CN106831646B - Thiadiazoles amides compound and application - Google Patents

Thiadiazoles amides compound and application Download PDF

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Publication number
CN106831646B
CN106831646B CN201510882355.2A CN201510882355A CN106831646B CN 106831646 B CN106831646 B CN 106831646B CN 201510882355 A CN201510882355 A CN 201510882355A CN 106831646 B CN106831646 B CN 106831646B
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compound
formula
bromine
chlorine
general formula
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CN106831646A (en
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吕亮
王刚
班兰凤
张稳
刘少武
梁爽
李斌
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/06—1,2,3-Thiadiazoles; Hydrogenated 1,2,3-thiadiazoles
    • 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
    • A01N43/82—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 three ring hetero atoms

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  • Life Sciences & Earth Sciences (AREA)
  • 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)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention belongs to Insecticidal and acaricidal agent fields.It is related to a kind of thiadiazoles amides compound and application.Thiadiazoles amides compound is as shown in general formula I:

Description

Thiadiazoles amides compound and application
Technical field
The invention belongs to Insecticidal and acaricidal agent fields.It is related to a kind of thiadiazoles amides compound and application.
Background technique
In use for some time due to Insecticidal and acaricidal agent, pest can generate resistance to it, and therefore, it is necessary to constantly invent Novel and improved compound and composition with desinsection, acaricidal activity.
Known certain thiadiazoles amide compounds have bactericidal activity, as CN1180297A discloses compound K C1(patent Middle compound 105), KC2(compound 388 in patent) and KC3(compound 137 in patent) and its bactericidal activity.Certain thiadiazoles Amide compound structure discloses, but without pertinent literature and active report, such as compound K C4(CAS:724435-73-8)
In the prior art, structure thiadiazoles amides compound as shown in general formula I of the present invention has not been reported.
Summary of the invention
The purpose of the present invention is to provide a kind of better thiadiazoles amides compounds of insecticidal activity, it can be applied to agriculture The prevention and treatment of pest, harmful mite in industry.
To achieve the above object, technical scheme is as follows:
Thiadiazoles amides compound as shown in general formula I,
In formula:
R1Selected from chlorine, bromine, iodine or C1-C6Halogenated alkyl；
R2Selected from hydrogen, halogen, nitro, cyano or C1-C6Halogenated alkyl.
Preferred technical solution is in the present invention, in general formula I:
R1Selected from chlorine, bromine, iodine or C1-C3Halogenated alkyl；
R2Selected from hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano or C1-C3Halogenated alkyl.
Further preferred technical solution is in the present invention, in general formula I:
R1Selected from chlorine, bromine, iodine, trifluoromethyl, pentafluoroethyl group, seven fluorine n-propyls or hepta-fluoroiso-propyl；
R2Selected from hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano, trifluoromethyl, pentafluoroethyl group, seven fluorine n-propyls or seven fluorine isopropyls Base.
Particularly preferred technical solution is in the present invention, in general formula I:
R1Selected from chlorine, bromine, iodine or trifluoromethyl；
R2Selected from chlorine, bromine, iodine, nitro, cyano or trifluoromethyl.
In the definition of compound of Formula I given above, collects term used and is generally defined as follows:
Halogenated alkyl refers to the group that alkyl is optionally substituted with one or more halogen atoms, such as chloroethyl, trifluoromethyl, difluoro first Base, hepta-fluoroiso-propyl etc..Halogen refers to fluorine, chlorine, bromine, iodine.
The technology of the present invention feature further includes the preparation method of compound of Formula I, outer except as otherwise indicating, each group in reaction equation It is as defined above.
In suitable solvent, temperature is -10 DEG C of boiling points for arriving suitable solvent for Compounds of formula II and compound of formula III 0.5-48 hours obtained target compound I of lower reaction.
Suitable solvent is selected from methylene chloride, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydro Furans, dioxane, N,N-dimethylformamide or dimethyl sulfoxide etc..
Suitable alkali is added to reacting advantageous, suitable alkali includes the alkali metal such as hydrogen compound of lithium, sodium or potassium as hydrogenated Sodium, the alkali metal such as hydroxide of lithium, sodium or potassium such as sodium hydroxide, can also be the carbonate such as sodium carbonate of alkali metal, can also To be organic base such as triethylamine, sodium tert-butoxide etc..
Compounds of formula II can refer to following documents preparation: Bioorganic&Medicinal ChemistryLetters, 2007,17(24):6836-6840；Journal of Agricultural and Food Chemistry,2009,57(10): 4279-4286.Compound of formula III be it is commercially available or can refer to following documents preparation: WO2006134468A, Journal of Organic Chemistry,2013,78(10):5103-5109；Synthesis,2009,8:1305-1308.
Table 1 lists the structure and physical property of partial Formula Compound I.
The structure and physical property of 1 partial Formula Compound I of table
Serial number R1 R2 Appearance (fusing point (DEG C))
1 Cl H Faint yellow solid (113-114)
2 Br H White solid (117-118)
3 I H White solid (119-120)
4 CF3 H Yellow solid (98-99)
5 Cl Cl White solid (180-181)
6 Cl Br White solid (172-173)
7 Br Br White solid (190-192)
8 I I White solid (170-171)
9 Cl CN
10 Cl NO2
11 Br CN
12 Br NO2
13 I CN
14 I NO2
15 Cl CF3
16 Br CF3
17 I CF3
18 Br CF(CF3)2
19 I CF(CF3)2
20 I CF(CF3)2
21 CF3 CF3
Part of compounds1H NMR(300MHz,CDCl3) data are as follows:
Compound 1:8.63-8.66 (d, 1H), 8.25 (s, 1H), 7.73 (s, 1H), 7.62-7.64 (d, 1H), 3.064 (s,3H)。
Compound 2:8.61-8.64 (d, 1H), 8.27 (s, 1H), 7.89 (s, 1H), 7.65-7.68 (d, 1H), 3.08 (s, 3H)。
Compound 3:8.39-8.41 (d, 2H), 8.11 (s, 1H), 7.69-7.71 (d, 1H), 7.33-7.69 (t, 1H).
Compound 4:8.57-8.60 (d, 1H), 8.02 (s, 1H), 7.95 (s, 1H), 7.90-7.93 (d, 1H), 3.03 (s, 3H)。
Compound 5:7.72 (s, 2H), 7.39 (s, 1H), 3.03 (s, 3H).
Compound 6:7.87 (s, 1H), 7.76 (s, 1H), 7.52 (s, 1H), 3.02 (s, 3H).
Compound 7:7.92 (s, 2H), 7.41 (s, 1H), 3.04 (s, 3H).
Compound 8:8.15 (s, 2H), 7.47 (s, 1H), 3.05 (s, 3H).
Compared with known thiadiazoles amides compound, thiadiazoles amides compound of the invention has unexpected High desinsection, acaricidal activity.Therefore, the invention also includes the purposes that compound of Formula I is used to control pest, harmful mite.
The invention also includes the insecticidal and acaricidal compositions using compound of Formula I as active component.The desinsection, mite killing group The weight percentage in object as the compound of Formula I of active component is closed between 1-99%.In the insecticidal and acaricidal composition It further include agriculturally acceptable carrier.
Composition of the 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.Such as: these chemicals can be made At 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 Surfactant appropriate is added.
Technical solution of the present invention further includes the method for pest control, harmful mite: insecticidal and acaricidal composition of the invention is applied In on the pest or its somatomedin.The more suitable effective quantity generally selected is 10 grams to 1000 grams of per hectare.
It is one or more for certain applications, such as can be agriculturally added in insecticidal and acaricidal composition of the invention Thus other fungicide, Insecticides (tech) & Herbicides (tech), plant growth regulator or fertilizer etc. can produce additional advantage and effect.
It should be appreciated that various transformation and change can be carried out in scope defined by the claims of the present invention.
Specific embodiment
Following synthetic example, biological activity determination embodiment can be used to further illustrate the present invention, but not mean that limit The system present invention.
Synthetic example
The preparation of 1 compound 1 of embodiment:
In reaction flask be added the chloro- 4- 5-trifluoromethylaniline of 2- (280 milligrams, 1.43 mMs), sodium hydride (45 milligrams, 60%, 1.86 mMs) and 10 milliliters of tetrahydrofurans, lower dropwise addition 4- methyl-1,2,3- thiadiazoles -5- formyl chlorides are stirred at room temperature 10 milliliters of tetrahydrofuran solution of (275 milligrams, 1.70 mMs).Drop finishes, and reacts at room temperature, end of reaction after 2 hours.Reaction Liquid is poured into 30 milliliters of water, takes organic layer, and organic layer successively uses saturated sodium bicarbonate aqueous solution, saturated common salt water washing, nothing Water magnesium sulfate is dry, and solvent to the greatest extent is steamed in decompression.Residue purifies (leacheate: ethyl acetate: petroleum ether=1:10) by column chromatography, Obtain 400 milligrams of compounds 1, yield 87%.
The preparation of 2 compound 5 of embodiment:
2,6- dichlor-4-trifluoromethyl aniline (250 milligrams, 1.09 mMs), triethylamine (133 millis are added in reaction flask Gram, 1.31 mMs) and 10 milliliters of acetonitriles, lower dropwise addition 4- methyl-1,2,3- thiadiazoles -5- formyl chlorides (177 millis are stirred at room temperature Gram, 1.09 mMs) 10 milliliters of acetonitrile solution.Drop finishes, and is heated to reflux, end of reaction after 3 hours.Reaction solution is poured into 30 milliliters In water, organic layer is taken, organic layer uses saturated sodium bicarbonate aqueous solution, saturated common salt water washing respectively, and anhydrous magnesium sulfate is dry, subtracts Pressure steams solvent to the greatest extent.Residue purifies (leacheate: ethyl acetate: petroleum ether=1:8) by column chromatography, obtains 120 milligrams of compounds 5, yield 31%.
Other compound of Formula I of the invention can refer to above method synthesis.
Biological activity determination embodiment
According to the dissolubility of untested compound, compound of Formula I raw medicine acetone or dimethyl sulfoxide dissolution, then with 1 ‰ Tween 80 solution be configured to 50 milliliters of prepare liquid of required concentration, the content of acetone or dimethyl sulfoxide in the solution is no more than 10%.
The measurement of 3 insecticidal activity of embodiment
3.1 kill the active measurement of diamondback moth
The leaf dish that cabbage leaves are broken into punch to 2 centimetres of diameter, with Airbrush spraying treatment, pressure 10psi (it is roughly equal to 0.7kg/cm2), every leaf dish front and back sides are spraying, spouting liquid 0.5mL.Every processing accesses 10 2 age test worms after drying in the shade, often Handle 3 repetitions.It is put into 25 DEG C after processing, cultivates in 60~70% observation ward of relative humidity, investigation survival borer population after 72 hours, It calculates the death rate and is classified.
According to the above test method, partially in the compound of examination, following compounds are when concentration is 600ppm to pickles The control efficiency of moth is preferable, and preventive effect >=80% is compound 1 to 5,7.
The measurement of 3.2 mythimna separates
Maize leaf is cut into long 2 centimetres of leaf section, with Airbrush spraying treatment, pressure is that 10psi (is roughly equal to 0.7kg/ cm2), every leaf section front and back sides are spraying, spouting liquid 0.5mL.Every processing accesses 10 2 age test worms, 3 weights of every processing after drying in the shade It is multiple.It is put into 25 DEG C after processing, cultivates in 60~70% observation ward of relative humidity, investigation survival borer population after 72 hours calculates dead Rate is simultaneously classified.
According to the above test method, partially in the compound of examination, following compounds are when concentration is 600ppm to mythimna separata Control efficiency it is preferable, preventive effect >=80% is compound 1 to 5,7.
According to the above test method, the compounds of this invention 1,5 and 7 and known compound KC are chosen1、KC2、KC3And KC4Into Parallel determination (control compound be self-control, structure through nuclear magnetic resonance spectroscopy confirm) of the row to mythimna separata insecticidal activity, test knot Fruit is shown in Table 2.
Table 2: part the compounds of this invention is compared with known compound is to mythimna separata insecticidal activity
3.3 kill the active measurement of black peach aphid
6 cm dishes of diameter are taken, one layer of filter paper is covered at ware bottom, and appropriate tap water moisturizing is added dropwise.From the sweet of culture black peach aphid Clip suitable size (about 3 centimetres of diameter) and the cabbage leaves with 15~30 aphids on blue plant remove alatae and leaf The positive aphid of piece, after investigating radix, blade back is placed in culture dish upwards, carries out spraying place with hand-held Airbrush sprayer Reason, pressure are that 10psi (is roughly equal to 0.7kg/cm2), spouting liquid 0.5mL, 3 repetitions of every processing handle and are placed on standard sight Interior, investigation survival borer population, calculates the death rate after 48 hours.
According to the above test method, the compounds of this invention 3 and 4 is chosen.With known compound KC1、KC2And KC4It carries out to peach The parallel determination of aphid insecticidal activity, test result are shown in Table 3.
Table 3: part the compounds of this invention is compared with known compound is to black peach aphid insecticidal activity
The measurement of embodiment 4, acaricidal activity
To the active measurement of Tetranychus cinnabarinus adult mite
Measuring method: taking two panels true leaf Kidney bean seedling, spraying with Airbrush after connecting Tetranychus cinnabarinus adult mite and investigating radix Device carries out whole strain spraying treatment, and pressure is that 10psi (is roughly equal to 0.7kg/cm2), spouting liquid 0.5mL.3 repetitions of every processing, place Reason is placed on standard sight room, and investigation survival mite number after 72 hours calculates the death rate and is classified.
According to the above test method, partially in the compound of examination, following compounds are when concentration is 600ppm to cinnabar The control efficiency of tetranychid is preferable, and preventive effect >=80% is compound 3,4,5 and 7.

Claims (5)

1. a kind of thiadiazoles amides compound, it is characterised in that: compound as shown in general formula I,
I
In formula:
R1Selected from chlorine, bromine, iodine or C1-C3Halogenated alkyl；
R2Selected from hydrogen, chlorine or bromine.
2. compound described in accordance with the claim 1, which is characterized in that in general formula I:
R1Selected from chlorine, bromine, iodine or trifluoromethyl；
R2Selected from hydrogen, chlorine or bromine.
3. a kind of compound of Formula I described in accordance with the claim 1 is used to prepare insecticide, acaricidal use in agriculture field On the way.
4. a kind of insecticidal and acaricidal composition is active component and agriculture containing compound shown in general formula I as described in claim 1 Acceptable carrier in industry, the weight content in composition as the compound of Formula I of active component are 1-99%.
5. a kind of method of control pest, harmful mite, it is characterised in that: by composition as claimed in claim 4 with 10 grams of per hectare It is imposed on to 1000 grams of effective doses on the medium of the pest for needing to control, harmful mite or its growth.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1163139C (en) * 1995-03-31 2004-08-25 日本农药株式会社 Agricultural and horticultural disease controller and method for controlling diseases
CN1294121C (en) * 2001-05-31 2007-01-10 日本农药株式会社 Substituted anilide derivatives, intermediates thereof, agricultural and horticultural chemicals and their usage
JP2007126454A (en) * 2005-10-06 2007-05-24 Taisho Pharmaceut Co Ltd Anilide derivative

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1163139C (en) * 1995-03-31 2004-08-25 日本农药株式会社 Agricultural and horticultural disease controller and method for controlling diseases
CN1294121C (en) * 2001-05-31 2007-01-10 日本农药株式会社 Substituted anilide derivatives, intermediates thereof, agricultural and horticultural chemicals and their usage
JP2007126454A (en) * 2005-10-06 2007-05-24 Taisho Pharmaceut Co Ltd Anilide derivative

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
1,2,3-噻二唑类化合物农药生物活性的研究进展;龙武等;《广州化工》;20150930;第43卷(第18期);31-35
具有农药活性的1,2,3-噻二唑衍生物;王威等;《农药》;20150731;第54卷(第7期);469-475

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