Method for synthesizing cyclic sulfonamide and sulfonyl olefin through mechanical light excitation

Abstract

The invention discloses a method for synthesizing cyclic sulfonamide and sulfonyl olefin through mechanical light excitation, and particularly relates to a method for synthesizing cyclic sulfonamide and sulfonyl olefin by adding a reaction raw material, a triboluminescent material and a grinding medium into a ball milling tank and synthesizing cyclic sulfonamide and sulfonyl olefin through a mechanical ball milling method. According to the method, the triboluminescent material is activated by utilizing mechanical energy, and photons are continuously generated in a solid-phase reaction mixture to participate in the reaction, so that the photosynthesis of gram-scale cyclic sulfonamide and sulfonyl olefin can be realized at normal temperature without a light source, a new path is provided for replacing a photosynthesis means by mechanical synthesis, and the method is suitable for industrial production. The method is mild in condition, high in reaction rate and high in yield.

Description

Technical Field

[0001] The invention relates to a method for synthesizing cyclic sulfonamide and sulfonyl olefin by mechanical light excitation, and belongs to the technical field of mechanical synthesis. Background Art

[0002] Mechanochemical synthesis is an important chemical synthesis method that does not require the participation of reaction solvents and is an important field of sustainable chemistry. In the past few decades, mechanochemical synthesis methods have been used to synthesize many important substances, especially in industrial production. However, due to the opacity of mechanochemical equipment, many important photochemical syntheses are difficult to achieve by mechanochemical means.

[0003] Cyclic sulfonamides and sulfonyl olefins are important compounds for the synthesis of sulfone derivatives, bioactive inhibitors, and natural medicines. Among the currently reported synthetic methods, important progress has been made in the synthesis of cyclic sulfonamides and sulfonyl olefins in solution by light irradiation. However, the mechanochemical synthesis method, which has broad significance in industrial production, is still difficult to achieve. This is due to the natural low efficiency and poor penetration of light radiation in solid-phase reactions, and the mechanochemical equipment made of stainless steel does not support the penetration of light radiation during the reaction. Therefore, it is urgent to develop new methods in mechanochemistry to achieve the effective combination of photochemistry and mechanochemistry, and to solve the problem of achieving photosynthesis of cyclic sulfonamides and sulfonyl olefins by mechanochemical means. Summary of the invention

[0004] The purpose of the present invention is to provide a method for synthesizing cyclic sulfonamides and sulfonyl olefins by mechanical light excitation, creatively utilizing triboluminescent materials, particularly strontium europium dysprosium aluminate, strontium europium dysprosium aluminate, strontium europium aluminate, strontium europium dysprosium magnesium silicate, strontium europium nitrogen silicate, barium europium nitrogen silicate, and zinc copper sulfide, and the effectiveness of the method is demonstrated in the synthesis of cyclic sulfonamides and sulfonyl olefins. The method of the present invention activates the triboluminescent material by utilizing mechanical energy, and continuously generates photons in the solid phase reaction mixture to participate in the reaction. Therefore, the photosynthesis of cyclic sulfonamides and sulfonyl olefins on a gram scale is achieved without the need for a light source, providing a new path for mechanical synthesis to replace photosynthesis.

[0005] The implementation process of the present invention is as follows: A method for synthesizing cyclic sulfonamide by mechanical light excitation, wherein the synthesis route is as follows: adding compound (I), a reaction amount of a high-valent iodine reagent, a triboluminescent material and a grinding medium into a ball mill, and synthesizing compound (II) by mechanical ball milling,

[0006] R 1is selected from phenyl, substituted aryl, alkyl, naphthyl and thiophene, wherein the substituent in the substituted aryl is selected from C1-C5 alkyl, C1-C5 alkoxy, nitro, halogen and phenylethynyl; R 2 , R 3 Selected from hydrogen, C1~C5 alkyl, cyclohexyl; R 4 The substituted aryl group is selected from the group consisting of C3-C4 alkyl, phenyl, naphthyl, pyridine, thiophene, furan, substituted aryl and biphenyl, wherein the substituent in the substituted aryl group is selected from the group consisting of C1-C5 alkyl, C1-C5 alkoxy, nitro, halogen and phenylethynyl.

[0007] The high-valent iodine reagent is selected from trifluoroiodobenzene, iodobenzene acetate, dichloroiodobenzoylbenzene (PhICl2), diiodobenzoyl diacetate (PIDA), diaryliodonium salt (Ph2I + X − ), iodobenzoic acid (PhIO2), Dess-Martin's oxidation reagent (DMP), 2-iodobenzoic acid (IBX) .

[0008] The triboluminescent material is selected from strontium europium dysprosium aluminate, strontium europium aluminate, strontium europium dysprosium magnesium silicate, strontium europium nitrogen silicate, barium europium nitrogen silicate or zinc copper sulfide.

[0009] The grinding medium is a stainless steel ball, an agate ball, a zirconium oxide ball or an aluminum oxide ball.

[0010] Additives are also added to the above reaction, and the additives are selected from aluminum oxide, silicon dioxide, sodium sulfate , sodium carbonate, sodium hydroxide, triethylamine.

[0011] A method for synthesizing sulfonyl olefins by mechanical light excitation, wherein the synthesis route is as follows: Compound (III), compound (IV), a catalytic amount of tris(tetramethoxyphenyl)amine, a triboluminescent material and a grinding medium are added to a ball mill, and compound (V) is synthesized by mechanical ball milling.

[0012] R 1 is selected from phenyl, substituted aryl, benzoyl, pyrazole and piperidine, wherein the substituent in the substituted aryl is selected from C1-C5 alkyl, C1-C5 alkoxy, nitro, halogen, and the aryl is such as phenyl, naphthyl, etc.; R 2 , R 3The substituent is selected from phenyl, substituted aryl, C11~C13 substituted olefin, indolyl, thienyl, furanyl, biphenyl, pyridyl and naphthyl, wherein the substituent in the substituted aryl is selected from C1~C5 alkyl, C1~C5 alkoxy, nitro and halogen; the substituent in the C11~C13 substituted olefin is phenyl, and the C11~C13 ring number does not include phenyl.

[0013] The triboluminescent material is selected from strontium europium dysprosium aluminate, strontium europium aluminate, strontium europium dysprosium magnesium silicate, strontium europium nitrogen silicate, barium europium nitrogen silicate, and zinc copper sulfide.

[0014] The molar ratio of compound (III) to compound (IV) is (1~2):1~2).

[0015] The grinding medium is a stainless steel ball, an agate ball, a zirconium oxide ball or an aluminum oxide ball.

[0016] The present invention provides the use of triboluminescent materials in the above-mentioned cyclic sulfonamides and sulfonyl olefins, wherein the triboluminescent materials are selected from strontium europium dysprosium aluminate, strontium europium aluminate, strontium europium dysprosium magnesium silicate, strontium europium nitrogen silicate, barium europium nitrogen silicate, and zinc copper sulfide.

[0017] The reaction temperature for the mechanical photoexcitation synthesis of cyclic sulfonamides and sulfonyl olefins is room temperature, and increasing the temperature is beneficial to the reaction.

[0018] Advantages of the present invention: The method of the present invention uses mechanical energy to activate the triboluminescent material, and continuously generates photons in the solid phase reaction mixture to participate in the reaction. Therefore, without the need for a light source, the photosynthesis of cyclic sulfonamides and sulfonyl olefins on a gram scale is achieved, providing a new path for mechanical synthesis to replace photosynthesis. The present invention has excellent characteristics in using mechanochemical methods to replace photosynthesis of cyclic sulfonamides and sulfonyl olefins. It does not require the use of a light source and a reaction solvent, and can achieve the synthesis of cyclic sulfonamides and sulfonyl olefins on a gram scale at room temperature, with mild conditions, fast reaction rate, and high yield. DETAILED DESCRIPTION

[0019] The present invention is further described in detail below by way of examples, but the present invention is not limited to the examples listed. The experimental methods in the following examples without specifying specific conditions are implemented according to conventional methods and conditions.

[0020] Example 1: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), N-(2,2-dimethyl-4-phenylbutyl)-4-methylbenzenesulfonamide (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq), sodium carbonate (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was then closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The milled reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0021]

[0022] White solid, yield 90%, 1 H NMR (400 MHz, Chloroform- d ) δ 7.56 (d, J = 8.0Hz, 2H), 7.30 – 7.27 (m, 4H), 7.23 (d, J = 8.1 Hz, 3H), 4.73 (dd, J = 9.4,7.2 Hz, 1H), 3.47 (dd, J = 10.4, 1.5 Hz, 1H), 3.37 (d, J = 10.4 Hz, 1H), 2.42(s, 3H), 2.09 – 2.00 (m, 1H), 1.75 (dd, J = 12.8, 9.4 Hz, 1H), 1.08 (s, 3H), 0.79 (s, 3H); High-resolution mass spectrometry (ESI ionization source), m / z [C 19 H 23 NO2S +Na] + Theoretical value: 352.1342, measured value: 352.1347.

[0023] Example 2: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), N-[4-(4-fluorophenyl)-2,2-dimethylbutyl]-4-methylbenzenesulfonamide (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq), sodium carbonate (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was then closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The milled reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0024]

[0025] White solid, yield 76%, 1 H NMR (400 MHz, Chloroform- d ) δ 7.53 (d, J = 8.2Hz, 2H), 7.25 – 7.21 (m, J = 7.2 Hz, 4H), 6.93 (t, J = 8.6 Hz, 2H), 4.67 (dd, J = 9.4, 7.2 Hz, 1H), 3.43 (d, J = 10.4 Hz, 1H), 3.33 (d, J = 10.4 Hz, 1H), 2.40 (s, 3H), 2.00 – 1.97 (m, 1H), 1.68 (dd, J = 12.8, 9.4 Hz, 1H), 1.05 (s,3H), 0.75 (s, 3H); High resolution mass spectrometry (ESI ionization source), m / z [C 19 H 22 FNO2S+Na] + Theoretical value: 370.1247, measured value: 370.1241.

[0026] Example 3: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), N-[4-(4-chlorophenyl)-2,2-dimethylbutyl]-4-methylbenzenesulfonamide (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq), sodium carbonate (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was then closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The milled reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0027]

[0028] White solid, yield 78%, 1 H NMR (400 MHz, Chloroform- d ) δ 7.69 (d, J = 8.0Hz, 2H), 7.61– 7.60 (m, 1H), 7.30 – 7.28 (m, 3H), 7.23 (d, J = 7.7 Hz, 1H),7.20 – 7.12 (m, 1H), 5.07 (t, J = 8.2 Hz, 1H), 3.43 (d, J = 10.6 Hz, 1H),3.36 (d, J = 10.6 Hz, 1H), 2.42 (s, 3H), 2.14 (dd, J = 12.8, 7.5 Hz, 1H),1.60 (dd, J = 12.9, 8.9 Hz, 1H), 1.03 (s, 3H), 0.62 (s, 3H); High resolution mass spectrometry (ESI ionization source), m / z [C 19 H 22 ClNO2S+Na] + Theoretical value: 386.0952, measured value: 386.0951.

[0029] Example 4: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), N-[4-(3-bromophenyl)-2,2-dimethylbutyl]-4-methylbenzenesulfonamide (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq), sodium carbonate (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was then closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The milled reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0030]

[0031] White solid, yield 76%, 1 H NMR (400 MHz, Chloroform- d ) δ 7.56 (d, J = 7.9Hz, 2H), 7.30 – 7.28 (m, 3H), 7.24 – 7.22 (m, 3H), 4.73 (dd, J = 9.5, 7.3 Hz,1H), 3.47 (d, J = 10.6 Hz, 1H), 3.37 (d, J = 10.3 Hz, 1H), 2.42 (s, 3H), 2.05(dd, J = 12.8, 7.3 Hz, 1H), 1.75 (dd, J = 12.9, 9.5 Hz, 1H), 1.08 (s, 3H), 0.79 (s, 3H); High-resolution mass spectrometry (ESI ionization source), m / z [C 19 H 22 CBrNO2S+Na] + Theoretical value: 430.0447, measured value: 430.0444.

[0032] Example 5: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), N-[4-(4-phenylethynylphenyl)-2,2-dimethylbutyl]-4-methylbenzenesulfonamide (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was then closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The milled reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0033]

[0034] White solid, yield 63%, 1 H NMR (400 MHz, Chloroform- d ) δ 7.57 – 7.50 (m,4H), 7.42 (d, J = 8.0 Hz, 2H), 7.38 – 7.32 (m, 3H), 7.26 – 7.21 (m, 4H), 4.72(t, J = 8.3 Hz, 1H), 3.45 (d, J = 10.4 Hz, 1H), 3.34 (d, J = 10.4 Hz, 1H), 2.41 (s, 3H), 2.02 (dd, J = 12.5, 7.0 Hz, 2H), 1.70 (dd, J = 12.8, 9.3 Hz,1H), 1.06 (s, 3H), 0.78 (s, 3H); High resolution mass spectrometry (ESI ionization source), m / z [C 27 H 27 NO2S+Na] + Theoretical value: 452.1655, measured value: 452.16548.

[0035] Example 6: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), N-[4-(2-naphthyl)-2,2-dimethylbutyl]-4-methylbenzenesulfonamide (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq), sodium carbonate (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was then closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The milled reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0036]

[0037] White solid, yield 81%, 1 H NMR (400 MHz, Chloroform- d ) δ 7.79 (d, J = 6.9Hz, 1H), 7.76 – 7.71 (m, 2H), 7.67 (s, 1H), 7.52 (d, J = 8.0 Hz, 2H), 7.48 –7.41 (m, 2H), 7.37 (dd, J = 8.5, 1.8 Hz, 1H), 7.12 (d, J = 7.9 Hz, 2H), 4.89(dd, J = 9.4, 7.3 Hz, 1H), 3.53 (d, J = 10.3 Hz, 1H), 3.42 (d, J = 10.4 Hz,1H), 2.33 (s, 3H), 2.12 – 2.04 (m, 1H), 1.81 (dd, J = 12.9, 9.4 Hz, 1H), 1.09(s, 3H), 0.84 (s, 3H); High resolution mass spectrometry (ESI ionization source), m / z [C 23 H 25 NO2S+H] + Theoretical value: 380.1679, measured value: 380.1680.

[0038] Example 7: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), N-[4-(2-iodo-5-thienyl)-2,2-dimethylbutyl]-4-methylbenzenesulfonamide (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq), sodium carbonate (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was then closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The milled reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0039]

[0040] Yellow solid, yield 75%, 1 H NMR (400 MHz, Chloroform- d ) δ 7.50 (d, J = 8.0Hz, 2H), 7.20 (d, J = 7.9 Hz, 2H), 6.99 (d, J = 3.6 Hz, 1H), 6.66 (d, J = 3.6Hz, 1H), 5.04 (t, J = 7.8 Hz, 1H), 3.40 (d, J = 9.6 Hz, 1H), 3.20 (d, J =10.1 Hz, 1H), 2.41 (s, 3H), 2.08 (dd, J = 13.0, 7.6 Hz, 1H), 1.79 (dd, J =12.9, 8.4 Hz, 1H), 1.07 (s, 3H), 0.88 (s, 3H); High resolution mass spectrometry (ESI ionization source), m / z [C 17 H 20 INO2S2+Na] + Theoretical value: 483.9872, measured value: 483.9869.

[0041] Example 8: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), 4-methyl-N-[2-(phenylmethyl)ethyl]benzenesulfonamide (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq), sodium carbonate (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was then closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The ground reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0042]

[0043] White solid, yield 76%, 1 H NMR (400 MHz, Chloroform- d ) δ 7.77 (d, J = 8.1Hz, 2H), 7.51 (d, J = 6.8 Hz, 2H), 7.38 – 7.33 (m, 5H), 6.29 (s, 1H), 3.82(td, J = 7.6, 5.2 Hz, 1H), 3.68 – 3.63 (m, 1H), 3.53 (q, J = 7.3 Hz, 1H),3.40 (dt, J = 10.7, 6.9 Hz, 1H), 2.45 (s, 3H); High resolution mass spectrometry (ESI ionization source), m / z [C 16 H 17 NO3S+H] + Theoretical value: 304.1002, measured value: 304.1003.

[0044] Example 9: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), 3-phenylpropylaminosulfonate (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq), sodium carbonate (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The ground reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0045]

[0046] Colorless oil, 16.6 mg, 1 H NMR (400 MHz, Chloroform- d ) δ 7.44 – 7.33 (m, 5H), 4.92 – 4.82 (m, 2H), 4.66 (dd, J = 11.7, 4.9 Hz, 1H), 4.35 (d, J = 9.5 Hz,1H), 2.32 – 2.18 (m, 1H), 2.03 (dd, J = 14.5, 2.4 Hz, 1H); High-resolution mass spectrometry (ESI ionization source), m / z [C9H 11 NO3S+H] + Theoretical value: 214.0532, measured value: 214.0535.

[0047] Example 10: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), N-[4-(4-tert-butylphenyl)-2,2-dimethylbutyl]-4-methylbenzenesulfonamide (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq), sodium carbonate (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The milled reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0048]

[0049] White solid, yield 83%, 1 H NMR (400 MHz, Chloroform- d ) δ 7.47 (d, J = 8.0Hz, 2H), 7.23 (d, J = 8.1 Hz, 2H), 7.15 – 7.13 (m, 4H), 4.71 (dd, J = 9.5,7.3 Hz, 1H), 3.49 (d, J = 10.3 Hz, 1H), 3.32 (d, J = 10.3 Hz, 1H), 2.37 (s,3H), 2.06 – 1.98 (m, 1H), 1.74 (dd, J = 12.8, 9.5 Hz, 1H), 1.30 (s, 9H), 1.06(s, 3H), 0.82 (s, 3H); High resolution mass spectrometry (ESI ionization source), m / z [C 23 H 31 NO2S+H] + Theoretical value: 386.2148, measured value: 386.2150.

[0050] Example 11: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), N-[4-(4-methylphenyl)-2,2-dimethylbutyl]-4-methylbenzenesulfonamide (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq), sodium carbonate (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The milled reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0051]

[0052] White solid, yield 82%, 1 H NMR (400 MHz, Chloroform- d ) δ 7.55 (d, J = 8.0Hz, 2H), 7.22 (d, J= 7.9 Hz, 2H), 7.17 (d, J = 7.8 Hz, 2H), 7.08 (d, J = 7.8Hz, 2H), 4.65 (dd, J = 9.4, 7.2 Hz, 1H), 3.42 (d, J = 10.4 Hz, 1H), 3.34 (d, J = 10.4 Hz, 1H), 2.40 (s, 3H), 2.32 (s, 3H), 1.99 (dd, J = 12.4, 7.2 Hz,1H), 1.72 (dd, J = 12.8, 9.4 Hz, 1H), 1.05 (s, 3H), 0.74 (s, 3H); High resolution mass spectrometry (ESI ionization source), m / z [C 20 H 25 NO2S+Na] + Theoretical value: 366.1498, measured value: 366.1496.

[0053] Example 12: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), N-[4-(4-methoxyphenyl)-2,2-dimethylbutyl]-4-methylbenzenesulfonamide (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq), sodium carbonate (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The milled reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0054]

[0055] White solid, yield 85%, 1 H NMR (400 MHz, Chloroform- d ) δ 7.52 (d, J = 8.2Hz, 2H), 7.21 – 7.17 (m, 4H), 6.79 (d, J = 8.7 Hz, 2H), 4.65 (dd, J= 9.4,7.2 Hz, 1H), 3.78 (s, 3H), 3.43 (d, J = 9.7 Hz, 1H), 3.32 (d, J = 10.3 Hz,1H), 2.39 (s, 3H), 1.98 (dd, J = 12.6, 6.7 Hz, 1H), 1.71 (dd, J = 12.8, 9.4Hz, 1H), 1.05 (s, 3H), 0.77 (s, 3H); High resolution mass spectrometry (ESI ionization source), m / z [C 20 H 25 NO3S+H] + Theoretical value: 360.1628, measured value: 360.1634.

[0056] Example 13: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), 2-nitro-N-(4-phenylbutyl)benzenesulfonamide (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq), sodium carbonate (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The ground reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0057]

[0058] White solid, yield 87%, 1 H NMR (400 MHz, Chloroform- d ) δ 7.67 (d, J = 8.0Hz, 2H), 7.30 – 7.26 (m, 5H), 7.25 – 7.23 (m, 1H), 7.22 – 7.20 (m, 1H), 4.78(dd, J= 8.0, 3.6 Hz, 1H), 3.65 – 3.56 (m, 1H), 3.46 – 3.36 (m, 1H), 2.41 (s,3H), 1.99 – 1.93 (m, 1H), 1.82– 1.77 (m, 2H), 1.67 – 1.61 (m, 1H); High resolution mass spectrometry (ESI ionization source), m / z [C 17 H 19 NO2S+Na] + Theoretical value: 324.1029, measured value: 324.1030.

[0059] Example 14: In a 5.0 ml stainless steel grinding jar were added 20 stainless steel balls (3 mm), N-(2,2-dimethyl-4-phenylbutyl)methanesulfonamide (0.2 mmol, 1.0 eq), sodium iodide (0.2 mmol, 1.0 eq), hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq), sodium carbonate (0.8 mmol, 4.0 eq) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%). The jar was closed and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out 4 times, each for 30 minutes, at a frequency of 30 Hz. The milled reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The crude product was separated by thin layer chromatography to obtain the target sulfonamide.

[0060]

[0061] White solid, yield 93%, 1 H NMR (400 MHz, Chloroform- d ) δ 8.11 (d, J = 8.7Hz, 2H), 7.57 (d, J = 8.7 Hz, 2H), 7.22 – 7.14 (m, 3H), 7.10 (d, J = 6.8 Hz,2H), 4.87 (dd, J = 9.8, 7.2 Hz, 1H), 3.66 (d, J = 10.0 Hz, 1H), 3.30 (d, J =10.0 Hz, 1H), 2.17 – 2.12 (m, 1H), 1.79 (dd, J= 12.9, 9.8 Hz, 1H), 1.13 (s, 3H), 1.03 (s, 3H); High resolution mass spectrometry (ESI ionization source), m / z [C 18 H 20 N2O4S+Na] + Theoretical value: 383.1036, measured value: 383.1033.

[0062] Example 15: This example differs from Example 1 only in that hydroxytoluenesulfonyl iodobenzene (0.8 mmol, 4.0 eq.) is replaced with [hydroxy(methanesulfonyloxy)iodo]benzene (0.8 mmol, 4.0 eq.) and the yield is 13%.

[0063] Example 16: The only difference between this example and Example 1 is that strontium europium dysprosium aluminate (less than 15 microns, 100wt%) is replaced with strontium europium aluminate (less than 15 microns, 100wt%), and the yield is 44%.

[0064] Example 17: The only difference between this example and Example 1 is that strontium europium dysprosium aluminate (less than 15 microns, 100wt%) is replaced with strontium europium dysprosium magnesium silicate (less than 15 microns, 100wt%), and the yield is 37%.

[0065] Example 18: The only difference between this example and Example 1 is that strontium europium dysprosium aluminate (less than 15 microns, 100wt%) is replaced with strontium europium nitrogen silicate (less than 15 microns, 100wt%), and the yield is 22%.

[0066] Example 19: The only difference between this example and Example 1 is that strontium europium dysprosium aluminate (less than 15 microns, 100wt%) is replaced with barium europium nitrogen silicate (less than 15 microns, 100wt%), and the yield is 32%.

[0067] Example 20: This example differs from Example 1 only in that sodium carbonate (0.8 mmol, 4.0 equivalents) is replaced with sodium hydroxide (0.6 mmol, 3.0 equivalents), and the yield is 46%.

[0068] Example 21: This example differs from Example 1 only in that sodium carbonate (0.8 mmol, 4.0 eq.) is replaced with triethylamine (0.6 mmol, 3.0 eq.) and the yield is 43%.

[0069] Example 22: Similar to the synthesis method of Example 1, different amide cyclization products can be obtained by changing the substrate. The specific substrate types and yield data are shown in Table 1, but the scope of the substrate is not limited to the table.

[0070]

[0071]

[0072]

[0073]

[0075] Example 23: In a glove box, sulfonyl chloride (0.4 mmol, 2.0 eq), 1,1-diphenylethylene (0.2 mmol, 1.0 eq), tri(4-methoxyphenyl)amine (0.02 mmol, 10 mol%) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%) were added to a 5.0 ml stainless steel grinding jar containing 5 stainless steel balls (5 mm). The jar was sealed in the glove box and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out at a frequency of 30 Hz for 180 min. The ground reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The corresponding product was isolated by thin layer chromatography.

[0076]

[0077] White solid, yield 89%, 1 H NMR (400 MHz, CDCl3) δ 7.47 (d, J = 7.9 Hz, 2H),7.39 – 7.34 (m, 2H), 7.30 (t, J = 7.5 Hz, 4H), 7.20 (d, J = 7.7 Hz, 2H), 7.15(d, J = 8.0 Hz, 2H), 7.10 (d, J = 7.5 Hz, 2H), 6.99 (s, 1H), 2.38 (s, 3H); High resolution mass spectrometry (ESI ionization source), m / z [C 21 H 18 O2S+H] + Theoretical value: 335.1100, measured value: 335.1107.

[0078] Example 24: In a glove box, 3,4,5-trifluorobenzenesulfonyl chloride (0.4 mmol, 2.0 eq.), 1,1-diphenylethylene (0.2 mmol, 1.0 eq.), tri(4-methoxyphenyl)amine (0.02 mmol, 10 mol%) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%) were added to a 5.0 ml stainless steel grinding jar containing 5 stainless steel balls (5 mm). The jar was sealed in the glove box and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out at a frequency of 30 Hz for 180 min. The ground reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The corresponding product was isolated by thin layer chromatography.

[0079]

[0080] White solid, yield 76%, 1 H NMR (400 MHz, CDCl3) δ 7.48 – 7.46 (m, 2H), 7.39– 7.36 (m, 4H), 7.29 (s, 1H), 7.24 (s, 1H), 7.15 (t, J = 6.3 Hz, 2H), 7.10(d, J = 7.4 Hz, 2H), 7.04 (s, 1H); High resolution mass spectrometry (ESI ionization source), m / z [C 20 H 13 F3O2S+H] + Theoretical value: 375.0661, measured value: 375.0667.

[0081] Example 25: In a glove box, 2-chloroethanesulfonyl chloride (0.4 mmol, 2.0 eq.), 1,1-diphenylethylene (0.2 mmol, 1.0 eq.), tri(4-methoxyphenyl)amine (0.02 mmol, 10 mol%) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%) were added to a 5.0 ml stainless steel grinding jar containing 5 stainless steel balls (5 mm). The jar was sealed in the glove box and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out at a frequency of 30 Hz for 180 min. The ground reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The corresponding product was isolated by thin layer chromatography.

[0082]

[0083] White solid, yield 65%, 1H NMR (400 MHz, CDCl3) δ 7.47 – 7.44 (m, 4H), 7.40– 7.35 (m, 4H), 7.29 (d, J = 7.5 Hz, 2H), 6.80 (s, 1H), 3.77 (t, J = 6.9 Hz,2H), 3.15 (t, J = 7.0 Hz, 2H); High resolution mass spectrometry (ESI ionization source), m / z [C 16 H 15 ClO2S+H] + Theoretical value: 307.0554, measured value: 307.0558.

[0084] Example 26: In a glove box, benzoazolesulfonyl chloride (0.4 mmol, 2.0 eq.), 1,1-diphenylethylene (0.2 mmol, 1.0 eq.), tri(4-methoxyphenyl)amine (0.02 mmol, 10 mol%) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%) were added to a 5.0 ml stainless steel grinding jar containing 5 stainless steel balls (5 mm). The jar was sealed in the glove box and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out at a frequency of 30 Hz for 180 min. The milled reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The corresponding product was isolated by thin layer chromatography.

[0085]

[0086] Brown solid, yield 78%, 1 H NMR (400 MHz, CDCl3)δ 9.17 (s, 1H), 8.09 (d, J =8.6 Hz, 1H), 8.00 (s, 1H), 7.76 (d, J = 8.4 Hz, 1H), 7.39 – 7.35 (m, 1H),7.32 – 7.27 (m,, 3H), 7.23 – 7.16 (m, 4H), 7.12 (s, 1H), 7.00 (d, J = 7.5 Hz,2H); High resolution mass spectrometry (ESI ionization source), m / z [C 21 H 15 NO2S2+Na] + Theoretical value: 400.0436, measured value: 400.0444.

[0087] Example 27: In a glove box, 3-methylpyrazolesulfonyl chloride (0.4 mmol, 2.0 eq), 1,1-diphenylethylene (0.2 mmol, 1.0 eq), tri(4-methoxyphenyl)amine (0.02 mmol, 10 mol%) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%) were added to a 5.0 ml stainless steel grinding jar containing 5 stainless steel balls (5 mm). The jar was sealed in the glove box and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out at a frequency of 30 Hz for 180 min. The ground reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The corresponding product was isolated by thin layer chromatography.

[0088]

[0089] Orange solid, yield 72%, 1 H NMR (400 MHz, CDCl3) δ 7.45 (s, 1H), 7.39 – 7.37(m, 3H), 7.32 – 7.30 (m, 3H), 7.22 (d, J = 7.7 Hz, 2H), 7.17 (d, J = 7.4 Hz,2H), 7.07 (s, 2H), 3.75 (s, 3H); High resolution mass spectrometry (ESI ionization source), m / z [C 18 H 16 N2O2S+Na] + Theoretical value: 347.0825, measured value: 347.0822.

[0090] Example 28: In a glove box, piperidinesulfonyl chloride (0.4 mmol, 2.0 eq), 1,1-diphenylethylene (0.2 mmol, 1.0 eq), tri(4-methoxyphenyl)amine (0.02 mmol, 10 mol%) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%) were added to a 5.0 ml stainless steel grinding jar containing 5 stainless steel balls (5 mm). The jar was sealed in the glove box and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out at a frequency of 30 Hz for 180 min. The ground reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The corresponding product was isolated by thin layer chromatography.

[0091]

[0092] Brown solid, yield 49%, 1H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 3.4 Hz, 4H),7.35 – 7.31 (m, 4H), 7.27 (s, 1H), 7.24 (s, 1H), 6.64 (s, 1H), 3.07 – 3.05(m, 4H), 1.57 – 1.54 (m, 4H), 1.54 – 1.52 (m, 2H); High resolution mass spectrometry (ESI ionization source), m / z [C 19 H 21 NO2S+Na] + Theoretical value: 350.1185, measured value: 350.1186.

[0093] Example 29: In a glove box, 2,4,6-trimethylbenzenesulfonyl chloride (0.4 mmol, 2.0 eq.), 1,1-diphenylethylene (0.2 mmol, 1.0 eq.), tri(4-methoxyphenyl)amine (0.02 mmol, 10 mol%) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%) were added to a 5.0 ml stainless steel grinding jar containing 5 stainless steel balls (5 mm). The jar was sealed in the glove box and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out at a frequency of 30 Hz for 180 min. The ground reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The corresponding product was isolated by thin layer chromatography.

[0094]

[0095] White solid, yield 80%, 1 H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 7.1 Hz, 1H),7.35 (t, J = 7.5 Hz, 2H), 7.30 (d, J = 4.3 Hz, 1H), 7.23 (dd, J = 6.8 Hz,4H), 7.10 (s, 1H), 7.02 (d, J = 7.4 Hz, 2H), 6.79 (s, 2H), 2.48 (s, 6H), 2.28(s, 3H); High resolution mass spectrometry (ESI ionization source), m / z [C 23 H 22 O2S+H] + Theoretical value: 363.1413, measured value: 363.1416.

[0096] Example 30: In a glove box, 4-tert-butylbenzenesulfonyl chloride (0.4 mmol, 2.0 eq.), 1,1-diphenylethylene (0.2 mmol, 1.0 eq.), tri(4-methoxyphenyl)amine (0.02 mmol, 10 mol%) and strontium europium dysprosium aluminate (less than 15 μm, 100 wt%) were added to a 5.0 ml stainless steel grinding jar containing 5 stainless steel balls (5 mm). The jar was sealed in the glove box and placed in a ball mill (Retsch MM 400). The mechanochemical reaction was carried out at a frequency of 30 Hz for 180 min. The ground reaction mixture was passed through a silica gel column (eluted with ethyl acetate) and the filtrate was evaporated to dryness. The corresponding product was isolated by thin layer chromatography.

[0097]

[0098] White solid, yield 88%, 1 H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 8.1 Hz, 2H),7.40 – 7.34 (m, 4H), 7.30 – 7.24 (m, 4H), 7.23 (d, J = 7.7 Hz, 2H), 7.10 (d,J = 7.5 Hz, 2H), 7.05 (s, 1H), 1.33 (s, 9H); High resolution mass spectrometry (ESI ionization source), m / z [C 24 H 24 O2S+H] + Theoretical value: 377.1570, measured value: 377.1572.

[0099] Example 31: This example differs from Example 23 only in that 1,1-diphenylethylene (0.2 mmol, 1.0 eq.) is replaced with 5-methylene-6,7,8,9-tetrahydro-5H-benzo[7]annulene (0.2 mmol, 1.0 eq.).

[0100]

[0101] White solid, yield 85%, 1H NMR (400 MHz, CDCl3)δ 7.58 (d, J = 8.0 Hz, 2H),7.15 (d, J = 8.1 Hz, 2H), 7.11 (d, J = 5.7 Hz, 2H), 7.08 – 7.04 (m, 1H), 7.00(d, J = 7.2 Hz, 1H), 6.24 (t, J = 7.2 Hz, 1H), 4.22 (s, 2H), 2.57 (t, J = 7.0Hz, 2H), 2.36 (s, 3H), 2.11 (p, J = 7.1 Hz, 2H), 1.84 (q, J = 7.2 Hz, 2H); High resolution mass spectrometry (ESI ionization source), m / z [C 19 H 20 O2S+H] + Theoretical value: 313.1257, measured value: 313.1267.

[0102] Example 32: This example differs from Example 23 only in that 1,1-diphenylethylene (0.2 mmol, 1.0 eq.) is replaced with 1-phenyl-1-cyclohexene (0.2 mmol, 1.0 eq.) with a yield of 63%.

[0103]

[0104] White solid, yield 63%, 1 H NMR (400 MHz, CDCl3)δ 7.39 (d, J = 7.9 Hz, 2H), 7.07 – 7.05 (m, 3H), 7.02 (d, J = 1.7 Hz, 2H), 6.98 (d, J = 8.3 Hz, 2H), 6.23(t, J = 4.0 Hz, 1H), 4.36 (d, J = 5.5 Hz, 1H), 2.79 (dd, J = 14.2, 3.1 Hz,1H), 2.42 – 2.32 (m, 1H), 2.30 (s, 3H), 2.23 (d, J = 6.3 Hz, 1H), 2.15 – 2.11(m, 1H), 1.93 – 1.85 (m, 1H), 1.76 – 1.70 (m, 1H); High resolution mass spectrometry (ESI ionization source), m / z [C 19 H 20 O2S+H] + Theoretical value: 313.1257, measured value: 313.1259.

[0105] Example 33: This example differs from Example 23 only in that 1,1-diphenylethylene (0.2 mmol, 1.0 eq.) is replaced with 1-phenylcyclohept-1-ene (0.2 mmol, 1.0 eq.) with a yield of 88%.

[0106]

[0107] White solid, yield 88%, 1 H NMR (400 MHz, CDCl3) δ 7.57 (d, J = 7.9 Hz, 2H),7.09 – 7.05 (m, 5H), 6.99 – 6.92 (m, 2H), 6.29 (dd, J = 9.3, 4.7 Hz, 1H),4.41 (t, J = 5.0 Hz, 1H), 2.92 – 2.80 (m, 1H), 2.64 – 2.52 (m, 1H), 2.45 –2.36 (m, 1H), 2.31 (s, 3H), 2.26 (d, J = 19.2 Hz, 1H), 2.02 – 1.95 (m, 1H),1.90 – 1.83 (m, 2H), 1.41 (d, J = 10.9 Hz, 1H); High-resolution mass spectrometry (ESI ionization source), m / z [C 20 H 22 O2S+H] + Theoretical value: 327.1413, measured value: 327.1413.

[0108] Example 34: This example differs from Example 23 only in that 1,1-diphenylethylene (0.2 mmol, 1.0 equivalent) is replaced with 1-phenylcyclopentadeca-1-ene (0.2 mmol, 1.0 equivalent)

[0109] Pale yellow solid, yield 81%, 1H NMR (400 MHz, CDCl3)δ 7.61 (d, J = 8.0 Hz, 2H), 7.23 – 7.16 (m, 5H), 6.88 (d, J = 5.8 Hz, 2H), 5.84 (dd, J = 10.2, 4.3 Hz,1H), 3.85 (dd, J = 12.5, 3.0 Hz, 1H), 2.40 (s, 3H), 2.16 – 2.06 (m, 2H), 2.02(d, J = 11.3 Hz, 1H), 1.97 – 1.89 (m, 1H), 1.66 (d, J = 10.3 Hz, 1H), 1.41 –1.22 (m, 18H), 1.11 (t, J = 6.9 Hz, 1H); High-resolution mass spectrometry (ESI ionization source), m / z [C 28 H 38 O2S+H] + Theoretical value: 439.2665, measured value: 439.2664.

[0110] Example 35: The only difference between this example and Example 23 is that strontium europium dysprosium aluminate (less than 15 microns, 100wt%) is replaced with strontium magnesium europium dysprosium silicate (less than 15 microns, 100wt%), and the yield is 46%.

[0111] Example 36: The only difference between this example and Example 23 is that strontium europium dysprosium aluminate (less than 15 microns, 100wt%) is replaced with strontium europium nitrogen silicate (less than 15 microns, 100wt%), and the yield is 49%.

[0112] Example 37: The only difference between this example and Example 23 is that strontium europium dysprosium aluminate (less than 15 microns, 100wt%) is replaced with barium europium nitrogen silicate (less than 15 microns, 100wt%), and the yield is 53%.

[0113] Example 38: Similar to the synthesis method of Example 23, different sulfonated products can be obtained by changing the substrate. The specific substrate type and yield data are shown in Table 2, but the substrate range is not limited to the table.

[0114]

[0115] Finally, it is necessary to explain here that the above embodiments are only used to further illustrate the technical solution of the present invention in detail and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art can understand that according to the above content of the present invention, some modifications or adjustments can be made to the present invention. These modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. A method for synthesizing cyclic sulfonamides by mechanical light excitation, characterized in that The synthesis route is as follows: Compound (I), a reaction amount of a high-valent iodine reagent, a triboluminescent material and a grinding medium are added to a ball mill, and compound (II) is synthesized by mechanical ball milling. ； The R 1 is selected from phenyl, substituted aryl, alkyl, naphthyl and thiophene, wherein the substituent in the substituted aryl is selected from C1-C5 alkyl, C1-C5 alkoxy, nitro, halogen and phenylethynyl; R 2 , R 3 is selected from hydrogen, C1-C5 alkyl, cyclohexyl; R 4 A group selected from C3-C4 alkyl, phenyl, naphthyl, pyridine, thiophene, furan, substituted aryl and biphenyl, wherein the substituent in the substituted aryl is selected from C1-C5 alkyl, C1-C5 alkoxy, nitro, halogen and phenylethynyl; The high-valent iodine reagent is selected from trifluoroiodobenzene, iodobenzene acetate, dichloroiodobenzoylbenzene, diacetate iodobenzoylbenzene, diaryl iodide salt, iodobenzoylbenzene, Dess-Martin oxidant, 2-iodobenzoic acid, ； The triboluminescent material is selected from strontium europium dysprosium aluminate, strontium europium aluminate, strontium europium dysprosium magnesium silicate, strontium europium nitrogen silicate, barium europium nitrogen silicate or zinc copper sulfide.

2. The method for synthesizing cyclic sulfonamides by mechanical light excitation according to claim 1, characterized in that: The grinding medium is a stainless steel ball, an agate ball, a zirconium oxide ball or an aluminum oxide ball.

3. The method for synthesizing cyclic sulfonamide by mechanical light excitation according to claim 1, characterized in that: An additive is also added to the above reaction, and the additive is selected from aluminum oxide, silicon dioxide, sodium sulfate, sodium carbonate, sodium hydroxide, and triethylamine.

4. The method for synthesizing cyclic sulfonamide by mechanical light excitation according to claim 1, characterized in that: The triboluminescent material is strontium europium dysprosium aluminate.

5. The method for synthesizing cyclic sulfonamide by mechanical light excitation according to claim 1, characterized in that: The reaction temperature is room temperature.

6. A method for synthesizing sulfonyl olefins by mechanical photoexcitation, characterized in that The synthesis route is as follows: Compound (III), compound (IV), a catalytic amount of tris(tetramethoxyphenyl)amine, a triboluminescent material and a grinding medium are added to a ball mill, and compound (V) is synthesized by mechanical ball milling. ； R 1 is selected from phenyl, substituted aryl, benzoyl, pyrazole and piperidine, wherein the substituent in the substituted aryl is selected from C1-C5 alkyl, C1-C5 alkoxy, nitro and halogen; R 2 , R 3 is selected from phenyl, substituted aryl, C11-C13 substituted olefin, indolyl, thienyl, furyl, biphenyl, pyridyl and naphthyl, wherein the substituent in the substituted aryl is selected from C1-C5 alkyl, C1-C5 alkoxy, nitro and halogen, and the substituent in the C11-C13 substituted olefin is phenyl; The triboluminescent material is selected from strontium europium dysprosium aluminate, strontium europium aluminate, strontium europium dysprosium magnesium silicate, strontium europium nitrogen silicate, barium europium nitrogen silicate, and zinc copper sulfide.

7. The method for synthesizing sulfonyl olefins by mechanical light excitation according to claim 6, characterized in that: The molar ratio of compound (III) to compound (IV) is (1~2):(1~2).

8. The method for synthesizing sulfonyl olefins by mechanical light excitation according to claim 6, characterized in that: The grinding medium is a stainless steel ball, an agate ball, a zirconium oxide ball or an aluminum oxide ball.

9. The method for synthesizing sulfonyl olefins by mechanical light excitation according to claim 6, characterized in that: The reaction temperature is room temperature.

10. Use of triboluminescent materials in the synthesis of cyclic sulfonamides and sulfonyl olefins, wherein the triboluminescent materials are selected from strontium europium dysprosium aluminate, strontium europium aluminate, strontium europium dysprosium magnesium silicate, strontium europium nitrogen silicate, barium europium nitrogen silicate, and zinc copper sulfide.

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