CN114988993B - Method for preparing vanillin by one-step method - Google Patents
Method for preparing vanillin by one-step method Download PDFInfo
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- CN114988993B CN114988993B CN202210657170.1A CN202210657170A CN114988993B CN 114988993 B CN114988993 B CN 114988993B CN 202210657170 A CN202210657170 A CN 202210657170A CN 114988993 B CN114988993 B CN 114988993B
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- reaction
- vanillin
- hydrogen peroxide
- methoxy
- hydroxy
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- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 60
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 84
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 68
- CGQCWMIAEPEHNQ-UHFFFAOYSA-N Vanillylmandelic acid Chemical compound COC1=CC(C(O)C(O)=O)=CC=C1O CGQCWMIAEPEHNQ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 19
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 17
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 3
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005070 sampling Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 230000002572 peristaltic effect Effects 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229960002510 mandelic acid Drugs 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 244000263375 Vanilla tahitensis Species 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing vanillin by a one-step method, which comprises the steps of reacting 3-methoxy-4-hydroxy-mandelic acid aqueous solution with hydrogen peroxide in an acidic system in the presence of ferric sulfate serving as a catalyst to prepare vanillin. The method provided by the invention uses hydrogen peroxide as an oxidant, toluene as an extractant, and the oxidation reaction and the decarboxylation reaction are carried out simultaneously, so that the process is simplified, the production efficiency is greatly improved, and the production cost is reduced; meanwhile, the invention does not need air or oxygen as a reaction raw material, so that a large amount of waste gas generated in the oxidation process is avoided, sodium sulfate generated in the reaction process is greatly reduced, and the three-waste treatment difficulty is reduced.
Description
Technical Field
The invention relates to a method for preparing vanillin by a one-step method, and belongs to the technical field of perfume chemical synthesis.
Background
Vanillin, commonly known as vanillin, has a chemical name of 3-methoxy-4-hydroxybenzaldehyde, has a special fragrance of vanilla, is usually white or pale yellow crystalline powder, is a synthetic spice with the largest yield in the world, and is widely applied to the food and spice processing industry. Because of the wide application and importance of vanillin in various industries, the synthesis process of vanillin has been a long-felt research hotspot.
At present, two main processes for preparing vanillin are available, one is to adopt copper oxide (or other transition metal oxides) as an oxidant, and prepare vanillin after oxidizing mandelic acid for decarboxylation. CN1016190188 discloses a method for preparing vanillin by chemical oxidation, which has high yield, but the related materials are solid-liquid mixtures with high solid content, and the requirements on the separation performance of equipment are high.
The second main process is to use a catalyst to catalyze oxygen to oxidize mandelic acid and decarboxylate to obtain vanillin, and the process is simple, but can generate a large amount of exhaust emission.
The main disadvantage of the prior art vanillin prepared from 3-methoxy-4-hydroxy-mandelic acid is that the reaction has to be carried out in two steps, oxidation and decarboxylation. In addition, since the oxidation step is performed under alkaline conditions and the decarboxylation step is performed under acidic conditions, a large amount of wastewater and sodium sulfate are generated during the pH adjustment, and the environmental protection cost is increased.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a method for preparing vanillin by a one-step method from 3-methoxy-4-hydroxy-mandelic acid and hydrogen peroxide using ferric sulfate as a catalyst and toluene as an extractant. The inventor finds that the yield of the product obtained by the oxidation reaction under the alkaline condition is higher and the yield under the acid condition is lower in the process of researching the mandelic acid oxidation process. Under the acidic condition, when the reaction conversion rate is low, the oxidation and the decarboxylation are synchronously carried out, and the yield of the corresponding product vanillin is high, but as the raw materials are gradually consumed, the vanillin is further oxidized, aldehyde groups in the vanillin are converted into other groups, and therefore the yield of the product is reduced. The invention provides an implementable industrialization scheme based on the method.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing vanillin by a one-step method, which comprises the step of reacting 3-methoxy-4-hydroxy-mandelic acid aqueous solution with hydrogen peroxide in an acidic system in the presence of ferric sulfate serving as a catalyst to prepare vanillin.
In the invention, the 3-methoxy-4-hydroxy-mandelic acid is prepared into aqueous solution for use; the concentration of the 3-methoxy-4-hydroxy-mandelic acid aqueous solution is 4-8wt%, preferably 5-6wt%.
In the present invention, the toluene is used in an amount of 100.0 to 400.0% by mass, preferably 200.0 to 300.0% by mass, based on the aqueous solution of 3-methoxy-4-hydroxy-mandelic acid. The toluene is used as an extractant in the reaction, and vanillin generated by the reaction can be immediately transferred to an oil phase, so that the vanillin is prevented from further generating series side reaction with hydrogen peroxide in an aqueous phase.
In the invention, the concentration of the hydrogen peroxide is 15.0-65.0wt%, preferably 45.0-55.0wt%;
preferably, the molar ratio of the hydrogen peroxide to the 3-methoxy-4-hydroxy-mandelic acid is 0.98-1.02:1, preferably 1.0-1.01:1;
preferably, the hydrogen peroxide is added dropwise in a continuous feeding mode, the feeding time is 18.0-32.0h, preferably 24.0-28.0h, and the feeding time is not counted in the reaction time; the feeding temperature is the reaction temperature;
preferably, the hydrogen peroxide is pre-cooled to 0-10 ℃, preferably 5 ℃ before being added.
In the invention, the dosage of the ferric sulfate catalyst is 2.0-10.0 percent, preferably 4.0-8.0 percent of the mass of the 3-methoxy-4-hydroxy-mandelic acid.
In the present invention, the pH of the acidic system is 4.0 to 7.0, preferably 5.0 to 6.0; the pH of the system can be adjusted by conventional means, for example by adding an acid selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, preferably sulfuric acid, in a dilute aqueous acid solution having a concentration of 1-10% by weight.
In the present invention, the reaction temperature is 10.0 to 60.0 ℃, preferably 20.0 to 50.0 ℃; the time is 0.2-0.8h, preferably 0.4-0.6h.
In the invention, the reaction is carried out by nitrogen replacement before the initial stage of the reaction and the reaction is carried out under normal pressure.
In the present invention, the reaction is carried out under stirring at a stirring speed of 400.0 to 3000.0rpm, preferably 1000.0 to 2000.0rpm.
In the invention, after the reaction is finished, post-treatment operations such as liquid separation, drying and the like are also included, and are conventional methods in the field, and the invention has no special requirement.
According to the method disclosed by the invention, the conversion rate of the raw material 3-methoxy-4-hydroxy-mandelic acid is more than 99%, the vanillin selectivity is more than 95%, and the product purity is more than 97%.
According to the preparation method disclosed by the invention, heterogeneous reaction is adopted, oxidation and decarboxylation are synchronously carried out in a water phase in the reaction process, when the decarboxylation is finished, the solubility of vanillin in an oil phase is far greater than that of the water phase, vanillin generated by the reaction is immediately transferred to the oil phase, and because an oxidant and a catalyst are in the water phase, the vanillin dissolved in the oil phase is not contacted with the oxidant, so that further reaction of vanillin is prevented, and the product yield of vanillin is improved. After the reaction is finished, cooling the reaction liquid, standing for liquid separation, and evaporating an oil phase to obtain the vanillin.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the method uses hydrogen peroxide as an oxidant, toluene as an extractant, and oxidation reaction and decarboxylation reaction are carried out simultaneously, so that the process is simplified, the production efficiency is greatly improved, and the production cost is reduced; meanwhile, the invention does not need air or oxygen as a reaction raw material, so that a large amount of waste gas generated in the oxidation process is avoided, sodium sulfate generated in the reaction process is greatly reduced, and the three-waste treatment difficulty is reduced.
Drawings
FIG. 1 is a GC chromatogram of the vanillin product (oil phase) prepared in example 1.
Detailed Description
The following further describes the technical scheme of the present invention, but is not limited thereto, and all modifications and equivalents of the technical scheme of the present invention are included in the scope of the present invention without departing from the scope of the technical scheme of the present invention.
HPLC analysis conditions: chromatographic model: shimadzu LC-20A; the sample injection amount is 5 mu L; the UV detection wavelength is 310nm; column incubator: 40 ℃; flow rate: 0.4ml/min; and (5) quantifying by an external standard method.
The main raw materials in the examples are as follows, and all the other raw materials are common commercial raw materials unless otherwise specified:
| reagent name | Reagent specification | Manufacturing factories |
| 3-methoxy-4-hydroxy-mandelic acid | CP | Wanhua chemistry |
| Hydrogen peroxide | AR | Xiyong reagent |
| Ferric sulfate | AR | Xiyong reagent |
| Toluene (toluene) | Quality grade product | Qingdao Lidong |
Example 1
1137.5g of 3-methoxy-4-hydroxy-mandelic acid aqueous solution (with the concentration of 4wt percent, 0.229 mol), 1706g of toluene and 4.1g of ferric sulfate catalyst are weighed and added into a 5L reaction kettle, the pH value is regulated to 6.5 by adopting a dilute sulfuric acid aqueous solution with the concentration of 1wt percent, after nitrogen replacement, stirring is started, the rotating speed is set to 1000rpm, and the temperature is controlled to 15 ℃ by adopting a high-low temperature tank; weighing 15.47g of hydrogen peroxide (with the concentration of 50wt percent and 0.228 mol), precooling to 5 ℃, dropwise adding the hydrogen peroxide into a reaction kettle by adopting a peristaltic pump, ending the dropwise adding, continuing to perform heat preservation reaction for 0.3h, and ending the reaction. The conversion of the sample was 99.2% and the selectivity was 96.3%.
After the reaction solution was returned to room temperature, the reaction solution was transferred to a separating funnel, allowed to stand for 1 hour, the upper oil phase was taken, toluene in the oil phase was separated by a rotary evaporator, and 32.944g of a vanillin product was obtained, with a purity of 97.5%.
Example 2
Weighing 1011g of 3-methoxy-4-hydroxy-mandelic acid aqueous solution (with the concentration of 4.5wt%,0.229 mol), 2022g of toluene and 4.55g of ferric sulfate catalyst, adding into a 5L reaction kettle, adjusting the pH value to 4.5 by adopting a dilute sulfuric acid aqueous solution with the concentration of 10wt%, after nitrogen replacement, starting stirring, setting the rotating speed to 3000rpm, and controlling the temperature to 10 ℃ by adopting a high-low temperature tank; 17.71g of hydrogen peroxide (concentration of 45wt percent, 0.234 mol) is weighed, after precooling to 5 ℃, the hydrogen peroxide is dripped into a reaction kettle by adopting a peristaltic pump, the dripping is finished for 24 hours, the heat preservation reaction is continued for 0.8 hour, and the reaction is finished. The conversion of the sample was 99.5% and the selectivity was 95.3%.
After the reaction solution was returned to room temperature, the reaction solution was transferred to a separating funnel, allowed to stand for 1 hour, the upper oil phase was taken, toluene in the oil phase was separated by a rotary evaporator, and 31.85g of vanillin product was obtained with a purity of 98%.
Example 3
Weighing 910g of 3-methoxy-4-hydroxy-mandelic acid aqueous solution (with the concentration of 5wt%,0.229 mol), 3185g of toluene and 1.37g of ferric sulfate catalyst, adding into a 5L reaction kettle, adjusting the pH value to 4 by adopting a dilute hydrochloric acid aqueous solution with the concentration of 8wt%, after nitrogen replacement, starting stirring, setting the rotating speed to 700rpm, and controlling the temperature to 50 ℃ by adopting a high-low temperature tank; 11.78g of hydrogen peroxide (concentration is 65wt percent, 0.225 mol) is weighed, after precooling to 5 ℃, the hydrogen peroxide is dripped into a reaction kettle by adopting a peristaltic pump, the dripping is finished for 28 hours, the heat preservation reaction is continued for 0.6 hour, and the reaction is finished. The conversion of the sample was 99.8% and the selectivity was 96.55%.
After the reaction solution was returned to room temperature, it was transferred to a separating funnel, allowed to stand for 1 hour, the upper oil phase was taken, toluene in the oil phase was separated by a rotary evaporator, and 32.33g of a vanillin product was obtained, with a purity of 98.5%.
Example 4
758g of 3-methoxy-4-hydroxy-mandelic acid aqueous solution (with the concentration of 6wt percent, 0.229 mol), 758g of toluene and 1.82g of ferric sulfate catalyst are weighed and added into a 5L reaction kettle, the pH value is regulated to 7 by adopting a dilute sulfuric acid aqueous solution with the concentration of 1wt percent, after nitrogen replacement, stirring is started, the rotating speed is set to 2500rpm, and the temperature is controlled to 60 ℃ by adopting a high-low temperature tank; 14.42g of hydrogen peroxide (concentration of 55wt percent, 0.233 mol) is weighed, after precooling to 5 ℃, the hydrogen peroxide is dripped into a reaction kettle by adopting a peristaltic pump, the dripping is finished for 21 hours, the heat preservation reaction is continued for 0.5 hour, and the reaction is finished. The conversion of the sample was 100% and the selectivity was 96.5%.
After the reaction solution was returned to room temperature, it was transferred to a separating funnel, allowed to stand for 1 hour, the upper oil phase was taken, toluene in the oil phase was separated by a rotary evaporator, and 32.66g of vanillin product was obtained with a purity of 97.2%.
Example 5
700g of 3-methoxy-4-hydroxy-mandelic acid aqueous solution (with the concentration of 6.5wt percent, 0.229 mol), 1750g of toluene and 3.64g of ferric sulfate catalyst are weighed and added into a 5L reaction kettle, the pH value is regulated to 5 by adopting a dilute sulfuric acid aqueous solution with the concentration of 2wt percent, after nitrogen replacement, stirring is started, the rotating speed is set to 1500rpm, and the temperature is controlled to 55 ℃ by adopting a high-low temperature tank; 52.09g of hydrogen peroxide (with the concentration of 15wt percent and 0.230 mol) is weighed, after precooling to 5 ℃, the hydrogen peroxide is dripped into a reaction kettle by adopting a peristaltic pump, the dripping is finished for 18 hours, the heat preservation reaction is continued for 0.7 hour, and the reaction is finished. The conversion of the sample was 99.8% and the selectivity was 95.1%.
And (3) after the reaction solution is recovered to room temperature, transferring the reaction solution to a separating funnel, standing for 1h, taking an upper oil phase, and separating toluene in the oil phase by using a rotary evaporator to obtain 32g of vanillin product with the purity of 97.9%.
Example 6
650g of 3-methoxy-4-hydroxy-mandelic acid aqueous solution (with the concentration of 7wt percent, 0.229 mol), 2600g of toluene and 2.73g of ferric sulfate catalyst are weighed and added into a 5L reaction kettle, the pH value is regulated to 5.5 by adopting a phosphoric acid aqueous solution with the concentration of 2.5 percent, after nitrogen replacement, stirring is started, the rotating speed is set to 400rpm, and the temperature is controlled to 20 ℃ by adopting a high-low temperature tank; 13.09g of hydrogen peroxide (concentration is 60wt percent, 0.231 mol) is weighed, after precooling to 5 ℃, the hydrogen peroxide is dripped into a reaction kettle by adopting a peristaltic pump, the dripping is finished for 26 hours, the heat preservation reaction is continued for 0.4 hour, and the reaction is finished. The conversion of the sample was 99.7% and the selectivity was 95.4%.
After the reaction solution was returned to room temperature, it was transferred to a separating funnel, allowed to stand for 1 hour, the upper oil phase was taken, toluene in the oil phase was separated by a rotary evaporator, and 33.32g of vanillin product was obtained with a purity of 97.6%.
Example 7
568.7g of 3-methoxy-4-hydroxy-mandelic acid aqueous solution (with the concentration of 8wt%,0.229 mol), 1706g of toluene and 0.91g of ferric sulfate catalyst are weighed and added into a 5L reaction kettle, the pH value is regulated to 6 by adopting a dilute sulfuric acid aqueous solution with the concentration of 1wt%, after nitrogen replacement, stirring is started, the rotating speed is set to 2000rpm, and the temperature is controlled to 35 ℃ by adopting a high-low temperature tank; 26.30g of hydrogen peroxide (concentration of 30wt percent, 0.232 mol) is weighed, after precooling to 5 ℃, the hydrogen peroxide is dripped into a reaction kettle by adopting a peristaltic pump, the dripping is finished for 32 hours, the heat preservation reaction is continued for 0.2 hour, and the reaction is finished. The conversion of the sample was 99.9% and the selectivity was 96.09%.
After the reaction solution was returned to room temperature, the reaction solution was transferred to a separating funnel, allowed to stand for 1 hour, the upper oil phase was taken, toluene in the oil phase was separated by a rotary evaporator, and 32.45g of a vanillin product was obtained, with a purity of 98.3%.
Comparative example 1
Vanillin was prepared according to the method of example 1, except that: no toluene extractant is added, other operations are unchanged, sampling analysis is carried out after the reaction is finished, the conversion rate of raw materials is 83.6%, and the selectivity is 72.63%; the vanillin product was obtained in an amount of 22.1g and a purity of 90%.
Comparative example 2
Vanillin was prepared according to the method of example 1, except that: toluene is replaced by ethyl acetate with equal mass, other operations are unchanged, sampling analysis is carried out after the reaction is finished, the conversion rate of raw materials is 46%, and the selectivity is 66%; 12g of vanillin product with a purity of 85% are obtained.
Comparative example 3
Vanillin was prepared according to the method of example 1, except that: toluene is replaced by benzene with equal mass, other operations are unchanged, sampling analysis is carried out after the reaction is finished, the conversion rate of raw materials is 59%, and the selectivity is 77%; 19.5g of vanillin product is obtained with a purity of 81%.
Comparative example 4
Vanillin was prepared according to the method of example 1, except that: toluene is replaced by ethylbenzene with equal mass, other operations are unchanged, sampling analysis is carried out after the reaction is finished, the conversion rate of raw materials is 24%, and the selectivity is 82%; 9g of vanillin product is obtained, with a purity of 73%.
Comparative example 5
Vanillin was prepared according to the method of example 1, except that: no ferric sulfate catalyst is added, other operations are unchanged, sampling analysis is carried out after the reaction is finished, the raw material conversion rate is 10%, and the selectivity is 95%; 3.4g of vanillin product is obtained with a purity of 96%.
Comparative example 6
Vanillin was prepared according to the method of example 1, except that: the ferric sulfate is replaced by cobalt sulfate with equal mass, other operations are unchanged, sampling analysis is carried out after the reaction is finished, the raw material conversion rate is 80%, and the selectivity is 60%; 18.5g of vanillin product is obtained with a purity of 89%.
Comparative example 7
Vanillin was prepared according to the method of example 1, except that: the ferric sulfate is replaced by ferric chloride with equal mass, other operations are unchanged, sampling analysis is carried out after the reaction is finished, the raw material conversion rate is 85%, and the selectivity is 82%; 26g of vanillin product is obtained with a purity of 93%.
Comparative example 8
Vanillin was prepared according to the method of example 1, except that: replacing ferric sulfate with ferric acetate with equal mass, sampling and analyzing after the reaction is finished, wherein the raw material conversion rate is 40% and the selectivity is 78%; 12.8g of vanillin product is obtained with a purity of 85%.
Comparative example 9
Vanillin was prepared according to the method of example 1, except that: replacing hydrogen peroxide with equivalent copper oxide, keeping other operations unchanged, and sampling and analyzing the raw material after the reaction is finished, wherein the conversion rate is 50% and the selectivity is 92%; 16.3g of vanillin product is obtained with a purity of 98%.
Comparative example 10
Vanillin was prepared according to the method of example 1, except that: the hydrogen peroxide is replaced by the same amount of oxygen, other operations are unchanged, the conversion rate of the sampling analysis raw material after the reaction is finished is 54%, and the selectivity is 66%; 13g of vanillin product is obtained with a purity of 92%.
Claims (20)
1. A one-step method for preparing vanillin is characterized in that ferric sulfate is used as a catalyst, and 3-methoxy-4-hydroxy-mandelic acid aqueous solution and hydrogen peroxide react in an acidic system in the presence of toluene to prepare vanillin.
2. The method of claim 1, wherein the aqueous solution of 3-methoxy-4-hydroxy-mandelic acid is at a concentration of 4-8wt%.
3. The method according to claim 2, wherein the aqueous solution of 3-methoxy-4-hydroxy-mandelic acid is at a concentration of 5-6wt%.
4. The method according to claim 1, wherein the toluene is used in an amount of 100.0 to 400.0% by mass of the aqueous solution of 3-methoxy-4-hydroxy-mandelic acid.
5. The method according to claim 4, wherein the toluene is used in an amount of 200.0 to 300.0% by mass of the aqueous solution of 3-methoxy-4-hydroxy-mandelic acid.
6. The method of claim 1, wherein the hydrogen peroxide concentration is 15.0-65.0wt%.
7. The method of claim 6, wherein the hydrogen peroxide concentration is 45.0-55.0wt%.
8. The method of claim 1, wherein the molar ratio of hydrogen peroxide to 3-methoxy-4-hydroxy-mandelic acid is 0.98-1.02:1.
9. The method of claim 8, wherein the molar ratio of hydrogen peroxide to 3-methoxy-4-hydroxy-mandelic acid is 1.0-1.01:1.
10. The method according to claim 1, wherein the hydrogen peroxide is continuously fed for 18.0-32.0 hours, and the feeding time is not counted in the reaction time; the feeding temperature is the reaction temperature.
11. The method of claim 10, wherein the hydrogen peroxide is added dropwise.
12. The method of claim 10, wherein the feed time is 24.0 to 28.0 hours.
13. The method according to claim 1, wherein the amount of the ferric sulfate catalyst is 2.0-10.0% of the mass of the 3-methoxy-4-hydroxy-mandelic acid.
14. The method according to claim 13, wherein the amount of the ferric sulfate catalyst is 4.0-8.0% by mass of the 3-methoxy-4-hydroxy-mandelic acid.
15. The method of claim 1, wherein the acidic system has a pH of 4.0 to 7.0.
16. The method of claim 15, wherein the acidic system has a pH of 5.0 to 6.0.
17. The method of claim 1, wherein the reaction is carried out at a temperature of 10.0 to 60.0 ℃ for a time of 0.2 to 0.8 hours.
18. The method of claim 17, wherein the reaction is carried out at a temperature of 20.0 to 50.0 ℃ for a time of 0.4 to 0.6 hours.
19. The process according to claim 1, wherein the reaction is carried out under stirring at a speed of 400.0 to 3000.0rpm;
the reaction is preceded by a nitrogen substitution.
20. The method of claim 19, wherein the agitation speed is 1000.0-2000.0rpm.
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| CN102351916A (en) * | 2011-08-24 | 2012-02-15 | 山东福田药业有限公司 | Method for preparing D-arabinose |
| CN106660916A (en) * | 2014-09-09 | 2017-05-10 | 巴斯夫欧洲公司 | Method for producing an aroma substance |
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| CN102351916A (en) * | 2011-08-24 | 2012-02-15 | 山东福田药业有限公司 | Method for preparing D-arabinose |
| CN106660916A (en) * | 2014-09-09 | 2017-05-10 | 巴斯夫欧洲公司 | Method for producing an aroma substance |
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| 可溶性铜盐配合物Cu( OH) 2－4 氧化扁桃酸制备香兰素;钮东方等;《精细化工》;第31卷(第11期);1372-1375 * |
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