Method for producing freuic acid derivatives, furan derivatives, phthalocyanine derivatives, and isoindoline derivatives

Abstract

The method for producing a folic acid derivative can include an oxidation step of obtaining a folic acid derivative by oxidizing a furfural derivative in a reaction system having a pH of 3 to 12. The method for producing a furan derivative can include a decarboxylation step of obtaining a furan derivative by decarboxylating a folic acid derivative without using a catalyst, or by using an oxide of a transition metal having a valence of 1 to 3 as a catalyst, or by using a high-boiling solvent. The method for producing a furan derivative can include the above oxidation step of obtaining a folic acid derivative and the above decarboxylation step of obtaining a furan derivative. The method for producing a phthalocyanine derivative or an isoindoline derivative can include obtaining a phthalocyanine derivative or an isoindoline derivative from the furan derivative obtained by any one of the above methods for producing a furan derivative.

Description

[Technical Field]

[0001] The present invention relates to a method for producing frucic acid derivatives, furan derivatives, phthalocyanine derivatives, and isoindoline derivatives. [Background technology]

[0002] Furan is used as a raw material in various industries such as pigments, dyes, pharmaceuticals, pesticides, fragrances, polymers, and resins. It has many uses, particularly in the field of organic chemistry, not only as a starting material for synthesizing other organic compounds such as phthalocyanines, but also as a solvent, chemical intermediate, and polymerization initiator. For example, the global furan resin market was valued at US$15.66 billion in 2021 and is projected to reach US$23.68 billion by 2029, representing a compound annual growth rate of 5.3% ("Furran Resin Market - Global Industry Analysis and Forecast by Type, Application and Region (2022-2029)" [online], [Retrieved June 6, 2023] Internet).<URL: https: / / www.maximizemarketresearch.com / market-report / global-furan-resins-market / 116002 / > (See reference). With increasing demand for furans, and due to issues such as the depletion of fossil fuel resources and greenhouse gas emissions, there is a need for a smooth transition from fossil-derived furans to biomass-derived furans, and the development of more efficient new manufacturing technologies is urgently needed.

[0003] Known methods for producing furan include those using furfural, froic acid, 5-hydroxymethylfurfural, butane, butadiene, cis-1,4-dihydroxy-2-butene, tetrahydrofuran, or aldotetrose as starting materials. Furfural is the most frequently used starting material due to its structural usefulness. For example, Non-Patent Document 1 describes a method for producing furan using furfural as a starting material. Non-Patent Document 2 describes a method for producing furan using froic acid as a starting material. It is known that froic acid can be obtained using furfural as a starting material (see, for example, Patent Documents 1, 2, and 3). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Chinese Patent No. 109485624 Specification [Patent Document 2] Chinese Patent No. 111217775 Specification [Non-patent literature]

[0005] [Non-Patent Document 1] Chemical Communications,2012,48,4253-4255 [Non-Patent Document 2] Chemistry European Journal,2013,19,14034-14038 [Non-Patent Document 3] Angewandte Chemie,International Edition,2016,55,36,10806-10810 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, the conventional furan production methods described above require expensive metal catalysts such as Re, Ru, Ir, Pt, Pd, and Au, and in some cases, two or more metal catalysts are necessary. Furthermore, depending on the reaction system, the use of pressurized O2 or H2 may be required to advance the equilibrium state. In addition, since most reactions must be carried out at high temperatures of 140-300°C, high-temperature reactors such as autoclaves are required. These manufacturing constraints limit scale-up and are a major factor in significantly increasing production costs. Furthermore, the conventional method described above for obtaining furic acid from furfural is prone to furfural peroxidation, which easily generates by-products (peroxides), leaving room for further improvement in terms of purity and yield. [Means for solving the problem]

[0007] Therefore, the present invention aims to provide a simpler and less expensive method for producing froic acid derivatives, furan derivatives, phthalocyanine derivatives, and isoindoline derivatives.

[0008] In other words, the present invention is as follows: [1] An oxidation step to obtain a froic acid derivative represented by general formula (2) by oxidizing a furfural derivative represented by general formula (1), as shown in reaction formula (I), the oxidation step includes an oxidation step in which the pH of the reaction system is 3 to 12. [ka] During the ceremony, R 1 This represents a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, or an optionally substituted aryl group having 6 to 12 carbon atoms. R 2 and R 3Each independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 28 carbon atoms which may be substituted, a cycloalkyl group having 3 to 7 carbon atoms which may be substituted, or an aryl group having 6 to 12 carbon atoms which may be substituted, or R 2 and R 3 form a closed ring to form a 5- to 8-membered ring, A method for producing a folic acid derivative. [2] In the oxidation step, as an additive, one or more compounds selected from the group consisting of formic acid, hydrochloric acid, nitric acid, phosphoric acid, phosphoric anhydride, polyphosphoric acid, pyrophosphoric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, phosphorous acid, and salts thereof, and compounds represented by general formulas (A1) to (A4) are used.

Chemical formula

Chemical formula

[10] A method for producing a furan derivative according to any one of [7] to [9], wherein in the oxidation step, O2, H2O2, O3, KMnO4, KClO3, or NaClO is used as the oxidizing agent.

[11] A method for producing a furan derivative according to any one of [7] to

[10] , wherein the oxidation step is performed at a temperature of 0 to 120°C.

[12] A method for producing a furan derivative according to any one of [5] to

[11] , wherein the biomass content of the furan derivative is 1% or more.

[13] A method for producing a phthalocyanine derivative from a furan derivative obtained by a method for producing a furan derivative described in any of [5] to

[12] , Step (A) of obtaining a compound represented by general formula (4) from a furan derivative represented by general formula (3), Step (B) is to obtain a compound represented by general formula (5) from the compound represented by general formula (4) obtained in step (A), Step (C) to obtain a phthalocyanine derivative represented by general formula (6) or (7) from the compound represented by general formula (5) obtained in step (B) above, and Includes, [ka] [ka] [ka] [ka] During the ceremony R 1 This represents a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, or an optionally substituted aryl group having 6 to 12 carbon atoms. R 2 and R 3 Each of these independently represents a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or R 2 and R 3 This means that it forms a closed ring with 5 to 8 members. M 2 This represents a metal atom. A method for producing phthalocyanine derivatives.

[14] A method for producing an isoindoline derivative from a furan derivative obtained by a method for producing a furan derivative described in any of [5] to

[12] , Step (a) of obtaining a compound represented by general formula (4) from a furan derivative represented by general formula (3), Step (b) is to obtain a compound represented by general formula (5) from the compound represented by general formula (4) obtained in step (a), Step (C) to obtain at least one isoindoline derivative represented by general formulas (8) to (11) from the compound represented by general formula (5) obtained in step (b) above, and Includes, [ka] [ka] [ka] [ka] [ka] [ka] During the ceremony R 1 This represents a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, or an optionally substituted aryl group having 6 to 12 carbon atoms. R 2 and R 3 Each of these independently represents a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or R 2 and R 3 This refers to a ring that is closed and forms a 5-8 membered ring. A method for producing isoindoline derivatives. [Effects of the Invention]

[0009] According to the present invention, a simpler and less expensive method for producing freuic acid derivatives, furan derivatives, phthalocyanine derivatives, and isoindoline derivatives can be provided. [Modes for carrying out the invention]

[0010] The following describes in detail a specific embodiment of the present invention. The present invention is not limited to the following description and can be extended within the scope of its gist. In this specification, the term "approximately identical" means not only "identical" but also identical to the extent that it does not impair the effects of the present invention.

[0011] <Method for producing freuic acid derivatives> One embodiment of the method for producing a froic acid derivative includes an oxidation step to obtain a froic acid derivative represented by general formula (2) by oxidizing a furfural derivative represented by general formula (1), as shown in the reaction formula (I) below, wherein the pH of the reaction system is 3 to 12. [ka]

[0012] In general formulas (1) and (2), R 1 R may represent a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, or an optionally substituted aryl group having 6 to 12 carbon atoms. 2 and R 3 Each independently represents a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or R 2 and R 3 This can be considered as forming a 5-8 membered ring through ring closure.

[0013] Examples of the halogen atoms mentioned above include fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms.

[0014] For the linear or branched alkyl groups having 1 to 28 carbon atoms that may be substituted as described above, the number of carbon atoms is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3. Furthermore, one or more non-adjacent -CH2- atoms present in the alkyl group may be replaced with, for example, -C≡C-, -NH-, -N=, -CH=CH-, -O-, -S-, -COO-, -OCO-, or -CO-, and one or more hydrogen atoms present in the alkyl group may be replaced with, for example, a halogen atom such as a fluorine atom or a phenyl group.

[0015] Regarding the substituted cycloalkyl groups having 3 to 7 carbon atoms, the number of carbon atoms is preferably 3 to 6, and more preferably 3 to 5. Furthermore, one or more non-adjacent -CH2- atoms present in the cycloalkyl group may be replaced with, for example, -O-, -S-, -NH-, -N=, -COO-, -OCO-, or -CO-, and one or more hydrogen atoms present in the cycloalkyl group may be replaced with, for example, a halogen atom such as a fluorine atom or a phenyl group.

[0016] For the substituted aryl groups having 6 to 12 carbon atoms, the number of carbon atoms is preferably 6 to 10, and more preferably 6 to 9. One or more non-adjacent -CH= atoms present in the aryl group may be replaced with, for example, -N= atoms, and one or more hydrogen atoms present in the aryl group may be replaced with, for example, halogen atoms such as fluorine atoms or phenyl groups.

[0017] R 2 and R 3 This may involve ring closure to form a 5- to 8-membered ring. Furthermore, the ring structure may contain an -OH group, a -COOH group, -NH-, -S-, or -O-.

[0018] Specific examples of furfural derivatives represented by general formula (1) are not limited to these, but include, for example, the following furfural derivatives (1-1) to (1-7). [ka]

[0019] Specific examples of froic acid derivatives represented by general formula (2) are not limited to these, but include, for example, the following froic acid derivatives (2-1) to (2-7). [ka]

[0020] <Oxidation process> In the oxidation step of the method for producing a furfural derivative according to the above embodiment, a furfural derivative represented by general formula (2) can be obtained by the oxidation reaction of a furfural derivative represented by general formula (1). In this oxidation reaction, the pH of the reaction system can be maintained within the range of 3 to 12 throughout the reaction. Generally, peroxidation is likely to occur in the oxidation reaction of furfural derivatives, but in the oxidation reaction of the above embodiment, by controlling the pH of the reaction system within the range of 3 to 12, it is possible to suppress the generation of peroxides (e.g., furanone derivatives, succinic acid derivatives, maleic acid derivatives, fumaric acid derivatives, etc.) due to excessive oxidation, so that furfural derivatives can be obtained with high purity and yield. The pH of the reaction system changes as the oxidation reaction progresses, but it is preferable that it remains within the range of 3 to 12 throughout the reaction. The lower limit of pH is preferably 4 or higher, preferably 5 or higher, preferably 6 or higher, and preferably 7 or higher. The upper limit of pH may be 11 or lower, or 10 or lower. These upper and lower limits may be either one or any combination. One method for controlling the pH of the reaction system within the above range is to add the additives described later.

[0021] The oxidizing agent used in the oxidation reaction is not particularly limited as long as it allows the reaction to proceed favorably, but for example, O2, H2O2, O3, KMnO4, KClO3, or NaClO may be used. Among these oxidizing agents, H2O2 is preferred. The amount of oxidizing agent added is not particularly limited as long as it is sufficient to allow the reaction to proceed well. However, relative to the furfural derivative represented by general formula (1), for example, the lower limit is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 100 mol% or more. Similarly, the upper limit is preferably 1000 mol% or less, more preferably 800 mol% or less, and even more preferably 400 mol% or less. These upper and lower limits may be used individually or in any combination.

[0022] In the oxidation reaction, it is preferable to use one or more compounds selected from the group consisting of formic acid, hydrochloric acid, nitric acid, phosphoric acid, phosphoric anhydride, polyphosphoric acid, pyrophosphoric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, phosphorous acid, and salts thereof, as well as compounds represented by general formulas (A1) to (A4), as additives. [ka]

[0023] In general formulas (A1) and (A2), X is an -OH group, -OM 1 Base, or -R 4 It can be used to represent M 1 R is often used to represent alkali metal atoms. 4 Y may represent a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, or an optionally substituted aryl group having 6 to 12 carbon atoms. 1 This includes hydrogen atoms, alkali metal atoms, and -COR 5 Alternatively, it may represent a functional group represented by general formula (B), R 5X may represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 28 carbon atoms (which may be substituted), a cycloalkyl group having 3 to 7 carbon atoms (which may be substituted), or an aryl group having 6 to 12 carbon atoms (which may be substituted). Z may represent a sulfur atom or a phosphorus atom. W may represent an oxygen atom or be substantially the same as X above. n1 may be an integer from 1 to 10.

[0024] M 1 Examples of alkali metal atoms include Li, Na, or K. Y 1 Examples of alkali metal atoms include Li, Na, K, Rb, or Cs. R 4 and R 5 The preferred range and preferred examples of R in the above general formulas (1) and (2) are 1 The same can be applied as to the points mentioned above. n1 is preferably an integer between 1 and 8, and more preferably an integer between 1 and 5.

[0025] [ka]

[0026] In general formula (B), R 6 This may represent a hydrogen atom, a linear or branched alkyl group having 1 to 28 carbon atoms (which may be substituted), a cycloalkyl group having 3 to 7 carbon atoms (which may be substituted), or an aryl group having 6 to 12 carbon atoms (which may be substituted). R 6 The preferred range and preferred examples of R in the above-mentioned general formulas (1) and (2) are 1 The same may apply as to the examples given. Among these functional groups, protonated triethylamine is preferred.

[0027] X is particularly preferably a -CH3 group. Y 1It is more preferably a hydrogen atom or an alkali metal atom, and even more preferably a hydrogen atom, Li, Na, K, Rb, or Cs.

[0028] [ka]

[0029] In general formulas (A3) and (A4), X may be considered, independently, to be substantially the same as X in general formulas (A1) and (A2) above. 2 n2 may represent an alkaline earth metal atom. Z may be approximately the same as Z in the above general formulas (A1) and (A2). W may represent an oxygen atom, or be approximately the same as X in the above general formulas (A1) and (A2). n2 and n3 may each be an integer between 1 and 10, independently of each other. Y 2 Examples of alkaline earth metal atoms include Be, Mg, Ca, Sr, or Ba. n2 is preferably an integer between 1 and 8, and more preferably an integer between 1 and 5. n3 is preferably an integer between 1 and 8, and more preferably an integer between 1 and 5.

[0030] The above additives are more preferably one or more compounds selected from the group consisting of phosphates and compounds represented by general formulas (A1) to (A4), and even more preferably one or more compounds selected from the group consisting of NaH2PO4, potassium acetate, sodium acetate, and triethylammonium acetate. In the oxidation reaction of furfural derivatives, as the reaction progresses, the pH of the reaction system decreases (i.e., shifts towards the acidic side), making it easier for peroxides to form, and these peroxides then act as autocatalysts. However, by adding an additive, the reaction system is neutralized, making it easier to maintain the pH between 3 and 12, and allowing furfural derivatives to be obtained with higher purity and yield.

[0031] The amount of additive added relative to the furfural derivative represented by general formula (1) is preferably 50 mol% or more, 70 mol% or more, and 100 mol% or more as a lower limit. The upper limit is preferably 500 mol% or less, 300 mol% or less, and 200 mol% or less. These upper and lower limits may be used individually or in any combination. The timing of adding the additive is not particularly limited, as long as the pH of the reaction system can be maintained within the range of 3 to 12. The entire amount of the additive can be added before or during the reaction at any time. Alternatively, it may be added in several portions before or during the reaction.

[0032] The solvent used in the oxidation reaction is not particularly limited as long as it allows the reaction to proceed favorably. For example, water, 1,4-dioxane, isobutyl methyl ketone, toluene, xylene, alkylbenzene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, ethanol, methanol, isopropanol, tert-amyl alcohol, or ethyl acetate may be used. Furthermore, the above oxidation reaction will also proceed without a solvent.

[0033] The oxidation reaction temperature is preferably 0 to 120°C, more preferably 5 to 100°C, and even more preferably 30 to 90°C. The oxidation reaction in the above embodiment can be carried out at a lower temperature than in the conventional technology. In the conventional technology, it is considered necessary to carry out the reaction at a high temperature (140 to 300°C). In certain embodiments, a high-temperature reactor is not required, thereby reducing equipment costs and allowing for easy scale-up. The duration of the oxidation reaction is not particularly limited and may be set according to the reaction temperature, the type of additives and oxidizing agent, etc.

[0034] The method for producing a froic acid derivative according to one embodiment may include other steps, such as a purification step to remove reaction by-products.

[0035] One embodiment of the method for producing a froic acid derivative is simple and inexpensive, can be carried out using standard laboratory equipment, and can be easily scaled up. Furthermore, because the reaction is carried out under relatively mild reaction conditions, it is easy to control the reaction, and the generation of by-products (peroxides) due to peroxidation is minimal.

[0036] According to the method for producing a froic acid derivative of one embodiment, a froic acid derivative of high purity can be obtained. The purity (content) of the froic acid derivative is preferably 95.0% or higher at the lower limit, more preferably 98.0% or higher, and even more preferably 99.0% or higher. The upper limit is not particularly limited, with 100% being the most preferred, but it may be 99.999% or lower, or 99.5% or lower. These upper and lower limits may be either one or any combination. The content of reaction by-products such as peroxides is preferably 5.0% or less, more preferably 2.0% or less, and even more preferably 1.0% or less. The lower limit is not particularly limited, with 0% being the most preferred, but it may be 0.01% or more, or 0.1% or more. These upper and lower limits may be set individually or in any combination. The purity (content) of the froic acid derivative and the content of the reaction by-products can be determined, for example, by quantifying the froic acid and reaction by-products separately using gas chromatography-mass spectroscopy (GC-MS).

[0037] Furthermore, according to the method for producing a froic acid derivative of one embodiment, a froic acid derivative can be obtained in high yield. The lower limit of the yield of the froic acid derivative is preferably 10% or more, more preferably 50% or more, and even more preferably 80% or more. The upper limit is not particularly limited, with 100% being the most preferred, but it may be 95% or less, or 90% or less. These upper and lower limits may be either one or any combination.

[0038] <Method for producing furan derivatives> A method for producing a furan derivative according to one embodiment includes a decarboxylation step to obtain a furan derivative represented by general formula (3) by decarboxylating a frucic acid derivative represented by general formula (2), as shown in reaction formula (II), and comprises a decarboxylation step carried out without a catalyst or using an oxide of a 1- to 3-valent transition metal as a catalyst. [ka]

[0039] In general formulas (2) and (3), R 1 R may represent a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, or an optionally substituted aryl group having 6 to 12 carbon atoms. 2 and R 3 Each independently represents a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or R 2 and R 3 This can be considered as forming a 5-8 membered ring through ring closure.

[0040] The above R 1 ~R 3 The preferred range and preferred examples of R in the method for producing the froic acid derivative of the above embodiment are the R of general formulas (1) and (2). 1 ~R 3 The same can be applied as to the points mentioned above. Specific examples of froic acid derivatives represented by general formula (2) include those similar to those listed in the method for producing the froic acid derivative in the above embodiment.

[0041] Specific examples of furan derivatives represented by general formula (3) are not limited to these, but include, for example, the following furfural derivatives (3-1) to (3-7). [ka]

[0042] <Decarboxylation process> In the decarboxylation step of the method for producing a furan derivative according to the above embodiment, a furan derivative represented by general formula (3) can be obtained by the decarboxylation reaction of a freuic acid derivative represented by general formula (2). Unlike conventional techniques that use expensive and valuable metal catalysts (Re, Ru, Ir, Pt, Pd, Au, etc.), this decarboxylation reaction can be carried out without a catalyst, or using an inexpensive and readily available oxide of a 1- to 3-valent transition metal as a catalyst, thus making it easy to scale up and reducing manufacturing costs.

[0043] When carrying out a decarboxylation reaction without a catalyst, it is necessary to raise the reaction temperature relatively high in order to ensure that the decarboxylation proceeds smoothly. Therefore, it is more preferable to use oxides of 1- to 3-valent transition metals as catalysts. When a catalyst is used in a decarboxylation reaction, specific examples of catalysts include Cu2O, CuO, FeO, and Fe2O3. Among these catalysts, Cu2O is preferred. The amount of catalyst added is not particularly limited as long as it is sufficient to allow the reaction to proceed smoothly. However, relative to the frucic acid derivative represented by general formula (2), the lower limit is preferably 0.001 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.1 mol% or more. The upper limit is preferably 100 mol% or less, more preferably 50 mol% or less, and even more preferably 20 mol% or less. These upper and lower limits may be used individually or in any combination.

[0044] The solvent used in the decarboxylation reaction is not particularly limited as long as it allows the reaction to proceed smoothly. From the viewpoint of suppressing the sublimation of furan derivatives that occur when the reaction temperature is high, a high-boiling point solvent is preferred, such as dimethylacetamide (DMA), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dodecyl alcohol, diethylene glycol monobutyl ether, hexadecane, or alkylbenzene. Among these solvents, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or hexadecane are preferred. While the term "high-boiling point solvent" generally refers to solvents with a boiling point between 150°C and 280°C, other boiling points can also be considered high-boiling points, and any boiling point exceeding the aforementioned range can also be considered high-boiling point. Furthermore, the above decarboxylation reaction proceeds even without a solvent.

[0045] The temperature of the decarboxylation reaction is not particularly limited as long as it is a temperature at which the reaction proceeds favorably. For example, when the reaction is carried out without a catalyst, 50 to 300°C is preferred, 80 to 290°C is more preferred, and 100 to 280°C is even more preferred. When an oxide of a 1- to 3-valent transition metal is used as a catalyst, 50 to 280°C is preferred, 80 to 270°C is more preferred, and 100 to 250°C is even more preferred. The duration of the decarboxylation reaction is not particularly limited and may be set according to the reaction temperature, type of catalyst, etc.

[0046] One embodiment of the method for producing a furan derivative is a decarboxylation step to obtain a furan derivative represented by general formula (3) by decarboxylating a freuic acid derivative represented by general formula (2), as shown in reaction formula (II), and includes a decarboxylation step in which decarboxylation is carried out using a high-boiling point solvent. [ka]

[0047] In general formulas (2) and (3), R 1may represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 28 carbon atoms which may be substituted, a cycloalkyl group having 3 to 7 carbon atoms which may be substituted, or an aryl group having 6 to 12 carbon atoms which may be substituted. R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 28 carbon atoms which may be substituted, a cycloalkyl group having 3 to 7 carbon atoms which may be substituted, an aryl group having 6 to 12 carbon atoms which may be substituted, or R 2 and R 3 may be closed to form a 5- to 8-membered ring.

[0048] The preferred ranges and preferred examples of the above R 1 to R 3 may be the same as those listed for R 1 to R 3 in the general formulas (1) and (2) in the method for producing the folic acid derivative of the above-described embodiment. Specific examples of the folic acid derivative represented by the general formula (2) include the same ones as those listed in the method for producing the folic acid derivative of the above-described embodiment. Specific examples of the furan derivative represented by the general formula (3) include the same ones as those listed above.

[0049] 〈Decarboxylation step〉 In the decarboxylation step in the method for producing a furan derivative according to an embodiment, a furan derivative represented by the general formula (3) can be obtained by a decarboxylation reaction of the folic acid derivative represented by the general formula (2). The decarboxylation reaction may cause undesirable sublimation of the furan derivative at a high reaction temperature. Therefore, a catalyst is usually used to lower the reaction temperature and assist in preventing sublimation. In the decarboxylation step of the above-described embodiment, by using a high-boiling solvent, even when the reaction temperature is high, the decarboxylation reaction can be successfully advanced without causing undesirable sublimation of the furan derivative. In this way, the decarboxylation reaction can be successfully carried out with or without using a catalyst.

[0050] Specific examples of high-boiling point solvents include those similar to those listed above.

[0051] The decarboxylation reaction may be carried out with or without a catalyst. When a catalyst is used in the decarboxylation reaction, the catalyst is not particularly limited as long as it facilitates the reaction. From the viewpoint of ease of scale-up and reduction of manufacturing costs, the catalyst is preferably an oxide of a 1- to 3-valent transition metal. Specific examples of 1- to 3-valent transition metal oxides are the same as those listed above. The amount of catalyst added is not particularly limited as long as it is sufficient to allow the reaction to proceed smoothly. However, relative to the frucic acid derivative represented by general formula (2), the lower limit is preferably 0.001 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.1 mol% or more. The upper limit is preferably 100 mol% or less, more preferably 50 mol% or less, and even more preferably 20 mol% or less. These upper and lower limits may be used individually or in any combination.

[0052] The temperature of the decarboxylation reaction is not particularly limited as long as it allows the reaction to proceed smoothly. For example, when the reaction is carried out without a catalyst, 50 to 300°C is preferred, 80 to 290°C is more preferred, and 100 to 280°C is even more preferred. When an oxide of a 1- to 3-valent transition metal is used as a catalyst, 50 to 280°C is preferred, 80 to 270°C is more preferred, and 100 to 250°C is even more preferred. The duration of the decarboxylation reaction is not particularly limited and may be set according to the reaction temperature, type of catalyst, etc.

[0053] Another embodiment of a method for producing a furan derivative includes an oxidation step, as shown in reaction formula (III), in which a furfural derivative represented by general formula (1) is oxidized to obtain a froic acid derivative represented by general formula (2), wherein the pH of the reaction solution is 3 to 12; and a decarboxylation step, as shown in reaction formula (III), in which the froic acid derivative represented by general formula (2) obtained in the oxidation step is decarboxylated to obtain a furan derivative represented by general formula (3), wherein the decarboxylation is carried out without a catalyst or using an oxide of a 1-3 valent transition metal as a catalyst. [ka]

[0054] In general formulas (1) to (3), R 1 R may represent a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, or an optionally substituted aryl group having 6 to 12 carbon atoms. 2 and R 3 Each independently represents a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or R 2 and R 3 This can be considered as forming a 5-8 membered ring through ring closure.

[0055] The above R 1 ~R 3 The preferred range and preferred examples of R in the method for producing the froic acid derivative of the above embodiment are the R of general formulas (1) and (2). 1 ~R 3 The same can be applied as to the points mentioned above. Furthermore, specific examples of furfural derivatives represented by general formula (1), froic acid derivatives represented by general formula (2), and furan derivatives represented by general formula (3) are the same as those listed above.

[0056] <Oxidation process> In the oxidation step of the method for producing a furan derivative according to one embodiment, a furfural derivative represented by general formula (1) can be oxidized to obtain a froic acid derivative represented by general formula (2). In this oxidation reaction, the pH of the reaction system can be maintained within the range of 3 to 12 throughout the reaction. Generally, peroxidation is likely to occur in the oxidation reaction of froic acid derivatives, but in the oxidation reaction of the above embodiment, by controlling the pH of the reaction system within the range of 3 to 12, it is possible to suppress the generation of peroxides (e.g., succinic acid derivatives, furanone derivatives, maleic acid derivatives, fumaric acid derivatives, etc.) due to excessive oxidation, so that froic acid derivatives can be obtained with high purity and yield.

[0057] The preferred pH range of the reaction system may be the same as that given for the oxidation step in the above-mentioned method for producing the froic acid derivative. One method for controlling the pH of the reaction system within the above range is to add an additive, similar to the oxidation step in the above-mentioned method for producing the froic acid derivative.

[0058] In the oxidation reaction, the oxidizing agent, additive, and solvent listed in the oxidation step of the above-mentioned method for producing the froic acid derivative can be used. Furthermore, the timing of adding the additive may be the same as that of the oxidation step in the above-described method for producing the froic acid derivative.

[0059] The oxidation reaction temperature can be the same as that of the oxidation step in the above-mentioned method for producing the froic acid derivative. The oxidation reaction in the above embodiment can be carried out at a lower temperature than in the conventional technology. In the conventional technology, it is considered necessary to carry out the reaction at a high temperature (140-300°C). In certain embodiments, a high-temperature reactor is not required, thereby reducing equipment costs and allowing for easy scale-up. The duration of the oxidation reaction is not particularly limited and may be set according to the reaction temperature, the type of additives and oxidizing agent, etc.

[0060] <Decarboxylation process> In the decarboxylation step of one embodiment of the method for producing a furan derivative, a furan derivative represented by general formula (3) can be obtained by the decarboxylation reaction of a freuic acid derivative represented by general formula (2). This decarboxylation reaction can use a froic acid derivative represented by general formula (2), obtained in high purity and high yield by the oxidation step described above, as a raw material, thus enabling the production of furan derivatives in high purity and high yield. Unlike conventional techniques that use expensive and valuable metal catalysts (such as Re, Ru, Ir, Pt, Pd, and Au), this decarboxylation reaction can be carried out without a catalyst, or using inexpensive and readily available oxides of 1- to 3-valent transition metals as catalysts. Therefore, it is easy to scale up and manufacturing costs can be reduced. When carrying out a decarboxylation reaction without a catalyst, the reaction temperature is usually set to a relatively high temperature to ensure good decarboxylation. Therefore, it is more preferable to use oxides of 1- to 3-valent transition metals as catalysts.

[0061] The catalysts and solvents listed above can be used in the decarboxylation reaction. The temperature of the decarboxylation reaction can be the same as the temperature mentioned in the above embodiment. The duration of the decarboxylation reaction is not particularly limited and may be set according to the reaction temperature, type of catalyst, etc.

[0062] In the method for producing furan derivatives according to the above embodiment, the first oxidation step can be carried out under relatively mild reaction conditions, making it easy to control the reaction and resulting in less by-product (peroxide) generation due to peroxidation. Furthermore, since the second decarboxylation step can be carried out using the freuic acid derivative obtained in high purity and high yield by the first oxidation step, furan derivatives can be produced in high purity and yield. In addition, the reaction can be carried out without a catalyst or using an inexpensive and readily available catalyst. Therefore, although the method for producing the furan derivative in the above embodiment involves two steps, it is a simple and inexpensive manufacturing method that can be carried out using ordinary laboratory equipment, making it easy to scale up and reducing manufacturing costs.

[0063] Another embodiment of the method for producing a furan derivative includes an oxidation step, as shown in reaction formula (III), in which a furfural derivative represented by general formula (1) is oxidized to obtain a froic acid derivative represented by general formula (2), wherein the pH of the reaction solution is 3 to 12; and a decarboxylation step, as shown in reaction formula (III), in which the froic acid derivative represented by general formula (2) obtained in the oxidation step is decarboxylated to obtain a furan derivative represented by general formula (3), wherein the decarboxylation is carried out using a high-boiling point solvent. [ka]

[0064] In general formulas (1) to (3), R 1 R may represent a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, or an optionally substituted aryl group having 6 to 12 carbon atoms. 2 and R 3 Each independently represents a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or R 2 and R 3 This can be considered as forming a 5-8 membered ring through ring closure.

[0065] The above R 1 ~R 3 The preferred range and preferred examples of R in the method for producing the froic acid derivative of the above embodiment are the R of general formulas (1) and (2). 1 ~R 3 The same can be applied as to the points mentioned above. Furthermore, specific examples of furfural derivatives represented by general formula (1), froic acid derivatives represented by general formula (2), and furan derivatives represented by general formula (3) are the same as those listed above.

[0066] <Oxidation process> In the oxidation step of the method for producing a furan derivative according to one embodiment, a furfural derivative represented by general formula (1) can be oxidized to obtain a froic acid derivative represented by general formula (2). In this oxidation reaction, the pH of the reaction system can be maintained within the range of 3 to 12 throughout the reaction. Generally, peroxidation is likely to occur in the oxidation reaction of froic acid derivatives, but in the oxidation reaction of the above embodiment, by controlling the pH of the reaction system within the range of 3 to 12, it is possible to suppress the generation of peroxides (e.g., succinic acid derivatives, furanone derivatives, maleic acid derivatives, fumaric acid derivatives, etc.) due to excessive oxidation, so that froic acid derivatives can be obtained with high purity and yield.

[0067] The preferred pH range of the reaction system may be the same as that given for the oxidation step in the method for producing the froic acid derivative of the above embodiment. One method for controlling the pH of the reaction system within the above range is to add an additive, similar to the oxidation step in the method for producing the froic acid derivative of the above embodiment.

[0068] In the oxidation reaction, the oxidizing agent, additive, and solvent listed in the oxidation step of the method for producing the froic acid derivative of the above embodiment can be used. Furthermore, the timing of adding the additive may be the same as that of the oxidation step in the above-described method for producing the froic acid derivative.

[0069] The oxidation reaction temperature can be the same as that of the oxidation step in the above-mentioned method for producing the froic acid derivative. The oxidation reaction in the above embodiment can be carried out at a lower temperature than in the conventional technology. In the conventional technology, it is considered necessary to carry out the reaction at a high temperature (140-300°C). In certain embodiments, a high-temperature reactor is not required, thereby reducing equipment costs and allowing for easy scale-up. The duration of the oxidation reaction is not particularly limited and may be set according to the reaction temperature, the type of additives and oxidizing agent, etc.

[0070] <Decarboxylation process> In the decarboxylation step of the method for producing a furan derivative according to one embodiment, a furan derivative represented by general formula (3) can be obtained by the decarboxylation reaction of a frucic acid derivative represented by general formula (2). In the decarboxylation reaction, undesirable sublimation of the furan derivative may occur at high reaction temperatures. Therefore, a catalyst is usually used to lower the reaction temperature and help prevent sublimation. In the decarboxylation step of the above embodiment, by using a high-boiling point solvent, the decarboxylation reaction can be carried out successfully without undesirable sublimation of the furan derivative, even at high reaction temperatures. In this way, the decarboxylation reaction can be carried out successfully with or without the use of a catalyst.

[0071] Specific examples of high-boiling point solvents include those similar to those listed above.

[0072] The decarboxylation reaction may be carried out with or without a catalyst. Specific examples of catalysts are the same as those mentioned above. The temperature for the decarboxylation reaction can be the same as described above. The duration of the decarboxylation reaction is not particularly limited and may be set according to the reaction temperature, type of catalyst, etc.

[0073] In the method for producing furan derivatives according to the above embodiment, the first oxidation step is carried out under relatively mild reaction conditions, making it easy to control the reaction and resulting in minimal generation of by-products (peroxides) due to peroxidation. Furthermore, since the freuic acid derivative obtained in high purity and high yield through the first oxidation step is used in the second decarboxylation step in a high-boiling point solvent, furan derivatives can be produced in high purity and high yield. Therefore, although the method for producing the furan derivative in the above embodiment involves two steps, it is a simple and inexpensive manufacturing method that can be carried out using ordinary laboratory equipment, making it easy to scale up and reducing manufacturing costs.

[0074] The method for producing a furan derivative according to one embodiment may include other steps besides the oxidation step and the decarboxylation step described above. For example, it may include a purification step to remove reaction by-products.

[0075] According to the method for producing a furan derivative of one embodiment, a furan derivative of high purity can be obtained. The purity (content) of the furan derivative is preferably 99.5% or higher at the lower limit, more preferably 99.6% or higher, and even more preferably 99.7% or higher. The upper limit is not particularly limited, with 100% being the most preferred, but it may be 99.999% or lower, or 99.98% or lower. These upper and lower limits may be either one or any combination. The content of reaction by-products is preferably 0.5% or less at the upper limit, more preferably 0.3% or less, and even more preferably 0.2% or less. The lower limit is not particularly limited, with 0% being the most preferred, but it may be 0.001% or more, or 0.01% or more. These upper and lower limits may be set individually or in any combination. The purity (content) of the furan derivative and the content of the reaction by-products can be determined, for example, by quantifying the furan derivative and the reaction by-products respectively using gas chromatography-mass spectroscopy (GC-MS).

[0076] Furthermore, according to the method for producing furan derivatives of one embodiment, furan derivatives can be obtained in high yield. The lower limit of the yield of the furan derivative is preferably 99.5% or higher, more preferably 99.6% or higher, and even more preferably 99.7% or higher. The upper limit is not particularly limited, with 100% being the most preferred, but it may be 99.99% or lower, or 99.98% or lower. These upper and lower limits may be either one or any combination.

[0077] <Method for producing phthalocyanine derivatives> In one embodiment of the method for producing a phthalocyanine derivative, the furan derivative represented by general formula (3) obtained by the method for producing a furan derivative in the above embodiment can be used. A method for producing a phthalocyanine derivative according to one embodiment includes the steps of: (A) obtaining a compound represented by general formula (4) from a furan derivative represented by general formula (3); (B) obtaining a compound represented by general formula (5) from the compound represented by general formula (4) obtained in step (A); and (C) obtaining a phthalocyanine derivative represented by general formula (6) or (7) from the compound represented by general formula (5) obtained in step (B).

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka] In general formulas (4) to (7), R 1 R may represent a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, or an optionally substituted aryl group having 6 to 12 carbon atoms. 2 and R 3 Each independently represents a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or R 2 and R 3 This can be considered as forming a 5-8 membered ring through ring closure. In general formula (6), M2 This can be considered to represent a metal atom. The above R 1 ~R 3 The preferred range and preferred examples of R in the method for producing the froic acid derivative of the above embodiment are the R of general formulas (1) and (2). 1 ~R 3 The same can be applied as to the points mentioned above.

[0082] [Process (A)] In step (A), a compound represented by general formula (4) (DA intermediate) is produced by subjecting a furan derivative represented by general formula (3) and maleic anhydride to a Diels-Alder reaction. Specific examples of furan derivatives represented by general formula (3) are the same as those listed above.

[0083] Specific examples of compounds represented by general formula (4) (DA intermediates) are not limited to these, but include, for example, the following compounds (4-1) to (4-11). [ka]

[0084] The reaction solvent is not particularly limited as long as it allows the reaction to proceed smoothly, but chloroform, dioxane, ethyl acetate, alkylbenzene, toluene, xylene, or diethyl ether are preferred.

[0085] The reaction temperature is not particularly limited as long as it is a temperature at which the reaction proceeds favorably, but the lower limit is preferably -10°C or higher, more preferably 0°C or higher, even more preferably 10°C or higher, and particularly preferably 15°C or higher. The upper limit is preferably 100°C or lower, more preferably 80°C or lower, even more preferably 70°C or lower, and particularly preferably 50°C or lower. These upper and lower limits may be set individually or in any combination.

[0086] The reaction pressure is not particularly limited as long as it is at a temperature that allows the reaction to proceed suitably, but the lower limit is preferably 0.1 MPa or higher, preferably 0.2 MPa or higher, preferably 0.3 MPa or higher, and preferably 0.4 MPa or higher. The upper limit is preferably 5 MPa or lower, preferably 3 MPa or lower, preferably 1 MPa or lower, preferably 0.9 MPa or lower, preferably 0.8 MPa or lower, preferably 0.7 MPa or lower, preferably 0.6 MPa or lower, and preferably 0.5 MPa or lower. These upper and lower limits may be used individually or in any combination.

[0087] [Process (B)] In step (B), the compound represented by general formula (4) (DA intermediate) obtained in step (A) can be ring-opened and dehydrated to produce the compound represented by general formula (5) (phthalic anhydride derivative).

[0088] Specific examples of compounds represented by general formula (5) (phthalic anhydride derivatives) are not limited to these, but include, for example, the following compounds (5-1) to (5-11). [ka]

[0089] The reaction solvent is not particularly limited as long as it allows the reaction to proceed smoothly, but water, acetonitrile, toluene, xylene, alkylbenzene, or a mixture thereof is preferred. Furthermore, the ring-opening dehydration reaction can also be carried out without a solvent.

[0090] The reaction temperature is not particularly limited as long as it is a temperature that allows the reaction to proceed smoothly, but the lower limit is preferably 20°C or higher, preferably 25°C or higher, preferably 30°C or higher, preferably 35°C or higher, and preferably 40°C or higher. The upper limit is preferably 150°C or lower, preferably 140°C or lower, preferably 130°C or lower, preferably 120°C or lower, preferably 110°C or lower, and preferably 100°C or lower. These upper and lower limits may be used individually or in any combination.

[0091] The above ring-opening dehydration reaction preferably uses a catalyst. As the catalyst, the same compounds as those listed as additives in the oxidation step of the method for producing the froic acid derivative in the above embodiment can be used. Other compounds may also be used. The amount of catalyst added relative to the compound represented by general formula (4) (DA intermediate) is preferably 0.1 mol% or more, 0.5 mol% or more, 1 mol% or more, 5 mol% or more, 10 mol% or more, 20 mol% or more, 50 mol% or more, 70 mol% or more, 100 mol% or more, 150 mol% or more, 200 mol% or more, 250 mol% or more, and 300 mol% or more as a lower limit. The upper limit is preferably 3000 mol% or less, 2500 mol% or less, 2000 mol% or less, 1500 mol% or less, 1000 mol% or less, and 500 mol% or less. These upper and lower limits may be used individually or in any combination.

[0092] [Process (C)] In step (C), the compound represented by general formula (5) (phthalic anhydride derivative) obtained in step (B) above is mixed with urea and M 2 X(M 2 A phthalocyanine derivative represented by general formula (6) is produced by reacting it with a metal atom (where X is a halogen atom) in the presence of a catalyst. Furthermore, by performing a demetallation reaction on the obtained phthalocyanine derivative represented by general formula (6), a phthalocyanine derivative represented by general formula (7) can be produced.

[0093] The reaction solvent is not particularly limited as long as it allows the reaction to proceed smoothly, but alkylbenzene is preferred. Furthermore, the above reaction can also be carried out without a solvent.

[0094] The reaction temperature is not particularly limited as long as it is a temperature that allows the reaction to proceed smoothly, but the lower limit is preferably 100°C or higher, preferably 110°C or higher, preferably 120°C or higher, preferably 130°C or higher, preferably 140°C or higher, and preferably 150°C or higher. The upper limit is preferably 250°C or lower, preferably 240°C or lower, preferably 230°C or lower, preferably 220°C or lower, preferably 210°C or lower, and preferably 200°C or lower. These upper and lower limits may be used individually or in any combination.

[0095] M 2 X's M 2 can be used to represent a metal atom, and is preferably Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, or Pb, more preferably Al, Fe, Cu, or Zn, and even more preferably Cu or Zn. M 2 X may represent a halogen atom, and for example, it is preferably a chlorine atom.

[0096] The catalyst is not particularly limited as long as it facilitates the reaction, but a molybdenum catalyst is preferred, and ammonium molybdate(IV) tetrahydrate is more preferred. The amount of the catalyst added is preferably 0.001 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.1 mol% or more, relative to the compound represented by general formula (5) (phthalic anhydride derivative), as a lower limit. As an upper limit, it is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 3 mol% or less. These upper and lower limits may be set individually or in any combination.

[0097] The demetallation reaction of phthalocyanine derivatives represented by general formula (6) is not particularly limited, but examples include the method described in Chemical Communication, 2009, 1970-1971.

[0098] The method for producing a phthalocyanine derivative according to one embodiment is simple and inexpensive because it can produce the furan derivative, which is the raw material, using the method for producing a furan derivative according to the above embodiment. It can be carried out using ordinary laboratory equipment, is easy to scale up, and reduces manufacturing costs.

[0099] <Method for producing isoindoline derivatives> In one embodiment of the method for producing an isoindoline derivative, the furan derivative represented by general formula (3) obtained by the method for producing a furan derivative of the above embodiment can be used. A method for producing an isoindoline derivative according to one embodiment includes the steps of: (a) obtaining a compound represented by general formula (4) from a furan derivative represented by general formula (3); (b) obtaining a compound represented by general formula (5) from the compound represented by general formula (4) obtained in step (a); and (C) obtaining at least one isoindoline derivative represented by general formulas (8) to (11) from the compound represented by general formula (5) obtained in step (b). [ka] [ka] [ka] [ka] [ka] [ka] In general formulas (4), (5) and (8) to (11), R 1 R may represent a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, or an optionally substituted aryl group having 6 to 12 carbon atoms. 2 and R 3Each independently represents a hydrogen atom, a halogen atom, an optionally substituted linear or branched alkyl group having 1 to 28 carbon atoms, an optionally substituted cycloalkyl group having 3 to 7 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or R 2 and R 3 This can be considered as forming a 5-8 membered ring through ring closure. The above R 1 ~R 3 The preferred range and preferred examples of R in the method for producing the froic acid derivative of the above embodiment are the R of general formulas (1) and (2). 1 ~R 3 The same can be applied as to the points mentioned above.

[0100] [Process (a)] In step (a), a compound represented by general formula (4) (DA intermediate) is produced by subjecting a furan derivative represented by general formula (3) and maleic anhydride to a Diels-Alder reaction. Specific examples of furan derivatives represented by general formula (3) are the same as those listed above. Specific examples of the compound represented by general formula (4) (DA intermediate) include those similar to those listed in step (A) of the method for producing the phthalocyanine derivative in the embodiment described above.

[0101] Preferred reaction solvents include those similar to those listed in step (A) of the method for producing the phthalocyanine derivative in the above-described embodiment. The preferred ranges for reaction temperature and reaction pressure may be the same as those listed in step (A) of the method for producing the phthalocyanine derivative in the above-described embodiment.

[0102] [Step (b)] In step (b), the compound represented by general formula (4) (DA intermediate) obtained in step (a) can be ring-opened and dehydrated to produce the compound represented by general formula (5) (phthalic anhydride derivative).

[0103] Specific examples of compounds represented by general formula (5) (phthalic anhydride derivatives) include those similar to those listed in step (B) of the method for producing phthalocyanine derivatives in the embodiment described above.

[0104] Preferred reaction solvents are the same as those listed in step (B) of the method for producing the phthalocyanine derivative in the embodiment described above. The ring-opening dehydration reaction can also be carried out without a solvent. The preferred range of reaction temperature may be the same as that given in step (B) of the method for producing the phthalocyanine derivative in the above-described embodiment. The preferred catalyst and its preferred amount may be the same as those listed in step (B) of the method for producing the phthalocyanine derivative in the above embodiment.

[0105] [Process (C)] In step (C), an isoindoline derivative represented by general formula (8) is produced by reacting the compound represented by general formula (5) (phthalic anhydride derivative) obtained in step (b) with urea or NH3 gas and a nitrate of ammonium, lithium, sodium, potassium, magnesium, calcium, or aluminum in the presence of a catalyst.

[0106] The reaction solvent is not particularly limited as long as it allows the reaction to proceed smoothly, but methanol, ethanol, isopropyl alcohol, DMSO, DMF, or water are preferred.

[0107] The reaction temperature is not particularly limited as long as it is a temperature that allows the reaction to proceed smoothly, but the lower limit is preferably 20°C or higher, preferably 40°C or higher, preferably 60°C or higher, preferably 80°C or higher, and preferably 100°C or higher. The upper limit is preferably 280°C or lower, preferably 260°C or lower, preferably 240°C or lower, preferably 220°C or lower, preferably 200°C or lower, and preferably 180°C or lower. These upper and lower limits may be used individually or in any combination.

[0108] Urea or NH3 gas can be used as an amine source. It is preferable to add nitrates of ammonium, lithium, sodium, potassium, magnesium, calcium, or aluminum to replace all oxygen atoms with nitrogen atoms and prevent side reactions such as oligomerization and polymerization.

[0109] The catalyst is not particularly limited as long as it facilitates the reaction, but a molybdenum catalyst is preferred, and ammonium molybdate(IV) tetrahydrate is more preferred. The amount of the catalyst added is preferably 0.001 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.1 mol% or more, relative to the compound represented by general formula (5) (phthalic anhydride derivative), as a lower limit. As an upper limit, it is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 3 mol% or less. These upper and lower limits may be set individually or in any combination.

[0110] Furthermore, by reacting the obtained isoindoline derivative represented by general formula (8) with barbituric acid, an isoindoline derivative represented by general formula (9) can be produced. By reacting the obtained isoindoline derivative represented by general formula (8) with barbituric acid and 2-cyano-N-methylacetamide, isoindoline derivatives represented by general formulas (10) and (11) can be produced. Examples of reactions between isoindoline derivatives represented by general formula (8) and barbituric acid include, but are not limited to, the methods described in The Journal of Organic Chemistry 2019, 84, 10, 6217-6222, Chinese Patent Application Publication No. 103289434, Chinese Patent Application Publication No. 102585542, Japanese Patent Publication No. 2019-112537, or International Publication No. 2009 / 074533. Examples of reactions involving an isoindoline derivative represented by general formula (8) with barbituric acid and 2-cyano-N-methylacetamide include, but are not limited to, the methods described in Japanese Patent Publication No. 2020-026503, Japanese Patent Publication No. 2023-022808, International Publication No. 2022 / 014635, or Japanese Patent Publication No. 2022139293.

[0111] Specific examples of reaction solvents include those similar to those mentioned in the synthesis of isoindoline derivatives represented by the general formula (8) above. The preferred range of reaction temperature may be the same as that given for the synthesis of isoindoline derivatives represented by the general formula (8) above. The catalyst is not particularly limited as long as it allows the reaction to proceed favorably, but acids such as formic acid, hydrochloric acid, nitric acid, sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid are preferred, and acetic acid is more preferred for the synthesis of formulas (9) to (11). The amount of the catalyst added is preferably 0.001 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.1 mol% or more, relative to the compound represented by general formula (5) (phthalic anhydride derivative), as a lower limit. As an upper limit, it is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 3 mol% or less. These upper and lower limits may be set individually or in any combination.

[0112] The method for producing isoindoline derivatives according to one embodiment is simple and inexpensive because it can produce the furan derivative, which is the raw material, using the method for producing furan derivatives according to the above embodiment. It can be carried out using ordinary laboratory equipment, is easy to scale up, and reduces manufacturing costs.

[0113] In one embodiment of the method for producing a furfural derivative, from the viewpoint of reducing environmental impact, it is preferable that the furfural derivative used as a raw material is derived from biomass. Further, from the perspective of reducing environmental impact, it is preferable that the starting material, i.e., the furfural derivative or folic acid derivative, of the production method of the furan derivative in one embodiment is derived from biomass. Further, from the perspective of reducing environmental impact, it is preferable that the starting material, i.e., the furan derivative, of the production method of the phthalocyanine derivative in one embodiment is derived from biomass.

[0114] In the present disclosure, biomass refers to plants as a source of alternative energy. Biomass is usually mainly composed of two components, lignin and (hemi)cellulose. Both lignin and (hemi)cellulose are polymers. Lignin is composed of aromatic monomers, and (hemi)cellulose is composed of sugars with 5 carbon atoms and sugars with 6 carbon atoms. In the production methods of the folic acid derivative and the furan derivative in one embodiment, both the lignin-derived starting material and the (hemi)cellulose-derived starting material can be used as starting materials.

[0115] The biomass-derived furfural derivative can be produced, for example, from sugars derived from (hemi)cellulose as described in Japanese Patent No. 5791838. The biomass-derived folic acid derivative can be produced, for example, using the production method of the folic acid derivative in one embodiment with the biomass-derived furfural derivative as a starting material. The biomass-derived furan derivative can be produced, for example, using the production method of the furan derivative in one embodiment with the biomass-derived furfural derivative or the biomass-derived folic acid derivative as a starting material.

[0116] The biomass content of the furfural derivative, furic acid derivative, and furan derivative used as raw materials in the method for producing the froic acid derivative, furan derivative, and phthalocyanine derivative of one embodiment is preferably 1% or more, preferably 5% or more, preferably 10% or more, preferably 15% or more, preferably 20% or more, preferably 25% or more, preferably 30% or more, preferably 35% or more, preferably 40% or more, preferably 45% or more, preferably 50% or more, preferably 55% or more, preferably 60% or more, preferably 65% ​​or more, preferably 70% or more, preferably 75% or more, preferably 80% or more, more preferably 85% or more, even more preferably 90% or more, and particularly preferably 95% or more. The upper limit of the biomass content is not particularly limited and may be, for example, 100% or less.

[0117] Furthermore, the biomass content of the froic acid derivative, furan derivative, and phthalocyanine derivative obtained by the method for producing the froic acid derivative, furan derivative, and phthalocyanine derivative of one embodiment is preferably 1% or more, preferably 5% or more, preferably 10% or more, preferably 15% or more, preferably 20% or more, preferably 25% or more, preferably 30% or more, preferably 35% or more, preferably 40% or more, preferably 45% or more, preferably 50% or more, preferably 55% or more, preferably 60% or more, preferably 65% ​​or more, preferably 70% or more, preferably 75% or more, preferably 80% or more, more preferably 85% or more, even more preferably 90% or more, and particularly preferably 95% or more. The upper limit of the biomass content is not particularly limited and may be, for example, 100% or less.

[0118] In this specification, biomass content is defined as the amount of biomass-derived carbon (radiocarbon) in total carbon, calculated by measurement according to ASTM-D6866-18. 14 The content (mass%) of C) may be used. The carbon in petroleum-derived compounds and compositions usually contains radioactive carbon atoms. 14 Since C is not included, 14By measuring carbon (C), it is possible to determine whether the generated compound or composition is derived from petroleum or biomass.

[0119] In this specification, "radioactive carbon atoms" 14 The phrase "contains C" can be interpreted not only in the context of the segregation approach, but also in the context of the mass balance approach and the book-and-claim approach (Reference: Enabling Cirrcular Economy for Chemical with the Mass Balance Approach, the Ellen MacAthur Foundation network).

[0120] When biomass raw materials are available through the mass balance method or the book-and-claim method, it becomes easier to set the biomass content of the raw materials used in the above-mentioned methods for producing froic acid derivatives, furan derivatives, and phthalocyanine derivatives to 1-100%. This disclosure focuses on biomass content including biomass raw materials obtained through the mass balance method and the book-and-claim method. [Examples]

[0121] The embodiments will be described below with reference to specific examples and comparative examples, but the specific embodiments are not limited to these examples.

[0122] The measurement methods used in the examples and comparative examples are described below.

[0123] [Nuclear magnetic resonance analysis (NMR)] Regarding the reaction product obtained, 1 Molecular structure analysis was performed using 1H-NMR. The acquisition of the target product was confirmed by identifying the peak originating from the target product. The measurement conditions were as follows: <Measurement equipment and conditions> Measurement device: JNM-ECM400S (manufactured by JEOL RESONANCE) Resonance frequency: 400MHz Total number of times: 16 Solvent: DMSO-d6 Sample concentration: 5 mg / 1 mL

[0124] [Gas Chromatography Mass Spectrometry (GC-MS)] Gas chromatography-mass spectrometry was performed on the furans synthesized in Examples 5 and 6 and the furan from Comparative Example 1. If necessary, the furans were dissolved in methanol, ethanol, ether, or tetrahydrofuran to a concentration of 0.5–3.0 mg / mL to prepare the measurement solution. The measurement conditions were as follows: <Measurement equipment and conditions> Measurement equipment: GC7890B MSD5977B (manufactured by Agilent Technologies) Column: InertCap-5MS (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm) (manufactured by Agilent Technologies) Carrier gas: Helium Carrier gas flow rate: 1.42 mL / min Injection volume: 1μL Split ratio: 30:1 Evaporation chamber temperature: 280℃ Column temperature program: Hold at 40°C for 2 minutes → Increase temperature at 10°C / min and hold at 280°C for 4 minutes. Ion source: EI

[0125] (Example 1) 60 g of sodium phosphate and 48 g of furfural were added to a 500 mL four-necked flask equipped with a mechanical stirrer, condenser, dropping funnel, and thermometer. The reaction mixture was stirred and heated to 55°C, after which 170 g of 30% H2O2 was added dropwise over 1 hour. The reaction mixture was then maintained at 55°C for 8 hours. Throughout the reaction, the pH of the reaction system remained within the range of 3 to 5. Next, the reaction mixture was cooled to room temperature, the pH was adjusted to 12 using NaOH solution, and then extracted with ethyl acetate. The resulting extract was acidified with hydrochloric acid, filtered, and the furfural acid (white solid) was recovered. The recovered freuic acid was placed in a 100 mL round-bottom flask fitted with a distillation apparatus, and 0.04 g of Cu2O and 3 mL of N-methyl-2-pyrrolidone were added. The reaction mixture was kept at 185°C for 2 hours with stirring. Finally, furan (a colorless liquid) was collected (2.8 g, yield 8%).

[0126] (Example 2) In a 1 L four-necked flask equipped with a mechanical stirrer, condenser, dropping funnel, and thermometer, 101.19 g of triethylamine, 120 g of potassium acetate, and 48 g of furfural were added. The reaction mixture was stirred and heated to 55°C, after which 170 g of 30% H2O2 was added dropwise over 1 hour. The reaction mixture was then maintained at 55°C for 6 hours. Throughout the reaction, the pH of the reaction system remained in the range of 9 to 12. Next, the reaction mixture was cooled to room temperature, adjusted to pH 12 using NaOH solution, and then extracted with ethyl acetate. The resulting extract was acidified with hydrochloric acid, filtered, and the furfural acid (white solid) was recovered. After adding the recovered freuic acid to a 300 mL round-bottom flask fitted with a distillation apparatus, 0.32 g of Cu2O and 25 mL of N-methyl-2-pyrrolidone were added. The reaction mixture was kept at 185°C for 2 hours with stirring. Finally, furan (colorless liquid) was collected (22.8 g, yield 66%).

[0127] (Example 3) 41 g of sodium acetate and 48 g of furfural were added to a 500 mL four-necked flask equipped with a mechanical stirrer, condenser, dropping funnel, and thermometer. The reaction mixture was stirred and heated to 55°C, after which 170 g of 30% H2O2 was added dropwise over 1 hour. The reaction mixture was then maintained at 55°C for 8 hours. Throughout the reaction, the pH of the reaction system remained in the range of 8 to 10. Next, the reaction mixture was cooled to room temperature, the pH was adjusted to 12 using NaOH solution, and then extracted with ethyl acetate. The resulting extract was acidified with hydrochloric acid, filtered, and the furfural acid (white solid) was recovered. The recovered folic acid was placed in a 100 mL round-bottom flask equipped with a distillation apparatus, and 0.11 g of Cu2O and 9 mL of N-methyl-2-pyrrolidone were added. The reaction mixture was maintained at 185 °C for 2 hours while stirring. Finally, furan (a colorless liquid) was collected (8.2 g, yield 24%).

[0128] (Example 4) 147 g of potassium acetate and 48 g of furfural were added to a 500 mL four-necked flask equipped with a mechanical stirrer, a condenser, a dropping funnel and a thermometer. The reaction mixture was stirred and heated to 55 °C, and then 170 g of 30% H2O2 was added dropwise over 1 hour. Then, the reaction mixture was maintained at 55 °C for 8 hours. Throughout the reaction, the pH of the reaction system was within the range of 9 - 11. Next, the reaction mixture was cooled to room temperature, adjusted to pH 12 using a NaOH solution, and then extracted with ethyl acetate. The obtained extract was acidified with hydrochloric acid and filtered to recover folic acid (a white solid). The recovered folic acid was placed in a 100 mL round-bottom flask equipped with a distillation apparatus, and 0.28 g of Cu2O and 22 mL of N-methyl-2-pyrrolidone were added. The reaction mixture was maintained at 185 °C for 2 hours while stirring. Finally, furan (a colorless liquid) was collected (20 g, yield 58%).

[0129] (Example 5) 74 g of potassium acetate and 48 g of furfural were added to a 500 mL four-necked flask equipped with a mechanical stirrer, a condenser, a dropping funnel and a thermometer. The reaction mixture was stirred and heated to 75 °C, and then 68 g of 30% H2O2 was added dropwise over 1 hour. Then, the reaction mixture was maintained at 75 °C for 6 hours. Throughout the reaction, the pH of the reaction system was within the range of 9 - 11. Next, the reaction mixture was cooled to room temperature, adjusted to pH 12 using a NaOH solution, and then extracted with ethyl acetate. The obtained extract was acidified with hydrochloric acid and filtered to recover folic acid (a white solid). The recovered freuic acid was placed in a 100 mL round-bottom flask fitted with a distillation apparatus, and 0.28 g of Cu2O and 22 mL of N-methyl-2-pyrrolidone were added. The reaction mixture was kept at 185°C for 2 hours with stirring. Finally, furan (colorless liquid) was collected (20.6 g, yield 60%). The purity of furoic acid, as determined by GC-MS measurements, was over 99.5%, and it contained less than 0.5% of furanone, fumaric acid, maleic acid, or succinic acid. Furthermore, the purity of furan, as determined by GC-MS measurements, was 99.844%, and it contained 0.156% 2-methylfuran.

[0130] (Example 6) 74 g of potassium acetate and 48 g of furfural were added to a 500 mL four-necked flask equipped with a mechanical stirrer, condenser, dropping funnel, and thermometer. The reaction mixture was stirred and heated to 75°C, after which 68 g of 30% H2O was added dropwise over 1 hour. The reaction mixture was then maintained at 75°C for 6 hours. Throughout the reaction, the pH of the reaction system remained in the range of 9 to 11. Next, the reaction mixture was cooled to room temperature, the pH was adjusted to 12 using NaOH solution, and then extracted with ethyl acetate. The resulting extract was acidified with hydrochloric acid, filtered, and the furfural acid (white solid) was recovered. The recovered freuic acid was placed in a 200 mL round-bottom flask fitted with a distillation apparatus, and 0.29 g of Cu2O and 45 mL of N-ethyl-2-pyrrolidone were added. The reaction mixture was kept at 185°C for 2 hours with stirring. Finally, furan (a colorless liquid) was collected (20.6 g, yield 60%). The purity of froic acid, as determined by GC-MS measurements, was over 99.5%, and it contained less than 0.5% of furanone, fumaric acid, maleic acid, or succinic acid. Furthermore, the purity of furan, as determined by GC-MS measurements, was 99.880%, and it contained 0.120% 2-methylfuran.

[0131] (Example 7) 74 g of potassium acetate and 48 g of furfural were added to a 500 mL four-necked flask equipped with a mechanical stirrer, condenser, dropping funnel, and thermometer. The reaction mixture was stirred and heated to 75°C, after which 68 g of 30% H2O was added dropwise over 1 hour. The reaction mixture was then maintained at 75°C for 6 hours. Throughout the reaction, the pH of the reaction system remained in the range of 9 to 11. Next, the reaction mixture was cooled to room temperature, the pH was adjusted to 12 using NaOH solution, and then extracted with ethyl acetate. The resulting extract was acidified with hydrochloric acid, filtered, and the furfural acid (white solid) was recovered. The recovered freuic acid was placed in a 100 mL round-bottom flask equipped with a distillation apparatus and kept at 185°C for 2 hours with stirring. Finally, furan (colorless liquid) was collected (18.1 g, yield 52%).

[0132] (Example 8) 74 g of potassium acetate and 48 g of furfural were added to a 500 mL four-necked flask equipped with a mechanical stirrer, condenser, dropping funnel, and thermometer. The reaction mixture was stirred and heated to 75°C, after which 68 g of 30% H2O was added dropwise over 1 hour. The reaction mixture was then maintained at 75°C for 6 hours. Throughout the reaction, the pH of the reaction system remained in the range of 9 to 11. Next, the reaction mixture was cooled to room temperature, the pH was adjusted to 12 using NaOH solution, and then extracted with ethyl acetate. The resulting extract was acidified with hydrochloric acid, filtered, and the furfural acid (white solid) was recovered. The recovered freuic acid was placed in a 200 mL round-bottom flask fitted with a distillation apparatus, and 45 mL of N-ethyl-2-pyrrolidone was added. The reaction mixture was kept at 185°C for 2 hours with stirring. Finally, furan (colorless liquid) was collected (11.1 g, yield 32%).

[0133] (Example 9) 74 g of potassium acetate and 48 g of furfural were added to a 500 mL four-necked flask equipped with a mechanical stirrer, condenser, dropping funnel, and thermometer. The reaction mixture was stirred and heated to 75°C, after which 68 g of 30% H2O was added dropwise over 1 hour. The reaction mixture was then maintained at 75°C for 6 hours. Throughout the reaction, the pH of the reaction system remained in the range of 9 to 11. Next, the reaction mixture was cooled to room temperature, the pH was adjusted to 12 using NaOH solution, and then extracted with ethyl acetate. The resulting extract was acidified with hydrochloric acid, filtered, and the furfural acid (white solid) was recovered. The recovered freuic acid was placed in a 200 mL round-bottom flask fitted with a distillation apparatus, and 57 mL of hexadecane was added. The reaction mixture was kept at 185°C for 2 hours with stirring. Finally, furan (colorless liquid) was collected (9.7 g, yield 35%).

[0134] (Comparative Example 1) A commercially available furan (manufactured by Sinopharm Chemical Reagent) was used as Comparative Example 1 and compared with the example. The purity of furan, as determined from GC-MS measurements, was 100.000%. [Industrial applicability]

[0135] According to the present invention, fleucic acid derivatives, furan derivatives, phthalocyanine derivatives, and isoindoline derivatives can be produced in higher yield and at lower cost using a simpler manufacturing method than conventional methods. Therefore, each manufacturing method of the present invention can be easily scaled up and is a clean and green method that can greatly contribute to the future development of biomass-derived fleucic acid derivatives, furan derivatives, phthalocyanine derivatives, and isoindoline derivatives.

Claims

1. An oxidation step to obtain a froic acid derivative represented by general formula (2) by oxidizing a furfural derivative represented by general formula (1), as shown in reaction formula (I), wherein the pH of the reaction system is maintained within the range of 3 to 12 throughout the reaction, and one or more compounds selected from the group consisting of formic acid, acetic acid, hydrochloric acid, nitric acid, methanesulfonic acid, p-toluenesulfonic acid, phosphoric acid, anhydrous phosphoric acid, polyphosphate, pyrophosphate, phosphorous acid, triethylamine, and salts thereof are used as additives in an amount of 50 to 500 mol% relative to the furfural derivative represented by general formula (1), and as an oxidizing agent, O ２ H ２ O ２ , O ３ , KMnO ４ , KClO ３ or includes an oxidation step in which NaClO is used in an amount of 50 to 1000 mol% relative to the furfural derivative represented by the general formula (1) (except when an enzyme is used), 【Chemistry 1】 In the formula, R １ Each of the R3 groups independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, or a phenyl group, and one or more non-adjacent -CH2- groups present in the alkyl group may be replaced with -O-. A method for producing freuic acid derivatives.

2. A method for producing a froic acid derivative according to claim 1, wherein the oxidation step is carried out at a temperature of 0 to 120°C.

3. An oxidation step of obtaining a folic acid derivative represented by the general formula (2) by oxidizing a furfural derivative represented by the general formula (1) as shown in the reaction formula (III), wherein the pH of the reaction system is maintained within the range of 3 to 12 throughout the reaction, and as an additive, one or more compounds selected from the group consisting of formic acid, acetic acid, hydrochloric acid, nitric acid, phosphoric acid, phosphoric anhydride, polyphosphoric acid, pyrophosphoric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, phosphorous acid, triethylamine, and salts thereof are used in an amount of 50 to 500 mol% based on the furfural derivative represented by the general formula (1), and as an oxidizing agent, O ２ , H ２ O ２ , O ３ , KMnO ４ , KClO ３ , or NaClO is used in an amount of 50 to 1000 mol% based on the furfural derivative represented by the general formula (1) (except when an enzyme is used), and As shown in reaction equation (III), a decarboxylation step is performed to obtain a furan derivative represented by general formula (3) by decarboxylating the freuic acid derivative represented by general formula (2) obtained in the oxidation step, and the decarboxylation step is performed without a catalyst or using an oxide of a 1- to 3-valent transition metal as a catalyst. 【Chemistry 2】 In the formula, R １ Each of the R3 groups independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, or a phenyl group, and one or more non-adjacent -CH2- groups present in the alkyl group may be replaced with -O-. A method for producing furan derivatives.

4. An oxidation step to obtain a froic acid derivative represented by general formula (2) by oxidizing a furfural derivative represented by general formula (1), as shown in reaction formula (III), wherein the pH of the reaction system is maintained within the range of 3 to 12 throughout the reaction, and one or more compounds selected from the group consisting of formic acid, acetic acid, hydrochloric acid, nitric acid, phosphoric acid, phosphoric anhydride, polyphosphoric acid, pyrophosphoric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, phosphorous acid, triethylamine, and salts thereof are used as additives in an amount of 50 to 500 mol% relative to the furfural derivative represented by general formula (1), and as an oxidizing agent, O ２ H ２ O ２ , O ３ , KMnO ４ , KClO ３ , or an oxidation step using 50 to 1000 mol% of NaClO relative to the furfural derivative represented by the general formula (1) (except when an enzyme is used), As shown in reaction equation (III), a decarboxylation step is performed to obtain a furan derivative represented by general formula (3) by decarboxylating the freuic acid derivative represented by general formula (2) obtained in the oxidation step, the decarboxylation step being performed using a high-boiling point solvent. Includes, 【Transformation 3】 In the formula, R １ Each of the R3 groups independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, or a phenyl group, and one or more non-adjacent -CH2- groups present in the alkyl group may be replaced with -O-. A method for producing furan derivatives.

5. A method for producing a furan derivative according to claim 3 or 4, wherein the oxidation step is carried out at a temperature of 0 to 120°C.

6. A method for producing a furan derivative according to claim 3 or 4, wherein the biomass content of the furan derivative is 1% or more.

7. A method for producing phthalocyanine derivatives, A furan derivative manufacturing step for manufacturing the furan derivative represented by the method for manufacturing the furan derivative according to claim 3 or 4, Step (A) is to obtain a compound represented by general formula (4) from the furan derivative represented by general formula (3) obtained in the furan derivative manufacturing step, Step (B) is to obtain a compound represented by general formula (5) from the compound represented by general formula (4) obtained in step (A), Step (C) to obtain a phthalocyanine derivative represented by general formula (6) or (7) from the compound represented by general formula (5) obtained in step (B), Includes, 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 During the ceremony R １ Each of the R3 groups independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, or a phenyl group, and one or more non-adjacent -CH2- groups present in the alkyl group may be replaced with -O-. M ２ This represents a metal atom. A method for producing phthalocyanine derivatives.

8. A method for producing isoindoline derivatives, A furan derivative manufacturing step for manufacturing the furan derivative represented by the method for manufacturing the furan derivative according to claim 3 or 4, Step (a) of obtaining a compound represented by general formula (4) from the furan derivative represented by general formula (3) obtained in the furan derivative manufacturing step, Step (b) is to obtain a compound represented by general formula (5) from the compound represented by general formula (4) obtained in step (a), Step (C) to obtain at least one isoindoline derivative represented by general formulas (8) to (11) from the compound represented by general formula (5) obtained in step (b) above, and Includes, 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 In the formula, R １ Each of the R3 groups independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, or a phenyl group, and one or more non-adjacent -CH2- groups present in the alkyl group may be replaced with -O-. A method for producing isoindoline derivatives.

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