A method for preparing 2-imidazolidinone using carbon dioxide

Abstract

The present application relates to fine chemicals, and in particular to a method for preparing 2-imidazolidinone by using carbon dioxide. The method comprises reacting CO2 and ethylenediamine in the presence of inorganic sulfide to obtain 2-imidazolidinone. The method uses cheap and readily available sulfur-containing compounds as catalysts for activating CO2 for the first time, and converts ethylenediamine and CO2 into 2-imidazolidinone under relatively low temperature and supercritical conditions. Compared with the prior art, the reaction conditions of the present application are more simple and controllable, and do not require expensive and complex catalysts for post-processing, have the advantages of low energy consumption and low cost, and have extremely high popularization and application value.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of medicine, pesticides and fine chemicals such as aldehyde scavengers, and in particular to a method for preparing 2-imidazolidinone using carbon dioxide. BACKGROUND

[0002] 2-imidazolidinone is an organic compound, also known as ethylene urea, and is a colorless needle-like crystal that is easily soluble in water and hot ethanol, and is difficult to dissolve in diethyl ether.

[0003] 2-imidazolidinone has wide application value in the fields of chemical industry, medicine, pesticides, aldehyde removal, and fabric wrinkle removal. 2-imidazolidinone is not only an intermediate for new antibiotics such as mezlocillin and azlocillin, but also an intermediate for pesticides such as N-chloroformyl-2-imidazolidinone. In industrial production, 2-imidazolidinone is often used to synthesize curing agents for artificial resins, and to synthesize important solvents 1,3-dimethyl-2-imidazolidinone in industry. It is also the main component of various aldehyde scavengers, air fresheners, metal preservatives, and fabric softeners. Therefore, 2-imidazolidinone has very promising application prospects and has become a very popular fine chemical product.

[0004] The main preparation methods of 2-imidazolidinone include phosgene method, carbonate method, urea method, CO method, and CO2 method. In the past, 2-imidazolidinone was mainly prepared by using phosgene and ethylenediamine in sodium hydroxide aqueous solution. However, this method uses highly toxic phosgene, and a large amount of hydrogen chloride is discharged during the reaction, which can cause certain impact on the environment and equipment. Now, 2-imidazolidinone is mainly prepared by using ethylenediamine and urea at high temperature. This method not only produces ammonia gas, causing environmental pollution and equipment corrosion, but also can cause problems such as low yield due to improper temperature control and burning and coking. It is found that CO2 is also a good carbonyl source, and CO2 is abundant and cheap. Using CO2 to synthesize 2-imidazolidinone can not only solve the problem of CO2 emission, but also synthesize high value-added chemical products, realize the carbon cycle in nature, and meet the requirements of "atomic economy" and "green chemistry". Therefore, a variety of methods for synthesizing 2-imidazolidinone using carbon dioxide have been developed. However, these methods require high reaction temperature or the addition of expensive catalysts with complex post-treatment, and the production and separation costs are relatively high, which is not conducive to industrial production.

[0005] Therefore, in view of the high energy consumption and high cost of the prior art, how to provide a more green and economic synthesis method of imidazolidinone is a technical problem to be solved at present. SUMMARY

[0006] In view of the problems of high energy consumption and high cost in the prior art, the present application provides a green and economical synthesis method of 2-imidazolidone by activating CO2. The method uses a cheap and easily available sulfur-containing compound as a catalyst for activating CO2 for the first time, and converts ethylenediamine and CO2 into 2-imidazolidone under relatively low temperature and supercritical conditions. Compared with the prior art, the reaction conditions of the present application are more simple and controllable, and do not require expensive and complex post-processing catalysts, and have the advantages of low energy consumption and low cost, and have extremely high popularization and application value.

[0007] The present application aims to provide a preparation method of 2-imidazolidone, which comprises reacting CO2 and ethylenediamine in the presence of inorganic sulfide to obtain 2-imidazolidone.

[0008] According to the present application, the structure of the 2-imidazolidone is shown in formula (I):

[0009] According to the present application, the inorganic sulfide can be selected in a wide range, and in a preferred embodiment of the present application, the inorganic sulfide is at least one of metal sulfide, metal hydrosulfide and H2S; preferably, the inorganic sulfide is at least one of alkali metal sulfide, alkali metal hydrosulfide and H2S; more preferably, the inorganic sulfide is at least one of H2S, Na2S, K2S, NaHS and KHS.

[0010] According to the present application, the reaction conditions of the present application can be selected in a wide range, and the reaction is carried out in a solvent or without a solvent.

[0011] According to the present application, the molar ratio of ethylenediamine to inorganic sulfide can be selected in a wide range, and in a preferred embodiment of the present application, the reaction conditions include that the molar ratio of ethylenediamine to inorganic sulfide is 1:(0.5-4), preferably 1:(1-2).

[0012] According to the present application, the reaction pressure can be selected in a wide range, and in a preferred embodiment of the present application, the reaction conditions include that the reaction pressure is 1-14 MPa, preferably 3-12 MPa.

[0013] According to the present application, the temperature conditions of the reaction can be selected in a wide range, and in a preferred embodiment of the present application, the reaction conditions include that the temperature is 90-160 DEG C, preferably 130-160 DEG C.

[0014] According to the present application, the time conditions of the reaction can be selected in a wide range, and in a preferred embodiment of the present application, the reaction time is 4-24 h; preferably 5-12 h.

[0015] In one embodiment of the present application, when the reaction is carried out without solvent, the temperature and pressure conditions of the reaction are in the supercritical pressure and temperature range of CO2.

[0016] In a more preferred embodiment of the present application, the reaction conditions include: the temperature is 90-160°C, preferably 130-160°C; the reaction time is 4-24h, preferably 5-12h; and the reaction pressure is 1-14Mpa, preferably 3-12Mpa.

[0017] More preferably, the reaction pressure is adjusted by the amount of CO2 fed, and the CO2 pressure in the reaction vessel is 1-14Mpa, preferably 3-12Mpa. The amount and ratio of CO2 can be converted by the pressure of CO2 and the volume of the reaction vessel. In the present application, the volume of the reaction vessel (corresponding to the reaction kettle) is 15mL, of course, the volume of the reaction vessel suitable for the present application is wider, including but not limited to 15mL of reaction kettle.

[0018] According to the present application, when the reaction is carried out in a solvent, the solvent can be selected in a wide range, in a preferred embodiment of the present application, the solvent is selected from at least one of NMP, CH3OH, pyrrolidone, DMF, N,N-dimethylacetamide, DMSO, toluene, xylene; preferably, the solvent is selected from at least one of NMP, CH3OH and DMF.

[0019] According to the present application, in addition to the inorganic sulfide, CO2, ethylenediamine and optional solvent required for the above reaction, other additives can be added, or no additives can be added, and both can achieve the present application.

[0020] If an additive is added to the reaction system, the range of the additive is wider, in one specific embodiment of the present application, when the reaction is carried out in the presence of a solvent, an organic base can be added to the reaction system. Preferably, the organic base is at least one of amidine organic base, guanidine organic base and triethylamine; more preferably, the organic base is at least one of DBU, TBD, TMG, MTBD and DBN.

[0021] In the case of adding an organic base, the molar ratio of the organic base to the ethylenediamine can be selected in a wide range, in a preferred embodiment of the present application, the molar ratio of the organic base to the ethylenediamine is (0-0.6):1.

[0022] According to the technical scheme, the application relates to a synthesis method for synthesizing 2-imidazolidone by using inorganic sulfide to catalyze CO2 and ethylenediamine. The inorganic sulfide which is cheap and easy to obtain is used as a catalyst for activating CO2 for the first time. The ethylenediamine is converted into 2-imidazolidone under the conditions of supercritical alkali-free solvent or low-pressure alkali-containing solvent. The synthesis method uses CO2 as a carbonylation reagent, has high atom economy, almost no by-product is generated, conforms to the concept of "green chemistry", and is a feasible way for recycling carbon elements in nature.

[0023] Meanwhile, compared with the prior art, the reaction condition is more simple and controllable, and the catalyst which is expensive and has complex post-processing is not needed, so that the application has the advantages of low energy consumption and low cost, and has extremely high popularization and application value. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 The 2-imidazolidone nuclear magnetic hydrogen spectrum is shown in Fig. 1.

[0025] Figure 2 The 2-imidazolidone nuclear magnetic carbon spectrum is shown in Fig. 2. DETAILED DESCRIPTION

[0026] It is necessary to point out that the following examples are only used for further illustrating the application, and cannot be understood as limiting the protection scope of the application. Some non-essential improvements and adjustments of the application made by the person skilled in the art according to the content of the application still belong to the protection scope of the application.

[0027] In order to make the object, technical scheme and advantages of the application more clear, the following will describe the implementation mode of the application in combination with the drawings.

[0028] In the following examples, if no special description is given, the raw materials and equipment used are all conventional commercial products; and the equipment used is all conventional equipment in the field.

[0029] In the following examples, the calculation formula of the yield is: yield = (actual yield / theoretical yield) * 100%

[0030]

[0031] Wherein, m 2-咪唑烷酮 refers to the mass of 2-imidazolidone generated; m 乙二胺 refers to the mass of ethylenediamine added; M 乙二胺 refers to the molecular weight of ethylenediamine; M 2-咪唑烷酮 refers to the molecular weight of 2-imidazolidone.

[0032] Example 1

[0033] First, 10.1 mmol of ethylenediamine was weighed into a 15 mL polytetrafluoroethylene-lined stainless steel reaction kettle, then 9.7 mmol of H2S was added to the reaction kettle. After preheating at 140 °C for 30 min, 11 MPa of CO2 was introduced. The reaction was stirred at 140 °C for 5 h. After stopping the reaction, the excess CO2 and H2S gas was discharged, and then the product was taken out, obtaining 2-imidazolidone 0.7563 g, with a yield of 87.03%. The reaction formula is as follows:

[0034]

[0035] Example 2:

[0036] First, 20 mmol of ethylenediamine was weighed into a 15 mL polytetrafluoroethylene-lined stainless steel reaction kettle, then 26.2 mmol of H2S was added to the reaction kettle. After preheating at 140 °C for 30 min, 12 MPa of CO2 was introduced. The reaction was stirred at 140 °C for 6 h. After stopping the reaction, the excess CO2 and H2S gas was discharged, and then the product was taken out, obtaining 2-imidazolidone 1.447 g, with a yield of 84.03%.

[0037] Examples 3-7:

[0038] Examples 3-7 differ from Example 2 only in that the ratio of the reactants is different in the process of preparing 2-imidazolidone, and the rest is basically the same as Example 2.

[0039] The effect of different ratios of reactants in Examples 3-7 on the yield of 2-imidazolidone is shown in Table 1.

[0040] Table 1

[0041] Example Molar ratio (ethylenediamine: inorganic sulfide) Yield (%) 3 1：0.72 40.2 4 1：1.01 89.3 5 1：1.46 92.6 6 1：1.37 90.9 7 1：3.09 84.0

[0042] Examples 8-12

[0043] Examples 8-12 differ from Example 2 only in that the reaction pressure is different in the process of preparing 2-imidazolidone, and the rest is basically the same as Example 2.

[0044] The effect of different reaction pressures in Examples 8-12 on the yield of 2-imidazolidone is shown in Table 2.

[0045] Table 2

[0046] Example CO2 pressure (Mpa) Yield (%) 8 8 97.1 9 10 99.0 10 11 99.0 11 12 84.0 12 14 42.7

[0047] Examples 13-17

[0048] Examples 13-17 differ from Example 2 only in that the reaction temperature is different in the process of preparing 2-imidazolidone, and the rest is basically the same as Example 2.

[0049] The effect of different reaction temperature ratios on the yield of 2-imidazolidone in Examples 13-17 is shown in Table 3.

[0050] Table 3

[0051] Example Temperature (°C) Yield (%) 13 120 74.9 14 130 99.0 15 140 97.1 16 150 89.3 17 160 99.0

[0052] Examples 18-21

[0053] The difference between Examples 18-21 and Example 2 is only that the reaction time is different during the preparation of 2-imidazolidone, and the rest is basically the same as Example 2.

[0054] The effect of different reaction time ratios on the yield of 2-imidazolidone in Examples 18-21 is shown in Table 4.

[0055] Table 4

[0056] Example Reaction time (h) Yield (%) 18 4 76.9 19 5 99.0 20 6 99.0 21 12 99.0

[0057] Example 22

[0058] First, 20 mmol of ethylenediamine was weighed into a 15 mL polytetrafluoroethylene-lined stainless steel reaction kettle, 20 mmol of NaHS was added to the reaction kettle, and the reaction kettle was preheated at 110°C for 30 min, and 12 MPa CO2 was introduced. Stir the reaction at 110°C for 5h. After stopping the reaction, the excess CO2 gas was discharged, and after the reaction kettle was cooled, the product in the reaction kettle was extracted with ethyl acetate, rotary evaporation, drying, to obtain the reaction product 2-imidazolidone 1.423 g, the yield was 82.7%.

[0059] Example 23

[0060] The difference between Example 23 and Example 22 is only that the inorganic sulfide is K2S during the preparation of 2-imidazolidone, and the rest is basically the same as Example 22. The reaction product 2-imidazolidone 1.274 g was obtained with a yield of 73.9%.

[0061] Example 24

[0062] First, 20 mmol of ethylenediamine was weighed into a 15 mL polytetrafluoroethylene-lined stainless steel reaction kettle, 20 mmol of H2S was added to the reaction kettle, 2 mL of NMP (N-methyl pyrrolidone) was added, and the reaction kettle was preheated at 140°C for 30 min, and 10 MPa CO2 was introduced. Stir the reaction at 140°C for 5h. After stopping the reaction, the excess CO2 gas was discharged, and after the reaction kettle was cooled, the product in the reaction kettle was extracted with ethyl acetate, and after column chromatography separation, the reaction product 2-imidazolidone was obtained by recrystallization.

[0063] Examples 25-32

[0064] Examples 25-32 differ from Example 24 only in the type of organic solvent and inorganic sulfide used in the preparation of 2-imidazolidinone, and are otherwise substantially the same as Example 24.

[0065] The effect of different reaction solvents and different inorganic sulfides on the yield of 2-imidazolidinone in Examples 25-32 is shown in Table 5.

[0066] Table 5

[0067]

[0068]

[0069] Example 33

[0070] First, 20 mmol of ethylenediamine was weighed into a 15 mL polytetrafluoroethylene-lined stainless steel reaction kettle, 2 mL of NMP was added to the reaction kettle, and 12 mmol of DBU (1,8-diazabicycloundec-7-ene) was added, followed by 20 mmol of H2S. The reaction kettle was preheated at 90°C for 30 min, 3 MPa of CO2 was injected, and the reaction was stirred at 90°C for 4 h. After the reaction was stopped, the excess CO2 gas was discharged, and after the reaction kettle was cooled, the product in the reaction kettle was extracted with ethyl acetate, column chromatography was performed, and recrystallization was performed to obtain the reaction product 2-imidazolidinone, with a yield of 99%.

[0071] Example 34

[0072] Example 34 differs from Example 33 only in that the organic base used in the preparation of 2-imidazolidinone is TBD (1,5,7-triazabicyclo[4,4,0]dec-5-ene), and is otherwise substantially the same as Example 33. The reaction product 2-imidazolidinone was obtained in a yield of 1.38 g, with a yield of 80%.

[0073] Examples 35-42

[0074] Examples 35-42 differ from Example 33 only in the type of inorganic sulfide and organic solvent used in the preparation of 2-imidazolidinone, and are otherwise substantially the same as Example 33.

[0075] The effect of different inorganic sulfides on the yield of 2-imidazolidinone in Examples 35-42 is shown in Table 6.

[0076] Table 6

[0077] Example Inorganic sulfide Organic solvent Yield (%) 35 NaSH DMF 74.9 36 [K2S] DMF 69.3 37 NaSH CH3OH 74.9 38 [K2S] CH3OH 70.9 39 NaSH NMP 75.8 40 [K2S] NMP 72.1 41 [H2S] DMF 99.0 42 [H2S] CH3OH 99.0

[0078] Examples 43-57

[0079] Examples 43-57 differ from Example 33 only in that the reaction temperature, reaction pressure, reaction time and the amount of organic base added during the preparation of the 2-imidazolidinone are different. Otherwise, they are essentially the same as Example 33.

[0080] The effect of the different reaction temperature, reaction pressure, reaction time and the amount of organic base added on the yield of the 2-imidazolidinone in Examples 43-57 is shown in Table 7.

[0081] Table 7

[0082]

[0083]

[0084] Examples 58-65

[0085] Examples 58-65 differ from Example 34 only in that the inorganic sulfide and the type of organic solvent used during the preparation of the 2-imidazolidinone are different. Otherwise, they are essentially the same as Example 34. The results are shown in Table 8.

[0086] Table 8

[0087]

[0088]

[0089] Examples 66-79

[0090] Examples 66-79 differ from Example 34 only in that the reaction temperature, reaction pressure, reaction time and the amount of organic base added during the preparation of the 2-imidazolidinone are different. Otherwise, they are essentially the same as Example 34.

[0091] The effect of the different reaction temperature, reaction pressure, reaction time and the amount of organic base added on the yield of the 2-imidazolidinone in Examples 66-79 is shown in Table 9.

[0092] Table 9

[0093]

[0094]

[0095] The nuclear magnetic resonance hydrogen spectrum (see Figure 1), the nuclear magnetic resonance carbon spectrum (see Figure 2) and the nuclear magnetic data of the above examples were determined using an Agilent Technologies 500 MHZ nuclear magnetic resonance instrument. Figure 1 Figure 2

[0096] 1 H NMR (500 MHz, D20) δ 3.53 (s, 4H).​​13 C NMR (126 MHz, CDCI3) δ 165.64, 41.04.

[0097] The results demonstrate that the product obtained according to the present application is a 2-imidazolidinone of formula (I)

[0098] It should be noted that the above-mentioned examples are only used to explain the present application and do not constitute any limitation to the present application. The present application is described by referring to typical examples, but it should be understood that the words used therein are descriptive and explanatory words, not limiting words. The present application can be modified within the scope of the claims and revised without departing from the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and examples, it does not mean that the present application is limited to the specific examples disclosed therein, on the contrary, the present application can be extended to all other methods and applications having the same function.

[0099] All publications, patent applications, patents and other references mentioned in this specification are herein incorporated by reference. Unless otherwise defined, all technical and scientific terms used in this specification are intended to have the meanings commonly attributed to them by those of ordinary skill in the art. In case of conflict between the definitions in this specification and those in the incorporated references, the definitions in this specification are intended to control.

[0100] When the specification uses phrases such as "known to those of ordinary skill in the art", "prior art", or similar phrases to derive materials, substances, methods, steps, devices or components, etc., the objects derived by the phrases cover those commonly used in the art at the time of filing the present application, but also include those not commonly used at present, but will be recognized as suitable for similar purposes in the art.

[0101] The endpoints of the ranges and any values disclosed in this application document are not limited to the precise values stated. The ranges and values should be interpreted as being approximate. For numeric values, the endpoints of each range, the endpoints of each range and individual point values, and individual point values can be combined with each other to form one or more new numeric ranges, which should be considered as specifically disclosed herein. In the following, each technical solution can be combined with each other to form a new technical solution in principle, which should also be considered as specifically disclosed herein.

[0102] In the context of the present specification, unless explicitly stated otherwise, any matter or item not mentioned is directly applicable to those known in the art without any change.

[0103] ​Moreover, any implementation described herein can be freely combined with one or more other implementations described herein, and the resulting technical solutions or technical ideas are considered to be part of the original disclosure or original description of the present application, and should not be considered as new content that has not been disclosed or anticipated herein, unless the combination is considered to be obviously unreasonable by those skilled in the art.

Claims

1. A method for preparing 2-imidazolidineone, comprising reacting CO2 and ethylenediamine in the presence of an inorganic sulfide to obtain 2-imidazolidineone; wherein the inorganic sulfide is at least one of a metal sulfide and a metal hydride; When the reaction is carried out in the presence of a solvent, an organic base is added to the reaction system. The structure of the 2-imidazolidineone is shown in formula (Ⅰ): (I); The organic base is at least one of DBU and TBD.

2. The preparation method according to claim 1, characterized in that: The inorganic sulfide is at least one of Na2S, K2S, NaHS, and KHS.

3. The preparation method according to any one of claims 1-2, characterized in that: The reaction conditions include a molar ratio of ethylenediamine to inorganic sulfide of 1:(0.5-4).

4. The preparation method according to any one of claims 1-2, characterized in that: The reaction conditions include a molar ratio of ethylenediamine to inorganic sulfide of 1:(1-2).

5. The preparation method according to any one of claims 1-2, characterized in that: The reaction conditions include a reaction pressure of 1-14 MPa.

6. The preparation method according to any one of claims 1-2, characterized in that: The reaction conditions include a reaction pressure of 3-12 MPa.

7. The preparation method according to any one of claims 1-2, characterized in that: The conditions for the reaction include: The temperature is 90℃-160℃, and / or the reaction time is 4-24 h.

8. The preparation method according to any one of claims 1-2, characterized in that: The conditions for the reaction include: The temperature is 130-160 ℃, and / or the reaction time is 5-12 h.

9. The preparation method according to claim 1, characterized in that: The solvent is selected from at least one of NMP, CH3OH, pyrrolidone, DMF, N,N-dimethylacetamide, DMSO, toluene, and xylene.

10. The preparation method according to claim 1, characterized in that: The solvent is selected from at least one of NMP, CH3OH and DMF.

11. The preparation method according to claim 1, characterized in that: The molar ratio of the organic base to the ethylenediamine is (0-0.6):1.

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