CN110923744A - Method for constructing secondary amine compound through reductive amination reaction of electrochemical aldehyde - Google Patents
Method for constructing secondary amine compound through reductive amination reaction of electrochemical aldehyde Download PDFInfo
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Abstract
The invention discloses a method for constructing secondary amine compounds through reductive amination reaction of electrochemical aldehyde, which comprises the following steps: a series of compounds containing secondary amine frameworks are prepared by taking aldehyde compounds and amine compounds as raw materials and carrying out electrochemical cathode reduction reaction in an electrolytic system. Compared with the reported method, the invention does not use metal catalyst and external oxidant; the reaction raw materials and the electrolyte used in the invention have low price, no toxicity and no odor, and simple and convenient post-treatment, thereby being applicable to industrial production; the method has the advantages of mild reaction conditions, simple operation and high yield, and is a high-efficiency and practical synthesis method of the secondary amine compound.
Description
Technical Field
The invention relates to the field of organic matter synthesis, in particular to a method for constructing secondary amine compounds through reductive amination reaction of electrochemical aldehyde.
Background
Amines are an indispensable class of bioactive substances and are present in a variety of natural products, agrochemical substances and drugs, such as anti-Parkinsonian drugs, anti-Trypanosoma cruzi drugs and antihistamines for the treatment of rhinitis. Currently, a variety of synthetic methods for the construction and functionalization of amines have been established, with reductive amination being considered one of the most versatile and efficient methods. Reductive amination is the formation of an imine intermediate by the dehydrocondensation of an amine with a ketone or aldehyde followed by reduction to give the desired amine. In order to perform efficient, highly selective reductive amination, chemists have made great efforts to find suitable reducing systems and reducing agents. Since the middle of the 20 th century, Borch et al have begun to use stoichiometric NaBH4And NaBH3CN acts as a strong reducing agent for reductive amination. Later, more stable hydrosilanes became effective reducing agents, and their use in reductive amination generally required high temperatures, but did not require the use of inert atmospheres and dry solvents. In response to green chemistry, hydrogen has been widely used in recent years for a variety of transition metal catalyzed or lewis acid catalyzed reductive amination studies, but these studies typically require high pressure conditions. At the same time, some Rh-catalyzed reductive amination of aldehydes with CO as the reducing agent has also been successfully achieved. In order to develop a greener, more sustainable amine synthesis process, researchers are turning to metal-free catalytic systems that use simple, mild reaction conditions, inexpensive and readily available reaction materials, and low-toxicity solvents.
Electrochemical synthesis is considered to be an environmentally friendly and sustainable synthesis tool, and has received much attention in recent years. Electrochemical synthesis can realize a series of redox reactions by activating a substrate on the surface of an electrode by effectively utilizing energy. At the cathode surface of the cell, electrons are an ideal substitute for reducing agents for a series of reduction reactions, and can be used to achieve more efficient synthesis of organic molecules. Although hydrogen is a common hydrogen source for electrochemical reactions and is inconvenient to store and use, so far, although many electrochemical hydrogenation reports exist, the continuous search for a hydrogen source which is low in cost, safe and easy to store is still a research subject of great interest. In conclusion, it is of great significance to develop a new synthesis method of amine compounds with environmental protection and high efficiency and to find a hydrogen source which is safe and easy to store and is suitable for industrial production.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a method for constructing a secondary amine compound through a reductive amination reaction of electrochemical aldehyde, which can synthesize the secondary amine compound efficiently and environmentally.
A method of constructing secondary amines by an electrochemical reductive amination reaction of aldehydes according to an embodiment of the first aspect of the invention comprises the steps of: taking an aldehyde compound shown in a formula (I) and an amine compound shown in a formula (II) as raw materials, and preparing a secondary amine compound shown in a formula (III) through electrochemical cathode reduction reaction in an electrolytic system; the electrolytic system comprises an electrolyte, a solvent, an anode and a cathode;
in the formula, R1And R2Are each independently selected from alkyl, aryl and heteroaryl; r1And R2May be the same or different.
The method for constructing the secondary amine compound through the reductive amination reaction of the electrochemical aldehyde according to the embodiment of the invention has at least the following beneficial effects: the method does not use an external oxidant, does not use a noble metal catalyst, and has the advantages of simple conditions, less waste discharge, good functional group tolerance, high yield, mild reaction conditions and the like, so the method is a green, environment-friendly and efficient synthesis method, and can be suitable for industrial large-scale production.
According to some embodiments of the invention, wherein:
R1selected from aryl groups including unsubstituted phenyl, alkylphenyl, alkoxyphenyl, benzyloxyphenyl or halophenyl;
R2selected from aryl groups including unsubstituted phenyl, alkylphenyl, alkoxyphenyl or benzyloxyphenyl;
preferably, the alkylphenyl is a mono-, di-or tri-substituted alkylphenyl, wherein the alkyl substituent is an alkyl group having less than 8 carbon atoms, including but not limited to methyl, ethyl, propyl, and the like; the alkoxy phenyl is a mono-substituted or di-substituted alkoxy phenyl, wherein the alkoxy substituent is an alkyl with less than 10 carbon atoms, and includes but is not limited to methoxy, ethoxy and the like; the halogenated phenyl is monohalogenated phenyl, wherein halogen atoms are selected from F or Cl; the heterocyclic group is an oxygen-containing heterocyclic ring or a sulfur-containing heterocyclic ring, and further preferably, the oxygen-containing heterocyclic ring is furan and the sulfur-containing heterocyclic ring is thiophene.
According to some embodiments of the invention, the electrolyte comprises at least one of tetra-n-butylammonium tetrafluoroborate, tetra-n-butylammonium acetate, tetra-n-butylammonium hydrogen sulfate, or tetra-n-butylammonium hexafluorophosphate.
According to some embodiments of the present invention, the molar ratio of the aldehyde compound to the electrolyte is 1 (1-2);
preferably, the molar ratio of the aldehyde compound to the electrolyte is 1: (1-1.5).
According to some embodiments of the invention, the molar ratio of the aldehyde compound to the amine compound is 1 (1-3);
preferably, the molar ratio of the aldehyde compound to the amine compound is 1 (1.2-3).
According to some embodiments of the invention, the solvent comprises at least one of dimethylsulfoxide, ethanol, N-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, and 1, 4-dioxane;
preferably, the solvent is dimethyl sulfoxide; dimethyl sulfoxide (DMSO), a common and inexpensive solvent, has been shown to act as a hydrogen donor for organic reactions in the presence of bases, while converting to stable DMSO radicals; in the scheme, a low-toxicity solvent DMSO is used as a hydrogen donor, and metal and other external reducing agents are not needed, so that the important application of DMSO as a cheap and convenient hydrogen source in electrochemical synthesis is realized, and a method for efficiently obtaining a secondary amine compound through an electrochemical reductive amination reaction of aldehyde and amine at room temperature is provided.
According to some embodiments of the present invention, the volume of the solvent is (10 to 25) mL/mmol, and more preferably (10 to 15) mL/mmol, based on the molar amount of the aldehyde compound.
According to some embodiments of the invention, the anode and the cathode each comprise a carbon rod.
According to some embodiments of the invention, the direct current used for the reaction is (5-20) mA;
preferably, the direct current used for the reaction is (5 to 10) mA.
According to some embodiments of the invention, the reaction is carried out at a temperature of (25-40) DEG C; further preferably, the reaction is carried out at normal temperature.
According to some embodiments of the invention, the reaction time is (3-18) hours; further preferably, the reaction time is (4.5 to 7) hours.
According to some embodiments of the invention, after quenching, washing, extracting and concentrating after the reaction is finished, a compound containing a secondary amine skeleton is obtained by column chromatography;
preferably, ethyl acetate is added after the reaction is finished to quench the reaction, the reaction is washed and separated to obtain an organic phase, the aqueous phase is extracted by ethyl acetate, the organic phases are combined, dried, subjected to reduced pressure distillation to remove the solvent, and subjected to column chromatography to obtain the compound containing the secondary amine skeleton.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
Example 1: synthesis of N-benzylaniline
A three-necked round-bottomed flask was taken, and charged with 5mL of dimethyl sulfoxide, 53mg (0.50mmol) of benzaldehyde, 56mg (0.6mmol) of aniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and the mixture was electrochemically reacted at room temperature under stirring at 10mA for 4.5 hours with a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 96%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.25-7.19(m,4H),7.15(ddd,J＝6.9,4.0,1.7Hz,1H),7.07-7.03(m,2H),6.60(td,J＝7.3,1.0Hz,1H),6.52-6.47(m,2H),4.17(s,2H),3.73(s,1H).13C NMR(126MHz,CDCl3,ppm)δ＝148.3,139.6,129.4,128.8,127.7,127.4,117.7,113.0,48.4；HRMS(ESI)(m/z):calcd for C13H14N[M+H]+:184.1120,found:184.1117。
example 2: synthesis of N- (4-methylbenzyl) aniline
A three-necked round-bottomed flask was taken, and charged with 5mL of dimethyl sulfoxide, 60mg (0.50mmol) of 4-methylbenzaldehyde, 56mg (0.6mmol) of aniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and the mixture was electrochemically reacted at room temperature under stirring at 8mA current for 4.5 hours with a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 62%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.28(d,J＝7.9Hz,2H),7.21-7.16(m,4H),6.76-6.71(m,1H),6.65(dd,J＝8.6,0.9Hz,2H),4.30(s,2H),4.00(s,1H),2.36(s,3H).13C NMR(126MHz,CDCl3,ppm)δ＝148.2,136.9,136.4,129.4,129.3,127.6,117.5,112.8,48.1,21.2.MS(EI,70eV)m/z:197,180,152,118,105.HRMS(ESI)(m/z):calcdfor C14H16N[M+H]+:198.1277,found:198.1273。
example 3: synthesis of N- (4- (tert-butyl) benzyl) aniline
A three-necked round-bottomed flask was charged with 6mL of dimethyl sulfoxide, 81mg (0.50mmol) of 4-tert-butylbenzaldehyde, 56mg (0.6mmol) of aniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and the mixture was electrochemically reacted at room temperature under stirring at 8mA current for 5 hours with a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 98%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.40(m,2H),7.34(d,J＝8.5Hz,2H),7.21(m,2H),6.75(tt,J＝7.4,1.0Hz,1H),6.68(dd,J＝8.6,1.0Hz,2H),4.32(s,2H),4.16(s,1H),1.35(s,9H).13C NMR(126MHz,CDCl3,ppm)δ＝150.3,148.3,136.4,129.3,127.4,125.6,117.5,112.8,48.0,34.5,31.4.MS(EI,70eV)m/z:239,147,117.HRMS(ESI)(m/z):calcd for C17H22N[M+H]+:240.1747,found:240.1741。
example 4: synthesis of N- (4-methoxybenzyl) aniline
A three-necked round-bottomed flask was charged with 6mL of dimethyl sulfoxide, 68mg (0.50mmol) of 4-methoxybenzaldehyde, 56mg (0.6mmol) of aniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and the mixture was stirred at room temperature under a current of 10mA for electrochemical reaction for 4.5 hours while using a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 58%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.33(m,2H),7.22(m,2H),6.92(m,2H),6.75(m,1H),6.68(m,2H),4.29(s,2H),4.00(s,1H),3.84(d,J＝2.3Hz,3H).13C NMR(126MHz,CDCl3,ppm)δ＝158.9,148.2,131.4,129.3,128.8,117.5,114.0,112.8,55.3,47.8.MS(EI,70eV)m/z:213,121,91.HRMS(ESI)(m/z):calcd for C14H16NO[M+H]+:214.1226,found:214.1224。
example 5: synthesis of N- ([ [1,1' -biphenyl ] -4-ylmethyl) aniline
A three-necked round-bottomed flask was charged with 7mL of dimethyl sulfoxide, 91mg (0.50mmol) of 4-phenylbenzaldehyde, 56mg (0.6mmol) of aniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and the mixture was stirred at room temperature under a current of 10mA for electrochemical reaction for 5 hours while using a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 98%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.67-7.63(m,4H),7.53-7.49(m,4H),7.43-7.39(m,1H),7.28-7.24(m,2H),6.83-6.78(m,1H),6.75-6.71(m,2H),4.43(s,2H),4.14(s,1H).13C NMR(126MHz,CDCl3,ppm)δ＝148.2,140.9,140.2,138.6,129.4,128.9,128.0,127.4,127.3,127.1,117.7,112.9,48.0.MS(EI,70eV)m/z:259,167,152,129,104.HRMS(ESI)(m/z):calcd for C19H18N[M+H]+:260.1434,found:260.1429。
example 6: synthesis of N- (3-methoxybenzyl) aniline
A three-necked round-bottomed flask was charged with 6mL of dimethyl sulfoxide, 68mg (0.50mmol) of 3-methoxybenzaldehyde, 56mg (0.6mmol) of aniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and the mixture was stirred at room temperature under a current of 10mA for electrochemical reaction for 4.5 hours while using a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 83%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.29(d,J＝7.3Hz,1H),7.21(m,2H),6.99(m,2H),6.86(dd,J＝8.2,2.4Hz,1H),6.76(t,J＝7.3Hz,1H),6.67(dd,J＝8.5,0.8Hz,2H),4.34(s,2H),4.09(s,1H),3.83(s,3H).13C NMR(126MHz,CDCl3,ppm)δ＝159.9,148.2,141.2,129.7,129.3,119.8,117.6,113.0,112.9,112.7,55.2,48.3.MS(EI,70eV)m/z:213,121,91.HRMS(ESI)(m/z):calcd for C14H16NO[M+H]+:214.1226,found:214.1222。
example 7: synthesis of N- (3-fluorobenzyl) aniline
A three-necked round-bottomed flask was taken, and charged with 5mL of dimethyl sulfoxide, 62mg (0.50mmol) of 3-fluorobenzaldehyde, 56mg (0.6mmol) of aniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and electrochemically reacted at room temperature under a current of 10mA with a carbon rod as an anode and a carbon rod as a cathode for 5 hours. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 89%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.33(td,J＝7.9,5.9Hz,1H),7.20(ddd,J＝12.1,8.8,4.9Hz,3H),7.12(d,J＝9.7Hz,1H),6.98(td,J＝8.5,2.6Hz,1H),6.76(t,J＝7.3Hz,1H),6.67-6.63(m,2H),4.37(s,2H),4.14(s,1H).13C NMR(126MHz,CDCl3,ppm)δ＝163.2(d,J＝245.7Hz),147.8,142.3(d,J＝6.7Hz),130.1(d,J＝8.1Hz,),129.3,122.8(d,J＝2.7Hz),117.8,114.2(d,J＝12.4Hz),114.0(d,J＝12.1Hz),112.9,47.8.MS(EI,70eV)m/z:201,180,152,109.HRMS(ESI)(m/z):calcd for C13H13FN[M+H]+:202.1026,found:202.1023。
example 8: synthesis of N- (2-methoxybenzyl) aniline
A three-necked round-bottomed flask was charged with 6mL of dimethyl sulfoxide, 68mg (0.50mmol) of 2-methoxybenzaldehyde, 56mg (0.6mmol) of aniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and the mixture was stirred at room temperature under a current of 8mA for electrochemical reaction for 5 hours while using a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 97%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.34(dd,J＝7.4,1.5Hz,1H),7.27(d,J＝6.5Hz,1H),7.19(ddd,J＝7.4,5.7,2.1Hz,2H),6.94(m,2H),6.73(m,1H),6.68(dt,J＝3.2,1.6Hz,2H),4.36(s,2H),4.17(s,1H),3.89(s,3H).13C NMR(126MHz,CDCl3,ppm)δ＝157.4,148.4,129.2,128.9,128.3,127.3,120.5,117.4,113.1,110.2,55.3,43.5.MS(EI,70eV)m/z:213,121,91.HRMS(ESI)(m/z):calcd for C13H16NO[M+H]+:214.1226,found:214.1223。
example 9: synthesis of N- (3, 4-dimethoxybenzyl) aniline
A three-necked round-bottomed flask was charged with 6mL of dimethyl sulfoxide, 83mg (0.50mmol) of 3, 4-dimethoxybenzaldehyde, 56mg (0.6mmol) of aniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and the mixture was stirred at room temperature under a current of 10mA for electrochemical reaction for 4.5 hours while using a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 86%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.21(dd,J＝8.4,7.5Hz,2H),6.95(d,J＝6.3Hz,2H),6.86(d,J＝8.7Hz,1H),6.75(t,J＝7.3Hz,1H),6.68(d,J＝7.7Hz,2H),4.28(s,2H),4.00(s,1H),3.90(s,3H),3.90(s,3H).13C NMR(126MHz,CDCl3,ppm)δ＝149.1,148.2,131.9,129.3,119.7,117.6,112.9,111.1,110.8,56.0,55.9,48.3.MS(EI,70eV)m/z:243,151,121,107.HRMS(ESI)(m/z):calcd for C15H18NO2[M+H]+:244.1332,found:244.1328。
example 10: synthesis of N- (furan-2-ylmethyl) aniline
A three-necked round-bottomed flask was taken, and charged with 5mL of dimethyl sulfoxide, 48mg (0.50mmol) of furan-2-carbaldehyde, 56mg (0.6mmol) of aniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and electrochemically reacted at room temperature under stirring at 8mA current for 5 hours with a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 50%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.40(dd,J＝1.8,0.7Hz,1H),7.22(m,2H),6.77(tt,J＝7.4,1.0Hz,1H),6.71(m,2H),6.35(dd,J＝3.2,1.9Hz,1H),6.27(dd,J＝3.2,0.7Hz,1H),4.35(s,2H),4.06(s,1H).13C NMR(126MHz,CDCl3,ppm)δ＝152.7,147.6,142.0,129.3,118.0,113.2,110.4,107.0,41.4.MS(EI,70eV)m/z:173,145,115,81.HRMS(ESI)(m/z):calcd for C11H12NO[M+H]+:174.0913,found:174.0911。
example 11: synthesis of N- (thien-3-ylmethyl) aniline
A three-necked round-bottomed flask was taken, and charged with 5mL of dimethyl sulfoxide, 56mg (0.50mmol) of thiophene-2-carbaldehyde, 56mg (0.6mmol) of aniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and electrochemically reacted at room temperature under a current of 10mA with a carbon rod as an anode and a carbon rod as a cathode for 5 hours. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 31%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.34(dd,J＝4.9,3.0Hz,1H),7.22(m,3H),7.11(dd,J＝4.9,1.2Hz,1H),6.76(t,J＝7.3Hz,1H),6.69(dd,J＝8.5,0.9Hz,2H),4.37(s,2H),4.01(s,1H).13C NMR(126MHz,CDCl3,ppm)δ＝148.0,140.4,129.3,127.2,126.2,121.8,117.7,112.9,43.8.MS(EI,70eV)m/z:189,156,115,97.HRMS(ESI)(m/z):calcd for C11H12NS[M+H]+:190.0685,found:190.0681。
example 12: synthesis of N- (cyclohexylmethyl) aniline
A three-necked round-bottomed flask was charged with 5mL of dimethyl sulfoxide, 56mg (0.50mmol) of cyclohexanecarboxaldehyde, 93mg (1.0mmol) of aniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and the mixture was electrochemically reacted at room temperature under stirring at 8mA current for 5 hours with a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 44%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.20(m,2H),6.71(m,1H),6.63(dd,J＝8.5,0.9Hz,2H),3.75(s,1H),2.99(d,J＝6.7Hz,2H),1.86(dd,J＝13.6,1.8Hz,2H),1.78(m,2H),1.72(m,1H),1.61(m,1H),1.28(m,3H),1.02(dt,J＝12.1,9.2Hz,2H).13CNMR(126MHz,CDCl3,ppm)δ＝148.6,129.2,116.9,112.7,50.6,37.6,31.3,26.6,26.0.MS(EI,70eV)m/z:189,144,117,106.HRMS(ESI)(m/z):calcd for C13H19NNa[M+Na]+:212.1410,found:212.1414。
example 13: synthesis of N-benzyl-4-butylaniline
A three-necked round-bottomed flask was taken, and charged with 5mL of dimethyl sulfoxide, 53mg (0.50mmol) of benzaldehyde, 89mg (0.6mmol) of 4-n-butylaniline and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and electrochemically reacted at room temperature under stirring at 10mA current for 5 hours with a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 98%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.39(dt,J＝12.9,7.4Hz,4H),7.31(t,J＝7.2Hz,1H),7.03(d,J＝8.4Hz,2H),6.62(d,J＝8.4Hz,2H),4.34(s,2H),2.54(m,2H),1.58(m,2H),1.38(m,2H),0.95(t,J＝7.3Hz,3H).13C NMR(126MHz,CDCl3,ppm)δ＝146.2,139.7,132.1,129.2,128.6,127.6,127.2,112.9,48.7,34.7,34.0,22.4,14.0.MS(EI,70eV)m/z:239,196,91,77,65.HRMS(ESI)(m/z):calcd for C17H21NNa[M+Na]+:262.1566,found:262.1566。
example 14: synthesis of N-benzyl-4- (tert-butyl) aniline
A three-necked round-bottomed flask was charged with 5mL of dimethyl sulfoxide, 53mg (0.50mmol) of benzaldehyde, 89mg (0.6mmol) of 4-tert-butylaniline and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and the mixture was stirred at room temperature under a current of 10mA for electrochemical reaction for 6 hours while using a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 86%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.42(m,4H),7.34(td,J＝6.8,1.4Hz,1H),7.28(m,2H),6.67(m,2H),4.37(s,2H),3.85(m,1H),1.35(s,9H).13C NMR(126MHz,CDCl3,ppm)δ＝145.9,140.4,139.7,128.7,127.6,127.2,126.1,112.6,48.7,33.9,31.6.MS(EI,70eV)m/z:239,146,132,91,65.HRMS(ESI)(m/z):calcd for C17H21NNa[M+Na]+:262.1566,found:262.1571。
example 15: synthesis of N-benzyl-4-methoxyaniline
A three-necked round-bottomed flask was taken, and 6mL of dimethyl sulfoxide, 53mg (0.50mmol) of benzaldehyde, 74mg (0.6mmol) of 4-methoxyaniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate were added thereto, and the mixture was stirred at room temperature and 8mA current for electrochemical reaction for 6 hours with a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 47%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.38(m,4H),7.31(dt,J＝4.5,1.9Hz,1H),6.81(m,2H),6.64(m,2H),4.31(s,2H),3.97(s,1H),3.77(s,3H).13C NMR(126MHz,CDCl3,ppm)δ＝152.2,142.3,139.6,128.6,127.6,127.2,114.9,114.2,55.8,49.3.MS(EI,70eV)m/z:213,198,122,91,65.HRMS(ESI)(m/z):calcd for C14H15NONa[M+Na]+:236.1046,found:236.1049。
example 16: synthesis of N-benzyl-4-phenoxyaniline
A three-necked round-bottomed flask was taken, and then added with 7mL of dimethyl sulfoxide, 53mg (0.50mmol) of benzaldehyde, 111mg (0.6mmol) of 4-phenoxyaniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and the mixture was stirred at room temperature under a current of 10mA, and subjected to electrochemical reaction for 6 hours with a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 92%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.48(q,J＝7.1Hz,4H),7.39(m,3H),7.12(td,J＝7.4,0.6Hz,1H),7.06(m,2H),7.02(m,2H),6.72(d,J＝8.7Hz,2H),4.40(s,2H),3.93(s,1H).13C NMR(126MHz,CDCl3,ppm)δ＝159.2,147.8,144.9,139.5,129.7,128.8,127.7,127.4,122.1,121.4,117.2,114.0,48.9.MS(EI,70eV)m/z:275,91,77,65,51.HRMS(ESI)(m/z):calcd for C19H17NONa[M+Na]+:298.1202,found:298.1210。
example 17: synthesis of N-benzyl- [1,1' -biphenyl ] -4-amine
A three-necked round-bottomed flask was taken, and 7mL of dimethyl sulfoxide, 53mg (0.50mmol) of benzaldehyde, 101mg (0.6mmol) of 4-phenylaniline and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate were added thereto, and the mixture was stirred at room temperature under a current of 10mA for electrochemical reaction for 6 hours while using a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 62%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.59(m,2H),7.50(m,2H),7.43(m,6H),7.33(m,2H),6.76(m,2H),4.42(s,2H),4.27(s,1H).13C NMR(126MHz,CDCl3,ppm)δ＝147.5,141.3,139.3,130.5,128.7,128.7,128.0,127.6,127.4,126.4,126.1,113.2,48.4.MS(EI,70eV)m/z:259,115,91,65,51.HRMS(ESI)(m/z):calcd for C19H17NNa[M+Na]+:282.1253,found:282.1258。
example 18: synthesis of N-benzyl-4-chloroaniline
A three-necked round-bottomed flask was taken, and charged with 5mL of dimethyl sulfoxide, 53mg (0.50mmol) of benzaldehyde, 76mg (0.6mmol) of 4-chloroaniline and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and the mixture was stirred at room temperature under a current of 10mA for electrochemical reaction for 7 hours while using a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 65%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.38(d,J＝4.4Hz,4H),7.32(dd,J＝8.4,4.1Hz,1H),7.14(m,2H),6.58(m,2H),4.33(s,2H).13C NMR(126MHz,CDCl3,ppm)δ＝146.6,138.9,129.1,128.7,127.5,127.4,122.2,114.0,48.4.MS(EI,70eV)m/z:217,91,75,65,51.HRMS(ESI)(m/z):calcd for C13H13ClN[M+H]+:218.0731,found:218.0721。
example 19: synthesis of N-benzyl-3, 5-dimethylaniline
A three-necked round-bottomed flask was taken, and charged with 5mL of dimethyl sulfoxide, 53mg (0.50mmol) of benzaldehyde, 73mg (0.6mmol) of 3, 5-dimethylaniline and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and stirred at room temperature under a current of 10mA for electrochemical reaction for 5 hours while using a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 98%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.39(dt,J＝12.2,7.3Hz,4H),7.31(t,J＝6.9Hz,1H),6.44(s,1H),6.34(s,2H),4.34(s,2H),3.91(s,1H),2.27(s,6H).13CNMR(126MHz,CDCl3,ppm)δ＝148.2,139.6,139.0,128.6,127.6,127.2,119.7,110.8,48.4,21.5.MS(EI,70eV)m/z:211,91,77,64,39.HRMS(ESI)(m/z):calcd for C15H17NNa[M+Na]+:234.1253,found:234.1258。
example 20: synthesis of N-benzyl-3, 5-dimethoxyaniline
A three-necked round-bottomed flask was taken, and 6mL of dimethyl sulfoxide, 53mg (0.50mmol) of benzaldehyde, 92mg (0.6mmol) of 3, 5-dimethoxyaniline, and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate were added thereto, and the mixture was stirred at room temperature and 8mA current for electrochemical reaction for 6 hours with a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 30%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.38(m,5H),7.31(m,1H),5.93(t,J＝2.1Hz,1H),5.87(d,J＝2.1Hz,2H),4.33(s,2H),3.87(s,1H),3.76(s,6H).13C NMR(126MHz,CDCl3,ppm)δ＝161.7,150.1,139.2,128.7,127.6,127.3,91.8,89.9,55.2,48.4.MS(EI,70eV)m/z:243,166,91,73,65.HRMS(ESI)(m/z):calcd for C15H17NO2Na[M+Na]+:266.1152,found:266.1161。
example 21: synthesis of N-benzylcyclohexylamine
A three-necked round-bottomed flask was charged with 5mL of dimethyl sulfoxide, 53mg (0.50mmol) of benzaldehyde, 149mg (1.5mmol) of cyclohexylamine and 170mg (0.5mmol) of tetra-n-butylammonium hydrogensulfate, and the mixture was electrochemically reacted at room temperature under stirring at 8mA current for 6 hours with a carbon rod as an anode and a carbon rod as a cathode. After the reaction is finished, 10mL of ethyl acetate is added to quench the reaction, 5mL of saturated saline solution is added to wash the reaction, an organic phase is collected after layering, the water phase is extracted for 3 times by ethyl acetate, the amount of ethyl acetate used for each time is 5mL, the organic phases are combined, anhydrous sodium sulfate is added to dry the mixture, the solvent is removed by reduced pressure distillation, and the product is obtained by column chromatography, wherein the yield is 69%.
The characterization data of the product are:1H NMR(500MHz,CDCl3,ppm)δ＝7.34(d,J＝4.4Hz,4H),7.28(dd,J＝8.4,3.9Hz,1H),3.84(s,2H),2.52(ddd,J＝10.4,6.6,3.8Hz,1H),1.95(d,J＝10.1Hz,3H),1.77(m,2H),1.64(d,J＝11.8Hz,1H),1.21(m,6H).13C NMR(126MHz,CDCl3,ppm)δ＝140.8,128.4,128.2,126.8,56.2,51.0,33.5,26.2,25.0.MS(EI,70eV)m/z:189,158,146,132,91.HRMS(ESI)(m/z):calcd for C13H19N[M+Na]+:250.0838,found:250.0833。
as can be seen from the above examples 1 to 21: the reaction is applicable to various types of substrates, which shows that the reaction functional group has good tolerance, so the application range is wide; the reaction yield is high, and most of the reaction yield is up to more than 90%; the raw materials, the solvent and the like used in the reaction are cheap and easy to obtain, the reaction process is fast, and the operation is simple and safe, so that the method has the potential of large-scale production.
In summary, the beneficial effects of the invention include: the invention does not use metal catalyst and external oxidant, is green and environment-friendly and has low price; the reaction system, the reaction raw materials, the electrolyte and the hydrogen source used in the invention have low price, are nontoxic and tasteless, have simple and convenient post-treatment and are suitable for industrial production; the method has the advantages of mild reaction conditions, simple operation and high yield.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical fields are included in the scope of the present invention.
Claims (10)
1. A method for the construction of secondary amines by electrochemical reductive amination of aldehydes comprising the steps of: taking an aldehyde compound shown in a formula (I) and an amine compound shown in a formula (II) as raw materials, and preparing a secondary amine compound shown in a formula (III) through electrochemical cathode reduction reaction in an electrolytic system; the electrolytic system comprises an electrolyte, a solvent, an anode and a cathode;
in the formula, R1And R2Are each independently selected from alkyl, aryl and heteroaryl.
2. The method of claim 1, wherein: r1Selected from aryl groups including unsubstituted phenyl, alkylphenyl, alkoxyphenyl, benzyloxyphenyl or halophenyl;
R2the aryl group includes unsubstituted phenyl, alkylphenyl, alkoxyphenyl or benzyloxyphenyl.
3. The method of claim 1, wherein the electrolyte comprises at least one of tetra-n-butylammonium tetrafluoroborate, tetra-n-butylammonium acetate, tetra-n-butylammonium hydrogen sulfate, or tetra-n-butylammonium hexafluorophosphate.
4. The method according to claim 1, wherein the molar ratio of the aldehyde compound to the electrolyte is 1 (1-2).
5. The method according to claim 1, wherein the molar ratio of the aldehyde compound to the amine compound is 1 (1-3).
6. The method of claim 1, wherein the solvent comprises at least one of dimethylsulfoxide, ethanol, N-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, and 1, 4-dioxane.
7. The method of claim 1, wherein the anode and cathode each comprise a carbon rod.
8. The method of claim 1, wherein the direct current used for the reaction is (5 to 20) mA.
9. The method according to claim 1, wherein the reaction temperature is (25-40) ℃ and the reaction time is (3-18) hours.
10. The method of claim 1, wherein the compound containing a secondary amine skeleton is obtained by column chromatography after quenching, washing, extraction and concentration after the reaction is finished.
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