CN101792378B - Method for preparing anisaldehyde - Google Patents
Method for preparing anisaldehyde Download PDFInfo
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- CN101792378B CN101792378B CN 200910214322 CN200910214322A CN101792378B CN 101792378 B CN101792378 B CN 101792378B CN 200910214322 CN200910214322 CN 200910214322 CN 200910214322 A CN200910214322 A CN 200910214322A CN 101792378 B CN101792378 B CN 101792378B
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Abstract
The invention discloses a method for preparing anisaldehyde. The method comprises the following steps: (1) mixing anethole, organic solvents and water to obtain reaction materials; adding the reaction materials into a bubble reaction tower and introducing mixed gas of ozone and oxygen to carry out ozonization reaction; continuing introducing oxygen to expel redundant ozone after the ozonization reaction is over to obtain ozonization reaction liquid; and (2) heating anhydrous sodium sulfite solution to 60-80 DEG C and dropwise adding the ozonization reaction liquid to carry out reduction reaction; continuing reacting for 30-60min after dropwise adding the ozonization reaction liquid, cooling and standing the reactant and dividing the liquid to obtain the coarse anisaldehyde; and removing the organic solvents by distillation to obtain the anisaldehyde product. The method avoids a little side reaction in the process of ozonization, lowers the equipment and production cost, solves the key problems confronted by industrialized production, such as equipment corrosion due to presence of acetic acid, heavy environmental pollution and the like, and opens up a way for large-scale industrialized production.
Description
Technical field
The invention belongs to the spices preparation field, particularly a kind ofly with an organic solvent make the method that double solvents trans-anethole ozonization is produced aubepine with water.
Background technology
Aubepine (anisaldehyde, anisic aldehyde, p-methoxybenzaldehyde) claim again p-methoxybenzaldehyde,, chemistry aubepine by name.Sterling is colourless or weak yellow liquid, and with strong may blossom fragrance, fragrance is lasting, has simultaneously stronger antioxidant property.Density is 1.123g/ml (20 ℃), 2.5 ℃ of fusing points, 249.5 ℃ of boiling points, 144～200 ℃ (28kPa), 134～135 ℃ (1.6kPa), 83 ℃ (0.267kPa), relative density 1.1191 (15/4 ℃), specific refractory power 1.5720 (20 ℃), flash-point is 117.8 ℃.Slightly soluble in water is soluble in ethanol and ether.Molecular formula is C
8H
8O
2, molecular weight is 136.15.
Because aubepine has lasting hawthorn fragrance, the fragrant tempting multiple essence such as sweet floral type, cloves and hawthorn odor type that are widely used in preparing, preparation (the meticulous and specialty chemicals that are used for food, carbohydrate and beverage flavor, 2000, (12): 33-34; Fragrance flavor and cosmetic, 2005, (2): 21-22); Aspect organic intermediate, it is intermediate (herbal medicine, 1994,25 (10): 551 of preparation medicine Porphyrin-Based Sensitizer, vasodilator, oxyammonia card base penicillin etc.; Forest chemical engineering communication, 2004,38 (1): 31-35); On agricultural, it can be used as sterilant, biological growth inhibitor etc.
Aubepine is to be made through oxidation style by trans-anethole (claiming again star aniseed oil).The trans-anethole oxidation style mainly is divided three classes: conventional oxidation method, electrooxidation method and Ozonation.The traditional method that is prepared aubepine by trans-anethole is a lot, is with the sodium dichromate method the earliest and sulfuric acid-silver nitrate method oxidation trans-anethole prepares aubepine, but yield is very low, and preparation condition harshness, operational difficulty, production cost is high, environmental pollution is serious.Used again afterwards dichromate titration and permanganate method, the aubepine yield is also lower, about about 50%, and in reaction, to consume a large amount of acid, and produce a large amount of sewage, exist equally " three wastes " to pollute reluctant problem, and acid is to the machinery equipment seriously corroded, be difficult to use (chemistry world, 1988,29 (6): 253-256) in production.Zhong Wenhai improves the technique that manganese dioxide prepares aubepine, take the natural manganese dioxede in powder of higher-grade and dilute sulphuric acid as oxygenant, the aubepine productive rate brings up to 74%, but still there is the manganese salt pollution, equipment corrosion is serious, pollution is difficult to the shortcoming (fragrance flavor and cosmetics such as improvement, 1990, (4): 4-5).The electrooxidation method has two kinds of methods, and direct oxidation method namely in the presence of supporting electrolyte, is directly made the synthetic aubepine of oxygenant with electronics; Another kind is Indirect Electrooxidation, and namely in the presence of supporting electrolyte, electronics is oxidization electrolysis matter medium at first, and the medium of oxidation is the deoxidation trans-anethole again.In the thirties in last century, F.Fichter is take water as solvent, under agitation with PbO
2Be electrode, continuous current (1～2mA/cm
2) the electrolytic oxidation trans-anethole, obtaining 52% aubepine, current efficiency is 34.7%.Nineteen sixty-eight, Chadambaram Mn
3+/ Mn
2+Redox couple indirect electrooxidation trans-anethole has synthesized spices aubepine (J.Electrochem.Soc.India., 1968, (17): 95).Nineteen ninety-five, Li Zelin etc. have carried out comparatively deep research to the anode direct oxidation of trans-anethole.Take graphite or titanium base ruthenium as anode, stainless steel is negative electrode, and 80%～90% aqueous ethanolic solution is solvent, 0.25mol/L H
2SO
4Be supporting electrolyte, the concentration of trans-anethole is not more than 0.15mol/L, and the control anode potential is 1.3～1.5V electrolysis, and the productive rate that can get aubepine is about 60% (fine chemistry industry, 1995,12 (1): 16-18).This method power consumption is higher, and equipment requirements is higher, the product separation difficulty.It is to study more method over nearly 30 years that ozonization method prepares aubepine.Ozone has that oxidizing power is strong, selectivity good and the characteristics such as speed of response is fast, can decompose voluntarily after reaction finishes, and noresidue does not produce industrial unmanageable " three wastes ", is the oxygenant of a kind of " cleaning ".Methyl allylphenol is the unsaturated olefin with phenyl ring, and ozone can be for the efficient oxidation of two keys, and can the attack phenyl ring.So ozonization method is subject to the extensive concern of chemist with its numerous advantage, also become the focus of trans-anethole oxidation research.
The alkene ozonization starts from Germanization scholar in 1855
Research to the reaction of the organism such as ozone and ethene, thereafter C.Harries used the time in 15 years that organic ozonization is conducted extensive research since 1901, they are under-78 ℃, the condition of non-polar solvent pentamethylene, a large amount of aldehyde and ketone compound (Angew.Chem.internal.Edit.1975,14 (11): 745-752) have been synthesized.
Because the restriction of resource mainly concentrates on chain unsaturated olefin and some other unsaturated aromatic hydrocarbon to the research of ozonization abroad, and to the rarely seen report of the ozonization of trans-anethole.Recent years is more to the ozonization research of trans-anethole, 1997, Liu Lihua etc. are take trans-anethole as raw material, double solvents H makes solvent (wherein acetic acid content 5%), and the amount ratio of trans-anethole and solvent is 1: 3, and temperature of reaction is controlled at 25～30 ℃, gained ozonide intermediate reduces with S-WAT, the aubepine productive rate reaches 85% (Guangxi Chemical Industry, 1997,26 (1): 11-17) under this condition.
Easy envelope duckweed equals the ozonization method to Oleum Cinnamomi and olium anisi in 1998 and is studied, and draws the optimum process condition of Oleum Cinnamomi ozonization method, and it is feasible that the preliminary method that experimental results show that has been done in the ozonize of olium anisi, and proceeds further investigation.1999, they used homemade bubbling reactor, added a certain proportion of raw material and solvent (ratio is unexposed), cooled off at low temperatures 10min, then passed into ozone reaction 6h, reached reaction end, and the trans-anethole of analyzing after testing more than 95% is oxidized.They think that there is an optimum reacting time in ozonization, and the time of controlling well can obtain good result (Guangxi University's journal: natural science edition, 1998,23 (1): 54-56; The Guangxi Academy Of Sciences journal, 1999,15 (2): 49-51).
2002, Liu Xiongmin, beam Red Army etc. follow the tracks of ozonization with gas-chromatography, the ozonization that has contrasted vinylbenzene, trans-anethole and phenylacrolein is active, reaction conditions is: raw material and solvent ratio are 1: 6, amount ratio between vinylbenzene, trans-anethole and the phenylacrolein is 1: 1,0 ℃ of temperature of reaction, reaction times 2.5h, every the 30min sampling analysis, the result shows that the ozonization activity of trans-anethole is the highest, active order is trans-anethole＞vinylbenzene＞phenylacrolein (chemistry of forest product and industry, 2002,22 (1): 39-42; Chemistry world, 2002, (7): 349-350).
2003, Li Weiguang etc. studied the dehydrated alcohol equal solvent to the selectivity of three kinds of main two key thing trans-anetholes, α-pinene and estragole ozonize in the impact of anise-oil ozonize and the anise-oil.They have investigated respectively dehydrated alcohol, methyl alcohol, No. 120 solvent oils and hexanaphthene equal solvent, with water bath with thermostatic control control temperature of reaction at 15 ℃, liquor kalii iodide monitoring tail gas, when the liquor kalii iodide variable color, stopped reaction.Result of study shows, adopts the mixed solvent effect better, and the mass ratio of mixed solvent is dehydrated alcohol: hexanaphthene=1: 3, aubepine yield the highest (productive rate does not relate to) under this condition.Ozone has good selectivity (chemistry world, 2003, (9): 464-478) to trans-anethole.
2007, Wang Qingjun etc. were take trans-anethole as raw material, and the mixture of acetic acid and hexanaphthene is made solvent, and ozonization method prepares aubepine.Investigated the impact on reaction result of solvent, ozonize time, reductive agent consumption, reduction decomposition time and reduction temperature, Primary Study ozonization progression.The processing condition of optimizing are, m (acetic acid): m (hexanaphthene)=1: 4, and the ozonize time is 100min, n (NaHSO
3): n (trans-anethole)=1.1: 1, reduction decomposition time 60min, 80 ℃ of reduction temperatures.With this understanding, product yield 〉=84%, purity 〉=98% (Qingdao University of Science and Technology's journal (natural science edition), 2007,28 (2): 117-120).
2008, Gao Rong etc. adopted Ozonation to prepare aubepine take star aniseed oil as raw material.Their experimental technique is to add 15g trans-anethole raw material in there-necked flask, and normal hexane and dehydrated alcohol are double solvents, and raw material solvent ratio 4: 1 passes into ozone and reacts, and ozonide reduces with 15% sodium sulfite solution.On single factor experiment and Box-Benhnken test design basis, test and regression analysis obtains optimal processing parameter: oxidation time 21min, 8.45 ℃ of oxidizing temperatures, double solvents proportioning 4.27: 1 (g/g), yield reaches as high as 73.6% (Food science, 2008,29 (6): 174-177).
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, the object of the present invention is to provide a kind of preparation method of aubepine.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of aubepine comprises following operation steps:
(1) be 20 with mass ratio: (20～100): the trans-anethole of (1～20), organic solvent and water are mixed to get reaction raw materials; Reaction raw materials is added in the bubbling reactor, and temperature of reaction is controlled at 20～30 ℃, with 0.12～0.32m
3H
-1The flow of every kilogram of reaction raw materials passes into ozone (O
3) and oxygen (O
2) mixed gas, carry out ozonization; Continue logical oxygen 15min～30min after ozonization finishes to drive unnecessary ozone out of, obtain ozonization liquid; The quality percentage composition of ozone is 2%～8% in described ozone and the oxygen mixed gas;
(2) sodium sulphite anhydrous 99.3 solution is heated to 60～80 ℃, drips ozonization liquid and carry out reduction reaction, the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 1.5～2.5; Dropwise rear continuation reaction 30min～60min, cooling is left standstill, and separatory obtains the aubepine crude product; The aubepine crude product is removed organic solvent through distillation, obtain the aubepine product.
The aspect ratio of the described bubbling reactor of step (1) is 10～20: 1, and the outside of bubbling reactor adds the condensation chuck, and condensation area is 0.32～0.50m
2Every kilogram of reaction raw materials, gas distributor is equipped with in the bottom of bubbling reactor, and the aperture of gas distributor is 5～50 μ m, and the bubbling area of gas distributor is 0.008～0.01m
2Every kilogram of reaction raw materials, the low temperature reflux condensing works is equipped with at the top of bubbling reactor, and condensing temperature is-5～0 ℃.The material of described bubbling reactor is glass.
The described ozonization time of step (1) is 1.0～2.0h.
The described organic solvent of step (1) is acetone, butanone, ethyl acetate or acetonitrile.
The described organic solvent of step (1) shared quality percentage composition in reaction raw materials is 80%～95%.
The mass percentage concentration of the described sodium sulphite anhydrous 99.3 solution of step (2) is 10%～15%.
The quality of gained aubepine product is 9.7～14.4g, and detecting aubepine content through GC is 95～100%, and productive rate counts 50%～78% with aubepine.
Principle of the present invention is: the inventive method has been avoided using and has been contained the mixed solvent of acetic acid, thus the equipment corrosion of having avoided acid solvent to bring.Acetone in the reaction system organic solvent had both played the effect of acetic acid dissolved ozone intermediate, had played again the effect of hexanaphthene or n-hexane dissolution trans-anethole, and a kind of solvent of acetone has just played the effect of two kinds of solvents in the document, is to kill two birds with one stone; And the existence of water can increase the solubleness of ozone in reaction system, thereby increased the contact probability of ozone and trans-anethole, so that oxidation efficiency improves greatly, in addition, the ozonize intermediate generation reduction reaction that water can also and generate, make part trans-anethole ozonide be converted into aubepine, thereby saved the reductive agent consumption of back reduction step; The reaction of the inventive method is the gas-liquid inhomogeneous reaction, so reactor has vital impact to the efficient of reacting.
The present invention has following advantage and effect with respect to prior art: acetone is water-soluble better, and the solvability of trans-anethole in acetone is also fine, thereby has solved water and the immiscible shortcoming of organic phase, and system is homogeneous phase after mixing.In addition, acetone has good oxidation-resistance, and is difficult for and ozonide reacts, thereby avoided the generation of a lot of side reactions in the ozonation, and acetone is the organic solvent of commonly using, boiling point is lower, be easy to from product, separate, can recycling.Moreover, the solubleness of ozone in water is larger, and the transformation period is longer, and ozonization is easier to carry out so the introducing of water makes, and water is the solvent of cheap environmental protection, meets the development trend of Green Chemistry.The double solvents system that the present invention adopts is improved prior art mixed solvent system weak point, thereby so that the ozonization of trans-anethole is more pratical and feasible, is convenient to suitability for industrialized production.The present invention has reduced equipment cost and production cost, has solved the critical problem that acetic acid exists the suitability for industrialized production such as the equipment corrosion, the environmental pollution that bring are large to face, for large-scale industrial production has been established road.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) be that 20: 20: 1 trans-anethole, acetone and water is mixed to get reaction raw materials with mass ratio; Reaction raw materials is added in the bubbling reactor, and temperature of reaction is controlled at 20 ℃, with 0.12m
3H
-1The flow of every kilogram of reaction raw materials passes into ozone and oxygen mixed gas, carries out ozonization; Continue logical oxygen 15min after ozonization finishes to drive unnecessary ozone out of, obtain ozonization liquid; The quality percentage composition of ozone is 5% in described ozone and the oxygen mixed gas;
The aspect ratio of described bubbling reactor (material is glass) is 10: 1, and the outside of bubbling reactor adds the condensation chuck, and condensation area is 0.32m
2Every kilogram of reaction raw materials, gas distributor is equipped with in the bottom of bubbling reactor, and the aperture of gas distributor is 50 μ m, and the bubbling area of gas distributor is 0.008m
2Every kilogram of reaction raw materials, the low temperature reflux condensing works is equipped with at the top of bubbling reactor, and condensing temperature is-5 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; Be that 10% sodium sulphite anhydrous 99.3 solution places reduction reactor with mass percentage concentration, be heated to 60～80 ℃, drip ozonization liquid and carry out reduction reaction, the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 1.5; Dropwise rear continuation reaction 30min, cooling is left standstill, and separatory obtains the aubepine crude product; The aubepine crude product is removed organic solvent through distillation, obtain aubepine product 10.9g.GC detects aubepine content 95.4%, and productive rate counts 56.54% with aubepine.
Embodiment 2
(1) be that 20: 88: 12 trans-anethole, acetone and water is mixed to get reaction raw materials with mass ratio; Reaction raw materials is added in the bubbling reactor, and temperature of reaction is controlled at 30 ℃, with 0.32m
3H
-1The flow of every kilogram of reaction raw materials passes into ozone and oxygen mixed gas, carries out ozonization 1.0h; Continue logical oxygen 15min after ozonization finishes to drive unnecessary ozone out of, obtain ozonization liquid; The quality percentage composition of ozone is 5% in described ozone and the oxygen mixed gas;
The aspect ratio of described bubbling reactor is 20: 1, and the outside of bubbling reactor adds the condensation chuck, and condensation area is 0.50m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of bubbling reactor, and the aperture of gas distributor is 5 μ m, and the bubbling area of gas distributor is 0.01m
2/ kg reaction raw materials, the low temperature reflux condensing works is equipped with at the top of bubbling reactor, and condensing temperature is-5 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; Be that 10% sodium sulphite anhydrous 99.3 solution places reduction reactor with mass percentage concentration, be heated to 80 ℃, drip ozonization liquid and carry out reduction reaction, the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.5; Dropwise rear continuation reaction 40min, cooling is left standstill, and separatory obtains the aubepine crude product; The aubepine crude product is removed organic solvent through distillation, obtain aubepine product 12.8g.GC detects aubepine content 99.3%, and productive rate counts 69.12% with aubepine.
Embodiment 3
(1) be that 20: 51: 9 trans-anethole, butanone and water is mixed to get reaction raw materials with mass ratio; Reaction raw materials is added in the bubbling reactor, and temperature of reaction is controlled at 25 ℃, with 0.24m
3H
-1The flow of every kilogram of reaction raw materials passes into ozone and oxygen mixed gas, carries out ozonization 1.2h; Continue logical oxygen 25min after ozonization finishes to drive unnecessary ozone out of, obtain ozonization liquid; The quality percentage composition of ozone is 2% in described ozone and the oxygen mixed gas;
The aspect ratio of described bubbling reactor is 20: 1, and the outside of bubbling reactor adds the condensation chuck, and condensation area is 0.50m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of bubbling reactor, and the aperture of gas distributor is 5 μ m, and the bubbling area of gas distributor is 0.01m
2/ kg reaction raw materials, the low temperature reflux condensing works is equipped with at the top of bubbling reactor, and condensing temperature is-5 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; Be that 15% sodium sulphite anhydrous 99.3 solution places reduction reactor with mass percentage concentration, be heated to 60 ℃, drip ozonization liquid and carry out reduction reaction, the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.0; Dropwise rear continuation reaction 50min, cooling is left standstill, and separatory obtains the aubepine crude product; The aubepine crude product is removed organic solvent through distillation, obtain aubepine product 13.5g, GC detects aubepine content 100%, and productive rate counts 73.47% with aubepine.
Embodiment 4
(1) be that 20: 100: 20 trans-anethole, ethyl acetate and water is mixed to get reaction raw materials with mass ratio; Reaction raw materials is added in the bubbling reactor, and temperature of reaction is controlled at 25 ℃, with 0.28m
3H
-1The flow of every kilogram of reaction raw materials passes into ozone and oxygen mixed gas, carries out ozonization 1.5h; Continue logical oxygen 15min after ozonization finishes to drive unnecessary ozone out of, obtain ozonization liquid; The quality percentage composition of ozone is 8% in described ozone and the oxygen mixed gas;
The aspect ratio of described bubbling reactor is 15: 1, and the outside of bubbling reactor adds the condensation chuck, and condensation area is 0.40m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of bubbling reactor, and the aperture of gas distributor is 5 μ m, and the bubbling area of gas distributor is 0.01m
2/ kg reaction raw materials, the low temperature reflux condensing works is equipped with at the top of bubbling reactor, and condensing temperature is 0 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; Be that 15% sodium sulphite anhydrous 99.3 solution places reduction reactor with mass percentage concentration, be heated to 70 ℃, drip ozonization liquid and carry out reduction reaction, the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.0; Dropwise rear continuation reaction 60min, cooling is left standstill, and separatory obtains the aubepine crude product; The aubepine crude product is removed organic solvent through distillation, obtain aubepine product 12.9g, GC detects aubepine content 96.7%, and productive rate counts 68.05% with aubepine.
Embodiment 5
(1) be that 20: 38: 2 trans-anethole, acetone and water is mixed to get reaction raw materials with mass ratio; Reaction raw materials is added in the bubbling reactor, and temperature of reaction is controlled at 25 ℃, with 0.24m
3H
-1The flow of every kilogram of reaction raw materials passes into ozone and oxygen mixed gas, carries out ozonization 1.2h; Continue logical oxygen 30min after ozonization finishes to drive unnecessary ozone out of, obtain ozonization liquid; The quality percentage composition of ozone is 6% in described ozone and the oxygen mixed gas;
The aspect ratio of described bubbling reactor is 20: 1, and the outside of bubbling reactor adds the condensation chuck, and condensation area is 0.50m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of bubbling reactor, and the aperture of gas distributor is 5 μ m, and the bubbling area of gas distributor is 0.01m
2/ kg reaction raw materials, the low temperature reflux condensing works is equipped with at the top of bubbling reactor, and condensing temperature is-5 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; Be that 12% sodium sulphite anhydrous 99.3 solution places reduction reactor with mass percentage concentration, be heated to 60 ℃, drip ozonization liquid and carry out reduction reaction, the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.5; Dropwise rear continuation reaction 30min, cooling is left standstill, and separatory obtains the aubepine crude product; The aubepine crude product is removed organic solvent through distillation, obtain aubepine product 10.7g, GC detects aubepine content 98.1%, and productive rate counts 57.22% with aubepine.
Embodiment 6
(1) be that 20: 57: 3 trans-anethole, acetone and water is mixed to get reaction raw materials with mass ratio; Reaction raw materials is added in the bubbling reactor, and temperature of reaction is controlled at 25 ℃, with 0.20m
3H
-1The flow of every kilogram of reaction raw materials passes into ozone and oxygen mixed gas, carries out ozonization 2.0h; Continue logical oxygen 20min after ozonization finishes to drive unnecessary ozone out of, obtain ozonization liquid; The quality percentage composition of ozone is 4% in described ozone and the oxygen mixed gas;
The aspect ratio of described bubbling reactor is 10: 1, and the outside of bubbling reactor adds the condensation chuck, and condensation area is 0.32m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of bubbling reactor, and the aperture of gas distributor is 15 μ m, and the bubbling area of gas distributor is 0.008m
2/ kg reaction raw materials, the low temperature reflux condensing works is equipped with at the top of bubbling reactor, and condensing temperature is 0 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; Be that 12% sodium sulphite anhydrous 99.3 solution places reduction reactor with mass percentage concentration, be heated to 60 ℃, drip ozonization liquid and carry out reduction reaction, the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.0; Dropwise rear continuation reaction 35min, cooling is left standstill, and separatory obtains the aubepine crude product; The aubepine crude product is removed organic solvent through distillation, obtain aubepine product 11.1g, GC detects aubepine content 100%, and productive rate counts 60.50% with aubepine.
Embodiment 7
(1) be that 20: 72: 8 trans-anethole, acetone and water is mixed to get reaction raw materials with mass ratio; Reaction raw materials is added in the bubbling reactor, and temperature of reaction is controlled at 25 ℃, with 0.24m
3H
-1The flow of every kilogram of reaction raw materials passes into ozone and oxygen mixed gas, carries out ozonization 1.7h; Continue logical oxygen 18min after ozonization finishes to drive unnecessary ozone out of, obtain ozonization liquid; The quality percentage composition of ozone is 7% in described ozone and the oxygen mixed gas;
The aspect ratio of described bubbling reactor is 15: 1, and the outside of bubbling reactor adds the condensation chuck, and condensation area is 0.40m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of bubbling reactor, and the aperture of gas distributor is 5 μ m, and the bubbling area of gas distributor is 0.01m
2/ kg reaction raw materials, the low temperature reflux condensing works is equipped with at the top of bubbling reactor, and condensing temperature is 0 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; Be that 11% sodium sulphite anhydrous 99.3 solution places reduction reactor with mass percentage concentration, be heated to 80 ℃, drip ozonization liquid and carry out reduction reaction, the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.5; Dropwise rear continuation reaction 45min, cooling is left standstill, and separatory obtains the aubepine crude product; The aubepine crude product is removed organic solvent through distillation, obtain aubepine product 11.9g, GC detects aubepine content 97.9%, and productive rate counts 63.46% with aubepine.
Embodiment 8
(1) be that 20: 68: 12 trans-anethole, acetonitrile and water is mixed to get reaction raw materials with mass ratio; Reaction raw materials is added in the bubbling reactor, and temperature of reaction is controlled at 25 ℃, with 0.32m
3H
-1The flow of every kilogram of reaction raw materials passes into ozone and oxygen mixed gas, carries out ozonization 1.5h; Continue logical oxygen 15min after ozonization finishes to drive unnecessary ozone out of, obtain ozonization liquid; The quality percentage composition of ozone is 5% in described ozone and the oxygen mixed gas;
The aspect ratio of described bubbling reactor is 20: 1, and the outside of bubbling reactor adds the condensation chuck, and condensation area is 0.50m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of bubbling reactor, and the aperture of gas distributor is 5 μ m, and the bubbling area of gas distributor is 0.01m
2/ kg reaction raw materials, the low temperature reflux condensing works is equipped with at the top of bubbling reactor, and condensing temperature is-5 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; Be that 14% sodium sulphite anhydrous 99.3 solution places reduction reactor with mass percentage concentration, be heated to 60 ℃, drip ozonization liquid and carry out reduction reaction, the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.0; Dropwise rear continuation reaction 30min, cooling is left standstill, and separatory obtains the aubepine crude product; The aubepine crude product is removed organic solvent through distillation, obtain aubepine product 12.3g, GC detects aubepine content 98.6%, and productive rate counts 65.73% with aubepine.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. the preparation method of an aubepine is characterized in that comprising following operation steps:
(1) be 20:(20～100 with mass ratio): the trans-anethole of (1～20), organic solvent and water are mixed to get reaction raw materials; Reaction raw materials is added in the bubbling reactor, and temperature of reaction is controlled at 20～30 ℃, with 0.12～0.32m
3H
-1The flow of every kilogram of reaction raw materials passes into ozone and oxygen mixed gas, carries out ozonization; Continue logical oxygen 15min～30min after ozonization finishes to drive unnecessary ozone out of, obtain ozonization liquid; The quality percentage composition of ozone is 2%～8% in described ozone and the oxygen mixed gas;
(2) sodium sulphite anhydrous 99.3 solution is heated to 60～80 ℃, drips ozonization liquid and carry out reduction reaction, the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1:1.5～2.5; Dropwise rear continuation reaction 30min～60min, cooling is left standstill, and separatory obtains the aubepine crude product; The aubepine crude product is removed organic solvent through distillation, obtain the aubepine product;
The described organic solvent of step (1) is acetone, butanone, ethyl acetate or acetonitrile.
2. the preparation method of a kind of aubepine according to claim 1, it is characterized in that: the aspect ratio of the described bubbling reactor of step (1) is 10～20:1, and the outside of bubbling reactor adds the condensation chuck, and condensation area is 0.32～0.50m
2Every kilogram of reaction raw materials, gas distributor is equipped with in the bottom of bubbling reactor, and the aperture of gas distributor is 5～50 μ m, and the bubbling area of gas distributor is 0.008～0.01m
2Every kilogram of reaction raw materials, the low temperature reflux condensing works is equipped with at the top of bubbling reactor, and condensing temperature is-5～0 ℃.
3. the preparation method of a kind of aubepine according to claim 2, it is characterized in that: the material of described bubbling reactor is glass.
4. the preparation method of a kind of aubepine according to claim 1, it is characterized in that: the described ozonization time of step (1) is 1.0～2.0h.
5. the preparation method of a kind of aubepine according to claim 1, it is characterized in that: the described organic solvent of step (1) shared quality percentage composition in reaction raw materials is 80%～95%.
6. the preparation method of a kind of aubepine according to claim 1, it is characterized in that: the mass percentage concentration of the described sodium sulphite anhydrous 99.3 solution of step (2) is 10%～15%.
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| CN103012125A (en) * | 2012-11-08 | 2013-04-03 | 南宁辰康生物科技有限公司 | Method for preparing anisic acid |
| TW201601629A (en) * | 2013-10-02 | 2016-01-16 | Kyoyu Agri Co Ltd | Composition comprising harmful arthropod-attracting substance formed from plant-derived components and analogs thereof |
| CN106146287A (en) * | 2016-06-07 | 2016-11-23 | 湖南理工学院 | A kind of air oxidation low-purity valeraldehyde prepares the friendly process of positive valeric acid |
| CN112299970A (en) * | 2019-07-31 | 2021-02-02 | 成都三香汇香料有限公司 | Method for preparing natural benzaldehyde by oxidizing natural perfume |
| CN112390710A (en) * | 2019-08-14 | 2021-02-23 | 成都三香汇香料有限公司 | Preparation method of anisic aldehyde |
| CN113636920A (en) * | 2021-08-16 | 2021-11-12 | 广西大学 | Method for producing food-grade benzaldehyde by using cinnamon oil rectifying still bottom product |
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| CN1683304A (en) * | 2005-03-02 | 2005-10-19 | 大连理工大学 | Method for synthesizing anisic aldehyde by selective hydrogenation of methyl methoxybenzoate |
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| Charles E. Schiaffo et al.."Ozonolysis in Solvent/Water Mixtures: Direct Conversion of Alkenes to Aldehydes and Ketones".《J.Org.Chem》.2008,第73卷(第12期),p4688-4690. |
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