Sulfone compound and preparation method thereof
By using components such as arylsulfohydroxide-amic acid compounds and photocatalysts, the reaction between olefins and sulfonyl radicals is solved, and the problems of substrate range limitation and structural compatibility in the prior art are achieved, and the diversity synthesis and simplified process of sulfone-based compounds are achieved.
Patent Information
- Application Number
- CN202510019955.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-07
- Publication Date
- 2025-04-15
AI Technical Summary
The prior art has limited substrate range in the hydrogen sulfonation reaction of olefins and has structural compatibility problems, making it difficult to develop hydroxamic acid precursor compounds with diverse structures.
The sulfone compound is prepared by reacting with olefins and other components such as arylsulfohydroxide compounds, trialkyl phosphites, photocatalysts, diphenyl disulfides, sodium bicarbonate and water.
The scope of synthetic substrates for sulfone compounds has been expanded, the synthesis steps have been simplified, and the application efficiency of hydroxamic acid precursor compounds with structural diversity has been improved.
Smart Images
Figure CN119823006A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the field of organic synthesis, in particular to a method for preparing sulfone compounds. Background Art
[0002] Sulfur-containing groups are extremely important in the preparation of functional molecules. In this context, the sulfonyl group is a special fragment that is commonly found in marketed drugs and drug candidates. Among them, alkyl-substituted sulfone compounds are approved as drugs with anticancer, antimigraine, antimicrobial, anti-inflammatory, antiparasitic and antihypertensive activities. Related literature: (a) Yibo Song, etal. Light-promoted photocatalyst-free and redox-neutral hydrosulfonylation of unactivated alkenes using sulfinic acid. Green Chem., 2024, 26, 6578-6583. (b) T. Liu, Y. Li, L. Lai, J. Cheng, J. Sun and J. Wu, Photocatalytic Reaction of PotassiumAlkyltrifluoroborates and Sulfur Dioxide with Alkenes,Org.Lett.,2018,20,3605.(c)J.Wang and W.Yu,Hydrosulfonylation of Unactivated Alkenes by Visible LightPhotoredox Catalysis,Org.Lett.,2019,21,9236.(d)Yinan Zheng,Visible-light-induced anti-Markovnikov hydrosulfonation of styrenederivatives.Org.Chem.Front.,2020,7,2069-2074.
[0003] Sulfonyl groups can react with alkenes to form sulfone compounds by free radical addition, which is called the hydrosulfonation of alkenes. This reaction has certain disadvantages in practical applications, such as limited substrate range and inevitable structural compatibility issues. How to develop more structurally diverse hydroxamic acid precursor compounds and apply them to the hydrosulfonation of alkenes is of great significance to enrich the synthesis methods of sulfone compounds and can effectively promote the application of such compounds in biomedical research. Summary of the invention
[0004] In view of the above technical problems, the present invention proposes a sulfone compound and a preparation method thereof, which is a new synthesis method of hydroxamic acid compounds as sulfonyl radical precursors for preparing related sulfone compounds.
[0005] To achieve the above object, the technical solution of the present invention is implemented as follows:
[0006] A method for preparing a sulfone compound comprises the following steps:
[0007] (1) Aryl sulfonyl hydroxamic acid compounds, trialkyl phosphite, photocatalyst, diphenyl disulfide (Ph 2 S 2 ), sodium bicarbonate and water are added to a reaction vessel, and a solvent is added to dissolve; after degassing with argon Ar or nitrogen, an olefin compound is added to obtain a reaction solution;
[0008] (2) irradiating the reaction solution with a light source and stirring until the reaction is complete;
[0009] (3) After the reaction is completed, the solvent is recovered under reduced pressure and purified by column chromatography to obtain a sulfone compound.
[0010] The reaction formula is as follows:
[0011]
[0012] Furthermore, the structural formula of the benzenesulfonyl hydroxamic acid compound in the above step (1) is as follows: Wherein, Ar is selected from one of substituted phenyl, substituted furan, substituted pyrrole, substituted thiophene and bicyclic aromatic hydrocarbon substituents; the structural formula of the olefin compound is as follows: Among them, R 1 and R 2 Each is independently a C1-C18 straight chain or branched substituted olefin.
[0013] Furthermore, the bicyclic aromatic hydrocarbon in the above-mentioned bicyclic aromatic hydrocarbon substituent is any one of naphthyl, anthracenyl, indole, benzofuran and benzothiophene.
[0014] Further, Ar is selected from substituted phenyl groups.
[0015] Furthermore, the structural formula of the trialkyl phosphite in the above step (1) is as follows: P(OR′) 3 , wherein R' is a C1-C10 straight chain or branched alkyl group.
[0016] Furthermore, the photocatalyst in the above step (1) is an organic photosensitizer or a metal photocatalyst.
[0017] Preferably, the organic photosensitizer is 4CzIPN, and the metal photocatalyst is Ir[dF(CF 3)ppy] 2 (dtbbpy)PF 6 or [Ir[dF(Me)ppy] 2 (dtbpy)]PF 6 .
[0018] Furthermore, in the above step (1), the solvent is any one of acetonitrile, dichloromethane, dichloroethane, ethyl acetate, toluene and acetone.
[0019] Furthermore, in the above step (1), the molar ratio of the benzenesulfonyl hydroxamic acid compound, the olefin compound, the trialkyl phosphite, the photocatalyst and the diphenyl disulfide is 1:(1-10):(1-4):(0.01-0.1):(0.1-0.3). For example, the molar ratio of benzenesulfonyl hydroxamic acid compounds, olefin compounds, trialkyl phosphite, photocatalyst and diphenyl disulfide is 1:(1-4):(1-3):(0.01-0.05):(0.1-0.2); the molar ratio of benzenesulfonyl hydroxamic acid compounds, olefin compounds, trialkyl phosphite, photocatalyst and diphenyl disulfide is 1:(6-10):(2-4):(0.01-0.05):(0.2-0.3); the molar ratio of benzenesulfonyl hydroxamic acid compounds, olefin compounds, trialkyl phosphite, photocatalyst and diphenyl disulfide is 1:(3-10):(2-3):(0.04-0.1):(0.1-0.3); The molar ratio of the compound, olefin compound, trialkyl phosphite, photocatalyst and diphenyl disulfide is 1:(2-8):(3-4):(0.03-0.07):(0.1-0.3); the molar ratio of the sulfohydroxamic acid compound, olefin compound, trialkyl phosphite, photocatalyst and diphenyl disulfide is 1:1:1:0.01:0.1, 1:10:4:0.1:0.3, 1:10:1:0.01:0.2, 1:1:4:0.01:0.2, 1:10:2:0.02:0.2 or 1:5:3:0.05:0.2, etc., any ratio in the range of 1:(1-10):(1-4):(0.01-0.1):(0.1-0.3) is sufficient.
[0020] In the above step (2), the light source is an LED blue light, the wavelength of which corresponds to the maximum absorption of the photocatalyst, and the power is 1-45W.
[0021] The sulfone compound is prepared by the above-mentioned preparation method.
[0022] Furthermore, the above-mentioned sulfone compounds include but are not limited to any one of the following compounds:
[0023]
[0024] The beneficial effects of the present invention are as follows: the synthesis method of the sulfone compound provided by the present invention expands the scope of the synthetic substrate and greatly simplifies the synthetic steps. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0026] Figure 1 This is the reaction formula for preparing sulfone compounds in Example 1 of the present invention.
[0027] Figure 2 This is the reaction formula for preparing sulfone compounds in Example 2 of the present invention. DETAILED DESCRIPTION
[0028] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0029] Example 1
[0030] The preparation method of the sulfone compound of this embodiment, reaction formula (such as Figure 1 The steps are as follows:
[0031]
[0032] In a 10 mL Schlenk tube, benzenesulfonyl hydroxamic acid compound 1a (18.7 mg, 0.1 mmol, 1.0 equiv.), Ph 2 S 2 (4.37mg,0.02mmol,0.2equiv.),NaHCO 3 (10.08 mg, 0.12 mmol, 1.2 equiv.) and P(OEt) 3 (33.2 mg, 0.2 mmol, 2.0 equiv.) was dissolved in acetonitrile (1.5 mL) and a photocatalyst (Ir[dF(CF 3 )ppy] 2 (dtbpy))PF 6(0.002mmol) and 10 microliters of water were stirred for 15 minutes, and then olefin 2a (112.2mg, 1.0mmol, 10.0equiv.) was added. The reaction was stirred for 24 hours under room temperature (the light source was LED blue light, the power was 45W, and the wavelength was 450nm). The reaction was completed by TLC detection. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same below, PE:EA=6:1) to obtain sulfone compound 3aa (20.6mg, yield 77%).
[0033] 1 H NMR(300MHz,Chloroform-d)δ7.84-7.72(m,2H),7.33(d,J=8.1Hz,2H),3.75(t,J=6.3Hz,2H),3.37 (t,J=6.4Hz,2H),3.26(t,J=6.7Hz,2H),2.44(s,3H),1.42(h,J=7.1Hz,2H),0.78(t,J=7.4Hz,3H); 13 C NMR (75MHz, Chloroform-d) δ144.66,136.95,129.75,128.12,72.94,64.00,56.39,22.62,21.65,10.39.
[0034] Example 2
[0035] The preparation method of the sulfone compound of this embodiment, reaction formula (such as Figure 2 The steps are as follows:
[0036]
[0037] In a 10 mL Schlenk tube, benzenesulfonyl hydroxamic acid compound 1a (18.7 mg, 0.1 mmol, 1.0 equiv.), Ph 2 S 2 (4.37mg,0.02mmol,0.2equiv.),NaHCO 3 (10.08 mg, 0.12 mmol, 1.2 equiv.) and P(OEt) 3 (33.2 mg, 0.2 mmol, 2.0 equiv.) was dissolved in acetonitrile (1.5 mL) and a photocatalyst (Ir[dF(CF 3 )ppy] 2 (dtbpy))PF 6(0.002mmol) and 10 microliters of water were added, stirred for 15 minutes, and then olefin 2b (100.2mg, 1.0mmol, 10.0equiv.) was added. The reaction was stirred for 24 hours under room temperature (the light source was LED blue light, power was 45W, wavelength was 450nm), and the reaction was completed by TLC detection. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same below, PE:EA=3:1) to obtain sulfone compound 3ab (17.4mg, yield was 68%).
[0038] 1 H NMR(300MHz,Chloroform-d)δ7.78(d,J=8.0Hz,2H),7.34(d,J=8.0Hz,2H),3.74(t,J=6.3Hz,2H),3.37(t,J=6.3H z,2H),3.29(t,J=6.5Hz,2H),2.44(s,3H),1.40–1.28(m,2H),1.22(dd,J=13.6,6.4Hz,2H),0.83(t,J=7.3Hz,3H); 13 C NMR (75MHz, Chloroform-d) δ144.65,136.94,129.75,128.12,71.07,64.04,56.39,31.47,21.65,19.13,13.86.
[0039] Example 3
[0040] The preparation method of the sulfone compound of this embodiment, the reaction formula and steps are as follows:
[0041]
[0042] In a 10 mL Schlenk tube, benzenesulfonyl hydroxamic acid compound 1a (18.7 mg, 0.1 mmol, 1.0 equiv.), Ph 2 S 2 (4.37mg,0.02mmol,0.2equiv.),NaHCO 3 (10.08 mg, 0.12 mmol, 1.2 equiv.) and P(OEt) 3 (33.2 mg, 0.2 mmol, 2.0 equiv.) was dissolved in acetonitrile (1.5 mL) and a photocatalyst (Ir[dF(CF 3 )ppy] 2 (dtbpy))PF 6(0.002mmol) and 10 microliters of water were stirred for 15 minutes, and then olefin 2c (86.1mg, 1.0mmol, 10.0equiv.) was added. The reaction was stirred for 24 hours under room temperature (the light source was LED blue light, the power was 45W, and the wavelength was 450nm). The reaction was completed by TLC detection. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same below, PE:EA=3:1) to obtain sulfone compound 3ac (15mg, yield 62%).
[0043] 1 H NMR(300MHz,Chloroform-d)δ7.84-7.72(m,2H),7.33(d,J=8.1Hz,2H),3.75(t,J=6.3Hz,2H),3.37 (t,J=6.4Hz,2H),3.26(t,J=6.7Hz,2H),2.44(s,3H),1.42(h,J=7.1Hz,2H),0.78(t,J=7.4Hz,3H); 13 C NMR (75MHz, Chloroform-d) δ144.66,136.95,129.75,128.12,72.94,64.00,56.39,22.62,21.65,10.39.
[0044] Example 4
[0045] The preparation method of the sulfone compound of this embodiment, the reaction formula and steps are as follows:
[0046]
[0047] In a 10 mL Schlenk tube, benzenesulfonyl hydroxamic acid compound 1a (18.7 mg, 0.1 mmol, 1.0 equiv.), Ph 2 S 2 (4.37mg,0.02mmol,0.2equiv.),NaHCO 3 (10.08 mg, 0.12 mmol, 1.2 equiv.) and P(OEt) 3 (33.2 mg, 0.2 mmol, 2.0 equiv.) was dissolved in acetonitrile (1.5 mL) and a photocatalyst (Ir[dF(CF 3 )ppy] 2 (dtbpy))PF 6(0.002mmol) and 10 microliters of water were added, stirred for 15 minutes, and then olefin 2d (72.1mg, 1.0mmol, 10.0equiv.) was added. The reaction was stirred for 24 hours under room temperature (the light source was LED blue light, the power was 45W, and the wavelength was 450nm). The reaction was completed by TLC detection. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same below, PE:EA=3:1) to obtain sulfone compound 3ad (13.7mg, yield 60%).
[0048] 1 H NMR(300MHz,Chloroform-d)δ7.83-7.73(m,2H),7.34(d,J=8.0Hz,2H),3.75(t ,J=6.3Hz,2H),3.37(tt,J=7.0,4.1Hz,4H),2.44(s,3H),1.03(t,J=6.9Hz,3H); 13 CNMR(75MHz,Chloroform-d)δ144.69,136.95,129.74,128.15,66.58,63.79,56.38,21.66,14.83.
[0049] Example 5
[0050] The preparation method of the sulfone compound of this embodiment, the reaction formula and steps are as follows:
[0051]
[0052] In a 10 mL Schlenk tube, benzenesulfonyl hydroxamic acid compound 1a (18.7 mg, 0.1 mmol, 1.0 equiv.), Ph 2 S 2 (4.37mg,0.02mmol,0.2equiv.),NaHCO 3 (10.08 mg, 0.12 mmol, 1.2 equiv.) and P(OEt) 3 (33.2 mg, 0.2 mmol, 2.0 equiv.) was dissolved in acetonitrile (1.5 mL) and a photocatalyst (Ir[dF(CF 3 )ppy] 2 (dtbpy))PF 6(0.002mmol) and 10 microliters of water were added, stirred for 15 minutes, and then olefin 2e (100.2mg, 1.0mmol, 10.0equiv.) was added. The reaction was stirred for 24 hours under room temperature (the light source was LED blue light, the power was 45W, and the wavelength was 450nm). The reaction was completed by TLC detection. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same below, PE:EA=3:1) to obtain sulfone compound 3ae (15.9mg, yield 62%).
[0053] 1 H NMR(300MHz,Chloroform-d)δ7.79(d,J=8.1Hz,2H),7.34(d,J=8.0Hz,2H),3.74(t,J=6.4Hz,2H),3.38( t,J=6.4Hz,2H),3.06(d,J=6.6Hz,2H),2.44(s,3H),1.65(dd,J=8.5,4.8Hz,1H),0.76(d,J=6.7Hz,6H); 13 C NMR (75MHz, Chloroform-d) δ144.67,136.91,129.78,128.10,78.14,64.21,56.39,28.28,21.64,19.16.
[0054] Example 6
[0055] The preparation method of the sulfone compound of this embodiment, the reaction formula and steps are as follows:
[0056]
[0057] In a 10 mL Schlenk tube, benzenesulfonyl hydroxamic acid compound 1a (18.7 mg, 0.1 mmol, 1.0 equiv.), Ph 2 S 2 (4.37mg,0.02mmol,0.2equiv.),NaHCO 3 (10.08 mg, 0.12 mmol, 1.2 equiv.) and P(OEt) 3 (33.2 mg, 0.2 mmol, 2.0 equiv.) was dissolved in acetonitrile (1.5 mL) and a photocatalyst (Ir[dF(CF 3 )ppy] 2 (dtbpy))PF 6(0.002mmol) and 10 microliters of water were stirred for 15 minutes, and then olefin 2f (100.2mg, 1.0mmol, 10.0equiv.) was added. The reaction was stirred for 24 hours under room temperature (the light source was LED blue light, the power was 45W, and the wavelength was 450nm). The reaction was completed by TLC detection. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same below, PE:EA=3:1) to obtain sulfone compound 3af (14.1mg, yield 55%).
[0058] 1 H NMR (300MHz, Chloroform-d) δ7.79(d,J=8.0Hz,2H),7.33(d,J=7.9Hz,2H),3.71(t,J=6.4Hz,2H),3.34(t,J=6.4Hz,2H),2.44(s,3H),1.06(s,9H); 13 C NMR (75MHz, Chloroform-d) δ144.49,137.26,129.64,128.14,73.77,57.20,55.59,27.18,21.65.
[0059] Example 7
[0060] The preparation method of the sulfone compound of this embodiment, the reaction formula and steps are as follows:
[0061]
[0062] In a 10 mL Schlenk tube, benzenesulfonyl hydroxamic acid compound 1a (18.7 mg, 0.1 mmol, 1.0 equiv.), Ph 2 S 2 (4.37mg,0.02mmol,0.2equiv.),NaHCO 3 (10.08 mg, 0.12 mmol, 1.2 equiv.) and P(OEt) 3 (33.2 mg, 0.2 mmol, 2.0 equiv.) was dissolved in acetonitrile (1.5 mL) and a photocatalyst (Ir[dF(CF 3 )ppy] 2 (dtbpy))PF 6(0.002mmol) and 10 microliters of water, stirred for 15 minutes, and then olefin 2g (126.2mg, 1.0mmol, 10.0equiv.) was added. The reaction was stirred for 24 hours under room temperature (the light source was LED blue light, the power was 45W, and the wavelength was 450nm). The reaction was completed by TLC detection. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same below, PE:EA=3:1) to obtain sulfone compound 3ag (20.8mg, yield 74%).
[0063] 1 H NMR(300MHz,Chloroform-d)δ7.79(d,J=7.9Hz,2H),7.34(d,J=7.9Hz,2H),3.78(t,J=6.4Hz,2H),3.37(t ,J=6.4Hz,2H),3.14(dt,J=9.2,4.7Hz,1H),2.44(s,3H),1.66(dd,J=24.7,7.0Hz,4H),1.26–1.08(m,6H); 13 C NMR (75MHz, Chloroform-d) δ144.57,137.06,129.70,128.14,78.02,61.16,56.85,31.79,25.65,23.81,21.64.
[0064] Example 8
[0065] The preparation method of the sulfone compound of this embodiment, the reaction formula and steps are as follows:
[0066]
[0067] In a 10 mL Schlenk tube, benzenesulfonyl hydroxamic acid compound 1a (18.7 mg, 0.1 mmol, 1.0 equiv.), Ph 2 S 2 (4.37mg,0.02mmol,0.2equiv.),NaHCO 3 (10.08 mg, 0.12 mmol, 1.2 equiv.) and P(OEt) 3 (33.2 mg, 0.2 mmol, 2.0 equiv.) was dissolved in acetonitrile (1.5 mL) and a photocatalyst (Ir[dF(CF 3 )ppy] 2 (dtbpy))PF 6(0.002mmol) and 10 microliters of water were added, stirred for 15 minutes, and then olefin 2h (68.1mg, 1.0mmol, 10.0equiv.) was added. The reaction was stirred for 24 hours under room temperature (the light source was LED blue light, the power was 45W, and the wavelength was 450nm). The reaction was completed by TLC detection. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same below, PE:EA=3:1) to obtain sulfone compound 3ah (16.3mg, yield was 73%).
[0068] 1 H NMR(300MHz,Chloroform-d)δ7.76(d,J=7.9Hz,2H),7.33(d,J=7.9Hz,2H),3.46(p,J=8.0Hz,1H),2.43(s,3H) ,2.03(dt,J=13.3,6.8Hz,2H),1.93–1.79(m,2H),1.73(q,J=6.8,5.7Hz,2H),1.59(dq,J=8.4,5.4,4.1Hz,2H); 13 C NMR (75MHz, Chloroform-d) δ144.38,136.04,129.80,128.50,64.29,27.29,25.88,21.64.
[0069] Example 9
[0070] The preparation method of the sulfone compound of this embodiment, the reaction formula and steps are as follows:
[0071]
[0072] In a 10 mL Schlenk tube, benzenesulfonyl hydroxamic acid compound 1b (20.3 mg, 0.1 mmol, 1.0 equiv.), Ph 2 S 2 (4.37mg,0.02mmol,0.2equiv.),NaHCO 3 (10.08 mg, 0.12 mmol, 1.2 equiv.) and P(OEt) 3 (33.2 mg, 0.2 mmol, 2.0 equiv.) was dissolved in acetonitrile (1.5 mL) and a photocatalyst (Ir[dF(CF 3 )ppy] 2 (dtbpy))PF 6(0.002mmol) and 10 microliters of water were stirred for 15 minutes, and then olefin 2b (100.2mg, 1.0mmol, 10.0equiv.) was added. The reaction was stirred for 24 hours under room temperature (the light source was LED blue light, the power was 45W, and the wavelength was 450nm). The reaction was completed by TLC detection. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same below, PE:EA=3:1) to obtain sulfone compound 3bb (13.9mg, yield 51%).
[0073] 1 H NMR(300MHz,Chloroform-d)δ7.83(d,J=8.8Hz,2H),7.00(d,J=8.8Hz,2H),3.87(s,3H),3.74(t,J=6.4Hz,2H),3. 36(t,J=6.4Hz,2H),3.30(t,J=6.5Hz,2H),1.44–1.30(m,2H),1.22(dt,J=15.0,7.4Hz,2H),0.84(t,J=7.3Hz,3H); 13 C NMR (75MHz, Chloroform-d) δ163.75,131.45,130.31,114.30,71.08,64.13,56.57,55.71,31.50,19.15,13.86.
[0074] Example 10
[0075] The preparation method of the sulfone compound of this embodiment, the reaction formula and steps are as follows:
[0076]
[0077] In a 10 mL Schlenk tube, benzenesulfonyl hydroxamic acid compound 1a (18.7 mg, 0.1 mmol, 1.0 equiv.), Ph 2 S 2 (4.37mg,0.02mmol,0.2equiv.),NaHCO 3 (10.08 mg, 0.12 mmol, 1.2 equiv.) and P(OEt) 3 (33.2 mg, 0.2 mmol, 2.0 equiv.) was dissolved in acetonitrile (1.5 mL) and a photocatalyst (Ir[dF(CF 3 )ppy] 2 (dtbpy))PF 6(0.002mmol) and 10 microliters of water were added, stirred for 15 minutes, and then olefin 2i (100.2mg, 1.0mmol, 10.0equiv.) was added. The reaction was stirred for 24 hours under room temperature (the light source was LED blue light, power was 45W, wavelength was 450nm), and the reaction was completed by TLC detection. The reaction solution was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (volume ratio, the same below, PE:EA=3:1) to obtain sulfone compound 3ai (13.6mg, yield was 53%).
[0078] 1 H NMR(300MHz,Chloroform-d)δ7.78(d,J=8.1Hz,2H),7.36(d,J=8.0Hz,2H),3.03-2.91(m,2H),2.45(s,3H),0.97-0.86(m,2H),-0.01(s,9H); 13 C NMR (75MHz, Chloroform-d) δ144.53,135.77,129.88,128.30,52.83,21.67,9.22,-2.00.
[0079] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims
1. A method for preparing a sulfone compound, characterized in that: Here are the steps: (1) adding a benzenesulfonyl hydroxamic acid compound, a trialkyl phosphite, a photocatalyst, diphenyl disulfide, sodium bicarbonate and water into a reaction vessel, and adding a solvent to dissolve; after degassing with argon or nitrogen, adding an olefin compound to obtain a reaction solution; (2) irradiating the reaction solution with a light source and stirring until the reaction is complete; (3) After the reaction is completed, the solvent is recovered under reduced pressure and purified by column chromatography to obtain a sulfone compound.
2. The method for preparing a sulfone compound according to claim 1, characterized in that: The structural formula of the hydroxamic acid compound in step (1) is as follows: Wherein Ar is selected from one of substituted phenyl, substituted furan, substituted pyrrole, substituted thiophene and bicyclic aromatic hydrocarbon substituents; the olefin compound has the structural formula: Where R 1 and R 2 Each is independently a C1-C18 straight chain or branched substituted olefin.
3. The method for preparing a sulfone compound according to claim 2, characterized in that: The bicyclic aromatic hydrocarbon in the bicyclic aromatic hydrocarbon substituent is any one of naphthyl, anthracenyl, indole, benzofuran and benzothiophene.
4. The method for preparing a sulfone compound according to claim 3, characterized in that: The structural formula of the trialkyl phosphite in step (1) is as follows: P(OR′)3, wherein R′ is a C1-C10 straight-chain or branched-chain alkyl group.
5. The method for preparing a sulfone compound according to claim 4, characterized in that: The photocatalyst in step (1) is an organic photosensitizer or a metal photocatalyst.
6. The method for preparing a sulfone compound according to claim 5, characterized in that: The organic photosensitizer is 4CzIPN, and the metal photocatalyst is Ir[dF(CF3)ppy]2(dtbbpy)PF6 or [Ir[dF(Me)ppy]2(dtbpy)]PF6.
7. The method for preparing a sulfone compound according to claim 6, characterized in that: The solvent in step (1) is any one of acetonitrile, dichloromethane, dichloroethane, ethyl acetate, toluene and acetone.
8. The method for preparing a sulfone compound according to claim 7, characterized in that: In the step (1), the molar ratio of the aromatic hydroxamic acid compound, the olefin compound, the trialkyl phosphite, the photocatalyst and the diphenyl disulfide is 1:(1-10):(1-4):(0.01-0.1):(0.1-0.3).
9. The method for preparing a sulfone compound according to claim 8, characterized in that: In step (2), the light source is an LED blue light, the wavelength of which corresponds to the maximum absorption of the photocatalyst, and the power is 1-45W.
10. A sulfone compound prepared by the preparation method according to any one of claims 1 to 9.