Multi-nitrogen heterocyclic chemical 3, 5-bis (4-pyrazolyl)-4-amino-1, 2, 4-triazole and synthesis method thereof
By synthesizing 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole in a high-pressure reactor, the synthesis difficulties in the prior art have been solved, and the preparation of high-energy-density and multi-coordination-site compounds with high efficiency and low cost has been achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-26
- Publication Date
- 2026-03-31
AI Technical Summary
There is currently no effective method to synthesize 4-amino-1,2,4-triazole compounds with symmetrically substituted pyrazol groups at the 3,5 positions. Furthermore, the existing synthesis methods are complex and costly, making it difficult to meet the requirements for high energy density and multiple coordination sites.
Using 4-pyrazolic acid and hydrazine hydrate as starting materials, the reaction is carried out in a high-pressure reactor at a controlled temperature of 100-220℃ for 1-5 days to produce 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole. The post-processing is simple, and the hydrazine hydrate can be recycled.
A high-nitrogen-content 4-amino-1,2,4-triazole derivative with symmetrically substituted pyrazol groups at the 3,5 positions was successfully synthesized, enriching the library of polynitrogen heterocyclic compounds, reducing production costs, and making it suitable for scale-up production.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic synthetic functional materials technology, specifically relating to polynitrogen heterocyclic organic compounds, and particularly to a method for synthesizing the polynitrogen heterocyclic chemical 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole. Background Technology
[0002] Polynitrogenous heterocyclic compounds, due to their high nitrogen content, good thermal stability, and diverse molecular structures, show great application potential in energetic materials, coordination chemistry, medicinal chemistry, and materials science. 1,2,4-Triazole and pyrazole are both important nitrogen-containing heterocyclic cores, and their derivatives often exhibit broad biological activities, such as antibacterial, antituberculosis, and antitumor activity. They are also ideal candidates for constructing high-energy-density materials (HEDMs) because of the high bond energies of the CN and NNN bonds, and the fact that their decomposition products are mainly environmentally friendly N2.
[0003] Currently, there are numerous reports on monosubstituted 1,2,4-triazole or pyrazole derivatives. However, symmetrical molecules that simultaneously introduce two pyrazole groups into the 3 and 5 positions of the 1,2,4-triazole core while retaining the active amino group at position 4 are rarely reported. Such highly symmetrical molecules, rich in nitrogen atoms (N content exceeding 65%) and possessing multiple coordination sites (pyrazole N, triazole N, amino N), are expected to have the following unique advantages: (1) High energy density: The extremely high nitrogen content and abundant CN and NN bonds make it a potentially low-sensitivity, high-detonation-performance energetic material; (2) Excellent coordination ability: Multiple coordination sites enable it to interact with metals in multiple ways. Ion coordination enables the construction of novel and diverse metal-organic frameworks (MOFs) or complex structures. Polymers can be used in fields such as gas adsorption, catalysis, and sensing. (3) Potential biological activity: The compound incorporates two pharmacophore groups, 1,2,4-triazole and pyrazole, which may generate new biological activities.
[0004] Therefore, developing a novel 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole with a feasible synthetic method is of great theoretical and practical significance. Summary of the Invention
[0005] To address the shortcomings of existing technologies, the present invention aims to provide a polynitrogen heterocyclic chemical, 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, and a method for its synthesis. This application is the first to synthesize a 4-amino-1,2,4-triazole derivative with a symmetrically substituted pyrazolyl group at the 3,5-position, enriching the library of polynitrogen heterocyclic compounds. Furthermore, the synthetic method utilizes readily available starting materials, mild reaction conditions, and simple post-processing.
[0006] To achieve the above objectives, the present invention adopts the following technical solution: A polynitrogen heterocyclic chemical, 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, has the molecular formula C8H8N8 and its structure is shown in formula (I).
[0007] Formula (I).
[0008] Furthermore, a method for synthesizing the polynitrogen heterocyclic chemical 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole includes the following steps: First, 4-pyrazolic acid and hydrazine hydrate were added to the polytetrafluoroethylene liner of a high-pressure reactor and mixed thoroughly. Then, the high-pressure reactor containing the raw materials was placed under a certain temperature condition for reaction. After the reaction was completed, the mixture was cooled, washed, and centrifuged to obtain the target product 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole. The specific reaction route is as follows:
[0009] Furthermore, the molar ratio of 4-pyrazole carboxylic acid to hydrazine hydrate is 1:1 to 1:5.
[0010] Furthermore, the reaction temperature is 100-220℃.
[0011] Furthermore, the reaction time is 1-5 days.
[0012] Compared with the prior art, the positive and beneficial effects of this invention are as follows: (1) This invention synthesizes for the first time a 4-amino-1,2,4-triazole derivative with symmetrical pyrazolium substitution at the 3,5 position, enriching the library of polynitrogen heterocyclic compounds.
[0013] (2) By allowing an excess of hydrazine hydrate, the main reaction can be pushed in the forward direction, greatly improving the conversion rate of pyrazole 4-carboxylic acid. The excess hydrazine hydrate that did not participate in the reaction can be recycled, thereby reducing costs.
[0014] (3) The starting materials of the synthesis method of the present invention are inexpensive and readily available, the reaction process is simple, the reaction conditions are mild, the post-processing is simple, and the product yield is high, making it suitable for large-scale production.
[0015] (4) The target product molecule synthesized by the present invention combines high nitrogen content, multiple coordination sites and potential biological activity, and has important application value in many high-tech fields. Attached Figure Description
[0016] Figure 1 This is the NMR spectrum of 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, the target product synthesized in this invention. Detailed Implementation
[0017] The technical solutions of the present invention will be further described in detail below with reference to embodiments and accompanying drawings. These embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. All other embodiments obtained by those skilled in the art based on the embodiments in this application without inventive effort are within the scope of protection of this application.
[0018] Unless otherwise specified, the experimental methods described in the embodiments are conventional methods; unless otherwise specified, the reagents and materials are commercially available.
[0019] Example 1 A polynitrogen heterocyclic chemical, 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, has the molecular formula C8H8N8 and its structure is shown in formula (I):
[0020] Formula (I).
[0021] A method for synthesizing the polynitrogen heterocyclic chemical 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, comprising the following steps: Step S1: Using 4-pyrazole carboxylic acid and hydrazine hydrate as starting materials, 11.21 g (0.1 mol) of 4-pyrazole carboxylic acid and 6.25 g (0.1 mol) of hydrazine hydrate with a mass fraction of 80% were added sequentially to the inner liner of the high-pressure resistant reactor and mixed evenly. Step S2: The polytetrafluoroethylene inner liner containing the uniformly mixed raw materials is placed into a high-pressure reactor and reacted at 150°C for 2 days to generate 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole. After cooling, the product is washed with water and centrifuged to obtain the pure product 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, with a product yield of 85%. The specific reaction route is as follows: .
[0022] Example 2 A polynitrogen heterocyclic chemical, 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, has the molecular formula C8H8N8 and its structure is shown in formula (I):
[0023] Formula (I).
[0024] A method for synthesizing the polynitrogen heterocyclic chemical 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, comprising the following steps: Step S1: Using 4-pyrazole carboxylic acid and hydrazine hydrate as starting materials, 11.21 g (0.1 mol) of 4-pyrazole carboxylic acid and 12.5 g (0.2 mol) of hydrazine hydrate with a mass fraction of 80% were added sequentially to the inner liner of the high-pressure reactor and mixed evenly. Step S2: The polytetrafluoroethylene inner liner containing the uniformly mixed raw materials is placed into a high-pressure reactor and reacted at 200°C for 2 days to generate 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole. After cooling, the product is washed with water and centrifuged to obtain a white, pure product, 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, with a yield of 90%. The specific reaction route is as follows: .
[0025] Example 3 A polynitrogen heterocyclic chemical, 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, has the molecular formula C8H8N8 and its structure is shown in formula (I):
[0026] Formula (I).
[0027] A method for synthesizing the polynitrogen heterocyclic chemical 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, comprising the following steps: Step S1: Using 4-pyrazole carboxylic acid and hydrazine hydrate as starting materials, 11.21 g (0.1 mol) of 4-pyrazole carboxylic acid and 18.75 g (0.3 mol) of hydrazine hydrate with a mass fraction of 80% were added sequentially to the inner liner of the high-pressure reactor and mixed evenly. Step S2: The polytetrafluoroethylene inner liner containing the uniformly mixed raw materials is placed into a high-pressure reactor and reacted at 100°C for 5 days to generate 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole. After cooling, the product is washed with water and centrifuged to obtain a white, pure product, 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, with a product yield of 86%. The specific reaction route is as follows: .
[0028] Example 4 A polynitrogen heterocyclic chemical, 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, has the molecular formula C8H8N8 and its structure is shown in formula (I):
[0029] Formula (I).
[0030] A method for synthesizing the polynitrogen heterocyclic chemical 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, comprising the following steps: Step S1: Using 4-pyrazole carboxylic acid and hydrazine hydrate as starting materials, 11.21g (0.1mol) of 4-pyrazole carboxylic acid and 25g (0.4mol) of hydrazine hydrate with a mass fraction of 80% were added sequentially to the inner liner of the high-pressure reactor and mixed evenly. Step S2: The polytetrafluoroethylene inner liner containing the uniformly mixed raw materials is placed into a high-pressure reactor and reacted at 180°C for 3 days to generate 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole. After cooling, the product is washed with water and centrifuged to obtain a white, pure product, 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, with a product yield of 88%. The specific reaction route is as follows: .
[0031] Example 5 A polynitrogen heterocyclic chemical, 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, has the molecular formula C8H8N8 and its structure is shown in formula (I):
[0032] Formula (I).
[0033] A method for synthesizing the polynitrogen heterocyclic chemical 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, comprising the following steps: Step S1: Using 4-pyrazole carboxylic acid and hydrazine hydrate as starting materials, 11.21 g (0.1 mol) of 4-pyrazole carboxylic acid and 31.25 g (0.5 mol) of hydrazine hydrate with a mass fraction of 80% were added sequentially to the inner liner of the high-pressure reactor and mixed evenly. Step S2: The polytetrafluoroethylene inner liner containing the uniformly mixed raw materials is placed into a high-pressure reactor and reacted at 220°C for 1 day to generate 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole. After cooling, the product is washed with water and centrifuged to obtain a white, pure product, 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole, with a product yield of 83%. The specific reaction route is as follows: .
[0034] The target products synthesized in Examples 1-5 were subjected to NMR analysis, and the NMR spectra of the products were obtained as follows: Figure 1 As shown, its 1H-NMR (600 MHz, DMSO-d6) data are as follows: δ 13.25 (s, 2H); 8.42 (s, 2H); 8.10 (s, 2H); 6.16 (s, 2H), and the structural formula of the product is shown in the above formula (I).
[0035] Finally, it should be noted that although embodiments of the present invention have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the present invention.
Claims
1. A polyazacyclic chemical 3,5-di(4-pyrazolyl)-4-amino-1,2,4-triazole, characterized by, The molecular formula is C8H8N8, and the structure is shown as formula (I). Formula (I).
2. A method for synthesizing a polyazacyclic chemical, 3,5-di(4-pyrazolyl)-4-amino- 1,2,4-triazole, characterized by, The method comprises the following steps: firstly, 4-pyrazole carboxylic acid and hydrazine hydrate are used as starting materials, and are added into the inner liner of the polytetrafluoroethylene of a high-pressure resistant reaction kettle, and are uniformly mixed, then the high-pressure resistant reaction kettle containing the starting materials is placed in a certain temperature condition to carry out reaction, after the reaction is completed, cooling, washing and centrifugation are carried out, and the target product 3,5-di(4-pyrazolyl)-4-amino-1,2,4-triazole is obtained.
3. The process for the synthesis of polyazacyclic chemical 3,5-di(4-pyrazolyl)-4-amino- 1,2,4-triazole as claimed in claim 2, wherein, The molar ratio of the 4-pyrazole carboxylic acid to the hydrazine hydrate is 1:1-1:
5.
4. The method for synthesizing the polynitrogen heterocyclic chemical 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole according to claim 2, characterized in that, The reaction temperature is 100-220 DEG C.
5. The method for synthesizing the polynitrogen heterocyclic chemical 3,5-bis(4-pyrazolyl)-4-amino-1,2,4-triazole according to claim 2, characterized in that, The reaction time is 1-5 days.