CN113582946B - 3-aryl-5-thio-1,3,4-thiadiazole-2-thioketone derivative and preparation method and application thereof - Google Patents

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative, and a preparation method and application thereof. According to the invention, hydrazine derivatives, carbon disulfide, electron-deficient olefin derivatives, a photocatalyst, an alkali reagent and a polar organic solvent are mixed, and cyclization reaction is carried out under the condition of illumination, so as to obtain the 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivatives. The invention provides energy required by reaction by utilizing illumination after mixing raw materials, and promotes the reaction to obtain a target product.

Description

3-aryl-5-thio-1,3,4-thiadiazole-2-thioketone derivative and preparation method and application thereof

Technical Field

The invention belongs to the technical field of organic synthesis, and particularly relates to a 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative, and a preparation method and application thereof.

Background

1,3,4-thiadiazole derivatives are one of the important N, S-heterocyclic fragments in organic synthesis, widely exist in various natural products and drug molecules, and have various biological activities, including anti-inflammatory, antibacterial, anticonvulsant, antihypertensive, anxiolytic, antifungal, antioxidant and anticancer activities, and thus are receiving increasing attention.

In the prior art, the document "A KHSO ₄ Promoted Tandem Synthesis of 1,3,4-thiadiazoles from Thiohydrazides and DMF Derivatives(Gan Z,et al.A KHSO ₄ Promoted Tandem Synthesis of 1,3,4-thiadiazoles from Thiohydrazides and DMF Derivatives[J]Tetrahedron Letters,2020,61 (31): 152195.) "discloses a preparation method, and the synthetic route is as follows:

the document "Synthesis of 2-Imino-1,3,4-thiadiazoles from Hydrazides and Isothiocyanates via Sequential Oxidation and P (NMe) ₂ ) ₃ -Mediated Annulation Reactions(Huang Z,et al.Synthesis of 2-Imino-1,3,4-thiadiazoles from Hydrazides and Isothiocyanates via Sequential Oxidation and P(NMe ₂ ) ₃ -Mediated Annulation Reactions[J]The synthetic route disclosed in Organic Letters,2020,22 (11) "is:

however, the above synthesis processes all require reaction at high temperature, and the reaction process is unstable.

Disclosure of Invention

The invention aims to provide a 3-aryl-5-thio-1,3,4-thiadiazole-2-thioketone derivative and a preparation method thereof.

In order to achieve the above purpose, the invention provides the following technical scheme:

the invention provides a preparation method of a 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative, which comprises the following steps:

mixing a hydrazine derivative, carbon disulfide, an electron-deficient olefin derivative, a photocatalyst, an alkali reagent and a polar organic solvent, and carrying out cyclization reaction under the condition of illumination to obtain the 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative;

the hydrazine derivative is R ₁ -NH-NH ₂ (ii) a The electron-deficient olefin derivative is

Wherein, R is ¹ Is phenyl, alkyl substituted phenyl, alkoxy substituted phenyl, halogen substituted phenyl, haloalkyl substituted phenyl, heterocyclic or fused ring group;

the R is ² Is an ester group, an amide group or a sulfone group.

Preferably, said R ¹ Wherein said alkyl-substituted phenyl is C _1～10 Alkyl-substituted phenyl; the alkoxy substituted phenyl is methoxy substituted phenyl; the halogen substituted phenyl is fluorine substituted phenyl, chlorine substituted phenyl or bromine substituted phenyl; halogen in the halogenated alkyl substituted phenyl is fluorine, chlorine or bromine; said heterocyclyl is pyridyl; the condensed ring group is naphthyl.

Preferably, the alkyl-substituted phenyl is p-methylphenyl, m-methylphenyl, o-methylphenyl, 3,4-dimethylphenyl, or 3,5-dimethylphenyl; the alkoxy substituted phenyl is p-methoxyphenyl or o-methoxyphenyl; the halogen-substituted phenyl is p-fluorophenyl, p-chlorophenyl, p-bromophenyl, m-chlorophenyl, m-bromophenyl, o-fluorophenyl, o-chlorophenyl, o-bromophenyl or 3,5-dichlorophenyl; the halogenated alkyl substituted phenyl is p-trifluoromethyl phenyl.

Preferably, the hydrazine derivative is replaced by hydrochloride of the hydrazine derivative.

Preferably, the ester group is an ethyl ester group, a methyl ester group, an isobutyl ester group, a cyclohexyl ester group, a furan methyl ester group, a hydroxyethyl ester group, a benzyl ester group, an isooctyl ester group, a methoxyethyl ester group, a tert-butyl ester group, an itaconic acid dimethyl ester group, an itaconic acid diethyl ester group or an isobornyl ester group; the acylamino is N, N-dimethylamido, acyl morpholinyl or N-phenylamido; the sulfonyl is a phenyl sulfonyl.

Preferably, the photocatalyst comprises one or more of tris (2,2-bipyridine) dichlororuthenium, 10-methyl-9-mesitylacridine perchlorate, tris (2-phenylpyridine) iridium, eosin B, eosin Y and rose bengal;

the alkali reagent comprises one or more of potassium phosphate, potassium carbonate, cesium carbonate, sodium hydroxide, 1,8-diazabicyclo [5.4.0] undec-7-ene, triethylene diamine, potassium tert-butoxide, N-methylmorpholine, cesium pivalate, lithium carbonate, sodium bicarbonate and tetrabutylammonium bromide.

Preferably, the molar ratio of the hydrazine derivative, the carbon disulfide, the electron-deficient olefin derivative, the photocatalyst and the alkali reagent is 2-3: 4 to 5:1 to 2:0.03 to 0.05:3 to 4;

the dosage ratio of the electron-deficient olefin derivative to the polar organic solvent is 0.1-0.2 mol:1L;

the wavelength of the light source for illumination is 200-1000 nm, and the time is 6-24 h.

The invention also provides a 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative, wherein the 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative has a structure shown in a formula I:

the R is ¹ Is phenyl, alkyl substituted phenyl, alkoxy substituted phenyl, halogen substituted phenyl, haloalkyl substituted phenyl, heterocyclic or fused ring group;

R ² is an ester group, an amide group or a sulfone group.

Preferably, said R ¹ Is p-methylphenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-methoxyphenyl, p-trifluoromethylphenyl, o-fluorophenyl, o-methylphenyl, o-chlorophenyl, o-methoxyphenyl, m-methylphenyl, m-chlorophenyl, m-bromoPhenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-dichlorophenyl, naphthyl, pyridinyl, or phenyl;

the R is ² Is an ethyl ester group, a methyl ester group, an isobutyl ester group, a furan methyl ester group, a cyclohexyl ester group, a hydroxyl ethyl ester group, a benzyl ester group, a methoxy ethyl ester group, an isooctyl ester group, a tert-butyl ester group, an itaconic acid dimethyl ester group, an itaconic acid diethyl ester group, an isobornyl ester group, an N, N-dimethyl acylamino group, an acyl morpholinyl group, an N-phenyl acylamino group or a phenylsulfonyl group.

The invention also provides application of the 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative in the technical scheme in preparation of anti-inflammatory, antibacterial, anticonvulsant, antihypertensive, anxiolytic, antifungal, antioxidant or antitumor drugs.

The invention provides a preparation method of a 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative, which comprises the following steps: mixing a hydrazine derivative, carbon disulfide, an electron-deficient olefin derivative, a photocatalyst, an alkali reagent and a polar organic solvent, and carrying out cyclization reaction under the condition of illumination to obtain a 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative; the hydrazine derivative is R ¹ -NH-NH ₂ (ii) a The electron-deficient olefin derivative is

Wherein, R is ¹ Is phenyl, alkyl substituted phenyl, alkoxy substituted phenyl, halogen substituted phenyl, haloalkyl substituted phenyl, heterocyclic or fused ring group; the R is ² Is an ester group, an amide group or a sulfone group. According to the invention, after the raw materials are mixed, high-temperature heating is not required, energy required by the reaction is provided by illumination, and the reaction is promoted, so that a target product is obtained, and the method has the advantages of stable reaction process, mild condition and easiness in control.

Detailed Description

The invention provides a preparation method of a 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative, which comprises the following steps:

mixing a hydrazine derivative, carbon disulfide, an electron-deficient olefin derivative, a photocatalyst, an alkali reagent and a polar organic solvent, and carrying out cyclization reaction under the condition of illumination to obtain the 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative;

the hydrazine derivative is R ¹ -NH-NH ₂ (ii) a The electron-deficient olefin derivative is

Wherein R is ¹ Is phenyl, alkyl substituted phenyl, alkoxy substituted phenyl, halogen substituted phenyl, haloalkyl substituted phenyl, heterocyclic group or condensed ring group;

the R is ² Is an ester group, an amide group or a sulfone group.

In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.

In the present invention, the route of the cyclization reaction is:

in the invention, the hydrazine derivative is R ¹ -NH-NH ₂ 。

In the present invention, said R ¹ Is phenyl, alkyl substituted phenyl, alkoxy substituted phenyl, halogen substituted phenyl, halogenated hydrocarbon substituted phenyl, heterocyclic radical or condensed ring radical. In the present invention, the alkyl-substituted phenyl group is preferably C _1～10 The alkyl-substituted phenyl group is more preferably a p-methylphenyl group, a m-methylphenyl group, an o-methylphenyl group, a 3,4-dimethylphenyl group or a 3,5-dimethylphenyl group. In the present invention, the alkoxy-substituted phenyl group is preferably a methoxy-substituted phenyl group, and more preferably a p-methoxyphenyl group or an o-methoxyphenyl group. In the present invention, the halogen-substituted phenyl group is preferably a fluorine-substituted phenyl group, a chlorine-substituted phenyl group or a bromine-substituted phenyl group, and more preferably a p-fluorophenyl group, a p-chlorophenyl group, a p-bromophenyl group, a m-chlorophenyl group, a m-bromophenyl group, an o-fluorophenyl group, an o-chlorophenyl group, an o-bromophenyl group, a p-bromophenyl group, or a bromine-substituted phenyl groupTrifluoromethylphenyl or 3,5-dichlorophenyl. In the present invention, the halogen in the haloalkyl-substituted phenyl group is preferably fluorine, chlorine or bromine; the haloalkyl-substituted phenyl group is more preferably a p-trifluoromethylphenyl group. In the present invention, the heterocycle is preferably pyridyl. In the present invention, the condensed ring is preferably a naphthyl group.

In the present invention, the hydrazine derivative is preferably replaced with a hydrochloride of the hydrazine derivative.

In a specific embodiment of the present invention, the hydrazine derivative is 4-methylphenylhydrazine hydrochloride, 4-fluorophenylhydrazine hydrochloride, 4-chlorophenylhydrazine hydrochloride, 4-bromophenylhydrazine hydrochloride, 4-methoxyphenylhydrazine hydrochloride, 4-trifluoromethylphenylhydrazine hydrochloride, 2-methylphenylhydrazine hydrochloride, 2-fluorophenylhydrazine hydrochloride, 2-chlorophenylhydrazine hydrochloride, 2-methoxyphenylhydrazine hydrochloride, 3-methylphenylhydrazine hydrochloride, 3-chlorophenylhydrazine hydrochloride, 3-bromophenylhydrazine hydrochloride, 3,4-dimethylphenylhydrazine hydrochloride, 3,5-dimethylphenylhydrazine hydrochloride, 3,5-dichlorophenylhydrazine hydrochloride, 1-naphthylhydrazine hydrochloride, 2-pyridine hydrochloride or phenylhydrazine.

In the present invention, the electron-deficient olefin derivative is

In the present invention, said R ² Is an ester group, an amide group or a sulfone group. In the present invention, the ester group is preferably an ethyl ester group, a methyl ester group, an isobutyl ester group, a cyclohexyl ester group, a furan methyl ester group, a hydroxyethyl ester group, a benzyl ester group, an isooctyl ester group, a methoxyethyl ester group, a tert-butyl ester group, an itaconic acid dimethylester group, an itaconic acid diethylester group or an isobornyl ester group. In the present invention, the amide group is preferably an N, N-dimethylamide group, an acylaorpholinyl group or an N-phenylamide group. In the present invention, the sulfone group is preferably a phenylsulfonyl group.

In a particular embodiment of the invention, the electron deficient olefin derivative is in particular ethyl acrylate, methyl acrylate, isobutyl acrylate, methyl (tetrahydro-2-furanyl) 2-acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, benzyl acrylate, 2-methoxyethyl acrylate, 2-ethylhexyl acrylate, tert-butyl acrylate, dimethyl itaconate, diethyl itaconate, N-dimethylacrylamide, acryloylmorpholine, N-phenylacrylamide, phenylvinylsulfone or isobornyl acrylate.

In the present invention, the photocatalyst preferably comprises one or more of tris (2,2-bipyridine) dichlororuthenium, 10-methyl-9-mesitylacridine perchlorate, tris (2-phenylpyridine) iridium, eosin B, eosin Y and rose bengal; when the photocatalyst is two or more of the above specific choices, the proportion of the specific material in the present invention is not particularly limited, and those known to those skilled in the art may be used. In the invention, the photocatalyst can be changed into an excited state through visible light and then generates free radical transfer with a reactant to promote the reaction.

In the present invention, the alkali agent preferably includes one or more of potassium phosphate, potassium carbonate, cesium carbonate, sodium hydroxide, 1,8-diazabicyclo [5.4.0] undec-7-ene, triethylenediamine, potassium tert-butoxide, N-methylmorpholine, cesium pivalate, lithium carbonate, sodium bicarbonate and tetrabutylammonium bromide; when the alkali agent is two or more selected from the above specific choices, the proportion of the specific substance in the present invention is not particularly limited, and those known to those skilled in the art can be used. In the present invention, the alkali agent can provide an alkaline condition for the reaction to promote the reaction.

In the present invention, the polar organic solvent preferably comprises one or more of dimethyl sulfoxide, ethanol, N-dimethylformamide, toluene, N-methylpyrrolidone, isopropanol, acetonitrile, ethyl acetate, ethanol, tetrahydrofuran, 1,4-dioxane and dichloromethane; when the polar organic solvent is two or more selected from the above specific choices, the ratio of the specific substances in the present invention is not particularly limited, and those known to those skilled in the art may be used. In the present invention, the polar organic solvent is capable of dissolving the reactants and promoting the reaction.

In the present invention, the molar ratio of the hydrazine derivative, carbon disulfide, electron deficient olefin derivative, photocatalyst and alkali agent is preferably 2 to 3:4 to 5:1 to 2:0.03 to 0.05:3 to 4, more preferably 3:4 to 5:1 to 2: 0.03-0.05: 4, more preferably 3:5:1 to 2:0.03 to 0.05:4. in the present invention, the electron-deficient olefin derivative and the polar organic solvent are preferably used in a ratio of 0.1 to 0.2mol:1L, more preferably 0.15mol:1L of the compound.

The mixing method is not particularly limited, and those known to those skilled in the art can be used.

In the present invention, the wavelength of the light source for the illumination is preferably 200 to 1000nm, more preferably 300 to 900nm, and still more preferably 400 to 800nm; the time is preferably 6 to 24 hours, more preferably 7 to 23 hours, and still more preferably 8 to 22 hours.

In the present invention, the cyclization reaction is preferably carried out under stirring. The rotation speed of the stirring is not particularly limited in the present invention, and those known to those skilled in the art can be used.

After the cyclization reaction is completed, the present invention preferably further performs a purification treatment on the reaction solution obtained by the reaction. In the present invention, the purification treatment is preferably performed by column chromatography. In the present invention, the eluent for the column chromatography is preferably a mixed solvent of petroleum ether and ethyl acetate. In the present invention, the volume ratio of petroleum ether to ethyl acetate in the mixed solvent is preferably 1 to 40: 1. the method for implementing the column chromatography is not particularly required, and the method is implemented by adopting a mode known by the technical personnel in the field. According to the invention, petroleum ether and ethyl acetate are used as eluent to carry out column chromatography purification treatment on the reaction liquid after cyclization reaction, so that the 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative with high purity can be obtained. In the present invention, the high-performance liquid phase purity of the 3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative is preferably 98.5 to 99.9%, and more preferably 99 to 99.9%.

In the invention, the energy required by the cyclization reaction is provided by utilizing illumination, and the 3-aryl-5-thio-1,3,4-thiadiazole-2-thioketone derivative can be obtained under the normal temperature condition without additionally providing a heat source by combining the selection of the raw materials, so that the whole reaction condition is mild and is easy to control. In addition, the preparation method of the 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative provided by the invention has better tolerance on functional groups, can be used for preparing 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivatives with different substituents, and has the advantages of readily available raw materials and low cost.

The invention also provides a 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative, wherein the 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative has a structure shown in a formula I:

said R is ¹ Is phenyl, alkyl substituted phenyl, alkoxy substituted phenyl, halogen substituted phenyl, haloalkyl substituted phenyl, heterocyclic group or condensed ring group;

R ² is an ester group, an amide group or a sulfone group.

In the present invention, said R ¹ And R in the above hydrazine derivatives ¹ Keeping consistent; said R is ² And R in the above electron-deficient olefin derivatives ² Keeping the same is not described herein.

In the present invention, said R ¹ Preferably p-methylphenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-methoxyphenyl, p-trifluoromethylphenyl, o-fluorophenyl, o-methylphenyl, o-chlorophenyl, o-methoxyphenyl, m-methylphenyl, m-chlorophenyl, m-bromophenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-dichlorophenyl, naphthyl, pyridyl or phenyl.

In the present invention, said R ² Preferably an ethyl ester group, a methyl ester group, an isobutyl ester group, a furan methyl ester group, a cyclohexyl ester group, a hydroxyethyl ester group, a benzyl ester group, a methoxyethyl ester group, an isooctyl ester group, a tert-butyl ester group, an itaconic acid dimethylester group, an itaconic acid diethoxy group, an isobornyl ester group, an N, N-dimethylamide group, an acylmorpholinyl group, an N-phenylamido group or a phenylsulfonyl group.

In a specific embodiment of the present invention, the structure of the 3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative is specifically as follows:

the invention also provides application of the 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative in the technical scheme in preparation of anti-inflammatory, antibacterial, anticonvulsant, antihypertensive, anxiolytic, antifungal, antioxidant or antitumor drugs. The invention is not particularly limited in its manner of use, as is well known to those skilled in the art.

To further illustrate the present invention, the following examples are provided to describe the 3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivatives and their preparation and use in detail, but they should not be construed as limiting the scope of the present invention.

Example 1

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown in a formula I-1:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 4-methylphenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 56.5mg of a purified target product, wherein the yield is 76 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )2980，1730，1507，1415，1237，1039，839，571；

¹ H NMR(400MHz，CDCl ₃ )δ7.59(d，J＝8.4Hz，2H)，7.29(d，J＝8.2Hz，2H)，4.16(q，J＝7.1Hz，2H)，3.39(t，J＝6.8Hz，2H)，2.80(t，J＝6.8Hz，2H)，2.40(s，3H)，1.25(d，J＝7.2Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.7，171.0，155.4，139.4，136.0，129.6，125.5，61.2，33.9，28.0，21.4，14.2；

HRMS(ESI)calcd for C ₁₃ H ₁₄ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 327.02985；found m/z 327.02902。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-1.

Example 2

A3-aryl-5-sulfo-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-2:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 4-fluorohydrazinium hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20: 56.3mg of the purified target product is obtained, the yield is 82%, and the purity is 99.9%.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3125，3078，2981，1880，1729，1601，1504，1416，1334，1228，1033，928，834，715，694，564，514；

¹ H NMR(400MHz，CDCl ₃ )δ7.73(dd，J＝9.0，4.8Hz，2H)，7.17(t，J＝8.6Hz，2H)，4.16(q，J＝7.1Hz，2H)，3.40(t，J＝6.8Hz，2H)，2.80(t，J＝6.8Hz，2H)，1.25(t，J＝7.1Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.9(s)，171.0(s)，163.4(s)，160.9(s)，155.7(s)，134.3(d，J＝3.2Hz)，127.7(d，J＝8.8Hz)，123.4(s)，116.1(s)，115.9(s)，61.2(s)，34.1(s)，33.9(s)，28.0(s)，14.2(s)；

HRMS(ESI)calcd for C ₁₃ H ₁₃ FN ₂ O ₂ S ₃ [M+H] ⁺ m/z 345.02052；found m/z 345.02031。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-2.

Example 3

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown in a formula I-3:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 4-chlorophenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 55.4mg of a purified target product, wherein the yield is 77 percent, and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3125，3078，2981，1880，1729，1601，1504，1416，1334，1228，1033，928，834，715，694，564，514；

¹ H NMR(400MHz，CDCl ₃ )δ7.71(d，J＝8.8Hz，2H)，7.40(d，J＝8.8Hz，2H)，4.12(q，J＝7.1Hz，2H)，3.36(t，J＝6.8Hz，2H)，2.77(t，J＝6.8Hz，2H)，1.22(d，J＝14.3Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.6，170.9，155.9，136.8，134.5，129.1，126.8，61.1，33.9，28.0，14.3；

HRMS(ESI)calcd for C ₁₃ H ₁₃ ClN ₂ O ₂ S ₃ [M+H] ⁺ m/z 360.99005；found m/z 360.99070。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-3.

Example 4

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown in a formula I-4:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 4-bromophenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 51.1mg of a purified target product, wherein the yield is 71 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are as follows:

IR(KBr，cm ^-1 )2980，1731，1588，1487，1372，1278，1040，832，700，622，507；

¹ H NMR(400MHz，CDCl ₃ )δ7.68(d，J＝6.8Hz，2H)，7.61(d，J＝8.9Hz，2H)，4.19–4.15(m，2H)，3.40(t，J＝6.8Hz，2H)，2.80(t，J＝6.8Hz，2H)，1.27(d，J＝7.1Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.7，170.9，156.0，137.3，132.1，127.1，122.8，61.2，33.9，28.0，14.2；

HRMS(ESI)calcd for C ₁₃ H ₁₃ BrN ₂ O ₂ S ₃ [M+H] ⁺ m/z 404.93953；found m/z 404.94027。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-4.

Example 5

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown in a formula I-5:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 4-methoxyphenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 52.0mg of a purified target product, wherein the yield is 74 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are as follows:

IR(KBr，cm ^-1 )3063，2973，2842，1880，1732，1614，1510，1457，1343，1249，1156，1027，943，833，792，694，574；

¹ H NMR(400MHz，CDCl ₃ )δ7.61(d，J＝9.0Hz，2H)，6.97(d，J＝9.0Hz，2H)，4.15(q，J＝7.1Hz，2H)，3.83(s，3H)，3.38(t，J＝6.8Hz，2H)，2.79(t，J＝6.8Hz，2H)，1.25(t，J＝7.1Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.7，171.0，159.7，155.2，131.2，127.1，114.1，61.2，55.6，33.9，28.0，14.2；

HRMS(ESI)calcd for C ₁₄ H ₁₆ N ₂ O ₃ S ₃ [M+H] ⁺ m/z 357.03958；found m/z 357.04042。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-5.

Example 6

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown in a formula I-6:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 4-trifluoromethylphenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 49.0mg of the purified target product, wherein the yield is 62 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )2917，2856，1731，1616，1324，1235，1173，1128，1058，842，739，621，540；

¹ H NMR(400MHz，CDCl ₃ )δ7.99(d，J＝8.4Hz，2H)，7.75(d，J＝8.5Hz，2H)，4.17(q，J＝7.1Hz，2H)，3.43(t，J＝6.8Hz，2H)，2.85–2.79(m，2H)，1.26(dd，J＝7.1，3.6Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ186.0(s)，170.9(s)，156.3(s)，141.2-140.9(m)，131.0-130.6(m)，130.6-130.2(m)，127.9-127.3(m)，126.1(d，J＝3.7Hz)，125.6(s)，125.0-124.6(m)，122.3-121.9(m)，120.9-120.3(m)，61.2(s)，33.9(s)，28.0(s)，14.2(s)；

HRMS(ESI)calcd for C ₁₄ H ₁₃ F ₃ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 395.01640；found m/z 395.01613。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-6.

Example 7

A3-aryl-5-sulfo-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-7:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 2-methylphenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 43.8mg of a purified target product, wherein the yield is 64 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3057，2980，2929，2864，1722，1583，1490，1463，1331，1285，1128，1040，927，836，781，694，618，453；

¹ H NMR(400MHz，CDCl ₃ )δ7.45-7.29(m，4H)，4.16(q，J＝7.1Hz，2H)，3.44-3.34(m，2H)，2.78(t，J＝6.8Hz，2H)，2.26(d，J＝7.8Hz，3H)，1.26(t，J＝7.1Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ186.6(s)，171.0(s)，155.6(s)，137.6(s)，135.8(s)，131.5(s)，130.3(s)，127.7(s)，127.1(s)，61.2(s)，33.9(s)，28.0(s)，17.9(s)，14.2(s)；

HRMS(ESI)calcd for C ₁₄ H ₁₆ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 341.04467；found m/z 327.04554。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-7.

Example 8

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown in a formula I-8:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 2-fluorophenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 43.8mg of a purified target product, wherein the yield is 64 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3074，2980，2934，1729，1595，1485，1346，1156，1043，845，759，693，535，481；

¹ H NMR(400MHz，CDCl ₃ )δ7.58-7.52(m，1H)，7.52-7.44(m，1H)，7.33-7.24(m，2H)，4.17(q，J＝7.1Hz，2H)，3.45-3.35(m，2H)，2.81(t，J＝6.8Hz，2H)，1.27(t，J＝7.1Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ187.4(s)，171.0(s)，158.3(s)，155.8(d，J＝18.2Hz)，131.8(d，J＝8.0Hz)，129.1(s)，126.2(d，J＝12.3Hz)，124.7(d，J＝3.9Hz)，117.2(d，J＝19.0Hz)，111.3(s)，61.1(s)，33.8(s)，28.0(s)，14.2(s)；

HRMS(ESI)calcd for C ₁₃ H ₁₃ FN ₂ O ₂ S ₃ [M+H] ⁺ m/z 345.02052；found m/z 345.02031。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-8.

Example 9

A3-aryl-5-sulfo-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-9:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 2-chlorophenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining the target product 42.8mg after purification, the yield is 59 percent, and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are as follows:

IR(KBr，cm ^-1 )3063，2980，2930，1731，1630，1580，1482，1446，1416，1372，1344，1244，1104，1039，830，762，729，704，685，615，475，454；

¹ H NMR(400MHz，CDCl ₃ )δ7.59(d，J＝7.5Hz，1H)，7.53(d，J＝2.3Hz，1H)，7.51–7.44(m，2H)，4.18(q，J＝7.1Hz，2H)，3.41(t，J＝6.8Hz，2H)，2.82(t，J＝6.8Hz，2H)，1.28(s，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ187.4(s)，171.0(s)，155.7(s)，136.1(s)，132.3(s)，131.4(s)，130.8(s)，129.7(s)，127.9(s)，61.1(s)，33.8(s)，28.0(s)，14.2(s)；

HRMS(ESI)calcd for C ₁₃ H ₁₃ ClN ₂ O ₂ S ₃ [M+H] ⁺ m/z 360.99005；found m/z 360.99070。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-9.

Example 10

A3-aryl-5-sulfo-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-10:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 2-methoxyphenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 44.2mg of a purified target product, wherein the yield is 62 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3050，2978，2839，2040，1732，1600，1501，1467，1345，1256，1127，1043，928，834，755，697，567，472；

¹ H NMR(400MHz，CDCl ₃ )δ7.49-7.44(m，1H)，7.40(d，J＝8.1Hz，1H)，7.10-7.05(m，2H)，4.16(q，J＝7.1Hz，2H)，3.86(s，3H)，3.37(t，J＝6.9Hz，2H)，2.79(t，J＝6.9Hz，2H)，1.26(t，J＝7.1Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ187.5(s)，171.1(s)，154.8(s)，131.6(s)，128.9(s)，127.1(s)，120.8(s)，112.7(s)，61.1(s)，56.0(s)，33.8(s)，28.0(s)，14.2(s)；

HRMS(ESI)calcd for C ₁₄ H ₁₆ N ₂ O ₃ S ₃ [M+H] ⁺ m/z 357.03958；found m/z 357.04014。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-10.

Example 11

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown in a formula I-11:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 3-methylphenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 49.8mg of a purified target product, wherein the yield is 73 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3439，2980，1720，1609，1490，1372，1328，1183，1055，893，786，688，618，446；

¹ H NMR(400MHz，CDCl ₃ )δ7.50(s，1H)，7.44(m，1H)，7.24(d，J＝7.5Hz，1H)，4.17(q，J＝7.1Hz，2H)，3.40(t，J＝6.8Hz，2H)，2.81(t，J＝6.8Hz，2H)，2.42(s，3H)，1.26(t，J＝7.1Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.9(s)，171.09(s)，155.4(s)，139.2(s)，138.3(s)，123.0(s)，128.8(s)，126.2(s)，122.9(s)，61.2(s)，34.0(s)，28.0(s)，21.5(s)，14.2(s)；

HRMS(ESI)calcd for C ₁₄ H ₁₆ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 341.04467；found m/z 327.04554。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-11.

Example 12

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown in a formula I-12:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 3-chlorophenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 50.4mg of a purified target product, wherein the yield is 70 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3069，2980，2933，1730，1688，1588，1475，1331，1280，1223，1105，1045，927，862，783，730，682，621；

¹ H NMR(400MHz，CDCl ₃ )δ7.78(s，1H)，7.72(d，J＝7.3Hz，1H)，7.41(d，J＝8.5Hz，2H)，4.20-4.14(m，2H)，3.41(t，J＝6.8Hz，2H)，2.81(t，J＝6.8Hz，2H)，1.26(t，J＝7.1Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.9(s)，170.9(s)，156.0(s)，139.2(s)，134.5(s)，129.9(s)，129.1(s)，125.7(s)，123.7(s)，77.5(s)，77.1(s)，76.8(s)，61.2(s)，33.9(s)，28.0(s)，14.2(s)；

HRMS(ESI)calcd for C ₁₃ H ₁₃ ClN ₂ O ₂ S ₃ [M+H] ⁺ m/z 360.99005；found m/z 360.99070。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-12.

Example 13

A3-aryl-5-sulfo-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-13:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 3-bromophenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 55.5mg of a purified target product, wherein the yield is 68 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are as follows:

IR(KBr，cm ^-1 )3069，2979，1730，1682，1583，1474，1372，1330，1280，1047，869，846，782，717，681，615，445；

¹ H NMR(400MHz，CDCl ₃ )δ7.93(t，J＝1.9Hz，1H)，7.76(d，J＝8.1Hz，1H)，7.55(d，J＝8.8Hz，1H)，7.36(t，J＝8.1Hz，1H)，4.19-4.13(m，2H)，3.41(t，J＝6.8Hz，2H)，2.81(t，J＝6.8Hz，2H)，1.26(t，J＝7.1Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.9(s)，170.9(s)，156.0(s)，139.3(s)，132.1(s)，130.1(s)，128.6(s)，124.2(s)，122.2(s)，61.2(s)，33.9(s)，28.0(s)，14.2(s)；

HRMS(ESI)calcd for C ₁₃ H ₁₃ BrN ₂ O ₂ S ₃ [M+H] ⁺ m/z 404.93953；found m/z 404.94001。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-13.

Example 14

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-14:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 3, 4-dimethylphenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 41.5mg of a purified target product, wherein the yield is 59 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are as follows:

IR(KBr，cm ^-1 )3065，2923，1753，1680，1500，1372，1344，1285，1081，955，916，816，779，709，602，443；

¹ H NMR(400MHz，CDCl ₃ )δ185.8(s)，171.0(s)，155.2(s)，138.2(s)，137.7(s)，136.1(s)，130.1(s)，126.6(s)，123.2(s)，61.2(s)，34.0(s)，28.0(s)，19.9(s)，19.7(s)，14.2(s)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.7，171.0，155.4，139.4，136.0，129.6，125.5，61.2，33.9，28.0，21.4，14.2；

HRMS(ESI)calcd for C ₁₅ H ₁₈ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 355.06032；found m/z 355.06036。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-14.

Example 15

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-15:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 3, 5-dimethylphenylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 48.5mg of the purified target product, the yield is 69 percent, and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3097，2980，2929，1730，1691，1586，1471，1372，1325，1228，1134，1049，873，816，747，671，524；

¹ H NMR(400MHz，CDCl ₃ )δ7.28(s，2H)，7.07(s，1H)，4.17(q，J＝7.1Hz，2H)，3.40(t，J＝6.8Hz，2H)，2.80(t，J＝6.8Hz，2H)，2.38(s，6H)，1.27(t，J＝7.1Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.9(s)，171.0(s)，155.3(s)，139.0(s)，138.2(s)，131.0(s)，123.5(s)，61.6(s)，34.0(s)，28.0(s)，21.3(s)，14.2(s)；

HRMS(ESI)calcd for C ₁₅ H ₁₈ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 355.06032；found m/z 355.06036。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-15.

Example 16

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-16:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 3, 5-dichlorohydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 47.4mg of purified target product with 61 percent of yield and 99.9 percent of purity.

The structure of the resulting product was characterized, and the data for structural characterization are as follows:

IR(KBr，cm ^-1 )3078，3004，2985，2920，1740，1576，1435，1375，1186，1088，1065，1040，1016，888，857，805，772，668，585，475；

¹ H NMR(400MHz，CDCl ₃ )δ7.78(d，J＝1.8Hz，2H)，7.41(t，J＝1.8Hz，1H)，4.17(t，J＝7.1Hz，2H)，3.44(d，J＝6.9Hz，2H)，2.82(t，J＝6.8Hz，2H)，1.27(t，J＝7.1Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.9(s)，170.9(s)，156.4(s)，139.6(s)，135.1(s)，129.0(s)，124.0(s)，61.3(s)，33.9(s)，28.0(s)，14.2(s)；

HRMS(ESI)calcd for C ₁₃ H ₁₂ ClN ₂ O ₂ S ₃ [M+H] ⁺ m/z 394.95107；found m/z 394.95153。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-16.

Example 17

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-17:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 1-naphthylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 47.8mg of a purified target product, wherein the yield is 63 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are as follows:

IR(KBr，cm ^-1 )3062，2979，2934，1726，1628，1597，1508，1472，1395，1131，1045，991，949，865，772，735，694，630，537，512；

¹ H NMR(400MHz，CDCl ₃ )δ8.00(t，J＝7.4Hz，1H)，7.98-7.92(m，1H)，7.70-7.64(m，1H)，7.63-7.52(m，4H)，4.14(dt，J＝10.0，5.6Hz，2H)，3.37(t，J＝6.8Hz，2H)，2.76(t，J＝6.8Hz，2H)，1.24(t，J＝7.1Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ187.5(s)，171.0(s)，155.9(s)，135.0(s)，134.5(s)，130.7(s)，128.9(s)，128.7(s)，127.6(s)，126.9(s)，126.4(s)，125.4(s)，122.6(s)，61.1(s)，60.8(s)，33.9(s)，28.0(s)，14.2(d，J＝6.0Hz)；

HRMS(ESI)calcd for C ₁₇ H ₁₆ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 377.04467；found m/z 377.04533。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-17.

Example 18

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-18:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of 2-pyridylhydrazine hydrochloride, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining the purified target product 42.7mg with the yield of 85% and the purity of 99.9%.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )2980，1737，1641，1528，1417，1315，1118，1075，987，887，752，601，540，482，428；

¹ H NMR(400MHz，CDCl ₃ )δ8.29(d，J＝7.1Hz，1H)，7.34(t，J＝9.4Hz，1H)，6.79(t，J＝6.7Hz，1H)，4.69(t，J＝7.2Hz，1H)，4.13(q，J＝7.1Hz，1H)，2.95(t，J＝7.2Hz，1H)，1.21(t，J＝7.1Hz，2H)；

¹³ C NMR(100MHz，CDCl ₃ )δ170.4(s)，159.1(s)，145.3(s)，131.0(s)，126.1(s)，115.1(s)，113.1(s)，77.5(s)，77.1(s)，76.8(s)，61.0(s)，45.3(s)，32.6(s)，14.1(s)；

HRMS(ESI)calcd for C ₁₁ H ₁₃ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 252.08012；found m/z 252.08035。

according to the above data, the product obtained in this example conforms to the structure shown in formula one.

Example 19

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown in a formula I-19:

the preparation method comprises the following steps: adding 0.2mmol of ethyl acrylate, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 55.4mg of a purified target product, wherein the yield is 85 percent, and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )2990，2941，2853，1724，1682，1591，1487，1472，1345，1233，1152，1097，1033，951，922，828，769，707，691，608；

¹ H NMR(400MHz，CDCl ₃ )δ7.73(d，J＝7.6Hz，2H)，7.47(t，J＝7.6Hz，2H)，7.41(d，J＝7.3Hz，1H)，4.14(q，J＝7.1Hz，2H)，3.39(t，J＝6.8Hz，2H)，2.79(t，J＝6.8Hz，2H)，1.24(t，J＝7.1Hz，3H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.8(s)，171.0(s)，155.5(s)，138.4(s)，129.0(d，J＝9.8Hz)，125.6(s)，61.1(s)，34.0(s)，28.0(s)，14.2(s)；

HRMS(ESI)calcd for C ₁₃ H ₁₄ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 327.02985；found m/z 327.02902。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-19.

Example 20

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-20:

the preparation method comprises the following steps: adding 0.2mmol of methyl acrylate, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 55.4mg of a purified target product, wherein the yield is 85 percent, and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3442，2985，2945，2354，1728，1633，1487，1470，1345，1050，936，829，770，650，607，542；

¹ H NMR(400MHz，CDCl ₃ )δ7.73(d，J＝7.3Hz，2H)，7.50(t，J＝7.5Hz，2H)，7.44(d，J＝7.3Hz，1H)，3.70(s，3H)，3.41(t，J＝6.8Hz，2H)，2.83(t，J＝6.8Hz，2H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.8(s)，171.5(s)，155.5(s)，138.4(s)，129.1(d，J＝11.8Hz)，125.7(s)，52.2(s)，33.7(s)，27.9(s)；

HRMS(ESI)calcd for C ₁₂ H ₁₂ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 312.01337；found m/z 313.01433。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-20.

Example 21

A3-aryl-5-sulfo-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-21:

the preparation method comprises the following steps: adding 0.2mmol of isobutyl acrylate, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) ruthenium dichloride and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 52.8mg of the purified target product, wherein the yield is 74 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3064，2959，1729，1692，1593，1493，1396，1355，1226，1038，930，821，760，687，610，579，495；

¹ H NMR(400MHz，CDCl ₃ )δ7.74(d，J＝8.0Hz，2H)，7.48(t，J＝7.5Hz，2H)，7.42(d，J＝7.3Hz，1H)，3.88(d，J＝6.7Hz，2H)，3.40(t，J＝6.8Hz，2H)，2.82(t，J＝6.8Hz，2H)，1.92(dt，J＝13.4，6.7Hz，1H)，0.91(d，J＝6.7Hz，6H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.8(s)，171.0(s)，155.5(s)，138.4(s)，129.0(d，J＝9.5Hz)，125.6(s)，71.2(s)，34.8(s)，34.0(s)，28.0(s)，27.7(s)，19.1(s)；

HRMS(ESI)calcd for C ₁₅ H ₁₈ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 355.06032；found m/z 355.06098。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-21.

Example 22

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-22:

the preparation method comprises the following steps: adding 0.2mmol of 2-acrylic acid (tetrahydro-2-furyl) methyl ester, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) ruthenium dichloride and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20: 55.4mg of the purified target product is obtained, the yield is 79%, and the purity is 99.9%.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3064，2949，2870，1732，1691，1494，1338，1237，1040，920，824，735，689，611；

¹ H NMR(400MHz，CDCl ₃ )δ7.74(d，J＝7.8Hz，2H)，7.50(t，J＝7.5Hz，2H)，7.44(t，J＝6.8Hz，1H)，4.19(d，J＝3.1Hz，1H)，4.14-4.07(m，1H)，4.03(dd，J＝11.1，7.1Hz，1H)，3.87(dd，J＝15.0，6.7Hz，1H)，3.79(dd，J＝14.2，7.5Hz，1H)，3.42(t，J＝6.8Hz，2H)，2.88(t，J＝6.8Hz，2H)，2.05-1.96(m，1H)，1.95-1.87(m，2H)，1.63-1.55(m，1H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.8(s)，171.0(s)，155.4(s)，138.4(s)，129.0(d，J＝11.0Hz)，125.7(s)，76.3(s)，68.5(s)，67.1(s)，33.8(s)，27.9(d，J＝6.8Hz)，25.7(s)；

HRMS(ESI)calcd for C ₁₆ H ₁₈ N ₂ O ₃ S ₃ [M+H] ⁺ m/z 383.05523；found m/z 383.05627。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-22.

Example 23

A3-aryl-5-sulfo-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-23:

the preparation method comprises the following steps: adding 0.2mmol of cyclohexyl acrylate, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 58.6mg of the purified target product, wherein the yield is 77 percent, and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3069，2935，2857，1729，1592，1494，1452，1409，1338，1292，1236，1192，1155，1122，1040，823，760，703，688；

¹ H NMR(400MHz，CDCl ₃ )δ7.74(d，J＝7.7Hz，2H)，7.48(t，J＝7.5Hz，2H)，7.44-7.38(m，1H)，4.79(dd，J＝8.2，3.9Hz，1H)，3.39(t，J＝6.7Hz，2H)，2.78(t，J＝6.7Hz，2H)，1.82(d，J＝10.0Hz，2H)，1.70(d，J＝8.2Hz，2H)，1.57-1.48(m，1H)，1.34(ddd，J＝30.1，18.9，10.6Hz，5H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.8(s)，170.4(s)，155.6(s)，138.4(s)，129.0(d，J＝9.5Hz)，125.6(s)，73.6(s)，34.3(s)，31.6(s)，28.2(s)，25.3(s)，23.7(s)；

HRMS(ESI)calcd for C ₁₇ H ₂₀ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 381.07597；found m/z 381.07714。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-23.

Example 24

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-24:

the preparation method comprises the following steps: adding 0.2mmol of 2-hydroxyethyl acrylate, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 54.1mg of a purified target product, wherein the yield is 77 percent, and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3433，2957，1733，1688，1493，1341，1236，1189，1050，831，764，689，607，492；

¹ H NMR(400MHz，CDCl ₃ )δ7.73(d，J＝8.0Hz，2H)，7.50(t，J＝7.5Hz，2H)，7.44(t，J＝6.8Hz，1H)，4.26-4.20(m，2H)，3.84-3.77(m，2H)，3.42(t，J＝6.8Hz，2H)，2.88(t，J＝6.8Hz，2H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.9(s)，171.4(s)，155.5(s)，138.3(s)，129.1(d，J＝14.8Hz)，125.7(s)，66.5(s)，60.8(s)，33.8(s)，27.9(s)；

HRMS(ESI)calcd for C ₁₃ H ₁₄ N ₂ O ₃ S ₃ [M+H] ⁺ m/z 343.02393；found m/z 343.02474。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-24.

Example 25

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-25:

the preparation method comprises the following steps: adding 0.2mmol of benzyl acrylate, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 54.1mg of a purified target product, wherein the yield is 77 percent, and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3063，3032，2929，1730，1680，1592，1494，1454，1414，1339，1297，1234，1040，962，823，752，696，611，576；

¹ H NMR(400MHz，CDCl ₃ )δ7.75(d，J＝7.1Hz，2H)，7.50(t，J＝7.5Hz，2H)，7.44(d，J＝7.3Hz，1H)，7.39-7.33(m，5H)，5.16(s，2H)，3.43(t，J＝6.8Hz，2H)，2.88(t，J＝6.8Hz，2H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.8(s)，170.9(s)，155.5(s)，138.4(s)，135.4(s)，129.1(d，J＝10.1Hz)，128.8-128.3(m)，125.7(s)，121.4(s)，67.0(s)，34.0(s)，28.0(s)；

HRMS(ESI)calcd for C ₁₈ H ₁₆ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 389.04467；found m/z 389.04514。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-25.

Example 26

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-26:

the preparation method comprises the following steps: adding 0.2mmol of 2-methoxyethyl acrylate, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20: 54.1mg of the purified target product is obtained, the yield is 77%, and the purity is 99.9%.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3455，3071，2927，2888，2820，1730，1694，1592，1488，1406，1336，1235，1127，1025，928，823，761，689，611，579；

¹ H NMR(400MHz，CDCl ₃ )δ7.72(d，J＝7.9Hz，2H)，7.47(t，J＝7.6Hz，2H)，7.40(t，J＝7.4Hz，1H)，4.27-4.21(m，2H)，3.59-3.53(m，2H)，3.39(t，J＝6.8Hz，2H)，3.35(s，3H)，2.85(t，J＝6.8Hz，2H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.7(s)，171.1(s)，155.5(s)，138.4(s)，129.0(d，J＝10.9Hz)，125.7(s)，70.2(s)，64.1(s)，59.0(s)，33.8(s)，27.9(s)；

HRMS(ESI)calcd for C ₁₄ H ₁₆ N ₂ O ₃ S ₃ [M+H] ⁺ m/z 357.03958；found m/z 357.04056。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-26.

Example 27

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-27:

the preparation method comprises the following steps: adding 0.2mmol of 2-ethylhexyl acrylate, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 54.7mg of a purified target product, wherein the yield is 68 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are as follows:

IR(KBr，cm ^-1 )3066，2954，2873，1730，1694，1593，1494，1414，1337，1256，1182，1051，1006，980，822，760，688，611，571；

¹ H NMR(400MHz，CDCl ₃ )δ7.79-7.73(m，2H)，7.55-7.49(m，2H)，7.46(d，J＝7.3Hz，1H)，4.05(dd，J＝5.8，2.7Hz，2H)，3.44(dd，J＝9.0，4.7Hz，2H)，2.85(t，J＝6.8Hz，2H)，1.59(dt，J＝12.0，6.0Hz，1H)，1.39–1.29(m，8H)，0.90(t，J＝7.5Hz，6H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.9(s)，171.1(s)，155.4(s)，138.4(s)，129.0(d，J＝9.8Hz)，125.6(s)，67.6(s)，38.7(s)，34.0(s)，30.4(s)，28.9(s)，28.1(s)，23.8(s)，22.96(s)，14.07(s)，10.99(s)；

HRMS(ESI)calcd for C ₁₉ H ₂₆ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 411.12292；found m/z 411.12348。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-27.

Example 28

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-28:

the preparation method comprises the following steps: adding 0.2mmol of tert-butyl acrylate, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 57.1mg of a purified target product, wherein the yield is 81 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are as follows:

IR(KBr，cm ^-1 )3060，2976，2929，1728，1593，1493，1456，1366，1337，1309，1234，1149，1041，960，929，840，823，760，688，613，576；

¹ H NMR(400MHz，CDCl ₃ )δ7.77-7.71(m，2H)，7.52-7.46(m，2H)，7.44-7.38(m，1H)，3.36(t，J＝6.8Hz，2H)，2.72(t，J＝6.8Hz，2H)，1.45(s，9H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.8(s)，170.2(s)，155.7(s)，138.4(s)，129.0(d，J＝9.6Hz)，125.6(d，J＝1.0Hz)，81.7(s)，35.0(s)，28.2(d，J＝13.4Hz)；

HRMS(ESI)calcd for C ₁₅ H ₁₈ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 355.06032；found m/z 355.06100。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-28.

Example 29

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-29:

the preparation method comprises the following steps: adding 0.2mmol of dimethyl itaconate, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 58.7mg of a purified target product, wherein the yield is 75 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )3062，2999，2951，2842，1746，1693，1592，1493，1436，1238，1070，1043，1003，966，889，824，763，735，690，649，611，492；

¹ H NMR(400MHz，CDCl ₃ )δ7.77(dd，J＝8.4，1.1Hz，2H)，7.51(d，J＝7.9Hz，2H)，7.44(s，1H)，3.73(s，3H)，3.57(d，J＝6.5Hz，4H)，3.43(dd，J＝13.8，6.4Hz，1H)，3.35-3.27(m，1H)，2.85(dd，J＝16.9，6.9Hz，1H)，2.72(dd，J＝16.9，6.2Hz，1H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.9(s)，172.5(s)，171.3(s)，155.1(s)，138.4(s)，129.0(d，J＝12.6Hz)，125.6(s)，52.6(s)，52.0(s)，41.1(s)，34.6(s)，33.5(s)；

HRMS(ESI)calcd for C ₁₅ H ₁₆ N ₂ O ₄ S ₃ [M+H] ⁺ m/z 385.03450；found m/z 385.03544。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-29.

Example 30

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-30:

the preparation method comprises the following steps: adding 0.2mmol of diethyl itaconate, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 57.7mg of a purified target product, wherein the yield is 75 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are as follows:

IR(KBr，cm ^-1 )3487，3384，2931，2854，1625，1590，1487，1378，1224，1123，1071，975，899，734，692；

¹ H NMR(400MHz，CDCl ₃ )δ8.24(d，J＝8Hz，2H)，7.50(t，J＝8Hz，1H)，7.39(t，J＝8Hz，2H)，7.21-7.17(m，2H)，6.93-6.87(m，3H)，4.97(s，2H)，3.39-3.31(m，1H)，1.80-1.68(m，4H)，1.61-1.51(m，3H)，1.07-0.75(m，2H)；

¹³ C NMR(100MHz，CDCl ₃ )δ187.5，150.4，147.1，135.9，132.6，131.4，128.9，127.7，122.7，121.1，67.3，30.3，26.1，26.0；

HRMS(ESI)calcd for C ₂₀ H ₂₃ N ₃ O[M+H] ⁺ m/z 322.1919；found m/z 322.1919。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-30.

Example 31

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-31:

the preparation method comprises the following steps: adding 0.2mmol of N, N-dimethylacrylamide, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 47.1mg of purified target product with 72 percent of yield and 99.9 percent of purity.

The structure of the resulting product was characterized, and the data for structural characterization are as follows:

IR(KBr，cm ^-1 )3044，2926，1643，1593，1493，1401，1377，1262，1237，1140，1041，963，935，824，763，734，690，612，579，496；

¹ H NMR(400MHz，CDCl ₃ )δ7.73(d，J＝7.9Hz，2H)，7.49(t，J＝7.6Hz，2H)，7.42(t，J＝6.9Hz，1H)，3.45(t，J＝6.7Hz，2H)，2.95(d，J＝4.9Hz，6H)，2.79(t，J＝6.7Hz，2H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.7(s)，171.0(s)，155.4(s)，139.4(s)，135.9(s)，129.6(s)，125.5(s)，61.2(s)，33.9(s)，28.0(s)，21.4(s)，14.2(s)；

HRMS(ESI)calcd for C ₁₂ H ₁₁ N ₂ OS ₃ [M+H] ⁺ m/z 326.04500；found m/z 326.04556。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-31.

Example 32

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown in a formula I-32:

the preparation method comprises the following steps: adding 0.2mmol of acryloyl morpholine, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 46.7mg of the purified target product, wherein the yield is 63 percent and the purity is 99.9 percent.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )2962，2920，2854，1642，1593，1493，1458，1437，1339，1270，1235，1114，1046，1025，825，763，689，613；

¹ H NMR(400MHz，CDCl ₃ )δ7.71(d，J＝7.9Hz，2H)，7.48(t，J＝7.5Hz，2H)，7.42(t，J＝7.3Hz，1H)，3.63(d，J＝5.1Hz，2H)，3.58(dd，J＝9.1，4.4Hz，4H)，3.44(t，J＝6.8Hz，2H)，3.41-3.35(m，2H)，2.78(t，J＝6.8Hz，2H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.8(s)，168.7(s)，156.4(s)，138.4(s)，129.1(d，J＝13.3Hz)，125.7(s)，66.8(s)，66.4(s)，45.7(s)，42.1(s)，32.9(s)，28.3(s)；

HRMS(ESI)calcd for C ₁₅ H ₁₇ N ₃ O ₂ S ₃ [M+H] ⁺ m/z 368.05557；found m/z 368.05651。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-32.

Example 33

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-33:

the preparation method comprises the following steps: adding 0.2mmol of N-phenylacrylamide, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining the purified target product 46.7mg with 68% yield and 99.9% purity.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )2921，2850，1662，1598，1538，1494，1338，1236，1037，826，754，689，611；

¹ H NMR(400MHz，CDCl ₃ )δ7.75(d，J＝7.5Hz，2H)，7.62(s，1H)，7.53-7.43(m，5H)，7.31(t，J＝7.8Hz，2H)，7.13(s，1H)，3.52(t，J＝6.7Hz，2H)，2.85(t，J＝6.7Hz，2H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.8(s)，168.2(s)，157.0(s)，138.4(s)，137.4(s)，129.1(d，J＝12.5Hz)，125.6(s)，124.7(s)，119.9(s)，36.7(s)，28.5(s)；

HRMS(ESI)calcd for C ₁₇ H ₁₅ N ₃ OS ₃ [M+H] ⁺ m/z 374.04500；found m/z 374.04555。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-33.

Example 34

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown as a formula I-34:

the preparation method comprises the following steps: adding 0.2mmol of phenyl vinyl sulfone, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining 34.6mg of a purified target product, wherein the yield is 44% and the purity is 99.9%.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )2921，1695，1592，1493，1446，1410，1321，1236，1149，1084，1053，795，760，687，611，579，553，530；

¹ H NMR(400MHz，CDCl ₃ )δ7.87-7.83(m，2H)，7.66-7.59(m，3H)，7.54-7.42(m，6H)，3.61-3.54(m，2H)，3.44-3.38(m，2H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.7(s)，154.0(s)，138.2(d，J＝4.2Hz)，134.3(s)，129.5(s)，129.2(s)，129.1(s)，128.0(s)，125.5(s)，55.1(s)，25.6(s)；

HRMS(ESI)calcd for C ₁₆ H ₁₄ N ₂ O ₂ S ₄ [M+H] ⁺ m/z 395.00109；found m/z 395.00069。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-34.

Example 35

A3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivative has a structure shown in a formula I-35:

the preparation method comprises the following steps: adding 0.2mmol of isobornyl acrylate, 0.3mmol of phenylhydrazine, 0.5mmol of carbon disulfide, 0.4mmol of cesium carbonate, 0.003mmol of tris (2,2-bipyridine) dichlororuthenium and 1mL of acetonitrile into a reaction tube, mixing, stirring and reacting for 12 hours under the irradiation of a light source with the wavelength of 470nm, separating and purifying by column chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 20:1, obtaining the target product 42.6mg after purification, with 49% yield and 99.9% purity.

The structure of the resulting product was characterized, and the data for structural characterization are shown below:

IR(KBr，cm ^-1 )2954，2877，1729，1694，1593，1494，1454，1416，1339，1240，1182，1052，1006，980，943，823，760，737，703，689，611；

¹ H NMR(400MHz，CDCl ₃ )δ7.74(dt，J＝3.6，2.2Hz，2H)，7.54-7.40(m，3H)，4.70(dd，J＝7.7，3.4Hz，1H)，3.42-3.37(m，2H)，2.83-2.75(m，2H)，1.74(dddd，J＝21.2，16.4，7.9，3.1Hz，4H)，1.59-1.51(m，1H)，1.17-1.06(m，2H)，0.95(d，J＝7.2Hz，3H)，0.83(t，J＝4.3Hz，6H)；

¹³ C NMR(100MHz，CDCl ₃ )δ185.8(s)，170.3(s)，155.5(s)，138.4(s)，129.0(d，J＝10.2Hz)，125.6(s)，121.4(s)，81.9(s)，48.8(s)，47.0(s)，45.5(s)，38.7(s)，34.3(s)，33.7(s)，28.1(s)，27.0(s)，20.0(d，J＝15.2Hz)，11.6(s)；

HRMS(ESI)calcd for C ₂₁ H ₂₆ N ₂ O ₂ S ₃ [M+H] ⁺ m/z 435.12292；found m/z 435.12380。

from the above data, it can be seen that the product obtained in this example conforms to the structure shown in formula I-35.

From examples 1 to 35, the present invention provides a series of 3-aryl-5-thio-1,3,4-thiadiazole-2-thione derivatives. The invention provides the required energy for the reaction by utilizing illumination, combines the selection of the raw materials, can obtain the 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative under the normal temperature condition without additionally providing a heat source, has mild whole reaction condition and is easy to control. The 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative obtained by the invention has high purity and high application value.

Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.

Claims (4)

1. A preparation method of 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thione derivatives is characterized by comprising the following steps:

mixing a hydrazine derivative, carbon disulfide, an electron-deficient olefin derivative, a photocatalyst, an alkali reagent and a polar organic solvent, and carrying out cyclization reaction under the condition of illumination to obtain the 3-aryl-5-sulfo-1,3,4-thiadiazole-2-thioketone derivative;

the hydrazine derivative is R ¹ -NH-NH ₂ (ii) a The electron-deficient olefin derivative is

The R is ¹ Is phenyl, alkyl substituted phenyl, alkoxy substituted phenyl, halogen substituted phenyl, haloalkyl substituted phenyl, heterocyclic or fused ring group; the alkyl-substituted phenyl is C _1～10 Alkyl-substituted phenyl; the alkoxy substituted phenyl is methoxy substituted phenyl; the halogen substituted phenyl is fluorine substituted phenyl, chlorine substituted phenyl or bromine substituted phenyl; halogen in the halogenated alkyl substituted phenyl is fluorine, chlorine or bromine; said heterocyclyl is pyridyl; the condensed ring group is naphthyl;

the R is ² Is an ester group, an amide group or a sulfone group; the ester group is an ethyl ester group, a methyl ester group, an isobutyl ester group, a cyclohexyl ester group, a furan methyl ester group, a hydroxyethyl ester group, a benzyl ester group, an isooctyl ester group, a methoxyethyl ester group, a tert-butyl ester group, an itaconic acid dimethyl ester group, an itaconic acid diethyl ester group or an isobornyl ester group; the acylamino is N, N-dimethylamido, acyl morpholinyl or N-phenylamido; the sulfonyl is a phenyl sulfonyl;

the photocatalyst is tris (2,2-bipyridine) ruthenium dichloride;

the alkali reagent is one or more of potassium carbonate, cesium carbonate and lithium carbonate;

the polar organic solvent is acetonitrile;

the light source wavelength of the illumination is 470nm.

2. The method of claim 1, wherein the alkyl-substituted phenyl is p-methylphenyl, m-methylphenyl, o-methylphenyl, 3,4-dimethylphenyl, or 3,5-dimethylphenyl; the alkoxy substituted phenyl is p-methoxyphenyl or o-methoxyphenyl; the halogen-substituted phenyl is p-fluorophenyl, p-chlorophenyl, p-bromophenyl, m-chlorophenyl, m-bromophenyl, o-fluorophenyl, o-chlorophenyl, o-bromophenyl or 3,5-dichlorophenyl; the halogenated alkyl substituted phenyl is p-trifluoromethyl phenyl.

3. The production method according to claim 1 or 2, wherein the hydrazine derivative is replaced with a hydrochloride of the hydrazine derivative.

4. The preparation method according to claim 1, wherein the molar ratio of the hydrazine derivative, the carbon disulfide, the electron deficient olefin derivative, the photocatalyst and the alkali reagent is 2-3: 4 to 5:1 to 2:0.03 to 0.05:3 to 4;

the dosage ratio of the electron-deficient olefin derivative to the polar organic solvent is 0.1-0.2 mol:1L;

the illumination time is 6-24 h.