Thiazolothiazole triphenylamine derivatives, methods of synthesis and use in electrochromism

Abstract

The application discloses a thiazolothiazole triphenylamine derivative, a synthesis method thereof and application thereof in electrochromism, and belongs to the technical field of electrochromic materials. The application provides a thiazolothiazole triphenylamine derivative, and the derivative has a thiazolothiazole group, excellent optical performance and stable redox property. The preparation method of the derivative is a two-step one-pot method for preparing the thiazolothiazole triphenylamine derivative, and has the characteristics of simple process, method innovation and good substrate compatibility. The thiazolothiazole triphenylamine derivative is applied to preparation of an electrochromic device, and lays a foundation for popularization of the material.

Description

Technical Field

[0001] This invention relates to the field of electrochromic materials technology, and in particular to a thiazothiazolyl triphenylamine derivative, its synthesis method, and its application in electrochromism. Background Technology

[0002] Under the influence of an applied voltage, electrochromic materials can actively undergo stable and reversible optical changes. As materials with high added value and promising applications, they are widely used in advanced portable electronic products and artificial intelligence technologies such as smart windows, automotive anti-glare rearview mirrors, multi-functional displays, and memory. Triarylaniline compounds, as unique electrochromic materials, exhibit good thermal stability, excellent redox properties, and simple synthesis processes, making them important components in optical and electronic devices. However, existing triarylaniline electrochromic materials suffer from limited variety and poor electrochemical performance, insufficient to meet the growing demands of social development. Therefore, researching and developing triarylaniline electrochromic materials with high optical contrast, short response time, and excellent electrochemical cycling stability is of great significance for further promoting the practical application of electrochromic devices.

[0003] Triarylaniline, with a nitrogen atom at its center, consists of three aromatic rings arranged in a propeller-like configuration. Triphenylamine is the simplest of the triarylaniline compounds. This unique propeller structure endows triarylaniline with extremely strong hole transport capabilities and unique free radical properties, as well as excellent redox stability, high hole transport rate, low ionization potential, and strong fluorescence. Triarylaniline is considered one of the most widely used building blocks in organic functional materials, and can be used to construct organic optoelectronic materials with different properties. It is commonly used in the preparation of fluorescent probes, hole transporters, and electrochromic materials, possessing significant commercial application value. The synthesis of triphenylamine derivatives typically employs the Ullmann reaction, but this reaction requires harsh conditions and excessive copper powder catalysis, limiting the application of triphenylamine derivatives in the electrochromic field. Summary of the Invention

[0004] In view of the above-mentioned deficiencies of the prior art, in a first aspect of the present invention, a thiazo[a]thiazo[b]thiazo[c]]triphenylamine derivative with excellent optical properties and stable properties is provided, wherein the structural formula of the thiazo[a]thiazo[c]thiazo[b]]triphenylamine derivative is as follows:

[0005] Structural Formula I:

[0006] R1 and R2 are selected from any one of hydrogen, alkyl, alkoxy, aryl, and halogen groups, respectively;

[0007] R1 and R2 can be the same or different.

[0008] In a second aspect of the present invention, a method for preparing thiazothiazolium triphenylamine derivatives with simple process and good substrate compatibility is provided, comprising the following steps:

[0009] (1) The precursor was prepared by reacting 2,2-dimethylcyclohexane-1,3-dione with liquid bromine;

[0010] (2) The precursor is reacted with N,N-diphenylthiourea derivatives to prepare thiazolyl-thiazolyl triphenylamine derivatives.

[0011] Preferably, the specific operation of step (1) is as follows: under anaerobic conditions, 2,2-dimethylcyclohexane-1,3-dione, liquid bromine and solvent are mixed evenly and reacted; after the reaction is completed, excess liquid bromine is removed, the organic phase is collected by extraction, concentrated and dried to obtain the precursor.

[0012] More preferably, the molar ratio of the 2,2-dimethylcyclohexane-1,3-dione to the liquid bromine is 1:2 to 2.4.

[0013] More preferably, the reaction is carried out in two stages: the first stage is carried out at 0°C for 0.5 to 1 hour, and the second stage is carried out at 25 to 30°C for 2 to 3 hours.

[0014] More preferably, the solvent is acetic acid; the excess liquid bromine is removed by adding a saturated aqueous solution of potassium carbonate and a saturated aqueous solution of sodium metabisulfite.

[0015] Furthermore, the molar volume ratio of the 2,2-dimethylcyclohexane-1,3-dione to acetic acid, saturated potassium carbonate aqueous solution, and saturated sodium metabisulfite aqueous solution is 1 mol: 5-6 L: 3-5 L: 2-3 L, respectively.

[0016] Preferably, the specific operation of step (2) is as follows: under anaerobic conditions, the precursor is dissolved in a solvent, N,N-diphenylthiourea derivative is added to the resulting solution and reacted; after the reaction is completed, the filter cake is collected by filtration, and the filter cake is washed and dried to obtain thiazolyl-thiazolium triphenylamine derivative.

[0017] More preferably, the molar ratio of the precursor to the N,N-diphenylthiourea derivative is 1:2.5 to 3.

[0018] More preferably, the structural formula of the N,N-diphenylthiourea derivative is as follows:

[0019] Structural Formula II:

[0020] R1 and R2 are selected from any one of hydrogen, alkyl, alkoxy, aryl, and halogen groups, respectively;

[0021] R1 and R2 can be the same or different.

[0022] More preferably, the reaction is carried out at 80–85°C for 48–72 h.

[0023] More preferably, the solvent is anhydrous ethanol; the molar volume ratio of the precursor to anhydrous ethanol is 1 mol: 5-6 L.

[0024] The reaction process of the preparation method of the second aspect of the present invention is as follows:

[0025]

[0026] In a third aspect of the invention, the application of thiazothiazol triphenylamine derivatives of the first aspect of the invention or thiazothiazol triphenylamine derivatives prepared in the second aspect of the invention as electrochromic materials in the preparation of electrochromic devices is provided.

[0027] The specific method of the application includes the following steps:

[0028] S1. Assemble ITO conductive glass to form a device substrate with a cavity; dissolve a thiazothiazolyl triphenylamine derivative in a solvent to obtain a device solution;

[0029] S2. The device solution is sealed in the cavity of the device substrate to obtain an electrochromic device.

[0030] Preferably, in step S1, the concentration of the thiazothiazol triphenylamine derivative in the device solution is 2-4 mg / mL.

[0031] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0032] This invention provides a thiazothiazol triphenylamine derivative, which has a thiazothiazol group, excellent optical properties, and stable redox properties.

[0033] This invention provides a method for preparing thiazo[a]thiazolyl triphenylamine derivatives. The method involves reacting a pre-prepared carbonyl bromide (the precursor) with an N,N-diphenylthiourea derivative via a carbonyl-amino group reaction to form an imine bond. Subsequently, a sulfur atom undergoes a substitution reaction with a carbon-bromine bond. This two-step, one-pot method yields the thiazo[a]thiazolyl triphenylamine derivative. The method is characterized by its simplicity, innovation, and good substrate compatibility.

[0034] This invention also provides the application of thiazothiazolyl triphenylamine derivatives in the preparation of electrochromic devices. Attached Figure Description

[0035] Figure 1 This is a single-crystal structure diagram of the thiazothiazolyl triphenylamine derivative of Example 1. The numbers to the right of the atomic element abbreviations are their atomic numbers.

[0036] Figure 2 In the diagram, Figure a shows the test conditions for the cyclic stability test, and Figure b shows the test results after 175 cycles. Detailed Implementation

[0037] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0038] Example 1

[0039] Preparation:

[0040] (1) Under inert gas protection, 10 mmol of 2,2-dimethylcyclohexane-1,3-dione, 20 mmol of liquid bromine and 50 mL of acetic acid were mixed evenly. The mixture was first reacted at 0 °C for 1 h, and then at 25 °C for 3 h. After the reaction was completed, 30 mL of saturated potassium carbonate aqueous solution and 20 mL of saturated sodium metabisulfite aqueous solution were added to the resulting reaction solution. After stirring and mixing evenly, the resulting mixture was extracted with 100 mL of ethyl acetate and the organic phases were combined. The organic phases were concentrated with anhydrous magnesium sulfate and dried to obtain the precursor, which was named 4,6-dibromo-2,2-dimethylcyclohexane-1,3-dione.

[0041] (2) Under inert gas protection, 5 mmol of the precursor was dissolved in 25 mL of anhydrous ethanol, and 12.5 mmol of 1,1-diphenylthiourea was added to the resulting solution. After mixing evenly, the mixture was reacted at 85 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and a solid product was precipitated. The filter cake was collected by filtration, and the filter cake was washed and dried with anhydrous ethanol to obtain a thiazolyl triphenylamine derivative.

[0042] In this embodiment, part of the reaction process for the thiazothiazolidinediazole triphenylamine derivative is as follows:

[0043]

[0044] The physical properties and structure of the thiazo[a]thiazolium triphenylamine derivatives obtained in this embodiment were analyzed. The melting point of the substance was determined by an SGW X-4 micro melting point apparatus, and the melting point of the thiazo[a]thiazolium triphenylamine derivatives is between 261 and 262 °C.

[0045] NMR data: 1H NMR (400MHz, CDCl3): δ7.42-7.34(m,16H),7.22-7.18(m,4H),3.76(s,2H),1.61(s,6H). 13 C{ 1 H}NMR (100MHz, CDCl3): δ166.86,153.39,145.32,129.41,125.33,125.28,114.68,38.77,28.62,23.11.

[0046] High-resolution mass spectrometry data: HRMS calcd for C 34 H 29 N4S2[M+H] + 557.1828; found: 557.1835.

[0047] The thiazothiazolium triphenylamine derivatives were characterized using X-ray single-crystal diffraction, and their structural diagrams are shown below. Figure 1 As shown, the structure of the target product is corresponding to the structure of the product, proving that the conclusion of the synthesis of thiazothiazol triphenylamine derivatives is correct.

[0048] Example 2

[0049] Preparation:

[0050] (1) Under inert gas protection, 10 mmol of 2,2-dimethylcyclohexane-1,3-dione, 20 mmol of liquid bromine and 50 mL of acetic acid were mixed evenly. The mixture was first reacted at 0 °C for 1 h, and then at 25 °C for 3 h. After the reaction was completed, 30 mL of saturated potassium carbonate aqueous solution and 20 mL of saturated sodium metabisulfite aqueous solution were added to the resulting reaction solution. After stirring and mixing evenly, the resulting mixture was extracted with 100 mL of ethyl acetate and the organic phases were combined. The organic phases were concentrated with anhydrous magnesium sulfate and dried to obtain the precursor.

[0051] (2) Under inert gas protection, 5 mmol of the precursor was dissolved in 25 mL of anhydrous ethanol, and 12.5 mmol of 1,1-di(p-tolyl)thiourea was added to the resulting solution. After mixing evenly, the mixture was reacted at 85 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and a solid product was precipitated. The filter cake was collected by filtration, washed with anhydrous ethanol and dried to obtain a thiazolyl triphenylamine derivative.

[0052] In this embodiment, part of the reaction process for the thiazothiazolidinediazole triphenylamine derivative is as follows:

[0053]

[0054] This embodiment was characterized by NMR and high-resolution mass spectrometry. Similar to Example 1, a thiazothiazolyl triphenylamine derivative with the target structure of this embodiment was also obtained.

[0055] Example 3

[0056] Preparation:

[0057] (1) Under inert gas protection, 10 mmol of 2,2-dimethylcyclohexane-1,3-dione, 20 mmol of liquid bromine and 50 mL of acetic acid were mixed evenly. The mixture was first reacted at 0 °C for 1 h, and then at 25 °C for 3 h. After the reaction was completed, 30 mL of saturated potassium carbonate aqueous solution and 20 mL of saturated sodium metabisulfite aqueous solution were added to the resulting reaction solution. After stirring and mixing evenly, the resulting mixture was extracted with 100 mL of ethyl acetate and the organic phases were combined. The organic phases were concentrated with anhydrous magnesium sulfate and dried to obtain the precursor.

[0058] (2) Under inert gas protection, 5 mmol of the precursor was dissolved in 25 mL of anhydrous ethanol, and 12.5 mmol of 1,1-bis(p-methoxyphenyl)thiourea was added to the resulting solution. After mixing evenly, the mixture was reacted at 85 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and a solid product was precipitated. The filter cake was collected by filtration, washed with anhydrous ethanol and dried to obtain a thiazolyl triphenylamine derivative.

[0059] In this embodiment, part of the reaction process for the thiazothiazolidinediazole triphenylamine derivative is as follows:

[0060]

[0061] This embodiment was characterized by NMR and high-resolution mass spectrometry. Similar to Example 1, a thiazothiazolyl triphenylamine derivative with the target structure of this embodiment was also obtained.

[0062] Example 4

[0063] Preparation:

[0064] (1) Under inert gas protection, 10 mmol of 2,2-dimethylcyclohexane-1,3-dione, 20 mmol of liquid bromine and 50 mL of acetic acid were mixed evenly. The mixture was first reacted at 0 °C for 1 h, and then at 25 °C for 3 h. After the reaction was completed, 30 mL of saturated potassium carbonate aqueous solution and 20 mL of saturated sodium metabisulfite aqueous solution were added to the resulting reaction solution. After stirring and mixing evenly, the resulting mixture was extracted with 100 mL of ethyl acetate and the organic phases were combined. The organic phases were concentrated with anhydrous magnesium sulfate and dried to obtain the precursor.

[0065] (2) Under inert gas protection, 5 mmol of the precursor was dissolved in 25 mL of anhydrous ethanol, and 12.5 mmol of 1,1-dibisphenylthiourea was added to the resulting solution. After mixing evenly, the mixture was reacted at 85 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and a solid product was precipitated. The filter cake was collected by filtration, and the filter cake was washed and dried with anhydrous ethanol to obtain a thiazolyl triphenylamine derivative.

[0066] In this embodiment, part of the reaction process for the thiazothiazolidinediazole triphenylamine derivative is as follows:

[0067]

[0068] This embodiment was characterized by NMR and high-resolution mass spectrometry. Similar to Example 1, a thiazothiazolyl triphenylamine derivative with the target structure of this embodiment was also obtained.

[0069] Example 5

[0070] Preparation:

[0071] (1) Under inert gas protection, 10 mmol of 2,2-dimethylcyclohexane-1,3-dione, 20 mmol of liquid bromine and 50 mL of acetic acid were mixed evenly. The mixture was first reacted at 0 °C for 1 h, and then at 25 °C for 3 h. After the reaction was completed, 30 mL of saturated potassium carbonate aqueous solution and 20 mL of saturated sodium metabisulfite aqueous solution were added to the resulting reaction solution. After stirring and mixing evenly, the resulting mixture was extracted with 100 mL of ethyl acetate and the organic phases were combined. The organic phases were concentrated with anhydrous magnesium sulfate and dried to obtain the precursor.

[0072] (2) Under inert gas protection, 5 mmol of the precursor was dissolved in 25 mL of anhydrous ethanol, and 12.5 mmol of 1,1-bis(p-chlorophenyl)thiourea was added to the resulting solution. After mixing evenly, the mixture was reacted at 85 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and a solid product was precipitated. The filter cake was collected by filtration, washed with anhydrous ethanol and dried to obtain a thiazolyl triphenylamine derivative.

[0073] In this embodiment, part of the reaction process for the thiazothiazolidinediazole triphenylamine derivative is as follows:

[0074]

[0075] This embodiment was characterized by NMR and high-resolution mass spectrometry. Similar to Example 1, a thiazothiazolyl triphenylamine derivative with the target structure of this embodiment was also obtained.

[0076] Example 6

[0077] Preparation:

[0078] (1) Under inert gas protection, 10 mmol of 2,2-dimethylcyclohexane-1,3-dione, 24 mmol of liquid bromine and 60 mL of acetic acid were mixed evenly. The mixture was first reacted at 0 °C for 0.5 h, and then at 30 °C for 2 h. After the reaction was completed, 50 mL of saturated potassium carbonate aqueous solution and 30 mL of saturated sodium metabisulfite aqueous solution were added to the resulting reaction solution. After stirring and mixing evenly, the resulting mixture was extracted with 100 mL of ethyl acetate and the organic phases were combined. The organic phases were concentrated with anhydrous magnesium sulfate and dried to obtain the precursor.

[0079] (2) Under inert gas protection, 5 mmol of the precursor was dissolved in 30 mL of anhydrous ethanol, and 15 mmol of 1,1-diphenylthiourea was added to the resulting solution. After mixing evenly, the mixture was reacted at 80 °C for 72 h. After the reaction was completed, the mixture was cooled to room temperature and a solid product was precipitated. The filter cake was collected by filtration, and the filter cake was washed and dried with anhydrous ethanol to obtain a thiazolyl triphenylamine derivative.

[0080] This embodiment was characterized by NMR and high-resolution mass spectrometry. Similar to Example 1, a thiazothiazolyl triphenylamine derivative with the target structure of this embodiment was also obtained.

[0081] Example 7

[0082] Preparation:

[0083] (1) Under inert gas protection, 10 mmol of 2,2-dimethylcyclohexane-1,3-dione, 20 mmol of liquid bromine and 50 mL of acetic acid were mixed evenly. The mixture was first reacted at 0 °C for 1 h, and then at 25 °C for 3 h. After the reaction was completed, 30 mL of saturated potassium carbonate aqueous solution and 20 mL of saturated sodium metabisulfite aqueous solution were added to the resulting reaction solution. After stirring and mixing evenly, the resulting mixture was extracted with 100 mL of ethyl acetate and the organic phases were combined. The organic phases were concentrated with anhydrous magnesium sulfate and dried to obtain the precursor, which was named 4,6-dibromo-2,2-dimethylcyclohexane-1,3-dione.

[0084] (2) Under inert gas protection, 5 mmol of the precursor was dissolved in 25 mL of anhydrous ethanol, and 12.5 mmol of 1-(4-chlorophenyl)-1-phenylthiourea was added to the resulting solution. After mixing evenly, the mixture was reacted at 85 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and a solid product was precipitated. The filter cake was collected by filtration, washed with anhydrous ethanol and dried to obtain a thiazothiazolium triphenylamine derivative.

[0085] In this embodiment, part of the reaction process for the thiazothiazolidinediazole triphenylamine derivative is as follows:

[0086]

[0087] This embodiment was characterized by NMR and high-resolution mass spectrometry. Similar to Example 1, a thiazothiazolyl triphenylamine derivative with the target structure of this embodiment was also obtained.

[0088] Example 8

[0089] Preparation:

[0090] (1) Under inert gas protection, 10 mmol of 2,2-dimethylcyclohexane-1,3-dione, 20 mmol of liquid bromine and 50 mL of acetic acid were mixed evenly. The mixture was first reacted at 0 °C for 1 h, and then at 25 °C for 3 h. After the reaction was completed, 30 mL of saturated potassium carbonate aqueous solution and 20 mL of saturated sodium metabisulfite aqueous solution were added to the resulting reaction solution. After stirring and mixing evenly, the resulting mixture was extracted with 100 mL of ethyl acetate and the organic phases were combined. The organic phases were concentrated with anhydrous magnesium sulfate and dried to obtain the precursor, which was named 4,6-dibromo-2,2-dimethylcyclohexane-1,3-dione.

[0091] (2) Under inert gas protection, 5 mmol of the precursor was dissolved in 25 mL of anhydrous ethanol, and 12.5 mmol of 1-(4-methoxyphenyl)-1-phenylthiourea was added to the resulting solution. After mixing evenly, the mixture was reacted at 85 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and a solid product was precipitated. The filter cake was collected by filtration, washed with anhydrous ethanol and dried to obtain a thiazolyl triphenylamine derivative.

[0092] In this embodiment, part of the reaction process for the thiazothiazolidinediazole triphenylamine derivative is as follows:

[0093]

[0094] This embodiment was characterized by NMR and high-resolution mass spectrometry. Similar to Example 1, a thiazothiazolyl triphenylamine derivative with the target structure of this embodiment was also obtained.

[0095] Example 9

[0096] Preparation:

[0097] (1) Under inert gas protection, 10 mmol of 2,2-dimethylcyclohexane-1,3-dione, 20 mmol of liquid bromine and 50 mL of acetic acid were mixed evenly. The mixture was first reacted at 0 °C for 1 h, and then at 25 °C for 3 h. After the reaction was completed, 30 mL of saturated potassium carbonate aqueous solution and 20 mL of saturated sodium metabisulfite aqueous solution were added to the resulting reaction solution. After stirring and mixing evenly, the resulting mixture was extracted with 100 mL of ethyl acetate and the organic phases were combined. The organic phases were concentrated with anhydrous magnesium sulfate and dried to obtain the precursor, which was named 4,6-dibromo-2,2-dimethylcyclohexane-1,3-dione.

[0098] (2) Under inert gas protection, 5 mmol of the precursor was dissolved in 25 mL of anhydrous ethanol, and 12.5 mmol of 1-(4-methoxyphenyl)-1-(4-chlorophenyl)thiourea was added to the resulting solution. After mixing evenly, the mixture was reacted at 85 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and a solid product was precipitated. The filter cake was collected by filtration, washed with anhydrous ethanol and dried to obtain a thiazolyl triphenylamine derivative.

[0099] In this embodiment, part of the reaction process for the thiazothiazolidinediazole triphenylamine derivative is as follows:

[0100]

[0101] This embodiment was characterized by NMR and high-resolution mass spectrometry. Similar to Example 1, a thiazothiazolyl triphenylamine derivative with the target structure of this embodiment was also obtained.

[0102] Example 10

[0103] Application of thiazothiazolium triphenylamine derivatives in the preparation of electrochromic devices:

[0104] S1. First, use double-sided tape to create a rectangular frame of 1cm×2cm along the edge of a 2cm×3cm ITO conductive glass piece. Then, attach another ITO conductive glass piece of the same size to it to form a device substrate with a cavity and a thickness of 40μm. Dissolve the thiazothiazolium triphenylamine derivative synthesized in Example 1 in N,N-dimethylformamide to obtain a device solution with a concentration of 3mg / mL.

[0105] S2. Inject the device solution into the cavity of the device substrate using a syringe and seal it to obtain an electrochromic device.

[0106] The cyclic stability of the electrochromic device was tested under the following conditions: Figure 2As shown in Figure a, the initial voltage was 2.4V, applied for 30 seconds, followed by a reverse voltage of -2.4V, applied for 14 seconds, and finally de-energized for 100 seconds. Using these conditions, the cycle count was set to 500. The final experimental results are as follows. Figure 2 As shown in b, the device can still maintain good stability after 175 cycles, laying the foundation for the application of this type of material.

[0107] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. The application of a thiazothiazolium triphenylamine derivative as an electrochromic material in the fabrication of electrochromic devices, characterized in that, The structural formula of the thiazothiazolidinyl triphenylamine derivative is as follows: 。 2. An application as described in claim 1, characterized in that, The preparation method of the thiazothiazol triphenylamine derivative includes the following steps: (1) Under anaerobic conditions, 2,2-dimethylcyclohexane-1,3-dione, liquid bromine and solvent were mixed evenly and reacted; after the reaction was completed, excess liquid bromine was removed, the organic phase was collected by extraction, concentrated and dried to obtain the precursor; (2) Under anaerobic conditions, the precursor is dissolved in a solvent, and an N,N-diphenylthiourea derivative is added to the resulting solution and reacted. After the reaction is completed, the filter cake is collected by filtration, and the filter cake is washed and dried to obtain a thiazolyl triphenylamine derivative. The solvent is anhydrous ethanol. The molar volume ratio of the precursor to anhydrous ethanol is 1 mol: 5~6 L. The structural formula of the N,N-diphenylthiourea derivative is as follows: ； The partial reaction process of the thiazothiazolidinediazole triphenylamine derivative is as follows: 。 3. The application according to claim 2, characterized in that: The molar ratio of the 2,2-dimethylcyclohexane-1,3-dione to the liquid bromine is 1:2~2.4; the reaction is carried out in two stages, the first stage is carried out at 0°C for 0.5~1h, and the second stage is carried out at 25~30°C for 2~3h.

4. The application according to claim 2, characterized in that: The solvent is acetic acid; the excess liquid bromine is removed by adding saturated potassium carbonate aqueous solution and saturated sodium metabisulfite aqueous solution; the molar volume ratio of 2,2-dimethylcyclohexane-1,3-dione to acetic acid, saturated potassium carbonate aqueous solution and saturated sodium metabisulfite aqueous solution is 1 mol: 5~6 L: 3~5 L: 2~3 L respectively.

5. The application according to claim 2, characterized in that: The molar ratio of the precursor to the N,N-diphenylthiourea derivative is 1:2.5~3; the reaction is carried out at 80~85℃ for 48~72h.

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