Ruthenium complex taking fluorine ions as counter anions as well as synthesis method and application of ruthenium complex

Abstract

The invention discloses a ruthenium complex with fluorine ions as counter anions and a synthesis method and application thereof, and belongs to the technical field of organic synthesis.The ruthenium complex is selected from a compound with the structural formula such as Ru-A or Ru-B or a hydrate of the compound with the structural formula such as Ru-A or Ru-B. The synthesis method is simple, operation is easy, and the ruthenium complex is suitable for industrial production. The ruthenium complex can be used as a catalyst for catalyzing a fluorination reaction of a trifluoromethoxy aromatic compound, has the advantages of high catalytic activity, good substrate compatibility, high product yield and no need of an activating reagent, can be used for later-stage functional modification of complex molecules, and has a good application prospect in the field of organic synthesis; .

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, specifically to a ruthenium complex using fluoride ions as counterions to anions, its synthesis method, and its application. Background Technology

[0002] Ruthenium-aromatic η 6 Complexes, through the electron-withdrawing effect of ruthenium on aromatic rings, can significantly reduce the electron density of aromatic compounds and enhance their reactivity, providing an effective strategy for the transformation of aromatic compounds (Moriarty, RM; Gill, US and Ku, YY η). 6 -Arene-η 5 -cyclopentadienylrutheniumcomplexes and related systems. J. Organomet. Chem. 1988, 350 , 157-190.). Among them, η forms with aromatic compounds. 6 The metallic ruthenium in the complexes usually adopts cyclopentadienyl ligands. The research on cyclopentadienyl ligands is relatively thorough in the existing technology. However, the counter anions of ruthenium complexes are mostly concentrated in tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonate ion, bis(trifluoromethanesulfonyl)imide ion, etc. There are few research reports on achieving new reactivity by modifying the counter anions.

[0003] Trifluoromethoxybenzene compounds, as an important class of fluorine-containing molecules, have wide applications in medicinal chemistry (Wang, J.; Sánchez-Roselló, M.; Aceña, JL; Del PC; Sorochinsky, AE; Fustero, S.; Soloshonok, VA; Liu, H. Fluorine in Pharmaceutical Industry: Fluorine-Containing Drugs Introduced to the Market in the Last Decade (2001-2011). Chem. Rev. 2014, 114 , 2432-2506. ), but there are few reports on the transformation of trifluoromethoxybenzene compounds (Jeong, J.; Lee, JH; Lee, E. Iron-Catalyzed Borylation of ArylTrifluoromethoxides. Org. Lett. (2025, 27, 5852-5857.) Therefore, if a universal method for converting trifluoromethoxybenzene compounds into other active molecules (such as fluorobenzene) can be developed, it will greatly improve the efficiency of drug screening and structure-activity relationship studies.

[0004] Fluorinated aromatic compounds are widely used in the preparation of pharmaceuticals and pesticides due to their good lipophilicity and metabolic stability (Purser, S.; Moore, PR; Swallow, S.; Gouverneur, V. Fluorine in Medicinal Chemistry). Chem. Soc. Rev. 2008, 37 (320-330.) The safe and efficient introduction of fluorine atoms into organic molecules has always been a core challenge in the field of organic synthesis. Currently, the synthesis of fluorinated aromatics mainly follows two pathways: electrophilic fluorination and nucleophilic fluorination. For the electrophilic fluorination of aromatics, traditional electrophilic fluorinating agents (such as F2, CH3COOF, CF3OF, etc.) suffer from problems such as excessively high reactivity, high toxicity, and potential explosion, as well as demanding reaction conditions and poor selectivity. While novel electrophilic fluorinating agents offer improved safety, they are often expensive or require the prior preparation of activated precursors (Szpera, R.; Moseley, DFJ; Smith, LB; Sterling, AJ; Gouverneur, V. The Fluorination of CH Bonds: Developments and Perspectives). Angew. Chem., Int. Ed. 2019, 58 (14824-14848.). Nucleophilic fluorinating agents such as alkali metal fluorides (MF, such as KF, CsF, etc.) and organofluorine compounds (such as TBAF, etc.) have advantages such as low cost and easy availability. Therefore, nucleophilic fluorination is the most economical route for the preparation of fluoroaromatics. Classical strategies for the nucleophilic fluorination of aromatic compounds include the Balz-Schiemann reaction and aromatic nucleophilic substitution (S... N Nucleophilic fluorination reactions (Ar) are possible, but the substrate range is limited. Therefore, developing a method for nucleophilic fluorination that is safe, requires no activating reagent, has good substrate compatibility, and can be used for the late-stage modification of complex molecules is of great value. Summary of the Invention

[0005] To address the shortcomings of the existing technologies, this invention provides a ruthenium complex using fluoride ions as counter anions. This complex has a simple synthesis method, can efficiently introduce counter anions, can be used to catalyze the fluorination of trifluoromethoxy aromatic compounds, has high catalytic efficiency, good substrate compatibility, and can be used for the late-stage functionalization modification of complex molecules.

[0006] The specific technical solution adopted is as follows: A ruthenium complex with fluoride ions as counter anions, selected from compounds with structural formulas such as Ru-A or Ru-B, or hydrates of compounds with structural formulas such as Ru-A or Ru-B; ; In the above formula, R 1 Alkyl groups selected from C1 to C3.

[0007] The presence of fluoride ions as counter anions gives this ruthenium complex a significant advantage as a catalyst in fluorination reactions. This counter anion can directly participate in the fluorination reaction as a nucleophile. After the fluoride ions are consumed, the catalyst can continue to capture free fluoride ions in the system, thereby increasing the local fluoride ion concentration at the reactive sites while maintaining a low total fluoride concentration, thus favoring the occurrence of the fluorination reaction. Furthermore, if other counter anions such as tetrafluoroborate are used, their electrostatic repulsion may hinder the approach of free fluoride ions to the reactive sites, while directly using fluoride ions as counter anions effectively avoids this effect.

[0008] Furthermore, the ruthenium complexes using fluoride ions as counter anions are Ru-A1, Ru-A2, Ru-A3, Ru-B1 as shown in the following formulas, or any one of the following: Ru-A1 hydrate Ru-A1(·nH2O), Ru-A2 hydrate Ru-A2(·nH2O), Ru-A3 hydrate Ru-A3(·nH2O), and Ru-B1 hydrate Ru-B1(·nH2O). The amount of water of crystallization n in the hydrate is preferably 1 to 3. Experiments have verified that the catalytic activity of the ruthenium complexes mainly depends on the ruthenium metal center counteracting the fluoride anion; the presence or absence of water of crystallization and the amount of water of crystallization do not affect the catalytic activity of the ruthenium complexes.

[0009] ; The present invention also provides a method for synthesizing the ruthenium complex with fluoride ions as counter anions, comprising the following steps: Ruthenium trichloride hydrate was reduced by alcohol under an inert gas atmosphere. Then, polysubstituted cyclopentadiene and naphthalene were added to the reduction system and reacted at 85–150 °C for 12–20 hours. The reaction solution was concentrated and redissolved in water. After impurity removal, a first fluoride salt was added for anion exchange. After post-treatment, a ruthenium complex with fluoride ions as counter anions was prepared.

[0010] Preferably, the inert gas atmosphere is a nitrogen atmosphere or an argon atmosphere.

[0011] Preferably, the conditions for alcohol reduction of ruthenium trichloride hydrate are: temperature 60–90 °C, time 3–5 h.

[0012] Preferably, the structural formula of the polysubstituted cyclopentadiene is as follows: or R 1 The definition is the same as above.

[0013] Preferably, the first fluoride salt is selected from sodium fluoride, potassium fluoride, cesium fluoride, tetramethylammonium fluoride or silver fluoride, and more preferably silver fluoride.

[0014] Preferably, the molar ratio of ruthenium trichloride hydrate, polysubstituted cyclopentadiene, and naphthalene is 1:3 to 5:3 to 9.

[0015] Preferably, the molar ratio of the first fluoride salt to the ruthenium trichloride hydrate is 1.5 to 5:1.

[0016] Preferably, the precipitate in the reaction solution after anion exchange is removed to obtain a supernatant. The supernatant is concentrated and redissolved in dichloromethane. After filtration, the filtrate is added dropwise to an ether solution. The precipitated solid is washed and dried to obtain a ruthenium complex with fluoride ions as counteracting anions.

[0017] This invention also provides the application of the aforementioned ruthenium complex, which uses fluoride ions as counteracting anions, as a catalyst in the field of organic synthesis.

[0018] This invention also provides a method for fluorinating trifluoromethoxy-substituted aromatic compounds, utilizing the aforementioned ruthenium complex with fluoride ions as counter anions as a catalyst to catalyze the fluorination of trifluoromethoxy-substituted aromatic compounds. The reaction with the second fluoride salt yields a fluorinated aromatic compound. Wherein, R is a hydrogen or non-hydrogen substituent, preferably hydrogen, halogen, alkyl, substituted alkyl, alkenyl, alkynyl, substituted aryl, heteroaryl, substituted aryl, alkoxy, amino, ester, amide or sulfonyl, etc., and may also be glycosyl, quinolone bicyclic, dihydroxypurine, steroid, azole, etc., and the number of carbons of R is preferably ≤35, more preferably ≤31.

[0019] Preferably, the second fluoride salt is selected from sodium fluoride, potassium fluoride, cesium fluoride or tetramethylammonium fluoride, and for yield considerations, cesium fluoride is further preferred.

[0020] Furthermore, the reaction is carried out in an organic solvent system, such as 1,4-dioxane, N,N-dimethylformamide, N-methylpyrrolidone, ethylene glycol dimethyl ether, or tetrahydrofuran. For yield considerations, 1,4-dioxane is preferred as the organic solvent.

[0021] Furthermore, additives are added during the reaction process. These additives include 2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethylpiperidine hydrochloride, 1,2,2,6,6-pentamethylpiperidine, or diisopropylethylamine, etc. For yield considerations, 2,2,6,6-tetramethylpiperidine or 2,2,6,6-tetramethylpiperidine hydrochloride is preferred.

[0022] Preferably, the molar ratio of the trifluoromethoxy-substituted aromatic compound, the second fluoride salt, and the additive is 1:1.2 to 2.8:1.

[0023] Preferably, the molar ratio of the ruthenium complex with fluoride ions as counterions to the trifluoromethoxy-substituted aromatic compound is 1:3.3 to 20.

[0024] Preferably, the reaction conditions for the trifluoromethoxy-substituted aromatic compound with the second fluoride salt are: 120–140 °C for 24–48 h.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) This invention synthesizes a series of ruthenium complexes with fluoride ions as counter anions. The counter anions, fluoride ions, are introduced in the later stage of the complex synthesis. The synthesis method is simple and efficient. This strategy can be applied to the synthesis of various polysubstituted cyclopentadiene-type ruthenium complexes.

[0026] (2) The ruthenium complex synthesized in this invention, which uses fluoride ions as counter anions, can catalyze the fluorination reaction of trifluoromethoxy aromatic compounds. It has good catalytic activity, high product yield, and does not require activating reagents. It has good substrate compatibility and is of great value for the late-stage fluorination modification of complex molecules. Detailed Implementation

[0027] To make the objectives, features, and advantages of this invention more apparent and understandable, a detailed description is provided below through specific embodiments. Many specific details are set forth in the following description to provide a thorough understanding of the invention. However, the invention can be practiced in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below. Technical features in various embodiments of the invention can be combined appropriately without mutual conflict.

[0028] Unless otherwise specified, the operating methods in the following examples are generally performed under conventional conditions or as recommended by the manufacturer. Contents not described in detail in this specification are prior art known to those skilled in the art. Unless otherwise specified, the experimental materials used in the examples below can be purchased from conventional biochemical reagent companies.

[0029] Example 1 ; Ruthenium trichloride hydrate (5.2 g, 20.0 mmol) was dissolved in ethanol (100 mL) and stirred at 85 °C for 4 hours under nitrogen protection. After the reaction cooled, pentamethylcyclopentadiene (10.9 g, 80.0 mmol) and naphthalene (10.3 g, 80.0 mmol) were added to the reaction solution, and the reaction was continued to be stirred at 85 °C for 12 hours under nitrogen protection. After the reaction was completed, the solution was cooled to room temperature, concentrated by rotary evaporation, and redissolved in water (125 mL). The aqueous phase was washed three times with petroleum ether (125 mL * 3) and then filtered through diatomaceous earth. The filtrate was added to a 30 mL solution of water containing AgF (3.8 g, 30.0 mmol) under stirring, resulting in the formation of a large amount of silver chloride precipitate. The precipitate was filtered through a membrane, and the supernatant was concentrated by centrifugation and redissolved in dichloromethane. The black insoluble matter was then filtered through a membrane. The filtrate was added dropwise to an ether solution, resulting in the precipitation of a large amount of yellow solid. The solid was washed three times with ether and then dried under vacuum to obtain the hydrate Ru-A1(·nH2O) of the ruthenium complex Ru-A1 with fluoride ions as counter anions, where n is selected from 1 to 3.

[0030] The characterization data for Ru-A1(·nH2O) are as follows: 1 H NMR (500 MHz, Water- d2 ) δ 7.66 (dd, J = 6.8, 3.2 Hz, 1H), 7.51(dd, J = 6.7, 3.3 Hz, 1H), 6.47 (dd, J = 4.4, 2.4 Hz, 1H), 5.95 (dd, J = 4.4,2.4 Hz, 1H), 1.60 (s, 8H). 13 C NMR (126 MHz, Water- d2 ) δ 130.70, 127.39, 96.64, 93.67, 87.96,85.06, 8.61. 19 F NMR (471 MHz, Water- d2 ) δ -149.64.

[0031] Example 2 ; Ruthenium trichloride hydrate (1.3 g, 5.0 mmol) was dissolved in ethanol (30 mL) and stirred at 85 °C for 4 hours under nitrogen protection. After the reaction cooled, tetramethylethylcyclopentadiene (3.0 g, 20.0 mmol) and naphthalene (2.6 g, 20.0 mmol) were added to the reaction solution, and the mixture was stirred at 85 °C for another 12 hours under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, concentrated by rotary evaporation, and redissolved in water (50 mL). The aqueous phase was washed three times with petroleum ether (50 mL x 3) and then filtered through diatomaceous earth. The filtrate was then mixed with an AgF (1.6 g, 12.5 mmol) solution in water (12.5 mL) with stirring. A large amount of silver chloride precipitate was formed. The precipitate was filtered through a membrane, and the supernatant was concentrated by centrifugation and redissolved in dichloromethane. The black insoluble matter was then filtered through a membrane. The filtrate was added dropwise to an ether solution, and a large amount of yellow solid precipitated. The solid was washed three times with ether and then dried under vacuum to obtain the hydrate Ru-A2(·nH2O) of the ruthenium complex Ru-A2 with fluoride ions as counter anions, where n is selected from 1 to 3.

[0032] The characterization data for Ru-A2(·nH2O) are as follows: 1 H NMR (500 MHz, Water- d2 ) δ 7.67 - 7.62 (m, 2H), 7.51 (dd, J = 6.7, 3.2 Hz, 2H), 6.48 (dd, J = 4.4, 2.4 Hz, 2H), 5.96 (dd, J = 4.5, 2.4 Hz, 2H), 2.01 (q, J = 7.8 Hz, 2H), 1.62 (s, 6H), 1.60 (s, 6H), 0.88 (t, J = 8.1 Hz, 3H). 13 C NMR (126 MHz, Water- d2) δ 130.68, 127.43, 98.57, 96.68, 94.01,93.10, 87.84, 84.98, 17.40, 13.31, 8.52, 8.36. 19 F NMR (471 MHz, Chloroform-d) δ -148.47.

[0033] Example 3 ; Ruthenium trichloride hydrate (1.5 g, 5.6 mmol) was dissolved in ethanol (33 mL) and stirred at 85 °C for 4 hours under nitrogen protection. After the reaction cooled, tetramethylisopropylcyclopentadiene (3.7 g, 22.5 mmol) and naphthalene (2.9 g, 22.5 mmol) were added to the reaction solution, and the mixture was stirred at 85 °C for another 12 hours under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, concentrated by rotary evaporation, and redissolved in water (50 mL). The aqueous phase was washed three times with petroleum ether (50 mL x 3) and then filtered through diatomaceous earth. A solution of AgF (1.8 g, 14 mmol) in water (14 mL) was added to the filtrate with stirring. A large amount of silver chloride precipitate was formed. The precipitate was filtered through a membrane, and the supernatant was concentrated by centrifugation, redissolved in dichloromethane, and filtered through a membrane to remove the black insoluble residue. The filtrate was added dropwise to an ether solution, and a large amount of yellow solid precipitated. The solid was washed three times with ether and then dried under vacuum to obtain the hydrate Ru-A3(·nH2O) of the ruthenium complex Ru-A3 with fluoride ions as counter anions, where n is selected from 1 to 3.

[0034] The characterization data for Ru-A3(·nH2O) are as follows: 1 H NMR (500 MHz, water- d2 ) δ 7.68 (dd, J = 6.8, 3.1 Hz, 2H), 7.56 (dd, J = 6.8, 3.3 Hz, 2H), 6.68 - 6.48 (m, 2H), 6.07 (dd, J = 4.0, 1.9 Hz,2H), 2.58 (sept, J = 7.5 Hz, 1H), 1.65 (s, 6H), 1.52 (s, 6H), 1.21 (s, 3H), 1.19 (s, 3H). 13 C NMR (126 MHz, water-d2 ) δ 130.80, 127.52, 104.51, 96.88, 93.94,92.52, 87.76, 85.00, 25.47, 21.69, 9.31, 8.24. 19 F NMR (471 MHz, water- d2 ) δ -144.29.

[0035] Example 4 ; Ruthenium trichloride hydrate (392 mg, 1.5 mmol) was dissolved in ethanol (10 mL) and stirred at 85 °C for 4 hours under nitrogen protection. After the reaction cooled, 1,3,4-tritert-butyl-1,3-cyclopentadiene (1.8 g, 7.5 mmol) and naphthalene (1.5 g, 12.0 mmol) were added to the reaction solution, and the mixture was stirred at 150 °C for 20 hours under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, concentrated by rotary evaporation, and redissolved in water (25 mL). The aqueous phase was washed three times with petroleum ether (25 mL * 3) and then filtered through diatomaceous earth. The filtrate was then mixed with an aqueous solution of AgF (952 mg, 7.5 mmol) (7.5 mL) with stirring, resulting in a large amount of silver chloride precipitate. The precipitate was filtered through a membrane, and the supernatant was concentrated by centrifugation, redissolved in dichloromethane, and filtered through a membrane to remove the black insoluble residue. The filtrate was added dropwise to an ether solution, and a large amount of yellow solid precipitated. The solid was washed three times with ether and then dried under vacuum to obtain the hydrate Ru-B1(·nH2O) of the ruthenium complex Ru-B1 with fluoride ions as counter anions, where n is selected from 1 to 3.

[0036] The characterization data for Ru-B1(·nH2O) are as follows: 1 H NMR (500 MHz, Water- d2 ) δ 7.84 (dd, J = 6.8, 3.3 Hz, 2H), 7.68 (dd, J = 6.5, 3.1 Hz, 2H), 7.08 (dd, J = 4.6, 2.4 Hz, 2H), 6.35 (dd, J = 4.5,2.4 Hz, 2H), 5.01 (s, 2H), 1.21 (s, 18H), 1.08 (s, 9H). 13 C NMR (126 MHz, Water-d2 ) δ 131.64, 129.51, 112.11, 110.24, 98.67,85.53, 83.93, 77.78, 32.30, 32.11, 30.26, 29.38. 19 F NMR (565 MHz, water- d2 ) δ -141.63.

[0037] Application Example 1 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH2O ([Cp) synthesized in Example 1 was sequentially added to the reaction flask. * Ru(nap)]F·nH2O (8.4 mg, approx. 0.02 mmol) and cesium fluoride (36.5 mg, 0.24 mmol) were dissolved in 1,4-dioxane (1 mL), and finally ethyl 3-(trifluoromethoxy)benzoate (46.8 mg, 0.2 mmol) and 2,2,6,6-tetramethylpiperidine (28.3 mg, 0.2 mmol) were added. The reaction solution was reacted at 140 °C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature and passed through a silica gel column to give 23.9 mg of the product shown in the above formula, with a yield of 71%.

[0038] The product characterization data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.84 (dt, J = 7.7, 1.3 Hz, 1H), 7.72(ddd, J = 9.4, 2.8, 1.5 Hz, 1H), 7.41 (td, J = 8.0, 5.5 Hz, 1H), 7.32 - 7.18(m, 1H), 4.38 (q, J = 7.1 Hz, 2H), 1.40 (t, J = 7.1 Hz, 3H). 13 C NMR (126 MHz, Chloroform- d ) δ 165.62 (d, J C-F = 3.1 Hz), 162.68 (d, J C-F= 246.8 Hz), 132.82 (d, J C-F = 7.5 Hz), 130.07 (d, J C-F = 7.8 Hz), 125.40(d, J C-F = 3.1 Hz), 120.00 (d, J C-F = 21.3 Hz), 116.58 (d, J C-F = 23.0 Hz), 61.48, 14.40. 19 F NMR (376 MHz, Chloroform- d ) δ -112.55.

[0039] Application Example 2 ; Under an argon atmosphere, the ruthenium complex Ru-A2·nH2O (8.7 mg, approximately 0.02 mmol) synthesized in Example 2 and cesium fluoride (36.5 mg, 0.24 mmol) were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, ethyl 3-(trifluoromethoxy)benzoate (46.8 mg, 0.2 mmol) and 2,2,6,6-tetramethylpiperidine (28.3 mg, 0.2 mmol) were added. The reaction solution was reacted at 140 °C for 24 hours. After the reaction was complete, the reaction solution was cooled to room temperature and filtered through a silica gel column to obtain 23.2 mg of the product shown in the above formula, with a yield of 69%.

[0040] The characterization data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.84 (dt, J = 7.7, 1.3 Hz, 1H), 7.72(ddd, J = 9.4, 2.8, 1.5 Hz, 1H), 7.42 (td, J = 8.0, 5.5 Hz, 1H), 7.33 - 7.18(m, 1H), 4.39 (q, J = 7.1 Hz, 2H), 1.40 (t, J = 7.1 Hz, 3H). 13C NMR (126 MHz, Chloroform- d ) δ 165.62 (d, J C-F = 3.1 Hz), 162.68 (d, J C-F = 246.8 Hz), 132.82 (d, J C-F = 7.5 Hz), 130.07 (d, J C-F = 7.8 Hz), 125.40(d, J C-F = 3.1 Hz), 120.00 (d, J C-F = 21.3 Hz), 116.58 (d, J C-F = 23.0 Hz), 61.48, 14.40. 19 F NMR (376 MHz, Chloroform- d ) δ -112.55.

[0041] Application Example 3 ; Under an argon atmosphere, the ruthenium complex Ru-A3·nH2O (9.0 mg, approximately 0.02 mmol) synthesized in Example 3 and cesium fluoride (36.5 mg, 0.24 mmol) were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, ethyl 3-(trifluoromethoxy)benzoate (46.8 mg, 0.2 mmol) and 2,2,6,6-tetramethylpiperidine (28.3 mg, 0.2 mmol) were added. The reaction solution was reacted at 140 °C for 24 hours. After the reaction was complete, the reaction solution was cooled to room temperature and filtered through a silica gel column to obtain 21.9 mg of the product shown in the above formula, with a yield of 65%.

[0042] The characterization data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.84 (dt, J = 7.7, 1.3 Hz, 1H), 7.72(ddd, J = 9.4, 2.8, 1.5 Hz, 1H), 7.42 (td, J= 8.0, 5.5 Hz, 1H), 7.33 - 7.18(m, 1H), 4.39 (q, J = 7.1 Hz, 2H), 1.40 (t, J = 7.1 Hz, 3H). 13 C NMR (126 MHz, Chloroform- d ) δ 165.62 (d, J C-F = 3.1 Hz), 162.68 (d, J C-F = 246.8 Hz), 132.82 (d, J C-F = 7.5 Hz), 130.07 (d, J C-F = 7.8 Hz), 125.40(d, J C-F = 3.1 Hz), 120.00 (d, J C-F = 21.3 Hz), 116.58 (d, J C-F = 23.0 Hz), 61.48, 14.40. 19 F NMR (376 MHz, CDCl3) δ -112.55.

[0043] Application Example 4 ; Under an argon atmosphere, the ruthenium complex Ru-B1·nH2O (10.7 mg, approximately 0.02 mmol) synthesized in Example 4 and cesium fluoride (36.5 mg, 0.24 mmol) were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, ethyl 3-(trifluoromethoxy)benzoate (46.8 mg, 0.2 mmol) and 2,2,6,6-tetramethylpiperidine (28.3 mg, 0.2 mmol) were added. The reaction solution was reacted at 140 °C for 24 hours. After the reaction was complete, the reaction solution was cooled to room temperature and filtered through a silica gel column to obtain 7.1 mg of the product shown in the above formula, with a yield of 21%.

[0044] The characterization data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d) δ 7.84 (dt, J = 7.7, 1.3 Hz, 1H), 7.72(ddd, J = 9.4, 2.8, 1.5 Hz, 1H), 7.42 (td, J = 8.0, 5.5 Hz, 1H), 7.33 - 7.18(m, 1H), 4.39 (q, J = 7.1 Hz, 2H), 1.40 (t, J = 7.1 Hz, 3H). 13 C NMR (126 MHz, Chloroform- d ) δ 165.62 (d, J C-F = 3.1 Hz), 162.68 (d, J C-F = 246.8 Hz), 132.82 (d, J C-F = 7.5 Hz), 130.07 (d, J C-F = 7.8 Hz), 125.40(d, J C-F = 3.1 Hz), 120.00 (d, J C-F = 21.3 Hz), 116.58 (d, J C-F = 23.0 Hz),61.48, 14.40. 19 F NMR (376 MHz, CDCl3) δ -112.55。

[0045] Application Example 5 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH₂O (16.8 mg, approximately 0.04 mmol) synthesized in Example 1 and cesium fluoride (36.5 mg, 0.24 mmol) were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, 4-(trifluoromethoxy)chlorobenzene (39.3 mg, 0.2 mmol) and 2,2,6,6-tetramethylpiperidine (28.3 mg, 0.2 mmol) were added. The reaction solution was reacted at 140 °C for 24 hours. After the reaction was complete, the reaction solution was cooled to room temperature and filtered through a silica gel column to obtain 13.1 mg of the product shown in the above formula, with a yield of 50%.

[0046] The characterization data of the product are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.42 - 7.24 (m, 2H), 7.09 - 6.97(m, 2H). 13 C NMR (151 MHz, Chloroform- d ) δ 161.5 (d, J C-F = 246.0 Hz), 129.7 (d, J C-F J C-F = 8.2 Hz), 128.8 (d, J C-F = 3.3 Hz), 116.9 (d, J C-F = 22.3 Hz). 19 F NMR (376 MHz, Chloroform- d ) δ -115.95.

[0047] Application Example 6 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH₂O (8.4 mg, approximately 0.02 mmol) synthesized in Example 1, cesium fluoride (36.5 mg, 0.24 mmol), and 4-(trans, trans-4-propylbicyclohexyl)-trifluoromethoxybenzene (73.7 mg, 0.2 mmol) were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, 2,2,6,6-tetramethylpiperidine (28.3 mg, 0.2 mmol) was added. The reaction solution was reacted at 140 °C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, dry-loaded, and filtered through a silica gel column to obtain 52.0 mg of the product shown in the above formula, with a yield of 86%.

[0048] The characterization data of the product are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 7.17 - 7.11 (m, 2H), 6.99 - 6.92 (m,2H), 2.42 (tt, J = 12.2, 3.4 Hz, 1H), 1.95 - 1.86 (m, 2H), 1.86 - 1.81 (m,2H), 1.80 - 1.70 (m, 4H), 1.44 - 1.34 (m, 2H), 1.31 (p, J = 7.3 Hz, 2H), 1.20- 1.09 (m, 6H), 1.08 - 0.94 (m, 3H), 0.88 (t, J = 7.3 Hz, 3H). 13 C NMR (126 MHz, Chloroform- d ) δ 161.26 (d, J C-F = 242.8 Hz), 143.68,128.19 (d, J C-F = 7.8 Hz), 115.03 (d, J C-F = 20.8 Hz), 44.08, 43.55, 43.04,39.98, 37.79, 34.94, 33.76, 30.48, 30.26, 20.20, 14.56. 19 F NMR (471 MHz, Chloroform- d) δ -118.01.

[0049] Application Example 7 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH₂O (8.4 mg, approximately 0.02 mmol) synthesized in Example 1 and cesium fluoride (36.5 mg, 0.24 mmol) were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, 2-methyl-1-(4-trifluoromethoxyphenyl)propene (43.2 mg, 0.2 mmol) and 2,2,6,6-tetramethylpiperidine (28.3 mg, 0.2 mmol) were added. The reaction solution was reacted at 120 °C for 24 hours. After the reaction was complete, the reaction solution was cooled to room temperature, dry-loaded, and filtered through a silica gel column to obtain 8.7 mg of the product shown in the above formula, with a yield of 29%.

[0050] The characterization data of the product are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 7.19-7.10 (m, 2H), 7.00 - 6.93 (m,2H), 6.21 (s, 1H), 1.89 (d, J = 1.4 Hz, 3H), 1.80 (d, J = 1.4 Hz, 3H). 13 C NMR (126 MHz, Chloroform- d ) δ 161.0 (d, J C-F = 243.7 Hz), 135.3, 134.6 (d, J C-F = 3.4 Hz), 130.0 (d, J C-F = 7.4 Hz), 124.3, 114.8 (d, J C-F = 21.1Hz), 26.9, 19.6. 19 F NMR (471 MHz, Chloroform- d ) δ -116.98.

[0051] Application Example 8 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH₂O (8.4 mg, approximately 0.02 mmol) synthesized in Example 1 and cesium fluoride (36.5 mg, 0.24 mmol) were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, 2-(4-trifluoromethoxyphenyl)pyridine (47.8 mg, 0.2 mmol) and 2,2,6,6-tetramethylpiperidine (28.3 mg, 0.2 mmol) were added. The reaction solution was reacted at 120 °C for 24 hours. After the reaction was complete, the reaction solution was cooled to room temperature and filtered through a silica gel column to obtain 31.2 mg of the product shown in the above formula, with a yield of 90%.

[0052] The characterization data of the product are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 8.81 (s, 1H), 8.60 (d, J = 4.7 Hz, 1H), 7.83 (dt, J = 7.9, 2.0 Hz, 1H), 7.62 - 7.49 (m, 2H), 7.36 (dd, J = 8.0,4.8 Hz, 1H), 7.21 - 7.11 (m, 2H). 13 C NMR (126 MHz, Chloroform- d ) δ 163.08 (d, J C-F = 247.8 Hz), 148.65,148.31, 135.90, 134.37, 134.12, 128.97 (d, J C-F = 8.3 Hz), 123.73, 116.23 (d, J C-F = 21.6 Hz). 19 F NMR (471 MHz, Chloroform- d ) δ -114.12.

[0053] Application Example 9 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH₂O (8.4 mg, approximately 0.02 mmol) synthesized in Example 1 and cesium fluoride (36.5 mg, 0.24 mmol) were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, p-trifluoromethoxyanisole (38.4 mg, 0.2 mmol) and 2,2,6,6-tetramethylpiperidine (28.3 mg, 0.2 mmol) were added. The reaction solution was reacted at 140 °C for 48 hours. After the reaction was complete, the reaction solution was cooled to room temperature. Due to the low boiling point of the product, DME (18.0 mg, 0.2 mmol) was added as an internal standard. After thorough mixing, 0.1 mL of the reaction solution was transferred to an NMR tube, diluted to 0.6 mL with deuterated chloroform, and subjected to NMR analysis. The yield of the product shown in the above formula was determined to be 68%.

[0054] The characterization data of the product are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 7.11-7.05 (m, 2H), 6.89- 6.84 (m,2H), 3.82 (s, 3H).

[0055] Application Example 10 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH₂O (8.4 mg, approximately 0.02 mmol) synthesized in Example 1 and cesium fluoride (36.5 mg, 0.24 mmol) were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, p-4-trifluoromethoxy-N,N-dimethylaniline (41.0 mg, 0.2 mmol) and 2,2,6,6-tetramethylpiperidine (28.3 mg, 0.2 mmol) were added. The reaction solution was reacted at 140 °C for 48 hours. After the reaction was complete, the reaction solution was cooled to room temperature. Due to the low boiling point of the product, DME (18.0 mg, 0.2 mmol) was added as an internal standard. After thorough mixing, 0.1 mL of the reaction solution was transferred to an NMR tube, diluted to 0.6 mL with deuterated chloroform, and subjected to NMR analysis. The yield of the product shown in the above formula was determined to be 66%.

[0056] The characterization data of the product are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 6.95-6.90 (m, 2H), 6.69-6.65 (m, 2H), 2.86 (s, 6H).

[0057] Application Example 11 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH₂O (8.4 mg, approximately 0.02 mmol) synthesized in Example 1 and cesium fluoride (36.5 mg, 0.24 mmol) were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, ethyl p-4-trifluoromethoxybenzoate (46.8 mg, 0.2 mmol) and 2,2,6,6-tetramethylpiperidine (28.3 mg, 0.2 mmol) were added. The reaction solution was reacted at 120 °C for 24 hours. After the reaction was complete, the reaction solution was cooled to room temperature, dry-loaded, and filtered through a silica gel column to obtain 28.3 mg of the product shown in the above formula, with a yield of 84%.

[0058] The characterization data of the product are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 8.06 (dd, J = 8.8, 5.5 Hz, 2H), 7.10(t, J = 8.7 Hz, 2H), 4.37 (q, J = 7.1 Hz, 2H), 1.39 (t, J = 7.1 Hz, 3H). 13 C NMR (126 MHz, Chloroform- d ) δ 165.85 (d, J C-F = 253.26 Hz), 165.85,132.20 (d, J = 9.2 Hz), 126.89 (d, J = 3.1 Hz), 115.58 (d, J = 21.9 Hz), 61.24, 14.46. 19 F NMR (471 MHz, Chloroform- d ) δ -106.08.

[0059] Application Example 12 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH₂O (8.4 mg, approximately 0.02 mmol) synthesized in Example 1 and cesium fluoride (36.5 mg, 0.24 mmol) were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, N,N-diethyl-4-trifluoromethoxybenzamide (52.2 mg, 0.2 mmol) and 2,2,6,6-tetramethylpiperidine (28.3 mg, 0.2 mmol) were added. The reaction solution was reacted at 120 °C for 24 hours. After the reaction was complete, the reaction solution was cooled to room temperature, dry-loaded, and filtered through a silica gel column to obtain 32.5 mg of the product shown in the above formula, with a yield of 83%.

[0060] The characterization data of the product are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 7.38 - 7.25 (m, 2H), 7.08 - 6.95 (m,2H), 3.33 (br, 4H), 1.28 - 0.91 (br, 6H). 13 C NMR (126 MHz, Chloroform- d ) δ 170.51, 163.18 (d, J C-F = 248.7 Hz), 133.42 (d, J C-F = 3.6 Hz), 128.63 (d, J C-F = 8.3 Hz), 115.58 (d, J C-F = 21.7Hz), 43.49, 39.55, 14.25, 13.02. 19 F NMR (471 MHz, Chloroform- d ) δ -111.41.

[0061] Application Example 13 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH₂O synthesized in Example 1 (8.4 mg, approximately 0.02 mmol), cesium fluoride (36.5 mg, 0.24 mmol), and (1S,4S)-2-tert-butoxycarbonyl-5-[4-(trifluoromethoxy)benzenesulfonyl]-2,5-diazabicyclo[2.2.1]heptane (84.5 mg, 0.2 mmol) were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, 2,2,6,6,-tetramethylpiperidine (28.3 mg, 0.2 mmol) was added. The reaction solution was reacted at 120 °C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and the sample was loaded onto a silica gel column using a dry method to obtain 66.7 mg of the product shown in the above formula, with a yield of 94%.

[0062] The characterization data of the product are as follows: 1 H NMR (500 MHz, Chloroform- d , rotamers) δ 7.85 (dd, J = 8.5, 5.0 Hz,2H), 7.24 - 7.11 (m, 2H), 4.57 - 4.31 (m, 2H), 3.40 (m, 1H), 3.32 - 3.05 (m,1H), 1.71 (m, 1H), 1.41 (m, 9H), 1.37 - 1.29 (m, 1H). 13 C NMR (126 MHz, Chloroform- d, rotamers) δ 165.24 (d, J C-F = 255.5Hz), 153.95, 134.68, 129.99 (d, J C-F = 9.1 Hz), 116.54 (d, J C-F = 22.5 Hz),80.12, 60.40, 59.83, 57.38, 56.50, 55.22, 55.06, 53.77, 53.46, 36.69, 36.21,28.43, 28.36. 19 F NMR (471 MHz, Chloroform- d , rotamers) δ -104.64, -104.83.

[0063] Application Example 14 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH₂O (8.4 mg, approximately 0.02 mmol), cesium fluoride (85.1 mg, 0.56 mmol), and 2,2,6,6,-tetramethylpiperidine hydrochloride (35.5 mg, 0.2 mmol) synthesized in Example 1 were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, N,N-dimethyl-4-trifluoromethoxybenzylamine (43.8 mg, 0.2 mmol) was added. The reaction solution was reacted at 120 °C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and the sample was loaded onto a silica gel column using a dry method to obtain 17.2 mg of the product shown in the above formula, with a yield of 56%.

[0064] The characterization data of the product are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 7.27-7.22 (m, 2H), 7.03-6.91 (m,2H), 3.37 (s, 2H), 2.21 (s, 6H) 13 C NMR (126 MHz, Chloroform- d ) δ 161.8 (d, J C-F = 243 Hz), 134.6 (d, J C-F = 3.1 Hz), 130.9 (d, J C-F = 7.7 Hz), 115.2 (d, J C-F = 21 Hz), 63.5, 45.2. 19 F NMR (471 MHz, Chloroform- d , rotamers) δ -117.0.

[0065] Application Example 15 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH₂O (8.4 mg, approximately 0.02 mmol), cesium fluoride (36.5 mg, 0.24 mmol), and an abiraterone derivative (107.5 mg, 0.2 mmol) synthesized in Example 1 were dissolved in 1,4-dioxane (1 mL) sequentially in a reaction flask. Finally, 2,2,6,6,-tetramethylpiperidine (28.3 mg, 0.2 mmol) was added. The reaction solution was reacted at 120 °C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and the sample was loaded onto a silica gel column using a dry method to obtain 66.7 mg of the product shown in the above formula, with a yield of 83%.

[0066] The characterization data of the product are as follows: 1 H NMR (500 MHz, Chloroform-d) δ 8.63 (d, J = 2.3 Hz, 1H), 8.46 (dd, J = 4.8, 1.6 Hz, 1H), 7.83 (dt, J = 7.7, 1.3 Hz, 1H), 7.72 (ddd, J = 9.4,2.7, 1.5 Hz, 1H), 7.65 (m, J = 7.9, 2.0 Hz, 1H), 7.41 (m, 1H), 7.27 - 7.09(m, 2H), 6.00 (dd, J = 3.3, 1.8 Hz, 1H), 5.62 - 5.32 (m, 1H), 4.97 - 4.75 (m,1H), 2.54 - 2.42 (m, 2H), 2.28 (ddd, J = 15.8, 6.6, 3.3 Hz, 1H), 2.05 (m,4H), 1.93 (dt, J = 13.4, 3.6 Hz, 1H), 1.85 - 1.66 (m, 4H), 1.61 (m, 2H), 1.50(td, J = 12.3, 4.9 Hz, 1H), 1.30 - 1.22 (m, 2H), 1.13 (m, 4H), 1.06 (s, 3H). 13 C NMR (126 MHz, Chloroform- d ) δ 164.99, 162.67 (d,J C-F = 246.8 Hz),151.79, 147.99 (d, J C-F = 6.9 Hz), 140.00, 133.87, 133.12, 130.04 (d, J C-F =7.6 Hz), 129.40, 125.41 (d, J C-F = 3.0 Hz), 123.18, 122.71, 119.94 (d, J =21.2 Hz), 116.58 (d, J C-F = 23.0 Hz), 75.05, 57.59, 50.38, 47.46, 38.28,37.04, 36.96, 35.33, 31.93, 31.66, 30.54, 27.92, 20.96, 19.43, 16.70. 19 F NMR (471 MHz, Chloroform- d , rotamers) δ -112.58.

[0067] Application Example 16 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH₂O (8.4 mg, approximately 0.02 mmol), cesium fluoride (36.5 mg, 0.24 mmol), and a galactose derivative (89.7 mg, 0.2 mmol) synthesized in Example 1 were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, 2,2,6,6,-tetramethylpiperidine (28.3 mg, 0.2 mmol) was added. The reaction solution was reacted at 120 °C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and the sample was loaded onto a silica gel column using a dry method to obtain 67.2 mg of the product shown in the above formula, with a yield of 88%.

[0068] The characterization data of the product are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 8.22 - 7.77 (m, 2H), 7.10 (t, J =8.6 Hz, 2H), 5.56 (d, J= 5.0 Hz, 1H), 4.65 (dd, J = 7.9, 2.5 Hz, 1H), 4.52(dd, J = 11.5, 4.6 Hz, 1H), 4.42 (dd, J = 11.5, 7.7 Hz, 1H), 4.39 - 4.28 (m,2H), 4.17 (ddd, J = 7.0, 4.6, 1.9 Hz, 1H), 1.51 (s, 3H), 1.48 (s, 3H), 1.36(s, 3H), 1.33 (s, 3H). 13 C NMR (126 MHz, Chloroform- d ) δ 165.96 (d, J C-F = 253.8 Hz), 165.64,132.40 (d, J C-F = 9.3 Hz), 126.46 (d, J C-F = 2.9 Hz), 115.66 (d, J C-F = 22.0Hz), 109.89, 108.97, 96.48, 71.29, 70.89, 70.66, 66.29, 64.21, 26.16, 26.12,25.12, 24.64. 19 F NMR (471 MHz, Chloroform- d , rotamers) δ -105.65。

[0069] Application Example 17 ; Under an argon atmosphere, the ruthenium complex Ru-Al·nH₂O (8.4 mg, approximately 0.02 mmol), cesium fluoride (36.5 mg, 0.24 mmol), and the acetone-protected theophylline derivative (91.0 mg, 0.2 mmol) synthesized in Example 1 were dissolved in 1,4-dioxane (1 mL) in a reaction flask. Finally, 2,2,6,6,-tetramethylpiperidine (28.3 mg, 0.2 mmol) was added. The reaction solution was reacted at 120 °C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and the sample was dry-loaded and filtered through a silica gel column to obtain 74.2 mg of the product shown in the above formula, with a yield of 96%.

[0070] The characterization data of the product are as follows: 1 H NMR (500 MHz, Chloroform- d ) δ 7.99 - 7.65 (m, 2H), 7.19 (t, J =8.6 Hz, 2H), 4.79 - 4.60 (m, 1H), 4.54 (dd, J = 13.8, 2.6 Hz, 1H), 4.25 (dd, J = 13.9, 9.0 Hz, 1H), 4.19 (dd, J = 8.8, 6.7 Hz, 1H), 3.69 (dd, J = 8.8, 5.6Hz, 1H), 3.62 (s, 3H), 3.42 (s, 3H), 1.25 (s, 3H), 1.17 (s, 3H). 13 C NMR (126 MHz, Chloroform- d ) δ 164.07 (d, J C-F = 251.8 Hz), 155.61,152.49, 151.76, 148.86, 132.21 (d, J C-F = 8.5 Hz), 125.00 (d, J C-F = 3.4 Hz), 116.08 (d, J C-F = 22.0 Hz), 110.42, 107.77, 75.23, 66.98, 50.01, 29.99, 28.22,26.39, 25.11. 19 F NMR (471 MHz, Chloroform- d , rotamers) δ -109.31.

[0071] The embodiments described above provide a detailed explanation of the technical solutions of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, additions, or similar substitutions made within the scope of the principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A ruthenium complex using fluoride ions as counterions to anions, characterized in that, Selected from compounds with structural formulas such as Ru-A or Ru-B, or hydrates of compounds with structural formulas such as Ru-A or Ru-B; ； In the above formula, R 1 Alkyl groups selected from C1 to C3.

2. The method for synthesizing ruthenium complexes using fluoride ions as counter anions according to claim 1, characterized in that, Includes the following steps: Ruthenium trichloride hydrate was reduced by alcohol under an inert gas atmosphere. Then, polysubstituted cyclopentadiene and naphthalene were added to the reduction system and reacted at 85–150 °C for 12–20 hours. The reaction solution was concentrated and redissolved in water. After impurity removal, a first fluoride salt was added for anion exchange. After post-treatment, a ruthenium complex with fluoride ions as counter anions was prepared.

3. The method for synthesizing ruthenium complexes using fluoride ions as counter anions according to claim 2, characterized in that, The structural formula of polysubstituted cyclopentadiene is or R 1 The first fluoride salt is selected from C1 to C3 alkyl groups; and / or, the first fluoride salt is selected from sodium fluoride, potassium fluoride, cesium fluoride, tetramethylammonium fluoride, or silver fluoride.

4. The method for synthesizing ruthenium complexes using fluoride ions as counter anions according to claim 2, characterized in that, The molar ratio of ruthenium trichloride hydrate, polysubstituted cyclopentadiene, and naphthalene is 1:3 to 5:3 to 9; and / or, the molar ratio of the amount of the first fluoride salt added to the amount of ruthenium trichloride hydrate is 1.5 to 5:

1.

5. The application of the ruthenium complex with fluoride ions as counteracting anions as a catalyst according to claim 1 in the field of organic synthesis.

6. A method for fluorinating a trifluoromethoxy-substituted aromatic compound, characterized in that, Using the ruthenium complex of claim 1, which uses fluoride ions as counter anions, as a catalyst, to catalyze the catalysis of trifluoromethoxy-substituted aromatic compounds. The reaction with the second fluoride salt yields a fluorinated aromatic compound. R is a hydrogen or non-hydrogen substituent.

7. The method for fluorinating trifluoromethoxy-substituted aromatic compounds according to claim 6, characterized in that, The second fluoride salt is selected from sodium fluoride, potassium fluoride, cesium fluoride, or tetramethylammonium fluoride; and / or, the reaction is carried out in an organic solvent system, wherein the organic solvent is 1,4-dioxane, N,N-dimethylformamide, N-methylpyrrolidone, ethylene glycol dimethyl ether, or tetrahydrofuran.

8. The method for fluorinating trifluoromethoxy-substituted aromatic compounds according to claim 6, characterized in that, Additives were also added during the reaction process. The additives were 2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethylpiperidine hydrochloride, 1,2,2,6,6-pentamethylpiperidine or diisopropylethylamine. The molar ratio of trifluoromethoxy-substituted aromatic compounds, second fluoride salts and additives was 1:1.2 to 2.8:

1.

9. The method for fluorinating trifluoromethoxy-substituted aromatic compounds according to claim 6, characterized in that, The molar ratio of ruthenium complexes with fluoride ions as counter anions to trifluoromethoxy-substituted aromatic compounds is 1:3.3–20.

10. The method for fluorinating trifluoromethoxy-substituted aromatic compounds according to claim 6, characterized in that, The reaction conditions for trifluoromethoxy-substituted aromatic compounds with second fluoride salts are: 120–140 °C, 24–48 h.

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