CN113045584A - Fluorine dinitroethoxy furazapyrazine compound and synthetic method thereof - Google Patents
Fluorine dinitroethoxy furazapyrazine compound and synthetic method thereof Download PDFInfo
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- CN113045584A CN113045584A CN201911382919.0A CN201911382919A CN113045584A CN 113045584 A CN113045584 A CN 113045584A CN 201911382919 A CN201911382919 A CN 201911382919A CN 113045584 A CN113045584 A CN 113045584A
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Abstract
The invention discloses a fluorine dinitroethoxy furazan pyrazine compound and a synthesis method thereof. The compound takes 5, 6-dichlorofurazano [3,4-b ] pyrazine as a raw material to perform nucleophilic substitution with fluorine dinitroethanol in dichloromethane, so as to obtain a target compound 5, 6-bis (2-fluorine-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine. The synthetic route is simple and easy to implement, and can provide reference for the synthesis of the fluorine dinitroethoxy energetic derivative; the target compound has excellent performance, can be applied to the field of propellants or explosives, has high mechanical and thermal sensitivity, and simultaneously has good detonation performance.
Description
Technical Field
The invention belongs to the field of synthesis of energetic materials, and relates to a furazan pyrazine compound and a synthesis method thereof.
Background
The introduction of the fluorine dinitroethyl into the heterocycle can not only improve the detonation performance of the compound, but also improve the thermodynamic stability of the compound due to the existence of fluorine atoms, and becomes an important research direction in the field of energetic materials.
At present, there are two main methods for constructing energetic compounds by using fluorine dinitroethyl to replace halogen atoms: (1) acetone is used as a reaction solvent, sodium phosphate dodecahydrate is used as a basic catalyst to synthesize the fluorine dinitroethyl substituted energetic compound (Chemistry Select,2017,2(16): 4567-4571). (2) Triethylamine is used as a reaction catalyst and heated to 80 ℃ to synthesize the fluorine dinitroethyl substituted energetic compound (New Journal of Chemistry,2017,41(21): 12700-. The two methods use solvents with high toxicity and have mild reaction conditions.
Disclosure of Invention
The invention aims to provide a furazano pyrazine compound and a synthesis method thereof.
The purpose of the invention is realized as follows: a fluorine dinitroethoxy furazapyrazine compound is named as 5, 6-di (2-fluorine-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine and has the following structure:
the synthesis method of the compound comprises the following steps:
(1) a step of reacting 5, 6-dichlorofurazano [3,4-b ] pyrazine (1) with 2-fluoro-2, 2-dinitroethanol in the presence of a catalyst 2,4, 6-trimethylpyridine to prepare 5-chloro-6- (2-fluoro-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine (2),
(2) a step of reacting 5-chloro-6- (2-fluoro-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine (2) with 2-fluoro-2, 2-dinitroethanol in the presence of a catalyst 4-dimethylaminopyridine to prepare a target product 5, 6-bis (2-fluoro-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine (3),
further, the molar ratio of the 5, 6-dichlorofurazano [3,4-b ] pyrazine (1) to the 2-fluoro-2, 2-dinitroethanol is 1-3: 1.
further, the molar ratio of the catalyst 2,4, 6-trimethylpyridine to the 5, 6-dichlorofurazano [3,4-b ] pyrazine (1) is 1: 1.
further, in the step (1), the reaction temperature is 25-50 ℃, and the reaction time is 1-3 hours.
Further, in the step (1), dichloromethane is used as a solvent in the reaction system.
Further, the molar ratio of the 5-chloro-6- (2-fluoro-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine (2) to the 2-fluoro-2, 2-dinitroethanol is 1-3: 1.
further, the molar ratio of the used amount of the catalyst 4-dimethylaminopyridine to the 5-chloro-6- (2-fluoro-2, 2-dinitroethoxy) furazan is 1: 1.
further, in the step (2), the reaction temperature is 25-50 ℃, and the reaction time is 1-3 hours.
Further, in the step (2), dichloromethane is used as a solvent in the reaction system.
Compared with the prior art, the invention has the advantages that:
(1) the prepared furazan pyrazine compound is rich in nitrogen and oxygen, high in energy density, aromatic and high in enthalpy of formation and other excellent performances.
(2) The prepared furazan pyrazine compound has a polynitro structure, and can endow the compound with higher density and energy.
(3) The prepared furazan pyrazine compound has better thermodynamic stability due to the existence of fluorine atoms.
(4) The synthesis method has the advantages of mild synthesis conditions, simple steps and high reaction yield.
(5) The synthetic product is applied to the field of propellants or explosives, has better performance, can endow a compound with higher density and energy due to a multi-nitro structure, and has wide application prospect.
Drawings
FIG. 1 is a crystal structure diagram of the objective product of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples.
The preparation method of the target product comprises the following steps: (1) dissolving 5, 6-dichlorofurazano [3,4-b ] pyrazine (1) in dichloromethane, adding 2-fluoro-2, 2-dinitroethanol and 2,4, 6-trimethylpyridine into the system, stirring, filtering by a silica gel short column, eluting by dichloromethane, and concentrating an eluent under reduced pressure to obtain 5-chloro-6- (2-fluoro-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine (2); (2) dissolving a compound 5-chloro-6- (2-fluoro-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine (2) in dichloromethane, adding 2-fluoro-2, 2-dinitroethanol and 4-dimethylaminopyridine into the system, stirring, filtering through a silica gel short column, eluting with dichloromethane, and concentrating an eluent under reduced pressure to obtain the 5, 6-bis (2-fluoro-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine (3).
Example 1
Synthesis of 5, 6-bis (2-fluoro-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine:
(1) 5, 6-dichlorofurazano [3,4-b ] pyrazine (1) (152mg, 0.8mmol) was dissolved in dichloromethane (6mL), 2-fluoro-2, 2-dinitroethanol (126mg, 0.8mmol), 2,4, 6-trimethylpyridine (99mg, 0.8mmol) were added to the system, which was then stirred at room temperature (25 ℃ C.) for 1h, filtered through a short column of silica gel, eluted with dichloromethane and concentrated under reduced pressure to give 5-chloro-6- (2-fluoro-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine (2). (2) Compound 2(200mg, 0.65mmol) was dissolved in methylene chloride (4mL), and 2-fluoro-2, 2-dinitroethanol (100mg, 0.65mmol) and 4-dimethylaminopyridine (80mg, 0.65mmol) were added to the system. The reaction was stirred at room temperature (25 ℃) for 1h, filtered through a short column of silica gel, eluted with dichloromethane and the eluent was concentrated under reduced pressure to give 5, 6-bis (2-fluoro-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine (3) (240mg, 87% yield). The crystal structure is shown in figure 1, and the crystal data are shown in table 1, table 2 and table 3.
1H NMR(500MHz,Acetone-d6)δ6.07(d,J＝15.6Hz,4H)ppm.
13C NMR(126MHz,Acetone-d6)δ64.55,120.45,149.94,153.39ppm.
19F NMR(470MHz,Acetone-d6)δ-110.73ppm.。
Example 2
The reaction temperature in the step (1) and the reaction temperature in the step (2) are both 40 ℃, the other conditions are the same as in the example 1, and the yield is 72 percent.
Example 3
The reaction time of the step (1) and the step (2) is 2 hours, the other conditions are the same as the example 1, and the yield is 76%.
TABLE 1 Crystal data
TABLE 1 fractional atomic coordinate and Isotropic or Equivalent Isotropic Displacement parameters
TABLE 2 atomic Displacement parameters
TABLE 3 geometric parameters
Claims (10)
1. A fluorine dinitroethoxy furazapyrazine compound is characterized in that the compound has the following structure:
2. a synthetic method of a fluorine dinitroethoxy furazan pyrazine compound is characterized by comprising the following steps:
(1) a step of reacting 5, 6-dichlorofurazano [3,4-b ] pyrazine 1 with 2-fluoro-2, 2-dinitroethanol in the presence of a catalyst 2,4, 6-trimethylpyridine to prepare 5-chloro-6- (2-fluoro-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine 2,
(2) a step of reacting 5-chloro-6- (2-fluoro-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine 2 with 2-fluoro-2, 2-dinitroethanol in the presence of a catalyst 4-dimethylaminopyridine to prepare a target product 3,
3. the process of claim 2, wherein the molar ratio of 5, 6-dichlorofurazano [3,4-b ] pyrazine (1) to 2-fluoro-2, 2-dinitroethanol is from 1 to 3: 1.
4. the process of claim 2 wherein the molar ratio of 2,4, 6-trimethylpyridine to 5, 6-dichlorofurazano [3,4-b ] pyrazine as the catalyst is 1: 1.
5. the method of claim 2, wherein in the step (1), the reaction temperature is 25 to 50 ℃ and the reaction time is 1 to 3 hours.
6. The method of claim 2, wherein in step (1), dichloromethane is used as a solvent for the reaction system.
7. The method of claim 2, wherein the molar ratio of 5-chloro-6- (2-fluoro-2, 2-dinitroethoxy) furazano [3,4-b ] pyrazine to 2-fluoro-2, 2-dinitroethanol is 1 to 3: 1.
8. the process of claim 2 wherein the molar ratio of catalyst 4-dimethylaminopyridine to 5-chloro-6- (2-fluoro-2, 2-dinitroethoxy) furazan is 1: 1.
9. the method of claim 2, wherein in the step (2), the reaction temperature is 25 to 50 ℃ and the reaction time is 1 to 3 hours.
10. The method of claim 2, wherein in step (2), dichloromethane is used as a solvent for the reaction system.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114874236A (en) * | 2022-06-24 | 2022-08-09 | 中国工程物理研究院化工材料研究所 | Five-membered aza-condensed ring framework and preparation method thereof |
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Non-Patent Citations (1)
| Title |
|---|
| DAVID E. CHAVEZ，等: "Energetic Trinitro- and Dinitro-Fluoroethyl Ethers of 1,2,4,5-Tetrazines", 《ANGEWANDTE CHEMIE，INTERNATIONAL EDITION》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114874236A (en) * | 2022-06-24 | 2022-08-09 | 中国工程物理研究院化工材料研究所 | Five-membered aza-condensed ring framework and preparation method thereof |
| CN114874236B (en) * | 2022-06-24 | 2023-05-05 | 中国工程物理研究院化工材料研究所 | Five-membered aza condensed ring skeleton and preparation method thereof |
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Application publication date: 20210629 |