Process for producing folic 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 folic acid derivatives, furan derivatives, phthalocyanine derivatives, and isoindoline derivatives.

Background Art

[0002] Furan is used as a raw material in various industries such as pigments, dyes, pharmaceuticals, agricultural chemicals, fragrances, polymers, and resins. It is not only used as a starting material for synthesizing other organic compounds such as phthalocyanine, but also has many uses in the field of organic chemistry, such as being used as a solvent, a chemical intermediate, and a polymerization initiator. For example, the global furan resin market was estimated to be $15.66 billion in 2021 and is predicted to reach $23.68 billion at an annual average growth rate of 5.3% by 2029 (see "Furan Resin Market - Global Industry Analysis and Forecast by Type, Application, and Region (2022 - 2029)" [online], [searched on June 6, 2023] Internet <URL: https: / / www.maximizemarketresearch.com / market-report / global-furan-resins-market / 116002 / >). With the increasing demand for furan, due to problems such as the depletion of fossil raw material resources and the emission of greenhouse gases, a smooth transition from fossil-derived furan to biomass-derived furan is required, and the development of more efficient new manufacturing technologies is urgent.

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

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0005]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in the above conventional method for producing furan, expensive metal catalysts such as Re, Ru, Ir, Pt, Pd, and Au are required, and in some cases, two or more metal catalysts are necessary. Also, depending on the reaction system, the use of pressurized O2 or H2 may be required to shift the equilibrium state. Furthermore, since most reactions need to be carried out at a high temperature of 140 to 300 °C, a high-temperature reactor such as an autoclave is required. These manufacturing constraints limit scale-up and are factors contributing to a significant increase in manufacturing costs. In addition, in the above conventional method for obtaining folic acid from furfural, since furfural is prone to peroxidation, by-products (peroxides) are likely to be generated, and there is room for further improvement in terms of purity and yield.

Means for Solving the Problems

[0007] Therefore, an object of the present invention is to provide a method for producing a folic acid derivative, a furan derivative, a phthalocyanine derivative, and an isoindoline derivative that is simpler and cheaper.

[0008] That is, the present invention is as follows. [1] As shown in Reaction Formula (I), 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), the oxidation step including a reaction system having a pH of 3 to 12, [Chemical Formula] In the formula, R 1 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, 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] In the formula, X represents an -OH group, an -OM 1 group, or -R 4 and represents M 1 represents an alkali metal atom, R 4 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. Y 1 represents a hydrogen atom, an alkali metal atom, -COR 5 , or a functional group represented by general formula (B). R 5 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. Z represents a sulfur atom or a phosphorus atom. W represents an oxygen atom or is substantially the same as the above X. n1 is an integer from 1 to 10. [Chemical formula] R in the general formula (B) 6 represents 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,

Chemical formula

Chemical formula

[10] The 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] The method for producing a furan derivative according to any one of [7] to

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

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

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

[13] A method for producing a phthalocyanine derivative from a furan derivative obtained by the method for producing a furan derivative according to any one of [5] to

[12] , a step (A) of obtaining a compound represented by the general formula (4) from the furan derivative represented by the general formula (3); a step (B) of obtaining a compound represented by the general formula (5) from the compound represented by the general formula (4) obtained in the step (A); a step (C) of obtaining a phthalocyanine derivative represented by the general formula (6) or (7) from the compound represented by the general formula (5) obtained in the step (B), comprising

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[14] A method for producing an isoindoline derivative from a furan derivative obtained by the method for producing a furan derivative according to any one of [5] to

[12] , a step (a) of obtaining a compound represented by the general formula (4) from the furan derivative represented by the general formula (3); a step (b) of obtaining a compound represented by the general formula (5) from the compound represented by the general formula (4) obtained in the step (a); a step (C) of obtaining at least one of the isoindoline derivatives represented by the general formulas (8) to (11) from the compound represented by the general formula (5) obtained in the step (b); comprising

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0009] According to the present invention, it is possible to provide a method for producing a folic acid derivative, a furan derivative, a phthalocyanine derivative, and an isoindoline derivative that is simpler and cheaper.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, certain embodiments of the present invention will be described in detail. 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 "substantially the same" means not only "the same" but also the same to the extent that the effects of the present invention are not impaired.

[0011] <Method for Producing a Folic Acid Derivative> The method for producing a folic acid derivative according to one embodiment is 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 following reaction formula (I), and includes an oxidation step in which the pH of the reaction system is 3 to 12.

Chemical formula

[0012] In the general formulas (1) and (2), R 1 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. R 2 and R 3 each independently 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, an aryl group having 6 to 12 carbon atoms which may be substituted, or R 2 and R 3 may form a 5- to 8-membered ring by closing the ring.

[0013] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

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

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

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

[0017] R 2 and R 3 may form a 5- to 8-membered ring by closing the ring. Further, the ring structure may have an -OH group, -COOH group, -NH-, -S-, or -O- in the ring structure.

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

Chemical formula

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

Chemical formula

[0020] 〈Oxidation step〉 In the oxidation step in the method for producing the folic acid derivative of the above embodiment, a folic acid derivative represented by the general formula (2) can be obtained by an oxidation reaction of the fulfulal derivative represented by the general formula (1). In the 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 the folic acid derivative. However, 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 occurrence of excessive oxidation to peroxides (for example, furanone derivatives, succinic acid derivatives, maleic acid derivatives, fumaric acid derivatives, etc.). Therefore, the folic acid derivative can be obtained with high purity and yield. The pH of the reaction system changes as the oxidation reaction progresses, but it is preferably within the range of 3 to 12 throughout the reaction. As the lower limit value of the pH, 4 or more is preferable, 5 or more is preferable, 6 or more is preferable, and 7 or more is preferable. Also, as the upper limit value of the pH, it may be 11 or less, or it may be 10 or less. These upper limit values and lower limit values may be any one alone or any combination. Examples of the method for controlling the pH of the reaction system within the above range include, for example, the method of adding an additive 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. For example, O2, H2O2, O3, KMnO4, KClO3, or NaClO may be used. Among these oxidizing agents, H2O2 is preferred. The addition amount of the oxidizing agent is not particularly limited as long as it allows the reaction to proceed well. However, with respect to the fulvaleraldehyde derivative represented by the general formula (1), for example, as the lower limit, 50 mol% or more is preferable, 80 mol% or more is more preferable, and 100 mol% or more is even more preferable. As the upper limit, for example, 1000 mol% or less is preferable, 800 mol% or less is more preferable, and 400 mol% or less is even more preferable. These upper and lower limits may be any single one or any combination thereof.

[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, and compounds represented by general formulas (A1) to (A4).

Chemical formula

[0023] In general formulas (A1) and (A2), X may represent an -OH group, an -OM 1 group, or an -R 4 group. M 1 may represent an alkali metal atom. R 4 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. Y 1 may represent a hydrogen atom, an alkali metal atom, a -COR 5 group, or a functional group represented by the general formula (B). R 5may 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 may be substantially the same as the above X. n1 may be an integer of 1 to 10.

[0024] M 1 Examples of the alkali metal atom of 1 include Li, Na, or K. Y 1 Examples of the alkali metal atom of 1 include Li, Na, K, Rb, or Cs. R 4 and R 5 The preferred ranges and preferred examples of 4 and 5 may be the same as those listed for R in the above general formulas (1) and (2). 1 n1 is preferably an integer of 1 to 8, more preferably an integer of 1 to 5.

[0025]

Chemical formula

[0026] In general formula (B), R 6 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 ranges and preferred examples of 6 may be the same as those listed for R in the above general formulas (1) and (2). Among these functional groups, protonated triethylamine is preferred. 1

[0027] X is particularly preferably a -CH3 group. Y 1 ​​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] [Chemical formula]

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

[0030] As the above additive, one or more compounds selected from the group consisting of phosphates and the compounds represented by general formulas (A1) to (A4) are more preferable, and one or more compounds selected from the group consisting of NaH2PO4, potassium acetate, sodium acetate, and triethylammonium acetate are even more preferable. In the oxidation reaction of the furfural derivative, as the reaction proceeds, the pH of the reaction system decreases (that is, it shifts to the acidic side), and peroxides are likely to be generated and the generated peroxides act as autocatalysts. However, when an additive is added, the reaction system is neutralized and it becomes easier to maintain the pH at 3 to 12, and the folic acid derivative can be obtained with higher purity and yield.

[0031] The addition amount of the additive is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 100 mol% or more with respect to the furfural derivative represented by the general formula (1). Further, as the upper limit value, it is preferably 500 mol% or less, more preferably 300 mol% or less, and still more preferably 200 mol% or less. These upper and lower limit values may be any one alone or 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 total amount of the additive can be added at any timing before or during the reaction. Further, 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 suitably. 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. Further, the above oxidation reaction can proceed even without a solvent.

[0033] The temperature of the oxidation reaction is preferably 0 to 120°C, more preferably 5 to 100°C, and still more preferably 30 to 90°C. The oxidation reaction of the above embodiment can be carried out at a lower temperature than the prior art. In the prior art, it is considered necessary to carry out the reaction at a high temperature (140 to 300°C). In a specific embodiment, a high-temperature reactor is not required, and therefore, the equipment cost can be reduced and it can be easily scaled up. The time of the oxidation reaction is not particularly limited and may be set according to the reaction temperature, the type of the additive and the oxidizing agent, etc.

[0034] The method for producing the folic acid derivative of one embodiment may include other steps such as a purification step for removing reaction by-products.

[0035] The production method of the folic acid derivative according to one embodiment is simple and inexpensive, and thus can be carried out with ordinary laboratory equipment and can be easily scaled up. Further, since the reaction is carried out under relatively mild reaction conditions, the reaction is easy to control and the generation of by-products (peroxides) due to peroxidation is also small.

[0036] According to the production method of the folic acid derivative of one embodiment, a folic acid derivative with high purity can be obtained. The purity (content) of the folic acid derivative preferably has a lower limit value of 95.0% or more, more preferably 98.0% or more, and still more preferably 99.0% or more. The upper limit value is not particularly limited, and 100% is most preferable, but it may be 99.999% or less, or may be 99.5% or less. These upper limit values and lower limit values may be any one alone or any combination. The content of reaction by-products such as peroxides preferably has an upper limit value of 5.0% or less, more preferably 2.0% or less, and still more preferably 1.0% or less. The lower limit value is not particularly limited, and 0% is most preferable, but it may be 0.01% or more, or may be 0.1% or more. These upper limit values and lower limit values may be any one alone or any combination. The purity (content) of the folic acid derivative and the content of the reaction by-products can be determined, for example, by quantifying folic acid and the reaction by-products respectively by gas chromatography-mass spectrum (GC-MS).

[0037] Further, according to the production method of the folic acid derivative of one embodiment, a folic acid derivative can be obtained in a high yield. The yield of the folic acid derivative preferably has a lower limit value of 10% or more, more preferably 50% or more, and still more preferably 80% or more. The upper limit value is not particularly limited, and 100% is most preferable, but it may be 95% or less, or may be 90% or less. These upper limit values and lower limit values may be any one alone or any combination.

[0038] <Production Method of Furan Derivative> The method for producing a furan derivative according to an embodiment is a decarboxylation step of obtaining a furan derivative represented by the general formula (3) by decarboxylating a folic acid derivative represented by the general formula (2) as shown in the reaction formula (II), and includes a decarboxylation step of performing decarboxylation without a catalyst or using an oxide of a transition metal having a valence of 1 to 3 as a catalyst.

Chemical formula

[0039] In the general formulas (2) and (3), R 1 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. R 2 and R 3 each independently 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, an aryl group having 6 to 12 carbon atoms which may be substituted, or R 2 and R 3 may form a 5- to 8-membered ring by closing the ring.

[0040] The preferred ranges and preferred examples of the above R 1 ~R 3 may be the same as those listed for R 1 ~R 3 in the general formulas (1) and (2) in the method for producing a folic acid derivative according to the above embodiment. Specific examples of the folic acid derivative represented by the general formula (2) may be the same as those listed in the method for producing a folic acid derivative according to the above embodiment.

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

Chemical formula

[0042] 〈Decarboxylation step〉 In the decarboxylation step in the method for producing a furan derivative according to the above embodiment, a furan derivative represented by the general formula (3) can be obtained by the decarboxylation reaction of the folic acid derivative represented by the general formula (2). Different from the conventional technology that uses expensive and precious metal catalysts (Re, Ru, Ir, Pt, Pd, Au, etc.), this decarboxylation reaction can be carried out without a catalyst or using an oxide of a trivalent transition metal that is inexpensive and easily available as a catalyst. Therefore, scale-up is easy and the production cost can be reduced.

[0043] When the decarboxylation reaction is carried out without a catalyst, it is necessary to set the reaction temperature relatively high in order to promote decarboxylation well. Therefore, it is more preferable to use an oxide of a trivalent transition metal as a catalyst. When a catalyst is used in the decarboxylation reaction, specific examples of the catalyst include Cu2O, CuO, FeO, Fe2O3, etc. Among these catalysts, Cu2O is preferable. The addition amount of the catalyst is not particularly limited as long as the reaction proceeds well. However, with respect to the folic acid derivative represented by the general formula (2), as a lower limit value, for example, 0.001 mol% or more is preferable, 0.01 mol% or more is more preferable, and 0.1 mol% or more is even more preferable. As an upper limit value, for example, 100 mol% or less is preferable, 50 mol% or less is more preferable, and 20 mol% or less is even more preferable. These upper and lower limit values may be any one alone or any combination.

[0044] The solvent used in the decarboxylation reaction is not particularly limited as long as it allows the reaction to proceed favorably. From the perspective of suppressing the sublimation of the furan derivative that occurs when the reaction temperature is high, it is preferably a high-boiling solvent. For example, 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, etc. may be mentioned. Among these solvents, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or hexadecane is preferred. Note that the high-boiling solvent generally may mean a solvent with a boiling point of 150 to 280 °C, but other boiling points can also be regarded as high-boiling points, and in particular, any boiling point exceeding the previously described range can also be regarded as a high-boiling point. Also, the above decarboxylation reaction proceeds even without a solvent.

[0045] The temperature of the decarboxylation reaction is not particularly limited as long as it allows the reaction to proceed 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. Also, when using an oxide of a trivalent transition metal 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 time of the decarboxylation reaction is not particularly limited and may be set according to the reaction temperature, the type of catalyst, etc.

[0046] The method for producing a furan derivative according to one embodiment is a decarboxylation step of obtaining a furan derivative represented by the general formula (3) by decarboxylating a folic acid derivative represented by the general formula (2) as shown in the reaction formula (II), and includes a decarboxylation step of performing decarboxylation using a high-boiling solvent.

Chemical formula

[0047] In the 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 form a 5- to 8-membered ring by closing the ring.

[0048] The preferred ranges and preferred examples of the above R 1 ~R 3 may be the same as those listed for R 1 ~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 of one 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). In the decarboxylation reaction, undesirable sublimation of the furan derivative may occur due to 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 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 the high-boiling solvent include the same ones as 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 can suitably promote the reaction. From the viewpoints of ease of scale-up and reduction of production cost, the catalyst is preferably an oxide of a transition metal having a valence of 1 to 3. Specific examples of the oxide of a transition metal having a valence of 1 to 3 include the same ones as those listed above. The addition amount of the catalyst is not particularly limited as long as it can promote the reaction well. However, with respect to the folic acid derivative represented by the general formula (2), the lower limit is preferably, for example, 0.001 mol% or more, more preferably 0.01 mol% or more, and still more preferably 0.1 mol% or more. The upper limit is preferably, for example, 100 mol% or less, more preferably 50 mol% or less, and still more preferably 20 mol% or less. These upper and lower limits may be any one alone or any combination.

[0052] The temperature of the decarboxylation reaction is not particularly limited as long as it can suitably promote the reaction. For example, when carried out without a catalyst, 50 to 300 °C is preferable, 80 to 290 °C is more preferable, and 100 to 280 °C is still more preferable. When an oxide of a transition metal having a valence of 1 to 3 is used as the catalyst, 50 to 280 °C is preferable, 80 to 270 °C is more preferable, and 100 to 250 °C is still more preferable. The time of the decarboxylation reaction is not particularly limited and may be set according to the reaction temperature, the type of catalyst, etc.

[0053] Another method for producing a furan derivative according to an embodiment includes an oxidation step of obtaining a folic acid derivative represented by the general formula (2) by oxidizing a fulfulral derivative represented by the general formula (1) as shown in the reaction formula (III), the oxidation step being carried out at a pH of 3 to 12 of the reaction solution, and a decarboxylation step of obtaining a furan derivative represented by the general formula (3) by decarboxylating the folic acid derivative represented by the general formula (2) obtained in the oxidation step as shown in the reaction formula (III), the decarboxylation step being carried out without a catalyst or using an oxide of a transition metal having a valence of 1 to 3 as a catalyst.

Chemical formula

[0054] In the general formulas (1) to (3), R 1 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. R 2 and R 3 each independently 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, an aryl group having 6 to 12 carbon atoms which may be substituted, or R 2 and R 3 may form a 5- to 8-membered ring by closing the ring.

[0055] 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 method for producing a folic acid derivative according to the above embodiment. Also, specific examples of each of the fulfulral derivative represented by the general formula (1), the folic acid derivative represented by the general formula (2), and the furan derivative represented by the general formula (3) may be the same as those listed above.

[0056] 〈Oxidation step〉 In the oxidation step in the method for producing a furan derivative according to an embodiment, a folic acid derivative represented by the general formula (2) can be obtained by an oxidation reaction of a furfural derivative represented by the 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 easily occurs in the oxidation reaction of a folic acid derivative. However, 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 excessive progress of oxidation and the generation of peroxides (for example, succinic acid derivatives, furanone derivatives, maleic acid derivatives, fumaric acid derivatives, etc.). Therefore, a folic acid derivative can be obtained with high purity and yield.

[0057] The preferred range of the pH of the reaction system may be the same as that mentioned in the oxidation step of the method for producing the above folic acid derivative. As a method for controlling the pH of the reaction system within the above range, for example, a method of adding an additive can be mentioned, similar to the oxidation step of the method for producing the above folic acid derivative.

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

[0059] The temperature of the oxidation reaction can be the same as the temperature in the oxidation step of the method for producing the above folic acid derivative. The oxidation reaction of the above embodiment can be carried out at a lower temperature than the prior art. In the prior art, it is considered necessary to react at a high temperature (140 to 300 °C). In a specific embodiment, a high-temperature reactor is not required, so that the equipment cost can be reduced and it can be easily scaled up. The time of the oxidation reaction is not particularly limited and may be set according to the reaction temperature, the types of additives and oxidizing agents, etc.

[0060] 〈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 the decarboxylation reaction of a folic acid derivative represented by the general formula (2). Since the decarboxylation reaction can use the folic acid derivative represented by the general formula (2) obtained with high purity and high yield in the above oxidation step as a raw material, a furan derivative can be obtained with high purity and high yield. Unlike the prior art that uses expensive and precious metal catalysts (Re, Ru, Ir, Pt, Pd, Au, etc.), the decarboxylation reaction can be carried out without a catalyst or using oxides of trivalent transition metals that are inexpensive and easily available as a catalyst. Therefore, it is easy to scale up and the manufacturing cost can be reduced. When the decarboxylation reaction is carried out without a catalyst, usually, the reaction temperature is set relatively high in order to promote decarboxylation well. Therefore, it is more preferable to use oxides of trivalent transition metals as a catalyst.

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

[0062] In the method for producing a furan derivative according to the above embodiment, since the first-stage oxidation step can be carried out under relatively mild reaction conditions, the reaction is easy to control and the generation of by-products (peroxides) due to peroxidation is also small. In addition, since the second-stage decarboxylation step can be carried out using the folic acid derivative obtained with high purity and high yield in the first-stage oxidation step, a furan derivative can be produced with high purity and good yield. Also, the reaction can be carried out without a catalyst or using a catalyst that is inexpensive and easily available. Therefore, although the method for producing a furan derivative according to the above embodiment has two steps, it is a simple and inexpensive production method and can be carried out with ordinary laboratory equipment. Therefore, it is easy to scale up and the manufacturing cost can be reduced.

[0063] Another method for producing a furan derivative according to an embodiment includes an oxidation step of obtaining a folic acid derivative represented by the general formula (2) by oxidizing a fulfulral derivative represented by the general formula (1) as shown in the reaction formula (III), the oxidation step being carried out at a pH of 3 to 12 of the reaction solution, and a decarboxylation step of obtaining a furan derivative represented by the general formula (3) by decarboxylating the folic acid derivative represented by the general formula (2) obtained in the oxidation step as shown in the reaction formula (III), the decarboxylation step being carried out using a high-boiling solvent.

Chemical formula

[0064] In the general formulas (1) to (3), R 1 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. R 2 and R 3 each independently 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, an aryl group having 6 to 12 carbon atoms which may be substituted, or R 2 and R 3 may form a 5- to 8-membered ring by closing the ring.

[0065] 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 method for producing a folic acid derivative according to the above embodiment. In addition, specific examples of the fulfulral derivative represented by the general formula (1), the folic acid derivative represented by the general formula (2), and the furan derivative represented by the general formula (3) may be the same as those listed above.

[0066] 〈Oxidation Step〉 In the oxidation step of the method for producing a furan derivative according to one embodiment, a folic acid derivative represented by the general formula (2) can be obtained by an oxidation reaction of a furfural derivative represented by the 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 a folic acid derivative. However, in the oxidation reaction of the above-described embodiment, by controlling the pH of the reaction system within the range of 3 to 12, it is possible to suppress the excessive progress of oxidation and the generation of peroxides (for example, succinic acid derivatives, furanone derivatives, maleic acid derivatives, fumaric acid derivatives, etc.). Therefore, a folic acid derivative can be obtained with high purity and yield.

[0067] The preferred range of the pH of the reaction system may be the same as that described in the oxidation step of the method for producing a folic acid derivative according to the above embodiment. As a method for controlling the pH of the reaction system within the above range, for example, a method of adding an additive can be mentioned, similar to the oxidation step of the method for producing a folic acid derivative according to the above embodiment.

[0068] In the oxidation reaction, the oxidizing agent, additive, and solvent described in the oxidation step of the method for producing a folic acid derivative according to the above embodiment can be used. Also, the timing of adding the additive may be the same as that in the oxidation step of the method for producing the folic acid derivative.

[0069] The temperature of the oxidation reaction can be the same as that in the oxidation step of the method for producing a folic acid derivative. The oxidation reaction of the above embodiment can be carried out at a lower temperature than the prior art. In the prior art, it is considered necessary to carry out the reaction at a high temperature (140 to 300 °C). In a specific embodiment, a high-temperature reactor is not required, and therefore, the equipment cost can be reduced and it can be easily scaled up. The time of the oxidation reaction is not particularly limited and may be set according to the reaction temperature, the types of additives and oxidizing agents, etc.

[0070] 〈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 the decarboxylation reaction of a folic acid derivative represented by the general formula (2). In the decarboxylation reaction, undesirable sublimation of the furan derivative may occur due to 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 embodiment, by using a high-boiling solvent, even when the reaction temperature is high, the decarboxylation reaction can proceed smoothly without undesirable sublimation of the furan derivative. In this way, the decarboxylation reaction can be carried out successfully with or without using a catalyst.

[0071] Specific examples of the high-boiling solvent include the same ones as those listed above.

[0072] The decarboxylation reaction may be carried out with or without using a catalyst. Specific examples of the catalyst include the same ones as those listed above. The temperature of the decarboxylation reaction can be the same as that described above. The time of the decarboxylation reaction is not particularly limited and may be set according to the reaction temperature, the type of catalyst, etc.

[0073] In the method for producing a furan derivative according to the above embodiment, since the first-stage oxidation step is carried out under relatively mild reaction conditions, the reaction is easy to control and the generation of by-products (peroxides) due to peroxidation is also small. In addition, since the decarboxylation step of the second stage is carried out in a high-boiling solvent using the folic acid derivative obtained with high purity and high yield by the first-stage oxidation step, a furan derivative can be produced with high purity and good yield. Therefore, the method for producing a furan derivative according to the above embodiment, although it has two stages, is a simple and inexpensive production method and can be carried out with ordinary laboratory equipment, so it is easy to scale up and the production cost can be reduced.

[0074] The method for producing a furan derivative according to an embodiment may each include other steps other than the oxidation step and the decarboxylation step. For example, it may include steps such as a purification step for removing reaction by-products.

[0075] According to the method for producing a furan derivative according to an embodiment, a furan derivative with high purity can be obtained. The purity (content) of the furan derivative preferably has a lower limit value of 99.5% or more, more preferably 99.6% or more, and even more preferably 99.7% or more. The upper limit value is not particularly limited, and 100% is most preferred, but it may be 99.999% or less, or may be 99.98% or less. These upper and lower limit values may be either alone or in any combination. The content of the reaction by-products preferably has an upper limit value of 0.5% or less, more preferably 0.3% or less, and even more preferably 0.2% or less. The lower limit value is not particularly limited, and 0% is most preferred, but it may be 0.001% or more, or may be 0.01% or more. These upper and lower limit values may be either alone 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 by gas chromatography-mass spectrometry (GC-MS).

[0076] Also, according to the method for producing a furan derivative according to an embodiment, a furan derivative can be obtained in a high yield. The yield of the furan derivative preferably has a lower limit value of 99.5% or more, more preferably 99.6% or more, and even more preferably 99.7% or more. The upper limit value is not particularly limited, and 100% is most preferred, but it may be 99.99% or less, or may be 99.98% or less. These upper and lower limit values may be either alone or in any combination.

[0077] <Method for Producing Phthalocyanine Derivative> The method for producing a phthalocyanine derivative according to one embodiment can use the furan derivative represented by the general formula (3) obtained by the method for producing a furan derivative according to the above one embodiment. The method for producing a phthalocyanine derivative according to one embodiment includes a step (A) of obtaining a compound represented by the general formula (4) from the furan derivative represented by the general formula (3), a step (B) of obtaining a compound represented by the general formula (5) from the compound represented by the general formula (4) obtained in the step (A), and a step (C) of obtaining a phthalocyanine derivative represented by the general formula (6) or (7) from the compound represented by the general formula (5) obtained in the step (B).

[0078]

Chemical formula

[0079]

Chemical formula

[0080]

Chemical formula

[0081]

Chemical formula

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

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

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

[0085] The reaction temperature is not particularly limited as long as it allows the reaction to proceed favorably. However, as the lower limit, - 10°C or higher is preferred, 0°C or higher is more preferred, 10°C or higher is further preferred, and 15°C or higher is particularly preferred. As the upper limit, 100°C or lower is preferred, 80°C or lower is more preferred, 70°C or lower is further preferred, and 50°C or lower is particularly preferred. These upper and lower limits may be any single value or any combination thereof.

[0086] The reaction pressure is not particularly limited as long as the reaction proceeds suitably at a temperature, but as the lower limit, 0.1 MPa or more is preferable, 0.2 MPa or more is preferable, 0.3 MPa or more is preferable, 0.4 MPa or more is preferable. As the upper limit, 5 MPa or less is preferable, 3 MPa or less is preferable, 1 MPa or less is preferable, 0.9 MPa or less is preferable, 0.8 MPa or less is preferable, 0.7 MPa or less is preferable, 0.6 MPa or less is preferable, 0.5 MPa or less is preferable. These upper and lower limits may be any one alone or any combination.

[0087] [Step (B)] In step (B), by subjecting the compound (DA intermediate) represented by the general formula (4) obtained in the above step (A) to ring-opening dehydration, the compound (phthalic anhydride derivative) represented by the general formula (5) can be produced.

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

[0089] The reaction solvent is not particularly limited as long as the reaction proceeds suitably, but water, acetonitrile, toluene, xylene, alkylbenzene, or a mixed solvent thereof is preferable. Further, the above ring-opening dehydration reaction can also be carried out without a solvent.

[0090] The reaction temperature is not particularly limited as long as the reaction proceeds suitably at a temperature, but as the lower limit, 20°C or more is preferable, 25°C or more is preferable, 30°C or more is preferable, 35°C or more is preferable, 40°C or more is preferable. As the upper limit, 150°C or less is preferable, 140°C or less is preferable, 130°C or less is preferable, 120°C or less is preferable, 110°C or less is preferable, 100°C or less is preferable. These upper and lower limits may be any one alone or any combination.

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

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

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

[0094] The reaction temperature is not particularly limited as long as the reaction can proceed suitably. However, as the lower limit, 100°C or higher is preferable, 110°C or higher is more preferable, 120°C or higher is more preferable, 130°C or higher is more preferable, 140°C or higher is more preferable, and 150°C or higher is more preferable. As the upper limit, 250°C or lower is preferable, 240°C or lower is more preferable, 230°C or lower is more preferable, 220°C or lower is more preferable, 210°C or lower is more preferable, and 200°C or lower is more preferable. These upper and lower limits may be any single value or any combination thereof.

[0095] M 2 M of X 2 may preferably represent a metal atom, for example, 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, Zn, and even more preferably Cu, Zn. M 2 X of M may preferably represent a halogen atom, for example, preferably a chlorine atom.

[0096] The catalyst is not particularly limited as long as it can suitably promote the reaction, but a molybdenum catalyst is preferable, and ammonium molybdate(IV) tetrahydrate is more preferable. The addition amount of the above catalyst is preferably 0.001 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.1 mol% or more with respect to the compound (anhydrous phthalic acid derivative) represented by the general formula (5). The upper limit 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 any single value or any combination thereof.

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

[0098] The production method of the phthalocyanine derivative according to one embodiment can produce the furan derivative as a raw material by using the production method of the furan derivative according to the above one embodiment. Therefore, it is simple and inexpensive, can be carried out with ordinary laboratory equipment, is easy to scale up, and can reduce the production cost.

[0099] <Method for Producing Isoindoline Derivative> The production method of the isoindoline derivative according to one embodiment can use the furan derivative represented by the general formula (3) obtained by the production method of the furan derivative according to the above one embodiment. The production method of the isoindoline derivative according to one embodiment includes a step (a) of obtaining a compound represented by the general formula (4) from the furan derivative represented by the general formula (3), a step (b) of obtaining a compound represented by the general formula (5) from the compound represented by the general formula (4) obtained in the step (a), and a step (C) of obtaining at least one of the isoindoline derivatives represented by the general formulas (8) to (11) from the compound represented by the general formula (5) obtained in the step (b).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

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

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

[0102] [Step (b)] In step (b), the compound (DA intermediate) represented by the general formula (4) obtained in the above step (a) is subjected to ring-opening dehydration to produce a compound (phthalic anhydride derivative) represented by the general formula (5).

[0103] Specific examples of the compound (phthalic anhydride derivative) represented by the general formula (5) include the same ones as those listed in step (B) in the method for producing a phthalocyanine derivative according to the above-described embodiment.

[0104] Preferred reaction solvents include the same ones as those listed in step (B) in the method for producing a phthalocyanine derivative according to the above-described embodiment. The ring-opening dehydration reaction can also be carried out without a solvent. The suitable range of the reaction temperature may be the same as that listed in step (B) in the method for producing a phthalocyanine derivative according to the above-described embodiment. Preferred catalysts and their preferred amounts may be the same as those listed in step (B) in the method for producing a phthalocyanine derivative according to the above-described embodiment.

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

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

[0107] The reaction temperature is not particularly limited as long as it allows the reaction to proceed favorably, but as the lower limit, 20°C or higher is preferred, 40°C or higher is preferred, 60°C or higher is preferred, 80°C or higher is preferred, 100°C or higher is preferred. As the upper limit, 280°C or lower is preferred, 260°C or lower is preferred, 240°C or lower is preferred, 220°C or lower is preferred, 200°C or lower is preferred, 180°C or lower is preferred. These upper and lower limits can be any single one or any combination thereof.

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

[0109] The catalyst is not particularly limited as long as it can preferably promote the reaction, but a molybdenum catalyst is preferred, and ammonium molybdate (IV) tetrahydrate is more preferred. The addition amount of the above catalyst is preferably 0.001 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.1 mol% or more with respect to the compound (phthalic anhydride derivative) represented by the general formula (5) as the lower limit. As the 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 any single one or any combination.

[0110] Furthermore, an isatin derivative represented by the general formula (9) can be produced by reacting the obtained isatin derivative represented by the general formula (8) with barbituric acid. By reacting the obtained isatin derivative represented by the general formula (8) with barbituric acid and 2-cyano-N-methylacetamide, isatin derivatives represented by the general formulas (10) and (11) can be produced. Examples of the reaction between the isatin derivative represented by the 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 Unexamined Patent Application Publication No. 2019 - 112537, or International Publication No. 2009 / 074533. Examples of the reaction of the isoindoline derivative represented by the general formula (8) with barbituric acid and 2-cyano-N-methylacetamide include, but are not limited to, the methods described in JP-A-2020-026503, JP-A-2023-022808, WO 2022 / 014635, or JP-A-2022139293.

[0111] Specific examples of the reaction solvent include the same ones as those mentioned in the synthesis of the isoindoline derivative represented by the general formula (8) above. The preferred range of the reaction temperature may be the same as that mentioned in the synthesis of the isoindoline derivative 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 the formulas (9) to (11). The addition amount of the above catalyst is preferably 0.001 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.1 mol% or more, based on the compound (phthalic anhydride derivative) represented by the general formula (5) as the lower limit. The upper limit 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 any single value or any combination thereof.

[0112] The method for producing the isoindoline derivative according to one embodiment can produce the starting furan derivative using the method for producing the furan derivative according to the above one embodiment, so it is simple and inexpensive, can be carried out with ordinary laboratory equipment, is easy to scale up, and can reduce the production cost.

[0113] From the viewpoint of reducing the environmental load, the starting furaldehyde derivative is preferably derived from biomass in the method for producing the folic acid derivative according to one embodiment. Further, from the viewpoint of reducing environmental impact, it is preferable that the starting material, i.e., the furfural derivative or the folic acid derivative, of the production method of the furan derivative according to one embodiment is derived from biomass. Further, from the viewpoint of reducing environmental impact, it is preferable that the starting material, i.e., the furan derivative, of the production method of the phthalocyanine derivative according to 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 method of the folic acid derivative and the production method of the furan derivative according to 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 according to 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 according to 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 derivatives, folic acid derivatives, and furan derivatives, which are raw materials used in the production method of folic acid derivatives, furan derivatives, and phthalocyanine derivatives according to 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, still 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] Also, the biomass content of the folic acid derivatives, furan derivatives, and phthalocyanine derivatives obtained by the production method of folic acid derivatives, furan derivatives, and phthalocyanine derivatives according to 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, still more preferably 90% or more, and particularly preferably 95% or more in any method. The upper limit of the biomass content is not particularly limited and may be, for example, 100% or less.

[0118] In this specification, the biomass content may be the content (mass%) of carbon of biomass origin (radiocarbon atom 14 C) in all carbon, calculated by measurement according to ASTM-D6866-18. Since the carbon of petroleum-derived compounds and compositions usually does not contain radiocarbon atoms 14 C, this 14By measuring C, it is possible to confirm whether the generated compound or composition is a petroleum-derived compound or a biomass-derived compound.

[0119] As used herein, "containing radioactive carbon atoms 14 C" may include not only the meaning in the segregation approach, but also the meanings in the mass balance approach and the book-and-claim approach (Reference: Enabling Cirrcular Ecoonmy for Chemical with the Mass Balance Approach, the Ellen MacAthur Foundation network).

[0120] When biomass raw materials are available by the mass balance method or the book-and-claim method, it becomes easier to set the biomass degree of the raw materials used in the above-described methods for producing folic acid derivatives, furan derivatives, and phthalocyanine derivatives to 1 to 100%. In the present disclosure, the biomass degree including biomass raw materials by the mass balance method and the book-and-claim method is targeted.

Examples

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

[0122] Hereinafter, the measurement methods used in the examples and comparative examples will be described.

[0123] [Nuclear Magnetic Resonance Analysis (NMR)] For the obtained reaction product, 1 molecular structure analysis by 1H-NMR was performed. By confirming the peak derived from the target product, it was confirmed that the target product was indeed obtained. The measurement conditions are as follows. 〈Measuring Device and Conditions〉 Measuring device: JNM-ECM400S (manufactured by JEOL RESONANCE) Resonance frequency: 400 MHz Number of integrations: 16 times Solvent: DMSO-d6 Sample concentration: 5 mg / 1 mL

[0124] [Gas Chromatography-Mass Spectrometry (GC-MS)] For the furans synthesized in Examples 5 and 6 and the furan of Comparative Example 1, gas chromatography-mass spectrometry was performed. If necessary, the furan was dissolved in methanol, ethanol, ether, or tetrahydrofuran to a concentration of 0.5 to 3.0 mg / mL to obtain a measurement solution. The measurement conditions were as follows. 〈Measuring device and conditions〉 Measuring device: 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: 1 μL Split ratio: 30:1 Vaporization chamber temperature: 280 °C Column temperature program: Hold at 40 °C for 2 min → Heat at 10 °C / min and hold at 280 °C for 4 min Ion source: EI

[0125] (Example 1) To a 500 mL four-necked flask equipped with a mechanical stirrer, a condenser, a dropping funnel, and a thermometer, 60 g of sodium phosphate and 48 g of furfural were added. 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 held at 55 °C for 8 hours. Throughout the reaction, the pH of the reaction system was within the range of 3 to 5. Next, the reaction mixture was cooled to room temperature, adjusted to pH 12 using an NaOH solution, and then extracted with ethyl acetate. The obtained extract was acidified with hydrochloric acid and filtered to recover folic acid (white solid). The recovered folic acid was placed in a 100 mL round-bottom flask equipped with a distillation apparatus, and 0.04 g of Cu2O and 3 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 (2.8 g, yield 8%).

[0126] (Example 2) 101.19 g of triethylamine, 120 g of potassium acetate, and 48 g of furfural were added to a 1 L 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. Thereafter, the reaction mixture was maintained at 55 °C for 6 hours. Throughout the reaction, the pH of the reaction system was within the range of 9 to 12. Next, the reaction mixture was cooled to room temperature, adjusted to pH 12 using an 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). After the recovered folic acid was placed in a 300 mL round-bottom flask equipped with a distillation apparatus, 0.32 g of Cu2O and 25 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 (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, 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. Thereafter, 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 8 to 10. Next, the reaction mixture was cooled to room temperature, adjusted to pH 12 using an 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 0.11 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. Thereafter, 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 to 11. Next, the reaction mixture was cooled to room temperature, adjusted to pH 12 using an 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. Thereafter, 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 to 11. Next, the reaction mixture was cooled to room temperature, adjusted to pH 12 using an 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 (20.6 g, yield 60%). The purity of the folic acid determined from the GC-MS measurement values was over 99.5%, and it contained less than 0.5% of furanone, fumaric acid, maleic acid, or succinic acid. Also, the purity of the furan determined from the GC-MS measurement values was 99.844%, and it contained 0.156% of 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, 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. Thereafter, 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 to 11. Next, the reaction mixture was cooled to room temperature, adjusted to pH 12 using an 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 200 mL round-bottom flask equipped with a distillation apparatus, and 0.29 g of Cu2O and 45 mL of N-ethyl-2-pyrrolidone were added. The reaction mixture was maintained at 185 °C for 2 hours while stirring. Finally, furan (a colorless liquid) was collected (20.6 g, yield 60%). The purity of the folic acid determined from the GC-MS measurement values was over 99.5%, and it contained less than 0.5% of furanone, fumaric acid, maleic acid, or succinic acid. Also, the purity of the furan determined from the GC-MS measurement values was 99.880%, and it contained 0.120% of 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, 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 in the range of 9 to 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 phthalic acid (white solid). The recovered phthalic acid was placed in a 100 mL round-bottom flask equipped with a distillation apparatus and maintained at 185 °C for 2 hours while 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, 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 in the range of 9 to 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 phthalic acid (white solid). The recovered phthalic acid was placed in a 200 mL round-bottom flask equipped with a distillation apparatus, and 45 mL of N-ethyl-2-pyrrolidone was added. The reaction mixture was maintained at 185 °C for 2 hours while stirring. Finally, furan (colorless liquid) was collected (11.1 g, yield 32%).

[0133] (Example 9) To a 500 mL four-necked flask equipped with a mechanical stirrer, a condenser, a dropping funnel, and a thermometer, 74 g of potassium acetate and 48 g of furfural were added. The reaction mixture was stirred and heated to 75 °C, and then 68 g of 30% H2O2 was added dropwise over 1 hour. Thereafter, 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 to 11. Next, the reaction mixture was cooled to room temperature, adjusted to pH 12 using an NaOH solution, and then extracted with ethyl acetate. The obtained extract was acidified with hydrochloric acid and filtered to recover phthalic acid (white solid). The recovered phthalic acid was placed in a 200 mL round-bottom flask equipped with a distillation apparatus, and 57 mL of hexadecane was added. The reaction mixture was maintained at 185 °C for 2 hours while stirring. Finally, furan (colorless liquid) was collected (9.7 g, yield 35%).

[0134] (Comparative Example 1) Commercially available furan (manufactured by Sinopharm Chemical Reagent) was used as Comparative Example 1 and compared with the examples. The purity of furan determined from the GC-MS measurement values was 100.000%.

Industrial Applicability

[0135] According to the present invention, phthalic acid derivatives, furan derivatives, phthalocyanine derivatives, and isoindoline derivatives can be produced respectively by a simpler production method than conventional ones, with higher yields and at lower costs. Therefore, each production method of the present invention can be easily scaled up and can greatly contribute to the future production development of phthalic acid derivatives, furan derivatives, phthalocyanine derivatives, and isoindoline derivatives derived from biomass, and is a clean and green method.

Claims

1. 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 (I), the oxidation step including a reaction system having a pH of 3 to 12, 【Chemical 1】 wherein, R １ 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, R ２ and R ３ each 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, an aryl group having 6 to 12 carbon atoms which may be substituted, or, R ２ and R ３ which form a 5- to 8-membered ring by closing the 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, methanesulfonic acid, p-toluenesulfonic acid, phosphoric acid, phosphoric anhydride, polyphosphoric acid, pyrophosphoric acid, phosphorous acid, and salts thereof, and compounds represented by the general formulas (A1) to (A4) are used, 【Chemical 2】 wherein, X represents -OH group, -OM １ group, or -R ４ wherein M １ represents an alkali metal atom, R ４ 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, Y １ represents a hydrogen atom, an alkali metal atom, -COR ５ , or a functional group represented by the general formula (B), R ５ 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, Z represents a sulfur atom or a phosphorus atom, W represents an oxygen atom or is substantially the same as the X, n1 is an integer of 1 to 10, 【Chemical Formula 3】 R of the general formula (B) ６ represents 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, 【Chemical Formula 4】 X in the general formulas (A3) and (A4) is independently substantially the same as X in the general formulas (A1) and (A2), Y ２ represents an alkaline earth metal atom, Z is substantially the same as Z in the general formulas (A1) and (A2), W represents an oxygen atom or is substantially the same as X in the general formulas (A1) and (A2), n2 and n3 are each independently an integer of 1 to 10, The method for producing a folic acid derivative according to claim 1.

3. In the oxidation step, O ２ , H ２ O ２ , O ３ , KMnO ４ , KClO ３ , or NaClO is used. The method for producing a folic acid derivative according to claim 1 or 2.

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

5. A decarboxylation step of obtaining a furan derivative represented by the general formula (3) by decarboxylating a folic acid derivative represented by the general formula (2) as shown in the reaction formula (II), the decarboxylation step including decarboxylation without a catalyst or using an oxide of a trivalent transition metal as a catalyst, 【Chemical Formula 5】 wherein, R １ 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, R ２ and R ３ each 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, an aryl group having 6 to 12 carbon atoms which may be substituted, or R ２ and R ３ which form a 5- to 8-membered ring by closing the ring A method for producing a furan derivative.

6. A decarboxylation step of obtaining a furan derivative represented by the general formula (3) by decarboxylating a folic acid derivative represented by the general formula (2) as shown in the reaction formula (II), the decarboxylation step including decarboxylation using a high-boiling solvent, 【Chemical Formula 6】 wherein, R １ 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, R ２ and R ３ each 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, an aryl group having 6 to 12 carbon atoms which may be substituted, or R ２ and R ３ which form a 5- to 8-membered ring by closing the ring A method for producing a furan derivative.

7. 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), the oxidation step having a reaction system with a pH of 3 to 12, and As shown in Reaction Formula (III), a decarboxylation step of obtaining a furan derivative represented by General Formula (3) by decarboxylating the folic acid derivative represented by General Formula (2) obtained in the oxidation step, the decarboxylation step being carried out without a catalyst or using an oxide of a transition metal having a valence of 1 to 3 as a catalyst, 【Chemical Formula 7】 wherein, R １ 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, R ２ and R ３ each 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, an aryl group having 6 to 12 carbon atoms which may be substituted, or R ２ and R ３ which form a 5- to 8-membered ring by closing the ring A method for producing a furan derivative. **Claim 8** As shown in Reaction Formula (III), an oxidation step of obtaining a folic acid derivative represented by General Formula (2) by oxidizing a furfural derivative represented by General Formula (1), the oxidation step being carried out at a pH of 3 to 12 in the reaction system, As shown in Reaction Formula (III), a decarboxylation step of obtaining a furan derivative represented by General Formula (3) by decarboxylating the folic acid derivative represented by General Formula (2) obtained in the oxidation step, the decarboxylation step being carried out using a high-boiling solvent comprising 【Chemical Formula 8】 wherein, R １ 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, R ２ and R ３ each 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, an aryl group having 6 to 12 carbon atoms which may be substituted, or R ２ and R ３ which form a 5- to 8-membered ring by closing the ring A method for producing a furan derivative. **Claim 9** 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 9】 wherein, X represents -OH group, -OM １ group, or -R ４ wherein M １ represents an alkali metal atom, R ４ 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, Y １ represents a hydrogen atom, an alkali metal atom, -COR ５ , or a functional group represented by the general formula (B). R ５ 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, Z represents a sulfur atom or a phosphorus atom, W represents an oxygen atom or is substantially the same as X, n1 is an integer of 1 to 10, 【Chemical 10】 R of the general formula (B) ６ represents 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. 【Chemical 11】 X in General Formulas (A3) and (A4) is each independently substantially the same as X in General Formulas (A1) and (A2), Y ２ represents an alkaline earth metal atom, and Z is substantially the same as Z in General Formulas (A1) and (A2), W represents an oxygen atom or is substantially the same as X in General Formulas (A1) and (A2), n2 and n3 are each independently an integer of 1 to 10 The method for producing a furan derivative according to Claim 7 or 8. **Claim 10** In the oxidation step, O ２ , H ２ O ２ , O ３ , KMnO ４ , KClO ３ , or NaClO is used. The method for producing a furan derivative according to claim 7 or 8. **Claim 11** The method for producing a furan derivative according to Claim 7 or 8, wherein the oxidation step is carried out at a temperature of 0 to 120°C. **Claim 12** The method for producing a furan derivative according to any one of Claims 5 to 8, wherein the biomass degree of the furan derivative is 1% or more. **Claim 13** A method for producing a phthalocyanine derivative from a furan derivative obtained by the method for producing a furan derivative according to any one of Claims 5 to 8, a step (A) of obtaining a compound represented by General Formula (4) from the furan derivative represented by General Formula (3), Step (B) of obtaining a compound represented by the general formula (5) from the compound represented by the general formula (4) obtained in the above step (A), Step (C) of obtaining a phthalocyanine derivative represented by the general formula (6) or (7) from the compound represented by the general formula (5) obtained in the above step (B), which comprises 【Chemical 12】 【Chemical 13】 【Chemical 14】 【Chemical Formula 15】 wherein R １ 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, R ２ and R ３ each 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, an aryl group having 6 to 12 carbon atoms which may be substituted, or R ２ and R ３ form a 5- to 8-membered ring by closing the ring, M ２ represents a metal atom, A method for producing a phthalocyanine derivative.

14. A method for producing an isoindoline derivative from a furan derivative obtained by the method for producing a furan derivative according to any one of Claims 5 to 8, Step (a) of obtaining a compound represented by the general formula (4) from the furan derivative represented by the general formula (3), Step (b) of obtaining a compound represented by the general formula (5) from the compound represented by the general formula (4) obtained in the above step (a), Step (C) of obtaining at least one of the isoindoline derivatives represented by the general formulas (8) to (11) from the compound represented by the general formula (5) obtained in the above step (b), which comprises 【Chemical Formula 16】 【Chemical 17】 【Chemical 18】 【Chemical 19】 【Chemical 20】 【Chemical 21】 wherein R １ 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, R ２ and R ３ each 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, an aryl group having 6 to 12 carbon atoms which may be substituted, or, R ２ and R ３ which form a 5- to 8-membered ring by closing a ring A method for producing an isoindoline derivative.

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