KR20160115239A - Heterogeneous catalyst for production of (E)-1,3-diaryl propenes and preparation method of (E)-1,3-diaryl propenes using the same - Google Patents
Heterogeneous catalyst for production of (E)-1,3-diaryl propenes and preparation method of (E)-1,3-diaryl propenes using the same Download PDFInfo
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- KR20160115239A KR20160115239A KR1020150042492A KR20150042492A KR20160115239A KR 20160115239 A KR20160115239 A KR 20160115239A KR 1020150042492 A KR1020150042492 A KR 1020150042492A KR 20150042492 A KR20150042492 A KR 20150042492A KR 20160115239 A KR20160115239 A KR 20160115239A
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Abstract
The present invention relates to a heterogeneous catalyst for producing (E) -1,3-diarylpropene and a process for producing (E) -1,3-diarylpropene using the same.
The heterogeneous catalyst according to the present invention is a heterogeneous catalyst for the preparation of (E) -1,3-diarylpropene which is a representative compound produced through the Tsuji-Trost reaction. The (E) -1,3 -Diarylpropene enables a reaction in a solvent containing water to be environmentally friendly, has a high yield of reaction, and is capable of continuously maintaining excellent reaction yield even when the reaction is repeated several times. to be. In addition, the heterogeneous catalyst according to the present invention is economical because it is not necessary to use a surfactant.
Description
The present invention relates to a heterogeneous catalyst for producing (E) -1,3-diarylpropene and a process for producing (E) -1,3-diarylpropene using the same.
Various transition metal complexes are conventionally used as catalysts for organic synthesis reactions. Several thousands of ligands and transition metal complexes have been reported and are known to be very effective in the synthesis of C-H, C-C, C-O and C-N.
On the other hand, Tsuji-Trost reaction is one of the most useful methods for making allyl-introduced compounds, and allylation reaction of nucleophiles under palladium catalyst. (E) -1,3-diarylpropene is a representative compound prepared by performing such Tsuji-Trost reaction. The Tsuji-Trost reaction, which is applied to prepare (E) -1,3-diarylpropene and the like, usually reacts with organic solvents using phosphorus derivatives and bases as Pd catalysts and ligands. In order to apply this reaction industrially, it is economically and environmentally advantageous to recover and recycle expensive Pd catalyst. Therefore, even if a homogeneous catalyst is used, it is necessary to carry out continuous research for separating harmful Pd catalyst after the reaction and recovering and reusing expensive ligands. Recently, a method for immobilizing a catalyst through a covalent bond to an insoluble support has attracted a great deal of attention in the course of such studies. As part of such efforts, methods have been developed in which Pd is supported and stabilized by using an ionic liquid, a polymer, graphene oxide or a derivative thereof. In other words, methods for conducting the Tsuji-Trost reaction using a heterogeneous catalyst have been developed. However, the heterogeneous catalyst for the Tsuji-Trost reaction, which has been developed to date, is still less efficient than the homogeneous catalyst in terms of reactivity. Nonetheless, the development of sustainable, environmentally friendly, economical and efficient heterogeneous catalysts is urgently required for large-scale Tsuji-Trost reactions. In addition, as one of the sustainable and environmentally friendly methods, development of a heterogeneous catalyst capable of reacting in water is required. As the heterogeneous catalysts developed so far, only the technology for reacting with the organic solvent exists, and the development of the technique using the solvent containing water is not enough. In this way, organic solvents used in the Tsuji-Trost reaction in the existing technologies are a major cause of environmental pollution. Therefore, it is urgent to develop a heterogeneous catalyst capable of proceeding the Tsuji-Trost reaction by using water-containing solvent which is cheap, safe and easily supplied than any organic solvent.
It is an object of the present invention to solve the above-described problems, and it is an object of the present invention to provide a process for producing a specific compound by performing a Tsuji-Trost reaction in a solvent containing water and eliminating the need to use a surfactant, And which is excellent in reaction efficiency even when it is reused several times. It is another object of the present invention to provide a production method which enables the production of a specific compound by using a heterogeneous catalyst which satisfies the above objects.
According to an aspect of the present invention, there is provided a heterogeneous catalyst comprising:
As a heterogeneous catalyst for the production of (E) -1,3-diarylpropene using a solvent containing water and following the Tsuji-Trost reaction,
(E) -1,3-diaryl propene is characterized in that palladium nanoparticles are supported on reversed phase silica gel or N-isopropylacrylamide and 4-vinylpyridine copolymer gel.
A process for producing (E) -1,3-diarylpropene according to still another aspect of the present invention comprises
(E) -1,3-diaryl propene prepared by a reaction involving the following reaction formula using a heterogeneous catalyst.
<Reaction Scheme>
Wherein R 1 = hydrogen, halide, methoxy or ethoxy, or diethylamino group, and R 2 = hydrogen, halide, alkyl group having 1 to 3 carbon atoms, methoxy group A carboxyl group, an ester group, a nitro group or a phenyl group, and R 1 and R 2 may be the same or different)
The heterogeneous catalyst according to the present invention is a heterogeneous catalyst for the preparation of (E) -1,3-diarylpropene which is a representative compound produced through the Tsuji-Trost reaction. The (E) -1,3 -Diarylpropene is a heterogeneous catalyst capable of reaction in a solvent including water to be environmentally friendly as well as excellent in yield of reaction and capable of continuously maintaining excellent reaction yield even when the reaction is repeated several times . In addition, the heterogeneous catalyst according to the present invention is economical because it is not necessary to use a surfactant.
Fig. 1 shows the results of measurement of nuclear magnetic resonance (NMR) data of Example 13. Fig.
2 shows the results of measurement of nuclear magnetic resonance (NMR) data of Example 14. Fig.
3 shows the results of measurement of nuclear magnetic resonance (NMR) data of Example 15. Fig.
Fig. 4 shows the results of measurement of nuclear magnetic resonance (NMR) data of Example 16. Fig.
Therefore, the inventors of the present invention have made extensive efforts to develop a heterogeneous catalyst which promotes the production of a specific compound through the Tsuji-Trost reaction and which is excellent in reactivity in a solvent containing water and does not require addition of an additional surfactant. (E) -1,3-diarylpropene and a process for producing (E) -1,3-diarylpropene using the same.
Specifically, the heterogeneous catalyst according to the present invention comprises
As a heterogeneous catalyst for the production of (E) -1,3-diarylpropene by using a solvent containing water and following the Tsuji-Trost reaction, a reaction product of reversed phase silica gel or N-isopropyl acrylamide and 4-vinylpyridine copolymer gel (E) -1,3-diarylpropene, characterized in that palladium nanoparticles are supported on the support.
The Tsuji-Trost reaction in the present invention is one of the most useful methods for producing an allyl group-introduced compound. The present invention relates to an allylation reaction of a nucleophilic agent under a palladium catalyst.
On the other hand, the (E) -1,3-diarylpropene corresponds to a representative compound prepared through the Tsuji-Trost reaction. Conventional techniques for preparing a specific compound by performing the Tsuji-Trost reaction have been problematic in that most of technologies for synthesizing a compound using an organic solvent are not environmentally friendly. In addition, a recent technology for solving such a problem has a problem that addition of an additional surfactant is required, and the reaction yield and reaction yield due to reuse are not excellent. On the other hand, with this technology, when the reaction catalyst is reused three to four times, the yield of the reaction is remarkably decreased thereafter. Accordingly, the present inventors have developed a heterogeneous catalyst for the production of (E) -1,3-diarylpropene as a representative compound produced by carrying out the Tsuji-Trost reaction.
As a result, when the (E) -1,3-diarylpropene is prepared using the heterogeneous catalyst according to the present invention, the reaction in a solvent containing water is enabled, thereby being environmentally friendly, Is a heterogeneous catalyst capable of continuously maintaining excellent reaction yield even when the reaction is repeated several times. In addition, the heterogeneous catalyst according to the present invention is economical because it is not necessary to use a surfactant.
On the other hand, the preferable temperature at which the heterogeneous catalyst functions as a catalyst in the reaction may be 25-90 ° C. Thus, when the temperature is in the range of 25-90 캜, the reaction yield can be improved more remarkably. On the other hand, the more preferred temperature at which the reaction catalyst functions as a catalyst in the reaction may be a temperature corresponding to 70-90 ° C. When the catalyst functions as a reaction catalyst at 70-90 ° C, a trace amount (for example, 1 mol% The reaction yield can be as high as 85-99.9% and the reaction time can be shortened to less than 10 hours, which is preferable. When the reaction is carried out at a temperature outside the temperature range of 70-90 ° C, for example, at 60 ° C, the use of the reaction catalyst may significantly lower the reaction yield than that at 70-90 ° C It is not preferable.
On the other hand, when the reaction catalyst participates in the reaction, the preferred concentration can be in the range of 0.1-15 mol%. Since the effect of the present invention can be attained only when a small amount of the reaction catalyst is added to the reaction, it is preferable that the reaction amount is more than 0.1 mol%. When the amount exceeds 15 mol%, the maximum amount of the reaction catalyst It is preferable that the concentration is not exceeded. That is, when the concentration of the reaction catalyst is more than 15 mol%, it is not preferable because a reaction catalyst which does not participate in the reaction and is mixed unnecessarily is present. On the other hand, as a preferable example, 10 mol% may be applicable.
On the other hand, the heterogeneous catalyst according to the present invention can maintain a good reaction yield even when the number of times of reuse is increased. On the other hand, in the case of the heterogeneous catalyst according to the prior art, even if the Tsuji-Trost reaction is carried out in water, the reaction yield is remarkably lowered compared to the present invention if the catalyst is reused only 3-4 times.
A process for producing (E) -1,3-diarylpropene according to still another aspect of the present invention comprises
(E) -1,3-diaryl propene prepared by a reaction involving the following reaction formula using a heterogeneous catalyst.
<Reaction Scheme>
In the above reaction formula, X = a halide, an acetate group or a carbonate group, R 1 = hydrogen, a halide, a methoxy group or an ethoxy group or a diethylamino group, R 2 = hydrogen, a halide, A hydroxy group, an aldehyde group, a carboxyl group, an ester group, a nitro group or a phenyl group, and R 1 and R 2 may be the same or different.
The solvent in the above reaction formula may be a solvent including water.
When the (E) -1,3-diarylpropene is prepared by the above production method according to the present invention, it is possible to react in a solvent containing water, and it is not necessary to use a separate surfactant. In addition, even if the reaction catalyst is reused several times, it is possible to keep the initial excellent reaction yield continuously, which is preferable. The reason why the effect of the present invention can be achieved is that the heterogeneous catalyst used in the production of (E) -1,3-diarylpropene is used.
The heterogeneous catalyst which makes it possible to achieve the effects of the present invention is a reaction catalyst for the production of (E) -1,3-diarylpropene, preferably a reversed phase silica gel or N-isopropylacrylamide and 4- The palladium nanoparticles may be supported on the vinyl pyridine copolymer gel. In the case where the heterogeneous catalyst corresponds to the illustrated heterogeneous catalyst, the effect to be achieved in the present invention is to enable reaction in a solvent containing water, to eliminate the necessity of using an additional surfactant, It can be kept excellent.
The base of the reaction formula is preferably at least one selected from the group consisting of K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 and KF.
On the other hand, the reaction temperature according to the reaction formula may be a reaction at a temperature of 25-90 ° C. Thus, when the temperature is in the range of 25-90 캜, the reaction yield can be improved more remarkably. On the other hand, the more preferable temperature of the aqueous solution in which the heterogeneous catalyst is mixed and reacted may be a temperature corresponding to 70-90 ° C. When the reaction is carried out at 70-90 ° C, a very small amount (for example, 1 mol% or less) Even when a catalyst is used, the reaction yield can be as high as 85-99.9%, and the reaction time can be shortened to less than 10 hours, which is preferable. When the reaction is carried out at a temperature outside the temperature range of 70-90 ° C, for example, at 60 ° C, the use of the reaction catalyst may significantly lower the reaction yield than that at 70-90 ° C It is not preferable.
On the other hand, it is preferable that the heterogeneous catalyst is used in a concentration of 0.1-15 mol%. However, since the effect of the present invention can be attained by adding a trace amount of the heterogeneous catalyst, it is preferable that the heterogeneous catalyst is more than 0.1 mol% It is preferable that it does not exceed the above-mentioned concentration because it corresponds to the maximum concentration which can participate in the reaction as a reaction catalyst. On the other hand, as a preferable example, 10 mol% may be applicable.
On the other hand, the heterogeneous catalyst is excellent in the reaction yield even when the production process according to the present invention is repeatedly used several times.
On the other hand, the reaction time according to the reaction formula is preferably 4-24 hours.
Further, after completion of the reaction according to the above reaction formula, the product may be extracted using an organic solvent, and the organic solvent is preferably at least one selected from the group consisting of ethyl acetate, methyl ethyl ketone, methylene chloride, chloroform and diethyl ether Do.
On the other hand, as one preferred embodiment of the process for producing (E) -1,3-diarylpropene according to the present invention,
1) dissolving a compound represented by the following formula (1), a compound represented by the following formula (2), a base and a heterogeneous catalyst in a solvent containing water to obtain a mixed solution; And
2) obtaining (E) -1,3-diarylpropene in the mixed solution;
May be a preferred embodiment of the present invention.
R 1 is hydrogen, a halide, a methoxy group or an ethoxy group, or a diethylamino group, and R 2 = hydrogen, a halide, a carbon number of 1 to 3, An alkyl group, a methoxy group or an ethoxy group, a hydroxy group, an aldehyde group, a carboxyl group, an ester group, a nitro group or a phenyl group, and R 1 and R 2 may be the same or different.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Example
< Example One- Example 6: Reaction temperature optimization reaction>
[Reaction Scheme 1]
1. Cinnamyl carbonate + Phenylboronic acid + K 2 CO 3 + H 2 O
2. Addition of heterogeneous catalyst
3. Heating
4. After termination of reaction, EA was added and extraction (10 ml × 2 times)
6. The EA layer was separated, the water was removed with MgSO 4 ,
7. Evaporation
8. Separation of product (Hexane: Diethyl ether = 30: 1) by column chromatography
9. Vacuum drying.
In Examples 1 to 6, the same reaction as in
As can be seen in Table 1, in the case of Example 1-Example 3 in which the temperature was changed to 60 ° C, it was difficult to exceed the final reaction yield of 85%. And the reaction time significantly exceeded 10 hours. However, in Example 4-Example 6 in which the reaction temperature was 80 캜, the reaction yield exceeded 85%, a considerable number exceeded 90%, and the reaction time was less than 10 hours in all cases. Therefore, when PNIPAM Pd, which is a heterogeneous catalyst capable of promoting the reaction in water, was used, it was confirmed that the optimum temperature condition for achieving the highest reaction yield was a temperature of 70-90 ° C corresponding to about 80 ° C.
< Example 7- Example 12: Optimization of base usage>
[Reaction Scheme 2]
1. Cinnamyl carbonate + Phenylboronic acid + Base + H 2 O
2. Addition of heterogeneous catalyst
3. Heating
4. After termination of reaction, EA was added and extraction (10 ml × 2 times)
6. The EA layer was separated, the water was removed with MgSO 4 ,
7. Evaporation
8. Separation of product (Hexane: Diethyl ether = 30: 1) by column chromatography
9. Vacuum drying.
Meanwhile, the reaction yield according to the amount of the base was confirmed by Example 7-Example 12, and more specific reaction conditions and final reaction yield were confirmed in Table 2 below.
As can be seen from the above Table 2, the reaction yields of 85% were started when the base was added, and the reaction yield was not particularly limited to a specific amount. That is, it was confirmed that the reaction yield was remarkably increased when a trace amount of base was added.
< Example 13- Example 25: Various (E) -1,3- Diaryl propene Synthesis>
[Reaction Scheme 3]
In Example 13 to Example 25, various kinds of (E) -1,3-diarylpropene were synthesized by carrying out the same reaction as in
On the other hand, nuclear magnetic resonance (NMR) data of the (E) -1,3-diarylpropene compound obtained as the final object in Examples 13 to 16 were measured, - Fig. 4 (Fig. 1: Example 13, Fig. 2: Example 14, Fig. 3: Example 15, Fig. At this time, measurement conditions of nuclear magnetic resonance (NMR) are as follows.
1. Device: Bruker 400 MHz
2. Measuring range: minus 0.5-11 ppm
3. Number of scans: 8
From the nuclear magnetic resonance spectral data of FIG. 1 to FIG. 4, it was confirmed that the target material prepared according to the present invention is a pure compound. In addition, the process for producing (E) -1,3-diarylpropene according to the above example is a process for producing a high-purity compound at a high yield under environmentally friendly conditions, in which an organic solvent is not used, as compared with the conventional process.
< Example 26- Example 35: Measurement of reaction yield of heterogeneous catalysts>
[Reaction Scheme 4]
The reaction was carried out as in
(%)
As can be seen in Table 4, the reaction was carried out ten times, and the reaction yield was all above 90% even though the heterogeneous catalyst was continuously reused. From these results, it was confirmed that even when the heterogeneous catalyst was used several times, the initial reaction yield was maintained constantly.
Comparative Example
Meanwhile, according to this embodiment, Tsuji-Trost reaction was carried out in water to prepare 5 mol% of Pd / C catalyst, another heterogeneous catalyst used for synthesizing (E) -1,3- The reaction was not completed, and when 10 mol% was used, the reaction was completed. In the case of Pd / C, however, the filtration process is complicated and takes a long time after completing the reaction.
From these results, it was confirmed that the use of the heterogeneous catalyst according to the present invention maintained the excellent reaction yield despite the continuous reuse rather than the comparative example.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. It is natural.
Claims (10)
A heterogeneous catalyst for the production of (E) -1,3-diarylpropene characterized in that palladium nanoparticles are supported on reversed phase silica gel or N-isopropylacrylamide and 4-vinylpyridine copolymer gel.
<Reaction Scheme>
Wherein R 1 = hydrogen, halide, methoxy or ethoxy, or a diethylamino group, and R 2 = hydrogen, halide, alkyl group having 1-3 carbon atoms, methoxy group A hydroxy group, an aldehyde group, a carboxyl group, an ester group, a nitro group or a phenyl group, and R 1 and R 2 are the same or different)
A process for producing (E) -1,3-diarylpropene, wherein the solvent in the above reaction formula is water-containing solvent.
(E) -1,3-diarylpropene characterized in that palladium nanoparticles are supported on reversed phase silica gel or N-isopropylacrylamide and 4-vinylpyridine copolymer gel.
(E) -1,3-diarylpropene is characterized in that 0.1 to 15 mol% of the heterogeneous catalyst is used.
Wherein the base of the above reaction formula is at least one selected from the group consisting of K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 and KF.
(E) -1,3-diarylpropene characterized in that the reaction temperature according to the above reaction formula is 25-90 占 폚.
(E) -1,3-diarylpropene, wherein the reaction time according to the reaction formula is 4-24 hours.
A process for producing (E) -1,3-diarylpropene characterized by extracting a product with an organic solvent after completion of the reaction according to the above reaction formula.
Wherein the organic solvent is at least one selected from the group consisting of ethyl acetate, methyl ethyl ketone, methylene chloride, chloroform and diethyl ether.
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