CN103833638B - Phenylpyrazole base acrylonitrile compound and application thereof - Google Patents
Phenylpyrazole base acrylonitrile compound and application thereof Download PDFInfo
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- CN103833638B CN103833638B CN201210482920.2A CN201210482920A CN103833638B CN 103833638 B CN103833638 B CN 103833638B CN 201210482920 A CN201210482920 A CN 201210482920A CN 103833638 B CN103833638 B CN 103833638B
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- 0 *C(OC=*=C(c(cc1)n[n]1-c1ccccc1)C#N)=O Chemical compound *C(OC=*=C(c(cc1)n[n]1-c1ccccc1)C#N)=O 0.000 description 7
- KZCITRBVJXGSMJ-UHFFFAOYSA-N CCCO/C(/Cl)=[O]/C Chemical compound CCCO/C(/Cl)=[O]/C KZCITRBVJXGSMJ-UHFFFAOYSA-N 0.000 description 1
- IJNRBGYVKVGQMR-UHFFFAOYSA-N N#CCc(cc1)n[n]1-c1ccccc1 Chemical compound N#CCc(cc1)n[n]1-c1ccccc1 IJNRBGYVKVGQMR-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
- A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
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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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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Abstract
The invention discloses a kind of phenylpyrazole base acrylonitrile compound or its steric isomer of novel structure, compound structure is as shown in general formula I:
, in formula: R
1be selected from C
1-C
6alkyl, halo C
1-C
6alkyl, C
3-C
8cycloalkyl, C
1-C
6alkoxyl group or phenyl, benzene ring hydrogen also can be replaced by following substituting group further: halogen, cyano group, nitro, methyl or halogenated methyl; R
2be selected from chlorine, trifluoromethyl or nitro.Compound of Formula I has excellent desinsection, acaricidal activity, can be used for pest control, evil mite.
Description
Technical field
The invention belongs to Insecticidal and acaricidal agent field.Be specifically related to a kind of phenylpyrazole base acrylonitrile compound and application thereof.
Background technology
Due to Insecticidal and acaricidal agent in use for some time, insect, evil mite can produce resistance to it, therefore, need constantly invention novel with the compound of the tool desinsection improved, acaricidal activity and composition.Meanwhile, along with people are to the growing needs such as agricultural and animal products and the pay attention to day by day to environment protection, also need lower, the environment amenable new Insecticidal and acaricidal agent of use cost always.
Nissan Chemical Ind Ltd, in WO9740009 and JP2005008628 application, discloses the ethene derivatives having desinsection, kill mite or fungicidal activity, reports compound K C respectively
1(in WO9740009 patent numbering II-15) and compound K C
2the preparation of (in JP2005008628 patent numbering 1) and insecticidal activity, these two compounds are distinguished all more than 80% the preventive effect of black peach aphid under the concentration of 500ppm.In WO2007100160 and WO2007100161 application, further disclose compound K C
3the preparation of (in patent numbering 1), insecticidal activity and synthesising process research, compound K C
3under the concentration of 25ppm, to black peach aphid, there is high prevention effect.
In the prior art, the preparation of phenylpyrazole base acrylonitrile compound as representative of the present invention and desinsection thereof, acaricidal activity have no open.
Summary of the invention
The object of the present invention is to provide a kind of phenylpyrazole base acrylonitrile compound of novel structure, the control of insect, evil mite in the health that it can be applicable to agricultural, forestry or non-treatment object.
Technical scheme of the present invention is as follows:
The invention provides a kind of phenylpyrazole base acrylonitrile compound, as shown in general formula I:
In formula:
R
1be selected from C
1-C
6alkyl, halo C
1-C
6alkyl, C
3-C
8cycloalkyl, C
1-C
6alkoxyl group or phenyl, benzene ring hydrogen also can be replaced by following substituting group further: halogen, cyano group, nitro, methyl or halogenated methyl;
R
2be selected from chlorine, trifluoromethyl or nitro;
Or its steric isomer.
The present invention further preferred compound is, in general formula I:
R
1be selected from C
1-C
6alkyl, halo C
1-C
6alkyl, C
3-C
8cycloalkyl, C
1-C
6alkoxyl group or phenyl;
R
2be selected from chlorine, trifluoromethyl or nitro;
Or its steric isomer.
The present invention further preferred compound is, in general formula I:
R
1be selected from C
3-C
6alkyl, halo C
3-C
6alkyl or C
1-C
4alkoxyl group;
R
2be selected from trifluoromethyl;
Or its steric isomer.
In the definition of the compound of Formula I provided above, collect term used and be generally defined as follows:
Alkyl refers to straight or branched form, such as methyl, ethyl, n-propyl, sec.-propyl etc.Cycloalkyl comprises cyclopropyl, cyclobutyl, Cvclopropvlmethvl, methylcyclopropyl groups etc.Haloalkyl refers to the group that alkyl is optionally substituted with one or more halogen atoms, as chloroethyl, trifluoromethyl etc.Alkoxyl group refers to that alkyl end is connected with the group of Sauerstoffatom, such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy etc.Halogen refers to fluorine, chlorine, bromine, iodine.Steric isomer refers in formula I, and substituting group CN and OCOR on carbon-carbon double bond B is in the same side (Z configuration) of B key or both sides (E).
Compound of Formula I of the present invention can be prepared by the following method, and in reaction formula, each group definition is the same.
In formula: L represents suitable leavings group, as chlorine, bromine or tolysulfonyl oxygen base etc.
Compounds of formula II and compound of formula III in suitable solvent, temperature reacts 0.5-48 hour obtained target compound I under-10 DEG C to reflux temperature.
Suitable solvent is selected from methylene dichloride, chloroform, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dioxane, DMF or dimethyl sulfoxide (DMSO) etc.
Add suitable alkaloids favourable to reaction.Suitable alkali can be selected from organic bases, such as triethylamine, DMA, pyridine, sodium methylate, sodium tert-butoxide or potassium tert.-butoxide etc.; Or mineral alkali is as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate or sodium hydride etc.
According to the difference of reaction conditions or the difference of starting raw material, there is steric isomerism in compound of Formula I.Such as, substituting group CN and OCOR on carbon-carbon double bond B
1in the same side (Z configuration) or both sides (E) of B key.By selecting suitable starting raw material or controlling reaction conditions, the excessive product of a kind of isomer or individual isomer can be obtained.Also by carrying out the separation of conventional means to crude product, such as, by the method such as column chromatography, recrystallization, individual isomer can be obtained.The structure of these isomer is by X-ray single crystal diffraction, and the conventionals method of analysis such as nucleus magnetic resonance are determined.
Compound of formula III has commercially available.
The preparation method of Compounds of formula II is as follows:
In formula: L
1represent suitable leavings group, as chlorine, bromine, pyrazolyl, imidazolyl, ester group or tolysulfonyl oxygen base etc.
Compound of Formula IV and compounds of formula V are in suitable solvent, in the presence of base, temperature reacts 0.5-48 hour obtained general formula compound II under-10 DEG C to boiling point.
Suitable solvent is mainly selected from: methylene dichloride, chloroform, tetracol phenixin, benzene, toluene, methyl alcohol, ethanol, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dioxane, N, dinethylformamide, dimethyl sulfoxide (DMSO), 2-methylpentane, methylcyclopentane, hexane, hexanaphthene, methylcyclohexane, heptane, octane, nonane, butyl ether, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, ethylene glycol bisthioglycolate butyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether etc., or the mixture of as above two or three different solvents.
Add suitable alkaloids favourable to reaction.Suitable alkali is selected from organic bases as triethylamine, N, accelerine, pyridine, 2-picoline, 3-picoline, 4-picoline, aldehydecollidine, 2,3-lutidine, 2,4-lutidine, 3,5-lutidine, 2,6-lutidine, 2,4,6-trimethylpyridine, quinoline, sodium methylate, sodium ethylate, sodium tert-butoxide or potassium tert.-butoxide etc., or mineral alkali is as sodium hydroxide, potassium hydroxide, sodium carbonate or salt of wormwood etc.
The preparation of compound of Formula IV is see the working method described in DE2633992.
Compounds of formula V can be obtained by ortho-substituted benzoic acid, and ortho-substituted benzoic acid has commercially available.
Table 1 lists structure and the physical properties of partial Formula I.
Table 1
Part of compounds
1hNMR (300MHz, CDCl
3) data are as follows:
Compound 4:7.96 (d, 1H), 7.91 (d, 1H), 7.79-7.67 (m, 3H), 7.49-7.44 (m, 3H), 7.36-7.33 (m, 2H), 6.80 (d, 1H), 2.79-2.77 (m, 1H), 1.20 (d, 6H).
Compound 8:7.96 (d, 1H), 7.90 (d, 1H), 7.77-7.63 (m, 3H), 7.50-7.45 (m, 3H), 7.36-7.33 (m, 2H), 6.80 (d, 1H), 1.23 (s, 9H).
Compound 10:7.96 (d, 1H), 7.91 (d, 1H), 7.79-7.67 (m, 3H), 7.49-7.44 (m, 3H), 7.36-7.33 (m, 2H), 6.80 (d, 1H), 3.63 (s, 2H), 1.30 (s, 6H).
Compound 11:7.96 (d, 1H), 7.91 (d, 1H), 7.79-7.67 (m, 3H), 7.49-7.44 (m, 3H), 7.36-7.33 (m, 2H), 6.80 (d, 1H), 1.90-1.80 (m, 1H), 1.09-1.03 (m, 4H).
Compound 12:7.96 (d, 1H), 7.91 (d, 1H), 7.79-7.67 (m, 3H), 7.49-7.44 (m, 3H), 7.36-7.33 (m, 2H), 6.77 (d, 1H), 3.42-3.36 (m, 1H), 2.36-2.21 (m, 4H), 2.04-1.94 (m, 2H).
Compound 15:8.17 (d, 1H), 8.05 (d, 1H), 7.96 (d, 1H), 7.80-7.63 (m, 4H), 7.55-7.49 (m, 3H), 7.48-7.40 (m, 2H), 7.29-7.23 (m, 3H), 6.77 (d, 1H).
Compound 29:8.00 (d, 1H), 7.91 (d, 1H), 7.79-7.67 (m, 3H), 7.49-7.44 (m, 3H), 7.36-7.33 (m, 2H), 6.87 (d, 1H), 3.95 (d, 2H), 2.06-1.91 (m, 1H), 0.91 (d, 6H).
Compound 36:8.15 (d, 1H), 7.91 (d, 1H), 7.79-7.67 (m, 3H), 7.49-7.44 (m, 3H), 7.36-7.33 (m, 2H), 6.82 (d, 1H), 1.19 (s, 9H).
Compound 43:8.17 (d, 1H), 8.05 (d, 1H), 7.92 (d, 1H), 7.80-7.63 (m, 4H), 7.55-7.49 (m, 3H), 7.48-7.40 (m, 2H), 7.29-7.23 (m, 3H), 6.77 (d, 1H).
Compound 54:8.23 (d, 1H), 8.00 (d, 1H), 7.92 (d, 1H), 7.80-7.71 (m, 4H), 7.50-7.45 (m, 2H), 7.36-7.26 (m, 1H), 4.25-4.16 (m, 2H), 1.30 (t, 3H).。
Compound 57:8.23 (d, 1H), 8.00 (d, 1H), 7.92 (d, 1H), 7.80-7.71 (m, 4H), 7.50-7.45 (m, 2H), 7.36-7.26 (m, 1H), 6.22 (d, 1H), 3.90 (d, 1H), 2.10-1.94 (m, 2H), 0.95 (d, 6H).
Compound 64:7.96 (d, 1H), 7.74-7.72 (m, 3H), 7.50-7.30 (m, 6H), 6.80 (d, 1H), 1.29 (s, 9H).
Compound 65:7.71 (d, 1H), 7.75-7.30 (m, 9H), 5.80 (d, 1H), 1.34 (s, 9H).
Phenylpyrazole base acrylonitrile compound of the present invention has high desinsection, acaricidal activity, can prevent and treat the various pests such as small cabbage moth, beet armyworm, prodenia litura, bollworm, meadow mythimna separata, cabbage looper, pea aphid, bean aphid, aphis fabae, cotten aphid, apple aphid, black peach aphid, corn leaf aphids, aleyrodid, leafhopper, plant hopper, planthopper, mealybug, web stinkbug, tomato bug, Nezara viridula smaragdula Fabricius., the smelly stinkbug of rice, cotton thrips, alfalfa thrips, soybean thrip, colorado potato bug, click beetle, fly, mosquito, mite.Compare with known acrylonitrile compound, phenylpyrazole base acrylonitrile compound of the present invention has beyond thought high insecticidal activity.Therefore, the present invention also comprises the purposes of compound of Formula I for Control pests, evil mite.
The present invention also comprises desinsection, miticide composition using compound of Formula I as active ingredient.In this desinsection, miticide composition, the weight percentage of active ingredient is between 1-99%.Acceptable carrier in agricultural, forestry or health is also comprised in this desinsection, miticide composition.
Composition of the present invention can the form of preparation be used.Compound of Formula I is dissolved or dispersed in carrier as active ingredient or is mixed with preparation to be easier to dispersion when using as Insecticidal and acaricidal agent.Such as: these chemicals can be made into wettable powder or missible oil.In these compositions, at least add a kind of liquid or solid carrier, and suitable tensio-active agent can be added when needed.
Technical scheme of the present invention also comprises the method for pest control, evil mite: desinsection of the present invention, miticide composition are imposed on the insect of needs control, harmful mite or its growth medium.The comparatively suitable effective amount of usual selection is per hectare 10 grams to 1000 grams, and preferably having effective amount is per hectare 50 grams to 500 grams.
For some application, such as, one or more other sterilant, Insecticides (tech) & Herbicides (tech), plant-growth regulator or fertilizer etc. agriculturally can be added in desinsection of the present invention, miticide composition, additional advantage and effect can be produced thus.
Should it is clear that, in claim limited range of the present invention, can various conversion and change be carried out.
Embodiment
Following synthesis example and raw test-results of surveying can be used to further illustrate the present invention, but do not mean that restriction the present invention.
Synthetic example
The preparation of embodiment 1, compound 8
(1) preparation of 3-methyl isophthalic acid-phenyl-1H-pyrazoles
In reaction flask, add phenylhydrazine (5.00 grams, 0.046 mole), 4,4-dimethoxy-2-butanone (7.30 grams, 0.055 mole), ethanol 40 milliliters, is warming up to backflow, refluxes 2 hours.In reaction solution, drip concentrated hydrochloric acid (0.5 milliliter), continue backflow 2 hours.Less than 30 DEG C are cooled to after reaction terminates, in reaction solution impouring 200 ml water, with 3 × 150 milliliters of extraction into ethyl acetate, gained organic phase is with after saturated sodium-chloride water solution (150 milliliters) washing, with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates obtains 5.00 grams of 3-methyl isophthalic acid-phenyl-1H-pyrazoles by pillar layer separation (leacheate: ethyl acetate: sherwood oil=1:10), yellow oil, yield 68%.
(2) preparation of 3-brooethyl-1-phenyl-1H-pyrazoles
3-methyl isophthalic acid-phenyl-1H-pyrazoles (0.50 gram is added in reaction flask, 0.003 mole), toluene 5 milliliters, be warming up to 70 DEG C, add N-bromo-succinimide (0.40 gram, 0.003 mole) to reaction solution, Diisopropyl azodicarboxylate (catalytic amount), finish, reaction solution is warming up to backflow, back flow reaction 1 hour.Less than 30 DEG C are cooled to after reaction terminates, in reaction solution impouring 50 ml water, with 3 × 50 milliliters of extraction into ethyl acetate, after the washing of gained organic phase saturated sodium bicarbonate aqueous solution (50 milliliters), saturated sodium-chloride water solution (50 milliliters), with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates obtains 0.40 gram of 3-brooethyl-1-phenyl-1H-pyrazoles by pillar layer separation (leacheate: ethyl acetate: sherwood oil=1:100), yellow oil, yield 56%.
(3) preparation of 2-(1-phenyl-1H-pyrazole-3-yl) acetonitrile
3-brooethyl-1-phenyl-1H-pyrazoles (0.55 gram, 0.003 mole) is added, dimethyl sulfoxide (DMSO) 5 milliliters, sodium cyanide (0.15 gram, 0.003 mole), room temperature reaction 6 hours in reaction flask.By in reaction solution impouring 100 ml water after reaction terminates, with 3 × 100 milliliters of extraction into ethyl acetate, gained organic phase is with after saturated sodium-chloride water solution (100 milliliters) washing, with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates obtains 0.20 gram of 2-(1-phenyl-1H-pyrazole-3-yl) acetonitrile by pillar layer separation (leacheate: ethyl acetate: sherwood oil=1:20), yellow oil, yield 36%.
(4) preparation of 3-(2-trifluoromethyl)-2-(1-phenyl-1H-pyrazole-3-yl)-3-hydroxy nitrile
Under ice-water bath, 2-(1-phenyl-1H-pyrazole-3-yl) acetonitrile (0.50 gram, 0.003 mole) is added, (2-trifluoromethyl) (1H-pyrazol-1-yl) ketone (0.96 gram in reaction flask, 0.004 mole), tetrahydrofuran (THF) 5 milliliters, stir about 1 hour, adds potassium tert.-butoxide (0.67 gram in batches, 0.006 mole), reinforced end, reaction solution is warming up to room temperature, room temperature reaction 6 hours.In reaction solution impouring 100 ml water, with 100 milliliters of extraction into ethyl acetate, the acid adjustment of gained aqueous phase concentrated hydrochloric acid is 2 ~ 3 to pH value, with 3 × 100 milliliters of extraction into ethyl acetate, organic phase, after saturated sodium bicarbonate aqueous solution (100 milliliters), saturated sodium-chloride water solution (100 milliliters) washing, with anhydrous magnesium sulfate drying, obtains 0.90 gram of 3-(2-trifluoromethyl)-2-(1-phenyl-1H-pyrazole-3-yl)-3-hydroxy nitrile after concentrated, yellow solid, yield 85%.
(5) preparation of compound 8
Under ice-water bath, 3-(2-trifluoromethyl)-2-(1-phenyl-1H-pyrazole-3-yl)-3-hydroxy nitrile (0.36 gram is added in reaction flask, 0.001 mole), acetonitrile 5 milliliters, triethylamine (0.10 gram, 0.001 mole), again by pivalyl chloride (0.12 gram, 0.001 mole) be added drop-wise in reaction flask, drip and terminate, be warming up to stirring at room temperature and react 2 hours, in reaction solution impouring 50 ml water, with ethyl acetate 3 × 100 milliliters extraction, gained organic phase is with saturated sodium bicarbonate aqueous solution (100 milliliters), after saturated sodium-chloride water solution washing (100 milliliters), with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates is by pillar layer separation (leacheate: ethyl acetate: sherwood oil=1:15), obtain 0.30 g of compound 8, yellow oil, yield 68%.
The preparation of embodiment 2, compound 26
Under ice-water bath, 3-(2-trifluoromethyl)-2-(1-phenyl-1H-pyrazole-3-yl)-3-hydroxy nitrile (0.36 gram is added in reaction flask, 0.001 mole), acetonitrile 5 milliliters, triethylamine (0.10 gram, 0.001 mole), again by Vinyl chloroformate (0.11 gram, 0.001 mole) be added drop-wise in reaction flask, drip and terminate, be warming up to stirring at room temperature and react 2 hours, in reaction solution impouring 50 ml water, with ethyl acetate 3 × 100 milliliters extraction, gained organic phase is with saturated sodium bicarbonate aqueous solution (100 milliliters), after saturated sodium-chloride water solution washing (100 milliliters), with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates is by pillar layer separation (leacheate: ethyl acetate: sherwood oil=1:15), obtaining 0.21 g of compound 26 is one group of stereoisomer mixture (E:Z=4:1), yellow solid, yield 49%.
The preparation of embodiment 3, compound 36
(1) preparation of 3-(2-nitrophenyl)-2-(1-phenyl-1H-pyrazole-3-yl)-3-hydroxy nitrile
Under ice-water bath, 2-(1-phenyl-1H-pyrazole-3-yl) acetonitrile (0.73 gram, 0.004 mole) is added, (2-nitrophenyl) (1H-pyrazol-1-yl) ketone (1.09 grams in reaction flask, 0.005 mole), tetrahydrofuran (THF) 10 milliliters, stir about 1 hour, adds potassium tert.-butoxide (0.90 gram in batches, 0.008 mole), reinforced end, reaction solution is warming up to room temperature, room temperature reaction 6 hours.In reaction solution impouring 150 ml water, with 100 milliliters of extraction into ethyl acetate, the acid adjustment of gained aqueous phase concentrated hydrochloric acid is 2 ~ 3 to pH value, with 3 × 150 milliliters of extraction into ethyl acetate, organic phase, after saturated sodium bicarbonate aqueous solution (150 milliliters), saturated sodium-chloride water solution (150 milliliters) washing, with anhydrous magnesium sulfate drying, obtains 0.72 gram of 3-(2-nitrophenyl)-2-(1-phenyl-1H-pyrazole-3-yl)-3-hydroxy nitrile after concentrated, yellow solid, yield 54%.
(2) preparation of compound 36
Under ice-water bath, 3-(2-nitrophenyl)-2-(1-phenyl-1H-pyrazole-3-yl)-3-hydroxy nitrile (0.33 gram is added in reaction flask, 0.001 mole), acetonitrile 5 milliliters, triethylamine (0.10 gram, 0.001 mole), again by pivalyl chloride (0.12 gram, 0.001 mole) be added drop-wise in reaction flask, drip and terminate, be warming up to stirring at room temperature and react 2 hours, in reaction solution impouring 50 ml water, with ethyl acetate 3 × 100 milliliters extraction, gained organic phase is with saturated sodium bicarbonate aqueous solution (100 milliliters), after saturated sodium-chloride water solution washing (100 milliliters), with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates is by pillar layer separation (leacheate: ethyl acetate: sherwood oil=1:15), obtain 0.14 g of compound 36, yellow oil, yield 36%.
The preparation of embodiment 4, compound 64,65
(1) preparation of 3-(2-chloro-phenyl-)-2-(1-phenyl-1H-pyrazole-3-yl)-3-hydroxy nitrile
Under ice-water bath, 2-(1-phenyl-1H-pyrazole-3-yl) acetonitrile (3.00 grams, 0.016 mole) is added, (2-chloro-phenyl-) (1H-pyrazol-1-yl) ketone (3.92 grams in reaction flask, 0.019 mole), tetrahydrofuran (THF) 40 milliliters, stir about 1 hour, adds potassium tert.-butoxide (3.59 grams in batches, 0.032 mole), reinforced end, reaction solution is warming up to room temperature, room temperature reaction 6 hours.In reaction solution impouring 150 ml water, with 100 milliliters of extraction into ethyl acetate, the acid adjustment of gained aqueous phase concentrated hydrochloric acid is 2 ~ 3 to pH value, with 3 × 150 milliliters of extraction into ethyl acetate, organic phase, after saturated sodium bicarbonate aqueous solution (150 milliliters), saturated sodium-chloride water solution (150 milliliters) washing, with anhydrous magnesium sulfate drying, obtains 3.10 grams of 3-(2-chloro-phenyl-)-2-(1-phenyl-1H-pyrazole-3-yl)-3-hydroxy nitriles after concentrated, yellow solid, yield 61%.
(2) preparation of compound 64
Under ice-water bath, 3-(2-chloro-phenyl-)-2-(1-phenyl-1H-pyrazole-3-yl)-3-hydroxy nitrile (0.64 gram is added in reaction flask, 0.002 mole), acetonitrile 5 milliliters, triethylamine (0.30 gram, 0.003 mole), again by pivalyl chloride (0.36 gram, 0.003 mole) be added drop-wise in reaction flask, drip and terminate, be warming up to stirring at room temperature and react 2 hours, in reaction solution impouring 50 ml water, with ethyl acetate 100 milliliters extraction, gained organic phase is with saturated sodium bicarbonate aqueous solution (100 milliliters), after saturated sodium-chloride water solution washing (100 milliliters), with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates is by pillar layer separation (leacheate: ethyl acetate: sherwood oil=1:15), obtain compound 64, yellow solid 0.42 gram, yield 52%.
(3) preparation of compound 65
3-(2-chloro-phenyl-)-2-(1-phenyl-1H-pyrazole-3-yl)-3-hydroxy nitrile (1.61 grams is added in reaction flask, 0.005 mole), sodium bicarbonate (0.84 gram, 0.010 mole), toluene 100 milliliters, DMAP (catalytic amount), Tetrabutyl amonium bromide (catalytic amount), be warming up to 70 DEG C, again by pivalyl chloride (0.72 gram, 0.006 mole) toluene (3 milliliters) solution be added drop-wise in reaction flask, drip and terminate, continue reaction 2 hours.Reaction solution is cooled to less than 30 DEG C, in reaction solution impouring 50 ml water, with ethyl acetate 100 milliliters extraction, after the washing of gained organic phase saturated sodium bicarbonate aqueous solution (100 milliliters), saturated sodium-chloride water solution (100 milliliters), with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates is by pillar layer separation (leacheate: ethyl acetate: sherwood oil=1:30), obtain compound 65, yellow solid 0.42 gram, yield 21%.
Biological activity determination
According to the solvability of testing compound, former medicinal acetone or methyl-sulphoxide dissolve, and then become the liquid to be measured 50 milliliters of desired concn with the tween 80 solution preparation of 1 ‰, acetone or methyl-sulphoxide content is in the solution no more than 10%.Desinsection, to kill the active classification of mite mortality ratio as follows: A:100%; B:99%-80%; C:79%-60%; D:59%-0.
The mensuration of embodiment 5, insecticidal activity
5.1 mensuration of killing black peach aphid activity
Cut-off footpath 6 cm dishes, covers one deck filter paper at the bottom of ware, and drips appropriate tap water moisturizing.Clip suitable size (diameter about 3 centimetres) from the cabbage plant cultivating black peach aphid and the long cabbage leaves having 15 ~ 30 aphids, remove the aphid of alatae and face of blade, after investigation radix, blade back is upwards placed in culture dish, carry out spraying process with hand-held Airbrush atomizer, pressure is that 10psi (is roughly equal to 0.7kg/cm
2), spouting liquid is 0.5mL, and often process 3 times and repeat, process is placed on standard sight indoor, and 48 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio and classification.
According to above method, partial test compound and known compound KC
1(the II-15 compound in WO9740009), compound K C
2(No. 1 compound in JP2005008628) and compound K C
3(No. 1 compound in WO2007100160) has carried out the replicate(determination) of killing black peach aphid activity.Test-results is in table 2.
Table 2: phenylpyrazole acrylonitrile compound and known compound KC
1, KC
2, KC
3kill the parallel comparison of black peach aphid activity
4.2 mensuration of killing small cabbage moth activity
Cabbage leaves punch tool is broken into the leaf dish of diameter 2 centimetres, with Airbrush spraying process, pressure is that 10psi (is roughly equal to 0.7kg/cm
2), every leaf dish pros and cons spraying, spouting liquid is 0.5mL.Often process access after drying in the shade and try worm 10 2 ages, often process 3 times and repeat.Put into 25 DEG C, relative humidity 60 ~ 70% observation indoor cultivation after process, 72 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio and classification.
In the compound of part for examination, following compounds is better to the prevention effect of small cabbage moth when concentration is 100ppm, and mortality ratio is more than B level: 8,11,12,26,28,29.
The mensuration of 4.3 mythimna separates
Maize leaf is cut into the leaf section of long 2 centimetres, with Airbrush spraying process, pressure is that 10psi (is roughly equal to 0.7kg/cm
2), every leaf section pros and cons spraying, spouting liquid is 0.5mL.Often process access after drying in the shade and try worm 10 2 ages, often process 3 times and repeat.Put into 25 DEG C, relative humidity 60 ~ 70% observation indoor cultivation after process, 72 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio and classification.
In the compound of part for examination, following compounds is better to the prevention effect of mythimna separata when concentration is 600ppm, and mortality ratio is more than B level: 8,10,11,12,15,28,29,57.
The mensuration of embodiment 5, acaricidal activity
Carmine spider mite is become to the mensuration of mite activity
Measuring method: get two panels true leaf Kidney bean seedling, connects carmine spider mite and becomes mite and after investigating radix, carry out whole strain spraying process with Airbrush atomizer, pressure is that 10psi (is roughly equal to 0.7kg/cm
2), spouting liquid is 0.5mL.Often process and repeat for 3 times, process is placed on standard sight room, and 72 hours " Invest, Then Investigate " survival mite numbers, calculate mortality ratio and classification.
In the compound of part for examination, following compounds is better to the prevention effect of mite when concentration is 100ppm, and mortality ratio reaches more than B level: 4,8,11,12,26,28,29.
Claims (5)
1. a phenylpyrazole base acrylonitrile compound, as shown in general formula I:
In formula:
R
1be selected from C
1-C
6alkoxyl group;
R
2be selected from trifluoromethyl;
Or its cis-trans-isomer.
2. according to compound according to claim 1, it is characterized in that, in general formula I:
R
1be selected from isopropoxy or isobutoxy;
R
2be selected from trifluoromethyl;
Or its cis-trans-isomer.
3. one kind controls the purposes of aphid according to compound of Formula I according to claim 1.
4. a killing aphis composition, be active ingredient and acceptable carrier in agricultural, forestry or health containing, for example compound shown in general formula I according to claim 1, in composition, the weight percentage of active ingredient is 1-99%.
5. control a method for aphid, it is characterized in that: composition according to claim 4 is imposed on the aphid of needs control or the medium of its growth with the effective dose of per hectare 10 grams to 1000 grams.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1216530A (en) * | 1996-04-25 | 1999-05-12 | 日产化学工业株式会社 | Ethylene derivatives and pest controlling agents |
| WO2007100160A1 (en) * | 2006-03-03 | 2007-09-07 | Nissan Chemical Industries, Ltd. | Acrylonitrile compounds |
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|---|---|---|---|---|
| CN1216530A (en) * | 1996-04-25 | 1999-05-12 | 日产化学工业株式会社 | Ethylene derivatives and pest controlling agents |
| CN101817784A (en) * | 1996-04-25 | 2010-09-01 | 日产化学工业株式会社 | Ethene derivatives and the pesticides that contains this derivative |
| WO2007100160A1 (en) * | 2006-03-03 | 2007-09-07 | Nissan Chemical Industries, Ltd. | Acrylonitrile compounds |
| WO2007100161A1 (en) * | 2006-03-03 | 2007-09-07 | Nissan Chemical Industries, Ltd. | Method for preferential production of geometric isomers and isolation method |
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