CN115991635A - Method for industrially synthesizing eugenol by utilizing o-methoxyphenyl allyl ether - Google Patents
Method for industrially synthesizing eugenol by utilizing o-methoxyphenyl allyl ether Download PDFInfo
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- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000005770 Eugenol Substances 0.000 title claims abstract description 44
- 229960002217 eugenol Drugs 0.000 title claims abstract description 44
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 24
- KWRBXILMRLLABD-UHFFFAOYSA-N 1-methoxy-2-prop-2-enoxybenzene Chemical compound COC1=CC=CC=C1OCC=C KWRBXILMRLLABD-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- 229940075630 samarium oxide Drugs 0.000 claims abstract description 20
- 229910001954 samarium oxide Inorganic materials 0.000 claims abstract description 20
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000005821 Claisen rearrangement reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000006462 rearrangement reaction Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 230000008707 rearrangement Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- -1 o-methoxyphenylpropenyl ether Chemical compound 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000002265 prevention Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- 229960001867 guaiacol Drugs 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 235000009518 sodium iodide Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- 241000219926 Myrtaceae Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 244000223014 Syzygium aromaticum Species 0.000 description 1
- 235000016639 Syzygium aromaticum Nutrition 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000010634 clove oil Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Classifications
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for industrially synthesizing eugenol by utilizing o-methoxy phenyl allyl ether, which is mainly characterized in that the o-methoxy phenyl allyl ether is added into nano samarium oxide, and the claisen rearrangement occurs by heating catalysis, so that the yield of eugenol is increased, the cost is greatly reduced, and the method is safe and environment-friendly.
Description
Technical Field
The invention relates to the technical field of production and preparation of feeds and food additives, in particular to a method for extracting eugenol from o-methoxy phenyl allyl ether which is a byproduct of industrialized eugenol synthesis, and specifically relates to a method for industrially synthesizing eugenol by utilizing o-methoxy phenyl allyl ether.
Background
Eugenol, chemical name 4-allyl-2-methoxyphenol. Is a colorless or pale yellow liquid with flos Caryophylli taste. Is miscible with alcohol, ether, chloroform, and volatile oil, soluble in glacial acetic acid and caustic solution, and insoluble in water. Has the functions of inhibiting bacteria and killing viruses, can be used as soap, is taken as spice, and is more used as a feed additive, thereby being widely used.
At present, the sources of eugenol are mainly:
1. the natural eugenol is mainly prepared by distilling the dry bud of clove which is a myrtaceae plant and is rich in clove oil to obtain volatile oil, extracting (dissolving and separating phenol and non-phenol oil in a constant sodium hydroxide solution, extracting by petroleum ether, acidifying, neutralizing, rectifying and the like), wherein the raw materials are greatly influenced by climate and harvest, have unstable sources and have larger fluctuation of quality, so that the method is unfavorable for industrial production.
2. Patent No. US4048236 describes the production of eugenol by the reaction of guaiacol and allyl chloride with copper salts such as cuprous chloride, cupric oxide, cupric acetate, cupric phosphate, cupric sulfate, etc. as catalysts, respectively. The proposal has the advantages of large wastewater amount, low conversion rate, 50-68% selectivity of eugenol and low selectivity. The reaction is a strongly exothermic reaction, so that allyl chloride needs to be slowly added dropwise, making the reaction control difficult, and the reaction has problems of corrosion of equipment and the like due to the copper salt as a catalyst. The content of eugenol synthesized by the reaction is 45%, the content of O-eugenol is 13%, the boiling point difference of the two components is 1-2 ℃, and the pure eugenol cannot be obtained by industrialized conventional rectification, so that the industrialized possibility is low.
The patent No. JPA1977025727 adopts cuprous chloride as a catalyst, guaiacol and allyl chloride react at 20-25 ℃, and a large amount of sodium iodide is added to participate in the system reaction. The reaction has a large amount of wastewater, the concentration of sodium iodide in the wastewater is as high as 30%, the wastewater is very difficult to treat, and the cost of sodium iodide is very high, so the production cost is very high. In the reaction process, the material system is very viscous, equipment and pipelines are blocked in the industrial process, and the corrosiveness is strong, so that the service life of the equipment pipelines is greatly shortened. The conversion rate can reach 87%, but the eugenol selectivity is only 60%, and a large amount of O-eugenol is additionally arranged, so that the eugenol product can not be separated and purified by the conventional rectification method.
The patent number CN105294409A adopts the prepared solid catalyst, adopts copper nitrate and cobalt nitrate to dissolve, precipitate and calcine to prepare the solid catalyst, and then utilizes guaiacol and allyl chloride to react at 16-25 ℃ to prepare eugenol, the conversion rate of guaiacol is more than 95%, and the selectivity is about 90%. The preparation of the catalyst increases the production cost, so that the industrialization possibility is reduced. In the patent, the eugenol and the O-eugenol are separated, potassium carbonate and n-octane are adopted for separation, then hot water is used for dissolution, and the subsequent rectification and purification are carried out, so that the preparation process is long, the waste water amount is large, and the production cost is high.
And the method provided by the inventor of the patent application No. 202211270722.X can effectively synthesize eugenol in an industrialized mode and purify the eugenol, mainly adopts a molecular sieve preparation mode in the preparation and purification stages of the catalyst in the synthesis stage, solves the industrialized synthesis of eugenol, greatly reduces the cost, and is safe and environment-friendly. During the synthesis stage of this technique, some amount of o-methoxyphenylallyl ether is produced.
The production and preparation enterprises of the professional additives of the enterprise system where the inventor is located have great demands for eugenol, so that the research direction of how to efficiently and industrially synthesize and prepare eugenol is focused, wherein if some byproducts, such as: the o-methoxy phenyl allyl ether is utilized and is further excavated, so that great commercial value is brought.
Disclosure of Invention
The invention aims to solve the problems and provide a method for industrially synthesizing eugenol by utilizing o-methoxy phenyl allyl ether, which mainly aims to increase the yield of eugenol, greatly reduce the cost, and is safe and environment-friendly by adding the o-methoxy phenyl allyl ether into nano samarium oxide and heating and catalyzing a mode of generating claisen rearrangement.
The invention solves the technical problems by adopting the following technical scheme:
a method for industrially synthesizing eugenol by utilizing o-methoxy phenyl allyl ether is characterized by comprising the following steps: the specific method comprises the following steps:
adding nano samarium oxide into o-methoxy phenyl allyl ether in a stirring and heating reaction kettle, introducing nitrogen for oxidation prevention, heating and catalyzing to generate claisen rearrangement, cooling after the reaction is finished, recovering a catalyst through a filter centrifuge or a filter press to obtain a eugenol crude product, and obtaining a eugenol finished product through a solvent recovery step or a reduced pressure rectification mode of the crude product.
Preferably, the addition amount of the catalyst nano samarium oxide is 0.1mol percent to 20mol percent of o-methoxyphenylpropenyl ether, the preferred addition amount is 1mol percent to 10mol percent, and the particle size of the catalyst nano samarium oxide is less than 150nm;
preferably, the temperature at the time of heating is 110-180 ℃, preferably 140 ℃;
preferably, the reaction rearrangement time is 5-18h, preferably 12;
preferably, the rearrangement reaction system thereof is not limited to a solvent and a solvent-free, preferably a solvent-free.
The beneficial effects of the invention are as follows: the conversion rate of the o-methoxyphenylpropenyl ether and the yield of eugenol are greatly improved by adding nano samarium oxide for catalytic rearrangement. The conversion rate of rearrangement is up to 95%, and the yield of eugenol is up to 65%.
Drawings
FIG. 1 is a GC diagram of the product of example 2 of the invention after purification;
FIG. 2 is a GC diagram of the product of example 3 of the invention after purification;
Detailed Description
The following specific examples illustrate a method of the present invention for the industrial synthesis of eugenol using o-methoxyphenylallyl ether.
Example 1
Step 1: 0.1mol of samarium oxide and urea were added to nitric acid, diluted with pure water to obtain 0.05mol/L, and after accelerating 1.0mol/L urea solution, the mixture was stirred at 90℃for 1.5 hours and cooled, 20ml of butanol was added thereto, followed by centrifugation, washing with pure water three times, and vacuum drying to form crystalline particles. Roasting for 2 hours at 450 ℃ to obtain the nano samarium oxide.
Step 2: the 0.1mol of o-methoxy allyl phenyl ether and 0.05mol of nano samarium oxide are placed in a round bottom flask, and then are vibrated by ultrasonic waves for 60min to form a good dispersion system. And (3) introducing nitrogen to perform rearrangement reaction for 12h at 140 ℃. After the reaction, cooling, adding 30ml of normal hexane into the reaction solution, and filtering to recover the nano samarium oxide. The filtrate is recovered under reduced pressure to obtain 16.39g of crude product, and the conversion rate is 100% and the yield is 65% after gc detection.
Step 3: and (3) recovering the nano samarium oxide obtained in the step (2), washing, and drying. Repeating rearrangement of the 2 o-methoxy allyl phenyl ether, and repeating for 5 times to obtain 100%,98%,95%,91% and 90% conversion rate respectively, wherein the following table is:
| sequence number | 1 | 2 | 3 | 4 | 5 |
| Conversion/% | 100 | 98 | 95 | 91 | 90 |
Example 2
Step 1: 0.1mol of guaiacol, 0.11mol of allyl chloride, 0.1g of potassium iodide, 12.5g of anhydrous potassium carbonate and 20ml of anhydrous acetone were heated under reflux for 8 hours. Cooling, diluting with 40ml of water, extracting with n-hexane, washing the extract with 10% sodium hydroxide solution, drying with anhydrous potassium carbonate, evaporating to remove solvent, and distilling the residue under reduced pressure to obtain o-methoxy allyl phenyl ether;
step 2: and (3) placing the o-methoxy allyl phenyl ether obtained in the step (1) and 0.05mol of nano samarium oxide into a round-bottomed flask, introducing nitrogen for protection, and carrying out rearrangement reaction for 12h at 140 ℃. After the reaction, cooling, adding 30ml of normal hexane into the reaction solution, and filtering to recover the nano samarium oxide. The filtrate is recovered to obtain 16.35g of crude product, and the gc detection shows that the crude product contains 56.88 percent of eugenol, and the yield is 55 percent.
Example 3
Step 1: sodium phenolate solution was prepared from 0.11mol of sodium hydroxide, 0.1mol of guaiacol and 25ml of tap water. To a round bottom flask was added 0.4g of cuprous chloride and 2 ml of 28% aqueous ammonia and stirred well to form a cuprammonium complex, 10g of sodium chloride and 1.2mol of allyl chloride were added and cooled to 12 ℃. Dropwise adding sodium phenolate solution (dropwise adding time is about 60 min) while stirring, wherein the dropwise adding temperature is not higher than 22 ℃, and the dropwise adding reaction is completed for 90min. Adding a certain amount of 30% dilute sulfuric acid to regulate pH of the reaction solution to be less than 7, adding 30ml of n-hexane for extraction, separating the solution, recovering the solvent, and performing reduced pressure distillation to obtain a solution containing 17% of o-allyl phenyl ether and 58% of eugenol;
step 2: the crude mixture distilled in step 1 and 0.05mol of nano samarium oxide were placed in a round bottom flask. Introducing nitrogen for protection, carrying out rearrangement reaction at 140 ℃ for 12 hours, cooling after the reaction is finished, adding 30ml of normal hexane into the reaction liquid, and filtering to recover the nano samarium oxide. The filtrate was recovered to give 16.3g of crude product containing 71% of eugenol as measured by gc, and the yield was 69% based on guaiacol as a substrate.
Example 4
Step 1: putting 0.1mol of o-methoxy allyl phenyl ether and 0.05mol of nano samarium oxide into a round bottom flask, adding different solvents, and stirring to form a good dispersion system. And (3) introducing nitrogen to perform rearrangement reaction for 12h at 140 ℃. Cooling after the reaction is finished, and filtering to recover the nano samarium oxide. Recovering the filtrate under reduced pressure to obtain crude product, and detecting by GC, wherein the conversion rate and yield of different solvents are as follows
| Sequence number | Solvent(s) | Conversion rate | Selectivity of |
| 1 | DMF | 65％ | 65％ |
| 2 | Ph | 80％ | 65％ |
| 3 | PhMe | 79％ | 24％ |
| 4 | PhCl | 79％ | 40％ |
| 5 | Solvent-free | 100 | 65％ |
The above examples are only 3 preferred embodiments of the present invention, and the ordinary changes and substitutions made by those skilled in the art within the scope of the present invention should be included in the scope of the present invention.
Claims (5)
1. The method for industrially synthesizing eugenol by utilizing o-methoxyphenyl allyl ether is characterized by comprising the following steps of: the specific method comprises the following steps:
adding nano samarium oxide into o-methoxy phenyl allyl ether in a stirring and heating reaction kettle, introducing nitrogen for oxidation prevention, heating and catalyzing to generate claisen rearrangement, cooling after the reaction is finished, recovering a catalyst through a filter centrifuge or a filter press to obtain a eugenol crude product, and obtaining a eugenol finished product through a solvent recovery step or a reduced pressure rectification mode of the crude product.
2. The method for industrially synthesizing eugenol by using o-methoxyphenyl allyl ether according to claim 1, wherein the method comprises the following steps: the addition amount of the catalyst nano samarium oxide is 0.1mol percent to 20mol percent of o-methoxyphenylpropenyl ether, the preferable addition amount is 1mol percent to 10mol percent, and the particle size of the catalyst nano samarium oxide is smaller than 150nm.
3. The method for industrially synthesizing eugenol by using o-methoxyphenyl allyl ether according to claim 1, wherein the method comprises the following steps: the temperature at the time of heating is 110 to 180 ℃, preferably 140 ℃.
4. The method for industrially synthesizing eugenol by using o-methoxyphenyl allyl ether according to claim 1, wherein the method comprises the following steps: the reaction rearrangement time is 5-18h, preferably 12.
5. The method for industrially synthesizing eugenol by using o-methoxyphenyl allyl ether according to claim 1, wherein the method comprises the following steps: the rearrangement reaction system thereof is not limited to a solvent and a solvent-free, but is preferably a solvent-free one.
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- 2022-10-31 CN CN202211341264.4A patent/CN115991635A/en active Pending
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