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

Abstract

The present invention provides a method for catalytically activating carbon dioxide as a carbonylation reagent with inorganic sulfur. In this method, carbon dioxide can replace toxic and harmful carbonylation reagents to synthesize carbonyl-containing fine chemicals in the presence of H2S and a base. The said method has a high atom economy and can reduce the generation of by-products.

Description

Technical Field

[0001] The present invention relates to the field of organic synthesis. Specifically, the present invention provides a method for catalytic activation of carbon dioxide as a carbonylating reagent by inorganic sulfur. Background Art

[0002] The development of new methods for green and sustainable organic synthesis has received increasing attention. Green, pollution-free and recyclable basic components play a key role in such methods. Among them, CO2 is an ideal carbon source component due to its non-toxic, abundant content and recyclable characteristics. CO2 is both the waste gas emitted from fossil fuel combustion and a cheap, non-toxic, non-flammable and renewable C1 resource. From the perspective of green chemistry, due to its unique carbonyl structure, chemically converting it into high-value-added fine chemicals as a carbonylating reagent is not only an effective way to reduce the atmospheric CO2 concentration but also an important strategy for sustainable energy development. Therefore, it is of great significance to utilize CO2 in a sustainable manner to synthesize high-value-added chemical products.

[0003] Among various organic conversions of CO2, the use of CO2 for carbonylation to synthesize heterocyclic structures containing carbonyl has attracted increasing attention. CO2 is used to replace carbon source gases such as CO and phosgene, which are highly toxic and pose potential safety hazards to users. In recent years, the carbonylation reaction of C-H bond with CO2 has made remarkable progress due to its high atomic economy and high economic efficiency. More importantly, since the carbon price of CO2 is higher than that of CO, it can be ideally considered as the combination of CO and an oxidant (CO2 = CO + [O]), so that such carbonylation can be realized under neutral conditions in redox reactions, thereby achieving the purposes of reducing production costs, reducing heavy metal residues and solving safety hazards.

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

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

[0006] The present invention provides a method for preparing carbonyl compounds using CO2 as a carbonylating reagent, and H2S is used as a catalyst in the method.

[0007] The present invention also provides a method for the reaction of CO2 as a carbonylating reagent to prepare carbonyl compounds with the participation of H2S. In the method, H2S not only acts as a catalyst to catalyze the carbonylation reaction but also participates in the reaction as a reactant.

[0008] The present invention also provides a method for preparing carbonyl compounds by using H2S to participate in the reaction of CO2 as a carbonylation reagent. In this method, H2S serves as both a catalyst for catalyzing the carbonylation reaction and a reducing agent participating in the reaction.

[0009] In the first aspect of the present invention, there is provided a method for preparing carbonyl compounds using carbon dioxide as a carbonylation reagent, characterized in that the method is carried out in the presence of H2S and an optional base.

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

[0011]

[0012] (i) Reacting a compound of formula Ia with CO2 in an optional inert solvent in the presence of an optional base and an inorganic sulfur reagent to obtain a compound of formula I;

[0013]

[0014] (ii) Reacting a compound of formula IIa with CO2 in an optional inert solvent in the presence of a base and an inorganic sulfur reagent to obtain a compound of formula II;

[0015] Wherein, R1 and R2 are each independently selected from the group consisting of: substituted or unsubstituted C1-C 12 alkyl (such as substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C8 alkyl), substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl; or R1 and R2 together form a group selected from the group consisting of: substituted or unsubstituted C1-C6 alkylene, substituted or unsubstituted C6-C 10 aryl, substituted or unsubstituted 5-12 membered heteroaryl;

[0016] Ring A is a substituted or unsubstituted C6-C 10 aryl, or a substituted or unsubstituted 5-12 membered heteroaryl;

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

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

[0019] R is selected from the group consisting of: H, substituted or unsubstituted C1-C 12alkyl (such as substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C8 alkyl), substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C1-C6 alkoxy, SO2CH3, or phenyl unsubstituted or substituted by 1-4 substituents 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 selected from the group consisting of: H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, NH2, NO2, SO2CH3, or phenyl unsubstituted or substituted by 1-4 substituents 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 form -(CH2) n -, where n is selected from 2, 3, 4, 5 or 6;

[0021] And the said substitution means that one or more hydrogen atoms on the group are replaced by substituents selected from the group consisting of: halogen, oxygen atom (i.e. =O), C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 haloalkyl, NO2, SO2CH3, phenyl, 5-12-membered heteroaryl, 3-8-membered cycloalkyl, 5-12-membered saturated or partially unsaturated heterocycle; where the said phenyl, heteroaryl, cycloalkyl or heterocycle is unsubstituted or substituted by 1-4 substituents selected from the group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3;

[0022] Or, two substituents adjacent or attached to the same carbon atom together form -(CH2) n -, where n is selected from 2, 3, 4, 5 or 6.

[0023] In another preferred example, the base is an organic base; preferably, the base is selected from the group consisting of: C1-C 12 tertiary amines, C1-C 12 secondary amines, C1-C 12 primary amines, C2-C 12 amidines, C2-C 12 guanidines, C3-C 12 pyridines, C3-C 12Imidazoles; preferably, the base is selected from the group consisting of: DBU, TBD, MTBD, DBN, TMG, DABCO, ethylenediamine, triethylamine, DIPEA, DMAP, pyridine, or a combination thereof; preferably, the molar ratio of the reaction substrate to the base is 1:0 - 5 (such as 1:0.1 - 5).

[0024] In another preferred embodiment, the method comprises steps (a), (b), (c), (d), (e), (f), or (g);

[0025]

[0026] (a) Reacting o-iodoaniline with CO2 and hydrogen sulfide in the presence of a base in an optional inert solvent to obtain benzothiazolone derivatives;

[0027]

[0028] (b) Reacting o-nitroiodobenzene with CO2 and hydrogen sulfide in the presence of a base in an optional inert solvent to synthesize benzothiazolone derivatives;

[0029]

[0030] (c) Reacting propargylamine derivatives with CO2 and hydrogen sulfide in the presence of an optional base in an optional inert solvent to synthesize thiazolidin-2-one derivatives;

[0031] Wherein, R4 is selected from the group consisting of: H, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted phenyl;

[0032] R5, R6, and R7 are each independently selected from the group consisting of: H, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, phenyl, 5-12 membered heteroaryl, 5-12 membered saturated or partially unsaturated heterocycle, and the phenyl, heteroaryl, or heterocycle is unsubstituted or substituted with 1-4 substituents 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 form -(CH2) n -, wherein, n is selected from 2, 3, 4, 5, or 6;

[0033]

[0034] (d) Reacting o-aminobenzonitrile with CO2 and hydrogen sulfide in the presence of a base in an optional inert solvent to synthesize thioquinazoline dione derivatives;

[0035] Among them, R8 is one or more substituents selected from the following groups located on the benzene ring: H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, NO2, SO2CH3, or a phenyl group that is unsubstituted or substituted by 1-4 substituents selected from the following groups: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3;

[0036]

[0037] (e) In an optional inert solvent, in the presence of a base, reacting an aromatic o-aminodisulfide with CO2 under the action of hydrogen sulfide to synthesize benzothiazolone derivatives;

[0038]

[0039] (f) In an optional inert solvent, in the presence of an optional base, reacting a diamine, an alkanolamine or a mercaptoamine with CO2 under the action of hydrogen sulfide to synthesize imidazolidinone derivatives, oxazolidinone derivatives or thiazolidinone derivatives; wherein, U is O, S or NR;

[0040] M is a substituted or unsubstituted C2-C4 alkylene group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 5-12-membered heteroaryl group, wherein the definition of substitution is as described in claim 2;

[0041] (g) In an optional inert solvent, in the presence of an optional base, reacting an amine with CO2 under the action of hydrogen sulfide to synthesize urea derivatives;

[0042]

[0043] R9 is selected from the following groups: H, substituted or unsubstituted C1-C 12 alkyl (such as substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C8 alkyl), substituted or unsubstituted C3-C8 cycloalkyl, phenyl, 5-12-membered heteroaryl, 5-12-membered saturated or partially unsaturated heterocycle, and the phenyl, heteroaryl or heterocycle is unsubstituted or substituted by 1-4 substituents selected from the following groups: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3.

[0044] In another preferred example, the inert solvent is selected from the following groups: NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH2Cl2, CHCl3, CCl4, toluene, ethyl acetate, supercritical CO2, or a combination thereof.

[0045] In another preferred example, in the said reaction, the molar ratio of the reaction substrate to CO2 is 1:1 - 100.

[0046] In another preferred example, during the said reaction process, CO2 is continuously introduced into the reactor, and the pressure of the CO2 in the reactor is 0.1 - 12 MPa.

[0047] In another preferred example, in the said reaction, the molar ratio of the reaction substrate to the hydrogen sulfide is 1:0.05 - 20.

[0048] In another preferred example, during the said reaction process, H2S is continuously introduced into the reactor, and the pressure of the H2S in the reactor is 0.05 - 1.5 Mpa.

[0049] In another preferred example, in the said reaction, the reaction temperature is room temperature to 150 °C.

[0050] It should be understood that within the scope of the present invention, the above various technical features of the present invention and the technical features specifically described hereinafter (such as in the examples) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be elaborated one by one here. Detailed implementation manners

[0051] Through long - term and in - depth research, the present inventors unexpectedly found that by using H2S as a catalyst, CO2 can be efficiently catalyzed to react with a series of substrates as a carbonyl source to prepare carbonylated compounds. This carbonylation reaction can occur alone or together 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 - mentioned discovery, the inventors completed the present invention.

[0052] Synthesis method using CO2 as a carbonylation reagent

[0053] The present invention provides a method for preparing carbonylated compounds using carbon dioxide as a carbonylation reagent, and the said method is carried out in the presence of H2S. The said H2S can be used as a simple catalyst or, while catalyzing, also as a reactant to further react with the reaction substrate or generate an intermediate.

[0054] Specifically, the said method includes step (i) or step (ii):

[0055]

[0056] (i) In an inert solvent, in the presence of a base and an inorganic sulfur reagent, reacting a compound of formula Ia with CO2 to obtain a compound of formula I (wherein the compound of formula Ia can be a mixture of R1-X and R2-Y, or a compound in which R1-X and R2Y together form a compound having two reactive functional groups X and Y);

[0057]

[0058] (ii) In an inert solvent, in the presence of a base and an inorganic sulfur reagent, reacting a compound of formula IIa with CO2 to obtain a compound of formula II;

[0059] Wherein the definitions of each group are as described above.

[0060] In a preferred embodiment of the present invention, the above steps are carried out in the presence of a base, and the base is preferably an organic base. Preferably, the base is selected from the following group: C1-C 12 tertiary amines, C1-C 12 secondary amines, C1-C 12 primary amines, C2-C 12 amidines, C2-C 12 guanidines, C3-C 12 pyridines, C3-C 12 imidazoles, DBU, TBD, MTBD, DBN, TMG, DABCO, ethylenediamine, triethylamine, DIPEA, DMAP, pyridine, or a combination thereof; preferably, the molar ratio of the reaction substrate to the base is 1:0.1-5.

[0061] In the above method, 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 a combination thereof. In particular, since a carbon dioxide gas stream is required in the method of the present invention, a preferred embodiment is to use supercritical CO2 as the solvent.

[0062] In the above method, the molar ratio of the reaction substrate to CO2 is not particularly limited and can be 1:1-100.

[0063] During the reaction process, CO2 is continuously introduced into the reactor. In a preferred reaction method, the pressure of CO2 in the reactor is 0.1-12 MPa; such as 0.2-10 MPa, 0.5-10 MPa, 0.6-10 MPa, 0.8-8 MPa, or 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa or 6 MPa.

[0064] In the described reaction, the molar ratio of the reaction substrate to the inorganic sulfur is preferably 1:0.05 - 20.

[0065] During the described reaction process, H2S is continuously introduced into the reactor, and preferably the pressure of H2S in the reactor is 0.08 - 1.5 Mpa, such as 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1 MPa, 1.1 MPa, 1.2 MPa, 1.3 MPa, 1.4 MPa.

[0066] The temperature of the described reaction is not particularly limited, and preferably it is carried out at room temperature (usually 0 - 40 °C) to 150 °C, such as 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C.

[0067] 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 through steps (a), (b), (c), (d), (e), (f);

[0068] (a) o-Iodoaniline reacts with CO2 and hydrogen sulfide to synthesize benzothiazolone derivatives

[0069]

[0070] In an inert solvent, in the presence of a base, o-iodoaniline reacts with CO2 and hydrogen sulfide to obtain benzothiazolone derivatives. In the above reaction, the base is preferably DABCO, DBU, TBD, or Et3N; more preferably DBU or Et3N. The solvent is preferably NMP or DMF, and the amount of the base used is preferably 1 - 3 equivalents. In particular, when the reactant used is an organic base or can be used as a solvent, the described reaction can also be carried out without a solvent or in the absence of an organic base.

[0071] In another preferred example, in step (a), the pressure ratio of CO2 to H2S is (1 - 8):(0.1 - 0.8).

[0072] In another preferred example, in step (a), the method reacts at 70 - 100 °C, preferably at 80 - 90 °C.

[0073] In another preferred example, in step (a), in the method, the pressure of CO2 in the reactor is 2 - 5 MPa, and the pressure of H2S in the reactor is 0.3 - 0.5 Mpa.

[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; the amount of the base used is preferably 2 - 5 equivalents, more preferably 2 - 4 equivalents.

[0077] In another preferred example, in the step (b), the pressure ratio of CO2 to H2S is (1 - 8):(0.5 - 1.5), preferably 2 - 4:1.

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

[0079] In another preferred example, in the step (b), the reaction is carried out at 70 - 100 °C, preferably at 80 - 90 °C. In another preferred example, in the step (a), in the method, the pressure of CO2 in the reactor is 2 - 5 MPa, and the pressure of H2S in the reactor is 0.5 - 1 MPa.

[0080] (c) Propargylamine reacts with CO2 and hydrogen sulfide to synthesize thiazolidin-2-one derivatives

[0081]

[0082] In an inert solvent and in the presence of a base, a propargylamine derivative reacts with CO2 and hydrogen sulfide to synthesize thiazolidin-2-one derivatives;

[0083] wherein, R4 is selected from the group consisting of: H, substituted or unsubstituted C1 - C6 alkyl;

[0084] R5, R6 and R7 are each independently selected from the group consisting of: H, substituted or unsubstituted C1 - C6 alkyl, or phenyl which is unsubstituted or substituted by 1 - 3 substituents 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 form - (CH2) n -, wherein, n is selected from 2, 3, 4, 5 or 6;

[0085] In the above reaction, the base is preferably DBU, Et3N, TBD or K2CO3, more preferably DBU, Et3N or TBD; the solvent is preferably CH3OH, DMF, NMP or DMSO, more preferably DMSO; the amount of the base used is preferably 0.5 - 1.5 equivalents, more preferably 0.6 - 1.2 equivalents.

[0086] In another preferred embodiment, in the step (c), the pressure ratio of CO2 to H2S is 1:(0.2 - 1.5), more preferably 1:0.8 - 1.2.

[0087] In another preferred embodiment, in the step (c), the reaction is carried out at 20 - 60 °C, preferably at 20 - 40 °C.

[0088] In another preferred embodiment, in the step (c), in the method, the pressure of CO2 in the reactor is 0.8 - 1.2 MPa, and the pressure of H2S in the reactor is 0.5 - 1 MPa (preferably 0.8 - 1 MPa).

[0089] (d) o - aminobenzonitrile reacts with CO2 and hydrogen sulfide to synthesize thio - benzamide or thio - quinazoline - dione derivatives

[0090]

[0091] In an inert solvent and in the presence of a base, o - aminobenzonitrile reacts with CO2 and hydrogen sulfide to synthesize thio - benzamide or thio - quinazoline - dione derivatives; in this reaction, CO2 and H2S act as reactants together to form a six - membered ring structure. In the above reaction, the base is preferably DBU; the solvent is preferably DMF, and the amount of the base used is preferably 0.2 - 2 equivalents, more preferably 0.8 - 2 equivalents.

[0092] In another preferred embodiment, in the step (d), the pressure ratio of CO2 to H2S is (2 - 5):(0.2 - 1.2), more preferably 3 - 10:1.

[0093] In another preferred embodiment, in the step (d), the reaction is carried out at 40 - 60 °C, preferably at 45 - 55 °C. In another preferred embodiment, in the step (d), in the method, the pressure of CO2 in the reactor is 2 - 5 MPa, and the pressure of H2S in the reactor is 0.4 - 1 MPa.

[0094] (e) Aromatic o - aminodisulfide reacts with CO2 under the action of hydrogen sulfide to synthesize benzothiazolone derivatives

[0095]

[0096] In an inert solvent, in the presence of a base, an aromatic o - aminodisulfide reacts with CO₂ under the action 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, DMSO, more preferably NMP; the amount of the base used is preferably 0.2 - 2 equivalents, more preferably 0.4 - 1.2 equivalents.

[0097] In another preferred example, in the step (e), the pressure ratio of CO₂ to H₂S is (1 - 5):(0.1 - 1.2).

[0098] In another preferred example, in the step (e), the method reacts at 25 - 100 °C, preferably at 80 - 90 °C.

[0099] In another preferred example, in the step (e), in the method, the pressure of CO₂ in the reactor is 1 - 5 MPa, and the pressure of H₂S in the reactor is 0.2 - 1.0 Mpa.

[0100] (f) Diamines, alkanolamines or mercaptoamines react with CO₂ under the action of hydrogen sulfide to synthesize imidazolidinone, oxazolidinone or thiazolidinone derivatives

[0101]

[0102] In an optional inert solvent, in the presence of an optional base, diamines, alkanolamines or mercaptoamines react with CO₂ under the action of hydrogen sulfide to synthesize imidazolidinone derivatives, oxazolidinone derivatives or thiazolidinone derivatives;

[0103] Wherein, U is O, S or NR;

[0104] M is a substituted or unsubstituted C₂ - C₄ alkylene group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 5 - 12 - membered heteroaryl group, wherein the definition of substitution is as described above.

[0105] When U is NR and M is a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 5 - 12 - membered heteroaryl group:

[0106] In the above reaction, the base is preferably DABCO, DBU, TMG or Et₃N, preferably DBU or TMG; the solvent is preferably NMP, DMF, ethylene glycol or dichloromethane, preferably NMP; the amount of the base used is preferably 0.1 - 2 equivalents. In particular, when the reactants used are organic bases or can be used as solvents, the reaction can also be carried out without a solvent or in the absence of an organic base.

[0107] In another preferred example, in the step (f), the pressure ratio of CO2 to H2S is (1 - 65):1.

[0108] In another preferred example, in the step (f), the method reacts at 20 - 60 °C, preferably at 30 - 50 °C. In another preferred example, in the step (f), in the method, the pressure of CO2 in the reactor is 1 - 5 MPa, and the pressure of H2S in the reactor is 0.05 - 1.5 Mpa.

[0109] When U is NR and M is a substituted or unsubstituted C2 - C4 alkylene group:

[0110] In the above reaction, the base is preferably DBU, TBD, DIPEA or Et3N, preferably DBU, DIPEA or Et3N; the solvent is preferably NMP, DMF, ethylene glycol or dichloromethane, preferably NMP; the amount of the base used is preferably 0.1 - 1 equivalent, more preferably 0.2 - 0.6 equivalent. 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.

[0111] In another preferred example, in the step (f), the pressure ratio of CO2 to H2S is (3 - 35):1, more preferably (3 - 25):1.

[0112] In another preferred example, in the step (f), the method reacts at 80 - 120 °C.

[0113] In another preferred example, in the step (f), in the method, the pressure of CO2 in the reactor is 1 - 5 MPa, and the pressure of H2S in the reactor is 0.2 - 1 Mpa.

[0114] When U is S:

[0115] In the above reaction, the base is preferably DABCO, DBU, TMG, TBD or Et3N, preferably DBU, Et3N, or TMG; the solvent is preferably NMP, DMF, ethylene glycol or dichloromethane, preferably NMP or DMF; the amount of the base used is preferably 0.1 - 2 equivalents.

[0116] 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. In addition, when the pressure of CO2 and the reaction temperature meet the conditions for forming supercritical carbon dioxide, the reaction can also be carried out in the absence of a solvent.

[0117] In another preferred example, in the step (f), the pressure ratio of CO2 to H2S is (3 - 25):1.

[0118] In another preferred example, in the step (f), the method reacts at 20 - 60 °C, preferably at 30 - 50 °C.

[0119] In another preferred example, in the step (f), in the method, the pressure of CO2 in the reactor is 3 - 12 MPa, and the pressure of H2S in the reactor is 0.2 - 1.0 Mpa.

[0120] (g) Amine reacts with CO2 under the action of hydrogen sulfide to synthesize urea derivatives

[0121]

[0122] In an optional inert solvent and in the presence of an optional base, amine reacts with CO2 under the action of hydrogen sulfide to synthesize urea derivatives;

[0123] R9 is selected from the group: H, substituted or unsubstituted C1 - C 12 alkyl (such as substituted or unsubstituted C1 - C6 alkyl, substituted or unsubstituted C1 - C8 alkyl), substituted or unsubstituted C3 - C8 cycloalkyl, phenyl, 5 - 12 - membered heteroaryl, 5 - 12 - membered saturated or partially unsaturated heterocycle, and the phenyl, heteroaryl or heterocycle is unsubstituted or substituted by 1 - 4 substituents selected from the group: halogen, C1 - C6 alkyl, C1 - C6 haloalkyl, C1 - C6 alkoxy, OH, NO2, NH2, SO2CH3;

[0124] In the above reaction, the base is preferably DBU, TMG or Et3N, preferably DBU; the solvent is preferably NMP, DMF or methanol, preferably NMP; the amount of the base used is preferably 0.1 - 2 equivalents, but since the substrate organic amine used can be used as a base or a solvent, the reaction can also be carried out in the absence of an organic base and / or in the absence of a solvent.

[0125] In another preferred example, in the step (f), the pressure ratio of CO2 to H2S is (5 - 20):1.

[0126] In another preferred example, in the step (f), the method reacts at 90 - 130 °C, preferably at 30 - 50 °C.

[0127] In another preferred example, in the step (f), in the method, the pressure of CO2 in the reactor is 5 - 20 MPa, and the pressure of H2S in the reactor is 0.5 - 2 Mpa.

[0128] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. The experimental methods without specific conditions noted in the following embodiments are generally carried out under conventional conditions or according to the conditions recommended by the manufacturers. Unless otherwise specified, percentages and parts are calculated by weight.

[0129] The first type of inorganic sulfur serves as both a raw material and a catalyst

[0130] Example 1 Synthesis of benzothiazolone derivatives by reacting o-iodoaniline with CO2 and hydrogen sulfide

[0131]

[0132] The reaction method is as follows:

[0133] 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 to the reaction kettle in sequence, then tighten the reaction kettle. Introduce the corresponding amount of H2S into the reaction kettle, stir and react at 90 °C for 30 min, then introduce the corresponding amount of CO2 into the reaction kettle, and continue to stir and react at the corresponding temperature for 24 h. After the reaction is completed, cool the reaction kettle to room temperature, slowly exhaust the gas in the reaction kettle, open the reaction kettle, transfer the reaction solution to a 250 ml separating funnel, extract the reaction solution with ethyl acetate, and dry the organic phase with anhydrous magnesium sulfate. The product is obtained by column chromatography separation.

[0134] Optimize the conditions according to the above steps, and the reaction results are shown in the following table:

[0135]

[0136]

[0137] Note: In the above reactions, the raw material is 1 mmol of o-iodoaniline; the solvent is 2 ml; CuI is 0.2 mmol; the reaction time is 24 h.

[0138] Using the method in entry 2 above, and replacing with other reaction substrates, the following various products are obtained:

[0139] Characterization of the compound:

[0140]

[0141] Dry-column packing and dry-sample loading column chromatography (200-300 mesh silica gel) separation: Using petroleum ether: ethyl acetate (V / V) = 4:1 as the eluent, 144 mg of white solid benzothiazolone is separated, and the separation yield is 95%.

[0142] Characterization data of benzothiazol-2-one (2a): 1 H NMR (CDCl3, 500 MHz): δ (ppm) 10.01 (brs, 1H), 7.41 (d, 1H, J = 7.5 Hz), 7.30 - 7.26 (m, 1H), 7.17 - 7.14 (m, 2H). 13 C NMR (CDCl3, 125 MHz): 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. m.p.: 139 - 140 °C.

[0143]

[0144] Column chromatography separation by dry loading column and dry sample loading (200 - 300 mesh silica gel): Using petroleum ether: ethyl acetate (V / V) = 3:1 as the eluent, 138 mg of white solid was obtained, and the separation yield was 84%.

[0145] Characterization data of 6-methylbenzothiazol-2-one: 1 H NMR (DMSO-d6, 500 MHz): δ (ppm) 11.75 (brs, 1H), 7.36 (s, 1H), 7.07 - 7.09 (m, 1H), 7.00 (d, 1H, J = 8 Hz), 2.30 (s, 3H); 13 C NMR (DMSO-d6, 125 MHz): δ (ppm) 169.8, 133.9, 131.7, 127.0, 123.2, 122.5, 111.1, 20.5; MS (ESI): m / z calcd for C8H7NOS [M+1] + : 166.0, found 165.0. m.p.: 170 - 171 °C.

[0146]

[0147] Column chromatography separation by dry loading column and dry sample loading (200 - 300 mesh silica gel): Using petroleum ether: ethyl acetate (V / V) = 2:1 as the eluent, 134 mg of white solid was obtained, and the separation yield was 82%.

[0148] Characterization data of 5-methylbenzothiazol-2-one: 11H NMR (DMSO-d6, 500 MHz): δ (ppm) 11.79 (s, 1H), 7.42 (d, J = 7.9 Hz, 1H), 6.98–6.91 (m, 2H), 2.32 (s, 3H). 13 13C NMR (DMSO-d6, 126 MHz) δ (ppm) 170.31, 136.34, 136.04, 123.49, 122.37, 119.95, 111.84, 20.98; MS (ESI): m / z calcd for C8H7NOS [M+1]+: 166.1, found 165.0.

[0149]

[0150] Dry-column chromatography (200 - 300 mesh silica gel) separation with dry-column packing and dry-sample loading: Using petroleum ether: ethyl acetate (V / V) = 3:1 as the eluent, 158 mg of white solid was obtained with a separation yield of 88%.

[0151] Characterization data of 6-methoxybenzothiazol-2-one: 1 1H NMR (DMSO-d6, 500 MHz): δ (ppm) 11.66 (brs, 1H), 7.23 (d, 1H, J = 2.5 Hz), 7.02 (d, 1H, J = 8.5 Hz), 6.86 (dd, 1H, J1 = 8.5 Hz, J2 = 2.5 Hz), 3.73 (s, 3H); 13C NMR (DMSO-d6, 126 MHz): 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, found 181.1.

[0152]

[0153] Dry-column chromatography (200 - 300 mesh silica gel) separation with dry-column packing and dry-sample loading: Using petroleum ether: ethyl acetate (V / V) = 3:1 as the eluent, 144 mg of white solid was obtained with a separation yield of 85%.

[0154] Characterization data of 6-fluorobenzothiazol-2-one: 1 1H NMR (500 MHz, DMSO-d6) δ (ppm) 11.91 (s, 1H), 7.57 (ddt, J = 9.1, 2.2, 0.8 Hz, 1H), 7.16–7.08 (m, 2H). 1313C NMR (DMSO-d6, 126 MHz) δ (ppm) 169.83, 157.89 (d, J = 119.3 Hz), 132.85 (d, J = 1.9 Hz), 124.66 (d, J = 5.5 Hz), 113.55 (d, J = 12.0 Hz), 112.38 (d, J = 4.3 Hz), 109.95 (d, J = 13.7 Hz). MS (ESI): m / z calcd for C7HFNOS [M+1]+: 170.1, found 169.1.

[0155]

[0156] Dry-column chromatography separation with dry loading (200 - 300 mesh silica gel): Using petroleum ether: ethyl acetate (V / V) = 3:1 as the eluent, 175 mg of white solid was obtained with a separation yield of 81%.

[0157] Characterization data of 6-trifluoromethylbenzothiazol-2-one: 1 1H NMR (DMSO-d6, 500 MHz): δ (ppm) 12.22 (brs, 1H), 7.85 (d, 1H, J = 8.5 Hz), 7.48 (dd, 1H, J1 = 8.0 Hz, J2 = 1.0 Hz), 7.33 (d, 1H, J = 1.5 Hz); 13C NMR (DMSO-d6, 125 MHz): δ (ppm) 169.7, 136.7, 128.4 (d, J = 1.25 Hz), 126.9 (q, J = 31.9.5 Hz), 124.0 (q, J = 270.5 Hz), 123.8, 119.0 (q, J = 3.9 Hz), 107.6 (q, J = 4.1 Hz); MS (EI): m / z calcd for C8H4F3NOS [M+1]+: 220.0, found 219.0. m.p.: 216 - 218 °C.

[0158]

[0159] Dry-column chromatography separation with dry loading (200 - 300 mesh silica gel): Using dichloromethane: ethyl acetate (V / V) = 20:1 as the eluent, 144 mg of white solid was obtained with a separation yield of 63%.

[0160] Characterization data of 6-bromobenzothiazol-2-one: 11H NMR (DMSO-d6, 500 MHz): δ (ppm) 12.02 (brs, 1H), 7.86 (d, 1H, J = 2.0 Hz), 7.44 (dd, 1H, J1 = 8.5, J2 = 2.5 Hz), 7.05 (d, 1H, J = 8.5 Hz); 13 13C NMR (DMSO-d6, 125 MHz): 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. m.p.: 231 - 232 °C.

[0161]

[0162] Column chromatography separation by dry packing and dry sample loading (200 - 300 mesh silica gel): Using dichloromethane:ethyl acetate (V / V) = 100:3 as the eluent, 121 mg of white solid was obtained, and the separation yield was 66%.

[0163] Characterization data of 6-chlorobenzothiazol-2-one: 1 1H NMR (DMSO-d6, 500 MHz): δ (ppm) 12.02 (brs, 1H), 7.74 (d, 1H, J = 2.0 Hz), 7.32 (dd, 1H, J1 = 8.5, J2 = 2.5 Hz), 7.11 (d, 1H, J = 8.5 Hz); 13 13C NMR (DMSO-d6, 125 MHz): δ (ppm) 169.7, 135.3, 126.4, 125.2, 122.4, 122.7; MS (ESI): m / z calcd for C7H4ClNOS [M+1]+: 186.0, found 185.0. m.p.: 212 - 214 °C.

[0164]

[0165] Column chromatography separation by dry packing and dry sample loading (200 - 300 mesh silica gel): Using dichloromethane:ethyl acetate (V / V) = 100:3 as the eluent, 124 mg of white solid was obtained, and the separation yield was 76%.

[0166] Characterization data of 2-methylbenzothiazol-2-one: 11H NMR (500 MHz, DMSO-d6) δ (ppm) 7.64 (d, J = 7.8 Hz, 1H), 7.39 (t, J = 7.7 Hz, 1H), 7.30 (d, J = 8.1 Hz, 1H), 7.21 (t, J = 7.6 Hz, 1H), 3.41 (s, 3H). 13 13C NMR (126 MHz, DMSO-d6) δ (ppm) 137.61, 126.60, 123.17, 122.70, 121.28, 111.32.

[0167]

[0168] Dry-column packing and dry-sample loading column chromatography (200 - 300 mesh silica gel) separation: Petroleum ether: ethyl acetate (V / V) = 3:1 was used as the eluent, and 110 mg of white solid was obtained with a separation yield of 67%.

[0169] Characterization data of 6-aminobenzothiazol-2-one: 1 1H NMR (500 MHz, DMSO-d6) δ (ppm) 11.34 (s, 1H), 6.80 (d, J = 8.4 Hz, 1H), 6.69 (d, J = 2.2 Hz, 1H), 6.51 (dd, J = 8.4, 2.3 Hz, 1H), 4.94 (s, 2H). 13C NMR (126 MHz, 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.

[0170] Example 2 Synthesis of benzothiazolone derivatives by the reaction of o-nitroiodobenzene with CO2 and hydrogen sulfide

[0171]

[0172] The reaction method is as follows:

[0173] Weigh 1 mmol of o - halonitrobenzene, 2 mmol of base, 0.2 mmol of copper(I) iodide (CuI), and 2 ml of solvent, and add them into the reaction kettle in sequence, then tighten the reaction kettle. Introduce the corresponding amount of H₂S into the reaction kettle, stir and react for 30 min at the corresponding temperature, then introduce the corresponding amount of CO₂ into the reaction kettle, and continue to stir and react for 24 h at the corresponding temperature. After the reaction is completed, cool the reaction kettle to room temperature, slowly exhaust the gas in the reaction kettle, open the reaction kettle, 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.

[0174] Optimize the conditions according to the above steps, and the reaction results are shown in the following table:

[0175]

[0176]

[0177] Note: In each of the above reactions, the raw material is 1 mmol of o - iodonitrobenzene; the solvent is 2 ml; CuI is 0.2 mmol; the reaction time is 24 h.

[0178] Adopt the method in entry 9 above, and use other reaction substrates to obtain the following products:

[0179]

[0180] Dry column packing and dry sample loading for column chromatography (200 - 300 mesh silica gel) separation: Use petroleum ether: ethyl acetate (V / V) = 3:1 as the eluent, and separate to obtain 117 mg of white solid, with a separation yield of 71%.

[0181] 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 for C8H7NOS[M + 1]+:166.0,found 165.0.

[0182]

[0183] Dry-column chromatography with dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 3:1 as the developing solvent, 117 mg of white solid was separated, and the separation yield was 71%.

[0184] Characterization data of 7-methylbenzothiazol-2-one: 1H NMR (500 MHz, DMSO-d6) δ 11.87 (s, 1H), 7.20 (t, J = 7.8 Hz, 1H), 6.97 (dd, J = 7.7, 5.0 Hz, 2H), 2.28 (s, 3H). 13C NMR (126 MHz, 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.

[0185]

[0186] Dry-column chromatography with dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 3:1 as the developing solvent, 127 mg of white solid was separated, and the separation yield was 70%.

[0187] Characterization data of 5-methoxybenzothiazol-2-one: 1 1H NMR (500 MHz, DMSO-d6) δ (ppm) 11.80 (s, 1H), 7.44 (d, J = 8.7 Hz, 204H), 6.74 (dd, J = 8.7, 2.5 Hz, 249H), 6.66 (d, J = 2.5 Hz, 245H), 3.75 (s, 704H). 13 13C NMR (126 MHz, 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.

[0188]

[0189] Dry-column chromatography with dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 3:1 as the developing solvent, 140 mg of white solid was separated, and the separation yield was 67%.

[0190] Characterization data of 5-methoxycarbonylbenzothiazol-2-one: 11H NMR (500 MHz, DMSO-d6) δ (ppm) 12.14 (s, 1H), 7.75–7.68 (m, 3H), 7.63 (s, 1H), 3.87 (s, 4H). 13 13C NMR (126 MHz, 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 / z calcd for C9H7NO3S [M+1]+: 220.0, found 219.0.

[0191]

[0192] Dry-column packing and dry-sample loading column chromatography (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 5:1 as the eluent, 116 mg of white solid was obtained, and the separation yield was 63%.

[0193] Characterization data of 7-chlorobenzothiazol-2-one: 1 1H NMR (500 MHz, DMSO-d6) δ (ppm) 12.22 (s, 1H), 7.33 (t, J = 8.0 Hz, 1H), 7.26 (d, J = 7.1 Hz, 1H), 7.11 (d, J = 7.9 Hz, 1H). 13 13C NMR (126 MHz, 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.

[0194]

[0195] Dry-column packing and dry-sample loading column chromatography (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 3:1 as the eluent, 126 mg of white solid was obtained, and the separation yield was 75%.

[0196] Characterization data of 5-fluorobenzothiazol-2-one: 1 1H NMR (500 MHz, DMSO-d6) δ (ppm) 12.02 (s, 1H), 7.60 (dd, J = 8.7, 5.4 Hz, 1H), 7.00 (td, J = 9.1, 2.6 Hz, 1H), 6.93 (dd, J = 9.3, 2.6 Hz, 1H).13 CNMR (DMSO-d6, 126 MHz) δ (ppm) 170.68, 161.02 (d, J = 57.9 Hz), 137.31 (d, J = 6.1 Hz), 124.17 (d, J = 4.8 Hz), 118.72 (d, J = 1.2 Hz), 109.74 (d, J = 11.7 Hz), 99.22 (d, J = 13.7 Hz). MS (EI): m / z calcd for C7H5NOS [M]+: 169.0, found 169.0. m.p.: 172 - 174 °C.

[0197]

[0198] Dry-column packing and dry-sample loading column chromatography (200 - 300 mesh silica gel) separation: Using petroleum ether: ethyl acetate (V / V) = 3:1 as the developing solvent, 118 mg of white solid was separated, and the separation yield was 64%.

[0199] Characterization data of 5-chlorobenzothiazol-2-one: 1 H NMR (500 MHz, DMSO-d6) δ (ppm) 12.05 (s, 1H), 7.61 (d, J = 8.4 Hz, 1H), 7.19 (dd, J = 8.4, 2.1 Hz, 1H), 7.12 (s, 1H). 13 C NMR (126 MHz, DMSO-d6) δ (ppm) 170.12, 137.47, 130.83, 124.26, 122.45, 122.22, 122.19, 111.24; MS (ESI): m / z calcd for C7H4ClNOS [M + 1]+: 186.0, found 185.0. m.p.: 224 - 226 °C.

[0200]

[0201] Dry-column packing and dry-sample loading column chromatography (200 - 300 mesh silica gel) separation: Using petroleum ether: ethyl acetate (V / V) = 3:1 as the developing solvent, 154 mg of white solid was separated, and the separation yield was 67%.

[0202] Characterization data of 5-bromobenzothiazol-2-one: 1 H NMR (500 MHz, DMSO-d6) δ (ppm) 12.04 (s, 1H), 7.56 (d, J = 8.4 Hz, 1H), 7.31 (dd, J = 8.4, 2.0 Hz, 1H), 7.24 (d, J = 1.9 Hz, 1H). 1313C 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.

[0203] Example 3 Synthesis of Thiazolidin-2-one Derivatives by the Reaction of Propargylamine with CO2 and Hydrogen Sulfide

[0204]

[0205] Add 2 mmol of propargylamine, 1.2 mmol of base, and 2 mL of solvent to a 10 mL reaction kettle. Place a magnetic stir bar and tighten the reaction kettle. After purging and replacing the gas three times with N2 gas in combination with a vacuum pump, charge the corresponding amount of H2S. Stir until the pressure no longer changes, then charge 1 MPa of CO2. Stir and react at the corresponding temperature for 24 h. After the reaction is completed, open the kettle and extract the reaction solution with ethyl acetate. Collect and combine the organic phases, dry with anhydrous magnesium sulfate for 30 min, filter off the desiccant, and remove the solvent under reduced pressure to obtain the crude product. The crude product is separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate or dichloromethane / methanol) to obtain the target product.

[0206] Optimize the conditions according to the above steps. The reaction results are shown in the following table:

[0207]

[0208] Note: All the starting materials charged are 2 mmol; 2-methyl-3-butyn-2-amine; the solvent is 2 ml; the reaction is for 24 hours.

[0209] Using the method in entry 3 above and replacing with other reaction substrates, the following products are obtained:

[0210] Characterization of Compounds

[0211]

[0212] Column chromatography (200 - 300 mesh silica gel) separation by wet packing and dry loading of the column: Using petroleum ether:ethyl acetate (V / V) = 1:2 as the eluent, the separation yield is 24%.

[0213] 5-methylenethiazolidin-2-one: 1 1H NMR(500MHz,CDCl3)δ6.53(s,1H),5.23(q,J=2.2Hz,1H),5.18–5.11(m,1H),4.31(s,2H)ppm; 1313C NMR (125 MHz, CDCl3) δ 173.1, 138.8, 106.9, 49.4 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C4H5NOS 116.0165; Found 116.0167.

[0214]

[0215] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Petroleum ether: ethyl acetate (V / V) = 2:1 was used as the eluent, and the separation yield was 81%.

[0216] 4,4-dimethyl-5-methylenethiazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 6.32 (s, 1H), 5.19 (d, J = 2.2 Hz, 1H), 5.11–5.06 (m, 1H), 1.50 (s, 6H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 169.7, 149.3, 104.9, 62.7, 29.9 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C6H9NOS 144.0478; Found 144.0474

[0217]

[0218] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Dichloromethane: methanol (V / V) = 200:1 was used as the eluent, and the separation yield was 80%.

[0219] (Z)-5-benzylidene-3-butyl-4,4-diethylthiazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.40–7.31 (m, 4H), 7.25–7.21 (m, 1H), 6.39 (s, 1H), 3.21–3.14 (m, 2H), 1.95–1.83 (m, 2H), 1.78–1.69 (m, 2H), 1.69–1.63 (m, 2H), 1.41–1.32 (m, 2H), 0.96 (t, J = 7.4 Hz, 3H), 0.86 (t, J = 7.2 Hz, 6H) ppm; 1313C NMR (125 MHz, CDCl3) δ 168.8, 136.4, 136.3, 128.8, 128.1, 127.1, 118.2, 75.9, 42.6, 34.1, 31.0, 20.8, 13.9, 7.8 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C 18 H 25 NOS 304.1730; Found 304.1725.

[0220]

[0221] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel): Petroleum ether: ethyl acetate (V / V) = 2:1 was used as the eluent, and the separation yield was 92%.

[0222] (Z)-4-benzylidene-1-butyl-3-thia-1-azaspiro[4.5]decan-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.40–7.30 (m, 4H), 7.28–7.22 (m, 1H), 6.96 (s, 1H), 3.29–3.21 (m, 2H), 2.07 (d, J = 10.4 Hz, 2H), 1.87–1.72 (m, 7H), 1.63–1.50 (m, 2H), 1.40–1.25 (m, 3H), 0.94 (t, J = 7.4 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 168.1, 139.6, 136.3, 128.6, 128.5, 127.5, 122.7, 69.7, 42.4, 33.7, 32.2, 24.7, 22.8, 20.5, 13.9 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C 19 H 25 NOS 316.1730; Found 316.1722.

[0223]

[0224] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel): Petroleum ether: ethyl acetate (V / V) = 3:1 was used as the eluent, and the separation yield was 92%.

[0225] (Z)-5-benzylidene-3-butyl-4-phenylthiazolidin-2-one:According to the general procedure, the crude residue was purified by flash chromatography (PE / EA = 3 / 1) to give the product as a yellow solid (589 mg, 91%). m.p. = 83–86 °C; 1 1H NMR (500 MHz, CDCl3) δ 7.45–7.37 (m, 5H), 7.35–7.30 (m, 2H), 7.25–7.19 (m, 3H), 6.31 (s, 1H), 5.48 (s, 1H), 3.76–3.65 (m, 1H), 2.77–2.65 (m, 1H), 1.53–1.42 (m, 2H), 1.33–1.23 (m, 2H), 0.88 (t, J = 7.4 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 168.0, 139.4, 135.7, 132.4, 129.4, 129.1, 128.7, 128.1, 127.4, 123.3, 69.9, 42.9, 29.2, 20.0, 13.8 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C 20 H 21 NOS 324.1417; Found 324.1409.

[0226]

[0227] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel): Petroleum ether: ethyl acetate (V / V) = 2:1 was used as the eluent, and the separation yield was 99%.

[0228] (Z)-4-benzyl-5-benzylidene-3-butylthiazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.33 (t, J = 7.6 Hz, 2H), 7.29–7.20 (m, 4H), 7.19–7.11 (m, 4H), 6.07 (s, 1H), 4.69–4.49 (m, 1H), 3.92 (dt, J = 14.5, 8.0 Hz, 1H), 3.13 (dd, J = 13.6, 4.1 Hz, 1H), 3.10–2.98 (m, 2H), 1.69–1.55 (m, 2H), 1.41–1.29 (m, 2H), 0.95 (t, J = 7.4 Hz, 3H) ppm; 1313C NMR (125 MHz, CDCl3) δ 168.1, 135.4, 135.2, 131.0, 129.9, 128.6, 128.5, 127.9, 127.3, 127.1, 122.4, 66.6, 42.5, 40.5, 29.6, 20.0, 13.7 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C 21 H 23 NOS 338.1573; Found 338.1542.

[0229]

[0230] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Petroleum ether: ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the separation yield was 90%.

[0231] (Z)-5-benzylidene-3-butyl-4-propylthiazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.37 (t, J = 7.7 Hz, 2H), 7.31 (d, J = 7.3 Hz, 2H), 7.23 (d, J = 7.3 Hz, 1H), 6.49 (s, 1H), 4.56 (s, 1H), 3.85–3.74 (m, 1H), 3.05–2.93 (m, 1H), 1.97–1.87 (m, 1H), 1.79–1.68 (m, 1H), 1.66–1.49 (m, 2H), 1.47–1.30 (m, 4H), 0.95 (t, J = 7.4 Hz, 6H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 168.1, 135.8, 132.5, 128.8, 128.1, 127.3, 121.1, 65.2, 42.3, 36.4, 29.6, 20.1, 16.1, 14.1, 13.9 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C 17 H 23 NOS 290.1573; Found 290.1558.

[0232]

[0233] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Petroleum ether: ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the separation yield was 92%.

[0234] (Z)-3-butyl-4,4-dimethyl-5-(4-methylbenzylidene)thiazolidin-2-one: 1HNMR (500 MHz, CDCl3) δ 7.23 (d, J = 8.2 Hz, 2H), 7.17 (d, J = 8.0 Hz, 2H), 6.50 (s, 1H), 3.29–3.23 (m, 2H), 2.34 (s, 3H), 1.68–1.59 (m, 2H), 1.55 (s, 6H), 1.41–1.31 (m, 2H), 0.95 (t, J = 7.4 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 167.1, 138.3, 137.1, 133.3, 129.4, 128.1, 119.0, 68.0, 42.5, 31.7, 28.3, 21.3, 20.5, 13.9 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C 17 H 23 NOS2 90.1573; Found 290.1568.

[0235]

[0236] Column chromatography was performed by wet packing and dry loading (200 - 300 mesh silica gel). Petroleum ether: ethyl acetate (V / V) = 2:1 was used as the eluent, and the separation yield was 81%.

[0237] (Z)-3-butyl-5-(4-methoxybenzylidene)-4,4-dimethylthiazolidin-2-one: 1 HNMR (500 MHz, CDCl3) δ 7.27 (d, J = 10.5 Hz, 2H), 6.90 (d, J = 8.8 Hz, 2H), 6.47 (s, 1H), 3.82 (s, 3H), 3.29–3.22 (m, 2H), 1.68–1.60 (m, 2H), 1.54 (s, 6H), 1.40–1.31 (m, 2H), 0.95 (t, J = 7.4 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 167.2, 158.7, 136.9, 129.5, 128.9, 118.6, 114.2, 68.0, 55.4, 42.5, 31.7, 28.3, 20.5, 13.9 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C 17 H 23 NO2S 306.1522; Found 306.1516.

[0238]

[0239] Column chromatography with wet packing and dry sample loading (using 200 - 300 mesh silica gel) separation: Petroleum ether: Ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the separation yield was 83%.

[0240] (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),3.30–3.23(m,2H),1.68–1.60(m,2H),1.55(s,6H),1.42–1.31(m,2H),0.95(t,J=7.3Hz,3H)ppm; 13 C NMR(125MHz,CDCl3)δ166.5,140.5,134.7,132.8,129.4,128.9,117.8,68.1,42.6,31.7,28.3,20.5,13.9ppm;HRMS(ESI)m / z:[M+H] + Calcd for C 16 H 20 ClNOS 310.1027;Found310.1021.

[0241]

[0242] Column chromatography with wet packing and dry sample loading (using 200 - 300 mesh silica gel) separation: Petroleum ether: Ethyl acetate (V / V) = 1:2 was used as the developing solvent, and the separation yield was 87%.

[0243] (Z)-5-benzylidene-4,4-dimethylthiazolidin-2-one: 1 H NMR(500MHz,DMSO-d6)δ8.79(s,1H),7.43–7.33(m,4H),7.25(t,J=7.3Hz,1H),6.74(s,1H),1.50(s,6H)ppm; 13 CNMR(125MHz,DMSO-d6)δ166.1,140.8,136.0,128.6,127.7,126.9,118.7,63.5,29.7ppm;HRMS(ESI)m / z:[M+H] + Calcd for C 12 H 13 NOS 220.0791;Found 220.0788.

[0244]

[0245] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether: ethyl acetate (V / V) = 2:1 as the developing solvent, the separation yield is 94%.

[0246] (Z)-5-benzylidene-4,4-dimethyl-3-propylthiazolidin-2-one: 1 H NMR (500 MHz, CDCl3) δ 7.41–7.29 (m, 4H), 7.25–7.21 (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 = 7.4 Hz, 3H) ppm; 13 C NMR (125 MHz, CDCl3) δ 166.9, 139.3, 136.0, 128.6, 128.0, 127.1, 118.9, 67.9, 44.2, 28.2, 22.7, 11.5 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C 15 H 19 NOS 262.1260; Found 262.1257.

[0247]

[0248] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether: ethyl acetate (V / V) = 2:1 as the developing solvent, the separation yield is 87%.

[0249] (Z)-5-benzylidene-3-butyl-4,4-dimethylthiazolidin-2-one: 1 H NMR (500 MHz, CDCl3) δ 7.39–7.31 (m, 4H), 7.25–7.21 (m, 1H), 6.53 (s, 1H), 3.30–3.24 (m, 2H), 1.69–1.60 (m, 2H), 1.56 (s, 6H), 1.41–1.32 (m, 2H), 0.95 (t, J = 7.4 Hz, 3H) ppm; 13 C NMR (125 MHz, CDCl3) δ 166.9, 139.6, 136.2, 128.7, 128.2, 127.3, 119.0, 68.1, 42.5, 31.7, 28.4, 20.6, 13.9 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C 16 H 21 NOS 276.1417; Found 276.1416.

[0250]

[0251] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Petroleum ether: Ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the separation yield was 89%.

[0252] (Z)-3-benzyl-5-benzylidene-4,4-dimethylthiazolidin-2-one: 1 H NMR (500 MHz, CDCl3) δ 7.40 - 7.33 (m, 4H), 7.32 - 7.29 (m, 4H), 7.27–7.23 (m, 2H), 6.53 (s, 1H), 4.62 (s, 2H), 1.49 (s, 6H) ppm; 13 C NMR (125 MHz, CDCl3) δ 168.1, 139.1, 138.1, 136.0, 128.8, 128.7, 128.2, 127.5, 127.4, 127.3, 119.3, 68.4, 45.3, 28.5 ppm; HRMS (ESI) m / z: [M + H] + Calcd for C 19 H 19 NOS 310.1260; Found 310.1250.

[0253]

[0254] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Petroleum ether: Ethyl acetate (V / V) = 4:1 was used as the developing solvent, and the separation yield was 46%.

[0255] (Z)-5-benzylidene-3-isopropyl-4,4-dimethylthiazolidin-2-one: 1 H NMR (500 MHz, CDCl3) δ 7.40–7.31 (m, 4H), 7.25–7.20 (m, 1H), 6.46 (s, 1H), 3.58–3.47 (m, 1H), 1.56 (s, 6H), 1.49 (d, J = 6.8 Hz, 6H) ppm; 13 C NMR (125 MHz, CDCl3) δ 165.6, 139.8, 136.3, 128.7, 128.2, 127.1, 118.8, 69.1, 47.7, 28.3, 20.5 ppm; HRMS (ESI) m / z: [M + H] + Calcd for C 15 H 19 NOS 262.1260; Found 262.1256

[0256]

[0257] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Petroleum ether: ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the separation yield was 75%.

[0258] (Z)-5-(4-bromobenzylidene)-3-butyl-4,4-dimethylthiazolidin-2-one: 1 HNMR(500MHz,CDCl3)δ7.49(d,J=8.5Hz,2H),7.20(d,J=8.6Hz,2H),6.45(s,1H),3.29–3.24(m,2H),1.68–1.60(m,2H),1.55(s,6H),1.40–1.32(m,2H),0.95(td,J=7.4,1.1Hz,3H)ppm; 13 C NMR(125MHz,CDCl3)δ166.5,140.7,135.1,131.9,129.7,121.0,117.9,68.1,42.6,31.7,28.3,20.6,13.9ppm;MS(ESI)m / z:[M+H] + Calcd for C 16 H 20 BrNOS 354.1;Found354.1.

[0259]

[0260] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Petroleum ether: ethyl acetate (V / V) = 1:3 was used as the developing solvent, and the separation yield was 79%.

[0261] (Z)-3-butyl-4,4-dimethyl-5-(pyridin-3-ylmethylene)thiazolidin-2-one: 1 H NMR(500 MHz,CDCl3)δ8.52(d,J=55.4Hz,2H),7.70(d,J=7.5Hz,1H),7.32(s,1H),6.49(s,1H),3.31–3.24(m,2H),1.66–1.63(m,2H),1.58(s,6H),1.41–1.32(m,2H),0.95(t,J=7.3Hz,3H)ppm; 13 C NMR(125MHz,CDCl3)δ166.1,150.1,147.9,142.9,134.2,115.4,68.3,42.7,31.7,28.4,20.5,13.9ppm;HRMS(ESI)m / z:[M+H] + Calcd for C 15 H 22N2OS277.1369; Found 277.1376.

[0262]

[0263] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether: ethyl acetate (V / V) = 4:1 as the developing solvent, the separation yield is 82%.

[0264] (Z)-3-butyl-4,4-dimethyl-5-(thiophen-2-ylmethylene)thiazolidin-2-one: 1 HNMR(500MHz,CDCl3)δ7.33(d,J = 5.0Hz,1H),7.07–7.04(m,1H),7.02(d,J = 3.1Hz,1H),6.74(s,1H),3.29–3.23(m,2H),1.66–1.61(m,2H),1.54(s,6H),1.40–1.31(m,2H),0.95(t,J = 7.4Hz,3H)ppm; 13 C NMR(125MHz,CDCl3)δ166.4,140.2,137.9,127.5,126.6,126.0,112.0,67.7,42.7,31.7,28.3,20.5,13.9ppm; HRMS(ESI)m / z:[M + H] + Calcd forC 14 H 19 NOS2282.0981; Found 282.0981.

[0265]

[0266] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether: ethyl acetate (V / V) = 4:1 as the developing solvent, the separation yield is 40%.

[0267] (Z)-3-butyl-5-(cyclopropylmethylene)-4,4-dimethylthiazolidin-2-one: 1 HNMR(500MHz,CDCl3)δ4.99(d,J = 8.8Hz,1H),3.22–3.14(m,2H),1.63–1.55(m,2H),1.39(s,6H),1.37–1.28(m,3H),1.23–1.16(m,1H),0.92(t,J = 7.4Hz,3H),0.85–0.78(m,2H),0.44–0.39(m,2H)ppm; 1313C NMR (125 MHz, CDCl3) δ 167.5, 136.9, 122.9, 66.4, 42.3, 31.8, 28.0, 20.5, 13.9, 13.1, 7.3 ppm; MS (ESI) m / z: [M+H] + Calcd for C 13 H 21 NOS 240.1; Found 240.2.

[0268]

[0269] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 4:1 as the eluent, the separation yield was 72%.

[0270] (Z)-5-benzylidene-3-cyclopropyl-4,4-dimethylthiazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.39–7.31 (m, 4H), 7.25–7.21 (m, 1H), 6.54 (s, 1H), 2.39–2.33 (m, 1H), 1.67 (s, 6H), 0.99–0.94 (m, 2H), 0.93–0.88 (m, 2H) ppm. 13 13C NMR (125 MHz, CDCl3) δ 168.8, 138.9, 136.1, 128.7, 128.2, 127.3, 119.0, 69.6, 28.3, 24.3, 6.4 ppm; MS (ESI) m / z: [M+H] + Calcd for C 15 H 17 NOS 260.1; Found 260.2.

[0271]

[0272] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 4:1 as the eluent, the separation yield was 85%.

[0273] (Z)-5-benzylidene-3-hexyl-4,4-dimethylthiazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.39–7.32 (m, 4H), 7.26–7.21 (m, 1H), 6.53 (s, 1H), 3.29–3.22 (m, 2H), 1.69–1.62 (m, 2H), 1.56 (s, 6H), 1.38–1.28 (m, 6H), 0.89 (t, J = 6.3 Hz, 3H) ppm; 1313C NMR (125 MHz, CDCl3) δ 166.9, 139.5, 136.2, 128.7, 128.2, 127.2, 119.0, 68.1, 42.7, 31.6, 29.6, 28.4, 27.0, 22.72, 14.1 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C 18 H 25 NOS 304.1730; Found 304.1734.

[0274]

[0275] Column chromatography (200 - 300 mesh silica gel) with wet packing and dry sample loading: Petroleum ether: ethyl acetate (V / V) = 2:1 was used as the eluent, and the separation yield was 86%.

[0276] (Z)-5-benzylidene-4,4-dimethyl-3-octylthiazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.40–7.31 (m, 4H), 7.26–7.21 (m, 1H), 6.53 (s, 1H), 3.28–3.23 (m, 2H), 1.70–1.62 (m, 2H), 1.56 (s, 6H), 1.34–1.23 (m, 10H), 0.88 (t, J = 6.7 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 166.9, 139.5, 136.2, 128.7, 128.2, 127.3, 119.0, 68.1, 42.8, 31.9, 29.7, 29.3(9), 29.3(7), 28.4, 27.3, 22.8, 14.2 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C 20 H 29 NOS 332.2043; Found 332.2049.

[0277]

[0278] Column chromatography (200 - 300 mesh silica gel) with wet packing and dry sample loading: Petroleum ether: ethyl acetate (V / V) = 5:1 was used as the eluent, and the separation yield was 35%.

[0279] 3-benzyl-5-methylenethiazolidin-2-one: 11H NMR (500 MHz, CDCl3) δ 7.39–7.34 (m, 2H), 7.33–7.29 (m, 1H), 7.27 (d, J = 7.9 Hz, 2H), 5.17–5.14 (m, 1H), 5.14–5.11 (m, 1H), 4.53 (s, 2H), 4.17–4.13 (m, 2H) ppm. 13 13C NMR (125 MHz, CDCl3) δ 169.1, 135.5, 135.4, 129.0, 128.3, 128.2, 106.6, 53.9, 48.3 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C4H5NOS: 206.1; Found 206.0.

[0280]

[0281] Column chromatography was performed by wet packing of the column and dry loading of the sample (silica gel, 200 - 300 mesh). Petroleum ether: ethyl acetate (V / V) = 4:1 was used as the eluent, and the separation yield was 94%.

[0282] (Z)-5-benzylidene-3-hexyl-4-(p-tolyl)thiazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.31 (t, J = 7.7 Hz, 2H), 7.25 (d, J = 3.1 Hz, 2H), 7.24–7.17 (m, 5H), 6.28 (s, 1H), 5.43 (s, 1H), 3.73–3.65 (m, 1H), 2.74–2.66 (m, 1H), 2.37 (s, 3H), 1.51–1.43 (m, 2H), 1.33–1.21 (m, 2H), 0.88 (t, J = 7.3 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 168.0, 139.0, 136.4, 135.8, 132.7, 130.0, 128.7, 128.1, 127.3(3), 127.3(1), 123.1, 69.7, 42.8, 29.2, 21.4, 20.1, 13.8 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C 21 H 23 NOS 338.1573; Found 338.1578.

[0283]

[0284] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 4:1 as the developing solvent, the separation yield is 66%.

[0285] (Z)-5-benzylidene-3-butyl-4-(4-chlorophenyl)thiazolidin-2-one: 1 H NMR(500MHz,CDCl3)δ7.40(d,J=8.3Hz,2H),7.33(d,J=8.2Hz,4H),7.23(d,J=7.6Hz,3H),6.28(s,1H),5.45(s,1H),3.71(dt,J=15.4,7.9Hz,1H),2.73–2.66(m,1H),1.51–1.42(m,2H),1.34–1.21(m,2H),0.89(t,J=7.3Hz,3H)ppm; 13 C NMR(125MHz,CDCl3)δ168.0,138.0,135.5,135.1,131.9,129.7,128.7,128.7,128.1,127.6,123.6,69.1,42.9,29.2,20.0,13.8ppm;HRMS(ESI)m / z:[M+H] + Calcd for C 20 H 20 ClNOS 358.1027;Found 358.1031.

[0286]

[0287] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 4:1 as the developing solvent, the separation yield is 83%.

[0288] (Z)-5-benzylidene-3-butyl-4-(thiophen-3-yl)thiazolidin-2-one: 1 H NMR(500MHz,CDCl3)δ7.39–7.31(m,4H),7.22(dd,J=13.3,5.9Hz,2H),7.08(d,J=6.1Hz,1H),6.34(s,1H),5.61(s,1H),3.71–3.63(m,1H),2.84–2.76(m,1H),1.53–1.40(m,2H),1.34–1.22(m,3H),0.89(t,J=7.3Hz,3H)ppm; 1313C NMR (125 MHz, CDCl3) δ 167.6, 140.2, 135.7, 131.5, 128.7, 128.1 (3), 128.1 (2), 127.9, 127.4, 125.8, 124.0, 123.2, 65.4, 42.9, 29.3, 20.1, 13.8 ppm; HRMS (ESI) m / z: [M+H] + Calcd for C 18 H 19 NOS2 330.0981; Found 330.0981.

[0289] The second type of hydrogen sulfide as a catalyst

[0290] Example 4: o-Phenylenediamine reacts with CO2 under the action of hydrogen sulfide to synthesize benzimidazolone derivatives

[0291]

[0292] Add 2 mmol of o-phenylenediamine, an organic base and 1 mL of a suitable solvent into a 15 mL high-pressure reactor in sequence, and tighten the reactor; introduce the required amounts of H2S and CO2 gases into the reactor in sequence; finally, react the reactor continuously at a suitable temperature for 12 hours; after the reaction is completed, add a certain amount of distilled water to the reaction solution to completely precipitate the product, and then obtain the target product through suction filtration and drying in sequence.

[0293] Optimize the conditions according to the above steps, and the reaction results are shown in the following table:

[0294] Entry Solvent Base (mmol) <![CDATA[H2S(P MPa )]]> <![CDATA[CO2(P MPa )]]> t(℃) Yield (%) 1 NMP DBU (3) 0.08 1.5 40 86 2 NMP DBU (2) 0.08 1.5 40 86 3 NMP DBU (1) 0.08 1.5 40 79

[0295] 4 NMP DBU (2) 0.3 1.5 40 87 5 NMP DBU (2) 0.15 1.5 40 87 6 NMP DBU (2) 0.08 1.5 40 87 7 NMP DBU (2) 0.03 1.5 40 69 8 NMP DBU (2) 0 1.5 40 NR 9 NMP DBU (2) 0.08 5 40 86 10 NMP DBU (2) 0.08 4 40 86 11 NMP DBU (2) 0.08 3 40 87 12 NMP DBU (2) 0.08 1 40 82 13 NMP DBU (2) 0.08 0 40 NR 14 NMP DBU (2) 0.08 1.5 60 84 15 NMP DBU (2) 0.08 1.5 50 86 16 NMP DBU (2) 0.08 1.5 30 85 17 NMP DBU (2) 0.08 1.5 20 83 18 DMSO DBU (2) 0.08 1.5 40 NR 19 NMP DBU (2) 0.08 1.5 40 87 20 NMP TMG (2) 0.08 1.5 40 86 21 NMP DBU (2) 0.08 1.5 40 87

[0296] Note: In each of the above reactions, the raw material is 2 mmol of o-phenylenediamine; the solvent is 1 ml.

[0297] Using the same method in entry 6 and changing to other reaction substrates, the following compounds are obtained:

[0298]

[0299] A white solid product of 233 mg is obtained through filtration and drying, and the separation yield is: 87%

[0300] 1 1H NMR (500 MHz, DMSO-d6, TMS): δ (ppm) 10.57 (s, 2H), 6.91 (s, 4H).

[0301] 1313C NMR (126 MHz, DMSO-d6, TMS): δ (ppm) 155.28 (C), 129.67 (C), 120.43 (CH), 108.46 (CH).

[0302] MS (ESI): m / z calcd for C7H6NO [M+H] + : 135.06, found 135.1.

[0303]

[0304] The solid product (265 mg) was obtained by filtration and drying. Isolated yield: 89.5%

[0305] 1 1H NMR (500 MHz, DMSO-d6, TMS): δ (ppm) 10.47 (d, 2H, J = 20.0 Hz), 6.80 (d, 1H, J = 10.0 Hz), 6.73 (d, 2H, J = 10.0 Hz), 2.27 (s, 3H).

[0306] 13 13C NMR (125 MHz, DMSO-d6, TMS): δ (ppm) 155.29, 129.72, 129.21, 127.31, 120.75, 108.87, 108.03, 20.91.

[0307]

[0308] The solid product (266 mg) was obtained by filtration and drying. Isolated yield: 90%

[0309] 1 1H NMR (500 MHz, DMSO-d6, TMS): δ (ppm) 10.65 (s, 1H), 10.53 (s, 1H), 6.82 (t, 1H, J1 = J2 = 10.0 Hz), 6.74 (t, 1H, J1 = J2 = 10.0 Hz), 2.25 (s, 3H).

[0310] 13 13C NMR (125 MHz, DMSO-d6, TMS): δ (ppm) 155.47, 129.23, 128.55, 121.56, 120.34, 117.13, 106.05, 16.17.

[0311]

[0312] The solid product (289 mg) was obtained by filtration and drying. Isolated yield: 89.2%

[0313] 1 1H NMR (500 MHz, DMSO-d6, TMS): δ (ppm) 10.34 (s, 2H), 6.70 (s, 2H), 2.17 (s, 6H).

[0314] 13 13C NMR (125 MHz, DMSO-d6, TMS): δ (ppm) 155.41, 127.75, 109.54.

[0315]

[0316] The solid product (176 mg) was obtained by filtration and drying. Isolated yield: 58%

[0317] 1 1H NMR (500 MHz, DMSO-d6, TMS): δ (ppm) 10.74 (s, 1H), 10.63 (s, 1H), 6.87 (dd, J = 8.5, 4.7 Hz, 1H), 6.80 - 6.69 (m, 2H).

[0318] 13 13C NMR (125 MHz, DMSO-d6, TMS): δ (ppm) 158.42, 156.13 (d, J = 110.2 Hz), 130.36 (d, J = 13.0 Hz), 126.06, 108.77 (d, J = 9.6 Hz), 106.52 (d, J = 23.8 Hz), 96.51 (d, J = 28.2 Hz).

[0319]

[0320] The solid product (264 mg) was obtained by filtration and drying. Isolated yield: 78%

[0321] 1 1H NMR (500 MHz, DMSO-d6, TMS): δ (ppm) 10.76 (s, 2H), 6.97 - 6.90 (m, 3H).

[0322] 13 13C NMR (125 MHz, DMSO-d6, TMS): δ (ppm) 155.19, 130.82, 128.60, 124.47, 120.09, 109.50, 108.36.

[0323]

[0324] The solid product (421 mg) was obtained by filtration and drying. Isolated yield: 98.7%

[0325] 1 H NMR (500 MHz, DMSO-d6, TMS): δ (ppm) 10.76 (s, 2H), 7.05 (t, 2H, J1 = J2 = 10.0 Hz), 6.88 (d, 1H, J = 10.0 Hz).

[0326] 13 C NMR (125 MHz, DMSO-d6, TMS): δ (ppm) 155.03, 131.20, 128.98, 122.89, 111.98, 111.02, 110.06.

[0327]

[0328] The solid product (255 mg) was obtained by filtration and drying. Isolated yield: 63%

[0329] 1 H NMR (500 MHz, DMSO-d6, TMS): δ (ppm) 10.99 (s, 2H), 7.28 (dd, J = 8.2, 1.7 Hz, 1H), 7.16 (d, J = 1.7 Hz, 1H), 7.09 (d, J = 8.1 Hz, 1H).

[0330] 13 C NMR (125 MHz, DMSO-d6, TMS): δ (ppm) 155.36, 132.88, 129.85, 124.89 (q, J = 271.8 Hz), 120.95 (q, J = 3.2 Hz), 117.91 (q, J = 4.2 Hz), 108.58, 104.98 (q, J = 4.0 Hz).

[0331]

[0332] The solid product (371 mg) was obtained by filtration and drying. Isolated yield: 78%

[0333] 1 H NMR (500 MHz, 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 = 5.0 Hz), 7.44 (d, 1H, J = 10.0 Hz), 7.33 (s, 1H), 7.08 (d, 1H, J = 10.0 Hz).

[0334] 1313C NMR (125 MHz, 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.

[0335]

[0336] The solid product (206 mg) was obtained by filtration and drying. Isolated yield: 63%

[0337] 1 1H NMR (500 MHz, DMSO-d6, TMS): δ (ppm) 10.50 (s, 1H), 10.37 (s, 1H), 6.81 (d, 1H, J = 5.0 Hz), 6.52 (d, 2H, J = 10.0 Hz), 3.70 (s, 3H).

[0338] 13 13C NMR (125 MHz, DMSO-d6, TMS): δ (ppm) 155.64, 154.33, 130.49, 123.56, 108.71, 106.07, 95.27, 55.42.

[0339]

[0340] The solid product (358 mg) was obtained by filtration and drying. Isolated yield: 97%

[0341] 1 1H NMR (500 MHz, DMSO-d6, TMS): δ (ppm) 10.07 (s, 2H), 7.21 (t, 2H, J1 = J2 = 5.0 Hz), 7.11 (d, 2H, J = 5.0 Hz), 6.52 (d, 2H, J = 5.0 Hz).

[0342] 13 13C NMR (125 MHz, DMSO-d6, TMS): δ (ppm) 150.09, 137.67, 134.15, 128.03, 117.65, 113.66, 104.01.

[0343] Example 5 Reaction of o-aminothiophenol with CO2 under the action of hydrogen sulfide to synthesize benzothiazolone derivatives

[0344]

[0345] Take 2 mmol of the starting o-aminothiophenol compound, place it in a 15 mL stainless steel autoclave equipped with a magnetic stir bar, and then sequentially add 2 mmol of base and 2 mL of solvent to the autoclave. Tighten the autoclave. First, charge the corresponding amount of hydrogen sulfide gas, then introduce the corresponding amount of CO2, and then stir and react at the appropriate temperature for 24 h. After the reaction is completed, cool to room temperature, exhaust the gas in the autoclave, extract with ethyl acetate, combine the organic phases, and dry with anhydrous magnesium sulfate. Filter off the desiccant, remove the solvent under reduced pressure to obtain the crude product, and purify the target product by column chromatography.

[0346] Optimize the conditions according to the above steps, and the reaction results are shown in the following table:

[0347]

[0348]

[0349] Note: All the starting materials used are 2 mmol of o-aminothiophenol; the solvent is 2 mL; the reaction time is 24 h.

[0350] Using the same method as in entry 7 and changing to other reaction substrates, the following compounds were obtained:

[0351]

[0352] Column chromatography separation by dry packing and dry sample loading (200 - 300 mesh silica gel): Using dichloromethane:ethyl acetate (V / V) = 20:1 as the eluent, 143 mg of white solid was separated, and the separation yield was 94.4%.

[0353] Characterization data of 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.m.p.:139 - 140℃。

[0354]

[0355] Dry-column chromatography with dry sample loading (200 - 300 mesh silica gel) separation: Using dichloromethane:ethyl acetate (V / V) = 5:1 as the eluent, 141 mg of white solid was obtained, and the separation yield was 76.2%.

[0356] Characterization data of 6-chlorobenzothiazol-2-one (1b): 1 H NMR (DMSO-d6, 500 MHz): δ (ppm) 12.02 (brs, 1H), 7.74 (d, 1H, J = 2.0 Hz), 7.32 (dd, 1H, J1 = 8.5, J2 = 2.5 Hz), 7.11 (d, 1H, J = 8.5 Hz); 13 C NMR (DMSO-d6, 125 MHz): 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. m.p.: 212 - 214 °C.

[0357]

[0358] Dry-column chromatography with dry sample loading (200 - 300 mesh silica gel) separation: Using dichloromethane:ethyl acetate (V / V) = 20:1 as the eluent, 195 mg of white solid was obtained, and the separation yield was 85%.

[0359] Characterization data of 6-bromobenzothiazol-2-one (1c): 1 H NMR (DMSO-d6, 500 MHz): δ (ppm) 12.02 (brs, 1H), 7.86 (d, 1H, J = 2.0 Hz), 7.44 (dd, 1H, J1 = 8.5, J2 = 2.5 Hz), 7.05 (d, 1H, J = 8.5 Hz); 13 C NMR (DMSO-d6, 125 MHz): 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. m.p.: 231 - 232 °C.

[0360]

[0361] Dry column packing and dry sample loading for 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, and the separation yield was 67.9%.

[0362] Characterization data of 6 - (trifluoromethyl)benzothiazol - 2 - one (1d): 1 1H NMR (DMSO - d6, 500 MHz): δ (ppm) 12.22 (brs, 1H), 7.85 (d, 1H, J = 8.5 Hz), 7.48 (dd, 1H, J1 = 8.0 Hz, J2 = 1.0 Hz), 7.33 (d, 1H, J = 1.5 Hz); 13 13C NMR (DMSO - d6, 125 MHz): δ (ppm) 169.7, 136.7, 128.4 (d, J = 1.25 Hz), 126.9 (q, J = 31.95 Hz), 124.0 (q, J = 270.5 Hz), 123.8, 119.0 (q, J = 3.9 Hz), 107.6 (q, J = 4.1 Hz); MS (EI): m / z calcd for C8H4F3NOS [M] + : 219.2, found 219.0. m.p.: 216 - 218 °C.

[0363]

[0364] Dry column packing and dry sample loading for 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, and the separation yield was 94%.

[0365] Characterization data of 6 - methoxybenzothiazol - 2 - one (1e): 1 1H NMR (DMSO - d6, 500 MHz): δ (ppm) 11.658 (brs, 1H), 7.23 (d, 1H, J = 2.5 Hz), 7.02 (d, 1H, J = 8.5 Hz), 6.86 (dd, 1H, J1 = 8.5 Hz, J2 = 2.5 Hz), 3.73 (s, 3H); 13 13C NMR (DMSO - d6, 125 MHz): 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. m.p.: 161 - 163 °C.

[0366]

[0367] Dry-column chromatography with dry sample loading (using 200 - 300 mesh silica gel) separation: Dichloromethane:ethyl acetate (V / V) = 50:1 was used as the developing solvent, and 160 mg of white solid was obtained with a separation yield of 96.8%.

[0368] Characterization data of 6-methylbenzothiazol-2-one: 1 H NMR (DMSO-d6, 500 MHz): δ (ppm) 11.75 (brs, 1H), 7.36 (s, 1H), 7.07 - 7.09 (m, 1H), 7.00 (d, 1H, J = 8 Hz), 2.30 (s, 3H); 13 C NMR (DMSO-d6, 125 MHz): 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. m.p.: 170 - 171 °C.

[0369]

[0370] Dry-column chromatography with dry sample loading (using 200 - 300 mesh silica gel) separation: 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%.

[0371] Characterization data of 5-chlorobenzothiazol-2-one: 1 H NMR (DMSO-d6, 500 MHz): δ (ppm) 12.04 (brs, 1H), 7.61 (d, 1H, J = 8.5 Hz), 7.19 (dd, 1H, J1 = 8.5, J2 = 2.5 Hz), 7.12 (d, 1H, J = 2.0 Hz); 13 C NMR (DMSO-d6, 125 MHz): 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. m.p.: 224 - 226 °C.

[0372]

[0373] Dry-column chromatography with dry sample loading (using silica gel of 200 - 300 mesh) separation: Using dichloromethane:ethyl acetate (V / V) = 5:1 as the developing solvent, 164 mg of white solid was separated, and the separation yield was 99.3%.

[0374] Characterization data of 4-methylbenzothiazol-2-one: 1 H NMR (DMSO-d6, 500 MHz): δ (ppm) 11.73 (brs, 1H), 7.37 (dd, 1H, J1 = 7.5, J2 = 0.5 Hz), 7.08 - 7.09 (m, 1H), 7.03 (t, 1H, J = 7.5 Hz), 2.32 (s, 3H); 13 C NMR (DMSO-d6, 125 MHz): 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. m.p.: 211 - 212 °C.

[0375]

[0376] Dry-column chromatography with dry sample loading (using silica gel of 200 - 300 mesh) separation: Using ethyl acetate:petroleum ether (V / V) = 3:1 as the developing solvent, 155 mg of white solid was separated, and the separation yield was 67.9%.

[0377] Characterization data of methylsulfonylbenzothiazol-2-one: 1 H NMR (DMSO-d6, 500 MHz): δ (ppm) 12.41 (brs, 1H), 8.22 (d, 1H, J = 7.0 Hz), 7.812 (dd, 1H, J = 7.5 Hz, J = 2.0 Hz), 7.31 (d, 1H, J = 8.0 Hz), 3.20 (s, 3H); 13 C NMR (DMSO-d6, 125 MHz): 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. m.p.: 241 - 244 °C.

[0378] Example 6 Synthesis of benzothiazolone derivatives by the reaction of aromatic o - aminodisulfide with CO2 under the action of hydrogen sulfide

[0379]

[0380] 0.5 mmol of disulfide, 0.5 mmol of base, and 2 mL of solvent were successively added into a reaction kettle, and the reaction kettle was tightened. An appropriate amount of H2S was introduced, preheated, and the corresponding amount of CO2 was introduced. The reaction was carried out at the corresponding temperature for 12 hours. After the reaction was completed, the reaction kettle was cooled to room temperature, the gas in the reaction kettle was slowly exhausted, extracted with ethyl acetate and saturated brine, the organic phases were combined, and column chromatography was carried out to obtain the target product.

[0381] The conditions were optimized according to the above steps, and the reaction results are shown in the following table:

[0382]

[0383]

[0384] Note: The starting materials used were 0.5 mmol of disulfide (dimer of o-aminothiophenol); the solvent was 2 mL; the molar ratio in the table was the mol ratio of disulfide:DBU; the reaction time was 12 h.

[0385] Using the same method as in entry 3 and changing to other reaction substrates, the following compounds were obtained:

[0386]

[0387] 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 eluent, 148 mg of white solid was separated, and the separation yield was 98%.

[0388] 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.m.p.:139 - 140℃。

[0389]

[0390] Dry-column chromatography (using 200 - 300 mesh silica gel) with dry sample loading for separation: Using dichloromethane:ethyl acetate (V / V) = 20:1 as the developing solvent, 180 mg of white solid was obtained, and the separation yield was 97.2%.

[0391] Characterization data: 1 H NMR (DMSO-d6, 500 MHz): δ (ppm) 12.02 (brs, 1H), 7.74 (d, 1H, J = 2.0 Hz), 7.32 (dd, 1H, J1 = 8.5, J2 = 2.5 Hz), 7.11 (d, 1H, J = 8.5 Hz); 13 C NMR (DMSO-d6, 125 MHz): 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. m.p.: 212 - 214 °C.

[0392]

[0393] Dry-column chromatography (using 200 - 300 mesh silica gel) with dry sample loading for separation: Using dichloromethane:ethyl acetate (V / V) = 20:1 as the developing solvent, 179 mg of white solid was obtained, and the separation yield was 78.3%.

[0394] Characterization data: 1 H NMR (DMSO-d6, 500 MHz): δ (ppm) 12.02 (brs, 1H), 7.86 (d, 1H, J = 2.0 Hz), 7.44 (dd, 1H, J1 = 8.5, J2 = 2.5 Hz), 7.05 (d, 1H, J = 8.5 Hz); 13 C NMR (DMSO-d6, 125 MHz): 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. m.p.: 231 - 232 °C.

[0395]

[0396] Dry-column chromatography (using 200 - 300 mesh silica gel) with dry sample loading for separation: Using dichloromethane:ethyl acetate (V / V) = 20:1 as the developing solvent, 169 mg of white solid was obtained, and the separation yield was 93.5%.

[0397] Characterization data: 1 H NMR (DMSO-d6, 500 MHz): δ (ppm) 11.658 (brs, 1H), 7.23 (d, 1H, J = 2.5 Hz), 7.02 (d, 1H, J = 8.5 Hz), 6.86 (dd, 1H, J1 = 8.5 Hz, J2 = 2.5 Hz), 3.73 (s, 3H); 13 C NMR (DMSO-d6, 125 MHz): 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. m.p.: 161 - 163 °C.

[0398]

[0399] Column chromatography separation by dry packing and dry sample loading (200 - 300 mesh silica gel): Using dichloromethane:ethyl acetate (V / V) = 20:1 as the eluent, 149 mg of white solid was obtained, and the separation yield was 90%.

[0400] Characterization data: 1 H NMR (DMSO-d6, 500 MHz): δ (ppm) 11.73 (brs, 1H), 7.37 (dd, 1H, J1 = 7.5 Hz, J2 = 0.5 Hz), 7.08 - 7.09 (m, 1H), 7.03 (t, 1H, J = 7.5 Hz), 2.32 (s, 3H). 13 C NMR (DMSO-d6, 125 MHz): δ (ppm) 170.4, 135.0, 127.6, 122.8, 122.5, 121.3, 120.0, 17.4; MS (EI): m / z calcd for C7H5NOS [M] + : 165.1, found 165.0. m.p.: 211 - 212 °C.

[0401]

[0402] Column chromatography separation by dry packing and dry sample loading (200 - 300 mesh silica gel): Using dichloromethane:ethyl acetate (V / V) = 20:1 as the eluent, 157 mg of white solid was obtained, and the separation yield was 95.4%.

[0403] Characterization data: 11H NMR (DMSO-d6, 500 MHz): δ (ppm) 11.75 (brs, 1H), 7.36 (s, 1H), 7.07 - 7.09 (m, 1H), 7.00 (d, 1H, J = 8 Hz), 2.30 (s, 3H); 13 13C NMR (DMSO-d6, 125 MHz): 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 + : 165.0, found 165.0. m.p.: 170 - 171 °C.

[0404]

[0405] Column chromatography separation with dry loading and dry sample application (200 - 300 mesh silica gel): Using dichloromethane:ethyl acetate (V / V) = 20:1 as the eluent, 154 mg of white solid was obtained, and the separation yield was 93.5%.

[0406] Characterization data: 1 1H NMR (DMSO-d6, 500 MHz): δ (ppm) 11.73 (brs, 1H), 7.37 (dd, 1H, J1 = 7.5, J2 = 0.5 Hz), 7.08 - 7.09 (m, 1H), 7.03 (t, 1H, J = 7.5 Hz), 2.32 (s, 3H); 13 13C NMR (DMSO-d6, 125 MHz): 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 + : 165.1, found 165.0. m.p.: 211 - 212 °C.

[0407]

[0408] Column chromatography separation with dry loading and dry sample application (200 - 300 mesh silica gel): Using dichloromethane:ethyl acetate (V / V) = 1:2 as the eluent, 140 mg of white solid was obtained, and the separation yield was 61%.

[0409] Characterization data: 11H NMR (DMSO-d6, 500 MHz): δ (ppm) 12.41 (brs, 1H), 8.22 (d, 1H, J = 7.0 Hz), 7.812 (dd, 1H, J = 7.5 Hz, J = 2.0 Hz), 7.31 (d, 1H, J = 8.0 Hz), 3.20 (s, 3H); 13 13C NMR (DMSO-d6, 125 MHz): 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. m.p.: 241 - 244 °C.

[0410]

[0411] Dry column packing and dry sample loading for column chromatography (silica gel 200 - 300 mesh) separation: Using dichloromethane:ethyl acetate (V / V) = 20:1 as the eluent, 128 mg of white solid was obtained, and the separation yield was 76%.

[0412] Characterization data: 1 1H NMR (DMSO-d6, 500 MHz): δ (ppm) 12.39 (brs, 1H), 7.43 (d, 1H, J = 7.5 Hz), 7.12 - 7.22 (m, 2H). 13 13C NMR (DMSO-d6, 125 MHz): δ (ppm) 169.7, 147.1 (d, J = 243.8 Hz), 125.5 (d, J = 3.8 Hz), 124.3 (d, J = 14.6 Hz), 123.0 (d, J = 6.5 Hz), 118.6 (d, J = 6.0 Hz), 112.7 (d, J = 16.9 Hz); MS (EI): m / z calcd for C7H5NOS [M] + : 169.0, found 169.0. m.p.: 172 - 174 °C.

[0413] Example 7 Synthesis of imid(oxa or thia)zolidinone derivatives by the reaction of diamine, alkanolamine or mercaptoamine with CO2 under the action of hydrogen sulfide

[0414]

[0415] Weigh 2 mmol of diamine, 0.8 mmol of base, and 2 ml of solvent, and add them to the reaction kettle in sequence, then tighten the reaction kettle. Introduce the corresponding amount of H2S into the reaction kettle, introduce the corresponding amount of CO2 at an appropriate temperature, and then stir and react for 4 h. After the reaction is completed, cool the reaction kettle to room temperature, slowly exhaust the gas in the reaction kettle, open the reaction kettle, and obtain the target product through extraction, column chromatography or recrystallization.

[0416] Optimize the conditions according to the above steps, and the reaction results are shown in the following table:

[0417]

[0418]

[0419] Note: All the raw materials input are 2 mmol of ethylenediamine; the solvent is 2 ml of NMP. In entry 17, ethylenediamine is used as the base and NMP is added as the solvent.

[0420] Adopt the same method as in entry 10, and use other reaction substrates. The reaction results are as follows:

[0421] Characterization of the compound:

[0422]

[0423] The target product pure product of 170.2 mg was obtained by extraction with ethyl acetate, column chromatography, and recrystallization, and the yield was 99%.

[0424] imidazolidin-2-one: white solid, 1 1H NMR (500 MHz, CDCl3) δ 3.52 (s, 1H). 13 13C NMR (126 MHz, CDCl3) δ 165.64, 41.04.

[0425]

[0426] The target product pure product of 153.7 mg was obtained by extraction with ethyl acetate, column chromatography, and recrystallization, and the yield was 68%. 1,3-Dimethylimidazolidin-2-one: Colorless oil, 1 1H NMR (500 MHz, CDCl3): δ = 2.79 (s, 6H, 2CH3), 3.27 (s, 4H, 2CH2); 13 13C NMR (126 MHz, CDCl3): δ = 31.3, 44.9, 161.9.

[0427]

[0428] The target product pure product (216.5 mg) was obtained by extraction with ethyl acetate and column chromatography, and the yield was 91%.

[0429] 4,5-Diphenylimidazolidin-2-one: white solid, 1 H NMR (500 MHz, CDCl3): δ 7.38 - 7.34 (m, 6H), 7.27 - 7.30 (m, 4H), 5.83 (s, 2H), 4.57 (s, 2H). 13 C NMR (126 MHz, CDCl3) δ 163.1, 140.2, 128.7, 128.2, 126.4, 65.9;

[0430]

[0431] The target product pure product (241.74 mg) was obtained by extraction with ethyl acetate and multiple column chromatographies, and the yield was 85%.

[0432] 1,3-Diethylimidazolidin-2-one: Colorless oil, 95%. 1 H NMR (500 MHz, CDCl3): δ 3.23 (s, 4H), 3.19 (q, J = 7.2 Hz, 4H), 1.05 (t, J = 7.2 Hz, 6H). 13 C NMR (500 MHz, CDCl3): δ 161.3, 42.3, 38.9, 12.9.

[0433]

[0434] The target product pure product (278.49 mg) was obtained by extraction with ethyl acetate and column chromatography, and the yield was 99%.

[0435] octahydro-2H-benzo[d]imidazol-2-one: colourless solid, 1 H NMR (500 MHz, CDCl3) δ 4.75 (s, 2H), 3.67 (s, 2H), 1.66 (s, 4H), 1.61–1.49 (m, 2H), 1.31 (dt, J = 9.6, 5.5 Hz, 2H); 13 C NMR (126 MHz, CDCl3) δ 77.67, 52.45, 28.85, 20.88.

[0436]

[0437] Extraction and column chromatography gave 192 mg of the pure product with a yield of 75%.

[0438] 1,3-Dimethyl-3,4,5,6-tetrahydropyrimidin-2(1H)-one: 1 H NMR(500MHz,CDCl3):δ=1.97(quintet,J=6.0Hz,2H,CH2),2.92(s,6H,2CH3),3.24(t,J=6.0Hz,4H,2CH2); 13 C NMR(126MHz,CDCl3):δ=22.1,35.5,47.8,156.7.

[0439]

[0440] Filtration gave 188 mg of the pure target product with a yield of 73%.

[0441] 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). 13 C NMR(126MHz,DMSO-d6)δ155.26,51.06,27.20,23.89.

[0442]

[0443] Extraction with ethyl acetate and column chromatography gave 174.4 mg of the pure target product with a yield of 99%.

[0444] 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.

[0445]

[0446] Column chromatography and recrystallization from dichloromethane and ethyl acetate gave 182 mg of the target product with a yield of 91%.

[0447] 4-methylimidazolidin-2-one: white solid, 1H NMR (500 MHz, CDCl3) δ 5.00 (s, 2H), 3.92 (h, J=8.3 Hz, 1H), 3.61 (t, J=8.4 Hz, 1H), 3.17–2.99 (m, 1H), 1.25 (d, J=6.4 Hz, 3H). 13 C NMR (126 MHz, CDCl3) δ 163.90, 48.41, 48.01, 21.15.

[0448]

[0449] The target pure product (164.1 mg) was obtained by filtration, with a yield of 72%.

[0450] 1-methyltetrahydropyrimidin-2(1H)-one: white solid, 1 1H NMR (500 MHz, DMSO-d6) δ 6.11 (s, 1H), 3.15 (t, J=5.5 Hz, 2H), 3.09 (t, J=5.5 Hz, 2H), 2.74 (s, 3H), 1.79 (p, J=6.6, 5.9 Hz, 2H). 13 C NMR (126 MHz, DMSO-d6) δ 46.95, 22.02

[0451]

[0452] The target pure product (221.1 mg) was obtained by extraction with ethyl acetate and column chromatography, with a yield of 97%.

[0453] ethylimidazolidin-2-one: Colorless oil, 1 1H NMR (500 MHz, CDCl3) δ 3.50–3.35 (m, 6H), 3.25 (q, J=7.2 Hz, 2H), 1.12 (t, J=7.2 Hz, 3H). 13 C NMR (126 MHz, CDCl3) δ 162.59, 44.39, 38.25, 38.09, 12.69.

[0454]

[0455] The target pure product (172.4 mg) was obtained by extraction with ethyl acetate and separated by column chromatography, with a yield of 99%.

[0456] 2-Oxazolidinone: 1H NMR (500 MHz, CDCl3) δ 3.64 (t, 2H), 4.46 (t, 2H), 6.68 (s, 1H). 13 C NMR (126 MHz, CDCl3), δ 41.0, 65.5, 161.5.

[0457]

[0458] Column chromatography was performed by wet packing the column and dry loading the sample (using silica gel of 200 - 300 mesh). Dichloromethane and ethyl acetate (V / V = 3:1) were used as the eluent. A pale yellow solid (280.6 mg) was obtained with a separation yield of 86%.

[0459] 4-phenyloxazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ (ppm) 7.42 - 7.33 (m, 5H), 5.88 (s, 1H), 4.99 - 4.92 (m, 1H), 4.74 (t, J = 8.7 Hz, 1H), 4.19 (dd, J = 8.6, 7.0 Hz, 1H). 13 C NMR (126 MHz, DMSO-d6) δ (ppm) 159.37, 141.48, 129.19, 128.44, 126.51, 71.84, 55.57. ESI-MS calcd for C9H 10 NO2[M + H] + 164.06, found 164.10.

[0460]

[0461] Column chromatography was performed by wet packing the column and dry loading the sample (using silica gel of 200 - 300 mesh). Dichloromethane and ethyl acetate (V / V = 3:1) were used as the eluent. A white solid (229.5 mg) was obtained with a separation yield of 70%.

[0462] 5-phenyloxazolidin-2-one: white solid, 1 1H NMR (500 MHz, CDCl3) δ (ppm) 7.43 - 7.36 (m, 5H), 5.77 (brs, 1H), 5.63 (t, J = 8.1 Hz, 1H), 3.99 (t, J = 9.0 Hz, 1H), 3.55 (t, J = 8.4 Hz, 1H). 1313C NMR (126 MHz, CDCl3) δ (ppm) 159.66, 138.38, 128.92, 125.66, 77.90, 48.29. ESI-MS calcd for C9H 10 NO2 [M+H] + 164.06, found 164.10.

[0463]

[0464] Column chromatography with wet packing and wet sample loading (200 - 300 mesh silica gel) was used for separation. Dichloromethane and ethyl acetate (V / V = 1:1) were used as the eluent. The product was obtained with a mass of 201.6 mg and a separation yield of 99%.

[0465] 4-methyloxazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ (ppm) 6.45 (brs, 1H), 4.50 (t, J = 8.1 Hz, 1H), 4.05 - 3.99 (m, 1H), 3.96 - 3.93 (m, 1H), 1.30 (d, J = 6.1 Hz, 3H). 13 13C NMR (126 MHz, CDCl3) δ (ppm) 160.11, 71.65, 48.25, 20.78. ESI-MS calcd for C4H8NO2 [M+H] + 102.05, found 102.10.

[0466]

[0467] Column chromatography with wet packing and wet sample loading (200 - 300 mesh silica gel) was used for separation. Dichloromethane and ethyl acetate (V / V = 1:1) were used as the eluent. The product was obtained with a mass of 182.2 mg and a separation yield of 90%.

[0468] 5-methyloxazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ (ppm) 5.82 (brs, 1H), 4.81 - 4.75 (m, 1H), 3.71 (t, J = 8.3 Hz, 1H), 3.21 (t, J = 7.0 Hz, 1H), 1.46 (d, J = 6.3 Hz, 3H). 13 13C NMR (126 MHz, CDCl3) δ (ppm) 160.04, 77.21, 73.50, 47.40, 20.52. ESI-MS calcd for C4H8NO2 [M+H] +102.05, found 102.10.

[0469]

[0470] Column chromatography with wet packing and wet sample loading (using silica gel of 200 - 300 mesh) was carried out for separation. Dichloromethane and ethyl acetate (V / V = 5:1) were used as the developing agent, and 225.6 mg of the product was obtained with a separation yield of 99%.

[0471] 4-ethyloxazolidin-2-one: 1 H NMR (500 MHz, CDCl3) δ (ppm) 5.80 (brs, 1H), 4.04 (dd, J = 8.6, 6.0 Hz, 1H), 3.84 - 3.79 (m, 1H), 1.57 - 1.66 (m, 2H), 0.95 (t, J = 7.5 Hz, 3H). 13 C NMR (126 MHz, CDCl3) δ (ppm) 159.73, 69.95, 53.75, 28.15, 9.29. ESI-MS calcd for C5H 10 NO2[M + H] + 116.06, found 116.10.

[0472]

[0473] Column chromatography with wet packing and wet sample loading (using silica gel of 200 - 300 mesh) was carried out for separation. Methanol and dichloromethane (V / V = 1:5) were used as the developing agent, and 225.9 mg of white solid was obtained with a separation yield of 100%.

[0474] 5,5-dimethyloxazolidin-2-one: 1 H NMR (500 MHz, CDCl3) δ (ppm) 5.11 (brs, 1H), 3.35 (s, 2H), 1.48 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ (ppm) 159.34, 81.02, 52.64, 27.19. ESI-MS calcd for C5H 10 NO2[M + H] + 116.06, found 116.15.

[0475]

[0476] Column chromatography was performed with wet packing and wet sample loading (using silica gel of 200 - 300 mesh). Methanol and dichloromethane (V / V = 1:5) were used as the eluent. A white solid (93.5 mg) was obtained with a separation yield of 41%.

[0477] 4,4-dimethyloxazolidin-2-one: 1 H NMR(500MHz,CDCl3)δ(ppm)6.11(brs,1H),4.09(s,2H),1.37(s,6H). 13 C NMR(126MHz,CDCl3)δ(ppm)158.84,76.90,55.19,27.59.ESI-MS calcd for C5H 10 NO2[M+H] + 116.06,found 116.10.

[0478]

[0479] Column chromatography was performed with wet packing and dry sample loading (using silica gel of 200 - 300 mesh). Dichloromethane and ethyl acetate (V / V = 2:1) were used as the eluent. A white solid (317.3 mg) was obtained with a separation yield of 90%.

[0480] (R)-4-benzyloxazolidin-2-one: 1 H NMR(500MHz,DMSO-d6)δ(ppm)7.78(brs,1H),7.33-7.21(m,5H),4.25(t,J=8.3Hz,1H),4.08-3.96(m,2H),2.84-2.72(m,2H). 13 CNMR(126MHz,DMSO-d6)δ(ppm)159.04,136.99,129.82,128.84,126.98,68.46,52.93,40.68.ESI-MS calcd for C 10 H 12 NO2[M+H] + 178.08,found 178.05.

[0481]

[0482] Column chromatography was performed with wet packing and wet sample loading (using silica gel of 200 - 300 mesh). Dichloromethane and ethyl acetate (V / V = 2:1) were used as the eluent. A white solid (237.2 mg) was obtained with a separation yield of 94%.

[0483] (S)-4-isopropyloxazolidin-2-one: 1 1H NMR(500MHz,CDCl3)δ(ppm)6.47(brs),4.44 (t,J=8.7Hz,1H),4.10(dd,J=8.7,6.3Hz,1H),3.63-3.59(m,1H),1.77-1.70(m,1H),0.97(d,J=6.7Hz,3H),0.90(d,J=6.8Hz,3H). 13 13C NMR(126MHz,CDCl3)δ(ppm)160.25,68.59,58.34,32.67,17.99,17.62.ESI-MS calcd for C6H 12 NO2[M+H] + 130.08,found 130.10.

[0484]

[0485] The target product pure product (172.0 mg) was obtained by extraction with ethyl acetate and separation by column chromatography, and the yield was 86%.

[0486] 1,3-Oxazinan-2-one: 1 1H 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,). 13 13C NMR(126MHz,DMSO d6)δ21.79,39.78,67.04,153.74.

[0487]

[0488] The target product pure product (171.0 mg) was obtained by extraction with ethyl acetate and separation by column chromatography, and the yield was 84%.

[0489] thiazolidin-2-one: 1 1H NMR(500MHz,CDCl3)δ3.37(t,J=3.6Hz,2H),3.59(t,J=3.6Hz,2H),6.99(s,1H)

[0490] Example 8 Reaction of 2-aminobenzonitrile with CO2 under the action of H2S to synthesize thioquinazoline dione derivatives

[0491]

[0492] A magnetic stir bar was placed into a 10 mL stainless steel autoclave, and 1 mmol of o-aminobenzonitrile derivative, an appropriate amount of H2S and 2 mL of solvent were added successively. The autoclave was tightly sealed. Carbon dioxide at a specified pressure was charged into the autoclave, and the mixture was stirred for reaction for 24 h. The reaction was stopped and cooled. The gas in the autoclave was slowly exhausted, the autoclave was opened, and the mixture was extracted with ethyl acetate and saturated brine. The organic phases were combined and concentrated under reduced pressure to obtain a crude product. The pure target product was obtained by column chromatography using petroleum ether and ethyl acetate.

[0493] The conditions were optimized according to the above steps, and the reaction results are shown in the following table:

[0494]

[0495]

[0496] Note: In each of the above reactions, the raw material was 1 mmol of o-aminobenzonitrile; the solvent was 2 mL; the molar ratio was the molar ratio of the raw material and DBU; the reaction time was 24 h.

[0497] Using the method in entry 9 and changing the substrates, the following compounds were obtained:

[0498]

[0499] Column chromatography separation by dry packing and dry sample loading (200 - 300 mesh silica gel): Gradient elution was used, with petroleum ether and ethyl acetate as eluents, petroleum ether:ethyl acetate (V / V) = 1:1. After separation, 235.2 mg of yellow solid 6,7-dimethoxy-2-oxo-4-thioquinazoline-1,3-dione was obtained, and the yield of column chromatography separation was 99%. The analysis results showed that the structure of the obtained target product was correct.

[0500] 1 H NMR (500 MHz, 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 (126 MHz, 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

[0501]

[0502] Dry column packing and dry sample loading for column chromatography (200 - 300 mesh silica gel) separation: Gradient elution was used, with petroleum ether and ethyl acetate as eluents. The ratio of petroleum ether to ethyl acetate (V / V) was 2:1, and then the polarity was increased to 1:1. After separation, 184 mg of yellow solid 6-fluoro-2-oxo-4-thioquinazoline dione was obtained, and the column chromatography separation yield was 94%. The analysis results showed that the structure of the obtained target product was correct.

[0503] 1 H NMR (500 MHz, DMSO-d6) δ = 12.91 (s, 1H), 11.67 (s, 1H), 7.96 (dd, J = 9.7, 3.0 Hz, 1H), 7.58 (td, J = 8.5, 3.0 Hz, 1H), 7.20 (dd, J = 9.0, 4.6 Hz, 1H). 13 C NMR (126 MHz, DMSO-d6) δ = 190.86 (d, J = 3.3 Hz), 157.63 (d, J = 240.0 Hz), 147.13, 134.92, 123.63 (d, J = 24.9 Hz), 120.94 (d, J = 8.19 Hz), 118.26 (d, J = 8.06 Hz), 114.76 (d, J = 25.3 Hz). MS (ESI): m / z calcd for C8H5FN2OS [M] + : 197.01, found 196.9

[0504]

[0505] Dry column packing and dry sample loading for column chromatography (200 - 300 mesh silica gel) separation: Gradient elution was used, with petroleum ether and ethyl acetate as eluents. The ratio of petroleum ether to ethyl acetate (V / V) was 3:1. After separation, 217 mg of white solid 6-bromo-2-oxo-4-thioquinazoline dione was obtained, and the column chromatography separation yield was 85%. The analysis results showed that the structure of the obtained target product was correct.

[0506] 1 H NMR (500 MHz, DMSO-d6) δ = 12.94 (s, 1H), 11.75 (s, 1H), 8.37 (dd, J = 2.4, 1.0 Hz, 1H), 7.83 (ddd, J = 8.6, 2.4, 1.0 Hz, 1H), 7.13 (dd, J = 8.7, 1.1 Hz, 1H). 1313C NMR (126 MHz, 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。

[0507]

[0508] Column chromatography separation by dry packing and dry sample loading (200 - 300 mesh silica gel): Gradient elution was used with petroleum ether and ethyl acetate as eluents, petroleum ether:ethyl acetate (V / V) = 2:1. After separation, 162 mg of yellow solid 7-fluoro-2-oxo-4-thioquinazoline dione was obtained, and the column chromatography separation yield was 83%. The analysis results showed that the structure of the obtained target product was correct.

[0509] 1 1H NMR (500 MHz, DMSO-d6) δ = 12.77 (s, 1H), 11.65 (s, 1H), 8.27 (t, J = 7.3 Hz, 1H), 7.59 (dd, J = 8.8, 6.6 Hz, 1H), 7.37–7.29 (m, 1H). 13 13C NMR (126 MHz, DMSO-d6) δ = 190.80, 162.40, 150.31, 146.01, 141.27, 127.28, 120.12, 111.07 (d, J = 11.3 Hz). MS(ESI): m / z calcd for C8H5FN2OS [M] + :, 197.01 found 197.3.

[0510]

[0511] Column chromatography separation by dry packing and dry sample loading (200 - 300 mesh silica gel): Gradient elution was used with petroleum ether and ethyl acetate as eluents, petroleum ether:ethyl acetate (V / V) = 2:1. After separation, 219 mg of yellow solid 7-trifluoromethyl-2-oxo-4-thioquinazoline dione was obtained, and the column chromatography separation yield was 89%. The analysis results showed that the structure of the obtained target product was correct.

[0512] 1 1H NMR (500 MHz, DMSO-d6) δ = 13.05 (s, 1H), 11.81 (s, 1H), 8.47 (d, J = 8.5 Hz, 1H), 7.53–7.47 (m, 1H), 7.45 (d, J = 1.7 Hz). 1313C NMR (126 MHz, DMSO-d6) δ = 191.30, 147.06, 138.48, 134.17 (q, J = 32.8 Hz), 132.04, 123.34 (q, J = 273.7 Hz), 122.36, 118.84 (q, J = 3.8 Hz), 113.15 (q, J = 3.8 Hz). MS (ESI): m / z calcd for C9H5F3N2OS [M] + : 247.01, found 247.3.

[0513]

[0514] 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, petroleum ether:ethyl acetate (V / V) = 2:1. After separation, 138 mg of yellow solid 7-chloro-2-oxo-4-thioquinazoline-4-one was obtained, and the column chromatography separation yield was 65%. The analysis results showed that the structure of the obtained target product was correct.

[0515] 1 1H NMR (500 MHz, DMSO-d6) δ = 12.71 (s, 1H), 11.56 (s, 1H), 8.23 (t, J = 8.4 Hz, 1H), 7.48 (dd, J = 8.5, 1.2 Hz, 1H), 6.54–6.40 (m, 1H). 13 13C NMR (126 MHz, DMSO-d6) δ = 191.92, 170.17, 151.67, 136.49, 130.76, 115.32, 113.52, 112.55. MS (ESI): m / z calcd for C8H5ClN2OS [M] + : 212.65, found 212.3。

[0516]

[0517] 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, petroleum ether:ethyl acetate (V / V) = 2:1. After separation, 172 mg of yellow solid 7-methyl-2-oxo-4-thioquinazoline-4-one was obtained, and the column chromatography separation yield was 89%. The analysis results showed that the structure of the obtained target product was correct.

[0518] 11H NMR (500 MHz, DMSO-d6) δ = 12.66 (s, 1H), 11.56 (s, 1H), 8.19 (d, J = 8.3 Hz, 1H), 7.03 (d, J = 8.4 Hz, 1H), 6.94 (s, 1H), 2.35 (s, 3H). 13 13C NMR (126 MHz, DMSO-d6)) δ = 188.97, 148.23, 146.65, 137.75, 131.11, 125.24, 119.85, 114.69. MS (ESI): m / z calcd for C9H8N2OS [M] + : 193.04, found 193.2。

[0519]

[0520] Column chromatography separation by dry packing and dry sample loading (200 - 300 mesh silica gel): Gradient elution was used with petroleum ether and ethyl acetate as eluents, petroleum ether:ethyl acetate (V / V) = 1:1. After separation, 80 mg of brown solid 6-nitro-2-oxo-4-thioxoquinazoline-3,4-dione was obtained. The column chromatography separation yield was 36%. The analysis results showed that the structure of the obtained target product was correct.

[0521] 1 1H NMR (500 MHz, DMSO-d6) δ = 12.51 (s, 1H), 11.28 (s, 1H), 7.48 (d, J = 2.6 Hz, 1H), 7.00 (dd, J = 8.7, 2.6 Hz, 1H), 6.92–6.89 (m, 1H). 13 13C NMR (126 MHz, DMSO-d6) δ = 191.01, 158.80, 144.50, 128.55, 123.74, 122.13, 116.09, 111.20. MS (ESI): m / z calcd for C8H5N3O3S [M] + : 223.01, found 223.4。

[0522]

[0523] Column chromatography separation by dry packing and dry sample loading (200 - 300 mesh silica gel): Gradient elution was used with petroleum ether and ethyl acetate as eluents, petroleum ether:ethyl acetate (V / V) = 2:1. After separation, 133 mg of yellow solid 5-fluoro-2-oxo-4-thioxoquinazoline-3,4-dione was obtained. The column chromatography separation yield was 68%. The analysis results showed that the structure of the obtained target product was correct.

[0524] 11H NMR (500 MHz, DMSO-d6) δ = 11.85 (s, 1H), 11.20 (s, 1H), 7.35 (t, J = 8.1 Hz, 1H), 6.68 (d, J = 8.3 Hz, 1H), 6.50 (d, J = 7.8 Hz, 1H). 13 13C NMR (126 MHz, DMSO-d6) δ = 186.47, 154.09, 147.11, 141.12, 134.24, 111.58, 110.66, 104.63. MS (ESI): m / z calcd for C8H5FN2OS [M] + : 197.01, found 197.2

[0525]

[0526] Dry-column packing and dry-sample loading column chromatography (200 - 300 mesh silica gel) separation: Gradient elution was adopted, using petroleum ether and ethyl acetate as eluents, petroleum ether:ethyl acetate (V / V) = 2:1. After separation, 240 mg of yellow solid 6-trifluoromethyl-2-oxo-4-thioquinazolinone was obtained, and the column chromatography separation yield was 97%. The analysis results showed that the structure of the obtained target product was correct.

[0527] 1 1H NMR (500 MHz, DMSO-d6) δ = 13.06 (s, 1H), 11.97 (d, J = 3.8 Hz, 1H), 8.57–8.53 (m, 1H), 8.01–7.94 (m, 1H), 7.34 (dd, J = 8.6, 3.8 Hz, 1H). 13 13C NMR (126 MHz, DMSO-d6) δ = 191.24, 147.13, 141.10, 131.40 (q, J = 3.0 Hz), 127.52 (q, J = 4.4 Hz), 123.84 (q, J = 272.2 Hz), 123.36 (q, J = 32.8 Hz), 119.82, 117.43. MS (ESI): m / z calcd for C9H5F3N2OS [M] + : 247.01, found 247.3.

[0528] Example 10 Reaction of benzylamine with CO2 under the action of hydrogen sulfide to synthesize substituted urea derivatives

[0529]

[0530] In a 15 mL high-pressure reactor, 2 mmol of benzylamine, DBU, and 1 mL of a suitable solvent were added in sequence, and the reactor was tightened; the required amounts of H2S and CO2 gases were introduced into the reactor in sequence; finally, the reactor was continuously reacted at a suitable temperature for 24 hours; after the reaction was completed, a certain amount of distilled water was added to the reaction solution to completely precipitate the product, and then the target product was obtained by filtration and drying in sequence.

[0531] The conditions were optimized according to the above steps, and the reaction results are shown in the following table:

[0532]

[0533] Note: In each of the above reactions, the raw material was 2 mmol of benzylamine; the solvent was 1 mL, and NR: no reaction.

[0534] Using the same method as in entry 4 and replacing with other reaction substrates, the following compounds were obtained:

[0535]

[0536] Through filtration and drying, 205 mg of a white powdery product was obtained, and the yield was 91%.

[0537] 1 H NMR (500 MHz, DMSO-d6) δ 7.31 (t, J = 7.5 Hz, 4H), 7.28–7.18 (m, 6H), 6.43 (t, J = 6.1 Hz, 2H), 4.23 (d, J = 6.0 Hz, 4H).

[0538] 13 C NMR (126 MHz, DMSO-d6) δ 158.08, 140.89, 128.19, 126.96, 126.52, 42.98.

[0539] MS (ESI): m / z calcd for C 15 H 17 N2O [M + H] + : 241.10, found 241.13, m.p.: 168 - 169 °C

[0540]

[0541] Through filtration and drying, 244 mg of a pale yellow powdery product was obtained, and the yield was 86%.

[0542] 11H NMR (500 MHz, Chloroform-d) δ 4.58 (s, 2H), 3.18–3.10 (m, 4H), 1.47 (q, J = 6.8 Hz, 4H), 1.28 (d, J = 10.4 Hz, 20H), 0.88 (t, J = 6.4 Hz, 6H).

[0543] 13 13C NMR (126 MHz, Chloroform-d) δ 158.50, 40.63, 31.83, 30.31, 29.36, 29.27, 26.96, 22.66, 14.09.

[0544] MS (ESI): m / z calcd for C 19 H 40 N3O [M + H + CH3CN] + : 326.30, found 326.32, m.p.: 89 - 91 °C

[0545]

[0546] The white powder product (163 mg) was obtained by filtration and drying, with a yield of 71%.

[0547] 1 1H NMR (500 MHz, DMSO-d6) δ 5.72 (t, J = 5.7 Hz, 2H), 2.94 (q, J = 6.8, 6.4 Hz, 4H), 1.32 (q, J = 6.8 Hz, 4H), 1.27–1.18 (m, 12H), 0.85 (t, J = 6.7 Hz, 6H). 13 13C NMR (126 MHz, Chloroform-d) δ 158.62, 40.58, 31.59, 30.29, 26.63, 22.60, 14.03.

[0548] MS (ESI): m / z calcd for C 13 H 29 N2O [M + H] + : 229.20, found 229.23, m.p.: 73 - 76 °C

[0549]

[0550] The white powder product (129 mg) was obtained by filtration and drying, with a yield of 64%.

[0551] 11H NMR (500 MHz, DMSO-d6) δ 5.71 (t, J = 5.9 Hz, 2H), 2.95 (q, J = 6.7 Hz, 4H), 1.34 (p, J = 7.1 Hz, 4H), 1.31–1.18 (m, 8H), 0.86 (t, J = 7.1 Hz, 6H).

[0552] 13 13C NMR (126 MHz, DMSO-d6) δ 158.52, 40.55, 30.19, 29.06, 22.35, 14.39.

[0553] MS (ESI): m / z calcd for C 11 H 25 N2O [M+H] + : 201.15, found 201.20, m.p.: 86 - 88 °C

[0554]

[0555] After reacting for 36 h, a white crystalline product (157 mg) was obtained by filtration and drying, with a yield of 73%.

[0556] 1 1H NMR (500 MHz, TFA-d) δ 5.11 (s, 2H), 3.54 (d, J = 9.8 Hz, 4H), 3.35 (d, J = 10.0 Hz, 4H), 3.22 (d, J = 11.6 Hz, 2H), 2.86 (ddt, J = 42.0, 22.0, 11.2 Hz, 12H).

[0557] 13 13C NMR (126 MHz, TFA-d) δ 159.93, 55.32, 35.04, 27.30, 26.93.

[0558] MS (ESI): m / z calcd for C 13 H 25 N2O [M+H] + : 225.10, found 225.20, m.p.: 229 - 230 °C

[0559]

[0560] A yellow powdery product (243 mg) was obtained by filtration and drying, with a yield of 91%.

[0561] 11H NMR (500 MHz, DMSO-d6) δ 7.35–7.15 (m, 10H), 6.27 (d, J = 8.1 Hz, 2H), 4.72 (q, J = 7.0 Hz, 2H), 1.30 (dd, J = 10.8, 7.5 Hz, 6H).

[0562] 13 13C NMR (126 MHz, DMSO-d6) δ 156.54, 145.67, 128.27, 126.50, 125.72, 48.50, 23.40.

[0563] MS (ESI): m / z calcd for C 17 H 21 N2O [M+H] + : 269.10, found 269.17, m.p.: 122 - 123 °C

[0564]

[0565] The product was obtained as a silver-white powdery substance (244 mg) by filtration and drying, with a yield of 91%.

[0566] 1 1H NMR (500 MHz, DMSO-d6) δ 7.29 (t, J = 7.5 Hz, 4H), 7.23–7.16 (m, 6H), 5.89 (t, J = 5.1 Hz, 2H), 3.22 (q, J = 6.7 Hz, 4H), 2.67 (d, J = 7.2 Hz, 4H).

[0567] 13 13C NMR (126 MHz, DMSO-d6) δ 157.97, 139.81, 128.72, 128.35, 126.02, 40.97, 36.23.

[0568] MS (ESI): m / z calcd for C 17 H 21 N2O [M+H] + : 269.10, found 269.17, m.p.: 138 - 140 °C

[0569]

[0570] The product was obtained as a white powdery substance (285 mg) by filtration and drying, with a yield of 96%.

[0571] 11H NMR (500 MHz, DMSO-d6) δ 7.26 (t, J = 7.5 Hz, 2H), 7.17 (dd, J = 15.1, 7.4 Hz, 3H), 5.88 (d, J = 5.3 Hz, 1H), 2.98 (t, J = 6.6 Hz, 2H), 2.58–2.53 (m, 2H), 1.66 (q, J = 7.3 Hz, 2H).

[0572] 13 13C NMR (126 MHz, DMSO-d6) δ 158.22, 141.91, 128.33, 128.32, 125.74, 38.84, 32.58, 31.93.

[0573] MS (ESI): m / z calcd for C 19 H 25 N2O [M+H] + : 297.20, found 297.20, m.p.: 92 - 93 °C

[0574]

[0575] The white powdery product (233 mg) was obtained by filtration and drying, with a yield of 86%.

[0576] 1 1H NMR (500 MHz, DMSO-d6) δ 7.20 (d, J = 4.7 Hz, 1H), 7.14 (s, 3H), 6.27 (t, J = 5.5 Hz, 1H), 4.21 (d, J = 4.9 Hz, 2H), 2.26 (s, 3H).

[0577] 13 13C NMR (126 MHz, DMSO-d6) δ 157.93, 138.37, 135.45, 129.94, 127.22, 126.73, 125.77, 41.02, 18.58.

[0578] MS (ESI): m / z calcd for C 17 H 21 N2O [M+H] + : 269.10, found 269.17, m.p.: 237 - 238 °C

[0579]

[0580] The white crystalline product (260 mg) was obtained by filtration and drying, with a yield of 84%.

[0581] 11H NMR (500 MHz, DMSO-d6) δ 7.35 (d, J = 8.3 Hz, 4H), 7.26 (d, J = 8.2 Hz, 4H), 6.66 (t, J = 5.8 Hz, 2H), 4.20 (d, J = 5.7 Hz, 4H).

[0582] 13 13C NMR (126 MHz, DMSO-d6) δ 158.20, 140.09, 131.09, 128.88, 128.19, 42.34.

[0583] MS (ESI): m / z calcd for C 15 H 16 Cl2N2NaO2 [M + Na + H2O] + : 350.05, found 350.05, m.p.: 253 - 254 °C

[0584]

[0585] The off-white crystalline product (344 mg) was obtained by filtration and drying, with a yield of 86%.

[0586] 1 1H NMR (500 MHz, DMSO-d6) δ 7.49 (d, J = 7.9 Hz, 4H), 7.19 (d, J = 7.9 Hz, 4H), 6.53 (t, J = 5.8 Hz, 2H), 4.18 (d, J = 6.0 Hz, 4H).

[0587] 13 13C NMR (126 MHz, DMSO-d6) δ 158.10, 140.50, 131.11, 129.27, 119.56, 42.42.

[0588] MS (ESI): m / z calcd for C 15 H 16 Br2N2NaO2 [M + Na + H2O] + : 439.95, found 439.95, m.p.: 268 - 270 °C

[0589]

[0590] The white powdery product (257 mg) was obtained by filtration and drying, with a yield of 85%.

[0591] 11H NMR (500 MHz, DMSO-d6) δ 7.17 (d, J = 8.5 Hz, 4H), 6.86 (d, J = 8.6 Hz, 4H), 6.30 (s, 2H), 4.14 (s, 4H), 3.72 (s, 6H).

[0592] 13 13C NMR (126 MHz, DMSO-d6) δ 158.15, 132.79, 128.40, 113.70, 55.13, 42.50.

[0593] MS (ESI): m / z calcd for C 17 H 21 N2O3 [M + H] + : 301.10, found 301.16, m.p.: 178 - 180 °C

[0594]

[0595] The light yellow solid product (290 mg) was obtained by filtration and drying, with a yield of 74%.

[0596] 1 1H NMR (500 MHz, DMSO-d6) δ 7.31 (d, J = 6.9 Hz, 8H), 7.28–7.18 (m, 12H), 6.95 (d, J = 8.1 Hz, 2H), 5.88 (d, J = 8.0 Hz, 2H).

[0597] 13 13C NMR (126 MHz, DMSO-d6) δ 156.79, 144.01, 128.87, 127.25, 127.22, 57.41.

[0598] MS (ESI): m / z calcd for C 27 H 25 N2O [M + H] + : 393.15, found 393.20, m.p.: 283 - 284 °C

[0599]

[0600] The off-white powdery product (106 mg) was obtained by filtration and drying, with a yield of 39%.

[0601] 11H NMR (500 MHz, DMSO-d6) δ 9.23 (s, 2H), 7.04 (d, J = 8.1 Hz, 4H), 6.69 (d, J = 7.2 Hz, 4H), 6.18 (d, J = 6.0 Hz, 2H), 4.09 (d, J = 5.8 Hz, 4H).

[0602] 13 13C NMR (126 MHz, DMSO-d6) δ 157.97, 156.08, 130.92, 128.38, 114.95, 42.57.

[0603] MS (ESI): m / z calcd for C 15 H 17 N2O3 [M + H] + : 273.05, found 273.12, m.p.: 185 - 187 °C

[0604]

[0605] The white crystalline product (240 mg) was obtained by filtration and drying, with a yield of 89%.

[0606] 1 1H NMR (500 MHz, DMSO-d6) δ 7.17 – 7.08 (m, 8H), 6.33 (t, J = 6.1 Hz, 2H), 4.17 (d, J = 6.0 Hz, 4H), 2.27 (s, 6H).

[0607] 13 13C NMR (126 MHz, DMSO-d6) δ 157.91, 137.68, 135.41, 128.62, 126.87, 42.59, 20.54.

[0608] MS (ESI): m / z calcd for C 17 H 21 N2O [M + H] + : 269.10, found 269.17, m.p.: 216 - 218 °C

[0609]

[0610] The white solid product (203 mg) was obtained by filtration and drying, with a yield of 63%.

[0611] 11H NMR (500 MHz, DMSO-d6) δ 7.16 (s, 8H), 6.33 (t, J = 6.0 Hz, 2H), 4.18 (d, J = 5.9 Hz, 4H), 2.85 (hept, J = 6.7 Hz, 2H), 1.18 (d, J = 6.9 Hz, 12H).

[0612] 13 13C NMR (126 MHz, DMSO-d6) δ 157.92, 146.59, 138.11, 126.98, 125.97, 42.67, 33.01, 23.87.

[0613] MS (ESI): m / z calcd for C 21 H 29 N2O [M + H] + : 325.15, found 325.23, m.p.: 122 - 123 °C

[0614]

[0615] The white powdery product (287 mg) was obtained by filtration and drying, with a yield of 78%.

[0616] 1 1H NMR (500 MHz, DMSO-d6) δ 8.15 (d, J = 8.4 Hz, 1H), 8.08 (d, J = 9.5 Hz, 1H), 7.97–7.89 (m, 2H), 7.85–7.77 (m, 2H), 7.60–7.42 (m, 8H), 6.42 (dd, J = 20.3, 8.1 Hz, 2H), 5.55 (h, J = 6.9 Hz, 2H), 1.46 (dd, J = 22.3, 6.9 Hz, 6H).

[0617] 13 13C NMR (126 MHz, DMSO-d6) δ 156.36, 141.29, 133.41, 130.42, 128.57, 127.14, 126.04, 125.54, 123.24, 121.84, 44.65, 22.53.

[0618] MS (ESI): m / z calcd for C 25 H 25 N2O [M + H] + : 369.15, found 369.20, m.p.: 223 - 225 °C

[0619]

[0620] Through filtration and drying, 331 mg of a pale yellow solid product was obtained with a yield of 87%.

[0621] 1 H NMR (500 MHz, DMSO-d6) δ 7.56 (d, J = 8.2 Hz, 2H), 7.46 (d, J = 2.0 Hz, 2H), 7.24 (dd, J = 8.3, 2.0 Hz, 2H), 6.69 (t, J = 6.2 Hz, 2H), 4.21 (d, J = 6.1 Hz, 4H).

[0622] 13 C NMR (126 MHz, DMSO-d6) δ 157.97, 142.39, 130.80, 130.36, 128.96, 128.83, 127.29, 41.96.

[0623] MS (ESI): m / z calcd for C 15 H 14 Cl4N2NaO2 [M + Na + H2O] + : 419.95, found 419.97, m.p.: 174 - 176 °C

[0624]

[0625] Through filtration and drying, 196 mg of a white powdery product was obtained with a yield of 89%.

[0626] 1 H NMR (500 MHz, DMSO-d6) δ 7.55 (s, 2H), 6.40–6.30 (m, 4H), 6.18 (d, J = 3.2 Hz, 2H), 4.20 (d, J = 5.7 Hz, 4H).

[0627] 13 C NMR (126 MHz, DMSO-d6) δ 157.40, 153.54, 141.89, 110.41, 106.22, 40.02, 39.85, 39.69, 39.52, 39.35, 39.19, 39.02, 36.37.

[0628] MS (ESI): m / z calcd for C 11 H 13 N2O3 [M + H] + : 221.00, found 221.09, m.p.: 126 - 128 °C

[0629]

[0630] A yellow oil was obtained through a separation column with a yield of 89%.

[0631] 1 H NMR(500MHz,DMSO-d6)δ6.08–6.02(m,2H),3.75(dq,J=13.9,6.4Hz,4H),3.59(q,J=7.5Hz,2H),3.10(dq,J=14.3,5.2Hz,2H),3.05–2.95(m,2H),1.89–1.72(m,6H),1.52–1.41(m,2H).

[0632] 13 C NMR(126MHz,DMSO-d6)δ158.68,78.10,67.40,43.56,28.43,25.50.

[0633] MS(ESI):m / z calcd for C 11 H 21 N2O3[M+H] + :229.10,found 229.16,Pyrolysistemperature:140℃

[0634]

[0635] A yellow solid product of 370 mg was obtained through filtration and drying with a yield of 93%.

[0636] 1 H NMR(500MHz,TFA-d)δ4.92(t,J=7.1Hz,4H),3.23(p,J=6.9Hz,4H),2.90(d,J=31.6Hz,36H),2.43(td,J=6.7,2.9Hz,6H).

[0637] 13 C NMR(126MHz,TFA-d)δ160.26,109.99,43.49,33.13,30.76,30.65,30.55,30.51,30.18,29.82,27.62,23.70,14.05.

[0638] MS(ESI):m / z calcd for C 25 H 52 KN2O[M+K] + :435.30,found 435.37,m.p.:105-106℃

[0639]

[0640] Through filtration and drying, 311 mg of a white solid product was obtained with a yield of 83%.

[0641] 1 H NMR (500 MHz, DMSO-d6) δ 7.67 (d, J = 8.0 Hz, 4H), 7.46 (d, J = 7.9 Hz, 4H), 6.69 (t, J = 6.2 Hz, 2H), 4.32 (d, J = 6.0 Hz, 4H).

[0642] 13 C NMR (126 MHz, DMSO-d6) δ 158.14, 145.99, 127.57, 127.30 (q, J = 32.1 Hz), 125.09 (q, J = 3.9 Hz), 124.44 (q, J = 272.4 Hz), 42.67.

[0643] MS (ESI): m / z calcd for C 17 H 15 F6N2O [M+H] + : 377.05, found 377.11, m.p.: 106 - 161 °C

[0644]

[0645] A pale yellow oily substance was obtained through a separation column with a yield of 92%.

[0646] 1 H NMR (500 MHz, DMSO-d6) δ 8.50 (d, J = 4.7 Hz, 2H), 7.76 (t, J = 7.6 Hz, 2H), 7.30 (d, J = 7.8 Hz, 2H), 7.28–7.21 (m, 2H), 6.75 (t, J = 5.8 Hz, 2H), 4.34 (d, J = 5.8 Hz, 4H).

[0647] 13 C NMR (126 MHz, DMSO-d6) δ 159.69, 158.12, 148.69, 136.62, 121.90, 120.84, 44.96.

[0648]

[0649] Through filtration and drying, 197 mg of a brownish-yellow powdery product was obtained with a yield of 78%.

[0650] 11H NMR (500 MHz, DMSO-d6) δ 7.36 (d, J = 4.7 Hz, 2H), 6.93 (d, J = 4.3 Hz, 4H), 6.50 (t, J = 6.0 Hz, 2H), 4.38 (d, J = 5.8 Hz, 4H).

[0651] 13 13C NMR (126 MHz, DMSO-d6) δ 157.40, 144.22, 126.60, 124.66, 38.12.

[0652] MS (ESI): m / z calcd for C 11 H 13 N2OS2 [M+H] + : 253.00, found 253.05, m.p.: 163 - 165 °C

[0653] All documents mentioned in this invention are incorporated herein by reference as if each individual document was specifically and individually incorporated by reference. In addition, it should be understood that after reading the above teachings of this invention, those skilled in the art can make various changes or modifications to this invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

Claims

1. A method for preparing carbonyl compounds using carbon dioxide as a carbonylation reagent, characterized in that, The described method is carried out in the presence of H2S and an optional base; and the described method includes step (b), (c), or (d); (b) In an optional inert solvent, in the presence of a base, o-nitroiodobenzene reacts with CO2 and hydrogen sulfide to synthesize benzothiazolone derivatives; R3 is one or more groups selected from the group consisting of: H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, NH2, NO2, SO2CH3, or a phenyl group that is unsubstituted or substituted with 1-4 substituents selected from the group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; In step (b), the base is selected from the group consisting of: DBU, TBD, MTBD, DBN, TMG, DABCO, ethylenediamine (EDA), triethylamine (EtN3), diisopropylethylamine (DIPEA), DMAP, pyridine, or a combination thereof; 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 a combination thereof; and the reaction is carried out in the presence of CuI; (c) In an optional inert solvent, in the presence of an optional base, propargylamine derivatives react with CO2 and hydrogen sulfide to synthesize thiazolidin-2-one derivatives; Among them, R4 is selected from the following group: H, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted phenyl; R5, R6, and R7 are each independently selected from the group consisting of: H, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, phenyl, 5-12 membered heteroaryl, 5-12 membered saturated or partially unsaturated heterocycle, and said phenyl, heteroaryl, or heterocycle is unsubstituted or substituted with 1-4 substituents 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 form -(CH2) n -, where n is selected from 2, 3, 4, 5, or 6; In step (c), the base is selected from the group consisting of: DBU, TBD, MTBD, DBN, TMG, DABCO, ethylenediamine (EDA), triethylamine (EtN3), diisopropylethylamine (DIPEA), DMAP, pyridine, or a combination thereof; 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 a combination thereof; (d) In an optional inert solvent, in the presence of a base, o-aminobenzonitrile reacts with CO2 and hydrogen sulfide to synthesize thioquinazoline dione derivatives; Wherein, R8 is one or more substituents selected from the group consisting of: H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, NO2, SO2CH3, or a phenyl group that is unsubstituted or substituted with 1-4 substituents selected from the group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; In step (d), the base is selected from the group consisting of: DBU, TBD, MTBD, DBN, TMG, DABCO, ethylenediamine, triethylamine, DIPEA, DMAP, pyridine, or a combination thereof; 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 a combination thereof.

2. A method for preparing carbonyl compounds using carbon dioxide as a carbonylation reagent, characterized in that, The described method includes step (a): (a) In an optional inert solvent, in the presence of a base, o-iodoaniline is reacted with CO2 and hydrogen sulfide to obtain benzothiazolone derivatives; R3 is one or more groups selected from the group consisting of: H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, NH2, NO2, SO2CH3, or phenyl which is unsubstituted or substituted by 1-4 substituents selected from the group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3.

3. A method for preparing carbonyl compounds using carbon dioxide as a carbonylation reagent, characterized in that, The method described above includes step (e): (e) In an optional inert solvent, in the presence of a base, aromatic o-aminodisulfide is reacted with CO2 under the action of hydrogen sulfide to synthesize benzothiazolone derivatives; Among them, the base is selected from the group consisting of: DBU, TBD, MTBD, DBN, TMG, DABCO, ethylenediamine (EDA), triethylamine (EtN3), diisopropylethylamine (DIPEA), DMAP, pyridine, or a combination thereof; 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 a combination thereof.

4. A method for preparing carbonyl compounds using carbon dioxide as a carbonylation reagent, characterized in that, The method described above includes step (f); (f) In an optional inert solvent, in the presence of an optional base, diamine, alkanolamine or mercaptoamine is reacted with CO2 under the action of hydrogen sulfide to synthesize imidazolidinone derivatives, oxazolidinone derivatives or thiazolidinone derivatives; where U is O, S or NR; R is selected from the group consisting of: H, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C1-C6 alkoxy, SO2CH3, or phenyl which is unsubstituted or substituted by 1-4 substituents selected from the group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; M is a substituted or unsubstituted C2-C4 alkylene group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 5-12 membered heteroaryl group, where the substitution means that one or more hydrogen atoms on the group are replaced by substituents selected from the group consisting of: halogen, =O, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 haloalkyl, NO2, SO2CH3, phenyl, 5-12 membered heteroaryl, 3-8 membered cycloalkyl, 5-12 membered saturated or partially unsaturated heterocycle; where the phenyl, heteroaryl, cycloalkyl or heterocycle is unsubstituted or substituted by 1-4 substituents selected from the group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3.

5. A method for preparing carbonyl compounds using carbon dioxide as a carbonylation reagent, characterized in that, The method described above includes step (g): (g) In an optional inert solvent, in the presence of an optional base, an amine is reacted with CO2 under the action of hydrogen sulfide to synthesize urea derivatives; R9 is selected from the group consisting of: H, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, phenyl, 5-12 membered heteroaryl, 5-12 membered saturated or partially unsaturated heterocycle, and said phenyl, heteroaryl or heterocycle is unsubstituted or substituted with 1-4 substituents selected from the group consisting of: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3.

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

7. The method according to claim 1, 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 claim 1, wherein In the reaction described above, the molar ratio of the reaction substrate to the hydrogen sulfide is 1:0.05 - 20.

9. The method according to claim 1, 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 claim 1, characterized in that, In the described reaction, the reaction temperature is from room temperature to 150 °C.

Images