CN109651379B

CN109651379B - Pentaaza and/or oxo-dithio-dicyclo-dienone-containing compound and microwave solvent thermal synthesis method and application thereof

Info

Publication number: CN109651379B
Application number: CN201910100877.0A
Authority: CN
Inventors: 陈连清; 吴忠达; 马权
Original assignee: South Central University for Nationalities
Current assignee: South Central Minzu University
Priority date: 2019-01-31
Filing date: 2019-01-31
Publication date: 2020-08-28
Anticipated expiration: 2039-01-31
Also published as: CN109651379A

Abstract

The invention relates to the technical field of organic synthesis, in particular to pentaaza and/or oxo-dithio-bicyclo-diene ketone compounds and a microwave solvothermal synthesis method thereof, and also relates to application of the compounds in insect killing, bacteriostasis and weeding and research on fluorescence property and photodegradation efficiency. The ketene structure is introduced into nitrogen, oxygen and sulfur heterocycles simultaneously according to the splicing principle of an active structure, so that a series of green, environment-friendly, multifunctional, strong-drug-effect and novel-structure compounds, namely pentaaza and/or oxo-dithiodienone compounds are successfully synthesized, the purpose of reducing the drug dosage by connecting a plurality of groups with drug activity on one molecule is achieved, a specific microwave solvothermal synthesis method is provided, the synthesis method can change reaction raw material components to synthesize the compounds with different structures according to actual conditions, and the insecticidal, bacteriostatic and herbicidal activities, the fluorescent property and the photodegradation property of the compounds are tested, so that good effects are achieved.

Description

Pentaaza and/or oxo-dithio-dicyclo-dienone-containing compound and microwave solvent thermal synthesis method and application thereof

Technical Field

The invention relates to the technical field of organic synthesis, in particular to a pentaaza and/or oxo-dithio-bicyclo-diene ketone compound and a microwave solvothermal synthesis method thereof, and also relates to application of the compound in insecticidal, bacteriostatic and herbicidal medicaments and application of the compound in degradable fluorescent pesticides.

Background

The common heteroatoms are nitrogen, oxygen and sulfur, and nitrogen, oxygen and sulfur heterocyclic compounds are a very important class of heterocyclic molecules, and most of the heterocyclic molecules have biological activity and pharmacological activity. As intermediates of medicines, pesticides, natural medicines, dyes and other chemicals, nitrogen, oxygen, sulfur heterocyclic compounds and derivatives thereof are applied more and more widely, and the occupied position in production and life is more and more important. Therefore, artificial synthesis of nitrogen, oxygen and sulfur heterocyclic compounds is very necessary, and various methods can be used for synthesizing the heterocyclic compounds so far, but the search and development of a novel, efficient, environment-friendly, mild reaction condition and simple and convenient method for quickly synthesizing the compound which has a novel structure and simultaneously contains nitrogen, oxygen and sulfur heterocyclic skeleton still has certain challenges. The nitrogen-containing heterocyclic compound generally has unique biological activity, low toxicity and high systemic property, is easy to carry out structural modification, conveniently introduces various functional groups, and is often used as a structural unit of medicines and pesticides. In 2011, a synthetic method for forming nitrogen-nitrogen bonds by catalysis of a copper complex is reported by a Rao subject group, cuprous iodide is used as a catalyst in the reaction, and alpha-aryl alkenyl azide aldehyde and arylamine are subjected to a series reaction to generate pyrazole compounds, and the pyrazole compounds have the characteristics of wide action spectrum, strong drug effect and the like, and can be used for the aspects of pain relief, inflammation resistance, oxidase inhibitors, insect killing, bacteriostasis, weeding and the like.

Ketene is an organic synthesis reagent with very active chemical properties, which is synthesized as early as the beginning of the century, and has great potential in the aspect of photophysical properties, so that the ketene research interest is aroused, and the ketene is one of the more ideal frequency doubling materials discovered so far. Has wide biological activity due to unique structural properties, and mainly shows in the aspects of killing pests, weeding, resisting viruses, resisting inflammation and the like. The most representative compound is cyclohexenone herbicide designed and synthesized by Bandyopadhyay et al, and the herbicidal activity of the compound is evaluated, which shows that the compound has good herbicidal activity.

Some compounds with excellent photosensitive property are sensitive materials for detecting trace organic pesticide residues in grains and food, and the interaction between the compounds and a detected object causes rearrangement of electronic dipole moment to cause change of absorption spectrum, so that the compounds can be easily detected. The spectrum technology is a rapid nondestructive detection method widely researched and used in recent years, wherein the fluorescence spectrum technology is used for detecting pesticide residues by exciting a fluorescent substance in a crop body through light source pulse amplitude modulation and then acquiring a fluorescence emission spectrum through a reflection principle. At present, few reports about fluorescent pesticides exist in the field, and the reports about fluorescent properties of pesticide structures themselves are less.

At present, nitrogen, oxygen and sulfur heterocyclic compounds are complex in synthesis operation steps and poor in selectivity, reaction conditions need to be controlled more rigorously to generate target products, aftertreatment is difficult, energy and raw materials are consumed more greatly, the yield of final products is low, and the industrial batch production is not facilitated. Alkyl, aryl and other heterocyclic derivatives are introduced into nitrogen, oxygen and sulfur heterocycles, but the introduction of an enone structure is less, and pentaaza-or oxo-dithiobicyclo-diene ketones which simultaneously introduce the enone into the nitrogen, oxygen and sulfur heterocycles and form a bicyclic structure are more rarely used.

With the rapid development of microwave technology, microwave organic synthesis reaction, in which reactants are reacted under the radiation of microwave, needs a special reaction technology unlike conventional organic synthesis reaction, has been gradually applied to various fields. In 1986, Richard Gedye et al first introduced microwave into organic synthesis reaction by using a microwave closed reactor, which was placed in a microwave source with reactants and then subjected to microwave irradiation to complete the reaction. The solvothermal synthesis method has been applied to synthesis of various inorganic catalysts, porous materials with metal organic frameworks and the like, and can be used for placing reactants in a high-temperature high-pressure closed container for reaction, so that the dissolution and dispersion of the reactants and the effective collision degree of molecules under the condition of violent overturning boiling are far higher than that of mechanical stirring under normal pressure, and the yield of target products is greatly improved.

Disclosure of Invention

As most of nitrogen, oxygen and sulfur heterocyclic compounds have stronger biological and pharmacological activities, for example, the nitrogen-containing heterocyclic compound pyrazole compounds have good application prospects in the aspects of disinsection, bacteriostasis, weeding and the like, and the ketene compounds have great potential in the aspects of photophysical properties and weeding activity. On the basis of summary documents, the applicant combines the antibacterial activity, the insecticidal activity, the super-strong herbicidal activity and the photophysical performance of a compound with a ketene structure according to the principle that functional groups with different activities are aggregated in the same molecule to obviously improve the biological activity of the compound, uses primary amine, alkyl alcohol, hydrazine hydrate, binary sulfonyl chloride and binary acyl halide with various structures as main raw materials, uses strong acid and weak base salts as catalysts and inorganic base as alkaline reagents, synthesizes a series of novel compounds containing pentaaza or oxo-dithiabicyclo-ketene by a microwave solvothermal synthesis method, tests the antibacterial, insecticidal and herbicidal activities, the fluorescent property and the photodegradation efficiency of the compounds, and obtains better effects. The synthesized compound with the self-fluorescence property can be used for detecting the drug residue in crops, and the structure of the compound has certain self-degradation capability under the illumination condition, so that the compound completely accords with the concept of green pesticides, and is expected to play a certain role in the practical application of the pesticides.

Based on the consideration, the ketene structure is simultaneously introduced into nitrogen, oxygen and sulfur heterocycles according to the active structure splicing principle, a series of green, environment-friendly, multifunctional, strong-drug-effect and novel-structure compounds, namely pentaaza or oxo-dithio-dicyclic dienone compounds are successfully synthesized, the purpose of reducing the drug dosage by connecting a plurality of groups with drug activity on one molecule is achieved, and a specific synthetic method is provided, and the components of reaction raw materials can be changed according to actual conditions to synthesize the compounds with different structures.

Compared with the traditional heating reflux method, the microwave solvothermal synthesis method combines the advantages of the common microwave synthesis method and the solvothermal synthesis method into a whole, and has the advantages that the common microwave synthesis method and the solvothermal synthesis method are not comparable. The method mainly embodies that high-temperature and high-pressure conditions can be formed in a closed solvent thermal reaction kettle under microwave radiation, the reactant is dispersed in a solvent, rolls and boils to increase the collision degree between each reaction molecule, the collision probability on the molecular level is improved, the defects of stirring and uneven heating of the traditional synthetic method are overcome, the reaction time is shortened, the working efficiency is improved, the heating speed is high, the heating is even, no temperature gradient exists, the hysteresis effect exists, the method is a very effective novel organic synthetic method, substances which are difficult to synthesize under normal temperature and normal pressure can be synthesized, the yield of products can be greatly improved, a large amount of preparation can be realized, and the method has an industrial application prospect. In view of the advantages of the microwave solvothermal synthesis method, the invention firstly applies the microwave solvothermal synthesis method to synthesize the pentaaza-and/or oxo-dithio-dicyclic dienone compound.

Based on the above considerations, the present invention has mainly six objects:

the first purpose of the invention is to provide pentaaza and/or oxo-dithio-dicyclo-dienone compounds, the structural formula of which is shown as the general formula (IV):

in the structural general formula (IV): r₁Selected from the group consisting of saturated alkyl, 2-carbinol-propyl, cycloalkyl, pyridazinyl, quinolinyl, benzothiazolyl, piperidinyl, thiadiazolyl, pyrimidinyl, indolyl, 2-ethyl-furyl, 2-ethyl-tetrahydro-furyl, 4-propylmorpholine, substituted thiazolyl, unsubstituted thiazolyl, substituted phenyl, and substituted thiazolylOne of substituted phenyl, substituted naphthyl, unsubstituted naphthyl, substituted pyridyl and unsubstituted pyridyl;

in the substituted phenyl, the substitution is mono-substitution or multi-substitution, the substitution position is ortho-position, meta-position or para-position of a benzene ring, and the substituted group is halogen, alkyl, alkoxy, nitro or trifluoromethyl;

in the substituted naphthyl, the substitution is single substitution, the substituted position is alpha-position or beta-position, and the substituted group is halogen, alkyl, alkoxy or nitro;

in the substituted pyridyl, the substitution is mono-substituted or multi-substituted, the substituted position is 2-position, 4-position, 5-position or 6-position of a pyridine ring, and the substituted group is halogen or alkyl;

in the substituted thiazolyl, the substitution is single substitution, the substituted position is 4-position or 5-position of thiazole ring, and the substituted group is halogen or nitro;

in the structural general formula (IV): y is a partially fluoroalkyl chain, perfluoroalkyl chain, saturated alkyl chain or alkenyl chain, preferably-CF₂-、-CH₂-or-HC ═ CH-;

in the structural general formula (IV): m ═ C ═ O or O ═ S ═ O;

in the structural general formula (IV): n is more than or equal to 1, preferably, n is more than or equal to 1 and less than or equal to 8;

preferably, R is₁Is composed of

Wherein X is halogen;

most preferably, said R₁Is composed of

The second purpose of the invention is to provide a method for synthesizing the compound with the structural formula shown as the general formula (IV), and the method is efficient, environment-friendly, simple and convenient and has low cost.

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

a method for synthesizing pentaaza-and/or oxo-dithio-bicyclic dienone compounds with the structural formula is disclosed, wherein the synthetic route is as follows:

the specific operation steps are as follows:

adding compound (I) into polytetrafluoroethylene lining of microwave reaction kettle

Reaction solvent R₂OH and a catalyst, the reaction kettle is sealed and then placed into a microwave reactor, the microwave power is adjusted to be 200-800W (preferably 450W), the reaction is carried out for 60-420min at 70-300 ℃ (preferably at 120-160 ℃ for 300min, most preferably at 120 ℃ for 300min), after the reaction is finished, an extract C is used for extraction, an organic phase is collected and evaporated to dryness to obtain a compound (II)

(II) reacting the compound (II)

Adding into a polytetrafluoroethylene lining, adding hydrazine hydrate solution and alkyl alcohol, placing the lining into a reaction kettle, sealing the reaction kettle, placing into a microwave reactor, adjusting the microwave power to 300-360min, most preferably 360min at 150 deg.C), removing solvent by rotary evaporation after reaction is stopped, extracting with extract A, collecting organic phase, and extracting with anhydrous MgSO₄Drying, vacuum filtering, adsorbing the filtrate with silica gel, dry sampling, preparing eluent A, purifying by column chromatography to obtain compound (Ш)

(III) adding a compound (Ш) into the polytetrafluoroethylene lining of the microwave reaction kettle

Sealing a reaction kettle, putting the reaction kettle into a microwave reactor, adjusting the microwave power to be 500-350 ℃ and heating to be 100-350 ℃, reacting for 90-540min (preferably reacting for 360min at 180-250 ℃, most preferably reacting for 360min at 180 ℃), pouring the reaction liquid into a rotary evaporation bottle after the reaction is finished and the temperature is reduced to room temperature, removing the organic solvent by using a rotary evaporator to obtain a crude product, adding saturated Na into the crude product₂CO₃Adjusting pH of the solution to 7-8 to remove acidic impurities, adding extract B, extracting, and adding anhydrous MgSO₄Drying, filtering, adsorbing the filtrate with silica gel powder, preparing a sample by a dry method, preparing an eluent B with a certain proportion, and separating and purifying the product by column chromatography to obtain a product (IV);

the structural formula of the compound (IV) is

Wherein R is₁Y, n and M are as defined above;

the compound (I) and the reaction solvent R in the step (one)₂The ratio of-OH to catalyst addition was 1 mmol: 2-10 ml: 0.5-5mmol, preferably 1 mmol: 2-4 ml: 1-2mmol, most preferably 1 mmol: 3 ml: 1mmol of the active component;

adding hydrazine hydrate and alkyl alcohol into the compound (II) in the step (II) and the hydrazine hydrate solution in a proportion of 1 mmol: 3-12 mmol: 1-10ml, preferably 1 mmol: 5-8 mmol: 1-3 ml; most preferably 1 mmol: 6 mmol: 2 ml;

in the step (III), the adding amount ratio of the compound (III), the organic solvent, the alkaline reagent and the acyl halide (or sulfonyl chloride) derivative is 1 mmol: 1-10 ml: 1-5 mmol: 1-1.5mmol, preferably 1 mmol: 2.5-4 ml: 1-2 mmol: 1-1.5 mmol; most preferably 1 mmol: 3 ml: 1.5 mmol: 1.2 mmol;

further, the catalyst in the step (one) is selected from SnCl₄、CoCl₂、Fe₂(SO₄)₃、ZnCl₂、 CuCl₂、FeCl₃、CuSO₄、AlCl₃With Fe (NO)₃)₃At least one of;

preferably, the catalyst is SnCl₄、CuCl₂、ZnCl₂And/or FeCl₃Most preferably FeCl₃；

Further, the reaction solvent R in the step (one)₂-OH is selected from at least one of ethanol, n-propanol, n-butanol, isobutanol, n-pentanol and n-hexanol;

preferably, the reaction solvent R₂-OH is ethanol, n-propanol and/or n-butanol;

further, the alkyl alcohol in the step (two) is selected from at least one of methanol, ethanol, isopropanol, n-butanol, ethylene glycol, isoamyl alcohol, 1, 2-propylene glycol, 1, 3-butylene glycol and diethylene glycol;

preferably, the alkyl alcohol is methanol, ethanol, isopropanol and/or n-butanol; most preferred is methanol or ethanol.

Further, the alkaline reagent in the step (III) is selected from NaH, LiOH, NaOH and Na₂CO₃、 KOH、Cs₂CO₃、Ca(OH)₂And K₂CO₃At least one of;

preferably, the alkaline reagent is NaH, NaOH and/or KOH;

further, the organic solvent in the step (III) is selected from at least one of DMAP, formamide, cyclohexane, tetramethylethylenediamine, pyridine, tetrahydrofuran, DMF and DMSO;

preferably, the organic solvent is pyridine, tetrahydrofuran, DMSO and/or DMF;

further, the hydrazine hydrate solution in the step (II) is a hydrazine hydrate aqueous solution with the concentration of 50-85 wt%;

further, when the acyl halide (or sulfonyl chloride) derivative is selected from a sulfonyl chloride derivative, the sulfonyl chloride derivative is 1, 2-disulfonyl chloroethane, 1, 4-disulfonyl chlorobutane and/or 1, 6-disulfonyl hexane;

further, when the acyl halide (or sulfonyl chloride) derivative is acyl halide chloride derivative, the acyl halide derivative is hexafluoroglutaryl chloride, adipoyl dichloride and/or fumaric dichloride;

further, the eluent A and the eluent B are both a mixture of ethyl acetate, methanol and petroleum ether;

further, the eluent A in the step (two) is a mixture of ethyl acetate, methanol and petroleum ether in a volume ratio of 1:2: 4;

further, the eluent B in the step (three) is a mixture of ethyl acetate, methanol and petroleum ether in a volume ratio of 1:1: 2;

further, the extract A, the extract B and the extract C are all a mixture of ethyl acetate and water;

further, the extract C in the step (one) is a mixture of ethyl acetate and water in a volume ratio of 1: 4;

further, the extract A in the step (II) is a mixture of ethyl acetate and water in a volume ratio of 1: 2;

further, the extract B in the step (III) is a mixture of ethyl acetate and water in a volume ratio of 1: 2.5;

further, the mass ratio of the silica gel powder used for adsorbing the sample in the step (II) and the step (III) in the dry method to the raw material (referred to as filtrate) is 1: 1.2;

the compounds (I) are described in the relevant literature: 5-amino-3-cyano-1- (2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivatives such as Chenlianqing, Chenguizhou, Chengson and the like, and photophysical properties [ J ]. the university of south China college (Nature science edition), 2011,30(1):5-8. the synthesis process is self-made and the synthesis flow is as follows:

r in structure (I)₁As previously described;

the third purpose of the invention is to provide the application of the pentaaza-and/or oxo-dithiobicyclo-dienone-containing compounds in the medicines for preventing and treating the harmful insects of orthoptera, thysanoptera, homoptera, heteroptera, lepidoptera, coleopteran and diptera.

The fourth purpose of the invention is to provide the application of the pentaaza and/or oxo-dithio-dicyclo-dienone compound in antibacterial drugs, and in order to achieve the fourth purpose of the invention, the pentaaza and/or oxo-dithio-dicyclo-dienone compound prepared by the invention is used for the antibacterial activity test of gram-positive bacteria (bacillus anthracis), and has good prevention and treatment effects.

The fifth purpose of the invention is to provide the application of the pentaaza-and/or oxo-dithio-dicyclic dienone compound in the medicines for preventing and killing gramineous weeds and/or broadleaf weeds. In order to realize the fifth purpose of the invention, the pentaaza-and/or oxo-dithiobicyclo-dienone-containing compound prepared by the invention is used for preventing and killing wild oat, setaria viridis, alopecurus canadensis, barnyard grass, polygonum orientale, curdlan, sesbania and the like, wherein the wild oat is preferably used as an experimental object of herbicidal activity, and good prevention and control effects are achieved.

The sixth purpose of the invention is to research the application of the pentaaza-and/or oxo-dithio-bicyclo-diene ketone compound in preparing fluorescent pesticide and the light degradation performance thereof under the illumination condition, and to realize the sixth purpose of the invention, the pentaaza-and/or oxo-dithio-bicyclo-diene ketone compound prepared by the invention is subjected to a fluorescence spectrum test and a light degradation performance test, and the fluorescence performance and the light degradation performance are respectively studied. The test shows that: the compound has high fluorescence quantum yield, is a good fluorescent pesticide, can test fluorescence without adding a photosensitizer, can detect pesticide residues by using a fluorometer and test the transmission process of the pesticide in a plant body, and has good degradation performance under the illumination condition.

The pentaaza and/or oxo-dithio-bicyclo-ketene-containing fluorescent pesticide with the structural formula is designed and synthesized by an active structure splicing principle, and the pentaaza and/or oxo-dithio-bicyclo-ketene-containing fluorescent pesticide is expected to have practical application values in the aspects of preventing and treating harmful insects, inhibiting bacteria and weeding and serving as a degradable fluorescent pesticide, and obtains good insecticidal effect, antibacterial effect and weeding effect and good fluorescent and photodegradable performances through activity tests.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) according to the invention, according to the principle of superposition of the pharmaceutical activities that functional groups with different activities gather in the same molecule and the biological activity of the compound can be obviously improved, the insecticidal activity and the antibacterial activity of nitrogen, oxygen and sulfur heterocyclic compounds are combined with the ultra-strong herbicidal activity and the good photophysical performance of ketene compounds, a series of novel pentaaza-and/or oxo-dithio-bicyclo-ketene compounds are synthesized, and the insecticidal, antibacterial and herbicidal activities, and the fluorescent and photodegradable performances of the compounds are tested, so that good effects are obtained;

(2) in the synthesis method, the problems of large energy consumption, complex post-treatment, low yield and single structure of the synthesized compound in the traditional synthesis method are solved, primary amine, alkyl alcohol, hydrazine hydrate, binary acyl halide (or binary sulfonyl chloride) are used as main raw materials, strong acid and weak base salt is used as a catalyst, inorganic base is used as an alkaline reagent, and the pentaaza-and/or oxo-dithiadicyclic dienone compound is synthesized by a microwave solvothermal synthesis method.

(3) The invention uses a microwave solvothermal synthesis method in the synthesis reaction process, can place reaction raw materials and a solvent in a high-temperature high-pressure closed reaction kettle for reaction under the strong radiation of microwaves, not only can effectively prevent the volatilization of toxic substances, but also can ensure that the dissolution and the dispersion of reactants are uniform and the reaction activity of chemical substances is greatly improved, so that the yield of the pentaaza-and/or oxo-dithio-dicyclic dienone compound is greatly improved.

Drawings

FIG. 1 shows Compound IV of example 8₁-IV₆Fluorescence spectrum of (2).

Detailed Description

The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.

The following compounds (I) in examples 1 to 6₁-I₆)

For the applicant, according to the references described in the summary of the invention: synthesis of 5-amino-3-cyano-1- (2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivatives of Chenlianqing, Chenguizhou, Chengsen, et al and photophysical properties thereof [ J]The university of south China university (Nature science edition), 2011,30(1):5-8.

The volume of the polytetrafluoroethylene liner used in each of the following examples was 100 mL.

In each example, the mass ratio of silica gel powder used for adsorbing a sample prepared by a dry method to raw materials (referred to as filtrate) is 1: 1.2.

The bis-sulfonyl chlorides used in the examples below were obtained by oxidation of chlorine with water using the corresponding thiols, which are commercially available, or can be synthesized using methods known in the art, along with the bis-acid halides and other reagents.

In the following examples: the volume ratio of ethyl acetate to water used in the extraction in the step (II), the step (III) and the step (IV) is 1:4, 1:2 and 1:2.5 respectively.

Example 1 pentaazabicyclo dienone-containing Compounds IV₁Synthesis of (2)

Compound IV₁The synthetic route is as follows:

the specific operation steps are as follows:

the furfuryl amine and ethyl 2, 3-dicyanopropionate are taken as raw materials, and reference is made to the following references: synthesis of 5-amino-3-cyano-1- (2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivatives of Chenlianqing, Chenguizhou, Chengsen, et al and photophysical properties thereof [ J]5-amino-1-furan-2-methylene-1H-pyrazole-3-carbonitrile (I) prepared by the method of 5-8, proceedings of the university of the southern China (Nature science, ed.), 2011,30(1):5-8₁) The yield of the step (I): 98.6 percent, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(II) adding 12mmol of 5-amino-1-furan-2-methylene-1H-pyrazole-3-carbonitrile (I) into a 100mL polytetrafluoroethylene lining₁) 36mL of absolute ethanol and 12mmol of FeCl₃Putting the lining into a reaction kettle, sealing the reaction kettle, putting the reaction kettle into a microwave reactor, adjusting the power of the microwave reactor to 450W, heating the reaction kettle to 120 ℃, reacting the reaction kettle for 300min at the temperature of 120 ℃, extracting the reaction product for 1 time by using ethyl acetate and water after the reaction is finished, collecting an organic phase, and evaporating the ethyl acetate to dryness to obtain the ethyl 5-amino-1-furan-2-methylene-1H-pyrazole-3-carboxylate (II)₁) And (d) yield of step (ii): 93.4%, the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(III) adding 10mmol of 5-amino-1-furan-2-methylene-1H-pyrazole-3-carboxylic acid ethyl ester (II)₁) Adding into 100mL polytetrafluoroethylene lining, adding 60mmol 50 wt% hydrazine hydrate and 20mL methanol, placing the lining into a reaction kettle, sealing the reaction kettle, placing into a microwave reactor, adjusting the power of the microwave reactor to 500W, heating to 150 deg.C, reacting at 150 deg.C for 360min, after the reaction is stopped, removing excessive hydrazine hydrate and methanol by rotary evaporation, extracting with ethyl acetate and water for 1 time, collecting organic phase, and extracting with anhydrous MgSO₄Drying, vacuum filtering, adsorbing the filtrate with silica gel, dry sampling, and mixing with ethyl acetate, methanol and ethanol at a volume ratio of 1:2:4Purifying the product by column chromatography using petroleum ether mixed solvent as eluent to obtain 5-amino-1-furan-2-methylene-1H-pyrazole-3-carboxylic acid hydrazide (III)₁) And (5) yield of the step (III): 87.8 percent, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(IV) to 100mL of a polytetrafluoroethylene inner liner was added 10mmol of 5-amino-1-furan-2-methylene-1H-pyrazole-3-carboxylic acid hydrazide (III)₁) 15mmol NaH, 30mL DMF and 12mmol hexafluoroglutaryl chloride, the lining is put into a reaction kettle, the reaction kettle is sealed and then put into a microwave reactor, the microwave power is 650W, the temperature is raised to 180 ℃, the reaction is carried out for 360min at 180 ℃, after the reaction is finished and the temperature is reduced to room temperature, the reaction liquid is poured into a rotary evaporation bottle, the organic solvent is removed by using a rotary evaporator, a brown yellow viscous oily substance is obtained, and saturated Na is added into the brown yellow viscous oily substance₂CO₃Adjusting pH of the solution to 7-8 to remove acidic impurities, adding ethyl acetate and water, extracting for 2 times, adding anhydrous MgSO into the organic phase after extraction₄Drying, vacuum filtering, adsorbing the filtrate with silica gel powder, dry sampling, preparing mixed solvent of ethyl acetate, methanol and petroleum ether at volume ratio of 1:1:2 as eluent, and separating and purifying the product by column chromatography to obtain 4,4,5,5,6, 6-hexafluoro-13-furan-2-methylene-2, 8,9,12, 13-pentaaza-bicyclo [9.2.1 ] product]Tetradeca-1 (14), 11-diene-3, 7,10 trione (IV)₁) And (d) yield of step (iv): 92.3 percent. mp is 196.3-197.8 ℃.¹HNMR(CDCl₃, 400MHz):9.76(s,1H,N-H),8.45(s,1H,N-H),8.16(s,1H,N-H),7.24(s,1H,C-H), 6.38-5.13(m,2H,C-H),5.76(s,1H,N-H),2,26(m,2H,C-H₂).Anal.calc.for C₁₄H₉F₆N₅O₄:C,39.54；H,2.13；N,16.47；found C,39.36；H,2.18；N,16.50。

Example 2 pentaazabicyclo dienone-containing Compounds IV₂Synthesis of (2)

Compound IV₂The synthetic route is as follows:

the specific operation steps are as follows:

taking n-butylamine and ethyl 2, 3-dicyanopropionate as raw materials, and referring to references: synthesis of 5-amino-3-cyano-1- (2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivatives of Chenlianqing, Chenguizhou, Chengsen, et al and photophysical properties thereof [ J]5-amino-1-butyl-1H-pyrazole-3-carbonitrile (I) prepared by the method of 5-8, proceedings of university of south China (Nature science, ed.), 2011,30(1)₂) The yield of the step (I): 93.5%, the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(II) adding 12mmol of 5-amino-1-butyl-1H-pyrazole-3-carbonitrile (I) into a 100mL polytetrafluoroethylene lining₂) 36mL of n-propanol and 12mmol of SnCl₄Putting the lining into a reaction kettle, sealing the reaction kettle, putting the reaction kettle into a microwave reactor, adjusting the power of the microwave reactor to 450W, heating the reaction kettle to 120 ℃, reacting the reaction kettle for 300min at the temperature of 120 ℃, extracting the reaction kettle for 1 time by using ethyl acetate and water after the reaction is finished, collecting an organic phase, and evaporating the ethyl acetate to dryness to obtain the propyl 5-amino-1-butyl-1H-pyrazole-3-carboxylate (II)₂) And (d) yield of step (ii): 89.3 percent, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(III) adding 10mmol of 5-amino-1-butyl-1H-pyrazole-3-carboxylic acid propyl ester (II)₂) Adding into 100mL polytetrafluoroethylene lining, adding 60mmol 50 wt% hydrazine hydrate and 20mL anhydrous ethanol, placing the lining into a reaction kettle, sealing the reaction kettle, placing into a microwave reactor, adjusting the power of the microwave reactor to 500W, heating to 140 ℃, reacting at 140 ℃ for 360min, after the reaction stops, removing excessive hydrazine hydrate and ethanol by rotary evaporation, extracting with ethyl acetate and water for 1 time, collecting organic phase, and extracting with anhydrous MgSO₄Drying, vacuum filtering, adsorbing the filtrate with silica gel, dry sampling, preparing mixed solvent of ethyl acetate, methanol and petroleum ether at volume ratio of 1:2:4 as eluent, and purifying by column chromatography to obtain 5-amino-1-butyl-1H-pyrazole-3-carboxylic acid hydrazide (III)₂) And (5) yield of the step (III): 85.8 percent, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(IV) to a 100mL polytetrafluoroethylene liner was added 10mmol of 5-amino-1-butyl-1H-pyrazole-3-carboxylic acid hydrazide (III)₂) 15mmol NaOH, 30mL DMSO and 12mmol adipoyl dichloride, the lining is put into a reaction kettle, the reaction kettle is sealed and then put into a microwave reactor, the microwave power is 650W, the temperature is increased to 180 ℃, the reaction is carried out for 360min at 180 ℃, after the reaction is finished and the temperature is reduced to room temperature, the reaction liquid is poured into a rotary evaporation bottle, the organic solvent is removed by using a rotary evaporator, a brown yellow viscous oily substance is obtained, and saturated Na is added into the brown yellow viscous oily substance₂CO₃Adjusting pH of the solution to 7-8 to remove acidic impurities, adding ethyl acetate and water, extracting for 2 times, adding anhydrous MgSO into the organic phase after extraction₄Drying, suction filtering, adsorbing the filtrate with silica gel powder, dry sampling, preparing mixed solvent of ethyl acetate, methanol and petroleum ether with volume ratio of 1:1:2 as eluent, and separating and purifying the product by column chromatography to obtain 14-butyl-2, 9,10,13, 14-pentaazabicyclo [10.2.1 ] product]Pentadecane-1 (15), 12-diene-3, 8, 11-trione (IV)₂) And (d) yield of step (iv): 86.7 percent. mp is 184.3-185.2 ℃.¹HNMR(CDCl₃,400MHz):9.84(s,1H,N-H),8.72(s, 1H,N-H),6.25(s,1H,C-H),5.46(s,1H,N-H),3,43(m,2H,C-H2),2,16(m,4H,C-H₂), 1,66(m,4H,C-H₂),1.44-1.24(m,4H,C-H₂),0.86(m,3H,C-H₃).Anal.calc.for C₁₄H₂₁N₅O₃:C,54.71；H,6.89；N,22.79；found C,54.68；H,6.88；N,22.81。

Example 3 pentaazabicyclo dienone-containing Compounds IV₃Synthesis of (2)

Compound IV₃The synthetic route is as follows:

the specific operation steps are as follows:

1-naphthylamine and ethyl 2, 3-dicyanopropionate are taken as raw materials, and reference is made to the following references: synthesis of 5-amino-3-cyano-1- (2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivatives, Chenlianqing, Chenguizhou, Chengusen, et al, and photophysics thereofPerformance [ J]5-amino-1-naphthalen-1-yl-1H-pyrazole-3-carbonitrile (I) prepared by the method of proceedings of the university of the south of the China (Nature's science, ed.), 2011,30(1):5-8₃) The yield of the step (I): 94.5%, the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(II) adding 12mmol of 5-amino-1-naphthalene-1-yl-1H-pyrazole-3-carbonitrile (I) into a 100mL polytetrafluoroethylene lining₃) 36mL of absolute ethanol and 12mmol of ZnCl₂Putting the lining into a reaction kettle, sealing the reaction kettle, putting the reaction kettle into a microwave reactor, adjusting the power of the microwave reactor to 450W, heating the reaction kettle to 120 ℃, reacting the reaction kettle for 300min at the temperature of 120 ℃, extracting the reaction kettle for 1 time by using ethyl acetate and water after the reaction is finished, collecting an organic phase, and evaporating the ethyl acetate to dryness to obtain the ethyl 5-amino-1-naphthalene-1-yl-1H-pyrazole-3-carboxylate (II)₃) And (d) yield of step (ii): 90.4%, the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(III) adding 10mmol of 5-amino-1-naphthalene-1-yl-1H-pyrazole-3-carboxylic acid ethyl ester (II)₃) Adding into 100mL polytetrafluoroethylene lining, adding 60mmol 50 wt% hydrazine hydrate and 20mL isopropanol, placing the lining into a reaction kettle, sealing the reaction kettle, placing into a microwave reactor, adjusting the power of the microwave reactor to 500W, heating to 150 deg.C, reacting at 150 deg.C for 360min, removing excessive hydrazine hydrate and isopropanol by rotary evaporation after the reaction is stopped, extracting with ethyl acetate and water for 1 time, collecting organic phase, and extracting with anhydrous MgSO₄Drying, vacuum filtering, adsorbing the filtrate with silica gel, dry sampling, preparing mixed solvent of ethyl acetate, methanol and petroleum ether at volume ratio of 1:2:4 as eluent, and purifying by column chromatography to obtain 5-amino-1-naphthalene-1-yl-1H-pyrazole-3-carboxylic acid hydrazide (III)₃) And (5) yield of the step (III): 86.7 percent, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(IV) to 100mL of a polytetrafluoroethylene inner liner was added 10mmol of 5-amino-1-naphthalen-1-yl-1H-pyrazole-3-carboxylic acid hydrazide (III)₃) 15mmol KOH, 30mL formamide and 12mmol fumaric chloride, placing the lining into a reaction kettle, sealing the reaction kettle, placing the reaction kettle into a microwave reactor, and performing microwave treatmentHeating to 180 deg.C at power of 650W, reacting at 180 deg.C for 360min, cooling to room temperature after reaction, pouring the reaction solution into a rotary evaporation bottle, removing organic solvent with rotary evaporator to obtain brown yellow viscous oily substance, adding saturated Na₂CO₃Adjusting pH of the solution to 7-8 to remove acidic impurities, adding ethyl acetate and water, extracting for 2 times, adding anhydrous MgSO into the organic phase after extraction₄Drying, vacuum filtering, adsorbing the filtrate with silica gel powder, dry sampling, eluting with mixed solvent of ethyl acetate, methanol and petroleum ether at volume ratio of 1:1:2, and purifying by column chromatography to obtain 12-naphthalene-1-yl-2, 7,8,11, 12-pentaaza-bicyclo [8.2.1 ] bicyclo [12]Trideca-1 (13),4, 10-triene-3, 6, 9-trione (IV)₃) And (d) yield of step (iv): 88.5 percent. mp is 205.4-206.2 ℃.¹HNMR(CDCl₃,400MHz):9.72(s,1H,N-H), 8.84(s,1H,N-H),7.84-7.78(d,3H,Ar-H),7.54-7.45(d,4H,Ar-H),6.22(s,1H,C-H), 5.56(s,1H,N-H),4,16(m,4H,C-H).Anal.calc.for C₁₈H₁₃N₅O₃:C,62.24；H,3.77；N, 20.16；found C,62.26；H,3.67；N,20.12。

Example 4 pentaaza-and oxo-dithiobicyclo-dienones IV₄Synthesis of (2)

Compound IV₄The synthetic route of (2):

the specific operation steps are as follows:

the method comprises the following steps of (I) taking m-nitroaniline and ethyl 2, 3-dicyanopropionate as raw materials, and referring to reference documents: synthesis of 5-amino-3-cyano-1- (2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivatives of Chenlianqing, Chenguizhou, Chengsen, et al and photophysical properties thereof [ J]5-amino-1- (3-nitro-phenyl) -1H-pyrazole-3-carbonitrile (I) prepared by the method of 5-8, proceedings of the university of the south of China (Nature's science, ed.), 2011,30(1):5-8₄) The yield of the step (I): 91.2%, the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(II) adding 12mmol of 5-amino-1- (3-nitro-phenyl) -1H-pyrazole-3-carbonitrile (I) into a 100mL polytetrafluoroethylene lining₄) 36mL of absolute ethanol and 12mmol of CuCl₂Putting the lining into a reaction kettle, sealing the reaction kettle, putting the reaction kettle into a microwave reactor, adjusting the power of the microwave reactor to 450W, heating the reaction kettle to 120 ℃, reacting the reaction kettle for 300min at the temperature of 120 ℃, extracting the reaction kettle for 1 time by using ethyl acetate and water after the reaction is finished, collecting an organic phase, and evaporating the ethyl acetate to dryness to obtain the 5-amino-1- (3-nitro-phenyl) -1H-pyrazole-3-carboxylic acid ethyl ester (II)₄) And (d) yield of step (ii): 93.2 percent, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(III) 10mmol of 5-amino-1- (3-nitro-phenyl) -1H-pyrazole-3-carboxylic acid ethyl ester (II)₄) Adding into 100mL polytetrafluoroethylene lining, adding 60mmol 50 wt% hydrazine hydrate and 20mL anhydrous ethanol, placing the lining into a reaction kettle, sealing the reaction kettle, placing into a microwave reactor, adjusting the power of the microwave reactor to 500W, heating to 150 deg.C, reacting at 150 deg.C for 360min, after the reaction stops, removing hydrazine hydrate and ethanol by rotary evaporation, extracting with ethyl acetate and water for 1 time, collecting organic phase, and extracting with anhydrous MgSO 2₄Drying, vacuum filtering, adsorbing the filtrate with silica gel, dry sampling, preparing mixed solvent of ethyl acetate, methanol and petroleum ether at volume ratio of 1:2:4 as eluent, and purifying the product by column chromatography to obtain 5-amino-1- (3-nitro-phenyl) -1H-pyrazole-3-carboxylic acid hydrazide (III)₄) And (5) yield of the step (III): 84.6 percent, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(IV) to a 100mL polytetrafluoroethylene liner was added 10mmol of 5-amino-1- (3-nitro-phenyl) -1H-pyrazole-3-carboxylic acid hydrazide (III)₄) 15mmol NaH, 30mL THF and 12mmol 1, 2-disulfonyl ethyl chloride, the lining is placed into a reaction kettle, the reaction kettle is sealed and then placed into a microwave reactor, the microwave power is 650W, the temperature is raised to 165 ℃, the reaction is carried out for 360min at 165 ℃, after the reaction is finished and the temperature is reduced to room temperature, the reaction liquid is poured into a rotary evaporation bottle, the organic solvent is removed by using a rotary evaporator, a light yellow powdery substance is obtained, saturated Na is added into the light yellow powdery substance₂CO₃Adjusting pH of the solution to 7-8 to remove acidic impurities, adding ethyl acetate and water, extracting for 2 times, adding anhydrous MgSO into the organic phase after extraction₄Drying, vacuum filtering, adsorbing the filtrate with silica gel powder, dry sampling, preparing mixed solvent of ethyl acetate, methanol and petroleum ether at volume ratio of 1:1:2 as eluent, and separating and purifying the product by column chromatography to obtain 12- (3-nitro-phenyl) -3,3,6, 6-tetraoxo-3 lambda⁶,6λ⁶Dithio-2, 7,8,11, 12-pentaaza-bicyclo [8.2.1 ]]Trideca-1 (13), 10-dien-9-one (IV)₄) And (d) yield of step (iv): 85.4 percent. mp is 186.2-187.8 ℃.¹HNMR (CDCl₃,400MHz):8.44(s,1H,N-H),7.86-7.77(d,2H,Ar-H),7.54(s,2H,Ar-H), 6.52(s,1H,C-H),5.35(s,1H,N-H),4.65(s,1H,N-H),2,96(m,4H,C-H2).Anal.calc. for C₁₂H₁₂N₆O₇S₂:C,34.61；H,2.90；N,20.18；found C,34.58；H,2.92；N,20.16。

Example 5 pentaaza-oxo-dithiobicyclo-dienones IV₅Synthesis of (2)

Compound IV₅The synthetic route of (2):

the specific operation steps are as follows:

taking 2-aminopyridine and ethyl 2, 3-dicyanopropionate as raw materials, and referring to references: synthesis of 5-amino-3-cyano-1- (2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivatives of Chenlianqing, Chenguizhou, Chengsen, et al and photophysical properties thereof [ J]5-amino-1-pyridin-2-yl-1H-pyrazole-3-carbonitrile (I) prepared by the method of proceedings of the university of south China (Nature science, ed.), 2011,30(1):5-8₅) The yield of the step (I): 93.2 percent, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(II) adding 12mmol of 5-amino-1-pyridine-2-yl-1H-pyrazole-3-carbonitrile (I) into a 100mL polytetrafluoroethylene lining₅) 36mL of n-butanol and 12mmol of FeCl₃The lining is put into a reaction kettle which is sealedSealing, placing in a microwave reactor, adjusting the power of the microwave reactor to 450W, heating to 130 deg.C, reacting at 130 deg.C for 300min, extracting with ethyl acetate and water for 1 time after the reaction is completed, collecting organic phase, and evaporating ethyl acetate to obtain 5-amino-1-pyridin-2-yl-1H-pyrazole-3-carboxylic acid butyl ester (II)₅) And (d) yield of step (ii): 88.8 percent, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(III) adding 10mmol of 5-amino-1-pyridin-2-yl-1H-pyrazole-3-carboxylic acid butyl ester (II)₅) Adding into 100mL polytetrafluoroethylene lining, adding 60mmol 50 wt% hydrazine hydrate and 20mL ethylene glycol, placing the lining into a reaction kettle, sealing the reaction kettle, placing into a microwave reactor, adjusting the power of the microwave reactor to 500W, heating to 160 ℃, reacting at 160 ℃ for 360min, after the reaction stops, removing excessive hydrazine hydrate and ethylene glycol by rotary evaporation, extracting with ethyl acetate and water for 1 time, collecting organic phase, and extracting with anhydrous MgSO₄Drying, vacuum filtering, adsorbing the filtrate with silica gel, dry sampling, preparing mixed solvent of ethyl acetate, methanol and petroleum ether at volume ratio of 1:2:4 as eluent, and purifying the product by column chromatography to obtain 5-amino-1-pyridin-2-yl-1H-pyrazole-3-carboxylic acid hydrazide (III)₅) And (5) yield of the step (III): 87.4 percent, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(IV) to 100mL of a polytetrafluoroethylene inner liner was added 10mmol of 5-amino-1-pyridin-2-yl-1H-pyrazole-3-carboxylic acid hydrazide (III)₅) 15mmol NaH, 30mL DMAP and 12mmol 1, 4-disulfonyl chlorobutane, placing the lining into a reaction kettle, sealing the reaction kettle, placing the reaction kettle into a microwave reactor, heating to 190 ℃ under the microwave power of 650W, reacting for 360min at 190 ℃, pouring the reaction liquid into a rotary evaporation bottle after the reaction is finished and the temperature is reduced to room temperature, removing the organic solvent by using a rotary evaporator to obtain a light yellow powdery substance, adding saturated Na into the light yellow powdery substance₂CO₃Adjusting pH of the solution to 7-8 to remove acidic impurities, adding ethyl acetate and water, extracting for 2 times, adding anhydrous MgSO into the organic phase after extraction₄Drying, vacuum filtering, adsorbing the filtrate with silica gel powder, and dryingPreparing a sample, preparing a mixed solvent of ethyl acetate, methanol and petroleum ether with a volume ratio of 1:1:2 as an eluent, and separating and purifying the product by column chromatography to obtain a product 3,3,8, 8-tetraoxo 14-pyridin-2-yl-3 lambda⁶,8λ⁶Dithio-2, 9,10,13, 14-pentaaza-bicyclo [10.2.1]Pentadecane-1 (15), 12-dien-11-one (IV)₅) And (d) yield of step (iv): 87.2 percent. mp is 191.8-192.4 ℃.¹HNMR(CDCl₃, 400MHz):8.63(s,1H,N-H),8.46(s,1H,Py-H),7.86-7.77(m,3H,Py-H),6.34(s, 1H,C-H),5.35(s,1H,N-H),4.85(s,1H,N-H),2,41-2.37(m,4H,C-H₂),1.23-1.14(m, 4H,C-H₂).Anal.calc.for C₁₃H₁₆N₆O₅S₂:C,38.99；H,4.03；N,20.99；found C,38.97； H,4.08；N,21.04。

Example 6 pentaaza-oxo-dithiobicyclo-dienones IV₆Synthesis of (2)

Compound IV₆The synthetic route of (2):

the specific operation steps are as follows:

p-isopropylaniline and ethyl 2, 3-dicyanopropionate were used as starting materials, reference is made to the following references: synthesis of 5-amino-3-cyano-1- (2, 6-dichloro-4-trifluoromethylphenyl) pyrazole derivatives of Chenlianqing, Chenguizhou, Chengsen, et al and photophysical properties thereof [ J]5-amino-1- (4-isopropyl-phenyl) -1H-pyrazole-3-carbonitrile (I) prepared by the method of 5-8, proceedings of the university of the south of China (Nature's science, ed.), 2011,30(1):5-8₆) The yield of the step (I): 88.9%, the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(II) adding 12mmol of 5-amino-1- (4-isopropyl-phenyl) -1H-pyrazole-3-carbonitrile (I) into a 100mL polytetrafluoroethylene lining₆) 36mL of absolute ethanol and 12mmol of CoCl₂Placing the lining into a reaction kettle, sealing the reaction kettle, placing the reaction kettle into a microwave reactor, adjusting the power of the microwave reactor to 450W, heating to 130 ℃, reacting at 130 ℃ for 300min, and using ethyl acetate after the reaction is finishedExtracting with water for 1 time, collecting organic phase, evaporating ethyl acetate to obtain 5-amino-1- (4-isopropyl-phenyl) -1H-pyrazole-3-carboxylic acid ethyl ester (II)₆) And (d) yield of step (ii): 91.6 percent, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(III) adding 10mmol of 5-amino-1- (4-isopropyl-phenyl) -1H-pyrazole-3-carboxylic acid ethyl ester (II)₆) Adding into 100mL polytetrafluoroethylene lining, adding 60mmol 50 wt% hydrazine hydrate and 20mL ethylene glycol, placing the lining into a reaction kettle, sealing the reaction kettle, placing into a microwave reactor, adjusting the power of the microwave reactor to 500W, heating to 160 ℃, reacting at 160 ℃ for 360min, after the reaction stops, removing hydrazine hydrate and ethylene glycol by rotary evaporation, extracting with ethyl acetate and water for 1 time, collecting organic phase, and extracting with anhydrous MgSO₄Drying, vacuum filtering, adsorbing the filtrate with silica gel, dry sampling, preparing mixed solvent of ethyl acetate, methanol and petroleum ether at volume ratio of 1:2:4 as eluent, and purifying the product by column chromatography to obtain 5-amino-1- (4-isopropyl-phenyl) -1H-pyrazole-3-carboxylic acid hydrazide (III)₆) And (5) yield of the step (III): 84.5 percent, and the structural formula of the compound is confirmed by infrared and nuclear magnetic resonance hydrogen spectrum detection.

(IV) to a 100mL polytetrafluoroethylene liner was added 10mmol of 5-amino-1- (4-isopropyl-phenyl) -1H-pyrazole-3-carboxylic acid hydrazide (III)₆) 15mmol NaH, 30mL DMF and 12mmol 1, 6-disulfonyl hexane, placing the lining into a reaction kettle, sealing the reaction kettle, placing the reaction kettle into a microwave reactor, heating to 180 ℃ under the microwave power of 650W, reacting for 360min at 180 ℃, pouring the reaction liquid into a rotary evaporation bottle after the reaction is finished and the temperature is reduced to room temperature, removing the organic solvent by using a rotary evaporator to obtain a light yellow powdery substance, adding saturated Na into the light yellow powdery substance₂CO₃Adjusting pH of the solution to 7-8 to remove acidic impurities, adding ethyl acetate and water, extracting for 2 times, adding anhydrous MgSO into the organic phase after extraction₄Drying, vacuum filtering, adsorbing the filtrate with silica gel powder, dry sampling, preparing mixed solvent of ethyl acetate, methanol and petroleum ether at volume ratio of 1:1:2 as eluent, and separating and purifying the product by column chromatographyTo obtain the product 16- (4-isopropyl-phenyl) -3,3,10, 10-tetraoxo-3 lambda⁶,10λ⁶Dithio-2, 11,12,15, 16-pentaaza-bicyclo [12.2.1]Heptadeca-1 (17), 14-dien-13-one (IV)₆) And (d) yield of step (iv): 85.7 percent. mp is 188.7-189.5 ℃.¹HNMR(CDCl₃,400MHz):8.74(s,1H,N-H),7.36-7.30(d,2H,Ar-H),7.14(s,2H, Ar-H),6.74(s,1H,C-H),5.62(s,1H,N-H),4.25(s,1H,N-H),3,26(m,4H,C-H₂), 3,04(s,1H,C-H),2,42-2.36(m,8H,C-H₂),1,08(s,6H,C-H₃).Anal.calc.for C₁₉H₂₇N₅O₅S₂:C,48.60；H,5.80；N,14.91；found C,48.58；H,5.82；N,14.93。

Comparative example 7 pentaazabicyclo dienone-containing Compounds IV₁Condition optimization of synthesis

Experimental exploration one: examination of the Synthesis of 5-amino-1-furan-2-methylene-1H-pyrazole-3-carboxylic acid ethyl ester (II) in step (II) of example 1₁) The synthesis method and catalyst of (2) have the same effects as those of the compound synthesized in the step (ii) of example 1 in terms of the other operations and the amounts of reagents.

(1) The limited power is 450W, the catalyst is FeCl₃Reaction temperature of 120 ℃ and reaction time of 300min, and the synthesis by examining the oil bath heating method, the solvothermal synthesis method, the ultrasonic wave irradiation method and the microwave solvothermal synthesis method, respectively (II)₁) The influence of (c). The oil bath heating method comprises the following steps: adding reactants into a round-bottom flask, and directly heating by using an oil bath pot under the condition of introducing air; an ultrasonic wave radiation method comprises the following steps: adding reactants into a flask, putting the flask into an ultrasonic reactor for reaction, and heating by using a water bath under the condition of introducing air; the solvothermal synthesis method comprises the following steps: adding the reactant into a polytetrafluoroethylene lining, screwing down a cover, putting into a reaction kettle, and putting into an oven for reaction.

TABLE 1 different synthetic methods vs. Synthesis (II)₁) Effect of yield

The yield is the yield of step (two).

The product (II) can be seen from Table 1₁) The yield of the method is greatly influenced by the synthesis method, and the microwave solvothermal synthesis method has higher yield than other three synthesis methods under the condition that other conditions are not changed.

(2) Limiting the microwave power to be 450W, adopting the microwave solvothermal synthesis method as the synthesis method, adopting the reaction temperature of 120 ℃ and the reaction time of 300min, and respectively investigating AlCl as the catalyst₃、CuCl₂、Fe(NO₃)₃And FeCl₃For synthesis of (II)₁) The influence of (c).

TABLE 2 Synthesis of different catalyst pairs (II)₁) Effect of yield

The yield is the yield of step (two). From Table 2 it can be seen that FeCl, a strong acid and a weak base salt, is used when compared to other catalysts₃When used as a catalyst, the catalyst can greatly improve the product (II)₁) The yield of (a).

The synthetic product (II) can be obtained by the above experimental exploration₁) The optimum conditions of (2): the microwave solvent thermal synthesis method is a synthesis method, and the microwave power is 450W, FeCl₃Is catalyst, reaction temperature is 120 ℃ and reaction time is 300 min.

Experiment exploration two: investigation of example 1 Synthesis of 5-amino-1-furan-2-methylene-1H-pyrazole-3-carboxylic acid hydrazide (III) in step (III)₁) The influence of the alkyl alcohol (a) solvent on the reaction results, other operations and the amounts of reagents used were the same as those for the synthesis of the compound in step (III) of example 1.

The microwave power is limited to be 500W, the microwave solvothermal synthesis method is taken as the synthesis method, the reaction temperature is 150 ℃ and the reaction time is 360min, and the synthesis of methanol, absolute ethyl alcohol, n-butyl alcohol and isopropanol is respectively examined (III)₁) The influence of (c).

TABLE 3 Synthesis of different alkyl alcohol pairs (III)₁) Effect of yield

The yields are the yields of step (three). It can be seen from Table 3 that when more polar ethanol and methanol were used as solvents, the product (III)₁) The yield of the product is higher, but the effect of using methanol is better.

Experiment exploration is three: examine the synthesis of the final product (IV) in step (IV) of example 1, respectively₁) The influence of the alkaline reagent and the organic solvent on the reaction results, other operations and the amounts of the reagents used were the same as those in the synthesis of the compound in the step (iv) in example 1.

(1) Respectively inspecting alkaline reagents NaH, KOH, NaOH and Na by limiting the microwave power to be 650W, taking a microwave solvothermal synthesis method as a synthesis method, taking DMF as a solvent, and taking reaction temperature of 180 ℃ and reaction time of 360min₂CO₃、K₂CO₃And Cs₂CO₃For synthesis of (IV)₁) The influence of (c).

TABLE 4 Synthesis of (IV) with different alkaline reagent pairs₁) Effect of yield

The yields were all the yields of step (IV). It can be seen from Table 4 that when different alkaline agents are used, the product (IV) is obtained₁) The yield of (IV) has a significant influence, and the product (IV) is more advantageously formed when using more basic NaH, KOH and NaOH₁) Among them, NaH is the most effective.

(2) Limiting the microwave power to 650W, taking a microwave solvothermal synthesis method as a synthesis method, taking an alkaline reagent as NaH, taking the reaction temperature to 180 ℃ and taking the reaction time to 360min, and respectively inspecting the organic solvents THF, cyclohexane, DMSO, pyridine and DMF (IV) for pair synthesis₁) The influence of (c).

TABLE 5 different organic solvent pairs Synthesis (IV)₁) Effect of yield

The yields were all the yields of step (IV). As can be seen from Table 5, the product (IV) was obtained in THF, DMSO, pyridine and DMF as solvents without changing the other conditions₁) Wherein the yield of DMF as solvent can reach 92.7%.

The synthetic product (IV) can be obtained by the above experimental exploration₁) The optimum conditions of (2): the microwave solvent synthesis method is a synthesis method, the microwave power is 650W, NaH as an alkaline reagent, DMF as an organic solvent, the reaction temperature is 180 ℃ and the reaction time is 360 min.

Example 8 pentaaza-and/or oxo-dithiobicyclo-dienones (IV)₁-IV₆) Investigation of fluorescence Properties

Compound IV₁-IV₆The fluorescence emission spectra data are shown in Table 6.

TABLE 6 Compound IV₁-IV₆Fluorescence emission spectroscopy data of

Note: in CH₂Cl₂In solution, the concentration is 0.5mol/L, and the quantum yield is phi_fQuinine hydrogen sulfate as a reference, with fluorescence quantum yield measured at 0.546

Compound IV₁-IV₆Respectively dissolve in CH₂Cl₂The fluorescence absorption spectrum of the solution prepared in the method is shown in figure 1, and the concentration of the solution is 0.3 mol/L. Using the equation phi_s＝Φ_f(η_s ²A_rI_s/η_r ²A_sI_r) Calculating the fluorescence quantum yield, wherein_sIs the quantum yield, phi, of the sample_fIs the quantum yield of the reference, η_sIs the refractive index of the solvent, A_sAnd A_rIs the absorbance of the sample and the excitation wavelength of the reference, I_sAnd I_rIs the comprehensive region of the emission bands of the sample and reference, and is quinine sulfate (0.5mol/L, phi)_f0.546) as reference.

As can be seen from fig. 1: when E is_xAt 205nm, compound IV₁、IV₂、IV₃、IV₅And IV₆The fluorescence quantum yield test shows that the fluorescence absorption peaks have stronger fluorescence absorption peaks at 456, 490nm, 469,497nm, 465,501nm, 478,507nm, 485,517nm and 476,506nm respectively: the compound has better fluorescence quantum yield and is a better luminescent material.

Example 9 pentaaza-and/or oxo-dithiobicyclo-dienones (IV)₁-IV₆) Study of photodegradability

Using xenon lamp (350W) as light source for simulating sunlight, and respectively using compound IV₁-IV₆For photodegradation of the substrate, the initial concentrations were all 1.5 × 10^-4mol/L. In view of the compound IV₁-IV₆The solubility in pure water is low, and acetonitrile is added as a cosolvent in the preparation process. Determination of Compound IV Using high Performance liquid chromatography₁-IV₆The chromatographic conditions are that a chromatographic column is a phenomenex C18 chromatographic column (250 nm × 4.6.6 mm,5 mu m), the mobile phase is acetonitrile with the volume ratio of 70:30, the flow rate is 1.0mL/min, the detection wavelength is 250nm, the sample amount is 20 mu L, the experiment is repeated for 3 times, the result is averaged, the degradation rate is calculated, and the compound IV is researched₁-IV₆The photodegradability of (c). The results are shown in Table 7.

TABLE 7 Compound IV₁-IV₆Rate of photodegradation at different times

Slave watch7 to a compound IV₁-IV₆The photodegradation rate is low within 8 hours, and the drug effect can be well exerted; compound IV₁-IV₆The photodegradation rate is higher after 72 hours, the pesticide residue is low, and the pesticide is environment-friendly and is a green and environment-friendly pesticide.

Example 10 pentaaza-and/or oxo-dithiobicyclo-dienones (IV)₁-IV₆) Study on insecticidal Activity of cabbage caterpillars

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, surfactant 2-sodium naphthalenesulfonate formaldehyde condensate accounting for 5 percent of the total mass is diluted in antifreeze glycol accounting for 5 percent of the total mass, water accounting for 25 percent of the total mass is slowly added into the solution, pentaaza and/or oxo-dithiadicyclo dienone compounds which are prepared in the embodiment and account for 25 percent of the total mass and auxiliary agents accounting for 5 percent of the total mass (the auxiliary agents comprise 25 percent of preservative benzoic acid, 25 percent of defoamer organic silicon and 50 percent of thickener xanthan gum) are added into the solution under the condition of rapid stirring, the mixture is ground after the addition is finished, and finally, water accounting for 35 percent of the total mass is added. Compounds IV of examples 1 to 6₁-IV₆All the above operations are carried out to obtain corresponding suspending agents, and the prepared suspending agents are diluted by water to respectively prepare compounds IV₁-IV₆A diluted suspending agent with a concentration of 100 mg/L.

The slide immersion test was performed using 100mg/L of diluted suspension of each of the prepared 6 groups of compounds. Placing cabbage caterpillar to be tested on the glass slide double-sided adhesive tape, then placing for 2h in an indoor environment at the temperature of 25 +/-1 ℃, removing dead and inactive individuals, and recording the number of live insects. Immersing one end of the insect into diluted suspending agent with concentration of 100mg/L of each compound prepared in advance, taking out after 5s, and quickly sucking the insect body and redundant liquid medicine around the insect body with absorbent paper. The slides were then incubated for 4D at a temperature of 25 ± 1 ℃ under light (L: D ═ 16h:8h), examined 1 time every 24h and the results recorded. The body was touched with a brush pen, and the dead one was killed. 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 8.

TABLE 8 Compound IV₁-IV₆Activity against cabbage caterpillar at a concentration of 100mg/L

Example 11 pentaaza-and/or oxo-dithiobicyclo-dienones (IV)₁-IV₆) Research on bacteriostatic activity of bacillus anthracis

Compounds IV prepared in examples 1 to 6₁-IV₆The compounds are respectively dissolved in DMSO to be prepared into the concentration of 0.1% (m/v, m/v is g/mL, the same below), then each compound is respectively diluted to 5 concentrations of 0.85, 0.65, 0.45, 0.25 and 0.1mg/L by using 1% (m/v) acetic acid distilled water solution to be used as test samples, a positive control drug is linezolid, 1% (m/v) acetic acid distilled water is directly used for preparing 5 concentrations of 0.85, 0.65, 0.45, 0.25 and 0.1mg/L, and a negative control group is 1% (m/v) acetic acid solution. Circular sterilized filter paper sheets with the diameter of 6mm are respectively placed into the prepared solutions with different concentrations by using tweezers, and the negative control and the positive control are performed in the same way. These sections were attached to agar solid media coated with Bacillus anthracis. Then placing the culture medium in a constant temperature incubator, culturing for 36h at 30 ℃, accurately measuring the diameters of all inhibition zones by using a vernier caliper after removing, and evaluating the inhibition activity of the tested compound, wherein, + represents high activity, and, + represents medium activity, and-represents weak activity. The test results are shown in Table 9. It can be seen that the concentration of 0.85mg/L is IV₁、IV₄And IV₆The concentration of IV is 0.65mg/L and the best antibacterial effect is₃、IV₄、IV₅And IV₆The concentration of the antibacterial agent is 0.45mg/L, and only IV with good antibacterial effect₄And IV₅When the concentration is lower than 0.25mg/L, the bacteriostatic effect of the compound solution is not good at high concentration.

TABLE 9 Compound IV₁-IV₆Bacteriostatic activity against bacillus anthracis

Example 12 pentaaza-and/or oxo-dithiobicyclo-dienones (IV)₁-IV₆) Research on herbicidal activity of wild oats

Using 6 groups of the diluted suspension concentrates of example 10 at a concentration of 100mg/L, 1kg of wet soil was filled in 6 culture tanks, and the soil water was maintained. Sowing 30 wild oat seeds with the depth of 5mm in each tank, growing for a plurality of days at room temperature, and when the wild oat seeds grow to the 2-leaf stage, respectively dripping 8-12 drops of the compound IV into each tank₁-IV₆The mortality rate of the diluted suspending agent with the concentration of 100mg/L is observed after two days, the experiment is repeated for 3 times, and the result is averaged. The results are shown in Table 10.

TABLE 10 Compound IV₁-IV₆Activity assay for wild oat

From the results in Table 10, it is clear that Compound IV₁-IV₆Has better weeding effect on wild oat.

Claims

1. Pentaaza-and/or oxo-dithiobicyclo-dienone-containing compounds have a structural formula shown as a general formula (IV):

in the structural general formula (IV):

r1 is

In the structural general formula (IV): when M is C ═ O, - (Y) n-is-CF₂CF₂CF₂-、-CH₂CH₂CH₂CH₂-or-CH ═ CH-;

when M is O ═ S ═ O, - (Y) n-is-CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂-or-CH ═ CH-.

2. A method for synthesizing pentaaza-and/or oxo-dithiobicyclo-dienones as claimed in claim 1, comprising the following steps:

Reaction solvent R₂OH and a catalyst, the reaction kettle is sealed and then is placed into a microwave reactor, the microwave power is adjusted to be 200-800W, the reaction is carried out for 60-420min at the temperature of 70-300 ℃, the extract C is used for extraction after the reaction is finished, the organic phase is collected and evaporated to dryness to obtain a compound (II)

(II) reacting the compound (II)

Adding into polytetrafluoroethylene lining, adding hydrazine hydrate solution and alkyl alcohol, placing the lining into a reaction kettle, sealing the reaction kettle, placing into a microwave reactor, adjusting the microwave power to be 300-900W, placing into the microwave reactor, reacting at 350 ℃ for 90-480min, removing the solvent after the reaction is stopped, extracting with an extract A, collecting an organic phase, and using anhydrous MgSO₄Drying, vacuum filtering, adsorbing the filtrate with silica gel, dry sampling, preparing eluent A, purifying by column chromatography to obtain compound (Ш)

Sealing a reaction kettle, putting the reaction kettle into a microwave reactor, adjusting the microwave power to be 500-class power of 1000W, heating to be 100-class power of 350 ℃, reacting at 100-class power of 350 ℃ for 90-540min, after the reaction is finished and the temperature is reduced to be room temperature, removing the organic solvent by rotary evaporation to obtain a crude product, adding saturated Na into the crude product, and adding the saturated Na into the crude product₂CO₃Adjusting pH to 7-8, adding extract B, extracting, and adding anhydrous MgSO₄Drying, filtering, adsorbing the filtrate with silica gel powder, preparing a sample by a dry method, preparing an eluent B with a certain proportion, and separating and purifying the product by column chromatography to obtain a product (IV);

the compound (I) and the reaction solvent R in the step (one)₂The ratio of-OH to catalyst addition was 1 mmol: 2-10 ml: 0.5-5 mmol; the reaction solvent R in the step (one)₂-OH is selected from at least one of ethanol, n-propanol, n-butanol, isobutanol, n-pentanol and n-hexanol;

adding hydrazine hydrate and alkyl alcohol into the compound (II) in the step (II) and the hydrazine hydrate solution in a proportion of 1 mmol: 3-12 mmol: 1-10 ml;

in the step (III), the adding amount ratio of the compound (III), the organic solvent, the alkaline reagent and the acyl halide derivative is 1 mmol: 1-10 ml: 1-5 mmol: 1-1.5 mmol;

the acyl halide derivative is hexafluoroglutaryl chloride, adipoyl dichloride or butenedioyl chloride.

3. A method for synthesizing pentaaza-and/or oxo-dithiobicyclo-dienones as claimed in claim 1, comprising the following steps:

Reaction ofSolvent R₂OH and a catalyst, the reaction kettle is sealed and then is placed into a microwave reactor, the microwave power is adjusted to be 200-800W, the reaction is carried out for 60-420min at the temperature of 70-300 ℃, the extract C is used for extraction after the reaction is finished, the organic phase is collected and evaporated to dryness to obtain a compound (II)

(II) reacting the compound (II)

Sealing a reaction kettle, putting the reaction kettle into a microwave reactor, adjusting the microwave power to be 500-class power of 1000W, heating to be 350-class power of 100 ℃, reacting at the temperature of 350-class power of 100 ℃ for 90-540min, after the reaction is finished and the temperature is reduced to be room temperature, removing the organic solvent by rotary evaporation to obtain a crude product, adding saturated Na into the crude product, and adding the saturated Na into the crude product₂CO₃Adjusting pH to 7-8, adding extract B, extracting, and adding anhydrous MgSO₄Drying, filtering, adsorbing the filtrate with silica gel powder, dry sampling, preparing eluent B, and separating and purifying by column chromatographyTo obtain a product (IV);

the compound (I) and the reaction solvent R in the step (one)₂The ratio of-OH to catalyst addition was 1 mmol: 2-10 ml: 0.5-5 mmol;

the reaction solvent R in the step (one)₂-OH is selected from at least one of ethanol, n-propanol, n-butanol, isobutanol, n-pentanol and n-hexanol;

adding hydrazine hydrate and alkyl alcohol into the compound (II) and the hydrazine hydrate solution in the step (II) according to the proportion of 1 mmol: 3-12 mmol: 1-10 ml;

in the step (III), the adding amount ratio of the compound (III), the organic solvent, the alkaline reagent and the sulfonyl chloride derivative is 1 mmol: 1-10 ml: 1-5 mmol: 1-1.5 mmol;

the sulfonyl chloride derivative is: 1, 2-disulfonylchloroethane, 1, 4-disulfonylchlorobutane or 1, 6-disulfonylcyclohexane.

4. The process according to claim 2 or 3, wherein the catalyst in step (one) is selected from SnCl₄、CoCl₂、Fe₂(SO₄)₃、ZnCl₂、CuCl₂、FeCl₃、CuSO₄、AlCl₃With Fe (NO)₃)₃At least one of (1).

5. The method according to claim 2 or 3,

the alkyl alcohol in the step (II) is at least one selected from methanol, ethanol, isopropanol, n-butanol, ethylene glycol, isoamyl alcohol, 1, 2-propylene glycol, 1, 3-butanediol and diethylene glycol;

the organic solvent in the step (III) is at least one selected from formamide, cyclohexane, tetramethylethylenediamine, pyridine, tetrahydrofuran, DMF and DMSO.

6. The method according to claim 2 or 3, wherein the alkaline agent in step (III) is selected from NaH, LiOH, NaOH, Na₂CO₃、KOH、Cs₂CO₃、Ca(OH)₂And K₂CO₃At least one of (1).

7. The method according to claim 2 or 3, wherein the hydrazine hydrate solution in the step (two) is a hydrazine hydrate aqueous solution with a concentration of 50 to 85 wt%.

8. Use of pentaaza-and/or oxodithiobicyclo-dienones according to claim 1 in medicaments for combating orthoptera, thysanoptera, homoptera, heteroptera, lepidoptera, coleoptera and diptera harmful insects.

9. Use of pentaaza-and/or oxo-dithiobicyclo-dienones according to claim 1 for the preparation of bacteriostatic medicaments.

10. Use of pentaaza-and/or oxo-dithiobicyclo-dienones as claimed in claim 1 for the preparation of a medicament for controlling grassy weeds and/or broad-leaved weeds.

11. Use of pentaaza-and/or oxo-dithiobicyclo-dienones according to claim 1 for the preparation of self-degradable fluorescent pesticides.