Synthetic method of aryl thioether compound

Abstract

The invention discloses a synthesis method of an aryl thioether compound, which is characterized in that tetramethylthiourea which is cheap and easy to obtain is used as a sulfur source, and C-H thioetherification reaction of aromatic hydrocarbon is directly realized through a one-pot two-step method. According to the method provided by the invention, efficient conversion of aromatic hydrocarbon is realized at room temperature by utilizing light induction, the reaction condition is mild, and the operation is simple. Compared with the traditional method reported before, the method disclosed by the invention has the advantages that the use of a metal catalyst and mercaptan with pungent smell is avoided, the requirement of developing green and environment-friendly chemistry is met, and the method has a wide substrate application range, good functional group compatibility, various complex natural products and drug molecules and a very good application prospect.

Description

Technical Field

[0001] The invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing an aryl sulfide compound. Background Art

[0002] As an important organic compound, thioether is widely present in natural products and drug molecules, and has biological activity against mental illness, AIDS, and bacterial infection. One of the prominent strategies for constructing thioethers is the cross-coupling of aryl halides and thiols under transition metal catalysis, for example: Ghosh, I., Shlapakov, N., Karl, TA et al. General cross-coupling reactions with adaptive dynamic homogeneous catalysis. Nature 619, 87-93 (2023). However, this strategy is generally not environmentally friendly, and thiols have a certain toxic effect on transition metals, which complicates the reaction. And the harsh reaction conditions that are incompatible with biologically active molecules are required, which limits the substrate range of the reaction and affects the complex diversity and later functionalization of the thioether product structure. Summary of the invention

[0003] In order to solve the problems of metal residue and single structure of thioetherification products in the prior art, the present invention provides a method for synthesizing aryl thioether compounds. The method of the present invention avoids the use of metal catalysts and thiols with pungent odors, has a wide range of substrate applications, good functional group compatibility, including various complex natural products and drug molecules, and has good application prospects.

[0004] The present invention provides a method for synthesizing an aryl sulfide compound, which uses aromatic hydrocarbons and sulfur oxides as raw materials, obtains the corresponding aryl sulfonium salt in the presence of trifluoromethanesulfonic anhydride, and then continues to add tetramethylthiourea and an alcohol compound without separation, and realizes the CH thioetherification reaction of aromatic hydrocarbons by visible light induction in the presence of a base, and obtains an aryl alkyl sulfide compound after separation and purification. The synthesis route is as follows:

[0005]

[0006] Where R1 is C 1-10 Alkyl, C 6-20 aryl or heteroaryl, and the C 1-10 Alkyl, C 6-20 The aryl or heteroaryl group may be substituted with a hydroxyl, halogen, thiol, amine, carbonyl, ester or ether group; R2 represents C 1-10 alkyl, and the C 1-10The alkyl group may be substituted with a hydroxyl group, a halogen group, a mercapto group, an amine group, a carbonyl group, an ester group, or an ether group.

[0007] The sulfur oxide is dibenzothiophene oxide or thianthrene oxide.

[0008]

[0009] Further, the aromatic hydrocarbon is selected from the compounds having the following structures:

[0010]

[0011] Furthermore, the alcohol compound is selected from at least one of the following structural compounds:

[0012]

[0013] The base is selected from at least one of potassium phosphate, cesium carbonate, potassium carbonate, sodium carbonate, potassium tert-butoxide, sodium tert-butoxide, 1,8-diazobispiro[5.4.0]undec-7-ene (DBU), and 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG).

[0014] The reaction is carried out in an organic solvent, and the organic solvent is selected from at least one of 1,4-dioxane, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, dichloroethane, acetone and dichloromethane.

[0015] The molar ratio of the aromatic hydrocarbon to the alcohol compound is 1.0-2.0:1.

[0016] The molar ratio of the sulfur oxide to the alcohol compound is 1.0-2.0:1.

[0017] The molar ratio of the trifluoromethanesulfonic anhydride to the alcohol compound is 1.0-2.0:1.

[0018] The molar ratio of the tetramethylthiourea to the alcohol compound is 2.0-4.0:1.

[0019] The molar ratio of the base to the alcohol compound is 1.0-3.0:1.

[0020] The present invention uses aromatic hydrocarbons and sulfur oxides as raw materials, and obtains corresponding aryl sulfonium salts in the presence of trifluoromethanesulfonic anhydride without separation. Tetramethylthiourea and alcohol compounds are continuously added, and in the presence of a base, the CH thioetherification reaction of the aromatic hydrocarbons is achieved by visible light induction, and aryl alkyl sulfide compounds are obtained after separation and purification. Compared with the previously reported method, the present method uses tetramethylthiourea instead of thiol as a sulfur source, and avoids the use of metal catalysts. It has a wide range of substrate application and good functional group compatibility, including various complex natural products and drug molecules, and has good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 For compound 3a 1 H-NMR spectrum.

[0022] Figure 2 For compound 3a 13 C-NMR spectrum. DETAILED DESCRIPTION

[0023] Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein can be applied to the methods of the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only.

[0024] The present invention provides a method for synthesizing an aryl sulfide compound, wherein aromatic hydrocarbons and sulfur oxides are used as raw materials, and in the presence of trifluoromethanesulfonic anhydride, a corresponding aryl sulfonium salt is obtained without separation. Tetramethylthiourea and an alcohol compound are continuously added, and in the presence of a base, a CH thioetherification reaction of the aromatic hydrocarbon is achieved by visible light induction, and an aryl alkyl sulfide compound is obtained after separation and purification:

[0025]

[0026] Wherein, R1 represents an alkyl group or hydrogen, R2 represents an alkyl group (primary alkyl group, secondary alkyl group), and the sulfur oxide represents dibenzothiophene oxide or thianthrene oxide.

[0027] Furthermore, R1 is C 1-10 Alkyl, C 6-20 aryl or heteroaryl, and the C 1-10 Alkyl, C 6-20 The aryl or heteroaryl group may be substituted with a hydroxyl, halogen, thiol, amine, carbonyl, ester or ether group; R2 represents C 1-10 alkyl, and the C 1-10 The alkyl group may be substituted with a hydroxyl group, a halogen group, a mercapto group, an amine group, a carbonyl group, an ester group, or an ether group.

[0028] The aromatic hydrocarbon compound is preferably a compound shown below:

[0029]

[0030] The alcohol compound is preferably a compound shown in the following items:

[0031]

[0032] In an embodiment of the present invention, the molar ratio of tetramethylthiourea to alcohol compound is 2.0-4.0:1, more preferably 2.5-4.0:1, and most preferably 3.0-4.0:1.

[0033] In an embodiment of the present invention, the molar ratio of the base to the alcohol compound is 1.0-3.0:1, more preferably 1.5-3.0:1, and most preferably 1.5-2.0:1.

[0034] In an embodiment of the present invention, the molar ratio of the aromatic hydrocarbon to the alcohol compound is 1.0-2.0:1, more preferably 1.5-2.0:1, and most preferably 1.5:1.

[0035] In an embodiment of the present invention, the molar ratio of the sulfur oxide to the alcohol compound is 1.0-2.0:1, more preferably 1.5-2.0:1, and most preferably 1.5:1.

[0036] In an embodiment of the present invention, the molar ratio of trifluoromethanesulfonic anhydride to the alcohol compound is 1.0-2.0:1, more preferably 1.5-2.0:1, and most preferably 1.5:1.

[0037] In one embodiment of the present invention, the wavelength of the light source is between 365 nm and 600 nm, preferably 365-465 nm, more preferably 390-420 nm, and the irradiation time is 12-24 hours, preferably 16-24 hours, more preferably 18-20 hours.

[0038] In an embodiment of the present invention, the organic solvent is at least one selected from 1,4-dioxane, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, dichloroethane, acetone and dichloromethane, more preferably acetonitrile.

[0039] In the preparation method of the present invention, the yield of the target product can be as high as 98%.

[0040] In order to further illustrate the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention. All other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0041] The drugs used in the following examples of the present invention were purchased from the following reagent companies:

[0042] Acetonitrile (C2H3N, 99.9%), dimethyl sulfoxide (C2H6OS, 99.9%), dichloroethane (C2H4Cl2, 99.5%), acetone (C2H6O, 99.5%), trifluoromethanesulfonic anhydride (C2F6O5S2, 98%), tetramethylthiourea (C5H 12 N2S, 98%) were purchased from J&K, 1,4-dioxane (C4H8O2, 99.5%), tetrahydrofuran (C4H8O, 99.5%), and dichloromethane (CH2Cl2, 99.9%) were purchased from Anergy.

[0043] Embodiment 1:

[0044]

[0045] The specific method is as follows:

[0046] 3-Chloro-6-methyldibenzo[c,f][1,2]thiazepine-11(6H)-one 5,5-dioxide (0.3mmol) and dibenzothiophene oxide (0.3mmol) were added to a 10mL Schlenk reaction tube (Beijing Xinweier Glass Instrument Co., Ltd., F580810 reaction tube, capacity 10mL). The air in the tube was completely replaced with argon three times, trifluoromethanesulfonic anhydride (0.3mmol) and acetonitrile (1mL). The reaction was carried out at -78°C for 15 minutes, and then the reaction was heated to room temperature for 1 hour. After the reaction was completed, cesium carbonate (0.3mmol) was added to neutralize the strong acid produced during the reaction, and then tetramethylthiourea (0.6mmol), cesium carbonate (0.4mmol) and CD3OD (0.2mmol) were added under argon atmosphere. The reaction system was continuously stirred at room temperature for 20 hours under 420nm LED light irradiation (using IKA magnetic stirrer, RCT basic model, stirring speed 500 rpm). After the reaction was completed, the reaction was quenched with H2O, and the reaction solution was extracted with ethyl acetate (3*10 mL), and the combined organic phase was concentrated by rotary evaporation (Buchhi Rotary Evaporator R-3, Switzerland). The concentrated residue was passed through a chromatographic column (Beijing Xinweier Glass Instrument Co., Ltd., C383040C sand plate storage ball chromatography column, 35 / 20, The product was separated by chromatography (effective length: 500 mm). (The product is a colorless liquid, 69.8 mg in total, with a yield of 98%, and the eluent is ethyl acetate: petroleum ether = 1:10 to 1:2)

[0047] 1H NMR (600MHz, Chloroform-d) δ8.11(s,1H),7.96–7.88(m,2H),7.67(d,J=8.5Hz,1H),7.50(d,J=8.0Hz,1H),7.28–7.24(m,1H),3.31(s,3H).

[0048] 13 C NMR (151MHz, Chloroform-d) δ189.1,138.8,138.3,138.3,137.5,134.1,133.3,133.3,133.0,131.2,128.7,125.6,125.3,39.1.

[0049] HRMS(ESI)(m / z):[M+H] + ,C 15 H 10 D3ClNO3S2 + Calculated value: 357.0208; actual value: 357.0206. Example 2:

[0050]

[0051] The method is the same as Example 1, and the yields are shown in Table 1.

[0052] 1 H NMR(600MHz,Chloroform-d)δ7.02(d,J=2.5Hz,1H),6.95(dd,J=8.6,2.5Hz,1H), 6.68(d,J=8.6Hz,1H),4.24(q,J=7.1Hz,2H),1.60(s,6H),1.26(t,J=7.1Hz,3H).

[0053] 13 C NMR (151MHz, Chloroform-d) δ174.1,150.7,133.7,128.1,124.7,124.4,118.2,80.7,61.6,25.0,14.1.

[0054] HRMS(ESI)(m / z):[M+H] + ,C 13 H 15 D3ClO3S + Calculated value: 292.0848; Actual value: 292.0850.

[0055] Embodiment 3:

[0056]

[0057] The specific method is as follows:

[0058] Flurbiprofen methyl ester (0.3mmol) and thianthrene oxide (0.3mmol) were added to a 10mL Schlenk reaction tube (Beijing Xinweier Glass Instrument Co., Ltd., F580810 reaction tube, capacity 10mL). The air in the tube was completely replaced with argon three times, trifluoromethanesulfonic anhydride (0.3mmol), acetonitrile (1mL). The reaction was carried out under -78°C for 15 minutes, and then the reaction was heated to room temperature for 1 hour. After the reaction was completed, cesium carbonate (0.3mmol) was added to neutralize the strong acid produced during the reaction, and then tetramethylthiourea (0.6mmol), cesium carbonate (0.4mmol), and CD3OD (0.2mmol) were added under argon atmosphere. The reaction system was stirred continuously at room temperature for 20 hours under 420nm LED light irradiation (using IKA magnetic stirrer, RCT basic type, stirring speed 500 rpm). After the reaction was completed, the reaction was quenched with H2O, and the reaction solution was extracted with ethyl acetate (3*10 mL), and the combined organic phase was concentrated by rotary evaporation (Buchhi Rotary Evaporator R-3, Switzerland). The concentrated residue was passed through a chromatographic column (Beijing Xinweier Glass Instrument Co., Ltd., C383040C sand plate storage ball chromatography column, 35 / 20, The product was separated by chromatography (effective length: 500 mm). (The product is a colorless liquid, 58.9 mg in total, with a yield of 96%, and the eluent is ethyl acetate: petroleum ether = 1:10 to 1:2)

[0059] 1 H NMR(600MHz,Chloroform-d)δ7.46(d,J=6.7Hz,2H),7.37(t,J=8.0Hz,1H),7.31(d,J=8.4Hz, 2H), 7.12 (dd, J=13.5, 9.7Hz, 2H), 3.76 (q, J=7.2Hz, 1H), 3.70 (s, 3H), 1.53 (d, J=7.2Hz, 3H).

[0060] 13 C NMR(151MHz,Chloroform-d)δ174.4,159.7(d,J=248.4Hz),141.8(d,J=7.6Hz),138.2,132.1,130.5(d,J=4.0H z), 129.3 (d, J = 3.1Hz), 127.2 (d, J = 13.3Hz), 126.4, 123.6 (d, J = 3.2Hz), 115.3 (d, J = 23.6Hz), 52.2, 44.9, 18.4.

[0061] 19 F NMR(565MHz,Chloroform-d)δ-117.4.

[0062] HRMS(ESI)(m / z):[M+H] + ,C 17 H 15 D3FO2S + Calculated value: 308.1194; Actual value: 308.1196.

[0063] Embodiment 4:

[0064]

[0065] The method is the same as Example 1, and the yields are shown in Table 1.

[0066] 1 H NMR(600MHz,Chloroform-d)δ6.66(s,1H),3.88(s,3H),2.63(s,3H),2.38(s,3H).

[0067] 13 C NMR (151MHz, Chloroform-d) δ158.3,140.7,137.1,127.0,122.7,111.0,56.1,21.5,19.4.

[0068] HRMS(ESI)(m / z):[M+H] + ,C 10 H 11 D3C10S + Calculated value: 220.0637; Actual value: 220.0640.

[0069] Embodiment 5:

[0070]

[0071] The method is the same as Example 1, and the yields are shown in Table 1.

[0072] 1 H NMR(600MHz,Chloroform-d)δ7.77(dd,J=8.7,2.5Hz,1H),7.56(d,J=2.5Hz,1H), 7.36–7.31(m,3H),7.28(s,5H),7.00(d,J=8.8Hz,2H),4.91(s,2H),3.09(s,3H).

[0073] 13C NMR (151MHz, Chloroform-d) δ155.5,151.7,148.0,136.2,135.3,134.3,134.1,129.0,128.8,128.7,128.3,120.6,117.7,111.9,54.0,40.5.

[0074] HRMS(ESI)(m / z):[M+H] + ,C 21 H 18 D3N2O5S2 + Calculated value: 448.1075; Actual value: 448.1072.

[0075] Embodiment 6:

[0076]

[0077] The method is the same as Example 1, and the yields are shown in Table 1.

[0078] 1 H NMR (600MHz, Chloroform-d) δ7.68(d,J=1.1Hz,1H),7.39(d,J=6.6Hz,2H),6.93(d,J=26.3Hz,2H),3.95(s,3H),3.93(s,3H).

[0079] 13 C NMR(151MHz,Chloroform-d)δ166.0,162.5(dd,J=249.6,12.1Hz),159.6(dd,J=250.5,11.9Hz),156.1,135.3,131.3(dd,J=9. 4,4.6Hz),131.2,129.6,127.9,124.6,123.9(dd,J=13.7,3.9Hz),111.7(dd,J=21.1,3.8Hz),104.5(t,J=25.9Hz),61.6,52.4.

[0080] 19 F NMR (565MHz, Chloroform-d) δ -110.5 (d, J = 7.9Hz), -113.2 (d, J = 7.8Hz).

[0081] HRMS(ESI)(m / z):[M+H] + ,C 16 H 12 D3F2O3S + Calculated value: 328.0893; Actual value: 328.0895.

[0082] Embodiment 7:

[0083]

[0084] The method is the same as Example 1, and the yields are shown in Table 1.

[0085] 1 H NMR(600MHz,Chloroform-d)δ8.46(s,1H),7.94(s,1H),7.87(d,J=8.5Hz,1H),7.83(d,J=8.3Hz,1H),7. 65(d,J=8.3Hz,1H),7.40(d,J=7.6Hz,2H),7.38–7.27(m,16H),7.21(d,J=6.0Hz,2H),7.03(d,J=8.5Hz,1 H),4.94–4.83(m,4H),4.79(d,J=10.3Hz,1H),4.71(d,J=9.7Hz,1H),4.65–4.59(m,2H),4.55(d,J=11.9H z,1H),3.83(d,J=10.9Hz,1H),3.78–3.72(m,2H),3.68(t,J=9.3Hz,1H),3.59–3.51(m,2H),3.28(s,3H).

[0086] 13 C NMR(151MHz,Chloroform-d)δ188.8,140.3,138.7,138.3,138.3,138.0,137.8,134.6,134.3,133.4,133.3,132.4,130.7,128.5,128.5,128 .5,128.4,128.3,128.0,128.0,127.9,127.9,127.8,127.8,127.6,12 5.3,124.9,87.0,86.7,81.1,79.1,75.9,75.6,75.1,73.5,69.1,38.8.

[0087] HRMS(ESI)(m / z):[M+H] + ,C 48 H 45 ClNO8S2 + Calculated value: 862.2270; Actual value: 862.2267.

[0088] Embodiment 8:

[0089]

[0090] The method is the same as Example 1, and the yields are shown in Table 1.

[0091] 1 H NMR(600MHz,Chloroform-d)δ8.24(s,1H),7.94(d,J=1.9Hz,1H),7.92(d,J=8.2Hz,1H),7.68(dd,J=8.2 ,2.1Hz,1H),7.52(d,J=8.3Hz,1H),7.23(d,J=7.9Hz,1H),4.28–4.15(m,9H),3.95(s,2H),3.32(s,3H).

[0092] 13 C NMR(151MHz,Chloroform-d)δ189.1,139.2,138.8,138.3,135.9,135.7,134 .2,133.4,133.3,132.0,131.0,125.5,125.0,69.4,69.2,68.6,39.1,34.8.

[0093] HRMS(ESI)(m / z):[M+H] + ,C 25 H 21 ClFeNO3S2 + Calculated value: 537.9995; Actual value: 537.9991.

[0094] Embodiment 9:

[0095]

[0096] The method is the same as Example 3, and the yields are shown in Table 1.

[0097] 1 H NMR(600MHz,Chloroform-d)δ8.17–8.13(m,1H),7.60–7.54(m,1H),7.23(d,J=8.7Hz,2H),6.97–6.90(m,4H),6.89–6.82(m,3 H),6.74(d,J=8.4Hz,1H),5.62–5.55(m,1H),4.18(dd,J=9.9,5.3Hz,1H),4.07(dd,J=9.9,4.8Hz,1H),1.48(d,J=6.4Hz,3H).

[0098] 13C NMR (151MHz, Chloroform-d) δ163.1,156.7,155.3,150.3,146.7,138.8,131.2,129.5,120.6,118.4,116.8,115.8,111.7,71.1,69.3,17.0.

[0099] HRMS(ESI)(m / z):[M+H] + ,C 21 H 19 D3NO3S + Calculated value: 371.1503; Actual value: 371.1501.

[0100] Embodiment 10:

[0101]

[0102] The method is the same as Example 1, and the yields are shown in Table 1.

[0103] 1 H NMR(600MHz,Chloroform-d)δ7.68(d,J=2.2Hz,1H),7.40(dd,J=8.5,2.2Hz,1H),6.83(d,J=8.5Hz,1H ),4.17–4.06(m,2H),3.88(s,3H),3.63(q,J=7.1Hz,1H),1.42(d,J=7.1Hz,3H),1.20(t,J=7.1Hz,3H).

[0104] 13 C NMR (151MHz, Chloroform-d) δ172.5,156.4,139.3,135.3,124.6,111.9,111.6,61.2,56.3,46.0,17.1,14.1.

[0105] HRMS(ESI)(m / z):[M+Na] + ,C 12 H 15 BrNaO3S + Calculated value: 340.9817; Actual value: 340.9820.

[0106] Embodiment 11:

[0107]

[0108] The method is the same as Example 1, and the yields are shown in Table 1.

[0109] 1H NMR(600MHz,Chloroform-d)δ7.76(d,J=2.2Hz,1H),7.48(dd,J=8.5,2.3Hz,1H),6.85(d,J=8.6Hz,1H),3.90(s,3H),3. 66–3.60(m,1H),2.35(d,J=2.4Hz,1H),1.74–1.67(m,2H),1.57–1.45(m,2H),1.35–1.24(m,4H),0.89(t,J=7.0Hz,3H).

[0110] 13 C NMR (151MHz, Chloroform-d) δ156.3,139.2,135.2,125.3,111.9,111.6,83.6,72.6,56.3,39.7,34.8,31.2,26.8,22.5,14.0.

[0111] HRMS(ESI)(m / z):[M+H] + ,C 15 H 20 BrOS + Calculated value: 327.0413; Actual value: 327.0414.

[0112] Embodiment 12:

[0113]

[0114] The method is the same as Example 1, and the yields are shown in Table 1.

[0115] 1 H NMR(600MHz,Chloroform-d)δ7.70(d,J=2.2Hz,1H),7.41(dd,J=8.5,2.2Hz,1H),6.82(d,J=8.5Hz,1H),5.07–5.02( m,1H),4.19–4.12(m,1H),3.87(s,3H),3.59–3.52(m,1H),2.02–1.95(m,1H),1.88–1.73(m,2H),1.67–1.55(m,3H).

[0116] 13 C NMR (151MHz, Chloroform-d) δ155.6,137.2,133.1,126.9,112.1,111.7,86.2,64.6,56.3,31.4,25.5,21.6.

[0117] HRMS(ESI)(m / z):[M+H] + ,C 12 H 16 BrO2S + Calculated value: 303.0049; Actual value: 303.0052.

[0118] Embodiment 13:

[0119]

[0120] The method is the same as Example 1, and the yields are shown in Table 1.

[0121] 1 H NMR(600MHz,Chloroform-d)δ7.64(d,J=2.0Hz,1H),7.32(dd,J=8.6,2.1Hz,1H),7.31–7.27(m,4H),7.24–7.2 0(m,1H),6.79(d,J=8.6Hz,1H),6.31(d,J=15.8Hz,1H),6.24–6.16(m,1H),3.86(s,3H),3.60(d,J=7.3Hz,2H).

[0122] 13 C NMR (151MHz, Chloroform-d) δ155.4,137.1,136.7,133.0,132.9,128.5,127.6,127.4,126.3,125.0,112.0,111.7,56.3,39.0.

[0123] HRMS(ESI)(m / z):[M+H] + ,C 16 H 16 BrOS + Calculated value: 335.0100; Actual value: 335.0103.

[0124] Embodiment 14:

[0125]

[0126] The method is the same as Example 1, and the yields are shown in Table 1.

[0127] 1H NMR(600MHz,Chloroform-d)δ7.65(d,J=2.2Hz,1H),7.37(dd,J=8.5,2.3Hz,1H),6.83(d,J=8.6Hz,1H), 4.53(t,J=6.7Hz,1H), 4.45(t,J=6.7Hz,1H), 3.88(s,3H), 3.10(t,J=6.7Hz,1H), 3.07(t,J=6.7Hz,1H).

[0128] 13 C NMR (151MHz, Chloroform-d) δ155.8, 137.0, 132.9, 126.5, 112.3, 112.1, 81.5 (d, J = 172.4Hz), 56.4, 35.5 (d, J = 21.4Hz).

[0129] 19 F NMR(565MHz,Chloroform-d)δ-213.4.

[0130] HRMS(ESI)(m / z):[M+H] + ,C9H 11 BrFOS + Calculated value: 264.9693; Actual value: 264.9684.

[0131] Table 1

[0132]

[0133]

[0134] The above is a detailed introduction to the method for synthesizing aryl alkyl sulfide compounds provided by the present invention. The above is only an embodiment of the present invention and does not limit the scope of the present invention. Without departing from the principle of the present invention, the present invention can be improved and modified, and these improvements and modifications are also included in the scope of patent protection of the present invention.

Claims

1. A method for synthesizing an aryl sulfide compound, characterized in that: Aromatic hydrocarbons and sulfur oxides are used as raw materials, in the presence of trifluoromethanesulfonic anhydride, to obtain the corresponding aryl sulfonium salt, without separation, tetramethylthiourea and alcohol compounds are added, in the presence of a base, CH thioetherification reaction of the aromatic hydrocarbons is achieved by visible light induction, and aryl alkyl sulfide compounds are obtained after separation and purification; The synthetic route is as follows: Where R1 is C 1-10 Alkyl, C 6-20 aryl or heteroaryl, and the C 1-10 Alkyl, C 6-20 The aryl or heteroaryl group may be substituted with a hydroxyl, halogen, thiol, amine, carbonyl, ester or ether group; R2 represents C 1-10 alkyl, and the C 1-10 The alkyl group may be substituted with hydroxyl, halogen, thiol, amine, carbonyl, ester or ether groups; The sulfur oxide is dibenzothiophene oxide or thianthrene oxide; 2. The method according to claim 1, characterized in that: The aromatic hydrocarbon is selected from the compounds of the following structures:

3. The method according to claim 1, characterized in that: The alcohol compound is selected from at least one of the following structural compounds:

4. The method according to claim 1, 2 or 3, characterized in that: The molar ratio of the aromatic hydrocarbon to the alcohol compound is 1.0-2.0:

1.

5. The method according to claim 1 or 3, characterized in that: The molar ratio of the sulfur oxide to the alcohol compound is 1.0-2.0:1; the molar ratio of the trifluoromethanesulfonic anhydride to the alcohol compound is 1.0-2.0:

1.

6. The method according to claim 1 or 3, characterized in that: The molar ratio of the tetramethylthiourea to the alcohol compound is 2.0-4.0:

1.

7. The method according to claim 1, characterized in that: The base is selected from at least one of potassium phosphate, cesium carbonate, potassium carbonate, sodium carbonate, potassium tert-butoxide, sodium tert-butoxide, 1,8-diazobispiro[5.4.0]undec-7-ene, and 2-tert-butyl-1,1,3,3-tetramethylguanidine.

8. The method according to claim 1 or 7, characterized in that: The molar ratio of the base to the alcohol compound is 1.0-3.0:

1.

9. The method according to claim 1, characterized in that: The reaction is carried out in an organic solvent, and the organic solvent is selected from at least one of 1,4-dioxane, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, dichloroethane, acetone and dichloromethane.

10. The method according to claim 1, characterized in that: The wavelength range of the light source is between 365nm and 600nm, and the irradiation time is 12-24 hours.

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