CN102992970B - The synthetic method of trans-anethole - Google Patents
The synthetic method of trans-anethole Download PDFInfo
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- CN102992970B CN102992970B CN201210539029.8A CN201210539029A CN102992970B CN 102992970 B CN102992970 B CN 102992970B CN 201210539029 A CN201210539029 A CN 201210539029A CN 102992970 B CN102992970 B CN 102992970B
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- dewatering agent
- anethole
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- RUVINXPYWBROJD-ONEGZZNKSA-N C/C=C/c(cc1)ccc1OC Chemical compound C/C=C/c(cc1)ccc1OC RUVINXPYWBROJD-ONEGZZNKSA-N 0.000 description 1
- RELLLNVFFUWXHI-UHFFFAOYSA-N CCC(c(cc1)ccc1OC)O Chemical compound CCC(c(cc1)ccc1OC)O RELLLNVFFUWXHI-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention discloses a kind of preparation method of chemical perfume, is specifically related to a kind of synthetic method of trans-anethole.Described synthetic method comprises: will to anisole propyl alcohol at 90-150 DEG C with dewatering agent and the common Reactive Synthesis trans-anethole of water entrainer and anise camphor.The synthetic method of trans-anethole of the present invention can obviously reduce the requirement of reaction to equipment while ensureing reaction conversion ratio, effectively reduces its production cost in industrial applications.
Description
Technical field
The present invention relates to a kind of preparation method of chemical perfume, be specifically related to a kind of synthetic method of trans-anethole.
Background technology
Trans-anethole, chemical name is anise camphor, and it is a kind of conventional chemical industry plant perfume, and its structure is as shown below:
The preparation of existing trans-anethole generally can adopt the mode of separation or chemosynthesis from natural phant, and from natural phant, be separated the preparation method products obtained therefrom output obtaining trans-anethole less, raw materials cost drops into higher; The mode that trans-anethole is prepared in existing chemosynthesis mainly obtains product trans-anethole, i.e. anise camphor after carrying out dehydration reaction to anisole propyl alcohol; The reaction process of above-mentioned chemosynthesis is as follows:
The building-up process of above-mentioned trans-anethole has higher reaction conversion ratio in order to allow raw material to anisole propyl alcohol in dehydrating step, it mainly adopts strong acid at high temperature to react as medium, or adopts dehydration catalyst costly to carry out the mode of reacting.But at high temperature the catalytic reaction mode that obtains trans-anethole to anisole propyl alcohol Dehydration is comparatively harsh to equipment requirements as medium for described employing strong acid, and suitability for industrialized production not only cost is high, and more difficultly industrially to promote; In the mode of the dehydration catalyst (such as titanium dioxide) that described employing is expensive, although follow-up catalyzer after treatment can reprocessing cycle use, because the price of catalyzer own is more expensive, still higher according to its production cost of the industrialized mode of production.
Summary of the invention
In view of this, the invention provides a kind of synthetic method of trans-anethole, it can ensure obviously reduce the requirement of reaction to equipment while reaction conversion ratio, effectively reduces its production cost in industrial applications.
For solving above technical problem, technical scheme of the present invention is the synthetic method adopting a kind of formula 1 compound:
Comprise: by formula 2 compound at 90-150 DEG C with dewatering agent and water entrainer common Reactive Synthesis formula 1 compound:
Preferably, the synthesis step of described synthetic method is: dewatering agent and water entrainer are mixed and be heated to backflow after add formula 2 compound, building-up reactions obtains formula 1 compound.
Preferably, the feed postition of described formula 2 compound is for dripping.
Preferably, described dewatering agent is that at least one is selected from polyacrylamide, sal enixum, sodium pyrosulfate, monoammonium sulfate, hydrolith, anhydrous sodium sulphate, anhydrous magnesium sulfate.
Preferably, described dewatering agent is sal enixum.
Preferably, described water entrainer is that at least one is selected from toluene, benzene, o-Xylol, m-xylene, p-Xylol.
Preferably, described water entrainer is m-xylene.
Preferably, described formula 2 compound be at 100-120 DEG C with dewatering agent and water entrainer common Reactive Synthesis formula 1 compound.
Preferably, the part by weight of described dewatering agent and formula 2 compound is 1:500-800, and the part by weight of described water entrainer and formula 2 compound is 3-8:1.
Compared with prior art, its principle is as follows in the present invention:
The synthetic method of trans-anethole of the present invention and formula 1 compound mainly adopts formula 2 compound namely to anisole propyl alcohol and dewatering agent, the water entrainer mode of building-up reactions at 90-150 DEG C jointly; The reaction raw materials adopted in synthetic method of the present invention includes anisole propyl alcohol, dewatering agent and water entrainer, and the difference of itself and existing technique is not adopt acidic medium and hot conditions.The reaction conditions of the technique of existing catalytic dehydration synthesis trans-anethole is improved in synthetic method of the present invention, synthetic method employing dewatering agent of the present invention and the mode that water entrainer is common and substrate formula 2 compound reacts, thus in the process of reaction, the moisture that reaction produces can be taken out of reaction system timely; Synthetic method of the present invention does not need to react under high temperature and strong acid media, also not necessarily need price dewatering agent costly simultaneously, can make synthetic method of the present invention on the basis ensureing feed stock conversion, reduce reaction conditions to the requirement of equipment, thus reduce its production cost in suitability for industrialized production.
Namely formula 2 compound of the present invention can be commercially available prod to anisole propyl alcohol, also can be own product.
The synthetic method of trans-anethole of the present invention and formula 1 compound preferably adopts the synthesis step of described synthetic method to be: dewatering agent and water entrainer mixed and add formula 2 compound after being heated to backflow, building-up reactions obtains formula 1 compound.
The synthesis step of synthetic method of the present invention can be directly by formula 2 compound namely to the mode that anisole propyl alcohol, dewatering agent reflux with water entrainer mixing post-heating, also can adopt the mode adding formula 2 compound after first dewatering agent and water entrainer being mixed and heated to backflow again.Synthetic method of the present invention preferably adopts the latter further can improve reaction conversion ratio, thus improves the yield of product trans-anethole.
Further, the synthetic method of trans-anethole of the present invention and formula 1 compound preferably adopts the feed postition of described formula 2 compound for dripping when adopting above-mentioned synthesis step.The present invention is in except the dewatering agent of reflux state and the mixture of water entrainer except formula 2 compound is added dropwise to by employing, also can adopt the mode directly added; Synthetic method of the present invention preferably adopts the former further can improve reaction conversion ratio.
The synthetic method of trans-anethole of the present invention and formula 1 compound preferably adopts described dewatering agent to be that at least one is selected from polyacrylamide, sal enixum, sodium pyrosulfate, monoammonium sulfate, hydrolith, anhydrous sodium sulphate, anhydrous magnesium sulfate.Dewatering agent of the present invention can be any one in existing dewatering agent, except above-mentioned several except also can be selected from titanium dioxide, molecular sieve, Vanadium Pentoxide in FLAKES etc.; The present invention preferably adopts described dewatering agent to be a kind of or several arbitrarily mode in polyacrylamide, sal enixum, sodium pyrosulfate, monoammonium sulfate, hydrolith, anhydrous sodium sulphate, anhydrous magnesium sulfate, dewatering agent kind in optimal way of the present invention is on the low side on cost compared to titanium dioxide, molecular sieve or Vanadium Pentoxide in FLAKES etc., therefore adopts the preferred embodiment for the present invention further can reduce its cost in the industrial production.
In addition, the reaction conditions needed for dewatering agent kind that the present invention preferably adopts is comparatively gentle, and temperature is lower and without the need to strong acid or strongly basic medium; Therefore, the preferred dewatering agent of employing the present invention further can reduce the requirement to equipment.
Further, the synthetic method of trans-anethole of the present invention and formula 1 compound preferably adopts described dewatering agent to be sal enixum.The present invention selects sal enixum to be the preferred version of dewatering agent as synthetic method of the present invention further in the dewatering agent of above-mentioned preferred employing.
The synthetic method of trans-anethole of the present invention and formula 1 compound preferably adopts described water entrainer to be that at least one is selected from toluene, benzene, o-Xylol, m-xylene, p-Xylol.Water entrainer of the present invention can be any one water entrainer existing.The present invention preferably adopts the water entrainer of phenyl ring class.Benzene ring type compounds is comparatively common as water entrainer, meanwhile, compared to other, the such as water entrainer of macromolecular compound class, its cost is lower and be easy to get.
Further, the synthetic method of trans-anethole of the present invention and formula 1 compound preferably adopts described water entrainer to be m-xylene.Water entrainer of the present invention preferably adopt above-mentioned several time, when m-xylene is wherein as water entrainer, the selectivity of dehydration reaction can be improved preferably, thus improve the quality of products obtained therefrom trans-anethole.
The synthetic method of trans-anethole of the present invention and formula 1 compound preferably adopt described formula 2 compound at 100-120 DEG C with dewatering agent and water entrainer common Reactive Synthesis formula 1 compound.Synthesis reaction temperature in synthetic method of the present invention is 90-150 DEG C, depends primarily on the activity of water entrainer itself and the temperature of reaction needed for water azeotropic and catalyzer.When the present invention preferably adopts synthesis reaction temperature to be 100-120 DEG C, in reaction system, side reaction is less, and reaction conversion ratio is higher, thus better can improve the yield of product.Preferred, when adopting sal enixum to be dewatering agent, synthesis reaction temperature is the 100-120 DEG C of preferred embodiment for building-up reactions of the present invention.
The synthetic method of trans-anethole of the present invention and formula 1 compound preferably adopts the part by weight of described dewatering agent and formula 2 compound to be 1:500-800, and the part by weight of described water entrainer and formula 2 compound is 3-8:1.The part by weight of dewatering agent of the present invention, water entrainer and formula 2 between compound can be preferably aforementioned proportion, and the reaction conversion ratio of gained reaction system is improved further, can avoid the waste of material simultaneously.
Further, the synthetic method of trans-anethole of the present invention and formula 1 compound preferably adopts the part by weight of described dewatering agent and formula 2 compound to be 1:500-600, and the part by weight of described water entrainer and formula 2 compound is 5-8:1.Synthetic method of the present invention adopts above-mentioned preferred version more further can improve reaction conversion ratio.
Embodiment
In order to make those skilled in the art understand technical scheme of the present invention better, below in conjunction with specific embodiment, the present invention is described in further detail.
Trans-anethole (anise camphor): to anisole propyl alcohol:
Embodiment 1
Each material is taken according to following weight proportioning:
To anisole propyl alcohol 500kg
Dewatering agent-anhydrous sodium sulphate 1kg
Water entrainer-toluene 1500kg
Weighed dewatering agent and water entrainer are placed in reactor, and be uniformly mixed and be heated to 100 DEG C of appearance backflows, then will be added dropwise in recirculate mixing thing to anisole propyl alcohol, control time for adding is 6-8 hour; After anisole propyl alcohol is dripped, maintaining the temperature between 100-150 DEG C and react 30min-2 hour, getting final product stopped reaction when not there are flowing out in water trap.
Detected by LC/MS by above-mentioned reaction mixture sampling, obtaining reaction conversion ratio is 90.2%; Gained reaction mixture obtains product trans-anethole 400kg through aftertreatment, and product yield is 90.1%.
Embodiment 2
Each material is taken according to following weight proportioning:
To anisole propyl alcohol 500kg
Dewatering agent-anhydrous magnesium sulfate 1kg
Water entrainer-benzene 4000kg
Weighed dewatering agent and water entrainer are placed in reactor, and be uniformly mixed and be heated to 80 DEG C of appearance backflows, then will be added dropwise in recirculate mixing thing to anisole propyl alcohol, control time for adding is 6-8 hour; After anisole propyl alcohol is dripped, maintaining the temperature between 90-150 DEG C and react 30min-2 hour, getting final product stopped reaction when not there are flowing out in water trap.
Detected by LC/MS by above-mentioned reaction mixture sampling, obtaining reaction conversion ratio is 90.6%; Gained reaction mixture obtains product trans-anethole 401kg through aftertreatment, and product yield is 90.1%.
Embodiment 3
Each material is taken according to following weight proportioning:
To anisole propyl alcohol 800kg
Dewatering agent-hydrolith 1kg
Water entrainer-p-Xylol 2400kg
Weighed dewatering agent and water entrainer are placed in reactor, and be uniformly mixed and be heated to 115 DEG C of appearance backflows, then will be added dropwise in recirculate mixing thing to anisole propyl alcohol, control time for adding is 6-8 hour; After anisole propyl alcohol is dripped, maintaining the temperature between 120-150 DEG C and react 30min-2 hour, getting final product stopped reaction when not there are flowing out in water trap.
Detected by LC/MS by above-mentioned reaction mixture sampling, obtaining reaction conversion ratio is 90.3%; Gained reaction mixture obtains product trans-anethole 634kg through aftertreatment, and product yield is 89.1%.
Embodiment 4
Each material is taken according to following weight proportioning:
To anisole propyl alcohol 800kg
Dewatering agent-sal enixum 1kg
Water entrainer-o-Xylol 6400kg
Weighed dewatering agent and water entrainer are placed in reactor, and be uniformly mixed and be heated to 120 DEG C of appearance backflows, then will be added dropwise in recirculate mixing thing to anisole propyl alcohol, control time for adding is 6-8 hour; After anisole propyl alcohol is dripped, maintaining the temperature between 120-150 DEG C and react 30min-2 hour, getting final product stopped reaction when not there are flowing out in water trap.
Detected by LC/MS by above-mentioned reaction mixture sampling, obtaining reaction conversion ratio is 91.4%; Gained reaction mixture obtains product trans-anethole 640kg through aftertreatment, and product yield is 90.0%.
Embodiment 5
Each material is taken according to following weight proportioning:
To anisole propyl alcohol 600kg
Dewatering agent-4A molecular sieve 1kg
Water entrainer-p-Xylol 3000kg
Weighed dewatering agent and water entrainer are placed in reactor, and be uniformly mixed and be heated to 120 DEG C of appearance backflows, then will be added dropwise in recirculate mixing thing to anisole propyl alcohol, control time for adding is 6-8 hour; After anisole propyl alcohol is dripped, maintaining the temperature between 120-150 DEG C and react 30min-2 hour, getting final product stopped reaction when not there are flowing out in water trap.
Detected by LC/MS by above-mentioned reaction mixture sampling, obtaining reaction conversion ratio is 94.2%; Gained reaction mixture obtains product trans-anethole 500kg through aftertreatment, and product yield is 93.4%.
Embodiment 6
Each material is taken according to following weight proportioning:
To anisole propyl alcohol 600kg
Dewatering agent-sal enixum 1kg
Water entrainer-m-xylene 3600kg
Weighed dewatering agent and water entrainer are placed in reactor, and be uniformly mixed and be heated to 115 DEG C of appearance backflows, then will be added dropwise in recirculate mixing thing to anisole propyl alcohol, control time for adding is 6-8 hour; After anisole propyl alcohol is dripped, maintaining the temperature between 120-150 DEG C and react 30min-2 hour, getting final product stopped reaction when not there are flowing out in water trap.
Detected by LC/MS by above-mentioned reaction mixture sampling, obtaining reaction conversion ratio is 94.5%; Gained reaction mixture obtains product trans-anethole 500kg through aftertreatment, and product yield is 93.3%.
Below be only the preferred embodiment of the present invention, it should be pointed out that above-mentioned preferred implementation should not be considered as limitation of the present invention, protection scope of the present invention should be as the criterion with claim limited range.For those skilled in the art, without departing from the spirit and scope of the present invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. the synthetic method of formula 1 compound:
It is characterized in that comprising: by formula 2 compound at 90-150 DEG C with dewatering agent and water entrainer common Reactive Synthesis formula 1 compound:
Described dewatering agent is that one is selected from sal enixum, sodium pyrosulfate, monoammonium sulfate, hydrolith, anhydrous sodium sulphate, anhydrous magnesium sulfate; Described water entrainer is that one is selected from toluene, benzene, o-Xylol, m-xylene, p-Xylol; The part by weight of described dewatering agent and formula 2 compound is 1:500-800, and the part by weight of described water entrainer and formula 2 compound is 3-8:1; The synthesis step of described synthetic method is: dewatering agent and water entrainer are mixed and be heated to backflow after add formula 2 compound, building-up reactions obtains formula 1 compound.
2. building-up reactions according to claim 1, is characterized in that: the feed postition of described formula 2 compound is for dripping.
3. synthetic method according to claim 1, is characterized in that: described dewatering agent is sal enixum.
4. synthetic method according to claim 1, is characterized in that: described water entrainer is m-xylene.
5. synthetic method according to claim 1, is characterized in that: described formula 2 compound at 100-120 DEG C with dewatering agent and water entrainer common Reactive Synthesis formula 1 compound.
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Citations (2)
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| CN1856458A (en) * | 2003-09-25 | 2006-11-01 | 住友化学株式会社 | Process for producing a-methylstyrene |
| WO2009111443A2 (en) * | 2008-03-03 | 2009-09-11 | Honeywell International Inc. | Heat transfer system comprising brazed aluminum, method, heat transfer fluid, and additive package |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1856458A (en) * | 2003-09-25 | 2006-11-01 | 住友化学株式会社 | Process for producing a-methylstyrene |
| WO2009111443A2 (en) * | 2008-03-03 | 2009-09-11 | Honeywell International Inc. | Heat transfer system comprising brazed aluminum, method, heat transfer fluid, and additive package |
Non-Patent Citations (2)
| Title |
|---|
| Neutral Ionic Liquid [hmim]Br as a Green Reagent and Solvent for the Mild and Efficient Dehydration of Benzyl Alcohols into (E)-Arylalkenes Under Microwave Irradiation;Rakesh Kumar等;《Eur. J. Org. Chem.》;20081231;第5577-5582页 * |
| 苯乙烯生产现状及工艺技术进展;饶兴鹤;《化工生产与技术》;20021025(第05期);第32-36页 * |
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