A kind of alkyl perfluoroalkyl ketone compound and preparation method thereof

Abstract

The present invention provides an alkyl perfluoroalkyl ketone compound and a preparation method thereof, which belongs to the technical field of chemical synthesis. The preparation method comprises: compound a and compound b react in the presence of a photosensitizer and silane under an inert gas atmosphere in a solvent under light irradiation to obtain compound c. The preparation method has the advantages of being green and environmentally friendly, high yield, mild reaction conditions, high selectivity, etc.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to an alkyl perfluoroalkyl trifluoromethyl ketone compound and a preparation method thereof. Background Art

[0002] Ketone is one of the most important functional groups in organic chemistry. It is particularly important to construct ketone compounds directly, efficiently, atom-economically and environmentally friendly. Among the numerous ketone compounds, alkyl trifluoromethyl ketones have significantly improved the lipophilicity and membrane permeability of such compounds due to the introduction of fluorine atoms, thus having high biological activity. Therefore, alkyl trifluoromethyl ketone compounds have a wide range of applications in the fields of biomedicine and materials chemistry (T.absoluta, A.Dominguez, M.Puigmart, MPBosch, G.Rosell, R.Crehuet, A.Ortiz, C.Quero, A.Guerrero, J.Agric.Food Chem., 2016, 64, 3523-3532). The construction of traditional trialkyl fluoromethyl ketone compounds mainly relies on the oxidation of alkyl trifluoromethyl alcohol compounds (M. Mertens, P. Wessig, F. Meyer-Almes, Chem. Eur. J., 2017, 23, 3107-3116.), and nucleophilic substitution of ketone compounds (CB Kelly, M. A Mercadantea, N. E. Leadbeater, Chem. Commun., 2013, 49, 11133-11148.), and the harsh reaction conditions and expensive trifluoromethylation reagents greatly hinder the construction of such compounds. In recent years, the efficient construction of alkyl trifluoromethyl ketone compounds through free radical pathways has gradually become a hot topic of concern, but the current research is not mature enough and needs further improvement and breakthroughs.

[0003] Therefore, there is an urgent need for a green, environmentally friendly, high-yield method for preparing alkyl perfluoroalkyl ketone compounds. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides an alkyl perfluoroalkyl ketone compound and a preparation method thereof.

[0005] In one aspect, the present invention provides a method for preparing compound C, comprising:

[0006]

[0007] Compound a and compound b react in the presence of a photosensitizer and silane in an inert gas atmosphere in a solvent under light irradiation to obtain compound c.

[0008] in,

[0009] R is selected from substituted or unsubstituted C 1- C 30 Alkyl, substituted or unsubstituted C1-C 30 Heteroalkyl, substituted or unsubstituted C1-C 30 Cycloheteroalkyl;

[0010] Rf is selected from the group consisting of perfluorinated C1-C 10 alkyl;

[0011] X is selected from a chlorine atom, a bromine atom or an iodine atom, and is preferably a bromine atom.

[0012] In some embodiments, the alkyl group is a hydrocarbon containing normal carbon atoms, secondary carbon atoms, tertiary carbon atoms, or cyclic carbon atoms.

[0013] In some embodiments, the C 1- C 30 The alkyl group is C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C 10 Alkyl, C 11 Alkyl, C 12 Alkyl, C 13 Alkyl, C 14 Alkyl, C 15 Alkyl, C 16 Alkyl, C 17 Alkyl, C 18 Alkyl, C 19 Alkyl, C 20 Alkyl, C 21 Alkyl, C 22 Alkyl, C 23 Alkyl, C 24 Alkyl, C 25 Alkyl, C 26 Alkyl, C 27 Alkyl, C 28 Alkyl, C 29 Alkyl or C 30 alkyl.

[0014] In some embodiments, the C 1- C 10 The alkyl group is C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl or C 10 alkyl.

[0015] In some embodiments, the C 1- C 10The alkyl group is methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (i-Pr, i-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(CH3)CH2CH H3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH2CH 2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH(CH 3)CH2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3 and octyl (-(CH2)7CH3).

[0016] In some embodiments, the substituted or unsubstituted C1-C 30 The heteroalkyl group in the heteroalkyl group means that one or more carbon atoms in a linear or branched saturated hydrocarbon group are independently substituted by one or more heteroatoms, and the one or more heteroatoms are independently selected from nitrogen atoms, oxygen atoms, phosphorus atoms and sulfur atoms.

[0017] In some embodiments, the substituted or unsubstituted C 1- C 30 The cycloheteroalkyl group in the cycloheteroalkyl group represents a saturated cyclic hydrocarbon group in which one or more carbon atoms are independently substituted by one or more heteroatoms, and the one or more heteroatoms are independently selected from nitrogen atoms, oxygen atoms, phosphorus atoms and sulfur atoms.

[0018] In some embodiments, the perfluorinated C1-C 10 The alkyl group is selected from trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, undecafluoropentyl, tridecafluorohexyl, pentafluoroheptyl, heptadecafluorooctyl, nonadecafluorononyl, heneicosaefluorodecyl.

[0019] In some embodiments, the substituted or unsubstituted C 1- C 30 Alkyl groups include unsubstituted straight chain C 1- C 30 Alkyl, unsubstituted cyclic C 1- C 30 Alkyl, unsubstituted branched C 1- C 30 Alkyl, aryl substituted straight chain C 1- C 30 Alkyl, aryl substituted branched C 1- C 30 Alkyl, ester substituted straight chain C 1- C 30 Alkyl, ester substituted branched C 1- C 30 Alkyl, heteroatom substituted straight chain C 1- C 30 Alkyl, heteroatom substituted branched C 1- C 30 Alkyl, heteroatom substituted cyclic C 1- C 30 Alkyl, halogen substituted straight chain C 1- C 30 Alkyl, halogen substituted branched C 1- C 30 Alkyl, halogen substituted cyclic C 1- C 30 alkyl.

[0020] In some embodiments, the aryl group may have 6 to 20 carbon atoms (e.g., C6 aryl, C7 aryl, C8 aryl, C9 aryl, C 10 Aryl, C 11 Aryl, C 12 Aryl, C 13 Aryl, C 14 Aryl, C 15 Aryl, C 16 Aryl, C 17 Aryl, C 18 Aryl, C 19 Aryl or C 20 In some embodiments, the aryl group includes phenyl, substituted phenyl, naphthyl, anthracenyl, biphenyl and the like, or similar groups.

[0021] In some embodiments, the halogen is selected from a fluorine atom, a chlorine atom, and a bromine atom.

[0022] In some embodiments, the substitution in the "substituted or unsubstituted" independently indicates that one or more hydrogen atoms on the group are replaced by a substituent selected from the group consisting of an ester group, a benzoyl group, a tert-butyloxycarbonyl group, =O, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a C1-C10 alkyl group, a C3-C10 cycloalkyl group, a C1-C10 heteroalkyl group, a C3-C10 cycloheteroalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C6-C10 aryl group or a C6-C10 heteroaryl group,

[0023] wherein R1, R2, R3, and R4 are independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a methyl group, or an ethyl group.

[0024] In some embodiments, the cycloalkyl group represents a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing 3-20 carbon atoms. In one embodiment, the cycloalkyl group contains 3-20 carbon atoms. In one embodiment, the cycloalkyl group contains 3-12 carbon atoms. In another embodiment, the cycloalkyl group contains 3-8 carbon atoms; in yet another embodiment, the cycloalkyl group contains 3-6 carbon atoms. The cycloalkyl group may be independently unsubstituted or substituted with one or more substituents described herein.

[0025] In some embodiments, the alkenyl group comprises at least one unsaturated site, i.e., a carbon-carbon sp 2 In some embodiments, the alkenyl group may have 2 to 10 carbon atoms (C2-C 10 alkenyl), 2 to 12 carbon atoms (C2-C 12 In some embodiments, the alkenyl group includes ethylene or vinyl (-CH=CH2), allyl (-CH2CH=CH2), cyclopentenyl (-C5H7) or 5-hexenyl (-CH2CH2CH2CH2CH=CH2).

[0026] In some embodiments, the alkynyl group is a hydrocarbon containing a positive carbon atom, a secondary carbon atom, a tertiary carbon atom, or a ring carbon atom having at least one unsaturated site, i.e., a carbon-carbon sp triple bond. In some embodiments, the alkynyl group may have 2 to 10 carbon atoms (C2-C 10 Alkynyl), 2 to 12 carbon atoms (C2-C 12In some embodiments, the alkynyl group includes ethynyl (-C=CH), propargyl (-CH2C=CH) or the like.

[0027] In some embodiments, the aryl group is an aromatic hydrocarbon group derived by removing a hydrogen atom from a single carbon atom of a parent aromatic ring system. In some embodiments, the aryl group may have 6 to 20 carbon atoms, 6 to 14 carbon atoms, or 6 to 10 carbon atoms. In some embodiments, the aryl group includes phenyl, naphthalene, anthracene, biphenyl, substituted benzene, or a group derived therefrom, or a similar group.

[0028] In some embodiments, the heteroaryl group refers to an aromatic heterocyclic group having at least one heteroatom in the ring, that is, an aromatic heterocyclic group obtained by replacing at least one ring carbon atom in the aromatic group with at least one heteroatom. In some embodiments, the heteroatom in the heteroaryl group can be an oxygen atom, a sulfur atom or a nitrogen atom. In some embodiments, the heteroaryl group includes any of the following groups: indolyl, isoindolyl, 1,3-dioxoisoindolyl, purinyl, benzofuranyl, benzothienyl, carbazolyl, quinolyl, isoquinolyl, pyridazinyl or pyrimidinyl, etc.

[0029] In some embodiments, the compound a is selected from the following structures of compound 1-a to compound 47-a:

[0030]

[0031]

[0032] In some embodiments, the compound b is selected from the following structures of compound 1-b, compound 2-b, and compound 3-b:

[0033]

[0034] In some embodiments, the compound c is selected from the following structures of compound 1-compound 47:

[0035]

[0036]

[0037] In some embodiments, the photosensitizer is selected from at least one of an iridium photosensitizer, a ruthenium photosensitizer, or an organic photosensitizer.

[0038] In some embodiments, the iridium photosensitizer includes [Ir(dF(Me)ppy2)(dtbbpy)]PF, [Ir(dF(CF3)(ppy)2(dtbbpy)]PF6, [Ir(pF(CF3)ppy)2(bpy)]PF6, [Ir(ppy)2(bpy)]PF6, [Ir(p-CF3-ppy)2(bpy)]PF6, [Ir(dtbppy)2(dtbbpy)]PF6,

[0039] [Ir(m-CF3(CF3)ppy)2bpy]PF6, [Ir(ppyCF3)2bpy]PF6, fac-Ir(ppy)3, [Ir(dmppy)2(dtbbpy)]PF6,

[0040] [Ir(ppy)2(dtbbpy)]PF6 or [Ir(dF(CF3)ppy)2bpy]PF6, [Ir(dF(CF3)(ppy)2(5,5'-dCF3bpy)]PF6,

[0041] At least one of [Ir(dF(CF3)(ppy)2(4,4'-dCF3bpy)]PF6.

[0042] In some preferred embodiments, the iridium photosensitizer includes [Ir(dF(Me)ppy2)(dtbbpy)]PF6,

[0043]

[0044] In some embodiments, the ruthenium-based photosensitizer includes at least one of [Ru(bpy)3](PF6) or [Ru(bpz)3](PF6).

[0045] In some preferred embodiments, the ruthenium photosensitizer includes Ru(bpy)3(PF6)2,

[0046]

[0047] In some embodiments, the organic photosensitizer includes at least one of EosinY, 4-CzIPN, 4CzPN, 3DPA2FBN, or 3DPAIFPN.

[0048] In some preferred embodiments, the organic photosensitizer includes 3DPAIFPN,

[0049]

[0050] In some embodiments, the silane includes at least one of triphenylsilane (Ph3SiH), tris(trimethylsilyl)silane ((TMS)3SiH), diphenylsilane (Ph2SiH2), phenyldimethylsilane (PhMe2SiH), trimethoxysilane ((MeO)3SiH), triethoxysilane ((EtO)3SiH), diethoxymethylsilane ((MeO)2MeSiH). In some preferred embodiments, the silane includes triphenylsilane (Ph3SiH).

[0051] In some embodiments, the inert gas includes at least one of nitrogen, helium, neon, and argon.

[0052] In some embodiments, the solvent includes at least one of methyl tert-butyl ether (MTBE), dimethyl sulfoxide (DMSO), acetonitrile (CH3CN), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-Me-THF), ethylene glycol dimethyl ether (DME), 1,4-dioxane (1,4-dioxane), ether (Et2O), dichloromethane (DCM), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), and toluene (Toluene). In some preferred embodiments, the solvent is at least one of methyl tert-butyl ether (MTBE) or 1,4-dioxane (1,4-dioxane). In some more preferred embodiments, the solvent is methyl tert-butyl ether (MTBE).

[0053] In some embodiments, the illumination is blue light.

[0054] In some embodiments, the wavelength of the blue light is 400 nm to 480 nm. In some embodiments, the wavelength of the blue light is 440 nm.

[0055] In some embodiments, the molar ratio of compound b to compound a is 1.0:1.0-15.0:1.0. In some embodiments, the molar ratio of compound b to compound a is 1.0:1.0-10.0:1.0. In some embodiments, the molar ratio of compound b to compound a is 1.0:1.0-6.0:1.0. In some embodiments, the molar ratio of compound b to compound a is 1.0:1.0-

[0056] In some embodiments, the molar ratio of compound b to compound a is 1.0:1.0-4.0:1.0.

[0057] In some embodiments, the molar ratio of the silane to compound a is 1.0:1.0-20.0:1.00. In some preferred embodiments, the molar ratio of the silane to compound a is 2.0:1.0-10.0:1.0. In some preferred embodiments, the molar ratio of the silane to compound a is 2.0:1.0-8.0:1.0. In some more preferred embodiments, the molar ratio of the silane to compound a is 4.0:1.0.

[0058] In some embodiments, the molar ratio of the photosensitizer to compound a is 0.005:1.000-0.100:1.000. In some preferred embodiments, the molar ratio of the photosensitizer to compound a is 0.010:1.000-0.050:1.000. In some more preferred embodiments, the molar ratio of the photosensitizer to compound a is 0.020:1.000-0.040:1.000.

[0059] In some embodiments, the molar ratio of the pyridine reagent to compound a is 0.1:1.0-5.0:1.0. In some preferred embodiments, the molar ratio of the pyridine reagent to compound a is 0.5:1.0-3.0:1.0. In some more preferred embodiments, the molar ratio of the pyridine reagent to compound a is 1.0:1.0-2.0:1.0.

[0060] In some embodiments, the reaction temperature of the reaction is 10°C-40°C. In some embodiments, the reaction temperature of the reaction is 15°C-35°C. In some embodiments, the reaction temperature of the reaction is 20°C-30°C. In some embodiments, the reaction temperature of the reaction is 22°C-28°C. In some embodiments, the reaction temperature of the reaction is 24°C-26°C.

[0061] In some embodiments, the preparation method further comprises: compound a and compound b react under light irradiation in the presence of a photosensitizer, silane, a base and a pyridine reagent in an inert gas atmosphere in a solvent to obtain compound c.

[0062] In some embodiments, the base includes dipotassium hydrogen phosphate (K2HPO4), potassium dihydrogen phosphate (KH2PO4), tripotassium phosphate

[0063] In some preferred embodiments, the base comprises at least one of triethylenediamine (DABCO) or dipotassium hydrogen phosphate (K2HPO4). In some more preferred embodiments, the base is dipotassium hydrogen phosphate (K2HPO4).

[0064] In some embodiments, the pyridine reagent includes at least one of pyridine, 4-dimethylaminopyridine (DMAP), 2-methylpyridine, 2-bromopyridine, 2,6-dimethoxypyridine, 2,6-dimethylpyridine, 2,6-dichloropyridine, 2,6-diethoxypyridine, 2,6-dipropoxypyridine, 2,6-dicyclohexylpyridine, 2,4,6-trimethoxypyridine, 2,4,6-triethoxypyridine, and 2,6-dichloropyridine nitrogen oxide. In some preferred embodiments, the pyridine reagent is at least one of 2,6-di-n-propoxypyridine or 2,4,6-triethoxypyridine. In some preferred embodiments, the pyridine reagent is 2,6-di-n-propoxypyridine.

[0065] In some embodiments, the molar ratio of the base to compound a is 0.1:1.0-5.0:1.0, preferably 0.2:1.0-1.5:1.0, and more preferably 0.3:1.0-1.0:1.0.

[0066] In some embodiments, the compound c is any one of compound 1 to compound 44 and compound 47, the compound a corresponds to compound 1-a to compound 44-a and compound 47-a, respectively, and the compound b is compound 1-b.

[0067] In some embodiments, the compound c is compound 45, the compound a is compound 45-a, and the compound b is compound 2-b.

[0068] In some embodiments, the compound c is compound 46, the compound a is compound 46-a, and the compound b is compound 3-b.

[0069] In another aspect, the present invention provides a compound selected from the structures of the following compounds 1 to 47:

[0070]

[0071]

[0072] Beneficial Effects

[0073] Compared with the prior art, an embodiment of the present invention has at least one of the following beneficial effects:

[0074] (1) The use of the photosensitizer and silane provided by the present invention, especially the preferred photosensitizer and silane of the present invention, is conducive to the smooth conversion of primary, secondary and tertiary alkyl bromides into alkyl trifluoromethyl ketone compounds under mild conditions, while overcoming the shortcomings of the prior art such as harsh reaction conditions, poor selectivity and limited raw material sources.

[0075] (2) The use of the photosensitizer and silane provided by the present invention, especially the preferred photosensitizer and silane of the present invention, is beneficial to greatly promote and accelerate the occurrence of the reaction and improve the yield of the product.

[0076] (3) In the reaction provided by the present invention, the photosensitizer can be an iridium photosensitizer, a ruthenium photosensitizer or an organic photosensitizer; among which the iridium photosensitizer is preferably [Ir(dF(Me)ppy2)(dtbbpy)]PF6; the ruthenium photosensitizer is preferably Ru(bpy)3(PF6)2; the organic photosensitizer is preferably 3DPAIFPN; among all the photosensitizers, [Ir(dF(Me)ppy2)(dtbbpy)]PF6 is the most preferred, which is beneficial to improving the product yield.

[0077] (4) In the reaction provided by the present invention, the silane is preferably triphenylsilane or diphenylsilane, and more preferably triphenylsilane, which is beneficial to improving the product yield.

[0078] (5) In the reaction provided by the present invention, the molar ratio of the silane to the compound a is preferably 0.0:1.0-20.0:1.00, which is conducive to improving the yield of the product. The molar ratio of the silane to the compound a is more preferably 4.0:1, which is more conducive to improving the yield of the product.

[0079] (6) The use of the base provided by the present invention is beneficial to improving the yield of the product, wherein the base is preferably at least one of dipotassium hydrogen phosphate or triethylenediamine; more preferably dipotassium hydrogen phosphate.

[0080] (7) The molar ratio of the base to compound a of the present invention is preferably 0.1:1.0-5.0:1.0, which is conducive to improving the yield of the product. The molar ratio of the base to compound a is more preferably 0.3:1, which is more conducive to improving the yield of the product.

[0081] (8) The pyridine reagent provided by the present invention is used, and the pyridine reagent is preferably at least one of 2,6-di-n-propoxypyridine, 2,4,6-triethoxypyridine, 2,6-dichloropyridine-1-oxide, 2,6-dimethoxypyridine, 2,4,6-trimethoxypyridine, 2,6-diisopropoxypyridine, and 2,4,6-trimethylpyridine, more preferably at least one of 2,6-di-n-propoxypyridine, 2,6-dichloropyridine-1-oxide, and 2,6-dimethoxypyridine, and most preferably 2,6-di-n-propoxypyridine, which is beneficial to improving the product yield. .

[0082] (9) In the reaction provided by the present invention, the molar ratio of pyridine to compound a is preferably 0.1:1.0-5.0:1.0, which is conducive to improving the yield of the product. The molar ratio of the base to compound a is more preferably 1.0:1, which is more conducive to improving the yield of the product.

[0083] (10) In the reaction provided by the present invention, the solvent is preferably MTBE, THF or 1,4-dioxane, more preferably MTBE, which is beneficial to improving the product yield.

[0084] (11) The photosensitizer, silane and light provided by the present invention are necessary conditions for the reaction. Without any one of the conditions, the reaction cannot proceed. In addition, in addition to the photosensitizer, silane and light, adding pyridine and a base to the reaction is more conducive to improving the product yield. The photosensitizer, silane, pyridine, a base and light work together to promote the improvement of the product yield.

[0085] Terminology

[0086] Unless otherwise indicated, the following terms and phrases as used herein are intended to have the following meanings:

[0087] The term "plurality" means two or more, for example, 2, 3, 4 or 5.

[0088] In the present invention, expressions such as "compound a", "compound of formula a" and "compound represented by formula a" have the same meaning, and the same applies to other compounds.

[0089] In the present invention, "room temperature" refers to ambient temperature, which is from about 10°C to about 40°C. In some embodiments, "room temperature" refers to a temperature from about 15°C to about 35°C; in some embodiments, "room temperature" refers to a temperature from about 20°C to about 30°C; in some embodiments, "room temperature" refers to a temperature from about 20°C to about 35°C; in other embodiments, "room temperature" refers to a temperature from about 25°C to about 30°C; in other embodiments, "room temperature" refers to a temperature from about 22°C to about 28°C; in other embodiments, "room temperature" refers to a temperature from about 24°C to about 26°C; in yet other embodiments, "room temperature" refers to 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, etc.

[0090] The term "and / or" should be understood to mean any one of the optional items or a combination of any two or more of the optional items.

[0091] The term "optional" or "optionally" means that the subsequently described event or circumstance may but need not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not occur. For example, "optionally a condensing agent" means that a condensing agent may or may not be present.

[0092] The term "heteroatom" means an oxygen atom, a nitrogen atom or a sulfur atom.

[0093] The term "halogen" means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0094] In the above text of the present invention, regardless of whether the words "about" or "approximately" are used, all the numbers disclosed herein are approximate values. Based on the disclosed numbers, the value of each number may vary by less than ±10% or reasonable differences considered by those skilled in the art, such as ±1%, ±2%, ±3%, ±4% or ±5%.

[0095] The group "Ph" represents a phenyl group.

[0096] The group "Boc" represents tert-butyloxycarbonyl.

[0097] The group "Bz" represents a benzoyl group.

[0098] The group "Me" represents a methyl group.

[0099] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0100] The term "aryl" means an aromatic hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of a parent aromatic ring system.

[0101] The term "perfluorinated" means that all hydrogen atoms bonded to carbon atoms in the group are replaced by fluorine atoms.

[0102] In the present invention, "mmol" means millimole; "mol" means mole; "Kg" means kilogram; "g" means gram; "mg" means milligram; "eq" or "equiv" means equivalent; "L" means liter; "mL" means milliliter; "μl" means microliter; "℃" means degree Celsius; and "h" means hour. DETAILED DESCRIPTION

[0103] In order to enable those skilled in the art to better understand the technical solution of the present invention, some non-limiting embodiments are further disclosed below to further illustrate the present invention in detail.

[0104] The reagents used in the present invention can be purchased from the market or prepared by the method described in the present invention.

[0105] The Chinese meanings of the abbreviations or chemical formulas of the reagents used in the present invention are as follows:

[0106] Abbreviation or chemical formula Chinese meaning TFAA Trifluoroacetic anhydride DMSO Dimethyl sulfoxide <![CDATA[CH3CN]]> Acetonitrile THF Tetrahydrofuran 2-Me-THF 2-Methyltetrahydrofuran DME Ethylene glycol dimethyl ether 1,4-dioxane 1,4-Dioxane <![CDATA[Et2O]]> Ether DCM Dichloromethane DMF N,N-Dimethylformamide NMP N-Methylpyrrolidone Toluene Toluene DABCO N,N-Dimethylethanolamine MTBE Methyl tert-butyl ether

[0107] Abbreviations of reagents used in the present invention or structures or CAS numbers corresponding to chemical formulas:

[0108]

[0109]

[0110] Example 1: Screening of photosensitizers

[0111]

[0112] The photosensitizer (0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 1-a (26.4 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) as described in Table 1 were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, and irradiated with a 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added for dilution. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, phenyltrimethylsilane was added as an NMR internal standard, and the reaction yield was determined by NMR hydrogen spectrum. The results are shown in Table 1. Column chromatography separation and purification were performed to obtain compound 1 (colorless oily liquid). The conversion rate of compound 1-a and the yield of the product after separation and purification are shown in Table 1. An appropriate amount of the obtained compound 1 was taken for hydrogen spectrum and fluorine spectrum detection, and the results are as follows:

[0113] 1 H NMR (400MHz, Chloroform-d) δ4.16–4.11(m,2H),2.95(tt,J=11.2,3.7Hz,1H),2.84(t,J=12.9Hz,2H),1.92–1.87(m,2H),1.67–1.57(m,2H),1.46(s,9H).

[0114] 19 F NMR (376MHz, Chloroform-d) δ–77.30.

[0115] Table 1: Screening of photosensitizers

[0116]

[0117]

[0118] in conclusion:

[0119] (1) In the presence of a base, a pyridine reagent and a silane and under an inert gas atmosphere, the addition of a suitable photosensitizer can promote the reaction of compound 1-a and compound 1-b under light conditions to obtain compound 1;

[0120] (2) The photosensitizer that can be used in the present invention can be an iridium photosensitizer, a ruthenium photosensitizer or an organic photosensitizer; among which the iridium photosensitizer is preferably Ir[dF(Me)ppy]2(dtbbpy)PF6, Ir[dF(CF3)ppy]2(5,5'-dCF3bpy)PF6 or Ir[dF(CF3)ppy]2(4,4'-dCF3bpy)PF6; the ruthenium photosensitizer is preferably Ru(bpy)3(PF6)2; the organic photosensitizer is preferably 3DPAIFPN; among all the photosensitizers, Ir[dF(Me)ppy]2(dtbbpy)PF6 is the most preferred, which is most conducive to improving the product yield.

[0121] Example 2: Screening of silanes

[0122]

[0123] Ir[dF(Me)ppy]2(dtbbpy)PF6 (2.0 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 1-a (26.4 mg, 0.1 mmol, 1.0 equiv.) and silane (0.4 mmol, 4.0 equiv.) as shown in Table 2 were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, and irradiated with a 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, phenyltrimethylsilane was added as an NMR internal standard, and the reaction yield was determined by NMR hydrogen spectrum. The results are shown in Table 2. Column chromatography was used for separation and purification to obtain compound 1 (colorless oily liquid). The conversion rate of compound 1-a and the yield of the product after separation and purification are shown in Table 2. An appropriate amount of the obtained compound 1 was taken for hydrogen spectrum and fluorine spectrum detection, and the results were the same as those in Example 1.

[0124] Table 2: Screening of silanes

[0125]

[0126] in conclusion:

[0127] (1) In the presence of a photosensitizer, a base and a pyridine reagent under an inert gas atmosphere, adding a suitable silane compound can promote the reaction of compound 1-a and compound 1-b under light conditions to obtain compound 1;

[0128] (2) The silane complex of the present invention is preferably Ph3SiH, Ph2SiH2, PhMe2SiH, and more preferably Ph3SiH, which is beneficial to improving the product yield.

[0129] Example 3: Screening of bases

[0130]

[0131] Ir[dF(Me)ppy]2(dtbbpy)PF6 (2.0 mg, 0.002 mmol, 0.02 equiv.), a base as shown in Table 3 (0.03 mmol, 0.3 equiv.), compound 1-a (26.4 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, and irradiated with a 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, phenyltrimethylsilane was added as an NMR internal standard, and the reaction yield was determined by NMR hydrogen spectrum. The results are shown in Table 3. Column chromatography was used for separation and purification to obtain compound 1 (colorless oily liquid). The conversion rate of compound 1-a and the yield of the product after separation and purification are shown in Table 3. An appropriate amount of the obtained compound 1 was taken for hydrogen spectrum and fluorine spectrum detection, and the results were the same as those in Example 1.

[0132] Table 3: Screening of bases

[0133]

[0134] Conclusion: In the preparation method of compound 1, adding a suitable base is beneficial to improving the product yield compared to not adding a base. The base is preferably K2HPO4, KOAc or DABCO, and more preferably K2HPO4.

[0135] Example 4: Screening of solvents

[0136]

[0137] Ir[dF(Me)ppy]2(dtbbpy)PF6 (2.0 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 1-a (26.4 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, and 0.3 mL of the solvent shown in Table 4, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, and irradiated with a 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, phenyltrimethylsilane was added as an NMR internal standard, and the reaction yield was determined by NMR hydrogen spectrum. The results are shown in Table 4. Column chromatography was used for separation and purification to obtain compound 1 (colorless oily liquid). The conversion rate of compound 1-a and the yield of the product after separation and purification are shown in Table 4. An appropriate amount of the obtained compound 1 was taken for hydrogen spectrum and fluorine spectrum detection, and the results were the same as those in Example 1.

[0138] Table 4: Screening of solvents

[0139]

[0140] Conclusion: The solvent is preferably MTBE, THF or 1,4-dioxane, more preferably MTBE, which is beneficial to improve the product yield.

[0141] Example 5: Screening of pyridine reagents

[0142]

[0143] Ir[dF(Me)ppy]2(dtbbpy)PF6 (2.0 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 1-a (26.4 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, pyridine reagents (0.1 mmol, 1 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, and irradiated with a 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). Then the organic phases were combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, phenyltrimethylsilane was added as an NMR internal standard, and the reaction yield was determined by NMR hydrogen spectrum. The yield results (i.e., yield in Table 5) are shown in Table 5. Column chromatography was used for separation and purification to obtain compound 1 (colorless oily liquid). The conversion rate of compound 1-a (i.e., conv.of 1-a in Table 5) is shown in Table 5. An appropriate amount of the obtained compound 1 was taken for hydrogen spectrum and fluorine spectrum detection, and the results were the same as those in Example 1.

[0144] Table 5: Screening of pyridine reagents

[0145]

[0146] Conclusion: In the preparation process of compound 1, the pyridine reagent is preferably at least one of 2,6-di-n-propoxypyridine, 2,4,6-triethoxypyridine, 2,6-dichloropyridine-1-oxide, 2,6-dimethoxypyridine, 2,4,6-trimethoxypyridine, 2,6-diisopropoxypyridine, 2,4,6-trimethylpyridine, etc., more preferably at least one of 2,6-di-n-propoxypyridine, 2,6-dichloropyridine-1-oxide, 2,6-dimethoxypyridine, etc., most preferably 2,6-di-n-propoxypyridine, which is beneficial to improve the product yield.

[0147] Example 6: Control Experiment

[0148]

[0149] The photosensitizer (0.002mmol, 0.02equiv.) shown in Table 6, the silane (0.4mmol, 4.0equiv) shown in Table 6, the base (0.03mmol, 0.3equiv) shown in Table 6, and the pyridine reagent (0.1mmol, 1.0equiv) shown in Table 6 were mixed, and 0.3mL of methyl tert-butyl ether, compound 1-a (26.4mg, 0.1mmol, 1.0equiv) and compound 1-b (84.0mg, 0.40mmol, 4.0equiv) were added under nitrogen atmosphere, respectively, and experiments 1 to 4 and 6 in Table 6 were irradiated with a 30W blue light lamp for 12 hours at room temperature, and experiment 5 in Table 6 was placed in the dark for 12 hours, and then 5mL of saturated sodium bicarbonate aqueous solution and 5mL of ethyl acetate were added for dilution. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, phenyltrimethylsilane was added as an NMR internal standard, and the reaction yield was determined by NMR hydrogen spectrum. The yield results are shown in Table 6. Column chromatography was used for separation and purification to obtain compound 1 (colorless oily liquid). An appropriate amount of the obtained compound 1 was taken for hydrogen spectrum and fluorine spectrum detection, and the results were the same as those in Example 1.

[0150] Table 6: Reagents for control experiments

[0151]

[0152] Conclusion: Photosensitizer, silane and light are necessary conditions for the reaction. If any one of the conditions is missing, the reaction cannot proceed. In addition, if a high-yield product is to be obtained, adding pyridine and base to the reaction in addition to photosensitizer, silane and light will be more conducive to improving the product yield. Photosensitizer, silane, pyridine, base and light work synergistically with each other to promote the improvement of product yield.

[0153] Example 7: Preparation of Compound 2

[0154]

[0155] Ir[dF(Me)ppy]2(dtbbpy)PF6 (2.0 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 2-a (26.7 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, and irradiated with a 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 63% by nuclear magnetic hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 2 (colorless oily liquid) with a yield of 57%. An appropriate amount of the obtained compound 2 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 H NMR (400MHz, Chloroform-d) δ7.45–7.36(m,5H),4.68(brs,1H),3.86(brs,1H),3.15–2.99(m,3H),1.74(brs,2H).

[0156] 13 C NMR (101MHz, Chloroform-d) δ192.7 (q, J = 34.0Hz), 170.7, 135.7, 130.1, 128.8, 127.0, 115.8 (q, J = 291.1Hz), 43.2, 29.9, 27.1.

[0157] 19 F NMR (376MHz, Chloroform-d) δ–77.26.

[0158] Example 8: Preparation of Compound 4

[0159]

[0160] Ir[dF(Me)ppy]2(dtbbpy)PF6 (2.0 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 4-a (24.6 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, and irradiated with a 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 70% by nuclear magnetic hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 4 (colorless oily liquid) with a yield of 61%. An appropriate amount of the obtained compound 4 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 H NMR (400MHz, Chloroform-d) δ3.06 (p, J = 6.1Hz, 1H), 1.76–1.56 (m, 4H), 1.44–1.29 (m, 18H). 13 C NMR(101MHz,Chloroform-d)δ195.4(q,J=33.0Hz),116.0(q,J=291.6Hz),42.4,25.8,23.7,25.6,23.5,23.4,22.4

[0161] 19 F NMR (376MHz, Chloroform-d) delta -77.98.

[0162] Example 9: Preparation of Compound 6

[0163]

[0164] Ir[dF(Me)ppy]2(dtbbpy)PF6 (2.0 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 6-a (19.8 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, and irradiated with a 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 81% by nuclear magnetic hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 6 (colorless oily liquid) with a yield of 76%. An appropriate amount of the obtained compound 6 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 H NMR(400MHz,Chloroform-d)δ7.43–7.31(m,4H),7.27–7.23(m,1H),3.37(h,J=7.5Hz, 1H), 3.21 (dd, J=13.7, 6.4Hz, 1H), 2.75 (dd, J=13.7, 7.9Hz, 1H), 1.30 (d, J=6.9Hz, 3H).

[0165] 13 C NMR (151MHz, Chloroform-d) δ194.9 (q, J = 34.0Hz), 138.1, 129.2, 128.8, 127.0, 115.8 (q, J = 293.2Hz), 43.0, 38.3, 16.0.

[0166] 19 F NMR(376MHz,Chloroform-d)δ-77.98.

[0167] Example 10: Preparation of Compound 7

[0168]

[0169] Ir[dF(Me)ppy]2(dtbbpy)PF6 (2.0 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 7-a (26.9 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, irradiated with 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phases were then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 45% by nuclear magnetic hydrogen spectrum. Column chromatography was performed for separation and purification to obtain compound 7 (colorless oily liquid) with a yield of 37%. An appropriate amount of the obtained compound 7 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 H NMR(400MHz,Chloroform-d)δ7.50(d,J=8.0Hz,2H),7.35–7.29(m,2H),7.1893–7.0539(m,2H),3.0 2(h,J=6.7Hz,1H),2.44–2.30(m,2H),1.90–1.74(m,2H),1.70–1.60(m,2H),1.24(d,J=7.0Hz,3H).

[0170] 13 C NMR (101MHz, Chloroform-d) δ 195.3 (q, J = 33.5Hz), 170.3, 137.8, 129.2, 124.5, 119.9, 116.0 (q, J = 293.2Hz), 40.9, 37.3, 31.8, 22.8, 16.3.

[0171] 19 F NMR (376MHz, Chloroform-d) δ-77.85.

[0172] Example 11: Preparation of Compound 8

[0173]

[0174] Ir[dF(Me)ppy]2(dtbbpy)PF6 (2.0 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 8-a (29.5 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, irradiated with 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phases were then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 85% by nuclear magnetic hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 8 (colorless oily liquid) with a yield of 77%. An appropriate amount of the obtained compound 8 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 H NMR(400MHz,Chloroform-d)δ7.85(dd,J=5.4,3.1Hz,2H),7.72(dd,J=5.5,3.1Hz,2H),3.69(t,J=7.0Hz,2 H),3.03(h,J=6.9Hz,1H),1.89–1.77(m,1H),1.73–1.64(m,2H),1.55–1.44(m,1H),1.21(d,J=6.9Hz,3H).

[0175] 13 C NMR (101MHz, Chloroform-d) δ195.0 (q, J = 33.5Hz), 168.5, 134.2, 132.2, 123.4, 115.8 (q, J = 291.3Hz), 40.5, 37.5, 29.4, 26.1, 16.3.

[0176] 19 F NMR (376MHz, Chloroform-d) δ-78.00.

[0177] Example 12: Preparation of Compound 9

[0178]

[0179] Ir[dF(Me)ppy]2(dtbbpy)PF6 (2.0 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 9-a (32.0 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, irradiated with 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phases were then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 88% by nuclear magnetic hydrogen spectrum. Column chromatography was performed for separation and purification to obtain compound 9 (colorless oily liquid) with a yield of 78%. An appropriate amount of the obtained compound 9 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 H NMR(400MHz,Chloroform-d)δ7.93–7.88(m,2H),7.69–7.63(m,1H),7.59–7.53(m,2H),4.04(t,J =6.3Hz,2H),2.91(h,J=6.8Hz,1H),1.75–1.62(m,3H),1.44–1.24(m,3H),1.17(d,J=6.9Hz,3H).

[0180] 13 C NMR (101MHz, Chloroform-d) δ 195.1 (q, J = 33.3Hz), 136.2, 133.9, 129.4, 128.0, 115.8 (q, J = 291.3Hz), 70.3, 40.8, 31.6, 28.8, 23.0, 16.2.

[0181] 19 F NMR (376MHz, Chloroform-d) delta -77.99.

[0182] Example 13: Preparation of Compound 10

[0183]

[0184] Ir[dF(Me)ppy]2(dtbbpy)PF6 (2.0 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 10-a (33.8 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, irradiated with 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 75% by nuclear magnetic hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 10 (colorless oily liquid) with a yield of 63%. An appropriate amount of the obtained compound 10 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 H NMR(400MHz,Chloroform-d)δ7.96–7.89(m,2H),7.28–7.21(m,3H),4.04(t,J=6.2Hz,2 H), 2.93 (h, J = 6.9 Hz, 1H), 1.79–1.62 (m, 3H), 1.47–1.24 (m, 3H), 1.19 (d, J = 6.9 Hz, 3H).

[0185] 13 C NMR(101MHz,Chloroform-d)δ195.1(q,J=33.4Hz),165.9(d,J=255.2Hz),132.3(d,J=33.8Hz),13 0.8(d,J=94.4Hz), 116.8(d,J=22.5Hz), 115.8(q,J=291.3Hz), 70.4, 40.8, 31.7, 28.8, 23.0, 16.2.

[0186] 19 F NMR (376MHz, Chloroform-d) δ -78.02, -103.07.

[0187] Example 14: Preparation of Compound 12

[0188]

[0189] Ir[dF(Me)ppy]2(dtbbpy)PF6 (2.0 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 12-a (28.4 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, irradiated with 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 58% by nuclear magnetic hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 12 (colorless oily liquid) with a yield of 50%. An appropriate amount of the obtained compound 12 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 H NMR(600MHz,Chloroform-d)δ8.05–8.01(m,2H),7.58–7.54(m,1H),7.47–7.42(m,2H),4.32(t,J=6.6Hz,2 H),3.01(h,J=6.9Hz,1H),1.90–1.82(m,1H),1.82–1.75(m,2H),1.57–1.40(m,3H),1.23(d,J=6.9Hz,3H).

[0190] 13 C NMR (151MHz, Chloroform-d) δ 195.3 (q, J = 33.3Hz), 166.8, 133.1, 130.4, 129.7, 128.5, 115.7 (q, J = 291.3Hz), 64.6, 40.9, 32.0, 28.7, 23.6, 16.2.

[0191] 19 F NMR (565MHz, Chloroform-d) delta -77.98.

[0192] Example 15: Preparation of Compound 15

[0193]

[0194] Ir[dF(Me)ppy]2(dtbbpy)PF6 (2.0 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 15-a (29.8 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under nitrogen atmosphere, irradiated with 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 60% by nuclear magnetic hydrogen spectrum. Column chromatography was performed for separation and purification to obtain compound 15 (colorless oily liquid) with a yield of 57%. An appropriate amount of the obtained compound 15 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 H NMR(600MHz,Chloroform-d)δ4.07(t,J=6.5Hz,2H),3.55(t,J=6.1Hz,2H),2.98(h,J=6.9Hz,1H),2.34(t,J=6 .9Hz,2H),1.86–1.75(m,5H),1.67–1.60(m,2H),1.51–1.43(m,1H),1.40–1.31(m,2H),1.22(d,J=6.9Hz,3H).

[0195] 13 C NMR (151MHz, Chloroform-d) δ 195.3 (q, J = 33.7Hz), 173.3, 115.9 (q, J = 293.4Hz), 64.1, 44.6, 40.9, 33.5, 32.0, 28.6, 23.5, 22.4, 16.2.

[0196] 19 F NMR (565MHz, Chloroform-d) δ-78.01.

[0197] Example 16: Preparation of Compound 17

[0198]

[0199] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 17-a (25.0 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an NMR internal standard. The reaction yield was determined to be 60% by NMR hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 17 (colorless oily liquid) with a yield of 49%. An appropriate amount of the obtained compound 17 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 HNMR(400MHz,Chloroform-d)δ4.07(t,J=6.7Hz,2H),2.99(h,J=6.8Hz,1H),2.31(td,J=7.2,2.0Hz,2H),1.85–1. 75(m,1H),1.72–1.58(m,4H),1.53–1.43(m,1H),1.43–1.32(m,2H),1.22(d,J=6.9Hz,3H),0.93(t,J=7.4Hz,3H).

[0200] 13 C NMR (101MHz, Chloroform-d) δ 195.1 (q, J = 33.4Hz), 173.2, 115.8 (q, J = 291.3Hz), 64.5, 40.8, 34.0, 31.7, 30.8, 22.4, 19.3, 16.1, 13.8.

[0201] 19 F NMR (376MHz, Chloroform-d) delta -77.94.

[0202] Example 17: Preparation of Compound 18

[0203]

[0204] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 18-a (27.6 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an NMR internal standard. The reaction yield was determined to be 51% by NMR hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 18 (colorless oily liquid) with a yield of 39%. An appropriate amount of the obtained compound 18 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 HNMR(400MHz,Chloroform-d)δ4.79–4.71(m,1H),2.98(h,J=6.8Hz,1H),2.29(td,J=7.2,1 .4Hz,2H),1.87–1.77(m,3H),1.77–1.59(m,4H),1.59–1.30(m,7H),1.22(d,J=7.0Hz,3H).

[0205] 13 C NMR (101MHz, Chloroform-d) δ 195.1 (q, J = 33.4Hz), 172.6, 115.9 (q, J = 291.4Hz), 72.9, 40.8, 34.4, 31.8, 31.7, 25.5, 23.9, 22.5, 16.1.

[0206] 19 F NMR (376MHz, Chloroform-d) delta -77.93.

[0207] Example 18: Preparation of Compound 21

[0208]

[0209] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 21-a (35.2 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 68% by nuclear magnetic hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 21 (colorless oily liquid) with a yield of 55%. An appropriate amount of the obtained compound 21 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 HNMR(400MHz,Chloroform-d)δ2.86(tt,J=12.4,3.5Hz,1H),2.43(dd,J=19.2,8.7Hz,1H),2.08(dt,J=18.8,8.9Hz,1H),1 .96–1.89(m,3H),1.84–1.77(m,1H),1.67–1.24(m,14H),1.23–1.14(m,1H),1.14–1.01(m,1H),0.99(s,3H),0.85(s,3H).

[0210] 13 C NMR(101MHz,Chloroform-d)δ221.3,194.7(q,J=33.3Hz),116.0(q,J=293.5Hz),51.4,47.9,4 6.0,42.8,40.8,36.2,36.1,35.5,35.1,31.7,28.3,26.9,25.3,23.8,22.8,21.9,20.3,13.9.

[0211] 19 F NMR (376MHz, Chloroform-d) delta -77.60.

[0212] Example 19: Preparation of Compound 22

[0213]

[0214] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (5.3 mg, 0.03 mmol, 0.3 equiv.), compound 22-a (34.8 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (104.2 mg, 0.4 mmol, 4.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (84.0 mg, 0.4 mmol, 4.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 12 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 59% by nuclear magnetic hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 22 (colorless oily liquid) with a yield of 55%. An appropriate amount of the obtained compound 22 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 HNMR(400MHz,Chloroform-d)δ7.93–7.88(m,2H),7.70–7.63(m,1H),7.60–7.53(m,2H),4.03(td,J=6.4,2.1H z,2H),2.88(p,J=6.8Hz,1H),1.72–1.60(m,4H),1.51–1.38(m,2H),1.31–1.21(m,4H),0.90(t,J=7.3Hz,3H).

[0215] 13 C NMR (101MHz, Chloroform-d) δ 195.2 (q, J = 33.7Hz), 136.2, 133.9, 129.4, 128.0, 115.7 (q, J = 291.2Hz), 70.3, 46.2, 33.4, 30.5, 28.9, 23.2, 20.3, 14.0.

[0216] 19 F NMR (376MHz, Chloroform-d) δ-78.76.

[0217] Example 20: Preparation of Compound 24

[0218]

[0219] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (17.4 mg, 0.1 mmol, 1.0 equiv.), compound 24-a (21.2 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (208.4 mg, 0.8 mmol, 8.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (126.0 mg, 0.6 mmol, 6.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 20 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 82% by nuclear magnetic hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 24 (colorless oily liquid) with a yield of 82%. An appropriate amount of the obtained compound 24 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 HNMR (400MHz, Chloroform-d) δ7.32–7.26(m,2H),7.23–7.15(m,3H),2.73(t,J=6.7Hz,2H),2.65(t,J=7.1Hz,2H),1.78–1.63(m,4H).

[0220] 13 C NMR (101MHz, Chloroform-d) δ 190.5 (q, J = 34.7Hz), 141.8, 128.6, 128.5, 126.1, 115.7 (q, J = 290.4Hz), 36.3, 35.6, 30.6, 22.1.

[0221] 19 F NMR (376MHz, Chloroform-d) δ-79.34.

[0222] Example 21: Preparation of Compound 26

[0223]

[0224] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (17.4 mg, 0.1 mmol, 1.0 equiv.), compound 26-a (26.7 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (208.4 mg, 0.8 mmol, 8.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (126.0 mg, 0.6 mmol, 6.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 20 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an NMR internal standard. The reaction yield was determined to be 70% by NMR hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 26 (colorless oily liquid) with a yield of 69%. An appropriate amount of the obtained compound 26 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 HNMR(400MHz,Chloroform-d)δ7.60–7.55(m,2H),6.95–6.89(m,2H),4.01(t,J=6.3Hz ,2H),2.76(t,J=7.1Hz,2H),1.88–1.81(m,2H),1.80–1.73(m,2H),1.56–1.50(m,2H).

[0225] 13 C NMR (101MHz, Chloroform-d) δ 190.9 (q, J = 34.8Hz), 162.4, 134.1, 119.4, 116.0 (q, J = 290.2Hz), 104.1, 68.0, 36.3, 28.8, 25.4, 22.2.

[0226] 19 F NMR (565MHz, Chloroform-d) delta-79.33.

[0227] Example 22: Preparation of Compound 27

[0228]

[0229] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (17.4 mg, 0.1 mmol, 1.0 equiv.), compound 27-a (30.9 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (208.4 mg, 0.8 mmol, 8.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (126.0 mg, 0.6 mmol, 6.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 20 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an NMR internal standard. The reaction yield was determined to be 73% by NMR hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 27 (colorless oily liquid) with a yield of 66%. An appropriate amount of the obtained compound 27 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 HNMR (400MHz, Chloroform-d) δ7.86–7.81(m,2H),7.73–7.68(m,2H),3.68(t,J=7.2Hz,2H),2.70(t,J=7.2Hz,2H),1.72–1.64(m,4H),1.41–1.34(m,4H).

[0230] 13 C NMR (101MHz, Chloroform-d) δ 190.6 (q, J = 35.0Hz), 168.6, 134.1, 132.3, 123.4, 115.8 (q, J = 292.3Hz), 37.9, 36.4, 28.5, 28.4, 26.5, 22.3.

[0231] 19 F NMR (565MHz, Chloroform-d) delta-79.32.

[0232] Example 23: Preparation of Compound 30

[0233]

[0234] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (17.4 mg, 0.1 mmol, 1.0 equiv.), compound 30-a (29.2 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (208.4 mg, 0.8 mmol, 8.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (126.0 mg, 0.6 mmol, 6.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 20 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction liquid was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 80% by nuclear magnetic hydrogen spectrum. Column chromatography was separated and purified to obtain compound 30 (colorless oily liquid) with a yield of 71%. An appropriate amount of the obtained compound 30 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 HNMR(600MHz,Chloroform-d)δ4.08(t,J=6.6Hz,2H),3.96(dt,J=11.6,3.6Hz,2H),3.43(td,J=11.3,3.0H z,2H),2.72(t,J=7.1Hz,2H),2.58–2.48(m,1H),1.88–1.74(m,4H),1.74–1.60(m,4H),1.43–1.34(m,4H).

[0235] 13 C NMR (151MHz, Chloroform-d) δ 191.6 (q, J = 34.9Hz), 174.7, 115.7 (q, J = 290.3Hz), 67.3, 64.5, 40.3, 36.3, 28.8, 28.5, 28.5, 25.7, 22.4.

[0236] 19 F NMR (376MHz, Chloroform-d) δ-79.34.

[0237] Example 24: Preparation of Compound 32

[0238]

[0239] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (17.4 mg, 0.1 mmol, 1.0 equiv.), compound 32-a (28.4 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (208.4 mg, 0.8 mmol, 8.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (126.0 mg, 0.6 mmol, 6.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 20 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 75% by nuclear magnetic hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 32 (colorless oily liquid) with a yield of 68%. An appropriate amount of the obtained compound 32 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows: 1 HNMR(600MHz,Chloroform-d)δ8.05–8.01(m,2H),7.58–7.53(m,1H),7.46–7.42(t,J=7.8Hz,2H),4.32( t,J=6.8Hz,2H),2.72(t,J=7.2Hz,2H),1.78(p,J=6.8Hz,2H),1.71(p,J=7.2Hz,2H),1.52–1.38(m,4H).

[0240] 13 C NMR (151MHz, Chloroform-d) δ 191.6 (q, J = 34.6Hz), 166.8, 133.0, 130.5, 129.7, 128.5, 115.7 (q, J = 290.3Hz), 64.9, 36.4, 28.6, 28.5, 25.9, 22.4.

[0241] 19 F NMR (565MHz, Chloroform-d) delta-79.34.

[0242] Example 25: Preparation of Compound 35

[0243]

[0244] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (17.4 mg, 0.1 mmol, 1.0 equiv.), compound 35-a (30.9 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (208.4 mg, 0.8 mmol, 8.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (126.0 mg, 0.6 mmol, 6.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 20 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction liquid was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an NMR internal standard. The reaction yield was determined to be 71% by NMR hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 35 (colorless oily liquid) with a yield of 66%. An appropriate amount of the obtained compound 35 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows:

[0245] 1 H NMR(600MHz,Chloroform-d)δ8.15–8.11(m,2H),7.77–7.73(m,2H),4.35(t,J=6.6Hz,2H ), 2.73 (t, J = 7.1Hz, 2H), 1.80 (p, J = 6.6Hz, 2H), 1.72 (p, J = 7.1Hz, 2H), 1.51–1.38 (m, 4H).

[0246] 13 C NMR (151MHz, Chloroform-d) δ191.6 (q, J=35.0Hz), 165.1, 134.3, 132.4, 130. 2,118.1,116.5,115.7(q,J=290.4Hz),65.7,36.3,28.51,28.50,25.8,22.4.

[0247] 19 F NMR (565MHz, Chloroform-d) delta-79.34.

[0248] Example 26: Preparation of Compound 36

[0249]

[0250] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (17.4 mg, 0.1 mmol, 1.0 equiv.), compound 36-a (27.4 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (208.4 mg, 0.8 mmol, 8.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (126.0 mg, 0.6 mmol, 6.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 20 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an NMR internal standard. The reaction yield was determined to be 66% by NMR hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 36 (colorless oily liquid) with a yield of 62%. An appropriate amount of the obtained compound 36 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows:

[0251] 1 H NMR (600MHz, Chloroform-d) δ7.58 (dd, J=1.8, 0.9Hz, 1H), 7.17 (dd, J=3.5, 0.9Hz, 1H), 6.51 (dd, J= 3.5, 1.7Hz, 1H), 4.30 (t, J = 6.6Hz, 2H), 2.72 (t, J = 7.2Hz, 2H), 1.80–1.67 (m, 4H), 1.48–1.38 (m, 4H).

[0252] 13 C NMR (151MHz, Chloroform-d) δ 191.6 (q, J = 34.7Hz), 159.0, 146.4, 144.9, 118.0, 115.7 (q, J = 290.3Hz), 112.0, 64.9, 36.4, 28.6, 28.5, 25.7, 22.4.

[0253] 19 F NMR (565MHz, Chloroform-d) delta-79.34.

[0254] Example 27: Preparation of Compound 37

[0255]

[0256] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (17.4 mg, 0.1 mmol, 1.0 equiv.), compound 37-a (32.0 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (208.4 mg, 0.8 mmol, 8.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (126.0 mg, 0.6 mmol, 6.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 20 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an NMR internal standard. The reaction yield was determined to be 65% by NMR hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 37 (colorless oily liquid) with a yield of 57%. An appropriate amount of the obtained compound 37 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows:

[0257] 1 H NMR(600MHz,Chloroform-d)δ7.94–7.89(m,2H),7.69–7.63(m,1H),7.60–7.53(m,2H ),4.05(t,J=6.3Hz,2H),2.68(t,J=7.2Hz,2H),1.71–1.60(m,4H),1.40–1.27(m,4H).

[0258] 13 C NMR (151MHz, Chloroform-d) δ 191.5 (q, J = 34.7Hz), 136.3, 133.9, 129.4, 128.0, 115.7 (q, J = 290.3Hz), 70.6, 36.3, 28.7, 28.2, 25.2, 22.2.

[0259] 19 F NMR (376MHz, Chloroform-d) δ-79.34.

[0260] Example 28: Preparation of Compound 38

[0261]

[0262] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (17.4 mg, 0.1 mmol, 1.0 equiv.), compound 24-a (35.4 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (208.4 mg, 0.8 mmol, 8.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (126.0 mg, 0.6 mmol, 6.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 20 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an NMR internal standard. The reaction yield was determined to be 63% by NMR hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 38 (colorless oily liquid) with a yield of 59%. An appropriate amount of the obtained compound 38 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows:

[0263] 1 H NMR(600MHz,Chloroform-d)δ7.94–7.89(m,2H),7.69–7.64(m,1H),7.59–7.53(m,2H ),4.05(t,J=6.3Hz,2H),2.68(t,J=7.2Hz,2H),1.70–1.60(m,4H),1.40–1.27(m,4H).

[0264] 13 C NMR (151MHz, Chloroform-d) δ 191.5 (q, J = 34.6Hz), 136.3, 133.9, 129.4, 128.0, 115.7 (q, J = 290.3Hz), 70.6, 36.3, 28.7, 28.2, 25.2, 22.2.

[0265] 19 F NMR (376MHz, Chloroform-d) δ-79.34.

[0266] Example 29: Preparation of Compound 41

[0267]

[0268] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (17.4 mg, 0.1 mmol, 1.0 equiv.), compound 41-a (26.0 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (208.4 mg, 0.8 mmol, 8.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (126.0 mg, 0.6 mmol, 6.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 20 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 62% by nuclear magnetic hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 41 (colorless oily liquid) with a yield of 55%. An appropriate amount of the obtained compound 41 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows:

[0269] 1 H NMR (600MHz, Chloroform-d) δ4.12–4.08(m,2H),2.72(t,J=7.2Hz,2H),2.57–2.47(m,4H),1.98(s,1H),1.73–1.60(m,4H),1.41–1.35(m,4H).

[0270] 13 C NMR (151MHz, Chloroform-d) δ 191.6 (q, J = 34.6Hz), 172.0, 115.7 (q, J = 290.4Hz), 82.6, 69.1, 64.7, 36.3, 33.5, 28.4, 25.7, 22.3, 14.5.

[0271] 19 F NMR (376MHz, Chloroform-d) δ-79.32.

[0272] Example 30: Preparation of Compound 44

[0273]

[0274] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6 (2.3 mg, 0.002 mmol, 0.02 equiv.), K2HPO4 (17.4 mg, 0.1 mmol, 1.0 equiv.), compound 44-a (24.2 mg, 0.1 mmol, 1.0 equiv.) and triphenylsilane (208.4 mg, 0.8 mmol, 8.0 equiv.) were mixed, and 0.3 mL of methyl tert-butyl ether, 2,6-di-n-propoxypyridine (19.5 mg, 0.1 mmol, 1.0 equiv.) and compound 1-b (126.0 mg, 0.6 mmol, 6.0 equiv.) were added under a nitrogen atmosphere. The mixture was irradiated with a 30 W blue light lamp at room temperature for 20 hours, and then 5 mL of saturated sodium bicarbonate aqueous solution and 5 mL of ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL × 2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phase was then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 64% by nuclear magnetic hydrogen spectrum. Column chromatography was used for separation and purification to obtain compound 44 (colorless oily liquid) with a yield of 60%. An appropriate amount of the obtained compound 44 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows:

[0275] 1 H NMR (600MHz, Chloroform-d) δ2.18(hept,J=3.0Hz,1H),1.79(d,J=2.3Hz,2H),1.57(q,J=12.6Hz,4H),1.44–1.34(m,4H),1.26–1.14(m,2H),0.88(s,6H).

[0276] 13 C NMR (151MHz, Chloroform-d) δ 195.1 (q, J = 31.3Hz), 116.5 (q, J = 293.2Hz), 50.5, 47.1, 43.3, 42.6, 36.0, 30.9, 30.5, 28.9.

[0277] 19 F NMR (376MHz, Chloroform-d) delta-72.14.

[0278] Example 31: Preparation of Compound 46

[0279]

[0280] Ir[dF(CF3)ppy]2(5,5'-dCF3bbpy)PF6(2.3mg, 0.002mmol, 0.02equiv.), K2HPO4(17.4mg, 0.1mmol, 1.0equiv.), compound 24-a(21.2mg, 0.1mmol, 1.0equiv.) and triphenylsilane(208.4mg, 0.8mmol, 8.0equiv.) were mixed, 0.3mL methyl tert-butyl ether, 2,6-di-n-propoxypyridine(19.5mg, 0.1mmol, 1.0equiv.) and compound 3-b(246mg, 0.6mmol, 6.0equiv.) were added under nitrogen atmosphere, irradiated with 30W blue light lamp at room temperature for 20 hours, and then 5mL saturated sodium bicarbonate aqueous solution and 5mL ethyl acetate were added to dilute. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5mL×2). The organic phases were then combined and washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The organic phases were then concentrated, and phenyltrimethylsilane was added as an internal standard for nuclear magnetic resonance. The reaction yield was determined to be 46% by nuclear magnetic hydrogen spectrum. Column chromatography was performed for separation and purification to obtain compound 46 (colorless oily liquid) with a yield of 40%. An appropriate amount of the obtained compound 46 was taken for hydrogen spectrum, carbon spectrum and fluorine spectrum detection, and the results were as follows:

[0281] 1 H NMR (600MHz, Chloroform-d) δ7.26–7.32(m,2H),7.23–7.14(m,3H),2.76(t,J=6.7Hz,2H),2.65(t,J=7.2Hz,2H),1.77–7.62(m,4H).

[0282] 13 C NMR(151MHz,Chloroform-d)δ194.13(t,J=26.0Hz),141.8,128.6,128.5,126.1,117.5(qt,J=28 7.9, 33.5Hz), 108.8 (tt, J=267.8, 32.1Hz), 117.5 (qt, J=266.3, 33.4Hz), 37.9, 35.7, 30.5, 22.1.

[0283] 19 F NMR (377MHz, Chloroform-d) δ -80.60 (t, J = 8.8Hz), -121.17 (q, J = 9.0Hz), -126.64.

[0284] The method of the present invention has been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the methods and applications described herein within the content, spirit and scope of the present invention to implement and apply the technology of the present invention. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters. It is particularly important to point out that all similar replacements and modifications are obvious to those skilled in the art, and they are all considered to be included in the present invention.

Claims

1. A method for preparing compound C, comprising: ， Compound a and compound b react in the presence of a photosensitizer and silane in an inert gas atmosphere in a solvent under light irradiation to obtain compound c. in, R is selected from substituted or unsubstituted C 1- C 30 Alkyl, substituted or unsubstituted C1-C 30 heteroalkyl; The substituted or unsubstituted C 1- C 30 The alkyl group in the alkyl group is a hydrocarbon containing normal carbon atoms, secondary carbon atoms, and tertiary carbon atoms; The substituted or unsubstituted C1-C 30 The heteroalkyl group in the heteroalkyl group means that one or more carbon atoms in a straight-chain or branched saturated hydrocarbon group are independently substituted by one or more heteroatoms, and the one or more heteroatoms are independently selected from nitrogen atoms, oxygen atoms, phosphorus atoms and sulfur atoms; The substitution in the "substituted or unsubstituted" independently means that one or more hydrogen atoms on the group are replaced by a substituent selected from the group consisting of benzoyl, tert-butyloxycarbonyl, =0, fluorine atom, chlorine atom, bromine atom, cyano group, C1 ~ C10 alkyl, C3 ~ C10 cycloalkyl, C1 ~ C10 heteroalkyl, C3 ~ C10 cycloheteroalkyl, C2 ~ C6 alkenyl, C2 ~ C6 alkynyl, C6 ~ C10 aryl or C6 ~ C10 heteroaryl, , , , , , , , , , , , wherein R1, R2, R3, R4, and R5 are independently selected from hydrogen, fluorine, chlorine, bromine, cyano, methyl, or ethyl; and / or Rf is selected from the group consisting of perfluorinated C1-C 10 alkyl; X is selected from bromine atoms; The photosensitizer is selected from at least one of an iridium photosensitizer or an organic photosensitizer; The iridium photosensitizer is selected from at least one of Ir[dF(Me)ppy]2(dtbbpy)PF6, Ir[dF(CF3)ppy]2(5,5'-dCF3bpy)PF6, Ir[dF(CF3)ppy]2(4,4'-dCF3bpy)PF6, and Ir(ppy)3; The organic photosensitizer is selected from at least one of 4-CzIPN, 3DPA2FBN, and 3DPAIFPN; The silane is selected from at least one of triphenylsilane, diphenylsilane and phenyldimethylsilane. The solvent is selected from at least one of methyl tert-butyl ether, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, 1,4-dioxane, diethyl ether, dichloromethane and toluene.

2. The preparation method according to claim 1, The perfluorinated C1-C 10 The alkyl group is selected from trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, undecafluoropentyl, tridecafluorohexyl, pentafluoroheptyl, heptadecafluorooctyl, nonadecafluorononyl, heneicosaefluorodecyl.

3. The preparation method according to claim 1, wherein the substituted or unsubstituted C 1- C 30 Alkyl groups include unsubstituted straight chain C 1- C 30 Alkyl, unsubstituted branched C 1- C 30 Alkyl, C6-C 10 Aryl substituted straight chain C 1- C 30 Alkyl, C6-C 10 Aryl substituted branched C 1- C 30 Alkyl, halogen substituted straight chain C 1- C 30 Alkyl, halogen substituted branched C 1- C 30 alkyl; The halogen is selected from a fluorine atom, a chlorine atom and a bromine atom.

4. A method for preparing compound C, comprising: ， Compound a and compound b react in the presence of a photosensitizer and silane in an inert gas atmosphere in a solvent under light irradiation to obtain compound c. in, The photosensitizer is selected from at least one of an iridium photosensitizer or an organic photosensitizer; The iridium photosensitizer is selected from at least one of Ir[dF(Me)ppy]2(dtbbpy)PF6, Ir[dF(CF3)ppy]2(5,5'-dCF3bpy)PF6, Ir[dF(CF3)ppy]2(4,4'-dCF3bpy)PF6, and Ir(ppy)3; The organic photosensitizer is selected from at least one of 4-CzIPN, 3DPA2FBN, and 3DPAIFPN; The silane is selected from at least one of triphenylsilane, diphenylsilane and phenyldimethylsilane. The solvent is selected from at least one of methyl tert-butyl ether, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, 1,4-dioxane, ether, dichloromethane, and toluene; and the compound c is selected from the structures of the following compounds 1 to 19 and compounds 22 to 47: ； X is selected from bromine atoms; R and Rf correspond one to one with compound C.

5. The preparation method according to claim 1, The iridium photosensitizer is [Ir(dF(Me)ppy2)(dtbbpy)]PF6, ； The organic photosensitizer is 3DPAIFPN, 。 6. The preparation method according to any one of claims 1 to 5, wherein the silane is triphenylsilane; and / or The inert gas includes at least one of nitrogen, helium, neon and argon; and / or The solvent is at least one of methyl tert-butyl ether and 1,4-dioxane; and / or The illumination is blue light; and / or The wavelength of the blue light is 400nm~480nm; and / or The molar ratio of compound b to compound a is 1.0:1.0-15.0:1.0 and / or The molar ratio of the silane to the compound a is 1.0:1.0-20.0:1.00; and / or The molar ratio of the photosensitizer to compound a is 0.005:1.000-0.100:1.

000.

7. The preparation method according to any one of claims 1 to 5, wherein the molar ratio of compound b to compound a is 1.0:1.0-10.0:1.

0.

8. The preparation method according to any one of claims 1 to 5, wherein the molar ratio of compound b to compound a is 1.0:1.0-6.0:1.

0.

9. The preparation method according to any one of claims 1 to 5, wherein the molar ratio of compound b to compound a is 1.0:1.0-5.0:1.

0.

10. The preparation method according to any one of claims 1 to 5, wherein the molar ratio of compound b to compound a is 1.0:1.0-4.0:1.

0.

11. The preparation method according to any one of claims 1 to 5, wherein the solvent is methyl tert-butyl ether; and / or The molar ratio of compound b to compound a is 2.0:1.0-10.0:1.0; and / or The molar ratio of the photosensitizer to compound a is 0.010:1.000-0.050:1.

000.

12. The preparation method according to any one of claims 1 to 5, wherein the molar ratio of compound b to compound a is 2.0:1.0-8.0:1.

0.

13. The preparation method according to any one of claims 1 to 5, wherein the molar ratio of the silane to the compound a is 4.0:1.0; and / or The molar ratio of the photosensitizer to compound a is 0.020:1.000-0.040:1.

000.

14. A method for preparing compound C, comprising: ， Compound a and compound b react in the presence of a photosensitizer, silane, a base and a pyridine reagent in an inert gas atmosphere in a solvent under light irradiation to obtain compound c; in, R is selected from substituted or unsubstituted C 1- C 30 Alkyl, substituted or unsubstituted C1-C 30 heteroalkyl; The substituted or unsubstituted C 1- C 30 The alkyl group in the alkyl group is a hydrocarbon containing normal carbon atoms, secondary carbon atoms, and tertiary carbon atoms; The substituted or unsubstituted C1-C 30 The heteroalkyl group in the heteroalkyl group means that one or more carbon atoms in a straight-chain or branched saturated hydrocarbon group are independently substituted by one or more heteroatoms, and the one or more heteroatoms are independently selected from nitrogen atoms, oxygen atoms, phosphorus atoms and sulfur atoms; The substitution in the "substituted or unsubstituted" independently means that one or more hydrogen atoms on the group are replaced by a substituent selected from the group consisting of benzoyl, tert-butyloxycarbonyl, =0, fluorine atom, chlorine atom, bromine atom, cyano group, C1 ~ C10 alkyl, C3 ~ C10 cycloalkyl, C1 ~ C10 heteroalkyl, C3 ~ C10 cycloheteroalkyl, C2 ~ C6 alkenyl, C2 ~ C6 alkynyl, C6 ~ C10 aryl or C6 ~ C10 heteroaryl, , , , , , , , , , , , wherein R1, R2, R3, R4, and R5 are independently selected from hydrogen, fluorine, chlorine, bromine, cyano, methyl, or ethyl; and / or Rf is selected from the group consisting of perfluorinated C1-C 10 alkyl; X is selected from bromine atoms; The photosensitizer is selected from at least one of an iridium photosensitizer or an organic photosensitizer; The iridium photosensitizer is selected from at least one of Ir[dF(Me)ppy]2(dtbbpy)PF6, Ir[dF(CF3)ppy]2(5,5'-dCF3bpy)PF6, Ir[dF(CF3)ppy]2(4,4'-dCF3bpy)PF6, and Ir(ppy)3; The organic photosensitizer is selected from at least one of 4-CzIPN, 3DPA2FBN, and 3DPAIFPN; The silane is selected from at least one of triphenylsilane, diphenylsilane and phenyldimethylsilane. The solvent is selected from at least one of methyl tert-butyl ether, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, 1,4-dioxane, diethyl ether, dichloromethane and toluene; The pyridine reagent is selected from at least one of 2,6-dimethoxypyridine, 2,6-lutidine, 2,6-dichloropyridine, 2,6-dipropoxypyridine, 2,6-dicyclohexylpyridine, 2,4,6-trimethoxypyridine, 2,4,6-triethoxypyridine and 2,6-dichloropyridine nitrogen oxide.

15. The preparation method according to claim 14, The perfluorinated C1-C 10 The alkyl group is selected from trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, undecafluoropentyl, tridecafluorohexyl, pentafluoroheptyl, heptadecafluorooctyl, nonadecafluorononyl, heneicosaefluorodecyl.

16. The preparation method according to claim 14, wherein the substituted or unsubstituted C 1- C 30 Alkyl groups include unsubstituted straight chain C 1- C 30 Alkyl, unsubstituted branched C 1- C 30 Alkyl, C6-C 10 Aryl substituted straight chain C 1- C 30 Alkyl, C6-C 10 Aryl substituted branched C 1- C 30 Alkyl, halogen substituted straight chain C 1- C 30 Alkyl, halogen substituted branched C 1- C 30 alkyl; The halogen is selected from a fluorine atom, a chlorine atom and a bromine atom.

17. A method for preparing compound C, comprising: ， Compound a and compound b react in the presence of a photosensitizer, silane, a base and a pyridine reagent in an inert gas atmosphere in a solvent under light irradiation to obtain compound c; The photosensitizer is selected from at least one of an iridium photosensitizer or an organic photosensitizer; The iridium photosensitizer is selected from at least one of Ir[dF(Me)ppy]2(dtbbpy)PF6, Ir[dF(CF3)ppy]2(5,5'-dCF3bpy)PF6, Ir[dF(CF3)ppy]2(4,4'-dCF3bpy)PF6, and Ir(ppy)3; The organic photosensitizer is selected from at least one of 4-CzIPN, 3DPA2FBN, and 3DPAIFPN; The silane is selected from at least one of triphenylsilane, diphenylsilane and phenyldimethylsilane. The solvent is selected from at least one of methyl tert-butyl ether, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, 1,4-dioxane, diethyl ether, dichloromethane and toluene; The pyridine reagent is selected from at least one of 2,6-dimethoxypyridine, 2,6-lutidine, 2,6-dichloropyridine, 2,6-dipropoxypyridine, 2,6-dicyclohexylpyridine, 2,4,6-trimethoxypyridine, 2,4,6-triethoxypyridine, and 2,6-dichloropyridine nitrogen oxide; The compound c is selected from the following structures of compound 1-compound 19 and compound 22-compound 47: ； X is selected from bromine atoms; R and Rf correspond one to one with compound C.

18. The preparation method according to claim 14 or 17, The iridium photosensitizer is [Ir(dF(Me)ppy2)(dtbbpy)]PF6, ； The organic photosensitizer is 3DPAIFPN, 。 19. The preparation method according to claim 14 or 17, wherein the silane is triphenylsilane; and / or The inert gas includes at least one of nitrogen, helium, neon and argon; and / or The solvent is at least one of methyl tert-butyl ether and 1,4-dioxane; and / or The illumination is blue light; and / or The wavelength of the blue light is 400nm~480nm.

20. The preparation method according to claim 14 or 17, wherein the base is at least one selected from dipotassium hydrogen phosphate, potassium dihydrogen phosphate, tripotassium phosphate, lithium carbonate, cesium carbonate, potassium carbonate, potassium acetate, and triethylenediamine; and / or The pyridine reagent is at least one of 2,6-di-n-propoxypyridine or 2,4,6-triethoxypyridine.

21. The preparation method according to claim 14 or 17, wherein the base is at least one of triethylenediamine or dipotassium hydrogen phosphate.

22. The preparation method according to claim 14 or 17, wherein the base is dipotassium hydrogen phosphate.

23. The preparation method according to claim 14 or 17, wherein the pyridine reagent is 2,6-di-n-propoxypyridine.

24. The preparation method according to claim 14 or 17, wherein the molar ratio of the base to compound a is 0.1:1.0-5.0:1.0; and / or the molar ratio of the pyridine reagent to compound a is 0.1:1.0-5.0:1.

0.

25. The preparation method according to claim 14 or 17, wherein the molar ratio of the base to compound a is 0.2:1.0-1.5:1.

0.

26. The preparation method according to claim 14 or 17, wherein the molar ratio of the base to compound a is 0.3:1.0-1.0:1.

0.

27. The preparation method according to claim 14 or 17, wherein the molar ratio of the pyridine reagent to compound a is 0.5:1.0-3.0:1.

0.

28. The preparation method according to claim 14 or 17, wherein the molar ratio of the pyridine reagent to compound a is 1.0:1.0-2.0:1.0.

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