CN111233965A - Glycyrrhetinic acid derivative LGT and preparation method and application thereof - Google Patents
Glycyrrhetinic acid derivative LGT and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C07J63/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by expansion of only one ring by one or two atoms
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
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- A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
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Abstract
The invention discloses a glycyrrhetinic acid derivative LGT and a preparation method and application thereof, and the glycyrrhetinic acid derivative LGT has a structure shown in a general formula I:
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a glycyrrhetinic acid derivative LGT and a preparation method and application thereof.
Background
The active ingredients of licorice include Glycyrrhizin (GL) and Glycyrrhetinic Acid (GA), and GA is the main bioactive ingredient in licorice and is the main metabolite of GL.
A novel food additive of L-carnosine, carnosine is dipeptide composed of β -alanine and histidine, which can be synthesized in animal body, has significant inhibiting effect on lipid oxidation caused by free radicals and metal ions, has the effect of inhibiting fat oxidation and protecting flesh color in meat processing, is used for resisting beef oxidation with phytic acid, is added with 0.9g/kg of carnosine in daily ration to improve flesh color and oxidation stability of skeletal muscle, and has synergistic effect with vitamin E.
The toothpaste is an essential article for daily life, and can be divided into common toothpaste and medicinal toothpaste according to functions, while the antiallergic toothpaste is an important branch of the medicinal toothpaste as a household auxiliary prevention or treatment means for Dentine Hypersensitivity (DH).
At present, a glycyrrhetinic acid derivative LGT serving as a toothpaste desensitizer and a preparation method and application thereof are lacked.
Disclosure of Invention
The invention aims to provide a novel glycyrrhetinic acid derivative LGT serving as a toothpaste desensitizer, and a preparation method and application thereof.
In order to solve the problems in the prior art, the invention provides the following technical scheme: the invention relates to a glycyrrhetinic acid derivative LGT, which has a structure shown in a general formula I:
the preparation method of the glycyrrhetinic acid derivative LGT comprises the following steps:
(1) dissolving glycyrrhetinic acid and succinic anhydride in triethylamine, refluxing for 14-15h, after the reaction is finished, diluting with cold water, adjusting the pH value of the system to 3-4 with hydrochloric acid, filtering to obtain a brownish black solid, washing the precipitate with hot water, and separating a product by column chromatography to obtain a light yellow solid glycyrrhetinic acid acidification product ZKU;
(2) dissolving L-carnosine in distilled water, dissolving an acidification product ZKU of glycyrrhetinic acid in dimethylformamide with the same volume as the distilled water, dropwise adding the acidification product into the system, dropwise adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into the system, reacting at 55-65 ℃ for 20-30h, after the reaction is finished, carrying out vacuum concentration, precipitating for 3-5 times by using acetone, washing the precipitate by using ethanol and ethyl ether in sequence, and preparing the glycyrrhetinic acid derivative LGT.
Further, in the step (1), the molar ratio of the glycyrrhetinic acid to the succinic anhydride is 1: 4.
Further, in the step (1), the molar volume ratio of the glycyrrhetinic acid to the triethylamine is 1:10 mol/l.
Furthermore, in the step (1), the volume ratio of the triethylamine to the cold water is 1: 6.
Further, in the step (1), the volume ratio of ethanol to ethyl acetate is 7:4 in column chromatography.
Further, in the step (2), the mass ratio of the L-carnosine to the glycyrrhetinic acid acidification product ZKU is 226mg:286 mg.
Further, in the step (1), 2.4g (5mmol) of glycyrrhetinic acid and 2.4g (20mmol) of succinic anhydride are dissolved in 50ml of triethylamine and refluxed for 14-15h, after the reaction is finished, the mixture is diluted by 300ml of cold water, the pH value of the system is adjusted to be 3-4 by hydrochloric acid, a brownish black solid is obtained by filtration, hot water washing and precipitation are carried out, column chromatography is carried out, the volume ratio of ethanol to ethyl acetate is 7:4 during the column chromatography, and a product is separated to obtain a pale yellow solid glycyrrhetinic acid acidification product ZKU.
Further, in the step (2), 226mg L-carnosine is dissolved in distilled water, 286mg of glycyrrhetinic acid acidification matter ZKU is dissolved in 30ml of dimethylformamide and is dropwise added into the system, then 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is dropwise added into the system, the reaction is carried out for 20-30h at 55-65 ℃, after the reaction is finished, vacuum concentration is carried out, acetone is used for precipitation for 3-5 times, and the precipitate is washed by acetone, ethanol and ethyl ether in sequence, so that the glycyrrhetinic acid derivative LGT is prepared.
The glycyrrhetinic acid derivative LGT disclosed by the invention is used as a desensitizer to be applied to preparation of toothpaste.
Has the advantages that: the method has the advantages of simple synthesis, mild reaction conditions and excellent performance of the synthesized compound, and can provide a reliable tool for further research on the compound as a toothpaste desensitizer. The product synthesized by the invention is used in toothpaste, and has the effects of relieving the symptoms of gingivitis, such as red swelling and bleeding, and improving the resistance of teeth to external cold, hot, sour and sweet stimulation.
Detailed Description
The present invention is described in more detail below with reference to examples, but it should not be construed that the scope of the present invention is limited to the examples below, and any technologies implemented based on the above contents of the present invention are within the scope of the present invention.
Example 1
The invention relates to a glycyrrhetinic acid derivative LGT, which has a structure shown in a general formula I:
the preparation method of the glycyrrhetinic acid derivative LGT comprises the following steps:
(1) dissolving glycyrrhetinic acid and succinic anhydride in triethylamine, refluxing for 14-15h, after the reaction is finished, diluting with cold water, adjusting the pH value of the system to 3 with hydrochloric acid, filtering to obtain a brownish black solid, washing the precipitate with hot water, and separating the product by column chromatography to obtain a light yellow solid glycyrrhetinic acid acidification substance ZKU; the molar ratio of the glycyrrhetinic acid to the succinic anhydride is 1: 4. The molar volume ratio of the glycyrrhetinic acid to the triethylamine is 1:10 mol/l. The volume ratio of the triethylamine to the cold water is 1: 6. During column chromatography, the volume ratio of ethanol to ethyl acetate is 7: 4.
(2) Dissolving L-carnosine in distilled water, dissolving an acidification product ZKU of glycyrrhetinic acid in 30ml of dimethylformamide, dropwise adding the mixture into the system, dropwise adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into the system, reacting at 55 ℃ for 20 hours, after the reaction is finished, carrying out vacuum concentration, precipitating for 5 times by using acetone, and washing the precipitate by using acetone, ethanol and diethyl ether in sequence to obtain the glycyrrhetinic acid derivative LGT. The mass ratio of the L-carnosine to the glycyrrhetinic acid acidification matter ZKU is 226mg to 286 mg.
The glycyrrhetinic acid derivative LGT disclosed by the invention is used as a desensitizer to be applied to preparation of toothpaste.
Example 2
Example 2 differs from example 1 in that:
the preparation method of the glycyrrhetinic acid derivative LGT comprises the following steps: in the step (1), glycyrrhetinic acid and succinic anhydride are dissolved in triethylamine and refluxed for 15 hours, after the reaction is finished, the mixture is diluted by cold water, the pH value of the system is adjusted to be 4 by hydrochloric acid, a brownish black solid is obtained by filtering, the precipitate is washed by hot water, and a product is separated by column chromatography to obtain a light yellow solid glycyrrhetinic acid acidification matter ZKU.
In the step (2), L-carnosine is dissolved in distilled water, an acidification product ZKU of glycyrrhetinic acid is dissolved in 30ml of dimethylformamide and is dropwise added into the system, then 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is dropwise added into the system, the reaction is carried out for 30h at 65 ℃, after the reaction is finished, vacuum concentration is carried out, acetone is used for precipitation for 3 times, and the precipitate is washed by acetone, ethanol and ether in sequence, so that the glycyrrhetinic acid derivative LGT is prepared.
Example 3
Example 3 differs from example 1 in that:
the preparation method of the glycyrrhetinic acid derivative LGT comprises the following steps: in the step (1), glycyrrhetinic acid and succinic anhydride are dissolved in triethylamine and refluxed for 14 hours, after the reaction is finished, the mixture is diluted by cold water, the pH value of a system is adjusted to 3.5 by hydrochloric acid, brownish black solid is obtained by filtering, hot water is used for washing and precipitating, and a product is separated by column chromatography to obtain a light yellow solid glycyrrhetinic acid acidification compound ZKU.
In the step (2), L-carnosine is dissolved in distilled water, an acidification product ZKU of glycyrrhetinic acid is dissolved in 30ml of dimethylformamide and is dropwise added into the system, then 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is dropwise added into the system, the reaction is carried out for 25 hours at the temperature of 60 ℃, after the reaction is finished, vacuum concentration is carried out, acetone is used for precipitation for 4 times, and the precipitate is washed by acetone, ethanol and ether in sequence, so that the glycyrrhetinic acid derivative LGT is prepared.
Example 4
The preparation method of the glycyrrhetinic acid derivative LGT comprises the following steps: the invention relates to a preparation method of a glycyrrhetinic acid derivative LGT, which comprises the following steps:
in step (1), 2.4g (5mmol) of glycyrrhetinic acid and 2.4g (20mmol) of succinic anhydride are dissolved in 50ml of triethylamine and refluxed for 14-15 h. After the reaction is finished, diluting with 300ml of cold water, adjusting the pH value of the system to 3-4 by using hydrochloric acid, and filtering to obtain a brownish black solid. The precipitate was washed with hot water. Column chromatography V (ethanol): separating the product to obtain an acidification product ZKU of the glycyrrhetinic acid as a light yellow solid, wherein the ratio of V (ethyl acetate) to V (7: 4) is higher;
in the step (2), 226mg of L-carnosine was dissolved in distilled water, 286mg of glycyrrhetinic acid hydrochloride ZKU was dissolved in 30ml of dimethylformamide and added dropwise to the above system, and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride was added dropwise to the above system. Reacting for 20-30h at 55-65 ℃. After the reaction is finished, vacuum concentrating, precipitating with acetone for 3-5 times, and washing the precipitate with acetone, ethanol and diethyl ether in sequence to obtain the glycyrrhetinic acid derivative LGT.
1H NMR(600MHz,DMSO-d6),0.691(3H,s),0.760(3H,s),0.911(3H,s),1.040(6H,s),1.100(3H,s),1.353(3H,s)；2.09(1H,d,J＝0.86Hz),2.33(1H,s),2.40(2H,s),2.53(2H,s),2.65(2H,s),2.9(2H,s),3.0(1H,rn),4.3(1H,m),4.753(1H,s)；5.4(1H,s)；8.33(1H,s),8.40(1H,rn),8.74(1H,s),12.88(1H,s).MS(ESI):779.9([M+H]+).
Test example 1
Through experimental observation, the instant effect and the long-term effect of the glycyrrhetinic acid derivative LGT and the ultra-fast and high-cleanness special-effect anti-sensitivity toothpaste on the dentinal tubule sealing effect are selected, the desensitizer with the best effect is selected, and a theoretical basis is provided for the reasonable clinical application of the desensitizer.
The method comprises the following steps:
140 fresh intact third molars in vitro were collected, prepared into a dentinal hypersensitivity model and then randomly divided into a blank control group (n ═ 20), a glycyrrhetinic acid derivative LGT control group (n ═ 40), an acutangnin group (n ═ 40), and a high-dew group (n ═ 40). The blank control group was coated with distilled water, the remaining three groups were coated with desensitizing agent as required, and 20 samples were randomly drawn from each of the 3 desensitizing agent-coated groups for the brushing experiment. And observing the change of the dentin surface after the desensitizer is coated and after the tooth brushing experiment under a scanning electron microscope, analyzing the pictures of the scanning electron microscope by an image analysis system, calculating the average diameter and the relative area of the mouth of the open dentin tube, and performing statistical analysis on the result by using SPSS 21.0.
As a result:
the mean diameter of the open mouths of the dentinal tubules after application of the desensitizer was statistically different from the population (F788.245, P0.000); the average diameter of the open nozzles of the blank control group is obviously higher than that of the other three groups (P & lt0.000), the average diameter of the open nozzles of the glycyrrhetinic acid derivative LGT control group is obviously lower than that of the other three groups (P & lt0.000), and the average diameter of the open nozzles of the guonine group is not significantly different from that of the high dew cleaning group (P & lt0.139). After the tooth brushing experiment, the average diameter of the open mouth of the dentinal tubule in the three groups of the glycyrrhetinic acid derivative LGT control group, the Yongning group and the high-distillate special-effect anti-allergy toothpaste group is statistically different (F is 574.774, and P is 0.000); the average diameter of the open nozzles of the glycyrrhetinic acid derivative LGT comparative group is obviously lower than that of the Gaogening group (P is 0.000), the average diameter of the open nozzles of the glycyrrhetinic acid derivative LGT comparative group is obviously lower than that of the high-dew group (P is 0.000), and the average diameter of the open nozzles of the Gaogening group is obviously lower than that of the high-dew group (P is 0.008). The relative area of the open mouth of the dentinal tubules was statistically different between the four groups after application of the desensitizer (F5204.798, P0.000); the relative area of the open orifice was significantly higher in the blank than in the remaining three groups (P ═ 0.000),
the relative area of the open nozzles of the glycyrrhetinic acid derivative LGT contrast group is obviously lower than that of the Jieguing group (P is 0.000), the relative area of the open nozzles of the glycyrrhetinic acid derivative LGT contrast group is obviously lower than that of the high-distillate group (P is 0.000), and the relative area of the open nozzles of the Jieguing group is obviously lower than that of the high-distillate group (P is 0.026). After the tooth brushing experiment, the comparative total of the relative area of the open mouth of the dentinal tubule among the glycyrrhetinic acid derivative LGT comparative group, the Yongning group and the high-distillate special-effect anti-allergy toothpaste group is statistically different (F is 337.288,
p ═ 0.000); the relative area of the small open nozzles of the glycyrrhetinic acid derivative LGT contrast group is lower than that of the Jieguing group (P is 0.000), the relative area of the small open nozzles of the glycyrrhetinic acid derivative LGT contrast group is obviously lower than that of the high-distillate group (P is 0.000), and the relative area of the small open nozzles of the Jieguing group is obviously lower than that of the high-distillate group (P is 0.000). The diameter and relative area of each group coated with the desensitizer before and after the tooth brushing experiment were longitudinally compared, and the diameter and relative area of the glycyrrhetinic acid derivative LGT control group had no significant difference before and after the tooth brushing experiment (P ═ 0.066), and the others had significant differences (P < 0.05).
Conclusion
The glycyrrhetinic acid derivative LGT contrast group, the ultra-stable toothpaste and the high-distillate anti-sensitivity toothpaste can effectively seal dentinal tubules, and the sealing effect of the dentinal tubules after a brushing friction experiment is in turn from strong to weak
Glycyrrhetinic acid derivative LGT contrast group, GUGUNING, and GALUJIE antiallergic toothpaste. The immediate desensitizing effect and the long desensitizing effect of the glycyrrhetinic acid derivative LGT contrast group in the three desensitizers are optimal.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the foregoing description only for the purpose of illustrating the principles of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims, specification, and equivalents thereof.
Claims (10)
1. A glycyrrhetinic acid derivative LGT is characterized by having a structure shown in a general formula I:
2. the method for producing glycyrrhetinic acid derivative LGT according to claim 1, characterized by comprising the steps of:
(1) dissolving glycyrrhetinic acid and succinic anhydride in triethylamine, refluxing for 14-15h, after the reaction is finished, diluting with cold water, adjusting the pH value of the system to 3-4 with hydrochloric acid, filtering to obtain a brownish black solid, washing the precipitate with hot water, and separating a product by column chromatography to obtain a light yellow solid glycyrrhetinic acid acidification product ZKU;
(2) dissolving L-carnosine in distilled water, dissolving an acidification product ZKU of glycyrrhetinic acid in dimethylformamide with the same volume as the distilled water, dropwise adding the acidification product into the system, dropwise adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into the system, reacting at 55-65 ℃ for 20-30h, after the reaction is finished, carrying out vacuum concentration, precipitating for 3-5 times by using acetone, washing the precipitate by using ethanol and ethyl ether in sequence, and preparing the glycyrrhetinic acid derivative LGT.
3. The method for producing a glycyrrhetinic acid derivative LGT according to claim 2, wherein: in the step (1), the molar ratio of the glycyrrhetinic acid to the succinic anhydride is 1: 4.
4. The method for producing a glycyrrhetinic acid derivative LGT according to claim 3, wherein: in the step (1), the molar volume ratio of the glycyrrhetinic acid to the triethylamine is 1:10 mol/l.
5. The method for producing glycyrrhetinic acid derivative LGT according to claim 4, wherein: in the step (1), the volume ratio of the triethylamine to the cold water is 1: 6.
6. The method for producing a glycyrrhetinic acid derivative LGT according to claim 5, wherein: in the step (1), the volume ratio of ethanol to ethyl acetate is 7:4 during column chromatography.
7. The method for producing glycyrrhetinic acid derivative LGT according to claim 6, wherein: in the step (2), the mass ratio of the L-carnosine to the glycyrrhetinic acid acidification product ZKU is 226mg:286 mg.
8. The method for producing a glycyrrhetinic acid derivative LGT according to claim 2, wherein: in the step (1), 2.4g (5mmol) of glycyrrhetinic acid and 2.4g (20mmol) of succinic anhydride are dissolved in 50ml of triethylamine and refluxed for 14-15h, after the reaction is finished, the mixture is diluted by 300ml of cold water, the pH value of a system is adjusted to 3-4 by hydrochloric acid, a brownish black solid is obtained by filtration, hot water is used for washing and precipitating, column chromatography is carried out, the volume ratio of ethanol to ethyl acetate is 7:4 during the column chromatography, and a product is separated to obtain a light yellow solid glycyrrhetinic acid acidification product ZKU.
9. The method for producing a glycyrrhetinic acid derivative LGT according to claim 8, wherein: in the step (2), 226mg L-carnosine is dissolved in distilled water, 286mg of glycyrrhetinic acid acidification product ZKU is dissolved in 30ml of dimethylformamide and is dropwise added into the system, then 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is dropwise added into the system, the reaction is carried out for 20-30h at 55-65 ℃, after the reaction is finished, vacuum concentration is carried out, acetone is used for precipitation for 3-5 times, and the precipitation is sequentially washed by acetone, ethanol and ether, so that the glycyrrhetinic acid derivative LGT is prepared.
10. Use of a glycyrrhetinic acid derivative, LGT, according to any one of claims 1 to 9 as a desensitizing agent in the preparation of toothpaste.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115677813A (en) * | 2021-03-25 | 2023-02-03 | 河北中医学院 | Application of compound in TMEM16A agonist |
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2020
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| WO1990006102A1 (en) * | 1988-09-28 | 1990-06-14 | Peptide Technology Limited | Compound and method for the retardation of collagen cross-linking |
| JP2013155166A (en) * | 2012-02-01 | 2013-08-15 | Lion Corp | Dentifrice composition |
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| 董鑫: "三种不同脱敏剂对牙本质小管封闭作用的实验研究", 《中国优秀硕士学位论文全文数据库（电子期刊）医药卫生科技辑》 * |
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| CN115677813A (en) * | 2021-03-25 | 2023-02-03 | 河北中医学院 | Application of compound in TMEM16A agonist |
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Application publication date: 20200605 |