A method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane
By using ethyl acetate instead of pyridine solvent in tris(p-toluenesulfonyloxymethyl)nitromethane synthesis and performing acylation reactions at 15°C to 30°C, the harsh reaction conditions and toxicity in the prior art are solved. The big problem has achieved efficient and short-term synthesis, with a yield of 96.9%.
Patent Information
- Application Number
- CN202310607841.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-05-26
- Publication Date
- 2024-12-13
- Estimated Expiration
- 2043-05-26
AI Technical Summary
In the existing synthesis method of tris(p-toluenesulfonyloxymethyl)nitromethane, pyridine with high toxicity is used as a solvent, and the reaction is required for 24 hours at 0°C, and the reaction conditions are harsh.
Ethyl acetate was used as a solvent and the acylation reaction was carried out at a temperature of 15°C to 30°C, which shortened the reaction time to 18 hours, improved the product yield and reduced the toxicity of the reaction solvent.
A high yield of tris(p-toluenesulfonyloxymethyl)nitromethane synthesis was achieved, with moderate reaction temperature and short time, and the use of highly toxic pyridine was avoided, with a yield of 96.9%.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of functional materials, relates to a small molecule azide plasticizer, and specifically relates to a method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane. Background Art
[0002] The development of energetic compounds depends largely on the selection of energetic groups. Since the 1980s, an important progress and feature in the field of explosive synthesis research is the application of azide as an energetic group. Years of research have found that azide energetic compounds have many characteristics such as low impact sensitivity, high formation enthalpy, small molecular weight of fuel gas, no smoke generation, and low combustion temperature. Therefore, azide groups have been greatly favored in the development of energetic adhesives, energetic plasticizers and other additives. Among them, triazidomethylnitromethane is a new type of small molecule azide plasticizer, which is expected to be used in propellants or propellants. In addition, the high nitrogen content may make this compound a nitrogen generator.
[0003] Tris(p-toluenesulfonyloxymethyl)nitromethane is a precursor compound for synthesizing triazidomethylnitromethane. "Development of energetic additives for propellants in China" (Journal of Propulsion and Power, 1995, 11(4), 838-847) discloses a method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane, which uses tris(hydroxymethyl)nitromethane as a raw material and pyridine as a solvent, and reacts with p-toluenesulfonyl chloride at 0°C for 24 hours to generate tris(p-toluenesulfonyloxymethyl)nitromethane.
[0004] The synthesis method of tris(p-toluenesulfonyloxymethyl)nitromethane reported in the above literature requires the use of highly toxic pyridine as a reaction solvent, the reaction temperature needs to be lowered to 0°C, and the reaction time is relatively long, which is 24 hours. Summary of the invention
[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane to solve the technical problems of high reaction toxicity and harsh reaction conditions in the prior art method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane.
[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions to achieve the above problems:
[0007] The invention discloses a method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane. The method uses trishydroxymethylnitromethane and p-toluenesulfonyl chloride as raw materials, performs an acylation reaction in ethyl acetate solvent at a reaction temperature of 15°C to 30°C to generate tris(p-toluenesulfonyloxymethyl)nitromethane.
[0008] The present invention also has the following technical features:
[0009] Specifically, the yield of the synthesis method is 76.8% to 96.9%.
[0010] Preferably, the yield of the synthesis method is 85.1% to 96.9%.
[0011] More preferably, the yield of the synthesis method is 94.2% to 96.9%.
[0012] Specifically, the specific synthesis steps of the method are:
[0013] Under stirring, at a temperature of 20°C to 25°C, add trihydroxymethylnitromethane to ethyl acetate, then add p-toluenesulfonyl chloride, and react at 15°C to 30°C for 15h to 20h; after the reaction is completed, pour the reaction solution into ice water and stir to precipitate a large amount of light yellow solid, extract with dichloromethane, wash with water until neutral, remove dichloromethane under reduced pressure, and obtain a light yellow solid, namely tris(p-toluenesulfonyloxymethyl)nitromethane.
[0014] Preferably, the reaction is carried out at 25°C to 30°C for 18 hours.
[0015] Specifically, the mass ratio of tris(hydroxymethylnitromethane), p-toluenesulfonyl chloride and ethyl acetate is 1.0:
[0016] (3.4~4.7):(4.2~8.3).
[0017] Preferably, the mass ratio of tris(hydroxymethylnitromethane), p-toluenesulfonyl chloride and ethyl acetate is 1.0:4.2:6.0.
[0018] Compared with the prior art, the present invention has the following technical effects:
[0019] (I) The synthesis method of the present invention has a moderate reaction temperature, a short reaction time, a high product yield and a low toxicity of the reaction solvent.
[0020] (II) The present invention uses ethyl acetate to replace the more toxic pyridine. During the reaction, the temperature does not need to be controlled at 0°C, and the reaction can be carried out at 15°C to 30°C. The reaction time is reduced from 24h to 18h, and the yield is 96.9%.
[0021] The specific contents of the present invention are further explained in detail below in conjunction with embodiments. DETAILED DESCRIPTION
[0022] It should be noted that, unless otherwise specified, all raw materials in the present invention are raw materials known in the prior art.
[0023] In the present invention, the chemical structural formula of trimethylolnitromethane is:
[0024]
[0025] In the present invention, the chemical structural formula of tris(p-toluenesulfonyloxymethyl)nitromethane is:
[0026]
[0027] The present invention provides a synthesis route of tris(p-toluenesulfonyloxymethyl)nitromethane as follows:
[0028]
[0029] The synthesis route of the invention uses trihydroxymethylnitromethane as a raw material, and undergoes an acylation reaction with p-toluenesulfonyl chloride in ethyl acetate solvent to generate tris(p-toluenesulfonyloxymethyl)nitromethane.
[0030] Specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solution of this application fall within the protection scope of the present invention.
[0031] Embodiment 1:
[0032] The present embodiment provides a method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane, which comprises the following steps: adding 151 g of tris(hydroxymethyl)nitromethane to 1000 mL of ethyl acetate at a temperature of 20° C. to 25° C. under stirring, and then adding 634.2 g of p-toluenesulfonyl chloride, and reacting at 25° C. to 30° C. for 18 hours. After the reaction is completed, pouring the reaction solution into ice water and stirring to precipitate a large amount of light yellow solid, extracting with dichloromethane, washing with water until neutral, and removing dichloromethane under reduced pressure to obtain 594.0 g of light yellow solid, with a yield of 96.9% and a purity of 99.5% (HPLC).
[0033] Structure identification:
[0034] IR (KBr, cm -1 )ν: 3070 (benzene ring CH), 2987, 2928 (-CH), 1566, 1367 (-NO2),
[0035] 1599, 828, 808, 788 (benzene ring), 1192, 1175 (-SO2-).
[0036] 1H NMR (CDCl3-d6, 500 MHz), δ: 7.70 (d, 6H, meta-CH- of benzene ring CH3), 7.36 (d, 6H, ortho-CH- of benzene ring CH3), 4.29 (s, 6H, CH2), 2.46 (s, 9H, CH3).
[0037] 13 C NMR (CDCl3-d6, 125 MHz) δ: 146.14, 131.01, 130.32, 128.10 (C on the benzene ring), 87.26 (CH2), 64.30 (quaternary C), 21.77 (CH3).
[0038] Elemental analysis (C 25 H 27 O 11 S3N, %):
[0039] Calculated: C, 48.94; H, 4.40; N, 2.28.
[0040] Found: C, 48.89; H, 4.38; N, 2.25.
[0041] The above structural identification data confirm that the target compound obtained by the synthesis method of this embodiment is tris(p-toluenesulfonyloxymethyl)nitromethane.
[0042] Embodiment 2:
[0043] The present embodiment provides a method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane, which comprises the following steps: adding 151 g of tris(hydroxymethyl)nitromethane to 1400 mL of ethyl acetate at a temperature of 20° C. to 25° C. under stirring, and then adding 709.7 g of p-toluenesulfonyl chloride, and reacting at 25° C. to 30° C. for 15 hours. After the reaction is completed, pouring the reaction solution into ice water and stirring to precipitate a large amount of light yellow solid, extracting with dichloromethane, washing with water until neutral, and removing dichloromethane under reduced pressure to obtain 582.4 g of light yellow solid, with a yield of 95.0% and a purity of 99.4% (HPLC).
[0044] The structural identification data of this example is the same as that of Example 1.
[0045] Embodiment 3:
[0046] The present embodiment provides a method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane, which comprises the following steps: adding 151 g of tris(hydroxymethyl)nitromethane to 700 mL of ethyl acetate at a temperature of 20° C. to 25° C. under stirring, and then adding 513.4 g of p-toluenesulfonyl chloride, and reacting at 25° C. to 30° C. for 18 hours. After the reaction is completed, pouring the reaction solution into ice water and stirring to precipitate a large amount of light yellow solid, extracting with dichloromethane, washing with water until neutral, and removing dichloromethane under reduced pressure to obtain 471.3 g of light yellow solid, with a yield of 76.8% and a purity of 98.1% (HPLC).
[0047] The structural identification data of this example is the same as that of Example 1.
[0048] Embodiment 4:
[0049] The present embodiment provides a method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane, which comprises the following steps: adding 151 g of tris(hydroxymethyl)nitromethane to 1200 mL of ethyl acetate at a temperature of 20° C. to 25° C. under stirring, and then adding 664.4 g of p-toluenesulfonyl chloride, and reacting at 20° C. to 25° C. for 18 hours. After the reaction is completed, pouring the reaction solution into ice water and stirring to precipitate a large amount of light yellow solid, extracting with dichloromethane, washing with water until neutral, and removing dichloromethane under reduced pressure to obtain 577.5 g of light yellow solid, with a yield of 94.2% and a purity of 99.1% (HPLC).
[0050] The structural identification data of this example is the same as that of Example 1.
[0051] Embodiment 5:
[0052] The present embodiment provides a method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane, which comprises the following steps: adding 151 g of tris(hydroxymethyl)nitromethane to 900 mL of ethyl acetate at a temperature of 20° C. to 25° C. under stirring, and then adding 571.5 g of p-toluenesulfonyl chloride, and reacting at 20° C. to 25° C. for 15 hours. After the reaction is completed, pouring the reaction solution into ice water and stirring to precipitate a large amount of light yellow solid, extracting with dichloromethane, washing with water until neutral, and removing dichloromethane under reduced pressure to obtain 521.9 g of light yellow solid, with a yield of 85.1% and a purity of 99.2% (HPLC).
[0053] The structural identification data of this example is the same as that of Example 1.
[0054] Embodiment 6:
[0055] The present embodiment provides a method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane, which comprises the following steps: adding 151 g of tris(hydroxymethyl)nitromethane to 1100 mL of ethyl acetate at a temperature of 20° C. to 25° C. under stirring, and then adding 600.1 g of p-toluenesulfonyl chloride, and reacting at 20° C. to 25° C. for 20 hours. After the reaction is completed, pouring the reaction solution into ice water and stirring to precipitate a large amount of light yellow solid, extracting with dichloromethane, washing with water until neutral, and removing dichloromethane under reduced pressure to obtain 546.2 g of light yellow solid, with a yield of 89.1% and a purity of 99.1% (HPLC).
[0056] The structural identification data of this example is the same as that of Example 1.
[0057] Embodiment 7:
[0058] The present embodiment provides a method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane, which comprises the following steps: adding 151 g of tris(hydroxymethyl)nitromethane to 1000 mL of ethyl acetate at a temperature of 20° C. to 25° C. under stirring, and then adding 709.7 g of p-toluenesulfonyl chloride, and reacting at 15° C. to 20° C. for 20 hours. After the reaction is completed, pouring the reaction solution into ice water and stirring to precipitate a large amount of light yellow solid, extracting with dichloromethane, washing with water until neutral, and removing dichloromethane under reduced pressure to obtain 536.4 g of light yellow solid, with a yield of 87.5% and a purity of 99.3% (HPLC).
[0059] The structural identification data of this example is the same as that of Example 1.
Claims
1. A method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane, characterized in that: The specific synthesis steps of the method are: under stirring, at a temperature of 20°C to 25°C, tris(hydroxymethyl)nitromethane is added to ethyl acetate, and then p-toluenesulfonyl chloride is added, and an acylation reaction is carried out at a reaction temperature of 15°C to 30°C for 15h to 20h; after the reaction is completed, the reaction solution is poured into ice water and stirred to precipitate a large amount of light yellow solid, which is extracted with dichloromethane, washed with water until neutral, and dichloromethane is removed under reduced pressure to obtain a light yellow solid, namely tris(p-toluenesulfonyloxymethyl)nitromethane.
2. The method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane according to claim 1, characterized in that: The yield of this synthesis method is 76.8% to 96.9%.
3. The method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane according to claim 2, characterized in that: The yield of this synthesis method is 85.1% to 96.9%.
4. The method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane according to claim 1, characterized in that: The acylation reaction was carried out at a reaction temperature of 25°C to 30°C for 18 hours.
5. The method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane according to any one of claims 1 to 4, characterized in that: The mass ratio of tris(hydroxymethylnitromethane), p-toluenesulfonyl chloride and ethyl acetate is 1.0:(3.4-4.7):(4.2-8.3).
6. The method for synthesizing tris(p-toluenesulfonyloxymethyl)nitromethane according to claim 5, characterized in that: The mass ratio of tris(hydroxymethylnitromethane), p-toluenesulfonyl chloride and ethyl acetate is 1.0:4.2:6.0.