CN104557910A - Fluorine-containing syn-form novel nicotine compound and preparation method and application thereof - Google Patents
Fluorine-containing syn-form novel nicotine compound and preparation method and application thereof Download PDFInfo
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- CN104557910A CN104557910A CN201310482596.9A CN201310482596A CN104557910A CN 104557910 A CN104557910 A CN 104557910A CN 201310482596 A CN201310482596 A CN 201310482596A CN 104557910 A CN104557910 A CN 104557910A
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- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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- 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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Abstract
The invention relates to a fluorine-containing syn-form novel nicotine compound and a preparation method and application thereof, particularly provides a compound adopting a structure shown in formula (A) or acceptable salt in agricultural pharmacology of the compound, and a preparation method and application of the compound, and further relates to an agricultural composition comprising the compound or the acceptable salt in agricultural pharmacology and application of the composition. The compound has high insecticidal activity towards homoptera agricultural and forestry pests, such as plant hopper and whitefly.
Description
Technical field
The present invention relates to the insecticide of novel anabasine, and its preparation method and application.
Background technology
Neonicotinoid insecticide is considered to forth generation insecticide, is the classics representative of green pesticide.In chemical insecticide field, there is irreplaceable status.This insecticides acts on insect nAChR, is the potent activator of this receptor, has high selectivity.Its high-efficiency low-toxicity, environmental friendliness are the hot fields of current pesticides discovery.Since the phase at the beginning of the nineties in last century, Bayer A.G released Imidacloprid, each large agricultural chemicals companies releases 6 neonicotinoid insecticide, this insecticides has been current most important chemical insecticide kind, more than 120 national registrations, annual global marketing volume reaches more than 2,500,000,000 dollars, market share occupation rate is (European patent 247477,296453,685477,235725,235725,315826,192060,244777, Japan Patent 62292765,8259568,8291171) more than 20%;
But commercialization anabasine insecticide is efficient to sucking pest, lower to the activity of lepidoptera pest, cause insecticidal spectrum narrower.This insecticides is fat-soluble poor simultaneously, is difficult to infiltrate insect wax epidermis, affects the insecticidal activity of this compounds.And fluorine-containing neonicotinoid insecticide is expected to solve the problem, Beyer Co., Ltd will release first fluorine-containing neonicotinoid insecticide (Flupyradifurone) in 2014.Imply that fluorine-containing neonicotinoid insecticide has important development prospect;
Therefore, how carrying out structure of modification to having highly active Nitromethylene compounds, introducing fluorine element to produce new, more effective insecticide, solving the fat-soluble problem of anabasine insecticide, expand insecticidal spectrum, making it be applied to insecticide just becomes the technical issues that need to address of the present invention.
Summary of the invention
The object of the invention is fluorine-containing cis anabasine compound providing one class preventing and control insect and preparation method thereof;
Another object of the present invention is for not providing guarantor by attack of insect and invasion with the crop of results in growth;
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Embodiment
The present inventor is by long-term and deep research, based on the Nitromethylene structure of existing nitro-methylene-type neonicotinoid insecticide, reacted by trifluoroacetyl ethyl ester anil, triethyl orthoformate and nitromethylene-compound, synthesize a kind of novel anabasine compound, the insecticidal activity of this compound has higher insecticidal activity, and has the insecticidal spectrum of expansion.On this basis, inventor completes the present invention;
group definition
As used herein, term " five yuan or hexa-member heterocycle base " refers to such as, containing one or more heteroatomic five yuan or hexatomic ring being selected from nitrogen, oxygen or sulphur, pyridine radicals, thiazolyl, pyrimidine radicals, tetrahydrofuran base, Huo oxazolyl etc.
Compound of the present invention can contain an asymmetric center, and therefore occurs with the form of raceme, racemic mixture, single enantiomer, diastereomeric compound and single diastereomer.The asymmetric center that can exist, depends on various substituent character on molecule.Asymmetric center will produce two optical isomers independently, and all possible optical isomer and non-enantiomer mixture and pure or partial-purified compound comprise within the scope of the present invention.The present invention includes all isomeric form of compound.
the preparation method of the compounds of this invention
The compounds of this invention synthesizes by reactions steps as described above.Those skilled in the art can intermediate conventionally in document synthetic reaction step;
The preparation method of the compounds of this invention can be the preparation method that this area is commonly used, and the invention provides a kind of preferred compounds process for production thereof described in general formula (A), comprises method:
Under condition of no solvent, formula (b) compound, formula (c) compound and formula (d) compound are reacted, thus obtain formula (A) compound:
Above-mentioned various in, R
1, R
2as defined in claim 1;
In a preference, described reaction temperature is 100-150 DEG C, is preferably 110-130 DEG C.
the insecticidal activity of active substance of the present invention
Term " active substance of the present invention " or " reactive compound of the present invention " refer to acceptable salt in the compounds of this invention or its Pesticide Science, and it has the insecticidal activity significantly improved, and the insecticidal spectrum expanded;
Active matter mass-energy of the present invention is used as control and eliminates the insect of agriculture and forestry plant insect, stored grains widely, public health insect and endanger the insect etc. of animal health.In this manual, " insecticide " is the general designation of the material with the effect preventing and treating the above-mentioned all insects mentioned.The example of insect includes but not limited to: Homoptera insect: rice leafhopper (Nephotettix cincticeps), brown plant-hopper (Nilaparvata lugens), Kang Shi mealybug (Pseudococcus comstocki), arrowhead scales (Unaspis yanonensis), black peach aphid (Myzus persicae), cotten aphid (Aphis gossypii), aphis craccivora (Aphis medicagini), radish aphid (Lipaphis erysimi pseudobrassicae), pears class lace bug (Stephanitis nashi), or aleyrodid (Bemisia tabaci).Orthopteran: Groton bug (Blattella germanica), the large Lian of the U.S. (Periplaneta americana), African mole cricket (Gryllotalpa africana), or Asiatic migratory locust (Locus migratoria).Isoptera insect: S.invicta Buren (Solenopsis invicta), or coptotermes formosanus (Coptotermes formosanus).Dipteral insect: housefly (Musca domestica), Aedes aegypti (Aedes aegypti), plant fly (Delia platura), culex (Culex sp.), or Anopheles sinensis (Anopheles sinensis).The insect of harm animal health comprises calf tick (Hyalomma anatolicum), long pin blood tick (Haemaphysalis longicornis) etc.;
The compound that the present invention relates to especially to pierce-suck type, rasping-sucking mouthparts insect as: the agriculture and forestry injurious insects such as aphid, leafhopper, plant hopper, thrips, aleyrodid have special efficacy.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise percentage and number calculate by weight;
Embodiment 1:
Compou nd synthesis in embodiment is implemented according to the following step:
By chloro-for 5mmol2-5-(2-Nitromethylene-imidazolidine-1-ylmethyl)-pyridine, 5mL triethyl orthoformate, 6mmol trifluoroacetic ethyl acetoacetate anil adds in the round-bottomed flask of 50mL, return stirring 3 hours.After cooling, suction filtration, uses petroleum ether.Gained solid product column chromatography (carrene: methyl alcohol=10: 1) separation obtains yellow powdery solid;
Compound experimental data:
Compound 1
Productive rate: 70%.Fusing point: 184-185 DEG C.
1H NMR(CDCl
3)δ(ppm)：8.58(s，1H)，8.34(d，1H，J=1.6Hz，Py-H)，8.11(s，1H)，7.80(dd，1H，J
1＝2.0Hz，J
2＝8.0Hz，Py-H)，7.54(s，1H，Py-H)，7.53(s，1H，Ph-H)，7.35(m，3H，Ph-H)，7.17(t，1H，J=7.2Hz，Ph-H)，5.09(d，1H，J=15.2Hz，Py-CH
2)，4.42(d，1H，J=15.6Hz，Py-CH
2)，4.21-3.63(m，4H，N-CH
2-CH
2-N).IR(KBr,cm
-1)：3274，3203，3075，2898，1638，1551，1448，1351.
Compound 2
Productive rate: 80%.Fusing point: 148-149 DEG C.
1H NMR(DMSO-d6)δ(ppm)：8.50(s，1H)，8.33(d，1H，J=1.6Hz，Py-H)，8.09(s，1H)，7.78(dd，1H，J
1＝2.0Hz，J
2＝8.0Hz，Py-H)，7.39(d，2H，J=8.4Hz，Ph-H)，7.35(d，1H，J=8.0Hz，Ph-H)，7.13(m，2H，Ph-H)，5.08(d，1H，J=15.2Hz，Py-CH
2-)，4.41 (d，1H，J=15.2Hz，Py-CH
2-)，4.16-3.62(m，4H，N-CH
2-CH
2-N)，2.32(s，3H，-CH
3).IR(KBr，cm
-1)：3358，3281，3035，2922，2866，1639，1562，1539，1514，1454，818.
Compound 3
Productive rate: 72%.Fusing point: 183-184 DEG C.
1HNMR(DMSO-d6)δ(ppm)：8.35(d，1H，J=2.0Hz，Py-H)，8.25(s，1H)，8.14(s，1H)，7.81(dd，1H，J
1＝2.4Hz，J
2＝8.0Hz，Py-H)，7.36(d，1H，J=8.4Hz，Py-H)，7.27(m，2H，Ph-H)，7.07(m，2H，Ph-H)，5.06(d，1H，J=15.6Hz，Py-CH
2-)，4.42(d，1H，J＝15.6Hz，Py-CH2-)，4.20-3.62(m，4H，N-CH
2-CH
2-N)，2.27(m，3H，-CH
3)，2.10(s，3H，-CH
3).IR(KBr，cm
-1)：3390，3241，3062，2921，1640，1562，1458，1388，775，745.
Compound 4
Productive rate: 83%.Fusing point: 128-129 DEG C.
1H NMR(CDCl
3)δ(ppm)：8.37(d，1H，J=2.4Hz，Py-H)，8.11(s，1H)，7.98(s，1H)，7.84(dd，1H，J
1＝2.4Hz，J
2＝8.4Hz，Py-H)，7.39(d，1H，J=8.4Hz，Py-H)，7.34(d，1H，J=7.6H
Z，Py-H)，7.01(d，2H，J=8.4Hz，Ph-H)，5.08(d，1H，J=15.6Hz，Py-CH
2)，4.45(d，1H，J=15.6Hz，Py-CH
2)，4.18-3.89(m，4H，N-CH
2-CH
2-N)，2.31(s，3H，CH
3)，2.21(s，3H，CH
3).IR(KBr，cm
-1)：3392，3256，3018，2923，1639，1562，1451，1352，814，743.
Compound 5
Productive rate: 78%.Fusing point: 182-183 DEG C.
1H NMR(DMSO)δ(ppm)：10.06(s，1H)，9.82(s，1H)，8.39(d，1H，J=2.4Hz，Py-H)，8.38(s，1H)，7.85(dd，1H，J
1＝2.8Hz，J
2＝8.4Hz，Py-H)，7.59(s，1H，Ph-H)，7.57(d，1H，J=8Hz，Py-H)，7.10(d，1H，J=3.6Hz，Ph-H)，6.90(d，1H，J=7.2Hz，Ph-H)，4.89(d，1H，J=16Hz，Py-CH
2-)，4.66(d，1H，J=16Hz，Py-CH
2-)，4.08-3.81(m，4H，-N-CH
2-CH
2-N-)，2.26(s，3H，-CH
3)，2.15(s，3H，-CH
3).IR(KBr，cm
-1)：3256，1650，3090，2980，2840，1458，1270，1347，1531，1350，1650，806.
Compound 6
Productive rate: 68%.Fusing point: 202-203 DEG C.
1H NMR(CDCl
3)δ(ppm)：d9.99(s，1H)，8.39(s，1H)，8.30(s，1H，Py-H)，7.86(d，1H，J=8.4Hz，Py-H)，7.84(d，1H，J=8.4H
Z，Py-H)，7.10(s，3H，Ph-H)，4.88(d，1H，J=16Hz，Py-CH
2)，4.56(d，1H，J=16.4Hz，Py-CH
2)，4.03-3.57(m，4H，N-CH
2-CH
2-N)，2.13(s，6H，CH
3).IR(KBr，cm
-1)：3291，3069，3020，2918，1647，1562，1446，1378，778，745.
Compound 7
Productive rate: 84%.Fusing point: 185-186 DEG C.
1H NMR(CDCl
3)δ(ppm)：d9.98(s，1H)，9.94(s，1H)，8.41(d，1H，J=2Hz，Py-H)，8.31(s，1H)，7.89(dd，1H，J
1＝2.6Hz，J
2＝8.2Hz，Py-H)，7.56(d，1H，J=8.4H
Z，Py-H)，6.91(s，2H，Ph-H)，4.89(d，1H，J=16Hz，Py-CH
2)，4.57(d，1H，J=16.4Hz，Py-CH
2)，4.06-3.81(m，4H，N-CH
2-CH
2-N)，2.11(s，3H，CH
3)，2.095(s，6H，CH
3).IR(KBr，cm
-1)：3207，3069，2945，1656，1589，1458，1342，754，733.
Compound 8
Productive rate: 79%.Fusing point: 73-74 DEG C.
1H NMR(CDCl
3)δ(ppm)：d8.47(s，1H)，8.34(d，1H，J=2.0Hz，Py-H)，8.09(s，1H)，7.80(dd，1H，J
1＝2.4Hz，J
2＝8.4Hz，Py-H)，7.42(d，2H，J=8.4H
Z，Ph-H)，7.36(d，1H，J=8.4Hz，Py-H)，7.16(d，2H，J=8.4Hz，Ph-H)5.10(d，1H，J=15.2Hz，Py-CH
2)，4.41(d，1H，J=15.6Hz，Py-CH
2)，4.17-3.49(m，4H，N-CH
2-CH
2-N)，2.63(m，2H，Ph-CH
2)，1.23(m，3H，CH
3).IR(KBr，cm
-1)：3123，2976～2680，1688，1480，1328，1554，1358，1242，837.
Compound 9
Productive rate: 75%.Fusing point: 149-150 DEG C.
1H NMR(CDCl
3)δ(ppm)：d10.18(s，1H)，9.77(s，1H)，8.38(d，1H，J=2.0Hz，Py-H)，8.24(s，1H，Py-H)，7.85(dd，1H，J
1＝2.4Hz，J
2＝8.4Hz，Py-H)，7.48(m，1H，Ph-H)，7.14(m，2H，Ph-H)，4.87(d，1H，J=16.0Hz，Py-CH
2)，4.64(d，1H，J=16.4Hz，Py-CH
2)，4.04-3.84(m，4H，N-CH
2-CH
2-N)，1.52(m，2H，CH
2)，1.27(m，2H，CH
2)，0.89(m，3H，CH
3).IR(KBr，cm
-1)：3300，3150，2976，1480，1242，1328，1554，1358，1688，810.
Compound 10
Productive rate: 87%.Fusing point: 164-165 DEG C.
1H NMR(CDCl
3)δ(ppm)：8.44(s，1H)，8.34(d，1H，J=1.6Hz，Py-H)，8.08(s，1H)，7.79(dd，1H，J
1＝2.8Hz，J
2＝8.0Hz，Py-H)，7.44(m，2H，Ph-H)，7.38(d，1H，J=8.8Hz，Py-H)，6.86(d，2H，J=8.8Hz，Ph-H)，5.08(d，1H，J=15.2Hz，Py-CH
2-)，4.40(d，1H，J=15.2Hz，Py-CH
2-)，4.16-3.61(m，7H，N-CH
2-CH
2-N and O-CH
3)，IR(KBr，cm
-1)：3284，3130，2980，2840，1642，1554，1458，1356，1238，825.
Compound 11
Productive rate: 81%.Fusing point: 146-147 DEG C.
1H NMR(CDCl
3)δ(ppm)：8.44(s，1H)，8.36(d，1H，J=2.0Hz，Py-H)，8.20(dd，1H，J
1＝1.2Hz，J
2＝8.0Hz，Py-H)，8.09(s，1H)，7.84(dd，1H，J
1＝2.8Hz，J
2=8.4Hz，Py-H)，7.39(d，1H，J=8.4Hz，Ph-H)，7.11(m，1H，Ph-H)，6.97(m，2H Ph-H)，5.10(d，1H，J=15.6Hz，Py-CH
2-)，4.42(d，1H，J=15.2Hz，Py-CH
2-)，4.19-3.62(m，7H，N-CH
2-CH
2-Nand-O-CH
3).
Compound 12
Productive rate: 86%.Fusing point: 192-193 DEG C.
1H NMR(DMSO-d6)δ(ppm)：10.18(s，1H)，9.82(s，1H)，8.38(d，1H，J=2.4Hz，Py-H)，8.23(s，1H)，7.85(dd，1H，J
1＝2.4Hz，J
2＝8.4Hz，Py-H)，7.54(d，1H，J=8.4Hz，Py-H)，7.49(d，2H，J=8.8Hz，Ph-H)，6.91(m，2H，Ph-H)，4.87(d，1H，J=16.4Hz，Py-CH
2-)，4.63(d，1H，J=16.0Hz，Py-CH
2-)，4.08-3.80(m，6H，N-CH
2-CH
2-N and O-CH
2-)，1.31(s，3H，-CH
3).IR(KBr，cm
-1)：3435，3285，3071，2927，1632，1575，1535，1509，1474，1357，823.
Compound 13
Productive rate: 46%.Fusing point: 135-136 DEG C.
1H NMR(DMSO-d6)δ(ppm)：8.83(s，1H)，8.41(s，1H)，8.38 (d，1H，J=2.4Hz，Py-H)，8.17(s，1H)，8.06(m，1H)，7.80(dd，1H，J
1＝2.4Hz，J
2＝8.4Hz，Py-H)，7.37(d，1H，J=8.0Hz，Py-H)，7.08(m，3H，Ph-H)，5.08(d，1H，J=15.6Hz，Py-CH
2-)，4.42(d，1H，J=15.6Hz，Py-CH
2-)，4.22-3.62(m，4H，N-CH
2-CH
2-N).IR(KBr，cm
-1)：3650，3355，3066，2957，1642，1617，1567，1541，1454，755.
Compound 14
Productive rate: 53%.Fusing point: 192-193 DEG C.
1H NMR(CDCl
3)δ(ppm)：d8.59(s，1H)，8.35(d，1H，J=2.0Hz，Py-H)，8.09(s，1H)，7.80(dd，1H，J
1＝2.2Hz，J
2＝8.2Hz，Py-H)，7.51(m，2H，Ph-H)，7.37(d，1H，J=8.4Hz，Py-H)，7.05(m，2H，Ph-H)，5.09(d，1H，J=15.6Hz，Py-CH
2)，4.43(d，1H，J=15.2Hz，Py-CH
2)，4.17-3.62(m，6H，-CH
2-).IR(KBr，cm
-1)：3430，3250，2976，1688，1554，1480，1358，1328，1242，803.
Compound 15
Productive rate: 55%.Fusing point: 163-164 DEG C.
1H NMR(CDCl
3)δ(ppm)：
1H NMRδ(ppm)：8.49(s，1H)，8.37(d，1H，J=2.0Hz，Py-H)，8.19(d，J=6.8Hz，1H，Ph-H)，8.10(s，1H)，7.85(dd，1H，J
1＝2.4Hz，J
2＝8.4Hz，Py-H)，7.40(d，1H，J=8Hz，Py-H)，7.11(t，1H，J=8Hz，Ph-H)，6.97(t，1H，J=7.8Hz，Ph-H)，6.90(d，1H，J=8Hz，Ph-H)，5.13(d，1H，J=15.2Hz，Py-CH
2-)，4.43(d，1H，J=15.6Hz，Py-CH
2-)，4.21-3.63(m，4H，-N-CH
2-CH
2-N-).IR(KBr，cm
-1)：3353，3100，2980，2840，1640，1541，1459，1351，1250，825.
Compound 16
Productive rate: 61%.Fusing point: 176-177 DEG C.
1H NMR(CDCl
3)δ(ppm)：
1H NMRδ(ppm)：8.35(d，1H，J=2.4Hz，Py-H)，8.32(s，1H)，8.09(s，1H)，7.79(dd，1H，J
1＝2.4Hz，J
2＝8.8Hz，Py-H)，7.51(m，2H，Ph-H)，7.39(d，1H，J=8.4Hz，Py-H)，7.26(m，2H，Ph-H)，5.12(d，1H，J=15.2Hz，Py-CH
2-)，4.46(d，1H，J=15.6Hz，Py-CH
2-)，4.17-3.63(m，4H，-N-CH
2-CH
2-N-).IR(KBr，cm
-1)：3260，3130，2980，2840，1640，1564，1459，1358，1350，1240，824.
The insecticidal activity test of embodiment 2. the compounds of this invention
To the insecticidal activity of plant hopper
Plant hopper belongs to homoptera pest, has piercing mouth parts, is a kind of common crop pests.With brown planthopper (Nilaparvata lugens) for tested object, adopt spray-on process test;
Operating process: be that solvent is accurately mixed with 500,250ppm solution with acetone by testing compound, and make blank with aqueous acetone solution process.Each process repetition 3 glasss (namely repeating 3 times).With small manual sprayer every glass even spraying 2ml.Dispenser first 6 hours every basins connect rice fulgorid 10.Successively 3 batch experiment are carried out altogether.Process after 24 hours, the dead borer population of statistics examination worm, and calculate lethality (%).The results are shown in Table 1;
Lethality (%)=(contrast borer population-process alive borer population alive)/contrast borer population × 100% alive
Under table 1500ppm condition, compound is to the insecticidal activity of brown planthopper
The preparation of the insecticides of embodiment 3. containing the compounds of this invention
Oleaginous suspension
Prepare following component in proportion: any one compound in 25% (percentage by weight, lower same) compound 1-16; 5% polyoxyethylene sorbitol six oleate; 70% higher aliphatic hydrocarbon ils.Each component is ground together, until solid particle is down to less than about 5 microns in sand mill.The thick suspension of gained can directly use, but also uses after emulsification in water.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after having read above-mentioned instruction content of the present invention.
Claims (6)
1. there is the compound of structure shown in formula (A), or acceptable salt in the optical isomer of described compound or Pesticide Science:
In formula:
R
1for nitrogenous, the oxygen of nitrogenous, oxygen and/or sulphur five yuan or hexa-member heterocycle base, halo and/or five yuan of sulphur or hexa-member heterocycle base or substituted or unsubstituted phenyl, wherein said substituting group is that it is one or more to be selected from lower group: halogen, C
1 – 4haloalkyl or C
1 – 4halogenated alkoxy;
R
2be phenyl independently of one another, or the phenyl that substituting group replaces.
2. compound as claimed in claim 1, or acceptable salt in the optical isomer of described compound, cis-trans-isomer or Pesticide Science, is characterized in that, wherein R
1be selected from: pyridine radicals, thiazolyl, pyrimidine radicals, tetrahydrofuran base, oxazolyl or its halides;
In another preference, R
1for the thiazolyl of the pyridine radicals of halo, halo, the pyrimidine radicals of halo, the tetrahydrofuran base of halo or halo oxazolyl, more preferably described halides is chloro thing;
In another preference, R
1for
,
or
.
3. acceptable salt in compound as claimed in claim 1, or the optical isomer of described compound or Pesticide Science, is characterized in that, R
2for phenyl or replace phenyl.
4.
oneplant insecticides, it comprises:
The compound described in any one of claim 1-3 of (a) 0.001-99.99 % by weight, acceptable salt or their combination in its optical isomer or Pesticide Science; And
Acceptable carrier and/or excipient in (b) Pesticide Science;
In another preference, component (a) accounts for the 0.01-99.9 % by weight of described insecticides, preferred 0.05-90 % by weight.
5. the purposes of the insecticides stated as claim 4, is characterized in that, be selected from following insect: Homoptera, Semiptera, orthoptera, Isoptera or dipteral insect, preferred Homoptera insect for killing or preventing;
In another preference, described insect has pierce-suck type or rasping-sucking mouthparts;
In another preference, described insect is plant hopper, aleyrodid, leafhopper, thrips.
6. a preparation method for acceptable salt in the compound described in any one of claim 1-3 or its Pesticide Science, is characterized in that, comprise method:
Under condition of no solvent, formula (b) compound, formula (c) compound and formula (d) compound are reacted, thus obtains formula (A) compound;
Above-mentioned various in, R
1, R
2as defined in claim 1;
In a preference, described reaction temperature is 100-150 DEG C, is preferably 110-130 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662282A (en) * | 2019-03-07 | 2020-09-15 | 湖南化工研究院有限公司 | Aza-and pyridine compounds and intermediates thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4876263A (en) * | 1987-06-26 | 1989-10-24 | Nihon Tokushu Noyaku Seizo K.K. | Pesticidal nitro-substituted heterocyclic compounds |
| CN101812078A (en) * | 2010-04-12 | 2010-08-25 | 云南大学 | Heterocyclic dihydropyridine compound and synthesis method thereof |
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2013
- 2013-10-16 CN CN201310482596.9A patent/CN104557910B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4876263A (en) * | 1987-06-26 | 1989-10-24 | Nihon Tokushu Noyaku Seizo K.K. | Pesticidal nitro-substituted heterocyclic compounds |
| CN101812078A (en) * | 2010-04-12 | 2010-08-25 | 云南大学 | Heterocyclic dihydropyridine compound and synthesis method thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHENGJIAO YAN ET AL.: ""Three-component solvent-free synthesis of highly substituted bicyclic pyridines containing a ring-junction nitrogen"", 《GREEN CHEMISTRY》 * |
| 邵旭升 等: ""新烟碱类杀虫剂及稠环固定的顺式衍生物研究进展"", 《农药学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662282A (en) * | 2019-03-07 | 2020-09-15 | 湖南化工研究院有限公司 | Aza-and pyridine compounds and intermediates thereof |
| CN111662282B (en) * | 2019-03-07 | 2021-07-06 | 湖南化工研究院有限公司 | Aza-and pyridine compounds and intermediates thereof |
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