A method for synthesizing N-sulfoxide diaryl sulfoximine compounds

Abstract

The present invention discloses a method for synthesizing N-sulfoxide diaryl sulfoximine compounds, belonging to the technical field of organic chemistry. Using NH-diaryl sulfoximine 1 and dimethyl sulfoxide 2 as raw materials, an electrochemical reaction is carried out in the presence of a base and an electrolyte. Dimethyl sulfoxide removes a methyl group, which then reacts with the NH-diaryl sulfoximine as a sulfoxide source to synthesize N-sulfoxide diaryl sulfoximine compound 3. The electrochemical synthesis method of the present invention achieves N-H sulfoxidation in the absence of a catalyst and an oxidant. The solvent dimethyl sulfoxide also serves as the reaction raw material. The reaction conditions are mild, providing a new approach for the rapid synthesis of N-sulfoxide diaryl sulfoximine products.

Description

Technical Field

[0001] The invention relates to a method for synthesizing N-sulfoxide diaryl sulfoximine compounds, and belongs to the technical field of organic chemistry. Background Art

[0002] Sulfoximine compounds are widely found in bioactive molecules and have important applications in pharmaceuticals. For example, Roniciclib is a cyclin-dependent kinase inhibitor and oral cytotoxic agent; Ceralasertib is an ATR enzyme inhibitor used to treat cancers such as ovarian clear cell carcinoma. In addition, some sulfoximines can also act as PYK2 inhibitors, α-adrenergic receptor blockers, and protein kinase C inhibitors.

[0003] There are several methods for the NH arylthio or benzylic thiolation of sulfoximine, as well as the NH sulfonylation of sulfoximine:

[0004] A. For the NH arylthio or benzylthio reaction of sulfoximine: In 2016, the literature reported the copper-catalyzed NH arylthio reaction of sulfoximine with diaryl disulfide, adding 3eq sodium acetate and DMSO as solvent. In 2018, the literature reported the iodine-catalyzed NH arylthio reaction of sulfoximine with thiophenol, which required a large amount of hydrogen peroxide as an oxidant and polyethylene glycol (PEG). 400 . In 2018, the literature reported the copper-catalyzed NHarylthio or benzylic thiolation reaction of sulfoximine with thiophenol or benzylthiol. The reaction used the uncommon [Cu(DMAP)4]I as a catalyst and required oxygen as an oxidant. In 2018, the literature reported the NHarylthio or benzylic thiolation reaction of sulfoximine with N-arylthiosuccinimide or N-benzylthiosuccinimide catalyzed by the nanomaterial h-BN@Y-CD@Cu(OAc)2. The methods in the existing literature have the following disadvantages: the use of transition metal catalysts, the use of oxidants, especially the dangerous peroxide oxidant H2O2, the complex nanomaterials increase the difficulty of synthesis for organic chemists, and the use of N-arylthiosuccinimide or N-benzylthiosuccinimide has poor atom economy.

[0005] B. For the NH sulfonation reaction of sulfoximine: In 2020, the literature reported the iodine-catalyzed NH sulfonation reaction of sulfoximine with sodium arylsulfinate. The reaction still requires the dangerous peroxide H2O2.

[0006] Electrochemical organic synthesis has the advantages of not requiring oxidants or reducing agents, mild reaction conditions, and being green and environmentally friendly. It has become a hot area in organic synthesis in recent years. There are very few examples of dimethyl sulfoxide as a reaction substrate under electrochemistry. Dimethyl sulfoxide is used as a source of methyl and methylthiomethylsulfone groups. However, there are currently no reports of it as a source of methylsulfone groups. In 2018, the literature reported the electrochemical iron-catalyzed reaction of thiophenols or thiols with dimethyl sulfoxide to obtain methyl sulfoxide compounds. The sulfur in the product comes from the thiophenols or thiols, and dimethyl sulfoxide only serves as a methyl source. The reaction still requires the dangerous peroxide H2O2. In 2021, the literature reported the electrochemically promoted reaction of amines with dimethyl sulfoxide to obtain sulfonamide compounds, with dimethyl sulfoxide as the source of sulfone groups. The reaction needs to be completed by a free radical mechanism under the promotion of iodine. In 2024, the electrochemical C-H methylthiolation of 2-phenylimidazopyridines with dimethyl sulfoxide (DMSO) was reported. DMSO served as the source of the methylthio group, and the reaction proceeded via a free radical mechanism, again with iodine as a promoter. This electrochemical use of DMSO as a sulfoxide source in this reaction had never been reported before.

[0007] Therefore, developing a new reaction mode of dimethyl sulfoxide under electrochemical synthesis method, as a source of sulfoxide group, to realize sulfoxylation reaction has important research value. Summary of the Invention

[0008] In order to overcome the above-mentioned technical defects, the present application provides a method for efficiently synthesizing N-sulfoxide diaryl sulfoximine under electrochemistry using cheap and readily available dimethyl sulfoxide as a reaction substrate and solvent and NH sulfoximine as a raw material. The reaction does not require a catalyst or an oxidant and has mild reaction conditions. This method overcomes the previous electrochemical reaction involving dimethyl sulfoxide, which is carried out by a free radical mechanism and dimethyl sulfoxide is easily used as a methyl source, a methylthio source, or a methylsulfone source. The present invention changes the previous synthesis strategy and is carried out by a new sulfoxide positive ion mechanism. Dimethyl sulfoxide is selectively used as a sulfoxide source, thereby realizing the simple synthesis of N-sulfoxide diaryl sulfoximine, which is of important research value in the field of medicine.

[0009] The synthesis method of the N-sulfoxide diaryl sulfoximine compound of the present invention is represented by the following reaction equation:

[0010]

[0011] Where: Ar 1 Selected from phenyl, C1-C4 alkylphenyl, halogenated phenyl, C1-C4 alkoxyphenyl, dibenzothiophene; Ar 2 Selected from phenyl, acetylphenyl, C1-C4 alkylphenyl, halogenated phenyl, cyanophenyl, C1-C4 alkoxyphenyl, thienyl, dibenzothiophene.

[0012] The method comprises the following steps: using diaryl sulfoximine 1 and dimethyl sulfoxide 2 as raw materials, dimethyl sulfoxide also serving as a reaction solvent, and subjecting the N-sulfoxide diaryl sulfoximine compound 3 to an electrochemical constant current reaction in the presence of a base and an electrolyte.

[0013] Furthermore, in the above technical solution, the halogenated group is selected from fluoro, bromo, chloro or iodo.

[0014] Furthermore, in the above technical solution, during the constant current reaction, the electrode material is selected from Pt(+) / Pt(-), C(+) / Pt(-), Pt(+) / C(-), C(+) / C(-), Pt(+) / GF(-), Pt(+) / Ni(-); preferably Pt(+) / Pt(-).

[0015] Furthermore, in the above technical solution, the electrolyte is selected from tetrabutylammonium iodide, tetrabutylammonium acetate, tetrabutylammonium perchlorate, tetraethylammonium tetrafluoroborate, and tetrabutylammonium tetrafluoroborate; preferably tetrabutylammonium tetrafluoroborate.

[0016] Furthermore, in the above technical solution, the base is selected from K2CO3, PivOK, DBU; preferably K2CO3.

[0017] Furthermore, in the above technical solution, THF, MeCN, DMF, MeOH or HFIP is additionally added to the reaction system, preferably only DMSO solvent is used.

[0018] Furthermore, in the above technical solution, the current intensity is selected from 8-12 mA, preferably 10 mA.

[0019] Furthermore, in the above technical solution, the reaction temperature is selected from 20-60°C, preferably 40°C.

[0020] In order to further explore the reaction mechanism, the following comparative experiments were conducted, and the reaction results are as follows:

[0021] The reaction was inhibited using free radical inhibitors TEMPO, BHT, and 1,1-diphenylethylene. It was found that a large amount of product was still generated and the inhibition was not very good, indicating that the reaction may not proceed through a free radical mechanism. Taking the reaction of raw material 1a and dimethyl sulfoxide 2 to produce product 3a as an example, the possible reaction mechanism is as follows:

[0022]

[0023] Under the action of a base, diphenylsulfoximine 1a removes the hydrogen from the nitrogen to form a diphenylsulfoximine anion A. Dimethylsulfoxide 2 generates a methylsulfoxide cation under the action of an electrode, which then combines with the diphenylsulfoximine anion A to produce the target product 3a.

[0024] Beneficial effects of the invention:

[0025] The present invention uses diaryl sulfoximine as a raw material, and dimethyl sulfoxide (DMSO) removes one methyl group and combines with the diaryl sulfoximine as a sulfoxide source to obtain the target product, N-sulfoxydiaryl sulfoximine. This represents the first time that the NH sulfoxylation of sulfoximine has been achieved. Furthermore, unlike previous electrochemical reactions involving DMSO, which have all been based on free radical mechanisms, the present invention pioneers a new pathway based on a sulfoxide free radical mechanism, achieving a groundbreaking electrochemical sulfoxylation reaction using DMSO as a sulfoxide source.

[0026] The present invention has numerous advantages, including the absence of any catalysts or oxidants, particularly the avoidance of precious metal catalysts and hazardous peroxide oxidants, mild reaction conditions, and environmental friendliness. It provides a novel synthetic strategy for the synthesis of a series of N-sulfoxide diaryl sulfoximine products. DETAILED DESCRIPTION

[0027] Example 1

[0028] Optimization of reaction conditions

[0029] In a 10 mL non-diaphragm electrolytic cell equipped with two platinum electrodes (1 cm x 1 cm platinum sheet), compound 1a (0.2 mmol), electrolyte (0.2 mmol), base (0.2 mmol), and solvent (5 mL) were added in sequence. The power was turned on, the current intensity was set, and the current was passed. The reaction was allowed to react at a constant temperature for 10 hours. After the reaction, water was added, and the mixture was extracted with ethyl acetate. The mixture was dried over anhydrous Na2SO4, and the solvent was removed on a rotary evaporator. The desired product was separated by column chromatography using petroleum ether:ethyl acetate in a ratio of 1:2 as the eluent.

[0030] The optimized reaction results are as follows:

[0031] During the reaction condition screening process, the effects of electrode materials (labels 2-6), electrolytes (labels 7-10), bases (labels 11-12), organic solvents (13-17), current intensity (labels 18-19), and reaction temperature (labels 20-21) were examined. Ultimately, the optimal electrode materials were determined to be Pt(+) / Pt(-), the optimal electrolyte was n-Bu4NBF4, the optimal base was K2CO3, the optimal solvent was DMSO, the optimal current intensity was 10 mA, and the optimal reaction temperature was 40°C.

[0032]

[0033]

[0034]

[0035] Example 2:

[0036] In a 10 mL diaphragmless electrolytic cell equipped with two platinum electrodes (1 cm x 1 cm platinum sheet), compound 1a (0.2 mmol), n-Bu4NBF4 (0.2 mmol), and K2CO3 (0.2 mmol) were added sequentially, followed by the solvent DMSO (5 mL). The power supply was turned on, the current was set to 10 mA, and the current was passed. The reaction was allowed to proceed at 40°C for 10 hours. After the reaction, water was added, the mixture was extracted with ethyl acetate, dried over anhydrous Na2SO4, and the solvent was removed on a rotary evaporator. Column chromatography using petroleum ether:ethyl acetate in a ratio of 1:2 was performed to yield 43.8 mg of product 3a as a light yellow liquid in a 78% yield. 1 H NMR (600MHz, CDCl3) δ8.06 (d, J = 7.7Hz, 2H), 8.01 (d, J = 7.6Hz, 2H), 7.60-7.58 (m, 2H), 7.56-7.50 (m, 4H), 2.79 (s, 3H). 13 C NMR(151MHz, CDCl3)δ139.9,139.4,133.8,133.7,129.7,129.6,128.8,128.0,47.6.HRMS(ESI)calcd.for C 13 H 13 NNaO2S2 + ([M+Na] + ):302.0280,found:302.0281.

[0037] Example 3:

[0038] According to the reaction conditions of Example 2, only the structure of substrate 1 was changed, and the reaction results were as follows:

[0039] N-[methyl(oxo)-λ 4 -sulfanyl]-1-(4-methylphenyl)-1-oxo-1-phenyl-λ 6 -sulfanimine(3b):Pale yellow oil; 37.1mg, 63% yield; dr~1:1; 1H NMR(600 MHz,CDCl3)δ8.05(d,J=7.9 Hz,2H),8.00(d,J=7.9 Hz,2H),7.94(d,J=7.7 Hz,2H),7.90(d,J=7.7Hz,2H),7.59-7.58(m,2H),7.54-7.51(m,4H),7.34-7.32(m,4H),2.79(s,6H),2.40(s,3H),2.40(s,3H). 13 C NMR(151 MHz,CDCl3)δ145.1,144.9,140.3,139.8,136.9,136.2,133.7,133.6,130.4,130.3,129.7,129.6,128.9,128.6,128.1,128.0,47.6,21.7,21.7.HRMS(ESI)calcd.for C 14 H 16 NO2S2 + ([M+H] + ):294.0617,found:294.0615.

[0040]

[0041] 1-(4-methoxyphenyl)-N-[methyl(oxo)-λ 4 -sulfanyl]-1-oxo-1-phenyl-λ 6 -sulfanimine(3c):Pale yellow oil;37.5 mg,61%yield;dr~1:1; 1 H NMR(600 MHz,CDCl3)δ8.03(d,J=7.8 Hz,2H),8.00-7.97(m,4H),7.95(d,J=8.2 Hz,2H),7.58-7.56(m,2H),7.53-7.50(m,4H),6.99(t,J=7.7Hz,4H),3.84(s,3H),3.83(s,3H),2.78(s,6H). 13 CNMR(151 MHz,CDCl3)δ164.0,163.9,140.7,140.0,133.5,133.4,131.1,130.9,130.4,130.2,129.6,129.5,128.5,127.7,115.0,114.9,55.9,55.8,47.6.HRMS(ESI)calcd.forC 14 H15 NNaO3S2 + ([M+Na] + ):332.0386,found:332.0384.

[0042]

[0043] N-[methyl(oxo)-λ 4 -sulfanyl]-1-[4-(2-methylprop-2-yl)phenyl]-1-oxo-1-phenyl-λ 6 -sulfanimine(3d):Pale yellow oil;60.8 mg,91%yield;dr~1:1; 1 H NMR(600MHz,CDCl3)δ8.06(d,J=7.9 Hz,2H),8.02(d,J=7.9Hz,2H),7.96(d,J=8.1 Hz,2H),7.93(d,J=8.1 Hz,2H),7.59-7.57(m,2H),7.54-7.51(m,8H),2.78(s,6H),1.30(s,18H). 13 CNMR(151 MHz,CDCl3)δ157.8,157.8,140.3,139.8,136.7,136.1,133.7,133.5,129.7,129.5,128.7,128.7,128.0,127.9,126.8,126.7,47.6,35.4,35.4,31.1.HRMS(ESI)calcd.for C 17 H 22 NO2S2 + ([M+H] + ):336.1086,found:336.1083.

[0044]

[0045] 1-(4-fluorophenyl)-N-[methyl(oxo)-λ 4 -sulfanyl]-1-oxo-1-phenyl-λ 6 -sulfanimine(3e):Pale yellow oil;50.5 mg,85%yield;dr~1:1; 1H NMR(600MHz,CDCl3)δ8.08-8.06(m,2H),8.04(d,J=7.5 Hz,4H),7.99(d,J=7.6 Hz,2H),7.61-7.59(m,2H),7.54-7.53(m,4H),7.20(t,J=8.0 Hz,4H),2.79(s,6H). 13 C NMR(151 MHz,CDCl3)δ166.7,166.7,165.0,165.0,139.9,139.3,135.9,135.8,135.4,135.3,134.0,133.9,131.7,131.7,131.0,131.0,129.8,129.7,128.6,127.9,117.1,117.0,117.0,116.9,47.6,47.5.HRMS(ESI)calcd.for C 13 H 13 FNO2S2 + ([M+H] + ):298.0366,found:298.0370.

[0046]

[0047] 1-(4-chlorophenyl)-N-[methyl(oxo)-λ 4 -sulfanyl]-1-oxo-1-phenyl-λ 6 -sulfanimine(3f):Pale yellow oil;53.7 mg,86%yield;dr~1:1; 1 H NMR(600 MHz,CDCl3)δ8.04(d,J=7.8 Hz,2H),7.99(d,J=8.0 Hz,4H),7.95(d,J=7.9 Hz,2H),7.62-7.59(m,2H),7.57-7.52(m,4H),7.49(d,J=8.0 Hz,4H),2.79(s,6H). 13 C NMR(151 MHz,CDCl3)δ140.7,140.6,139.6,139.1,138.5,138.0,134.1,133.9,130.2,130.0,129.9,129.8,129.7,129.5,128.7,128.0,47.6,47.6.HRMS(ESI)calcd.forC 13 H 13 ClNO2S2+ (M+H + ):314.0071,found:314.0075.

[0048]

[0049] 1-(3-chlorophenyl)-N-[methyl(oxo)-λ 4 -sulfanyl]-1-oxo-1-phenyl-λ 6 -sulfanimine(3g):Pale yellow oil;29.5 mg,47%yield;dr~1:1; 1 H NMR(600 MHz,CDCl3)δ8.06(d,J=7.4 Hz,3H),8.02(d,J=7.6 Hz,3H),7.94(d,J=7.8 Hz,1H),7.89(d,J=7.8 Hz,1H),7.64-7.62(m,2H),7.60-7.55(m,6H),7.49-7.46(m,2H),2.81(s,6H). 13 CNMR(151 MHz,CDCl3)δ141.9,141.6,139.4,138.9,135.9,135.9,134.2,134.1,134.0,133.9,130.9,130.9,129.9,129.8,128.9,128.7,128.2,128.0,126.9,126.2,47.7,47.7.HRMS(ESI)calcd.for C 13 H 13 ClNO2S2 + ([M+H] + ):314.0071,found:314.0075.

[0050]

[0051] N-[methyl(oxo)-λ 4 -sulfanyl]-1,1-bis(4-methylphenyl)-1-oxo-λ 6 -sulfanimine(3h):Pale yellow oil;46.8 mg,76%yield; 1H NMR(600 MHz,CDCl3)δ7.91(d,J=8.0 Hz,2H),7.86(d,J=8.0 Hz,2H),7.31-7.29(m,4H),2.76(s,3H),2.38(s,3H),2.38(s,3H). 13 C NMR(151 MHz,CDCl3)δ144.8,144.7,137.1,136.5,130.3,130.2,128.7,128.0,47.5,21.7,21.6.HRMS(ESI)calcd.for C 15 H 18 NO2S2 + ([M+H] + ):308.0773,found:308.0777.

[0052]

[0053] 1,1-bis(4-methoxyphenyl)-N-[methyl(oxo)-λ 4 -sulfanyl]-1-oxo-λ 6 -sulfanimine(3i):Pale yellow oil;52.1 mg,77%yield; 1 H NMR(600 MHz,CDCl3)δ7.95(d,J=8.3 Hz,2H),7.90(d,J=8.3 Hz,2H),6.97(t,J=8.0 Hz,4H),3.83(s,3H),3.83(s,3H),2.76(s,3H). 13 C NMR(151 MHz,CDCl3)δ163.7,163.7,131.7,130.8,130.8,130.0,114.9,114.8,55.9,55.8,47.5.HRMS(ESI)calcd.for C 15 H 18 NO4S2 + ([M+H] + ):340.0672,found:340.0670.

[0054]

[0055] N-[methyl(oxo)-λ 4 -sulfanyl]-1,1-bis[4-(2-methylprop-2-yl)phenyl]-1-oxo-λ6 -sulfanimine(3j):Pale yellow oil;60.6 mg,77%yield; 1 H NMR(600 MHz,CDCl3)δ7.96(d,J=8.1 Hz,2H),7.93(d,J=8.1 Hz,2H),7.52(t,J=8.4 Hz,4H),2.77(s,3H),1.30(s,18H). 13 C NMR(151 MHz,CDCl3)δ157.6,157.6,137.0,136.4,128.6,127.8,126.8,126.6,47.6,35.3,35.3,31.1.HRMS(ESI)calcd.for C 21 H 29 NNaO2S2 + ([M+Na] + ):414.1532,found:414.1536.

[0056]

[0057] 1,1-bis(4-chlorophenyl)-N-[methyl(oxo)-λ 4 -sulfanyl]-1-oxo-λ 6 -sulfanimine(3k):Pale yellow oil;53.0 mg,76%yield; 1 H NMR(600 MHz,CDCl3)δ7.98(d,J=8.4 Hz,2H),7.93(d,J=8.3 Hz,2H),7.51(d,J=8.4 Hz,4H),2.80(s,3H). 13 C NMR(151 MHz,CDCl3)δ141.0,140.9,138.2,137.7,130.2,130.2,130.1,129.5,47.6.HRMS(ESI)calcd.forC 13 H 11 Cl2NNaO2S2 + ([M+Na] + ):369.9500,found:369.9504.

[0058]

[0059] 1-(4-methoxyphenyl)-N-[methyl(oxo)-λ4 -sulfanyl]-1-(4-methylphenyl)-1-oxo-λ 6 -sulfanimine(3l):Pale yellow oil;47.2 mg,73%yield;dr~1:1; 1 H NMR(600MHz,CDCl3)δ7.96(d,J=8.4 Hz,2H),7.90(dd,J=12.7,8.4 Hz,4H),7.84(d,J=7.9 Hz,2H),7.31-7.29(m,4H),6.98-6.96(m,4H),3.82(s,3H),3.82(s,3H),2.76(s,6H),2.38(s,3H),2.37(s,3H). 13 C NMR(151 MHz,CDCl3)δ163.8,163.8,144.6,144.5,137.5,136.8,131.2,130.9,130.5,130.3,130.2,130.1,128.5,127.7,114.9,114.8,55.8,55.8,47.5,21.6,21.6.HRMS(ESI)calcd.for C 15 H 17 NNaO3S2 + ([M+Na] + ):346.0542,found:346.0543.

[0060]

[0061] 1-[4-({[methyl(oxo)-λ 4 -sulfanyl]azanylidene}(4-methylphenyl)(oxo)-λ 6 -sulfanyl)phenyl]ethan-1-one(3m):Pale yellow oil;39.5 mg,59%yield;dr~1:1; 1<h2 style=";text-align:left;direction:ltr">HNMR(600 MHz,CDCl3)δ8.14(d,J=8.0 Hz,2H),8.09(d,J=8.1 Hz,2H),8.06(d,J=8.3 Hz,4H),7.95(d,J=7.8 Hz,2H),7.90(d,J=7.7 Hz,2H),7.35(d,J=6.4 Hz,4H),2.80(s,6H),2.62(s,3H),2.60(s,3H),2.42(s,3H),2.41(s,3H).<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> C NMR(151 MHz,CDCl3)δ196.7,196.7,145.6,145.5,144.3,144.1,140.7,140.6,136.1,135.6,130.6, 130.5,129.3,129.3,129.0,128.3,47.7,47.6,27.0,27.0,21.8,21.7.HRMS(ESI)calcd.for C<h2 style=";text-align:left;direction:ltr"> 16 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 18 <h2 style=";text-align:left;direction:ltr"> NO3S2<h2 style=";text-align:left;direction:ltr"> + <h2 style=";text-align:left;direction:ltr"> ([M+H]<h2 style=";text-align:left;direction:ltr"> + <h2 style=";text-align:left;direction:ltr"> ):336.0723,found:336.0722.<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0062] <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0063] <h2 style=";text-align:left;direction:ltr"> 4-[(4-chlorophenyl){[methyl(oxo)-λ<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> -sulfanyl]azanylidene}(oxo)-λ<h2 style=";text-align:left;direction:ltr"> 6 <h2 style=";text-align:left;direction:ltr"> -sulfanyl]benzene-1-carbonitrile(3n):Pale yellow oil;42.5 mg,63%yield;dr~1:1;<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> H NMR (600 MHz, CDCl3)δ8.16(d,J=8.5 Hz,2H),8.12(d,J=8.5 Hz,2H),7.99(d,J=8.7 Hz,2H),7.95(d,J=8.7 Hz,2H),7.83(dd,J=8.5,3.7 Hz,4H),7.54(d,J=8.5 Hz,4H),2.82(s,6H).<h2 style=";text-align:left;direction:ltr"> 13C NMR(151MHz,CDCl3)δ144.2,144.1,141.6,141.5,137.2,136.8,133.4,133.4,130.5,130.4,130.3,129.7,129.4,128.6,117.7,117.6,117.0,117.0,47.7,47.6.HRMS(ESI)calcd.for C 14 H 12 ClN2O2S2 + (M+H + ):339.0023,found:339.0025.

[0064]

[0065] N-[methyl(oxo)-λ 4 -sulfanyl]-1-oxo-1-phenyl-1-(thiophen-3-yl)-λ 6 -sulfanimine(3o):Pale yellow oil;38.2 mg,67%yield;dr~1:1; 1 H NMR(600MHz,CDCl3)δ8.10(d,J=7.9 Hz,2H),8.06(d,J=7.9 Hz,2H),7.83(d,J=3.4 Hz,1H),7.72-7.71(m,3H),7.62-7.59(m,2H),7.54(dd,J=13.7,6.9 Hz,4H),7.11(dt,J=13.6,4.1 Hz,2H),2.80(s,6H). 13 C NMR(151MHz,CDCl3)δ141.2,140.7,140.3,140.1,135.6,135.5,135.5,134.5,133.9,133.8,129.7,129.6,128.7,128.4,128.4,127.6,47.5,47.4.HRMS(ESI)calcd.for C 11 H 12 NO2S3 + (M+H + ):286.0025,found:286.0022.

[0066]

[0067] N-(5-oxido-5λ 4-dibenzo[b,d]thiophen-5-ylidene)methanesulfinamide(3p):Brown solid; 34.8 mg, 63% yield; 1 H NMR (600 MHz, CDCl3) δ8.02 (d, J = 7.7 Hz, 1H), 7.95 (d, J = 7.7 Hz, 1H), 7.80 (t, J = 8.0 Hz, 2H), 7.69-7.63 (m, 2H), 7.55 (t, J = 7.5Hz, 2H), 2.77 (s, 3H). 13 C NMR(151MHz, CDCl3)δ138.2,137.5,134.7,134.2,132.7,132.0,130.9,130.7,124.2,124.0,121.9,121.8,47.2.HRMS(ESI)calcd.for C 13 H 11 NNaO2S2 + (M+Na + ):300.0123,found:300.0120.

[0068] The above embodiments illustrate the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and improvements may be made to the present invention without departing from the scope of the principles of the present invention, and all such changes and improvements fall within the scope of protection of the present invention.

Claims

1. A method for synthesizing N-sulfoxide diaryl sulfoximine compounds, characterized in that: The method comprises the following steps: using NH-diaryl sulfoximine 1 and dimethyl sulfoxide 2 as raw materials, with dimethyl sulfoxide also serving as a solvent, and performing an electrochemical constant current reaction in the presence of a base and an electrolyte to obtain an N-sulfoxide diaryl sulfoximine compound 3; the base is selected from K2CO3 or PivOK; the constant current reaction has a current intensity of 8-12 mA; and the reaction equation is expressed as follows: Where: Ar 1 is selected from phenyl, C1-C4 alkylphenyl, halogenated phenyl, C1-C4 alkoxyphenyl, dibenzothienyl; Ar 2 Selected from phenyl, acetylphenyl, C1-C4 alkylphenyl, halogenated phenyl, cyanophenyl, C1-C4 alkoxyphenyl, thienyl, dibenzothienyl.

2. The method for synthesizing N-sulfoxide diaryl sulfoximine compounds according to claim 1, characterized in that: Halo is selected from fluoro, bromo, chloro or iodo.

3. The method for synthesizing N-sulfoxide diaryl sulfoximine compounds according to claim 1, characterized in that: Constant current reaction, the electrode material is selected from Pt(+) / Pt(-), C(+) / Pt(-) or Pt(+) / GF(-).

4. The method for synthesizing N-sulfoxide diaryl sulfoximine compounds according to claim 1, characterized in that: The electrolyte is selected from tetrabutylammonium iodide, tetrabutylammonium acetate, tetrabutylammonium perchlorate, tetraethylammonium tetrafluoroborate or tetrabutylammonium tetrafluoroborate.

5. The method for synthesizing N-sulfoxide diaryl sulfoximine compounds according to claim 1, characterized in that: THF, DMF or HFIP was additionally added to the reaction system.

6. The method for synthesizing N-sulfoxide diaryl sulfoximine compounds according to claim 1, characterized in that: The reaction temperature is selected from 20-60°C.

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