1. A synthetic method of alpha, beta-dichlorobenzene sulfoxide compounds, the structural formula of the alpha, beta-dichlorobenzene sulfoxide compounds is as follows:

1) r is hydrogen or one or more of substituent R, halogen, alkyl with 1-4 carbon atoms, carboxylic ester with 1-4 carbon atoms, phenyl, acetoxyl, trifluoromethyl, nitro, cyano, carboxyl, substituted aryl and halogen, wherein the number of the substituent R is 1-5, preferably 1 or 2;

the substituent in the substituted aryl is one or more of F, Cl, Br and alkyl with 1-4 carbon atoms, and the number of the substituent on the substituent is 1-5, preferably 1 or 2; halogen is one or more of F, Cl and Br;

2) r 'is hydrogen or one or more of substituent R' is halogen, alkyl with 1-4 carbon atoms and alkoxy with 1-4 carbon atoms, and the number of the substituent is 1-5, preferably 1 or 2; halogen is one or more of F, Cl and Br;

the method is characterized in that:

the synthetic route is shown as the following reaction formula, styrene derivatives (2), chlorine sources (3) and diphenyl disulfide (and/or thiophenol) compounds (4) are used as raw materials, and free radical addition reaction is carried out under electrochemical conditions to generate alpha, beta-dichlorobenzene sulfoxide compounds (1);

in the reaction formula, the substituent R and the substituent R' are the same as the structural formula (1).

2. A method of synthesis according to claim 1, characterized in that:

the mol ratio of the styrene derivative (2) to a chlorine source (taking a chlorine atom as a metering unit, the same below) (3) and diphenyl disulfide (and/or thiophenol, taking a sulfur atom as a metering unit, the same below) compounds (4) is 1:1-6: 0.5-2; the reaction time is 3-8 hours; the reaction temperature is 20-80 ℃;

introducing current of 5-25mA into the reaction system; carrying out a reaction in a reaction solvent in the presence of an electrolyte; and after the reaction is finished, separating the product to obtain the alpha, beta-dichlorobenzene sulfoxide compound (1).

3. A method of synthesis according to claim 1, characterized in that: reacting a styrene derivative (2) with a chlorine source (3) and a diphenyl disulfide (thiophenol) compound (4), wherein: the reaction solvent is one or more than two of acetonitrile and water in a volume ratio of 1:19-1:9, N-dimethylformamide and water in a volume ratio of 1:19-1:9, and acetone and water in a volume ratio of 1:19-1: 9; the preferable ratio of acetonitrile to water in the reaction solvent is 1:19-1:12, the optimal ratio is 1:15-1:12, and the optimal reaction is carried out on acetonitrile and water with the volume ratio of 1: 12;

when the styrene derivative (2) is reacted with a chlorine source (in terms of chlorine atom as a metering unit, hereinafter the same applies to) (3) and a diphenyl disulfide (and/or thiophenol) type compound (4), the styrene derivative (2) is preferably reacted with the chlorine source (3) and the diphenyl disulfide (and/or thiophenol in terms of sulfur atom as a metering unit, hereinafter the same applies to) type compound (4) in a molar ratio of 1:1 to 4:0.5 to 1.5, and the most preferable molar ratio is 1:1 to 3:0.5 to 1.

4. A method of synthesis according to claim 1, characterized in that: the reaction is carried out in a reaction vessel provided with a cathode and an anode, the anode and the cathode are oppositely arranged at a distance of 3-10mm, part or all of the cathode and the anode are arranged in the reaction liquid of the reaction system, and the area of the opposite surfaces of the anode and the cathode arranged in the reaction liquid is 25-100mm²Preferably 64-100mm²(ii) a An electric current is applied between a cathode and an anode in the reaction system.

5. A synthesis method according to claim 1 or 2, characterized in that: when the styrene derivative (2) reacts with the chlorine source (3) and the diphenyl disulfide (and/or thiophenol) compound (4), the reaction time is preferably 4-7 hours, and the optimal reaction time is 4-6 hours; the concentration of the styrene derivative (2) in the reaction solvent is 0.05 to 0.4M, preferably 0.05 to 0.3M, more preferably 0.1 to 0.2, most preferably 0.15M.

6. A synthesis method according to claim 1 or 2, characterized in that: when the styrene derivative (2) is reacted with the chlorine source (3) and the diphenyl disulfide (and/or thiophenol) compound (4), the reaction temperature is preferably from room temperature to 80 ℃ and the most preferable reaction temperature is from room temperature to 40 ℃.

7. A synthesis process according to claim 1 or 2 or 4, characterized in that: when the styrene derivative (2) is reacted with the chlorine source (3) and the diphenyl disulfide (and/or thiophenol) compound (4), the preferred current for the reaction is 10 to 20mA, and the most preferred current is 12 to 18 mA.

8. A synthesis method according to claim 1 or 4, characterized in that: when the styrene derivative (2) reacts with a chlorine source (3) and a diphenyl disulfide (and/or thiophenol) compound (4), the cathode and the anode are one or two of graphite, nickel, platinum or reticular glassy carbon electrodes; one or two of graphite and nickel electrodes are preferably used as the electrodes; the graphite is used as the anode, and the nickel is used as the cathode, so that the best effect is achieved.

9. A method of synthesis according to claim 2, characterized in that: when the styrene derivative (2) is reacted with a chlorine source (3) and a diphenyl disulfide (and/or thiophenol) compound (4), the electrolyte is an ionic liquid (e.g., one or more of 1-methyl-3-ethyl-imidazole tetrafluoroborate, 1-methyl-3-ethyl-imidazole hexafluorophosphate, 1-methyl-3-ethyl-imidazole perchlorate, N-hexylpyridinium tetrafluoroborate, 1-butyl-2, 3-dimethylimidazole chloride, 1-hexyl-2, 3-dimethylimidazole bromide, N-butylpyridinium tetrafluoroborate, 1-propyl-3-methylimidazole bromide, 1-ethyl-3-methylimidazole chloride) or a quaternary ammonium salt (e.g., tetramethyltetrafluoroborate, one or more of tetraethyl tetrafluoroborate, tetrabutyl hexafluorophosphate, tetrabutyl perchlorate, tetraethyl ammonium chloride, tetraethyl ammonium bromide, tetrabutyl ammonium bisulfate, tetraethyl amine p-toluenesulfonate, triethylamine hydrofluoride)One or more than two; it is preferable to use one or more of quaternary ammonium tetrafluoroborates (e.g., one or more of tetramethyltetrafluoroborate, tetraethyltetrafluoroborate, tetrabutyltetrafluoroborate) as the electrolyte; with tetramethyltetrafluoroborate (Me)₄NBF₄) Optimizing;

the concentration of the electrolyte in the reaction solvent is 0.025 to 1.0M, preferably 0.025 to 0.1M, and most preferably 0.025 to 0.05M.

10. A method of synthesis according to claim 1, characterized in that: when the styrene derivative (2) reacts with the diphenyl disulfide (and/or thiophenol) compound (4), the chlorine source is one or more than two of calcium chloride, magnesium chloride, lithium chloride, sodium chloride, potassium chloride and N-chlorosuccinimide; the most preferred chlorine source is N-chlorosuccinimide.

Background

Organic chlorides are common structural motifs in many biologically active natural products and polymers and are widely used as intermediates in organic synthesis (Grible, G.W.J.Nat.Prod.1992,55,1353-1395. G.l, B.; Bucher, C.; Burns, N.Z.Mar.drugs 2016,14, 206.; Sawada, H.in Encyclopedia of Polymeric Nanomaterials; Kobayashi, S., U.S.,k, eds.; springer Berlin, Heidelberg, 2015; pp 1-10.). Among the earliest organic reactions discovered, the dichlorination of olefins remained a very common method for incorporating chlorine atoms into organic molecules (Cresswell, A.J.; Eey, S.T.C.; Denmark, S.E.Angew.Chem., Int.Ed.2015,54, 15642-. The ideal reagent for this conversion is from a nucleophilic chlorine source, since in nature chlorine is almost completely present in chlorine equivalents. Thus, the combination of Cl-and strong oxidants has become a traditional practice for using electrophilic chlorinating agents such as Cl²An attractive alternative to (U.S. Pat. No. M.Bull. chem. Soc. Jpn.1974,47,3121-3124.Ho, T-L.; Gupta, B.G.B.; Olah, G.A.Synthesis 1977,676 677; Nugent, W.A.tetrahedron Le1978, 19,3427-3430.Donnelly, K.D.; Frad, W.E.; Gellerman, B.J.; Peterson, J.R.; Selle, B.J.tetrahedron Lett.1984,25,607-610.Mark, I.E.; Schrdson, P.R.Balley, M.A., A.G.D.J.tetrahedron, U.S. Pat. No. D., G.7, U.S. Pat. No. C.D.; E.S. D.S. D. Cheyne, U.S. Pat. No. 7, U.S. No. 11, U.7, U.S. Pat. No. 7, T.S. 11-3124. Ho.H.H.H.H.H. Ho, T.C. 7, T. J. Pat. D. No. 7, U.7, Val No. C. 7, U.S. J. C. J. No. D. No. 11, Val No. C. 7, U.S. C. No. 11, Val. No. 7, Val. 7, D. C. 7, D. 7, Val. 7, Val No. 7, D. 7, Val No. 7, Val. J. C. D. 7, Val No. C. D. 7, Val No. 7, Val No. D. No. C. 7, Val No. C. D. 7, Val No. 7, D. C. 7, Val No. P.S. D. P.7, D. P.S. D. 7, D. No. 7, Val No. D. P.S. P.7, Val. 7, P.P.P.P.P.P.P.P.P.P.S. P.P.P.P.P.S. P.P.P.P.P.P.P.P.P.P.7, Val et K. P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.C.C.C.C.C.C.C.P.P.C.C.C.C.P.P.P.P.P.C.C.C.C.C.C.C.C.C.P.P.P.P.P.P.P.P.P.H.H.P.C.C.C.P.P.P.P.P.P.P.P.P.P.C.4, P.P.P.4, Val.H.H.H.P.P.H.C.P.P.P.P.P.P.P.P.C.C.C.H.H.P.P.C, N.L.; ying,Y.；Heretsch,P.M.；Chen,J.S.J.Am.Chem.Soc.2011,133,8134-8137.；Landry,M.L.；Hu,D.X.；McKenna,G.M.；Burns,N.Z.J.Am.Chem.Soc.2016,138,5150-5158.)。

Sulfur is one of the most important elements, present in the form of amino acids and proteins. (J.T.Brosnan and M.E.Brosnan, J.Nutr, 2006,136,1636S.) many organosulfur compounds are commonly used in daily life as drugs (C.ZHAO, K.P.Rakesh, L.Ravidar, W.Y.Fang and H.L.Qin, Eur.J.Med.Chem.,2019,162, 679-S.734; D.A.Didivider and A.Montanaro, Ann.Allergy, Asthama, Immunol, 2008,100, 91-101.) they also gain significant importance in non-natural products, such as material chemistry, chemical biology 176, H.Ishitani, Y.Medito, Y.Nakara, W.Yoo and S.BAyaya shi, Asian J.org, Oreman, Okamura, J.8, Getsun, J.T.7.T.T.T.T.J.D.T.T.T.T.T.No. 8, J.T.T.T.T.T.T.T.T.T.T.T.T.T.S. No. 7, J.T.T.T.1, K.T.T.T.1, K.1, O.9, O.Q.Q.Q.Q.1, Eur.Q.Q.Q.1, Eur, Eur.Q.Q.Q.Q.Q.Q.1, Eur.Q.Q.Q.1, Eur.Q.C.C.1, Eur.C.though, Eur.C.C.S. 1, Eur.C.S. 1, Eur.S. 1, Eur.1, Eur.S. 1, Euro.S. 1, Eur.S. 1, Euro.S. 1, Euro, Euro.S. 11, Euro.S. 1, Euro, Euro.S. 1, Euro, Euro.S. 1, Euro, Eur. In organic synthesis, a transition metal catalytic system is mainly explored, and a synthesis tool box for carbon-sulfur (C-S) bond generation reaction is expanded (C. -F.Lee, Y. -C.Liu and S.S.Badsara, chem. -Asian J.,. 2014,9, 706-. Therefore, various metal-free and environmentally friendly synthetic methods are needed (a.k.sinha and d.equbal, Asian j.org.chem.,2019,8, 32-47.) electrochemical direct dehydrogenation C-H/S-H cross-coupling is a more attractive method of C-S bond formation than traditional coupling reactions (y.yuan and a.lei, nat. commun.,2020,11, 802.).

The method generally has the defects of harsh reaction conditions, addition of an oxidant, complicated steps, low atom economy, multiple byproducts and the like, and the alpha, beta-dichlorobenzene sulfoxide compounds are not successfully prepared. In the invention, under the condition of electrocatalysis, the styrene derivative (2) reacts with N-chlorosuccinimide (3) and diphenyl disulfide (thiophenol) compounds (4), and the three-functionalization of olefin is realized by one step to efficiently prepare a series of alpha, beta-dichlorobenzene sulfoxide compounds (1) with different structures. The reaction is simple and convenient to operate, environment-friendly, free of additional oxidant and capable of being prepared in large scale.

Disclosure of Invention

The invention aims to provide a method for preparing alpha, beta-dichlorobenzene sulfoxide compounds with easily obtained raw materials, simple and convenient operation, mild reaction conditions, environmental protection and atom economy.

In order to achieve the purpose, the technical scheme of the invention is as follows:

under the air atmosphere, the styrene derivative (2) and a chlorine source (3) and diphenyl disulfide (and/or thiophenol) compounds (4) are subjected to trifunctional reaction. And after the reaction is finished, performing product separation and characterization according to a conventional separation and purification method to obtain the corresponding alpha, beta-dichlorobenzene sulfoxide compound (1).

The technical scheme is characterized in that:

1. styrene derivatives, diphenyl disulfide (and/or thiophenol) compounds and N-chlorosuccinimide are taken as raw materials, and the substituent groups are as follows:

1) the substituent R is hydrogen or halogen (F, Cl or Br), alkyl with 1-4 carbon atoms, carboxylate with 1-4 carbon atoms, phenyl, acetoxyl, trifluoromethyl, nitro, cyano or carboxyl, and the number of the substituent is 1-5, preferably 1 or 2;

2) the substituent R' is one or more of hydrogen, halogen (F, Cl), alkyl with 1-4 carbon atoms and alkoxy with 1-4 carbon atoms, and the number of the substituent is 1-5, preferably 1 or 2;

2. the reaction solvent is one or more than two of acetonitrile and water, N-dimethylformamide and water, acetone and water; the reaction in acetonitrile and water is optimal;

3. when the styrene derivative (2) reacts with a chlorine source (3) (taking chlorine atoms as a metering unit, the same applies below) and a diphenyl disulfide (and/or thiophenol, taking sulfur atoms as a metering unit, the same applies below) compound (4), the optimal molar ratio is 1:1.5: 1; the ratio of acetonitrile to water in the reaction solvent is preferably 1: 12.

4. The reaction time is 3-8 hours, and the optimal reaction time is 4-6 hours.

5. The optimum reaction temperature is from room temperature to 40 ℃.

6. The reaction is carried out under constant current, the current intensity is 5-25mA, and the optimal current intensity is 15 mA.

7. Graphite, nickel, platinum or reticular glassy carbon electrodes are used in the reaction, and the best effect is achieved by taking graphite as an anode and nickel as a cathode.

8. The electrolyte used in the reaction is one or more of ionic liquid or quaternary ammonium salt; quaternary ammonium tetrafluoroborate is preferably used as the electrolyte; with tetramethyltetrafluoroborate (Me)₄NBF₄) And (4) optimizing.

9. The chlorine source is one of calcium chloride, magnesium chloride, lithium chloride, sodium chloride, potassium chloride and N-chlorosuccinimide; the most preferred chlorine source is N-chlorosuccinimide.

The invention has the following advantages:

1) electrochemical organic synthesis, and the use of environment-friendly 'electrons' as an oxidant avoids the use of the oxidant in the traditional olefin multi-functionalization reaction.

2) The reaction is carried out at normal temperature and normal pressure, does not need strong oxidant and inert gas protection, can be scaled up, and has high yield and simple and convenient operation and post-treatment.

3) The method for synthesizing the alpha, beta-dichlorobenzene sulfoxide compound is one method at present, and the used raw materials can be commercially obtained at low cost.

4) The multiple functional groups carried in the product can also continue to react to derive products of different structures.

In a word, the invention realizes the trifunctional reaction of the styrene, the N-chlorosuccinimide and the diphenyl disulfide (thiophenol) compounds under the electrochemical condition, and prepares the alpha, beta-dichlorobenzen sulfoxide compounds with high yield. The method is green and environment-friendly, does not need inert gas protection and additional oxidant, has wide substrate application range, good product functional group compatibility, cheap and easily-obtained raw materials, simple and convenient operation, high product yield, good atom economy and environmental protection.

Detailed Description

A5 mL reaction flask was charged with 1c (0.5mmol), boric acid (0.75mmol), and K in the order of₃PO₄(1.5mmol), PPPd ((Pd (PPh3)4) directly braided into a POP structure by hypercrosslinking, called PPPd) (1.4 wt% Pd,0.0005mmol), solvent (2ml, H2O/ethanol v/v ═ 2:3), and then sealed. Taken out of the glove box and heated to 80 ℃ in an oil bath for 6 h. The whole reaction mixture was then poured into 15mL of a saturated aqueous salt solution, extracted with 3X 20mL (3 times 20mL each), and dried over MgSO 4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate/petroleum ether ═ 1:5) to give the desired product I (yield: 96%). Then taking a new 5mL reaction bottle, adding the compound I (0.5mmol) and EtMgBr (1mmol) in an Ar glove box, reacting for 2h at normal temperature, and adding saturated NH after the reaction is finished₄Aqueous Cl was quenched, and the entire reaction mixture was poured into 15mL of saturated aqueous salt solution, extracted with 3X 20mL of ethyl acetate, and dried over MgSO 4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate/petroleum ether v/v ═ 1:10) to give the desired product II (yield: 80%). Finally compound II (0.4mmol) was added to HCl saturated Et₂To a solution of O (10mL), heated for 5h, after the reaction was completed, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate/petroleum ether v/v ═ 1:8) to obtain the desired product p, p' -DDD (yield: 63%). The compound 1c was successfully converted into 4, 4-dribbles by the above procedure, which were commonly used as standard samples for pesticide and pesticide residue analysis.

The following examples are provided to aid in the further understanding of the present invention, but the invention is not limited thereto.

Comparative example 1:

a dried 10ml two-neck glass tube, a magneton is added in the glass tube, a rubber plug is plugged on the bottle mouth of the side neck, a threaded polytetrafluoroethylene cap with two electronic leads is respectively connected with a 100PPI RVC anode electrode (0.5 X1.0X0.6cm) of Beijing Jingkoku scientific instruments Co., Ltd³Connected to an electronic lead by a 9cm long, 2mm diameter graphite rod), and a platinum sheet cathode electrode (0.5X1.0 cm)²) The distance between the closest points of the two electrodes was kept at 0.3cm, and the glass tube was inserted to a depth exceeding the reaction solution. Adding Mn (OTf)₂(3.5-3.6mg,5 mol% (relative to styrene)) and MgCl₂(57.0mg,0.6mmol,3.0equiv (relative to styrene)). The reaction flask was sealed and purged with nitrogen for 5 minutes, and then styrene (0.20mmol) and an electrolyte solution (0.10M LiClO) were sequentially added thereto by means of a syringe₄in MeCN,3.5mL) and acetic acid (0.40 mL). The reaction mixture was then flushed with nitrogen for 5 minutes. The nitrogen-filled balloon was maintained in a nitrogen atmosphere through the rubber stopper. The cell potential for electrolysis was 2.3V, starting at 40 deg.C (oil bath temperature). After complete consumption of the olefin starting material was determined by thin layer chromatography, the electrical input was turned off. The entire reaction mixture was then poured into 15mL of brine solution, extracted with 3X 20mL of ethyl acetate, and dried over MgSO 4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography (pure petroleum ether (60-90 ℃ C. fraction)) to obtain the desired product (yield: 85%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Comparative example 2:

the olefin (0.2mmol) and copper dichloride (0.8mmol,4equiv (relative to reaction 1), 107.6mg) were dissolved in MeCN (5mL) and placed in a 25mL Schlenk tube. Stirring was carried out under 38W white light led for 72h under nitrogen atmosphere. After the reaction was completed, the resulting mixture was poured into 15mL of a brine solution, extracted with 3X 20mL of ethyl acetate, and dried over MgSO 4. The solvent was removed under reduced pressure and the residue was purified by silica gel column chromatography (petroleum ether (60-90 ℃ C. fraction): methylene chloride v/v ═ 10:1) to give the desired product (yield: 70%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 1

Styrene 2a (46. mu.L, 0.4mmol), N-chlorosuccinimide 3a (80mg, 0.6mmol), 4, 4-dimethyldiphenyl disulfide 4a (49mg, 0.2mmol), tetramethylammonium tetrafluoroborate (16mg, 0.1mmol), and 3.7mL of CH were sequentially added to a 10mL reaction tube at room temperature under an air atmosphere₃CN and 0.3mL H₂O, using graphite as an anode (8 mm in length, 2mm in width, 50mm in height), nickel as a cathode (8 mm in length, 2mm in width, 50mm in height), inserting the lower ends of the anode and the cathode into the liquid surface to a depth of 8mm, and arranging the planes of the length and the height of the two electrodes (the anode and the cathode) in parallel with each other (the area of the opposite surfaces of the anode and the cathode placed in the reaction solution is 64 mm)²) The distance between the electrodes was 5mm, and a constant current of 15 milliamperes was applied between the electrodes to conduct the reaction for 4 hours. After completion of the reaction, extraction was performed with ethyl acetate (3 × 10mL, three times in total), the organic layers were combined, dried over anhydrous sodium sulfate, filtered, and the volatile components were removed under reduced pressure, followed by silica gel column chromatography (eluent was petroleum ether (fraction at 60-90 ℃)/ethyl acetate, v/v ═ 6:1) to obtain the objective product 1a (58.8mg, yield 83%) as a white solid. The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Compared with a comparative example, the method does not need a metal catalyst or nitrogen protection, is simple to operate, adds a sulfoxide group on the basis of the two chlorines, and uses water as an oxygen source, so that the method is clean and safe. The one-step three-functionalization reaction of olefin is realized for the first time, three chiral centers are constructed, four chemical bonds are formed, and the atom and step economy are high.

Example 2

The reaction procedure and the operating conditions were the same as in example 1, except that lithium perchlorate was used in equimolar amounts instead of tetramethylammonium tetrafluoroborate as the electrolyte, as in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 63%).

Example 3

The reaction procedure and operation conditions were the same as in example 1, except that tetrabutylammonium perchlorate was used in equimolar amounts instead of tetramethylammonium tetrafluoroborate as an electrolyte, in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 72%).

Example 4

The reaction procedure and operation conditions were the same as in example 1, except that tetrabutylammonium tetrafluoroborate was used in equimolar amounts instead of tetramethylammonium tetrafluoroborate as an electrolyte, in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 67%).

Example 5

The reaction procedure and operation conditions were the same as in example 1, except that tetrabutylammonium hexafluorophosphate was used in equimolar amounts instead of tetramethylammonium tetrafluoroborate as an electrolyte, in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 64%).

Example 6

The reaction procedure and operation conditions were the same as in example 1, except that tetraethylammonium chloride was used in equimolar amounts instead of tetramethylammonium tetrafluoroborate as an electrolyte, in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 61%).

Example 7

The reaction procedure and operation conditions were the same as in example 1, except that tetrabutylammonium bromide was used in equimolar amounts instead of tetramethylammonium tetrafluoroborate as an electrolyte, in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 55%).

Example 8

The reaction procedure and operation conditions were the same as in example 1, except that 1-ethyl-3-methylimidazolium tetrafluoroborate was used in equimolar amounts instead of tetramethylammonium tetrafluoroborate as an electrolyte, in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 70%).

Example 9

The reaction procedure and operation conditions were the same as in example 1, except that tetrabutylammonium hydrogen sulfate was used in equimolar amounts instead of tetramethylammonium tetrafluoroborate as an electrolyte, in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 58%).

Example 10

The reaction procedure and operation conditions were the same as in example 1, except that tetraethylammonium p-toluenesulfonate was used in equimolar amounts instead of tetramethylammonium tetrafluoroborate as an electrolyte, as in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 59%).

Example 11

The reaction procedure and operation conditions were the same as in example 1, except that tetrabutylammonium iodide was used in equimolar amounts instead of tetramethylammonium tetrafluoroborate as an electrolyte, in example 1. The reaction is stopped, and the target product 1a is not obtained after the post-treatment. Indicating that iodine is detrimental to the reaction.

Example 12

The reaction procedure and operating conditions were the same as in example 1, except that no electrolyte, tetramethylammonium tetrafluoroborate, was added. And (3) finding that the reaction system cannot conduct electricity normally, and finding that the target product 1a is not obtained after reaction post-treatment. Indicating that no electrolyte addition reaction occurred.

Example 13

The reaction procedure and operation conditions were the same as in example 1, except that an equal volume of DMF was used as a solvent instead of MeCN in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 15%).

Example 14

The reaction procedure and operation conditions were the same as in example 1, except that an equal volume of acetone was used as a solvent instead of MeCN, in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 39%).

Example 15

The reaction procedure and operating conditions were the same as in example 1, except that an equal volume of MeOH was used as the solvent instead of MeCN, as in example 1. The reaction is stopped, and the target product 1a is not obtained after the post-treatment.

Example 16

The reaction procedure and operation conditions were the same as in example 1, except that the same volume of DMSO was used as the solvent instead of MeCN. The reaction is stopped, and the target product 1a is not obtained after the post-treatment.

Example 17

The reaction procedure and operating conditions were the same as in example 1, except that an equal volume of DMA was used as the solvent instead of MeCN, as in example 1. The reaction is stopped, and the target product 1a is not obtained after the post-treatment.

Example 18

The reaction procedure and operation conditions were the same as in example 1, except that an equal volume of EtOH was used as a solvent instead of MeCN, in example 1. The reaction is stopped, and the target product 1a is not obtained after the post-treatment.

Example 19

The reaction procedure and operation conditions were the same as in example 1, except that an equal volume of THF was used as a solvent instead of MeCN, in example 1. The reaction is stopped, and the target product 1a is not obtained after the post-treatment.

Example 20

The reaction procedure and operation conditions were the same as those in example 1, except that C-C was used as an electrode instead of C-Ni as in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 72%).

Example 21

The reaction procedure and operation conditions were the same as those in example 1, except that C-Pt was used as an electrode instead of C-Ni, in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 67%).

Example 22

The reaction procedure and operation conditions were the same as those in example 1, except that RVC-Ni was used as an electrode instead of C-Ni in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 34%).

Example 23

The reaction procedure and operation conditions were the same as those in example 1, except that Pt-Pt was used as an electrode instead of C-Ni. The reaction is stopped, and the target product 1a is not obtained after the post-treatment.

Example 24

The reaction procedure and operation conditions were the same as those in example 1, except that Pt-Ni was used as an electrode instead of C-Ni. The reaction is stopped, and the target product 1a is not obtained after the post-treatment.

Example 25

The reaction procedure and operation conditions were the same as in example 1, except that 12mA instead of 15mA was used as the reaction current in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 64%).

Example 26

The reaction procedure and operation conditions were the same as in example 1, except that 18mA instead of 15mA was used as the reaction current in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 65%).

Example 27

The reaction procedure and operation conditions were the same as in example 1, except that the reaction was carried out in the absence of electric current, as in example 1. The reaction was stopped and no product was found to be formed. Indicating that the reaction needs to be carried out under electrochemical conditions.

Example 28

The reaction procedure and operation conditions were the same as in example 1, except that LiCl was used in equimolar amounts instead of NCS as a chlorine source, in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 60%).

Example 29

The reaction procedure and operation conditions were the same as in example 1, except that MgCl was used in example 1₂·6H₂O equimolar instead of NCS as chlorine source. The reaction was stopped and worked up to give the desired product 1a (yield: 47%).

Example 30

The reaction procedure and operation conditions were the same as those in example 1, except that CaCl was used in comparison with example 1₂Equimolar instead of NCS as chlorine source. The reaction was stopped and worked up to give the desired product 1a (yield: 50%).

Example 31

The reaction procedure and operation conditions were the same as in example 1, except that NaCl was used in equimolar amounts instead of NCS as a chlorine source, in comparison with example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 48%).

Example 32

The reaction procedure and operation conditions were the same as in example 1, except that KCl was used in equimolar amounts instead of NCS as a chlorine source, as in example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 26%).

Example 33

The reaction procedure and operation conditions were the same as in example 1, except that CuCl was used in example 1₂Equimolar instead of NCS as chlorine source. The reaction is stopped, and the target product 1a is not obtained after the post-treatment.

Example 34

The reaction procedure and operation conditions were the same as in example 1, except that NH was used in the reaction mixture of example 1₄Cl was equimolar as chlorine source instead of NCS. The reaction is stopped, and the target product 1a is not obtained after the post-treatment.

Example 35

The reaction procedure and operating conditions were the same as in example 1, except that HCl was used in equimolar amounts instead of NCS as the chlorine source, in comparison with example 1. The reaction was stopped and worked up to give the desired product 1a (yield: 47%).

Example 36

The reaction procedure and operation conditions were the same as in example 1, except that the reaction was carried out in a nitrogen atmosphere, as in example 1. The reaction was terminated, and the same workup as in example 1 above was carried out to give the objective product 1a (75.5mg, yield 80%). The oxygen of the sulfoxide in the target product 1a is shown to be derived from water added in the system.

Example 37

The reaction procedure and operation conditions were the same as in example 1, except that no water was added to the system, as in example 1. The reaction is stopped, and the target product 1a is not obtained after the post-treatment. Water is described as an indispensable oxygen source for the reaction.

Example 38

The reaction procedure and operation conditions were the same as in example 1, except that water was used as a solvent, as in example 1. The reaction is stopped, and the target product 1a is not obtained after the post-treatment. Indicating that acetonitrile is the necessary solvent for the reaction.

Example 39

The procedure of the reaction was as in example 1, except that the styrene derivative added to the reaction system was 4-fluorostyrene 2b (48. mu.L, 0.4 mmol). The reaction was stopped and worked up to give the desired product 1b as a white solid (80mg, yield 81%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 40

The procedure of the reaction was the same as in example 1, except that the styrene derivative added to the reaction system was 4-chlorostyrene 2c (48. mu.L, 0.4mmol) in comparison with example 1. The reaction was stopped and worked up to give the desired product 1c as a white solid (89.5mg, yield 86%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

EXAMPLE 41

The procedure and operation were the same as in example 1, except that the styrene derivative added to the reaction system was 4-bromostyrene 2d (52. mu.L, 0.4 mmol). The reaction was stopped and worked up to give the desired product 1d as a white solid (75.6mg, yield 64%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 42

The procedure of the reaction was the same as in example 1, except that the styrene derivative added to the reaction system was 2, 5-dimethylstyrene 2e (59. mu.L, 0.4 mmol). The reaction was stopped and worked up to give the desired product 1e as a white solid (83.1mg, yield 81%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 43

The procedure was as in example 1 except that the styrene derivative added to the reaction system was 4-vinylbenzoic acid 2f (59mg, 0.4 mmol). The reaction was stopped and worked up to give the desired product 1f as a white solid (47.8mg, yield 45%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 44

The procedure of the reaction was the same as in example 1, except that 2g (51. mu.L, 0.4mmol) of 2-chlorostyrene was added to the reaction system in the difference from example 1. The reaction was stopped and worked up to give the desired product as a white solid, 1g (75.6mg, yield 72%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 45

The procedure of the reaction was the same as in example 1, except that the styrene derivative added to the reaction system was 4-acetoxystyrene for 2h (61. mu.L, 0.4mmol) in comparison with example 1. The reaction was stopped and worked up to give the title product as a white solid for 1h (96.2mg, 86% yield). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 46

The procedure of the reaction was the same as in example 1, except that the styrene derivative added to the reaction system was 4-t-butylstyrene 2i (73. mu.L, 0.4 mmol). The reaction was stopped and worked up to give the desired product 1i as a white solid (71.1mg, yield 64%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 47

The procedure of the reaction was the same as in example 1, except that the styrene derivative added to the reaction system was 4-phenylstyrene 2j (72mg, 0.4 mmol). The reaction was stopped and worked up to give the desired product 1j (73.2mg, yield 63%) as a white solid. The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 48

The procedure and operation were the same as in example 1, except that the styrene derivative added to the reaction system was 4-trifluoromethylstyrene 2k (59. mu.L, 0.4 mmol). The reaction was stopped and worked up to give the desired product 1k as a white solid (76.9mg, yield 67%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 49

The reaction procedure and operation were the same as in example 1, except that the styrene derivative added to the reaction system was 2L (56. mu.L, 0.4mmol) of 4-chloromethylstyrene. The reaction was stopped and worked up to give the desired product 1l as a white solid (77.3mg, 71% yield). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 50

The procedure of the reaction was the same as in example 1, except that the styrene derivative added to the reaction system was 4-methylstyrene (2m, 53. mu.L, 0.4mmol) in example 1. The reaction was stopped and worked up to give the desired product 1m as a white solid (67.5mg, yield 69%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 51

The procedure of the reaction was the same as in example 1, except that the styrene derivative added to the reaction system was 4-nitrostyrene 2n (60mg, 0.4 mmol). The reaction was stopped and worked up to give the desired product 1n as a white solid (26.5mg, yield 25%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 52

The procedure and operation were the same as in example 1, except that the styrene derivative added to the reaction system was 4-cyanostyrene 2o (48. mu.L, 0.4 mmol). The reaction was stopped and worked up to give the desired product 1o as a white solid (54mg, 53% yield). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 53

The procedure was as in example 1 except that the styrene derivative added to the reaction system was methyl 4-vinylbenzoate 2p (65mg, 0.4 mmol). The reaction was stopped and worked up to give the desired product 1p as a white solid (66.5mg, yield 60%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 54

The reaction procedure was the same as in example 1, except that diphenyl disulfide (thiophenol) was added as diphenyl disulfide 4b (44mg, 0.2 mmol). The reaction was stopped and worked up to give the desired product 1q as a white solid (56mg, 62% yield). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 55

The procedure of the reaction was as in example 1, except that the diphenyl disulfide (thiophenol) compound added to the reaction system was 4, 4-dimethoxydiphenyl disulfide 4c (56mg, 0.2 mmol). The reaction was stopped and worked up to give the desired product 1r as a white solid (68.1mg, yield 69%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 56

The procedure of the reaction was as in example 1, except that the diphenyl disulfide (thiophenol) compound added to the reaction system was 4, 4-dichlorodiphenyl disulfide 4d (58mg, 0.2 mmol). The reaction was stopped and worked up to give the desired product 1s as a white solid (51.2mg, 51% yield). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 57

The procedure of the reaction was the same as in example 1, except that the diphenyl disulfide (thiophenol) compound added to the reaction system was 4-isopropylthiophenol 4e (63. mu.L, 0.4 mmol). The reaction was stopped and worked up to give the desired product 1t as a white solid (72.8mg, yield 71%). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Example 58

The procedure of the reaction was the same as in example 1, except that diphenyl disulfide (thiophenol) compound was added as 4-tert-butylthiophenol 4f (69. mu.L, 0.4mmol) to the reaction system in example 1. The reaction was stopped and worked up to give the desired product 1u as a white solid (66.1mg, 62% yield). The target product is confirmed by nuclear magnetic resonance spectrum and high resolution mass spectrum.

Typical compound characterization data

1- (((1R,2R) -1, 2-dichoro-2-phenylethyl) sulfinyl) -4-methylbenzene (1a): white solid.¹H NMR(CDCl₃,400MHz)δ7.56(m,2H),7.42-7.35(m,7H),5.24(d,J＝10.8Hz,1H),4.72(d,J＝10.8Hz,1H),2.43(s,3H)；¹³C NMR(CDCl₃,100MHz)δ142.5,137.3,137.2,130.0,129.5,128.9,128.0,124.9,82.5,60.5,21.6.C₁₅H₁₄Cl₂HRMS theoretical value of OS [ M + H]⁺313.0215; measured value 313.0187.

1-(((1R,2R)-1,2-dichloro-2-(4-fluorophenyl)ethyl)sulfinyl)-4-methylbenzene (1b): white solid.¹H NMR(CDCl₃,400MHz)δ7.56-7.53(m,2H),7.41-7.35(m,4H),7.09-7.04(m,2H),5.23(d,J＝10.7Hz,1H),4.67(d,J＝10.7Hz,1H),2.43(s,3H)；¹³C NMR(CDCl₃,100MHz)δ163.1(d,J＝248.0Hz),142.7,137.1,133.3(d,J＝3.2Hz),130.0,129.9(d,J＝8.5Hz),124.9,116.0(d,J＝21.8Hz),82.7,59.8,21.6.C₁₅H₁₃Cl₂HRMS theoretical value of FOS [ M + H ]]⁺331.0121; measured value 331.0107.

1-chloro-4- ((1R,2R) -1, 2-dichoro-2- (p-tolysulfinyl) ethyl) bezene (1c) white solid.¹H NMR(CDCl₃,400MHz)δ7.56-7.53(m,2H),7.38-7.32(m,6H),5.21(d,J＝10.7Hz,1H),4.66(d,J＝10.7Hz,1H),2.43(s,3H)；¹³C NMR(CDCl₃,100MHz)δ142.7,137.0,135.9,135.5,130.1,129.4,129.2,124.9,82.4,59.7,21.6.C₁₅H₁₃Cl₃HRMS theoretical value of OS [ M + H]⁺346.9826; measured value 346.9837.

1-bromo-4- ((1R,2R) -1, 2-dichoro-2- (p-tolysulfinyl) ethyl) bezene (1d) white solid.¹H NMR(CDCl₃,400MHz)δ7.55-7.49(m,4H),7.36(d,J＝8.1Hz,2H),7.29-7.25(m,2H),5.19(d,J＝10.7Hz,1H),4.66(d,J＝10.7Hz,1H),2.43(s,3H)；¹³C NMR(CDCl₃,100MHz)δ142.7,137.0,136.4,132.2,130.1,129.7,124.9,123.7,82.3,59.8,21.6.C₁₅H₁₃BrCl₂HRMS theoretical value of OS [ M + H]⁺390.9320; measured value 390.9324.

2- ((1R,2R) -1, 2-dichoro-2- (p-tolsulylfinyl) ethyl) -1, 4-dimethyllbenzene (1e): white solid.¹H NMR(CDCl₃,400MHz)δ7.57(d,J＝8.2Hz,2H),7.38(d,J＝7.9Hz,2H),7.18(s,1H),7.08-7.03(m,2H),5.54(d,J＝11.0Hz,1H),4.82(d,J＝10.8Hz,1H),2.44(s,3H),2.40(s,3H),2.31(s,3H)；¹³C NMR(CDCl₃,100MHz)δ142.5,137.3,136.4,135.4,133.6,130.9,130.1,130.0,127.5,124.9,82.7,56.3,21.6,21.1,19.1.C₁₇H₁₈Cl₂HRMS theoretical value of OS [ M + H]⁺341.0528; measured value 341.0533.

4-((1R,2R)-1,2-dichloro-2-(p-tolylsulfinyl)ethyl) benzoic acid (1f) white solid.¹H NMR(CDCl₃,400MHz)δ8.13-8.11(m,2H),7.58-7.51(m,4H),7.37(d,J＝8.0Hz,2H),5.33(d,J＝10.7Hz,1H),4.72(d,J＝10.7Hz,1H),2.43(s,3H)；¹³C NMR(CDCl₃,100MHz)δ170.9,142.9,142.8,136.7,130.9,130.5,130.1,128.3,125.0,82.2,59.6,21.7.C₁₇H₁₈Cl₂HRMS theoretical value of OS [ M + H]⁺357.0114; measured value 357.0113.

1-chloro-2- ((1R,2R) -1, 2-dichoro-2- (p-tolysulfinyl) ethyl) bezene (1g) a white solid.¹H NMR(CDCl₃,400MHz)δ7.56-7.53(m,2H),7.50-7.48(m,1H),7.42-7.39(m,1H),7.38-7.34(m,2H),7.33-7.27(m,2H),5.82(s,1H),4.90(s,1H),2.43(s,3H)；¹³C NMR(CDCl₃,100MHz)δ142.5,136.9,134.7,133.9,130.4,130.2,129.9,129.2,127.4,124.7,81.6,56.4,21.5.C₁₇H₁₈Cl₂HRMS theoretical value of OS [ M + H]⁺346.9826; measured value 346.9838.

4- ((1R,2R) -1, 2-dichoro-2- (p-tolsultyl) ethyl) phenyl acetate (1h) white solid.¹H NMR(CDCl₃,400MHz)δ7.55-7.53(m,2H),7.42-7.39(m,2H),7.35(d,J＝8.3Hz,2H),7.13-7.10(m,2H),5.23(d,J＝10.7Hz,1H),4.68(d,J＝10.7Hz,1H),2.42(s,3H),2.29(s,3H)；¹³C NMR(CDCl₃,100MHz)δ169.1,151.3,142.6,137.1,134.7,130.0,129.2,124.9,122.1,82.6,59.9,21.6,21.2.C₁₇H₁₆Cl₂O₃HRMS theoretical value of S [ M + H]⁺371.0270; measured value 371.0239.

1- (tert-butyl) -4- ((1R,2R) -1, 2-dichoro-2- (p-tolsulyfinyl) ethyl) bezene (1i): white solid.¹H NMR(CDCl₃,400MHz)δ7.56-7.55(m,2H),7.41-7.35(m,4H),7.33-7.30(m,3H),5.23(d,J＝10.7Hz,1H),4.73(d,J＝10.7Hz,1H),2.43(s,3H),1.31(s,3H)；¹³C NMR(CDCl₃,100MHz)δ152.7,142.5,137.3,134.2,130.0,127.7,126.0,124.9,82.7,60.5,34.9,31.3,21.7.C₁₉H₂₂Cl₂HRMS theoretical value of OS [ M + Na]⁺391.0661; measured value 391.0665.

4-((1R,2R)-1,2-dichloro-2-(p-tolylsulfinyl)ethyl) -1,1' -biphenyl (1j) as a white solid.¹H NMR(CDCl₃,400MHz)δ7.62-7.56(m,6H),7.48-7.42(m,4H),7.38-7.34(m,3H),5.30(d,J＝10.7Hz,1H),4.77(d,J＝10.8Hz,1H),2.44(s,3H)；¹³C NMR(CDCl₃,100MHz)δ142.6,142.5,140.2,137.2,136.2,130.1,129.0,128.5,127.9,127.7,127.3,124.9,82.6,60.4,21.7.C₂₁H₁₈Cl₂HRMS theoretical value of OS [ M + Na]⁺411.0348; measured value 411.0344.

1- (((1R,2R) -1, 2-dichoro-2- (4- (trifluoromethyl) phenyl) ethyl) sulfinyl) -4-meth ylbenzene (1k): white solid.¹H NMR(CDCl₃,400MHz)δ7.64(d,J＝8.2Hz,2H),7.57-7.52(m,4H),7.37(d,J＝8.0Hz,2H),5.28(d,J＝10.8Hz,1H),4.71(d,J＝10.7Hz,1H),2.43(s,3H)；¹³C NMR(CDCl₃,100MHz)δ142.8,141.1(d,J＝1.0Hz),136.8,131.6(q,J＝32.7Hz),130.1,128.6,126.0(q,J＝3.7Hz),124.9,123.8(q,J＝270.7Hz),82.1,59.5,21.7.C₁₆H₁₃Cl₂F₃HRMS theoretical value of OS [ M + H]⁺381.0089; measured value 381.0067.

1- (chloromethyl) -4- ((1R,2R) -1, 2-dichoro-2- (p-tolsulyfinyl) ethyl) bezene (1l) white solid.¹H NMR(CDCl₃,400MHz)δ7.56-7.53(m,2H),7.40-7.35(m,6H),5.24(d,J＝10.7Hz,1H),4.71(d,J＝10.7Hz,1H),4.57(s,2H),2.43(s,3H)；¹³C NMR(CDCl₃,100MHz)δ142.6,138.7,137.4,137.0,130.0,129.0,128.4,124.8,82.4,59.9,45.5,21.6.C₁₆H₁₅Cl₃HRMS theoretical value of OS [ M + H]⁺360.9982; measured value 360.9973.

1- (((1R,2R) -1, 2-dichoro-2- (p-tolyl) ethyl) sulfinyl) -4-methylbenzene (1m): white solid.¹H NMR(CDCl₃,400MHz)δ7.55(m,2H),7.36(d,J＝7.9Hz,2H),7.28(d,J＝8.2Hz,2H),7.18(d,J＝8.0Hz,2H),5.22(d,J＝10.8Hz,1H),4.73(d,J＝10.8Hz,1H),2.43(s,3H),2.35(s,3H)；¹³C NMR(CDCl₃,100MHz)δ142.4,139.6,137.2,134.3,129.9,129.6,127.8,124.8,82.6,60.4,21.6,21.3.C₁₆H₁₆Cl₂HRMS theoretical value of OS [ M + H]⁺327.0372; measured value 327.0373.

1- (((1R,2R) -1, 2-dichoro-2- (4-nitrophenyl) ethyl) sulfinyl) -4-methylbenzene (1n): white solid.¹H NMR(CDCl₃,400MHz)δ8.25-8.22(m,2H),7.61-7.57(m,2H),7.56-7.53(m,3H),5.31(d,J＝10.7Hz,1H),4.71(d,J＝10.7Hz,1H),2.43(s,3H)；¹³C NMR(CDCl₃,100MHz)δ148.3,143.9,142.9,136.5,130.0,129.1,124.8,124.1,81.8,58.8,21.5.C₁₅H₁₃Cl₂NO₃HRMS theoretical value of S [ M + H]⁺358.0066; measured value 358.0067.

4- ((1R,2R) -1, 2-dichoro-2- (p-tolysulfinyl) ethyl) benzyl) nitrile (1o) white solid.¹H NMR(CDCl₃,400MHz)δ7.67-7.63(m,2H),7.54-7.51(m,4H),7.35(d,J＝8.0Hz,2H),5.24(d,J＝10.7Hz,1H),4.70(d,J＝10.7Hz,1H),2.41(s,3H)；¹³C NMR(CDCl₃,100MHz)δ142.8,142.1,136.6,132.7,130.1,128.9,124.9,118.1,113.4,81.8,59.3,21.6.C₁₆H₁₃Cl₂HRMS theoretical value of NOS [ M-H]⁺336.0022; measured value 336.0020.

methyl 4- ((1R,2R) -1, 2-dichoro-2- (p-tolysulfinyl) ethyl) benzoate (1p): white solid.¹H NMR(CDCl₃,400MHz)δ8.07-8.02(m,2H),7.58-7.53(m,2H),7.51-7.46(m,2H),7.36(d,J＝8.0Hz,2H),5.26(d,J＝10.8Hz,1H),4.71(d,J＝10.8Hz,1H),3.91(s,3H),2.42(s,3H)；¹³C NMR(CDCl₃,100MHz)δ166.3,142.7,141.9,136.9,131.2,130.2,130.1,128.2,124.9,82.2,59.7,52.4,21.6.C₁₇H₁₆Cl₂O₃HRMS theoretical value of S [ M + H]⁺371.0270; measured value 371.0264.

((1R,2R) -1, 2-dichoro-2- (phenylsulfinyl) ethyl) bezene (1q): white solid.¹H NMR(CDCl₃,400MHz)δ7.69-7.65(m,2H),7.59-7.54(m,3H),7.42-7.36(m,5H),5.25(d,J＝10.8Hz,1H),4.75(d,J＝10.7Hz,1H)；¹³C NMR(CDCl₃,100MHz)δ140.4，137.1,131.8,129.5,129.2,128.9,127.9,124.8,82.5,60.5.C₁₄H₁₂Cl₂HRMS theoretical value of OS [ M + H]⁺:299.0059；Found:299.0054.

1-(((1R,2R)-1,2-dichloro-2-phenylethyl) sulfinyl) -4-methoxybezene (1r) a colorless liquid.¹H NMR(CDCl₃,400MHz)δ7.63-7.58(m,2H),7.42-7.34(m,5H),7.07-7.03(m,2H),5.23(d,J＝10.7Hz,1H),4.73(d,J＝10.7Hz,1H),3.85(s,3H)；¹³C NMR(CDCl₃,100MHz)δ162.6137.3,130.9,129.4,128.9,127.9,126.7,114.8,82.6,60.5,55.6.C₁₅H₁₄Cl₂O₂HRMS theoretical value of S [ M + H]⁺329.0164; measured value 329.0167.

1-chloro-4- (((1R,2R) -1, 2-dichoro-2-phenylethyl) sulfinyl) bezene (1s): white solid.¹H NMR(CDCl₃,400MHz)δ7.62-7.59(m,2H),7.55-7.52(m,2H),7.42-7.36(m,5H),5.23(d,J＝10.7Hz,1H),4.72(d,J＝10.7Hz,1H)；¹³C NMR(CDCl₃,100MHz)δ139.0，138.4,137.0,129.7,129.4,129.1,128.0,126.4,82.5,60.5.C₁₄H₁₁Cl₃HRMS theoretical value of OS [ M + H]⁺332.9669; measured value 332.9672.

1- (((1R,2R) -1, 2-dichoro-2-phenylethyl) sulfinyl) -4-isopopylpulbenzene (1t) is a white solid.¹H NMR(CDCl₃,400MHz)δ7.60-7.57(m,2H),7.46-7.36(m,7H),5.25(d,J＝10.7Hz,1H),4.74(d,J＝10.7Hz,1H),2.98(m,1H),1.28(d,J＝6.9Hz,6H)；¹³C NMR(CDCl₃,100MHz)δ153.3，137.3,137.2,129.4,128.9,127.9,127.4,124.9,82.6,60.5,34.2,23.8,23.7.C₁₇H₁₈Cl₂HRMS theoretical value of OS [ M + H]⁺341.0528; measured value 341.0523.

1- (tert-butyl) -4- (((1R,2R) -1, 2-dichoro-2-phenylethyl) sulfinyl) bezene (1u) white solid.¹H NMR(CDCl₃,400MHz)δ7.59-7.52(m,4H),7.40-7.34(m,5H),5.23(d,J＝10.7Hz,1H),4.74(d,J＝10.7Hz,1H),1.33(s,9H)；¹³C NMR(CDCl₃,100MHz)δ155.6，137.2,137.0,129.4,128.9,127.9,126.2,124.7,82.6,60.5,35.1,31.2.C₁₈H₂₀Cl₂HRMS theoretical value of OS [ M + H]⁺355.0685; measured value 355.0677.