High-purity hydroxypropyl tetrahydropyrantriol and synthetic method thereof
Through the combination of enzymatic reaction and supercritical extraction, the problems of reactant residue and boron residue in synthesis of hydroxypropyltetrahydropyrantriol are solved, and high-purity and low-cost synthesis is achieved, which is suitable for cosmetics and pharmaceutical fields.
Patent Information
- Application Number
- CN202510728041.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-03
- Publication Date
- 2025-08-19
AI Technical Summary
The existing hydroxypropyltetrahydropyrantriol synthesis methods have problems such as the residual reactant, the residual boron of boron, and the high synthesis cost, which limits its application in cosmetics and medicine fields.
The method of combining enzymatic reaction with supercritical extraction was adopted, and the reduction reaction was performed using glycosyltransferase and organotin compounds. The subsequent supercritical extraction was carried out using carbon dioxide and ethanol as the medium to remove impurities and avoid boron residues.
The synthesis of hydroxypropyltetrahydropyrantriol with few reactants, high purity and high safety is achieved, and is suitable for cosmetics and pharmaceutical fields with high purity and safety requirements.
Smart Images
Figure SMS_1
Abstract
Description
Technical Field
[0001] The present invention relates to the field of synthesis technology, in particular to high-purity hydroxypropyl tetrahydropyrantriol and a synthesis method thereof. Background Art
[0002] Hydroxypropyl tetrahydropyrantriol has garnered widespread attention in recent years. It possesses a variety of excellent properties. For example, it has an excellent ability to promote the synthesis of glycosaminoglycans in the extracellular matrix. This can effectively enhance skin moisturizing properties, increase skin elasticity, reduce wrinkle formation, and provide excellent repair and nourishing benefits to the skin.
[0003] Despite its numerous advantages, existing synthesis methods for hydroxypropyl tetrahydropyrantriol (HTTP) have hindered its further development. For example, traditional HTTP synthesis methods suffer from numerous drawbacks. Many synthetic routes introduce significant amounts of residual reactants, which not only reduce product purity and impact performance in high-end applications, but also pose potential safety risks. Furthermore, some synthetic processes rely on boron-containing reagents, making boron residues unavoidable in the final product. The accumulation of boron in the body can damage the nervous and reproductive systems, significantly limiting its application in safety-critical applications such as cosmetics and pharmaceutical excipients. Furthermore, the complex synthesis steps and expensive raw materials and reagents contribute to high synthesis costs, hindering large-scale industrial production and market expansion.
[0004] In view of the above problems, it is urgent to develop a method for synthesizing high-purity hydroxypropyl tetrahydropyrantriol that can overcome the defects of the prior art. Summary of the Invention
[0005] In view of the above problems, the present invention provides a high-purity hydroxypropyl tetrahydropyrantriol and a synthesis method thereof. The synthesis method can achieve the effect of less reactant residue and no boron residue.
[0006] To achieve the above object, the present invention adopts the following technical solutions: A method for synthesizing high-purity hydroxypropyl tetrahydropyrantriol comprises the following steps: mixing a carbohydrate raw material and a glycosyltransferase in a buffer solution to perform an enzymatic reaction, wherein the mass percentage of the glycosyltransferase in the carbohydrate raw material is 0.1%-5%; after the enzymatic reaction is completed, adding an organic tin compound to the reaction system under a protective gas atmosphere to perform a reduction reaction; after the reduction reaction, removing the solvent from the reaction system to obtain a concentrate; and performing supercritical extraction on the concentrate using carbon dioxide as a supercritical fluid and ethanol as an entrainer to obtain high-purity hydroxypropyl tetrahydropyrantriol.
[0007] Optionally, the glycosyltransferase is one or more of UDP-glucosyltransferase and GDP-mannosyltransferase.
[0008] Optionally, the organotin compound is tributyltin hydride.
[0009] Optionally, the carbohydrate raw material is one or more of glucose and mannose.
[0010] Optionally, the buffer is phosphate buffer.
[0011] Optionally, the temperature of the enzymatic reaction is 30-33° C.; and / or the time of the enzymatic reaction is 10-12 h.
[0012] Optionally, the reduction reaction temperature is 50-55° C.; and / or the reduction reaction time is 6-8 h.
[0013] Optionally, the temperature of the supercritical extraction is 40-45° C.; and / or, the pressure of the supercritical extraction is 25-28 MPa; and or, the time of the supercritical extraction is 1.5-2 h.
[0014] Optionally, the protective gas is one or more of nitrogen and argon.
[0015] High-purity hydroxypropyl tetrahydropyrantriol is synthesized by the above synthesis method.
[0016] Beneficial effects The synthesis method of this invention achieves the significant advantage of minimal residual reactants by combining a unique enzymatic reaction with subsequent meticulous processing steps. During the supercritical extraction step, reactant impurities can be efficiently separated from the target product, significantly improving the purity of the final product and meeting the stringent purity requirements of high-end applications.
[0017] Furthermore, since no boron-containing reagents are used in the entire synthesis process, the problem of boron residue is eliminated from the source, greatly improving the safety of the product and enabling it to be safely used in fields closely related to human health, such as cosmetics and medicine.
[0018] Furthermore, the present invention uses common and inexpensive carbohydrate raw materials, combines them with relatively efficient and precisely controlled enzymes, and cost-effective organotin compounds, and combines them with energy-saving and efficient supercritical extraction technology, effectively reducing synthesis costs and providing strong support for large-scale industrial production. DETAILED DESCRIPTION
[0019] One embodiment of the present invention provides a method for synthesizing high-purity hydroxypropyl tetrahydropyrantriol. The method comprises the following steps: mixing a carbohydrate raw material and a glycosyltransferase in a buffer solution for an enzymatic reaction, wherein the mass percentage of the glycosyltransferase in the carbohydrate raw material is 0.1%-5%. After the enzymatic reaction, an organotin compound is added to the reaction system under a protective gas atmosphere to perform a reduction reaction. After the reduction reaction, the solvent of the reaction system is removed to obtain a concentrate. The concentrate is subjected to supercritical extraction using carbon dioxide as a supercritical fluid and ethanol as an entrainer to obtain high-purity hydroxypropyl tetrahydropyrantriol. In this synthesis method, the rational combination of the enzymatic reaction and supercritical extraction steps can effectively reduce the residual amount of reactants and improve the purity of the product. Furthermore, the synthesis method of the present invention does not use boron-containing reagents, which can avoid the problem of boron residue in the product and improve the safety of the product.
[0020] As some optional examples of the mass percentage of glycosyltransferase in the carbohydrate raw material, the mass percentage of glycosyltransferase in the carbohydrate raw material can be 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc. It is understood that the mass percentage of glycosyltransferase in the carbohydrate raw material can also be other suitable selections within the range of 0.1%-5%.
[0021] Optionally, the glycosyltransferase is one or more of UDP-glucosyltransferase and GDP-mannosyltransferase.
[0022] Optionally, the carbohydrate raw material is one or more of glucose and mannose.
[0023] Optionally, the temperature of the enzymatic reaction is 30-33° C. For example, the temperature of the enzymatic reaction can be 30° C., 31° C., 32° C., 33° C., etc. It is understood that the temperature of the enzymatic reaction can also be other suitable selections within the range of 30-33° C.
[0024] Optionally, the time of the enzymatic reaction is 10-12 hours. For example, the time of the enzymatic reaction can be 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, etc. It is understandable that the time of the enzymatic reaction can also be other suitable selections within the scope of 10-12 hours.
[0025] Optionally, the buffer is phosphate buffer.
[0026] In the enzymatic reaction described above, a carbohydrate feedstock and a glycosyltransferase are mixed in a buffer solution for the enzymatic reaction, where the mass percentage of the glycosyltransferase in the carbohydrate feedstock is controlled between 0.1% and 5%. In this process, glycosyltransferases, including one or more of UDP-glucosyltransferase and GDP-mannosyltransferase, play a crucial catalytic role. By precisely controlling the dosage and combination of enzymes, the carbohydrate feedstock can be efficiently and effectively converted, laying the foundation for subsequent reactions.
[0027] In addition, the carbohydrate raw material can be selected from one or more of glucose and mannose. These carbohydrate raw materials are widely available, low in cost, and have good reactivity. The buffer is preferably a phosphate buffer, which can stabilize the pH value of the reaction system, provide a suitable acid-base environment for the enzymatic reaction, optimize the enzyme activity, and thus improve reaction efficiency and product selectivity. Furthermore, the pH value of the reaction system of the enzymatic reaction is 7-7.5.
[0028] Furthermore, the temperature of the enzymatic reaction is set to 30-33°C, and the reaction time is maintained at 10-12 hours. Under these conditions, the enzymatic reaction can proceed smoothly and efficiently, avoiding enzyme inactivation or increased side reactions due to excessively high temperature or excessively long time, and also preventing incomplete reactions due to excessively low temperature or too short time.
[0029] Optionally, the organotin compound is tributyltin hydride.
[0030] Optionally, the temperature of the reduction reaction is 50-55° C. For example, the temperature of the reduction reaction can be 50° C., 51° C., 52° C., 53° C., 54° C., 55° C., etc. It is understood that the temperature of the reduction reaction can also be other suitable selections within the range of 50-55° C.
[0031] Optionally, the reduction reaction time is 6-8 hours. Further optionally, the reduction reaction time can be 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, etc. It is understandable that the reduction reaction time can also be other suitable selections within the range of 6-8 hours.
[0032] Optionally, the protective gas is one or more of nitrogen and argon.
[0033] In the present invention, after the enzymatic reaction is completed, an organic tin compound is quickly added to the reaction system under a protective gas atmosphere to start the reduction reaction. The protective gas is selected from one or more of nitrogen and argon, which can effectively isolate the air, prevent the active substances in the reaction system from being oxidized, and ensure that the reduction reaction proceeds smoothly. The organic tin compound is preferably tributyltin hydride, which has a strong reducing ability and can accurately reduce the enzymatic reaction product, converting it into an intermediate that is closer to the target product, providing high-quality raw materials for subsequent steps. The temperature of the reduction reaction is controlled at 50-55°C and the reaction time is 6-8h, which can not only ensure that the reduction reaction is fully carried out, but also avoid excessive reduction or side reactions caused by temperature discomfort, thereby maximizing the reaction yield and product purity.
[0034] Furthermore, after the reduction reaction is complete, the solvent in the reaction system can be removed by methods such as vacuum distillation to obtain a concentrate. This step effectively enriches the reaction product and removes excess solvent impurities, preparing for subsequent supercritical extraction. It also facilitates the implementation and management of subsequent operations. It is understood that when removing the solvent, since removing all of the solvent may require a long time and high cost, it may be necessary to remove a large portion of the solvent.
[0035] Optionally, the temperature of supercritical extraction is 40-45° C. Further, the temperature of supercritical extraction can be 40° C., 41° C., 42° C., 43° C., 44° C., 45° C., etc. It is understood that the temperature of supercritical extraction can also be other suitable selections within the range of 40-45° C.
[0036] Optionally, the supercritical extraction pressure is 25-28 MPa. For example, the supercritical extraction pressure can be 25 MPa, 25.5 MPa, 26 MPa, 26.5 MPa, 27 MPa, 27.5 MPa, 28 MPa, etc. It is understood that the supercritical extraction pressure can be other suitable selections within the range of 25-28 MPa.
[0037] Optionally, the supercritical extraction time is 1.5-2 hours. For example, the supercritical extraction time can be 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2 hours, or other suitable selections.
[0038] The concentrate is subjected to supercritical extraction using carbon dioxide as the supercritical fluid and ethanol as the entrainer, yielding high-purity hydroxypropyl tetrahydropyrantriol. In its supercritical state, carbon dioxide combines the high diffusivity of a gas with the good solubility of a liquid, enabling rapid and precise penetration into the concentrate and full contact with the target product. Ethanol, acting as the entrainer, enhances carbon dioxide's solubility for hydroxypropyl tetrahydropyrantriol, further improving extraction efficiency. Under these optimized parameters, supercritical extraction efficiently separates the target product from the concentrate while effectively removing residual reactants, by-products, and other impurities, resulting in a high-purity final product.
[0039] Another embodiment of the present invention provides high-purity hydroxypropyl tetrahydropyrantriol. This high-purity hydroxypropyl tetrahydropyrantriol is synthesized by the above-described synthesis method. The hydroxypropyl tetrahydropyrantriol prepared by the synthesis method of the present invention has high purity, extremely low reactant residues, and almost no detectable boron residue, meeting the application standards of industries such as cosmetics and pharmaceuticals that have high purity requirements.
[0040] Another embodiment of the present invention provides a cosmetic comprising the high-purity hydroxypropyl tetrahydropyrantriol.
[0041] Example 1 The synthesis method of high-purity hydroxypropyl tetrahydropyrantriol in the present embodiment is: (1) Enzymatic reaction: 100 g of glucose was selected as the carbohydrate raw material and added to 500 mL of phosphate buffer with a pH of 7. Then 0.1 g of UDP-glucosyltransferase was added (the mass percentage of glycosyltransferase in the carbohydrate raw material was 0.1%). The reaction system was placed in a constant temperature environment of 30°C and stirred continuously for 12 hours.
[0042] (2) Reduction reaction: After the enzymatic reaction was completed, nitrogen was immediately introduced into the reaction vessel as a protective gas to form an inert atmosphere, and then 10 g of tributyltin hydride was added. The temperature was raised to 50° C. and stirring was maintained to carry out the reduction reaction for 8 h.
[0043] (3) Concentration step: A vacuum distillation apparatus is used to remove most of the solvent in the reaction system to obtain a concentrate.
[0044] (4) Supercritical extraction: The concentrate was transferred to a supercritical extraction device, where carbon dioxide was used as the supercritical fluid and ethanol as the entrainer. Supercritical extraction was performed at 40°C and 25 MPa for 2 hours. After the extraction, the extract was collected and the entrainer and carbon dioxide were removed by evaporation under reduced pressure, yielding a high-purity hydroxypropyl tetrahydropyrantriol product.
[0045] Example 2 The synthesis method of high-purity hydroxypropyl tetrahydropyrantriol in the present embodiment is: (1) Enzymatic reaction: 100 g of glucose was selected as the carbohydrate raw material and added to 500 mL of phosphate buffer with a pH of 7. Then 0.5 g of UDP-glucosyltransferase was added (the mass percentage of glycosyltransferase in the carbohydrate raw material was 0.5%). The reaction system was placed in a constant temperature environment of 30°C and stirred continuously for 12 hours.
[0046] (2) Reduction reaction: After the enzymatic reaction was completed, nitrogen was immediately introduced into the reaction vessel as a protective gas to form an inert atmosphere, and then 10 g of tributyltin hydride was added. The temperature was raised to 50° C. and stirring was maintained to carry out the reduction reaction for 8 h.
[0047] (3) Concentration step: A vacuum distillation apparatus is used to remove most of the solvent in the reaction system to obtain a concentrate.
[0048] (4) Supercritical extraction: The concentrate was transferred to a supercritical extraction device, where carbon dioxide was used as the supercritical fluid and ethanol as the entrainer. Supercritical extraction was performed at 40°C and 25 MPa for 2 hours. After the extraction, the extract was collected and the entrainer and carbon dioxide were removed by evaporation under reduced pressure, yielding a high-purity hydroxypropyl tetrahydropyrantriol product.
[0049] Example 3 The synthesis method of high-purity hydroxypropyl tetrahydropyrantriol in the present embodiment is: (1) Enzymatic reaction: 100 g of glucose was selected as the carbohydrate raw material and added to 500 mL of phosphate buffer with a pH of 7. Then 1 g of UDP-glucosyltransferase was added (the mass percentage of glycosyltransferase in the carbohydrate raw material was 1%). The reaction system was placed in a constant temperature environment of 30°C and stirred continuously for 12 hours.
[0050] (2) Reduction reaction: After the enzymatic reaction was completed, nitrogen was immediately introduced into the reaction vessel as a protective gas to form an inert atmosphere, and then 10 g of tributyltin hydride was added. The temperature was raised to 50° C. and stirring was maintained to carry out the reduction reaction for 8 h.
[0051] (3) Concentration step: A vacuum distillation apparatus is used to remove most of the solvent in the reaction system to obtain a concentrate.
[0052] (4) Supercritical extraction: The concentrate was transferred to a supercritical extraction device, where carbon dioxide was used as the supercritical fluid and ethanol as the entrainer. Supercritical extraction was performed at 40°C and 25 MPa for 2 hours. After the extraction, the extract was collected and the entrainer and carbon dioxide were removed by evaporation under reduced pressure, yielding a high-purity hydroxypropyl tetrahydropyrantriol product.
[0053] Example 4 The synthesis method of high-purity hydroxypropyl tetrahydropyrantriol in the present embodiment is: (1) Enzymatic reaction: 100 g of mannose was selected as the carbohydrate raw material and added to 800 mL of phosphate buffer with a pH of 7.2. Then, 2 g of GDP-mannosyltransferase was added (the mass percentage of glycosyltransferase in the carbohydrate raw material was 2%). The reaction system was placed in a constant temperature environment of 33°C and stirred continuously for 12 hours.
[0054] (2) Reduction reaction: After the enzymatic reaction was completed, nitrogen was immediately introduced into the reaction vessel as a protective gas to form an inert atmosphere, and then 15 g of tributyltin hydride was added. The temperature was raised to 55° C. and stirring was maintained to carry out the reduction reaction for 6 h.
[0055] (3) Concentration step: A vacuum distillation apparatus is used to remove most of the solvent in the reaction system to obtain a concentrate.
[0056] (4) Supercritical extraction: The concentrate was transferred to a supercritical extraction apparatus, where carbon dioxide was used as the supercritical fluid and ethanol as the entrainer. Supercritical extraction was performed at 45°C and 28 MPa for 1.5 hours. After the extraction, the extract was collected and the entrainer and carbon dioxide were removed by evaporation under reduced pressure, yielding a high-purity hydroxypropyl tetrahydropyrantriol product.
[0057] Example 5 The synthesis method of high-purity hydroxypropyl tetrahydropyrantriol in the present embodiment is: (1) Enzymatic reaction: 100 g of mannose was selected as the carbohydrate raw material and added to 800 mL of phosphate buffer with a pH of 7.2. Then, 3 g of GDP-mannosyltransferase was added (the mass percentage of glycosyltransferase in the carbohydrate raw material was 3%). The reaction system was placed in a constant temperature environment of 33°C and stirred continuously for 12 hours.
[0058] (2) Reduction reaction: After the enzymatic reaction was completed, nitrogen was immediately introduced into the reaction vessel as a protective gas to form an inert atmosphere, and then 15 g of tributyltin hydride was added. The temperature was raised to 55° C. and stirring was maintained to carry out the reduction reaction for 6 h.
[0059] (3) Concentration step: A vacuum distillation apparatus is used to remove most of the solvent in the reaction system to obtain a concentrate.
[0060] (4) Supercritical extraction: The concentrate was transferred to a supercritical extraction apparatus, where carbon dioxide was used as the supercritical fluid and ethanol as the entrainer. Supercritical extraction was performed at 45°C and 28 MPa for 1.5 hours. After the extraction, the extract was collected and the entrainer and carbon dioxide were removed by evaporation under reduced pressure, yielding a high-purity hydroxypropyl tetrahydropyrantriol product.
[0061] Example 6 The synthesis method of high-purity hydroxypropyl tetrahydropyrantriol in the present embodiment is: (1) Enzymatic reaction: 100 g of mannose was selected as the carbohydrate raw material and added to 800 mL of phosphate buffer with a pH of 7.2. Then, 4 g of GDP-mannosyltransferase was added (the mass percentage of glycosyltransferase in the carbohydrate raw material was 4%). The reaction system was placed in a constant temperature environment of 33°C and stirred continuously for 12 hours.
[0062] (2) Reduction reaction: After the enzymatic reaction was completed, nitrogen was immediately introduced into the reaction vessel as a protective gas to form an inert atmosphere, and then 15 g of tributyltin hydride was added. The temperature was raised to 55° C. and stirring was maintained to carry out the reduction reaction for 6 h.
[0063] (3) Concentration step: A vacuum distillation apparatus is used to remove most of the solvent in the reaction system to obtain a concentrate.
[0064] (4) Supercritical extraction: The concentrate was transferred to a supercritical extraction apparatus, where carbon dioxide was used as the supercritical fluid and ethanol as the entrainer. Supercritical extraction was performed at 45°C and 28 MPa for 1.5 hours. After the extraction, the extract was collected and the entrainer and carbon dioxide were removed by evaporation under reduced pressure, yielding a high-purity hydroxypropyl tetrahydropyrantriol product.
[0065] Example 7 The synthesis method of high-purity hydroxypropyl tetrahydropyrantriol in the present embodiment is: (1) Enzymatic reaction: 100 g of mannose was selected as the carbohydrate raw material and added to 800 mL of phosphate buffer with a pH of 7.2. Then, 5 g of GDP-mannosyltransferase was added (the mass percentage of glycosyltransferase in the carbohydrate raw material was 5%). The reaction system was placed in a constant temperature environment of 33°C and stirred continuously for 12 hours.
[0066] (2) Reduction reaction: After the enzymatic reaction was completed, nitrogen was immediately introduced into the reaction vessel as a protective gas to form an inert atmosphere, and then 15 g of tributyltin hydride was added. The temperature was raised to 55° C. and stirring was maintained to carry out the reduction reaction for 6 h.
[0067] (3) Concentration step: A vacuum distillation apparatus is used to remove most of the solvent in the reaction system to obtain a concentrate.
[0068] (4) Supercritical extraction: The concentrate was transferred to a supercritical extraction apparatus, where carbon dioxide was used as the supercritical fluid and ethanol as the entrainer. Supercritical extraction was performed at 45°C and 28 MPa for 1.5 hours. After the extraction, the extract was collected and the entrainer and carbon dioxide were removed by evaporation under reduced pressure, yielding a high-purity hydroxypropyl tetrahydropyrantriol product.
[0069] Comparative Example 1 The synthesis method of high-purity hydroxypropyl tetrahydropyrantriol in this comparative example is: (1) Enzymatic reaction: 100 g of mannose was selected as the carbohydrate raw material and added to 800 mL of phosphate buffer with a pH of 7.2. Then, 0.05 g of GDP-mannosyltransferase was added (the mass percentage of glycosyltransferase in the carbohydrate raw material was 0.05%). The reaction system was placed in a constant temperature environment of 33°C and stirred continuously for 12 hours.
[0070] (2) Reduction reaction: After the enzymatic reaction was completed, nitrogen was immediately introduced into the reaction vessel as a protective gas to form an inert atmosphere, and then 15 g of tributyltin hydride was added. The temperature was raised to 55° C. and stirring was maintained to carry out the reduction reaction for 6 h.
[0071] (3) Concentration step: A vacuum distillation apparatus is used to remove most of the solvent in the reaction system to obtain a concentrate.
[0072] (4) Supercritical extraction: The concentrate was transferred to a supercritical extraction apparatus, where carbon dioxide was used as the supercritical fluid and ethanol as the entrainer. Supercritical extraction was performed at 45°C and 28 MPa for 1.5 hours. After the extraction, the extract was collected and the entrainer and carbon dioxide were removed by evaporation under reduced pressure, yielding a high-purity hydroxypropyl tetrahydropyrantriol product.
[0073] Comparative Example 2 The synthesis method of high-purity hydroxypropyl tetrahydropyrantriol in this comparative example is: (1) Enzymatic reaction: 100 g of mannose was selected as the carbohydrate raw material and added to 800 mL of phosphate buffer with a pH of 7.2. Then, 5.5 g of GDP-mannosyltransferase was added (the mass percentage of glycosyltransferase in the carbohydrate raw material was 5.5%). The reaction system was placed in a constant temperature environment of 33°C and stirred continuously for 12 hours.
[0074] (2) Reduction reaction: After the enzymatic reaction was completed, nitrogen was immediately introduced into the reaction vessel as a protective gas to form an inert atmosphere, and then 15 g of tributyltin hydride was added. The temperature was raised to 55° C. and stirring was maintained to carry out the reduction reaction for 6 h.
[0075] (3) Concentration step: A vacuum distillation apparatus is used to remove most of the solvent in the reaction system to obtain a concentrate.
[0076] (4) Supercritical extraction: The concentrate was transferred to a supercritical extraction apparatus, where carbon dioxide was used as the supercritical fluid and ethanol as the entrainer. Supercritical extraction was performed at 45°C and 28 MPa for 1.5 hours. After the extraction, the extract was collected and the entrainer and carbon dioxide were removed by evaporation under reduced pressure, yielding a high-purity hydroxypropyl tetrahydropyrantriol product.
[0077] Test Case The purity of the hydroxypropyl tetrahydropyrantriol products in the examples and comparative examples was determined using high performance liquid chromatography-mass spectrometry (HPLC-MS). The results are shown in Table 1.
[0078] Table 1
[0079] As can be seen from Table 1, the enzymatic reaction, reduction reaction and supercritical extraction in the present invention can effectively improve the synthesis purity of hydroxypropyl tetrahydropyrantriol, and no boron residue is left in the synthetic product.
[0080] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
[0081] For those skilled in the art, according to the concept of the present invention, there may be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as limiting the present invention.
Claims
1. A method for synthesizing high-purity hydroxypropyl tetrahydropyrantriol, characterized in that: The method comprises the following steps: mixing a carbohydrate raw material and a glycosyltransferase in a buffer solution to carry out an enzymatic reaction, wherein the mass percentage of the glycosyltransferase in the carbohydrate raw material is 0.1%-5%; after the enzymatic reaction is completed, adding an organic tin compound to the reaction system under a protective gas atmosphere to carry out a reduction reaction; after the reduction reaction, removing the solvent of the reaction system to obtain a concentrate; and performing supercritical extraction on the concentrate using carbon dioxide as a supercritical fluid and ethanol as an entrainer to obtain high-purity hydroxypropyl tetrahydropyrantriol.
2. The synthetic method of high-purity hydroxypropyl tetrahydropyrantriol as claimed in claim 1, wherein The glycosyltransferase is one or more of UDP-glucosyltransferase and GDP-mannosyltransferase.
3. The synthetic method of high-purity hydroxypropyl tetrahydropyrantriol as claimed in claim 1, wherein The organotin compound is tributyltin hydride.
4. The synthetic method of high-purity hydroxypropyl tetrahydropyrantriol as claimed in claim 1, wherein The sugar raw material is one or more of glucose and mannose.
5. The synthetic method of high-purity hydroxypropyl tetrahydropyrantriol as claimed in claim 1, wherein The buffer is phosphate buffer.
6. The method for synthesizing high-purity hydroxypropyl tetrahydropyrantriol according to any one of claims 1 to 5, wherein: The temperature of the enzymatic reaction is 30-33° C.; and / or the time of the enzymatic reaction is 10-12 h.
7. The method for synthesizing high-purity hydroxypropyl tetrahydropyrantriol according to any one of claims 1 to 5, wherein: The temperature of the reduction reaction is 50-55° C.; and / or the time of the reduction reaction is 6-8 hours.
8. The method for synthesizing high-purity hydroxypropyl tetrahydropyrantriol according to any one of claims 1 to 5, wherein: The temperature of the supercritical extraction is 40-45° C.; and / or, the pressure of the supercritical extraction is 25-28 MPa; and / or, the time of the supercritical extraction is 1.5-2 h.
9. The method for synthesizing high-purity hydroxypropyl tetrahydropyrantriol according to any one of claims 1 to 5, wherein: The protective gas is one or more of nitrogen and argon.
10. A high-purity hydroxypropyl tetrahydropyrantriol, characterized in that: The compound is synthesized by the synthesis method according to any one of claims 1 to 9.