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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Abstract

本发明公开了一种通过共价连接锰卟啉电极电催化烯烃环氧化的方法,将含式I所示的烯烃类化合物、水、电解质、四丁基氢氧化铵和有机溶剂的混合均相溶液于设有电极的电解槽中反应,得到含有式II所示的环氧化物的反应液;所述电解池的阳极片为锰卟啉共价固定的碳布电极。本发明所提供的方法实验操作简单,安全性高,更加经济环保、绿色实用、产物的选择性高。可以有效克服传统合成路径的缺点,如反应时间长、反应温度高、不利于环保、需要高压等,解决该传统反应过程中步骤繁杂、反应时间长,需要昂贵催化剂,过量的强氧化剂,高反应温度和低原子效率等问题,并能够提高反应效率,适于工业化生产。

Figure 202210769478

The invention discloses a method for electrocatalyzing olefin epoxidation by covalently connecting manganese porphyrin electrodes. The reaction is carried out in an electrolytic cell provided with electrodes to obtain a reaction solution containing the epoxide represented by formula II; the anode sheet of the electrolytic cell is a carbon cloth electrode covalently fixed with manganese porphyrin. The method provided by the invention is simple in experimental operation, high in safety, more economical, environmentally friendly, green and practical, and has high product selectivity. It can effectively overcome the shortcomings of traditional synthesis routes, such as long reaction time, high reaction temperature, unfavorable environmental protection, high pressure, etc., and solves the traditional reaction process with complicated steps, long reaction time, expensive catalysts, excess strong oxidant, high reaction problems such as temperature and low atomic efficiency, and can improve the reaction efficiency, suitable for industrial production.

Figure 202210769478

Description

一种通过共价连接锰卟啉电极电催化烯烃环氧化的方法A method for electrocatalytic epoxidation of olefins by covalently linking manganese porphyrin electrodes

技术领域technical field

本发明属于有机化学合成领域,具体涉及一种通过共价连接锰卟啉电极高选择性电催化烯烃环氧化的方法。The invention belongs to the field of organic chemical synthesis, in particular to a method for highly selective electrocatalytic olefin epoxidation by covalently connecting manganese porphyrin electrodes.

背景技术Background technique

环氧化合物是许多化学产品的通用中间体,例如表面活性剂,环氧树脂,和药物等。这些环氧化合物通常是由烯烃氧化制得的。大多数烯烃环氧化反应采用过氧化物为基础的氧化剂,如叔丁基过氧化氢(TBHP)或氯过氧苯甲酸(mCPBA)。这两种途径都涉及到不易分离的副产物。为了解决上述问题,一些工艺使用催化剂原位生成过氧化氢作为氧化剂,从而可以高效合成环氧化合物。但是电化学反应过程中存在大量副反应,例如原料二聚等降低了反应的选择性。因此,如果可以合理设计出一种具有高选择性电催化烯烃环氧能力的电催化剂,则在药物研发等方面具有重大价值。对于催化剂的选择性研究也可在此基础上延伸至烯烃的其他产物上,从而提高催化剂的实用性。目前,已有电催化环氧化的相关报道,但是所用催化剂往往使用溶于体系的有机催化剂,因此存在难分离、易分解等缺点,因此,将催化剂固定于电极上可以改善这一点。Epoxy compounds are common intermediates for many chemical products, such as surfactants, epoxy resins, and pharmaceuticals. These epoxy compounds are usually prepared by oxidation of olefins. Most olefin epoxidation reactions employ peroxide-based oxidants such as tert-butyl hydroperoxide (TBHP) or chloroperoxybenzoic acid (mCPBA). Both pathways involve by-products that are not easily separable. In order to solve the above problems, some processes use catalysts to generate hydrogen peroxide in situ as an oxidant, so that epoxy compounds can be synthesized efficiently. However, there are a large number of side reactions in the electrochemical reaction process, such as dimerization of raw materials, which reduces the selectivity of the reaction. Therefore, if an electrocatalyst with the ability to electrocatalyze olefin epoxidation with high selectivity can be rationally designed, it will be of great value in drug R&D and so on. The study of catalyst selectivity can also be extended to other products of olefins on this basis, thereby improving the practicability of catalysts. At present, there are related reports on electrocatalytic epoxidation, but the catalysts used often use organic catalysts soluble in the system, so there are disadvantages such as difficult separation and easy decomposition. Therefore, fixing the catalyst on the electrode can improve this point.

电化学方法具有反应效率高、温度条件温和等优点,在反应中使用非均相催化剂负载于电极上不仅可方便的将产物与催化剂分离,同时可提高电化学反应的催化效率。将电化学与微反应器结合,在微反应器中进行电化学反应可以提高反应的传质,从而高效的催化反应发生。光催化可利用太阳光这一廉价丰富的能源,可以大大缩短传统化学合成的步骤。随着社会的发展和资源的枯竭,绿色化学的发展已经成为科学家的使命之一。为此,本发明提供了一种通过共价连接锰卟啉电极高选择性电催化烯烃环氧化的方法。Electrochemical methods have the advantages of high reaction efficiency and mild temperature conditions. The use of heterogeneous catalysts supported on electrodes in the reaction not only facilitates the separation of products and catalysts, but also improves the catalytic efficiency of electrochemical reactions. Combining electrochemistry with a microreactor, the electrochemical reaction in the microreactor can improve the mass transfer of the reaction, so that the efficient catalytic reaction occurs. Photocatalysis can utilize sunlight, a cheap and abundant energy source, which 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. To this end, the present invention provides a method for highly selective electrocatalytic epoxidation of olefins by covalently linking manganese porphyrin electrodes.

发明内容SUMMARY OF THE INVENTION

发明目的:本发明所要解决的技术问题是针对现有技术的不足,提供一种通过共价连接锰卟啉电极高选择性电催化烯烃环氧化的方法。Purpose of the invention: The technical problem to be solved by the present invention is to provide a method for highly selective electrocatalytic olefin epoxidation by covalently connecting manganese porphyrin electrodes.

为了解决上述技术问题,本发明公开了一种通过共价连接锰卟啉电极高选择性电催化烯烃环氧化的方法,反应路径如图2所示,将含式I所示的烯烃类化合物、水、电解质、四丁基氢氧化铵和有机溶剂的混合均相溶液于设有电极的电解槽中进行电解质反应,得到含有式II所示的环氧化物的反应液;所述电解池的阳极片为锰卟啉共价固定的碳布电极;In order to solve the above technical problems, the present invention discloses a method for highly selective electrocatalytic olefin epoxidation by covalently connecting manganese porphyrin electrodes. , water, an electrolyte, a mixed homogeneous solution of tetrabutylammonium hydroxide and an organic solvent to carry out an electrolyte reaction in an electrolytic cell provided with an electrode to obtain a reaction solution containing an epoxide shown in formula II; the anode sheet of the electrolytic cell It is a carbon cloth electrode covalently fixed by manganese porphyrin;

Figure BDA0003723393040000021
Figure BDA0003723393040000021

其中,R1选自苯、4-甲基苯、4-乙基苯、4-氯苯、4-甲氧基苯、4-硝基苯或萘环;优选为苯、4-甲基苯、4-氯苯、4-甲氧基苯或萘环;进一步优选为苯、4-甲基苯、4-氯苯或4-甲氧基苯。Wherein, R 1 is 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 ring; more preferably benzene, 4-methylbenzene, 4-chlorobenzene or 4-methoxybenzene.

其中,所述电解质为四丁基六氟磷酸铵、四丁基四氟硼酸铵和四丁基高氯酸铵中的任意一种或几种组合,优选为四丁基六氟磷酸铵。Wherein, the electrolyte is any one or a combination of tetrabutylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate and tetrabutylammonium perchlorate, preferably tetrabutylammonium hexafluorophosphate.

其中,所述有机溶剂为乙腈、甲醇、N,N-二甲基甲酰胺和碳酸丙烯酯中任意一种或几种组合,优选为碳酸丙烯酯。Wherein, the organic solvent is any one or a combination of acetonitrile, methanol, N,N-dimethylformamide and propylene carbonate, preferably propylene carbonate.

其中,所述混合均相溶液中,式I所示的烯烃类化合物的浓度为5-15mM,优选为7-13mM,进一步优选为10mM。Wherein, in the mixed homogeneous solution, the concentration of the olefin compound represented by formula I is 5-15 mM, preferably 7-13 mM, more preferably 10 mM.

其中,所述混合均相溶液中,电解质的浓度为0.05-0.15M,优选为0.07-0.13M,进一步优选为0.1M。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.

其中,所述混合均相溶液中,四丁基氢氧化铵与水组成的四丁基氢氧化铵水溶液中,四丁基氢氧化铵的质量分数为10-50%wt,优选为20-45%wt,进一步优选为35-45%wt,更进一步优选为40%wt。Wherein, in the mixed homogeneous solution, in the tetrabutylammonium hydroxide aqueous solution composed of tetrabutylammonium hydroxide and water, the mass fraction of tetrabutylammonium hydroxide is 10-50%wt, preferably 20-45%wt, more preferably 35-45% wt, more preferably 40% wt.

其中,所述混合均相溶液中,四丁基氢氧化铵水溶液与有机溶剂的体积比为1:14~24,优选为1:16~22,进一步优选为1:19。Wherein, in the mixed homogeneous 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.

其中,所述设有电极的电解槽包括非密封电解槽、阴极片、阳极片和直流电源;所述非密封电解槽的体积优选为25mL;所述电解槽中阴极片和阳极间距约1cm;所述阳极片为锰卟啉催化剂共价固定的碳布电极;所述阴极片为石墨碳电极或铂片电极,优选为铂片电极。Wherein, the electrolytic cell provided with electrodes includes an unsealed electrolytic cell, a cathode sheet, an anode sheet and a DC power supply; the volume of the unsealed electrolytic cell is preferably 25 mL; the distance between the cathode sheet and the anode in the electrolytic cell is about 1 cm; The anode sheet is a carbon cloth electrode covalently fixed with a manganese porphyrin catalyst; the cathode sheet is a graphite carbon electrode or a platinum sheet electrode, preferably a platinum sheet electrode.

其中,所述反应的温度为20-30℃,优选为室温。Wherein, the temperature of the reaction is 20-30°C, preferably room temperature.

其中,所述反应的电流强度为1-5mA,优选为2-4mA,进一步优选为3mA。Wherein, the current intensity of the reaction is 1-5 mA, preferably 2-4 mA, more preferably 3 mA.

其中,所述反应的停留时间为6-12h,优选为7-11h,进一步优选为8h。Wherein, the residence time of the reaction is 6-12h, preferably 7-11h, more preferably 8h.

其中,所述反应结束后,收集电解槽内液体,将含有式II所示的环氧化物的反应液经乙酸乙酯稀释五倍后,经水洗、干燥、过滤后,用乙酸乙酯和石油醚的混合溶剂淋洗分离,即得式II所示的环氧化物。Wherein, after the reaction is finished, the liquid in the electrolytic cell is collected, the reaction solution containing the epoxide shown in formula II is diluted five times with ethyl acetate, washed with water, dried and filtered, and then washed with ethyl acetate and petroleum The mixed solvent of ether is rinsed and separated to obtain the epoxide represented by formula II.

其中,所述乙酸乙酯和石油醚的混合溶剂的体积比为1:10-30。Wherein, the volume ratio of the mixed solvent of ethyl acetate and petroleum ether is 1:10-30.

有益效果:与现有技术相比,本发明具有如下优势:Beneficial effect: Compared with the prior art, the present invention has the following advantages:

本发明所提供的方法操作简单,安全性高,更加经济环保、绿色实用。可以有效克服传统合成路径的缺点,如反应时间长、反应温度高、原子效率低、成本高昂、不利环保等,解决该传统反应过程中步骤繁杂、反应时间长,过量的强氧化剂,高反应温度和低原子效率等问题,并能够提高反应效率,适于工业化生产。The method provided by the invention is simple to operate, high in safety, more economical, environmentally friendly, green and practical. It can effectively overcome the shortcomings of the traditional synthesis route, such as long reaction time, high reaction temperature, low atomic efficiency, high cost, unfavorable environmental protection, etc., and solves the traditional reaction process with complicated steps, long reaction time, excess strong oxidant, high reaction temperature, etc. And low atomic efficiency and other problems, and can improve the reaction efficiency, suitable for industrial production.

附图说明Description of drawings

下面结合附图和具体实施方式对本发明做更进一步的具体说明,本发明的上述和/或其他方面的优点将会变得更加清楚。The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, and the advantages of the above-mentioned and/or other aspects of the present invention will become clearer.

图1是本发明催化电极制备图。Fig. 1 is the preparation diagram of the catalytic electrode of the present invention.

图2是本发明的反应路径图。Fig. 2 is a reaction route diagram of the present invention.

具体实施方式Detailed ways

下述实施例中所述实验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials can be obtained from commercial sources unless otherwise specified.

以下实施例所述的电化学反应装置,包括直流电源、25mL电解槽、阴极片和阳极片;其中,所述电解槽分别设有阴极片(铂片)和阳极片(共价固定的锰卟啉催化剂的碳布电极);所述电解槽中阴极片和阳极间距约1cm。The electrochemical reaction device described in the following examples includes a DC 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 (covalently fixed manganese porphyrin). The carbon cloth electrode of the phosphonium catalyst); the distance between the cathode sheet and the anode in the electrolytic cell is about 1 cm.

其中,阳极片的制作采用特殊方法:采用两步法将锰卟啉连接到电极表面(参见图1),具体为:(1)四苯基卟啉核通过亚苯基连接剂与碳布共价连接,在四苯基卟啉的其中一个苯的对位上的氢用重氮基取代,之后该重氮基与碳布电极共价链接;(2)将卟啉修饰电极放置于30mL,0.05M Mn(OAc)2的DMF:CH3COOH(9:1)溶液中浸泡45分钟,然后用水冲洗并干燥以获得锰卟啉修饰电极(该电极的制备方法参见现有技术ACS SustainableChem.Eng.2019,7,3838-3848)。Among them, the production of the anode sheet adopts a special method: a two-step method is used to connect the manganese porphyrin to the electrode surface (see Figure 1), specifically: (1) The tetraphenyl porphyrin core is co-coated with the carbon cloth through a phenylene linker. The hydrogen on 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 to the carbon cloth electrode; (2) The porphyrin modified electrode is placed in 30 mL, 0.05M Mn(OAc)2 was soaked in DMF:CH3COOH (9:1) solution for 45 minutes, then rinsed with water and dried to obtain a manganese porphyrin modified electrode (for the preparation method of this electrode, please refer to the prior art ACS SustainableChem.Eng.2019 , 7, 3838-3848).

以下实施例中按照下述步骤:(1)将按比例配置好的混合均相溶液添加到电解槽中中;(2)调节所需电流;(4)收集流出反应液,以过柱称重方法计算产物收率;通过高效液相测得产物收率,再经柱层析分离得到目标产物。According to the following steps in the following examples: (1) adding the mixed homogeneous solution prepared in proportion to the electrolytic cell; (2) adjusting the required current; (4) collecting the outflow reaction solution and weighing it by passing through the column The product yield was calculated by the method; the product yield was measured by high performance liquid phase, and then the target product was obtained by column chromatography.

以下实施例中,若无特殊说明,所述反应的温度为室温。In the following examples, unless otherwise specified, the reaction temperature is room temperature.

其中,本发明中烯烃类化合物如表1所示。Among them, the olefin compounds in the present invention are shown in Table 1.

表1Table 1

Figure BDA0003723393040000041
Figure BDA0003723393040000041

其中,如表2所示的环氧化物,均为通过本发明方法合成得到的产物。Among them, the epoxides shown in Table 2 are all products synthesized by the method of the present invention.

表2Table 2

Figure BDA0003723393040000042
Figure BDA0003723393040000042

实施例1化合物2a的合成:Synthesis of Example 1 Compound 2a:

(1)将0.1mmol化合物1a苯乙烯、1mmol四丁基六氟磷酸铵和0.5mL 40%wt的四丁基氢氧化铵水溶液溶于碳酸丙烯酯(9.5mL)溶剂中,得到均相溶液,添加到电解槽中;反应前将两电极间距调至1cm,施加电流为1mA;反应时间8h;在反应结束后,收集反应液体,以HPLC的方法计算产物收率为79%。反应液体用乙酸乙酯稀释五倍后,经水洗、干燥、过滤后,用乙酸乙酯/石油醚(1:30)的混合溶剂淋洗下分离得到产物2a。(1) 0.1 mmol of compound 1a styrene, 1 mmol of tetrabutylammonium hexafluorophosphate and 0.5 mL of 40% wt tetrabutylammonium hydroxide aqueous solution were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, which was added to Before the reaction, the distance between the two electrodes was adjusted to 1cm, and the applied current was 1mA; the reaction time was 8h; after the reaction, the reaction liquid was collected, and the product yield was 79% calculated by HPLC. The reaction liquid was diluted five times with ethyl acetate, washed with water, dried, filtered, and rinsed with a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain product 2a.

(2)将0.1mmol(0.02403g)化合物1a苯乙烯、1mmol四丁基六氟磷酸铵和0.5mL40%wt的四丁基氢氧化铵水溶液溶于碳酸丙烯酯(9.5mL)溶剂中,得到均相溶液,添加到电解槽中;反应前将两电极间距调至1cm,施加电流为3mA;反应时间8h;在反应结束后,收集反应液体,以HPLC的方法计算产物收率为92%。反应液体用乙酸乙酯稀释五倍后,经水洗、干燥、过滤后,用乙酸乙酯/石油醚(1:30)的混合溶剂淋洗下分离得到产物2a。(2) 0.1 mmol (0.02403 g) of compound 1a styrene, 1 mmol of tetrabutylammonium hexafluorophosphate and 0.5 mL of a 40% wt tetrabutylammonium hydroxide aqueous solution were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution , added to the electrolytic cell; before the reaction, the distance between the two electrodes was adjusted to 1 cm, and the applied current was 3 mA; the reaction time was 8 h; after the reaction, the reaction liquid was collected, and the product yield was 92% calculated by HPLC. The reaction liquid was diluted five times with ethyl acetate, washed with water, dried, filtered, and rinsed with a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain product 2a.

(3)将0.1mmol化合物1a苯乙烯,和1mmol四丁基六氟磷酸铵和0.5mL 40%wt的四丁基氢氧化铵水溶液溶于碳酸丙烯酯(9.5mL)溶剂中,得到均相溶液,添加到电解槽中;反应前将两电极间距调至1cm,施加电流为5mA;反应时间8h;反应结束后,收集反应液体,以HPLC的方法计算产物收率为86%。反应液体用乙酸乙酯稀释五倍后,经水洗、干燥、过滤后,用乙酸乙酯/石油醚(1:30)的混合溶剂淋洗下分离得到产物2a。(3) Dissolve 0.1 mmol of compound 1a styrene, 1 mmol of tetrabutylammonium hexafluorophosphate and 0.5 mL of 40%wt tetrabutylammonium hydroxide aqueous solution in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, add Before the reaction, the distance between the two electrodes was adjusted to 1cm, and the applied current was 5mA; the reaction time was 8h; after the reaction, the reaction liquid was collected, and the product yield was 86% calculated by HPLC. The reaction liquid was diluted five times with ethyl acetate, washed with water, dried, filtered, and rinsed with a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain product 2a.

(4)将0.1mmol化合物1a苯乙烯,和1mmol四丁基六四氟硼酸铵和0.5mL 40%wt的四丁基氢氧化铵水溶液溶于碳酸丙烯酯(9.5mL)溶剂中,得到均相溶液,添加到电解槽中;反应前将两电极间距调至1cm,施加电流为3mA;反应时间8h;反应结束后,收集反应液体,以HPLC的方法计算产物收率为71%。反应液体用乙酸乙酯稀释五倍后,经水洗、干燥、过滤后,用乙酸乙酯/石油醚(1:30)的混合溶剂淋洗下分离得到产物2a。(4) 0.1 mmol of compound 1a styrene, 1 mmol of tetrabutylammonium hexatetrafluoroborate and 0.5 mL of 40%wt tetrabutylammonium hydroxide aqueous solution were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, Before the reaction, the distance between the two electrodes was adjusted to 1 cm, and the applied current was 3 mA; the reaction time was 8 h; after the reaction, the reaction liquid was collected, and the product yield was 71% calculated by HPLC. The reaction liquid was diluted five times with ethyl acetate, washed with water, dried, filtered, and rinsed with a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain product 2a.

(5)将0.1mmol化合物1a苯乙烯,和1mmol四丁基高氯酸铵和0.5mL 40%wt的四丁基氢氧化铵水溶液溶于碳酸丙烯酯(9.5mL)溶剂中,得到均相溶液,添加到电解槽中;反应前将两电极间距调至1cm,施加电流为3mA;反应时间8h;反应结束后,收集反应液体,以HPLC的方法计算产物收率为73%。反应液体用乙酸乙酯稀释五倍后,经水洗、干燥、过滤后,用乙酸乙酯/石油醚(1:30)的混合溶剂淋洗下分离得到产物2a。(5) Dissolve 0.1 mmol of compound 1a styrene, 1 mmol of tetrabutylammonium perchlorate and 0.5 mL of 40%wt tetrabutylammonium hydroxide aqueous solution in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, add Before the reaction, the distance between the two electrodes was adjusted to 1 cm, and the applied current was 3 mA; the reaction time was 8 h; after the reaction, the reaction liquid was collected, and the product yield was 73% calculated by HPLC. The reaction liquid was diluted five times with ethyl acetate, washed with water, dried, filtered, and rinsed with a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain product 2a.

(6)将0.1mmol化合物1a苯乙烯,和1mmol四丁基六氟磷酸铵和0.5mL 40%wt的四丁基氢氧化铵水溶液溶于N,N-二甲基甲酰胺(9.5mL)溶剂中,得到均相溶液,添加到电解槽中;反应前将两电极间距调至1cm,施加电流为3mA;反应时间8h;反应结束后,收集反应液体,以HPLC的方法计算产物收率为69%。反应液体用乙酸乙酯稀释五倍后,经水洗、干燥、过滤后,用乙酸乙酯/石油醚(1:30)的混合溶剂淋洗下分离得到产物2a。(6) 0.1 mmol of compound 1a styrene, 1 mmol of tetrabutylammonium hexafluorophosphate and 0.5 mL of a 40% wt tetrabutylammonium hydroxide aqueous solution were dissolved in N,N-dimethylformamide (9.5 mL) solvent, A homogeneous solution was obtained and added to the electrolytic cell; before the reaction, the distance between the two electrodes was adjusted to 1 cm, and the applied current was 3 mA; the reaction time was 8 h; after the reaction, the reaction liquid was collected, and the product yield was 69% calculated by HPLC. The reaction liquid was diluted five times with ethyl acetate, washed with water, dried, filtered, and rinsed with a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain product 2a.

实施例2化合物2b的合成:Synthesis of Example 2 Compound 2b:

将0.1mmol化合物1b 4-氯苯乙烯,和1mmol四丁基六氟磷酸铵和0.5mL 40%wt的四丁基氢氧化铵水溶液溶于碳酸丙烯酯(9.5mL)溶剂中,得到均相溶液,添加到电解槽中;反应前将两电极间距调至1cm,施加电流为3mA;反应时间8h;反应结束后,收集反应液体,以HPLC的方法计算产物收率为81%。反应液体用乙酸乙酯稀释五倍后,经水洗、干燥、过滤后,用乙酸乙酯/石油醚(1:30)的混合溶剂淋洗下分离得到产物2b。0.1 mmol of compound 1b 4-chlorostyrene, 1 mmol of tetrabutylammonium hexafluorophosphate and 0.5 mL of 40% wt aqueous solution of tetrabutylammonium hydroxide were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, which was added Before the reaction, the distance between the two electrodes was adjusted to 1 cm, and the applied current was 3 mA; the reaction time was 8 h; after the reaction, the reaction liquid was collected, and the product yield was 81% calculated by HPLC. The reaction liquid was diluted five times with ethyl acetate, washed with water, dried, filtered, and rinsed with a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain product 2b.

实施例3化合物2c的合成:Synthesis of Example 3 Compound 2c:

将0.1mmol化合物1c 4-甲基苯乙烯,1mmol四丁基六氟磷酸铵和0.5mL 40%wt的四丁基氢氧化铵水溶液溶于碳酸丙烯酯(9.5mL)溶剂中,得到均相溶液,添加到电解槽中;反应前将两电极间距调至1cm,施加电流为3mA;反应时间8h;反应结束后,收集反应液体,以HPLC的方法计算产物收率为89%。反应液体用乙酸乙酯稀释五倍后,经水洗、干燥、过滤后,用乙酸乙酯/石油醚(1:30)的混合溶剂淋洗下分离得到产物2c。0.1 mmol of compound 1c 4-methylstyrene, 1 mmol of tetrabutylammonium hexafluorophosphate and 0.5 mL of 40% wt aqueous solution of tetrabutylammonium hydroxide were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, added Before the reaction, the distance between the two electrodes was adjusted to 1 cm, and the applied current was 3 mA; the reaction time was 8 h; after the reaction, the reaction liquid was collected, and the product yield was 89% calculated by HPLC. The reaction liquid was diluted five times with ethyl acetate, washed with water, dried, filtered, and rinsed with a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain product 2c.

实施例4化合物2d的合成:Synthesis of Example 4 Compound 2d:

将0.1mmol化合物1d 4-甲氧基苯乙烯,1mmol四丁基六氟磷酸铵和0.5mL 40%wt的四丁基氢氧化铵水溶液溶于碳酸丙烯酯(9.5mL)溶剂中,得到均相溶液,添加到电解槽中;反应前将两电极间距调至1cm,施加电流为3mA;反应时间8h;反应结束后,收集反应液体,以HPLC的方法计算产物收率为94%。反应液体用乙酸乙酯稀释五倍后,经水洗、干燥、过滤后,用乙酸乙酯/石油醚(1:30)的混合溶剂淋洗下分离得到产物2d。0.1 mmol of compound 1d 4-methoxystyrene, 1 mmol of tetrabutylammonium hexafluorophosphate and 0.5 mL of 40% wt aqueous solution of tetrabutylammonium hydroxide were dissolved in propylene carbonate (9.5 mL) solvent to obtain a homogeneous solution, Before the reaction, the distance between the two electrodes was adjusted to 1cm, and the applied current was 3mA; the reaction time was 8h; after the reaction, the reaction liquid was collected, and the product yield was 94% calculated by HPLC. The reaction liquid was diluted five times with ethyl acetate, washed with water, dried, filtered, and rinsed with a mixed solvent of ethyl acetate/petroleum ether (1:30) to isolate the product 2d.

以下对比例1~对比例4中,所述电解槽分别设有阴极片(铂片)和阳极片(未负载催化剂的碳布电极)。In the following Comparative Examples 1 to 4, the electrolytic cells are respectively provided with a cathode sheet (platinum sheet) and an anode sheet (carbon cloth electrode without catalyst).

以下对比例1~对比例3中,所采用的催化剂为均相催化剂FeIII-bTAML,将其分散于体系中。In the following comparative examples 1 to 3, the catalyst used is a homogeneous catalyst Fe III -bTAML, which is dispersed in the system.

对比例1:非共价固定电催化剂催化苯乙烯氧化为氧化苯乙烯2aComparative Example 1: Non-covalently immobilized electrocatalyst catalyzed the oxidation of styrene to styrene oxide 2a

将15mM苯乙烯、0.75mM FeIII-bTAML、0.1M四丁基六氟磷酸铵溶于乙腈和磷酸缓冲液(v/v 4:1,pH=8)的混合溶液中,并置于电解槽中;两电极间距设置为1cm,在3mA电流下反应10h;反应结束后,收集反应液体,以HPLC的方法计算收率为66%。15 mM styrene, 0.75 mM Fe III -bTAML, 0.1 M tetrabutylammonium hexafluorophosphate were dissolved in a 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 was set to 1 cm, and the reaction was carried out at a current of 3 mA for 10 h; after the reaction was completed, the reaction liquid was collected, and the yield calculated by HPLC was 66%.

对比例2:非共价固定电催化剂催化4-氯苯乙烯氧化为4-氯氧化苯乙烯2bComparative Example 2: Non-covalently immobilized electrocatalyst catalyzed the oxidation of 4-chlorostyrene to 4-chlorostyrene oxy2b

将15mM 4-氯苯乙烯、0.75mM FeIII-bTAML、0.1M四丁基六氟磷酸铵溶于乙腈和磷酸缓冲液(v/v 4:1,pH=8)的混合溶液中,并置于电解槽中;两电极间距设置为1cm,在3mA电流下反应10h;反应结束后,收集反应液体,以HPLC的方法计算收率为57%。15 mM 4-chlorostyrene, 0.75 mM Fe III -bTAML, 0.1 M tetrabutylammonium hexafluorophosphate were dissolved in a mixed solution of acetonitrile and phosphate buffer (v/v 4:1, pH=8), juxtaposed In an electrolytic cell; the distance between the two electrodes was set to 1 cm, and the reaction was carried out under a current of 3 mA for 10 h; after the reaction was completed, the reaction liquid was collected, and the yield calculated by HPLC was 57%.

对比例3:非共价固定电催化剂催化4-甲氧基苯乙烯氧化为4-甲氧基氧化苯乙烯2dComparative Example 3: Non-covalently immobilized electrocatalyst catalyzed the oxidation of 4-methoxystyrene to 4-methoxystyrene oxide 2d

将15mM 4-甲氧基苯乙烯、0.75mM FeIII-bTAML、0.1M四丁基六氟磷酸铵溶于乙腈和磷酸缓冲液(v/v 4:1,pH=8)的混合溶液中,并置于电解槽中;两电极间距设置为1cm,在3mA电流下反应10h;反应结束后,收集反应液体,以HPLC的方法计算收率为51%。15mM 4-methoxystyrene, 0.75mM FeIII- bTAML , 0.1M tetrabutylammonium hexafluorophosphate were dissolved in a 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 was set to 1 cm, and the reaction was carried out under a current of 3 mA for 10 h; after the reaction was completed, the reaction liquid was collected, and the yield calculated by HPLC was 51%.

对比例4:同实施例1(2),区别在于仅将电解槽的阳极片用未负载催化剂的碳布电极替代,并将锰卟啉催化剂直接添加到反应体系中。Comparative Example 4: Same as Example 1 (2), the difference is that only the anode sheet of the electrolytic cell is replaced with a carbon cloth electrode without catalyst supported, and the manganese porphyrin catalyst is directly added to the reaction system.

将0.1mmol(0.02403g)化合物1a苯乙烯、1mmol四丁基六氟磷酸铵和0.5mL 40%wt的四丁基氢氧化铵水溶液溶于碳酸丙烯酯(9.5mL)溶剂中,同时加入0.0075mmol催化剂四苯基卟啉锰,得到均相溶液,添加到电解槽中;反应前将两电极间距调至1cm,施加电流为3mA;反应时间8h;在反应结束后,收集反应液体,以HPLC的方法计算产物收率为21%。反应液体用乙酸乙酯稀释五倍后,经水洗、干燥、过滤后,用乙酸乙酯/石油醚(1:30)的混合溶剂淋洗下分离得到产物2a。0.1 mmol (0.02403 g) of compound 1a styrene, 1 mmol of tetrabutylammonium hexafluorophosphate and 0.5 mL of a 40% wt aqueous solution of tetrabutylammonium hydroxide were dissolved in propylene carbonate (9.5 mL) solvent, and 0.0075 mmol of catalyst tetra Phenyl porphyrin manganese to obtain a homogeneous solution, which was added to the electrolytic cell; before the reaction, the distance between the two electrodes was adjusted to 1 cm, and the applied current was 3 mA; the reaction time was 8 h; after the reaction, the reaction liquid was collected and calculated by HPLC The product yield was 21%. The reaction liquid was diluted five times with ethyl acetate, washed with water, dried, filtered, and rinsed with a mixed solvent of ethyl acetate/petroleum ether (1:30) to obtain product 2a.

本发明提供了一种通过共价连接锰卟啉电极电催化烯烃环氧化的方法的思路及方法,具体实现该技术方案的方法和途径很多,以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。The present invention provides an idea and method for a method for electrocatalyzing olefin epoxidation by covalently connecting manganese porphyrin electrodes. There are many specific methods and approaches for realizing this technical solution. The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can also be made, and these improvements and modifications should also be regarded as the protection scope of the present invention. All components not specified in this embodiment can be implemented by existing technologies.

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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