Method for catalytic activation of carbon dioxide as a carbonylation reagent by inorganic sulfur

Abstract

This invention provides a method for inorganic sulfur-catalyzed activation of carbon dioxide as a carbonylating agent. In this method, carbon dioxide, in the presence of H2S and a base, can replace toxic and harmful carbonylating agents to synthesize carbonyl-containing fine chemicals. The method has high atom economy and can reduce the generation of byproducts.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis, and more specifically, it provides a method for inorganic sulfur-catalyzed activation of carbon dioxide as a carbonylation reagent. Background Technology

[0002] The development of green and sustainable organic synthesis methods has attracted increasing attention, with green, pollution-free, and recyclable components playing a crucial role. CO2, due to its non-toxic, abundant, and recyclable characteristics, is an ideal carbon source. It is both a waste gas from fossil fuel emissions and a cheap, non-toxic, non-flammable, and renewable C1 resource. From a green chemistry perspective, its unique carbonyl structure makes it an effective way to reduce atmospheric CO2 concentration and a vital strategy for sustainable energy development. Therefore, the sustainable utilization of CO2 to synthesize high-value-added chemical products is of great significance.

[0003] Among various organic transformations of CO2, the carbonylation synthesis of heterocyclic structures containing carbonyl groups using CO2 has attracted increasing attention. CO2 is being used to replace highly toxic carbon source gases such as CO and phosgene, which pose safety risks to users. In recent years, the carbonylation reaction of CH bonds with CO2 has made significant progress due to its high atomicity and high economic efficiency. More importantly, since the carbon valence of CO2 is higher than that of CO, it can be ideally considered as a combination of CO and an oxidant (CO2 = CO + [O]), thus enabling this type of carbonylation to be achieved under neutral conditions in redox reactions. This achieves the goals of reducing production costs, reducing heavy metal residues, and addressing safety hazards.

[0004] In summary, there is an urgent need in this field to develop a method for preparing carbonyl compounds using CO2 as a carbon source. Summary of the Invention

[0005] The purpose of this invention is to develop a method for preparing carbonyl compounds using CO2 as a carbonyl source.

[0006] This invention provides a method for preparing carbonyl compounds using CO2 as a carbonylating agent, wherein H2S is used as a catalyst in the method.

[0007] The present invention also provides a method for preparing carbonyl compounds by using H2S to participate in CO2 as a carbonylating agent. In the method, H2S acts as both a catalyst to catalyze the carbonylation reaction and a reactant to participate in the reaction.

[0008] The present invention also provides a method for preparing carbonyl compounds by using H2S to participate in CO2 as a carbonylating agent. In the method, H2S acts as both a catalyst to catalyze the carbonylation reaction and a reducing agent to participate in the reaction.

[0009] In a first aspect, the present invention provides a method for preparing carbonyl compounds using carbon dioxide as a carbonylating agent, characterized in that the method is carried out in the presence of H2S and a base.

[0010] In another preferred embodiment, the method includes step (i) or step (ii):

[0011]

[0012] (i) In an inert solvent, in the presence of a base and an inorganic sulfur reagent, the compound of formula Ia is reacted with CO2 to give the compound of formula I;

[0013]

[0014] (ii) In an inert solvent, in the presence of a base and an inorganic sulfur reagent, the compound of formula IIa is reacted with CO2 to give the compound of formula II;

[0015] Wherein, R1 and R2 are each independently selected from the group consisting of: substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl; or R1 and R2 together constitute a group selected from the group consisting of: substituted or unsubstituted C1-C6 alkylene, substituted or unsubstituted C6-C6 alkylene, substituted or unsubstituted C2-C6 alkenyl. 10 Aryl, substituted or unsubstituted 5-12 heteroaryl groups;

[0016] Ring A is either substituted or unsubstituted C6-C. 10 Aryl, or substituted or unsubstituted 5-12 heteroaryl groups;

[0017] X and Y are each independently selected from the following groups: halogen, CN, SH, OH, NH2, NHR, NO2;

[0018] U and V are each independently selected from the following groups: NH, NR, S, O, -C(=S)NH;

[0019] R is selected from the group consisting of: H, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, SO2CH3, or unsubstituted or substituted phenyl groups selected from the group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3;

[0020] R3 is one or more groups located on ring A selected from the group consisting of: H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, NO2, SO2CH3, or an unsubstituted or substituted phenyl group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; or R5 and R6 together form -(CH2). n - where n is selected from 2, 3, 4, 5 or 6;

[0021] Furthermore, the substitution refers to the substitution of one or more hydrogen atoms on the group by a substituent selected from the group consisting of: halogen, oxygen atom (i.e., =O), C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkoxy, C1-C6 haloalkyl, NO2, SO2CH3, or an unsubstituted or substituted phenyl group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; or two substituents adjacent to or attached to the same carbon atom together forming -(CH2). n - where n is selected from 2, 3, 4, 5 or 6.

[0022] In another preferred embodiment, the base is an organic base; more preferably, the base is selected from the group consisting of C1-C64. 12 Tertiary amines, C1-C 12 Secondary amines, C1-C 12 Primary amines, C2-C 12 Amidones, C2-C 12 Guanidines, C3-C 12 Pyridines, C3-C 12 Imidazole derivatives; preferably, the base is selected from the group consisting of DBU, TBD, MTBD, DBN, TMG, DABCO, ethylenediamine, triethylamine, DIPEA, DMAP, pyridine, or combinations thereof; preferably, the molar ratio of the reaction substrate to the base is 1:0.1-5.

[0023] In another preferred embodiment, the method includes steps (a), (b), (c), (d), (e), (f), (g), or (h);

[0024]

[0025] (a) In an inert solvent and in the presence of a base, o-iodoaniline was reacted with CO2 and hydrogen sulfide to give benzothiazolone derivatives;

[0026]

[0027] (b) In an inert solvent and in the presence of a base, o-nitroiodobenzene reacts with CO2 and hydrogen sulfide to synthesize benzothiazolone derivatives;

[0028]

[0029] (c) In an inert solvent and in the presence of a base, a propargylamine derivative was reacted with CO2 and hydrogen sulfide to synthesize a thiazolidin-2-one derivative.

[0030] R4 is selected from the following group: H, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted phenyl;

[0031] R5, R6, and R7 are each independently selected from the group consisting of: H, substituted or unsubstituted C1-C6 alkyl, or unsubstituted or substituted phenyl groups selected from the group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; or R5 and R6 together forming -(CH2). n - where n is selected from 2, 3, 4, 5 or 6;

[0032]

[0033] (d) In an inert solvent and in the presence of a base, o-aminobenzonitrile was reacted with CO2 and hydrogen sulfide to synthesize thioquinazoline dione derivatives.

[0034] R8 is selected from the group consisting of: H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, NO2, SO2CH3, or unsubstituted or substituted phenyl groups consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3;

[0035]

[0036] (e) In an inert solvent and in the presence of a base, benzothiazolone derivatives are synthesized by reacting aromatic o-amino disulfides with CO2 in the presence of hydrogen sulfide.

[0037]

[0038] (f) In an inert solvent and in the presence of a base, an imidazolidine ketone, an oxazolidine ketone, or a thiazolidine ketone is synthesized by reacting a diamine, an alkanolamine, or a mercaptoamine with CO2 in the presence of hydrogen sulfide; wherein U is O, S, or NR.

[0039] M is a substituted or unsubstituted C2-C4 alkylene group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 5-12 heteroaryl group, wherein the definition of substitution is as described in claim 2.

[0040] In another preferred embodiment, the inert solvent is selected from the group consisting of NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH2Cl2, CHCl3, CCl4, toluene, ethyl acetate, supercritical CO2, or combinations thereof.

[0041] In another preferred embodiment, the molar ratio of the reaction substrate to CO2 in the reaction is 1:1-100.

[0042] In another preferred embodiment, during the reaction process, CO2 is continuously introduced into the reactor, and the pressure of the CO2 in the reactor is 0.1-12 MPa.

[0043] In another preferred embodiment, the molar ratio of the reaction substrate to the hydrogen sulfide in the reaction is 1:0.05-20.

[0044] In another preferred embodiment, during the reaction process, H2S is continuously introduced into the reactor, and the pressure of H2S in the reactor is 0.05-1.5 MPa.

[0045] In another preferred embodiment, the reaction temperature is room temperature to 150°C.

[0046] It should be understood that, within the scope of this invention, the above-described technical features of this invention and the technical features specifically described below (such as in the embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be described in detail here. Detailed Implementation

[0047] Through long-term and in-depth research, the inventors unexpectedly discovered that using H2S as a catalyst can efficiently catalyze the reaction of CO2 as a carbonyl source with a series of substrates to prepare carbonylated compounds. This carbonylation reaction can occur alone or in conjunction with other reactions involving CO2 or H2S to prepare a series of products, which has potential application value in the field of fine chemical synthesis. Based on the above discovery, the inventors completed this invention.

[0048] Synthesis methods using CO2 as a carbonylating agent

[0049] This invention provides a method for preparing carbonyl compounds using carbon dioxide as a carbonylating agent, wherein the method is carried out in the presence of H2S. The H2S can act as a simple catalyst, or it can act as a reactant simultaneously with the substrate to undergo further reaction or generate intermediates.

[0050] Specifically, the method includes step (i) or step (ii):

[0051]

[0052] (i) In an inert solvent, in the presence of a base and an inorganic sulfur reagent, a compound of formula Ia is reacted with CO2 to obtain a compound of formula I (wherein, the compound of formula Ia may be a mixture of R1-X and R2-Y, or a compound formed by R1-X and R2Y having two reactive functional groups X and Y).

[0053]

[0054] (ii) In an inert solvent, in the presence of a base and an inorganic sulfur reagent, the compound of formula IIa is reacted with CO2 to give the compound of formula II;

[0055] Wherein, R1 and R2 are each independently selected from the group consisting of: substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl; or R1 and R2 together constitute a group selected from the group consisting of: substituted or unsubstituted C1-C6 alkylene, substituted or unsubstituted C6-C6 alkylene, substituted or unsubstituted C2-C6 alkenyl. 10 Aryl, substituted or unsubstituted 5-12 heteroaryl groups;

[0056] Ring A is either substituted or unsubstituted C6-C. 10 Aryl, or substituted or unsubstituted 5-12 heteroaryl groups;

[0057] X and Y are each independently selected from the following groups: H, halogen, CN, SH, OH, NH2, NHR, NO2;

[0058] U and V are each independently selected from the following groups: NR, S, O, -C(=S)NH;

[0059] R is selected from the group consisting of: H, halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, NO2, SO2CH3, or unsubstituted or substituted phenyl groups selected from the group consisting of: halogen, C1-C6 alkyl.

[0060] R3 is one or more groups located on ring A selected from the group consisting of: H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, NO2, SO2CH3, or an unsubstituted or substituted phenyl group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; or R5 and R6 together form -(CH2). n- where n is selected from 2, 3, 4, 5 or 6;

[0061] Furthermore, the substitution refers to the substitution of one or more hydrogen atoms on the group by a substituent selected from the group consisting of: halogen, oxygen atom (i.e., =O), C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkoxy, C1-C6 haloalkyl, NO2, SO2CH3, or an unsubstituted or substituted phenyl group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; or two substituents adjacent to or attached to the same carbon atom together forming -(CH2). n - where n is selected from 2, 3, 4, 5 or 6.

[0062] In a preferred embodiment of the present invention, the steps are carried out in the presence of an alkali, which is preferably an organic base. More preferably, the alkali is selected from the group consisting of C1-C64. 12 Tertiary amines, C1-C 12 Secondary amines, C1-C 12 Primary amines, C2-C 12 Amidones, C2-C 12 Guanidines, C3-C 12 Pyridines, C3-C 12 Imidazoles, DBU, TBD, MTBD, DBN, TMG, DABCO, ethylenediamine, triethylamine, DIPEA, DMAP, pyridine, or combinations thereof; preferably, the molar ratio of the reaction substrate to the base is 1:0.1-5.

[0063] In the method described, the choice of solvent is not particularly limited, and common inert solvents that do not affect the reaction can be used. Preferred solvents include: NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH2Cl2, CHCl3, CCl4, toluene, ethyl acetate, or combinations thereof. In particular, since the method of the present invention requires the use of a carbon dioxide gas stream, a preferred embodiment is to use supercritical CO2 as the solvent.

[0064] In the method described, there is no particular limitation on the molar ratio of the reaction substrate to CO2, which can be 1:1-100.

[0065] During the reaction process, CO2 is continuously introduced into the reactor. In the preferred reaction method, the pressure of CO2 in the reactor is 0.1-12 MPa.

[0066] In the reaction, the molar ratio of the reaction substrate to the inorganic sulfur is preferably 1:0.05-20.

[0067] During the reaction process, H2S is continuously introduced into the reactor, and preferably the pressure of H2S in the reactor is 0.08-1.5 MPa.

[0068] The temperature of the reaction is not particularly limited, but it is preferably carried out at room temperature (usually 0-40°C) to 150°C.

[0069] The above reaction can be used to prepare a series of compounds with characteristic structures. For example, compounds with corresponding structural units can be prepared by steps (a), (b), (c), (d), (e), and (f).

[0070] (a) o-Iodoaniline reacts with CO2 and hydrogen sulfide to synthesize benzothiazolone derivatives.

[0071]

[0072] In an inert solvent and in the presence of a base, o-iodoaniline is reacted with CO2 and hydrogen sulfide to yield benzothiazolone derivatives. In the above reaction, the base is preferably DABCO, DBU, TBD, or Et3N; the solvent is preferably NMP or DMF; and the amount of base used is preferably 1-3 equivalents.

[0073] In another preferred embodiment, in step (a), the pressure ratio of CO2 to H2S is (1-8):(0.1-0.8).

[0074] (b) o-Nitroiodobenzene reacts with CO2 and hydrogen sulfide to synthesize benzothiazolone derivatives.

[0075]

[0076] In an inert solvent and in the presence of a base, o-nitroiodobenzene reacts with CO2 and hydrogen sulfide to synthesize benzothiazolone derivatives; in the above reaction, the base is preferably DBU or Et3N; the solvent is preferably NMP or NMP / H2O; and the amount of base used is preferably 2-5 equivalents.

[0077] In another preferred embodiment, in step (b), the pressure ratio of CO2 to H2S is (1-8):(0.5-1.5).

[0078] In another preferred embodiment, the above reaction can be carried out under CuI catalysis.

[0079] (c) Synthesis of thiazolidin-2-one derivatives by reacting propargylamine with CO2 and hydrogen sulfide.

[0080]

[0081] Thiazolidine-2-one derivatives were synthesized by reacting propargylamine derivatives with CO2 and hydrogen sulfide in an inert solvent and in the presence of a base.

[0082] R4 is selected from the following group: H, substituted or unsubstituted C1-C6 alkyl groups;

[0083] R5, R6, and R7 are each independently selected from the group consisting of: H, substituted or unsubstituted C1-C6 alkyl, or unsubstituted or substituted phenyl groups selected from the group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; or R5 and R6 together forming -(CH2). n - where n is selected from 2, 3, 4, 5 or 6;

[0084] In the above reaction, the preferred base is DBU, Et3N, TBD or K2CO3; the preferred solvent is CH3OH, DMF, NMP or DMSO; and the preferred amount of base is 0.5-1.5 equivalents.

[0085] In another preferred embodiment, in step (c), the pressure ratio of CO2 to H2S is 1:(0.2-1.5).

[0086] (d) The reaction of o-aminobenzonitrile with CO2 and hydrogen sulfide synthesizes thiobenzamide or thioquinazolinid derivatives.

[0087]

[0088] In an inert solvent and in the presence of a base, o-aminobenzonitrile reacts with CO2 and hydrogen sulfide to synthesize thiobenzamide or thioquinazoline dione derivatives; in this reaction, CO2 and H2S are both reactants, forming a six-membered ring structure. In the above reaction, the base is preferably DBU; the solvent is preferably DMF; and the amount of base used is preferably 0.2-2 equivalents.

[0089] In another preferred embodiment, in step (d), the pressure ratio of CO2 to H2S is (2-5):(0.2-1.2).

[0090] (e) Aromatic o-amino disulfides react with CO2 in the presence of hydrogen sulfide to synthesize benzothiazolone derivatives.

[0091]

[0092] In an inert solvent and in the presence of a base, an aromatic o-amino disulfide is reacted with CO2 in the presence of hydrogen sulfide to synthesize benzothiazolone derivatives. In the above reaction, the base is preferably DBU, TMG, or Et3N; the solvent is preferably NMP, CH3OH, 1,4-dioxane, or DMSO; and the amount of base used is preferably 0.2-1.2 equivalents.

[0093] In another preferred embodiment, in step (e), the pressure ratio of CO2 to H2S is (1-5):(0.1-1.2).

[0094] (f) Diamines, alcoholamines, or thiolamines react with CO2 in the presence of hydrogen sulfide to synthesize imidazole (oxa or thiazolidinone) derivatives.

[0095]

[0096] In an optional inert solvent, and in the optional presence of a base, imidazolidine ketone derivatives, oxazolidine ketone derivatives, or thiazolidinone derivatives are synthesized by reacting diamines, alkanolamines, or mercaptoamines with CO2 in the presence of hydrogen sulfide.

[0097] Where U represents O, S, or NR;

[0098] M is a substituted or unsubstituted C2-C4 alkylene group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 5-12 heteroaryl group, wherein the definition of substitution is as described above.

[0099] In the above reaction, the base is preferably DABCO, DBU, or Et3N; the solvent is preferably NMP, DMF, ethylene glycol, or dichloromethane; and the amount of base used is preferably 0.1-2 equivalents. In particular, when the reactant used is an organic base, or can be used as a solvent, the reaction can also be carried out without a solvent or in the absence of an organic base.

[0100] In another preferred embodiment, in step (f), the pressure ratio of CO2 to H2S is (5-50):1.

[0101] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. Percentages and parts are by weight unless otherwise stated.

[0102] The first type of inorganic sulfur serves as both a raw material and a catalyst.

[0103] Example 1: Synthesis of benzothiazolone derivatives by reacting o-iodoaniline with CO2 and hydrogen sulfide.

[0104]

[0105] The reaction method is as follows:

[0106] Weigh 1 mol of o-haloaniline, 2 mol of base, 0.2 mol of cuprous iodide (CuI), and 2 ml of solvent, and add them sequentially to a reaction vessel, then tighten the vessel. Purge the corresponding amount of H₂S into the reaction vessel and stir at 90°C for 30 min. Then, purge the corresponding amount of CO₂ into the reaction vessel and continue stirring at the same temperature for 24 h. After the reaction is complete, cool the reaction vessel to room temperature, slowly purge the gas from the reaction vessel, open the reaction vessel, and transfer the reaction solution to a 250 ml separatory funnel. Extract the reaction solution with ethyl acetate and dry the organic phase with anhydrous magnesium sulfate. Separate the product by column chromatography.

[0107] The reaction conditions were optimized following the steps outlined above, and the results are shown in the table below:

[0108]

[0109] Note: In all the above reactions, the starting material was 1 mmol o-iodoaniline; the solvent was 2 ml; CuI was 0.2 mmol; and the reaction time was 24 h.

[0110] Using the method described in entry 2 above, but with different reaction substrates, the following products were obtained:

[0111] Characterization of compounds:

[0112]

[0113] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 4:1 was used as the developing solvent to separate 144 mg of white solid benzothiazolinone, with a separation yield of 95%.

[0114] Characterization data for benzothiazol-2-one (2a): 1 H NMR (CDCl3, 500MHz): δ (ppm) 10.01 (brs, 1H), 7.41 (d, 1H, J = 7.5Hz), 7.30-7.26 (m, 1H), 7.17-7.14 (m, 2H). 13 C NMR (CDCl3, 125MHz): δ (ppm) 172.8, 135.3, 126.5, 123.9, 123.3, 122.6, 111.7; MS (EI): m / z calcd for C7H5NOS[M] + :151.0,found 151.0.mp:139-140℃.

[0115]

[0116] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 3:1 was used as the developing solvent, and 138 mg of white solid was obtained, with a separation yield of 84%.

[0117] Characterization data of 6-methylbenzothiazol-2-one: 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 11.75 (brs, 1H), 7.36 (s, 1H), 7.07-7.09 (m, 1H), 7.00 (d, 1H, J = 8Hz), 2.30 (s, 3H); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 169.8, 133.9, 131.7, 127.0, 123.2, 122.5, 111.1, 20.5; MS (ESI): m / zcalcd for C8H7NOS[M+1] + :166.0,found 165.0.mp:170-171℃.

[0118]

[0119] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 2:1 was used as the developing solvent, and 134 mg of white solid was obtained, with a separation yield of 82%.

[0120] Characterization data of 5-methylbenzothiazol-2-one: 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 11.79 (s, 1H), 7.42 (d, J = 7.9Hz, 1H), 6.98–6.91 (m, 2H), 2.32 (s, 3H). 13 C NMR (DMSO-d6, 126MHz) δ (ppm) 170.31, 136.34, 136.04, 123.49, 122.37, 119.95, 111.84, 20.98; MS (ESI): m / z calcdfor C8H7NOS[M+1]+: 166.1, found 165.0.

[0121]

[0122] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 3:1 was used as the developing solvent, and 158 mg of white solid was obtained, with a separation yield of 88%.

[0123] Characterization data of 6-methoxybenzothiazol-2-one: 1 13C NMR(DMSO-d6,126MHz): δ(ppm)169.8,155.2,129.9,124.3,113.2,112.1,107.8,55.6; MS(ESI): m / z calcd for C8H7NO2S[M+1] + :182.1,found181.1.

[0124]

[0125] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 3:1 was used as the developing solvent, and 144 mg of white solid was obtained, with a separation yield of 85%.

[0126] Characterization data of 6-fluorobenzothiazol-2-one: 1 H NMR (DMSO-d6, 500MHz) δ (ppm) 11.91 (s, 1H), 7.57 (d, J = 7.9Hz, 1H), 7.21–7.06 (m, 2H). 13 C NMR (DMSO-d6, 126MHz) δ (ppm) 169.83, 158.84, 156.94, 132.86, 132.84, 124.62, 113.64, 113.45, 112.42, 112.35, 110.06, 109.85, 39.25. MS (ESI): m / z calcd for C7HFNOS[M+1] + :170.1, found 169.1.

[0127]

[0128] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 3:1 was used as the developing solvent, and 175 mg of white solid was obtained, with a separation yield of 81%.

[0129] Characterization data of 6-trifluoromethylbenzothiazol-2-one: 1 13C NMR (DMSO-d6, 125MHz): δ (ppm) 169.7, 136.7, 128.4 (d, J = 1.25Hz), 126.9 (q, J = 31.9.5 Hz), 124.0 (q, J = 270.5Hz), 123.8, 119.0 (q, J = 3.9Hz), 107.6 (q, J = 4.1Hz); MS (EI): m / z calcd for C8H4F3NOS[M+1]+:220.0,found 219.0.mp:216-218℃.

[0130]

[0131] Dry column packing and dry column chromatography (200-300 mesh silica gel): Dichloromethane:ethyl acetate (V / V) = 20:1 was used as the developing solvent, and 144 mg of white solid was obtained, with a separation yield of 63%.

[0132] Characterization data of 6-bromobenzothiazol-2-one: 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 12.02 (brs, 1H), 7.86 (d, 1H, J = 2.0Hz), 7.44 (dd, 1H, J1 = 8.5, J2 = 2.5Hz), 7.05 (d, 1H, J = 8.5Hz); 13 CNMR (DMSO-d6, 125MHz): δ (ppm) 169.7, 135.6, 129.2, 125.6, 125.0, 114.0, 113.1; MS (EI): m / z calcd for C7H4BrNOS[M+1]+: 229.9, found 228.9.mp: 231-232℃.

[0133]

[0134] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Dichloromethane:ethyl acetate (V / V) = 100:3 was used as the developing solvent, and 121 mg of white solid was obtained, with a separation yield of 66%.

[0135] Characterization data of 6-chlorobenzothiazol-2-one: 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 12.02 (brs, 1H), 7.74 (d, 1H, J = 2.0Hz), 7.32 (dd, 1H, J1 = 8.5, J2 = 2.5Hz), 7.11 (d, 1H, J = 8.5Hz); 13 CNMR (DMSO-d6, 125MHz): δ (ppm) 169.7, 135.3, 126.4, 125.2, 122.4, 122.7; MS (ESI): m / zcalcd for C7H4ClNOS[M+1]+: 186.0, found 185.0.mp: 212-214℃.

[0136]

[0137] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel) separation: using dichloromethane:ethyl acetate (V / V) = 100:3 as the developing solvent, 124 mg of white solid was obtained, with a separation yield of 76%.

[0138] Characterization data of 2-methylbenzothiazol-2-one: 1 H NMR (500MHz, DMSO-d6) δ (ppm) 7.64 (d, J = 7.8Hz, 1H), 7.39 (t, J = 7.7Hz, 1H), 7.30 (d, J = 8.1Hz, 1H), 7.21 (t, J = 7.6Hz, 1H), 3.41 (s, 3H). 13 C NMR (126MHz, DMSO-d6) δ (ppm) 137.61, 126.60, 123.17, 122.70, 121.28, 111.32.

[0139]

[0140] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 3:1 was used as the developing solvent, and 110 mg of white solid was obtained, with a separation yield of 67%.

[0141] Characterization data of 6-aminobenzothiazol-2-one: 1H NMR(500MHz,DMSO-d6)δ(ppm)11.34(s,1H),6.80(d,J=8.4Hz,1H),6.69(d,J=2.2Hz,1H),6.51(dd,J=8.4,2.3Hz,1H),4.94(s,2H).13C NMR (126MHz, DMSO-d6) δ (ppm) 169.31, 144.70, 126.35, 124.07, 112.92, 111.98, 107.03. MS (ESI): m / z calcd for C7H6N2OS[M+1]+: 167.1, found 166.1.

[0142] Example 2: Synthesis of benzothiazolone derivatives by reacting o-nitroiodobenzene with CO2 and hydrogen sulfide.

[0143]

[0144] The reaction method is as follows:

[0145] Weigh 1 mol of o-halononitrobenzene, 2 mol of base, 0.2 mol of cuprous iodide (CuI), and 2 ml of solvent, and add them sequentially to a reaction vessel, then tighten the vessel. Purge the corresponding amount of H₂S into the reaction vessel and stir at the appropriate temperature for 30 min. Then, purge the corresponding amount of CO₂ into the reaction vessel and continue stirring at the appropriate temperature for 24 h. After the reaction is complete, cool the reaction vessel to room temperature, slowly purge the gas from the reaction vessel, open the reaction vessel, and transfer the reaction solution to a 250 ml separatory funnel. Extract the reaction solution with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, and separate the product by column chromatography.

[0146] The reaction conditions were optimized following the steps outlined above, and the results are shown in the table below:

[0147]

[0148] Note: In all the above reactions, the starting material was 1 mmol o-iodonitrobenzene; the solvent was 2 ml; CuI was 0.2 mmol; and the reaction time was 24 h.

[0149] Using the method described in entry 9 above, but with different reaction substrates, the following products were obtained:

[0150]

[0151] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 3:1 was used as the developing solvent, and 117 mg of white solid was obtained, with a separation yield of 71%.

[0152] Characterization data of 5-methylbenzothiazol-2-one: 1 H NMR (500MHz, DMSO-d6) δ (ppm) 11.80 (s, 1H), 7.42 (d, J = 7.9Hz, 1H), 6.97–6.92 (m, 2H), 2.32 (s, 3H). 13 C NMR (126MHz, DMSO-d6) δ (ppm) 170.35, 136.35, 136.06, 123.52, 122.39, 119.97, 111.87, 21.00; MS (ESI): m / z calcd forC8H7NOS[M+1]+: 166.0, found 165.0.

[0153]

[0154] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 3:1 was used as the developing solvent, and 117 mg of white solid was obtained, with a separation yield of 71%.

[0155] Characterization data of 7-methylbenzothiazol-2-one: ¹H NMR (500MHz, DMSO-d6) δ 11.87 (s, 1H), 7.20 (t, J = 7.8Hz, 1H), 6.97 (dd, J = 7.7, 5.0Hz, 2H), 2.28 (s, 3H). ¹³C NMR (126MHz, DMSO-d6) δ 169.57, 136.09, 131.62, 126.25, 123.07, 122.98, 109.03, 19.70; MS (ESI): m / z calcd for C8H7NOS[M+1]+: 166.0, found 165.0.

[0156]

[0157] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 3:1 was used as the developing solvent, and 127 mg of white solid was obtained, with a separation yield of 70%.

[0158] Characterization data of 5-methoxybenzothiazol-2-one: 1 H NMR (500MHz, DMSO-d6) δ (ppm) 11.80 (s, 1H), 7.44 (d, J = 8.7Hz, 204H), 6.74 (dd, J = 8.7, 2.5Hz, 249H), 6.66 (d, J = 2.5Hz, 245H), 3.75 (s, 704H).13 C NMR (126MHz, DMSO-d6) δ (ppm) 170.91, 158.48, 137.27, 123.40, 114.19, 109.48, 97.39, 55.39; MS (ESI): m / z calcd for C8H7NO2S[M+1]+: 182.1, found 181.1.

[0159]

[0160] Dry column packing and dry column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 3:1 was used as the developing solvent, and 140 mg of white solid was obtained, with a separation yield of 67%.

[0161] Characterization data of 5-methyl benzothiazol-2-one: 1 H NMR (500MHz, DMSO-d6) δ (ppm) 12.14 (s, 1H), 7.75–7.68 (m, 3H), 7.63 (s, 1H), 3.87 (s, 4H). 13 C NMR(126MHz,DMSO-d6)δ(ppm)169.69,165.75,136.52,129.31,127.63,123.14,122.96,111.50,111.46,52.29.MS(ESI):m / zcalcd for C9H7NO3S[M+1]+:220.0,found 219.0.

[0162]

[0163] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 5:1 was used as the developing solvent, and 116 mg of white solid was obtained, with a separation yield of 63%.

[0164] Characterization data of 7-chlorobenzothiazol-2-one: 1 H NMR (500MHz, DMSO-d6) δ (ppm) 12.22 (s, 1H), 7.33 (t, J = 8.0Hz, 1H), 7.26 (d, J = 7.1Hz, 1H), 7.11 (d, J = 7.9Hz, 1H). 13C NMR (126MHz, DMSO-d6) δ (ppm) 168.56, 137.50, 127.83, 126.19, 122.61, 122.19, 110.34, 110.30, 109.54; MS (ESI): m / z calcd for C7H4ClNOS[M+1]+: 186.0, found 185.0.

[0165]

[0166] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 3:1 was used as the developing solvent, and 126 mg of white solid was obtained, with a separation yield of 75%.

[0167] Characterization data of 5-fluorobenzothiazol-2-one: 1 H NMR(500MHz, DMSO-d6)δ(ppm)12.03(s,1H),7.61(dd,J=8.7,5.4Hz,1H),7.01(td,J=9.1,2.6Hz,1H),6.94(dd,J=9.3,2.6Hz,1H).13C NMR (126MHz, DMSO-d6) δ170.68,161.98,160.06,137.36,137.26,124.21,124.13,118.73,118.71,109.84,109.65,99.33,99.11; MS (ESI): m / z calcd for C7HFNOS[M+1]+:170.1,found 169.1.mp:172-174℃.

[0168]

[0169] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 3:1 was used as the developing solvent, and 118 mg of white solid was obtained, with a separation yield of 64%.

[0170] Characterization data of 5-chlorobenzothiazol-2-one: 1 H NMR (500MHz, DMSO-d6) δ (ppm) 12.05 (s, 1H), 7.61 (d, J = 8.4Hz, 1H), 7.19 (dd, J = 8.4, 2.1Hz, 1H), 7.12 (s, 1H). 13C NMR (126MHz, DMSO-d6) δ (ppm) 170.12, 137.47, 130.83, 124.26, 122.45, 122.22, 122.19, 111.24; MS (ESI): m / zcalcd for C7H4ClNOS[M+1]+: 186.0, found 185.0.mp:224-226℃.

[0171]

[0172] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 3:1 was used as the developing solvent, and 154 mg of white solid was obtained, with a separation yield of 67%.

[0173] Characterization data of 5-bromobenzothiazol-2-one: 1 H NMR (500MHz, DMSO-d6) δ (ppm) 12.04 (s, 1H), 7.56 (d, J = 8.4Hz, 1H), 7.31 (dd, J = 8.4, 2.0Hz, 1H), 7.24 (d, J = 1.9Hz, 1H). 13 C NMR (126MHz, DMSO-d6) δ (ppm) 169.91, 137.70, 125.20, 124.59, 122.71, 118.74, 113.96; MS (ESI): m / z calcd for C7H4BrNOS[M+1]+: 229.9, found 228.9.

[0174] Example 3: Synthesis of thiazolidin-2-one derivatives by reacting propargylamine with CO2 and hydrogen sulfide.

[0175]

[0176] 2 mmol of propargylamine, 1.2 mmol of base, and 2 mL of solvent were added to a 10 mL reaction vessel. A magnetic stir bar was placed in the vessel and the vessel was tightened. The vessel was purged three times with N2 gas using a vacuum pump, followed by the introduction of the corresponding amount of H2S. The mixture was stirred until the pressure stabilized, then 1 MPa of CO2 was introduced, and the reaction was carried out at the appropriate temperature for 24 h. After the reaction was completed, the reaction mixture was extracted with ethyl acetate, and the organic phases were collected and combined. The mixture was dried with anhydrous magnesium sulfate for 30 min, filtered to remove the drying agent, and the solvent was removed under reduced pressure to obtain the crude product. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate or dichloromethane / methanol) to obtain the target product.

[0177] The reaction conditions were optimized following the steps outlined above, and the results are shown in the table below:

[0178]

[0179] Note: The raw materials used were all 2 mmol of 2-methyl-3-butyn-2-amine; the solvent was 2 ml; and the reaction time was 24 hours.

[0180] Using the method described in entry 7 above, but with different reaction substrates, the following products were obtained:

[0181] Characterization of compounds

[0182]

[0183] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 1:2 was used as the developing solvent, and the separation yield was 24%.

[0184] 5-methylenethiazolidin-2-one: 1 H NMR (500MHz, CDCl3) δ6.54(s,1H),5.24(s,1H),5.16(s,1H),4.31(s,2H). 13 C NMR(126MHz, CDCl3)δ172.98,138.70,106.71,49.29.MS(ESI):calcd for C4H5NOS:115.0[M].Found:116.0[M+H] + .

[0185]

[0186] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the separation yield was 81%.

[0187] 4,4-dimethyl-5-methylenethiazolidin-2-one: 1 H NMR (500MHz, CDCl3) δ6.32(s,1H),5.20(s,1H),5.08(s,1H),1.50(s,6H). 13 C NMR(126MHz, CDCl3)δ169.67,149.30,104.92,62.71,29.89.MS(EI):calcd for C6H9NOS:143.1[M].Found:142.9[M] + .

[0188]

[0189] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): using dichloromethane:methanol (V / V) = 200:1 as the developing solvent, the separation yield was 80%.

[0190] (Z)-5-benzylidene-3-butyl-4,4-diethylthiazolidin-2-one: 1 H NMR (500MHz, CDCl3) δ7.37(d,J=6.5Hz,4H),7.23(s,1H),6.39(s,1H),3.21–3.14(m,2H),1.95–1. 83(m,2H),1.79–1.56(m,5H),1.37(q,J=7.5Hz,2H),0.96(t,J=7.4Hz,3H),0.86(t,J=7.2Hz,6H). 13 C NMR (126MHz, CDCl3) δ168.67,136.30,136.17,128.62,127.97,126.96,118.08,75.75,42.42,34.00,30.84,20.63,13.74,7.66.MS(ESI):calcd for C 18 H 25 NOS: 303.2 [M]. Found: 304.2 [M+H] + .

[0191]

[0192] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): using petroleum ether:ethyl acetate (V / V) = 2:1 as the developing solvent, the separation yield was 92%.

[0193] (Z)-4-benzylidene-1-butyl-3-thia-1-azaspiro[4.5]decan-2-one: 1 H NMR(500MHz, CDCl3)δ7.40–7.30(m,4H),7.28–7.22(m,1H),6.96(s,1H),3.29–3.21(m,2H),2.07 (d,J=10.4Hz,2H),1.80(d,J=27.9Hz,7H),1.57(s,2H),1.41–1.24(m,3H),0.94(t,J=7.4Hz,3H). 13 C NMR(126MHz, CDCl3)δ168.14,139.55,136.34,128.60,128.52,127.48,122.72,69.69,42.40,33.65,32.24,24.65,22.76,20.50,13.95.MS(ESI):calcd forC 19 H25 NOS: 315.2 [M]. Found: 316.2 [M+H] + .

[0194]

[0195] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 3:1 was used as the developing solvent, and the separation yield was 92%.

[0196] (Z)-5-benzylidene-3-butyl-4-phenylthiazolidin-2-one: 1 H NMR(500MHz, CDCl3)δ7.45–7.36(m,5H),7.36–7.30(m,2H),7.27–7.17(m,3H),6.30(d,J=1.8Hz,1H),5.4 7(s,1H),3.77–3.63(m,1H),2.72(s,1H),1.48(d,J=9.7Hz,2H),1.33–1.23(m,2H),0.88(t,J=7.4Hz,3H). 13 C NMR (126MHz, CDCl3) δ168.05,139.39,135.75,132.46,129.38,129.14,128.69,128.09,127.38,69.93,42.89,29.22,20.06,13.81.MS(ESI):calcd forC 20 H 21 NOS:323.1[M]. Found:324.2[M+H] + .

[0197]

[0198] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): using petroleum ether:ethyl acetate (V / V) = 2:1 as the developing solvent, the separation yield was 99%.

[0199] (Z)-4-benzyl-5-benzylidene-3-butylthiazolidin-2-one: 1 H NMR (500MHz, CDCl3) δ7.41–7.04(m,10H),6.07(s,1H),4.63(s,1H),3.92(d,J=14.0Hz,1H ),3.16–2.97(m,3H),1.62(d,J=7.1Hz,2H),1.35(d,J=7.3Hz,2H),0.95(t,J=7.4Hz,3H). 13C NMR (126MHz, CDCl3) δ168.06,135.44,135.25,130.97,129.92,128.56,128.47,1 27.92,127.25,127.11,66.57,42.52,40.54,29.62,20.01,13.73.MS(ESI):calcd for C 21 H 23 NOS: 337.2 [M]. Found: 338.1 [M+H] + .

[0200]

[0201] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the separation yield was 90%.

[0202] (Z)-5-benzylidene-3-butyl-4-propylthiazolidin-2-one: 1 H NMR (500MHz, CDCl3) δ7.37(t,J=7.7Hz,2H),7.31(d,J=7.3Hz,2H),7.23(d,J=7.3Hz,1H),6.49(d,J=1.3Hz,1H),4.56(s,1H ),3.85–3.74(m,1H),2.99(ddd,J=13.9,8.7,5.1Hz,1H),1.89(s,1H),1.73(s,1H),1.54(s,2H),1.34(s,4H),0.95(s,6H). 13 C NMR(126MHz, CDCl3)δ168.07,135.84,132.45,128.76,128.10,127.30,121.09,65.16,42.34,36.39,29.58,20.17,16.06,14.15,13.87.MS(ESI):calcd for C 17 H 23 NOS: 289.2 [M]. Found: 290.0 [M+H] + .

[0203]

[0204] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): using petroleum ether:ethyl acetate (V / V) = 2:1 as the developing solvent, the separation yield was 92%.

[0205] (Z)-3-butyl-4,4-dimethyl-5-(4-methylbenzylidene)thiazolidin-2-one: 1HNMR(500MHz, CDCl3)δ7.23(d,J=8.2Hz,2H),7.17(d,J=8.0Hz,2H),6.50(s,1H),3.29–3.23(m, 2H),2.34(s,3H),1.64(t,J=8.0Hz,2H),1.55(s,6H),1.40–1.31(m,2H),0.95(t,J=7.4Hz,3H). 13 C NMR (126MHz, CDCl3) δ167.12,138.26,137.14,133.33,129.42,128.08,118.95,68.03,42.48,31.74,28.34,21.35,20.55,13.92.MS(ESI):calcd for C 17 H 23 NOS: 289.2 [M]. Found: 290.0 [M+H] + .

[0206]

[0207] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the separation yield was 81%.

[0208] (Z)-3-butyl-5-(4-methoxybenzylidene)-4,4-dimethylthiazolidin-2-one: 1 HNMR (500MHz, CDCl3) δ7.27(d,J=8.8Hz,2H),6.91(d,J=8.7Hz,2H),6.47(s,1H),3.82(d,J=0.6Hz,3 H),3.30–3.21(m,2H),1.64(t,J=7.9Hz,2H),1.55(s,6H),1.42–1.31(m,2H),0.95(t,J=7.4Hz,3H). 13 C NMR (126MHz, CDCl3) δ167.16,158.69,136.88,129.47,128.85,118.55,114.16,67.99,55.44,42.47,31.74,28.32,20.54,13.91.MS(ESI):calcd forC 17 H 23 NO2S:305.1[M].Found:306.1[M+H] + .

[0209]

[0210] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the separation yield was 83%.

[0211] (Z)-3-butyl-5-(4-chlorobenzylidene)-4,4-dimethylthiazolidin-2-one: 1 HNMR(500MHz, CDCl3)δ7.33(d,J=8.5Hz,2H),7.26(d,J=8.7Hz,2H),6.47(s,1H),3.32–3 .20(m,2H),1.68–1.60(m,2H),1.55(s,6H),1.36(q,J=7.5Hz,2H),0.95(t,J=7.3Hz,3H). 13 C NMR (126MHz, CDCl3) δ166.47,140.50,134.66,132.84,129.37,128.88,117.84,68.10,42.57,31.69,28.33,20.52,13.89.MS(ESI):calcd for C 16 H 20 ClNOS:309.1[M].Found:310.1[M+H] + .

[0212]

[0213] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 1:2 was used as the developing solvent, and the separation yield was 87%.

[0214] (Z)-5-benzylidene-4,4-dimethylthiazolidin-2-one: 1 H NMR (500MHz, CDCl3) δ7.41–7.30(m,4H),7.27–7.21(m,1H),6.77(s,1H),6.50(s,1H),1.60(s,6H). 13 C NMR(126MHz, CDCl3)δ169.53,140.32,135.82,128.63,127.96,127.25,119.43,63.63,30.17.MS(ESI):calcd for C 12 H 13 NOS: 219.1 [M]. Found: 220.1 [M+H] + .

[0215]

[0216] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the separation yield was 94%.

[0217] (Z)-5-benzylidene-4,4-dimethyl-3-propylthiazolidin-2-one: 1 H NMR (500MHz, CDCl3) δ7.41–7.29(m,4H),7.27–7.20(m,1H),6.53(s,1H),3.27–3.16(m,2H),1.74–1.63(m,2H),1.56(s,6H),0.94(t,J=7.4Hz,3H). 13 C NMR(126MHz, CDCl3)δ166.88,139.32,136.01,128.59,128.03,127.11,118.92,67.93,44.15,28.21,22.72,11.48.MS(ESI):calcd for C 15 H 19 NOS:261.1[M]. Found:262.2[M+H] + .

[0218]

[0219] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the separation yield was 87%.

[0220] (Z)-5-benzylidene-3-butyl-4,4-dimethylthiazolidin-2-one: 1 H NMR(500MHz, CDCl3)δ7.39–7.31(m,4H),7.23(t,J=7.8Hz,1H),6.53(s,1H),3.30–3.2 4(m,2H),1.65(t,J=7.9Hz,2H),1.56(s,6H),1.40–1.32(m,2H),0.95(t,J=7.4Hz,3H). 13 C NMR (126MHz, CDCl3) δ166.95,139.56,136.20,128.74,128.19,127.27,119.05,68.09,42.53,31.75,28.38,20.56,13.91.MS(ESI):calcd for C 16 H 21 NOS: 275.1 [M]. Found: 275.9 [M+H] + .

[0221]

[0222] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the separation yield was 89%.

[0223] (Z)-3-benzyl-5-benzylidene-4,4-dimethylthiazolidin-2-one: 1 H NMR (500MHz, CDCl3) δ7.40–7.29(m,8H),7.25(s,2H),6.53(s,1H),4.62(s,2H),1.49(s,6H). 13 CNMR(126MHz, CDCl3)δ168.05,139.14,138.07,136.03,128.77,128.75,128.20,127.51,127.39,127.34,68.37,45.29,28.49.MS(ESI):calcd for C 19 H 19 NOS: 309.1 [M]. Found: 310.1 [M+H] + .

[0224]

[0225] Separation by wet packing and dry loading column chromatography (200-300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 4:1 was used as the developing solvent, and the separation yield was 46%.

[0226] (Z)-5-benzylidene-3-isopropyl-4,4-dimethylthiazolidin-2-one: 1 H NMR (500MHz, CDCl3) δ7.35 (dt, J=14.1, 7.3Hz, 4H), 7.23 (t, J=6.3Hz, 1H), 6.46 (d ,J=1.9Hz,1H),3.52(dt,J=13.6,6.8Hz,1H),1.56(s,6H),1.49(d,J=6.8Hz,6H). 13 C NMR(126MHz, CDCl3)δ165.63,139.82,136.33,128.73,128.16,127.11,118.80,69.14,47.71,28.31,20.47.MS(ESI):calcd for C 15 H 19 NOS:261.1[M]. Found:262.2[M+H] + .

[0227] Type II hydrogen sulfide as a catalyst

[0228] Example 4: Synthesis of benzimidazole derivatives by reacting o-phenylenediamine with CO2 in the presence of hydrogen sulfide.

[0229]

[0230] Add 2 mmol o-phenylenediamine, 2 mmol base and 1 mL suitable solvent sequentially to a 15 mL high-pressure reactor, and tighten the reactor. Then, introduce the required amounts of H2S and CO2 gas into the reactor sequentially. Finally, allow the reactor to react continuously at a suitable temperature for 12 hours. After the reaction is complete, add a certain amount of distilled water to the reaction solution to allow the product to precipitate completely. Then, obtain the target product by sequentially filtering and drying.

[0231] The reaction conditions were optimized following the steps outlined above, and the results are shown in the table below:

[0232]

[0233]

[0234] Note: In all the above reactions, the starting material was 1 mmol of o-phenylenediamine; the solvent was 1 ml.

[0235] Using the same method as in entry 6, but with different reaction substrates, the following compounds were obtained:

[0236]

[0237] The product was filtered and dried to obtain 233 mg of a white solid, with a separation yield of 87%.

[0238] 1 H NMR (500MHz, DMSO-d6, TMS): δ (ppm) 10.57 (s, 2H), 6.91 (s, 4H).

[0239] 13 C NMR (126MHz, DMSO-d6, TMS): δ (ppm) 155.28 (C), 129.67 (C), 120.43 (CH), 108.46 (CH).

[0240] MS(ESI):m / z calcd for C7H6NO[M+H] + :135.06, found 135.1.

[0241]

[0242] 265 mg of solid product was obtained by filtration and drying, with a separation yield of 89.5%.

[0243] 1 H NMR (500MHz, DMSO-d6, TMS): δ (ppm) 10.47 (d, 2H, J = 20.0Hz), 6.80 (d, 1H, J = 10.0Hz), 6.73 (d, 2H, J = 10.0Hz), 2.27 (s, 3H).

[0244] 13 C NMR (125MHz, DMSO-d6, TMS): δ (ppm) 155.29, 129.72, 129.21, 127.31, 120.75, 108.87, 108.03, 20.91.

[0245]

[0246] 266 mg of solid product was obtained by filtration and drying, with a separation yield of 90%.

[0247] 1 H NMR (500MHz, DMSO-d6, TMS): δ (ppm) 10.65 (s, 1H), 10.53 (s, 1H), 6.82 (t, 1H, J1 = J2 = 10.0Hz), 6.74 (t, 1H, J1 = J2 = 10.0Hz), 2.25 (s, 3H).

[0248] 13 C NMR (125MHz, DMSO-d6, TMS): δ (ppm) 155.47, 129.23, 128.55, 121.56, 120.34, 117.13, 106.05, 16.17.

[0249]

[0250] 289 mg of solid product was obtained by filtration and drying, with a separation yield of 89.2%.

[0251] 1 H NMR (500MHz, DMSO-d6, TMS): δ (ppm) 10.34 (s, 2H), 6.70 (s, 2H), 2.17 (s, 6H).

[0252] 13 C NMR (125MHz, DMSO-d6, TMS): δ (ppm) 155.41, 127.75, 109.54.

[0253]

[0254] 176 mg of solid product was obtained by filtration and drying, with a separation yield of 58%.

[0255] 1 H NMR (500MHz, DMSO-d6, TMS): δ (ppm) 10.74 (s, 1H), 10.63 (s, 1H), 6.90-6.72 (m, 3H).

[0256] 13 C NMR (125MHz, DMSO-d6, TMS): δ (ppm) 158.28, 156.42, 155.54, 130.23, 125.94, 108.61, 101.38.

[0257]

[0258] 264 mg of solid product was obtained by filtration and drying, with a separation yield of 78%.

[0259] 1 H NMR (500MHz, DMSO-d6, TMS): δ (ppm) 10.76 (s, 2H), 6.97-6.90 (m, 3H).

[0260] 13 C NMR (125MHz, DMSO-d6, TMS): δ (ppm) 155.19, 130.82, 128.60, 124.47, 120.09, 109.50, 108.36.

[0261]

[0262] 421 mg of solid product was obtained by filtration and drying, with a separation yield of 98.7%.

[0263] 1 H NMR (500MHz, DMSO-d6, TMS): δ (ppm) 10.76 (s, 2H), 7.05 (t, 2H, J1 = J2 = 10.0Hz), 6.88 (d, 1H, J = 10.0Hz).

[0264] 13 C NMR (125MHz, DMSO-d6, TMS): δ (ppm) 155.03, 131.20, 128.98, 122.89, 111.98, 111.02, 110.06.

[0265]

[0266] 255 mg of solid product was obtained by filtration and drying, with a separation yield of 63%.

[0267] 1 H NMR (500MHz, DMSO-d6, TMS): δ (ppm) 11.06 (s, 1H), 10.97 (s, 1H), 7.30 (d, 1H, J = 5.0Hz), 7.17 (s, 1H), 7.10 (d, 1H, J = 5.0Hz).

[0268] 13 C NMR (125MHz, DMSO-d6, TMS): δ (ppm) 155.30, 132.85, 129.83, 124.85, 121.02, 117.85, 108.53, 104.90.

[0269]

[0270] The solid product was obtained by filtration and drying, with a separation yield of 78%.

[0271] 1 H NMR (500MHz, DMSO-d6, TMS): δ (ppm) 11.11 (s, 1H), 10.88 (s, 1H), 7.70-7.63 (m, 3H), 7. 55(t,2H,J1=J2=5.0Hz),7.44(d,1H,J=10.0Hz),7.33(s,1H),7.08(d,1H,J=10.0Hz).

[0272] 13 C NMR (125MHz, DMSO-d6, TMS): δ (ppm) 194.98, 155.38, 138.19, 134.02, 131.81, 129.66, 129.38, 129.17, 128.34, 124.44, 109.71, 107.98.

[0273]

[0274] 206 mg of solid product was obtained by filtration and drying, with a separation yield of 63%.

[0275] 1 H NMR (500MHz, DMSO-d6, TMS): δ (ppm) 10.50 (s, 1H), 10.37 (s, 1H), 6.81 (d, 1H, J = 5.0Hz), 6.52 (d, 2H, J = 10.0Hz), 3.70 (s, 3H).

[0276] 13C NMR (125MHz, DMSO-d6, TMS): δ (ppm) 155.64, 154.33, 130.49, 123.56, 108.71, 106.07, 95.27, 55.42.

[0277]

[0278] The solid product was obtained by filtration and drying, with a separation yield of 97%.

[0279] 1 H NMR (500MHz, DMSO-d6, TMS): δ (ppm) 10.07 (s, 2H), 7.21 (t, 2H, J1 = J2 = 5.0Hz), 7.11 (d, 2H, J = 5.0Hz), 6.52 (d, 2H, J = 5.0Hz).

[0280] 13 C NMR (125MHz, DMSO-d6, TMS): δ (ppm) 150.09, 137.67, 134.15, 128.03, 117.65, 113.66, 104.01.

[0281] Example 5: Synthesis of benzothiazolone derivatives by reacting o-aminothiophenol with CO2 in the presence of hydrogen sulfide.

[0282]

[0283] Two mmol of the starting material, an o-aminothiophenol, was placed in a 15 mL stainless steel high-pressure reactor equipped with a magnetic stir bar. Two mmol of base and two mL of solvent were then added sequentially, and the reactor was tightened. The reactor was first purged with the corresponding amount of hydrogen sulfide gas, followed by the corresponding amount of CO2. The mixture was then stirred at the appropriate temperature for 24 h. After the reaction was complete, the mixture was cooled to room temperature, the gas in the reactor was purged, and the mixture was extracted with ethyl acetate. The organic phases were combined and dried with anhydrous magnesium sulfate. The drying agent was removed by filtration, and the solvent was removed under reduced pressure to obtain the crude product. The crude product was then purified by column chromatography to obtain the target product.

[0284] The reaction conditions were optimized following the steps outlined above, and the results are shown in the table below:

[0285]

[0286] Note: The raw materials used were all 2 mmol o-aminothiophenol; the solvent was 2 mL; and the reaction time was 24 h.

[0287] Using the same method as in entry 7, but with different reaction substrates, the following compounds were obtained:

[0288]

[0289] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel) separation: using dichloromethane:ethyl acetate (V / V) = 20:1 as the developing solvent, 143 mg of white solid was obtained, with a separation yield of 94.4%.

[0290] Characterization data for benzothiazol-2-one (1a): 1 H NMR (CDCl3, 500MHz): δ (ppm) 10.01 (brs, 1H), 7.41 (d, 1H, J = 7.5Hz), 7.30-7.26 (m, 1H), 7.17-7.14 (m, 2H). 13 C NMR (CDCl3, 125MHz): δ (ppm) 172.8, 135.3, 126.5, 123.9, 123.3, 122.6, 111.7; MS (EI): m / z calcd for C7H5NOS[M] + :151.0,found 151.0.mp:139-140℃.

[0291]

[0292] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Dichloromethane:ethyl acetate (V / V) = 5:1 was used as the developing solvent, and 141 mg of white solid was obtained, with a separation yield of 76.2%.

[0293] Characterization data for 6-chlorobenzothiazol-2-one (1b): 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 12.02 (brs, 1H), 7.74 (d, 1H, J = 2.0Hz), 7.32 (dd, 1H, J1 = 8.5, J2 = 2.5Hz), 7.11 (d, 1H, J = 8.5Hz); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 169.7, 135.3, 126.4, 125.2, 122.4, 122.7; MS (EI): m / z calcd for C7H4ClNOS[M] + :185.1,found 185.0.mp:212-214℃.

[0294]

[0295] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel) separation: using dichloromethane:ethyl acetate (V / V) = 20:1 as the developing solvent, 195 mg of white solid was obtained, with a separation yield of 85%.

[0296] Characterization data for 6-bromobenzothiazol-2-one (1c): 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 12.02 (brs, 1H), 7.86 (d, 1H, J = 2.0Hz), 7.44 (dd, 1H, J1 = 8.5, J2 = 2.5Hz), 7.05 (d, 1H, J = 8.5Hz); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 169.7, 135.6, 129.2, 125.6, 125.0, 114.0, 113.1; MS (EI): m / z calcd for C7H4BrNOS[M] + :228.9,found 228.9.mp:231-232℃.

[0297]

[0298] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): using dichloromethane:ethyl acetate (V / V) = 20:1 as the developing solvent, 149 mg of white solid was obtained, with a separation yield of 67.9%.

[0299] Characterization data for 6-trifluoromethylbenzothiazol-2-one (1d): 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 12.22 (brs, 1H), 7.85 (d, 1H, J = 8.5Hz), 7.48 (dd, 1H, J1 = 8.0Hz, J2 = 1.0Hz), 7.33 (d, 1H, J = 1.5Hz); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 169.7, 136.7, 128.4 (d, J = 1.25Hz), 126.9 (q, J = 31.9.5 Hz), 124.0 (q, J = 270.5Hz), 123.8, 119.0 (q, J = 3.9Hz), 107.6 (q, J = 4.1Hz); MS (EI): m / z calcd for C8H4F3NOS[M] + :219.2,found 219.0.mp:216-218℃.

[0300]

[0301] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel) separation: using dichloromethane:ethyl acetate (V / V) = 10:1 as the developing solvent, 170 mg of white solid was obtained, with a separation yield of 94%.

[0302] Characterization data for 6-methoxybenzothiazol-2-one (1e): 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 11.658 (brs, 1H), 7.23 (d, 1H, J = 2.5Hz), 7.02 (d, 1H, J = 8.5Hz), 6.86 (dd, 1H, J1 = 8.5Hz, J2 = 2.5Hz), 3.73 (s, 3H); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 169.8, 155.2, 129.9, 124.3, 113.2, 112.1, 107.8, 55.6; MS (EI): m / z calcd for C8H7NO2S[M] + :180.9,found181.0.mp:161-163℃.

[0303]

[0304] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel) separation: using dichloromethane:ethyl acetate (V / V) = 50:1 as the developing solvent, 160 mg of white solid was obtained, with a separation yield of 96.8%.

[0305] Characterization data of 6-methylbenzothiazol-2-one: 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 11.75 (brs, 1H), 7.36 (s, 1H), 7.07-7.09 (m, 1H), 7.00 (d, 1H, J = 8Hz), 2.30 (s, 3H); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 169.8, 133.9, 131.7, 127.0, 123.2, 122.5, 111.1, 20.5; MS (EI): m / z calcdfor C8H7NOS[M] + :165.0,found 165.0.mp:170-171℃.

[0306]

[0307] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Dichloromethane:ethyl acetate (V / V) = 50:1 was used as the developing solvent, and 94 mg of white solid was obtained, with a separation yield of 51.0%.

[0308] Characterization data of 5-chlorobenzothiazol-2-one: 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 12.04 (brs, 1H), 7.61 (d, 1H, J = 8.5Hz), 7.19 (dd, 1H, J1 = 8.5, J2 = 2.5Hz), 7.12 (d, 1H, J = 2.0Hz); 13 CNMR (DMSO-d6, 125MHz): δ (ppm) 170.0, 137.4, 130.8, 124.3, 122.4, 122.2, 111.2; MS (EI): m / z calcd for C7H4ClNOS[M] + :184.9,found 185.0.mp:224-226℃.

[0309]

[0310] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Dichloromethane:ethyl acetate (V / V) = 5:1 was used as the developing solvent, and 164 mg of white solid was obtained, with a separation yield of 99.3%.

[0311] Characterization data of 4-methylbenzothiazol-2-one: 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 11.73 (brs, 1H), 7.37 (dd, 1H, J1 = 7.5, J2 = 0.5Hz), 7.08-7.09 (m, 1H), 7.03 (t, 1H, J = 7.5Hz), 2.32 (s, 3H); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 170.4, 135.0, 127.6, 122.8, 122.5, 121.3, 120.0, 17.4; MS (EI): m / z calcd for C8H7NOS[M] + :165.1,found 165.0.mp:211-212℃.

[0312]

[0313] Dry column packing and dry column chromatography (200-300 mesh silica gel): Ethyl acetate: petroleum ether (V / V) = 3:1 was used as the developing solvent, and 155 mg of white solid was obtained, with a separation yield of 67.9%.

[0314] Characterization data of methyl sulfone benzothiazol-2-one: 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 12.41 (brs, 1H), 8.22 (d, 1H, J = 7.0Hz), 7.812 (dd, 1H, J = 7.5Hz, J = 2.0Hz), 7.31 (d, 1H, J = 8.0Hz), 3.20 (s, 3H); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 170.2, 140.4, 134.6, 125.6, 124.2, 122.2, 111.5, 43.9; MS (EI): m / z calcd for C8H7NO3S2[M] + :229.0,found 228.8.mp:241-244℃.

[0315] Example 6: Synthesis of benzothiazolone derivatives by reacting aromatic o-amino disulfides with CO2 in the presence of hydrogen sulfide.

[0316]

[0317] 0.5 mmol of disulfide, 0.5 mmol of base, and 2 ml of solvent were added sequentially to the reaction vessel, which was then tightened. An appropriate amount of H₂S was introduced, and the mixture was preheated. The corresponding amount of CO₂ was then introduced, and the reaction was carried out at the appropriate temperature for 12 hours. After the reaction was complete, the reaction vessel was cooled to room temperature, and the gas in the vessel was slowly purged. The mixture was extracted with ethyl acetate and saturated brine. The organic phases were combined and separated by column chromatography to obtain the target product.

[0318] The reaction conditions were optimized following the steps outlined above, and the results are shown in the table below:

[0319]

[0320] Note: The raw material used was 0.5 mmol of disulfide (dimer of o-aminothiophenol); the solvent was 2 mL; the molar ratio in the table is the molar ratio of disulfide to DBU; the reaction time was 12 h.

[0321] Using the same method as in entry 3, but with different reaction substrates, the following compounds were obtained:

[0322]

[0323] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel) separation: using dichloromethane:ethyl acetate (V / V) = 20:1 as the developing solvent, 148 mg of white solid was obtained, with a separation yield of 98%.

[0324] Characterization data: 1 H NMR (CDCl3, 500MHz): δ (ppm) 10.01 (brs, 1H), 7.41 (d, 1H, J = 7.5Hz), 7.30-7.26 (m, 1H), 7.17-7.14 (m, 2H). 13 C NMR (CDCl3, 125MHz): δ (ppm) 172.8, 135.3, 126.5, 123.9, 123.3, 122.6, 111.7; MS (EI): m / z calcd for C7H5NOS[M] + :151.0,found151.0.mp:139-140℃.

[0325]

[0326] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel) separation: using dichloromethane:ethyl acetate (V / V) = 20:1 as the developing solvent, 180 mg of white solid was obtained, with a separation yield of 97.2%.

[0327] Characterization data: 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 12.02 (brs, 1H), 7.74 (d, 1H, J = 2.0Hz), 7.32 (dd, 1H, J1 = 8.5, J2 = 2.5Hz), 7.11 (d, 1H, J = 8.5Hz); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 169.7, 135.3, 126.4, 125.2, 122.4, 122.7; MS (EI): m / z calcd forC7H4ClNOS[M] + :185.1,found 185.0.mp:212-214℃.

[0328]

[0329] Dry column packing and dry column chromatography (200-300 mesh silica gel): Dichloromethane:ethyl acetate (V / V) = 20:1 was used as the developing solvent, and 179 mg of white solid was obtained, with a separation yield of 78.3%.

[0330] Characterization data: 1H NMR (DMSO-d6, 500MHz): δ (ppm) 12.02 (brs, 1H), 7.86 (d, 1H, J = 2.0Hz), 7.44 (dd, 1H, J1 = 8.5, J2 = 2.5Hz), 7.05 (d, 1H, J = 8.5Hz); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 169.7, 135.6, 129.2, 125.6, 125.0, 114.0, 113.1; MS (EI): m / z calcd forC7H4BrNOS[M] + :228.9,found 228.9.mp:231-232℃.

[0331]

[0332] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel) separation: using dichloromethane:ethyl acetate (V / V) = 20:1 as the developing solvent, 169 mg of white solid was obtained, with a separation yield of 93.5%.

[0333] Characterization data: 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 11.658 (brs, 1H), 7.23 (d, 1H, J = 2.5Hz), 7.02 (d, 1H, J = 8.5Hz), 6.86 (dd, 1H, J1 = 8.5Hz, J2 = 2.5Hz), 3.73 (s, 3H); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 169.8, 155.2, 129.9, 124.3, 113.2, 112.1, 107.8, 55.6; MS (EI): m / z calcd for C8H7NO2S[M] + :180.9,found 181.0.mp:161-163℃.

[0334]

[0335] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel) separation: using dichloromethane:ethyl acetate (V / V) = 20:1 as the developing solvent, 149 mg of white solid was obtained, with a separation yield of 90%.

[0336] Characterization data: 1H NMR (DMSO-d6, 500MHz): δ (ppm) 11.73 (brs, 1H), 7.37 (dd, 1H, J1 = 7.5Hz, J2 = 0.5Hz), 7.08-7.09 (m, 1H), 7.03 (t, 1H, J = 7.5Hz), 2.32 (s, 3H). 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 170.4, 135.0, 127.6, 122.8, 122.5, 121.3, 120.0, 17.4; MS (EI): m / zcalcd for C7H5NOS[M] + :165.1,found 165.0.mp:211-212℃.

[0337]

[0338] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Dichloromethane:ethyl acetate (V / V) = 20:1 was used as the developing solvent, and 157 mg of white solid was obtained, with a separation yield of 95.4%.

[0339] Characterization data: 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 11.75 (brs, 1H), 7.36 (s, 1H), 7.07-7.09 (m, 1H), 7.00 (d, 1H, J = 8Hz), 2.30 (s, 3H); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 169.8, 133.9, 131.7, 127.0, 123.2, 122.5, 111.1, 20.5; MS (EI): m / z calcd for C8H7NOS[M] + :165.0,found 165.0.mp:170-171℃.

[0340]

[0341] Dry column packing and dry column chromatography (200-300 mesh silica gel): Dichloromethane:ethyl acetate (V / V) = 20:1 was used as the developing solvent, and 154 mg of white solid was obtained, with a separation yield of 93.5%.

[0342] Characterization data: 1H NMR (DMSO-d6, 500MHz): δ (ppm) 11.73 (brs, 1H), 7.37 (dd, 1H, J1 = 7.5, J2 = 0.5Hz), 7.08-7.09 (m, 1H), 7.03 (t, 1H, J = 7.5Hz), 2.32 (s, 3H); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 170.4, 135.0, 127.6, 122.8, 122.5, 121.3, 120.0, 17.4; MS (EI): m / z calcdfor C8H7NOS[M] + :165.1,found 165.0.mp:211-212℃.

[0343]

[0344] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Dichloromethane:ethyl acetate (V / V) = 1:2 was used as the developing solvent, and 140 mg of white solid was obtained, with a separation yield of 61%.

[0345] Characterization data: 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 12.41 (brs, 1H), 8.22 (d, 1H, J = 7.0Hz), 7.812 (dd, 1H, J = 7.5Hz, J = 2.0Hz), 7.31 (d, 1H, J = 8.0Hz), 3.20 (s, 3H); 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 170.2, 140.4, 134.6, 125.6, 124.2, 122.2, 111.5, 43.9; MS (EI): m / z calcd for C8H7NO3S2[M] + :229.0,found 228.8.mp:241-244℃.

[0346]

[0347] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel) separation: using dichloromethane:ethyl acetate (V / V) = 20:1 as the developing solvent, 128 mg of white solid was obtained, with a separation yield of 76%.

[0348] Characterization data: 1H NMR (DMSO-d6, 500MHz): δ (ppm) 12.39 (brs, 1H), 7.43 (d, 1H, J = 7.5Hz), 7.12-7.22 (m, 2H). 13 C NMR (DMSO-d6, 125MHz): δ (ppm) 169.7, 147.1 (d, J = 243.8Hz), 125.5 (d, J = 3.8Hz), 124.3 ( d, J=14.6Hz), 123.0 (d, J=6.5Hz), 118.6 (d, J=6.0Hz), 112.7 (d, J=16.9Hz); MS (EI): m / z calcd for C7H5NOS[M] + :169.0,found169.0.mp:172-174℃.

[0349] Example 7: Synthesis of imidazole (oxa or thiazolidinone) derivatives by reacting diamines, alcoholamines, or thiolamines with CO2 in the presence of hydrogen sulfide.

[0350]

[0351] Weigh 2 mmol of diamine, 0.8 mmol of base, and 2 ml of solvent, and add them sequentially to the reaction vessel, then tighten the vessel. Introduce the corresponding amount of H₂S into the reaction vessel, and then introduce the corresponding amount of CO₂ at a suitable temperature. Stir the reaction for 4 hours. After the reaction is complete, cool the reaction vessel to room temperature, slowly purge the gas from the vessel, open the vessel, and obtain the target product by extraction, column chromatography, or recrystallization.

[0352] The reaction conditions were optimized following the steps outlined above, and the results are shown in the table below:

[0353]

[0354]

[0355] Note: All raw materials used were 2 mmol of ethylenediamine; the solvent was 2 ml of NMP. In Entry 25, ethylenediamine was used as both solvent and base (no other solvent or base was added during the reaction). In Entry 26, ethylenediamine was used as base, and NMP was added as solvent.

[0356] Using the same method as in entry 10, but with different reaction substrates, the reaction results are as follows:

[0357] Characterization of compounds:

[0358]

[0359] Ethyl acetate extraction, column chromatography, and recrystallization yielded 170.2 mg of the target product in pure form, with a yield of 99%.

[0360] imidazolidin-2-one:white solid, 1 H NMR (500MHz, CDCl3) δ3.52 (s, 1H). 13 C NMR (126MHz, CDCl3) δ165.64,41.04.

[0361]

[0362] Ethyl acetate extraction, column chromatography, and recrystallization yielded the target product in pure form, 153.7 mg, with a yield of 68%. 1,3-Dimethylimidazolidin-2-one: Colorless oil, ¹H NMR (500 MHz, CDCl₃): d = 2.79 (s, 6H, 2CH₃), 3.27 (s, 4H, 2CH₂). ¹³C NMR (126 MHz, CDCl₃): d = 31.3, 44.9, 161.9.

[0363]

[0364] Ethyl acetate extraction and column chromatography yielded 216.5 mg of the target product in pure form, with a yield of 91%.

[0365] 4,5-Diphenylimidazolidin-2-one:white solid,1H NMR(500MHz,CDCl3):δ7.38-7.34(m,6H),7.27-7.30(m,4H),5.83(s,2H),4.57(s,2H).13C NMR (126MHz, CDCl3) δ163.1,140.2,128.7,128.2,126.4,65.9;

[0366]

[0367] Ethyl acetate extraction and multiple column chromatography yielded 241.74 mg of the target product in pure form, with a yield of 85%.

[0368] 1,3-Diethylimidazolidin-2-one:Colorless oil,95%.H NMR (500MHz, CDCl3): δ3.23(s,4H),3.19(q,J=7.2Hz,4H),1.05(t,J=7.2Hz,6H).13C NMR (500MHz, CDCl3): δ161.3, 42.3, 38.9, 12.9.

[0369]

[0370] Ethyl acetate extraction and column chromatography yielded 278.49 mg of the target product in pure form, with a yield of 99%.

[0371] octahydro-2H-benzo[d]imidazol-2-one:colourless solid,1H NMR(500MHz, CDCl3)δ4.75(s,2H),3.67(s,2H),1.66(s,4H),1.61–1.49(m,2H),1.31(dt,J=9.6,5.5Hz,2H).13C NMR (126MHz, CDCl3) δ77.67,52.45,28.85,20.88.

[0372]

[0373] Extraction and column chromatography yielded 192 mg of pure product, with a yield of 75%.

[0374] 1,3-Dimethyl-3,4,5,6-tetrahydropyrimidin-2(1H)-one:H NMR(500MHz,CDCl3):d=1.97(quintet,J=6.0Hz,2H,CH2),2.92(s,6H,2CH3),3.24(t,J=6.0Hz,4H,2CH2)13C NMR (126MHz, CDCl3): d=22.1, 35.5, 47.8, 156.7.

[0375]

[0376] Filtration yielded 188 mg of the target product in pure form, with a yield of 73%.

[0377] 5,5-dimethyltetrahydropyrimidin-2(1H)-one:white solid,1H NMR(500MHz,DMSO-d6)δ6.06(s,2H),2.76(s,4H),0.94(s,6H).13C NMR(126MHz,DMSO-d6)δ155.26,51.06,27.20,23.89.

[0378]

[0379] Ethyl acetate extraction and column chromatography yielded 174.4 mg of the target product in pure form, with a yield of 99%.

[0380] 5-phenylimidazolidine-2,4-dione:white solid,1H NMR(500MHz,DMSO-d6)δ10.77(s,1H),8.39(s,1H),7.37(d,J=34.7Hz,6H),5.16(s,1H).13C NMR (126MHz, DMSO-d6) δ174.34,157.65,136.21,128.80,128.39,126.86,61.35.

[0381]

[0382] Column chromatography, recrystallization with dichloromethane and ethyl acetate yielded 182 mg of the target product, with a yield of 91%.

[0383] 4-methylimidazolidin-2-one: white solid, 1H NMR (500MHz, CDCl3) δ5.00 (s, 2H), 3.92 (h, J = 8.3Hz, 1H), 3.61 (t, J = 8.4Hz, 1H), 3.17–2.99 (m, 1H), 1.25 (d, J = 6.4Hz, 3H). 13 C NMR (126MHz, CDCl3) δ163.90,48.41,48.01,21.15.

[0384]

[0385] Filtration yielded 164.1 mg of the target product in pure form, with a yield of 72%.

[0386] 1-methyltetrahydropyrimidin-2(1H)-one:white solid, 1H NMR (500MHz, DMSO-d6) δ6.11(s,1H),3.15(t,J=5.5Hz,2H),3.09(t,J=5.5Hz,2H),2.74(s,3H),1.79(p,J=6.6,5.9Hz,2H). 13 C NMR(126MHz,DMSO-d6)δ46.95,22.02

[0387]

[0388] Ethyl acetate extraction and column chromatography yielded 221.1 mg of the target product in pure form, with a yield of 97%.

[0389] ethylimidazolidin-2-one: Colorless oil, 1H NMR (500MHz, CDCl3) δ3.50–3.35 (m, 6H), 3.25 (q, J = 7.2Hz, 2H), 1.12 (t, J = 7.2Hz, 3H).13C NMR (126MHz, CDCl3) δ162.59,44.39,38.25,38.09,12.69.

[0390]

[0391] Ethyl acetate extraction and column chromatography yielded 172.4 mg of the target product in pure form, with a yield of 99%.

[0392] 2-Oxazolidinone: 1H NMR (500MHz, CDCl3) δ3.64 (t, 2H), 4.46 (t, 2H), 6.68 (s, 1H). 13CNMR (126MHz, CDCl3), δ 41.0, 65.5, 161.5.

[0393]

[0394] Ethyl acetate extraction and column chromatography yielded 172.0 mg of the target product in pure form, with a yield of 86%.

[0395] 1,3-Oxazinan-2-one:H NMR(500MHz,DMSO d6)δ1.77-1.85(m,2H,NH-CH2-CH2-CH2-O),3.12-3.19(m,2H),4.15(t,J=5.4Hz,2H),7.13(s,1H,).13C NMR(126MHz,DMSOd6)δ21.79,39.78,67.04,153.74.

[0396]

[0397] Ethyl acetate extraction and column chromatography yielded 171.0 mg of the target product in pure form, with a yield of 84%.

[0398] thiazolidin-2-one:1H NMR(500MHz, CDCl3)δ3.37(t,2H,J=3.6H z,),3.59(t,2H,J=3.6H z,),6.9 9(s,1H,)

[0399] Example 8: Synthesis of thioquinazolinidone derivatives by reacting o-aminobenzonitrile with CO2 under the action of H2S.

[0400]

[0401] A magnetic stir bar was placed in a 10 mL stainless steel high-pressure reactor, and 1 mmol of o-aminobenzonitrile derivative, an appropriate amount of H2S, and 2 mL of solvent were added sequentially. The reactor was then tightened. Carbon dioxide was introduced into the reactor at the specified pressure, and the reaction was stirred for 24 h. The reaction was then stopped and the reactor was cooled. The gas inside the reactor was slowly purged, the reactor was opened, and the mixture was extracted with ethyl acetate and saturated brine. The organic phases were combined, and the crude product was obtained by vacuum distillation. The target product was purified by column chromatography with petroleum ether and ethyl acetate.

[0402] The reaction conditions were optimized following the steps outlined above, and the results are shown in the table below:

[0403]

[0404] Note: In all the above reactions, the starting material was 1 mmol o-aminobenzonitrile; the solvent was 2 ml; the molar ratio was the molar ratio of the starting material to DBU; and the reaction time was 24 h.

[0405] Using the method in entry 9, and different substrates, the following compounds were obtained:

[0406]

[0407] Dry-packed column chromatography (200-300 mesh silica gel) separation: Gradient elution was used with petroleum ether and ethyl acetate as eluents, with a petroleum ether:ethyl acetate (V / V) ratio of 1:1. After separation, 235.2 mg of a yellow solid, 6,7-dimethoxy-2-oxo-4-thioquinazoline dione, was obtained, with a column chromatography yield of 99%. Analytical results indicate that the obtained target product has the correct structure.

[0408] 1H NMR (500MHz, DMSO-d6) δ = 12.50 (s, 1H), 11.46 (s, 1H), 7.69 (s, 1H), 6.64 (s, 1H), 3.84 (s, 3H), 3.79 (s, 3H). 13 C NMR (126MHz, DMSO-d6)δ=188.97,156.06,147.50,144.71,134.94,113.90,110.09,97.30,56.05,55.63.MS(ESI):m / z calcd for C 10 H 10 N₂O₃S[M] + :239.04, found 239.2

[0409]

[0410] Dry-packed column chromatography (200-300 mesh silica gel) separation: Gradient elution was used with petroleum ether and ethyl acetate as eluents, with a petroleum ether:ethyl acetate (V / V) ratio of 2:1, which was later increased to 1:1. After separation, 184 mg of a yellow solid, 6-fluoro-2-oxo-4-thioquinazolinidone, was obtained, with a column chromatography yield of 94%. Analytical results indicate that the obtained target product has the correct structure.

[0411] 1 H NMR (500MHz, DMSO-d6) δ = 12.91 (s, 1H), 11.67 (s, 1H), 7.96 (dd, J = 9.7, 3.0Hz, 1H), 7.58 (td, J = 8.5, 3.0Hz, 1H), 7.20 (dd, J = 9.0, 4.6Hz, 1H). 13 C NMR (126MHz, DMSO-d6)δ=191.68,158.77,156.86,147.31,135.82,123.70,118.47,115.55.MS(ESI):m / z calcdfor C8H5FN2OS[M] + :197.01, found 196.9

[0412]

[0413] Dry packing and dry loading column chromatography (200-300 mesh silica gel) separation: gradient elution was used with petroleum ether and ethyl acetate as eluents, with a petroleum ether:ethyl acetate (V / V) ratio of 3:1. After separation, 217 mg of a white solid 6-bromo-2-oxo-4-thioquinazolinidone was obtained, with a column chromatography yield of 85%. The analytical results showed that the obtained target product had the correct structure.

[0414] 1 H NMR (500MHz, DMSO-d6) δ = 12.94 (s, 1H), 11.75 (s, 1H), 8.37 (dd, J = 2.4, 1.0Hz, 1H), 7.83 (ddd, J = 8.6, 2.4, 1.0Hz, 1H), 7.13 (dd, J = 8.7, 1.1Hz, 1H). 13 C NMR (126MHz, DMSO-d6) δ = 189.50, 147.08, 138.29, 137.44, 132.05, 121.64, 118.36, 114.79.MS (ESI): m / z calcd for C8H5BrN2OS[M] + :257.9,found 257.1.

[0415]

[0416] Dry-packed column chromatography (200-300 mesh silica gel) separation: Gradient elution was used with petroleum ether and ethyl acetate as eluents, with a petroleum ether:ethyl acetate (V / V) ratio of 2:1. After separation, 162 mg of a yellow solid, 7-fluoro-2-oxo-4-thioquinazoline dione, was obtained, with a column chromatography yield of 83%. Analytical results indicate that the obtained target product has the correct structure.

[0417] 1 H NMR (500MHz, DMSO-d6) δ = 12.77 (s, 1H), 11.65 (s, 1H), 8.27 (t, J = 7.3Hz, 1H), 7.59 (dd, J = 8.8, 6.6Hz, 1H), 7.37–7.29 (m, 1H). 13 C NMR (126MHz, DMSO-d6)δ=192.47,147.25,137.86,133.97,132.77,122.55,119.08,113.25.MS(ESI):m / z calcd forC8H5FN2OS[M] + :,197.01found 197.3.

[0418]

[0419] Dry packing and dry loading column chromatography (200-300 mesh silica gel): Gradient elution was used with petroleum ether and ethyl acetate as eluents, with a petroleum ether:ethyl acetate (V / V) ratio of 2:1. After separation, 219 mg of a yellow solid, 7-trifluoromethyl-2-oxo-4-thioquinazolinidone, was obtained. The column chromatography yield was 89%, and the analytical results showed that the target product had the correct structure.

[0420] 1 H NMR (500MHz, DMSO-d6) δ = 13.05 (s, 1H), 11.81 (s, 1H), 8.47 (d, J = 8.5Hz, 1H), 7.53–7.47 (m, 1H), 7.45 (d, J = 1.7Hz, 1H). 13 C NMR (126MHz, DMSO-d6) δ = 191.66, 149.23, 138.83, 134.14, 132.40, 122.71, 119.16, 113.84.MS (ESI): m / z calcd for C9H5F3N2OS[M] + :247.01,found 247.3.

[0421]

[0422] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel) separation: gradient elution was used with petroleum ether and ethyl acetate as eluents, with a petroleum ether:ethyl acetate (V / V) ratio of 2:1. After separation, 138 mg of a yellow solid 7-chloro-2-oxo-4-thioquinazolinidone was obtained, with a column chromatography yield of 65%. The analytical results showed that the obtained target product had the correct structure.

[0423] 1 H NMR (500MHz, DMSO-d6) δ = 12.71 (s, 1H), 11.56 (s, 1H), 8.23 ​​(t, J = 8.4Hz, 1H), 7.48 (dd, J = 8.5, 1.2Hz, 1H), 6.54–6.40 (m, 1H). 13 C NMR (126MHz, DMSO-d6)δ=191.92,170.17,151.67,136.49,130.76,115.32,113.52,112.55.MS(ESI):m / z calcd forC8H5ClN2OS[M] + :212.65,found 212.3.

[0424]

[0425] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel) separation: gradient elution was used with petroleum ether and ethyl acetate as eluents, with a petroleum ether:ethyl acetate (V / V) ratio of 2:1. After separation, 172 mg of a yellow solid 7-methyl-2-oxo-4-thioquinazolinidone was obtained, with a column chromatography yield of 89%. The analytical results showed that the obtained target product had the correct structure.

[0426] 1 H NMR (500MHz, DMSO-d6) δ = 12.66 (s, 1H), 11.56 (s, 1H), 8.19 (d, J = 8.3Hz, 1H), 7.03 (d, J = 8.4Hz, 1H), 6.94 (s, 1H), 2.35 (s, 3H). 13 C NMR (126MHz, DMSO-d6))δ=188.97,148.23,146.65,137.75,131.11,125.24,119.85,114.69.MS(ESI):m / z calcd forC9H8N2OS[M] + :193.04,found193.2.

[0427]

[0428] Dry packing and dry loading column chromatography (200-300 mesh silica gel) separation: gradient elution was used with petroleum ether and ethyl acetate as eluents, with a petroleum ether:ethyl acetate (V / V) ratio of 1:1. After separation, 80 mg of brown solid 6-nitro-2-oxo-4-thioquinazoline dione was obtained. The column chromatography yield was 36%, and the analytical results showed that the target product had the correct structure.

[0429] 1 H NMR (500MHz, DMSO-d6) δ = 12.51 (s, 1H), 11.28 (s, 1H), 7.48 (d, J = 2.6Hz, 1H), 7.00 (dd, J = 8.7, 2.6Hz, 1H), 6.92–6.89 (m, 1H). 13 C NMR (126MHz, DMSO-d6)δ=191.01,158.80,144.50,128.55,123.74,122.13,116.09,111.20.MS(ESI):m / z calcd forC8H5N3O3S[M] + :223.01,found 223.4.

[0430]

[0431] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Gradient elution was used with petroleum ether and ethyl acetate as eluents, with a petroleum ether:ethyl acetate (V / V) ratio of 2:1. After separation, 133 mg of a yellow solid 5-fluoro-2-oxo-4-thioquinazoline dione was obtained, with a column chromatography yield of 68%. The analytical results showed that the target product had the correct structure.

[0432] 1 H NMR (500MHz, DMSO-d6) δ = 11.85 (s, 1H), 11.20 (s, 1H), 7.35 (t, J = 8.1Hz, 1H), 6.68 (d, J = 8.3Hz, 1H), 6.50 (d, J = 7.8Hz, 1H). 13 C NMR (126MHz, DMSO-d6) δ = 186.47, 154.09, 147.11, 141.12, 134.24, 111.58, 110.66, 104.63.MS (ESI): m / z calcd forC8H5FN2OS[M] + :197.01,found 197.2

[0433]

[0434] Dry column packing and dry sample loading column chromatography (200-300 mesh silica gel): Gradient elution was used with petroleum ether and ethyl acetate as eluents, with a petroleum ether:ethyl acetate (V / V) ratio of 2:1. After separation, 240 mg of a yellow solid, 6-trifluoromethyl-2-oxo-4-thioquinazolinidone, was obtained. The column chromatography yield was 97%, and the analytical results showed that the target product had the correct structure.

[0435] 1 H NMR (500MHz, DMSO-d6) δ = 13.06 (s, 1H), 11.97 (d, J = 3.8Hz, 1H), 8.57–8.53 (m, 1H), 8.01–7.94 (m, 1H), 7.34 (dd, J = 8.6, 3.8Hz, 1H). 13 C NMR (126MHz, DMSO-d6)δ=190.90,162.47,147.31,141.69,132.45,127.71,123.41,119.99,118.13.MS(ESI):m / z calcd forC9H5F3N2OS[M] + :247.01,found 247.3.

[0436] All documents mentioned in this invention are incorporated herein by reference as if each document were individually incorporated by reference. Furthermore, it should be understood that after reading the foregoing teachings of this invention, those skilled in the art can make various alterations or modifications to this invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A method for preparing carbonyl compounds using carbon dioxide as a carbonylating agent, characterized in that, The method includes step (a); (a) In an inert solvent, in the presence of a base, o-iodoaniline is reacted with CO2 and hydrogen sulfide to give benzothiazolone derivatives; the reaction is carried out in the presence of cuprous iodide; The inert solvent is selected from the group consisting of: NMP and DMF; The alkali is selected from the following group: DBU, TBD, Et3N; R3 is a group selected from the following group: H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, -NH2.

2. A method for preparing carbonyl compounds using carbon dioxide as a carbonylating agent, characterized in that, The method includes step (b): (b) In an inert solvent and in the presence of a base, o-nitroiodobenzene is reacted with CO2 and hydrogen sulfide to synthesize benzothiazolone derivatives; the reaction is carried out in the presence of cuprous iodide; in step (b), the base is EtN3; the inert solvent is NMP; R3 is a group selected from the following group: H, halogen, C1-C6 alkyl, C1-C6 alkoxy, -OC(O)CH3.

3. A method for preparing carbonyl compounds using carbon dioxide as a carbonylating agent, characterized in that, The method includes step (e); (e) In an inert solvent and in the presence of a base, benzothiazolone derivatives are synthesized by reacting aromatic o-amino disulfides with CO2 in the presence of hydrogen sulfide. Wherein, R3 is a group selected from the following group: H, halogen, C1-C6 alkyl, C1-C6 alkoxy, -SO2CH3; The base is selected from the following group: DBU, TMG, triethylamine (EtN3); The inert solvent is selected from the group consisting of: NMP and 1,4-dioxane.

4. A method for preparing carbonyl compounds using carbon dioxide as a carbonylating agent, characterized in that, The method includes step (f); (f) Thiazolidinedion derivatives are synthesized by reacting mercaptoamines with CO2 in the presence of a base in an inert solvent; wherein U is S and R is H; The inert solvent is selected from the group consisting of: NMP, DMF, and 1,4-dioxane; The base is selected from the following group: DBU, TBD, TMG, triethylamine (EtN3); M is a C2 alkylene or substituted or unsubstituted phenyl group, wherein substitution means that one or more hydrogen atoms on the group are replaced by a substituent selected from the group consisting of: halogen, C1-C6 haloalkyl, C1-C6 alkyl, C1-C6 alkoxy, -SO2CH3.

5. The method according to any one of claims 1-4, characterized in that, The molar ratio of the reaction substrate to the base is 1:0.1-5.

6. The method according to any one of claims 1-4, characterized in that, In the reaction described, the molar ratio of the reaction substrate to CO2 is 1:1-100.

7. The method according to any one of claims 1-4, characterized in that, During the reaction process, CO2 is continuously introduced into the reactor, and the pressure of CO2 in the reactor is 0.1-12 MPa.

8. The method according to any one of claims 1-4, characterized in that, In the reaction, the molar ratio of the reaction substrate to the hydrogen sulfide is 1:0.05-20.

9. The method according to any one of claims 1-4, characterized in that, During the reaction process, H2S is continuously introduced into the reactor, and the pressure of H2S in the reactor is 0.05-1.5 MPa.

10. The method according to any one of claims 1-4, characterized in that, In the aforementioned reaction, the reaction temperature is between room temperature and 150°C.

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