CN109824585B - Method for preparing 1-aryl-2-quinolyl ethanol compound under catalysis of acidic ionic liquid - Google Patents
Method for preparing 1-aryl-2-quinolyl ethanol compound under catalysis of acidic ionic liquid Download PDFInfo
- Publication number
- CN109824585B CN109824585B CN201910248030.7A CN201910248030A CN109824585B CN 109824585 B CN109824585 B CN 109824585B CN 201910248030 A CN201910248030 A CN 201910248030A CN 109824585 B CN109824585 B CN 109824585B
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- aryl
- acidic ionic
- quinolyl
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Quinoline Compounds (AREA)
Abstract
The invention discloses a method for preparing a 1-aryl-2-quinolyl ethanol compound by catalysis of an acidic ionic liquid, belonging to the technical field of preparation of chemical materials. The invention discloses a method for preparing a 1-aryl-2-quinolyl ethanol compound under the catalysis of an acidic ionic liquid, which takes aromatic aldehyde and 2-methylquinoline as raw materials, and prepares the 1-aryl-2-quinolyl ethanol compound under the catalysis of the acidic ionic liquid catalyst, wherein the molar weight of the acidic ionic liquid catalyst is 8-13% of that of the 2-methylquinoline, and the molar ratio of the aromatic aldehyde to the 2-methylquinoline as a reaction raw material is 1: 1. according to the invention, the specific acidic ionic liquid is selected as the catalyst to catalyze the reaction of the aromatic aldehyde and the 2-methylquinoline to generate the 1-aryl-2-quinolyl ethanol compound, so that the using amount and the loss amount of the catalyst can be effectively reduced, the catalyst is more in recycling times, and the product is simple to separate and purify.
Description
Technical Field
The invention belongs to the technical field of chemical material preparation, and particularly relates to a method for preparing a 1-aryl-2-quinolyl ethanol compound by catalyzing aromatic aldehyde and 2-methylquinoline to react by using an acidic ionic liquid.
Background
Quinoline heterocyclic derivatives widely exist in the nature as alkaloids, are organic compounds with important biological activity and pharmacological activity, and are widely applied to the fields of pharmaceutical chemistry and agricultural chemistry. The compounds have the effects of resisting bacteria, allergy, malaria, tumor, cancer, hypertension, depression, memory and the like, are also used as HIV virus inhibitors, are also used as efficient catalysts or ligands, and play an important role in chiral molecule synthesis. In addition, the quinoline heterocyclic derivative also has important application in the field of fluorescent and phosphorescent probe molecules.
1-aryl-2-quinolylethanol compounds have a wide range of pharmaceutical activities as a quinolyl-containing azaheterocyclic aromatic hydrocarbon derivative. The preparation method is generally realized by the condensation reaction of various aromatic aldehydes and 2-methylquinoline, and a series of 1-aryl-2-quinolyl ethanol compounds can be prepared without using a catalyst in the preparation process, such as Shouchun et al by using high-temperature water as a reaction solvent and adding the catalyst. The method has the advantages of simple reaction process and no pollution, but also has the defects of low product yield, high reaction temperature, high reaction pressure, complex product purification process and the like (research on the reaction of 2-methylquinoline and 2-methylpyridine with aromatic aldehyde in high-temperature water [ J ], organic chemistry, 2017, 27: 2159-2164).
The acidic ionic liquid, especially the Bronsted acidic ionic liquid which is relatively stable to water and air, is applied to the process of preparing the 1, 3-bis (2-quinolyl) propane compound by the reaction of aromatic aldehyde and 2-methylquinoline due to the characteristics of multiple types, high density of active sites, uniform intensity distribution, difficult loss of the active sites and the like. For example, Liuchenjiang and the like react aromatic aldehyde and 2-methylquinoline compounds at 120 ℃ for 48 hours in solvent-free or toluene by using Bronsted acidic ionic liquid 1-ethyl-3-butylimidazole p-toluenesulfonate as a catalyst to prepare a series of 1, 3-bis (2-quinolyl) propane compounds. The method has the advantages of simple and easy operation, high yield, and partial reaction can be carried out under the condition of no solvent (
Synthesis of 1, 3-di (2-quinolyl) propane compound [ J ] by catalyzing reaction of aromatic aldehyde and 2-methylquinoline with acidic ionic liquid]Higher school chemistry, 2015, 36 (9): 1702-1706). However, the acidic ionic liquid catalyst is used in a large amount (20 mol percent) in the reaction, and the purification process of the product in the method is still complicated, and the separation is carried out by using column chromatography.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defects of the existing preparation process of the 1-aryl-2-quinolyl ethanol compound and provides a method for preparing the 1-aryl-2-quinolyl ethanol compound by using acidic ionic liquid as a catalyst. According to the invention, the specific acidic ionic liquid is selected as the catalyst to catalyze the reaction of the aromatic aldehyde and the 2-methylquinoline to generate the 1-aryl-2-quinolyl ethanol compound, so that the using amount and the loss amount of the catalyst can be effectively reduced, the catalyst is more in recycling times, and the product is simple to separate and purify.
2. Technical scheme
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention relates to a method for preparing a 1-aryl-2-quinolyl ethanol compound under the catalysis of an acidic ionic liquid, which takes aromatic aldehyde and 2-methylquinoline as raw materials to prepare the 1-aryl-2-quinolyl ethanol compound under the catalysis of the acidic ionic liquid catalyst as follows:
furthermore, the molar amount of the acidic ionic liquid catalyst is 8-13% of the molar amount of the 2-methylquinoline used.
Further, the molar ratio of the aromatic aldehyde and the 2-methylquinoline as the raw materials for the reaction is 1: 1.
further, the aromatic aldehyde is any one of benzaldehyde, p-chlorobenzaldehyde, p-methoxybenzaldehyde, p-nitrobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde and p-fluorobenzaldehyde.
Furthermore, the specific operation is as follows: respectively adding reaction raw materials, namely aromatic aldehyde, 2-methylquinoline and a catalyst into a reaction container containing a reaction solvent, carrying out heating reflux reaction under the protection of nitrogen, cooling to room temperature after the reaction is finished, adding ethyl acetate to precipitate crystals, carrying out suction filtration, and washing and vacuum drying the obtained filter residue to obtain the 1-aryl-2-quinolyl ethanol compound.
Furthermore, the reaction solvent is water, and the volume of the reaction solvent is 2-4 times of that of the 2-methylquinoline in millimole.
Furthermore, the heating reflux reaction time is 43-72 min, and filter residues obtained by suction filtration are washed for 3 times by ethyl acetate.
Furthermore, ethyl acetate is distilled from the filtrate obtained by suction filtration, and then the ethyl acetate is directly added into the reaction raw material for the next reaction.
Further, the filtrate after rotary evaporation of ethyl acetate can be reused for at least 5 times.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the method for preparing the 1-aryl-2-quinolyl ethanol compound under the catalysis of the acidic ionic liquid, aromatic aldehyde and 2-methylquinoline are used as raw materials, a specific acidic ionic liquid is selected as a catalyst, and the activity of the catalyst for preparing the 1-aryl-2-quinolyl ethanol compound under the catalysis of the catalyst is high, so that the yield of the obtained product is improved; meanwhile, the catalyst has less use amount and less loss amount in the use process, thereby being beneficial to improving the recycling performance of the catalyst.
(2) According to the method for preparing the 1-aryl-2-quinolyl ethanol compound under the catalysis of the acidic ionic liquid, the usage amount of the catalyst, the reaction time, the addition amount of the reaction solvent and the like are optimally designed, so that the reaction time is shortened, the yield of the obtained product is further improved, and the side reaction can be effectively prevented, so that the purity of the obtained product is improved.
(3) According to the method for preparing the 1-aryl-2-quinolyl ethanol compound under the catalysis of the acidic ionic liquid, the specific acidic ionic liquid catalyst is selected, and the process parameters are optimally designed, so that the utilization rate of reaction raw materials can be improved, the method is economical and efficient, the catalyst can be recycled for at least 5 times, and the yield reduction range of the obtained product in the recycling process is small.
(4) The method for preparing the 1-aryl-2-quinolyl ethanol compound under the catalysis of the acidic ionic liquid has the advantages of simple, convenient, green and economic whole preparation process, convenience for industrial large-scale production, simple purification process of the product and no need of column chromatography for separation.
Drawings
FIGS. 1 to 7 show the results of activity reproducibility tests of the catalytic systems of examples 1 to 7, respectively.
Detailed Description
The invention relates to a method for preparing a 1-aryl-2-quinolyl ethanol compound under the catalysis of an acidic ionic liquid, which takes aromatic aldehyde and 2-methylquinoline as raw materials, and carries out heating reflux reaction under the catalysis of an acidic ionic liquid catalyst and under the protection of nitrogen to catalytically prepare the 1-aryl-2-quinolyl ethanol compound, wherein the chemical reaction formula is as follows:
wherein: the molar ratio of the aromatic aldehyde to the 2-methylquinoline in the reaction is 1: 1, the molar weight of an acidic ionic liquid catalyst is 8-13% of that of 2-methylquinoline, the volume of reaction solvent water in milliliters is 2-4 times that of 2-methylquinoline in millimole, the reflux reaction time is 43-72 min, after the reaction is finished, cooling to room temperature, adding ethyl acetate, separating out crystals, carrying out suction filtration, washing obtained filter residues with ethyl acetate, drying in vacuum to obtain a 1-aryl-2-quinolyl ethanol compound, wherein the yield is 51-86%, after ethyl acetate is removed from obtained filtrate by rotary evaporation, directly adding reaction raw materials to carry out the next reaction, and the compound can be reused for at least 5 times without obvious reduction of the yield of the obtained product. The structural formula of the acidic ionic liquid is as follows:
aiming at the defects of large catalyst use amount and loss amount, relatively poor recycling performance, complex product purification process and the like existing in the existing 1-aryl-2-quinolyl ethanol compound preparation process, the invention selects the specific acidic ionic liquid as the catalyst, thereby effectively improving the catalytic efficiency of the catalyst, and the catalytic activity of the catalyst is high, so that the raw material consumption can be reduced, and the yield of the obtained product can be improved. Meanwhile, the catalyst has less usage amount and loss amount in the using process, the recycling performance is better, the catalyst can be recycled for at least 5 times, and the yield reduction amplitude of the obtained product in the recycling process of the catalyst is smaller. In addition, the reaction conditions are mild, the product is simple to separate and purify, the utilization rate of the raw materials is high, and the process parameters such as the usage amount of the catalyst, the reaction time and the like are optimized, so that the reaction time is shortened, the yield of the obtained product is further improved, the side reaction can be effectively prevented, and the purity of the obtained product is improved.
The aromatic aldehyde is any one of benzaldehyde, p-chlorobenzaldehyde, p-methoxybenzaldehyde, p-nitrobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde and p-fluorobenzaldehyde. The preparation method of the acidic ionic liquid catalyst of the present invention is described in the related literature (N, N-disulfo-1, 1, 3, 3-tetramethylguanidium carboxylateinic acids salts as reusable biogenic catalysts for multiple component synthesis of carboxylic acids [ alpha ] alcohols and carboxylic acids [ alpha ] acid derivatives [ J ], Journal of Molecular Liquids, 2017, 225: 585-591).
The essential features and the remarkable effects of the present invention can be obtained from the following examples, which are not intended to limit the present invention in any way, and those skilled in the art who have the benefit of this disclosure will be able to make numerous insubstantial modifications and adaptations to the present invention without departing from the scope of the present invention. The invention is further illustrated by the following specific embodiments in which the hydrogen and carbon nuclear magnetic resonance characterization of the reaction products in the examples is by an Avance III 500MHz nuclear magnetic resonance instrument from Bruker, Germany; the melting point of the reaction product was determined by the capillary method.
Example 1:
1.0mmol of m-nitrobenzaldehyde, 1.0mmol of 2-methylquinoline and 0.08mmol of acidic ionic liquid catalyst were added to a 100ml four-necked flask with a stirrer and a condenser, respectively, containing 2ml of water. Heating and refluxing for 46min under the protection of nitrogen, detecting by TLC (thin-plate chromatography), cooling to room temperature, adding 1ml ethyl acetate, separating out crystals, performing suction filtration, washing filter residue with ethyl acetate (2ml multiplied by 3), and performing vacuum drying to obtain 1- (3-nitrophenyl) -2- (quinoline-2-yl) ethanol with the yield of 85%, wherein m-nitrobenzaldehyde and 2-methylquinoline are directly added into the filtrate after ethyl acetate is evaporated in a rotary manner for recycling.
1- (3-Nitrophenyl) -2- (quinolin-2-yl) ethanol obtained in this example: m.p.154-156 ℃;1H NMR(500MHz，CDCl3):＝3.23～3.38(m，2H)，5.31(dd，J＝3.0Hz，J＝9.9Hz，1H)，6.46(br，1H)，7.17(d，J＝3.0Hz，1H)，7.45(t，J＝9.0Hz，1H)，7.50(t，J＝9.0Hz，1H)，7.64(t，J＝9.0Hz，1H)，7.75(dd，J＝4.8Hz，J＝9.0Hz，2H)，8.04～8.11(m，3H)，8.25(s，1H)。
the reaction is carried out by taking the example as a probe reaction, an activity repeatability test of a reaction catalytic system consisting of reaction solvent water and acidic ionic liquid is carried out, the catalytic system is repeatedly used for 6 times, and the yield change of the product 1- (3-nitrophenyl) -2- (quinolin-2-yl) ethanol is shown in figure 1.
Example 2:
1.0mmol of p-nitrobenzaldehyde, 1.0mmol of 2-methylquinoline and 0.08mmol of acidic ionic liquid catalyst were added to a 100ml four-necked flask with a stirrer and a condenser, respectively, containing 2ml of water. Heating and refluxing for reaction for 43min under the protection of nitrogen, detecting by TLC (thin-plate chromatography), cooling to room temperature, adding 1ml of ethyl acetate, separating out crystals, performing suction filtration, washing filter residues by ethyl acetate (2ml multiplied by 3), and performing vacuum drying to obtain 1- (4-nitrophenyl) -2- (quinoline-2-yl) ethanol with the yield of 86%, wherein after ethyl acetate is removed by rotary evaporation from filtrate, p-nitrobenzaldehyde and 2-methylquinoline are directly added for recycling.
1- (4-Nitrophenyl) -2- (quinolin-2-yl) ethanol obtained in this example: m.p.151-153 ℃;1H NMR(500MHz，CDCl3):＝3.25～3.37(m，2H)，5.42(br，1H)，6.16(d，J＝6.0Hz，1H)，7.19(d，J＝9.1Hz，1H)，7.58(d，J＝8.6Hz，1H)，7.61(d，J＝9.8Hz，1H)，7.75(t，J＝9.1Hz，1H)，7.81(d，J＝9.1Hz，1H)，8.04(d，J＝9.1Hz，2H)，8.12(d，J＝9.1Hz，1H)，8.20(d，J＝9.8Hz，1H)。
using this example as a probe reaction, an activity repeatability test of a reaction catalyst system composed of reaction solvent water and acidic ionic liquid was performed, the catalyst system was reused 6 times, and the yield change of the product 1- (4-nitrophenyl) -2- (quinolin-2-yl) ethanol is shown in FIG. 2.
Example 3:
1.0mmol of o-nitrobenzaldehyde, 1.0mmol of 2-methylquinoline and 0.09mmol of acidic ionic liquid catalyst were added to a 100ml four-necked flask with a stirrer and a condenser, respectively, containing 2ml of water. Heating and refluxing for reaction for 57min under the protection of nitrogen, detecting by TLC (thin-plate chromatography), cooling to room temperature, adding 1ml of ethyl acetate, separating out crystals, performing suction filtration, washing filter residues by ethyl acetate (2ml multiplied by 3), and performing vacuum drying to obtain 1- (2-nitrophenyl) -2- (quinoline-2-yl) ethanol with the yield of 75%, wherein after ethyl acetate is removed by rotary evaporation from filtrate, o-nitrobenzaldehyde and 2-methylquinoline are directly added for recycling.
1- (2-Nitrophenyl) -2- (quinolin-2-yl) ethanol obtained in this example: m.p.162-164 ℃;1H NMR(500MHz，CDCl3):＝3.27(s，1H)，3.53(d，J＝15.0Hz，1H)，5.76(d，J＝9.0Hz，1H)，6.62(br，1H)，7.28(d，J＝8.1Hz，1H)，7.39(t，J＝8.1Hz，1H)，7.57(d，J＝8.1Hz，1H)，7.64(t，J＝7.5Hz，1H)，7.79(d，J＝8.1Hz，1H)，7.82(d，J＝8.1Hz，1H)，7.97(dd，J＝8.1Hz，J＝1.2Hz，2H)，8.02(d，J＝7.8Hz，1H)，8.16(d，1H)。
using this example as a probe reaction, an activity repeatability test of a reaction catalyst system composed of reaction solvent water and acidic ionic liquid was performed, the catalyst system was reused 6 times, and the yield of the product 1- (2-nitrophenyl) -2- (quinolin-2-yl) ethanol was changed as shown in FIG. 3.
Example 4:
1.0mmol of benzaldehyde, 1.0mmol of 2-methylquinoline and 0.10mmol of acidic ionic liquid catalyst were added to a 100ml four-necked flask with a stirrer and a condenser, respectively, containing 3ml of water. Heating and refluxing for reaction for 64min under the protection of nitrogen, detecting by TLC (thin-plate chromatography), cooling to room temperature, adding 1ml of ethyl acetate, separating out crystals, performing suction filtration, washing filter residues by ethyl acetate (2ml multiplied by 3), and performing vacuum drying to obtain 1-phenyl-2- (quinoline-2-yl) ethanol with the yield of 68%, wherein benzaldehyde and 2-methylquinoline are directly added into the filtrate after ethyl acetate is removed by rotary evaporation for recycling.
1-phenyl-2- (quinoline) obtained in this example-2-yl) ethanol: m.p.123-125 ℃;1H NMR(500MHz，CDCl3):＝3.29～3.40(m，2H)，5.36(dd，J＝5.1Hz，J＝7.4Hz，1H)，6.20(br，1H)，7.25(d，J＝8.6Hz，1H)，7.31(d，J＝7.4Hz，1H)，7.38(t，J＝7.4Hz，2H)，7.50(d，J＝8.8Hz，2H)，7.56(d，J＝7.8Hz，1H)，7.76(t，J＝8.5Hz，1H)，7.87(d，J＝8.1Hz，1H)，8.11(t，J＝8.5Hz，2H)。
using this example as a probe reaction, an activity repeatability test of a reaction catalyst system composed of reaction solvent water and acidic ionic liquid was performed, the catalyst system was reused 7 times, and the yield change of the product 1-phenyl-2- (quinolin-2-yl) ethanol is shown in FIG. 4.
Example 5:
1.0mmol of p-methoxybenzaldehyde, 1.0mmol of 2-methylquinoline and 0.11mmol of acidic ionic liquid catalyst were added to a 100ml four-necked flask with a stirrer and a condenser, respectively, containing 4ml of water. Heating and refluxing for reaction for 67min under the protection of nitrogen, detecting by TLC (thin-plate chromatography), cooling to room temperature, adding 2ml of ethyl acetate, separating out crystals, performing suction filtration, washing filter residues by ethyl acetate (2ml multiplied by 3), and performing vacuum drying to obtain 1- (4-methoxyphenyl) -2- (quinoline-2-yl) ethanol with the yield of 56%, wherein p-methoxybenzaldehyde and 2-methylquinoline are directly added into the filtrate after ethyl acetate is evaporated in a rotary manner for recycling.
1- (4-methoxyphenyl) -2- (quinolin-2-yl) ethanol obtained in this example: m.p.135-137 ℃;1H NMR(500MHz，CDCl3):＝3.31(m，2H)，3.76(s，3H)，5.13(dd，J＝2.5Hz，J＝8.8Hz，1H)，5.95(br，1H)，6.47(d，J＝8.1Hz，2H)，7.22(d，J＝7.5Hz，1H)，7.38(t，J＝7.5Hz，2H)，7.52(t，J＝6.5Hz，1H)，7.67(t，J＝6.5Hz，1H)，7.74(d，J＝7.1Hz，1H)，8.08(d，J＝7.5Hz，2H)。
using this example as a probe reaction, an activity repeatability test of a reaction catalyst system composed of reaction solvent water and acidic ionic liquid was performed, the catalyst system was reused 7 times, and the yield change of the product 1- (4-methoxyphenyl) -2- (quinolin-2-yl) ethanol is shown in FIG. 5.
Example 6:
1.0mmol of p-fluorobenzaldehyde, 1.0mmol of 2-methylquinoline and 0.11mmol of acidic ionic liquid catalyst were respectively put into a 100ml four-necked flask with a stirrer and a condenser containing 2ml of water. Heating and refluxing for reaction for 64min under the protection of nitrogen, detecting by TLC (thin-plate chromatography), cooling to room temperature, adding 1ml of ethyl acetate, separating out crystals, performing suction filtration, washing filter residues by ethyl acetate (2ml multiplied by 3), and performing vacuum drying to obtain 1- (4-fluorophenyl) -2- (quinoline-2-yl) ethanol with the yield of 51%, wherein p-fluorobenzaldehyde and 2-methylquinoline are directly added into the filtrate after ethyl acetate is removed by rotary evaporation for recycling.
1- (4-fluorophenyl) -2- (quinolin-2-yl) ethanol obtained in this example: m.p.132-134 ℃;1H NMR(500MHz，CDCl3):＝3.32(m，1H)，5.34(m，1H)，7.09(m，2H)，7.26(m，2H)，7.46(t，J＝5.0Hz，2H)，7.58(dd，J＝10.0Hz，J＝4.9Hz，1H)，7.79(dd，J＝10.0Hz，J＝4.9Hz，1H)，7.84(t，J＝10.0Hz，1H)，8.14(m，2H)。
using this example as a probe reaction, an activity repeatability test of a reaction catalyst system composed of reaction solvent water and acidic ionic liquid was performed, the catalyst system was reused 6 times, and the yield of the product 1- (4-fluorophenyl) -2- (quinolin-2-yl) ethanol was changed as shown in FIG. 6.
Example 7:
1.0mmol of p-chlorobenzaldehyde, 1.0mmol of 2-methylquinoline and 0.13mmol of acidic ionic liquid catalyst were added to a 100ml four-necked flask with a stirrer and a condenser, respectively, containing 2ml of water. Heating and refluxing for reaction for 72min under the protection of nitrogen, detecting by TLC (thin-plate chromatography), cooling to room temperature, adding 1ml of ethyl acetate, separating out crystals, performing suction filtration, washing filter residues by ethyl acetate (2ml multiplied by 3), and performing vacuum drying to obtain 1- (4-chlorophenyl) -2- (quinoline-2-yl) ethanol with the yield of 54%, wherein after ethyl acetate is removed by rotary evaporation from the filtrate, p-chlorobenzaldehyde and 2-methylquinoline are directly added for recycling.
1- (4-chlorophenyl) -2- (quinolin-2-yl) ethanol obtained in this example: m.p.141-143 ℃;1H NMR(500MHz，CDCl3):＝3.33(d，J＝6.4Hz，2H)，5.38(t，J＝6.4Hz，1H)，6.42(br，1H)，7.25(d，J＝8.4Hz，1H)，7.39(d，J＝8.4Hz，2H)，7.50(d，J＝8.4Hz，2H)，7.61(t，J＝7.1Hz，1H)，7.80(t，J＝7.1Hz，1H)，7.87(d，J＝8.4Hz，1H)，8.13(d，J＝8.4Hz，1H)，8.18(d，J＝8.4Hz，1H)。
using this example as a probe reaction, an activity repeatability test of a reaction catalyst system composed of water as a reaction solvent and an acidic ionic liquid was performed, the catalyst system was reused 6 times, and the yield of the product 1- (4-chlorophenyl) -2- (quinolin-2-yl) ethanol was changed as shown in FIG. 7.
As can be seen in conjunction with fig. 1-7: if the reduction of the yield of the reaction product is 5%, the catalytic system consisting of the reaction solvent water and the acidic ionic liquid catalyst can be reused for at least 5 times without any treatment, wherein the catalytic system can be reused for 6 times when benzaldehyde and p-methoxybenzaldehyde are used as reaction raw materials.
Claims (8)
1. A method for preparing a 1-aryl-2-quinolyl ethanol compound under the catalysis of acidic ionic liquid is characterized by comprising the following steps: the method takes aromatic aldehyde and 2-methylquinoline as raw materials to prepare the 1-aryl-2-quinolyl ethanol compound under the catalysis of the following acidic ionic liquid catalyst:
the aromatic aldehyde is any one of benzaldehyde, p-chlorobenzaldehyde, p-methoxybenzaldehyde, p-nitrobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde and p-fluorobenzaldehyde.
2. The method for preparing the 1-aryl-2-quinolyl ethanol compound under the catalysis of the acidic ionic liquid as claimed in claim 1, wherein: the molar weight of the acidic ionic liquid catalyst is 8-13% of the molar weight of the 2-methylquinoline.
3. The method for preparing the 1-aryl-2-quinolyl ethanol compound under the catalysis of the acidic ionic liquid as claimed in claim 1, wherein: the molar ratio of the aromatic aldehyde to the 2-methylquinoline as the raw materials for the reaction is 1: 1.
4. a method for the acidic ionic liquid catalyzed preparation of 1-aryl-2-quinolinylethanol compounds as claimed in any one of claims 1 to 3, characterized in that it is operated: respectively adding reaction raw materials, namely aromatic aldehyde, 2-methylquinoline and a catalyst into a reaction container containing a reaction solvent, carrying out heating reflux reaction under the protection of nitrogen, cooling to room temperature after the reaction is finished, adding ethyl acetate to precipitate crystals, carrying out suction filtration, and washing and vacuum drying the obtained filter residue to obtain the 1-aryl-2-quinolyl ethanol compound.
5. The method for preparing 1-aryl-2-quinolyl ethanol compounds by catalysis of acidic ionic liquid as claimed in claim 4, wherein: the reaction solvent is water, and the volume of the reaction solvent is 2-4 times of that of 2-methylquinoline in millimole.
6. The method for preparing 1-aryl-2-quinolyl ethanol compounds by catalysis of acidic ionic liquid as claimed in claim 4, wherein: the heating reflux reaction time is 43-72 min, and filter residues obtained by suction filtration are washed for 3 times by ethyl acetate.
7. The method for preparing 1-aryl-2-quinolyl ethanol compounds by catalysis of acidic ionic liquid as claimed in claim 6, wherein: and (4) rotatably evaporating ethyl acetate from the filtrate obtained by suction filtration, and directly adding reaction raw materials to carry out the next reaction.
8. The method for preparing 1-aryl-2-quinolyl ethanol compounds catalyzed by acidic ionic liquid as claimed in claim 7, wherein: the filtrate after rotary evaporation of ethyl acetate can be reused for at least 5 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910248030.7A CN109824585B (en) | 2019-03-29 | 2019-03-29 | Method for preparing 1-aryl-2-quinolyl ethanol compound under catalysis of acidic ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910248030.7A CN109824585B (en) | 2019-03-29 | 2019-03-29 | Method for preparing 1-aryl-2-quinolyl ethanol compound under catalysis of acidic ionic liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109824585A CN109824585A (en) | 2019-05-31 |
| CN109824585B true CN109824585B (en) | 2020-08-14 |
Family
ID=66873688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910248030.7A Active CN109824585B (en) | 2019-03-29 | 2019-03-29 | Method for preparing 1-aryl-2-quinolyl ethanol compound under catalysis of acidic ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109824585B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615763B (en) * | 2019-08-26 | 2023-04-07 | 南方医科大学 | Green synthesis method of hydroxyquinoline compound |
-
2019
- 2019-03-29 CN CN201910248030.7A patent/CN109824585B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109824585A (en) | 2019-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Guo et al. | The development of double axially chiral phosphoric acids and their catalytic transfer hydrogenation of quinolines | |
| Zhao et al. | Organocatalytic enantioselective aminosulfenylation of α, β‐unsaturated aldehydes | |
| Aprile et al. | New ionic liquid-modified silica gels as recyclable materials for l-proline-or H–Pro–Pro–Asp–NH 2-catalyzed aldol reaction | |
| Wang et al. | Enantioselective hydrogenation of α-ketoamides over Pt/Al2O3 modified by cinchona alkaloids | |
| CN111822047B (en) | Method for synthesizing indole derivatives through magnetic mesoporous polymeric ionic liquid supported catalysis | |
| CN109824585B (en) | Method for preparing 1-aryl-2-quinolyl ethanol compound under catalysis of acidic ionic liquid | |
| Rostami et al. | [C 6 (MIm) 2] 2 W 10 O 32. 2H 2 O: A novel and powerful catalyst for the synthesis of 4-arylidene-2-phenyl-5 (4)-oxazolones under ultrasonic condition | |
| CN103483306B (en) | Method for preparing 2-amino-2-chromene derivatives by using polyamino ionic liquid as catalyst | |
| Janus et al. | Chiral protic imidazolium salts with a (−)-menthol fragment in the cation: synthesis, properties and use in the Diels–Alder reaction | |
| CN102351777B (en) | Preparation method for chiral 3-hydroxyl-3-methylene nitro indole-2-ketone derivative | |
| Chinnappan et al. | An efficient and recyclable PVDF-IL nanofiber composite for the reduction of functionalized carbonyl compounds | |
| Guo et al. | Synthesis of quinoline derivatives from anilines and aldehydes catalyzed by Cp2ZrCl2 and recyclable Cp2ZrCl2/MCM-41 system | |
| Kiasat et al. | n-Propyl-4-aza-1-azoniabicyclo [2.2. 2] octane chloride-SBA-15 (SBA-DABCO) as basic mesoporous catalyst for the synthesis of 1, 4-dihydropyridine hetrocyclic compounds | |
| Bugarin et al. | MgI 2-accelerated enantioselective Morita–Baylis–Hillman reactions of cyclopentenone utilizing a chiral DMAP catalyst | |
| CN107162970B (en) | Method for synthesizing 2-aryl-2, 3-dihydro-4 (1H) -quinolinone derivative under catalysis of high-acidity ionic liquid | |
| Wang et al. | Synthesis, characterization and ethylene oligomerization of nickel complexes bearing N-(2-(1 H-benzo [d] imidazol-2-yl) quinolin-8-yl) benzamide derivatives | |
| CN107382961B (en) | Method for preparing 2-thiocarbonyl-2H-thiopyran derivative by chitosan catalysis one-pot method | |
| CN105170180A (en) | Application of 4,5-methylene-L-proline as catalyst in direct asymmetric Aldol reaction | |
| CN106238098B (en) | A kind of preparation method and its catalyst for preparing of 1,2,4,5- tetra- substituted ramification of imidazole | |
| Li et al. | Synergistic catalysis of bifunctional polyacrylonitrile fiber for the synthesis of (E)-α, β-unsaturated esters from aldehydes by decarboxylative Doebner–Knoevenagel reaction | |
| CN103193716A (en) | Method for preparing 3,4-dihydropyrimidine-2 (1H)-ketone derivative via catalysis of acidic ionic liquid | |
| CN111574528B (en) | Method for preparing medical intermediate pyranoquinoline derivative | |
| Fang et al. | Enantioselectivity switch in asymmetric Michael addition reactions using phosphonium salts | |
| CN109970659B (en) | Method for preparing benzimidazole and quinazoline compounds by adopting supported nickel catalyst | |
| CN114539319B (en) | Chiral phosphine-dicyclophosphoramidite ligand and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |