CN114635145A - Electrochemical preparation method of imide derivative - Google Patents

Electrochemical preparation method of imide derivative Download PDF

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CN114635145A
CN114635145A CN202210385917.2A CN202210385917A CN114635145A CN 114635145 A CN114635145 A CN 114635145A CN 202210385917 A CN202210385917 A CN 202210385917A CN 114635145 A CN114635145 A CN 114635145A
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imide derivative
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黄精美
付志美
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South China University of Technology SCUT
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Abstract

The application discloses an electrochemical preparation method of an imide derivative, which comprises the step of carrying out electrochemical reaction on a compound Ar-COOH, a nitrile compound and dialkyl peroxide in the presence of an electrolyte to obtain the imide derivative
Figure DDA0003594979870000011
The method takes aryl formic acid or heteroaryl formic acid as a substrate to react with dialkyl peroxide and nitrile compounds under electrochemical conditions to synthesize the imide derivative in one step; the reaction does not need to add an additional metal catalyst, is environment-friendly, has mild conditions, easily obtained raw materials and simple and easy reaction; the preparation reaction widens the preparation method of the imide derivative, provides simpler and more convenient synthesis steps, and can be widely applied to the preparation of organic luminescent materials and agricultural productsMedicine and medicament.

Description

Electrochemical preparation method of imide derivative
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to an electrochemical preparation method of an imide derivative.
Background
Imides are important structural frameworks, widely present in natural products and drug molecules, and have important biological activities, such as anticancer, antibacterial, etc. In addition, imides are also widely used in the fields of organic light-emitting materials, agricultural chemicals, and the like. Due to their widespread use, imide synthesis is favored by many chemical researchers. The existing imide synthesis methods mainly comprise amide N-acylation, direct oxidation of N-alkyl amide, reaction of isocyanic compounds as nucleophilic reagents and the like. In 1965, the Miller group first discovered that imide derivatives were obtained by Mumm rearrangement of the reaction product of imidoyl chloride and carboxy silver. The products prior to rearrangement are oxime esters, which are highly unstable and therefore rearrange to produce more stable imide products [ David Y. Curtin, Larry L. Miller. tetrahedron letters.1965,23,1869-1876 ]. In 2006, the Nicolaou project group reported the use of high-valent iodine as the oxidant and the oxidation of amides to imides [ Nicolaou K C, Mathison C.Angewandte Chemie,2006,37(2):6146 6151 ]. In 2008, the Zhao project group used bromosuccinimide and cuprous bromide to catalyze the dehydrogenation coupling of aldehydes and amides to synthesize amides [ L.Wang, H.Fu, J.Y.Jiang, Y.F.Zhao.chemistry-A European Journal,2008,14(34):10722-10726 ]. In 2013, the Xi project group used CuCl as a catalyst and TBHP (tert-butyl hydroperoxide) as an oxidant to oxidize secondary amines to synthesize imide compounds [ Yan, X, Y, Fang, K, Liu, H, L, Xi, C, J.chem.Commun.,2013,49,10650-10652 ]. In 2013, the group of Grimuraud uses aryl diazonium salt, isocyanide and carboxylate as reactants, which generate nitrile phosphorus ylide intermediate during the reaction, followed by rearrangement to obtain imide compounds [ Basavanag U, Dos Santos A, El Kaim L, et al, three-Component Metal-Free aryl of Isocyanides [ J ]. Angewandte Chemie,2013,125(28):7335-7338 ]. In 2019, Yao's project group reported the synthesis of imide compounds using aryl halides, carboxylic acids and isocyanides as reactants under the catalytic action of metallic palladium [ Wang B, He D, Ren B G, Yao T L.chemical Communications,2020,56,900-903 ]. However, the above-mentioned production methods generally have disadvantages such as complicated raw materials (raw materials need to be activated in advance), participation of halogen or transition metal in the reaction, poor substrate adaptability, and many by-products. Therefore, it is necessary to develop a method for preparing an imide derivative which is efficient and environmentally friendly.
Disclosure of Invention
In order to overcome the problems of the prior art, an object of the present invention is to provide a method for electrochemically preparing an imide derivative; the second object of the present invention is to provide the use of such imide derivatives in electrochemical processes.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a method for electrochemically preparing imide derivatives, which comprises the following steps:
carrying out electrochemical reaction on a compound shown as a formula (I), a nitrile compound and dialkyl peroxide in the presence of an electrolyte to obtain an imide derivative shown as a formula (II);
Figure BDA0003594979850000021
in the formula (I), Ar is selected from substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl;
Figure BDA0003594979850000022
in the formula (II), Ar is selected from substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl; r1Selected from ethyl, isopropyl, tert-butyl, tert-amyl, cyclohexyl; r2Selected from methyl, ethyl, propyl, isopropyl;
the nitrile compound comprises at least one of acetonitrile, propionitrile, butyronitrile and isobutyronitrile.
Preferably, in formula (I), Ar is selected from substituted or unsubstituted aryl; further preferably, in formula (I), Ar is selected from substituted or unsubstituted phenyl.
Preferably, in formula (II), Ar is selected from substituted or unsubstituted aryl, R1Selected from isopropyl, tert-butyl, R2Selected from methyl, ethyl; further preferably, in formula (II), Ar is selected from substituted or unsubstituted phenyl, R1Selected from tert-butyl, R2Selected from methyl.
Preferably, the electrolyte comprises at least one of n-tetrabutyl perchlorate, n-tetrabutyl hexafluorophosphate and n-tetrabutyl tetrafluoroborate; further preferably, the electrolyte comprises at least one of n-tetrabutylammonium perchlorate, n-tetrabutylsodium perchlorate, n-tetrabutylammonium hexafluorophosphate and n-tetrabutylsodium hexafluorophosphate; still further preferably, the electrolyte is n-tetrabutylammonium perchlorate.
Preferably, the concentration of the electrolyte is 0.03mol/L-0.2 mol/L; further preferably, the concentration of the electrolyte is 0.05mol/L to 0.15 mol/L.
Preferably, the dialkyl peroxide comprises at least one of diethyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide and dicyclohexyl peroxide; further preferably, the dialkyl peroxide comprises at least one of diisopropyl peroxide, di-tert-butyl peroxide and di-tert-amyl peroxide; still more preferably, the dialkyl peroxide is di-tert-butyl peroxide.
Preferably, the molar ratio of the compound of formula (i) to the dialkyl peroxide is 1: (0.8-4); further preferably, the molar ratio of the compound of formula (i) to the dialkyl peroxide is 1: (1-3).
Preferably, the electrode for electrochemical reaction comprises at least one of a platinum electrode, a graphite electrode and a nickel electrode; further preferably, the electrode for electrochemical reaction is a platinum electrode.
Optionally, the platinum electrode is a platinum sheet electrode or a platinum mesh electrode.
Preferably, the current of the electrochemical reaction is 3mA-7 mA; further preferably, the current of the electrochemical reaction is 4mA-6 mA.
Preferably, the time of the electrochemical reaction is 2h-5 h; further preferably, the time of the electrochemical reaction is 2.5h-4 h.
Preferably, the temperature of the electrochemical reaction is 10-40 ℃; further preferably, the temperature of the electrochemical reaction is 15 ℃ to 30 ℃.
Preferably, the solvent for the electrochemical reaction comprises a nitrile compound.
The nitrile compound comprises at least one of acetonitrile, propionitrile, butyronitrile and isobutyronitrile.
Preferably, in the electrochemical reaction, the molar ratio of the compound represented by the formula (i) to the nitrile compound is 1: (200- > 1000); further preferably, in the electrochemical reaction, the molar ratio of the compound represented by the formula (i) to the nitrile compound is 1: (300-800).
Preferably, after the electrochemical reaction, a separation and purification step is further included.
Preferably, the step of separating and purifying comprises extraction.
In a second aspect, the present invention provides the use of the electrochemical preparation method of the imide derivative according to the first aspect of the present invention for preparing an organic light-emitting material, a pesticide, or a medicament.
The invention has the beneficial effects that:
the method takes aryl formic acid or heteroaryl formic acid as a substrate, and reacts with dialkyl peroxide and nitrile compounds under electrochemical conditions to synthesize an imide derivative in one step; the reaction does not need to add an additional metal catalyst, is environment-friendly, has mild conditions, easily obtained raw materials and simple and easy reaction; the preparation reaction widens the preparation method of the imide derivative, provides simpler and more convenient synthesis steps, and can be widely applied to the preparation of organic luminescent materials, pesticides and medicaments.
Specifically, the invention has the following advantages:
in the imide preparation method disclosed by the application, dialkyl peroxides are used as alkyl sources to synthesize the imide derivatives in an electrochemical organic synthesis method for the first time, so that the research direction and the application range of the imide derivatives are further expanded. Electrochemical organic synthesis is a green, efficient and environment-friendly synthesis method, and more attention is paid to electrochemical organic synthesis. The imide derivative can be synthesized under the conditions of normal temperature, normal pressure and constant current; according to the method, an additional metal catalyst is not required, so that the use of toxic, expensive and complex metal catalysts is effectively avoided; the reaction system disclosed by the application is simple and effective, atom-economical and environment-friendly; the raw materials used in the method are simple and easily available, and the aryl formic acid or the heteroaryl formic acid exists in a large amount in nature, and has low commercial price and stable property. In industry, di-tert-butyl peroxide can be prepared from tert-butanol at low commercial price, both of which are cheap and readily available raw materials. The method disclosed by the application avoids harsh conditions such as high temperature, high pressure and the like, the reaction is operated at normal temperature and normal pressure, the operation is simple and safe, and the method is suitable for large-scale industrial production.
Drawings
FIG. 1 is a NMR chart of the product prepared in example 1.
FIG. 2 is a NMR carbon spectrum of the product prepared in example 1.
FIG. 3 is a NMR chart of the product prepared in example 8.
FIG. 4 is a NMR carbon spectrum of the product prepared in example 8.
FIG. 5 is a NMR chart of the product prepared in example 9.
FIG. 6 is the NMR carbon spectrum of the product prepared in example 9.
FIG. 7 is a NMR chart of the product prepared in example 10.
FIG. 8 is a NMR carbon spectrum of the product prepared in example 10.
FIG. 9 is a NMR chart of the product prepared in example 11.
FIG. 10 is a NMR carbon spectrum of the product prepared in example 11.
FIG. 11 is a NMR chart of the product prepared in example 12.
FIG. 12 is a NMR carbon spectrum of the product prepared in example 12.
FIG. 13 is a NMR chart of the product prepared in example 13.
FIG. 14 is a NMR carbon spectrum of the product prepared in example 13.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available through commercial purchase.
Example 1
The procedure for the preparation of the imide derivatives of this example is as follows:
a platinum sheet is taken as an anode and a platinum sheet is taken as a cathode, 0.2mmol of benzoic acid, 0.6mmol of di-tert-butyl peroxide, 0.1mol/L of n-tetrabutylammonium perchlorate and 5mL (95.8mmol) of acetonitrile solvent are sequentially added into a 5mL round-bottom flask, a magnetic stirrer is switched on, the current is adjusted to be 5mA, and the reaction is carried out for 3 hours at room temperature. After the reaction is finished, ethyl acetate is used for extraction for three times, organic phases are combined, anhydrous magnesium sulfate is used for drying, separation and vacuum rotary evaporation are carried out, and the corresponding product is obtained after purification, wherein the yield is 88%. The imide derivative of this example was prepared according to the following reaction scheme:
Figure BDA0003594979850000041
FIG. 1 is the NMR spectrum of the product prepared in example 1, and FIG. 2 is the NMR spectrum of the product prepared in example 1. The specific nuclear magnetic data are as follows:1H NMR(500 MHz,CDCl3)δ8.02(d,J＝7.8Hz,2H),7.66(d,J＝7.5Hz,1H),7.54(t,J＝7.8Hz,2H),1.86(s,3H),1.51(s,9H)；13C NMR(126 MHz,CDCl3) δ 176.33,168.46,134.51,130.47,129.24,58.39,28.39, 25.83. The nuclear magnetic identification confirms that the product structure is the shown compound
Figure BDA0003594979850000051
The above test data were compared with the data of Lux M, Klussmann M.org.Lett.2020,22, 3697-.
Example 2
The procedure for the preparation of the imide derivatives of this example is as follows:
a platinum sheet is taken as an anode, a platinum net is taken as a cathode, 0.2mmol of benzoic acid, 0.6mmol of di-tert-butyl peroxide, 0.1mol/L of n-tetrabutylammonium perchlorate, 5mL of acetonitrile solvent and a magnetic stirrer are sequentially added into a 5mL round-bottom flask, a power supply is switched on, the current is adjusted to be 5mA, and the reaction is carried out for 3h at room temperature. After the reaction is finished, ethyl acetate is used for extraction for three times, organic phases are combined, anhydrous magnesium sulfate is used for drying, separation and vacuum rotary evaporation are carried out, and the corresponding product is obtained after purification, wherein the yield is 79%. The imide derivative of this example was prepared according to the following chemical formula:
Figure BDA0003594979850000052
example 3
The procedure for the preparation of the imide derivatives of this example is as follows:
and (2) taking a platinum sheet as an anode and a platinum sheet as a cathode, sequentially adding 0.2mmol of benzoic acid, 0.6mmol of di-tert-butyl peroxide, 0.15mol/L of n-tetrabutylammonium perchlorate and 5mL of acetonitrile solvent into a 5mL round-bottom flask, switching on a power supply, adjusting the current to be 5mA, and reacting for 3 hours at room temperature. After the reaction is finished, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous magnesium sulfate, separating, performing vacuum rotary evaporation, and purifying to obtain a corresponding product, wherein the yield is 86%. The imide derivative of this example was prepared according to the following chemical formula:
Figure BDA0003594979850000053
example 4
The procedure for the preparation of the imide derivatives of this example is as follows:
and (2) taking a platinum sheet as an anode and a platinum sheet as a cathode, sequentially adding 0.2mmol of benzoic acid, 0.6mmol of di-tert-butyl peroxide, 0.05mol/L of n-tetrabutylammonium perchlorate and 5mL of acetonitrile solvent into a 5mL round-bottom flask, switching on a power supply, adjusting the current to be 5mA, and reacting for 3 hours at room temperature. After the reaction is finished, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous magnesium sulfate, separating, performing vacuum rotary evaporation, and purifying to obtain a corresponding product, wherein the yield is 90%. The imide derivative of this example was prepared according to the following chemical formula:
Figure BDA0003594979850000061
example 5
The procedure for the preparation of the imide derivatives of this example is as follows:
and (2) taking a platinum sheet as an anode and a platinum sheet as a cathode, sequentially adding 0.2mmol of benzoic acid, 0.4mmol of di-tert-butyl peroxide, 0.05mol/L of n-tetrabutylammonium perchlorate and 5mL of acetonitrile solvent into a 5mL round-bottom flask, switching on a power supply, adjusting the current to be 5mA, and reacting for 3 hours at room temperature. After the reaction is finished, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous magnesium sulfate, separating, performing vacuum rotary evaporation, and purifying to obtain a corresponding product, wherein the yield is 85%.
Example 6
The procedure for the preparation of the imide derivatives of this example is as follows:
and (2) taking a platinum sheet as an anode and a platinum sheet as a cathode, sequentially adding 0.2mmol of benzoic acid, 0.3mmol of di-tert-butyl peroxide, 0.05mol/L of n-tetrabutylammonium perchlorate and 5mL of acetonitrile solvent into a 5mL round-bottom flask, switching on a power supply, adjusting the current to be 5mA, and reacting for 3 hours at room temperature. After the reaction is finished, ethyl acetate is used for extraction for three times, organic phases are combined, anhydrous magnesium sulfate is used for drying, separation and vacuum rotary evaporation are carried out, and the corresponding product is obtained after purification, wherein the yield is 93%.
Example 7
The procedure for the preparation of the imide derivatives of this example is as follows:
and (2) taking a platinum sheet as an anode and a platinum sheet as a cathode, sequentially adding 0.2mmol of benzoic acid, 0.2mmol of di-tert-butyl peroxide, 0.05mol/L of n-tetrabutylammonium perchlorate and 5mL of acetonitrile solvent into a 5mL round-bottom flask, switching on a power supply, adjusting the current to be 5mA, and reacting for 3 hours at room temperature. After the reaction is finished, ethyl acetate is used for extraction for three times, organic phases are combined, anhydrous magnesium sulfate is used for drying, separation and vacuum rotary evaporation are carried out, and the corresponding product is obtained after purification, wherein the yield is 93%.
Example 8
The procedure for the preparation of the imide derivatives of this example is as follows:
and (2) taking a platinum sheet as an anode and a platinum sheet as a cathode, sequentially adding 0.2mmol of 4-methylbenzoic acid, 0.4mmol of di-tert-butyl peroxide, 0.05mol/L of n-tetrabutylammonium perchlorate, 5mL of acetonitrile solvent and a magnetic stirrer into a 5mL round-bottom flask, switching on a power supply, adjusting the current to be 5mA, and reacting for 3 hours at room temperature. After the reaction is finished, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous magnesium sulfate, separating, performing vacuum rotary evaporation, and purifying to obtain a corresponding product, wherein the yield is 87%. The imide derivative of this example was prepared according to the following chemical formula:
Figure BDA0003594979850000071
FIG. 3 is the NMR hydrogen spectrum of the product prepared in example 8, and FIG. 4 is the NMR carbon spectrum of the product prepared in example 8. The specific nuclear magnetic data are as follows:1H NMR(500MHz,CDCl3)δ7.90(d,J＝7.9Hz,2H),7.33(d,J＝8.0Hz,2H),2.46(s,3H),1.85(s,3H),1.50(s,9H)ppm。13C NMR(126MHz,CDCl3) δ 176.10,168.42,145.82,133.00,130.67,129.97,58.21,28.37, 21.78. The product structure prepared by the test is the imide derivative of the example
Figure BDA0003594979850000072
Example 9
The procedure for the preparation of the imide derivatives of this example is as follows:
and (2) taking a platinum sheet as an anode and a platinum sheet as a cathode, sequentially adding 0.2mmol of 4-ethylbenzoic acid, 0.3mmol of di-tert-butyl peroxide, 0.05mol/L of n-tetrabutylammonium perchlorate, 5mL of acetonitrile solvent and a magnetic stirrer into a 5mL round-bottom flask, switching on a power supply, adjusting the current to be 5mA, and reacting for 3h at room temperature. After the reaction is finished, ethyl acetate is used for extraction for three times, organic phases are combined, anhydrous magnesium sulfate is used for drying, separation and vacuum rotary evaporation are carried out, and the corresponding product is obtained after purification, wherein the yield is 54%. The imide derivative of this example was prepared according to the following chemical formula:
Figure BDA0003594979850000073
FIG. 5 is the NMR spectrum of the product prepared in example 9, and FIG. 6 is the NMR spectrum of the product prepared in example 9. The specific nuclear magnetic data are as follows:1H NMR(500MHz,CDCl3)δ7.93(d,J＝8.1Hz,2H),7.35(d,J＝8.0Hz,2H),2.75(q,J＝7.5Hz,2H),1.86(s,3H),1.50(s,9H),1.29(t,J＝7.6Hz,3H)ppm.13C NMR(126MHz,CDCl3) δ 176.13,168.42,151.86,133.19,130.78,128.77,58.20,29.01,28.38,25.75, 14.95. The product prepared by the test has the structure of the imide derivative
Figure BDA0003594979850000074
Example 10
The procedure for the preparation of the imide derivatives of this example is as follows:
and (2) taking a platinum sheet as an anode and a platinum sheet as a cathode, sequentially adding 0.2mmol of 4-fluorobenzoic acid, 0.3mmol of di-tert-butyl peroxide, 0.05mol/L of n-tetrabutylammonium perchlorate, 5mL of acetonitrile solvent and a magnetic stirrer into a 5mL round-bottom flask, switching on a power supply, adjusting the current to be 5mA, and reacting for 3h at room temperature. After the reaction is finished, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous magnesium sulfate, separating, carrying out vacuum rotary evaporation, and purifying to obtain a corresponding product, wherein the yield is 91%. The imide derivative of this example was prepared according to the following chemical formula:
Figure BDA0003594979850000081
FIG. 7 is the NMR hydrogen spectrum of the product prepared in example 10, and FIG. 8 is the NMR carbon spectrum of the product prepared in example 10. The specific nuclear magnetic data are as follows:1H NMR(500MHz,CDCl3)δ8.04(dd,J＝8.5,5.4Hz,2H),7.21(t,J＝8.4Hz,2H),1.85(s,3H),1.49(s,9H)ppm.13C NMR(126MHz,CDCl3)δ175.15,168.33,166.60(d,JC-F＝259.6Hz),133.24(d,JC-F＝8.8Hz),132.06(d,JC-F＝2.5Hz),116.56(d,JC-F21.4Hz),58.52,28.42, 25.80. Prepared by testingThe product structure is the imide derivative of the example
Figure BDA0003594979850000082
Example 11
The procedure for the preparation of the imide derivatives of this example is as follows:
a platinum sheet is taken as an anode, a platinum sheet is taken as a cathode, 0.2mmol of 4-chlorobenzoic acid, 0.3mmol of di-tert-butyl peroxide, 0.05mol/L of n-tetrabutylammonium perchlorate, 5mL of acetonitrile solvent and a magnetic stirrer are sequentially added into a 5mL round-bottom flask, a power supply is switched on, the current is adjusted to be 5mA, and the reaction is carried out for 3 hours at room temperature. After the reaction is finished, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous magnesium sulfate, separating, carrying out vacuum rotary evaporation, and purifying to obtain a corresponding product, wherein the yield is 72%. The imide derivative of this example was prepared according to the following chemical formula:
Figure BDA0003594979850000083
FIG. 9 is the NMR hydrogen spectrum of the product prepared in example 11, and FIG. 10 is the NMR carbon spectrum of the product prepared in example 11. The specific nuclear magnetic data are as follows:1H NMR(500MHz,CDCl3)δ7.95(d,J＝8.6Hz,2H),7.51(d,J＝8.6Hz,2H),1.85(s,3H),1.49(s,9H)ppm.13C NMR(126MHz,CDCl3) δ 175.45,168.33,141.31,134.08,131.78,129.67,58.61,28.44, 25.88. The product structure prepared by the test is the imide derivative of the example
Figure BDA0003594979850000091
Example 12
The procedure for the preparation of the imide derivatives of this example is as follows:
and (2) taking a platinum sheet as an anode and a platinum sheet as a cathode, sequentially adding 0.2mmol of 4-bromobenzoic acid, 0.3mmol of di-tert-butyl peroxide, 0.05mol/L of n-tetrabutylammonium perchlorate and 5mL of acetonitrile solvent into a 5mL round-bottom flask, and then, switching on a power supply, adjusting the current to be 5mA, and reacting for 3 hours at room temperature. After the reaction is finished, ethyl acetate is used for extraction for three times, organic phases are combined, anhydrous magnesium sulfate is used for drying, separation and vacuum rotary evaporation are carried out, and the corresponding product is obtained after purification, wherein the yield is 71%. The imide derivative of this example was prepared according to the following chemical formula:
Figure BDA0003594979850000092
FIG. 11 is the NMR hydrogen spectrum of the product prepared in example 12, and FIG. 12 is the NMR carbon spectrum of the product prepared in example 12. The specific nuclear magnetic data are as follows:1H NMR(500MHz,CDCl3)δ7.87(d,J＝8.6Hz,2H),7.68(d,J＝8.6Hz,2H),1.85(s,3H),1.49(s,9H)ppm.13C NMR(126MHz,CDCl3) δ 175.64,168.32,134.51,132.68,131.82,130.12,58.62,28.44, 25.89. The product prepared by the test has the structure of the imide derivative
Figure BDA0003594979850000093
Example 13
The procedure for the preparation of the imide derivatives of this example is as follows:
a platinum sheet is used as an anode, a platinum sheet is used as a cathode, 0.2mmol of 4-tert-butylbenzoic acid, 0.3mmol of di-tert-butyl peroxide, 0.05mol/L of n-tetrabutylammonium perchlorate, 5mL of acetonitrile solvent and a magnetic stirrer are sequentially added into a 5mL round-bottom flask, a power supply is switched on, the current is adjusted to be 5mA, and the reaction is carried out for 3 hours at room temperature. After the reaction is finished, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous magnesium sulfate, separating, performing vacuum rotary evaporation, and purifying to obtain a corresponding product, wherein the yield is 86%. The imide derivative of this example was prepared according to the following chemical formula:
Figure BDA0003594979850000094
FIG. 13 is the NMR hydrogen spectrum of the product prepared in example 13, and FIG. 14 is the NMR carbon spectrum of the product prepared in example 13. Its concrete coreThe magnetic data are as follows:1H NMR(500MHz,CDCl3)δ7.93(d,J＝8.5Hz,2H),7.53(d,J＝8.5Hz,2H),1.86(s,3H),1.50(s,9H),1.36(s,9H)ppm.13C NMR(126MHz,CDCl3) δ 176.11,168.45,132.86,158.66,130.53,126.23,58.22,35.33,31.02,28.41, 25.78. The product prepared by the test has the structure of the imide derivative
Figure BDA0003594979850000101
Example 14
In the preparation steps of the imide derivative, a graphite/Ni electrode (graphite is used as an anode and Ni is used as a cathode) is adopted as an electrode, the rest steps are completely the same as the step in the example 1, and the yield of the corresponding product obtained after purification is 31 percent.
The electrochemical preparation method of the imide derivative disclosed by the embodiment of the application is simple and efficient, green and pollution-free, and can be widely applied to preparation of organic luminescent materials, pesticides, medicines and the like.
The above examples are preferred embodiments of the present invention, but the present invention is not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are intended to be included in the scope of the present invention.

Claims (10)

1. An electrochemical preparation method of imide derivatives is characterized in that: the method comprises the following steps:
carrying out electrochemical reaction on a compound shown as a formula (I), a nitrile compound and dialkyl peroxide in the presence of an electrolyte to obtain an imide derivative shown as a formula (II);
Ar-COOH (Ⅰ)；
in the formula (I), Ar is selected from substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl;
Figure FDA0003594979840000011
in the formula (II), Ar is selected from substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl; r is1Selected from ethyl, isopropyl, tert-butyl, tert-amyl, cyclohexyl; r2Selected from methyl, ethyl, propyl, isopropyl;
the nitrile compound comprises at least one of acetonitrile, propionitrile, butyronitrile and isobutyronitrile.
2. The electrochemical production method of an imide derivative as claimed in claim 1, wherein: the electrolyte comprises at least one of n-tetrabutyl perchlorate, n-tetrabutyl hexafluorophosphate and n-tetrabutyl tetrafluoroborate.
3. The electrochemical production method of an imide derivative as claimed in claim 2, wherein: the concentration of the electrolyte is 0.03mol/L-0.2 mol/L.
4. The electrochemical production method of an imide derivative as claimed in claim 1, wherein: the dialkyl peroxide comprises at least one of diethyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide and dicyclohexyl peroxide.
5. The electrochemical production method of an imide derivative according to claim 4 wherein: the molar ratio of the compound shown in the formula (I) to the dialkyl peroxide is 1: (0.8-4).
6. The electrochemical production method of an imide derivative as claimed in claim 1, wherein: the electrode for electrochemical reaction comprises at least one of a platinum electrode, a graphite electrode and a nickel electrode.
7. The electrochemical production method of an imide derivative as claimed in claim 1, wherein: the current of the electrochemical reaction is 3mA-7 mA.
8. The electrochemical production method of an imide derivative as claimed in claim 1, wherein: the time of the electrochemical reaction is 2-5 h; the temperature of the electrochemical reaction is 10-40 ℃.
9. The electrochemical production method of an imide derivative as claimed in claim 1, wherein: in the electrochemical reaction, the molar ratio of the compound shown as the formula (I) to the nitrile compound is 1: (200-1000).
10. Use of the electrochemical preparation method of an imide derivative as claimed in any one of claims 1 to 9 for the preparation of an organic light emitting material, a pesticide, or a medicament.
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Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
QIAO CHU ET AL.: "Three-component reaction for the synthesis of imides enabled by electrochemical C(sp3)–H functionalization", 《GREEN CHEM.》, pages 1 - 5 *
XIAOFENG ZHANG ET AL.: "Electrochemical Difunctionalization of Alkenes by a Four-Component Reaction Cascade Mumm Rearrangement: Rapid Access to Functionalized Imides", 《ANGEW. CHEM. INT. ED.》, vol. 2, pages 3465 - 3469 *
王春华等, 科学出版社 *

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