Thiol salt-based ionic liquid catalyst and preparation method thereof, and method for capturing and converting CO2 by using thiolate-based ionic liquid catalyst

Abstract

The invention provides a preparation method of a mercaptide-based ionic liquid catalyst and a method for capturing and converting CO2 by using the mercaptide-based ionic liquid catalyst. The mercaptide-based ionic liquid is prepared by carrying out simple neutralization reaction on mercaptan and organic alkali. The structural formula of the thiolate-based ionic liquid is as shown in formula (1): # imgabs0 #. Compared with the existing ionic liquid for capturing CO2, the thiolate-based ionic liquid not only has excellent CO2 capturing performance, but also is easy to desorb CO2. When the thiolate-based ionic liquid is used as a non-metal homogeneous catalyst to be applied to a cycloaddition reaction of carbon dioxide and ethylene oxide or propargylamine to generate cyclic carbonate and oxazolidinone, the thiolate-based ionic liquid shows excellent catalytic performance and stable recycling and reusing performance. The mercaptide-based ionic liquid integrates capture and conversion functions, can realize high-capacity capture, low-energy barrier release and efficient conversion of CO2, and has wide application in a CCUS technology.

Description

Technical Field

[0001] The present invention relates to the fields of environment, catalysis and organic synthesis. Specifically, the present invention provides a method for preparing a thiolate-based ionic liquid catalyst and its capture and conversion of CO2. Background Art

[0002] With the gradual increase in the concentration of CO2 in the atmosphere, which leads to the intensification of the greenhouse effect, the development of green and sustainable methods for reducing the atmospheric CO2 concentration has received increasing attention. Due to its non-toxicity, abundance, low cost, and recyclability, CO2 is an ideal carbon source component. Using it as an organic synthon for chemical conversion into high-value-added fine chemicals is not only an effective way to reduce the atmospheric CO2 concentration but also an important strategy for the sustainable development of energy. Therefore, the development of CO2 capture and utilization (CCU) technology in a sustainable manner has become a hot technology that needs to be developed urgently.

[0003] Due to the thermodynamic stability and kinetic inertness of CO2, the key to both capture and conversion lies in the activation of CO2. Ionic liquids have become ideal capture agents and activators to replace traditional organic amines and metal salts due to their unique properties such as negligible vapor pressure, non-flammability, low toxicity, high thermal stability, strong dissolution ability, and adjustable structure and properties. Currently, most of the ionic liquids used for the capture and conversion of CO2 have nitrogen (Angew.Chem.Int.Ed., 2011, 50, 4918 - 4922) and oxygen (Angew.Chem.Int.Ed. 2016, 55, 7166 - 7170) as anion active sites, and their interaction with CO2 is too strong, which is not conducive to the desorption and further conversion of CO2.

[0004] The inventors of the present invention found through research that sulfur anions have higher nucleophilicity than nitrogen and oxygen anions and can also react with CO2 to form a CO2 adduct similar to carbamate or carbonate - thiocarbonate. Moreover, since the bond energy of the C - S bond in thiocarbonate is less than that of the C - N and C - O bonds in carbamate or carbonate, thiocarbonate can easily release CO2, which makes sulfur anions a potential active site for CO2 activation. Therefore, designing an ionic liquid with sulfur anion sites as the active component is expected to achieve the integration of CO2 capture and conversion. Summary of the Invention

[0005] Based on the above findings, the object of the present invention is to provide a thiolate-based ionic liquid catalyst, its preparation, and a method for capturing and converting CO2. The thiolate-based ionic liquid is prepared by a simple neutralization reaction of a thiol with an organic base. Compared with the existing ionic liquids for capturing CO2, such thiolate-based ionic liquids not only have excellent CO2 capture performance but also are easy to desorb CO2. When such thiolate-based ionic liquids are used as non-metallic homogeneous catalysts in the cycloaddition reaction of carbon dioxide with ethylene oxide or propargylamine to form cyclic carbonates and oxazolidinones, they exhibit excellent catalytic performance and stable recovery and reuse performance. The thiolate-based ionic liquid of the present invention combines the functions of capture and conversion, can achieve high-capacity capture and low-energy-barrier release of CO2 as well as efficient conversion, and has a wide range of applications in CCUS technology.

[0006] The first aspect of the present invention is to provide a thiolate-based ionic liquid, and the structural formula of the thiolate-based ionic liquid is shown in Formula (1):

[0007] X is N or P, and R1, R2, R3, and R4 are each independently selected from: H, substituted or unsubstituted C1-C 20 alkyl (for example, it can be methyl, ethyl, C3, C5, C7, C9, C 11 , C 13 , C 15 , C 17 , C 20 alkyl, and alkyl with any integer value between 1 and 20 carbon atoms); or, X, R1, R2, R3, and R4 together form the following groups: imidazole, pyrrole, pyridine, morpholine, piperidine, amidine, or guanidine;

[0008] R5 is selected from substituted or unsubstituted C1-C6 alkyl, phenyl unsubstituted or substituted by 1-3 groups selected from the following: halogen (for example, it can be fluorine, chlorine, bromine, iodine), C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; or, R5 is selected from pyridine groups, pyrimidine groups, imidazole groups, or thiophene groups.

[0009] According to the present invention, the alkyl in C1-C6 alkyl, C1-C6 haloalkyl, and C1-C6 alkoxy can each be C1, C2, C3, C4, C5, or C6 alkyl.

[0010] The second aspect of the present invention is to provide a preparation method of the thiolate-based ionic liquid described in the first aspect, including using the reaction formulas of Method 1, Method 2, or Method 3 to react the reaction substrate providing the X group with the reaction substrate providing the S-R5 group in a solvent to obtain the one shown in Formula (1) Among them, in Method 3, R4 is H;

[0011]

[0012] In Method 2: Y is a halogen, preferably Cl or Br; Z is an alkali metal element, preferably Na or K.

[0013] According to the present invention, by using Method 1, Method 2 or Method 3, in the reaction substrate providing the X group, R1, R2, R3 and R4 respectively correspond to the groups R1, R2, R3 and R4 of the thiolate-based ionic liquid shown in formula (1). By using Method 1, Method 2 or Method 3, R5 in the reaction substrate providing the S-R5 group respectively corresponds to the group R5 of the thiolate-based ionic liquid shown in formula (1). R1, R2, R3, R4, and R5 in formula (1) are as described in the first aspect above and will not be elaborated here. wherein R1, R2, R3, R4, and R5 are as described in the first aspect above and will not be elaborated here.

[0014] In some preferred embodiments of the present invention, the conditions in Method 1, Method 2, and Method 3 each include:

[0015] The solvent is selected from at least one of H2O, EtOH, MeOH, NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH2Cl2, CHCl3, CCl4, toluene, and ethyl acetate; and / or,

[0016] Relative to providing 1 mmol of the reaction substrate providing the S-R5 group, the amount of the solvent used is 0.5 - 50 mL, such as 0.5, 1, 3, 5, 10, 20, 30, 40, 50 mL, and any two values or any interval of any two values; and / or,

[0017] The molar ratio of the reaction substrate providing the X group to the reaction substrate providing the S-R5 group is 1:(0.5 - 2), such as the ratio of 1 to 0.5, 1, 1.5, 2 and any two values or any interval of any two values; and / or,

[0018] The reaction conditions include: the temperature is 0 - 150 °C, such as 0, 20, 25, 30, 40, 50, 100, 150 °C, and any two values or any interval of any two values, and / or, the reaction time is 5 min - 48 h, such as 5 min, 10 min, 30 min, 1 h, 2 h, 5 h, 10 h, 25 h, 35 h, 48 h, and any two values or any interval of any two values.

[0019] The third aspect of the present invention is to provide an application of the thiolate-based ionic liquid described in the first aspect or the thiolate-based ionic liquid obtained by the preparation method described in the second aspect in capturing CO2 or converting CO2.

[0020] The fourth aspect of the present invention is to provide a method for capturing CO2 with a thiolate-based ionic liquid. Under the condition of having or without a solvent, the thiolate-based ionic liquid is contacted with CO2 to capture the CO2. The thiolate-based ionic liquid is the thiolate-based ionic liquid described in the first aspect or the thiolate-based ionic liquid obtained by the preparation method described in the second aspect.

[0021] Regarding the method for capturing CO2 with a thiolate-based ionic liquid, in some preferred embodiments of the present invention, under the condition of having a solvent, the solvent is selected from at least one of H2O, EtOH, MeOH, NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH2Cl2, CHCl3, CCl4, toluene, ethyl acetate; and / or, relative to providing 1 mmol of the thiolate-based ionic liquid, the amount of the solvent used is 0.5 - 50 mL, such as 0.5, 1, 3, 5, 10, 20, 30, 40, 50 mL, as well as any two values or any interval of any two values; and / or,

[0022] Under the condition of having or without a solvent, the conditions for the contact each include: the temperature is 0 - 25 °C, such as 0, 5, 10, 15, 20, 25 °C, as well as any two values or any interval of any two values, and / or, the pressure is 0.1 - 3.5 MPa, such as 0.1, 0.5, 1, 1.5, 2, 3, 3.5 MPa, as well as any two values or any interval of any two values; and / or,

[0023] The product obtained by contacting the thiolate-based ionic liquid with CO2 is the compound shown in formula (2)

[0024]

[0025] The fifth aspect of the present invention is to provide a preparation method of a cyclic carbonate derivative, including: in a solvent, in the presence of a thiolate-based ionic liquid, reacting ethylene oxide shown in formula (3) with CO2 to obtain a cyclic carbonate derivative shown in formula (4);

[0026] The thiolate-based ionic liquid is the thiolate-based ionic liquid described in the first aspect or the thiolate-based ionic liquid obtained by the preparation method described in the second aspect;

[0027]

[0028] Among them, R6 and R7 are each independently selected from H, substituted or unsubstituted C1-C 10 alkyl (for example, alkyl with 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms), C1-C6 alkoxy, C1-C6 haloalkyl, phenyl which is unsubstituted or substituted by 1-3 substituents selected from the following: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3.

[0029] According to the present invention, the alkyl in C1-C6 alkyl, C1-C6 haloalkyl, and C1-C6 alkoxy can each be alkyl of C1, C2, C3, C4, C5, or C6.

[0030] Regarding the preparation method of the cyclic carbonate derivatives, in some preferred embodiments of the present invention,

[0031] the solvent is selected from at least one of H2O, EtOH, MeOH, NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH2Cl2, CHCl3, CCl4, toluene, ethyl acetate, supercritical CO2; and / or,

[0032] relative to providing 1 mmol of ethylene oxide shown in formula (3), the amount of the solvent used is 0.5-50 mL, such as 0.5, 1, 3, 5, 10, 20, 30, 40, 50 mL, and any two values or any interval of any two values; and / or,

[0033] the molar ratio of ethylene oxide shown in formula (3) to CO2 is 1:1-100, such as the ratio of 1 to 1, 5, 10, 20, 40, 60, 80, 100 and any two values or any interval of any two values; and / or,

[0034] During the reaction process, CO2 is continuously introduced into the reactor, and the pressure of CO2 in the reactor is 0.1-12 MPa, such as 0.1, 0.3, 0.5, 1, 3, 6, 9, 12 MPa, and any two values or any interval of any two values; and / or,

[0035] the molar ratio of ethylene oxide shown in formula (3) to the thiolate-based ionic liquid is 1:0.05-20, such as the ratio of 1 to 0.05, 0.1, 0.4, 0.8, 1, 5, 10, 15, 20 and any two values or any interval of any two values; and / or,

[0036] The reaction temperature is 25 to 150 °C, such as 25, 50, 75, 100, 130, 150 °C, and any two values or any interval of any two values; and / or, the reaction time is 1 to 48 h, such as 1, 2, 5, 10, 15, 20, 30, 40, 48 h, and any two values or any interval of any two values.

[0037] The sixth aspect of the present invention is to provide a method for preparing an oxazolidinone derivative, comprising: reacting a propargylamine derivative represented by formula (5) with CO2 in a solvent in the presence of a thiolate-based ionic liquid to obtain an oxazolidinone derivative represented by formula (6);

[0038] The thiolate-based ionic liquid is the thiolate-based ionic liquid described in the first aspect or the thiolate-based ionic liquid obtained by the preparation method described in the second aspect;

[0039]

[0040] Among them, R8 and R9 are each independently selected from H, substituted or unsubstituted C1-C 10 alkyl, phenyl unsubstituted or substituted by 1-3 substituents selected from the following: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; or R8 and R9 are each independently selected from: naphthyl, furyl, thienyl, pyridyl, pyrrolyl;

[0041] R 10 、R 11 are each independently selected from H, substituted or unsubstituted C1-C6 alkyl, or phenyl unsubstituted or substituted by 1-3 substituents selected from the following: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; or R 10 、R 11 are each independently selected from: naphthyl, furyl, thienyl, pyridyl, pyrrolyl; or R 10 and R 11 together form -(CH2) n -, where n is selected from 2, 3, 4, 5 or 6.

[0042] According to the present invention, the alkyl in C1-C6 alkyl, C1-C6 haloalkyl, and C1-C6 alkoxy can each be an alkyl of C1, C2, C3, C4, C5, or C6.

[0043] Regarding the method for preparing an oxazolidinone derivative, in some preferred embodiments of the present invention,

[0044] The solvent is selected from at least one of H2O, EtOH, MeOH, NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH2Cl2, CHCl3, CCl4, toluene, ethyl acetate, and supercritical CO2; and / or,

[0045] Relative to providing 1 mmol of the propargylamine derivative shown in formula (5), the amount of the solvent used is 0.5 - 50 mL, such as 0.5, 1, 3, 5, 10, 20, 30, 40, 50 mL, and any two numerical values or any interval of any two numerical values; and / or,

[0046] The molar ratio of the propargylamine derivative shown in formula (5) to CO2 is 1:1 - 100, such as the ratio of 1 to 1, 5, 10, 20, 40, 60, 80, 100 and any two numerical values or any interval of any two numerical values; and / or,

[0047] During the reaction process, CO2 is continuously introduced into the reactor, and the pressure of the CO2 in the reactor is 0.1 - 12 MPa, such as 0.1, 0.3, 0.5, 1, 3, 6, 9, 12 MPa, and any two numerical values or any interval of any two numerical values; and / or,

[0048] The molar ratio of the propargylamine derivative shown in formula (5) to the thiolate-based ionic liquid is 1:0.05 - 20, such as the ratio of 1 to 0.05, 0.1, 0.4, 0.8, 1, 5, 10, 15, 20 and any two numerical values or any interval of any two numerical values; and / or,

[0049] The reaction temperature is 25 - 150 °C, such as 25, 50, 75, 100, 130, 150 °C, and any two numerical values or any interval of any two numerical values; and / or, the reaction time is 1 - 48 h, such as 1, 2, 5, 10, 15, 20, 30, 40, 48 h, and any two numerical values or any interval of any two numerical values.

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

[0051] The advantages of the present invention are:

[0052] The present invention provides a thiolate-based ionic liquid, a preparation method thereof, and a method for capturing and converting CO2. This ionic liquid is prepared by a simple neutralization reaction of a thiol with an organic base. Compared with the existing ionic liquids for capturing CO2, such thiolate-based ionic liquids not only have excellent CO2 capture performance but also are easy to desorb CO2. When such thiolate-based ionic liquids are used as non-metal homogeneous catalysts in the cycloaddition reaction of carbon dioxide with ethylene oxide or propargylamine to form cyclic carbonates and oxazolidinones, they exhibit excellent catalytic performance and stable recycling performance. The thiolate-based ionic liquid of the present invention combines the functions of capture and conversion, can achieve high-capacity capture and low-energy-barrier release of CO2 as well as efficient conversion, and has a wide range of applications in CCUS technology. Description of the Drawings

[0053] Figures 1 - 2 It corresponds to the reaction process of the thiolate-based ionic liquid capturing CO2 shown in the figure.

[0054] Figure 3 It is the temperature curve of desorbing CO2 after [TBP][2-Tp] captures CO2 in Example 2B.

[0055] Figure 4 It is the catalytic stability experiment of the thiolate-based ionic liquid [TBP][2-Tp] in Example 4 for the reaction of N-butyl-2-methyl-4-phenylbut-3-yn-2-amine with CO2 to prepare (Z)-5-benzylidene-3-butyl-4,4-dimethyloxazolidin-2-one. Detailed Embodiments

[0056] The present invention will be specifically described below in conjunction with specific embodiments. It is necessary to point out here that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention still fall within the protection scope of the present invention.

[0057] Next, the technical solutions of the present invention will be described in detail through specific embodiments.

[0058] Example 1

[0059] Preparation method of the thiolate-based ionic liquid:

[0060] Method 1: Preparation process of aprotic ionic liquid. Taking [TBP][2-Tp] as an example, 2-mercaptopyridine (0.0610 g, 0.55 mmol) was placed in a 40% w / w aqueous solution of tetrabutylphosphonium hydroxide (0.3453 g, 0.5 mmol) and stirred at room temperature for 12 hours. Then the solvent was evaporated under vacuum at 70 °C to obtain a yellow liquid [TBP][2-Tp].

[0061] Method 2: Mix tetrabutylphosphonium chloride (0.1471 g, 0.5 mmol), sodium pyridine-2-thiolate (0.0665 g, 0.5 mmol) and methanol (2 mL) solution and stir for 6 hours. Filter the precipitated NaCl and evaporate the solvent on a rotary evaporator. Then dissolve the product in dry DCM (2 mL) and remove the residual NaCl by filtration. Then evaporate the solvent under vacuum at 70 °C to obtain a yellow liquid [TBP][2-Tp].

[0062]

[0063] tetrabutylphosphonium pyridine-2-thiolate([TBP][2-Tp]) ; 1 H NMR (500 MHz, DMSO-d6) δ 7.85–7.76 (m, 1H), 6.97–6.89 (m, 1H), 6.86–6.75 (m, 1H), 6.34–6.25 (m, 1H), 2.27–2.19 (m, 8H), 1.49–1.35 (m, 16H), 0.90 (t, J = 7.1 Hz, 12H) ppm; 13 C NMR (125 MHz, DMSO-d6) δ 180.7, 147.1, 131.7, 128.7, 111.5, 23.4, 23.3, 22.7(1), 22.6(8), 17.6, 17.2, 13.2 ppm.

[0064] Method 3: Preparation process of protonic ionic liquid. Taking [DBUH][2-Tp] as an example, add ethanol (2 mL), DBU (1,8-diazabicycloundec-7-ene) (0.5 mmol, 0.0761 g) and 2-mercaptopyridine (0.5 mmol, 0.0555 g) into a 25 mL flask in a water bath at 25 °C and carry out the neutralization reaction for 12 hours. Then evaporate the solvent under vacuum at 70 °C and finally obtain a dark brown liquid [DBUH][2-Tp].

[0065]

[0066] 2,3,4,6,7,8,9,10-octahydro-1H-pyrimido[1,2-a]azepin-5-ium pyridine-2- thiolate([DBUH][2-Tp]) ; 1 H NMR (500 MHz, CDCl3) δ 9.57 (s, 1H), 8.09 (d, J = 5.5 Hz, 1H), 7.37 (d, J = 9.0 Hz, 1H), 7.05 (t, J = 6.0 Hz, 1H), 6.51 (t, J = 6.0 Hz, 1H), 3.36–3.32 (m, 6H), 2.74 (t, J = 5.5 Hz, 2H), 1.90–1.85 (m, 2H), 1.62–1.56 (m, 6H) ppm;13 13C NMR (125 MHz, CDCl3) δ 176.7, 165.2, 145.3, 134.6, 130.8, 113.8, 54.0, 48.6, 39.2, 33.0, 29.1, 27.1, 24.4, 20.1 ppm.

[0067]

[0068] Using the method as described above in Example 1, according to the above reaction formula, by changing the reaction substrates, the following respective products were obtained:

[0069] Referring to Method 1 in the above examples, [TMA][BnT]:

[0070]

[0071] tetramethylammonium phenylmethanethiolate([TMA][BnT]) ; 1 1H NMR (500 MHz, D2O) δ 7.38–7.26 (m, 4H), 7.19 (t, J = 6.3 Hz, 1H), 3.61 (s, 2H), 3.13 (s, 12H) ppm; 13 13C NMR (125 MHz, D2O) δ 147.6, 128.5, 127.8, 125.3, 55.1(8), 55.1(5), 55.1(1), 28.9 ppm.

[0072] Referring to Method 1 in the above examples, [TMA][4-Br-BT]:

[0073]

[0074] tetramethylammonium 4-bromobenzenethiolate([TMA][4-Br-BT]) ; 1 1H NMR (500 MHz, D2O) δ 7.25 (d, J = 8.5 Hz, 2H), 7.21 (d, J = 8.4 Hz, 2H), 3.15 (s, 12H) ppm; 13 13C NMR (125 MHz, D2O) δ 145.5, 134.6, 130.7, 114.0, 55.1(8), 55.1(4), 55.1(1) ppm.

[0075] Referring to Method 1 in the above examples, [TMA][4-Me-BT]:

[0076]

[0077] tetramethylammonium 4-methylbenzenethiolate([TMA][4-Me-BT]) ; 11H NMR (500 MHz, D2O) δ 7.25 (d, J = 8.0 Hz, 2H), 6.95 (d, J = 7.9 Hz, 2H), 3.12 (s, 12H), 2.21 (s, 3H) ppm; 13 13C NMR (125 MHz, D2O) δ 141.6, 132.9, 131.3, 128.9, 55.1(5), 55.1(2), 55.0(8), 19.6 ppm.

[0078] Referring to Method 1 in the above embodiments, [TMA][2-Tp]:

[0079]

[0080] tetramethylammonium pyridine-2-thiolate([TMA][2-Tp]) ; 1 1H NMR (500 MHz, D2O) δ 8.03 (d, J = 5.3 Hz, 1H), 7.41–7.35 (m, 2H), 6.93–6.87 (m, 1H), 3.13 (s, 12H) ppm; 13 13C NMR (125 MHz, D2O) δ 170.0, 146.7, 136.5, 129.3, 116.7, 55.1(7), 55.1(4), 55.1(1) ppm.

[0081] Referring to Method 1 in the above embodiments, [TMA][4-Tp]:

[0082]

[0083] tetramethylammonium pyridine-4-thiolate([TMA][4-Tp]) ; 1 1H NMR (500 MHz, D2O) δ 7.91 (d, J = 6.4 Hz, 2H), 7.34 (d, J = 6.4 Hz, 2H), 3.12 (s, 12H) ppm; 13 13C NMR (125 MHz, D2O) δ 165.4, 144.9, 129.3, 55.1(5), 55.1(2), 55.0(8) ppm.

[0084] Referring to Method 1 in the above embodiments, [TMA][2-5-Tp]:

[0085]

[0086] tetramethylammonium pyrimidine-2-thiolate([TMA][2-5-Tp]) ; 1 1H NMR (500 MHz, D2O) δ 8.27 (d, J = 5.0 Hz, 2H), 6.95 (t, J = 4.9 Hz, 1H), 3.17 (s, 12H) ppm;13 C NMR (125 MHz, D2O) δ 181.5, 156.3, 113.6, 55.2(0), 55.1(6), 55.1(3) ppm.

[0087] Referring to Method 1 in the above embodiments, [TMA][Py-NO]:

[0088]

[0089] tetramethylammonium 2-sulfidopyridine 1-oxide([TMA][Py-NO]) ; 1 H NMR (500 MHz, D2O) δ 8.06 (d, J = 6.4 Hz, 1H), 7.59 (d, J = 8.1 Hz, 1H), 7.20 (t, J = 7.7 Hz, 1H), 6.93 (t, J = 6.6 Hz, 1H), 3.18 (s, 12H) ppm; 13 C NMR (125 MHz, D2O) δ 163.8, 138.5, 132.6, 129.2, 117.5, 55.1(9), 55.1(6), 55.1(3) ppm.

[0090] Referring to either Method 1 or Method 2 in the above embodiments, [TEA][2-Tp]:

[0091]

[0092] tetraethylammonium pyridine-2-thiolate([TEA][2-Tp]) ; 1 H NMR (500 MHz, D2O) δ 8.13–7.97 (m, 1H), 7.48–7.26 (m, 2H), 6.97–6.81 (m, 1H), 3.26–3.12 (m, 8H), 1.32–1.10 (m, 12H) ppm; 13 C NMR (125 MHz, D2O) δ 170.1, 147.0, 136.2, 129.2, 116.7, 51.8(1), 51.7(8), 51.7(6), 6.5 ppm.

[0093] Referring to either Method 1 or Method 2 in the above embodiments, [TPA][2-Tp]:

[0094]

[0095] tetrapropylammonium pyridine-2-thiolate([TPA][2-Tp]) ; 11H NMR (500 MHz, D2O) δ 8.04 (d, J = 4.9 Hz, 1H), 7.44–7.33 (m, 2H), 6.96–6.87 (m, 1H), 3.17–3.12 (m, 8H), 1.73–1.64 (m, 8H), 0.94 (t, J = 7.3 Hz, 12H) ppm; 13 13C NMR (125 MHz, D2O) δ 169.9, 146.7, 136.4, 129.3, 116.7, 59.7(9), 59.7(7), 59.7(5), 14.7, 9.7 ppm.

[0096] Referring to Method 1 or Method 2 in the above embodiments, [TBA][2-Tp]:

[0097]

[0098] tetrabutylammonium pyridine-2-thiolate([TBA][2-Tp]) ; 1 1H NMR (500 MHz, D2O) δ 7.98 (d, J = 5.1 Hz, 1H), 7.49 (t, J = 7.6 Hz, 1H), 7.43 (d, J = 8.2 Hz, 1H), 6.96 (t, J = 6.2 Hz, 1H), 3.26–3.08 (m, 8H), 1.72–1.54 (m, 8H), 1.44–1.27 (m, 8H), 0.94 (t, J = 7.4 Hz, 12H) ppm; 13 13C NMR (125 MHz, D2O) δ 170.9, 143.7, 137.8, 130.4, 116.5, 58.0(5), 58.0(3), 58.0(1), 23.1, 19.1, 12.8 ppm.

[0099] Referring to Method 1 in the above embodiments, [TBA][2-5-Tp]:

[0100]

[0101] tetrabutylammonium pyrimidine-2-thiolate([TBA][2-5-Tp]) ; 1 1H NMR (500 MHz, CDCl3) δ 8.04 (d, J = 5.0 Hz, 2H), 6.38 (t, J = 4.5 Hz, 1H), 3.32 (t, J = 8.5 Hz, 8H), 1.61–1.54 (m, 8H), 1.37–1.30 (m, 8H), 0.90 (t, J = 7.5 Hz, 12H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 188.6, 155.3, 110.9, 59.0, 24.2, 19.8, 13.8. ppm.

[0102] Referring to Method 1 in the above embodiments, we obtain [TBA][NO2-BT]:

[0103]

[0104] tetrabutylammonium 4-nitrobenzenethiolate([TBA][NO 2 -BT]) ; 1 H NMR (500 MHz, CDCl3) δ 7.68 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 9.0 Hz, 2H), 3.19 (t, J = 8.5 Hz, 8H), 1.60–1.54 (m, 8H), 1.40–1.33 (m, 8H), 0.96 (t, J = 7.5 Hz, 12H) ppm; 13 C NMR (125 MHz, CDCl3) δ 133.6, 131.0, 124.2, 122.3, 58.9, 24.0, 19.7, 13.6 ppm.

[0105] Referring to either Method 1 or Method 2 in the above embodiments, we can obtain [TBA][Py-NO]

[0106]

[0107] tetrabutylammonium 2-sulfidopyridine 1-oxide ([TBA][Py-NO]) ; 1 H NMR (500 MHz, CDCl3) δ 7.99 (d, J = 6.0 Hz, 1H), 7.59 (d, J = 10.0 Hz, 1H), 6.68 (t, J = 8.0 Hz, 1H), 6.45 (t, J = 6.5 Hz, 1H), 3.36 (t, J = 8.5 Hz, 8H), 1.66 - 1.59 (m, 8H), 1.43 - 1.35 (m, 8H), 0.95 (t, J = 7.5 Hz, 12H) ppm; 13 C NMR (125 MHz, CDCl3) δ 167.7, 138.6, 133.3, 123.7, 114.1, 59.2, 24.3, 19.9, 13.8 ppm.

[0108] Referring to either Method 1 or Method 2 in the above embodiments, we can obtain [Ch][2-Tp]:

[0109]

[0110] 2-hydroxy-N,N,N-trimethylethan-1-aminium pyridine-2-thiolate ([Ch][2- Tp]) ; 11H NMR (500 MHz, D2O) δ 8.02 (d, J = 5.4 Hz, 1H), 7.45–7.37 (m, 2H), 6.93 (t, J = 6.1 Hz, 1H), 4.08–3.99 (m, 2H), 3.52–3.44 (m, 2H), 3.16 (s, 9H) ppm; 13 13C NMR (125 MHz, D2O) δ 170.1, 145.9, 136.9, 129.6, 116.7, 67.3(5), 67.3(2), 67.3(0), 55.51, 53.8(1), 53.7(8), 53.7(5) ppm.

[0111] Referring to Method 3 in the above embodiments, [TMG][2-5-Tp]:

[0112]

[0113] bis(dimethylamino)methaniminium pyrimidine-2-thiolate ([TMG][2-5-Tp]) ; 1 1H NMR (500 MHz, CDCl3) δ 8.22 (d, J = 5.0 Hz, 2H), 6.54 (t, J = 5.0 Hz, 1H), 2.96 (s, 12H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 186.3, 162.8, 155.6, 111.6, 40.1 ppm.

[0114] Referring to Method 3 in the above embodiments, [TMG][Py-NO]:

[0115]

[0116] bis(dimethylamino)methaniminium 2-sulfidopyridine 1-oxide ([TMG][Py- NO]) ; 1 1H NMR (500 MHz, CDCl3) δ 8.01 (d, J = 6.0 Hz, 1H), 7.65 (d, J = 8.5 Hz, 1H), 6.81 (t, J = 7.0 Hz, 1H), 6.53 (t, J = 6.5 Hz, 1H), 2.94 (s, 16H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 168.0, 162.9, 138.4, 133.8, 125.7, 114.6, 39.9 ppm.

[0117] Referring to Method 3 in the above embodiments, [TMG][4-Br-BT]:

[0118]

[0119] bis(dimethylamino)methaniminium 4-bromobenzenethiolate ([TMG][4-Br-BT]) ; 1 1H NMR (500 MHz, CDCl3) δ 7.24 (d, J = 8.0 Hz, 2H), 6.99 (d, J = 8.5 Hz, 2H), 2.86 (s, 12H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 163.0, 150.6, 135.0, 130.1, 112.8, 39.9 ppm.

[0120] Referring to Method 3 in the above embodiments, [TMG][2-Tp]:

[0121]

[0122] bis(dimethylamino)methaniminium pyridine-2-thiolate ([TMG][2-Tp]) ; 1 1H NMR (500 MHz, CDCl3) δ 8.06 (d, J = 6.5 Hz, 1H), 7.88 (s, 2H), 7.45 (d, J = 8.5 Hz, 1H), 7.19 (d, J = 8.5 Hz, 1H), 6.63 (t, J = 7.0 Hz, 1H), 2.83 (s, 12H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 176.3, 164.2, 142.6, 136.1, 132.1, 114.0, 39.8 ppm.

[0123] Referring to Method 3 in the above embodiments, [DBUH][MIT]:

[0124]

[0125] 2,3,4,6,7,8,9,10-octahydro-1H-pyrimido[1,2-a]azepin-5-ium 1-methyl- 1H-imidazole-2-thiolate ([DBUH][MIT]) ; 1 1H NMR (500 MHz, CDCl3) δ 6.65 (d, J = 8.0 Hz, 2H), 3.58 (s, 3H), 3.33 (t, J = 5.5 Hz, 2H), 3.25–3.22 (m, 4H), 2.51 (t, J = 3.5 Hz, 2H), 1.86–1.81 (m, 2H), 1.66–1.57 (m, 6H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 162.9, 160.8, 118.8, 116.1, 53.2, 48.6, 42.6, 36.0, 34.3, 29.7, 28.3, 25.6, 21.9 ppm.

[0126] Referring to Method 3 in the above embodiments, [DBUH][4-Tp]:

[0127]

[0128] 2,3,4,6,7,8,9,10-octahydro-1 H -pyrimido[1,2- a azepin-5-ium pyridine-4- thiolate ([DBUH][4-Tp]) ; 1 1H NMR (500 MHz, CDCl3) δ 7.83 (d, J = 6.0 Hz, 2H), 7.27 (d, J = 6.0 Hz, 2H), 3.46–3.41 (m, 4H), 3.32 (t, J = 6.0 Hz, 2H), 2.78 (t, J = 5.5 Hz, 2H), 1.99–1.75 (m, 2H), 1.72–1.58 (m, 6H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 166.1, 145.7, 129.9, 58.1, 54.5, 48.8, 38.2, 32.4, 29.1, 26.9, 24.1, 19.7 ppm.

[0129] Referring to Method 3 in the above embodiments, [DBUH][MDPT]:

[0130]

[0131] 2,3,4,6,7,8,9,10-octahydro-1H-pyrimido[1,2-a]azepin-5-ium 1-methyl-4, 5-dihydro-1H-pyrrole-2-thiolate ([DBUH][MDPT]) ; 1 1H NMR (500 MHz, CDCl3) δ 3.73 (t, J = 7.0 Hz, 2H), 3.26 (t, J = 5.5 Hz, 5H), 3.21–3.16 (m, 4H), 3.04 (t, J = 8.5 Hz, 2H), 2.38 (t, J = 3.5 Hz, 2H), 2.09–2.03 (m, 2H), 1.80–1.75 (m, 2H), 1.65–1.56 (m, 6H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 201.1, 161.6, 57.1, 52.9, 48.4, 44.7, 44.2, 37.3, 35.5, 29.8, 28.5, 26.0, 22.5, 19.4 ppm.

[0132] Referring to Method 3 in the above embodiments, DBUH][MTT]:

[0133]

[0134] 2,3,4,6,7,8,9,10-octahydro-1H-pyrimido[1,2-a]azepin-5-ium 4-methyl- 4H-1,2,4-triazole-3-thiolate ([DBUH][MTT]) ; 11H NMR (500 MHz, CDCl3) δ 7.84 (s, 1H), 3.61 (t, J = 5.5 Hz, 2H), 3.56 (s, 3H), 3.46–3.41 (m, 4H), 3.00 (t, J = 5.0 Hz, 2H), 2.06–2.01 (m, 2H), 1.82–1.65 (m, 6H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 166.9, 166.2, 142.0, 54.2, 48.8, 38.6, 32.5, 31.6, 29.3, 27.3, 24.4, 20.0 ppm.

[0135] Referring to Method 3 in the above embodiments, [DBUH][Py-NO]:

[0136]

[0137] 2,3,4,6,7,8,9,10 - octahydro - 1H - pyrimido[1,2 - a]azepin - 5 - ium 2 - sulfidopyridine 1 - oxide([DBUH][Py - NO]) ; 1 1H NMR (500 MHz, CDCl3) δ 7.99 (d, J = 6.5 Hz, 1H), 6.63 (d, J = 8.5 Hz, 1H), 6.95 (t, J = 7.0 Hz, 1H), 6.59 (t, J = 7.5 Hz, 1H), 3.55 (t, J = 7.0 Hz, 2H), 3.43–3.38 (m, 4H), 2.97 (t, J = 6.0 Hz, 2H), 2.01–1.96 (m, 2H), 1.72–1.64 (m, 6H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 167.7, 165.9, 136.0, 133.1, 128.0, 114.3, 54.3, 48.8, 38.7, 32.5, 29.2, 27.1, 24.1, 19.9 ppm.

[0138] Referring to Method 3 in the above embodiments, [DBUH][2 - 5 - Tp]:

[0139]

[0140] 2,3,4,6,7,8,9,10 - octahydro - 1H - pyrimido[1,2 - a]azepin - 5 - ium pyrimidine - 2 - thiolate([DBUH][2 - 5 - Tp]) ; 1 1H NMR (500 MHz, CDCl3) δ 8.39 (d, J = 5.0 Hz, 2H), 6.56 (t, J = 4.5 Hz, 1H), 3.50–3.45 (m, 6H), 2.93 (d, J = 6.0 Hz, 2H), 2.02–1.97 (m, 2H), 1.70–1.64 (m, 6H) ppm; 1313C NMR (125 MHz, CDCl3) δ 185.7, 166.1, 155.6, 111.0, 54.5, 48.8, 38.4, 32.4, 29.1, 26.9, 24.1, 19.7 ppm.

[0141] Referring to Method 3 in the above embodiments, obtain [DBUH][4 - Br - BT]:

[0142]

[0143] 2,3,4,6,7,8,9,10 - octahydro - 1H - pyrimido[1,2 - a]azepin - 5 - ium 4 - bromobenzenethiolate([DBUH][4 - Br - BT]) ; 1 1H NMR (500 MHz, CDCl3) δ 8.14 (s, 1H), 7.17 (d, J = 7.5 Hz, 2H), 6.89 (s, 2H), 3.33–3.28 (m, 4H), 3.18 (t, J = 5.5 Hz, 2H), 2.68 (t, J = 5.0 Hz, 2H), 1.85–1.81 (m, 2H), 1.63–1.48 (m, 6H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 165.4, 151.3, 135.2, 129.8, 112.2, 54.1, 48.5, 38.3, 32.3, 29.0, 26.8, 24.1, 19.7 ppm.

[0144] Referring to Method 3 in the above embodiments, obtain [DBUH][4 - MeO - BT]:

[0145]

[0146] 2,3,4,6,7,8,9,10 - octahydro - 1H - pyrimido[1,2 - a]azepin - 5 - ium 4 - methoxybenzenethiolate([DBUH][4 - MeO - BT]) ; 1 1H NMR (500 MHz, DMSO-d6) δ 7.04 (d, J = 10.0 Hz, 2H), 6.50 (d, J = 5.0 Hz, 2H), 3.61 (s, 3H), 3.46 (t, J = 4.5 Hz, 2H), 3.40 (t, J = 6.0 Hz, 2H), 3.17 (t, J = 5.5 Hz, 2H), 2.70 (t, J = 4.5 Hz, 2H), 1.85–1.81 (m, 2H), 1.61 (d, J = 5.0 Hz, 2H), 1.55–1.51 (m, 4H) ppm; 13 13C NMR: (125 MHz, DMSO-d6) δ 165.1, 133.2, 126.1, 113.8, 55.5, 53.5, 48.2, 40.0, 38.5, 32.0, 28.8, 26.7, 24.2, 19.8 ppm.

[0147] Referring to Method 3 in the above embodiments, we obtain [DBUH][4 - NO2 - BT]:

[0148]

[0149] 2,3,4,6,7,8,9,10 - octahydro - 1H - pyrimido[1,2 - a]azepin - 5 - ium 4 - nitrobenzenethiolate([DBUH][4 - NO2 - BT]) ; 1 H NMR(500 MHz, CDCl3) δ 7.75 (s, 2H), 7.41 (s, 2H), 3.46–3.41 (m, 4H), 3.32 (t, J = 6.0 Hz, 2H), 2.77 (t, J = 5.0 Hz, 2H), 2.01–1.95 (m, 2H), 1.74–1.63 (m, 6H) ppm; 13 C NMR(125 MHz, CDCl3) δ 165.0, 154.2, 134.0, 132.7, 113.4, 54.0, 48.6, 39.1, 32.9, 29.2, 27.2, 24.4, 20.2 ppm.

[0150] Referring to Method 3 in the above embodiments, we obtain [DBUH][DPT]:

[0151]

[0152] 2,3,4,6,7,8,9,10 - octahydro - 1H - pyrimido[1,2 - a]azepin - 5 - ium 3,4 - dihydro - 2H - pyrrole - 5 - thiolate([DBUH][DPT]) ; 1 H NMR(500 MHz, CDCl3) δ 3.60 (t, J = 7.5 Hz, 2H), 3.23 (t, J = 5.5 Hz, 2H), 3.17–3.13 (m, 4H), 2.85 (t, J = 8.0 Hz, 2H), 2.36 (t, J = 3.5 Hz, 2H), 2.18–2.11 (m, 2H), 1.77–1.72 (m, 2H), 1.56–1.52 (m, 6H) ppm; 13 C NMR(125 MHz, CDCl3) δ 205.5, 161.9, 52.9, 49.7, 48.4, 43.8, 43.5, 37.1, 29.8, 28.5, 25.9, 23.0, 22.4 ppm.

[0153] Referring to Method 3 in the above embodiments, we obtain [DBUH][SDI]:

[0154]

[0155] 2,3,4,6,7,8,9,10 - octahydro - 1H - pyrimido[1,2 - a]azepin - 5 - ium 2 - sulfido - 4,5 - dihydroimidazol - 1 - ide([DBUH][SDI]) ; 11H NMR (500 MHz, CDCl3) δ 3.67 (d, J = 2.0 Hz, 1H), 3.23 (t, J = 5.0 Hz, 2H), 3.17–3.12 (m, 4H), 2.34 (t, J = 3.5 Hz, 2H), 1.76–1.71 (m, 2H), 1.61–1.52 (m, 6H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 184.9, 161.7, 52.9, 48.5, 44.9, 44.2, 37.4, 29.9, 28.6, 26.1, 22.6 ppm.

[0156] Referring to Method 3 in the above embodiments, [DBUH][DTT]:

[0157]

[0158] 2,3,4,6,7,8,9,10 - octahydro - 1H - pyrimido[1,2 - a]azepin - 5 - ium 4,5 - dihydrothiazole - 2 - thiolate([DBUH][DTT]) ; 1 1H NMR (500 MHz, CDCl3) δ 4.02 (t, J = 8.0 Hz, 2H), 3.39 (t, J = 7.5 Hz, 4H), 3.35 (d, J = 6.5 Hz, 4H), 2.66 (d, J = 6.0 Hz, 2H), 1.94–1.89 (m, 2H), 1.62–1.70 (m, 6H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 192.3, 164.2, 57.3, 53.8, 48.7, 40.8, 35.1, 34.5, 29.5, 27.7, 25.0, 21.0 ppm.

[0159] Referring to Method 3 in the above embodiments, [DBUH][ODTT]:

[0160]

[0161] 2,3,4,6,7,8,9,10 - octahydro - 1H - pyrimido[1,2 - a]azepin - 5 - ium 4 - oxo - 4,5 - dihydrothiazole-2-thiolate([DBUH][ODTT]) ; 1 1H NMR (500 MHz, CDCl3) δ 3.87 (s, 2H), 3.55 (t, J = 6 Hz, 2H), 3.48 (t, J = 5.5 Hz, 2H), 3.45 (t, J = 6.0 Hz, 2H), 2.99 (t, J = 6.5 Hz, 2H), 2.04–1.99 (m, 2H), 1.75–1.67 (m, 6H) ppm; 13CNMR (125 MHz, CDCl3) δ 217.4, 192.0, 166.5, 54.4, 48.8, 43.6, 38.4, 32.4, 29.2, 27.0, 24.2, 19.7 ppm.

[0162] Example 2A

[0163] Method for capturing CO2 with thiolate-based ionic liquid:

[0164] Add 5 mmol of ionic liquid to a high-pressure reactor, install the high-pressure reactor and tighten the valve. Open the inlet and gradually introduce carbon dioxide gas into the reactor at a set flow rate. Monitor the carbon dioxide flow rate and the final flow. Ensure that the reactor pressure reaches 0.35 MPa, then close the gas cylinder, set the rotation speed to 600 rpm, and start the stirrer. Record the change in pressure inside the reactor and sample regularly. Wait for the reaction to reach equilibrium. Open the sample discharge valve, take out the sample, analyze the change in sample weight on an electronic balance with an accuracy of ±0.1 mg, and calculate the solubility of carbon dioxide to determine the carbon dioxide capture amount.

[0165] The calculation method for the carbon dioxide capture amount is as follows:

[0166] The absorption amount of CO2 is calculated by the weighing method:

[0167]

[0168] m 前 = Total mass of the reactor after adding T-ILs; m 后 = Total mass of the reactor after absorbing CO2;

[0169] m 吸收剂 = Total mass of the added T-ILs; Mco2 = Relative molecular mass of CO2;

[0170] M 吸收剂 = Relative molecular mass of T-ILs.

[0171] Using the method as described above, the amounts of CO2 captured by each of the thiolate-based ionic liquids are as follows:

[0172] T-ILs <![CDATA[Absorption capacity(mol CO2 / mol T-ILs)]]> [TBP][2-Tp] 1.55 [TBP][4-MeO-BT] 0.93 [TBP][4-Tp] 1.18 [TBP][4-Me-BT] 0.88 [TBA][2-Tp] 0.58 [TMA][2-Tp] 0.97 [Ch][2-Tp] 0.82 [DBUH][4-MeO-BT] 0.71

[0173] Note: The reaction process of some thiolate-based ionic liquids capturing CO2 can be found in the appendix Figure 1 、 Figure 2 。

[0174] It has been verified that the thiolate-based ionic liquids in Example 1 can all capture CO2.

[0175] Example 2B

[0176] Method for analyzing CO2: Taking [TBP][2-Tp] as an example, after using [TBP][2-Tp] to capture CO2 by the method in Example 2A, open the valve of the autoclave and raise the temperature to a certain temperature (see Figure 3 ) to analyze CO2. Calculate the amount of CO2 released by using the above calculation method for the amount of CO2 captured, and obtain the CO2 release efficiency at different temperatures.

[0177] It has been verified that other thiolate-based ionic liquids in the present invention are also easy to analyze after capturing CO2, which will be more conducive to the next round of cyclic absorption and conversion of CO2.

[0178] Example 3

[0179] Method for using thiolate-based ionic liquid as a catalyst to catalyze the reaction of ethylene oxide and CO2 to prepare cyclic carbonate:

[0180]

[0181] Add 1.0 mmol of epichlorohydrin, a certain amount of thiolate-based ionic liquid shown in the following table, and 2 mL of a suitable solvent to a 25 mL stainless steel autoclave equipped with a magnetic stirrer, and tighten the autoclave. After flushing and replacing the gas three times with N2 gas in cooperation with a vacuum pump, place the autoclave in a sand bath at a certain temperature and preheat for 0.5 h, then introduce CO2 at a certain pressure into the autoclave, and stir and react at a suitable temperature for a certain time (see the following table). After the reaction is completed, take out the autoclave and cool it to room temperature, extract the reaction solution with dichloromethane, collect and combine the organic phases, dry with anhydrous magnesium sulfate for 30 min, filter off the desiccant, and remove the solvent under reduced pressure to obtain the crude product. The crude product is separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain the target product.

[0182] Carry out according to the above steps, and the reaction results are shown in the following table:

[0183]

[0184]

[0185] Note: All the raw materials input are 1.0 mmol of epichlorohydrin, and the amount of epichlorohydrin is 100 mol%.

[0186]

[0187] Adopt the method in Entry 13 as described above, and according to the above reaction formula, replace with other reaction substrates to obtain the following various products:

[0188] Characterization of compounds

[0189] Compound characterization data:

[0190]

[0191] Dry column packing and dry sample loading column chromatography (200 - 300 mesh silica gel) separation: Using dichloromethane:methanol (V / V) = 75:1 as the developing solvent, the yield is 95%.

[0192] Chloromethyl-1,3-dioxolan-2-one ; 1 H NMR (500 MHz, CDCl3) δ 4.98–4.94 (m, 1H), 4.59 (t, J = 9.0 Hz, 1H), 4.43–4.40 (m, 1H), 3.72–3.79 (m, 2H) ppm; 13 C NMR: (125 MHz, CDCl3) δ 154.2, 74.4, 67.1, 43.7 ppm.

[0193]

[0194] Dry column packing and dry sample loading column chromatography (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 15:1 as the developing solvent, the yield is 90%.

[0195] 4-Phenyl-1,3-dioxolan-2-one ; 1 H NMR (500 MHz, CDCl3) δ 7.46–7.35 (m, 5H), 5.68 (t, J = 8.0 Hz, 1H), 4.80 (t, J = 8.5 Hz, 1H), 4.34 (t, J = 8.5 Hz, 1H) ppm; 13 C NMR (125 MHz, CDCl3) δ 154.9, 135.9, 129.8, 129.3, 126.0, 78.1, 71.3 ppm.

[0196]

[0197] Dry column packing and dry sample loading column chromatography (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 10:1 as the developing solvent, the yield is 92%.

[0198] 4-(Phenoxymethyl)-1,3-dioxolan-2-one ; 11H NMR (500 MHz, CDCl3) δ 7.31 (t, J = 7.5 Hz, 2H), 7.01 (t, J = 7.5 Hz, 1H), 6.90 (d, J = 9 Hz, 2H), 5.04–5.00 (m, 1H), 4.60 (t, J = 8.5 Hz, 1H), 4.54–4.51 (m, 1H), 4.25–4.22 (m, 1H), 4.15–4.12 (m, 1H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 157.9, 154.8, 129.8, 122.1, 114.7, 74.3, 67.0, 66.3 ppm.

[0199]

[0200] Column chromatography with dry packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether: ethyl acetate (V / V) = 20:1 as the eluent, the yield was 81%.

[0201] 4-(Butoxymethyl)-1,3-dioxolan-2-one ; 1 1H NMR (500 MHz, CDCl3) δ: 4.81–4.77 (m, 1H), 4.48 (t, J = 8.0 Hz, 1H), 4.37 (t, J = 8.0 Hz, 1H), 3.67 - 3.64 (m, 1H), 3.67–3.64 (m, 1H), 3.49 (t, J = 6.0 Hz, 2H), 1.57–1.51 (m, 2H), 1.38–1.31 (m, 2H), 0.90 (t, J = 7.5 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 155.1, 75.23, 72.0, 69.7, 66.4, 31.6, 19.2, 13.9 ppm.

[0202]

[0203] Column chromatography with dry packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether: ethyl acetate (V / V) = 10:1 as the eluent, the yield was 91%.

[0204] 4-Butyl-1,3-dioxolan-2-one ; 1 1H NMR (500 MHz, DMSO-d6) δ 4.81–4.73 (m, 1H), 4.56 (t, J = 8.1 Hz, 1H), 4.12 (t, J = 7.7 Hz, 1H), 1.74–1.61 (m, 2H), 1.38–1.23 (m, 4H), 0.88 (t, J = 6.9 Hz, 3H) ppm; 13CNMR(125MHz, DMSO-d6) δ 155.1, 77.2, 69.4, 32.7, 26.5, 21.9, 13.9 ppm.

[0205]

[0206] Dry-column packing and dry-sample loading column chromatography (200 - 300 mesh silica gel) separation: Petroleum ether: Ethyl acetate (V / V) = 10:1 was used as the developing solvent, and the yield was 93%.

[0207] 4-[(2-Propen-1-yloxy)methyl]-1,3-dioxolan-2-one ; 1 H NMR(500MHz, CDCl3) δ 5.88–5.80(m, 1H), 5.27–5.17(m, 2H), 4.82–4.78(m, 1H), 4.48(t, J = 8.5Hz, 1H), 4.38–4.35(m, 1H), 4.06–3.96(m, 2H), 3.68–3.65(m, 1H), 3.60–3.57(m, 1H) ppm; 13 C NMR(125MHz, CDCl3) δ 155.1, 133.8, 117.9, 75.2, 72.6, 68.9, 66.3 ppm.

[0208]

[0209] Dry-column packing and dry-sample loading column chromatography (200 - 300 mesh silica gel) separation: Petroleum ether: Ethyl acetate (V / V) = 10:1 was used as the developing solvent, and the yield was 91%.

[0210] Butylene carbonate ; 1 H NMR(500MHz, CDCl3) δ 4.69–4.63(m, 1H), 4.52(t, J = 8.5Hz, 1H), 4.09(t, J = 7.0Hz, 1H), 1.88–1.72(m, 2H), 1.03(t, J = 7.5Hz, 3H) ppm; 13 C NMR(125MHz, CDCl3) δ 155.2, 78.1, 69.1, 27.1, 8.7 ppm.

[0211] Example 4

[0212] Method for synthesizing oxazolidinone by the reaction of propargylamine with CO2 catalyzed by thiolate-based ionic liquid:

[0213]

[0214] 0.2 mmol of N-butyl-2-methyl-4-phenylbut-3-yn-2-amine, a certain amount of thiolate-based ionic liquid, and 1 mL of solvent were added to a 10 mL Schlenk reaction tube. A magnetic stir bar was placed in the tube and the reaction tube was sealed. After purging with N2 gas in combination with a vacuum pump three times, a balloon filled with CO2 was connected. The reaction was stirred at a certain temperature for a certain period of time (see the following table). After the reaction was completed, the reaction solution was extracted with ethyl acetate. The organic phases were collected and combined, dried with anhydrous magnesium sulfate for 30 min, the desiccant was filtered off, and the solvent was removed under reduced pressure to obtain the crude product. The crude product was separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain the target product.

[0215] The conditions were optimized according to the above steps, and the reaction results are shown in the following table:

[0216] Entry T-Ils(mol%) Solvent T(℃) Yield(%) 1 [TBP][2-Tp](10) DMSO 60 64 2 [TBP][2-Tp](30) DMSO 60 84 3 [TBP][2-Tp](50) DMSO 60 96 [TBP][2-Tp](1) DMSO 60 28 4 [TBP][2-Tp](10) DMSO 70 96 5 [TBP][2-Tp](10) DMSO 80 81 6 [TBP][BnT](10) DMSO 70 7 7 [TBP][4-Me-BT](10) DMSO 70 29 8 [TBP][4-Tp](10) DMSO 70 85 9 [TBP][2-Tp](10) DMSO 70 96 10 [TBP][MIT](10) DMSO 70 38 11 [TBP][2-5-Tp](10) DMSO 70 13 12 [TEA][2-Tp](10) DMSO 70 89 13 [TPA][2-Tp](10) DMSO 70 90 14 [TBA][2-Tp](10) DMSO 70 92 15 [DBUH][2-Tp](10) DMSO 70 49 16 [TBP][2-Tp](10) DMF 70 60 17 [TBP][2-Tp](10) NMP 70 46 18 [TBP][2-Tp](10) MeOH 70 24 19 [TBP][2-Tp](10) MeCN 70 13

[0217] Note: All the starting materials used were 0.2 mmol of N-butyl-2-methyl-4-phenylbut-3-yn-2-amine, and the amount of N-butyl-2-methyl-4-phenylbut-3-yn-2-amine was 100 mol%; the CO2 pressure was 0.1 MPa; the solvent was 1 mL; the reaction time was 8 h.

[0218]

[0219] Using the method of Entry 9 in the above table, according to the above reaction formula, other reaction substrates were used to obtain the following various products:

[0220] Characterization of the compound

[0221]

[0222] Column chromatography separation by wet packing and dry sample loading (200 - 300 mesh silica gel): Petroleum ether:ethyl acetate (V / V) = 2:1 was used as the eluent, and the yield was 96%.

[0223] (Z)-5-benzylidene-3-butyl-4,4-dimethyloxazolidin-2-one: 1 H NMR (500 MHz, CDCl3) δ 7.59 (d, J = 7.8 Hz, 2H), 7.33 (t, J = 7.6 Hz, 2H), 7.20 (t, J = 8.6 Hz, 1H), 5.46 (s, 1H), 3.28–3.11 (m, 2H), 1.71–1.61 (m, 2H), 1.50 (s, 6H), 1.43–1.34 (m, 2H), 0.96 (t, J = 7.3 Hz, 3H) ppm; 1313C NMR (125 MHz, CDCl3) δ 154.3, 153.6, 133.8, 128.6, 128.4, 126.8, 100.5, 62.3, 40.6, 31.7, 27.8, 20.4, 13.9 ppm.

[0224]

[0225] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 2:1 as the eluent, the yield is 95%.

[0226] (Z)-3-butyl-4,4-dimethyl-5-(4-methylbenzylidene)oxazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.48 (d, J = 8.2 Hz, 2H), 7.13 (d, J = 8.0 Hz, 2H), 5.42 (s, 1H), 3.23–3.17 (m, 2H), 2.33 (s, 3H), 1.70–1.62 (m, 2H), 1.48 (s, 6H), 1.42–1.33 (m, 2H), 0.96 (t, J = 7.4 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 154.4, 152.8, 136.6, 130.9, 129.3, 128.3, 100.4, 62.2, 40.5, 31.7, 27.8, 21.3, 20.4, 13.9 ppm.

[0227]

[0228] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 2:1 as the eluent, the yield is 75%.

[0229] (Z)-3-butyl-5-(4-methoxybenzylidene)-4,4-dimethyloxazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.53 (d, J = 8.6 Hz, 2H), 6.86 (d, J = 8.7 Hz, 2H), 5.40 (s, 1H), 3.81 (s, 3H), 3.24–3.15 (m, 2H), 1.69–1.62 (m, 2H), 1.48 (s, 6H), 1.42–1.33 (m, 2H), 0.96 (t, J = 7.4 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 158.5, 154.5, 151.9, 129.7, 126.6, 114.0, 100.0, 62.2, 55.4, 40.5, 31.7, 27.8, 20.4, 13.9 ppm.

[0230]

[0231] Column chromatography separation by wet packing and dry sample loading (200 - 300 mesh silica gel): Petroleum ether: Ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the yield was 98%.

[0232] (Z)-3-butyl-5-(4-chlorobenzylidene)-4,4-dimethyloxazolidin-2-one: 1 HNMR(500MHz,CDCl3)δ7.51(d,J = 8.5Hz,2H),7.28(d,J = 8.5Hz,2H),5.41(s,1H),3.25–3.16(m,2H),1.70–1.62(m,2H),1.49(s,6H),1.42–1.34(m,2H),0.96(t,J = 7.4Hz,3H)ppm; 13 C NMR(125MHz,CDCl3)δ154.2,154.1,132.3(8),132.3(5),129.6,128.7,99.4,62.4,40.6,31.6,27.7,20.4,13.9ppm.

[0233]

[0234] Column chromatography separation by wet packing and dry sample loading (200 - 300 mesh silica gel): Petroleum ether: Ethyl acetate (V / V) = 3:1 was used as the developing solvent, and the yield was 98%.

[0235] (Z)-3-butyl-4,4-dimethyl-5-(pyridin-3-ylmethylene)oxazolidin-2-one: 1 HNMR(500MHz,CDCl3)δ8.52(d,J = 79.2Hz,2H),8.14(d,J = 7.4Hz,1H),7.27(s,1H),5.45(s,1H),3.25–3.16(m,2H),1.70–1.61(m,2H),1.51(s,6H),1.42–1.34(m,2H),0.96(t,J = 7.3Hz,3H)ppm; 13 C NMR(125MHz,CDCl3)δ156.0,153.8,149.3(4),149.3(3),149.3(1),147.7,135.1,96.9,62.5,40.6,31.6,27.7,20.4,13.9ppm.

[0236]

[0237] Column chromatography with wet packing and dry sample loading (using silica gel of 200 - 300 mesh): Petroleum ether: Ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the yield was 95%.

[0238] (Z)-3-butyl-4,4-dimethyl-5-(thiophen-2-ylmethylene)oxazolidin-2-one: 1 H NMR (500 MHz, CDCl3) δ 7.24 (d, J = 4.4 Hz, 1H), 7.17–7.10 (m, 1H), 7.03–6.94 (m, 1H), 5.76 (s, 1H), 3.23–3.16 (m, 2H), 1.69–1.61 (m, 2H), 1.48 (s, 6H), 1.41–1.33 (m, 2H), 0.95 (t, J = 6.2 Hz, 3H) ppm; 13 C NMR (125 MHz, CDCl3) δ 153.9, 152.1, 136.4, 127.1, 126.0, 125.2, 94.8, 61.9, 40.6, 31.6, 27.6, 20.4, 13.9 ppm.

[0239]

[0240] Column chromatography with wet packing and dry sample loading (using silica gel of 200 - 300 mesh): Petroleum ether: Ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the yield was 93%.

[0241] (Z)-3-benzyl-5-benzylidene-4,4-dimethyloxazolidin-2-one: 1 H NMR (500 MHz, CDCl3) δ 7.60 (d, J = 8.0 Hz, 2H), 7.40–7.31 (m, 6H), 7.30 (d, J = 6.9 Hz, 1H), 7.24–7.18 (m, 1H), 5.46 (s, 1H), 4.52 (s, 2H), 1.39 (s, 6H) ppm; 13 C NMR (125 MHz, CDCl3) δ 154.9, 153.5, 137.6, 133.7, 128.8, 128.6, 128.4, 127.9, 127.8, 126.9, 100.8, 62.6, 44.3, 27.8 ppm.

[0242]

[0243] Column chromatography with wet packing and dry sample loading (using silica gel of 200 - 300 mesh): Petroleum ether: Ethyl acetate (V / V) = 2:1 was used as the developing solvent, and the yield was 98%.

[0244] (Z)-5-benzylidene-4,4-dimethyl-3-propyloxazolidin-2-one: 11H NMR (500 MHz, CDCl3) δ 7.59 (d, J = 7.8 Hz, 2H), 7.32 (t, J = 7.7 Hz, 2H), 7.20 (t, J = 7.4 Hz, 1H), 5.46 (s, 1H), 3.21–3.14 (m, 2H), 1.75–1.67 (m, 2H), 1.50 (s, 6H), 0.96 (t, J = 7.4 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 154.4, 153.6, 133.8, 128.6, 128.4, 126.9, 100.5, 62.3, 42.4, 27.7 (6), 22.8 (0), 11.5 ppm.

[0245]

[0246] Column chromatography was performed by wet packing and dry loading (200 - 300 mesh silica gel). Petroleum ether: ethyl acetate (V / V) = 2:1 was used as the eluent, and the yield was 83%.

[0247] (Z)-5-benzylidene-3-hexyl-4,4-dimethyloxazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.59 (d, J = 8.2 Hz, 2H), 7.32 (t, J = 7.7 Hz, 2H), 7.20 (t, J = 7.4 Hz, 1H), 5.45 (s, 1H), 3.25–3.15 (m, 2H), 1.73–1.62 (m, 2H), 1.49 (s, 6H), 1.33 (d, J = 9.8 Hz, 6H), 0.90 (t, J = 6.4 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 154.3, 153.6, 133.8, 128.6, 128.4, 126.9, 100.5, 62.3, 40.8, 31.6, 29.6, 27.8, 26.8, 22.7, 14.2 ppm.

[0248]

[0249] Column chromatography was performed by wet packing and dry loading (200 - 300 mesh silica gel). Petroleum ether: ethyl acetate (V / V) = 2:1 was used as the eluent, and the yield was 71%.

[0250] (Z)-5-benzylidene-4,4-dimethyl-3-octyloxazolidin-2-one: 11H NMR (500 MHz, CDCl3) δ 7.58 (d, J = 8.2 Hz, 2H), 7.32 (t, J = 7.6 Hz, 2H), 7.23–7.17 (m, 1H), 5.45 (s, 1H), 3.24–3.15 (m, 2H), 1.68–1.63 (m, 2H), 1.49 (s, 6H), 1.33–1.26 (m, 10H), 0.88 (t, J = 6.4 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 154.3, 153.6, 133.8, 128.6, 128.4, 126.8, 100.5, 62.3, 40.8, 31.9, 29.6, 29.3(8), 29.3(5), 27.8, 27.2, 22.8, 14.2 ppm.

[0251]

[0252] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel): Petroleum ether: ethyl acetate (V / V) = 2:1 was used as the eluent, and the yield was 99%.

[0253] (Z)-5-benzylidene-3-butyl-4-phenyloxazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.52 (d, J = 8.4 Hz, 2H), 7.46–7.39 (m, 3H), 7.34 (d, J = 7.9 Hz, 2H), 7.29 (t, J = 7.7 Hz, 2H), 7.18 (t, J = 7.4 Hz, 1H), 5.39 (s, 1H), 5.25 (s, 1H), 3.56–3.46 (m, 1H), 2.87–2.78 (m, 1H), 1.50–1.41 (m, 2H), 1.32–1.25 (m, 2H), 0.88 (t, J = 7.3 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 155.2, 147.8, 137.5, 133.6, 129.4(9), 129.4(5), 128.6, 128.5, 127.9, 127.1, 104.7, 64.0, 41.8, 29.1, 19.9, 13.8 ppm.

[0254]

[0255] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel): Petroleum ether: ethyl acetate (V / V) = 2:1 was used as the eluent, and the yield was 95%.

[0256] (Z)-5-benzylidene-3-butyl-4-propyloxazolidin-2-one: 11H NMR (500 MHz, CDCl3) δ 7.58 (d, J = 7.3 Hz, 2H), 7.33 (t, J = 7.7 Hz, 2H), 7.20 (t, J = 7.4 Hz, 1H), 5.47 (s, 1H), 4.55–4.50 (m, 1H), 3.65–3.57 (m, 1H), 3.06–2.99 (m, 1H), 1.91–1.81 (m, 1H), 1.73–1.65 (m, 1H), 1.62–1.56 (m, 2H), 1.42–1.31 (m, 4H), 0.96 (t, J = 7.4 Hz, 6H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 155.3, 147.1, 133.8, 128.6, 128.4, 126.9, 102.5, 58.5, 41.3, 34.6, 29.4, 20.1, 16.0, 14.1, 13.8 ppm.

[0257]

[0258] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 2:1 as the eluent, the yield is 99%.

[0259] (Z)-4-benzyl-5-benzylidene-3-butyloxazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.46 (d, J = 7.5 Hz, 2H), 7.30 (t, J = 8.0 Hz, 5H), 7.20 (d, J = 7.4 Hz, 3H), 5.19 (s, 1H), 4.68 (t, J = 5.4 Hz, 1H), 3.68–3.59 (m, 1H), 3.19–3.12 (m, 1H), 3.11–3.03 (m, 1H), 3.02–2.95 (m, 1H), 1.60–1.51 (m, 2H), 1.37–1.27 (m, 2H), 0.93 (t, J = 7.4 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 155.0, 146.1, 135.0, 133.5, 129.7, 128.9, 128.6, 128.5, 127.5, 127.0, 103.9, 59.6, 41.7, 40.0, 29.3, 20.0, 13.8 ppm.

[0260]

[0261] Column chromatography with wet packing and dry sample loading (200 - 300 mesh silica gel) separation: Using petroleum ether:ethyl acetate (V / V) = 2:1 as the eluent, the yield is 99%.

[0262] (Z)-5-benzylidene-3-butyl-4,4-diethyloxazolidin-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.60 (d, J = 8.0 Hz, 2H), 7.33 (t, J = 7.7 Hz, 2H), 7.20 (t, J = 7.4 Hz, 1H), 5.33 (s, 1H), 3.15–3.06 (m, 2H), 1.87–1.78 (m, 2H), 1.71–1.57 (m, 4H), 1.43–1.34 (m, 2H), 0.97 (t, J = 7.4 Hz, 3H), 0.86 (t, J = 7.3 Hz, 6H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 155.6, 150.1, 133.9, 128.6, 128.4, 126.8, 100.8, 70.6, 40.5, 32.2, 31.2, 20.6, 13.9, 7.9 ppm.

[0263]

[0264] Column chromatography was performed by wet packing of the column and dry loading of the sample (silica gel, 200 - 300 mesh). Petroleum ether:ethyl acetate (V / V) = 2:1 was used as the eluent, and the yield was 50%.

[0265] (Z)-4-benzylidene-1-butyl-3-oxa-1-azaspiro[4.5]decan-2-one: 1 1H NMR (500 MHz, CDCl3) δ 7.62 (d, J = 7.8 Hz, 2H), 7.33 (t, J = 7.7 Hz, 2H), 7.20 (t, J = 7.4 Hz, 1H), 5.80 (s, 1H), 3.22–3.14 (m, 2H), 1.88–1.77 (m, 7H), 1.74–1.64 (m, 4H), 1.41–1.32 (m, 2H), 1.29–1.25 (m, 1H), 0.95 (t, J = 7.4 Hz, 3H) ppm; 13 13C NMR (125 MHz, CDCl3) δ 154.4, 152.5, 134.1, 128.9, 128.6, 126.9, 103.8, 64.1, 40.4, 34.4, 31.8, 24.3, 21.8, 20.4, 13.9 ppm.

[0266] It has been verified that when the thiolate-based ionic liquid in the present invention is used as a non-metallic homogeneous catalyst in the cycloaddition reaction of carbon dioxide with ethylene oxide or propargylamine to produce cyclic carbonates and oxazolidinones, the catalytic activity can be maintained at 96% after being recycled 5 times. For example, the catalytic stability experiment of the thiolate-based ionic liquid [TBP][2-Tp] in the reaction of N-butyl-2-methyl-4-phenylbut-3-yn-2-amine with CO2 to prepare (Z)-5-benzylidene-3-butyl-4,4-dimethyl-oxazolidin-2-one is shown in Figure 4 . It can be seen that excellent catalytic performance and stable recycling performance are exhibited.

[0267] All the documents mentioned in the present invention are hereby incorporated by reference in this application as if each of them was individually incorporated by reference. In addition, it should be understood that after reading the above teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0268] It should be noted that the above-described embodiments are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described by referring to the typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words rather than limiting words. Modifications can be made to the present invention within the scope of the claims of the present invention as provided, and the present invention can be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein. On the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A thiolate-based ionic liquid, the structural formula of the thiolate-based ionic liquid being shown as formula (1): X is N or P, and R1, R2, R3 and R4 are each independently selected from: H, substituted or unsubstituted C1-C 20 alkyl; or, X, R1, R2, R3 and R4 together form the following groups: imidazoles, pyrroles, pyridines, morpholines, piperidines, amidines, guanidines; R5 is selected from a substituted or unsubstituted C1-C6 alkyl group, a phenyl group unsubstituted or substituted by 1-3 groups selected from the following: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; alternatively, R5 is selected from a pyridine group, a pyrimidine group, an imidazole group, a thiophene group.

2. A method for preparing the thiolate-based ionic liquid according to claim 1, which comprises reacting a reaction substrate providing an X group and a reaction substrate providing an S-R5 group in a solvent by using the reaction formula of Method 1, Method 2 or Method 3 to obtain the one shown in formula (1) wherein In Method 3, R4 is H; Method 1: Method 2: Method 3: In Method 2: Y is a halogen, preferably Cl or Br; Z is an alkali metal element, preferably Na or K.

3. The preparation method according to claim 2, wherein: The conditions in Method 1, Method 2, and Method 3 each include: The solvent is selected from at least one of H2O, EtOH, MeOH, NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH2Cl2, CHCl3, CCl4, toluene, ethyl acetate; and / or, Relative to the reaction substrate providing 1 mmol of the S-R5 group, the amount of the solvent used is 0.5-50 mL; and / or, The molar ratio of the reaction substrate providing the X group to the reaction substrate providing the S-R5 group is 1:(0.5-2); and / or, The reaction conditions include: the temperature is 0-150 °C, and / or, the reaction time is 5 min-48 h.

4. Use of the thiolate-based ionic liquid according to claim 1 or the thiolate-based ionic liquid obtained by the preparation method according to claim 2 or 3 in capturing CO2 or converting CO2.

5. A method for capturing CO2 with a thiolate-based ionic liquid, wherein, under conditions with or without a solvent, the thiolate-based ionic liquid is contacted with CO2 to capture the CO2, and the thiolate-based ionic liquid is the thiolate-based ionic liquid according to claim 1 or the thiolate-based ionic liquid obtained by the preparation method according to claim 2 or 3.

6. The method for capturing CO2 with a thiolate-based ionic liquid according to claim 5, wherein: Under conditions with a solvent, the solvent is selected from at least one of H2O, EtOH, MeOH, NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH2Cl2, CHCl3, CCl4, toluene, ethyl acetate; and / or, relative to providing 1 mmol of the thiolate-based ionic liquid, the amount of the solvent used is 0.5-50 mL; and / or, Under conditions with or without a solvent, the contact conditions each include: the temperature is 0-25 °C, and / or, the pressure is 0.1-3.5 MPa; and / or, The product obtained by contacting the thiolate-based ionic liquid with CO2 is a compound shown as formula (2) 7. A method for preparing a cyclic carbonate derivative, comprising: In a solvent, in the presence of a thiolate-based ionic liquid, ethylene oxide shown as formula (3) is reacted with CO2 to obtain a cyclic carbonate derivative shown as formula (4); The thiolate-based ionic liquid is the thiolate-based ionic liquid according to claim 1 or the thiolate-based ionic liquid obtained by the preparation method according to claim 2 or 3; Wherein, R6 and R7 are each independently selected from H, substituted or unsubstituted C1-C 10 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, phenyl which is unsubstituted or substituted by 1-3 substituents selected from the following: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3.

8. The preparation method of the cyclic carbonate derivative according to claim 7, wherein: the solvent is selected from at least one of H2O, EtOH, MeOH, NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH2Cl2, CHCl3, CCl4, toluene, ethyl acetate, supercritical CO2; and / or, relative to providing 1 mmol of the ethylene oxide shown in formula (3), the amount of the solvent used is 0.5 - 50 mL; and / or, the molar ratio of the ethylene oxide shown in formula (3) to CO2 is 1:1 - 100; and / or, during the reaction process, CO2 is continuously introduced into the reactor, and the pressure of the CO2 in the reactor is 0.1 - 12 MPa; and / or, the molar ratio of the ethylene oxide shown in formula (3) to the thiolate-based ionic liquid is 1:0.05 - 20; and / or, the reaction temperature is 25 - 150 °C; and / or, the reaction time is 1 - 48 h.

9. A method for preparing an oxazolidinone derivative, comprising: In a solvent, in the presence of a thiolate-based ionic liquid, the propargylamine derivative shown in formula (5) is reacted with CO2 to obtain the oxazolidinone derivative shown in formula (6); the thiolate-based ionic liquid is the thiolate-based ionic liquid described in claim 1 or the thiolate-based ionic liquid obtained by the preparation method described in claim 2 or 3; wherein, R8 and R9 are each independently selected from H, substituted or unsubstituted C1-C 10 alkyl, phenyl which is unsubstituted or substituted by 1-3 substituents selected from the following: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; or R8 and R9 are each independently selected from: naphthyl, furyl, thienyl, pyridyl, pyrrolyl; R 10 、R 11 are each independently selected from H, substituted or unsubstituted C1-C6 alkyl, or phenyl which is unsubstituted or substituted with 1-3 substituents selected from the following: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, OH, NO2, NH2, SO2CH3; or R 10 、R 11 are each independently selected from: naphthyl, furyl, thienyl, pyridyl, pyrrolyl; or R 10 and R 11 together form -(CH2) n -, where n is selected from 2, 3, 4, 5 or 6.

10. The preparation method of the oxazolidinone derivative according to claim 9, wherein: the solvent is selected from at least one of H2O, EtOH, MeOH, NMP, DMF, THF, DMSO, 1,4-dioxane, HMPA, CH2Cl2, CHCl3, CCl4, toluene, ethyl acetate, supercritical CO2; and / or, relative to providing 1 mmol of the propargylamine derivative shown in formula (5), the amount of the solvent used is 0.5 - 50 mL; and / or, the molar ratio of the propargylamine derivative shown in formula (5) to CO2 is 1:1 - 100; and / or, during the reaction process, CO2 is continuously introduced into the reactor, and the pressure of the CO2 in the reactor is 0.1 - 12 MPa; and / or, the molar ratio of the propargylamine derivative shown in formula (5) to the thiolate-based ionic liquid is 1:0.05 - 20; and / or, the reaction temperature is 25 - 150 °C; and / or, the reaction time is 1 - 48 h.

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