4, 6-dinitro-N1, N3-di (1H-tetrazole-5-yl) benzene-1, 3-diamine and synthetic method thereof

Abstract

The invention discloses an insensitive energetic compound 4, 6-dinitro-N1, N3-di (1H-tetrazole-5-yl) benzene-1, 3-diamine and a synthetic method thereof.The synthetic method comprises the steps that fuming nitric acid, concentrated sulfuric acid, 1, 3-difluorobenzene, 5-aminotetrazole and THF are used as raw materials, and synthesis of an intermediate 1, 5-difluoro-2, 4-dinitrobenzene is carried out, continuously stirring for a period of time to obtain a mixture, dropwise adding 1, 3-difluorobenzene into the mixture through a dropping funnel, slowly heating the system, and monitoring the reaction progress through TLC (Thin Layer Chromatography); after the reaction is completed, pouring a mixture into ice water, filtering to obtain a light yellow precipitate, adding a certain amount of 1, 5-difluoro-2, 4-dinitrobenzene and 5-aminotetrazole into THF, heating to a certain temperature, refluxing, and monitoring the reaction progress through TLC; after the reaction is completed, cooling reaction liquid to room temperature, and evaporating THF under reduced pressure; and recrystallizing the residue with ethyl acetate and petroleum ether, and filtering to obtain a yellow solid.

Description

Technical Field

[0001] The present invention relates to the technical field of insensitive energetic compounds, in particular to 4,6-dinitro-N 1 ,N 3 -bis(1H-tetrazolyl-5-yl)benzene-1,3-diamine and a method for synthesizing the same. Background Art

[0002] Tetrazole compounds are five-membered heterocyclic compounds containing four nitrogen atoms and are an important class of intermediates. The five-membered tetrazole heterocyclic ring is a high-nitrogen energetic structural unit containing high-energy CN, NN bonds (160 kJ·mol-1) and N=N bonds (418 kJ·mol-1). The nitrogen content is as high as 80.0%. It is an aromatic compound with a delocalized large π bond similar to that of a benzene ring. The tetrazole ring is a planar structure with the characteristics of low sensitivity, good stability, green cleaning, and easy adjustment. It has broad application prospects in the field of energetic materials. 1H-tetrazole is an isomer of tetrazole compounds. 5-aminotetrazole (5-AT) is a derivative of 1H-tetrazole with a nitrogen content of 82.33%. It is a functional group of a low-sensitivity, safe, green, and environmentally friendly high-nitrogen energetic material. Summary of the invention

[0003] The purpose of this section is to summarize some aspects of embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and the invention title of this application to avoid blurring the purpose of this section, the specification abstract and the invention title, and such simplifications or omissions cannot be used to limit the scope of the present invention.

[0004] To solve the above problems, the present invention adopts the following technical solutions.

[0005] 4,6-Dinitro-N 1 ,N 3 -bis(1H-tetrazolyl-5-yl)benzene-1,3-diamine and its synthesis method, using fuming nitric acid, concentrated sulfuric acid, 1,3-difluorobenzene, 5-aminotetrazolyl and THF as raw materials, through heating, refluxing, filtering, recrystallization and other methods to synthesize 4,6-dinitro-N 1 ,N 3 -bis(1H-tetrazol-5-yl)benzene-1,3-diamine.

[0006] As a further description of the above technical solution:

[0007] S1. Synthesis of intermediate 1,5-difluoro-2,4-dinitrobenzene: slowly add fuming nitric acid to concentrated sulfuric acid, continue stirring for a period of time to obtain a mixture, then drop 1,3-difluorobenzene into the mixture through a dropping funnel, slowly heat the system, and monitor the progress of the reaction by TLC; after the reaction is completed, pour the mixture into ice water and filter to obtain a light yellow precipitate;

[0008] S2. Add a certain amount of 1,5-difluoro-2,4-dinitrobenzene and 5-aminotetrazole to THF, heat to a certain temperature and reflux, and monitor the progress of the reaction by TLC; after the reaction is completed, cool the reaction solution to room temperature, and evaporate THF under reduced pressure; the residue is recrystallized with ethyl acetate and petroleum ether and filtered to obtain a yellow solid.

[0009] As a further description of the above technical solution:

[0010] The raw material volume ratio of the fuming nitric acid and concentrated sulfuric acid is 1:1.

[0011] As a further description of the above technical solution:

[0012] The raw material mass ratio of 1,3-difluorobenzene and concentrated sulfuric acid is 1:8.0-1:8.5.

[0013] As a further description of the above technical solution:

[0014] The heating reaction temperature is 105-115°C.

[0015] As a further description of the above technical solution:

[0016] The raw material molar ratio of 1,5-difluoro-2,4-dinitrobenzene and 5-aminotetrazole is 1:2.

[0017] As a further description of the above technical solution:

[0018] The raw material mass ratio of 1,5-difluoro-2,4-dinitrobenzene and THF is 1:10-1:11.

[0019] As a further description of the above technical solution:

[0020] The recrystallization volume ratio of ethyl acetate to petroleum ether is 1:1.

[0021] Compared with the prior art, the present invention has the following beneficial effects: the compound 4,6-dinitro-N 1 ,N 3-Bis(1H-tetrazolyl-5-yl)benzene-1,3-diamine, referred to as ZXC-92, can be used as a pesticide or plant growth hormone in agricultural production. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The 4,6-dinitro-N 1 ,N 3 -Structure of bis(1H-tetrazolyl-5-yl)phenyl-1,3-diamine;

[0023] Figure 2 Schematic diagram of the synthesis structure of the intermediate of the present invention;

[0024] Figure 3 The schematic diagram of the synthetic structure of the product ZXC-92 of the present invention;

[0025] Figure 4 is the hydrogen nuclear magnetic resonance spectrum of compound 2 (CDCl3) of the present invention;

[0026] Figure 5 is the carbon nuclear magnetic resonance spectrum of compound 2 (CDCl3) of the present invention;

[0027] Figure 6 is the nuclear magnetic resonance fluorine spectrum of compound 2 (CDCl3) of the present invention;

[0028] Figure 7 is the hydrogen nuclear magnetic resonance spectrum of the product ZXC-92 of the present invention;

[0029] Figure 8 The carbon nuclear magnetic resonance spectrum of the product ZXC-92 of the present invention is:

[0030] Fig. 9 The single crystal X-ray structure diagram of the product ZXC-92 of the present invention. DETAILED DESCRIPTION

[0031] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the accompanying drawings.

[0032] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0033] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure or characteristic that may be included in at least one implementation of the present invention. The term "in one embodiment" that appears in different places in this specification does not refer to the same embodiment, nor is it a separate or selective embodiment that is mutually exclusive with other embodiments. The present invention provides the following embodiments.

[0034] Example 1. Synthesis of intermediate 1,3-difluoro-4,6-dinitrobenzene

[0035] Under magnetic stirring at 0°C, fuming nitric acid (92%, 180 mL) was slowly added to concentrated sulfuric acid (180 mL), and stirring was continued for 10 minutes, and then 1,3-difluorobenzene (39.90 g, 35.0 mmol) was slowly dropped into the mixture through a dropping funnel. After dropping 1,3-difluorobenzene, the system was slowly heated to 110°C until the reaction was completed and monitored by TLC. The mixture was poured into ice water and filtered to obtain a light yellow precipitate.

[0036] Hydrogen spectrum: 1 H NMR (600MHz, CDCl3) δ9.00 (t, J = 7.4 Hz, 1H), 7.35 (t, J = 9.7 Hz, 1H).

[0037] Carbon spectrum: 13 C NMR (151MHz, CDCl3) δ159.8-159.7(d), 157.9-157.8(d), 125.4, 110.0, 109.8, 109.6.

[0038] Fluorine spectrum: 19 F NMR (565 MHz, CDCl3) δ -100.4 (t, J = 8.7 Hz). Example 2. 4,6-Dinitro-N 1 ,N 3 Synthesis of bis(1H-tetrazolyl-5-yl)benzene-1,3-diamine

[0039] A mixture of 1,5-difluoro-2,4-dinitrobenzene (4.080 g, 20.0 mmol), 5-aminotetrazole (3.4 g, 40.0 mmol) and THF (50.0 mL) was refluxed until the reaction was complete and monitored by TLC (about 37 hours). The mixture was cooled to room temperature and THF was evaporated under reduced pressure. The residue was recrystallized from ethyl acetate and petroleum ether (V / V=1:1) and filtered to give a yellow solid ZXC-92 (4.841 g, 72.5% yield).

[0040] Hydrogen spectrum: 1H NMR (600MHz, DMSO-d6) δ10.74(s,2H),9.04(s,1H),8.96(s,1H),3.76(br,2H).

[0041] Carbon spectrum: 13 C NMR (151MHz, DMSO-d6) δ154.9, 142.0, 127.5, 126.8, 104.2.

[0042] The above content is a further detailed description of the present invention in combination with specific implementation methods. It cannot be determined that the specific implementation of the present invention is limited to these descriptions. For ordinary technicians in the technical field to which the present invention belongs, several simple deductions or substitutions can be made without departing from the concept of the present invention, which should be regarded as belonging to the protection scope determined by the claims submitted for the present invention.

Claims

1. A 4,6-dinitro-N 1 ,N 3 -A method for synthesizing bis(1H-tetrazolyl-5-yl)benzene-1,3-diamine, characterized in that: 4,6-dinitro-N-(2-nitropropene)-2-nitropropene was synthesized by heating, refluxing, filtering and recrystallization with fuming nitric acid, concentrated sulfuric acid, 1,3-difluorobenzene, 5-aminotetrazolyl and THF as raw materials. 1 ,N 3 -bis(1H-tetrazol-5-yl)benzene-1,3-diamine.

2. A 4,6-dinitro-N- 1 ,N 3 -A method for synthesizing bis(1H-tetrazolyl-5-yl)benzene-1,3-diamine, characterized in that: S1. Synthesis of intermediate 1,5-difluoro-2,4-dinitrobenzene: slowly add fuming nitric acid to concentrated sulfuric acid, continue stirring for a period of time to obtain a mixture, then drop 1,3-difluorobenzene into the mixture through a dropping funnel, slowly heat the system, and monitor the progress of the reaction by TLC; after the reaction is completed, pour the mixture into ice water and filter to obtain a light yellow precipitate; S2. Add a certain amount of 1,5-difluoro-2,4-dinitrobenzene and 5-aminotetrazole to THF, heat to a certain temperature and reflux, and monitor the progress of the reaction by TLC; after the reaction is completed, cool the reaction solution to room temperature, and evaporate THF under reduced pressure; the residue is recrystallized with ethyl acetate and petroleum ether and filtered to obtain a yellow solid.

3. A 4,6-dinitro-N- 1 ,N 3 -A method for synthesizing bis(1H-tetrazolyl-5-yl)benzene-1,3-diamine, characterized in that: The raw material volume ratio of the fuming nitric acid and concentrated sulfuric acid is 1:

1.

4. A 4,6-dinitro-N- 1 ,N 3 -A method for synthesizing bis(1H-tetrazolyl-5-yl)benzene-1,3-diamine, characterized in that: The raw material mass ratio of 1,3-difluorobenzene and concentrated sulfuric acid is 1:8.0-1:8.

5.

5. A 4,6-dinitro-N- 1 ,N 3 -A method for synthesizing bis(1H-tetrazolyl-5-yl)benzene-1,3-diamine, characterized in that: The heating reaction temperature is 105-115°C.

6. A 4,6-dinitro-N- 1 ,N 3 -A method for synthesizing bis(1H-tetrazolyl-5-yl)benzene-1,3-diamine, characterized in that: The raw material molar ratio of 1,5-difluoro-2,4-dinitrobenzene and 5-aminotetrazole is 1:

2.

7. A 4,6-dinitro-N- 1 ,N 3 -A method for synthesizing bis(1H-tetrazolyl-5-yl)benzene-1,3-diamine, characterized in that: The raw material mass ratio of 1,5-difluoro-2,4-dinitrobenzene and THF is 1:10-1:

11.

8. A 4,6-dinitro-N- 1 ,N 3 -A method for synthesizing bis(1H-tetrazolyl-5-yl)benzene-1,3-diamine, characterized in that: The volume ratio of ethyl acetate to petroleum ether for recrystallization is 1:1.

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