阅读说明：本技术 一种作为护肤品抗氧剂的11-o-罗汉果醇肟酯衍生物以及一种护肤品 (11-O-momordica grosvenori oxime alcohol derivative serving as antioxidant of skin care product and skin care product ) 是由 李伟 黄华学 于 2020-06-01 设计创作，主要内容包括：本发明提供了一种作为护肤品抗氧剂的式(I)所示的11-O-罗汉果醇肟酯衍生物以及一种包括式(I)化合物作为抗氧化剂活性成分的护肤品。将式(I)所示化合物好角鲨烯复配后,作为护肤品的抗氧剂,发挥了协同增效作用,护肤品的抗氧化能力,特别是持久的抗氧化能力显著提高。本发明提供的含式(I)化合物的护肤品,成分天然无害,能够有效保护皮肤,使用后能够明显改善皮肤衰老情况。<Image he="351" wi="700" file="DDA0002517748090000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention provides an 11-O-mogrol oxime ester derivative shown in a formula (I) and a skin care product containing a compound shown in the formula (I) as an antioxidant active ingredient of the skin care product. After the compound shown in the formula (I) and squalene are compounded, the compound is used as an antioxidant of a skin care product, the synergistic interaction effect is exerted, and the oxidation resistance, particularly the lasting oxidation resistance of the skin care product is obviously improved. The skin care product containing the compound shown in the formula (I) provided by the invention has natural and harmless components, can effectively protect the skin, and can obviously improve the skin aging condition after being used.)

1. An 11-O-mogrol oxime ester derivative used as an antioxidant of skin care products has a structural formula shown in a formula (I):

2. a skin care product wherein the antioxidant comprises a compound of formula (I) as defined in claim 1.

3. The skin care product of claim 2 wherein the antioxidant further comprises squalene.

4. The skin care product according to claim 3, wherein the antioxidant comprises the compound represented by the formula (I) and squalene in a mass ratio of 1 to 5: 1-5, preferably 1-2: 1.

5. A skin care product comprises the following raw materials: antioxidant, humectant, emulsifier and auxiliary agent; the antioxidant comprises a compound of formula (I) as described in claim 1 and squalene; wherein the mass ratio of the compound shown in the formula (I) to squalene is 1-5: 1-5, preferably 1-2: 1.

6. The skin care product of claim 5, wherein the skin care product comprises the following raw materials, by weight, 0.5 to 1 part of an antioxidant active ingredient, 5 to 10 parts of a humectant, 1 to 2 parts of an emulsifier, 0 to 5 parts of an auxiliary agent, and 70 to 100 parts of a solvent.

7. A skin care product according to claim 5 or 6 wherein the humectant is selected from at least one of glycerol, propylene glycol, butylene glycol, lauryl alcohol, cetyl alcohol, stearyl alcohol, glyceryl trioctoate, isopropyl palmitate, lactic acid and glycine betaine; and/or

The emulsifier is at least one selected from oleate, polysorbate, alkyl glycoside, glyceryl monostearate, hydrogenated lecithin, magnesium stearate glycerol and potassium lauryl phosphate; and/or

The solvent is water and alcohol, and the mass ratio of the water to the alcohol is 8-10: 1.

8. The skin care product of claim 5 or 6, wherein the auxiliary agent comprises one or more of a lubricant, a stabilizer, a thickener, an antifoaming agent, a plant essential oil, a conditioner, a bactericide, an anti-inflammatory agent and an anti-UV agent;

the lubricant is at least one selected from paraffin, isopropyl myristate, luba gum and butyl stearate; and/or

The thickener is selected from at least one of sodium alginate, methyl glucose dioleate, cetostearyl alcohol, xanthan gum and carboxymethyl cellulose; and/or

The defoaming agent is selected from polydimethylsiloxane; and/or

The plant essential oil is at least one of lavender oil, bergamot oil, peppermint oil, aniseed oil, rose essential oil, lavender essential oil and sophora flower essential oil; and/or

The conditioner is at least one of sodium tollgate, beta-glucan and dipotassium glycyrrhizinate; and/or

The bactericide is selected from at least one of lauric acid monoglyceride, methylparaben, methyl paraben, isopropyl methylphenol, silver-loaded inorganic particles, lysozyme chloride and benzalkonium chloride; and/or

The anti-inflammatory agent is at least one selected from beta-glycyrrhetinic acid, indometacin and guaiacol; and/or

The uvioresistant agent is at least one selected from magnesium ascorbate, arbutin, kojic acid, ethyl methoxycinnamate, octyl salicylate and chlorphenone.

9. A skin care product comprises the following raw materials in parts by weight: 0.3-0.5 part of a compound shown in the formula (I), 0.2-0.4 part of squalene, 3-6 parts of glycerol, 3-6 parts of butanediol, 2-4 parts of propylene glycol, 0.5-2 parts of oleate, 0.3-1 part of polysorbate, 0.2-0.5 part of hydrogenated lecithin, 7-10 parts of absolute ethyl alcohol, 1-2 parts of polydimethylsiloxane, 1-1.5 parts of sodium alginate, 0.1-0.3 part of gum naloxone, 0.3-0.5 part of dipotassium glycyrrhizinate, 0.2-0.5 part of lavender oil, 0.5-1 part of gum naloxone, 0.5-1 part of monoglyceride laurate, 0.2-0.5 part of gum arabic, 0.02-0.1 part of sodium hyaluronate and 70-80 parts of deionized water.

10. A skin care product comprises the following raw materials in parts by weight: 0.3-0.4 part of a compound shown as a formula (I), 0.3-0.4 part of squalene, 3-6 parts of glycerol, 3-5 parts of butanediol, 2-4 parts of propylene glycol, 1-1.5 parts of glycerin monostearate, 0.5-1 part of potassium lauryl phosphate, 0.2-0.5 part of alkyl glycoside, 9-12 parts of absolute ethyl alcohol, 1-2 parts of polydimethylsiloxane, 1-1.5 parts of sodium alginate, 0.1-0.3 part of gum, 0.3-0.5 part of dipotassium glycyrrhizinate, 0.2-0.5 part of rose essential oil, 0.8-1.3 part of monoglyceride laurate, 0.3-0.7 part of isopropyl myristate, 0.02-0.1 part of sodium hyaluronate and 70-80 parts of deionized water.

Technical Field

The invention relates to the field of natural product modification, and in particular relates to a skin care product containing 11-O-mogrol oxime ester derivatives and squalene.

Background

The momordica grosvenori is a unique medicinal and edible plant in China, and is rich in various nutrient elements and bioactive substances such as flavone, polysaccharide, polyphenol and the like. Mogroside, especially mogroside V, is the most popular sweetener at present to replace sucrose, and is very popular in the European and American markets due to the characteristics of high sweetness and low calorie. The biological activity, particularly the antioxidation, of the mogroside is researched in the literature, and the mogroside V is found to have certain antioxidation capability and certain scavenging effect on hydroxyl and superoxide anion free radicals. Generally, mogroside is considered to have antioxidant activity because hydrogen atoms on aglycone have certain activity and can be combined with hydroxyl free radicals, and carbon atoms on saponin parent nucleus can form carbon free radicals and further be oxidized to form peroxy radicals. Aglycone and hydroxyl of tetracyclic triterpenoid saponin are key groups with antioxidant activity. However, the antioxidant mechanism of mogroside compounds has not been studied deeply and needs to be further researched. Mogrol (Mogrol) is aglycone of mogroside IA 1, IE 1, IE, III, IV, IEE, V and siamenoside I; 11-O-Mogrol (11-O-Mogrol) is an aglycone of 11-O-mogroside V, and it has been reported that 11-O-Mogrol has a low antioxidant activity and is not suitable for use as an antioxidant in foods or skin care products.

Squalene is a polyunsaturated hydrocarbon produced in metabolic processes such as human cholesterol synthesis, contains 6 isoprene double bonds, belongs to terpenoids, and contains squalene in a large amount of foods, wherein shark liver oil contains high content, and squalene content in a small amount of vegetable oils such as olive oil and rice bran oil is relatively high. Research shows that squalene has certain antioxidation, has the performance of improving the activity of superoxide dismutase (SOD) in vivo, can effectively inhibit lipid peroxidation, and further helps skin to resist damage caused by ultraviolet irradiation and other oxidation reactions.

With aging, the antioxidant active components in vivo are reduced, the protective function is reduced, and the cumulative damage of free radicals is increased, so that the organism is aged. The antioxidant skin care product sold at present generally contains irritant chemical components, has poor antioxidant effect and cannot meet the requirements of people. Reactive Oxygen Species (ROS) include oxygen ions, radicals, peroxides, and the like, and have strong reactivity due to the presence of unpaired electrons. ROS, which are mainly present in the environment, include oxidative radicals, hydroxyl radicals, superoxide, singlet oxygen. Since human skin is often exposed to the environment, it is vulnerable to various free radicals, causing damage. The antioxidant can protect human skin. However, more antioxidants in skin care are not required for antioxidant properties than food grade antioxidants. Because the antioxidant has strong oxidizability, the antioxidant can react with ROS preferentially to further achieve the purpose of protecting the skin, but if the antioxidant for the skin care product has too strong oxidizability, the antioxidant effect can be lost quickly after the antioxidant is applied to the skin, and the skin cannot be protected for a long time. In addition, since skin care products are often oily creams, antioxidants are also required to have a certain ratio of hydrophilic to lipophilic.

Due to the unique structural characteristics of oxime ester compounds, oxime ester compounds have been widely applied in the fields of biology, medicine, chemical industry, modern agriculture and the like, such as hormones, insecticides, anti-inflammatory agents, photoinitiators and the like. With the continuous and deep scientific research, the oxime ester compound has wider development prospect.

Disclosure of Invention

In order to further expand the application field of the fructus momordicae, in particular to develop a skin care product and a cosmetic containing the fructus momordicae active ingredient, the invention adopts the following technical scheme:

an 11-O-mogrol oxime ester derivative used as an antioxidant of skin care products has a structural formula shown in a formula (I):

the invention also provides a skin care product, wherein the antioxidant of the skin care product comprises the compound shown in the formula (I).

Furthermore, the skin care product provided by the invention also comprises squalene as an antioxidant.

Furthermore, in the skin care product provided by the invention, the mass ratio of the 11-O-mogrol oxime ester derivative shown in the formula (I) to squalene is 1-5: 1-5, preferably, the mass ratio of the 11-O-mogrol oxime ester derivative shown in the formula (I) to squalene is 1-2: 1.

The inventor finds that the oxime ester derivative obtained by carrying out oxime esterification on 11-O-mogrol with weaker antioxidant capacity has obviously improved antioxidant capacity, is more easily accepted by skin, and can effectively play roles in slowing down skin aging and protecting skin. The inventor unexpectedly discovers that the 11-O-mogrol oxime ester derivative shown in the formula (I) and squalene are compounded according to a certain proportion to be used as an antioxidant active ingredient in a skin care product, and the two components play a synergistic effect and can obviously improve the aging condition of skin.

As an embodiment of the present invention, a skin care product comprises the following raw materials: an antioxidant active ingredient, a humectant, an emulsifier and an auxiliary agent; the antioxidant active ingredients comprise 11-O-mogrol oxime ester derivatives shown in a formula (I) and squalene.

Further, the mass ratio of the 11-O-mogrol oxime ester derivative shown in the formula (I) to squalene is 1-5: 1-5, preferably 1-2: 1.

Furthermore, the skin care product comprises the following raw materials, 0.5-1 part of antioxidant active ingredient, 5-10 parts of humectant, 1-2 parts of emulsifier, 0-5 parts of auxiliary agent and 70100 parts of solvent in parts by weight.

In addition to the compounding of the 11-O-mogrol oxime ester derivative and squalene, the antioxidant active ingredient can also comprise levorotatory C, tea polyphenol, lecithin, dibutyl hydroxy toluene (BHT); butyl hydroxyanisole, -tocopherol, beta-carotene and astaxanthin.

The humectant is at least one selected from glycerol, propylene glycol, butylene glycol, lauryl alcohol, cetyl alcohol, stearyl alcohol, glyceryl tricaprylate, isopropyl palmitate, lactic acid and glycine betaine.

The emulsifier is at least one selected from oleate, polysorbate, alkyl glycoside, glyceryl monostearate, hydrogenated lecithin, magnesium stearate and potassium lauryl phosphate.

The solvent is water and alcohol, preferably deionized water and absolute ethyl alcohol, and the mass ratio of the water to the alcohol is 8-10: 1.

Besides the above essential components, the skin care composition of the present invention can also be added with various adjuvants according to the needs within the range of not affecting the effect of the skin care product, and the kinds and the dosage of the adjuvants can be selected by the skilled person according to the needs. The auxiliary agent is selected from a lubricant, a stabilizer, a thickening agent, a defoaming agent, plant essential oil, a conditioning agent, a bactericide, an anti-inflammatory agent, an anti-ultraviolet agent and the like.

The following illustrative descriptions are given for the above-mentioned auxiliaries, but should not be construed as limiting the scope of the present invention:

the lubricant is at least one selected from paraffin, isopropyl myristate, luba gum and butyl stearate;

the thickener is selected from at least one of sodium alginate, methyl glucose dioleate, cetostearyl alcohol, xanthan gum and carboxymethyl cellulose;

the defoaming agent is selected from polydimethylsiloxane;

the plant essential oil is at least one of lavender oil, bergamot oil, peppermint oil, aniseed oil, rose essential oil, lavender essential oil and sophora flower essential oil;

the conditioner is at least one of sodium tollgate, beta-glucan and dipotassium glycyrrhizinate;

the bactericide is at least one selected from lauric acid monoglyceride, methylparaben, methyl paraben, isopropyl methylphenol, silver-loaded inorganic particles, lysozyme chloride and benzalkonium chloride.

The anti-inflammatory agent is at least one selected from beta-glycyrrhetinic acid, indomethacin and guaiacol.

The uvioresistant agent is at least one selected from magnesium ascorbate, arbutin, kojic acid, ethyl methoxycinnamate, octyl salicylate and chlorphenone.

As one embodiment of the invention, the skin care product comprises the following raw materials in parts by weight: 0.3-0.5 part of a compound shown in the formula (I), 0.2-0.4 part of squalene, 3-6 parts of glycerol, 3-6 parts of butanediol, 2-4 parts of propylene glycol, 0.5-2 parts of oleate, 0.3-1 part of polysorbate, 0.2-0.5 part of hydrogenated lecithin, 7-10 parts of absolute ethyl alcohol, 1-2 parts of polydimethylsiloxane, 1-1.5 parts of sodium alginate, 0.1-0.3 part of gum naloxone, 0.3-0.5 part of dipotassium glycyrrhizinate, 0.2-0.5 part of lavender oil, 0.5-1 part of gum naloxone, 0.5-1 part of monoglyceride laurate, 0.2-0.5 part of gum arabic, 0.02-0.1 part of sodium hyaluronate and 70-80 parts of deionized water.

As another embodiment of the invention, the skin care product comprises the following raw materials in parts by weight: 0.3-0.4 part of a compound shown as a formula (I), 0.3-0.4 part of squalene, 3-6 parts of glycerol, 3-5 parts of butanediol, 2-4 parts of propylene glycol, 1-1.5 parts of glycerin monostearate, 0.5-1 part of potassium lauryl phosphate, 0.2-0.5 part of alkyl glycoside, 9-12 parts of absolute ethyl alcohol, 1-2 parts of polydimethylsiloxane, 1-1.5 parts of sodium alginate, 0.1-0.3 part of gum, 0.3-0.5 part of dipotassium glycyrrhizinate, 0.2-0.5 part of rose essential oil, 0.8-1.3 part of monoglyceride laurate, 0.3-0.7 part of isopropyl myristate, 0.02-0.1 part of sodium hyaluronate and 70-80 parts of deionized water.

The invention also provides a preparation method of the skin care product, which comprises the following steps: the skin care product is prepared by mixing the components uniformly according to the formula, heating to 70-80 ℃, and stirring for homogenization to obtain ointment-like substance.

Preferably, the components will be formulated into an oil phase material, which is insoluble in water, and a water phase material, which is soluble in water. Respectively preparing an oil phase mixture and a water phase mixture, adding the oil phase mixture into the water phase mixture at 50-60 ℃, stirring, emulsifying and homogenizing to obtain an ointment-like substance, namely the skin care product.

The beneficial effects obtained by the invention are as follows:

the 11-O-momordica grosvenori oxime alcohol derivative shown in the formula (I) is used as an antioxidant of the skin care product, and after the derivative is compounded with squalene, a synergistic effect is generated, and the antioxidant capacity, particularly the lasting antioxidant capacity of the skin care product is obviously improved. The skin care product containing the compound shown in the formula (I) provided by the invention has natural and harmless components, can effectively protect the skin, and can obviously improve the skin aging condition after being used.

Detailed Description

The present invention will be further described with reference to the following examples.

In the specific embodiment of the present invention, the "parts" are all parts by mass and the% refers to mass fraction, if specifically stated. The adjuvants or chemicals used in the examples of the present invention are commercially available in the usual manner unless otherwise specified.

Preparation examples preparation of compounds of formula (I):

(1) oximation and post-treatment: dissolving 23.8g of 11-O-mogrol in 150ml of absolute ethyl alcohol, adding 3.94g of hydroxylamine phosphate (containing 0.06mol of hydroxylamine) and 11g of diethylamine, carrying out reflux reaction at 85 ℃ for 6 hours, carrying out silica gel TLC (thin layer chromatography) inspection reaction, concentrating under reduced pressure until the solid content of the concentrated solution is 30%, cooling the concentrated solution to 8 ℃, stirring at the speed of 10r/min, crystallizing for 20 hours, carrying out suction filtration, and drying to obtain 22.6g of 11-oxime-mogrol.

(2) Esterification and post-treatment: dissolving 20.2g of 11-oxime-mogrol in 150ml of dichloromethane, adding 8.8g of diethylamine, dropwise adding 8.4g of benzoyl chloride at-10 ℃, and stirring at 0 ℃ for reacting for 6 hours; and after the silica gel TLC detection reaction is finished, pouring the reaction solution into ice water, separating the liquid, collecting an organic layer, washing the organic layer to be neutral by using water, concentrating the organic layer under reduced pressure until the solid content is 20%, adding 50g of column chromatography silica gel into the concentrated solution, uniformly stirring, and drying to constant weight to obtain the sample-mixing silica gel.

(3) Silica gel column chromatography separation: adding the sample-mixed silica gel slowly and uniformly above a silica gel column filled with silica gel in advance (the dosage of the silica gel in the silica gel column is 320g, the height-diameter ratio of the silica gel column is 5: 1), paving and compacting, eluting the silica gel column by using 4BV eluent (petroleum ether: ethyl acetate: 11: 1) at the eluting flow rate of 1 BV/h, collecting eluent, concentrating and drying to obtain 18.17g of 11-oxime benzyl ester-mogrol, the purity of which is 98.6 percent and the yield of which is 61.2 percent.

¹H NMR(CDCl₃)：1.13-1.21(m,15H),1.24-1.26(m,11H),1.29(q,2H)，1,43-1.47(m,5H),1.65(t，1H)，1.92(d,2H)1.97(t,1H)3.23(t，1H)，3.28(t,1H),,5.37(s,1H)，7.47(dd,2H),.7.60(t,1H),8.13(d,2H)。Anal.Calcd.for C₃₇H₅₅NO₅:C.74.82,H.9.34,N.2.36,O.13.48。m/z:593.52,Found:593.76。