CN115305490A - Method for synthesizing fluoroalkyl substituted dibenzosuberone compound by electrooxidation - Google Patents

Method for synthesizing fluoroalkyl substituted dibenzosuberone compound by electrooxidation Download PDF

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CN115305490A
CN115305490A CN202210113522.7A CN202210113522A CN115305490A CN 115305490 A CN115305490 A CN 115305490A CN 202210113522 A CN202210113522 A CN 202210113522A CN 115305490 A CN115305490 A CN 115305490A
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fluoroalkyl
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substituted
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dibenzosuberone
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张岩
陈聖杰
曾王玉
廖心怡
王依萌
徐敏
涂凤
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Zhejiang Normal University CJNU
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Abstract

The invention discloses a method for synthesizing fluoroalkyl-substituted dibenzosuberone compounds by electrooxidation, and relates to the technical field of organic synthesis. Specifically disclosed is: and carrying out an electrifying reaction on the o-propargyl propionyl biphenyl compound and the fluoroalkyl sodium sulfinate compound to obtain the fluoroalkyl-substituted dibenzosuberone compound. The preparation method comprises the steps of taking an o-propargyl propionyl biphenyl compound and a fluoroalkyl sodium sulfinate compound as raw materials, carrying out constant-current electrifying reaction on the o-propargyl propionyl biphenyl compound and the fluoroalkyl sodium sulfinate compound in an electrolyte solution, oxidizing fluoroalkyl sulfinate anions into fluoroalkyl free radicals under the conditions of specific reaction temperature and current, attacking the alpha position of a carbonyl of an alkynone reactant to obtain an alkenyl free radical, carrying out 7-endo-trig cycloaddition on the alkenyl free radical to another benzene ring to realize the construction of a seven-membered ring, and finally deprotonating to obtain the fluoroalkyl substituted dibenzosuberone compound.

Description

Method for synthesizing fluoroalkyl substituted dibenzosuberone compound by electrooxidation
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing fluoroalkyl-substituted dibenzosuberone compounds by electrooxidation.
Background
Colchicine is an alkaloid with various physiological activities which has been isolated and utilized by people for a long time. But because of obvious toxic and side effects, the compound can not be effectively developed and utilized in the aspect of tumor resistance. However, the natural class of colchicine and its analogues (having 6-7-6 polycyclic structure) derived from its structure were found to have low toxicity and good activity, with dibenzocycloheptane as its core backbone, representative compounds are shown below as NSC51046, ZD 6126 and N-acetylcocaine.
Figure BDA0003495564960000011
The direct construction around the dibenzosuberone skeleton has been of interest to organic synthesis chemists decades ago. On the other hand, introduction of fluorine atoms into drug molecules tends to achieve improved biological activities such as solubility, bioavailability, thermal stability, and the like. In recent years organic synthetic chemists have taken a great deal of work around the introduction of fluorine-containing groups into organic molecules.
Therefore, the search for a green and efficient method for synthesizing fluoroalkyl-substituted dibenzosuberone compounds is a very challenging and research-worthy task, which provides the possibility of searching for novel compounds with similar pharmacological activity to the natural class of colchicine.
Disclosure of Invention
The invention aims to provide a method for synthesizing fluoroalkyl-substituted dibenzosuberone by electrooxidation, which solves the problems in the prior art and can be used for synthesizing fluoroalkyl-substituted dibenzosuberone in a green and high-efficiency manner.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a method for synthesizing fluoroalkyl-substituted dibenzosuberone compounds by electrooxidation, which comprises the following steps:
carrying out an electrifying reaction on an o-propargyl propionyl biphenyl compound and a fluoroalkyl sodium sulfinate compound to obtain a fluoroalkyl substituted dibenzosuberone compound;
the o-propargyl propionyl biphenyl compound has a structure shown in a formula (I):
Figure BDA0003495564960000021
in formula (I):
ar is an aromatic ring;
R 1 is H, alkyl, halogen atom, ester group, nitro, cyano or alkoxy;
R 2 is aryl, alkyl or silicon;
the fluoroalkyl sodium sulfinate compound has a structure shown in a formula (II):
Figure BDA0003495564960000022
in formula (II): r is CF 3 Or CF 2 H。
In a further preferred embodiment of the present invention, the energization reaction is a constant current energization reaction of 3mA to 10mA, the reaction temperature is 25 ℃ to 70 ℃, and the reaction time is 4 h to 10h.
More preferably, the electrifying reaction is a constant current electrifying reaction of 4mA, the reaction temperature is 50 ℃, and the reaction time is 6h.
The synthesis process of the invention needs to ensure proper reaction temperature, the side reactions are increased due to the over-high reaction temperature, and the yield of the target product is reduced due to the over-low reaction temperature.
The electrifying reaction is carried out in an electrolytic cell, the anode material is carbon electrode graphite felt, and the cathode is platinum or nickel.
As a further preference of the present invention, the aromatic ring comprises an alkyl-, alkoxy-, aryl-, halogen-or ester-substituted benzene ring, furan, pyrrole or thiophene.
In a further preferred embodiment of the present invention, the aromatic ring is an alkyl-or alkoxy-substituted benzene ring.
As a further preferred aspect of the present invention, R is 1 Is alkyl or alkoxy.
As a further preferred aspect of the present invention, R is 2 Is an aryl group.
In a further preferred embodiment of the present invention, the molar ratio of the o-propargyl biphenyl compound to the fluoroalkyl sodium sulfinate compound is 1 (1 to 3).
As a further preferable aspect of the present invention, in the electrolyte solution used in the energization reaction, the electrolyte is tetrabutylammonium tetrafluoroborate, lithium tert-butoxide, tetrabutylammonium iodate, tetraethylammonium perchlorate, tetraethylammonium hexafluorophosphate, or tetrabutylammonium perchlorate; in the electrolyte solution used for the electrifying reaction, the solvent is at least one of acetonitrile, water, dichloroethane, methanol, isopropanol, ethyl acetate, N-dimethylformamide and tetrahydrofuran.
The concentration of the electrolyte solution for the electrifying reaction is 0.1mol/L.
As a further preferred of the present invention, the electrolyte is tetra-ethylamine perchlorate, and the solvent is a mixed solvent of acetonitrile and water; wherein the volume ratio of the acetonitrile to the water is 3:1.
The invention also provides fluoroalkyl-substituted dibenzosuberone compounds synthesized by the method.
The synthesis reaction of the present invention is illustrated by taking the sodium difluoroalkylsulfinate radical source as an example, and the reaction formula is as follows:
Figure BDA0003495564960000041
in the reaction process, the o-propargyl propionyl biphenyl compound is utilizedWith difluoromethyl radical (CF) in a solvent (preferably a mixed solvent of acetonitrile and water) 2 H) precursor sodium difluorosulfinate compound, and under the condition of anodic oxidation of an electrolytic cell, carrying out serial cyclization on free radicals to obtain the fluoroalkyl-substituted dibenzosuberone compound.
In the reaction, the ortho-alkynylbenzoyl biphenyl and the sodium difluorosulfinate compound react in electrolyte and solvent under the condition of passing current to obtain the fluoroalkyl-substituted dibenzosuberone compound. The reaction mechanism is presumed to be as follows:
Figure BDA0003495564960000051
firstly, carrying out oxidation reaction on difluoromethyl sulfinate ions at an anode, and losing electrons to generate difluoroalkyl radicals; the free radical attacks the carbon number of carbonyl alpha alkynyl of biphenyl to generate a free radical A with more stable thermodynamics, then the free radical A is cyclized and added to a benzene ring through 7-endo-trig to form a new free radical B, the new free radical B loses one electron to generate an aryl cation C, and then deprotonation is carried out to form the dibenzosuberone compound.
The invention discloses the following technical effects:
the preparation method comprises the steps of taking an o-propargyl propionyl biphenyl compound and a fluoroalkyl sodium sulfinate compound as raw materials, carrying out constant-current electrifying reaction on the o-propargyl propionyl biphenyl compound and the fluoroalkyl sodium sulfinate compound in an electrolyte solution, oxidizing fluoroalkyl sulfinate anions into fluoroalkyl free radicals under the conditions of specific reaction temperature and current, attacking the alpha position of a carbonyl of an alkynone reactant to obtain an alkenyl free radical, carrying out 7-endo-trig cycloaddition on the alkenyl free radical to another benzene ring to realize the construction of a seven-membered ring, and finally deprotonating to obtain the fluoroalkyl substituted dibenzosuberone compound.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 1 1 H NMR spectrum;
FIG. 2 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 1 13 C NMR spectrum;
FIG. 3 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 1 19 F NMR spectrum;
FIG. 4 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 2 1 H NMR spectrum;
FIG. 5 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 2 13 C NMR spectrogram;
FIG. 6 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 2 19 F NMR spectrum;
FIG. 7 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 3 1 H NMR spectrum;
FIG. 8 shows the fluoroalkyl-substituted dibenzosuberone compounds obtained in example 3 13 C NMR spectrum;
FIG. 9 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 3 19 F NMR spectrum;
FIG. 10 shows fluoroalkyl-substituted dibenzosuberone compounds prepared in example 4 1 H NMR spectrum;
FIG. 11 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 4 13 C NMR spectrum;
FIG. 12 shows fluoroalkyl-substituted dibenzosuberone compounds from example 4 19 F NMR spectrum;
FIG. 13 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 5 1 H NMR spectrum;
FIG. 14 shows fluoroalkyl-substituted diphenyl prepared in example 5Process for producing cycloheptanone compound 13 C NMR spectrum;
FIG. 15 shows fluoroalkyl-substituted dibenzosuberone compounds from example 5 19 F NMR spectrum.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
Example 1
To the reaction tube, exactly O-propargyl-propionyl-biphenyl 1a (102.6 mg,0.3mmol,1.0 equiv.), sodium difluoromethylsulfinate 2a (124.2 mg,0.9mmol, 3.0equiv.), tetraethylene perchlorate (92mg, 0.4mmol, 0.1M) and finally MeCN/H as a mixed solvent were added 2 O (v/v, 3. The reaction was carried out at 50 ℃ for 6h with constant current. All solvents were transferred to a round bottom flask. Silica was added to the flask and the solvent was evaporated in vacuo. Purification by silica gel column chromatography using n-hexane/EtOAc (v/v, 3:1) as eluent gave the corresponding product 3a in 57% yield. The reaction formula is as follows:
Figure BDA0003495564960000091
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,2H), 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). 13 C 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 F 2 O 3 [M+H]+: 393.1297,found:393.1274.
FIG. 1 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 1 1 H NMR spectrum.
FIG. 2 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 1 13 C NMR spectrum.
FIG. 3 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 1 19 F NMR spectrum.
Example 2
To the reaction tube, o-propargyl propionyl biphenyl 1b (126.0mg, 0.3mmol,1.0 equiv.), sodium difluoromethylsulfinate 2a (124.2mg, 0.9mmol, 3.0equiv.), tetraethylene perchlorate (92mg, 0.4mmol, 0.1M) were accurately added, and finally, a mixed solvent MeCN/H was added 2 O (v/v, 3. The reaction was carried out at 50 ℃ for 6h with constant current. All solvents were transferred to a round bottom flask. Silica was added to the flask and the solvent was evaporated in vacuo. Purification by silica gel column chromatography using n-hexane/EtOAc (v/v, 3:1) as eluent gave the corresponding product 3b in 55% yield. The reaction formula is as follows:
Figure BDA0003495564960000101
product nmr data: 1 H NMR(400MHz,CDCl 3 )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),7.07 (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 C NMR(101MHz,CDCl 3 )δ195.7, 161.1,156.0,145.3,142.9(t,J＝9.2Hz),140.3,138.5,133.7(t,J＝7.0Hz), 131.5,130.9,130.0,129.0,128.5,125.3,122.2,117.7,114.7,112.4(t,J＝8.9 Hz),110.0,106.9,99.3,55.6,55.6. 19 F NMR(377MHz,CDCl 3 )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 F 2 O 3 [M+H] + :471.0402,found:471.0373.
FIG. 4 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 2 1 H NMR spectrum.
FIG. 5 shows the fluoroalkyl-substituted dibenzosuberone compounds obtained in example 2 13 C NMR spectrum.
FIG. 6 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 2 19 F NMR spectrum.
Example 3
Accurately adding o-propargyl propionyl biphenyl 1 into a reaction tubec (111.6mg, 0.3mmol,1.0 equiv.), sodium difluoromethylsulfinate 2a (124.2mg, 0.9mmol, 3.0equiv.), tetraethyleneperchloric acid (92mg, 0.4mmol, 0.1M), and finally, the mixed solvent MeCN/H is added 2 O (v/v, 3. The reaction was carried out at 50 ℃ for 6h with constant current. All solvents were transferred to a round bottom flask. Silica was added to the flask and the solvent was evaporated in vacuo. Purification by silica gel column chromatography using n-hexane/EtOAc (v/v, 3:1) as eluent gave the corresponding product 3c in 60% yield. The reaction formula is as follows:
Figure BDA0003495564960000111
product nmr data: 1 H NMR(400MHz,CDCl 3 )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,CDCl 3 )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,CDCl 3 )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 F 2 O 4 [M+H] + :423.1403,found:423.1379.
FIG. 7 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 3 1 H NMR spectrum.
FIG. 8 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 3 13 C NMR spectrum.
FIG. 9 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 3 19 F NMR spectrum.
Example 4
To the reaction tube, o-propargyl-biphenyl 1a (102.6mg, 0.3mmol,1.0 equiv.) and sodium trifluoromethanesulfonate 2b (14. Sup. Th.) were accurately added0.4mg,0.9mmol, 3.0equiv.), perchloric acid tetraethylene amine (92mg, 0.4mmol, 0.1M), and finally adding a mixed solvent MeCN/H 2 O (v/v, 3. The reaction was carried out at 50 ℃ for 6h with constant current. All solvents were transferred to a round bottom flask. Silica was added to the flask and the solvent was evaporated in vacuo. Purification by silica gel column chromatography using n-hexane/EtOAc (v/v, 3:1) as eluent gave the corresponding product 3d in 46% yield. The reaction formula is as follows:
Figure BDA0003495564960000121
product nmr data: 1 H NMR(600MHz,CDCl 3 )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,CDCl 3 )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), 128.9,128.3,128.0,127.8,127.2,124.9,122.5,120.7,118.5,106.9,99.8,55.6, 55.6. 19 F NMR(565MHz,CDCl 3 )δ-52.63.HR–MS(ESI)m/z calc.for C 24 H 27 19 F 3 O 3 [M+H] + :411.1203,found:411.1195.
FIG. 10 shows fluoroalkyl-substituted dibenzosuberone compounds prepared in example 4 1 H NMR spectrum.
FIG. 11 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 4 13 C NMR spectrum.
FIG. 12 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 4 19 F NMR spectrum.
Example 5
To the reaction tube, exactly O-propargyl propionyl biphenyl 1e (124.2mg, 0.3mmol,1.0 equiv.), sodium difluoromethylsulfinate 2a (106.8mg, 0.9mmol, 3.0equiv.), tetraethylene perchlorate (92mg, 0.4mmol, 0.1M) and finally mixed solvent MeCN/H were added 2 O(v/v, 3. The reaction was carried out at 50 ℃ for 6h with constant current. All solvents were transferred to a round bottom flask. Silica was added to the flask and the solvent was evaporated in vacuo. Purification by silica gel column chromatography using n-hexane/EtOAc (v/v, 3:1) as eluent gave the corresponding product 3e in 45% yield. The reaction formula is as follows:
Figure BDA0003495564960000131
product nmr data: 1 H NMR(400MHz,CDCl 3 )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). 13 C NMR(101MHz,CDCl 3 )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),128.9,128.4,128.2,127.8, 126.9,118.5,112.6(t,J＝9.7Hz),110.2,106.7,100.1,55.7,55.6. 19 F NMR (377MHz,CDCl 3 )δ-60.03(s).HR–MS(ESI)m/z calc.for C 24 H 18 Cl 19 F 2 O 3 [M+H] + :427.0907,found:427.0868.
FIG. 13 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 5 1 H NMR spectrum.
FIG. 14 shows fluoroalkyl-substituted dibenzosuberone compounds from example 5 13 C NMR spectrum.
FIG. 15 shows fluoroalkyl-substituted dibenzosuberone compounds obtained in example 5 19 F NMR spectrum.
The reaction conditions were optimized as follows:
accurately adding o-propargyl propionyl biphenyl 1a (0.3 mmol,1.0 equiv.), sodium difluoromethylsulfinate 2a (0.9mmol, 3.0 equiv.), electrolyte 0.1M and solvent 4mL into a reaction tube; GF is taken as an anode, pt is taken as a cathode, constant current of 4mA is applied, and the reaction is carried out for 6h. All solvents were transferred to a round bottom flask. Silica was added to the flask and the solvent was evaporated in vacuo. The product 3a was obtained by purification by silica gel column chromatography using n-hexane/EtOAc (v/v, 3:1) as the eluent, and the yield was calculated. The reaction formula is as follows:
Figure BDA0003495564960000141
the parameter optimization procedure and yield are shown in table 1:
TABLE 1
Figure BDA0003495564960000142
Figure BDA0003495564960000151
In Table 1, [ a ] represents that the amount of sodium difluoromethylsulfinate 2a added was 0.9mmol, 3.0equiv; [ b ] represents the constant current of 3mA; [c] represents that constant current is switched on at 6mA; [d] expressed by using GF as an anode and Ni as a cathode; [e] the method is characterized in that Pt is used as an anode and Pt is used as a cathode; [f] indicating that no power is applied.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (10)

1. A method for synthesizing fluoroalkyl-substituted dibenzosuberone compounds by electrooxidation is characterized by comprising the following steps:
carrying out an electrifying reaction on an o-propargyl propionyl biphenyl compound and a fluoroalkyl sodium sulfinate compound to obtain a fluoroalkyl-substituted dibenzosuberone compound;
the o-propargyl propionyl biphenyl compound has a structure shown in a formula (I):
Figure FDA0003495564950000011
in formula (I):
ar is an aromatic ring;
R 1 is H, alkyl, halogen atom, ester group, nitro, cyano or alkoxy;
R 2 is aryl, alkyl or silicon;
the fluoroalkyl sodium sulfinate compound has a structure shown in a formula (II):
Figure FDA0003495564950000012
in formula (II): r is CF 3 Or CF 2 H。
2. The method according to claim 1, wherein the energization reaction is a constant current energization reaction of 3 mA-10 mA, the reaction temperature is 25-70 ℃, and the reaction time is 4-10 h.
3. The method of claim 1, wherein the aromatic ring comprises an alkyl, alkoxy, aryl, halogen, or ester substituted benzene ring, furan, pyrrole, or thiophene.
4. The method of claim 3, wherein the aromatic ring is an alkyl-or alkoxy-substituted benzene ring.
5. The method of claim 1, wherein R is 1 Is alkyl or alkoxy.
6. The method of claim 1, wherein R is 2 Is an aryl group.
7. The method according to claim 1, wherein the molar ratio of the o-propargyl biphenyl compound to the fluoroalkyl sodium sulfinate compound is 1 (1 to 3).
8. The method according to claim 1, wherein in the electrolyte solution used for the energization reaction, the electrolyte is tetrabutylammonium tetrafluoroborate, lithium tert-butoxide, tetrabutylammonium iodate, tetraethylammonium perchlorate, tetraethylammonium hexafluorophosphate, or tetrabutylammonium perchlorate; in the electrolyte solution used for the electrifying reaction, the solvent is at least one of acetonitrile, water, dichloroethane, methanol, isopropanol, ethyl acetate, N-dimethylformamide and tetrahydrofuran.
9. The method according to claim 8, wherein the electrolyte is tetraethylene perchlorate and the solvent is a mixed solvent of acetonitrile and water.
10. A fluoroalkyl substituted dibenzosuberone compound synthesized according to the method of any one of claims 1 to 9.
CN202210113522.7A 2022-01-30 2022-01-30 Method for synthesizing fluoroalkyl substituted dibenzosuberone compound by electrooxidation Pending CN115305490A (en)

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