CN114539046B - Process for preparing caronic acid and caronic anhydride - Google Patents
Process for preparing caronic acid and caronic anhydride Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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Abstract
The invention relates to a preparation method of a Carbonic acid or a derivative thereof, which comprises the following steps: mixing a catalytic system consisting of transition metal nitrate, inorganic halide and carbon nano tubes loaded with nitroxide free radical compounds with 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid or derivatives thereof in an organic solvent to obtain a reaction system; under the aerobic condition, carrying out oxidation reaction on the reaction system to obtain a reaction solution; filtering the reaction solution, and performing post-treatment on the filtrate to obtain the Caronic acid or the derivatives thereof. The invention also relates to a preparation method of the caronic anhydride or the derivatives thereof, which comprises the following steps: the preparation method is adopted to obtain the caronic acid or the derivatives thereof, and then the caronic acid anhydride or the derivatives thereof are obtained through cyclization reaction. When the catalytic system is adopted, the oxygen can be used as an oxidant to prepare the caronic acid or the derivatives thereof, and the caronic anhydride or the derivatives thereof are prepared through cyclization reaction, so that the catalytic system is environment-friendly, economical and efficient, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of pharmaceutical chemical industry, in particular to a preparation method of caronic acid or derivatives thereof and caronic anhydride or derivatives thereof.
Background
6, 6-dimethyl-3-oxabicyclo [3.1.0] hexane-2, 4-dione, commonly known as caron anhydride (Caronic anhydride), is an important pharmaceutical intermediate for producing the hepatitis C protease inhibitor boscalid (Boceprevir) and oral medicine (PF-07321332), and can be widely applied to pesticides and other organic synthesis fields. Wherein, the chemical structural formulas of the caron anhydride, the hepatitis C protease inhibitor and the PF-07321332 are as follows:
。
at present, chinese patent CN101020680A takes ethyl chrysanthemate as a raw material, and obtains caronic acid through oxidation of potassium permanganate in an acetone solvent, and then the caronic acid anhydride is prepared through dehydration cyclization in a system of acetic anhydride and sodium acetate. Chinese patent CN102391228A uses chrysanthemate as raw material, instead of ozone as oxidant to prepare caronic acid, and then caronic acid anhydride is prepared from caronic acid. In addition, the chrysanthemate is difficult to prepare, few in manufacturers and limited in production scale.
Chinese patent CN102070575a uses methyl isobutylene ketone as raw material, and carries out addition reaction with (ethoxycarbonylmethyl) dimethyl sulfur ylide to prepare (3-acetyl-2, 2-dimethylcyclopropane-1-ethyl formate), then synthesizes caronic acid by sodium hypochlorite oxidation, and prepares caronic anhydride from the caronic acid. Chinese patent CN104163759a discloses a method for preparing caronic acid from 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid. However, these methods all use sodium hypochlorite as an oxidizing agent for oxidation, which generates a large amount of waste water and waste salt, causing serious environmental pollution, and the large-scale industrial production of caronic anhydride with the rapidly increasing market demand by this method has been faced with serious challenges. Therefore, developing a clean and efficient catalytic system for preparing the caronic anhydride intermediate caronic acid is a technical problem to be solved by the skilled person.
Disclosure of Invention
Based on this, it is necessary to provide a process for producing caronic acid or its derivatives and caronic anhydride or its derivatives, which is environmentally friendly, economical and efficient, and suitable for large-scale industrial production, in view of the above-mentioned problems.
A process for the preparation of caronic acid or its derivatives comprising the steps of:
mixing 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid or a derivative thereof with a catalytic system in an organic solvent to obtain a reaction system, wherein the structural formula of the 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid or the derivative thereof is shown as a formula (1), and the catalytic system comprises transition metal nitrate, inorganic halide and carbon nanotubes loaded with nitroxide free radical compounds;
under the aerobic condition, carrying out oxidation reaction on the reaction system to obtain a reaction solution; and
filtering the reaction liquid, and performing post-treatment on the filtrate to obtain the caronic acid or the derivatives thereof with the structural formula shown in the formula (2);
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r in the formula (1) and the formula (2) 1 And R is 2 Independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, nitro or halogen.
In one embodiment, the carbon nanotube carrying a nitroxide compound is at least one selected from piperidine nitroxide compounds and phthalamides nitroxide compounds.
In one embodiment, the piperidine nitroxide compound is selected from at least one of M-1 to M-4,
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m-1 to M-4, R 1 、R 2 、R 3 、R 4 Independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl or substituted or unsubstituted C1-C5 alkoxy, R 5 Selected from hydroxy or amino, R 6 Selected from hydrogen, halogen, nitro, hydroxy, cyano, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C1-C5 alkoxy or substituted or unsubstituted C6-C40 aryl, n 1 An integer selected from 0-2, n 2 An integer selected from 0 to 5, n 3 An integer selected from 0-6, n 4 An integer selected from 0-7.
In one embodiment, the phthalamide nitroxide compound is selected from at least one of N-1 to N-3,
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in N-1 to N-3, R 5 Selected from hydroxy or amino, R 6 Selected from hydrogen, halogen, nitro, hydroxy, cyano, substituted or unsubstitutedSubstituted C1-C5 alkyl, substituted or unsubstituted C1-C5 alkoxy or substituted or unsubstituted C6-C40 aryl, X 1 -X 4 Each independently selected from C or N; n is n 5 An integer selected from 0-3, n 6 An integer selected from 0-1, n 7 An integer selected from 0-5.
In one embodiment, the transition metal of the transition metal nitrate is selected from at least one of iron, copper, chromium, manganese, cobalt, palladium.
In one embodiment, the inorganic halide is at least one selected from lithium halide, sodium halide, potassium halide, rubidium halide, cesium halide.
In one embodiment, the molar ratio of the 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid or a derivative thereof, the transition metal nitrate, the inorganic halide and the nitroxide compound in the nitroxide compound-loaded carbon nanotubes is 1:0.01-0.1:0.01-0.1:0.01-0.1.
In one embodiment, the method for constructing the aerobic condition comprises the following steps: introducing gas with the oxygen content of 5-100%, and maintaining the pressure at 0.1-6 MPa.
In one embodiment, in the step of oxidizing the reaction system, a gradient heating method is adopted, the temperature is firstly raised to 20-60 ℃, the temperature is kept for 2-6 h, and then the temperature is raised to 50-100 ℃, and the temperature is kept for 2-6 h.
In one embodiment, the post-treatment step comprises quenching the filtrate with a quencher, adjusting the pH to 1-4, and extracting with an organic solvent.
In one embodiment, in the step of filtering the reaction solution, the carbon nanotubes carrying the nitroxide compound are also recovered, and the recovered carbon nanotubes carrying the nitroxide compound are recycled to the catalytic system.
A process for the preparation of caronic anhydride or its derivatives comprising the steps of:
the preparation method is adopted to obtain the caronic acid or the derivatives thereof with the structural formula shown in the formula (2); and
carrying out cyclization reaction on the caronic acid or the derivatives thereof to obtain caronic anhydride or the derivatives thereof with the structural formula shown in formula (3);
；
r in formula (3) 1 And R is 2 Independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, nitro or halogen.
In one embodiment, in the step of performing the cyclization reaction on the caronic acid or the derivatives thereof, a gradient heating method is adopted, the temperature is firstly raised to 120-160 ℃, the temperature is kept for 2-6 h, then the temperature is raised to 150-200 ℃, and the temperature is kept for 2-6 h.
In one embodiment, in the step of subjecting the caronic acid or its derivative to the cyclization reaction, the dehydrating agent is at least one selected from acetic anhydride, sodium acetate, maleic anhydride, phthalic anhydride.
In one embodiment, the molar ratio of the dehydrating agent to the 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid or derivative thereof is from 2:1 to 4:1.
The invention adopts transition metal nitrate, inorganic halide and carbon nano tube of supported nitrogen-oxygen free radical compound to form a catalytic system, takes oxygen as an oxidant, smoothly prepares 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid or derivatives thereof into Carlong acid or derivatives thereof, and obtains Carlong anhydride or derivatives thereof through intramolecular dehydration cyclization reaction of the Carlong acid or derivatives thereof.
Meanwhile, the carbon nano tube loaded with the nitroxide free radical compound can be separated from the reaction liquid by simple filtration after the reaction is finished, and can be recycled. Therefore, the preparation method is environment-friendly, economical and efficient, and is suitable for large-scale industrial production.
Detailed Description
The present invention will be described in more detail below in order to facilitate understanding of the present invention. It should be understood, however, that the invention may be embodied in many different forms and is not limited to the implementations or embodiments described herein. Rather, these embodiments or examples are provided so that this disclosure will be thorough and complete.
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 invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments or examples only and is not intended to be limiting of the invention.
The preparation method of the caronic acid or the derivatives thereof provided by the invention comprises the following steps:
s11, mixing 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid or a derivative thereof with a catalytic system in an organic solvent to obtain a reaction system, wherein the structural formula of the 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid or the derivative thereof is shown as a formula (1), and the catalytic system comprises transition metal nitrate, inorganic halide and carbon nanotubes loaded with nitroxide free radical compounds;
s12, under the aerobic condition, carrying out an oxidation reaction on the reaction system to obtain a reaction solution;
s13, filtering the reaction liquid, and performing post-treatment on the filtrate to obtain the caronic acid or the derivative thereof with the structural formula shown in the formula (2);
、/>；
r in the formula (1) and the formula (2) 1 And R is 2 Independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, nitro or halogen.
In step S11, the transition metal of the transition metal nitrate is selected from at least one of iron, copper, chromium, manganese, cobalt, and palladium, and optionally, the transition metal nitrate is selected from at least one of ferric nitrate nonahydrate and cupric nitrate trihydrate.
Optionally, the inorganic halide is at least one selected from lithium halide, sodium halide, potassium halide, rubidium halide and cesium halide, the halogen atom is fluorine, chlorine, bromine and iodine, and further, the inorganic halide is at least one selected from potassium chloride and sodium chloride, and more preferably potassium chloride.
Optionally, in the carbon nanotube loaded with the nitroxide free radical compound, the nitroxide free radical compound is at least one of piperidine nitroxide free radical compound and phthalamide nitroxide free radical compound, further, the piperidine nitroxide free radical compound is at least one of M-1 to M-4, and the phthalamide nitroxide free radical compound is at least one of N-1 to N-3.
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M-1 to M-4, R 1 、R 2 、R 3 、R 4 Independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl or substituted or unsubstituted C1-C5 alkoxy, R 5 Selected from hydroxy or amino, R 6 Selected from hydrogen, halogen, nitro, hydroxy, cyano, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C1-C5 alkoxy or substituted or unsubstituted C6-C40 aryl, n 1 An integer selected from 0-2, n 2 An integer selected from 0 to 5, n 3 An integer selected from 0-6, n 4 An integer selected from 0-7.
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In N-1 to N-3, R 5 Selected from hydroxy or amino, R 6 Selected from hydrogen, halogen, nitro, hydroxy, cyano, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C1-C5 alkoxy or substituted or unsubstituted C6-C40 aryl, X 1 -X 4 Each independently selected from C or N; n is n 5 An integer selected from 0-3, n 6 An integer selected from 0-1, n 7 An integer selected from 0-5.
The invention uses the one-dimensional structure and high specific surface area of Carbon Nano Tubes (CNTs) and the excellent carrier property thereof to load the nitrogen-oxygen free radical compound on the carbon nano tubes, thereby not only having excellent catalytic property, but also being capable of recycling, and the carbon nano tubes loaded with the nitrogen-oxygen free radical compound after recycling can be recycled.
Optionally, the preparation method of the carbon nanotube loaded with the nitroxide free radical compound comprises the following steps:
preparing carboxylated carbon nanotubes: under the condition of heating and refluxing, carbon Nanotubes (CNTs) react in strong oxidizing acid, and then the reacted mixture is filtered, washed with deionized water to be neutral, and dried to obtain Carboxylated Carbon Nanotubes (CCNTs);
preparing a nitroxide free radical modified carbon nanotube: suspending the carboxylated carbon nano tube in an organic solvent, adding a nitroxide free radical compound, heating and stirring at a certain temperature for reacting for a period of time, and then filtering, washing and drying to obtain the carbon nano tube loaded with the nitroxide free radical compound.
Optionally, in the step of preparing the carboxylated carbon nanotubes, the strong oxidizing acid is at least one selected from concentrated nitric acid, concentrated sulfuric acid, a mixed acid of concentrated sulfuric acid and concentrated nitric acid, and a mixed acid of hydrogen peroxide and concentrated sulfuric acid, and the mass-volume ratio of the carbon nanotubes to the strong oxidizing acid is 1g: (10 mL-50 mL), the reaction temperature is 20-200 ℃, the reaction time is 2-24 h, and the carboxylation rate of the carbon nano tube in the obtained carboxylated carbon nano tube is 0.5-10 wt%.
Optionally, in the step of preparing the nitroxide-modified carbon nanotube, the organic solvent is at least one selected from benzene, toluene, acetonitrile, tetrahydrofuran, acetone, butanone, pyridine, chloroform, dichloromethane, dichloroethane, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide.
Optionally, when the nitroxide compound is selected from hydroxyl-containing nitroxide compounds, the step of preparing the nitroxide-modified carbon nanotubes is: suspending carboxylated carbon nanotube in organic solvent, adding condensing agent and nitroxide radical compound, heating and stirring at certain temperature to react for some time, filtering, washing and stoving to obtain the carbon nanotube with nitroxide radical compound.
Optionally, when the nitroxide compound is selected from amino-containing nitroxide compounds, the step of preparing the nitroxide-modified carbon nanotube is: suspending carboxylated carbon nanotubes in an organic solvent, adding thionyl chloride, stirring and reacting for a period of time under the condition of heating and refluxing, filtering, washing and drying to obtain carbon acyl chloride nanotubes (CONTs), suspending the carbon acyl chloride nanotubes in the organic solution, adding a condensing agent and a nitroxide free radical compound, heating and stirring and reacting for a period of time at a certain temperature, and filtering, washing and drying to obtain the carbon nanotubes loaded with the nitroxide free radical compound.
Wherein the condensing agent is at least one selected from sulfuric acid, benzenesulfonic acid and dicyclohexylcarbodiimide, the reaction temperature is 20-100 ℃, and the reaction time is 6-24 h.
Optionally, in the reaction system, the molar ratio of the 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid or a derivative thereof, the transition metal nitrate, the inorganic halide and the nitroxide free radical compound in the nitroxide free radical compound-loaded carbon nano tube is 1:0.01-0.1:0.01-0.1:0.01-0.1.
Optionally, the organic solvent is at least one selected from 1, 2-dichloroethane, 1-dichloroethane, 1, 2-dichloropropane, 1, 3-dichloropropane, dichloromethane, nitromethane, benzene, toluene, acetonitrile, ethyl acetate and tetrahydrofuran.
In step S12, in the step of performing a gradient heating reaction on the reaction system under an aerobic condition, the construction method of the aerobic condition is as follows: introducing gas with the oxygen content of 5-100%, and maintaining the pressure at 0.1-6 MPa.
Meanwhile, in the step of oxidizing the reaction system, a gradient heating method is adopted, the temperature is firstly increased to 20-60 ℃, the temperature is kept for 2-6 h, then the temperature is increased to 50-100 ℃, the temperature is kept for 2-6 h, so that hydroxyl groups are firstly oxidized to form aldehyde groups, and then carboxyl groups are further oxidized to form the carboxyl groups.
In the step, 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid or a derivative thereof with a structural formula shown in formula (1) is reacted to obtain caronic acid or a derivative thereof with a structural formula shown in formula (2), and the specific reaction equation is as follows:
。
it will be appreciated that in the caronic acid or its derivative represented by formula (2), R 1 And R is 2 The choice of (2) depends on 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid represented by formula (1) or a derivative thereof, both of which are the same.
In step S13, in the step of filtering the reaction solution, the carbon nanotubes loaded with the nitroxide free radical compound are also recovered, and optionally, the recovered carbon nanotubes loaded with the nitroxide free radical compound are recycled to the catalytic system in step S11.
In the step of carrying out post-treatment on the filtrate, the filtrate is quenched by a quenching agent, then the pH is adjusted to 1-4, and then the extraction is carried out by an organic solvent. Wherein the quenching agent is preferably sodium sulfite aqueous solution, and the organic solvent is preferably ethyl acetate.
In the preparation method, a catalytic system is formed by adopting transition metal nitrate, inorganic halide and a carbon nano tube loaded with a nitroxide free radical compound, and oxygen is used as an oxidant, so that 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid or derivatives thereof can be smoothly prepared into caronic acid or derivatives thereof under the reaction condition of gradient temperature rise, and the oxidant such as sodium hypochlorite and the like is not needed.
Meanwhile, the carbon nano tube loaded with the nitroxide free radical compound can be separated from a reaction system through simple filtration after the reaction is finished, and can be recycled.
Therefore, the preparation method is environment-friendly, economical and efficient, and is suitable for large-scale industrial production.
Based on the above, the invention also provides a preparation method of the caronic anhydride or the derivatives thereof, which comprises the following steps:
s21, obtaining the caronic acid or the derivatives thereof with the structural formula shown in the formula (2) by adopting the preparation method;
s22, carrying out cyclization reaction on the caronic acid or the derivatives thereof to obtain caronic anhydride or the derivatives thereof with the structural formula shown in the formula (3);
；
r in formula (3) 1 And R is 2 Independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, nitro or halogen.
In step S22, in the step of performing the cyclization reaction on the caronic acid or the derivative thereof, a gradient heating method is preferably adopted, optionally, the temperature is firstly raised to 120-160 ℃, the temperature is kept for 2-6 h, then the temperature is raised to 150-200 ℃, and the temperature is kept for 2-6 h, so that the cis-caronic acid or the derivative thereof and the trans-caronic acid or the derivative thereof are sequentially cyclized, and the caronic anhydride or the derivative thereof is obtained.
Optionally, in the step of performing the cyclization reaction on the caronic acid or the derivative thereof, the dehydrating agent is at least one selected from acetic anhydride, sodium acetate, maleic anhydride and phthalic anhydride, and the molar ratio of the dehydrating agent to the 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid or the derivative thereof is 2:1-4:1.
In the present invention, the specific reaction equations of step S21 and step S22 are as follows:
。
it will be appreciated that in the caronic acid or its derivative represented by formula (2) and the caronic anhydride or its derivative represented by formula (3), R 1 And R is 2 The selection of (2) depends on the 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid or its derivative represented by formula (1), and all three are the same.
Optionally, after the cyclization reaction is finished, the reaction solution is subjected to vacuum rectification to obtain the caronic anhydride or the derivative thereof shown in the formula (3).
Hereinafter, the preparation methods of the caronic acid or its derivatives and the caronic anhydride or its derivatives will be further described by the following specific examples.
In the following carbon nanotubes loaded with nitroxide compounds, the structural formulas of the nitroxide compounds are shown as NO-1 to NO-10.
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The preparation method of CNTs-1 comprises the following steps:
10g of carbon nanotubes and 150mL of 60% HNO 3 After mixing, stirring for 10 hours at 75 ℃, filtering, washing a filter cake with deionized water, and drying for 5 hours at 120 ℃ to obtain the carboxylated carbon nano tube CCNTs-1.
Suspending the carboxylated carbon nano tube CCNTs-1 in 60mL of toluene, adding 1.68g of nitrogen-oxygen free radical compound NO-1 and 1.0mL of 96% concentrated sulfuric acid, heating and stirring for 10h at 80 ℃, filtering, washing a filter cake with ethanol and deionized water, and drying for 5h at 120 ℃ to obtain the carbon nano tube CNTs-1 loaded with the nitrogen-oxygen free radical compound.
The preparation method of CNTs-2 comprises the following steps:
10g of carbon nanotubes and 150mL of 60% HNO 3 After mixing, stirring for 10 hours at 75 ℃, filtering, washing a filter cake with deionized water, and drying for 5 hours at 120 ℃ to obtain the carboxylated carbon nano tube CCNTs-2.
Suspending the carboxylated carbon nano tube CCNTs-2 in 50mL of thionyl chloride, refluxing for 4h, filtering, washing and drying to obtain the carbon nano tube CONTs-2, suspending the carbon nano tube CONTS-2 in 60mL of toluene solution, adding 1.29g of nitrogen-oxygen free radical compound NO-2 and 1.0mL of 96% concentrated sulfuric acid, heating and stirring for 10h at 80 ℃, filtering, washing a filter cake with ethanol and deionized water, and drying for 5h at 120 ℃ to obtain the carbon nano tube CNTs-2 loaded with the nitrogen-oxygen free radical compound.
The preparation methods of carbon nanotubes CNTs-3 to CNTs-10 loaded with nitroxide free radical compounds are the same as above, except that the reaction control parameters are different, and specific reaction parameters and reaction results are shown in Table 1.
TABLE 1
Examples
3.03g (0.0075 mol) of Fe (NO) 3 ) 3 ·9H 2 O, 1.12g (0.015 mol) of KCl and 10.80g of CNTs-1 (containing 0.0075mol of nitroxide free radical compound) in Table 1 are suspended in 150mL of methylene chloride solution, then added into a 250mL tetrafluoropolyethylene autoclave, then 21.63g (0.15 mol) of 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid is added, inert gas with 20% oxygen content is introduced to maintain the pressure in the autoclave at 1.2MPa, the temperature is kept at 40 ℃ for reaction for 3 hours, the temperature is continuously raised to 80 ℃, the reaction solution is taken out after the temperature is kept for 4 hours, 10.72g of CNTs-1 is obtained by filtration, and the recovery rate is 99.3%. The filtrate was then quenched with aqueous sodium sulfite, pH adjusted to 2 with dilute hydrochloric acid and extracted with ethyl acetate to give a solution containing caronic acid.
Adding acetic anhydride of 50mL into the solution containing the caronic acid, carrying out heat preservation and reflux reaction for 3 hours at 120 ℃, continuously heating to 160 ℃, and carrying out heat preservation and reflux reaction for 4 hours. Subsequent distillation under reduced pressure gave Carbonic anhydride 18.46. 18.46 g in 87.83% yield.
Examples
Examples 2 to 10 differ from example 1 in the reaction control parameters, the specific reaction materials are shown in Table 2, and the reaction parameters and results are shown in Table 3.
TABLE 2
TABLE 3 Table 3
Cyclic application test of carbon nanotubes loaded with nitroxide compounds:
the CNTs-1 filtered in example 1 were subjected to a mechanical experiment for preparing Carlong anhydride, and the data are shown in Table 4 below, and the procedure for specifically preparing Carlong anhydride was the same as in example 1.
TABLE 4 Table 4
As shown in Table 4, the carbon nanotubes loaded with the nitroxide free radical compound can be repeatedly used for a plurality of times, the recovery rate is still more than 95% after 20 times of application, and the reaction activity is not obviously reduced.
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 invention, which are described in detail and are not to be construed as limiting the scope of the invention. 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 invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. A method for preparing caronic acid, comprising the steps of:
mixing 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid with a catalytic system in an organic solvent to obtain a reaction system, wherein the catalytic system comprises transition metal nitrate, inorganic halide and carbon nano tubes loaded with nitrogen-oxygen free radical compounds, the transition metal of the transition metal nitrate is selected from at least one of iron, copper, chromium, manganese, cobalt and palladium, the inorganic halide is selected from at least one of sodium halide and potassium halide, and the carbon nano tubes loaded with nitrogen-oxygen free radical compounds have the structural formula selected from at least one of NO-1 to NO-10;
under the aerobic condition, carrying out oxidation reaction on the reaction system to obtain a reaction solution; and
filtering the reaction liquid, and performing post-treatment on the filtrate to obtain caronic acid;
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2. the method for producing a caronic acid according to claim 1, wherein the molar ratio of the 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid, the transition metal nitrate, the inorganic halide, and the nitroxide compound in the nitroxide compound-supported carbon nanotube in the reaction system is 1:0.01 to 0.1:0.01 to 0.1.
3. The method for preparing the caronic acid according to claim 1, wherein the construction method of the aerobic condition is as follows: introducing gas with the oxygen content of 5-100%, and maintaining the pressure at 0.1-6 MPa.
4. The method for preparing caronic acid according to claim 1, wherein in the step of oxidizing the reaction system, a gradient heating method is adopted, the temperature is firstly raised to 20 ℃ to 60 ℃, the temperature is kept for 2h to 6h, and then the temperature is raised to 50 ℃ to 100 ℃, and the temperature is kept for 2h to 6h.
5. The method for preparing caronic acid according to claim 1, wherein in the post-treatment step, the filtrate is quenched with a quencher, then the pH is adjusted to 1-4, and then extraction is performed with an organic solvent.
6. The method for producing a caronic acid according to claim 1, wherein in the step of filtering the reaction solution, carbon nanotubes carrying the nitroxide compound are recovered, and the recovered carbon nanotubes carrying the nitroxide compound are recycled to the catalytic system.
7. A method for preparing caronic anhydride, comprising the steps of:
a caronic acid obtained by the preparation process according to any one of claims 1 to 6; and
and carrying out cyclization reaction on the caronic acid to obtain caronic anhydride, wherein the caronic acid is subjected to cyclization reaction, and the method further comprises a dehydrating agent, wherein the dehydrating agent is at least one selected from acetic anhydride, sodium acetate, maleic anhydride and phthalic anhydride.
8. The method for preparing caronic anhydride according to claim 7, wherein in the step of cyclizing the caronic acid, a gradient heating method is adopted, the temperature is firstly raised to 120-160 ℃, the temperature is kept for 2-6 h, and then the temperature is raised to 150-200 ℃ and the temperature is kept for 2-6 h.
9. The method for preparing caron anhydride according to claim 7, wherein the molar ratio of the dehydrating agent to the 3-hydroxymethyl-2, 2-dimethylcyclopropanecarboxylic acid is 2:1-4:1.
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