CN108329364A - A method of preparing sweetener based on Exocarpium Citri Grandis - Google Patents
A method of preparing sweetener based on Exocarpium Citri Grandis Download PDFInfo
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- CN108329364A CN108329364A CN201810119807.5A CN201810119807A CN108329364A CN 108329364 A CN108329364 A CN 108329364A CN 201810119807 A CN201810119807 A CN 201810119807A CN 108329364 A CN108329364 A CN 108329364A
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- exocarpium citri
- citri grandis
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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
- C07H15/203—Monocyclic carbocyclic rings other than cyclohexane rings; Bicyclic carbocyclic ring systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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Abstract
The invention discloses one kind based on Exocarpium Citri Grandis, and aurantiin is raw material, prepares the preparation method and applications of novel sweet monosodium glutamate.The specific method is as follows：Aurantiin is obtained by Exocarpium Citri Grandis, then using aurantiin as raw material, synthesizing new sweetener (neohesperidin dihydrochalcone).It is low mainly to solve raw material sources costliness, product yield in existing invention, it is difficult to the problems such as repeating.The present invention has recovery rate high, and product content is high, and the novel sweet monosodium glutamate purity of gained is high, feature capable of being industrialized, while being also scientific utilization and the market exploitation of Exocarpium Citri Grandis, provides the foundation of science.
Description
Technical field：
The invention belongs to chemosynthesis technical fields, and in particular to a kind of side preparing sweetener based on Exocarpium Citri Grandis
Method.
Technical background：
Exocarpium Citri Grandis (Exocarpium citri grandis) is also known as Huajuhong, is that Rutaceae plants Citrus (Citrus)
The prematurity of plant Citrus grandis (Eitrus grandis Osbeek) or shaddock (c.grandis osbeek) or the drying of maturation
Outside rind.Exocarpium Citri Grandis is the distinctive traditional Chinese medicine in China, and ancient times are recorded and modern research shows that Exocarpium Citri Grandis includes a variety of work
Property ingredient, has the effects that resolving sputum, qi-regulating, invigorating the spleen, helps digestion, cold dispelling.As Exocarpium Citri Grandis is widely planted and as traditional medicine
Material is saturated in the market, and reasonable scientific development has been particularly important using Exocarpium Citri Grandis.And aurantiin is as Exocarpium Citri Grandis flavones
Main ingredient in class compound, and its content is high, is used as the synthesis material of novel sweet monosodium glutamate, is filled with raw material sources
Foot, the advantages such as mature production technology.
Sweetener neohesperidin dihydrochalcone (NHDC) is the derivative of chalcone, is by carrying out hydrogen to neohesperidin
Prepared by change dihydrochalcone flavonoids.It has sweet taste high, and pleasant impression is lasting, and salubrious pleasant, stability is good, heat
It is low, human body can be reduced to advantages such as the sensitivitys of bitter taste.As a kind of novel sweetener, it is better than sucrose and saccharin.While it
No mutagenicity, non-carcinogenesis, without cariogenicity, without apparent poisonous effect, accretion rate is fast, to human body blood lipid level and blood glucose water
It is flat to have no adverse effects.Currently, safeties of the NHDC in food has had been widely recognized, include the U.S., Japan, China
More than 30 a state approvals Deng including are used as food additives.
Currently, sweetener neohesperidin dihydrochalcone is mainly to be passed through with the raw material neohesperidin extracted in rutaceae
It crosses made from conversion hydrogenation.Although China's citrus resource very abundant, a large amount of orange peel can be generated, and most citrus
It is but very low that skin contains neohesperidin amount, it is difficult to which mass production is insufficient for the production requirement of sweetener.Therefore it is more suitable to find
Material synthesis sweetener neohesperidin dihydrochalcone, have become very urgent.And aurantiin is as Exocarpium Citri Grandis flavonoids
Main ingredient in object is closed, sweetener synthesis material is used as, with sufficient raw, content is high in Exocarpium Citri Grandis, production
The advantages such as technical maturity.It is raw material with the aurantiin in Exocarpium Citri Grandis, not only having solved the problems, such as sweetener, there is lack of raw materials, but also solving
The problem of Exocarpium Citri Rubrum is saturated on the market as medicinal material.
The method for preparing neohesperidin dihydrochalcone now is mainly to be carried out under pressure of the pressure more than 2.0MPa, this
Method also reduces safety in addition to increasing technology difficulty, and product yield is not high, more demanding to equipment and technology, is unfavorable for grasping
Make, as patent document CN103804439A discloses a kind of synthetic method of neohesperidin dihydrochalcone；Simultaneously using biography
When system technique purifies neohesperidin dihydrochalcone, activated carbon decolorizing is added, increases operating procedure, also brings in operation and draw
Enter the risk of impurity.
From the point of view of disclosed sweetener neohesperidin dihydrochalcone related invention patent, though the research done at present has related to
And the preparation of neohesperidin, neohesperidin dihydrochalcone, but still have yield is low, technology stability is poor, and energy consumption is big etc.
Deficiency.Meanwhile widely planting with Exocarpium Citri Grandis and being saturated in the market as traditional medicine, reasonable scientific development profit
It is particularly important with Exocarpium Citri Grandis.It goes to prepare novel sweet monosodium glutamate with method therefore, it is necessary to find new synthesis material and approach
Neohesperidin dihydrochalcone.
Invention content
The method that the object of the present invention is to provide a kind of to prepare sweetener based on Exocarpium Citri Grandis, mainly solves the prior art
Middle raw material sources are expensive, and product yield is low, it is difficult to the problems such as repeating, while providing a new side for the scientific utilization of Exocarpium Citri Grandis
To.
To achieve the above object, the present invention adopts the following technical scheme that：
Wherein, the method that sweetener is prepared based on Exocarpium Citri Grandis includes the following steps：
Step 1：Aurantiin sterling is extracted and prepared in Exocarpium Citri Grandis；
Step 2：Aurantiin is proportionally added into KOH solution, nitrogen protection is passed through, is heated back in 140~150 DEG C
2~3h is flowed, salt acid for adjusting pH is added after cooling, generates a large amount of yellow-white precipitations, being heated to 110~120 DEG C makes mixture solid
Dissolving, natural cooling 12-24 hours precipitate crystal, and filter, and ice water washs repeatedly, and vacuum drying obtains product acetophenone -4'-
Neohesperidin solid；
Step 3：Appropriate acetophenone -4'- neohesperidins and isovanillin are added in reaction bulb, addition solvent is appropriate,
Then stirring a period of time at room temperature is added catalyst and reaction medium glacial acetic acid is appropriate, heated back for 70-90 DEG C under nitrogen protection
10-18h is flowed, it is finally cooling that solid is precipitated, it filters and washs to obtain faint yellow solid with ethyl alcohol, be dried in vacuo, obtain new orange peel
Glycosides；
Step 4：Neohesperidin obtained by appropriate step 3 is dissolved in the water with sodium hydroxide, addition catalyst is appropriate,
It is placed in reaction kettle, is passed through hydrogen, in the case where adding lower pressure, stir or wave reaction a period of time.After reaction, it filters,
Filtrate adjusts pH with concentrated hydrochloric acid.It places refrigerator to stand overnight, filter, product is recrystallized with hot water, and filter cake is dry in vacuum drying chamber
It is dry overnight, obtain sweetener neohesperidin dihydrochalcone.
Further：The ratio 1 of aurantiin and potassium hydroxide solution described in step 2:10~1:20g/mL, hydrogen-oxygen
The liquid quality fraction for changing potassium is 10~20%.
Further：It is 4~7 that concentrated hydrochloric acid described in step 2, which adjusts PH,.
Further：The amount of acetophenone -4'- neohesperidins and isovanillin described in step 3 is molar ratio 1:1~
1:3；Solvent is ethyl alcohol, and the amount of addition is 1:100~10:100g/L (ethyl alcohol：Acetophenone -4'- neohesperidins)；Catalyst is four
Hydrogen pyrroles, the amount of addition are 1 with the molar ratio of acetophenone -4'- neohesperidins:1~1:3；The amount that glacial acetic acid is added and acetophenone-
The molar ratio of 4'- neohesperidins is 3:1~1:1.
Further：The mass ratio of neohesperidin and sodium hydroxide described in step 4 is 2:1~4:1, solid-liquid ratio
It is 1:10~1:20(g/mL)；Catalyst is palladium charcoal or Raney's nickel, and the quality of addition is the 1/4~1/7 of neohesperidin quality.
Further：Described in step 4 plus hydrogen pressurized conditions are 2~5 atmospheric pressure, reaction time 2-5h；Dense salt
Acid for adjusting pH is 1~4.
Further：The vacuum drying temperature is 45~60 DEG C, vacuum degree 0.08-0.1MPa.
Compared with prior art, advantage of the invention is that：
1, the present invention is reacted by inverse Michacle and inverse adol, is generated using the aurantiin extracted in Exocarpium Citri Grandis as raw material
Phloroacetophenone -4'- neohesperidins, then aldol condensation occurs with isovanillin and generates neohesperidin, finally under alkaline condition
Hydrogenation obtains neohesperidin dihydrochalcone.
2, preparation method of the invention is simple, purity, the high income of product, and has repeatability, can industrialize.
Description of the drawings：
Fig. 1 is the high-efficient liquid phase chromatogram of novel sweet monosodium glutamate neohesperidin dihydrochalcone.
Fig. 2 is the carbon-13 nmr spectra chromatogram of novel sweet monosodium glutamate neohesperidin dihydrochalcone.
Fig. 3 is the nuclear magnetic resonance spectroscopy chromatogram of novel sweet monosodium glutamate neohesperidin dihydrochalcone.
Case mode is embodied
It is further illustrated the present invention below in conjunction with specific implementation mode, but invents claimed range and be not limited to
Following embodiments.
Embodiment 1
The operating method that the present embodiment prepares novel sweet monosodium glutamate neohesperidin dihydrochalcone is come according to following three step
Implement：The preparation of phloroacetophenone -4'- neohesperidins：It weighs 8.0g aurantiins to be placed in three-necked flask, mass fraction, which is added, is
15% sodium hydroxide or potassium hydroxide 120mL, is passed through N2Noble gas protection is heated to 145~150 DEG C of reflux 2h, is added after cooling
Concentrated hydrochloric acid tune pH to 6.0 has a large amount of yellow-white precipitations to generate, and to 120 DEG C, solid dissolving, natural cooling is precipitated heating mixture
Crystal filters, and ice water washs repeatedly, obtains 5.6g product phloroacetophenone -4'- neohesperidins；
The preparation of neohesperidin：Acetophenone -4'- neohesperidin 4.76g, isovanillin 1.52g are weighed, ethyl alcohol is added
50mL stirs 15min at room temperature, and catalyst nafoxidine 0.71g, glacial acetic acid 0.3g is then added and is passed through N2Noble gas is protected, and 80
DEG C heating 12h, it is cooling that solid is precipitated, it filters and simultaneously washs to obtain faint yellow solid with ethyl alcohol, be dried to obtain 4.7g neohesperidins；
The preparation of neohesperidin dihydrochalcone：It weighs 2.0g sodium hydroxides and 4.0g neohesperidins is dissolved in 40mL water
In, palladium charcoal 0.8g is added, is passed through hydrogen, under 3 atmospheric pressures, waves reaction 3 hours.After reaction, it filters, collects
Filtrate, filtrate adjust pH to 2.0 with concentrated hydrochloric acid.Refrigerator overnight, filtering are placed, further hot water dissolving's recrystallization filters, 60 DEG C
Vacuum drying chamber dries 12h, obtains 3.4g neohesperidin dihydrochalcone, purity >=95.0%.
Embodiment 2
The operating method that the present embodiment prepares novel sweet monosodium glutamate neohesperidin dihydrochalcone is come according to following three step
Implement：The preparation of phloroacetophenone -4'- neohesperidins：It weighs 8.0g aurantiins to be placed in three-necked flask, mass fraction, which is added, is
15% sodium hydroxide or potassium hydroxide 120mL, is passed through N2Noble gas protection is heated to 145~150 DEG C of reflux 2h, is added after cooling
Concentrated hydrochloric acid tune pH to 6.0 has a large amount of yellow-white precipitations to generate, and to 120 DEG C, solid dissolving, natural cooling is precipitated heating mixture
Crystal filters, and ice water washs repeatedly, obtains 5.7g product phloroacetophenone -4'- neohesperidins；
The preparation of neohesperidin：Acetophenone -4'- neohesperidin 4.76g, isovanillin 1.52g are weighed, ethyl alcohol is added
50mL stirs 15min at room temperature, and catalyst nafoxidine 0.71g, glacial acetic acid 0.3g is then added and is passed through N2Noble gas is protected, and 80
DEG C heating 12h, it is cooling that solid is precipitated, it filters and simultaneously washs to obtain faint yellow solid with ethyl alcohol, dry 4.7g obtains neohesperidin；
The preparation of neohesperidin dihydrochalcone：It weighs 2.0g sodium hydroxides and 4.0g neohesperidins is dissolved in 40mL water
In, palladium charcoal 0.8g is added, is passed through hydrogen, under 3 atmospheric pressures, waves reaction 3 hours.After reaction, it filters, collects
Filtrate, filtrate adjust pH to 2.0 with concentrated hydrochloric acid.Refrigerator overnight, filtering are placed, further hot water dissolving's recrystallization filters, 60 DEG C
Vacuum drying chamber dries 12h, obtains 3.5g neohesperidin dihydrochalcones, purity >=95.0%.
Embodiment 3
The operating method that the present embodiment prepares novel sweet monosodium glutamate neohesperidin dihydrochalcone is come according to following three step
Implement：The preparation of phloroacetophenone -4'- neohesperidins：It weighs 8.0g aurantiins to be placed in three-necked flask, mass fraction, which is added, is
15% sodium hydroxide or potassium hydroxide 120mL, is passed through N2Noble gas protection is heated to 145~150 DEG C of reflux 2h, is added after cooling
Concentrated hydrochloric acid tune pH to 6.0 has a large amount of yellow-white precipitations to generate, and to 120 DEG C, solid dissolving, natural cooling is precipitated heating mixture
Crystal filters, and ice water washs repeatedly, obtains 5.7g product phloroacetophenone -4'- neohesperidins；
The preparation of neohesperidin:Acetophenone -4'- neohesperidin 4.76g, isovanillin 1.52g are weighed, ethyl alcohol is added
50mL stirs 15min at room temperature, and catalyst nafoxidine 0.71g, glacial acetic acid 0.3g is then added and is passed through N2Noble gas is protected, and 80
DEG C heating 12h, it is cooling that solid is precipitated, it filters and simultaneously washs to obtain faint yellow solid with ethyl alcohol, dry 4.7g obtains neohesperidin；
The preparation of neohesperidin dihydrochalcone：It weighs 2.0g sodium hydroxides and 4.0g neohesperidins is dissolved in 40mL water
In, palladium charcoal 0.8g is added, is passed through hydrogen, under 3 atmospheric pressures, waves reaction 3 hours.After reaction, it filters, collects
Filtrate, filtrate adjust pH to 2.0 with concentrated hydrochloric acid.Refrigerator overnight, filtering are placed, further hot water dissolving's recrystallization filters, 60 DEG C
Vacuum drying chamber dries 12h, obtains 3.5g neohesperidin dihydrochalcones, purity >=95.0%.
Claims (6)
1. a kind of method preparing sweetener based on Exocarpium Citri Grandis, which is characterized in that include the following steps：
Step 1：Aurantiin sterling is extracted and prepared in Exocarpium Citri Grandis；
Step 2：Aurantiin is proportionally added into KOH solution, nitrogen protection is passed through, it is heated to reflux 2 in 140~150 DEG C~
Salt acid for adjusting pH is added after cooling in 3h, generates a large amount of yellow-white precipitations, and being heated to 110~120 DEG C makes mixture solid dissolve,
Natural cooling 12-24 hours, precipitates crystal, and filters, and ice water washs repeatedly, and it is newly orange to obtain product acetophenone -4'- for vacuum drying
Skin glycosides solid；
Step 3：Appropriate acetophenone -4'- neohesperidins and isovanillin are added in reaction bulb, addition solvent is appropriate, room temperature
Lower stirring a period of time, catalyst then is added and reaction medium glacial acetic acid is appropriate, is heated to reflux for 70-90 DEG C under nitrogen protection
10-18h, it is finally cooling that solid is precipitated, it filters and washs to obtain faint yellow solid with ethyl alcohol, be dried in vacuo, obtain neohesperidin；
Step 4：Neohesperidin obtained by appropriate step 3 is dissolved in the water with sodium hydroxide, addition catalyst is appropriate, is placed in
In reaction kettle, it is passed through hydrogen, in the case where adding lower pressure, stirs or wave reaction a period of time；After reaction, it filters, filtrate
PH is adjusted with concentrated hydrochloric acid；It places refrigerator to stand overnight, filter, product is recrystallized with hot water, and filter cake is dried in vacuum drying chamber
Night obtains sweetener neohesperidin dihydrochalcone.
2. the method for preparing sweetener based on Exocarpium Citri Grandis as described in claim 1, it is characterised in that：Described in step 2
The mass fraction of potassium hydroxide solution is 10-15%, and the solid-liquid ratio of aurantiin and solution is 1:10~1:20g/mL；The acid
For concentrated hydrochloric acid, the pH ranging from 4~7 of adjusting.
3. the method for preparing sweetener based on Exocarpium Citri Grandis such as claim 1, it is characterised in that：Addition second described in step 3
The amount of acyl benzene -4'- neohesperidins and isovanillin is molar ratio 1:1~1:3；The solvent is ethyl alcohol, and ethyl alcohol and second is added
Acyl benzene -4'- neohesperidin amount ratios are 1:100~10:100g/L.
4. the method for preparing sweetener based on Exocarpium Citri Grandis such as claim 1, it is characterised in that：Catalyst described in step 3
For nafoxidine, the amount of addition is 1 with the molar ratio of acetophenone -4'- neohesperidins:1~1:3；The acid is glacial acetic acid, is added
The amount entered and the molar ratio of acetophenone -4'- neohesperidins are 3:1~1:1.
5. the method for preparing sweetener based on Exocarpium Citri Grandis such as claim 1, it is characterised in that：Addition described in step 4 is new
The mass ratio of aurantiamarin and sodium hydroxide is 2:1~4:1, solid-liquid ratio 1:10~1:20(g/mL)；The catalyst is
Palladium charcoal or Raney's nickel, the quality of addition are the 1/4~1/7 of neohesperidin quality；The pressurized conditions are 1~5 atmospheric pressure,
Reaction time is 2-5h；The salt acid for adjusting pH is 1~4.
6. the method for preparing sweetener based on Exocarpium Citri Grandis such as claim 1, it is characterised in that：The vacuum drying temperature
It is 40~50 DEG C, vacuum degree 0.08-0.1MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113367313A (en) * | 2021-06-23 | 2021-09-10 | 安徽银丰药业股份有限公司 | Low-bitter levo-menthol and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104119408A (en) * | 2014-06-25 | 2014-10-29 | 陕西嘉禾植物化工有限责任公司 | Method for synthesizing neohesperidin dihydrochalcone from naringin |
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2018
- 2018-02-06 CN CN201810119807.5A patent/CN108329364A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119408A (en) * | 2014-06-25 | 2014-10-29 | 陕西嘉禾植物化工有限责任公司 | Method for synthesizing neohesperidin dihydrochalcone from naringin |
Non-Patent Citations (2)
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| 彭颖: "《响应面优化化橘红柚皮苷超声辅助提取工艺》", 《食品工业科技》 * |
| 李爱平: "《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》", 15 February 2017 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113367313A (en) * | 2021-06-23 | 2021-09-10 | 安徽银丰药业股份有限公司 | Low-bitter levo-menthol and preparation method thereof |
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Application publication date: 20180727 |