CN103833668B - O-trifluoromethyl phenylpropen nitrile compounds and application thereof - Google Patents
O-trifluoromethyl phenylpropen nitrile compounds and application thereof Download PDFInfo
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- 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
- C07D277/22—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D277/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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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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- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/32—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole 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
Abstract
The invention discloses o-trifluoromethyl phenylpropen nitrile compounds or its stereoisomer of a kind of novel structure, compound structure is as shown in formula I:In formula: R is selected from C1‑C6Alkyl, halo C1‑C6Alkyl, C3‑C8Cycloalkyl or C1‑C6Alkoxyl；Q is selected from following group:R1Selected from H, halogen, methyl or trifluoromethyl；R2Selected from H or halogen.Compound of Formula I has the parasite killing of excellence, acaricidal activity, can be used for pest control, evil demodicid mite.
Description
Technical field
The invention belongs to Insecticidal and acaricidal agent field.Be specifically related to a kind of o-trifluoromethyl phenylpropen nitrile compounds and
Its application.
Background technology
Due to Insecticidal and acaricidal agent in use for some time, insect, evil demodicid mite can produce resistance to it, accordingly, it would be desirable to constantly
Invent tool parasite killing that is novel and that improve, the compound of acaricidal activity and compositions.Meanwhile, along with people are to days such as agricultural and animal products
The needs that benefit increases and the pay attention to day by day to environmental conservation, also have always a demand for use cost new killing lower, environment amenable
Worm, acaricide.
Nissan Chemical Ind Ltd, in WO9740009 applies for, discloses and has parasite killing, mite killing or bactericidal activity
Ethene derivatives, it was recently reported that compound K C1The insecticidal activity of (numbering II-15 in patent), to black peach aphid under the concentration of 500ppm
Preventive effect is more than 80%.In WO2007100160 and WO2007100161 applies for, further disclose compound K C2(in patent
Numbering 1) preparation, insecticidal activity and synthesising process research, compound K C2Under the concentration of 25ppm, black peach aphid is had high preventing
Control effect.
In the prior art, o-trifluoromethyl phenylpropen nitrile compounds as representative of the present invention and parasite killing, mite killing
Activity is not disclosed.
Summary of the invention
It is an object of the invention to provide the o-trifluoromethyl phenylpropen nitrile compounds of a kind of novel structure, it can be answered
Insect, the preventing and treating of evil demodicid mite in the health of agricultural, forestry or non-treatment purpose.
Technical scheme is as follows:
The invention provides a kind of o-trifluoromethyl phenylpropen nitrile compounds, as shown in formula I:
In formula:
R is selected from C1-C6Alkyl, halo C1-C6Alkyl, C3-C8Cycloalkyl or C1-C6Alkoxyl；
Q is selected from following group:
R1Selected from H, halogen, methyl or trifluoromethyl；
R2Selected from H or halogen；
Or its stereoisomer.
The further preferred compound of the present invention is, in formula I:
R is selected from C1-C6Alkyl, halo C1-C6Alkyl, C3-C8Cycloalkyl or C1-C6Alkoxyl；
Q is selected from following group:
R1Selected from H or halogen；
R2Selected from H or halogen；
Or its stereoisomer.
The present invention further preferably compound is, in formula I:
R is selected from C3-C6Alkyl, halo C3-C6Alkyl or C1-C4Alkoxyl；
Q is selected from following group:
R1Selected from H, fluorine or chlorine；
R2Selected from H, fluorine or chlorine；
Or its stereoisomer.
In the definition of compound of Formula I given above, collect term used and be typically defined as follows:
Alkyl refers to straight or branched form, such as methyl, ethyl, n-pro-pyl, isopropyl etc..Cycloalkyl includes ring third
Base, cyclobutyl, Cvclopropvlmethvl, methylcyclopropyl groups etc..Haloalkyl refers to the base that alkyl is optionally substituted with one or more halogen atoms
Group, such as chloroethyl, trifluoromethyl etc..Alkoxyl refers to that alkyl end is connected with the group of oxygen atom, such as methoxyl group, ethyoxyl,
Positive propoxy, isopropoxy etc..Halogen refers to fluorine, chlorine, bromine, iodine.Stereoisomer refers in Formulas I, taking on carbon-carbon double bond B
For base CN and OCOR in the same side (Z configuration) of B key or both sides (E).
The compound of Formula I of the present invention can be prepared by the following method, and in reaction equation, each group definition is the same.
In formula: L represents suitable leaving group, such as chlorine, bromine or tolysulfonyl epoxide etc..
Compounds of formula II and compound of formula III in suitable solvent, temperature be-10 DEG C to reaction under reflux temperature
0.5-48 hour prepared target compound I.
Suitable solvent is selected from dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrochysene
Furan, dioxane, N,N-dimethylformamide or dimethyl sulfoxide etc..
Add suitable alkaloids favourable to reaction.Suitable alkali can be selected from organic base, such as triethylamine, N, N-bis-
Monomethylaniline., pyridine, Feldalat NM, sodium tert-butoxide or potassium tert-butoxide etc.；Or inorganic base such as sodium hydroxide, potassium hydroxide, bicarbonate
Sodium, sodium carbonate or sodium hydride etc..
Difference according to reaction condition or the difference of initiation material, there is stereo-isomerism in compound of Formula I.Such as carbon
Substituent group CN in carbon double bond B and OCOR are in the same side (Z configuration) of B key or both sides (E).By selecting suitable initiateing
Raw material or control reaction condition, can obtain product or the individual isomer of a kind of isomer excess.Can also be by producing thick
Thing carries out the separation of conventional means, such as, by the method such as column chromatography, recrystallization, obtain individual isomer.These isomers
The conventionals method of analysis such as structure can pass through X-ray single crystal diffraction, nuclear magnetic resonance, NMR determine.
Compound of formula III is commercially available.
The preparation method of Compounds of formula II is as follows:
In formula: L1Represent suitable leaving group, such as chlorine, bromine, pyrazolyl, imidazole radicals, methoxyl group, ethyoxyl or to toluene
Sulfonyloxy etc..
Compound of Formula IV and compounds of formula V in suitable solvent, in the presence of base, temperature be-10 DEG C to boiling
The lower 0.5-48 hour prepared general formula compound II of reaction of point.
Suitable solvent is mainly selected from: dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, methanol, ethanol, ethyl acetate,
Acetonitrile, oxolane, dioxane, N,N-dimethylformamide, dimethyl sulfoxide, 2-methylpentane, methyl cyclopentane, oneself
Alkane, hexamethylene, hexahydrotoluene, heptane, octane, nonane, butyl ether, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol
Dibutyl ethers, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether etc., or as above two or three not
Mixture with solvent.
Add suitable alkaloids favourable to reaction.Suitable alkali is selected from organic base such as triethylamine, N, N-dimethyl benzene
Amine, pyridine, 2-picoline, 3-picoline, 4-picoline, aldehydecollidine, 2,3 dimethyl pyridine, 2,
4-lutidines, 3,5-lutidines, 2,6-lutidines, 2,4,6-trimethylpyridine, quinoline, Feldalat NM, ethanol
Sodium, sodium tert-butoxide or potassium tert-butoxide etc., or inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate etc..
The concrete preparation of compound of Formula IV sees the operational approach described in WO9740009, DE2633992.
Compounds of formula V can be prepared by o-trifluoromethyl benzoic acid, and o-trifluoromethyl benzoic acid is commercially available.
Table 1 lists structure and the physical property of partial Formula I.
Table 1
Part of compounds1H NMR(300MHz,CDCl3) data are as follows:
Compound 15:7.98-7.95 (m, 2H), 7.89 (d, 1H), 7.79 (d, 1H), 7.73-7.61 (m, 3H), 7.49-
7.44(m,3H),1.32(s,9H)。
Compound 16:7.81-7.79 (m, 1H), 7.61-7.56 (m, 3H), 7.46-7.43 (m, 2H), 7.37-7.28 (m,
4H),1.32(s,9H)。
Compound 17:7.98-7.95 (m, 2H), 7.89 (d, 1H), 7.79 (d, 1H), 7.70-7.63 (m, 3H), 7.47-
7.45(m,1H),1.58-1.52(q,2H),1.16(s,6H),0.58(t,3H)。
Compound 18:7.77 (d, 1H), 7.61-7.55 (m, 3H), 7.45-7.42 (m, 2H), 7.35-7.28 (m, 3H),
7.27-7.25(m,1H),1.69-1.60(q,2H),1.22(s,6H),0.82-0.77(t,3H)。
Compound 20:7.82-7.79 (m, 1H), 7.60-7.58 (m, 3H), 7.45-7.42 (m, 2H), 7.36-7.29 (m,
3H),7.28-7.27(m,1H),3.62(s,2H),1.36(s,6H)。
Compound 21:8.03-7.99 (m, 2H), 7.73-7.72 (m, 1H), 7.49-7.45 (m, 5H), 7.05-7.00 (m,
2H),1.95-1.80(m,2H),1.02-0.97(m,4H)。
Compound 25:7.96-7.90 (m, 2H), 7.80-7.77 (m, 2H), 7.72-7.60 (m, 3H), 7.47-7.44 (m,
3H),3.05-2.91(m,1H),1.80-1.74(m,4H),1.65-1.54(m,4H)。
Compound 31:8.00-7.98 (m, 2H), 7.89 (m, 1H), 7.80 (m, 1H), 7.72 (s, 1H), 7.73-7.67
(m,2H),7.46(m,3H),7.49-7.44(q,2H),4.28-4.20(q,2H),1.33-1.25(t,3H)。
Compound 295:8.00 (s, 1H), 7.97-7.92 (m, 2H), 7.81-7.75 (m, 2H), 7.69 (m, 2H), 7.46
(m,3H),1.27(s,9H)。
Compound 296:7.98-7.90 (m, 2H), 7.82-7.77 (m, 2H), 7.72 (s, 1H), 7.69 (m, 2H), 7.46
(m,3H),1.35(s,9H)。
Compound 311:8.01 (s, 1H), 7.94-7.90 (m, 2H), 7.82-7.77 (m, 2H), 7.69 (m, 2H), 7.46
(m,3H),4.24(q,2H),1.28(t,3H)。
Compound 455:8.15 (s, 1H), 7.80 (m, 2H), 7.66 (m, 2H), 7.46 (m, 1H), 7.06 (m, 2H), 1.27
(s,9H)。
Compound 457:8.14 (s, 1H), 7.81 (m, 2H), 7.65 (m, 2H), 7.47 (m, 1H), 7.06 (m, 2H), 1.59
(q,2H),1.22(s,6H),0.92(t,3H)。
Compound 469:8.25 (s, 1H), 7.84 (m, 2H), 7.73 (m, 2H), 7.47 (m, 1H), 7.06 (m, 2H), 3.85
(s,3H)。
Compound 475:8.26 (s, 1H), 7.85 (m, 2H), 7.72 (m, 2H), 7.47 (m, 1H), 7.06 (m, 2H), 4.86
(hept.,1H),1.28(d,6H)。
Compound 477:8.25 (s, 1H), 7.85 (m, 2H), 7.72 (m, 2H), 7.47 (m, 1H), 7.06 (m, 2H), 3.97
(d,2H),1.97(m,1H),0.95(d,6H)。
Compound 567:7.96 (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),2.83-2.79(m,1H),1.20(d,6H)。
Compound 575:7.96 (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 577:7.94 (d, 1H), 7.91 (d, 1H), 7.77-7.63 (m, 3H), 7.47 (m, 3H), 7.36-7.33
(m,2H),6.80(d,1H),1.62-1.59(q,2H),1.19(s,6H),0.57(t,3H)。
Compound 579:7.96 (d, 1H), 7.91 (m, 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 581:7.96 (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 583:7.96 (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 597:8.00 (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 655:7.94 (d, 1H), 7.88 (d, 1H), 7.78 (d, 1H), 7.71-7.63 (m, 4H), 7.55-7.52
(m,1H),7.39-7.37(m,1H),6.80(d,1H),1.23(s,9H)。
Compound 657:7.94 (d, 1H), 7.87 (d, 1H), 7.69-7.62 (m, 4H), 7.52 (d, 1H), 7.40-7.37
(m,2H),6.81(d,1H),1.62-1.59(m,2H),1.19(s,6H),0.57(t,3H)。
Compound 669:8.00 (d, 1H), 7.90 (d, 1H), 7.79 (d, 1H), 7.72-7.65 (m, 4H), 7.52 (d,
1H),7.40-7.34(m,2H),6.88(d,1H),3.81(s,3H)。
The o-trifluoromethyl phenylpropen nitrile compounds of the present invention has high parasite killing, acaricidal activity, can prevent and treat pickles
Moth, beet armyworm, Prodenia litura, bollworm, meadow mythimna separata, cabbage looper, pea aphid, bean aphid, aphis fabae, cotten aphid, apple aphid, Fructus Persicae
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, lucerne
The various pests such as Mu thrips, soybean thrip, colorado potato bug, click beetle, fly, mosquito, demodicid mite.With known acrylonitrile compound phase
Ratio, the o-trifluoromethyl phenylpropen nitrile compounds of the present invention has beyond thought high insecticidal activity.Therefore, the present invention is also
Including compound of Formula I for controlling insect, the purposes of evil demodicid mite.
Present invention additionally comprises the insecticidal and acaricidal composition using compound of Formula I as active component.This parasite killing, mite killing group
In compound, the weight percentage of active component is between 1-99%.This insecticidal and acaricidal composition also includes agricultural, forestry or
Acceptable carrier in health.
The compositions of the present invention can be used with the form of preparation.Compound of Formula I is dissolved or dispersed in as active component
In carrier or be configured to preparation so that more readily dispersible when using as Insecticidal and acaricidal agent.Such as: these chemicals can be made
Become wettable powder or cream.In these compositionss, at least add a kind of liquid or solid carrier, and the most permissible
Add suitable surfactant.
Technical scheme also includes pest control, the method for evil demodicid mite: the insecticidal and acaricidal composition of the present invention executed
In needing on insect, evil demodicid mite or its somatomedin controlled.The more suitable effective amount being generally selected is that per hectare 10 grams arrives
1000 grams, preferably effective dose is per hectare 50 grams to 500 grams.
Some is applied, such as, agriculturally can add one or more in the insecticidal and acaricidal composition of the present invention
Other antibacterial, Insecticides (tech) & Herbicides (tech), plant growth regulator or fertilizer etc., thus can produce additional advantage and effect.
It should be appreciated that, in scope defined by the claims of the present invention, various conversion and change can be carried out.
Detailed description of the invention
Following synthetic example and raw result of the test of surveying can be used to further illustrate the present invention, but are not intended to limit this
Bright.
Synthetic example
Embodiment 1, the preparation of compound 16,17
(1) synthesis of 4-chloromethyl-2-phenyl thiazole
Aminothiocarbonylbenzene (20.00 grams, 0.146 mole), methanol 200 milliliters, 1,3-dichloro third is added in there-necked flask
Ketone (22.21 grams, 0.157 mole), is warming up to backflow, back flow reaction 3 hours.Reaction is cooled to less than 30 DEG C after terminating, reaction
Liquid is poured in 50 milliliters of water, with 3 × 50 milliliters of ethyl acetate extractions, gained organic facies saturated sodium bicarbonate aqueous solution (50 millis
Rise), saturated sodium-chloride water solution (50 milliliters) washing after, be dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, residue pass through post color
Spectrum separates (leacheate: ethyl acetate: petroleum ether=1:10) and obtains 21.00 grams of 4-chloromethyl-2-phenyl thiazoles, yellow oil, yield
69%。
(2) synthesis of 4-cyanogen methyl-2-phenyl thiazole
In reaction bulb, add Cyanogran. (4.91 grams, 0.100 mole), 100 milliliters of water, drip 4-chloromethyl-2-phenyl
Ethanol (100 milliliters) solution of thiazole (21.00 grams, 0.100 mole), drips complete, is warming up to backflow, refluxes 16 hours.Instead
After should terminating, reactant liquor is poured in 200 milliliters of water, with 3 × 200 milliliters of ethyl acetate extractions, the saturated chlorination of gained organic facies
After sodium water solution (200 milliliters) washing, being dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, residue passes through pillar layer separation (drip washing
Liquid: ethyl acetate: petroleum ether=1:10) obtain 13.22 grams of 4-cyanogen methyl-2-phenyl thiazoles, yellow oil, yield 66%.
(3) synthesis of 3-(2-(trifluoromethyl) phenyl)-3-hydroxyl-2-(2-phenyl thiazole-5-base) acrylonitrile
Under ice-water bath, in reaction bulb, add 4-cyanogen methyl-2-phenyl thiazole (2.00 grams, 0.010 mole), (2-(three
Methyl fluoride) phenyl) (1H-pyrazol-1-yl) ketone (2.40 grams, 0.010 mole), oxolane 20 milliliters, stir about 1 hour,
Being dividedly in some parts potassium tert-butoxide (2.24 grams, 0.020 mole), charging terminates, and reactant liquor is warming up to room temperature, room temperature reaction 6 hours.Instead
Answering liquid to be poured in 100 milliliters of water, with 100 milliliters of ethyl acetate extractions, gained aqueous phase concentrated hydrochloric acid acid adjustment is 2 ~ 3 to pH value, with 3
× 100 milliliters of ethyl acetate extractions, organic facies is through saturated sodium bicarbonate aqueous solution (100 milliliters), saturated sodium-chloride water solution
After (100 milliliters) washing, it is dried with anhydrous magnesium sulfate, after concentration, obtains 2.10 grams of 3-(2-(trifluoromethyl) phenyl)-3-hydroxyl-2-
(2-phenyl thiazole-5-base) acrylonitrile, yellow oil, yield 61%.
(4) synthesis of compound 16
Under ice-water bath, in reaction bulb, add 3-(2-(trifluoromethyl) phenyl)-3-hydroxyl-2-(2-phenyl thiazole-5-
Base) acrylonitrile (0.37 gram, 0.001 mole), acetonitrile 10 milliliters, triethylamine (0.10 gram, 0.001 mole), then by 2,2-diformazan
Base butyl chloride (0.13 gram, 0.001 mole) is added drop-wise in reaction bulb, completion of dropwise addition, is warming up to be stirred at room temperature reaction 2 hours, instead
Liquid is answered to be poured in 50 milliliters of water, with ethyl acetate 100 milliliters extraction, gained organic facies saturated sodium bicarbonate aqueous solution (100 millis
Rise), saturated sodium-chloride water solution washing after (100 milliliters), be dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, residue passes through post
Chromatographic isolation (leacheate: ethyl acetate: petroleum ether=1:20), obtains 0.14 g of compound 16, yellow oil, yield 22%.
(5) synthesis of compound 17
3-(2-(trifluoromethyl) phenyl)-3-hydroxyl-2-(2-phenyl thiazole-5-base) acrylonitrile is added in reaction bulb
(0.74 gram, 0.002 mole), sodium bicarbonate (0.17 gram, 0.002 mole), toluene 20 milliliters, DMAP (catalysis
Amount), tetrabutyl ammonium bromide (catalytic amount), it is warming up to 100 DEG C, then by 2,2-dimethyl-butyrylchlorine (0.26 gram, 0.002 mole) drips
It is added in reaction bulb, completion of dropwise addition, continues reaction 2 hours.Reactant liquor is cooled to less than 30 DEG C, and reactant liquor is poured into 50 milliliters of water
In, with ethyl acetate 100 milliliters extraction, gained organic facies saturated sodium bicarbonate aqueous solution (100 milliliters), saturated sodium-chloride water
Solution washing after (100 milliliters), be dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, residue by pillar layer separation (leacheate:
Ethyl acetate: petroleum ether=1:30), obtain 0.25 g of compound 17, white solid, yield 39%.
Embodiment 2, the preparation of compound 469
(1) synthesis of 4-chloromethyl-2-(2,6-difluorophenyl) azoles
Addition 2,6-difluorobenzamide (10.00 grams, 0.064 mole) and 1,3-dichloro in 100 milliliters of round-bottomed flasks
Acetone (16.20 grams, 0.128 mole), is warming up to reflux and keep reacting under reflux conditions carry out 4 hours.After stopped reaction,
Naturally cooling to room temperature, be poured in 500 milliliters of water, with 3 × 100 milliliters of ethyl acetate extractions, organic facies is satisfied through 3 × 100 milliliters
After washing with sodium-chloride water solution, it is dried with anhydrous magnesium sulfate, pillar layer separation (leacheate: ethyl acetate: petroleum ether after concentration
=1:3) obtain 11.50 grams of 4-chloromethyl-2-(2,6-difluorophenyl) azoles, yellow solid, yield 76%.
(2) synthesis of 2-(2,6-difluorophenyl)-4-cyanogen methyl azoles
In the lower 50 milliliters of round-bottomed flasks of room temperature add 4-chloromethyl-2-(2,6-difluorophenyl) azoles (20.00 grams, 0.087
Mole), add 50 milliliters of abundant dissolvings of ethanol, add Cyanogran. (5.10 grams, 0.105 mole), be warming up to backflow and keep anti-
Should under reflux conditions carry out 4 hours.After stopped reaction, naturally cool to room temperature, be poured in 100 milliliters of water, with 3 × 30 milliliters
Ethyl acetate extracts, and organic facies, after 3 × 50 milliliters of saturated sodium-chloride water solution washings, is dried with anhydrous magnesium sulfate, after concentration
Pillar layer separation (leacheate: ethyl acetate: petroleum ether=1:1) obtains 14.60 grams of 2-(2,6-difluorophenyl)-4-cyanogen methyl
Azoles, white solid, yield 76%.
(3) conjunction of 3-hydroxyl-3-(2-trifluoromethyl)-2-(2-(2,6-difluorophenyl) azoles-4-base) acrylonitrile
Become
Under ice-water bath, in 100 milliliters of reaction bulbs add 2-(2,6-difluorophenyl)-4-cyanogen methyl azoles (2.00 grams,
0.009 mole), anhydrous tetrahydro furan 25 milliliters, (2-trifluoromethyl) (1H-pyrazol-1-yl) ketone (2.60 grams, 0.011
Mole), then potassium tert-butoxide (2.30 grams, 0.018 mole) is joined in reaction bulb on a small quantity in multiple times, it is warming up to be stirred at room temperature instead
Answer 4 hours, reactant liquor is poured in 50 milliliters of water, with ethyl acetate 2 × 20 milliliters washing, discard organic facies.By aqueous phase salt
Acid regulation system pH=2～3, separates out solid, and filtration is dried and obtained 2.00 grams of 3-hydroxyl-3-(2-trifluoromethyl)-2-(2-
(2,6-difluorophenyl) azoles-4-base) acrylonitrile, yellow solid, yield 67%.
(4) synthesis of compound 469
Under ice-water bath, be sequentially added in 50 milliliters of reaction bulbs 3-hydroxyl-3-(2-trifluoromethyl)-2-(2-(2,
6-difluorophenyl) azoles-4-base) acrylonitrile (0.30 gram, 0.001 mole), acetonitrile 15 milliliters and triethylamine (0.10 gram, 0.001
Mole), then methylchloroformate (0.10 gram, 0.001 mole) is added drop-wise in reaction bulb, it is warming up to reaction 4 hour is stirred at room temperature,
Reactant liquor is poured in 50 milliliters of water, is extracted with ethyl acetate (2 × 50 milliliters), and gained organic facies is with 15 milliliters of saturated sodium bicarbonates
After aqueous solution, 25 milliliters of saturated sodium-chloride water solution washings, being dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, residue passes through post
Chromatographic isolation (leacheate: ethyl acetate: petroleum ether=1:3) obtains 0.20 g of compound 469, white solid, yield 56%.
Embodiment 3, the preparation of compound 575
(1) synthesis of 3-methyl isophthalic acid-phenyl-1H-pyrazoles
Addition phenylhydrazine (5.00 grams, 0.046 mole) in reaction bulb, and 4,4-dimethoxy-2-butanones (7.30 grams, 0.055
Mole), ethanol 40 milliliters, it is warming up to backflow, refluxes 2 hours.In reactant liquor, drip concentrated hydrochloric acid (0.5 milliliter), continue backflow 2
Hour.Reaction is cooled to less than 30 DEG C after terminating, and reactant liquor is poured in 200 milliliters of water, extracts by 3 × 150 milliliters of ethyl acetate,
After gained organic facies is washed with saturated sodium-chloride water solution (150 milliliters), it is dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, remaining
Thing obtains 5.00 grams of 3-methyl isophthalic acid-phenyl-1H-pyrazoles by pillar layer separation (leacheate: ethyl acetate: petroleum ether=1:10),
Yellow oil, yield 68%.
(2) synthesis of 3-bromomethyl-1-phenyl-1H-pyrazoles
In reaction bulb, add 3-methyl isophthalic acid-phenyl-1H-pyrazoles (0.50 gram, 0.003 mole), toluene 5 milliliters, heat up
To 70 DEG C, add N-bromo-succinimide (0.40 gram, 0.003 mole), azodiisobutyronitrile (catalytic amount) to reactant liquor, add
Finishing, reactant liquor is warming up to backflow, back flow reaction 1 hour.Reaction is cooled to less than 30 DEG C after terminating, and reactant liquor is poured into 50 milliliters of water
In, with 3 × 50 milliliters of ethyl acetate extractions, gained organic facies saturated sodium bicarbonate aqueous solution (50 milliliters), saturated sodium-chloride
Aqueous solution (50 milliliters) washing after, be dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, residue by pillar layer separation (leacheate:
Ethyl acetate: petroleum ether=1:100) obtain 0.40 gram of 3-bromomethyl-1-phenyl-1H-pyrazoles, yellow oil, yield 56%.
(3) synthesis of 3-cyanogen methyl isophthalic acid-phenyl-1H-pyrazoles
3-bromomethyl-1-phenyl-1H-pyrazoles (0.55 gram, 0.003 mole), ethanol 15 milliliters, cyanogen is added in reaction bulb
Change sodium (0.15 gram, 0.003 mole), room temperature reaction 6 hours.Reactant liquor is poured in 100 milliliters of water after terminating by reaction, with 3 ×
100 milliliters of ethyl acetate extractions, after gained organic facies is washed with saturated sodium-chloride water solution (100 milliliters), use anhydrous magnesium sulfate
Being dried, after concentrating under reduced pressure, residue obtains 0.20 gram of 3-by pillar layer separation (leacheate: ethyl acetate: petroleum ether=1:20)
Cyanogen methyl isophthalic acid-phenyl-1H-pyrazoles, yellow oil, yield 36%.
(4) synthesis of 3-(2-trifluoromethyl)-2-(1-phenyl-1H-pyrazole-3-yl)-3-hydroxy nitrile
Under ice-water bath, in reaction bulb, add 3-cyanogen methyl isophthalic acid-phenyl-1H-pyrazoles (0.50 gram, 0.003 mole),
(2-trifluoromethyl) (1H-pyrazol-1-yl) ketone (0.96 gram, 0.004 mole), oxolane 5 milliliters, stir about 1 is little
Time, it being dividedly in some parts potassium tert-butoxide (0.67 gram, 0.006 mole), charging terminates, and reactant liquor is warming up to room temperature, and room temperature reaction 6 is little
Time.Reactant liquor is poured in 100 milliliters of water, and with the extraction of 100 milliliters of ethyl acetate, gained aqueous phase concentrated hydrochloric acid acid adjustment to pH value is 2 ~
3, with 3 × 100 milliliters of ethyl acetate extractions, organic facies is water-soluble through saturated sodium bicarbonate aqueous solution (100 milliliters), saturated sodium-chloride
After liquid (100 milliliters) washing, it is dried with anhydrous magnesium sulfate, after concentration, obtains 0.90 gram of 3-(2-trifluoromethyl)-2-(1-benzene
Base-1H-pyrazole-3-yl)-3-hydroxy nitrile, yellow solid, yield 85%, fusing point: 118-120 DEG C.
(5) synthesis of compound 575
Under ice-water bath, addition 3-(2-trifluoromethyl)-2-(1-phenyl-1H-pyrazole-3-yl) in reaction bulb-
3-hydroxy nitrile (0.36 gram, 0.001 mole), acetonitrile 5 milliliters, triethylamine (0.10 gram, 0.001 mole), then by pivaloyl
Chlorine (0.12 gram, 0.001 mole) is added drop-wise in reaction bulb, completion of dropwise addition, is warming up to reaction 2 hour is stirred at room temperature, and reactant liquor inclines
Enter in 50 milliliters of water, with ethyl acetate 3 × 100 milliliters extraction, gained organic facies saturated sodium bicarbonate aqueous solution (100 millis
Rise), saturated sodium-chloride water solution washing after (100 milliliters), be dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, residue passes through post
Chromatographic isolation (leacheate: ethyl acetate: petroleum ether=1:15), obtains 0.30 g of compound 575, yellow oil, yield 68%.
Embodiment 4, the preparation of compound 591
Under ice-water bath, addition 3-(2-trifluoromethyl)-2-(1-phenyl-1H-pyrazole-3-yl) in reaction bulb-
3-hydroxy nitrile (0.36 gram, 0.001 mole), acetonitrile 5 milliliters, triethylamine (0.10 gram, 0.001 mole), then by chloro-carbonic acid
Ethyl ester (0.11 gram, 0.001 mole) is added drop-wise in reaction bulb, completion of dropwise addition, is warming up to reaction 2 hour, reactant liquor are stirred at room temperature
It is poured in 50 milliliters of water, with ethyl acetate 3 × 100 milliliters extraction, gained organic facies saturated sodium bicarbonate aqueous solution (100 millis
Rise), saturated sodium-chloride water solution washing after (100 milliliters), be dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, residue passes through post
Chromatographic isolation (leacheate: ethyl acetate: petroleum ether=1:15), obtains 0.21 g of compound 591, is that one group of stereoisomer mixes
Compound (Z:E=1:2), yellow oil, yield 49%.
Biological activity determination
According to the dissolubility of testing compound, former medicinal acetone or dimethyl sulfoxide dissolve, then with 1 ‰ Tween 80 solution
Being configured to the liquid to be measured 50 milliliters of desired concn, acetone or dimethyl sulfoxide content in the solution is less than 10%.Parasite killing, mite killing
Mortality rate activity classification is as follows: A:100%；B:99%-80%；C:79%-60%；D:59%-0.
Embodiment 5, the mensuration of insecticidal activity
5.1 mensuration killing black peach aphid activity
Cut-off footpath 6 cm dishes, covers a metafiltration paper, and drips appropriate tap water moisturizing at the bottom of ware.From cultivating the sweet of black peach aphid
On blue plant, clip suitable size (diameter about 3 centimetres) and the long cabbage leaves having 15～30 aphids, remove alatae and leaf
The aphid in sheet front, after investigation radix, blade back is upwards placed in culture dish, carries out at spraying with hand-held Airbrush aerosol apparatus
Reason, pressure is that 10psi (is roughly equal to 0.7kg/cm2), spouting liquid is 0.5mL, often processes 3 times and repeats, processes and be placed on standard sight
Indoor, 48 hours " Invest, Then Investigate " survival borer populations, calculate mortality rate classification.
According to above method, partial test compound and known compound KC1(the II-15 chemical combination in WO9740009
Thing) and compound K C2(No. 1 compound in WO2007100160) has carried out killing the parallel assay of black peach aphid activity.Result of the test
It is shown in Table 2.
Table 2: o-trifluoromethyl phenyl acrylonitrile compounds and known compound KC1、KC2Kill the parallel comparison of black peach aphid activity
5.2 mensuration killing diamondback moth activity
Cabbage leaves card punch breaking into the leaf dish of diameter 2 centimetres, uses Airbrush spraying treatment, pressure is 10psi
(it is roughly equal to 0.7kg/cm2), every leaf dish positive and negative is sprayed, and spouting liquid is 0.5mL.Often process to access after drying in the shade and try worm, often 10 2 ages
Process 3 repetitions.Put into 25 DEG C, relative humidity 60～70% after process and observe indoor cultivation, 72 hours " Invest, Then Investigate " survival borer populations,
Calculate mortality rate classification.
In the part compound for examination, following compounds is preferable to the prevention effect of diamondback moth when concentration is 100ppm,
Mortality rate is more than B level: 15,17,18,19,20,21,22,575,581,583,591,595,597,655,657,669,675,
677。
The mensuration of 5.3 mythimna separates
Maize leaf being cut into the leaf section of long 2 centimetres, uses Airbrush spraying treatment, pressure is that 10psi (is roughly equal to 0.7kg/
cm2), every leaf section positive and negative is sprayed, and spouting liquid is 0.5mL.Often process to access after drying in the shade and try worm 10 2 ages, often process 3 weights
Multiple.Put into 25 DEG C, relative humidity 60～70% observation indoor cultivation, 72 hours " Invest, Then Investigate " survival borer populations after process, calculate mortality rate
And classification.
In the part compound for examination, following compounds is preferable, extremely to the prevention effect of mythimna separata when concentration is 100ppm
Rate of dying is more than B level: 15,16,17,18,19,20,21,22,31,455,457,475,477,657,669.
Embodiment 6, the mensuration of acaricidal activity
Tetranychus cinnabarinus is become the mensuration of demodicid mite activity
Assay method: take two panels true leaf Kidney bean Seedling, connects after Tetranychus cinnabarinus becomes demodicid mite and investigate radix, sprays with Airbrush
Device carries out whole strain spraying treatment, and pressure is that 10psi (is roughly equal to 0.7kg/cm2), spouting liquid is 0.5mL.Often process 3 times and repeat, place
Reason is placed on standard sight room, 72 hours " Invest, Then Investigate " survival demodicid mite numbers, calculates mortality rate classification.
In the part compound for examination, following compounds is preferable to the prevention effect of demodicid mite when concentration is 100ppm, dead
Rate reaches more than B level: 17,18,19,20,21,22,455,457,469,475,477,567,575,577,579,583,591,
595、597、655、657、669、675、677。
In the part compound for examination, following compounds is preferable to the prevention effect of demodicid mite when concentration is 10ppm, mortality rate
Reach more than B level: 18,20,21,455,457,475,477,655,657,675,677.
Claims (5)
1. an o-trifluoromethyl phenylpropen nitrile compounds, as shown in formula I:
In formula:
R is selected from the tert-butyl group, methyl tertbutyl or cyclopropyl；
Q is selected from following group:
R1Selected from H or fluorine；
R2Selected from H or fluorine；
Or its cis/trans isomer.
2. according to the compound described in claim 1, it is characterised in that in formula I:
R is selected from the tert-butyl group, methyl tertbutyl or cyclopropyl；
Q is selected from following group:
R1Selected from H；
R2Selected from H；
Or its cis/trans isomer.
3. one kind controls insect, the purposes of evil demodicid mite according to the compound of Formula I described in claim 1.
4. an insecticidal and acaricidal composition, is active component and agriculture containing compound shown in formula I as claimed in claim 1
Acceptable carrier in industry, forestry or health, in compositions, the weight percentage of active component is 1-99%.
5. one kind controls insect, the method for evil demodicid mite, it is characterised in that: by the compositions described in claim 4 with per hectare 10 grams
Impose on to the effective doses of 1000 grams on insect, evil demodicid mite or its medium grown needing to control.
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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 |
| CN1318061A (en) * | 1998-09-17 | 2001-10-17 | 日本曹达株式会社 | Thiazolylcinnamonitriles and pest controlling agents |
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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 |
| CN1318061A (en) * | 1998-09-17 | 2001-10-17 | 日本曹达株式会社 | Thiazolylcinnamonitriles and pest controlling agents |
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