CN106278847B

CN106278847B - Compound containing fluoroalkyl, preparation method and application thereof

Info

Publication number: CN106278847B
Application number: CN201510268169.XA
Authority: CN
Inventors: 张新刚; 安伦
Original assignee: Shanghai Institute of Organic Chemistry of CAS
Current assignee: Shanghai Institute of Organic Chemistry of CAS
Priority date: 2015-05-22
Filing date: 2015-05-22
Publication date: 2020-12-08
Anticipated expiration: 2035-05-22
Also published as: CN106278847A

Abstract

The invention discloses a compound containing monofluoroalkyl and a preparation method thereof. The invention provides a preparation method of a compound containing monofluoroalkyl, which comprises the following steps: in a solvent, under the condition of existence of alkali, an additive, a ligand and a catalyst, carrying out a suzuki coupling reaction on a compound A and a compound B to obtain a compound C, wherein the catalyst is nickel salt, and the nickel salt is NiL_nCl₂、NiL_nBr₂、NiL_nI₂Or NiQ₂·mH₂And O. The preparation method can introduce fluoroalkyl through one-step reaction, is efficient, simple and convenient, has good functional group compatibility and strong broad spectrum property, can avoid using a highly toxic reagent, is simple and safe in post-treatment operation, is environment-friendly, has cheap and low consumption of a catalyst, is mild in reaction conditions, high in reaction conversion rate, high in yield and low in production cost, and is suitable for industrial production.

Description

Compound containing fluoroalkyl, preparation method and application thereof

Technical Field

The invention relates to a compound containing fluoroalkyl, a preparation method and application thereof.

Background

Fluoroalkyl-substituted aromatic compounds have important applications in the fields of medicine, pesticides and material science. Although there have been some reports of introduction of fluoroalkyl groups into aromatic rings in recent years, there have been few reports of methods for synthesizing monofluoroalkyl group-containing compounds.

Due to the unique physical, chemical and biological properties of Fluorine atoms, this class of monofluoroalkyl containing compounds has very important applications in the field of Life Sciences ((a) B.E.Smart, J.Fluorine Chem.2001, 109, 3; (b) P.Maienfsch, R.G.Hall, Chimia.2004, 58, 93; (c) Special issue on "Fluorine in the Life Sciences", ChemBioChem.2004, 5, 557; (d) F.Babudri, G.M.Farinola, F.Naso, R.Ragni, Chem.Commun.2007, 1003; (e) K.M uller, C.Faeh, F.Diederich, Science, 1881; (f) S.Purser, P.R.Morse, S.Swall, V.Gouter, Gourm.37.2008, 320.Sourc.320.D.. The current methods for synthesizing such compounds using equivalent or catalytic amounts of transition metals also have only a few examples ((a) h.doi, i.ban, a.nonoyama, k.sumi, c.kuang, t.hosoya, h.tsukada, m.suzuki, chem.eur.j.2009, 15, 4165, (b) h.doi, m.goto, m.suzuki, fill.chem.soc.jpn.2012, 11, 1233, (c) y.zhao, b.gao, c.ni, j.hu, org.lett.2012, 14, 6080, (d) y.zhao, c.ni, f.jiang, b.gao, x.shen, j.huacs, catal.2013, 3, etc.) and these methods still have some shortages, reaction conditions, catalysts are expensive, and have poor spectrum compatibility. For example, reference b is based on a palladium-catalyzed cross-coupling reaction of an arylboronic acid ester with fluorobromomethane or fluoroiodomethane, but this reaction requires 40 times the equivalent of the arylboronic acid ester, the range of applicable substrates is limited, and the reaction efficiency needs to be improved. Therefore, it is a technical problem to be solved urgently at present to search a preparation method of monofluoroalkyl containing compound, which is efficient, simple, convenient, good in functional group compatibility, low in catalyst cost and dosage, mild in reaction condition, short in reaction step, high in reaction conversion rate, high in yield, and suitable for industrial production.

Disclosure of Invention

The invention aims to solve the technical problems of complex reaction steps, poor functional group compatibility, high catalyst price, high dosage, harsh reaction conditions, long reaction steps, low reaction conversion rate, low yield, unsuitability for industrial production and the like of the preparation method of the compound containing the monofluoroalkyl, and provides a preparation method and application of the compound containing the monofluoroalkyl. The preparation method can introduce fluoroalkyl through one-step reaction, is efficient, simple and convenient, has good functional group compatibility and strong broad spectrum property, can avoid using a highly toxic reagent, is simple and safe in post-treatment operation, is environment-friendly, has cheap and low consumption of a catalyst, is mild in reaction conditions, high in reaction conversion rate, high in yield and low in production cost, and is suitable for industrial production. The compound containing fluoroalkyl prepared by the invention has wide application in preparing medicines, pesticides or medical materials, and has good marketization prospect.

The invention provides a preparation method of a compound containing monofluoroalkyl, which comprises the following steps: in a solvent, under the condition that alkali, an additive, a ligand and a catalyst exist, carrying out a suzuki coupling reaction on a compound A and a compound B to obtain a compound C, wherein the catalyst is nickel salt, and the nickel salt is NiL_nCl₂(e.g., NiCl)₂·DME、NiCl₂(PPh₃)₂Or NiCl₂·dppe)、NiL_nBr₂、NiL_nI₂Or NiQ₂·mH₂O (e.g. NiCl)₂、NiBr₂、NiI₂、NiCl₂·6H₂O、NiBr₂·3H₂O、Ni(OAc)₂、Ni(acac)₂Or Ni (NO)₃)₂·6H₂O)；

Wherein Q is nitrate, acetate, acetylacetonate, chloride, bromide or iodide, and m is 0. ltoreq. m.ltoreq.10 (e.g. 0, 1,2, 3,4, 5, 6, 7, 8, 9 or 10); and 0. ltoreq. n < 3 (e.g. 0, 1,2 or 3); l is triphenylphosphine, o-methoxytriphenylphosphine, o-methyltriphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triamantalkylphosphine, 1,2 bis (diphenylphosphino) ethane (dppe), 1,3 bis (diphenylphosphino) propane (dppp), 14-bis (diphenylphosphino) butane (dppb), 1' -bis (diphenylphosphino) ferrocene (dppf), bis-diphenylphosphinomethane (dppm), 1, 2-bis-triphenylphosphine benzene (dppbz), dimethyl ethylene glycol Diether (DME), diethylene glycol dimethyl ether (Diglyme), and "substituted or unsubstituted 1, 10-phenanthroline" (said "unsubstituted 1, 10-phenanthroline" is preferably selected from the group consisting of

The "substituted 1, 10-phenanthroline" is preferably

) "substituted or unsubstituted pyridine" (said "substituted pyridine" is preferably

) Substituted or unsubstituted bipyridyl (said "substituted bipyridyl" is preferably

) Or

(e.g. in

) The term "substituted" as used in the "substituted or unsubstituted bipyridine", "substituted or unsubstituted 1, 10-phenanthroline" or "substituted or substituted pyridine" means substituted with C at a non-ortho position to the hetero atom₁～C₁₀Alkyl (preferably C)₁～C₆Alkyl of said "C₁～C₆Alkyl of "e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl), C₁～C₁₀Alkoxy (preferably C)₁～C₆Alkoxy of said "C₁～C₆Alkoxy of (e.g. methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy) and

when a plurality of substituents are present, the substituents may be the same or different; x is halogen (e.g. chlorine, bromine or iodine, preferably chlorine or bromine); r⁸、R⁹、R¹⁰And R¹¹Are each hydrogen or C₁～C₃Alkyl (e.g., methyl, ethyl, propyl, or isopropyl, preferably methyl); r¹²And R¹³Are respectively hydrogen and C₁～C₃Alkyl (e.g. methyl, ethyl, propyl or isopropyl, preferably methyl), C₅～C₁₀Aryl (e.g. phenyl) or R¹²、R¹³And the carbon atoms to which they are attached together form a 4-6 membered cyclic structure (e.g., a six membered cyclic structure

)。

R¹Is "substituted or unsubstituted C₃～C₁₅Aryl of (1) ("preferably substituted or unsubstituted C)₅～C₁₄Aryl of (b), said "substituted or unsubstituted C₅～C₁₄The aryl group of (a) is preferably a "substituted or unsubstituted phenyl group", "substituted or unsubstituted naphthyl group" or "substituted or unsubstituted fluorenyl group"; said "unsubstituted naphthyl" is for example

Said "unsubstituted fluorenyl" is, for example

Said "substituted fluorenyl" is, for example

Said "substituted phenyl" is preferably

4-tert-butylphenyl,

4-cyanophenyl group, 3-fluoro-4-cyanophenyl group, 3-cyanophenyl group,

3, 4-dichlorophenyl group,

4-phenoxyphenyl, 4-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl,

2-methylphenyl, 3-methylphenyl, 4-methylphenyl,

Or 3, 5-dichlorophenyl; ) And a substituted or unsubstituted C, wherein the heteroatom is an oxygen, sulfur or nitrogen atom, the number of heteroatoms is 1-3₂～C₁₅(preferably "C with 1 hetero atom being an oxygen or nitrogen atom and 1 hetero atom)₃～C₁₂The "hetero atom" is an oxygen or nitrogen atom, and the number of hetero atoms is 1C₃～C₁₂The heteroaryl group of (A) is preferably a substituted or unsubstituted pyridyl group,

Said "unsubstituted pyridyl" may be 2-pyridyl, 3-pyridyl or 4-pyridyl; said "substituted pyridyl" may be

) Or

Said "substituted or unsubstituted C₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅The "substitution" in "the heteroaryl group of (A) is by cyano, halogen (e.g., fluorine, chlorine, bromine or iodine), C₁～C₁₀Alkyl (preferably C)₁～C₆Alkyl of said "C₁～C₆Alkyl of "e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl), C₁～C₁₀Alkoxy (preferably C)₁～C₆Alkoxy of said "C₁～C₆Alkoxy of (e.g. methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy), C₅～C₁₀Aryloxy group of (preferably C)₅～C₆Aryloxy group of said "C₅～C₆Aryloxy group of "e.g. phenoxy"), C₁～C₁₀Alkylthio (preferably C)₁～C₆Alkylthio of said "C₁～C₆Alkylthio of (A) such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio or tert-butylthio), C₁～C₁₀Is preferably C₁～C₆Said "C" is₁～C₆Alkyl silyl group of (e.g., "methylsilyl group", "trimethylsilyl group", "ethylsilyl group", "propylsilyl group", "isopropylsilyl group", "butylsilyl group", "isobutylsilyl group" or "tert-butylsilyl group"), "halogen-substituted C₁～C₁₀Alkyl of (2) ("said halogen-substituted C)₁～C₁₀The halogen in the "alkyl group of (1)" is preferably fluorine, chlorine or bromine, the number of the halogen is 1 to 4, and when a plurality of halogen atoms are present, the halogen atoms may be the same or different; said "halogen-substituted C₁～C₁₀Alkyl group of (2)' C₁～C₁₀Alkyl of (2)' preferably C₁～C₆Alkyl of (a), the"C" of₁～C₆The alkyl group of (1) may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a tert-butyl group. Said "halogen-substituted C₁～C₁₀Alkyl of (A) is "preferably" C substituted by one or more of fluorine, chlorine and bromine atoms₁～C₆Alkyl of (2), said "C substituted by one or more of fluorine, chlorine and bromine atoms₁～C₆The alkyl group of (a) is preferably "methyl group substituted with one or more of fluorine, chlorine and bromine atoms", "ethyl group substituted with one or more of fluorine, chlorine and bromine atoms", "propyl group substituted with one or more of fluorine, chlorine and bromine atoms", "isopropyl group substituted with one or more of fluorine, chlorine and bromine atoms", "butyl group substituted with one or more of fluorine, chlorine and bromine atoms", "isobutyl group substituted with one or more of fluorine, chlorine and bromine atoms" or "tert-butyl group substituted with one or more of fluorine, chlorine and bromine atoms"; said "fluorine atom-substituted methyl group" is preferably trifluoromethyl group), "halogen-substituted C₁～C₁₀Alkoxy of (C) (said "halogen-substituted C)₁～C₁₀The halogen in the "alkoxy group of (1)" is preferably fluorine, chlorine or bromine, the number of the halogen is 1 to 4, and when a plurality of halogen atoms are present, the halogen atoms may be the same or different; said "halogen-substituted C₁～C₁₀Alkoxy group of (2)' C₁～C₁₀Alkyl of (2)' preferably C₁～C₆Alkyl of said "C₁～C₆The alkyl group of (1) may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a tert-butyl group. Said "halogen-substituted C₁～C₁₀Alkoxy of (A) is "preferably" C substituted by one or more of fluorine, chlorine and bromine atoms₁～C₆Alkoxy of (b), said "C substituted by one or more of fluorine, chlorine and bromine atoms₁～C₆The alkoxy group of (A) is preferably "methoxy group substituted with one or more of fluorine, chlorine and bromine atoms", "ethoxy group substituted with one or more of fluorine, chlorine and bromine atoms", "propoxy group substituted with one or more of fluorine, chlorine and bromine atoms", "fluorineAn isopropoxy group substituted with one or more of chlorine and bromine atoms, a butoxy group substituted with one or more of fluorine, chlorine and bromine atoms, an isobutoxy group substituted with one or more of fluorine, chlorine and bromine atoms, or a tert-butoxy group substituted with one or more of fluorine, chlorine and bromine atoms; said "methoxy group substituted with fluorine atom" is preferably trifluoromethoxy group), C₃～C₁₀Aryl (preferably C)₃～C₆Aryl of said "C₃～C₆Aryl of (a) is preferably phenyl,

(e.g. in

)、

(e.g. in

)、

(e.g. in

)、

(preferred is

) When a plurality of substituents are present, the substituents may be the same or different; wherein R is³、R⁴、R⁶And R⁷Each independently is a hydrogen atom or C₁～C₆Alkyl (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or tert-butyl); r⁵Is a hydrogen atom, C₁～C₆Alkyl (e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl orT-butyl) or "C with 1-2 heteroatoms being nitrogen atoms₃～C₆(iii) a heterocycloalkyl group of (i) (said "C having 1 to 2 hetero atoms and a nitrogen atom as a hetero atom₃～C₆The heterocycloalkyl group of (1) is preferably C in which the heteroatom is a nitrogen atom and the number of heteroatoms is 1₃～C₄The "hetero atom is a nitrogen atom, and the number of hetero atoms is 1C₃～C₄Heterocycloalkyl of (A) such as

)。

R²Is H or substituted or unsubstituted C₁～C₁₀Alkyl (said "unsubstituted C)₁～C₁₀Alkyl groups of "such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, or decyl; said "substituted C₁～C₁₀Alkyl groups of "such as substituted methyl, substituted ethyl, substituted propyl, substituted butyl, substituted pentyl, substituted hexyl, substituted heptyl, substituted nonyl, or substituted decyl; said "substituted methyl" is for example

Said "substituted propyl" is, for example

) (ii) a Said "substituted or unsubstituted C₁～C₁₀The substituent mentioned in "alkyl" means substituted by C₅～C₁₀Aryl (preferably phenyl) of (a).

In the present invention, the compound A (A)

) Further preferred is any of the following compounds:

in the present invention, TMS represents trimethylsilyl.

In the present invention, the compound

Further preferred is any of the following compounds:

in the present invention, the compound

Further preferred is any of the following compounds:

in the preparation method of the monofluoroalkyl-containing compound, the solvent can be a conventional solvent in the prior art for the Suzuki coupling reaction, and in the invention, one or more of an ether solvent, an alcohol solvent, a chlorinated hydrocarbon solvent, an aromatic hydrocarbon solvent and a sulfoxide solvent are particularly preferred, and an ether solvent is further preferred. The ether solvent is preferably ethylene glycol dimethyl ether (DME) and/or 1, 4-dioxane. The alcohol solvent is preferably isopropanol. The aromatic hydrocarbon solvent can be toluene; the sulfoxide solvent can be dimethyl sulfoxide; the chlorinated hydrocarbon solvent can be 1, 2-dichloroethane.

In the method for producing a monofluoroalkyl group-containing compound, the volume molar ratio of the solvent to the compound B is preferably 1mL/mmol to 100mL/mmol, and more preferably 1mL/mmol to 10 mL/mmol.

In the preparation method of the compound containing the monofluoroalkyl, the base can be the same as the base in the fieldThe conventional bases for the Suzuki coupling reaction, particular preference being given in the context of the present invention to alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal phosphates or "alkali metals and C₁～C₄Salts formed with alcohols "; the alkali metal carbonate is preferably one or more of potassium carbonate, sodium carbonate and cesium carbonate, more preferably potassium carbonate and/or sodium carbonate, and still more preferably potassium carbonate. The alkali metal phosphate is preferably potassium phosphate. Said "alkali metal with C₁～C₄Salts with alcohols "C₁～C₄Alcohol "is preferably methanol, ethanol, propanol, isopropanol or tert-butanol; said "alkali metal with C₁～C₄The "alkali metal" described in the "alcohol-forming salt" is preferably lithium, sodium, potassium, rubidium or cesium; said "alkali metal with C₁～C₄The salt of an alcohol is preferably lithium tert-butoxide.

In the preparation method of the monofluoroalkyl-containing compound, the molar ratio of the base to the compound B is preferably 1-5, and more preferably 2-3.

In the preparation method of the monofluoroalkyl-containing compound, the ligand can be a ligand conventional in the field of the suzuki coupling reaction, a nitrogen-containing bidentate ligand or a nitrogen-containing tridentate ligand is particularly preferred in the invention, and the nitrogen-containing bidentate ligand is preferably substituted or unsubstituted bipyridyl (the substituted bipyridyl is preferably selected from the group consisting of

) Substituted or unsubstituted 1, 10-phenanthroline (said "unsubstituted 1, 10-phenanthroline" is preferably

The "substituted 1, 10-phenanthroline" is preferably

) Or

(e.g. in

). The nitrogen-containing tridentate ligand is preferably a "substituted or unsubstituted pyridine" (the "substituted pyridine" is preferably

) The term "substituted" as used in the "substituted or unsubstituted bipyridine", "substituted or unsubstituted 1, 10-phenanthroline" or "substituted or substituted pyridine" means substituted with C at a non-ortho position to the hetero atom₁～C₁₀Alkyl (preferably C)₁～C₆Alkyl of said "C₁～C₆Alkyl of (2) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl), C₁～C₁₀Alkoxy (preferably C)₁～C₆Alkoxy of said "C₁～C₆Alkoxy of (e.g. methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy) and

when a plurality of substituents are present, the substituents may be the same or different; r⁸、R⁹、R¹⁰And R¹¹Are each hydrogen or C₁～C₃Alkyl (e.g., methyl, ethyl, propyl, or isopropyl); r¹²And R¹³Are respectively hydrogen and C₁～C₃Alkyl (e.g. methyl, ethyl, propyl or isopropyl), C₅～C₁₀Aryl (e.g. phenyl) or R¹²、R¹³And the carbon atoms to which they are attached together form a 4-6 membered cyclic structure (e.g., a six membered cyclic structure

)。

In the process for producing a monofluoroalkyl group-containing compound, the ligand is more preferably

Still further preferred

In the preparation method of the monofluoroalkyl group-containing compound, the molar ratio of the ligand to the compound B is preferably 0.01 to 0.1, and more preferably 0.05 to 0.1.

In the preparation method of the compound containing monofluoroalkyl, the nickel salt is preferably nickel dimethyldiethoxide chloride (NiCl)₂DME), 1,2 bis (diphenylphosphino) ethanenickel chloride (NiCl)₂Dppe), nickel chloride (NiCl)₂) Nickel bromide (NiBr)₂) Nickel iodide (NiI)₂) Nickel chloride hexahydrate (NiCl)₂·6H₂O), nickel bromide trihydrate (NiBr)₂·3H₂O), nickel acetate (Ni (OAc)₂) Nickel acetylacetonate (Ni (acac)₂) Bis (triphenylphosphine) nickel chloride (NiCl)₂(PPh₃)₂) Or nickel nitrate hexahydrate (Ni (NO)₃)₂·6H₂O); further preferred is nickel dimethyldiethoxide chloride (NiCl)₂DME), nickel nitrate hexahydrate (Ni (NO)₃)₂·6H₂O) or nickel chloride (NiCl) 1, 2-bis (diphenylphosphino) ethane₂Dppe), and still more preferably nickel dimethyletherchloride (NiCl)₂·DME)。

In the preparation method of the monofluoroalkyl-containing compound, the molar ratio of the catalyst to the compound B is preferably 0.01 to 0.1, and more preferably 0.05 to 0.1.

In the process for producing a monofluoroalkyl group-containing compound, the additive is preferably one or more of pyridine, 4-trifluoromethylpyridine, 4-methylpyridine, 2, 6-dimethylpyridine, 4-Dimethylaminopyridine (DMAP) and 4-methoxypyridine (4-MeO-Py), more preferably 4-Dimethylaminopyridine (DMAP) and/or 4-methoxypyridine (4-MeO-Py), and still more preferably 4-Dimethylaminopyridine (DMAP).

In the preparation method of the monofluoroalkyl-containing compound, the molar ratio of the compound A to the compound B is preferably 0.5-2, and more preferably 0.75-1.5.

In the preparation method of the monofluoroalkyl-containing compound, the molar ratio of the additive to the compound B is preferably 0.01 to 0.1, and more preferably 0.05 to 0.1.

In the preparation method of the compound containing the monofluoroalkyl, the temperature of the Suzuki coupling reaction is preferably 20-120 ℃, and more preferably 70-80 ℃.

In the preparation method of the monofluoroalkyl group-containing compound, the progress of the Suzuki coupling reaction can be monitored by a detection method (e.g., TLC, HPLC, or NMR) which is conventional in the art, and the reaction time is generally 1 hour to 48 hours, and more preferably 8 hours to 24 hours, with the disappearance of the compound B as a reaction end point.

The invention also provides a compound shown as a formula C,

R¹CHR²F

C

wherein R is¹And R²The definitions of (A) and (B) are as described above.

The invention also provides application of the compound C in preparation of medicines, pesticides or medical materials. Due to its unique properties (such as metabolic stability, lipid solubility, etc.), the compound C of the present invention can be widely applied in the fields of medicines, pesticides or medical materials, such as the cases reported in the following documents: (a) t.hiyama.organofluorine Compounds: chemistry and Applications, Springer, New York, 2000, (b) w.k.hagmann, j.med.chem.2008, 51, 4359, (c) c.ni, l.zhu, j.hu, Acta chim.sinica.2015, 78, 90, (d) D.O' hagan.chem.soc.rev.2008, 37, 308.

In the present invention, when not particularly specified, the "alkyl group" includes a branched or straight chain saturated aliphatic hydrocarbon group having a specified number of carbon atoms; as in "C₁～C₂₀Alkyl is defined to include groups having 1,2, 3,4, 5, 6, 7, 8, 9, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms in a straight or branched chain configuration. For example, "C₁～C₁₀The alkyl group "specifically includes methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like.

In the present invention, when not particularly specified, the "alkoxy group" represents a group formed by bonding an alkyl group to an oxygen atom, that is "

", R is alkyl.

In the present invention, when not particularly specified, the "alkylthio group" means a group formed by bonding an alkyl group to a sulfur atom, that is "

", R is alkyl.

In the present invention, the "alkylsilyl group" is a structure when not particularly specified

In, R¹’、R^2’And R³' at least one of them is an alkyl group, and the others are hydrogen groups.

In the present invention, when not specifically stated, the term "heterocycloalkyl" as used herein alone or as part of another group refers to a 4-12 membered monocyclic or polycyclic group containing 1-4 heteroatoms (e.g., one or more of nitrogen, oxygen, and sulfur), wherein each ring may contain one or more double bonds, but none of the rings have a completely conjugated pi-electron system. In addition, any heterocycloalkyl ring can be fused to a cycloalkyl, aryl, heteroaryl, or heterocycloalkyl ring. Heterocycloalkyl groups within the scope of this definition include, but are not limited to: oxazoline, oxetanyl, pyranyl, tetrahydropyranyl, azetidinyl, 1, 4-dioxanyl, hexahydroazepinyl, piperazinyl, piperidinyl, pyrrolidinyl, morpholinyl, thiomorpholinyl, dihydrofuranyl, dihydroimidazolyl, dihydroindolyl, dihydroisoxazolyl, dihydroisothiazolyl, dihydrooxadiazolyl, dihydrooxazolyl, dihydropyrazinyl, dihydropyrazolyl, dihydropyridinyl, dihydropyrimidinyl, dihydropyrrolyl, dihydrotetrazolyl, dihydrothiadiazolyl, dihydrothiazolyl, dihydrothienyl, dihydrotriazolyl, dihydroazetidinyl, tetrahydrofuranyl and tetrahydrothienyl, and N-oxides thereof. The heterocycloalkyl group may be attached to other groups via a carbon atom or a heteroatom therein.

In the present invention, unless otherwise specified, the term "aryl" refers to any stable monocyclic or bicyclic carbon ring of up to 7 atoms in each ring, wherein at least one ring is aromatic; examples of the above aryl unit include phenyl, naphthyl, tetrahydronaphthyl, 2, 3-indanyl, biphenyl, phenanthryl, anthryl or acenaphthenyl (acenaphthyl). It will be understood that where the aryl substituent is a bicyclic substituent and one of the rings is non-aromatic, the attachment is through an aromatic ring.

In the present invention, when not particularly specified, "aryloxy" means an aryl group having the number of carbon atoms as described, which is linked through an oxygen bridge. Thus, "aryloxy" encompasses the definition of aryl above.

In the present invention, when not specifically defined, the "heteroaryl" refers to a stable monocyclic or bicyclic ring of up to 7 atoms in each ring, wherein at least one ring is aromatic and contains 1 to 4 heteroatoms selected from O, N and S; heterocyclic aryl groups within the scope of this definition include, but are not limited to: acridinyl, carbazolyl, cinnolinyl, quinoxalinyl, pyrazolyl, indolyl, benzotriazolyl, furanyl, thienyl, benzothienyl, benzofuranyl, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, indolyl, pyrazinyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, tetrahydroquinoline. As defined below for heterocycles, "heterocycloaryl" is also to be understood to include any N-oxide derivative of a nitrogen-containing heteroaryl group. In the case where the heterocyclic aryl substituent is a bicyclic substituent and one ring is non-aromatic or contains no heteroatoms, it is understood that the attachment is via the aromatic ring or via the heteroatoms containing the ring, respectively.

In the present invention, when not specifically stated, "halogen" means fluorine, chlorine, bromine, iodine or astatine.

In the present invention, "C" defining the carbon number range_x1～C_y1"substituents (x1 and y1 are integers)" such as "C_x1～C_y1"alkyl group", "C_x1～C_y1"alkoxy group", "C_x1～C_y1Aryl of "or" C_x1～C_y1"heteroaryl or" C_x1～C_y1The alkoxycarbonyl groups of "each represent a carbon number not having a substituent, e.g. C₁～C₁₀Alkyl represents unsubstituted C₁～C₁₀An alkyl group.

The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.

The reagents and starting materials used in the present invention are commercially available.

In the invention, the room temperature refers to the ambient temperature and is 10-35 ℃.

The positive progress effects of the invention are as follows: the preparation method can introduce fluoroalkyl through one-step reaction, is efficient, simple and convenient, has good functional group compatibility and strong broad spectrum property, can avoid using a highly toxic reagent, is simple and safe in post-treatment operation, is environment-friendly, has cheap and low consumption of a catalyst, is mild in reaction conditions, high in reaction conversion rate, high in yield and low in production cost, and is suitable for industrial production. The compound containing fluoroalkyl prepared by the invention has wide application in preparing medicines, pesticides or medical materials due to unique properties (such as metabolic stability, fat solubility and the like), and has good market prospect.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

The raw materials adopted in the embodiment of the invention are commercially available, and can also be prepared by the methods reported in references X.Jiang, S.akthevil, K.Kulbitski, G.Nisnevich, M.Gandelman.J.Am.chem.Soc.2014, 136, 9548-.

Example 1

Into a 25mL reaction tube, 178mg (0.9mmol) of 4-biphenylboronic acid, 6.6mg (5 mol%, mol% means NiCl) were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 90% and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.61-7.69(m，4H)，7.45-7.52(m，4H)，7.40(t，J＝7.3Hz，1H)，5.45(d，J＝47.9Hz，2H).¹³C NMR(100MHz，CDCl₃)141.7(d，J＝3.2Hz)，140.6(d，J＝1.1Hz)，135.1(d，J＝17.1Hz)，128.8，128.0(d，J＝5.7Hz)，127.5，127.3(d，J＝1.4Hz)，127.1(d，J＝0.5Hz)，84.4(d，J＝166.0Hz).¹⁹F NMR(376MHz，CDCl₃)-206.2(t，J＝47.9Hz，1F).

Example 2

To a 25mL reaction tube, 195mg (0.9mmol) of 2-fluorobiphenyl-4-boronic acid, 6.6mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 83% and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.58-7.53(m，2H)，7.50-7.44(m，3H)，7.43-7.37(m，1H)，7.24-7.17(m，2H)，5.42(d，J＝47.5Hz，1H).¹³C NMR(125.7MHz，CDCl₃)159.7(d，J＝249.0Hz)，137.5(dd，J＝17.6，7.7Hz)，135.3，131.0(dd，J＝3.8，0.8Hz)，129.3(dd，J＝13.7，2.8Hz)，129.0(d，J＝2.9Hz)，128.5，127.9，123.0(dd，J＝6.1，3.7Hz)，114.9(dd，J＝23.9，6.4Hz)，83.5(dd，J＝168.0，1.6Hz).¹⁹F NMR(376MHz，CDCl₃) -117.4-117.7 (m, 1F), -209.3(t, J ═ 47.5Hz, 1F)_max 3034，2926，2361，1583，1421，1274，1011cm^-1.MS(EI)：m/z(％)204(M⁺100), 183, 170, 127. HRMS: normalized for (theoretical value) C₁₃H₁₀F₂: 204.0751, respectively; found (Found): 204.0750.

example 3

Into a 25mL reaction tube, 178mg (0.9mmol) of 3-biphenylboronic acid, 13.2mg (10 mol%, mol% means NiCl) were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 10.8mg (10 mol%, mol% being the percentage of phen to compound B) phen (1, 10' -phenanthroline), 14.4mg (10 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 90% and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.67-7.60(m，4H)，7.54-7.46(m，3H)，7.44-7.38(m，2H)，5.48(d，J＝47.8Hz，2H).¹³C NMR(125.7MHz，CDCl₃)141.6(d，J＝1.3Hz)，140.7，136.7(d，J＝17.1Hz)，129.0(d，J＝1.1Hz)，128.8，127.56，127.54(d，J＝2.0Hz)，127.1，126.3(d，J＝5.8Hz)，126.2(d，J＝5.9Hz)，84.6(d，J＝166.5Hz).¹⁹F NMR(376MHz，CDCl₃) -207.3(t, J ═ 47.9Hz, 1F)_max 3033，1598，1481，1241，1028cm^-1Ms (ei): m/z (%) 186(100), 165, 152, 109. HRMS: normalized for (theoretical value) C₁₃H₁₁F: 186.0845, respectively; found (Found): 186.0841.

example 4

To a 25mL reaction tube, 160mg (0.9mmol) of 4-tert-butylboronic acid, 6.6mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂FBr 1, 4-dioxane solution (concentration: 2M, 0.6mmol), stirred at 70 deg.C for 24 hr, and separatedThe yield is 75%, and the purity is more than 95% through hydrogen spectrum identification.¹H NMR(400MHz，CDCl₃)7.46(d，J＝7.9Hz，2H)，7.36(dd，J＝8.3Hz，1.8Hz，2H)，5.38(d，J＝48.1Hz，2H)，1.37(s，9H).¹³C NMR(125.7MHz，CDCl₃)151.9(d，J＝3.4Hz)，133.2(d，J＝17.2Hz)，127.6(d，J＝5.3Hz)，125.5(d，J＝1.9Hz)，84.5(d，J＝165.0Hz)，34.7，31.3.¹⁹F NMR(376MHz，CDCl₃)-204.4(t，J＝48.1Hz，1F).

Example 5

To a 25mL reaction tube, 175mg (0.9mmol) of 4-ethoxycarbonylphenylboronic acid, 6.6mg (5 mol%, mol% means NiCl) were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂After stirring a 1, 4-dioxane solution of FBr (concentration: 2M, 0.6mmol) at 70 ℃ for 24 hours, the isolated yield was 74% and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)8.07(d，J＝7.7Hz，2H)，7.43(d，J＝7.4Hz，2H)，5.45(d，J＝47.2Hz，2H)，4.39(q，J＝7.1Hz，2H)，1.40(t，J＝7.1Hz，3H).¹³C NMR(101MHz，CDCl₃)166.1，141.0(d，J＝17.2Hz)，130.6(d，J＝2.3Hz)，129.7，126.5(d，J＝6.5Hz)，83.6(d，J＝168.4Hz)，61.0，14.2.¹⁹F NMR(376MHz，CDCl₃) -212.7(t, J ═ 47.2Hz, 1F)_max2983，1716，1418，1310，1106，1021cm^-1.MS(EI)：m/z(％)182(M⁺) 154, 137(100). HRMS: normalized for (theoretical value) C₁₀H₁₁FO₂: 182.0743, respectively; found (Found): 182.0739.

Gram-scale synthesis: into a 100mL reaction tube, 2.91g (15mmol) of 4-ethoxycarbonylphenylboronic acid, 110mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 90mg (5 mol%, mol% being the percentage of phen to compound B) phen (1, 10' -phenanthroline), 122mg (5 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 2.76g (20mmol) K₂CO₃33mL of ethylene glycol dimethyl ether, 28mL of 1, 4-dioxane, and 5mL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 78% and the purity was greater than 95% as determined by hydrogen spectroscopy.

Example 6

To a 25mL reaction tube, 175mg (0.9mmol) of 3-ethoxycarbonylphenylboronic acid, 6.6mg (5 mol%, mol% means NiCl) were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 42% and the purity was greater than 95% by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)8.07-8.01(m，2H)，7.56(d，J＝7.8Hz，1H)，7.47(t，J＝7.7Hz，1H)，5.42(d，J＝47.5Hz，2H)，4.38(q，J＝7.1Hz，2H)，1.40(t，J＝7.1Hz，3H).¹³C NMR(101MHz，CDCl₃)166.1，136.5(d，J＝17.5Hz)，131.5(d，J＝5.8Hz)，130.8，129.7(d，J＝2.5Hz)，128.6，128.3(d，J＝6.2Hz)，83.9(d，J＝167.5Hz)，61.1，14.2.¹⁹F NMR(376MHz，CDCl₃) -208.9(t, J ═ 47.6Hz, 1F)_max 2983，1719，1447，1286，1107cm^-1.MS(EI)：m/z(％)182(M⁺) 154, 137(100). HRMS: normalized for (theoretical value) C₁₀H₁₁FO₂: 182.0743, respectively; found (Found): 182.0740.

example 7

To a 25mL reaction tube, 148mg (0.9mmol) of 4-acetylphenylboronic acid, 6.6mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 73% and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.96(d，J＝7.6Hz，2H)，7.43(dd，J＝7.9Hz，0.6Hz，2H)，5.43(d，J＝47.2Hz，2H)，2.59(s，3H).¹³C NMR(125.7MHz，CDCl₃)197.5，141.3(d，J＝17.0Hz)，137.0(d，J＝2.4Hz)，128.5，126.7(d，J＝6.7Hz)，83.5(d，J＝168.4Hz)，26.5.¹⁹F NMR(376MHz，CDCl₃) -213.1(t, J ═ 47.1Hz, 1F)_max 2961，2041，1685，1612，1414，1267，1012cm^-1.MS(EI)：m/z(％)152(M⁺) 149, 137(100), 109, 83. HRMS: normalized for (theoretical value) C₉H₉FO: 152.0637, respectively; found (Found): 152.0635.

example 8

To a 25mL reaction tube, 135mg (0.9mmol) of 3-formylphenylboronic acid, 13.2mg (10 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 10.8mg (10 mol%, mol% being the percentage of phen to compound B) phen (1, 10' -phenanthroline), 14.4mg (10 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 80% and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)10.05(s，1H)，7.91-7.86(m，2H)，7.65(d，J＝7.6Hz，1H)，7.58(t，J＝7.5Hz，1H)，5.47(d，J＝47.3Hz，2H).¹³C NMR(125.7MHz，CDCl₃)191.8，137.3(d，J＝17.7Hz)，136.6，132.9(d，J＝5.9Hz)，129.9(d，J＝2.4Hz)，129.3，128.0(d，J＝6.3Hz)，83.5(d，J＝168.2Hz).¹⁹F NMR(376MHz，CDCl₃) -212.7(t, J ═ 47.2Hz, 1F)_max2918，2849，1685，1420，1089cm^-1.MS(EI)：m/z(％)138(M⁺) 137, 109(100), 83. HRMS: normalized for (theoretical value) C₈H₇FO: 138.0481, respectively; found (Found): 138.0477.

example 9

To a 25mL reaction tube, 135mg (0.9mmol) of 4-formylphenylboronic acid, 6.6mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Nickel dimethyl Ether chloride), 5.4mg (5 mol%, mol% being the molar percentage of phen to Compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% beingMeaning the percentage of the molar amount of DMAP relative to the compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 67% and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(500MHz，CDCl₃)10.02(s，1H)，7.90(d，J＝7.5Hz，2H)，7.52(d，J＝7.8Hz，2H)，5.47(d，J＝47.0Hz，2H).¹³C NMR(125.7MHz，CDCl₃)191.7，142.8(d，J＝17.1Hz)，136.3(d，J＝2.1Hz)，129.9，126.9(d，J＝6.9Hz)，83.4(d，J＝169.4Hz).¹⁹F NMR(376MHz，CDCl₃) -214.2(t, J ═ 47.0Hz, 1F)_max 2958，2832，1701，1612，1426，1211cm^-1.MS(EI)：m/z(％)138(M⁺) 137(100), 109, 83 HRMS: normalized for (theoretical value) C₈H₇FO: 138.0481, respectively; found (Found): 138.0477.

example 10

To a 25mL reaction tube, 132mg (0.9mmol) of 4-cyanophenylboronic acid and 6.6mg (5 mol%, mol% means NiCl) of 4-cyanophenylboronic acid were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 81% and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(500MHz，CDCl₃)7.67(d，J＝7.7Hz，2H)，7.45(dd，J＝8.0Hz，0.6Hz，2H)，5.44(d，J＝46.9Hz，2H).¹³C NMR(125.7MHz，CDCl₃)141.4(d，J＝17.5Hz)，132.3，126.9(d，J＝6.9Hz)，118.4，112.2(d，J＝2.4Hz)，83.0(d，J＝169.9Hz).¹⁹F NMR(376MHz，CDCl₃)-215.1(t，J＝46.9Hz，1F).

Example 11

To a 25mL reaction tube, 149mg (0.9mmol) of 3-fluoro-4-cyanophenylboronic acid, 6.6mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 73% and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.69-7.62(m，1H)，7.25(s，1H)，7.23-7.20(m，1H)，5.45(d，J＝46.5Hz，2H).¹³C NMR(125.7MHz，CDCl₃)163.2(d，J＝260.1Hz)，144.7(dd，J＝18.4，7.8Hz)，133.8，122.1(dd，J＝7.4，3.6Hz)，114.0(dd，J＝20.9，8.1Hz)，113.6，101.2(d，J＝16.0Hz)，82.3(dd，J＝172.6，1.8Hz).¹⁹F NMR(376MHz，CDCl₃) -105.6(dd, J ═ 9.4, 6.3Hz, 1F), -217.4(t, J ═ 46.6Hz, 1F), IR (thin film process) v_max 3092，2962，2236，1625，1505，1430，1112，738cm^-1.MS(EI)：m/z(％)153(M⁺) 152(100), 125, 107, 75 HRMS: normalized for (theoretical value) C₈H₅F₂N: 153.0390, respectively; found (Found): 153.0385.

example 12

To a 25mL reaction tube, 132mg (0.9mmol) of 3-cyanophenylboronic acid and 6.6mg (5 mol%, mol% means NiCl) of 3-cyanophenylboronic acid were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂The 1, 4-dioxane solution of FBr (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 70% and the purity was greater than 95% by hydrogen spectroscopy.¹H NMR(500MHz，CDCl₃)7.67-7.61(m，2H)，7.62-7.57(m，1H)，7.51(t，J＝7.7Hz，1H)，5.41(d，J＝47.1Hz，2H).¹³C NMR(125.7MHz，CDCl₃)137.7(d，J＝18.1Hz)，132.1(d，J＝2.4Hz)，131.1(d，J＝6.2Hz)，130.3(d，J＝7.0Hz)，129.4，118.3，112.8，82.9(d，J＝169.5Hz).¹⁹F NMR(376MHz，CDCl₃) -212.3(t, J ═ 47.0Hz, 1F)_max 3067，2960，2231，1607，1485，1000cm^-1.MS(EI)：m/z(％)135(M⁺) 134(100), 115, 107 HRMS: normalized for (theoretical value) C₈H₆FN: 135.0484, respectively; found (Found): 135.0483.

example 13

To a 25mL reaction tube, 180mg (0.9mmol) of 4-methanesulfonylphenylboronic acid, 6.6mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Nickel dimethyl Ether chloride), 5.4mg (5 mol%, mol% being the percentage of phen to compound B), phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 84%, and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.97(d，J＝8.0Hz，2H)，7.56(d，J＝7.9Hz，2H)，5.49(d，J＝46.9Hz，2H)，3.06(s，3H).¹³C NMR(100MHz，CDCl₃)142.3(d，J＝17.5Hz)，140.4(d，J＝2.3Hz)，127.6，127.2(d，J＝6.9Hz)，83.0(d，J＝170.0Hz)，44.4.¹⁹F NMR(376MHz，CDCl₃) -215.1(t, J ═ 46.9Hz, 1F.) IR (thin film method) v_max 3078，3000，1601，1411，1305，1146，1010cm^-1.MS(EI)：m/z(％)188(M⁺) 173, 125, 109(100), 83. HRMS: normalized for (theoretical value) C₈H₉FO₂S: 188.0307, respectively; found (Found): 188.0309.

example 14

To a 25mL reaction tube, 230mg (0.9mmol) of 4- (sulfonylpyrroline) phenylboronic acid, 13.2mg (10 mol%, mol% means NiCl) were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 10.8mg (10 mol%, mol% being the percentage of phen to compound B) phen (1, 10' -phenanthroline), 14.4mg (10 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 50% and the purity was greater than 95% by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.86-7.81(m，2H)，7.53-7.47(m，2H)，5.46(d，J＝47.1Hz，2H)，3.26-3.20(m，4H)，1.78-1.70(m，4H).¹³C NMR(125.7MHz，CDCl₃)141.0(d，J＝17.5Hz)，137.1(d，J＝2.1Hz)，127.7，127.1(d，J＝6.7Hz)，83.3(d，J＝169.3Hz)，47.9，25.2.¹⁹F NMR(376MHz，CDCl₃) -213.7(t, J ═ 47.1 Hz.) IR (thin film process) v_max 3097，2886，1460，1334，1164cm^-1.MS(EI)：m/z(％)243(M⁺) 210, 173, 109, 83, 70(100). HRMS: normalized for (theoretical value) C₁₁H₁₄FNO₂S: 243.0729, respectively; found (Found): 243.0727.

example 15

To a 25mL reaction tube, 175mg (0.9mmol) of 4-trimethylsilylphenylboronic acid, 6.6mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 82%, and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.58(d，J＝7.7Hz，2H)，7.39(d，J＝7.0Hz，2H)，5.39(d，J＝47.8Hz，2H)，0.30(s，9H).¹³C NMR(100MHz，CDCl₃)141.3(d，J＝2.5Hz)，136.6(d，J＝17.0Hz)，133.6，126.7(d，J＝5.8Hz)，84.5(d，J＝166.1Hz)，-1.2.¹⁹F NMR(376MHz，CDCl₃) -207.7(t, J ═ 47.8Hz, 1F)_max 3073，2956，1398，1249，1107，989cm^-1.MS(EI)：m/z(％)182(M⁺) 167(100), 137, 77. HRMS: normalized for (theoretical value) C₁₀H₁₅And FSi: 182.0927, respectively; found (Found): 182.0930.

example 16

To a 25mL reaction tube, 172mg (0.9mmol) of 3, 4-dichlorophenylboronic acid and 13.2mg (10 mol%, mol% means NiCl) of₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 10.8mg (10 mol%, mol% being the percentage of phen to compound B) phen (1, 10' -phenanthroline), 14.4mg (10 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 50% and the purity was greater than 95% by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.49-7.43(m，2H)，7.20(d，J＝8.3Hz，1H)，5.33(d，J＝47.3Hz，2H).¹³C NMR(125.7MHz，CDCl₃)136.3(d，J＝18.0Hz)，132.8(d，J＝2.8Hz)，132.7，130.6，129.1(d，J＝6.7Hz)，126.3(d，J＝6.2Hz)，82.9(d，J＝169.2Hz).¹⁹F NMR(376MHz，CDCl₃)-210.1(t，J＝47.3Hz，1F).

Example 17

To a 25mL reaction tube, 251mg (0.9mmol) of 4- ((1-naphthyloxy) methyl) phenylboronic acid, 6.6mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether, 1.7mL1, 4-Dioxahexacyclic injection of 300uL CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 50% and the purity was greater than 95% by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)8.43-8.39(m，1H)，7.88-7.85(m，1H)，7.62-7.57(m，2H)，7.57-7.49(m，3H)，7.47(dd，J＝8.1Hz，1.7Hz，2H)，7.43-7.38(m，1H)，6.90(d，J＝7.5Hz，1H)，5.44(d，J＝47.8Hz，2H)，5.29(d，J＝1.0Hz，2H).¹³C NMR(125.7MHz，CDCl₃)154.3，137.7(d，J＝3.0Hz)，135.8(d，J＝17.0Hz)，134.5，127.7(d，J＝5.8Hz)，127.5，126.4，125.8，125.7，125.2，122.1，120.6，105.2，84.3(d，J＝166.2Hz)，69.6.¹⁹F NMR(376MHz，CDCl₃) -206.7(t, J ═ 47.9Hz, 1F)_max 3060，2927，1579，1469，1267，1096cm^- ¹.MS(EI)：m/z(％)266(M⁺) 123, (100), 115, 103, 77. HRMS: normalized for (theoretical value) C₁₈H₁₅FO: 266.1107, respectively; found (Found): 266.1105.

example 18

To a 25mL reaction tube, 155mg (0.9mmol) of 2-naphthoic acid, 6.6mg (5 mol%, mol% means NiCl) of₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 64% and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.90-7.83(m，4H)，7.54-7.47(m，3H)，5.55(d，J＝47.7Hz，2H).¹⁹F NMR(376MHz，CDCl₃)-206.6(t，J＝47.8Hz，1F).

Example 19

Into a 25mL reaction tube, 214mg (0.9mmol) of 9, 9-dimethylfluorene-2-boronic acid, 6.6mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 50% and the purity was greater than 95% by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.78-7.72(m，2H)，7.49-7.44(m，2H)，7.38-7.34(m，3H)，5.46(d，J＝48.1Hz，2H)，1.52(s，6H).¹³C NMR(125.7MHz，CDCl₃)154.0(d，J＝1.7Hz)，153.8，139.9(d，J＝3.4Hz)，138.6(d，J＝1.6Hz)，135.0(d，J＝16.4Hz)，127.6，127.0，126.8(d，J＝5.7Hz)，122.6，122.2(d，J＝5.7Hz)，120.2，120.0(d，J＝1.5Hz)，85.1(d，J＝165.9Hz)，46.9，27.1.¹⁹F NMR(376MHz，CDCl₃) -203.4(t, J ═ 48.1Hz, 1F.) IR (thin film method) v_max 2960，2923，1472，1449，1216，977cm^-1.MS(EI)：m/z(％)226(M⁺) 211, (100), 191, 178, 98. HRMS: normalized for (theoretical value) C₁₃H₁₀F₂: 226.1158, respectively; found (Found): 226.1154.

example 20

To a 25mL reaction tube, 191mg (0.9mmol) of dibenzofuran-4-boronic acid, 6.6mg (5 mol%, mol% means NiCl) were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 75% and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.96(d，J＝7.7Hz，2H)，7.62(d，J＝8.3Hz，1H)，7.55-7.46(m，2H)，7.41-7.35(m，2H)，5.81(d，J＝47.8Hz，2H).¹³C NMR(125.7MHz，CDCl₃)156.1，153.9(d，J＝3.8Hz)，127.4，126.9(d，J＝6.1Hz)，124.5(d，J＝1.2Hz)，123.9，122.9，122.7(d，J＝1.8Hz)，121.4(d，J＝3.1Hz)，120.7，120.1(d，J＝17.9Hz)，111.8，79.6(d，J＝165.9Hz).¹⁹F NMR(376MHz，CDCl₃)-210.6(t，J＝47.7Hz，1F).

Example 21

To a 25mL reaction tube, 193mg (0.9mmol) of 4-phenoxyphenylboronic acid and 13.2mg (10 mol%, mol% means NiCl) were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 10.8mg (10 mol%, mol% being the percentage of phen to compound B) phen (1, 10' -phenanthroline), 14.4mg (10 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂FBr 1, 4-dioxane solution (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, and then fluorine was addedSpectral yield 61%.¹⁹F NMR(376MHz，CDCl₃)-202.8(t，J＝48.3Hz，1F).GC-MS analysis：m/z(％)202(M⁺)，169，141，109(100)，77，51.

Example 22

To a 25mL reaction tube, 185mg (0.9mmol) of 4-trifluoromethoxybenzeneboronic acid and 6.6mg (5 mol%, mol% means NiCl) of 4-trifluoromethoxybenzeneboronic acid were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, giving a 78% fluorine spectrum yield.¹⁹F NMR(376MHz，CDCl₃)-208.7(t，J＝47.5Hz，1F).

Example 23

To a 25mL reaction tube, 185mg (0.9mmol) of 4-trifluoromethoxybenzeneboronic acid and 6.6mg (5 mol%, mol% means NiCl) of 4-trifluoromethoxybenzeneboronic acid were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, giving a 90% fluorine spectrum yield.¹⁹F NMR(376MHz，CDCl₃)-211.2(t，J＝47.4Hz，1F).

Example 24

To a 25mL reaction tube, 171mg (0.9mmol) of 4-trifluoromethylphenylboronic acid and 6.6mg (5 mol%, mol% means NiCl) were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, giving a fluorine spectrum yield of 84%.¹⁹F NMR(376MHz，CDCl₃)-213.5(t，J＝47.1Hz，1F).

Example 25

To a 25mL reaction tube, 164mg (0.9mmol) of 4-ethylthiophenylboronic acid, 6.6mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (5 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (5 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 166mg (1.2mmol) K₂CO₃2mL of ethylene glycol dimethyl ether and 1.7mL of 1, 4-dioxane were injected with 300uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, giving a 68% fluorine spectrum yield.¹⁹F NMR(376MHz，CDCl₃) -205.5(t, J ═ 48.1Hz, 1F), GC-MS Found (Found): m/z (%)170(M⁺)，155，142，135，109(100)，97，77，51.

Example 26

To a 25mL reaction tube, 134mg (0.45mmol) of estrone phenylboronic acid, 6.6mg (10 mol%, mol% means NiCl) were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (10 mol%, mol% being the percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (10 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 83mg (1.2mmol) K₂CO₃1mL of ethylene glycol dimethyl ether and 0.85mL of 1, 4-dioxane for injection of 150uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 56% and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.33(d，J＝7.9Hz，1H)，7.18(d，J＝7.8Hz，1H)，7.14(s，1H)，5.32(d，J＝48.1Hz，2H)，2.94(d，J＝4.9Hz，2H)，2.61-2.40(m，2H)，2.32(s，1H)，2.22-1.94(m，4H)，1.73-1.39(m，6H)，0.92(s，3H).¹³C NMR(100MHz，CDCl₃)220.7，140.4(d，J＝3.0Hz)，136.8，133.5(d，J＝16.9Hz)，128.4(d，J＝5.4Hz)，125.6，125.1(d，J＝5.2Hz)，84.5(d，J＝165.2Hz)，50.4，47.9，44.3，38.0，35.8，31.5，29.2，26.3，25.6，21.50，13.7.¹⁹F NMR(376MHz，CDCl₃) -204.6(t, J ═ 48.0Hz, 1F.) IR (thin film method) v_max 2967，1735，1612，1452，1255，978cm^-1.MS(EI)：m/z(％)286(M⁺) 253, 242, 229, 164, 107(100). HRMS: normalized for (theoretical value) C₁₉H₂₃FO: 286.1733, respectively; found (Found): 286.1735.

example 27

To a 25mL reaction tube, 184mg (0.45mmol) was added

6.6mg (10 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (10 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (10 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 83mg (1.2mmol) K₂CO₃1mL of ethylene glycol dimethyl ether and 0.85mL of 1, 4-dioxane for injection of 150uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 50% and the purity was greater than 95% by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)8.05(d，J＝7.9Hz，2H)，7.45(d，J＝7.6Hz，2H)，5.96(d，J＝3.6Hz，1H)，5.51(d，J＝2.7Hz，1H)，5.46(d，J＝47.2Hz，2H)4.64(d，J＝3.7Hz，1H)，4.37-4.30(m，2H)，4.14-4.05(m，2H)，1.56(s，3H)，1.41(s，3H)，1.32(s，2H)，1.26(s，3H).¹³C NMR(125.7MHz，CDCl₃)164.7，141.8(d，J＝17.3Hz)，130.0，129.6(d，J＝2.1Hz)，126.6(d，J＝6.7Hz)，112.4，109.4，105.1，83.5(d，J＝169.1Hz)，83.4，80.0，76.7，72.5，67.3，26.8，26.7，26.2，25.2.¹⁹F NMR(376MHz，CDCl₃) -213.6(t, J ═ 47.1Hz, 1F)_max cm^- ¹2990，2940，1729，1617，1386，1016cm^-1.MS(ESI)：m/z(％)419(M+Na)⁺339(100), 299, 274, 167.hrms (esi): normalized for (theoretical value) C₂₀H₂₅FNaO₇: 419.1482, respectively; found (Found): 419.1477.

example 28

To a 25mL reaction tube, 184mg (0.45mmol) of 4- (sulfonyl-2-ethoxycarbonylpiperidine) phenylboronic acid, 6.6mg (10 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 5.4mg (10 mol%, mol% referring to the molar percentage of phen to compound B) phen (1, 10' -phenanthroline), 7.4mg (10 mol%, mol% referring to the molar percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 83mg (1.2mmol) K₂CO₃1mL of ethylene glycol dimethyl ether and 0.85mL of 1, 4-dioxane for injection of 150uL of CH₂A solution of FBr in 1, 4-dioxane (concentration: 2M, 0.6mmol) was stirred at 70 ℃ for 24 hours, the isolated yield was 50% and the purity was greater than 95% by hydrogen spectroscopy.¹H NMR(400MHz，CDCl₃)7.79(d，J＝8.2Hz，2H)，7.45(d，J＝8.0Hz，2H)，5.43(d，J＝47.1Hz，2H)，4.72(d，J＝5.1Hz，1H)，4.04-3.90(m，2H)，3.76(d，J＝10.1Hz，1H)，3.24-3.15(m，1H)，2.12(d，J＝14.2Hz，1H)，1.77-1.60(m，3H)，1.54-1.40(m，1H)，1.30-1.20(m，1H)，1.12(t，J＝7.1Hz，3H).¹³C NMR(100MHz，CDCl₃)170.5，140.7(d，J＝17.5Hz)，140.0(d，J＝2.4Hz)，127.4，126.8(d，J＝6.7Hz)，83.2(d，J＝169.3Hz)，61.0，55.0，42.6，27.8，24.6，19.9，14.0.¹⁹F NMR(376MHz，CDCl₃) -213.7(t, J ═ 47.1Hz, 1F)_max cm^-12974，2888，1743，1381，1159，1050cm^-1.MS(MALDI)：m/z(％)347(M+NH₄)⁺(100)，330(M+H)⁺Hrms (maldi): normalized for (theoretical value) C₁₅H₂₁O₄NFS: found (Found) (M + H)⁺：330.1169.

Example 29

To a 25mL reaction tube, 74.9mg (0.6mmol) DMAP (4-dimethylaminopyridine), 2mL ethylene glycol dimethyl ether, 1.7mL 1, 4-dioxane were added and 300uL CH was injected₂After stirring a 1, 4-dioxane solution of FBr (concentration: 2M, 0.6mmol) at room temperature for 8 hours, the isolated yield was 82% and the purity was greater than 95% as determined by hydrogen spectroscopy.¹H NMR(400MHz，DMSO-d₆)8.51(d，J＝7.9Hz，2H)，7.16(d，J＝7.8Hz，2H)，6.19(d，J＝50.4Hz，2H)，3.26(s，6H).¹³C NMR(125.7MHz，DMSO-d₆)156.8，142.2(d，J＝1.2Hz)，107.8，92.1(d，J＝202.1Hz)，40.3.¹⁹F NMR(376MHz，DMSO-d₆)-164.6(t，J＝50.4Hz，1F).MS(ESI)：m/z(％)155.9，155.0(M-⁷⁹Br，100)⁺.

Example 30

Into a 25mL reaction tube, 66mg (0.45mmol) of 4-cyanophenylboronic acid and 3.3mg (5 mol%, mol% means NiCl) of 4-cyanophenylboronic acid were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 2.7mg (5 mol%, mol% being the percentage of phen to compound B) phen (1, 10' -phenanthroline), 3.7mg (5 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 83mg (1.2mmol) K₂CO₃1mL of ethylene glycol dimethyl ether and 0.85mL of 1, 4-dioxane for injection of 150uL

The 1, 4-dioxane solution (concentration: 2M, 0.3mmol) was stirred at 70 ℃ for 24 hours, and the isolated yield was 57%.¹H NMR(400MHz，CDCl₃)7.62(d，J＝8.1Hz，1H)，7.33(d，J＝8.2Hz，1H)，7.30-7.21(m，1H)，7.10(d，J＝6.3Hz，1H)，5.68(ddd，J＝47.1，7.2，5.4Hz，1H)，3.17(dddd，J＝31.0，19.5，14.2，6.3Hz，1H).¹³C NMR(125.7MHz，CDCl₃)144.8(d，J＝20.5Hz)，135.3(d，J＝4.5Hz)，132.2，129.5，128.5，127.0，126.1(d，J＝7.3Hz)，118.5，112.1(d，J＝1.5Hz)，93.7(d，J＝177.4Hz)，43.7(d，J＝23.7Hz).¹⁹F NMR(376MHz，CDCl₃)-177.9(ddd，J＝47.0，25.6，19.2Hz，1F).

Example 31

To a 25mL reaction tube, 87mg (0.45mmol) of 4-ethoxycarbonylphenylboronic acid and 3.3mg (5 mol%, mol% means NiCl) were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 2.7mg (5 mol%, mol% being the percentage of phen to compound B) phen (1, 10' -phenanthroline), 3.7mg (5 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 83mg (1.2mmol) K₂CO₃1mL of ethylene glycol dimethyl ether and 0.85mL of 1, 4-dioxane for injection of 150uL

The 1, 4-dioxane solution (concentration: 2M, 0.3mmol) was stirred at 70 ℃ for 24 hours, and the isolated yield was 70%.¹HNMR(500MHz，CDCl₃)8.05(d，J＝8.0Hz，2H)，7.34(d，J＝8.4Hz，2H)，7.32-7.25(m，3H)，7.16(d，J＝6.9Hz，2H)，5.70(ddd，J＝47.2，7.6，5.2Hz，1H)，4.41(q，J＝7.1Hz，2H)，3.21(dddd，J＝26.6，19.4，14.2，6.4Hz，2H)，1.42(t，J＝7.1Hz，3H).¹³C NMR(125.7MHz，CDCl₃)166.2，144.5(d，J＝20.0Hz)，135.9(d，J＝4.3Hz)，130.3(d，J＝1.5Hz)，129.6，129.5，128.4，126.80，125.4(d，J＝7.1Hz)，94.2(d，J＝176.0Hz)，61.0，43.8(d，J＝23.9Hz)，14.3.¹⁹F NMR(376MHz，CDCl₃) -176.4(ddd, J ═ 47.4, 26.7, 18.6Hz, 1F). IR (thin film process) v_max 3086，1941，1713，1614，1472，1280，1042cm^-1Ms (ei): m/z (%) 272(M +), 227, 181, 91(100). HRMS: normalized for (theoretical value) C₁₇H₁₇FO₂: 272.1213, respectively; found (Found): 272.1213.

example 32

To a 25mL reaction tube, 74mg (0.45mmol) of 4-acetylphenylboronic acid, 3.3mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 2.7mg (5 mol%, mol% being the percentage of phen to compound B) phen (1, 10' -phenanthroline), 3.7mg (5 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 83mg (1.2mmol) K₂CO₃1mL of ethylene glycol dimethyl ether and 0.85mL of 1, 4-dioxane for injection of 150uL

The 1, 4-dioxane solution (concentration: 2M, 0.3mmol) was stirred at 70 ℃ for 24 hours, and the isolated yield was 60%.¹H NMR(500MHz，CDCl₃)7.96(d，J＝8.0Hz，2H)，7.39(d，J＝8.3Hz，2H)，7.29(t，J＝7.4Hz，2H)，7.20(d，J＝7.4Hz，1H)，7.17(dd，J＝7.5，0.5Hz，2H)，5.52(ddd，J＝11.7，7.9，4.2Hz，1H)，2.68(t，J＝7.4Hz，2H)，2.61(s，3H)，2.01-1.72(m，4H).¹³C NMR(125.7MHz，CDCl₃)197.5，145.5(d，J＝19.9Hz)，141.6，136.8(d，J＝1.3Hz)，128.5，128.3(d，J＝0.6Hz)，125.9，125.4，125.33，93.7(d，J＝172.7Hz)，36.6(d，J＝23.1Hz)，35.4，26.6，26.5(d，J＝3.9Hz).¹⁹F NMR(376MHz，CDCl₃) -178.9(ddd, J ═ 48.1, 28.2, 18.8Hz, 1F), ms (ei): m/z (%) 271(M +1)270(M +), 255, 207, 165, 104, 91(100), 77, 43. HRMS: normalized for (theoretical value) C₁₈H₁₉FO: 270.1420, respectively; found (Found): 270.1425.

example 33

To a 25mL reaction tube, 86mg (0.45mmol) of 4-trifluoromethyl was addedPhenylboronic acid, 3.3mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 2.7mg (5 mol%, mol% being the percentage of phen to compound B) phen (1, 10' -phenanthroline), 3.7mg (5 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 83mg (1.2mmol) K₂CO₃1mL of ethylene glycol dimethyl ether and 0.85mL of 1, 4-dioxane for injection of 150uL

The 1, 4-dioxane solution (concentration: 2M, 0.3mmol) was stirred at 70 ℃ for 24 hours, and the isolated yield was 70%.¹H NMR(500MHz，CDCl₃)7.64(d，J＝8.1Hz，2H)，7.42(d，J＝8.0Hz，2H)，7.31(t，J＝7.5Hz，2H)，7.22(d，J＝7.4Hz，1H)，7.19(d，J＝7.1Hz，2H)，5.52(ddd，J＝47.4，7.9，3.9Hz，1H)，2.70(t，J＝7.4Hz，2H)，2.02-1.74(m，4H).¹⁹F NMR(376MHz，CDCl₃) -62.6(s, 3F), -178.8(ddd, J ═ 47.8, 28.6, 18.8Hz, 1F). IR (thin film process) v_max 3030，1931，1621，1463，1325，1066cm^-1Ms (ei): m/z (%) 269(M +), 277, 177, 127, 104, 91(100), 65. HRMS: normalized for (theoretical value) C₁₇H₁₆F₄: 296.1188, respectively; found (Found): 296.1190.

example 34

To a 25mL reaction tube, 68mg (0.45mmol) of 4-formylphenylboronic acid, 3.3mg (5 mol%, mol% means NiCl)₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 2.7mg (5 mol%, mol% being the percentage of phen to compound B) phen (1, 10' -phenanthroline), 3.7mg (5 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 83mg (1.2mmol) K₂CO₃1mL of ethylene glycolMethylether, 0.85mL 1, 4-dioxane, injected 150uL

The 1, 4-dioxane solution (concentration: 2M, 0.3mmol) was stirred at 70 ℃ for 24 hours, and the isolated yield was 85%.¹H NMR(500MHz，CDCl₃)10.01(s，1H)，7.88(d，J＝8.1Hz，2H)，7.47(d，J＝8.0Hz，2H)，5.50(ddd，J＝47.9，8.0，4.7Hz，1H)，1.96-1.75(m，2H)，1.42-1.19(m，12H)，0.87(t，J＝6.8Hz，3H).¹³C NMR(125.7MHz，CDCl₃)191.7，147.3(d，J＝19.9Hz)，136.0(d，J＝1.2Hz)，129.8，125.8(d，J＝7.6Hz)，93.8(d，J＝172.9Hz)，37.2(d，J＝23.0Hz)，31.8，29.34，29.3，29.1，24.8(d，J＝4.0Hz)，22.6，14.0.¹⁹F NMR(376MHz，CDCl₃) 179.3(ddd, J ═ 48.1, 29.0, 18.4Hz, 1F). IR (thin film method) v_max 3389，2926，1705，1612，1466，1210，1065cm^-1Ms (ei): m/z (%) 250(M +), 138(100), 132, 109, 91, 71, 57, 43. HRMS: normalized for (theoretical value) C₁₆H₂₃FO: 250.1733, respectively; found (Found): 250.1734.

example 35

1, 4-dioxane solution (concentration: 2M,0.3mmol), and after stirring at 70 ℃ for 24 hours, the isolated yield was 81%.¹HNMR.¹HNMR(500MHz，CDCl₃)7.66(d，J＝8.1Hz，2H)，7.42(d，J＝8.4Hz，2H)，5.47(ddd，J＝47.8，8.0，4.6Hz，1H)，1.93-1.74(m，2H)，1.44-1.13(m，12H)，0.87(t，J＝7.0Hz，3H).¹³C NMR(125.7MHz，CDCl₃)145.9(d，J＝20.3Hz)，132.2，125.9(d，J＝7.7Hz)，118.6，111.9(d，J＝1.6Hz)，93.4(d，J＝173.6Hz)，37.2(d，J＝22.9Hz)，31.8，29.33，29.2，29.1，24.8(d，J＝4.0Hz)，22.6，14.0.¹⁹F NMR(376MHz，CDCl₃) -180.0(ddd, J ═ 47.8, 30.0, 18.8Hz, 1F). IR (thin film method) v_max cm^-12927, 2856, 2230, 1612, 1466, 1061.ms (ei): m/z (%) 247(M +), 135(100), 129, 107, 71, 57 HRMS: normalized for (theoretical value) C₁₆H₂₂NF: 247.1736, respectively; found (Found): 247.1735.

example 36

To a 25mL reaction tube, 89mg (0.45mmol) of 4-biphenylboronic acid and 3.3mg (5 mol%, mol% means NiCl) of 4-biphenylboronic acid were added₂Molar percentages of DME and Compound B) NiCl₂DME (Dimethylethylenediethernickel chloride), 2.7mg (5 mol%, mol% being the percentage of phen to compound B) phen (1, 10' -phenanthroline), 3.7mg (5 mol%, mol% being the percentage of DMAP to compound B) DMAP (4-dimethylaminopyridine), 83mg (1.2mmol) K₂CO₃1mL of ethylene glycol dimethyl ether and 0.85mL of 1, 4-dioxane for injection of 150uL

The 1, 4-dioxane solution (concentration: 2M, 0.3mmol) was stirred at 70 ℃ for 24 hours, and the fluorine spectrum yield was 50%.

Examples 37 to 50

To a 25mL reaction tube, 4-biphenylboronic acid (0.45mmol), a nickel salt, a ligand, a base, an additive, and a solvent (2mL) were added, and 150uL of CH was injected₂The reaction was terminated by stirring a 1, 4-dioxane solution (concentration: 2M, 0.6mmol) of FBr at 70 ℃ for 12 hours.

The reaction conditions and the product fluorine spectrum yield of each of examples 37 to 48 are shown in table 1, and the target compound was obtained as a white solid; the fluorine spectrum yield refers to the fluorine spectrum yield taking fluorobenzene as an internal standard.

TABLE 1

Examples 51 to 79

The reaction conditions and the product yields of examples 51 to 79 are shown in table 2, and the objective compound was obtained as a white solid.

TABLE 2

Examples 80 to 81

To a 25mL reaction tube, 4-biphenylboronic acid (0.45mmol), a nickel salt, a ligand, a base, an additive, and a solvent (2mL) were added, and 1 was injected50uL CH₂The reaction was terminated by stirring a 1, 4-dioxane solution (concentration: 2M, 0.6mmol) of FBr at 70 ℃ for 24 hours.

The reaction conditions and the product yields of each of examples 80 to 81 are shown in Table 3, and the objective compound was obtained as a white solid.

TABLE 3

All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.

Claims

1. A process for preparing a monofluoroalkyl containing compound, comprising the steps of: in a solvent, under the condition that alkali, an additive, a ligand and a catalyst exist, carrying out a suzuki coupling reaction on a compound A and a compound B to obtain a compound C, wherein the catalyst is nickel salt, and the nickel salt is NiL_nCl₂、NiL_nBr₂、NiL_nI₂Or NiQ_2·mH₂O；

Wherein Q is nitrate radical, and m is more than or equal to 0 and less than or equal to 10; and n is 1,2 or 3; l is triphenylphosphine, o-methoxytriphenylphosphine, o-methyltriphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triamantylphosphine, 1,2 bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1' -bis (diphenylphosphino) ferrocene, bis-diphenylphosphinomethane, 1, 2-bis-triphenylphosphine benzene, dimethyl ethylene glycol diether, diethylene glycol dimethyl ether, substituted or unsubstitutedSubstituted 1, 10-phenanthroline "," substituted or unsubstituted pyridine ", substituted or unsubstituted bipyridine or

The "substitution" in the "substituted or unsubstituted bipyridine", "substituted or unsubstituted 1, 10-phenanthroline" or "substituted or unsubstituted pyridine" means a substitution by C in a non-ortho position to a hetero atom₁～C₁₀Alkyl of (C)₁～C₁₀Alkoxy group of (1) and

when a plurality of substituents are present, the substituents may be the same or different; x is halogen; r⁸、R⁹、R¹⁰And R¹¹Are each hydrogen or C₁～C₃Alkyl groups of (a); r¹²And R¹³Are respectively hydrogen and C₁～C₃Alkyl of (C)₅～C₁₀Aryl or R of¹²、R¹³And the carbon atoms to which they are attached together form a 4-6 membered cyclic structure; r¹Is "substituted or unsubstituted C₃～C₁₅Aryl of (2) and (2) substituted or unsubstituted C, the hetero atom being an oxygen, sulfur or nitrogen atom, the number of hetero atoms being 1 to 3₂～C₁₅Heteroaryl of "or

Said "substituted or unsubstituted C₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅The "substitution" in "heteroaryl group of (A) is by cyano, halogen, C₁～C₁₀Alkyl of (C)₁～C₁₀Alkoxy group of (C)₅～C₁₀Aryloxy group of (A), C₁～C₁₀Alkylthio of, C₁～C₁₀Alkylsilyl group, "halogen substituted C₁～C₁₀Alkyl of (2), "halogen substitutedC₁～C₁₀Alkoxy group of ″, C₃～C₁₀Aryl of (a),

When a plurality of substituents are present, the substituents may be the same or different; wherein R is³、R⁴、R⁶And R⁷Are each a hydrogen atom or C₁～C₆Alkyl groups of (a); r⁵Is a hydrogen atom, C₁～C₆Alkyl or "C with 1-2 hetero atoms being nitrogen atoms₃～C₆The heterocycloalkyl group of (1); r²Is H or substituted or unsubstituted C₁～C₁₀Alkyl groups of (a); said "substituted or unsubstituted C₁～C₁₀The substituent mentioned in "alkyl" means substituted by C₅～C₁₀Aryl of (a);

the solvent is an ether solvent and/or an alcohol solvent, the ether solvent is ethylene glycol dimethyl ether and/or 1, 4-dioxane, and the alcohol solvent is isopropanol;

the alkali is alkali metal carbonate, alkali metal phosphate or' alkali metal and C₁～C₄Alcohol-formed salt ", the alkali metal carbonate is potassium carbonate and/or sodium carbonate, the alkali metal phosphate is potassium phosphate, and the alkali metal and C are₁～C₄The salt of an alcohol "is lithium tert-butoxide;

the additive is one or more of pyridine, 4-trifluoromethyl pyridine, 4-methyl pyridine, 2, 6-dimethyl pyridine, 4-dimethylamino pyridine and 4-methoxyl pyridine.

2. A process for preparing a monofluoroalkyl containing compound according to claim 1, wherein:

m is 0, 1,2, 3,4, 5, 6, 7, 8, 9 or 10;

and/or the presence of a gas in the gas,

when the L is substituted or unsubstituted 1, 10-phenanthroline, the unsubstituted 1, 10-phenanthroline is

And/or the presence of a gas in the gas,

when said "substituted" in said "substituted or unsubstituted bipyridine", "substituted or unsubstituted 1, 10-phenanthroline" or "substituted or unsubstituted pyridine" in said L means substituted with C in a non-ortho position to the heteroatom₁～C₁₀When substituted with an alkyl group of (1), "C" as mentioned₁～C₁₀Alkyl of is C₁～C₆Alkyl groups of (a);

and/or the presence of a gas in the gas,

when said "substituted" in said "substituted or unsubstituted bipyridine", "substituted or unsubstituted 1, 10-phenanthroline" or "substituted or unsubstituted pyridine" in said L means substituted with C in a non-ortho position to the heteroatom₁～C₁₀When substituted with an alkoxy group of (1), "C" as mentioned₁～C₁₀Alkoxy of is C₁～C₆Alkoxy group of (a);

and/or the presence of a gas in the gas,

when X is halogen, the halogen is chlorine, bromine or iodine;

and/or the presence of a gas in the gas,

when said R is⁸、R⁹、R¹⁰And R¹¹Are respectively C₁～C₃When the alkyl group is substituted, said "C" is₁～C₃Alkyl of "is methyl, ethyl, propyl or isopropyl;

and/or the presence of a gas in the gas,

when said R is¹²And R¹³Are respectively C₁～C₃When the alkyl group is substituted, said "C" is₁～C₃Alkyl of "is methyl, ethyl, propyl or isopropyl;

and/or the presence of a gas in the gas,

when said R is¹²And R¹³Are respectively C₅～C₁₀In the case of the aryl group of (a),said "C₅～C₁₀Aryl of (a) is phenyl;

and/or the presence of a gas in the gas,

when said R is¹²、R¹³And the carbon atoms to which they are attached together form a 4-6 membered cyclic structure, said six membered cyclic structure is

And/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅When said "substituted" in "heteroaryl" is substituted with halo, said "halo" is fluoro, chloro, bromo, or iodo;

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅Said "substitution" in "heteroaryl group of (A) is by C₁～C₁₀When substituted with an alkyl group of (1), "C" as mentioned₁～C₁₀Alkyl of is C₁～C₆Alkyl groups of (a);

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅Said "substitution" in "heteroaryl group of (A) is by C₁～C₁₀When substituted with an alkoxy group of (1), "C" as mentioned₁～C₁₀Alkoxy of is C₁～C₆Alkoxy group of (a);

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The aryl "or" heteroatom of (A) isSubstituted or unsubstituted C having 1 to 3 oxygen, sulfur or nitrogen atoms, hetero atoms₂～C₁₅Said "substitution" in "heteroaryl group of (A) is by C₅～C₁₀When substituted with an aryloxy group of (2), "C" as described₅～C₁₀Aryloxy of is C₅～C₆An aryloxy group of (a);

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅Said "substitution" in "heteroaryl group of (A) is by C₁～C₁₀When alkylthio of (A) is substituted, said "C₁～C₁₀Alkylthio of "is C₁～C₆Alkylthio groups of (a);

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅Said "substitution" in "heteroaryl group of (A) is by C₁～C₁₀When substituted with an alkylsilyl group of (a), "C" as mentioned₁～C₁₀The alkylsilyl group of (A) is C₁～C₆Alkyl silicon group of (1);

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅The "substitution" of "said heteroaryl group is C substituted with halogen₁～C₁₀When said alkyl group is substituted, said "halogen-substituted C₁～C₁₀Is "C substituted by one or more of fluorine, chlorine and bromine atoms₁～C₆Alkyl groups of (a);

and/or the presence of a gas in the gas,

when said R is¹The "substitution or non-substitution" as described in (1)Substituted C₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅The "substitution" of "said heteroaryl group is C substituted with halogen₁～C₁₀When substituted with an alkoxy group of (a), "halogen-substituted C" as mentioned₁～C₁₀Alkoxy of (A) is "C substituted by one or more of fluorine, chlorine and bromine atoms₁～C₆Alkoxy groups of ";

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅Said "substitution" in "heteroaryl group of (A) is by C₃～C₁₀When substituted with an aryl group of (1), "C" as mentioned₃～C₁₀Aryl of is C₃～C₆Aryl of (a);

and/or the presence of a gas in the gas,

when said R is³、R⁴、R⁶And R⁷Are respectively C₁～C₆When the alkyl group is substituted, said "C" is₁～C₆The alkyl group of (1) "is methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl;

and/or the presence of a gas in the gas,

when said R is⁵Is C₁～C₆When the alkyl group is substituted, said "C" is₁～C₆The alkyl group of (1) "is methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl;

and/or the presence of a gas in the gas,

when said R is⁵Is "C with 1-2 hetero atoms being nitrogen atoms₃～C₆In the case of the heterocycloalkyl group of (1), the "hetero atom" is a nitrogen atom and the number of hetero atoms is 1 to 2₃～C₆The heterocycloalkyl group of (A) is a C having 1 heteroatom as a nitrogen atom₃～C₄The heterocycloalkyl group of (1);

and/or the presence of a gas in the gas,

when said R is²Is substituted or unsubstituted C₁～C₁₀Said "unsubstituted C" is an alkyl group of₁～C₁₀The alkyl group of "is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl or decyl;

and/or the presence of a gas in the gas,

when said R is²Is substituted or unsubstituted C₁～C₁₀Said "substituted C" for alkyl₁～C₁₀The alkyl group of (a) is substituted methyl, substituted ethyl, substituted propyl, substituted butyl, substituted pentyl, substituted hexyl, substituted heptyl, substituted nonyl, or substituted decyl;

and/or the presence of a gas in the gas,

when said R is²Is substituted or unsubstituted C₁～C₁₀And said "substituted or unsubstituted C₁～C₁₀The substituent mentioned in "alkyl" means substituted by C₅～C₁₀When substituted with an aryl group of (1), "C" as mentioned₅～C₁₀Aryl of (a) is phenyl.

3. A process for preparing a monofluoroalkyl containing compound according to claim 2, wherein:

when said "substituted" in said "substituted or unsubstituted bipyridine", "substituted or unsubstituted 1, 10-phenanthroline" or "substituted or unsubstituted pyridine" in said L means substituted with C in a non-ortho position to the heteroatom₁～C₆When substituted with an alkyl group of (A), said C₁～C₆Alkyl of (a) is methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl;

and/or the presence of a gas in the gas,

when said "substituted" in said "substituted or unsubstituted bipyridine", "substituted or unsubstituted 1, 10-phenanthroline" or "substituted or unsubstituted pyridine" in said L means substituted with C in a non-ortho position to the heteroatom₁～C₆When substituted by alkoxy of (A), said C₁～C₆The alkoxy is methoxy or ethoxyPropoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy;

and/or the presence of a gas in the gas,

when said L is

When it is used, the

Is composed of

And/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅Said "substitution" in "heteroaryl group of (A) is by C₁～C₆When substituted with an alkyl group of (1), "C" as mentioned₁～C₆The alkyl group of (1) "is methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl;

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅Said "substitution" in "heteroaryl group of (A) is by C₁～C₆When substituted with an alkoxy group of (1), "C" as mentioned₁～C₆The alkoxy group of "is methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy;

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" heteroatom of aryl is oxygen,A sulfur or nitrogen atom, a hetero atom number of 1 to 3, substituted or unsubstituted C₂～C₁₅Said "substitution" in "heteroaryl group of (A) is by C₅～C₆When substituted with an aryloxy group of (2), "C" as described₅～C₆The aryloxy group of (1) is phenoxy;

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅Said "substitution" in "heteroaryl group of (A) is by C₁～C₆When alkylthio of (A) is substituted, said "C₁～C₆The "alkylthio group of (a)" is a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group or a tert-butylthio group;

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅Said "substitution" in "heteroaryl group of (A) is by C₁～C₆When substituted with an alkylsilyl group of (a), "C" as mentioned₁～C₆The alkyl silicon group' is methyl silicon group, trimethyl silicon group, ethyl silicon group, propyl silicon group, isopropyl silicon group, butyl silicon group, isobutyl silicon group or tert-butyl silicon group;

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅The "substitution" in "heteroaryl group of (a) is C substituted by one or more of" fluorine, chlorine and bromine atoms₁～C₆When said "alkyl group" is substituted, said "C substituted by one or more of fluorine, chlorine and bromine atoms₁～C₆The alkyl group of (A) is "a methyl group substituted with one or more of fluorine, chlorine and bromine atoms"),"ethyl group substituted by one or more of fluorine, chlorine and bromine atoms", "propyl group substituted by one or more of fluorine, chlorine and bromine atoms", "isopropyl group substituted by one or more of fluorine, chlorine and bromine atoms", "butyl group substituted by one or more of fluorine, chlorine and bromine atoms", "isobutyl group substituted by one or more of fluorine, chlorine and bromine atoms" or "tert-butyl group substituted by one or more of fluorine, chlorine and bromine atoms";

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅The "substitution" in "heteroaryl group of (a) is C substituted by one or more of" fluorine, chlorine and bromine atoms₁～C₆When said "alkoxy group" is substituted, said "C substituted by one or more of fluorine, chlorine and bromine atoms₁～C₆The "alkoxy group of (a) is" methoxy group substituted with one or more of fluorine, chlorine and bromine atoms "," ethoxy group substituted with one or more of fluorine, chlorine and bromine atoms "," propoxy group substituted with one or more of fluorine, chlorine and bromine atoms "," isopropoxy group substituted with one or more of fluorine, chlorine and bromine atoms "," butoxy group substituted with one or more of fluorine, chlorine and bromine atoms "," isobutoxy group substituted with one or more of fluorine, chlorine and bromine atoms "or" tert-butoxy group substituted with one or more of fluorine, chlorine and bromine atoms ";

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅Said "substitution" in "heteroaryl group of (A) is by C₃～C₆When substituted with an aryl group of (1), "C" as mentioned₃～C₆Aryl of (a) is phenyl;

and/or the presence of a gas in the gas,

when said R is¹Described in (1) "Substituted or unsubstituted C₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅Said "substitution" in "heteroaryl" is by

When substituted, the

Is composed of

And/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅Said "substitution" in "heteroaryl" is by

When substituted, the

Is composed of

And/or the presence of a gas in the gas,

When substituted, the

Is composed of

And/or the presence of a gas in the gas,

when said R is⁵Is "C with 1 heteroatom being a nitrogen atom₃～C₄In the case of the heterocycloalkyl group, the "hetero atom" is a nitrogen atom and the number of hetero atoms is 1C₃～C₄The heterocycloalkyl group of is

And/or the presence of a gas in the gas,

when said R is²When substituted methyl, the "substituted methyl" is

And/or the presence of a gas in the gas,

when said R is²When substituted propyl, the "substituted propyl" is

4. A process for preparing a monofluoroalkyl containing compound according to claim 3, wherein:

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅When the "substitution" in "heteroaryl group of (a) is a substitution with a" methyl group substituted with one or more of fluorine, chlorine and bromine atoms ", the" methyl group substituted with a fluorine atom "is a trifluoromethyl group;

and/or the presence of a gas in the gas,

when said R is¹The "substituted or unsubstituted C" as described in (1)₃～C₁₅The "or" hetero atom of the aryl group of (a) is an oxygen, sulfur or nitrogen atom, the number of hetero atoms is 1 to 3, substituted or unsubstituted C₂～C₁₅When the "substitution" in the "heteroaryl group of (a) is a substitution with a methoxy group substituted with one or more of" fluorine, chlorine and bromine atoms ", the" methoxy group substituted with a fluorine atom "is a trifluoromethoxy group;

and/or the presence of a gas in the gas,

When substituted, the

Is composed of

Or

And/or the presence of a gas in the gas,

when the L is substituted or unsubstituted 1, 10-phenanthroline, the substituted 1, 10-phenanthroline is

And/or the presence of a gas in the gas,

when L is "substituted or unsubstituted pyridine", the "substituted pyridine" is

And/or the presence of a gas in the gas,

when L is "substituted or unsubstituted bipyridine", the "substituted bipyridine" is

5. A process for preparing a monofluoroalkyl containing compound according to claim 1, wherein:

when said R is¹Is "substituted or unsubstituted C₃～C₁₅When said aryl group is "substituted or unsubstituted C₃～C₁₅Aryl of is substituted or unsubstituted C₅～C₁₄Aryl of (a);

and/or the presence of a gas in the gas,

when said R is¹Is "C, substituted or unsubstituted, with 1 to 3 heteroatoms being oxygen, sulfur or nitrogen atoms₂～C₁₅In the case of the heteroaryl group of (1), the "hetero atom" is an oxygen, sulfur or nitrogen atom having 1 to 3 hetero atoms, and is a substituted or unsubstituted C₂～C₁₅The heteroaryl group of (A) is C in which the heteroatom is oxygen or nitrogen and the number of heteroatoms is 1₃～C₁₂The heteroaryl group of (1).

6. A process for preparing a monofluoroalkyl containing compound according to claim 5, wherein:

when said R is¹Is "substituted or unsubstituted C₅～C₁₄When said aryl group is "substituted or unsubstituted C₅～C₁₄The aryl group of (a) is a "substituted or unsubstituted phenyl group", "substituted or unsubstituted naphthyl group" or "substituted or unsubstituted fluorenyl group";

and/or the presence of a gas in the gas,

when said R is¹Is "C with 1 hetero atom being an oxygen or nitrogen atom₃～C₁₂In the case of the heteroaryl group of (1), the "hetero atom" is an oxygen or nitrogen atom, and the number of hetero atoms is 1₃～C₁₂The heteroaryl group of (A) is a substituted or unsubstituted pyridineA base group

7. The process for preparing a monofluoroalkyl containing compound according to claim 6, wherein:

when said R is¹When it is "substituted or unsubstituted naphthyl", said "unsubstituted naphthyl" is

And/or the presence of a gas in the gas,

when said R is¹When the group is a "substituted or unsubstituted fluorenyl group", the "unsubstituted fluorenyl group" is

And/or the presence of a gas in the gas,

when said R is¹When the "substituted or unsubstituted fluorenyl group" is used, the "substituted fluorenyl group" is

And/or the presence of a gas in the gas,

when said R is¹When it is "substituted or unsubstituted phenyl", said "substituted phenyl" is

4-tert-butylphenyl,

4-cyanophenyl group, 3-fluoro-4-cyanophenyl group, 3-cyanophenyl group,

3, 4-dichlorophenyl group,

4-phenoxyphenyl, 4-trifluoromethylphenyl, 3-trifluoromethylphenyl,

2-methylphenyl, 3-methylphenyl, 4-methylphenyl,

Or 3, 5-dichlorophenyl;

and/or the presence of a gas in the gas,

when said R is¹When it is a "substituted or unsubstituted pyridyl group", said "unsubstituted pyridyl group" is a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group;

and/or the presence of a gas in the gas,

when said R is¹When it is "substituted or unsubstituted pyridyl", said "substituted pyridyl" is

8. A process for preparing a monofluoroalkyl containing compound according to claim 1, wherein:

the compound A is any one of the following compounds:

wherein TMS represents trimethylsilyl;

and/or the presence of a gas in the gas,

the compound B is any one of the following compounds:

and/or the presence of a gas in the gas,

the compound C is any one of the following compounds:

。

9. a process for preparing a monofluoroalkyl containing compound according to claim 1, wherein:

in the preparation method of the compound containing the fluoroalkyl, the volume mol ratio of the solvent to the compound B is 1 mL/mmol-100 mL/mmol;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the fluoroalkyl, the molar ratio of the alkali to the compound B is 1-5;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the monofluoroalkyl, the ligand is a nitrogen-containing bidentate ligand or a nitrogen-containing tridentate ligand;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the fluoroalkyl, the molar ratio of the ligand to the compound B is 0.01-0.1;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the monofluoroalkyl, the nickel salt is dimethyl ethylene diether nickel chloride, 1,2 bis (diphenylphosphino) ethane nickel chloride, ditriphenylphosphine nickel chloride or nickel nitrate hexahydrate;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the fluoroalkyl, the molar ratio of the compound A to the compound B is 0.5-2;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the fluoroalkyl, the molar ratio of the catalyst to the compound B is 0.01-0.1;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the fluoroalkyl, the molar ratio of the additive to the compound B is 0.01-0.1;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the monofluoroalkyl, the temperature of the Suzuki coupling reaction is 20-120 ℃;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the monofluoroalkyl, the time of the Suzuki coupling reaction is 1-48 hours.

10. A process for preparing a monofluoroalkyl containing compound according to claim 9 wherein:

in the preparation method of the compound containing the fluoroalkyl, the volume mol ratio of the solvent to the compound B is 1 mL/mmol-10 mL/mmol;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the fluoroalkyl, the molar ratio of the alkali to the compound B is 2-3;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing monofluoroalkyl, when the ligand is a nitrogen-containing bidentate ligand, the nitrogen-containing bidentate ligand is substituted or unsubstituted bipyridine, substituted or unsubstituted 1, 10-phenanthroline or

And/or the presence of a gas in the gas,

in the preparation method of the monofluoroalkyl-containing compound, when the ligand is a nitrogen-containing tridentate ligand, the nitrogen-containing tridentate ligand is substituted or unsubstituted pyridine;

the 'substituted or unsubstituted bipyridine', 'substituted or unsubstituted 1, 10-phenanthroline'Or "substituted" as in "substituted or unsubstituted pyridine" means substituted with C in the non-ortho position to the heteroatom₁～C₁₀Alkyl of (C)₁～C₁₀Alkoxy group of (1) and

when a plurality of substituents are present, the substituents may be the same or different; r⁸、R⁹、R¹⁰And R¹¹Are each hydrogen or C₁～C₃Alkyl groups of (a); r¹²And R¹³Are respectively hydrogen and C₁～C₃Alkyl of (C)₅～C₁₀Aryl or R of¹²、R¹³And the carbon atoms to which they are attached together form a 4-6 membered cyclic structure;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the fluoroalkyl, the molar ratio of the ligand to the compound B is 0.05-0.1;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the fluoroalkyl, the molar ratio of the compound A to the compound B is 0.75-1.5;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the fluoroalkyl, the molar ratio of the catalyst to the compound B is 0.05-0.1;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the fluoroalkyl, the molar ratio of the additive to the compound B is 0.05-0.1;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the monofluoroalkyl, the temperature of the Suzuki coupling reaction is 70-80 ℃;

and/or the presence of a gas in the gas,

in the preparation method of the compound containing the monofluoroalkyl, the time of the Suzuki coupling reaction is 8 to 24 hours.

11. A process for preparing a monofluoroalkyl containing compound according to claim 10 wherein: in the preparation method of the monofluoroalkyl containing compound, when the "substitution" in the "substituted or unsubstituted bipyridyl", "substituted or unsubstituted 1, 10-phenanthroline" or "substituted or unsubstituted pyridine" in the ligand means that the "substitution" is carried out by C at a non-ortho position to the heteroatom₁～C₁₀When substituted with an alkyl group of (A), said C₁～C₁₀Alkyl of (A) is C₁～C₆Alkyl groups of (a);

and/or the presence of a gas in the gas,

in the preparation method of the monofluoroalkyl containing compound, when the "substitution" in the "substituted or unsubstituted bipyridyl", "substituted or unsubstituted 1, 10-phenanthroline" or "substituted or unsubstituted pyridine" in the ligand means that the "substitution" is carried out by C at a non-ortho position to the heteroatom₁～C₁₀When substituted by alkoxy of (A), said C₁～C₁₀Alkoxy of C₁～C₆Alkoxy group of (a);

and/or the presence of a gas in the gas,

when said ligand is said R⁸、R⁹、R¹⁰And R¹¹Are respectively C₁～C₃When there is an alkyl group, said C₁～C₃Alkyl of (a) is methyl, ethyl, propyl or isopropyl;

and/or the presence of a gas in the gas,

when said ligand is said R¹²And R¹³Are respectively C₅～C₁₀Aryl of (2), said C₅～C₁₀Aryl of (a) is phenyl;

and/or the presence of a gas in the gas,

when said ligand is said R¹²And R¹³Are respectively C₁～C₃When there is an alkyl group, said C₁～C₃Alkyl of (a) is methyl, ethyl, propyl or isopropyl;

and/or the presence of a gas in the gas,

when said ligand is said R¹²And R¹³And the carbon atoms to which they are attached together form a 4-6 membered cyclic structure, said six membered cyclic structure is

12. A process for preparing a monofluoroalkyl containing compound according to claim 11 wherein:

in the preparation method of the monofluoroalkyl containing compound, when the "substitution" in the "substituted or unsubstituted bipyridyl", "substituted or unsubstituted 1, 10-phenanthroline" or "substituted or unsubstituted pyridine" in the ligand means that the "substitution" is carried out by C at a non-ortho position to the heteroatom₁～C₆When substituted with an alkyl group of (A), said C₁～C₆Alkyl of (a) is methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl;

and/or the presence of a gas in the gas,

in the preparation method of the monofluoroalkyl containing compound, when the "substitution" in the "substituted or unsubstituted bipyridyl", "substituted or unsubstituted 1, 10-phenanthroline" or "substituted or unsubstituted pyridine" in the ligand means that the "substitution" is carried out by C at a non-ortho position to the heteroatom₁～C₆When substituted by alkoxy of (A), said C₁～C₆The alkoxy group of (a) is methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy.

13. A process for preparing a monofluoroalkyl containing compound according to claim 12 wherein: in the preparation method of the compound containing monofluoroalkyl, when the 'nitrogen-containing bidentate ligand' is substituted or unsubstituted bipyridyl, the 'substituted bipyridyl' is

And/or the presence of a gas in the gas,

in the preparation method of the compound containing monofluoroalkyl, when the 'nitrogen-containing bidentate ligand' is substituted or unsubstituted 1, 10-phenanthroline, the 'unsubstituted 1, 10-phenanthroline' is

And/or the presence of a gas in the gas,

in the preparation method of the compound containing monofluoroalkyl, when the 'nitrogen-containing bidentate ligand' is substituted or unsubstituted 1, 10-phenanthroline, the 'substituted 1, 10-phenanthroline' is

And/or the presence of a gas in the gas,

in the preparation method of the compound containing monofluoroalkyl, when the 'nitrogen-containing bidentate ligand' is

When it is used, the

Is composed of

And/or the presence of a gas in the gas,

in the preparation method of the compound containing monofluoroalkyl, when the nitrogen-containing tridentate ligand is substituted or unsubstituted pyridine, the substituted pyridine is