WO2023039940A1 - Procédé de préparation de n,n,n-tripivaloyle-1,3,5-triaminobenzène - Google Patents

Procédé de préparation de n,n,n-tripivaloyle-1,3,5-triaminobenzène Download PDF

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WO2023039940A1
WO2023039940A1 PCT/CN2021/121084 CN2021121084W WO2023039940A1 WO 2023039940 A1 WO2023039940 A1 WO 2023039940A1 CN 2021121084 W CN2021121084 W CN 2021121084W WO 2023039940 A1 WO2023039940 A1 WO 2023039940A1
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reaction
tripivaloyl
triaminotoluene
solvent
oxidant
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黄木华
张志豪
杨天宇
付浩熹
刘博瀚
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北京理工大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to the fields of chemical industry and materials, and mainly relates to a method for preparing N,N,N-tripivaloylated-1,3,5-triaminobenzene.
  • Polypropylene is a partially crystalline resin and is widely used in industry. Its mechanical properties, optical properties and heat resistance are closely related to its crystallinity and crystal morphology. During processing, unmodified polypropylene melts tend to form larger spherulites, which affect the performance of the final product. Adding a nucleating agent to the polypropylene processing formula can reduce the size of spherulites and improve product quality.
  • N,N,N-tripivaloyl-1,3,5-triaminobenzene (trade name: XT-386) has been confirmed as an amide nucleating agent because of its stable and efficient characteristics. It has a good effect of inducing polypropylene nucleation, and can produce high-transparency polypropylene products at a lower dosage. crystallization.
  • XT386 is mainly obtained by N-pivaloylation of 1,3,5-triaminobenzene, and the difficulty of synthesizing 1,3,5-triaminobenzene makes its synthesis cost high. Therefore, based on the relatively difficult synthesis of 1,3,5-triaminobenzene and the low yield of its N-acylation reaction, those skilled in the art urgently need a simple, efficient, safe, low-pollution and low-pollution A cost-effective method to prepare N,N,N-tripivaloyl-1,3,5-triaminobenzene (trade name: XT-386).
  • the present invention provides a method for preparing N,N,N-tripivaloylated-1,3,5-triaminobenzene to achieve simple, efficient, safe, low-pollution and low-cost synthesis N,N,N-tripivaloyl-1,3,5-triaminobenzene.
  • the specific content is as follows:
  • the invention provides a method for preparing N,N,N-tripivaloylated-1,3,5-triaminobenzene, the method comprising:
  • Step 1 Using 2,4,6-trinitrotoluene shown in structural formula IV as a raw material, first obtain the first intermediate product III by hydrogenation reduction, and then use pivalic anhydride to treat the first intermediate product in an alkaline environment.
  • the product III is subjected to an acylation reaction to obtain N,N,N-tripivaloyl-2,4,6-triaminotoluene shown in the structural formula II;
  • Step 2 Demethylation is performed on the N,N,N-tripivaloyl-2,4,6-triaminotoluene, and after the demethylation reaction is completed, it is purified to obtain the compound shown in the structural formula I 1,3,5-Tripivalamidobenzene;
  • the hydrogen pressure range used is 0.1-0.8 MPa
  • the mass ratio of the catalyst used to the 2,4,6-trinitrotoluene is 0.05:1-0.3 : 1
  • the reaction temperature is 15 ⁇ 75 DEG C
  • the reaction time is 0.5 ⁇ 12h
  • the reaction solvent includes at least one of methanol, ethanol, isopropanol, acetonitrile, chloroform, ethyl acetate and tetrahydrofuran;
  • the catalyst is palladium/carbon catalyst or Raney nickel catalyst.
  • the molar ratio of the pivalic anhydride to the 2,4,6-trinitrotoluene is 5:1 to 30:1; the reaction temperature of the acylation reaction is 5 ⁇ 35°C, the reaction time is 0.5 ⁇ 5h;
  • the molar ratio of the base used in the alkaline environment to the 2,4,6-trinitrotoluene is 5:1 to 30:1; the base is triethylamine, diisopropylethylamine, pyridine and At least one or more of potassium carbonate.
  • the demethylation reaction includes: an oxidation reaction and a decarboxylation reaction.
  • the oxidant system used in the oxidation reaction is a first oxidant system;
  • the first oxidant system is: an oxidant system composed of potassium permanganate and magnesium sulfate;
  • potassium permanganate is an oxidant
  • magnesium sulfate is a pro-oxidant
  • the mol ratio of the potassium permanganate to the N,N,N-tripivaloyl-2,4,6-triaminotoluene is 3: 1-10:1
  • the molar ratio of the magnesium sulfate to the N,N,N-tripivaloyl-2,4,6-triaminotoluene is 1:1-5:1.
  • the oxidant system used in the oxidation reaction is a second oxidant system;
  • the second oxidant system is: an oxidant system consisting of potassium dichromate and dilute sulfuric acid;
  • potassium dichromate is an oxidant
  • dilute sulfuric acid is a catalyst
  • the molar ratio of the potassium dichromate to the N,N,N-tripivaloyl-2,4,6-triaminotoluene is 3:1 ⁇ 10:1
  • the dilute sulfuric acid is dilute sulfuric acid with a mass fraction of 5 ⁇ 40%
  • the molar ratio of the dilute sulfuric acid to the N,N,N-tripivaloyl-2,4,6-triaminotoluene It is 1:10 ⁇ 1:2.
  • the reaction temperature of the oxidation reaction is 60-130°C, and the reaction time is 1-5h;
  • the reaction solvent of the oxidation reaction is a two-solvent mixed system composed of water and an organic solvent, and the two-solvent mixed system and the N,N,N-tripivaloyl-2,4,6-triaminotoluene
  • the mass ratio is 5:1-20:1.
  • the two-solvent mixed system is a mixed solvent formed by mixing water and tert-butanol in a ratio of 1:1 to 1:5, and a mixed solvent formed by mixing water and hexafluoroisopropanol in a ratio of 1:1 to 1:5 or water and 1,4-dioxane in a ratio of 1:1 to 1:5.
  • the oxidant system used in the oxidation reaction is a third oxidant system;
  • the third oxidant system is: composed of oxygen, N-hydroxyphthalimide and metal salt solution oxidant system;
  • the oxygen is an oxidizing agent
  • the N-hydroxyphthalimide and the metal salt are catalysts
  • the metal salt is one of copper acetate, copper chloride, copper sulfate and copper nitrate
  • the molar ratio of the N-hydroxyphthalimide, the metal salt and the N,N,N-tripivaloyl-2,4,6-triaminotoluene is 0.1 ⁇ 0.3:0.1 ⁇ 0.3:1, the reaction temperature is 60-90°C, the reaction time is 6-12 hours, and the reaction solvent is any one of methanol, ethanol, isopropanol, acetone, acetonitrile, chloroform, ethyl acetate and tetrahydrofuran.
  • the temperature of the decarboxylation reaction is 60-180° C., and the time is 2-6 hours.
  • the invention provides a method for preparing N,N,N-tripivaloyl-1,3,5-triaminobenzene.
  • the method uses 2,4,6-triaminotoluene (TNT) as the main raw material to prepare N,N,N-tripivaloyl through two steps of catalytic hydrogenation-in-situ acylation and in-situ demethylation Na-1,3,5-triaminobenzene (XT-386).
  • the catalytic hydrogenation reaction is used to convert the energetic group nitro group into a safe and stable amino group, so as to prevent the energetic group nitro group in TNT from causing a safety hazard in the entire synthesis process; then adding an acid anhydride, It not only protects the amino group, but also obtains a branched structure similar to the target product; finally, a highly selective demethylation reaction is performed to directly obtain the target product with high economic value.
  • the synthetic route is simple, the reaction conditions are milder than the existing methods, and the yield is higher; moreover, the raw materials used in the synthetic route are the most common in military industry or chemical industry All chemical substances, solvents and catalysts can be recovered to greatly improve the economic benefits of atoms. Therefore, the method provided by the invention can greatly reduce the time and economic cost required for synthesizing TATB.
  • the present invention at least also includes the following advantages:
  • the TNT used is the waste dismantling drug TNT, which has the advantages of huge production reserve, low price, stable performance, mature process and lower cost than other raw materials, which greatly reduces the cost. It is the best choice to replace the 1,3,5-triaminobenzene used in the prior art.
  • the method provided by the present invention has short synthesis steps, simple operation of each step, fast reaction rate, high reaction conversion rate, easy separation and collection of intermediate and final products, used catalysts and solvents can also be recycled and reused, and the production process is simple. Therefore, the method provided by the present invention is not only conducive to realizing the mass production of N,N,N-tripivaloyl-1,3,5-triaminobenzene, but also conducive to synchronizing the current economical and green production.
  • the method provided by the present invention has high reaction yields in each step, is environmentally friendly, and produces fewer by-products than existing methods, which not only reduces the discharge of waste in the synthesis process, but also can effectively ensure that the target product N, N, N-three
  • the quality and purity of pivaloyl-1,3,5-triaminobenzene is conducive to the production of high-quality N,N,N-tripivaloyl-1,3,5-triaminobenzene.
  • the present invention provides a novel synthetic method for N,N,N-tripivaloyl-1,3,5-triaminobenzene, using decommissioned 2,4,6-trinitrotoluene as raw material,
  • N,N,N-tripivaloyl-1,3,5-triaminobenzene (trade name: XT-386) can be prepared quickly and efficiently.
  • the intermediate is stable in nature, non-explosive, the product is insensitive, and the reaction conditions of each step are relatively mild, which greatly reduces the cost, shortens the synthesis time, and effectively reduces the danger in the synthesis process.
  • Figure 1 shows a flow chart of the method for preparing N,N,N-tripivaloylated-1,3,5-triaminobenzene in an embodiment of the present invention
  • Fig. 2 is the proton nuclear magnetic resonance spectrogram of raw material 2,4,6-trinitrotoluene of the present invention
  • Fig. 3 is the carbon nuclear magnetic resonance spectrogram of raw material 2,4,6-trinitrotoluene of the present invention
  • Fig. 4 is the infrared spectrogram of raw material 2,4,6-trinitrotoluene of the present invention.
  • Fig. 5 is the NMR spectrum of N,N,N-tripivaloyl-2,4,6-triaminotoluene prepared in Example 1 of the present invention
  • Figure 6 is the carbon nuclear magnetic resonance spectrum of N,N,N-tripivaloyl-2,4,6-triaminotoluene prepared in Example 1 of the present invention
  • Fig. 7 is the infrared spectrogram of N,N,N-tripivaloyl-2,4,6-triaminotoluene prepared in Example 1 of the present invention
  • Fig. 8 is a high-resolution mass spectrum of N,N,N-tripivaloyl-2,4,6-triaminotoluene prepared in Example 1 of the present invention
  • Fig. 9 is the H NMR spectrum of 1,3,5-tripivalamidobenzene prepared in Example 1 of the present invention.
  • Figure 10 is the carbon nuclear magnetic resonance spectrum of 1,3,5-tripivalamidobenzene prepared in Example 1 of the present invention.
  • Fig. 11 is the infrared spectrogram of 1,3,5-tripivalamidobenzene prepared in Example 1 of the present invention.
  • Figure 12 is the high-resolution mass spectrum of 1,3,5-tripivalamidobenzene prepared in Example 1 of the present invention.
  • Fig. 13 is the haze and the crystallization temperature of the raw material polypropylene selected in the embodiment of the present invention.
  • Fig. 14 shows the haze and crystallization temperature of the 1,3,5-tripivalamidophenylene polypropylene prepared in Example 1 of the present invention.
  • the embodiment of the present invention provides a method for preparing N,N,N-tripivaloylated-1,3,5-triaminobenzene, as shown in Figure 1, the method includes:
  • the hydrogen pressure range used is 0.1-0.8 MPa
  • the mass ratio of the catalyst used to 2,4,6-trinitrotoluene is 0.05:1-0.3 : 1
  • the reaction temperature is 15 ⁇ 75 DEG C
  • the reaction time is 0.5 ⁇ 12h
  • the reaction solvent includes at least one of methanol, ethanol, isopropanol, acetonitrile, chloroform, ethyl acetate and tetrahydrofuran;
  • the catalyst is palladium/carbon catalyst or Raney nickel catalyst.
  • step 1 the molar ratio of pivalic anhydride to 2,4,6-trinitrotoluene is 5:1 to 30:1; the reaction temperature of the acylation reaction is 5 to 35°C, The reaction time is 0.5 ⁇ 5h.
  • the catalytic hydrogenation-in situ acylation reaction first utilizes the catalytic hydrogenation reaction to convert the energetic group nitro group into a safe and stable amino group, so as to avoid the energetic group nitro group in TNT from causing damage to the whole synthesis process. Potential safety hazards, greatly improving the safety of the entire process.
  • the acylation reaction in this implementation step can also proceed smoothly without adding an additional base. Therefore, compared with the existing acylation reaction, the acylation reaction in this implementation step has milder reaction conditions.
  • the reaction solution after the acylation reaction needs to be post-treated to obtain the N,N,N-tripivaloyl-2 shown in the structural formula II , 4,6-triaminotoluene finished product.
  • the specific process of post-treatment includes: first suction filter the reaction solution after the acylation reaction, then wash the filter residue with 70°C preheated absolute ethanol for 3 to 5 times, combine the filtrate, and then pour the combined filtrate 70°C preheated absolute ethanol was added dropwise to the mixture, cooled, suction filtered, and the solid obtained after suction filtration was washed with ethanol for 3 to 5 times, and then dried.
  • the drying operation may be: drying in a vacuum oven at a drying temperature of 30°C to 80°C.
  • the demethylation reaction specifically includes: an oxidation reaction and a decarboxylation reaction.
  • Oxidation reaction refers to: under the action of oxidant system, the methyl group in the N,N,N-tripivaloyl-2,4,6-triaminotoluene shown in structural formula II is oxidized to obtain 2,4 ,6-Tripivalylaminobenzoic acid.
  • the operation of the decarboxylation reaction can be as follows: heat the product obtained after the oxidation reaction (ie 2,4,6-tripivalylaminobenzoic acid) and soda lime at 60-180°C for 2-6 hours, and use it after the co-heating reaction Wash away soda lime with water to obtain N,N,N-tripivaloylated-1,3,5-triaminobenzene.
  • the optimum temperature range for heating is 70-90°C.
  • the oxidant system used in the oxidation reaction is the first oxidant system;
  • the first oxidant system is: an oxidant system composed of potassium permanganate and magnesium sulfate;
  • potassium permanganate is an oxidant
  • magnesium sulfate is a pro-oxidant
  • the molar ratio of potassium permanganate to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 3:1 ⁇ 10: 1
  • the molar ratio of magnesium sulfate to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 1:1 ⁇ 5:1.
  • the oxidant system used in the oxidation reaction is the second oxidant system;
  • the second oxidation system is: an oxidation system composed of potassium dichromate and dilute sulfuric acid;
  • potassium dichromate is an oxidant
  • dilute sulfuric acid is a catalyst
  • the molar ratio of potassium dichromate to the N,N,N-tripivaloyl-2,4,6-triaminotoluene is 3:1 ⁇ 10 : 1 dilute sulfuric acid is dilute sulfuric acid with a mass fraction of 5-40%, and the molar ratio of dilute sulfuric acid to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 1:10-1:2.
  • the reaction temperature of the oxidation reaction is 60-130°C, and the reaction time is 1-5h;
  • the reaction solvent of the oxidation reaction is a dual-solvent mixed system composed of water and an organic solvent, and the mass ratio of the dual-solvent mixed system to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 5:1 ⁇ 20:1.
  • the inventors found that when the oxidation reaction was carried out, the N,N,N-tripivaloyl-2,4,6-triaminotoluene shown in the structural formula II was in the oxidation reaction system with water as the solvent , is insoluble in water and floats on the water surface, so the N,N,N-tripivaloyl-2,4,6-triaminotoluene shown in the structural formula II is not easy to occur in the oxidation reaction system using water as the solvent demethylation reaction.
  • the inventor first explored the physical properties of N,N,N-tripivaloyl-2,4,6-triaminotoluene shown in structural formula II, and obtained its It has the physical characteristics of extremely small density and super hydrophobicity, and in view of this characteristic, the inventor proposes adding an organic solvent to water to make a dual-solvent mixed system, in order to increase the N,N,N-three shown in the structural formula II
  • the solubility of pivaloyl-2,4,6-triaminotoluene enables it to be oxidized smoothly by oxidants in water (potassium permanganate or potassium dichromate).
  • organic solvents when selecting an organic solvent, consider the strong oxidizing properties of the oxidizing agent.
  • the oxidation reaction can be carried out smoothly.
  • the conditions that the organic solvent selected by the inventor needs to have include: both can dissolve the N,N,N-tripivaloyl-2,4,6-triaminotoluene shown in structural formula II, and have the ability not to be affected by potassium permanganate or Potassium dichromate is an organic solvent with strong oxidation resistance, and it is also miscible with water.
  • the inventors selected organic solvents in this embodiment tert-butanol, hexafluoroisopropanol, and 1,4-dioxane.
  • the two-solvent mixed system can be a mixed solvent formed by mixing water and tert-butanol at a ratio of 1:1 to 1:5, or it can be a mixture of water and hexafluoroisopropanol at a ratio of 1:1 to 1
  • the oxidant system used in the oxidation reaction is the third oxidant system;
  • the third oxidant system is: an oxidant composed of oxygen, N-hydroxyphthalimide and metal salt solution system;
  • oxygen is an oxidizing agent
  • N-hydroxyphthalimide and a metal salt are catalysts
  • the metal salt is one of copper acetate, copper chloride, copper sulfate and copper nitrate;
  • the molar ratio of N-hydroxyphthalimide, metal salt and N,N,N-tripivaloyl-2,4,6-triaminotoluene is 0.1 ⁇ 0.3:
  • the reaction temperature is 60 ⁇ 90°C
  • the reaction time is 6 ⁇ 12h
  • the reaction solvent is any one of methanol, ethanol, isopropanol, acetone, acetonitrile, chloroform, ethyl acetate and tetrahydrofuran.
  • the temperature of the decarboxylation reaction is 60-180° C., and the time is 2-6 hours.
  • Step 1 Preparation of N,N,N-tripivaloyl-2,4,6-triaminotoluene represented by structural formula II.
  • the reduction reaction and the in-situ acylation reaction are combined in the same system. details as follows:
  • TNT 2,4,6-trinitrotoluene
  • a mixture of ethyl acetate (30ml)/pivalic anhydride (87ml, 0.45mol, 10eq) to obtain a TNT solution
  • Pd/C catalyst 0.3g
  • triethylamine 64ml, 10eq
  • transfer to the high-pressure stirred reactor vacuumize the high-pressure stirred reactor, fill with nitrogen, repeat several times, and finally vacuumize to ensure that there is no air residue , continue to feed hydrogen for high-pressure (0.6MPa) reduction reaction and in-situ N-acylation reaction at room temperature, the reaction lasts for 4 hours, and the reaction temperature is 30 ° C. After the reaction, a dark red solution and Pd/C catalyst are obtained.
  • the post-processing step is: after filtering out the Pd/C catalyst (the specific process is: firstly filter the reaction solution after the reaction, then wash the filter residue with 70°C preheated absolute ethanol for 3 to 5 times, and combine the filtrate), Add dropwise anhydrous ethanol preheated at 70°C to the filtrate, and when the filtrate is cooled, more white solids will precipitate, and the white powdery solids will be obtained by filtration. Drying at 60° C. gave N,N,N-tripivaloyl-2,4,6-triaminotoluene (5.4 g, yield 96%).
  • this step 1 the reduction reaction of hydrogenation and the in-situ acylation reaction are completed in the same reaction system, and 2,4,6-trinitrotoluene undergoes a reduction reaction with hydrogen to generate the first intermediate product 2,4,6-Triaminotoluene, in-situ acylation reaction with pre-added pivalic anhydride directly to generate N,N,N-tripivaloyl-2,4,6-triaminotoluene.
  • This step effectively combines the reduction reaction and the in-situ acylation reaction into one-step operation, reduces the processing process of the intermediate, achieves the purpose of simplifying the operation process, avoids the problem of intermediate product loss caused by complex operations, and is conducive to large-scale production , such as industrial production.
  • Fig. 2 Fig. 3 and Fig. 4 the H NMR spectrum, C NMR spectrum and infrared spectrum of the raw material 2,4,6-trinitrotoluene IV in step 1 of Example 1 of the present invention are shown.
  • the nuclear magnetic resonance hydrogen of the intermediate product N,N,N-tripivaloyl-2,4,6-triaminotoluene in Step 1 of Example 1 of the present invention is shown spectrum, carbon nuclear magnetic resonance spectrum, infrared spectrum and high resolution mass spectrum.
  • Step 2 Preparation of 1,3,5-tripivalamidobenzene represented by structural formula I.
  • the obtained 1,3,5-tripivalamidobenzene (10 g) and polypropylene (10 kg) were subjected to twin-screw extrusion at 190° C. and 30 rpm to prepare polypropylene flakes by pelletizing and injection molding.
  • the haze and crystallization temperature of polypropylene before and after adding a nucleating agent are shown.
  • the haze of polypropylene raw material is 78.85%, and the crystallization temperature is 115.5°C; after adding a nucleating agent, the haze is 67.8% , the crystallization temperature is 124.8°C, and the effect is consistent with the nucleation performance of XT-386 sold in the market.
  • step 1 in this embodiment is similar to the implementation content of step 1 in the above-mentioned embodiment 1, the difference is that the mass ratio of Pd/C catalyst to TNT is 0.05:1, the pressure of hydrogen is 0.8MP, pivalic anhydride and TNT
  • the molar ratio of the base is 5:1
  • the molar ratio of the base is diisopropylethylamine and TNT is 5:1
  • the reaction solvent is methanol
  • the reduction reaction temperature is 15°C
  • the reduction reaction time is 0.5h
  • the acylation reaction temperature is 5°C
  • the acylation reaction time was 0.5h
  • the yield was 88%.
  • Step 2 Preparation of 1,3,5-tripivalamidobenzene.
  • step 1 in this embodiment is similar to the implementation content of step 1 in the above-mentioned embodiment 1, the difference is: the mass ratio of Pd/C catalyst to TNT is 0.1:1, the pressure of hydrogen is 0.1MP, pivalic anhydride and TNT
  • the molar ratio of the base is 15:1
  • the base is pyridine and the molar ratio of TNT is 15:1
  • the reaction solvent is ethanol
  • the reduction reaction temperature is 30°C
  • the reduction reaction time is 5h
  • the acylation reaction temperature is 15°C
  • the acylation reaction time For 2h, the yield was 83%.
  • the filtrate was collected by filtration. Concentrate the filtrate under reduced pressure to 1/5 of the original volume, add concentrated hydrochloric acid to adjust the pH of the solution to acidity, put it in a refrigerator for 6 hours, and obtain 1,3,5-tripivalamidobenzene (0.29g, Yield 78%).
  • step 1 in this embodiment is similar to the implementation content of step 1 in the above-mentioned embodiment 1, the difference is: the mass ratio of Pd/C catalyst to TNT is 0.3:1, the pressure of hydrogen is 0.3MP, pivalic anhydride and TNT
  • the molar ratio of the base is 20:1
  • the molar ratio of potassium carbonate and TNT is 15:1
  • the reaction solvent is isopropanol
  • the reduction reaction temperature is 50°C
  • the reduction reaction time is 8h
  • the acylation reaction temperature is 20°C.
  • the acylation reaction time was 4h, and the yield was 89%.
  • step 2 in this embodiment is similar to the implementation content of step 2 in the above-mentioned example 1, the difference is that: potassium permanganate and N,N,N-tripivaloyl-2,4,6-triaminotoluene
  • the mass ratio is 3:1; the mass ratio of magnesium sulfate to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 1:1;
  • the reaction solvent of the oxidation reaction is water and tert-butanol according to A mixed solvent mixed at a ratio of 1:1, the mass ratio of the two-solvent mixed system to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 5:1;
  • the reaction temperature of the oxidation reaction is 60°C, the reaction time of the oxidation reaction is 1h; the temperature of the decarboxylation reaction is 60°C, and the time is 2h.
  • the final yield of 1,3,5-tripivalamidobenzene
  • step 1 in this embodiment is similar to the implementation content of step 1 in the above-mentioned embodiment 1, the difference is that the mass ratio of Pd/C catalyst to TNT is 0.3:1, the pressure of hydrogen is 0.1MP, pivalic anhydride and TNT The molar ratio is 30:1, the reaction solvent is acetonitrile, the reduction reaction temperature is 75°C, the reduction reaction time is 12h, the acylation reaction temperature is 35°C, the acylation reaction time is 5h, and the yield is 90%.
  • step 2 in this embodiment is similar to the implementation content of step 2 in the above-mentioned example 1, the difference is that: potassium permanganate and N,N,N-tripivaloyl-2,4,6-triaminotoluene
  • the mass ratio is 5:1; the mass ratio of magnesium sulfate to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 3:1;
  • the reaction solvent of the oxidation reaction is water and tert-butanol according to A mixed solvent mixed at a ratio of 1:3, the mass ratio of the two-solvent mixed system to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 15:1; the reaction temperature of the oxidation reaction is 80°C, the reaction time of the oxidation reaction is 3h; the temperature of the decarboxylation reaction is 90°C, and the time is 4h.
  • step 1 in this embodiment is similar to the implementation content of step 1 in the above-mentioned embodiment 1, the difference is that the mass ratio of Raney nickelizing agent to TNT is 0.3:1, the pressure of hydrogen is 0.1MP, pivalic anhydride and The molar ratio of TNT was 30:1, the reaction solvent was chloroform, the reduction reaction temperature was 75°C, the reduction reaction time was 12h, the acylation reaction temperature was 35°C, the acylation reaction time was 5h, and the yield was 90%.
  • step 2 in this embodiment is similar to the implementation content of step 2 in the above-mentioned example 1, the difference is that: potassium permanganate and N,N,N-tripivaloyl-2,4,6-triaminotoluene
  • the mass ratio is 10:1; the mass ratio of magnesium sulfate to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 5:1;
  • the reaction solvent of the oxidation reaction is water and tert-butanol according to A mixed solvent mixed at a ratio of 1:5, the mass ratio of the two-solvent mixed system to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 20:1; the reaction temperature of the oxidation reaction is 130°C, the reaction time for the oxidation reaction is 5h; the temperature for the decarboxylation reaction is 12°C, and the time is 6h.
  • step 1 of the present embodiment is similar to the implementation content of step 1 in the above-mentioned embodiment 1, the difference is: the mass ratio of Raney nickelizing agent to TNT is 0.05:1, the pressure of hydrogen is 0.1MP, pivalic anhydride and The molar ratio of TNT was 5:1, the reaction solvent was tetrahydrofuran, the reduction reaction temperature was 15°C, the reduction reaction time was 0.5h, the acylation reaction temperature was 5°C, the acylation reaction time was 0.5h, and the yield was 82%.
  • step 2 in this embodiment is similar to the implementation content of step 2 in the above-mentioned embodiment 2, the difference is that potassium dichromate and N,N,N-tripivaloyl-2,4,6-triaminotoluene
  • the molar ratio is 3:1; dilute sulfuric acid is dilute sulfuric acid with a mass fraction of 5%, and the molar ratio of dilute sulfuric acid to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 1:10; oxidation
  • the reaction solvent of the reaction is a mixed solvent mixed with water and tert-butanol at a ratio of 1:1.
  • the final yield of 1,3,5-tripivalamidobenzene was 83%.
  • step 1 in this embodiment is the same as the implementation content of step 1 in the above-mentioned embodiment 1, and will not be repeated in this embodiment.
  • step 2 in this embodiment is similar to the implementation content of step 2 in the above-mentioned embodiment 2, the difference is that potassium dichromate and N,N,N-tripivaloyl-2,4,6-triaminotoluene
  • the molar ratio is 6:1; dilute sulfuric acid is dilute sulfuric acid with a mass fraction of 15%, and the molar ratio of dilute sulfuric acid to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 1:6; oxidation
  • the reaction solvent of the reaction is a mixed solvent mixed with water and tert-butanol in a ratio of 1:3.
  • the final yield of 1,3,5-tripivalamidobenzene was 85%.
  • step 1 in this embodiment is the same as the implementation content of step 1 in the above-mentioned embodiment 1, and will not be repeated in this embodiment.
  • step 2 in this embodiment is similar to the implementation content of step 2 in the above-mentioned embodiment 2, the difference is that potassium dichromate and N,N,N-tripivaloyl-2,4,6-triaminotoluene
  • the molar ratio is 10:1; dilute sulfuric acid is dilute sulfuric acid with a mass fraction of 35%, and the molar ratio of dilute sulfuric acid to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 1:4; oxidation
  • the reaction solvent of the reaction is a mixed solvent mixed with water and tert-butanol in a ratio of 1:5.
  • the mass ratio of the two-solvent mixed system to N,N,N-tripivaloyl-2,4,6-triaminotoluene It is 20:1; the reaction temperature of the oxidation reaction is 130°C, and the reaction time of the oxidation reaction is 5h; the temperature of the decarboxylation reaction is 180°C, and the time is 2h.
  • the final yield of 1,3,5-tripivalamidobenzene was 87%.
  • step 1 in this embodiment is the same as the implementation content of step 1 in the above-mentioned embodiment 1, and will not be repeated in this embodiment.
  • step 2 in this embodiment is similar to the implementation content of step 2 in the above-mentioned embodiment 2, the difference is that potassium dichromate and N,N,N-tripivaloyl-2,4,6-triaminotoluene
  • the molar ratio is 10:1; dilute sulfuric acid is dilute sulfuric acid with a mass fraction of 40%, and the molar ratio of dilute sulfuric acid to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 1:2; oxidation
  • the reaction solvent of the reaction is a mixed solvent mixed with water and hexafluoroisopropanol in a ratio of 1:1, and the mixed solvent of the two-solvent mixed system and N,N,N-tripivaloyl-2,4,6-triaminotoluene
  • the mass ratio is 5:1; the reaction temperature of the oxidation reaction is 60° C., and the reaction time of the oxidation reaction is 1 h.
  • step 1 in this embodiment is the same as the implementation content of step 1 in the above-mentioned embodiment 1, and will not be repeated in this embodiment.
  • step 2 in this embodiment is similar to the implementation content of step 2 in the above-mentioned embodiment 2, the difference is that the reaction solvent of the oxidation reaction is a mixed solvent formed by mixing water and hexafluoroisopropanol in a ratio of 1:3, and the two
  • the mass ratio of the solvent mixture system to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 10:1; the reaction temperature of the oxidation reaction is 90°C, and the reaction time of the oxidation reaction is 3h.
  • the final yield of 1,3,5-tripivalamidobenzene was 88%.
  • step 1 in this embodiment is the same as the implementation content of step 1 in the above-mentioned embodiment 1, and will not be repeated in this embodiment.
  • step 2 in this embodiment is similar to the implementation content of step 2 in the above-mentioned embodiment 2, the difference is that the reaction solvent of the oxidation reaction is a mixed solvent mixed with water and hexafluoroisopropanol in a ratio of 1:5, and the two
  • the mass ratio of the solvent mixture system to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 20:1; the reaction temperature of the oxidation reaction is 130°C, and the reaction time of the oxidation reaction is 5h.
  • the final yield of 1,3,5-tripivalamidobenzene was 89%.
  • step 1 in this embodiment is the same as the implementation content of step 1 in the above-mentioned embodiment 1, and will not be repeated in this embodiment.
  • step 2 in this example is similar to the implementation content of step 2 in the above example 2, the difference is that the reaction solvent of the oxidation reaction is a mixture of water and 1,4-dioxane in a ratio of 1:1. Solvent, the mass ratio of the two-solvent mixed system to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 5:1; the reaction temperature of the oxidation reaction is 60°C, and the reaction time of the oxidation reaction is 1h. The final yield of 1,3,5-tripivalamidobenzene was 85%.
  • step 1 in this embodiment is the same as the implementation content of step 1 in the above-mentioned embodiment 1, and will not be repeated in this embodiment.
  • step 2 in this example is similar to the implementation content of step 2 in the above-mentioned example 2, the difference is that the reaction solvent of the oxidation reaction is a mixture of water and 1,4-dioxane in a ratio of 1:3. Solvent, the mass ratio of the two-solvent mixed system to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 10:1; the reaction temperature of the oxidation reaction is 100°C, and the reaction time of the oxidation reaction is 3h. The final yield of 1,3,5-tripivalamidobenzene was 86%.
  • the reaction solvent of the oxidation reaction is a mixture of water and 1,4-dioxane in a ratio of 1:3.
  • Solvent the mass ratio of the two-solvent mixed system to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 10:1; the reaction temperature of the oxidation reaction is 100°C, and the reaction time
  • step 1 in this embodiment is the same as the implementation content of step 1 in the above-mentioned embodiment 1, and will not be repeated in this embodiment.
  • step 2 in this example is similar to the implementation content of step 2 in the above example 2, the difference is that the reaction solvent of the oxidation reaction is a mixture of water and 1,4-dioxane in a ratio of 1:5 Solvent, the mass ratio of the two-solvent mixed system to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 5:1; the reaction temperature of the oxidation reaction is 130°C, and the reaction time of the oxidation reaction is 5h. The final yield of 1,3,5-tripivalamidobenzene was 87%.
  • the reaction solvent of the oxidation reaction is a mixture of water and 1,4-dioxane in a ratio of 1:5 Solvent
  • the mass ratio of the two-solvent mixed system to N,N,N-tripivaloyl-2,4,6-triaminotoluene is 5:1
  • the reaction temperature of the oxidation reaction is 130°C
  • step 1 in this embodiment is the same as the implementation content of step 1 in the above-mentioned embodiment 1, and will not be repeated in this embodiment.
  • step 2 of this embodiment is similar to the implementation content of step 2 in the above-mentioned embodiment 3, the difference is that: the metal salt is copper chloride; N-hydroxyphthalimide, metal salt and N,N,N -The molar ratio of pivaloyl-2,4,6-triaminotoluene is 0.1:0.1:1, the reaction temperature is 60° C., the reaction time is 6 h, and the reaction solvent is methanol. The final yield of 1,3,5-tripivalamidobenzene was 77%.
  • step 1 in this embodiment is the same as the implementation content of step 1 in the above-mentioned embodiment 1, and will not be repeated in this embodiment.
  • step 2 in this embodiment is similar to the implementation content of step 2 in the above-mentioned embodiment 3, the difference is that the metal salt is copper sulfate; N-hydroxyphthalimide, metal salt and N,N,N-
  • the molar ratio of pivaloyl-2,4,6-triaminotoluene is 0.1:0.2:1, the reaction temperature is 80° C., the reaction time is 8 h, and the reaction solvent is isopropanol.
  • the final yield of 1,3,5-tripivalamidobenzene was 76%.
  • step 1 in this embodiment is the same as the implementation content of step 1 in the above-mentioned embodiment 1, and will not be repeated in this embodiment.
  • step 2 in this embodiment is similar to the implementation content of step 2 in the above-mentioned embodiment 3, the difference is that the metal salt is copper nitrate; N-hydroxyphthalimide, metal salt and N,N,N-
  • the molar ratio of pivaloyl-2,4,6-triaminotoluene is 0.1:0.3:1, the reaction temperature is 90° C., the reaction time is 10 h, and the reaction solvent is acetone.
  • the final yield of 1,3,5-tripivalamidobenzene was 73%.
  • step 1 in this embodiment is the same as the implementation content of step 1 in the above-mentioned embodiment 1, and will not be repeated in this embodiment.
  • step 2 in this example is similar to the implementation content of step 2 in the above example 3, the difference is: N-hydroxyphthalimide, metal salt and N,N,N-tripivaloyl-2 ,
  • the molar ratio of 4,6-triaminotoluene is 0.2:0.1:1, the reaction temperature is 60°C, the reaction time is 12h, and the reaction solvent is ethyl acetate.
  • the final yield of 1,3,5-tripivalamidobenzene was 77%.
  • step 1 in this embodiment is the same as the implementation content of step 1 in the above-mentioned embodiment 1, and will not be repeated in this embodiment.
  • step 2 in this embodiment is similar to the implementation content of step 2 in the above-mentioned embodiment 3, the difference is that the metal salt is copper nitrate; N-hydroxyphthalimide, metal salt and N,N,N- The molar ratio of pivaloyl-2,4,6-triaminotoluene is 0.3:0.3:1, and the reaction solvent is acetonitrile. The final yield of 1,3,5-tripivalamidobenzene was 73%.
  • the obtained intermediate product N,N,N-tripivaloyl-2,4,6-triaminotoluene has a hydrogen nuclear magnetic resonance spectrum, a carbon nuclear magnetic resonance spectrum, an infrared spectrum and a high Resolution mass spectrogram, respectively identical with Fig. 5, Fig. 6, Fig. 7 and Fig. 8, the proton nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum, infrared spectrogram and The high-resolution mass spectrograms are the same as those in Fig. 9, Fig. 10, Fig. 11 and Fig. 12, and are not repeated in Examples 2-20.

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Abstract

L'invention concerne un procédé de préparation de N,N,N-tripivaloyle-1,3,5-triaminobenzène. Le procédé comprend : l'étape 1, qui consiste à mettre à disposition du 2,4,6-trinitrotoluène en tant que matière première, et le faire réagir avec avec de l'hydrogène et de l'anhydride pivalique en séquence pour obtenir du N,N,N-tripivaloyle-2,4,6-triaminotoluène ; et l'étape 2, qui consiste à soumettre le N,N,N-tripivaloyle-2,4,6-triaminotoluène obtenu à une réaction de déméthylation, de manière à obtenir du N,N,N-tripivaloyle-1,3,5-triaminobenzène. le procédé de préparation utilise du 2,4,6-trinitrotoluène déclassé, et les réactifs ou les catalyseurs utilisés sont également tous des produits communs dans l'industrie chimique ; ainsi, le procédé présente des avantages en terme de faibles coûts et de matières premières simples et facilement disponibles. De plus, le procédé de préparation présente également des caractéristiques telles que des étapes de synthèse courtes, chaque étape étant simple à mettre en œuvre, un rendement élevé, un taux de réaction rapide, et les produits intermédiaires et finaux étant facilement séparés et collectés ; le procédé étant favorable à une production industrielle en masse de N,N,N-tripivaloyle-1,3,5-triaminobenzène.
PCT/CN2021/121084 2021-09-18 2021-09-27 Procédé de préparation de n,n,n-tripivaloyle-1,3,5-triaminobenzène WO2023039940A1 (fr)

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CN1747995A (zh) * 2003-02-14 2006-03-15 西巴特殊化学品控股有限公司 树脂组合物
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GB589716A (en) * 1945-03-28 1947-06-27 Andrew Mclean Improvements in or relating to the production of triamino-monocyclic aromatic hydrocarbons
CN1747995A (zh) * 2003-02-14 2006-03-15 西巴特殊化学品控股有限公司 树脂组合物
CN107400058A (zh) * 2016-05-19 2017-11-28 北京理工大学 2,4,6-三甲基苯-1,3,5-三胺以及n,n,n-三酰化产物的合成方法
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