Heliotropin and synthesis method thereof

Abstract

A synthesis method of heliotropin relates to the technical field of heliotropin synthesis, and comprises the following steps: S1, uniformly mixing glyoxylic acid, glacial acetic acid and benzodioxole, then slowly dropwise adding concentrated sulfuric acid under a first temperature condition, reacting for a period of time, slowly dropwise adding nitric acid under a second temperature condition, reacting for a period of time, then adding hydrochloric acid, and reacting for a period of time to obtain a mixed solution; reaction liquid is obtained; s2, filtering the reaction liquid obtained in the step S1 to obtain a heliotropin crude product and filtrate; s3, recovering the filtrate obtained by filtering in S2, and washing, filtering and drying the heliotropin crude product obtained in S2 to obtain heliotropin; the heliotropin is prepared by a one-pot method, so that the synthesis steps are simplified, the whole synthesis method is simpler and more convenient to operate, the synthesis efficiency is improved, redundant wastewater is not generated, meanwhile, the recovery rate of filtrate can reach 95-99%, and the cost of raw materials is reduced.

Description

Technical Field

[0001] This invention relates to the field of hesperidin synthesis technology, specifically to a hesperidin and its synthesis method. Background Technology

[0002] Jasmine aldehyde (3,4-methylenedioxybenzaldehyde), an important fine chemical intermediate, is widely used in fragrances, cosmetics, pharmaceuticals, and food additives. Its unique sweet aroma and long-lasting scent make it a core component of floral fragrances such as carnation, lily, and violet, and it also plays an irreplaceable role in electroplating, polishing, and pharmaceutical synthesis. However, the content of jasmine aldehyde in natural sources (such as locust flowers and laurel leaves) is extremely low, making it difficult to meet industrial demands. Therefore, chemical synthesis has become the main production method for jasmine aldehyde.

[0003] There are two traditional synthesis processes for hesperidin: ozone oxidation and sodium dichromate oxidation. Although these two methods are simple, ozone oxidation has problems such as reliance on imported raw materials, high energy consumption, and many by-products, while sodium dichromate oxidation is prone to environmental pollution due to the use of heavy metal oxidants. With the development of industrial technology, the efficiency of traditional synthesis processes has been improved by introducing new catalysts and optimizing reaction conditions, but it is still not satisfactory.

[0004] To address the aforementioned issues, Chinese invention patent CN117756773A discloses a process for preparing hesperidin, which uses glyoxylic acid, acetic acid, concentrated sulfuric acid, and piperine as raw materials, nitric acid as an oxidant, and sodium nitrite as a catalyst, and finally prepares hesperidin through distillation, decolorization, and crystallization. Although the above patent can improve the yield of hesperidin, it involves many steps, is complex to operate, and generates a large amount of wastewater that needs to be treated before discharge, increasing costs. In addition, the solvent cannot be directly recycled and requires secondary treatment. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a method for synthesizing jasmine aldehyde, so as to solve the problems of complex operation, difficult solvent recovery and large amount of wastewater generation in the existing jasmine aldehyde synthesis method.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A method for synthesizing hesperidin includes the following steps:

[0008] S1. Mix glyoxylic acid, glacial acetic acid and piperine evenly, then slowly add concentrated sulfuric acid dropwise under the first temperature condition. After reacting for a period of time, slowly add nitric acid dropwise under the second temperature condition. After reacting for a period of time, the reaction solution is obtained.

[0009] S2. Filter the reaction solution obtained from S1 to obtain crude hesperidin and filtrate;

[0010] S3. Recover the filtrate obtained from S2 filtration, and wash, filter, and dry the crude hesperidin obtained from S2 to obtain hesperidin.

[0011] Preferably, in step S1, the reaction equation is:

[0012]

[0013] Preferably, in step S1, the molar ratio of glyoxylic acid, glacial acetic acid and piperine ring is (1-1.3):(2-10):1.

[0014] Preferably, in step S1, the first temperature condition is -15 to 25°C, and the reaction time is 12 to 30 hours.

[0015] Preferably, in step S1, the molar ratio of concentrated sulfuric acid to pepper rings is (0.5-1):1.

[0016] Preferably, in step S1, the second temperature condition is 0–40°C, and the reaction time is 2–5 h.

[0017] Preferably, in step S1, the concentration of nitric acid is 40% to 68%, and the molar ratio of nitric acid to piperine rings is (1.5 to 3):1.

[0018] Preferably, in step S2, the filtration method is pressure filtration or vacuum filtration.

[0019] Preferably, in step S3, washing and filtration are performed alternately three times, and the washing uses desalinated water at a temperature below 40°C.

[0020] The present invention also provides a jasmine aldehyde, which is prepared by the aforementioned synthesis method.

[0021] Compared with existing technologies, this invention has the following advantages: First, this invention simplifies the synthesis steps by preparing hesperidin in a one-pot process, making the entire synthesis method simpler and more convenient, and improving synthesis efficiency; second, the raw materials do not generate excess wastewater during the reaction process, solving the problem of large wastewater discharge and avoiding the need for additional wastewater treatment; finally, the filtrate recovery rate in this invention can reach 95-99%, and the recovered filtrate can provide some solvent for the next synthesis of hesperidin, thus reducing the amount of solvent added in the next synthesis and lowering the synthesis cost.

[0022] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Detailed Implementation

[0023] To make the technical means, creative features, objectives, and effects of this invention clearer and easier to understand, the invention will be further described below in conjunction with specific embodiments:

[0024] Example 1

[0025] S1. Add 7.70g of glyoxylic acid, 48g of glacial acetic acid and 12g of piperine to a 500ml three-necked flask and mix well. Then slowly add 7.84g of concentrated sulfuric acid at 0℃. After reacting for 20h, continue to slowly add 15.12g of 40% nitric acid at 0℃. After reacting for 5h, the reaction solution is obtained.

[0026] S2. The reaction solution obtained in S1 is filtered to obtain crude hesperidin and filtrate.

[0027] S3. The filtrate obtained from S2 is recovered, and the crude hesperidin obtained from S2 is subjected to three alternating desalination washings and natural air drying to obtain hesperidin.

[0028] Example 2

[0029] S1. Add 5.92g of glyoxylic acid, 9.6g of glacial acetic acid and 12g of piperine to a 500ml three-necked flask and mix well. Then, slowly add 3.92g of concentrated sulfuric acid at -15℃. After reacting for 30h, continue to slowly add 7.56g of 68% nitric acid at 20℃. After reacting for 3h, the reaction solution is obtained.

[0030] S2. The reaction solution obtained in S1 is filtered under pressure to obtain crude hesperidin and filtrate.

[0031] S3. The filtrate obtained from S2 is recovered, and the crude hesperidin obtained from S2 is subjected to three alternating desalination washings and natural air drying to obtain hesperidin.

[0032] Example 3

[0033] S1. Add 6.5g of glyoxylic acid, 25g of glacial acetic acid and 12g of piperine to a 500ml three-necked flask and mix well. Then slowly add 5.56g of concentrated sulfuric acid at 25℃. After reacting for 15h, continue to slowly add 12.34g of 50% nitric acid at 20℃. After reacting for 2h, the reaction solution is obtained.

[0034] S2. The reaction solution obtained in S1 is filtered under pressure to obtain crude hesperidin and filtrate.

[0035] S3. The filtrate obtained from S2 is recovered, and the crude hesperidin obtained from S2 is subjected to three alternating desalination washings and natural air drying to obtain hesperidin.

[0036] Example 4

[0037] S1. Add 7.32g of glyoxylic acid, 36.8g of glacial acetic acid and 12g of piperine to a 500ml three-necked flask and mix well. Then, slowly add 6.75g of concentrated sulfuric acid at 10℃. After reacting for 12h, continue to slowly add 13.78g of 60% nitric acid at 15℃. After reacting for 2.5h, the reaction solution is obtained.

[0038] S2. The reaction solution obtained in S1 is filtered to obtain crude hesperidin and filtrate.

[0039] S3. The filtrate obtained from S2 is recovered, and the crude hesperidin obtained from S2 is subjected to three alternating desalination washings and natural air drying to obtain hesperidin.

[0040] Example 5

[0041] S1. Add the filtrate recovered in Example 1, 7.70 g of glyoxylic acid and 12 g of piperine to a 500 ml three-necked flask and mix well. After reacting for 20 h, slowly add 15.12 g of 40% nitric acid at 0 °C. After reacting for 5 h, the reaction solution is obtained.

[0042] S2. The reaction solution obtained in S1 is filtered to obtain crude hesperidin and filtrate.

[0043] S3. The filtrate obtained from S2 is recovered, and the crude hesperidin obtained from S2 is subjected to three alternating desalination washings and natural air drying to obtain hesperidin.

[0044] The glyoxylic acid in the above embodiments is solid glyoxylic acid with a purity of 99%.

[0045] The quality, yield, purity, and filtrate recovery rate of the hesperidin prepared in Examples 1-5 were tested, and the test results are shown in the table below.

[0046]

[0047]

[0048] As can be seen from the table above, the purity of the jasmine aldehyde prepared in Examples 1-5 is consistently 99%, indicating that the synthesis method has good purity control, high process stability, and few by-products.

[0049] Regarding the yield, Example 4 had the shortest reaction time compared to the other examples, resulting in incomplete reaction and thus the lowest yield. In contrast, the yields of Examples 1-3 and Example 5 were consistently above 85%.

[0050] Regarding the filtrate recovery rate, Examples 1-5 all have a high filtrate recovery rate. In comparison, Example 5 uses the recovered filtrate from Example 1, which contains impurities, so its recovery rate is slightly lower.

[0051] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A method for synthesizing hesperidin, characterized in that, Includes the following steps: S1. Mix glyoxylic acid, glacial acetic acid and piperine evenly, then slowly add concentrated sulfuric acid dropwise under the first temperature condition. After reacting for a period of time, slowly add nitric acid dropwise under the second temperature condition. After reacting for a period of time, the reaction solution is obtained. S2. Filter the reaction solution obtained from S1 to obtain crude hesperidin and filtrate; S3. Recover the filtrate obtained from S2 filtration, and wash, filter, and dry the crude hesperidin obtained from S2 to obtain hesperidin.

2. The method for synthesizing hesperidin according to claim 1, characterized in that, In step S1, the reaction equation is:

3. The method for synthesizing hesperidin according to claim 1, characterized in that, In step S1, the molar ratio of glyoxylic acid, glacial acetic acid and piperine ring is (1-1.3):(2-10):

1.

4. The method for synthesizing hesperidin according to claim 1, characterized in that, In step S1, the first temperature condition is -15 to 25°C, and the reaction time is 12 to 30 hours.

5. The method for synthesizing hesperidin according to claim 1, characterized in that, In step S1, the molar ratio of concentrated sulfuric acid to pepper rings is (0.5-1):

1.

6. The method for synthesizing hesperidin according to claim 1, characterized in that, In step S1, the second temperature condition is 0–40°C, and the reaction time is 2–5 h.

7. The method for synthesizing hesperidin according to claim 1, characterized in that, In step S1, the concentration of nitric acid is 40% to 68%, and the molar ratio of nitric acid to piperine rings is (1.5 to 3):

1.

8. The method for synthesizing hesperidin according to claim 1, characterized in that, In step S2, the filtration method is pressure filtration or vacuum filtration.

9. The method for synthesizing hesperidin according to claim 1, characterized in that, In step S3, washing and filtration need to be performed alternately three times, and the washing uses desalinated water at a temperature below 40°C.

10. A type of hesperidin, characterized in that, It is prepared by the synthesis method according to any one of claims 1-9.

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