Acenaphthequinone diimine palladium functionalized super-crosslinked microporous polymer as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic porous materials, and relates to an acenaphthequinone diimine palladium functionalized super-crosslinked microporous polymer as well as a preparation method and application thereof. The preparation method specifically comprises the following steps: carrying out Friedel-Crafts alkylation reaction on (1E, 2E)-N1, N2-bis [2, 4, 6-tri-(benzhydryl phenyl)] acenaphthylene-1, 2-diimine and dimethyl formal, 1, 3, 5-triphenylbenzene or tetraphenylmethane, so as to obtain an organic porous polymer; and carrying out coordination on the organic porous polymer and PdCl2 to obtain the acenaphthequinone diimine palladium functionalized super-crosslinked microporous polymer with catalytic activity. The super-crosslinked microporous polymer has the advantages of high stability, large specific surface area and high palladium loading capacity, and can catalyze the direct C-H bond arylation reaction of brominated aromatic hydrocarbon and heteroaromatic hydrocarbon to synthesize a linked heteroaryl compound; the preparation method of the organic porous polymer catalytic material is simple and suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic porous materials, and particularly relates to a acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer and a preparation method and application thereof. BACKGROUND

[0002] The double heteroaryl structure refers to a compound skeleton formed by directly connecting two aromatic rings (i.e. heteroaromatic rings) composed of carbon and heteroatoms (such as N, O, S, etc.) through a single bond. Due to its stability of aromatic system and unique electronic properties of heteroatoms, the double heteroaryl structure has wide applications in the fields of pharmaceutical research, organic optoelectronic functional materials, and chemical sensing and imaging. The synthesis methods of the double heteroaryl structure mainly include two categories: traditional pre-functionalization cross-coupling and direct activation / functionalization of C-H bond. Compared with the traditional transition metal-catalyzed cross-coupling reaction which relies on functionalized metal reagents, the direct C-H arylation reaction has the advantages of simple synthesis steps, high economic efficiency, high atom utilization rate, and environmental friendliness, and is considered as a more concise and effective synthesis strategy.

[0003] At present, the catalytic system of C-H direct arylation is mostly a homogeneous catalytic system. The acenaphthenequinone diimine ligand used in the homogeneous catalytic system constructs an efficient, stable, and highly selective catalytic system by virtue of the synergistic effect of its strong sigma-donating ability and rigid bidentate chelation mode. However, the homogeneous catalytic system still faces some challenges, such as the difficulty in synthesizing bulky or stereospecific acenaphthenequinone diimine-palladium complexes, which restricts the further optimization of the structural diversity and catalytic performance; at the same time, the homogeneous catalyst is difficult to be effectively recovered and reused from the reaction system, which not only increases the process cost, but also brings difficulties to the product purification. In addition, although the existing technology involves the use of alpha-diimine palladium functionalized monomers and polyacetylene benzene monomers to construct a catalytically active heterogeneous catalytic material through one-step coupling reaction. However, the entire synthesis route is complicated and high in cost. At the same time, the control of the polymerization reaction (such as molecular weight, crosslinking degree, pore size distribution) is difficult, which may lead to large differences in material performance of different batches of production, poor reproducibility, and is not conducive to the large-scale production and application. SUMMARY

[0004] The purpose of the present application is to provide an acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer and a preparation method and application thereof, so as to overcome the shortcomings of the prior art and synthesize a novel acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer as a heterogeneous catalytic ligand. The ligand has high catalytic efficiency and good recyclability for the construction of organic compounds with double heteroaryl structure by Pd-catalyzed direct C-H arylation reaction.

[0005] In order to achieve the above-mentioned purpose, the technical scheme of the present application is as follows: In a first aspect, the present application provides a functionalized hypercrosslinked microporous polymer of acenaphthenequinone diimine palladium, which has a structural unit shown in any one of formula I-III:

[0006] Formula I

[0007] Formula II

[0008] Formula III.

[0009] In the structural unit shown in any one of formula I-III, the wavy line indicates the same monomer infinite connection.

[0010] Hypercrosslinked microporous microporous polymers (HCPs) as a kind of high stability crosslinked amorphous polymers with permanent nanometer holes have been widely concerned. Compared with other organic porous materials, the polymer has the following advantages: 1) simple synthesis method, easy to mass production; 2) the monomer of the synthesized material does not need to be functionalized, which is easy to obtain and low in price; 3) the obtained polymer material has a large specific surface area. HCPs materials have been widely used in the fields of gas adsorption / separation / storage, energy storage, molecular recognition / sensor, light emission / harvesting, heterogeneous catalysis, etc. The new type of acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer designed and synthesized in the present application is used as a heterogeneous catalytic ligand, and the polymer has high catalytic efficiency and good recyclability for the construction of organic compounds with heteroaryl structure by Pd-catalyzed direct C-H arylation reaction.

[0011] In some other embodiments, the specific surface area of the acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer is 530-890 m 2 ·g -1 ; The content of metal palladium in the acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer is 3.0-4.0 wt%.

[0012] The acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer has a large number of micropores and mesopores, presents a porous structure, has the advantages of high stability, large specific surface area, high palladium loading, etc., and can efficiently catalyze the direct C-H bond arylation reaction of brominated aromatic hydrocarbons and heteroaromatic hydrocarbons to synthesize biheteroaryl compounds.

[0013] In a second aspect, the present application provides a preparation method of the acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer of the first aspect, which comprises the following steps: (1E, 2E)-N, N'-bis (diphenylmethyl) -1, 2-diphenyl ethanediamine and acenaphthenequinone are subjected to ketone amine condensation reaction to obtain (1E, 2E)-N,1 ,N 2 bis[2,4,6-tris-(diphenylmethyIphenyl)]acenaphthylene-1,2-diimine; (1E,2E)-N 1 ,N 2 bis[2,4,6-tris-(diphenylmethyIphenyl)]acenaphthylene-1,2-diimine and a cross-linking agent to prepare acenaphthylenequinone diimine functionalized hypercrosslinked microporous polymer by a Friedel-Crafts alkylation reaction; The cross-linking agent is one or more of dimethyIformaldehyde, chloro(methoxy)methane and 1,2-dichloroethane; The acenaphthylenequinone diimine functionalized hypercrosslinked microporous polymer and palladium dichloride are subjected to a coordination reaction to prepare acenaphthylenequinone diimine palladium functionalized hypercrosslinked microporous polymer.

[0014] The FeCl3 catalyzed Friedel-Crafts alkylation reaction synthesis strategy adopted in the present application is simple, convenient and feasible, and is suitable for industrial production. The material prepared in the present application has higher catalytic activity (the catalyst is used in an amount of 0.15 mol% to efficiently catalyze), and can efficiently catalyze the direct C-H bond arylation reaction of bromoarene and heteroarene to synthesize biheteroaryl compounds.

[0015] In some other embodiments, the molar ratio of 2, 4, 6-tris-(diphenylmethyl) aniline and acenaphthylene is (2-3): 1. The temperature of the ketone amine condensation reaction is 140-150°C, and the reaction time is 4-10 h.

[0016] Specifically, 2, 4, 6-tris-(diphenylmethyl) aniline and acenaphthylene are uniformly mixed, zinc dichloride and acetic acid are added, and the mixture is reacted at 140-150°C for 4-10 h. After the reaction is completed, the mixture is cooled to room temperature, filtered, washed with ethyl acetate, and the obtained orange-red precipitate is fully dissolved in dichloromethane, potassium oxalate solution is added, the obtained mixed phase solution is stirred at room temperature, the organic phase is extracted and collected, the organic solvent is removed under vacuum, and the obtained orange-yellow solid is recrystallized in dichloromethane and hexane to obtain the product.

[0017] More specifically, in some other embodiments, the molar ratio of 2, 4, 6-tris-(diphenylmethyl) aniline and acenaphthylene is 2:1, 2.2:1, 2.5:1, 2.8:1 or 3:1. The temperature of the ketone amine condensation reaction is 140, 145 or 150°C, and the reaction time is 4, 5, 6, 7, 8, 9 or 10 h. The above ranges can ensure that the raw materials are fully reacted, and the product has high yield and few side reactions.

[0018] In some other embodiments, (1E,2E)-N 1 ,N 2In the Friedel-Crafts alkylation reaction of bis[2,4,6-tris-(diphenylmethylphenyl)]acenaphthylene-1,2-diimine and the cross-linking agent, a comonomer, which is one or both of 1, 3, 5-triphenylbenzene and tetraphenylmethane, can also be added; The molar ratio of (1E,2E)-N1,N2-bis[2,4,6-tris-(diphenylmethylphenyl)]acenaphthylene-1,2-diimine, the cross-linking agent and the comonomer is 1:(10-30):(0-1); The atmosphere of the Friedel-Crafts alkylation reaction is an inert atmosphere, the temperature is 60-80℃, and the reaction time is 20-30 h.

[0019] Specifically, (1E,2E)-N1,N2-bis[2,4,6-tris-(diphenylmethylphenyl)]acenaphthylene-1,2-diimine, dimethyl glycol formaldehyde and an organic solvent are uniformly mixed; or, (1E,2E)-N1,N2-bis[2,4,6-tris-(diphenylmethylphenyl)]acenaphthylene-1,2-diimine, dimethyl glycol formaldehyde, a comonomer (one or both of 1, 3, 5-triphenylbenzene and tetraphenylmethane) and an organic solvent are uniformly mixed, then a Lewis acid catalyst, iron trichloride, is added to the reaction system under the protection of a nitrogen atmosphere, and then the reaction system is placed in an oil bath at 60-80℃ and stirred for 20-30 h, and the obtained solid product is filtered, washed, Soxhlet extracted and vacuum dried to obtain an acenaphthylenequinone diimine functionalized hypercrosslinked microporous polymer. The amount of iron trichloride used is the same as the amount of dimethyl glycol formaldehyde used.

[0020] More specifically, the molar ratio of (1E,2E)-N1,N2-bis[2,4,6-tris-(diphenylmethylphenyl)]acenaphthylene-1,2-diimine, the cross-linking agent and the comonomer is 1:10:0, 1:13:0, 1:20:0, 1:26:0, 1:30:0, 1:10:1, 1:13:1, 1:20:1, 1:26:1 or 1:30:1; the atmosphere of the Friedel-Crafts alkylation reaction is nitrogen or argon, the temperature is 60, 65, 70, 75 or 80℃, and the reaction time is 20, 24, 26 or 30 h. Within this range, it can be ensured that the raw materials are fully reacted, and the product has a high yield and few side reactions.

[0021] In some other embodiments, the molar ratio of the acenaphthylenequinone diimine functionalized hypercrosslinked microporous polymer and dichloropalladium is 1:(2-3); The temperature of the coordination reaction is 70-90℃, and the reaction time is 10-15 h.

[0022] Specifically, acenaphthenequinone diimine functionalized hypercrosslinked microporous polymer and palladium dichloride are mixed in an organic solvent, the reaction system is placed in an 80℃ oil bath and stirred for 12 hours, and then filtered, washed, Soxhlet extracted, and dried to obtain acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer.

[0023] More specifically, the molar ratio of acenaphthenequinone diimine functionalized hypercrosslinked microporous polymer and palladium dichloride is 1:2, 1:2.5, or 1:3; the temperature of the coordination reaction is 70, 75, 80, 85, or 90℃, and the reaction time is 10, 12, or 15 h. Within this range, it can be ensured that the raw materials are fully reacted, and the product has high yield and few side reactions.

[0024] In some other embodiments, the catalyst used in the ketone amine condensation reaction and the Friedel-Crafts alkylation reaction is one of anhydrous ferric chloride, anhydrous aluminum chloride, and anhydrous zinc chloride, and the solvent used is one of chloroform, 1,2-dichloroethane, methanol, ethanol, and acetic acid.

[0025] Specifically, the catalyst used in the ketone amine condensation reaction is anhydrous zinc chloride, and the solvent is acetic acid; the catalyst used in the Friedel-Crafts alkylation reaction is anhydrous ferric chloride, and the solvent is chloroform or 1,2-dichloroethane; and the solvent used in the coordination reaction is methanol or ethanol.

[0026] In a third aspect, the present application provides the use of the acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer of the first aspect in catalyzing the direct C-H activation reaction of heteroaromatic bromide and heteroaromatic compound.

[0027] In a fourth aspect, the present application provides a method for the direct C-H activation reaction of heteroaromatic bromide and heteroaromatic compound, which comprises mixing the acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer of the first aspect, heteroaromatic bromide, heteroaromatic compound, base, additive, and solvent, and then performing the reaction under the protection of an inert atmosphere.

[0028] The solvent used in the C-H arylation reaction is DMAc, the base is potassium carbonate, and the additive is pivalic acid.

[0029] In some other embodiments, the molar ratio of the acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer, heteroaromatic bromide, heteroaromatic compound, base, and additive is 1:(1-2):(0.001-0.005):(1-3):(0.2-0.5). The heteroaromatic bromide is one of 3-bromopyridine, 5-bromopyrimidine, 5-bromo-2-methylpyridine, 4-bromoisoquinoline, 5-bromo-2-methoxypyridine, and 2-bromothiophene. The heteroarene compound is one of 2,4-dimethylthiazole, 2-methylthiophene, 3,5-dimethylisoxazole, benzothiophene, 2-methylfuran, and 4-bromoisoquinoline, 4-methylthiazole, and 1,2-dimethylimidazole; The temperature of the reaction is 120-140 DEG C, and the reaction time is 10-15 h.

[0030] Specifically, the temperature of the C-H arylization reaction is 120, 130, or 140 DEG C, and the reaction time is 10, 12, or 15 h.

[0031] The present application has the following beneficial effects: (1) The acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer provided by the present application uses (1E,2E)-N 1 ,N 2 -dibis[2,4,6-tri-(diphenylmethylphenyl)]acenaphthylene-1,2-diimine as a monomer to synthesize the functionalized hypercrosslinked microporous polymer, the acenaphthenequinone diimine structure monomer is uniformly distributed in the hypercrosslinked microporous polymer skeleton, and rich active sites for coordination with metal ions are provided; the large steric hindrance acenaphthenequinone diimine structure in the acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer can inhibit the agglomeration of palladium, thereby improving the catalytic activity of palladium. At the same time, the acenaphthenequinone diimine structure is combined with palladium through a chemical bond, which can effectively reduce the loss of palladium ions and ensure that the hypercrosslinked microporous polymer catalyst can be recycled multiple times while still maintaining activity.

[0032] (2) The prepared acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer can be used as a heterogeneous palladium supported catalyst to efficiently catalyze the direct C-H bond arylization reaction of heteroarene bromide and heteroarene compound to construct a double heterocyclic structure compound, and has high catalytic efficiency and good recyclability.

[0033] (3) The preparation method of the present application is efficient and simple, suitable for large-scale preparation, and has the prospect of industrial application. BRIEF DESCRIPTION OF DRAWINGS

[0034] The drawings accompanying the specification of the present application serve to provide further understanding of the present application, and the illustrative embodiments of the present application and the description thereof serve to explain the present application, and do not constitute an improper limitation on the present application.

[0035] Figure 1 is the nuclear magnetic resonance hydrogen spectrum of the monomer (1E,2E)-N 1 ,N 2 -dibis[2,4,6-tri-(diphenylmethylphenyl)]acenaphthylene-1,2-diimine in the present application embodiment 1; Figure 2 is the nuclear magnetic resonance hydrogen spectrum of the monomer (1E,2E)-N 1 ,N 2- Carbon spectrum of bis[2,4,6-tris-(diphenylmethyIphenyl)]acenaphthylene-1,2-diimine; Figure 3 DIM prepared for Example 1 AQ - Solid state nuclear magnetic resonance 13 C spectrum of Pd-HCP-1 material; Figure 4 DIM prepared for Example 1 AQ - Pd 3d X-ray photoelectron spectrum of Pd-HCP-1 material; Figure 5 DIM prepared for Example 1 AQ - N 1s X-ray photoelectron spectrum of Pd-HCP-1 material; Figure 6 DIM prepared for Example 1 AQ - Thermogravimetric analysis of Pd-HCP-1 material; Figure 7 DIM prepared for Example 1 AQ - Powder X-ray diffraction of Pd-HCP-1 material; Figure 8 DIM prepared for Example 1 AQ - Scanning electron micrograph of Pd-HCP-1 material; Figure 9 DIM prepared for Example 1 AQ - Nitrogen adsorption curve of Pd-HCP-1 material; Figure 10 DIM prepared for Example 1 AQ - Pore size distribution of Pd-HCP-1 material. DETAILED DESCRIPTION

[0036] Those skilled in the art will appreciate that the following examples are intended to illustrate but not limit the scope of the present application. Unless otherwise indicated, the conditions in the examples were conventional or those recommended by the manufacturer. Where the manufacturer of a used component is not indicated, it is a conventional product available commercially.

[0037] Example 1 This example provides a method for preparing a Pd-acenaphthene diimine functionalized hypercrosslinked microporous polymer catalyst, comprising the following steps: (1) (1E, 2E)-N 1 ,N 2 The synthetic route of bis[2, 4, 6-tris-(diphenylmethyIphenyl)]acenaphthylene-1, 2-diimine is shown below:

[0038] In a 100 mL round bottom flask, 1.18 g (2.0 mmol, 2.0 eq) 2, 4, 6-tri-(diphenyl methylene) aniline, 0.19 g (1.0 mmol, 1.0 eq) acenaphthenequinone, 0.16 g ZnCl2(1.2 mmol, 1.2 eq) and 15 mL acetic acid were added. The reaction system was placed in an oil bath at 140 °C for 4 h. After the reaction was completed, orange-red precipitate was generated in the bottle. After cooling to room temperature, the precipitate was filtered and washed with ethyl acetate. The obtained orange-red precipitate was dissolved in 25 mL dichloromethane, potassium oxalate solution was added, and the obtained mixed phase solution was stirred at room temperature for 6 h. After extraction with ethyl acetate, the organic phase was washed with water three times, and then anhydrous sodium sulfate was added to the organic phase for drying. The organic solvent was removed under vacuum to obtain an orange-yellow solid, which was recrystallized in dichloromethane and hexane to obtain the product. Yield 1.0 g (76%).

[0039] (2) Synthesis route of acenaphthenequinone diimine functionalized hypercrosslinked microporous polymer (named DIM AQ -HCP-1) is as follows:

[0040] Under the protection of nitrogen atmosphere, a magnetic stirrer was added to a dry and clean 50 mL round bottom flask. (1E, 2E)-N 1 ,N 2 -bis[2, 4, 6-tri-(diphenyl methylene phenyl)] acenaphthene-1, 2-diimine (0.3 mmol, 398 mg), dimethylformaldehyde (304 mg, 4.0 mmol) were dispersed in 5 mL 1, 2-dichloroethane, and anhydrous ferric chloride (649 mg, 4.0 mmol) was added as a catalyst at room temperature. The reaction system was placed in an oil bath at 80 °C and stirred for 24 h. After cooling to room temperature, the solid obtained by filtering the reaction was washed with methanol, chloroform, water and acetone several times. The washed solid was placed in a methanol solution for Soxhlet extraction, and then vacuum dried at 80 °C to obtain a yellow-brown solid powder, which was acenaphthenequinone diimine functionalized hypercrosslinked microporous polymer, named DIM AQ -HCP-1.

[0041] (3) Synthesis route of acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer catalyst (named DIM AQ -Pd-HCP-1) is as follows:

[0042] Under nitrogen atmosphere, DIM AQHCP-1 (100 mg) and palladium dichloride (22 mg) were added to 10 mL of methanol as solvent, and the mixture was stirred at 80 °C for 12 h. Heating and stirring were then stopped, and the mixture was cooled to room temperature. The resulting mixture was filtered, and the solid was washed several times with dichloromethane, methanol, water, and acetone to remove unreacted palladium chloride. The solid was then extracted with methanol using a Soxhlet extract and vacuum dried at 80 °C to obtain a brownish-yellow powder, which is the palladium diimide functionalized hypercrosslinked microporous polymer catalyst, named DIM. AQ -Pd-HCP-1.

[0043] The content of palladium in the synthesized hypercrosslinked microporous polymer was measured to be 3.15 wt% using an ICP testing instrument, confirming the successful loading of palladium chloride onto DIM. AQ DIM was generated in the HCP-1 material framework. AQ -Pd-HCP-1 hypercrosslinked microporous polymer catalyst.

[0044] Figure 1 The functionalized monomer (1E,2E)-N obtained in Example 1 1 N 2 The 1H NMR spectrum of bis[2,4,6-tris-(diphenylmethylphenyl)]acenaphthene-1,2-diimine, Figure 2 The functionalized monomer (1E,2E)-N obtained in Example 1 1 N 2 The carbon spectrum of bis[2,4,6-tris-(diphenylmethylphenyl)]acenaphthene-1,2-diimine, by Figure 1 and Figure 2 It can be confirmed that 1 The assignment of each signal in the 1H NMR spectrum conforms to the theoretical assignment of hydrogen signal peaks. Further characterization by carbon NMR spectroscopy confirms that the monomer structure is the target monomer of this invention, (1E,2E)-N. 1 N 2 -bis[2,4,6-tris-(diphenylmethylphenyl)]acenaphthene-1,2-diimide.

[0045] Figure 3 It is a hypercrosslinked microporous polymer DIM AQ -HCP-1 solid-state NMR 13 C spectrum. (From DIM) AQ -HCP-1 solid-state NMR 13 The C-spectrum shows that the broad signal in the 124-145 ppm range belongs to the functionalized monomer (1E, 2E)-N. 1 N 2The carbon atoms in the benzene and naphthalene rings of bis[2,4,6-tris-(diphenylmethylphenyl)]acenaphthene-1,2-diimine are attributed to tertiary carbon atoms in the functionalized monomers. The signal peak at 56 and 52 ppm is attributed to the methylene carbon in the linker. This indicates the successful synthesis of the hypercrosslinked microporous polymer DIM via a ferric chloride-catalyzed Friedel-Crafts alkylation reaction. AQ -HCP-1.

[0046] Figure 4 DIM is a palladium-functionalized hypercrosslinked microporous polymer catalyst for acenaphthene diimine. AQ X-ray photoelectron spectroscopy (XPS) of Pd 3d from Pd-HCP-1. XPS spectroscopy shows Pd 3d... 5 / 2 The binding energies (BE) of the orbitals are 343.3 eV and 338.0 eV, indicating that DIM... AQ Pd species in -Pd-HCP-1 exist in the +2 valence state.

[0047] Figure 5 DIM is a palladium-functionalized hypercrosslinked microporous polymer catalyst for acenaphthene diimine. AQ N 1s X-ray photoelectron spectrum of -Pd-HCP-1. XPS spectrum shows DIM AQ The binding energy of N 1s in -Pd-HCP-1 shifted positively from 400.1 eV to 398.8 eV, further indicating a strong coordination interaction between the N,N-bident ligand and PdCl2.

[0048] Figure 6 DIM prepared in Example 1 AQ Thermogravimetric analysis (TGA) plot of Pd-HCP-1. Thermogravimetric analysis (TGA) shows that the above material is stable up to 310℃ under a nitrogen atmosphere.

[0049] Figure 7 The DIM prepared in Example 1 AQ Powder X-ray diffraction pattern of Pd-HCP-1. Powder X-ray diffraction (PXRD) indicates that this material is an amorphous structure.

[0050] Figure 8 For DIM AQ Scanning electron microscope (SEM) image of Pd-HCP-1. The SEM image shows DIM. AQ -Pd-HCP-1 is composed of abundant bulk structures and a small amount of nanosheets.

[0051] Figure 9 and Figure 10 DIM AQThe nitrogen adsorption curve and pore size distribution of Pd-HCP-1. The specific surface area and pore size analyzer measured the DIM AQ The specific surface area of Pd-HCP-1 is 538.9 m 2 g -1 The pore size distribution curve shows that there are a large number of micropores and mesopores in the material.

[0052] Example 2 Different from Example 1, in the preparation method of step (2) acenaphthenequinone diimine functionalized hypercrosslinked microporous polymer (named DIM AQ -HCP-2), 1, 3, 5-triphenylbenzene is also added, specifically: Under the protection of nitrogen atmosphere, a magnetic stirrer is added in a dry and clean 50 mL round-bottom flask, (1E, 2E)-N 1 ,N 2 -Disubstituted [2, 4, 6-tri-(diphenylmethylphenyl)]acenaphthylene-1, 2-diimine (0.3 mmol, 398 mg), 1, 3, 5-triphenylbenzene (91.8 mg, 0.3 mmol), dimethylformaldehyde (608 mg, 8.0 mmol) are dispersed in 5 mL 1, 2-dichloroethane, anhydrous ferric chloride (1.23 g, 8.0 mmol) is added as a catalyst at room temperature, the reaction system is placed in an 80 ℃ oil bath and stirred for 24 hours, after cooling to room temperature, the solid obtained by filtering the reaction is washed with methanol, chloroform, water and acetone for several times, the washed solid is placed in a methanol solution for Soxhlet extraction, and then vacuum dried at 80 ℃ to obtain a yellow-brown solid powder, which is acenaphthenequinone diimine functionalized hypercrosslinked microporous polymer, named DIM AQ -HCP-2.

[0053] Other preparation methods are consistent with Example 1, and the prepared acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer catalyst (named DIM AQ -Pd-HCP-2).

[0054] Example 3 Different from Example 1, in the preparation method of step (2) acenaphthenequinone diimine functionalized hypercrosslinked microporous polymer (named DIM AQ -HCP-3), tetraphenylmethane is also added, specifically: Under the protection of nitrogen atmosphere, a magnetic stirrer is added in a dry and clean 50 mL round-bottom flask, (1E, 2E)-N 1 ,N 2- Bis[2, 4, 6-tris-(diphenylmethy1phenyl)]acenaphthylene-1, 2-diimine (0.3 mmol, 398 mg), tetraphenylmethane (96.0 mg, 0.3 mmol), dimethylformaldehyde (608 mg, 8.0 mmol) were dispersed in 5 mL of 1, 2-dichloroethane, anhydrous ferric chloride (1.23 g, 8.0 mmol) was added as catalyst at room temperature, the reaction system was placed in an 80 °C oil bath and stirred for 24 h, after cooling to room temperature, the solid obtained by filtering the reaction was washed with methanol, chloroform, water and acetone for several times, the washed solid was placed in a methanol solution for Soxhlet extraction, and then dried at 80 °C under vacuum to obtain a yellow-brown solid powder, which was acenaphthylenequinone diimine functionalized hypercrosslinked microporous polymer, named as DIM AQ HCP-3.

[0055] Other preparation methods are consistent with example 1, and the acenaphthylenequinone diimine palladium functionalized hypercrosslinked microporous polymer catalyst (named as DIM AQ Pd-HCP-3) is prepared.

[0056] Application example 1 The acenaphthylenequinone diimine palladium functionalized hypercrosslinked microporous polymer prepared by the application is used to catalyze the direct C-H arylation reaction of aryl bromide and heteroarene, and the catalytic yield and recycling of the catalyst are verified, as follows: 1. The DIM AQ Pd-HCP-1 porous catalyst prepared in example 1 is applied to catalyze the direct C-H activation reaction of heteroarene bromide and heteroarene, specifically as follows: (1) 2, 4-dimethylthiazole and 5-bromo-2-methylpyridine are reacted to synthesize a heteroaromatic ring compound, and the specific steps are as follows: A reaction tube equipped with a stirring magnet was charged with DIM AQ Pd-HCP-1 (0.5 mol%), 5-bromo-2-methylpyridine (0.2 mmol), 2, 4-dimethylthiazole (0.3 mmol), K2CO3 (0.3 mmol), PivOH (0.06 mmol) and 1.0 mL of DMAc. The reaction mixture was stirred at 130 °C for 12 h. After the reaction was completed (monitored by TLC), the reaction mixture was cooled to room temperature, then the mixture was centrifuged, and the solid was washed with EtOAc (3×5 mL), the organic phases were combined and washed with dichloromethane for three times, the organic layer was dried over anhydrous Na2SO4, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude product was purified by silica gel column chromatography with petroleum ether / ethyl acetate (6 / 1, v / v) as eluent, and the product was obtained by 1 H NMR and 13C10 NMR characterization confirmed the obtained compound, with a yield of 98%.

[0057] (2) The synthesis of a heterocyclic aromatic compound by catalytic reaction of 2,4-dimethylthiazole with 5-bromo-2-methoxypyridine is as follows: Add DIM to a reaction tube equipped with a magnetic stir bar. AQ -Pd-HCP-1 (0.5 mol%), 5-bromo-2-methoxypyridine (0.2 mmol), 2,4-dimethylthiazole (0.3 mmol), K2CO3 (0.3 mmol), PivOH (0.06 mmol), and 1.0 mL DMAc. The reaction mixture was stirred at 130 °C for 12 h. After the reaction was complete (monitored by TLC), the reaction mixture was cooled to room temperature, centrifuged, and the solids were washed with EtOAc (3 × 5 mL). The combined organic phases were extracted and washed three times with dichloromethane. The organic layer was dried over anhydrous Na2SO4, filtered, and the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (6 / 1, v / v) as the eluent. 1 H NMR and 13 The compound was identified by C10 NMR characterization, with a yield of 95%.

[0058] (3) The synthesis of heterocyclic aromatic compounds by catalyzing the reaction of 2,4-dimethylthiazole with p-bromoacetophenone is as follows: Add DIM to a reaction tube equipped with a magnetic stir bar. AQ -Pd-HCP-1 (0.5 mol%), p-bromoacetophenone (0.2 mmol), 2,4-dimethylthiazole (0.3 mmol), K2CO3 (0.3 mmol), PivOH (0.06 mmol), and 1.0 mL DMAc. The reaction mixture was stirred at 130 °C for 12 h. After the reaction was complete (monitored by TLC), the reaction mixture was cooled to room temperature, centrifuged, and the solids were washed with EtOAc (3 × 5 mL). The combined organic phases were extracted and washed three times with dichloromethane. The organic layer was dried over anhydrous Na2SO4, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (10 / 1, v / v) as the eluent. 1 H NMR and 13 The compound was identified by C10 NMR characterization, with a yield of 95%.

[0059] (4) The synthesis of bi-heterocyclic aromatic compounds by catalytic reaction of 2-methylthiophene with 5-bromopyrimidine is as follows: Add DIM to a reaction tube equipped with a magnetic stir bar. AQPd-HCP-1 (0.5 mol%), 5-bromopyrimidine (0.2 mmol), 2-methylthiophene (0.3 mmol), K2CO3 (0.3 mmol), PivOH (0.06 mmol) and 1.0 mL DMAc. The reaction mixture was stirred at 130 °C for 12 h. After completion of the reaction (monitored by TLC), the reaction mixture was cooled to room temperature, then the mixture was centrifuged and the solid was washed with EtOAc (3 x 5 mL), the organic phases were combined and washed with dichloromethane three times, the organic layer was dried over anhydrous Na2SO4, filtered and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica gel with petroleum ether / ethyl acetate (10 / 1, v / v) as eluent, and the product was characterized by1H NMR and13C NMR to be the resulting compound with a yield of 84%. 1 H NMR and 13 C NMR characterization to be the resulting compound with a yield of 84%.

[0060] (5) Catalyze 3,5-dimethylisoxazole to react with 3-bromopyridine to synthesize a heteroaromatic ring compound, the specific steps are as follows: In the reaction tube equipped with a stirring magnet, DIM AQ Pd-HCP-1 (0.5 mol%), 3-bromopyridine (0.2 mmol), 3,5-dimethylisoxazole (0.3 mmol), K2CO3 (0.3 mmol), PivOH (0.06 mmol) and 1.0 mL DMAc. The reaction mixture was stirred at 130 °C for 12 h. After completion of the reaction (monitored by TLC), the reaction mixture was cooled to room temperature, then the mixture was centrifuged and the solid was washed with EtOAc (3 x 5 mL), the organic phases were combined and washed with dichloromethane three times, the organic layer was dried over anhydrous Na2SO4, filtered and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica gel with petroleum ether / ethyl acetate (10 / 1, v / v) as eluent, and the product was characterized by1H NMR and13C NMR to be the resulting compound with a yield of 90%. 1 H NMR and 13 C NMR characterization to be the resulting compound with a yield of 90%.

[0061] (6) Catalyze imidazopyridine to react with 5-bromo-2-methylpyridine to synthesize a heteroaromatic ring compound, the specific steps are as follows: In the reaction tube equipped with a stirring magnet, DIM AQPd-HCP-1 (0.5 mol%), 5-bromo-2-methylpyridine (0.2 mmol), imidazopyridine (0.3 mmol), K2CO3 (0.3 mmol), PivOH (0.06 mmol) and 1.0 mL of DMAc. The reaction mixture was stirred at 130 °C for 12 h. After completion of the reaction (monitored by TLC), the reaction mixture was cooled to room temperature, the mixture was centrifuged and the solid was washed with EtOAc (3 x 5 mL), the organic phases were combined and washed with dichloromethane three times, the organic layer was dried over anhydrous Na2SO4, filtered and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica gel using petroleum ether / dichloromethane (10 / 1, v / v) as eluent, and the product was characterized by1H NMR and13C NMR to be the resulting compound with a yield of 97%. 1 H NMR and 13 C NMR characterization to be the resulting compound with a yield of 97%.

[0062] (7) Catalyze the reaction of benzothiophene and 3-bromopyridine to synthesize a heteroaromatic ring compound, the specific steps are as follows: In the reaction tube equipped with a stirring magnet, DIM AQ Pd-HCP-1 (0.5 mol%), 3-bromopyridine (0.2 mmol), benzothiophene (0.3 mmol), K2CO3 (0.3 mmol), PivOH (0.06 mmol) and 1.0 mL of DMAc. The reaction mixture was stirred at 130 °C for 12 h. After completion of the reaction (monitored by TLC), the reaction mixture was cooled to room temperature, the mixture was centrifuged and the solid was washed with EtOAc (3 x 5 mL), the organic phases were combined and washed with dichloromethane three times, the organic layer was dried over anhydrous Na2SO4, filtered and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica gel using petroleum ether / dichloromethane (20 / 1, v / v) as eluent, and the product was characterized by1H NMR and13C NMR to be the resulting compound with a yield of 83%. 1 H NMR and 13 C NMR characterization to be the resulting compound with a yield of 83%.

[0063] (8) Catalyze the reaction of 2-methylfuran and 4-bromoisoquinoline to synthesize a heteroaromatic ring compound, the specific steps are as follows: In the reaction tube equipped with a stirring magnet, DIM AQPd-HCP-1 (0.5 mol%), 4-bromoisoquinoline (0.2 mmol), 2-methylfuran (0.3 mmol), K2CO3 (0.3 mmol), PivOH (0.06 mmol) and 1.0 mL DMAc. The reaction mixture was stirred at 130 °C for 12 h. After completion of the reaction (monitored by TLC), the reaction mixture was cooled to room temperature, then the mixture was centrifuged and the solid was washed with EtOAc (3 x 5 mL), the organic phase was combined and extracted with dichloromethane three times, the organic layer was dried over anhydrous Na2SO4, filtered and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (10 / 1, v / v) as eluent, and the product was characterized by1H NMR and13C NMR to be the desired compound with a yield of 66%. 1 H NMR and 13 C NMR characterization to be the resulting compound with a yield of 66%.

[0064] 2. Recycling of the catalyst The DIM AQ -Pd-HCP-1 catalyst was recovered by centrifugation. The recovered DIM AQ -Pd-HCP-1 catalyst was washed with ethyl acetate and methanol / water to remove the residual product, and was used again after simple drying. The direct C-H activation reaction of 2,4-dimethylthiazole with 5-bromo-2-methylpyridine was selected to investigate the recyclability of the DIM AQ -Pd-HCP-1 catalyst, and the study showed that the catalyst could be recycled for 5 times without loss of activity. The average yield of the 5 recycling experiments was 90%.

[0065] 3. The direct C-H activation reaction of 2,4-dimethylthiazole with 5-bromo-2-methylpyridine catalyzed by DIM AQ -Pd-HCP-1 (Example 1), DIM AQ -Pd-HCP-2 (Example 2), DIM AQ -Pd-HCP-3 (Example 3), palladium chloride and DIM AQ -HCP-1, and the specific results are shown in Table 1.

[0066] Table 1 Performance of the catalyst

[0067] As can be seen from Table 1, the DIM AQ -Pd-HCP-1 has high catalytic activity due to the high loading amount of palladium catalyst.

[0068] The above merely provides the preferred embodiments of the present application, and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the principles and technical scope of the present application shall fall into the scope of the present application.

Claims

1. A acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer, characterized in that, The acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer has a structural unit shown in any one of formula I-III: Formula I Formula II Formula III.

2. The acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer of claim 1, wherein, The specific surface area of the acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer is 530-890 m 2 ·g -1 , the content of metal palladium is 3.0-4.0 wt%.

3. A process for the preparation of the acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer according to claim 1 or 2, characterized in that, The method comprises the following steps: (1E,2E)-N 1 ,N 2 -bis[2,4,6-tris-(diphenylmethylphenyl)]acenaphthylene-1,2-diimine; (1E,2E)-N 1 ,N 2 A functionalized hypercrosslinked microporous polymer of acenaphthoquinone diimine was prepared by subjecting (1E,2E)-N The crosslinking agent is one or more of dimethylene formaldehyde, chloro(methoxy)methane and 1,2-dichloroethane; The acenaphthenequinone diimine functionalized hypercrosslinked microporous polymer and the palladium dichloride are subjected to a coordination reaction to obtain the acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer.

4. The method for preparing the acenaphthene diimine palladium-functionalized hypercrosslinked microporous polymer according to claim 3, characterized in that, The molar ratio of the 2,4,6-tris(benzhydryl)aniline and the acenaphthenequinone is (2-3):1; The temperature of the ketone amine condensation reaction is 140-150℃, and the reaction time is 4-10 h.

5. The method for preparing the acenaphthene diimine palladium-functionalized hypercrosslinked microporous polymer according to claim 3, characterized in that, said (1E,2E)-N 1 ,N 2 In the presence of said (1E,2E)-N 1 ,N 2 - bis[2,4,6-tris-(diphenylmethylphenyl)]acenaphthylene-1,2-diimine and crosslinking agent, a comonomer is also added, which is one or both of 1,3,5-triphenylbenzene and tetraphenylmethane; The molar ratio of the (1E,2E)-N1,N2-bis[2,4,6-tris(benzhydrylphenyl)]acenaphthene-1,2-diimine, the crosslinking agent and the comonomer is 1:(10-30):(0-1). The atmosphere of the Friedel-Crafts alkylation reaction is inert atmosphere, the temperature is 60-80℃, and the reaction time is 20-30 h.

6. The method for preparing the acenaphthene diimine palladium-functionalized hypercrosslinked microporous polymer according to claim 3, characterized in that, The molar ratio of the acenaphthenequinone diimine functionalized hypercrosslinked microporous polymer and the palladium dichloride is 1:(2-3). The temperature of the coordination reaction is 70-90℃, and the reaction time is 10-15 h.

7. The method for preparing the acenaphthene diimine palladium-functionalized hypercrosslinked microporous polymer according to claim 3, characterized in that, The catalyst used in the ketone amine condensation reaction and the Friedel-Crafts alkylation reaction is one of anhydrous ferric chloride, anhydrous aluminum chloride and anhydrous zinc chloride, and the solvent used is one of chloroform, 1,2-dichloroethane, methanol, ethanol and acetic acid.

8. Application of the acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer in the direct C-H activation reaction of heteroaromatic bromide and heteroaromatic compound.

9. A method for direct C-H activation reaction of heteroarene bromide and heteroarene compound, characterized in that, The acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer, the heteroaromatic bromide, the heteroaromatic compound, the base, the additive and the solvent are mixed, and then the reaction is carried out under the protection of inert atmosphere.

10. The method of direct C-H activation of heteroarene bromide and heteroarene compounds according to claim 9, characterized in that, The molar ratio of the acenaphthenequinone diimine palladium functionalized hypercrosslinked microporous polymer, the heteroaromatic bromide, the heteroaromatic compound, the base and the additive is 1:(1-2):(0.001-0.005):(1-3):(0.2-0.5). The heteroaromatic bromide is one of 3-bromopyridine, 5-bromopyrimidine, 5-bromo-2-methylpyridine, 4-bromoisoquinoline, 5-bromo-2-methoxypyridine and 2-bromothiophene; The heteroaromatic compound is one of 2,4-dimethylthiazole, 2-methylthiophene, 3,5-dimethylisoxazole, benzothiophene, 2-methylfuran and 4-bromoisoquinoline, 4-methylthiazole and 1,2-dimethylimidazole; The temperature of the reaction is 120-140℃, and the reaction time is 10-15 h.

Images