Acoustic resonance synthesis method of 1, 4-diformyl-2, 3, 5, 6-tetrahydroxypiperazine
The synthesis of 1,4-dicarboxy-2,3,5,6-tetrahydroxypiperazine at room temperature using acoustic resonance enhancement technology solved the problems of long synthesis time and low yield, achieving a highly efficient synthesis effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-25
- Publication Date
- 2026-04-07
AI Technical Summary
The synthesis of 1,4-dicarboxy-2,3,5,6-tetrahydroxypiperazine in the existing technology is time-consuming and yields are low, especially the aldehyde-amine condensation reaction time, which is more than 2 hours and the yield is about 80%, indicating room for improvement.
Acoustic resonance enhancement technology was used to carry out the reaction of formamide, glyoxal and alkaline solution at room temperature, which shortened the reaction time to 5-10 minutes and increased the yield to 90%. The alkaline solution used included sodium hydroxide, potassium hydroxide or triethylamine.
The reaction time was significantly shortened and the yield was increased, achieving efficient synthesis that can be completed at room temperature without additional heating or cooling.
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic synthesis, and in particular relates to an acoustic resonance synthesis method for 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine. Background Technology
[0002] Cage-type polynitro energetic compound 4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazatetracyclic [5.5.0.0] 5,9 .0 3,11 1,4-Dicosane, abbreviated as TEX, has a three-dimensional cage-like molecular structure with significant ring strain. It also boasts a high nitrogen content, low hydrocarbon content, easily achieves oxygen equilibrium, and exhibits a higher enthalpy of combustion. Furthermore, TEX exhibits low mechanical sensitivity, good thermal stability, and excellent detonation performance, making it a high-quality, insensitive explosive that meets all application requirements. Compared to other cage-like nitrogen heterocyclic energetic materials, the synthesis of TEX is simple, involving only two steps. The first step involves the condensation of formamide and glyoxal with an aldehyde-amine reaction under alkaline conditions to obtain 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine (DFTHP), followed by nitration to yield the target compound. The synthesis of the intermediate DFTHP via the first step of the aldehyde-amine condensation reaction typically takes a long time (over 2 hours) with a yield of approximately 80%, leaving room for further improvement. Summary of the Invention
[0003] In view of the defects or deficiencies of the prior art, the present invention provides an acoustic resonance synthesis method for 1,4-dicarboxy-2,3,5,6-tetrahydroxypiperazine.
[0004] Therefore, the present invention provides an acoustic resonance synthesis method for 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine, comprising: reacting formamide, glyoxal, and alkaline solution for 5–10 min under acoustic resonance and room temperature (20–30°C, preferably 25°C) conditions to synthesize 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine; wherein the acoustic resonance acceleration is 196–980 m / s². 2 The alkaline solution is selected from sodium hydroxide aqueous solution, potassium hydroxide aqueous solution or triethylamine.
[0005] In a further embodiment, the reaction solution after 5–10 min of reaction is filtered, washed, and dried to obtain the aldehyde-amine condensation product 1,4-dicarboxylo-2,3,5,6-tetrahydroxypiperazine.
[0006] An optional configuration is that the molar ratio of formamide, glyoxal, and alkali is 1:1 to 1.1:0.1 to 0.2.
[0007] This invention utilizes acoustic resonance enhancement technology to achieve the above-mentioned objectives and synthesizes 1,4-dicarboxy-2,3,5,6-tetrahydroxypiperazine (DFTHP), achieving unexpected results. On the one hand, it significantly shortens the reaction time (from more than 2 hours to 5-10 minutes); and on the other hand, it increases the reaction yield (from ~80% to 90%). Furthermore, the reaction can be carried out at room temperature without the need for additional heating or cooling. Detailed Implementation
[0008] Unless otherwise specified, the scientific and technical terms used in this article are based on the understanding of those skilled in the art.
[0009] The technical solution of the present invention will be clearly and completely described below with reference to embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following reference to the embodiments is exemplary and is only used to explain the present invention, and should not be construed as limiting the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0010] Example 1:
[0011] (1) Add 3.6g (80mmol) of formamide, 12.76g (88mmol) of glyoxal aqueous solution (mass fraction of 40%) and 1.62g (16mmol) of triethylamine to the reactor;
[0012] (2) Fix the reactor on the acoustic resonance reaction platform and adjust the acceleration of the acoustic resonance reaction platform to 196 m / s². 2 The reaction time at room temperature (25℃) is 10 min;
[0013] (3) After filtration, washing with water (50 mL, 3 times), washing with ethanol (50 mL, 3 times), and drying (50℃, 12 hours), 7.00 g (34.0 mmol) of DFTHP was obtained, with a yield of 85.0%.
[0014] Characterization of the resulting product structure:
[0015] 1 H NMR(DMSO-d6,500MHz)δ:8.26(s,2H),6.01(d,4H),5.45(d,2H),4.96(d,2H)ppm. 13 C NMR(DMSO-d6,126MHz)δ:164.99,164.91,79.91,79.53,73.18,72.85ppm.IR(KBr,cm -1):3329,3227,2723,1670,1434,1402,1292,1074,1052,938,656.
[0016] Its structural formula has been identified as follows:
[0017] Example 2:
[0018] In this embodiment, the acceleration of the acoustic resonance response platform is adjusted to 294 m / s² in step (2). 2 The rest was the same as in Example 1, yielding 7.42 g (36.0 mmol) of DFTHP, with a yield of 90.0%.
[0019] Example 3:
[0020] In this embodiment, the acceleration of the acoustic resonance response platform is adjusted to 980 m / s² in step (2). 2 The rest was the same as in Example 1, yielding 7.11 g (34.4 mmol) of DFTHP, with a yield of 86.0%.
[0021] Example 4:
[0022] In this embodiment, the acceleration of the acoustic resonance response platform is adjusted to 294 m / s² in step (2). 2 The reaction time was 5 min, and the rest was the same as in Example 1, yielding 7.33 g (35.6 mmol) of DFTHP, with a yield of 89.0%.
[0023] Example 5:
[0024] In this embodiment, the acceleration of the acoustic resonance response platform is adjusted to 294 m / s² in step (2). 2 The reaction time was 8 min, and the rest was the same as in Example 1, yielding 7.37 g (35.8 mmol) of DFTHP, with a yield of 89.5%.
[0025] Example 6:
[0026] In this embodiment, the amount of glyoxal aqueous solution (mass fraction of 40%) added in step (1) was 11.6g (80mmol), and the rest was the same as in Example 4, resulting in 7.26g (35.2mmol) of DFTHP, with a yield of 88.1%.
[0027] Example 7:
[0028] In this embodiment, the amount of triethylamine added in step (1) was 1.22 g (12 mmol), and the rest was the same as in Example 4, yielding 7.19 g (34.9 mmol) of DFTHP, with a yield of 87.2%.
[0029] Example 8:
[0030] In this embodiment, the amount of triethylamine added in step (1) was 0.81 g (8 mmol), and the rest was the same as in Example 7, yielding 7.09 g (34.4 mmol) of DFTHP, with a yield of 86.0%.
[0031] Example 9:
[0032] (1) Add 3.6 g (80 mmol) of formamide, 12.76 g (88 mmol) of glyoxal aqueous solution (mass fraction of 40%) and 4.6 mL (8 mmol) of potassium hydroxide solution (mass fraction of 10%) to the reactor;
[0033] (2) Fix the reactor on the acoustic resonance reaction platform and adjust the acceleration of the acoustic resonance reaction platform to 196 m / s². 2 The reaction time at room temperature (25℃) is 10 min;
[0034] (3) After filtration, washing with water (50 mL, 3 times), washing with ethanol (50 mL, 3 times), and drying (50℃, 12 hours), 7.11 g (34.4 mmol) of aldehyde-amine condensation product DFTHP was obtained, with a yield of 86.0%.
[0035] Example 10:
[0036] In this embodiment, the acceleration of the acoustic resonance response platform is adjusted to 294 m / s² in step (2). 2 The rest was the same as in Example 9, yielding 7.55 g (36.6 mmol) of the aldehyde-amine condensation product DFTHP, with a yield of 91.6%.
[0037] Example 11:
[0038] In this embodiment, the amount of potassium hydroxide solution (mass fraction of 10%) added in step (1) was 6.8 mL (12 mmol), and the rest was the same as in Example 9, yielding 7.32 g (35.5 mmol) of aldehyde-amine condensation product DFTHP, with a yield of 88.8%.
[0039] Example 12:
[0040] (1) Add 3.6 g (80 mmol) of formamide, 12.76 g (88 mmol) of glyoxal aqueous solution (mass fraction of 40%) and 3.2 mL (8 mmol) of sodium hydroxide solution (mass fraction of 10%) to the reactor;
[0041] (2) Fix the reactor on the acoustic resonance reaction platform and adjust the acceleration of the acoustic resonance reaction platform to 196 m / s². 2 The reaction time at room temperature (25℃) is 10 min;
[0042] (3) After filtration, washing with water (50 mL, 3 times), washing with ethanol (50 mL, 3 times), and drying (50℃, 12 hours), 6.91 g (33.6 mmol) of DFTHP was obtained, with a yield of 84.0%.
[0043] Example 13:
[0044] In this embodiment, the acceleration of the acoustic resonance response platform is adjusted to 294 m / s² in step (2). 2 The rest was the same as in Example 12, yielding 7.48 g (36.4 mmol) of DFTHP, with a yield of 91%.
[0045] Example 14:
[0046] In this embodiment, the amount of sodium hydroxide solution (mass fraction of 10%) added in step (1) was 4.8 mL (12 mmol), and the rest was the same as in Example 12, yielding 7.28 g (35.3 mmol) of DFTHP, with a yield of 88.3%.
[0047] Comparative Examples 1-6:
[0048] 3.6 g (80 mmol) of formamide, 12.76 g (88 mmol) of glyoxal aqueous solution (40% by mass) and 1.62 g (16 mmol) of triethylamine were added to a reactor. The mixture was stirred thoroughly and the reaction temperature and time were adjusted. After the reaction was completed, the mixture was filtered, washed with water (50 mL, 3 times), washed with ethanol (50 mL, 3 times), and dried (50 °C, 12 hours) to obtain 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine (DFTHP).
[0049] Table 1. Relationship between different reaction temperatures and times and product yield under conventional stirring methods
[0050] Serial Number Temperature (°C) Time (hours) Yield (%) 1 25 2 76 2 25 3 78 3 25 4 77 4 35 3 79 5 45 3 81 6 55 3 72
[0051] It is evident that, under traditional stirring conditions, the highest yield, reaching 78%, is achieved at room temperature and a reaction time of 3 hours. Increasing the reaction temperature improves the yield, with the highest yield of 81% (number 5) observed at 45°C. Further increases in temperature lead to a decrease in yield, possibly due to increased side reactions.
[0052] Therefore, it can be seen that the acoustic resonance enhancement technology can achieve highly efficient alkaline (including inorganic and organic alkaline) catalytic aldehyde-amine condensation reaction, which can significantly shorten the reaction time (from more than 2 hours to 5-10 minutes) and improve the reaction yield (from ~80% to 90%). Moreover, the reaction can be carried out at room temperature without the need for additional heating or cooling.
[0053] It is understood that the above embodiments are merely illustrative of preferred embodiments of the present invention, and the invention is not limited thereto. For those skilled in the art, various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these modifications and improvements are also within the scope of protection of the present invention.
Claims
1. A method for the acoustic resonance synthesis of 1,4-dicarboxylo-2,3,5,6-tetrahydroxypiperazine, characterized in that, The method includes: 1,4-Diformyl-2,3,5,6-Tetrahydroxypiperazine was synthesized by reacting formamide, glyoxal, and alkaline solution for 5–10 min under acoustic resonance and room temperature conditions; the acceleration of the acoustic resonance was 196–980 m / s². 2 , The alkaline solution is selected from sodium hydroxide aqueous solution, potassium hydroxide aqueous solution or triethylamine.
2. The method for acoustic resonance synthesis of 1,4-dicarboxylo-2,3,5,6-tetrahydroxypiperazine according to claim 1, characterized in that, After the reaction solution was filtered, washed and dried, the aldehyde-amine condensation product 1,4-dicarboxylo-2,3,5,6-tetrahydroxypiperazine was obtained.
3. The method for acoustic resonance synthesis of 1,4-dicarboxyloyl-2,3,5,6-tetrahydroxypiperazine according to claim 1, characterized in that, The molar ratio of formamide, glyoxal, and alkali is 1:1 to 1.1:0.1 to 0.2.