Silanized phytosphingosine as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of chemical synthesis, and particularly relates to silanized phytosphingosine as well as a preparation method and application thereof. The preparation method comprises the following steps: S1, dissolving phytosphingosine in a solvent to obtain a mixed solution; s2, heating the mixed solution, adding double-end epoxy silicone oil, and carrying out a heat preservation reaction; s3, after the heat preservation reaction is completed, taking out a reaction mixed solution, and carrying out rotary evaporation, so that the solvent is completely volatilized to obtain silanized phytosphingosine; the molar ratio of the phytosphingosine to the double-end epoxy silicone oil is 1: (0.5-0.6). The preparation method provided by the invention has the advantages of simplicity, capability of realizing industrial batch production, high utilization rate of phytosphingosine and high yield of silanized phytosphingosine, and the obtained silanized phytosphingosine can be dissolved in various oils and fats at normal temperature.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a silylated phytosphingosine and a preparation method and application thereof. Background Art

[0002] Phytosphingosine is scientifically known as 2-amino-1,3,4-octadecanetriol, and is a sphingolipid compound. As one of the components of the cell membrane, phytosphingosine is a precursor of ceramide naturally present in the surface layer of the skin, and as a signaling lipid molecule, it participates in regulating various signal transduction processes such as cell growth, differentiation, aging, and programmed cell death.

[0003] Phytosphingosine is a natural antibacterial lipid derived from the skin. It has a significant inhibitory effect on harmful bacteria such as Propionibacterium acnes, Malassezia and Candida albicans. At the same time, phytosphingosine is a core contributor to maintaining the stability of the skin barrier. It can promote the expression of TGase1 (transglutaminase 1), promote the formation of keratin capsule, and mature keratinocytes. It can also promote the expression of Caspase-14 (caspase-14) and BLMH (bleomycin hydrolase), thereby promoting the degradation of filaggrin into a natural moisturizing factor. It has high application value in the field of cosmetics.

[0004] However, phytosphingosine is neither soluble in water nor soluble in the absolute part of the cosmetics quasi-grease (such as vegetable oil, animal fat, mineral oil and silicone oil, etc.), and its application in cosmetics is greatly restricted. In order to overcome the solubility problem of phytosphingosine in grease in the prior art, it is prepared into nano liposomes, such as the Chinese patent of publication number CN105496886B discloses a phytosphingosine skin care lotion, and the technical scheme prepares nano liposomes by adding cholesterol and hydrogenated lecithin, improves the affinity of phytosphingosine and ceramide to oil phase, and absorption effect is better. However, the preparation of nano liposomes usually requires complicated process and technology, resulting in relatively high production cost. Summary of the invention

[0005] In view of the above problems, the present invention provides a silylated phytosphingosine and a preparation method and application thereof. The preparation method of the silylated phytosphingosine provided by the present invention has the advantages of being simple, capable of industrialized batch production, high utilization rate of phytosphingosine, and high yield of silylated phytosphingosine. The obtained silylated phytosphingosine can be dissolved in various oils and fats at room temperature.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0007] The present invention provides a method for preparing silylated phytosphingosine, comprising the following steps:

[0008] S1. dissolving phytosphingosine in a solvent to obtain a mixed solution;

[0009] S2, heating the mixed solution, adding double-ended epoxy silicone oil to carry out heat preservation reaction;

[0010] S3. After the heat preservation reaction is completed, the reaction mixture is taken out and subjected to rotary evaporation to completely evaporate the solvent to obtain silylated phytosphingosine; the molar ratio of the phytosphingosine to the double-terminal epoxy silicone oil is 1:0.5-0.6.

[0011] In some preferred embodiments, the molar ratio of the phytosphingosine to the double-terminal epoxy silicone oil is 1:0.55-0.6.

[0012] Most preferably, the molar ratio of the phytosphingosine to the double-terminal epoxy silicone oil is 1:0.6.

[0013] In some preferred embodiments, the solvent is selected from at least one of methanol, ethanol, chloroform and dimethyl sulfoxide, preferably ethanol.

[0014] In some preferred embodiments, phytosphingosine is dissolved in a solvent by heating.

[0015] In some preferred embodiments, the mass ratio of phytosphingosine to the solvent is 1:8-12, preferably 1:10.

[0016] In some preferred embodiments, the reaction temperature of the insulation reaction is 65-100° C., and the reaction time is 6-12 h.

[0017] In some preferred embodiments, the reaction temperature of the insulation reaction is 85-100° C., and the reaction time is 9-12 h.

[0018] Most preferably, the reaction temperature of the insulation reaction is 100° C. and the reaction time is 12 h.

[0019] The second aspect of the present invention provides silylated phytosphingosine obtained by the preparation method of the silylated phytosphingosine.

[0020] The third aspect of the present invention provides the use of the silylated phytosphingosine obtained by the preparation method of the silylated phytosphingosine in cosmetics or skin care products.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The preparation method of silylated phytosphingosine provided by the present invention has the advantages of being simple, capable of industrialized mass production, having a high utilization rate of phytosphingosine and a high yield of silylated phytosphingosine; the obtained silylated phytosphingosine can be dissolved in various oils and fats at room temperature, thereby expanding the application of phytosphingosine in cosmetics; and the silylated phytosphingosine can increase its slipperiness due to the introduction of silicone oil, thereby improving the skin feel of the cosmetics. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is the H NMR spectrum of the silylated sphingosine of Example 1;

[0024] Figure 2 is the H NMR spectrum of the silylated sphingosine of Example 2;

[0025] Figure 3 is the H NMR spectrum of the silylated sphingosine of Example 3;

[0026] Figure 4 is the H NMR spectrum of the silylated sphingosine of Example 4;

[0027] Figure 5 is the H NMR spectrum of the silylated sphingosine of Example 5;

[0028] Figure 6 is the H NMR spectrum of the silylated sphingosine of Example 6;

[0029] Figure 7 is the H NMR spectrum of the silylated sphingosine of Example 7;

[0030] Figure 8 The solubility diagram of silylated sphingosine and phytosphingosine in caprylic / capric triglyceride of Example 3 and Comparative Examples 1-2;

[0031] Fig. 9 The solubility diagram of silylated sphingosine and phytosphingosine in white oil of Example 3 and Comparative Examples 1-2 is shown;

[0032] Fig.10 The solubility diagram of silylated sphingosine and phytosphingosine in polydimethylsiloxane of Example 3 and Comparative Examples 1-2;

[0033] Fig.11 This is a solubility diagram of silylated sphingosine of Example 3 and Comparative Examples 1-2 and phytosphingosine in sunflower seed oil;

[0034] Figure 8-Figure 11 In the figure, a is Example 3, b is Comparative Example 1, c is Comparative Example 2, and d is phytosphingosine. DETAILED DESCRIPTION

[0035] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0036] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0037] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0038] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0039] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0040] In the following examples and comparative examples, unless otherwise specified, all raw materials used were commercially available or prepared by conventional methods in the art.

[0041] Among them, the molecular weight of the double-terminal epoxy silicone oil is 2200, purchased from Guangzhou Siluoke New Materials Co., Ltd., model 3592F2, epoxy equivalent 900;

[0042] Phytosphingosine was purchased from Guangzhou Xufan Trading Co., Ltd., model number P0101-S2308001;

[0043] The other silicone oils in the comparative example were purchased from Aladdin, the average molecular weight of the dual-terminal amino silicone oil was 2500, and the average molecular weight of the dual-terminal hydroxyl silicone oil was 2000.

[0044] Example 1

[0045] The preparation method of silylated phytosphingosine is as follows:

[0046] S1. Add 1.5875 g of phytosphingosine powder to 15.875 g of ethanol, heat to 60° C., stir and mix, and obtain a mixed solution after it is fully dissolved;

[0047] S2, the mixed solution was heated to 85°C, 5.5 g of double-ended epoxy silicone oil was added and the mixture was kept warm for 9 hours;

[0048] S3. After the heat preservation reaction is completed, the reaction mixture is taken out and the ethanol is completely evaporated by rotary evaporation for 2 hours to obtain silylated phytosphingosine.

[0049] Example 2

[0050] The preparation method of silylated phytosphingosine is as follows:

[0051] S1. Add 1.5875 g of phytosphingosine powder to 15.875 g of ethanol, heat to 60° C., stir and mix, and obtain a mixed solution after it is fully dissolved;

[0052] S2, the mixed solution was heated to 85°C, 6.05 g of double-ended epoxy silicone oil was added and the mixture was kept warm for 9 hours;

[0053] S3. After the heat preservation reaction is completed, the reaction mixture is taken out and the ethanol is completely evaporated by rotary evaporation for 2 hours to obtain silylated phytosphingosine.

[0054] Example 3

[0055] The preparation method of silylated phytosphingosine is as follows:

[0056] S1. Add 1.5875 g of phytosphingosine powder to 15.875 g of ethanol, heat to 60° C., stir and mix, and obtain a mixed solution after it is fully dissolved;

[0057] S2, the mixed solution was heated to 100°C, 6.6 g of double-ended epoxy silicone oil was added and the mixture was kept warm for 12 h;

[0058] S3. After the heat preservation reaction is completed, the reaction mixture is taken out and the ethanol is completely evaporated by rotary evaporation for 2 hours to obtain silylated phytosphingosine.

[0059] Example 4

[0060] The preparation method of silylated phytosphingosine is as follows:

[0061] S1. Add 1.5875 g of phytosphingosine powder to 15.875 g of ethanol, heat to 60° C., stir and mix, and obtain a mixed solution after it is fully dissolved;

[0062] S2, the mixed solution was heated to 65°C, 6.05 g of double-ended epoxy silicone oil was added and the mixture was kept warm for 9 hours;

[0063] S3. After the heat preservation reaction is completed, the reaction mixture is taken out and the ethanol is completely evaporated by rotary evaporation for 2 hours to obtain silylated phytosphingosine.

[0064] Example 5

[0065] The preparation method of silylated phytosphingosine is as follows:

[0066] S1. Add 1.5875 g of phytosphingosine powder to 15.875 g of ethanol, heat to 60° C., stir and mix, and obtain a mixed solution after it is fully dissolved;

[0067] S2, the mixed solution was heated to 100°C, 6.05 g of double-ended epoxy silicone oil was added and the mixture was kept warm for 9 hours;

[0068] S3. After the heat preservation reaction is completed, the reaction mixture is taken out and the ethanol is completely evaporated by rotary evaporation for 2 hours to obtain silylated phytosphingosine.

[0069] Example 6

[0070] The preparation method of silylated phytosphingosine is as follows:

[0071] S1. Add 1.5875 g of phytosphingosine powder to 15.875 g of ethanol, heat to 60° C., stir and mix, and obtain a mixed solution after it is fully dissolved;

[0072] S2, the mixed solution was heated to 85°C, 6.05 g of double-ended epoxy silicone oil was added and the mixture was kept warm for 6 hours;

[0073] S3. After the heat preservation reaction is completed, the reaction mixture is taken out and the ethanol is completely evaporated by rotary evaporation for 2 hours to obtain silylated phytosphingosine.

[0074] Example 7

[0075] The preparation method of silylated phytosphingosine is as follows:

[0076] S1. Add 1.5875 g of phytosphingosine powder to 15.875 g of ethanol, heat to 60° C., stir and mix, and obtain a mixed solution after it is fully dissolved;

[0077] S2, the mixed solution was heated to 85°C, 6.05 g of double-ended epoxy silicone oil was added and the mixture was kept warm for 12 hours;

[0078] S3. After the heat preservation reaction is completed, the reaction mixture is taken out and the ethanol is completely evaporated by rotary evaporation for 2 hours to obtain silylated phytosphingosine.

[0079] The silylated phytosphingosine prepared in Example 1-7 was subjected to H NMR spectrum detection, and the spectrum is shown in Figure 1-7 , analyze the amount of each characteristic group in the product to the total product, and calculate the residual rate of double-terminal epoxy silicone oil and the yield of silylated phytosphingosine:

[0080] 1. Calculation formula for the residual rate of double-terminal epoxy silicone oil: Residual rate of double-terminal epoxy silicone oil (%) = peak area of ​​epoxy group after reaction / total NMR peak area. The results are shown in Table 1.

[0081] 2. Calculation formula for the yield of silylated phytosphingosine: yield of silylated phytosphingosine (%) = (1-remaining double-terminal epoxy silicone oil content + theoretical excess epoxy silicone oil amount in reaction) * 100%. The results are shown in Table 2.

[0082] Table 1

[0083] sample Double-ended epoxy silicone oil residual rate (%) Example 1 39.39 Example 2 39.39 Example 3 21.21 Example 4 36.63 Example 5 30.30 Example 6 45.45 Example 7 30.30

[0084] Table 2

[0085] sample Silylated phytosphingosine yield (%) Example 1 60.61 Example 2 70.61 Example 3 98.79 Example 4 73.37 Example 5 79.70 Example 6 64.55 Example 7 79.70

[0086] It can be seen from Table 1 and Table 2 that the silylated phytosphingosine prepared by using phytosphingosine as raw material, ethanol as solvent and double-terminal epoxy silicone oil has high utilization rate of phytosphingosine raw material and high yield.

[0087] Comparative Example 1

[0088] The preparation method of silanized phytosphingosine is different from that of Example 3 only in that the double-terminated epoxy silicone oil is replaced by a double-terminated amino silicone oil, and the rest is the same.

[0089] Comparative Example 2

[0090] The preparation method of silylated phytosphingosine is different from that of Example 3 only in that the double-terminal epoxy silicone oil is replaced by a double-terminal hydroxy silicone oil, and the rest is the same.

[0091] Effect Example 1

[0092] The silylated phytosphingosine of Example 3 and Comparative Examples 1-2 and phytosphingosine were added to caprylic / capric triglyceride at 60°C, and the added amount was 20wt% of caprylic / capric triglyceride. The results are shown in Figure 8 .

[0093] Effect Example 2

[0094] The silylated phytosphingosine of Example 3 and Comparative Examples 1-2 and phytosphingosine were added to white oil at 60°C, with the addition amount being 20 wt % of the white oil. The results are shown in FIG. Fig. 9 .

[0095] Effect Example 3

[0096] The silylated phytosphingosine of Example 3 and Comparative Examples 1-2 and phytosphingosine were added to polydimethylsiloxane at 60°C, and the added amount was 20 wt% of the polydimethylsiloxane. The results are shown in Fig.10 .

[0097] Effect Example 4

[0098] The silylated phytosphingosine of Example 3 and Comparative Examples 1-2 and phytosphingosine were added to sunflower seed oil at 60°C, and the added amount was 20wt% of the sunflower seed oil. The results are shown in Fig.11 .

[0099] Depend on Figure 8-Figure 11 It can be seen that the silylated phytosphingosine prepared using double-ended epoxy silicone oil has good solubility in various oils and fats at 60°C, while the silylated phytosphingosine and phytosphingosine of Comparative Examples 1-2 are not easily soluble in various oils and fats at 60°C.

[0100] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions of the technical solution of the present invention by ordinary technicians in this field do not deviate from the essence and scope of the technical solution of the present invention.

Claims

1. A method for preparing silylated phytosphingosine, characterized in that: The following steps are involved: S1. dissolving phytosphingosine in a solvent to obtain a mixed solution; S2, heating the mixed solution, adding double-ended epoxy silicone oil to carry out heat preservation reaction; S3. After the heat preservation reaction is completed, the reaction mixture is taken out and subjected to rotary evaporation to completely evaporate the solvent to obtain silylated phytosphingosine; the molar ratio of the phytosphingosine to the double-terminal epoxy silicone oil is 1:0.5-0.

6.

2. The preparation method according to claim 1, characterized in that: The molar ratio of the phytosphingosine to the double-terminal epoxy silicone oil is 1:0.55-0.

6.

3. The preparation method according to claim 2, characterized in that: The mass ratio of the phytosphingosine to the double-terminal epoxy silicone oil is 1:0.

6.

4. The preparation method according to claim 1, characterized in that: The solvent is selected from at least one of methanol, ethanol, chloroform and dimethyl sulfoxide.

5. The preparation method according to claim 1, characterized in that: The mass ratio of the phytosphingosine to the solvent is 1:8-12.

6. The preparation method according to claim 1, characterized in that: The reaction temperature of the heat preservation reaction is 65-100° C., and the reaction time is 6-12 hours.

7. The preparation method according to claim 6, characterized in that: The reaction temperature of the insulation reaction is 85-100° C., and the reaction time is 9-12 hours.

8. The preparation method according to claim 7, characterized in that: The reaction temperature of the insulation reaction is 100° C. and the reaction time is 12 h.

9. Silylated phytosphingosine obtained by the method for preparing silylated phytosphingosine according to any one of claims 1 to 8.

10. Use of the silylated phytosphingosine obtained by the preparation method of silylated phytosphingosine according to any one of claims 1 to 8 in cosmetics or skin care products.

Images