CN114196974A - Electrochemical synthesis method of vanillin - Google Patents
Electrochemical synthesis method of vanillin Download PDFInfo
- Publication number
- CN114196974A CN114196974A CN202111551027.6A CN202111551027A CN114196974A CN 114196974 A CN114196974 A CN 114196974A CN 202111551027 A CN202111551027 A CN 202111551027A CN 114196974 A CN114196974 A CN 114196974A
- Authority
- CN
- China
- Prior art keywords
- vanillin
- solution
- hydroxy
- synthesis method
- electrochemical synthesis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 34
- 238000001308 synthesis method Methods 0.000 title claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 61
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims abstract description 39
- JMFRWRFFLBVWSI-UHFFFAOYSA-N cis-coniferyl alcohol Natural products COC1=CC(C=CCO)=CC=C1O JMFRWRFFLBVWSI-UHFFFAOYSA-N 0.000 claims abstract description 35
- ZENOXNGFMSCLLL-UHFFFAOYSA-N vanillyl alcohol Chemical compound COC1=CC(CO)=CC=C1O ZENOXNGFMSCLLL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 31
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 238000004440 column chromatography Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 13
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 99
- 239000000243 solution Substances 0.000 claims description 57
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 52
- 238000005868 electrolysis reaction Methods 0.000 claims description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 239000011780 sodium chloride Substances 0.000 claims description 26
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- 239000003208 petroleum Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- FIMJSWFMQJGVAM-UHFFFAOYSA-N chloroform;hydrate Chemical compound O.ClC(Cl)Cl FIMJSWFMQJGVAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 29
- 239000012074 organic phase Substances 0.000 description 24
- 238000004809 thin layer chromatography Methods 0.000 description 24
- 230000008569 process Effects 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- DKZBBWMURDFHNE-UHFFFAOYSA-N trans-coniferylaldehyde Natural products COC1=CC(C=CC=O)=CC=C1O DKZBBWMURDFHNE-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical class [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HBMCQTHGYMTCOF-UHFFFAOYSA-N 4-hydroxyphenyl acetate Chemical compound CC(=O)OC1=CC=C(O)C=C1 HBMCQTHGYMTCOF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000009935 nitrosation Effects 0.000 description 1
- 238000007034 nitrosation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 oxides thereof Chemical compound 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
Abstract
The invention relates to an electrochemical synthesis method of vanillin, which comprises the following steps: (1) dispersing 4-hydroxy-3-methoxybenzyl alcohol, TEMPO and electrolyte in a solvent to obtain a solution A; (2) electrolyzing by taking the obtained solution A as electrolyte, a platinum sheet as a cathode and a platinum sheet as an anode to obtain a solution B; (3) and sequentially carrying out extraction, rotary evaporation and column chromatography separation on the obtained solution B to obtain a target product. The invention adopts an electrochemical synthesis method to carry out selective oxidation reaction on 4-hydroxy-3-methoxybenzyl alcohol in a liquid-liquid two-phase heterogeneous reaction system to prepare vanillin. Compared with the prior art, the product yield is higher and reaches 43%, the synthetic method has low solvent usage amount, is beneficial to reducing the production cost, is green, environment-friendly, efficient and economical, is convenient to operate, and shows good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and relates to an electrochemical synthesis method of vanillin.
Background
Vanillin is also called vanillin, and its chemical name is 4-hydroxy-3-methoxy benzylAldehyde of the formula C8H8O3. Vanillin has vanilla bean fragrance and strong milk fragrance, has effects of increasing aroma and fixing aroma, and can be widely used in industries of cosmetics, tobacco, cake, candy, baked food and the like. It can also be used as plant growth promoter, bactericide, lubricant defoamer, and is also an important intermediate for synthesizing medicines and other perfumes. Besides, it can be used as glazing agent in electroplating industry, ripener in agriculture, deodorant in rubber products, anti-hardening agent in plastic products and medical intermediate, etc. and is widely used.
Vanillin is obtained in a plurality of ways, and the main methods are three methods: plant extraction method, nitrosation method using guaiacol as raw material and glyoxylic acid method. The three methods have the problems of low yield, poor oxidation stability and the like which cannot be solved. In addition, the use of toxic and harmful transition metals such as monochloromethane and cobalt salts and oxides thereof or the use of tetrabutylammonium chloride and other transfer catalysts leads to the generation of a large amount of wastewater.
Disclosure of Invention
The invention aims to provide an electrochemical synthesis method of vanillin, which overcomes the defects of low vanillin yield, use of toxic and harmful transition metals and oxides thereof or use of a phase transfer catalyst to generate a large amount of wastewater in the vanillin synthesis process and the like in the prior art, and is environment-friendly, efficient, economical and feasible.
The purpose of the invention can be realized by the following technical scheme:
an electrochemical synthesis method of vanillin comprises the following steps:
(1) dispersing 4-hydroxy-3-methoxybenzyl alcohol, TEMPO and electrolyte in a solvent to obtain a solution A;
(2) electrolyzing by taking the obtained solution A as electrolyte, a platinum sheet as a cathode and a platinum sheet as an anode to obtain a solution B;
(3) and sequentially carrying out extraction, rotary evaporation and column chromatography separation on the obtained solution B to obtain a target product.
Further, in the step (1), the electrolyte is sodium chloride, and the solvent is a mixed solution of chloroform and water.
Furthermore, the molar ratio of the 4-hydroxy-3-methoxy benzyl alcohol to the TEMPO to the sodium chloride is 1: (0.03-0.2): (0.3-3).
Furthermore, in the mixed solution of chloroform and water, the volume ratio of chloroform to water is 1: 1, and the adding amount ratio of the 4-hydroxy-3-methoxybenzyl alcohol to the chloroform-water mixed solution is 1.14 g: (1-45) mL.
Furthermore, the molar ratio of the 4-hydroxy-3-methoxy benzyl alcohol to the TEMPO is preferably 1: 0.05. the TEMPO is used in catalytic amount, which is favorable for the treatment of the reaction.
Further, in the step (1), the mass of TEMPO is not less than 0.05% of the mass of 4-hydroxy-3-methoxybenzyl alcohol, and the mass of electrolyte is not less than 0.5% of the mass of 4-hydroxy-3-methoxybenzyl alcohol.
Further, in the step (2), in the electrolysis process, the current is 5mA, the temperature is 25-60 ℃, and the electrolysis time is 15-72 h.
Further, in the step (3), an extracting agent used in the extraction process is ethyl acetate.
Further, in the step (3), in the rotary evaporation process, the pressure is 400-600 mm Hg, the temperature is 40-60 ℃, and the rotary evaporation time is 5 min. Rotary evaporation was performed to remove ethyl acetate.
Further, in the step (3), in the column chromatography separation process, the developing agent is a mixed solution of petroleum ether and ethyl acetate.
Furthermore, in the mixed liquid of the petroleum ether and the ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is 3: 1.
the invention develops a green synthesis technology of vanillin with low requirement conditions and meeting the green chemical purpose, and provides a method for preparing vanillin by taking 4-hydroxy-3-methoxy benzyl alcohol and TEMPO as raw materials through electrochemical oxidation. In the electrolysis process, a direct current power supply is used as a power supply, and two platinum sheets are respectively connected as a cathode and an anode through a copper wire and a platinum wire.
Referring to fig. 1, the reaction equation for synthesizing vanillin according to the present invention is shown in fig. 1, wherein 4-hydroxy-3-methoxybenzyl alcohol is subjected to selective oxidation reaction in a liquid-liquid two-phase heterogeneous reaction system, wherein a mixed solution of chloroform and water is used as a solvent system, TEMPO is used as a catalyst, sodium chloride is used as an electrolyte, and a platinum sheet is used as an electrode to prepare vanillin.
The method adopts TEMPO to selectively catalyze and oxidize the 4-hydroxy-3-methoxy benzyl alcohol under the electrocatalysis condition, and the reaction is carried out in a liquid-liquid two-phase heterogeneous reaction system, so the reaction speed is high, and the yield reaches up to 43 percent.
Under the condition of electrifying, NaCl is dissolved in water and is electrolyzed to generate NaClO, so that the solution has ClO–。ClO–TEMPO can be further generated into ammonium oxide salt with selective oxidation effect and Cl is generated–And simultaneously the ammonium oxide salt is reduced back to TEMPO after the oxidation of 4-hydroxy-3-methoxybenzyl alcohol, constituting a reaction cycle until the 4-hydroxy-3-methoxybenzyl alcohol is completely converted into 4-hydroxy-3-methoxybenzaldehyde. TEMPO inhibits excessive oxidation of the reaction product to the acid.
The invention widely researches documents when designing process conditions, the usage amount of TEMPO in the reaction of selectively oxidizing 4-hydroxy-3-methoxybenzyl alcohol into 4-hydroxy-3-methoxybenzaldehyde by using TEMPO as a catalyst is 0.1-equivalent, and the use of 0.05 percent can reduce the cost of the catalyst because TEMPO is difficult to recover in the reaction. If the TEMPO quality is too low in the synthesis process, the conversion rate is reduced, and the reaction time is prolonged; if the quality of the electrolyte is too low, the resistance of the reaction solution is increased, the required power supply voltage is increased, the cost is increased, the process safety is reduced, and the conversion rate is also suddenly reduced.
Compared with the prior art, the invention has the following advantages:
(1) the method takes 4-hydroxy-3-methoxybenzyl alcohol as a raw material, sodium chloride as electrolyte, a mixed solution of chloroform and water as a solvent system, and selectively oxidizes the 4-hydroxy-3-methoxybenzyl alcohol to prepare the 4-hydroxy-3-methoxybenzaldehyde under the action of a catalyst TEMPO and constant direct current, wherein the product yield reaches 43%;
(2) in the synthetic method, toxic and harmful transition metals such as methane chloride and cobalt salt, oxides thereof, tetrabutylammonium chloride and other transfer catalysts are not used, the waste water discharge is less in the production process, and the green synthetic target of the p-methoxybenzaldehyde is basically realized by using clean and green electric power;
(3) the reaction solvent used in the invention is low in dosage, which is beneficial to reducing the production cost;
(4) the preparation method has the advantages of simplicity, convenience in operation, mild reaction conditions, environmental friendliness and the like, and shows a good industrial application prospect.
Drawings
FIG. 1 is a reaction equation for synthesizing vanillin in accordance with the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of the product prepared in example 3.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, all of the conventional commercial starting materials and conventional processing techniques are used.
Example 1:
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken2O、1.5mLCHCl33.9mg TEMPO and 14.6mg NaCl were mixed to obtain a solution A, and electrolysis was performed using the obtained solution A as an electrolyte, a platinum sheet as a cathode and a platinum sheet as an anode to obtain a solution B. In the electrolysis process, the current is 5mA, the temperature is 50 ℃, and the electrolysis time is 15 h. Solution B was extracted with 20mL ethyl acetate to give an organic phase which was checked by Thin Layer Chromatography (TLC). And separating and purifying the obtained organic phase by rotary evaporation (the pressure is 400 mm Hg, the temperature is 40 ℃, the rotary evaporation time is 5min) and column chromatography (a developing agent: petroleum ether/ethyl acetate: 3: 1, volume ratio) in sequence to obtain a white solid, wherein the yield of vanillin is 43 percent by calculation.
Example 2:
taking 1.14g of 4-hydroxy-3-methoxybenzyl alcohol and 2mL of H2O、2mL CHCl3The solution A was obtained by mixing 60mg of TEMPO and 219mg of NaCl, and electrolysis was carried out using the obtained solution A as an electrolyte, a platinum sheet as a cathode and a platinum sheet as an anode to obtain a solution B. In the electrolysis process, the current is 5mA, the temperature is 50 ℃, and the electrolysis time is 24 h. Solution B was extracted with 80mL ethyl acetate to give an organic phase which was checked by Thin Layer Chromatography (TLC). And separating and purifying the obtained organic phase by rotary evaporation (the pressure is 400 mm Hg, the temperature is 40 ℃, the rotary evaporation time is 5min) and column chromatography (a developing agent: petroleum ether/ethyl acetate: 3: 1, volume ratio) in sequence to obtain a white solid, wherein the yield of vanillin is 41% by calculation.
Example 3:
taking 11.42g of 4-hydroxy-3-methoxybenzyl alcohol and 5mL of H2O、5mL CHCl3780mg TEMPO and 2.19g NaCl were mixed to obtain a solution A, and electrolysis was carried out using the obtained solution A as an electrolyte, a platinum sheet as a cathode and a platinum sheet as an anode to obtain a solution B. In the electrolysis process, the current is 5mA, the temperature is 50 ℃, and the electrolysis time is 72 h. Solution B was extracted with 500mL of ethyl acetate to give an organic phase which was checked by Thin Layer Chromatography (TLC). And separating and purifying the obtained organic phase by rotary evaporation (the pressure is 400 mm Hg, the temperature is 40 ℃, the rotary evaporation time is 5min) and column chromatography (a developing agent: petroleum ether/ethyl acetate: 3: 1, volume ratio) in sequence to obtain a white solid, wherein the yield of vanillin is calculated to be 38%.
The nuclear magnetic characterization of the product obtained in this example is shown in fig. 2:
1H NMR (400MHz, Chloroform-d) δ 9.84(d, J ═ 2.4Hz, 1H), 7.45(H, J ═ 2.4Hz, 2H), 7.06(dd, J ═ 8.6, 2.5Hz, 1H), 6.43(t, J ═ 2.9Hz, 1H), 3.98(d, J ═ 2.3Hz, 3H). The results show that vanillin was successfully synthesized.
Example 4:
compared with example 1, most of them are the same, except that the molar ratio of 4-hydroxy-3-methoxybenzyl alcohol, TEMPO and sodium chloride is adjusted to 1: 0.03: 0.5.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken2O、1.5mLCHCl32.3mg TEMPO and 14.6mg NaCl to obtain a solution A, and electrolyzing the solution A serving as an electrolyte, a platinum sheet serving as a cathode and a platinum sheet serving as an anode to obtain a solution B. In the electrolysis process, the current is 5mA, the temperature is 50 ℃, and the electrolysis time is 15 h. Solution B was extracted with 20mL ethyl acetate to give an organic phase which was checked by Thin Layer Chromatography (TLC). And separating and purifying the obtained organic phase by rotary evaporation (the pressure is 400 mm Hg, the temperature is 40 ℃, the rotary evaporation time is 5min) and column chromatography (a developing agent: petroleum ether/ethyl acetate: 3: 1, volume ratio) in sequence to obtain a white solid, wherein the yield of vanillin is calculated to be 37%.
Example 5:
compared with example 1, most of them are the same, except that the molar ratio of 4-hydroxy-3-methoxybenzyl alcohol, TEMPO and sodium chloride is adjusted to 1: 0.2: 0.5.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken2O、1.5mLCHCl315.4mg TEMPO and 14.6mg NaCl were mixed to obtain a solution A, and electrolysis was performed using the obtained solution A as an electrolyte, a platinum sheet as a cathode and a platinum sheet as an anode to obtain a solution B. In the electrolysis process, the current is 5mA, the temperature is 50 ℃, and the electrolysis time is 15 h. Solution B was extracted with 20mL ethyl acetate to give an organic phase which was checked by Thin Layer Chromatography (TLC). And separating and purifying the obtained organic phase by rotary evaporation (the pressure is 400 mm Hg, the temperature is 40 ℃, the rotary evaporation time is 5min) and column chromatography (a developing agent: petroleum ether/ethyl acetate: 3: 1, volume ratio) in sequence to obtain a white solid, wherein the yield of vanillin is 41% by calculation.
Example 6:
compared with example 1, the molar ratio of 4-methoxybenzyl alcohol, TEMPO and sodium chloride is adjusted to 1: 0.05: 0.3.
example 7:
compared with example 1, the molar ratio of 4-methoxybenzyl alcohol, TEMPO and sodium chloride is adjusted to 1: 0.05: 3.
example 8:
most of them were the same as in example 1, except that the temperature during the electrolysis was adjusted to 25 ℃ in this example.
Example 9:
most of them were the same as in example 1, except that the temperature during the electrolysis was adjusted to 60 ℃ in this example.
Example 10:
compared with example 1, most of the same results, except that in this example, the pressure is 400 mmHg and the temperature is 40 ℃ and the pressure is 600 mmHg and the temperature is 60 ℃.
Example 11:
compared with example 1, most of the same results, except that in this example, the pressure is 400 mmHg and the temperature is 40 ℃ and the pressure is 500 mmHg and the temperature is 50 ℃.
Comparative example 1:
compared to example 1, most of them are identical, except that TEMPO is not added in this comparative example.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken2O、1.5mLCHCl3And 14.6mg of NaCl to obtain a solution A, and carrying out electrolysis with the obtained solution A as an electrolyte, a platinum sheet as a cathode and a platinum sheet as an anode to obtain a solution B. In the electrolysis process, the current is 5mA, the temperature is 50 ℃, and the electrolysis time is 15 h. Solution B was extracted with 20mL ethyl acetate to give an organic phase which was checked by Thin Layer Chromatography (TLC). The obtained organic phase is separated and purified by rotary evaporation (the pressure is 400 mm Hg, the temperature is 40 ℃, the rotary evaporation time is 5min) and column chromatography (a developing solvent: petroleum ether/ethyl acetate is 3: 1, the volume ratio) in turn to obtain a white solid, and the yield of the 4-hydroxy-3-methoxybenzaldehyde is reduced to 2 percent by calculation. The yield suddenly drops, which shows that the addition of TEMPO has a great promoting effect on the reaction.
Comparative example 2:
compared with example 1, most of them were the same except that the reaction temperature was adjusted to 80 ℃.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken2O、1.5mLCHCl33.9mg TEMPO and 14.6mg NaCl were mixed to obtain a solution A, and electrolysis was performed using the obtained solution A as an electrolyte, a platinum sheet as a cathode and a platinum sheet as an anode to obtain a solution B. In the electrolysis process, the current is 5mA, the temperature is 80 ℃, and the electrolysis time is 15 h. Solution B was extracted with 20mL ethyl acetate to give an organic phase which was checked by Thin Layer Chromatography (TLC). The obtained organic phase is separated and purified by rotary evaporation (the pressure is 400 mm Hg, the temperature is 40 ℃, the rotary evaporation time is 5min) and column chromatography (a developing solvent: petroleum ether/ethyl acetate is 3: 1, the volume ratio) in turn to obtain a white solid, and the yield of the 4-hydroxy-3-methoxybenzaldehyde is reduced to 2 percent by calculation. The yield suddenly dropped, and the calculated yield of 4-hydroxy-3-methoxybenzaldehyde decreased to 15%. High temperatures are not favorable for this reaction.
Comparative example 3:
compared with example 1, most of them were the same except that the reaction temperature was adjusted to 0 ℃.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken2O、1.5mLCHCl33.9mg TEMPO and 14.6mg NaCl were mixed to obtain a solution A, and electrolysis was performed using the obtained solution A as an electrolyte, a platinum sheet as a cathode and a platinum sheet as an anode to obtain a solution B. In the electrolysis process, the current is 5mA, the temperature is 0 ℃, and the electrolysis time is 15 h. Solution B was extracted with 20mL ethyl acetate to give an organic phase which was checked by Thin Layer Chromatography (TLC). The obtained organic phase is separated and purified by rotary evaporation (the pressure is 400 mm Hg, the temperature is 40 ℃, the rotary evaporation time is 5min) and column chromatography (a developing solvent: petroleum ether/ethyl acetate is 3: 1, the volume ratio) in turn to obtain a white solid, and the yield of the 4-hydroxy-3-methoxybenzaldehyde is reduced to 7 percent by calculation. The reaction proceeds unfavorably at low temperature and the reaction time is greatly prolonged.
Comparative example 4:
compared to example 1, most of them were the same, except that 3.9mg TEMPO was changed to 31.2mg TEMPO and 14.6mg NaCl was changed to 87.6mg NaCl.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken2O、1.5mLCHCl331.2mg of TEMPO and 87.6mg of NaCl were mixed to obtain a solution A, and electrolysis was carried out using the obtained solution A as an electrolyte, a platinum sheet as a cathode and a platinum sheet as an anode to obtain a solution B. In the electrolysis process, the current is 5mA, the temperature is 50 ℃, and the electrolysis time is 15 h. Solution B was extracted with 20mL ethyl acetate to give an organic phase which was checked by Thin Layer Chromatography (TLC). And separating and purifying the obtained organic phase by rotary evaporation (the pressure is 400 mm Hg, the temperature is 40 ℃, the rotary evaporation time is 5min) and column chromatography (a developing agent: petroleum ether/ethyl acetate: 3: 1, volume ratio) in sequence to obtain a white solid, and calculating the yield of the 4-hydroxy-3-methoxybenzaldehyde to be 45%. Increasing the TEMPO and NaCl ratio did not have much effect on product yield.
Comparative example 5:
compared to example 1, most of them are the same except that the electrolysis process is omitted.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken2O、1.5mLCHCl33.9mg TEMPO and 14.6mg NaCl were mixed and the resulting solution was stirred at 50 ℃ for 15 h. After the reaction, the resulting solution was extracted with 20mL of ethyl acetate to obtain an organic phase, which was detected by Thin Layer Chromatography (TLC). The obtained organic phase is separated and purified by rotary evaporation (the pressure is 400 mm Hg, the temperature is 40 ℃, the rotary evaporation time is 5min) and column chromatography (a developing solvent: petroleum ether/ethyl acetate: 3: 1, volume ratio) in sequence to obtain a white solid, and the yield of the 4-hydroxy-3-methoxybenzaldehyde is calculated to be 3%. Indicating that the passage of electricity is critical to the progress of the reaction.
Comparative example 6:
compared with example 1, most of them are the same except that the current 5mA is changed to 20 mA.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken2O、1.5mLCHCl33.9mg TEMPO and 14.6mg NaCl were mixed to obtain a solution A, and electrolysis was performed using the obtained solution A as an electrolyte, a platinum sheet as a cathode and a platinum sheet as an anode to obtain a solution B. In the electrolysis process, the current is 20mA, the temperature is 50 ℃, and the electrolysis time is 15 h. Use of solution BExtraction with 20mL ethyl acetate gave an organic phase which was checked by Thin Layer Chromatography (TLC). And separating and purifying the obtained organic phase by rotary evaporation (the pressure is 400 mm Hg, the temperature is 40 ℃, the rotary evaporation time is 5min) and column chromatography (a developing agent: petroleum ether/ethyl acetate: 3: 1, volume ratio) in sequence to obtain a white solid, and calculating the yield of the 4-hydroxy-3-methoxybenzaldehyde to be 29%. Indicating that the current is too high to facilitate the reaction.
Comparative example 7:
compared with example 1, the electrolysis time is mostly the same except that the electrolysis time 15h is changed to 24 h.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken2O、1.5mLCHCl33.9mg TEMPO and 14.6mg NaCl were mixed to obtain a solution A, and electrolysis was performed using the obtained solution A as an electrolyte, a platinum sheet as a cathode and a platinum sheet as an anode to obtain a solution B. In the electrolysis process, the current is 5mA, the temperature is 50 ℃, and the electrolysis time is 24 h. Solution B was extracted with 20mL ethyl acetate to give an organic phase which was checked by Thin Layer Chromatography (TLC). And separating and purifying the obtained organic phase by rotary evaporation (the pressure is 400 mm Hg, the temperature is 40 ℃, the rotary evaporation time is 5min) and column chromatography (a developing agent: petroleum ether/ethyl acetate: 3: 1, volume ratio) in sequence to obtain a white solid, and calculating the yield of the 4-hydroxy-3-methoxybenzaldehyde to be 40%.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. An electrochemical synthesis method of vanillin is characterized by comprising the following steps:
(1) dispersing 4-hydroxy-3-methoxybenzyl alcohol, TEMPO and electrolyte in a solvent to obtain a solution A;
(2) electrolyzing by taking the obtained solution A as electrolyte, a platinum sheet as a cathode and a platinum sheet as an anode to obtain a solution B;
(3) and sequentially carrying out extraction, rotary evaporation and column chromatography separation on the obtained solution B to obtain a target product.
2. The electrochemical synthesis method of vanillin in claim 1, wherein in the step (1), the electrolyte is sodium chloride, and the solvent is a mixture of chloroform and water.
3. The electrochemical synthesis method of vanillin in claim 2, wherein the molar ratio of the 4-hydroxy-3-methoxybenzyl alcohol to the TEMPO to the sodium chloride is 1: (0.03-0.2): (0.3-3).
4. The electrochemical synthesis method of vanillin according to claim 2, wherein the volume ratio of chloroform to water in the mixed solution of chloroform and water is 1: 1, and the adding amount ratio of the 4-hydroxy-3-methoxybenzyl alcohol to the chloroform-water mixed solution is 1.14 g: (1-45) mL.
5. The electrochemical synthesis method of vanillin in claim 1, wherein in the step (1), the mass of TEMPO is not less than 0.05% of the mass of 4-hydroxy-3-methoxybenzyl alcohol, and the mass of electrolyte is not less than 0.5% of the mass of 4-hydroxy-3-methoxybenzyl alcohol.
6. The electrochemical synthesis method of vanillin in claim 1, wherein in the step (2), the current is 5mA, the temperature is 25-60 ℃ and the electrolysis time is 15-72 h.
7. The electrochemical synthesis method of vanillin in claim 1, wherein in the step (3), the extractant used in the extraction process is ethyl acetate.
8. The electrochemical synthesis method of vanillin in claim 1, wherein in the step (3), the pressure is 400-600 mm Hg, the temperature is 40-60 ℃, and the rotary evaporation time is 5 min.
9. The electrochemical synthesis method of vanillin in claim 1, wherein in the step (3), the developing solvent used in the column chromatography separation process is a mixed solution of petroleum ether and ethyl acetate.
10. The electrochemical synthesis method of vanillin in claim 9, wherein the volume ratio of the petroleum ether to the ethyl acetate in the mixed solution of the petroleum ether and the ethyl acetate is 3: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111551027.6A CN114196974B (en) | 2021-12-17 | 2021-12-17 | Electrochemical synthesis method of vanillin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111551027.6A CN114196974B (en) | 2021-12-17 | 2021-12-17 | Electrochemical synthesis method of vanillin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114196974A true CN114196974A (en) | 2022-03-18 |
| CN114196974B CN114196974B (en) | 2023-11-24 |
Family
ID=80655102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111551027.6A Active CN114196974B (en) | 2021-12-17 | 2021-12-17 | Electrochemical synthesis method of vanillin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114196974B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103842555A (en) * | 2011-08-11 | 2014-06-04 | 巴斯夫欧洲公司 | Method for producing vanillin by electrochemically oxidizing aqueous lignin solutions or suspensions |
-
2021
- 2021-12-17 CN CN202111551027.6A patent/CN114196974B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103842555A (en) * | 2011-08-11 | 2014-06-04 | 巴斯夫欧洲公司 | Method for producing vanillin by electrochemically oxidizing aqueous lignin solutions or suspensions |
Non-Patent Citations (2)
| Title |
|---|
| JOSEPH T. HILL-COUSINS ET. AL.: "TEMPO-Mediated Electrooxidation of Primary and Secondary Alcohols in a Microfluidic Electrolytic Cell", 《CHEMSUSCHEM》 * |
| TSUTOMU INOKUCHI ET. AL.: "Indirect Electrooxidation of Alcohols by a Double Mediatory System with Two Redox Couples of [R,N+=O]/R,NO\' and [Br\' or Br+]/Br- in an Organic-Aqueous Two-Phase Solution", 《J. ORG. CHEM.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114196974B (en) | 2023-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1053707A (en) | Process for preparing p-benzoquinone diketals | |
| CN109778222B (en) | Method for preparing aldehyde substance and aromatic ester simultaneously by paired electrodes and used electrodes | |
| CN113737206A (en) | Synthesis method for preparing sulfoxide compound from thioether under electrochemistry | |
| CN110777391B (en) | Electric reduction preparation method of gefitinib intermediate | |
| JP4755458B2 (en) | Method for producing 2-alkyne-1-acetal | |
| CN114196974B (en) | Electrochemical synthesis method of vanillin | |
| Torii et al. | Electrooxidative cleavage of carbon-carbon linkages. 1. Preparation of acyclic oxoalkanoates from 2-hydroxy-and 2-acetoxy-1-cycloalkanones and cycloalkanone enol acetates | |
| CN109321939B (en) | Electrochemical synthesis method of thiazole compound | |
| EP3668830B1 (en) | Electrochemical method for producing valeric acid | |
| EP0021769B1 (en) | Processes for producing 2,6-dimethyl-3-alkoxy-oct-1-en-8-ol, dehydrocitronellol and 2-(2'-methyl-1'-propenyl)-4-methyltetrahydropyran | |
| JPH0711471A (en) | Preparation of perfluoropolyether | |
| CN102311408B (en) | Method for preparing styrene oxide by waste water zero discharge process | |
| CN112410807B (en) | Preparation method of tetra-substituted sulfonated vinyl ether under electrocatalysis | |
| KR0146373B1 (en) | Process for the preparation of dodecanedioic | |
| Shtelman et al. | A new method for the synthesis of disilylalkanes by Kolbe anodic oxidation of α-silylcarboxylic acids | |
| US11773128B2 (en) | Electrocatalytic synthesis of dihydrochalcones | |
| Ghobadi et al. | Electrosynthesis of cinnamic acid by electrocatalytic carboxylation of phenylacetylene in the presence of [Ni II (Me 4-NO 2 Bzo [15] tetraeneN 4)] complex: An EC′ CCC′ C mechanism | |
| Christofis et al. | Reduction of some organic compounds by electrochemically generated titanium (III) | |
| JPS6342713B2 (en) | ||
| JPH0210814B2 (en) | ||
| CN110656347A (en) | Electroreduction preparation method of olanzapine intermediate | |
| CN115417756B (en) | Process for preparing vanillin from eugenol by one-pot method | |
| CN110016689B (en) | Electrochemical preparation method of allyl alcohol | |
| JPH0219195B2 (en) | ||
| CN109518211B (en) | Electrochemical synthesis method of aromatic acyl-coupled compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |