CN103833670A - 2-chloro thiazolyl acrylonitrile compound and application thereof - Google Patents

2-chloro thiazolyl acrylonitrile compound and application thereof Download PDF

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CN103833670A
CN103833670A CN201210484280.9A CN201210484280A CN103833670A CN 103833670 A CN103833670 A CN 103833670A CN 201210484280 A CN201210484280 A CN 201210484280A CN 103833670 A CN103833670 A CN 103833670A
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CN103833670B (en
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杨辉斌
李斌
宋玉泉
褚岩凤
王斌
刘红翼
冯聪
英君伍
陈霖
于海波
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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Shenyang Research Institute of Chemical Industry Co Ltd
Sinochem Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • 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
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

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Abstract

The invention discloses a 2-chloro thiazolyl acrylonitrile compound or a stereisomer thereof with a novel structure. The structure of the compound is shown as the general formula I in the specification, wherein R is one of alkyl of C1-C6, halogenated alkyl of C1-C6, cycloalkyl of C3-C8 and alkoxy of C1-C6; Q is selected from the group shown as the specification; R1 is one of H, halogen, methyl and trifluoromethyl; R2 is one of H and halogen. The compound in the general formula I has excellent insect and mite killing activity, and can be used for preventing and controlling insects and mites.

Description

2-chlorine thiazolyl acrylonitrile compounds and application thereof
Technical field
The invention belongs to Insecticidal and acaricidal agent field.Be specifically related to a kind of 2-chlorine thiazolyl acrylonitrile compounds 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 compound and the composition of improved tool desinsection, acaricidal activity.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 application, discloses the ethene derivatives that has desinsection, kills mite or fungicidal activity, has reported following compounds KC 1the insecticidal activity of (numbering II-63 in patent), under the concentration of 500ppm to black peach aphid preventive effect more than 80%.In WO2007100160 and WO2007100161 application, compound K C is further disclosed 2preparation, insecticidal activity and the synthesising process research of (in patent, numbering 1), compound K C 2under the concentration of 25ppm, black peach aphid is had to high prevention effect.
Figure BDA00002458174800011
In the prior art, as 2-chlorine thiazolyl acrylonitrile compounds shown in the present and desinsection thereof, acaricidal activity have no open.
Summary of the invention
The object of the present invention is to provide a kind of 2-chlorine thiazolyl acrylonitrile compounds of novel structure, it can be applicable to the control of insect in the health of agricultural, forestry or non-therapeutic purpose, evil mite.
Technical scheme of the present invention is as follows:
The invention provides a kind of 2-chlorine thiazolyl acrylonitrile compounds, as shown in general formula I:
Figure BDA00002458174800012
In formula:
R is selected from C 1-C 6alkyl, halo C 1-C 6alkyl, C 3-C 8cycloalkyl or C 1-C 6alkoxyl group;
Q is selected from following group:
Figure BDA00002458174800021
R 1be selected from H, halogen, methyl or trifluoromethyl;
R 2be selected from H or halogen;
Or its steric isomer.
The further preferred compound of the present invention is, in general formula I:
R is selected from C 1-C 6alkyl, halo C 1-C 6alkyl, C 3-C 8cycloalkyl or C 1-C 6alkoxyl group;
Q is selected from following group:
Figure BDA00002458174800022
R 1be selected from H or halogen;
R 2be selected from H or halogen;
Or its steric isomer.
The present invention further preferred compound is, in general formula I:
R is selected from C 3-C 6alkyl, halo C 3-C 6alkyl or C 1-C 4alkoxyl group;
Q is selected from following group:
R 1be selected from H, fluorine or chlorine;
R 2be selected from H, fluorine or chlorine;
Or its steric isomer.
In the definition of the compound of Formula I providing, collect term General Definition used as follows above:
Alkyl refers to straight or branched form, such as methyl, ethyl, n-propyl, sec.-propyl etc.Cycloalkyl comprises cyclopropyl, cyclobutyl, cyclopropyl methyl, methyl cyclopropyl etc.Haloalkyl refers to the group that alkyl is replaced by 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 the substituting group CN on carbon-carbon double bond B and OCOR are in the same side of B key (Z configuration) or both sides (E configuration).
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.
Figure BDA00002458174800031
In formula: L represents suitable leavings group, as chlorine, bromine or tolysulfonyl oxygen base etc.
General formula I I compound with compound of formula III in suitable solvent, temperature makes target compound I for-10 DEG C for 0.5-48 hour to reacting under 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 to reacting favourable.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 the difference of reaction conditions or starting raw material, there is steric isomerism in compound of Formula I.For example the substituting group CN on carbon-carbon double bond B and OCOR are in the same side of B key (Z configuration) or both sides (E configuration).By selecting suitable starting raw material or controlling reaction conditions, can obtain the excessive product of a kind of isomer or individual isomer.Also can by crude product being carried out to the separation of conventional means, for example, by methods such as column chromatography, recrystallizations, obtain individual isomer.The structure of these isomer can be passed through 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 general formula I I compound is as follows:
Figure BDA00002458174800032
In formula: L 1represent suitable leavings group, as chlorine, bromine, pyrazolyl, imidazolyl, methoxyl group, oxyethyl group or tolysulfonyl oxygen base etc.
General formula I V compound with general formula V compound in suitable solvent, under the existence of alkali, temperature makes general formula compound II for-10 DEG C for 0.5-48 hour to reacting under 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 as above mixture of two or three different solvents.
Add suitable alkaloids to reacting favourable.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 working method of describing in concrete preparation WO9740009, the DE2633992 of general formula I V compound.
The concrete preparation of general formula V compound is referring to Tetrahedron Lett., 2005,46,2251, J.Med.Chem., 1973,16,978, US6096898.
Table 1 has been listed structure and the physical properties of part compound of Formula I.
Figure BDA00002458174800041
Table 1
Figure BDA00002458174800042
Figure BDA00002458174800051
Figure BDA00002458174800061
Figure BDA00002458174800081
Figure BDA00002458174800101
Figure BDA00002458174800111
Figure BDA00002458174800131
Figure BDA00002458174800141
Figure BDA00002458174800161
Figure BDA00002458174800171
Figure BDA00002458174800181
Figure BDA00002458174800191
Figure BDA00002458174800201
Figure BDA00002458174800211
Figure BDA00002458174800221
Figure BDA00002458174800231
Figure BDA00002458174800241
Figure BDA00002458174800251
Figure BDA00002458174800261
Figure BDA00002458174800271
Figure BDA00002458174800281
Figure BDA00002458174800291
Part of compounds 1h NMR (300MHz, CDCl 3) data are as follows:
Compound 15:7.93 (m, 2H), 7.66 (s, 1H), 7.47 (m, 3H), 2.63 (s, 3H), 1.26 (s, 9H).
Compound 16:7.67 (m, 2H), 7.52 (s, 1H), 7.41 (m, 3H), 2.19 (s, 3H), 1.33 (s, 9H).
Compound 17:7.94 (m, 2H), 7.66 (s, 1H), 7.47 (m, 3H), 2.63 (s, 3H), 1.62 (q, 2H), 1.21 (s, 6H), 0.77 (t, 3H).
Compound 31:7.96 (m, 2H), 7.75 (s, 1H), 7.47 (m, 3H), 4.28 (m, 2H), 2.60 (s, 3H), 1.34 (t, 3H).
Compound 295:8.04 (m, 3H), 7.48 (m, 3H), 2.60 (s, 3H), 1.36 (s, 9H).
Compound 296:7.85 (m, 3H), 7.44 (m, 3H), 2.28 (s, 3H), 1.36 (s, 9H).
Compound 311:8.07 (m, 3H), 7.50 (m, 3H), 4.34 (q, 2H), 2.59 (s, 3H), 1.39 (t, 3H).
Compound 455:8.14 (s, 1H), 7.48 (m, 1H), 7.07 (m, 2H), 2.60 (s, 3H), 1.27 (s, 9H).
Compound 457:8.14 (s, 1H), 7.46 (m, 1H), 7.06 (m, 2H), 2.60 (s, 3H), 1.65 (q, 2H), 1.23 (s, 6H), 0.80 (t, 3H).
Compound 469:8.18 (s, 1H), 7.49 (m, 1H), 7.07 (m, 2H), 3.94 (s, 3H), 2.59 (s, 3H).
Compound 575:7.95 (d, 1H), 7.70 (m, 2H), 7.48 (m, 2H), 7.35 (m, 1H), 6.75 (d, 1H), 2.61 (s, 3H), 1.29 (s, 6H).
Compound 577:7.95 (d, 1H), 7.71 (m, 2H), 7.47 (m, 2H), 7.36 (m, 1H), 6.76 (d, 1H), 2.63 (s, 3H), 1.65 (q, 2H), 1.24 (s, 6H), 0.79 (t, 3H).
Compound 589:7.99 (d, 1H), 7.72 (m, 2H), 7.48 (m, 2H), 7.36 (m, 1H), 6.81 (d, 1H), 3.90 (s, 3H), 2.59 (s, 3H).
2-chlorine thiazolyl acrylonitrile compounds 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 fleahopper, Nezara viridula smaragdula Fabricius., the smelly stinkbug of rice, cotton thrips, alfalfa thrips, soya bean thrips, colorado potato bug, click beetle, fly, mosquito, mite.Compare with known acrylonitrile compound, 2-chlorine thiazolyl acrylonitrile compounds 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, the 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%.In this desinsection, miticide composition, also comprise acceptable carrier in agricultural, forestry or health.
Composition of the present invention can preparation form use.Compound of Formula I is easier to as solubilization of active ingredient or when being scattered in carrier or being mixed with preparation to using as Insecticidal and acaricidal agent disperse.For example: 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 can add when needed suitable tensio-active agent.
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 insect, evil mite or its growth medium of needs control.Conventionally the comparatively suitable significant quantity of selecting is 10 grams to 1000 grams of per hectares, and preferably significant quantity is 50 grams to 500 grams of per hectares.
For some application, for example in agricultural, can in desinsection of the present invention, miticide composition, add one or more other sterilant, Insecticides (tech) & Herbicides (tech), plant-growth regulator or fertilizer etc., can produce thus additional advantage and effect.
Should be clear and definite, in claim limited range of the present invention, can carry out various conversion and change.
Embodiment
Following synthetic example and the 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 15,16
(1) preparation of 4-chloromethyl-2-phenyl thiazole
Figure BDA00002458174800301
In there-necked flask, add thiobenzamide (20.00 grams, 0.146 mole), 200 milliliters of methyl alcohol, 1,3-DCA (22.21 grams, 0.157 mole), is warming up to backflow, back flow reaction 3 hours.After finishing, reaction is cooled to below 30 DEG C, in reaction solution impouring 50 ml waters, with 3 × 50 milliliters of ethyl acetate extractions, after gained saturated sodium bicarbonate aqueous solution (50 milliliters) for organic phase, saturated sodium-chloride water solution (50 milliliters) washing, with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates separates (leacheate: ethyl acetate: sherwood oil=1:10) by column chromatography and obtains 21.00 grams of 4-chloromethyl-2-phenyl thiazoles, yellow oil, yield: 69%.
(2) preparation of 2-(2-phenyl thiazole-4-yl) acetonitrile
Figure BDA00002458174800311
In reaction flask, add sodium cyanide (4.91 grams, 0.100 mole), 100 milliliters, water, ethanol (100 milliliters) solution of dropping 4-chloromethyl-2-phenyl thiazole (21.00 grams, 0.100 mole), dropwises, and is warming up to backflow, refluxes 16 hours.Reaction finish after by reaction solution impouring 200 ml waters, with 3 × 200 milliliters of ethyl acetate extractions, gained is for organic phase after saturated sodium-chloride water solution (200 milliliters) washing, with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates separates (leacheate: ethyl acetate: sherwood oil=1:10) by column chromatography and obtains 13.22 grams of 2-(2-phenyl thiazole-4-yl) acetonitrile, yellow solid, yield 66%.
(3) preparation of 3-(the chloro-4-methylthiazol-5-of 2-yl)-3-hydroxyl-2-(2-phenyl thiazole-4-yl) vinyl cyanide
Under ice-water bath, in reaction flask, add 2-(2-phenyl thiazole-4-yl) acetonitrile (3.00 grams, 0.015 mole), (3.72 grams of (the chloro-4-methylthiazol-5-of 2-yl) (1H-pyrazol-1-yl) ketones, 0.018 mole), 40 milliliters of tetrahydrofuran (THF)s, stir about 1 hour adds (3.36 grams of potassium tert.-butoxides in batches, 0.030 mole), reinforced end, reaction solution is warming up to room temperature, room temperature reaction 6 hours.In reaction solution impouring 150 ml waters, with 100 milliliters of ethyl acetate extractions, gained water is 2 ~ 3 by concentrated hydrochloric acid acid adjustment to pH value, with 3 × 150 milliliters of ethyl acetate extractions, organic phase is after saturated sodium bicarbonate aqueous solution (150 milliliters), saturated sodium-chloride water solution (150 milliliters) washing, with anhydrous magnesium sulfate drying, after concentrated, obtain 2.63 grams of 3-(the chloro-4-methylthiazol-5-of 2-yl)-3-hydroxyl-2-(2-phenyl thiazole-4-yl) vinyl cyanide, yellow solid, yield 51%.
(4) preparation of compound 15
Figure BDA00002458174800313
Under ice-water bath, in reaction flask, add (0.36 gram of 3-(the chloro-4-methylthiazol-5-of 2-yl)-3-hydroxyl-2-(2-phenyl thiazole-4-yl) vinyl cyanide, 0.001 mole), 10 milliliters of acetonitriles, (0.10 gram of triethylamine, 0.001 mole), again by (0.12 gram of pivalyl chloride, 0.001 mole) be added drop-wise in reaction flask, drip and finish, be warming up to stirring at room temperature reaction 2 hours, in reaction solution impouring 50 ml waters, with 100 milliliters of extractions of ethyl acetate, gained is saturated sodium bicarbonate aqueous solution (100 milliliters) for organic phase, after saturated sodium-chloride water solution washing (100 milliliters), with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates separates (leacheate: ethyl acetate: sherwood oil=1:20) by column chromatography, obtain 0.21 and digest compound 15, yellow oil, yield 49%.
(5) preparation of compound 16
Figure BDA00002458174800321
In reaction flask, add (0.72 gram of 3-(the chloro-4-methylthiazol-5-of 2-yl)-3-hydroxyl-2-(2-phenyl thiazole-4-yl) vinyl cyanide, 0.002 mole), sodium bicarbonate (0.34 gram, 0.004 mole), 20 milliliters of toluene, DMAP (catalytic amount), Tetrabutyl amonium bromide (catalytic amount), is warming up to 100 DEG C, again by (0.24 gram of pivalyl chloride, 0.002 mole) be added drop-wise in reaction flask, drip and finish, continue reaction 2 hours.Reaction solution is cooled to below 30 DEG C, in reaction solution impouring 50 ml waters, with 100 milliliters of extractions of ethyl acetate, gained after saturated sodium bicarbonate aqueous solution (100 milliliters), saturated sodium-chloride water solution washing (100 milliliters), is used anhydrous magnesium sulfate drying, after concentrating under reduced pressure for organic phase, resistates separates (leacheate: ethyl acetate: sherwood oil=1:30) by column chromatography, obtain 0.30 and digest compound 16, yellow oil, yield 41%.
The preparation of embodiment 2, compound 469
(1) 4-chloromethyl-2-(preparation of 2,6-difluorophenyl) oxazole
Figure BDA00002458174800322
In 100 milliliters of round-bottomed flasks, add 2,6-difluorobenzamide (10.00 grams, 0.064 mole) and 1,3-DCA (16.20 grams, 0.128 mole), be warming up to and reflux and keep reaction under reflux conditions to carry out 4 hours.After stopped reaction, naturally cool to room temperature, in impouring 500 ml waters, with 3 × 100 milliliters of ethyl acetate extractions, organic phase is after 3 × 100 milliliters of saturated sodium-chloride water solution washings, with anhydrous magnesium sulfate drying, concentrated rear pillar chromatographic separation (leacheate: ethyl acetate: sherwood oil=1:3) obtains 11.50 grams of 4-chloromethyl-2-(2,6-difluorophenyl) oxazole, yellow solid, yield 76%.
(2) preparation of 2-(2,6-difluorophenyl)-4-Qing Jia Ji oxazole
In the lower 50 milliliters of round-bottomed flasks of room temperature, add 4-chloromethyl-2-(2, (20.00 grams of 6-difluorophenyl) oxazoles, 0.087 mole), add 50 milliliters of ethanol fully to dissolve, add (5.10 grams of sodium cyanides, 0.105 mole), be warming up to and reflux and keep reaction under reflux conditions to carry out 4 hours.After stopped reaction, naturally cool to room temperature, in impouring 100 ml waters, with 3 × 30 milliliters of ethyl acetate extractions, organic phase is after 3 × 50 milliliters of saturated sodium-chloride water solution washings, with anhydrous magnesium sulfate drying, concentrated rear pillar chromatographic separation (leacheate: ethyl acetate: sherwood oil=1:1) obtains 14.60 grams of 2-(2,6-difluorophenyl)-4-Qing Jia Ji oxazole, white solid, yield 76%.
(3) 3-hydroxyl-3-(the chloro-4-methylthiazol-5-of 2-yl)-2-(preparation of 2-(2,6-difluorophenyl) oxazole-4-yl) vinyl cyanide
Under ice-water bath, in 100 milliliters of reaction flasks, add 2-(2,6-difluorophenyl) (2.00 grams of-4-Qing Jia Ji oxazoles, 0.009 mole), 25 milliliters of anhydrous tetrahydro furans, (2.50 grams of (the chloro-4-methylthiazol-5-of 2-yl) (1H-pyrazol-1-yl) ketones, 0.011 mole), again by (2.30 grams of potassium tert.-butoxides, 0.018 mole) join in multiple times in reaction flask on a small quantity, be warming up to stirring at room temperature reaction 4 hours, by reaction solution impouring 50 ml waters, with 2 × 20 milliliters of washings of ethyl acetate, discard organic phase.Water is used to hydrochloric acid regulation system pH=2～3, separate out solid, filtration is dried and is obtained 2.00 grams of intermediate 3-hydroxyl-3-(the chloro-4-methylthiazol-5-of 2-yl)-2-(2-(2,6-difluorophenyl) oxazole-4-yl) vinyl cyanide, yellow solid, yield 58%.
(4) preparation of compound 469
Figure BDA00002458174800332
Under ice-water bath, in 50 milliliters of reaction flasks, add successively 3-hydroxyl-3-(the chloro-4-methylthiazol-5-of 2-yl)-2-(2-(2, 6-difluorophenyl) oxazole-4-yl) (0.30 gram of vinyl cyanide, 0.001 mole), (0.10 gram of 15 milliliters of acetonitriles and triethylamine, 0.001 mole), again by (0.10 gram of methyl-chloroformate, 0.001 mole) be added drop-wise in reaction flask, be warming up to stirring at room temperature reaction 4 hours, in reaction solution impouring 50 ml waters, be extracted with ethyl acetate (2 × 50 milliliters), 15 milliliters of saturated sodium bicarbonate aqueous solutions for gained organic phase, after 25 milliliters of saturated sodium-chloride water solution washings, with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates separates (leacheate: ethyl acetate: sherwood oil=1:3) by column chromatography and obtains 0.20 and digest compound 469, yellow oil, yield 51%.
The preparation of embodiment 3, compound 575
(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), 40 milliliters of ethanol, are warming up to backflow, reflux 2 hours.In reaction solution, drip concentrated hydrochloric acid (0.5 milliliter), continue to reflux 2 hours.After finishing, reaction is cooled to below 30 DEG C, in reaction solution impouring 200 ml waters, with 3 × 150 milliliters of ethyl acetate extractions, gained is for organic phase after saturated sodium-chloride water solution (150 milliliters) washing, with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates separates (leacheate: ethyl acetate: sherwood oil=1:10) by column chromatography and obtains 5.00 grams of 3-methyl isophthalic acid-phenyl-1H-pyrazoles, yellow oil, yield 68%.
(2) preparation of 3-brooethyl-1-phenyl-1H-pyrazoles
Figure BDA00002458174800334
In reaction flask, add (0.50 gram of 3-methyl isophthalic acid-phenyl-1H-pyrazoles, 0.003 mole), 5 milliliters of toluene, 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.After finishing, reaction is cooled to below 30 DEG C, in reaction solution impouring 50 ml waters, with 3 × 50 milliliters of ethyl acetate extractions, after gained saturated sodium bicarbonate aqueous solution (50 milliliters) for organic phase, saturated sodium-chloride water solution (50 milliliters) washing, with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates separates (leacheate: ethyl acetate: sherwood oil=1:100) by column chromatography and obtains 0.40 gram of 3-brooethyl-1-phenyl-1H-pyrazoles, yellow oil, yield 56%.
(3) preparation of 2-(1-phenyl-1H-pyrazole-3-yl) acetonitrile
Figure BDA00002458174800341
In reaction flask, add 3-brooethyl-1-phenyl-1H-pyrazoles (0.55 gram, 0.003 mole), 5 milliliters of dimethyl sulfoxide (DMSO), sodium cyanide (0.15 gram, 0.003 mole), room temperature reaction 6 hours.Reaction finish after by reaction solution impouring 100 ml waters, with 3 × 100 milliliters of ethyl acetate extractions, gained is for organic phase after saturated sodium-chloride water solution (100 milliliters) washing, with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates separates (leacheate: ethyl acetate: sherwood oil=1:20) by column chromatography and obtains 0.20 gram of 2-(1-phenyl-1H-pyrazole-3-yl) acetonitrile, yellow oil, yield 36%.
(4) preparation of 3-hydroxyl-3-(the chloro-4-methylthiazol-5-of 2-yl)-2-(1-phenylpyrazole-3-yl) vinyl cyanide
Under ice-water bath, in 50 milliliters of reaction flasks, add (0.80 gram of 1-phenyl-3-cyanogen methyl isophthalic acid H-pyrazoles, 0.004 mole), 25 milliliters of anhydrous tetrahydro furans, (1.20 grams of (the chloro-4-methylthiazol-5-of 2-yl) (1H-pyrazol-1-yl) ketones, 0.005 mole), again by (1.00 grams of potassium tert.-butoxides, 0.09 mole) join in multiple times on a small quantity in reaction flask, be warming up to stirring at room temperature reaction 4 hours, by in reaction solution impouring 50 ml waters, with 2 × 20 milliliters of washings of ethyl acetate, discard organic phase.Water, with hydrochloric acid regulation system pH=2～3, is separated out to solid, and filtration is dried and is obtained 0.90 gram of intermediate 3-hydroxyl-3-(the chloro-4-methylthiazol-5-of 2-yl)-2-(1-phenylpyrazole-3-yl) vinyl cyanide, yellow solid, yield 60%.(5) preparation of compound 575
Figure BDA00002458174800343
Under ice-water bath, in 50 milliliters of reaction flasks, add successively (0.30 gram of 3-hydroxyl-3-(the chloro-4-methylthiazol-5-of 2-yl)-2-(1-phenylpyrazole-3-yl) vinyl cyanide, 0.001 mole), (0.11 gram of 15 milliliters of acetonitriles and triethylamine, 0.001 mole), again by (0.12 gram of pivaloyl chloride, 0.001 mole) be added drop-wise in reaction flask, be warming up to stirring at room temperature reaction 4 hours, in reaction solution impouring 50 ml waters, be extracted with ethyl acetate (2 × 50 milliliters), 15 milliliters of saturated sodium bicarbonate aqueous solutions for gained organic phase, after 25 milliliters of saturated sodium-chloride water solution washings, with anhydrous magnesium sulfate drying, after concentrating under reduced pressure, resistates separates (leacheate: ethyl acetate: sherwood oil=1:5) by column chromatography and obtains 0.15 and digest compound 575, yellow oil, yield 44%.
Biological activity determination
According to the solvability of testing compound, former medicinal acetone or methyl-sulphoxide dissolve, and then become 50 milliliters of the liquid to be measured of desired concn with 1 ‰ tween 80 solution preparation, and acetone or the methyl-sulphoxide content in solution is 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 4, insecticidal activity
4.1 kill the mensuration of black peach aphid activity
6 centimetres, cut-off footpath culture dish, covers one deck filter paper at the bottom of ware, and drips appropriate tap water moisturizing.Clip suitable size (3 centimetres of diameters) and the long cabbage leaves that has 15～30 aphids from the cabbage plant of cultivation black peach aphid, remove the aphid of alatae and face of blade, after investigation radix, blade back is upwards placed in culture dish, with the processing of spraying of hand-held Airbrush atomizer, pressure is that 10psi (is roughly equal to 0.7kg/cm 2), spouting liquid is 0.5mL, and every processing repeats for 3 times, processes and is placed in standard observation ward, and 48 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio classification.
According to above method, partial test compound and known compound KC 1(the II-63 compound in WO9740009) and compound K C 2(No. 1 compound in WO2007100160) carried out killing the replicate(determination) of black peach aphid activity.Test-results is in table 2.
Table 2:2-chlorine thiazolyl acrylonitrile compound and known compound KC 1, KC 2kill the active parallel comparison of black peach aphid
Figure BDA00002458174800351
4.2 kill the mensuration of small cabbage moth activity
Cabbage leaves is broken into the leaf dish of 2 centimetres of diameters with punch tool, process with Airbrush spraying, pressure is that 10psi (is roughly equal to 0.7kg/cm 2), every leaf dish pros and cons spraying, spouting liquid is 0.5mL.After drying in the shade, every processing access tries worm 10 2 ages, and every processing repeats for 3 times.After processing, put into 25 DEG C, relative humidity 60～70% observation indoor cultivation, 72 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio classification.
In the compound of part for examination, following compounds prevention effect to small cabbage moth in the time that concentration is 600ppm is better, and mortality ratio is more than B level: 15,16,17,31,455,457,477,577.
The mensuration of 4.3 mythimna separates
Maize leaf is cut into the leaf section of long 2 centimetres, processes with Airbrush spraying, pressure is that 10psi (is roughly equal to 0.7kg/cm 2), every leaf section pros and cons spraying, spouting liquid is 0.5mL.After drying in the shade, every processing access tries worm 10 2 ages, and every processing repeats for 3 times.After processing, put into 25 DEG C, relative humidity 60～70% observation indoor cultivation, 72 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio classification.
In the compound of part for examination, following compounds prevention effect to mythimna separata in the time that concentration is 100ppm is better, and mortality ratio is more than B level: 15,16,17,18.
The mensuration of embodiment 5, acaricidal activity
Carmine spider mite is become to the mensuration of mite activity
Measuring method: get two true leaf Kidney bean seedlings, connect carmine spider mite and become mite and investigate after 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.Every processing repeats for 3 times, processes and is placed on standard observation ward, and 72 hours " Invest, Then Investigate " survival mite numbers, calculate mortality ratio classification.
In the compound of part for examination, following compounds prevention effect to mite in the time that concentration is 100ppm is better, more than mortality ratio reaches B level: 15,16,17,18,456,575,577,589,595,597.
In the compound of part for examination, following compounds prevention effect to mite in the time that concentration is 10ppm is better, more than mortality ratio reaches B level: 16,456,595.

Claims (6)

1. a 2-chlorine thiazolyl acrylonitrile compounds, as shown in general formula I:
Figure FDA00002458174700011
In formula:
R is selected from C 1-C 6alkyl, halo C 1-C 6alkyl, C 3-C 8cycloalkyl or C 1-C 6alkoxyl group;
Q is selected from following group:
R 1be selected from H, halogen, methyl or trifluoromethyl;
R 2be selected from H or halogen;
Or its steric isomer.
2. according to compound claimed in claim 1, it is characterized in that, in general formula I:
R is selected from C 1-C 6alkyl, halo C 1-C 6alkyl, C 3-C 8cycloalkyl or C 1-C 6alkoxyl group;
Q is selected from following group:
Figure FDA00002458174700013
R 1be selected from H or halogen;
R 2be selected from H or halogen;
Or its steric isomer.
3. according to compound claimed in claim 2, it is characterized in that, in general formula I:
R is selected from C 3-C 6alkyl, halo C 3-C 6alkyl or C 1-C 4alkoxyl group;
Q is selected from following group:
Figure FDA00002458174700014
R 1be selected from H, fluorine or chlorine;
R 2be selected from H, fluorine or chlorine;
Or its steric isomer.
One kind according to compound of Formula I Control pests claimed in claim 1, evil mite purposes.
5. desinsection, a miticide composition, containing compound shown in general formula I as claimed in claim 1 is acceptable carrier in active ingredient and agricultural, forestry or health, in composition, the weight percentage of active ingredient is 1-99%.
6. a method for Control pests, evil mite, is characterized in that: composition claimed in claim 5 is imposed on the medium of insect, evil mite or its growth of needs control with the effective dose of 10 grams to 1000 grams of per hectares.
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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

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