Nicotinamide and preparation method thereof
By using Fe-ZSM-5 molecular sieve catalyst, combined with oxidation and ammonization reaction, the pollution and high cost problems in the traditional nicotinamide synthesis process are solved, and a high yield and low cost preparation of nicotinamide is achieved.
Patent Information
- Application Number
- CN202510604625.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-12
- Publication Date
- 2025-08-12
AI Technical Summary
The traditional nicotinamide synthesis process has problems such as severe pollution, low yield and unrecyclable catalysts, resulting in high costs.
Fe-ZSM-5 molecular sieve was used as a catalyst, and oxidation reaction was performed by mixing 3-methylpyridine, hydrogen peroxide solution and water to form a niacin solution, and then ammonia gas was introduced for ammonia reaction to prepare niacinamide.
A green and environmentally friendly high-yield nicotinamide preparation is achieved, with a yield of more than 80%. The catalyst can be used multiple times, reducing costs.
Smart Images
Figure CN120463644A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of organic synthesis, and in particular to nicotinamide and a preparation method thereof. Background Art
[0002] Nicotinamide is the main form of vitamin B3 and is widely used in anti-aging skin care products, diabetes treatment, and food nutrition fortification. The traditional nicotinamide synthesis process has the following problems: (1) Severe pollution: The conventional oxidation step uses concentrated nitric acid or potassium permanganate, which produces a large amount of acidic waste liquid. (2) Low yield: Multiple steps are required, and the total yield is less than 60%. (3) Catalysts are not recyclable: Precious metal catalysts (such as vanadium and molybdenum oxides) are difficult to reuse and are expensive. Therefore, a green and environmentally friendly method for preparing nicotinamide with high yield and low cost is urgently needed. Summary of the Invention
[0003] The purpose of the present invention is to provide nicotinamide and a preparation method thereof.
[0004] To achieve the above object, a method for preparing nicotinamide comprises the following steps: mixing 3-methylpyridine, Fe-ZSM-5 molecular sieve, hydrogen peroxide solution and water, performing an oxidation reaction to obtain a nicotinic acid solution, and introducing ammonia gas into the nicotinic acid solution to perform an amination reaction to obtain nicotinamide.
[0005] Preferably, the mass volume ratio of the 3-methylpyridine, Fe-ZSM-5 molecular sieve, hydrogen peroxide solution and water is 9-11 g: 1.3-1.5 g: 14-16 mL: 50 mL.
[0006] Preferably, the mass volume ratio of the 3-methylpyridine, Fe-ZSM-5 molecular sieve, hydrogen peroxide solution and water is 10 g:1.4 g:15 mL:50 mL.
[0007] Preferably, the mass of iron in the Fe-ZSM-5 molecular sieve accounts for 1%-5% of the total mass of the Fe-ZSM-5 molecular sieve.
[0008] Preferably, the mass of iron in the Fe-ZSM-5 molecular sieve accounts for 2%-3% of the total mass of the Fe-ZSM-5 molecular sieve.
[0009] Preferably, the mass concentration of the hydrogen peroxide solution is 25%-40%.
[0010] Preferably, the temperature of the oxidation reaction is 70-90° C., and the time of the oxidation reaction is 1-3 hours.
[0011] Preferably, ammonia gas is introduced until the pH of the nicotinic acid solution is 8-9.
[0012] Preferably, the temperature of the amination reaction is 50-70° C., and the time of the amination reaction is 1-2 h.
[0013] The present invention also provides nicotinamide prepared by the above-mentioned preparation method of nicotinamide.
[0014] The present invention has the following beneficial effects:
[0015] The present invention provides a method for preparing nicotinamide, comprising the steps of mixing 3-methylpyridine, Fe-ZSM-5 molecular sieve, a hydrogen peroxide solution, and water, conducting an oxidation reaction to obtain a nicotinic acid solution, and introducing ammonia gas into the nicotinic acid solution to conduct an amination reaction to obtain nicotinamide. The present invention uses Fe-ZSM-5 molecular sieve as a catalyst, which exhibits dual oxidation and amination activities, is low-cost, and can be reused multiple times. Using hydrogen peroxide as an oxidant, no toxic substances are generated, and the only byproduct is water, making it environmentally friendly.
[0016] The present invention provides a method for preparing nicotinamide, which has a simple process, is easy to operate, and can be used for large-scale production. Nicotinamide is prepared in a one-step process through oxidation-amination, with a yield of >80%.
[0017] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 1 is a flow chart of the method for preparing nicotinamide according to Example 1 of the present invention. DETAILED DESCRIPTION
[0019] The present invention provides a method for preparing nicotinamide, comprising the following steps: mixing 3-methylpyridine, Fe-ZSM-5 molecular sieve, a hydrogen peroxide solution and water, performing an oxidation reaction to obtain a nicotinic acid solution, and introducing ammonia gas into the nicotinic acid solution to perform an amination reaction to obtain nicotinamide.
[0020] In some embodiments of the present invention, the mass volume ratio of the 3-methylpyridine, Fe-ZSM-5 molecular sieve, hydrogen peroxide solution and water is 9-11 g: 1.3-1.5 g: 14-16 mL: 50 mL.
[0021] In some embodiments of the present invention, the mass volume ratio of the 3-methylpyridine, Fe-ZSM-5 molecular sieve, hydrogen peroxide solution and water is 10 g:1.4 g:15 mL:50 mL.
[0022] In some embodiments of the present invention, the mass of iron in the Fe-ZSM-5 molecular sieve accounts for 1% to 5% of the total mass of the Fe-ZSM-5 molecular sieve.
[0023] In some embodiments of the present invention, the mass of iron in the Fe-ZSM-5 molecular sieve accounts for 2%-3% of the total mass of the Fe-ZSM-5 molecular sieve.
[0024] In some embodiments of the present invention, the mass concentration of the hydrogen peroxide solution is 25%-40%.
[0025] In some embodiments of the present invention, the temperature of the oxidation reaction is 70-90° C., and the time of the oxidation reaction is 1-3 hours.
[0026] In some embodiments of the present invention, ammonia gas is introduced until the pH of the nicotinic acid solution is 8-9.
[0027] In some embodiments of the present invention, the temperature of the amination reaction is 50-70° C., and the time of the amination reaction is 1-2 h.
[0028] In some embodiments of the present invention, after the amination reaction, the amination reaction solution is filtered, the filter residue Fe-ZSM-5 molecular sieve is recovered, and the filtrate is concentrated and crystallized to obtain nicotinamide.
[0029] In some embodiments of the present invention, the Fe-ZSM-5 molecular sieve can be recycled multiple times, and the number of recycling times is ≥ 4. When the Fe-ZSM-5 molecular sieve recycled four times is used as a raw material, the yield of nicotinamide is > 80%.
[0030] The present invention also provides nicotinamide prepared by the above-mentioned preparation method of nicotinamide.
[0031] The present invention is further described below with reference to the accompanying drawings and examples. Unless otherwise defined, technical or scientific terms used herein shall have the same meanings as those commonly understood by persons of ordinary skill in the art to which the present invention pertains. The above-mentioned features or features described in the specific examples of the present invention may be combined in any manner. These specific examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention.
[0032] Example 1
[0033] Mix 10 g of 3-methylpyridine, 1.5 g of Fe-ZSM-5 molecular sieve, 15 mL of 30% hydrogen peroxide solution, and 50 mL of water, and perform an oxidation reaction at 80° C. for 2 h to obtain a nicotinic acid solution.
[0034] Ammonia gas was introduced into the nicotinic acid solution until the pH of the nicotinic acid solution reached 8. The amination reaction was carried out at 60° C. for 1 h to obtain an amination reaction solution. The amination reaction solution was filtered, and the Fe-ZSM-5 molecular sieve in the filter residue was recovered. The obtained filtrate was concentrated and recrystallized to obtain nicotinamide (11.7 g, yield 88.1%).
[0035] The process of the nicotinamide preparation method provided in Example 1 is as follows Figure 1 shown.
[0036] The nicotinamide prepared in this example was subjected to hydrogen and carbon spectrum analysis. 1 H NMR (300MHz, DMSO-d6): δ: 9 (s, 1H), 8.68 (d, J = 6Hz), 8.2 (d, J = 6Hz), 8.15 (s, 1H), 7.56 (s, 1H), 7.47 (dd, J = 3.6Hz, 1H); 13 C NMR (100MHz, DMSO-d6): δ: 166.4, 151.7, 148.6, 135.2, 129.7, 123.2.
[0037] Example 2
[0038] The Fe-ZSM-5 molecular sieve obtained in Example 1 was filtered and recovered for the next preparation of nicotinamide.
[0039] Mix 10 g of 3-methylpyridine, 1.45 g of Fe-ZSM-5 molecular sieve, 15 mL of 30% hydrogen peroxide solution, and 50 mL of water, and perform an oxidation reaction at 70° C. for 1.5 hours to obtain a nicotinic acid solution.
[0040] Ammonia gas was introduced into the nicotinic acid solution until the pH of the nicotinic acid solution reached 8. The amination reaction was carried out at 65° C. for 1 h to obtain an amination reaction solution. The amination reaction solution was filtered, and the Fe-ZSM-5 molecular sieve in the filter residue was recovered. The obtained filtrate was concentrated and recrystallized to obtain nicotinamide (11.47 g, yield 86.4%).
[0041] Example 3
[0042] The Fe-ZSM-5 molecular sieve obtained in Example 2 was filtered and recovered, and nicotinamide was prepared again.
[0043] Mix 10 g of 3-methylpyridine, 1.40 g of Fe-ZSM-5 molecular sieve, 15 mL of 30% hydrogen peroxide solution, and 50 mL of water, and perform an oxidation reaction at 85° C. for 1 hour to obtain a nicotinic acid solution.
[0044] Ammonia gas was introduced into the nicotinic acid solution until the pH of the nicotinic acid solution reached 9. An amination reaction was carried out at 50° C. for 2 h to obtain an amination reaction solution. The amination reaction solution was filtered, and the Fe-ZSM-5 molecular sieve in the filter residue was recovered. The obtained filtrate was concentrated and recrystallized to obtain nicotinamide (11.26 g, yield 84.8%).
[0045] Example 4
[0046] The Fe-ZSM-5 molecular sieve obtained in Example 3 was filtered and recovered, and nicotinamide was prepared again.
[0047] Mix 10 g of 3-methylpyridine, 1.37 g of Fe-ZSM-5 molecular sieve, 15 mL of 30% hydrogen peroxide solution, and 50 mL of water, and perform an oxidation reaction at 90° C. for 1 hour to obtain a nicotinic acid solution.
[0048] Ammonia gas was introduced into the nicotinic acid solution until the pH of the nicotinic acid solution reached 7. An amination reaction was carried out at 70° C. for 1.5 h to obtain an amination reaction solution. The amination reaction solution was filtered, and the Fe-ZSM-5 molecular sieve in the filter residue was recovered. The obtained filtrate was concentrated and recrystallized to obtain nicotinamide (11.17 g, yield 84.1%).
[0049] Example 5
[0050] The Fe-ZSM-5 molecular sieve obtained in Example 4 was filtered and recovered, and nicotinamide was prepared again.
[0051] Mix 10 g of 3-methylpyridine, 1.32 g of Fe-ZSM-5 molecular sieve, 15 mL of 30% hydrogen peroxide solution, and 50 mL of water, and perform an oxidation reaction at 70° C. for 3 h to obtain a nicotinic acid solution.
[0052] Ammonia gas was introduced into the nicotinic acid solution until the pH of the nicotinic acid solution reached 8. An amination reaction was carried out at 50° C. for 2 h to obtain an amination reaction solution. The amination reaction solution was filtered, and the Fe-ZSM-5 molecular sieve in the filter residue was recovered. The obtained filtrate was concentrated and recrystallized to obtain nicotinamide (11.17 g, yield 82.7%).
[0053] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solutions of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.
Claims
1. A method for preparing nicotinamide, characterized in that: The method comprises the following steps: mixing 3-methylpyridine, Fe-ZSM-5 molecular sieve, hydrogen peroxide solution and water, performing oxidation reaction to obtain nicotinic acid solution, introducing ammonia gas into the nicotinic acid solution, performing an amination reaction to obtain nicotinamide.
2. The method for preparing nicotinamide according to claim 1, wherein: The mass volume ratio of the 3-methylpyridine, Fe-ZSM-5 molecular sieve, hydrogen peroxide solution and water is 9-11 g: 1.3-1.5 g: 14-16 mL: 50 mL.
3. The method for preparing nicotinamide according to claim 2, wherein: The mass volume ratio of the 3-methylpyridine, Fe-ZSM-5 molecular sieve, hydrogen peroxide solution and water is 10 g:1.4 g:15 mL:50 mL.
4. The method for preparing nicotinamide according to claim 1, wherein: The mass of iron in the Fe-ZSM-5 molecular sieve accounts for 1% to 5% of the total mass of the Fe-ZSM-5 molecular sieve.
5. The method for preparing nicotinamide according to claim 4, characterized in that: The mass of iron in the Fe-ZSM-5 molecular sieve accounts for 2%-3% of the total mass of the Fe-ZSM-5 molecular sieve.
6. The method for preparing nicotinamide according to claim 1, characterized in that: The mass concentration of the hydrogen peroxide solution is 25%-40%.
7. The method for preparing nicotinamide according to claim 1, characterized in that: The temperature of the oxidation reaction is 70-90° C., and the time of the oxidation reaction is 1-3 hours.
8. The method for preparing nicotinamide according to claim 1, characterized in that: Ammonia gas was introduced until the pH of the nicotinic acid solution was 8-9.
9. The method for preparing nicotinamide according to claim 1, wherein: The temperature of the amination reaction is 50-70° C., and the time of the amination reaction is 1-2 hours.
10. Nicotinamide prepared by the method for preparing nicotinamide according to any one of claims 1 to 9.