A bis-oxazoline pyridine functionalized porous organic polymer and preparation and use thereof

Abstract

The application discloses a bisoxazoline pyridine functionalized porous organic polymer and preparation and application thereof; firstly, a styryl functionalized PyBox monomer (VPyBox) is designed and synthesized, and VPyBox, styrene and divinylbenzene are subjected to free radical polymerization under initiation of azobisisobutyronitrile in a certain proportion to obtain a series of porous organic polymers (POP-PyBox); the POP-PyBox can be used as a solid N , N , N tridentate ligand for Co-catalyzed hydrosilylation of arylalkynes with diphenylsilane; the heterogeneous catalyst system developed by the application has a catalytic activity comparable to that of a homogeneous catalyst reported in the literature, and the catalyst is easy to separate and recover; the recovered catalyst can be recycled for more than 6 times, which can not only greatly reduce the preparation cost of vinylsilane, but also simplify the post-treatment process and reduce the three wastes, and has a good practical application prospect.

Description

Technical Field

[0001] This invention relates to a bisoxazoline pyridine-functionalized porous organic polymer (POP-PyBox) and its preparation method, as well as its application as a solid NNN tridentate ligand in Co-catalyzed hydrosilylation of alkynes. Background Technology

[0002] Vinylsilanes are an important class of organic compounds, widely used in agrochemicals, drug development, and novel functional materials. Transition metal-catalyzed hydrosilylation of alkynes is one of the main methods for preparing these compounds. Traditional catalytic systems primarily rely on noble metals such as Pt, Pd, Rh, and Ir. Due to the limited reserves and high prices of these noble metals, in recent years, academia and industry have focused on developing inexpensive transition metals (such as Co, Fe, and Ni) for catalyzing this reaction, achieving fruitful results. Among them, the cobalt-bisoxazoline (PyBox-Co) developed by Professor Huang Zheng's group at the Shanghai Institute of Organic Chemistry in 2016 is one of the most efficient catalysts. Ang. Chem. Int. Ed. 2016 55 (10839-10843). The method uses 0.5 mmol% PyBox-CoCl2 as a precatalyst, 1 mol% NaBHEt3 as an activating agent, and THF as the reaction medium. The reaction is carried out at room temperature for 1-2 h. Many arylacetylenes can undergo hydrosilylation with diphenylsilanes to obtain the corresponding vinylsilanes. The reaction has good regioselectivity, mainly producing the Markovnikov addition product 1,1-disubstituted olefin (2), and the proportion of the anti-Markovnikov addition product 1,2-disubstituted olefin (2') is generally less than 10%.

[0003]

[0004] However, the reactions reported above are carried out under homogeneous conditions, and the catalyst PyBox-CoCl2 cannot be recovered and reused. In particular, the ligand PyBox requires a multi-step synthetic reaction to obtain, resulting in high preparation costs.

[0005] To overcome the aforementioned limitations, this invention designs and prepares a PyBox-functionalized porous organic polymer (POP-PyBox), which is then used as a solid NNN tridentate ligand for online coordination with CoCl2 to catalyze the hydrosilylation of alkynes. The reaction proceeds under heterogeneous conditions, with the catalyst insoluble in the reaction medium. After the reaction, the catalyst can be separated from the product and recovered through simple centrifugation or filtration. The recovered catalyst can be reused multiple times while maintaining its catalytic activity. This not only significantly reduces production costs but also simplifies the post-processing and reduces waste emissions.

[0006] Summary of the Invention

[0007] The present invention aims to provide a novel bisoxazoline pyridine-functionalized porous organic polymer (POP-PyBox), its preparation method and application.

[0008] This invention first designs and synthesizes a styrene-functionalized PyBox monomer (VPyBox), and then performs free radical polymerization of VPyBox, styrene (ST), and divinylbenzene (DVB) in a certain ratio under the initiation of azobisisobutyronitrile (AIBN) to obtain a series of porous organic polymers (POP-PyBox). Using POP-PyBox as a ligand, it undergoes online coordination with CoCl2 to obtain the corresponding POP-PyBox-CoCl2 complex, which is then subjected to NaO... t After online activation, Bu is used to catalyze the hydrosilylation reaction of aryl alkynes with silanes.

[0009] The heterogeneous catalyst system of this invention exhibits catalytic activity and selectivity comparable to homogeneous catalysts reported in the literature, and the catalyst is easily separated and recovered. The recovered catalyst can be recycled more than 6 times while still maintaining good catalytic activity.

[0010] The technical solution of the present invention is as follows: A 4-styrene-functionalized bisoxazoline pyridine monomer, abbreviated as VPyBox, is shown in Formula VII:

[0011] The preparation method of the VPyBox of the present invention includes the following steps: (1) Mix 4-hydroxypyridine-2,6-dicarboxylic acid as shown in Formula I with methanol, add SOCl2 dropwise at 0~5℃, then raise to room temperature and continue stirring for 36 h. After post-treatment of the reaction solution, the intermediate shown in Formula II is obtained: dimethyl 4-hydroxypyridine-2,6-dicarboxylic acid. The 4-hydroxypyridine-2,6-dicarboxylic acid shown in formula I is commercially available.

[0012] The molar ratio of 4-hydroxypyridine-2,6-dicarboxylic acid, methanol, and SOCl2 shown in Formula I is 1:10~20:2.0~4.0, preferably 1:15:3.0; Specific post-processing method: After the reaction is completed, methanol is recovered by rotary evaporation at 40°C. The residue is dissolved in dichloromethane, washed with water until neutral, dried with anhydrous sodium sulfate, and the solvent is recovered by rotary evaporation to obtain the intermediate shown in Formula II.

[0013] (2) The intermediate shown in Formula II was mixed with PBr5 and stirred at 80°C for 6 h. The reaction solution was post-treated to obtain the intermediate shown in Formula III: 4-bromopyridine-2,6-dicarboxylic acid dimethyl ester. The molar ratio of the intermediate shown in Formula II to PBr5 is 1:1.0~2.0, preferably 1:1.5; Specific post-processing method: After the reaction is completed, the temperature is lowered to room temperature, a mixed solution of dichloromethane and methanol (volume ratio 1:1) is added, the mixture is stirred for 1 h, then washed with 1 mol / L Na2CO3 and saturated NaCl, dried with anhydrous sodium sulfate, the solvent is recovered by rotary evaporation, and the residue is recrystallized from methanol to obtain the intermediate shown in Formula III.

[0014] (3) Dissolve the intermediate shown in Formula III and KOH in methanol, stir at 65°C for 5 h, and then treat the reaction solution to obtain the intermediate shown in Formula IV: 4-bromopyridine-2,6-dicarboxylic acid; The molar ratio of the intermediate shown in Formula III to KOH is 1:1.0~4.0, preferably 1:2.5; Specific post-processing method: After the reaction is completed, the reaction solution is rotary evaporated to recover methanol, the residue is dissolved in water, 10% hydrochloric acid aqueous solution is added dropwise until pH≈1, filtered, the filter cake is washed with water, and vacuum dried to obtain the intermediate shown in Formula IV;

[0015] (4) The intermediate shown in Formula IV, oxalyl chloride, N , N - Dimethylformamide (catalyst) was dissolved in dichloromethane and reacted at room temperature for 6 h. The mixture was then evaporated under reduced pressure (to recover the solvent and oxalyl chloride) to obtain an acyl chloride derivative. The obtained acyl chloride derivative, valine, and triethylamine were dissolved in dichloromethane and reacted at room temperature for 2 h. The reaction solution was post-treated to obtain the intermediate shown in formula V: 4-bromo-2,6-bis[ N -(1'-hydroxy-3'-methylbut-2'-yl)]carbamoylpyridine; The intermediate shown in Formula IV, oxalyl chloride, N , N The molar ratio of dimethylformamide is 1:2.0~6.0:0.02~0.1, preferably 1:3.0:0.05; The molar ratio of acyl chloride derivative, valine, and triethylamine is 1:2.0~4.0:2.0~6.0, preferably 1:3.0:4.0; Specific post-processing method: After the reaction is completed, the reaction solution is washed successively with 5% hydrochloric acid aqueous solution and 5% sodium bicarbonate aqueous solution, dried with anhydrous sodium sulfate, the solvent is recovered by rotary evaporation, and the residue is purified by silica gel column chromatography (ethyl acetate / petroleum ether = 1 / 1, v / v) to obtain the intermediate shown in formula V.

[0016] (5) Under a N2 atmosphere, the intermediate shown in Formula V, 4-vinylphenylboronic acid, palladium chloride, RuPhox (2-dicyclohexylphosphine-2',6'-diisopropoxy-1,1'-biphenyl), and cesium carbonate were mixed in THF / H2O, heated to 75℃ and stirred for 8 h. After post-treatment, the reaction solution was used to obtain the intermediate shown in Formula VI: 4-(4'-vinyl)phenyl-2,6-bis[ N -(1'-hydroxy-3'-methylbut-2'-yl)]carbamoylpyridine; The molar ratio of the intermediate shown in Formula V, 4-vinylphenylboronic acid, palladium chloride, RuPhox, and cesium carbonate is 1:1.0~2.0:0.04~0.15:0.08~0.20:2.0~5.0, preferably 1:1.2:0.08:0.12:3.0; In the solvent THF / H2O, the volume ratio of THF to H2O is 6~12:1, preferably 9:1; Specific post-processing method: After the reaction is completed, the mixture is cooled to room temperature. Diatomaceous earth and anhydrous sodium sulfate are added to the reaction solution and stirred for 30 min. The mixture is filtered, and the solvent is recovered by rotary evaporation of the filtrate. The residue is purified by silica gel column chromatography (ethyl acetate / petroleum ether = 1 / 2, v / v) to obtain the intermediate shown in Formula VI.

[0017] (6) Under N2 atmosphere, the intermediate shown in Formula VI was dissolved in dichloromethane, cooled to -20℃, and DAST (diethylaminotrifluoride) was added dropwise. The reaction was carried out for 30 min. After post-treatment, the product shown in Formula VII was obtained: 4-(4'-vinyl)phenyl-2,6-bis(4'-isopropyl-4',5'-dihydrooxazol-2'-yl)pyridine (VPyBox). The molar ratio of the intermediate shown in Formula VI to DAST is 1:3~6, preferably 1:4; Specific post-processing method: After the reaction is completed, saturated sodium bicarbonate aqueous solution is added to quench the reaction, the organic layer is separated, the aqueous layer is extracted with dichloromethane, the organic layers are combined, dried with anhydrous sodium sulfate, the solvent is recovered by rotary evaporation, and the residue is purified by silica gel column chromatography (ethyl acetate / petroleum ether = 1 / 4, v / v) to obtain the product shown in Formula VII.

[0018] A bisoxazoline pyridine-functionalized porous organic polymer, abbreviated as POP-PyBox, is shown in Formula VIII:

[0019] In equation VIII, x:y:z = 1:0 ~ 8:12.

[0020] The method for preparing the POP-PyBox of the present invention includes: Under a nitrogen atmosphere, VPyBox, styrene, divinylbenzene, and azobisisobutyronitrile were dissolved in toluene and polymerized at 80°C for 24 h. After cooling to room temperature, the resulting blocky solid was washed (ultrasonically washed with tetrahydrofuran) and vacuum dried (60°C, 12 h) to obtain POP-PyBox (which was then ground into powder for later use). The molar ratio of VPyBox, styrene, and divinylbenzene is 1:0 to 8:12; The mass ratio of azobisisobutyronitrile to VPyBox is 0.1~0.2:1, preferably 0.12:1; The mass ratio of toluene to VPyBox is 6~9:1, preferably 7.5:1.

[0021] The POP-PyBox of this invention can be used as a solid N , N , N Tridentate ligands are used in the Co-catalyzed hydrosilylation reaction of aryl alkynes with diphenylsilanes. Specifically: Under nitrogen protection, POP-PyBox, CoCl2, and anhydrous tetrahydrofuran were mixed and stirred at room temperature for 1 h. Sodium tert-butoxide, diphenylsilane as shown in formula A, and aryl alkyne as shown in formula B were added and stirred at room temperature for 4-8 h. The reaction solution was post-treated to obtain the hydrosilylated product as shown in formula C. The preferred molar ratio of diphenylsilane (Formula A), aryl alkyne (Formula B), POP-PyBox, CoCl2, and sodium tert-butoxide is 1.2:1:0.15:0.01:0.03. Specific post-processing method: After the reaction is completed, the reaction system is exposed to air and stirred for 10 min to quench the reaction. After centrifugation, the supernatant is collected. The solid is washed with THF and reused. The organic phases are combined and the solvent is recovered by rotary evaporation. The residue is purified by silica gel column chromatography (ethyl acetate / petroleum ether = 1 / 10~1 / 3, v / v) to obtain the hydrosilylated product shown in formula C. The reaction formula is as follows:

[0022] In equations B and C, Ar represents aryl, heteroaryl, substituted aryl, or substituted heteroaryl; the substituted aryl or substituted heteroaryl has one or more substituents, each of which is independently selected from: C1-C3 alkyl, C1-C3 alkoxy, phenyl, amino, halogen, trifluoromethyl, C1-C3 alkyl acyl, C1-C3 alkoxy acyl, or cyano. Aryl groups, for example: phenyl, naphthyl; heteroaryl groups, for example: thiophene, pyridine.

[0023] Compared with the prior art, the beneficial effects of the present invention are reflected in: This invention designs and develops a novel bisoxazoline pyridine-functionalized porous organic polymer, which can be used as a solid... N , N , N Tridentate ligands are used in the Co-catalyzed hydrosilylation reaction of aryl alkynes with diphenylsilanes.

[0024] The heterogeneous catalyst system developed in this invention exhibits catalytic activity comparable to homogeneous catalysts reported in the literature. Furthermore, the catalyst is easily separated and recovered, and the recovered catalyst can be recycled more than six times. This not only significantly reduces the preparation cost of vinylsilanes but also simplifies the post-processing and reduces waste, demonstrating promising prospects for practical applications. Attached Figure Description

[0025] Figure 1 : Aggregate monomer VPyBox 1 H NMR spectrum (500 MHz).

[0026] Figure 2 : Aggregate monomer VPyBox 13 C NMR spectrum (125 MHz).

[0027] Figure 3 HRMS (ESI+) plot of the polymer monomer VPyBox.

[0028] Figure 4 N2 adsorption-desorption isotherms of polymer POP-PyBox-3.

[0029] Figure 5 Pore ​​size distribution diagram of polymer POP-PyBox-3.

[0030] Figure 6 Physical images of polymer POP-PyBox-1, 2, 3, and 4.

[0031] Figure 7 IR diagrams of polymer POP-PyBox-3 and monomer VByBox.

[0032] Figure 8TGA diagram of polymer POP-PyBox-3.

[0033] Figure 9 SEM image of polymer POP-PyBox-3.

[0034] Figure 10 TEM image of polymer POP-PyBox-3.

[0035] Figure 11 : Results of continuous recycling of the catalyst system POP-PyBox-3-Co for 6 cycles. Detailed Implementation

[0036] The present invention is further described below through specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0037] Example 1: Preparation of styrene-functionalized bisoxazoline pyridine ligand (VPyBox)

[0038] Preparation of Intermediate II: In a 100 mL round-bottom reaction flask, 12.0 g (65.5 mmol) of 4-hydroxypyridine-2,6-dicarboxylic acid and 40 mL of methanol were added. After stirring to dissolve, the mixture was cooled to 0–5 °C in an ice bath. Then, SOCl2 (23.4 g, 196.5 mmol) was added dropwise over 30 min. After the addition was complete, the cold bath was removed, and the reaction was continued to be stirred at room temperature for 36 hours. The reaction progress was monitored by TLC. After the reaction was completed, methanol was recovered by rotary evaporation under reduced pressure at 40 °C. The residue was dissolved in dichloromethane, washed with water until neutral, and the organic phase was dried over anhydrous sodium sulfate. After filtration, the mother liquor was evaporated under reduced pressure to recover the solvent, yielding 12.5 g of a yellow solid, with a yield of 91%. 1 H NMR (500 MHz, DMSO-) d 6 ): δ=11.66 (s, 1H), 7.54 (s, 2H), 3.89 (s, 6H) ppm.

[0039] Preparation of Intermediate III: Intermediate II (3.0 g, 14.3 mmol) and phosphorus pentabromide (9.1 g, 21.4 mmol) were added to a 50 mL round-bottom reaction flask. The mixture was heated to 80 °C and stirred at this temperature for 6 hours, with the reaction progress monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature, and 30 mL of chloroform and 30 mL of methanol were added. The mixture was stirred for 1 hour to remove excess phosphorus pentabromide. The mixture was then washed successively with 1 mol / L Na₂CO₃ (15 mL × 3) and saturated NaCl (15 mL × 3), dried over anhydrous sodium sulfate, filtered, and the mother liquor was evaporated under reduced pressure to recover the solvent. The residue was recrystallized from methanol to give 3.1 g of a white solid, with a yield of 95%. 1H NMR (500MHz, DMSO-) d 6 ): δ=8.43 (s, 2H) 4.00 (s, 6H) ppm.

[0040] Preparation of Intermediate IV: Intermediate III (8.0 g, 30.0 mmol), potassium hydroxide (4.2 g, 75.0 mmol), and 60 mL of methanol were added to a 100 mL round-bottom reaction flask. The mixture was heated to 65 °C and stirred for 5 hours, with TLC monitoring the reaction progress. After the reaction was complete, the solvent was recovered by rotary evaporation under reduced pressure at 40 °C. The residue was dissolved in 60 mL of water, and 30 mL of 10% hydrochloric acid aqueous solution was slowly added dropwise to adjust the pH of the solution to approximately 1. The mixture was filtered, and the filter cake was dried to give 7.0 g of white solid, with a yield of 96%. 1 H NMR (500 MHz, DMSO-) d 6 ): δ=8.38 (s, 2H) ppm.

[0041] Preparation of Intermediate V: In a 50 mL round-bottom reaction flask, intermediate IV (2.0 g, 8.2 mmol) and 20 mL dichloromethane were added and stirred to dissolve. 0.2 mL DMF was added dropwise, followed by slow addition of oxaloyl chloride (3.1 g, 24.6 mmol) over 5–10 min at room temperature. After the addition was complete, the reaction was stirred at room temperature for 6 h, and the reaction progress was monitored by TLC. After the reaction was complete, the solvent was recovered by rotary evaporation under reduced pressure at 40 °C to obtain 1.2 g of acyl chloride intermediate, which was dissolved in 10 mL dichloromethane for later use. In another 50 mL round-bottom reaction flask, valine (2.5 g, 24.6 mmol), triethylamine (3.3 g, 32.8 mmol), and 20 mL dichloromethane were added and stirred to dissolve. The mixture was then transferred to a 0 °C cold bath, and the dichloromethane solution of the obtained acyl chloride intermediate was slowly added dropwise. After the addition was complete, the cold bath was removed, and the reaction was stirred at room temperature for 2 h, and the reaction progress was monitored by TLC. After the reaction was completed, the reaction solution was washed successively with 5% hydrochloric acid aqueous solution (15 mL × 3) and 5% sodium bicarbonate aqueous solution (15 mL × 3). The organic phase was dried with anhydrous sodium sulfate, filtered, and the mother liquor was evaporated under reduced pressure to recover the solvent. The residue was purified by silica gel column chromatography to obtain 2.3 g of white solid, with a yield of 78%. 1 H NMR (500 MHz, DMSO- d 6 ): δ=8.56 (d, J =9.2 Hz, 2H), 8.31 (s, 2H), 4.74 (s, 2H), 3.77-3.72 (m, 2H), 3.61-3.59 (m, 4H), 1.99 (Octa, J=6.9Hz, 2H), 0.94 (d, J =6.8 Hz, 6H), 0.90 (d, J =6.8Hz, 6H)ppm.

[0042] Preparation of intermediate VI: Under a nitrogen atmosphere, intermediate V (2.0 g, 3.9 mmol), palladium chloride (55.0 mg, 0.31 mmol), RuPhox (218.5 mg, 0.5 mmol), cesium carbonate (3.8 g, 11.7 mmol), 4-vinylphenylboronic acid (0.7 g, 4.7 mmol), and 20 mL of solvent (THF:H2O = 9:1) were added sequentially to a 50 mL Young tube. The temperature was raised to 75 °C and the reaction was carried out for 8 hours. The reaction progress was monitored by TLC. After the reaction was completed, diatomaceous earth and anhydrous sodium sulfate were added to the reaction solution, and the mixture was stirred for 1 hour. The mixture was filtered, and the solvent was recovered by rotary evaporation under reduced pressure from the mother liquor. The residue was purified by silica gel column chromatography to give 1.7 g of white solid, with a yield of 80%. 1 H NMR (500 MHz, CDCl3): δ=8.58 (d, J =9.2Hz, 2H), 8.45 (s, 2H), 7.91 (d, J =8.1Hz, 2H), 7.66 (d, J =8.1Hz, 2H), 6.81 (dd, J =17.6, 11.0Hz, 1H), 5.96 (d, J =17.8Hz, 1H), 5.37 (d, J =11.0 Hz, 1H), 4.79 (t, J =5.4Hz, 2H), 3.84-3.79 (m, 2H), 3,66-3.58 (m, 2H), 2.03 (Octa, J =6.9Hz, 2H), 0.97 (d, J =6.8Hz, 1H), 0.94 (d, J =6.8 Hz, 6H)ppm.

[0043] Preparation of VII (VByBox monomer): Under a nitrogen atmosphere, intermediate VI (1.0 g, 2.3 mmol) and 20 mL of dichloromethane were added to a 100 mL round-bottom reaction flask. After stirring and dissolving, the reaction solution was cooled to -20 °C, and (diethylamino)sulfur trifluoride (DAST) (1.48 g, 9.2 mmol) was slowly added dropwise. The reaction was carried out for 30 minutes, and the reaction progress was monitored by TLC. After the reaction was completed, the reaction was quenched with saturated NaHCO3, the organic phase was separated, and the aqueous phase was extracted with dichloromethane. The extracts and organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the mother liquor was rotary evaporated to recover the solvent. The residue was purified by silica gel column chromatography to give 1.7 g of pale yellow solid, with a yield of 92%. 1 H NMR (500 MHz, CDCl3): δ=8.34 (s, 2H), 7.64 (d, J =8.0 Hz, 2H), 7.41 (d, J =8.1Hz, 2H), 6.64 (dd, J =17.6, 10.8Hz, 1H), 5.73 (d, J =17.4Hz, 1H), 5.21 (d, J =10.9Hz, 1H), 4.45 (t, J =9.1Hz, 2H), 4.16 (t, J =8.4 Hz, 2H), 4.11-4.06 (m, 2H), 1.81 (Octa, J =6.8Hz, 2H), 0.97 (d, J =6.7Hz, 6H), 0.85 (d, J =6.7Hz, 6H)ppm; 13 C NMR (125MHz, CDCl3): δ=161.4, 148.3, 146.4, 138.0, 134.92, 134.73, 126.34, 126.07, 122.1, 114.4, 71.9, 70.0, 31.8, 18.1, 17.3 ppm; HRMS (ESI+) m / z:[M+H] + Calculated for C 25 H 30 N3O2404.2338, found 404.2337; [2M+Na] + Calculated for C 50 H 58 N6O4Na829.4417, found 829.4446.

[0044] Example 2: Preparation of POP-PyBox, a porous organic polymer functionalized with bisoxazoline pyridine

[0045] Preparation of POP-OIP-X: Under a nitrogen atmosphere, VPyBox monomer, styrene, divinylbenzene, azobisisobutyronitrile, and toluene were added to a 15 mL Young tube. The mixture was stirred at room temperature for 1 hour to ensure homogeneity, and then at 80 °C... o Static polymerization was carried out at C for 24 hours. After the reaction was completed, the gel-like polymer was removed, ultrasonically washed three times with tetrahydrofuran, and then subjected to polymerization at 60°C. o Vacuum dried at C for 12 hours, then ground to obtain a white powdery solid.

[0046] The molar ratio of VPyBox, styrene, and divinylbenzene is: 1:0:12; 1:3:12; 1:4:12; 1:8:12; The corresponding polymers are labeled as POP-PyBox-1, POP-PyBox-2, POP-PyBox-3 and POP-PyBox-4, respectively.

[0047] Furthermore, the prepared polymer POP-PyBox-X (X=1, 2, 3, 4) was subjected to... N Elemental analysis was performed to determine the loading of PyBox; the specific surface area, pore volume, and pore size of POP-PyBox-X were measured by nitrogen isothermal adsorption-desorption experiments, and the specific data are shown in Table 1.

[0048] Table 1. Hole Structure Properties of POP-PyBox-X and PyBox Load Capacity

[0049] Furthermore, more detailed IR, TGA, SEM, and TEM analyses were performed on the optimal polymer POP-PyBox-3, and the specific spectra are shown in the attached figures.

[0050] Example 3: POP-PyBox-3 / CoCl2 / NaO t Bu catalyzes the hydrosilylation reaction of alkynes with diphenylsilanes.

[0051] Under nitrogen protection, POP-PyBox-3 (65 mg, 0.15 mmol), 0.5 mL of 2.6 mg / mL CoCl2 tetrahydrofuran solution (equivalent to 1.3 mg cobalt chloride, 0.01 mmol), and 2.5 mL of anhydrous tetrahydrofuran were added sequentially to a 15 mL Young tube. The mixture was stirred at room temperature for 1 h. The color of the ligand POP-PyBox-3 changed from pale yellow to green, while the solution became colorless. 10 μL of 3.0 mol / L sodium tert-butoxide tetrahydrofuran solution (equivalent to 2.8 mg sodium tert-butoxide, 0.03 mmol) was added to the above reaction solution. Then, diphenylsilane (221 mg, 1.2 mmol) and phenylacetylene (102 mg, 1.0 mmol) were added sequentially. The mixture was reacted at room temperature for 4–8 h, and the reaction process was monitored by GC. After the reaction was complete, the mixture was exposed to air and stirred for 10 min to quench the reaction. After centrifugation, the supernatant was collected, and the solid was washed with 2 mL × 3 mL of THF for reuse. The organic phases were combined, and the solvent was recovered by rotary evaporation under reduced pressure. The residue was purified by column chromatography to obtain the corresponding hydrosilylation addition product, and the yield was calculated. The product was characterized by nuclear magnetic resonance spectroscopy and gas chromatography-mass spectrometry. Specific experimental results are shown in Table 2.

[0052] Table 2 POP-PyBox-3 / CoCl2 / NaO t Bu-catalyzed hydrosilylation addition reaction of alkynes with Ph2SiH2

[0053] Characterization data of the products prepared in Examples 3-19: Example 3: White solid, melting point: 60℃; 1 H NMR (500 MHz, CDCl3): δ=7.59-7.50 (m, 4H), 7.41-7.31 (m, 8H), 7.29-7.19 (m, 3H), 6.26 (dd, J =2.5, 1.0 Hz, 1H), 5.63 (d, J =2.5 Hz, 1H), 5.40 (d, J =0.9 Hz, 1H) ppm; GC-MS (EI): m / z=286.1[M + ,52%],183.0 (100%).

[0054] Example 4: White solid, melting point: 64℃; 1 H NMR (500 MHz, CDCl3): δ=7.72-7.62 (m, 4H), 7.35-7.48 (m, 6H), 7.32 (d,J =7.8 Hz, 2H), 7.20 (d, J =7.8 Hz, 2H), 6.25 (d, J =2.4 Hz, 1H), 5.88 (d, J =2.5 Hz, 1H), 5.40 (s, 1H), 2.25 (s, 3H) ppm; GC-MS (EI): m / z=300.1[M + [35%], 183.0 (100%), 105.0 (100%).

[0055] Example 5: Colorless liquid, 1 H NMR (500 MHz, CDCl3): δ=7.68 (d, J =7.2 Hz, 4H), 7.50-7.32 (m, 6H), 7.12-7.22 (m, 3H), 6.86-7.02 (m, 1H), 6.32 (s , 1H), 5.73 (s, 1H), 5.52 (s, 1H), 2.38 (s, 3H) ppm; GC-MS (EI): m / z=300.1[M + [38%], 183.0 (100%), 105.0 (100%).

[0056] Example 6: White solid, melting point: 42℃; 1 H NMR (500 MHz, CDCl3): δ=7.78-7.62 (m, 4H), 7.55-7.36 (m, 6H), 7.30-7.05 (m, 3H), 7.10 (dd, J =7.4, 1.5 Hz, 1H), 6.00 (dd, J =3.1, 0.8 Hz, 1H), 5.82 (d, J =3.1 Hz, 1H), 5.40 (s, 1H), 2.30 (s, 3H) ppm; GC-MS (EI): m / z=300.1[M + ,18%],183.0 (100%),105.0 (100%).

[0057] Example 7: White solid, melting point: 110℃; 1 H NMR (500 MHz, CDCl3): δ=7.70-7.52 (m, 6H), 7.50-7.44 (m, 2H), 7.52-7.40 (m, 11H), 6.35 (dd, J=2.5, 0.9 Hz, 1H), 5.70 (d, J =2.4 Hz, 1H), 5.41 (s, 1H) ppm; GC-MS (EI): m / z=362.1[M + ,36%],183.0 (100%).

[0058] Example 8: White solid, melting point: 70℃; 1 H NMR (500 MHz, CDCl3): δ=7.60-7.40 (m, 4H), 7.45-7.33 (m, 8H), 6.92-6.80 (m, 2H) 6.30 (dd, J =2.4, 1.0 Hz, 1H), 5.58 (d, J =2.4 Hz, 1H), 5.46 (d, J =0.9 Hz, 1H), 3.75 (s, 3H) ppm; GC-MS (EI): m / z=315.1[M + ,16%],183.0 (100%),223.0 (100%).

[0059] Example 9: Colorless liquid; 1 H NMR (500 MHz, CDCl3): δ=7.52 (dd, J =8.0, 1.6 Hz, 4H), 7.35-7.51 (m, 6H), 7.22 (d, J =8.0 Hz, 2H), 6.50 (d, J =8.0 Hz, 2H), 6.34 (dd, J =2.4, 1.0 Hz, 1H), 5.62 (d, J =2.4 Hz, 1H), 5.33 (s, 1H), 3.52 (br, 2H) ppm; GC-MS (EI): m / z=301.1[M + [55%], 118.1 (100%), 183.0 (100%).

[0060] Example 10: Colorless liquid; 1 H NMR (500 MHz, CDCl3): δ=7.68-7.50 (m, 4H), 7.42-7.23 (m, 8H), 6.90 (t, J =8.7 Hz, 2H), 6.37 (d, J =2.4 Hz, 1H), 5.71 (d, J=2.4 Hz, 1H), 5.40 (s, 1H) ppm; GC-MS (EI): m / z=304.1[M + ,55%],183.0 (100%).

[0061] Example 11: White solid, melting point: 47℃; 1 H NMR (500 MHz, CDCl3): δ=7.66-7.42 (m, 4H), 7.46-7.38 (m, 6H), 7.20-7.12 (m, 4H), 6.20 (dd, J =2.3, 1.0 Hz, 1H), 5.73 (d, J =2.3 Hz, 1H), 5.35 (s, 1H) ppm; GC-MS (EI): m / z=320.1[M + , 55%], 322.0 [M+2, 20%], 183.0 (100%).

[0062] Example 12: White solid, melting point: 82℃; 1 H NMR (500 MHz, CDCl3): δ=7.70-7.55 (m, 4H), 7.50-7.41 (m, 8H), 7.25-7.18 (m, 2H), 6.30 (dd, J =2.4, 0.9 Hz, 1H), 5.71 (d, J =2.3 Hz, 1H), 5.38 (s, 1H) ppm; GC-MS (EI): m / z=364.0[M + , 12%], 366.0 [M+2, 14%], 183.0 (100%).

[0063] Example 13: Colorless liquid; 1 H NMR (500 MHz, CDCl3): δ=7.68-7.46 (m, 6H), 7.49-7.28 (m, 8H), 6.30 (dd, J =2.2, 0.9 Hz, 1H), 5.75 (d, J =2.3 Hz, 1H), 5.40 (s, 1H) ppm; GC-MS (EI): m / z=354.1[M + ,52%],183.0 (100%).

[0064] Example 14: White solid, melting point: 75℃ 1H NMR (500 MHz, CDCl3): δ=7.90 (d, J =8.4 Hz, 2H), 7.51-7.62 (m, 4H), 7.30-7.45 (m, 8H), 6.25 (d, J =2.4 Hz, 1H), 5.72 (d, J =2.4 Hz, 1H), 5.35 (s, 1H), 2.50 (s, 3H) ppm; GC-MS (EI): m / z=328.1[M + ,12%],183.0 (100%).

[0065] Example 15: White solid, melting point: 70℃; 1 H NMR (500 MHz, CDCl3); δ=7.90-7.85 (m, 2H), 7.67-7.58 (m, 4H), 7.47-7.36 (m, 8H), 6.24 (dd, J =2.3, 0.9 Hz, 1H), 5.82 (d, J =2.3 Hz, 1H), 5.40 (s, 1H), 3.82 (s, 3H) ppm; GC-MS (EI): m / z=344.1[M + ,26%],183.0 (100%).

[0066] Example 16: Colorless liquid, 1 H NMR (500 MHz, CDCl3): δ=8.12 (dd, J =8.3, 1.3 Hz, 1H), 7.85 (dd, J =7.6, 1.7 Hz, 1H), 7.80-7.75 (m, 1H), 7.71-7.65 (m, 4H), 7.54-7.30 (m, 9H), 7.20 (dd, J =7.0, 1.2 Hz, 1H), 6.22 (dd, J =3.1, 0.9 Hz, 1H), 6.15 (d, J =3.1 Hz, 1H), 5.30 (s, 1H) ppm; GC-MS (EI): m / z=311.1[M + ,26%],183.0 (100%).

[0067] Example 17: White solid, melting point: 54℃; 1H NMR (500 MHz, CDCl3): δ=7.64-7.50 (m, 4H), 7.48-7.31 (m, 6H), 7.28-7.20 (m, 2H), 7.22 (dd, J =2.8, 1.4 Hz, 1H), 6.30 (dd, J =2.4, 0.9 Hz, 1H), 5.58 (d, J =2.4 Hz, 1H), 5.40 (d, J =0.8 Hz, 1H) ppm; GC-MS (EI): m / z=336.1[M + ,26%],183.0 (100%).

[0068] Example 18: White solid, melting point: 55℃; 1 H NMR (500 MHz, CDCl3): δ=7.61 (d, J =7.2 Hz, 4H), 7.30-7.42 (m, 6H), 7.10 (d, J =5.2 Hz, 1H), 6.92 (d, J =3.6 Hz, 1H), 6.88 (t, J =4.4 Hz, 1H), 6.30 (s, 1H), 5.52 (d, J =1.6 Hz, 1H), 5.42 (s, 1H) ppm; GC-MS (EI): m / z=292.1[M + ,42%],183.0 (100%),105 (100%).

[0069] Example 19: Colorless liquid; 1 H NMR (500 MHz, CDCl3): δ=8.60 (d, J =2.4 Hz, 1H), 8.40 (dd, J =4.8, 1.6 Hz, 1H), 7.51-7.60 (m, 5H), 7.31-7.40 (m, 6H), 7.12 (dd, J =8.0, 4.8 Hz, 1H), 6.32 (d, J =2.4 Hz, 1H), 5.80 (d, J =2.4 Hz, 1H), 5.40 (s, 1H) ppm; GC-MS (EI): m / z=287.1[M + ,12%],183.0 (100%).

[0070] Example 20: POP-PyBox-1 / CoCl2 / NaO t Bu-catalyzed hydrosilylation reaction of phenylacetylene and diphenylsilane

[0071] Replacing POP-PyBox-3 with POP-PyBox-1 in Example 3, while keeping other conditions unchanged, yielded 275 mg of hydrosilylated product with a yield of 96% and a ratio of 2:2'=84:16.

[0072] Example 21: POP-PyBox-2 / CoCl2 / NaO t Bu3 catalyzes the hydrosilylation reaction of phenylacetylene with diphenylsilane.

[0073] Replacing POP-PyBox-3 with POP-PyBox-2 in Example 3, while keeping other conditions unchanged, yielded 272 mg of hydrosilylated product with a yield of 95% and a ratio of 2:2' = 90:10.

[0074] Example 22: POP-PyBox-4 / CoCl2 / NaO t Bu-catalyzed hydrosilylation reaction of phenylacetylene and diphenylsilane

[0075] Replacing POP-PyBox-3 with POP-PyBox-4 in Example 3, while keeping other conditions unchanged, yielded 243 mg of hydrosilylated product with a yield of 85% and a ratio of 2:2'=96:4.

[0076] Example 23: POP-PyBox-3 / CoBr2 / NaO t Bu-catalyzed hydrosilylation reaction of phenylacetylene and diphenylsilane

[0077] Replacing CoCl2 with CoBr2 in Example 3, while keeping other conditions unchanged, yielded 222 mg of hydrosilylated product, with a yield of 78% and a ratio of 2:2' = 92:8.

[0078] Example 24: Hydrosilylation of phenylacetylene with diphenylsilane catalyzed by POP-PyBox-3 / CoCl2 / NaBHEt3

[0079] NaO in Example 3 t Replacing Bu with NaBHEt3, while keeping other conditions unchanged, yielded 187 mg of hydrosilylated product, with a yield of 65% and a ratio of 2:2' = 89:10.

[0080] Example 25: Recovery and Recycling of Catalyst POP-PyBox-3-Co

[0081] Under nitrogen protection, the POP-PyBox-3-Co catalyst, after centrifugation and THF washing, was transferred to a 15 mL Young tube. 3.0 mL of THF and 10 μL of a 3.0 mol / L sodium tert-butoxide tetrahydrofuran solution (equivalent to 2.8 mg, 0.03 mmol of sodium tert-butoxide) were added. The mixture was stirred at room temperature for 5–10 min, followed by the sequential addition of phenylacetylene (102 mg, 1.0 mmol) and diphenylsilane (221 mg, 1.2 mmol). The reaction mixture was stirred at room temperature for 4 hours. GC analysis showed a phenylacetylene conversion greater than 99%. After the same post-treatment, 275 mg of the catalyst was obtained, with a yield of 96%. Using the same procedure, the POP-PyBox-3-Co catalyst could be recycled more than 6 times while maintaining certain catalytic activity. The results are shown in the attached figure. Figure 11 As shown.

Claims

1. A 4-styrene-functionalized bisoxazoline pyridine monomer, abbreviated as VPyBox, as shown in Formula VII: 。 2. The method for preparing VPyBox as described in claim 1, characterized in that, Includes the following steps: (1) Mix 4-hydroxypyridine-2,6-dicarboxylic acid as shown in Formula I with methanol, add SOCl2 dropwise at 0~5℃, then raise to room temperature and continue stirring for 36 h. After post-treatment of the reaction solution, the intermediate shown in Formula II is obtained: dimethyl 4-hydroxypyridine-2,6-dicarboxylic acid. (2) The intermediate shown in Formula II was mixed with PBr5 and stirred at 80°C for 6 h. The reaction solution was post-treated to obtain the intermediate shown in Formula III: 4-bromopyridine-2,6-dicarboxylic acid dimethyl ester. (3) Dissolve the intermediate shown in Formula III and KOH in methanol, stir at 65°C for 5 h, and then treat the reaction solution to obtain the intermediate shown in Formula IV: 4-bromopyridine-2,6-dicarboxylic acid; (4) The intermediate shown in Formula IV, oxalyl chloride, N , N Dimethylformamide was dissolved in dichloromethane and reacted at room temperature for 6 h. The mixture was then evaporated under reduced pressure to obtain an acyl chloride derivative. The obtained acyl chloride derivative, valine, and triethylamine were dissolved in dichloromethane and reacted at room temperature for 2 h. The reaction solution was post-treated to obtain the intermediate shown in formula V: 4-bromo-2,6-bis[ N -(1'-hydroxy-3'-methylbut-2'-yl)]carbamoylpyridine; (5) Under a N2 atmosphere, the intermediate shown in Formula V, 4-vinylphenylboronic acid, palladium chloride, RuPhox, and cesium carbonate were mixed in THF / H2O, heated to 75°C, and stirred for 8 h. After post-treatment, the reaction solution was used to obtain the intermediate shown in Formula VI: 4-(4'-vinyl)phenyl-2,6-bis[ N -(1'-hydroxy-3'-methylbut-2'-yl)]carbamoylpyridine; (6) Under N2 atmosphere, the intermediate shown in formula VI was dissolved in dichloromethane, cooled to -20℃, DAST was added dropwise, and the reaction was carried out for 30 min. After post-treatment, the product shown in formula VII was obtained: 4-(4'-vinyl)phenyl-2,6-bis(4'-isopropyl-4',5'-dihydrooxazol-2'-yl)pyridine (VPyBox). 。 3. A bisoxazoline pyridine-functionalized porous organic polymer, abbreviated as POP-PyBox, as shown in Formula VIII: In equation VIII, x:y:z = 1:0 ~ 8:

12.

4. The method for preparing the POP-PyBox as described in claim 3, characterized in that, include: Under a nitrogen atmosphere, the VPyBox, styrene, divinylbenzene, and azobisisobutyronitrile of claim 1 were dissolved in toluene and polymerized at 80°C for 24 h. After cooling to room temperature, the resulting blocky solid was washed and vacuum dried to obtain POP-PyBox.

5. The method for preparing the POP-PyBox as described in claim 4, characterized in that, The molar ratio of VPyBox, styrene, and divinylbenzene is 1:0 to 8:

12.

6. The method for preparing the POP-PyBox as described in claim 4, characterized in that, The mass ratio of azobisisobutyronitrile to VPyBox is 0.1~0.2:

1.

7. The method for preparing the POP-PyBox as described in claim 4, characterized in that, The mass ratio of toluene to VPyBox is 6~9:

1.

8. The POP-PyBox as described in claim 3 as a solid N , N , N - Application of tridentate ligands in the Co-catalyzed hydrosilylation reaction of aryl alkynes with diphenylsilanes.

9. The application as described in claim 8, characterized in that, The application method is as follows: Under nitrogen protection, POP-PyBox, CoCl2, and anhydrous tetrahydrofuran were mixed and stirred at room temperature for 1 h. Sodium tert-butoxide, diphenylsilane as shown in formula A, and aryl alkyne as shown in formula B were added and stirred at room temperature for 4-8 h. The reaction solution was post-treated to obtain the hydrosilylated product as shown in formula C. The reaction formula is as follows: In equations B and C, Ar represents aryl, heteroaryl, substituted aryl, or substituted heteroaryl; the substituted aryl or substituted heteroaryl has one or more substituents, each of which is independently selected from: C1-C3 alkyl, C1-C3 alkoxy, phenyl, amino, halogen, trifluoromethyl, C1-C3 alkyl acyl, C1-C3 alkoxy acyl, or cyano.

10. The application as described in claim 9, characterized in that, The molar ratio of diphenylsilane (Formula A), aryl alkyne (Formula B), POP-PyBox, CoCl2, and sodium tert-butoxide is 1.2:1:0.15:0.01:0.03.

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