CN114934285B - Method for electrocatalytic olefin epoxidation through covalent connection of manganese porphyrin electrode - Google Patents
Method for electrocatalytic olefin epoxidation through covalent connection of manganese porphyrin electrode Download PDFInfo
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Abstract
The invention discloses a method for electrocatalytic olefin epoxidation by covalent connection of manganese porphyrin electrodes, which comprises the steps of reacting a mixed homogeneous solution containing olefin compounds shown in a formula I, water, electrolyte, tetrabutylammonium hydroxide and an organic solvent in an electrolytic tank provided with electrodes to obtain a reaction solution containing epoxide shown in a formula II; the anode sheet of the electrolytic cell is a carbon cloth electrode covalently immobilized by manganese porphyrin. The method provided by the invention has the advantages of simple experimental operation, high safety, more economy, environmental protection, practicability and high selectivity of the product. The method can effectively overcome the defects of the traditional synthetic route, such as long reaction time, high reaction temperature, environmental protection inconvenience, high pressure requirement and the like, solve the problems of complicated steps, long reaction time, expensive catalyst requirement, excessive strong oxidant, high reaction temperature, low atomic efficiency and the like in the traditional reaction process, can improve the reaction efficiency, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for high-selectivity electrocatalytic olefin epoxidation through covalent connection of manganese porphyrin electrodes.
Background
Epoxy compounds are versatile intermediates for many chemical products, such as surfactants, epoxy resins, and pharmaceuticals. These epoxy compounds are generally prepared by the oxidation of olefins. Most olefin epoxidation reactions employ peroxide-based oxidizing agents such as t-butyl hydroperoxide (TBHP) or chloroperoxybenzoic acid (mCPBA). Both of these approaches involve by-products that are not easily separated. In order to solve the above problems, some processes use a catalyst to generate hydrogen peroxide in situ as an oxidizing agent, so that an epoxy compound can be synthesized with high efficiency. However, there are a large number of side reactions during the electrochemical reaction, such as dimerization of raw materials, etc., which reduce the selectivity of the reaction. Therefore, if an electrocatalyst with high-selectivity electrocatalytic olefin epoxy capability can be reasonably designed, the electrocatalyst has great value in aspects of medicine research and development and the like. The selectivity research of the catalyst can be extended to other products of olefin on the basis, so that the practicability of the catalyst is improved. At present, there are reports on electrocatalytic epoxidation, but the catalyst used often uses an organic catalyst dissolved in the system, so that the catalyst has the defects of difficult separation, easy decomposition and the like, and the catalyst can be fixed on an electrode to improve the problems.
The electrochemical method has the advantages of high reaction efficiency, mild temperature condition and the like, and the heterogeneous catalyst is used for being loaded on the electrode in the reaction, so that the product can be conveniently separated from the catalyst, and the catalytic efficiency of the electrochemical reaction can be improved. The electrochemistry is combined with the microreactor, and the mass transfer of the reaction can be improved by performing the electrochemistry reaction in the microreactor, so that the efficient catalytic reaction occurs. The photocatalysis can utilize sunlight which is cheap and abundant energy, and can greatly shorten the steps of traditional chemical synthesis. With the development of society and exhaustion of resources, the development of green chemistry has become one of the scientists' lives. To this end, the present invention provides a method for the highly selective electrocatalytic epoxidation of olefins by covalent attachment of manganese porphyrin electrodes.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing a method for high-selectivity electrocatalytic olefin epoxidation by covalent connection of manganese porphyrin electrodes.
In order to solve the technical problems, the invention discloses a method for high-selectivity electrocatalytic olefin epoxidation by covalent connection of manganese porphyrin electrodes, wherein the reaction path is shown in figure 2, and a mixed homogeneous solution containing olefin compounds shown in a formula I, water, electrolyte, tetrabutylammonium hydroxide and an organic solvent is subjected to electrolyte reaction in an electrolytic tank provided with the electrodes to obtain a reaction solution containing epoxide shown in a formula II; the anode sheet of the electrolytic cell is a carbon cloth electrode covalently immobilized by manganese porphyrin;
wherein R is 1 Selected from benzene, 4-methylbenzene, 4-ethylbenzene, 4-chlorobenzene, 4-methoxybenzene, 4-nitrobenzene or naphthalene rings; preferably benzene, 4-methylbenzene, 4-chlorobenzene, 4-methoxybenzene or naphthalene ring; further preferred is benzene, 4-methylbenzene, 4-chlorobenzene or 4-methoxybenzene.
Wherein the electrolyte is any one or a combination of a plurality of tetrabutylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate and tetrabutylammonium perchlorate, and is preferably tetrabutylammonium hexafluorophosphate.
Wherein the organic solvent is any one or a combination of acetonitrile, methanol, N-dimethylformamide and propylene carbonate, and propylene carbonate is preferred.
Wherein, in the mixed homogeneous phase solution, the concentration of the olefin compound shown in the formula I is 5-15mM, preferably 7-13mM, and more preferably 10mM.
Wherein, in the mixed homogeneous solution, the concentration of the electrolyte is 0.05-0.15M, preferably 0.07-0.13M, and more preferably 0.1M.
Wherein in the mixed homogeneous phase solution, the mass fraction of tetrabutylammonium hydroxide in the tetrabutylammonium hydroxide aqueous solution formed by tetrabutylammonium hydroxide and water is 10-50% wt, preferably 20-45% wt, more preferably 35-45% wt, and even more preferably 40% wt.
In the mixed homogeneous phase solution, the volume ratio of the tetrabutylammonium hydroxide aqueous solution to the organic solvent is 1:14-24, preferably 1:16-22, and more preferably 1:19.
Wherein the electrolytic cell provided with the electrode comprises a non-sealing electrolytic cell, a cathode plate, an anode plate and a direct current power supply; the volume of the unsealed electrolytic cell is preferably 25mL; the distance between the cathode plate and the anode in the electrolytic tank is about 1cm; the anode sheet is a carbon cloth electrode covalently fixed by a manganese porphyrin catalyst; the cathode sheet is a graphite carbon electrode or a platinum sheet electrode, preferably a platinum sheet electrode.
Wherein the temperature of the reaction is 20-30 ℃, preferably room temperature.
Wherein the current intensity of the reaction is 1-5mA, preferably 2-4mA, and more preferably 3mA.
Wherein the residence time of the reaction is from 6 to 12 hours, preferably from 7 to 11 hours, more preferably 8 hours.
And after the reaction is finished, collecting liquid in an electrolytic tank, diluting the reaction liquid containing the epoxide shown in the formula II by five times by using ethyl acetate, washing with water, drying, filtering, and eluting and separating by using a mixed solvent of ethyl acetate and petroleum ether to obtain the epoxide shown in the formula II.
Wherein, the volume ratio of the mixed solvent of ethyl acetate and petroleum ether is 1:10-30.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
the method provided by the invention is simple to operate, high in safety, more economical, environment-friendly, green and practical. The method can effectively overcome the defects of the traditional synthetic route, such as long reaction time, high reaction temperature, low atomic efficiency, high cost, unfavorable environmental protection and the like, solve the problems of complicated steps, long reaction time, excessive strong oxidant, high reaction temperature, low atomic efficiency and the like in the traditional reaction process, can improve the reaction efficiency, and is suitable for industrial production.
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The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is a schematic representation of the preparation of a catalytic electrode according to the present invention.
FIG. 2 is a reaction scheme of the present invention.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
The electrochemical reaction device described in the following examples comprises a direct current power supply, a 25mL electrolytic cell, a cathode sheet and an anode sheet; wherein the electrolytic tank is respectively provided with a cathode plate (platinum plate) and an anode plate (carbon cloth electrode of a covalently fixed manganese porphyrin catalyst); the distance between the cathode plate and the anode in the electrolytic tank is about 1cm.
The manufacturing method of the anode plate adopts a special method: the two-step method is used for connecting manganese porphyrin to the surface of an electrode (see fig. 1), specifically: (1) The tetraphenylporphyrin core is covalently linked with the carbon cloth through a phenylene linking agent, hydrogen at the para position of one of the benzenes of the tetraphenylporphyrin is replaced by a diazo group, and then the diazo group is covalently linked with the carbon cloth electrode; (2) The porphyrin-modified electrode was placed in 30mL of a 0.05M solution of Mn (OAc) 2 in DMF: CH3COOH (9:1) for 45 minutes, then washed with water and dried to obtain a manganese porphyrin-modified electrode (see ACS Sustainable chem. Eng.2019,7,3838-3848, preparation method of the electrode).
The following procedure is followed in the examples below: (1) Adding the mixed homogeneous solution prepared in proportion into an electrolytic tank; (2) regulating the desired current; (4) Collecting effluent reaction liquid, and calculating the product yield by a column passing weighing method; and measuring the product yield through a high performance liquid phase, and separating through column chromatography to obtain a target product.
In the following examples, the temperature of the reaction was room temperature unless otherwise specified.
The olefin compounds in the present invention are shown in Table 1.
TABLE 1
Among them, the epoxides shown in Table 2 are all synthesized by the method of the present invention.
TABLE 2
Example 1 synthesis of compound 2 a:
(1) 0.1mmol of compound 1a styrene, 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40% wt aqueous tetrabutylammonium hydroxide solution were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, which was added to an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 1mA; the reaction time is 8 hours; after the reaction was completed, the reaction liquid was collected, and the product yield was 79% by HPLC method. The reaction liquid is diluted five times by ethyl acetate, washed by water, dried and filtered, and then is eluted by a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain a product 2a.
(2) 0.1mmol (0.02403 g) of compound 1a styrene, 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40% wt aqueous tetrabutylammonium hydroxide were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, which was added to an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3mA; the reaction time is 8 hours; after the reaction was completed, the reaction liquid was collected, and the product yield was 92% by HPLC method. The reaction liquid is diluted five times by ethyl acetate, washed by water, dried and filtered, and then is eluted by a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain a product 2a.
(3) 0.1mmol of compound 1a styrene, and 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40% wt aqueous tetrabutylammonium hydroxide were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, which was added to an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 5mA; the reaction time is 8 hours; after the completion of the reaction, the reaction liquid was collected, and the product yield was 86% by HPLC. The reaction liquid is diluted five times by ethyl acetate, washed by water, dried and filtered, and then is eluted by a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain a product 2a.
(4) 0.1mmol of compound 1a styrene, and 1mmol of tetrabutylammonium hexafluoroborate and 0.5mL of 40% by weight aqueous tetrabutylammonium hydroxide solution were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, which was added to an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3mA; the reaction time is 8 hours; after the completion of the reaction, the reaction liquid was collected, and the product yield was 71% by HPLC. The reaction liquid is diluted five times by ethyl acetate, washed by water, dried and filtered, and then is eluted by a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain a product 2a.
(5) 0.1mmol of compound 1a styrene, and 1mmol of tetrabutylammonium perchlorate and 0.5mL of 40% wt aqueous tetrabutylammonium hydroxide solution were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, which was added to an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3mA; the reaction time is 8 hours; after the reaction was completed, the reaction liquid was collected, and the product yield was 73% by HPLC method. The reaction liquid is diluted five times by ethyl acetate, washed by water, dried and filtered, and then is eluted by a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain a product 2a.
(6) 0.1mmol of compound 1a styrene, and 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40% wt aqueous tetrabutylammonium hydroxide were dissolved in N, N-dimethylformamide (9.5 mL) solvent to obtain a homogeneous solution, which was added to an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3mA; the reaction time is 8 hours; after the reaction was completed, the reaction liquid was collected, and the product yield was 69% by HPLC method. The reaction liquid is diluted five times by ethyl acetate, washed by water, dried and filtered, and then is eluted by a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain a product 2a.
Example 2 synthesis of compound 2 b:
0.1mmol of Compound 1b 4-chlorostyrene, and 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40% by weight aqueous tetrabutylammonium hydroxide solution were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, which was added to an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3mA; the reaction time is 8 hours; after the completion of the reaction, the reaction liquid was collected, and the product yield was 81% by HPLC. The reaction liquid is diluted five times by ethyl acetate, washed by water, dried and filtered, and then is eluted by a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain a product 2b.
Example 3 synthesis of compound 2 c:
0.1mmol of 1c 4-methylstyrene, 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40% by weight aqueous tetrabutylammonium hydroxide solution were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, which was added to the electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3mA; the reaction time is 8 hours; after the reaction, the reaction liquid was collected, and the product yield was 89% by HPLC. The reaction liquid is diluted five times by ethyl acetate, washed by water, dried and filtered, and then is eluted by a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain a product 2c.
Example 4 synthesis of compound 2 d:
0.1mmol of 1d 4-methoxystyrene, 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40% wt aqueous tetrabutylammonium hydroxide were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, which was added to an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3mA; the reaction time is 8 hours; after the reaction was completed, the reaction liquid was collected, and the product yield was 94% by HPLC method. The reaction liquid is diluted five times by ethyl acetate, washed by water, dried and filtered, and then is eluted by a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain a product 2d.
In comparative examples 1 to 4 below, the electrolytic cell was provided with a cathode sheet (platinum sheet) and an anode sheet (carbon cloth electrode without catalyst supported), respectively.
In comparative examples 1 to 3 below, the catalyst used was a homogeneous catalyst Fe III -bTAML, dispersed in the system.
Comparative example 1: non-covalent immobilized electrocatalyst for catalyzing oxidation of styrene to styrene oxide 2a
15mM styrene, 0.75mM Fe III -bTAML, 0.1M tetrabutylammonium hexafluorophosphate in a mixed solution of acetonitrile and phosphate buffer (v/v 4:1, ph=8) and placed in an electrolyzer; the distance between the two electrodes is set to be 1cm, and the current is 3mAReacting for 10 hours; after the completion of the reaction, the reaction liquid was collected, and the yield was 66% by HPLC.
Comparative example 2: non-covalent immobilized electrocatalyst for catalyzing oxidation of 4-chlorostyrene to 4-styrene oxychloride 2b
15mM 4-chlorostyrene, 0.75mM Fe III -bTAML, 0.1M tetrabutylammonium hexafluorophosphate in a mixed solution of acetonitrile and phosphate buffer (v/v 4:1, ph=8) and placed in an electrolyzer; the distance between the two electrodes is set to be 1cm, and the reaction is carried out for 10 hours under 3mA current; after the completion of the reaction, the reaction liquid was collected, and the yield was 57% by HPLC.
Comparative example 3: non-covalent immobilized electrocatalyst for catalyzing oxidation of 4-methoxystyrene to 4-methoxystyrene 2d
15mM 4-methoxystyrene, 0.75mM Fe III -bTAML, 0.1M tetrabutylammonium hexafluorophosphate in a mixed solution of acetonitrile and phosphate buffer (v/v 4:1, ph=8) and placed in an electrolyzer; the distance between the two electrodes is set to be 1cm, and the reaction is carried out for 10 hours under 3mA current; after the completion of the reaction, the reaction liquid was collected, and the yield was calculated to be 51% by HPLC.
Comparative example 4: the same as in example 1 (2) except that only the anode sheet of the electrolytic cell was replaced with a carbon cloth electrode without a catalyst, and that a manganese porphyrin catalyst was directly added to the reaction system.
0.1mmol (0.02403 g) of compound 1a styrene, 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40% wt aqueous tetrabutylammonium hydroxide were dissolved in propylene carbonate (9.5 mL) solvent, and simultaneously 0.0075mmol of catalyst tetraphenylporphyrin manganese was added to obtain a homogeneous solution, which was added to an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3mA; the reaction time is 8 hours; after the reaction was completed, the reaction liquid was collected, and the product yield was 21% by HPLC method. The reaction liquid is diluted five times by ethyl acetate, washed by water, dried and filtered, and then is eluted by a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain a product 2a.
The invention provides a method for electrocatalytic olefin epoxidation by covalent connection of manganese porphyrin electrodes, and a plurality of methods and approaches for realizing the technical scheme, the above description is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by those skilled in the art without departing from the principle of the invention, and the improvements and modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (7)
1. A method for electrocatalytic olefin epoxidation by covalent connection of manganese porphyrin electrode is characterized in that a mixed homogeneous solution containing olefin compounds shown in a formula I, water, electrolyte, tetrabutylammonium hydroxide and organic solvent is reacted in an electrolytic tank provided with an electrode to obtain a reaction solution containing epoxide shown in a formula II;
the anode sheet of the electrolytic cell is a carbon cloth electrode covalently immobilized by manganese porphyrin, and the specific preparation method comprises the following steps: (1) The tetraphenylporphyrin core is covalently linked with the carbon cloth through a phenylene linking agent, hydrogen at the para position of one of the benzenes of the tetraphenylporphyrin is replaced by a diazo group, and then the diazo group is covalently linked with the carbon cloth electrode; (2) Porphyrin modified electrode was placed in 30mL,0.05M Mn (OAc) 2 Soaking in a solution of CH3COOH 9:1 for 45 minutes, then washing with water and drying;
wherein R is 1 Selected from benzene, 4-methylbenzene, 4-ethylbenzene, 4-chlorobenzene, 4-methoxybenzene, 4-nitrobenzene or naphthalene rings;
the electrolyte is any one or a combination of a plurality of tetrabutylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate and tetrabutylammonium perchlorate;
the organic solvent is any one or a combination of a plurality of acetonitrile, methanol, N-dimethylformamide and propylene carbonate;
in the mixed homogeneous phase solution, the concentration of the olefin compound shown in the formula I is 5-15mM;
in the mixed homogeneous phase solution, the concentration of electrolyte is 0.05-0.15M;
in the mixed homogeneous phase solution, the mass fraction of tetrabutylammonium hydroxide is 10-50%wt;
in the mixed homogeneous phase solution, the dosage ratio of water to organic solvent is 0.001-0.010mol/mL;
the temperature of the reaction is 20-30 ℃; the amperage of the reaction was 1-5mA.
2. The method of claim 1, wherein R 1 Selected from benzene, 4-methylbenzene, 4-chlorobenzene, 4-methoxybenzene or naphthalene rings.
3. The method of claim 1, wherein R 1 Selected from benzene, 4-methylbenzene, 4-chlorobenzene or 4-methoxybenzene.
4. The method of claim 1, wherein the electrolyte is tetrabutylammonium hexafluorophosphate.
5. The method of claim 1, wherein the organic solvent is propylene carbonate.
6. The process according to claim 1, wherein the residence time of the reaction is from 6 to 12 hours.
7. The method according to claim 1, wherein after the reaction is finished, the reaction solution containing the epoxide shown in the formula II is diluted by ethyl acetate, washed with water, dried, filtered, and then eluted and separated by a mixed solvent of ethyl acetate and petroleum ether, thereby obtaining the epoxide shown in the formula II.
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