METHOD FOR CATALYTICALLY ACTIVATING CARBON DIOXIDE AS CARBONYLATION REAGENT WITH INORGANIC SULFUR

Abstract

Provided is a method for catalytically activating carbon dioxide as a carbonylation reagent with inorganic sulfur. In the method, carbon dioxide can be used to replace a toxic and harmful carbonylation reagent in the presence of H.sub.2S and an alkali for the synthesis of a carbonyl-containing fine chemical product. The method has a relatively high atomic economy and can reduce the generation of by-products.

Claims

1. A method for preparing carbonyl compounds using carbon dioxide as a carbonylation reagent, wherein the method is performed in the presence of H.sub.2S and a optional base.

2. The method of claim 1, wherein the method comprises step (i) or step (ii): ##STR00158## (i) in an optional inert solvent, reacting a compound of formula Ia with CO.sub.2 in the presence of optional a base and an inorganic sulfur reagent to obtain a compound of formula I; ##STR00159## (ii) in an optional inert solvent, reacting a compound of formula IIa with CO.sub.2 in the presence of a base and an inorganic sulfur reagent to obtain a compound of formula II; Wherein, R.sub.1 and R.sub.2 are each independently selected from the group consisting of: substituted or unsubstituted C.sub.1-C.sub.12 alkyl (e.g. substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.1-C.sub.8 alkyl), substituted or unsubstituted C.sub.3-C.sub.8 cycloalkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, and substituted or unsubstituted C.sub.2-C.sub.6 alkynyl; or R.sub.1 and R.sub.2 together form a group selected from the group consisting of: substituted or unsubstituted C.sub.1-C.sub.6 alkylene, substituted or unsubstituted C.sub.6-C.sub.10 aryl, and substituted or unsubstituted 5-12-membered heteroaryl; ring A is substituted or unsubstituted C.sub.6-C.sub.10aryl, or substituted or unsubstituted 5-12-membered heteroaryl; X and Y are independently selected from the group consisting of: halogen, CN, SH, OH, NH.sub.2, NHR, and NO.sub.2; U and V are independently selected from the group consisting of: NR, S, O, and C(?S)NH; R is selected from the group consisting of: H, substituted or unsubstituted C.sub.1-C.sub.12 alkyl (such as substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.1-C.sub.8 alkyl), substituted or unsubstituted C.sub.3-C.sub.8 cycloalkyl, substituted or unsubstituted C.sub.1-C.sub.6 alkoxy, SO.sub.2CH.sub.3, and phenyl unsubstituted or substituted with 1-4 substituents selected from the group consisting of: halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, OH, NO.sub.2, NH.sub.2, and SO.sub.2CH.sub.3. R.sub.3 is one or more groups on the ring A and selected from the group consisting of: H, halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkyl, NH.sub.2, NO.sub.2, SO.sub.2CH.sub.3, and phenyl unsubstituted or substituted with 1-4 substituents selected from the group consisting of: halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, OH, NO.sub.2, NH.sub.2, SO.sub.2CH.sub.3; or R.sub.5 and R.sub.6 together form a (CH.sub.2).sub.n, wherein, n is selected from 2, 3, 4, 5 or 6; and the substituted means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of: halogen, oxygen atom (i.e., ?O), C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkyl, NO.sub.2, SO.sub.2CH.sub.3, phenyl, 5-12-membered heteroaryl, 3-8-membered cycloalkyl, 5-12-membered saturated or partially unsaturated heterocycle; wherein, the phenyl, heteroaryl, cycloalkyl or heterocycle is unsubstituted or substituted by 1-4 substituents selected from the group consisting of: halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6alkoxy, OH, NO.sub.2, NH.sub.2, and SO.sub.2CH.sub.3; or, two substituents adjacent or attached to the same carbon atom together form a (CH.sub.2).sub.n, wherein, n is selected from 2, 3, 4, 5 or 6.

3. The method of claim 1, wherein the base is an organic base; preferably, the base is selected from the group consisting of: C.sub.1-C.sub.12tertiary amines, C.sub.1-C.sub.12secondary amines, C.sub.1-C.sub.12primary amines, C.sub.2-C.sub.12 amidines, C.sub.2-C.sub.12 guanidines, C.sub.3-C.sub.12 pyridines, C.sub.3-C.sub.12 imidazoles; preferably, the base is selected from the group consisting of: DBU, TBD, MTBD, DBN, TMG, DABCO, ethylenediamine (EDA), triethylamine (EtN.sub.3), diisopropylethylamine (DIPEA), DMAP, pyridine, and combinations thereof; preferably, the molar ratio of the reaction substrate to the base is 1:0-5 (e. g., 1:0.1-5).

4. The method of claim 1, wherein the method comprises steps (a), (b), (c), (d), (e), (f) or (g); ##STR00160## (a) in an optional inert solvent, reacting an o-iodoaniline with CO.sub.2 and H.sub.2S in the presence of a base to obtain a benzothiazolone derivative; ##STR00161## (b) in an optional inert solvent, reacting an o-nitroiodobenzene with CO.sub.2 and H.sub.2S in the presence of a base to synthesize a benzothiazolone derivative; ##STR00162## (c) in an optional inert solvent, reacting a propargylamine derivative with CO.sub.2 and H.sub.2S in the presence of an optional base to synthesize a thiazolidin-2-one derivative; wherein, R.sub.4 is selected from the group consisting of: H, substituted or unsubstituted C.sub.1-C.sub.12alkyl, substituted or unsubstituted C.sub.3-C.sub.8cycloalkyl, and substituted or unsubstituted phenyl; R.sub.5, R.sub.6 and R.sub.7 are independently selected from the group consisting of: H, substituted or unsubstituted C.sub.1-C.sub.12alkyl, substituted or unsubstituted C.sub.3-C.sub.8cycloalkyl, phenyl, 5-12 membered heteroaryl, and 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, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, OH, NO.sub.2, NH.sub.2, SO.sub.2CH.sub.3; or R.sub.5 and R.sub.6 together form a (CH.sub.2).sub.n, wherein, n is selected from 2, 3, 4, 5 or 6; ##STR00163## (d) in an optional inert solvent, reacting an o-aminobenzonitrile with CO.sub.2 and H.sub.2S in the presence of a base to synthesize a thioquinazolindione derivative; wherein, R.sub.8 is one or more substituents on the benzene ring and selected from the group consisting of: H, halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6haloalkyl, NO.sub.2, SO.sub.2CH.sub.3, and phenyl unsubstituted or substituted with 1-4 substituents selected from the group consisting of: halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, OH, NO.sub.2, NH.sub.2, and SO.sub.2CH.sub.3; ##STR00164## (e) in an optional inert solvent, in the presence of a base, reacting an aromatic o-aminodisulfide with CO.sub.2 in the presence of H.sub.2S to synthesize a benzothiazolone derivative; ##STR00165## (f) In an optional inert solvent, in the presence of an optional base, reacting an diamine, an alcoholamine or a mercaptoamine with CO.sub.2 in the presence of H.sub.2S to synthesize an imidazolidinone derivative, an oxazolidinone derivative or a thiazolidinone derivative; wherein U is O, S or NR; M is substituted or unsubstituted C.sub.2-C.sub.4alkylene, substituted or unsubstituted phenyl, or substituted or unsubstituted 5-12 membered heteroaryl, wherein the definition of the substituted is as described in claim 2; (g) in an optional inert solvent, in the presence of an optional base, reacting an amine with CO.sub.2 in the presence of H.sub.2S to synthesize a urea derivative; ##STR00166## each R.sub.9 are selected from the group consisting of: H, substituted or unsubstituted C.sub.1-C.sub.12alkyl (such as substituted or unsubstituted C.sub.1-C.sub.6alkyl, substituted or unsubstituted C.sub.1-C.sub.8alkyl), substituted or unsubstituted C.sub.3-C.sub.8cycloalkyl, phenyl, 5-12-membered heteroaryl, and 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, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, OH, NO.sub.2, NH.sub.2, and SO.sub.2CH.sub.3.

5. The method of claim 1, wherein the inert solvent is selected from the group consisting of NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH.sub.2Cl.sub.2, CHCl.sub.3, CCl.sub.4, toluene, ethyl acetate, supercritical CO.sub.2, and combinations thereof.

6. The method of claim 1, wherein in the reaction, the molar ratio of the reaction substrate to the CO.sub.2 is 1:1-100.

7. The method of claim 1, wherein during the reaction, the CO.sub.2 is continuously introduced into the reactor, and the pressure of the CO.sub.2 in the reactor is 0.1-12 MPa.

8. The method of claim 1, wherein in the reaction, the molar ratio of the reaction substrate to H.sub.2S is 1:0.05-20.

9. The method according to claim 1, wherein during the reaction, H.sub.2S is continuously introduced into the reactor, and the pressure of H.sub.2S in the reactor is 0.05-1.5 MPa.

10. The method according to claim 1, wherein the reaction temperature is from room temperature to 150? C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0042] After a long and thorough research, the present inventors unexpectedly found that H.sub.2S can be used as a catalyst to catalyze the reaction of CO.sub.2 as a carbonyl source with a series of substrates to prepare carbonylated compounds with high efficiency. This carbonylation reaction can occur alone or together with other reactions involving CO.sub.2 or H.sub.2S to prepare a series of products, which has potential application value in the field of fine chemical synthesis. Based on the above findings, the inventors completed the present invention.

Synthesis of CO.SUB.2 .as Carbonylation Reagents

[0043] The present invention provides a method for preparing carbonyl compounds using carbon dioxide as a carbonylation reagent, wherein the method is performed in the presence of H.sub.2S.H.sub.2S can be used as a catalyst only, or as a reactant at the same time as the catalyst, thereby reacting further with the reaction substrate or generating an intermediate.

[0044] Specifically, the method comprises step (i) or step (ii):

##STR00010## [0045] (i) in an inert solvent, reacting a compound of formula Ia with CO.sub.2 in the presence of a base and an inorganic sulfur reagent to obtain a compound of formula I (wherein the compound of formula Ia can be a mixture of R.sub.1X and R.sub.2Y, or a compound with two reactive functional groups X and Y formed by R.sub.1X and R.sub.2Y together);

##STR00011## [0046] (ii) in an inert solvent, reacting a compound of formula IIa with CO.sub.2 in the presence of a base and an inorganic sulfur reagent to obtain a compound of formula II. [0047] wherein, the definition of each group is as described above.

[0048] In a preferred embodiment of the present invention, the step is carried out in the presence of a base, which may preferably be an organic base. Preferably, the base is selected from the group consisting of: C.sub.1-C.sub.12 tertiary amines, C.sub.1-C.sub.12 secondary amines, C.sub.1-C.sub.12 primary amines, C.sub.2-C.sub.12 amidines, C.sub.2-C.sub.12 guanidines, C.sub.3-C.sub.12 pyridines, C.sub.3-C.sub.12 imidazoles, DBU, TBD, MTBD, DBN, TMG, DABCO, ethylenediamine, triethylamine, DIPEA, DMAP, pyridine, and combinations thereof; preferably, the molar ratio of the reaction substrate to the base is 1:0.1-5.

[0049] In the method, a conventional inert solvent that does not affect the reaction may be used, and the preferred solvent includes: NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH.sub.2Cl.sub.2, CHCl.sub.3, CCl.sub.4, toluene, ethyl acetate, or a combination thereof. In particular, since the method of the invention requires the use of a CO.sub.2 flow, a preferred embodiment is to use supercritical CO.sub.2 as a solvent.

[0050] The molar ratio of reaction substrate to CO.sub.2 in the method is not particularly limited, which can be 1:1-100.

[0051] In the reaction process, CO.sub.2 is continuously introduced into the reactor. In a preferred reaction method, the pressure of the CO.sub.2 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.

[0052] In the reaction, the molar ratio of the reaction substrate to the inorganic sulfur is preferably 1:0.05-20.

[0053] In the reaction process, H.sub.2S is continuously introduced into the reactor, and preferably the pressure of the H.sub.2S 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, or 1.4 MPa.

[0054] The temperature of the reaction is not particularly limited, and preferably can be carried out at room temperature (typically 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., or 140? C.

[0055] The above reaction can be used to prepare a series of compounds with characteristic structures, for example, compounds with corresponding structural units can be prepared by steps (a), (b), (c), (d), (e) or (f);

(a) Synthesis of Benzothiazolone Derivatives by the Reaction of o-Iodoaniline with CO.SUB.2 .and H.SUB.2.S

[0056] ##STR00012##

[0057] In an inert solvent, reacting an o-iodoaniline with CO.sub.2 and H.sub.2S in the presence of a base to obtain a benzothiazolone derivative. In the above reaction, the base is preferably DABCO, DBU, TBD, or Et.sub.3N; more preferably DBU or Et.sub.3N. The solvent is preferably NMP or DMF, and the amount of base is preferably 1-3 equivalents. In particular, when the reactant is an organic base or can be used as a solvent, the reaction may also be carried out without a solvent or without an organic base.

[0058] In another preferred embodiment, in step (a), the pressure ratio of the CO.sub.2 to the H.sub.2S is (1-8):(0.1-0.8).

[0059] In another preferred embodiment, in step (a), the process is reacted at 70-100? C., preferably 80-90? C.

[0060] In another preferred embodiment, in step (a), in the process, the pressure of the CO.sub.2 in the reactor is 2-5 MPa, and the pressure of the H.sub.2S in the reactor is 0.3-0.5 MPa.

(b) Synthesis of Benzothiazolone Derivatives by the Reaction of o-Nitroiodobenzene with CO.SUB.2 .and H.SUB.2.S

[0061] ##STR00013##

[0062] In an inert solvent, reacting an o-nitroiodobenzene with CO.sub.2 and H.sub.2S in the presence of a base to synthesize a benzothiazolone derivative. In the above reaction, the base is preferably DBU or Et.sub.3N; the solvent is preferably NMP or NMP/H.sub.2O; and the amount of base is preferably 2-5 equivalents, preferably 2-4 equivalents.

[0063] In another preferred embodiment, in step (b), the pressure ratio of CO.sub.2 to H.sub.2S is (1-8):(0.5-1.5), preferably 2-4:1.

[0064] In another preferred embodiment, the reaction may be carried out under CuI catalysis.

[0065] In another preferred embodiment, in step (b), the process is reacted at 70-100? C., preferably 80-90? C. In another preferred embodiment, in step (a), in the process, the pressure of the CO.sub.2 in the reactor is 2-5 MPa, and the pressure of the H.sub.2S in the reactor is 0.5-1 MPa.

[0066] ##STR00014##

[0067] In an inert solvent, reacting an propargylamine derivative with CO.sub.2 and H.sub.2S in the presence of a base to synthesize a thiazolidin-2-one derivative. [0068] wherein, R.sub.4 is selected from the group consisting of: H, substituted or unsubstituted C.sub.1-C.sub.6alkyl; [0069] R.sub.5, R.sub.6 and R.sub.7 are independently selected from the group consisting of: H, substituted or unsubstituted C.sub.1-C.sub.6alkyl, and phenyl unsubstituted or substituted with 1-3 substituents selected from the group consisting of: halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, OH, NO.sub.2, NH.sub.2, SO.sub.2CH.sub.3; or R.sub.5 and R.sub.6 together form a (CH.sub.2).sub.n, wherein, n is selected from 2, 3, 4, 5 or 6;

[0070] In the above reaction, the base is preferably DBU, Et.sub.3N, TBD or K.sub.2CO.sub.3, more preferably DBU, Et.sub.3N or TBD; the solvent is preferably CH.sub.3OH, DMF, NMP or DMSO, preferably DMSO; and the amount of the base is preferably 0.5-1.5 equivalents, preferably 0.6-1.2 equivalents.

[0071] In another preferred embodiment, in step (c), the pressure ratio of the CO.sub.2 to the H.sub.2S is 1:(0.2-1.5), preferably 1:0.8-1.2.

[0072] In another preferred embodiment, in step (c), the process is reacted at 20-60? C., preferably at 20-40? C.

[0073] In another preferred embodiment, in step (c), in the process, the pressure of the CO.sub.2 in the reactor is 0.8-1.2 MPa, and the pressure of the H.sub.2S in the reactor is 0.5-1 MPa (preferably 0.8-1 MPa).

(d) Synthesis of Thiobenzamide or Thioquinazolindione Derivatives by the Reaction of Orthoaminobenzonitrile with CO.SUB.2 .and H.SUB.2.S

[0074] ##STR00015##

[0075] In an inert solvent, reacting an o-aminobenzonitrile with CO.sub.2 and H.sub.2S in the presence of a base to synthesize a thiobenzamide or a thioquinazolindione derivative; in the reaction, CO.sub.2 and H.sub.2S are both used as reactants 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 is preferably 0.2-2 equivalents, preferably 0.8-2 equivalents.

[0076] In another preferred embodiment, in step (d), the pressure ratio of CO.sub.2 to H.sub.2S is (2-5):(0.2-1.2), preferably 3-10:1.

[0077] In another preferred embodiment, in step (d), the process is reacted at 40-60? C., preferably 45-55? C. In another preferred embodiment, in step (d), in the process, the pressure of the CO.sub.2 in the reactor is 2-5 MPa, and the pressure of the H.sub.2S in the reactor is 0.4-1 MPa.

(e) Synthesis of Benzothiazolone Derivatives by the Reaction of Aromatic o-Aminodisulfides with CO.SUB.2 .in the Presence of H.SUB.2.S

[0078] ##STR00016##

[0079] In an inert solvent, in the presence of a base, reacting an aromatic o-aminodisulfide with CO.sub.2 in the presence of H.sub.2S to synthesize a benzothiazolone derivative; in the above reaction, the base is preferably DBU, TMG, or Et.sub.3N; the solvent is preferably NMP, CH.sub.3OH, 1,4-dioxane, or DMSO, more preferably NMP; the amount of base used is preferably 0.2-2 equivalents, more preferably 0.4-1.2 equivalent.

[0080] In another preferred embodiment, in step (e), the pressure ratio of the CO.sub.2 to the H.sub.2S is (1-5):(0.1-1.2).

[0081] In another preferred embodiment, in step (e), the process is reacted at 25-100? C., preferably at 80-90? C.

[0082] In another preferred embodiment, in step (e), in the process, the pressure of the CO.sub.2 in the reactor is 1-5 MPa, and the pressure of the H.sub.2S in the reactor is 0.2-1.0 MPa.

(f) Synthesis of Imidazolidinone (Oxazolidinone or Thiazolidinone) Derivatives by the Reaction of Diamine, Alcoholamine or Mercaptoamine with CO.SUB.2 .in the Presence of H.SUB.2.S

[0083] ##STR00017## [0084] in an optional inert solvent, in the presence of an optional base, reacting a diamine, an alcoholamine or a mercaptoamine with CO.sub.2 in the presence of H.sub.2S to synthesis an imidazolidinone derivative, an oxazolidinone derivative or a thiazolidinone derivative; [0085] wherein, U is O, S or NR; [0086] M is substituted or unsubstituted C.sub.2-C.sub.4alkylene, substituted or unsubstituted phenyl, or substituted or unsubstituted 5-12 membered heteroaryl, wherein the definition of substitutions are as described above.

When U is NR and M is a Substituted or Unsubstituted Phenyl, or a Substituted or Unsubstituted 5-12-Membered Heteroaryl Group

[0087] In the above reaction, the base is preferably DABCO, DBU, TMG or Et.sub.3N, preferably DBU or TMG; the solvent is preferably NMP, DMF, ethylene glycol or dichloromethane, preferably NMP; and the amount of the base is preferably 0.1-2 equivalents. In particular, when the reactant is an organic base or can be used as a solvent, the reaction may also be carried out without a solvent or without an organic base.

[0088] In another preferred embodiment, in step (f), the pressure ratio of CO.sub.2 to H.sub.2S is (1-65):1.

[0089] In another preferred embodiment, in step (f), the process is reacted at 20-60? C., preferably at 30-50? C. In another preferred embodiment, in step (f), in the process, the pressure of the CO.sub.2 in the reactor is 1-5 MPa, and the pressure of the H.sub.2S in the reactor is 0.05-1.5 MPa.

When U is NR and M is a Substituted or Unsubstituted C.SUB.2.-C.SUB.4.Alkylene

[0090] In the above reaction, the base is preferably DBU, TBD, DIPEA or Et.sub.3N, preferably DBU, DIPEA or Et.sub.3N; the solvent is preferably NMP, DMF, ethylene glycol or dichloromethane, preferably NMP; and the amount of base is preferably 0.1-1 equivalent, more preferably 0.2-0.6 equivalent. In particular, when the reactant is an organic base or can be used as a solvent, the reaction may also be carried out without a solvent or without an organic base.

[0091] In another preferred embodiment, in step (f), the pressure ratio of CO.sub.2 to H.sub.2S is (3-35):1, preferably (3-25):1.

[0092] In another preferred embodiment, in step (f), the process is reacted at 80-120? C.

[0093] In another preferred embodiment, in step (f), in the process, the pressure of the CO.sub.2 in the reactor is 1-5 MPa, and the pressure of the H.sub.2S in the reactor is 0.2-1 MPa.

When U is S

[0094] In the above reaction, the base is preferably DABCO, DBU, TMG, TBD or Et.sub.3N, preferably DBU, Et.sub.3N, or TMG; the solvent is preferably NMP, DMF, ethylene glycol or dichloromethane, preferably NMP or DMF; and the amount of base is preferably 0.1-2 equivalents.

[0095] In particular, when the reactant is an organic base or can be used as a solvent, the reaction may also be carried out without a solvent or without an organic base. In addition, it can also be performed in the absence of solvent when the pressure of CO.sub.2 and the reaction temperature are compatible with the conditions for the formation of supercritical CO.sub.2.

[0096] In another preferred embodiment, in step (f), the pressure ratio of CO.sub.2 to H.sub.2S is (3-25):1.

[0097] In another preferred embodiment, in step (f), the process is reacted at 20-60? C., preferably at 30-50? C.

[0098] In another preferred embodiment, in step (f), in the process, the pressure of the CO.sub.2 in the reactor is 3-12 MPa, and the pressure of the H.sub.2S in the reactor is 0.2-1.0 MPa.

(g) Synthesis of Urea Derivatives by the Reaction of Benzylamine and CO.SUB.2 .in the Presence of H.SUB.2.S

[0099] ##STR00018## [0100] in an optional inert solvent, in the presence of an optional base, reacting an amine with CO.sub.2 in the presence of H.sub.2S to synthesis an urea derivative.

[0101] R.sub.9 are selected from the group consisting of: H, substituted or unsubstituted C.sub.1-C.sub.12alkyl (such as substituted or unsubstituted C.sub.1-C.sub.6alkyl, substituted or unsubstituted C.sub.1-C.sub.8alkyl), substituted or unsubstituted C.sub.3-C.sub.8cycloalkyl, phenyl, 5-12-membered heteroaryl, and 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, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, OH, NO.sub.2, NH.sub.2, and SO.sub.2CH.sub.3;

[0102] In the above reaction, the base is preferably DBU, TMG or Et.sub.3N, preferably DBU; the solvent is preferably NMP, DMF or methanol, preferably NMP; the amount of base is preferably 0.1-2 equivalents, however, since the substrate organic amine can be used as a base or solvent, the reaction can also be carried out in the absence of an organic base, and/or in the absence of a solvent.

[0103] In another preferred embodiment, in step (f), the pressure ratio of CO.sub.2 to H.sub.2S is (5-20):1.

[0104] In another preferred embodiment, in step (f), the method is reacted at 90-130? C., preferably at 30-50? C.

[0105] In another preferred embodiment, in step (f), in the process, the pressure of the CO.sub.2 in the reactor is 5-20 MPa, and the pressure of the H.sub.2S in the reactor is 0.5-2 MPa.

[0106] The present invention is 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 following embodiments do not indicate the specific conditions of the experimental method, usually according to the conventional conditions, or according to the conditions recommended by the manufacturer. Percentages and servings are calculated by weight unless otherwise stated.

Class I Inorganic Sulfur as Both Raw Material and Catalyst

Example 1 Synthesis of Benzothiazolone Derivatives by the Reaction of o-Iodoaniline with CO.SUB.2 .and H.SUB.2.S

[0107] ##STR00019##

The Reaction Method is as Follows

[0108] 1 mol of o-halogenated aniline, 2 mol of base, 0.2 mol of cuprous iodide (CuI) and 2 ml of solvent were weighed and added into the reactor sequentially and the reactor was tightened. The corresponding amount of H.sub.2S was introduced into the reactor, and the reaction was stirred at 90? C. for 30 min, then the corresponding amount of CO.sub.2 was introduced into the reactor, and the reaction was continued to be stirred at the corresponding temperature for 24 h. After the reaction, the reactor was cooled to room temperature, and the reactor was opened after the gas in the reactor was slowly exhausted, then the reaction mixture was transferred to a 250 ml partition funnel and extracted with ethyl acetate. The organic phase was dried with anhydrous magnesium sulfate, then separated by column chromatography to obtained the product.

[0109] The conditions were optimized according to the above steps, and the reaction results are shown in the following table:

TABLE-US-00001 Sol- T molar ratio (o- P(MPa) Yield Entry vent base (? C.) iodoaniline:DBU) CO.sub.2 H.sub.2S (%) 1 NMP DABCO 90 1:2 3 0.3 0 2 NMP DBU 90 1:2 3 0.3 95 3 NMP TBD 90 1:2 3 0.3 56 4 NMP Et.sub.3N 90 1:2 3 0.3 90 6 NMP 90 1:0 3 0.3 0 7 NMP DBU 90 1:2 5 0.3 87 8 NMP DBU 90 1:2 2 0.3 88 9 NMP DBU 90 1:2 3 0 0 10 NMP DBU 90 1:2 3 0.5 90 11 DMF DBU 90 1:2 3 0.5 76 12 NMP DBU 80 1:2 3 0.5 89 13 NMP DBU 70 1:2 3 0.5 78 14 NMP DBU 100 1:2 3 0.5 91 Note: In each of the above entries, the raw material was 1 mmol o-iodoaniline; the solvent used was 2 ml; CuI used was 0.2 mmol; and reacted for 24 h.

Using the Method as in Entry 2 Above While Changing Other Reaction Substrates, the Following Individual Products were Obtained

Characterization of Compounds

[0110] ##STR00020##

[0111] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=4:1 as developing solvent, 144 mg of white solid benzothiazolone was obtained with a yield after separation of 95%.

[0112] Characterization data of benzothiazol-2-one (2a): .sup.1H NMR (CDCl.sub.3, 500 MHz): ? (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). .sup.13C NMR (CDCl.sub.3, 125 MHz): ? (ppm) 172.8, 135.3, 126.5, 123.9, 123.3, 122.6, 111.7; MS (EI): m/z calcd for C.sub.7H.sub.5NOS [M].sup.+: 151.0, found 151.0. m.p.: 139-140? C.

##STR00021##

[0113] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=3:1 as developing agent, 138 mg of white solid was obtained with a yield after separation of 84%.

[0114] Characterization data of 6-methylbenzothiazol-2-one:.sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (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); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (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].sup.+: 166.0, found 165.0. m.p.: 170-171? C.

##STR00022##

[0115] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=2:1 as developing agent, 13 4 mg of white solid was obtained with a yield after separation of 82%.

[0116] Characterization data of 5-methylbenzothiazole-2-one:.sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (ppm) 11.79 (s, 1H), 7.42 (d, J=7.9 Hz, 1H), 6.98-6.91 (m, 2H), 2.32 (s, 3H). .sup.13C NMR (DMSO-d.sub.6, 126 MHz) ? (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.

##STR00023##

[0117] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=3:1 as developing agent, 158 mg of white solid was obtained with a yield after separation of 88%.

[0118] Characterization data of 6-methoxybenzothiazol-2-one:.sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (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, J.sub.1=8.5 Hz, J.sub.2=2.5 Hz), 3.73(s, 3H); 13C NMR (DMSO-d.sub.6, 126 MHz): ? (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].sup.+: 182.1, found 181.1.

##STR00024##

[0119] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=3:1 as developing agent, 144 mg of white solid was obtained with a yield after separation of 85%.

[0120] Characterization data of 6-fluorobenzothiazole-2-one: .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? (ppm) 11.91 (s, 1H), 7.57 (ddt, J=9.1, 2.2, 0.8 Hz, 1H), 7.16-7.08 (m, 2H). .sup.13C NMR (DMSO-d.sub.6, 126 MHz) ? (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.

##STR00025##

[0121] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=3:1 as developing agent, 175 mg of white solid was obtained with a yield after separation of 81%.

[0122] Characterization data of 6-trifluoromethylbenzothiazol-2-one: .sup.1H NMR (DMSO-d 6,500 MHz): ? (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-d 6, 125 MHz): ? (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.

##STR00026##

[0123] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=20:1 as developing agent, 144 mg of white solid was obtained with a yield after separation of 63%.

[0124] Characterization data of 6-bromobenzothiazol-2-one: .sup.1H NMR (DMSO-d.sub.6, 500 MHZ): ? (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); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (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.

##STR00027##

[0125] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=100:3 as developing agent, 121 mg of white solid was obtained with a yield after separation of 66%.

[0126] Characterization data of 6-chlorobenzothiazol-2-one: .sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (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); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (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.

##STR00028##

[0127] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=100:3 as developing agent, 124 mg of white solid was obtained with a yield after separation of 76%.

[0128] Characterization data of 2-methylbenzothiazole -2-one: .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? (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). .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? (ppm)137.61, 126.60, 123.17, 122.70, 121.28, 111.32.

##STR00029##

[0129] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=3:1 as developing agent, 110 mg of white solid was obtained with a yield after separation of 67%.

[0130] Characterization data of 6-aminobenzothiazole-2-one: .sup.1H NMR (500 MHz, DMSO-d6) ? (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) ? (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.

Example 2 Synthesis of Benzothiazolone Derivatives by the Reaction of o-Nitroiodobenzene with CO.SUB.2 .and H.SUB.2.S

[0131] ##STR00030##

[0132] The reaction method was as follows:

[0133] 1 mmol of o-halogenated nitrobenzene, 2 mmol of base, 0.2 mmol of cuprous iodide (CuI) and 2 ml of solvent were weighed and added to the reactor sequentially and the reactor was tightened. The corresponding amount of H.sub.2S was introduced into the reactor, and the reaction was stirred at the corresponding temperature for 30 min, then the corresponding amount of CO.sub.2 was introduced into the reactor, and the reaction was continued to be stirred at the corresponding temperature for 24 h. After the reaction, the reactor was cooled to room temperature, and the reactor was opened after the gas in the reactor was slowly exhausted, then the reaction mixture was transferred to a 250 ml partition funnel and extracted with ethyl acetate. The organic phase was dried with anhydrous magnesium sulfate, and separated by column chromatography to obtain the product.

[0134] The conditions were optimized according to the above steps, and the reaction results were shown in the following table:

TABLE-US-00002 o-iodine P(MPa) Entry base Additive Solvent T/? C. nitrobenzene:base CO.sub.2 H.sub.2S Yield (%) 1 DBU NMP 90 1:3 3 0.5 0 2 DBU NMP/H.sub.2O 90 1:3 3 0.5 0 3 Et.sub.3N NMP 90 1:3 3 0.5 31 4 Et.sub.3N NMP/H.sub.2O 90 1:3 3 1 32 5 Et.sub.3N H.sub.2O 90 1:3 3 1 0 6 Et.sub.3N NMP 90 1:3 3 1 32 7 DBU CuI NMP 90 1:3 3 1 34 8 Et.sub.3N CuI NMP 90 1:2 3 1 75 9 Et.sub.3N CuI NMP 90 1:3 3 1 90 10 Et.sub.3N CuI NMP 90 1:4 3 1 86 11 Et.sub.3N CuI NMP 80 1:3 3 1 76 Note: in each of the above entries, the raw material was 1 mmol o-iodonitrobenzene; the solvent used was 2 ml; CuI used was 0.2 mmol; and was reacted for 24 h.

Using the Method as in Entry 9 Above While Changing Other Reaction Substrates, the Following Individual Products were Obtained

[0135] ##STR00031##

[0136] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=3:1 as developing agent, 117 mg of white solid was obtained with a yield after separation of 71%.

[0137] Characterization data of 5-methylbenzothiazole-2-one: .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? (ppm) 11.80 (s, 1H), 7.42 (d, J=7.9 Hz, 1H), 6.97-6.92 (m, 2H), 2.32 (s, 3H). .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? (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.

##STR00032##

[0138] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=3:1 as developing agent, 117 mg of white solid was obtained with a yield after separation of 71%.

[0139] Characterization data of 7-methylbenzothiazole-2-one: 1H NMR (500 MHz, DMSO-d6) ? 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) ? (ppm) 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.

##STR00033##

[0140] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=3:1 as developing agent, 127 mg of white solid was obtained with a yield after separation of 70%.

[0141] Characterization data of 5-methoxybenzothiazole-2-one: .sup.1H NMR (500 MHz, DMSO-d6) ? (ppm)11.80 (s, 1H), 7.44 (d, J=8.7 Hz, 1H), 6.74 (dd, J=8.7, 2.5 Hz, 1H), 6.66 (d, J=2.5 Hz, 1H), 3.75 (s, 3H). .sup.13C NMR (126 MHz, DMSO-d6) ? (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.

##STR00034##

[0142] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=3:1 as developing agent, 140 mg of white solid was obtained with a yield after separation of 67%.

[0143] Characterization data of 5-methyl ester benzothiazole-2-one: .sup.1H NMR (500 MHz, DMSO-d6) ? (ppm) 12.14 (s, 1H), 7.75-7.68 (m, 3H), 7.63 (s, 1H), 3.87 (s, 4H). .sup.13C NMR (126 MHz, DMSO-d6) ? (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.

##STR00035##

[0144] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=5:1 as developing agent, 116 mg of white solid was obtained with a yield after separation of 63%.

[0145] Characterization data of 7-chlorobenzothiazole-2-one: .sup.1H NMR (500 MHz, DMSO-d6) ? (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). .sup.13C NMR (126 MHz, DMSO-d6) ? (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.

##STR00036##

[0146] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=3:1 as developing agent, 126 mg of white solid was obtained with a yield after separation of 75%.

[0147] Characterization data of 5-fluorobenzothiazole-2-one: .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? (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). .sup.13C NMR (DMSO-d.sub.6, 126 MHz) ? (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.

##STR00037##

[0148] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=3:1 as developing agent, 118 mg of white solid was obtained with a yield after separation of 64%.

[0149] Characterization data of 5-chlorobenzothiazole-2-one: .sup.1H NMR (500 MHz, DMSO-d6) ? (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). .sup.13C NMR (126 MHz, DMSO-d6) ? (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.

##STR00038##

[0150] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=3:1 as developing agent, 154 mg of white solid was obtained with a yield after separation of 67%.

[0151] Characterization data of 5-bromobenzothiazol-2-one: .sup.1H NMR (500 MHz, DMSO-d6) ? (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). .sup.13C NMR (126 MHz, DMSO-d6) ? (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.

Example 3 Synthesis of Thiazolidine-2-One Derivatives by Reaction of Propargylamine with CO.SUB.2 .and H.SUB.2.S

[0152] ##STR00039##

[0153] 2 mmol of propargylamine, 1.2 mmol of base and 2 mL of solvent were added into a 10 mL reactor, a magnet was placed and the reactor was tightened. After the air in the reactor was replaced with N.sub.2 gas for three times, the corresponding amount of H.sub.2S was introduced, and stirred until the pressure was stabilized. 1 MPa CO.sub.2 was introduced, and the reaction was stirred at the corresponding temperature for 24 h. The reaction mixture was extracted with ethyl acetate after the reaction was completed, then the organic phase was collected and combined, dried with anhydrous magnesium sulfate for 30 min, filtered to remove the desiccant, and the solvent was removed under reduced pressure to obtain the crude product. The crude product was purified by column chromatography (eluent: petroleum ether/ethyl acetate or dichloromethane/methanol) to obtain the target product.

[0154] The conditions were optimized according to the above steps, and the results are shown in the following table:

TABLE-US-00003 base P(MPa) Yield Entry (equiv.) Solvent H.sub.2S CO.sub.2 T(? C.) (%) 1 DBU(1.0) DMSO 1 1 60 68 2 DBU(1.0) DMSO 1 1 25 81 3 DBU(0.6) DMSO 1 1 25 81 4 Et.sub.3N(0.6) DMSO 1 1 25 71 5 TBD(0.6) DMSO 1 1 25 80 6 K.sub.2CO.sub.3(0.6) DMSO 1 1 25 39 Note: the raw material is 2 mmol: 2-methyl -3 butyne -2-amine; the solvent are 2 ml; and reacted for 24 hours.

Using the Method as in Entry 3 Above While Changing Other Reaction Substrates, the Following Individual Products were Obtained

Characterization of Compounds

[0155] ##STR00040##

[0156] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=1:2 as developing agent, the yield after separation was 24%.

[0157] 5-methylenethiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 6.53 (s, 1H), 5.23 (q, J=2.2 Hz, 1H), 5.18-5.11 (m, 1H), 4.31 (s, 2H) ppm; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 173.1, 138.8, 106.9, 49.4 ppm; HRMS(ESI) m/z:[M+H].sup.+ Calcd for C.sub.4H.sub.5NOS 116.0165; Found 116.0167.

##STR00041##

[0158] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=2:1 as developing agent, the yield after separation was 81%.

[0159] 4,4-dimethyl-5-methylenethiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 6.32 (s, 1H), 5.19 (d, J=2.2 Hz, 1H), 5.11-5.06 (m, 1H), 1.50 (s, 6H) ppm; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 169.7, 149.3, 104.9, 62.7, 29.9 ppm; HRMS(ESI) m/z: [M+H].sup.+ Calcd for C.sub.6H.sub.9NOS 144.0478; Found 144.0474

##STR00042##

[0160] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:methanol (V/V)=200:1 as developing agent, the yield after separation was 80%.

[0161] (Z)-5-benzylidene-3-butyl-4,4-diethylthiazolidin-2-one:.sup.1H NMR (500 MHz, CDCl.sub.3) ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.18H.sub.25NOS 304.1730; Found 304.1725.

##STR00043##

[0162] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=2:1 as developing agent, the yield after separation was 92%.

[0163] (Z)-4-benzylidene-1-butyl-3-thia-1-azaspiro[4.5]decan-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.19H.sub.25NOS 316.1730; Found 316.1722.

##STR00044##

[0164] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=3:1 as developing agent, the yield after separation was 92%.

[0165] (Z)-5-benzylidene-3-butyl-4-phenylthiazolidin-2-one: According to 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.; .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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.sub.20H.sub.21NOS 324.1417; Found 324.1409.

##STR00045##

[0166] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=2:1 as developing agent, the yield after separation was 99%.

[0167] (Z)-4-benzyl-5-benzylidene-3-butylthiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.21H.sub.23NOS 338.1573; Found 338.1542.

##STR00046##

[0168] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=2:1 as developing agent, the yield after separation was 90%.

[0169] (Z)-5-benzylidene-3-butyl-4-propylthiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.17H.sub.23NOS 290.1573; Found 290.1558.

##STR00047##

[0170] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=2:1 as developing agent, the yield after separation was 92%.

[0171] (Z)-3-butyl-4,4-dimethyl-5-(4-methylbenzylidene)thiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.17H.sub.23NOS 290.1573; Found 290.1568.

##STR00048##

[0172] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=2:1 as developing agent, the yield after separation was 81%.

[0173] (Z)-3-butyl-5-(4-methoxybenzylidene)-4,4-dimethylthiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.17H.sub.23NO.sub.2S 306.1522; Found 306.1516.

##STR00049##

[0174] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=2:1 as developing agent, the yield after separation was 83%.

[0175] (Z)-3-butyl-5-(4-chlorobenzylidene)-4,4-dimethylthiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 7.33 (d, J=8.5 Hz, 2H), 7.26 (d, J=8.7 Hz, 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=7.3 Hz, 3H) ppm; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 166.5, 140.5, 134.7, 132.8, 129.4, 128.9, 117.8, 68.1, 42.6, 31.7, 28.3, 20.5, 13.9 ppm; HRMS(ESI) m/z: [M+H].sup.+ Calcd for C.sub.16H.sub.20ClNOS 310.1027; Found 310.1021.

##STR00050##

[0176] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=1:2 as developing agent, the yield after separation was 87%.

[0177] (Z)-5-benzylidene-4.4-dimethylthiazolidin-2-one: .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 8.79 (s, 1H), 7.43-7.33 (m, 4H), 7.25 (t, J=7.3 Hz, 1H), 6.74 (s, 1H), 1.50 (s, 6H) ppm; .sup.13C NMR (125 MHz, DMSO-d.sub.6) ? 166.1, 140.8, 136.0, 128.6, 127.7, 126.9, 118.7, 63.5, 29.7 ppm; HRMS(ESI) m/z: [M+H].sup.+ Calcd for C.sub.12H.sub.13NOS 220.0791; Found 220.0788.

##STR00051##

[0178] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=2:1 as developing agent, the yield after separation was 94%.

[0179] (Z)-5-benzylidene-4,4-dimethyl-3-propylthiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) 1 ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.15H.sub.19NOS 262.1260; Found 262.1257.

##STR00052##

[0180] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=2:1 as developing agent, the yield after separation was 87%.

[0181] (Z)-5-benzylidene-3-butyl-4,4-dimethylthiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.16H.sub.21NOS 276.1417; Found 276.1416.

##STR00053##

[0182] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=2:1 as developing agent, the yield after separation was 89%.

[0183] (Z)-3-benzyl-5-benzylidene-4,4-dimethylthiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.19H.sub.19NOS 310.1260; Found 310.1250.

##STR00054##

[0184] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=4:1 as developing agent, the yield after separation was 46%.

[0185] (Z)-5-benzylidene-3-isopropyl-4,4-dimethylthiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.15H.sub.19NOS 262.1260; Found 262.1256

##STR00055##

[0186] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=2:1 as developing agent, the yield after separation was 75%.

[0187] (Z)-5-(4-bromobenzylidene)-3-butyl-4,4-dimethylthiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 7.49 (d, J=8.5 Hz, 2H), 7.20 (d, J=8.6 Hz, 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, 1.1 Hz, 3H) ppm; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 166.5, 140.7, 135.1, 131.9, 129.7, 121.0, 117.9, 68.1, 42.6, 31.7, 28.3, 20.6, 13.9 ppm; MS(ESI) m/z: [M+H].sup.+ Calcd for C.sub.16H.sub.20BrNOS 354.1; Found 354.1.

##STR00056##

[0188] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether: ethyl acetate (V/V)=1:3 as developing agent, the yield after separation was 79%.

[0189] (Z)-3-butyl-4.4-dimethyl-5-(pyridin-3-ylmethylene)thiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 8.52 (d, J=55.4 Hz, 2H), 7.70 (d, J=7.5 Hz, 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=7.3 Hz, 3H) ppm; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 166.1, 150.1, 147.9, 142.9, 134.2, 115.4, 68.3, 42.7, 31.7, 28.4, 20.5, 13.9 ppm; HRMS(ESI) m/z: [M+H].sup.+ Calcd for C.sub.15H.sub.22N.sub.2OS 277.1369; Found 277.1376.

##STR00057##

[0190] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=4:1 as developing agent, the yield after separation was 82%.

[0191] (Z)-3-butyl-4,4-dimethyl-5-(thiophen-2-ylmethylene)thiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 7.33 (d, J=5.0 Hz, 1H), 7.07-7.04 (m, 1H), 7.02 (d, J=3.1 Hz, 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=7.4 Hz, 3H) ppm; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 166.4, 140.2, 137.9, 127.5, 126.6, 126.0, 112.0, 67.7, 42.7, 31.7, 28.3, 20.5, 13.9 ppm; HRMS(ESI) m/z: [M+H].sup.+ Calcd for C.sub.14H.sub.19NOS.sub.2 282.0981; Found 282.0981.

##STR00058##

[0192] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=4:1 as developing agent, the yield after separation was 40%.

[0193] (Z)-3-butyl-5-(cyclopropylmethylene)-4,4-dimethylthiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 4.99 (d, J=8.8 Hz, 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=7.4 Hz, 3H), 0.85-0.78 (m, 2H), 0.44-0.39 (m, 2H) ppm; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.13H.sub.21NOS 240.1; Found 240.2.

##STR00059##

[0194] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=4:1 as developing agent, the yield after separation was 72%.

[0195] (Z)-5-benzylidene-3-cyclopropyl-4.4-dimethylthiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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. .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.15H.sub.17NOS 260.1; Found 260.2.

##STR00060##

[0196] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=4:1 as developing agent, the yield after separation was 85%.

[0197] (Z)-5-benzylidene-3-hexyl-4,4-dimethylthiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.18H.sub.25NOS 304.1730; Found 304.1734.

##STR00061##

[0198] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=2:1 as developing agent, the yield after separation was 86%.

[0199] (Z)-5-benzylidene-4,4-dimethyl-3-octylthiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.20H.sub.29NOS 332.2043; Found 332.2049.

##STR00062##

[0200] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=5:1 as developing agent, the yield after separation was 35%.

[0201] 3-benzyl-5-methylenethiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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. .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.4H.sub.5NOS: 206.1; Found 206.0.

##STR00063##

[0202] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=4:1 as developing agent, the yield after separation was 94%.

[0203] (Z)-5-benzylidene-3-hexyl-4-(p-tolyl)thiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.21H.sub.23NOS 338.1573; Found 338.1578.

##STR00064##

[0204] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=4:1 as developing agent, the yield after separation was 66%.

[0205] (Z)-5-benzylidene-3-butyl-4-(4-chlorophenyl)thiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 7.40 (d, J=8.3 Hz, 2H), 7.33 (d, J=8.2 Hz, 4H), 7.23 (d, J=7.6 Hz, 3H), 6.28 (s, 1H), 5.45 (s, 1H), 3.71 (dt, J=15.4, 7.9 Hz, 1H), 2.73-2.66 (m, 1H), 1.51-1.42 (m, 2H), 1.34-1.21 (m, 2H), 0.89 (t, J=7.3 Hz, 3H) ppm; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 168.0, 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, 13.8 ppm; HRMS(ESI) m/z: [M+H].sup.+ Calcd for C.sub.20H.sub.20ClNOS 358.1027; Found 358.1031.

##STR00065##

[0206] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): petroleum ether:ethyl acetate (V/V)=4:1 as developing agent, the yield after separation was 83%.

[0207] (Z)-5-benzylidene-3-butyl-4-(thiophen-3-yl)thiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 7.39-7.31 (m, 4H), 7.22 (dd, J=13.3, 5.9 Hz, 2H), 7.08 (d, J=6.1 Hz, 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=7.3 Hz, 3H) ppm; .sup.13C NMR (125 MHz, CDCl.sub.3) ? 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].sup.+ Calcd for C.sub.18H.sub.19NOS.sub.2 330.0981; Found 330.0981.

Class II H.SUB.2.S as Catalyst

Example 4 Synthesis of Benzimidazolone Derivatives by the Reaction of o-Phenylenediamine and CO.SUB.2 .in the Presence of H.SUB.2.S

[0208] ##STR00066##

[0209] 2 mmol of o-phenylenediamine, organic base and 1 mL of suitable solvent were added sequentially into a 15 mL high-pressure reactor, and the reactor was tightened; the required amount of H.sub.2S and CO.sub.2 gas was sequentially introduced into the reactor; finally, the mixture was continuously reacted at a suitable temperature for 12 hours; after the reaction was completed, a certain amount of distilled water was added to the reaction mixture to precipitate the product completely, and then filtered and dried sequentially to obtain the product.

[0210] The conditions were optimized according to the above steps, and the results are shown in the following table:

TABLE-US-00004 Yield Entry Solvent base (mmol) H.sub.2S (P.sub.MPa) CO.sub.2(P.sub.MPa) t (? C.) (%) 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 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 Note: In each of the above entries, the raw material was 2 mmol o-phenylenediamine; and the solvent is 1 ml.

Using the Method as in Entry 6 while Changing other Reaction Substrates, the Following Products were Obtained

[0211] ##STR00067##

[0212] 233 mg of white solid product was obtained by filtration and drying, separation yield: 87%

[0213] .sup.1H NMR (500 MHz, DMSO-d.sub.6, TMS): ? (ppm) 10.57 (s, 2H), 6.91 (s, 4H).

[0214] .sup.13C NMR (126 MHz, DMSO-d.sub.6, TMS): ? (ppm) 155.28(C), 129.67(C), 120.43(CH), 108.46(CH).

[0215] MS (ESI): m/z calcd for C.sub.7H.sub.6NO[M+H].sup.+: 135.06, found 135.1.

##STR00068##

[0216] 265 mg of solid product was obtained by filtration and drying, separation yield: 89.5%

[0217] .sup.1H NMR (500 MHz, DMSO-d.sub.6, TMS): ? (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).

[0218] .sup.13C NMR (125 MHz, DMSO-d.sub.6, TMS): ? (ppm) 155.29, 129.72, 129.21, 127.31, 120.75, 108.87, 108.03, 20.91.

##STR00069##

[0219] 266 mg of solid product, was obtained by filtration and drying, separation yield: 90%

[0220] .sup.1H NMR (500 MHz, DMSO-d.sub.6, TMS): ? (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).

[0221] .sup.13C NMR (125 MHz, DMSO-d.sub.6, TMS): ? (ppm) 155.47, 129.23, 128.55, 121.56, 120.34, 117.13, 106.05, 16.17.

##STR00070##

[0222] 289 mg of solid product, was obtained by filtration and drying, separation yield: 89.2%

[0223] .sup.1H NMR (500 MHz, DMSO-d.sub.6, TMS): ? (ppm) 10.34 (s, 2H), 6.70 (s, 2H), 2.17 (s, 6H).

[0224] .sup.13C NMR (125 MHz, DMSO-d.sub.6, TMS): ? (ppm) 155.41, 127.75, 109.54.

##STR00071##

[0225] 176 mg of solid product, was obtained by filtration and drying, separation yield: 58%

[0226] .sup.1H NMR (500 MHz, DMSO-d.sub.6, TMS): ? (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).

[0227] .sup.13C NMR (125 MHz, DMSO-d.sub.6, TMS): ? (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).

##STR00072##

[0228] 264 mg of solid product, was obtained by filtration and drying, separation yield: 78%

[0229] .sup.1H NMR (500 MHz, DMSO-d.sub.6, TMS): ? (ppm) 10.76 (s, 2H), 6.97-6.90 (m, 3H).

[0230] .sup.13C NMR (125 MHz, DMSO-d.sub.6, TMS): ? (ppm) 155.19, 130.82, 128.60, 124.47, 120.09, 109.50, 108.36.

##STR00073##

[0231] 421 mg of solid product, was obtained by filtration and drying, separation yield: 98.7%

[0232] .sup.1H NMR (500 MHz, DMSO-d.sub.6, TMS): ? (ppm) 10.76 (s, 2H), 7.05 (t, 2H, J1=J2=10.0 Hz), 6.88 (d, 1H, J=10.0 Hz).

[0233] .sup.13C NMR (125 MHz, DMSO-d.sub.6, TMS): ? (ppm) 155.03, 131.20, 128.98, 122.89, 111.98, 111.02, 110.06.

##STR00074##

[0234] 255 mg of solid product, was obtained by filtration and drying, separation yield: 63%

[0235] .sup.1H NMR (500 MHz, DMSO-d.sub.6, TMS): ? (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).

[0236] .sup.13C NMR (125 MHz, DMSO-d.sub.6, TMS): ? (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).

##STR00075##

[0237] 371 mg of solid product, was obtained by filtration and drying, separation yield: 78%

[0238] .sup.1H NMR (500 MHz, DMSO-d.sub.6, TMS): ? (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).

[0239] .sup.13C NMR (125 MHz, DMSO-d.sub.6, TMS): ? (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.

##STR00076##

[0240] 206 mg of solid product, was obtained by filtration and drying, separation yield: 63%

[0241] .sup.1H NMR (500 MHz, DMSO-d.sub.6, TMS): ? (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).

[0242] .sup.13C NMR (125 MHz, DMSO-d.sub.6, TMS): ? (ppm) 155.64, 154.33, 130.49, 123.56, 108.71, 106.07, 95.27, 55.42.

##STR00077##

[0243] 358 mg of solid product, was obtained by filtration and drying, separation yield: 97%

[0244] .sup.1H NMR (500 MHz, DMSO-d6, TMS): ? (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).

[0245] .sup.13C NMR (125 MHz, DMSO-d6, TMS): ? (ppm) 150.09, 137.67, 134.15, 128.03, 117.65, 113.66, 104.01.

Example 5 Synthesis of Benzothiazolone Derivatives by Reaction of o-Aminothiophenol and CO.SUB.2 .in the Presence of H.SUB.2.S

[0246] ##STR00078##

[0247] 2 mmol of the o-aminothiophenol was placed in a 15 mL stainless steel autoclave equipped with magnet stirrer, and then 2 mmol of base and 2 mL of solvent were added to the autoclave in order, and the autoclave was tightened. The corresponding amount of H.sub.2S was introduced, then the corresponding amount of CO.sub.2 was introduced. And the reaction mixture was stirred vigorously at the reaction temperature for 24 h. Upon completion, the autoclave was cooled down to room temperature and slowly depressurized. The solution was extracted with ethyl acetate, and the organic phases were combined and dried with anhydrous magnesium sulfate. The desiccant was removed by filtration and the solvent was removed under reduced pressure to obtain the crude product, which was purified by column chromatography to obtain the target product.

[0248] The conditions were optimized according to the above steps, and the results were shown in the following table:

TABLE-US-00005 molar ratio of o- P.sub.CO2 Entry Solvent base aminothiophenol:base (MPa) P.sub.H2S(MPa) T(? C.) Yield (%) 1 NMP DBU 1:1 3 0 40 trace 2 NMP DBU 1:1 3 0.2 40 85.1 3 NMP DBU 1:1 3 0.5 40 89.3 4 NMP DBU 1:1 3 1 40 94.4 5 NMP DBU .sup.1:0.5 3 0.2 40 83.7 6 NMP DBU 1:1 3 0.2 40 90.2 7 NMP DBU 1:2 3 0.2 40 89.7 8 NMP DBU 1:1 4 0.2 40 89.7 9 NMP DBU 1:1 5 0.2 40 91.8 10 DBU 1:1 8 1.0 40 75.0 11 DBU 1:1 10 1.0 40 83.0 12 DBU 1:1 12 1.0 40 77.0 13 NMP DBU 1:1 3 0.2 20 80.0 14 NMP DBU 1:1 3 0.2 50 92.2 15 NMP DBU 1:1 3 0.2 70 89.3 16 DMF DBU 1:1 3 0.2 40 77 17 NMP Et.sub.3N 1:1 3 0.2 40 82.4 18 NMP TMG 1:1 3 0.2 40 90.5 Note: The raw material was 2 mmol o-aminothiophenol; the solvent was2 mL; and the reaction time was 24 hours.

Using the Method as in Entry 7 while Changing Other Reaction Substrates, the Following Products were Obtained

[0249] ##STR00079##

[0250] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=20:1 as developing agent, 143 mg of white solid was obtained with a yield after separation of 94.4%.

[0251] Characterization data of benzothiazol-2-one (1a):.sup.1H NMR (CDCl.sub.3, 500 MHz): ? (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). .sup.13C NMR (CDCl.sub.3, 125 MHz): ? (ppm) 172.8, 135.3, 126.5, 123.9, 123.3, 122.6, 111.7; MS (EI): m/z calcd for C.sub.7H.sub.5NOS [M].sup.+: 151.0, found 151.0. m.p.: 139-140? C.

##STR00080##

[0252] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=5:1 as developing agent, 141 mg of white solid was obtained with a yield after separation of 76.2%.

[0253] Characterization data of 6-chlorobenzothiazole-2-one (1b):.sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (ppm) 12.02 (brs, 1H), 7.74 (d, 1H, J=2.0Hz), 7.32 (dd, 1H, J.sub.1=8.5, J.sub.2=2.5 Hz), 7.11 (d, 1H, J=8.5 Hz); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 169.7, 135.3, 126.4, 125.2, 122.4, 122.7; MS (EI): m/z calcd for C.sub.7H.sub.4ClNOS [M].sup.+: 185.1, found 185.0. m.p.: 212-214? C.

##STR00081##

[0254] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=20:1 as developing agent, 195 mg of white solid was obtained with a yield after separation of 85%.

[0255] Characterization data of 6-bromobenzothiazole-2-one (1c):.sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (ppm) 12.02 (brs, 1H), 7.86 (d, 1H, J=2.0 Hz), 7.44 (dd, 1H, J.sub.1=8.5, J.sub.2=2.5 Hz), 7.05 (d, 1H, J=8.5 Hz); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 169.7, 135.6, 129.2, 125.6, 125.0, 114.0, 113.1; MS (EI): m/z calcd for C.sub.7H.sub.4BrNOS [M].sup.+: 228.9, found 228.9. m.p.: 231-232? C.

##STR00082##

[0256] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=20:1 as developing agent, 149 mg of white solid was obtained with a yield after separation of 67.9%.

[0257] Characterization data of 6-trifluoromethylbenzothiazole-2-one (1d): .sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (ppm) 12.22 (brs, 1H), 7.85 (d, 1H, J=8.5 Hz), 7.48 (dd, 1H, J.sub.1=8.0 Hz, J.sub.2=1.0 Hz), 7.33 (d, 1H, J=1.5 Hz); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (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 C.sub.8H.sub.4F.sub.3NOS [m].sup.+: 219.2, found 219.0. m.p.: 216-218? C.

##STR00083##

[0258] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=10:1 as developing agent, 170 mg of white solid was obtained with a yield after separation of 94%.

[0259] Characterization data of 6-methoxybenzothiazole-2-one (1e): .sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (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, J.sub.1=8.5 Hz, J.sub.2=2.5 Hz), 3.73(s, 3H); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 169.8, 155.2, 129.9, 124.3, 113.2, 112.1, 107.8, 55.6; MS (EI): M/z calcd for C.sub.8H.sub.7NO.sub.2S [M].sup.+: 180.9, found 181.0. m.p.: 161-163? C.

##STR00084##

[0260] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=50:1 as developing agent, 160 mg of white solid was obtained with a yield after separation of 96.8%.

[0261] Characterization data of 6-methylbenzothiazole-2-one:.sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (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); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 169.8, 133.9, 131.7, 127.0, 123.2, 122.5, 111.1, 20.5; MS (EI): m/z calcd for C.sub.8H.sub.7NOS [m].sup.+: 165.0, found 165.0. m.p: 170-171? C.

##STR00085##

[0262] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=50:1 as developing agent, 94 mg of white solid was obtained with a yield after separation of 51.0%.

[0263] Characterization data of 5-chlorobenzothiazol-2-one: .sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (ppm) 12.04 (brs, 1H), 7.61 (d, 1H, J=8.5 Hz), 7.19 (dd, 1H, J.sub.1=8.5, J.sub.2=2.5 Hz), 7.12 (d, 1H, J=2.0 Hz); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 170.0, 137.4, 130.8, 124.3, 122.4, 122.2, 111.2; MS (EI): m/z calcd for C.sub.7H.sub.4ClNOS [M].sup.+: 184.9, found 185.0. m.p.: 224-226? C.

##STR00086##

[0264] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=5:1 as developing agent, 164 mg of white solid was obtained with a yield after separation of 99.3%.

[0265] Characterization data of 4-methylbenzothiazole-2-one: .sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (ppm) 11.73 (brs, 1H), 7.37 (dd, 1H, J.sub.1=7.5, J.sub.2=0.5 Hz), 7.08-7.09 (m, 1H), 7.03 (t, 1H, J=7.5 Hz), 2.32 (s, 3H); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 170.4, 135.0, 127.6, 122.8, 122.5, 121.3, 120.0, 17.4; MS (EI): m/z calcd for C.sub.8H.sub.7NOS [M].sup.+: 165.1, found 165.0. m.p.: 211-212? C.

##STR00087##

[0266] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): ethyl acetate:petroleum ether (V/V)=3:1 as developing agent, 155 mg of white solid was obtained with a yield after separation of 67.9%.

[0267] Characterization data of methylsulfonyl benzothiazole-2-one: .sup.1H NMR(DMSO-d.sub.6, 500 MHz): ? (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); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 170.2, 140.4, 134.6, 125.6, 124.2, 122.2, 111.5, 43.9; MS (EI): m/z calcd for C.sub.8H.sub.7NO.sub.3S.sub.2 [M].sup.+: 229.0, found 228.8. m.p.: 241-244? C.

Example 6 Synthesis of Benzothiazolone Derivatives by the Reaction of Aromatic o-Aminodisulfides with CO.SUB.2 .in the Presence of H.SUB.2.S

[0268] ##STR00088##

[0269] 0.5 mmol of disulfide, 0.5 mmol of base, and 2 ml of solvent were added into the reactor sequentially, and the reactor was tightened, the appropriate amount of H.sub.2S was introduced, preheated, and corresponding amount of CO.sub.2 was introduced, then reacted at the corresponding temperature for 12 hours. After the reaction was completed, the reactor was cooled to room temperature, the gas in the reactor was slowly exhausted, then extracted with ethyl acetate and saturated salt water, the organic phases were combined and separated by column chromatography to obtain the target product.

[0270] The conditions were optimized according to the above steps, and the results were shown in the following table:

TABLE-US-00006 CO.sub.2 H.sub.2S Tem- Molar ratio pres- pres- pera- (Sub- Sol- sure sure ture Yield Entry base strate:base) vent (MPa) (MPa) (? C.) (%) 1 DBU 1:1 NMP 3 0 50 0 2 DBU 1:1 NMP 3 0.2 50 87 3 DBU 1:1 NMP 3 0.3 50 97 4 DBU 1:1 NMP 3 0.4 50 97 5 DBU 1:1 NMP 3 0.6 50 94 6 DBU 1:1 NMP 3 0.8 50 96 7 DBU 1:1 NMP 3 1.0 50 94 8 DBU 1:0 NMP 3 0.3 50 0 9 DBU .sup.1:0.4 NMP 3 0.3 50 92 11 DBU 1:2 NMP 3 0.3 50 84 12 DBU 1:1 NMP 1 0.3 50 83 13 DBU 1:1 NMP 0 0.3 50 0 14 DBU 1:1 NMP 5 0.3 50 92 15 DBU 1:1 NMP 3 0.3 25 90 16 DBU 1:1 NMP 3 0.3 80 86 17 DBU 1:1 NMP 3 0.3 100 97 18 Et.sub.3N 1:1 NMP 3 0.3 50 75 19 TMG 1:1 NMP 3 0.3 50 90 20 DBU 1:1 CH.sub.3OH 3 0.3 50 6.8 21 DBU 1:1 1,4- 3 0.3 50 61 dioxane 22 DBU 1:1 DMSO 3 0.3 50 34 Note: the raw material was 0.5 mmol disulfide (dimer of o-aminothiophenol); the solvent was 2 mL; the molar ratio in the table was the mol ratio of disulfide:DBU; and the reaction time was 12 h.

Using the Method as in Entry 3 while Changing Other Reaction Substrates, the Following Products were Obtained

[0271] ##STR00089##

[0272] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=20:1 as developing agent, 148 mg of white solid was obtained with a yield after separation of 98%.

[0273] Characterization data: .sup.1H NMR (CDCl.sub.3, 500 MHz): ? (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). .sup.13C NMR (CDCl.sub.3, 125 MHz): ? (ppm) 172.8, 135.3, 126.5, 123.9, 123.3, 122.6, 111.7; MS (EI): m/z calcd for C.sub.7H.sub.5NOS [M].sup.+: 151.0, found 151.0. m.p.: 139-140? C.

##STR00090##

[0274] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=20:1 as developing agent, 180 mg of white solid was obtained with a yield after separation of 97.2%.

[0275] Characterization data: .sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (ppm) 12.02 (brs, 1H), 7.74 (d, 1H, J=2.0 Hz), 7.32 (dd, 1H, J.sub.1=8.5, J.sub.2=2.5 Hz), 7.11 (d, 1H, J=8.5 Hz); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 169.7, 135.3, 126.4, 125.2, 122.4, 122.7; MS (EI): m/z calcd for C.sub.7H.sub.4ClNOS [m].sup.+: 185.1, found 185.0. m.p.: 212-214? C.

##STR00091##

[0276] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=20:1 as developing agent, 179 mg of white solid was obtained with a yield after separation of 78.3%.

[0277] Characterization data: .sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (ppm) 12.02 (brs, 1H), 7.86 (d, 1H, J=2.0 Hz), 7.44 (dd, 1H, J.sub.1=8.5, J.sub.2=2.5 Hz), 7.05 (d, 1H, J=8.5 Hz); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 169.7, 135.6, 129.2, 125.6, 125.0, 114.0, 113.1; MS (EI): m/z calcd for C.sub.7H.sub.4BrNOS [m].sup.+: 228.9, found 228.9. m.p.: 231-232? C.

##STR00092##

[0278] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=20:1 as developing agent, 169 mg of white solid was obtained with a yield after separation of 93.5%.

[0279] Characterization data: .sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (ppm) 11.658 (brs, 1 H), 7.23 (d, 1H, J=2.5 Hz), 7.02 (d, 1H, J=8.5 Hz), 6.86 (dd, 1H, J.sub.1=8.5 Hz, J.sub.2=2.5 Hz), 3.73(s, 3H); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 169.8, 155.2, 129.9, 124.3, 113.2, 112.1, 107.8, 55.6; MS (EI): m/z calcd for C.sub.8H.sub.7NO.sub.2S [M].sup.+: 180.9, found 181.0. m.p.: 161-163? C.

##STR00093##

[0280] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=20:1 as developing agent, 149 mg of white solid was obtained with a yield after separation of 90%.

[0281] Characterization data: .sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (ppm) 11.73 (brs, 1H), 7.37 (dd, 1H, J.sub.1=7.5 Hz, J.sub.2=0.5 Hz), 7.08-7.09 (m, 1H), 7.03 (t, 1H, J=7.5 Hz), 2.32(s, 3H). .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 170.4, 135.0, 127.6, 122.8, 122.5, 121.3, 120.0, 17.4; MS (EI): m/z calcd for C.sub.7H.sub.5NOS [m].sup.+: 165.1, found 165.0. m.p: 211-212? C.

##STR00094##

[0282] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=20:1 as developing agent, 157 mg of white solid was obtained with a yield after separation of 95.4%.

[0283] Characterization data: .sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (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); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 169.8, 133.9, 131.7, 127.0, 123.2, 122.5, 111.1, 20.5; MS (EI): m/z calcd for C.sub.8H.sub.7NOS [m].sup.+: 165.0, found 165.0. m.p.: 170-171? C.

##STR00095##

[0284] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=20:1 as developing agent, 154 mg of white solid was obtained with a yield after separation of 93.5%.

[0285] Characterization data: .sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (ppm) 11.73 (brs, 1H), 7.37 (dd, 1H, J.sub.1=7.5, J.sub.2=0.5 Hz), 7.08-7.09 (m, 1H), 7.03 (t, 1H, J=7.5 Hz), 2.32 (s, 3H); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 170.4, 135.0, 127.6, 122.8, 122.5, 121.3, 120.0, 17.4; MS (EI): m/z calcd for c.sub.8h.sub.7NOS [m].sup.+: 165.1, found 165.0. m.p: 211-212? C.

##STR00096##

[0286] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=1:2 as developing agent, 140 mg of white solid was obtained with a yield after separation of 61%.

[0287] Characterization data: .sup.1H NMR(DMSO-d.sub.6, 500 MHz): ? (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); .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (ppm) 170.2, 140.4, 134.6, 125.6, 124.2, 122.2, 111.5, 43.9; MS (EI): m/z calcd for C.sub.8H.sub.7NO.sub.3S.sub.2 [m].sup.+: 229.0, found 228.8. m.p.: 241-244? C.

##STR00097##

[0288] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): dichloromethane:ethyl acetate (V/V)=20:1 as developing agent, 128 mg of white solid was obtained with a yield after separation of 76%.

[0289] Characterization data: .sup.1H NMR (DMSO-d.sub.6, 500 MHz): ? (ppm) 12.39 (brs, 1H), 7.43 (d, 1H, J=7.5 Hz), 7.12-7.22 (m, 2H). .sup.13C NMR (DMSO-d.sub.6, 125 MHz): ? (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 C.sub.7H.sub.5NOS [m].sup.+: 169.0, found 169.0. m.p.: 172-174? C.

Example 7 Synthesis of Imidazolidinone (Oxazolidinone or Thiazolidinone) Derivatives by the Reaction of Diamine, Alcoholamine or Mercaptoamine with CO.SUB.2 .in the Presence of H.SUB.2.S

[0290] ##STR00098##

[0291] 2 mmol of diamine, 0.8 mmol of base, and 2 mL of solvent were weighed and added to the reactor sequentially, and the reactor was tightened. The corresponding amount of H.sub.2S was introduced into the reactor, and the corresponding amount of CO.sub.2 was introduced at a suitable temperature, and then the mixture was stirred for 4 h. After the reaction was completed, the reactor was cooled to room temperature, and the reactor was opened after the gas in the reactor was slowly exhausted, then extracted, separated by column chromatography and recrystallized to obtain the target product.

[0292] The conditions were optimized according to the above steps, and the results were shown in the following table:

TABLE-US-00007 Base P(MPa) Yield Entry (equivalent) Solvent H.sub.2S CO.sub.2 Time(h) T(? C.) (%) 1 DBU(0.4) NMP 0.2 3 8 100 99 2 DBU(0.4) NMP 0.2 3 4 100 99 3 DBU(0.4) NMP 0.2 3 2 100 89 4 DBU(0.4) NMP 0.2 3 1 100 80 5 DBU(0.4) NMP 0.2 3 4 120 99 6 DBU(0.4) NMP 0.2 1 4 110 93 7 DBU(0.4) NMP 0.2 1 4 90 99 8 DBU(0.4) NMP 0.2 1 4 90 88 9 DBU(0.4) NMP 0.2 3 4 90 99 10 DBU(0.4) NMP 0.2 5 4 90 89 11 DBU(0.6) NMP 0.2 3 4 90 99 12 DBU(0.4) NMP 0.2 3 4 90 99 13 DBU(0.2) NMP 0.2 3 4 90 82 14 DBU(0.4) NMP 0.4 3 4 90 96.4 15 DBU(0.4) NMP 1 3 4 90 89.9 16 DBU(0.4) DMF 0.2 3 4 90 98 17 NMP 0.2 3 12 90 79% 18 Et.sub.3N(0.4) NMP 0.2 3 4 90 73% 19 DIPEA NMP 0.2 3 4 90 76% 20 NaSH (0.4) NMP 0.2 3 4 90 12% 21 K.sub.2CO.sub.3(0.4) NMP 0.2 3 4 90 8% Note: the raw material was 2 mmol ethylenediamine; the solvent was 2 ml NMP. In entry 17, ethylenediamine was used as base and NMP was added as solvent.

Using the Method as in Entry 10 While Changing Other Reaction Substrates, the Reaction Results are as Follows

Characterization of Compounds

[0293] ##STR00099##

[0294] Extracted with ethyl acetate, separated by column chromatography and recrystallized, 170.2 mg of the pure target product was obtained with a yield of 99%.

[0295] Imidazolidin-2-one: white solid, .sup.1H NMR (500 MHz, CDCl.sub.3) ? 3.52 (s, 1H). .sup.13C NMR (126 MHz, CDCl.sub.3) ? 165.64, 41.04.

##STR00100##

[0296] Extracted with ethyl acetate, separated by column chromatography and recrystallized, 153.7 mg of the pure target product was obtained with a yield of 68%. 1,3-Dimethylimidazolidin-2-one: Colorless oil, .sup.1HNMR (500 MHz, CDCl.sub.3): d=2.79 (s,6H, 2CH.sub.3), 3.27 (s, 4H,2CH.sub.2); .sup.13C NMR (126 MHz, CDCl.sub.3): d=31.3, 44.9, 161.9.

##STR00101##

[0297] Extracted with ethyl acetate, and separated by column chromatography, 216.5 mg of the pure target product was obtained with a yield of 91%.

[0298] 4,5-Diphenylimidazolidin-2-one: white solid, .sup.1H NMR (500 MHz, CDCl.sub.3): ? 7.38-7.34 (m, 6H), 7.27-7.30 (m, 4H), 5.83 (s, 2H), 4.57 (s, 2H). .sup.13C NMR (126 MHz, CDCl.sub.3) ? 163.1, 140.2, 128.7, 128.2, 126.4, 65.9;

##STR00102##

[0299] Extracted with ethyl acetate, and separated by multiple column chromatography, 241.74 mg of the pure target product was obtained with a yield of 85%.

[0300] 1,3-Diethylimidazolidin-2-one: Colorless oil, 95%. .sup.1H NMR (500 MHz, CDCl.sub.3): ? 3.23 (s, 4H), 3.19 (q, J=7.2 Hz, 4H), 1.05 (t, J=7.2 Hz, 6H). .sup.13C NMR (500 MHz, CDCl.sub.3): ? 161.3, 42.3, 38.9, 12.9.

##STR00103##

[0301] Extracted with ethyl acetate, and separated by column chromatography, 278.49 mg of the pure target product was obtained with a yield of 99%.

[0302] octahydro-2H-benzo[d]imidazol-2-one: colourless solid, .sup.1H NMR (500 MHz, CDCl.sub.3) ? 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); .sup.13C NMR (126 MHz, CDCl.sub.3) ? 77.67, 52.45, 28.85, 20.88.

##STR00104##

[0303] Extracted, and separated by column chromatography, 192 mg of the pure target product was obtained with a yield of 75%.

[0304] 1,3-Dimethyl-3,4,5,6-tetrahydropyrimidin-2(1H)-one: .sup.1H NMR (500 MHz, CDCl.sub.3): d=1.97 (quintet, J=6.0 Hz, 2H, CH.sub.2), 2.92 (s, 6H, 2 CH.sub.3), 3.24 (t, J=6.0 Hz, 4H, 2 CH.sub.2); .sup.13C NMR (126 MHz, CDCl.sub.3): d=22.1, 35.5, 47.8, 156.7.

##STR00105##

[0305] Filtrated, 188 mg of pure target product was obtained with a yield of 73%.

[0306] 5,5-dimethyltetrahydropyrimidin-2(1H)-one: white solid, 1H NMR (500 MHz, DMSO-d6) ? 6.06 (s, 2H), 2.76 (s, 4H), 0.94 (s, 6H). .sup.13C NMR (126 MHz, DMSO-d6) ? 155.26, 51.06, 27.20, 23.89.

##STR00106##

[0307] Extracted with ethyl acetate, and separated by column chromatography, 174.4 mg of the pure target product was obtained with a yield of 99%.

[0308] 5-phenylimidazolidine-2,4-dione: white solid, 1H NMR (500 MHz, DMSO-d6) ? 10.77 (s, 1H), 8.39 (s, 1H), 7.37 (d, J=34.7 Hz, 6H), 5.16 (s, 1H). 13C NMR (126 MHz, DMSO-d6) ? 174.34, 157.65, 136.21, 128.80, 128.39, 126.86, 61.35.

##STR00107##

[0309] Spreated by column chromatography, and recrystallized with dichloromethane and ethyl acetate, 182 mg of the target product was obtained with a yield of 91%.

[0310] 4-methylimidazolidin-2-one: white solid, 1H NMR (500 MHz, CDCl.sub.3) ? 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). .sup.13C NMR (126 MHz, CDCl.sub.3) ? 163.90, 48.41 , 48.01 , 21.15.

##STR00108##

[0311] Filtrated, 164.1 mg of pure target product was obtained with a yield of 72%.

[0312] 1-methyltetrahydropyrimidin-2(1H)-one: white solid, .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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). .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 46.95, 22.02

##STR00109##

[0313] Extracted with ethyl acetate, and separated by column chromatography, 221.1 mg of the pure target product was obtained with a yield of 97%.

[0314] ethylimidazolidin-2-one: Colorless oil, .sup.1H NMR (500 MHz, CDCl.sub.3) ? 3.50-3.35 (m, 6H), 3.25 (q, J=7.2 Hz, 2H), 1.12 (t, J=7.2 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) ? 162.59, 44.39, 38.25, 38.09, 12.69.

##STR00110##

[0315] Extracted with ethyl acetate, and separated by column chromatography, 172.4 mg of the pure target product was obtained with a yield of 99%.

[0316] 2-Oxazolidinone: 1H NMR (500 MHz, CDCl.sub.3) ? 3.64 (t, 2H), 4.46 (t, 2H), 6.68 (s, 1H). .sup.13CNMR (126 MHz, CDCl.sub.3), ? 41.0, 65.5, 161.5.

##STR00111##

[0317] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): methylene chloride and ethyl acetate (V/V=3:1) as developing agent, 280.6 mg of light yellow solid was obtained with a yield after separation of 86%.

[0318] 4-phenyloxazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? (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). .sup.13C NMR (126 MHz, DMSO-d6) ? (ppm) 159.37, 141.48, 129.19, 128.44, 126.51, 71.84, 55.57. ESI-MS calcd for C.sub.9H.sub.10NO.sub.2 [M+H].sup.+ 164.06, found 164.10.

##STR00112##

[0319] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): methylene chloride and ethyl acetate (V/V=3:1) as developing agent, 229.5 mg of pale yellow solid was obtained with a yield after separation of 70%.

[0320] 5-phenyloxazolidin-2-one: white solid, .sup.1H NMR (500 MHz, CDCl.sub.3) ? (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). .sup.13C NMR (126 MHz, CDCl.sub.3) ? (ppm) 159.66, 138.38, 128.92, 125.66, 77.90, 48.29. ESI-MS calcd for C.sub.9H.sub.10NO.sub.2 [M+H].sup.+ 164.06, found 164.10.

##STR00113##

[0321] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): methylene chloride and ethyl acetate (V/V=1:1) as developing agent, 201.6 mg of product was obtained with a yield after separation of 99%.

[0322] 4-methyloxazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? (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). .sup.13C NMR (126 MHz, CDCl.sub.3) ? (ppm) 160.11, 71.65, 48.25, 20.78. ESI-MS calcd for C.sub.4H.sub.8NO.sub.2 [M+H].sup.+ 102.05, found 102.10.

##STR00114##

[0323] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): methylene chloride and ethyl acetate (V/V=1:1) as developing agent, 182.2 mg of product was obtained with a yield after separation of 90%.

[0324] 5-methyloxazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? (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). .sup.13C NMR (126 MHz, CDCl.sub.3) ? (ppm) 160.04, 77.21, 73.50, 47.40, 20.52. ESI-MS calcd for C.sub.4H.sub.8NO.sub.2 [M+H].sup.+ 102.05, found 102.10.

##STR00115##

[0325] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): methylene chloride and ethyl acetate (V/V=5:1) as developing agent, 225.6 mg of product was obtained with a yield after separation of 99%.

[0326] 4-ethyloxazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? (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). .sup.13C NMR (126 MHz, CDCl.sub.3) ? (ppm) 159.73, 69.95, 53.75, 28.15, 9.29. ESI-MS calcd for C.sub.5H.sub.10NO.sub.2 [M+H].sup.+ 116.06, found 116.10.

##STR00116##

[0327] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): methanol and methylene chloride (V/V=1:5) as developing agent, 225.9 mg of white solid was obtained with a yield after separation of 100%.

[0328] 5,5-dimethyloxazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? (ppm) 5.11(brs, 1H), 3.35 (s, 2H), 1.48 (s, 6H). .sup.13C NMR (126 MHz, CDCl.sub.3) ? (ppm) 159.34, 81.02, 52.64, 27.19. ESI-MS calcd for C.sub.5H.sub.10NO.sub.2 [M+H].sup.+ 116.06, found 116.15.

##STR00117##

[0329] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel): methanol and methylene chloride (V/V=1:5) as developing agent, 93.5 mg of white solid was obtained with a yield after separation of 41%.

[0330] 4,4-dimethyloxazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? (ppm) 6.11 (brs, 1H), 4.09 (s, 2H), 1.37 (s, 6H). .sup.13C NMR (126 MHz, CDCl.sub.3) ? (ppm) 158.84, 76.90, 55.19, 27.59. ESI-MS calcd for C.sub.5H.sub.10NO.sub.2 [M+H].sup.+ 116.06, found 116.10.

##STR00118##

[0331] Separated by wet packing and dry sample loading column chromatography (200-300 mesh silica gel): methylene chloride and ethyl acetate (V/V=2:1) as developing agent, 317.3 mg of white solid was obtained with a yield after separation of 90%.

[0332] (R)-4-benzyloxazolidin-2-one: .sup.1H NMR (500 MHz, DMSO-d6) ? (ppm) 7.78 (brs, 1H), 7.33-7.21 (m, 5H), 4.25 (t, J=8.3 Hz, 1H), 4.08-3.96 (m, 2H), 2.84-2.72 (m, 2H). .sup.13C NMR (126 MHz, DMSO-d6) ? (ppm) 159.04, 136.99, 129.82, 128.84, 126.98, 68.46, 52.93, 40.68. ESI-MS calcd for C.sub.10H.sub.12NO.sub.2 [M+H].sup.+ 178.08, found 178.05.

##STR00119##

[0333] Separated by wet packing and wet sample loading column chromatography (200-300 mesh silica gel): methylene chloride and ethyl acetate (V/V=2:1) as developing agent, 237.2 mg of white solid was obtained with a yield after separation of 94%.

[0334] (S)-4-isopropyloxazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? (ppm) 6.47(brs), 4.44 (t, J=8.7 Hz, 1H), 4.10 (dd, J=8.7, 6.3 Hz, 1H), 3.63-3.59 (m, 1H), 1.77-1.70 (m, 1H), 0.97 (d, J=6.7 Hz, 3H), 0.90 (d, J=6.8 Hz, 3H). .sup.13C NMR (126 MHz, CDCl.sub.3) ? (ppm) 160.25, 68.59, 58.34, 32.67, 17.99, 17.62. ESI-MS calcd for C.sub.6H.sub.12NO.sub.2 [M+H].sup.+ 130.08, found 130.10.

##STR00120##

[0335] Extracted with ethyl acetate, and separated by column chromatography, 172.0 mg of the pure target product was obtained with a yield of 86%.

[0336] 1,3-Oxazinan-2-one: .sup.1H NMR (500 MHz, DMSO d.sub.6) ? 1.77-1.85 (m, 2H, NHCH2-CH2-CH2-O), 3.12-3.19 (m, 2H), 4.15 (t, J=5.4 Hz, 2H), 7.13 (s, 1H,). .sup.13C NMR (126 MHz, DMSO d.sub.6) ? 21.79, 39.78, 67.04, 153.74.

##STR00121##

[0337] Extracted with ethyl acetate, and separated by column chromatography, 171.0 mg of the pure target product was obtained with a yield of 84%.

[0338] thiazolidin-2-one: .sup.1H NMR (500 MHz, CDCl.sub.3) ? 3.37 (t, J=3.6 Hz, 2H), 3.59 (t, J=3.6 Hz, 2H), 6.99 (s, 1H)

Example 8 Synthesis of Thioquinazolindione Derivatives by Reaction of o-Aminobenzonitrile and CO.SUB.2 .in the Presence of H.SUB.2.S

[0339] ##STR00122##

[0340] A magnet was placed into a 10 mL stainless steel high pressure reactor, and 1 mmol of o-aminobenzonitrile derivative, appropriate amount of H.sub.2S and 2 ml of solvent were added sequentially, and the reactor was tightened. Carbon dioxide was introduced to the reactor at the specified pressure, stirred for 24h, then the reaction was ended and cooled down. The gas in the reactor was slowly exhausted, the reactor was opened and extracted with ethyl acetate and saturated salt water. The organic phases were combined and the crude product was obtained by distillation under reduced pressure. The pure target product was obtained by column chromatography (eluted with petroleum ether and ethyl acetate).

[0341] The conditions were optimized according to the above steps, and the reaction results are shown in the following table:

TABLE-US-00008 CO.sub.2 H.sub.2S pres- pres- Tempera- Molar ratio sure sure ture Yield Entry (Substrate:base) Solvent (MPa) (MPa) (? C.) (%) 1 1:1 DMF 4 1 40 34 2 1:1 DMF 4 0.8 40 37 3 1:1 DMF 4 0.6 40 20 4 1:1 DMF 4 0.6 50 92 5 1:1 DMF 4 0.4 50 66 6 1:1 DMF 4 0.8 50 81 7 1:1 DMF 0 0.6 50 0 8 1:1 DMF 2 0.6 50 83 9 1:1 DMF 5 0.6 50 99 10 .sup.1:0.5 DMF 5 0.6 50 58 11 .sup.1:1.8 DMF 5 0.6 50 99 12 1:1 NMP 5 0.6 50 95 Note: In each of the above reactions, the raw material was 1 mmol o-aminobenzonitrile; the solvent was 2 ml; the molar ratio was the molar ratio of raw material to DBU; and reacted for 24 h.

Using the Method as in Entry 9 while Changing Other Reaction Substrates, the Following Products were Obtained

[0342] ##STR00123##

[0343] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel) with gradient elution, petroleum ether and ethyl acetate as eluent, petroleum ether:ethyl acetate (V/V)=1:1, 235.2 mg of yellow solid 6,7-dimethoxy-2-oxo-4-thioquinazolindione was obtained with a yield after separation of 99%. The analysis results show that the obtained target product has a correct structure.

[0344] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ?=12.50 (s, 1H), 11.46 (s, 1H), 7.69 (s, 1H), 6.64 (s, 1H), 3.84 (s, 3H), 3.79 (s, 3H). .sup.13C NMR (126 MHz, DMSO-d.sub.6) ?=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.sub.10H.sub.10N.sub.2O.sub.3S [M].sup.+: 239.04, found 239.2

##STR00124##

[0345] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel) with gradient elution, petroleum ether and ethyl acetate as eluent, petroleum ether:ethyl acetate (V/V)=2:1, and the polarity is increased to 1:1, 184 mg of yellow solid 6-fluoro-2-oxo-4-thioquinazolindione was obtained with a yield after separation of 94%. The analysis results shown that the obtained target product has a correct structure.

[0346] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ?=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). .sup.13C NMR (126 MHz, DMSO-d.sub.6) ?=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 C.sub.8H.sub.5FN.sub.2OS [M].sup.+: 197.01, found 196.9

##STR00125##

[0347] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel) with gradient elution, petroleum ether and ethyl acetate as eluent, petroleum ether:ethyl acetate (V/V)=3:1, 217 mg of white solid 6-bromo-2-oxo-4-thioquinazolindione was obtained with a yield after separation of 85%, and the analysis results shown that the obtained target product has a correct structure.

[0348] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ?=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). .sup.13C NMR (126 MHz, DMSO-d.sub.6) ?=189.50, 147.08, 138.29, 137.44, 132.05, 121.64, 118.36, 114.79. MS (ESI): m/z calcd for C.sub.8H.sub.5BrN.sub.2OS [M].sup.+: 257.9, found 257.1.

##STR00126##

[0349] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel) with gradient elution, petroleum ether and ethyl acetate as eluent, petroleum ether:ethyl acetate (V/V)=2:1, 162 mg of yellow solid 7-fluoro-2-oxo-4-thioquinazolindione was obtained with a yield after separation of 83%. The analysis results show that the obtained target product has a correct structure.

[0350] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ?=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). .sup.13C NMR (126 MHz, DMSO-d.sub.6) ?=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 C.sub.8H.sub.5FN.sub.2OS [M].sup.+:, 197.01 found 197.3.

##STR00127##

[0351] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel) with gradient elution, petroleum ether and ethyl acetate as eluent, petroleum ether:ethyl acetate (V/V)=2:1, 219mg of yellow solid 7-trifluoromethyl-2-oxo-4-thioquinazolindione was obtained with a yield after separation of 89%, and the analysis results shown that the obtained target product has a correct structure.

[0352] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ?=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, 1H). .sup.13C NMR (126 MHz, DMSO-d.sub.6) ?=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 C.sub.9H.sub.5F.sub.3N.sub.2OS [M].sup.+: 247.01, found 247.3.

##STR00128##

[0353] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel) with gradient elution, petroleum ether and ethyl acetate as eluent, petroleum ether:ethyl acetate (V/V)=2:1, 138 mg of yellow solid 7-chloro-2-oxo-4-thioquinazolindione was obtained with a yield after separation of 65%, and the analysis results shown that the obtained target product has a correct structure.

[0354] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ?=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). .sup.13C NMR (126 MHz, DMSO-d.sub.6) ?=191.92, 170.17, 151.67, 136.49, 130.76, 115.32, 113.52, 112.55. MS (ESI): m/z calcd for C.sub.8H.sub.5ClN.sub.2OS [M].sup.+: 212.65, found 212.3.

##STR00129##

[0355] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel) with gradient elution, petroleum ether and ethyl acetate as eluent, petroleum ether:ethyl acetate (V/V)=2:1, 172 mg of yellow solid 7-methyl-2-oxo-4-thioquinazolindione was obtained with a yield after separation of 89%, and the analysis results shown that the obtained target product has a correct structure.

[0356] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ?=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). .sup.13C NMR (126 MHz, DMSO-d.sub.6)) ?=188.97, 148.23, 146.65, 137.75, 131.11, 125.24, 119.85, 114.69. MS (ESI): m/z calcd for C.sub.9H.sub.8N.sub.2OS [M].sup.+: 193.04, found 193.2.

##STR00130##

[0357] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel) with gradient elution, petroleum ether and ethyl acetate as eluent, petroleum ether:ethyl acetate (V/V)=1:1, 80 mg of brown solid 6-nitro-2-oxo-4-thioquinazolindione was obtained with a yield after separation of 36%, and the analysis results shown that the obtained target product has a correct structure.

[0358] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ?=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). .sup.13C NMR (126 MHz, DMSO-d.sub.6) ?=191.01, 158.80, 144.50, 128.55, 123.74, 122.13, 116.09, 111.20. MS (ESI): m/z calcd for C.sub.8H.sub.5N.sub.3O.sub.3S [M].sup.+: 223.01, found 223.4.

##STR00131##

[0359] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel) with gradient elution, petroleum ether and ethyl acetate as eluent, petroleum ether:ethyl acetate (V/V)=2:1, 133 mg of yellow solid 5-fluoro-2-oxo-4-thioquinazolindione was obtained with a yield after separation of 68%, and the analysis results shown that the obtained target product has a correct structure.

[0360] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ?=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). .sup.13C NMR (126 MHz, DMSO-d.sub.6) ?=186.47, 154.09, 147.11, 141.12, 134.24, 111.58, 110.66, 104.63. MS (ESI): m/z calcd for C.sub.8H.sub.5FN.sub.2OS [M].sup.+: 197.01, found 197.2

##STR00132##

[0361] Separated by dry packing and dry sample loading column chromatography (200-300 mesh silica gel) with gradient elution, petroleum ether and ethyl acetate as eluent, petroleum ether:ethyl acetate (V/V)=2:1, 240 mg of yellow solid 6-trifluoromethyl-2-oxo-4-thioquinazolindione was obtained with a yield after separation of 97%, and the analysis results shown that the obtained target product has a correct structure.

[0362] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ?=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). .sup.13C NMR (126 MHz, DMSO-d.sub.6) ?=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 C.sub.9H.sub.5F.sub.3N.sub.2OS [M].sup.+: 247.01, found 247.3.

Example 10 Synthesis of Substituted Urea Derivatives by Reaction of Benzylamine and CO.SUB.2 .in the Presence of H.SUB.2.S

[0363] ##STR00133##

[0364] 2 mmol of benzylamine, DBU and 1 mL of suitable solvent were added sequentially in a 15 mL high-pressure reactor, and the reactor was tightened; the required amount of H.sub.2S and CO.sub.2 gas was sequentially introduced into the reactor; finally, the reactor was continued to be stirred at a suitable temperature for 24 hours; after the reaction was completed, a certain amount of distilled water was added to the reaction mixture to precipitate the product completely, and then filtered and dried sequentially to obtain the product.

[0365] The conditions were optimized according to the above steps, and the reaction results were shown in the following table:

TABLE-US-00009 Base n(mmol) Yield Entry (equivalent) T(? C.) H.sub.2S CO.sub.2 Solvent Time(h) (%) 1 DBU(0.5) 100 1 10 NMP 24 64 2 DBU(0) 100 1 10 NMP 24 75 3 DBU(0) 110 1 10 NMP 24 85 4 DBU(0) 120 1 10 NMP 24 91 5 DBU(0) 130 1 10 NMP 24 86 6 DBU(0) 120 2 10 NMP 24 84 7 DBU(0) 120 0.5 10 NMP 24 72 8 DBU(0) 120 0 10 NMP 24 NR 9 DBU(0) 120 1 6 NMP 24 71 10 DBU(0) 120 1 20 NMP 24 80 11 DBU(0) 120 1 10 NMP 36 71 12 DBU(0) 120 1 10 NMP 12 59 Note: In each of the above reactions, the raw material was 2 mmol benzylamine; the solvent was 1 ml, NR: no reaction.

Using the Method as in Entry 4 while Changing Other Reaction Substrates, the Following Products were Obtained

[0366] ##STR00134##

[0367] 205 mg of white powder product was obtained by filtration and drying, with a yield of 91%.

[0368] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0369] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 158.08, 140.89, 128.19, 126.96, 126.52, 42.98.

[0370] MS (ESI): m/z calcd for C.sub.15H.sub.17N.sub.2O [M+H].sup.+: 241.10, found 241.13, m.p.: 168-169? C.

##STR00135##

[0371] 244 mg of light yellow powder product was obtained by filtration and drying, with a yield of 86%.

[0372] .sup.1H NMR (500 MHz, Chloroform-d) ? 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).

[0373] .sup.13C NMR (126 MHz, Chloroform-d) ? 158.50, 40.63, 31.83, 30.31, 29.36, 29.27, 26.96, 22.66, 14.09.

[0374] MS (ESI): m/z calcd for C.sub.19H.sub.40N.sub.3O [M+H+CH.sub.3CN].sup.+: 326.30, found 326.32, m.p.: 89-91? C.

##STR00136##

[0375] 163 mg of white powder product was obtained by filtration and drying, with a yield of 71%.

[0376] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0377] .sup.13C NMR (126 MHz, Chloroform-d) ? 158.62, 40.58, 31.59, 30.29, 26.63, 22.60, 14.03.

[0378] MS (ESI): m/z calcd for C.sub.13H.sub.29N.sub.2O [M+H].sup.+: 229.20, found 229.23, m.p.: 73-76? C.

##STR00137##

[0379] 129 mg of white powder product was obtained by filtration and drying, with a yield of 64%.

[0380] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0381] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 158.52, 40.55, 30.19, 29.06, 22.35, 14.39.

[0382] MS (ESI): m/z calcd for C.sub.11H.sub.25N.sub.2O [M+H].sup.+: 201.15, found 201.20, m.p.: 86-88? C.

##STR00138##

[0383] After 36 h of reaction, 157 mg of white crystalline product was obtained by filtration and drying, with a yield of 73%.

[0384] .sup.1H NMR (500 MHz, TFA-d) ? 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).

[0385] .sup.13C NMR (126 MHz, TFA-d) ? 159.93, 55.32, 35.04, 27.30, 26.93.

[0386] MS (ESI): m/z calcd for C.sub.13H.sub.25N.sub.2O [M+H].sup.+: 225.10, found 225.20, m.p.: 229-230? C.

##STR00139##

[0387] 243 mg of light yellow powder product was obtained by filtration and drying, with a yield of 91%.

[0388] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0389] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 156.54, 145.67, 128.27, 126.50, 125.72, 48.50, 23.40.

[0390] MS (ESI): m/z calcd for C.sub.17H.sub.21N.sub.2O [M+H].sup.+: 269.10, found 269.17, m.p.: 122-123? C.

##STR00140##

[0391] 244 mg of silvery white powder product was obtained by filtration and drying, with a yield of 91%.

[0392] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0393] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 157.97, 139.81, 128.72, 128.35, 126.02, 40.97, 36.23.

[0394] MS (ESI): m/z calcd for C.sub.17H.sub.21N.sub.2O [M+H].sup.+: 269.10, found 269.17, m.p.: 138-140? C.

##STR00141##

[0395] 285 mg of white powder product was obtained by filtration and drying, with a yield of 96%.

[0396] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0397] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 158.22, 141.91, 128.33, 128.32, 125.74, 38.84, 32.58, 31.93.

[0398] MS (ESI): m/z calcd for C.sub.19H.sub.25N.sub.2O [M+H].sup.+: 297.20, found 297.20, m.p.: 92-93? C.

##STR00142##

[0399] 233 mg of white powder product was obtained by filtration and drying, with a yield of 86%.

[0400] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0401] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 157.93, 138.37, 135.45, 129.94, 127.22, 126.73, 125.77, 41.02, 18.58.

[0402] MS (ESI): m/z calcd for C.sub.17H.sub.21N.sub.2O [M+H].sup.+: 269.10, found 269.17, m.p.: 237-238? C.

##STR00143##

[0403] 260 mg of white crystalline product was obtained by filtration and drying, with a yield of 84%.

[0404] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0405] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 158.20, 140.09, 131.09, 128.88, 128.19, 42.34.

[0406] MS (ESI): m/z calcd for C.sub.15H.sub.16Cl.sub.2N.sub.2NaO.sub.2 [M+Na+H.sub.2O].sup.+: 350.05, found 350.05, m.p.: 253-254? C.

##STR00144##

[0407] 344 mg a offwhite crystalline product was obtained by filtration and drying, with a yield of 86%.

[0408] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0409] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 158.10, 140.50, 131.11, 129.27, 119.56, 42.42.

[0410] MS (ESI): m/z calcd for C.sub.15H.sub.16Br.sub.2N.sub.2NaO.sub.2 [M+Na+H.sub.2O].sup.+: 439.95, found 439.95, m.p.: 268-270? C.

##STR00145##

[0411] 257 mg of white powder product was obtained by filtration and drying, with a yield of 85%

[0412] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0413] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 158.15, 132.79, 128.40, 113.70, 55.13, 42.50.

[0414] MS (ESI): m/z calcd for C.sub.17H.sub.21N.sub.2O.sub.3 [M+H].sup.+: 301.10, found 301.16, m.p.: 178-180? C.

##STR00146##

[0415] 290 mg of light yellow solid product was obtained by filtration and drying, with a yield of 74%.

[0416] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0417] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 156.79, 144.01, 128.87, 127.25, 127.22, 57.41.

[0418] MS (ESI): m/z calcd for C.sub.27H.sub.25N.sub.2O [M+H].sup.+: 393.15, found 393.20, m.p.: 283-284? C.

##STR00147##

[0419] 106 mg of off-white powder product was obtained by filtration and drying, with a yield of 39%.

[0420] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0421] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 157.97, 156.08, 130.92, 128.38, 114.95, 42.57.

[0422] MS (ESI): m/z calcd for C.sub.15H.sub.17N.sub.2O.sub.3 [M+H].sup.+: 273.05, found 273.12, m.p.: 185-187? C.

##STR00148##

[0423] 240 mg of white crystalline product was obtained by filtration and drying, with a yield of 89%.

[0424] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0425] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 157.91, 137.68, 135.41, 128.62, 126.87, 42.59, 20.54.

[0426] MS (ESI): m/z calcd for C.sub.17H.sub.21N.sub.2O [M+H].sup.+: 269.10, found 269.17, m.p.: 216-218? C.

##STR00149##

[0427] 203 mg of white solid product product was obtained by filtration and drying, with a yield of 63%.

[0428] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0429] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 157.92, 146.59, 138.11, 126.98, 125.97, 42.67, 33.01, 23.87.

[0430] MS (ESI): m/z calcd for C.sub.21H.sub.29N.sub.2O [M+H].sup.+: 325.15, found 325.23, m.p.: 122-123? C.

##STR00150##

[0431] 287 mg of white powder product was obtained by filtration and drying, with a yield of 78%.

[0432] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0433] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 156.36, 141.29, 133.41, 130.42, 128.57, 127.14, 126.04, 125.54, 123.24, 121.84, 44.65, 22.53.

[0434] MS (ESI): m/z calcd for C.sub.25H.sub.25N.sub.2O [M+H].sup.+: 369.15, found 369.20, m.p.: 223-225? C.

##STR00151##

[0435] 33.1 mg of light yellow solid product was obtained by filtration and drying, with a yield of 87%.

[0436] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0437] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 157.97, 142.39, 130.80, 130.36, 128.96, 128.83, 127.29, 41.96.

[0438] MS (ESI): m/z calcd for C.sub.15H.sub.14ClN.sub.2NaO.sub.2 [M+Na+H.sub.2O].sup.+: 419.95, found 419.97, m.p.: 174-176? C.

##STR00152##

[0439] 196 mg of white powder product was obtained by filtration and drying, with a yield of 89%.

[0440] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0441] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 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.

[0442] MS (ESI): m/z calcd for C.sub.11H.sub.13N.sub.2O.sub.3 [M+H].sup.+: 221.00, found 221.09, m.p.: 126-128? C.

##STR00153##

[0443] A yellow oil was obtained by separation column with a yield of 89%.

[0444] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 6.08-6.02 (m, 2H), 3.75 (dq, J=13.9, 6.4 Hz, 4H), 3.59 (q, J=7.5 Hz, 2H), 3.10 (dq, J=14.3, 5.2 Hz, 2H), 3.05-2.95 (m, 2H), 1.89-1.72 (m, 6H), 1.52 - 1.41 (m, 2H).

[0445] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 158.68, 78.10, 67.40, 43.56, 28.43, 25.50.

[0446] MS (ESI): m/z calcd for C.sub.11H.sub.21N.sub.2O.sub.3 [M+H].sup.+: 229.10, found 229.16, Pyrolysis temperature: 140? C.

##STR00154##

[0447] 370 mg of yellow solid product was obtained by filtration and drying, with a yield of 93%.

[0448] .sup.1H NMR (500 MHz, TFA-d) ? 4.92 (t, J=7.1 Hz, 4H), 3.23 (p, J=6.9 Hz, 4H), 2.90 (d, J=31.6 Hz, 36H), 2.43 (td, J=6.7, 2.9 Hz, 6H).

[0449] .sup.13C NMR (126 MHz, TFA-d) ? 160.26, 109.99, 43.49, 33.13, 30.76, 30.65, 30.55, 30.51, 30.18, 29.82, 27.62, 23.70, 14.05.

[0450] MS (ESI): m/z calcd for C.sub.25H.sub.52KN.sub.2O [M+K].sup.+: 435.30, found 435.37, m.p.: 105-106? C.

##STR00155##

[0451] 311 mg of white solid product product was obtained by filtration and drying, with a yield of 83%.

[0452] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0453] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 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.

[0454] MS (ESI): m/z calcd for C.sub.17H.sub.15F.sub.6N.sub.2O [M+H].sup.+: 377.05, found 377.11, m.p.: 106-161? C.

##STR00156##

[0455] A light yellow oil was obtained by separation column with a yield of 92%.

[0456] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0457] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 159.69, 158.12, 148.69, 136.62, 121.90, 120.84, 44.96.

##STR00157##

[0458] 197 mg of brown yellow powder product was obtained by filtration and drying, with a yield of 78%.

[0459] .sup.1H NMR (500 MHz, DMSO-d.sub.6) ? 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).

[0460] .sup.13C NMR (126 MHz, DMSO-d.sub.6) ? 157.40, 144.22, 126.60, 124.66, 38.12.

[0461] MS (ESI): m/z calcd for C.sub.11H.sub.13N.sub.2OS.sub.2 [M+H].sup.+: 253.00, found 253.05, m.p.: 163-165? C.

[0462] All documents referred to in the present invention are incorporated by reference herein as if each document is individually incorporated by reference. Further, it should be understood that upon reading the above teaching of the present invention, various modifications or modifications may be made to the present invention by those skilled in the art, and those equivalents also fall within the scope defined by the appended claims of the present application.

METHOD FOR CATALYTICALLY ACTIVATING CARBON DIOXIDE AS CARBONYLATION REAGENT WITH INORGANIC SULFUR

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Abstract

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