CN103772451B - Astacin derivative and preparation method thereof - Google Patents
Astacin derivative and preparation method thereof Download PDFInfo
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- CN103772451B CN103772451B CN201410045776.5A CN201410045776A CN103772451B CN 103772451 B CN103772451 B CN 103772451B CN 201410045776 A CN201410045776 A CN 201410045776A CN 103772451 B CN103772451 B CN 103772451B
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Abstract
The invention provides an astacin derivative. The astacin derivative is prepared by the following steps: adding a compound for providing succinic acid radicals into astacin or an organic liquid in which the astacin is dissolved, carrying out a heating reaction, adding water for stirring after the reaction is ended, standing and precipitating, and collecting the precipitate; adding sugar-based molecules into the liquid of the compound dissolved with the precipitate, and connecting with the sugar-based molecules through an esterification reaction. The astacin bisuccinic acid sugar ester derivatives prepared by the method can serve as feed additives in industries of aquatic products and livestock and poultry, can serve as food coloring agents to be used for coloring in industries such as grains, meat products and aquatic products, can be used for coloring and processing in industries in pharmaceuticals and cosmetics and can serve as functional ingredients to be used for developing health-care foods. Due to high water solubility, the application range of the astacin is greatly widened. The water dispersibility of the prepared astacin bisuccinic acid sugar ester derivative is enhanced compared with the astacin, and the application field is widened.
Description
Technical field
The invention belongs to active substance preparing technical field, be specifically related to two succsinic acid glycolipid derivant of a kind of astacin and preparation method thereof.
Background technology
Astacin (Astacene, 3,3 '-dihydroxy-2,3,2 ', 3 '-tetradehydro-b, b '-carotene-b, b-dione) be also referred to as astacene, be a kind of non-vitamin a source xenthophylls, belong to carotenoid, its structural formula is as shown in (II):
Astacin has the protection of painted, anti-oxidant, light, promotes the several functions such as breeding, is very subject to the concern of the industries such as domestic and international food, medicine, makeup, aquaculture.But astacin is as a kind of carotenoids material, and pole is insoluble in water, thus greatly limit its investigation and application in aqueous phase solution.Meanwhile, because astacin is water-soluble low, its specific absorption in animal body and bioavailability is caused to reduce.This makes the dispersity improved in the water-soluble or aqueous phase solution of astacin become the key of its research.
At present normal adopt the means such as emulsification or micro encapsulation to increase it is water-soluble.Patent ZL200810044646.4 discloses the preparation method of stable water-soluble carotenoid dry powder, this invention is by the organic solution of the acetone or Virahol that are dissolved with carotenoid composition, join under fully stirring in the aqueous phase solution containing tensio-active agent and stable auxiliary composition and fully mix, then the organic solvent in this mixing solutions is removed, add the assistant formation auxiliary material of carotenoid composition quality 1 ~ 12 times more wherein, and spraying dry after stirring, obtain powder-like product.But the product that the method obtains, when being soluble in the aqueous phase solution, exists transparency not good, or long-time placement causes the problems such as poor stability.
Summary of the invention
The object of the present invention is to provide a kind of astacin derivative and preparation method thereof, i.e. a kind of astacin derivative of polymer polarity, improve the water-fast shortcoming of astacin itself, thus make up the deficiencies in the prior art.
First the present invention provides a kind of astacin derivative, and its chemical general formula is:
Wherein, Sugar is any one or several in glucose, fructose, semi-lactosi, lactose or gentiobiose.
The preparation method of derivative of the present invention, its step is as follows:
1) first astacin and amber acid radical react, and generate the compound of following chemical structural formula;
Concrete steps are as follows: to astacin or dissolved astacin organic solution in add and provide the compound of amber acid radical to carry out reacting by heating, add water after reaction terminates and stir, staticly settle, collecting precipitation thing;
2) in the solution being dissolved with compound prepared by step 1), add glycosyl molecule, connect upper glycosyl molecule by esterification, make astacin derivative.
The wherein organic solution of step 1) is one or more in acetone, tetrahydrofuran (THF), dioxy six alkane;
The compound providing amber acid radical in step 1), is preferably succinyl oxide;
Step 2) in solution, be preferably volume fraction be the ethanolic soln of 50% ~ 95%;
Glycosyl molecule is one or more in glucose, fructose, semi-lactosi, lactose, gentiobiose.
The purification process of the astacin derivative that the present invention also provides aforesaid method to prepare, is add precipitation agent by the solution being dissolved with astacin derivative prepared by the method for stating, by water dissolution after collecting precipitation, obtains the astacin derivative aqueous solution; Again the aqueous solution is dehydrated, obtain the astacin derivative of purifying.
Precipitation agent is one or more in acetone, tetrahydrofuran (THF), Virahol, pyridine, ethylene glycol, alcohol ether.
The two succsinic acid glycolipid derivant of astacin prepared by the inventive method can be used as the fodder additives such as aquatic products, livestock and poultry; The painted of the industry processing such as grain, meat product, fishery products can be used for as food colorant; The processing that may be used for the industry such as pharmaceuticals and makeup is painted; Can be used as the exploitation of functional ingredient for protective foods.Because it is good water-soluble, substantially increase the range of application of astacin.The two succsinic acid glycolipid derivant of astacin prepared by the present invention strengthens compared with the water dispersible of astacin, expands its Application Areas.The present invention's astacin reacts with succinyl oxide, carbohydrate ligands successively, obtains a kind of glycolipid derivant, and each radical moiety interacts maybe can produce synergistic function, strengthens biological activity.Method technique of the present invention is simple, and reaction conditions is gentle, and product is easily separated, make whole reaction process environmental protection, consume energy low.
Accompanying drawing explanation
Fig. 1: the preparation flow figure of derivative of the present invention; Wherein, Sugar is one or more in glucose, fructose, semi-lactosi, lactose and gentiobiose.
Fig. 2: the chemical structural formula of the two succsinic acid glucose ester derivative of astacin of the embodiment of the present invention 1.
Fig. 3: the chemical structural formula of the two succsinic acid fructose ester derivative of astacin of the embodiment of the present invention 2.
Fig. 4: the chemical structural formula of the two succsinic acid lactose ester derivative of astacin of the embodiment of the present invention 3.
Fig. 5: the chemical structural formula of the two succsinic acid semi-lactosi ester derivative of astacin of the embodiment of the present invention 4.
Fig. 6: the two succsinic acid gentiobiose ester derivative chemical structural formula of astacin of the embodiment of the present invention 5.
Fig. 7: the two succsinic acid gentiobiose ester derivative thin-layer chromatogram of astacin of the present invention.
Fig. 8: the two spectral scan figure of succsinic acid gentiobiose ester derivative under wavelength region is 200nm ~ 800nm of astacin of the present invention.
Embodiment
The present invention utilizes astacin, succinyl oxide and carbohydrate ligands to prepare the two succsinic acid glycolipid derivant of astacin, improves its water soluble characteristic, is conducive to the range of application expanding astacin.The sugar unit such as glucose, fructose itself does not possess biological activity usually, but after utilizing acid to carry out esterification to it, or its biological activity has mutual synergism.
Two succsinic acid glycolipid derivant of astacin of the present invention and preparation method thereof, concrete steps are as follows:
Raw material: with astacin powder or with the astacin solution of specific organic solvent dissolution for raw material, structural formula is such as formula (II);
1) hydroxy esterification: add succinyl oxide in raw material, the mol ratio of astacin and succinyl oxide is 1:1 ~ 1:20, heating, and temperature controls at 10 ~ 100 DEG C, reaction 0.5 ~ 12h; Add water after having reacted to stir, staticly settle, collected by filtration thing, obtain hydroxy esterification product (III);
Because succinyl oxide is a kind of cyclic acid anhydride, its hydroxyl is connected, and therefore it and hydroxyl reaction product exist with the form of dibasic acid monoester, and introduce a hydroxy-acid group.After reaction, by adding water in reaction system, make the two succinate Precipitation of the astacin of generation.
2) carboxyl esterification: the product (III) step (1) obtained and specific sugar unit react in ethanol/water system, the addition of sugar unit is 1 ~ 10 times of molar weight of above-mentioned product (III), temperature controls at 10 ~ 100 DEG C, reaction 0.5 ~ 12h, after having reacted, in reaction system, add precipitation agent, collecting precipitation, then use water dissolution, obtain the astacin derivative aqueous solution;
The solution that step (2) obtains is dehydrated, obtains the two succsinic acid glycolipid derivant of astacin.
Below in conjunction with specific embodiment, method of the present invention is described in detail.
The preparation of the two succsinic acid glucose ester derivative of embodiment 1 astacin
Take 1g astacin powder, add the succinyl oxide of 3 times of molar weights, be heated to 50 DEG C, reaction 2h; Reacted in backward reaction system and slowly added water stirring, treat that it occurs precipitation, collected by filtration thing, obtains hydroxy esterification product; The hydroxy esterification product obtained is dissolved in 80% ethanol, adds the glucose of 3 times of molar weights, under 50 DEG C of conditions, reaction 2h, after having reacted, slowly adds acetone to Precipitation in reaction system, collecting precipitation, then uses water dissolution, obtains the astacin derivative aqueous solution; Dehydrate, obtain the two succsinic acid glucose ester derivative of astacin, its chemical structural formula as shown in Figure 2, compound IV.
The preparation of the two succsinic acid fructose ester derivative of embodiment 2 astacin
Take the acetone soln that 10mL contains 0.1g astacin, add the succinyl oxide of 4 times of molar weights, be heated to 60 DEG C, reaction 1.5h; Reacted in backward reaction system and slowly added water stirring, treat that it occurs precipitation, collected by filtration thing, obtains hydroxy esterification product; The hydroxy esterification product obtained is dissolved in 95% ethanol, adds the fructose of 2 times of molar weights, under 65 DEG C of conditions, reaction 1h, after having reacted, slowly adds ethylene glycol to Precipitation in reaction system, collecting precipitation, then uses water dissolution, obtains the astacin derivative aqueous solution; Dehydrate, obtain the two succsinic acid fructose ester derivative of astacin, its chemical structural formula as shown in Figure 3, compound V.
The preparation of the two succsinic acid lactose ester derivative of embodiment 3 astacin
Take the dioxy six alkane solution that 1L contains 10g astacin, add the succinyl oxide of 7 times of molar weights, be heated to 40 DEG C, reaction 8h; Reacted in backward reaction system and slowly added water stirring, treat that it occurs precipitation, collected by filtration thing, obtains hydroxy esterification product; The hydroxy esterification product obtained is dissolved in 75% ethanol, adds the lactose of 8 times of molar weights, under 75 DEG C of conditions, reaction 4h, after having reacted, slowly adds tetrahydrofuran (THF) to Precipitation in reaction system, collecting precipitation, then uses water dissolution, obtains the astacin derivative aqueous solution; Dehydrate, obtain the two succsinic acid lactose ester derivative of astacin, its chemical structural formula as shown in Figure 3, compound VI.
The preparation of the two succsinic acid semi-lactosi ester derivative of embodiment 4 astacin
Take the tetrahydrofuran solution that 10mL contains 0.5g astacin, add the succinyl oxide of 5 times of molar weights, be heated to 90 DEG C, reaction 1h; Reacted in backward reaction system and slowly added water stirring, treat that it occurs precipitation, collected by filtration thing, obtains hydroxy esterification product; The hydroxy esterification product obtained is dissolved in 90% ethanol, adds the semi-lactosi of 7 times of molar weights, under 70 DEG C of conditions, reaction 3h, after having reacted, slowly adds acetone to Precipitation in reaction system, collecting precipitation, then uses water dissolution, obtains the astacin derivative aqueous solution; Dehydrate, obtain the two succsinic acid semi-lactosi ester derivative of astacin, its chemical structural formula as shown in Figure 3, compound VI I.
The preparation of the two succsinic acid gentiobiose ester derivative of embodiment 5 astacin
Take the acetone soln that 100mL contains 4g astacin, add the succinyl oxide of 6 times of molar weights, be heated to 100 DEG C, reaction 0.5h; Reacted in backward reaction system and slowly added water stirring, treat that it occurs precipitation, collected by filtration thing, obtains hydroxy esterification product; The hydroxy esterification product obtained is dissolved in 70% ethanol, adds the gentiobiose of 6 times of molar weights, under 90 DEG C of conditions, reaction 0.5h, after having reacted, slowly adds alcohol ether to Precipitation in reaction system, collecting precipitation, then uses water dissolution, obtains the astacin derivative aqueous solution; Dehydrate, obtain the two succsinic acid gentiobiose ester derivative of astacin, its chemical structural formula as shown in Figure 3, compound VI II.
It is red-purple or brick-red powder that embodiment prepares the two succsinic acid gentiobiose ester derivative of astacin, get the two succsinic acid gentiobiose ester derivative of astacin prepared by astacin sample, the two succsinic acid of astacin and the present embodiment respectively, carry out thin-layer chromatographic analysis, in this, as the foundation to derivative qualitative analysis, choose normal hexane: acetone (4:1) is as developping agent, obtain thin-layer chromatogram as shown in Figure 7, by calculating R
fvalue can be found out, astacin after reacting with succsinic acid, two succinic acid derivative (structural formula as I II) R of the astacin obtained
fvalue obviously reduces, illustrates derivative polarity comparatively astacin increase, the two succinic acid derivative of astacin reacts with gentiobiose further, the astacin obtained pair succsinic acid gentiobiose ester derivative (structural formula as shown in Figure 6, compound VI II) R
fvalue reduces further, illustrates that polarity increases further.Within the scope of 200nm ~ 800nm, POP scanning is carried out to derivative prepared by this embodiment, the spectrogram obtained as shown in Figure 8, show it in spectrogram has two places to absorb within the scope of 200nm ~ 800nm, and main absorption peak is 486nm, and another absorption peak is positioned at 383nm place.
Above embodiment specific organic solvent used can be one or more the mixture of acetone, tetrahydrofuran (THF) and dioxy six in alkane; Discrete cell used is one or more in glucose, fructose, semi-lactosi, lactose and gentiobiose; Precipitation agent used is one or more in acetone, tetrahydrofuran (THF), Virahol, pyridine, ethylene glycol and alcohol ether.Its concrete consumption and relevant operational parameter should do suitable adjustment depending on particular case.
Astacin and derivative thereof the dispersivity test in aqueous phase solution: under 25 DEG C of conditions, take the aqueous solution as solvent, utilize high pressure liquid chromatography (HPLC), carried out dispersivity test to the derivative of astacin and preparation thereof, correlation data is listed as follows (table 1):
Table 1: the dispersity of derivative in aqueous phase liquid of astacin and preparation thereof
Note 1.: Compound II per is astacin, compound III is the two succinic acid derivative of astacin, compound IV is the two succsinic acid glucose ester derivative of astacin, compound V is the two succsinic acid fructose ester derivative of astacin, compound VI is the two succsinic acid lactose ester derivative of astacin, compound VI I is the two succsinic acid semi-lactosi ester derivative of astacin, and compound VI II is the two succsinic acid gentiobiose ester derivative of astacin.
Note 1.:
*for response value is not obvious.
Result shows, compared with raw material astacin, the dispersity of astacin derivative in aqueous phase solution synthesized by the present invention is significantly improved, i.e. water-soluble increase.These results suggest that the water-soluble of astacin derivative prepared by the present invention significantly improves, solve because solubleness is limited and limit its investigation and application problem in aqueous phase solution.The two succsinic acid glycolipid derivant of the standby astacin of the present invention can be used as the fodder additives such as aquatic products, livestock and poultry; The painted of the industry processing such as grain, meat product, fishery products can be used for as food colorant; The processing that may be used for the industry such as pharmaceuticals and makeup is painted.Result of use shows, it can effectively replace existing food colorant, and does not have toxic side effect.
Claims (4)
1. an astacin derivative, is characterized in that, the chemical general formula of described astacin derivative is:
Wherein, Sugar is any one in glucose, fructose, semi-lactosi, lactose or gentiobiose.
2. the preparation method of astacin derivative according to claim 1, its step is as follows:
1) to astacin or dissolved astacin organic solution in add succinyl oxide and carry out reacting by heating, add water after reaction terminates and stir, staticly settle, collecting precipitation thing, generate the compound of following chemical structural formula;
The solvent of described organic solution is any one in acetone, tetrahydrofuran (THF), dioxy six alkane;
2) step 1 is being dissolved with) add glycosyl molecule in the solution of compound prepared, connect upper glycosyl molecule by esterification, make astacin derivative;
Described glycosyl molecule is any one in glucose, fructose, semi-lactosi, lactose, gentiobiose;
The solvent of described solution to be volume fraction be 50% ~ 95% ethanolic soln.
3. the purification process of an astacin derivative according to claim 1, it is characterized in that, described purification process is after method according to claim 2 makes astacin derivative, precipitation agent is added by the solution of dissolving astacin derivative, by water dissolution after collecting precipitation, obtain the astacin derivative aqueous solution; Again the aqueous solution is dehydrated, obtain the astacin derivative of purifying; Described precipitation agent is any one in acetone, tetrahydrofuran (THF), Virahol, pyridine, ethylene glycol, alcohol ether.
4. astacin derivative according to claim 1 is preparing aquatic products, additive for farm animal feed, the application in grain, meat product, fishery products tinting material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367837A (en) * | 2007-08-17 | 2009-02-18 | 中国科学院海洋研究所 | Astaxanthin phosphoric acid ester derivant and preparation thereof |
| CN102341006A (en) * | 2009-03-05 | 2012-02-01 | 巴斯夫欧洲公司 | Powdered compositions of astaxanthin derivatives II |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367837A (en) * | 2007-08-17 | 2009-02-18 | 中国科学院海洋研究所 | Astaxanthin phosphoric acid ester derivant and preparation thereof |
| CN102341006A (en) * | 2009-03-05 | 2012-02-01 | 巴斯夫欧洲公司 | Powdered compositions of astaxanthin derivatives II |
Non-Patent Citations (3)
| Title |
|---|
| 《Plasma appearance and tissue accumulation of non-esterified, free astaxanthin in C57BLy6 mice after oral dosing of a disodium disuccinate diester of astaxanthin (HeptaxTM)》;Lori A. Showalter;《Comparative Biochemistry and Physiology》;20040331;第137卷(第3期);Fig 1 * |
| Henry L. Jackson.《Synthesis, characterization, and direct aqueous superoxide anion scavenging of a highly water-dispersible astaxanthin-amino acid conjugate》.《Bioorganic & * |
| Medicinal Chemistry Letters》.2004,第14卷(第15期),3985-3991. * |
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