Asymmetric vinyl functionalized monophosphine compound as well as preparation method and application thereof

Abstract

The invention provides an asymmetric vinyl functionalized monophosphine compound as well as a preparation method and application thereof, and belongs to the field of monophosphine compounds. The asymmetric vinyl functionalized monophosphine compound disclosed by the invention can be subjected to polymerization reaction to prepare a porous organic polymer because of containing unsaturated double bonds, so that the number of monophosphine compounds is increased, and the application of the porous organic polymer can be promoted.

Description

Technical Field

[0001] The invention relates to the field of monophosphine compounds, and in particular to an asymmetric vinyl functionalized monophosphine compound and a preparation method and application thereof. Background Art

[0002] The trivalent organic phosphine, phosphite or phosphoramidite ligands in the phosphine ligands are both σ electron donors and π electron acceptors. As a "soft base", they have good coordination ability with late transition metals such as ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, etc. As homogeneous catalysts, metal-phosphine complexes prepared from phosphine ligands and late transition metals are widely used in the activation or construction of carbon-hydrogen bonds, saturated carbon-carbon bonds, unsaturated carbon-carbon bonds, carbon-nitrogen bonds, carbon-oxygen bonds, carbon-halogen bonds, etc., and often show high catalytic activity and selectivity in the reaction. However, they are difficult to separate and recover when dissolved in the reaction system, which greatly limits their application in large-scale production.

[0003] In order to facilitate the recovery and reuse of metal-phosphine complex catalysts, researchers first combine functionalized phosphine ligands with inorganic materials by adsorption or chemical bonding to prepare phosphorus-containing heterogeneous catalysts. However, inorganic materials have a single active site on the surface and very limited chemical modification potential, which greatly restricts the development of catalysts based on phosphine ligands and inorganic carriers.

[0004] Currently, common phosphorus-containing porous organic polymers (POPs) are usually pore-based materials formed by covalently linking phosphine compounds. Compared with metal-phosphine complexes, porous organic polymers have the advantages of large specific surface area, developed pores and easy separation from solvent systems. Compared with phosphine ligand-inorganic carrier catalysts, they have the advantages of stable molecular skeleton, adjustable modification and strong modifiability. Therefore, porous organic polymers have broad application prospects in separation, heterogeneous catalysis, pollutant capture, gas storage, etc.

[0005] Currently, there are few monophosphine compounds used to prepare porous organic polymers. Common monophosphine compounds used to prepare porous organic polymers include Figure 1 The small number of monophosphine compounds also limits the application of porous organic polymers to a certain extent. Summary of the invention

[0006] The invention provides an asymmetric vinyl functionalized monophosphine compound and a preparation method and application thereof. The asymmetric vinyl functionalized monophosphine compound of the invention expands the number of monophosphine compounds.

[0007] The present invention provides an asymmetric vinyl functionalized monophosphine compound having a structural formula shown in Formula I:

[0008]

[0009] R includes deuterium, halogen, amino, cyano, nitro, alkyl, alkoxy, haloalkoxy, alkenyl, alkynyl, -C(O)OR1, -C(O)R1, -C(O)N(R1)2, -NHC(O)R1, phenyl, substituted phenyl, 5-6 membered heteroaryl, substituted 5-6 membered heteroaryl, C3-8 membered cycloalkyl or substituted C3-8 membered cycloalkyl;

[0010] The R1 includes hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl.

[0011] An asymmetric vinyl functionalized monophosphine compound, characterized in that it has a structural formula shown in Formula I:

[0012]

[0013] R includes deuterium, halogen, amino, cyano, nitro, alkyl, alkoxy, haloalkoxy, alkenyl, alkynyl, -C(O)OR1, -C(O)R1, -C(O)N(R1)2, -NHC(O)R1, phenyl, substituted phenyl, 5-6 membered heteroaryl, substituted 5-6 membered heteroaryl, C3-8 membered cycloalkyl or substituted C3-8 membered cycloalkyl;

[0014] The R1 includes hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl.

[0015] Preferably, the alkyl group includes one of methyl, ethyl and propyl;

[0016] The alkoxy group in the alkoxy group and the halogenated alkoxy group includes one of methoxy, ethoxy and propoxy;

[0017] The alkenyl group includes one of vinyl, propenyl, butenyl, pentenyl and hexenyl;

[0018] The alkynyl group includes one of ethynyl, propynyl, butynyl, pentynyl and hexynyl;

[0019] The number of substituents in the substituted phenyl, substituted 5-6-membered heteroaryl and substituted C3-8-membered cycloalkyl is 1 to 3;

[0020] The substituents in the substituted phenyl, substituted 5-6 membered heteroaryl and substituted C3-8 membered cycloalkyl include halogen, hydroxyl, amino, cyano, C 1-3 Alkyl, C 1-3 Alkoxy and halogenated C 1-3 At least one of the alkoxy groups.

[0021] Preferably, it has a structural formula shown in any one of formulas I-1 to I-18:

[0022]

[0023] The present invention also provides a method for preparing the asymmetric vinyl functionalized monophosphine compound described in the above technical solution, comprising the following steps:

[0024] Mixing 4-halogenated styrene, alkyl lithium and an organic solvent to carry out a lithium-halogen exchange reaction to obtain a reaction solution containing a styrene lithium reagent;

[0025] The reaction solution is mixed with a solution of a compound of the structural formula shown in Formula II to carry out a nucleophilic substitution reaction to obtain the asymmetric vinyl functionalized monophosphine compound;

[0026]

[0027] Preferably, the method for preparing the compound having the structural formula shown in Formula II comprises the following steps:

[0028] Mixing aromatic phenyl ammonium hypophosphite, a compound of the structural formula represented by formula III, a catalyst and a polar organic solvent to carry out a cross-coupling reaction to obtain a compound of the structural formula represented by formula II;

[0029]

[0030] Preferably, the molar ratio of 4-bromostyrene to alkyllithium is 1:1 to 3;

[0031] The molar ratio of the compound of the structural formula shown in formula II to 4-bromostyrene is 1:1 to 1.5.

[0032] Preferably, the compound of the structural formula shown in formula II has the structural formula shown in any one of formulas II-1 to II-18:

[0033]

[0034] Preferably, the temperature of the lithium halogen exchange reaction is -78°C to 0°C, and the time is 0.5 to 2 hours.

[0035] Preferably, the temperature of the nucleophilic substitution reaction is -78 to 30°C, and the time is 12 to 24 hours.

[0036] The present invention also provides the use of the asymmetric vinyl functionalized monophosphine compound described in the above technical solution or the asymmetric vinyl functionalized monophosphine compound prepared by the preparation method described in the above technical solution in the preparation of porous organic polymers.

[0037] The asymmetric vinyl functionalized monophosphine compound of the present invention can undergo polymerization reaction to prepare porous organic polymers because of its unsaturated double bonds, thereby expanding the number of monophosphine compounds and promoting the application of porous organic polymers. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 It is a common monophosphine compound used to prepare porous organic polymers;

[0039] Figure 2 The synthetic route of the asymmetric vinyl functionalized monophosphine compound in the examples;

[0040] Figure 3 is the hydrogen spectrum of the asymmetrically vinyl-functionalized monophosphine compound of Example 1;

[0041] Figure 4 is the phosphorus spectrum of the asymmetrically vinyl-functionalized monophosphine compound of Example 1;

[0042] Figure 5 is the hydrogen spectrum of ethyl phenyl hypophosphite used in Example 1;

[0043] Figure 6 is the carbon spectrum of ethyl phenyl phosphinate used in Example 1;

[0044] Figure 7 is the phosphorus spectrum of phenyl ethyl hypophosphite used in Example 1;

[0045] Figure 8 This is the SEM image of Pd@POL-dppe in Application Example 1. DETAILED DESCRIPTION

[0046] The present invention provides an asymmetric vinyl functionalized monophosphine compound having a structural formula shown in Formula I:

[0047]

[0048] R includes deuterium, halogen, amino, cyano, nitro, alkyl, alkoxy, haloalkoxy, alkenyl, alkynyl, -C(O)OR1, -C(O)R1, -C(O)N(R1)2, -NHC(O)R1, phenyl, substituted phenyl, 5-6 membered heteroaryl, substituted 5-6 membered heteroaryl, C3-8 membered cycloalkyl or substituted C3-8 membered cycloalkyl;

[0049] The R1 includes hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl.

[0050] In the present invention, the alkyl group preferably includes one of a methyl group, an ethyl group and a propyl group;

[0051] The alkoxy group in the alkoxy group and the halogenated alkoxy group preferably includes one of methoxy group, ethoxy group and propoxy group;

[0052] The alkenyl group preferably includes one of vinyl, propenyl, butenyl, pentenyl and hexenyl;

[0053] The alkynyl group preferably includes one of ethynyl, propynyl, butynyl, pentynyl and hexynyl;

[0054] The number of substituents in the substituted phenyl, substituted 5-6 membered heteroaryl and substituted C3-8 membered cycloalkyl is preferably 1 to 3;

[0055] The substituents in the substituted phenyl, substituted 5-6 membered heteroaryl and substituted C3-8 membered cycloalkyl preferably include halogen, hydroxyl, amino, cyano, C 1-3 Alkyl, C 1-3 Alkoxy and halogenated C 1-3 At least one of the alkoxy groups.

[0056] In the present invention, the asymmetric vinyl functionalized monophosphine compound preferably has a structural formula shown in any one of Formulas I-1 to I-18:

[0057]

[0058] The present invention also provides a method for preparing the asymmetric vinyl functionalized monophosphine compound described in the above technical solution, comprising the following steps:

[0059] Mixing 4-halogenated styrene, alkyl lithium and an organic solvent to carry out a lithium-halogen exchange reaction to obtain a reaction solution;

[0060] The reaction solution is mixed with a solution of a compound of the structural formula shown in Formula II to carry out a nucleophilic substitution reaction to obtain the asymmetric vinyl functionalized monophosphine compound;

[0061]

[0062] The invention mixes 4-halogenated styrene, alkyl lithium and an organic solvent to carry out lithium halogen exchange reaction to obtain a reaction solution.

[0063] In the present invention, the mixing preferably includes: dissolving 4-halostyrene in a part of the organic solvent to obtain a 4-halostyrene solution; dissolving alkyl lithium in the remaining organic solvent to obtain an alkyl lithium solution; and dropping the alkyl lithium solution into the 4-halostyrene solution.

[0064] In the present invention, the molar ratio of the 4-halostyrene to the alkyllithium is preferably 1:1-1.5. In a specific embodiment of the present invention, the molar ratio of the 4-halostyrene to the alkyllithium may be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:1.5; the 4-halostyrene preferably includes 4-bromostyrene; and the alkyllithium preferably includes n-butyllithium.

[0065] In the present invention, the solid-liquid ratio of the 4-halostyrene to part of the organic solvent is preferably 1g:20-60mL. In a specific embodiment of the present invention, the solid-liquid ratio of the 4-halostyrene to part of the organic solvent may be 1g:20mL, 1g:30mL, 1g:40mL, 1g:50mL or 1g:60mL; the concentration of the alkyl lithium solution is preferably 2.5-13M; the organic solvent preferably includes tetrahydrofuran and / or n-hexane.

[0066] In the present invention, the temperature of the lithium halogen exchange reaction is preferably -78 to 0°C. In a specific embodiment of the present invention, the temperature of the lithium halogen exchange reaction can be -78°C, -75°C, -60°C, -50°C, -40°C, -30°C, -20°C, -10°C or 0°C; the time is 0.5 to 2h. In a specific embodiment of the present invention, the time of the lithium halogen exchange reaction can be 0.5h, 1h, 1.5h or 2h. The time of the lithium halogen exchange reaction starts from the end of the dropwise addition.

[0067] In the present invention, the lithium halogen exchange reaction is preferably carried out in an inert environment under stirring conditions.

[0068] In the lithium-halide exchange reaction, 4-halogenated styrene reacts with alkyl lithium to produce p-styrene lithium.

[0069] After obtaining the reaction solution, the present invention mixes the reaction solution with a solution of a compound of the structural formula shown in Formula II to carry out a nucleophilic substitution reaction to obtain the asymmetric vinyl functionalized monophosphine compound.

[0070] In the present invention, the molar ratio of the compound of formula II to 4-halogenated styrene is preferably 1:1 to 1.1. The concentration of the compound of formula II in the solution of the compound of formula II is preferably 0.98 to 2.9 mol / L. In a specific embodiment of the invention, the concentration of the compound of formula II in the solution of the compound of formula II can be 0.98 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L or 2.9 mol / L; the solvent of the solution preferably includes tetrahydrofuran.

[0071] In the present invention, the method for preparing the compound having the structural formula shown in Formula II comprises the following steps:

[0072] Mixing aromatic phenyl ammonium hypophosphite, a compound of the structural formula represented by formula III, a catalyst and a polar organic solvent to carry out a cross-coupling reaction to obtain a compound of the structural formula represented by formula II;

[0073]

[0074] In the present invention, the chemical formula of the aromatic phenyl ammonium hypophosphite is: PhNH3.OP(O)H2.

[0075] In the present invention, the molar ratio of the aromatic phenyl ammonium hypophosphite to the compound of the structural formula represented by formula III is preferably 1:1.1.

[0076] In the present invention, the molar ratio of the aromatic phenyl ammonium hypophosphite to the catalyst is preferably 1:0.01; the catalyst preferably includes metal palladium and / or Pd(OAc)2-dppp; and the molar ratio of Pd(OAc)2 to dppp is preferably 1:1.

[0077] In the present invention, the liquid-to-solid ratio of the aromatic phenyl ammonium hypophosphite to the polar organic solvent is preferably 1 g:60 mL; the polar organic solvent preferably includes one or more of acetonitrile, tetrahydrofuran, 1,2-dichloroethane, dioxane, dichloromethane, ether, chloroform and N,N-dimethylformamide.

[0078] In the present invention, the temperature of the cross-coupling reaction is preferably 100° C., and the time is preferably 6 h.

[0079] After the cross-coupling reaction is completed, the present invention preferably performs post-treatment on the obtained product; the post-treatment preferably includes: extraction and separation.

[0080] The compound of the structural formula shown in Formula II has the structural formula shown in Formula II-1 to II-18:

[0081]

[0082]

[0083] In the present invention, the temperature of the nucleophilic substitution reaction is preferably -78 to 30°C. In a specific embodiment of the present invention, the temperature of the nucleophilic substitution reaction can be -78°C, -75°C, -60°C, -50°C, -40°C, -30°C, -20°C, -10°C, 0°C, 10°C, 20°C or 30°C; the time is preferably 12 to 24h. In a specific embodiment of the present invention, the time of the nucleophilic substitution reaction can be 12h, 15h, 18h, 20h or 24h. In the present invention, the nucleophilic substitution reaction is preferably carried out under stirring conditions.

[0084] In the present invention, the nucleophilic substitution reaction is preferably carried out in an inert environment.

[0085] After the nucleophilic substitution reaction is completed, the present invention preferably mixes the obtained product with a quencher for quenching, then mixes the quenched product with an extractant to extract and separate organic matter to obtain an organic phase; the organic phase is mixed with a solid desiccant and dried and then purified to obtain the asymmetric vinyl functionalized monophosphine compound.

[0086] In the present invention, the quenching agent preferably includes a saturated aqueous ammonium chloride solution; the extracting agent preferably includes water and ethyl acetate; the volume ratio of water:ethyl acetate is preferably 3:1; the solid desiccant preferably includes anhydrous magnesium sulfate, and the purification method preferably includes elution after column chromatography.

[0087] In the present invention, the eluent for elution preferably includes petroleum ether and ethyl acetate; the volume ratio of the petroleum ether to ethyl acetate is preferably 3:1.

[0088] The present invention also provides the use of the asymmetric vinyl functionalized monophosphine compound described in the above technical solution or the asymmetric vinyl functionalized monophosphine compound prepared by the preparation method described in the above technical solution as a porous organic polymer precursor.

[0089] The asymmetric vinyl functionalized monophosphine compound provided by the present invention and its preparation method and application are described in detail below in conjunction with the examples, but they should not be construed as limiting the scope of protection of the present invention.

[0090] The synthetic route of the asymmetric vinyl functionalized monophosphine compound of the embodiment of the present invention is as follows: Figure 2 shown.

[0091] Arylphenyl ethyl hypophosphite (having a structure shown in any one of formulas II-1 to II-18) is prepared by the method disclosed in the document "Palladium-catalyzed phosphorus-carbon bond formation: cross-coupling reactions of alkyl phosphinates with aryl, heteroaryl, alkenyl, benzylic, andallylic halides and triflates" (Applications of Catalysis in Academia and Industry, 2005, 61 (26): 6315-6329. DOI: 10.1016 / j.tet.2005.03.107.):

[0092] The aromatic phenyl ammonium hypophosphite, the compound of the structural formula represented by formula III, a catalyst and a polar organic solvent are mixed and subjected to a cross-coupling reaction at 100° C. for 6 hours, followed by extraction and separation to obtain the compound of the structural formula represented by formula II;

[0093] The molar ratio of aromatic phenyl ammonium hypophosphite to the compound of the structural formula shown in formula III is 1:1.1.

[0094] The molar ratio of the aromatic phenyl ammonium hypophosphite to the catalyst is 1:0.01; the catalyst is Pd(OAc)2-dppp (the molar ratio of Pd(OAc)2 to dppp is 1:1).

[0095] The liquid-to-solid ratio of the aromatic phenyl ammonium hypophosphite to acetonitrile is 1 g:60 mL.

[0096] Example 1

[0097] Under inert gas, add 4-bromostyrene (1.0 g, 27.5 mmol) and 20 mL of freshly treated anhydrous tetrahydrofuran into a round-bottom flask to obtain a reaction solution; then cool the reaction solution to -78°C, and add 2.25 mL of an n-butyllithium solution (solvent: n-hexane) containing 27.5 mmol of n-butyllithium dropwise into the reaction solution with a syringe. After the addition of butyllithium is completed, continue stirring for 1 hour to obtain a p-vinylphenyllithium solution.

[0098] At -78°C, the obtained p-vinylphenyl lithium solution was added dropwise to 10 mL of 2.9 mol / L tetrahydrofuran solution of ethyl phenyl hypophosphite using a syringe. After the addition was completed, the mixture was naturally warmed to room temperature and stirred overnight. After the reaction was completed, 15 mL of saturated aqueous ammonium chloride solution was added for quenching, and ethyl acetate (the volume ratio of water to ethyl acetate was 3:1) was used for extraction. The organic phase was dried by adding anhydrous magnesium sulfate, purified by column chromatography, and eluted with an eluent (the volume ratio of petroleum ether to ethyl acetate was 3:1) to obtain 0.965 g of a colorless oil (I-1) with a yield of 72%.

[0099] Example 2

[0100] Under inert gas, add 4-bromostyrene (5.0 g, 27.5 mmol) and 60 mL of freshly treated anhydrous tetrahydrofuran into a round-bottom flask to obtain a reaction solution; then cool the reaction solution to -78°C, and add 11 mL of an n-butyllithium solution (the solvent is n-hexane) containing 27.5 mmol of n-butyllithium dropwise into the reaction solution with a syringe. After the addition of butyllithium is completed, continue stirring for 1 hour to obtain a p-vinylphenyllithium solution.

[0101] At -78 ° C, the obtained p-vinylphenyl lithium solution was added dropwise to 30 mL of 0.98 mol / L tetrahydrofuran solution of ethyl phenyl hypophosphite using a syringe. After the addition was completed, the temperature was naturally returned to room temperature and stirred overnight. After the reaction was completed, 45 mL of saturated ammonium chloride aqueous solution was added for quenching, and ethyl acetate (the volume ratio of water to ethyl acetate was 3:1) was used for extraction. The organic phase was dried by adding anhydrous magnesium sulfate, purified by column chromatography, and eluted with an eluent (the volume ratio of petroleum ether to ethyl acetate was 3:1) to obtain any one of the other I-2 to I-18.

[0102] (1) Example 1 Hydrogen Spectrum of Asymmetric Vinyl-functionalized Monophosphine Compound ( 1 HNMR, 500 MHz, DMSO-d6, as Figure 3 Chemical shift (ppm): δ7.76-7.49 (m, 9H), 6.78 (dd, J = 17.6, 11.0 Hz, 1H), 5.97 (d, J = 17.7 Hz, 1H), 5.40 (d, J = 11.0 Hz, 1H).

[0103] (2) Phosphorus spectrum of the asymmetric vinyl functionalized monophosphine compound of Example 1 ( 31 P NMR, 500 MHz, CDCl3-d6, as Figure 4 As shown), chemical shift (ppm): δ32.44.

[0104] (3) Hydrogen spectrum of ethyl phenylphosphinate used in Example 1 ( 1HNMR, 600MHz, CDCl3-d6, such as Figure 5 Chemical shift (ppm): 1HNMR 7.81-7.73 (m, 2H), 7.60-7.55 (m, 1H), 7.50 (td, J = 7.7, 3.5 Hz, 2H), 4.20-4.07 (m, 2H), 1.37 (t, J = 7.1 Hz, 3H).

[0105] (4) Carbon spectrum of ethyl phenyl phosphite used in Example 1 ( 1 CNMR, 600MHz, CDCl3-d6, such as Figure 6 As shown), chemical shift (ppm): 13C NMR δ 133.80, 133.07, 130.95, 130.87, 128.81, 128.72, 77.28, 76.85, 76.30, 62.08, 62.03, 16.29.

[0106] (5) Phosphorus spectrum of ethyl phenylphosphinate used in Example 1 ( 31 PNMR, 600MHz, CDCl3-d6, such as Figure 7 As shown), chemical shift (ppm): δ24.80.

[0107] The above elemental analysis, hydrogen spectrum and phosphorus spectrum test results show that the sample is consistent with the asymmetric vinyl functionalized monophosphine compound of Example 1.

[0108] In summary, the present invention provides a brand-new structure and preparation method, the preparation method is relatively simple to operate, simple in purification, with fewer steps and high yield.

[0109] Application Example 1

[0110] The compound obtained in Example 1 (100 mg) and AIBN (100 mg) were added to 5 mL of THF and reacted at 100° C. for 24 h to obtain a porous organic phosphine ligand polymer.

[0111] 100 mg of porous organic phosphine ligand polymer (POL-dppe) and 15 mg of Pd(PPh3)2Cl were dissolved in 10 mL of THF and stirred at room temperature for more than 24 h. After evaporating THF under vacuum, yellow solid Pd@POL-dppe was obtained.

[0112] The SEM image of Pd@POL-dppe in Application Example 1 is shown below: Figure 8 shown.

[0113] Depend on Figure 8 It can be seen that Pd@POL-dppe has a porous structure.

[0114] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An asymmetric vinyl functionalized monophosphine compound, characterized in that: It has the structural formula shown in Formula I: R includes deuterium, halogen, amino, cyano, nitro, alkyl, alkoxy, haloalkoxy, alkenyl, alkynyl, -C(O)OR1, -C(O)R1, -C(O)N(R1)2, -NHC(O)R1, phenyl, substituted phenyl, 5-6 membered heteroaryl, substituted 5-6 membered heteroaryl, C3-8 membered cycloalkyl or substituted C3-8 membered cycloalkyl; The R1 includes hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl.

2. The asymmetric vinyl functionalized monophosphine compound according to claim 1, characterized in that The alkyl group includes one of a methyl group, an ethyl group and a propyl group; The alkoxy group in the alkoxy group and the halogenated alkoxy group includes one of methoxy, ethoxy and propoxy; The alkenyl group includes one of vinyl, propenyl, butenyl, pentenyl and hexenyl; The alkynyl group includes one of ethynyl, propynyl, butynyl, pentynyl and hexynyl; The number of substituents in the substituted phenyl, substituted 5-6-membered heteroaryl and substituted C3-8-membered cycloalkyl is 1 to 3; The substituents in the substituted phenyl, substituted 5-6 membered heteroaryl and substituted C3-8 membered cycloalkyl include halogen, hydroxyl, amino, cyano, C 1-3 Alkyl, C 1-3 Alkoxy and halogenated C 1-3 At least one of the alkoxy groups.

3. The asymmetric vinyl functionalized monophosphine compound according to claim 1 or 2, characterized in that: It has the structural formula shown in any one of formulas I-1 to I-18:

4. The method for preparing the asymmetric vinyl functionalized monophosphine compound according to any one of claims 1 to 3, characterized in that: The following steps are involved: Mixing 4-halogenated styrene, alkyl lithium and an organic solvent to carry out a lithium-halogen exchange reaction to obtain a reaction solution containing a styrene lithium reagent; The reaction solution is mixed with a solution of a compound of the structural formula shown in Formula II to carry out a nucleophilic substitution reaction to obtain the asymmetric vinyl functionalized monophosphine compound; 5. The preparation method according to claim 4, characterized in that: The method for preparing the compound having the structural formula shown in Formula II comprises the following steps: Mixing aromatic phenyl ammonium hypophosphite, a compound of the structural formula represented by formula III, a catalyst and a polar organic solvent to carry out a cross-coupling reaction to obtain a compound of the structural formula represented by formula II; 6. The preparation method according to claim 4, characterized in that: The molar ratio of 4-bromostyrene to alkyllithium is 1:1-3; The molar ratio of the compound of the structural formula shown in formula II to 4-bromostyrene is 1:1 to 1.

5.

7. The preparation method according to claim 4, characterized in that: The compound of the structural formula shown in Formula II has the structural formula shown in any one of Formulas II-1 to II-18:

8. The preparation method according to claim 4, characterized in that: The temperature of the lithium halogen exchange reaction is -78°C to 0°C, and the time is 0.5 to 2 hours.

9. The preparation method according to claim 4, characterized in that: The temperature of the nucleophilic substitution reaction is -78 to 30° C., and the time is 12 to 24 hours.

10. Use of the asymmetric vinyl functionalized monophosphine compound according to any one of claims 1 to 3 or the asymmetric vinyl functionalized monophosphine compound prepared by the preparation method according to any one of claims 4 to 9 in the preparation of porous organic polymers.

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