WO2013003977A1 - Compound of 2,5-disubstituted-3-nitroimino-1,2,4-triazoline and preparation method and use as pesticide thereof - Google Patents

Compound of 2,5-disubstituted-3-nitroimino-1,2,4-triazoline and preparation method and use as pesticide thereof Download PDF

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WO2013003977A1
WO2013003977A1 PCT/CN2011/001096 CN2011001096W WO2013003977A1 WO 2013003977 A1 WO2013003977 A1 WO 2013003977A1 CN 2011001096 W CN2011001096 W CN 2011001096W WO 2013003977 A1 WO2013003977 A1 WO 2013003977A1
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substituted
c1
unsubstituted
compound
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Chinese (zh)
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覃兆海
马永强
苏旺苍
赵邦斌
方江升
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合肥星宇化学有限责任公司
中国农业大学
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D249/00Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/081,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/101,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/14Nitrogen atoms
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N51/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring

Abstract

Disclosed in the present invention are the preparation method and use of a compound of 2,5-disubstituted-3-nitroimino-1,2,4-triazoline and its precursor nitroideneamino-guanidine compound. Their structural formulae are shown as formulae I and VI, wherein R1 is a saturated or unsaturated C1-C10 aliphatic alkyl, saturated or unsaturated C1-C10 fluorine substituted aliphatic alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted thiazole, substituted or unsubstituted pyrazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted isoxazolyl, or tetrahydrofuran; R2 is a hydrogen, saturated or unsaturated C1-C10 aliphatic alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furyl, substituted or unsubstituted naphthyl. Tests on pesticidal activity demonstrate that compounds of formulae (I) and (VI) have a very high prevention effect against crop pests, such as aphids, plant hoppers, tetranychid mites, cotton bollworm and beet armyworm, etc., and can therefore be used as a plant pesticide.

Description

 2,5-disubstituted -3-nitroimino-1,2,4-triazoline compound and preparation method thereof and application thereof as insecticide

 The present invention relates to 2,5-disubstituted-3-niminoimido-1,2,4-triazoline compounds and precursors thereof, nitroaminoamino compounds, processes for their preparation, and their use as insecticides Application of the agent.

Background technique

 The imidacloprid developed by Bayer in the 1980s is an outstanding representative of neonicotinoid insecticides. It has excellent control effects on sucking pests, certain chewable pests, soil pests and pet fleas. A wide range of applications. Subsequently, it was found that dehydropyridinium, a metabolite of imidacloprid in the soil, has stronger insecticidal activity than it, which has caused great interest. However, the synthesis of dehydropyrimidin is not easy, and it has not been able to be industrialized on a large scale.

Invention disclosure

 The object of the present invention is to provide an insecticidal active compound 2,5-disubstituted-3-niminoimido-1,2,4-triazoline having a structure similar to dehydropyrimidin, and a precursor compound nitro group for preparing the same Aminoguanidine compounds.

 The structural formula of the 2,5-disubstituted-3-niminoimido-1,2,4-triazoline compound provided by the present invention is as shown in Formula I, and the precursor compound thereof is nitroamino hydrazine. The structural formula of the compound is as shown in formula VI:

N'N0 2

NN0 2

 NH X R

N Η 2 Ν « 2

 Ri H

 (; Formula I) (; Formula VI)

 In formula I and formula VI:

! ^ is a C1~C10 saturated or unsaturated aliphatic hydrocarbon group, a C1~C10 saturated or unsaturated fluoroaliphatic hydrocarbon group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted thiazolyl group, a substituted or Unsubstituted pyrazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted isoxazolyl, or tetrahydrofuranyl; wherein, substituted phenyl, substituted pyridyl, substituted thiazolyl, substituted The substituents in the pyrazolyl, substituted oxazolyl and substituted isoxazolyl groups may be independently selected from any one or more of the following groups: halogen (specifically F, Cl, Br, I), amino group, hydroxyl group, C1~C5 alkyl group, C1~C5 alkoxy group, C1~C5 fluorine Alkanoyl group and a fluoroalkoxy group of C1 to C5;

 Is a hydrogen, C1 to C10 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted naphthyl group; wherein the substitution The substituent in the phenyl group may be halogen, hydroxy, amino, C1 to C5 alkyl, C1 to C5 alkoxy, C1 to C5 fluoroalkyl or C1 to C5 fluoroalkoxy, aryl (e.g., phenyl, pyridyl, imidazolyl, oxazolyl, thiazolyl), aryloxy (e.g., phenoxy, pyridyloxy), etc., the substituent in the substituted pyridyl group may be halogen, C1 a C5 alkyl group, a C1 to C5 alkoxy group, a C1 to C5 fluoroalkyl group, a C1 to C5 fluoroalkoxy group, an aryloxy group (e.g., a phenoxy group, a pyridyloxy group), etc. The substituent in the substituted furyl group may be a halogen, a trifluoromethyl group or the like, and the substituent in the substituted naphthyl group may be a C1 to C5 alkyl group, a hydroxyl group, a nitro group, a halogen group, an amino group or the like.

Preferred is (: 1 to (: 10 unsaturated aliphatic hydrocarbon group, halopy pyridyl group, halothiazolyl group, or tetrahydrofuranyl group; preferably R 2 is hydrogen, substituted phenyl group, or C1 to C7 saturated or unsaturated aliphatic hydrocarbon group) .

More preferred! ^ is vinyl, ethynyl, chloropyridyl, chlorothiazolyl, tetrahydrofuran-3-yl; more preferably R 2 is hydrogen, halophenyl or C3 to C7 saturated or unsaturated aliphatic hydrocarbon.

 The saturated or unsaturated aliphatic hydrocarbon group in the present invention may be a straight chain or a branched chain.

 A method for preparing a 2,5-disubstituted-3-niminoimido-1,2,4-triazoline of the formula I and a nitroamino hydrazine compound of the formula VI, provided by the present invention, Includes the following steps:

1) nitroguanidine reacts with hydrazine hydrate to form nitroaminoguanidine of formula II;

Figure imgf000004_0001

 (Formula II)

 2) reacting the nitroaminopurine of the formula II with a carbonyl compound of the formula III under acid catalysis to form a nitroaminoguanidine of the formula IV;

0 NN0 2

Human H 2 N human N'N丫

H R 2 Η ΐ

 (Formula III) (Formula IV)

3) reacting a compound of formula IV with a compound of formula V or a sulfonate; and reacting under base catalysis to form a compound of formula VI; NN0 2

H 2 N people « 2

 R X ^ H

 (Formula V) (Formula VI)

 4) reacting a compound represented by formula VI in a weakly acidic or weakly basic medium to form a compound of the formula I;

Wherein formula III and formula VI wherein R 2 is as defined in Formula VI, Formula I is the same as R 2;

 In the middle! The definition of ^ is the same as in the formula I, X is Cl, Br, I, OTos (p-toluenesulfonyloxy) or OTf (trifluoromethanesulfonyloxy);

CH3 ~^G^ S02 ° _ F 3 CS0 2 0—

 a p-toluenesulfonyloxytrifluoromethanesulfonate group, wherein the reaction in the step 1) is carried out in a solvent, the solvent may be water; the reaction temperature of the reaction is 45-70 ° C, in the reaction The molar ratio of nitroguanidine to hydrazine hydrate can be 1: (1-1.5).

 The reaction in the step 2) is carried out in a solvent, and the solvent may be anhydrous ethanol or methanol; the reaction temperature of the reaction may be 50-80 ° C; the acid used in the reaction may specifically be acetic acid or Toluenesulfonic acid. Step 2) The molar ratio of the nitroaminopurine to the carbonyl compound of the formula III in the reaction may be 1: (1-2).

 The reaction in the step 3) is carried out in a solvent, which may be DMF (; dimethylformamide) or DME (; dimethylacetamide;); the reaction temperature may be 0-50 ° C; The base used in the reaction may specifically be sodium hydride, sodium ethoxide, sodium methoxide or sodium amide. Step 3) The molar ratio of the compound of the formula IV to the compound of the formula V may be 1: (1.2-2.5).

 The reaction in the step 4) is carried out in a solvent, which may be water, methanol, ethanol, acetonitrile; the temperature of the reaction is 0-100 ° C; the weakly acidic medium may be dilute hydrochloric acid, dilute sulfuric acid, Phosphoric acid or acetic acid; the weakly basic medium may be an aqueous solution of sodium carbonate, an aqueous solution of sodium acetate, dilute sodium hydroxide, pyridine, or triethylamine.

 Another object of the present invention is to provide a 2,5-disubstituted-1,2,4-triazoline-3-nitroimine compound of the formula I and a nitroamino hydrazine compound of the formula VI the use of.

The 2,5-disubstituted-1,2,4-triazoline-3-niminoimine compound represented by the structural formula of the formula I provided by the present invention and the nitroaminoamino compound represented by the formula VI The use of the compound of formula I and VI or a pharmaceutically acceptable salt thereof or a pharmaceutical composition containing any of them Application in plant pesticides.

 Still another object of the present invention is to provide two plant insecticides and their formulations.

 The plant insecticidal drug or preparation provided by the invention, wherein the active ingredient is a 2,5-disubstituted-1,2,4-triazoline-3-niminoimine compound represented by the formula I; A nitroaminoguanidine compound of the formula VI or a pharmaceutically acceptable salt thereof.

 The mass percentage of the active ingredient in the plant insecticide or preparation is from 0.01% to 99.99%.

 The insecticidal formulation can be processed into any acceptable dosage form as desired. For example, it may be a suspending agent, an emulsion, an aerosol, a wettable powder, an emulsifiable concentrate, a granule, or the like.

 Examples of preparation methods for the dosage form are as follows:

 Preparation of suspending agent: The active ingredient content in the commonly used formula is 5%-35%. The water, the main drug, the water dispersing agent, the suspending agent and the antifreezing agent are added to the sander and ground to prepare a suspending agent.

 Preparation of wettable powder: According to the formulation requirements, the original drug, various surfactants and solid diluents are thoroughly mixed, and after superfine pulverization, a predetermined content of the wettable powder product is obtained. In order to prepare a wettable powder suitable for spraying, a mixture of the original drug and a finely divided solid powder such as a clay, an inorganic silicate, a carbonate, and a wetting agent, a binder and/or a dispersing agent may also be used.

 Preparation of emulsifiable concentrate: It is prepared by dissolving the active ingredient in an organic solvent according to the formulation requirements, adding emulsifier and other auxiliary agents. The solvent may be toluene, xylene, methanol, etc., and if necessary, a cosolvent; other additives, including stabilizers, penetrants, and corrosion inhibitors.

 The compounds of formula I and formula VI provided by the present invention and insecticidal drugs or preparations using the same as active ingredients can control and eliminate a wide range of pests, including sucking insects (Sucking insects), mites (; Biting insects) ) and other plant pests, storage of cereal pests and health pests that cause health hazards.

 Examples of the pests are as follows:

 Homopteran pests include pests of the family Polygonaceae, Fanicidae, Polygonaceae, Hibiscus, Aphididae and Polygonaceae. The pests of the genus Polygonaceae may be cotton aphid, soybean meal, peach aphid, peach meal, radish or cabbage aphid; the pests of the plant may be brown planthopper or rice planthopper; the pests of the whitefly may be beech white; The pests of the genus Polygonaceae can be black-tailed spider mites; the pests of the genus Polygonaceae can be genus.

Lepidopteran pests include the Noctuidae and the Plutella xylostella pests. The pest of the Noctuidae can be Beet armyworm, Spodoptera litura or Helicoverpa armigera; the pest of the genus Hydrangea can be Plutella xylostella. The true eyeworm includes the leafhopper pest. The leaf worm can specifically be cinnabar leafhopper.

 The plant insecticidal drugs or preparations provided by the present invention can be used for controlling plant pests. Especially for sucking pests, scraping mouthparts pests, such as various types of aphids, flying locusts, leaf mites, leaf mites, white mites, scorpion horses have special effects, and are highly effective against cotton bollworm and beet armyworm.

 It is still another object of the present invention to provide a method of controlling plant pests.

 The method for controlling plant pests provided by the present invention is to apply the plant insecticidal drug or preparation provided by the present invention to plant leaves and/or fruits and/or seeds, and the leaves and/or fruits and/or seeds of the plants are being In an environment in which growth or anticipation is to be grown; the active ingredient of the plant insecticide or formulation is applied at a concentration of from 1 to 600 mg/L, preferably at a concentration of from 3 to 50 mg/L.

The best way to implement the invention

 The 2,5-disubstituted 3-nitroiminyl-1,2,4-triazoline compound and the nitroaminoamino compound of the present invention can be synthesized by the following reaction steps:

Figure imgf000007_0001

 The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are not intended to limit the scope of the invention. The experimental methods in the following examples which are not specified in the specific examples are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer. The percentages and parts are calculated by mass unless otherwise stated.

 2-(2-chloropyridine-5-methyl)-3-nitroimino-1,2,4-triazoline and 2-(2-chlorothiazol-5-methyl)-5-butyl The exemplified by the present invention, the 2,5-disubstituted-3-niminoimido-1,2 represented by the formula (I) provided by the present invention is exemplified. A method for preparing a 4-triazoline compound.

 Example 1. 2-(2-Chloropyridin-5-methyl)-3-nitroimino-1,2,4-triazoline (R1 in the formula I is 2-chloropyridin-5-yl, R2 Synthesis of hydrogen):

 (l) Synthesis of N'-nitroaminopurine

In a 250 mL three-necked flask, 5.0 g (0.048 mol) of nitroguanidine and 70 mL of water were successively introduced. When heated to 55 ° C under magnetic stirring, an aqueous solution of hydrazine hydrate having a mass percentage of 85% was slowly added dropwise from the dropping funnel (wherein the mass of hydrazine hydrate added was 3.5 g (0.059 mol)). The reaction was continued for 20 minutes while maintaining the temperature of the material between 55 and 60 °C. When the material turns into an orange-yellow clear liquid, use ice The water bath was rapidly cooled, and concentrated hydrochloric acid (37% by mass) was slowly added dropwise to about 6 mL to a pH of 5 to 6; cooling was continued to 2 to 3 ° C for 1 hour. The mixture was filtered under reduced pressure, washed with a small portion of ice water, and then recrystallized from hot water to give a pale yellow powder (yield: y-nitroamino hydrazine) 2.74 g, yield 48%, melting point 191 to 192 °C.

 The structural characterization data is as follows:

1H NMR (DMSO-d 6 , 5 ppm): 4.69 (s, 2H, -NHNH 2 ), 7.56 (s, lH, -NHNH 2 ), 8.27 (s, lH, -NHNO 2 ), 9.33 (s, lH, C =Ng).

 (2) Synthesis of Ν'-nitroform acetal

 In a 250 ml three-necked flask, 2.0 g (0.017 mol) of N-nitroaminopurine, 30 mL of anhydrous methanol and 0.25 mL of glacial acetic acid were sequentially added, and heated to 50 ° C under magnetic stirring, and slowly dripped from a constant pressure dropping funnel. Add 40% formaldehyde 1.6 g (0.02 mol), add dropwise, heat to reflux, and reflux for 1.0 hour. The temperature was lowered, cooled, and a large amount of white crystals were precipitated to obtain 2.1 g, and the yield was 95%, which was directly used for the next reaction.

 (3) Synthesis of Ν'-nitro-N-(2-chloropyridine-5-methyl)formal amide

In a 250 mL three-necked flask, 2.6 g (0.02 mol) of N-nitroformaldehyde acetaminophen, 40 mL of anhydrous DMF and a small amount of KI were placed in this order, and a drying tube was installed, magnetic stirring was started, and the temperature was lowered with an ice water bath. The temperature was lowered to below 10 ° C, and 1.37 g (0.04 mol) of sodium hydride having a mass content of 70% was added in three portions, and reacted for 1 hour. A solution of 4.8 g (0.03 mol) of 2-chloro-5-chloromethylpyridine and 20 mL of anhydrous DMF was slowly added dropwise from the dropping funnel. After the addition is completed, the ice water bath is removed and the temperature is naturally raised to room temperature. After reacting for 16 hours at room temperature, slowly add 200 mL of water, a dark red viscous compound appeared, and column chromatography (petroleum ether: ethyl acetate = 2:3, v/v) gave a white solid (Ν'- Base _ Ν - (2-chloro-pyridin-5-methyl) formaldehyde acetaminophen) l. lg, yield 21%, m.p. 124~ 126 °C.

 The structural characterization data is as follows:

1H NMR (DMSO-d 6 , 5 ppm): 6.88 (d, 1H), 7.13 (d, lH), 8.41 (brs, lH), 8.74 (brs,

1H), 11.67(S, 1H)

 (4) Synthesis of 2-(2-chloropyridine-5-methyl)-3-nitroimino--1,2,4-triazoline

Into a 250 mL three-necked flask, 3.0 g of N,-nitro-N-(2-chloropyridin-5-methyl)formalaminoguanidine and 80 mL of a 5 mol/L aqueous acetic acid solution were successively introduced, and the mixture was heated to reflux for 5 hours. Cooled, red oil precipitated, column chromatography (petroleum ether: ethyl acetate = 1: 1, v/v), white Color crystal (2-(2-chloropyridine-5-methyl)-3-nitroimino-1,2,4-triazoline) 1.2 g, yield 40%, m.p.: 113~115.

 The structural characterization data is as follows:

1H NMR (DMSO-d 6 , 5 ppm): 5.27 (s, 2H), 7.53 (d, lH), 7.79 (q, lH), 8.41 (d, 1H), 8.53 (s, lH), 14.05 (brs, lH) Example 2, 2-(2-chlorothiazol-5-methyl)-5-butyl-3-nitroimino-1,2,4-triazoline (in the formula I, R1 is 2-chloro Synthesis of thiazol-5-yl, R2 is butyl)

 (1) Synthesis of Ν'-nitro-n-pentanal acetal

 In a 250 ml three-necked flask, 2.0 g (0.017 mol) of N-nitroaminopurine, 30 mL of anhydrous methanol and 0.25 mL of glacial acetic acid were sequentially added, and heated to 50 ° C under magnetic stirring, and slowly dripped from a constant pressure dropping funnel. 1.7 g (0.02 mol) of n-pentanal was added, and the addition was completed, and the mixture was heated to reflux for 1.0 hour. The temperature was lowered, the solvent was evaporated under reduced pressure, and the obtained crude product was recrystallized from ethanol- petroleum ether (3:1 by volume) to give a pale yellow powder ( Ν'- nitro-n-pental acetal) 2.6 g, yield 83 %, melting point 94~95 °C.

 (2) Synthesis of Ν'-nitro-N-(2-chlorothiazole-5-methyl)-n-pental acetal

 In a 250 mL three-necked flask, N,-nitro-n-pental acetal, 3.7 g (0.02 mol), anhydrous DMF 40 mL, and a small amount of KI were placed in this order. A dry tube was installed, magnetic stirring was started, and the temperature was lowered with an ice water bath. The temperature was lowered to below 10 ° C, and 1.37 g (0.04 mol) of sodium hydride having a mass content of 70% was added in three portions and reacted for 1 hour. A solution of 2-chloro-5 chloromethylthiazole 5.1 g (0.03 mol) and anhydrous DMF 20 mL was slowly added dropwise from the dropping funnel. After the addition is completed, the ice water bath is removed and the temperature is naturally raised to room temperature. After reacting at room temperature for 16 hours, it was slowly added to 200 mL of water to precipitate a solid. After standing, filtration, water washing, and drying, colorless needle crystals (Ν'-nitro-N-2-(2-chlorothiazol-5-methyl)-n-pental acetal) 3.2 g, yield 51%. Recrystallization from ethanol-petroleum ether (volume ratio 1: 2), melting point 60~61 °C.

The structure characterization data is as follows: 1H NMR (CDCl 3 , 5 ppm): 0.93 (t, 3H), 1.28-1.38 (m, 2H) ; 1.48-1.58 (m, 2H), 2.36-2.42 (m, 2H), 5.25 ( s, 2H), 7.39 (t, lH), 7.42 (s, lH), 7.42 (brs, lH), 8.99 (brs, lH)

 (3) Synthesis of 2-(2-chlorothiazole-5-methyl)-5-butyl-3-nitroimino--1,2,4-triazoline

In a 250 mL three-necked flask, 3.0 g of N,-nitro-N-2-(2-chlorothiazole-5-methyl) was sequentially introduced. N-pentanal aminoguanidine and 80 mL of a 5 mol/L aqueous acetic acid solution were heated to reflux for 5 hours. Cooling, red oily precipitation, column chromatography (petroleum ether: ethyl acetate = 2:3, v/v) to give white crystals (2-(2-chloropyridine-5-methyl)-3-nit. Amino-1,2,4-triazoline) 1.2g, yield 40%, melting point: 88~90°C o

The structural characterization data is as follows: 1H NMR (DMSO-d 6 , 5 ppm): 0.89 (t, 3H), 1.26-

1.36 (m, 2H), 1.58-1.67 (m, 2H), 2.66-2.71 (m, 2H), 5.39 (s, 2H), 7.75 (s, lH), 13.85

(brs, lH)

 The structures of the synthesized compounds are shown in Tables 1 and 2.

 Table 1. Structure and analytical data of Compound I

N N0 2

Figure imgf000010_0001
Figure imgf000011_0001
Figure imgf000012_0001
Table 2. Structure and analytical data for Compound VI

NN0 2 H

 (formula VI)

Figure imgf000012_0002
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Example 3, the insecticidal activity test of the compound of formula I and formula VI provided by the present invention

Aphids belong to Homoptera pests and have a sucking mouth device, which is a common pest of common crops. Peach tooth

Figure imgf000015_0002

Gossypii), 缢 缢 蚜 (radish 蚜) (z^op s er /m/) is the test object, tested by dipping method. Among them, the peach aphid was collected from the cabbage field in Haidian District, Beijing. The peach aphid was collected from Taoshu, Haidian District, Beijing. The cotton aphid was collected from Mudu Tree, Haidian District, Beijing. The vegetable tube was collected from the cabbage field in Haidian District, Beijing. The 3 day old nymph was measured.

O. Triton X-100. The mass percentage of 0.5% mother liquor is used to make a mass percentage of 0.5% mother liquor, and the mass content is 0.1% Triton X-100. The aqueous solution is formulated into a measuring solution having a concentration of 0.06% (i.e., 600 ppm) (the solution can be diluted to the desired concentration when the concentration is low;). Select the leaves with sputum, leave 3 days old, and immerse the leaves with sputum for 5s in the liquid. After drying, record the number of insects, put them into the culture dish with moisturizing filter paper, cover and put (25± 1) In the °C light incubator, each agent is treated with 30 heads. On the top, set a blank control. Check the results after 5-48 hours.

 The criteria for death judgment are: Lightly touching the worm, and the individual who cannot crawl normally is regarded as a dead individual.

 Corrected mortality (%) = (sample mortality - blank control mortality) I (1-blank control mortality) χ 100%.

 The cinnabar is a female cockroach i Tetranychus cinnabarinus Boisduva, taken from the singular beta cotton field. Weigh 12 mg of the compound sample in a 20 mL weighing bottle with a one-tenth of a balance, and then add 2 mL of acetone/methanol (1:1) mixed solvent to the weighing bottle with a 1~5 mL pipette, until it is fully dissolved. Thereafter, 18 ml of an aqueous solution containing 0.1% Tween-80 was added, and the mixture was thoroughly mixed to obtain a measuring solution of 600 μg h .

Operation process: The insecticidal activity is determined by the dipping method. The bean leaves transferred to the cinnabar leafhopper are immersed in the liquid for 5 s. After drying, the number of insects is recorded in a petri dish with moisturizing filter paper, and the petiole is moisturized. Cotton moisturizing, capped and placed in a (25 ± 1) ° C light incubator. Each drug is processed more than 20 times. Check the results after 48 hours. The criteria for death are: Light-touched worms, individuals who cannot crawl normally are considered dead individuals.

 Helicoverpa armigera is a pest of Lepidoptera, and has a chewing mouth. The sample of the compound is weighed in a one-tenth of a 10,000-week volume, and the mother liquor is prepared with dimethylformamide (DMF), and then 0.1% Triton

An aqueous solution of X-100 was prepared to determine the drug solution.

Operation process: Clean the cotton leaf, use a puncher to cut the clean leek leaf into a 2cm diameter leaf dish, soak it in the liquid for 10s, dry it, put the leaf dish into the 10-hole test box, and connect the cotton bollworm 2nd instar larvae, 1 per hole, add plastic wrap, cover and put in (27±1) °C light incubator. Check the results after 48 hours. Death occurs when the needle touches the insect body and the reaction is abnormal or non-responsive.

 Beet armyworm, Lepidoptera, Lepidoptera, has a chewing mouth, and is formulated with a drug: a compound sample is weighed in a one-tenth of a milliliter bottle, and a mother liquor is prepared with dimethylformamide (DMF). 0. 1% Triton X-100 aqueous solution was prepared to determine the drug solution.

 Operation process: Wash the leek leaves and use a puncher to cut the clean leek leaves into diameters.

2cm leaf dish, immersed in the liquid for 10s, dry and put the leaf dish into the 10-hole test box, connect the 2nd instar larva of beet armyworm, one hole per hole, add plastic wrap, cover and put in (27 ±1) °C in the light incubator. The results were checked after 48 hours. Death occurs when the needle touches the insect body and the reaction is abnormal or non-responsive. The insecticidal activity results are shown in Tables 3 and 4. Table 3. Compound I killing activity against aphids (^OOppm)

 Compound corrected mortality (%)

Taoyuan (48hrs) melon (cotton) 蚜 (24hrs) peach 蚜 (24hrs) 菜缢管蚜 (24hrs;i 1-01 42.6 55.8 33.2 75.0

1-02 32.0 45.5 40.1 44.4

1-03 75.3 50.9 25.2 100

1-04 32.3 41.7 27.6 60.3

1-05 55.5 50.0 46.3 62.3

1-06 26.7 54.3 15.3 51.8

1-07 30.0 47.5 43.2 75.2

1-08 100 32.6 94.7 100

1-09 72.2 41.7 55.5 81.6

I -10 78.0 57.7 60.2 85.8

1-11 52.3 14.3 40.2 77.3

1-12 46.9 34.4 23.8 63.8

1-13 85.2 60.4 79.6 88.2

1-14 93.5 100 97.8 100

1-15 76.4 55.6 65.6 93.0

1-16 77.8 46.2 60.3 90.8

1-17 56.0 30.0 25.9 77.3

1-18 66.0 67.4 32.3 69.7

1-19 76.2 88.9 78.6 7.0

1-20 16.8 59.4 20.6 50.1

1-21 87.5 100 100 100

1-22 13.2 55.0 25.2 7.3

1-23 56.6 57.1 75.3 62.3

1-24 60.8 27.7 26.1 36.2

1-25 89.9 46.7 90.5 100

1-26 91.7 55.9 89.3 100

1-27 100 100 98.0 100

1-28 68.2 73.0 69.8 48.9

1-29 60.5 20.0 56.9 67.4

1-30 72.0 44.7 68.6 73.6

1-31 59.2 68.1 63.5 21.0

1-32 88.0 44.1 80.2 94.6

1-33 54.6 40.0 65.3 32.0

1-34 100 96.7 94.4 99.2

I 35 42.2 30.6 36.4 24.4

1-36 68.5 56.0 59.0 46.8

1-37 88.7 60.6 92.2 86.5

1-38 56.4 65.1 64.3 32.6

1-39 90.3 73.8 88.8 95.7

1-40 83.3 40.3 86.4 78.9

1-41 100 96.9 66.7 95.4

1-42 86.5 31.3 78.8 100

1-43 95.6 61.5 87.6 96.7

1-44 32.3 25.7 55.5 45.2

1-45 78.9 78.1 65.2 77.3

1-46 76.2 63.3 55.8 31.4

1-47 89.5 85.4 82.5 72.3

1-48 68.8 45.0 75.6 94.9

1-49 76.9 54.8 52.0 96.7

1-50 65.2 54.8 46.5 71.1

1-51 58.5 47.7 75.3 40.4

1-52 69.6 40.3 50.0 49.2

1-53 95.8 100 97.0 100 Imidacloprid 100 62.3 100 62.3 Table 4. Insecticidal activity of compound VI

Figure imgf000017_0001
Figure imgf000018_0001
Further screening results of some compounds are shown in Table 5.

Table 5. Insecticidal activity of some compounds I and VI against aphids Corrected mortality (%)

 Compound peach 蚜 melon! ;棉;!蚜菜缢管蚜

 lOppm 3ppm lOppm 3ppm lOppm 3ppm

< 1 -08 98.3 92.5 45.5 13.2 88.7 65.4

1 -14 Ο 99.4 94.6 99.4 95.6 100 98.8

1 -21 96.5 93.4 98.3 95.1 99.8 96.7

1 -25 88.6 80.7 75.2 60.3 95.7 88.3

1 -26 81.4 82.3 65.5 50.2 88.9 86.4

1 -27 100 98.6 98.7 96.3 100 99.4

1 -34 98.2 90.3 92.6 89.6 90.5 90.2

1 -37 78.6 65.8 69.7 63.5 88.2 79.1

1 -39 82.4 78.2 69.5 60.8 86.9 70.2

1 -41 98.4 90.4 88.3 89.0 90.5 86.4

1 -42 66.6 56.8 50.4 51.7 87.6 80.5

1 -43 79.4 60.3 69.8 42.0 88.4 80.2

1 -53 100 95.6 95.4 92.6 100 98.7

VI -07 75.5 60.6 45.3 26.8 65.2 50.2

 61.2 46.9 79.8 72.5 59.4 46.3

VI -26 52.4 50.5 23.7 22.0 53.5 21.4

VI -33 66.8 61.5 77.3 54.6 44.1 23.5

 59.8 47.6 42.5 15.9 66.4 36.8

VI -41 100 99.8 92.3 90.6 100 99.6

VI -46 45.2 30.0 65.4 48.3 23.2 4.0

 76.6 62.5 78.5 62.0 80.4 75.1

VI -53 100 94.3 90.2 91.0 100 99.8 Table 6. Compounds VI-41 and VI-53 for field control of aphids

Figure imgf000019_0001

 "WP" stands for wettable powder; "SC" stands for suspending agent.

 Table 7. Compound VI-41 and VI-53 for field control of rice planthopper

Figure imgf000019_0002

 In the table, "WP" stands for wettable powder; "SC" stands for suspending agent. Industrial application

The present invention provides a 2,5-disubstituted-3-niminoimido-1,2,4-triazoline compound of the formula I and a precursor compound thereof, and a nitro group of the formula VI. Preparation methods and applications of terpenoids. The above compounds are extensively investigated and rationally designed by the inventors of the present invention, and The screening of the quantitative compound has a high insecticidal activity, and the preparation method is simple, and provides a preferred process route, which has good safety and low cost, and the practical application value of the compound is greatly improved.

 Insecticidal activity experiments showed that the 2,5-disubstituted 3-nitroimido-1,2,4-triazoline compounds of formula (I) and the nitroaminosamines of formula (VI) The compound has high control effect against crop pests such as aphids, planthoppers, leafhoppers, cotton bollworms, and beet armyworm, and can be used as a plant insecticide. 2

Figure imgf000020_0001

 (Formula I) (Formula VI)

Claims

Rights request
 A compound of formula I or a pharmaceutically acceptable salt thereof:
N'N0 2
R 2
 (Formula I)
 Wherein: C1 to C10 saturated or unsaturated aliphatic hydrocarbon group, C1 to C10 saturated or unsaturated fluoroaliphatic hydrocarbon group, substituted or unsubstituted phenyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted thiazolyl group, substituted Or an unsubstituted pyrazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted isoxazolyl group, or a tetrahydrofuranyl group;
 It is hydrogen, a C1 to C10 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted naphthyl group.
 The compound according to claim 1 or a pharmaceutically acceptable salt thereof, wherein: the substituted phenyl group, the substituted pyridyl group, the substituted thiazolyl group, the substituted pyrazolyl group, The substituents in the substituted oxazolyl and substituted isoxazolyl are independently selected from any of the following groups: halogen, amino, hydroxy, C1 to C5 alkyl, C1 to C5 alkoxy And a fluoroalkyl group of C1 to C5 and a fluoroalkoxy group of C1 to C5.
 The compound according to claim 1 or 2, or a pharmaceutically acceptable salt thereof, wherein: (1: (1:10) unsaturated fatty hydrocarbon group, halopyridyl group, halothiazolyl group, Or tetrahydrofuranyl; preferably a vinyl group, an ethynyl group, a chloropyridyl group, a chlorothiazolyl group or a tetrahydrofuran-3-yl group.
 The compound according to claim 1, wherein the substituent in the substituted phenyl group is a halogen, a hydroxyl group, an amino group, or a C1 to C5 alkyl group, or a pharmaceutically acceptable salt thereof. a C1-C5 alkoxy group, a C1-C5 fluoroalkyl group, a C1-C5 fluoroalkoxy group, an aryl group or an aryloxy group; the substituent in the substituted pyridyl group is a halogen, C1 to C5 An alkyl group, a C1 to C5 alkoxy group, a C1 to C5 fluoroalkyl group, a C1 to C5 fluoroalkoxy group, or an aryloxy group; the substituent in the substituted furyl group is 3⁄4 or C1 a C5 alkyl group; the substituent in the substituted naphthyl group is a halogen, a hydroxyl group, an amino group, a nitro group, a carboxyl group or a cyano group.
The compound according to claim 1 or 4, or a pharmaceutically acceptable salt thereof, wherein: the hydrogen, the substituted phenyl group, or the C1 to C7 saturated or unsaturated aliphatic hydrocarbon group; preferably hydrogen or halogen A substituted phenyl group, or a C3~C7 saturated or unsaturated aliphatic hydrocarbon group.
6. A compound of formula VI or a pharmaceutically acceptable salt thereof:
NN0 2
 F?! H
 (formula VI)
 among them: ! ^ is a C1~C10 saturated or unsaturated aliphatic hydrocarbon group, a C1~C10 saturated or unsaturated fluoroaliphatic hydrocarbon group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted thiazolyl group, a substituted or Unsubstituted pyrazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted isoxazolyl, or tetrahydrofuranyl;
 It is hydrogen, a C1 to C10 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted naphthyl group.
 The compound according to claim 6 or a pharmaceutically acceptable salt thereof, wherein: the substituted phenyl group, the substituted pyridyl group, the substituted thiazolyl group, the substituted pyrazolyl group, The substituents in the substituted oxazolyl and substituted isoxazolyl are independently selected from any of the following groups: halogen, amino, hydroxy, C1 to C5 alkyl, C1 to C5 alkoxy And a fluoroalkyl group of C1 to C5 and a fluoroalkoxy group of C1 to C5.
 The compound according to claim 6 or 7, or a pharmaceutically acceptable salt thereof, wherein: (1: (1:10) unsaturated fatty hydrocarbon group, halopyridyl group, halothiazolyl group, Or tetrahydrofuranyl; preferably a vinyl group, an ethynyl group, a chloropyridyl group, a chlorothiazolyl group or a tetrahydrofuran-3-yl group.
The compound according to claim 6 or a pharmaceutically acceptable salt thereof, wherein: in the R 2 , the substituent in the substituted phenyl group is a halogen, a hydroxyl group, an amino group, or a C1 to C5 alkane. a C1 to C5 alkoxy group, a C1 to C5 fluoroalkyl group, a C1 to C5 fluoroalkoxy group, an aryl group or an aryloxy group; the substituent in the substituted pyridyl group is a halogen, C1 a C5 alkyl group, a C1 to C5 alkoxy group, a C1 to C5 fluoroalkyl group, a C1 to C5 fluoroalkoxy group, or an aryloxy group; the substituent in the substituted furyl group is 3⁄4 Or an alkyl group of C1 to C5; the substituent in the substituted naphthyl group is a halogen, a hydroxyl group, an amino group, a nitro group, a carboxyl group or a cyano group.
 The compound according to claim 6 or 9, or a pharmaceutically acceptable salt thereof, wherein: the hydrogen, the substituted phenyl group, or the C1 to C7 saturated or unsaturated aliphatic hydrocarbon group; preferably hydrogen or halogen A substituted phenyl group, or a C3~C7 saturated or unsaturated aliphatic hydrocarbon group.
11. A process for the preparation of a compound of formula VI according to any one of claims 6-10, comprising the steps of: 1) reacting nitroguanidine with hydrazine hydrate to form nitroaminoguanidine of formula II;
Figure imgf000023_0001
 (Formula II)
2) reacting a nitroamino hydrazine of the formula II with a carbonyl compound of the formula III under acid catalysis to form a nitroaminoguanidine of the formula IV;
Figure imgf000023_0002
 (Formula III) (Formula IV)
 3) reacting a compound of the formula IV with a compound of the formula V under a base catalysis to produce a compound of the formula VI;
NN0 2
R X Ri H
 (Formula V) (Formula VI)
Wherein R 2 in formula III and formula VI has the same definition as in formula VI;
 In the middle! The definition of ^ is the same as the formula VI.
X in the formula V is Cl, Br, ^"O or P 3 e S G 2 G-.
12. The method according to claim 11, wherein: the reaction in step 1) is carried out in a solvent, the solvent is water; the reaction temperature of the reaction is 45-70 ° C ; The molar ratio of nitroguanidine to hydrazine hydrate is 1: (1-1.5).
The method according to claim 11, wherein the reaction in the step 2) is carried out in a solvent, the solvent is anhydrous ethanol or methanol; and the reaction temperature of the reaction is 50-80 ° C ; The acid used in the reaction is acetic acid or p-toluenesulfonic acid; the molar ratio of the nitroaminoguanidine to the carbonyl compound of the formula III in the reaction is 1: (1-2).
 14. The method according to claim 11, wherein: the reaction in the step 3) is carried out in a solvent, the solvent is dimethylformamide or dimethylacetamide; and the reaction temperature of the reaction is 0-50 ° C; The base used in the reaction is sodium hydride, sodium ethoxide, sodium methoxide or sodium amide; the molar ratio of the compound of formula IV to the compound of formula V in the reaction can be 1: (- 2.5).
15. A process for the preparation of a compound of formula I according to any one of claims 1 to 5 comprising the step of: subjecting a compound of formula VI to a ring closure reaction to form a compound of formula I.
16. The method according to claim 15, wherein: the ring-closing reaction is carried out in the presence of a weakly acidic or weakly basic medium, which is dilute hydrochloric acid, dilute sulfuric acid, phosphoric acid or acetic acid; The weakly alkaline medium is an aqueous solution of sodium carbonate, an aqueous solution of sodium acetate, dilute sodium hydroxide, pyridine or triethylamine;
 The reaction solvent for the ring closure reaction is water, methanol or ethanol; the temperature of the reaction is 0-
100 ° C.
 Use of a compound according to any one of claims 1 to 10, or a pharmaceutically acceptable salt thereof, or a pharmaceutical composition containing any of them, for the preparation of a plant insecticide.
 18. Use according to claim 17, characterized in that the plant insecticide is used to kill at least one of the following pests: a homopteran pest, a lepidopteran pest and a true eucalyptus pest.
 The use according to claim 18, wherein the homopteran pest is at least one of the following six families: Aphididae, Aphididae, Aphisidae, Hibiscus, Acacia The Lepidoptera pest is a Noctuidae and/or a Hymenoptera family; the true Aphid pest is a leafhopper pest.
 A plant insecticidal drug or preparation, which comprises the compound according to any one of claims 1 to 10 or a pharmaceutically acceptable salt thereof.
 The plant insecticidal drug or preparation according to claim 20, characterized in that the mass percentage of the active ingredient in the plant insecticide or preparation is from 0.01% to 99.99%.
 The plant insecticide or preparation according to claim 20 or 21, characterized in that the plant insecticide or preparation is for killing homonymous pests and/or lepidopteran pests and/or sincere Target pests.
 The plant insecticidal drug or preparation according to claim 22, wherein the homopteran pest is at least one of the following six families: Aphididae, Aphididae, Aphididae, Wood The Lepidoptera, the genus Lepidoptera, and the genus Lepidoptera are the genus Noctuidae and/or the genus Hymenoptera;
 Use of the plant insecticidal medicament or preparation according to any one of claims 20 to 23 for controlling plant pests.
 A method for controlling plant pests, which comprises applying the plant insecticidal drug or preparation according to any one of claims 20 to 23 to plant leaves and/or fruits and/or seeds, and plant leaves and/or fruits. And/or the seed is growing or expected to grow in an environment; the active ingredient of the plant insecticide or formulation is applied at a concentration of from 1 to 600 mg/L, preferably at a concentration of from 3 to 50 mg/L.
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