CN101792378A - Method for preparing anisaldehyde - Google Patents
Method for preparing anisaldehyde Download PDFInfo
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- CN101792378A CN101792378A CN 200910214322 CN200910214322A CN101792378A CN 101792378 A CN101792378 A CN 101792378A CN 200910214322 CN200910214322 CN 200910214322 CN 200910214322 A CN200910214322 A CN 200910214322A CN 101792378 A CN101792378 A CN 101792378A
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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
(anisaldehyde, anisic aldehyde p-methoxybenzaldehyde) claim white shore difficult to understand again, chemistry aubepine by name to aubepine.Pure product are colourless or weak yellow liquid, have intensive may blossom fragrance, and fragrance is lasting, has stronger antioxidant property simultaneously.Density is 1.123g/ml (20 ℃), 2.5 ℃ of fusing points, and 249.5 ℃ of boiling points, 144～200 ℃ (28kPa), 134～135 ℃ (1.6kPa), 83 ℃ (0.267kPa), and 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 of aubepine has persistent hawthorn fragrance, the fragrant tempting multiple essence such as sweet floral type, cloves and hawthorn odor type that are widely used in preparing, be used for food, carbohydrate and beverage preparation (meticulous and specialty chemicals, 2000, (12): 33-34 with essence; 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 star aniseed oil again).The trans-anethole oxidation style mainly is divided three classes: conventional oxidation method, electrooxidation method and ozone oxidation method.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 height, environmental pollution are serious.Used dichromate titration and permanganate method afterwards again, 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 " three wastes " to pollute reluctant problem equally, and acid is to the machinery equipment seriously corroded, on producing, be difficult to use (chemistry world, 1988,29 (6): 253-256).Zhong Wenhai improves the technology that manganese dioxide prepares aubepine, with natural manganese dioxede in powder of higher-grade and dilute sulphuric acid is 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 shortcoming (fragrance flavor and cosmetics such as improvement, 1990, (4): 4-5).The electrooxidation method has two kinds of methods, and direct oxidation method promptly in the presence of supporting electrolyte, is directly made the synthetic aubepine of oxygenant with electronics; Another kind is the indirect electrooxidation method, and promptly 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 solvent with water, 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.With graphite or titanium base ruthenium is anode, and stainless steel is a negative electrode, and 80%～90% aqueous ethanolic solution is a 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 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 that has phenyl ring, and ozone can be at the oxidation efficiently of two keys, and can the attack phenyl ring.So ozonization method is subjected 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 organism such as ozone and ethene, thereafter C.Harries used the time in 15 years that organic ozonization has been carried out extensive studies 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, the research to ozonization abroad mainly concentrates on chain unsaturated olefin and some other unsaturated aromatic hydrocarbon, and to the rarely seen report of the ozonization of trans-anethole.Domestic more to the ozonization research of trans-anethole in recent years, 1997, Liu Lihua etc. are raw material with the trans-anethole, 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.
Easily the envelope duckweed equals the ozonization method of Oleum Cinnamomi and olium anisi to be studied in 1998, 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 proceed further investigation.1999, they used homemade bubbling reactor, added a certain proportion of raw material and solvent (ratio is unexposed), cooled off 10min at low temperatures, fed ozone reaction 6h then, 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, contrasted the ozonization activity of vinylbenzene, trans-anethole and phenylacrolein, 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 selectivity of dehydrated alcohol equal solvent to three kinds of main two key thing trans-anetholes, α-Pai Xi and estragole ozonize in the influence of anise-oil ozonize and the anise-oil.They have investigated dehydrated alcohol, methyl alcohol, No. 120 solvent oils and hexanaphthene equal solvent respectively, with the water bath with thermostatic control control reaction temperature 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 a 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 raw material with the trans-anethole, and the mixture of acetate and hexanaphthene is made solvent, and ozonization method prepares aubepine.Investigated the influence of solvent, ozonize time, reductive agent consumption, reduction decomposition time and reduction temperature, tentatively inquired into ozonization progression reaction result.Optimized process conditions is, m (acetate): 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. were raw material with the star aniseed oil, adopted the ozone oxidation legal system to be equipped with aubepine.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 feeds 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 preparing anisaldehyde.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparing anisaldehyde comprises following operation steps:
(1) be 20 with mass ratio: (20～100): the trans-anethole of (1～20), organic solvent and water mixing obtain reaction raw materials; Reaction raw materials is added in the blistering reaction tower, and temperature of reaction is controlled at 20～30 ℃, with 0.12～0.32m
3H
-1The flow of every kilogram of reaction raw materials feeds ozone (O
3) and oxygen (O
2) mixed gas, carry out ozonization; Ozonization finishes the back and continues logical oxygen 15min～30min to drive redundant ozone out of, obtains 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 the back and continue 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 blistering reaction tower of step (1) is 10～20: 1, and the outside of blistering reaction tower 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 blistering reaction tower, 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 blistering reaction tower, and condensing temperature is-5～0 ℃.The material of described blistering reaction tower is a 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 acetate, thus the equipment corrosion of having avoided acid solvent to bring.Acetone in the reaction system organic solvent had both played the effect of acetate dissolved ozone intermediate, had played the effect of hexanaphthene or n-hexane dissolution trans-anethole again, 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, make oxidation efficiency improve 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 fundamental influence 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 in the ozonize process generation of a lot of side reactions, and acetone is the organic solvent of using always, boiling point is lower, be easy to from product, separate, can recycling.Moreover, the solubleness of ozone in water is bigger, 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 is made 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 acetate and has had the critical problems that suitability for industrialized production faced such as the equipment corrosion, the environmental pollution that bring be big, 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 thereto.
Embodiment 1
(1) be that 20: 20: 1 trans-anethole, acetone and water mix and obtains reaction raw materials with mass ratio; Reaction raw materials is added in the blistering reaction tower, and temperature of reaction is controlled at 20 ℃, with 0.12m
3H
-1The flow of every kilogram of reaction raw materials feeds ozone and oxygen mixed gas, carries out ozonization; Ozonization finishes the back and continues logical oxygen 15min to drive redundant ozone out of, obtains ozonization liquid; The quality percentage composition of ozone is 5% in described ozone and the oxygen mixed gas;
The aspect ratio of described blistering reaction tower (material is a glass) is 10: 1, and the outside of blistering reaction tower 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 blistering reaction tower, 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 blistering reaction tower, and condensing temperature is-5 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; With mass percentage concentration is that 10% sodium sulphite anhydrous 99.3 solution places reduction reactor, is heated to 60～80 ℃, drips ozonization liquid and carries out reduction reaction, and the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 1.5; Dropwise the back and continue 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 mix and obtains reaction raw materials with mass ratio; Reaction raw materials is added in the blistering reaction tower, and temperature of reaction is controlled at 30 ℃, with 0.32m
3H
-1The flow of every kilogram of reaction raw materials feeds ozone and oxygen mixed gas, carries out ozonization 1.0h; Ozonization finishes the back and continues logical oxygen 15min to drive redundant ozone out of, obtains ozonization liquid; The quality percentage composition of ozone is 5% in described ozone and the oxygen mixed gas;
The aspect ratio of described blistering reaction tower is 20: 1, and the outside of blistering reaction tower adds the condensation chuck, and condensation area is 0.50m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of blistering reaction tower, 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 blistering reaction tower, and condensing temperature is-5 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; With mass percentage concentration is that 10% sodium sulphite anhydrous 99.3 solution places reduction reactor, is heated to 80 ℃, drips ozonization liquid and carries out reduction reaction, and the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.5; Dropwise the back and continue 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 mix and obtains reaction raw materials with mass ratio; Reaction raw materials is added in the blistering reaction tower, and temperature of reaction is controlled at 25 ℃, with 0.24m
3H
-1The flow of every kilogram of reaction raw materials feeds ozone and oxygen mixed gas, carries out ozonization 1.2h; Ozonization finishes the back and continues logical oxygen 25min to drive redundant ozone out of, obtains ozonization liquid; The quality percentage composition of ozone is 2% in described ozone and the oxygen mixed gas;
The aspect ratio of described blistering reaction tower is 20: 1, and the outside of blistering reaction tower adds the condensation chuck, and condensation area is 0.50m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of blistering reaction tower, 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 blistering reaction tower, and condensing temperature is-5 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; With mass percentage concentration is that 15% sodium sulphite anhydrous 99.3 solution places reduction reactor, is heated to 60 ℃, drips ozonization liquid and carries out reduction reaction, and the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.0; Dropwise the back and continue 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 mix and obtains reaction raw materials with mass ratio; Reaction raw materials is added in the blistering reaction tower, and temperature of reaction is controlled at 25 ℃, with 0.28m
3H
-1The flow of every kilogram of reaction raw materials feeds ozone and oxygen mixed gas, carries out ozonization 1.5h; Ozonization finishes the back and continues logical oxygen 15min to drive redundant ozone out of, obtains ozonization liquid; The quality percentage composition of ozone is 8% in described ozone and the oxygen mixed gas;
The aspect ratio of described blistering reaction tower is 15: 1, and the outside of blistering reaction tower adds the condensation chuck, and condensation area is 0.40m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of blistering reaction tower, 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 blistering reaction tower, and condensing temperature is 0 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; With mass percentage concentration is that 15% sodium sulphite anhydrous 99.3 solution places reduction reactor, is heated to 70 ℃, drips ozonization liquid and carries out reduction reaction, and the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.0; Dropwise the back and continue 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 mix and obtains reaction raw materials with mass ratio; Reaction raw materials is added in the blistering reaction tower, and temperature of reaction is controlled at 25 ℃, with 0.24m
3H
-1The flow of every kilogram of reaction raw materials feeds ozone and oxygen mixed gas, carries out ozonization 1.2h; Ozonization finishes the back and continues logical oxygen 30min to drive redundant ozone out of, obtains ozonization liquid; The quality percentage composition of ozone is 6% in described ozone and the oxygen mixed gas;
The aspect ratio of described blistering reaction tower is 20: 1, and the outside of blistering reaction tower adds the condensation chuck, and condensation area is 0.50m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of blistering reaction tower, 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 blistering reaction tower, and condensing temperature is-5 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; With mass percentage concentration is that 12% sodium sulphite anhydrous 99.3 solution places reduction reactor, is heated to 60 ℃, drips ozonization liquid and carries out reduction reaction, and the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.5; Dropwise the back and continue 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 mix and obtains reaction raw materials with mass ratio; Reaction raw materials is added in the blistering reaction tower, and temperature of reaction is controlled at 25 ℃, with 0.20m
3H
-1The flow of every kilogram of reaction raw materials feeds ozone and oxygen mixed gas, carries out ozonization 2.0h; Ozonization finishes the back and continues logical oxygen 20min to drive redundant ozone out of, obtains ozonization liquid; The quality percentage composition of ozone is 4% in described ozone and the oxygen mixed gas;
The aspect ratio of described blistering reaction tower is 10: 1, and the outside of blistering reaction tower adds the condensation chuck, and condensation area is 0.32m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of blistering reaction tower, 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 blistering reaction tower, and condensing temperature is 0 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; With mass percentage concentration is that 12% sodium sulphite anhydrous 99.3 solution places reduction reactor, is heated to 60 ℃, drips ozonization liquid and carries out reduction reaction, and the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.0; Dropwise the back and continue 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 mix and obtains reaction raw materials with mass ratio; Reaction raw materials is added in the blistering reaction tower, and temperature of reaction is controlled at 25 ℃, with 0.24m
3H
-1The flow of every kilogram of reaction raw materials feeds ozone and oxygen mixed gas, carries out ozonization 1.7h; Ozonization finishes the back and continues logical oxygen 18min to drive redundant ozone out of, obtains ozonization liquid; The quality percentage composition of ozone is 7% in described ozone and the oxygen mixed gas;
The aspect ratio of described blistering reaction tower is 15: 1, and the outside of blistering reaction tower adds the condensation chuck, and condensation area is 0.40m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of blistering reaction tower, 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 blistering reaction tower, and condensing temperature is 0 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; With mass percentage concentration is that 11% sodium sulphite anhydrous 99.3 solution places reduction reactor, is heated to 80 ℃, drips ozonization liquid and carries out reduction reaction, and the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.5; Dropwise the back and continue 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 mix and obtains reaction raw materials with mass ratio; Reaction raw materials is added in the blistering reaction tower, and temperature of reaction is controlled at 25 ℃, with 0.32m
3H
-1The flow of every kilogram of reaction raw materials feeds ozone and oxygen mixed gas, carries out ozonization 1.5h; Ozonization finishes the back and continues logical oxygen 15min to drive redundant ozone out of, obtains ozonization liquid; The quality percentage composition of ozone is 5% in described ozone and the oxygen mixed gas;
The aspect ratio of described blistering reaction tower is 20: 1, and the outside of blistering reaction tower adds the condensation chuck, and condensation area is 0.50m
2/ kg reaction raw materials, gas distributor is equipped with in the bottom of blistering reaction tower, 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 blistering reaction tower, and condensing temperature is-5 ℃.
(2) ozonization liquid is transferred to the constant voltage dropper; With mass percentage concentration is that 14% sodium sulphite anhydrous 99.3 solution places reduction reactor, is heated to 60 ℃, drips ozonization liquid and carries out reduction reaction, and the mass ratio of described ozonization liquid and sodium sulphite anhydrous 99.3 solution is 1: 2.0; Dropwise the back and continue 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.
The foregoing description is a preferred implementation 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 (7)
1. preparing anisaldehyde is characterized in that comprising following operation steps:
(1) be 20 with mass ratio: (20～100): the trans-anethole of (1～20), organic solvent and water mixing obtain reaction raw materials; Reaction raw materials is added in the blistering reaction tower, and temperature of reaction is controlled at 20～30 ℃, with 0.12～0.32m
3H
-1The flow of every kilogram of reaction raw materials feeds ozone and oxygen mixed gas, carries out ozonization; Ozonization finishes the back and continues logical oxygen 15min～30min to drive redundant ozone out of, obtains 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 the back and continue 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.
2. a kind of preparing anisaldehyde according to claim 1 is characterized in that: the aspect ratio of the described blistering reaction tower of step (1) is 10～20: 1, and the outside of blistering reaction tower 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 blistering reaction tower, 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 blistering reaction tower, and condensing temperature is-5～0 ℃.
3. a kind of preparing anisaldehyde according to claim 2 is characterized in that: the material of described blistering reaction tower is a glass.
4. a kind of preparing anisaldehyde according to claim 1 is characterized in that: the described ozonization time of step (1) is 1.0～2.0h.
5. a kind of preparing anisaldehyde according to claim 1 is characterized in that: the described organic solvent of step (1) is acetone, butanone, ethyl acetate or acetonitrile.
6. a kind of preparing anisaldehyde according to claim 1 is characterized in that: the described organic solvent of step (1) shared quality percentage composition in reaction raw materials is 80%～95%.
7. a kind of preparing anisaldehyde according to claim 1 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105578879A (en) * | 2013-10-02 | 2016-05-11 | 协友株式会社 | 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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2009
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105578879A (en) * | 2013-10-02 | 2016-05-11 | 协友株式会社 | 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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