Synthetic method of indene alkyl substituted polyfluorinated aromatic hydrocarbon

Abstract

The invention discloses a synthetic method of indene alkyl substituted polyfluorinated aromatic hydrocarbon, which comprises the following steps: reacting 2-iodo styrene compound, 7-oxa norbornadiene and polyfluorinated aromatic hydrocarbon as raw materials in an organic solvent under the combined action of a palladium catalyst, a ligand, alkali and an additive, and post-processing after the reaction is finished to obtain the indene alkyl substituted polyfluorinated aromatic hydrocarbon compound, the reaction formula is as follows: in the # imgabs0 # formula, R1 is selected from one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group and a halogen; r2 is selected from one of a hydrogen atom, an alkyl group, an alkoxy group, an ester group, an acyl group and a cyano group; r is alkyl; n is the number of fluorine atoms in the polyfluorinated aromatic hydrocarbon. According to the present invention, the easily prepared 2-iodo styrene compound, the commercial 7-oxa norbornadiene and the polyfluorinated aromatic hydrocarbon are adopted as the raw materials, and the one-pot method is adopted to construct the indene ring and the three carbon-carbon bonds so as to achieve the rapid construction of the indene alkyl substituted polyfluorinated aromatic hydrocarbon skeleton; the reaction has the advantages that operation is simple, raw materials are easy to obtain, substrate applicability is wide, and a target product is easy to separate.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for synthesizing indenyl-substituted polyfluoroaromatic hydrocarbons. Background Art

[0002] Alkylated polyfluoroaromatic hydrocarbons are commonly found in natural products and bioactive molecules, and have received extensive attention in the fields of medicine, dyes, pesticides, biology, etc. Among them, palladium-catalyzed intramolecular tandem cyclization / alkylation strategies of polyfluoroaromatic hydrocarbons have received great attention. For example, in 2016, Liang's group reported palladium-catalyzed intramolecular Heck / intermolecular C-H alkylation of polyfluoroaromatic hydrocarbons with o-iodoaniline-derived acrylamide. Subsequently, the group achieved the alkylation of polyfluoroaromatic hydrocarbons via the Narasaka-Heck reaction. Using a similar strategy, Zhang's group established a Pd / XuPhos catalytic system for enantioselective cascade Heck / intermolecular C-H alkylation of o-iodophenol-derived allyl ethers with various polyfluoroaromatic hydrocarbons. However, these methods are limited by the use of o-iodophenol allyl ether or aromatic acrylamide as reaction substrates, and have the problems of limited substrate range and difficulty in preparation, relatively single synthesis methods, and poor product diversity. Summary of the invention

[0003] In view of the above problems existing in the prior art, the purpose of the present invention is to provide a convenient method for synthesizing indenyl-substituted polyfluoroaromatic compounds, which utilizes simple and readily available reaction raw materials and synthesizes indenyl-substituted polyfluoroaromatic compounds in a one-pot multi-step manner through a palladium-catalyzed intermolecular tandem cycloalkylation reaction process.

[0004] To achieve the above object, the present invention adopts the following technical solution:

[0005] A method for synthesizing indenyl-substituted polyfluoroaromatic hydrocarbons, which uses 2-iodostyrene compounds, 7-oxa-norbornadiene and polyfluoroaromatic hydrocarbons as raw materials, reacts in an organic solvent under the joint action of a palladium catalyst, a ligand, a base and an additive, and obtains an indenyl-substituted polyfluoroaromatic hydrocarbon compound through post-treatment after the reaction is completed;

[0006] The reaction formula of the synthesis method is as follows:

[0007]

[0008] In the formula, R 1 is selected from one of hydrogen atom, alkyl group, alkoxy group, aryl group and halogen; R 2 It is selected from one of hydrogen atom, alkyl group, alkoxy group, ester group, acyl group and cyano group; R is alkyl group; n is the number of fluorine atoms in the polyfluoroaromatic hydrocarbon.

[0009] Preferably, R in the 2-iodostyrene compound1 One selected from hydrogen, methyl, methoxy, phenyl, trifluoromethyl, fluorine and chlorine; R in polyfluorinated aromatic hydrocarbons 2 It is selected from one of hydrogen atom, methyl, benzyloxymethyl, methoxy, acetyl, tert-butyl acrylate, cyano, tert-butyldimethylsilyloxymethyl; R is one of methyl, ethyl, propyl or n-butyl; the number n of fluorine atoms in the polyfluoroaromatic hydrocarbon is 3, 4 or 5.

[0010] Preferably, the palladium catalyst is one of palladium acetate, palladium chloride, palladium trifluoroacetate, bis(tricyclohexylphosphine)palladium dichloride or bis(acetonitrile)palladium dichloride.

[0011] Preferably, the ligand is one of triphenylphosphine, tri(p-methylphenyl)phosphine, tri(p-methoxyphenyl)phosphine, tri(p-fluorophenyl)phosphine, tricyclohexylphosphine tetrafluoroborate, tri-tert-butylphosphine tetrafluoroborate, 1,2-bis(diphenylphosphine)ethane, bis(diphenylphosphine)methane, 1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphine)propane, and 4,5-bisdiphenylphosphine-9,9-dimethyloxanthene.

[0012] Preferably, the base is one of cesium carbonate, cesium acetate, potassium carbonate, sodium acetate, potassium phosphate, triethylamine, and diisopropylamine.

[0013] Preferably, the organic solvent is one of ethylene glycol dimethyl ether, toluene, dioxane, acetonitrile, tetrahydrofuran or 1,2-dichloroethane.

[0014] Preferably, the additive is one of silver carbonate, silver acetate, silver nitrate and cuprous iodide.

[0015] Preferably, the molar ratio of the 2-iodostyrene compound, 7-oxa-norbornadiene, polyfluoroaromatic hydrocarbon, palladium catalyst, ligand, base and additive is 0.1:0.2:0.3:0.01:0.02:0.3:0.2; and the concentration of the 2-iodostyrene compound in the reaction solution is 0.1 mol / L.

[0016] Preferably, the reaction temperature is 110-150°C, the reaction time is 10-24h, more preferably 130°C for 16h.

[0017] Preferably, the post-treatment step is as follows: after the reaction is completed, the reaction system is cooled, the organic solvent is removed by rotary evaporation under reduced pressure, and the residue is concentrated. The residue is mixed with silica gel and separated by column chromatography to obtain an indenyl-substituted polyfluoroaromatic compound; the eluent for column chromatography separation is a mixture of petroleum ether and ethyl acetate in a volume ratio of 200 to 10:1.

[0018] By adopting the above technology, compared with the prior art, the beneficial effects of the present invention are as follows:

[0019] 1. The present invention has the advantages of low reaction cost, safe and readily available raw materials, good functional group tolerance, and wide substrate universality;

[0020] 2. A variety of indenyl-substituted polyfluoroaromatic compounds were obtained, not limited to nitrogen or oxygen heterocyclic frameworks, which expanded the scope of alkylated polyfluoroaromatics.

[0021] 3. The present invention effectively combines the indene ring skeleton and polyfluoroaromatic hydrocarbons, providing a convenient and effective strategy for preparing bioactive molecules containing similar skeletons. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The H-NMR spectrum of the product structure of Example 1;

[0023] Figure 2 This is the H-NMR spectrum of the product structure of Example 2;

[0024] Figure 3 This is the H-NMR spectrum of the product structure of Example 3;

[0025] Figure 4 This is the H-NMR spectrum of the product structure of Example 4;

[0026] Figure 5 This is the H-NMR spectrum of the product structure of Example 5;

[0027] Figure 6 This is the H-NMR spectrum of the product structure of Example 6;

[0028] Figure 7 This is the H-NMR spectrum of the product structure of Example 7;

[0029] Figure 8 This is the H-NMR spectrum of the product structure of Example 8;

[0030] Fig. 9 This is the H-NMR spectrum of the product structure of Example 9;

[0031] Fig.10 This is the H-NMR spectrum of the product structure of Example 10;

[0032] Fig.11 This is the H-NMR spectrum of the product structure of Example 11. DETAILED DESCRIPTION

[0033] The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto;

[0034] Embodiment 1:

[0035]

[0036] 1-iodo-2-(prop-1-en-2-yl)benzene (24.3 mg, 0.1 mmol), dimethyl 7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate (42.0 mg, 0.2 mmol), 2,3,5,6-tetrafluoroanisole (54.0 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (7.4 mg, 0.01 mmol), tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol), cesium carbonate (97.8 mg, 0.3 mmol) and silver carbonate (54.8 mg, 0.2 mmol) were added to a 25 mL reaction bottle in sequence, followed by addition of 1.0 ml of 1,2-dichloroethane, sealing the bottle, and stirring in an oil bath at 130° C. for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the residue was separated by column chromatography (petroleum ether / ethyl acetate = 100:1-50:1, v / v) to obtain the target product (51%).

[0037] 1 H NMR(400MHz,Chloroform-d)δ7.30(t,J=4.7Hz,1H),7.12(d,J=2.2Hz,3H),6.52(d,J=5.5Hz,1H),6.24(dt,J=5 .3,2.5Hz,1H),3.92(d,J=1.3Hz,3H),3.07(dt,J=13.5,1.8Hz,1H),2.90(dt,J=13.4,1.8Hz,1H),1.29(s,3H).

[0038] Embodiment 2:

[0039]

[0040] 1-iodo-4-methyl-2-(prop-1-en-2-yl)benzene (25.8 mg, 0.1 mmol), dimethyl 7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate (42.0 mg, 0.2 mmol), 2,3,5,6-tetrafluoroanisole (54.0 mg, 0.3 mmol), palladium acetate (2.2 mg, 0.01 mmol), tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol), cesium carbonate (97.8 mg, 0.3 mmol) and silver carbonate (54.8 mg, 0.2 mmol) were added to a 25 mL reaction bottle in sequence, followed by adding 1.0 ml of 1,2-dichloroethane, sealing the bottle, and stirring in an oil bath at 130° C. for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the residue was separated by column chromatography (petroleum ether / ethyl acetate = 100:1-50:1, v / v) to obtain the target product (52%).

[0041] 1 H NMR(400MHz,Chloroform-d)δ7.20(s,1H),7.10(d,J=7.5Hz,1H),7.02(d,J=7.6Hz,1H),6.57(d,J=5.5Hz,1H),6.24(dd,J=5 .4,2.7Hz,1H),4.01(t,J=1.3Hz,3H),3.14(dt,J=13.4,1.6Hz,1H),2.91(dt,J=13.4,1.6Hz,1H),2.40(s,3H),1.34(s,3H).

[0042] Embodiment 3:

[0043]

[0044] 4-Chloro-2-iodo-1-(prop-1-en-2-yl)benzene (27.8 mg, 0.1 mmol), dimethyl 7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate (42.0 mg, 0.2 mmol), 2,3,5,6-tetrafluoroanisole (54.0 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (7.4 mg, 0.01 mmol), tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol), cesium carbonate (97.8 mg, 0.3 mmol) and silver carbonate (54.8 mg, 0.2 mmol) were added to a 25 mL reaction bottle in sequence, followed by addition of 1.0 ml of 1,2-dichloroethane, sealing, and stirring in an oil bath at 130° C. for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the residue was separated by column chromatography (petroleum ether / ethyl acetate = 100:1-50:1, v / v) to obtain the target product (53%).

[0045] 1 H NMR(400MHz,Chloroform-d)δ7.29(d,J=8.5Hz,1H),7.20–7.12(m,2H),6.53(d,J=5.5Hz,1H),6.40(dt, J=5.3,2.5Hz,1H),4.01(t,J=1.4Hz,3H),3.13(dt,J=13.5,1.8Hz,1H),3.06–2.96(m,1H),1.36(s,3H).

[0046] Embodiment 4:

[0047]

[0048] 4-Fluoro-2-iodo-1-(prop-1-en-2-yl)benzene (26.2 mg, 0.1 mmol), dimethyl 7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate (42.0 mg, 0.2 mmol), 2,3,5,6-tetrafluoroanisole (54.0 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (7.4 mg, 0.01 mmol), tri-tert-butylphosphine tetrafluoroborate (5.8 mg, 0.02 mmol), potassium carbonate (41.4 mg, 0.3 mmol) and silver carbonate (54.8 mg, 0.2 mmol) were added to a 25 mL reaction bottle in sequence, followed by addition of 1.0 ml of 1,2-dichloroethane, sealing the bottle, and stirring in an oil bath at 130° C. for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the residue was separated by column chromatography (petroleum ether / ethyl acetate = 100:1-50:1, v / v) to obtain the target product (47%).

[0049] 1 H NMR(400MHz,Chloroform-d)δ7.29(dd,J=9.0,4.9Hz,1H),6.87(ddt,J=9.3,4.6,2.4Hz,2H),6.54(d,J=5.6Hz,1H),6.4 1(dt,J=5.3,2.5Hz,1H),4.01(t,J=1.2Hz,3H),3.13(dt,J=13.5,1.8Hz,1H),3.01(dt,J=13.6,1.9Hz,1H),1.37(s,3H).

[0050] Embodiment 5:

[0051]

[0052] 2-iodo-1-methyl-3-(prop-1-en-2-yl)benzene (25.8 mg, 0.1 mmol), dimethyl 7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate (42.0 mg, 0.2 mmol), 2,3,5,6-tetrafluoroanisole (54.0 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (7.4 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), cesium carbonate (97.8 mg, 0.3 mmol) and silver carbonate (54.8 mg, 0.2 mmol) were added to a 25 mL reaction bottle in sequence, followed by adding 1.0 ml of 1,4-dioxane, sealing the bottle, and stirring in an oil bath at 130° C. for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the residue was separated by column chromatography (petroleum ether / ethyl acetate = 100:1-50:1, v / v) to obtain the target product (62%).

[0053] 1 H NMR(400MHz,Chloroform-d)δ7.20(d,J=7.4Hz,1H),7.11(t,J=7.4Hz,1H),7.02(d,J=7.4Hz,1H),6.72(d,J=5.6Hz,1H),6.31(dt ,J=5.3,2.5Hz,1H),4.01(d,J=1.5Hz,3H),3.14(dt,J=13.5,1.8Hz,1H),2.91(dt,J=13.5,1.9Hz,1H),2.36(s,3H),1.33(s,3H).

[0054] Embodiment 6:

[0055]

[0056] 1-(But-1-en-2-yl)-2-iodo-4-methoxybenzene (28.8 mg, 0.1 mmol), dimethyl 7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate (42.0 mg, 0.2 mmol), 2,3,5,6-tetrafluoroanisole (54.0 mg, 0.3 mmol), palladium acetate (2.2 mg, 0.01 mmol), tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol), cesium carbonate (97.8 mg, 0.3 mmol) and silver carbonate (54.8 mg, 0.2 mmol) were added to a 25 mL reaction bottle in sequence, followed by addition of 1.0 ml of 1,2-dichloroethane, sealing the bottle, and stirring in an oil bath at 130° C. for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the residue was separated by column chromatography (petroleum ether / ethyl acetate = 100:1-10:1, v / v) to obtain the target product (45%).

[0057] 1 H NMR(400MHz,Chloroform-d)δ7.24–7.15(m,1H),6.72(dq,J=5.1,2.5Hz,2H),6.57(d,J=5.6Hz,1H),6.28(dt,J=5.5,2.6Hz, 1H),3.98(d,J=1.3Hz,3H),3.79(s,3H),3.20–3.10(m,1H),3.08–2.98(m,1H),1.90(q,J=7.4Hz,2H),0.55(t,J=7.4Hz,3H).

[0058] Embodiment 7:

[0059]

[0060] 1-(But-1-en-2-yl)-2-iodobenzene (25.8 mg, 0.1 mmol), dimethyl 7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate (42.0 mg, 0.2 mmol), 2,3,5,6-tetrafluoroanisole (54.0 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (7.4 mg, 0.01 mmol), tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol), cesium carbonate (97.8 mg, 0.3 mmol) and silver carbonate (54.8 mg, 0.2 mmol) were added to a 25 mL reaction bottle in sequence, followed by addition of 1.0 ml of 1,2-dichloroethane, sealing the bottle, and stirring in an oil bath at 130° C. for 14 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the residue was separated by column chromatography (petroleum ether / ethyl acetate = 200:1-50:1, v / v) to obtain the target product (48%).

[0061] 1 H NMR(400MHz,Chloroform-d)δ7.33(q,J=4.2,3.4Hz,1H),7.22–7.14(m,3H),6.63(d,J=5.6Hz,1H),6.25(dt,J=5.4,2.6Hz,1H),3. 98(d,J=1.3Hz,3H),3.17(dt,J=13.5,1.8Hz,1H),3.04(dt,J=13.4,1.8Hz,1H),1.93(qd,J=7.2,2.7Hz,2H),0.54(t,J=7.4Hz,3H).

[0062] Embodiment 8:

[0063]

[0064] 1-iodo-2-(prop-1-en-2-yl)benzene (24.3 mg, 0.1 mmol), dimethyl 7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate (42.0 mg, 0.2 mmol), 1,2,3,5,6-pentafluorobenzene (50.4 mg, 0.3 mmol), palladium trifluoroacetate (3.3 mg, 0.01 mmol), tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol), potassium phosphate (63.3 mg, 0.3 mmol) and silver carbonate (54.8 mg, 0.2 mmol) were added to a 25 mL reaction bottle in sequence, followed by adding 1.0 ml of 1,4-dioxane, sealing the bottle, and stirring in an oil bath at 130° C. for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the residue was separated by column chromatography (petroleum ether / ethyl acetate = 200:1-100:1, v / v) to obtain the target product (60%).

[0065] 1 H NMR(400MHz,Chloroform-d)δ7.43–7.36(m,1H),7.19(t,J=4.0Hz,3H),6.59(d,J=5.6Hz,1H),6.3 1(dt,J=5.4,2.6Hz,1H),3.18(dt,J=13.5,2.0Hz,1H),3.07(dt,J=13.4,2.0Hz,1H),1.40(s,3H).

[0066] Embodiment 9:

[0067]

[0068] 1-iodo-2-(prop-1-en-2-yl)benzene (24.3 mg, 0.1 mmol), dimethyl 7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate (42.0 mg, 0.2 mmol), 1,2,4,5-tetrafluorobenzene (45.0 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (7.4 mg, 0.01 mmol), tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol), cesium carbonate (97.8 mg, 0.3 mmol) and silver carbonate (54.8 mg, 0.2 mmol) were added to a 25 mL reaction bottle in sequence, followed by adding 1.0 ml of toluene, sealing the bottle, and stirring in an oil bath at 130° C. for 14 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the residue was separated by column chromatography (petroleum ether / ethyl acetate = 200:1-100:1, v / v) to obtain the target product (50%).

[0069] 1H NMR(400MHz,Chloroform-d)δ7.39(t,J=4.4Hz,1H),7.20(d,J=3.1Hz,3H),6.85(tt,J=9.6,7.4Hz,1H),6.60(d,J =5.5Hz,1H),6.33(dt,J=5.6,2.6Hz,1H),3.22(dq,J=13.3,1.6Hz,1H),3.05(dq,J=13.2,1.6Hz,1H),1.39(s,3H).

[0070] Embodiment 10:

[0071]

[0072] 1-iodo-2-(prop-1-en-2-yl)benzene (24.3 mg, 0.1 mmol), dimethyl 7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate (42.0 mg, 0.2 mmol), 2,4,5-trifluorobenzonitrile (47.1 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (7.4 mg, 0.01 mmol), tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol), cesium carbonate (97.8 mg, 0.3 mmol) and silver carbonate (54.8 mg, 0.2 mmol) were added to a 25 mL reaction bottle in sequence, followed by addition of 1.0 ml of 1,2-dichloroethane, sealing, and stirring in an oil bath at 130° C. for 12 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the residue was separated by column chromatography (petroleum ether / ethyl acetate = 200:1-50:1, v / v) to obtain the target product (42%).

[0073] 1 H NMR(400MHz,Chloroform-d)δ7.35–7.30(m,1H),7.16–7.07(m,4H),6.51(d,J=5. 5Hz, 1H), 6.24 (dt, J=5.5, 2.7Hz, 1H), 3.11 (qt, J=13.3, 1.7Hz, 2H), 1.35 (s, 3H).

[0074] Embodiment 11:

[0075]

[0076] 1-iodo-2-(prop-1-en-2-yl)benzene (24.3 mg, 0.1 mmol), dimethyl 7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate (42.0 mg, 0.2 mmol), tert-butyldimethyl((2,3,5,6-tetrafluorobenzyl)oxy)silane (88.2 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (7.4 mg, 0.01 mmol), tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol), cesium carbonate (97.8 mg, 0.3 mmol) and silver acetate (33.4 mg, 0.2 mmol) were added to a 25 mL reaction bottle in sequence. 1.0 mL of ethylene glycol dimethyl ether was then added, the mixture was sealed, and the mixture was stirred in an oil bath at 130° C. for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and then the residue was separated by column chromatography (petroleum ether / ethyl acetate = 200:1-100:1, v / v) to obtain the target product (66%).

[0077] 1 H NMR(400MHz,Chloroform-d)δ7.32(p,J=2.7Hz,1H),7.16–7.04(m,3H),6.52(d,J=5.6Hz,1H),6.26(dt,J=5.3,2.5Hz,1H), 4.65(t,J=1.6Hz,2H),3.14(dt,J=13.3,1.8Hz,1H),2.95(dt,J=13.2,1.8Hz,1H),1.31(s,3H),0.81(s,9H),-0.01(s,6H).

[0078] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for synthesizing indenyl-substituted polyfluoroaromatic hydrocarbons, characterized in that: Using 2-iodostyrene compound, 7-oxa-norbornadiene and polyfluoroaromatic hydrocarbon as raw materials, reacting in an organic solvent under the joint action of a palladium catalyst, a ligand, a base and an additive, and after the reaction is completed, post-treatment is performed to obtain an indenyl-substituted polyfluoroaromatic hydrocarbon compound; The reaction formula of the synthesis method is as follows: In the formula, R 1 is selected from one of hydrogen atom, alkyl group, alkoxy group, aryl group and halogen; R 2 It is selected from one of hydrogen atom, alkyl group, alkoxy group, ester group, acyl group and cyano group; R is alkyl group; n is the number of fluorine atoms in the polyfluoroaromatic hydrocarbon.

2. The method for synthesizing indenyl-substituted polyfluoroaromatic hydrocarbons according to claim 1, characterized in that: In the 2-iodostyrene compound, R 1 One selected from hydrogen, methyl, methoxy, phenyl, trifluoromethyl, fluorine and chlorine; R in polyfluorinated aromatic hydrocarbons 2 It is selected from one of hydrogen atom, methyl, benzyloxymethyl, methoxy, acetyl, tert-butyl acrylate, cyano, tert-butyldimethylsilyloxymethyl; R is one of methyl, ethyl, propyl or n-butyl; the number n of fluorine atoms in the polyfluoroaromatic hydrocarbon is 3, 4 or 5.

3. The method for synthesizing indenyl-substituted polyfluoroaromatic hydrocarbons according to claim 1, characterized in that: The palladium catalyst is one of palladium acetate, palladium chloride, palladium trifluoroacetate, bis(tricyclohexylphosphine)palladium dichloride or bis(acetonitrile)palladium dichloride.

4. The method for synthesizing indenyl-substituted polyfluoroaromatic hydrocarbons according to claim 1, characterized in that: The ligand is one of triphenylphosphine, tri(p-methylphenyl)phosphine, tri(p-methoxyphenyl)phosphine, tri(p-fluorophenyl)phosphine, tricyclohexylphosphine tetrafluoroborate, tri-tert-butylphosphine tetrafluoroborate, 1,2-bis(diphenylphosphine)ethane, bis(diphenylphosphine)methane, 1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphine)propane, and 4,5-bisdiphenylphosphine-9,9-dimethylxanthene.

5. The method for synthesizing indenyl-substituted polyfluoroaromatic hydrocarbons according to claim 1, characterized in that: The base is one of cesium carbonate, cesium acetate, potassium carbonate, sodium acetate, potassium phosphate, triethylamine and diisopropylamine.

6. The method for synthesizing indenyl-substituted polyfluoroaromatic hydrocarbons according to claim 1, characterized in that: The organic solvent is one of ethylene glycol dimethyl ether, toluene, dioxane, acetonitrile, tetrahydrofuran or 1,2-dichloroethane.

7. The method for synthesizing indenyl-substituted polyfluoroaromatic hydrocarbons according to claim 1, characterized in that: The additive is one of silver carbonate, silver acetate, silver nitrate and cuprous iodide.

8. The method for synthesizing indenyl-substituted polyfluoroaromatic hydrocarbons according to claim 1, characterized in that: The molar ratio of the 2-iodostyrene compound, 7-oxa-norbornadiene, polyfluoroaromatic hydrocarbon, palladium catalyst, ligand, base and additive is 0.1:0.2:0.3:0.01:0.02:0.3:0.2; the concentration of the 2-iodostyrene compound in the reaction solution is 0.1 mol / L.

9. The method for synthesizing indenyl-substituted polyfluoroaromatic hydrocarbons according to claim 1, characterized in that: The reaction temperature is 110-150° C., and the reaction time is 10-24 hours.

10. The method for synthesizing indenyl-substituted polyfluoroaromatic hydrocarbons according to claim 1, characterized in that: The post-treatment step is: after the reaction is completed, the reaction system is cooled, the organic solvent is removed by rotary evaporation under reduced pressure, and the residue is concentrated. The residue is mixed with silica gel and separated by column chromatography to obtain an indenyl-substituted polyfluoroaromatic compound; the eluent for column chromatography separation is a mixture of petroleum ether and ethyl acetate in a volume ratio of 200 to 10:1.

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