CN104649997B - 2,4-dimethylthiazole acrylonitrile compound and application thereof - Google Patents
2,4-dimethylthiazole acrylonitrile compound and application thereof Download PDFInfo
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- CN104649997B CN104649997B CN201310606461.9A CN201310606461A CN104649997B CN 104649997 B CN104649997 B CN 104649997B CN 201310606461 A CN201310606461 A CN 201310606461A CN 104649997 B CN104649997 B CN 104649997B
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- 0 CC(C(c1c(CCC*)nc(C)[s]1)=O)I Chemical compound CC(C(c1c(CCC*)nc(C)[s]1)=O)I 0.000 description 3
- RJXLUGSJEMSDPK-UHFFFAOYSA-N Cc(cc1)n[n]1-c1ccccc1 Chemical compound Cc(cc1)n[n]1-c1ccccc1 RJXLUGSJEMSDPK-UHFFFAOYSA-N 0.000 description 1
- GNBSSNABAIZHKN-UHFFFAOYSA-N ClCc1c[s]c(-c2ccccc2Br)n1 Chemical compound ClCc1c[s]c(-c2ccccc2Br)n1 GNBSSNABAIZHKN-UHFFFAOYSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N NNc1ccccc1 Chemical compound NNc1ccccc1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
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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
- C07D277/22—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
- A01N43/72—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
- 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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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a 2,4-dimethylthiazole acrylonitrile compound or a stereoisomer thereof with a novel structure. The structure of the compound is shown as the general formal (I) in the specification, wherein R is selected from alkyl of C1-C6, halogenated alkyl of C1-C6, naphthene of C3-C8 or alkoxy of C1-C6; Q is selected from the group as shown in the specification; R1 is selected from H, halogen, methyl or trifluoromethyl; R2 is selected from halogen; R3 and R4 are respectively selected from H, halogen, methyl or trifluoromethyl; or the stereoisomer is selected. 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
Technical field
The invention belongs to Insecticidal and acaricidal agent field.Specifically related to a kind of 2,4- dimethylthiazoles base acrylonitrile compound
And its application.
Background technology
Due to Insecticidal and acaricidal agent in use for some time, insect, evil mite can produce resistance to it, accordingly, it would be desirable to constantly
The new and improved tool desinsection of invention, the compound of acaricidal activity and composition.Meanwhile, as people are to days such as agricultural and animal products
Needs and the pay attention to day by day to environmental protection that benefit increases, also have always a demand for that use cost is lower, environment amenable new kill
Worm, acaricide.
Nissan Chemical Ind Ltd is disclosed with desinsection, mite killing or bactericidal activity in WO9740009 applications
Ethene derivatives.In JP2003201280 applications, compound K C is further disclosed1And KC2（Numbering is respectively 82 in patent
With 83）Insecticidal activity, compound K C1And KC2Under the concentration of 500ppm to the preventive effect of tick more than 80%.
In the prior art, the preparation of 2,4- dimethylthiazole base acrylonitrile compounds as representative of the present invention and its kill
Worm, acaricidal activity are not disclosed.
The content of the invention
It is an object of the invention to provide a kind of novel 2, the 4- dimethylthiazole base acrylonitrile compounds of structure, it can
It is applied to the preventing and treating of insect, evil mite in the health of agricultural, forestry or non-treatment purpose.
Technical scheme is as follows：
The invention provides one kind 2,4- dimethylthiazole base acrylonitrile compounds, as shown in formula I：
In formula：
R is selected from C1-C6Alkyl, C1-C6Haloalkyl, C3-C8Cycloalkyl or C1-C6Alkoxyl；
Q is selected from following group：
R1Selected from H, halogen, methyl or trifluoromethyl；
R2Selected from halogen；
R3、R4It is respectively selected from H, halogen, methyl or trifluoromethyl；
Or its stereoisomer.
Present invention compound still more preferably is, in formula I：
R is selected from C1-C6Alkyl, C1-C6Haloalkyl, C3-C8Cycloalkyl or C1-C6Alkoxyl；
Q is selected from following group：
R1Selected from H or halogen；
R2Selected from halogen；
R3、R4It is respectively selected from H or halogen；
Or its stereoisomer.
Present invention compound still more preferably is, in formula I：
R is selected from C3-C6Alkyl, C3-C6Haloalkyl or C1-C4Alkoxyl；
Q is selected from following group：
R1Selected from H, fluorine or chlorine；
R2Selected from fluorine or chlorine；
R3、R4It is respectively selected 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-propyl, 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.Alkoxyl refers to that alkyl end is connected with the group of oxygen atom, for example methoxyl group, ethyoxyl,
Positive propoxy, isopropoxy etc..Halogen refers to fluorine, chlorine, bromine, iodine.Stereoisomer referred in Formulas I, taking on carbon-carbon double bond
For base CN and OCOR in the same side of double bond（Z configurations）Or both sides（E）.
The compound of Formula I of the present invention can be prepared by the following method, and each group definition is the same in reaction equation.
In formula：L represents suitable leaving group, such as chlorine, bromine or tolysulfonyl epoxide.
Compounds of formula II and compound of formula III are in suitable solvent, temperature is -10 DEG C and reacts under reflux temperature
0.5-48 hours are obtained target compound I.
Suitable solvent is selected from dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrochysene
Furans, dioxane, N,N-dimethylformamide or dimethyl sulfoxide (DMSO) etc..
Suitable alkaloids are added to reacting favourable.Suitable alkali is selected from organic base, such as triethylamine, N, N- dimethyl
Aniline, pyridine, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide etc.；Or inorganic base such as NaOH, potassium hydroxide, sodium acid carbonate, carbon
Sour sodium or sodium hydride etc..
According to the difference or the difference of initiation material of reaction condition, there is stereo-isomerism in compound of Formula I.Such as carbon
Substituent CN and OCOR in carbon double bond is in the same side of double bond（Z configurations）Or both sides（E）.By selecting appropriate starting
Raw material or control reaction condition, can obtain a kind of excessive product of isomers or individual isomer.Can also be by thick product
Thing carries out the separation of conventional meanses, such as, by methods such as column chromatography, recrystallizations, obtain individual isomer.These isomers
Structure can be determined by conventionals method of analysis such as X-ray single crystal diffraction, nuclear magnetic resonance.
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 reaction 0.5-48 hours of point are obtained general formula compound II.
Suitable solvent is mainly selected from：Dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, methyl alcohol, ethanol, ethyl acetate,
Acetonitrile, tetrahydrofuran, dioxane, N,N-dimethylformamide, dimethyl sulfoxide (DMSO), 2- methylpentanes, methyl cyclopentane, oneself
Alkane, hexamethylene, hexahydrotoluene, heptane, octane, nonane, butyl ether, ethylene glycol dimethyl ether, ethylene glycol Anaesthetie Ether, ethylene glycol
Dibutyl ethers, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether etc., or as above two or three not
With the mixture of solvent.
Suitable alkaloids are added to reacting favourable.Suitable alkali is selected from organic base such as triethylamine, N, N- dimethyl benzenes
Amine, pyridine, 2- picolines, 3- picolines, 4- picolines, aldehydecollidine, 2,3 dimethyl pyridine, 2,
4- lutidines, 3,5- lutidines, 2,6- lutidines, 2,4,6- trimethylpyridines, quinoline, sodium methoxide, ethanol
Sodium, sodium tert-butoxide or potassium tert-butoxide etc., or inorganic base such as NaOH, potassium hydroxide, sodium carbonate or potassium carbonate etc..
The concrete method of operating prepared described in WO9740009, DE2633992 of compound of Formula IV.
The concrete preparation of compounds of formula V referring to Russ.J.Appl.Chem., 2008,81 (3), 513-515;
WO2007125061;WO2011111683。
Table 1 lists the structure and physical property of partial Formula I.
Table 1
Part of compounds1H NMR(300MHz,CDCl3) data are as follows：
Compound 17：8.31(m,1H),7.72(s,1H),7.43(m,1H),7.24(m,2H),2.71(s,3H),2.63
(s,3H),1.61(q,2H),1.19(s,6H),0.76(t,3H)。
Compound 55：8.22(m,1H),7.76(s,1H),7.49(m,1H),7.39(m,2H),2.72(s,3H),2.63
(s,3H),1.24(s,9H)。
Compound 57：8.22(m,1H),7.76(s,1H),7.51(m,1H),7.40(m,2H),2.72(s,3H),2.63
(s,3H),1.59(q,2H),1.16(s,6H),0.73(t,3H)。
Compound 97：8.03(m,1H),7.76(s,1H),7.69(m,1H),7.41(m,1H),7.30(m,1H),2.71
(s,3H),2.62(s,3H),1.58(q,2H),1.14(s,6H),0.72(t,3H)。
Compound 255：7.93(m,2H),7.62(s,1H),7.46(m,3H),2.50(s,3H),2.40(s,3H),1.27
(s,9H)。
Compound 271：8.06(m,2H),8.04(s,1H),7.48(m,3H),4.32(q,2H),2.72(s,3H),2.59
(s,3H),1.37(t,3H)。
Compound 335：8.07(s,1H),7.95(m,1H),7.52(m,1H),7.39(m,2H),2.71(s,3H),2.61
(s,3H),1.30(s,9H)。
Compound 337：8.07(s,1H),7.96(m,1H),7.52(m,1H),7.39(m,2H),2.71(s,3H),2.60
(s,3H),1.66(q,2H),1.25(s,6H),0.80(t,3H)。
Compound 377：8.07(s,1H),7.89(m,1H),7.71(m,1H),7.38(m,2H),2.70(s,3H),2.60
(s,3H),1.65(q,2H),1.24(s,6H),0.80(t,3H)。
Compound 417：8.11(s,1H),7.48(m,1H),7.05(m,2H),2.71(s,3H),2.60(s,3H),1.63
(q,2H),1.24(s,6H),0.79(t,3H)。
Compound 431：8.15(s,1H),7.47(m,1H),7.05(m,2H),4.30(q,2H),2.72(s,3H),2.59
(s,3H),1.26(t,3H)。
Compound 535：7.94(d,2H),7.71(m,2H),7.47(m,2H),7.34(m,1H),6.73(d,2H),2.71
(s,3H),2.62(s,3H),1.28(s,9H)。
Compound 536：7.83(d,2H),7.63(m,2H),7.45(m,2H),7.31(m,1H),6.11(d,2H),2.71
(s,3H),2.22(s,3H),1.36(s,9H)。
Compound 551：7.97(d,2H),7.73(m,2H),7.47(m,2H),7.33(m,1H),6.79(d,2H),4.30
(q,2H),2.73(s,3H),2.62(s,3H),1.33(t,3H)。
Compound 577：8.02(m,1H),7.93(m,1H),7.32(m,1H),7.28(d,1H),7.24(m,1H),6.75
(d,1H),2.71(s,3H),2.61(s,3H),1.63(q,2H),1.22(s,6H),0.78(t,3H)。
Compound 591：8.08(m,1H),7.98(m,1H),7.31(m,1H),7.29(d,1H),7.24(m,1H),6.82
(d,1H),4.27(q,2H),2.72(s,3H),2.60(s,3H),1.31(t,3H)。
Compound 592：7.94(m,1H),7.86(m,1H),7.29(m,1H),7.25(d,1H),7.21(m,1H),6.10
(d,1H), 4.31(q,2H),2.72(s,3H),2.25(s,3H),1.37(t,3H)。
2, the 4- dimethylthiazole base acrylonitrile compounds of the present invention have high desinsection, acaricidal activity, can prevent and treat little
Diamond-back 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, green rice bug, the smelly stinkbug of rice, cotton thrips,
The various pests such as alfalfa thrips, soybean thrip, colorado potato bug, click beetle, fly, mosquito, mite.With known acrylonitrile compound phase
Than 2, the 4- dimethylthiazole base acrylonitrile compounds of the present invention have unexpected high insecticidal activity.Therefore, the present invention
Also include that compound of Formula I is used to control the purposes of insect, evil mite.
Present invention additionally comprises using compound of Formula I as the insecticidal and acaricidal composition of active component.The desinsection, mite killing group
The weight percentage of active component is between 1-99% in compound.In the insecticidal and acaricidal composition also include agricultural, forestry or
Acceptable carrier in health.
The composition of the present invention can be applied in the form of preparation.Compound of Formula I is dissolved or dispersed in as active component
It is more readily dispersible in carrier or when being configured to preparation to use as Insecticidal and acaricidal agent.For example：These chemicals can be made
Into wettable powder or missible oil.In these compositions, a kind of liquid or solid carrier is at least added, and when needed can be with
Add appropriate surfactant.
Technical scheme also includes pest control, the method for evil mite：The insecticidal and acaricidal composition of the present invention is applied
On insect, evil mite or its somatomedin for needing control.The more suitable effective amount for generally selecting is arrived for 10 grams of per hectare
1000 grams, preferred effective dose is 50 grams to 500 grams of per hectare.
For some applications, for example, agriculturally can add one or more in the insecticidal and acaricidal composition of the present invention
Other bactericide, 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.
Specific embodiment
Following synthetic example and raw test result can be used to further illustrate the present invention, but be not intended to limit this
It is bright.
Synthetic example
The preparation of embodiment 1, compound 97
(1) preparation of 2- bromines thiobenzamide
2- brombenzamides are added into there-necked flask（50.00 grams, 0.25 mole）, Lawesson reagents（109.10 grams,
0.27 mole）, 200 milliliters of toluene is warming up to backflow, back flow reaction 8 hours.Reaction is down to room temperature after terminating, and filters.Filtrate Jing
Concentrate after 2 × 200 milliliters of water washings, without further purification, in directly applying to the next step.
(2) preparation of 4- chloromethyls -2- (2- bromophenyls) thiazole
The 2- bromine thiobenzamides of preparation, 200 milliliters of methyl alcohol, 1,3-DCA are walked on adding into there-necked flask
（34.30 grams, 0.27 mole）, it is warming up to backflow, back flow reaction 16 hours.Reaction is down to room temperature after terminating, and filters.Filtrate is dense
Contracting, residue passes through pillar layer separation（Leacheate：Ethyl acetate:Petroleum ether=1:10）Obtain 15.80 grams of 4- chloromethyl -2- (2-
Bromophenyl) thiazole, white solid, two step total recoverys：22%.
(3) preparation of 2- (2- (2- bromophenyls) thiazole-4-yl) acetonitrile
4- chloromethyl -2- (2- bromophenyls) thiazole is added into reaction bulb（15.80 grams, 0.055 mole）, dimethyl sulfoxide (DMSO)
100 milliliters, Cymag（5.40 grams, 0.110 mole）, react 16 hours under room temperature.Reactant liquor is poured into 500 millis by reaction after terminating
In rising water, solid is separated out in system, filtration is dried and obtains 14.40 grams of 2- (2- (2- bromophenyls) thiazole-4-yl) acetonitrile, and white is solid
Body, m.p.92-95 DEG C, yield 94%.
(4) system of 3- (2,4- dimethylthiazole -5- bases) -3- hydroxyl -2- (2- (2- bromophenyls) thiazole-4-yl) acrylonitrile
It is standby
Under ice-water bath, 2- (2- (2- bromophenyls) thiazole-4-yl) acetonitrile is added into reaction bulb（1.67 grams, 0.006 rubs
You）, (2,4- dimethylthiazole -5- bases) (1H- pyrazol-1-yls) ketone（1.24 grams, 0.006 mole）, 20 milliliters of tetrahydrofuran,
After stir about 30 minutes, potassium tert-butoxide is dividedly in some parts（1.35 grams, 0.012 mole）, charging terminates, and reactant liquor is warming up to room temperature,
Room temperature reaction 2 hours.After stopping reaction, decompression steams the solvent in system, after residue is fully dissolved with 200 milliliters of water, uses
Concentrated hydrochloric acid acid adjustment to pH value is 2～3, and solid is separated out in system, and filtration is dried and obtains 2.23 grams of 3- (2,4- dimethylthiazole -5-
Base) -3- hydroxyl -2- (2- (2- bromophenyls) thiazole-4-yl) acrylonitrile, yellow solid, yield 89%.
(5) preparation of compound 97
3- (2,4- dimethylthiazole -5- bases) -3- hydroxyl -2- (2- (2- bromophenyls) thiazole -4- are added into reaction bulb
Base) acrylonitrile（0.42 gram, 0.001 mole）, 15 milliliters of acetonitrile, triethylamine（0.25 milliliter, 0.002 mole）, then by 2,2- bis-
Methylbutyryl chlorine（0.15 milliliter, 0.001 mole）It is added drop-wise in reaction bulb, completion of dropwise addition, is warming up to that reaction is stirred at room temperature is 2 little
When, reactant liquor is poured in 50 milliliters of water, with 100 milliliters of extractions of ethyl acetate, gained organic phase saturated sodium bicarbonate aqueous solution
（100 milliliters）, saturated sodium-chloride water solution washing after（100 milliliters）, it is dried with anhydrous magnesium sulfate, after reduced pressure concentration, residue
By pillar layer separation（Leacheate：Ethyl acetate:Petroleum ether=1:4）, obtain 0.50 g of compound 97, yellow viscous liquid,
Yield 96%.
The preparation of embodiment 2, compound 335
(1) the 4- chloromethyls -2- (preparations of 2- chlorphenyl) oxazoles
2- chlorobenzamides are added in 100 milliliters of round-bottomed flasks（2.80 grams, 0.018 mole）With 1,3- dichloroacetones
（4.60 grams, 0.036 mole）, melting is heated to, it is further continued for being warming up to and flows back and keep reaction to carry out 4 under reflux conditions little
When.After stopping reaction, room temperature is naturally cooled to, in being poured into 50 milliliters of water, extracted with 3 × 10 milliliters of ethyl acetate, organic phase Jing 3
After × 20 milliliters of saturated sodium-chloride water solution washings, it is dried with anhydrous magnesium sulfate, pillar layer separation after concentration（Leacheate：Acetic acid
Ethyl ester:Petroleum ether=1:3）Obtain 3.10 grams of 4- chloromethyl -2- (2- chlorphenyl) oxazoles, yellow solid, yield 77%.
(2) preparation of 2- (2- chlorphenyls) -4- Qing Jia Ji oxazoles
4- chloromethyl -2- (2- chlorphenyl) oxazoles are added in the lower 500 milliliters of round-bottomed flasks of room temperature（45.50 grams, 0.20 rubs
You）, 200 milliliters of dimethyl sulfoxide (DMSO), Cymag（14.66 grams, 0.30 mole）, react 24 hours under room temperature.Reaction will after terminating
Reactant liquor is poured in 1000 milliliters of water, and solid is separated out in system, and filtration is dried and obtains 39.40 grams of 2- (2- (2- chlorphenyl) Evil
Azoles -4- bases) acetonitrile, yellow solid, yield 90%.
(3) 3- (2,4- dimethylthiazole -5- the bases) -3- hydroxyl -2- (systems of 2- (2- chlorphenyl) oxazole -4- bases) acrylonitrile
It is standby
Under ice-water bath, 2- (2- (2- chlorphenyl) oxazole -4- bases) acetonitriles are added into reaction bulb（1.31 grams, 0.006 rubs
You）, (2,4- dimethylthiazole -5- bases) (1H- pyrazol-1-yls) ketone（1.24 grams, 0.006 mole）, 20 milliliters of tetrahydrofuran,
After stir about 30 minutes, potassium tert-butoxide is dividedly in some parts（1.35 grams, 0.012 mole）, charging terminates, and reactant liquor is warming up to room temperature,
Room temperature reaction 2 hours.After stopping reaction, decompression steams the solvent in system, after residue is fully dissolved with 200 milliliters of water, uses
Concentrated hydrochloric acid acid adjustment to pH value is 2～3, and solid is separated out in system, and filtration is dried and obtains 2.06 grams of 3- (2,4- dimethylthiazole -5-
Base) -3- hydroxyl -2- (2- (2- chlorphenyl) oxazole -4- bases) acrylonitrile, beige solid, yield 96%.
(4) preparation of compound 335
3- (2,4- dimethylthiazole -5- bases) -3- hydroxyl -2- (2- (2- chlorphenyl) oxazole -4- are added into reaction bulb
Base) acrylonitrile（0.36 gram, 0.001 mole）, 15 milliliters of acetonitrile, triethylamine（0.25 milliliter, 0.002 mole）, then by pivaloyl
Chlorine（0.20 milliliter, 0.001 mole）It is added drop-wise in reaction bulb, completion of dropwise addition, is warming up to and reaction 2 hours, reactant liquor is stirred at room temperature
In being poured into 50 milliliters of water, with 100 milliliters of extractions of ethyl acetate, gained organic phase saturated sodium bicarbonate aqueous solution（100 milliliters）、
After saturated sodium-chloride water solution washing（100 milliliters）, it is dried with anhydrous magnesium sulfate, after reduced pressure concentration, residue passes through column chromatography
Separate（Leacheate：Ethyl acetate:Petroleum ether=1:4）, obtain 0.32 g of compound 335, yellow viscous liquid, yield 73%.
The preparation of embodiment 3, compound 431
(1) 3- (2,4- dimethylthiazole -5- bases) -3- hydroxyl -2- (2- (2,6- difluorophenyl) oxazole -4- bases) acrylonitrile
Preparation
Under ice-water bath, 2- (2- (2,6- difluorophenyl) oxazole -4- bases) acetonitriles are added into reaction bulb（1.32 gram,
0.006 mole）, (2,4- dimethylthiazole -5- bases) (1H- pyrazol-1-yls) ketone（1.24 grams, 0.006 mole）, tetrahydrofuran
20 milliliters, stir about is dividedly in some parts potassium tert-butoxide after 30 minutes（1.35 grams, 0.012 mole）, charging terminates, and reactant liquor heats up
To room temperature, room temperature reaction 2 hours.After stopping reaction, decompression steams the solvent in system, and residue is fully molten with 200 milliliters of water
Xie Hou, is 2～3 with concentrated hydrochloric acid acid adjustment to pH value, and solid is separated out in system, and filtration is dried and obtains 2.06 grams of 3- (2,4- dimethyl
Thiazole -5- bases) -3- hydroxyl -2- (2- (2,6- difluorophenyl) oxazole -4- bases) acrylonitrile, beige solid, yield 95%.
(2) preparation of compound 431
Into reaction bulb add 3- (2,4- dimethylthiazole -5- bases) -3- hydroxyl -2- (2- (2,6- difluorophenyl) oxazoles -
4- yls) acrylonitrile（0.36 gram, 0.001 mole）, 15 milliliters of acetonitrile, triethylamine（0.25 milliliter, 0.002 mole）, then by chloromethane
Acetoacetic ester（0.15 milliliter, 0.001 mole）It is added drop-wise in reaction bulb, completion of dropwise addition, is warming up to and reaction 2 hours is stirred at room temperature, instead
Liquid is answered to be poured in 50 milliliters of water, with 100 milliliters of extractions of ethyl acetate, gained organic phase saturated sodium bicarbonate aqueous solution（100 millis
Rise）, saturated sodium-chloride water solution washing after（100 milliliters）, it is dried with anhydrous magnesium sulfate, after reduced pressure concentration, residue passes through post
Chromatographic isolation（Leacheate：Ethyl acetate:Petroleum ether=1:4）, obtain 0.15 g of compound 431, light yellow viscous liquid, cooling
After can separate out yellow, waxy solid, yield 37%.
The preparation of embodiment 4, compound 535,536
(1) preparation of 3- methyl isophthalic acids-phenyl -1H- pyrazoles
Phenylhydrazine is added into reaction bulb（5.00 grams, 0.046 mole）, 4,4- dimethoxy-2-butanones（7.30 grams, 0.055
Mole）, 40 milliliters of ethanol is warming up to backflow, flows back 2 hours.Concentrated hydrochloric acid is added dropwise in reactant liquor（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, is extracted with 3 × 150 milliliters of ethyl acetate,
Gained organic phase saturated sodium-chloride water solution（150 milliliters）After washing, it is dried with anhydrous magnesium sulfate, it is remaining after reduced pressure concentration
Thing passes through pillar layer separation（Leacheate：Ethyl acetate:Petroleum ether=1:10）5.00 grams of 3- methyl isophthalic acids-phenyl -1H- pyrazoles are obtained,
Yellow oil, yield 68%.
(2) preparation of 3- bromomethyls -1- phenyl -1H- pyrazoles
3- methyl isophthalic acids-phenyl -1H- pyrazoles is added into reaction bulb（0.50 gram, 0.003 mole）, 5 milliliters of toluene, intensification
To 70 DEG C, to reactant liquor N- bromo-succinimides are added（0.40 gram, 0.003 mole）, azodiisobutyronitrile (catalytic amount), plus
Finish, 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, extracted with 3 × 50 milliliters of ethyl acetate, gained organic phase saturated sodium bicarbonate aqueous solution（50 milliliters）, saturated sodium-chloride
The aqueous solution（50 milliliters）After washing, it is dried with anhydrous magnesium sulfate, after reduced pressure concentration, residue passes through 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) preparation of 2- (1- phenyl -1H- pyrazole-3-yls) acetonitrile
3- bromomethyl -1- phenyl -1H- pyrazoles is added into reaction bulb（0.55 gram, 0.003 mole）, the milli of dimethyl sulfoxide (DMSO) 5
Rise, Cymag（0.15 gram, 0.003 mole）, room temperature reaction 6 hours.Reaction is poured into reactant liquor in 100 milliliters of water after terminating,
Extracted with 3 × 100 milliliters of ethyl acetate, gained organic phase saturated sodium-chloride water solution（100 milliliters）After washing, anhydrous sulphur is used
Sour magnesium is dried, and after reduced pressure concentration, residue passes through pillar layer separation（Leacheate：Ethyl acetate:Petroleum ether=1:20）Obtain 0.20
Gram 2- (1- phenyl -1H- pyrazole-3-yls) acetonitrile, yellow oil, yield 36%.
(4) preparation of 3- hydroxyls -3- (2,4- dimethylthiazole -5- bases) -2- (1- Phenylpyrazole -3- bases) acrylonitrile
1- phenyl -3- cyanogen methyl isophthalic acid H- pyrazoles is sequentially added into 500 milliliters of there-necked flasks（10.00 grams, 0.055 mole）,
2,4- dimethylthiazole -5- base Ethyl formates（12.00 grams, 0.065 mole）, 200 milliliters of normal heptane, the milli of ethylene glycol diethyl ether 50
Rise, to install and be passed through nitrogen 20 minutes after water knockout drum, backflow is reheated, by 28% sodium methoxide/methanol solution（21.00 grams, 0.110 rubs
You）It is slowly dropped in reaction bulb, continues to keep reaction to carry out under reflux conditions 2 hours after completion of dropping.Stop reaction,
Room temperature is naturally cooled to, in pouring 1000 milliliters of water into, water is mutually used hydrochloric acid regulation system pH=2～3, separate out solid, filtration is dried
Obtain 8.00 grams of intermediate 3- hydroxyl -3- (2,4- dimethylthiazole -5- bases) -2- (1- Phenylpyrazole -3- bases) acrylonitrile, yellow
Solid, yield 44%.
(5) preparation of compound 535,536
3- hydroxyl -3- (2,4- dimethylthiazole -5- bases) -2- (1- phenyl pyrazolines are sequentially added into 500 milliliters of reaction bulbs
Azoles -3- bases) acrylonitrile（0.70 gram, 0.002 mole）, 100 milliliters of toluene and sodium acid carbonate（0.40 gram, 0.004 mole）With urge
The DMAP and TBAB of change amount, is heated to 70 DEG C.It is slowly dropped into pivaloyl chloride（0.30 gram, 0.003 mole）, continue after completion of dropping
Reaction is kept to carry out under reflux conditions 1 hour.After stopping reaction, reactant liquor is poured in 50 milliliters of water, is extracted with ethyl acetate
（2 × 50 milliliters）, gained organic phase washed with 15 milliliters of saturated sodium bicarbonate aqueous solutions, 25 milliliters of saturated sodium-chloride water solutions
Afterwards, it is dried with anhydrous magnesium sulfate, after reduced pressure concentration, residue passes through pillar layer separation（Leacheate：Ethyl acetate:Petroleum ether=
1:20）Obtain 0.10 g of compound 535 successively, yellow solid, m.p.131-132 DEG C, yield 11%；0.40 g of compound 536,
Yellow solid, m.p.141-142 DEG C, yield 45%.
Biological activity determination
According to the dissolubility of testing compound, active compound acetone or dimethyl sulfoxide dissolve, then with 1 ‰ Tween 80 solution
50 milliliters of the prepare liquid of desired concn is configured to, acetone or dimethyl sulfoxide content in the solution is less than 10%.
The measure of embodiment 5, insecticidal activity
5.1 measure for killing black peach aphid activity
Diameter 6cm culture dishes are taken, a metafiltration paper is covered at ware bottom, and appropriate running water moisturizing is added dropwise.From the wild cabbage of culture black peach aphid
Clip suitable size and length has the cabbage leaves of 30-50 head black peach aphids on plant, removes alatae and positive aphid, and blade back is upwards
It is placed in culture dish.With Airbrush spraying machines in leave dual sides even spraying（Atomisation pressure：10psi, converts into 0.7kg/
cm2,；Spouting liquid：0.5mL；Spraying distance：15-20cm）.Culture dish is moved in standard sight room（23-25 DEG C, 40-60%
R.H., L/D is 13h：11h）, then at ware bottom appropriate running water is added dropwise to keep blade fresh if needed during observation.
According to above method, partial test compound and known compound KC1（No. 82 chemical combination in JP2003201280
Thing）With compound K C2（No. 83 compounds in JP2003201280）Carry out killing the parallel determination of black peach aphid activity.Result of the test
It is shown in Table 2.
Table 2：Part the compounds of this invention and known compound KC1、KC2Kill the parallel comparison of black peach aphid activity（The death rate, %）
*：Expression is not surveyed
5.2 measure for killing diamondback moth activity
Using spray-on process.The cabbage leaves of hot-house culture are selected, surface wax layer is removed, with card punch a diameter of 3cm is broken into
Circular leaf dish, the order by experimental design from low dosage to high dose, with airbrush manual spray hoses by the medicine for preparing
Liquid is uniformly sprayed on leave dual sides, in being placed in the culture dish of a diameter of 6cm for being placed with filter paper, neat being good for is accessed after drying in the shade naturally
Health test worm（3 ages）, 10 are often processed, if clear water is processed as blank.Examination material after process is placed in into the observation of certain condition
In room, life or death borer population is investigated after 72h, calculate the death rate, and virulence regression equation, LC are calculated with DPS softwares50Value and 95% put
The indexs such as letter limit.
In compound of the part for examination, following compounds are preferable to the prevention effect of diamondback moth when concentration is 600ppm,
The death rate is more than or equal to 80%：17、31、55、57、71、111、255、271、337、377、391、417、431、551、577、
591、592。
In compound of the part for examination, following compounds are preferable to the prevention effect of diamondback moth when concentration is 100ppm,
The death rate is more than or equal to 80%：431.
The measure of 5.3 mythimna separates
Using spray-on process.The fresh corn middle part blade for selecting greenhouse production is cut into 3cm segments, by experimental design from low dosage
To the order of high dose, the liquid for preparing uniformly is sprayed on into leave dual sides, is placed in the culture of a diameter of 6cm for being placed with filter paper
In ware, neat healthy test worm is accessed after drying in the shade naturally（3 ages）, 10 are often processed, if clear water is processed as blank.To process
Examination material afterwards is placed in the observation ward of certain condition, and life or death borer population is investigated after 72h, calculates the death rate, and is calculated with DPS softwares
LC50Value.
In compound of the part for examination, following compounds are preferable to the prevention effect of mythimna separata when concentration is 100ppm, extremely
Rate of dying is more than or equal to 80%：17、31、55、57、71、97、111、417、551、591.
The measure of embodiment 6, acaricidal activity
To Tetranychus cinnabarinus into the active measure of mite
Select the Kidney bean seedling with two panels true leaf within 1 day before treatment, transplant in culture dixie cup, one plant per glass.Wait to transplant
After seedling restore normal growth, lobus cardiacus and a piece of true leaf are cut off in first three hour is processed, on remaining a piece of true leaf 30- is connected
The Tetranychus cinnabarinus of 50 stalwartnesses records radix into mite, often processes and is repeated 2 times, and sets blank.Enter within 72 hours after process
Row investigation, records the mite number dead, living on whole strain Kidney bean seedling, calculates the death rate.
In compound of the part for examination, following compounds are preferable to the prevention effect of mite when concentration is 10ppm, the death rate
More than or equal to 80%：17、31、55、57、71、97、255、271、335、337、351、377、391、417、551、577、591、
592。
Claims (5)
1. one kind 2,4- dimethylthiazole base acrylonitrile compounds, as shown in formula I：
In formula：
R is selected from C1-C6Alkyl or C1-C6Alkoxyl；
Q is selected from following group：
R1Selected from H or halogen；
R2Selected from halogen；
R3、R4It is respectively selected from H or halogen；
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 C3-C6Alkyl or C1-C4Alkoxyl；
Q is selected from following group：
R1Selected from H, fluorine or chlorine；
R2Selected from fluorine or chlorine；
R3、R4It is respectively selected from H, fluorine or chlorine；
Or its cis-trans-isomer.
3. a kind of compound of Formula I according to described in claim 1 controls the purposes of agricultural pests, evil mite.
4. a kind of agricultural insecticidal, miticide composition, are active component containing compound shown in formula I as claimed in claim 1
Agriculturally acceptable carrier, the weight percentage of active component is 1-99% in composition.
It is 5. a kind of to control agricultural pests, the method for evil mite, it is characterised in that：By the composition described in claim 4 with per hectare
10 grams to 1000 grams of effective dose is imposed on the medium of the agricultural pests, evil mite or its growth that need control.
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