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CN111454114B - By using 13 C 2 High purity geraniol synthesis 13 C 2 Method of myrcene - Google Patents

By using 13 C 2 High purity geraniol synthesis 13 C 2 Method of myrcene Download PDF

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CN111454114B
CN111454114B CN202010393597.6A CN202010393597A CN111454114B CN 111454114 B CN111454114 B CN 111454114B CN 202010393597 A CN202010393597 A CN 202010393597A CN 111454114 B CN111454114 B CN 111454114B
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myrcene
geraniol
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陈雨雷
伍君
方宁静
张�雄
阮善龙
刘大成
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Changsha Beita Pharmatech Co ltd
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    • 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
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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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Abstract

By using 13 C 2 High purity geraniol synthesis 13 C 2 -a method of myrcene comprising the steps of: (1) Will be 13 C 2 -geraniol is dissolved in an organic solvent, hydrogen peroxide and p-toluenesulfonic acid monohydrate are added for stirring reaction, TLC monitors the reaction progress, and after the reaction is completed, the obtained reaction liquid is concentrated under reduced pressure and purified by silica gel column chromatography to obtain an intermediate; (2) Dissolving the intermediate in an organic solvent, stirring and heating the mixture with potassium tert-butoxide and 18-crown ether-6 dissolved in the organic solvent under the protection of nitrogen, monitoring the reaction progress by TLC, stirring and cooling the obtained reaction liquid after the reaction is completed, adding diethyl ether for extraction, respectively washing the organic phase with water, saturated sodium bicarbonate aqueous solution and saturated saline water in sequence, drying, purifying by silica gel column chromatography, and obtaining high purity 13 C 2 -myrcene. The invention does not use metal catalyst or additive, has mild process conditions, has the advantages of simplicity, high efficiency, economy and green, and is especially suitable for isotopes 13 C or 14 C labeling and synthesis of non-isotopic labeled myrcene.

Description

By using 13 C 2 High purity geraniol synthesis 13 C 2 Method of myrcene
Technical Field
The present invention relates to a kind of 13 C 2 -myrcene synthesis method, in particular to a method for synthesizing myrcene by using 13 C 2 High purity geraniol synthesis 13 C 2 Method for myrcene, which method is equally applicable to myrcene and laurene 14 C 2 -synthesis of myrcene.
Background
Myrcene has pleasant sweet balsam smell, is an important chemical raw material and an intermediate in the perfume industry, and is widely applied to synthesizing various rare perfume products such as citronellal, neotame, ambroxol and the like, and is also an important raw material in the pharmaceutical industry such as vitamin synthesis, insect repellent, antitumor active substances and the like. The natural myrcene can be extracted from plant essential oils such as verbena, myrcia, laurel leaf and olibanum gum oil, but the content of the myrcene in the natural essential oil is low, and the natural essential oil is limited by seasons, climates and other factors, so that the harvested yield and quality of the natural essential oil are unstable, and the market demand can not be met all the time; but can obtain laurene products by extracting beta-pinene in turpentine and then cracking in industry, the method has low cost and high yield, and is widely applied in industry; it has also been reported that myrcene can be obtained by a chemical synthesis method, for example, isoprene is used as a raw material, alkali metal potassium and sodium are used as catalysts, diisopropylamine is used as a shape selective agent and a polymerization inhibitor, and the method has the advantages of wide raw material sources, short reaction steps, simple process operation and the like, but the industrial production cannot be realized at present due to the problems of poor myrcene selectivity, low yield, high cost and the like. Whichever method is used, the overall yield of myrcene and the purity of the product are not high. Wherein, the beta-pinene cracking method widely adopted in industry can only obtain laurene products with the mass fraction of 70-80 percent.
In the prior art, myrcene is prepared by using geraniol, such as high-temperature and high-pressure dehydration or by adding various dehydration reagents (alkali, dehydration reagents and the like), and a distillation method is generally adopted to purify the product, but the method needs high temperature and high pressure, consumes energy and time, has higher equipment requirements and higher cost, and more importantly, the dehydration product is easy to exist in a plurality of isomers under the conditions of high temperature and high pressure, the purity of the target product is low, the subsequent purification process is complex, and the time and the labor are wasted; although in order to reduce the occurrence of isomerization side reactions, precious metal catalysts are generally used in industry to synthesize myrcene, such as catalytic synthesis by using metal palladium catalysts, the method can only reduce the occurrence of isomer side reactions to a certain extent, and more importantly, the cost of the metal palladium catalysts is high, which is not beneficial to industrial production, and the environmental problems related to precious metal reagent recovery and pollution are not well solved, so that the safety is poor.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects existing in the prior art and providing a method which is simple, efficient, mild in process condition, free of metal catalyst or additive, economical, green and high in yield 13 C 2 High purity geraniol synthesis 13 C 2 -a method of myrcene.
The technical scheme adopted for solving the technical problems is as follows: by using 13 C 2 High purity geraniol synthesis 13 C 2 -a method of myrcene comprising the steps of:
(1) Will be 13 C 2 -geraniol is dissolved in an organic solvent, 3, 4-dihydro-2H-pyran and p-toluenesulfonic acid monohydrate are added for stirring reaction, TLC monitors the reaction progress, and after the reaction is completed, the obtained reaction liquid is concentrated under reduced pressure and purified by silica gel column chromatography to obtain an intermediate;
(2) Dissolving the intermediate in an organic solvent, stirring and heating the mixture with potassium tert-butoxide and 18-crown ether-6 dissolved in the organic solvent under the protection of nitrogen, monitoring the reaction progress by TLC, stirring and cooling the obtained reaction liquid after the reaction is completed, adding diethyl ether for extraction, respectively washing the organic phase with water, saturated sodium bicarbonate aqueous solution and saturated saline water in sequence, drying, purifying by silica gel column chromatography, and obtaining high purity 13 C 2 -myrcene.
Preferably, in step (1), the 13 C 2 The feeding mole ratio of the geraniol, the 3, 4-dihydro-2H-pyran and the p-toluenesulfonic acid monohydrate is 1 (1.0-1.8): 0.01-0.03.
Preferably, in the step (2), the feeding mole ratio of the intermediate, the potassium tert-butoxide and the 18-crown ether-6 is 1 (8-12): 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 is described in 13 C 2 High purity geraniol synthesis 13 C 2 Method for synthesizing laurene with high purity 14 C 2 -use of myrcene.
The invention is described in 13 C 2 High purity geraniol synthesis 13 C 2 -application of myrcene method in synthesizing high-purity myrcene.
The synthetic route of the invention is as follows: by combining 13 C 2 The hydroxyl group of the geraniol is converted into an easy leaving group (THP) intermediate, and then the intermediate is separated under alkaline condition to obtain high purity 13 C 2 -myrcene.
Figure BDA0002486515160000021
Note that: * To stabilize isotopes 13 C or radioisotope 14 C。
Compared with the prior art, the invention has the beneficial effects that: firstly, no metal catalyst or additive is used, so that the method is economical and green, the process condition is 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 raw materials required by synthesis are simple and easily obtained, the intermediate is stable, the conventional controllable temperature of 50-70 ℃ is adopted in the heating reaction process, and the 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 product is obtained 13 C 2 The chemical purity of the myrcene is up to 99 percent, the isotope abundance is high, and the myrcene is especially suitable for isotopes 13 C、 14 C labeling and synthesis of non-isotopic labeled myrcene.
Detailed Description
The invention is further illustrated below with reference to examples.
The chemical reagents used in the examples of the present invention, unless otherwise specified, were all obtained by conventional commercial means.
In practice said geraniol [ ] 13 C 2 ) Or geraniol 14 C 2 ) The synthetic route of (2) is as follows:
Figure BDA0002486515160000031
note that: * To stabilize isotopes 13 C or radioisotope 14 C。
Reference example 1
1. The synthesis of intermediate 1 is performed as follows:
(1) Adding commercially available marked acetic acid into a three-mouth bottle with a condenser tube 13 C 2 ) Namely, raw material 1 (2.00 g,32.24 mmol), trifluoroacetic anhydride (15.78 g,75.11 mmol) and DMAP (40 mg,0.32 mmol) are stirred and heated to 60 ℃, bromine (5.87 g,36.75 mmol) is slowly added dropwise for 1 hour, and after the dropwise addition, the mixture is kept at 60 ℃ for continuous stirring for 1 hour;
(2) Stopping heating, stirring the reaction system, cooling to room temperature, adding benzyl alcohol (20 ml), stirring, heating to 60 ℃, and continuing stirring for 12h;
(3) The heating was stopped, the reaction solution was cooled down to room temperature with stirring, the reaction system was diluted with saturated sodium hydrogencarbonate (40 ml), extracted with diethyl ether (60 ml. Times.4), the organic phases were combined, washed with saturated aqueous sodium hydrogencarbonate (50 ml) and saturated aqueous sodium thiosulfate (50 ml), the resulting product was dried over anhydrous sodium sulfate, filtered with water, the resulting filtrate was concentrated under reduced pressure, and the resulting concentrate was stirred and purified by silica gel column chromatography (PE: EA gradient v/v=1:0.fwdarw.20:1) to give 6.90g (yield: 92.6%) of anhydrous oil, intermediate 1.
2. Intermediate 2 was synthesized as follows:
(1) A single-port reaction flask with a condenser is added with intermediate 1 (6.89 g,29.82 mmol) and raw material 2 (5.45 g,32.80 mmol), stirred and heated to 125 ℃ under nitrogen protection, stirred for 4h;
(2) TLC (PE: ea=1:1) spot-on plate showed that the reaction was complete, little intermediate 1 remained, and a large amount of intermediate 2 was formed;
(3) The reaction system was stopped from heating, cooled to room temperature, stirred with silica gel, and purified by column chromatography (PE: ea=20:1→5:1→1:1→1:2) to give 8.48g (yield: 98.7%) of intermediate 2 as a colorless oil.
3. The synthesis of intermediate 3 is performed as follows:
(1) Sodium hydride (1.22 g,30.49 mmol) was added to the dried reaction flask, the air in the reaction flask was replaced with nitrogen, anhydrous tetrahydrofuran (30 ml) was added, intermediate 2 (8.45 g,29.31 mmol) dissolved in 10ml of anhydrous tetrahydrofuran was added dropwise at 0℃and stirring was continued at room temperature for 0.5h after the addition, raw material 3 (3.70 g,29.31 mmol) was added dropwise, and the reaction system was stirred and warmed to 50℃overnight.
(2) The reaction system was cooled to room temperature with stirring, quenched with water, extracted with diethyl ether (100 ml. Times.3), the organic phases were combined, dried over anhydrous sodium sulfate, and the resulting product was concentrated under reduced pressure and purified by column chromatography on silica gel (PE: ea=1:0) to give 3.55g (yield: 46.5%) of intermediate 3 as a pale yellow oil.
4. Geraniol 13 C 2 ) The specific operation is as follows:
(1) LAH (0.94 g,24.75 mmol) was added to anhydrous tetrahydrofuran (15 ml), aluminum trichloride (1.18 g,8.84 mmol) was added in portions under nitrogen protection, the reaction system was cooled to 0℃and intermediate 3 (3.54 g,13.60 mmol) dissolved in 5ml of anhydrous tetrahydrofuran was slowly added dropwise, after the dropwise addition, the reaction system was naturally warmed to room temperature and stirred for 2h;
(2) TLC (PE: ea=100:1) without intermediate 3 and reaction was completed.
(3) Water (0.94 ml), 15% aqueous sodium hydroxide solution (0.94 ml), water (2.82 ml) were sequentially added to the reaction system, stirring was continued for 15min, concentration under reduced pressure was performed, and the obtained concentrated product was purified by silica gel column chromatography (PE: EA=10:1),
reference example 2
Reference example 2 differs from reference example 1 only in that the starting material 1 added in the synthesis of intermediate 1 is labeled acetic acid 14 C 2 ) Reference to geraniol 14 C 2 ) Obtaining pale yellow oily matter, namely geraniol @ through the synthetic route 14 C 2 ) 1.92g (yield: 90.1%).
Example 1
The embodiment comprises the following steps:
(1) 1.85g (11.84 mmol) of the mixture obtained in reference example 1 are placed in a dry three-port reaction flask 13 C 2 Geraniol was dissolved in 40mL anhydrous tetrahydrofuran, 1.49g (17.71 mmol) of 3, 4-dihydro-2H-pyran and 50mg of p-toluenesulfonic acid monohydrate were added, the reaction was stirred at room temperature overnight, TLC (PE: ea=10:1) monitored for progress of the reaction when the reaction was complete (no 13 C 2 Geraniol), the reaction mixture was concentrated under reduced pressure (-0.08 MPa), and purified by silica gel column chromatography (PE: EA gradient v/v 1:0→30: 1) 1.46g of intermediate was obtained in a yield of 51.2%;
( 2) 1.40g (5.82 mmol) of the intermediate was dissolved in 5mL of anhydrous tetrahydrofuran and reacted with 58.7mL (58.73 mmol) of 1M potassium tert-butoxide and 3.11g (11.77 mmol) of 18-crown-6 dissolved in an organic solvent in a dry three-port reaction flask under nitrogen with stirring at a temperature of 60℃for 14h, TLC (PE: EA=45: 1) After the reaction was completed (no intermediate) and the reaction mixture was cooled to room temperature with stirring, 100mL of diethyl ether was added to conduct extraction, and the organic phase was washed successively with 50mL of water, 50mL of saturated aqueous sodium bicarbonate and 50mL of saturated aqueous saline, respectively, dried over anhydrous sodium sulfate, and purified by silica gel column chromatography (PE) to give 680mg (purity 99.81%) ) 13 C 2 Myrcene is produced in a yield of 84.5%.
Example 2
The embodiment comprises the following steps:
(1) In a dry three-port reaction flask, 1.85g (11.84 mmol) of commercially available geraniol (purity 98%) was dissolved in 40mL of anhydrous tetrahydrofuran, 1.49g (17.71 mmol) of 3, 4-dihydro-2H-pyran and 50mg of p-toluenesulfonic acid monohydrate were added, the reaction was stirred at room temperature overnight, TLC (PE: EA=10:1) monitored for progress of the reaction, and when the reaction was complete (geraniol), the obtained reaction solution was concentrated under reduced pressure (-0.08 MPa) and purified by silica gel column chromatography (PE: EA gradient v/v 1:0→30:1) to give 1.46g of intermediate with a yield of 51.2%;
(2) 1.39g (5.78 mmol) of the intermediate was dissolved in 5mL of anhydrous tetrahydrofuran in a dry three-port reaction flask, reacted with 58.7mL (58.73 mmol) of 1M potassium tert-butoxide and 3.11g (11.77 mmol) of 18-crown ether-6 dissolved in an organic solvent under nitrogen protection with stirring at a temperature of 60℃for 12 hours, TLC (PE: EA=45:1) monitored the progress of the reaction, and after completion of the reaction (no intermediate), the obtained reaction solution was stirred to room temperature, extracted with 100mL of diethyl ether, the organic phase was washed successively with 50mL of water, 50mL of saturated aqueous sodium bicarbonate and 50mL of saturated aqueous saline, dried over anhydrous sodium sulfate, and purified by silica gel column chromatography (PE) to obtain 584mg (purity 99.63%) of myrcene in a yield of 73.1%.
Example 3
The embodiment comprises the following steps:
(1) 1.85g (11.84 mmol) of the mixture obtained in reference example 2 were placed in a dry three-port reaction flask 14 C 2 Geraniol was dissolved in 40mL anhydrous tetrahydrofuran, 1.49g (17.71 mmol) of 3, 4-dihydro-2H-pyran and 50mg of p-toluenesulfonic acid monohydrate were added, the reaction was stirred at room temperature overnight, TLC (PE: ea=10:1) monitored for progress of the reaction when the reaction was complete (no 13 C 2 -geraniol), the reaction mixture was concentrated under reduced pressure (-0.08 MPa), and the PE was purified by silica gel column chromatography with EA gradient v/v 1:0→30:1, 1.46g of intermediate is obtained, and the yield is 51.6%;
( 2) 1.34g (5.58 mmol) of the intermediate was dissolved in 5mL of anhydrous tetrahydrofuran and reacted with 58.7mL (58.73 mmol) of 1M potassium tert-butoxide and 3.11g (11.77 mmol) of 18-crown-6 dissolved in an organic solvent in a dry three-port reaction flask under nitrogen with stirring at a temperature of 70℃for 14h, TLC (PE: EA=45: 1) After the reaction was completed (no intermediate) and the reaction mixture was cooled to room temperature with stirring, 100mL of diethyl ether was added to conduct extraction, and the organic phase was washed successively with 50mL of water, 50mL of saturated aqueous sodium bicarbonate and 50mL of saturated aqueous saline, respectively, dried over anhydrous sodium sulfate, and purified by silica gel column chromatography (PE) to give 614mg (purity 99.78%) ) 14 C 2 Myrcene, yield 79.6%.

Claims (7)

1. The method comprises the following steps of 13 C 2 High purity geraniol synthesis 13 C 2 -a method of myrcene, characterized by: the method comprises the following steps:
(1) Will be 13 C 2 -geraniol is dissolved in an organic solventAdding 3, 4-dihydro-2H-pyran and p-toluenesulfonic acid monohydrate into a solvent, stirring for reaction, monitoring the reaction progress by TLC, concentrating the obtained reaction liquid under reduced pressure after the reaction is completed, and purifying by silica gel column chromatography to obtain an intermediate;
(2) Dissolving the intermediate in an organic solvent, stirring and heating the mixture with potassium tert-butoxide and 18-crown ether-6 dissolved in the organic solvent under the protection of nitrogen, monitoring the reaction progress by TLC, stirring and cooling the obtained reaction liquid after the reaction is completed, adding diethyl ether for extraction, respectively washing the organic phase with water, saturated sodium bicarbonate aqueous solution and saturated saline water in sequence, drying, purifying by silica gel column chromatography, and obtaining high purity 13 C 2 -myrcene;
the said 13 C 2 The synthetic route for geraniol is as follows:
Figure QLYQS_1
wherein is a stable isotope 13 C。
2. According to claim 1 13 C 2 High purity geraniol synthesis 13 C 2 -a method of myrcene, characterized by: in step (1), the 13 C 2 The feeding mole ratio of the geraniol, the 3, 4-dihydro-2H-pyran and the p-toluenesulfonic acid monohydrate is 1 (1.0-1.8): 0.01-0.03.
3. According to claim 1 or 2 13 C 2 High purity geraniol synthesis 13 C 2 -a method of myrcene, characterized by: in the step (2), the feeding mole ratio of the intermediate, the potassium tert-butoxide and the 18-crown ether-6 is 1 (8-12) to 1-3.
4. According to claim 1 or 2 13 C 2 High purity geraniol synthesis 13 C 2 -a method of myrcene, characterized by: in the step (1), the vacuum degree of the reduced pressure concentration is-0.08 to-0.09MPa。
5. A method according to claim 3 13 C 2 High purity geraniol synthesis 13 C 2 -a method of myrcene, characterized by: in the step (1), the vacuum degree of the reduced pressure concentration is minus 0.08 to minus 0.09MPa.
6. According to claim 1 or 2 13 C 2 High purity geraniol synthesis 13 C 2 -a method of myrcene, characterized by: the organic solvent is anhydrous tetrahydrofuran.
7. A method according to claim 3 13 C 2 High purity geraniol synthesis 13 C 2 -a method of myrcene, characterized by: the organic solvent is anhydrous tetrahydrofuran.
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