KR102397424B1 - Dicarboxyl acid aromatic heterocyclic compound and method for preparing thereof - Google Patents

Abstract

The present invention relates to a method for preparing an aromatic dicarboxylic acid heterocyclic compound and a dicarboxylic acid aromatic heterocyclic composition obtained therefrom. According to the present invention, a bio-based hydroxyl-free aromatic heterocyclic compound is oxidized under a heterogeneous catalyst. This has the effect of preparing an oxide with improved yield and purity.

Description

Dicarboxylic acid aromatic heterocyclic compound and preparation method {Dicarboxyl acid aromatic heterocyclic compound and method for preparing thereof}

The present invention relates to a preparation method using a hydroxyl-free aromatic heterocyclic compound as a raw material for preparing an aromatic heterocyclic dicarboxylic acid compound, and to a dicarboxylic acid aromatic heterocyclic composition obtained therefrom.

In order to reduce greenhouse gases, developed countries such as the United States and Europe are strengthening carbon dioxide emission regulations. Accordingly, the demand for biochemical industries that can reduce dependence on existing fossil raw material resources and reduce greenhouse gases is increasing. In other words, the chemical industry is changing from oil-dependent to bio-dependent.

For example, a technology for replacing polyethylene terephthalate (PET), which is mainly used for beverage bottles or food storage containers, with bio-PET (bio-PET) is being actively studied.

A dicarboxylic acid aromatic heterocyclic compound useful as a monomer in the preparation of bio-PET is a derivative prepared by oxidizing 5-hydroxymethylfurfural. Since the 5-hydroxymethylfurfural (HMF) is obtained from sugar, it is a derivative of a widely available raw material in nature.

For reference, the oxidation reaction for 5-HMF is 2,5-furandianion crosslinking agent (FDCA), 2,4-furandianion crosslinking agent and 2-carboxy-5-formylfuran (FFCA), as shown in the following reaction scheme. An aromatic heterocyclic compound of monocarboxylic acid or dicarboxylic acid comprising can be obtained as the main product.

A process for oxidation of HMF in which the aromatic heterocyclic compound of monocarboxylic acid or dicarboxylic acid can be obtained as a main product is known in the literature. For example, US 4,977,283 to Hoechst describes a process for the oxidation of HMF carried out by means of a metal catalyst belonging to the platinum group in an aqueous environment of pH 6.5 to 8. This patent discloses that the ratio between various oxidation products and by-products can be controlled by adjusting the pH. According to the information contained in this patent, the adjustment of the pH can be achieved by maintaining the pH usually below 8 via a base, acid or buffer solution, such as a base such as sodium or potassium hydroxide.

In addition, the patent application US 2008/0103318 ( Battelle ) describes a method for the oxidation of HMF catalyzed by platinum supported on a support.

However, the oxidation methods of HMF as described above have a high manufacturing cost and are performed as a batch reaction. It requires an irrelevant time, and there is a problem in that the productivity of the reactor is lowered. In addition, in order to use the catalyst repeatedly, a process of separating the catalyst and the product is required, and there is a problem in that the catalyst's early activity decreases due to a change in temperature, etc.

US Patent No. 4,977,283

One aspect of the present invention is a method for producing an eco-friendly and improved dicarboxylic acid aromatic heterocyclic compound using a bio-based novel hydroxyl-free aromatic heterocyclic compound used for synthesizing dicarboxylic acid aromatic heterocyclic compound as a raw material is intended to provide

Another object of the present invention is to provide a dicarboxylic acid aromatic heterocyclic compound, or a crude dicarboxylic acid aromatic heterocyclic composition comprising the same, which can be mass-produced by a continuous process and has greatly improved production efficiency.

According to one embodiment of the present invention,

A method for producing an aromatic heterocyclic compound of dicarboxylic acid by oxidizing a raw material of an aromatic heterocyclic compound in a polar solvent in the presence of a heterogeneous catalyst, the method comprising:

The raw material for the aromatic heterocyclic compound provides a method for preparing a dicarboxylic acid aromatic heterocyclic compound, which is a hydroxyl-free compound having a structure represented by the following Chemical Formula 1:

[Formula 1]

(Wherein, any one of R1 and R2 is an aldehyde, the rest are substituted or unsubstituted (C1-C20)alkyl, acetoxy or aldehyde, and the substituted (C1-C20)alkyl is bromine, chlorine, It may be substituted with one or more functional groups selected from the group consisting of fluorine and iodine.)

In addition, the hydroxyl-free aromatic heterocyclic compound may have one or more structures selected from the following Chemical Formulas 2 to 4:

[Formula 2]

[Formula 3]

[Formula 4]

In addition, the aromatic heterocyclic compound having a structure represented by Formula 1 may be used in a modified state into a structure represented by Formula 3 or a structure represented by Formula 4 below:

[Formula 3]

[Formula 4]

In this case, the oxidation reaction is

A catalyst for producing an aromatic heterocyclic compound having a structure represented by the following formula (3) by subjecting an aromatic heterocyclic compound raw material having a structure represented by the following formula (2) to an oxidation reaction at a fourth temperature in a polar solvent in the presence of an onium-based compound and an ion activator pre-oxidation step; and

Oxidation to produce a dicarboxylic acid aromatic heterocyclic compound by oxidizing an aromatic heterocyclic compound having a structure represented by Formula 3 in a polar solvent (H2O) in the presence of a basic material and a heterogeneous catalyst at a fifth temperature higher than the fourth temperature step; may include.

[Formula 2]

[Formula 3]

The fourth temperature may be 10 °C to 80 °C.

The catalyst-free oxidation step may be performed for 1 hr to 10 hr.

The fifth temperature may be 100 °C to 200 °C.

The oxidation step may be performed for 3 hr to 24 hr.

In addition, the oxidation reaction is

a primary catalyst pre-oxidation step of oxidizing a raw material for an aromatic heterocyclic compound having a structure represented by the following Chemical Formula 2 in a polar solvent at a sixth temperature;

a secondary catalyst pre-oxidation step of substituting the polar solvent with another type of polar solvent and performing an oxidation reaction at a seventh temperature lower than the sixth temperature to produce an aromatic heterocyclic compound having a structure represented by the following Chemical Formula 4; and

an oxidation step of oxidizing an aromatic heterocyclic compound having a structure represented by Chemical Formula 4 in a polar solvent at an eighth temperature lower than the sixth temperature in the presence of a heterogeneous catalyst to produce a dicarboxylic acid aromatic heterocyclic compound; may include

[Formula 2]

[Formula 4]

The sixth temperature may be 100 °C to 200 °C.

The first catalyst-free oxidation step may be performed for 8 hr to 24 hr.

The seventh temperature may be 10 °C to 80 °C.

The second catalyst pre-oxidation step may be performed for 15 hr to 32 hr.

The eighth temperature may be 10 °C to 80 °C.

The oxidation step may be performed for 1 hr to 10 hr.

In addition, the onium-based compound is a compound composed of a tetraalkylammonium cation having an alkyl group having 4 to 10 carbon atoms and an anion having a pKa value of 3 or less, based on 1 mole of the aromatic heterocyclic compound represented by Formula 2, in a molar ratio of 0.4 to 1.0. can

In addition, the polar solvent is at least one selected from acetonitrile, acetone, dimethylformamide, dimethyl sulfoxide, water, ethanol, methanol, and t-butyl hypochlorite (t-BuOCl), an aromatic hetero It can be used in an amount of 2 to 5 moles based on 1 mole of the ring compound.

The ion activator may use at least one selected from NaOAC and KOAc in an amount of 1 to 10 moles based on 1 mole of the aromatic heterocyclic compound represented by Formula 2 above.

The basic compound is one or more selected from sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, and dibasic and tribasic phosphate buffers, the pH of the reaction solution exceeds 7 It may be continuously added to the reaction solution in a range maintained at 11 or less, or may be added intermittently before, during, or after the reaction.

According to another embodiment of the present invention,

As a dicarboxylic acid aromatic composition prepared by using an aromatic heterocyclic compound as a raw material,

It provides a dicarboxylic acid aromatic heterocyclic composition, which is a crude oxide comprising a dicarboxylic acid aromatic heterocyclic compound having a structure represented by the following formula (5):

[Formula 5]

In addition, the dicarboxylic acid aromatic heterocyclic composition is an aromatic heterocyclic compound having a structure represented by the following formula (2), an aromatic heterocyclic compound having a structure represented by the following formula (3), an aromatic heterocyclic compound having a structure represented by the following formula (4), At least one selected from an aromatic heterocyclic compound (FFCA) having a structure represented by the following Chemical Formula 6 and an aromatic heterocyclic compound having a structure represented by the following Chemical Formula 7 may be further included.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 6]

[Formula 7]

The new bio-based raw material according to one aspect of the present invention is not only environmentally friendly in that it is a material converted from wood, but also has an effect suitable for use in the oxidation reaction of an aromatic heterocyclic compound by replacing the conventionally used 5-HMF.

The dicarboxylic acid aromatic heterocyclic compound according to another aspect of the present invention can be provided in a high yield of 95% or more in the crude composition by continuing the synthesis reaction of the raw material.

Furthermore, the method for producing an aromatic heterocyclic dicarboxylic acid according to another aspect of the present invention is to continuously synthesize a product with a high yield, thereby eliminating the disadvantages of the conventional method for batch synthesizing 5-HMF as a raw material. There is an effect that can be carried out by improving energy efficiency and productivity without a pressure control process in the reactor.

Hereinafter, a method for producing a dicarboxylic acid aromatic heterocyclic compound using the aromatic heterocyclic compound of the present invention as a raw material and a heterogeneous catalyst used therein will be described in detail.

Throughout the specification, when a part "includes" a certain element, it means that other elements may be further included, rather than excluding other elements, unless otherwise stated.

In the present invention, "metal precursor" is a concept that refers to a chemical substance prepared in advance to react a metal. For example, the term “transition metal precursor” is a concept that refers to a chemical substance prepared in advance to react a transition metal.

<First aspect of the present invention>

A first aspect of the present invention is a hydroxyl-free aromatic heterocyclic compound comprising an aromatic heterocyclic ring and a hydroxyl-free terminal as a raw material for producing a dicarboxylic acid aromatic heterocyclic compound.

In the present invention, the hydroxyl-free aromatic heterocyclic compound may have a structure represented by the following Chemical Formula 1:

[Formula 1]

(Wherein, any one of R1 and R2 is an aldehyde, the rest are substituted or unsubstituted (C1-C20)alkyl, acetoxy or aldehyde, and the substituted (C1-C20)alkyl is bromine, chlorine, It may be substituted with one or more functional groups selected from the group consisting of fluorine and iodine.)

The compound of Formula 1 is a compound converted from wood, and is a compound used for the first time in preparing an aromatic heterocyclic dicarboxylic acid compound. Unless otherwise specified herein, halogen refers to chlorine, bromine, fluoro, iodine.

In the present invention, the term "aromatic heterocyclic ring" refers to a structure that provides a skeleton when preparing a dicarboxylic acid aromatic heterocyclic compound.

For example, at least one selected from the group consisting of furan, thiophene and pyrrole may be used as the aromatic heterocycle.

In addition, the hydroxyl-free terminal may be at least one selected from the group consisting of an aldehyde group, an acetoxy group, and an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group may be unsubstituted or halogen-substituted.

In Formula 1, when R1 is an aldehyde, R2 is selected from hydrogen, aldehyde, acetoxy, halogen, C1-C20 alkyl, C1-C20 alkoxy, wherein C1-C20 alkyl or C1-C20 alkoxy is unsubstituted or one type It may be one substituted with more than one halogen atom.

In addition, in Formula 1, when R1 is an aldehyde, R2 is selected from acetoxy or C1-C20 alkyl, wherein C1-C20 alkyl may be substituted with one or more halogen atoms.

In this case, the hydroxyl-free aromatic heterocyclic compound may have one or more structures selected from the following Chemical Formulas 2 to 4.

[Formula 2]

[Formula 3]

[Formula 4]

<Second aspect of the present invention>

A second aspect of the present invention is a heterogeneous catalyst having a structure in which a cation of a metal catalyst component is bonded to a porous central metal-organic framework material as a catalyst for preparing an aromatic heterocyclic dicarboxylic acid compound. In the present invention, the porous central metal-organic framework refers to a porous organic-inorganic compound formed by binding of a central metal ion with an organic ligand, and includes organic and inorganic materials in or on the surface of the framework and has molecular or nano-sized pore structures. It may include a crystalline compound having

In addition, in the present invention, the metal catalyst component has an activity that contributes to the improvement of product yield by using the raw material of the first aspect when preparing the dicarboxylic acid aromatic heterocyclic compound, and is a component inserted into the pore structure of the framework material. refers to

As the metal catalyst, at least one selected from Fe, Ni, Ru, Rh, Pd, Os, Ir, Au and Pt, which may have various oxidation numbers, may be used, and in particular, Ru, Pd, Pt, and Au may be preferably used. can

In addition, the central metal may be selected from among skeletal support materials such as Mg and Al, active metals such as Mn and Co, and activation promoting metals such as Ce, depending on the activity of the reaction target.

For example, two types of active metals, Mn and Co, can be selected and used as the central metal, or the activation-promoting metal of Ce, which is known to have excellent storage and transfer ability for reactive oxygen species, is used alone. It can be used as a central metal.

As a specific example, the central metal framework material used in the present invention may include a structure represented by the following Chemical Formula 9.

[Formula 8]

(Mn) _a -(Co) _b -(Ce) _c -O _d

(In the above formula, a, b and c represent oxidation numbers, the sum of a, b and c is 1 or more, the sum of a and c is greater than 0, and d is an integer greater than 1 than a+b+c. am)

The central metal framework material having such a structure has a binding site of the pore structure, and when a metal catalyst component containing an element capable of binding to the binding site of the pore structure is bound, a functionalized heterogeneous catalyst can be provided.

In this case, the organic framework material may be provided using an anionic crosslinking agent. In the present invention, the anionic crosslinking agent provides an anion to serve as a crosslinking agent between the porous central metal and the subsequently bonded metal catalyst component, thereby providing a form in which the cation of the metal catalyst component is strongly adsorbed on the particles of the porous central metal. refers to

In the case of an aliphatic material without a ring structure, the anionic crosslinking agent volatilizes before the particles are agglomerated and creates pores. Since it acts as a pore-inducing material, there is no need for a separate surfactant. to provide a ligand that induces subsequent adsorption binding.

The anionic crosslinking agent may be a material that provides at least one polyvalent anion selected from the group consisting of citric acid, tartaric acid, malic acid, malonic acid and tartaric acid.

In the present invention, the heterogeneous catalyst may use the aforementioned porous metal as a carrier, or a material known in the art such as carbon may be used.

In this case, the shape of the carrier may vary. It is not limited to a spherical shape with micropores, a cylindrical columnar shape, and the like.

As the catalyst, Ru-MnCo ₂ O ₄ , Au-CeO ₂ and the like may be used, and Pt/C, Pd/C, Rh/C, etc. known as heterogeneous catalysts in the art may be used in combination or by replacing them.

The amount of the catalyst used is not particularly limited, but for example, with respect to 1 mole of the raw aromatic heterocyclic compound having the structure represented by Formula 1, a molar ratio of 600 moles or less based on the central metal and the metal catalyst component in the catalyst, or 50 to 600 moles molar ratio.

The heterogeneous catalyst according to the present invention overcomes the disadvantage that it is not easy to separate because it is melted in the reaction solution when using a homogeneous catalyst, and provides the advantage of being able to be recycled multiple times after separation, and it increases the yield when preparing the dicarboxylic acid aromatic heterocyclic compound. .

The catalyst may be circulated at least once in an oxidation reaction to be described later, in a specific example 4 times or more.

In addition, the heterogeneous catalyst may be to produce a dicarboxylic acid aromatic heterocyclic compound by oxidizing an aromatic heterocyclic raw material having a structure represented by the following formula (1):

[Formula 1]

(Wherein, any one of R1 and R2 is an aldehyde and the rest is a substituted or unsubstituted (C1-C20)alkyl, acetoxy or aldehyde, and the substituted (C1-C20)alkyl is bromine, chlorine, fluorine and It may be substituted with one or more functional groups selected from the group consisting of iodine.)

In addition, the heterogeneous catalyst is an oxidation reaction of at least one compound selected from a compound having a structure represented by the following Chemical Formula 2, a compound having a structure represented by Chemical Formula 3, and a compound having a structure represented by Chemical Formula 4 in a polar solvent to the following Chemical Formula 5 It is possible to produce oxides having the structure represented by:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In addition, the dicarboxylic acid aromatic heterocyclic compound may have a structure represented by the following formula (5):

[Formula 5]

In addition, the heterogeneous catalyst is Ru/MnCo ₂ O ₄ , Au/CeO ₂ , Ru/C, Pt/C 0.4 to 1.0 mole based on 1 mole of an aromatic heterocyclic compound having a structure represented by Formula 1 at least one selected from the group consisting of It may be used as rain.

<Third aspect of the present invention>

A third aspect of the present invention is a method for preparing the aforementioned heterogeneous catalyst.

The heterogeneous catalyst is first prepared as a porous central metal-organic framework by reacting a solution containing a porous central metal oxide with an anionic crosslinking agent. Then, the porous central metal-organic framework material is impregnated with the metal catalyst component precursor and then pyrolyzed to prepare it. Specifically, the manufacturing method includes a first step, a second step and a third step. The name of each stage is a name given to distinguish each stage from other stages, and does not include all technical meanings of each stage.

The first step is a step of preparing a solution containing the porous central metal oxide (hereinafter also referred to as a porous central metal precursor).

The porous central metal oxide is, for example, when the transition metal is manganese, dimethyl manganese, diethyl manganese, manganese acetate, manganese acetate dihydrate, manganese acetylacetonate, manganese acetylacetonate hydrate, manganese iodide, manganese bromide, Manganese chloride, manganese fluoride, manganese fluoride tetrahydrate, manganese carbonate, manganese cyanide, manganese nitrate, manganese nitrate hexahydrate, manganese oxide, manganese peroxide, manganese perchlorate, manganese perchlorate hexahydrate, manganese sulfate, diphenyl It may be at least one selected from the group consisting of manganese, manganese naphthalate, manganese oleate and manganese stearate.

Accordingly, the same can be applied to the case where the porous central metal is not manganese.

The aforementioned porous central metal may be provided in a form having a molecular or nano-sized pore structure to provide a support, that is, a carrier.

The porous central metal may be at least one selected from the group consisting of Mn, Co, Mg and Ce.

The second step is a step of preparing a porous central metal-organic framework material by reacting the porous central metal oxide solution of the first step with an anionic crosslinking agent.

The anion crosslinking agent provides an anion to serve as a crosslinking agent between the porous central metal and the metal catalyst component to be subsequently bonded, thereby providing a form in which the cation of the metal catalyst component is adsorbed on the particles of the porous central metal, citric acid, Tartaric acid, malic acid, malonic acid, tartaric acid and the like can be used.

Specifically, the second step includes step 2-1, step 2-2, and step 2-3.

Step 2-1 is a step of mixing the porous central metal oxide solution and the anionic crosslinking agent. The porous central metal oxide may be used in the form of a solution using water, alcohol, and a mixture thereof.

In addition, the porous central metal oxide and the anion crosslinking agent may be mixed in a molar ratio of 1:1 to 1:5, for example, to prepare a mixed solution.

Step 2-2 is a step of first reacting the mixed solution after raising the temperature of the mixed solution after step 2-1 to a first temperature. The range of the first temperature may be, for example, in the range of 40°C to 200°C, and most preferably in the range of 100°C to 180°C. At this time, the pressure is maintained as it is.

Step 2-3 is a step of raising the temperature of the mixed solution after step 2-2 to a second temperature higher than the first temperature, followed by a secondary reaction of the mixed solution. The range of the second temperature may be in the range of 400 °C to 1000 °C, and it is preferable that the temperature is higher than the first temperature. At this time, the pressure is maintained as it is. In addition, the reaction time at this time is, for example, 2 to 24 hours, preferably 3 to 12 hours is preferable.

In the third step, the porous central metal-organic framework material prepared after the second step (specifically, the second step 2-3) is impregnated with the precursor solution of the metal catalyst component to obtain a structure in which the cation of the metal catalyst component is bonded. step to provide.

Specifically, the third step includes steps 3-1 and 3-2.

The step 3-1 is a step of impregnating the reactant after the second step (specifically, the second step 2-3) in a solution of the precursor of the metal catalyst component obtained by dissolving the precursor of the metal catalyst component in a solvent. Step 3-1 may be performed within a range of 40° C. to 80° C., and the pressure may be maintained at normal pressure.

Step 3-2 is a step of sintering the impregnated material after step 3-1 at a third temperature lower than the second temperature. The range of the third temperature may be in the range of 40 to 800°C, or 100 to 600°C, and preferably a temperature higher than the first temperature. At this time, the pressure is maintained as it is.

The solvent used to prepare the porous central metal oxide solution of step 2-1 and the precursor solution of the metal catalyst component of step 3-1 is to control the concentration of the mixed solution, and water, alcohol, and a combination thereof this can be used

<Fourth aspect of the present invention>

In the method for producing an aromatic dicarboxylic acid compound, the aforementioned raw material of the aromatic heterocyclic compound is subjected to an oxidation reaction in a polar solvent in the presence of a heterogeneous catalyst to prepare a dicarboxylic acid aromatic heterocyclic compound. Since the raw material has been described in detail in the first aspect, a detailed description of the repeated description will be omitted.

As described above, the raw material of the present invention may be an aromatic heterocyclic compound having a structure represented by Chemical Formula 1, for example, an aromatic heterocyclic compound having a structure represented by Chemical Formula 2.

The aromatic heterocyclic compound having the structure represented by the formula (2) may be used in a modified state into the structure represented by the following formula (3) or the structure represented by the following formula (4).

[Formula 3]

[Formula 4]

In order to increase the reaction efficiency in the oxidation reaction, the conversion rate should be maximized and the molar ratio of the two reacting functional groups should be close to 1:1. Maximizing conversion can be achieved by lengthening the reaction time or increasing the reaction temperature, but it is not easy to control the moles of the two reacting groups to be 1:1, and this is often the case in oxidation reactions with certain dicarboxylic acids. It acts as a limiting factor in producing an aromatic compound (eg, a dicarboxylic acid aromatic compound represented by Chemical Formula 5) in high yield. For this reason, when preparing a dicarboxylic acid aromatic compound having a structure represented by Chemical Formula 5, a high yield of dicarbonate can be obtained in two steps as follows, rather than preparing by oxidation by adding a dicarboxylic acid heteroaromatic compound having a structure represented by Chemical Formula 2 It is preferred to prepare a levonic acid aromatic compound. That is, first, a catalyst-free oxidation reaction is performed prior to the catalytic oxidation reaction to obtain a compound in which one terminal is oxidized, and in step 2, the other terminal is oxidized by oxidation under a catalyst.

As a specific example, the oxidation reaction according to the present invention may be represented by the following two cases depending on the reformed structure.

For example, when the oxidation reaction includes a catalyst-free oxidation step and an oxidation step, the name of each step is a name given to distinguish each step from other steps, and does not include all technical meanings of each step.

The catalyst-free oxidation step is a step of generating an aromatic heterocyclic compound having a structure represented by the following Chemical Formula 3.

[Formula 3]

The aromatic heterocyclic compound having the corresponding structure is prepared by oxidizing a raw material for an aromatic heterocyclic compound having a structure represented by the following Chemical Formula 2 in a polar solvent in the presence of an onium-based compound and an ion activator at a fourth temperature. The fourth temperature may be 10 °C to 80 °C, or 30 °C to 50 °C. The pressure may be normal pressure, and the reaction may be performed for 1 hr to 10 hr, or 2 hr to 6 hr.

[Formula 2]

The onium-based compound used in the present invention is a compound composed of an onium-based cation and an anion having a pKa value of 3 or less. (or aryl) phosphonium cations;

There are many anions with a pKa value of 3 or less, but among them, halide anions are preferable because they are easily formed by a neutralization reaction with onium-based cations.

The onium-based compound is, for example, in tetrabutylammonium chloride (TBAC), tetrahexylammonium chloride (THAC), tetraoctylammonium chloride (TOAC), tetrabutylammonium bromide (TBAB) and tetrabutylammonium iodide (TBAI). It may be at least one selected species.

The onium-based compound used in the present invention may be used in a molar ratio of 0.4 to 1.0 based on 1 mole of the aromatic heterocyclic compound represented by Formula 2 above.

In addition, the ion activator may be, for example, at least one selected from NaOAC and KOAc, and may be used in an amount of 1 to 5 moles based on 1 mole of the aromatic heterocyclic compound represented by Formula 2 above.

In addition, the polar solvent may be, for example, at least one selected from acetonitrile, acetone, dimethylformamide, dimethyl sulfoxide, water, ethanol, methanol, and t-butyl hypochlorite (t-BuOCl), and represented by Formula 2 It can be used in an amount of 1 to 5 moles based on 1 mole of the aromatic heterocyclic compound.

The oxidation step is a step of generating a desired dicarboxylic acid aromatic heterocyclic compound from an aromatic heterocyclic compound having a structure represented by Chemical Formula 3.

The target compound is prepared by oxidation reaction at a fifth temperature higher than the fourth temperature in a polar solvent in the presence of a basic material and a heterogeneous catalyst. The fifth temperature may be 80 ℃ to 200 ℃, it is preferable to carry out in a temperature range higher than the fourth temperature. The pressure may be atmospheric conditions, and the reaction may be performed for 2 to 10 hours.

The basic compound used in the present invention, for example, may be selected from salts of sodium, lithium, calcium, magnesium or ammonium substituted with 1 to 4 alkyl groups having 1 to 15 carbon atoms, monoethanolamine, diethanol You can also choose from amines, triethanolamines, aminoethyl propanediol, methyl glucamine, and mixtures thereof.

As a specific example, as the basic compound, at least one selected from sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, and dibasic and tribasic phosphate buffer solutions may be used. can

As a weak base, the basic compound may be in a range to maintain the pH of the reaction solution at more than 7 and below 11, and as a specific example, it may be added continuously to the reaction solution or intermittently added before, during, or after the reaction.

The heterogeneous catalyst is, for example, Ru-MnCo ₂ O ₄ , Au-CeO ₂ and at least one of Pt/C can be used, and considering the product production efficiency and the aspect that can be recycled at least once, or at least 4 times, Ru- Preference is given to using MnCo ₂ O ₄ .

In this case, a known polar solvent may be used as the polar solvent, and for example, dimethyl sulfoxide, ethanol, acetonitrile, or the like may be used. The polar solvent may be used in an amount ranging from 10 to 100 wt% based on the weight of the aromatic heterocyclic compound having the structure represented by Chemical Formula 3, but is not limited thereto.

As another example, when the oxidation reaction includes a first catalyst-free oxidation step, a second catalyst-free oxidation step, and an oxidation step, the name of each step is a name given to distinguish each step from other steps, and is a technical description of each step. Not all meanings are included.

The first catalyst pre-oxidation step is a step of partially generating an aromatic heterocyclic compound having a structure represented by the following Chemical Formula 4.

[Formula 4]

The aromatic heterocyclic compound having the corresponding structure is prepared by oxidizing a raw material of the aromatic heterocyclic compound having the structure represented by the following Chemical Formula 2 in a polar solvent at a sixth temperature. The sixth temperature may be 100 °C to 200 °C. The pressure may be normal pressure, and the reaction may be performed for 8 hr to 24 hr.

In this case, a known polar solvent may be used as the polar solvent, and for example, dimethyl sulfoxide, ethanol, acetonitrile, or the like may be used. The polar solvent may be used in an amount ranging from 10 to 100 wt% based on the weight of the aromatic heterocyclic compound having the structure represented by Chemical Formula 2, but is not limited thereto.

The secondary catalyst pre-oxidation step is a step of maximally producing an aromatic heterocyclic compound having a structure represented by Formula (4).

The aromatic heterocyclic compound having the corresponding structure is prepared by substituting a different type of polar solvent for the polar solvent used in the first catalyst pre-oxidation step and further oxidizing it at a 7th temperature lower than the 6th temperature.

In this case, the polar solvent to be substituted may use a known polar solvent, for example, t-BuOCl having improved solubility than the solvent before substitution may be used. The polar solvent may be used in an amount ranging from 10 to 100 wt% based on the weight of the aromatic heterocyclic compound having the structure represented by Chemical Formula 2, but is not limited thereto.

The seventh temperature may be in the range of 10°C to 80°C, and it is preferable that the temperature is lowered than the sixth temperature. At this time, the pressure may be normal pressure, and the reaction may be performed for 1 hr to 10 hr.

The oxidation step is a step of producing a desired dicarboxylic acid aromatic heterocyclic compound from the aromatic heterocyclic compound having the structure shown.

The desired compound is prepared by oxidation reaction in a polar solvent at an eighth temperature between the sixth and seventh temperatures in the presence of a heterogeneous catalyst. The eighth temperature may be in the range of 10°C to 80°C, and it is preferable that the temperature is lowered than the sixth temperature. At this time, the pressure may be normal pressure, and the reaction may be performed for 2 to 15 hours.

The heterogeneous catalyst is, for example, Ru-MnCo ₂ O ₄ , Au-CeO ₂ , Ru/C and at least one of Pt/C can be used, and the product production efficiency and the aspect that can be recycled at least once, or at least 4 times In consideration, it is preferable to use Ru-MnCo ₂ O ₄ or Au-CeO ₂ .

In this case, the polar solvent used may be a known polar solvent, for example, ethanol may be used. The polar solvent may be used in an amount ranging from 10 to 100 wt% based on the weight of the aromatic heterocyclic compound having the structure represented by Chemical Formula 4, but is not limited thereto.

<The fifth aspect of the present invention>

A fifth aspect of the present invention is a crude composition prepared using the aromatic heterocyclic compound raw material according to the first aspect and the heterogeneous catalyst according to the second aspect.

The composition of the fifth aspect includes a dicarboxylic acid aromatic heterocyclic compound.

The target compound as the dicarboxylic acid aromatic heterocyclic compound is a compound having a structure represented by the following formula (5).

[Formula 5]

In this case, the composition is inevitably a raw material (corresponding to an aromatic heterocyclic compound having a structure represented by Formula 2), a modifying material (an aromatic heterocyclic compound having a structure represented by Formula 3, or an aromatic heterocyclic compound having a structure represented by Formula 4) , an additional oxide (aromatic heterocyclic compound (FFCA) having a structure represented by the following formula (6) or an aromatic heterocyclic compound having a structure represented by the following formula (7)) may be included.

[Formula 6]

[Formula 7]

For reference, the reaction targeted by the present invention is an oxidation reaction in the presence of a heterogeneous catalyst using the above-mentioned raw materials, specifically, an aromatic heterocyclic compound represented by the following formula (1) with an oxidizing agent (oxygen gas, etc.) in the presence of a heterogeneous catalyst It is a reaction that oxidizes unsaturated groups included in the backbone by contacting them.

As the oxide of the aromatic heterocyclic compound obtained in these reactions (hereinafter referred to as the dicarboxylic acid aromatic heterocyclic compound or the reaction product), the unsaturated group contained in the backbone is oxidized, and as shown in the following reaction formula, a 2,5-furandianion crosslinking agent (FDCA) ), a 2,4-furandionic anion crosslinking agent, 2-carboxy-5-formyl furan (corresponding to FFCA) or levulinic acid.

Since these products generally have a higher melting point than the raw aromatic heterocyclic compound, they are difficult to take out from the reactor in a molten state, and thus require post-treatment such as purification or crystallization. For example, the melting point of 5-chloromethylfurfural as an aromatic heterocyclic compound is 37 degrees, whereas the melting point of 2,5-furandianion crosslinking agent is 342 degrees.

In addition, for efficient separation of these products, it is preferable to obtain as much as possible a dicarboxylic acid aromatic heterocyclic compound having a structure represented by the above formula (5).

For example, in the composition according to the fifth aspect of the present invention, the dicarboxylic acid aromatic heterocyclic compound having the structure represented by Chemical Formula 5 may be 95 wt% or more, and the remainder may be obtained by including the remaining materials.

<Sixth aspect of the present invention>

A sixth aspect of the present invention is an apparatus for producing an aromatic heterocyclic dicarboxylic acid compound by oxidizing a raw material for an aromatic heterocyclic compound in a polar solvent in the presence of a heterogeneous catalyst.

The manufacturing apparatus of the sixth aspect includes a reactor, a storage tank for the raw material of the aromatic heterocyclic compound, and a supply apparatus for an oxidizing agent. At this time, the reactor may be a cylinder-type column reactor in which an active catalyst-supported carrier is internally charged, but is not limited thereto.

In addition, the oxidizing agent supply device has a structure connected to a pipe connecting the storage tank of the aromatic heterocyclic compound raw material and the reactor, and may supply the raw material into the reactor in a pressurized state.

The arrangement structure of the oxidizing agent supply device is preferable because the raw material is transferred into the reactor in a pressurized state, so there is no need to separately or additionally control the pressurization condition in the reactor, and the degree of reaction activation can be increased by the raw material. Do.

The reactor pressure may be controlled within the range of 1 to 5 atmospheres by the oxidizing agent supplied through the oxidizing agent supply device, and the reactor temperature may be controlled within the range of 40° C. to 200° C.

The oxidizing agent may be at least one selected from the group consisting of oxygen and air, and the carrier may be independently selected from the group consisting of carbon, aluminum, cerium, zirconium, and magnesium.

In this case, the raw aromatic heterocyclic compound may have a structure represented by Formula 1 above.

The cylinder type column reactor may be one in which the aforementioned heterogeneous catalyst is internally charged. Since the heterogeneous catalyst is the same as that described above, a detailed description thereof will be omitted.

The gaseous dicarboxylic acid aromatic heterocyclic compound discharged from the reactor may be separated in a purification reactor or a crystallization reactor, and may include a dicarboxylic acid aromatic heterocyclic compound collecting unit at a lower portion of the purification reactor or the crystallization reactor.

The reactor may include a first oxidation reactor and a second oxidation reactor. In this case, the first oxidation reactor may be used as a reactor for the catalyst-free oxidation reaction, and the second oxidation reactor may be used as a reactor for the catalytic oxidation reaction.

If necessary, the first oxidation reactor may be used as a reactor for the first catalyst-free oxidation reaction and the second catalyst-free oxidation reaction, and the second oxidation reactor may be used as a reactor for the catalytic oxidation reaction.

For example, the solution in which the aromatic heterocyclic compound is dissolved in a polar solvent is supplied by the pressure difference between the reactor and the storage tank of the raw material of the aromatic heterocyclic compound, and the reaction time (residence time) is controlled by controlling the flow rate using a valve do.

In addition, as a reactor, the solution in which the reaction is completed by passing through a column (eg, a cylinder-type column) in which the heterogeneous catalyst is fixedly packed is transferred to a post-treatment reactor and stored in a collection container through purification and/or crystallization process.

The dicarboxylic acid aromatic heterocyclic compound conversion solution stored in the collection container is discharged from the bottom to separate the solvent, the heterogeneous catalyst and the dicarboxylic acid aromatic heterocyclic compound to recover the dicarboxylic acid aromatic heterocyclic compound as a reaction product.

According to the present invention, since the storage tank filled with the aromatic heterocyclic compound solution is pressurized with an oxidizing agent (oxygen or air), oxygen can be dissolved in the solvent to improve reactivity, and the reaction pressure in the reactor can be controlled.

As a specific example, the aromatic heterocyclic compound, which is a raw material mixed with a solvent, is pressurized with oxygen gas discharged from the oxygen supply tank or from the reactor during transport, and the entire amount of the raw material is dissolved in the solvent containing the reaction product under the pressure conditions in the reactor. Adjust to a concentration that can be achieved.

When pressurizing the oxygen gas discharged from the reactor in the reactor, the flow rate and the like may be adjusted using a control valve or the like. The oxygen supply position may be a reactor, a raw material supply tank for pressurizing the raw material aromatic heterocyclic compound solution with oxygen, or a raw material supply line for supplying the raw material solution to the reactor.

The supply position of the aromatic heterocyclic compound, which is a raw material, is at the upper end of the reactor to maximize the reaction rate, but is not limited thereto.

In the reactor, the raw material aromatic heterocyclic compound solution comes into contact with the fixed bed catalyst and oxygen to cause an oxidation reaction, and at this time, the raw material aromatic heterocyclic compound to be automatically or semi-automatically introduced into the reactor through the liquid mass feeder and control valve provided at the upper end of the reactor It is possible to control the solution content, the input amount of oxygen, the speed, etc. together.

In general, the oxidation reaction rate of the aromatic heterocyclic compound is affected by the amount of oxygen gas dissolved in the reaction solution. In the method of the present invention, the oxygen adsorption amount of the catalyst can also be increased by automatically or semi-automatically injecting the raw material of the aromatic heterocyclic compound pressurized with oxygen into the reactor. Therefore, it is possible to proceed the reaction advantageously.

In addition, the storage tank of the raw material aromatic heterocyclic compound is charged by dissolving the aromatic heterocyclic compound in the above-described polar solvent at a concentration of 0.5 to 5.0wt%, or 0.5 to 2.0wt%, for example, or charging the aromatic heterocyclic compound alone do.

When the aromatic heterocyclic compound is charged alone, the polar solvent supplied from the polar solvent supply tank may be supplied to the pipe connecting the storage tank of the aromatic heterocyclic compound and the reactor to match the above-mentioned concentration.

The raw material prepared as described above is pressurized to 100 bar or less with the oxidizing agent (oxygen gas) supplied from the oxidizing agent storage tank to the pipe. At this time, since the pressurization pressure is proportional to the amount of oxygen dissolved in the raw material solution, using a high pressure can improve the reaction rate.

As the heterogeneous catalyst filled in the reactor, various noble metals or metal precursors, including the catalyst of the second aspect, are taken and dissolved in various polar solvents to prepare a noble metal or metal precursor solution. Activated carbon, graphene, carbon nanotubes, etc. are used in order to use carbon selected as a carrier for the noble metal catalyst because of its very high selectivity to oxygen.

The carbon carrier is preferably washed with a nitric acid solution, washed three times or more with purified water, and then dried and used. A high degree of dispersion can be obtained even by an excess solution impregnation method in which the noble metal is supported.

For example, a platinum precursor solution may be prepared, impregnated with a carbon carrier having a high specific surface area, and then washed and dried.

As another example, to prepare a ternary oxide catalyst of Ru, Mn, and Co, each Mn precursor and Co precursor solution are prepared, surface-modified using an anionic crosslinking agent, and then impregnated in a Ru precursor (if necessary, a Ru precursor solution). Can be washed and dried.

As another example, in order to prepare a binary oxide catalyst of Au and Ce, a Ce precursor solution may be prepared, surface-modified using an anionic crosslinking agent, and then impregnated in the Au precursor solution, and then washed and dried.

These washed and dried carbon carriers (eg, activated carbon) or carriers having a structure represented by the above formula (9) are put into a round flask, and then mixed and supported using a rotary evaporator. After the purified water is evaporated and removed, the carbon material or the carrier having the structure represented by Chemical Formula 9 is dried in a dryer. The dried carbon body or the carrier having the structure represented by the above formula (9) is reduced by heating to 400 to 500 degrees in an electric furnace under a hydrogen atmosphere, and a noble metal-supported carbon body or a heterogeneous catalyst on which a metal catalyst component is supported can be completed. In this case, the reduction temperature may be the temperature of a conventional reduction reaction.

The carbon body on which the prepared catalyst component is supported or the catalyst having the structure represented by Chemical Formula 9 described above is charged in a vertically installed tubular reactor. At this time, if the catalyst-free oxidation reactor and the oxidation reactor exist, the catalyst is charged in the tubular reactor for the oxidation reactor.

After charging, the reactor temperature is maintained in a vacuum at 100 to 500 degrees to remove adsorbed impurities to perform catalyst charging in the reactor.

The reactor (corresponding to the tower filled with catalyst) is controlled in the range of 1-10 bar using an oxidizing agent such as oxygen gas, and below 1 bar, the reaction rate decreases due to adsorption of oxygen, and the reaction rate increases at 10 bar or more. very vague Therefore, the pressure is optimally 2-4 bar.

In addition, the oxidation reaction temperature of the reactor is carried out in the range of 40 to 200 degrees. Below 40°C, the reaction rate is slow, and above 200°C, the adsorption of oxygen to the catalyst surface is reduced and the reactivity decreases. The optimal condition is 40-180 degrees the best.

A solution in which an aromatic heterocyclic compound or a modified compound thereof is dissolved is supplied using a liquid mass feeder to the upper part of the oxidation reaction reactor (catalyst packed column). The supplied aromatic heterocyclic compound solution or a solution in which the modified compound is dissolved flows to the lower part of the reactor by gravity, and reacts with the catalyst for oxidation reaction.

Separation of the reaction product and the solvent may be performed using a method used in a conventional chemical product manufacturing process. For example, the reaction product may be heated or cooled, and then the solvent may be distilled off, or the reaction product crystal may be formed and then the product may be recovered or the product crystal may be recovered.

According to the method of the present invention, since it is possible to carry out a continuous reaction under appropriate reaction conditions using an optimal raw material and a heterogeneous catalyst to provide a desired product, a desired reaction product can be efficiently prepared.

Hereinafter, the present invention will be described with reference to Examples, but the following Examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.

<Example>

Preparation Example 1: Preparation of Raw Material 1 having a structure represented by Chemical Formula 1

As a raw material, a compound having a structure represented by Formula 1 below, R1=aldehyde, R2=ChH ₂ Cl (corresponding to a compound having a structure represented by Formula 2) was prepared by converting from wood.

Preparation Example 2: Preparation of Raw Material 2 having a structure represented by Formula 1

As a raw material, a compound in which R1=R2=aldehyde (corresponding to 5-hydroxymethyl furfural, which does not conform to the proviso of Formula 1) among compounds having a structure represented by the following formula (1) was converted from saccharides and prepared.

Preparation Example 3: Heterogeneous catalyst (4wt% Ru-MnCo ₂ O ₄ ) Preparation

Mn precursor (Mn(CH ₃ COO) ₂ ) and Co precursor (Co(CH ₄ COO) ₃ ) were taken at a 1:1 weight ratio level and dissolved in 50 times the weight of each precursor solution in solvent DIW, Mn precursor solution and Co precursor The solution was prepared.

The prepared precursor solution was mixed and then mixed with a citric acid solution as an anionic crosslinking agent to prepare a porous central metal-organic framework.

The porous central metal-organic framework material was activated to have a spherical shape to generate binding sites, thereby obtaining spherical Ru-MnCo ₂ O ₄ .

Then, as a metal catalyst component, the Ru precursor (RuCl ₃ *3H ₂ O) and the MnCo ₂ O ₄ were stirred for 12 hrs in an N ₂ atmosphere, and NaBH ₄ was dropped to 10 times the level of the Ru precursor and 500 rpm. Stirring was reacted for 24 hours at room temperature in an N ₂ atmosphere to obtain 4% Ru/MnCo ₂ O ₄ .

Preparation Example 4: Heterogeneous catalyst (2wt% Au-CeO ₂ ) Preparation

A Ce precursor solution was prepared by taking a Ce precursor (Ce(CH ₃ COO) ₂ ) and dissolving it in 20 g of a solvent H ₂ O and 0.01 mol of an aqueous NaOH solution. A spherical CeO ₂ support was obtained by stirring at room temperature in a nitrogen atmosphere for 12 hours.

As an inactive catalyst component, the Au precursor (AuCl ₃ *3H ₂ O) and the CeO ₂ support were stirred in a 12 hr N ₂ atmosphere, and NaNH ₄ was dropped 10 times the level of the Au precursor and stirred at a speed of 500 rpm N The reaction was carried out at room temperature in ₂ atmospheres for 24 hours to obtain a 2 wt% Au-CeO ₂ catalyst.

Preparation Example 5: Heterogeneous catalyst (4wt% Ru-MnCo ₂ O ₄ ) Preparation

Mn precursor (Mn(CH ₃ COO) ₂ ) and Co precursor (Co(CH ₄ COO) ₃ ) were taken at a 1:1 weight ratio level and dissolved in 50 times the weight of each precursor solution in solvent DIW, Mn precursor solution and Co precursor The solution was prepared.

The prepared precursor solution was mixed and stirred at room temperature under N ₂ atmosphere for 12 hours to obtain a framework material.

Then, as a metal catalyst component, the Ru precursor (RuCl ₃ *3H ₂ O) and the MnCo ₂ O ₄ were stirred for 12 hrs in an N ₂ atmosphere, and NaBH ₄ was dropped to 10 times the level of the Ru precursor and 500 rpm. Stirring was reacted for 24 hours at room temperature in an N ₂ atmosphere to obtain 4% Ru/MnCo ₂ O ₄ .

<Example 1: Oxidation reaction experiment>

The reactor includes a reaction part, and two types of columns made of SUS material with a diameter of 20 cm and a height of 100 cm are connected. It was filled with a heterogeneous catalyst, Ru-MnCo ₂ O ₄ 1.5 kg.

Here, the Ru-MnCo ₂ O ₄ was filled using the one prepared in Preparation Example 3. After charging, the vacuum was maintained at the reactor temperature at 150°C to remove adsorbed impurities.

In the storage tank of the raw material aromatic heterocyclic compound, an aromatic heterocyclic compound (compound of formula 1, R1 = aldehyde, R2 = CH ₂ Cl, corresponding to the material prepared in Preparation Example 1) at a concentration of 1 wt% is acetonitrile as a polar solvent was dissolved in and filled with 5 liters. After filling, it was pressurized to 3 bar with oxygen gas. At this time, since the pressurization pressure is proportional to the amount of oxygen dissolved in the aromatic heterocyclic compound, using a high pressure can improve the reaction rate.

The raw material was supplied to the upper part of the column in a state of a solution pressurized in oxygen using a liquid mass feeder to the column of the previous stage, and the internal pressure of the column was adjusted in the range of 1-5 bar. The supplied aromatic heterocyclic compound solution flows to the lower part of the column by gravity, and at this time, 15 g of tetrabutylammonium chloride (TBAC) and 10 g of NaOAc as an ion activator are added to the column of the previous stage as an onium compound. did.

At this time, as a result of confirming the structure by extracting some of the reactants, it was confirmed that the compound had a structure represented by the following formula (3).

[Formula 3]

Then, the reactant is transferred to the rear column to contact the catalyst in the column, and 3wt% NaHCO ₃ (in DIW solution) is added to the reactant 3 for the oxidation reaction while intermittently introducing NaHCO ₃ to satisfy the pH of the reaction solution in the range of 7 to 11. It was washed with water three times in culture to obtain a crude composition containing oxides.

<Example 2: Oxidation reaction experiment>

The same method as in Example 1 was performed, except that 2 wt% Au-CeO ₂ of Preparation Example 4 was used in 4 wt% Ru-MnCo ₂ O ₄ of Preparation Example 3 Using the same apparatus as in Example 1 Oxidation The reaction was carried out.

Specifically, the reactor includes a reaction unit, and two columns made of SUS material with a diameter of 20 cm and a height of 100 cm are connected. The reaction part of the rear stage was filled with 1.5 kg of Au-CeO ₂ as a heterogeneous catalyst.

Here, the Au-CeO ₂ was charged using the one prepared in Preparation Example 4. After charging, the vacuum was maintained at the reactor temperature at 150°C to remove adsorbed impurities.

In the storage tank of the raw material aromatic heterocyclic compound, an aromatic heterocyclic compound (compound of formula 1, R1 = aldehyde, R2 = CH ₂ Cl, corresponding to the material prepared in Preparation Example 1) at a concentration of 1 wt%) as a polar solvent in DMSO It was dissolved and filled to 5 liters. After filling, it was pressurized to 3 bar with oxygen gas. At this time, since the pressurization pressure is proportional to the amount of oxygen dissolved in the aromatic heterocyclic compound, using a high pressure can improve the reaction rate.

The raw material was supplied to the upper part of the column in a state of a solution pressurized in oxygen using a liquid mass feeder to the column of the previous stage, and the internal pressure of the column was adjusted in the range of 1-5 bar. The supplied aromatic heterocyclic compound solution flows to the lower part of the column by gravity, and at this time, a part of the catalyst-free oxidation reactant is extracted and the structure is confirmed. As a result, it was confirmed that the compound has a structure represented by the following Chemical Formula 4.

[Formula 4]

Then, the solvent (DMSO) in the column of the previous stage was replaced with tert-butyl hypochlorite (Tert-BUTYL HYPOCHLORITE), and the reaction was carried out at room temperature for 24 hours.

In addition, as a result of confirming the structure by extracting some of the reactants, it was confirmed that the compound was also a compound having a structure represented by Chemical Formula 4 above.

Then, the obtained reactant is transferred to the rear column to contact the catalyst in the column, and 3 wt% NaHCO ₃ in DIW solition is performed for the oxidation reaction while intermittently adding NaHCO ₃ to satisfy the reaction solution pH 7 to 11. 3 times the reactant It was washed with water, and a crude composition containing oxide was obtained.

<Comparative Example 1: Oxidation reaction experiment>

The same process was repeated except that the raw material of Preparation Example 1 used in Example 1 was replaced with the raw material of Preparation Example 2 to obtain a crude composition containing an oxide.

<Comparative Example 2: Oxidation reaction experiment>

The same method as in Example 1 was performed, except that 4 wt% Ru-MnCo ₂ O ₄ of Preparation Example 5 was used instead of 1 wt% Ru-MnCo ₂ O ₄ of Preparation Example 3 The same apparatus as in Example 1 was used. was used to carry out the oxidation reaction.

Specifically, the reactor includes a reaction unit, and two columns made of SUS material with a diameter of 20 cm and a height of 100 cm are connected. The reaction part of the rear stage was filled with a heterogeneous catalyst, Ru-MnCo ₂ O ₄ 1.5 kg.

Here, the Ru-MnCo ₂ O ₄ was filled using the one prepared in Preparation Example 5. After charging, the vacuum was maintained at the reactor temperature at 150°C to remove adsorbed impurities.

In the storage tank of the raw material aromatic heterocyclic compound, an aromatic heterocyclic compound (compound of formula 1, R1 = aldehyde, R2 = CH ₂ Cl, corresponding to the material prepared in Preparation Example 1) at a concentration of 1 wt% is acetonitrile as a polar solvent was dissolved in and filled with 5 liters. After filling, it was pressurized to 3 bar with oxygen gas. At this time, since the pressurization pressure is proportional to the amount of oxygen dissolved in the aromatic heterocyclic compound, using a high pressure can improve the reaction rate.

The raw material was supplied to the upper part of the column in a state of a solution pressurized in oxygen using a liquid mass feeder to the column of the previous stage, and the internal pressure of the column was adjusted in the range of 1-5 bar. The supplied aromatic heterocyclic compound solution flows to the lower part of the column by gravity, and at this time, 15 g of tetrabutylammonium chloride (TBAC) and 10 g of NaOAc as an ion activator are added to the column of the previous stage as an onium compound. did.

At this time, as a result of confirming the structure by extracting some of the reactants, it was confirmed that the compound had a structure represented by the following formula (3).

[Formula 3]

Then, the reactant is transferred to the rear column to contact the catalyst in the column, and 3wt% NaHCO ₃ in DIW solution is added to the reactant 3 times the amount of NaHCO ₃ for the oxidation reaction while intermittently adding NaHCO 3 to satisfy the pH 7-11 was washed with water three times, and a crude composition containing oxide was obtained.

<Evaluation>

1) Yield evaluation

Through component analysis of the crude composition synthesized by the methods presented in Examples 1 and 2 and Comparative Examples 1 and 2, a compound having a structure represented by the following Chemical Formula 5, a compound having a structure represented by the following Chemical Formula 6, and Chemical Formula 7 The content of the compound having the structure represented by was measured and shown in Table 1 below.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Formula 5 compound (wt%) 99 98 65.5 73.5 Formula 6 structure compound (wt%) 0.3 0.4 30 23 Formula 7 compound (wt%) 0.7 1.6 4.5 3.5

As shown in Table 1, when the raw material of Preparation Example 1 presented in the present invention was used, yields of 98 wt% or more were confirmed for all of the heterogeneous catalysts of Preparation Examples 3 to 4.

On the other hand, when the raw material of Comparative Example 1 was used, a poor yield of 65.5% was confirmed for each of the heterogeneous catalysts of Preparation Examples 3 to 5.

In addition, when the catalyst of Preparation Example 5 prepared without using the appropriate crosslinking agent of Comparative Example 2 was used, a poor yield of 73.5% was confirmed.

2) Purity evaluation

The purity of the compound having the structure represented by Chemical Formula 5 confirmed in the yield evaluation was measured by HPLC using the sample obtained in Example 1 and the standard product of Aldrich Corporation of the United States used as a standard material in the relevant field as a control example, and the purity was compared. The analysis results are shown in Table 2 below.

division Example 1 contrast example water 97.5 95

As shown in Table 2, it was confirmed that the compound synthesized in excess using the raw material provided by the present invention showed high purity.

3)Conversion rate evaluation

As a result of measuring the conversion rate according to the temperature and reaction pressure during the oxidation reaction of the crude composition obtained in Examples 1 to 2, the compound having the structure represented by Chemical Formula 5 in the range of 100°C to 180°C was obtained in 1 to 4 atm pressure units. It was confirmed that an excellent conversion rate was exhibited.

4) Evaluation of the influence of pressure

The effect of pressure at the same temperature was evaluated during the evaluation of the conversion rate of item 3). The pressure affects the oxygen adsorption power of carbon and platinum, or the oxygen adsorption power of the central metal, transition metal, and metal catalyst component, and it was confirmed that an excellent conversion rate was exhibited at 1 to 5 atmospheres, particularly 2 atmospheres. .

Features, structures, effects, etc. exemplified in each of the above-described embodiments may be combined or modified for other embodiments by those of ordinary skill in the art to which the embodiments belong. Accordingly, the contents related to such combinations and modifications should be interpreted as being included in the scope of the present invention.

Claims (15)

A method for producing an aromatic heterocyclic compound of dicarboxylic acid by oxidizing a raw material of an aromatic heterocyclic compound in a polar solvent in the presence of a heterogeneous catalyst, the method comprising:
The aromatic heterocyclic compound raw material is a hydroxyl-free compound having a structure represented by the following formula (1),
The heterogeneous catalyst is a method for preparing a dicarboxylic acid aromatic heterocyclic compound having a structure in which a cation of a metal catalyst component is bonded to a porous central metal-organic framework material:
[Formula 1]

(Wherein, any one of R1 and R2 is an aldehyde, the rest are substituted or unsubstituted (C1-C20)alkyl, acetoxy or aldehyde, and the substituted (C1-C20)alkyl is bromine, chlorine, substituted with one or more functional groups selected from the group consisting of fluorine and iodine). According to claim 1,
The hydroxyl-free aromatic heterocyclic compound is a method for producing a dicarboxylic acid aromatic heterocyclic compound having at least one structure selected from the following Chemical Formulas 2 to 4.
[Formula 2]

[Formula 3]

[Formula 4]

According to claim 1,
The aromatic heterocyclic compound having a structure represented by the formula (1) is used in a modified state to a structure represented by the following formula (3) or a structure represented by the following formula (4):
[Formula 3]

[Formula 4]

4. The method of claim 3,
The oxidation reaction is
A catalyst for producing an aromatic heterocyclic compound having a structure represented by the following formula (3) by subjecting an aromatic heterocyclic compound raw material having a structure represented by the following formula (2) to an oxidation reaction at a fourth temperature in a polar solvent in the presence of an onium-based compound and an ion activator pre-oxidation step; and
Oxidation step of generating a dicarboxylic acid aromatic heterocyclic compound by oxidizing the aromatic heterocyclic compound having the structure represented by Chemical Formula 3 at a fifth temperature higher than the fourth temperature in a polar solvent in the presence of a basic material and a heterogeneous catalyst; Method for producing a dicarboxylic acid aromatic heterocyclic compound comprising:
[Formula 2]

[Formula 3]

5. The method of claim 4,
The fourth temperature is in the range of 10 ℃ to 80 ℃, the fifth temperature is a method of producing a dicarboxylic acid aromatic heterocyclic compound in the range of 100 ℃ to 200 ℃. 5. The method of claim 4,
The catalyst-free oxidation step is performed for 1 hr to 10 hr, and the oxidation step is performed for 3 hr to 24 hr. A method for producing a dicarboxylic acid aromatic heterocyclic compound. a primary catalyst pre-oxidation step of oxidizing a raw material for an aromatic heterocyclic compound having a structure represented by the following Chemical Formula 2 in a polar solvent at a sixth temperature;
a secondary catalyst pre-oxidation step of substituting the polar solvent with another type of polar solvent and performing an oxidation reaction at a seventh temperature lower than the sixth temperature to produce an aromatic heterocyclic compound having a structure represented by the following Chemical Formula 4; and
an oxidation step of oxidizing an aromatic heterocyclic compound having a structure represented by Chemical Formula 4 in a polar solvent at an eighth temperature lower than the sixth temperature in the presence of a heterogeneous catalyst to produce a dicarboxylic acid aromatic heterocyclic compound; Method for producing a dicarboxylic acid aromatic heterocyclic compound comprising:
[Formula 2]

[Formula 4]

8. The method of claim 7,
The sixth temperature is within the range of 100 ℃ to 200 ℃,
The seventh temperature is within the range of 10 ℃ to 80 ℃,
The eighth temperature is a method of producing a dicarboxylic acid aromatic heterocyclic compound within the range of 10 ℃ to 80 ℃. 8. The method of claim 7,
The first catalyst-free oxidation step is performed for 8 hr to 24 hr,
The secondary catalyst pre-oxidation step is performed for 15 hr to 32 hr,
The oxidation step is a method for producing a dicarboxylic acid aromatic heterocyclic compound carried out for 1 hr to 10 hr. 5. The method of claim 4,
The onium-based compound is a dicarboxylic acid using a compound composed of an onium cation having an alkyl group having 4 to 10 carbon atoms and an anion having a pKa value of 3 or less in a molar ratio of 0.4 to 1.0 based on 1 mole of the aromatic heterocyclic compound represented by Formula 2 A method for producing an aromatic heterocyclic compound. 8. The method of claim 4 or 7,
The polar solvent is at least one selected from acetonitrile, acetone, dimethylformamide, dimethyl sulfoxide, water, ethanol, methanol and t-butyl hypochlorite 2 based on 1 mole of the aromatic heterocyclic compound represented by Formula 2 A method for producing a dicarboxylic acid aromatic heterocyclic compound used in a molar ratio of to 5. 5. The method of claim 4,
The ion activator is a method for producing a dicarboxylic acid aromatic heterocyclic compound using at least one selected from NaOAC and KOAc in an amount of 1 to 10 moles based on 1 mole of the aromatic heterocyclic compound represented by Formula 2 above. 5. The method of claim 4,
The basic compound is one or more selected from sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, and dibasic and tribasic phosphate buffers, the pH of the reaction solution exceeds 7 11. A method for producing a dicarboxylic acid aromatic heterocyclic compound which is continuously added to the reaction solution in a range maintained below 11 or intermittently added before, during, or after the reaction. A dicarboxylic acid aromatic composition prepared by using an aromatic heterocyclic compound prepared according to the method for preparing an aromatic dicarboxylic acid aromatic heterocyclic compound according to claim 1 or 7 as a raw material,
A crude dicarboxylic acid aromatic heterocyclic composition comprising a dicarboxylic acid aromatic heterocyclic compound having a structure represented by the following formula (5).
[Formula 5]

15. The method of claim 14,
The dicarboxylic acid aromatic heterocyclic composition is an aromatic heterocyclic compound having a structure represented by Formula 2 below, an aromatic heterocyclic compound having a structure represented by Formula 3 below, an aromatic heterocyclic compound having a structure represented by Formula 4 below, and Formula A dicarboxylic acid aromatic heterocyclic composition comprising at least one selected from an aromatic heterocyclic compound (FFCA) having a structure represented by 6 and an aromatic heterocyclic compound having a structure represented by the following formula (7).
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 6]

[Formula 7]