JP7476498B2 - Method for producing 4-hydroxybenzoic acid or its derivatives and method for producing chemical products - Google Patents

Description

The present invention relates to a method for producing 4-hydroxybenzoic acid or a derivative thereof and a method for producing a chemical product.

Cyclic compounds such as aromatic carboxylic acid compounds are used, for example, as raw materials for resins such as engineering plastics and pharmaceuticals, as well as for fragrances and cosmetics, or as raw materials for these.

Such cyclic compounds are traditionally produced using fossil resources such as petroleum, natural gas, and coal as raw materials. In recent years, however, there have been attempts to use biomass resources as raw materials due to concerns over global warming caused by the depletion of fossil resources and the increase in carbon dioxide concentrations.

For example, Patent Document 1 discloses a method of producing methane from biomass by microbial fermentation, producing benzene from the methane by a catalytic reaction, and then producing a benzene derivative from the benzene. The benzene derivative produced in this way is used as a raw material for aromatic polymers, making it possible to realize polymers that are not dependent on fossil resources.

JP 2004-123666 A

However, the conventional methods are still not efficient enough in producing benzene derivatives. Specifically, because benzene derivatives (such as phthalic acid) are produced from biomass via methane and benzene, there is a problem that the amount of benzene derivatives synthesized is small compared to the effort and energy input.

There is also a demand for increasing the purity of the benzene derivatives produced. Patent Document 1 discloses purifying benzene using a method such as distillation, which can increase the purity of the benzene derivatives, but this still consumes a lot of energy.

An object of the present invention is to provide a production method capable of producing solid, high-purity 4-hydroxybenzoic acid or a derivative thereof in a high yield, and a production method for chemical products capable of producing high-quality chemical products.

These objects can be achieved by the present invention described below in (1) to (8) .
(1) a concentration step of repeatedly contacting a raw material liquid containing 4-hydroxybenzoic acid or a derivative thereof with a heated heat transfer surface under a pressure of 80 kPa or less and heating the raw material liquid to 20 to 90° C. , thereby evaporating a solvent contained in the raw material liquid and concentrating the raw material liquid;
an activated carbon treatment step of adding 0.01 to 3 g of activated carbon to 100 g of the concentrated raw liquid;
a crystallization step in which the pH of the raw material liquid that has been treated with activated carbon is changed at a temperature in the range of 20 to 60° C. to cause the solute in the raw material liquid to precipitate as a solid;
a solid-liquid separation step of recovering the solid as a powder from the raw material liquid;
The present invention relates to a method for producing 4-hydroxybenzoic acid or a derivative thereof.

(2) The method for producing 4-hydroxybenzoic acid or a derivative thereof according to the above (1), wherein the concentrating step includes repeating a process of reducing pressure and a process of returning to normal pressure.

(3) The method for producing 4-hydroxybenzoic acid or a derivative thereof according to the above (1) or (2) , wherein the crystallization step includes an operation of adding seed crystals .

(4) The method for producing 4-hydroxybenzoic acid or a derivative thereof according to any one of (1) to (3) above, wherein the temperature of the activated carbon treatment is 30 to 150° C.

(5) The method for producing 4-hydroxybenzoic acid or a derivative thereof according to any one of (1) to (4) above, wherein the solid-liquid separation step is a step of filtering and separating the solid from the raw material liquid.

(6) The method for producing 4-hydroxybenzoic acid or a derivative thereof according to any one of (1) to (5) above, further comprising a raw material liquid preparation step of preparing the raw material liquid from biomass.

(7) The method for producing 4-hydroxybenzoic acid or a derivative thereof according to any one of (1) to (6) , wherein the powder has an ISO whiteness of 70% or more as measured in accordance with the ISO whiteness test method specified in JIS P 8148: 2001.

(8) A method for producing a chemical product , comprising the method for producing 4-hydroxybenzoic acid or a derivative thereof according to any one of (1) to (7) above.

According to the present invention, it is possible to produce solid, highly pure 4-hydroxybenzoic acid or a derivative thereof in high yield.
Furthermore , according to the present invention, high-quality chemical products can be produced in high yields .

FIG. 1 is a process diagram illustrating an embodiment of a method for producing a cyclic compound or a derivative thereof of the present invention.

The method for producing the cyclic compound or its derivative, the cyclic compound or its derivative, and the chemical product of the present invention will be described in detail below based on the preferred embodiment shown in the attached drawings.

<Method for producing cyclic compound or derivative thereof>
First, an embodiment of the method for producing the cyclic compound or a derivative thereof of the present invention will be described.

Figure 1 is a process diagram illustrating an embodiment of the method for producing a cyclic compound or a derivative thereof of the present invention.

The method for producing a cyclic compound or a derivative thereof according to this embodiment (hereinafter, abbreviated as "method for producing a cyclic compound") includes a raw liquid preparation step S01 for preparing a raw liquid from biomass, a concentration step S02 for concentrating the raw liquid, an activated carbon treatment step S03 for contacting the raw liquid with activated carbon, a crystallization step S04 for subjecting the raw liquid to a crystallization process to precipitate the solute of the raw liquid as a solid, and a solid-liquid separation step S05 for recovering a solid cyclic compound or a derivative thereof from the raw liquid. According to this method for producing a cyclic compound, a solid, high-purity cyclic compound or a derivative thereof can be produced with a high yield.

Each step will be explained below. In the following explanation, cyclic compounds or their derivatives will be abbreviated to "cyclic compounds."

(Raw material liquid preparation step S01)
A raw material liquid is prepared from biomass by the method described in International Publication WO2015/156271.

(Concentration step S02)
Next, the obtained raw liquid is concentrated. Examples of the raw liquid include the liquid containing the reaction product between the above-mentioned sugars and the transformant.

Concentration methods include, for example, distillation, adsorption, extraction, membrane separation, dialysis, reverse osmosis, etc., and one or more of these may be used in combination.

Of these, the concentration process is a process in which the raw liquid is brought into contact with a heated heat transfer surface to evaporate the solvent contained in the raw liquid, and is preferably a process in which the raw liquid is repeatedly brought into contact with the heat transfer surface. According to such a process, the heat transfer surface can be constantly wetted with the raw liquid when the solvent contained in the raw liquid is evaporated, so that the occurrence of scorching can be suppressed.

Specifically, the raw liquid is placed in a mixing tank whose inner wall surface is a heat transfer surface, and the raw liquid that has accumulated at the bottom is pumped up and concentrated using a device that stirs the raw liquid while spraying it on the inner wall surface. This makes it possible to make maximum use of the effective area of the heat transfer surface, and increases the concentration efficiency. It also prevents the heat transfer surface from drying out and prevents the coloring of the precipitated solid.

The heating temperature in the concentration step is not particularly limited, but is preferably about 15 to 120°C, and more preferably about 20 to 90°C. This increases the efficiency of concentration while suppressing the occurrence of scorching and denaturation of solutes.

The raw material solution in the concentration step may be placed under reduced pressure. This promotes evaporation of the solvent and increases the concentration efficiency. There are no particular limitations on the pressure of the environment in which the raw material solution is placed, but it is preferably 80 kPa or less, and more preferably 0.1 to 50 kPa.

For the concentration, a salt of the cyclic compound may be prepared using a basic substance, and then dissolved in an aqueous medium.
Furthermore, the concentration step may be carried out as necessary and may be omitted.

In addition, by concentrating the raw liquid, the ratio (yield) of the amount of solids that can be recovered from a unit amount of raw liquid can be increased. This makes it possible to reduce the time and energy required for the crystallization process described below, and to increase the production efficiency of solids (production capacity of solids per unit time).

In the concentration process, there is a risk that the concentration efficiency will gradually decrease as the concentration progresses. In consideration of this problem, in this process, if necessary, a process of repeatedly reducing pressure and returning to normal pressure may be performed during the concentration. This causes the air bubbles to contract and expand, encouraging the bubbles to rise and burst, thereby efficiently eliminating the air bubbles. As a result, the decrease in concentration efficiency can be suppressed.

The pressure in the decompression operation is not particularly limited, but is preferably about 0.1 to 100 kPa, and more preferably about 1 to 80 kPa. This allows the contained air bubbles to rise and burst efficiently, and promotes concentration while sufficiently suppressing a decrease in concentration efficiency.

The ratio of the time for the depressurization operation to the time for the normal pressure return operation is adjusted appropriately depending on the degree of bubble generation and the concentration speed, but as an example, it is preferable for it to be about 1:10 to 10:1. This allows for efficient removal of bubbles.

The time for the decompression operation is not particularly limited, but is preferably about 1 to 10 seconds, for example. This allows air bubbles to be removed efficiently.

(Activated carbon treatment step S03)
Next, the raw liquid is subjected to activated carbon treatment.

Activated carbon is added to the raw liquid and stirred. This allows the solutes in the raw liquid to be decolorized.

The temperature for the activated carbon treatment is preferably about 30 to 150°C. The time for the activated carbon treatment is not particularly limited, but is preferably about 10 minutes to 10 hours.

The amount of activated carbon added per 100 g of raw liquid is not particularly limited, but is preferably 0.01 to 3 g, and more preferably 0.1 to 1 g, which can suppress the solute from being adsorbed by the activated carbon while providing a sufficient decolorizing effect.
The activated carbon treatment may be carried out as necessary and may be omitted.

(Crystallization step S04)
Next, the raw liquid is subjected to a crystallization process to precipitate the solute of the raw liquid as a solid. This crystallization process involves a process in which the solubility of the solute in the solution is reduced to precipitate a solid, and a solid substance with high purity can be recovered by a subsequent solid-liquid separation process. This makes it possible to easily produce cyclic compounds that are useful as raw materials for daily necessities, cosmetics, pharmaceuticals, foods, etc.

The crystallization process can be any process that causes the solute to precipitate as a solid from the raw liquid.

Specific examples include a process in which the temperature of the raw liquid is changed to utilize the temperature dependency of solubility for crystallization, a process in which the solvent is evaporated from the raw liquid by heating or reducing pressure, etc., a process in which a solvent in which the solute has low solubility is added to utilize the solvent-type dependency of solubility for crystallization, and a process in which the pH of the raw solution is changed to utilize the pH responsiveness of solubility for crystallization, and the like. One or a combination of these processes can be used.

For example, when using a process for crystallization that utilizes pH responsiveness, the solubility of cyclic compounds contained in the solute in water generally decreases at low pH. Therefore, by lowering the pH to, for example, about 1 to 4 in the crystallization process, the solubility can be reduced and the solute can be precipitated.

The temperature at this time is not particularly limited, but is preferably about 15 to 80°C, and more preferably about 20 to 60°C. This allows both the crystallization process capacity and yield to be achieved.

The crystallization process may be a batch process or a continuous process.
For the crystallization operation, a known stirring tank is used.

To promote crystallization, seed crystals containing the solid components to be precipitated may be added as necessary. This promotes crystallization with the seed crystals acting as nuclei, increasing the crystallization efficiency and facilitating high purity.

(Solid-liquid separation step S05)
Next, the solid cyclic compound is recovered from the raw liquid. This allows the solid, high-purity cyclic compound to be efficiently recovered by solid-liquid separation. Such cyclic compounds are easy to handle and do not require further purification or can reduce the time and effort required for further purification, making them easy to use as, for example, chemical products or their raw materials.

Examples of solid-liquid separation include filtration, sedimentation, dehydration under reduced pressure, and dehydration under pressure, among which filtration is preferably used from the viewpoints of ease of operation and accuracy of separation. Specifically, a centrifugal filter can be used.
The solid-liquid separation operation may be a batch operation or a continuous operation.

If necessary, the product can then be washed with a poor solvent and then dried to recover a more pure solid cyclic compound.

<Cyclic Compound or Derivative>
Next, embodiments of the cyclic compound or a derivative thereof of the present invention will be described.

The cyclic compound or its derivative according to this embodiment is, for example, a compound represented by the following formula (1).

［式（１）中、環Ａは、飽和環、部分飽和環もしくは芳香環の５員環、飽和環、部分飽和環もしくは芳香環の６員環、または、５員環もしくは６員環を含む縮合環であり、Ｘは単結合または１つ以上の炭素数を含む結合であり、Ｙは水素原子またはアルキル基、Ｒ^２～Ｒ^６（環Ａが５員環の場合はＲ^２～Ｒ^５）は、独立して、水素原子、水酸基、アミノ基、アルコキシ基、カルボキシル基またはカルボニル基である。］

[In formula (1), ring A is a five-membered saturated ring, partially saturated ring, or aromatic ring, a six-membered saturated ring, partially saturated ring, or aromatic ring, or a fused ring containing a five-membered ring or a six-membered ring, X is a single bond or a bond containing one or more carbon atoms, Y is a hydrogen atom or an alkyl group, and R ² to R ⁶ (R ² to R ⁵ when ring A is a five-membered ring) are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group.]

The derivative of a cyclic compound is any one of the compounds represented by the above formula (1), compounds derived from the compounds represented by the above formula (1), and salts of the compounds represented by the above formula (1), or a mixture of two or more of these.

Compounds derived from the compound represented by (1) above include esters, acid anhydrides, amides, acid halides, etc. of the compound represented by (1) above. Examples of esters include methyl esters, ethyl esters, propyl esters, butyl esters, etc.

Examples of salts of the compound represented by (1) above include sodium salts, potassium salts, ammonium salts, etc.

In addition, such cyclic compounds are preferably derived from biomass and are in powder form. This makes it possible to obtain chemical products or chemical product raw materials that have a low environmental impact and are easy to handle.

In addition, such cyclic compounds preferably have an ISO whiteness of 70% or more, more preferably 80% or more, measured according to the ISO whiteness test method specified in JIS P 8148:2001. Such cyclic compounds have few impurities and can be used as chemical products or raw materials for chemical products. In particular, when producing light-colored chemical products, it is necessary to prevent the color of the raw materials from transferring to the chemical product. In such cases, by using a cyclic compound with an ISO whiteness within the above range, color defects are less likely to occur and high-quality chemical products can be obtained.

The ISO whiteness is measured using a spectrophotometer (e.g., PF7000R manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS P 8148:2001 "Method of measurement of ISO whiteness (diffuse blue light reflectance)".

Here, the compound represented by formula (1) will be further explained.
Examples of the saturated ring, partially saturated ring, or aromatic 5-membered ring include a furan structure, a thiophene structure, a pyrrole structure, a pyrrolidine structure, a tetrahydrofuran structure, a 2,3-dihydrofuran structure, a pyrazole structure, an imidazole structure, an oxazole structure, an isoxazole structure, a thiazole structure, and an isothiazole structure.

Examples of the six-membered saturated ring include hydrocarbon-based saturated rings such as a cyclohexane structure, nitrogen-containing saturated rings such as a piperidine structure, piperazine structure, triazinane structure, tetraazinane structure, pentazinane structure, and quinuclidine structure, oxygen-containing saturated rings such as a tetrahydropyran structure and a morpholine structure, and sulfur-containing saturated rings such as a tetrahydrothiopyran structure.

Examples of the six-membered partially saturated ring include hydrocarbon partially saturated rings such as a cyclohexene structure or a cyclohexadiene structure, nitrogen-containing partially saturated rings such as a piperidine structure, oxygen-containing partially saturated rings such as a pyran structure, and sulfur-containing partially saturated rings such as a thiazine structure.

Examples of the six-membered aromatic ring include hydrocarbon aromatic rings such as a benzene structure, and nitrogen-containing aromatic rings (nitrogen-containing unsaturated rings) such as a pyridine structure, pyridazine structure, pyrimidine structure, pyrazine structure, triazine structure, tetrazine structure, and pentazine structure.

Examples of fused rings include a fused ring of a 6-membered ring and a 5-membered ring, and a fused ring of two 6-membered rings. Of these, examples of fused rings of a 6-membered ring and a 5-membered ring include indole-based structures such as indole, indolenine, indoline, isoindole, isoindolenine, isoindoline, isodolizine, purine, and indolizidine. Examples of fused rings of two 6-membered rings include quinoline-based structures such as quinoline, isoquinoline, quinolizidine, quinoxaline, cinnoline, quinazoline, phthalazine, naphthyridine, and pteridine.

X is a single bond or a bond containing one or more carbon atoms.
When X is a single bond, the oxygen atom is directly bonded to a ring-constituting atom of ring A.

On the other hand, examples of bonds containing one or more carbon atoms include hydrocarbon groups having 1 to 4 carbon atoms, ether bonds, ester bonds, amide bonds, carbonyl groups, vinylidene groups, etc., and these may be used alone or in combination of two or more.

Of these, the hydrocarbon group having 1 to 4 carbon atoms may be either linear or branched, and may be either saturated or unsaturated. The hydrogen atom of the hydrocarbon group may be substituted with a substituent such as an alkyl group having 1 to 2 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, or a halogen atom.

In addition to the bonds described above, X may contain any atom or atomic group. For example, X may be an atomic group that contains a carbonyl group and a bond containing one or more carbon atoms.

Y is a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 to 4.

When ring A is a 6-membered ring, R ² to R ⁶ are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group, and when ring A is a 5-membered ring, R ² to R ⁵ are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group.

When ring A is a 6-membered ring and any of R ² to R ⁶ is a carbonyl group, or when ring A is a 5-membered ring and any of R ² to R ⁵ is a carbonyl group, the ring-constituting atom of ring A is a carbon atom and there is a double bond between the carbon atom and an oxygen atom, which is referred to as a carbonyl group.

Specific examples of cyclic compounds include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, mellophanic acid, prenitic acid, pyromellitic acid, phenylacetic acid, hydroxyphenylacetic acid, phenylbutyric acid (phenyllactate), hydroxyphenylbutyric acid, phenylpyruvic acid, hydroxyphenylpyruvic acid, phenyllactic acid, hydroxyphenyllactic acid, anthranilic acid, hydroatropic acid, atropic acid, hydrophenyllactic acid, phenylacetate ... Cinnamic acid (coumaric acid), cinnamic acid, salicylic acid (2-hydroxybenzoic acid), m-salicylic acid (3-hydroxybenzoic acid), p-salicylic acid (4-hydroxybenzoic acid), methoxybenzoic acid, aminobenzoic acid, hydroxybenzoic acid, pyrocatechuic acid (2,3-dihydroxybenzoic acid), β-resorcylic acid (2,4-dihydroxybenzoic acid), gentisic acid (2,5-dihydroxybenzoic acid), γ-resorcylic acid (2,6-dihydroxybenzoic acid), protocatechuic acid (3,4-dihydroxybenzoic acid), α-resorcylic acid (3,5-dihydroxybenzoic acid), trihydroxybenzoic acid, vanillic acid (4-hydroxy-3-methoxybenzoic acid), isovanillic acid (3-hydroxy-4-methoxybenzoic acid), veratric acid, gallic acid, syringic acid, asaronic acid, mandelic acid, vanillylmandelic acid, anisic acid, homoprotocatechuic acid, homovanillic acid, homoisovanillic acid, homoveratric acid, homophthalic acid, homoisophthalic acid, homo These include terephthalic acid, phthalonic acid, isophthalonic acid, terephthalonic acid, atrolactic acid, tropic acid, mellitic acid, phloretic acid, dihydrocaffeic acid, hydroferulic acid, hydroisoferulic acid, umbellic acid, caffeic acid (caffeic acid), ferulic acid, isoferulic acid, sinapic acid, syringic acid, dehydroquinic acid, dehydroshikimic acid, shikimic acid, chorismic acid, L-tryptophan, L-tyrosine, prephenic acid, arogenic acid, and L-phenylalanine.

Other specific examples of cyclic compounds include polyphenols such as flavonoids, lignans, chalcones, stilbenoids, alkaloids, curcuminoids, terpenoids, saponins, various glycosides, and various polyphenol-based aromatic compounds, as well as amino acids and vitamins.

Among these, examples of flavonoids include anthocyanidins such as aurantidin, cyanidin, delphinidin, europinidin, luteolinidin, pelargonidin, malvidin, peonidin, petunidin, and rosinidin, anthocyanins such as procyanidin, flavanones such as naringenin, eriocitrin, pinocembrin, and eriodictyol, flavans such as catechin, flavones such as apigenin, luteolin, baicalein, and chrysin, flavonols such as quercetin and kaempferol, isoflavones, isoflavones, isoflavanes, isoflavandiols, and isoflavonoids such as genistein, as well as neoflavonoids, biflavonoids, aurones, prenylated flavonoids, and O-methylated flavonoids.

Examples of lignans include pinoresinol, lariciresinol, secoisolariciresinol, matairesinol, hydroxymatairesinol, syringaresinol, sesamin, arctigenin, sesaminol, podophyllotoxin, and steganacin.

Further examples of stilbenoids include aglycones such as piceatannol, pinosylvin, pterostilbene, resveratrol, 4'-methoxyresveratrol, pinostilbene, and piciatannol, and oligomers such as α-viniferin, ampelopsin A, ampelopsin E, diptoindonesin C-kawane, diptoindonesin F-dammarbua, ε-viniferin, flexosol A, gnetin H, hemsleyanol D, hopeaphenol, diptoindonesin B, and vaticanol B.

Curcuminoids include, for example, curcumin and shogaol.

Further examples of terpenoids include carotenoids such as lutein, vitamin A, vitamin E, and beta-carotene, as well as steroids such as sitosterol.

Examples of various glycosides include phenolic glycosides such as salicin, β-glucogallin, salicylic acid glucoside, salidroside, gastrodin, poplin, phloridzin, and arbutin, coumarin glycosides such as esculin, flavonoid glycosides such as hesperidin and rutin, and stilbenoid glycosides such as astringin, piceid, and diptoindonesin A.

Furthermore, various polyphenol-based aromatic compounds include, for example, tyrosol, hydroxytyrosol, esculetin, phloretin, rosmarinic acid, salvianic acid A, reticuline, paracoumaryl alcohol, coniferyl alcohol, caffeyl alcohol, etc.

Furthermore, examples of amino acids include phenylalanine and tyrosine.
Furthermore, examples of vitamins include vitamin A, vitamin D, and vitamin E.

Further specific examples of cyclic compounds include aromatic compounds, alicyclic compounds, aliphatic compounds, and heterocyclic compounds.

Among these, examples of aromatic compounds include vanillin, 2-phenylethanol, phenylacetic acid, cinnamic alcohol, isoeugenol, ferulic acid, 4-aminobenzoic acid, anethole, estragole, methyl anthranilate, methyl cinnamate, ethyl cinnamate, phenylacetaldehyde, cinnamic aldehyde, cinnamyl acetate, resorcin, 4-vinylphenol, 4-vinyl-2-methoxyphenol, 3,4-dihydroxystyrene, dopamine, levodopa, hydroquinone, coumarin, 7-hydroxycoumarin, 4-hydroxycoumarin, and xiamenmycin A.

Examples of alicyclic compounds include carveol, perilla alcohol, borneol, methyl jasmonate, 1,8-cineole, L-menthone, valencene, nootkatone, α-pinene, camphene, L-carvone, perilla aldehyde, myrtenal, L-menthyl acetate, and β-ionone.

Furthermore, examples of aliphatic compounds include cis-3-hexenol, cis-3-hexenyl acetate, acetoin, nerol, farnesol, arginine, muconic acid, etc.

Examples of heterocyclic compounds include niacin, niacinamide, maltol, and indole. Among these, an example of indole is 5,6-dihydroxyindole.

On the other hand, examples of derivatives of cyclic compounds include esters, acid anhydrides, amides, acid halides, salts, etc. of the above-mentioned compounds, or all compounds derived from cyclic compounds.

The molecular weight of the cyclic compound or its derivative is not particularly limited, but is preferably 120 to 1,000, and more preferably 130 to 800.

When ring A of the cyclic compound represented by formula (1) is a five-membered saturated or partially saturated ring in which all of the ring-constituting atoms are carbon atoms, it is preferable that one or more of the carbon atoms of ring A to which R ² to R ⁵ and X are bonded are asymmetric carbon atoms. When ring A of the cyclic compound represented by formula (1) is a six-membered saturated or partially saturated ring in which all of the ring-constituting atoms are carbon atoms, it is preferable that one or more of the carbon atoms of ring A to which R ² to R ⁶ and X are bonded are asymmetric carbon atoms.

In such a case, the cyclic compound becomes a stereoisomer. In this case, according to the present embodiment, it is possible to produce a cyclic compound with a high purity of a specific stereoisomer and a low content of other stereoisomers in a high yield. As a result, the complicated process of removing unnecessary stereoisomers is no longer necessary, and the production cost can be reduced.

In addition, in the cyclic compound represented by the above formula (1), when the carbon atom of ring A to which X is bonded is ^C1 , the carbon atom of ring A to which ^R2 is bonded is ^C2 , the carbon atom of ring A to which ^R3 is bonded is ^C3 , the carbon atom of ring A to which ^R4 is bonded is ^C4 , the carbon atom of ring A to which ^R5 is bonded is ^C5 , and the carbon atom of ring A to which ^R6 is bonded is ^C6 , it is preferable that the combination of these carbon atoms being asymmetric carbon atoms is one type selected from the group consisting of the following (a) to (h):

(a) ^C1
(b) ^C2
(c) ^C3
(d) ^C4
(e) ^C1 and ^C4
(f) ^C3 and ^C4
(g) ^C1 , ^C3 and ^C4
(h) ^C3 , ^C4 and ^C5

The following formula (2) is a formula in which the above C ¹ to C ⁶ indications are added to the cyclic compound represented by the above formula (1).

［式（２）中、環Ａは、飽和環、部分飽和環もしくは芳香環の５員環、飽和環、部分飽和環もしくは芳香環の６員環、または、５員環もしくは６員環を含む縮合環であり、Ｘは単結合または１つ以上の炭素数を含む結合であり、Ｙは水素原子またはアルキル基、Ｒ^２～Ｒ^６（環Ａが５員環の場合はＲ^２～Ｒ^５）は、独立して、水素原子、水酸基、アミノ基、アルコキシ基、カルボキシル基またはカルボニル基である。また、Ｃ^１～Ｃ^６は、それぞれ、環Ａの環構成原子としての炭素原子である。］

[In formula (2), ring A is a five-membered saturated ring, partially saturated ring, or aromatic ring, a six-membered saturated ring, partially saturated ring, or aromatic ring, or a fused ring containing a five-membered ring or a six-membered ring; X is a single bond or a bond containing one or more carbon atoms; Y is a hydrogen atom or an alkyl group; R ² to R ⁶ (R ² to R ⁵ when ring A is a five-membered ring) are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group; and C ¹ to C ⁶ are each carbon atoms constituting ring A.]

The cyclic compound and its derivatives are preferably compounds represented by the above formula (2), and more preferably 3-dehydroquinate, 3-dehydroshikimic acid, shikimic acid, chorismic acid, or prephenic acid. These compounds are used in many fields, and their structures are represented by the following formula:

3-dehydroquinate

・3-dehydroshikimic acid

・Shikimic acid

- Chorismic acid

- Prephenic acid

The uses of the above-mentioned cyclic compounds or their derivatives are not particularly limited, but examples of such uses include various chemical products such as fragrance compositions, cosmetic compositions, pharmaceuticals, pesticides, chemicals, materials for electrical and electronic parts, synthetic fibers, resins, and food additives. Cyclic compounds or their derivatives are also used as raw materials for various chemical products. Examples of such raw materials include raw materials for fragrances, cosmetic materials, pharmaceutical materials, pesticide raw materials, chemical raw materials, raw materials for electrical and electronic parts, raw materials for synthetic fibers, raw materials for resins, and raw materials for food additives. Note that raw materials refer to intermediates used in the synthesis of chemical products.

The method for producing the cyclic compound or its derivative of the present invention has been described above based on the embodiments, but the present invention is not limited to these.

For example, the method for producing a cyclic compound or a derivative thereof of the present invention may include any step added to the above embodiment.

Next, specific examples of the present invention will be described.
1. Preparation of cyclic compounds (Example 1)
[1] First, biomass was pretreated to obtain a sugar mixture.

[2] Next, the grown transformant was reacted with a sugar mixture to obtain a culture solution. The culture solution was centrifuged to obtain a supernatant (raw liquid).

[3] Next, the solvent (water) of the obtained raw liquid was evaporated to obtain a concentrated liquid.
[4] Next, activated carbon was added to the concentrated liquid, and the concentrated liquid was subjected to activated carbon treatment. Note that 0.4 g of activated carbon was used per 100 g of the concentrated liquid.

[5] Next, hydrochloric acid was added to lower the pH from 8 to 3, thereby carrying out a crystallization procedure to precipitate the solute.
[6] Next, the precipitated solid was separated by filtration, and the solid precipitate was collected.

[7] Next, the resulting precipitate was washed with a poor solvent and then dried to obtain solid 4-hydroxybenzoic acid (cyclic compound).

(Examples 2 to 9)
Except for changing the production conditions as shown in Table 1, the same procedure as in Example 1 was carried out to obtain 4-hydroxybenzoic acid (cyclic compound).

Comparative Example
[1] First, methane was produced from biomass through microbial fermentation.

[2] Next, methane was used as a raw material and reacted with a catalyst made of zeolite carrying molybdenum and iron to produce benzene, which was then purified by distillation.
[3] Next, 4-hydroxybenzoic acid was derived from benzene.

(Reference example)
A commercially available reagent of 4-hydroxybenzoic acid was prepared.

2. Evaluation of cyclic compounds 2.1 Purity measurement The purity of 4-hydroxybenzoic acid in the cyclic compounds obtained in each of the Examples and Comparative Examples was measured by high performance liquid chromatography (HPLC). The purity was defined as the ratio of the mass of 4-hydroxybenzoic acid to the total mass of the recovered solid (unit: mass%).

The measurement conditions are as follows.
<HPLC analysis conditions for 4-hydroxybenzoic acid>
Column: COSMOSIL 5C18-AR-II (φ4.6 mm × 250 mm) manufactured by Nacalai Tesque Mobile phase: water/methanol/perchloric acid = 4/1/0.0075 (vol/vol/vol) isocratic elution Flow rate: 1 mL/mmin
Column temperature: 40°C
Detection method: Photodiode array (PDA) detector (210 nm)
The measurement results are shown in Table 1.

2.2 Yield Evaluation The yield of 4-hydroxybenzoic acid was measured for the cyclic compounds obtained in each of the Examples and Comparative Examples by high performance liquid chromatography (HPLC) and mass measurement. The yield was calculated by calculating the amount of 4-hydroxybenzoic acid in the raw liquid by high performance liquid chromatography (HPLC), calculating the recovered amount from the mass of the recovered solid and the purity of 4-hydroxybenzoic acid, and expressing it as the ratio (unit: %) of the recovered 4-hydroxybenzoic acid to the amount of 4-hydroxybenzoic acid in the raw liquid.
The measurement results are shown in Table 1.

2.3 Evaluation of Whiteness The ISO whiteness of the cyclic compounds obtained in the Examples and Comparative Examples and the commercially available reagent of the Reference Example was measured using a spectrophotometer.
The measurement results are shown in Table 1.

2.4 Evaluation of Processing Capacity The productivity of the cyclic compound (amount of solid recovered per unit time) in each Example and Comparative Example was relatively evaluated. Specifically, the productivity of the cyclic compound in the Comparative Example was set to 1, and the relative value of the productivity in each Example was calculated.
The calculation results are shown in Table 1.

As is clear from Table 1, in each example, a cyclic compound with high purity was recovered in high yield. In addition, the cyclic compounds recovered in each example had a relatively high degree of whiteness.

S01 Raw liquid preparation step S02 Concentration step S03 Activated carbon treatment step S04 Crystallization step S05 Solid-liquid separation step

Claims (8)

a concentrating step of concentrating the raw material liquid containing 4-hydroxybenzoic acid or a derivative thereof by repeatedly contacting the raw material liquid with a heated heat transfer surface under a pressure of 80 kPa or less and heating the raw material liquid to 20 to 90° C. , thereby evaporating a solvent contained in the raw material liquid;
an activated carbon treatment step of adding 0.01 to 3 g of activated carbon to 100 g of the concentrated raw liquid;
a crystallization step in which the pH of the raw material liquid that has been treated with activated carbon is changed at a temperature in the range of 20 to 60° C. to cause the solute in the raw material liquid to precipitate as a solid;
a solid-liquid separation step of recovering the solid as a powder from the raw material liquid;
The present invention relates to a method for producing 4-hydroxybenzoic acid or a derivative thereof. 2. The method for producing 4-hydroxybenzoic acid or a derivative thereof according to claim 1, wherein the concentrating step includes a process of repeating a pressure reduction operation and a pressure return operation. 3. The method for producing 4-hydroxybenzoic acid or a derivative thereof according to claim 1, wherein the crystallization step includes an operation of adding seed crystals. The method for producing 4-hydroxybenzoic acid or a derivative thereof according to any one of claims 1 to 3 , wherein the temperature of the activated carbon treatment is 30 to 150°C. 5. The method for producing 4 -hydroxybenzoic acid or a derivative thereof according to claim 1, wherein the solid-liquid separation step is a step of filtering and separating the solid from the raw material liquid. 6. The method for producing 4-hydroxybenzoic acid or a derivative thereof according to claim 1, further comprising a raw material liquid preparation step of preparing the raw material liquid from biomass. 7. The method for producing 4-hydroxybenzoic acid or a derivative thereof according to any one of claims 1 to 6 , wherein the powder has an ISO whiteness of 70% or more as measured in accordance with the ISO whiteness test method specified in JIS P 8148 :2001. A method for producing a chemical product , comprising the method for producing 4-hydroxybenzoic acid or a derivative thereof according to any one of claims 1 to 7 .

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