CN100532377C - Compound containing tetrazine polynitrobenzene and synthesis method thereof - Google Patents
Compound containing tetrazine polynitrobenzene and synthesis method thereof Download PDFInfo
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- CN100532377C CN100532377C CNB2006101525820A CN200610152582A CN100532377C CN 100532377 C CN100532377 C CN 100532377C CN B2006101525820 A CNB2006101525820 A CN B2006101525820A CN 200610152582 A CN200610152582 A CN 200610152582A CN 100532377 C CN100532377 C CN 100532377C
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- trinitrobenzene
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Abstract
The invention discloses a compound with tetrazine multi-nitrobenzol with molecular structural formula as formula I and synthesizing method, which is characterized by the following: realizing the synthesis of tetrazine molecular with rich nitrogen and multinitrobenzol compound; adopting organic solvent in the liquid phase reaction as large-polarity solvent; culturing monocrystalline through fitful polarity solvent.
Description
Technical field
The present invention relates to a kind of compound and synthetic method thereof that contains the tetrazine trinitrobenzene, belong to the synthetic field of explosive.
Background technology
Generally all contain nitryl group in traditional organic energy-containing compound molecular structure, its Enthalpies of Formation is generally lower, is generally negative value or approaches zero, and the energy that is discharged is mainly derived from and generates CO
2And H
2The exothermic process of O.As the energetic material of a class unique properties, the energy of rich nitrogen energetic material depends primarily on the high Enthalpies of Formation that molecule itself is had, rather than the oxidation scission of c h bond.Contain a large amount of N-N and C-N key in the nitrogen-enriched compounds molecule, thereby have high positive Enthalpies of Formation, simultaneously,, therefore, show dual positive-effect, can improve the density of material, regulate oxygen balance again easily because carbon, hydrogen richness in the compound are low relatively.Tetrazine kind compound is typical case's representative of nitrogen-enriched compounds, as a kind of novel energetic material, the tetrazine nitrogen-enriched compounds can be used for high-energy insensitive explosive, low characteristic signal propellant, gas-evolution agent, pyrotechnic composition and high-performance environment-friendly fireworks etc., almost relate to the every field that energetic material is used, cause extensive concern.A large amount of compounds that contains the tetrazine molecule is arranged, as shown below, higher Enthalpies of Formation and density (Angew.Chem.Int.Ed.2000,39,1791, Angew.Chem.Int.Ed.2004,43,5658 are arranged; Org.Lett.2004,6,2889).
The shortcoming of these compounds be have to contain sensitivity low, poor heat stability very unsettled containing can group as nitrine; Perhaps synthetic method will be passed through polystep reaction, and side reaction is many, and the condition harshness is quite numerous and diverse, is difficult for realizing, more is difficult to extensive synthesizing, and the production cost height is difficult to realize using.
Summary of the invention
The objective of the invention is to generate the low problem of heat in order to solve trinitrobenzene, by the tetrazine molecule of rich nitrogen being introduced the method for trinitrobenzene, make resultant both contain the tetrazine molecule of rich nitrogen, the covalent molecule that contains trinitrobenzene again, increase the insensitiveness and the oxygen balance coefficient of newly-generated compound, improved Enthalpies of Formation, and the trinitrobenzene mature production technology, low price, new synthetic compound reduces cost easily.
The molecular structure of The compounds of this invention is:
The present invention is achieved by the following scheme.
By halo trinitrobenzene and 3-amino-1,2,4, nucleophilic substitution reaction between the 5-tetrazine, synthesized a kind of nitrogen-enriched compounds that contains the tetrazine trinitrobenzene, the organic solvent in the liquid phase reaction is that the big solvent of polarity is one of acetonitrile, acetone, 2-butanone, dioxane, tetrahydrofuran (THF), nitrogen dimethylformamide, ethanol or methyl alcohol, and product is the mixed solvent of ethyl acetate and acetone by the polarity appropriate solvent, mol ratio is 1:1～9, cultivates to obtain red monocrystalline.Simple synthetic method without nitrogen protection, is applicable to the tetrazine molecule of multiple Halogen oil of mirbane or rich nitrogen, purifies easily, is easy to mass production, and waste liquid can reclaim, and saves cost, helps environmental protection, and its synthetic line is referring to accompanying drawing 1.
Concrete synthetic method:
With halo trinitrobenzene and 3-amino-6 (3)-1,2,4, the 5-tetrazine directly mixes stirring, and mol ratio is 1.0～2.0, be heated to 20 ℃～120 ℃, be cooled to 0 ℃～30 ℃ behind the stopped reaction, revolve inspissation and contract, obtain red precipitate, dry more than 1 hour in the water-bath baking oven under 40 ℃, product is dissolved in the mixed solvent of ethyl acetate and acetone, mol ratio is 1:1～9, slowly volatilization can obtain red monocrystalline, and productive rate is more than 70%.
This step is adopted different reaction conditionss according to the difference of different halogeno-benzene parent electric energy power, and faster than chloro trinitrobenzene speed of response as bromo trinitrobenzene speed of response, the corresponding reaction times is just short.
Product can be by infrared, UV, visible light, and monocrystalline characterizes.
The present invention has following beneficial effect:
1. solve trinitrobenzene and generate the low problem of heat,, make resultant both contain the tetrazine molecule of rich nitrogen, contain trinitrobenzene again, increased the oxygen balance coefficient, improved the mole Enthalpies of Formation by the tetrazine molecule of rich nitrogen being introduced the method for trinitrobenzene.
2. the synthetic covalent molecule that contains the tetrazine trinitrobenzene has increased the conjugation of molecule, and intramolecularly has covalent linkage, strengthens the stability of synthetic compound, has reduced sensitivity.
3. reaction conditions gentleness, the time is short, and the yield height is a large amount of easily synthetic.
4. can reach waste liquid and reclaim with different organic solvents, save cost, be beneficial to environmental protection.
5. synthetic method is simpler, and product is single, is easy to separation and purification, and equipment is simple, simple monocrystal cultivation method.
6. trinitrobenzene mature production technology, cost is low, and the one-tenth instinct of new synthetic compound reduces, and is easy to practical application.
Description of drawings
Accompanying drawing 1: the synthetic line of tetrazine trinitrobenzene.
Accompanying drawing 2: the infrared spectra of tetrazine trinitrobenzene is with reference to figure:
3094cm in infrared figure
-1The characteristic peak of the corresponding imino-in peak illustrates that this compound contains imino-, the 2929cm in infrared figure
-1The peak, the characteristic peak at corresponding alkyl peak, 1542 and 1343cm in infrared
-1Characteristic peak, the nitro peak on the corresponding phenyl ring illustrates that this compound contains nitro.
Accompanying drawing 3: the uv-vis spectra of tetrazine trinitrobenzene is with reference to figure:
Characteristic peak is respectively 253,342,404nm.
Accompanying drawing 4: the single crystal structure figure of tetrazine trinitrobenzene:
Can confirm as by single crystal structure and to contain 3-imino--(2,4, the 6-trinitrobenzene)-6 (3)-1,2,4, the compound of 5-tetrazine.
Embodiment
In conjunction with the embodiments, further the present invention is made an explanation.
Embodiment one
3-imino--(2,4, the 6-trinitrobenzene)-6 (3, the 5-dimethyl pyrazole)-1,2,4,5-tetrazine synthetic method, synthetic route are referring to accompanying drawing 1, with 1.5mmo chloro trinitrobenzene and 1mmol 3-amino-6 (3, the 5-dimethyl pyrazole)-1,2,4, the 5-tetrazine is dissolved in the acetonitrile of 20mL, and heating is at 80 ℃ of backflow 6h, be cooled to 20 ℃ behind the stopped reaction, revolve inspissation and contract, column chromatography purification obtains red precipitate.Dry more than 1 hour in the water-bath baking oven under 40 ℃.Product is dissolved in the mixed solvent of ethyl acetate and acetone, and mol ratio is 2, and slowly volatilization can obtain red monocrystalline, productive rate 75% (based on the chloro trinitrobenzene).Sign is seen: infrared spectrogram is seen accompanying drawing 2, and the ultraviolet-visible spectrogram is seen accompanying drawing 3, and the single crystal structure spectrogram is seen accompanying drawing 4.
Embodiment two
3-imino--(2,4, the 6-trinitrobenzene)-6 (3, the 5-dimethyl pyrazole)-1,2,4,5-tetrazine synthetic method, synthetic route are referring to accompanying drawing 1, with 1.5mmol bromo trinitrobenzene and 1mmol 3-amino-6 (3, the 5-dimethyl pyrazole)-1,2,4, the 5-tetrazine is dissolved in the acetonitrile of 20mL, and heating is at 80 ℃ of backflow 2h, be cooled to 20 ℃ behind the stopped reaction, revolve inspissation and contract, column chromatography purification obtains red precipitate.Dry more than 1 hour in the water-bath baking oven under 40 ℃.Product is dissolved in the mixed solvent of ethyl acetate and acetone, and mol ratio is 2, and slowly volatilization can obtain red monocrystalline, productive rate 85% (based on the bromo trinitrobenzene).Sign is seen: infrared spectrogram is seen accompanying drawing 2, and the ultraviolet-visible spectrogram is seen accompanying drawing 3, and the single crystal structure spectrogram is seen accompanying drawing 4.
Embodiment three
3-imino--(2,4, the 6-trinitrobenzene)-6 (3)-1,2,4,5-tetrazine synthetic method, synthetic route is referring to accompanying drawing 1, with 1.5mmol chloro trinitrobenzene and 1mmol 3-amino-6 (3)-1,2,4, the 5-tetrazine is dissolved in the N of 20mL, dinethylformamide, heating is cooled to 20 ℃ at 80 ℃ of backflow 4h behind the stopped reaction, ethyl acetate (3 * 20mL) and water extraction, revolve inspissation and contract, column chromatography purification obtains red precipitate.Dry more than 1 hour in the water-bath baking oven under 40 ℃.Product is dissolved in the mixed solvent of ethyl acetate and acetone, and mol ratio is 2, and slowly volatilization can obtain red monocrystalline, productive rate 78% (based on the chloro trinitrobenzene).Sign is seen: infrared spectrogram is seen accompanying drawing 2, and the ultraviolet-visible spectrogram is seen accompanying drawing 3, and the single crystal structure spectrogram is seen accompanying drawing 4.
Embodiment four
3-imino--(2,4, the 6-trinitrobenzene)-6 (3)-1,2,4,5-tetrazine synthetic method, synthetic route is referring to accompanying drawing 1, with 1.5mmol bromo trinitrobenzene and 1mmol 3-amino-6 (3)-1,2,4, the 5-tetrazine is dissolved in the N of 20mL, dinethylformamide, heating is cooled to 20 ℃ at 80 ℃ of backflow 6h behind the stopped reaction, ethyl acetate (3 * 20mL) and water extraction, revolve inspissation and contract, column chromatography purification obtains red precipitate.Dry more than 1 hour in the water-bath baking oven under 40 ℃.Product is dissolved in the mixed solvent of ethyl acetate and acetone, and mol ratio is 2, and slowly volatilization can obtain red monocrystalline, productive rate 79% (based on the bromo trinitrobenzene).Sign is seen: infrared spectrogram is seen accompanying drawing 2, and the ultraviolet-visible spectrogram is seen accompanying drawing 3, and the single crystal structure spectrogram is seen accompanying drawing 4.
Embodiment five
3-imino--(2,4, the 6-trinitrobenzene)-6 (3, the 5-dimethyl pyrazole)-1,2,4,5-tetrazine synthetic method, synthetic route are referring to accompanying drawing 1, with 1.5mmol chloro trinitrobenzene and 1mmol 3-amino-6 (3, the 5-dimethyl pyrazole)-1,2,4, the 5-tetrazine is dissolved in the tetrahydrofuran (THF) of 20mL, and heating is at 70 ℃ of backflow 8h, be cooled to 20 ℃ behind the stopped reaction, revolve inspissation and contract, column chromatography purification obtains red precipitate.Dry more than 1 hour in the water-bath baking oven under 40 ℃.Product is dissolved in the mixed solvent of ethyl acetate and acetone, and mol ratio is 2, and slowly volatilization can obtain red monocrystalline, productive rate 87% (based on the chloro trinitrobenzene).Sign is seen: infrared spectrogram is seen accompanying drawing 2, and the ultraviolet-visible spectrogram is seen accompanying drawing 3, and the single crystal structure spectrogram is seen accompanying drawing 4.
Embodiment six
3-imino--(2,4, the 6-trinitrobenzene)-6 (3, the 5-dimethyl pyrazole)-1,2,4,5-tetrazine synthetic method, synthetic route are referring to accompanying drawing 1, with 1mmol bromo trinitrobenzene and 1.5mmol 3-amino-6 (3, the 5-dimethyl pyrazole)-1,2,4, the 5-tetrazine is dissolved in the tetrahydrofuran (THF) of 20mL, backflow 4h, be cooled to 20 ℃ behind the stopped reaction, revolve inspissation and contract, column chromatography purification obtains red precipitate.Dry more than 1 hour in the water-bath baking oven under 40 ℃.Product is dissolved in the mixed solvent of ethyl acetate and acetone, and mol ratio is 2, and slowly volatilization can obtain red monocrystalline, productive rate 78% (based on the bromo trinitrobenzene).Sign is seen: infrared spectrogram is seen accompanying drawing 2, and the ultraviolet-visible spectrogram is seen accompanying drawing 3, and the single crystal structure spectrogram is seen accompanying drawing 4.
Embodiment seven
3-imino--(2,4, the 6-trinitrobenzene)-6 (3, the 5-dimethyl pyrazole)-1,2,4,5-tetrazine synthetic method, synthetic route are referring to accompanying drawing 1, with 1mmol chloro trinitrobenzene and 1.5mmol 3-amino-6 (3, the 5-dimethyl pyrazole)-1,2,4, the 5-tetrazine is dissolved in the ethanol of 20mL, and heating is at 80 ℃ of backflow 9h, be cooled to 20 ℃ behind the stopped reaction, revolve inspissation and contract, column chromatography purification obtains red precipitate.Dry more than 1 hour in the water-bath baking oven under 40 ℃.Product is dissolved in the mixed solvent of ethyl acetate and acetone, and mol ratio is 2, and slowly volatilization can obtain red monocrystalline, productive rate 79% (based on the chloro trinitrobenzene).Sign is seen: infrared spectrogram is seen accompanying drawing 2, and the ultraviolet-visible spectrogram is seen accompanying drawing 3, and the single crystal structure spectrogram is seen accompanying drawing 4.
Embodiment eight
3-imino--(2,4, the 6-trinitrobenzene)-6 (3, the 5-dimethyl pyrazole)-1,2,4,5-tetrazine synthetic method, synthetic route are referring to accompanying drawing 1, with 1mmol bromo trinitrobenzene and 1.5mmol 3-amino-6 (3, the 5-dimethyl pyrazole)-1,2,4, the 5-tetrazine is dissolved in the ethanol of 20mL, and heating is at 80 ℃ of backflow 7h, be cooled to 20 ℃ behind the stopped reaction, revolve inspissation and contract, column chromatography purification obtains red precipitate.Dry more than 1 hour in the water-bath baking oven under 40 ℃.Product is dissolved in the mixed solvent of ethyl acetate and acetone, and mol ratio is 2, and slowly volatilization can obtain red monocrystalline, productive rate 83% (based on the bromo trinitrobenzene).Sign is seen: infrared spectrogram is seen accompanying drawing 2, and the ultraviolet-visible spectrogram is seen accompanying drawing 3, and the single crystal structure spectrogram is seen accompanying drawing 4.
Claims (5)
1. compound that contains the tetrazine trinitrobenzene is characterized in that molecular structure is:
2. a kind of synthetic method that contains the compound of tetrazine trinitrobenzene as claimed in claim 1, it is characterized in that: by halo trinitrobenzene and 3-amino-1,2,4, the nucleophilic substitution reaction of 5-tetrazine, with halo trinitrobenzene and 3-amino-6 (3) 1,2,4,5-tetrazine, mol ratio are 1.0～2.0, directly mix at polar organic solvent and stir, polar organic solvent is an acetonitrile, acetone, 2-butanone, dioxane, tetrahydrofuran (THF), N, dinethylformamide, ethanol, methyl alcohol or methylene dichloride are heated to 20～120 ℃, are cooled to 0～30 ℃ behind the stopped reaction, revolving inspissation contracts, dry more than 1 hour in the water-bath baking oven under 30～80 ℃, obtain red precipitate, with red precipitate dry more than 1 hour in the water-bath baking oven under 40 ℃, mixed solvent by ethyl acetate and acetone, mol ratio is 1:1～9, and slowly volatilization is cultivated and obtained red monocrystalline.
3. a kind of synthetic method that contains the compound of tetrazine trinitrobenzene as claimed in claim 2 is characterized in that the halo trinitrobenzene is chloro trinitrobenzene or bromo trinitrobenzene.
4. a kind of synthetic method that contains the compound of tetrazine trinitrobenzene as claimed in claim 2 is characterized in that reaction is without nitrogen protection.
5. a kind of synthetic method that contains the compound of tetrazine trinitrobenzene as claimed in claim 2, the sign that it is characterized in that this compound of synthetic is by infrared, and nuclear-magnetism and monocrystalline and ultraviolet-visible spectral method characterize.
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| CN107843584B (en) * | 2017-11-03 | 2020-07-14 | 首都师范大学 | Bisulfite ion identification and detection method |
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Non-Patent Citations (6)
| Title |
|---|
| 3, 6-di(azido)-1,2,4,5-tetrazine: a procursor for the preparationof carbon nanospheres and nitrogen-rich carbon nitrides. My Hang V. Huynh, et al.Angew. Chem. Ind. Ed.,Vol.43 . 2004 |
| 3, 6-di(azido)-1,2,4,5-tetrazine: a procursor for the preparationof carbon nanospheres and nitrogen-rich carbon nitrides. My Hang V. Huynh, et al.Angew. Chem. Ind. Ed.,Vol.43 . 2004 * |
| 3,3'-azobis(6-amino-1,2,4,5-tetrazine):a novel high-nitrogenenergetic material. David E. Chavez, et al.Angew. Chem. Int. Ed.,Vol.39 No.10. 2000 |
| 3,3'-azobis(6-amino-1,2,4,5-tetrazine):a novel high-nitrogenenergetic material. David E. Chavez, et al.Angew. Chem. Int. Ed.,Vol.39 No.10. 2000 * |
| Novel high-nitrogen materials based on nitroguanyl-substitutedtetrazines,. David E. Chavez, et al.Organic Letters,,Vol.6 No.17. 2004 |
| Novel high-nitrogen materials based on nitroguanyl-substitutedtetrazines,. David E. Chavez, et al.Organic Letters,,Vol.6 No.17. 2004 * |
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