CN119977903A - Method and catalyst for synthesizing oxazolidinone compounds based on carbon dioxide and alcohol amine - Google Patents
Method and catalyst for synthesizing oxazolidinone compounds based on carbon dioxide and alcohol amine Download PDFInfo
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Abstract
The application provides a method for synthesizing an oxazolidinone compound based on carbon dioxide and alcohol amine, a catalyst, the oxazolidinone compound prepared based on carbon dioxide and alcohol amine and application of cerium-based composite oxide in the preparation of the oxazolidinone compound based on carbon dioxide and alcohol amine, wherein the method comprises the steps of taking carbon dioxide and alcohol amine as raw materials, and reacting the alcohol amine with the carbon dioxide under the action of a solid catalyst to generate the oxazolidinone compound; wherein the solid catalyst comprises cerium-based composite oxide, and the reaction process comprises liquid phase carboxylation and cyclodehydration. The method provided by the application can enable the catalyst to be easily separated from the product, and can enable the reactant alcohol amine to have higher conversion rate.
Description
Technical Field
The application relates to the technical field of carbon dioxide catalytic conversion utilization, in particular to a method and a catalyst for synthesizing an oxazolidinone compound based on carbon dioxide and alcohol amine, the oxazolidinone compound prepared based on carbon dioxide and alcohol amine, and application of a cerium-based composite oxide in preparing the oxazolidinone compound based on carbon dioxide and alcohol amine.
Background
Abuse and misuse of antibiotics lead to rapid development of drug-resistant bacteria of various antibiotics and antibacterial drugs, which seriously threatens the life health of patients with infectious diseases. Oxazolidinone antibacterial agents (such as linezolid, radzolid, etc.) are novel chemical total synthesis antibacterial agents after sulfenamides and fluoroquinolones, and exert antibacterial effects by inhibiting bacterial protein synthesis, and the core unit is oxazolidinone. The oxazolidone antibacterial agent is prepared by reacting carbon dioxide with nitrogen-containing organic matters, so that the problems of greenhouse effect and the like caused by carbon dioxide can be eliminated, and the oxazolidone antibacterial agent can be converted into high-added-value medicines. In theory, the carboxycyclization of amino alcohol and carbon dioxide is the simplest green route for converting carbon dioxide to oxazolidinones. On the one hand, amino alcohols (derivatives of various amino acids) are an ideal chemical that is readily available, inexpensive and generally safe, and on the other hand, cyclization of amino alcohols and carbon dioxide produces only water as a stoichiometric by-product, being an ideal green synthetic route. Homogeneous metal-organic catalysts such as electrophiles such as trialkylphosphines, high energy phosphorus compounds or strong bases such as DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene), trialkylamines and guanidine and organotitanium complexes can promote the synthesis of oxazolidinones from carbon dioxide and alcohol amines, but these processes use large amounts of condensing agents resulting in substantial cost increases and the formation of large amounts of waste (e.g., alkylphosphine oxides, etc.) which are difficult to remove from the product. Therefore, there is an urgent need to develop a reaction system for synthesizing oxazolidinones with high selectivity, which is easy to separate.
Disclosure of Invention
Based on the method, the catalyst, the oxazolidone prepared based on the carbon dioxide and the alcohol amine and the application of the cerium-based composite oxide in the preparation of the oxazolidone based on the carbon dioxide and the alcohol amine are provided by the application, and the catalyst can be easily separated and removed from a system after the reaction by the preparation method.
In a first aspect, the present application provides a method for synthesizing an oxazolidinone compound based on carbon dioxide and an alcohol amine, comprising:
Carbon dioxide and alcohol amine are used as raw materials, and the alcohol amine and the carbon dioxide react under the action of a solid catalyst to generate the oxazolidinone compound, wherein the solid catalyst comprises cerium-based composite oxide, and the reaction process comprises liquid phase carboxylation and cyclodehydration.
In some embodiments of the application, the cerium-based composite oxide includes one or more of a first cerium-based composite oxide, a second cerium-based composite oxide, and a third cerium-based composite oxide;
The first cerium-based composite oxide comprises CeM1 x1Oy1, wherein M1 comprises a first metal cation different from Ce, and the values of x1 and y1 enable the algebraic sum of the valence of the CeM1 x1Oy1 to be zero;
The second cerium-based composite oxide comprises CeO 2-M2x2Oy2, wherein M2 comprises a second metal cation different from Ce, and the values of x2 and y2 enable the algebraic sum of the valence of M2 x2Oy2 to be zero;
The third cerium-based composite oxide comprises M3'-CeM3 x3Oy3, wherein M3 comprises a third metal cation different from Ce, M3' comprises a fourth metal cation, and the values of x3 and y3 enable the algebraic sum of the valence of the CeM3 x3Oy3 to be zero;
optionally, each of the M1, the M2, and the M3 independently comprises at least one of Zn 2+、La3+、In3+、Al3+ and Zr 4+;
Optionally, the M3' comprises at least one of Na +、Li+、Ba2+ or Co x'+.
In some embodiments of the application, one or more of the following conditions are met:
(1) In the CeO 2-M2x2Oy2, the molar ratio of Ce to M2 is recorded as Ce/M2, and then Ce/M2 is more than 0 and less than or equal to 1000, and is optionally more than 0 and less than or equal to 10, and further optionally more than 0.25 and less than or equal to 4;
(2) In the M3'-CeM3 x3Oy3, the molar ratio of M3' to Ce is expressed as M3'/Ce, and then 0< M3'/Ce is less than or equal to 1, alternatively 0< M3'/Ce is less than or equal to 0.5, and further alternatively 0< M3'/Ce is less than or equal to 0.1;
Optionally, the third cerium-based composite oxide is M3' -CeZr x3O2, wherein the molar ratio of Ce to Zr is Ce/Zr, then 0< Ce/Zr is less than or equal to 1000, optionally 0< Ce/Zr is less than or equal to 10, further optionally 0.25< Ce/Zr is less than or equal to 4.
In some embodiments of the application, one or more of the following conditions are met:
(1) The first cerium-based composite oxide is CeZr x1O2, wherein the molar ratio of Ce to Zr is recorded as (Ce/Zr) ', and is 0< (Ce/Zr)'.
(2) The second cerium-based composite oxide includes one or more of CeO 2-ZnO、CeO2-La2O3、CeO2-In2O3 and CeO 2-Al2O3.
In some embodiments of the application, the alcohol amine comprises one or more of a substituted or unsubstituted ethanolamine, a substituted or unsubstituted propanolamine;
Optionally, the alcohol amine comprises one or more of ethanolamine, 3-amino-1, 2-propanediol, and propanolamine.
In some embodiments of the application, the reaction is carried out in a solution of the alcohol amine;
Optionally, the solvent in the solution comprises one or more of acetonitrile, water, 1, 4-dioxane and mesitylene, further optionally acetonitrile.
In some embodiments of the application, one or more of the following conditions are met:
(1) The reaction temperature is 100-300 ℃, can be selected to be 100-240 ℃, and can be further selected to be 120-220 ℃;
(2) The reaction time is 0.5-100 h, optionally 0.5-60 h, and further optionally 0.5-48 h;
(3) In the reaction process, the pressure of the carbon dioxide is 1atm to 40atm, alternatively 1atm to 20atm, and further alternatively 2atm to 16atm;
(4) The reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 200 rpm-1500 rpm.
In some embodiments of the application, the ratio of the alcohol amine to the solid catalyst is (100-1500): 4-700), optionally (200-1300): 4-700, further optionally (300-1300): 4-700);
optionally, the alcohol amine is used in an amount of 100 mg-1500 mg, optionally 200-1300 mg, and further optionally 300 mg-1300 mg;
optionally, the dosage of the solid catalyst is 4 mg-700 mg, and 34 mg-684 mg is selected.
In a second aspect, the application provides an oxazolidinone compound prepared based on carbon dioxide and an alcohol amine, prepared by the preparation method of the first aspect of the application.
In a third aspect, the present application provides an application of a cerium-based composite oxide in preparing an oxazolidinone compound based on carbon dioxide and an alcohol amine, where the cerium-based composite oxide is the cerium-based composite oxide adopted in the preparation method according to the first aspect of the present application.
The preparation method provided by the application adopts a specific solid catalyst-cerium-based composite oxide, and the catalyst can exist in a solid form before and after the reaction, so that compared with the traditional homogeneous metal organic catalyst, the catalyst is easy to separate and remove from a product after the reaction is finished, and meanwhile, the catalyst also has higher selectivity for the reaction of alcohol amine and carbon dioxide, so that the alcohol amine has higher conversion rate.
Detailed Description
The present application will be described more fully hereinafter in order to facilitate an understanding of the present application. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
For simplicity, only a few numerical ranges are explicitly disclosed. However, any lower limit may be combined with any upper limit to form a range not explicitly recited, and any lower limit may be combined with any other lower limit to form a range not explicitly recited, as may any upper limit combined with any other upper limit. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. It is noted that, as used herein, unless otherwise indicated, the term "and/or" includes any and all combinations of one or more of the associated listed items, "above," below, "and" comprise the present number, and the meaning of "multiple" in "one or more" is two or more.
Herein, reference is made to a value interval (i.e., a range of values), where the distribution of the optional values within the value interval is considered continuous, and includes two value endpoints (i.e., a minimum value and a maximum value) of the value interval, and each value between the two value endpoints, unless otherwise indicated. When a numerical range merely points to integers within the numerical range, unless expressly stated otherwise, both endpoints of the numerical range are inclusive of the integer between the two endpoints, and each integer between the two endpoints is equivalent to the integer directly recited. When multiple numerical ranges are provided to describe a feature or characteristic, the numerical ranges may be combined. In other words, unless otherwise indicated, the numerical ranges disclosed herein are to be understood as including any and all subranges subsumed therein. The "numerical value" in the numerical interval may be any quantitative value, such as a number, a percentage, a proportion, or the like. "numerical intervals" allows for the broad inclusion of numerical interval types such as percentage intervals, proportion intervals, ratio intervals, and the like.
In this document, a plurality of steps are referred to in a method flow, and unless explicitly stated differently herein, the steps are not strictly limited to the order of execution, which may be performed in other orders than as described. Moreover, any step may comprise a plurality of sub-steps or phases, which are not necessarily performed at the same time, but may be performed at different times, the order of their execution is not necessarily sequential, but may be performed in turn or alternately or simultaneously with other steps or sub-steps or portions of phases of other steps.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. Guidance is provided throughout this application by a series of embodiments, which may be used in various combinations. In the various examples, the list is merely a representative group and should not be construed as exhaustive.
Currently, in the reaction of cyclizing amino alcohols and carbon dioxide to oxazolidinones, the usual catalysts are homogeneous metal-organic catalysts such as trialkylphosphines, high-energy phosphorus compounds or strong bases such as DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene), trialkylamines and guanidine, and organotitanium complexes. Although homogeneous metal organic catalysts promote the synthesis of oxazolidinones from carbon dioxide and alcohol amine, the catalysts and reactants are usually in liquid phase, and can be mixed with the reactants and products in liquid phase reaction, and a large amount of byproducts (such as alkyl phosphine oxides and the like) are easy to form, so that the catalyst and the byproducts are difficult to remove from the products after the reaction is finished. In view of this, the inventors have proposed the following technical solution of the present application.
In a first aspect, the present application provides a method for synthesizing an oxazolidinone compound based on carbon dioxide and an alcohol amine, which may include the following step S1:
S1, taking carbon dioxide and alcohol amine as raw materials, and reacting the alcohol amine with the carbon dioxide under the action of a solid catalyst to generate the oxazolidinone compound, wherein the solid catalyst comprises cerium-based composite oxide, and the reaction process comprises liquid phase carboxylation and cyclodehydration.
The preparation method provided by the application adopts a specific solid catalyst-cerium-based composite oxide, and the catalyst can exist in a solid form before and after the reaction, so that compared with the traditional homogeneous metal organic catalyst, the catalyst is easy to separate and remove from a product after the reaction is finished, and meanwhile, the catalyst has higher selectivity for the reaction of alcohol amine and carbon dioxide, so that the alcohol amine has higher conversion rate.
Therefore, the alcohol amine is converted into the oxazolidinone compound through the action of the specific solid catalyst, the catalyst is cheap and easy to obtain, and the catalyst and the product are easy to separate. Based on the method, the preparation method of the alcohol amine-based oxazolidinone compound has higher research value and application prospect.
The term "cerium-based composite oxide" as used herein refers to a composite oxide formed on the basis of cerium element together with one or more other metal elements.
In some embodiments, the cerium-based composite oxide includes one or more of a first cerium-based composite oxide, a second cerium-based composite oxide, and a third cerium-based composite oxide;
The first cerium-based composite oxide comprises CeM1 x1Oy1, wherein M1 comprises a first metal cation different from Ce, and the values of x1 and y1 enable the algebraic sum of the valence of the CeM1 x1Oy1 to be zero;
The second cerium-based composite oxide comprises CeO 2-M2x2Oy2, wherein M2 comprises a second metal cation different from Ce, and the values of x2 and y2 enable the algebraic sum of the valence of M2 x2Oy2 to be zero;
The third cerium-based composite oxide comprises M3'-CeM3 x3Oy3, wherein M3 comprises a third metal cation different from Ce, M3' comprises a fourth metal cation, and the algebraic sum of the valence of CeM3 x3Oy3 is zero by the values of x3 and y 3.
In the present application, "CeO 2-M2x2Oy2" refers to a cerium-based composite oxide formed by chemical bonding between CeO 2 and M2 x2Oy2, and "M3'-CeM3 x3Oy3" refers to a cerium-based composite oxide having a third metal cation M3' supported on CeM3 x3Oy3.
In some embodiments, each of the M1, the M2, and the M3 independently comprises at least one of Zn 2+、La3+、In3+、Al3+ and Zr 4+.
In some embodiments, the M3' comprises at least one of Na +、Li+、Ba2+ or Co x'+.
In some embodiments, the molar ratio of Ce to M2 in CeO 2-M2x2Oy2 is referred to as Ce/M2, then 0< Ce/M2.ltoreq.1000. For example, ce/M2 may be 0.5,1,10,50,100,200,300,400,500,600,700,800,900,1000 or within a range consisting of any of the above values. Optionally 0< Ce/M2 is less than or equal to 10, and further optionally 0.25< Ce/M2 is less than or equal to 4. Thus, ceO 2-M2x2Oy2 has higher selectivity and catalytic performance, and alcohol amine has higher conversion rate.
In some embodiments, the molar ratio of M3 'to Ce in the M3' -CeM3 x3Oy3 is expressed as M3'/Ce, then 0< M3'/Ce.ltoreq.1. For example, M3'/Ce may be 0.5%,1%,5%,10%,50%,80%,100% or within a range comprised of any of the above values. Optionally 0< M3'/Ce is less than or equal to 0.5, and further optionally 0< M3'/Ce is less than or equal to 0.1. Thus, the M3' -CeM3 x3Oy3 has higher selectivity and catalytic performance, and the alcohol amine has higher conversion rate.
In some embodiments, the third cerium-based composite oxide is M3' -CeZr x3O2, wherein the molar ratio of Ce to Zr, ce/Zr, is 0< Ce/Zr.ltoreq.1000. For example, ce/Zr may be 0.5,1,3,10,50,100,200,300,400,500,600,700,800,900,1000 or within a range consisting of any of the above values. The catalyst is optionally 0< Ce/Zr.ltoreq.10, more optionally 0.25< Ce/Zr.ltoreq.4, and particularly optionally 3. Thus, the M3' -CeZr x3O2 has higher selectivity and catalytic performance, and the alcohol amine has higher conversion rate.
In some embodiments, the first cerium-based composite oxide is CeZr x1O2, wherein the molar ratio of Ce to Zr is referred to as (Ce/Zr)', then 0< (Ce/Zr) < 1000. For example, (Ce/Zr)' may be 0.5,1,10,50,100,200,300,400,500,600,700,800,900,1000 or within the range consisting of any of the above values. Can be selected to be 0< (Ce/Zr) '. Further alternatively, 0.25< (Ce/Zr)'. Thus, ceZr x1O2 has higher selectivity and catalytic performance, and alcohol amine has higher conversion rate.
In some embodiments, the second cerium-based composite oxide includes one or more of CeO 2-ZnO、CeO2-La2O3、CeO2-In2O3 and CeO 2-Al2O3.
In some embodiments, the alcohol amine comprises one or more of a substituted or unsubstituted ethanolamine, a substituted or unsubstituted propanolamine.
In some embodiments, the alcohol amine comprises one or more of ethanolamine, 3-amino-1, 2-propanediol, and propanolamine.
In some embodiments, the reaction is performed in a solution of an alcohol amine.
In some embodiments, the solvent in the solution comprises one or more of acetonitrile, water, 1, 4-dioxane, and mesitylene, optionally acetonitrile.
In some embodiments, the reaction may include the following step S10:
And S10, adding alcohol amine, a solvent and a solid catalyst into a reactor, sealing, replacing with high-purity CO 2, removing residual air in the reactor, introducing high-purity CO 2 into the reactor at room temperature after replacement, and then raising the temperature to a specified reaction temperature for reaction.
In some embodiments, the reactor may be an autoclave reactor.
In some embodiments, the number of substitutions with high purity CO 2 may be 5 to 8.
In some embodiments, the reaction is carried out with stirring at a speed of 200rpm to 1500rpm. For example, the rotational speed may be 400 rpm, 600 rpm, 800 rpm, 1000 rpm, 1200 rpm, 1500rpm or within a range comprised of any of the above values. Optionally, the rotation speed is 1000 rpm.
In some embodiments, the ratio of the alcohol amine to the solid catalyst is (100-1500): 4-700. For example, the ratio of the amounts may be 100:700,305:684,610:342,1500:700,750:171,915:34,100:4,1220:17,1500:4 or within a range comprised of any of the above values. The method is characterized by comprising the steps of (200-1300), 34-684, 300-1300 and 34-684. Thus, the catalyst is beneficial to promoting the exertion of the catalytic performance of the solid catalyst, and the alcohol amine has higher conversion rate.
In some embodiments, the alcohol amine is used in an amount of 100mg to 1500mg. For example, the amount of alcohol amine may be 100mg, 305 mg, 610 mg, 750 mg, 915 mg, 1220 mg, 1500mg, or within a range consisting of any of the above values. 200 to 1300mg is selected, and 300mg to 1300mg is further selected.
In some embodiments, the solid catalyst is used in an amount of 4mg to 700mg. For example, the solid catalyst may be used in an amount of 4mg, 8mg, 17 mg, 34mg, 171 mg, 342 mg, 684mg, 700mg, or in a range consisting of any of the above values. 34 mg-684 mg can be selected. Thus, the catalyst is beneficial to promoting the exertion of the catalytic performance of the solid catalyst, and the alcohol amine has higher conversion rate.
In some embodiments, the temperature of the reaction is 100 ℃ to 300 ℃. For example, the temperature may be 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, or within a range consisting of any of the above values. The temperature is selected to be 100-240 ℃, and further selected to be 120-220 ℃. Thus, the alcohol amine has higher conversion rate.
The reaction temperature refers to the real-time temperature of the reactor.
In some embodiments, the reaction time is 0.5h to 100h. For example, the reaction time may be 0.5h, 1h, 2h, 4h, 8h, 12h, 24h, 48h or within a range consisting of any of the above values. The time is 0.5 to 60 hours, and further 0.5 to 48 hours. Thus, the alcohol amine has higher conversion rate.
In some embodiments, the pressure of the carbon dioxide is 1atm to 40atm during the reaction. For example, the pressure of carbon dioxide may be 1atm, 2atm, 4 atm, 6atm, 8atm, 10 atm, 12 atm, 14 atm, 16atm, or within a range consisting of any of the above values. Alternatively 1atm to 20atm, further alternatively 2atm to 16atm, and particularly alternatively 8atm. Thus, the alcohol amine has higher conversion rate.
It should be noted that the cerium-based composite oxide of the present application may be a commercial product or a commercial product, or may be prepared by a conventional method or a well-known method.
In some embodiments, the preparation method of the cerium-based composite oxide includes a coprecipitation method, an impregnation method, and the like. Alternatively, the cerium-based composite oxide is prepared by a coprecipitation method.
In some embodiments, the step of obtaining the first cerium-based composite oxide and/or the second cerium-based composite oxide by the coprecipitation method may include:
and S20, uniformly mixing a cerium salt solution and a non-cerium metal salt solution, continuously stirring and dropwise adding an alkaline reagent until the solution is alkaline and a precipitate is completely separated out, and performing first roasting treatment on the precipitate to obtain the first cerium-based composite oxide and/or the second cerium-based composite oxide.
In some embodiments, the precipitate may also be subjected to one or more of the steps of standing aging, filtering, washing, drying, and the like, prior to subjecting the precipitate to the first calcination treatment.
In some embodiments, the alkaline reagent comprises one or more of ammonia, naOH, or KOH.
In some embodiments, the source of cerium in the cerium salt solution comprises one or more of cerium nitrate, cerium amine nitrate, cerium chloride, optionally cerium amine nitrate.
In some embodiments, the source of non-cerium metal in the non-cerium metal salt solution comprises one or more of a nitrate, an oxy-nitrate, and a chloride salt of the non-cerium metal. In other embodiments, the non-cerium metal includes at least one of Zn, la, in, al and Zr, optionally Zr. For example, where the non-cerium metal is zirconium, the zirconium source comprises zirconyl nitrate and/or zirconium chloride, optionally zirconyl nitrate.
It will be appreciated that in the above preparation step S20, the first cerium-based composite oxide and/or the second cerium-based composite oxide having different (Ce/non-cerium metal) molar ratios can be obtained by adjusting the ratio of the cerium source and the non-cerium metal source to be added and the pH of the solution at the time of preparation.
In some embodiments, in the above preparation step S20, the mixed solution of the cerium salt solution and the non-cerium metal salt solution may be further subjected to a heat treatment to promote the precipitation of the precipitate. Optionally, the heating temperature is 0-100 ℃, and the continuous stirring time is 1-12 h.
In some embodiments, the temperature at which the precipitate is subjected to the first firing treatment is 300 ℃ to 1000 ℃. For example, the temperature of the first firing treatment may be 300 ℃, 400 ℃, 600 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 1000 ℃, or within a range consisting of any of the above values. The temperature is 400-900 ℃, and further 400-850 ℃. Thus, the prepared cerium-based composite oxide has higher selectivity and catalytic performance.
In some embodiments, the third cerium-based composite oxide M3' -CeZr x3O2 may be prepared by the following steps on the basis of step S20:
S30, dipping third metal cations M3' on the first cerium-based composite oxide and/or the second cerium-based composite oxide, enabling the third metal cations M3' to be combined and loaded on the first cerium-based composite oxide and/or the second cerium-based composite oxide, and obtaining M3' -CeZr x3O2 through steps of drying, second roasting and the like.
In some embodiments, the temperature of the second firing process is 300 ℃ to 1000 ℃. For example, the temperature of the second firing treatment may be 300 ℃, 400 ℃, 600 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 1000 ℃, or within a range consisting of any of the above values. The temperature is 400-900 ℃, and further 400-850 ℃. Thus, the prepared cerium-based composite oxide has higher selectivity and catalytic performance.
It can be understood that in the above step S30, the third cerium-based composite oxide M3' -CeZr x3O2 with different M3'/Ce molar ratios can be obtained by controlling the molar concentration (molar percentage) of the third metal ion M3 '.
In a second aspect, the present application provides an oxazolidinone compound prepared based on carbon dioxide and an alcohol amine, prepared by the preparation method of the first aspect of the present application.
In a third aspect, the present application provides an application of a cerium-based composite oxide in preparing an oxazolidinone compound based on carbon dioxide and an alcohol amine, where the cerium-based composite oxide is the cerium-based composite oxide adopted in the preparation method according to the first aspect of the present application.
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since numerous modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1
Preparation of cerium-based composite oxide
After 0.2 mol/L of ceric nitrate solution and 0.2 mol/L of zirconyl nitrate solution are uniformly mixed according to the Ce/Zr molar ratio of 3:1, 1 mol/L of ammonia water is added dropwise until the pH value of the solution is=10. 1h was vigorously stirred at room temperature to give a precipitate of hydroxide, which was dried at 110℃after multiple washes 12: 12 h. Finally, the mixture is placed in a muffle furnace and baked at 700 ℃ for 3h, so that the cerium-based composite oxide is marked as CeZrO 2 (3:1) -700, wherein 3:1 represents Ce/Zr molar ratio of 3:1 and 700 represents baking temperature.
Preparation of oxazolidinones
The reaction of carbon dioxide and alcohol amine to prepare oxazolidinone compound is carried out in a liquid phase batch reactor. The preparation method comprises the following steps of adding 34 mg of CeZrO 2 (3:1) -700, 610 mg ethanolamine and 16.4 g acetonitrile prepared by the steps of adding into a polytetrafluoroethylene lining, sealing, replacing with 8 atm of high-purity CO 2 for 5 times, removing residual air in a kettle, introducing 8 atm of high-purity CO 2 into the reaction kettle at room temperature after replacement, then raising the temperature to 140 ℃, and stirring and reacting 2h by 1000 rpm. The reaction products were detected by gas chromatography and the results are shown in Table 1.
Examples 2 to 5
The preparation method of the cerium-based composite oxide and the oxazolidone preparation process in examples 2 to 5 are basically the same as example 1, except that the molar ratio of Ce/Zr in the solutions in examples 2 to 5 is 1:3, 1:1, 2:1 and 4:1, respectively, and the molar ratio of Ce/Zr in the prepared cerium-based composite oxide is 1:3, 1.06:1, 2.17:1 and 3.96:1 as measured by XRF (X-ray fluorescence spectroscopy). The reaction products were detected by gas chromatography and the results are shown in Table 1.
TABLE 1 influence of composition on catalytic Performance of carbon dioxide reacted with ethanolamine to prepare 2-oxazolidinones
As can be seen, the higher conversion rate of ethanolamine and the higher selectivity of 2-oxazolidinone can be realized by controlling the Ce/Zr molar ratio in the cerium-based composite oxide within a more suitable range, namely the cerium-based composite oxide has higher catalytic performance, and the catalytic performance is better when the Ce/Zr molar ratio is (1-4): 1.
Examples 6 to 12
The preparation method of the cerium-based composite oxide and the oxazolidone preparation process in examples 6 to 12 are substantially the same as those in example 1, except that the firing temperatures for preparing the cerium-based composite oxide in examples 6 to 12 are 400 ℃, 500 ℃, 600 ℃, 750 ℃, 800 ℃, 850 ℃ and 900 ℃, respectively. The reaction products were checked by gas chromatography and the results are shown in Table 2.
TABLE 2 influence of calcination temperature on catalytic performance of cerium-based composite oxide CeZrO 2 (3:1)
It can be seen that the higher conversion rate of ethanolamine and the higher selectivity of 2-oxazolidinone can be achieved by controlling the roasting temperature in a proper range when preparing the cerium-based composite oxide, namely, the cerium-based composite oxide has higher catalytic performance, and the catalytic performance is better when the roasting temperature is 500-900 ℃.
Examples 13 to 19
The preparation method of the cerium-based composite oxide and the preparation process of the oxazolidinone in examples 13 to 19 are basically the same as those in example 9, except that the reaction time of the cerium-based composite oxide CeZrO 2 (3:1) -750 in examples 13 to 19 for catalyzing carbon dioxide and ethanolamine to prepare 2-oxazolidinone is 0.5 h, 1h, 4h, 8 h, 12 h, 24h, 48 h, respectively. The reaction products were detected by gas chromatography and the results are shown in Table 3.
TABLE 3 influence of the reaction time on the catalytic performance of the cerium-based composite oxide CeZrO 2 (3:1) -750
As can be seen, the reaction time of catalyzing carbon dioxide and ethanolamine to prepare 2-oxazolidone by using the cerium-based composite oxide CeZrO 2 (3:1) -750 is controlled in a proper range, so that the ethanolamine has higher conversion rate, the 2-oxazolidone has higher selectivity, namely the cerium-based composite oxide has higher catalytic performance, and the catalytic performance is better when the reaction time is 2-48 h.
Examples 20 to 23
The preparation method of the cerium-based composite oxide in examples 20 to 23 and the preparation process of the oxazolidinone are basically the same as those in example 9, except that the reaction temperatures of the cerium-based composite oxide CeZrO 2 (3:1) -750 in examples 20 to 23 for catalyzing carbon dioxide and ethanolamine to prepare 2-oxazolidinone are 120 ℃, 160 ℃, 180 ℃ and 200 ℃, respectively. The reaction products were checked by gas chromatography and the results are shown in Table 4.
TABLE 4 influence of the reaction temperature on the catalytic properties of CeZrO 2 (3:1) -750
As can be seen, the reaction temperature for preparing 2-oxazolidone by catalyzing carbon dioxide and ethanolamine by using cerium-based composite oxide CeZrO 2 (3:1) -750 is controlled in a proper range, so that the ethanolamine has higher conversion rate, the 2-oxazolidone has higher selectivity, namely the cerium-based composite oxide has higher catalytic performance, and the catalytic performance is better when the reaction temperature is 140-200 ℃.
Example 24
The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in example 24 are substantially the same as those in example 21, except that the cerium-based composite oxide CeZrO 2 (3:1) -750 in example 24 is added in an amount of 17: 17 mg. The reaction products were detected by gas chromatography and the results are shown in Table 5.
Example 25
The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in example 25 are substantially the same as those in example 22, except that the cerium-based composite oxide CeZrO 2 (3:1) -750 in example 25 is added in an amount of 8 mg. The reaction products were detected by gas chromatography and the results are shown in Table 5.
Example 26
The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in example 26 are substantially the same as those in example 23, except that the cerium-based composite oxide CeZrO 2 (3:1) -750 in example 25 is added in an amount of 4 mg. The reaction products were detected by gas chromatography and the results are shown in Table 5.
Table 5 CeZrO 2 (3:1) -750 catalytic Properties
It can be seen that the ethanolamine can have higher conversion rate and the 2-oxazolidinone has higher selectivity, namely the cerium-based composite oxide has higher catalytic performance by controlling the dosage ratio of the ethanolamine to the catalyst in a more appropriate range.
Examples 27 to 31
The preparation method of the cerium-based composite oxide and the preparation process of the oxazolidinone in examples 27 to 31 are basically the same as those in example 9, except that the reaction pressures of CO 2 of the cerium-based composite oxide CeZrO 2 (3:1) -750 in examples 27 to 31 for catalyzing carbon dioxide and ethanolamine to prepare 2-oxazolidinone are 2 atm, 4 atm, 6 atm, 10 atm and 12 atm respectively. The reaction products were checked by gas chromatography and the results are shown in Table 6.
TABLE 6 influence of carbon dioxide pressure on CeZrO 2 (3:1) -750 catalytic properties
As can be seen, the CO 2 reaction pressure for preparing 2-oxazolidone by catalyzing carbon dioxide and ethanolamine by using cerium-based composite oxide CeZrO 2 (3:1) -750 is controlled in a proper range, so that the ethanolamine has higher conversion rate, the 2-oxazolidone has higher selectivity, namely the cerium-based composite oxide has higher catalytic performance, and the catalytic performance is better when the reaction pressure is 4 atm-12 atm.
Examples 32 to 35
The preparation method of the cerium-based composite oxide and the preparation process of the oxazolidinone in examples 32 to 35 are basically the same as those in example 14, except that the cerium-based composite oxide CeZrO 2 (3:1) -750 in examples 32 to 35 catalyzes the addition of carbon dioxide and ethanolamine to prepare 2-oxazolidinone with ethanolamine in amounts of 305 mg, 458 mg, 915 mg and 1220 mg, respectively. The reaction products were checked by gas chromatography and the results are shown in Table 7.
TABLE 7 influence of ethanolamine addition on CeZrO 2 (3:1) -750 catalytic Performance
It can be seen that the ratio of the alcohol amine to the catalyst is controlled within a proper range, so that the alcohol amine has a high conversion rate, the 2-oxazolidinone has a high selectivity, namely the cerium-based composite oxide has a high catalytic performance, and the catalytic performance is better when the ratio of the alcohol amine to the catalyst is (305-915): 34.
Example 36
The preparation method of the cerium-based composite oxide in example 36 and the preparation process of the oxazolidinone are basically the same as those in example 17, except that the cerium-based composite oxide CeZrO 2 (3:1) -750 in example 36 catalyzes the preparation of 2-oxazolidinone from carbon dioxide and ethanolamine, the addition amount of ethanolamine is 305 mg, and the addition amount of the cerium-based composite oxide is 684 mg. The reaction products were checked by gas chromatography and the results are shown in Table 8.
Example 37
The catalyst preparation and oxazolidone preparation procedure in example 37 were substantially the same as in example 36, except that the cerium-based composite oxide CeZrO 2 (3:1) -750 in example 37 catalyzed carbon dioxide and ethanol amine to produce 2-oxazolidone had a CO 2 reaction pressure of 16 atm. The reaction products were checked by gas chromatography and the results are shown in Table 8.
Example 38
The preparation method of the cerium-based composite oxide in example 38 and the preparation process of the oxazolidinone are basically the same as in example 36, except that the cerium-based composite oxide CeZrO 2 (3:1) -750 in example 38 catalyzes the preparation of 2-oxazolidinone from carbon dioxide and ethanolamine, the ethanolamine addition amount is 915 mg, and the cerium-based composite oxide addition amount is 342 mg. The reaction products were checked by gas chromatography and the results are shown in Table 8.
Table 8 CeZrO 2 (3:1) -750 catalytic Properties
Examples 39 to 41
The preparation method of the cerium-based composite oxide in examples 39 to 41 and the preparation process of the oxazolidinone are basically the same as those in example 37, except that the reaction time in the preparation of 2-oxazolidinone by catalyzing carbon dioxide and ethanolamine with CeZrO 2 (3:1) -750 in examples 39 to 41 is 1h, 2h and 4h respectively. The reaction products were checked by gas chromatography and the results are shown in Table 9.
TABLE 9 influence of the reaction time on the catalytic properties of CeZrO 2 (3:1) -750
Examples 42 to 43
The preparation method of the cerium-based composite oxide in examples 42 to 43 and the preparation process of the oxazolidinone are basically the same as those in example 9, except that the cerium-based composite oxide CeZrO 2 (3:1) -750 in examples 42 to 43 catalyzes the preparation of 2-oxazolidinone from carbon dioxide and ethanolamine in the solvents of 1, 4-dioxane and mesitylene respectively. The reaction products were checked by gas chromatography and the results are shown in Table 10.
TABLE 10 influence of solvents on the catalytic properties of CeZrO 2 (3:1) -750
It can be seen that the selection of a suitable solvent can lead to higher conversion of ethanolamine and higher selectivity of 2-oxazolidinone, namely higher catalytic performance of cerium-based composite oxide.
Example 44
The preparation method of the cerium-based composite oxide in example 44 and the preparation process of oxazolidinone are substantially the same as in example 9, except that cerium-based composite oxide CeZrO 2 (3:1) -750 in example 44 catalyzes the conversion of 610 mg ethanolamine into 750 mg propanolamine in the preparation of 2-oxazolidinone from carbon dioxide and ethanolamine. The reaction products were checked by gas chromatography and the results are shown in Table 11.
Example 45
The preparation method of the cerium-based composite oxide in example 45 and the preparation process of oxazolidinone are substantially the same as in example 9, except that cerium-based composite oxide CeZrO 2 (3:1) -750 in example 45 catalyzes the conversion of 610 mg ethanolamine to 910 mg of 3-amino-1, 2-propanediol in the preparation of 2-oxazolidinone from carbon dioxide and ethanolamine. The reaction products were checked by gas chromatography and the results are shown in Table 11.
TABLE 11 influence of ethanolamine addition on CeZrO 2 (3:1) -750 catalytic Performance
Example 46
Preparation of cerium-based composite oxide
After 0.2 mol/L of cerous nitrate solution and 0.2 mol/L of zirconium oxide nitrate solution are uniformly mixed in a Ce/Zr molar ratio of 3:1, 1mol/L of ammonia water is added dropwise until the pH value of the solution is=10. 1h was vigorously stirred at room temperature to give a precipitate of hydroxide, which was dried at 110℃after multiple washes 12: 12 h. Finally, the mixture was placed in a muffle furnace and baked at 600 ℃ for 3h hours, and the obtained cerium-based composite oxide was named as CeZrO 2 (3:1) -600.
1:1 Mol% sodium hydroxide (Na/Ce molar ratio=0.01) was impregnated on CeZrO 2 (3:1) -600 catalyst and dried at 110 ℃ for 12 h. Finally, the mixture was placed in a muffle furnace and baked at 600℃for 3 h. The resulting cerium-based composite oxide was designated as 1% Na-CeZrO 2 (3:1) -600.
The oxazolidinone preparation procedure in example 46 was essentially the same as in example 9. The reaction products were checked by gas chromatography and the results are shown in Table 12.
Examples 47 to 48
The preparation method of the cerium-based composite oxide and the preparation process of the oxazolidinone in examples 47 to 48 are basically the same as those in example 46, except that the molar percentage of sodium hydroxide in examples 47 to 48 is regulated so that the Na/Ce ratio of the prepared cerium-based composite oxide is 0.05 and 0.10, respectively. The reaction products were checked by gas chromatography and the results are shown in Table 12.
Examples 49 to 51
The preparation method of the cerium-based composite oxide in examples 49 to 51 and the preparation process of the oxazolidinone are basically the same as those in example 46, except that lithium hydroxide, barium chloride and cobalt nitrate are respectively used for replacing sodium hydroxide in examples 49 to 51, and the mole percentages of the lithium hydroxide, the barium chloride and the cobalt nitrate are regulated so that the prepared cerium-based composite oxide is 1% Li-CeZrO 2(3:1)-600、0.5%Ba-CeZrO2 (3:1) -750 and 0.5% Co-CeZrO 2 (3:1) -750 respectively. The reaction products were checked by gas chromatography and the results are shown in Table 12.
Effect of table 12 adjuvants on the catalytic properties of CeZrO 2 (3:1) -750
It can be seen that the molar ratio of Na/Ce is controlled within a proper range, so that the ethanolamine has higher conversion rate, the 2-oxazolidinone has higher selectivity, namely the cerium-based composite oxide has higher catalytic performance, and the catalytic performance is better when the molar ratio of Na/Ce is (0.01-0.05): 1.
Example 52
Preparation of cerium-based composite oxide
After 0.2 mol/L of zinc nitrate solution and 0.2 mol/L of zirconium oxide nitrate solution were uniformly mixed in a Ce/Zn molar ratio of 3:1, 1 mol/L of ammonia water was added dropwise until the ph=10 of the solution. 1h was vigorously stirred at room temperature to give a precipitate of hydroxide, which was dried at 110℃after multiple washes 12: 12 h. Finally, placing the mixture in a muffle furnace to bake at 600 ℃ for 3 h, and obtaining the cerium-based composite oxide which is named as CeO 2 -ZnO (3:1) -600, wherein 3:1 represents Ce/Zn molar ratio of 3:1 and 600 represents baking temperature.
The oxazolidinone preparation procedure of example 52 was essentially the same as that of example 1, except that CeO 2 -ZnO (3:1) -600 was used as catalyst in example 52. The reaction products were checked by gas chromatography and the results are shown in Table 13.
Examples 53 to 55
The process for preparing oxazolidinones of examples 53-55 is substantially the same as example 52, except that CeO2-La2O3(3:1)-600、CeO2-In2O3(3:1)-600、CeO2-Al2O3(3:1)-600 is used as a catalyst in examples 53-55. The reaction products were checked by gas chromatography and the results are shown in Table 13.
Catalytic performance of carbon dioxide and ethanolamine reactions to prepare 2-oxazolidinones in Table 13 CeO 2-MxOy
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (10)
1. A method for synthesizing an oxazolidinone compound based on carbon dioxide and an alcohol amine, comprising:
Carbon dioxide and alcohol amine are used as raw materials, and the alcohol amine and the carbon dioxide react under the action of a solid catalyst to generate the oxazolidinone compound, wherein the solid catalyst comprises cerium-based composite oxide, and the reaction process comprises liquid phase carboxylation and cyclodehydration.
2. The method of claim 1, wherein the cerium-based composite oxide comprises one or more of a first cerium-based composite oxide, a second cerium-based composite oxide, and a third cerium-based composite oxide;
The first cerium-based composite oxide comprises CeM1 x1Oy1, wherein M1 comprises a first metal cation different from Ce, and the values of x1 and y1 enable the algebraic sum of the valence of the CeM1 x1Oy1 to be zero;
The second cerium-based composite oxide comprises CeO 2-M2x2Oy2, wherein M2 comprises a second metal cation different from Ce, and the values of x2 and y2 enable the algebraic sum of the valence of M2 x2Oy2 to be zero;
The third cerium-based composite oxide comprises M3'-CeM3 x3Oy3, wherein M3 comprises a third metal cation different from Ce, M3' comprises a fourth metal cation, and the values of x3 and y3 enable the algebraic sum of the valence of the CeM3 x3Oy3 to be zero;
optionally, each of the M1, the M2, and the M3 independently comprises at least one of Zn 2+、La3+、In3+、Al3+ and Zr 4+;
Optionally, the M3' comprises at least one of Na +、Li+、Ba2+ or Co x'+.
3. The method of claim 2, wherein one or more of the following conditions are met:
(1) In the CeO 2-M2x2Oy2, the molar ratio of Ce to M2 is recorded as Ce/M2, and then Ce/M2 is more than 0 and less than or equal to 1000, and is optionally more than 0 and less than or equal to 10, and further optionally more than 0.25 and less than or equal to 4;
(2) In the M3'-CeM3 x3Oy3, the molar ratio of M3' to Ce is expressed as M3'/Ce, and then 0< M3'/Ce is less than or equal to 1, alternatively 0< M3'/Ce is less than or equal to 0.5, and further alternatively 0< M3'/Ce is less than or equal to 0.1;
Optionally, the third cerium-based composite oxide is M3' -CeZr x3O2, wherein the molar ratio of Ce to Zr is Ce/Zr, then 0< Ce/Zr is less than or equal to 1000, optionally 0< Ce/Zr is less than or equal to 10, further optionally 0.25< Ce/Zr is less than or equal to 4.
4. The method of claim 2, wherein one or more of the following conditions are met:
(1) The first cerium-based composite oxide is CeZr x1O2, wherein the molar ratio of Ce to Zr is recorded as (Ce/Zr) ', and is 0< (Ce/Zr)'.
(2) The second cerium-based composite oxide includes one or more of CeO 2-ZnO、CeO2-La2O3、CeO2-In2O3 and CeO 2-Al2O3.
5. The method of any one of claims 1-4, wherein the alcohol amine comprises one or more of a substituted or unsubstituted ethanolamine, a substituted or unsubstituted propanolamine;
Optionally, the alcohol amine comprises one or more of ethanolamine, 3-amino-1, 2-propanediol, and propanolamine.
6. The method according to any one of claims 1 to 4, wherein the reaction is carried out in a solution of the alcohol amine;
Optionally, the solvent in the solution comprises one or more of acetonitrile, water, 1, 4-dioxane and mesitylene, further optionally acetonitrile.
7. The method of any one of claims 1-4, wherein one or more of the following conditions are satisfied:
(1) The reaction temperature is 100-300 ℃, can be selected to be 100-240 ℃, and can be further selected to be 120-220 ℃;
(2) The reaction time is 0.5-100 h, optionally 0.5-60 h, and further optionally 0.5-48 h;
(3) In the reaction process, the pressure of the carbon dioxide is 1atm to 40atm, alternatively 1atm to 20atm, and further alternatively 2atm to 16atm;
(4) The reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 200 rpm-1500 rpm.
8. The method according to any one of claims 1 to 4, wherein the ratio of the alcohol amine to the solid catalyst is (100 to 1500): 4 to 700, optionally (200 to 1300): 4 to 700, further optionally (300 to 1300): 4 to 700;
optionally, the alcohol amine is used in an amount of 100 mg-1500 mg, optionally 200-1300 mg, and further optionally 300 mg-1300 mg;
optionally, the dosage of the solid catalyst is 4 mg-700 mg, and 34 mg-684 mg is selected.
9. An oxazolidinone compound prepared based on carbon dioxide and an alcohol amine, which is characterized by being prepared by the method of any one of claims 1-8.
10. Use of a cerium-based composite oxide for preparing an oxazolidinone compound based on carbon dioxide and an alcohol amine, characterized in that the cerium-based composite oxide is the cerium-based composite oxide used in the method according to any one of claims 1 to 8.
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| EP0478073A2 (en) * | 1990-09-20 | 1992-04-01 | Union Carbide Chemicals And Plastics Company, Inc. | Processes for the preparation of carboxylated compounds |
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| EP0478073A2 (en) * | 1990-09-20 | 1992-04-01 | Union Carbide Chemicals And Plastics Company, Inc. | Processes for the preparation of carboxylated compounds |
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