CN110551011A - synthesis method of hesperetin dihydrochalcone - Google Patents
synthesis method of hesperetin dihydrochalcone Download PDFInfo
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- CN110551011A CN110551011A CN201910918666.8A CN201910918666A CN110551011A CN 110551011 A CN110551011 A CN 110551011A CN 201910918666 A CN201910918666 A CN 201910918666A CN 110551011 A CN110551011 A CN 110551011A
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- C07—ORGANIC CHEMISTRY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/20—Carbocyclic rings
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Abstract
The invention provides a synthesis method of hesperetin dihydrochalcone, which overcomes the problem that no literature records about hesperetin dihydrochalcone synthesis process for reference of manufacturers at present. The invention adopts a one-pot method, takes hesperidin as a starting material, is placed in a sodium hydroxide solution or a potassium hydroxide solution for catalytic hydrogenation to prepare hesperidin dihydrochalcone, is added with acid for neutralization, and is hydrolyzed under an acidic condition to obtain the hesperetin dihydrochalcone.
Description
Technical Field
the invention belongs to the technical field of food additives, and particularly relates to a synthesis method of hesperetin dihydrochalcone.
Background
Because of the increasing proportion of diabetes patients in the world, the demand of sugar in human diet is changing, the exploration of natural low-calorie sweeteners is deepening, and meanwhile, the natural low-calorie sweeteners provide guarantee for the health of human beings. The healthy natural low-calorie sweetener is extracted from plants, is prepared by a biological method or a simple reduction reaction, has good taste, low addition amount and low calorie, can meet the pursuit of people for sweet taste, and can reduce the health hidden trouble caused by excessive sugar intake, so the natural low-calorie sweetener has good safety and is easy to accept by consumers and is popular in the market. At present, the natural high-power sweetener mainly comprises stevioside, glycyrrhizin, mogroside, aspartame, thaumatin and the like.
Neohesperidin dihydrochalcone is a common sweetener sold in the market at present, has high sweetness, is about 1800 times of the sweetness of cane sugar by measurement, has higher sweetness and small addition amount, but has the defect of slow sweetness, and the taste is not very good. The hesperetin dihydrochalcone is a novel sweetener, the sweetness of the hesperetin dihydrochalcone is equivalent to that of neohesperidin dihydrochalcone, the addition amount is small, the calorie of the product can be reduced, the defect of slow sweetness of the neohesperidin dihydrochalcone is overcome, the taste is pure, and the requirement of healthy diet is met. However, the synthesis process of hesperetin dihydrochalcone is rarely researched and is deficient in resources, and a synthesis process which is simple in process, high in yield and content and can be directly used by manufacturers is not found at present.
therefore, under the large background that the cases of diabetes mellitus and the like are increasing, the synthesis process of the novel healthy sweetener of hesperetin dihydrochalcone has social value.
disclosure of Invention
In order to get rid of the dilemma that no literature records the synthesis process of hesperetin dihydrochalcone at present and can be used by manufacturers for reference, the invention provides a synthesis method of hesperetin dihydrochalcone, and provides a simple process for producing the natural low-calorie sweetener for the public.
The mechanism of the invention is as follows:
a one-pot method is adopted, hesperidin is used as a starting raw material, the starting raw material is placed in alkali liquor for catalytic hydrogenation to prepare hesperidin dihydrochalcone, acid is added for neutralization, and the hesperetin dihydrochalcone is obtained through hydrolysis under an acidic condition.
Wherein hesperidin is extracted from immature bitter orange of citrus trees widely planted in south, and has no sweet taste; the raw material has wide sources and is concentrated in Hunan, Hubei, Sichuan, Guangdong and the like.
In order to achieve the purpose, the technical solution provided by the invention is as follows:
The synthesis method of hesperetin dihydrochalcone is characterized by comprising the following steps:
1) preparation of hesperidin dihydrochalcone
Adding a sodium hydroxide solution or a potassium hydroxide solution with the mass concentration of 5-10% into raw material hesperidin, adding a catalytic amount of Raney nickel catalyst (other hydrogenation catalysts can be used, but the catalytic effect of the Raney nickel catalyst is optimal, and the catalytic rate is most appropriate), uniformly stirring, heating to 40-45 ℃, and carrying out hydrogenation reaction to obtain a solution containing hesperidin dihydrochalcone;
2) Preparation of hesperetin dihydrochalcone crude product
and adjusting the pH value of the solution containing the hesperidin dihydrochalcone to 2-4, heating and refluxing to complete hydrolysis, cooling to below 10 ℃, crystallizing, filtering and drying to obtain a crude hesperetin dihydrochalcone product.
Further, step 2) is followed by:
step 3) preparing the hesperetin dihydrochalcone refined product
and recrystallizing the crude hesperetin dihydrochalcone product by using ethanol with the volume concentration of 45-55% of 10-15 times, filtering, and drying to obtain the refined hesperetin dihydrochalcone product.
Further, in the step 1), the mass ratio of the raw material hesperidin to the sodium hydroxide solution is 1: 10-12.
Further, in the step 1), the temperature is raised to 40 ℃, and hydrogenation reaction is carried out for 3 hours.
Further, in the step 1), the mass ratio of the raw material hesperidin to the sodium hydroxide solution is 1: 10;
The addition amount of the Raney nickel catalyst is 3% of the raw material hesperidin in mass.
Further, the specific steps of step 2) are:
Adjusting the pH value of the solution containing hesperidin dihydrochalcone to 2 by using hydrochloric acid, heating, carrying out reflux reaction for 5 hours until complete hydrolysis, cooling to below 10 ℃, crystallizing for 24 hours, carrying out suction filtration and drying to obtain a crude product of hesperetin dihydrochalcone; the hydrochloric acid is used for adjusting the pH value of the solution, so that the cost is low, other oxidation reactions cannot occur, and the quality of the product in the preparation process is favorably controlled.
further, in the step 1), the mass concentration of the sodium hydroxide solution or the potassium hydroxide solution is 5%.
Further, the specific steps of step 3) are:
and recrystallizing the crude hesperetin dihydrochalcone product by using ethanol with the volume concentration of 10 times and mass concentration of 50%, filtering, and drying to obtain a refined hesperetin dihydrochalcone product.
The invention has the advantages that:
the invention adopts a one-pot method to prepare the hesperetin dihydrochalcone with high content and high yield, takes hesperidin as a raw material to carry out hydrogenation reaction in an alkaline environment, and then carries out hydrolysis reaction in an acidic environment to prepare the hesperetin dihydrochalcone. The method has the advantages of abundant raw material sources, easy acquisition, and environment-friendly solvent used in the preparation process, and is suitable for production and processing of food additives.
the hesperetin dihydrochalcone can be used as a sweetening agent, a flavoring agent and a flavoring agent, is used in products such as food, medicine, feed, daily chemical products and the like, has pure taste, and can be used in life as a substitute product of popular sweet products such as sucrose and the like.
Detailed Description
the present invention will be described in further detail with reference to the following specific examples:
example 1
A synthesis method of hesperetin dihydrochalcone comprises the following steps:
1) Preparation of hesperidin dihydrochalcone
Adding 1000g of sodium hydroxide solution with the mass concentration of 5% into 100g of raw material hesperidin, adding 3g of Raney nickel catalyst, uniformly stirring, heating to 40 ℃, and carrying out hydrogenation reaction for 3h to obtain a solution containing hesperidin dihydrochalcone;
2) preparation of hesperetin dihydrochalcone crude product
Adjusting the pH value of the solution containing hesperidin dihydrochalcone to 2 by using hydrochloric acid, heating up, refluxing, reacting for 5 hours until complete hydrolysis, cooling to below 10 ℃, crystallizing for 24 hours, filtering by suction, and drying to obtain a crude hesperetin dihydrochalcone product.
Step 3) preparing the hesperetin dihydrochalcone refined product
Recrystallizing the crude hesperetin dihydrochalcone obtained in the step 2) by using ethanol with the mass concentration of 50% of 10 times of the volume, filtering and drying to obtain 28g of a refined hesperetin dihydrochalcone product, and detecting the content of the refined hesperetin dihydrochalcone product to be 95.5% by using HPLC.
Example 2
A synthesis method of hesperetin dihydrochalcone comprises the following steps:
1) Preparation of hesperidin dihydrochalcone
Adding 1200g of sodium hydroxide solution with the mass concentration of 8% into 100g of raw material hesperidin, adding 3g of Raney nickel catalyst, uniformly stirring, heating to 45 ℃, and carrying out hydrogenation reaction for 3h to obtain a solution containing hesperidin dihydrochalcone;
2) Preparation of hesperetin dihydrochalcone crude product
adjusting the pH value of the solution containing hesperidin dihydrochalcone to 3 by using hydrochloric acid, heating up, carrying out reflux reaction for 5 hours until complete hydrolysis, cooling to below 10 ℃, crystallizing for 24 hours, carrying out suction filtration and drying to obtain a crude hesperetin dihydrochalcone product;
step 3) preparing the hesperetin dihydrochalcone refined product
Recrystallizing the crude hesperetin dihydrochalcone obtained in the step 2) by using ethanol with the volume concentration of 12 times of 55%, performing suction filtration and drying to obtain 27g of a refined hesperetin dihydrochalcone product, and detecting the content of 96.0% by using HPLC.
example 3
A synthesis method of hesperetin dihydrochalcone comprises the following steps:
1) Preparation of hesperidin dihydrochalcone
Adding 550g of potassium hydroxide solution with the mass concentration of 10% into 50g of raw material hesperidin, adding 1.5g of Raney nickel catalyst, uniformly stirring, heating to 42 ℃, and carrying out hydrogenation reaction for 3h to obtain a solution containing hesperidin dihydrochalcone;
2) Preparation of hesperetin dihydrochalcone crude product
Adjusting the pH value of the solution containing hesperidin dihydrochalcone to 3 by using hydrochloric acid, heating up, carrying out reflux reaction for 5 hours until complete hydrolysis, cooling to below 10 ℃, crystallizing for 24 hours, carrying out suction filtration and drying to obtain a crude hesperetin dihydrochalcone product;
Step 3) preparing the hesperetin dihydrochalcone refined product
Recrystallizing the crude hesperetin dihydrochalcone obtained in the step 2) by using ethanol with the volume concentration of 15 times being 45%, performing suction filtration and drying to obtain 13g of a refined hesperetin dihydrochalcone product, and detecting the content to be 94.5% by using HPLC.
Example 4
A synthesis method of hesperetin dihydrochalcone comprises the following steps:
1) Preparation of hesperidin dihydrochalcone
Adding 1500g of sodium hydroxide solution with the mass concentration of 5% into 150g of raw material hesperidin, adding 4.5g of Raney nickel catalyst, uniformly stirring, heating to 40 ℃, and carrying out hydrogenation reaction for 3h to obtain a solution containing hesperidin dihydrochalcone;
2) Preparation of hesperetin dihydrochalcone crude product
adjusting the pH value of the solution containing hesperidin dihydrochalcone to 2 by using hydrochloric acid, heating up, refluxing, reacting for 5 hours until complete hydrolysis, cooling to below 10 ℃, crystallizing for 24 hours, filtering by suction, and drying to obtain a crude product of hesperetin dihydrochalcone;
Step 3) preparing the hesperetin dihydrochalcone refined product
Recrystallizing the crude hesperetin dihydrochalcone obtained in the step 2) by using ethanol with the mass concentration of 50% of 10 times of the volume, filtering and drying to obtain 41.5g of a refined hesperetin dihydrochalcone product, and detecting the content of the refined hesperetin dihydrochalcone product by using HPLC (high performance liquid chromatography) to be 97.1%.
example 5
A synthesis method of hesperetin dihydrochalcone comprises the following steps:
1) Preparation of hesperidin dihydrochalcone
Adding 200g of potassium hydroxide solution with the mass concentration of 5% into 20g of raw material hesperidin, adding 0.6g of Raney nickel catalyst, uniformly stirring, heating to 40 ℃, and carrying out hydrogenation reaction for 3h to obtain a solution containing hesperidin dihydrochalcone;
2) Preparation of hesperetin dihydrochalcone crude product
Adjusting the pH value of the solution containing hesperidin dihydrochalcone to 4 by using hydrochloric acid, heating up, refluxing, reacting for 5 hours until complete hydrolysis, cooling to below 10 ℃, crystallizing for 24 hours, filtering by suction, and drying to obtain a crude hesperetin dihydrochalcone product.
Step 3) preparing the hesperetin dihydrochalcone refined product
recrystallizing the crude hesperetin dihydrochalcone obtained in the step 2) by using ethanol with the mass concentration of 13 times of the volume of 50%, performing suction filtration and drying to obtain 4.9g of a refined hesperetin dihydrochalcone product, and detecting the content of the refined hesperetin dihydrochalcone product to be 95.5% by using HPLC.
while the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications or substitutions can be easily made by those skilled in the art within the technical scope of the present disclosure.
Claims (8)
1. A synthesis method of hesperetin dihydrochalcone is characterized by comprising the following steps:
1) Preparation of hesperidin dihydrochalcone
Adding a sodium hydroxide solution or a potassium hydroxide solution with the mass concentration of 5-10% into raw material hesperidin, adding a catalytic amount of Raney nickel catalyst, uniformly stirring, heating to 40-45 ℃, and carrying out hydrogenation reaction to obtain a solution containing hesperidin dihydrochalcone;
2) Preparation of hesperetin dihydrochalcone crude product
And adjusting the pH value of the solution containing the hesperidin dihydrochalcone to 2-4, heating and refluxing to complete hydrolysis, cooling to below 10 ℃, crystallizing, filtering and drying to obtain a crude hesperetin dihydrochalcone product.
2. the synthesis method of hesperetin dihydrochalcone according to claim 1, further comprising, after step 2):
Step 3) preparing the hesperetin dihydrochalcone refined product
and recrystallizing the crude hesperetin dihydrochalcone product by using ethanol with the volume concentration of 45-55% of 10-15 times, filtering, and drying to obtain the refined hesperetin dihydrochalcone product.
3. The synthesis method of hesperetin dihydrochalcone according to claim 1, characterized in that: in the step 1), the mass ratio of the raw material hesperidin to the sodium hydroxide solution is 1: 10-12.
4. The synthesis method of hesperetin dihydrochalcone according to claim 1, characterized in that: in the step 1), the temperature is raised to 40 ℃, and hydrogenation reaction is carried out for 3 hours.
5. The synthesis method of hesperetin dihydrochalcone according to claim 3, characterized in that: in the step 1), the mass ratio of the raw material hesperidin to the sodium hydroxide solution is 1: 10; the addition amount of the Raney nickel catalyst is 3% of the raw material hesperidin in mass.
6. The synthesis method of hesperetin dihydrochalcone according to claim 1, characterized in that the specific steps of step 2) are:
Adjusting the pH value of the solution containing the hesperidin dihydrochalcone to 2 by using hydrochloric acid, heating up, refluxing, reacting for 5 hours until complete hydrolysis, cooling to below 10 ℃, crystallizing for 24 hours, filtering by suction, and drying to obtain a crude hesperetin dihydrochalcone product.
7. The synthesis method of hesperetin dihydrochalcone according to claim 1, characterized in that: in the step 1), the mass concentration of the sodium hydroxide solution or the potassium hydroxide solution is 5%.
8. The synthesis method of hesperetin dihydrochalcone according to claim 1, characterized in that the specific steps of step 3) are:
And recrystallizing the crude hesperetin dihydrochalcone product by using ethanol with the volume concentration of 10 times and mass concentration of 50%, filtering, and drying to obtain a refined hesperetin dihydrochalcone product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851484A (en) * | 2021-01-25 | 2021-05-28 | 三原润禾生物科技有限公司 | Method for synthesizing phloretin from naringenin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1404306A (en) * | 1973-02-22 | 1975-08-28 | Givaudan & Cie Sa | Manufacture of hesperetin dihydrochalcone glucoside |
| CN101787062A (en) * | 2010-03-17 | 2010-07-28 | 广东省食品工业研究所 | Hesperetin dihydrochalcone-7-O-glucoside and preparation method and application thereof |
| CN105801636A (en) * | 2016-03-24 | 2016-07-27 | 济南诚汇双达化工有限公司 | Synthetic method for naringin dihydrochalcone |
| CN107602636A (en) * | 2017-08-15 | 2018-01-19 | 涟源康麓生物科技有限公司 | The preparation method of new hesperidin methyl dihydrochalcone |
-
2019
- 2019-09-26 CN CN201910918666.8A patent/CN110551011A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1404306A (en) * | 1973-02-22 | 1975-08-28 | Givaudan & Cie Sa | Manufacture of hesperetin dihydrochalcone glucoside |
| CN101787062A (en) * | 2010-03-17 | 2010-07-28 | 广东省食品工业研究所 | Hesperetin dihydrochalcone-7-O-glucoside and preparation method and application thereof |
| CN105801636A (en) * | 2016-03-24 | 2016-07-27 | 济南诚汇双达化工有限公司 | Synthetic method for naringin dihydrochalcone |
| CN107602636A (en) * | 2017-08-15 | 2018-01-19 | 涟源康麓生物科技有限公司 | The preparation method of new hesperidin methyl dihydrochalcone |
Non-Patent Citations (2)
| Title |
|---|
| ANNETT BRAUNE等: "Degradation of Neohesperidin Dihydrochalcone by Human Intestinal Bacteria", 《OURNAL OF AGRICULTURAL AND FOOD CHEMISTRY》 * |
| STEPHEN J. BLOOR: "Overview of Methods for Analysis and Identification of Flavonoids", 《METHODS IN ENZYMOLOGY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851484A (en) * | 2021-01-25 | 2021-05-28 | 三原润禾生物科技有限公司 | Method for synthesizing phloretin from naringenin |
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Application publication date: 20191210 |