A method of preparing sulfinyl and sulfonyl compounds by sulfinylation

Abstract

The application provides a method for preparing sulfinic acid compounds, sulfinic acid salt compounds, sulfonic acid salt compounds and sulfonyl compounds through sulfinylation, comprising the following steps: under the conditions of a protective atmosphere and light, performing a sulfinylation reaction on an alkyl compound and a sulfur dioxide donor under the condition of a catalyst to obtain an alkyl sulfinic acid compound. The main catalyst comprises a metal salt, and the metal elements in the metal salt comprise one or more of Fe, Cu and Ce; the cocatalyst comprises one or more of chlorosilane, a tetraalkylammonium chloride, an alkali metal chloride and hydrochloric acid. The method in the application has high catalytic efficiency (TON>350000, TOF>50000 / h), high selectivity (the conversion selectivity of sulfinic acid is >99%), high conversion rate (sulfinic acid is close to complete conversion), and is low in cost, high in atomic economy, basically free of waste in the production process, and green, low-carbon and environmentally friendly.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, and particularly relates to a method for preparing sulfinic acid compounds, sulfinate compounds, sulfonate compounds and sulfonyl compounds by sulfinylation. Background Technology

[0002] Sulfonation of alkanes refers to the reaction of alkanes with sulfur dioxide in the presence of light and a catalyst to produce alkyl sulfinic acids. The resulting sulfinic acids can be further neutralized with a base to yield alkyl sulfinates. Alkyl sulfinic acids are then neutralized with a base in air to yield alkyl sulfonates. Alkyl sulfinic acids react with one or more electrophiles, oxidizing functionalizing agents, nucleophiles, etc., to produce compounds such as alkyl sulfones, sulfonates, sulfonyl fluorides, and sulfonamides. The preparation of these sulfonyl compounds typically requires the reaction of the corresponding sulfonyl chloride with a nucleophile. However, sulfonyl chlorides originate from the oxidation of thiols and disulfides, or the nucleophilic addition of Grignard reagents to sulfur dioxide substitutes, resulting in high production costs, low conversion rates, and poor atom economy. Summary of the Invention

[0003] The purpose of this invention is to provide a method for preparing sulfinic acid compounds, sulfinate compounds, sulfonate compounds and sulfonyl compounds by sulfinylation. The method of this invention has high catalytic efficiency, high conversion rate and low cost.

[0004] This invention provides a method for preparing sulfinic acid compounds by sulfinylation, comprising the following steps:

[0005] Under a protective atmosphere and light conditions, alkyl compounds are subjected to sulfinylation with sulfur dioxide donors under catalytic conditions to obtain alkyl sulfinic acid compounds.

[0006] The sulfur dioxide donor includes one or more of the following: sulfurous acid solution, 1,4-diazabicyclo[2.2.2]octane-1,4-dion-1,4-disulfinate, K2S2O5, Na2S2O5, and sulfur dioxide gas.

[0007] The catalyst includes a main catalyst and a co-catalyst;

[0008] The main catalyst comprises a metal salt, wherein the metal element in the metal salt includes one or more of Fe, Cu and Ce; the co-catalyst comprises one or more of chlorosilane, tetraalkylammonium chloride, alkali metal chloride and hydrochloric acid.

[0009] This invention provides a method for preparing sulfinylation compounds, comprising the following steps:

[0010] The alkyl sulfinic acid compound was prepared according to the method described above, and then neutralized with a base to obtain an alkyl sulfinate compound.

[0011] This invention provides a method for preparing sulfonate compounds by sulfinization, comprising the following steps:

[0012] The alkyl sulfinic acid compound was prepared according to the method described above, and then neutralized with an alkali in an oxygen-containing atmosphere to obtain an alkyl sulfonate compound.

[0013] This invention provides a method for preparing sulfonyl compounds by sulfinization, comprising the following steps:

[0014] Alkyl sulfinic acid compounds were prepared according to the method described above, and then reacted with electrophilic reagents or oxidizing agents to obtain alkyl sulfonyl compounds.

[0015] Preferably, the metal salt includes one or more of the following: metal halides, nitrates, sulfates, acetates, trifluoromethanesulfonates, tetrafluoroborates, hexafluorophosphates, trifluoroacetates, citrates, oxalates, acrylates, tris(2,2,6,6-tetramethyl-3,5-heptadecanoic acid) salts, and acetylacetone salts.

[0016] Preferably, the molar ratio of the metal element in the main catalyst to the co-catalyst is 1:(4~200000).

[0017] Preferably, the alkyl compound comprises substituted or unsubstituted C1-C20 alkanes;

[0018] The substituents in the substituted C1-C20 alkanes include one or more of the following: hydroxyl, carbonyl, C4-C20 aromatic, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C1-C10 ester, cyano, halogen, C1-C10 phosphate, amino, C2-C10 alkenyl, C2-C10 alkynyl, C1-C10 amino, amide, C1-C10 sulfonyl, C1-C10 sulfinyl, and C1-C10 alkoxy.

[0019] Preferably, the molar ratio of the metal element to the alkyl compound in the main catalyst is 1:(20~8000000).

[0020] Preferably, the molar ratio of the sulfur dioxide donor to the alkyl compound is 1:(1~80), based on the number of moles of sulfur dioxide in the sulfur dioxide donor.

[0021] Preferably, the temperature of the sulfinylation reaction is 20~35°C, the time of the sulfinylation reaction is 7~36 hours, and the pressure of the sulfinylation reaction is 0.1~5 MPa.

[0022] Preferably, in the illumination conditions, the wavelength of the light source is 365~400nm and the power of the light source is 5~100W.

[0023] Preferably, the sulfinylation reaction is carried out in a solvent environment, the solvent including water and / or an organic solvent, the organic solvent including one or more of acetonitrile, acetone, ethyl acetate, dichloromethane, 1,2-dichloroethane and chloroform; the volume ratio of water to organic solvent is 1:(0~9).

[0024] Preferably, the alkyl sulfinic acid compound is reacted with an electrophilic reagent in the presence of a basic reagent to obtain an alkyl sulfone compound;

[0025] Alternatively, an alkyl sulfinic acid compound may be reacted with an oxidizing agent to obtain an oxidation product; said oxidation product includes alkyl sulfonate compounds, alkyl sulfonyl chloride compounds, alkyl sulfonyl fluoride compounds, or alkyl sulfonamide compounds.

[0026] Preferably, when the alkyl compound has multiple reaction sites, the cocatalyst further includes a site-selective cocatalyst;

[0027] The site-selective cocatalysts include organosulfur compounds.

[0028] This invention provides a method for preparing sulfinic acid compounds by sulfinization, comprising the following steps: under a protective atmosphere and light irradiation, an alkyl compound is reacted with a sulfur dioxide donor under catalytic conditions to obtain an alkyl sulfinic acid compound. Specifically, alkyl compounds with multiple reaction sites can be regioselectively reacted with organosulfides (such as benzo[a]naphthalene(1,2-D]thiazole, thiamethoxam, etc.) to obtain regioselective alkyl sulfinic acids. Alkalinization of alkyl sulfinic acids can yield alkyl sulfonates; alkalization and oxidation of alkyl sulfinic acids can yield alkyl sulfonate compounds; alkyl sulfinic acids can react with one or more of electrophilic reagents, oxidative functionalizing reagents, nucleophilic reagents, etc., to obtain alkyl sulfonyl compounds; the catalyst includes a main catalyst and a co-catalyst; the main catalyst includes a metal salt, wherein the metal element in the metal salt includes one or more of Fe, Cu, and Ce; the co-catalyst includes one or more of chlorosilanes, tetraalkylammonium chloride, alkali metal chlorides, and hydrochloric acid. The method in this invention has high catalytic efficiency (TON>350000, TOF>50000 / h), high selectivity (selectivity of sulfurous acid conversion>99%), high conversion rate (sulfurous acid is close to complete conversion), and low cost, high atom economy, and the production process generates virtually no waste, making it green, low-carbon and environmentally friendly. Attached Figure Description

[0029] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0030] Figure 1 The above is the 1H NMR spectrum of the product prepared by FeCl3 as the main catalyst in Example 1 of this invention.

[0031] Figure 2 The image shows the carbon NMR spectrum of the product prepared by FeCl3 as the main catalyst in Example 1 of this invention.

[0032] Figure 3 The above is the 1H NMR spectrum of the main product prepared by using isobutane as a substrate in Example 12 of this invention.

[0033] Figure 4 The carbon NMR spectrum of the main product prepared using isobutane as a substrate in Example 12 of this invention;

[0034] Figure 5 The above is the 1H NMR spectrum of the minor product prepared using isobutane as a substrate in Example 12 of this invention.

[0035] Figure 6 The carbon NMR spectrum of the minor product prepared using isobutane as a substrate in Example 12 of this invention;

[0036] Figure 7 The above is the 1H NMR spectrum of the product prepared using ethane as a substrate in Example 13 of this invention.

[0037] Figure 8 The image shows the carbon NMR spectrum of the product prepared using ethane as a substrate in Example 13 of this invention.

[0038] Figure 9 The above is the 1H NMR spectrum of the product prepared using methane as a substrate in Example 14 of this invention.

[0039] Figure 10 The image shows the carbon NMR spectrum of the product prepared using methane as a substrate in Example 14 of this invention.

[0040] Figure 11 The 1H NMR spectrum of the product prepared by the gram-scale reaction using butane as a substrate in Example 16 of this invention;

[0041] Figure 12 The carbon NMR spectrum of the product prepared by the gram-scale reaction using butane as a substrate in Example 16 of this invention;

[0042] Figure 13 The above is the 1H NMR spectrum of the alkyl sulfinate prepared using NaOH and Na2CO3 as bases in Example 21 of this invention.

[0043] Figure 14 The carbon NMR spectrum of the alkyl sulfinates prepared using NaOH and Na2CO3 as alkalis in Example 21 of this invention;

[0044] Figure 15 The above is the 1H NMR spectrum of the alkyl sulfonate prepared in Example 22 of this invention using NaOH as a base, reacting for 10 hours under an air atmosphere.

[0045] Figure 16 The above is the 1H NMR spectrum of the sulfonamide prepared in Example 23 of this invention;

[0046] Figure 17 The image shows the carbon NMR spectrum of the sulfonamide prepared in Example 23 of this invention.

[0047] Figure 18 The 1H NMR spectrum of the sulfonate ester prepared in Example 24 of this invention;

[0048] Figure 19 The carbon NMR spectrum of the sulfonate ester prepared in Example 24 of this invention;

[0049] Figure 20 The 1H NMR spectrum of the sulfonyl fluoride prepared in Example 25 of this invention;

[0050] Figure 21 The carbon NMR spectrum of the sulfonyl fluoride prepared in Example 25 of this invention;

[0051] Figure 22 The NMR spectrum of sulfonyl fluoride prepared in Example 25 of this invention;

[0052] Figure 23 The 1H NMR spectrum of the product prepared using 3-pentanone as a substrate in Example 26 of this invention;

[0053] Figure 24 The carbon NMR spectrum of the product prepared using 3-pentanone as a substrate in Example 26 of this invention;

[0054] Figure 25 The above is the 1H NMR spectrum of the product prepared using n-pentane as a substrate in Example 27 of this invention.

[0055] Figure 26 The image shows the carbon NMR spectrum of the product prepared using n-pentane as a substrate in Example 27 of this invention.

[0056] Figure 27The 1H NMR spectrum of the product prepared using 2,3-dimethylbutane as a substrate in Example 28 of this invention;

[0057] Figure 28 This is the carbon NMR spectrum of the product prepared using 2,3-dimethylbutane as a substrate in Example 28 of the present invention;

[0058] Figure 29 The above is the 1H NMR spectrum of the product prepared using cyclohexanone as a substrate in Example 29 of this invention.

[0059] Figure 30 The carbon NMR spectrum of the product prepared using cyclohexanone as a substrate in Example 29 of this invention;

[0060] Figure 31 The yields of different liquid alkane substrates in Example 11 of this invention;

[0061] Figure 32 The yields of different gaseous alkane substrates in Example 12 of this invention;

[0062] Figure 33 The yields of different substrates in Example 26 of this invention;

[0063] Figure 34 The yields of different open-chain alkane substrates in Example 27 of this invention;

[0064] Figure 35 The yields of branched-chain alkane substrates with different structures in Example 28 of this invention;

[0065] Figure 36 This demonstrates the selective reaction effect of cyclic alkanes with multiple reaction sites in Example 29 of the present invention.

[0066] Figure 37 This demonstrates the effect of the sulfur-containing organic reagent on the selective reaction of methyl valerate in Example 30 of the present invention. Detailed Implementation

[0067] This invention provides a method for preparing sulfinic acid compounds by sulfinylation, comprising the following steps:

[0068] Under a protective atmosphere and light conditions, alkyl compounds are subjected to sulfinylation with sulfur dioxide donors under catalytic conditions to obtain alkyl sulfinic acid compounds.

[0069] The sulfur dioxide donor includes one or more of the following: sulfurous acid solution (aqueous sulfur dioxide solution), 1,4-diazabicyclo[2.2.2]octane-1,4-dion-1,4-disulfinate (DABSO), K2S2O5, Na2S2O5, and sulfur dioxide gas.

[0070] The catalyst includes a main catalyst and a co-catalyst;

[0071] The main catalyst comprises a metal salt, wherein the metal element in the metal salt includes one or more of Fe, Cu and Ce; the co-catalyst comprises one or more of chlorosilane, tetraalkylammonium chloride, alkali metal chloride and hydrochloric acid.

[0072] In this invention, the sulfinylation reaction prepares alkyl sulfinic acid as shown in Formula I:

[0073] Formula I.

[0074] Wherein, R refers to alkyl; M refers to catalyst; cat. refers to catalytic amount; [Cl] refers to chloride ion donor in the cocatalyst; [S] refers to optional organosulfur compounds in the cocatalyst; and hν refers to light irradiation.

[0075] In this invention, the alkyl compound is preferably a substituted or unsubstituted C1-C20 alkyl compound. The unsubstituted C1-C20 alkyl compound preferably includes one or more of C1-C20 straight-chain alkanes, C1-C20 branched alkanes, and C3-C10 cycloalkanes, and can be gaseous and / or liquid alkanes, such as one or more of methane, ethane, propane, n-butane, isobutane, n-pentane, n-hexane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. The substituted C1-C20 alkyl compound is a C1-C20 alkyl compound that is not substituted. Based on the structure of a substituted C1-C20 alkyl compound, an alkyl compound substituted by a primary substituent, wherein the primary substituent preferably includes one or more of the following: hydroxyl, carbonyl, C4-C20 aromatic group, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C1-C10 ester group, cyano, halogen group, amino, C2-C10 alkenyl, C2-C10 alkynyl, C1-C10 amino, amide, C1-C10 sulfonyl, C1-C10 sulfinyl, and C1-C10 alkoxy.

[0076] In some embodiments of the present invention, the primary substituent may be further replaced by a secondary substituent, which preferably includes one or more of the following: hydroxyl, C1-C10 alkyl, C1-C10 cycloalkyl, C3-C20 heterocycloalkyl, C1-C10 alkoxy, C4-C10 heteroaryl, C2-C10 alkenyl, C2-C10 alkynyl, carbonyl, cyano, C1-C10 silyl, C1-C10 ester, amino, C1-C10 amine, amide, C1-C10 sulfonyl, C1-C10 sulfinyl, halogen, nitro, mercapto, carboxyl, and phenyl.

[0077] In some embodiments of the present invention, the C1-C10 ester groups in the primary and secondary substituents can be one or more of C1-C10 straight-chain ester groups, C1-C10 branched-chain ester groups, and C3-C10 lactone groups; the C1-C10 alkoxy groups in the primary and secondary substituents can be one or more of C1-C10 straight-chain alkoxy groups, C3-C10 branched-chain alkoxy groups, and C3-C10 cycloalkoxy groups; the heteroatoms in the C3-C20 heterocyclic alkyl groups in the primary and secondary substituents can be one or more of O, N, and S; the amide groups in the primary and secondary substituents can be amide groups and / or lactam groups, wherein the amide group can be one or more of primary amide groups (-CONH2), C2-C10 secondary amide groups, and C3-C10 tertiary amide groups. The lactam group can be a C3-C10 lactam group; the C1-C10 sulfonyl group in the primary and secondary substituents can be a C1-C10 chain sulfonyl group and / or a C2-C10 cyclic sulfone group; the C1-C10 sulfinyl group in the primary and secondary substituents can be a C1-C10 chain sulfinyl group and / or a C2-C10 cyclic sulfoxide group; the amine group in the primary and secondary substituents can be one or more of primary amine, secondary amine and tertiary amine groups; the substituted or unsubstituted C4-C20 aromatic group in the primary and secondary substituents preferably includes one or more of substituted or unsubstituted C6-C20 phenyl, substituted or unsubstituted C6-C20 fused-ring aryl, substituted or unsubstituted C4-C20 heteroaryl, and substituted or unsubstituted C4-C20 fused-heterocyclic aryl.

[0078] In this invention, the term "substitution" can refer to the substitution of hydrogen atoms or the substitution of carbon atoms.

[0079] In this invention, the sulfur dioxide donor is preferably a sulfurous acid solution (an aqueous solution of sulfur dioxide), and the concentration of the sulfurous acid solution is preferably 0.5~3 mol / L, more preferably 1~2.5 mol / L, such as 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, preferably within the range of any of the above values ​​as the upper or lower limit. The ratio of the molar number of sulfur dioxide in the sulfur dioxide donor to the molar number of alkyl compounds is preferably 1:(1~80), more preferably 1:(1~40), such as 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0080] In this invention, the catalyst comprises a main catalyst and a co-catalyst. The main catalyst preferably comprises a metal salt, and the metal in the metal salt preferably comprises one or more of Fe, Cu, and Ce, more preferably a metal salt containing Fe. The metal salt preferably comprises one or more of metal halides, sulfates, nitrates, acetates, trifluoromethanesulfonates, tetrafluoroborates, hexafluorophosphates, trifluoroacetates, citrates, oxalates, acrylates, tris(2,2,6,6-tetramethyl-3,5-heptadecanoic acid) salts, and acetylacetone salts. The metal halide is preferably one or more of metal chlorides, metal bromides, metal iodides, and metal fluorides. Specifically, in some embodiments of this invention, the main catalyst can be one or more of ferric halides (such as ferric chloride, ferric bromide), ferrous halides (such as ferrous chloride, ferrous bromide), copper chloride, cuprous chloride, and cerium chloride. The molar ratio of the metal element in the main catalyst to the sulfur dioxide in the sulfur dioxide donor is preferably 1:(20). (~1000000), more preferably 1:(20~10000), such as 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:67, 1:70, 1:75, 1:80, 1:83, 1:90, 1:95, 1:100, 1:200, 1:500, 1:1000, 1:5000, 1:10000, 1:100000, 1:100000, 1:1000000, preferably any of the above. The numerical value is a range of upper or lower limits; the molar ratio of the metal element to the alkyl compound in the main catalyst is preferably 1:(20~8000000), more preferably 1:(20~80000), such as 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:67, 1:70, 1:75, 1:80, 1:83, 1:90, 1:95, 1:100, 1:150, 1:200, 1:250. 1:300, 1:350, 1:400, 1:450, 1:500, 1:550, 1:600, 1:650, 1:700, 1:750, 1:800, 1:850, 1:900, 1:950, 1:1000, 1:2000, 1:5000, 1:10000, 1:50000, 1:100000, 1:1000000, 1:5000000, 1:8000000, preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0081] In this invention, the chloride-containing co-catalyst assists the metal element in the main catalyst in forming a complex of metal and chloride ions, such as ferric chloride complex. Ferric chloride is excited under light to generate ferrous iron and chloride radicals. The chloride radicals abstract hydrogen from the alkyl C-H bonds to generate alkyl radicals, which capture sulfur dioxide to obtain alkyl sulfinyl radicals. These radicals further oxidize ferrous iron to ferric iron, generating alkyl sulfinic acid, thus completing the catalytic cycle. The co-catalyst preferably comprises one or more of chlorosilanes, tetraalkylammonium chloride, alkali metal chlorides, and hydrochloric acid. Preferably, the chlorosilane is a C1-C30 alkylchlorosilane, more preferably trimethylchlorosilane. The tetraalkylammonium chloride comprises one or more of tetramethylammonium chloride, tetraethylammonium chloride, and tetrabutylammonium chloride. The alkali metal chloride is one or more of LiCl, NaCl, KCl, and CsCl. The molar ratio of the metal element in the main catalyst to the chloride-containing co-catalyst is preferably 1:(4~200000), more preferably 1:(4~2000), such as 1:4, 1:4.5, 1:5, 1:5.5, 1: 6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000, 1:2000, 1:5000, 1:10000, 1:100000, 1:200000, preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0082] In this invention, when the alkyl compound has multiple reaction sites, the cocatalyst further includes a site-selective cocatalyst; the site-selective cocatalyst includes an organosulfur compound, which can improve the selectivity of the reaction, enabling the multi-site reaction substrate to achieve regioselective reaction results. The site-selective cocatalyst preferably includes one or more of phenyl sulfide derivatives and thiophene derivatives. Preferably, the phenyl sulfide derivative includes one or more of methylphenyl sulfide, diphenyl sulfide, thiane, phenoxthiazide, 10-methylphenthiazide, and 10-phenylphenthiazide; the thiophene derivative includes one or more of dibenzothiophene, benzo[1,2-D]thiazole, and benzo[B]naphthalene[1,2-D]thiophene (BNT). The molar ratio of the metal element in the main catalyst to the site-selective co-catalyst is preferably 1:(0.1~100), more preferably 1:(0.5~40), such as 1:0.5, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18, 1:20, 1:22, 1:25, 1:30, 1:35, 1:40, preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0083] In this invention, the sulfinylation reaction is preferably carried out under a protective atmosphere, which preferably includes nitrogen and / or argon.

[0084] In this invention, the sulfinylation reaction is carried out in a solvent environment, wherein the solvent preferably includes water and / or an organic solvent, more preferably a mixture of water and an organic solvent, wherein the organic solvent is preferably one or more of acetonitrile, acetone, ethyl acetate, dichloromethane, 1,2-dichloroethane and chloroform; the volume ratio of water to organic solvent is preferably 1:(0~9), more preferably 1:(1~8), such as 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0085] In this invention, the sulfinylation reaction is carried out under illumination by a light source. The wavelength of the light source is preferably 365-400 nm, and the power of the light source is preferably 5-100 W, more preferably 10-90 W, such as 5 W, 10 W, 15 W, 20 W, 25 W, 30 W, 35 W, 40 W, 45 W, 50 W, 55 W, 60 W, 65 W, 70 W, 75 W, 80 W, 85 W, 90 W, 95 W, 100 W, preferably within the range of values ​​above, which may be the upper or lower limit.

[0086] In this invention, the temperature of the sulfinylation reaction is preferably room temperature, such as 20~35°C, more preferably 25~30°C; the time of the sulfinylation reaction is preferably 7~36 hours, more preferably 10~25 hours, such as 7 hours, 10 hours, 15 hours, 18 hours, 19 hours, 20 hours, 25 hours, 30 hours, 36 hours, preferably within the range of any of the above values ​​as the upper or lower limit; the pressure of the sulfinylation reaction is preferably 0.1~5 MPa, such as 0.1 MPa, 0.5 MPa, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, 3 MPa, 3.5 MPa, 4 MPa, 4.5 MPa, 5 MPa, preferably within the range of any of the above values ​​as the upper or lower limit.

[0087] Furthermore, the present invention allows the prepared alkyl sulfinic acid compound to be directly neutralized with a base without separation, thus preparing alkyl sulfinates in a one-pot process, as shown in Formula II:

[0088] Formula II.

[0089] Wherein, R refers to alkyl; M refers to catalyst; cat. refers to catalytic amount; [Cl] refers to chloride ion donor in the cocatalyst; [S] refers to optional organosulfur compounds in the cocatalyst; hν refers to light irradiation; and M′ refers to the metal ion of the basic reagent.

[0090] In this invention, the alkaline reagent is preferably one or more of Na2CO3, NaOH, K2CO3, KOH, K2HPO4, Na3PO4, Na2HPO4, Li2CO3, LiOH and Cs2CO3, and the molar ratio of sulfur dioxide in the sulfur dioxide donor to the alkaline reagent is preferably 1:(1~3), more preferably 1:(1~2).

[0091] In this invention, the temperature of the neutralization reaction between the alkyl sulfinic acid compound and the alkaline reagent is preferably 20~35°C, more preferably 25~30°C, such as room temperature; the pressure of the neutralization reaction is preferably atmospheric pressure; and the time of the neutralization reaction is preferably 8~16 hours, more preferably 10~12 hours.

[0092] Furthermore, the present invention allows the prepared alkyl sulfinic acid compound to be directly neutralized with a base in an oxygen-containing atmosphere without separation, thus preparing alkyl sulfinates in a one-pot process, as shown in Formula III:

[0093] Formula III.

[0094] Wherein, R refers to alkyl; M refers to catalyst; cat. refers to catalytic amount; [Cl] refers to chloride ion donor in the cocatalyst; [S] refers to optional organosulfur compounds in the cocatalyst; hν refers to light irradiation; and M′ refers to the metal ion of the basic reagent.

[0095] In this invention, the alkaline reagent is preferably one or more of Na2CO3, NaOH, K2CO3, KOH, NaHCO3, Na3PO4, Li2CO3, LiOH and Cs2CO3, and the molar ratio of sulfur dioxide in the sulfur dioxide donor to the alkaline reagent is preferably 1:(1~3), more preferably 1:(1~2); the oxygen-containing atmosphere is preferably air and / or oxygen.

[0096] In this invention, the temperature of the neutralization reaction between the alkyl sulfinic acid compound and the alkaline reagent in an oxygen-containing atmosphere is preferably 20~35°C, more preferably 25~30°C, such as room temperature. The pressure of the neutralization reaction is preferably atmospheric pressure, and the time of the neutralization reaction is preferably 8~16 hours, more preferably 10~12 hours.

[0097] Furthermore, this invention allows for the direct reaction of the prepared alkyl sulfinic acid compound with an electrophilic reagent in the presence of a basic reagent, without the need for separation, thus preparing an alkyl sulfone compound in a one-pot process, as shown in Formula IV:

[0098] Formula IV.

[0099] Where R refers to alkyl; M refers to catalyst; cat. refers to catalytic amount; [Cl] refers to chloride ion donor in the co-catalyst; [S] refers to optional organosulfur compounds in the co-catalyst; hν refers to light irradiation; E + R' refers to an electrophilic reagent; R′ refers to the hydrocarbon group in a haloalkanes.

[0100] In this invention, the electrophilic reagent is preferably a haloalkane, more preferably one or more of 3-bromopropene, benzyl bromide, iodomethane and methyl chloroacetate; the basic reagent is preferably one or more of NaHCO3, Na2CO3 and NaOH; the molar ratio of sulfur dioxide to haloalkane in the sulfur dioxide donor is preferably 1:(1~5), more preferably 1:(2~4); the molar ratio of sulfur dioxide in the sulfur dioxide donor to the molar ratio of basic reagent is preferably 1:(1~3), more preferably 1:(1~2).

[0101] In this invention, the reaction temperature of the alkyl sulfinic acid compound with the electrophilic reagent is preferably 60-80°C, more preferably 65-75°C, the reaction time is preferably 5-6 hours, and the reaction pressure is preferably atmospheric pressure.

[0102] Furthermore, the present invention can react the prepared alkyl sulfinic acid compound with Selectfluor under alkaline conditions to obtain an alkyl sulfonyl fluoride compound; or react the alkyl sulfinic acid compound with an oxidizing functionalizing agent and a nucleophilic agent simultaneously to obtain an alkyl sulfonate compound or an alkyl sulfonamide compound, as shown in Formula V:

[0103] Formula V.

[0104] Wherein, R refers to alkyl; M refers to catalyst; cat. refers to catalytic amount; [Cl] refers to chloride ion donor in the cocatalyst; [S] refers to optional organosulfur compounds in the cocatalyst; hν refers to light irradiation; and [O] represents oxidative functionalizing agent.

[0105] In this invention, the selective fluorine reagent preferably includes Selectfluor; the reaction temperature of the alkyl sulfinic acid compound with the selective fluorine reagent is preferably room temperature, such as 20~35°C, more preferably 25~30°C, the reaction time is preferably 0.5~2 hours, more preferably 1~1.5 hours, and the pressure is preferably atmospheric pressure.

[0106] In this invention, the alkaline reagent is preferably NaHCO3 and / or Na2CO3, and the oxidative functionalizing reagent is preferably one or more of PhI(OAc)2, NaClO, and NCS (N-chlorosuccinimide); the nucleophile is preferably an alcohol or amine, such as one or more of methanol, ethanol, isopropanol, tetrahydropyrrole, morpholine, and aniline; the molar ratio of sulfur dioxide donor to oxidative functionalizing reagent is 1:(1~3); the reaction temperature is preferably 0~35℃, more preferably 0~30℃, such as 0℃, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, preferably a range of values ​​with any of the above values ​​as the upper or lower limit; the reaction time is preferably 1~3 hours, and the reaction pressure is preferably atmospheric pressure.

[0107] This invention provides a method for preparing sulfonyl compounds by sulfinization, comprising the following steps: under a protective atmosphere and light irradiation, an alkyl compound is reacted with a sulfurous acid solution under catalytic conditions to undergo a sulfinization reaction to obtain alkyl sulfinic acid. Specifically, alkyl compounds with multiple reaction sites can be regioselectively reacted with organosulfides (such as benzo[1,2-D]thiazole, thiamethoxam, etc.) to obtain regioselective alkyl sulfinic acids. Alkalinization of alkyl sulfinic acids yields sodium sulfite; alkalization and oxidation of alkyl sulfinic acids yields sodium sulfonate; alkyl sulfinic acids react with one or more of electrophilic reagents, oxidative functionalizing reagents, nucleophilic reagents, etc., to obtain alkyl sulfonyl compounds; the catalyst includes a main catalyst and a co-catalyst; the main catalyst includes a metal salt, wherein the metal element in the metal salt includes one or more of Fe, Cu, and Ce; the co-catalyst includes one or more of chlorosilanes, tetraalkylammonium chloride, alkali metal chlorides, hydrochloric acid, and organosulfides. The method in this invention has high catalytic efficiency (TON>350000, TOF>50000 / h), high selectivity (selectivity of sulfurous acid conversion>99%), high conversion rate (sulfurous acid is close to complete conversion), and low cost, high atom economy, and the production process generates virtually no waste, making it green, low-carbon and environmentally friendly.

[0108] To further illustrate the present invention, the following detailed description of a method for preparing sulfinic acid compounds, sulfinate compounds, sulfonate compounds, and sulfonyl compounds by sulfinylation, in conjunction with embodiments, is provided by the present invention, but should not be construed as limiting the scope of protection of the present invention.

[0109] The abbreviations used in the following embodiments are:

[0110] Tetrabutylammonium chloride (TBACl), trimethylchlorosilane (TMSCl), 1,4-diazabicyclo[2.2.2]octane-1,4-dion-1,4-disulfinic acid (DABSO), dichloromethane (DCM), thiathracene (TT), benzo[B]naphthalene[1,2-D]thiophene (BNT).

[0111] Example 1: Effect of the type of main catalyst on the reaction

[0112]

[0113] Specific steps: Taking FeCl3 as an example, before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution. In a nitrogen glove box, cyclohexane (216 μL, 2 mmol, 4 eq.), FeCl3 (0.5 mL, 0.001 M, 0.1 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and sulfurous acid solution (0.5 mL, 1.0 M, 0.5 mmol, 1.0 eq.) was added to the reaction solution using a syringe. Subsequently, the reaction solution was allowed to react at room temperature for 7 hours under 50 W 365 nm LED illumination.

[0114] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), benzyl bromide (119 μL, 1 mmol, 2 eq.), and methanol (1 mL) were added to the reaction solution, and the reaction was carried out at 65 °C for 4 hours. The product was characterized by NMR. 1 H NMR (400 MHz, CDCl3)δ 7.40 (d, J = 2.1 Hz, 5H), 4.20 (d, J = 1.9 Hz, 2H), 2.73 (tt, J = 12.2, 3.2Hz, 1H), 2.13 (m, 2H), 1.98 – 1.83 (m, 2H), 1.75 – 1.64 (m, 1H), 1.63 – 1.49 (m, 2H), 1.23 (m, 3H). 13 C NMR (101 MHz, CDCl3) δ 130.6, 129.0, 128.9, 127.9, 59.0, 56.1, 25.1, 25.0, 25.0.

[0115] Specifically, such as Figures 1-2 As shown, Figure 1 The above is the 1H NMR spectrum of the product prepared by FeCl3 as the main catalyst in Example 1 of this invention. Figure 2 The image shows the carbon NMR spectrum of the product prepared by FeCl3 as the main catalyst in Example 1 of this invention.

[0116] Other embodiments simply require replacing FeCl3 with an equimolar amount of a metal salt, with all other steps remaining the same. The gas-phase yield was determined using mesitylene as an internal standard, and the results are shown in Table 1.

[0117] Table 1. Effect of main catalyst type on the reaction

[0118]

[0119] As shown in Table 1, FeCl3 works very well as the main catalyst, and other metal salts also show moderate to excellent yields.

[0120] Example 2: Effect of Co-catalyst Type

[0121]

[0122] Specific steps: Taking TBACl as an example, in a nitrogen glove box, cyclohexane (54 μL, 0.5 mmol, 4 eq.), FeCl3 (4.1 mg, 0.025 mmol, 5 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4.5 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and sulfurous acid solution (0.5 mL, 1.0 M, 0.5 mmol, 1.0 eq.) was added to the reaction solution using a syringe. Subsequently, the reaction solution was allowed to react at room temperature for 7 hours under 50 W 365 nm LED illumination.

[0123] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), benzyl bromide (119 μL, 1 mmol, 2 eq.) and methanol (1 mL) were added to the reaction solution, and the reaction solution was reacted at 65 °C for 4 hours.

[0124] Other embodiments simply involve replacing TBACl with a different type of chloride; the other steps remain the same. The gas-phase yield was determined using mesitylene as an internal standard, and the results are shown in Table 2.

[0125] Table 2 Effect of type of co-catalyst on the reaction

[0126]

[0127] As shown in Table 2, TBACl is more effective as a co-catalyst than other chlorides.

[0128] Example 3 Effect of Co-catalyst Dosage

[0129]

[0130] Specific steps: Taking 20 mol% TBACl as an example, before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution. In a nitrogen glove box, cyclohexane (216 μL, 2 mmol, 4 eq.), FeCl3 (0.5 mL, 0.001 M, 0.1 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and sulfurous acid solution (0.5 mL, 1.0 M, 0.5 mmol, 1.0 eq.) was added to the reaction solution using a syringe. Subsequently, the reaction solution was reacted at room temperature for 7 hours under 50 W 365 nm LED light.

[0131] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), benzyl bromide (119 μL, 1 mmol, 2 eq.) and methanol (1 mL) were added to the reaction solution, and the reaction solution was reacted at 65 °C for 4 hours.

[0132] Other embodiments only require changing the amount of TBACl, while the other steps remain the same. The gas phase yield was determined using mesitylene as an internal standard, and the results are shown in Table 3.

[0133] Table 3 Effect of co-catalyst dosage on the reaction

[0134]

[0135] As shown in Table 3, both decreasing and increasing the amount of TBACl will lead to a worse reaction effect.

[0136] Example 4 Effect of Alkane Equivalent

[0137]

[0138] Specific steps: Taking cyclohexane as 1 eq. and FeCl3 as 0.1 mol% as an example, before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3-acetonitrile solution. In a nitrogen glove box, alkane (54 μL, 0.5 mmol, 4 eq.), FeCl3 (0.5 mL, 0.001 M, 0.1 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and sulfurous acid solution (0.5 mL, 1.0 M, 0.5 mmol, 1.0 eq.) was added to the reaction solution using a syringe. Subsequently, the reaction solution was reacted at room temperature for 7 hours under 50 W 365 nm LED light source illumination.

[0139] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), benzyl bromide (119 μL, 1 mmol, 2 eq.) and methanol (1 mL) were added to the reaction solution, and the reaction solution was reacted at 65 °C for 4 hours.

[0140] Other embodiments only require changing the amount of FeCl3 or cyclohexane; the other steps are the same. The gas-phase yield was determined using mesitylene as an internal standard, and the results are shown in Table 4.

[0141] Table 4 Effect of alkane equivalent on the reaction

[0142]

[0143] As shown in Table 4, higher amounts of FeCl3 and cyclohexane can improve the reaction conversion rate, and the reaction has extremely high catalytic efficiency.

[0144] Example 5: Effect of Organic Solvent Type

[0145]

[0146] Specific steps: Taking acetonitrile as an example, before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3-acetonitrile solution. In a nitrogen glove box, cyclohexane (216 μL, 2 mmol, 4 eq.), FeCl3 (0.5 mL, 0.001 M, 0.1 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and sulfurous acid solution (0.5 mL, 1.0 M, 0.5 mmol, 1.0 eq.) was added to the reaction solution using a syringe. Subsequently, the reaction solution was allowed to react at room temperature for 7 hours under 50 W 365 nm LED illumination.

[0147] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), benzyl bromide (119 μL, 1 mmol, 2 eq.) and methanol (1 mL) were added to the reaction solution, and the reaction solution was reacted at 65 °C for 4 hours.

[0148] Other embodiments simply require replacing all acetonitrile with other solvents, while keeping the other steps the same. The gas phase yield was determined using mesitylene as an internal standard, and the results are shown in Table 5.

[0149] Table 5. Effect of solvent type on the reaction

[0150]

[0151] As shown in Table 5, acetonitrile is a better solvent for the reaction than other solvents.

[0152] Example 6 Effect of Solvent Ratio

[0153]

[0154] Specific steps: Taking an acetonitrile to water volume ratio of 1:1 as an example, before each reaction, FeCl3 (1.6 mg, 0.01 mmol) is dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0155] In a nitrogen-filled glove box, cyclohexane (86 μL, 0.8 mmol, 4 eq.), FeCl3 (0.2 mL, 0.001 M, 0.1 mol%), TBACl (11.1 mg, 0.04 mmol, 0.2 eq.), acetonitrile, and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and sulfurous acid solution (0.2 mL, 1.0 M, 0.2 mmol, 1.0 eq.) was added to the reaction solution using a syringe. The reaction solution was then incubated at room temperature for 7 hours under a 50 W 365 nm LED light source.

[0156] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), benzyl bromide (119 μL, 1 mmol, 2 eq.) and methanol (1 mL) were added to the reaction solution, and the reaction solution was reacted at 65 °C for 4 hours.

[0157] Other embodiments only require the addition of additional water to the reaction to change the solvent ratio; the other steps are the same. The gas-phase yield was determined using mesitylene as an internal standard, and the results are shown in Table 6.

[0158] Table 6 Effect of solvent ratio on the reaction

[0159]

[0160] As shown in Table 6, the reaction effect is best when the volume ratio of acetonitrile to water is 9:1.

[0161] Example 7: The Influence of Light Source

[0162]

[0163] Specific steps: Taking a 50 W 365 nm LED light source as an example, before each reaction, FeCl3 (1.6 mg, 0.01 mmol) is dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0164] In a nitrogen-filled glove box, cyclohexane (216 μL, 2 mmol, 4 eq.), FeCl3 (0.5 mL, 0.001 M, 0.1 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and sulfurous acid solution (0.5 mL, 1.0 M, 0.5 mmol, 1.0 eq.) was added to the reaction solution using a syringe. The reaction solution was then incubated at room temperature for 7 hours under a 50 W 365 nm LED light source.

[0165] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), benzyl bromide (119 μL, 1 mmol, 2 eq.) and methanol (1 mL) were added to the reaction solution, and the reaction solution was reacted at 65 °C for 4 hours.

[0166] Other embodiments only require changing the wavelength and power of the light source; the other steps remain the same. The gas phase yield was determined using mesitylene as an internal standard, and the results are shown in Table 7.

[0167] Table 7 Effect of light source on reaction

[0168]

[0169] As shown in Table 7, the 50 W 365 nm LED light source has the best response effect. Reducing the power of the light source or extending the wavelength will lead to a worse response effect.

[0170] Example 8: Impact of SO2 Sources

[0171]

[0172] Specific steps: Taking sulfurous acid solution as an example, before each reaction, FeCl3 (1.6 mg, 0.01 mmol) is dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0173] In a nitrogen-filled glove box, cyclohexane (216 μL, 2 mmol, 4 eq.), FeCl3 (0.5 mL, 0.001 M, 0.1 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and sulfurous acid solution (0.5 mL, 1.0 M, 0.5 mmol, 1.0 eq.) was added to the reaction solution using a syringe. The reaction solution was then incubated at room temperature for 7 hours under a 50 W 365 nm LED light source.

[0174] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), benzyl bromide (119 μL, 1 mmol, 2 eq.) and methanol (1 mL) were added to the reaction solution, and the reaction solution was reacted at 65 °C for 4 hours.

[0175] Other embodiments simply require replacing the sulfurous acid solution with other SO2 sources and adding 0.5 mL of water to the reaction to maintain the same solvent ratio; all other steps remain the same. The gas-phase yield was determined using mesitylene as an internal standard, and the results are shown in Table 8.

[0176] Table 8. Effect of SO2 source on the reaction

[0177]

[0178] As shown in Table 8, the reaction is most effective when sulfurous acid solution is used as the SO2 source.

[0179] Example 9: The Influence of Light Source

[0180]

[0181] Specific steps: Taking a 50 W 365 nm LED light source as an example, before each reaction, FeCl3 (1.6 mg, 0.01 mmol) is dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0182] In a nitrogen-filled glove box, cyclohexane (216 μL, 2 mmol, 4 eq.), FeCl3 (0.5 mL, 0.001 M, 0.1 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and sulfurous acid solution (0.5 mL, 1.0 M, 0.5 mmol, 1.0 eq.) was added to the reaction solution using a syringe. The reaction solution was then incubated at room temperature for 7 hours under a 50 W 365 nm LED light source.

[0183] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), benzyl bromide (119 μL, 1 mmol, 2 eq.) and methanol (1 mL) were added to the reaction solution, and the reaction solution was reacted at 65 °C for 4 hours.

[0184] Other embodiments only require changing the wavelength and power of the light source; the other steps remain the same. The gas phase yield was determined using mesitylene as an internal standard, and the results are shown in Table 9.

[0185] Table 9 Effect of light source on reaction

[0186]

[0187] As shown in Table 9, the 50 W 365 nm LED light source has the best response effect, and the response effect will be worse if the wavelength is extended.

[0188] Example 10 Effect of Alkali

[0189]

[0190] Specific steps: Taking FeCl3 as an example, before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution. In a nitrogen glove box, cyclohexane (216 μL, 2 mmol, 4 eq.), FeCl3 (0.5 mL, 0.001 M, 0.1 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and sulfurous acid solution (0.5 mL, 1.0 M, 0.5 mmol, 1.0 eq.) was added to the reaction solution using a syringe. Subsequently, the reaction solution was allowed to react at room temperature for 7 hours under 50 W 365 nm LED illumination.

[0191] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), benzyl bromide (119 μL, 1 mmol, 2 eq.) and methanol (1 mL) were added to the reaction solution, and the reaction solution was reacted at 65 °C for 4 hours.

[0192] Other embodiments only require changing the type of alkali; the other steps remain the same. The gas phase yield was determined using mesitylene as an internal standard, and the results are shown in Table 10.

[0193] Table 10 Effect of base on reaction

[0194]

[0195] As shown in Table 10, both inorganic and organic bases are effective for the reaction, with NaHCO3, Na3PO4, DIPEA, and Collidine showing the best results and yielding near-equivalent yields.

[0196] Example 11 Liquid Alkane Substrate Expansion

[0197]

[0198] In the above reaction formula, R1 and R2 are substituents, representing substrates with different structures. Specifically, the substrate structures are cyclohexane, cyclopentane, cycloheptane, cyclooctane, n-hexane, and 2,3-dimethylbutane.

[0199] Specific steps: Taking cyclohexane as an example, before each reaction, FeCl3 (1.6 mg, 0.01 mmol) is dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0200] In a nitrogen-filled glove box, cyclohexane (216 μL, 2 mmol, 4 eq.), FeCl3 (0.5 mL, 0.001 M, 0.1 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and sulfurous acid solution (0.5 mL, 1.0 M, 0.5 mmol, 1.0 eq.) was added to the reaction solution using a syringe. The reaction solution was then incubated at room temperature for 7 hours under a 50 W 365 nm LED light source.

[0201] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), benzyl bromide (119 μL, 1 mmol, 2 eq.) and methanol (1 mL) were added to the reaction solution, and the reaction solution was reacted at 65 °C for 4 hours.

[0202] After the reaction is complete, when it is necessary to determine the crude yield, mesitylene is added to the reaction solution as an internal standard. After shaking well, a small amount of the reaction solution is taken for gas chromatography-mass spectrometry analysis of the conversion and yield. When it is necessary to separate the product, the reaction solution is poured into 30 mL of water and extracted with DCM (4 × 15 mL). The resulting organic phase is dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography to obtain the product.

[0203] Other embodiments only require changing the type of alkane; the other steps remain the same. Yields are as follows: Figure 31 As shown, Figure 31 The yields of different liquid alkane substrates in Example 11 of this invention are given.

[0204] Figure 31 In the diagram, the circular shading represents the minor regioisomer, a, b, and c represent different reaction sites, and the product ratios for the corresponding reaction sites are indicated in the parentheses below. rr indicates the selection ratio for different reaction sites.

[0205] Example 12: Gaseous Alkane Substrate Expansion

[0206]

[0207] In the above reaction formula, R1 and R2 are substituents, representing gaseous alkane substrates with different structures, specifically butane, isobutane, and propane.

[0208] Specific steps: Taking isobutane as an example, before each reaction, FeCl3 (1.6 mg, 0.01 mmol) is dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0209] In a nitrogen-filled glove box, FeCl3 (0.05 mL, 0.001 M, 0.01 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4.45 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and the gas in the flask was replaced with gaseous alkanes by bubbling for 10 minutes in an ice bath. Then, 0.5 mL of sulfurous acid solution, pre-diluted to 1 M, was added to the reaction solution using a syringe. Subsequently, the reaction solution was allowed to react at room temperature for 7 hours under 50 W 365 nm LED illumination.

[0210] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), benzyl bromide (119 μL, 1 mmol, 2 eq.), and methanol (1 mL) were added to the reaction solution, and the reaction was carried out at 65 °C for 4 hours. After the reaction was completed, the reaction solution was poured into 30 mL of water and extracted with DCM (4 × 15 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography to obtain the product. NMR characterization of the product: Primary product: 1 H NMR (400 MHz, CDCl3) δ 7.39 (brs, 5H), 4.20 (s, 2H), 2.72 (d, J = 6.6 Hz, 2H), 2.31 (dh, J = 13.3, 6.7 Hz, 1H), 1.07 (d, J = 6.7Hz, 6H). 13 C NMR (101 MHz, CDCl3) δ 130.6, 129.1, 129.0, 128.3, 60.7, 58.4, 23.5, 22.8. Tertiary products: 1 H NMR (400 MHz, CDCl3) δ 7.54 – 7.32 (m, 5H), 4.19 (s,2H), 1.43 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 131.2, 128.7, 127.2, 60.0, 52.8,23.8.

[0211] Specifically, such as Figures 3-6 As shown, Figure 3 The above is the 1H NMR spectrum of the main product prepared by using isobutane as a substrate in Example 12 of this invention. Figure 4 The carbon NMR spectrum of the main product prepared using isobutane as a substrate in Example 12 of this invention; Figure 5 The above is the 1H NMR spectrum of the minor product prepared using isobutane as a substrate in Example 12 of this invention. Figure 6 The image shows the carbon NMR spectrum of the minor product prepared using isobutane as a substrate in Example 12 of this invention.

[0212] Other embodiments only require changing the type of alkane; the other steps remain the same. Yields are as follows: Figure 32 As shown, Figure 32 The yields of different gaseous alkane substrates in Example 12 of this invention are given.

[0213] Figure 32In the diagram, the circular shading represents the minor regioisomer, and the proportion of the product at the corresponding reaction position is indicated in the corresponding parentheses below. rr indicates the selection ratio of different reaction positions.

[0214] Example 13 Reaction of ethane

[0215]

[0216] Specific steps: Before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0217] In a nitrogen-filled glove box, FeCl3 (0.05 mL, 0.001 M, 0.01 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4.45 mL), and a magnetic stirrer were added to a high-pressure photoreactor. The reactor was then removed from the glove box, and 0.5 mL of sulfurous acid solution diluted to 1 M was added. The high-pressure photoreactor was then completely sealed. The reactor was purged three times with 3 MPa ethane, followed by 3 MPa ethane refill. Subsequently, the reaction solution was allowed to react at room temperature for 7 hours under 50 W 365 nm LED illumination.

[0218] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), benzyl bromide (119 μL, 1 mmol, 2 eq.), and methanol (1 mL) were added to the reaction solution, and the reaction was carried out at 65 °C for 4 hours. After the reaction was completed, the reaction solution was poured into 30 mL of water and extracted with DCM (4 × 15 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography to obtain a white solid product. The yield was 94%, and the tonnage (TON) was 9400. NMR characterization of the product: 1 H NMR (400 MHz, CDCl3) δ 7.39(m, 5H), 4.21 (s, 2H), 2.84 (q, J = 7.5 Hz, 2H), 1.33 (t, J = 7.5 Hz, 3H). 13 CNMR (101 MHz, CDCl3) δ 130.5, 129.1, 129.0, 128.1, 58.7, 45.4, 6.4.

[0219] Specifically, such as Figures 7-8 As shown, Figure 7 The above is the 1H NMR spectrum of the product prepared using ethane as a substrate in Example 13 of this invention. Figure 8 The image shows the carbon NMR spectrum of the product prepared using ethane as a substrate in Example 13 of this invention.

[0220] Example 14 Screening of Methane Reaction Conditions

[0221]

[0222] Specific steps: Taking item 5 in Table 11 as an example, before each reaction, FeCl3 (162.2 mg, 1 mmol) is dissolved in acetonitrile (10 mL) to prepare a 0.1 M FeCl3 acetonitrile solution.

[0223] In a nitrogen-filled glove box, FeCl3 (0.02 mL, 0.1 M, 1 mol%), TBACl (11.1 mg, 0.04 mmol, 0.2 eq.), acetonitrile (4.48 mL), and a magnetic stirrer were added to a high-pressure photoreactor. The reactor was then removed from the glove box, and 0.5 mL of sulfurous acid solution diluted to 1 M was added. The high-pressure photoreactor was then completely sealed. The reactor was purged three times with 5 MPa methane, followed by refilling with 5 MPa methane. Subsequently, the reaction solution was allowed to react at room temperature for 36 hours under 50 W 365 nm LED illumination.

[0224] NaHCO3 (33.6 mg, 0.4 mmol, 2 eq.), benzyl bromide (48 μL, 0.4 mmol, 2 eq.), and methanol (1 mL) were added to the reaction solution, and the reaction was carried out at 65 °C for 4 hours. After the reaction was completed, the reaction solution was poured into 30 mL of water and extracted with DCM (4 × 15 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography to obtain a white solid product. The yield was 55%. NMR characterization of the product: 1 H NMR (400 MHz, CDCl3) δ 7.41 (s, 5H), 4.25 (s, 2H), 2.75 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 130.5, 129.2, 128.3, 61.3, 39.0.

[0225] Specifically, such as Figures 9-10 As shown, Figure 9 The above is the 1H NMR spectrum of the product prepared using methane as a substrate in Example 14 of this invention. Figure 10 This is the carbon NMR spectrum of the product prepared using methane as a substrate in Example 14 of this invention.

[0226] Other embodiments only require changing the amount of catalyst or the reaction time; the other steps are the same. The yield was determined by 1H NMR spectroscopy using CH2Br2 as an internal standard, and the results are shown in Table 11.

[0227] Table 11 Screening of reaction conditions for methane

[0228]

[0229] As shown in Table 11, since methane is relatively inert, it is necessary to increase the FeCl3 catalyst equivalent and extend the reaction time to improve the yield. The highest yield is 63% (as shown in Item 7), and the highest conversion number reaches 2600 (as shown in Item 1).

[0230] Example 15 Cyclooctane gram-scale reaction

[0231]

[0232] Specific steps: Before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0233] In a nitrogen-filled glove box, cyclohexane (3.46 mL, 32 mmol, 4 eq.), FeCl3 (0.8 mL, 0.001 M, 0.01 mol%), TBACl (444.7 mg, 1.6 mmol, 0.2 eq.), acetonitrile (72 mL), and a magnetic stir bar were added to a 150 mL Schlenk tube. The Schlenk tube was removed from the glove box, and under nitrogen purging, 8 mL of pre-diluted 1 M sulfurous acid solution was added. The reaction mixture was then incubated at room temperature for 10 hours under 50 W 365 nm LED illumination.

[0234] NaHCO3 (1.34 g, 16 mmol, 2 eq.), benzyl bromide (1.9 mL, 16 mmol, 2 eq.), and methanol (16 mL) were added to the reaction solution, and the mixture was reacted at 65 °C for 4 hours. After the reaction was completed, the reaction solution was poured into 100 mL of water and extracted with DCM (4 × 50 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and recrystallized (in n-hexane) to obtain a white solid product (1.64 g, 86%).

[0235] Example 16: Gram-scale reaction of isobutane, butane, and propane

[0236]

[0237] Specific steps: Taking butane as an example, before each reaction, FeCl3 (1.6 mg, 0.01 mmol) is dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0238] In a nitrogen-filled glove box, FeCl3 (0.8 mL, 0.001 M, 0.01 mol%), TBACl (444.7 mg, 1.6 mmol, 0.2 eq.), acetonitrile (72 mL), and a magnetic stir bar were added to a 150 mL Schlenk tube. The Schlenk tube was removed from the glove box, and the gas in the reaction flask was replaced with gaseous alkanes by bubbling for 10 minutes in an ice bath. Under alkane purging, 8 mL of pre-diluted 1 M sulfurous acid solution was added to the reaction mixture. The reaction mixture was then incubated at room temperature for 10 hours under a 50 W 365 nm LED light source.

[0239] NaHCO3 (1.34 g, 16 mmol, 2 eq.), benzyl bromide (1.9 mL, 16 mmol, 2 eq.), and methanol (16 mL) were added to the reaction solution, and the mixture was reacted at 65 °C for 4 hours. After the reaction was complete, the reaction solution was poured into 100 mL of water and extracted with DCM (4 × 50 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography to obtain a colorless oily liquid product (1.43 g, 84%). NMR characterization of the product: Secondary product: 1 H NMR (400 MHz, CDCl3) δ 7.48 –7.31 (m, 5H), 4.20 (s, 2H), 2.82 – 2.78 (m, 1H), 2.08 – 1.98 (m, 1H), 1.61 –1.50 (m, 1H), 1.34 (d, J = 6.9 Hz, 3H), 0.98 (t, J = 7.5 Hz, 3H). 13 C NMR (101MHz, CDCl3) δ 130.7, 129.0, 128.9, 127.9, 57.1, 56.4, 22.1, 12.2, 11.0. Primary products: 1 H NMR (400 MHz, CDCl3) δ 7.47 – 7.33 (m, 5H), 4.20 (s, 2H), 2.77 – 2.70(m, 2H), 1.76 (tt, J = 8.1, 6.5 Hz, 2H), 1.43 – 1.32 (m, 2H), 0.89 (t, J =7.3 Hz, 3H).13 C NMR (101 MHz, CDCl3) δ 130.6, 129.0, 129.0, 128.2, 59.4,50.8, 23.7, 21.7, 13.6.

[0240] Specifically, such as Figures 11-12 As shown, Figure 11 The 1H NMR spectrum of the product prepared by the gram-scale reaction using butane as a substrate in Example 16 of this invention; Figure 12 The image shows the carbon NMR spectrum of the product prepared by the gram-scale reaction using butane as a substrate in Example 16 of this invention.

[0241] Using isobutane at 0.1 MPa as a raw material, 1.20 g of product was prepared according to the method in this example, with a yield of 71%.

[0242] Using propane at 0.1 MPa as a raw material, 1.09 g of product was prepared according to the method in this example, with a yield of 69%.

[0243] Example 17 Ethane gram-scale reaction

[0244]

[0245] Specific steps: Before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0246] In a nitrogen-filled glove box, FeCl3 (0.8 mL, 0.001 M, 0.01 mol%), TBACl (444.7 mg, 1.6 mmol, 0.2 eq.), acetonitrile (72 mL), and a magnetic stirrer were added to a high-pressure photoreactor. The reactor was then removed from the glove box, and 8 mL of sulfurous acid solution diluted to 1 M was added. The high-pressure photoreactor was then completely sealed. The reactor was purged five times with 3 MPa ethane, followed by purging with 3 MPa ethane. Subsequently, the reaction solution was allowed to react at room temperature for 10 hours under 50 W 365 nm LED illumination.

[0247] The reaction solution was transferred to a 150 mL reaction flask, and NaHCO3 (1.34 g, 16 mmol, 2 eq.), benzyl bromide (1.9 mL, 16 mmol, 2 eq.), and methanol (16 mL) were added. The mixture was reacted at 65 °C for 4 hours. After the reaction was completed, the reaction solution was poured into 100 mL of water and extracted with DCM (4 × 50 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography to obtain a white solid product (1.03 g, 70%).

[0248] Example 18 Methane Scale-up Reaction

[0249]

[0250] Specific steps: In a nitrogen glove box, FeCl3 (8.1 mg, 0.05 M, 1 mol%), TBACl (277.9 mg, 1 mmol, 0.2 eq.), acetonitrile (45 mL), and a magnetic stirrer were added to the high-pressure photoreactor. The reactor was removed from the glove box, and 5 mL of sulfurous acid solution diluted to 1 M was added. The high-pressure photoreactor was then completely sealed. The reactor was purged five times with 1 MPa methane, followed by 5 MPa methane. Subsequently, the reaction solution was allowed to react at room temperature for 10 hours under 50 W 365 nm LED illumination.

[0251] The reaction solution was transferred to a 150 mL reaction flask, and NaHCO3 (840.1 g, 10 mmol, 2 eq.), benzyl bromide (11.9 mL, 10 mmol, 2 eq.), and methanol (10 mL) were added. The mixture was reacted at 65 °C for 4 hours. After the reaction was completed, the reaction solution was poured into 100 mL of water and extracted with DCM (4 × 50 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography to obtain a white solid product (0.30 g, 35%).

[0252] Example 19 Cyclohexane flow reaction

[0253]

[0254] Specific steps: In a nitrogen glove box, add cyclohexane (3.46 mL, 32 mmol, 4 eq.), FeCl3 (13.0 mg, 0.08 mmol, 1 mol%), TBACl (444.7 mg, 1.6 mmol, 0.2 eq.), acetonitrile (72 mL), and a magnetic stir bar to a 100 mL round-bottom flask. Remove the flask from the glove box, add 8 mL of pre-diluted 1 M sulfurous acid solution to the reaction mixture under nitrogen purging, and shake the reaction mixture thoroughly. Transfer the reaction mixture to a 100 mL syringe, and use a syringe pump as the fluid delivery power and PFA tubing as the fluid line for flow reaction (V = 5.8 mL, v = 0.29 mL / min, t...). R = 20 min).

[0255] After the reaction was complete, NaHCO3 (1.34 g, 16 mmol, 2 eq.), benzyl bromide (1.9 mL, 16 mmol, 2 eq.), and methanol (16 mL) were added to the reaction solution, and the mixture was reacted at 65 °C for 4 hours. The reaction solution was then poured into 100 mL of water and extracted with DCM (4 × 50 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and recrystallized (in n-hexane) to obtain a white solid product (1.73 g, 91%).

[0256] Example 20 Preparation of alkyl sulfinic acid from cyclohexane

[0257]

[0258] Specific steps: Before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0259] In a nitrogen-filled glove box, cyclohexane (3.46 mL, 32 mmol, 4 eq.), FeCl3 (0.8 mL, 0.001 M, 0.01 mol%), acetonitrile (72 mL), and a magnetic stir bar were added to a 150 mL Schlenk tube. The Schlenk tube was removed from the glove box, and under nitrogen purging, 8 mL of pre-diluted 1 M sulfurous acid solution and 133 μL of concentrated hydrochloric acid (1.6 mmol, 20 mol%) were added to the reaction mixture. The reaction mixture was then incubated at room temperature for 10 hours under 50 W 365 nm LED illumination.

[0260] After the reaction was complete, the reaction solution was concentrated by rotary evaporation, diluted with 50 mL of DCM and washed with 150 mL of water. The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain a colorless oily liquid product (1.07 g, 90%, TON = 9000, TOF = 900 h). -1 ).

[0261] Example 21 Preparation of alkyl sulfinates by one-pot cyclohexane method

[0262]

[0263] Specific steps: Before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0264] In a nitrogen-filled glove box, cyclohexane (3.46 mL, 32 mmol, 4 eq.), FeCl3 (0.8 mL, 0.001 M, 0.01 mol%), acetonitrile (72 mL), and a magnetic stir bar were added to a 150 mL Schlenk tube. The Schlenk tube was removed from the glove box, and under nitrogen purging, 8 mL of pre-diluted 1 M sulfurous acid solution and 133 μL of concentrated hydrochloric acid (1.6 mmol, 20 mol%) were added to the reaction mixture. The reaction mixture was then incubated at room temperature for 10 hours under 50 W 365 nm LED illumination.

[0265] NaOH (384.0 mg, 9.6 mmol, 1.2 eq., dissolved in 10 mL MeOH) and Na₂CO₃ (1.70 g, 16 mmol, 2 eq.) were added to the reaction mixture, and the mixture was reacted at room temperature for 10 hours. After the reaction was completed, the reaction solution was concentrated by rotary evaporation, 50 mL of methanol was added, and the mixture was sonicated for 5 minutes. The filtrate was concentrated by rotary evaporation to obtain an oily crude product. 60 mL of diethyl ether was added to the crude product, and the mixture was sonicated for 5 minutes. After filtration, a white solid product (1.36 g, 99%) was obtained. Based on this, the TON (total oxygen) for conversion to sulfinic acid was calculated to be 9900, and the TOF (total oxygen) was calculated to be 990 h⁻¹. -1 Product NMR characterization: 1 H NMR (400 MHz, D2O) δ 2.08 –1.98 (m, 1H), 1.98 – 1.78 (m, 4H), 1.74 – 1.64 (m, 1H), 1.41 – 1.15 (m, 5H). 13 C NMR (101 MHz, DO) δ 65.8, 25.6, 25.1, 24.5.

[0266] Specifically, such as Figures 13-14 As shown, Figure 13 The above is the 1H NMR spectrum of the alkyl sulfinate prepared using NaOH and Na2CO3 as bases in Example 21 of this invention. Figure 14 This is the carbon NMR spectrum of the alkyl sulfinate prepared using NaOH and Na2CO3 as alkalis in Example 21 of the present invention.

[0267] Other embodiments only require changing the type of alkali (in other embodiments, a single type of alkali is used instead of both NaOH and Na2CO3) or the reaction time; all other steps remain the same. Yields are all isolated yields, and the results are shown in Table 12.

[0268] Table 12 Preparation of alkyl sulfinates by different bases

[0269]

[0270] The reaction times in Table 12 all refer to the reaction time of the final step. As can be seen from Table 12, gram-scale reactions with conventional bases can achieve very good yields (>90%). The final step, being an acid-base reaction, can proceed relatively quickly; with K₂CO₃, the reaction is essentially complete in 1 hour.

[0271] Example 22 Preparation of alkyl sulfonates by one-pot cyclohexane method

[0272]

[0273] Specific steps: Before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0274] In a nitrogen-filled glove box, cyclohexane (3.46 mL, 32 mmol, 4 eq.), FeCl3 (0.8 mL, 0.001 M, 0.01 mol%), acetonitrile (72 mL), and a magnetic stir bar were added to a 150 mL Schlenk tube. The Schlenk tube was removed from the glove box, and under nitrogen purging, 8 mL of pre-diluted 1 M sulfurous acid solution and 133 μL of concentrated hydrochloric acid (1.6 mmol, 20 mol%) were added to the reaction mixture. The reaction mixture was then incubated at room temperature for 10 hours under 50 W 365 nm LED illumination.

[0275] NaOH (384.0 mg, 9.6 mmol, 1.2 eq., dissolved in 10 mL MeOH) was added to the reaction mixture, and the mixture was exposed to air and reacted at room temperature for 10 hours. After the reaction was complete, the reaction solution was concentrated by rotary evaporation, 50 mL of methanol was added, and the mixture was sonicated for 5 minutes. The filtrate was concentrated by rotary evaporation to obtain an oily crude product. 60 mL of diethyl ether was added to this crude product, and the mixture was sonicated for 5 minutes. After filtration, a white solid product (1.34 g, 90%) was obtained. NMR characterization of the product: 1 H NMR (400 MHz, D2O) δ 2.88– 2.71 (m, 1H), 2.21 – 2.07 (m, 2H), 1.95 – 1.81 (m, 2H), 1.77 – 1.66 (m,1H), 1.48 – 1.13 (m, 5H).

[0276] Specifically, such as Figure 15 As shown, Figure 15 The above is the 1H NMR spectrum of the alkyl sulfonate prepared in Example 22 of this invention using NaOH as a base, reacting for 10 hours under an air atmosphere.

[0277] Other embodiments only require changes to the type of alkali, reaction time, or the use of oxygen; the other steps remain the same. All yields are separate yields, and the results are shown in Table 13.

[0278] Table 13 Preparation of alkyl sulfonates by different bases

[0279]

[0280] a The reaction was carried out using an oxygen ball instead of air.

[0281] As shown in Table 13, gram-scale reactions with conventional bases can achieve good yields (>70%). The final step using Na₂CO₃ yields 72% in 2 hours, and the reaction rate is faster with oxygen than with air, with the reaction essentially complete in 5 hours.

[0282] Example 23 Preparation of sulfonamides by one-pot cyclohexane method

[0283]

[0284] Specific steps: Before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0285] In a nitrogen-filled glove box, cyclohexane (216 μL, 2 mmol, 4 eq.), FeCl3 (0.05 mL, 0.001 M, 0.01 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4.45 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and 0.5 mL of pre-diluted 1 M sulfurous acid solution was added to the reaction mixture using a syringe. The reaction mixture was then incubated at room temperature for 7 hours under 50 W 365 nm LED illumination.

[0286] Tetrahydropyrrole (125 μL, 1.5 mmol, 3 eq.) was added to the reaction solution, followed by dropwise addition of 1.25 M NaClO solution (1.2, 1.5 mmol, 3 eq.) at room temperature. After the addition was complete, the reaction solution was stirred at room temperature for 8 hours. After the reaction was complete, the reaction solution was poured into 30 mL of water and extracted with DCM (4 × 15 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography (petroleum ether: ethyl acetate = 8:1) to give a colorless oily liquid product (78.0 mg, 72%). NMR characterization of the product: 1 H NMR(400 MHz, CDCl3) δ 3.42 – 3.25 (m, 4H), 2.90 (tt, J =12.1, 3.5 Hz, 1H), 2.12 – 2.00 (m, 2H), 1.94 – 1.76 (m, 6H), 1.69 – 1.59 (m,1H), 1.49 (qd, J = 12.4, 3.5 Hz, 2H), 1.29 – 1.07 (m, 3H). 13 C NMR (101 MHz, CDCl3) δ 61.0, 48.1, 26.4, 26.0, 25.2, 25.2.

[0287] Specifically, such as Figures 16-17 As shown, Figure 16 The above is the 1H NMR spectrum of the sulfonamide prepared in Example 23 of this invention; Figure 17 The image shows the carbon NMR spectrum of the sulfonamide prepared in Example 23 of this invention.

[0288] Example 24 Preparation of sulfonates by one-pot cyclohexane method

[0289]

[0290] Specific steps: Before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0291] In a nitrogen-filled glove box, cyclohexane (216 μL, 2 mmol, 4 eq.), FeCl3 (0.05 mL, 0.001 M, 0.01 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4.45 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and 0.5 mL of pre-diluted 1 M sulfurous acid solution was added to the reaction mixture using a syringe. The reaction mixture was then incubated at room temperature for 7 hours under 50 W 365 nm LED illumination.

[0292] NaHCO3 (84.0 mg, 1 mmol, 2 eq.), iodobenzene acetate (241.6 mg, 0.75 mmol, 1.5 eq.), and methanol (1 mL) were added to the reaction mixture, and the reaction was allowed to proceed for 15 minutes. After the reaction was complete, the reaction mixture was poured into 30 mL of water and extracted with DCM (4 × 15 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography (petroleum ether: ethyl acetate = 20:1) to give a colorless oily liquid product (30.1 mg, 34%). NMR characterization of the product: 1 H NMR(400 MHz, CDCl3) δ 3.87 (s, 3H), 3.02 (tt, J = 12.1, 3.5 Hz, 1H), 2.23 – 2.12 (m, 2H), 1.93 – 1.83 (m, 2H), 1.72 – 1.65 (m, 1H), 1.63 – 1.49 (m, 2H), 1.35 – 1.12 (m, 3H). 13 C NMR (101 MHz, CDCl3) δ 59.5, 55.0, 26.4, 25.0, 25.0.

[0293] Specifically, such as Figures 18-19 As shown, Figure 18 The 1H NMR spectrum of the sulfonate ester prepared in Example 24 of this invention; Figure 19 The image shows the carbon NMR spectrum of the sulfonate ester prepared in Example 24 of this invention.

[0294] Example 25 Preparation of sulfonyl fluoride by one-pot method with cyclohexane

[0295]

[0296] Specific steps: Before each reaction, FeCl3 (1.6 mg, 0.01 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.001 M FeCl3 acetonitrile solution.

[0297] In a nitrogen-filled glove box, cyclohexane (216 μL, 2 mmol, 4 eq.), FeCl3 (0.05 mL, 0.001 M, 0.01 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4.45 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and 0.5 mL of pre-diluted 1 M sulfurous acid solution was added to the reaction mixture using a syringe. The reaction mixture was then incubated at room temperature for 7 hours under 50 W 365 nm LED illumination.

[0298] NaHCO3 (84.0 mg, 1 mmol, 2 eq.) and a selective fluorine reagent (352.4 mg, 1 mmol, 2 eq.) were added to the reaction mixture, and the reaction was carried out at room temperature for 1 hour. After the reaction was completed, the reaction solution was poured into 30 mL of water and extracted with DCM (4 × 15 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography (petroleum ether: ethyl acetate = 50:1) to give a colorless oily liquid product (65.0 mg, 78%). NMR characterization of the product: 1 H NMR (400 MHz, CDCl3) δ3.30 (ttd, J = 12.1, 3.5, 1.7 Hz, 1H), 2.34 – 2.22 (m, 2H), 2.02 – 1.89 (m,2H), 1.79 – 1.72 (m, 1H), 1.72 – 1.61 (m, 2H), 1.31 (dddd, J = 24.6, 15.9,12.5, 9.3 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 61.0, 60.9, 26.5, 24.7, 24.7. 19 FNMR (377 MHz, CDCl3) δ 40.8.

[0299] Specifically, such as Figures 20-21 As shown, Figure 20 The 1H NMR spectrum of the sulfonyl fluoride prepared in Example 25 of this invention; Figure 21 The image shows the carbon NMR spectrum of the sulfonyl fluoride prepared in Example 25 of this invention.

[0300] Example 26 Functional Group Tolerance

[0301]

[0302] Specific steps: Taking 3-pentanone as an example, before each reaction, FeCl3 (162.2 mg, 1 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.1 M FeCl3-acetonitrile solution. In a nitrogen glove box, 3-pentanone (212 μL, 2 mmol, 4 eq.), FeCl3 (0.05 mL, 0.1 M, 1 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4.45 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and 0.5 mL of sulfurous acid solution diluted to 1 M was added to the reaction solution using a syringe. Subsequently, the reaction solution was reacted at room temperature for 7 hours under 50 W 365 nm LED light. NaHCO3 (84.0 mg, 1 mmol, 2 eq.), 3-bromopropene (119 μL, 1 mmol, 2 eq.), and methanol (1 mL) were added to the reaction solution, and the reaction was carried out at 65 °C for 4 hours. After the reaction was completed, the reaction solution was poured into 30 mL of water and extracted with DCM (4 × 15 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography (petroleum ether: ethyl acetate = 3:1) to give a white solid product (86.5 mg, 91%). NMR characterization of the product: 1 H NMR (400 MHz, CDCl3) δ 5.98 – 5.84 (m, 1H), 5.55 – 5.43(m, 2H), 3.71 (d, J = 7.4 Hz, 2H), 3.24 (t, J = 7.3 Hz, 2H), 2.94 (t, J = 7.3Hz, 2H), 2.49 (q, J = 7.3 Hz, 2H), 1.06 (t, J = 7.3 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 207.0, 125.0, 124.8, 58.5, 45.6, 36.0, 33.7, 7.7.

[0303] Specifically, such as Figures 23-24 As shown, Figure 23 The 1H NMR spectrum of the product prepared using 3-pentanone as a substrate in Example 26 of this invention; Figure 24This is the carbon NMR spectrum of the product prepared using 3-pentanone as a substrate in Example 26 of the present invention.

[0304] Other substrate expansions were carried out according to the standard procedure described above. The reaction conditions described above can be substituted with single variables, such as different catalyst equivalents, different alkyl compounds, different component ratios, or different reaction times, while the other steps remain the same.

[0305] In the reaction formula of this embodiment, R1 and R2 represent substituents to represent substrates with different structures. Specifically, the different substrate structures are as follows:

[0306] Yields of different substrates, such as Figure 33 As shown, Figure 33 The yields of different substrates in Example 26 of this invention are shown. Figure 33 The circular shading in the image represents a minor regioisomer.

[0307] Reaction conditions: alkyl compound (2 mmol, 4 eq.), sulfurous acid solution (0.5 mmol, 1 eq.), FeCl3 (1 mol%), TBACl (27.8 mg, 0.1 mmol, 0.2 eq.), acetonitrile (4.5 mL), irradiated for 16 hours at room temperature under a 50 W 365 nm light source. rr = position selectivity. a 2 equivalents of alkyl compounds. b 5 mol% FeCl3. c 10 equivalents of alkyl compound, irradiated with light for 7 hours. d 10 mol% FeCl3.

[0308] Example 27 Selective reaction of open-chain alkanes with multiple reaction sites

[0309]

[0310] Specific steps: Taking n-pentane as an example, before each reaction, FeCl3 (162.2 mg, 1 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.1 M FeCl3-acetonitrile solution. In a nitrogen glove box, n-pentane (576 μL, 5 mmol, 4 eq.), FeCl3 (0.05 mL, 0.1 M, 1 mol%), trimethylchlorosilane (12.7 μL, 0.1 mmol, 0.2 eq.), benzo[a]naphthyl(1,2-D)thiazole (23.4 mg, 0.1 mmol, 20 mol%), acetonitrile (4.45 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and 0.5 mL of sulfurous acid solution diluted to 1 M was added to the reaction solution using a syringe. Subsequently, the reaction solution was reacted at room temperature for 7 hours under 50 W 365 nm LED illumination. Na₂CO₃ (106.0 mg, 1 mmol, 2 eq.), 3-bromopropene (119 μL, 1 mmol, 2 eq.), and methanol (1 mL) were added to the reaction solution, and the reaction was carried out at 65 °C for 4 hours. After the reaction was complete, the reaction solution was poured into 30 mL of water and extracted with DCM (4 × 15 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography (petroleum ether: ethyl acetate = 8:1) to give a pale yellow oily liquid product (49.6 mg, 56%). NMR characterization of the product: 1 HNMR(400 MHz, CDCl3) δ 5.97 – 5.87 (m, 1H), 5.51 – 5.39 (m, 2H), 3.68 (d, J =7.3 Hz, 2H), 3.00 – 2.86 (m, 2H), 1.86 – 1.76 (m, 2H), 1.44 – 1.28 (m, 4H), 0.89 (t, J = 7.0 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 125.3, 124.5, 57.7, 51.3, 30.6, 22.2, 21.5, 13.8.

[0311] Specifically, such as Figures 25-26 As shown, Figure 25 The above is the 1H NMR spectrum of the product prepared using n-pentane as a substrate in Example 27 of this invention. Figure 26 This is the carbon NMR spectrum of the product prepared using n-pentane as a substrate in Example 27 of the present invention.

[0312] Other embodiments only require changing the type of alkane; the other steps remain the same.

[0313] The open-chain alkane substrate structure is as follows:

[0314]

[0315] Yields of different open-chain alkane substrates, such as Figure 34 As shown, Figure 34 The yields of different open-chain alkane substrates in Example 27 of this invention.

[0316] Example 28 Selective reaction of branched alkanes with multiple reaction sites

[0317]

[0318] Specific steps: Taking 2,3-dimethylbutane as an example, before each reaction, FeCl3 (162.2 mg, 1 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.1 M FeCl3-acetonitrile solution. In a nitrogen glove box, 2,3-dimethylbutane (651 μL, 5 mmol, 4 eq.), FeCl3 (0.05 mL, 0.1 M, 1 mol%), trimethylchlorosilane (12.7 μL, 0.1 mmol, 0.2 eq.), thiaanthracene (21.6 mg, 0.1 mmol, 20 mol%), acetonitrile (4.45 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and 0.5 mL of pre-diluted 1 M sulfurous acid solution was added to the reaction solution using a syringe. Subsequently, the reaction solution was reacted at room temperature for 7 hours under 50 W 365 nm LED illumination. Na₂CO₃ (106.0 mg, 1 mmol, 2 eq.), 3-bromopropene (119 μL, 1 mmol, 2 eq.), and methanol (1 mL) were added to the reaction solution, and the reaction was carried out at 65 °C for 4 hours. After the reaction was complete, the reaction solution was poured into 30 mL of water and extracted with DCM (4 × 15 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography (petroleum ether: ethyl acetate = 8:1) to give a pale yellow oily liquid product (79.6 mg 84%). NMR characterization of the product: 1 HNMR(400 MHz, CDCl3) δ 5.96 – 5.85 (m, 1H), 5.51 – 5.34 (m, 2H), 3.67 (d, J =7.4 Hz, 2H), 2.95 (dd, J= 13.9, 3.7 Hz, 1H), 2.69 (dd, J = 13.9, 9.0 Hz, 1H),2.17 – 2.04 (m, 1H), 1.78 – 1.64 (m, 1H), 1.05 (d, J = 6.9 Hz, 3H), 0.86 (d, J =6.9 Hz, 3H), 0.82 (d, J = 6.9 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 143.7, 142.7, 77.2, 73.6, 51.4, 50.7, 37.7, 36.1, 34.1.

[0319] Specifically, such as Figures 27-28 As shown, Figure 27 The 1H NMR spectrum of the product prepared using 2,3-dimethylbutane as a substrate in Example 28 of this invention; Figure 28 This is the carbon NMR spectrum of the product prepared using 2,3-dimethylbutane as a substrate in Example 28 of the present invention.

[0320] Other embodiments only require changing the type of alkane; the other steps remain the same.

[0321] The structure of the branched alkane substrate is as follows:

[0322]

[0323] Yields of branched-chain alkane substrates with different structures, such as Figure 35 As shown, Figure 35 The yields of branched-chain alkane substrates with different structures in Example 28 of this invention are shown.

[0324] Figure 35 middle, a Use 5 equivalent substrates; b Use 2 equivalent substrates

[0325] Example 29 Selective reaction of cyclic alkanes with multiple reaction sites

[0326]

[0327] Specific steps: Taking cyclohexanone as an example, before each reaction, FeCl3 (162.2 mg, 1 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.1 M FeCl3-acetonitrile solution. In a nitrogen glove box, cyclohexanone (103 μL, 1 mmol, 2 eq.), FeCl3 (0.075 mL, 0.1 M, 1.5 mol%), trimethylchlorosilane (12.7 μL, 0.1 mmol, 0.2 eq.), BNT (1.2 mg, 0.005 mmol, 1 mol%), acetonitrile (4.425 mL), and a magnetic stir bar were added to an 8 mL reaction flask, and the perforated threaded cap with a PTFE gasket was tightened. The reaction flask was removed from the glove box, and 0.5 mL of sulfurous acid solution, pre-diluted to 1 M, was added to the reaction solution using a syringe. Subsequently, the reaction solution was reacted at room temperature for 8 hours under 50 W 365 nm LED illumination. Na₂CO₃ (106.0 mg, 1 mmol, 2 eq.), 3-bromopropene (87 μL, 1 mmol, 2 eq.), and methanol (1 mL) were added to the reaction solution, and the reaction was carried out at 65 °C for 5 hours. After the reaction was complete, the reaction solution was poured into 30 mL of water and extracted with DCM (4 × 15 mL). The resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography (petroleum ether: ethyl acetate = 8:1) to give a white solid (51.5 mg, 51%). NMR characterization of the product: 1 H NMR (400 MHz, CDCl3)δ 6.07 – 5.90 (m, 1H), 5.60 – 5.43 (m, 2H), 3.80 (d, J = 7.3 Hz, 2H), 3.45 –3.29 (m, 1H), 2.71 – 2.57 (m, 2H), 2.49 – 2.30 (m, 4H), 2.25 – 2.10 (m, 2H). 13 C NMR (101 MHz, CDCl3) δ 207.7, 124.9, 56.3, 55.8, 38.7, 24.5.

[0328] Specifically, such as Figures 29-30 As shown, Figure 29 The above is the 1H NMR spectrum of the product prepared using cyclohexanone as a substrate in Example 29 of this invention. Figure 30 This is the carbon NMR spectrum of the product prepared using cyclohexanone as a substrate in Example 29 of the present invention.

[0329] Other embodiments only require changing the type of alkane; the other steps remain the same.

[0330] The structure of a cyclic alkane with multiple reaction sites is as follows:

[0331]

[0332] The selective reactivity of cyclic alkanes with multiple reaction sites, such as Figure 36 As shown, Figure 36 This demonstrates the selective reaction effect of cyclic alkanes with multiple reaction sites in Example 29 of the present invention.

[0333] Note: Figure 36 The values ​​in the middle represent the separation yield. dr = diastereomer ratio

[0334] Example 30: Test of the selective reaction of sulfur-containing organic reagents on methyl valerate

[0335] Specific steps: Taking methyl valerate as an example, before each reaction, FeCl3 (162.2 mg, 1 mmol) was dissolved in acetonitrile (10 mL) to prepare a 0.1 M FeCl3 acetonitrile solution. In a nitrogen glove box, methyl valerate (564 μL, 5 mmol, 10 eq.), FeCl3 (0.05 mL, 0.1 M, 1 mol%), trimethylchlorosilane (12.7 μL, 0.1 mmol, 0.2 eq.), and sulfur-containing organic compounds (see details) were added. Figure 37 Add 0.1 mmol (20 mol%), acetonitrile (4.45 mL), and a magnetic stir bar to an 8 mL reaction flask, and tighten the threaded cap with a PTFE gasket. Remove the reaction flask from the glove box and add 0.5 mL of sulfurous acid solution diluted to 1 M using a syringe. Then, react the reaction solution at room temperature for 7 hours under 50 W 365 nm LED illumination. Add NaHCO3 (84.0 mg, 1 mmol, 2 eq.), 3-bromopropene (119 μL, 1 mmol, 2 eq.), and methanol (1 mL) to the reaction solution, and react at 65 °C for 4 hours. After the reaction, pour the reaction solution into 30 mL of water and extract with DCM (4 × 15 mL). The resulting organic phase is dried over anhydrous sodium sulfate, concentrated, and separated by silica gel column chromatography (petroleum ether: ethyl acetate = 8:1) to give a pale yellow oily liquid product (yield and selectivity are shown in [reference]). Figure 37 , Figure 37 This is a test of the selective reaction effect of the sulfur-containing organic reagent on methyl valerate in Example 30 of the present invention. Selectivity refers to the product at site c / the sum of the products at sites a+b+c).

[0336] .

[0337] Example 31: Ratio of main catalyst to organic sulfide

[0338]

[0339] For specific steps, please refer to Example 30, with corresponding changes to the amounts of FeCl3 and BNT.

[0340] Table 14 Screening of FeCl3 and BNT Doses

[0341]

[0342] As can be seen from the above examples, the iron catalyst and SO2 source in this invention are both inexpensive and readily available, the reaction conditions are mild, and the catalytic effect far exceeds the data reported in published patents and papers (the highest conversion number does not exceed 100). The method in this invention has a conversion number exceeding 9000, is suitable for synthesizing high-value-added sulfonyl compounds from inexpensive light alkanes and SO2, and is suitable for commercialization. The addition of sulfurized organic compounds can enable substrates with multiple reaction sites to exhibit regioselectivity in the reaction, thereby obtaining position-specific products.

[0343] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing sulfinic acid compounds by sulfinylation, characterized in that, Includes the following steps: Under a protective atmosphere and light conditions, alkyl compounds are subjected to sulfinylation with sulfur dioxide donors under catalytic conditions to obtain alkyl sulfinic acid compounds. The sulfur dioxide donor includes one or more of the following: sulfurous acid solution, 1,4-diazabicyclo[2.2.2]octane-1,4-dionyl-1,4-disulfinic acid, K2S2O5, Na2S2O5, and sulfur dioxide gas; The catalyst includes a main catalyst and a co-catalyst; The main catalyst comprises a metal salt, wherein the metal element in the metal salt includes one or more of Fe, Cu and Ce; the co-catalyst comprises one or more of chlorosilane, tetraalkylammonium chloride, alkali metal chloride and hydrochloric acid.

2. A method for preparing sulfinylation compounds, characterized in that, Includes the following steps: An alkyl sulfinic acid compound is prepared according to the method in claim 1, and the alkyl sulfinic acid compound is neutralized with a base to obtain an alkyl sulfinate compound.

3. A method for preparing sulfonate compounds by sulfinization, characterized in that, Includes the following steps: The alkyl sulfinic acid compound is prepared according to the method in claim 1, and the alkyl sulfinic acid compound is neutralized with an alkali in an oxygen-containing atmosphere to obtain an alkyl sulfonate compound.

4. A method for preparing sulfonyl compounds by sulfinization, characterized in that, Includes the following steps: The alkyl sulfinic acid compound is prepared according to the method in claim 1, and the alkyl sulfinic acid compound is reacted with an electrophilic reagent or an oxidizing agent to obtain an alkyl sulfonyl compound.

5. The method according to any one of claims 1 to 4, characterized in that, The metal salts include one or more of the following: metal halides, nitrates, sulfates, acetates, trifluoromethanesulfonates, tetrafluoroborates, hexafluorophosphates, trifluoroacetates, citrates, oxalates, acrylates, tris(2,2,6,6-tetramethyl-3,5-heptadecanoic acid) salts, and acetylacetone salts.

6. The method according to any one of claims 1 to 4, characterized in that, The molar ratio of the metal element in the main catalyst to the co-catalyst is 1:(4~200000).

7. The method according to any one of claims 1 to 4, characterized in that, The alkyl compounds include substituted or unsubstituted C1-C20 alkanes; The substituents in the substituted C1-C20 alkanes include one or more of the following: hydroxyl, carbonyl, C4-C20 aromatic, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C1-C10 ester, cyano, halogen, C1-C10 phosphate, amino, C2-C10 alkenyl, C2-C10 alkynyl, C1-C10 amino, amide, C1-C10 sulfonyl, C1-C10 sulfinyl, and C1-C10 alkoxy.

8. The method according to any one of claims 1 to 4, characterized in that, The molar ratio of the metal element to the alkyl compound in the main catalyst is 1:(20~8000000).

9. The method according to any one of claims 1 to 4, characterized in that, The molar ratio of the sulfur dioxide donor to the alkyl compound is 1:(1~80), based on the number of moles of sulfur dioxide in the sulfur dioxide donor.

10. The method according to any one of claims 1 to 4, characterized in that, The sulfinylation reaction is carried out at a temperature of 20-35°C, for a time of 7-36 hours, and at a pressure of 0.1-5 MPa.

11. The method according to any one of claims 1 to 4, characterized in that, In the aforementioned lighting conditions, the wavelength of the light source is 365~400nm, and the power of the light source is 5~100W.

12. The method according to any one of claims 1 to 4, characterized in that, The sulfinylation reaction is carried out in a solvent environment, the solvent including water and / or an organic solvent, the organic solvent including one or more of acetonitrile, acetone, ethyl acetate, dichloromethane, 1,2-dichloroethane and chloroform; the volume ratio of water to organic solvent is 1:(0~9).

13. The method for preparing sulfonyl compounds by sulfinization according to claim 4, characterized in that, Alkyl sulfinic acid compounds are reacted with electrophilic reagents in the presence of a basic reagent to obtain alkyl sulfone compounds; Alternatively, an alkyl sulfinic acid compound may be reacted with an oxidizing agent to obtain an oxidation product; said oxidation product includes alkyl sulfonate compounds, alkyl sulfonyl chloride compounds, alkyl sulfonyl fluoride compounds, or alkyl sulfonamide compounds.

14. The method according to any one of claims 1 to 4, characterized in that, When the alkyl compound has multiple reaction sites, the cocatalyst further includes a site-selective cocatalyst; The site-selective cocatalysts include organosulfur compounds.

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