CN111454114A - One kind is used13C2High purity of geraniol synthesis13C2Method for producing myrcene - Google Patents
One kind is used13C2High purity of geraniol synthesis13C2Method for producing myrcene Download PDFInfo
- Publication number
- CN111454114A CN111454114A CN202010393597.6A CN202010393597A CN111454114A CN 111454114 A CN111454114 A CN 111454114A CN 202010393597 A CN202010393597 A CN 202010393597A CN 111454114 A CN111454114 A CN 111454114A
- Authority
- CN
- China
- Prior art keywords
- myrcene
- reaction
- geraniol
- high purity
- synthesis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
One kind is used13C2High purity of geraniol synthesis13C2-a process for myrcene comprising the steps of: (1) will be provided with13C2Dissolving geraniol in an organic solvent, adding hydrogen peroxide and p-toluenesulfonic acid monohydrate, stirring for reaction, monitoring the reaction process by T L C, concentrating the obtained reaction solution under reduced pressure after the reaction is completed, purifying the reaction solution by silica gel column chromatography to obtain an intermediate, (2) dissolving the intermediate in the organic solvent, stirring the intermediate with potassium tert-butoxide and 18-crown-6 dissolved in the organic solvent under the protection of nitrogen, heating for reaction, monitoring the reaction process by T L C, stirring the obtained reaction solution for cooling after the reaction is completed, adding diethyl ether for extraction, and sequentially cleaning the organic phase with water, a saturated sodium bicarbonate aqueous solution and a saturated salt solutionDrying, purifying by silica gel column chromatography to obtain high purity13C2-myrcene. The invention does not use metal catalyst or additive, has mild process conditions, has the advantages of simplicity, high efficiency, economy and greenness, and is particularly suitable for isotope13C or14C-labeled and non-isotopic-labeled myrcene.
Description
Technical Field
The invention relates to a13C2A method for synthesizing (E) -myrcene, in particular to a method for synthesizing (E) -myrcene13C2High purity of geraniol synthesis13C2Method for preparing myrcene, which is equally applicable to myrcene and14C2-synthesis of myrcene.
Background
The myrcene has pleasant sweet balsam smell, is an important chemical raw material and intermediate in the perfume industry, is widely applied to synthesizing various rare perfume products such as citronellal, lyral, ambergris ketone and the like, and is also an important raw material in the pharmaceutical industry such as synthetic vitamin, insect repellent, antitumor active substances and the like, natural myrcene can be extracted from plant essential oil such as verbena, bay leaf, mastic oil and the like, but the yield and quality of the collected myrcene are unstable due to the lower content of myrcene in the natural essential oil and the limitation of factors such as season, climate and the like, so that the market demand can not be met all the time, and myrcene products can be obtained by industrially extracting β -pinene from turpentine and then cracking the myrcene products.
At present, myrcene is prepared by geraniol in the prior art, such as high-temperature high-pressure dehydration or by adding various dehydration reagents (alkali, dehydration reagents and the like), the product is generally purified by a distillation method, but the method needs high temperature and high pressure, consumes energy and time, has higher requirements on equipment and higher cost, and more importantly, the dehydration product has a plurality of isomers under the high-temperature high-pressure condition, the purity of the target product is not high, the subsequent purification process is complex, and the method wastes time and labor; although in order to reduce the occurrence of side reactions of isomerization, noble metal catalysts are generally used in the industry for synthesizing myrcene, for example, the noble metal catalysts are used for catalytic synthesis, the method can only reduce the occurrence of side reactions of isomers to a certain extent, more importantly, the cost of the metal palladium catalysts is very high, which is not beneficial to industrial production, and the environmental problems related to the recovery and pollution of noble metal reagents are not well solved, so that the safety is poor.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a simple and efficient use with mild process conditions, no use of metal catalysts or additives, economy, greenness and high yield13C2High purity of geraniol synthesis13C2-myrcene.
The technical scheme adopted by the invention for solving the technical problems is as follows: one kind is used13C2High purity of geraniol synthesis13C2-a process for myrcene comprising the steps of:
(1) will be provided with13C2-geraniol is dissolved in an organic solvent, 3, 4-dihydro-2H-pyran and p-toluenesulfonic acid monohydrate are added, the mixture is stirred for reaction, T L C monitors the reaction process, and after the reaction is completed, the obtained reaction solution is decompressed and concentrated, and purified through silica gel column chromatography to obtain an intermediate;
(2) dissolving the intermediate in an organic solvent, stirring the intermediate and potassium tert-butoxide and 18-crown ether-6 dissolved in the organic solvent under the protection of nitrogen, heating for reaction, monitoring the reaction process by T L C, stirring the obtained reaction solution for cooling after the reaction is completed, adding diethyl ether for extraction, and respectively using water and saturated carbonic acidSequentially washing organic phase with sodium bicarbonate water solution and saturated salt solution, drying, and purifying by silica gel column chromatography to obtain high purity13C2-myrcene.
Preferably, in step (1), the13C2The feeding molar ratio of geraniol, 3, 4-dihydro-2H-pyran and p-toluenesulfonic acid monohydrate is 1 (1.0-1.8) to (0.01-0.03).
Preferably, in the step (2), the feeding molar ratio of the intermediate, the potassium tert-butoxide and the 18-crown-6 is 1 (8-12) to (1-3). Preferably, the organic solvent is anhydrous tetrahydrofuran.
Preferably, the vacuum degree of the reduced pressure concentration is-0.08 to-0.09 MPa.
Preferably, the organic solvent is anhydrous tetrahydrofuran.
The invention of said13C2High purity of geraniol synthesis13C2Method for synthesizing high-purity myrcene14C2-use of myrcene.
The invention of said13C2High purity of geraniol synthesis13C2Application of the method of myrcene in synthesis of high-purity myrcene.
The synthetic route of the invention is as follows: by mixing13C2Conversion of the hydroxyl group of geraniol into a readily removable group (THP) intermediate, followed by leaving the intermediate under alkaline conditions, obtaining a high purity13C2-myrcene.
Note: is a stable isotope13C or radioactive isotopes14C。
Compared with the prior art, the invention has the beneficial effects that: firstly, no metal catalyst or additive is used, the method is economical and green, the process conditions are mild, high temperature and high pressure are not needed, the requirement on equipment is low, and the method is particularly suitable for industrial production; the required raw materials are synthesized, the intermediate is simple and easy to obtain and stable, and the conventional controllable temperature of 50-70 ℃ is adopted in the heating reaction processThe operability is strong; secondly, the purification method is a normal pressure normal phase silica gel column purification method for collecting low polarity components, no isomerization side reaction exists, and the target product13C2The chemical purity of the-myrcene is as high as 99 percent, the isotopic abundance is high, and the method is particularly suitable for isotopes13C、14C-labeled and non-isotopic-labeled myrcene.
Detailed Description
The present invention will be further described with reference to the following examples.
The chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
In the practice of geraniol: (13C2) Or geraniol (14C2) The synthetic route of (A) is as follows:
note: is a stable isotope13C or radioactive isotopes14C。
Reference example 1
1. The synthesis of the intermediate 1 specifically comprises the following steps:
(1) adding commercially labeled acetic acid (A) into a three-neck flask with a condenser tube13C2) Namely raw material 1(2.00g, 32.24mmol), trifluoroacetic anhydride (15.78g, 75.11mmol) and DMAP (40mg, 0.32mmol), stirring and heating to 60 ℃, slowly dropping liquid bromine (5.87g, 36.75mmol), dropping for 1 hour, keeping the temperature at 60 ℃ after dropping, and continuing stirring for 1 hour;
(2) stopping heating, stirring the reaction system, cooling to room temperature, adding benzyl alcohol (20ml), stirring, heating to 60 ℃, and continuing stirring for 12 hours;
(3) stopping heating, cooling the reaction solution to room temperature under stirring, adding saturated sodium bicarbonate (40ml) to dilute the reaction system, extracting with ether (60ml × 4 times), combining organic phases, washing the organic phase with saturated aqueous sodium bicarbonate (50ml) and saturated aqueous sodium thiosulfate (50ml), drying the obtained product anhydrous sodium sulfate, adding water, filtering, concentrating the obtained filtrate under reduced pressure, mixing the obtained concentrate with a sample, and purifying by silica gel column chromatography (PE: EA gradient is that v/v is 1:0 → 20:1) to obtain 6.90g of anhydrous oily matter, namely intermediate 1 (yield: 92.6%).
2. The intermediate 2 is synthesized by the following specific operations:
(1) adding the intermediate 1(6.89g, 29.82mmol) and the raw material 2(5.45g, 32.80mmol) into a single-mouth reaction bottle with a condensing tube, stirring under the protection of nitrogen, heating to 125 ℃, and stirring for 4 hours;
(2) dot panel T L C (PE: EA ═ 1: 1) showed completion of the reaction, leaving very little intermediate 1 and generating a large amount of intermediate 2;
(3) the reaction system was warmed to room temperature, and then the reaction system was cooled to room temperature, and then the mixture was subjected to silica gel column chromatography (PE: EA ═ 20:1 → 5: 1 → 1:1 → 1: 2) to obtain 8.48g (yield: 98.7%) of a colorless oily intermediate 2.
3. The intermediate 3 is synthesized by the following specific operations:
(1) sodium hydride (1.22g, 30.49mmol) was added to the dried reaction flask, the air in the reaction flask was replaced with nitrogen, anhydrous tetrahydrofuran (30ml) was added, intermediate 2(8.45g, 29.31mmol) dissolved in 10ml of anhydrous tetrahydrofuran was added dropwise at 0 ℃, stirring was continued at room temperature for 0.5h after completion of the dropwise addition, starting material 3(3.70g, 29.31mmol) was added dropwise, and the reaction system was stirred and warmed to 50 ℃ overnight.
(2) The reaction system was stirred and cooled to room temperature, water was added to quench, ether extraction (100ml × 3 times) was performed, the organic phases were combined, the organic phases were dried over anhydrous sodium sulfate, and the resulting product was concentrated under reduced pressure and purified by silica gel column chromatography (PE: EA ═ 1:0) to obtain 3.55g in total of intermediate 3 as a pale yellow oil (yield: 46.5%).
4. Geraniol (13C2) The specific operation is as follows:
(1) l AH (0.94g, 24.75mmol) is added into anhydrous tetrahydrofuran (15ml), aluminum trichloride (1.18g, 8.84mmol) is added in batches under the protection of nitrogen, the temperature of the reaction system is reduced to 0 ℃, intermediate 3(3.54g, 13.60mmol) dissolved in 5ml of anhydrous tetrahydrofuran is slowly dropped, and after dropping, the reaction system is naturally heated to room temperature and stirred for 2 h;
(2) t L C (PE: EA ═ 100: 1) was completed without intermediate 3.
(3) Adding water (0.94ml), 15% sodium hydroxide aqueous solution (0.94ml) and water (2.82ml) to the reaction system in this order, stirring for 15min, concentrating under reduced pressure, purifying the resulting concentrated product by silica gel column chromatography (PE: EA ═ 10: 1),
reference example 2
Reference example 2 differs from reference example 1 only in that starting material 1 added in the synthesis of intermediate 1 is labeled acetic acid: (14C2) Reference is made to geraniol (14C2) The synthesis route of (1) to obtain a pale yellow oil, namely geraniol (14C2)1.92g (yield: 90.1%).
Example 1
The embodiment comprises the following steps:
(1) in a dry three-necked reaction flask, 1.85g (11.84mmol) of the product obtained in reference example 1 was placed13C2Geraniol was dissolved in 40m L anhydrous tetrahydrofuran, 1.49g (17.71mmol)3, 4-dihydro-2H-pyran and 50mg p-toluenesulfonic acid monohydrate were added, the reaction was stirred at room temperature overnight, and the progress of the reaction was monitored by T L C (PE: EA ═ 10: 1) when the reaction was complete (no water)13C2Geraniol), the reaction solution obtained was concentrated under reduced pressure (-0.08MPa) and purified by silica gel column chromatography (PE: EA gradient v/v 1:0 → 30: 1) 1.46g of intermediate is obtained, and the yield is 51.2%;
(2) dissolving 1.40g (5.82mmol) of intermediate in 5M L anhydrous tetrahydrofuran in a dry three-neck reaction bottle, reacting with 58.7M L (58.73mmol)1M potassium tert-butoxide and 3.11g (11.77mmol) 18-crown-6 dissolved in an organic solvent at 60 ℃ under stirring and under nitrogen protection for 14h, monitoring the reaction progress with T L C (PE: EA ═ 45: 1), cooling the reaction solution to room temperature under stirring after the reaction is complete (no intermediate), adding 100M L diethyl ether for extraction, washing the organic phase with 50M L water, 50M L saturated sodium bicarbonate aqueous solution and 50M L saturated saline water in sequence, drying over anhydrous sodium sulfate, and purifying by silica gel column chromatography (PE) to obtain 680mg (purity 99.81%)13C2Myrcene, yield 84.5%.
Example 2
The embodiment comprises the following steps:
(1) in a dry three-necked reaction flask, 1.85g (11.84mmol) of commercially available geraniol (purity 98%) was dissolved in 40m L anhydrous tetrahydrofuran, 1.49g (17.71mmol) of 3, 4-dihydro-2H-pyran and 50mg of p-toluenesulfonic acid monohydrate were added, the reaction was stirred at room temperature overnight, T L C (PE: EA ═ 10: 1) was monitored for the progress of the reaction, and when the reaction was completed (geraniol), the resulting reaction solution was concentrated under reduced pressure (-0.08MPa), and purified by silica gel column chromatography (PE: EA gradient v/v 1:0 → 30: 1) to obtain 1.46g of intermediate with a yield of 51.2%;
(2) in a dry three-necked flask, 1.39g (5.78mmol) of intermediate was dissolved in 5M L anhydrous tetrahydrofuran, and reacted with 58.7M L (58.73mmol) of potassium 1M T-butoxide and 3.11g (11.77mmol) of 18-crown-6 dissolved in an organic solvent under stirring at 60 ℃ for 12h, T L C (PE: EA: 45: 1) was monitored for the progress of the reaction, and when the reaction was complete (no intermediate), the reaction mixture was cooled to room temperature under stirring, 100M L ether was added for extraction, and the organic phase was washed with 50M L water, 50M L saturated aqueous sodium bicarbonate solution and 50M L saturated saline, respectively, dried over anhydrous sodium sulfate, and purified by silica gel column chromatography (PE) to give 584mg (purity 99.63%) of myrcene with a yield of 73.1%.
Example 3
The embodiment comprises the following steps:
(1) in a dry three-necked reaction flask, 1.85g (11.84mmol) of the product obtained in reference example 2 was placed14C2Geraniol was dissolved in 40m L anhydrous tetrahydrofuran, 1.49g (17.71mmol)3, 4-dihydro-2H-pyran and 50mg p-toluenesulfonic acid monohydrate were added, the reaction was stirred at room temperature overnight, and the progress of the reaction was monitored by T L C (PE: EA ═ 10: 1) when the reaction was complete (no water)13C2Geraniol), the reaction solution obtained is concentrated under reduced pressure (-0.08MPa), and PE is purified by silica gel column chromatography with an EA gradient of v/v 1:0 → 30: 1, obtaining 1.46g of intermediate with the yield of 51.6 percent;
(2) dissolving 1.34g (5.58mmol) of intermediate in 5M L anhydrous tetrahydrofuran in a dry three-neck reaction bottle, reacting with 58.7M L (58.73mmol)1M potassium tert-butoxide and 3.11g (11.77mmol) 18-crown-6 dissolved in an organic solvent at 70 ℃ under stirring and under the protection of nitrogen for 14h, monitoring the reaction progress by T L C (PE: EA ═ 45: 1), stirring the obtained reaction solution to room temperature after the reaction is completed (no intermediate), adding 100M L diethyl ether for extraction, and respectively using 50M L water and 50M L saturated carbonThe organic phase was washed with an aqueous sodium hydrogen carbonate solution and 50m L saturated brine in this order, dried over anhydrous sodium sulfate, and purified by silica gel column chromatography (PE) to give 614mg (purity: 99.78%)14C2Myrcene, yield 79.6%.
Claims (9)
1. A kind of13C2High purity of geraniol synthesis13C2-myrcene, characterized in that: the method comprises the following steps:
(1) will be provided with13C2-geraniol is dissolved in an organic solvent, 3, 4-dihydro-2H-pyran and p-toluenesulfonic acid monohydrate are added, the mixture is stirred for reaction, T L C monitors the reaction process, and after the reaction is completed, the obtained reaction solution is decompressed and concentrated, and purified through silica gel column chromatography to obtain an intermediate;
(2) dissolving the intermediate in an organic solvent, stirring and heating the intermediate and potassium tert-butoxide and 18-crown ether-6 dissolved in the organic solvent for reaction under the protection of nitrogen, monitoring the reaction process by T L C, stirring and cooling the obtained reaction solution after the reaction is completed, adding diethyl ether for extraction, sequentially washing the organic phase with water, saturated sodium bicarbonate aqueous solution and saturated salt solution, drying, and purifying by silica gel column chromatography to obtain the high-purity sodium bicarbonate13C2-myrcene.
2. The method of claim 113C2High purity of geraniol synthesis13C2-myrcene, characterized in that: in the step (1), the13C2The feeding molar ratio of geraniol, 3, 4-dihydro-2H-pyran and p-toluenesulfonic acid monohydrate is 1 (1.0-1.8) to (0.01-0.03).
3. The method according to claim 1 or 213C2High purity of geraniol synthesis13C2-myrcene, characterized in that: in the step (2), the feeding molar ratio of the intermediate, potassium tert-butoxide and 18-crown ether-6 is 1 (8-12) to 1-3.
4. The method according to claim 1 or 213C2-geraniolSynthesis of high purity13C2-myrcene, characterized in that: in the step (1), the vacuum degree of the reduced pressure concentration is-0.08 to-0.09 MPa.
5. The method of claim 313C2High purity of geraniol synthesis13C2-myrcene, characterized in that: in the step (1), the vacuum degree of the reduced pressure concentration is-0.08 to-0.09 MPa.
6. The method according to claim 1 or 213C2High purity of geraniol synthesis13C2-myrcene, characterized in that: the organic solvent is anhydrous tetrahydrofuran.
7. The method of claim 313C2High purity of geraniol synthesis13C2-myrcene, characterized in that: the organic solvent is anhydrous tetrahydrofuran.
8. A process as claimed in any one of claims 1 to 713C2High purity of geraniol synthesis13C2Method for synthesizing high-purity myrcene14C2-use of myrcene.
9. A process as claimed in any one of claims 1 to 713C2High purity of geraniol synthesis13C2Application of the method of myrcene in synthesis of high-purity myrcene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010393597.6A CN111454114B (en) | 2020-05-11 | 2020-05-11 | By using 13 C 2 High purity geraniol synthesis 13 C 2 Method of myrcene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010393597.6A CN111454114B (en) | 2020-05-11 | 2020-05-11 | By using 13 C 2 High purity geraniol synthesis 13 C 2 Method of myrcene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111454114A true CN111454114A (en) | 2020-07-28 |
| CN111454114B CN111454114B (en) | 2023-07-14 |
Family
ID=71677962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010393597.6A Active CN111454114B (en) | 2020-05-11 | 2020-05-11 | By using 13 C 2 High purity geraniol synthesis 13 C 2 Method of myrcene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111454114B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651665A (en) * | 2021-08-23 | 2021-11-16 | 万华化学集团股份有限公司 | Preparation method of myrcene |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3475484A (en) * | 1967-11-17 | 1969-10-28 | Givaudan Corp | Process for the preparation of esters from myrcene hydrohalides |
| CN1302286A (en) * | 1998-05-28 | 2001-07-04 | 弗门尼舍有限公司 | Slow release of fragrant compounds is perfoumery using 2-benzoyl benzoates, 2-alkanoyl benzoates or alpha-keto esters |
| CN1434014A (en) * | 2003-02-21 | 2003-08-06 | 中国科学院广州化学研究所 | Improved process for synthesizing citronellol from dihydromyrcene |
| CN102884028A (en) * | 2009-12-18 | 2013-01-16 | 丹尼斯科美国公司 | Purification of isoprene from renewable resources |
| CN104640540A (en) * | 2012-04-14 | 2015-05-20 | 中央研究院 | Enhanced anti-influenza agents conjugated with anti-inflammatory activity |
| CN105026368A (en) * | 2013-02-22 | 2015-11-04 | 莎尤纳诺新加坡私人有限公司 | Process for the isolation of carotenoids |
| US20180339958A1 (en) * | 2015-11-23 | 2018-11-29 | Retrotope, Inc. | Site-specific isotopic labeling of 1,4-diene systems |
-
2020
- 2020-05-11 CN CN202010393597.6A patent/CN111454114B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3475484A (en) * | 1967-11-17 | 1969-10-28 | Givaudan Corp | Process for the preparation of esters from myrcene hydrohalides |
| CN1302286A (en) * | 1998-05-28 | 2001-07-04 | 弗门尼舍有限公司 | Slow release of fragrant compounds is perfoumery using 2-benzoyl benzoates, 2-alkanoyl benzoates or alpha-keto esters |
| CN1434014A (en) * | 2003-02-21 | 2003-08-06 | 中国科学院广州化学研究所 | Improved process for synthesizing citronellol from dihydromyrcene |
| CN102884028A (en) * | 2009-12-18 | 2013-01-16 | 丹尼斯科美国公司 | Purification of isoprene from renewable resources |
| CN104640540A (en) * | 2012-04-14 | 2015-05-20 | 中央研究院 | Enhanced anti-influenza agents conjugated with anti-inflammatory activity |
| CN105026368A (en) * | 2013-02-22 | 2015-11-04 | 莎尤纳诺新加坡私人有限公司 | Process for the isolation of carotenoids |
| US20180339958A1 (en) * | 2015-11-23 | 2018-11-29 | Retrotope, Inc. | Site-specific isotopic labeling of 1,4-diene systems |
Non-Patent Citations (10)
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651665A (en) * | 2021-08-23 | 2021-11-16 | 万华化学集团股份有限公司 | Preparation method of myrcene |
| CN113651665B (en) * | 2021-08-23 | 2023-03-03 | 万华化学集团股份有限公司 | Preparation method of myrcene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111454114B (en) | 2023-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chung | Selective reduction of mono-and disubstituted olefins by sodium borohydride and cobalt (II) | |
| JP7330537B2 (en) | Preparation of 3-hydroxy-3,6-dimethylhexahydrobenzofuran-2-one and its derivatives | |
| CN111454114A (en) | One kind is used13C2High purity of geraniol synthesis13C2Method for producing myrcene | |
| CN108893204B (en) | Method for synthesizing refined lanolin by inert gas with water method | |
| Jones et al. | The Claisen rearrangement in synthesis: acceleration of the Johnson orthoester protocol en route to bicyclic lactones | |
| CN110950745B (en) | Preparation method of phenylacetaldehyde | |
| CN106366057A (en) | Synthetic method of sofosbuvir intermediate | |
| CN109305912B (en) | Method for preparing 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate by condensing isobutyraldehyde | |
| Mishra et al. | Preparation, absolute configuration, and thermolysis of (3R: 5R)-(+)-trans-3, 5-dimethyl-1-pyrazoline | |
| EP0850925A1 (en) | Process for preparation of 13-cis-retinoic acid | |
| CN110734354B (en) | Method for preparing biaryl compound from alcohol compound | |
| CN111620876B (en) | Synthetic method of Rudesiwei key intermediate | |
| CN108610322B (en) | Preparation method of R-glyceraldehyde acetonide | |
| JPH06321860A (en) | Dehydrogenation of methanol | |
| CN110590522A (en) | Synthesis method of megastigmatrienone | |
| CN110845305A (en) | Method for preparing L-menthol by adopting modified homogeneous catalyst | |
| US6090952A (en) | (2R, 3S, 22R, 23R)-2,3,22,23-tetrahydroxy-24-ethyl-β-homo-7-oxa-5α-cholesta n-6-one and a process for preparing the same | |
| CN115417740B (en) | Preparation method of (R) -13-methyl heptadecane | |
| CN115536494B (en) | Synthesis method of 1- (4-bromophenyl) -1, 4-butanediol | |
| CN116969821A (en) | Method for photo-thermal catalysis of hydration carbonylation reaction of 4-tert-butyl phenylacetylene by using carbon nano tube | |
| CN103508999A (en) | Maxacalcitol synthesizing intermediate and preparation method and application thereof | |
| CN115368217B (en) | Synthesis method of 3,4, 5-trimethoxytoluene | |
| JPS6130544A (en) | Preparation of 1,3,5-trialkyl-2,4,6-tris(3,5-dialkyl-4-hydroxybenzyl)benzene | |
| CN114195619B (en) | Preparation method of 2-methyl-3-buten-2-ol | |
| CN113929575B (en) | Preparation method of (1R, 2S) -methyl dihydrojasmonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |