CN117229227A - 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine and synthesis method thereof - Google Patents
3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine and synthesis method thereof Download PDFInfo
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- CN117229227A CN117229227A CN202311043850.5A CN202311043850A CN117229227A CN 117229227 A CN117229227 A CN 117229227A CN 202311043850 A CN202311043850 A CN 202311043850A CN 117229227 A CN117229227 A CN 117229227A
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- tetrazine
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- ethoxycarbonylmethyl
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- -1 ethoxycarbonylmethyl-1, 2,4, 5-tetrazine Chemical compound 0.000 title claims abstract description 33
- 238000001308 synthesis method Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims abstract description 18
- ZPTORXXRWBRLQR-UHFFFAOYSA-N 6-chloro-1,2,4,5-tetrazin-3-amine Chemical compound NC1=NN=C(Cl)N=N1 ZPTORXXRWBRLQR-UHFFFAOYSA-N 0.000 claims abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 11
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 11
- 239000012312 sodium hydride Substances 0.000 claims description 11
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical class [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 11
- 238000005474 detonation Methods 0.000 abstract description 5
- 230000000269 nucleophilic effect Effects 0.000 abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- HTJMXYRLEDBSLT-UHFFFAOYSA-N 1,2,4,5-tetrazine Chemical compound C1=NN=CN=N1 HTJMXYRLEDBSLT-UHFFFAOYSA-N 0.000 description 5
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical group C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002244 furazanes Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003536 tetrazoles Chemical group 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application provides 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine and a synthesis method thereof, wherein the structural formula is shown as follows:
Description
Technical Field
The application belongs to the technical field of energetic materials, relates to an energetic material intermediate, and in particular relates to 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine and a synthesis method thereof.
Background
After the methylene in diethyl malonate is connected with two electron withdrawing groups of carbonyl, the acidity and the leaving property of C-H are enhanced, a certain electronegativity is reflected, and the carbanion formed after leaving is a good nucleophilic attack reagent, and can generate a plurality of typical nucleophilic attack reactions, such as addition reaction with carbonyl carbon in aldehyde and ketone, nucleophilic substitution reaction with haloalkane, and the like. In the field of energetic materials, diethyl malonate (or diethyl ethoxycarbonylmethyl) substituted aromatic ring compounds can be changed into energetic compounds such as geminal dinitrate and nitroxymethyl through hydrolysis, nitration and other reactions, and are important intermediate compounds.
Diethyl malonate-substituted carbon aromatic ring compounds have been studied very well, e.g., alpha-aryl of beta-diketones with aryl halides catalyzed by CuO/aluminum amide
(Tetrahedron Letters,2014,55 (50), 6873-6877) reported the catalytic reaction of 4-chlorobenzaldehyde with diethyl malonate to give 4- (3-diethyl malonate) benzaldehyde, the reaction equation being as follows:
disclosure of Invention
Aiming at the defects existing in the prior art, the application aims to provide 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine and a synthesis method thereof, which solve the technical problem that an energetic material intermediate in the prior art is difficult to have good nucleophilic attack reaction and high detonation performance.
In order to solve the technical problems, the application adopts the following technical scheme:
3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine having the structural formula shown below:
the application also provides a preparation method of the 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine, which comprises the following steps:
sequentially adding diethyl malonate and dry tetrahydrofuran into a reaction container at the temperature of minus 10 ℃ to 10 ℃, then adding sodium hydride in batches, reacting for 30min to 90min at the temperature of 20 ℃ to 30 ℃ after the addition, cooling to the temperature of minus 10 ℃ to 10 ℃, dropwise adding tetrahydrofuran solution containing 3-amino-6-chloro-1, 2,4, 5-tetrazine into the reaction container, and reacting for 2h to 4h at the temperature of 20 ℃ to 30 ℃ after the dropwise addition.
And step two, after the reaction is finished, distilling at room temperature under reduced pressure to remove the solvent, adding water into the system, dropwise adding a saturated sodium bisulphite solution to be neutral, extracting for a plurality of times, merging organic phases, washing with water, drying and evaporating to dryness to obtain a target product, namely 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine.
Preferably, in the first step, the molar ratio of 3-amino-6-chloro-1, 2,4, 5-tetrazine, diethyl malonate and sodium hydride is 1.0 (2.0-6.0): 2.0-6.0.
Preferably, the method is carried out according to the following steps:
sequentially adding diethyl malonate and dry tetrahydrofuran into a 250mL three-necked flask at the temperature of 0 ℃, then adding sodium hydride in batches, reacting for 60min at the temperature of 25 ℃ after the addition, cooling to the temperature of 0 ℃, dropwise adding a tetrahydrofuran solution containing 3-amino-6-chloro-1, 2,4, 5-tetrazine into the mixture, and reacting for 3h at the temperature of 25 ℃ after the dropwise addition, wherein the molar ratio of 3-amino-6-chloro-1, 2,4, 5-tetrazine to diethyl malonate to sodium hydride is 1.0:4.0:4.0.
And step two, after the reaction is finished, distilling at room temperature under reduced pressure to remove the solvent, adding water into the system, dropwise adding a saturated sodium bisulphite solution to neutrality, extracting with ethyl acetate for three times, combining organic phases, washing with water, drying with anhydrous magnesium sulfate, and evaporating to dryness to obtain purple solid 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine.
Compared with the prior art, the application has the following technical effects:
the application firstly replaces 1,2,4, 5-tetrazine with diethyl malonate to prepare the energetic intermediate compound. The prepared energetic material intermediate has good nucleophilic attack reaction and high detonation performance.
(II) the 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine is an energy-containing material intermediate, and the geminal dinitration substituted and nitroxymethyl substituted 1,2,4, 5-tetrazine compound with excellent performance can be obtained through further reaction, which is not reported at present.
The following examples illustrate the application in further detail.
Detailed Description
All materials and equipment used in the present application are known in the art, unless otherwise specified.
In the field of aza-aromatic rings related to energetic materials, few diethyl malonate substituted compounds are reported, and particularly 1,2,4, 5-tetrazine with high detonation performance is not reported.
Compared with other five-membered polyazacyclic rings such as triazole, tetrazole, furazane, pyrazole and the like, the 1,2,4, 5-tetrazine has higher formation enthalpy, density and oxygen balance, so that among five-membered polyazacyclic ring energetic compounds with similar structures, the compound with the 1,2,4, 5-tetrazine skeleton tends to have higher detonation performance, and therefore, the 1,2,4, 5-tetrazine is an excellent energetic compound unit skeleton.
The application provides 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine, which has the following structural formula:
the compound takes diethyl malonate and 3-amino-6-chloro-1, 2,4, 5-tetrazine as raw materials, and the synthetic route is as follows:
wherein Et refers to an ethyl group.
The compound is used as an energy material intermediate, and can obtain the gem-dinitrated methyl substituted and nitroxymethyl substituted 1,2,4, 5-tetrazine compound with excellent performance through subsequent further reaction.
The following specific embodiments of the present application are provided, and it should be noted that the present application is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical scheme of the present application fall within the protection scope of the present application.
Example 1:
the embodiment provides a synthesis method of 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine, which comprises the following steps:
sequentially adding 2.0g diethyl malonate and 50mL dry tetrahydrofuran into 250mL three-port bottles at the temperature of 0 ℃, adding 0.8g 60% sodium hydride in mass fraction in batches, reacting at the temperature of 25 ℃ for 60min after the addition, cooling to the temperature of 0 ℃, dropwise adding 10mL tetrahydrofuran solution containing 1.31g 3-amino-6-chloro-1, 2,4, 5-tetrazine, and reacting for 3h after the dropwise addition to the temperature of 25 ℃.
And step two, after the reaction is finished, distilling at room temperature under reduced pressure to remove the solvent, adding 50mL of water into the system, dropwise adding a saturated sodium bisulphite solution to neutrality, extracting with 75mL of ethyl acetate three times, merging organic phases, washing with water, drying with anhydrous magnesium sulfate, and evaporating to dryness to obtain 2.28g of purple solid 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine, wherein the yield is 89%.
Structural characterization:
elemental analysis: c (C) 9 H 13 N 5 O 4
Theoretical value (%): c (42.35), H (5.13), N (27.44);
measured value (%): c (42.09), H (5.11), N (27.55).
1 H-NMR(DMSO,δ,ppm):7.20,s,br,2H,5.66,s,1H,4.19,q,4H,J＝8.0Hz,1.21,t,6H,J＝8.0Hz。
13 C-NMR(DMSO,δ,ppm):172.9(-C＝O),161.9(tetrazine),158.7(tetrazine),58.9(-CH-),41.4(-CH 2 -),14.3(-CH 3 )。
From the above structural characterization results, the purple solid prepared in this example is the target product 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine.
Example 2:
the embodiment provides a synthesis method of 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine, which comprises the following steps:
sequentially adding 1.0g diethyl malonate and 30mL dry tetrahydrofuran into 250mL three-port bottles at the temperature of minus 10 ℃, adding 0.4g 60% sodium hydride in mass fraction in batches, reacting at the temperature of 20 ℃ for 30min after the addition is finished, cooling to the temperature of minus 10 ℃, dropwise adding 10mL tetrahydrofuran solution containing 1.31g 3-amino-6-chloro-1, 2,4, 5-tetrazine, and reacting for 2h after the dropwise addition is finished, and rising to the temperature of 20 ℃.
And step two, after the reaction is finished, distilling at room temperature under reduced pressure to remove the solvent, adding 30mL of water into the system, dropwise adding a saturated sodium bisulphite solution to neutrality, extracting with 30mL of ethyl acetate three times, merging organic phases, washing with water, drying with anhydrous magnesium sulfate, and evaporating to dryness to obtain 1.77g of purple solid 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine, wherein the yield is 69%.
The structure identification result of this example was the same as that of example 1.
Example 3:
the embodiment provides a synthesis method of 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine, which comprises the following steps:
step one, sequentially adding 3.0g diethyl malonate and 70mL dry tetrahydrofuran into a 250mL three-port bottle at 10 ℃, adding 1.2g 60% sodium hydride in mass fraction in batches, reacting at 20-30 ℃ for 90min after the addition, cooling to 10 ℃, dropwise adding 10mL tetrahydrofuran solution containing 1.31g 3-amino-6-chloro-1, 2,4, 5-tetrazine, and reacting for 4h at 30 ℃.
And step two, after the reaction is finished, distilling at room temperature under reduced pressure to remove the solvent, adding 70mL of water into the system, dropwise adding a saturated sodium bisulphite solution to neutrality, extracting with 120mL of ethyl acetate for three times, merging organic phases, washing with water, drying with anhydrous magnesium sulfate, and evaporating to dryness to obtain 2.02g of purple solid 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine, wherein the yield is 79%.
The structure identification result of this example was the same as that of example 1.
Claims (4)
1. 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine, characterized by the following structural formula:
2. a process for the preparation of 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine according to claim 1, comprising the steps of:
sequentially adding diethyl malonate and dry tetrahydrofuran into a reaction container at the temperature of minus 10 ℃ to 10 ℃, then adding sodium hydride in batches, reacting for 30 to 90 minutes at the temperature of 20 ℃ to 30 ℃ after the addition is finished, cooling to the temperature of minus 10 ℃ to 10 ℃, dropwise adding tetrahydrofuran solution containing 3-amino-6-chloro-1, 2,4, 5-tetrazine into the reaction container, and reacting for 2 to 4 hours at the temperature of 20 ℃ to 30 ℃ after the dropwise addition is finished;
and step two, after the reaction is finished, distilling at room temperature under reduced pressure to remove the solvent, adding water into the system, dropwise adding a saturated sodium bisulphite solution to be neutral, extracting for a plurality of times, merging organic phases, washing with water, drying and evaporating to dryness to obtain a target product, namely 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine.
3. The process for producing 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine according to claim 2, wherein in the first step, the molar ratio of 3-amino-6-chloro-1, 2,4, 5-tetrazine, diethyl malonate and sodium hydride is 1.0 (2.0 to 6.0).
4. A process for the preparation of 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine according to claim 2, characterised in that it is carried out according to the following steps:
sequentially adding diethyl malonate and dry tetrahydrofuran into a 250mL three-mouth bottle at 0 ℃, then adding sodium hydride in batches, reacting for 60min at 25 ℃ after the addition, cooling to 0 ℃, dropwise adding a tetrahydrofuran solution containing 3-amino-6-chloro-1, 2,4, 5-tetrazine into the mixture, and reacting for 3h at 25 ℃ after the dropwise adding, wherein the molar ratio of the 3-amino-6-chloro-1, 2,4, 5-tetrazine to the diethyl malonate to the sodium hydride is 1.0:4.0:4.0;
and step two, after the reaction is finished, distilling at room temperature under reduced pressure to remove the solvent, adding water into the system, dropwise adding a saturated sodium bisulphite solution to neutrality, extracting with ethyl acetate for three times, combining organic phases, washing with water, drying with anhydrous magnesium sulfate, and evaporating to dryness to obtain purple solid 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311043850.5A CN117229227A (en) | 2023-08-18 | 2023-08-18 | 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine and synthesis method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311043850.5A CN117229227A (en) | 2023-08-18 | 2023-08-18 | 3-amino-6-bis ethoxycarbonylmethyl-1, 2,4, 5-tetrazine and synthesis method thereof |
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2023
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