CN115057996A - Preparation method and application of 4CzIPN-type porous organic polymer - Google Patents

Abstract

The invention relates to a method for preparing Porous Organic Polymers (POPs) based on 2,4,5, 6-tetra (9H-carbazole-9-yl) isophthalonitrile (4CZIPN) fluorescent moleculesThe preparation method comprises the step of quickly and efficiently constructing 4CzIPN POPs through Friedel-Crafts alkylation reaction of an optically active unit 4CzIPN and a connecting matter Formaldehyde Dimethyl Acetal (FDA), wherein the tail end of a polymer network contains a certain amount of hydrophilic ether residues so as to improve the dispersibility of the POPs in a water phase. The polymer is applied to a high-efficiency heterogeneous photocatalyst at the same time, and C (sp) can be constructed in an aqueous phase ³ ) The reaction has the advantages of mild conditions, wide substrate application range, greenness, sustainability and the like, and the development of another application of the compound can realize direct phosphorylation of commercially available anticoagulant medicaments ticlopidine and clopidogrel and oxidation of mustard gas simulant 2-chloroethyl sulfide (CEES), thereby showing great application prospect.

Description

Preparation method and application of 4CzIPN-type porous organic polymer

technical field

The invention belongs to the field of material chemistry, and relates to organic synthesis technology, in particular to a preparation method and application of a 4CzIPN type porous organic polymer.

Background technique

Light energy is the most accessible, green and sustainable ideal energy, and is favored by chemists. In the past decade, photoredox catalysis has received extensive attention as a powerful synthetic strategy for realizing complex chemical transformations. However, most organic compounds cannot absorb visible light, and photocatalysts are required to act as light absorption media to realize the conversion of light energy to chemical energy.

The currently widely used small-molecule organic photosensitizers are expensive, heavy metal residues, easy to photobleach, and difficult to recycle. In recent years, porous organic polymers (POPs), as an emerging organic heterogeneous photocatalyst, can not only eliminate the contamination of organic products by trace homogeneous photocatalysts due to their recyclability and reusability, but also simplify the The processing and purification steps in large-scale reactions show strong application prospects.

As an excellent green organic synthesis reaction medium, water has many advantages such as safety, cheapness, non-toxicity and environmental protection. The development of water-phase synthesis reactions is of great significance and fully conforms to the concept of green chemistry. Unfortunately, in the prior art, there are very limited examples of aqueous photocatalytic reactions. This situation can be explained by Marcus's theory, mainly due to the high dielectric constant of water and the increased interaction distance caused by the poor solubility of the substrate and the photocatalyst in water, which leads to the unfavorable thermodynamics of the water-phase photocatalytic reaction.

SUMMARY OF THE INVENTION

The purpose of the present invention is to overcome the deficiencies of the prior art and provide a 4CzIPN type porous organic polymer, which is proved by experiments to be an efficient heterogeneous photocatalyst, which can construct C(sp3)-P bonds in the aqueous phase And selective oxidation of sulfide, the reaction has many advantages such as mild conditions, wide substrate application range, green and sustainable, and at the same time, the polymer can also realize the direct phosphorylation of commercially available anticoagulant drugs ticlopidine and clopidogrel. and oxidation of the mustard gas simulant 2-chloroethyl sulfide (CEES), showing great application prospects.

The present invention solves its technical problem by adopting the following technical solutions to realize:

A kind of 4CzIPN type porous organic polymer, its synthetic method process is as follows:

Among them, 4CzIPN stands for 2,4,5,6-tetrakis(9H-carbazol-9-yl)isophthalonitrile, FDA stands for formaldehyde dimethyl acetal, and POP stands for porous organic polymer.

Polymerization for the synthesis of 4CzIPN-type porous organic polymers: The 4CzIPN-type POP1-3 was rapidly and efficiently constructed by Friedel-Crafts alkylation of optically active unit 4CzIPN with the linker formaldehyde dimethyl acetal (FDA).

The synthetic method steps for the synthesis of 4CzIPN-type porous organic polymers are: adding FeCl3 to a solution of _4CzIPN in 1,2-dichloroethane, stirring at room temperature, and adding formaldehyde dimethyl acetal, first at 45 ° C The mixture solution was stirred at 80° C. until the cross-linking reaction was completed, and the crude product solution of POP-1 was obtained. FDA was added to the crude product solution of POP-1 again, and the stirring was continued at 80° C. until the cross-linking reaction was completed to obtain a crude product solution of POP-2. Similarly, FDA was added to the dissolution of the crude product of POP-2, and stirring was continued at 80° C. until the cross-linking reaction was completed to obtain a crude product solution of POP-3. Methanol was added to the above crude product solution with continuous stirring, the precipitate was filtered, and the resulting solid was stirred in concentrated hydrochloric acid. The suspension was filtered again and washed with water and methanol. After extraction with methanol/dichloromethane in a Soxhlet extractor, tetrahydrofuran was used. The solid product is vacuum dried to obtain porous organic polymers POP-1, POP-2 and POP-3 with different cross-linking degrees.

The 4CzIPN-type porous organic polymer can be applied to catalyze the visible light-induced C(sp ³ )–H bond phosphorylation functionalization reaction, and the reaction equation is as follows:

The phosphorylating reagents include: diarylphosphorus oxide, H-phosphite, and phenylphosphinate. R groups include: phenyl, 2-pyridyl, benzyl.

The C(sp ³ )–H bond phosphorylation functionalization reaction conditions are as follows: using tetrahydroisoquinoline and phosphorylation reagent as starting materials, 4CzIPN type porous organic polymer as photocatalyst, at room temperature, air or In an oxygen atmosphere, 460nm LED blue light is illuminated. After the reaction is complete, a series of C(sp ³ )–H bond functionalized products can be obtained by separation and purification. The polymer photocatalysts can be separated by filtration or centrifugation, and can be reused .

The application of 4CzIPN-type porous organic polymers can also be applied to catalyze visible light-induced selective sulfide oxidation reactions, and the reaction equation is as follows:

Wherein R ¹ is methyl or methyl, and R ² is aryl, H-phosphite, or phenylphosphinate. R groups include: phenyl, 2-pyridyl, benzyl.

The reaction conditions of visible light-induced selective oxidation of sulfides are as follows: thioether is used as starting material, 4CzIPN-type porous organic polymer is used as photocatalyst, and 460nm LED blue light is irradiated at room temperature in air or oxygen atmosphere. After the reaction is complete , a series of C(sp ³ )–H bond functionalized products can be obtained by separation and purification, in which the polymer photocatalysts can be separated by filtration or centrifugation, and can be reused.

The application of 4CzIPN-type porous organic polymers in aqueous photocatalytic reactions can also realize direct phosphorylation of commercially available anticoagulant drugs ticlopidine and clopidogrel and oxidation of mustard gas mimic 2-chloroethyl sulfide (CEES). .

Advantages and effects of the patent application of the present invention:

In order to solve the thermodynamic problem of water-phase photoredox catalysis, the present invention designs a chemically active unit 2,4,5,6-tetra(9H-carbazol-9-yl through the Friedel-Crafts alkylation reaction promoted by FeCl3 ₎ ) isophthalonitrile (4CzIPN) and formaldehyde dimethyl acetal (FDA) to synthesize a covalently linked metal-free porous organic polymer (POPs) containing a certain number of ether residues at the end of the polymer network , Through the introduction of hydrophilic functional group side arms, the dispersion of the interface between the heterogeneous photocatalyst and the aqueous solution is enhanced, and the interaction distance between the substrate and the photocatalyst is reduced, thereby eliminating or alleviating the unfavorable thermodynamics of the aqueous photocatalytic reaction. . The material proved to be an efficient heterogeneous photocatalyst, which can construct C(sp3)-P bonds in the aqueous phase and selectively oxidize sulfides, with mild reaction conditions, wide substrate application, green and sustainable and many other advantages. This method can also realize the direct phosphorylation of the commercially available anticoagulant drugs ticlopidine and clopidogrel and the oxidation of the mustard gas simulant 2-chloroethyl sulfide (CEES), showing great application prospects.

Detailed ways

The present invention will be further described in detail below through specific examples. The following examples are only descriptive, not restrictive, and cannot limit the protection scope of the present invention.

A preparation method of 4CzIPN polymer POP-1, the steps are as follows:

The synthetic method steps for the synthesis of 4CzIPN-type porous organic polymers are as follows: add 5.84 g FeCl3 to a solution of _3.15 g 4CzIPN in 80 ml 1,2-dichloroethane, stir at room temperature for 30 minutes, and add 1.12 ml formaldehyde For dimethyl acetal, the mixture solution was first stirred at 45° C. for 5 hours, and then continued to be stirred at 80° C. for 24 hours until the cross-linking reaction was completed to obtain a crude product solution of POP-1. Add FDA to the POP-1 crude product solution again, continue to stir at 80 ° C until the cross-linking reaction is completed, add 30 ml of methanol to the above crude product solution and continue to stir, filter the precipitate, and stir the obtained solid in concentrated hydrochloric acid for 2 hours . The suspension was filtered again and washed with water and methanol. After extraction with methanol/dichloromethane for 24 hours in a Soxhlet extractor, extraction with tetrahydrofuran for an additional 24 hours. The solid product is vacuum-dried to obtain the porous organic polymer POP-1.

Example 1

In a 10 mL reaction tube, N-phenyltetrahydroisoquinoline (0.2 mmol), phosphorus reagent (0.4 mmol) and photocatalyst (2.0 mg) were mixed well in 1 mL of water, stirred at room temperature, and the blue LED light source was open. Irradiate for 12h. The reaction was monitored by TLC, and when the substrate was completely consumed, 5.0 mL of water was added to the reaction system and extracted with ethyl acetate (3 x 5.0 mL). The organic phases were combined, dried over anhydrous Na ₂ SO ₄ , filtered, and the organic solvent was spin-dried under reduced pressure. The crude product was separated by neutral alumina column chromatography using petroleum ether/ethyl acetate as the eluent to obtain the target product 1.

The specific results are as follows:

White solid (75.3 mg, 92% yield); m.p. 199.7–202.1 °C; 1H NMR (400 MHz, Chloroform-d) δ 7.89–7.77 (m, 2H), 7.76–7.67 (m, 2H), 7.63–7.51 ( m, 1H), 7.54–7.42 (m, 3H), 7.36 (td, J=7.5, 3.0Hz, 2H), 7.23–7.03 (m, 4H), 6.96 (t, J=7.5Hz, 1H), 6.84 –6.78(m,3H),6.68(d,J=7.7Hz,1H),5.59(d,J=8.0Hz,1H),4.20–3.84(m,1H),3.64–3.58(m,1H), 2.95–2.58(m,2H).13CNMR(101MHz,Chloroform-d)δ150.0(d,J=7.8Hz),136.9(d,J=4.2Hz),132.30(d,J=92.7Hz),132.26 (d, J=8.5Hz), 131.9 (d, J=2.9Hz), 131.74, 131.65 (d, J=1.9Hz), 131.4 (d, J=88.3Hz), 123.0, 129.3 (d, J=2.2 Hz),129.1,128.4(d,J=11.1Hz),128.3(d,J=11.3Hz),127.8(d,J=3.3Hz),127.4(d,J=2.9Hz),125.5(d,J =2.6Hz),119.5,116.8,62.0(d,J=79.6Hz),45.2,25.6.31P NMR(162MHz,Chloroform-d)δ30.65.HRMS(ESI-TOF)m/z:[M+Na ]+calcd for C27H24NNaOP432.1488 found432.1487.

Example 2

In a 10 mL reaction tube, N-phenyltetrahydroisoquinoline (0.2 mmol), phosphorus reagent (0.4 mmol) and photocatalyst (2.0 mg) were mixed well in 1 mL of water, stirred at room temperature, and the blue LED light source was open. Irradiate for 12h. The reaction was monitored by TLC, and when the substrate was completely consumed, 5.0 mL of water was added to the reaction system and extracted with ethyl acetate (3 x 5.0 mL). The organic phases were combined, dried over anhydrous Na ₂ SO ₄ , filtered, and the organic solvent was spin-dried under reduced pressure. The crude product was separated by neutral alumina column chromatography using petroleum ether/ethyl acetate as the eluent to obtain the target product 2.

White solid (77.0 mg, 91% yield); mp 213.9–215.6°C; ¹ H NMR (400 MHz, Chloroform-d) δ 7.90–7.79 (m, 2H), 7.78–7.66 (m, 2H), 7.56 ( t,J＝6.9Hz,1H),7.49-7.45(m,3H),7.38(td,J＝7.5,2.7Hz,2H),7.17(t,J＝7.4Hz,1H),7.09(d,J =7.4Hz,1H),7.02-6.92(m,3H),6.75(d,J=8.4Hz,2H),6.67(d,J=7.7Hz,1H),5.51(d,J=11.5Hz,1H) ), 4.17–3.81 (m, 1H), 3.66–3.43 (m, 1H), 2.96–2.51 (m, 2H), 2.25 (s, 3H). ¹³ C NMR (101MHz, Chloroform-d) δ148.0 ( d,J=9.1Hz),136.9(d,J=4.3Hz),132.5(d,J=95.5Hz),132.2(d,J=8.4Hz),131.8(d,J=2.7Hz),131.74( d, J=8.6Hz), 131.72 (d, J=90.9Hz), 131.6 (d, J=2.7Hz), 129.9, 129.7, 129.3 (d, J=1.8Hz), 128.4 (d, J=11.1Hz) ),128.3(d,J=11.3Hz),127.8(d,J=3.1Hz),127.3(d,J=3.0Hz),125.4(d,J=2.6Hz),117.7,62.0(d,J= 80.6Hz), 45.7, 25.1, 20.5. ³¹ P NMR (162MHz, Chloroform-d) δ30.22.

Example 3

In a 10 mL reaction tube, mix N-phenyltetrahydroisoquinoline (0.2 mmol), phosphorus reagent (0.4 mmol) and photocatalyst (2.0 mg) in 1 mL of water, stir at room temperature, and open the blue LED light source Irradiate for 12h. The reaction was monitored by TLC, and when the substrate was completely consumed, 5.0 mL of water was added to the reaction system and extracted with ethyl acetate (3 x 5.0 mL). The organic phases were combined, dried over anhydrous Na ₂ SO ₄ , filtered, and the organic solvent was spin-dried under reduced pressure. The crude product was separated by neutral alumina column chromatography using petroleum ether/ethyl acetate as the eluent to obtain the target product 3.

White solid (79.8 mg, 85% yield); mp 228.9–229.8°C; ¹ H NMR (400 MHz, Chloroform-d) δ 7.85 (t, J=8.9 Hz, 2H), 7.76 (t, J=9.3 Hz) ,2H),7.55–7.44(m,4H),7.39–7.35(m,2H),7.17(t,J=7.1Hz,2H),6.86–6.80(m,3H),6.58(s,1H), 6.08(s, 1H), 5.47(d, J＝10.0Hz, 1H), 4.15(t, J＝10.6Hz, 1H), 3.83(s, 3H), 3.65(d, J＝10.9Hz, 1H), 3.38(s, 3H), 3.00–2.35(m, 2H). ¹³ C NMR (101MHz, Chloroform-d) δ150.3(d, J=9.2Hz), 148.2(d, J=2.9Hz), 146.5( d, J＝2.6Hz), 132.5(d, J＝95.3Hz), 132.3(d, J＝8.5Hz), 132.1(d, J＝87.8Hz), 131.8(d, J＝2.8Hz), 131.7( d, J＝1.7Hz), 131.6(d, J＝2.2Hz), 129.14, 129.11, 128.6(d, J＝11.0Hz), 128.3(d, J＝11.3Hz), 121.0, 119.9, 117.5, 112.0( d, J=2.2Hz), 110.4 (d, J=2.6Hz), 61.2 (d, J=81.3Hz), 55.8, 55.3, 45.4, 24.7. ³¹ P NMR (162MHz, Chloroform-d) δ23.07. HRMS(ESI-TOF)m/z:[M+Na] ⁺ calcd for C ₂₉ H ₂₈ NNaO ₃ P492.1699found492.1703.

Example 4

In a 10 mL reaction tube, N-phenyltetrahydroisoquinoline (0.2 mmol), phosphorus reagent (0.4 mmol) and photocatalyst (2.0 mg) were mixed well in 1 mL of water, stirred at room temperature, and the blue LED light source was open. Irradiate for 12h. The reaction was monitored by TLC, and when the substrate was completely consumed, 5.0 mL of water was added to the reaction system and extracted with ethyl acetate (3 x 5.0 mL). The organic phases were combined, dried over anhydrous Na ₂ SO ₄ , filtered, and the organic solvent was spin-dried under reduced pressure. The crude product was separated by neutral alumina column chromatography using petroleum ether/ethyl acetate as the eluent to obtain the target product 4.

White solid (54.9mg, 67% yield); m.p.165.5–167.3°C; 1H NMR (400MHz, Chloroform-d) δ 8.25–8.08 (m, 1H), 8.11–7.96 (m, 2H), 8.00–7.77 ( m, 2H), 7.61–7.51 (m, 3H), 7.37–7.31 (m, 2H), 7.30–7.20 (m, 3H), 7.16 (q, J=7.6Hz, 2H), 7.01–6.80 (m, 1H), 6.57 (d, J=7.7Hz, 1H), 6.54–6.44 (m, 2H), 4.17–4.10 (m, 1H), 3.64–3.58 (m, 1H), 3.46–3.39 (m, 1H) ,3.02–2.95(m,1H).13C NMR(101MHz,Chloroform-d)δ157.1(d,J＝3.0Hz),147.3,137.3,136.9(d,J＝3.8Hz),132.2(d,J =96.4Hz), 132.0(d, J=8.6Hz), 131.9(d, J=89.4Hz), 131.8(d, J=2.8Hz), 131.5(d, J=9.4Hz), 131.3(d, J = 2.9Hz), 131.2, 128.7 (d, J = 2.3 Hz), 128.5 (d, J = 11.2 Hz), 127.7, 127.6 (d, J = 4.0 Hz), 127.4 (d, J = 2.9 Hz), 125.6 (d, J=2.4Hz), 112.7, 106.1, 56.7 (d, J=76.1Hz), 42.3, 27.4.31P NMR (162MHz, Chloroform-d) δ 33.32.HRMS (ESI-TOF) m/z: [M+Na]+calcdfor C26H23N2NaOP433.1440found433.1440.

Example 5

In a 10 mL reaction tube, N-phenyltetrahydroisoquinoline (0.2 mmol), phosphorus reagent (0.4 mmol) and photocatalyst (2.0 mg) were mixed well in 1 mL of water, stirred at room temperature, and the blue LED light source was open. Irradiate for 12h. The reaction was monitored by TLC, and when the substrate was completely consumed, 5.0 mL of water was added to the reaction system and extracted with ethyl acetate (3 x 5.0 mL). The organic phases were combined, dried over anhydrous Na ₂ SO ₄ , filtered, and the organic solvent was spin-dried under reduced pressure. The crude product was separated by neutral alumina column chromatography using petroleum ether/ethyl acetate as the eluent to obtain the target product 5.

White solid (41.4 mg, 60% yield); ¹ H NMR (400 MHz, Chloroform-d) δ 7.50–7.35 (m, 1H), 7.28 (t, J=8.0 Hz, 2H), 7.25–7.11 (m, 3H), 7.02(d, J＝8.3Hz, 2H), 6.82(t, J＝7.3Hz, 1H), 5.23(d, J＝20.0Hz, 1H), 4.43–3.85 (m, 5H), 3.69– 3.63 (m, 1H), 3.27–2.89 (m, 2H), 1.28 (t, J=7.1Hz, 3H), 1.17 (t, J=7.1Hz, 3H). ¹³ C NMR (101MHz, Chloroform-d) δ149.4(d,J＝5.8Hz),136.5(d,J＝5.6Hz),130.7,129.2,128.8(d,J＝2.6Hz),128.2(d,J＝4.6Hz),127.4(d, J=3.3Hz), 125.9(d, J=2.9Hz), 118.5, 114.8, 63.3(d, J=7.2Hz), 62.3(d, J=7.7Hz), 58.8(d, J=159.2Hz), 43.5, 26.8, 16.5 (d, J=5.5Hz), 16.4 (d, J=5.9Hz). ³¹ PNMR (162MHz, Chloroform-d) δ22.18.

Example 6

In a 10 mL reaction tube, N-phenyltetrahydroisoquinoline (0.2 mmol), phosphorus reagent (0.4 mmol) and photocatalyst (2.0 mg) were mixed well in 1 mL of water, stirred at room temperature, and the blue LED light source was open. Irradiate for 12h. The reaction was monitored by TLC, and when the substrate was completely consumed, 5.0 mL of water was added to the reaction system and extracted with ethyl acetate (3 x 5.0 mL). The organic phases were combined, dried over anhydrous Na ₂ SO ₄ , filtered, and the organic solvent was spin-dried under reduced pressure. The crude product was separated by neutral alumina column chromatography using petroleum ether/ethyl acetate as the eluent to obtain the target product 6.

White solid (64.9 mg, 86% yield); ¹ H NMR (400 MHz, Chloroform-d) δ 7.84–7.59 (m, 2H), 7.60–7.31 (m, 4H), 7.27–7.17 (m, 2H), 7.14–7.08 (m, 2H), 7.07–6.96 (m, 1H), 6.92 (d, J=8.2Hz, 1H), 6.85–6.66 (m, 2H), 5.25 (t, J=13.6Hz, 1H) ,4.44–3.79(m,3H),3.62–3.50(m,1H),3.16–2.36(m,2H),1.36–1.21(m,3H). ^13C NMR(101MHz,Chloroform-d)δ149.59,149.55 ,149.5,136.8,136.7,136.51,136.46,132.6,132.5,132.4,132.34,132.31,132.3,132.19,132.17,131.0,130.6,130.4,130.2,129.8,129.2,129.01,128.99,128.96,128.9,128.54,128.50 ,128.44,128.42,128.33,128.29,128.25,128.21,128.17,127.4,127.33,127.30,125.73,125.70,125.7,118.7,118.3,115.5,114.6,62.8,61.7,61.62,61.59,61.55,61.3,61.2,60.5 , 43.8, 43.7, 27.1, 25.9, 16.6, 16.5. ³¹ PNMR (162MHz, Chloroform-d) δ37.70, 37.04.

Example 7

In a 10 mL reaction tube, ticlopidine (0.2 mmol), phosphorus reagent (0.4 mmol) and photocatalyst (2.0 mg) were mixed uniformly in 1 mL of water, stirred at room temperature, and irradiated with a blue LED light source for 12 h. The reaction was monitored by TLC, and when the substrate was completely consumed, 5.0 mL of water was added to the reaction system and extracted with ethyl acetate (3 x 5.0 mL). The organic phases were combined, dried over anhydrous Na ₂ SO ₄ , filtered, and the organic solvent was spin-dried under reduced pressure. The crude product was separated by neutral alumina column chromatography using petroleum ether/ethyl acetate as the eluent to obtain the target product 7.

White solid (47.24 mg, 51% yield); mp 169.5–170.8°C; ¹ H NMR (400 MHz, Chloroform-d) δ 7.80–7.70 (m, 2H), 7.70–7.60 (m, 2H), 7.58– 7.42 (m, 4H), 7.37 (td, J=7.6, 2.8Hz, 2H), 7.31 (d, J=7.9Hz, 1H), 7.26–7.16 (m, 1H), 7.17–7.00 (m, 2H) ,6.92(d,J＝5.2Hz,1H),5.96(d,J＝5.2Hz,1H),4.65(d,J＝11.0Hz,1H),3.97(dd,J＝13.9,1.6Hz,1H) ,3.89–3.47(m,2H),3.08–2.98(m,2H),2.66–2.59(m,1H). ¹³ C NMR(101MHz,Chloroform-d)δ136.9(d,J=7.0Hz), 135.9, 134.6, 132.4 (d, J=98.2Hz), 131.84, 131.83 (d, J=78.8Hz), 131.8 (d, J=2.8Hz), 131.4, 131.3, 131.1, 129.5, 128.4 (d, J= 3.0Hz), 128.3 (d, J=2.3Hz), 128.2, 126.64, 126.57, 126.3, 121.5 (d, J=1.7Hz), 61.0 (d, J=85.9Hz), 55.5 (d, J=13.2Hz) ), 46.0, 20.0. ³¹ PNMR(162MHz, Chloroform-d)δ28.77.HRMS(ESI-TOF)m/z:[M+H] ⁺ calcd for C ₂₆ H ₂₄ ClNOPS 464.0999found464.0998.

Example 8

In a 10 mL reaction tube, clopidogrel (0.2 mmol), phosphorus reagent (0.4 mmol) and photocatalyst (2.0 mg) were mixed uniformly in 1 mL of water, stirred at room temperature, and irradiated with a blue LED light source for 12 h. The reaction was monitored by TLC, and when the substrate was completely consumed, 5.0 mL of water was added to the reaction system and extracted with ethyl acetate (3 x 5.0 mL). The organic phases were combined, dried over anhydrous Na ₂ SO ₄ , filtered, and the organic solvent was spin-dried under reduced pressure. The crude product was separated by neutral alumina column chromatography using petroleum ether/ethyl acetate as the eluent to obtain the target product 8.

White solid (21.9 mg, 21% yield); mp 169.5–170.8°C; ¹ H NMR (400 MHz, Chloroform-d) δ 8.22–8.01 (m, 2H), 8.00–7.81 (m, 2H), 7.63– 7.53 (m, 6H), 7.40–7.29 (m, 2H), 7.25–7.13 (m, 2H), 6.95 (d, J=5.2Hz, 1H), 5.97 (d, J=5.1Hz, 1H), 5.42 –4.78(m, 2H), 4.18 – 3.59(m, 1H), 3.57(s, 3H), 2.88 – 2.78(m, 1H), 2.67(dd, J=14.6, 5.8Hz, 1H), 2.51(dt , J=16.4, 4.3Hz, 1H). ¹³ C NMR(101MHz, Chloroform-d)δ171.6, 136.5(d, J=6.7Hz), 134.4(d, J=25.0Hz), 132.21(d, J=97.1 Hz),132.20(d,J=8.9Hz),132.0(d,J=8.5Hz),131.9(d,J=2.8Hz),131.8(d,J=92.4Hz),131.5(d,J=2.8 Hz), 130.1, 129.8, 129.5, 128.5(d, J=11.2Hz), 128.0(d, J=11.7Hz), 127.3, 126.9, 126.3, 126.0, 122.0(d, J=1.7Hz), 63.8(d , J=11.6Hz), 60.7 (d, J=82.1Hz), 52.2, 43.0, 20.6. ³¹ P NMR (162MHz, Chloroform-d) δ 29.95. HRMS (ESI-TOF) m/z: [M+ Na] ⁺ calcd for C ₂₈ H ₂₅ ClNNaO ₃ PS 544.0837found544.0837.

Example 9

In a 10 mL reaction tube, thioether (0.2 mmol) photocatalyst (2.0 mg) was mixed uniformly in 1 mL of water, stirred at room temperature, and irradiated with a blue LED light source for 12 h. The reaction was monitored by TLC, and when the substrate was completely consumed, 5.0 mL of water was added to the reaction system and extracted with ethyl acetate (3 x 5.0 mL). The organic phases were combined, dried over anhydrous Na ₂ SO ₄ , filtered, and the organic solvent was spin-dried under reduced pressure. The crude product was separated by medium silica gel column chromatography using petroleum ether/ethyl acetate as the eluent to obtain the target product 9.

¹ H NMR (400MHz, Chloroform-d) δ 7.67 (dd, J=8.0, 1.6 Hz, 2H), 7.58-7.50 (m, 3H), 2.75 (s, 3H). ¹³ CNMR (101MHz, Chloroform-d) )δ145.7,131.0,129.4,123.5,44.0.

Example 10

In a 10 mL reaction tube, thioether (0.2 mmol) photocatalyst (2.0 mg) was mixed uniformly in 1 mL of water, stirred at room temperature, and irradiated with a blue LED light source for 12 h. The reaction was monitored by TLC, and when the substrate was completely consumed, 5.0 mL of water was added to the reaction system and extracted with ethyl acetate (3 x 5.0 mL). The organic phases were combined, dried over anhydrous Na ₂ SO ₄ , filtered, and the organic solvent was spin-dried under reduced pressure. The crude product was separated by medium silica gel column chromatography using petroleum ether/ethyl acetate as the eluent to obtain the target product 10.

¹ H NMR (400MHz, Chloroform-d)δ7.67(d,J=2.1Hz,2H),7.66-7.64(m,2H),7.46(d,J=3.6Hz,2H),7.45-7.42(m , 4H). ¹³ CNMR (101MHz, Chloroform-d) δ145.6, 131.1, 129.3, 124.8.

Example 11

In a 10 mL reaction tube, 2-chloroethyl sulfide (0.2 mmol) photocatalyst (2.0 mg) was mixed uniformly in 1 mL of water, stirred at room temperature, and irradiated with a blue LED light source for 12 h. The reaction was monitored by TLC, and when the substrate was completely consumed, 5.0 mL of water was added to the reaction system and extracted with ethyl acetate (3 x 5.0 mL). The organic phases were combined, dried over anhydrous Na ₂ SO ₄ , filtered, and the organic solvent was spin-dried under reduced pressure. The crude product was separated by medium silica gel column chromatography using petroleum ether/ethyl acetate as the eluent to obtain the target product 11.

¹ H NMR (400MHz, Chloroform-d)δ4.17-3.73(m,2H),3.29-3.01(m,2H),2.82(q,J=7.2Hz,2H),1.39(t,J=7.5Hz , 3H). ¹³ C NMR (101MHz, Chloroform-d) δ54.2, 46.1, 37.0, 6.8.

Although the embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, therefore , the scope of the present invention is not limited to the contents disclosed in the embodiments.

Claims (5)

1. A porous organic polymer of the 4CzIPN type, characterized in that: the synthesis method comprises the following steps:

wherein, 4CzIPN represents 2,4,5, 6-tetra (9H-carbazole-9-yl) isophthalonitrile, FDA represents formaldehyde dimethyl acetal, POP represents a porous organic polymer, and the 4CzIPN type POP1-3 is quickly and efficiently constructed through Friedel-Crafts alkylation reaction of the optically active unit 4CzIPN and the connecting substance formaldehyde dimethyl acetal FDA.

2. The porous organic polymer of 4CzIPN type according to claim 1, wherein: the synthetic method comprises the following steps: FeCl is added ₃ Adding into 1, 2-dichloroethane solution of 4CzIPN, stirring at room temperature, adding formaldehyde dimethyl acetal, stirring at 45 deg.C, stirring at 80 deg.C to obtain POP-1 crude product solution, and adding into POP-1 crude productAdding FDA into the product solution, continuously stirring at 80 ℃ until the crosslinking reaction is completed to obtain a crude product solution of POP-2, simultaneously adding FDA into the dissolution of the crude product of POP-2, continuously stirring at 80 ℃ until the crosslinking reaction is completed to obtain a crude product solution of POP-3, adding methanol into the crude product solution, continuously stirring, filtering and precipitating, stirring the obtained solid in concentrated hydrochloric acid, filtering the suspension again, washing the suspension with water and methanol, extracting with methanol/dichloromethane in a Soxhlet extractor, and then vacuum-drying the solid product with tetrahydrofuran to obtain porous organic polymers POP-1, POP-2 and POP-3 with different crosslinking degrees.

3. The application of a porous organic polymer of 4CzIPN type is characterized in that: applying the 4CzIPN type porous organic polymer to catalyze visible light induced C (sp) ³ ) -H bond phosphorylation functionalization reaction, said reaction equation being as follows:

wherein the phosphorylating reagent comprises: phosphorus diaryloxide, H-phosphite, phenylphosphinate, the R group including: phenyl, 2-pyridyl, benzyl,

the reaction conditions include: using tetrahydroisoquinoline and a phosphorylation reagent as initial raw materials, using a 4CzIPN type porous organic polymer as a photocatalyst, irradiating 460nm LED blue light at room temperature in the air or oxygen atmosphere, and after complete reaction, separating and purifying to obtain a series of C (sp) ³ ) -H-bond functionalized products, wherein the polymeric photocatalyst is separable by filtration or centrifugation and reusable.

4. The application of a porous organic polymer of 4CzIPN type is characterized in that: the 4CzIPN type porous organic polymer is applied to catalyzing a visible light-induced selective oxidation sulfide reaction, and the reaction equation is as follows:

wherein R is ¹ A methyl or methyl group, R ² Is aryl, H-phosphite, phenyl phosphinite, and the R group comprises: phenyl, 2-pyridyl and benzyl, and the reaction conditions comprise: taking thioether as a starting material, taking a 4CzIPN type porous organic polymer as a photocatalyst, irradiating 460nm LED blue light at room temperature in the air or oxygen atmosphere, and after complete reaction, separating and purifying to obtain a series of C (sp) ³ ) -H-bond functionalized products, wherein the polymeric photocatalyst is separable by filtration or centrifugation and reusable.

5. The application of a porous organic polymer of 4CzIPN type is characterized in that: the 4CzIPN type porous organic polymer is applied to realizing direct phosphorylation of commercially available anticoagulant drugs of ticlopidine and clopidogrel and oxidation of mustard gas simulant 2-chloroethyl sulfide CEES.