Method for directly aminating aromatic alkane carbon-hydrogen bonds through electrochemical catalysis

Abstract

The invention belongs to the field of fine organic synthesis, and particularly relates to a method for directly aminating aromatic alkane carbon-hydrogen bonds through electrochemical catalysis, which efficiently converts primary or secondary aromatic alkanes into corresponding amination reaction products through one-step reaction. Compared with the conventional common method, the method has the remarkable advantages that (1) the first-grade or second-grade aromatic alkane which is wide in source and low in price is used as an initial raw material; (2) a metal catalyst, an exogenous oxidant and alkali are not involved, electrons are used as a clean oxidation medium, and the addition of a traditional exogenous oxidant is abandoned, so that the cost is reduced, and the environmental pollution is reduced; (3) activation and functionalization of inert carbon-hydrogen bonds are realized under mild reaction conditions; and (4) a sulfonyl imide substrate is used as a nitrogen source to introduce an amino group in the reaction, so that a target product can be obtained at a relatively ideal separation yield, and the product is rich in structure.

Description

Technical Field

[0001] The invention belongs to the field of fine organic synthesis, and in particular relates to a method for electrochemically catalyzing direct amination reaction of aromatic alkane carbon-hydrogen bonds. Background Art

[0002] C–H bonds are widely present in various organic compound molecules and are the most basic and core chemical bonds in organic molecules. Traditional valence bond construction strategies often require pre-functionalization of raw materials, followed by functional group transformation to achieve structural diversity derivatization. The C–H bond activation strategy is to directly use inert C–H bonds for functional group transformation, thereby avoiding the cumbersome multi-step pre-functionalization process. This is a very attractive synthetic strategy in the field of synthetic chemistry. However, it is quite challenging to achieve inert C–H activation functionalization under mild conditions: C–H bonds have high bond energy and are not easily activated by catalysis, and C–H bonds have low polarity and are not easily recognized and acted upon by catalysts. Currently, under metal catalysis systems, C–H bond activation strategies have been used to construct C–C bonds, C–O bonds, C–N bonds, C–X bonds, and so on.

[0003] Nitrogen-containing groups exist in the molecular skeletons of various drugs, and they can be converted into other functional groups through a variety of chemical or biocatalytic methods. Most amine compounds are widely used in the field of medicine and health because of their good biological and pharmaceutical activities, such as the anti-breast cancer drug letrozole; at the same time, some amine-containing small molecules are also monomers of functional materials, such as nylon. At present, the construction of amine products is mainly achieved by the substitution reaction of alkyl halides and N-containing nucleophiles under alkaline conditions. The problems with this method are: the reaction needs to be under alkaline conditions, and there is a problem of poor compatibility of the reaction functional groups and limited application of substrates; currently, most N-alkylation reactions use alkyl halides as raw materials, and the raw materials must be obtained from the pre-halogenation reaction of alkanes, which increases the reaction steps and the atom economy and yield are not high; alkyl halides are easily eliminated under alkaline conditions to produce olefin by-products, resulting in a low yield of N-alkylation reactions. The direct N–H / C–H coupling process between amines and alkanes in the presence of oxidants is an ideal and green strategy for constructing various amine compounds. However, the current N-alkylation reaction achieved through this strategy often requires an excess of chemical oxidants and is difficult to control the reaction regioselectivity.

[0004] At present, the construction of C-N bonds relies on pre-functionalized substrates such as aryl halides, alkyl halides, aryl halides, alkyl halides, etc., and the C-H bond activation amination reaction is carried out under the catalysis of transition metal catalysts, palladium, rhodium, copper, etc. to form new C-N bonds. For example: In 2012, Professor Gwilherm Evano's group reported a method for efficiently constructing C(sp)-N by copper-mediated oxidative cross-coupling of imines and terminal alkynes. This method was used to synthesize a series of nitrogen-containing precursors of azides and dienes (Org. Lett., 2012, 14, 6-9.). Professor Buchwald of the Massachusetts Institute of Technology and Professor Hartwig of the University of California, Berkeley, in the transition metal-catalyzed C(sp 2 )–N bond construction: The Buchwald-Hartwig amination reaction provides an efficient and universal method for building C–N bonds, which helps the efficient synthesis of nitrogen-containing active drug molecules and material monomers. 2 )–H bond amination reaction, C(sp 3 )–H bond amination reactions are more challenging, and chemists currently still rely on traditional synthetic methods: nucleophilic substitution reactions between nitrogen nucleophiles and alkyl halides. In terms of metal catalysis: In 2019, Prof. Warren used Cu catalysts to achieve highly selective coupling reactions of primary and secondary alkane C–H bonds with ammonia. The catalyst showed highly selective activation of primary and secondary C–H bonds in the amidation reactions of linear and cyclic alkanes with aromatic azides (Angew. Chem. Int. Ed. 2019, 58, 3421–3425.). In terms of photocatalysis, in 2023, Abigail G. Doyle reported a visible light redox catalysis method that can activate primary and secondary benzyl C (sp 3 )–H bond to achieve nucleophilic amination. In terms of electrocatalysis, in 2021, the research group of Professor Xu Haichao of Xiamen University reported a site-selective electrochemical amination reaction, which can achieve benzyl C–H amination through electrochemical selective oxidation without the participation of external oxidants or metal catalysts (Angew. Chem. Int. Ed. 2021, 60, 2943-2947.). At present, transition metal-catalyzed C(sp 2The research on the construction of C–H) / C–N bonds has become increasingly mature, with clear reaction mechanisms and efficient catalytic systems, and has been widely used in academic and industrial fields. However, with the pursuit of green chemistry and clean and efficient use of energy, metal-free, ligand-free, mild conditions, green and highly regioselective C–N bond formation reactions are still hot topics in the field of chemistry. In this context, the present invention realizes the dehydrogenative cross-coupling reaction of the primary or secondary C–H of cheap aryl alkanes with the N–H bonds of o-phenylsulfimide to form C(sp 3 –H) / C–N bonds and C(sp 2 The present invention has developed a method for constructing C-H bonds by activating functional groups of C-H bonds under mild conditions using a green electrochemical oxidative dehydrogenation strategy. It has high atom economy, good yield, and mild conditions, and is used for the efficient and green preparation of nitrogen-containing drug small molecules. Summary of the invention

[0005] Purpose of the invention: The technical problem to be solved by the present invention is to address the deficiencies of the prior art, such as: ① the use of highly polar and high boiling point solvents; ② the need for an equivalent amount of strong base, resulting in limitations in substrate application; ③ the halogenated hydrocarbon raw materials need to be functionalized in advance, and alkanes cannot be used directly in the catalytic process; ④ the reaction temperature is high and the time is long, etc., to provide a method for the direct amination reaction of aromatic alkane carbon-hydrogen bonds.

[0006] In order to solve the above technical problems, the present invention discloses a method for direct amination of aromatic alkanes carbon-hydrogen bonds. The present invention provides a green and efficient preparation method for direct amination products of aromatic alkanes carbon-hydrogen bonds. Using aromatic alkanes as substrates, electrochemical oxidation rather than transition metal catalysis is used to green and efficiently activate carbon-hydrogen bonds in aromatic alkanes to successfully construct C-N bonds, and prepare a series of primary or secondary aromatic alkane inert C-H amination products. The method described in the present invention is a new method for electrochemically oxidizing and activating the C-H of primary or secondary aromatic alkanes to construct C-N coupling reactions under mild conditions without metals. The method uses cheap and readily available primary or secondary aromatic alkanes instead of traditional halogenated hydrocarbons as raw materials, sulfonyl imide substrates as ammonia sources, does not require transition metal catalysts, bases and organic ligands, and uses clean electrons as oxidants to green and efficiently achieve electrochemical oxidation of aromatic alkanes carbon-hydrogen bond amination products.

[0007] The specific technical solutions are as follows:

[0008] A method for electrochemical oxidation of aromatic alkane carbon-hydrogen bonds for direct amination reaction, wherein an aromatic alkane compound and a sulfonimide compound are subjected to an electrochemical reaction in the presence of an electrolyte to obtain an amination product;

[0009] The structural formula of the aromatic alkane compound is shown in Formula I, the structural formula of the sulfonimide compound is shown in Formula II or Formula III, and the structural formula of the amination product is shown in Formula IV or Formula V.

[0010]

[0011] Preferably, the aromatic alkane of formula I and the sulfonimide compound of formula II undergo an electrochemical reaction in the presence of an electrolyte to obtain an amination product of formula IV; the aromatic alkane of formula I and the sulfonimide compound of formula III undergo an electrochemical reaction in the presence of an electrolyte to obtain an amination product of formula V.

[0012] Among them, R 1 Any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a fluoroalkyl group, a halogen group, an ester group, a cyano group, a nitro group, a phenyl group, a substituted phenyl group, a furyl group, a substituted furyl group, a pyrrolyl group, a substituted pyrrolyl group, a thienyl group, or a substituted thienyl group;

[0013] R 2 , R 3 , R 4 , R 5 and R 6 Each of them is independently selected from any one of a hydrogen atom, an alkyl group, an alkoxy group, a fluoroalkyl group, a halogen, an acyl group, an ester group, a vinyl group, a phenyl group, a substituted phenyl group, a furyl group, a substituted furyl group, a pyrrolyl group, a substituted pyrrolyl group, a thienyl group and a substituted thienyl group;

[0014] When R 6 When R is selected from hydrogen atoms, the aromatic alkane is a primary aromatic alkane; 6 When the aromatic alkane is selected from any one of alkyl, alkoxy, fluoroalkyl, halogen, acyl, ester, vinyl, phenyl, substituted phenyl, furyl, substituted furyl, pyrrolyl, substituted pyrrolyl, thienyl and substituted thienyl, the aromatic alkane is a secondary aromatic alkane. 1 Any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a fluoroalkyl group, a halogen group, a phenyl group, a cyano group, and an ester group; R 2 , R 3 , R 4 and R 5 R is independently selected from any one of an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group and a thienyl group. 6 Any one selected from a hydrogen atom, an alkyl group, a vinyl group, a phenyl group or a substituted phenyl group.

[0015] Preferably, the primary aromatic alkane includes any one of the following I-1 to I-12:

[0016]

[0017] Preferably, the secondary aromatic alkane includes any one of the following I-13 to I-31:

[0018]

[0019]

[0020] Preferably, the sulfonimide compound is selected from any one of II-1 to II-5, III-1, and III-2:

[0021]

[0022] Preferred amination products obtained from primary aromatic alkanes include any one of the following IV-1 to 15, V-1 or V-2:

[0023]

[0024]

[0025] Preferably, the amination product obtained from the secondary aromatic alkane includes any one of the following IV-16 to IV-36:

[0026]

[0027]

[0028] The molar ratio of the aromatic alkane compound to the sulfonimide compound is 4 to 6:1, preferably 4:1.

[0029] Wherein, the electrolyte includes any one of potassium bromide, ammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, potassium iodide or sodium bromide. Preferably, the electrolyte includes any one of sodium bromide, ammonium bromide or potassium bromide. More preferably, sodium bromide is used.

[0030] Wherein, the molar ratio of the electrolyte to the aromatic alkane compound is 1:2-4.

[0031] Wherein, the cathode material and the anode material of the electrochemical reaction are any one of a carbon rod or a platinum sheet. Preferably, the platinum sheet is the anode and the carbon rod is the cathode.

[0032] Wherein, the electrochemical reaction has a reaction current of 10-30 mA, preferably 20 mA, a reaction temperature of 60-80° C., and a reaction time of 3-8 hours. Preferably, the reaction is carried out at 80° C. for 5 hours.

[0033] Wherein, the electrochemical reaction includes a reaction solvent, and the reaction solvent is acetonitrile. 0.1-0.4 mmol of aromatic alkane compounds are added to each mL of acetonitrile. Preferably, 0.2-0.4 mmol of aromatic alkane compounds are added to each mL of acetonitrile.

[0034] Preferably, the method described herein uses cheap aromatic alkanes as raw materials, sulfonyl imide substrates as ammonia sources, clean electrons as oxidants, platinum sheets as anodes and carbon rods as cathodes, sodium bromide (NaBr) as electrolytes, and does not require the addition of any exogenous catalysts and oxidants. The reaction temperature is 80°C, and no acid-base reagents are used. The yield is medium to excellent, and high value-added products of alkane carbon-hydrogen bond activation amination are smoothly constructed. Further preferably, the electrochemical oxidation reaction is to dissolve aromatic alkane raw materials and sulfonyl imide ammonia sources and electrolyte sodium bromide in solvent acetonitrile in an undivided electrolytic cell, with platinum sheets as anodes and carbon rods as cathodes, under air conditions, the reaction temperature is 80°C, the current is 20mA, and the reaction is performed for 5 hours to obtain alkane carbon-hydrogen bond activation amination products. More preferably, in the acetonitrile reaction solution, the concentration of aromatic alkane compounds is 0.2mmol / mL.

[0035] Beneficial effects:

[0036] At present, transition metal catalytic oxidation to construct C–N coupling reactions faces difficulties such as poor regioselectivity, complex catalytic systems, large amounts of catalysts, expensive raw materials, many system byproducts, and low catalyst activity. Based on this challenge, the present invention provides an electrochemical oxidation strategy to achieve direct carbon-hydrogen bond amination reactions of inert primary or secondary aromatic alkane substrates. The invention reaction does not require the participation of catalysts and bases, uses NaBr as electrolyte, platinum sheets as anodes and carbon rods as cathodes, and has a reaction temperature of 80°C. The reaction has a wide range of applications and mild reaction conditions. A total of 17 primary aromatic alkane benzyl carbon-hydrogen bond direct oxidation amination products and 21 secondary aromatic alkane carbon-hydrogen bond direct amination products were efficiently prepared with moderate to excellent yields, providing a simple version for the green preparation of active drug small molecules, and also providing new ideas for the high-value utilization of cheap alkanes. Compared with the currently widely used substitution reaction using halogenated hydrocarbons as raw materials in a strong base and a polar high-boiling point solvent, the substrate of this invention has good universality, high yield and atom economy, and the oxidation process is simple to operate with low energy consumption, which reduces the production cost of such products and promotes the development of green processes.

[0037] The method improves the reaction efficiency, has a clean and green reaction process, high reaction safety, low environmental damage, and simple and easy post-processing. Compared with the prior art, the beneficial effects of the present invention are as follows:

[0038] (1) The present invention utilizes the electrochemical oxidation process as the driving force of the reaction and uses green electrons as the oxidant. There is no need to add additional metal catalysts and alkalis, and there is no need to use the currently widely used equivalent oxidants (such as TEMPO, KMnO4, BQ, etc.). The reaction is a neutral system and the post-processing is simple.

[0039] (2) The present invention directly uses primary or secondary aromatic alkane compounds as raw materials, which are cheap and readily available, have a simple and green reaction system, and have little harm to the environment, replacing the currently widely used halogenated alkanes. At the same time, the high-value conversion and utilization of cheap alkanes can be achieved.

[0040] (3) The present invention is carried out in an electrolytic cell, which has simple and safe operation, high mass transfer efficiency and short reaction time.

[0041] (4) Based on the technology of the present invention, the green and efficient preparation of multiple alkane direct oxidation amination compounds was achieved with medium to excellent yields, indicating that the technology has wide applicability and universality for promotion and application.

[0042] The method of the present invention has mild reaction conditions, is easy to control, has high atom economy, and the reaction process is green, environmentally friendly, and energy-efficient. The prepared product has high economic value and application potential, and is expected to be widely used in the fields of green organic synthesis methods and bioactive molecule creation. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments, and the above and / or other advantages of the present invention will become more clear.

[0044] Figure 1 It is the general reaction formula of the present invention.

[0045] Figure 2 This is a diagram of a conventional electrochemical reaction device used in the present invention.

[0046] Figure 3 This is a diagram of a gram-scale reaction apparatus.

[0047] Figure 4 This is a diagram of the reaction products at the gram level. DETAILED DESCRIPTION

[0048] The present invention is further described in detail below in conjunction with specific examples, but the protection scope of the present invention is not limited thereto, and also includes other oxidative amination reactions and products of corresponding skeletons derived from this technology. The experimental methods mentioned in the following examples are all conventional methods, i.e., common and general methods. The reagents and materials, if not otherwise specified, can be purchased from commercial channels.

[0049] The general reaction formula in the following examples is as follows Figure 1 As shown, the electrochemical reaction device is Figure 2 shown.

[0050] In the following examples, Examples 1 to 35 are electrochemically catalyzed direct amination of primary aromatic alkanes to generate primary carbon-hydrogen bond amination products, and Examples 36 to 71 are electrochemically catalyzed direct amination of secondary aromatic alkanes to generate secondary carbon-hydrogen bond amination products.

[0051] Example 1

[0052]

[0053] Under air atmosphere, o-benzylsulfimide (0.5mmol, 91.6mg), electrolyte potassium bromide (1mmol, 119.0mg), acetonitrile (ACN, 10mL), and p-methylanisole (2mmol, 244.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure, and the target product was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 16%.

[0054] The specific NMR data are as follows: 1 H NMR (400MHz, CDCl3): δ8.04 (dd, J=6.8, 1.3Hz, 1H), 7.92 (dd, J=6.9, 1.3Hz, 1H), 7.87 –7.79(m,2H),7.45(d,J=8.7Hz,2H),6.88(d,J=8.7Hz,2H),4.85(s,2H),3.79(s,3H); 13 C NMR (101MHz, CDCl3): δ159.6,158.9,137.7,134.8,134.3,130.4,127.4,126.6,125.2,121.0,114.1,55.3,42.3.

[0055] Example 2

[0056] The implementation method of this experiment is the same as that of Example 1, except that the electrolyte is ammonium bromide. Under air atmosphere, o-benzylsulfimide (0.5mmol, 91.6mg), ammonium bromide (1mmol, 97.9mg), acetonitrile (10mL), and p-methylanisole (2mmol, 244.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as a cathode and a platinum sheet (10mm×10mm×0.1mm) was used as an anode, a current of 20mA was applied, the reaction temperature was 80°C, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, and the measured separation yield was 34%.

[0057] Example 3

[0058] The implementation method of this experiment is the same as that of Example 1, except that the electrolyte is tetraethylammonium bromide (Et4NBr).

[0059] Under air atmosphere, o-phenylsulfonimide (0.5mmol, 91.6mg), tetraethylammonium bromide (1mmol, 210.2mg), acetonitrile (10mL), and p-methylanisole (2mmol, 244.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction, and it was found that no target product was generated.

[0060] Example 4

[0061] The implementation method of this experiment is the same as that of Example 1, except that the electrolyte is tetrabutylammonium bromide (TBABr).

[0062] In an open electrolytic cell (30 mL) under air atmosphere, o-phenylsulfonimide (0.5 mmol, 91.6 mg), tetrabutylammonium bromide (1 mmol, 322.4 mg), acetonitrile (10 mL), and p-methylanisole (2 mmol, 244.3 mg, 252.1 μL) were added respectively. A carbon sheet (10 mm × 10 mm × 1 mm) was used as the cathode and a platinum sheet (10 mm × 10 mm × 0.1 mm) was used as the anode. A current of 20 mA was applied, the reaction temperature was 80 ° C, and the reaction was carried out for 5 h. The product was monitored by TLC during the reaction, and it was found that no target product was generated.

[0063] Example 5

[0064] The implementation method of this experiment is the same as that of Example 1, except that the electrolyte is potassium iodide.

[0065] Under air atmosphere, o-phenylsulfonimide (0.5mmol, 91.6mg), potassium iodide (1mmol, 166.0mg), acetonitrile (10mL), and p-methylanisole (2mmol, 244.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction, and it was found that no target product was generated.

[0066] Example 6

[0067] The implementation method of this experiment is the same as that of Example 1, except that the electrolyte is sodium bromide. Under air atmosphere, o-benzenesulfonimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and p-methylanisole (2mmol, 244.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as a cathode and a platinum sheet (10mm×10mm×0.1mm) was used as an anode, a current of 20mA was applied, the reaction temperature was 80°C, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 76%.

[0068] The product yields obtained under the reaction conditions described in Examples 1 to 6 are shown in Table 1.

[0069] Table 1 Effect of different electrolyte types on product yield under the reaction conditions described in Examples 1 to 6

[0070]

[0071] Note: Table 1 a Product yields are obtained from actual separations; b The product yield was obtained by TLC spot plate observation.

[0072] Example 7

[0073] The implementation method of this experiment is the same as that of Example 6, except that the anode and cathode materials are both platinum sheet electrodes.

[0074] In an open electrolytic cell (30 mL) under air atmosphere, o-benzylsulfonimide (0.5 mmol, 91.6 mg), sodium bromide (1 mmol, 102.9 mg), acetonitrile (10 mL), and p-methylanisole (2 mmol, 244.3 mg) were added respectively. Platinum sheets (10 mm × 10 mm × 0.1 mm) were used as anode and cathode, and a current of 20 mA was applied. The reaction temperature was 80 ° C and the reaction was carried out for 5 h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate = 5 / 1) to obtain the target product: 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 38%.

[0075] Example 8

[0076] The implementation method of this experiment is the same as that of Example 6, except that the anode is a carbon sheet and the cathode is a platinum sheet.

[0077] Under air atmosphere, o-benzylsulfonimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and p-methylanisole (2mmol, 244.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A platinum sheet (10mm×10mm×0.1mm) was used as the cathode, a carbon sheet (10mm×10mm×1mm) was used as the anode, a current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, with an isolated yield of 12%.

[0078] The product yields obtained under the reaction conditions described in Examples 6 to 8 are shown in Table 2.

[0079] Table 2 Effect of different electrode materials on product yield under the reaction conditions described in Examples 6 to 8

[0080] Reaction conditions Example 7 Example 8 Example 6 Material (anode / cathode) Platinum sheet / platinum sheet Carbon rod / Platinum sheet Platinum sheet / carbon rod <![CDATA[Yield a (%)]]> 38.0 12.0 76.0

[0081] Note: Table 2 a Product yields were obtained from the actual isolation.

[0082] Example 9

[0083] The implementation method of this experiment is the same as that of Example 6, except that the current is 15mA. Under air atmosphere, o-benzenesulfonimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and p-methylanisole (2mmol, 244.3mg, 252.1μL) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as a cathode and a platinum sheet (10mm×10mm×0.1mm) was used as an anode, and a current of 15mA was applied. The reaction temperature was 80°C and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 14%.

[0084] Example 10

[0085] The implementation method of this experiment is the same as that of Example 6, except that the current is 25 mA.

[0086] Under air atmosphere, o-benzylsulfimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and p-methylanisole (2mmol, 244.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 25mA was applied, the reaction temperature was 80°C, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 73%. The product yields obtained under the reaction conditions described in Examples 9-10 are shown in Table 3.

[0087] Table 3 Effect of different currents on product yields under the reaction conditions described in Examples 9 to 10

[0088] Example 9 Example 10 Example 6 Current (mA) 15 25 20 <![CDATA[Yield a (%)]]> 14.0 73.0 76.0

[0089] Note: Table 3 a Product yields were obtained from the actual isolation.

[0090] Embodiment 11

[0091] The implementation method of this experiment is the same as that of Example 6, except that the reaction time is 3h. Under air atmosphere, o-benzenesulfonimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and p-methylanisole (2mmol, 244.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as a cathode and a platinum sheet (10mm×10mm×0.1mm) was used as an anode, a current of 20mA was applied, the reaction temperature was 80°C, and the reaction was carried out for 3h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 64%.

[0092] Example 12

[0093] The implementation method of this experiment is the same as that of Example 6, except that the reaction time is 10h. Under air atmosphere, o-benzenesulfonimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and p-methylanisole (2mmol, 244.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as a cathode and a platinum sheet (10mm×10mm×0.1mm) was used as an anode, a current of 20mA was applied, the reaction temperature was 80°C, and the reaction was carried out for 10h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 12%. As shown in Table 4.

[0094] Table 4 Effect of different reaction times on product yield under the reaction conditions of Examples 11 to 12

[0095] Embodiment 11 Example 12 Example 6 Time (h) 3 10 5 <![CDATA[Yield a (%)]]> 64.0 12.0 76.0

[0096] Note: Table 4 a Product yields were obtained from the actual isolation.

[0097] Embodiment 13

[0098] The implementation method of this experiment is the same as that of Example 6, except that the solvent is N,N-dimethylformamide (DMF). Under air atmosphere, o-phenylsulfonimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), DMF (10mL), and p-methylanisole (2mmol, 244.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80°C, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction, and it was found that no target product was generated.

[0099] Embodiment 14

[0100] The implementation method of this experiment is the same as that of Example 6, except that the solvent is 1,2-dichloroethane (DCE).

[0101] In an air atmosphere, o-phenylsulfonimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), DCE (10mL), and p-methylanisole (2mmol, 244.3mg, 252.1μL) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80°C, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction, and it was found that no target product was generated. The product yields obtained under the reaction conditions described in Examples 13 to 14 are shown in Table 5.

[0102] Table 5 Effect of different solvent types on product yield under the reaction conditions described in Examples 13-14

[0103] Embodiment 13 Embodiment 14 Example 6 Solvent (10 mL) DMF DCE ACN <![CDATA[Yield a (%)]]> <![CDATA[0 b ]]> <![CDATA[0 b ]]> 76.0

[0104] Note: Table 5 a Product yields are obtained from actual separations; b The product yield was obtained by TLC spot plate observation.

[0105] Embodiment 15

[0106] The implementation method of this experiment is the same as that of Example 6, except that the reaction temperature is room temperature.

[0107] In an open electrolytic cell (30 mL) under air atmosphere, o-benzylsulfonimide (0.5 mmol, 91.6 mg), sodium bromide (1 mmol, 102.9 mg), acetonitrile (10 mL), and p-methylanisole (2 mmol, 244.3 mg) were added respectively. A carbon sheet (10 mm × 10 mm × 1 mm) was used as the cathode and a platinum sheet (10 mm × 10 mm × 0.1 mm) was used as the anode. A current of 20 mA was applied. The reaction temperature was room temperature and the reaction lasted for 5 h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product. The target product was separated by column chromatography (petroleum ether / ethyl acetate = 5 / 1) to obtain the target product: 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 11%.

[0108] Example 16

[0109] The implementation method of this experiment is the same as that of Example 6, except that the reaction temperature is 40°C. In an air atmosphere, o-benzenesulfonimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and p-methylanisole (2mmol, 244.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as a cathode and a platinum sheet (10mm×10mm×0.1mm) was used as an anode, a current of 20mA was applied, the reaction temperature was 40°C, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 18%.

[0110] Embodiment 17

[0111] The implementation method of this experiment is the same as that of Example 6, except that the reaction temperature is 60°C.

[0112] In an open electrolytic cell (30 mL) under air atmosphere, o-benzylsulfonimide (0.5 mmol, 91.6 mg), sodium bromide (1 mmol, 102.9 mg), acetonitrile (10 mL), and p-methylanisole (2 mmol, 244.3 mg) were added respectively. A carbon sheet (10 mm × 10 mm × 1 mm) was used as the cathode and a platinum sheet (10 mm × 10 mm × 0.1 mm) was used as the anode. A current of 20 mA was applied, the reaction temperature was 60 ° C, and the reaction was carried out for 5 h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate = 5 / 1) to obtain the target product: 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 34%.

[0113] The product yields obtained under the reaction conditions described in Examples 15 to 17 are shown in Table 6.

[0114] Table 6 Effect of different reaction temperatures on product yields under the reaction conditions described in Examples 15 to 17

[0115] Embodiment 15 Example 16 Embodiment 17 Example 6 Reaction temperature (℃) Room temperature 40 60 80 <![CDATA[Yield a (%)]]> 11.0 18.0 34.0 76.0

[0116] Note: Table 6 a Product yields were obtained from the actual isolation.

[0117] Embodiment 18

[0118] The implementation method of this experiment is the same as that of Example 6, except that 1,8-diazabicycloundec-7-ene (DBU) (1 mmol) is added as an organic base. In an air atmosphere, o-phenylsulfonimide (0.5 mmol, 91.6 mg), sodium bromide (1 mmol, 102.9 mg), acetonitrile (10 mL), p-methylanisole (2 mmol, 244.3 mg), and DBU (1 mmol, 152.4 mg) are added to an open electrolytic cell (specification 30 mL) respectively. A carbon sheet (10 mm × 10 mm × 1 mm) is used as a cathode and a platinum sheet (10 mm × 10 mm × 0.1 mm) is used as an anode. A current of 20 mA is applied, the reaction temperature is 80 ° C, and the reaction is carried out for 5 hours. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate = 5 / 1) to obtain the target product: 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 18%.

[0119] Embodiment 19

[0120] The implementation method of this experiment is the same as that of Example 6, except that Na2CO3 (1 mmol) is added as an inorganic base. In an air atmosphere, o-phenylsulfonimide (0.5 mmol, 91.6 mg), sodium bromide (1 mmol, 102.9 mg), Na2CO3 (1 mmol, 104.0 mg), acetonitrile (10 mL), and p-methylanisole (2 mmol, 244.3 mg) are added to an open electrolytic cell (specification 30 mL) respectively. A carbon sheet (10 mm × 10 mm × 1 mm) is used as a cathode and a platinum sheet (10 mm × 10 mm × 0.1 mm) is used as an anode. A current of 20 mA is applied, the reaction temperature is 80 ° C, and the reaction is carried out for 5 hours. During the reaction, the product was monitored by TLC. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate = 5 / 1) to obtain the target product: 2-(4-methoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 26%. The product yields obtained under the reaction conditions described in Examples 18 to 19 are shown in Table 7

[0121] Table 7 Effect of different added bases on product yield under the reaction conditions described in Examples 18 to 19

[0122] Embodiment 18 Embodiment 19 Example 6 Base (1.0 mmol) DBU <![CDATA[Na2CO3]]> - <![CDATA[Yield a (%)]]> 18.0 26.0 76.0

[0123] Note: Table 7 a Product yields were obtained from the actual isolation.

[0124] Embodiment 20

[0125]

[0126] Under air atmosphere, o-benzenesulfonimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and 4-tert-butyltoluene (2mmol, 296.5mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(4-tert-butylbenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 49%. The specific NMR data are as follows: 1HNMR (400MHz, CDCl3): δ8.07–8.03(m,1H),7.93(dd,J=6.9,1.3Hz,1H),7.88–7.79( m,2H),7.45(d,J=8.4Hz,2H),7.41–7.34(d,J=8.4Hz,2H),4.88(s,2H),1.30(s,9H); 13 C NMR (101MHz, CDCl3): δ158.9,151.2,137.7,134.8,134.3,131.4,128.6,127.4,125.7,125.2,121.0,42.4,34.6,31.3.

[0127] Embodiment 21

[0128]

[0129] In an open electrolytic cell (30 mL) under air atmosphere, o-benzylsulfimide (0.5 mmol, 91.6 mg), sodium bromide (1 mmol, 102.9 mg), acetonitrile (10 mL), and p-chlorotoluene (2 mmol, 253.2 mg) were added respectively. A carbon sheet (10 mm × 10 mm × 1 mm) was used as the cathode and a platinum sheet (10 mm × 10 mm × 0.1 mm) was used as the anode. A current of 20 mA was applied, the reaction temperature was 80 ° C, and the reaction was carried out for 5 h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate = 5 / 1) to obtain the target product: 2-(4-chlorobenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 57%.

[0130] The specific NMR data are as follows:

[0131] 1 H NMR (400MHz, CDCl3): δ7.99(d,J=6.6Hz,1H),7.87(d,J=7.2Hz,1H),7.84–7.74(m,2H),7.41–7.35(m,2H),7.29–7.22(m,2H),4.80(s,2H). 13 C NMR (101MHz, CDCl3): δ158.9,137.7,135.0,134.5,134.3,133.0,130.2,128.9,127.2,125.3,121.1,42.0.

[0132] Embodiment 22

[0133]

[0134] Under air atmosphere, o-benzylsulfimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and p-bromotoluene (2mmol, 342.1mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(4-bromobenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 48%.

[0135] The specific NMR data are as follows:

[0136] 1 H NMR (400MHz, CDCl3): δ7.99 (dd, J=6.6, 1.0Hz, 1H), 7.87 (dd, J=7.0, 1.2Hz, 1H), 7.7 9(dtd,J=17.6,7.4,1.3Hz,2H),7.44–7.39(m,2H),7.35–7.30(m,2H),4.78(s,2H); 13 C NMR (101MHz, CDCl3): δ158.9,137.7,135.0,134.5,133.5,131.9,130.5,128.8,127.2,125.3,121.1,42.0.

[0137] Embodiment 23

[0138]

[0139] Under air atmosphere, o-benzylsulfimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and p-xylene (2mmol, 212.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(4-methylbenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a yellow solid, with an isolated yield of 74%.

[0140] The specific NMR data are as follows:

[0141] 1 H NMR (400MHz, CDCl3): δ8.05(d,J=7.0Hz,1H),7.92(d,J=6.7Hz,1H),7.83(dtd,J=17.0, 7.4,1.3Hz,2H),7.40(d,J=8.1Hz,2H),7.16(d,J=7.8Hz,2H),4.87(s,2H),2.33(s,3H); 13 C NMR (101MHz, CDCl3): δ158.9,138.1,137.8,134.8,134.3,131.5,129.4,128.8,127.4,125.2,121.0,42.5,21.2.

[0142] Embodiment 24

[0143]

[0144] Under air atmosphere, o-benzenesulfonimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and methyl 3-methylbenzoate (2mmol, 300.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: methyl 3-[(1,1-dioxo-3-oxobenzo[d]isothiazol-2(3H)-yl)methyl]benzoate, a white solid, with an isolated yield of 32%. The specific NMR data are as follows:

[0145] 1 H NMR (400MHz, CDCl3): δ8.18(s,1H),8.07(dd,J=7.0,1.5Hz,1H),8.00(d,J=7.8Hz,1H),7.94(d,J=7.2Hz,1H) ,7.86(dtd,J=17.2,7.4,1.3Hz,2H),7.71(d,J=7.7Hz,1H),7.45(t,J=7.7Hz,1H),4.96(s,2H),3.91(s,3H); 13C NMR (101MHz, CDCl3): δ166.7,158.9,137.7,135.0,134.9,134.5,133.1,130.7,129.8,129.6,128.9,127.2,125.4,121.1,52.3,42.3.

[0146] Embodiment 25

[0147]

[0148] Under air atmosphere, o-benzylsulfimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and 2-fluorotoluene (2mmol, 220.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(2-fluorobenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 29%.

[0149] The specific NMR data are as follows:

[0150] 1 H NMR (400MHz, CDCl3): δ8.11–8.07(m,1H),7.94(dd,J=6.9,1.4Hz,1H),7.86(dtd,J=16.3,7.4,1.3Hz,2H) ,7.48(td,J=7.6,1.5Hz,1H),7.31(tdd,J=7.3,5.3,1.7Hz,1H),7.17–7.05(m,2H),5.02(d,J=1.1Hz,2H); 13 C NMR(101MHz,CDCl3)13C NMR (101MHz, CDCl3) δ162.0, 159.5, 158.8, 137.8, 134.9, 134.4, 130.4 (d, J = 3.1Hz), 130.2 (d, J = 8.0Hz), 127.2, 125.4, 124.4 (d, J = 4.1Hz), 121.6 (d, J = 14.0Hz), 121.1, 115.6 (d, J = 21.1Hz), 36.0 (d, J = 21.1Hz); 19 F NMR (376MHz, CDCl3): δ-117.13.

[0151] Embodiment 26

[0152]

[0153] Under air atmosphere, o-benzylsulfimide (0.5mmol, 91.6mg), o-xylene (2mmol, 212.3mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and o-xylene (2mmol, 212.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm x 0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(2-methylbenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 60%. The specific NMR data are as follows:

[0154] 1 H NMR (400MHz, CDCl3): δ8.11–8.07(m,1H),7.93(dd,J=6.7,1.6Hz,1H),7.86(dtd,J=14.4, 7.4,1.4Hz,2H),7.42(dd,J=7.8,1.9Hz,1H),7.25–7.16(m,3H),4.96(s,2H),2.47(s,3H); 13 C NMR (101MHz, CDCl3): δ159.0,137.9,136.3,134.9,134.4,132.1,130.5,128.7,128.4,127.3,126.3,125.3,121.0,40.6,19.3.

[0155] Embodiment 27

[0156]

[0157] Under air atmosphere, o-benzylsulfimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and mesitylene (2mmol, 240.4mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(3,5-dimethylbenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 35%.

[0158] The specific NMR data are as follows:

[0159] 1 H NMR (400MHz, CDCl3): δ8.06(d,J=6.8Hz,1H),7.93(d,J=6.8Hz,1H),7.84(dtd ,J=16.3,7.4,1.2Hz,2H),7.11(s,2H),6.94(s,1H),4.84(s,2H),2.30(s,6H); 13 C NMR (101MHz, CDCl3): δ156.0,138.3,137.8,134.8,134.4,130.0,127.4,126.4,125.3,121.0,42.6,21.3.

[0160] Embodiment 28

[0161]

[0162] Under air atmosphere, o-benzylsulfimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and 2,3-dichlorotoluene (2mmol, 322.1mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(2,3-dichlorobenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 42%. The specific NMR data are as follows:

[0163] 1 H NMR (400MHz, CDCl3): δ8.12(d,J=6.7Hz,1H),7.99–7.85(m,3H),7.44(d,J=8.0Hz,1H),7.34(d,J=8.4Hz,1H),7.19(t,J=7.9Hz,1H),5.10(s,2H); 13 C NMR (101MHz, CDCl3): δ158.9,137.8,135.1,134.6,134.2,133.5,131.5,130.2,127.5,127.0,125.5,121.2,40.7.

[0164] Embodiment 29

[0165]

[0166] Under air atmosphere, o-benzylsulfimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and 2,6-dimethylanisole (2mmol, 272.4mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(2-methoxy-3-methylbenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 33%. The specific NMR data are as follows:

[0167] 1 H NMR (400MHz, CDCl3): δ8.08 (dd, J=6.9, 1.7Hz, 1H), 7.93 (dd, J=6.8, 1.4Hz, 1H), 7.89–7.79 (m, 2H) ,7.24(s,1H),7.14(d,J=7.1Hz,1H),6.99(t,J=7.6Hz,1H),5.03(s,2H),3.87(s,3H),2.33(s,3H); 13 C NMR (101MHz, CDCl3): δ159.0,156.6,138.0,134.8,134.3,131.6,131.2,127.4,127.4,127.0,125.3,124.2,121.0,60.6,37.6,16.1.

[0168] Embodiment 30

[0169]

[0170] Under air atmosphere, o-benzenesulfonimide (0.5mmol, 91.6mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and 2,6-dimethoxytoluene (2mmol, 304.2mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80℃, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: 2-(2,6-dimethoxybenzyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide, a white solid, with an isolated yield of 60%. The specific NMR data are as follows:

[0171] 1 H NMR (400MHz, CDCl3): δ8.07–8.03(m,1H),7.85–7.73(m,2H),7.30–7.23(m,2H),6.56(d,J=8.4Hz,2H),5.13(s,2H),3.87(s,6H); 13 C NMR (101MHz, CDCl3): δ159.3,158.5,138.2,134.4,133.9,130.2,127.5,125.0,120.5,110.1,103.6,55.9,32.1.

[0172] Embodiment 31

[0173]

[0174] In an open electrolytic cell (30 mL) under air atmosphere, N-acetyl p-toluenesulfonamide (0.5 mmol, 106.6 mg), sodium bromide (1 mmol, 102.9 mg), acetonitrile (10 mL), and p-methyl anisole (2 mmol, 244.1 mg) were added respectively. A carbon sheet (10 mm × 10 mm × 1 mm) was used as the cathode and a platinum sheet (10 mm × 10 mm × 0.1 mm) was used as the anode. A current of 20 mA was applied, the reaction temperature was 80 ° C, and the reaction was carried out for 5 h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate = 5 / 1) to obtain the target product: N-(4-methoxybenzyl)-N-toluenesulfonyl acetamide, a white solid, with an isolated yield of 42%.

[0175] The specific NMR data are as follows:

[0176] 1 H NMR (400MHz, CDCl3): δ7.59(d,J=8.3Hz,2H),7.34(d,J=8.6Hz,2H),7.26(d,J=8.0 Hz,2H),6.86(d,J=8.6Hz,2H),5.02(s,2H),3.81(s,3H),2.42(s,3H),2.27(s,3H); 13 C NMR (101MHz, CDCl3): δ170.4,159.2,144.8,136.7,129.8,128.9,127.7,113.9,55.3,49.0,29.71,25.0,21.6.

[0177] Embodiment 32

[0178]

[0179] In an open electrolytic cell (30 mL) under air atmosphere, N-(tert-butyloxycarbonyl)-p-toluenesulfonamide (0.5 mmol, 135.7 mg), sodium bromide (1 mmol, 102.9 mg), acetonitrile (10 mL), and p-methylanisole (2 mmol, 244.3 mg) were added respectively. A carbon sheet (10 mm × 10 mm × 1 mm) was used as the cathode and a platinum sheet (10 mm × 10 mm × 0.1 mm) was used as the anode. A current of 20 mA was applied, the reaction temperature was 80 ° C, and the reaction was carried out for 5 h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product. The target product was separated by column chromatography (petroleum ether / ethyl acetate = 5 / 1) to obtain the target product: tert-butyl-N-(4-methoxybenzyl)-N-p-toluenesulfonylcarbamate, a green liquid, with an isolated yield of 61%. The specific NMR data are as follows:

[0180] 1 H NMR (400MHz, CDCl3): δ7.54(d,J=8.3Hz,2H),7.38(d,J=8.7Hz,2H),7.20(d,J=8.1 Hz,2H),6.87(d,J=8.7Hz,2H),4.98(s,2H),3.82(s,3H),2.40(s,3H),1.31(s,9H); 13 C NMR (101MHz, CDCl3): δ159.2,151.2,144.0,137.3,129.9,129.6,129.1,127.9,113.8,84.4,55.3,49.1,27.9,21.6.

[0181] Embodiment 33

[0182]

[0183] In an open electrolytic cell (30 mL) under air atmosphere, N-(4-methylbenzenesulfonyl)benzamide (0.5 mmol, 137.7 mg), sodium bromide (1 mmol, 102.9 mg), acetonitrile (10 mL), and p-methylanisole (2 mmol, 244.3 mg) were added respectively. A carbon sheet (10 mm × 10 mm × 1 mm) was used as the cathode and a platinum sheet (10 mm × 10 mm × 0.1 mm) was used as the anode. A current of 20 mA was applied, the reaction temperature was 80 ° C, and the reaction was carried out for 5 h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product. The target product was separated by column chromatography (petroleum ether / ethyl acetate = 5 / 1) to obtain the target product: N-(4-methoxybenzyl)-N-p-toluenesulfonylbenzamide, a yellow solid, with an isolated yield of 40%. The specific NMR data are as follows:

[0184] 1 H NMR (400MHz, CDCl3): δ7.58(d,J=8.3Hz,2H),7.44(d,J=8.3Hz,3H),7.38–7.30(m,2H),7.22(d,J =8.1Hz,2H),7.13(d,J=8.7Hz,2H),6.78(d,J=8.7Hz,2H),4.92(s,2H),3.78(s,3H),2.41(s,3H); 13 C NMR (101MHz, CDCl3): δ171.6,159.2,144.6,136.1,135.1,131.7,129.6,129.4,128.5,128.3,128.3,128.2,113.9,55.3,50.7,21.7.

[0185] Embodiment 34

[0186]

[0187] Under air atmosphere, bisbenzenesulfonimide (0.5mmol, 148.7mg), sodium bromide (1mmol, 102.9mg), acetonitrile (10mL), and p-methylanisole (2mmol, 244.3mg) were added to an open electrolytic cell (specification 30mL) respectively. A carbon sheet (10mm×10mm×1mm) was used as the cathode and a platinum sheet (10mm×10mm×0.1mm) was used as the anode. A current of 20mA was applied, the reaction temperature was 80°C, and the reaction was carried out for 5h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate=5 / 1) to obtain the target product: N-(4-methoxybenzyl)-N-benzenesulfonylbenzenesulfonamide, a white solid, with an isolation yield of 81%. The specific NMR data are as follows: 1 H NMR (400MHz, CDCl3): δ7.79 (d, J = 7.1Hz, 4H), 7.57 (t, J = 7.4Hz, 2H), 7.43 (t, J = 7. 9Hz, 4H), 7.32 (d, J = 8.6Hz, 2H), 6.77 (d, J = 8.7Hz, 2H), 4.88 (s, 2H), 3.80 (s, 3H); 13 C NMR (101MHz, CDCl3): δ159.6,140.2,133.6,130.8,128.8,128.1,126.6,113.8,55.4,52.1.

[0188] Embodiment 35

[0189]

[0190] In an open electrolytic cell (30 mL) under air atmosphere, N-(phenylsulfonyl)thiophene-2-sulfonamide (0.5 mmol, 151.7 mg), sodium bromide (1 mmol, 102.9 mg), acetonitrile (10 mL), and p-methylanisole (2 mmol, 244.3 mg) were added respectively. A carbon sheet (10 mm × 10 mm × 1 mm) was used as the cathode and a platinum sheet (10 mm × 10 mm × 0.1 mm) was used as the anode. A current of 20 mA was applied, the reaction temperature was 80 ° C, and the reaction was carried out for 5 h. The product was monitored by TLC during the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by column chromatography (petroleum ether / ethyl acetate = 5 / 1) to obtain the target product: N-(4-methoxybenzyl)-N-phenylsulfonylthiophene-2-sulfonamide, a yellow solid, with an isolated yield of 53%. The specific NMR data are as follows:

[0191] 1 H NMR (400MHz, CDCl3): δ7.78–7.72(m,2H),7.62(d,J=4.4Hz,2H),7.57(t,J=7.5Hz,1H),7.43(t,J=7. 9Hz,2H),7.35(d,J=8.7Hz,2H),7.06–7.01(m,1H),6.80(d,J=8.7Hz,2H),4.90(s,2H),3.81(s,3H); 13 C NMR (101MHz, CDCl3): δ159.6,140.2,140.1,134.8,133.9,133.6,130.8,128.8,128.1,127.2,126.5,113.8,55.4,52.2.

[0192] Embodiment 36

[0193]

[0194] In a clean, dry, undivided glass electrolytic cell, o-benzylsulfimide (0.5 mmol, 91.6 mg), electrolyte sodium bromide (1.0 mmol, 102.9 mg), solvent acetonitrile (10 mL), diphenylmethane (2.0 mmol, 336.0 μL) were added in sequence. Then, a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20 mA was passed at 80°C. The reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation. The product 2-dibenzylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate = 5 / 1). The product was 151.8 mg of white powder with a yield of 87.0%. The specific NMR data are as follows: 1H NMR (400MHz, CDCl3): δ8.00(dd,J=6.9,0.8Hz,1H),7.93–7.89(m,1H),7.88–7.79(m,2H),7.47–7.41(m,4H),7.40–7.30(m,6H),6.51(s,1H); 13 C NMR (101 MHz, CDCl3): δ 158.4, 137.7, 136.5, 134.8, 134.3, 129.0, 128.5, 128.3, 127.1, 125.3, 120.9, 60.4. The data were consistent with those reported in the literature (R I. Robinson, R Fryatt, C Wilson, S Woodward Sulfonamide Ligands Attained Through Opening of Saccharin Derivatives. Eur. J. Org. Chem. 2006, 19, 4483–4489).

[0195] Unless otherwise specified, the electrode materials described in Examples 36 to 70 have the following specifications: carbon sheet 10 mm × 10 mm × 1 mm, platinum sheet 10 mm × 10 mm × 0.1 mm.

[0196] Embodiment 37

[0197] The experimental method of this embodiment is the same as that of Example 36, except that the electrolyte is tetrabutylammonium acetate (TBAOAc).

[0198] Into a clean, dry, undivided glass electrolytic cell were added o-benzylsulfimide (0.5 mmol, 91.6 mg), electrolyte tetrabutylammonium acetate (1.0 mmol, 301.5 mg), solvent acetonitrile (10 mL), and diphenylmethane (2.0 mmol, 336.0 μL) in sequence. Subsequently, a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20 mA was passed at 80° C. The reaction was stirred for 5 hours. The reaction solution was tested by TLC spot plate and no formation of the product 2-diphenylmethylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was detected.

[0199] Embodiment 38

[0200] The experimental method of this embodiment is the same as that of Example 36, except that the electrolyte is tetrabutylammonium bromide (TBABr).

[0201] Into a clean, dry, undivided glass electrolytic cell were added o-benzylsulfimide (0.5 mmol, 91.6 mg), electrolyte tetrabutylammonium bromide (1.0 mmol, 322.4 mg), solvent acetonitrile (10 mL), and diphenylmethane (2.0 mmol, 336.0 μL) in sequence. Subsequently, a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20 mA was passed at 80° C. The reaction was stirred for 5 hours. The reaction solution was tested by TLC spot plate and no formation of the product 2-dibenzylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was detected.

[0202] Embodiment 39

[0203] The experimental method of this embodiment is the same as that of Example 36, except that the electrolyte is tetrabutylammonium hydroxide (TBAOH).

[0204] In a clean, dry, undivided glass electrolytic cell, o-benzylsulfimide (0.5 mmol, 91.6 mg), electrolyte tetrabutylammonium hydroxide (1.0 mmol, 260.3 μL), solvent acetonitrile (10 mL), and diphenylmethane (2.0 mmol, 336.0 μL) were added in sequence. Then, a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20 mA was passed at 80° C. The reaction was stirred for 5 hours. The reaction solution was detected by TLC spot plate to only produce a trace amount of the product 2-diphenylmethylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide.

[0205] Embodiment 40

[0206] The experimental method of this embodiment is the same as that of Example 36, except that the electrolyte is potassium bromide.

[0207] In a clean, dry, undivided glass electrolytic cell, o-benzylsulfimide (0.5 mmol, 91.6 mg), electrolyte potassium bromide (1.0 mmol, 119.0 mg), solvent acetonitrile (10 mL), and diphenylmethane (2.0 mmol, 336.0 μL) were added in sequence. Then, a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20 mA was passed at 80° C. The reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation. The product 2-dibenzylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography (petroleum ether / ethyl acetate=5 / 1) as a white powder (26.4 mg). The yield was 15.1%.

[0208] Embodiment 41

[0209] The experimental method of this embodiment is the same as that of Example 36, except that the electrolyte is ammonium bromide.

[0210] In a clean, dry, undivided glass electrolytic cell, o-benzylsulfimide (0.5 mmol, 91.6 mg), electrolyte ammonium bromide (1.0 mmol, 97.9 mg), solvent acetonitrile (10 mL), diphenylmethane (2.0 mmol, 336.0 μL) were added in sequence, and then a constant current of 20 mA was passed through the electrolytic cell at 80° C. with a platinum sheet as anode and a carbon rod as cathode, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-dibenzylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which was a white powder of 60.7 mg and a yield of 34.5%. The yields of the products obtained under the reaction conditions described in Examples 36 to 41 are shown in Table 8.

[0211] Table 8 Effect of different electrolyte types on product yield under the reaction conditions described in Examples 36 to 41

[0212]

[0213] Note: Table 8 a Product yields are obtained from actual separations; b The product yield was obtained by TLC spot plate observation.

[0214] Embodiment 42

[0215] The experimental method of this example is the same as that of Example 36, except that the solvent is DCE. In a clean, dry, undivided glass electrolytic cell, o-phenylmethanesulfonimide (0.5 mmol, 91.6 mg), electrolyte sodium bromide (1.0 mmol, 102.9 mg), solvent DCE 10 mL, and diphenylmethane (2.0 mmol, 336.0 μL) were added in sequence, and then a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20 mA was passed under 80° C. and the reaction was stirred for 5 hours. The reaction solution was tested by TLC spot plate and no product 2-dibenzylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was detected.

[0216] Embodiment 43

[0217] The experimental method of this example is the same as that of Example 36, except that the solvent is DMF. In a clean, dry, undivided glass electrolytic cell, o-phenylmethanesulfimide (0.5 mmol, 91.6 mg), electrolyte sodium bromide (1.0 mmol, 102.9 mg), solvent DMF (10 mL), and diphenylmethane (2.0 mmol, 336.0 μL) were added in sequence, and then a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20 mA was passed at 80° C. and the reaction was stirred for 5 hours. The reaction solution was tested by TLC spot plate and no product 2-diphenylmethylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was detected.

[0218] The product yields obtained under the reaction conditions described in Examples 42 to 43 are shown in Table 9.

[0219] Table 9 Effect of different solvent types on product yield under the reaction conditions described in Examples 42-43

[0220] Embodiment 42 Embodiment 43 Embodiment 36 Solvent (10 mL) DCE DMF ACN <![CDATA[Yield a (%)]]> <![CDATA[0 b ]]> <![CDATA[0 b ]]> 87.0

[0221] Note: Table 9 a Product yields are obtained from actual separations; b The product yield was obtained by TLC spot plate observation.

[0222] Embodiment 44

[0223] The experimental method of this example is the same as that of Example 36, except that the reaction temperature is room temperature.

[0224] In a clean, dry, undivided glass electrolytic cell, o-benzylsulfimide (0.5 mmol, 91.6 mg), electrolyte sodium bromide (1.0 mmol, 102.9 mg), solvent acetonitrile (10 mL), and diphenylmethane (2.0 mmol, 336.0 μL) were added in sequence. Then, a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20 mA was passed at room temperature. The reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation. The product 2-dibenzylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography (petroleum ether / ethyl acetate=5 / 1) as a white powder, 16.1 mg, with a yield of 9.2%.

[0225] Embodiment 45

[0226] The experimental method of this example is the same as that of Example 36, except that the reaction temperature is 40°C.

[0227] In a clean, dry, undivided glass electrolytic cell, o-benzylsulfimide (0.5 mmol, 91.6 mg), electrolyte sodium bromide (1.0 mmol, 102.9 mg), solvent acetonitrile (10 mL), and diphenylmethane (2.0 mmol, 336.0 μL) were added in sequence. Then, a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20 mA was passed at 40° C. The reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation. The product 2-dibenzylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1). The product was 31.4 mg of white powder with a yield of 18.0%.

[0228] Embodiment 46

[0229] The experimental method of this example is the same as that of Example 36, except that the reaction temperature is 60°C.

[0230] In a clean, dry, undivided glass electrolytic cell, o-benzylsulfimide (0.5 mmol, 91.6 mg), electrolyte sodium bromide (1.0 mmol, 102.9 mg), solvent acetonitrile (10 mL), and diphenylmethane (2.0 mmol, 336.0 μL) were added in sequence. Then, a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20 mA was passed at 60° C. The reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation. The product 2-dibenzylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1). The product was 59.3 mg of white powder with a yield of 34.0%.

[0231] The product yields obtained under the reaction conditions described in Examples 44 to 46 are shown in Table 10.

[0232] Table 10 Effect of different reaction temperatures on product yields under the reaction conditions described in Examples 44 to 46

[0233] Embodiment 44 Embodiment 45 Embodiment 46 Embodiment 36 Reaction temperature (℃) Room temperature 40 60 80 <![CDATA[Yield a (%)]]> 9.2 18.0 34.0 87.0

[0234] Note: Table 10 a Product yields were obtained from the actual isolation.

[0235] Embodiment 47

[0236] The experimental method of this embodiment is the same as that of Embodiment 36, except that the constant current is 15 mA.

[0237] In a clean, dry, undivided glass electrolytic cell, o-benzylsulfimide (0.5 mmol, 91.6 mg), electrolyte sodium bromide (1.0 mmol, 102.9 mg), solvent acetonitrile (10 mL), and diphenylmethane (2.0 mmol, 336.0 μL) were added in sequence. Then, a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 15 mA was passed at 80° C. The reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation. The product 2-dibenzylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography (petroleum ether / ethyl acetate=5 / 1) as a white powder (24.4 mg). The yield was 14.0%.

[0238] Embodiment 48

[0239] The experimental method of this embodiment is the same as that of Embodiment 36, except that the constant current is 25 mA.

[0240] In a clean, dry, undivided glass electrolytic cell, o-benzylsulfimide (0.5 mmol, 91.6 mg), electrolyte sodium bromide (1.0 mmol, 102.9 mg), solvent acetonitrile (10 mL), and diphenylmethane (2.0 mmol, 336.0 μL) were added in sequence. Then, a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 25 mA was passed at 80° C. The reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation. The product 2-dibenzylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1). The product was 127.4 mg of white powder with a yield of 73.0%.

[0241] The product yields obtained under the reaction conditions described in Examples 47 to 48 are shown in Table 11.

[0242] Table 11 Effect of different currents on product yields under the reaction conditions described in Examples 47-48

[0243] Embodiment 47 Embodiment 48 Embodiment 36 Current (mA) 15 25 20 <![CDATA[Yield a (%)]]> 14.0 73.0 87.0

[0244] Note: Table 11 a Product yields were obtained from the actual isolation.

[0245] Embodiment 49

[0246] The experimental method of this embodiment is the same as that of embodiment 36, except that the cathode and the anode are both platinum electrodes. In a clean, dry, undivided glass electrolytic cell, o-phenylmethanesulfimide (0.5 mmol, 91.6 mg), electrolyte sodium bromide (1.0 mmol, 102.9 mg), solvent acetonitrile (10 mL), diphenylmethane (2.0 mmol, 336.0 μL) were added in sequence, and then a constant current of 20 mA was passed through the electrolytic cell at 80° C. with the platinum sheet as the anode and the platinum sheet as the cathode, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-dibenzhydrylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which was a white powder of 66.3 mg with a yield of 38.0%.

[0247] Embodiment 50

[0248] The experimental method of this embodiment is the same as that of embodiment 36, except that the carbon rod is used as the anode and the platinum sheet is used as the cathode. In a clean and dry undivided electrolytic cell, o-phenylmethanesulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), diphenylmethane (2.0mmol, 336.0μL) are added in sequence, and then a constant current of 20mA is passed through the electrolytic cell at 80°C with the carbon rod as the anode and the platinum sheet as the cathode. The stirring reaction is started for 5 hours. After the reaction is completed, the solvent is removed by rotary evaporation, and the product 2-dibenzhydrylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide is obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which is a white powder of 20.9mg and a yield of 12.0%. The yield of the product obtained under the reaction conditions described in embodiments 49 to 50 is shown in Table 12.

[0249] Table 12 Effect of different electrode materials on product yield under the reaction conditions described in Examples 49 to 50

[0250] Embodiment 49 Embodiment 50 Embodiment 36 Material (anode / cathode) Platinum sheet / Platinum sheet Carbon rod / platinum sheet Platinum sheet / carbon rod <![CDATA[Yield a (%)]]> 38.0 12.0 87.0

[0251] Note: Table 12 a Product yields were obtained from the actual isolation.

[0252] Embodiment 51

[0253]

[0254] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 4-fluorodiphenylmethane. In a clean and dry undivided glass electrolytic cell, o-phenylmethanesulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-fluorodiphenylmethane (2.0mmol, 372.2mg) were added in sequence, and then a constant current of 20mA was passed through the electrolytic cell at 80°C with a platinum sheet as anode and a carbon rod as cathode, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-[(4-fluorophenyl)(phenyl)methyl]benzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which was a white powder with a content of 151.7mg and a yield of 82.6%.

[0255] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ8.00(d,J=7.0Hz,1H),7.92(d,J=7.1Hz,1H),7.89–7.79 (m,2H),7.48–7.41(m,4H),7.41–7.33(m,3H),7.10–7.01(m,2H),6.48(s,1H); 13 C NMR (101MHz, CDCl3): δ163.8,161.4,158.4,137.7,136.4,134.9,134.4,132.4 ,131.1,131.1,128.7,128.6,128.4,127.0,125.3,120.9,115.5,115.3,59.7; 19 FNMR (376MHz,CDCl3):δ-113.6.

[0256] Embodiment 52

[0257]

[0258] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 4-chlorodiphenylmethane. In a clean and dry undivided glass electrolytic cell, o-phenylmethanesulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-chlorodiphenylmethane (2.0mmol, 404.1mg) were added in sequence, and then a constant current of 20mA was passed through the electrolytic cell at 80°C with a platinum sheet as anode and a carbon rod as cathode, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-[(4-chlorophenyl)(phenyl)methyl]benzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which was a white powder, 141.1mg, and a yield of 73.5%.

[0259] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ8.00 (d, J = 7.5Hz, 1H), 7.94–7.79 (m, 3H), 7.46–7.30 (m, 9H), 6.46 (s, 1H); 13 C NMR (101MHz, CDCl3): δ158.4,137.6,136.0,135.2,134.9,134.4,134.3,130.5,128.9,128.7,128.6,128.5,127.0,125.3,121.0,59.7.

[0260] Embodiment 53

[0261]

[0262] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 4-bromodiphenylmethane. In a clean and dry undivided glass electrolytic cell, o-phenylmethanesulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-bromodiphenylmethane (2.0mmol, 492.0mg) were added in sequence, and then a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20mA was passed under the condition of 80°C, and the stirring reaction was started for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-[(4-bromophenyl)(phenyl)methyl]benzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which was a white powder, 160.6mg, and a yield of 75.0%.

[0263] The specific NMR data are: 1H NMR (400MHz, CDCl3): δ8.00(d,J=7.4Hz,1H),7.93–7.80(m,3H),7.49(d,J=8.5Hz, 2H),7.43–7.42(d,J=6.2Hz,2H),7.37–7.32(dd,J=12.1,7.7Hz,5H),6.44(s,1H); 13 C NMR (101MHz, CDCl3): δ158.4,137.6,135.9,135.8,134.9,134.4,131.7,130.8,128.9,128.6,128.5,127.0,125.3,122.5,121.9,59.2.

[0264] Embodiment 54

[0265]

[0266] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 4-methoxydiphenylmethane. In a clean and dry undivided glass electrolytic cell, o-phenylmethanesulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-methoxydiphenylmethane (2.0mmol, 396.2mg) were added in sequence, and then a constant current of 20mA was passed through the electrolytic cell at 80°C with a platinum sheet as anode and a carbon rod as cathode, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-[(4-methoxyphenyl)(phenyl)methyl]benzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which was a yellow oily substance with a yield of 145.1mg and a yield of 76.5%.

[0267] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ7.99(d,J=6.9Hz,1H),7.90(d,J=7.2Hz,1H),7.83(dt,J=21.2,7.4Hz ,2H),7.48–7.40(m,3H),7.40–7.31(m,4H),6.89(d,J=8.8Hz,2H),6.47(s,1H),3.80(s,3H); 13 C NMR (101MHz, CDCl3): δ159.5,158.4,137.8,137.0,134.7,134.3,130.7,128.5,128.5,128.4,128.1,127.2,125.2,120.9,113.8,60.1,55.3.

[0268] Embodiment 55

[0269]

[0270] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 4-phenyldiphenylmethane. In a clean and dry undivided glass electrolytic cell, o-phenylmethanesulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-phenyldiphenylmethane (2.0mmol, 488.2mg) were added in sequence, and then a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20mA was passed under the condition of 80°C, and the stirring reaction was started for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-[(1,1'-biphenyl)(4-phenyl)methyl]benzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), yellow powder, 180.3mg, yield 84.7%.

[0271] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ8.02(d,J=7.1Hz,1H),7.93(d,J=7.5Hz,1H),7.84(dt,J=21.5, 7.5Hz,2H),7.59(d,J=8.5Hz,4H),7.56–7.47(m,4H),7.46–7.31(m,6H),6.54(s,1H); 13 C NMR (101MHz, CDCl3): δ158.5,141.1,140.6,137.7,136.5,135.6,134.8,13 4.3,129.4,129.1,128.8,128.5,128.3,127.5,127.2,125.3,120.9,60.1.

[0272] Embodiment 56

[0273]

[0274] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 4-tert-butyldiphenylmethane. In a clean and dry undivided glass electrolytic cell, o-phenylmethanesulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-tert-butyldiphenylmethane (2.0mmol, 448.2mg) were added in sequence, and then a constant current of 20mA was passed through the electrolytic cell at 80°C with a platinum sheet as anode and a carbon rod as cathode, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-[(4-tert-butylphenyl)(phenyl)methyl]benzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), yellow powder, 130.3mg, yield 64.6%.

[0275] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ7.86(d,J=7.3Hz,1H),7.78(d,J=7.5Hz,1H),7.67(dt,J=20 .9,7.1Hz,2H),7.37(d,J=7.0Hz,2H),7.31–7.20(m,7H),6.38(s,1H),1.21(s,9H); 13 C NMR (101MHz, CDCl3): δ158.4,151.1,137.7,136.8,134.8,134.3,133.5,1 29.0,128.8,128.5,128.2,127.2,125.4,125.3,120.9,60.1,34.6,31.4.

[0276] Embodiment 57

[0277]

[0278] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 1-benzyl-3-methylbenzene. In a clean and dry undivided electrolytic cell, o-benzylsulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 1-benzyl-3-methylbenzene (2.0mmol, 364.2mg) were added in sequence, and then a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20mA was passed under the condition of 80°C, and the stirring reaction was started for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-[(3-methylphenyl)(phenyl)methyl]benzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which was a white powder, 130.8mg, and a yield of 72.0%.

[0279] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ7.99(dd,J=7.3,1.3Hz,1H),7.91(d,J=7.0Hz,1H),7.82(dtd,J=20.9,7.4,1.3Hz,2H),7 .45(dd,J=7.4,1.6Hz,2H),7.39–7.32(m,3H),7.26–7.25(m,3H),7.17–7.11(m,1H),6.47(s,1H),2.33(s,3H); 13 C NMR (101MHz, CDCl3): δ158.5,138.2,137.7,136.7,136.6,134.8,134.3,129. 6,129.1,129.1,128.5,128.4,128.3,127.1,126.1,125.3,120.9,60.5,21.6.

[0280] Embodiment 58

[0281]

[0282] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 4,4'-dimethyldiphenylmethane. Electrochemical autoclave anodic oxidation reaction: o-phenylmethanesulfonimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4,4'-dimethyldiphenylmethane (2.0mmol, 392.2mg) are added in a clean and dry undivided glass electrolytic cell in sequence, and then a platinum sheet is used as an anode and a carbon rod is used as a cathode in the electrolytic cell, a constant current of 20mA is passed at 80°C, and the reaction is stirred for 5 hours. After the reaction is completed, the solvent is removed by rotary evaporation, and the product 2-(di-p-tolylmethyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide is obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), white powder, 100.6mg, yield 53.3%.

[0283] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ7.99(d,J=7.1Hz,1H),7.90(d,J=7.9Hz,1H),7.81(dtd,J=20.9, 7.4,1.2Hz,2H),7.36(d,J=8.1Hz,4H),7.17(d,J=8.0Hz,4H),6.46(s,1H),2.35(s,6H); 13C NMR (101MHz, CDCl3): δ169.4,158.5,150.4,137.7,136.2,134.7,134.3,129.0,127.3,125.1,121.6,120.8,52.5,21.1,17.7.

[0284] Embodiment 59

[0285]

[0286] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 4-fluoroethylbenzene. In a clean and dry undivided glass electrolytic cell, o-phenylmethanesulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-fluoroethylbenzene (2.0mmol, 248.2mg) were added in sequence, and then a constant current of 20mA was passed through the electrolytic cell at 80°C with a platinum sheet as anode and a carbon rod as cathode, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-[1-(4-fluorophenyl)ethyl]benzisothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which was a white powder, 30.5mg, and a yield of 20.0%.

[0287] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ7.97(d,J=6.9Hz,1H),7.89(d,J=6.9Hz,1H),7.81(dtd,J=20.5,7.4,1.3Hz,2H) ,7.58(ddt,J=8.2,5.0,3.0Hz,2H),7.04(t,J=8.7Hz,2H),5.43(q,J=7.3Hz,1H),2.01(d,J=7.3Hz,3H); 13 C NMR (101MHz, CDCl3): δ163.7,161.2,148.1,137.7,134.7,134.3,129.6,127.3,125.1,120.8,115.4,52.4,17.8; 19 F NMR (376 MHz, CDCl3): δ-113.9.

[0288] Embodiment 60

[0289]

[0290] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 4-bromoethylbenzene. In a clean and dry undivided glass electrolytic cell, o-phenylmethanesulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-bromoethylbenzene (2.0mmol, 368.0mg) were added in sequence, and then a constant current of 20mA was passed through the electrolytic cell at 80°C with a platinum sheet as anode and a carbon rod as cathode, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-[1-(4-bromophenyl)ethyl]benzisothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), white powder, 49.9mg, yield 27.3%.

[0291] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ7.87(d,J=8.3Hz,1H),7.80–7.73(m,2H),7.72–7.66(m,1H),7.5 4(d,J=8.5Hz,2H),7.36(d,J=8.5Hz,2H),6.25(q,J=6.5Hz,1H),1.80(d,J=6.6Hz,3H); 13 C NMR (101MHz, CDCl3): δ168.3,143.5,138.1,134.2,133.4,132.0,128.3,127.2,123.3,123.1,121.9,80.1,21.5.

[0292] Embodiment 61

[0293]

[0294] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 4-ethylanisole. In a clean and dry undivided glass electrolytic cell, o-phenylsulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-ethylanisole (2.0mmol, 272.2mg) were added in sequence, and then a constant current of 20mA was passed through the electrolytic cell at 80°C with a platinum sheet as anode and a carbon rod as cathode, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-(1-(4-methoxyphenyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide was obtained as a white powder, 137.4mg, and the yield was 86.5%.

[0295] The specific NMR data are: 1H NMR (400MHz, CDCl3): δ7.96 (dd, J=6.7, 0.9Hz, 1H), 7.88 (dd, J=6.9, 0.9Hz, 1H), 7.82 (td, J=7.5, 1.3Hz, 1H), 7.77 (td ,J=7.4,1.4Hz,1H),7.57–7.46(m,2H),6.91–6.85(m,2H),5.42(q,J=7.3Hz,1H),3.79(s,3H),2.00(d,J=7.3Hz,3H); 13 C NMR (101MHz, CDCl3): δ159.4,158.5,137.8,134.6,134.2,130.6,129.2,127.4,125.0,120.6,113.8,55.3,52.7,17.8.

[0296] Embodiment 62

[0297]

[0298] The experimental method of this embodiment is different from that of embodiment 36 in that the substrate is 4-ethylphenethyl ether. In a clean and dry undivided glass electrolytic cell, o-phenylmethanesulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-ethylphenethyl ether (2.0mmol, 300.2μL) were added in sequence, and then a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20mA was passed at 80°C, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-(1-(4-ethoxyphenyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), yellow powder, 121.6mg, yield 73.4%.

[0299] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ7.96(dd,J=6.7,0.9Hz,1H),7.89–7.86(m,1H),7.84–7.75(m,2H),7.52–7.50(m,2H),6.88– 6.86(m,2H),5.34(q,J=7.3Hz,1H),3.94(qd,J=7.0,3.0Hz,2H),1.93(d,J=7.3Hz,2H),1.32(t,J=7.0,2.1Hz,3H); 13CNMR (101MHz, CDCl3): δ158.8,158.5,137.8,134.6,134.2,130.4,129.1,127.4,125.0,120.7,114.3,63.4,52.7,17.8,14.8.

[0300] Embodiment 63

[0301]

[0302] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 4-ethylbiphenyl. In a clean and dry undivided glass electrolytic cell, o-phenylmethanesulfonimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-ethylbiphenyl (2.0mmol, 364.5mg) were added in sequence, and then a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell. A constant current of 20mA was passed at 80°C, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-[1-(1,1'-biphenyl)-4-ethyl]benzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which was a white powder, 116.8mg, and a yield of 64.3%.

[0303] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ7.91(d,J=8.0Hz,1H),7.83(d,J=7.7Hz,1H),7.74(dtd,J=21.2,7.5,1.2Hz,2H),7.62–7.57( m,2H),7.54–7.46(m,4H),7.35(t,J=7.5Hz,2H),7.26(t,J=6.1Hz,1H),5.42(q,J=7.2Hz,1H),1.99(d,J=7.3Hz,3H); 13 C NMR (101MHz, CDCl3): δ158.6,141.1,140.6,137.8,137.7,134.7,134.3,128.8,128.1,127.4,127.2,127.2,125.1,120.8,52.8,17.7.

[0304] Embodiment 64

[0305]

[0306] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 4-methylethylbenzene. In a clean and dry undivided glass electrolytic cell, o-phenylmethanesulfonimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-methylethylbenzene (2.0mmol, 240.2mg) were added in sequence, and then a constant current of 20mA was passed through the electrolytic cell at 80°C with a platinum sheet as anode and a carbon rod as cathode, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-(1-(p-tolyl)ethyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which was a white powder, 46.1mg, and a yield of 30.6%.

[0307] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ7.96(d,J=7.1Hz,1H),7.88(d,J=7.0Hz,1H),7.80(dtd,J=20.6,7.4,1.3Hz,2H), 7.48(d,J=8.1Hz,2H),7.17(d,J=7.9Hz,2H),5.43(q,J=7.2Hz,1H),2.33(s,3H),2.01(d,J=7.3Hz,3H); 13 C NMR (101MHz, CDCl3): δ158.5,138.0,137.8,135.6,134.6,134.2,129.2,127.6,127.4,125.0,120.7,52.9,21.2,17.7.

[0308] Embodiment 65

[0309]

[0310] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is methyl 4-ethylbenzoate. In a clean and dry undivided glass electrolytic cell, o-phenylsulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), methyl 4-ethylbenzoate (2.0mmol, 328.2mg) were added in sequence, and then a constant current of 20mA was passed through the electrolytic cell at 80°C with a platinum sheet as anode and a carbon rod as cathode, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 4-[1-(1,1-dioxide-3-oxobenzo[d]isothiazol-2(3H)-yl)ethyl]methyl benzoate was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), yellow powder, 43.2mg, yield 25.0%.

[0311] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ7.93–7.87(m,1H),7.82(d,J=6.9Hz,1H),7.74(dtd,J=20.2,7.4,1.3Hz,2H ),7.58–7.52(m,2H),7.04–6.97(m,2H),5.36(q,J=7.3Hz,1H),2.21(s,3H),1.95(d,J=7.3Hz,3H). 13 C NMR (101MHz, CDCl3): δ169.4,158.5,150.4,137.7,136.2,134.7,134.3,129.0,127.3,125.1,121.6,120.8,52.5,21.1,17.7.

[0312] Embodiment 66

[0313]

[0314] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is 3-ethylbenzonitrile. In a clean and dry undivided glass electrolytic cell, o-benzylsulfimide (0.5mmol, 91.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 3-ethylbenzonitrile (2.0mmol, 262.4mg) were added in sequence, and then a constant current of 20mA was passed through the electrolytic cell at 80°C with a platinum sheet as anode and a carbon rod as cathode, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 3-[1-(1,1-dioxido-3-oxobenzo[d]isothiazol-2(3H)-yl)ethyl]benzonitrile was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), yellow powder, 45.6mg, yield 29.2%.

[0315] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ7.99(d,J=7.8Hz,1H),7.94–7.90(m,1H),7.90–7.85(m,2H),7.84–7.79(m,2 H),7.60(dt,J=7.7,1.4Hz,1H),7.47(t,J=7.8Hz,1H),5.43(q,J=7.3Hz,1H),2.03(d,J=7.3Hz,3H); 13C NMR (101MHz, CDCl3): δ158.5,140.4,137.6,135.0,134.5,132.1,131.9,131.3,129.4,127.0,125.2,120.9,118.6,112.8,52.0,17.4.

[0316] Embodiment 67

[0317]

[0318] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrate is estragole. In a clean and dry undivided glass electrolytic cell, o-phenylsulfimide (0.5 mmol, 91.6 mg), electrolyte sodium bromide (1.0 mmol, 102.9 mg), solvent acetonitrile (10 mL), estragole (2.0 mmol, 296.2 mg) were added in sequence, and then a platinum sheet was used as an anode and a carbon rod was used as a cathode in the electrolytic cell, and a constant current of 20 mA was passed under the condition of 80° C., and the stirring reaction was started for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-[1-(4-methoxyphenyl)allyl]benzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which was a white powder, 58.5 mg, and a yield of 35.5%.

[0319] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ8.07(d,J=7.4Hz,1H),7.93(d,J=7.4Hz,1H),7.85(dt,J=15.1,7.1Hz,2H),7.33(d,J=8.6Hz, 2H), 6.84 (d, J = 8.7Hz, 2H), 6.73 (d, J = 15.7Hz, 1H), 6.19 (dt, J = 15.7, 6.8Hz, 1H), 4.52 (d, J = 6.7Hz, 2H), 3.80 (s, 3H); 13 C NMR (101MHz, CDCl3): δ159.6,158.7,137.8,134.9,134.8,134.3,128.8,128.0,127.5,125.2,121.0,119.2,114.0,55.3,41.2.

[0320] Embodiment 68

[0321]

[0322] The experimental method of this example is the same as that of Example 36, except that the substrate is salvin. In a clean, dry, undivided glass electrolytic cell, o-phenylsulfimide (0.5 mmol, 91.6 mg), electrolyte sodium bromide (1.0 mmol, 102.9 mg), solvent acetonitrile (10 mL), salvin (2.0 mmol, 488.7 mg) were added in sequence, and then a constant current of 20 mA was passed through the electrolytic cell at 80° C. with a platinum sheet as the anode and a carbon rod as the cathode. The reaction was stirred for 5 hours, and the solvent was removed by rotary evaporation after the reaction was completed. The product 2-(7-acetyl-5-(tert-butyl)-3,3-dimethyl-2,3-dihydro-1H-inden-1-yl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained as a yellow powder, 70.9 mg, and a yield of 33.3%.

[0323] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ8.12–8.06(m,1H),7.83–7.73(m,3H),7.68(d,J=1.7Hz,1H),7.41(d,J=1. 7Hz,1H),6.50(dd,J=8.9,7.2Hz,1H),2.65–2.50(m,2H),2.49(s,3H),1.39(s,9H),1.25(s,6H); 13 C NMR (101MHz, CDCl3): δ199.9,158.5,154.8,153.0,138.1,136.0,134.4,134.0,131.3,1 27.1,125.3,125.1,123.3,120.2,56.6,46.9,42.2,35.0,31.4,31.3,29.7,29.2,27.7.

[0324] Embodiment 69

[0325]

[0326] The experimental method of this embodiment is the same as that of Example 36, except that the substrates are 4-ethylanisole and N-acetyl toluenesulfonamide. In a clean, dry, undivided glass electrolytic cell, N-acetyl toluenesulfonamide (0.5mmol, 106.6mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-ethylanisole (2.0mmol, 272.2mg) were added in sequence, and then a constant current of 20mA was introduced at 80°C with a platinum sheet as anode and a carbon rod as cathode in the electrolytic cell, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product N-[1-(4-methoxyphenyl)ethyl]-N-(toluenesulfonyl)acetamide was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which was a colorless oily liquid of 57.8mg with a yield of 33.3%.

[0327] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ7.69(d,J=8.4Hz,2H),7.32–7.27(m,4H),6.83(d,J=8.8Hz,2H) , δ5.74(q,J=7.1Hz,1H),3.79(s,3H),2.44(s,3H),2.20(s,3H),1.80(d,J=7.1Hz,3H); 13 C NMR (101MHz, CDCl3): δ170.4,158.8,144.8,137.0,131.9,129.8,128.6,127.9,113.6,56.3,55.3,26.4,21.6,18.1.

[0328] Embodiment 70

[0329]

[0330] The experimental method of this embodiment is the same as that of embodiment 36, except that the substrates are 4-ethylanisole and N-(tert-butyloxycarbonyl)-toluenesulfonamide. In a clean and dry undivided glass electrolytic cell, N-(tert-butyloxycarbonyl)-toluenesulfonamide (0.5mmol, 135.7mg), electrolyte sodium bromide (1.0mmol, 102.9mg), solvent acetonitrile (10mL), 4-ethylanisole (2.0mmol, 272.2mg) were added in sequence, and then a constant current of 20mA was passed through the electrolytic cell at 80°C with a platinum sheet as anode and a carbon rod as cathode, and the reaction was stirred for 5 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product tert-butyl N-(toluenesulfonyl)-N-[1-(4-methoxyphenyl)ethyl]carbamate was obtained by column chromatography separation (petroleum ether / ethyl acetate=5 / 1), which was a yellow oily liquid with a content of 97.9mg and a yield of 48.3%.

[0331] The specific NMR data are: 1 H NMR (400MHz, CDCl3): δ7.78(d,J=8.3Hz,2H),7.30(d,J=8.1Hz,2H),7.24(d,J=8.5Hz,2H),6.84(d, J=8.8Hz,2H),5.74(q,J=7.0Hz,1H),3.80(s,3H),2.44(s,3H),1.86(d,J=7.0Hz,3H),1.18(s,9H); 13 C NMR (101MHz, CDCl3): δ158.6,150.7,144.0,137.4,133.0,129.3,128.1,128.1,113.5,83.9,55.7,55.3,27.8,21.6,18.7.

[0332] Embodiment 71

[0333] In order to verify the amplification effect of the amination reaction of the present invention, this example carried out a gram-scale reaction, and the reaction apparatus was as follows: Figure 3 As shown, o-phenylmethanesulfonimide (6mmol, 1.10g), electrolyte sodium bromide (6.0mmol, 0.62g), solvent acetonitrile (60mL), diphenylmethane (24.0mmol, 4.0mL) were added to a 100mL three-necked flask in sequence, and then a platinum sheet was used as an anode and a carbon rod was used as a cathode in an electrolytic cell. A constant current of 20mA was passed at 80°C, and the reaction was stirred for 24 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the product 2-dibenzylbenzo[d]isothiazol-3(2H)-one-1,1-dioxide was obtained by column chromatography separation (petroleum ether / ethyl acetate = 5 / 1). The product was 1.18g of white powder with a yield of 53.3%. The product is as shown in FIG. Figure 4 shown.

[0334] The present invention provides an electrochemical direct oxidative dehydrogenation amination reaction under mild conditions without the participation of metal catalysts and bases, using alkanes as raw materials, and successfully prepares a variety of aromatic alkane amination products based on this reaction.

[0335] The present invention provides a method and method for electrochemically catalyzing the direct amination reaction of aromatic hydrocarbon bonds. There are many methods and approaches to implement the technical solution. The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention. All components not specified in this embodiment can be implemented by existing technologies.

Claims

1. A method for electrochemically catalyzing the direct amination reaction of aromatic hydrocarbon bonds, characterized in that: The aromatic alkane compound and the sulfonimide compound are subjected to an electrochemical reaction in the presence of an electrolyte to obtain an amination product; Wherein, the structural formula of the aromatic alkane compound is shown in Formula I, the structural formula of the sulfonimide compound is shown in Formula II or Formula III, and the structural formula of the amination product is shown in Formula IV or Formula V; in, R 1 Any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a fluoroalkyl group, a halogen group, an ester group, a cyano group, a nitro group, a phenyl group, a substituted phenyl group, a furyl group, a substituted furyl group, a pyrrolyl group, a substituted pyrrolyl group, a thienyl group, or a substituted thienyl group; R 2 , R 3 , R 4 , R 5 and R 6 Each of them is independently selected from any one of a hydrogen atom, an alkyl group, an alkoxy group, a fluoroalkyl group, a halogen, an acyl group, an ester group, a vinyl group, a phenyl group, a substituted phenyl group, a furyl group, a substituted furyl group, a pyrrolyl group, a substituted pyrrolyl group, a thienyl group and a substituted thienyl group; When R 6 When R is selected from hydrogen atoms, the aromatic alkane is a primary aromatic alkane; 6 When the aromatic alkane is selected from any one of alkyl, alkoxy, fluoroalkyl, halogen, acyl, ester, vinyl, phenyl, substituted phenyl, furyl, substituted furyl, pyrrolyl, substituted pyrrolyl, thienyl and substituted thienyl, the aromatic alkane is a secondary aromatic alkane.

2. The method according to claim 1, characterized in that The R 1 Any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a fluoroalkyl group, a halogen group, a phenyl group, a cyano group, and an ester group; The R 2 , R 3 , R 4 and R 5 Each of them is independently selected from any one of an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group and a thienyl group; The R 6 Any one selected from a hydrogen atom, an alkyl group, a vinyl group, a phenyl group or a substituted phenyl group.

3. The method according to claim 1, characterized in that The molar ratio of the aromatic alkane compound to the sulfonimide compound is 4-6:

1.

4. The method according to claim 1, characterized in that The electrolyte includes any one of potassium bromide, ammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, potassium iodide or sodium bromide.

5. The method according to claim 1, characterized in that The molar ratio of the electrolyte to the aromatic alkane compound is 1:2-4.

6. The method according to claim 1, characterized in that The cathode material and the anode material of the electrochemical reaction are either carbon rods or platinum sheets.

7. The method according to claim 1, characterized in that The electrochemical reaction has a reaction current of 10 to 30 mA.

8. The method according to claim 1, characterized in that The electrochemical reaction has a reaction temperature of 60 to 80° C. and a reaction time of 3 to 8 hours.

9. The method according to claim 1, characterized in that: The electrochemical reaction is carried out in a reaction solvent, and the reaction solvent is acetonitrile.

10. The method according to claim 9, characterized in that Add 0.1-0.4 mmol of aromatic alkane compounds to each mL of acetonitrile.

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