Gem-difluoroolefin functionalized siloxane compound as well as preparation method and application thereof

Abstract

The invention relates to the technical field of organic synthesis, in particular to a gem-difluoroolefin functionalized siloxane compound as well as a preparation method and application thereof.The preparation method comprises the following steps: mixing trifluoromethyl olefin A, a silane compound B, a photocatalyst C, a reagent D capable of passing through hydrogen and an organic solvent E, stirring at room temperature in an inert atmosphere, and reacting through visible light irradiation to obtain the gem-difluoroolefin functionalized siloxane compound. And separating and purifying after reaction to obtain a target product. According to the preparation method, the reaction condition is mild, the reaction can be completed under the room temperature condition, and high temperature and high pressure or transition metal catalysts are not needed. The reaction substrate of the preparation method has high functional group compatibility, resists sensitive functional groups such as halogen, alkoxy, hydroxyl and amino, and is wide in application range.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis, specifically to a gemdifluoroolefin-functionalized siloxane compound, its preparation method, and its applications. Background Technology

[0002] Siloxane compounds are widely used in materials science, surface treatment, and organic synthesis due to their unique chemical stability and interfacial activity. Traditional siloxane functionalization methods often require transition metal catalysts or high-temperature, high-pressure conditions, which present problems such as harsh reaction conditions and poor tolerance of functional groups. Furthermore, the introduction of fluorine-containing groups can significantly improve the hydrophobicity and chemical stability of materials, but the directional construction of gem-difluoroolefin structures in existing technologies still faces challenges, especially the urgent need to develop efficient and mild synthetic strategies.

[0003] To address the aforementioned problems, this invention proposes a method for preparing gem-difluoroolefin-functionalized siloxane compounds based on photocatalytic radical reactions. This method does not require the participation of transition metals, has mild reaction conditions, and exhibits excellent functional group compatibility. Summary of the Invention

[0004] To address the aforementioned problems, one objective of this invention is to provide a method for preparing gemdifluoroolefin-functionalized siloxane compounds that is mild, simple, efficient, and does not depend on transition metals.

[0005] The second objective of this invention is to provide a gemdifluoroolefin-functionalized siloxane compound applicable to the fields of materials science, surface treatment, and organic synthesis.

[0006] The third objective of this invention is to provide an application of a gemdifluoroolefin-functionalized siloxane compound.

[0007] One of the technical solutions adopted to achieve the objective of this invention is: a method for preparing a gemdifluoroolefin functionalized siloxane compound, comprising the following steps: mixing trifluoromethyl olefin A, silane compound B, photocatalyst C, hydrogen-binding reagent D and organic solvent E, stirring at room temperature under an inert atmosphere, reacting under visible light irradiation, and separating and purifying to obtain the target product after the reaction is completed; The structural formula of the trifluoromethyl olefin A is as follows: ; The structural formula of silane compound B is: ; The structural formula of the gemino-difluoroolefin-functionalized siloxane compound is as follows: ; Among them, R 1 It is an aryl group. The TMSO group is a trimethylsiloxy group.

[0008] Preferably, the aryl group is any one of phenyl, naphthyl, anthryl, chrysenyl, perylenyl, benzopyrenyl, indolyl, quinolinyl, dibenzo furanyl, with one or more substituents, which are the same or different when there are multiple substituents.

[0009] Preferably, the substituent is at least one of C1-C20 alkyl, halogen atom, C1-C20 alkoxy, hydroxyl, amino.

[0010] Preferably, the alkyl group is C1-C10 alkyl, and the alkoxy group is C1-C10 alkoxy.

[0011] Preferably, the alkyl group is C1-C6 alkyl, and the alkoxy group is C1-C6 alkoxy.

[0012] The alkyl group is linear or branched.

[0013] Preferably, the photocatalyst C is any one of tris[2-phenylpyridine-C2,N] iridium(III), rhodamine 6G, rhodamine B, 2,4,5,6-tetra(9-carbazolyl)-1,3-dicyanobenzene (4CzIPN), solvent red 43, erythrosin B, solvent red 49, solvent red 24, fluorescein.

[0014] Preferably, the hydride reagent D is selected from at least one of quinuclidine compounds.

[0015] The quinuclidine compound includes at least one of acetylchrysin, quinuclidinol, aminoquinuclidine hydrochloride, quinuclidinone, quinuclidine, cyanquinuclidine, quinuclidine-3-carboxylic acid.

[0016] The thiol compound includes at least one of benzenethiol, 1,2-ethanedithiol, 1,6-hexanedithiol, butanethiol, triisopropylsilane thiol.

[0017] Preferably, the organic solvent E is at least one of dichloromethane, 1,4-dioxane, methyl tert-butyl ether, acetonitrile, toluene, chlorobenzene, chloroform, cyclopentane, n-pentane, n-hexane, cyclohexane, 1,2-dichloroethane, acetone.

[0018] Preferably, the visible light is blue light or visible light containing blue light.

[0019] Preferably, the molar ratio of the trifluoromethyl olefin A to the silane compound B is 1:1-6, the amount of the photocatalyst C is 0.01%-1% of the molar amount of the silane compound B, the concentration of the silane compound B in the mixed solution is 0.1 M-2 M, and the amount of the hydride reagent D is 1%-20% of the molar amount of the silane compound B.

[0020] The technical scheme adopted by the present application to achieve the second purpose is: a kind of difluoro olefin functionalized siloxane compound is prepared by the preparation method.

[0021] The technical scheme adopted by the present application to achieve the third purpose is: application of a kind of difluoro olefin functionalized siloxane compound, which is applied to the precursor of polysiloxane synthesis.

[0022] The siloxane functional group of the difluoro olefin functionalized siloxane compound can be used as a precursor of polysiloxane, and the difluoro olefin can remain as a further functionalization site after the formation of the polymer.

[0023] The present application has the following advantages and beneficial effects: (1) The preparation method of the present application has mild reaction conditions, and the reaction can be completed at room temperature without the need for high temperature and pressure or transition metal catalysts.

[0024] (2) The reaction substrate of the preparation method of the present application has high functional group compatibility, tolerates sensitive functional groups such as halogen, alkoxy, hydroxyl, amino, etc., and has a wide range of applications.

[0025] (3) The preparation method of the present application is simple and efficient, uses visible light catalysis strategy, the reaction system is simple, and the product is easy to separate and purify.

[0026] (4) The difluoro olefin functionalized siloxane compound prepared by the present application has both the hydrophobicity of the parent element and the interfacial activity of siloxane, and the olefin can be used as a high-performance silane coupling agent or surface treatment agent. The siloxane functional group of the difluoro olefin functionalized siloxane compound of the present application can be used as a precursor of polysiloxane, and the difluoro olefin can remain as a further functionalization site after the formation of the polymer. DETAILED DESCRIPTION

[0027] The present application will be described in detail below in conjunction with the examples, which are implemented on the premise of the technical scheme of the present application, and give detailed implementation modes and specific operation processes, but the protection scope of the present application is not limited to the following examples.

[0028] In the following examples, if not otherwise specified, they are all conventional methods; the reagents and materials, if not otherwise specified, can be obtained from commercial channels.

[0029] It should be noted that the examples in the present application and the features in the examples can be combined with each other without conflict.

[0030] Example 1:

[0031] In an argon-filled glove box, a dry screw-cap vial equipped with a magnetic stir bar was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl alkene A1 (0.1 mmol), and substrate silane B (0.25 mmol) successively. The vial was sealed and removed from the glove box. Irradiation was then carried out at room temperature using a blue LED lamp for 24 h with stirring. The crude product was purified by column chromatography on 200-300 mesh silica gel, and 43.9 mg of colorless oil was obtained as the final product in a yield of 56%.

[0032] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 7.35 – 7.29 (m, 2H), 7.02 (t, J = 8.7Hz, 2H), 1.65 (dd, J = 3.2, 2.1 Hz, 2H), 0.03 (s, 18H), -0.06 (s, 3H). 13 C NMR(151 MHz, CDCl3, 25 o C) δ 162.1 (d, J = 246.4 Hz), 153.1 (dd), 130.3 (dd, J = 7.8,3.8 Hz), 115.5, 115.4, 88.8 (dd, J = 14.7 Hz), 18.6, 2.0, 0.3. 19 F NMR (376 MHz,CDCl3, 25 o C) δ -92.35 (d, J = 48.1 Hz, 1F), -95.06 (d, J = 47.7 Hz, 1F), -116.29(s, 1F). Example 2:

[0033] In an argon-filled glove box, a dry screw-cap vial equipped with a magnetic stir bar was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl alkene A2 (0.1 mmol), and substrate silane B (0.25 mmol) successively. The vial was sealed and removed from the glove box. Irradiation was then carried out using a blue LED lamp at room temperature with stirring for 24 h. The crude product was purified by column chromatography on 200-300 mesh silica gel, and 52.6 mg of colorless oil was obtained as the final product in 60% yield.

[0034] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 7.59 (d, J = 8.1 Hz, 2H), 7.48 (d, J = 8.1Hz, 2H), 1.70 (dd, J = 3.2, 2.2 Hz, 2H), 0.02 (s, 18H), -0.02 (s, 3H). 13 C NMR(151 MHz, CDCl3, 25 o C) δ 153.4 (dd, J = 290.4, 286.1 Hz), 123.0, 129.3 (t, J =32.6 Hz), 129.0 (t, J = 3.6 Hz), 125.8 (d, J = 3.9 Hz), 125.5 (d), 89.1 (dd, J =24.5, 13.8 Hz), 18.2, 2.0, 0.2. 19 F NMR (376 MHz, CDCl3, 25 o C) δ -62.6 (s, 3F),-89.08 (d, J = 43.2 Hz, 1F), -92.10 (d, J = 43.3 Hz, 1F). Example 3:

[0035] In an argon-filled glovebox, a dry screw-cap vial equipped with a magnetic stir bar was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl alkene A3 (0.1 mmol), and substrate silane B (0.25 mmol). After the vial was sealed, it was removed from the glovebox. Irradiation was then performed at room temperature using a blue LED lamp for 24 h with stirring. The crude product was purified by column chromatography on 200-300 mesh silica gel, and 43.5 mg of colorless oil was obtained in 48% yield.

[0036] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 7.63 – 7.56 (m, 4H), 7.49 – 7.43 (m,4H), 7.39 – 7.33 (m, 1H), 1.75 (dd, J = 3.2, 2.1 Hz, 2H), 0.06 (s, 18H), -0.00(s, 3H). 13 C NMR (151 MHz, CDCl3, 25 o C) δ 152.99 (dd, J = 289.0, 284.7 Hz),140.95, 139.91, 134.31, 128.92, 128.79 (t, J = 3.7 Hz), 127.43, 127.18,127.02, 89.05 (dd, J = 23.5, 14.1 Hz), 18.14, 1.81, 0.09. 19 F NMR (376 MHz,CDCl3, 25 o C) δ -91.59 (d, J = 45.7 Hz, 1F), -94.29 (d, J = 46.9 Hz, 1F). Example 4:

[0037] In an argon-filled glove box, a dry screw-cap vial equipped with a magnetic stir bar was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl alkene A4 (0.1 mmol), and substrate silane B (0.25 mmol) in that order. The vial was sealed and removed from the glove box. Irradiation was then carried out at room temperature using a blue LED lamp for 24 h with stirring. The crude product was purified by column chromatography on silica gel (200-300 mesh) to give 56.6 mg of colorless oil in 69% yield.

[0038] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 7.29 (s, 4H), 1.65 (dd, J = 3.2, 2.1 Hz,2H), 0.03 (s, 18H), -0.06 (s, 3H). 13 C NMR (151 MHz, CDCl3, 25 o C) δ 152.90 (dd,J = 289.1, 285.3 Hz), 134.02 – 133.66 (m), 132.86, 129.74 (t, J = 3.8 Hz),128.48, 88.59 (dd, J = 24.0, 14.2 Hz), 18.14, 1.79, 0.11. 19 F NMR (376 MHz,CDCl3, 25 o C) δ -91.31 (d, J = 46.1 Hz, 1F), -94.05 (d, J = 45.8 Hz, 1F). Example 5:

[0039] In an argon-filled glove box, a dry screw-cap vial equipped with a magnetic stir bar was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl alkene A4 (0.1 mmol), and substrate silane B (0.25 mmol) in that order. The vial was sealed and removed from the glove box. Irradiation was then carried out at room temperature using a blue LED lamp for 24 h with stirring. The crude product was purified by column chromatography on silica gel (200-300 mesh) to give 56.6 mg of colorless oil in 69% yield.

[0040] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 7.35 (d, J = 2.0 Hz, 1H), 7.33 (t, J = 2.3Hz, 1H), 7.29 (dd, J = 1.6 Hz, 1H), 7.27 (d, J = 1.6 Hz, 1H), 1.68 (dd, J = 3.2,2.1 Hz, 2H), 1.31 (s, 9H), 0.01 (s, 18H), -0.05 (s, 3H). 13 C NMR (151 MHz,CDCl3, 25 o C) δ 152.9 (dd, J = 3.7 Hz), 150.0, 132.2 (d, J = 4.2 Hz), 128.0 (t, J =3.5 Hz), 125.2, 89.0 (dd, J = 23.2, 14.4 Hz), 34.6, 31.4, 18.1, 1.8, 0.0. 19 F NMR(376 MHz, CDCl3, 25 o C) δ -92.68 (d, J = 8.0 Hz, 1F), -95.23 (d, J = 8.5 Hz, 1F). Example 6:

[0041] In an argon-filled glove box, a dry reaction tube equipped with a Teflon-lined screw cap was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl olefin A6 (0.1 mmol) and substrate silane B (0.25 mmol) successively with a magnetic stirring bar. The reaction tube was sealed and removed from the glove box. Subsequently, irradiation was performed using a blue LED lamp at room temperature with stirring for 24 h. The crude product was purified by column chromatography on 200-300 mesh silica gel, and 25.0 mg of colorless oil was finally obtained in 64% yield.

[0042] 1H NMR (400 MHz, CDCl3, 25 o C) δ 7.25 (d, J = 7.0 Hz, 2H), 7.14 (d, J = 8.0Hz, 2H), 2.34 (s, 3H), 1.68 (dd, J = 3.2, 2.1 Hz, 2H), 0.04 (d, J = 0.8 Hz, 18H),-0.07 (s, 3H). 13 C NMR (151 MHz, CDCl3, 25 o C) δ 152.8 (dd, J = 287.9, 284.1 Hz),136.8, 132.3 (t, J = 4.2 Hz), 129.0, 128.3 (t, J = 3.5 Hz), 89.1 (dd, J = 23.3,14.6 Hz), 21.2, 18.3, 1.8, 0.1. 19 FNMR (376 MHz, CDCl3, 25 o C) δ -91.63 (d, J =49.2 Hz, 1F), -94.22 (d, J = 48.7 Hz, 1F). Example 7:

[0043] In an argon-filled glove box, a dry reaction tube equipped with a Teflon-lined screw cap with a magnetic stir bar was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl alkene A7 (0.1 mmol) and substrate silane B (0.25 mmol) successively. The reaction tube was sealed and removed from the glove box. Subsequently, irradiation was performed using a blue LED lamp at room temperature with stirring for 24 h. The crude product was purified by column chromatography on 200-300 mesh silica gel, and 32.9 mg of colorless oil was finally obtained in 85% yield.

[0044] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 8.62 (s, 1H), 8.48 (d, J= 3.4 Hz, 1H),7.65 (dd, J = 2.6, 1.4 Hz, 1H), 7.31 – 7.21 (m, 1H), 1.68 (dd, J = 3.1, 2.1 Hz,2H), 0.02 (s, 18H), -0.03 (s, 3H). 13 C NMR (151 MHz, CDCl3, 25 o C) δ 153.1 (dd, J = 286.5 Hz), 149.5 (d, J = 4.6 Hz), 148.2, 135.6 (t, J = 3.6 Hz), 131.4 (t, J = 4.9Hz), 123.2, 86.8 (dd, J = 25.0, 14.3 Hz), 17.7, 1.8, 0.1. 19 F NMR (376 MHz,CDCl3, 25 o C) δ -89.21 (d, J = 43.8 Hz, 1F), -92.41 (d, J = 44.4 Hz, 1F). Example 8:

[0045] In an argon-filled glove box, a dry reaction tube equipped with a Teflon-lined screw cap with a magnetic stir bar was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl alkene A8 (0.1 mmol), and substrate silane B (0.25 mmol) sequentially. The reaction tube was sealed and removed from the glove box. Irradiation was then carried out at room temperature using a blue LED lamp with stirring for 24 h. The crude product was purified by column chromatography on 200-300 mesh silica gel, and 22.7 mg of colorless oil was obtained as the final product with a yield of 57%.

[0046] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 7.36 (t, J= 1.2 Hz, 1H), 7.28 – 7.27(m, 1H), 7.25 – 7.21 (m, 2H), 1.74 – 1.62 (m, 2H), 0.05 (s, 18H), -0.01 (s,3H). 13 C NMR (151 MHz, CDCl3, 25 o C) δ 152.8 (t, J = 285.5 Hz), 137.0, 134.0 (dd, J = 5.5, 2.3 Hz), 129.3, 128.3, 127.0,126.4, 88.5 (dd, J = 26.0, 18.4 Hz), 17.9,1.6, -0.1. 19 FNMR (376 MHz, CDCl3, 25 o C) δ -89.84 (d, J = 44.9 Hz, 1F), -92.40(d, J = 44.6 Hz, 1F). Example 9:

[0047] In an argon-filled glove box, a dry reaction tube equipped with a Teflon-lined screw cap with a magnetic stir bar was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl alkene A9 (0.1 mmol) and substrate silane B (0.25 mmol) successively. The reaction tube was sealed and removed from the glove box. Subsequently, irradiation was performed using a blue LED lamp at room temperature with stirring for 24 h. The crude product was purified by column chromatography on 200-300 mesh silica gel, and finally 21.5 mg of colorless oil was obtained in a yield of 63%.

[0048] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 7.22 – 7.12 (m, 4H), 2.30 (s, 3H),1.60 – 1.58 (m, 2H), 0.02 (s, 18H), -0.06 (s, 3H). 13 C NMR (151 MHz, CDCl3,25 o C) δ 151.8 (dd, J= 285.9, 283.0 Hz), 136.7, 134.9 (d, J = 6.2 Hz), 130.3, 129.8 (d, J = 3.7 Hz), 127.6, 125.7, 87.8 (dd, J = 22.8, 19.6 Hz), 19.8, 19.7 (d, J = 2.5 Hz), 1.8, 0.2. 19 FNMR (376 MHz, CDCl3, 25 o C) δ -92.05 (d, J = 49.5 Hz, 1F), -94.85 (d, J = 49.4 Hz, 1F). Example 10:

[0049] In an argon-filled glove box, quinine ring D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl olefin A10 (0.1 mmol), and substrate silane B (0.25 mmol) were sequentially added to a dry reaction tube equipped with a magnetic stir bar and a screw cap lined with polytetrafluoroethylene. The reaction tube was then sealed and removed from the glove box. The mixture was then irradiated with a blue LED lamp at room temperature and stirred for 24 hours. The crude product was purified by silica gel column chromatography (200–300 mesh) to yield 29.0 mg of a colorless oil, with a yield of 75%.

[0050] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 7.24 – 7.19 (m, 1H), 7.15 (d, J = 1.9Hz, 2H), 7.05 (d, J = 7.6 Hz, 1H), 2.35 (s, 3H), 1.68 (dd, J = 3.2, 2.1 Hz, 2H), 0.03 (s, 18H), -0.06 (s, 3H). 13 C NMR (151 MHz, CDCl3, 25 o C) δ 152.8 (dd, J =288.1, 284.4 Hz), 137.8, 135.3 (t,J = 4.2 Hz), 129.1 (t, J = 3.3 Hz), 128.2,127.9, 125.6 (t, J = 3.4 Hz), 89.3 (dd, J = 23.1, 14.5 Hz), 21.6, 18.4, 1.8,0.1. 19 FNMR (376 MHz, CDCl3, 25 o C) δ -91.47 (d, J = 47.8 Hz, 1F), -93.99 (d, J =48.7 Hz, 1F). Example 11:

[0051] In an argon-filled glove box, a dry reaction tube equipped with a Teflon-lined screw cap with a magnetic stir bar was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl alkene A11 (0.1 mmol), and substrate silane B (0.25 mmol) sequentially. The reaction tube was sealed and removed from the glove box. Irradiation was then carried out at room temperature using a blue LED lamp for 24 h with stirring. The crude product was purified by column chromatography on 200-300 mesh silica gel, and 31.1 mg of colorless oil was obtained as the final product in 84% yield.

[0052] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 7.19 – 7.11 (m, 4H), 1.57 (dd, J = 3.2,2.1 Hz, 2H), -0.06 (s, 18H), -0.12 (s, 3H). 13 C NMR (151 MHz, CDCl3, 25 o C) δ153.0 (dd), 137.3 (t, J = 4.4 Hz), 134.2, 129.5, 128.5 (t, J = 3.6 Hz), 127.2,126.6 (t, J = 3.8 Hz), 88.7 (dd, J = 24.4, 13.8 Hz), 18.1, 1.8, 0.1.19 H NMR (400 MHz, CDC13, 25 o C) δ -89.84 (d, J = 44.9 Hz, 1F), -92.40 (d, J = 45.0 Hz, 1F). Example 12:

[0053] In an argon-filled glove box, a dry screw-capped reaction tube equipped with a Teflon®-lined magnetic stir bar was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl alkene A12 (0.1 mmol), and substrate silane B (0.25 mmol) sequentially. The reaction tube was sealed and removed from the glove box. Irradiation was then performed using a blue LED lamp at room temperature with stirring for 24 h. The crude product was purified by column chromatography on 200-300 mesh silica gel, and 17.3 mg of colorless oil was obtained as the final product in 44% yield.

[0054] 1 H NMR (400 MHz, CDC13, 25 o C) δ 7.19 (t, J = 7.8 Hz, 1H), 6.93 (dq, J =7.8, 1.4 Hz, 1H), 6.83 (dt, J = 2.9, 1.5 Hz, 1H), 6.71 (ddd, J = 8.1, 2.6, 0.9Hz, 1H), 4.68 (s, 1H), 1.65 (dd, J = 3.2, 2.1 Hz, 2H), 0.03 (s, 18H), -0.06 (s,3H). 13 C NMR (151 MHz, CDC13, 25 o C) δ 155.4, 153.8 (dd, J = 289.0 Hz), 137.0129.5, 121.1 (t, J = 3.6 Hz), 115.5 (t, J = 3.7 Hz), 114.1, 89.1 (dd), 18.2, 1.8,0.1. 19 F NMR (376 MHz, CDC13, 25o C) δ -90.64 (d, J = 46.1 Hz, 1F), -92.96 (d, J =46.4 Hz, 1F). Example 13:

[0055] In an argon-filled glove box, a dry screw-capped reaction tube equipped with a Teflon®-lined magnetic stir bar was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl alkene A13 (0.1 mmol), and substrate silane B (0.25 mmol) sequentially. The reaction tube was sealed and removed from the glove box. Irradiation was then performed using a blue LED lamp at room temperature with stirring for 24 h. The crude product was purified by column chromatography on 200-300 mesh silica gel, and 38.1 mg of colorless oil was obtained as the final product in 84% yield.

[0056] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 7.96 (d, J = 7.7 Hz, 1H), 7.89 (dd, J =7.5, 1.4 Hz, 1H), 7.60 (d, J = 8.2 Hz, 1H), 7.52 – 7.43 (m, 1H), 7.42 – 7.37(m, 1H), 7.35 (d, J = 1.3 Hz, 1H), 7.32 (d, J = 7.6 Hz, 1H), 1.98 – 1.91 (m, 2H),-0.02 (s, 18H), -0.12 (s, 3H). 13 C NMR (151 MHz, CDCl3, 25 o C) δ 156.4, 155.5 –152.8 (m), 151.2, 128.2 (t, J = 2.7 Hz), 127.6, 124.9, 124.6, 123.1, 123.0,121.0, 120.2 (dd, J = 5.3, 2.6 Hz), 120.1, 112.1, 85.2(dd, J= 26.5, 17.2 Hz), 18.4, 2.0, 0.1. 19 FNMR (376 MHz, CDCl3, 25 o C) δ -90.25 (d, J = 43.1 Hz, 1F), -91.95 (d, J = 43.1 Hz, 1F). Example 14:

[0057] In an argon-filled glove box, a dry Schlenk tube equipped with a Teflon-lined screw cap was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl alkene A14 (0.1 mmol) and substrate silane B (0.25 mmol) successively with a magnetic stirring bar. The Schlenk tube was sealed and removed from the glove box. Subsequently, irradiation was performed at room temperature using a blue LED lamp for 24 h with stirring. The crude product was purified by column chromatography on 200-300 mesh silica gel, and 20.8 mg of colorless oil was obtained as the final product with a yield of 49%.

[0058] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 7.97 – 7.91 (m, 1H), 7.88 – 7.84 (m,1H), 7.80 (m, 1H), 7.52 – 7.48 (m, 2H), 7.47 – 7.39 (m, 2H), 1.79 (d, J = 22.3Hz, 2H), -0.03 (s, 18H), -0.09 (s, 3H). 13 C NMR (151 MHz, CDCl3, 25 o C) δ 152.5(dd, J = 286.6, 283.9 Hz), 134.0, 133.2 (d, J = 6.1 Hz), 131.5, 128.6, 128.2,127.5 (d, J = 3.6 Hz), 126.2, 125.9, 125.5, 125.4, 87.2 (dd, J = 23.6, 19.3 Hz),20.4, 1.8, 0.3. 19FNMR (376 MHz, CDCl3, 25 o C) δ -91.03 (d, J = 48.6 Hz, 1F), -93.52 (d, J = 47.7 Hz, 1F). Example 15:

[0059] In an argon-filled glove box, quinine ring D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl olefin A15 (0.1 mmol), and substrate silane B (0.25 mmol) were sequentially added to a dry reaction tube equipped with a magnetic stir bar and a screw cap lined with polytetrafluoroethylene. The reaction tube was then sealed and removed from the glove box. The mixture was then irradiated with a blue LED lamp at room temperature and stirred for 24 hours. The crude product was purified by silica gel column chromatography (200–300 mesh) to yield 32.3 mg of a colorless oil, with a yield of 80%.

[0060] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 6.95 (s, 2H), 6.88 (s, 1H), 2.31 (s,6H), 1.66 (dd, J = 3.2, 2.1 Hz, 2H), 0.03 (s, 18H), -0.05 (s, 3H). 13 C NMR (151MHz, CDCl3, 25 o C) δ 152.8 (dd, J = 287.7, 284.5 Hz), 137.6, 135.2 (t, J = 4.2Hz), 128.8, 126.3 (t, J = 3.3 Hz), 89.3 (dd, J = 22.9, 14.7 Hz), 21.5, 18.4, 1.8,0.1. 19 FNMR (376 MHz, CDCl3, 25 o C) δ -91.70 (d, J = 48.3 Hz, 1F), -94.02 (d, J =48.8 Hz, 1F). Example 16: In an argon-filled glove box, a dry screw-cap vial equipped with a PTFE lined magnetic stir bar was charged with quinuclidine D (0.01 mmol), 4CzIPN C (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethyl alkene A16 (0.1 mmol), and substrate silane B (0.25 mmol) in that order. The vial was sealed and removed from the glove box. Irradiation was then performed using a blue LED lamp at room temperature with stirring for 24 h. The crude product was purified by column chromatography on 200-300 mesh silica gel. The final product was obtained as colorless oil in 68% yield.

[0061] 1 H NMR (400 MHz, CDCl3, 25 o C) δ 7.12 (t, J = 8.3 Hz, 1H), 7.05 (d, J = 1.4Hz, 1H), 7.02 (d, J = 4.2 Hz, 1H), 2.26 (d, J = 1.9 Hz, 3H), 1.65 (dd, J = 3.2, 2.1Hz, 2H), 0.04 (s, 18H), -0.05 (s, 3H). 13 C NMR (151 MHz, CDCl3, 25 o C) δ 161.2(d, J = 243.8 Hz), 153.0 (dd, J = 289.4, 284.7 Hz), 134.7 (p, J = 4.8 Hz), 131.1(d, J = 5.5 Hz), 123.7 (q, J = 3.4 Hz), 123.7 (d, J = 17.4 Hz), 115.1 (t, J = 3.8Hz), 114.9 (t, J = 3.7 Hz), 88.6 (dd, J = 24.4, 14.1 Hz), 18.1, 14.4 (d, J = 3.4Hz), 1.8, -0.1. 19 FNMR (376 MHz, CDCl3, 25 oC) δ -90.36 (d, J = 46.1 Hz, 1F), -92.74 (d, J = 46.2 Hz, 1F), -117.85 (t, J = 9.8 Hz, 1F). Example 17

[0062] In an argon-filled glove box, a dry screw-cap reaction tube equipped with a Teflon liner was charged with acetyl cryptophycin D (0.01 mmol), 2,4,5,6-tetrakis(9- carbazolyl)-1,3-dicyanobenzene (0.0015 mmol), N,N-dimethylacetamide (1.0 mL), trifluoromethyl olefin (0.1 mmol), and substrate silane (0.25 mmol) in sequence. The reaction tube was sealed and removed from the glove box. Irradiation was then performed at room temperature using a blue LED lamp for 12 h with stirring. The yield was determined by1H NMR to be 36%. 19 F NMR (565 MHz, CDCl3,25

[0063] 1 H NMR (600 MHz, CDCl3,25 o C) δ 7.39–7.30 (m, 4H), 7.23 (d, J = 6.7 Hz,1H), 1.73–1.67 (m, 2H), 0.03 (s, 18H), -0.06 (s, 3H). 13 C NMR (151 MHz, CDCl3,25 o C): δ 152.9 (dd, J = 288.3, 284.5 Hz), 135.4–135.2 (m), 128.5–128.4 (m),128.3, 89.3 (dd, J = 23.3, 14.4 Hz), 18.3, 1.8, 0.1. 19 F NMR (565 MHz, CDCl3,25 o C): δ -91.22 (d, J = 47.5 Hz, 1F), -93.92 (d, J = 47.7 Hz, 1F). Example 18

[0064] In an argon-filled glove box, a dry screw-cap vial equipped with a magnetic stir bar was charged with acrylquinolinium D (0.01 mmol), bis[2-(2,4-difluorophenyl)-5- methylpyridine][2-phenylpyridyl]iridium bis(hexafluorophosphate) (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethylalkene (0.1 mmol), and substrate silane (0.25 mmol). The vial was sealed and removed from the glove box. Irradiation was then performed at room temperature using a blue LED lamp for 12 h with stirring. The yield was determined by1H NMR to be 62%. 19 F NMR (565 MHz, CDCl3,25

[0065] 1 H NMR (600 MHz, CDCl3,25 o C)δ 7.39–7.30 (m, 4H), 7.23 (d, J = 6.7 Hz,1H), 1.73–1.67 (m, 2H), 0.03 (s, 18H), -0.06 (s, 3H). 13 C NMR (151 MHz, CDCl3,25 o C): δ 152.9 (dd, J = 288.3, 284.5 Hz), 135.4–135.2 (m), 128.5–128.4 (m),128.3, 89.3 (dd, J = 23.3, 14.4 Hz), 18.3, 1.8, 0.1. 19 F NMR (565 MHz, CDCl3,25 o C):δ -91.22 (d, J = 47.5 Hz, 1F), -93.92 (d, J = 47.7 Hz, 1F). Example 19

[0066] In an argon-filled glove box, a dry screw-cap vial equipped with a magnetic stir bar was charged with acrylquinolinium D (0.01 mmol), bis[2-(2,4-difluorophenyl)-5- methylpyridine][2-phenylpyridyl]iridium bis(hexafluorophosphate) (0.0015 mmol), acetonitrile (1.0 mL), trifluoromethylalkene (0.1 mmol), and substrate silane (0.25 mmol). The vial was sealed and removed from the glove box. Irradiation was then performed at room temperature using a blue LED lamp for 12 h with stirring. The yield was determined by1H NMR to be 62%. 19 F NMR (565 MHz, CDCl3,25

[0067] 1 H NMR (600 MHz, CDCl3,25 o C)δ 7.39–7.30 (m, 4H), 7.23 (d, J = 6.7 Hz,1H), 1.73–1.67 (m, 2H), 0.03 (s, 18H), -0.06 (s, 3H). 13 C NMR (151 MHz, CDCl3,25 o C): δ 152.9 (dd, J = 288.3, 284.5 Hz), 135.4–135.2 (m), 128.5–128.4 (m),128.3, 89.3 (dd, J = 23.3, 14.4 Hz), 18.3, 1.8, 0.1. 19 F NMR (565 MHz, CDCl3,25 o C):δ -91.22 (d, J = 47.5 Hz, 1F), -93.92 (d, J = 47.7 Hz, 1F). Application Example 1 The polyorganosiloxane polymer prepared in Example 17 was added to a 20 mL reaction bottle, cyclohexane was added as a solvent, then an aqueous sodium hydroxide solution was added, and the reaction was carried out at 60°C to obtain a polyorganosiloxane polymer having a molecular weight of 15,000. The polyorganosiloxane polymer prepared in Example 17 was added to a 20 mL reaction bottle, cyclohexane was added as a solvent, then an aqueous sodium hydroxide solution was added, and the reaction was carried out at 60°C to obtain a polyorganosiloxane polymer having a molecular weight of 15,000.

[0068] The above only describes the preferred embodiments of the present application, and does not limit the embodiments and protection scope of the present application. Those skilled in the art should be able to realize that any equivalent replacement and obvious changes made according to the content of the present application should be included in the protection scope of the present application.

Claims

1. A method for producing a co-difluoroolefin-functionalized siloxane compound, characterized by, The method comprises the following steps: The trifluoromethyl olefin A, silane compound B, photocatalyst C, hydrogenation reagent D and organic solvent E are mixed, stirred at room temperature under inert atmosphere, and reacted under visible light irradiation, and the target product is obtained after separation and purification. In the formula, the structure of the trifluoromethyl olefin A is ; The structural formula of the silane compound B is ; The structural formula of the difluoroalkene-functionalized siloxane compound is, ; wherein R 1 is aryl.

2. The method for producing a difluoroolefin-functional siloxane compound according to claim 1, characterized by, The aryl group is any one of phenyl, naphthyl, anthryl, chrysenyl, perylenyl, benzopyrenyl, indolyl, quinolyl and dibenzofuranyl, and has one or more substituents, which are the same or different when there are multiple substituents.

3. The method for producing a difluoroolefin-functional siloxane compound according to claim 2, characterized by, The substituent is at least one of C1-C20 alkyl, halogen atom, C1-C20 alkoxy, hydroxyl and amino.

4. The method for producing a bifluoroolefin-functional siloxane compound according to claim 1, characterized by, The photocatalyst C is any one of tris[2-phenylpyridine-C2,N]iridium(III), rhodamine 6G, rhodamine B, 2,4,5,6-tetra(9-carbazolyl)-1,3-dicyanobenzene, solvent red 43, erythrosin B, solvent red 49, solvent red 24 and fluorescein.

5. The method of producing a difluoroolefin-functional siloxane compound according to claim 1, characterized by: The hydrogenation reagent D is at least one of quinine compounds.

6. The method of preparing a bifluoroolefin-functional siloxane compound according to claim 1, characterized by: The organic solvent E is at least one of dichloromethane, 1,4-dioxane, methyl tert-butyl ether, acetonitrile, toluene, chlorobenzene, chloroform, cyclopentane, n-pentane, n-hexane, cyclohexane, 1,2-dichloroethane and acetone.

7. The method of producing a difluoroolefin-functional siloxane compound according to claim 1, characterized by: The visible light is blue light or visible light containing blue light.

8. The method for producing a difluoroolefin-functional siloxane compound according to claim 1, characterized by, The molar ratio of the trifluoromethyl olefin A to the silane compound B is 1:1-6, the amount of the photocatalyst C is 0.01%-1% of the molar amount of the silane compound B, the concentration of the silane compound B in the mixed solution is 0.1 M-2 M, and the amount of the hydrogenation reagent D is 1%-20% of the molar amount of the silane compound B.

9. A gem-difluoroalkene-functionalized siloxane compound characterized in that, The method is prepared by any one of claims 1-8.

10. Use of a gem-difluoro olefin functionalized siloxane compound characterized in that: The gem-difluoro olefin functional siloxane compound is applied to synthesis of a polysiloxane precursor.

Images