CN117051414A - Method for electrochemically synthesizing aryl sulfonyl fluoride compound - Google Patents
Method for electrochemically synthesizing aryl sulfonyl fluoride compound Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 30
- 125000004391 aryl sulfonyl group Chemical group 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- -1 aryl triflate Chemical compound 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 14
- 239000012429 reaction media Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- BIOPPFDHKHWJIA-UHFFFAOYSA-N anthracene-9,10-dinitrile Chemical group C1=CC=C2C(C#N)=C(C=CC=C3)C3=C(C#N)C2=C1 BIOPPFDHKHWJIA-UHFFFAOYSA-N 0.000 claims description 15
- PHXQIAWFIIMOKG-UHFFFAOYSA-N NClO Chemical compound NClO PHXQIAWFIIMOKG-UHFFFAOYSA-N 0.000 claims description 13
- PNFCPDDYELHQKF-UHFFFAOYSA-N 4-phenylbenzenesulfonyl fluoride Chemical compound C1=CC(S(=O)(=O)F)=CC=C1C1=CC=CC=C1 PNFCPDDYELHQKF-UHFFFAOYSA-N 0.000 claims description 11
- FWZMWMSAGOVWEZ-UHFFFAOYSA-N potassium;hydrofluoride Chemical compound F.[K] FWZMWMSAGOVWEZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- IZZYABADQVQHLC-UHFFFAOYSA-N 4-methylbenzenesulfonyl fluoride Chemical compound CC1=CC=C(S(F)(=O)=O)C=C1 IZZYABADQVQHLC-UHFFFAOYSA-N 0.000 claims description 6
- OQQACBCYXICOKO-UHFFFAOYSA-N 3-tert-butylbenzenesulfonyl fluoride Chemical compound C(C)(C)(C)C=1C=C(C=CC=1)S(=O)(=O)F OQQACBCYXICOKO-UHFFFAOYSA-N 0.000 claims description 5
- QHEMDSDRFAIOOU-UHFFFAOYSA-N 4-methoxybenzenesulfonyl fluoride Chemical compound COC1=CC=C(S(F)(=O)=O)C=C1 QHEMDSDRFAIOOU-UHFFFAOYSA-N 0.000 claims description 5
- LGWYRYDAHZTSKX-UHFFFAOYSA-N naphthalene-2-sulfonyl fluoride Chemical compound C1=CC=CC2=CC(S(=O)(=O)F)=CC=C21 LGWYRYDAHZTSKX-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 150000002989 phenols Chemical class 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010504 bond cleavage reaction Methods 0.000 description 5
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- 229940095102 methyl benzoate Drugs 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000007876 drug discovery Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical class FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/11—Halogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The application discloses a method for electrochemically synthesizing an aryl sulfonyl fluoride compound, which is characterized by comprising the following steps: s1, mixing reaction raw materials including aryl triflate, DABSO and potassium bifluoride in an electrolytic tank under an inert atmosphere; then adding a reaction medium and an electrolyte into the electrolytic tank, and then adding an organic solvent for dissolution; s2, inserting electrodes into the electrolytic tank, and electrifying to perform electrochemical reaction; s3, extracting, drying and purifying after the reaction to obtain the aryl sulfonyl fluoride compound. Compared with the traditional synthesis method for preparing the aryl sulfonyl fluoride compound by breaking the C-O bond in activated phenols and derivatives thereof, the synthesis method provided by the application has the advantages of low requirements on instruments and equipment, no use of metal catalysts, cost saving, mild reaction conditions, simple operation steps, short reaction time and high yield.
Description
Technical Field
The application relates to the technical field of electrochemical synthesis, in particular to a method for electrochemically synthesizing an aryl sulfonyl fluoride compound.
Background
The sulfonyl fluoride compound has special reactivity, stable balance, oxidation-reduction resistance and high thermodynamic stability for nucleophilic substitution reaction, and is a high-value synthetic fragment in organic synthesis. Fluorosulfonyl group (SO) 2 F) Can be found in almost all fields of modern chemistry, such as drug discovery, chemical biology, material science, etc. However, the introduction of fluorosulfonyl groups (SO 2 F) The method of (2) is also very limitedFurther studies and applications of its response are severely limited. Therefore, the exploration of a novel method for efficiently constructing sulfonyl fluoride compounds by using simple raw materials is of great significance.
Phenol and its homologs are widely present in lignin, so that development of chemical reactions using phenol derivatives as starting materials has a broad application prospect. However, the p-pi bond conjugation results in a phenolic compound having a very reactive acidic hydroxyl group and a high dissociation energy C-O bond, which makes the direct C-O bond cleavage coupling reaction of the phenolic compound difficult to achieve. Thus, conversion of phenolic compounds to phenolic derivatives, such as aryl triflates, not only eliminates the acidity of the phenolic hydroxyl groups, but also reduces the bond energy of the c—o bonds. In recent years, transition metal catalyzed aryl triflates have received much attention through C-O bond activation reactions, which typically require the addition of equivalent amounts of metal reducing agents or in combination with photocatalysis (ref. M.Ratushnyy, N.Kvasovs, S.Sarkar, V.Gevorgyan, visible Light-Induced Palladium-Catalyzed Generation of Aryl Radicals from Aryl triflates. Angew. Chem. Int. Ed.2020,59, 10316-10320). However, in practical production, particularly in pharmaceutical synthetic chemistry, the requirements for the residual amounts of metals are very demanding and trace amounts of metals often require high costs during post-treatment. Thus, there is a great need to develop green, highly efficient nonmetallic catalyzed fluorination of carbon-halogen bond sulfonyl. The organic electrochemical synthesis is a green, mild and efficient synthesis strategy, however, because the direct electrode reduction of the aryl triflate can generate S-O bond cleavage, generate trifluoromethyl sulfonyl free radical and corresponding phenoxide, and can not generate C-O bond cleavage to generate aryl free radical. Thus, it can be predicted that: under the reducing condition, S-O in the aryl triflate is cracked to generate phenolic compounds, and the C-O is cracked to generate the most vigorous competition reaction of aryl radicals. It follows that the formation of aryl radicals by C-O bond cleavage by Single Electron Transfer (SET) of aryl triflates with suitable electron donors is critical in avoiding S-O bond cleavage.
The application envisages whether an aryl triflate can be used as a starting material to synthesize an aryl sulfonyl fluoride compound at room temperature without metal catalysis in the form of a medium.
Disclosure of Invention
In the existing synthesis method, a metal reagent and a noble metal catalyst are often used, and the problem of high cost exists; the photocatalysis synthesis method is adopted, which has the problem of narrower light source and substrate range; aiming at the problems of the existing synthesis method, the application provides a novel electrochemical synthesis process with low cost, simple synthesis steps and wide raw material sources.
The application is realized by the following technical scheme:
a method for electrochemically synthesizing an aromatic sulfonyl fluoride compound, comprising the steps of:
s1, mixing reaction raw materials including aryl triflate, DABSO and potassium bifluoride in an electrolytic tank under an inert atmosphere;
then adding a reaction medium and an electrolyte into the electrolytic tank, and then adding an organic solvent for dissolution;
s2, inserting electrodes into the electrolytic tank, and electrifying to perform electrochemical reaction;
s3, extracting, drying and purifying after the reaction to obtain the aryl sulfonyl fluoride compound.
The application provides a method for preparing an aromatic trifluoro methanesulfonate, DABSO and potassium fluohydride (KHF) 2 ) As a raw material, 9, 10-dicyanoanthracene is used as a medium, acetonitrile is used as a solvent, n Bu 4 NClO 4 as an electrolyte, an aromatic sulfonyl fluoride compound is directly produced by electrochemical reaction in a nitrogen atmosphere.
Specifically, the application provides a method for electrochemically synthesizing an aryl sulfonyl fluoride compound by taking a phenol derivative as a raw material.
Further, a method for electrochemically synthesizing an aryl sulfonyl fluoride compound comprises the following steps: the molar ratio of the aryl trifluoro methane sulfonate, DABSO and potassium fluohydride in the step S1 is (1-3): 1: (3-5).
Preferably, the molar ratio between the aryl triflate, DABSO and potassium fluorohydride is 4:3:12.
further, a method for electrochemically synthesizing an aryl sulfonyl fluoride compound comprises the following steps: the concentration of the aryl trifluoro methane sulfonate in the step S1 in the organic solvent is 0.1-0.5 mmol/ml.
Preferably, the concentration of the aryl triflate is 0.2mmol/ml.
Further, a method for electrochemically synthesizing an aryl sulfonyl fluoride compound comprises the following steps: the concentration of the reaction medium in the step S1 in the organic solvent is 0.01-0.1 mmol/ml; the reaction medium is 9, 10-dicyanoanthracene.
Preferably, the concentration of 9, 10-dicyanoanthracene is 0.04mmol/ml.
Further, a method for electrochemically synthesizing an aryl sulfonyl fluoride compound comprises the following steps: the concentration of the electrolyte in the step S1 in the organic solvent is 0.01-0.1 mmol/ml; the electrolyte is n Bu 4 NClO 4 。
Preferably, the method comprises the steps of, n Bu 4 NClO 4 is 0.05mmol/ml.
Further, a method for electrochemically synthesizing an aryl sulfonyl fluoride compound comprises the following steps: the organic solvent is acetonitrile.
Further, a method for electrochemically synthesizing an aryl sulfonyl fluoride compound comprises the following steps: and S2, inserting a platinum electrode as an anode and an RVC electrode as a cathode into the electrolytic tank, and then conducting electrochemical reaction by constant-voltage direct current of 10-15 mA for 1-3 hours.
Further, a method for electrochemically synthesizing an aryl sulfonyl fluoride compound comprises the following steps: the extractant used in step S3 is ethyl acetate.
Further, a method for electrochemically synthesizing an aryl sulfonyl fluoride compound comprises the following steps: and step S3, purifying by adopting a column chromatography separation method.
Further, a method for electrochemically synthesizing an aryl sulfonyl fluoride compound comprises the following steps: the aryl sulfonyl fluoride compound obtained in the step S3 is one of p-methylbenzenesulfonyl fluoride, p-phenylbenzenesulfonyl fluoride, p-methoxybenzenesulfonyl fluoride, m-tertiary butyl benzenesulfonyl fluoride, 3-methyl-4-sulfonyl fluoride methyl benzoate and 2-naphthalene sulfonyl fluoride.
(p-toluenesulfonyl fluoride), +.>(p-phenylbenzenesulfonyl fluoride),(p-methoxybenzenesulfonyl fluoride), - (Y-O) and (C) are shown in the specification>(m-tert-butylbenzenesulfonyl fluoride),(3-methyl-4-sulfonylfluorobenzoic acid methyl ester), -/->(2-naphthalenesulfonyl fluoride).
The application has the beneficial effects that:
(1) The synthesis method provided by the application has simple steps, and solves the problems of narrow range of metal reagents, expensive metal catalysts, light sources and substrates and the like in the conventional synthesis method. The electrochemical method provided by the application is only carried out at room temperature, the reaction condition is mild, and no metal residue exists in the product. Because the electrochemical reaction only needs to be electrified and does not need complex photochemical reaction equipment, the synthesis method has low requirements on instruments and equipment. In addition, the electric energy is directly applied to the reaction, and the energy conversion is not needed, so that the reaction cost is reduced to a certain extent.
(2) The synthesis method of the application uses aryl trifluoro methane sulfonate, DABSO and KHF 2 As raw materials, 9, 10-dicyanoanthracene is used as a medium and acetonitrile is used as a solvent, and the aryl sulfonyl is prepared by an electrochemical methodThe fluorine compound has higher yield, and the yield can reach more than 60 percent.
(3) Compared with the traditional synthesis method, the synthesis method has low requirements on instruments and equipment, does not use a metal catalyst, saves cost, has mild reaction conditions and simple operation steps, has short reaction time, and can be applied to the fields of scientific research, medical treatment, industry and the like.
Detailed Description
The technical solutions of the present application will be clearly and completely described below in conjunction with specific embodiments, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the application, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
There is provided a method for electrochemically synthesizing an aromatic sulfonyl fluoride compound, comprising the steps of:
s1, mixing reaction raw materials including aryl triflate, DABSO and potassium bifluoride in an electrolytic tank under an inert atmosphere;
then adding a reaction medium and an electrolyte into the electrolytic tank, and then adding an organic solvent for dissolution;
s2, inserting electrodes into the electrolytic tank, and electrifying to perform electrochemical reaction;
s3, extracting, drying and purifying a product obtained by the reaction to obtain the aryl sulfonyl fluoride compound.
The reaction process of the above synthetic method is as follows:
wherein: 1 represents an aryl triflate, 2 represents DABSO, M-1 represents 9, 10-dicyanoanthracene, meCN represents acetonitrile, ar represents an aryl group, and-OTf represents a triflate.
Example 1
A method for electrochemically synthesizing an aromatic sulfonyl fluoride compound (specifically, synthesizing p-toluenesulfonyl fluoride), which is characterized by comprising the following steps:
s1, under the atmosphere of nitrogen, 0.20mmol of0.15mmol DABSO and 0.60mmol Potassium fluorohydride (KHF) 2 ) Adding into a 10.0ml diaphragm-free electrolytic cell;
then adding 0.04mmol of reaction medium (9, 10-dicyanoanthracene) and 0.05mmol of electrolyte into the electrolytic tank n Bu 4 NClO 4 ) Then adding 1.0ml of organic solvent (acetonitrile) and stirring for dissolving for 10 minutes;
s2, inserting a platinum (Pt) electrode serving as an anode and an RVC electrode serving as a cathode into the electrolytic tank, and then introducing 12mA constant-voltage direct current to perform electrochemical reaction for 3 hours;
s3, after the reaction is finished, adding the reaction solution into 10ml of ethyl acetate, washing 2 times with 2.5ml of water, extracting, drying an organic phase with anhydrous sodium sulfate, separating by column chromatography to obtain 26.1mg of p-toluenesulfonyl fluoride, calculating the yield to be 75%, wherein the structural formula of the obtained product p-toluenesulfonyl fluoride is
1 HNMR(500MHz,CDCl 3 )δ7.89(dd,J＝8.4,1.7Hz,2H),7.42(d,J＝8.1Hz,2H),2.49(s,3H). 13 CNMR(126MHz,CDCl 3 )δ147.1,130.3,130.1(d,J＝19Hz),128.4,21.8. 19 FNMR(376MHz,Chloroform-d)δ66.30.
Example 2
A method for electrochemically synthesizing an aromatic sulfonyl fluoride compound (specifically, synthesizing p-phenyl benzenesulfonyl fluoride), which is characterized by comprising the following steps:
s1, under the atmosphere of nitrogen, 0.20mmol of0.15mmol DABSO and 0.60mmol Potassium fluorohydride (KHF) 2 ) Adding into a 10.0ml diaphragm-free electrolytic cell;
then adding 0.04mmol of reaction medium (9, 10-dicyanoanthracene) and 0.05mmol of electrolyte into the electrolytic tank n Bu 4 NClO 4 ) Then adding 1.0ml of organic solvent (acetonitrile) and stirring for dissolving for 10 minutes;
s2, inserting a platinum (Pt) electrode serving as an anode and an RVC electrode serving as a cathode into the electrolytic tank, and then introducing 12mA constant-voltage direct current to perform electrochemical reaction for 3 hours;
s3, after the reaction is finished, adding the reaction solution into 10ml of ethyl acetate, washing 2 times with 2.5ml of water, extracting, drying an organic phase with anhydrous sodium sulfate, separating by column chromatography to obtain 38.2mg of p-phenylbenzenesulfonyl fluoride, and calculating the yield to be 81%, wherein the structural formula of the obtained p-phenylbenzenesulfonyl fluoride is
1 HNMR(500MHz,CDCl 3 )δ8.10–8.01(m,2H),7.85–7.73(m,2H),7.67–7.59(m,2H),7.55–7.41(m,3H). 13 CNMR(126MHz,CDCl 3 )δ148.7,138.5,131.4(d,J＝20Hz),129.3,129.2,129.0,128.2,127.5. 19 FNMR(376MHz,CDCl 3 )δ66.52.
Example 3
A method for electrochemically synthesizing an aromatic sulfonyl fluoride compound (specifically, synthesizing p-methoxybenzenesulfonyl fluoride), which is characterized by comprising the following steps:
s1, under the atmosphere of nitrogen, 0.20mmol of0.15mmol DABSO and 0.60mmol Potassium fluorohydride (KHF) 2 ) Adding into a 10.0ml diaphragm-free electrolytic cell;
then adding 0.04m to the electrolytic cellmol of reaction medium (9, 10-dicyanoanthracene) and 0.05mmol of electrolyte n Bu 4 NClO 4 ) Then adding 1.0ml of organic solvent (acetonitrile) and stirring for dissolving for 10 minutes;
s2, inserting a platinum (Pt) electrode serving as an anode and an RVC electrode serving as a cathode into the electrolytic tank, and then introducing 12mA constant-voltage direct current to perform electrochemical reaction for 3 hours;
s3, after the reaction is finished, adding the reaction solution into 10ml of ethyl acetate, washing 2 times with 2.5ml of water, extracting, drying an organic phase with anhydrous sodium sulfate, separating by column chromatography to obtain 30.1mg of p-phenylbenzenesulfonyl fluoride, and calculating the yield to be 79%, wherein the structural formula of the obtained p-methoxybenzenesulfonyl fluoride is
1 HNMR(500MHz,CDCl 3 )δ7.89(dd,J＝8.4,1.7Hz,2H),7.42(d,J＝8.1Hz,2H),2.49(s,3H). 13 CNMR(126MHz,CDCl 3 )δ147.1,130.3,130.1(d,J＝2Hz),128.4,21.8. . 19 FNMR(471MHz,CDCl 3 )δ66.30.
Example 4
A method for electrochemically synthesizing an aromatic sulfonyl fluoride compound (specifically, synthesizing m-tert-butylbenzenesulfonyl fluoride), which is characterized by comprising the following steps:
s1, under the atmosphere of nitrogen, 0.20mmol of0.15mmol DABSO and 0.60mmol Potassium fluorohydride (KHF) 2 ) Adding into a 10.0ml diaphragm-free electrolytic cell;
then adding 0.04mmol of reaction medium (9, 10-dicyanoanthracene) and 0.05mmol of electrolyte into the electrolytic tank n Bu 4 NClO 4 ) Then adding 1.0ml of organic solvent (acetonitrile) and stirring for dissolving for 10 minutes;
s2, inserting a platinum (Pt) electrode serving as an anode and an RVC electrode serving as a cathode into the electrolytic tank, and then introducing 12mA constant-voltage direct current to perform electrochemical reaction for 3 hours;
s3, after the reaction is finished, adding the reaction solution into 10ml of ethyl acetate, washing 2 times with 2.5ml of water, extracting, drying an organic phase with anhydrous sodium sulfate, separating by column chromatography to obtain 34.6mg of p-phenylbenzenesulfonyl fluoride, calculating the yield to be 80%, wherein the structural formula of the obtained product m-tert-butylbenzenesulfonyl fluoride is
1 HNMR(500MHz,CDCl 3 )δ8.01(s,1H),7.83(t,J＝7.0Hz,2H),7.57(t,J＝7.9Hz,1H),1.37(s,9H). 13 CNMR(126MHz,CDCl 3 )δ153.6,132.9,132.8,129.5,125.6,125.1,35.2,31.0. 19 FNMR(471MHz,CDCl 3 )δ65.92.
Example 5
A method for electrochemically synthesizing an aromatic sulfonyl fluoride compound (specifically, synthesizing 3-methyl-4-sulfonyl fluoride methyl benzoate), which is characterized by comprising the following steps:
s1, under the atmosphere of nitrogen, 0.20mmol of0.15mmol DABSO and 0.60mmol Potassium fluorohydride (KHF) 2 ) Adding into a 10.0ml diaphragm-free electrolytic cell;
then adding 0.04mmol of reaction medium (9, 10-dicyanoanthracene) and 0.05mmol of electrolyte into the electrolytic tank n Bu 4 NClO 4 ) Then adding 1.0ml of organic solvent (acetonitrile) and stirring for dissolving for 10 minutes;
s2, inserting a platinum (Pt) electrode serving as an anode and an RVC electrode serving as a cathode into the electrolytic tank, and then introducing 12mA constant-voltage direct current to perform electrochemical reaction for 3 hours;
s3, after the reaction is finished, adding the reaction solution into 10ml of ethyl acetate, washing 2 times with 2.5ml of water, extracting, drying an organic phase with anhydrous sodium sulfate, separating by column chromatography to obtain 36.7mg of p-phenylbenzenesulfonyl fluoride, calculating the yield of the p-phenylbenzenesulfonyl fluoride to be 65%,the structural formula of the obtained product 3-methyl-4-sulfonyl fluoride methyl benzoate is
1 HNMR(400MHz,CDCl 3 )δ8.16–8.08(m,2H),8.04(dt,J＝8.2,1.7Hz,1H),3.98(s,3H),2.82–2.69(m,3H). 13 CNMR(101MHz,CDCl 3 )δ165.1,139.4,136.0,135.9(J＝23Hz),133.7,130.2,127.5,52.9,20.3. 19 FNMR(376MHz,CDCl 3 )δ60.26.
Example 6
A method for electrochemically synthesizing an aromatic sulfonyl fluoride compound (specifically, synthesizing 2-naphthalene sulfonyl fluoride), which is characterized by comprising the following steps:
s1, under the atmosphere of nitrogen, 0.20mmol of0.15mmol DABSO and 0.60mmol Potassium fluorohydride (KHF) 2 ) Adding into a 10.0ml diaphragm-free electrolytic cell;
then adding 0.04mmol of reaction medium (9, 10-dicyanoanthracene) and 0.05mmol of electrolyte into the electrolytic tank n Bu 4 NClO 4 ) Then adding 1.0ml of organic solvent (acetonitrile) and stirring for dissolving for 10 minutes;
s2, inserting a platinum (Pt) electrode serving as an anode and an RVC electrode serving as a cathode into the electrolytic tank, and then introducing 12mA constant-voltage direct current to perform electrochemical reaction for 3 hours;
s3, after the reaction is finished, adding the reaction solution into 10ml of ethyl acetate, washing 2 times with 2.5ml of water, extracting, drying an organic phase with anhydrous sodium sulfate, separating by column chromatography to obtain 31.2mg of p-phenylbenzenesulfonyl fluoride, and calculating the yield to be 76%, wherein the structural formula of the obtained product 2-naphthalenesulfonyl fluoride is
1 HNMR(400MHz,CDCl 3 )δ8.54(d,J＝1.9Hz,1H),8.09–7.84(m,4H),7.73-7.62(m,2H). 13 CNMR(101MHz,CDCl 3 )δ136.0,131.7,130.9,130.4,130.1,129.8,129.6,128.3,128.1,122.1. 19 FNMR(376MHz,CDCl 3 )δ66.37.
The above embodiments 1 to 5 differ in that: the types of the used raw material aryl trifluoro methane sulfonate are different, and the rest reaction conditions are the same; the products obtained are different.
Example 6
Example 6 differs from example 1 in that: the proportions and concentrations of the raw materials are different, and the rest are the same as in example 1; the yield of example 6 was 73%.
The molar ratio between the aryl triflate, DABSO and potassium fluorohydride in example 1 above was 4:3:12; the concentration of the aryl triflate is 0.2mmol/ml; the concentration of 9, 10-dicyanoanthracene is 0.04mmol/ml; n Bu 4 NClO 4 is 0.05mmol/ml.
The molar ratio between the aryl triflate, DABSO and potassium fluorohydride in example 6 was adjusted to 2:1:3, a step of; the concentration of the aryl trifluoro methane sulfonate is regulated to be 0.1mmol/ml; adjusting the concentration of 9, 10-dicyanoanthracene to 0.02mmol/ml; will be n Bu 4 NClO 4 The concentration of (C) was adjusted to 0.03mmol/ml.
Example 7
Example 7 differs from example 1 in that: the proportions and concentrations of the raw materials are different, and the rest are the same as in example 1; the yield of example 7 was 74.5%.
Example 7 the molar ratio between aryl triflate, DABSO and potassium fluorohydride was adjusted to 3:1:5, a step of; the concentration of the aryl trifluoro methane sulfonate is adjusted to be 0.5mmol/ml; adjusting the concentration of 9, 10-dicyanoanthracene to 0.1mmol/ml; will be n Bu 4 NClO 4 The concentration of (C) was adjusted to 0.1mmol/ml.
The application provides a method for electrochemically synthesizing an aryl sulfonyl fluoride compound by taking a phenol derivative as a raw material, which has simple synthesis steps, and compared with the traditional synthesis method for preparing the aryl sulfonyl fluoride compound by breaking a C-O bond in activated phenols and derivatives thereof, the synthesis method provided by the application has low requirements on instruments and equipment, does not use a metal catalyst, saves cost, has mild reaction conditions, has simple operation steps, short reaction time and high yield.
The above-described preferred embodiments of the present application are only for illustrating the present application, and are not to be construed as limiting the present application. Obvious changes and modifications of the application, which are introduced by the technical solution of the present application, are still within the scope of the present application.
Claims (10)
1. A method for electrochemically synthesizing an aromatic sulfonyl fluoride compound, comprising the steps of:
s1, mixing reaction raw materials including aryl triflate, DABSO and potassium bifluoride in an electrolytic tank under an inert atmosphere;
then adding a reaction medium and an electrolyte into the electrolytic tank, and then adding an organic solvent for dissolution;
s2, inserting electrodes into the electrolytic tank, and electrifying to perform electrochemical reaction;
s3, extracting, drying and purifying after the reaction to obtain the aryl sulfonyl fluoride compound.
2. The method for electrochemical synthesis of an aromatic sulfonyl fluoride compound according to claim 1, wherein the molar ratio of aromatic triflate, DABSO and potassium fluorohydride in step S1 is (1-3): 1: (3-5).
3. The method for electrochemical synthesis of an aromatic sulfonyl fluoride compound according to claim 1, wherein the concentration of the aromatic triflate in the organic solvent in step S1 is 0.1 to 0.5mmol/ml.
4. The method for electrochemical synthesis of an aromatic sulfonyl fluoride compound according to claim 1, wherein the concentration of the reaction medium in the organic solvent in step S1 is 0.02 to 0.1mmol/ml; the reaction medium is 9, 10-dicyanoanthracene.
5. The method for electrochemical synthesis of an aromatic sulfonyl fluoride compound according to claim 1, wherein the concentration of the electrolyte in the organic solvent in step S1 is 0.03 to 0.1mmol/ml; the electrolyte is n Bu 4 NClO 4 。
6. The method for electrochemical synthesis of an aromatic sulfonyl fluoride compound according to claim 1, wherein the organic solvent is acetonitrile.
7. The method for electrochemical synthesis of an aromatic sulfonyl fluoride compound according to claim 1, wherein in step S2, a platinum electrode is inserted as a positive electrode and an RVC electrode is inserted as a negative electrode in the electrolytic cell, and then a constant voltage direct current of 10-15 mA is applied to perform electrochemical reaction for 1-3 hours.
8. The method for electrochemical synthesis of an aromatic sulfonyl fluoride compound according to claim 1, wherein the extractant used in step S3 is ethyl acetate.
9. The method for electrochemical synthesis of an aromatic sulfonyl fluoride compound according to claim 1, wherein step S3 is a purification by column chromatography.
10. The method for electrochemical synthesis of an aromatic sulfonyl fluoride compound according to claim 1, wherein the aromatic sulfonyl fluoride compound obtained in step S3 is one of p-toluenesulfonyl fluoride, p-phenylbenzenesulfonyl fluoride, p-methoxybenzenesulfonyl fluoride, m-tert-butylbenzenesulfonyl fluoride, methyl 3-methyl-4-sulfonyl fluorobenzoate and 2-naphthalenesulfonyl fluoride.
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