CN114934285A - Method for electrocatalysis of olefin epoxidation by covalent connection of manganoporphyrin electrode - Google Patents

Method for electrocatalysis of olefin epoxidation by covalent connection of manganoporphyrin electrode Download PDF

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CN114934285A
CN114934285A CN202210769478.5A CN202210769478A CN114934285A CN 114934285 A CN114934285 A CN 114934285A CN 202210769478 A CN202210769478 A CN 202210769478A CN 114934285 A CN114934285 A CN 114934285A
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郭凯
张皓宇
何伟
方正
张文艳
李晓伟
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Nanjing Tech University
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Abstract

The invention discloses a method for electrocatalysis olefin epoxidation by covalently connecting manganese porphyrin electrodes, which comprises the steps of reacting a mixed homogeneous solution containing an olefin compound shown as a formula I, water, an electrolyte, tetrabutyl ammonium hydroxide and an organic solvent in an electrolytic cell provided with an electrode to obtain a reaction solution containing an epoxide shown as a formula II; the anode plate of the electrolytic cell is a carbon cloth electrode covalently fixed by manganese porphyrin. The method provided by the invention is simple in experimental operation, high in safety, more economical, more environment-friendly, green and practical, and high in product selectivity. The method can effectively overcome the defects of the traditional synthesis path, such as long reaction time, high reaction temperature, inconvenience for environmental protection, high pressure requirement and the like, solves the problems of complicated steps, long reaction time, requirement of expensive catalyst, 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

Method for electrocatalysis of olefin epoxidation by covalent connection of manganoporphyrin electrode
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for high-selectivity electrocatalysis of olefin epoxidation by covalently connecting manganese porphyrin electrodes.
Background
Epoxy compounds are versatile intermediates for many chemical products, such as surfactants, epoxy resins, and pharmaceuticals, among others. These epoxy compounds are generally prepared by the oxidation of olefins. Most olefin epoxidation reactions employ peroxide-based oxidants such as t-butyl hydroperoxide (TBHP) or chloroperoxybenzoic acid (mCPBA). Both of these routes involve by-products that are not easily separable. 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 efficiently synthesized. However, there are a lot of side reactions during the electrochemical reaction, such as dimerization of raw materials, etc., which decrease the selectivity of the reaction. Therefore, if an electrocatalyst with high selectivity and capability of electrocatalysis olefin epoxidation can be reasonably designed, the electrocatalyst has great value in aspects of drug development and the like. The selectivity research on the catalyst can also be extended to other products of olefin on the basis of the selectivity research, so that the practicability of the catalyst is improved. At present, the electrocatalytic epoxidation is reported, but the used catalyst is often an organic catalyst dissolved in the system, so that the organic catalyst is difficult to separate and easy to decompose, and the like, so that the problem can be improved by fixing the catalyst on an electrode.
The electrochemical method has the advantages of high reaction efficiency, mild temperature condition and the like, and the heterogeneous catalyst is 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 electrochemical reaction is combined with the microreactor, and the mass transfer of the reaction can be improved by carrying out the electrochemical reaction in the microreactor, so that the high-efficiency catalytic reaction is generated. 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 the exhaustion of resources, the development of green chemistry has become one of the missions of scientists. Therefore, the invention provides a method for high-selectivity electrocatalysis of olefin epoxidation by covalently connecting manganese porphyrin electrodes.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art and provides a method for high-selectivity electrocatalysis of olefin epoxidation by covalently connecting manganese porphyrin electrodes.
In order to solve the technical problems, the invention discloses a method for high-selectivity electrocatalysis of olefin epoxidation by covalently connecting manganese porphyrin electrodes, wherein the reaction path is shown in figure 2, and a mixed homogeneous solution containing an olefin compound shown in formula I, water, an electrolyte, tetrabutylammonium hydroxide and an organic solvent is subjected to an electrolyte reaction in an electrolytic cell provided with electrodes to obtain a reaction solution containing an epoxide shown in formula II; the anode plate of the electrolytic cell is a carbon cloth electrode covalently fixed by manganese porphyrin;
Figure BDA0003723393040000021
wherein R is 1 Selected from benzene, 4-methylbenzene, 4-ethylbenzene, 4-chlorobenzene, 4-methoxybenzene, 4-nitrobenzene or naphthalene ring; preferably benzene, 4-methylbenzene, 4-chlorobenzene, 4-methoxybenzene or naphthalene rings; further preferred is benzene, 4-methylbenzene, 4-chlorobenzene or 4-methoxybenzene.
The electrolyte is one or a combination of more of tetrabutylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate and tetrabutylammonium perchlorate, and tetrabutylammonium hexafluorophosphate is preferably used.
Wherein, the organic solvent is any one or combination of more of acetonitrile, methanol, N-dimethylformamide and propylene carbonate, and is preferably propylene carbonate.
Wherein, in the mixed homogeneous solution, the concentration of the olefin compound shown in the formula I is 5-15mM, preferably 7-13mM, and more preferably 10 mM.
Wherein the concentration of the electrolyte in the mixed homogeneous solution is 0.05-0.15M, preferably 0.07-0.13M, and more preferably 0.1M.
Wherein, in the mixed homogeneous solution, the mass fraction of the tetrabutylammonium hydroxide in the tetrabutylammonium hydroxide aqueous solution composed of 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 tetrabutyl ammonium hydroxide aqueous solution to the organic solvent is 1: 14-24, preferably 1: 16-22, and more preferably 1: 19.
The electrolytic cell with the electrodes comprises an unsealed electrolytic cell, a cathode sheet, an anode sheet and a direct current power supply; the volume of the unsealed electrolytic cell is preferably 25 mL; the distance between the cathode plate and the anode in the electrolytic cell is about 1 cm; 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, and preferably a platinum sheet electrode.
Wherein the reaction temperature is 20-30 ℃, and room temperature is preferred.
The current intensity of the reaction is 1 to 5mA, preferably 2 to 4mA, and more preferably 3 mA.
Wherein the residence time of the reaction is 6 to 12 hours, preferably 7 to 11 hours, and more preferably 8 hours.
After the reaction is finished, collecting liquid in an electrolytic cell, diluting reaction liquid containing the epoxide shown in the formula II by ethyl acetate for five times, washing, drying, filtering, and leaching 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 the ethyl acetate and the petroleum ether is 1: 10-30.
Has the beneficial effects 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, more environment-friendly, green and more practical. The method can effectively overcome the defects of the traditional synthesis path, such as long reaction time, high reaction temperature, low atom efficiency, high cost, unfavorable environmental protection and the like, solves the problems of complicated steps, long reaction time, excessive strong oxidant, high reaction temperature, low atom 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 further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a diagram of the preparation of a catalytic electrode according to the present invention.
FIG. 2 is a diagram of the reaction pathway 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 are commercially available, unless otherwise specified.
The electrochemical reaction apparatus described in the following examples includes a direct current power supply, a 25mL electrolytic cell, a cathode sheet, and an anode sheet; wherein, the electrolytic cell is respectively provided with a cathode sheet (platinum sheet) and an anode sheet (carbon cloth electrode of manganese porphyrin catalyst which is fixed by covalence); the distance between the cathode plate and the anode in the electrolytic cell is about 1 cm.
The anode sheet is manufactured by a special method: manganese porphyrin is connected to the surface of the electrode by adopting a two-step method (see figure 1), specifically: (1) the tetraphenylporphyrin core is covalently linked to the carbon cloth via a phenylene linker, the hydrogen at the para-position of one of the benzenes of the tetraphenylporphyrin is replaced with a diazo group, which is then covalently linked to the carbon cloth electrode; (2) the porphyrin modified electrode was immersed in 30mL of 0.05M Mn (OAc)2 solution of DMF: CH3COOH (9:1) for 45 minutes, then washed with water and dried to obtain a manganoporphyrin modified electrode (see prior art ACS Sustainable chem. Eng.2019,7, 3838-3848).
The following procedure was followed in the examples below: (1) adding the mixed homogeneous solution prepared in proportion into an electrolytic cell; (2) adjusting the required current; (4) collecting the effluent reaction liquid, and calculating the product yield by a column-passing weighing method; and measuring the product yield through a high performance liquid chromatography, and separating through column chromatography to obtain the target product.
In the following examples, the reaction temperature is room temperature unless otherwise specified.
The olefinic compounds of the present invention are shown in Table 1.
TABLE 1
Figure BDA0003723393040000041
The epoxides shown in Table 2 are all the products synthesized by the method of the present invention.
TABLE 2
Figure BDA0003723393040000042
Example 1 synthesis of compound 2 a:
(1) dissolving 0.1mmol of a compound 1a styrene, 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40 wt% tetrabutylammonium hydroxide aqueous solution in a propylene carbonate (9.5mL) solvent to obtain a homogeneous solution, and adding the homogeneous solution into an electrolytic bath; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 1 mA; the reaction time is 8 h; after the reaction was completed, the reaction liquid was collected, and the product yield was 79% by HPLC. After the reaction liquid is diluted five times by ethyl acetate, the reaction liquid is washed by water, dried and filtered, and then is separated under the leaching of a mixed solvent of ethyl acetate/petroleum ether (1: 30) to obtain a product 2 a.
(2) Dissolving 0.1mmol (0.02403g) of the compound 1a styrene, 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40% wt aqueous tetrabutylammonium hydroxide solution in propylene carbonate (9.5mL) solvent to obtain a homogeneous solution, and adding the homogeneous solution to an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3 mA; the reaction time is 8 h; after the reaction was completed, the reaction liquid was collected, and the product yield was 92% by HPLC. After the reaction liquid is diluted five times by ethyl acetate, the reaction liquid is washed by water, dried and filtered, and then is separated under the leaching of a mixed solvent of ethyl acetate/petroleum ether (1: 30) to obtain a product 2 a.
(3) Dissolving 0.1mmol of the compound 1a styrene, 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40 wt% tetrabutylammonium hydroxide aqueous solution in a propylene carbonate (9.5mL) solvent to obtain a homogeneous solution, and adding the homogeneous solution to an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 5 mA; the reaction time is 8 h; after the reaction was completed, the reaction liquid was collected, and the product yield was 86% by HPLC. Diluting the reaction liquid by ethyl acetate five times, washing, drying and filtering, and then leaching and separating by a mixed solvent of ethyl acetate/petroleum ether (1: 30) to obtain a product 2 a.
(4) Dissolving 0.1mmol of compound 1a styrene, and 1mmol of tetrabutylammonium hexatetrafluoroborate and 0.5mL of 40% wt tetrabutylammonium hydroxide aqueous solution in propylene carbonate (9.5mL) solvent to obtain a homogeneous solution, and adding the homogeneous solution to an electrolytic bath; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3 mA; the reaction time is 8 h; after the reaction was completed, the reaction liquid was collected, and the product yield was 71% by HPLC. After the reaction liquid is diluted five times by ethyl acetate, the reaction liquid is washed by water, dried and filtered, and then is separated under the leaching of a mixed solvent of ethyl acetate/petroleum ether (1: 30) to obtain a product 2 a.
(5) Dissolving 0.1mmol of compound 1a styrene, 1mmol of tetrabutylammonium perchlorate and 0.5mL of 40% wt tetrabutylammonium hydroxide aqueous solution in propylene carbonate (9.5mL) solvent to obtain a homogeneous solution, and adding the homogeneous solution into an electrolytic bath; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3 mA; the reaction time is 8 h; after the reaction was completed, the reaction liquid was collected, and the product yield was 73% by HPLC. After the reaction liquid is diluted five times by ethyl acetate, the reaction liquid is washed by water, dried and filtered, and then is separated under the leaching of a mixed solvent of ethyl acetate/petroleum ether (1: 30) to obtain a product 2 a.
(6) Dissolving 0.1mmol of the compound 1a styrene, 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40 wt% tetrabutylammonium hydroxide aqueous solution in N, N-dimethylformamide (9.5mL) to obtain a homogeneous solution, and adding the homogeneous solution to an electrolytic bath; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3 mA; the reaction time is 8 h; after the reaction was completed, the reaction liquid was collected, and the product yield was 69% by HPLC. After the reaction liquid is diluted five times by ethyl acetate, the reaction liquid is washed by water, dried and filtered, and then is separated under the leaching of a mixed solvent of ethyl acetate/petroleum ether (1: 30) to obtain a product 2 a.
Example 2 synthesis of compound 2 b:
dissolving 0.1mmol of the compound 1b 4-chlorostyrene, 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40% wt tetrabutylammonium hydroxide aqueous solution in a propylene carbonate (9.5mL) solvent to obtain a homogeneous solution, and adding the homogeneous solution to an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3 mA; the reaction time is 8 h; after the reaction was completed, the reaction liquid was collected, and the product yield was 81% by HPLC. Diluting the reaction liquid by ethyl acetate five times, washing, drying and filtering, and then leaching and separating by a mixed solvent of ethyl acetate/petroleum ether (1: 30) to obtain a product 2 b.
Example 3 synthesis of compound 2 c:
dissolving 0.1mmol of a compound 1c 4-methylstyrene, 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of a 40% wt aqueous tetrabutylammonium hydroxide solution in a propylene carbonate (9.5mL) solvent to obtain a homogeneous solution, and adding the homogeneous solution into an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3 mA; the reaction time is 8 h; after the reaction was completed, the reaction liquid was collected, and the product yield was 89% by HPLC. After the reaction liquid is diluted five times by ethyl acetate, the reaction liquid is washed by water, dried and filtered, and then is separated under the leaching of a mixed solvent of ethyl acetate/petroleum ether (1: 30) to obtain a product 2 c.
Example 4 synthesis of compound 2 d:
dissolving 0.1mmol of a compound 1d 4-methoxystyrene, 1mmol of tetrabutylammonium hexafluorophosphate and 0.5mL of 40 wt% tetrabutylammonium hydroxide aqueous solution in a propylene carbonate (9.5mL) solvent to obtain a homogeneous solution, and adding the homogeneous solution into an electrolytic cell; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3 mA; the reaction time is 8 h; after the reaction was completed, the reaction liquid was collected, and the product yield was 94% by HPLC. After the reaction liquid is diluted five times by ethyl acetate, the reaction liquid is washed by water, dried and filtered, and then is separated under the leaching of a mixed solvent of ethyl acetate/petroleum ether (1: 30) to obtain a product 2 d.
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 not supporting a catalyst), respectively.
In comparative examples 1 to 3 below, the catalyst used was homogeneous catalyst Fe III -bTAML, dispersed in the system.
Comparative example 1: non-covalent fixed electric catalyst for catalyzing styrene oxidation to styrene oxide 2a
15mM styrene, 0.75mM Fe III -bTAML, 0.1M tetrabutylammonium hexafluorophosphate dissolved in mixed solution of acetonitrile and phosphate buffer (v/v 4: 1, pH 8) and placed in an electrolytic cell; the distance between the two electrodes is set to be 1cm, and the reaction is carried out for 10 hours under the current of 3 mA; after the completion of the reaction, the reaction liquid was collected, and the yield was 66% by HPLC.
Comparative example 2: non-covalent fixed electrocatalyst for catalyzing oxidation of 4-chloro-phenylethene to 4-chloro-phenylethene 2b
15mM 4-chlorostyrene, 0.75mM Fe III -bTAML, 0.1M tetrabutylammonium hexafluorophosphate dissolved in a mixed solution of acetonitrile and phosphate buffer (v/v 4: 1, pH 8) and placed in an electrolytic cell; setting the distance between the two electrodes to be 1cm, and reacting for 10 hours under the current of 3 mA; after completion of the reaction, the reaction liquid was collected, and the yield was 57% by HPLC.
Comparative example 3: non-covalent fixed electrocatalyst catalysis 4-methoxy styrene oxidation to 4-methoxy styrene oxide 2d
15mM 4-methoxystyrene, 0.75mM Fe III -bTAML, 0.1M tetrabutylammonium hexafluorophosphate dissolved in mixed solution of acetonitrile and phosphate buffer (v/v 4: 1, pH 8) and placed in an electrolytic cell; setting the distance between the two electrodes to be 1cm, and reacting for 10 hours under the current of 3 mA; after the reaction, the reaction liquid was collectedThe yield was 51% by HPLC.
Comparative example 4: the difference from example 1(2) is that only the anode sheet of the electrolytic cell was replaced with a carbon cloth electrode not supporting a catalyst, and a manganoporphyrin catalyst was directly added to the reaction system.
Dissolving 0.1mmol (0.02403g) of a compound 1a styrene, 1mmol tetrabutylammonium hexafluorophosphate and 0.5mL of 40 wt% tetrabutylammonium hydroxide aqueous solution in a propylene carbonate (9.5mL) solvent, and simultaneously adding 0.0075mmol of a catalyst manganese tetraphenylporphyrin to obtain a homogeneous solution, and adding the homogeneous solution to an electrolytic bath; before the reaction, the distance between the two electrodes is adjusted to 1cm, and the applied current is 3 mA; the reaction time is 8 h; after the reaction was completed, the reaction liquid was collected, and the product yield was 21% by HPLC. After the reaction liquid is diluted five times by ethyl acetate, the reaction liquid is washed by water, dried and filtered, and then is separated under the leaching of a mixed solvent of ethyl acetate/petroleum ether (1: 30) to obtain a product 2 a.
The present invention provides a method and a concept for electrocatalytic olefin epoxidation by covalent bonding of manganoporphyrin electrodes, and a method and a way for realizing the technical scheme are numerous, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of modifications and embellishments can be made without departing from the principle of the present invention, and the modifications and embellishments should be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.

Claims (10)

1. A method for electrocatalytic olefin epoxidation by covalently connecting manganese porphyrin electrodes is characterized in that a mixed homogeneous solution containing an olefin compound shown as a formula I, water, an electrolyte, tetrabutylammonium hydroxide and an organic solvent is reacted in an electrolytic bath provided with electrodes to obtain a reaction solution containing an epoxide shown as a formula II; the anode plate of the electrolytic cell is a carbon cloth electrode covalently fixed by manganese porphyrin;
Figure FDA0003723393030000011
wherein R is 1 Selected from benzene, 4-methylbenzene, 4-ethylbenzene, 4-chlorobenzene, 4-methoxybenzene, 4-nitrobenzene or naphthalene rings.
2. The method according to claim 1, wherein the electrolyte is any one or a combination of tetrabutylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate and tetrabutylammonium perchlorate.
3. The method according to claim 1, wherein the organic solvent is any one or a combination of acetonitrile, methanol, N-dimethylformamide and propylene carbonate.
4. The method of claim 1, wherein the concentration of the olefinic compound of formula I in the mixed homogeneous solution is 5-15 mM.
5. The method of claim 1, wherein the mixed homogeneous solution has an electrolyte concentration of 0.05 to 0.15M.
6. The method according to claim 1, wherein the mixed homogeneous solution contains tetrabutylammonium hydroxide in a mass fraction of 10-50% wt.
7. The method of claim 1, wherein the mixed homogeneous solution has a ratio of water to organic solvent of 0.001-0.010 mol/mL.
8. The method of claim 1, wherein the reaction temperature is 20-30 ℃; the current intensity of the reaction is 1-5 mA.
9. The process according to claim 1, wherein the residence time of the reaction is between 6 and 12 hours.
10. 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 by water, dried, filtered, and then leached and separated by a mixed solvent of ethyl acetate and petroleum ether, so that the epoxide shown in the formula II is obtained.
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CN108541277A (en) * 2016-01-21 2018-09-14 西门子股份公司 The electrolysis system and method for ethylene oxide are prepared for electrochemistry
CN113106473A (en) * 2021-04-14 2021-07-13 南京工业大学 Method for preparing 1, 3-benzoxazine derivative through continuous electrochemical microreactor device

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Publication number Priority date Publication date Assignee Title
CN108541277A (en) * 2016-01-21 2018-09-14 西门子股份公司 The electrolysis system and method for ethylene oxide are prepared for electrochemistry
CN108033932A (en) * 2017-12-15 2018-05-15 万华化学集团股份有限公司 A kind of preparation method of Styryl oxide
CN113106473A (en) * 2021-04-14 2021-07-13 南京工业大学 Method for preparing 1, 3-benzoxazine derivative through continuous electrochemical microreactor device

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FETHI BEDIOUI: "POLY(PYRROLE MANGANESE PORPHYRIN) FILM ELECTRODE AS A CATALYST IN ELECTRO-ASSISTED OXfDATION REACTIONS USING MOLECULAR OXYGEN: COMPARISON WITH DESCRIBED HOMOGENEOUS SYSTEMS" *

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