CN114196974B - Electrochemical synthesis method of vanillin - Google Patents
Electrochemical synthesis method of vanillin Download PDFInfo
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- CN114196974B CN114196974B CN202111551027.6A CN202111551027A CN114196974B CN 114196974 B CN114196974 B CN 114196974B CN 202111551027 A CN202111551027 A CN 202111551027A CN 114196974 B CN114196974 B CN 114196974B
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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 42
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 30
- 238000001308 synthesis method Methods 0.000 title claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 44
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 36
- 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
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 30
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 27
- 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 12
- 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 56
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 51
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 28
- 239000011780 sodium chloride Substances 0.000 claims description 25
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- 239000003208 petroleum Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000010025 steaming Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000012074 organic phase Substances 0.000 description 24
- 238000004809 thin layer chromatography Methods 0.000 description 24
- 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 12
- 238000002156 mixing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 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
- 239000003205 fragrance Substances 0.000 description 3
- 230000003647 oxidation Effects 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
- 230000000694 effects Effects 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
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 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
- 238000005481 NMR spectroscopy Methods 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
- 150000007513 acids Chemical class 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
- 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
- 150000001868 cobalt Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 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
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 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
- 235000013305 food Nutrition 0.000 description 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 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
- 239000000543 intermediate 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
- -1 methyl chloride, cobalt salts Chemical class 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
- 230000009935 nitrosation Effects 0.000 description 1
- 238000007034 nitrosation reaction Methods 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
- 239000012450 pharmaceutical intermediate 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
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method 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
- 230000005070 ripening Effects 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
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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) The solution A is taken as electrolyte, a platinum sheet is taken as a cathode, and a platinum sheet is taken as an anode, and electrolysis is carried out to obtain a solution B; (3) The obtained solution B is sequentially subjected to extraction, rotary evaporation and column chromatography separation to obtain a target product. The invention adopts an electrochemical synthesis method to carry out selective oxidation reaction on 4-hydroxy-3-methoxy benzyl alcohol in a heterogeneous reaction system of liquid-liquid two phases, thus obtaining vanillin. Compared with the prior art, the method has the advantages of higher product yield which is up to 43%, low solvent consumption, contribution to reducing production cost, environment friendliness, high efficiency, economy, convenient operation and 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 known as vanillin, and has a chemical name of 4-hydroxy-3-methoxybenzaldehyde and a molecular formula of C 8 H 8 O 3 . The vanillin has the fragrance of vanilla beans and rich milk fragrance, plays roles in flavoring and fixing fragrance, and is widely applied to industries of cosmetics, tobacco, cakes, candies, baked foods and the like. Can also be used as plant growth promoter, bactericide, lubricant defoamer, etc., and is also an important intermediate for synthesizing medicines and other spices. Besides, it can be used as a polishing agent in electroplating industry, a ripening agent in agriculture, a deodorant in rubber products, an anti-hardening agent in plastic products, a pharmaceutical intermediate, etc., and has a very wide application range.
The vanillin is obtained by a plurality of ways, and the main methods are as follows: plant extraction method, nitrosation method and glyoxylate method using guaiacol as raw material. These three methods have problems of low yield, poor oxidation stability, and the like, which cannot be solved. In addition, the use of transition metals such as methyl chloride, cobalt salts and the like, which are toxic and harmful, and their oxides, or the use of tetrabutylammonium chloride and the like, transfer catalysts, results in 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, the use of toxic and harmful transition metal and oxides thereof or the use of a phase transfer catalyst to generate a large amount of wastewater in the vanillin synthesis process in the prior art, and provides an environment-friendly, efficient, economical and feasible vanillin synthesis method.
The aim of the invention can be achieved 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) The solution A is taken as electrolyte, a platinum sheet is taken as a cathode, and a platinum sheet is taken as an anode, and electrolysis is carried out to obtain a solution B;
(3) The obtained solution B is sequentially subjected to extraction, rotary evaporation and column chromatography separation 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.
Further, 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).
Further, in the mixed solution of chloroform and water, the volume ratio of chloroform to water is 1:1, and the ratio of the addition amount of the 4-hydroxy-3-methoxybenzyl alcohol and the mixed solution of chloroform and water is 1.14g: (1-45) mL.
Still further, the molar ratio of 4-hydroxy-3-methoxybenzyl alcohol to TEMPO is preferably 1:0.05. the TEMPO is used in catalytic amount to facilitate the reaction treatment.
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 15-72h.
In the step (3), the extractant used in the extraction process is ethyl acetate.
Further, in the step (3), the pressure is 400-600 mmHg, the temperature is 40-60 ℃ and the spin-steaming time is 5min in the spin-steaming process. The rotary evaporation was performed to remove ethyl acetate.
In the step (3), the developing agent is a mixed solution of petroleum ether and ethyl acetate in the column chromatography separation process.
Further, in the mixed solution of petroleum ether and ethyl acetate, the volume ratio of petroleum ether to ethyl acetate is 3:1.
the invention develops a green synthesis technology of vanillin with low demand conditions and meeting the aim of green chemistry, which is a method for preparing vanillin by electrochemical oxidation by taking 4-hydroxy-3-methoxybenzyl alcohol and TEMPO as raw materials. In the electrolysis process, a direct-current power supply is used as a power supply, and two platinum sheets are respectively connected with a copper wire and a platinum wire to serve as a cathode and an anode.
Referring to fig. 1, the reaction equation for synthesizing vanillin is shown in the invention, 4-hydroxy-3-methoxybenzyl alcohol is subjected to selective oxidation reaction in a liquid-liquid two-phase heterogeneous reaction system, wherein a mixed liquid 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.
Under the electrocatalytic condition, the invention adopts TEMPO to selectively catalyze and oxidize the 4-hydroxy-3-methoxybenzyl alcohol, and the reaction is carried out in a heterogeneous reaction system of liquid-liquid two phases, so that the reaction speed is high, and the yield is up to 43%.
Under the condition of electrifying, naCl is dissolved in water and electrolyzed to generate NaClO so that the solution is provided withWith ClO – 。ClO – Then TEMPO can be further formed into ammonium oxide salt with selective oxidation and Cl is formed – Meanwhile, the ammonium oxide salt is reduced back to TEMPO after oxidizing 4-hydroxy-3-methoxybenzyl alcohol, so as to form a reaction cycle until the 4-hydroxy-3-methoxybenzyl alcohol is completely converted into 4-hydroxy-3-methoxybenzaldehyde. TEMPO can inhibit excessive oxidation of reaction products to acids.
The invention researches the literature widely when designing the process conditions, and the usage amount of TEMPO is 0.1-equivalent in the reaction of selectively oxidizing 4-hydroxy-3-methoxybenzyl alcohol into 4-hydroxy-3-methoxybenzaldehyde by using TEMPO as a catalyst, and the cost of the catalyst can be reduced by using 0.05% because TEMPO is difficult to recover in the reaction. In the synthesis process, if the quality of TEMPO is too low, the conversion rate is reduced, and the reaction time is prolonged; if the electrolyte quality is too low, the resistance of the reaction solution becomes high, the power supply voltage is required to be 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) According to the invention, 4-hydroxy-3-methoxybenzyl alcohol is used as a raw material, sodium chloride is used as an electrolyte, a mixed solution of chloroform and water is used as a solvent system, and under the action of a catalyst TEMPO and constant direct current, 4-hydroxy-3-methoxybenzyl alcohol is selectively oxidized to prepare 4-hydroxy-3-methoxybenzaldehyde, so that the product yield reaches 43%;
(2) In the synthetic method, transition metal such as methane chloride, cobalt salt and the like and oxides thereof, tetrabutylammonium chloride and the like which are toxic and harmful are not used in the process, the waste water emission is less in the production process, clean and green electric power is used, and the green synthetic target of the p-methoxybenzaldehyde is basically realized;
(3) The reaction solvent is low in use amount, so that the production cost is reduced;
(4) The invention has the advantages of simple preparation method, convenient operation, mild reaction condition, environment protection and the like, and has good industrial application prospect.
Drawings
FIG. 1 is a reaction equation for synthesizing vanillin in accordance with the invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the product prepared in example 3.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following examples, unless otherwise specified, the raw materials or processing techniques are indicated as being conventional commercially available raw material products or conventional processing techniques in the art.
Example 1:
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken 2 O、1.5mLCHCl 3 Mixing 3.9mg of TEMPO and 14.6mg of NaCl to obtain a solution A, and carrying out electrolysis by taking the obtained solution A as an electrolyte, taking a platinum sheet as a cathode and taking the 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 15h. Solution B was extracted with 20mL ethyl acetate to give an organic phase, which was detected by Thin Layer Chromatography (TLC). The obtained organic phase was separated and purified by rotary evaporation (pressure 400 mmhg, temperature 40 ℃, rotary evaporation time 5 min) and column chromatography (developing agent: petroleum ether/ethyl acetate=3:1, volume ratio) to obtain a white solid, and the vanillin yield was calculated to be 43%.
Example 2:
taking 1.14g of 4-hydroxy-3-methoxybenzyl alcohol and 2mL of H 2 O、2mL CHCl 3 Mixing 60mg TEMPO and 219mg NaCl to obtain solution A, and carrying out electrolysis by taking the obtained solution A as an electrolyte, taking a platinum sheet as a cathode and taking the platinum sheet as an anode to obtain solution B. In the electrolysis process, the current is 5mA, the temperature is 50 ℃, and the electrolysis time is 24 hours. Solution B was extracted with 80mL ethyl acetate to give an organic phase which was detected by Thin Layer Chromatography (TLC). The obtained organic phase is sequentially subjected to rotary evaporation (400 mmHg pressure, 40deg.C rotary evaporation time of 5 min) and column chromatography (developing agent: petroleum ether)Ethyl acetate=3: 1, volume ratio) to obtain white solid, the vanillin yield is calculated to be 41%.
Example 3:
11.42g of 4-hydroxy-3-methoxybenzyl alcohol and 5mL of H were taken 2 O、5mL CHCl 3 780mg TEMPO and 2.19g NaCl are mixed to obtain a solution A, and the solution A is used as an electrolyte, a platinum sheet is used as a cathode, and a platinum sheet is used as an anode for electrolysis to obtain a solution B. In the electrolysis process, the current is 5mA, the temperature is 50 ℃, and the electrolysis time is 72h. Solution B was extracted with 500mL ethyl acetate to give an organic phase, which was detected by Thin Layer Chromatography (TLC). The obtained organic phase was separated and purified by rotary evaporation (pressure 400 mmhg, temperature 40 ℃, rotary evaporation time 5 min) and column chromatography (developing agent: petroleum ether/ethyl acetate=3:1, volume ratio) to obtain a white solid, and the vanillin yield was calculated to be 38%.
The product obtained in this example was subjected to nuclear magnetic characterization, and the results are shown in fig. 2:
1H NMR (400 MHz, chloroform-d) δ9.84 (d, J=2.4 Hz, 1H), 7.45 (H, J=2.4 Hz, 2H), 7.06 (dd, J=8.6, 2.5Hz, 1H), 6.43 (t, J=2.9 Hz, 1H), 3.98 (d, J=2.3 Hz, 3H). The results showed that vanillin was successfully synthesized.
Example 4:
in comparison with example 1, the same process was carried out in a large part except that the molar ratio of 4-hydroxy-3-methoxybenzyl alcohol, TEMPO and sodium chloride was adjusted to 1:0.03:0.5.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken 2 O、1.5mLCHCl 3 Mixing 2.3mg of TEMPO and 14.6mg of NaCl to obtain a solution A, and carrying out electrolysis by taking the obtained solution A as an electrolyte, taking a platinum sheet as a cathode and taking the 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 15h. Solution B was extracted with 20mL ethyl acetate to give an organic phase, which was detected by Thin Layer Chromatography (TLC). The organic phase was subjected to rotary evaporation (pressure: 400 mmhg, temperature: 40 ℃, rotary evaporation time: 5 min) and column chromatography (developing solvent: petroleum ether/ethyl acetate=3:1, volume ratio) to obtain white solid, the vanillin yield is calculated to be 37%.
Example 5:
in comparison with example 1, the same process was carried out in a large part except that the molar ratio of 4-hydroxy-3-methoxybenzyl alcohol, TEMPO and sodium chloride was adjusted to 1:0.2:0.5.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken 2 O、1.5mLCHCl 3 Mixing 15.4mg TEMPO and 14.6mg NaCl to obtain solution A, and carrying out electrolysis by taking the obtained solution A as an electrolyte, taking a platinum sheet as a cathode and taking the platinum sheet as an anode to obtain solution B. In the electrolysis process, the current is 5mA, the temperature is 50 ℃, and the electrolysis time is 15h. Solution B was extracted with 20mL ethyl acetate to give an organic phase, which was detected by Thin Layer Chromatography (TLC). The obtained organic phase was separated and purified by rotary evaporation (pressure 400 mmhg, temperature 40 ℃, rotary evaporation time 5 min) and column chromatography (developing agent: petroleum ether/ethyl acetate=3:1, volume ratio) to obtain a white solid, and the vanillin yield was calculated to be 41%.
Example 6:
in comparison with example 1, the same process was carried out in a large part except that the molar ratio of 4-methoxybenzyl alcohol, TEMPO and sodium chloride was adjusted to 1:0.05:0.3.
example 7:
in comparison with example 1, the same process was carried out in a large part except that the molar ratio of 4-methoxybenzyl alcohol, TEMPO and sodium chloride was adjusted to 1:0.05:3.
example 8:
the temperature during electrolysis was adjusted to 25℃in this example, except that the temperature was changed to 25℃in comparison with example 1.
Example 9:
the temperature during electrolysis was adjusted to 60℃in this example, except that the temperature was changed to 60℃in comparison with example 1.
Example 10:
in comparison with example 1, the same process was carried out in the same manner as in example 1 except that the "pressure was 400 mmHg, the" temperature was 40 ℃ and the "pressure was 600 mmHg, and the" temperature was 60 ℃.
Example 11:
in comparison with example 1, the same process was carried out in the same manner as in example 1 except that the "pressure was 400 mmHg, the" temperature was 40 ℃ and the "pressure was 500 mmHg, and the" temperature was 50 ℃.
Comparative example 1:
in comparison with example 1, the vast majority 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 taken 2 O、1.5mLCHCl 3 And 14.6mg of NaCl are mixed to obtain a solution A, and electrolysis is carried out by taking the obtained solution A as an electrolyte, taking a platinum sheet as a cathode and taking the 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 15h. Solution B was extracted with 20mL ethyl acetate to give 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 mmHg, the temperature is 40 ℃, the rotary evaporation time is 5 min) and column chromatography (developing agent: petroleum ether/ethyl acetate=3:1, the volume ratio) to obtain white solid, and the yield of 4-hydroxy-3-methoxybenzaldehyde is reduced to 2% by calculation. The yield suddenly drops, indicating that the addition of TEMPO has a greater promoting effect on the reaction.
Comparative example 2:
in comparison with example 1, the reaction temperature was adjusted to 80℃in the vast majority of cases.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken 2 O、1.5mLCHCl 3 Mixing 3.9mg of TEMPO and 14.6mg of NaCl to obtain a solution A, and carrying out electrolysis by taking the obtained solution A as an electrolyte, taking a platinum sheet as a cathode and taking the 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 15h. Solution B was extracted with 20mL ethyl acetate to give an organic phase, which was detected by Thin Layer Chromatography (TLC). The obtained organic phase was subjected to rotary evaporation (400 mmHg at 40deg.C for 5 min) and column chromatography (development)And (3) opening agent: petroleum ether/ethyl acetate = 3:1, volume ratio) to obtain white solid, and the yield of the 4-hydroxy-3-methoxybenzaldehyde is reduced to 2% by calculation. The yield suddenly drops, and the yield of 4-hydroxy-3-methoxybenzaldehyde is reduced to 15 percent through calculation. High temperatures are detrimental to the reaction.
Comparative example 3:
in comparison with example 1, the reaction temperature was adjusted to 0℃in the vast majority of cases.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken 2 O、1.5mLCHCl 3 Mixing 3.9mg of TEMPO and 14.6mg of NaCl to obtain a solution A, and carrying out electrolysis by taking the obtained solution A as an electrolyte, taking a platinum sheet as a cathode and taking the 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 15h. Solution B was extracted with 20mL ethyl acetate to give 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 mmHg, the temperature is 40 ℃, the rotary evaporation time is 5 min) and column chromatography (developing agent: petroleum ether/ethyl acetate=3:1, the volume ratio) to obtain white solid, and the yield of 4-hydroxy-3-methoxybenzaldehyde is reduced to 7% by calculation. The low temperature is unfavorable for the reaction, and the reaction time can be greatly prolonged.
Comparative example 4:
the vast majority of the same was compared to example 1, 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 taken 2 O、1.5mLCHCl 3 Mixing 31.2mg TEMPO and 87.6mg NaCl to obtain solution A, and electrolyzing with the solution A as electrolyte, platinum sheet as cathode and platinum sheet as anode to obtain solution B. In the electrolysis process, the current is 5mA, the temperature is 50 ℃, and the electrolysis time is 15h. Solution B was extracted with 20mL ethyl acetate to give an organic phase, which was detected by Thin Layer Chromatography (TLC). The obtained organic phase is separated and purified by rotary evaporation (pressure is 400 mmHg, temperature is 40 ℃, rotary evaporation time is 5 min) and column chromatography (developing agent: petroleum ether/ethyl acetate=3:1, volume ratio)The white solid was obtained and the yield of 4-hydroxy-3-methoxybenzaldehyde was 45%. Increasing the TEMPO to NaCl ratio did not have a significant effect on the product yield.
Comparative example 5:
in comparison with example 1, the vast majority are identical, except that the electrolysis process is omitted.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken 2 O、1.5mLCHCl 3 3.9mg TEMPO and 14.6mg NaCl were mixed to give a solution which was stirred at 50℃for 15h. The solution obtained after completion of the reaction was extracted with 20mL of ethyl acetate to obtain an organic phase, which was detected by Thin Layer Chromatography (TLC). The obtained organic phase was separated and purified by rotary evaporation (pressure 400 mmhg, temperature 40 ℃, rotary evaporation time 5 min) and column chromatography (developing solvent: petroleum ether/ethyl acetate=3:1, volume ratio) to obtain a white solid, and the yield of 4-hydroxy-3-methoxybenzaldehyde was calculated to be 3%. Indicating that the energizing has a decisive effect on the reaction progress.
Comparative example 6:
most of the same as in example 1 except that the current 5mA was changed to 20mA.
76.1mg of 4-hydroxy-3-methoxybenzyl alcohol and 1.5mL of H were taken 2 O、1.5mLCHCl 3 Mixing 3.9mg of TEMPO and 14.6mg of NaCl to obtain a solution A, and carrying out electrolysis by taking the obtained solution A as an electrolyte, taking a platinum sheet as a cathode and taking the 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 15h. Solution B was extracted with 20mL ethyl acetate to give an organic phase, which was detected by Thin Layer Chromatography (TLC). The obtained organic phase was separated and purified by rotary evaporation (pressure 400 mmhg, temperature 40 ℃, rotary evaporation time 5 min) and column chromatography (developing solvent: petroleum ether/ethyl acetate=3:1, volume ratio) to obtain a white solid, and the yield of 4-hydroxy-3-methoxybenzaldehyde was calculated to be 29%. Indicating that the current is too high and unfavorable for the reaction.
Comparative example 7:
in comparison with example 1, the same operation was carried out for the most part, except that the electrolysis time was changed to 24h for 15h.
And taking 76.1mg of 4-hydroxy-3-methoxybenzyl alcohol, 1.5mL of H 2 O、1.5mLCHCl 3 Mixing 3.9mg of TEMPO and 14.6mg of NaCl to obtain a solution A, and carrying out electrolysis by taking the obtained solution A as an electrolyte, taking a platinum sheet as a cathode and taking the 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 hours. Solution B was extracted with 20mL ethyl acetate to give an organic phase, which was detected by Thin Layer Chromatography (TLC). The obtained organic phase was separated and purified by rotary evaporation (pressure 400 mmhg, temperature 40 ℃ C., rotary evaporation time 5 min) and column chromatography (developing solvent: petroleum ether/ethyl acetate=3:1, volume ratio) to obtain a white solid, and the yield of 4-hydroxy-3-methoxybenzaldehyde was calculated to be 40%.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments 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-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (5)
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) The solution A is taken as electrolyte, a platinum sheet is taken as a cathode, and a platinum sheet is taken as an anode, and electrolysis is carried out to obtain a solution B;
(3) The obtained solution B is sequentially subjected to extraction, rotary evaporation and column chromatography separation to obtain a target product;
in the step (1), the electrolyte is sodium chloride, and the solvent is a mixed solution of chloroform and water;
the molar ratio of the 4-hydroxy-3-methoxybenzyl alcohol to the TEMPO to the sodium chloride is 1: (0.03 to 0.2): (0.3-3);
in the mixed solution of chloroform and water, the volume ratio of chloroform to water is 1:1, and the ratio of the addition amount of the 4-hydroxy-3-methoxybenzyl alcohol and the mixed solution of chloroform and water is 1.14g: (1-45) mL;
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;
in the step (2), in the electrolysis process, the current is 5mA, the temperature is 25-60 ℃, and the electrolysis time is 15-72h.
2. The electrochemical synthesis method of vanillin according to claim 1, wherein in step (3), the extractant used in the extraction process is ethyl acetate.
3. The electrochemical synthesis method of vanillin according to claim 1, wherein in the step (3), the pressure is 400-600 mmhg, the temperature is 40-60 ℃, and the spin-steaming time is 5min.
4. The electrochemical synthesis method of vanillin according to claim 1, wherein in the step (3), the developing agent used in the column chromatography separation process is a mixture of petroleum ether and ethyl acetate.
5. The electrochemical synthesis method of vanillin according to claim 4, wherein in the mixed solution of petroleum ether and ethyl acetate, the volume ratio of petroleum ether to ethyl acetate is 3:1.
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| Title |
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| TEMPO-Mediated Electrooxidation of Primary and Secondary Alcohols in a Microfluidic Electrolytic Cell;Joseph T. Hill-Cousins et. al.;《ChemSusChem》;第第5卷卷;第326-331页 * |
| 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.》.1991,第第56卷卷第2416-2421页. * |
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