Xanthate derivatizing reagent, its preparation method and application

Abstract

The application discloses a preparation method of xanthate derivative reagent. The xanthate derivative reagent is prepared from amide or sulfonamide as raw material, through chlorination and nucleophilic substitution reaction with xanthate metal salt. The method comprises the following steps: (1) adding a first solvent to the amide or sulfonamide, stirring, adding t-butyl hypochlorite, and reacting at 20-40 DEG C for 5-60 min; filtering and drying the reaction mixture to obtain an intermediate product N-chloroamide or N-chlorosulfonamide; (2) adding a second solvent to the xanthate metal salt, stirring to obtain a xanthate metal salt solution, dissolving the N-chloroamide or N-chlorosulfonamide in the second solvent, and then adding dropwise into the xanthate metal salt solution, and reacting at 10-40 DEG C for 4-20 h to obtain the corresponding xanthate derivative reagent. The xanthate derivative reagent is a new reagent, and has a wide range of suitable substrates and mild reaction conditions.

Description

Technical Field

[0001] This invention belongs to the field of xanthate technology, specifically relating to a xanthate derivatization reagent, its preparation method, and its application. Background Technology

[0002] Organosulfur compounds have become a focus of organic synthesis research due to their widespread presence in bioactive molecules, pharmaceutical compounds, natural products, and functional molecules. For example, vortioxetine, a drug molecule used to treat depression, penicillin, a classic antibiotic, L-cysteine ​​with detoxification functions, and the pesticide thiram are all sulfur-containing compounds. Xanthate esters and their analogues are a special class of sulfur-containing compounds with SC(S) bonds, and their potential applications in synthetic intermediates and bioactive molecules have garnered widespread attention, possessing significant theoretical research value and practical application.

[0003] Xanthate groups, as important functional groups, are often used as intermediates in organic synthesis, aiding in the later functionalization transformations of compounds. For example, alkyl xanthates can be converted into (Z)-olefins via the Chugaev elimination reaction, which may be a key intermediate in the manufacture of viscose from cellulose. Furthermore, the well-known Barton-McCombie deoxygenation reaction uses alcohols as a source of alkyl radicals, significantly influencing the modification of bioactive molecules and natural product molecules containing hydroxyl groups. Another widespread application of xanthates is the preparation of Leuckart's thiophenol under alkaline conditions. In polymers, the RAFT polymerization process of xanthates can introduce xanthate groups into long-chain alkyl groups, thereby overcoming the tendency for chain termination in traditional polymerization reactions and making free radical polymerization more controllable. This reaction characteristic provides a new method and pathway for the functional modification of polymer materials. Furthermore, alkyl xanthate compounds, under free radical initiation or light irradiation, can undergo further transformations from alkyl compounds into valuable products, such as alkenylation / aminening / deuteration / hydroxylation / azidation / thiolation / trifluoromethylthiolation reactions of alkane CH bonds. Introducing this functional group into natural product molecules can significantly aid in the later functional group modification of natural products. In addition, xanthate groups and their analogues are widely found in bioactive molecules such as agrochemicals (insecticides and fungicides) and pharmaceuticals (nervous system agents and anticancer agents). The sulfur-containing compounds such as thiophenols, thioethers, disulfides, sulfoxides, and sulfones, which are further transformed from xanthate groups, are also the core frameworks of bioactive molecules and functional materials.

[0004] These developments have drawn increasing attention from academia and industry to xanthate chemistry. Therefore, developing different methods to introduce xanthate groups into target organic compounds has significant theoretical and practical value.

[0005] Currently, there are several methods for directly introducing xanthate esters into molecules: The first type is nucleophilic xanthate esterification, which involves the nucleophilic substitution reaction of xanthate metal salts with alkyl / aryl halides (iodides, bromides, fluorides), aryl diazonium salts, or aryl hypervalent iodide reagents. This allows the xanthate group to be introduced into the target organic molecule. (References: Synthesis 1978, 365-368; J. Org. R = aryl, alkyl; X = I, Br, F) Chem., 2018, 83, 8768-8774; Org. Lett., 2021, 23, 3115-3119), (Reference: J. Med. Chem. 2011, 54, 4678-4693) (Reference: Org. Lett. 2023, 25, 272-276); Similarly, aryl xanthates can also be obtained by coupling reactions of aryl halides or arylboronic acids with potassium ethyl xanthate mediated by metals or metal-organic frameworks. (Reference: J.Org.Chem. 2011, 76, 6819-6824) (Reference: Synlett 2018, 29, 986-992); The second type is radical xanthate esterification, where alkyl or aryl radicals are captured by radical xanthate ester reagents, thus introducing xanthate groups into the target molecule. For example, Alexanian recently reported direct CH xanthate esterification of alkanes or decarboxylation xanthate esterification of alkyl carboxylic acids under redox neutral conditions using Blue LED and radical xanthate ester reagents. (Reference: J. Am. Chem. Soc. 2016, 138, 13854-13857) (Reference: J.Am.Chem.Soc.2020, 142, 44-49).

[0006] However, the first and second methods currently have significant limitations in terms of the range of reaction substrates. Carbonyl compounds, aliphatic amines, phenols, and other substrates cannot undergo satisfactory xanthate esterification using these methods. Furthermore, the reagents used in radical xanthate esterification reactions are relatively expensive and cumbersome to prepare, which may limit their future applications. Due to the diversity of organic molecular structures, especially since many drug lead compounds are electron-rich substrates, electrophilic xanthate esterification is a promising method, but it has been rarely reported due to the lack of suitable electrophilic reagents.

[0007] The search for a practical synthetic auxiliary agent, serving as a universal, electrophilic xanthate esterifying agent with a broad substrate range, capable of introducing xanthate groups into electron-rich target molecules via a simple method, is of significant theoretical and industrial value, particularly for modifying complex bioactive molecules such as drugs or natural products. Therefore, addressing the current lack of a broad-spectrum electrophilic xanthate esterifying agent, developing novel and effective electrophilic xanthate esterifying agents, and finding methods for preparing diverse compounds containing xanthate groups that are simple in procedure, have a wide substrate range, mild reaction conditions, and high conversion and yield are urgent technical problems that need to be solved. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides an electrophilic xanthate derivatization reagent, its preparation method, and its application. The xanthate derivatization reagent is a novel reagent with a wide range of applicable substrates and mild reaction conditions.

[0009] Preparation method of xanthate derivatizing reagents: Using amides or sulfonamides as raw materials, after chlorination, they undergo a nucleophilic substitution reaction with xanthate metal salts to prepare electrophilic xanthate derivatizing reagents. The reaction mechanism is as follows: The specific preparation method is as follows: (1) Add the first solvent to the amide or sulfonamide, stir, then add tert-butyl hypochlorite, react at 20-40℃ for 5-60 min, filter the reaction mixture, dry it, and obtain the intermediate product N-chloroamide or N-chlorosulfonamide. (2) Add a second solvent to the xanthate metal salt, stir to obtain a xanthate metal salt solution, then dissolve the N-chloroamide or N-chlorosulfonamide in the second solvent, and then add it dropwise to the xanthate metal salt solution. React at 10-40℃ for 4-20h to obtain the corresponding xanthate ester derivatization reagent. Wherein, the first solvent is at least one of aromatic solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, sulfoxide solvents, amide solvents, or alcohol solvents; the second solvent is at least one of aromatic solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, sulfoxide solvents, amide solvents, or alcohol solvents.

[0010] Preferably, in step (1), the molar ratio of amide or sulfonamide to tert-butyl hypochlorite is 1:(1-1.5); and in step (2), the molar ratio of (N-chloroamide or N-chlorosulfonamide) to xanthate metal salt is 1:(1-1.5).

[0011] Preferably, the first solvent is an alcohol solvent. More preferably, the first solvent is methanol.

[0012] Preferably, the second solvent is a nitrile solvent. More preferably, the second solvent is acetonitrile.

[0013] Preferably, in step (1), the molar ratio of amide or sulfonamide to tert-butyl hypochlorite is 1:(1-1.2); and in step (2), the molar ratio of (N-chloroamide or N-chlorosulfonamide) to xanthate metal salt is 1:(1-1.2).

[0014] Preferably, step (1) is carried out at 25-30℃ for 5-10 min; step (2) is carried out at 20-30℃ for 14-16 h.

[0015] Preferably, the amide or sulfonamide is any one of the following compounds 1a to 1q:

[0016] Preferably, the xanthate metal salt is represented as: Wherein, M is lithium, sodium, potassium, rubidium, or cesium; more preferably, M is sodium or potassium; R is an alkoxy group OR 1 The corresponding xanthate derivatizing reagent is a xanthate esterification reagent; Or R is an alkylthio group SR 2 The corresponding xanthate derivatization reagent is a xanthate thioesterification reagent; Or R is an alkylamine group NR 3 R 4 The corresponding xanthate derivatizing reagent is a xanthamide reagent; Among them, R 1 R 2 For C1-C 12 Chain alkyl groups, C1-C containing other groups 12 Chain alkyl or C3-C 10Cycloalkyl groups; R 3 R 4 They are either chain alkyl groups or C1-C groups containing other groups. 12 Chain alkyl; or R 3 R 4 Together they form C3-C 10 Cyclic alkyl or heterocyclic groups.

[0017] More preferably, M is lithium or sodium.

[0018] Preferably, the OR 1 for n = 0-11, R 5 It is a chain alkyl group, a chain alkyl group containing other groups, a cyclic alkyl group, or a heterocyclic group; Or the OR 1 for n = 0-8, R 6 It can be alkyl, alkoxy, fluoroalkyl, halogen, ester, cyano, nitro, acyl, ether, or amino. Or the OR 1 for R 7 It is methylene, N-tert-butyloxycarbonyl, oxygen or sulfur; Or the OR 1 for n = 1-6, R 8 It is a five-membered heterocycle formed by alkyl, alkoxy, fluoroalkyl, halogen, ester, cyano, nitro, acyl, ether, or amino groups, where X is one or more heteroatoms selected from N, O, and S. The SR 2 for n = 1 - 11, R 9 It can be aryl, chain-like, or cycloalkyl; The NR 3 R 4 for R 3 R 4 For C1-C 12 Chain alkyl groups or C1-C groups containing other groups 12 Chain alkyl, or R 3 R 4 Together they form C3-C 10 Cycloalkyl groups; Or the NR 3 R 4 for R 10 It is an alkyl, alkoxy, fluoroalkyl, halogen, ester, cyano, nitro, acyl, ether, or amino group; X is a five-membered heterocycle formed by one or more heteroatoms from N, O, and S.

[0019] More preferably, the OR 1 for When n=0, R 5 It is isopropyl or adamantyl; when n=1, R 5 It is a methyl group; when n=2, R 5 It is tert-butanol or thiophene; when n=3, R 5 It is vinyl, trifluoromethyl, or methoxy; when n=4, R 5 It is chlorine; when n=5, R 5 It is an ester group; when n=6, R 5 It is hydrogen or bromine; Or the OR 1 for When n=1, R 6 It is methoxy, trifluoromethyl, or chloro; when n=2, R 6 It is hydrogen or N-tert-butoxycarbonyl; Or the OR 1 for n=3, R 8 The hydrogen atom is X, which is an indole ring. The SR 2 for When n=1, R 9 It can be methyl, phenyl, or benzyl; when n=11, R 9 It is a methyl group.

[0020] The NR 3 R 4 for R 3 R 4 All are ethyl or R 3 R 4 Together they form a morpholine ring; Or the NR 3 R 4 for R 10 It is hydrogen, and X is an indole ring.

[0021] More preferably, the amide is compound 1j.

[0022] More preferably, the OR 1 It is any one of the following groups 3a to 3s: The SR 2 It is any one of the following groups 3t to 3w: The NR 3 R 4It is any one of the following groups 3x to 3z:

[0023] When the amide is compound 1j, the xanthate metal salt is potassium xanthate, the R group in the potassium xanthate is any one of the above groups 3a to 3z, and the second solvent is acetonitrile, the corresponding reactions and the generated xanthate derivatizing reagents are as follows:

[0024] A xanthate derivatization reagent is prepared by any of the preparation methods described above.

[0025] An application of a method for preparing a xanthate derivatization reagent: The application is as follows: a xanthate derivatization reagent is reacted with a target molecule to directly introduce xanthate, xanthate thioester, or xanthamide groups into the target molecule, wherein the target molecule is an aryl / alkenylboronic acid, a carbonyl compound, a fatty amine, a phenol, or a bioactive molecule; wherein the xanthate derivatization reagent is the xanthate derivatization reagent described in this invention.

[0026] Preferably, the bioactive molecule is a boric acid derivative of coumarin, a fatty amine bioactive molecule, or a phenol bioactive molecule.

[0027] Preferably, (1) when the target molecule is an aryl / alkenylboronic acid or a boronic acid derivative of coumarin, the specific reaction is as follows: Under an inert atmosphere, the target molecule aryl / alkenylboronic acid or coumarin boric acid derivative, copper catalyst, ligand, base and xanthate derivatizing agent are mixed, a solvent is added, and the mixture is stirred at 25-80°C for 4-20 h to obtain the corresponding xanthate derivatized product; preferably, the mixture is stirred at 60-70°C for 14-16 h. The solvent is one or more selected from aromatic solvents, halogenated hydrocarbon solvents, ether solvents, nitrile solvents, and amide solvents; preferably, the solvent is a nitrile solvent; more preferably, the solvent is acetonitrile. The alkali is one or more selected from carbonates, phosphates, hydroxide metal salts, and tert-butanol metal salts; preferably, the alkali is a carbonate; more preferably, the alkali is sodium carbonate. The ligand is a nitrogen-containing bidentate ligand or a nitrogen-containing tripentate ligand; preferably, the ligand is a nitrogen-containing bidentate ligand; more preferably, the ligand is bipyridine; The copper catalyst is a monovalent copper catalyst or a divalent copper catalyst; preferably, the copper catalyst is a divalent copper catalyst; more preferably, the copper catalyst is anhydrous copper sulfate. The molar ratio of the aryl / alkenylboronic acid or coumarin boric acid derivative to the xanthate derivatizing reagent, base, copper catalyst, and ligand is 1:(1-1.5):(0.25-1.5):(0.02-0.2):(0.02-0.2); preferably, the molar ratio of the aryl / alkenylboronic acid or coumarin boric acid derivative to the xanthate derivatizing reagent, base, copper catalyst, and ligand is 1:(1-1.2):(0.5-0.6):(0.05-0.06):(0.05-0.06). (2) When the target molecule is a carbonyl compound, the reaction is as follows: Under an inert atmosphere, a carbonyl compound, a base, and a xanthate derivatizing agent are mixed, a solvent is added, and the mixture is stirred at 20-100°C for 4-20 hours to obtain the corresponding xanthate derivatized product; preferably, the mixture is stirred at 70-80°C for 14-16 hours. The solvent is one or more selected from aromatic solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, sulfoxide solvents, amide solvents, and alcohol solvents; preferably, the solvent is a halogenated hydrocarbon solvent; more preferably, the solvent is 1,2-dichloroethane; The alkali is one or more selected from carbonates, phosphates, hydroxide metal salts, and tert-butanol metal salts; preferably, the alkali is a carbonate; more preferably, the alkali is potassium carbonate. The molar ratio of the carbonyl compound, the base, and the xanthate derivatizing agent is 1:(1-2):(1-2); preferably, the molar ratio of the carbonyl compound, the base, and the xanthate derivatizing agent is 1:(1-1.5):(1-1.5). (3) When the target molecule is a fatty amine or a fatty amine bioactive molecule, the reaction is as follows: Under an inert atmosphere, the target molecule, aliphatic amine or aliphatic amine bioactive molecule, is mixed with a xanthate derivatization reagent, a solvent is added, and the mixture is stirred at 10-40°C for 4-20 h to obtain the corresponding xanthate derivatization product; preferably, the mixture is stirred at 20-25°C for 14-16 h. The solvent is one or more selected from aromatic solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, sulfoxide solvents, amide solvents, and alcohol solvents; preferably, the solvent is an aromatic solvent; more preferably, the solvent is toluene; The molar ratio of the fatty amine or fatty amine bioactive molecule to the xanthate derivatizing agent is 1:(1-2); preferably, the molar ratio of the fatty amine or fatty amine bioactive molecule to the xanthate derivatizing agent is 1:(1-1.5). (4) When the target molecule is a phenol or a phenolic bioactive molecule, the reaction is as follows: Under an inert atmosphere, the target molecule phenol or phenol-based bioactive molecule is mixed with a xanthate derivatization reagent and a base, a solvent is added, and the mixture is stirred at 20-100°C for 4-20 hours to obtain the corresponding xanthate derivatization product; preferably, the mixture is stirred at 70-80°C for 14-16 hours. The solvent is one or more selected from aromatic solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, sulfoxide solvents, amide solvents, and alcohol solvents; preferably, the solvent is a halogenated hydrocarbon solvent; more preferably, the solvent is 1,2-dichloroethane; The alkali is one or more selected from carbonates, phosphates, hydroxide metal salts, and tert-butanol metal salts; preferably, the alkali is a carbonate; more preferably, the alkali is cesium carbonate. The molar ratio of the phenol or phenolic bioactive molecule to the base and xanthate derivatizing agent is 1:(1-2):(1-2); preferably, the molar ratio of the phenol or phenolic bioactive molecule to the base and xanthate derivatizing agent is 1:(1-1.5):(1.2-1.5).

[0028] Advantages of this invention: The xanthate derivatization reagent provided by this invention is an electrophilic reagent. The preparation method is simple and convenient, low in cost, applicable to a wide range of substrates, with mild reaction conditions, high reaction conversion rate, high yield, good purity of the obtained product, and can modify bioactive molecules, thus having broad prospects for industrial production. Detailed Implementation

[0029] Example 1 A method for preparing a xanthate esterification reagent: (1) 9.9 g (100 mmol, 1.0 equiv) succinimide (compound 1a in this invention) was added to 100 mL of methanol, stirred, and then 12.4 mL (110 mmol, 1.1 equiv) tert-butyl hypochlorite was added. After reacting at 20 °C for 60 min, the reaction mixture was filtered and dried to obtain 12.2 g N-chlorosuccinimide, with a yield of 92.5%. (2) Acetonitrile was added to potassium ethyl xanthate (8.0 g, 50.0 mmol, 1.0 equiv) and stirred to obtain potassium ethyl xanthate acetonitrile solution. Then, N-chlorosuccinimide (6.68 g, 50.0 mmol, 1.0 equiv) was dissolved in acetonitrile. The N-chlorosuccinimide acetonitrile solution was added dropwise to the potassium ethyl xanthate acetonitrile solution using a constant pressure dropping funnel. After the addition was complete, the reaction was carried out at 20 °C for 15 h and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 1.1 g of the corresponding yellow oily product, with a yield of 10%.

[0030] The obtained yellow oily product was analyzed, and the results are as follows: S-(2,5-Dioxopyrrolidin-1-yl)O-ethyl carbonodithioate: 1 H NMR (400MHz, CDCl3) δ4.60 (q, J = 7.1Hz, 2H), 2.81 (s, 4H), 1.43 (t, J = 7.1Hz, 3H); 13 C NMR (101MHz, CDCl3) δ184.4,172.6,70.7,28.5,13.4ppm. The obtained yellow oily product was confirmed to be a xanthate esterification reagent.

[0031] Example 2 A method for preparing a xanthate esterification reagent: (1) 100 mL of methanol was added to 12.8 g (100 mmol, 1.0 equiv) of 5,5-dimethylhydantoin (1 g of the compound in this invention), stirred, and then 27.0 mL (240 mmol, 2.4 equiv) of tert-butyl hypochlorite was added. After reacting at 40 °C for 5 min, the reaction mixture was filtered and dried to obtain 18.8 g of 1,3-dichloro-5,5-dimethylhydantoin, with a yield of 95.4%. (2) Acetonitrile was added to potassium ethyl xanthate (4.0 g, 25.0 mmol, 2.5 equiv) and stirred to obtain potassium ethyl xanthate acetonitrile solution. Then, 1,3-dichloro-5,5-dimethylhydantoin (1.97 g, 10.0 mmol, 1.0 equiv) was dissolved in acetonitrile. The 1,3-dichloro-5,5-dimethylhydantoin acetonitrile solution was added dropwise to the potassium ethyl xanthate acetonitrile solution using a constant pressure dropping funnel. After the addition was complete, the reaction was carried out at 30 °C for 15 h and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain the corresponding yellow solid product of 933.1 mg, with a yield of 33%.

[0032] The obtained yellow oily product was analyzed, and the results are as follows: S-(3-Chloro-4,4-dimethyl-2,5-dioxoimidazolidin-1-yl)O-ethylcarbonodithioate: 1 H NMR (400MHz, CDCl3) δ4.62 (q, J = 7.1Hz, 2H), 1.48 (s, 6H), 1.45 (d, J = 7.2Hz, 3H); 13 C NMR (101MHz, CDCl3) δ183.2,172.9,152.0,70.1,58.5,25.2,13.5ppm. The obtained product was confirmed to be a xanthate esterification reagent.

[0033] Example 3 A method for preparing a xanthate esterification reagent: (1) 100 mL of methanol was added to 14.7 g (100 mmol, 1.0 equiv) of phthalimide (compound 1j in this invention) to obtain a suspension. The suspension was stirred, and then 16.9 mL (150 mmol, 1.5 equiv) of tert-butyl hypochlorite was added. The mixture was reacted at 20 °C for 20 min. The reaction mixture was filtered, dried, and vacuum dried to obtain 17.0 g of N-chlorophthalimide, with a yield of 93.7%. (2) Potassium ethyl xanthate (7.85 g, 49.0 mmol, 1.0 equiv) was placed in a 500 mL round-bottom flask and dissolved in acetonitrile. N-chlorophthalimide (8.9 g, 49.0 mmol, 1.0 equiv) was then dissolved in acetonitrile. The N-chlorophthalimide acetonitrile solution was then slowly added dropwise to the round-bottom flask containing potassium ethyl xanthate using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 15 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 9.4 g of the corresponding white solid product, with a yield of 72%.

[0034] The obtained white solid product was analyzed, and the results are as follows: S-(1,3-Dioxoisoindolin-2-yl)O-ethyl carbonodithioate: 1H NMR (400MHz, CDCl3) δ7.96 (dd, J=5.5, 3.1Hz, 2H), 7.82 (dd, J=5.6, 3.1Hz, 2H), 4.60 (q, J=7.1Hz, 2H), 1.30 (t, J=7.1Hz, 3H); 13 C NMR (101MHz, CDCl3) δ208.8,166.2,135.1,132.1,124.3,71.4,13.6ppm. The obtained product was confirmed to be a xanthate esterification reagent.

[0035] Example 4 A method for preparing a xanthate esterification reagent: (1) 13.5 mL (120 mmol, 1.2 equiv) of tert-butyl hypochlorite was injected into 100 mL of methanol suspension containing 18.3 g (100 mmol, 1.0 equiv) of saccharin (compound 1p in this invention). After stirring and reacting at 20 °C for 20 min, the suspension was filtered under reduced pressure and dried under vacuum to obtain 21.7 g of N-chlorosaccharin, with a yield of 99.7%. (2) Potassium ethyl xanthate (5.16 g, 32.2 mmol, 1.0 equiv) was placed in a 500 mL round-bottom flask and dissolved in acetonitrile. N-chlorosaccharin (7.0 g, 32.2 mmol, 1.0 equiv) was then dissolved in acetonitrile. The N-chlorosaccharin acetonitrile solution was then slowly added dropwise to the round-bottom flask containing potassium ethyl xanthate using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 15 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 1.95 g of the corresponding white solid product, with a yield of 20%.

[0036] The obtained white solid product was analyzed, and the results are as follows: S-(1,1-Dioxido-3-oxobenzo[d]isothiazol-2(3H)-yl)O-ethyl carbonodithioate: 1 H NMR (400MHz, CDCl3) δ8.16(dt,J=7.6,1.0Hz,1H),7.99–7.92(m,2H),7.92–7.86(m,1H),4.73(q,J=7.1Hz,2H),1.51(t,J=7.1Hz,3H); 13C10 NMR (101 MHz, CDCl3) δ 180.4, 156.2, 136.4, 135.0, 126.5, 125.8, 121.4, 69.0, 13.5 ppm. The obtained product was confirmed to be a xanthate ester.

[0037] Example 5 A method for preparing a xanthate esterification reagent: (1) Same as step (1) in Example 3, to obtain N-chlorophthalimide; (2) Potassium O-(4-chlorobutyl)methylthioate (OR in this invention) 1 Potassium xanthate (1.11 g, 4.99 mmol) corresponding to group 3d was placed in a 500 mL round-bottom flask and dissolved in acetonitrile. N-chlorophthalimide (907 mg, 4.99 mmol) was then dissolved in acetonitrile. The N-chlorophthalimide acetonitrile solution was then slowly added dropwise to the round-bottom flask containing the corresponding potassium xanthate using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 15 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 1.2 g of the corresponding white solid product, with a yield of 73%.

[0038] The obtained white solid product was analyzed, and the results are as follows: O-(4-Chlorobutyl)S-(1,3-dioxoisoindolin-2-yl)carbonodithioate 6d: 1 HNMR (400MHz, CDCl3) δ7.97 (dd, J=5.6, 3.1Hz, 2H), 7.84 (dd, J=5.5, 3.1Hz, 2H), 4 .57(t,J=6.1Hz,2H),3.42(t,J=6.3Hz,2H),1.88–1.79(m,2H),1.77–1.66(m,2H); 13 C NMR (101MHz, CDCl3) δ208.7,166.3,135.3,132.0,124.5,74.3,44.2,28.8,25.6ppm. The obtained product was confirmed to be a xanthate esterification reagent.

[0039] Example 6 A method for preparing a xanthate esterification reagent: (1) Same as step (1) in Example 3, to obtain N-chlorophthalimide; (2) Potassium O-(pent-4-en-1-yl)methylthioate (OR in this invention) 1 Potassium xanthate (3.0 g, 14.97 mmol) corresponding to a 3 g group was placed in a 250 mL round-bottom flask and dissolved in acetonitrile. N-chlorophthalimide (2.72 g, 14.97 mmol) was then dissolved in acetonitrile. The N-chlorophthalimide acetonitrile solution was then slowly added dropwise to the round-bottom flask containing the corresponding potassium xanthate using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 15 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 2.3 g of the corresponding white solid product, with a yield of 50%.

[0040] The obtained white solid product was analyzed, and the results are as follows: S-(1,3-Dioxoisoindolin-2-yl)O-(pent-4-en-1-yl)carbonodithioate 6g: 1 HNMR (400MHz, CDCl3) δ7.96 (dd, J=5.4, 3.3Hz, 2H), 7.83 (dd, J=5.5, 3.1Hz, 2H), 5.73–5.50 (m,1H),4.93–4.82(m,2H),4.53(t,J=6.4Hz,2H),1.96(q,J=7.3Hz,2H),1.78–1.69(m,2H); 13 CNMR (101 MHz, CDCl3) δ 208.7, 166.3, 136.7, 135.2, 132.1, 124.5, 115.9, 74.5, 29.7, 27.3 ppm. The obtained product was confirmed to be a xanthate ester.

[0041] Example 7 A method for preparing a xanthate esterification reagent: (1) Same as step (1) in Example 3, to obtain N-chlorophthalimide; (2) Potassium phthaloethyl methylthioate (OR in this invention) 1Potassium xanthate (3.87 g, 16.37 mmol) corresponding to the 3p group was placed in a 250 mL round-bottom flask and dissolved in acetonitrile. N-chlorophthalimide (2.97 g, 16.37 mmol) was then dissolved in acetonitrile. The N-chlorophthalimide acetonitrile solution was then slowly added dropwise to the round-bottom flask containing the corresponding potassium xanthate using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 15 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 3.96 g of the corresponding white solid product, with a yield of 70%.

[0042] The obtained white solid product was analyzed, and the results are as follows: S-(1,3-Dioxoisoindolin-2-yl)O-phenethyl carbonodithioate 6p: 1 H NMR (400MHz, CDCl3) δ7.95 (dd, J=5.5, 3.1Hz, 2H), 7.84 (dd, J=5.6, 3.1Hz, 2H), 7 .13(d,J=3.0Hz,3H),7.03(s,2H),4.76(t,J=6.9Hz,2H),2.98(t,J=6.9Hz,2H); 13 C NMR (101MHz, CDCl3) δ208.7,166.2,136.5,135.1,132.1,128.7,128.7,126.9,124.5,75.0,34.5ppm. The obtained product was confirmed to be a xanthate esterification reagent.

[0043] Example 8 A method for preparing a xanthate esterification reagent: (1) Same as step (1) in Example 3, to obtain N-chlorophthalimide; (2) Potassium salt of O-(2-(thiophen-3-yl)ethyl)meththioate (OR in this invention) 1Potassium xanthate (922.6 mg, 3.81 mmol) corresponding to the 3r group was placed in a 250 mL round-bottom flask and dissolved in acetonitrile. N-chlorophthalimide (691 mg, 3.81 mmol) was then dissolved in acetonitrile. The N-chlorophthalimide acetonitrile solution was then slowly added dropwise to the round-bottom flask containing the corresponding potassium xanthate using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 15 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 1.21 g of the corresponding white solid product, with a yield of 91%.

[0044] The obtained white solid product was analyzed, and the results are as follows: S-(1,3-Dioxoisoindolin-2-yl)O-(2-(thiophen-3-yl)ethyl)carbonodithioate 6r: 1 H NMR (400MHz, CDCl3) δ7.95 (dd, J=5.5, 3.1Hz, 2H), 7.83 (dd, J=5.5, 3.1Hz, 2H), 7.13 (dd, J=5.0 ,3.0Hz,1H),6.82(s,1H),6.79(d,J=5.1Hz,1H),4.74(t,J=6.7Hz,2H),2.99(t,J=6.7Hz,2H); 13 CNMR (101 MHz, CDCl3) δ 208.7, 166.2, 136.6, 135.2, 132.0, 127.9, 126.1, 124.5, 121.9, 74.4, 29.0 ppm. The obtained product was confirmed to be a xanthate esterification reagent.

[0045] Example 9 A method for preparing a xanthate esterification reagent: (1) 100 mL of methanol was added to 12.9 g (100 mmol, 1.0 equiv) of isocyanuric acid (compound 1f in this invention) to obtain a suspension. The suspension was stirred, and then 40.5 mL (360 mmol, 3.6 equiv) of tert-butyl hypochlorite was added. The mixture was reacted at 20 °C for 20 min. The reaction mixture was filtered and dried under vacuum to obtain 20.8 g of trichloroisocyanuric acid, with a yield of 89.5%. (2) Potassium O-(3-methoxypropyl)methylthioate (OR in this invention) 1Potassium xanthate (6.0 g, 30.0 mmol) corresponding to the 3e group was placed in a 250 mL round-bottom flask and dissolved in acetonitrile. Trichloroisocyanuric acid (2.32 g, 10.0 mmol) was then dissolved in acetonitrile. The trichloroisocyanuric acid acetonitrile solution was then slowly added dropwise to the O-(3-methoxypropyl)methylthioate potassium acetonitrile solution using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 15 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 1.63 g of the corresponding white solid product, with a yield of 45%.

[0046] The obtained white solid product was analyzed, and the results are as follows: S-(3,5-Dichloro-2,4,6-trioxo-1,3,5-triazinan-1-yl)O-(3-methoxypropyl)carbonodithioate: 1 HNMR (400MHz, CDCl3) δ3.66 (q, J = 5.7Hz, 2H), 3.48 (t, J = 6.0Hz, 2H), 3.28 (s, 3H), 1.75 (p, J = 5.9Hz, 2H); 13 C10 NMR (101 MHz, CDCl3) δ 183.2, 172.9, 152.0, 71.3, 61.0, 58.7, 32.0 ppm. The obtained product was confirmed to be a xanthate esterification reagent.

[0047] Example 10 A method for preparing a xanthate esterification reagent: (1) 19.7 g (100 mmol, 1.0 equiv) of 1,8-naphthalenediamide (compound 1n in this invention) was added to methanol to obtain a suspension. The suspension was stirred, and then 11.3 mL (100 mmol, 1.0 equiv) of tert-butyl hypochlorite was added. The mixture was reacted at 20 °C for 20 min. The reaction mixture was filtered and dried under vacuum to obtain 19.0 g of N-chloro-1,8-naphthalenediamide, with a yield of 82.0%. (2) Potassium salt of O-(1-(tert-butoxycarbonyl)piperidin-4-yl)meththioate (OR in this invention) 1Potassium xanthate (3.15 g, 10.0 mmol) corresponding to group 3j was placed in a 250 mL round-bottom flask and dissolved in acetonitrile. Then, N-chloro-1,8-naphthalenediamide (2.32 g, 10.0 mmol) was dissolved in acetonitrile. The N-chloro-1,8-naphthalenediamide acetonitrile solution was then slowly added dropwise to the acetonitrile solution of O-(1-(tert-butoxycarbonyl)piperidin-4-yl)methylthioate potassium salt using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 14 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 2.93 g of the corresponding white solid product, with a yield of 62%.

[0048] The obtained white solid product was analyzed, and the results are as follows: Tert-butyl4-((((1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)thio)carbonothioyl)oxy)piperidine-1-carboxylate: 1 H NMR (400MHz, CDCl3) δ8.61 (dd, J=7.2, 1.2Hz, 2H), 8.26 (dd, J=8.3, 1.2Hz, 2H), 7.78 (dd, J=8.3, 7.2H z,2H),5.62(tt,J=7.1,3.6Hz,1H),3.29(s,4H),1.96–1.79(m,2H),1.74–1.64(m,2H),1.40(s,9H); 13 C10 NMR (101 MHz, CDCl3) δ 207.8, 163.9, 154.6, 134.7, 132.0, 131.1, 129.4, 127.0, 122.5, 80.8, 79.9, 29.8, 28.4 ppm. The obtained product was confirmed to be a xanthate ester.

[0049] Example 11 A method for preparing a xanthate esterification reagent: (1) 21.6 g (100 mmol, 1.0 equiv) of pyromellitic diimide (compound 1o in this invention) was added to methanol to obtain a suspension. The suspension was stirred, and then 27.1 mL (240 mmol, 2.4 equiv) of tert-butyl hypochlorite was added. The mixture was reacted at 20 °C for 20 min. The reaction mixture was filtered and dried under vacuum to obtain 25.0 g of N-chloropyromellitic diimide, with a yield of 87.7%. (2) O-(4-methoxybenzyl)methylthiocarbonate potassium salt (OR in this invention)1 Potassium xanthate (5.04 g, 20.0 mmol) corresponding to group 3l was placed in a 250 mL round-bottom flask and dissolved in acetonitrile. N-chlorobenzoyl diimide (2.85 g, 10.0 mmol) was then dissolved in acetonitrile. The N-chlorobenzoyl diimide acetonitrile solution was then slowly added dropwise to the acetonitrile solution of O-(4-methoxybenzyl)methylthiocarbonate potassium salt using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 15 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 2.64 g of the corresponding white solid product, with a yield of 57%.

[0050] The obtained white solid product was analyzed, and the results are as follows: S-(6-Chloro-1,3,5,7-tetraoxo-3,5,6,7-tetrahydropyrrolo[3,4-f]isoindol-2(1H)-yl)O-(4-methoxybenzyl)carbonodithioate: 1 H NMR (400MHz, CDCl3) δ8.26 (s, 2H), 7.34 (d, J = 8.3Hz, 2H), 6.84 (d, J = 8.3Hz, 2H), 4.25 (s, 2H), 3.77 (s, 3H); 13 CNMR (101MHz, CDCl3) δ208.56,167.31,165.91,137.45,136.67,133.52,129.05,128.71,128.58,118.07,55.6ppm The obtained product was confirmed to be a xanthate esterification reagent.

[0051] Example 12 A method for preparing a xanthate esterification reagent: (1) 29.7 g (100 mmol, 1.0 equiv) of bis(benzenesulfonyl)imide (compound 1q in this invention) was added to methanol to obtain a suspension. The suspension was stirred, and then 13.6 mL (120 mmol, 1.2 equiv) of tert-butyl hypochlorite was added. The mixture was reacted at 20 °C for 20 min. The reaction mixture was filtered and dried under vacuum to obtain 30.2 g of N-chlorobis(benzenesulfonyl)imide, with a yield of 91.0%. (2) Potassium O-(3-(1H-indole-1-propyl)methylthioate (OR in this invention) 1Potassium xanthate (2.89 g, 10.0 mmol) corresponding to the 3s group was placed in a 250 mL round-bottom flask and dissolved in acetonitrile. Then, N-chlorobisbenzenesulfonamide (3.32 g, 10.0 mmol) was dissolved in acetonitrile. The N-chlorobisbenzenesulfonamide acetonitrile solution was then slowly added dropwise to an acetonitrile solution of O-(3-(1H-indole-1-propyl)methylthioate potassium salt using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 15 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 2.41 g of the corresponding white solid product, with a yield of 44%.

[0052] The obtained white solid product was analyzed, and the results are as follows: N-(((3-(1H-Indol-1-yl)propoxy)carbonothioyl)thio)-N-(phenylsulfonyl)benzenesulfonamide: 1 HNMR (400MHz, CDCl3) δ8.02(d,J=7.6Hz,4H),7.67(t,J=7.6Hz,2H),7.62(d,J=7.8Hz,1H),7.57(t,J=7.6Hz,4H),7.46(d,J=8.2Hz,1H),7 .31(d,J=3.1Hz,1H),7.24–7.15(m,1H),7.15–7.06(m,1H),6.55–6.47(m,1H),4.22(t,J=6.8Hz,2H),3.96(t,J=6.4Hz,2H),1.98(m,2H); 13 C NMR (101MHz, CDCl3) δ208.7,139.1,134.0,129.2,128.0,136.2,128.8,128.7,121.5,120.9,119.4,110.0,101.2,61.7,42.7,20.9ppm The obtained product was confirmed to be a xanthate esterification reagent.

[0053] Example 13 A method for preparing a xanthate thioesterification reagent: (1) Same as step (1) in Example 3, to obtain N-chlorophthalimide; (2) Potassium trithiocarbonate (SR in this invention) 2Potassium xanthate (1.76 g, 10.0 mmol) was placed in a 250 mL round-bottom flask and dissolved in acetonitrile. N-chlorophthalimide (1.82 g, 10.0 mmol) was then dissolved in acetonitrile. The N-chlorophthalimide acetonitrile solution was then slowly added dropwise to the round-bottom flask containing potassium trithiocarbonate using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 15 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 2.23 g of the corresponding yellow solid product, with a yield of 79%.

[0054] The obtained yellow solid product was analyzed, and the results are as follows: 1,3-Dioxoisoindolin-2-yl ethylcarbonotrithioate 6t: 1 H NMR (400MHz, CDCl3) δ8.00 (dd, J=5.5, 3.1Hz, 2H), 7.86 (dd, J=5.5, 3.1Hz, 2H), 3.31 (d, J=14.9Hz, 2H), 1.29 (t, J=7.5Hz, 3H); 13 C10 NMR (101 MHz, CDCl3) δ 222.03, 166.06, 135.34, 131.93, 124.68, 31.06, 12.73 ppm. The obtained product was confirmed to be a xanthate thioesterification reagent.

[0055] Example 14 A method for preparing a xanthate thioesterification reagent: (1) Same as step (1) in Example 3, to obtain N-chlorophthalimide; (2) Phenethyl trithiocarbonate potassium salt (SR in this invention) 2 Potassium xanthate (2.52 g, 10.0 mmol) was placed in a 250 mL round-bottom flask and dissolved in acetonitrile. Then, N-chlorophthalimide (1.82 g, 10.0 mmol) was dissolved in acetonitrile. The N-chlorophthalimide acetonitrile solution was then slowly added dropwise to the round-bottom flask containing potassium phenylethyl trithiocarbonate using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 15 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 2.62 g of the corresponding yellow solid product, with a yield of 73%.

[0056] The obtained yellow solid product was analyzed, and the results are as follows: 1,3-dioxoisoindolin-2-ylphenethyl carbonotrithioate 6v: 1 H NMR (400MHz, CDCl3) δ7.97(dd,J=5.6,3.1Hz,2H),7.86(dd,J=5.5,3.1Hz,2H),7.21–7.40(m,5H),3.59(m,2H),3.00(m,2H); 13 C NMR (101MHz, CDCl3) δ222.0,217.5,166.1,139.4,135.3,131.9,128.8,128.7,126.9,124.7,38.0,34.2ppm. The product obtained was confirmed to be a xanthate thioesterification reagent.

[0057] Example 15 A method for preparing a xanthan amidation reagent: (1) Same as step (1) in Example 3, to obtain N-chlorophthalimide; (2) Sodium diethyldithiocarbamate (NR in this invention) 3 R 4 Sodium xanthate (5.13 g, 10.0 mmol) corresponding to 3x was placed in a 250 mL round-bottom flask and dissolved in acetonitrile. N-chlorophthalimide (5.46 g, 10.0 mmol) was then dissolved in acetonitrile. The N-chlorophthalimide acetonitrile solution was then slowly added dropwise to the round-bottom flask containing sodium diethyldithiocarbamate using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 15 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain the corresponding yellow solid product of 942.0 mg, with a yield of 32%.

[0058] The obtained yellow solid product was analyzed, and the results are as follows: 1,3-Dioxoisoindolin-2-yldiethylcarbamodithioate 6x: 1 H NMR (400MHz, CDCl3) δ7.91 (dd, J=5.5, 3.0Hz, 2H), 7.78 (dd, J=5.5, 3.1Hz, 2H), 4.05 ( q,J=7.1Hz,2H),3.51(q,J=7.3Hz,2H),1.41(t,J=7.2Hz,3H),1.23(t,J=7.3Hz,3H); 13C NMR (101MHz, CDCl3) δ174.4,165.1,134.8,132.2,124.3,48.3,47.6,13.9,11.1ppm. The obtained product was confirmed to be a xanthan amidating agent.

[0059] Example 16 A method for preparing a xanthan amidation reagent: (1) Same as step (1) in Example 3, to obtain N-chlorophthalimide; (2) Potassium morpholine-4-methylthioate (NR in this invention) 3 R 4 Potassium xanthate (2.01 g, 10.0 mmol) corresponding to 3y was placed in a 250 mL round-bottom flask and dissolved in acetonitrile. N-chlorophthalimide (1.82 g, 10.0 mmol) was then dissolved in acetonitrile. The N-chlorophthalimide acetonitrile solution was then slowly added dropwise to the round-bottom flask containing potassium morpholine-4-methylthioate using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 12 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 1.60 g of the corresponding white solid product, with a yield of 52%.

[0060] The obtained white solid product was analyzed, and the results are as follows: 1,3-dioxoisoindolin-2-ylmorpholine-4-carbodithioate 6y: 1 H NMR (400MHz, CDCl3) δ7.91 (dd, J=5.5, 3.0Hz, 2H), 7.78 (dd, J=5.5, 3.1Hz, 2H) 3.82 (t, J=5.2Hz, 4H), 3.73 (t, J=6.0Hz, 4H); 13 C NMR (101MHz, CDCl3) δ175.7,163.1,140.8,134.8,123.3,66.1,49.7ppm. The obtained product was confirmed to be a xanthan amidating agent.

[0061] Example 17 A method for preparing a xanthan amidation reagent: (1) Same as step (1) in Example 3, to obtain N-chlorophthalimide; (2) Potassium 1H-indole dithiocarbamate (NR in this invention) 3 R 4Potassium xanthate (2.31 g, 10.0 mmol) corresponding to 3z was placed in a 250 mL round-bottom flask and dissolved in acetonitrile. N-chlorophthalimide (1.82 g, 10.0 mmol) was then dissolved in acetonitrile. The N-chlorophthalimide acetonitrile solution was then slowly added dropwise to the round-bottom flask containing potassium 1H-indole dithiocarbamate using a constant-pressure dropping funnel. After the addition was complete, the reaction was carried out at 25 °C for 14 h, and the reaction was monitored by TLC. The solvent was then removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 2.06 g of the corresponding white solid product, with a yield of 61%.

[0062] The obtained white solid product was analyzed, and the results are as follows: 1,3-dioxoisoindolin-2-yl 1H-indole-1-carbodithioate 6z: 1 H NMR (400MHz, CDCl3) δ7.93 (dd, J=5.5, 3.0Hz, 2H), 7.80 (dd, J=5.5, 3.1Hz, 2H), 7.59–7.51 (m, 1H), 7.28 –7.22(m,1H),7.20–7.10(m,1H),7.07–7.00(m,1H),6.97(d,J=3.1Hz,1H),6.41(dd,J=3.1,0.8Hz,1H); 13 C NMR (101MHz, CDCl3) δ176.4,164.1,135.3,134.8,132.2,124.3,130.3,125.1,124.9,123.5,120.7,116.4,108.9ppm. The obtained product was confirmed to be a xanthan amidating agent.

[0063] Example 18 The xanthate esterification reagent (referred to as reagent 4j) obtained in Example 3 was reacted with 4-phenylphenylboronic acid as follows: Under argon atmosphere, 0.5 mmol of 4-phenylphenylboronic acid, reagent 4j, 0.25 mmol of sodium carbonate, 0.025 mmol of anhydrous copper sulfate, and 0.025 mmol of ligand were placed in a 25 mL sealed tube, followed by the addition of 5 mL of acetonitrile. The reaction was carried out at 60 °C for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain the corresponding product. The reaction mechanism of 4-phenylphenylboronic acid substrate, reagent 4j, base, copper salt, and ligand under different conditions is as follows: yield (crude NMR yield), 1,3,5-trimethoxybenzene as internal standard: The ligands used are The reaction conditions and yields are shown in Table 1. Table 1 Reaction conditions and yield

[0064] Example 19 Reagent 4j was reacted with a carbonyl compound, as follows: Under argon atmosphere, 0.5 mmol of β-keto ester (methyl 1-oxo-2,3-dihydro-1H-indene-2-carboxylate), 0.6 mmol of reagent 4j, and 0.55 mmol of potassium carbonate were placed in a 25 mL sealed tube, followed by the addition of 5 mL of DCE. The reaction was allowed to proceed for 15 hours. After the reaction, the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain the corresponding xanthate product. Using 1,3,5-trimethoxybenzene as an internal standard, the yield was the crude NMR yield. The reaction conditions and results are shown in Table 2. The reaction mechanism is as follows: Table 2 Reaction conditions and results

[0065] Example 20 Reagent 4j was reacted with aliphatic amines as follows: Under argon atmosphere, 0.5 mmol of benzylamine and 0.6 mmol of reagent 4j were placed in a 25 mL sealed tube, followed by the addition of 5 mL of toluene. The reaction was carried out at 25 °C for 16 hours. After the reaction was completed, the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain the corresponding xanthate product. The yield was the crude NMR yield. 1,3,5-trimethoxybenzene was used as an internal standard. The reaction results are shown in Table 3. The reaction mechanism is as follows: Table 3 Reaction conditions and results

[0066] Example 21 The reagent 4j was reacted with phenol as follows: Under argon atmosphere, 0.5 mmol of phenol, 4 ml of reagent, and 0.55 mmol of base were placed in a 25 mL sealed tube, followed by the addition of 5 mL of 1,2-dichloroethane. The reaction was carried out at 80 °C for 16 hours. After the reaction, the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain the corresponding xanthate product. The yield was the crude NMR yield. 1,3,5-trimethoxybenzene was used as an internal standard. The reaction results are shown in Table 4. The reaction mechanism is as follows: Table 4 Reaction conditions and results

[0067] Example 22 The reaction of reagent 4j with 4-methoxyphenylboronic acid: Under argon atmosphere, 0.5 mmol of 4-methoxyphenylboronic acid, 0.6 mmol of reagent 4j, 0.25 mmol of sodium carbonate, 0.025 mmol of anhydrous copper sulfate, and 0.025 mmol of 2,2'-bipyridine were placed in a 25 mL sealed tube, followed by the addition of 5 mL of acetonitrile. The reaction was carried out at 60 °C for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 81.8 mg of the corresponding product, with a yield of 72%.

[0068] The product was analyzed, as follows: O-Ethyl S-(4-methoxyphenyl)carbonodithioate: 1 H NMR (400MHz, CDCl3) δ7.56–7.34(m,2H),6.97–6.90(m,2H),4.60(q,J=7.2Hz,2H),3.83(s,3H),1.33(t,J=7.1Hz,3H); 13 CNMR (101MHz, CDCl3) δ195.9,157.8,147.1,122.8,114.5,70.5,55.6,13.9ppm. Therefore, the substance obtained is Xanthate groups were successfully incorporated into the target molecule.

[0069] Example 23 The reaction of reagent 4j with trans-β-styreneboronic acid: Under argon atmosphere, 0.5 mmol of trans-β-styreneboronic acid, 0.6 mmol of reagent 4j, 0.25 mmol of sodium carbonate, 0.025 mmol of anhydrous copper sulfate, and 0.025 mmol of 2,2'-bipyridine were placed in a 25 mL sealed tube, followed by the addition of 5 mL of acetonitrile. The reaction was carried out at 60 °C for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 103.1 mg of the corresponding product, with a yield of 92%. The product was analyzed as follows: (E)-O-Ethyl S-styryl carbonodithioate: 1H NMR(400MHz, CDCl3)7.46–7.40(m,2H),7.40–7.33(m,2H),7.32–7.30(m,1H),7.30 –7.26(m,1H),6.76(d,J=16.1Hz,1H),4.70(q,J=7.1Hz,2H),1.45(t,J=7.1Hz,3H); 13 C NMR (101MHz, CDCl3) δ211.6,136.0,133.0,128.9,128.5,126.7,121.0,70.3,13.9ppm. Therefore, the obtained substance is... Xanthate groups were successfully incorporated into the target molecule.

[0070] Example 24 Under argon atmosphere, 0.5 mmol of 4-phenylphenylboronic acid, 0.6 mmol of reagent 6d (the reagent obtained in Example 5), 0.25 mmol of sodium carbonate, 0.025 mmol of anhydrous copper sulfate, and 0.025 mmol of 2,2'-bipyridine were placed in a 25 mL sealed tube, followed by the addition of 5 mL of acetonitrile. The reaction was carried out at 60 °C for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 135.6 mg of the corresponding product, with a yield of 81%. The obtained product was analyzed as follows: S-([1,1'-Biphenyl]-4-yl)O-(4-chlorobutyl)carbonodithioate: 1 H NMR (400MHz, CDCl3) δ7.65 (dd, J=14.4, 7.7Hz, 4H), 7.59 (d, J=8.4Hz, 2H), 7.48 (t, J=7.5Hz, 2H), 7.40 (t,J=7.3Hz,1H),4.58(t,J=6.1Hz,2H),3.44(t,J=6.4Hz,2H),1.90–1.82(m,2H),1.78–1.69(m,2H); 13 C NMR (101MHz, CDCl3) δ212.9,143.1,140.0,135.6,129.1,128.7,128.2,128.1,127.3,73.4,44.4,29.1,25.7ppm. Therefore, the product obtained is Xanthate groups were successfully incorporated into the target molecule.

[0071] Example 25 Procedure: Under argon atmosphere, 0.5 mmol of 4-phenylphenylboronic acid, 0.6 mmol of reagent (6 g, obtained in Example 6), 0.25 mmol of sodium carbonate, 0.025 mmol of anhydrous copper sulfate, and 0.025 mmol of 2,2'-bipyridine were placed in a 25 mL sealed tube, followed by the addition of 5 mL of acetonitrile. The reaction was carried out at 60 °C for 15 hours. After the reaction, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 113.9 mg of the product, with a yield of 72%. The product was analyzed as follows: S-([1,1'-Biphenyl]-4-yl)O-(pent-4-en-1-yl)carbonodithioate: 1 H NMR (400MHz, CDCl3) δ7.70–7.58(m,6H),7.49(t,J=7.5Hz,2H),7.41(t,J=7.3Hz,1H),5.87–5.61 (m,1H),4.99(d,J=11.7Hz,2H),4.58(t,J=6.3Hz,2H),2.04(q,J=7.2Hz,2H),1.86–1.76(m,2H); 13 CNMR(101MHz, CDCl3)δ213.0,143.0,140.0,137.2,135.6,129.1,128.9,128.1,128.0,127.3,115.8,73.7,30.0,27.5ppm. Therefore, the product obtained is Xanthate groups were successfully incorporated into the target molecule.

[0072] Example 26 Under argon atmosphere, 0.5 mmol of 4-phenylphenylboronic acid, 0.6 mmol of reagent 6p (the reagent obtained in Example 7), 0.25 mmol of sodium carbonate, 0.025 mmol of anhydrous copper sulfate, and 0.025 mmol of 2,2'-bipyridine were placed in a 25 mL sealed tube, followed by the addition of 5 mL of acetonitrile. The reaction was carried out at 60 °C for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 143.5 mg of the corresponding product, with a yield of 82%. The obtained product was analyzed as follows: S-([1,1'-Biphenyl]-4-yl)O-phenethyl carbonodithioate: 1H NMR (400MHz, CDCl3) δ7.69 (dd, J=7.9, 3.7Hz, 4H), 7.55 (dd, J=13.7, 7.5Hz, 4H), 7.46 (t, J=7.3Hz ,1H),7.28(d,J=6.3Hz,3H),7.08(d,J=7.8Hz,2H),4.82(t,J=6.6Hz,2H),3.04(t,J=6.6Hz,2H); 13 C NMR (101MHz, CDCl3) δ212.7,143.0,140.1,137.4,135.6,129.2,129.1,128.7,128.2,128.1,127.4,127.1,126.8,74.6,34.6ppm. Therefore, the product obtained is Xanthate groups were successfully incorporated into the target molecule.

[0073] Example 27 Under argon atmosphere, 0.5 mmol of 4-phenylphenylboronic acid, 0.6 mmol of reagent 6r (the reagent obtained in Example 8), 0.25 mmol of sodium carbonate, 0.025 mmol of anhydrous copper sulfate, and 0.025 mmol of 2,2'-bipyridine were placed in a 25 mL sealed tube, followed by the addition of 5 mL of acetonitrile. The reaction was carried out at 60 °C for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 140.4 mg of the corresponding product, with a yield of 79%. The obtained product was analyzed as follows: S-([1,1'-Biphenyl]-4-yl)O-(2-(thiophen-3-yl)ethyl)carbonodithioate: 1 HNMR (400MHz, CDCl3) δ7.73–7.64(m,4H),7.57(d,J=8.3Hz,2H),7.52(t,J=7.6Hz,2H),7.45(t,J=7.3Hz,1H),7.23 (dd,J=4.9,3.0Hz,1H),6.84(d,J=2.3Hz,1H),6.82(d,J=3.6Hz,1H),4.79(t,J=6.5Hz,2H),3.06(t,J=6.5Hz,2H); 13 C NMR (101MHz, CDCl3) δ211.6,141.9,138.9,136.4,134.5,128.1,127.6,127.2,127.1,127.0,126.3,124.7,121.0,72.9,28.0ppm. Therefore, the product obtained is Xanthate groups were successfully incorporated into the target molecule.

[0074] Example 28 Under argon atmosphere, 0.5 mmol of 4-phenylphenylboronic acid, 0.6 mmol of reagent 6x (prepared in Example 10), 0.25 mmol of sodium carbonate, 0.025 mmol of anhydrous copper sulfate, and 0.025 mmol of 2,2'-bipyridine were placed in a 25 mL sealed tube, followed by the addition of 5 mL of acetonitrile. The reaction was carried out at 60 °C for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 97.9 mg of the corresponding product, with a yield of 65%. The product was analyzed as follows: S-[1,1'-Biphenyl]-4-yl diethylcarbamodithioate: 1 H NMR (400MHz, CDCl3) δ7.73–7.62(m,4H),7.57(d,J=8.4Hz,2H),7.46(t,J=7.4Hz,2H),7.38(t,J=7. 4Hz, 1H), 4.05 (q, J = 7.1Hz, 2H), 3.88 ( q, J = 7.0Hz, 2H), 1.42 ( t, J = 7.0Hz, 3H), 1.31 ( t, J = 7.1Hz, 3H); 13 C NMR (101MHz, CDCl3) δ196.0,142.8,140.3,137.6,130.5,129.0,127.9,127.9,127.4,50.0,47.5,12.9,11.8ppm. Therefore, the product is... Xanthan amide groups were successfully incorporated into the target molecule phenylboronic acid.

[0075] Example 29 Reaction with carbonyl compounds: Under argon atmosphere, 0.5 mmol of methyl 6-fluoro-1-oxo-2,3-indene-2-carboxylate, 0.6 mmol of reagent 4j, and 0.55 mmol of potassium carbonate were placed in a 25 mL sealed tube, followed by the addition of 5 mL of 1,2-dichloroethane. The reaction was carried out at 80 °C for 16 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 104.1 mg of the product, with a yield of 63%. The product was analyzed as follows: Methyl2-((ethoxycarbonothioyl)thio)-6-fluoro-1-oxo-2,3-dihydro-1H-indene-2-carboxylate: 1 H NMR (400MHz, CDCl3) δ7.52–7.36(m,3H),4.46(qd,J=7.2,2.5Hz,2H),4.21(d ,J=17.6Hz,1H),3.75(s,3H),3.59(d,J=17.5Hz,1H),1.07(t,J=7.1Hz,3H); 19 F NMR (376MHz, CDCl3) δ-112.7 (m, 1F); 13 C NMR (101MHz, CDCl3) δ209.0, 194.4, 166.9, 162.7 (d, J = 251.5Hz), 147.8, 135.9 (d, J = 8.1Hz), 127. 7(d,J=8.1Hz),124.0(d,J=24.2Hz),111.1(d,J=22.2Hz),70.57,67.96,54.29,40.96,13.04ppm. It can be seen that the product obtained is Xanthate groups were successfully incorporated into the carbonyl group of the target molecule.

[0076] Example 30 Under argon atmosphere, 0.5 mmol of methyl 4-bromo-1-oxo-2,3-indene-2-carboxylate, 0.6 mmol of reagent 6d (the reagent prepared in Example 5), and 0.55 mmol of potassium carbonate were placed in a 25 mL sealed tube, followed by the addition of 5 mL of 1,2-dichloroethane. The reaction was carried out at 80 °C for 16 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 179.3 mg of the corresponding product, with a yield of 79%. The obtained substance was analyzed, and the results are as follows: Methyl4-bromo-2-(((4-chlorobutoxy)carbonothioyl)thio)-1-oxo-2,3-dihydro-1H-indene-2-carboxylate: 1H NMR (400MHz, CDCl3) δ7.85(d,J=7.8Hz,1H),7.76(d,J=7.6Hz,1H),7.36(t,J=7.7Hz,1H),4.50–4.39(m,2H),4.16( d,J=18.3Hz,1H),3.75(s,3H),3.53(d,J=18.2Hz,1H),3.46(t,J=6.4Hz,2H),1.74–1.65(m,2H),1.65–1.57(m,2H); 13 C NMR (101MHz, CDCl3) δ209.0,194.5,166.7,151.8,138.9,136.1,130.2,124.2,121.6,73.6,67.1,54.4,44.2,42.5,28.8,25.3ppm. It can be seen that the product obtained is Xanthate groups were successfully incorporated into the carbonyl group of the target molecule.

[0077] Example 31 Under argon atmosphere, 0.5 mmol of methyl 4-bromo-1-oxo-2,3-indene-2-carboxylate, 0.6 mmol of reagent 6r (the reagent obtained in Example 8), and 0.55 mmol of potassium carbonate were placed in a 25 mL sealed tube, followed by the addition of 5 mL of 1,2-dichloroethane. The reaction was carried out at 80 °C for 16 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 199.9 mg of the corresponding product, with a yield of 85%. The product was analyzed as follows: 4-bromo-1-oxo-2-(((2-(thiophen-3-yl)ethoxy)carbonothioyl)thio)-2,3-dihydro-1H-indene-2-carboxylate: 1 H NMR (400MHz, CDCl3) δ7.83(d,J=7.8Hz,1H),7.73(d,J=7.5Hz,1H),7.33(t,J=7.7Hz,1H),7.26(td,J=6.4,5.6,3.4Hz,1H),6.97(d,J=1.8H z,1H),6.87(dd,J=4.9,1.4Hz,1H),4.71–4.60(m,2H),4.13(d,J=18.3Hz,1H),3.73(s,3H),3.48(d,J=18.3Hz,1H),2.82(t,J=7.1Hz,2H); 13C NMR (101MHz, CDCl3) δ209.0,194.5,166.7,152.0,138.9,136.6,136.0,130.1,128.0,126.2,124.1,122.0,121.6,73.8,67.2,54.3,42.5,28.5ppm. It can be seen that the product obtained is Xanthate groups were successfully incorporated into the carbonyl group of the target molecule.

[0078] Example 32 Under argon atmosphere, 0.5 mmol of methyl 4-bromo-1-oxo-2,3-indene-2-carboxylate, 0.6 mmol of reagent 6t (the reagent obtained in Example 9), and 0.55 mmol of potassium carbonate were placed in a 25 mL sealed tube, followed by the addition of 5 mL of 1,2-dichloroethane. The reaction was carried out at 80 °C for 16 hours. After the reaction, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 67.7 mg of the corresponding product, with a yield of 33%. The product was analyzed as follows: 4-bromo-2-(((ethylthio)carbonothioyl)thio)-1-oxo-2,3-dihydro-1H-indene-2-carboxylate: 1 H NMR (400MHz, CDCl3) δ7.83(d,J=7.7Hz,1H),7.74(d,J=7.6Hz,1H),7.33(t,J=7.7Hz,1H),4.35(d, J=18.4Hz,1H),3.75(s,3H),3.57(d,J=18.4Hz,1H),3.30(q,J=7.4Hz,2H),1.33(t,J=7.4Hz,3H); 13 C NMR (101MHz, CDCl3) δ219.8,194.4,166.5,152.6,139.0,136.0,130.0,124.1,121.7,69.0,54.4,41.9,32.3,12.9ppm. It can be seen that the product obtained is Xanthate groups were successfully incorporated into carbonyl compounds.

[0079] Example 33 Under argon atmosphere, 0.5 mmol of 4-bromobenzylamine and 0.6 mmol of reagent 4j were placed in a 25 mL sealed tube, followed by the addition of 5 mL of toluene. The reaction was carried out at room temperature for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to give 98.3 mg of the corresponding xanthate product, with a yield of 64% and a dr ratio of 1.9:1. The product was analyzed as follows: N-(4-Bromobenzyl)-S-(ethoxycarbonothioyl)thiohydroxylamine: 1 H NMR(400MHz, CDCl3)δ7.45(dd,J=8.3,1.6Hz,2H),7.22–7.14(m,1.30H),7.13–7.08(m,0.70H),7.02(s,0.31H),6.47(s,0.56H),4.70(d,J =5.9Hz,1.30H,major),4.53(q,J=7.1Hz,0.70H),4.49(q,J=7.1Hz,1.30H),4.37(d,J=6.0Hz,0.70H,minor),1.31(td,J=7.1,3.6Hz,3H); 13 C NMR (101MHz, CDCl3) δ191.0,190.1,136.1,135.8,132.0,131.9,129.6,129.4,121.8,121.8,68.3,66.8,48.4,46.5,14.3,14.3ppm. It can be seen that the product obtained is Xanthan ester groups were successfully incorporated into fatty amines.

[0080] Example 34 Under argon atmosphere, 0.5 mmol of 4-methoxybenzylamine and 0.6 mmol of reagent 6t (prepared in Example 9) were placed in a 25 mL sealed tube, followed by the addition of 5 mL of toluene. The reaction was carried out at room temperature for 16 hours. After the reaction, the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 97.4 mg of the corresponding xanthate product, with a yield of 71% and a dr ratio of 3.4:1. The product was analyzed as follows: S-((Ethylthio)carbonothioyl)-N-(4-methoxybenzyl)thiohydroxylamine: 1H NMR (400MHz, CDCl3) δ7.23(d,J=8.6Hz,2H),7.12(s,1H),6.86(d,J=8.7Hz,2H),4.80(d,J=4.9Hz,1.55H ,major),4.50(d,J=5.3Hz,0.45H,minor),3.78(d,J=4.3Hz,3H),3.37–3.20(m,2H),1.42–1.27(m,3H); 13 C NMR (101MHz, CDCl3) δ 198.0, 159.5, 129.9, 129.5, 128.3, 127.3, 114.4, 114.3, 55.4, 50.7, 50.0, 30.8, 29.9, 14.4, 13.9 ppm. It can be seen that the obtained product is... Xanthate groups were successfully incorporated into aliphatic amines.

[0081] Example 35 Under argon atmosphere, 0.5 mmol of 4-methoxyphenol, 0.7 mmol of reagent 4j, and 0.55 mmol of cesium carbonate were placed in a 25 mL sealed tube, followed by the addition of 5 mL of 1,2-dichloroethane. The reaction was carried out at 80 °C for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to give 103.6 mg of the corresponding xanthate product, with a yield of 85%. The product was analyzed as follows: O-Ethyl SO-(4-methoxyphenyl)carbonothio(thioperoxoate): 1 H NMR (400MHz, CDCl3) δ7.06–6.98(m,2H),6.95–6.87(m,2H),4.58(q,J=7.1Hz,2H),3.80(s,3H),1.45(t,J=7.1Hz,3H); 13 C NMR (101MHz, CDCl3) δ 195.9, 157.8, 147.1, 122.8, 114.5, 70.5, 55.6, 13.9 ppm. Therefore, the obtained product is... Xanthan ester groups were successfully incorporated into the target phenolic molecule.

[0082] Example 36 Under argon atmosphere, 0.5 mmol of 4-iodophenol, 0.7 mmol of reagent 6t (the reagent obtained in Example 9), and 0.55 mmol of cesium carbonate were placed in a 25 mL sealed tube, followed by the addition of 5 mL of 1,2-dichloroethane. The reaction was carried out at 80 °C for 16 hours. After the reaction was completed, the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 88.0 mg of the corresponding xanthate product, with a yield of 66%. The product was analyzed as follows: SO-(4-Chlorophenyl)S-ethyl carbonodithio(thioperoxoate): 1 H NMR (400MHz, CDCl3) δ7.43–7.32(m,2H),7.07–6.98(m,2H),3.22(q,J=7.4Hz,2H),1.41(t,J=7.5Hz,3H); 13 CNMR (101MHz, CDCl3) δ214.8,152.9,132.1,129.8,123.7,31.5,13.2ppm. It can be seen that the product obtained is Xanthate groups were successfully incorporated into phenolic substances.

[0083] Example 37 Reaction with 7-hydroxycoumarinboric acid derivatives: Under argon atmosphere, 0.5 mmol (2-oxo-2H-chromen-7-yl)boric acid, 0.6 mmol reagent 4j, 0.25 mmol sodium carbonate, 0.025 mmol anhydrous copper sulfate, and 0.025 mmol 2,2'-bipyridine were placed in a 25 mL sealed tube, followed by the addition of 5 mL acetonitrile. The reaction was carried out at 60 °C for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 103.9 mg of the corresponding xanthate product, with a yield of 78%. The product was analyzed as follows: O-EthylS-(2-oxo-2H-chromen-7-yl)carbonodithioate: 1 H NMR (400MHz, CDCl3) δ7.72(d,J=10.2Hz,1H),7.52(d,J=8.1Hz,1H),7.49(d,J=1.6Hz,1H),7. 39(dd,J=8.0,1.6Hz,1H),6.49(d,J=9.6Hz,1H),4.62(q,J=7.1Hz,2H),1.35(t,J=7.1Hz,3H); 13C NMR (101MHz, CDCl3) δ210.8,160.1,153.9,142.8,134.3,130.7,128.3,123.2,119.9,118.2,70.9,13.7ppm. It can be seen that the product obtained is Xanthate groups have been successfully incorporated into coumarin compounds.

[0084] Example 38 Reaction with aliphatic amine bioactive molecules: Under argon atmosphere, 0.5 mmol of methyl 2-amino-3-phenylpropionate and 0.6 mmol of reagent 4J were placed in a 25 mL sealed tube, followed by the addition of 5 mL of toluene. The reaction was carried out at room temperature for 16 hours. After the reaction was complete, the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to give 87.4 mg of the corresponding xanthate product, with a yield of 58% and a dr ratio of 3.3:1. The product was analyzed as follows: Methyl((ethoxycarbonothioyl)thio)-L-phenylalaninate: 1 H NMR (400MHz, CDCl3) δ7.32–7.21(m,3H),7.15–7.05(m,2H),6.96(d,J=7.9Hz, 0.23H),6.63(d,J=7.9Hz,0.77H),5.27–5.12(m,0.77H),4.83–4.66(m,0.23H ),4.54–4.33(m,2H),3.71(d,J=3.9Hz,3H),3.34–3.14(m,1.53H,major),3.1 4–2.93(m,0.47H,minor),1.30(t,J=7.1Hz,2.29H),1.25(t,J=7.1Hz,0.71H); 13 C NMR (101MHz, CDCl3) δ 190.1, 189.4, 171.6, 170.6, 135.6, 135.4, 129.4, 129.3, 128.9, 128.7, 127.5, 127.3, 68.1, 66.8, 58.3, 56.7, 52.6, 52.5, 38.7, 37.3, 14.3, 14.1 ppm. It can be seen that the obtained product is... Xanthate groups have been successfully incorporated into aliphatic amine bioactive molecules.

[0085] Example 39 Under argon atmosphere, 0.5 mmol vanillin, 0.7 mmol reagent 4j, and 0.55 mmol cesium carbonate were placed in a 25 mL sealed tube, followed by the addition of 5 mL of 1,2-dichloroethane. The reaction was carried out at 80 °C for 16 hours. After the reaction, the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 121.6 mg of the corresponding xanthate product, with a yield of 89%. The product was analyzed as follows: O-Ethyl SO-(4-formyl-2-methoxyphenyl)carbonothio(thioperoxoate): 1 H NMR (400MHz, CDCl3) δ9.93 (s, 1H), 7.53–7.43 (m, 2H), 7.22 (d, J = 7.8Hz, 1H), 4.56 (q, J = 7.2Hz, 2H), 3.87 (s, 3H), 1.43 (t, J = 7.1Hz, 3H); 13 C NMR (101MHz, CDCl3) δ 193.8, 191.0, 152.0, 146.7, 135.7, 124.7, 123.9, 111.4, 71.0, 56.2, 13.8 ppm. It can be seen that the obtained product is... Xanthate groups have been successfully incorporated into phenolic bioactive molecules.

[0086] Example 40 The xanthate esterifying reagent 4j of this invention reacts with 4-chlorophenylboronic acid to generate a 4-chlorophenyl xanthate ester product, which can then be converted to successfully synthesize the insecticide Tetradifon. The reaction mechanism is as follows: The specific preparation method is as follows: (1) Synthesis of 4-chlorothiophenol Under argon atmosphere, 15 mmol of p-chlorophenylboronic acid, 18 mmol of reagent 4j, 7.5 mmol of sodium carbonate, 0.75 mmol of anhydrous copper sulfate, and 0.75 mmol of 2,2'-bipyridine were placed in a 100 mL round-bottom flask, followed by the addition of 30 mL of acetonitrile. The reaction was carried out at 60 °C for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to obtain 2.55 g of the corresponding ethyl p-chlorophenyl xanthate product, with a yield of 73%. Subsequently, 7.32 mmol of this product was placed in a 100 mL round-bottom flask, and 31.5 mmol of potassium hydroxide and 30 mL of ethanol were added. The mixture was refluxed overnight. After the reaction was completed, the solvent was removed by rotary evaporation under reduced pressure, and the residue was purified by rapid silica gel column chromatography to obtain 952.7 mg of the corresponding p-chlorothiophenol, with a yield of 90%. The product was analyzed as follows: 4-Chlorobenzenethiol: 1 H NMR (400MHz, CDCl3) δ7.20 (s, 4H), 3.45 (s, 1H); 13 CNMR (101 MHz, CDCl3) δ 131.7, 130.8, 129.3, 129.2 ppm. The obtained product was confirmed to be... (2) Synthesis of (4-chlorophenyl)(2,4,5-trichlorophenyl) sulfide Under argon atmosphere, 5.88 mmol of 1,2,4-trichloro-5-iodobenzene, 5.88 mmol of p-chlorothiophenol, 11.76 mmol of potassium carbonate, 0.59 mmol of cuprous iodide, and 11.76 mmol of ethylene glycol were placed in a 25 mL sealed tube, followed by the addition of 6 mL of isopropanol. The reaction was carried out at 80 °C for 30 hours. After the reaction was complete, the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to give 1.83 g of the corresponding thioether product, with a yield of 96%. The product was analyzed as follows: (4-Chlorophenyl)(2,4,5-trichlorophenyl)sulfane: 1 H NMR (400MHz, CDCl3) δ7.48(s,1H),7.39(s,4H),6.94(s,1H); 13 C10 NMR (101 MHz, CDCl3) δ 136.8, 135.6, 135.0, 131.7, 131.3, 130.8, 130.2, 130.0, 129.6, 129.3 ppm. The obtained product was confirmed to be... (3) Synthetic insecticide Tetradifon 1 mmol of (4-chlorophenyl)(2,4,5-trichlorophenyl) sulfide and 4 mmol of m-CPBA were placed in a 25 mL sealed tube, followed by the addition of 5 mL of dichloromethane. The reaction was carried out at 40 °C for 12 hours. After the reaction was completed, the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by rapid silica gel column chromatography to give the corresponding product Tetradifon 250.9 mg, with a yield of 70%. The product was analyzed as follows: 1,2,4-Trichloro-5-((4-chlorophenyl)sulfonyl)benzene: 1 H NMR (400MHz, CDCl3) δ8.40(s,1H),7.90–7.86(m,2H),7.54(s,1H),7.52–7.48(m,2H); 13C10 NMR (101 MHz, CDCl3) δ 141.0, 139.3, 137.8, 137.6, 133.4, 132.5, 132.2, 131.4, 130.3, 129.6 ppm. The obtained product was confirmed to be...

[0087] The advantage of this method is that the first step of preparing thiophene involves reacting room-temperature stable and readily available arylboronic acid with the electrophilic reagent 4j of this invention to prepare the aryl xanthate esterified product, which is then hydrolyzed. In contrast, the traditional preparation of Leuckart's thiophene requires the use of dangerous and easily explosive aryl diazonium salts as starting materials to react with potassium ethyl xanthate.

Claims

1. The application of a xanthate derivatization reagent, characterized in that: The application is as follows: using a xanthate derivatization reagent to react with the target molecule, directly introducing xanthate, xanthate thioester or xanthamide groups into the target molecule, wherein the target molecule is arylboronic acid or a boric acid derivative of coumarin, carbonyl compound, fatty amine or phenol; The xanthate derivatizing agent is prepared by the following method: using an amide or sulfonamide as a raw material, after chlorination, it undergoes a nucleophilic substitution reaction with a xanthate metal salt to prepare an electrophilic xanthate derivatizing agent. The reaction mechanism is as follows: ; Wherein, the amide or sulfonamide is any one of the following compounds 1a to 1q: ; The xanthate metal salt is represented as follows: Where M is lithium, sodium, potassium, rubidium, or cesium; R is an alkoxy group OR 1 The OR 1 It is any one of the following groups 3a to 3s: ； Or R is an alkylthio group SR 2 The SR 2 It is any one of the following groups 3t to 3w: ; Or R is an alkylamine group NR 3 R 4 The NR 3 R 4 It is any one of the following groups 3x to 3z: ; (i) When the target molecule is an arylboronic acid or a boric acid derivative of coumarin, the specific reaction is as follows: Under an inert atmosphere, the target molecule arylboronic acid or a boric acid derivative of coumarin, a copper catalyst, a ligand, a base, and a xanthate derivatizing agent are mixed, a solvent is added, and the mixture is stirred at 25-80°C for 4-20 hours to obtain the corresponding xanthate derivatized product. The solvent is one or more of the following: aromatic solvents, halogenated hydrocarbon solvents, ether solvents, nitrile solvents, and amide solvents; The base is one or more of the following: carbonates, phosphates, hydroxide metal salts, and tert-butanol metal salts; The ligand is a nitrogen-containing bidentate ligand or a nitrogen-containing tripentate ligand; The copper catalyst is a monovalent copper catalyst or a divalent copper catalyst; The molar ratio of the arylboronic acid or coumarin boric acid derivative to the xanthate derivatization reagent, base, copper catalyst, and ligand is 1:(1-1.5):(0.25-1.5):(0.02-0.2):(0.02-0.2). (ii) When the target molecule is a carbonyl compound, the carbonyl compound is methyl 1-oxo-2,3-dihydro-1H-indene-2-carboxylate, methyl 6-fluoro-1-oxo-2,3-indene-2-carboxylate, or methyl 4-bromo-1-oxo-2,3-indene-2-carboxylate, and the corresponding product structures are respectively ; The reaction is as follows: Under an inert atmosphere, the target molecule carbonyl compound, base and xanthate derivatizing agent are mixed, a solvent is added, and the reaction is stirred at 20-100℃ for 4-20 h to obtain the corresponding xanthate derivatized product. The solvent is one or more of the following: aromatic solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, sulfoxide solvents, amide solvents, and alcohol solvents. The base is one or more of the following: carbonates, phosphates, hydroxide metal salts, and tert-butanol metal salts; The molar ratio of the carbonyl compound, the base, and the xanthate derivatizing agent is 1:(1-2):(1-2); (iii) When the target molecule is an aliphatic amine, the reaction is as follows: Under an inert atmosphere, the target molecule fatty amine is mixed with a xanthate derivatization reagent, a solvent is added, and the mixture is stirred at 10-40℃ for 4-20 hours to obtain the corresponding xanthate derivatization product. The solvent is one or more of the following: aromatic solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, sulfoxide solvents, amide solvents, and alcohol solvents. The molar ratio of the fatty amine to the xanthate derivatizing agent is 1:(1-2). (iv) When the target molecule is a phenol, the reaction is as follows: Under an inert atmosphere, the target phenolic molecule is mixed with a xanthate derivatizing reagent and a base, a solvent is added, and the mixture is stirred at 20-100℃ for 4-20 hours to obtain the corresponding xanthate derivatized product. The solvent is one or more of the following: aromatic solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, sulfoxide solvents, amide solvents, and alcohol solvents. The base is one or more of the following: carbonates, phosphates, hydroxide metal salts, and tert-butanol metal salts; The molar ratio of the phenols to the base and xanthate derivatizing reagent is 1:(1-2):(1-2).

2. The application according to claim 1, characterized in that: The xanthate derivatizing agent was prepared by the following method: (1) Add the first solvent to the amide or sulfonamide, stir, then add tert-butyl hypochlorite, react at 20-40℃ for 5-60 min, filter the reaction mixture, dry it, and obtain the intermediate product N-chloroamide or N-chlorosulfonamide. (2) Add a second solvent to the xanthate metal salt, stir to obtain a xanthate metal salt solution, then dissolve the N-chloroamide or N-chlorosulfonamide in the second solvent, and then add it dropwise to the xanthate metal salt solution. React at 10-40℃ for 4-20h to obtain the corresponding xanthate ester derivatization reagent. Wherein, the first solvent is at least one of aromatic solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, sulfoxide solvents, amide solvents, or alcohol solvents; the second solvent is at least one of aromatic solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, sulfoxide solvents, amide solvents, or alcohol solvents.

3. The application according to claim 2, characterized in that: In step (1), the molar ratio of amide or sulfonamide to tert-butyl hypochlorite is 1:(1-1.5); in step (2), the molar ratio of N-chloroamide or N-chlorosulfonamide to xanthate metal salt is 1:(1-1.5).

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