CN109336879B - 3-pyridyl-1, 2, 4-oxadiazole compound and application thereof - Google Patents

3-pyridyl-1, 2, 4-oxadiazole compound and application thereof Download PDF

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CN109336879B
CN109336879B CN201811321039.8A CN201811321039A CN109336879B CN 109336879 B CN109336879 B CN 109336879B CN 201811321039 A CN201811321039 A CN 201811321039A CN 109336879 B CN109336879 B CN 109336879B
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pyridyl
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oxadiazole compound
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王明慧
许良忠
刘连才
孙鉴昕
崔焕奇
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Qingdao University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

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Abstract

The invention provides a 3-pyridyl-1, 2, 4-oxadiazole compound, which has a structure shown in a general formula I:
Figure DDA0001857512160000011
wherein R is selected from:
Figure DDA0001857512160000012

Description

3-pyridyl-1, 2, 4-oxadiazole compound and application thereof
The invention belongs to the field of agricultural insecticides and acaricides, and relates to a 3-pyridyl-1, 2, 4-oxadiazole compound and application thereof.
Background of the inventionin agriculture, crop yield reduction and quality reduction are caused by insect pests and mite pests, and the prevention and control technology of the prior art mainly depends on chemical pesticides. Due to the long-term frequent use of chemical pesticides, harmful organisms have serious drug resistance to the chemical pesticides, so that the control effect is reduced and the control cost is increased. The development of novel insecticides with different action mechanisms is an important means for overcoming or delaying the drug resistance of pests. The 1,2, 4-oxadiazole compound belongs to a five-membered heterocyclic compound, has wide physiological and biological activities, not only has the physiological activities of resisting inflammation, reducing blood pressure, reducing blood fat and the like in medicines, but also has the biological activities of killing insects, sterilizing, weeding and the like in the research and development of new pesticides. CN 104054719a discloses a bioactive compound (KC) with the following structure, which has a new action mechanism and excellent product performance due to its brand new chemical structure, and simultaneously, is used for the prevention and treatment of nematodes in crops such as soybean, cotton, corn, etc., has the characteristics of low dose, long lasting effect, low public hazard, etc., and has been commercialized as a novel nematode-preventing agent creation variety (product code Tioxazafen).
Figure BDA0001857512150000011
The compound (KC) is a disubstituted oxadiazole compound, has a new action mechanism and excellent product performance due to a brand-new chemical structure, has the characteristics of low dose, long lasting effect, low pollution and the like when being used for preventing and treating the nematodes of crops such as soybeans, cotton, corns and the like, and is commercialized as a novel nematode preventing agent creation variety (a commercial product code of Tioxazafen). The compounds of the general formula I according to the invention and their use in pesticides have not been disclosed in the prior art.
The invention aims to provide a 3-pyridyl-1, 2, 4-oxadiazole compound agricultural insecticide and acaricide which is novel in structure, simple and convenient in synthesis method, safe and efficient and can be used for preventing and controlling agricultural or forestry pests and mites.
The technical scheme of the invention is as follows:
a3-pyridyl-1, 2, 4-oxadiazole compound has a structure shown in a general formula I:
Figure BDA0001857512150000012
wherein R is selected from:
Figure BDA0001857512150000013
Figure BDA0001857512150000014
the compounds of the general formula I according to the invention can be prepared by the following reaction, wherein each group is as defined above.
Figure BDA0001857512150000021
Toluene is used as a solvent, the intermediate A is heated to reflux, and the reaction is carried out for 4 hours to obtain the compound (general formula I). The preparation method of the intermediate A is shown in the synthesis example of the specification. Table 1 lists the structures and physical properties of the compounds of formula I.
Table 1 partial structure and physical properties of compounds of general formula i
Figure BDA0001857512150000022
The invention has the advantages and positive effects that:
the compound (general formula I) has the advantages of novel structure and simple preparation method, and has high-efficiency insecticidal and acaricidal effects. Compared with a comparative compound (KC), the compound has good inhibition and killing effects on diamondback moth and mite eggs. The compound (general formula I) has unexpected comprehensive properties of treating more than one drug, reducing prevention and treatment cost, overcoming or delaying the drug resistance of harmful organisms and the like. The compound of the general formula I has good biodegradability, is environment-friendly, has no toxicity to human, livestock and beneficial organisms, is used as a new pesticide creation variety, and has very wide development and application prospects.
The invention also comprises the application of the compound in the general formula I in controlling pests and mites in agriculture and forestry.
The compound can be used alone or in combination with other active substances to improve the comprehensive performance of the product in the aspect of preventing and controlling pests and mites.
The invention also comprises an insecticidal composition taking the compound shown in the general formula I as an active component, wherein the weight percentage of the active component in the composition is 1-99%. The insecticidal composition also comprises an agriculturally or forestry acceptable carrier.
The compositions of the present invention may be administered in the form of a formulation. The compound of the general formula I is used as an active component to be dissolved or dispersed in a carrier or a solvent, and is added with a proper surfactant to be prepared into missible oil, a suspending agent, a microemulsion or wettable powder and the like.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims.
The specific implementation mode is as follows:
the following synthetic examples and results of biological tests are provided to further illustrate the invention, but are not meant to limit the invention.
Synthesis examples
Example 1 preparation of Compound Ia
(1) Synthesis of N-hydroxynicotinamide imine:
Figure BDA0001857512150000031
0.19mol (13.21g) of hydroxylamine hydrochloride, 0.2mol (20.2g) of triethylamine and 100mL of ethanol are added into a 250mL three-neck flask as a solvent, the mixture is heated and refluxed for half an hour, then 0.1mol (10.4g) of 3-cyanopyridine is added, the mixture is stirred and refluxed for 4 hours, TLC is used for monitoring the reaction to be complete, ethanol is removed by rotary evaporation, 200g of water is added, triethylamine is removed, and the mixture is filtered by suction to obtain 11.86g of white solid, and the yield is 86.56%.
(2) Synthesis of 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carbonyl chloride
Figure BDA0001857512150000032
To a 250ml three-port flask, 15.1g (0.05mol) of 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylic acid, 100ml of toluene and 7.14g (0.06mol) of thionyl chloride were sequentially added, and the mixture was heated to 80 ℃ to react for 3 hours under controlled temperature. After the reaction, toluene and thionyl chloride were distilled off to obtain 15.97g of 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carbonyl chloride in a yield of 99.5%.
(3) Intermediate AaThe synthesis of (2):
Figure BDA0001857512150000033
0.05mol (6.85g) of N-hydroxynicotinamide imine, 100mL of acetonitrile serving as a solvent and 0.055mol (5.5g) of triethylamine serving as an acid-binding agent are added into a 250mL three-neck flask, stirred, and 0.05mol (16.5g) of 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carbonyl chloride is diluted by 50mL of ethyl acetate and added into a reaction bottle dropwise to react for 2 hours after the dropwise addition. TLC monitoring till the reaction is complete, adding a proper amount of saturated aqueous sodium bicarbonate solution, performing suction filtration to obtain a brown solid, and washing with methanol to obtain a yellow solid 18.1g with the yield of 96.02%.
(4) Compound IaThe synthesis of (2):
Figure BDA0001857512150000041
into a 250mL reaction flask, 12.6g (0.03mol) of Compound A was addeda100mL of toluene was heated to reflux for 4h, TLC monitored to completion, and toluene was removed by rotary evaporation to give 11.2g of a yellow solid in 92.56% yield. Melting point 165-.1H NMR(500MHz,DMSO-d6)δ8.89(d,J＝2.1Hz,1H),8.78(dd,J＝4.8,1.6Hz,1H),8.67(dd,J＝4.7,1.5Hz,1H),8.42(dd,J＝8.1,1.5Hz,1H),8.15(dt,J＝8.1,2.0Hz,1H),7.87(s,1H),7.85(dd,J＝8.1,4.7Hz,1H),7.60(dd,J＝8.0,4.8Hz,1H).
Other compounds of formula I of the present invention may be prepared according to the above methods.
Nuclear magnetic data for other compounds are as follows:
compound IbIs/are as follows1H NMR(500MHz,DMSO-d6)δ(ppm)：8.92(d,J＝2.1Hz,1H),8.79(dd,J＝4.8,1.7Hz,1H),8.63(dd,J＝4.7,1.6Hz,1H),8.37(dd,J＝8.2,1.6Hz,1H),8.17(dt,J＝8.0,2.0Hz,1H),7.79(dd,J＝8.1,4.7Hz,1H),7.60(dd,J＝8.0,4.8Hz,1H),7.27(s,1H),6.58–6.35(m,1H),4.60(td,J＝14.9,3.3Hz,2H)。
Compound IcIs/are as follows1H NMR(500MHz,DMSO-d6)δ(ppm)：9.27(d,J＝2.1Hz,1H),8.83(dd,J＝4.9,1.7Hz,1H),8.47(dt,J＝8.0,1.9Hz,1H),8.21(d,J＝1.8Hz,2H),8.08(t,J＝1.9Hz,1H),7.67(dd,J＝8.0,4.8Hz,1H)。
Compound IdIs/are as follows1H NMR(500MHz,DMSO-d6)δ(ppm)：9.25(d,J＝2.2Hz,1H),8.82(dd,J＝4.8,1.7Hz,1H),8.44(dt,J＝8.0,2.0Hz,1H),7.65(dd,J＝8.0,4.8Hz,1H),4.23(s,3H),2.64(q,J＝7.5Hz,2H),1.22(t,J＝7.5Hz,3H).
Compound IeIs/are as follows1H NMR(500MHz,DMSO-d6)δ(ppm)：9.14(d,J＝2.1Hz,1H),8.80(dd,J＝4.9,1.8Hz,1H),8.32(dt,J＝8.0,2.0Hz,1H),7.64(dd,J＝8.0,4.8Hz,1H),7.18(d,J＝9.3Hz,1H),3.05(d,J＝8.4Hz,1H),2.57(t,J＝8.9Hz,1H),1.43(s,3H),1.31(s,3H)。
Biological activity assay
Example 2 insecticidal Activity assay
The method for testing the activity of killing the plutella xylostella comprises the following steps: the compound of the invention adopts a leaf dipping method proposed by the International Resistance Action Committee (IRAC) for measuring the activity of the plutella xylostella. Soaking cabbage leaves with the prepared liquid medicine to be detected by using straight-head ophthalmological forceps for 3-5 seconds, throwing off residual liquid, 1 piece each time, wherein 3 pieces of each sample are put on the processing paper in sequence according to the sample marking sequence. After the liquid medicine is dried, the liquid medicine is put into a straight pipe with the length of 10cm and provided with a mark, 30 heads of 3-year-old plutella xylostella larvae are inoculated, and the pipe orifice is covered by gauze. The test treatment is placed in a standard treatment chamber, the result is checked for 48h, the insect body is touched by pulling the needle, and the insect is dead. Mortality was calculated (3 replicates were taken and averaged).
At a concentration of 50ppm, the compound Ia、Ib、IcThe fatality rate to diamondback moth is 100%; at 10ppm, compound Ia、IbThe lethality rate to the diamondback moth is higher than 70 percent; selecting compound I according to the above methodbThe diamondback moth killing activity is determined in parallel with the known compound KC. The test results are shown in Table 2.
TABLE 2 survey of diamondback moth killing activity
Figure BDA0001857512150000051
As can be seen from the test results, the compounds of the present invention have excellent pesticidal activity.
Example 3 acaricidal Activity assay
Acaricidal activity test methods: the spray method proposed by the International resistance Commission (IRAC) was used. The young leaves of the kidney beans are beaten into leaf disks with the diameter of 2 cm by a puncher, the leaf disks are treated by Airbrush spray, a test compound with a certain concentration is sprayed on the front and back surfaces of each leaf disk, the spraying amount is 0.5 ml, and 20 test insects (3 years old) are inoculated in each treatment after the leaf disks are dried in the shade. After treatment, the mixture is placed into a room with the temperature of 24 ℃ and the relative humidity of 60-70% and without illumination for culture, the number of the survival insects is investigated after 48 hours, and the death rate is calculated. (3 replicates were taken and averaged).
In part of tested compounds, the following compounds have better control effect on tetranychus cinnabarinus at the concentration of 50ppm, and the death rate is more than 90 percent: i isa、Ib、Ic、Ie(ii) a Among some tested compounds, the following compounds have better control effect on tetranychus urticae at 10ppm, and the death rate is more than 90 percent: i isa、Ib、Ie(ii) a Selecting compound I according to the above methodaTetranychus cinnabarinus killing activity is determined in parallel with known compound KC. The test results are shown in Table 3.
TABLE 3 Activity assay Table for Tetranychus cinnabarinus
Figure BDA0001857512150000052
As can be seen from the test results, the compound of the present invention has excellent acaricidal activity.

Claims (3)

1. A3-pyridyl-1, 2, 4-oxadiazole compound has a structure shown in formula I:
Figure FDA0003057157820000011
wherein R is selected from:
Figure FDA0003057157820000012
2. use of a 3-pyridyl-1, 2, 4-oxadiazole compound according to claim 1 as an agricultural or forestry acaricide.
3. An acaricide composition comprising the compound of formula I as described in claim 1 as an active ingredient and an agriculturally or forestry acceptable carrier.
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Citations (5)

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CN101820761A (en) * 2007-08-13 2010-09-01 达沃股份有限公司 Be used to control composition and the method for nematode
CN103130769A (en) * 2013-01-25 2013-06-05 青岛科技大学 3-difluoro ethoxy-pyrazole amides compounds and application thereof
CN103664850A (en) * 2013-12-26 2014-03-26 青岛科技大学 Spirodiclofen sulfonate compound and application thereof
CN105037329A (en) * 2015-09-06 2015-11-11 青岛科技大学 Fluorine-containing tetrazine pyrazol acaricide
CN108341808A (en) * 2018-03-28 2018-07-31 青岛科技大学 Yi Zhong oxadiazoles connect pyrazole compound and application thereof

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US20170094972A1 (en) * 2015-10-06 2017-04-06 Syngenta Participations Ag Compounds and Compositions Having Knock-Down Activity Against Insect Pests

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101820761A (en) * 2007-08-13 2010-09-01 达沃股份有限公司 Be used to control composition and the method for nematode
CN103130769A (en) * 2013-01-25 2013-06-05 青岛科技大学 3-difluoro ethoxy-pyrazole amides compounds and application thereof
CN103664850A (en) * 2013-12-26 2014-03-26 青岛科技大学 Spirodiclofen sulfonate compound and application thereof
CN105037329A (en) * 2015-09-06 2015-11-11 青岛科技大学 Fluorine-containing tetrazine pyrazol acaricide
CN108341808A (en) * 2018-03-28 2018-07-31 青岛科技大学 Yi Zhong oxadiazoles connect pyrazole compound and application thereof

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