Process for the electrooxidative synthesis of fluoralkyl substituted dibenzocycloheptanone compounds

Abstract

This invention discloses a method for the electro-oxidative synthesis of fluoroalkyl-substituted dibenzocycloheptanone compounds, relating to the field of organic synthesis technology. Specifically, it discloses an electrochemical reaction of an o-propynoyl biphenyl compound and a sodium fluoroalkyl sulfinate compound to obtain fluoroalkyl-substituted dibenzocycloheptanone compounds. Using an o-propynoyl biphenyl compound and a sodium fluoroalkyl sulfinate compound as raw materials, the two are subjected to a constant current electrochemical reaction in an electrolyte solution. Under specific reaction temperature and current conditions, the fluoroalkyl sulfinate anion is oxidized to a fluoroalkyl radical. This radical attacks the α-position of the carbonyl group of the ketene reactant to obtain an alkenyl radical. The alkenyl radical then undergoes 7-endo-trig cyclization to another benzene ring to construct a seven-membered ring. Finally, deprotonation yields the fluoroalkyl-substituted dibenzocycloheptanone compounds.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to a method for the electro-oxidative synthesis of fluoroalkyl-substituted dibenzocycloheptanone compounds. Background Technology

[0002] Colchicine is an alkaloid with various physiological activities that has been isolated and utilized by humans for a long time. However, due to its significant toxic side effects, it has not been effectively developed and utilized in anti-tumor applications. Nevertheless, natural colchicine derivatives (with a 6-7-6 polycyclic structure) have been found to have low toxicity and good activity, with dibenzocycloheptanine as their core skeleton. Representative compounds are shown below: NSC51046, ZD 6126, and N-acetylcoichine.

[0003]

[0004] The direct construction of the dibenzocycloheptanone skeleton has been a research interest for organic synthetic chemists for decades. On the other hand, introducing fluorine atoms into drug molecules often improves biological activity, such as solubility, bioavailability, and thermal stability. In recent years, organic synthetic chemists have conducted extensive work on introducing fluorine-containing groups into organic molecules.

[0005] Therefore, finding green and efficient methods for synthesizing fluoroalkyl-substituted dibenzocycloheptanone compounds is a very challenging and valuable research endeavor, which offers the possibility of finding novel compounds with pharmacological activities similar to those of the natural colchicine class. Summary of the Invention

[0006] The purpose of this invention is to provide a method for the electro-oxidative synthesis of fluoroalkyl-substituted dibenzocycloheptanone compounds, in order to solve the problems existing in the prior art, thereby achieving a green and efficient synthesis of fluoroalkyl-substituted dibenzocycloheptanone compounds.

[0007] To achieve the above objectives, the present invention provides the following solution:

[0008] This invention provides a method for the electro-oxidative synthesis of fluoroalkyl-substituted dibenzocycloheptanone compounds, comprising the following steps:

[0009] An electrochemical reaction is performed between an orthopropynyl biphenyl compound and a sodium fluoroalkyl sulfinate compound to obtain the fluoroalkyl-substituted dibenzocycloheptanone compound.

[0010] The o-propionyl biphenyl compounds have the structure shown in formula (I):

[0011]

[0012] In formula (I):

[0013] Ar is an aromatic ring;

[0014] R 1 It can be H, alkyl, halogen atom, ester group, nitro group, cyano group or alkoxy group;

[0015] R 2 It can be aryl, alkyl, or silyl;

[0016] The sodium fluoroalkyl sulfinate compound has the structure shown in formula (II):

[0017]

[0018] In equation (II): R is CF3 or CF2H.

[0019] As a further preferred embodiment of the present invention, the energizing reaction is a constant current energizing reaction of 3mA to 10mA, the reaction temperature is 25 to 70°C, and the reaction time is 4 to 10 hours.

[0020] More preferably, the energizing reaction is a constant current energizing reaction of 4mA, the reaction temperature is 50℃, and the reaction time is 6h.

[0021] The synthesis process of this invention requires a suitable reaction temperature. If the reaction temperature is too high, it will increase the number of side reactions, and if the reaction temperature is too low, it will reduce the yield of the target product.

[0022] The electrolytic reaction is carried out in an electrolytic cell, with the anode material being a carbon electrode graphite felt and the cathode being platinum or nickel.

[0023] As a further preferred embodiment of the present invention, the aromatic ring includes alkyl, alkoxy, aryl, halogenated or ester-substituted benzene rings, furans, pyrroles or thiophenes.

[0024] As a further preferred embodiment of the present invention, the aromatic ring is a benzene ring substituted with alkyl or alkoxy groups.

[0025] As a further preferred embodiment of the present invention, the R 1 It is an alkyl or alkoxy group.

[0026] As a further preferred embodiment of the present invention, the R 2 It is an aryl group.

[0027] As a further preferred embodiment of the present invention, the molar ratio of the o-propyne biphenyl compound to the sodium fluoroalkyl sulfinate compound is 1:(1-3).

[0028] As a further preferred embodiment of the present invention, the electrolyte solution used in the electrostatic reaction is tetrabutylammonium tetrafluoroborate, lithium tert-butoxide, tetrabutylammonium iodate, tetraethylammonium perchlorate, tetraethylammonium hexafluorophosphate, or tetrabutylammonium perchlorate; the solvent in the electrolyte solution used in the electrostatic reaction is at least one selected from acetonitrile, water, dichloroethane, methanol, isopropanol, ethyl acetate, N,N-dimethylformamide, and tetrahydrofuran.

[0029] The concentration of the electrolyte solution used in the electrolytic reaction is 0.1 mol / L.

[0030] As a further preferred embodiment of the present invention, the electrolyte is tetraethylamine perchlorate, and the solvent is a mixed solvent of acetonitrile and water; wherein the volume ratio of acetonitrile to water is 3:1.

[0031] The present invention also provides fluoroalkyl-substituted dibenzocycloheptanone compounds synthesized by the method.

[0032] Taking sodium difluoroalkyl sulfinate as an example, the synthesis reaction of this invention is illustrated below:

[0033]

[0034] During the reaction, o-propionyl biphenyl compounds react with sodium difluorosulfinate compounds, which are precursors of difluoromethyl radicals (CF2H·), in a solvent (preferably a mixture of acetonitrile and water). Under anodic oxidation conditions in an electrolytic cell, fluoroalkyl-substituted dibenzocycloheptanone compounds are obtained through free radical tandem cyclization.

[0035] In the above reaction, o-alkynylbenzene reacts with sodium difluorosulfinate in an electrolyte and solvent under current-driven conditions to yield fluoroalkyl-substituted dibenzocycloheptanone compounds. The reaction mechanism is hypothesized as follows:

[0036]

[0037] First, the difluoromethyl sulfinate ion undergoes oxidation at the anode, losing electrons to generate a difluoroalkyl radical. This radical attacks the α-alkynyl carbon position of the carbonyl group of biphenyl, generating a more thermodynamically stable radical A. Radical A then undergoes 7-endo-trig cyclization to the benzene ring to form a new radical B. Radical B then loses an electron to generate an aryl cation C, which is subsequently deprotonated to form a dibenzocycloheptanone compound.

[0038] The present invention discloses the following technical effects:

[0039] This invention uses o-propyneyl biphenyl compounds and sodium fluoroalkyl sulfinates as raw materials. The two compounds are reacted with a constant current in an electrolyte solution. Under specific reaction temperature and current conditions, the fluoroalkyl sulfinate anion is oxidized to a fluoroalkyl radical. This radical attacks the carbonyl α-position of the acetylene reactant to obtain an alkenyl radical. The alkenyl radical then undergoes 7-endo-trig cyclization to add to another benzene ring to achieve the construction of a seven-membered ring. Finally, deprotonation yields a fluoroalkyl-substituted dibenzocycloheptanone compound. Attached Figure Description

[0040] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0041] Figure 1 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 1 1 H NMR spectrum;

[0042] Figure 2 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 1 13 C NMR spectrum;

[0043] Figure 3 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 1 19 F NMR spectrum;

[0044] Figure 4 The fluoroalkyl-substituted dibenzocycloheptanone compounds obtained in Example 2 1 H NMR spectrum;

[0045] Figure 5 The fluoroalkyl-substituted dibenzocycloheptanone compounds obtained in Example 2 13 C NMR spectrum;

[0046] Figure 6 The fluoroalkyl-substituted dibenzocycloheptanone compounds obtained in Example 2 19 F NMR spectrum;

[0047] Figure 7 The fluoroalkyl-substituted dibenzocycloheptanone compounds obtained in Example 3 1 H NMR spectrum;

[0048] Figure 8 The fluoroalkyl-substituted dibenzocycloheptanone compounds obtained in Example 313 C NMR spectrum;

[0049] Figure 9 The fluoroalkyl-substituted dibenzocycloheptanone compounds obtained in Example 3 19 F NMR spectrum;

[0050] Figure 10 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 4 1 H NMR spectrum;

[0051] Figure 11 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 4 13 C NMR spectrum;

[0052] Figure 12 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 4 19 F NMR spectrum;

[0053] Figure 13 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 5 1 H NMR spectrum;

[0054] Figure 14 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 5 13 C NMR spectrum;

[0055] Figure 15 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 5 19 F NMR spectrum. Detailed Implementation

[0056] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0057] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0058] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0059] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0060] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0061] Example 1

[0062] In a reaction tube, o-propargyl biphenyl 1a (102.6 mg, 0.3 mmol, 1.0 equiv.), sodium difluoromethyl sulfinate 2a (124.2 mg, 0.9 mmol, 3.0 equiv.), and tetraethylamine perchlorate (92 mg, 0.4 mmol, 0.1 M) were accurately added, followed by a mixed solvent of MeCN / H2O (v / v, 3:1, 4 mL). The reaction was carried out at 50 °C for 6 h under constant current. All solvent was transferred to a round-bottom flask. Silica was added to the flask, and the solvent was evaporated under vacuum. Purification was performed by silica gel column chromatography using n-hexane / EtOAc (v / v, 3:1) as the eluent to obtain the corresponding product 3a in 57% yield. The reaction formula is as follows:

[0063]

[0064] Product NMR data: 1 H NMR (400MHz, CDCl3) δ7.92 (d, J=7.8Hz, 1H),7.69–7.65(m,1H),7.59–7.50(m,2H),7.35–7.32(m,3H),7.22(s,2 H),6.78(d,J=2.4Hz,1H),6.41(d,J=2.3Hz,1H),6.12(t,J=53.6Hz,1H), 3.89(s,3H),3.27(s,3H). 13C NMR (101MHz, CDCl3) δ196.0,160.9,160.1, 145.4,144.1(t,J=9.3Hz),140.2,139.4,136.4,133.4(t,J=6.6Hz),131.43, 128.9,128.4,128.0,127.7,125.3,118.4,112.6(t,J=8.9Hz),110.3,106.9, 99.6,55.6,55.6. 19 F NMR(377MHz, CDCl3)δ-100.79(d,J=315.9Hz), -114.66(d,J=315.9Hz).HR–MS(ESI)m / z calc.for C 24 H 18 19 F2O3[M+H]+:393.1297,found:393.1274.

[0065] Figure 1 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 1 1 H NMR spectrum.

[0066] Figure 2 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 1 13 C10 NMR spectrum.

[0067] Figure 3 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 1 19 F NMR spectrum.

[0068] Example 2

[0069] In a reaction tube, o-propargyl biphenyl 1b (126.0 mg, 0.3 mmol, 1.0 equiv.), sodium difluoromethyl sulfinate 2a (124.2 mg, 0.9 mmol, 3.0 equiv.), and tetraethylamine perchlorate (92 mg, 0.4 mmol, 0.1 M) were accurately added, followed by a mixed solvent of MeCN / H2O (v / v, 3:1, 4 mL). The reaction was carried out at 50 °C for 6 h under constant current. All solvent was transferred to a round-bottom flask. Silica was added to the flask, and the solvent was evaporated under vacuum. Purification was performed by silica gel column chromatography using n-hexane / EtOAc (v / v, 3:1) as the eluent to obtain the corresponding product 3b in 55% yield. The reaction formula is as follows:

[0070]

[0071] Product NMR data: 1 H NMR (400MHz, CDCl3) δ7.88 (d, J=7.9Hz, 1H),7.67–7.63(m,1H),7.52(d,J=4.2Hz,2H),7.44(d,J=8.5Hz,2H),7.0 7(d,J=7.7Hz,2H),6.74(d,J=2.4Hz,1H),6.38(d,J=2.3Hz,1H),6.10(d,J =53.9Hz,1H),3.87(s,3H),3.31(s,3H). 13 CNMR(101MHz,CDCl3)δ195.7, 161.1,156.0,145.3,142.9(t,J=9.2Hz),140.3,138.5,133.7(t,J=7.0Hz),1 31.5,130.9,130.0,129.0,128.5,125.3,122.2,117.7,114.7,112.4(t,J=8.9 Hz),110.0,106.9,99.3,55.6,55.6. 19 F NMR(377MHz, CDCl3)δ-100.45(d,J=317.2Hz),-114.86(d,J=317.0Hz).HR–MS(ESI)m / z calc.for C 24 H 17 19 F2O3[M+H] + :471.0402,found:471.0373.

[0072] Figure 4 The fluoroalkyl-substituted dibenzocycloheptanone compounds obtained in Example 2 1 H NMR spectrum.

[0073] Figure 5 The fluoroalkyl-substituted dibenzocycloheptanone compounds obtained in Example 2 13 C10 NMR spectrum.

[0074] Figure 6 The fluoroalkyl-substituted dibenzocycloheptanone compounds obtained in Example 2 19 F NMR spectrum.

[0075] Example 3

[0076] In a reaction tube, o-propargyl biphenyl 1c (111.6 mg, 0.3 mmol, 1.0 equiv.), sodium difluoromethyl sulfinate 2a (124.2 mg, 0.9 mmol, 3.0 equiv.), and tetraethylamine perchlorate (92 mg, 0.4 mmol, 0.1 M) were accurately added, followed by a mixed solvent of MeCN / H2O (v / v, 3:1, 4 mL). The reaction was carried out at 50 °C for 6 h under constant current. All solvent was transferred to a round-bottom flask. Silica was added to the flask, and the solvent was evaporated under vacuum. Purification was performed by silica gel column chromatography using n-hexane / EtOAc (v / v, 3:1) as the eluent to obtain the corresponding product 3c in 60% yield. The reaction formula is as follows:

[0077]

[0078] Product NMR data: 1 H NMR (400MHz, CDCl3) δ7.54 (d, J=8.5Hz, 1H),7.40(d,J=2.3Hz,1H),7.34–7.31(m,3H),7.22(s,2H),7.06(dd,J=8. 5,2.4Hz,1H),6.76(d,J=2.4Hz,1H),6.40(d,J=2.4Hz,1H),6.11(t,J=54.0 Hz,1H),3.96(s,3H),3.88(s,3H),3.26(s,3H). 13 C NMR(101MHz,CDCl3)δ 194.8,162.0,160.9,160.2,143.8(t,J=9.4Hz),140.1,139.6139.1,138.6, 128.4,128.0,127.7,118.5,115.2,114.2,113.8,112.8(t,J=8.4Hz),110.5, 106.9,99.6,55.7,55.6,55.6. 19 F NMR(377MHz, CDCl3)δ-100.86(d,J=315.3Hz),-115.01(d,J=315.3Hz).HR–MS(ESI)m / z calc.for C 25 H 21 19 F2O4[M+H] + :423.1403,found:423.1379.

[0079] Figure 7 The fluoroalkyl-substituted dibenzocycloheptanone compounds obtained in Example 31 H NMR spectrum.

[0080] Figure 8 The fluoroalkyl-substituted dibenzocycloheptanone compounds obtained in Example 3 13 C10 NMR spectrum.

[0081] Figure 9 The fluoroalkyl-substituted dibenzocycloheptanone compounds obtained in Example 3 19 F NMR spectrum.

[0082] Example 4

[0083] In a reaction tube, o-propargyl biphenyl 1a (102.6 mg, 0.3 mmol, 1.0 equiv.), sodium trifluoromethyl sulfinate 2b (140.4 mg, 0.9 mmol, 3.0 equiv.), and tetraethylamine perchlorate (92 mg, 0.4 mmol, 0.1 M) were accurately added, followed by a mixed solvent of MeCN / H2O (v / v, 3:1, 4 mL). The reaction was carried out at 50 °C for 6 h under constant current. All solvent was transferred to a round-bottom flask. Silica was added to the flask, and the solvent was evaporated under vacuum. Purification was performed by silica gel column chromatography using n-hexane / EtOAc (v / v, 3:1) as the eluent to obtain the corresponding product 3d in 46% yield. The reaction formula is as follows:

[0084]

[0085] Product NMR data: 1 H NMR (600MHz, CDCl3) δ7.94(d,J=7.9Hz, 1H),7.70(t,J=7.5Hz,1H),7.56(t,J=7.4Hz,1H),7.50(d,J=7.5Hz,1H), 7.29–7.28(m,3H),7.22(s,2H),6.76(d,J=2.1Hz,1H),6.39(d,J=2.1Hz,1H),3.88(s,3H),3.26(s,3H). 13 C NMR (151MHz, CDCl3) δ195.2,161.1, 160.6,145.0(q,J=2.0Hz),140.0,139.9,136.4,131.6,130.08(q,J=19.2Hz),12 8.9,128.3,128.0,127.8,127.2,124.9,122.5,120.7,118.5,106.9,99.8,55.6, 55.6. 19F NMR(565MHz,CDCl3)δ-52.63.HR–MS(ESI)m / z calc.forC 24 H 27 19 F3O3[M+H] + :411.1203,found:411.1195.

[0086] Figure 10 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 4 1 H NMR spectrum.

[0087] Figure 11 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 4 13 C10 NMR spectrum.

[0088] Figure 12 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 4 19 F NMR spectrum.

[0089] Example 5

[0090] In a reaction tube, o-propargyl biphenyl 1e (124.2 mg, 0.3 mmol, 1.0 equiv.), sodium difluoromethyl sulfinate 2a (106.8 mg, 0.9 mmol, 3.0 equiv.), and tetraethylamine perchlorate (92 mg, 0.4 mmol, 0.1 M) were accurately added, followed by a mixed solvent of MeCN / H2O (v / v, 3:1, 4 mL). The reaction was carried out at 50 °C for 6 h under constant current. All solvent was transferred to a round-bottom flask. Silica was added to the flask, and the solvent was evaporated under vacuum. Purification was performed by silica gel column chromatography using n-hexane / EtOAc (v / v, 3:1) as the eluent to obtain the corresponding product 3e in 45% yield. The reaction formula is as follows:

[0091]

[0092] Product NMR data: 1 H NMR (400MHz, CDCl3) δ7.87 (s, 1H), 7.50–7.45 (m, 2H), 7.33–7.28 (m, 3H), 7.18 (s, 2H), 6.71 (d, J = 2.3Hz, 1H), 6.40(d,J=2.2Hz,1H),6.10(t,J=53.9Hz,1H),3.88(s,3H),3.25(s,3H). 13C NMR (101MHz, CDCl3) δ194.9, 161.1, 160.3, 144.4 (t, J = 9.3Hz), 143.7, 139.2,138.8,138.2,137.4,133.4(t,J=6.8Hz),128.9,128.4,128.2,12 7.8,126.9,118.5,112.6(t,J=9.7Hz),110.2,106.7,100.1,55.7,55.6. 19 F NMR (377MHz, CDCl3)δ-60.03(s).HR–MS(ESI)m / z calc.for C 24 H 18 Cl 19 F2O3[M+H] + :427.0907,found:427.0868.

[0093] Figure 13 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 5 1 H NMR spectrum.

[0094] Figure 14 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 5 13 C10 NMR spectrum.

[0095] Figure 15 The fluoroalkyl-substituted dibenzocycloheptanone compound obtained in Example 5 19 F NMR spectrum.

[0096] The optimization process for reaction conditions is as follows:

[0097] In a reaction tube, accurately add o-propargyl biphenyl 1a (0.3 mmol, 1.0 equiv.), sodium difluoromethyl sulfinate 2a (0.9 mmol, 3.0 equiv.), 0.1 M electrolyte, and 4 mL solvent; use GF as the anode and Pt as the cathode, and apply a constant current of 4 mA for 6 h. Transfer all solvent to a round-bottom flask. Add silica to the flask and evaporate the solvent under vacuum. Purify the product 3a by silica gel column chromatography using n-hexane / EtOAc (v / v, 3:1) as the eluent to calculate the yield. The reaction equation is as follows:

[0098]

[0099] The parameter optimization process and yield are shown in Table 1:

[0100] Table 1

[0101]

[0102]

[0103] In Table 1, [a] indicates that the amount of sodium difluoromethyl sulfinate 2a added is 0.9 mmol, 3.0 equiv.; [b] indicates a constant current of 3 mA; [c] indicates a constant current of 6 mA; [d] indicates that GF is used as the anode and Ni is used as the cathode; [e] indicates that Pt is used as the anode and Pt is used as the cathode; [f] indicates no current is applied.

[0104] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A method for electrooxidative synthesis of fluorinated alkyl-substituted dibenzocycloheptanone compounds, characterized by, The method comprises the following steps: The o-propargyl biphenyl compound and the sodium fluoroalkyl sulfinate compound are subjected to an electric current reaction to obtain the fluoroalkyl substituted dibenzoheptanone compound; The o-propargyl biphenyl compound has a structure as shown in formula (I): （I） In formula (I): Ar is an alkyl or an alkoxy substituted benzene ring; R 1 R is H, an alkyl group, a halogen atom, an ester group, a nitro group, a cyano group or an alkoxy group; R 2 is aryl, alkyl or silyl; The sodium fluoroalkyl sulfinate compound has a structure as shown in formula (II): (I) In formula (II), R is CF3 or CF2H; The electric current reaction is a constant current electric current reaction with a current of 3 mA to 10 mA, a reaction temperature of 50 to 70 DEG C and a reaction time of 4 to 10 h; The anode material of the electric current reaction is a carbon electrode graphite felt, and the cathode material is platinum or nickel; The molar ratio of the o-propargyl biphenyl compound to the sodium fluoroalkyl sulfinate compound is 1: (1 to 3) ; In the electrolyte solution used in the electric current reaction, the electrolyte is tetrabutylammonium tetrafluoroborate, tetrabutylammonium iodate, tetraethylammonium perchlorate, tetraethylammonium hexafluorophosphate or tetrabutylammonium perchlorate; in the electrolyte solution used in the electric current reaction, the solvent is at least one of acetonitrile and water.

2. The method of claim 1, wherein, The electrolyte is tetraethylammonium perchlorate, and the solvent is a mixed solvent of acetonitrile and water.

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