are:
Disease index (DI)=[∑ (the strain number of sick value of series × this sick level disease) × 100] ÷ (maximum × investigation strain number of sick level);
Preventive effect=[(contrast average disease index-process average disease index) ÷ contrasts average disease index] × 100.
The in vitro fungicidal activity measurement result of table 4
(note :-represent and do not test, ET is second mite azoles)
Table 5 part of compounds live body bacteriostatic activity test result
(note :-representing and do not test, ET is second mite azoles, and X represents Azoxystrobin, and * represents the inhibiting rate of dimethomorph under 12.5mg/L concentration.)
With second mite azoles and commercialization sterilant Azoxystrobin, dimethomorph for contrast, mutual-through type is that the compound of I has carried out in vitro and live body fungicidal activity test, result shows that general formula is that the part of compounds of I is withered to cucumber under concentration 50 μ g/mL, peanut foxiness, apple wheel line, tomato early epidemic, gibberella saubinetii, potato late blight, rape sclerotium, cucumber grey mold, rice banded sclerotial blight, Phytophthora capsici have in vitro fungicidal activity very well, wherein to apple wheel line and rape sclerotium successful, the inhibit activities of part of compounds to apple wheel line reaches more than 89%; Under concentration 200 μ g/mL, general formula is that the part of compounds of I has fine live body fungicidal activity to rape sclerotium, rice banded sclerotial blight, wheat white powder, cucumber rod spore tikka, the mould live body of epidemic disease, cucumber grey mold.
Embodiment 6: the contraposition of part 4-phenyl contains alcohol oxime ether structure oxazoline compounds weeding activity:
Mensuration program is as follows:
A. isolated activity measures:
Rape Plating, be in the culture dish of 6cm, complete the original shape filter paper that diameter is 5.6cm at diameter, the filter paper of culture dish adds the testing compound solution of 2ml aimed concn, Semen Brassicae campestris was soaked seed before 6 hours in experiment beginning, eachly repeat placement 15 Semen Brassicae campestriss, then place and remain on 30 ± 1 DEG C in dark conditions, after 66 hours, measure rape radicle length, contrast with blank and try to achieve growth inhibition ratio.
Barnyard grass small-radius curve track, first one deck granulated glass sphere is added in bottom in the beaker of 50mL, then on granulated glass sphere, spread the filter paper of suitable size, 5mL testing compound solution is pipetted with pipettor, when testing by barnyard grass presprouting of seeds to showing money or valuables one carries unintentionally, 10 barnyard grasses sowed by each beaker, to be then placed under growth lamp Continuous irradiation 72 hours, remain on 28 ± 1 DEG C, evaluated the weeding activity of testing compound by the growing state compared with blank group barnyard grass.
B. pot experiment
Be the Nutrition Soil putting into appropriate amount in the dixie cup of 7cm at diameter, then add a certain amount of water, by presprouting of seeds before sowing, after planting cover certain thickness soil, cultivate in culture condition room, note keeping the growth of moisture, light and temperature suitable for plant.Process is divided into soil treatment and cauline leaf process, after planting testing compound to be sprayed at the processing mode of soil surface during soil treatment, cauline leaf process is seed germination and grows, possesses the examination material of certain growth cauline leaf before treatment, select in the same size, growth phase is synchronous, to gramineous weeds generally in 1.5 leaf phases, broadleaf weeds processed in the 2-3 leaf phase.
The in vitro Herbicidal result of table 6
(note :-represent and do not test, ET is second mite azoles)
Table 6 pot experiment Herbicidal result
(note :-represent and do not test, ET is second mite azoles, the local albefaction of * leaf margin)
With second mite azoles for contrast, mutual-through type is that the compound of I has carried out in vitro rape Plating, barnyard grass small-radius curve track and live body pot experiment, result shows that general formula is that the compound of I has fine inhibit activities to rape and barnyard grass, wherein compound 6 successful under concentration 100 μ g/mL; Under concentration 100 grams/acre, general formula is that the part of compounds of I has all shown certain weeding activity and whitening action to rape, three-coloured amaranth, barnyard grass and lady's-grass soil treatment and cauline leaf process.
Claims (7)
- The contraposition of 1.4-phenyl contains oxazoline class Insecticiding-miticiding sterilization weedicide (shown in general formula I structure) of alcohol oxime ether structure,It is characterized in that the compound shown in general formula I is:
- 2. 4-phenyl according to claim 1 contraposition contains the preparation method of alcohol oxime ether structure oxazoline class I, it is characterized in that it comprises the steps:Wherein R defines as shown in claim 1 general formula I.
- 3. 4-phenyl according to claim 1 contraposition contains the oxazoline class Insecticiding-miticiding sterilization weedicide of alcohol oxime ether structure, it is characterized in that the contraposition of 4-phenyl contain alcohol oxime ether structure oxazoline compounds 1 ~ 11 show well kill carmine spider mite children mite and mite ovum active, and all show higher than second mite azoles kill carmine spider mite children mite and mite ovum active.
- 4. 4-phenyl according to claim 3 contraposition contains the acaricidal activity of alcohol oxime ether structure oxazoline compounds, it is characterized in that compound 5-11 shows the lethality rate of 100% to carmine spider mite children mite activity under the concentration of 0.0001mg/L, compound 5,9,10 pairs of carmine spider mite mite ovum activity are all 100% under the concentration of 0.0001mg/L.
- 5. 4-phenyl according to claim 1 contraposition contains the oxazoline class Insecticiding-miticiding sterilization weedicide of alcohol oxime ether structure, it is characterized in that the oxazoline compounds 1 ~ 11 that the contraposition of 4-phenyl contains alcohol oxime ether structure can prevent and treat oriental armyworm, bollworm, Pyrausta nubilalis (Hubern)., small cabbage moth, beet armyworm, mosquito larvae.
- 6. 4-phenyl according to claim 1 contraposition contains the oxazoline class Insecticiding-miticiding sterilization weedicide of alcohol oxime ether structure, it is characterized in that the oxazoline compounds 1 ~ 11 that the contraposition of 4-phenyl contains alcohol oxime ether structure can suppress following ten kinds of pathogenic bacterias: cucumber is withered, peanut foxiness, apple take turns line, tomato early epidemic, gibberella saubinetii, potato late blight, rape sclerotium, cucumber grey mold, rice banded sclerotial blight, Phytophthora capsici.
- 7. 4-phenyl according to claim 1 contraposition contains the oxazoline class Insecticiding-miticiding sterilization weedicide of alcohol oxime ether structure, it is characterized in that the oxazoline compounds 1 ~ 11 that the contraposition of 4-phenyl contains alcohol oxime ether structure can prevent and kill off following weeds: rape, three-coloured amaranth, barnyard grass and lady's-grass.
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Cited By (4)
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| CN105348211A (en) * | 2015-09-25 | 2016-02-24 | 南开大学 | Oxazoline compound with 4-phenyl para-position containing thioether and derivative structure thereof, preparation and application as pest and mite killing agent |
| WO2021057852A1 (en) * | 2019-09-24 | 2021-04-01 | 南开大学 | Oxazoline compound, synthesis method therefor and application thereof |
| CN112624995A (en) * | 2019-09-24 | 2021-04-09 | 南开大学 | Novel synthesis method of 2, 4-diphenyl-4, 5-dihydrooxazoline compound |
| CN115433141A (en) * | 2022-09-06 | 2022-12-06 | 贵州大学 | Alpha-oximido phenylacetamide compound, preparation method thereof and application thereof as agricultural bactericide |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348211A (en) * | 2015-09-25 | 2016-02-24 | 南开大学 | Oxazoline compound with 4-phenyl para-position containing thioether and derivative structure thereof, preparation and application as pest and mite killing agent |
| CN105348211B (en) * | 2015-09-25 | 2018-02-23 | 南开大学 | The contraposition of 4 phenyl contains thioether and its derived structure oxazoline compounds, preparation and application as insecticidal/acaricidal agent |
| WO2021057852A1 (en) * | 2019-09-24 | 2021-04-01 | 南开大学 | Oxazoline compound, synthesis method therefor and application thereof |
| CN112624995A (en) * | 2019-09-24 | 2021-04-09 | 南开大学 | Novel synthesis method of 2, 4-diphenyl-4, 5-dihydrooxazoline compound |
| CN112624995B (en) * | 2019-09-24 | 2022-11-11 | 南开大学 | Synthesis method of 2, 4-diphenyl-4, 5-dihydrooxazoline compound |
| CN115433141A (en) * | 2022-09-06 | 2022-12-06 | 贵州大学 | Alpha-oximido phenylacetamide compound, preparation method thereof and application thereof as agricultural bactericide |
| CN115433141B (en) * | 2022-09-06 | 2023-08-22 | 贵州大学 | Alpha-oximino phenylacetamide compound, preparation method thereof and application thereof as agricultural bactericide |
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