CN112661737A - Method for synthesizing coumarin-3-carboxylic acid by low-temperature co-melting liquid catalysis - Google Patents
Method for synthesizing coumarin-3-carboxylic acid by low-temperature co-melting liquid catalysis Download PDFInfo
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- CN112661737A CN112661737A CN202011517941.4A CN202011517941A CN112661737A CN 112661737 A CN112661737 A CN 112661737A CN 202011517941 A CN202011517941 A CN 202011517941A CN 112661737 A CN112661737 A CN 112661737A
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- carboxylic acid
- coumarin
- chloride
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- 239000007788 liquid Substances 0.000 title claims abstract description 44
- ACMLKANOGIVEPB-UHFFFAOYSA-N 2-oxo-2H-chromene-3-carboxylic acid Chemical compound C1=CC=C2OC(=O)C(C(=O)O)=CC2=C1 ACMLKANOGIVEPB-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 238000003181 co-melting Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000005496 eutectics Effects 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 78
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 36
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 32
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 27
- 235000019743 Choline chloride Nutrition 0.000 claims description 27
- 229960003178 choline chloride Drugs 0.000 claims description 27
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 26
- 229960003237 betaine Drugs 0.000 claims description 24
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 16
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 16
- 235000005074 zinc chloride Nutrition 0.000 claims description 16
- 239000011592 zinc chloride Substances 0.000 claims description 16
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims 12
- 239000012071 phase Substances 0.000 claims 3
- 239000008346 aqueous phase Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 description 3
- HJJPJSXJAXAIPN-UHFFFAOYSA-N arecoline Chemical compound COC(=O)C1=CCCN(C)C1 HJJPJSXJAXAIPN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- GXHFUVWIGNLZSC-UHFFFAOYSA-N meldrum's acid Chemical compound CC1(C)OC(=O)CC(=O)O1 GXHFUVWIGNLZSC-UHFFFAOYSA-N 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention discloses a method for synthesizing coumarin-3-carboxylic acid by low-temperature co-melting liquid catalysis, and belongs to the technical field of coumarin-3-carboxylic acid synthesis methods. The specific embodiment is that salicylaldehyde and malonic acid are taken as raw materials, added into a reactor, and catalyzed by low-temperature co-melting liquid to synthesize coumarin-3-carboxylic acid; adding water into the obtained reaction product, layering, recovering an oil phase, continuously participating in the reaction, cooling and crystallizing a water phase, and filtering to obtain a coumarin-3-carboxylic acid product; recovering the low-temperature co-melted liquid in the water phase for reuse. The invention uses salicylaldehyde and malonic acid as raw materials, the raw materials have wide sources and low price, the utilization rate of raw material molecules is high, the produced by-products and pollution are less, low-temperature eutectic liquid is used, the catalyst has the volatility similar to salt and the liquidity of liquid, the catalytic performance is good, the separation and recovery are convenient, the continuous operation can be realized, the defect of low conversion rate of single-pass reaction is overcome, and the total yield is high.
Description
Technical Field
The invention belongs to the technical field of coumarin-3-carboxylic acid synthesis methods, and particularly relates to a method for synthesizing coumarin-3-carboxylic acid by low-temperature co-melting liquid catalysis.
Background
Coumarin-3-carboxylic acid is an important chemical intermediate, and has important application value in the fields of photochemistry and sensors.
The traditional chemical synthesis of coumarin-3-carboxylic acid usually uses salicylaldehyde/meldrum's acid and salicylaldehyde/diethyl malonate as raw materials, and the reaction products also have alcohols besides the coumarin-3-carboxylic acid. The reaction is usually carried out in a solvent system, and the catalysts used are choline chloride, sulfamic acid, H2SO4、SnCl2·2H2O, and the like. The synthesis route has long reaction time, high raw material price and low molecular utilization rate; the reaction process has more byproducts, and the reaction product can be separated in a complex separation process to obtain a product of the coumarin-3 carboxylic acid; meanwhile, the reuse rate of the catalyst is lower; so that the whole process is low in environmental friendliness.
Disclosure of Invention
The invention aims to provide a method for synthesizing coumarin-3-carboxylic acid by low-temperature eutectic liquid catalysis, which solves the problems of long reaction time, large raw material consumption and the like.
A method for synthesizing coumarin-3-carboxylic acid by low-temperature eutectic liquid catalysis is characterized by comprising the following steps:
1) taking salicylaldehyde and malonic acid as raw materials, adding the raw materials into a reactor, and synthesizing coumarin-3-carboxylic acid under the catalysis of low-temperature co-melting liquid;
2) adding water into the reaction product obtained in the step 1), layering, recovering an oil phase, continuously participating in the reaction, cooling and crystallizing a water phase, and filtering to obtain a coumarin-3-carboxylic acid product;
3) recovering the low-temperature co-melted liquid in the water phase for reuse.
The method for catalytically synthesizing the coumarin-3-carboxylic acid by using the low-temperature co-molten liquid is characterized in that the low-temperature co-molten liquid is ethylene glycol/choline chloride, choline chloride/p-methylbenzene sulfonic acid, choline chloride/ferric chloride, choline chloride/zinc chloride, betaine/p-methylbenzene sulfonic acid, betaine/ferric chloride, betaine/zinc chloride, ethylene glycol/choline chloride/p-methylbenzene sulfonic acid, ethylene glycol/choline chloride/ferric chloride, ethylene glycol/choline chloride/zinc chloride, ethylene glycol/betaine/p-methylbenzene sulfonic acid, ethylene glycol/betaine/ferric chloride or ethylene glycol/betaine/zinc chloride.
3. The method for the low-temperature eutectic liquid catalytic synthesis of coumarin-3-carboxylic acid as claimed in claim 1, wherein the catalytic reaction in step 1) is carried out under the conditions of a reaction temperature of 85-180 ℃ and a reaction residence time of 30-640 min.
The method for synthesizing the coumarin-3-carboxylic acid by the low-temperature eutectic liquid catalysis is characterized in that the catalytic reaction in the step 1) is carried out under the microwave catalysis condition, the microwave power is 100-400 w, the reaction temperature is 85-180 ℃, and the reaction residence time is 5-20 min.
The method for synthesizing the coumarin-3-carboxylic acid by the low-temperature eutectic liquid catalysis is characterized in that the initial molar ratio of salicylaldehyde to malonic acid in the step 1) is 1.1-1.5: 1, and the running molar ratio is 1: 1.
The method for catalytically synthesizing coumarin-3-carboxylic acid by using the low-temperature co-melting liquid is characterized in that the using amount of the low-temperature co-melting liquid in the step 1) is 1-5% of the total mass of reactants. 7. The method for the catalytic synthesis of coumarin-3-carboxylic acid with the low-temperature eutectic liquid according to claim 2, wherein the molar ratio of materials in the low-temperature eutectic liquid is 1: 1-4, choline chloride/p-methylbenzenesulfonic acid ═ 1: 1-2.5, choline chloride/ferric chloride ═ 1: 1-3, choline chloride/zinc chloride ═ 1: 1-3, betaine/p-methylbenzenesulfonic acid ═ 1: 2.5, betaine/ferric chloride ═ 1: 1-3, betaine/zinc chloride ═ 1: 1-3, ethylene glycol/choline chloride/p-methylbenzenesulfonic acid ═ 1: 1: 1-2.5, ethylene glycol/choline chloride/ferric chloride ═ 1: 1: 1-3, ethylene glycol/choline chloride/zinc chloride ═ 1: 1: 1-3, ethylene glycol/betaine/p-methylbenzenesulfonic acid ═ 1: 1: 1-2.5, ethylene glycol/betaine/ferric chloride ═ 1: 1: 1-3, ethylene glycol/betaine/zinc chloride ═ 1: 1:1 to 3.
The method for synthesizing coumarin-3-carboxylic acid by low-temperature eutectic liquid catalysis is characterized in that the crystallization temperature in the step 2) is-5-30 ℃.
The method for catalytically synthesizing the coumarin-3-carboxylic acid by using the low-temperature co-melting liquid is characterized in that the method for recovering the low-temperature co-melting liquid in the water phase in the step 3) is evaporation, flash evaporation, thin-film evaporation, rotary evaporation or membrane separation.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention uses salicylaldehyde and malonic acid as raw materials, has wide raw material sources, low price, high utilization rate of raw material molecules and less generated by-products and pollution.
2) The invention uses low-temperature co-melting liquid, the catalyst has the volatility similar to salt and the liquidity of liquid, can play the roles of a solvent and the catalyst in a reaction system, and has good catalytic performance (high selectivity) and convenient separation and recovery.
3) The synthesis process disclosed by the invention can be continuously operated, solves the defect of low conversion rate of a single-pass reaction, and has high total yield.
Drawings
FIG. 1 is a schematic flow diagram of the present invention.
Detailed Description
The invention is further described in the following with reference to the drawings and examples of the description, but the scope of the invention is not limited thereto.
As shown in fig. 1, a method for synthesizing coumarin-3-carboxylic acid by low-temperature co-melting liquid catalysis, which comprises the steps of adding salicylaldehyde and malonic acid serving as raw materials into a reactor, and synthesizing coumarin-3-carboxylic acid under the catalysis of the low-temperature co-melting liquid; adding water into the obtained reaction product, placing the reaction product in an oil-water separator for oil-water separation and layering, recovering an oil phase, continuously participating in the reaction, cooling and crystallizing a water phase, and filtering to obtain a coumarin-3-carboxylic acid product; and recovering the low-temperature co-melted liquid in the water phase for recycling, recycling part of water to the oil-water separator, and discharging part of water.
The specific experimental operating conditions and product yields are shown in Table 1
TABLE 1 yield of product obtained under different operating conditions
As can be seen from table 1, the yield of coumarin-3-carboxylic acid prepared by the present invention can reach 98.7%, so that the conversion per pass and the total yield can be effectively improved by the method of the present invention.
Claims (9)
1. A method for synthesizing coumarin-3-carboxylic acid by low-temperature eutectic liquid catalysis is characterized by comprising the following steps:
1) taking salicylaldehyde and malonic acid as raw materials, adding the raw materials into a reactor, and synthesizing coumarin-3-carboxylic acid under the catalysis of low-temperature co-melting liquid;
2) adding water into the reaction product obtained in the step 1), layering, recovering an oil phase, continuously participating in the reaction, cooling and crystallizing a water phase, and filtering to obtain a coumarin-3-carboxylic acid product;
3) recovering the low-temperature co-melted liquid in the water phase for reuse.
2. The method for the catalytic synthesis of coumarin-3-carboxylic acid with low-temperature co-molten liquid as claimed in claim 1, wherein the low-temperature co-molten liquid is ethylene glycol/choline chloride, choline chloride/p-methylbenzenesulfonic acid, choline chloride/ferric chloride, choline chloride/zinc chloride, betaine/p-methylbenzenesulfonic acid, betaine/ferric chloride, betaine/zinc chloride, ethylene glycol/choline chloride/p-methylbenzenesulfonic acid, ethylene glycol/choline chloride/ferric chloride, ethylene glycol/choline chloride/zinc chloride, ethylene glycol/betaine/p-methylbenzenesulfonic acid, ethylene glycol/betaine/ferric chloride or ethylene glycol/betaine/zinc chloride.
3. The method for the low-temperature eutectic liquid catalytic synthesis of coumarin-3-carboxylic acid as claimed in claim 1, wherein the catalytic reaction in step 1) is carried out under the conditions of a reaction temperature of 85-180 ℃ and a reaction residence time of 30-640 min.
4. The method for synthesizing coumarin-3-carboxylic acid by low-temperature eutectic liquid catalysis according to claim 1, wherein the catalytic reaction in step 1) is performed under microwave catalysis with a microwave power of 100-400 w, a reaction temperature of 85-180 ℃ and a reaction residence time of 5-20 min.
5. The method for the low-temperature co-melting liquid catalytic synthesis of coumarin-3-carboxylic acid as claimed in claim 1, wherein the initial molar ratio of salicylaldehyde to malonic acid in step 1) is 1.1-1.5: 1.
6. The method for catalytically synthesizing coumarin-3-carboxylic acid by using low-temperature co-melting liquid as claimed in claim 1, wherein the amount of the low-temperature co-melting liquid used in step 1) is 1-5% of the total mass of the reactants.
7. The method for the catalytic synthesis of coumarin-3-carboxylic acid with the low-temperature eutectic liquid according to claim 2, wherein the molar ratio of materials in the low-temperature eutectic liquid is 1: 1-4, choline chloride/p-methylbenzenesulfonic acid ═ 1: 1-2.5, choline chloride/ferric chloride ═ 1: 1-3, choline chloride/zinc chloride ═ 1: 1-3, betaine/p-methylbenzenesulfonic acid ═ 1: 2.5, betaine/ferric chloride ═ 1: 1-3, betaine/zinc chloride ═ 1: 1-3, ethylene glycol/choline chloride/p-methylbenzenesulfonic acid ═ 1: 1: 1-2.5, ethylene glycol/choline chloride/ferric chloride ═ 1: 1: 1-3, ethylene glycol/choline chloride/zinc chloride ═ 1: 1: 1-3, ethylene glycol/betaine/p-methylbenzenesulfonic acid ═ 1: 1: 1-2.5, ethylene glycol/betaine/ferric chloride ═ 1: 1: 1-3, ethylene glycol/betaine/zinc chloride ═ 1: 1:1 to 3.
8. The method for the low-temperature eutectic liquid catalytic synthesis of coumarin-3-carboxylic acid as claimed in claim 1, wherein the crystallization temperature in step 2) is-5 to 30 ℃.
9. The method for the catalytic synthesis of coumarin-3-carboxylic acid by using low-temperature co-molten liquid according to claim 1, wherein the method for recovering the low-temperature co-molten liquid in the aqueous phase in the step 3) is evaporation, flash evaporation, thin-film evaporation, rotary evaporation or membrane separation.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011517941.4A CN112661737A (en) | 2020-12-21 | 2020-12-21 | Method for synthesizing coumarin-3-carboxylic acid by low-temperature co-melting liquid catalysis |
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| CN202011517941.4A CN112661737A (en) | 2020-12-21 | 2020-12-21 | Method for synthesizing coumarin-3-carboxylic acid by low-temperature co-melting liquid catalysis |
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| CN112661737A true CN112661737A (en) | 2021-04-16 |
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| CN202011517941.4A Pending CN112661737A (en) | 2020-12-21 | 2020-12-21 | Method for synthesizing coumarin-3-carboxylic acid by low-temperature co-melting liquid catalysis |
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| CN (1) | CN112661737A (en) |
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2020
- 2020-12-21 CN CN202011517941.4A patent/CN112661737A/en active Pending
Non-Patent Citations (6)
| Title |
|---|
| FARIBA KESHAVARZIPOUR ET AL.: ""The synthesis of coumarin derivatives using choline chloride/zinc chloride as a deep eutectic solvent"", 《J IRAN CHEM SOC》 * |
| HULYA CELIK ONAR: ""Comparison of Antioxidant Activities of Mono-, Di- and Tri-substituted Coumarins"", 《JOTCSA》 * |
| MAJID M. HERAVI ET AL.: ""SOLID STATE SYNTHESIS OF SUBSTITUTED COUMARIN-3-CARBOXYLIC ACIDS VIA THE KNOEVENAGEL CONDENSATION UNDER MICROWAVE IRRADIATION"", 《PHOSPHORUS, SULFUR, AND SILICON》 * |
| SUNANDA BALASO PHADTARE ET AL.: ""Greener coumarin synthesis by Knoevenagel condensation using biodegradable choline chloride"", 《ENVIRON CHEM LETT》 * |
| XINWEI HE ET AL.: ""Synthesis of coumarin-3-carboxylic esters via FeCl3-catalyzed multicomponent reaction of salicylaldehydes, Meldrum’s acid and alcohols"", 《TETRAHEDRON》 * |
| 李进军等主编, 武汉大学出版社 * |
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