CN109529936B - Application of MOPs (metal oxide polymers) loaded bidentate chelate metal catalyst in suzuki reaction - Google Patents

Application of MOPs (metal oxide polymers) loaded bidentate chelate metal catalyst in suzuki reaction Download PDF

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CN109529936B
CN109529936B CN201811518944.2A CN201811518944A CN109529936B CN 109529936 B CN109529936 B CN 109529936B CN 201811518944 A CN201811518944 A CN 201811518944A CN 109529936 B CN109529936 B CN 109529936B
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mops
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CN109529936A (en
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向德轩
徐伟
刘希
陈迪钊
胡扬剑
欧阳跃军
李元祥
林红卫
汤艳
江依帆
涂镜
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
    • B01J2231/4227—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group with Y= Cl

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Abstract

The invention relates to an application of MOPs (metal oxide nanoparticles) loaded bidentate chelate metal catalyst in Suzuki reaction, wherein the MOPs loaded bidentate chelate metal catalyst has a structure shown as a general formula (I):
Figure DDA0001902732740000011
wherein Ar is an aromatic or heteroaromatic ring of 5 to 6 ring atoms;
Figure DDA0001902732740000012
is a substituted or unsubstituted aromatic or heteroaromatic ring of 5 to 6 ring atoms; each X1Independently selected from one of halogen anion, acetate, nitrate and sulfate; n is an integer, R1Is H, methyl or substituted or unsubstituted aryl, and when n is 0, R1Is not H; r2Is H or alkyl; m is a transition metal. The MOPs loaded bidentate chelate metal catalyst has higher stability and better effect of catalyzing Suzuki reaction.

Description

Application of MOPs (metal oxide polymers) loaded bidentate chelate metal catalyst in suzuki reaction
Technical Field
The invention relates to the technical field of catalysts, in particular to an application of MOPs (metal oxide polymers) loaded bidentate chelate type metal catalyst in Suzuki-Miyaura reaction.
Background
Organic microporous polymers (MOPs) are a class of materials composed of organic elements and having a structure containing a large number of interconnected or closed pores. The organic microporous polymer has the advantages of small density, high specific surface area, easy structure regulation and control and strong chemical activity, can be widely applied to various aspects such as adsorption and storage, separation and purification, heterogeneous catalysis, photoelectric devices and the like, and relates to the fields of new energy, environmental protection, chemical industry, information industry and the like. The advantages of the functionalized MOPs in heterogeneous catalysis are more obvious, and are mainly reflected in that: 1) the MOPs as a carrier can effectively prevent the agglomeration of metal nano particles, so that the MOPs can still maintain higher catalytic activity after being recycled for many times; 2) the application is wide, and a metal organic framework can be embedded into a rigid catalyst (such as a bipyridine framework, a porphyrin framework and the like) through modification to obtain an organic porous catalyst; 3) the interconnected pore channel structure and high specific surface area of the material are favorable for mass transfer of the substrate and combination of the substrate and the catalytic active sites. However, since the metal nanoparticles on the MOPs are combined with the MOPs through coordination, the stability of the functionalized MOPs needs to be improved to further improve the catalytic effect.
Disclosure of Invention
Therefore, it is necessary to provide a MOPs-supported bidentate chelate metal catalyst with higher stability for catalyzing Suzuki reactions, so as to realize better catalytic effect.
The application of MOPs (metal oxide catalysts) loaded with bidentate chelate metal catalysts in Suzuki reactions is disclosed, wherein the MOPs loaded with bidentate chelate metal catalysts have the structure shown as the general formula (I):
Figure BDA0001902732720000021
wherein the content of the first and second substances,
ar is an aromatic or heteroaromatic ring of 5 to 6 ring atoms;
Figure BDA0001902732720000022
is a substituted or unsubstituted aromatic or heteroaromatic ring of 5 to 6 ring atoms;
each X1Independently selected from one of halogen anion, acetate, nitrate and sulfate;
n is an integer, R1Is H, methyl or substituted or unsubstituted aryl, and when n is 0, R1Is not H;
R2is H or alkyl;
m is a transition metal.
In one embodiment, Ar is one of the following structures:
Figure BDA0001902732720000023
in one embodiment, R1H and methyl;
or R1Is a group having any one of the following structures:
Figure BDA0001902732720000031
wherein the content of the first and second substances,
Figure BDA0001902732720000032
as defined above.
In one embodiment, n is an integer of 0 to 5, wherein when n is 0, the imidazole ring is directly bonded to R1And (4) connecting.
In one embodiment, the MOPs support bidentate chelating metal catalyst is selected from one of the following polymers:
Figure BDA0001902732720000033
wherein, M and X1As defined above.
In one embodiment, M is Pd2+、Ni3+、Ru3+、Pt2+Or Cu2+。
In one embodiment, the MOPs-supported bidentate chelate type metal catalyst comprises an organic microporous polymer, a transition metal M bonded to the organic microporous polymer through a coordination bond, and an anion X coordinated to the transition metal M1The organic microporous polymer is prepared from the following monomers: compound (II), benzene and dimethoxymethane; and the transition metal M forms coordination with carbon on 2-position of imidazole ring in the organic microporous polymer to form a six-membered cyclic ligand;
the structure of the compound (II) is as follows:
Figure BDA0001902732720000041
wherein R is3Is H, methyl or aryl, and when n is 0, R3Is not H; x2Is a halogen anion; ar, R2As defined above.
In one embodiment, the MOPs loaded bidentate chelate metal catalyst is prepared by the following method:
mixing the compound (II), benzene, dimethoxymethane and 1, 2-dichloroethane at the temperature of between 5 ℃ below zero and 5 ℃, adding iron salt serving as a catalyst, and reacting at the temperature of between 80 and 85 ℃ for 20 to 30 hours to obtain a polymer (III);
in the atmosphere of protective gas, reacting a polymer (III) with a transition metal salt in an organic solvent at 80-85 ℃ for 10-12 h to obtain a MOPs loaded bidentate chelate metal catalyst with a structure shown as a general formula (I);
wherein the structures of the compound (II) and the polymer (III) are as follows:
Figure BDA0001902732720000042
wherein R is3Is H, methyl or aryl, and when n is 0, R3Is not H; x2Is a halogen anion; ar, R2As defined above.
In one embodiment, the Suzuki reaction refers to a reaction of compound a and compound b to produce compound b; wherein the structures of compounds a-c are as follows:
Figure BDA0001902732720000051
wherein R is4、R5Independently selected from H, alkyl, alkoxy, halogen or cyano.
In one embodiment, R4、R5Independently selected from H, methyl, methoxy, halogen or cyano.
In one embodiment, R4Selected from H, methyl or methoxy; r5Selected from H, methyl, halogen or cyano.
In one embodiment, R4And R5At least one of which is H.
The MOPs loaded bidentate chelate metal catalyst has a novel structure shown as a general formula (I), wherein M and an organic framework form a six-membered ring ligand, so that M and the organic framework have stronger coordination capacity, and the MOPs loaded bidentate chelate metal catalyst has higher stability.
In addition, the MOPs loaded bidentate chelate metal catalyst has strong coordination capacity of M and an organic framework, so that the synthesis reaction of the catalyst can be promoted, the synthesis reaction condition of the catalyst is heated and synthesized, and the yield is higher.
The MOPs loaded bidentate chelate metal catalyst is an organic microporous polymer, and has a large number of pores and a high specific surface area. The specific surface area of the MOPs loaded bidentate chelate metal catalyst has an important influence on the catalytic performance of the catalyst. The larger the specific surface area of the MOPs loaded bidentate chelate metal catalyst is, the larger the contact opportunities among reactants and between the reactants and the catalyst are, and the better the catalytic effect is. The presence of a large number of micropores in the present invention also has an important influence on the catalytic performance. The more micropores are, the larger the specific surface area and the volume of the micropores are, the reactants entering the micropores can be limited in a smaller space, and the contact probability among the reactants and between the reactants and the catalyst is improved, so that the catalytic effect is improved, and the method is particularly suitable for Suzuki reaction.
The MOPs-loaded bidentate chelate metal catalyst is used for Suzuki reaction and has a good catalytic effect. On one hand, the catalyst of the invention has higher specific surface area, and on the other hand, the content of metal Pd in the novel catalyst of the invention is far higher than that in the comparative catalyst, so that more reaction sites can be provided. The reasons may be: the monomer used by the catalyst is a bidentate chelate ligand, and can be better and more firmly coordinated with metal to fix the metal on the catalyst. The content of metallic Pd in the catalyst also has very important influence on the catalytic performance. The higher the content of metal Pd, the higher the contact probability of the metal Pd and reactants, and the better the catalytic effect. In addition, because of the formation of the bidentate chelate metal complex in the catalyst and the synergistic effect of the azacarbene and the pyridine ligand, the space structure and the electronic effect of the formed complex can be better adjusted, and the catalyst is stabilized and activated, so that the catalytic effect is finally provided.
Drawings
FIG. 1 is an infrared spectrum of a polymer (III) obtained in examples 1 to 3 and a MOPs-supported bidentate chelate metal catalyst obtained in examples 14 to 16;
FIG. 2 is an X-ray photoelectron spectrum of the MOPs-supported bidentate chelate metal catalyst prepared in examples 14 to 16;
FIG. 3 shows BET adsorption/desorption curves of the polymer (III) obtained in examples 1 to 3 and the MOPs-supported bidentate chelate metal catalyst obtained in example 16;
FIG. 4 is an SEM spectrum of the MOPs-supported bidentate chelate metal catalyst obtained in example 14 and an elemental distribution diagram of C, N and Pd;
FIG. 5 is an SEM image and an elemental distribution chart of C, N and Pd for MOPs-supported bidentate chelate metal catalyst prepared in example 15;
FIG. 6 is an SEM image and an elemental distribution chart of C, N and Pd for MOPs supporting the bidentate chelate metal catalyst prepared in example 16;
FIG. 7 is a nuclear magnetic spectrum of a product obtained by the Suzuki reaction in application example 5.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
One embodiment of the present invention provides a MOPs supported bidentate chelate metal catalyst having a structure represented by general formula (I):
Figure BDA0001902732720000071
wherein the content of the first and second substances,
ar is an aromatic or heteroaromatic ring of 5 to 6 ring atoms;
Figure BDA0001902732720000081
is 5 to 6 substituted or unsubstitutedAn aromatic or heteroaromatic ring of ring atoms;
each X1Independently selected from one of halogen anion, acetate, nitrate and sulfate;
n is an integer, R1Is H, methyl or substituted or unsubstituted aryl, and when n is 0, R1Is not H;
R2is H or alkyl;
m is a transition metal.
The bond in the above formula is attached at a ring, meaning that it can be attached at any position on the ring; when there are multiple substituents on the same ring, the attachment position of each substituent is not the same.
The MOPs loaded bidentate chelate metal catalyst has a structure shown as a general formula (I), wherein M and an organic framework form a six-membered ring ligand, so that M and the organic framework have stronger coordination capacity, and the MOPs loaded bidentate chelate metal catalyst has higher stability. In addition, the MOPs loaded bidentate chelate metal catalyst has strong coordination capacity of M and an organic framework, so that the reaction can be promoted, the reaction condition is more heated, and the yield is higher.
Figure BDA0001902732720000082
Is a substituted or unsubstituted aromatic or heteroaromatic ring of 5 to 6 ring atoms. In particular, the amount of the solvent to be used,
Figure BDA0001902732720000083
is connected on a benzene ring through a methylene group,
Figure BDA0001902732720000084
the aromatic or heteroaromatic ring of 5 to 6 ring atoms in (A) may be further substituted, for example
Figure BDA0001902732720000085
Wherein the aromatic or heteroaromatic ring of 5 to 6 ring atoms is continuously linked to 1-2 substituted or unsubstituted aromatic or heteroaromatic rings of 5 to 6 ring atoms via a methylene group, and so onAnd (3) continuing to polymerize to form a larger molecular structure, thereby obtaining the organic microporous polymer.
In one embodiment, Ar is one of the following structures:
Figure BDA0001902732720000086
wherein the dotted line indicates the position of the attachment of Ar to the imidazole ring.
Further, R2Is H, 3-CH3，4-CH3，5-CH3，3-CH2CH3，4-CH2CH3，5-CH2CH3，4-CH2CH2CH3，4-CH2CH2CH2CH3And the like.
In one embodiment, R1Is a group having any one of the following structures:
Figure BDA0001902732720000091
wherein the content of the first and second substances,
Figure BDA0001902732720000092
is as defined above, i.e. R1Two substituted or unsubstituted aromatic or heteroaromatic rings of 5 to 6 ring atoms connected by a methylene group to each phenyl ring in the above structure; the aromatic ring or the heteroaromatic ring can be substituted, and 1-2 substituted or unsubstituted aromatic rings or heteroaromatic rings with 5 to 6 ring atoms are continuously connected through methylene, so that a larger molecular structure is formed, and the organic microporous polymer is formed.
Further, one selected from the following polymers:
Figure BDA0001902732720000093
wherein, M and X1The definition of (A) is as previously described.
Further, n is an integer of 0-5, wherein when n is 0, the imidazole ring is directly connected with R1And (4) connecting. For example, when n is 0, R1Is a substituted or unsubstituted aryl group. For example, when n is 1, R1Is a substituted or unsubstituted aryl group. Wherein aryl is for example phenyl.
In one embodiment, X1Is Cl, Br or I. In a specific example, X1Is Cl.
In one embodiment, M is Pd2+、Ni3+、Ru3+、Pt2+Or Cu2+. Further, for catalyzing Suzuki coupling reaction, M is preferably Pd2+。
An embodiment of the present invention further provides a preparation method of any one of the MOPs supported bidentate chelate metal catalysts, including the following steps S1 to S2.
Step S1: mixing the compound (II), benzene, dimethoxymethane and 1, 2-dichloroethane at the temperature of between 5 ℃ below zero and 5 ℃, adding iron salt as a catalyst, and reacting for 20 to 30 hours at the temperature of between 80 and 85 ℃ to obtain the polymer (III).
Wherein the structures of the compound (II) and the polymer (III) are as follows:
Figure BDA0001902732720000101
wherein R is3Is H, methyl or aryl, when n is 0, R3Is not H; x2Is a halogen anion; ar, R2The definition of (A) is as previously described. Aryl groups therein are for example phenyl.
Figure BDA0001902732720000102
Is a substituted or unsubstituted aromatic or heteroaromatic ring of 5 to 6 ring atoms. In particular, the amount of the solvent to be used,
Figure BDA0001902732720000103
is connected on a benzene ring through a methylene group,
Figure BDA0001902732720000104
the aromatic or heteroaromatic ring of 5 to 6 ring atoms in (A) may be further substituted, for example
Figure BDA0001902732720000105
The aromatic or heteroaromatic ring with 5 to 6 ring atoms is continuously connected with 1-2 substituted or unsubstituted aromatic or heteroaromatic rings with 5 to 6 ring atoms through methylene, and the polymerization is continuously carried out in such a way to form a larger molecular structure, so that the organic microporous polymer is obtained. Wherein, the aromatic ring or heteroaromatic ring with 5 to 6 ring atoms can be the benzene ring formed by the benzene raw material in the step S1, and can also be the Ar ring in the compound (II), so that the benzene ring in the compound (II) is further polymerized to form the organic microporous polymer.
For example, when n is 0, R3Not being H, i.e. R3Is methyl or aryl if R3Is methyl, correspondingly R1Is methyl, if R3Is aryl, correspondingly R1Is substituted or unsubstituted aryl; for example R1Is a group having any one of the following structures:
Figure BDA0001902732720000111
wherein the content of the first and second substances,
Figure BDA0001902732720000112
is as defined above, i.e. R1Two substituted or unsubstituted aromatic or heteroaromatic rings of 5 to 6 ring atoms connected by a methylene group to each phenyl ring in the above structure; the aromatic ring or the heteroaromatic ring can be substituted, and 1-2 substituted or unsubstituted aromatic rings or heteroaromatic rings with 5 to 6 ring atoms are continuously connected through methylene, so that a larger molecular structure is formed, and the organic microporous polymer is formed.
Further, the compound (II) is obtained by the reaction of N-heterocyclic carbene (NHC) with the following structure and 2-halogenated methylpyridine compound; the structure of the N-heterocyclic carbene (NHC) is as follows:
Figure BDA0001902732720000113
further, R3In the case of aryl, the N-heterocyclic carbene (NHC) can be prepared by Ullmann reaction:
Figure BDA0001902732720000114
further, when N ≠ 0, the N-heterocyclic carbene may be prepared by the following method:
Figure BDA0001902732720000121
wherein, X3Is a halogen atom.
Wherein the iron salt can be ferric chloride, etc.
In one embodiment, the step of heating to 80-85 ℃ after adding iron salt as a catalyst adopts a step-type heating mode: firstly heating to 30-35 ℃ and preserving heat for 0.5-1 h, then heating to 5-10 ℃ and preserving heat for 0.5-1 h each time until the temperature is heated to 80-85 ℃. Therefore, the problems that the reaction is just too violent, the materials are sprayed out, and then the materials are wasted and dangers are caused are solved, and the reaction is controlled better.
Further, the step of heating to 80-85 ℃ after adding iron salt as a catalyst adopts a step-type heating mode: firstly heating to 30 ℃ and preserving heat for 1h, then heating to 10 ℃ and preserving heat for 1h each time until the temperature is raised to 80 ℃ and reacting for 24 h.
Specifically, the product obtained by the reaction in step S1 is a brownish black solid, and the obtained solid is washed with methanol for several times, subjected to soxhlet extraction with methanol, and vacuum-dried.
Step S2: in the protective gas atmosphere, reacting the polymer (III) with a transition metal salt in an organic solvent at the temperature of 80-85 ℃ for 10-12 h to obtain the MOPs loaded bidentate chelate metal catalyst with the structure shown as the general formula (I).
Wherein the transition goldThe metal salt can be halide, acetate, nitrate or sulfate of metal ions; accordingly, X in the resulting catalyst1Is halogen anion, acetate, nitrate or sulfate. Among them, the halogen anion is preferably Cl, Br or I.
In one embodiment, the method further comprises a purification step of loading the MOPs with the bidentate chelate metal catalyst: and (3) separating the reaction liquid after the reaction to obtain a solid, washing the solid with acetone, and drying the solid in vacuum by using acetone in a Soxhlet extractor to obtain the purified MOPs loaded bidentate chelate metal catalyst.
The preparation method is simple, the reaction conditions are mild, the yield is high, the prepared MOPs loaded bidentate chelate metal catalyst has high thermal stability, the specific surface area is large and is up to 964m2g-1。
The MOPs-supported bidentate chelate metal catalyst comprises an organic microporous polymer, a transition metal M bonded on the organic microporous polymer through a coordination bond and an anion X coordinated with the transition metal M1. Wherein the organic microporous polymer is prepared from the following monomers: compound (II), benzene and dimethoxymethane; and the transition metal M forms coordination with carbon at the 2-position of the imidazole ring in the organic microporous polymer to form a six-membered cyclic ligand.
An embodiment of the invention also provides an application of any MOPs loaded bidentate chelate type metal catalyst in Suzuki coupling reaction, and the MOPs loaded bidentate chelate type metal catalyst has a structure shown in the general formula (I).
Preferably, M is Pd.
In one embodiment, the Suzuki coupling reaction refers to the reaction of compound a and compound b to form compound c; wherein the structures of compounds a-c are as follows:
Figure BDA0001902732720000131
wherein R is4、R5Independently selected from H, alkyl, alkoxy, halogen or cyano, X4Is halogen anion.
Therein is provided withIn one embodiment, R4、R5Independently selected from H, methyl, methoxy, halogen or cyano.
Further, R4Selected from H, methyl or methoxy; r5Selected from H, methyl, halogen or cyano.
The MOPs-loaded bidentate chelate metal catalyst is used for catalyzing Suzuki coupling reaction, and has higher catalytic activity and higher catalytic stability.
The following are specific examples.
The preparation method of the MOPs loaded bidentate chelate metal catalyst comprises the following steps:
1) synthesis of MOPs supported bidentate chelate ligand polymer (III):
compound (II) (0.5g), benzene (0.5g), dimethoxymethane (1.0g) and 1, 2-dichloroethane (5mL) were charged in a three-necked flask with stirring. The reaction solution was cooled to 0 ℃ in an ice-water mixture, stirred, and then ferric trichloride (3g) was added and stirred uniformly. Gradually heating to 30 ℃, and preserving heat for 1.0 hour; gradually heating to 40 ℃, and preserving heat for 1.0 hour; gradually heating to 50 ℃, and preserving heat for 1.0 hour; gradually heating to 60 ℃, and preserving heat for 1.0 hour; gradually heating to 70 ℃, and preserving heat for 1.0 hour; gradually heating to 80 ℃, and preserving heat for 24.0 hours. Washing the obtained solid with methanol for 3 times, performing Soxhlet extraction with methanol for 24 hours, and vacuum-drying at 80 ℃ for 24 hours to obtain a product which is brownish black solid powder, namely MOPs loaded bidentate chelate ligand polymer (III).
Figure BDA0001902732720000141
Examples 1 to 13 are synthesis examples of the MOPs supporting the bidentate chelate ligand polymer (III) in the step 1); examples 1 to 13 polymers (III) were obtained by reacting the raw materials shown in table 1 below according to the reaction procedure described above, as shown in table 1.
TABLE 1
Figure BDA0001902732720000142
Figure BDA0001902732720000151
The structures of the compounds (III-1, III-2, III-3) prepared in examples 1 to 3 are as follows:
Figure BDA0001902732720000152
2) preparation of MOPs loaded bidentate chelate metal catalyst
Polymer (III) (1.0g) and transition metal salt MX were weighed in this order1 2Or MX1 3(0.3g) was added to 5mL of N, N' -dimethylformamide and reacted at 80 ℃ for 12 hours under a nitrogen atmosphere. After the reaction was complete, the solid was centrifuged and washed with acetone (20 mL. times.3). The resulting material was loaded into a soxhlet extractor and extracted with acetone for 48 hours. And drying the solid for 24 hours under vacuum to obtain the catalyst MOPs-M containing the organic microporous material, namely the MOPs loaded bidentate chelate metal catalyst.
Figure BDA0001902732720000161
Examples 14 to 33 are preparation examples of the MOPs supported bidentate chelate metal catalyst of the step 2), and examples 14 to 33 were prepared by reacting the raw materials shown in the following table 2 according to the above reaction procedure, and the obtained product was the MOPs supported bidentate chelate metal catalyst of the general formula (I), as shown in table 2.
TABLE 2
Figure BDA0001902732720000162
Figure BDA0001902732720000171
For example, the structural formulas of the MOPs-supported bidentate chelate metal catalysts (I-1, I-2, I-3) prepared in examples 14 to 16 are respectively as follows:
Figure BDA0001902732720000172
comparative example 1
Step 1): compound (IV) (0.5g), benzene (0.5g), dimethoxymethane (1.0g) and 1, 2-dichloroethane (5mL) were charged in a three-necked flask with stirring. The reaction solution was cooled to 0 ℃ in an ice-water mixture, stirred, and then ferric trichloride (3g) was added and stirred uniformly. Gradually heating to 30 ℃, and preserving heat for 1.0 hour; gradually heating to 40 ℃, and preserving heat for 1.0 hour; gradually heating to 50 ℃, and preserving heat for 1.0 hour; gradually heating to 60 ℃, and preserving heat for 1.0 hour; gradually heating to 70 ℃, and preserving heat for 1.0 hour; gradually heating to 80 ℃, and preserving heat for 24.0 hours. Washing the obtained solid with methanol for 3 times, performing Soxhlet extraction with methanol for 24 hours, and vacuum drying at 80 ℃ for 24 hours to obtain brownish black solid powder, namely MOPs supported ligand polymer (V).
Figure BDA0001902732720000181
Step 2): polymer (V) (1.0g) and palladium chloride (0.3g) were sequentially weighed and added to 5mL of N, N' -dimethylformamide, and reacted at 80 ℃ for 12 hours under a nitrogen atmosphere. After the reaction was complete, the solid was centrifuged and washed with acetone (20 mL. times.3). The resulting material was loaded into a soxhlet extractor and extracted with acetone for 48 hours. And drying the solid for 24 hours under vacuum to obtain the catalyst MOPs-M containing the organic microporous material, namely the MOPs loaded metal catalyst (VI).
Figure BDA0001902732720000182
FIG. 1 is an infrared spectrum of a polymer (III) obtained in examples 1 to 3 and MOPs-supported bidentate chelate metal catalysts obtained in examples 14 to 16, and FIG. 2 is a graph showing an exampleBond energy spectrograms of MOPs-supported bidentate chelate metal catalysts prepared in examples 14-16; as can be seen from FIGS. 1 and 2, the MOPs supported bidentate chelate metal catalyst was successfully prepared, and Pd in the MOPs supported bidentate chelate metal catalyst was Pd2+。
FIG. 3 shows BET adsorption/desorption curves of the polymer (III) obtained in examples 1 to 3 and the MOPs-supported bidentate chelate metal catalyst obtained in example 16; as can be seen from FIG. 3, the specific surface area of the MOPs-supported bidentate chelate metal catalyst was as large as 947m2g-1。
FIG. 4 is an SEM spectrum of the MOPs-supported bidentate chelate metal catalyst obtained in example 14 and an elemental distribution diagram of C, N and Pd; FIG. 5 is an SEM image and an elemental distribution chart of C, N and Pd for MOPs-supported bidentate chelate metal catalyst prepared in example 15; FIG. 6 is an SEM image and an elemental distribution chart of C, N and Pd for MOPs supporting the bidentate chelate metal catalyst prepared in example 16; wherein a, b, c and d in FIGS. 4-6 are the corresponding SEM and element distribution diagrams of C, N and Pd, respectively; from FIGS. 4-6, the morphology of the catalyst and the success of the catalyst preparation can be seen.
Table 3 shows BET specific surface area, micropore volume and Pd of the polymer (III) obtained in part of the examples and the MOPs having the structure (I) obtained in part of the examples as supported on the bidentate chelate metal catalyst2+A content parameter;
wherein S isBETThe BET specific surface area, pressure range (P/P0 ═ 0.05 to 0.20); sMicroIs the specific surface area of the micropores; vmicroIs the micropore volume; [ Pd]Pd for inductively coupled plasma emission Spectroscopy (ICP) determination2+The content of (a).
TABLE 3
Figure BDA0001902732720000191
Figure BDA0001902732720000201
Examples of catalytic applications.
Application example 1
The (I-1) MOPs-Pd obtained in example 1 was used to catalyze a Suzuki coupling reaction.
First, 2.5mmol of the halogenated aromatic hydrocarbon (a), 4mmol of the arylphenylboronic acid (b) and 5mmol of K are weighed3PO4Adding the mixture into a round-bottom flask for standby, adding 50mg of the prepared MOPs loaded bidentate chelate metal catalyst (I-1), finally weighing 15mL of ethanol and 15mL of water, adding the mixture into the round-bottom flask, and uniformly stirring. Then transferring the reaction system into an oil bath at the temperature of 80 ℃, and reacting for 1.0 hour under magnetic stirring; and (4) after the reaction is completed, stirring, cooling to room temperature, filtering, drying, and purifying by column chromatography to obtain the product (c).
The equation for the catalytic reaction is shown below, with the corresponding catalyst on the right:
Figure BDA0001902732720000202
the following table 4 shows examples 1 to 20 of applications of the MOPs prepared according to the present invention supporting the bidentate chelate metal and comparative examples 1 to 5 of applications of the catalyst prepared in comparative example 1.
Specifically, application examples 2 to 14 were carried out using the catalyst (I-1) prepared in example 14 for the catalytic reaction similar to that of application example 1 described above; application examples 15 to 20 are substantially the same as application example 1, and the application example 15 is different in that: the catalyst used was catalyst (I-2) in an amount of 25mg, except that in practical example 16: the catalyst used was catalyst (I-3) in an amount of 25mg, except that in practical example 17: the catalyst (I-1) was used in an amount of 25mg, except that in practical example 18: catalyst (I-1) was used in an amount of 25mg, a reaction temperature of 25 ℃ and a reaction time of 10 hours, except that in practical example 19: the catalyst (I-1) was used in an amount of 25mg, the reaction temperature was 100 ℃ and application example 20 was different in that: the amount of the catalyst (I-1) used was 100 mg.
Specifically, the halogenated aromatic hydrocarbon (a) and the arylphenylboronic acid (b) used in application examples 1 to 20 and application examples comparative examples 1 to 5 correspond to the product (c) produced, as shown in table 4.
Specifically, the catalysts used in application example comparative examples 1 to 5 were the catalysts prepared in comparative example 1, and the other test conditions in application example comparative examples 1 to 5 were the catalytic tests in application examples 5, 17, 18, 19, and 20, respectively, to obtain the yields shown in table 4 below. The reaction equations of the application example comparative examples 1 to 5 and the catalysts used are shown in the following formula.
Figure BDA0001902732720000211
TABLE 4
Figure BDA0001902732720000212
Figure BDA0001902732720000221
Wherein the yield of comparative example 3 of the application example is 0, which means that the product was not isolated by the above-mentioned method; fig. 7 is a nuclear magnetic spectrum of a product obtained by the suzuki reaction according to application example 5, and it can be seen that the structure of the obtained product corresponds to that of application example 5 in table 4.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. The application of MOPs (metal oxide catalysts) loaded bidentate chelate metal catalyst in Suzuki reaction is characterized in that the MOPs loaded bidentate chelate metal catalyst has a structure shown as a general formula (I):
Figure DEST_PATH_IMAGE001
（I）
wherein the content of the first and second substances,
ar is an aromatic or heteroaromatic ring of 5 to 6 ring atoms;
Figure 107968DEST_PATH_IMAGE002
is a substituted or unsubstituted aromatic or heteroaromatic ring of 5 to 6 ring atoms;
each X1Independently selected from one of halogen anion, acetate, nitrate and sulfate;
n is an integer, R1Is H, methyl or substituted or unsubstituted aryl, and when n =0, R1Is not H;
R2is H or alkyl;
m is Pd2+、Ni3+、Ru3+、Pt2+Or Cu2+；
The MOPs loaded bidentate chelate metal catalyst is prepared by the following method:
mixing the compound (II), benzene, dimethoxymethane and 1, 2-dichloroethane at the temperature of-5 ℃, adding iron salt as a catalyst, and reacting at the temperature of 80-85 ℃ for 20-30 h to obtain a polymer (III);
in a protective gas atmosphere, reacting a polymer (III) with a transition metal salt in an organic solvent at 80-85 ℃ for 10-12 h to obtain a MOPs-supported bidentate chelate metal catalyst with a structure shown as a general formula (I);
wherein the structures of the compound (II) and the polymer (III) are as follows:
Figure DEST_PATH_IMAGE003
wherein R is3Is H, methyl or aryl, and when n =0, R3Is not H; x2Is halogen anion.
2. The use of claim 1, wherein Ar is one of the following structures:
Figure 447944DEST_PATH_IMAGE004
。
3. the use of claim 1, wherein R is1H and methyl;
or R1Is a group having any one of the following structures:
Figure DEST_PATH_IMAGE005
。
4. the use according to claim 1, wherein n is an integer of 0 to 5, wherein when n is 0, the imidazole ring is directly bonded to R1And (4) connecting.
5. The use of claim 1, wherein the MOPs support a bidentate chelating metal catalyst selected from one of the following polymers:
Figure 149053DEST_PATH_IMAGE006
。
6. use according to any one of claims 1 to 5, wherein X is1Is Cl, Br or I.
7. The use according to claim 1, wherein the suzuki reaction is a reaction of compound a and compound b to produce compound c; the structures of the compounds a-c are as follows:
Figure DEST_PATH_IMAGE007
；
wherein R is4、R5Independently selected from H, alkyl, alkoxy, halogen or cyano.
8. The use of claim 7, wherein R is4、R5Independently selected from H, methyl, methoxy, halogen or cyano.
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