WO2011085575A1 - Ortho-heterocyclyl formanilide compounds, their synthesis methods and use - Google Patents

Abstract

Ortho-heterocyclyl formanilide compounds represented by formula (I) or (II), their synthesis methods and use are disclosed. In the formulas, X₁, X₂, Z, R₁ or R₂ is defined as in description. The ortho-heterocyclyl formanilide compounds have good effect for the prevention and cure of harmful insects and can be used for preparing pesticides in the field of agriculture or gardening.

Description

 Description o-heterocyclic anilide compound and synthesis method and application thereof

 The invention belongs to the field of pesticides, and particularly relates to an o-heterocyclic anilide compound which can be used as an insecticide and a preparation method thereof. The prevention and control of pests has always been the core field of pesticide scientific research. The widespread use of pesticides has led to the effective management of most pests. With the increasing use of pesticides, the problem of drug resistance caused by the use of organic synthetic insecticides has become more prominent. Therefore, low toxicity compounds acting on new targets have become an inevitable trend in pesticide research.

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 The object of the present invention is to provide a class of o-heterocyclic anilide compounds which have excellent control effects against various pests and are characterized by high efficiency, safety and good environmental compatibility, so as to meet crop protection and high-efficiency and safe insecticides. Demand.

 Another object of the present invention is to provide a process for the preparation of the above compounds.

 Still another object of the invention is to provide the use of the above compounds in the preparation of insecticides.

 The object of the invention can be achieved by the following measures:

 ( I ) , (Π

In the formula, ₁ or ₂ are independently hydrogen, halogen or cyano; Z is oxygen or sulfur;

Ri or R ₂ are each independently a C1 to C5 fluorenyl group, a C1 to C5 halogenated fluorenyl group, a hydroxyl group, a C1 to C5 decyloxy group, a Cl~C5 halogenated fluorenyloxy group, a fluorenyl group, a C1 to C5 thiol group, an amino group. , C1~C5 垸amino group (including hydrazine, hydrazine-diamino group), C1~C5 halogenated hydrazine amino group, C1~C5 oxiranylamino group, C1~C5 decyl sulfonamide group, C1~C5 acyl group, C1~C5 Amido, halogen, cyano or thiocyano.

The X or X ₂ in the present invention are each independently preferably H, F, CI, Br or CN; X, or X ₂ are each independently further preferably H, F, CI or Br; wherein _{1 is} most preferably CI, Br or CN, X _{2 is} most preferably CI, Br or CN.

In the present invention, or R ₂ each independently preferably is C1 to C5 fluorenyl, hydroxy, C1 to C5 decyloxy, fluorenyl, C1 to C5 thiol, amino, C1 to C5 decylamino, C1 to C5 decyl sulfonate. An amide group, a C1 to C5 amide group, a halogen, a cyano group or a thiocyano group; and C1 to C5 in each of the above substituents may further preferably be C1 to C3. Specifically speaking! ^ or R ₂ may be independently selected from the group consisting of: -CH ₃ , -C ₂ H ₅ , -CH(CH ₃ ) ₂ , -OH, -OCH ₃ , -OC ₂ H ₅ , -OCH (CH _{3 2} , -SH, -SCH ₃ , -SC ₂ H ₅ , -SCH(CH ₃ ) ₂ , -NH ₂ , -NHCH ₃ , -NHC ₂ H ₅ , -N(CH ₃ ) ₂ , -NHCH(CH ₃ ) ₂ , -NHOCH ₃ -NHOC ₂ H ₅ , -NHOCH(CH ₃ ) ₂ , -N(CH ₃ ) ₂ -NHCF ₃ -NHCHF ₂ -NHCH ₂ F, -NHCOCH ₃ , -NHCOC ₂ H ₅ , - NHS0 ₂ CH ₃ , -NHS0 ₂ C ₂ H ₅ , halogen, cyano or thiocyano group.

 Further preferably, Ri is a C1 to C5 fluorenyl group, a hydroxy group, a decyl group, a C1 to C5 thiol group, an amino group, a C1 to C5 fluorenylamino group, a C1 to C5 decyl sulfonylamino group, a C1 to C5 amide group, a halogen, a cyano group or a sulfur. The cyano group is most preferably a C1 to C3 fluorenyl group, a hydroxy group, a decyl group, a C1 to C3 thiol group, an amino group, a C1 to C3 fluorenylamino group, a C1 to C3 fluorenyl sulfonamide group, a Cl~C3 amide group, a halogen (preferably C1). Or Br), cyano or thiocyano.

R _{2 is} further preferably a C1 to C5 mercapto group, an amino group, a C1 to C5 mercaptoamino group, a C1 to C5 mercaptosulfonylamino group, a Cl~C5 amido group, a halogen, a cyano group or a thiocyano group, and most preferably a C1 to C3 group. Base, amino group, C1~C3 oxime amino group, Cl~C3 decyl sulfonamide group, C1~C3 amide group, halogen (preferably C1 or Br), cyano group or thiocyano group.

 The preparation methods of the o-heterocyclic anilide compounds represented by the general formulae (I) and (Π) are as follows:

 Z is oxygen, 1^ is. 1~. 5 thiol, amino, halogen, cyano or thiocyano group, when X is under neutral conditions, in a polar aprotic solvent, the intermediate M1 is reacted with the corresponding hydrazide reagent R ONHN ^ at room temperature Ring opening gives a compound of the formula (I 1 ), the reaction route of which is:

Ri为 C1〜C5卤代垸基或 C1〜C5酰基时， 也可按上式进行制备。 为 C1〜C5垸氨基、 C1〜C5卤代垸氨基、 C1〜C5垸氧氨基、 C1〜C5垸基磺酰胺基或 C1〜C5酰基时， 将 为氨基的化合物 II与垸基化试剂、 垸氧化试剂、 垸基磺酰化试剂或酰基化试剂进行反应 即可制备。 为硫氰基时， 将 为卤素的化合物与硫氰化钠进行反应即可制备。

When Ri is a C1 to C5 halogenated fluorenyl group or a C1 to C5 acyl group, it can also be produced according to the above formula. When it is a C1~C5 oxime amino group, a C1~C5 halogenated oxime amino group, a C1~C5 oxime oxyamino group, a C1~C5 decyl sulfonamide group or a C1 ～C5 acyl group, the compound II which is an amino group and a thiolation reagent, hydrazine It can be prepared by reacting an oxidizing reagent, a mercaptosulfonylating reagent or an acylating reagent. When it is a thiocyano group, a compound which is a halogen can be prepared by reacting with sodium thiocyanate.

 Z is oxygen, ! ^ is hydroxyl, when X is, firstly intermediate M1 is reacted with hydrazine hydrate to prepare intermediate M2. Under neutral conditions, polar protic solvent, intermediate M2 reacts with triphosgene or phosgene at reflux temperature. Get the formula

 When Ri is a C1~C5 decyloxy group or a C1~C5 halogenated decyloxy group, the compound of the formula 12 can be reacted with a thiolation reagent.

Z is oxygen, ! ^ is sulfhydryl, when X is, under basic conditions, polar protic solvent, at reflux temperature, intermediate M2 and disulfide should be routed as follows:

 When Ri is a C1 to C5 thiol group, a compound of the formula 13 can be reacted with a thiolation reagent to prepare.

When Z and X are used, intermediate M2 is reacted with carbon disulfide or halogenated hydrocarbon under basic conditions in a polar protic solvent at reflux temperature to obtain intermediate M3, and organic weak acid is used as a catalyst in the solvent. The M3 reaction is dehydrated and condensed to obtain a compound represented by the formula (I4); or the intermediate M1 is reacted with the corresponding reagent NH2NHCS to obtain M3, and then the organic weak acid is used as a catalyst in the solvent, and the M3 reaction is dehydrated and condensed to obtain a ring. A compound of the formula (I 4), the reaction route is:

The preparation of the compound of formula I when Z is S can be prepared according to the above formula, and can be directly used when it is an anthracenyl group or a halogenated fluorenyl group.

The route of M2-M3-I4, when R is an amino group or other group (such as hydroxy, thiol, cyano), the M1-M3-I4 pathway can also be used. When. 1~. 5 methoxy, C1~C5 halogenated methoxy, C1~C5 垸amino, C1~C5 halogenated guanidine amino group, C1~C5 oxiranylamino group, C1~C5 decyl sulfonamide group or C1~C5 acyl group It can be prepared by further reaction with 14 using the corresponding guanidylation, sulfonamidation or acylation reagent. When it is a thiocyano group, a compound which is a halogen is reacted with sodium thiocyanate to prepare.

The intermediate M4 is condensed with the corresponding reagent HON=CNH ₂ R ₂ under basic conditions in a polar protic solvent at 70-80 ° C or reflux temperature to obtain a compound of the formula (Π). , the reaction route is:

R _{2 is} as defined above, and is preferably a C1 to C5 fluorenyl group, a C1 to C5 halogenated fluorenyl group, a hydroxyl group, a decyl group, an amino group, a Cl~C5 fluorenylamino group, a C1 to C5 decyl sulfonylamino group or a C1 to C5 acyl group. Halogen, cyano or thiocyano. When R ₂ is a Cl~C5 oxime amino group, a C1~C5 decyl sulfonamide group or a C1 ～C5 acyl group, the compound prepared by the above formula may be further used with the corresponding thiolation, sulfonamide or acylation reagent. Reaction preparation. When R ₂ is a thiocyano group, a compound in which R ₂ is a halogen is reacted with sodium thiocyanate to prepare.

The acidic condition or the weak acid described in the present invention is an organic acid such as methanesulfonic acid or p-toluenesulfonic acid; the basic condition is a strong base or a weak base, and the strong base is sodium hydroxide, potassium hydroxide, sodium alkoxide or the like; The weak base is pyridine, triethylamine, etc.; The polar protic solvent is a solvent such as an alcohol, toluene or benzene; and the polar aprotic solvent is a solvent such as DMF. The solvent mentioned separately in the present invention may generally be a polar protic solvent or a polar aprotic solvent.

 Intermediate M2 is prepared by reacting raw material (Ml) with hydrazine hydrate at a temperature of -10~30 °C (refer to patent CN 200910033297),

 M M 2

 The compounds of the formula (I) and (Π) have excellent control activity against insects, and thus the compounds of the present invention can be used as an insecticide to protect plants such as agriculture and horticulture. The insects are lepidopteran pests such as cotton bollworm, beet armyworm, diamondback moth, cabbage caterpillar, rice leaf roller and rice stem borer, and homopteran pests such as spider mites, planthoppers, locusts, whiteflies, etc. , Diptera pests such as housefly, leaf miner, mosquito, etc., Orthoptera and coleoptera and other pests. Of course, the pests to which the compounds of the present invention are controll are not limited to the scope of the above examples.

 When the compound of the present invention represented by the general formulae (I) and (?) is used as an insecticide in the fields of agriculture, horticulture, etc., it may be used alone or in the form of a pesticidal composition, such as by formula (I) Or the formula (Π) is an active ingredient, and a pesticide adjuvant commonly used in the art is processed into an aqueous emulsion, a suspension, a water-dispersible granule, an emulsifiable concentrate, and the like.

 Commonly used pesticide additives include: liquid carriers such as water; organic solvents such as toluene, xylene, cyclohexane, methanol, butanol, ethylene glycol, acetone, dimethylformamide, diethyl ether, dimethyl sulfoxide, animals and Vegetable oils and fatty acids; commonly used surfactants such as emulsifiers and dispersants, including anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants; other additives such as wetting agents, thickeners, etc. .

 When the compound of the present invention represented by the general formulae (I) and (?) is used as an active ingredient in the insecticide, the content in the insecticide may be selected from the range of 0.1% to 99.5%. The appropriate active ingredient content can be determined according to the form of the preparation and the method of administration. Usually, the aqueous emulsion contains from 5% to 50% by weight of the active ingredient, preferably in an amount of from 10% to 40%; in the suspension, from 5% to 50% of the active ingredient, preferably Its content is 5% to 40%.

For example, for the aqueous emulsion or suspending agent, the compound of the present invention as an active ingredient can be uniformly mixed with an auxiliary agent such as a solvent and a surfactant, and can be diluted with water to a specified concentration during use. The water-dispersible granules can be prepared by mixing and pulverizing the compound of the present invention, a solid carrier, a surfactant, and the like as an active ingredient. Dilute with water when using. Of course, the processing method of the preparation is by no means limited to the above. A person skilled in the art can select an appropriate method depending on the active ingredient, the purpose of use, and the like.

 The insecticide of the present invention may contain other insecticides, acaricides, fungicides, insect growth regulators, plant growth, in addition to the compounds represented by the general formulae (I) and (Π) as active ingredients. Any suitable active ingredient such as a regulator and a soil amendment.

 For the use of the insecticide of the present invention, conventional application methods such as stem and leaf spray, surface application, soil treatment, and seed treatment can be selected. For example, when a stem and leaf spray is used, the compound represented by the general formulae (I) and (Π) as an active ingredient can be used in an aqueous emulsion, a suspension, a water-dispersible granule, and a concentration range of 1 to 1000 mg/L. The emulsifiable concentrate preferably has a concentration of from 1 to 500 mg/L.

 The novel o-heterocyclic anilide compound disclosed by the invention has excellent control effects on harmful insects, and therefore the compound can be used for preparing insecticides in the fields of agriculture, horticulture and the like, and has the advantages of high efficiency, low toxicity and environmental friendliness.

In order to facilitate a further understanding of the present invention, the embodiments provided below are described in more detail. These examples are for illustrative purposes only and are not intended to limit the scope or implementation of the invention.

Example 1

 Reaction

Compound NO.l (X=H, R=CH ₃ ): 3-bromo-N-{2-[2-(5-methyl-1,3,4-oxadiazole)]-6-methylbenzene Synthesis of -1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide)

Take 2.0 g (4.4 mmol) of 2-(3-bromo-1-(3-chloro-2-pyridyl)-1 H-pyrazole)-5-methyl-4 H-3,1-benzoxazine -4- Ketone (Ml) was suspended in 40 mL of DMF, added with 0.4 g of acetohydrazide, and reacted at room temperature overnight. The solution was clarified the next day. The reaction solution was slowly added to 100 mL of water with stirring. The solid was slowly precipitated and stirring was continued for 2 h. Filtered and dried to obtain 1.45 g of finished product. Compound NO. 2 (X=CL, R=CH ₃ ): 3-bromo-N-{4-chloro-2-[2-(5-methyl-1,3,4-oxadiazole)]-6 Synthesis of -methylphenyl}-1-(3-chloro-2-pyridyl)-1Η-pyrazole-5-carboxamide

Synthesis of Compound N0.1 as in Example 1, 2-(3-bromo-1-(3-chloro-2-pyridyl)-1 H-pyrazole)-7-chloro-5-methyl-4H Reaction of -3,1-benzoxazin-4-one (M1C1) with acetohydrazide gave the title compound (N0.2) 1.51 g. Compound N0.23 (X=CN, R=CH ₃ ): 3-bromo-N-{4-cyano 2-[2-(5-amino-1,3,4-oxadiazole)]-6- Synthesis of methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

 The title compound was obtained according to the procedure of the compound 10.1. Example 2:

 Reaction formula:

化合物 N0.3 (X=CL， R=OH) _: 3-溴 -N-{4-氯 -2-[2-(5-羟基 -1,3,4-噁二唑 )]-6-甲基苯 基 }-1-(3-氯 -2-吡啶基 HH-吡唑 -5-甲酰胺的合成

Compound N0.3 (X=CL, R=OH) _: 3-bromo-N-{4-chloro-2-[2-(5-hydroxy-1,3,4-oxadiazole)]-6- Synthesis of phenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

 Add 10 g (2.07 mmol) of M2 and 0.8 g (2.68 mol) of triphosgene to 20 mL of toluene and reflux for 4 h. After concentration, the filtrate was slowly poured into water, stirred for more than 2 h, allowed to stand, filtered, washed with water until The filtrate pH = 7, filtered, and recrystallized from diethyl ether to give 10 g of solid product. Example 3:

Reaction formula

Compound NO.4 (X=CL, R=SH) _: 3-bromo-N-{4-chloro-2-[2-(5-fluorenyl-1,3,4-oxadiazole)]-6- Synthesis of phenyl}-l-(3-chloro-2-pyridyl)-1Η-pyrazole-5-carboxamide

Add 0.97g (2.0 mmol) of intermediate M2 and 5 mL of carbon disulfide to 20 mL of pyridine, heat to 50 V for 3 days, and then pour the reaction into ice water and stir for 2 h, then let stand, wait for solid. After the analysis, the mixture was filtered, washed with alcohol, washed with water, and dried to obtain 0.85 g of product. Compound N0.7 (X=Br, R=SH) _: 3-bromo-N-{4-bromo-2-[2-(5-fluorenyl-1,3,4-oxadiazole)]-6- Synthesis of phenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

The title compound was obtained by the synthesis of the compound of Example N. Compound N0.24 (X=CN, R=SH) _: 3-bromo-N-{4-cyano-2-[2-(5-fluorenyl-1,3,4-oxadiazole)]-6- Synthesis of methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

 Synthesis according to the synthesis of the compound of Example N0.4 gave the corresponding title compound. Example 4:

 Reaction formula

1 ₃

 Compound N0.5 (X=CL, R^CHs): 3-bromo-N-{4-chloro-2-[2-(5-fluorenyl-1,3,4-oxadiazole)]-6 Synthesis of -methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

Dissolve 1.3 g (2.4 mmol) of 1 ₃ in 5 mL of 10% sodium hydroxide solution, then add 0.2 mL of methyl iodide (3.0 Methyl) 20 mL of ethanol solution. After reacting for 10 h at room temperature, it was poured into 50 mL of water, stirred for 2 h, then allowed to stand, filtered, washed with water, and recrystallized from ethanol to give the corresponding title compound 0.88 ° Compound No. 6 (X=CL, R = S CH (CH _{3 2} ): 3-bromo-N-{4-chloro-2-[2-(5-indoleisopropyl-1,3,4-oxadiazole)]-6-methylphenyl}-l- Synthesis of (3-Chloro-2-pyridyl)-1Η-pyrazole-5-carboxamide

 The title compound 1.20 g was obtained by the title compound. Compound No. 8 (X=Br, R^CHs): 3-bromo-N-{4-bromo-2-[2-(5-fluorenyl-1,3,4-oxadiazole)]-6 Synthesis of -methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

: 3-溴 -N-{4-氰基 -2-[2-(5-巯甲基 -1,3,4-噁二唑 )]-6- 甲基苯基 }-1-(3-氯 -2-吡啶基 HH-吡唑 -5-甲酰胺的合成 The title compound was obtained by the synthesis of the compound of Example N. Compound N0.25 (X=CN,

: 3-bromo-N-{4-cyano-2-[2-(5-fluorenyl-1,3,4-oxadiazole)]-6-methylphenyl}-1-(3- Synthesis of Chloro-2-pyridylHH-pyrazole-5-carboxamide

 The title compound was obtained by the synthesis of the compound of compound N0.5. Example 5:

 Reaction formula

 M 3 1 4

Compound NO.9 (X=CL, R=SCH ₃ ): 3-bromo-N-{4-chloro-2-[2-(5-fluorenyl-1,3,4-thiadiazole)]- Synthesis of 6-Methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

Add 0.97 g ( 1.70 mmol) M3 (R is SCH ₃ ) and 0.38 g ( 1.97 mmol) of p-toluenesulfonic acid to 20 mL of toluene, heat to reflux for 2 h, desolvate and recrystallize with cyclohexane, dry. The corresponding title compound was obtained in 0.82 g. Compound N0.26 (X=CN, R=SCH ₃ ): 3-bromo-N-{4-chloro-2-[2-(5-fluorenyl-1,3,4-thiadiazole)]- 6-A Synthesis of phenyl}-l-(3-chloro-2-pyridyl)-m-pyrazole-5-carboxamide

The title compound was obtained by the synthesis of the compound of Example N. Compound NO. 10 (X=CL, R=NH ₂ ) _: 3-bromo-N-{4-chloro-2-[2-(5-amino-1,3,4-thiadiazole)]-6- Synthesis of methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

0.2 mL of methyl sulfonic acid was added dropwise to 20 mL of a toluene solution containing 1.0 g (2.73 mmol) of M3 (R is NH ₂ ), heated to reflux for 3 h, cooled to room temperature, and the reaction was continued overnight. The reaction mixture was suspended in ethyl acetate (35 mL). Compound N0.27 (X=Br, R=NH ₂ ): 3-bromo-N-{4-bromo-2-[2-(5-amino-1,3,4-thiadiazole)]-6- Synthesis of methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

The title compound was obtained by the synthesis of the compound of Example No.10. Compound N0.28 (X=CN, R=NH ₂ ) _: 3-bromo-N-{4-cyano-2-[2-(5-amino-1,3,4-thiadiazole)]-6 Synthesis of -methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

The title compound was obtained by the synthesis of the compound of Example No.10. Compound N0.39 (X=CN, R=CH ₃ ): 3-bromo-N-{4-cyano-2-[2-(5-methyl-1,3,4-thiadiazole)]- Synthesis of 6-Methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

 The title compound was obtained by the synthesis of the compound of Example N. Compound NO. 40 (X = Br, R = OH): 3-bromo-N-{4-cyano-2-[2-(5-methyl-1,3,4-thiadiazole)]-6 Synthesis of -methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

The title compound was obtained by the synthesis of the compound of Example N. Compound N0.41 (X=CI, R=SH) _: 3-bromo-N-{4-cyano-2-[2-(5-methyl-1,3,4-thiadiazole)]-6 Synthesis of -methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

The title compound was obtained by the synthesis of the compound of Example N. Example 6

Compound NO.ll (X=CL, R=CH ₃ ) : 3-bromo-N-{4-chloro-2-[2-(5-methyl-1,2,4-oxadiazole)]-6 Synthesis of -methylphenyl}-l-(3-chloro-2-pyridyl)-1Η-pyrazole-5-carboxamide

Add 1.0 g (2.07 mmol) of M4 and 0.33 g (4.46 mol) of Ν'-hydroxyethyl hydrazine to 15 mL of ethanol, cool to 0 °C in an ice bath, and slowly add ethanol solution of sodium ethoxide (from 0.1 g). The sodium metal was added to 10 mL of ethanol and stirred for 30 min to obtain), and after cooling to room temperature, the reaction was kept for 2 h, and the reaction was heated under reflux overnight. After cooling to room temperature on the next day, it was filtered, and the filtrate was slowly poured into water, stirred for 2 h or more, allowed to stand, filtered, washed with water, and dried to give a white solid product (0.6 g). Compound N0.12 (X=Br, R=CH ₃ ) : 3-bromo-N-{4-bromo-2-[2-(5-methyl-1,2,4-oxadiazole)]-6 Synthesis of -methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

 The title compound was obtained by the synthesis of the compound of the compound of Example No. 11. Compound N0.29 (X=CL, R=CN): 3-bromo-N-{4-chloro-2-[2-(5-cyano-1,2,4-oxadiazole)]-6- Synthesis of methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

M4 was synthesized with HON=CNH ₂ CN according to the method of the synthesis of the compound of the present invention. Compound NO. 30 (X=CL, R=NH ₂ ) _: 3-bromo-N-{4-chloro-2-[2-(5-amino-1,2,4-oxadiazole)]-6- Synthesis of methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

M4 was synthesized with HON = CNH ₂ NH ₂ to give the corresponding title compound.

Compound N0.45 (X=CN, R=Br) _: 3-bromo-N-{4-cyano-2-[2-(5-bromo-1,2,4-oxadiazole)]-6- Methylbenzene Synthesis of }}-l-(3-chloro-2-pyridyl)-1Η-pyrazole-5-carboxamide

M4 was synthesized with HON=CNH ₂ Br according to the method of the compound of Example N0.29 to give the corresponding title compound. Compound N0.46 (X=Br, R=SCN): 3-bromo-N-{4-bromo-2-[2-(5-thiocyano-1,2,4-oxadiazole)]-6 Synthesis of -methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

 Take 2.0 g (3.6 mmol) of 3-bromo-N-{4-bromo-2-[2-(5-chloro-1,2,4-oxadiazole)]-6-methylphenyl}-1- (3-Chloro-2-pyridyl)-1H-pyrazole-5-carboxamide was suspended in 20 mL of DMF, added with 0.5 g of sodium thiocyanate, reacted at room temperature overnight, desolvated under reduced pressure, washed with water, filtered. The Cyclohexanide was recrystallized and dried to give the corresponding title compound 1.0 g.

化合物 N0.13 (X=CL， R=NH₂)_: 3-溴 -N-{4-氯 -2-[2-(5-氨基 -1,3,4-噁二唑 )]-6-甲基苯 基 }-1-(3-氯 -2-吡啶基 HH-吡唑 -5-甲酰胺的合成

Compound N0.13 (X=CL, R=NH ₂ ) _: 3-bromo-N-{4-chloro-2-[2-(5-amino-1,3,4-oxadiazole)]-6- Synthesis of methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

Take 2.0 g (4.2 mmol) of 2-(3-bromo-1-(3-chloro-2-pyridyl)-1 H-pyrazole)-5-methyl-4 H-3,1-benzoxazine -4-ketone (Ml) was suspended in 40 mL of DMF, added with 0.8 g of semicarbazide, reacted at room temperature overnight, added with 1.0 g of p-toluenesulfonic acid and 20 mL of toluene, heated to reflux for 4 h, desolvated with cyclohexane. It was recrystallized and dried to give the title compound (NO. 13). Compound N0.14 (X=Br, R=NH ₂ ): 3-bromo-N-{4-bromo-2-[2-(5-amino-1,3,4-oxadiazole)]-6- Synthesis of methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide The title compound was obtained by the synthesis of the compound of Example No.13. Compound N0.31 (X=CL, R=CN): 3-bromo-N-{4-chloro-2-[2-(5-cyano-1,3,4-oxadiazole)]-6- Synthesis of methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

Take 2.0 g (4.2 mmol) of 2-(3-bromo small (3-chloro-2-pyridyl)-1 H-pyrazole)-5-methyl-4 H-3,1-benzoxazine-4 - Ketone (Ml) was suspended in 40 mL of DMF, added with 0.8 g of CNCONHNH ₂ , reacted at room temperature overnight, added with 1.0 g of p-toluenesulfonic acid and 20 mL of toluene, heated to reflux for 4 h, desolvated and recrystallized from cyclohexane. The title compound (N0.31) 1.2 g was obtained. Compound N0.32 (X=CL, R=CL): 3-bromo-N-{4-chloro-2-[2-(5-chloro-1,3,4-oxadiazole)]-6- Synthesis of phenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

M1 was synthesized with CLCONHNH ₂ according to the procedure of the compound of Example N0.31 to give the corresponding title compound. Compound N0.33 (X=CL, R=SCN): 3-bromo-N-{4-chloro-2-[2-(5-thiocyano-1,3,4-oxadiazole)]-6 Synthesis of -methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

 Take 2.0 g (3.8 mmol) of 3-bromo-N-{4-chloro-2-[2-(5-chloro-1,3,4-oxadiazole)]-6-methylphenyl}-1- (3-Chloro-2-pyridyl)-1H-pyrazole-5-carboxamide was suspended in 20 mL of DMF, added with 0.5 g of sodium thiocyanate, reacted at room temperature overnight, desolvated under reduced pressure, washed with water, filtered. The Cyclohexanide was recrystallized and dried to give the corresponding title compound (1.3 g). Compound N0.47 (X=Br, R=CN): 3-bromo-N-{4-bromo-2-[2-(5-cyano-1,3,4-oxadiazole)]-6- Synthesis of methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

M1 was synthesized with CNCONHNH ₂ according to the procedure of the compound of Example N0.31 to give the corresponding title compound. Compound N0.48 (X=CN, R=SCN): 3-bromo-N-{4-cyano-2-[2-(5-thiocyano-1,3,4-oxadiazole)]- Synthesis of 6-methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

Take 2.0 g (3.7 mmol) of 3-bromo-N-{4-cyano-2-[2-(5-chloro-1,3,4-oxadiazole)]-6-methylphenyl}-1 -(3-Chloro-2-pyridyl)-1H-pyrazole-5-carboxamide was suspended in 20 mL of DMF, added with 0.5 g of sodium thiocyanate, allowed to react at room temperature overnight, desolvated under reduced pressure, washed with water, filtered The Cyclohexanide was recrystallized and dried to give the corresponding title compound. Example 8

 Reaction

1 5 1 6 Compound N0.15 (X=CL, Z=0, R ² =CH ₃ ): 3-bromo-N-{4-chloro-2-[2-(5-methylamino-1,3, Synthesis of 4-oxadiazole)]-6-methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

Dissolve 2.0 _§ ( 411111101) 1 5 in 5 mL of 10% sodium hydroxide solution, then add 20 mL of 0.4 mL (6.0 mmol) ethanol solution containing methyl iodide. After reacting at room temperature for 10 h, pour into 50 mL of water, stir for 2 h, then let stand, filter, wash with water, recrystallize from ethanol and dry to give the corresponding title compound 1.4 Compound N0.16 (X=CL, Z=S, R ² =CH ₃ ): 3-bromo-N-{4-chloro-2-[2-(5-methylamino-1,3,4-thiadiazole)]-6-methylphenyl}-1-(3- Synthesis of Chloro-2-pyridylHH-pyrazole-5-carboxamide

The title compound was obtained by the synthesis of the compound of Example N0.15. Compound N0.17 ((X=CL, Z=0, R ² =S0 ₂ CH ₃ ): 3-bromo-N-{4-chloro-2-[2-(5-methanesulfonylamino-1,3) ,4-oxadiazole)]-6-methylphenyl}-1-(3-chloro-2-pyridyl)-1Η-pyrazole-5-carboxamide

Dissolve 2.0 g (4 mmol) of I 5 in 20 mL of toluene and 1 mL of triethylamine solution, then add 0.7 g (6 mmol) of methylsulfonyl chloride, react at room temperature for 2 h, pour into 50 mL of water, stir, and let stand. the aqueous layer, after the solvent was distilled off under reduced pressure, dried and recrystallized from ethanol to give the corresponding title compound (N0.17) 1.8 compound N0.18 ((X = CL, Z = S, R 2 = S0 2 CH 3): 3 -Bromo-N-{4-chloro-2-[2-(5-methanesulfonylamino-1,3,4-thiadiazole)]-6-methylphenyl}-1-(3-chloro- Synthesis of 2-pyridyl)-1Η-pyrazole-5-carboxamide

The title compound was obtained by the synthesis of the compound of Example N0.17. Compound NO.21 ((X=CL, Z=0, R ² =COCH ₃ ): 3-bromo-N-{4-chloro-2-[2-(5acetamido-1,3,4-oxine) Synthesis of oxazolidine]--6-methylphenyl}-l-(3-chloro-2-pyridyl)-1Η-pyrazole-5-carboxamide

Dissolve 2.0 g (4 mmol) of 1 5 in 20 mL of toluene mL triethylamine solution, then add 0.47 g (6 mmol) of acetyl chloride, react at room temperature for 2 h, pour into 50 mL of water, stir, and let stand, remove the water layer. , evaporated and dried under reduced pressure to give the corresponding the solvent, the title compound was recrystallized from ethanol (N0.21) 1.8 go compound N0.22 ((X = CL, Z = S, R 2 = COCH 3): 3- bromo -N -{4-Chloro-2-[2-(5-acetylamido-1,3,4-thiadiazole)]-6-methylphenyl}-1-(3-chloro-2-pyridyl) Synthesis of -1Η-pyrazole-5-carboxamide

 The title compound is obtained by the synthesis of the above compound N0.21. Example 9

 Reaction formula:

Compound N0.19 ((X=CL, Z=0, R ² = R ³ =CH ₃ ): 3-bromo-N-{4-chloro-2-[2-(5-dimethylamino-1,3) ,4-oxadiazole)]-6-methylphenyl}-1-(3-chloro-2-pyridyl)-1Η-pyrazole-5-carboxamide

 2.0 g (4 mmol) 1 5 was added to 10 mL of 30% formaldehyde and 10 mL of formic acid solution, and the reaction was refluxed for 5 h. After cooling, 10% aqueous sodium hydroxide solution was added to pH=10, filtered, washed with water and dried to give the title compound ( N0.19) 1.6 g. Compound NO.20 ((X=CL, Z=S, R^ R^CHs): 3-bromo-N-{4-chloro-2-[2-(5-dimethylamino-1,3,4- Synthesis of thiadiazole]]-6-methylphenyl}-1-(3-chloro-2-pyridyl)-1Η-pyrazole-5-carboxamide

The title compound was obtained by the synthesis of the compound of Example N0.19.

化合物 N0.34 (X=CL， R=CN): 3-溴 -N-{4-氯 -2-[2-(5-氰基 -1,3,4-噻二唑 )]-6-甲基苯 基 }-1-(3-氯 -2-吡啶基 )-1Η-吡唑 -5-甲酰胺的合成

Compound N0.34 (X=CL, R=CN): 3-bromo-N-{4-chloro-2-[2-(5-cyano-1,3,4-thiadiazole)]-6- Synthesis of methylphenyl}-1-(3-chloro-2-pyridyl)-1Η-pyrazole-5-carboxamide

Take 2.0 g (4.2 mmol) of 2-(3-bromo-1-(3-chloro-2-pyridyl)-1 H-pyrazole)-5-methyl-4 H-3,1-benzoxazine -4-ketone (Ml) was suspended in 40 mL of DMF, and 0.5 g of CNC=SNHNH _{2 was} added to the solution. The reaction was carried out at room temperature overnight, and 1.0 g of p-toluenesulfonic acid and 20 mL of toluene were added, and heated to reflux for 4 h. After desolvation, It was washed with water, filtered, and then crystallised from hexanes, Compound N0.35 (X=Br, R=CN): 3-bromo-N-{4-bromo-2-[2-(5-cyano-1,3,4-thiadiazole)]-6- Synthesis of methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

 The title compound was obtained by the synthesis of the compound of the compound N0.34.

Compound N0.36 (X=CN, R=CL): 3-bromo-N-{4-cyano-2-[2-(5-chloro-1,3,4-thiadiazole)]-6- Synthesis of methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

Synthesis of M1 and CLC=SNHNH ₂ gave the corresponding title compound. Compound N0.37 (X=CL, R=CL): 3-bromo-N-{4-chloro-2-[2-(5-chloro-1,3,4-thiadiazole)]-6- Synthesis of phenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

M1 was synthesized with CLCONHNH ₂ to give the corresponding title compound. Compound N0.38 (X=CL, R=SCN): 3-bromo-N-{4-bromo-2-[2-(5-thiocyano-1,3,4-thiadiazole)]-6 Synthesis of -methylphenyl}-1-(3-chloro-2-pyridyl)-1Η-pyrazole-5-carboxamide

 Take 2.0 g (3.8 mmol) of 3-bromo-N-{4-chloro-2-[2-(5-chloro-1,3,4-thiadiazole)]-6-methylphenyl}-1- (3-Chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide was suspended in 20 mL of DMF, added with 0.5 g of sodium thiocyanate, allowed to react at room temperature overnight, desolvated under reduced pressure, washed with water, filtered, and evaporated. The crystals were recrystallized and dried to give the corresponding title compound 1.0 g. Example 11

Reaction formula:

Compound N0.42 ((X=Br , R =COCH3 ): 3-bromo-N-{4-bromo-2-[2-(5-acetylamido-1,2,4-carbazone)]-6 Synthesis of -methylphenyl}-1-(3-chloro-2-pyridylHH-pyrazole-5-carboxamide

 2.2 g (4 mmol) 18 was dissolved in 20 mL of toluene and 1 mL of triethylamine solution, then 0.47 g (6 mmol) of acetyl chloride was added, reacted at room temperature for 2 h, poured into 50 mL of water, stirred, and allowed to stand, and the aqueous layer was separated. The solvent was evaporated under reduced pressure, and the residue was evaporated to crystalljjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj (5-Methanesulfonylamino-1,2,4-oxadiazole)]-6-methylphenyl}-1-(3-chloro-2-pyridyl)-1Η-pyrazole-5-carboxamide Synthesis

Dissolve 2.0 g (4 mmol) of 18 in 20 mL of toluene and 1 mL of triethylamine solution, then add 0.7 g (6 mmol) of methylsulfonyl chloride, react at room temperature for 2 h, pour into 50 mL of water, stir, stand, and remove water. The solvent was evaporated under reduced pressure. Compound N0.44 (X=CN, R=NHCH ₃ ): 3-bromo-N-{4-cyano-2-[2-(5-methylamino-1,2,4-oxadiazole)]- Synthesis of 6-Methylphenyl}-1-(3-chloro-2-pyridyl)-1Η-pyrazole-5-carboxamide

 Dissolve 2.0 g (4 mmol) of I8 in 5 mL of 10% sodium hydroxide solution, then add 20 mL of 0.4 mL (6.0 mmol) ethanol solution containing methyl iodide. After reacting for 10 h at room temperature, it was poured into 50 mL of water, stirred for 2 h, then allowed to stand, filtered, washed with water, and recrystallized from ethanol to give the title compound 1.4 g. The compounds prepared in the examples are shown in Tables 1 and 2:

 Table 1

 General formula X z R

 NO. Morphology Melting point / V

1 IH 0 CH ₃ white powder 258. 2-260. 1

2 I C1 0 CH ₃ white powder 202. 1-204. 2

3 I C1 0 OH light yellow powder 221. 9-224. 1

4 I C1 0 SH Brown powder 169. 8-171. 6

5 I C1 0 SCH ₃ white powder 165. 2-167. 5

6 I C1 0 SCH (CH ₃ ) ₂ white powder 230. 0-232. 5

7 I Br 0 SH white powder 245. 5-248. 1

8 I Br 0 SCH ₃ white powder 192. 5-195. 3

9 I CI s SCH ₃ brownish yellow powder 119. 7-121. 1

10 I CI s NH ₂ light brown powder 317. 2-320. 9

11 II CI CH ₃ white powder 172. 9-175. 5

12 II Br CH ₃ white powder 193. 5-196. 5

13 I CI 0 NH ₂ light brown powder 255. 2-258. 0

14 I Br 0 NH ₂ light brown powder 278. 3-280. 1

15 I CI 0 NHCH3 white powder 289. 5-293. 7

16 I CI s NHCH3 white powder 310. 0-313. 5

17 I CI 0 NHS0 ₂ CH ₃ yellow powder 254. 6-260

18 I CI s NHS0 ₂ CH ₃ yellow powder 273. 7-276. 5

19 I CI 0 N(CH ₃ ) ₂ brownish yellow powder 310. 5-313. 7

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COCC.0/OlOZN3/X3d S.SS80/T10Z OAV (CDCl ₃ ) 10.67 (s, lH), 9.93 (s, lH), 8.55 (d, J = 4.6, lH), 8.02 - 7.85 (m, 2H), 7.62 (s, lH), 7.48 - 7.22 (m , l H), 7.19 (s, lH), 2.92 (s, 3H), 2.31 (s, 3H)

(DMSO-d ₆ ) 9.80 (s, lH), 8.42 - 7.94 (m, lH), 7.66 (d, 7 = 7.9, 2H), 7.44 (d, 7 = 7.2, 1H), 7.53 - 7.11 (m, 2H), 2.74(s, 3H), 2.48 (s, 3H)

(DMSO-d ₆ ) 1.89 (s, 3H), 2.15 (s, 3H), 7.37 (slH), 7.43 (s, lH), 7.59 (dd, lH, J = 6 Hz), 8.17 (d, lH, J =6H), 8.50 (d, lH, J = 6 Hz), 9.94 (s, lH), 10.23 (s, lH) (DMSO-d ₆ ) 10.50 (s, lH), 8.59 (s, lH), 8.50 ( Dd, J = 4.5, 1.7, lH), 8.18 (s, lH), 7.72 - 7.65 (m, 2H), 7.40 (s, 1H), 2.21 (S, 3H), 1.82 (S, 1H)

(CDCl ₃ ) 9.94 (s, lH), 8.46 (s, lH), 7.85 (d, J = 7.4, lH), 7.71 (s, lH), 7.38 (s, 2H), 7.19 (s, lH), 2.81(s,3H), 2.26(s,3H)

(CDCl ₃ ) 9.94 (s, lH), 8.46 (s, lH), 7.85 (d, J = 7.4, lH), 7.71 (s, lH), 7.38 (s, 2H), 7.19 (s, lH), 2.81(s,3H), 2.26(s,3H)

(DMSO-d ₆ ) 10.38 (s, lH), 8.68 - 8.33 (m, lH), 8.27 - 7.94 (m, lH), 7.92 - 7.66 (m, lH), 7.65 - 7.44 (m, 2 H), 7.37(s,3H), 2.18(s,3H)

(DMSO-d ₆ ) 10.38 (s, lH), 8.68 - 8.33 (m, lH), 8.27 - 7.94 (m, lH), 7.92 - 7.66 (m, lH), 7.65 - 7.44 (m, 2 H), 7.37(s,3H), 2.18(s,3H)

(DMSO-d ₆ ) 10.50 (s, 1H), 8.64 (s, 1H), 8.13 (s, 1H), 7.75- 7.33 (m, 4H), 2.36 (s, 3H) (DMSO-d ₆ ) 10.20 ( s, lH), 8.58-8.13 (m, lH), 8.38-8.04 (m, lH), 7.93-7.58 (m, lH), 7.75-7.53 (m, 2 H), 7.47 (s, 3H), 2.40 (s, 3H)

(DMSO-d ₆ ) 10.60 (s, 1H), 8.54 (s, 1H), 8.22 (s, 1H), 7.73 - 7.46 (m, 4H), 2.26 (s, 3H) (DMSO-d ₆ ) 8.68 ( d, J = 4.2, lH), 8.15 (s, lH), 7.96 (d, J = 7.8, lH), 7.84 (s, lH), 7.65 (s, lH), 7.31 (s, lH), 2.56 ( s, 3H)

(DMSO-d ₆ ) 10.40 (s, 1H), 8.64 (s, 1H), 8.32 (s, 1H), 7.85 - 7.53 (m, 4H), 2.56 (s, 3H) (DMSO-d ₆ ) 8.55 ( d, J = 4.2, lH), 7.95 (s, lH), 7.86 (d, J = 7.8, lH), 7.78 (s, lH), 7.64 (s, lH), 7.21 (s, lH), 2.36 ( s, 3H)

(DMSO-d ₆ ) 8.85 (d, J = 4.2, lH), 8.15 (s, lH), 7.89 (d, J = 7.8, lH), 7.78 (s, lH), 7.64 (s, lH), 7.22 (s,lH), 2.44(s,3H)

(DMSO-d ₆ ) 8.75 (d, J = 4.2, lH), 7.95 (s, lH), 7.86 (d, J = 7.8, lH), 7.76 (s, lH), 7.64 (s, lH), 7.31 (s,lH), 2.26(s,3H)

(DMSO-d ₆ ) 10.38 (s, 1H), 8.47 (s, 1H), 8.13 (s, 1H), 7.73 - 7.43 (m, 4H), 2.26 (s, 3H) (DMSO-d ₆ ) 10.50 ( s, 1H), 8.54 (s, 1H), 8.13 (s, 1H), 7.63 - 7.33 (m, 4H), 2.35(s, 3H) (CDC13) 10.56 (s, lH), 8.65-8.44 (m, lH), 8.18-7.87 (m, 2H), 7.55-7.38 (m, 2H), 7.21 (s, 1H), 2.63 (s, 3H), 2.30 (s, 3H)

(DMSO-d6) 12.38 (s, 1H), 10.30 (s, 1H), 8.47 (s, 1H), 8.20 (s, 1H), 7.66 - 7.38 (m, 4H), 2.36 (s, 3H)

(DMSO-d6) 9.80 (s, lH), 8.83 (d, J = 4.2, 1H), 7.95 (s, lH), 7.86 (d, J = 7.8, lH), 7.64 (s, lH), 7.54 ( s,lH),7 .ll(s,lH), 2.38(s,3H)

(CDC13) 10.88 (s, lH), 9.90 (s, lH), 8.65 (d, J = 4.6, lH), 8.22 - 7.86 (m, 2H), 7.72 (s, lH), 7.46 - 7.22 (m, l H), 7.19 (s, lH), 2.84 (s, 3H), 2.31 (s, 3H)

 43 (DMSO-d6) 9.80 (s, lH), 8.42 - 7.94 (m, lH), 7.66 (d, J = 7.9, 2H), 7.30 (d, J = 7.2, 1H), 7.42 - 7.04

(m, 2H), 2.66(s, 3H), 2.48 (s, 3H)

 44 (CDC13) 10.38 (s, lH), 9.16 (s, lH), 8.25 (s, lH), 7.52 (d, J = 7.4, lH), 7.73 (s, lH), 7.46 (s, 2H),

 7.21(s,lH), 2.68(s,3H), 2.20(s,3H)

 45 (DMSO-d6) 10.81 (s, 1H), 8.74 (s, 1H), 8.03 (s, 1H), 7.95- 7.53 (m, 4H), 2.46 (s, 3H)

46 (DMSO-d6) 10.42 (s, 1H), 8.53 (s, 1H), 8.10 (s, 1H), 7.75- 7.38 (m, 4H), 2.36 (s, 3H)

47 (DMSO-d6) 8.85 (d, J = 4.2, lH), 7.65 (s, lH), 7.86 (d, J = 7.8, lH), 7.76 (s, lH), 7.42 (s, lH), 7.31 (s,lH),

2.46(s,3H)

 48 (DMSO-d6) 8.55 (d, J = 4.2, lH), 7.85 (s, lH), 7.86 (d, J = 7.8, lH), 7.78 (s, lH), 7.64 (s, lH), 7.20 (s,lH),

2.33(s,3H)

An example of a preparation containing the compound of the present invention as an active ingredient, which is useful as an insecticide in the fields of agriculture, horticulture and flower cultivation, will be described below. However, embodiments of the invention are not limited to the following. Formulation Example 1: Water emulsion

 20 parts of the compound of the present invention, 12 parts of toluene, 6 parts of epoxy oxime-epoxypropene block copolymer, 6 parts of xanthan gum, 8.5 parts of ethylene glycol/propylene glycol composite antifreeze, 0.8 parts of silicone, water 46.7 parts, according to the water emulsion processing technology, an aqueous emulsion having an active ingredient of 20% was obtained. Formulation Example 2: Suspending agent:

 25 parts of the compound of the present invention, 6 parts of a wetting agent to sodium methyl fatty amide sulfonate, 2 parts of a suspending nonylphenol ethoxylate ether condensate, 6 parts of a tackifier carboxymethyl cellulose 1 part of preservative sodium salicylate, 2 parts of antifreeze propylene glycol, 1 part of antifoaming silicone oil, 57 parts of water, 25% suspension of active ingredient according to the suspension processing technology.

Formulation Example 3: Emulsifiable Oil

 10 parts of the compound of the present invention, 40 parts of xylene, 35 parts of dimethylformamide, and 15 parts of Tween 80 emulsifier were obtained by an oil slick processing technique to obtain an emulsifiable concentrate having an active ingredient of 10%. Formulation Example 4: Water-dispersible granules

80 parts of the compound of the present invention, 2 parts of the wetting agent PO-EO block polyether, 10 parts of the dispersing agent naphthalenesulfonic acid condensate sodium salt, 1 part of the disintegrant polypyrrolidone, 7 parts of diatomaceous earth, The water-dispersible granule processing process gives an active ingredient of 80% Water-dispersible granules. Test examples of the insecticide using the compound of the present invention as an active ingredient will be described below. However, embodiments of the invention are not limited to the following. Test Example 1: Insecticidal effect on Plutella xylostella

 The 3rd instar larvae were selected and tested for insecticidal effects using a leaf-fed feeding method. According to the constitution of Formulation Example 3, the compounds of the examples of the present invention were each made into an insecticide. The obtained insecticide emulsifiable concentrate is diluted with purified water and uniformly mixed to obtain a desired concentration of the chemical solution. Select amaranth, wash and dry, use a puncher to make a leaf dish, dip in the liquid for 10 seconds, and then dry it naturally and put it into the dish. Each dish was connected to P. xylostella 3 instar larvae 10 times, repeated 3 times, the number of dead insects was investigated in the first ld and 3d, the mortality was counted, and the insecticidal effect was evaluated. Mortality statistics are shown in the table below.

 NO. dose mg/L Id mortality%> 2d mortality%> 3d mortality%>

1 100 0.00 10.00 20.00

2 100 0.00 40.00 100.00

3 100 19.05 76.19 90.48

4 100 0.00 65.00 100.00

5 100 100 100.00 100.00

6 100 4.76 80.95 100.00

7 100 5.26 68.42 94.74

8 100 0.00 80.95 47.62

9 100 0 0 50.00

10 100 31.82 72.73 100.00

11 100 42.86 71.43 100.00

12 100 9.52 85.71 100.00

13 100 12.54 77.22 95.33

14 100 7.00 53.25 82.33

15 100 22.00 66.00 95.00

16 100 18.13 57.32 90.12

17 100 7.32 51.66 80.23

18 100 9.44 60.23 87.66

19 100 2.55 45.67 82.00

20 100 4.88 55.45 88.22 21 100 8.53 32.55 80.11

22 100 7.77 27.63 77.75

23 100 18.55 46.23 95.12

24 100 7.09 30.22 66.06

25 100 5.22 37.73 64.23

26 100 8.15 30.43 70.32

27 100 21.01 57.66 96.32

28 100 23.15 67.22 100.00

29 100 12.53 55.11 82.22

30 100 10.13 45. 66 80.78

31 100 5.34 34.53 66.02

32 100 8.15 23.66 68.34

33 100 15.17 33.33 78.65

34 100 20.12 47.63 90.55

35 100 18.45 57.72 92.55

36 100 6.78 32.44 56.30

37 100 8.78 27.83 45.05

38 100 10.28 38.23 66.68

39 100 4.55 27.52 70.66

40 100 2.28 38.13 78.54

41 100 7.52 18.78 67.03

42 100 6.98 34.63 82.24

43 100 11.66 29.15 87.82

44 100 8.22 32.12 78.23

45 100 5.52 17.66 48.92

46 100 7.09 20.12 56.73

47 100 9.55 28.44 73.12

48 100 3.33 16.53 35.32 Compound No.2, No.4, No.5, No.6, No.l0, No.ll, No.12, etc. The killing rate reached 100 at the 3rd day of 100mg/L. %. Test Example 2: Insecticidal effect on broad bean meal The 3 day old nymphs of Vicia faba, which were continuously raised in the room, were selected for the insecticidal effect test by the dipping method. According to the constitution of Formulation Example 3, the compounds of the present invention were each made into an insecticide. The obtained insecticide emulsifiable concentrate was diluted with purified water to prepare a 400 mg/L drug solution. Five scorpions were inoculated on 30~50mm high broad bean seedlings, and after 24h, they were removed into sorghum. About 30 heads of each of the broad bean seedlings were primilated, and the third day was 3 days old. The broad bean seedlings were cut at the base and the base number was recorded. The stalked broad bean seedlings were immersed in the liquid for 5 s, taken out, and inserted into a vial containing water (three times for each concentration). After treatment, it was moved to the observation room, and the number of dead and live insects was checked at 72 hours, and the mortality rate was counted (the aphid was unable to move as the death standard). Compound No. 2 had a mortality rate of 96.04% on day 3 at a concentration of 400 mg/L. The mortality of the compound ?^0.35 on the third day at a concentration of 400113⁄4/1 was 95.16%.

Trial 3: Killing effect on Chilo suppressalis

 The 3rd instar larvae of Chilo suppressalis were used, and the insecticidal effect test was carried out by using the rice seedling feeding method. According to the constitution of Formulation Example 3, the compounds of the examples of the present invention were each made into an insecticide. The obtained insecticide emulsifiable concentrate is diluted with purified water and uniformly mixed to obtain a desired concentration of the chemical solution. The rice seedlings were selected and divided into 10 strains/group, which were taken out in the liquid for 10 seconds, and then naturally dried to be placed in the finger tube. Each tube was connected to 10 larvae of the third instar larvae, and the larvae were counted three times. The number of dead insects was counted on the first ld, 3d, 5d, and 7d, and the mortality was evaluated to evaluate the insecticidal effect. Compound No. 11 had a mortality rate of 16.67, 36.67, 43.33, and 90.00% at the first ld, 3d, 5d, and 7d after treatment. Compound No. 34 had a mortality rate of 17.61, 34.61, 42.13, and 91.01% at ld, 3d, 5d, and 7d after treatment, respectively.

Claims

Claim 1. An o-heterocyclic anilide compound represented by the formula (I) or (Π),

C5 halodecyloxy, fluorenyl, C1~C5 thiol, amino, C1~C5 垸amino, C1~C5 halogenated fluorenylamino, C1~C5 oxiranylamino, C1~C5 decylsulfonylamino, C1~ C5 acyl group, C1 to C5 amide group, halogen, cyano group or thiocyano group. The o-heterocyclic anilide compound according to claim 1, wherein the ₁ or _{2 is} independently H, F, CI, Br or CN. The o-heterocyclic anilide compound according to claim 2, wherein the ₁ or _{2 is} independently CI, Br or CN. 4. The o heterocyclic carboxanilides compound according to claim 1, wherein said one or ^ ₁₂ are each independently alkyl with C1~C5, a hydroxyl group, C1~C5 embankment group, a mercapto group, C1 to C5 thiol, amino, Cl~C5 decylamino, C1 to C5 decylsulfonylamino, C1 to C5 amide, halogen, cyano or thiocyano.  The o-heterocyclic anilide compound according to claim 4, which is characterized by the above. 1 to C5 fluorenyl, hydroxy, decyl, C1 to C5 thiol, amino, C1 to C5 fluorenylamino, C1 to C5 decylsulfonylamino, C1 to C5 amide, halogen, cyano or thiocyano. The o-heterocyclic anilide compound according to claim 4, wherein R ₂ is a Cl~C5 fluorenyl group, an amino group, a C1 to C5 fluorenylamino group, a C1 to C5 decyl sulfonamide group, C1 to C5 amide group, halogen, cyano group or thiocyano group. The process for producing an o-heterocyclic anilide compound according to any one of claims 1 to 6, wherein Z is oxygen, ^为为. 1~. 5 fluorenyl, amino, halogen, cyano or thiocyano group, when X is under neutral conditions, in a polar aprotic solvent, at room temperature, the intermediate M1 is reacted with the corresponding hydrazide reagent CONHNH2 to open the ring. A compound of the formula (I 1 ) is obtained, the reaction route of which is:

 Z is oxygen, ! ^ is hydroxyl, when X is, firstly intermediate M1 is reacted with hydrazine hydrate to prepare intermediate M2. Under neutral conditions, polar protic solvent, intermediate M2 reacts with triphosgene or phosgene at reflux temperature. Get general formula

 Z is oxygen, is a sulfhydryl group, and when X is, under basic conditions, in a polar protic solvent, at the reflux temperature, the intermediate M2 and the second line are:

When 7^ S, X is, under intermediate conditions, in a polar protic solvent, intermediate M2 is reacted with carbon disulfide or halogenated hydrocarbon at reflux temperature to obtain intermediate M3, and then organic weak acid is used in the solvent. Catalyst, M3 reaction Dehydration and condensation synthesis to obtain a compound represented by the formula (I 4); or reacting the intermediate M1 with the corresponding reagent NH NHCSRi to obtain M3, and then using an organic weak acid as a catalyst in a solvent, and dehydrating and synthesizing the ring by M3 reaction As shown in (1 4)

 M 1 The process for producing an o-heterocyclic anilide compound according to claim 1, which is characterized in that, under basic conditions, in a polar protic solvent, at 70-80 ° C or at reflux temperature, the intermediate M4 is The corresponding reaction reagent HON=CNH ₂ R _{2 is} condensed into a ring to obtain a compound represented by the formula (II), and the reaction route is:

9. Use of a compound according to any one of claims 1 to 6 for the preparation of an insecticide.  An insecticidal composition comprising the compound according to any one of claims 1 to 6 as an active ingredient, together with a pesticide adjuvant, as an aqueous emulsion, a suspension, a water-dispersible granule or an emulsion.