CN111689900B

CN111689900B - Aryl pyrazole sulfonyl hydrazide metal complex and ultrasonic radiation synthesis method and application thereof

Info

Publication number: CN111689900B
Application number: CN202010547887.1A
Authority: CN
Inventors: 陈连清; 杨镜; 吴忠达
Original assignee: South Central University for Nationalities
Current assignee: South Central Minzu University
Priority date: 2020-06-16
Filing date: 2020-06-16
Publication date: 2021-08-17
Anticipated expiration: 2040-06-16
Also published as: CN111689900A

Abstract

The invention relates to the technical field of organic synthesis, in particular to an aryl pyrazole sulfonyl hydrazide metal complex, a method for synthesizing a compound of the type by using an ultrasonic radiation method, and application of the compound of the type. The applicant selects an aryl pyrazole hydrazide compound as a raw material, takes organic amine as an acid-binding agent, adopts a proper solvent, reacts with sulfonyl chloride under the action of an ultrasonic radiation method to obtain an aryl pyrazole sulfonyl hydrazide structure derivative, and coordinates with metal ions to form an aryl pyrazole sulfonyl hydrazide metal complex. And tests are carried out on the bacteriostatic activity, the insecticidal activity and the herbicidal activity of the compounds, so that a certain control effect is obtained.

Description

Aryl pyrazole sulfonyl hydrazide metal complex and ultrasonic radiation synthesis method and application thereof

Technical Field

The invention relates to the technical field of organic synthesis, in particular to an aryl pyrazole sulfonyl hydrazide metal complex, a method for synthesizing a compound of the type by using an ultrasonic radiation method, and application of the compound of the type.

Background

In recent years, with the emphasis of scientists on the problems of inhibiting germs, preventing weeds and controlling pests, more and more pure organic insecticides have been invented, including arylpyrazole compounds and hydrazide compounds. The arylpyrazole compounds are receiving more and more attention from many researchers due to their biological high efficiency, low toxicity and structural diversity. The arylpyrazole compounds can interfere the chloride ion passage through gamma-aminobutyric acid regulation chloride channel, so that the activity of the normal central nervous system of pests is damaged, and the insecticidal effect is achieved. The arylpyrazole structure is photosensitive, can be well photodegraded, is environment-friendly, and can be widely applied to the agricultural field as a green pesticide. The arylpyrazole compounds are not only used for killing insects, but also have good effects on preventing and controlling weeds and inhibiting germs.

Hydrazide compounds are also the hot material of researchers in the field of pesticides. The hydrazide compound has wide biological activity and particularly has good effect on preventing and removing weeds, for example, the primisulfuron herbicide, which is independently innovated by the institute of elemental organic chemistry of southern Kao university, monosulfuron and monosulfuron ester, has good effect on preventing and removing dicotyledonous weeds and most monocotyledonous weeds. The hydrazide compound has the characteristics of high efficiency, long lasting period, small drug resistance, high selectivity and the like, and is widely applied to the fields of gardening and flowers. Hydrazide compounds are also useful as insect growth regulators and in the treatment of tumors and malaria.

In order to combine the weeding efficiency of hydrazide compounds with the insecticidal efficiency of aryl pyrazole compounds and optimize the functions of bacteriostasis, weeding, insecticidal and the like of pesticides, a plurality of researchers splice a hydrazide structure and an aryl pyrazole structure in the same compound by utilizing the splicing principle of an active substructure to generate a structure synergistic effect, and more efficient multifunctional compounds are designed, such as novel pyrazole bishydrazide compounds, novel pyridine bipyrazole bishydrazide compounds and other pyrazole bishydrazide compounds, but related sulfonyl hydrazide compounds are very few, and the aryl pyrazole sulfonyl hydrazide compounds are not reported.

It is known that metal complexes have a very important influence on living systems, and many metal complexes play irreplaceable roles in other compounds. The metal complex maintains acid-base balance of cells and organisms in a form of releasing ions, maintains life activities of the cells and the organisms, and constitutes an important component of certain complex compounds of the cells. In recent years, many metal-containing drugs have been invented, such as 1, 3-diphenyl-4-formaldehyde pyrazole and Cu synthesized by Kiran Singh et al²⁺、Ni²⁺、Co²⁺、Zn²⁺And the like. The pyrazole metal complex has high biological activity in the aspects of disinsection, bacteriostasis, anti-inflammation and antivirus, and has important significance for the application in the aspect of medicine. The metal complex can be dissociated in insect body and then matched with other metal ions, so that the metal ions necessary for maintaining insect vital signs are lost to cause abnormal operation of organism, thereby achieving the purpose of killingThe purpose of the insect is.

In order to enable antibacterial, weeding and insecticidal activities to be better, the applicant designs an aryl pyrazole sulfonyl hydrazide ligand to be coordinated with metal ions to form an aryl pyrazole sulfonyl hydrazide metal complex by utilizing a splicing principle so as to wait for synthesizing a more efficient bioactive molecule. Although the splicing of a hydrazide structure and an arylpyrazole structure in one compound is reported, the synthesis of an arylpyrazole sulfonyl hydrazide metal complex by the splicing of a sulfonyl hydrazide structure and an arylpyrazole structure in one compound and the coordination of the sulfonyl hydrazide structure and the arylpyrazole structure with a metal ion is not reported yet.

At present, the synthesis of organometallic complexes is generally carried out by hydrothermal synthesis, conventional solution method, etc. The hydrothermal method involves high temperature and high pressure, so that the reaction conditions are strict and the repeated operability is poor. The conventional solution method has long reaction time and low yield. In recent years, ultrasound has led to intensive research by scientists because it can be easily handled and can accelerate chemical reactions. The transmission of ultrasonic waves in a medium can cause intense friction among medium molecules and heat dissipation, and various secondary ultrasonic effects such as thermal effect, chemical effect and other physical effects are generated. The ultrasonic wave can generate 5000K high temperature and 5 x 10K around the cavitation bubble in a very short time due to the acoustic cavitation effect⁴High pressure of kPa allows chemical reactions to be carried out that are difficult or impossible to carry out under normal conditions. The cavitation and secondary effect of ultrasonic radiation to the reactant can initiate the instantaneous high temperature and high pressure required by chemical reaction to form local high energy center, promote the violent stirring and homogeneous mixing of the reaction liquid, shorten the reaction time and raise the reaction yield. The ultrasonic radiation method has been widely applied to reduction reaction, oxidation reaction, addition reaction, substitution reaction, condensation reaction, hydrolysis reaction, etc., but the literature of the application of ultrasonic wave to the synthesis of the arylpyrazole sulfonyl hydrazide metal complex has been reported only rarely.

Disclosure of Invention

The sulfonyl hydrazide structure and the aryl pyrazole structure have good bacteriostatic, herbicidal and insecticidal activities, and the metal complex can exchange with other metal ions in an insect body so as to delete the necessary metal ions and enable pests to lose vital signs. The applicant intends to apply the active substructure splicing principle to splice the sulfonyl hydrazide structure and the aryl pyrazole structure in a compound and then coordinate with metal ions to synthesize the aryl pyrazole sulfonyl hydrazide metal complex.

Based on the consideration, the applicant designs the content of the invention, namely selecting an arylpyrazole hydrazide product as a raw material, taking organic amine as an acid-binding agent, adopting a proper solvent, reacting with sulfonyl chloride under the action of an ultrasonic radiation method to obtain an arylpyrazole sulfonyl hydrazide structure derivative, and then coordinating with metal ions to form an arylpyrazole sulfonyl hydrazide metal complex. The cavitation effect and the secondary effect of the ultrasonic radiation method are utilized to generate instantaneous high temperature and high pressure to form a local high-energy center, so that the reaction liquid is vigorously stirred and is uniformly mixed in all directions, the defects of a hydrothermal synthesis method and a conventional solution method are overcome, the reaction speed is accelerated, and the yield is greatly improved. The method has the advantages of short reaction time, mild reaction conditions and simple and convenient operation, can synthesize the arylpyrazole sulfonyl hydrazide metal complex which is difficult to synthesize at normal temperature and normal pressure at ordinary times, and can greatly improve the yield of the product.

Based on the above inventive concept, it is a first object of the present invention to provide an arylpyrazole sulfonyl hydrazide metal complex (vi) having a structural formula shown in general formula (vi):

in the general formula (VI), R₁Any one selected from the following groups:

-CH₂CH₃、—CH₂CH₂CH₃、—CH₂CH₂CH₂CH₃、—CH₂CH₂CH₂CH₂CH_3、

preferably, said R is₁Any one selected from the following groups:

most preferably, said R₁Is as follows;

or

In the general formula (VI), R₂Any one selected from the following groups: saturated alkane, mono-substituted or multi-substituted benzene ring, mono-substituted or multi-substituted aromatic ring and unsaturated alkene, wherein the substitution is chain alkyl substitution, cycloalkyl substitution or halogenation.

Preferably, R₂Any one selected from the following groups: -CCl₃、-CH₂CH₃、-CH₂CH₂CH₂CH₃、

More preferably, R is₂Any one selected from the following groups:

-CH₂CH₃、

in the general formula (VI), R₃Any one selected from the following groups: mono-substituted or multi-substituted benzene ring, wherein the substitution is chain alkyl substitution, cycloalkyl substitution or halogenation.

Preferably, R₃Selected from any of the following groupsThe method comprises the following steps:

more preferably, R₃Is composed of

In the general formula (VI), M is selected from any one of the following metals: fe. Ni, Zn, Mn, Cu, Mo, Pt, Co, Cd, In.

The second purpose of the invention is to provide a general synthetic method for synthesizing the compound with the structural formula shown as the general formula (VI), which has the advantages of high efficiency, environmental protection, simplicity, convenience and low cost.

In order to realize the second purpose of the invention, the technical scheme of the invention is as follows:

a process for the synthesis of a compound of formula (vi) comprising the steps of:

(I) aryl pyrazole compound

With compounds R₁Adding the-X into N, N-dimethylformamide, adding NaH solid, reacting at 60-180 deg.C for 6-18h (preferably at 80-130 deg.C for 7-14h) in ultrasonic reactor, and separating and purifying by column chromatography to obtain product (II)

The synthetic route of the compound shown in the general formula (II) is shown as follows:

(II) mixing the product (II) with anhydrous FeCl₃Adding into absolute ethyl alcohol, heating and refluxing for 6-12h (preferably at 90-Heating and refluxing for 7-10h at 120 ℃, and finally separating and purifying by column chromatography to obtain a product (III);

thirdly, adding the product (III) and hydrazine hydrate into absolute ethyl alcohol, heating and refluxing for 9-12h at 80-120 ℃ (preferably heating and refluxing for 9-11h at 80-110 ℃), and finally separating and purifying by column chromatography to obtain the product (IV)

The synthetic route of the compound shown in the general formula (IV) is shown as follows:

(IV) reacting the product (IV) with sulfonyl chloride

Adding the mixture into dichloromethane, adding organic amine (preferably triethylamine) serving as an acid-binding agent into the dichloromethane, and reacting for 0.5 to 5 hours (preferably reacting for 2.0 to 4.5 hours at 70 to 95 ℃) under ultrasonic radiation at 60 to 120 ℃ to obtain an aryl pyrazole sulfonyl hydrazide ligand (V)

Adding the aryl pyrazole sulfonyl hydrazide ligand (V) and a metal salt solution into an organic solvent, reacting for 2-10h (preferably reacting for 3.5-6h at 75-90 ℃) at 55-105 ℃ under ultrasonic radiation, and separating a product (VI) after the reaction is finished;

further, in the step (a), an arylpyrazole compound

Compound R₁-the mass ratio of X to NaH is 5: (1-5): (1-5), preferably 5: (1-3): (1-2).

Further, the product (II) in the step (II) is mixed with anhydrous FeCl₃The mass ratio of (5-10): (3-8), preferably (5-7): (3-6);

further, the mass ratio of the product (III) to the hydrazine hydrate in the step (III) is (5-10): (1-5), preferably (5-7): (1-2);

further, the product (IV) in the step (IV) is reacted with sulfonyl chloride

The mass ratio of (4-10): (1-5), preferably (4-7): (1-4);

further, in the step (V), the mass ratio of the aryl pyrazole sulfonyl hydrazide ligand (V) to the metal salt in the metal salt solution is (5-8): (5-8).

The synthetic route of the compound shown in the general formula (VI) is shown as follows:

the R is₁、R₂、R₃As defined above; the metal salt is ferric salt, nickel salt, zinc salt, manganese salt, copper salt, molybdenum salt, platinum salt, cobalt salt, cadmium salt or indium salt, and the compound R₁X in X is-Cl or-Br.

Further, the solvent used for dissolving the metal salt solution is at least one of ethylene glycol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, preferably ethanol.

Further, the organic solvent is benzene, toluene, acetone, tetrahydrofuran, DMF or DMSO.

Further, the ferric salt is ferric nitrate, ferric acetate, ferric sulfate or ferric chloride;

further, the nickel salt is nickel acetate, nickel sulfate, nickel nitrate or nickel chloride;

further, the zinc salt is zinc acetate, zinc chloride, zinc nitrate or zinc sulfate;

further, the manganese salt is manganese nitrate, manganese sulfate, manganese acetate or manganese chloride;

further, the copper salt is copper nitrate, copper acetate, copper sulfate, copper carbonate or copper chloride;

further, the molybdenum salt is molybdenum chloride, phosphomolybdic acid or molybdenum nitrate;

further, the platinum salt is platinum nitrate or platinum chloride;

further, the cobalt salt is cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt carbonate or cobalt chloride;

further, the cadmium salt is cadmium nitrate, cadmium acetate, cadmium sulfate, cadmium carbonate or cadmium chloride;

further, the indium salt is indium nitrate, indium sulfate or indium chloride.

The third purpose of the invention is to provide the application of the compound with the structural formula shown as the general formula (VI) in the plant bactericide.

The aryl pyrazole sulfonyl hydrazide metal complex prepared by the invention can be used for inhibiting phytophthora capsici, rice blast, wheat scab, rice sheath blight, wheat powdery mildew and the like.

The fourth purpose of the invention is to provide the application of the compound with the structural formula shown as the general formula (VI) in the preparation of medicines for preventing and removing gramineous weeds and/or dicotyledonous weeds.

The aryl pyrazole sulfonyl hydrazide metal complex prepared by the invention can be used for preventing and killing gramineous weeds and/or dicotyledonous weeds such as wild oats, brome, jointed wheat, alopecurus, barnyard grass, bluegrass, setaria viridis, mulukhiya, monochoria japonica, bidens, lemna, glufosinate, sesbania and the like.

The fifth purpose of the invention is to provide the application of the compound with the structural formula shown as the general formula (VI) in the drugs for preventing and controlling harmful insects (including orthoptera, thysanoptera, homoptera, heteroptera, lepidoptera, coleoptera and diptera) and/or mites.

The aryl pyrazole sulfonyl hydrazide metal complex prepared by the invention can be used for controlling harmful insects (including orthoptera, thysanoptera, homoptera, heteroptera, lepidoptera, coleoptera and diptera) and/or mite pests in the orthoptera such as cockroaches; thysanoptera such as thrips gossypii, thrips oryzae, thrips citrullus; homopterans such as black tail hoppers, FENG, aphids; heteropterans such as cabbage stinkbug; lepidoptera such as Oriental armyworm, prodenia litura, diamondback moth, beet armyworm, Trichoplusia ni, and cabbage caterpillar; coleoptera, such as rice flatworm; insect pests of the order diptera, such as Aedes aegypti, Culex; the mite pests such as cotton spider mite, panonychus citri and tetranychus urticae.

Compared with the prior art, the compound of the general formula (VI) and the ultrasonic radiation synthesis thereof have the following advantages and beneficial effects:

1. the novel compound-arylpyrazole sulfonyl hydrazide metal complex synthesized by the invention has a molecular structure containing a sulfonyl hydrazide structure, an arylpyrazole structure and metal ions, the sulfonyl hydrazide structure and the arylpyrazole structure have good antibacterial, weeding and insecticidal activities, and the metal complex can be exchanged with other metal ions in an insect body so as to delete the metal ions necessary for maintaining the vital signs of the insect and enable the insect to lose the vital activity. By using the active substructure splicing principle, the aryl pyrazole sulfonyl hydrazide metal complex which is synthesized by splicing the sulfonyl hydrazide structure and the aryl pyrazole structure in one compound and then matching with metal ions has good synergistic inhibition effect on the pathogenic bacteria, has good control activity on various weeds, has good control effect on various pests, has low toxicity on beneficial organisms, generates control effect synergistic effect, and is a multifunctional, efficient and low-residue green pesticide.

2. The method synthesizes the aryl pyrazole sulfonyl hydrazide metal complex by using an ultrasonic radiation method for the first time. Compared with the common solution method, the ultrasonic radiation method has the characteristics of simple and safe operation, short reaction time, high yield, no pollution to the environment, high yield, easy post-treatment, easy realization of industrialization and the like.

3. The synthesized aryl pyrazole sulfonyl hydrazide metal complex is an antibacterial, weeding and insecticidal drug which is efficient, high in selectivity, low in residue and friendly to environment. The synthetic raw material cost for synthesizing the aryl pyrazole sulfonyl hydrazide metal complex is low, the reaction condition is mild, the operation is simple, the yield is high, and the method can be widely applied to the fields of agriculture, horticulture, flowers and health, so that the method has great development and application values.

Detailed Description

The products of the present invention, their synthesis and use are further illustrated by the following specific examples, which should not be construed as limiting the scope of the invention in any way.

The reagents used in the following examples are commercially available or may be synthesized by methods known in the art. Model number SM100 of the ultrasonic reactor used.

Example 1 Arylpyrazole sulfonylhydrazide Metal copper Complex (Compound (VI)₁) Synthesis of

Formation of Compound (VI)₁) The reaction formula (A) is as follows:

the specific operation steps are as follows:

(1) 5.0g of arylpyrazole compound I₁Adding 1.1g of 1-chlorobutane into 40ml of N-dimethylformamide, adding 2.0g of NaH solid into the dimethylformamide, reacting in an ultrasonic reactor (fixed power 140W) at 80 ℃ for 8h, and finally separating and purifying by column chromatography to obtain 5.3g of a product (II)₁) The yield is as follows: 96.7 percent.

(2) 5.0g of product (II)₁) With 3.4g of anhydrous FeCl₃Adding into 30mL anhydrous ethanol, heating and refluxing at 90 deg.C for 10h, and separating and purifying by column chromatography to obtain 5.2g product (III)₁) The yield of this step: 95.0 percent.

(3) 5.0g of (III) are then added₁) Adding 1.0g hydrazine hydrate into 30mL absolute ethyl alcohol solvent, heating and refluxing for 9h at 80 ℃, and finally separating and purifying by column chromatography to obtain 4.5g product aryl pyrazole hydrazide compound (IV)₁) The yield of this step: 93.1 percent.

(4) A100 mL flask was charged with 4.5g of an arylpyrazole hydrazide compound (IV)₁) 20.0mL of dichloromethane and 1.6g of benzenesulfonyl chloride, then adding a drop of triethylamine as an acid-binding agent (about 0.05mL, the same applies below), placing the mixture into an ultrasonic reactor (fixed power 140W) to react for 2.5 hours at the temperature of 80 ℃, and performing suction filtrationDrying to obtain 5.5g of aryl pyrazole sulfonyl hydrazide ligand (V)₁) The yield of this step: 97.4 percent.

(5) Then 5.0g of arylpyrazole sulfonylhydrazide ligand (V) was added to a 100mL three-necked flask₁) THF 30mL, copper acetate 25mL ethanol solution (6g copper acetate dissolved in absolute ethanol 25 mL), install reflux condenser and thermometer, put three-necked flask into ultrasonic reactor (fixed power 170W) to react, water bath heating to 85-90 deg.C, reaction time is 3.5 h. After the reaction is finished, preparing a sample by a dry method, and separating by column chromatography (V)_{Ethyl acetate}：V_{Petroleum ether}1: 1) 5.3g of the compound (VI) are obtained₁) The yield of this step: 98.0 percent. mp 176.5-176.0 deg.C IR (KBr, cm)^-1):3225(N-H),3083(CH₂-H),1320(O ═ S ═ O),1673(-C ═ O),1608 (vibration of pyrazole ring skeleton), 1538 and 1479 (vibration of benzene ring skeleton), 1315(C-F),883 (aromatic ring C-H).¹HNMR(CDCl₃,400MHz)δ:10.12(s,1H,N-H),10.06(s,1H,N-H),7.93(s,2H,Ar-H),7.54(s,2H,Ar-H),7.36(s,2H,Ar-H),7.24(s,1H,Ar-H),4.0(s,1H,N-H),3.06(s,2H,CH₂),1.56(s,2H,CH₂),0.96(s,3H,C-H₃)。

Example 2 Arylpyrazole sulfonylhydrazide manganese Metal Complex (Compound (VI)₂) Synthesis of

Formation of Compound (VI)₂) The reaction formula (A) is as follows:

the method sequentially comprises the following steps:

(1) 5.0g of arylpyrazole compound I₂Adding 1.3g propionyl chloride into 40ml LN, N-dimethylformamide, adding 2.0g NaH solid, reacting at 80 deg.C for 9h in ultrasonic reactor (fixed power 140W), and separating and purifying by column chromatography to obtain 5.6g product (II)₂) The yield is as follows: 93.1 percent.

(2) 5.0g of product (II)₂) With 3.5g of anhydrous FeCl₃Adding into 40mL anhydrous ethanol, heating and refluxing at 100 deg.C for 8h, and separating and purifying by column chromatography to obtain 6.0g product (III)₂) The yield of this step: 96.7 percent.

(3) 6.0g of product (III) are then introduced₂) Adding 1.5g hydrazine hydrate into absolute ethyl alcohol, heating and refluxing for 9h at 100 ℃, and finally separating and purifying by column chromatography to obtain 5.6g product (IV) of aryl pyrazole hydrazide compound₂) The yield of this step: 95.8 percent.

(4) A100 mL flask was charged with 5.5g of an arylpyrazole hydrazide compound (IV)₂) 20.0mL of dichloromethane and 2.6g of trichloromethylsulfonyl chloride, then adding a drop of triethylamine as an acid-binding agent, putting the mixture into an ultrasonic reactor (fixed power 140W) to react for 3 hours at the temperature of 90 ℃, and performing suction filtration and drying to obtain 7.5g of aryl pyrazole sulfonyl hydrazide ligand (V)₂). Yield of this step: 98.0 percent.

(5) In a 100mL three-necked flask was added 7.0g of arylpyrazole sulfonylhydrazide ligand (V)₂) 30mL of THF and 20mL of manganese acetate ethanol solution (6g of manganese acetate dissolved in 20mL of absolute ethanol), a reflux condenser tube and a thermometer are arranged, the three-necked flask is placed into an ultrasonic reactor (with fixed power of 150W) for reaction, the temperature is heated to 80-90 ℃ in a water bath, and the reaction time is 3.5 h. After the reaction is finished, preparing a sample by a dry method, and separating by column chromatography (V)_{Ethyl acetate}：V_{Petroleum ether}1: 1) 7.3g of the compound (VI) were obtained₂) The yield of this step: 95.6 percent. mp 160.6-161.1 deg.C IR (KBr, cm)^-1) 3254(N-H),1314(C-F),3080(C-H),1320(O ═ S ═ O),1724(-C ═ O),1606 (pyrazole ring skeleton vibration), 1530 and 1399 (benzene ring skeleton vibration), 1314(C-F),884 (aromatic ring C-H).¹HNMR(CDCl₃,400MHz)δ:10.15(s,1H,N-H),10,03(s,1H,N-H),8.2(s,1H,Ar-H),7.50(s,1H,Ar-H),7.1(s,1H,Ar-H),2.20(s,1H,C-H₂),1.9(s,H,N-H),1.2(s,H,C-H₃)。

Example 3 Arylpyrazole sulfonylhydrazide Metal Zinc (Compound (VI)₃) Synthesis of

Formation of Compound (VI)₃) The reaction formula (A) is as follows:

the method sequentially comprises the following steps:

(1) 5.0g of arylpyrazole compound I₃Adding 3.0g of paranitrobenzoyl chloride into 40ml of N, N-dimethylformamide, adding 1.0g of NaH solid into the dimethylformamide, reacting the mixture for 7 hours at 120 ℃ in an ultrasonic reactor (fixed power of 140W), and finally separating and purifying by column chromatography to obtain 7.1g of a product (II)₃) The yield is as follows: 96.3 percent.

(2) 7.0g of product (II)₃) With 6.0g of anhydrous FeCl₃Adding into 30mL anhydrous ethanol, heating and refluxing at 100 deg.C for 8h, and separating and purifying by column chromatography to obtain 7.5g product (III)₃) The yield of this step: 97.4 percent.

(3) 7.3g of product (III) are then introduced₃) Adding 1.5g hydrazine hydrate into 35mL absolute ethyl alcohol, heating and refluxing for 9h at 100 ℃, and finally separating and purifying by column chromatography to obtain 6.7g product aryl pyrazole hydrazide compound (IV)₃) The yield of this step: 94.5 percent.

(4) 6.5g of arylpyrazole hydrazide compound (IV) was placed in a 100mL flask₃) 20.0mL of dichloromethane and 1.7g of ethylsulfonyl chloride, then adding a drop of triethylamine as an acid-binding agent, putting the mixture into an ultrasonic reactor (fixed power 140W) to react at the temperature of 85 ℃ for 3.5h, filtering and drying to obtain 7.4g of aryl pyrazole sulfonyl hydrazide ligand (V, the amount of the aryl pyrazole sulfonyl hydrazide ligand is less than the amount of the aryl pyrazole sulfonyl hydrazide ligand in the reaction solution, and the like₃) The yield of this step: 95.1 percent.

(5) In a 100mL three-necked flask was added 7.0g of arylpyrazole sulfonylhydrazide ligand (V)₃) 35mL of THF and 30mL of zinc acetate ethanol solution (7g of zinc acetate dissolved in 30mL of absolute ethanol), a reflux condenser tube and a thermometer are arranged, the three-necked flask is placed into an ultrasonic reactor (with fixed power of 180W) for reaction, the temperature is heated to 85-90 ℃ in a water bath, and the reaction time is 6.0 h. After the reaction is finished, preparing a sample by a dry method, and separating by column chromatography (V)_{Ethyl acetate}：V_{Petroleum ether}1: 1) 7.2g of the compound (VI 3) was obtained. Yield of this step: 96.5 percent. mp is 174.6-175.1 deg.C, IR (KBr, cm)^-1) 3250(N-H),3070(C-H),1669(-C ═ O),1615 (pyrazole ring bone)Frame vibration), 1546 and 1378 (benzene ring skeleton vibration), 1314(C-F),1320(O ═ S ═ O),889 (aromatic ring C-H).¹HNMR(CDCl₃,400MHz)δ:8.5(s,2H,Ar-H),8.21(s,3H,Ar-H),8.15(s,2H,N-H),7.2(s,2H,Ar-H),6.8(s,H,Ar-H),2.93(s,H,C-H₃),2.75(s,H,C-H₂)2.35(s,H,C-H₃),2.0(s,H,N-H)。

Example 4 Arylpyrazole sulfonylhydrazide Metal copper Complex (Compound (VI)₄) Synthesis of

Formation of Compound (VI)₄) The reaction formula (A) is as follows:

the method sequentially comprises the following steps:

(1) 5.0g of arylpyrazole compound I₄Adding 2.7g of p-chlorobenzoyl chloride into 40ml of N-dimethylformamide, adding 1.0g of NaH solid into the dimethylformamide, reacting the mixture for 10 hours at 130 ℃ in an ultrasonic reactor (fixed power of 140W), and finally separating and purifying the mixture by column chromatography to obtain 6.8g of a product (II)₄). Yield: 95.7 percent.

(2) 6.5g of product (II)₄) With 5.8g of anhydrous FeCl₃Adding into 35mL anhydrous ethanol, heating and refluxing at 120 deg.C for 7h, and separating and purifying by column chromatography to obtain 6.5g product (III)₄) The yield of this step: 94.2 percent.

(3) 6.0g of product (III) are then introduced₄) Adding 1.3g hydrazine hydrate into 30mL absolute ethyl alcohol, heating and refluxing for 10h at 100 ℃, and finally separating and purifying by column chromatography to obtain 5.6g product aryl pyrazole hydrazide compound (IV)₄) The yield of this step: 94.3 percent.

(4) A100 mL flask was charged with 5.0g of an arylpyrazole hydrazide compound (IV)₄) 20mL of dichloromethane and 1.6g of 1-butanesulfonyl chloride, then a drop of triethylamine is added as an acid-binding agent, the mixture is put into an ultrasonic reactor (fixed power 140W) to react for 3.5h at the temperature of 80 ℃, and the mixture is filtered, filtered and dried to obtain 5.9g of aryl pyrazole sulfonyl hydrazide ligand (V is the ligand of the aryl pyrazole sulfonyl hydrazide)₄) The yield of this step: 95.2 percent.

(5) In thatA100 mL three-necked flask was charged with 5.5g of an arylpyrazole sulfonylhydrazide ligand (V)₄) THF 30mL, copper acetate 25mL ethanol solution (6g copper acetate dissolved in absolute ethanol 25 mL), install reflux condenser tube and thermometer, put three-necked flask into ultrasonic reactor (fixed power 180W) to react, water bath heating 80-85 deg.C, reaction time is 5.0 h. After the reaction is finished, preparing a sample by a dry method, and separating by column chromatography (V)_{Ethyl acetate}：V_{Petroleum ether}1: 1) 5.8g of the compound (VI) are obtained₄). Yield of this step: 96.2 percent. mp is 185.7-186.6 deg.C, IR (KBr, cm)^-1) 3253(N-H),3070(C-H),1679(-C ═ O),1615 (vibration of pyrazole ring skeleton), 1546 and 1380 (vibration of benzene ring skeleton), 1314(C-F),890 (aromatic ring C-H).¹HNMR(CDCl₃,400MHz)δ:10,14(s,2H,N-H),10,14(s,2H,N-H),10.03(s,2H,Ar-H),7.75(s,2H,Ar-H),7.4(s,2H,Ar-H),7.1(s,2H,Ar-H),3.48(s,1H,C-H₂),2.55(s,1H,C-H₂),2.1(s,1H,N-H),1.43(s,1H,C-H₂),1.21(s,1H,C-H₂),1.13(s,1H,C-H₃),0.93(s,1H,C-H₃)。

Example 5 Arylpyrazole sulfonylhydrazide Metal molybdenum (Compound (VI)₅) Synthesis of

Formation of Compound (VI)₅) The reaction formula (A) is as follows:

the method sequentially comprises the following steps:

(1) 5.0g of arylpyrazole compound I₅Adding 2.4g of benzene sulfonyl chloride into 40ml of N-dimethylformamide, adding 1.0g of NaH solid into the dimethylformamide, reacting the mixture for 10 hours at 120 ℃ in an ultrasonic reactor (the fixed power is 140W), and finally separating and purifying the mixture by column chromatography to obtain 6.5g of a product (II)₅) The yield is as follows: 94.5 percent.

(2) 6.0g of product (II)₅) With 4.0g of anhydrous FeCl₃Added to 35mL of anhydrous ethyl acetateHeating and refluxing in alcohol at 120 deg.C for 8 hr, and separating and purifying by column chromatography to obtain 6.2g of product (III)₅) The yield of this step: 94.6 percent.

(3) 6.0g of product (III) are then introduced₅) Adding 1.8g hydrazine hydrate into 35mL absolute ethyl alcohol, heating and refluxing for 9h at 90 ℃, and finally separating and purifying by column chromatography to obtain 5.5g product aryl pyrazole hydrazide compound (IV)₅) The yield of this step: 94.2 percent.

(4) A100 mL flask was charged with 5.5g of an arylpyrazole hydrazide compound (IV)₅) Adding a drop of triethylamine as an acid-binding agent into 20mL of dichloromethane and 2.4g of 4-tert-butylbenzene sulfonyl chloride, placing the mixture into an ultrasonic reactor (fixed power 140W) to react for 4 hours at the temperature of 75 ℃, and performing suction filtration and drying to obtain 6.9g of aryl pyrazole sulfonyl hydrazide ligand (V)₅). Yield of this step: 93.7 percent.

(5) 6.5g of aryl pyrazole sulfonylhydrazide ligand (V) was added to a 100mL three-necked flask₅) 40mL of THF and 30mL of cobalt acetate ethanol solution (5.5g of cobalt acetate is dissolved in 30mL of absolute ethanol), a reflux condenser tube and a thermometer are arranged, the three-neck flask is placed into an ultrasonic reactor (fixed power 190W) for reaction, the temperature is heated to 80-90 ℃ in a water bath, and the reaction time is 4 hours. After the reaction is finished, preparing a sample by a dry method, and separating by column chromatography (V)_{Ethyl acetate}：V_{Petroleum ether}1: 1) 6.7g of the compound (VI) were obtained₅) The yield of this step: 95.7 percent. mp 255.3-256.6 ℃ IR (KBr, cm)^-1) 3225(N-H),3075(C-H),1669(-C ═ O),1620 (vibrating pyrazole ring skeleton), 1545 and 1380 (vibrating benzene ring skeleton), 1316(C-F),889 (aromatic ring C-H).¹HNMR(CDCl₃,400MHz)δ:10.10(s,1H,N-H),10.05(s,1H,N-H),8.73(s,2H,Ar-H),765(s,2H,Ar-H),7.57(s,2H,Ar-H),7.44(s,1H,Ar-H),7.33(s,2H,Ar-H),5.7(s,2H,Ar-H),4.2(s,1H,N-H),1.44(s,3H,C-H₃)。

Example 6 Arylpyrazole sulfonylhydrazide metallic Nickel (Compound (VI)₆) Synthesis of

Formation of Compound (VI)₆) The reaction formula (A) is as follows:

the method sequentially comprises the following steps:

(1) 5.0g of arylpyrazole compound I₆Adding 1.9g of ethylsulfonyl chloride into 40ml of N-dimethyl formyl solution, adding 1.0g of NaH solid into the solution, reacting the solution at 100 ℃ for 12 hours in an ultrasonic reactor (fixed power 140W), and finally separating and purifying by column chromatography to obtain 5.9g of a product (II)₆) The yield is as follows: 93.7 percent.

(2) 5.5g of product (II)₆) With 4.5g of anhydrous FeCl₃Adding into 40mL anhydrous ethanol, heating and refluxing at 120 deg.C for 7h, and separating and purifying by column chromatography to obtain 5.8g product (III)₆) The yield of this step: 95.1 percent.

(3) 5.5g of product (III)₆) Adding 1.5g hydrazine hydrate into 35mL absolute ethyl alcohol, heating and refluxing for 10h at 110 ℃, and finally separating and purifying by column chromatography to obtain 5.0g product aryl pyrazole hydrazide compound (IV)₆) The yield of this step: 93.6 percent.

(4) A100 mL flask was charged with 5.0g of an arylpyrazole hydrazide compound (IV)₆) Adding a drop of triethylamine as an acid-binding agent into 20mL of dichloromethane and 2.4g of p-nitrobenzenesulfonyl chloride, placing the mixture into an ultrasonic reactor (constant power 140W) to react for 3 hours at the temperature of 85 ℃, and performing suction filtration and drying to obtain 6.6g of aryl pyrazole sulfonyl hydrazide ligand (V)₆) The yield of this step: 94.8 percent.

(5) 6.5g of aryl pyrazole sulfonylhydrazide ligand (V) was added to a 100mL three-necked flask₆) 40mL of DMF and 25mL of nickel acetate ethanol solution (8g of nickel acetate is dissolved in 25mL of absolute ethanol), a reflux condenser tube and a thermometer are arranged, the three-neck flask is placed into an ultrasonic reactor (with fixed power of 180W) for reaction, the temperature is heated to 75-85 ℃ in water bath, and the reaction time is 4 hours. After the reaction is finished, preparing a sample by a dry method, and separating by column chromatography (V)_{Ethyl acetate}：V_{Petroleum ether}1: 1) 6.8g of the compound (VI) are obtained₆) The yield of this step: 95.7 percent. The mp is 193.6-194.5 ℃, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

Example 7 Arylpyrazole sulfonylhydrazide metallic iron (Compound (VI)₇) Synthesis of

Formation of Compound (VI)₇) The reaction formula (A) is as follows:

the method sequentially comprises the following steps:

(1) 5.0g of arylpyrazole compound I₇Adding 1.7g phenylacetyl chloride into 40ml N-dimethylformamide, adding 1.0g NaH solid, reacting at 90 deg.C for 14h in ultrasonic reactor (fixed power 140W), and separating and purifying by column chromatography to obtain 6.0g product (II)₇) The yield is as follows: 95.5 percent.

(2) 6.0g of product (II)₇) With 5.1g of anhydrous FeCl₃Adding into 40mL anhydrous ethanol, heating and refluxing at 110 deg.C for 10h, and separating and purifying by column chromatography to obtain 6.1g product (III)₇) The yield of this step: 94.7 percent.

(3) 6.0g of product (III) are then introduced₇) Adding 1.5g hydrazine hydrate into 40mL absolute ethyl alcohol, heating and refluxing for 11h at 90 ℃, and finally separating and purifying by column chromatography to obtain 5.6g product aryl pyrazole hydrazide compound (IV)₇) The yield of this step: 95.5 percent.

(4) A100 mL flask was charged with 5.5g of an arylpyrazole hydrazide compound (IV)₇) 20mL of dichloromethane and 1.8g of 4-fluorobenzenesulfonyl chloride, then adding a drop of triethylamine as an acid-binding agent, putting the mixture into an ultrasonic reactor (with fixed power of 140W), reacting for 2.5h at the temperature of 95 ℃, filtering by suction, and drying to obtain 6.7g of aryl pyrazole sulfonyl hydrazide ligand (V is the ligand of the aryl pyrazole sulfonyl hydrazide)₇) The yield of this step: 97.1 percent.

(5) 6.5g of aryl pyrazole sulfonylhydrazide ligand (V) was added to a 100mL three-necked flask₇) 40mL of DMSO and 30mL of iron acetate ethanol solution (6.5g of iron acetate dissolved in 30mL of absolute ethanol), a reflux condenser tube and a thermometer are arranged, the three-necked flask is placed into an ultrasonic reactor (with fixed power of 160W) for reaction, the temperature is heated to 75-85 ℃ in a water bath, and the reaction time is 3.5 h. After the reaction is finished, preparing a sample by a dry method, and separating by column chromatography (V)_{Ethyl acetate}：V_{Petroleum productsEther compounds}1: 1) 6.2g of the compound (VI) are obtained₇) The yield of this step: 95.3 percent. mp is 178.2-179.6 ℃, the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

Example 8 Arylpyrazole sulfonylhydrazide manganese Metal (Compound (VI)₈) Synthesis of

Formation of Compound (VI)₈) The reaction formula (A) is as follows:

the method sequentially comprises the following steps:

(1) 5.0g of arylpyrazole compound I₈Adding 2.5g of cinnamoyl chloride into 40mLN, N-dimethylformamide, adding 1.0g of NaH solid into the dimethylformamide, reacting the mixture for 12 hours at 90 ℃ in an ultrasonic reactor (fixed power of 140W), and finally separating and purifying by column chromatography to obtain 6.5g of a product (II)₈) The yield is as follows: 94.2 percent.

(2) 6.5g of product (II)₈) With 5.0g of anhydrous FeCl₃Adding into 40mL anhydrous ethanol, heating and refluxing at 100 deg.C for 9h, and separating and purifying by column chromatography to obtain 7.0g product (III)₈) The yield of this step: 97.7 percent.

(3) 7.0g of product (III) are then introduced₈) Adding 2.0g hydrazine hydrate into 45mL absolute ethyl alcohol, heating and refluxing for 9h at 90 ℃, and finally separating and purifying by column chromatography to obtain 6.5g product aryl pyrazole hydrazide compound (IV)₈) The yield of this step: 95.4 percent.

(4) 6.5g of arylpyrazole hydrazide compound (IV) was placed in a 100mL flask₈) 20mL of dichloromethane and 2.4g of thiophene-2-sulfonyl chloride, then adding a drop of triethylamine as an acid-binding agent, putting the mixture into an ultrasonic reactor (with fixed power of 140W) to react for 3 hours at the temperature of 90 ℃, and performing suction filtration and drying to obtain 8.3g of aryl pyrazole sulfonyl hydrazide ligand (V8), wherein the yield of the step is as follows: 96.5 percent.

(5) A100 mL three-necked flask was charged with 8.0g of an arylpyrazole sulfonylhydrazide ligand (V)₈) 45mL of benzene solution, 20mL of manganese acetate in ethanol (6g of manganese acetate in 20)mL absolute ethyl alcohol), a reflux condenser tube and a thermometer are arranged, the three-mouth bottle is placed into an ultrasonic reactor (with fixed power of 160W) for reaction, the temperature is heated to 75-80 ℃ in water bath, and the reaction time is 5 h. After the reaction is finished, preparing a sample by a dry method, and separating by column chromatography (V)_{Ethyl acetate}：V_{Petroleum ether}1: 1) 8.5g of the compound (VI) are obtained₈) The yield of this step: 97.7 percent. The mp is 192.5-193.6 ℃, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

Example 9 Arylpyrazole sulfonylhydrazide metallic iron (Compound (VI)₉) Synthesis of

Formation of Compound (VI)₉) The reaction formula (A) is as follows:

the method sequentially comprises the following steps:

(1) 5.0g of arylpyrazole compound I₉Adding 1.2g chloropropene into 40ml N-dimethyl formamide, adding 1.0g NaH solid, reacting at 110 deg.C for 13h in ultrasonic reactor (fixed power 140W), and separating and purifying by column chromatography to obtain 5.4g product (II)₉) The yield is as follows: 96.2 percent.

(2) 5.0g of product (II)₉) With 4.5g of anhydrous FeCl₃Adding into 36mL anhydrous ethanol, heating and refluxing at 100 deg.C for 9h, and separating and purifying by column chromatography to obtain 5.2g product (III)₉) The yield of this step: 92.7 percent.

(3) 5.0g of product (III) are then introduced₉) Adding 1.0g hydrazine hydrate into 40mL absolute ethyl alcohol, heating and refluxing for 10h at 90 ℃, and finally separating and purifying by column chromatography to obtain 4.6g product aryl pyrazole hydrazide compound (IV)₉) The yield of this step: 95.8 percent.

(4) A100 mL flask was charged with 4.5g of an arylpyrazole hydrazide compound (IV)₉) 20mL of dichloromethane, 3.2g of 2,4, 6-trichlorobenzenesulfonyl chloride, then adding a drop of triethylamine as an acid-binding agent, putting the mixture into an ultrasonic reactor (with fixed power of 140W) to react for 4.5 hours at the temperature of 70 ℃, and pumpingFiltering and drying to obtain 7.0g of aryl pyrazole sulfonyl hydrazide ligand (V)₉) The yield of this step: 97.0 percent.

(5) In a 100mL three-necked flask was added 7.0g of arylpyrazole sulfonylhydrazide ligand (V)₉) 40mL of toluene solution and 25mL of iron acetate ethanol solution (6g of iron acetate dissolved in 25mL of absolute ethanol), a reflux condenser tube and a thermometer are arranged, the three-necked flask is placed into an ultrasonic reactor (with fixed power of 170W) for reaction, the temperature is heated to 75-85 ℃ in a water bath, and the reaction time is 4 hours. After the reaction is finished, preparing a sample by a dry method, and separating by column chromatography (V)_{Ethyl acetate}：V_{Petroleum ether}1: 1) 7.4g of the compound (VI) are obtained₉) The yield of this step: 96.8 percent. The mp is 195.6-196.1 ℃, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

Example 10 Arylpyrazole sulfonylhydrazide Metal Zinc (Compound (VI)₁₀) Synthesis of

Formation of Compound (VI)₁₀) The reaction formula (A) is as follows:

the method sequentially comprises the following steps:

(1) 5.0g of arylpyrazole compound I₁₀Adding 2.0g of 2-chloroethane sulfonyl chloride into 40mLN, N-dimethylformamide, adding 1.0g of NaH solid, reacting at 110 ℃ for 14h in an ultrasonic reactor (fixed power 140W), and finally separating and purifying by column chromatography to obtain 6.0g of product (II)₁₀) The yield is as follows: 98.0 percent.

(2) 6.0g of product (II)₁₀) With 4.0g of anhydrous FeCl₃Adding into 40mL anhydrous ethanol, heating and refluxing at 120 deg.C for 8h, and separating and purifying by column chromatography to obtain 6.3g product (III)₁₀) The yield of this step: 96.2 percent.

(3) 6.0g of product (III) are then introduced₁₀) And 1.Adding 5g of hydrazine hydrate into absolute ethyl alcohol, heating and refluxing for 10h at 100 ℃, and finally separating and purifying by column chromatography to obtain 5.6g of arylpyrazole hydrazide compound (IV)₁₀) The yield of this step: 97.7 percent.

(4) A100 mL flask was charged with 5.5g of an arylpyrazole hydrazide compound (IV)₁₀) 20mL of dichloromethane and 2.1g of 4-methoxybenzenesulfonyl chloride, then a drop of triethylamine is added as an acid-binding agent, the mixture is put into an ultrasonic reactor (with fixed power of 140W) to react for 3 hours at the temperature of 80 ℃, and 7.0g of aryl pyrazole sulfonyl hydrazide ligand (V) is obtained after suction filtration and drying₁₀) The yield of this step: 96.7 percent.

(5) In a 100mL three-necked flask was added 7.0g of arylpyrazole sulfonylhydrazide ligand (V)₁₀) 40mL of acetone solution and 30mL of zinc acetate ethanol solution (7g of zinc acetate dissolved in 30mL of absolute ethanol), a reflux condenser tube and a thermometer are arranged, the three-necked flask is placed into an ultrasonic reactor (with fixed power of 180W) for reaction, and the reaction is carried out in a water bath for 5 hours under the condition of heating to 80-90 ℃. After the reaction is finished, preparing a sample by a dry method, and separating by column chromatography (V)_{Ethyl acetate}：V_{Petroleum ether}1: 1) 7.3g of the compound (VI) were obtained₁₀) The yield of this step: 96.1 percent. mp is 183.2-184.6 ℃, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

Comparative example 11 Synthesis of Arylpyrazole sulfonylhydrazide Metal copper Complex (Compound (VI 1))

Compound (VI 1) was prepared by separately or simultaneously changing the temperature, reaction time and heating pattern of step (5) of example 1 and the other steps were the same as in example 1, and the preparation results are shown in Table 1 below together with the results of example 1, and the yield in Table 1 is the yield of step (5).

TABLE 1 Synthesis and yield of Compound (VI 1) under different conditions

From the three groups of comparative examples 1-3, the yield is influenced by temperature and time, and the yield is obviously improved by using ultrasonic treatment under normal pressure compared with the yield without ultrasonic treatment.

Example 12 Water solubility of aryl pyrazole sulfonylhydrazide Metal Complex

The sulfonyl hydrazide structure and metal ions have higher hydrophilicity, so that the water solubility of the whole compound can be improved when the sulfonyl hydrazide structure and the metal ions are combined with the arylpyrazole compound, and the higher the solubility of the compound in water is, the more the toxicity of the compound in water can be detected. For comparison with fipronil, the water solubility of the compound (VI 1-10) in water at 25 ℃ and pH 7.0 was compared, and the results are shown in Table 2.

TABLE 2 Water solubility of Compound (VI 1-10) in Water at 25 ℃ and pH 7.0

Example 13 preparation of an aryl pyrazole sulfonylhydrazide Metal Complex pesticide for experiments

The pesticide formulation prepared in this example was a suspending agent, and the term "total mass" hereinafter means "total mass of the suspending agent prepared".

Firstly, 10 parts of a sodium naphthalenesulfonate formaldehyde condensate which is a surfactant and accounts for 5 percent of the total mass is respectively diluted into 10 parts of ethylene glycol which is an appropriate antifreeze and accounts for 5 percent of the total mass, water which accounts for 25 percent of the total mass is respectively and slowly added into the solution, the compounds (VI 1 to VI 10) which are prepared in the examples 1 to 10 and auxiliary agents (a preservative, benzoic acid, an antifoaming agent, organosilicon and a thickening agent, xanthan gum) which account for 25 percent of the total mass are respectively and sequentially added into 10 groups of solutions under the condition of rapid stirring, the materials are ground after the addition is finished, and finally, water which accounts for 35 percent of the total mass is added. And diluting the prepared suspending agent with water to respectively prepare diluted suspending agents with the concentrations of the compounds (VI 1-VI 10) of 20, 40, 60, 80, 100, 120, 140, 160, 200 and 300 mg/L. I.e. 10 compound groups, 5 concentration gradients per group.

The diluted suspension concentrates prepared were ready for use in the following examples.

Example 14 evaluation of fungicidal Activity

Using 10 groups of the diluted suspensions of example 13 each having a concentration of 160mg/L, 5mL of the diluted suspension was poured into a petri dish, and 10mL of potato dextrose agar (PSA) medium was added to prepare a test compound-containing plate (drug-containing plate) having a final mass concentration of 80 mg/L. The cultured test bacteria were punched out into 5 mm-diameter cake with a punch, and placed in a drug-containing plate with 3 pieces per dish. Blank control was performed without drug. After culturing for 48h in an incubator at the temperature of 25 +/-1 ℃, measuring the expansion diameter of each treated hypha, further calculating the bacteriostasis rate of each hypha, and comparing the hypha with a fipronil control. The results of the bactericidal activity test on 5 plant pathogens are shown in table 3.

TABLE 3 Activity test of Compounds (VI 1 to 10) against pathogenic bacteria

From the results in table 3, it can be seen that: fipronil has 40-50% inhibition effect on pathogenic bacteria, and the compounds (VI 1-VI 10) have 80-95% inhibition effect on various pathogenic bacteria.

Example 15 evaluation of biological Activity of Polygala crotalarioides

Using 10 groups of the diluted suspension concentrates of example 13 with a concentration of 160mg/L, 1kg of wet soil was filled in 10 culture tanks, and the soil water was maintained. 50 seeds of the myrtle are sown in each tank, the depth is 5mm, the myrtle grows for a plurality of days at room temperature, when the myrtle grows to the 2-leaf stage, 10-15 drops of 160mg/L diluted suspending agent of the compound (VI 1-10) are respectively dripped into each tank, the death rate is observed after two days, the experiment is repeated for 3 times, and the average value is obtained. The results are shown in Table 4.

TABLE 4 Activity test of compound (VI 1-10) Myrtle

Compound (I)	Fipronil	(Ⅵ₁)	(Ⅵ₂)	(Ⅵ₃)	(Ⅵ₄)	(Ⅵ₅)	(Ⅵ₆)	(Ⅵ₇)	(Ⅵ₈)	(Ⅵ9)	(Ⅵ₁₀)
												Mortality (%)	67.8	92.3	91.0	93.3	88.3	93.3	89.3	87.9	90.2	92.1	92.6

From the results in table 4, it can be seen that: the compounds (VI 1 to VI 10) have better weeding effect on the alopecurus as compared with the fipronil.

Example 16 evaluation of biological Activity of Rainflorescence

10 groups of 160mg/L diluted suspending agents were used, respectively, at an area of 10m²The small test fields are sown with 200 seeds of the long-noded sedge, buried in a soil layer with the depth of 0.5cm, drenched and cultivated in a greenhouse. When the plant grows to the 4-leaf stage, each small test field is uniformly sprayed with 300mL of 160mg/L diluted suspending agent of a compound (VI 1-VI 10), the mortality is observed after two days, the experiment is repeated for 3 times, and the result is averaged. The activity is divided into A, B, C, D grades relative to a blank control by percentage, wherein the mortality rate of 100-90 percent is A grade, the mortality rate of 90-70 percent is B grade, the mortality rate of 70-50 percent is C grade, and the mortality rate of 0-50 percent is D grade. The test results are shown in Table 5.

TABLE 5 Activity of Compounds (VI 1-10) on Podospora damascena at a test concentration of 160mg/L

Compound (I)

Fipronil

(Ⅵ₁)

(Ⅵ₂)

(Ⅵ₃)

(Ⅵ₄)

(Ⅵ₅)

(Ⅵ₆)

(Ⅵ₇)

(Ⅵ₈)

(Ⅵ9)

(Ⅵ₁₀)

Active grade

C

A

B

A

B

A

B

A

From the results in table 5, it can be seen that: the active grade of the fipronil on the long-standing rain flower is C, the active grade of the compounds (VI 1-VI 10) on the long-standing rain flower is A or B, and the compounds (VI 1-VI 10) have better weeding effect on the long-standing rain flower than the fipronil.

Example 17 evaluation of biological Activity against aphids

Using the diluted suspensions of 160mg/L concentration of 10 groups of compounds prepared in example 13, two seedlings of rice were selected and soaked in the solution, and after 5 seconds, they were taken out and dried, and placed in large test tubes, 40 plants per tube, then 20 or more aphids of 5-year-old nymphs were introduced, and the mouths of the tubes were wrapped with white gauze and placed at room temperature, and after 24 hours, the number of the surviving and dead insects was checked. The experiment was repeated 3 times. The results were averaged. The activity is classified into A, B, C, D grades relative to a blank control in percentage, wherein the mortality rate of 100-90% is A grade, the mortality rate of 90-70% is B grade, the mortality rate of 70-50% is C grade, and the mortality rate of 0-50% is D grade. The test results are shown in Table 6.

TABLE 6 Activity of Compounds (VI 1-10) against aphids at a concentration tested of 160mg/L

Compound (I)

Fipronil

(Ⅵ₁)

(Ⅵ₂)

(Ⅵ₃)

(Ⅵ₄)

(Ⅵ₅)

(Ⅵ₆)

(Ⅵ₇)

(Ⅵ₈)

(Ⅵ9)

(Ⅵ₁₀)

Active grade

C

B

A

B

A

B

A

B

From the results in table 6, it can be seen that: the level of the fipronil activity to aphids is C, the level of the compound (VI 1-VI 10) activity to aphids is A or B, and the compound (VI 1-VI 10) has better control function to aphids than the fipronil.

Example 18 evaluation of biological Activity of Tetranychus urticae

Placing the spider mites to be tested on the double-sided adhesive tape of the glass slide in an indoor environment at the temperature of 25 +/-1 ℃ for 2 hours, removing dead and inactive individuals, and recording the number of live mites. Soaking one end with mite into diluted suspending agent with concentration of 100mg/L prepared for each compound, taking out after 5s, and quickly sucking off excess medicinal liquid around mite body with absorbent paper. The culture was incubated for 3D at 25. + -. 1 ℃ under light (L: D: 16 h: 8h) and the results were examined 1 time every 24 h. The body was touched with a brush pen, and the mite with the mite was dead. The diluted suspension test for each compound was repeated 3 times and the results averaged. The activity is divided into A, B, C, D grades relative to a blank control by percentage, wherein the mortality rate of 100-90 percent is A grade, the mortality rate of 90-70 percent is B grade, the mortality rate of 70-50 percent is C grade, and the mortality rate of 0-50 percent is D grade. The test results are shown in Table 7.

TABLE 7 Compound (VI)₁～Ⅵ₁₀) Activity against Tetranychus urticae at a concentration of 100mg/L

Compound (I)

Fipronil

(Ⅵ₁)

(Ⅵ₂)

(Ⅵ₃)

(Ⅵ₄)

(Ⅵ₅)

(Ⅵ₆)

(Ⅵ₇)

(Ⅵ₈)

(Ⅵ9)

(Ⅵ₁₀)

Active grade

C

B

A

B

A

B

From the results in Table 7, it can be seen that: the activity level of the fipronil to the tetranychus urticae is C, the activity level of the compounds (VI 1-VI 10) to the tetranychus urticae is A or B, and the compounds (VI 1-VI 10) have better control effect on the tetranychus urticae than the fipronil.

Example 19 evaluation of biological Activity of Chinese honeybees

To verify whether the safety of apis cerana bees was improved by using diluted suspensions of 80 and 160mg/L concentrations of 10 groups of compounds prepared in example 13, the total toxicity (contact toxicity and stomach toxicity) of apis cerana bees was determined by the spray method using worker bees as test insects, and the results are shown in table 8.

TABLE 8 toxicity test results of compounds (VI 1-10) on Apis cerana at 48h

From the results in Table 8, it can be seen that: fipronil has high toxicity to Chinese bees, has a poisoning rate of 10% at 80mg/L, and has a poisoning death rate of approximately half at 160mg/L, which reaches 45%; it is mainly manifested as a flaccid body or death. The compound (VI 1-10) has relatively low comprehensive toxicity to Chinese bees, no poisoning is shown when the compound is treated at 80mg/L, and a slight poisoning symptom is shown in 1 Chinese bee in a test that only one group of compounds are treated at 160mg/L (the compound (VI 5)). If the treatment mass concentration with the poisoning rate not higher than 3% is defined as the safe mass concentration, the safe mass concentration of the compound (VI 1-10) to China bees is at least 160mg/L, which is at least 1 time higher than that of fipronil (<80 mg/L).

Example 20 evaluation of photodegradability of Compounds (VI 1 to 10)

Xenon lamp (350W) is used as a light source for simulating sunlight, and compounds (VI 1-10) are respectively used as photodegradation substrates with the concentration of 1 multiplied by 10^-4mol/L. In view of the formation ofThe compound (VI 1-10) has low solubility in pure water, and acetonitrile is added as a cosolvent. And (3) determining the concentration of the compound (VI 1-10) degraded at different moments by using high performance liquid chromatography. The chromatographic conditions were as follows: the chromatographic column is a phenomenex C18 chromatographic column (250nm multiplied by 4.6mm,5 μm); mobile phase is V_Acetonitrile：V_{Water (W)}62: 38; the flow rate is 1.0 mL/min; the detection wavelength is 250 nm; the amount of the sample was 20. mu.L. The experiment was repeated 3 times and the results averaged. And (3) calculating the degradation rate, and exploring the photodegradability of the compound (VI 1-10). The results are shown in Table 9.

TABLE 9 photodegradation rates of the compounds (VI 1-10) at different times

From table 9, it can be seen that: the compound (VI 1-10) has low photodegradation rate within 8 hours and can well exert the drug effect; the compound (VI 1-10) has high photodegradation rate after 72 hours, has low pesticide residue, is environment-friendly and is a green and environment-friendly pesticide.

Claims

1. An aryl pyrazole sulfonyl hydrazide metal complex, which has a structural formula shown in a general formula (VI):

in the general formula (VI), R₁Any one selected from the following groups:

—CH₂CH₂CH₂CH₃、

R₂any one selected from the following groups: -CCl₃、-CH₂CH₃、-CH₂CH₂CH₂CH₃、

R₃Any one selected from the following groups:

m is selected from any one of the following metals: fe. Ni, Zn, Mn, Cu, Mo.

2. A method for synthesizing arylpyrazole sulfonyl hydrazide metal complex as claimed in claim 1, comprising the steps of:

in a first step, arylpyrazole compounds

With compounds R₁Adding the-X into N, N-dimethylformamide, adding NaH solid, reacting at 60-180 deg.C for 6-18h in ultrasonic reactor, and separating and purifying by column chromatography to obtain product (II)

Secondly, the product (II) is mixed with anhydrous FeCl₃Adding the mixture into absolute ethyl alcohol, heating and refluxing the mixture for 6 to 12 hours at the temperature of between 90 and 150 ℃, and finally separating and purifying the mixture by column chromatography to obtain a product (III)

In a third step, the product (III) is hydratedAdding hydrazine into anhydrous ethanol, heating and refluxing at 80-120 deg.C for 9-12h, and separating and purifying by column chromatography to obtain product (IV)

The fourth step is to react the product (IV) with sulfuryl chloride

Adding the mixture into dichloromethane, adding organic amine serving as an acid-binding agent into the dichloromethane, and reacting for 0.5 to 5 hours at the temperature of 60 to 120 ℃ under ultrasonic radiation to obtain an aryl pyrazole sulfonyl hydrazide ligand (V)

Fifthly, adding the aryl pyrazole sulfonyl hydrazide ligand (V) and a metal salt solution into an organic solvent, reacting for 2-10h at 55-105 ℃ under ultrasonic radiation, and separating a product (VI) after the reaction is finished;

the R is₁、R₂、R₃As defined above; the metal salt is ferric salt, nickel salt, zinc salt, manganese salt, copper salt and molybdenum salt, and the compound R₁X in X is-Cl or-Br.

3. The method of claim 2, wherein the organic solvent is benzene, toluene, acetone, tetrahydrofuran, DMF, or DMSO.

4. The method of claim 2, wherein the iron salt is ferric nitrate, ferric acetate, ferric sulfate, or ferric chloride; the nickel salt is nickel acetate, nickel sulfate, nickel nitrate or nickel chloride; the zinc salt is zinc acetate, zinc chloride, zinc nitrate or zinc sulfate; the manganese salt is manganese nitrate, manganese sulfate, manganese acetate or manganese chloride; the copper salt is copper nitrate, copper acetate, copper sulfate, copper carbonate or copper chloride; the molybdenum salt is molybdenum chloride, phosphomolybdic acid or molybdenum nitrate.

5. The use of an arylpyrazole sulfonyl hydrazide metal complex as claimed in claim 1 in a plant fungicide.

6. Use of an arylpyrazole sulfonyl hydrazide metal complex as claimed in claim 1 in a herbicide for controlling gramineous weeds and/or dicotyledonous weeds.

7. Use of the arylpyrazole sulfonyl hydrazide metal complex as claimed in claim 1 in a medicament for controlling harmful insect and/or acarid pests.