Preparation method of meta-position sulfonylation polysubstituted pyridine compound

Abstract

The invention discloses a preparation method of a meta-position sulfonylation polysubstituted pyridine compound, and belongs to the technical field of organic synthesis. The method comprises the following steps: adding alkenyl amide as shown in a formula I and a sulfonylation reagent as shown in a formula II into an organic solvent, adding a catalyst and an oxidizing agent at the same time to promote a reaction, and after the reaction is finished, performing separation and purification to obtain the meta-position sulfonylation polysubstituted pyridine compound as shown in a formula III, wherein, R1 is selected from an alkyl group, an alkoxy group and an aryl group; r2 is selected from aryl; r3 is selected from hydrogen atom and alkyl; r4 is selected from aryl; and R5 is selected from alkyl and aryl. The reaction process is simple, various catalysts are not needed, the meta-position sulfonylation polysubstituted pyridine compound can be efficiently obtained in one step through the free radical tandem cyclization reaction, and the yield reaches up to 92%. The prepared compound can be used as a novel insecticide for preventing and treating agricultural pests, has a good effect and is relatively low in cost.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for preparing a meta-sulfonylated multi-substituted pyridine compound. Background Art

[0002] Sulfonylated pyridines are an important class of heterocyclic compounds containing sulfonyl groups. They exist in many natural products and bioactive molecules and have a wide range of biological activities. They can also be used as basic raw materials for various transformations and then applied in the field of functional materials. Therefore, the synthesis of sulfonylated pyridines has attracted widespread attention from synthetic chemists, and many synthetic methods have been developed in the past few decades. However, due to the inherent electronic properties of pyridine, most of the existing synthetic methods can only prepare ortho- or para-sulfonylated pyridines, while there are relatively few studies on the synthesis of meta-sulfonylated pyridines. However, these meta-sulfonylated pyridines play a vital role in pharmaceutical chemistry and agrochemicals, such as Alvelestat, a new neutrophil elastase inhibitor, Omidenepag, a drug for the treatment of open-angle glaucoma and ocular hypertension, and Oxazosulfy, a broad-spectrum insecticide with a new mechanism of action. Therefore, scientists have been developing new methods for the simple and efficient preparation of meta-sulfonylated pyridines. At present, there are mainly two methods for synthesizing meta-sulfonylated pyridine compounds:

[0003] 1. Coupling reaction of meta-preactivated pyridine with sulfonylating agent (Adv.Synth.Catal.2019,361,1154-1159; Adv.Synth.Catal.2019,361,956-960; ACS Catal.2019,9,10668-10673; Org.Lett.2013,15,6226-6229.).

[0004]

[0005] 2. Dearomatization strategy, that is, the unsubstituted pyridine is temporarily converted into a dihydropyridine intermediate in the reaction system, then reacts with an electrophile or a nucleophile, and finally re-aromatizes to generate the target product (Angew. Chem. Int. Ed. 2024, 63, e202409561; Nat. Comm. 2024, 15, 7428-7435.).

[0006]

[0007] Although the above two methods can synthesize some meta-phosphonylated pyridine compounds, there are still some disadvantages: in method 1, expensive transition metal catalysts and ligands are required, and this method has poor functional group compatibility and is not suitable for the preparation of polysubstituted pyridines; in method 2, there are few reagents that can dearomatize pyridine, and the dihydropyridine intermediate is unstable. Therefore, it is of great application prospect to develop a simple and efficient synthetic strategy and use cheap and readily available chemical reagents to prepare meta-sulfonylated pyridine compounds under mild reaction conditions. Summary of the invention

[0008] In view of the above technical problems, the present invention proposes a method for preparing meta-sulfonylated polysubstituted pyridine compounds. To achieve the above objectives, the present invention provides the following technical solutions:

[0009] A method for preparing a meta-sulfonylated polysubstituted pyridine compound comprises the following steps: adding an ene amide represented by formula I and a sulfonylation agent represented by formula II to an organic solvent, adding a catalyst and an oxidant to promote the reaction, and separating and purifying after the reaction to obtain a meta-sulfonylated polysubstituted pyridine compound represented by formula III;

[0010]

[0011] Among them, R 1 is selected from alkyl, alkoxy or aryl; R 2 is selected from aryl; R 3 is selected from a hydrogen atom or an alkyl group; R 4 is selected from aryl; R 5 Selected from alkyl or aryl.

[0012] The invention uses tertiary enamide and sulfonylhydrazide reagent as basic raw materials, and obtains meta-sulfonylated pyridine compounds with different substitutions in one step through intramolecular free radical tandem cyclization-aromatization reaction. The reaction raw materials of the invention are cheap and easy to obtain, the atom economy is high, the substrate is widely universal, and the operability is strong.

[0013] Furthermore, the molar ratio of the enamide, sulfonylating agent, catalyst and oxidant is 1:(1-2):(0.1-0.4):(2-4). The present invention has been proved through optimization experiments that the reaction can be smoothly carried out within this molar ratio range, and the difference is only in the yield. When the ratio is 1:1.5:0.2:3, the yield is the highest, so 1:1.5:0.2:3 is preferred.

[0014] Furthermore, the organic solvent is selected from any one of acetonitrile, toluene, N,N-dimethylformamide, tetrahydrofuran, tert-butyl alcohol and dichloromethane. The concentration of the organic solvent is 0.1 mol / L.

[0015] Furthermore, the catalyst is copper bromide.

[0016] Furthermore, the oxidant is dicumyl peroxide.

[0017] Furthermore, the reaction temperature is 40-120°C, and the reaction time is 8-30 hours. The present invention has found through optimization experiments that the reaction temperature can occur within this range, but the reaction time is different and the reaction yield is also different. The yield is the highest when the reaction is carried out at 90-100°C for 10-12 hours. Therefore, the preferred reaction temperature is 90-100°C and the reaction time is 10-12 hours.

[0018] Furthermore, the R 1 When it is an alkyl group, the alkyl group is selected from methyl, ethyl, isopropyl; R 1 When it is an alkoxy group, the alkoxy group is tert-butoxy or benzyloxy; R 1 When aryl is aryl, aryl is selected from phenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl or 4-fluorophenyl;

[0019] The R 2 When aryl is aryl, aryl is selected from phenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 3-bromophenyl, 2-bromophenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-methoxyphenyl or 2-naphthyl;

[0020] The R 3 When it is an alkyl group, the alkyl group is a methyl group or an ethyl group;

[0021] The R 4 When aryl is aryl, aryl is selected from phenyl, 4-methoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-chlorophenyl, 4-cyanophenyl, 4-trifluoromethylphenyl, 4-phenylphenyl, 1-naphthyl or thienyl;

[0022] The R 5 When R is an aryl group, the aryl group is selected from phenyl, 4-methoxyphenyl, 4-methylphenyl, 4-chlorophenyl, 4-bromophenyl, 4-nitrophenyl or thienyl; 5 When selected from alkyl, alkyl is ethyl, butyl or cyclopropyl.

[0023] The meta-sulfonylated multi-substituted pyridine compounds prepared by the method can be used to prevent agricultural pests.

[0024] Compared with the prior art, the present invention has the following advantages and technical effects:

[0025] 1. The reaction process of the present invention is simple and does not require multiple catalysts. Through the free radical tandem cyclization reaction, meta-sulfonylated polysubstituted pyridine compounds can be obtained in one step with high efficiency, and the yield is as high as 92%.

[0026] 2. The reaction of the present invention does not require the participation of highly toxic reagents, and also avoids expensive precious metal catalysts. The synthesis of the target product can be achieved using conventional reaction reagents, solvents and catalysts.

[0027] 3. The reaction substrate sulfonylating agent used in the method of the present invention does not need to be prepared and can be directly purchased commercially, thereby avoiding cumbersome reaction steps and improving the atom economy of the reaction.

[0028] 4. The reaction conditions involved in the present invention are relatively suitable, do not require high-pressure reaction, do not require a strict anhydrous and oxygen-free environment, are very simple to operate, have a high product yield, and the active groups can be further derivatized.

[0029] 5. The compounds provided by the present invention can be used as new pesticides for controlling agricultural pests, have good effects, and are relatively low in cost. DETAILED DESCRIPTION

[0030] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0031] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0032] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0033] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0034] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0035] The embodiment of the present invention provides a new method for preparing a meta-sulfonyl polysubstituted pyridine compound, comprising the following steps: adding an ene amide represented by formula I and a sulfonylating agent represented by formula II to an organic solvent, adding a catalyst and an oxidant to promote the reaction, and separating and purifying after the reaction to obtain a meta-sulfonyl polysubstituted pyridine compound represented by formula III; the reaction is as follows:

[0036]

[0037] Among them, R 1 is selected from alkyl, alkoxy or aryl; R 2 is selected from aryl; R 3 is selected from a hydrogen atom or an alkyl group; R 4 is selected from aryl; R 5 Selected from alkyl or aryl.

[0038] In some feasible embodiments, the molar ratio of the enamide, sulfonylating agent, catalyst and oxidant is 1:(1-2):(0.1-0.4):(2-4). As a typical but non-limiting example, in the following preferred embodiments of the present invention, the molar ratio of the enamide, sulfonylating agent, catalyst and oxidant can be selected as 1:1.5:0.2:3.

[0039] In some feasible embodiments, the organic solvent is selected from any one of acetonitrile, toluene, N,N-dimethylformamide, tetrahydrofuran, tert-butyl alcohol and dichloromethane. As a typical but non-limiting example, in the following preferred embodiments of the present invention, the organic solvent can be selected from dichloromethane. The concentration of the organic solvent is 0.1 mol / L.

[0040] In some feasible embodiments, the catalyst is copper bromide.

[0041] In some feasible embodiments, the oxidant is dicumyl peroxide.

[0042] In some feasible embodiments, the reaction temperature is 40-120°C, and the reaction time is 8-30 hours. The preferred reaction temperature is 90-100°C, and the reaction time is 10-12 hours. As a typical but non-limiting example, in the following preferred embodiments of the present invention, the reaction temperature can be selected to be 90°C, and the reaction time can be selected to be 12 hours.

[0043] In some feasible embodiments, the R 1 When it is an alkyl group, the alkyl group is methyl, ethyl, or isopropyl; R 1 When it is an alkoxy group, the alkoxy group is tert-butoxy or benzyloxy; R 1 When it is an aryl group, the aryl group is phenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl or 4-fluorophenyl.

[0044] In some feasible embodiments, the R 2 When it is an aryl group, the aryl group is phenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 3-bromophenyl, 2-bromophenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-methoxyphenyl or 2-naphthyl.

[0045] In some feasible embodiments, the R 3 When it is an alkyl group, the alkyl group is a methyl group or an ethyl group.

[0046] In some feasible embodiments, the R 4 When it is an aryl group, the aryl group is phenyl, 4-methoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-chlorophenyl, 4-cyanophenyl, 4-trifluoromethylphenyl, 4-phenylphenyl, 1-naphthyl or thienyl.

[0047] In some feasible embodiments, the R 5 When it is an aryl group, the aryl group is phenyl, 4-methoxyphenyl, 4-methylphenyl, 4-chlorophenyl, 4-bromophenyl, 4-nitrophenyl, or thienyl; R 5 When it is an alkyl group, the alkyl group is ethyl, butyl or cyclopropyl.

[0048] Exemplarily, the specific operation steps of the new method provided by the present invention are as follows: under air atmosphere, the enamide (0.2mmol, 1.0equiv) shown in formula I and the sulfonylhydrazine reagent (0.3mmol, 1.5equiv) shown in formula II are added to an organic solvent, and reacted at a reaction temperature of T degrees Celsius for 12 hours under the action of a catalyst (0.04mmol, 0.2equiv) and an oxidant (0.6mmol, 3.0equiv). After the reaction is completed, separation and purification are performed to obtain the meta-sulfonylated polysubstituted pyridine compound shown in formula III.

[0049] The "room temperature" in the present invention refers to 20-30°C unless otherwise specified.

[0050] The raw materials used in the present invention are all purchased from the market. Sulfonyl hydrazide reagent was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; enamide was homemade, and the preparation method was referenced in J. Org. Chem. 2022, 87, 3014-3024; the catalyst was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; and the oxidant was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0051] The technical solution of the present invention is further illustrated by the following embodiments.

[0052] Example 1

[0053] The compound represented by the structural formula IIIaa is prepared as follows:

[0054]

[0055] Under air atmosphere, a 10 ml reaction tube was added with a compound of formula Ia (0.2 mmol, 1.0 equiv), benzenesulfonyl hydrazide of formula IIa (0.3 mmol, 1.5 equiv), CuBr2 (0.04 mmol, 0.2 equiv), diisopropylbenzene peroxide (0.6 mmol, 3.0 equiv, DCP) and 2.0 mL of dichloromethane (DCM) with a concentration of 0.1 mol / L, and then the reaction tube was sealed and heated to 90° C. in an oil bath for 12 h. After the reaction was completed, the mixture was cooled to room temperature and directly separated and purified by silica gel column chromatography (volume ratio of petroleum ether: ethyl acetate = 4:1) to obtain a compound of formula IIIaa with a yield of 85%.

[0056] The characterization data of the obtained compound are as follows:

[0057] The compound is a white solid with a melting point of mp: 158-160°C;

[0058] 1 H NMR(500MHz,Chloroform-d)δ9.50(s,1H),7.56-7.52(m,2H),7.50-7.42(m,4H) ,7.37-7.33(m,1H),7.32-7.21(m,6H),6.81(dd,J=8.0,1.3Hz,2H),1.90(s,3H);

[0059] 13C NMR(126MHz,Chloroform-d)δ164.0,150.6,146.3,140.7,139.8,134.45,134.4 2,133.0,131.7,129.2,129.1,129.0,128.8,128.5,128.3,128.2,128.0,18.1;

[0060] HRMS (ESI) m / z [M+H] + Calcd.for C 24 H 20 NO2S 386.1209; Found 386.1216.

[0061] Example 2-12

[0062] The compound represented by the structural formula IIIaa is prepared by the following reaction formula:

[0063]

[0064] Except that the compound of formula Ia is different from that in Example 1, the types and amounts of other reaction reagents, reaction conditions and operations are the same as those in Example 1. The structure of the specific compound of formula Ia is shown in Table 1.

[0065] Table 1

[0066]

[0067]

[0068]

[0069] Example 13

[0070] The compound shown in the structural formula IIIba is prepared as follows:

[0071]

[0072] The preparation method is the same as that of Example 1, and the compound represented by formula IIIba is prepared with a yield of 87%.

[0073] The characterization data of the obtained compound are as follows:

[0074] The compound is a white solid with a melting point of mp: 164-166°C;

[0075] 1H NMR (500MHz, Chloroform-d) δ9.48 (s, 1H), 7.49-7.41 (m, 3H), 7.36-7.32 (m, 1H), 7.30-7.21 (m, 8H), 6.79 (d, J = 7.3Hz, 2H), 2.41 (s, 3H), 1.90 (s, 3H);

[0076] 13 C NMR(126MHz,Chloroform-d)δ164.1,150.5,146.3,140.8,139.0,137.0,134.6,134 .2,133.0,131.6,129.20,129.16,129.1,128.7,128.25,128.15,128.0,21.5,18.2;

[0077] HRMS (ESI) m / z [M+H] + Calcd.for C 25 H 22 NO2S 400.1366; Found 400.1375.

[0078] Embodiment 14

[0079] The compound shown in the structural formula IIIca is prepared by the following reaction formula:

[0080]

[0081] The preparation method is the same as that of Example 1, and the compound represented by formula IIIca is prepared with a yield of 61%.

[0082] The characterization data of the obtained compound are as follows:

[0083] The compound is a white solid with a melting point of mp: 168-170°C;

[0084] 1 H NMR(500MHz,Chloroform-d)δ9.48(s,1H),7.55-7.50(m,2H),7.49-7.44(m,1H),7.35(t,J=7.6 Hz,1H),7.31-7.22(m,6H),7.04-6.97(m,2H),6.80(d,J=7.2Hz,2H),3.87(s,3H),1.92(s,3H);

[0085] 13C NMR(126MHz,Chloroform-d)δ163.6,160.3,150.6,146.3,140.8,134.6,133.9,133 .0,132.2,131.4,130.8,129.2,128.7,128.25,128.16,1278.0,113.9,55.5,18.3;

[0086] HRMS (ESI) m / z [M+H] + Calcd.for C 25 H 22 NO3S 416.1315; Found 416.1307.

[0087] Embodiment 15

[0088] The compound shown in the structural formula IIIda is prepared by the following reaction formula:

[0089]

[0090] The preparation method is the same as that of Example 1, and the compound represented by formula IIIda is prepared with a yield of 80%.

[0091] The characterization data of the obtained compound are as follows:

[0092] The compound is a white solid with a melting point of mp: 164-165°C;

[0093] 1 H NMR(500MHz,Chloroform-d)δ9.49(s,1H),7.56-7.52(m,2H),7.51-7.45(m,1H),7.3 8-7.33(m,1H),7.31-7.22(m,6H),7.21-7.14(m,2H),6.82-6.77(m,2H),1.89(s,3H);

[0094] 13 C NMR(126MHz,Chloroform-d)δ163.2(d,J C-F =249.5Hz),162.9,150.8,146.4,140.7,135.8,134.6,134.3,133.1,131.7,131.2(d,J C-F =8.8Hz),129.1,128.8,128.4,128.2,128.0,115.6(d,J C-F =21.4Hz),18.1;

[0095] HRMS (ESI) m / z [M+H] + Calcd.for C 24 H 19 FNO2S 404.1115; Found 404.1108.

[0096] Example 16

[0097] The compound shown in the structural formula IIIea is prepared by the following reaction formula:

[0098]

[0099] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIea is prepared with a yield of 75%.

[0100] The characterization data of the obtained compound are as follows:

[0101] The compound is a white solid with a melting point of mp: 169-170°C;

[0102] 1 H NMR(500MHz,Chloroform-d)δ9.49(s,1H),7.51-7.43(m,5H),7.37-7.33(m,1H),7.31-7.21(m,6H),6.82-6.76(m,2H),1.89(s,3H);

[0103] 13 C NMR(126MHz,Chloroform-d)δ162.8,150.8,146.5,140.6,138.2,135.2,134.7, 134.3,133.1,131.7,130.6,129.1,128.79,128.76,128.4,128.2,128.0,18.1;

[0104] HRMS (ESI) m / z [M+H] + Calcd.for C 24 H 19 ClNO2S 420.0820; Found 420.0826.

[0105] Embodiment 17

[0106] The compound shown in the structural formula IIIfa is prepared as follows:

[0107]

[0108] The preparation method is the same as that of Example 1, and the compound represented by formula IIIfa is prepared with a yield of 70%.

[0109] The characterization data of the obtained compound are as follows:

[0110] The compound is a white solid, melting point mp: 189-191°C;

[0111] 1 H NMR(500MHz,Chloroform-d)δ9.49(s,1H),7.62(d,J=8.4Hz,2H),7.48(dq,J=8.6,4.0Hz,1H),7 .45-7.40(m,2H),7.35(t,J=7.5Hz,1H),7.30-7.22(m,6H),6.79(d,J=7.0Hz,2H),1.89(s,3H);

[0112] 13 C NMR(126MHz,Chloroform-d)δ162.8,150.8,146.5,140.6,138.7,134.7,134.2 ,133.1,131.7,131.6,130.9,129.1,128.8,128.4,128.2,128.0,123.5,18.1;

[0113] HRMS (ESI) m / z [M+H] + Calcd.for C 24 H 19 BrNO2S 464.0314,466.0294; Found464.0321,466.0301.

[0114] Embodiment 18

[0115] The compound shown in the structural formula of formula IIIga is prepared, and the reaction formula is as follows:

[0116]

[0117] The preparation method is the same as that of Example 1, and the compound represented by formula IIIga is prepared with a yield of 72%.

[0118] The characterization data of the obtained compound are as follows:

[0119] The compound is a white solid with a melting point of mp: 173-175°C;

[0120] 1H NMR (500MHz, Chloroform-d) δ9.49 (s, 1H), 7.67 (d, J = 8.0Hz, 1H), 7.50-7.46 (m, 1H), 7.44 (t, J = 7. 4Hz,1H),7.37-7.31(m,3H),7.31-7.28(m,4H),7.27-7.22(m,2H),6.84-6.78(m,2H),1.72(s,3H);

[0121] 13 C NMR(126MHz,Chloroform-d)δ163.6,150.2,146.4,140.7,135.3,134.1,133.1,133.0, 130.3,130.0,129.3,129.1,128.8,128.4,128.2,128.13,128.06,127.9,122.1,17.0;

[0122] HRMS (ESI) m / z [M+H] + Calcd.for C 24 H 19 BrNO2S 464.0314,466.0294; Found464.0320,466.0300.

[0123] Embodiment 19

[0124] The compound shown in the structural formula IIIha is prepared as follows:

[0125]

[0126] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIha is prepared with a yield of 75%.

[0127] The characterization data of the obtained compound are as follows:

[0128] The compound is a white solid with a melting point of mp: 172-174°C;

[0129] 1 H NMR(500MHz,Chloroform-d)δ9.49(s,1H),7.69(d,J=1.8Hz,1H),7.58(d,J=7.9Hz,1H),7. 50-7.44(m,2H),7.38-7.33(m,2H),7.29-7.22(m,6H),6.79(d,J=7.5Hz,2H),1.89(s,3H);

[0130] 13C NMR(126MHz,Chloroform-d)δ162.4,150.8,146.4,141.7,140.6,135.0,134.2,133.1 ,132.2,132.1,131.8,130.0,129.1,128.8,128.4,128.2,128.0,127.7,122.6,18.0;

[0131] HRMS (ESI) m / z [M+H] + Calcd.for C 24 H 19 BrNO2S 464.0314,466.0294; Found464.0324,466.0303.

[0132] Embodiment 20

[0133] The compound shown in the structural formula IIIia is prepared by the following reaction formula:

[0134]

[0135] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIia is prepared with a yield of 90%.

[0136] The characterization data of the obtained compound are as follows:

[0137] The compound is a white solid, melting point mp: 173-174°C;

[0138] 1 H NMR(500MHz,Chloroform-d)δ9.55(s,1H),8.03(s,1H),7.94(d,J=8.4Hz,1H),7.91-7.87(m,2H),7.68-7.63(m,1H),7 .56-7.50(m,2H),7.47(t,J=7.0Hz,1H),7.35(t,J=7.5Hz,1H),7.32-7.22(m,6H),6.83(d,J=7.5Hz,2H),1.95(s,3H);

[0139] 13C NMR(126MHz,Chloroform-d)δ163.9,150.7,146.4,140.8,137.2,137.1,134.5,134.4,133.4,133.1, 131.9,129.2,128.9,128.8,128.6,128.3,128.22,128.19,128.0,127.9,127.0,126.7,126.6,18.2;

[0140] HRMS (ESI) m / z [M+H] + Calcd.for C 28 H 22 NO2S 436.1366; Found 436.1375.

[0141] Embodiment 21

[0142] The compound shown in the structural formula IIIja is prepared as follows:

[0143]

[0144] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIja is prepared with a yield of 92%.

[0145] The characterization data of the obtained compound are as follows:

[0146] The compound is a white solid with a melting point of mp: 162-164°C;

[0147] 1 H NMR(500MHz,Chloroform-d)δ9.52(s,1H),7.55-7.50(m,3H),7.50-7.42(m,3H),7.32 -7.27(m,5H),7.11(t,J=7.6Hz,2H),6.70(d,J=7.5Hz,1H),1.85(s,3H),1.57(s,3H);

[0148] 13 C NMR(126MHz,Chloroform-d)δ164.0,150.4,146.8,140.4,139.7,136.2,134.3,133.9,13 3.3,131.6,130.1,129.4,129.1,129.0,128.9,128.8,128.51,128.47,125.8,19.4,17.3;

[0149] HRMS (ESI) m / z [M+H] +Calcd.for C 25 H 22 NO2S 400.1366;Found 400.1359.

[0150] Embodiment 22

[0151] The compound shown in the structural formula of formula IIIka is prepared, and the reaction formula is as follows:

[0152]

[0153] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIka is prepared with a yield of 90%.

[0154] The characterization data of the obtained compound are as follows:

[0155] The compound is a white solid with a melting point of mp: 151-153°C;

[0156] 1 H NMR(500MHz,Chloroform-d)δ9.50(s,1H),7.55-7.51(m,2H),7.50-7.41(m,4H),7.32-7.27(m,4H),7.1 9(t,J=7.5Hz,1H),7.14(d,J=7.6Hz,1H),6.74(d,J=7.5Hz,1H),6.41(s,1H),2.19(s,3H),1.90(s,3H);

[0157] 13 C NMR(126MHz,Chloroform-d)δ164.0,150.7,146.3,140.8,139.9,137.7,134.5,134.4,13 2.9,131.6,129.4,129.1,129.0,128.9,128.6,128.5,128.14,128.05,126.5,21.5,18.0;

[0158] HRMS (ESI) m / z [M+H] + Calcd.for C 25 H 22 NO2S 400.1366; Found 400.1358.

[0159] Embodiment 23

[0160] The compound shown in the structural formula IIIla is prepared, and the reaction formula is as follows:

[0161]

[0162] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIla is prepared with a yield of 80%.

[0163] The characterization data of the obtained compound are as follows:

[0164] The compound is a white solid, melting point mp: 142-144°C;

[0165] 1 H NMR(500MHz,Chloroform-d)δ9.51(s,1H),7.54(d,J=7.3Hz,2H),7.51-7.42(m,4H),7.35-7.27(m,4H),7 .20(t,J=7.5Hz,1H),7.15(d,J=7.6Hz,1H),6.74(d,J=7.4Hz,1H),6.41(s,1H),2.19(s,3H),1.91(s,3H);

[0166] 13 C NMR(126MHz,Chloroform-d)δ163.7,151.1,146.1,140.7,139.5,137.7,134.7,134. 3,133.0,131.9,129.4,129.2,129.1,128.6,128.5,128.2,128.1,126.4,21.5,18.1;

[0167] HRMS (ESI) m / z [M+H] + Calcd.for C 25 H 22 NO2S 400.1366; Found 400.1360.

[0168] Embodiment 24

[0169] The compound shown in the structural formula IIIma is prepared as follows:

[0170]

[0171] The preparation method is the same as that of Example 1, and the compound represented by formula IIIma is prepared with a yield of 76%.

[0172] The characterization data of the obtained compound are as follows:

[0173] The compound is a white solid with a melting point of mp: 170-172°C;

[0174] 1H NMR(500MHz,Chloroform-d)δ9.48(s,1H),7.56-7.50(m,2H),7.50-7.42(m,4H),7. 35-7.27(m,4H),6.81-6.75(m,2H),6.72(d,J=8.3Hz,2H),3.86(s,3H),1.91(s,3H);

[0175] 13 C NMR(126MHz,Chloroform-d)δ164.0,159.6,150.5,146.3,140.8,140.0,134.9,1 33.0,132.2,130.5,129.1,128.9,128.7,128.5,127.9,126.5,113.6,55.4,18.1;

[0176] HRMS (ESI) m / z [M+H] + Calcd.for C 25 H 22 NO3S 416.1315; Found 416.1308.

[0177] Embodiment 25

[0178] The compound shown in the structural formula of formula IIIna is prepared, and the reaction formula is as follows:

[0179]

[0180] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIna is prepared with a yield of 75%.

[0181] The characterization data of the obtained compound are as follows:

[0182] The compound is a white solid with a melting point of mp: 190-191°C;

[0183] 1 H NMR(500MHz,Chloroform-d)δ9.49(s,1H),7.55-7.43(m,6H),7.38-7.32(m,4H),7.25-7.20(m,2H),6.79-6.72(m,2H),1.91(s,3H);

[0184] 13C NMR(126MHz,Chloroform-d)δ164.2,149.3,146.3,140.6,139.5,134.7,134.6 ,133.3,132.8,131.6,130.6,129.2,129.1,128.9,128.6,128.5,127.9,18.1;

[0185] HRMS (ESI) m / z [M+H] + Calcd.for C 24 H 19 ClNO2S 420.0820; Found 420.0813.

[0186] Embodiment 26

[0187] The compound shown in the structural formula IIIoa is prepared, and the reaction formula is as follows:

[0188]

[0189] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIoa is prepared with a yield of 78%.

[0190] The characterization data of the obtained compound are as follows:

[0191] The compound is a white solid with a melting point of mp: 229-230°C;

[0192] 1 H NMR (500MHz, Chloroform-d) δ9.47 (s, 1H), 7.58-7.45 (m, 8H), 7.38-7.31 (m, 4H), 6.97 (d, J = 8.1Hz, 2H), 1.89 (s, 3H);

[0193] 13 C NMR(126MHz,Chloroform-d)δ164.6,148.1,146.6,140.6,139.40,139.37,133. 9,133.6,131.9,130.8,130.2,129.3,129.1,128.6,127.8,118.4,112.5,18.1;

[0194] HRMS (ESI) m / z [M+H] + Calcd.for C 25 H 19 N2O2S 411.1162; Found 411.1157.

[0195] Embodiment 27

[0196] The compound shown in the structural formula IIIpa is prepared as follows:

[0197]

[0198] The preparation method is the same as that of Example 1, and the compound represented by formula IIIpa is prepared with a yield of 70%.

[0199] The characterization data of the obtained compound are as follows:

[0200] The compound is a white solid, melting point mp: 186-187°C;

[0201] 1 H NMR (500MHz, Chloroform-d) δ9.51 (s, 1H), 7.56-7.45 (m, 8H), 7.33-7.27 (m, 4H), 6.96 (d, J = 7.9Hz, 2H), 1.91 (s, 3H);

[0202] 13 C NMR (126MHz, DMSO-d6) δ169.7,146.5,141.0,140.8,138.9,135.3,133.7,130.7,129.9,129.4,128.7(q,J C-F =31.5Hz),128.3,128.2,127.8,127.6,126.5,126.1,124.6(q,J C-F =3.8Hz),124.2(q,J C-F =273.4Hz),120.5,15.7;

[0203] HRMS (ESI) m / z [M+H] + Calcd.for C 25 H 19 F3NO2S 454.1083; Found 454.1090.

[0204] Embodiment 28

[0205] The compound shown in the structural formula IIIqa is prepared, and the reaction formula is as follows:

[0206]

[0207] The preparation method is the same as that of Example 1, and the compound represented by formula IIIqa is prepared with a yield of 78%.

[0208] The characterization data of the obtained compound are as follows:

[0209] The compound is a white solid with a melting point of mp: 176-178°C;

[0210] 1 H NMR(500MHz,DMSO-d6)δ9.35(s,1H),7.72(d,J=7.3Hz,2H),7.65-7.59(m,3H),7.55-7.47(m,7H),7 .41(t,J=7.4Hz,1H),7.37(t,J=7.8Hz,2H),7.34-7.30(m,2H),6.90(d,J=8.1Hz,2H),1.90(s,3H);

[0211] 13 C NMR (126MHz, DMSO-d6) δ163.3,149.5,145.4,140.0,139.9,139.6,139.4,134.0,133.5,13 3.0,131.5,129.5,129.1,129.04,128.99,128.8,128.2,127.8,127.3,126.8,126.1,17.8;

[0212] HRMS (ESI) m / z [M+H] + Calcd.for C 30 H 24 NO2S 462.1522;Found 462.1528.

[0213] Embodiment 29

[0214] The compound shown in the structural formula IIIra is prepared by the following reaction formula:

[0215]

[0216] The preparation method is the same as that of Example 1, and the compound represented by formula IIIra is prepared with a yield of 86%.

[0217] The characterization data of the obtained compound are as follows:

[0218] The compound is a white solid with a melting point of mp: 194-196°C;

[0219] 1H NMR(500MHz,Chloroform-d)δ9.63(s,1H),7.90(d,J=8.2Hz,1H),7.77(d,J=8.2Hz,1H),7.60-7.52(m,3H),7.5 1-7.42(m,3H),7.35-7.27(m,2H),7.10-7.00(m,4H),6.87(t,J=7.6Hz,2H),6.65(d,J=8.3Hz,1H),1.79(s,3H);

[0220] 13 C NMR(126MHz,Chloroform-d)δ163.8,149.0,146.7,139.7,139.5,135.5,133.1,132.7,132.6,131.5 ,130.5,129.4,129.2,129.1,128.6,128.5,128.4,128.2,127.8,126.7,125.9,125.2,124.1,17.4;

[0221] HRMS (ESI) m / z [M+H] + Calcd.for C 28 H 22 NO2S 436.1366;Found 436.1372.

[0222] Embodiment 30

[0223] The compound shown in the structural formula IIIsa is prepared, and the reaction formula is as follows:

[0224]

[0225] The preparation method is the same as that of Example 1, and the compound represented by formula IIIsa is prepared with a yield of 80%.

[0226] The characterization data of the obtained compound are as follows:

[0227] The compound is a white solid, melting point mp: 180-181°C;

[0228] 1H NMR(500MHz,Chloroform-d)δ9.51(s,1H),7.53(dd,J=8.1,1.7Hz,2H),7.51-7.44(m,4H),7.44-7.41(m,2H),7.38( dd,J=5.1,1.2Hz,1H),7.34(t,J=7.8Hz,2H),7.03(dd,J=5.1,3.5Hz,1H),6.80(dd,J=3.5,1.2Hz,1H),2.03(s,3H);

[0229] 13 C NMR (126MHz, Chloroform-d) δ164.1,146.5,143.8,140.5,139.6,136.0,133.8,133.6,133.2,130.3,129.1,128.9,128.5,128.4,127.9,126.9,18.2;

[0230] HRMS (ESI) m / z [M+H] + Calcd.for C 22 H 18 NO2S2392.0773;Found 392.0780.

[0231] Embodiment 31

[0232] The compound shown in the structural formula IIIta is prepared by the following reaction formula:

[0233]

[0234] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIta is prepared with a yield of 50%.

[0235] The characterization data of the obtained compound are as follows:

[0236] The compound is a white solid with a melting point of mp: 135-137°C;

[0237] 1 H NMR(500MHz,Chloroform-d)δ9.57(s,1H),8.06(td,J=5.8,5.1,3.2Hz,2H),7.57(s,1H),7.53- 7.36(m,5H),7.45-7.37(m,2H),7.29(q,J=7.7Hz,4H),7.23(t,J=7.8Hz,2H),7.08-7.03(m,2H);

[0238] 13C NMR (126MHz, Chloroform-d) δ161.2,151.1,149.7,140.6,137.4,136.2,134.2,133.1,130.7,129.4,129.1,128.8,128.7,128.0,127.9,127.7,123.2;

[0239] HRMS (ESI) m / z [M+H] + Calcd.for C 23 H 18 NO2S 372.1053; Found 372.1045.

[0240] Embodiment 32

[0241] The compound shown in the structural formula IIIua is prepared as follows:

[0242]

[0243] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIua is prepared with a yield of 74%.

[0244] The characterization data of the obtained compound are as follows:

[0245] The compound is a white solid, melting point mp: 161-163°C;

[0246] 1 H NMR(500MHz,Chloroform-d)δ9.48(s,1H),7.50-7.42(m,6H),7.36-7.31(m,1H),7.30-7.26( m,4H),7.21(t,J=7.6Hz,2H),6.86-6.80(m,2H),2.33(q,J=7.4Hz,2H),0.63(t,J=7.4Hz,3H);

[0247] 13 C NMR(126MHz,Chloroform-d)δ164.7,149.9,146.3,140.7,140.2,137.8,134.9,13 3.6,133.0,129.7,128.8,128.7,128.49,128.47,128.2,127.9,127.7,22.7,14.7;

[0248] HRMS (ESI) m / z [M+H] + Calcd.for C 25 H 22NO2S 400.1366;Found 400.1373.

[0249] Embodiment 33

[0250] The compound shown in the structural formula IIIab is prepared, and the reaction formula is as follows:

[0251]

[0252] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIab is prepared with a yield of 78%.

[0253] The characterization data of the obtained compound are as follows:

[0254] The compound is a white solid with a melting point of mp: 183-185°C;

[0255] 1 H NMR(500MHz,Chloroform-d)δ9.47(s,1H),7.55-7.50(m,2H),7.49-7.42(m,3H),7.39-7.33(m,1H),7.26(t, J=7.61Hz,2H),7.17(d,J=8.1Hz,2H),7.07(d,J=8.0Hz,2H),6.83(d,J=7.1Hz,2H),2.37(s,3H),1.89(s,3H);

[0256] 13 C NMR(126MHz,Chloroform-d)δ163.9,150.5,146.3,144.0,139.9,137.9,134.7,13 4.6,131.6,129.4,129.2,129.1,128.9,128.5,128.3,128.10,128.07,21.7,18.1;

[0257] HRMS (ESI) m / z [M+H] + Calcd.for C 25 H 22 NO2S 400.1366; Found 400.1375.

[0258] Embodiment 34

[0259] The compound shown in the structural formula IIIac is prepared by the following reaction formula:

[0260]

[0261] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIac is prepared with a yield of 80%.

[0262] The characterization data of the obtained compound are as follows:

[0263] The compound is a white solid, melting point mp: 180-181°C;

[0264] 1 H NMR(400MHz,Chloroform-d)δ9.46(s,1H),7.55-7.50(m,2H),7.50-7.42(m,3H),7.39-7.34(m,1H),7 .32-7.27(m,2H),7.23-7.17(m,2H),6.90-6.82(m,2H),6.78-6.69(m,2H),3.83(s,3H),1.89(s,3H);

[0265] 13 C NMR(101MHz,Chloroform-d)δ163.8,163.4,150.3,146.3,140.0,135.0,134.8,1 32.5,131.5,130.3,129.3,129.1,128.9,128.5,128.3,128.2,114.0,55.8,18.1;

[0266] HRMS (ESI) m / z [M+H] + Calcd.for C 25 H 22 NO3S 416.1315; Found 416.1322.

[0267] Embodiment 35

[0268] The compound shown in the structural formula IIIad is prepared by the following reaction formula:

[0269]

[0270] The preparation method is the same as that of Example 1, and the compound represented by formula IIIad is prepared with a yield of 68%.

[0271] The characterization data of the obtained compound are as follows:

[0272] The compound is a white solid with a melting point of mp: 187-189°C;

[0273] 1H NMR(400MHz,Chloroform-d)δ9.52(s,1H),8.13-8.05(m,2H),7.56-7.52(m,2H),7.51-7.45(m,4 H),7.44(d,J=2.0Hz,1H),7.43-7.37(m,1H),7.30-7.23(m,2H),6.86-6.78(m,2H),1.92(s,3H);

[0274] 13 C NMR(101MHz,Chloroform-d)δ165.0,150.4,150.2,146.5,146.4,139.6,134.2 ,133.4,131.9,129.4,129.3,129.2,129.1,128.8,128.6,128.4,123.8,18.1;

[0275] HRMS (ESI) m / z [M+H] + Calcd.for C 24 H 19 N2O4S 431.1060; Found 431.1068.

[0276] Embodiment 36

[0277] The compound shown in the structural formula IIIae is prepared by the following reaction formula:

[0278]

[0279] The preparation method is the same as that of Example 1, and the compound represented by formula IIIae is prepared with a yield of 72%.

[0280] The characterization data of the obtained compound are as follows:

[0281] The compound is a white solid with a melting point of mp: 196-198°C;

[0282] 1 H NMR(500MHz,Chloroform-d)δ9.48(s,1H),7.55-7.51(m,2H),7.50-7.42(m,3H),7.41-7.36(m,1H),7 .29(t,J=7.6Hz,2H),7.24(d,J=8.7Hz,2H),7.19(d,J=8.7Hz,2H),6.84(d,J=7.1Hz,2H),1.91(s,3H);

[0283] 13C NMR (126MHz, Chloroform-d) δ164.3,150.4,146.3,139.81,139.76,139.2,134.4,134.2,131.8,129.5,129.3,129.1,129.0,128.5,128.3,18.1;

[0284] HRMS (ESI) m / z [M+H] + Calcd.for C 24 H 19 ClNO2S 420.0820; Found 420.0811.

[0285] Embodiment 37

[0286] The compound shown in the structural formula IIIaf is prepared by the following reaction formula:

[0287]

[0288] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIaf is prepared with a yield of 75%.

[0289] The characterization data of the obtained compound are as follows:

[0290] The compound is a white solid with a melting point of mp: 179-181°C;

[0291] 1 H NMR(400MHz,Chloroform-d)δ9.48(s,1H),7.55-7.51(m,2H),7.51-7.44(m,3H),7.43-7. 36(m,3H),7.29(dd,J=8.3,7.0Hz,2H),7.16-7.08(m,2H),6.87-6.80(m,2H),1.90(s,3H);

[0292] 13 C NMR(101MHz,Chloroform-d)δ164.4,150.4,146.4,139.9,139.8,134.4,134 .1,132.0,131.7,129.5,129.3,129.10,129.07,128.5,128.4,128.3,18.1;

[0293] HRMS (ESI) m / z [M+H] + Calcd.for C 24 H 19BrNO2S 464.0314,466.0294; Found464.0307,466.0287.

[0294] Embodiment 38

[0295] The compound shown in the structural formula IIIag is prepared, and the reaction formula is as follows:

[0296]

[0297] The preparation method is the same as that of Example 1, and the compound represented by formula IIIag is prepared with a yield of 70%.

[0298] The characterization data of the obtained compound are as follows:

[0299] The compound is a white solid with a melting point of mp: 164-166°C;

[0300] 1 H NMR(500MHz,Chloroform-d)δ9.42(s,1H),7.57-7.51(m,3H),7.50-7.42(m,3H),7.41-7.36(m,1H),7.3 6-7.30(m,2H),6.99-6.93(m,2H),6.90(dd,J=3.8,1.4Hz,1H),6.85(dd,J=5.0,3.8Hz,1H),1.93(s,3H);

[0301] 13 C NMR(126MHz,Chloroform-d)δ164.1,150.4,146.0,141.9,139.8,135.1,134 .6,134.2,131.7,129.1,129.00,128.98,128.5,128.4,128.2,127.3,18.1;

[0302] HRMS (ESI) m / z [M+H] + Calcd.for C 22 H 18 NO2S2392.0773;Found 392.0765.

[0303] Embodiment 39

[0304] The compound shown in the structural formula IIIah is prepared as follows:

[0305]

[0306] The preparation method is the same as that of Example 1, and the compound represented by Formula IIIah is prepared with a yield of 65%.

[0307] The characterization data of the obtained compound are as follows:

[0308] The compound is a white solid with a melting point of mp: 151-153°C;

[0309] 1 H NMR(400MHz,Chloroform-d)δ9.24(s,1H),7.57-7.53(m,2H),7.53-7.42(m,6H) ),7.33-7.28(m,2H),2.69(q,J=7.4Hz,2H),2.02(s,3H),1.16(t,J=7.4Hz,3H);

[0310] 13 C NMR (101MHz, Chloroform-d) δ164.2,150.3,147.4,139.8,135.0,131.7,131.5,129.1,129.0,128.7,128.5,49.9,18.3,7.3;

[0311] HRMS (ESI) m / z [M+H] + Calcd.for C 20 H 20 NO2S 338.1209; Found 338.1217.

[0312] Application Example 1

[0313] Test of the insecticidal biological activity of the compounds of formula III prepared in Example 1 and Examples 13-39 against the larvae of Plutella xylostella

[0314] (1) Determination method: Weigh 4 mg of the newly prepared compound and dissolve it in 4 mL of a mixed solvent of methanol and acetone (volume ratio 1:1) to prepare a 1000 mg / L solution. Take 1 mL of the solution and dilute it 50 times to prepare a 20 mg / L solution for use, and the remaining 3 mL of the solution is diluted 20 times to prepare a 50 mg / L solution for use. The control drug group (Oxazosulfyl, purchased from Shanghai Yifei Biotechnology Co., Ltd.) was set up in the same way, and distilled water with methanol and acetone was used as a blank control experimental group. In addition, circular cabbage leaves with a diameter of 4 cm were prepared, and two solutions of different mass concentrations were evenly sprayed on different cabbage leaves using an airbrush sprayer. The cabbage leaves were then placed in a culture dish lined with filter paper and dried naturally in the shade. Then, 10 third-instar larvae of the diamondback moth were added to each cabbage leaf and raised in an incubator for 48 hours. The number of live and dead diamondback moths at 24 hours and 48 hours were recorded respectively.

[0315] (2) Activity expression: The corrected mortality rate is used to characterize the insecticidal activity of the compound. The higher the mortality rate, the higher the insecticidal activity of the compound.

[0316] Mortality rate / % = number of dead insects / number of test insects × 100

[0317] Corrected mortality / % = (treatment mortality - control mortality) / (1-control mortality) × 100

[0318] (3) The experimental results are shown in Table 2.

[0319] Table 2 Insecticidal activity test results of target compounds

[0320]

[0321]

[0322] Analysis of the data in Table 2 shows that some of the newly prepared compounds represented by the structural formula III have certain insecticidal activity against diamondback moth larvae at concentrations of 20 mg / L and 50 mg / L, among which the compounds represented by the structural formula IIIda, IIIoa, IIIpa, IIIsa, IIIad, and IIIah have a higher lethality against the 3rd instar diamondback moth larvae, and IIIpa and IIIah have the best insecticidal activity, which is close to the insecticidal effect of Oxazosulfyl. The results also show that the lethality of the compounds provided by the present invention against the 3rd instar diamondback moth larvae is positively correlated with the duration of medication.

[0323] The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. A method for preparing a meta-sulfonylated polysubstituted pyridine compound, characterized in that: The following steps are involved: The enamide of formula I and the sulfonylating agent of formula II are added to an organic solvent, and a catalyst and an oxidant are added to promote the reaction. After the reaction is completed, the mixture is separated and purified to obtain a meta-sulfonyl polysubstituted pyridine compound of formula III; Among them, R 1 is selected from alkyl, alkoxy or aryl; R 2 is selected from aryl; R 3 is selected from a hydrogen atom or an alkyl group; R 4 is selected from aryl; R 5 Selected from alkyl or aryl.

2. The method for preparing the meta-sulfonylated polysubstituted pyridine compound according to claim 1, characterized in that: The molar ratio of the enamide, the sulfonylating agent, the catalyst and the oxidizing agent is 1:(1-2):(0.1-0.4):(2-4).

3. The method for preparing the meta-sulfonylated polysubstituted pyridine compound according to claim 2, characterized in that: The molar ratio of the enamide, the sulfonylating agent, the catalyst and the oxidant is 1:1.5:0.2:

3.

4. The method for preparing the meta-sulfonylated polysubstituted pyridine compound according to claim 1, characterized in that: The organic solvent is selected from any one of acetonitrile, toluene, N,N-dimethylformamide, tetrahydrofuran, tert-butanol and dichloromethane.

5. The method for preparing the meta-sulfonylated polysubstituted pyridine compound according to claim 4, characterized in that: The concentration of the organic solvent is 0.1 mol / L.

6. The method for preparing meta-sulfonylated polysubstituted pyridine compounds according to claim 1, characterized in that: The catalyst is copper bromide.

7. The method for preparing meta-sulfonylated polysubstituted pyridine compounds according to claim 1, characterized in that: The oxidant is dicumyl peroxide.

8. The method for preparing meta-sulfonylated polysubstituted pyridine compounds according to claim 1, characterized in that: The reaction temperature is 40-120° C., and the reaction time is 8-30 hours.

9. The method for preparing the meta-sulfonylated polysubstituted pyridine compound according to claim 8, characterized in that: The reaction temperature is 90-100° C. and the reaction time is 10-12 hours.

10. The method for preparing meta-sulfonylated polysubstituted pyridine compounds according to claim 1, characterized in that: The R 1 When it is an alkyl group, the alkyl group is selected from methyl, ethyl or isopropyl; R 1 When it is an alkoxy group, the alkoxy group is selected from tert-butoxy or benzyloxy; R 1 When aryl is aryl, aryl is selected from phenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl or 4-fluorophenyl; The R 2 When aryl is aryl, aryl is selected from phenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 3-bromophenyl, 2-bromophenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-methoxyphenyl or 2-naphthyl; The R 3 When it is an alkyl group, the alkyl group is a methyl group or an ethyl group; The R 4 When aryl is aryl, aryl is selected from phenyl, 4-methoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-chlorophenyl, 4-cyanophenyl, 4-trifluoromethylphenyl, 4-phenylphenyl, 1-naphthyl or thienyl; The R 5 When R is an aryl group, the aryl group is selected from phenyl, 4-methoxyphenyl, 4-methylphenyl, 4-chlorophenyl, 4-bromophenyl, 4-nitrophenyl or thienyl; 5 When it is an alkyl group, the alkyl group is ethyl, butyl or cyclopropyl.

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