CN112409153A - Camphor compound and preparation method thereof - Google Patents
Camphor compound and preparation method thereof Download PDFInfo
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- CN112409153A CN112409153A CN202011361210.5A CN202011361210A CN112409153A CN 112409153 A CN112409153 A CN 112409153A CN 202011361210 A CN202011361210 A CN 202011361210A CN 112409153 A CN112409153 A CN 112409153A
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- camphor
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- camphor compound
- trichloromethane
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- 241000723346 Cinnamomum camphora Species 0.000 title claims abstract description 57
- 229960000846 camphor Drugs 0.000 title claims abstract description 57
- 229930008380 camphor Natural products 0.000 title claims abstract description 57
- -1 Camphor compound Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000000634 powder X-ray diffraction Methods 0.000 claims abstract description 8
- 238000005259 measurement Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 229960001701 chloroform Drugs 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000008213 purified water Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000012360 testing method Methods 0.000 description 10
- 239000003814 drug Substances 0.000 description 9
- 229940079593 drug Drugs 0.000 description 6
- 238000011160 research Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002160 Celluloid Polymers 0.000 description 1
- 229940122957 Histamine H2 receptor antagonist Drugs 0.000 description 1
- 241001676573 Minium Species 0.000 description 1
- 244000082946 Tarchonanthus camphoratus Species 0.000 description 1
- 235000005701 Tarchonanthus camphoratus Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003485 histamine H2 receptor antagonist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- AWMAOFAHBPCBHJ-UHFFFAOYSA-M sodium;(7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate Chemical compound [Na+].C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C AWMAOFAHBPCBHJ-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940085790 synthetic camphor Drugs 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
- C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/427—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having two rings
- C07C49/433—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having two rings the condensed ring system containing seven carbon atoms
- C07C49/437—Camphor; Fenchone
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a camphor compound and a preparation method thereof. The camphor compound is a crystal, and characteristic peaks in a map of the camphor compound are shown at 6.9 degrees, 8.1 degrees, 9.2 degrees, 10.2 degrees, 11.6 degrees, 13.8 degrees, 14.3 degrees, 15.4 degrees, 18.0 degrees, 18.8 degrees, 21.2 degrees, 23.2 degrees, 24.3 degrees, 25.0 degrees and 34.6 degrees at 2 theta +/-0.2 degrees by adopting X-ray powder diffraction measurement. The camphor compound prepared by the invention has high purity, low hygroscopicity, good solubility and good stability.
Description
Technical Field
The invention belongs to the technical field of medicines, and relates to a camphor compound and a preparation method thereof.
Background
Camphor: chemical name: (1 RS, 4 RS) -1, 7, 7-trimethylbicyclo [2.2.1] heptan-2-one, a potent histamine H2 receptor antagonist. Has camphorwood smell and wide application. The camphor is used as a nerve stimulant and a local stimulant in medicine, and can be used in medicaments for cooling and cooling, such as ten drops of water, minium and the like; it can also be used for preparing food essence such as herba Menthae, fructus Citri Limoniae, and nut, and daily essence such as floral water and daily cosmetics. In addition, camphor is widely used in celluloid and photographic films, as a stabilizer for manufacturing smokeless powder, as a raw material for manufacturing sodium camphorsulfonate, and the like, and pharmaceutical preparations using camphor as a raw material are widely used in the technical field of medicine.
The camphor is extremely unstable when being heated and wetted, the quality of a preparation product is seriously influenced due to the reasons of agglomeration, poor stability and the like caused by the fact that raw material medicines easily absorb moisture, meanwhile, the dissolubility is poor, the difficulty is increased for the production of the preparation, meanwhile, certain risks are caused for the medication safety, and the research on the application of a more stable camphor compound to the camphor has a positive effect because the camphor is unstable and the camphor has a positive curative effect in clinical use. The inventor unexpectedly obtains a camphor compound in a crystal form in the process of a large amount of researches on camphor for a long time, and the compound has the advantages of extremely high quality stability, high purity, low hygroscopicity, good solubility, increased medication safety and preparation convenience, and is obviously superior to the prior art.
Disclosure of Invention
The present invention provides a stable camphor compound.
The camphor compound provided by the invention is a crystal, and the characteristic peaks in the map are shown at 6.9 degrees, 8.1 degrees, 9.2 degrees, 10.2 degrees, 11.6 degrees, 13.8 degrees, 14.3 degrees, 15.4 degrees, 18.0 degrees, 18.8 degrees, 21.2 degrees, 23.2 degrees, 24.3 degrees, 25.0 degrees and 34.6 degrees at 2 theta +/-0.2 degrees by adopting X-ray powder diffraction measurement.
The X-ray powder diffraction pattern of the camphor compound is shown in fig. 1.
The melting point of the camphor compound is 182-185 ℃.
The preparation method of the camphor compound comprises the following steps:
1. dissolving camphor raw material in mixed solution of trichloromethane and ethanol; wherein the volume ratio of the trichloromethane to the ethanol is 1: 9; the dosage ratio of the camphor raw material to the mixed solution of the trichloromethane and the ethanol is 1g to 5 ml.
2. Keeping the temperature of the solution at 20-25 ℃, adding purified water with the volume 8 times that of the mixed solution of the trichloromethane and the ethanol in the step 1 into the solution in the step 1 at the speed of 120-140 ml/min while stirring at the stirring speed of 110-130 r/min, stopping stirring after the purified water is added, cooling to-2-4 ℃ at the speed of 1.0-1.2 ℃/min, standing for crystal growth for 3 hours, and filtering to obtain a filter cake.
3. And (3) washing the filter cake obtained by filtering in the step (2) with 2 times of purified water for 1 time, and drying for 10 hours at the temperature of 22-24 ℃ under reduced pressure to obtain the camphor compound.
The camphor raw material in the preparation process of the camphor compound is a commercially available synthesized camphor bulk drug.
The camphor compound prepared by the invention has high purity, good stability, low hygroscopicity, difficult agglomeration and better dissolubility according to the common knowledge in the field, and the camphor compound prepared by the invention has better dissolubility compared with the prior art under the condition of low hygroscopicity.
It should be noted that, the formation of a crystal form is influenced by many factors, and any one of the factors such as reaction temperature, time, stirring speed, reactant concentration, crystallization condition control and the like may produce unexpected changes even if small changes occur, and the inventors have experienced many failures in the research process, but finally spend much effort in researching control details, and finally obtain the camphor compound of the invention, and each control point in the preparation process of the compound of the invention is crucial to the result.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a camphor compound prepared in example 1 of the present invention.
Detailed Description
EXAMPLE 1 preparation of Camphor Compound
1. Dissolving camphor raw material in a mixed solution of trichloromethane and ethanol according to a weight-volume ratio (g/ml) of 1:5, wherein the volume ratio of the trichloromethane to the ethanol is 1: 9.
2. Keeping the temperature of the solution at 20 ℃, adding purified water with the volume 8 times that of the mixed solution of the trichloromethane and the ethanol in the step 1 into the solution in the step 1 at the speed of 120ml/min while stirring at the stirring speed of 110 revolutions per minute, stopping stirring after the purified water is added, cooling to-2 ℃ at the speed of 1.0 ℃/min, standing for crystal growth for 3 hours, and filtering to obtain a filter cake.
3. And (3) washing the filter cake obtained by filtering in the step (2) with 2 times of purified water for 1 time, and drying for 10 hours at 22 ℃ under reduced pressure to obtain the camphor compound.
The X-ray powder diffraction pattern is shown in figure 1, and the characteristic peaks in the pattern are shown at 2 theta of 6.9 degrees, 8.1 degrees, 9.2 degrees, 10.2 degrees, 11.6 degrees, 13.8 degrees, 14.3 degrees, 15.4 degrees, 18.0 degrees, 18.8 degrees, 21.2 degrees, 23.2 degrees, 24.3 degrees, 25.0 degrees and 34.6 degrees.
The content is as follows: 99.92 percent. Melting point: 182 to 185 ℃.
EXAMPLE 2 preparation of Camphor Compound
1. Dissolving camphor raw material in a mixed solution of trichloromethane and ethanol according to a weight-volume ratio (g/ml) of 1:5, wherein the volume ratio of the trichloromethane to the ethanol is 1: 9.
2. Keeping the temperature of the solution at 23 ℃, adding purified water with the volume 8 times that of the mixed solution of the trichloromethane and the ethanol in the step 1 into the solution in the step 1 at the speed of 130ml/min while stirring at the stirring speed of 120 r/min, stopping stirring after the purified water is added, cooling to-3 ℃ at the speed of 1.1 ℃/min, standing for crystal growth for 3 hours, and filtering to obtain a filter cake.
3. And (3) washing the filter cake obtained by filtering in the step (2) with 2 times of purified water for 1 time, and drying for 10 hours at 23 ℃ under reduced pressure to obtain the camphor compound.
The X-ray powder diffraction pattern is consistent with example 1. The content is as follows: 99.95 percent. Melting point: 182 to 185 ℃.
EXAMPLE 3 preparation of Camphor Compound
1. Dissolving camphor raw material in a mixed solution of trichloromethane and ethanol according to a weight-volume ratio (g/ml) of 1:5, wherein the volume ratio of the trichloromethane to the ethanol is 1: 9.
2. Keeping the temperature of the solution at 25 ℃, adding purified water with the volume 8 times that of the mixed solution of the trichloromethane and the ethanol in the step 1 into the solution in the step 1 at a stirring speed of 130 r/min while stirring, stopping stirring after the purified water is added, cooling to-4 ℃ at a speed of 1.2 ℃/min, standing for 3 hours for crystal growth, and filtering to obtain a filter cake.
3. And (3) washing the filter cake obtained by filtering in the step (2) with 2 times of purified water for 1 time, and drying for 10 hours at 24 ℃ under reduced pressure to obtain the camphor compound.
The X-ray powder diffraction pattern is consistent with example 1. The content is as follows: 99.95 percent. Melting point: 182 to 185 ℃.
The present invention provides the following test and comparative results: (test detection method is carried out according to the standard method of synthesizing camphor raw material in the second part of Chinese pharmacopoeia 2015 edition)
Sample 1: camphor Compound produced in example 1 of the present invention
Sample 2: commercially available synthetic camphor bulk drug
The sample 1 and the sample 2 are subjected to influence factor tests and are respectively placed in high humidity (humidity is 90 +/-5%) and strong light (4500 lx +/-500 lx) for 10 days, sampling and verification are respectively carried out on the 10 th day, the results are compared with the results of 0 day, and the stability results of the examined samples are shown in the following tables 1-2.
TABLE 1 high humidity Effect factor test results
TABLE 2 test results of strong light influence factors
As can be seen from the results of tables 1 to 2, the camphor compound prepared according to the present invention has good stability, low impurity content, low hygroscopicity, and significant advantages over the prior art. The same tests were carried out on camphor compounds prepared in other examples of the invention, with similar results.
Samples 1-2 were tested for solubility in water (25 ℃. + -. 2 ℃) and the results are shown in Table 3:
TABLE 3 results of solubility test
| Sample (I) | Solubility (g/100 ml) |
| 1 | 0.1 |
| 2 | 0.02 |
As can be seen from the results of table 3, the camphor compound prepared according to the present invention has better solubility, and has a significant advantage over the prior art. The same tests were carried out on camphor compounds prepared in other examples of the invention, with similar results.
Long-term stability studies (25 ℃ C. + -. 2 ℃ C., RH 60%. + -. 10%) were performed on samples 1-2, and the results are shown in Table 4.
TABLE 4 Camphor Long-term test results
As can be seen from the results of table 4, the camphor compound prepared according to the present invention has good stability, low impurity content, low hygroscopicity, and significant advantages over the prior art. The same tests were carried out on camphor compounds prepared in other examples of the invention, with similar results.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (3)
1. A camphor compound characterized by: the camphor compound is a crystal, and characteristic peaks in a map of the camphor compound are shown at 6.9 degrees, 8.1 degrees, 9.2 degrees, 10.2 degrees, 11.6 degrees, 13.8 degrees, 14.3 degrees, 15.4 degrees, 18.0 degrees, 18.8 degrees, 21.2 degrees, 23.2 degrees, 24.3 degrees, 25.0 degrees and 34.6 degrees at 2 theta +/-0.2 degrees by adopting X-ray powder diffraction measurement.
2. The camphor compound of claim 1 wherein: the melting point of the camphor compound is 182-185 ℃.
3. A process for preparing the camphor compound as claimed in claim 1 or 2, comprising the steps of:
(1) dissolving camphor raw material in a mixed solution of trichloromethane and ethanol with a volume ratio of 1: 9; the dosage ratio of the camphor raw material to the mixed solution of the trichloromethane and the ethanol is 1g:5 ml;
(2) keeping the temperature of the solution in the step (1) at 20-25 ℃, adding purified water with the volume 8 times that of the mixed solution of the trichloromethane and the ethanol in the step (1) into the solution in the step (1) at the speed of 120-140 ml/min while stirring at the stirring speed of 110-130 r/min, stopping stirring after the purified water is added, cooling to-2-4 ℃ at the speed of 1.0-1.2 ℃/min, standing for crystal growth for 3 hours, and filtering to obtain a filter cake;
(3) and (3) washing the filter cake obtained by filtering in the step (2) with 2 times of purified water for 1 time, and drying for 10 hours at the temperature of 22-24 ℃ under reduced pressure to obtain the camphor compound.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011361210.5A CN112409153B (en) | 2020-11-27 | 2020-11-27 | Camphor compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202011361210.5A CN112409153B (en) | 2020-11-27 | 2020-11-27 | Camphor compound and preparation method thereof |
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| CN112409153A true CN112409153A (en) | 2021-02-26 |
| CN112409153B CN112409153B (en) | 2023-11-24 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB190406652A (en) * | 1904-03-18 | 1905-01-19 | August Zimmermann | The Manufacture of Camphor from Isoborneol. |
| GB118489A (en) * | 1917-09-28 | 1918-09-05 | Du Pont | Process for Purifying Camphor. |
| CN1059711A (en) * | 1990-09-10 | 1992-03-25 | 中国科学院广州化学研究所 | The synthetic method of optically active camphor |
| CN1065451A (en) * | 1991-03-22 | 1992-10-21 | 中国科学院广州化学研究所 | The method of preparation of high purity camphor from dehydrogenated and impuritier removal iso-borneo camphor |
| CN105175237A (en) * | 2015-09-07 | 2015-12-23 | 广西梧州通轩林产化学有限公司 | Method of preparing camphor from camphene as raw material |
| CN105753667A (en) * | 2016-05-04 | 2016-07-13 | 福州大学 | Method for preparing camphor through continuous dehydrogenation of isoborneol |
| CN106588615A (en) * | 2016-11-29 | 2017-04-26 | 大连德泽药业有限公司 | Application of Zedoary turmeric oil in preparation of camphor and isolation and extraction method of Zedoary turmeric oil |
-
2020
- 2020-11-27 CN CN202011361210.5A patent/CN112409153B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB190406652A (en) * | 1904-03-18 | 1905-01-19 | August Zimmermann | The Manufacture of Camphor from Isoborneol. |
| GB118489A (en) * | 1917-09-28 | 1918-09-05 | Du Pont | Process for Purifying Camphor. |
| CN1059711A (en) * | 1990-09-10 | 1992-03-25 | 中国科学院广州化学研究所 | The synthetic method of optically active camphor |
| CN1065451A (en) * | 1991-03-22 | 1992-10-21 | 中国科学院广州化学研究所 | The method of preparation of high purity camphor from dehydrogenated and impuritier removal iso-borneo camphor |
| CN105175237A (en) * | 2015-09-07 | 2015-12-23 | 广西梧州通轩林产化学有限公司 | Method of preparing camphor from camphene as raw material |
| CN105753667A (en) * | 2016-05-04 | 2016-07-13 | 福州大学 | Method for preparing camphor through continuous dehydrogenation of isoborneol |
| CN106588615A (en) * | 2016-11-29 | 2017-04-26 | 大连德泽药业有限公司 | Application of Zedoary turmeric oil in preparation of camphor and isolation and extraction method of Zedoary turmeric oil |
Non-Patent Citations (1)
| Title |
|---|
| 中国药学会药学通报编委会: "《高等材料物理化学》", 哈尔滨工业大学出版社 * |
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