A method for extracting phellandrene

Abstract

The present invention discloses a method for extracting phellandrene. The method comprises the following steps: (1) crushing the branches and leaves of camphor tree into fragments of 60 to 100 mesh; (2) placing the crushed fragments in water vapor for distillation for 30 to 50 minutes, then taking them out and placing them in a mixed solution, stirring them evenly and soaking them for 3 to 5 hours; (3) extracting the mixed material soaked in step (2) with supercritical carbon dioxide fluid to obtain a crude extract; and (4) separating the phellandrene in the crude extract by silica gel column chromatography. The present application can effectively improve the extraction rate of the crude extract and the final phellandrene yield during the camphor tree treatment process by combining softening, mixed solution soaking and supercritical fluid extraction processes. The technical solution of the present invention is used to extract phellandrene from camphor tree, and the yield can reach up to about 10%, which can maximize the extraction of phellandrene in camphor tree and improve its utilization rate.

Description

Technical Field

[0001] The invention belongs to the technical field of plant extraction, and particularly relates to a method for extracting phellandrene. Background Art

[0002] Phellandrene is a monocyclic terpene compound found in a variety of volatile oils such as eucalyptus oil, anise oil, cumin oil, cinnamon leaf oil, turpentine, etc. It includes two isomers, a-phellandrene and β-phellandrene. It has a fresh citrus-pepper aroma, active chemical properties, and can provide C 10 The molecular skeleton and endocyclic and exocyclic double bonds have unique application prospects in the field of fine chemistry and can be directly used to process spices or bioactive pesticides; a more valuable application is to synthesize high-end spices, bioactive substances, pharmacologically active substances and functional materials through chemical reactions based on its structural characteristics, so as to more fully tap its utilization value.

[0003] Phellandrene can be obtained through synthetic synthesis or extraction from essential oils and specific plants. However, the content of phellandrene in natural plants is low. Furthermore, phellandrene is unstable, easily decomposing upon distillation at normal pressure and isomerizing into terpinene. Existing extraction methods significantly limit the yield of phellandrene from natural plants or essential oils. Therefore, there is an urgent need for a more efficient method for extracting phellandrene. Summary of the Invention

[0004] In view of the above-mentioned deficiencies in the prior art, the present invention provides a method for extracting phellandrene, which can effectively solve the problem of low extraction efficiency of the prior art.

[0005] To achieve the above-mentioned purpose, the technical solution adopted by the present invention to solve the technical problem is:

[0006] A method for extracting phellandrene comprises the following steps:

[0007] (1) Crush the branches and leaves of camphor tree into pieces of 60-100 mesh;

[0008] (2) placing the crushed fragments in water vapor for distillation for 30 to 50 minutes, then taking them out and placing them in a mixed solution, stirring them evenly and soaking them for 3 to 5 hours; the components of the mixed solution include phosphate, organic solvent, methyl formate and alkyl halide;

[0009] (3) extracting the mixed material after soaking in step (2) with supercritical carbon dioxide fluid to separate and obtain a crude extract;

[0010] (4) Silica gel column chromatography was used to separate phellandrene from the crude extract.

[0011] Furthermore, the final concentration of phosphate in the mixed solution is 0.5-2 mg / mL, the final concentration of methyl formate is 1.5-5 mg / mL, and the final concentration of alkyl halide is 0.1-0.5 mg / mL.

[0012] Furthermore, the final concentration of phosphate in the mixed solution is 0.5 mg / mL, the final concentration of methyl formate is 3 mg / mL, and the final concentration of alkyl halide is 0.3 mg / mL.

[0013] Furthermore, the phosphate is sodium dihydrogen phosphate, potassium phosphate or sodium superphosphate.

[0014] Furthermore, the alkyl halide is dichloromethane.

[0015] Furthermore, the organic solvent is ethanol or ether.

[0016] Furthermore, the weight of the crushed fragments is 0.5 to 3 wt.% of the mixed solution.

[0017] Furthermore, the extraction temperature is 25-30° C., the gas flow rate is 15-25 kg / h, and the extraction time is 3-5 h.

[0018] Furthermore, during separation by silica gel column chromatography, n-hexane was used as the eluent at a flow rate of 1 to 2 mL / min.

[0019] Furthermore, the eluent flow rate is 2 mL / min.

[0020] Beneficial effects of the present invention:

[0021] 1. The present application combines softening, mixed solution immersion and supercritical fluid extraction processes to effectively improve the extraction rate of crude extracts and the final yield of phellandrene during the treatment of camphor trees. The technical solution of the present invention is used to extract phellandrene from camphor trees, and the yield can reach up to about 10%. The phellandrene in camphor trees can be extracted to the maximum extent, thereby improving its utilization rate.

[0022] 2. This application constructs a mixed solution for soaking camphor tree fragments by compounding phosphate, organic solvent, methyl formate and alkyl halide. In the mixed solution, phosphate constructs a weakly alkaline environment and is compounded with organic solvent, methyl formate and alkyl halide, which significantly improves the extraction rate of the crude extract and further ensures the yield of subsequent products.

[0023] 3. Phellandrene is unstable and easily decomposes and isomerizes into terpinene. Therefore, this application utilizes supercritical fluid extraction to extract phellandrene from the crude extract, minimizing the impact of decomposition and isomerization on yield. The technical solution constructed in this application demonstrates that the yield of phellandrene can be effectively guaranteed, reaching as high as approximately 10%, significantly exceeding the extraction rate of unstable substances using conventional methods such as steam distillation. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is the mass spectrum of phellandrene. DETAILED DESCRIPTION

[0025] The specific embodiments of the present invention are described below to facilitate understanding of the present invention by those skilled in the art. However, it should be clear that the present invention is not limited to the scope of the specific embodiments. For those skilled in the art, as long as various changes are within the spirit and scope of the present invention as defined and determined by the appended claims, these changes are obvious, and all inventions and creations utilizing the concepts of the present invention are protected.

[0026] Example 1

[0027] A method for extracting phellandrene comprises the following steps:

[0028] (1) Crush 500 g of camphor tree branches and leaves into 60 mesh pieces;

[0029] (2) The crushed fragments were placed in water vapor for distillation for 35 minutes, then taken out and placed in a mixed solution, stirred evenly and soaked for 3 hours; the mixed solution included sodium dihydrogen phosphate, ether, methyl formate and dichloromethane; wherein the final concentration of phosphate was 0.5 mg / mL, the final concentration of methyl formate was 3 mg / mL, the final concentration of alkyl halide was 0.3 mg / mL, and the volume of ether was 2000 mL;

[0030] (3) extracting the mixed material after soaking in step (2) with supercritical carbon dioxide fluid to separate and obtain a crude extract; the extraction temperature is 25° C., the gas flow rate is 20 kg / h, and the extraction time is 3.5 h;

[0031] (4) Using n-hexane as the eluent, silica gel column chromatography was used to separate phellandrene from the crude extract at an eluent flow rate of 2 mL / min.

[0032] Example 2

[0033] A method for extracting phellandrene comprises the following steps:

[0034] (1) Crush 500 g of camphor tree branches and leaves into 100 mesh pieces;

[0035] (2) The crushed fragments were placed in water vapor for distillation for 30 minutes, then taken out and placed in a mixed solution, stirred evenly and soaked for 3.5 hours; the mixed solution included sodium dihydrogen phosphate, ether, methyl formate and dichloromethane; wherein the final concentration of sodium dihydrogen phosphate was 0.5 mg / mL, the final concentration of methyl formate was 1.5 mg / mL, the final concentration of dichloromethane was 0.1 mg / mL, and the volume of ether was 2000 mL;

[0036] (3) extracting the mixed material after soaking in step (2) with supercritical carbon dioxide fluid to separate and obtain a crude extract; the extraction temperature is 25° C., the gas flow rate is 15 kg / h, and the extraction time is 3 h;

[0037] (4) Using n-hexane as the eluent, silica gel column chromatography was used to separate phellandrene from the crude extract at an eluent flow rate of 2 mL / min.

[0038] Example 3

[0039] A method for extracting phellandrene comprises the following steps:

[0040] (1) Crush 500 g of camphor tree branches and leaves into 80 mesh pieces;

[0041] (2) The crushed fragments were placed in water vapor for distillation for 50 minutes, then taken out and placed in a mixed solution, stirred evenly and soaked for 3 hours; the mixed solution included sodium dihydrogen phosphate, ether, methyl formate and dichloromethane; wherein the final concentration of sodium dihydrogen phosphate was 2 mg / mL, the final concentration of methyl formate was 2 mg / mL, the final concentration of dichloromethane was 0.5 mg / mL, and the volume of ether was 2000 mL;

[0042] (3) extracting the mixed material after soaking in step (2) with supercritical carbon dioxide fluid to separate and obtain a crude extract; the extraction temperature is 25° C., the gas flow rate is 15 kg / h, and the extraction time is 3 h;

[0043] (4) Using n-hexane as the eluent, silica gel column chromatography was used to separate phellandrene from the crude extract at an eluent flow rate of 2 mL / min.

[0044] Comparative Example 1

[0045] A method for extracting phellandrene comprises the following steps:

[0046] (1) Crush 500 g of camphor tree branches and leaves into 80 mesh pieces;

[0047] (2) The crushed fragments were placed in steam for distillation for 50 min, then taken out and soaked in a mixed enzyme solution for 5 h;

[0048] (3) extracting the mixed material after soaking in step (2) with supercritical carbon dioxide fluid to separate and obtain a crude extract; the extraction temperature is 25° C., the gas flow rate is 15 kg / h, and the extraction time is 3 h;

[0049] (4) Using n-hexane as the eluent, silica gel column chromatography was used to separate phellandrene from the crude extract at an eluent flow rate of 2 mL / min.

[0050] Comparative Example 2

[0051] A method for extracting phellandrene comprises the following steps:

[0052] (1) Crush 500 g of camphor tree branches and leaves into 80 mesh pieces;

[0053] (2) The crushed fragments were placed in steam for distillation for 50 min, then taken out and soaked in a mixed enzyme solution for 5 h;

[0054] (3) Extraction with ether or ethanol, followed by vacuum distillation to obtain a crude extract;

[0055] (4) Using n-hexane as the eluent, silica gel column chromatography was used to separate phellandrene from the crude extract at an eluent flow rate of 2 mL / min.

[0056] Comparative Example 3

[0057] A method for extracting phellandrene comprises the following steps:

[0058] (1) Crush 500 g of camphor tree branches and leaves into 60 mesh pieces;

[0059] (2) The crushed fragments were placed in water vapor for distillation for 35 minutes, then taken out and placed in a mixed solution, stirred evenly and soaked for 3 hours; the mixed solution included sodium dihydrogen phosphate, ether, methyl formate and dichloromethane; wherein the final concentration of phosphate was 0.5 mg / mL, the final concentration of methyl formate was 3 mg / mL, the final concentration of alkyl halide was 0.3 mg / mL, and the volume of ether was 2000 mL;

[0060] (3) extracting with ether and then obtaining a crude extract by steam distillation;

[0061] (4) Using n-hexane as the eluent, silica gel column chromatography was used to separate phellandrene from the crude extract at an eluent flow rate of 2 mL / min.

[0062] Comparative Example 4

[0063] A method for extracting phellandrene comprises the following steps:

[0064] (1) Crush 500 g of camphor tree branches and leaves into 80 mesh pieces;

[0065] (2) The crushed fragments were placed in water vapor for distillation for 50 minutes, then taken out and placed in a mixed solution, stirred evenly and soaked for 3 hours; the mixed solution included sodium dihydrogen phosphate, ether, dimethyl carbonate and dichloromethane; wherein the final concentration of sodium dihydrogen phosphate was 2 mg / mL, the final concentration of dimethyl carbonate was 2 mg / mL, the final concentration of dichloromethane was 0.5 mg / mL, and the volume of ether was 2000 mL;

[0066] (3) extracting the mixed material after soaking in step (2) with supercritical carbon dioxide fluid to separate and obtain a crude extract; the extraction temperature is 25° C., the gas flow rate is 15 kg / h, and the extraction time is 3 h;

[0067] (4) Using n-hexane as the eluent, silica gel column chromatography was used to separate phellandrene from the crude extract at an eluent flow rate of 2 mL / min.

[0068] Comparative Example 5

[0069] A method for extracting phellandrene comprises the following steps:

[0070] (1) Crush 500 g of camphor tree branches and leaves into 80 mesh pieces;

[0071] (2) The crushed fragments were placed in water vapor for distillation for 50 minutes, then taken out and placed in a mixed solution, stirred evenly and soaked for 3 hours; the mixed solution included ether and methyl formate; wherein the final concentration of methyl formate was 2 mg / mL and the volume of ether was 2000 mL;

[0072] (3) extracting the mixed material after soaking in step (2) with supercritical carbon dioxide fluid to separate and obtain a crude extract; the extraction temperature is 25° C., the gas flow rate is 15 kg / h, and the extraction time is 3 h;

[0073] (4) Using n-hexane as the eluent, silica gel column chromatography was used to separate phellandrene from the crude extract at an eluent flow rate of 2 mL / min.

[0074] Comparative Example 6

[0075] A method for extracting phellandrene comprises the following steps:

[0076] (1) Crush 500 g of camphor tree branches and leaves into 60 mesh pieces;

[0077] (2) The crushed fragments were placed in water vapor for distillation for 35 minutes, then taken out and placed in a mixed solution, stirred evenly and soaked for 3 hours; the mixed solution included phosphoric acid, ether, methyl formate and dichloromethane; wherein the final concentration of phosphate was 0.5 mg / mL, the final concentration of methyl formate was 3 mg / mL, the final concentration of alkyl halide was 0.3 mg / mL, and the volume of ether was 2000 mL;

[0078] (3) extracting the mixed material after soaking in step (2) with supercritical carbon dioxide fluid to separate and obtain a crude extract; the extraction temperature is 25° C., the gas flow rate is 20 kg / h, and the extraction time is 3.5 h;

[0079] (4) Using n-hexane as the eluent, silica gel column chromatography was used to separate phellandrene from the crude extract at an eluent flow rate of 2 mL / min.

[0080] Experimental example

[0081] 1. The product separated by the method described in Example 1 of the present application was identified, and its mass spectrum was as follows: Figure 1 As shown, it is shown that the product separated by the technical solution of the present application is phellandrene.

[0082] 2. The yields of the crude extract and the final phellandrene according to the schemes described in Examples 1 to 3 and Comparative Examples 1 to 4 of the present application were tested. The results are shown in Table 1.

[0083] Table 1 Product yield

[0084]

[0085]

[0086] As can be seen from the data in Table 1, the yields of the crude extracts and phellandrene obtained in Examples 1 to 3 of the present application are significantly better than those in the comparative examples. For comparative examples 1 and 2, the yields of the crude extracts and phellandrene obtained by combining conventional enzymatic hydrolysis and ether extraction processes are significantly reduced, indicating that the technical solution described in the present application has an excellent extraction rate.

[0087] Comparative Examples 3 to 6 replaced some steps and changed the components of the mixed solvent. It can be seen that the modified technical solutions also had a significant impact on the yields of the crude extract and phellandrene, and some were even only comparable to those of conventional treatments. This shows that only with the cooperation of the technical solution described in this application can a high yield of phellandrene be obtained.

[0088] Finally, it should be noted that the above specific implementation methods are only used to illustrate the technical solutions of the present invention and are not limiting. Although the present invention has been described in detail with reference to examples, those skilled in the art should understand that the technical solutions of the present invention can be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. A method for extracting phellandrene, characterized in that: The following steps are involved: (1) Crush the branches and leaves of Cinnamomum camphora into 60-100 mesh pieces; (2) The crushed fragments are placed in water vapor for distillation for 30 to 50 minutes, then taken out and placed in a mixed solution, stirred evenly and soaked for 3 to 5 hours; the components of the mixed solution include phosphate with a final concentration of 0.5 to 2 mg / mL, an organic solvent, methyl formate with a final concentration of 1.5 to 5 mg / mL, and 0.1 to 0.5 mg / mL of alkyl halide; the phosphate is sodium dihydrogen phosphate, potassium phosphate or sodium superphosphate; the alkyl halide is dichloromethane; the organic solvent is ethanol or ether; (3) extracting the mixed material after soaking in step (2) with supercritical carbon dioxide fluid to separate and obtain a crude extract; (4) Silica gel column chromatography was used to separate phellandrene from the crude extract.

2. The method for extracting phellandrene according to claim 1, wherein The final concentration of phosphate in the mixed solution was 0.5 mg / mL, the final concentration of methyl formate was 3 mg / mL, and the final concentration of alkyl halide was 0.3 mg / mL.

3. The method for extracting phellandrene according to claim 1, wherein The weight of the crushed fragments is 0.5~3wt.% of the mixed solution.

4. The method for extracting phellandrene according to claim 1, wherein The extraction temperature is 25~30℃, the gas flow rate is 15~25kg / h, and the extraction time is 3~5h.

5. The method for extracting phellandrene according to claim 1, wherein During the separation by silica gel column chromatography, n-hexane is used as the eluent for elution at a flow rate of 1-2 mL / min.

6. The method for extracting phellandrene according to claim 5, characterized in that: The eluent flow rate was 2 mL / min.

Images