Dinaphthofuran derivative and method for producing the same

Abstract

To provide a novel dinaphthofuran derivative having a single functional group (reactive group or functional group).SOLUTION: A novel dinaphthofuran derivative is prepared, which is represented by formula (1) below. [In the formula, R1 and R2 represent linear hydrocarbon groups having oxygen atoms and / or unsaturated carbon bonds; R3 and R4 independently represent substituents different from R1 and R2; n represents 0 or 1; m represents an integer of 0 to 5; and k represents an integer of 0 to 6].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a novel dinaphthofuran derivative and a method for producing the same. [Background technology]

[0002] Dinaphtho[2,1-b:1',2'-d]furan (hereinafter simply referred to as "dinaphthofuran") has a polycyclic aromatic hydrocarbon skeleton and is therefore expected to be used in electrical and electronic materials, optical materials, coating agents, and the like. Dinaphthofuran derivatives substituted with various substituents are known.

[0003] Many disubstituted dinaphthofuran derivatives are known, and for example, JP 2014-133713 A (Patent Document 1) discloses derivatives in which aryl groups or heterocyclic groups are substituted at the 5- and 9-positions of dinaphthofuran.

[0004] JP 2018-512726 A (Patent Document 2) discloses a derivative in which an aryl group or a heterocyclic group is substituted at the 6-position of a dinaphthofuran. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2014-133713 A [Patent Document 2] Special Publication No. 2018-512726 Summary of the Invention [Problem to be solved by the invention]

[0006] As disclosed in Patent Document 1, many disubstituted dinaphthofuran derivatives are known, but almost no monosubstituted dinaphthofuran derivatives are known. Patent Document 2 discloses dinaphthofuran derivatives in which an aryl group or a heterocyclic group is substituted at the 6-position of dinaphthofuran, but these derivatives have no active group, low reactivity and functionality, and low solubility in organic solvents.

[0007] Accordingly, an object of the present invention is to provide a novel dinaphthofuran derivative having a single functional group (reactive group or functional group) and a method for producing the same.

[0008] Another object of the present invention is to provide a novel dinaphthofuran derivative having excellent solubility in organic solvents and a method for producing the same. [Means for solving the problem]

[0009] As a result of intensive research to achieve the above-mentioned object, the present inventors have found that a novel dinaphthofuran derivative in which a chain hydrocarbon group having an oxygen atom and / or an unsaturated carbon bond (ethylenically unsaturated bond) is substituted at the 5- or 6-position of dinaphthofuran has reactivity and functionality, and have completed the present invention.

[0010] That is, the dinaphthofuran derivative according to embodiment [1] of the present invention is represented by the following formula (1).

[0011] [ka]

[0012] [In the formula, R 1 and R 2 represents a chain hydrocarbon group having an oxygen atom and / or an unsaturated carbon bond, R 3 and R 4 is independently R 1 and R 2 represents a substituent different from n is 0 or 1, m represents an integer of 0 to 5; k is an integer from 0 to 6.

[0013] To facilitate understanding of the invention, the dinaphthofuran rings in the above formula (1) are given position numbers (numbers 1 to 13).

[0014] The dinaphthofuran derivative according to the embodiment [2] of the present invention is a compound represented by the formula (1) of the embodiment [1], wherein R 1 or R 2 represents any group selected from the following formulae (1a), (1b) and (1c).

[0015] [ka]

[0016] [In the formula, X 1 , X 2 , X 4 , X 5 each independently represents a hydrogen atom or a chain hydrocarbon (aliphatic hydrocarbon) group, and X 3 represents a hydrogen atom, an optionally substituted chain hydrocarbon group, or an acyl group.

[0017] The dinaphthofuran derivative according to embodiment [3] of the present invention is an embodiment in which n is 1 in formula (1) of embodiment [1] or [2] above.

[0018] The dinaphthofuran derivative according to the embodiment [4] of the present invention is the above-mentioned embodiment [2] or [3], wherein X of the formula (1a), (1b) or (1c) is 1 and X 2 represents a hydrogen atom or an alkyl group, and X 3 represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkenoyl group (alkenylcarbonyl group), and X 4 and X 5 indicates a hydrogen atom.

[0019] The dinaphthofuran derivative according to the embodiment [5] of the present invention is, in any one of the above embodiments [2] to [4], X of the above formula (1b) 3represents an alkenyl group or a (meth)acryloyl group.

[0020] The dinaphthofuran derivative according to the embodiment [6] of the present invention, in any one of the above embodiments [2] to [5], is a compound represented by the formula (1a) and (1b), 1 and X 2 indicates a hydrogen atom, and X 3 represents a hydrogen atom, an alkenyl group, or a (meth)acryloyl group.

[0021] The dinaphthofuran derivative according to the embodiment [7] of the present invention, in any one of the above embodiments [1] to [6], is represented by the following formula (2c).

[0022] [ka]

[0023] [In the formula, R 3 and R 4 are independently the groups [-CHX 2 (OX 3a )] and X 2 represents a hydrogen atom or an aliphatic hydrocarbon group, and X 3a represents an alkenyl group or a (meth)acryloyl group, m represents an integer of 0 to 5, and k represents an integer of 0 to 6.

[0024] The method for producing a dinaphthofuran derivative according to embodiment [8] of the present invention is a method for producing the dinaphthofuran derivative according to any one of embodiments [1] to [7] above, comprising an acyl group substitution step of reacting a dinaphthofuran compound represented by the following formula (2) with an acylating agent to substitute an acyl group at the 5-position or 6-position of the dinaphthofuran compound.

[0025] [ka]

[0026] [In the formula, R 3 and R 4 are independently R1 and R 2 m represents an integer of 0 to 5; k represents an integer of 0 to 6; and at least one of the 5-position and the 6-position is a group R 3 not replaced by

[0027] The method for producing a dinaphthofuran derivative according to embodiment [9] of the present invention is a method in which, in the acyl group substitution step of embodiment [8], the dinaphthofuran compound is reacted with the acylating agent in the presence of an acid catalyst to substitute an acyl group at the 5-position of the dinaphthofuran compound represented by formula (2).

[0028] The method for producing a dinaphthofuran derivative according to embodiment

[10] of the present invention is a method in which, in the acyl group substitution step of embodiment [8], the dinaphthofuran compound is reacted with an organolithium compound and the acylating agent to substitute an acyl group at the 6-position of the dinaphthofuran compound represented by formula (2).

[0029] The manufacturing method according to embodiment

[11] of the present invention comprises the steps of: A method for producing a dinaphthofuran derivative represented by the following formula (2c): an acyl group substitution step of reacting a dinaphthofuran compound represented by the following formula (2) with an acylating agent to substitute an acyl group at the 5-position of the dinaphthofuran compound to obtain an acyl-substituted product; a reduction step of reducing the acyl-substituted product to obtain a hydroxyl-containing dinaphthofuran derivative; and The production method includes an etherification step of reacting the hydroxyl group-containing dinaphthofuran derivative with an etherification agent to obtain the dinaphthofuran derivative represented by the formula (2c).

[0030] [ka]

[0031] [In the formula, R 3 and R 4 are independently the groups [-CHX 2 (OX 3a)] and X 2 represents a hydrogen atom or an aliphatic hydrocarbon group, and X 3a represents an alkenyl group, m represents an integer of 0 to 5, and k represents an integer of 0 to 6.

[0032] [ka]

[0033] [In the formula, R 3 and R 4 each independently represents a group [-CHX 2 (OX 3a )], m represents an integer of 0 to 5, k represents an integer of 0 to 6, and at least one of the 5-position and the 6-position is a group R 3 not replaced by

[0034] The manufacturing method according to embodiment

[12] of the present invention comprises the steps of: A method for producing a dinaphthofuran derivative represented by the following formula (2c): an acyl group substitution step of reacting a dinaphthofuran compound represented by the following formula (2) with an acylating agent to substitute an acyl group at the 5-position of the dinaphthofuran compound to obtain an acyl-substituted product; a reduction step of reducing the acyl-substituted product to obtain a hydroxyl-containing dinaphthofuran derivative; and The production method includes an esterification step of reacting the hydroxyl group-containing dinaphthofuran derivative with an esterifying agent to obtain the dinaphthofuran derivative represented by the formula (2c).

[0035] [ka]

[0036] [In the formula, R 3 and R 4 are independently the groups [-CHX 2 (OX 3a )] and X 2 represents a hydrogen atom or an aliphatic hydrocarbon group, and X 3arepresents a (meth)acryloyl group, m represents an integer of 0 to 5, and k represents an integer of 0 to 6.

[0037] [ka]

[0038] [In the formula, R 3 and R 4 each independently represents a group [-CHX 2 (OX 3a )], m represents an integer of 0 to 5, k represents an integer of 0 to 6, and at least one of the 5-position and the 6-position is a group R 3 not replaced by

[0039] The liquid composition according to embodiment

[13] of the present invention includes a liquid composition comprising the dinaphthofuran derivative according to any one of embodiments [1] to [7] above and an organic solvent.

[0040] In this specification and the claims, "dinaphthofuran" is used to mean dinaphtho[2,1-b:1',2'-d]furan. Effect of the Invention

[0041] The present invention provides a novel dinaphthofuran derivative in which a chain hydrocarbon group having an oxygen atom and / or an unsaturated carbon bond (particularly an ethylenically unsaturated bond) is substituted at the 5th or 6th position of dinaphthofuran. Furthermore, this novel dinaphthofuran derivative has excellent solubility in organic solvents. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] [New dinaphthofuran derivatives and their properties] The novel dinaphthofuran derivative of the present invention is represented by the following formula (1).

[0043] [ka]

[0044] [In the formula, R 1 and R 2 represents a chain hydrocarbon group having an oxygen atom and / or an unsaturated carbon bond, and R 3 and R 4 is independently R 1 and R 2 represents a substituent different from that represented by the formula (1), n ​​represents 0 or 1, m represents an integer of 0 to 5, k represents an integer of 0 to 6, and the numbers 1 to 13 represent position numbers.

[0045] In the formula (1), R 1 and R 2 Examples of the chain hydrocarbon group having an oxygen atom include hydroxyalkyl groups (e.g., hydroxymethyl groups, hydroxyethyl groups, hydroxypropyl groups, hydroxyhexyl groups, etc.) 1-12 alkyl groups, acyl groups (e.g., acetyl, propionyl, butyryl, valeryl, hexanoyl, etc.) 2-12 acyl groups, etc.), alkoxy groups (e.g., methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc. 1-12 Alkoxy groups, etc.), acyloxy groups (e.g., acetyloxy groups, propionyloxy groups, butyryloxy groups, valeroxy groups, hexanoyloxy groups, etc.) 2-12 acyl group, etc.), polyether group (e.g., polyoxy C such as polyoxymethylene group, polyoxyethylene group, polyoxypropylene group, etc. 1-4 Among these, hydroxy C groups such as hydroxymethyl group and 1-hydroxyethyl group are included. 1-6 Alkyl groups (especially hydroxy C 1-3 C such as alkyl group, methoxy group, etc. 1-3 Alkoxy groups are preferred.

[0046] R 1 and R 2Examples of the chain hydrocarbon group having an unsaturated hydrocarbon bond include alkenyl groups (e.g., vinyl groups, allyl groups, isopropenyl groups, 1-propenyl groups, 1-butenyl groups, 2-butenyl groups, 3-butenyl groups, pentenyl groups, hexenyl groups, etc. 2-12 alkenyl groups, alkynyl groups (e.g., ethynyl, propynyl groups, etc.) 2-12 Alkynyl groups, alkadienyl groups (e.g., allenyl groups, 1,3-butadienyl groups, 1,4-hexadienyl groups, etc.) 3-12 Among these, vinyl groups, 1-propenyl groups, etc. 2-4 The propenyl group is preferred.

[0047] R 1 and R 2 Examples of the chain hydrocarbon group having an oxygen atom and an unsaturated hydrocarbon group include a group having an unsaturated carboxylic acid skeleton [e.g., a C group such as a (meth)acryloyloxy group, a crotonoyloxy group, a pentenoyloxy group, or a hexenoyloxy group]. 3-12 groups having an alkenoyloxy group, etc.], alkenyl ether groups (e.g., vinyl ether groups, allyl ether groups, etc. 2-12 Among these, (meth)acryloyloxy C groups such as (meth)acryloyloxymethyl group and 1-[(meth)acryloyloxy]ethyl group are examples. 1-3 C such as alkyl group, vinyloxy group, and allyloxy group 2-4 Alkenyloxy groups are preferred.

[0048] These groups may be used alone or in combination of two or more. 1 and R 2 is preferably any group selected from the following formulae (1a), (1b) and (1c).

[0049] [ka]

[0050] [In the formula, X 1 , X 2 , X 4 , X 5 each independently represents a hydrogen atom or a chain hydrocarbon group; 3 represents a hydrogen atom, an optionally substituted chain hydrocarbon group, or an acyl group.

[0051] X 1 ~X 5 Examples of the chain hydrocarbon group include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decyl, and dodecyl groups. 1-12 alkyl groups, alkenyl groups (e.g., vinyl groups, allyl groups, isopropenyl groups, 1-propenyl groups, 1-butenyl groups, 2-butenyl groups, 3-butenyl groups, pentenyl groups, hexenyl groups, etc.) 2-12 alkenyl groups, etc.

[0052] X 3 The substituent of the chain hydrocarbon group is, for example, a linear or branched C group such as a hydroxyl group, an alkoxy group (e.g., a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. 1-6 Alkoxy groups, etc.

[0053] Preferred X 3 Examples of the chain hydrocarbon group include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl groups. 1-6 alkyl groups, hydroxyalkyl groups (e.g., hydroxymethyl groups, hydroxyethyl groups, hydroxypropyl groups, etc.) 1-6 alkyl groups, alkenyl groups (e.g., vinyl groups, allyl groups, isopropenyl groups, 1-propenyl groups, 1-butenyl groups, 2-butenyl groups, 3-butenyl groups, etc.) 2-6 alkenyl groups, etc.

[0054] X 3The acyl group of C 1-12 Acyl groups, such as formyl groups; acetyl groups, propionyl groups, butyryl groups, valeryl groups, hexanoyl groups, etc. 2-12 Alkanoyl groups; (meth)acryloyl groups, crotonoyl groups, pentenoyl groups, hexenoyl groups, etc. 3-12 alkenoyl groups and the like.

[0055] In the formula (1a), the group X 1 Examples of the alkyl group include a hydrogen atom and an alkyl group. 1-6 An alkyl group is preferred, a hydrogen atom, C 1-3 An alkyl group is more preferable, and a hydrogen atom, a methyl group, etc. 1-2 Alkyl groups are most preferred.

[0056] In the formula (1b), the group X 2 Examples of the alkyl group include a hydrogen atom and an alkyl group. 1-6 An alkyl group is preferred, a hydrogen atom, C 1-3 An alkyl group is more preferable, and a hydrogen atom, a methyl group, etc. 1-2 Alkyl groups are most preferred.

[0057] Group X 3 Examples of the alkyl group include a hydrogen atom, an alkyl group, an alkenyl group, and an acyl group. 1-3 Alkyl group, C 2-6 Alkenyl group, C 3-6 Alkenoyl groups are preferred, C 2-5 Alkenyl group, C 3-5 Alkenoyl groups are more preferred, and C groups such as vinyl groups and allyl groups are preferred. 2-4 An alkenyl group or a (meth)acryloyl group is more preferred, and an allyl group is most preferred.

[0058] In the formula (1c), the group X 4 and group X 5 Examples of the alkyl group include a hydrogen atom and an alkyl group. 1-6An alkyl group is preferred, and a C 1 1―3 An alkyl group is more preferred, and a hydrogen atom is even more preferred.

[0059] R 3 and R 4 The substituents (non-reactive or non-polymerizable substituents) of R 1 and R 2 Any group different from the above may be used, and examples thereof include a halogen atom, a hydrocarbon group, an alkoxy group, a nitro group, and a cyano group.

[0060] Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0061] Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include a linear or branched C alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. 1-6 Examples of the cycloalkyl group include a C alkyl group such as a cyclopentyl group and a cyclohexyl group. 5-10 Examples of the aryl group include C aryl groups such as phenyl and naphthyl groups. 6-14 Examples of the aralkyl group include C aryl groups such as benzyl groups and phenethyl groups. 6-10 Aryl C 1-6 Alkyl groups and the like.

[0062] Examples of the alkoxy group include C alkoxy groups such as methoxy groups, ethoxy groups, propoxy groups, and butoxy groups. 1-6 Examples of the alkyl group include an alkoxy group.

[0063] These substituents may be used alone or in combination of two or more. Among these, alkyl groups are preferred, and linear or branched C groups such as methyl groups and ethyl groups are preferred. 1-3 Alkyl groups are particularly preferred.

[0064] R 1 The number of substitutions n may be 0 or 1, and is preferably 1 from the viewpoint of excellent solvent solubility.

[0065] Substituent R 3 The number of substitutions m may be an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and most preferably 0.

[0066] Substituent R 4 The number of substitutions k may be an integer of 0 to 6, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and most preferably 0.

[0067] When m and / or k are 1 or more, the group R 3 and / or the group R 4 The substitution position of the group R 3 is the 1-6 position of the dinaphthofuran skeleton, and the R group 4 may be substituted at any of the 8-13 positions of the dinaphthofuran skeleton. 3 and / or the group R 4 When substituted, the group R 3 and / or the group R 4 The types of may be the same or different. When n is 1, the group R 3 may be substituted at any of the 1-4 and 6-positions of the dinaphthofuran skeleton, and when n is 0, the group R 3 may be substituted at any of positions 1 to 5 of the dinaphthofuran skeleton.

[0068] Representative compounds represented by the formula (1) include, for example, dinaphthofuran derivatives represented by the following formulas (2a) to (2h).

[0069] [ka]

[0070] (In the formula, R 3 , R 4, m, and k are the same as those in formula (1), and X 1 , X 2 , X 4 , X 5 is the same as the above formulas (1a) to (1c), and X 3a is an optionally substituted chain hydrocarbon group or an acyl group.

[0071] (Dinaphthofuran derivative (2a)) The dinaphthofuran derivative represented by the formula (2a) [dinaphthofuran derivative (2a)] is a compound represented by the formula (1) in which n is 1 and a group R 1 is a dinaphthofuran derivative (5-acyl compound) represented by the above formula (1a).

[0072] In the formula (2a), the group X 1 Examples of the alkyl group include linear or branched C alkyl groups such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a decyl group, and a dodecyl group. 1-12 Among these, hydrogen atom, C 1-6 Alkyl groups are preferred, C 1-3 Alkyl groups are more preferred, and C 1-2 Alkyl groups are more preferred.

[0073] Substituent R 3 and its number of substitutions m, and the substituent R 4 The number of substitutions k is determined by the R 3 , R 4 , m and k.

[0074] Representative dinaphthofuran derivatives (2a) include 5-C dinaphthofuran derivatives such as 5-acetyldinaphthofuran, 5-propionyldinaphthofuran, 5-butyryldinaphthofuran, 5-valeryldinaphthofuran, and 5-hexanoyldinaphthofuran. 2-7 Alkanoyl-dinaphthofuran and the like.

[0075] The refractive index of the dinaphthofuran derivative (2a) at a temperature of 25° C. and a wavelength of 589 nm may be 1.6 or more (particularly 1.7 or more), for example, 1.6 to 1.8, preferably 1.63 to 1.78, further preferably 1.65 to 1.75, and even more preferably 1.68 to 1.72.

[0076] In this specification and claims, the refractive index can be measured in accordance with the method described in the examples below.

[0077] The dinaphthofuran derivative (2a) has excellent solubility in organic solvents. Examples of the organic solvent include aromatic hydrocarbons (particularly, toluene), cyclic ethers [particularly, tetrahydrofuran (THF)], amides (particularly, N,N-dimethylformamide), esters (particularly, ethyl acetate), alkylene glycol ether acetates (particularly, propylene glycol monomethyl ether acetate (PGMEA)), (meth)acrylic acid esters (particularly, methyl methacrylate), and aromatic vinyls (particularly, styrene).

[0078] The solubility of the dinaphthofuran derivative (2a) in THF may be 1% by mass or more (particularly 3% by mass or more), for example, 2 to 30% by mass, preferably 3 to 20% by mass, and more preferably 3.5 to 10% by mass.

[0079] In the present specification and claims, the solubility in an organic solvent can be measured in accordance with the method described in the examples below.

[0080] (Dinaphthofuran derivative (2b)) The dinaphthofuran derivative represented by formula (2b) [dinaphthofuran derivative (2b)] is a compound represented by formula (1), in which n is 1 and the group R 1 represents formula (1b), and X 3 represents a hydrogen atom.

[0081] In the formula (2b), the group X 2Examples of the group X in the formula (2a) include a hydrogen atom; 1 Among these, hydrogen atom, C 1-6 Alkyl groups are preferred, C 1-3 Alkyl groups are more preferred, and C 1-2 Alkyl groups are more preferred.

[0082] Substituent R 3 and its number of substitutions m, and the substituent R 4 The number of substitutions k is determined based on the R 3 , R 4 , m and k.

[0083] Representative dinaphthofuran derivatives (2b) include 5-hydroxy C dinaphthofuran derivatives such as 5-(1-hydroxyethyl)dinaphthofuran, 5-(1-hydroxypropyl)dinaphthofuran, and 5-(1-hydroxybutyl)dinaphthofuran. 2-7 Alkyl dinaphthofuran and the like.

[0084] The refractive index of the dinaphthofuran derivative (2b) at a temperature of 25° C. and a wavelength of 589 nm may be 1.6 or more (particularly 1.65 or more), for example, 1.6 to 1.8, preferably 1.63 to 1.78, further preferably 1.65 to 1.75, and even more preferably 1.68 to 1.72.

[0085] The dinaphthofuran derivative (2b) has excellent solubility in organic solvents. Examples of organic solvents include alkanols (particularly, methanol), aromatic hydrocarbons (particularly, toluene), cyclic ethers [particularly, tetrahydrofuran (THF)], amides (particularly, N,N-dimethylformamide), esters (particularly, ethyl acetate), alkylene glycol ether acetates (particularly, propylene glycol monomethyl ether acetate (PGMEA)), (meth)acrylic acid esters (particularly, methyl methacrylate), and aromatic vinyls (particularly, styrene). Among these organic solvents, the solubility is particularly high in THF and N,N-dimethylformamide.

[0086] The solubility of the dinaphthofuran derivative (2b) in THF may be 10% by mass or more, for example, 10 to 70% by mass, preferably 20 to 50% by mass, and more preferably 30 to 40% by mass.

[0087] The solubility of the dinaphthofuran derivative (2b) in N,N-dimethylformamide may be 10% by mass or more, for example, 10 to 80% by mass, preferably 30 to 60% by mass, and more preferably 40 to 50% by mass.

[0088] (Dinaphthofuran derivative (2c)) The dinaphthofuran derivative represented by formula (2c) [dinaphthofuran derivative (2c)] is a compound represented by formula (1), in which n is 1 and the group R 1 corresponds to formula (1b), and X 3 represents a chain hydrocarbon group or an acyl group which may have a substituent.

[0089] In the formula (2c), the group X 2 Examples of the group X in the formula (2a) include a hydrogen atom; 1 Among these, hydrogen atom, C 1-6 Alkyl groups are preferred, C 1-3 Alkyl groups are more preferred, and C 1-2 Alkyl groups are more preferred.

[0090] Group X 3a Examples of the acyl group include a formyl group; an acetyl group, a propionyl group, a butyryl group, a valeryl group, a hexanoyl group, and the like. 2-12 Alkanoyl groups; (meth)acryloyl groups, crotonoyl groups, pentenoyl groups, hexenoyl groups, etc. 3-12 Alkenyl groups and the like. 3-6 Alkenoyl groups are preferred, C 3-5 An alkenoyl group is more preferred, and a (meth)acryloyl group is even more preferred.

[0091] Group X 3a Examples of the chain hydrocarbon group include the group X in the formula (1b). 3 Alkyl groups and alkenyl groups (e.g., vinyl groups, allyl groups, isopropenyl groups, 1-propenyl groups, 1-butenyl groups, 2-butenyl groups, 3-butenyl groups, pentenyl groups, hexenyl groups, etc.) exemplified as 2-12 Of these, C groups such as ethyl groups are 1-3 C such as alkyl group, vinyl group, and allyl group 2-6 Alkenyl groups are preferred, C 2-4 Alkenyl groups are more preferred, and C such as allyl groups. 3-4 Alkenyl groups are more preferred.

[0092] X 3a The substituent of the chain hydrocarbon group is, for example, a linear or branched C group such as a hydroxyl group, an alkoxy group (e.g., a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. 1-6 Among these, a hydroxyl group is preferred. Furthermore, X 3a The chain hydrocarbon group is more preferably a chain hydrocarbon group having no substituent.

[0093] Preferred group X 3a As for C 3-12 Alkenoyl group, C 2-6 Alkenyl groups are exemplified, among which (meth)acryloyl groups, C2-4 Alkenyl groups are more preferred, and C such as allyl groups. 3-4 Alkenyl groups are more preferred.

[0094] Substituent R 3 and its number of substitutions m, and the substituent R 4 The number of substitutions k is determined by the R 3 , R 4 , m and k.

[0095] Representative group X 3a Examples of the dinaphthofuran derivative (2c) in which is an acyl group such as a (meth)acryloyl group include 5-(meth)acryloyloxy C such as 5-[1-(acryloyloxy)ethyl]dinaphthofuran and 5-[1-(methacryloyloxy)ethyl]dinaphthofuran. 2-6 Alkyl dinaphthofuran and the like.

[0096] Representative group X 3a Examples of the dinaphthofuran derivative (2c) in which is a chain hydrocarbon group which may have a substituent include 5-C dinaphthofuran derivatives such as 5-(1-methoxyethyl)dinaphthofuran. 1-3 Alkoxy C 2-7 5-C alkyldinaphthofuran, 5-[1-(vinyloxy)ethyl]dinaphthofuran, 5-[1-(allyloxy)ethyl]dinaphthofuran, etc. 2-10 Alkenyloxy C 2-7 Alkyl dinaphthofuran and the like.

[0097] The refractive index of the dinaphthofuran derivative (2c) at a temperature of 25° C. and a wavelength of 589 nm may be 1.6 or more (particularly 1.65 or more), for example, 1.6 to 1.8, preferably 1.63 to 1.75, further preferably 1.65 to 1.73, and even more preferably 1.67 to 1.71.

[0098] In particular, the group X 3aThe refractive index of the dinaphthofuran derivative (2c) in which is an acyl group [particularly, a (meth)acryloyl group] is, for example, 1.6 to 1.8, preferably 1.63 to 1.75, further preferably 1.64 to 1.72, and even more preferably 1.66 to 1.7.

[0099] In particular, the group X 3a The refractive index of the dinaphthofuran derivative (2c) in which is an alkenyl group [particularly, an allyl group] is, for example, 1.6 to 1.8, preferably 1.62 to 1.75, further preferably 1.63 to 1.72, and even more preferably 1.65 to 1.7.

[0100] In particular, the group X 3a is an alkyl group [especially C 1-3 The refractive index of the dinaphthofuran derivative (2c) in which the alkyl group is a substituted or unsubstituted alkyl group is, for example, 1.6 to 1.8, preferably 1.65 to 1.75, further preferably 1.68 to 1.73, and even more preferably 1.7 to 1.72.

[0101] The dinaphthofuran derivative (2c) has excellent solubility in organic solvents. Examples of the organic solvent include alkanols (particularly, methanol), aromatic hydrocarbons (particularly, toluene), cyclic ethers (particularly, tetrahydrofuran (THF)), amides (particularly, N,N-dimethylformamide), esters (particularly, ethyl acetate), alkylene glycol ether acetates (particularly, propylene glycol monomethyl ether acetate (PGMEA)), (meth)acrylic acid esters (particularly, methyl methacrylate), and aromatic vinyls (particularly, styrene).

[0102] In particular, the group X 3aThe dinaphthofuran derivative (2c) in which is an acyl group [particularly, a (meth)acryloyl group] has high solubility in aromatic hydrocarbons (particularly, toluene), cyclic ethers [particularly, tetrahydrofuran (THF)], amides (particularly, N,N-dimethylformamide), esters (particularly, ethyl acetate), alkylene glycol ether acetates [particularly, propylene glycol monomethyl ether acetate (PGMEA)], (meth)acrylic acid esters (particularly, methyl methacrylate), and aromatic vinyls (particularly, styrene), and has even higher solubility in toluene, THF, N,N-dimethylformamide, ethyl acetate, PGMEA, methyl methacrylate, and styrene, and has even higher solubility in toluene, THF, N,N-dimethylformamide, methyl methacrylate, and styrene, and has the highest solubility in THF.

[0103] Group X 3a The solubility of the dinaphthofuran derivative (2c) in THF, in which the group X is an acyl group [particularly, a (meth)acryloyl group], may be 50% by mass or more. 3 The dinaphthofuran derivative (2c) in which is an acryloyl group has high solubility in organic solvents, and may have a solubility of 50 mass % or more in toluene, THF, N,N-dimethylformamide and methyl methacrylate.

[0104] Group X 3a The solubility of the dinaphthofuran derivative (2c) in ethyl acetate, in which is an acyl group, may be 10% by mass or more, for example, 10 to 70% by mass, preferably 30 to 60% by mass, and more preferably 40 to 50% by mass.

[0105] In particular, the group X 3aThe dinaphthofuran derivative (2c) in which is an alkenyl group (particularly, an allyl group) has high solubility in aromatic hydrocarbons (particularly, toluene), cyclic ethers [particularly, tetrahydrofuran (THF)], amides (particularly, N,N-dimethylformamide), esters (particularly, ethyl acetate), alkylene glycol ether acetates [particularly, propylene glycol monomethyl ether acetate (PGMEA)], (meth)acrylic acid esters (particularly, methyl methacrylate), and aromatic vinyls (particularly, styrene), has even higher solubility in toluene, THF, N,N-dimethylformamide, ethyl acetate, PGMEA, methyl methacrylate, and styrene, and has extremely high solubility in toluene, THF, N,N-dimethylformamide, methyl methacrylate, and styrene.

[0106] Group X 3a The dinaphthofuran derivative (2c) in which is an alkenyl group (particularly, an allyl group) may have a solubility of 50 mass % or more in toluene, THF, N,N-dimethylformamide, PGMEA, methyl methacrylate, and styrene.

[0107] In particular, the group X 3a is an alkyl group (especially C 1-3 The dinaphthofuran derivative (2c), which is an alkyl group), has high solubility in aromatic hydrocarbons (particularly toluene), cyclic ethers [particularly tetrahydrofuran (THF)], amides (particularly N,N-dimethylformamide), esters (particularly ethyl acetate), alkylene glycol ether acetates [particularly propylene glycol monomethyl ether acetate (PGMEA)], (meth)acrylic acid esters (particularly methyl methacrylate), and aromatic vinyls (particularly styrene), and has even higher solubility in toluene, THF, N,N-dimethylformamide, ethyl acetate, PGMEA, methyl methacrylate, and styrene, and has the highest solubility in toluene, THF, and styrene.

[0108] Group X 3a is an alkyl group (especially C 1-3The solubility of the dinaphthofuran derivative (2c) (which is an alkyl group) in THF may be 10% by mass or more, for example, 10 to 50% by mass, preferably 15 to 40% by mass, and more preferably 20 to 30% by mass.

[0109] The dinaphthofuran derivative (2c) has a high refractive index despite its high solubility in organic solvents, and therefore may be used as a refractive index enhancer. Furthermore, the dinaphthofuran derivative (2c) has superior solubility in organic solvents compared to the corresponding dinaphthothiophene derivative.

[0110] (Dinaphthofuran derivative (2d)) The dinaphthofuran derivative represented by formula (2d) [dinaphthofuran derivative (2d)] is a compound represented by formula (1), in which n is 1 and the group R 1 is a dinaphthofuran derivative (5-vinyl compound) represented by formula (1c).

[0111] In the formula (2d), the group X 4 and X 5 Examples of the group X in the formula (1c) include a hydrogen atom; 4 , X 5 Among these, hydrogen atom, methyl group, and other C 1-6 Alkyl groups are preferred, C 1-3 An alkyl group is more preferred, and a hydrogen atom is even more preferred.

[0112] Substituent R 3 and its number of substitutions m, and the substituent R 4 The number of substitutions k is determined based on the R 3 , R 4 , m and k.

[0113] Representative dinaphthofuran derivatives (2d) include, for example, 5-C dinaphthofuran derivatives such as 5-vinyldinaphthofuran, 5-(1-propenyl)dinaphthofuran, and 5-isobutenyldinaphthofuran. 2-4alkenyldinaphthofuran and the like.

[0114] The refractive index of the dinaphthofuran derivative (2d) at a temperature of 25° C. and a wavelength of 589 nm may be 1.6 or more (particularly 1.7 or more), for example, 1.6 to 1.9, preferably 1.65 to 1.85, further preferably 1.7 to 1.8, and more preferably 1.73 to 1.77.

[0115] The dinaphthofuran derivative (2d) has excellent solubility in organic solvents. Examples of organic solvents include alkanols (particularly, methanol), aromatic hydrocarbons (particularly, toluene), cyclic ethers [particularly, tetrahydrofuran (THF)], amides (particularly, N,N-dimethylformamide), esters (particularly, ethyl acetate), alkylene glycol ether acetates [particularly, propylene glycol monomethyl ether acetate (PGMEA)], (meth)acrylic acid esters (particularly, methyl methacrylate), and aromatic vinyls (particularly, styrene). Among these organic solvents, the solubility is high in toluene, THF, N,N-dimethylformamide, ethyl acetate, PGMEA, methyl methacrylate, and styrene, and the solubility is particularly high in toluene, THF, N,N-dimethylformamide, and styrene.

[0116] The solubility of the dinaphthofuran derivative (2d) in THF may be 10% by mass or more, for example, 10 to 50% by mass, preferably 15 to 40% by mass, and more preferably 20 to 30% by mass.

[0117] (Dinaphthofuran derivative (2e)) The dinaphthofuran derivative represented by the formula (2e) [dinaphthofuran derivative (2e)] is a compound represented by the formula (1), in which n is 0 and a group R 2 is a dinaphthofuran derivative (6-acyl compound) represented by the above formula (1a).

[0118] In the formula (2e), the group X 1 Examples of the group X in the formula (1a) include a hydrogen atom; 1Among these, hydrogen atom, methyl group, and other C 1-6 An alkyl group is preferred, and a C 1-3 An alkyl group is more preferred, and a hydrogen atom is even more preferred.

[0119] Substituent R 3 and its number of substitutions m, and the substituent R 4 The number of substitutions k is determined by the R 3 , R 4 , m and k.

[0120] Representative dinaphthofuran derivatives (2e) include, for example, 6-C dinaphthofuran derivatives such as 6-formyldinaphthofuran, 6-acetyldinaphthofuran, 6-propionyldinaphthofuran, 6-butyryldinaphthofuran, 6-valeryldinaphthofuran, and 6-hexanoyldinaphthofuran. 1-7 acyl dinaphthofuran and the like.

[0121] The refractive index of the dinaphthofuran derivative (2e) at a temperature of 25° C. and a wavelength of 589 nm may be 1.6 or more (particularly 1.7 or more), for example, 1.6 to 1.9, preferably 1.65 to 1.8, further preferably 1.68 to 1.78, and even more preferably 1.7 to 1.75.

[0122] The dinaphthofuran derivative (2e) has excellent solubility in organic solvents. Examples of organic solvents include aromatic hydrocarbons (particularly, toluene), cyclic ethers (particularly, tetrahydrofuran (THF)), amides (particularly, N,N-dimethylformamide), and aromatic vinyls (particularly, styrene). Among these organic solvents, the dinaphthofuran derivative (2e) has high solubility in THF.

[0123] The solubility of the dinaphthofuran derivative (2e) in THF may be 1% by mass or more (particularly 3% by mass or more), for example, 1 to 30% by mass, preferably 2 to 10% by mass, and more preferably 3 to 5% by mass.

[0124] (Dinaphthofuran derivatives (2f)) The dinaphthofuran derivative represented by formula (2f) [dinaphthofuran derivative (2f)] is a compound represented by formula (1), in which n is 0 and the group R 2 represents formula (1b), and X 3 represents a hydrogen atom.

[0125] In the formula (2f), the group X 2 Examples of the group X in the formula (1b) include a hydrogen atom; 2 Among these, hydrogen atom, C 1-6 Alkyl groups are preferred, C 1-3 An alkyl group is more preferable, and a hydrogen atom, a methyl group, etc. 1-2 An alkyl group is more preferred, and a hydrogen atom is most preferred.

[0126] Substituent R 3 and its number of substitutions m, and the substituent R 4 The number of substitutions k is determined based on the R 3 , R 4 , m and k.

[0127] Representative dinaphthofuran derivatives (2f) include, for example, 6-hydroxy C dinaphthofuran derivatives such as 6-hydroxymethyl dinaphthofuran, 6-(1-hydroxyethyl) dinaphthofuran, 6-(1-hydroxypropyl) dinaphthofuran, and 6-(1-hydroxybutyl) dinaphthofuran. 1-7 Alkyl dinaphthofuran and the like.

[0128] The refractive index of the dinaphthofuran derivative (2f) at a temperature of 25° C. and a wavelength of 589 nm may be 1.6 or more (particularly 1.65 or more), for example, 1.6 to 1.9, preferably 1.63 to 1.8, further preferably 1.65 to 1.78, and even more preferably 1.7 to 1.75.

[0129] The dinaphthofuran derivative (2f) has excellent solubility in organic solvents. Examples of organic solvents include aromatic hydrocarbons (particularly toluene), cyclic ethers [particularly tetrahydrofuran (THF)], amides (particularly N,N-dimethylformamide), and aromatic vinyls (particularly styrene). Among these organic solvents, the solubility is high in THF and N,N-dimethylformamide, and is particularly high in THF.

[0130] The solubility of the dinaphthofuran derivative (2f) in THF may be 3% by mass or more, for example, 3 to 30% by mass, and preferably 3.5 to 10% by mass.

[0131] (Dinaphthofuran derivatives (2g)) The dinaphthofuran derivative represented by the formula (2g) [dinaphthofuran derivative (2g)] is a compound represented by the formula (1), in which n is 0 and the group R 2 corresponds to formula (1b), and X 3 represents a chain hydrocarbon group or an acyl group which may have a substituent.

[0132] In the formula (2g), the group X 2 Examples of the group X in the formula (2a) include a hydrogen atom; 1 Among these, hydrogen atom, methyl group, and other C 1-6 An alkyl group is preferred, and a C 1-3 An alkyl group is more preferred, and a hydrogen atom is even more preferred.

[0133] Group X 3a Examples of the acyl group include the group X in the formula (2c). 3a Among the above acyl groups, the following acyl groups are exemplified: 3-6 Alkenoyl groups are preferred, C 3-5 An alkenoyl group is more preferred, and a (meth)acryloyl group is even more preferred.

[0134] Group X 3aExamples of the chain hydrocarbon group include the group X in the formula (1b). 3 the alkyl group exemplified as above, the group X in the formula (1b) 3 Examples of the alkenyl groups include the alkenyl groups exemplified as:

[0135] Of these, C such as ethyl groups 1-3 C such as alkyl group, vinyl group, and allyl group 2-6 Alkenyl groups are preferred, C 2-4 Alkenyl groups are more preferred, and C such as allyl groups. 3-4 Alkenyl groups are more preferred.

[0136] X 3a The substituent of the chain hydrocarbon group is, for example, a linear or branched C group such as a hydroxyl group, an alkoxy group (e.g., a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. 1-6 Among these, a hydroxyl group is preferred. Furthermore, X 3a The chain hydrocarbon group is more preferably a chain hydrocarbon group having no substituent.

[0137] Preferred group X 3a As for C 3-12 Alkenoyl group, C 2-6 Alkenyl groups are exemplified, among which (meth)acryloyl groups, C 2-4 Alkenyl groups are more preferred, and C such as allyl groups. 3-4 Alkenyl groups are more preferred.

[0138] Substituent R 3 and its number of substitutions m, and the substituent R 4 The number of substitutions k is determined based on the R 3 , R 4 , m and k.

[0139] Representative group X 3aExamples of the dinaphthofuran derivative (2g) in which is an acyl group such as a (meth)acryloyl group include 6-(meth)acryloyloxymethyl-dinaphthofuran, 6-methacryloyloxymethyl-dinaphthofuran, 6-[1-(acryloyloxy)ethyl]dinaphthofuran, and 6-[1-(methacryloyloxy)ethyl]dinaphthofuran. 1-7 Alkyl dinaphthofuran and the like.

[0140] Representative group X 3a Examples of the dinaphthofuran derivative (2g) in which is a chain hydrocarbon group include 6-C dinaphthofuran derivatives such as 6-methoxymethyldinaphthofuran and 6-(1-methoxyethyl)dinaphthofuran. 1-3 Alkoxy C 1-6 6-C alkyl dinaphthofuran, 6-vinyloxymethyl-dinaphthofuran, 6-[1-(vinyloxy)ethyl]dinaphthofuran, 6-allyloxymethyl-dinaphthofuran, 6-[1-(allyloxy)ethyl]dinaphthofuran, etc. 2-10 Alkenyloxy C 1-7 Alkyl dinaphthofuran and the like.

[0141] The refractive index of the dinaphthofuran derivative (2g) at a temperature of 25° C. and a wavelength of 589 nm may be 1.6 or more (particularly 1.65 or more), for example, 1.6 to 1.8, preferably 1.63 to 1.75, further preferably 1.65 to 1.7, and more preferably 1.67 to 1.69.

[0142] The dinaphthofuran derivative (2g) has excellent solubility in organic solvents. Examples of organic solvents include aromatic hydrocarbons (particularly toluene), cyclic ethers [particularly tetrahydrofuran (THF)], amides (particularly N,N-dimethylformamide), esters (particularly ethyl acetate), alkylene glycol ether acetates [particularly propylene glycol monomethyl ether acetate (PGMEA)], (meth)acrylic acid esters (particularly methyl methacrylate), and aromatic vinyls (particularly styrene). Among these organic solvents, THF has high solubility.

[0143] The solubility of the dinaphthofuran derivative (2g) in THF may be 5% by mass or more, for example, 5 to 50% by mass, preferably 10 to 30% by mass, and more preferably 15 to 20% by mass.

[0144] (Dinaphthofuran derivative (2h)) The dinaphthofuran derivative represented by formula (2h) [dinaphthofuran derivative (2h)] is a compound represented by formula (1), in which n is 0 and the group R 2 is a dinaphthofuran derivative (6-vinyl compound) represented by formula (1c).

[0145] In the formula (2h), the group X in the formula (1c) 4 and X 5 Examples of the group X in the formula (2a) include a hydrogen atom; 1 Among these, hydrogen atom, methyl group, and other C 1-3 An alkyl group is preferred, and a hydrogen atom is particularly preferred.

[0146] Substituent R 3 and its number of substitutions m, and the substituent R 4 The number of substitutions k is determined based on the R 3 , R 4 , m and k.

[0147] Representative dinaphthofuran derivatives (2h) include, for example, 6-C dinaphthofuran derivatives such as 6-vinyl dinaphthofuran, 6-(1-propenyl) dinaphthofuran, and 6-isobutenyl dinaphthofuran. 2-4 alkenyldinaphthofuran and the like.

[0148] The refractive index of the dinaphthofuran derivative (2h) at a temperature of 25° C. and a wavelength of 589 nm may be 1.6 or more (particularly 1.7 or more), for example, 1.6 to 1.9, preferably 1.65 to 1.85, further preferably 1.7 to 1.8, and more preferably 1.73 to 1.77.

[0149] The dinaphthofuran derivative (2h) has excellent solubility in organic solvents. Examples of organic solvents include alkanols (particularly, methanol), aromatic hydrocarbons (particularly, toluene), cyclic ethers [particularly, tetrahydrofuran (THF)], amides (particularly, N,N-dimethylformamide), esters (particularly, ethyl acetate), alkylene glycol ether acetates [particularly, propylene glycol monomethyl ether acetate (PGMEA)], (meth)acrylic acid esters (particularly, methyl methacrylate), and aromatic vinyls (particularly, styrene). Among these organic solvents, the solubility in toluene, THF, N,N-dimethylformamide, ethyl acetate, PGMEA, methyl methacrylate, and styrene is high, and the solubility in toluene, THF, N,N-dimethylformamide, and styrene is particularly high.

[0150] [Method of producing a new dinaphthofuran derivative] The dinaphthofuran derivative of the present invention can be produced by a conventional method. For example, it may be produced by a production method including an acyl group substitution step of substituting an acyl group at the 5- or 6-position of a dinaphthofuran compound represented by the following formula (2).

[0151] [ka]

[0152] [In the formula, R 3 and R 4 are independently R 1 and R 2 represents a substituent different from, m represents an integer of 0 to 5, and k represents an integer of 0 to 6.

[0153] Furthermore, the dinaphthofuran derivative of the present invention may be produced, for example, by the methods shown below depending on the target compound.

[0154] (Method for producing dinaphthofuran derivative (2a)) The dinaphthofuran derivative (2a) can be obtained via the acyl group substitution step. For example, as shown in the following reaction formula, the dinaphthofuran derivative (2a) can be produced via a first acyl group substitution step in which a dinaphthofuran compound represented by the formula (2) [dinaphthofuran compound (2) unsubstituted at the 5-position] is reacted with an acylating agent in the presence of an acid catalyst to obtain the dinaphthofuran derivative (2a).

[0155] [ka]

[0156] [In the formula, R 3 , R 4 , m, and k are the same as those in formula (1), and X 1 is the same as formula (1a) above.

[0157] Representative examples of the dinaphthofuran compound (2) include compounds in which both m and k are 0, that is, dinaphthofuran.

[0158] The reaction between the dinaphthofuran compound (2) and an acylating agent may be, for example, a Friedel-Crafts acylation reaction.

[0159] As the acylating agent, an acyl compound used in a conventional Friedel-Crafts acylation reaction can be used. Examples of the acyl compound include acyl halides (e.g., C halides such as formyl chloride, acetyl chloride, propionyl chloride, and crotonyl chloride). 1-13 Acyl chloride; formyl bromide, acetyl bromide, propionyl bromide, crotonyl bromide, etc. 1-13 Acyl bromides; formyl iodine, acetyl iodine, propionyl iodine, crotonyl iodine, etc. 1-13 acyl iodine, etc.); carboxylic acid amides (e.g., N,N-dimethylacetamide, N,N-dimethylpropionamide, etc.) 1-13 Acyl-N,N-diC 1-12alkylamines, etc.); carboxylic acid esters (e.g., methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, phenyl propionate, etc. C 1-13 Alkanoic acid esters, etc.; carboxylic acids (e.g., acetic acid, propionic acid, crotonic acid, etc.) 1-13 Alkanoic acid, etc.; carboxylic acid anhydrides (e.g., acetic anhydride, propionic anhydride, crotonic anhydride, etc.) 1-13 Alkanoic acid, etc.

[0160] These acylating agents can be used alone or in combination of two or more. Among these acylating agents, carboxylic acid anhydrides such as acetic anhydride are preferred.

[0161] The proportion of the acylating agent may be 0.5 mol or more relative to 1 mol of the dinaphthofuran compound (2), and is, for example, 0.5 to 3 mol, preferably 0.8 to 2 mol, further preferably 0.9 to 1.5 mol, more preferably 1 to 1.4 mol, and most preferably 1.1 to 1.3 mol.

[0162] Examples of the acid catalyst include inorganic acids [for example, strong acids such as sulfuric acid, hydrogen chloride (or hydrochloric acid), nitric acid, and phosphoric acid; homo- or heteropolyacids such as tungstophosphoric acid, molybdophosphoric acid, tungstosilicic acid, and molybdosilicic acid], organic acids [for example, sulfonic acids (alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and trifluoromethanesulfonic acid; arenesulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, and naphthalenesulfonic acid)], and Lewis acids [for example, aluminum chloride, iron chloride, tin chloride, titanium chloride, phosphorus oxychloride, and boron trifluoride etherate].

[0163] These acid catalysts can be used alone or in combination of two or more. Among these acid catalysts, Lewis acids are preferred because they allow the reaction to proceed efficiently and selectively, and aluminum chloride is particularly preferred.

[0164] The proportion of the acid catalyst is, for example, 0.1 to 10 mol, preferably 0.3 to 8 mol, further preferably 0.5 to 5 mol, more preferably 1.5 to 4 mol, and most preferably 2 to 3 mol, relative to 1 mol of the dinaphthofuran compound (2).

[0165] The reaction may be carried out in the presence or absence of a solvent, which may be either an aprotic solvent or a protic solvent.

[0166] The aprotic solvent may be either an aprotic nonpolar solvent or an aprotic polar solvent.

[0167] Examples of aprotic non-polar solvents include hydrocarbons, specifically, aliphatic hydrocarbons [e.g., hexane, heptane, octane, decane, dodecane, etc.], alicyclic hydrocarbons [e.g., cyclohexane, etc.], aromatic hydrocarbons [e.g., mono- or tetra-C hydrocarbons such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, ethyltoluene, propylbenzene, and cumene, etc.], 1-4 Alkyl-benzene, etc.

[0168] Examples of aprotic polar solvents include chain ethers (e.g., dialkyl ethers such as diethyl ether, diisopropyl ether, and t-butyl methyl ether); glycol ethers (e.g., methyl cellosolve, methyl carbitol, and dimethoxyethane); cyclic ethers (e.g., propylene oxide, dioxolane, dioxole, trioxane, furan, tetrahydrofuran (THF), 1,3-dioxane, 1,4-dioxane, dioxene, 2-methylfuran, pyran, and tetrahydropyran); ketones (e.g., acetone, methyl ethyl ketone (MEK), ), methyl isobutyl ketone (MIBK), cyclohexanone, etc.; esters [e.g., methyl acetate, ethyl acetate, etc.]; nitriles [e.g., acetonitrile, benzonitrile, etc.]; amides [e.g., N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, N-methyl-2-pyrrolidone, etc.]; sulfoxides [e.g., dimethyl sulfoxide (DMSO), methyl ethyl sulfoxide, diethyl sulfoxide, etc.]; and halogenated hydrocarbons such as methylene chloride, methylene dichloride, and chloroform.

[0169] Examples of protic solvents include alkanols (e.g., methanol, ethanol, propanol, isopropanol, hexanol, heptanol, octanol, decanol, lauryl alcohol, and the like). 1-12 alkanols, etc.); aliphatic polyhydric alcohols (e.g., ethylene glycol, propylene glycol, etc. C 2-4 Di-C such as alkylene glycol and diethylene glycol 2-4 alkylene glycols, etc.

[0170] These solvents can be used alone or in combination of two or more. Among these solvents, the solvents used in the conventional Friedel-Crafts acylation reaction are preferred, including halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.); aromatic hydrocarbons (e.g., mono- or di-C hydrocarbons such as toluene); 1-2More preferred are alkyl-benzenes, and even more preferred are halogenated hydrocarbons such as dichloromethane.

[0171] The proportion of the solvent is, for example, 10 to 3000 parts by mass, preferably 100 to 1000 parts by mass, more preferably 200 to 800 parts by mass, and even more preferably 300 to 500 parts by mass, relative to 100 parts by mass of the dinaphthofuran compound (2).

[0172] The reaction temperature may be, for example, about -10 to 20°C, preferably about 0 to 10°C, and more preferably about 0 to 5°C.

[0173] The reaction may be carried out in an inert gas (e.g., nitrogen; rare gases such as argon and helium, etc.). The reaction may be carried out under normal pressure or under pressure. After completion of the reaction, the reaction product may be separated and purified by a conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, etc., or a combination of these methods.

[0174] (Method for producing dinaphthofuran derivative (2b)) The dinaphthofuran derivative (2b) can be produced by a production method including the acyl group substitution step and a reduction step of reducing the dinaphthofuran derivative obtained in the acyl group substitution step. For example, as shown in the following reaction formula, the dinaphthofuran derivative (2b) can be produced via a reduction step of reducing the dinaphthofuran derivative (2a) obtained in the first acyl group substitution step with a reducing agent to obtain the dinaphthofuran derivative (2b).

[0175] [ka]

[0176] [In the formula, R 3 , R 4 , m, and k are the same as those in formula (1), and X 1 , X 2 are the same as formulas (1a) and (1b) above.

[0177] Representative dinaphthofuran derivatives (2a) include, for example, those in which both m and k are 0 and 1 is an alkyl group such as a methyl group, that is, 5-acyldinaphthofuran such as 5-acetyldinaphthofuran.

[0178] The reducing agent can be appropriately selected depending on the target compound, and examples of the reducing agent that can be used include metal hydride compounds and hydrogen gas.

[0179] The reducing agent reduces at least the carbonyl group to a group X 1 In some cases, the unsaturated carbon bond contained in X may be reduced. 2 X 1 may be a reduced group.

[0180] In the reduction treatment using a metal hydride compound as a reducing agent, examples of the metal hydride compound include borohydride compounds [e.g., lithium borohydride, lithium aminoborohydride, lithium triethylborohydride, lithium tri(s-butyl)borohydride, potassium borohydride, potassium tri(s-butyl)borohydride, calcium borohydride, sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride, zinc borohydride, nickel borohydride, and diborane]; aluminum hydride compounds [e.g., lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, etc.], etc. These metal hydride compounds can be used alone or in combination of two or more kinds. Among these, borohydride compounds such as sodium borohydride are preferred.

[0181] The proportion of the metal hydride compound is, for example, 0.1 to 10 mol, preferably 0.3 to 5 mol, further preferably 0.5 to 3 mol, more preferably 0.8 to 2 mol, and most preferably 1 to 1.5 mol, per 1 mol of the dinaphthofuran derivative (2a).

[0182] In the reduction treatment using a metal hydride compound, the reaction may be carried out in the presence of a reaction solvent, which can be appropriately selected depending on the reducing agent, and is preferably a protic solvent.

[0183] Examples of the protic solvent include the protic solvents exemplified in the section on the production method of the dinaphthofuran derivative (2a). The protic solvents can be used alone or in combination of two or more. Among these, C 1-6 Alkanols are preferred.

[0184] The proportion of the protic solvent is, for example, 10 to 1000 parts by mass, preferably 30 to 500 parts by mass, more preferably 50 to 300 parts by mass, and even more preferably 80 to 200 parts by mass, relative to 100 parts by mass of the dinaphthofuran derivative (2a).

[0185] In the reduction treatment using a metal hydride compound, the reaction temperature is, for example, 0 to 100°C, preferably 5 to 50°C, further preferably 10 to 40°C, and further preferably 20 to 30°C.

[0186] In the reduction treatment using a metal hydride compound, the reaction may be carried out in an inert gas (e.g., nitrogen; rare gases such as argon and helium, etc.) The reaction may be carried out under normal pressure or under pressure.

[0187] In the reduction treatment using hydrogen gas as the reducing agent, a hydrogenation catalyst (catalytic reduction catalyst) may be used as the catalyst.

[0188] In the reduction treatment using hydrogen gas, examples of the hydrogenation catalyst include nickel catalysts (e.g., Raney nickel catalysts, etc.); platinum catalysts (e.g., platinum carbon, platinum black, platinum oxide (Adams catalyst), etc.), palladium catalysts, rhodium catalysts, ruthenium catalysts (ruthenium carbon, ruthenium oxide, ruthenium black, etc.); and rhenium catalysts. These hydrogenation catalysts can be used alone or in combination of two or more. Among these, nickel catalysts such as Raney nickel catalysts are preferred.

[0189] The proportion of the hydrogenation catalyst is, for example, 0.01 to 100 parts by mass, preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the dinaphthofuran derivative (2a).

[0190] In the reduction treatment using hydrogen gas, the reaction temperature is, for example, 30 to 150°C, preferably 50 to 100°C, further preferably 70 to 90°C, and further preferably 75 to 85°C.

[0191] In the reduction treatment using hydrogen gas, the reaction may be carried out under normal pressure or under increased pressure, but is preferably carried out under increased pressure. The reaction pressure is, for example, 0.01 to 10 MPa, preferably 0.05 to 5 MPa, more preferably 0.1 to 1 MPa, and even more preferably 0.3 to 0.7 MPa.

[0192] In any reduction treatment, after completion of the reaction, the reaction product may be separated and purified by a conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, or a combination of these means.

[0193] (In formula (2c), X 3a (Method for producing dinaphthofuran derivatives in which the acyl group is In the formula (2c), X 3a The dinaphthofuran derivative in which R is an acyl group [first dinaphthofuran derivative (2c)] can be produced by a production method including the acyl group substitution step, the reduction step, and an esterification step of reacting the dinaphthofuran derivative obtained in the reduction step with an esterifying agent to obtain the dinaphthofuran derivative (2c). For example, as shown in the following reaction formula, the dinaphthofuran derivative can be produced via an esterification step (first esterification step) of reacting the dinaphthofuran derivative (2b) obtained in the reduction step with an esterifying agent in the presence of a catalyst to obtain the first dinaphthofuran derivative (2c).

[0194] [ka]

[0195] [In the formula, X 3a represents an acyl group, and R 3 , R 4 , m, and k are the same as those in formula (1), and X 2 is the same as formula (1b) above.

[0196] Representative dinaphthofuran derivatives (2b) include, for example, those in which both m and k are 0 and the X 2 represents a methyl group, i.e., 5-hydroxyethyldinaphthofuran [5-(1-hydroxyethyl)dinaphthofuran].

[0197] The esterification agent is X 3a For example, acyl chloride [e.g., acetyl chloride, propionyl chloride, etc. 2-12 Alkanoyl chlorides; (meth)acryloyl chloride, crotonoyl chloride, pentenoyl chloride, hexenoyl chloride, etc. 3-12 Alkenoyl chlorides, etc.], acyl bromides [e.g. acetyl bromide, propionyl bromide, etc. C 2-12 Alkanoyl bromides; (meth)acryloyl bromide, crotonoyl bromide, pentenoyl bromide, hexenoyl bromide, etc. 3-12 Alkenoyl bromides, etc.], acyl iodines [e.g., acetyl iodine, propionyl iodine, etc. C 2-12 Alkanoyl iodine; (meth)acryloyl iodine, crotonoyl iodine, pentenoyl iodine, hexenoyl iodine, etc. 3-12 alkenoyl iodine, etc.], carboxylic acids or their esters (e.g., carboxylic acids such as acetic acid, propionic acid, etc. or their C 1-3 alkyl esters, etc.

[0198] These esterifying agents can be used alone or in combination of two or more. Among these, acyl halides are preferred, and C esters such as (meth)acryloyl chloride are preferred.3-6 Alkenoyl chlorides are particularly preferred.

[0199] The proportion of the esterifying agent may be, for example, 0.5 mol or more, and is, for example, 0.5 to 5 mol, preferably 0.8 to 3 mol, further preferably 1 to 2.5 mol, more preferably 1.2 to 2 mol, and most preferably 1.3 to 1.8 mol, relative to 1 mol of the dinaphthofuran derivative (2b).

[0200] As the catalyst, a conventional esterification catalyst can be used depending on the type of esterifying agent. A preferred esterification catalyst is a base catalyst. Examples of the base catalyst include alkali metal hydroxides (e.g., lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (e.g., lithium carbonate, sodium carbonate, potassium carbonate, etc.), alkali metal hydrogen carbonates (e.g., sodium hydrogen carbonate, potassium hydrogen carbonate, etc.), alkaline earth metal hydroxides (e.g., magnesium hydroxide, calcium hydroxide, etc.), alkaline earth metal carbonates (e.g., magnesium carbonate, etc.), alkaline earth metal hydrogen carbonates (e.g., magnesium hydrogen carbonate, etc.), alkali metal hydrides (e.g., sodium hydride, potassium hydride, etc.), alkaline earth metal hydrides (e.g., calcium hydride, etc.), alkali metal alcoholates (e.g., alkaline earth metal hydrides, sodium methylate, sodium ethylate, potassium t-butoxide, etc.), ammonia, tertiary amines (e.g., tri-C such as trimethylamine and triethylamine, etc.), and the like. 1-4 alkylamines, etc.), heterocyclic amines (4-dimethylaminopyridine, morpholine, piperidine, etc.), quaternary ammonium salts (e.g., tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide (TBAB), etc.) 1-4 Alkyl ammonium halides; Tri-C such as trioctylmethyl ammonium chloride 1-12 Alkyl C 1-4 Alkyl ammonium halides; benzyl trimethyl ammonium chloride, benzyl tributyl ammonium chloride, etc. 1-4alkyl ammonium halides, etc.

[0201] These base catalysts can be used alone or in combination of two or more. Among these, triC such as triethylamine 1-4 Alkylamines and / or heterocyclic amines such as 4-dimethylaminopyridine are preferred.

[0202] The proportion of the catalyst (particularly the base catalyst) is, for example, 0.1 to 10 mol, preferably 0.3 to 5 mol, further preferably 0.5 to 3 mol, more preferably 1 to 2.5 mol, and most preferably 1.3 to 2.3 mol, per mol of the dinaphthofuran derivative (2b).

[0203] The esterification step may be carried out in the presence of a solvent. Examples of the solvent include the aprotic solvents exemplified in the section on the production method of the dinaphthofuran derivative (2a). The aprotic solvents may be used alone or in combination of two or more. Among the aprotic solvents, aprotic polar solvents are preferred, and cyclic ethers such as THF are particularly preferred.

[0204] The proportion of the solvent is, for example, 10 to 3000 parts by mass, preferably 100 to 1000 parts by mass, more preferably 300 to 800 parts by mass, and even more preferably 400 to 600 parts by mass, relative to 100 parts by mass of the dinaphthofuran derivative (2b).

[0205] The reaction temperature is, for example, 0 to 80°C, preferably 10 to 60°C, and more preferably 15 to 55°C.

[0206] The reaction may be carried out in an inert gas (e.g., nitrogen; rare gases such as argon and helium, etc.). The reaction may be carried out under normal pressure or under pressure. After completion of the reaction, the reaction product may be separated and purified by a conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, etc., or a combination of these methods.

[0207] (In formula (2c), X 3a (Method for producing a dinaphthofuran derivative in which the alkyl group is a chain hydrocarbon group which may have a substituent) In the formula (2c), X 3a The dinaphthofuran derivative (2c) in which R is a chain hydrocarbon group which may have a substituent can be produced by a production method including the acyl group substitution step, the reduction step, and an etherification step of reacting the dinaphthofuran derivative obtained in the reduction step with an etherification agent to obtain the dinaphthofuran derivative (2c). For example, as shown in the following reaction formula, the dinaphthofuran derivative (2b) can be produced via an etherification step (first etherification step) of reacting the dinaphthofuran derivative (2b) obtained in the reduction step with an etherification agent in the presence of a catalyst to obtain the second dinaphthofuran derivative (2c).

[0208] [ka]

[0209] [In the formula, X 3a represents a chain hydrocarbon group which may have a substituent, R 3 , R 4 , m, and k are the same as those in formula (1), and X 2 is the same as formula (1b) above.

[0210] Representative dinaphthofuran derivatives (2b) include, for example, those in which both m and k are 0 and the X 2 represents a methyl group, i.e., 5-(hydroxyethyl)dinaphthofuran and the like.

[0211] The etherification agent is X 3a Corresponding to the above, a halogenated chain hydrocarbon (halo chain hydrocarbon) which may have a substituent can be used.

[0212] Examples of the halo-chain hydrocarbon include halogenated alkanes (haloalkanes) and halogenated alkenes (haloalkenes).

[0213] Examples of haloalkanes include alkyl chlorides [e.g., C chlorides such as methyl chloride, ethyl chloride, propyl chloride (3-chloropropane), butyl chloride, and hexyl chloride]. 1-12 alkyl, etc.], alkyl bromides [e.g., methyl bromide, ethyl bromide, propyl bromide, butyl bromide, hexyl bromide, etc. 1-12 alkyl iodides, alkyl iodides (e.g., methyl iodide, ethyl iodide, propyl iodide, butyl iodide, hexyl iodide, etc.) 1-12 Alkyl, etc.

[0214] Examples of haloalkenes include chlorinated alkenes [e.g., chlorinated C such as vinyl chloride, allyl chloride (3-chloropropene), butene chloride, pentene chloride, and hexene chloride]. 2-12 alkene, etc.], alkene bromides (e.g., vinyl bromide, allyl bromide, propene bromide, butene bromide, pentene bromide, hexene bromide, etc.) 2-10 alkene iodides, alkene iodides (e.g., vinyl iodide, allyl iodide, propene iodide, butene iodide, pentene iodide, hexene iodide, etc.) 2-12 Alkenes, etc.

[0215] The substituent of the halo-chain hydrocarbon is, for example, a linear or branched C alkoxy group such as a hydroxyl group, an alkoxy group (e.g., a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. 1-6 Alkoxy groups, etc. Among these, hydroxyl groups are preferred. Furthermore, the halo-chain hydrocarbon is more preferably a halo-chain hydrocarbon that does not have a substituent.

[0216] These etherifying agents can be used alone or in combination of two or more. 1-6 Alkyl, haloC 2-6 Alkenes are preferred, haloC such as methyl iodide. 1-3 Alkyl, halo C such as allyl chloride 2-4 Alkenes are particularly preferred.

[0217] The ratio of the etherification agent may be, for example, 0.5 mol or more, for example, 0.5 to 10 mol, preferably 1 to 8 mol, and more preferably 1.5 to 6 mol, relative to 1 mol of the dinaphthofuran derivative (2b). In particular, the ratio of the haloalkane is, for example, 0.5 to 5 mol, preferably 0.8 to 4 mol, more preferably 1 to 3 mol, more preferably 1.2 to 2.8 mol, and most preferably 1.5 to 2.5 mol, relative to 1 mol of the dinaphthofuran derivative (2b). The ratio of the haloalkene is, for example, 0.5 to 10 mol, preferably 1 to 8 mol, more preferably 2 to 6 mol, more preferably 3 to 5 mol, and most preferably 3.5 to 4.5 mol, relative to 1 mol of the dinaphthofuran derivative (2b).

[0218] As the catalyst, a conventional etherification catalyst can be used depending on the type of etherification agent. A preferred etherification catalyst is a base catalyst. Examples of the base catalyst include the base catalysts exemplified in the section on the production method of the first dinaphthofuran derivative (2c). The base catalysts can be used alone or in combination of two or more.

[0219] Among the above-mentioned base catalysts, alkali metal hydroxides and quaternary ammonium salts are preferred, and alkali metal hydroxides and benzyl trimethylsilyl C 1-4 A combination with an alkyl ammonium halide is particularly preferred. The quaternary ammonium salt may function as a phase transfer catalyst.

[0220] As the base catalyst, an alkali metal hydroxide and a quaternary ammonium salt (particularly, benzyl trimethylsilyl C 1-4 When the quaternary ammonium salt is combined with an alkyl ammonium halide, the proportion of the quaternary ammonium salt is, for example, 0.01 to 100 mol, preferably 0.1 to 10 mol, further preferably 0.5 to 5 mol, more preferably 1 to 3 mol, and most preferably 1.5 to 2 mol, relative to 100 mol of the alkali metal hydroxide.

[0221] The proportion of the base catalyst is, for example, 1 to 30 mol, preferably 3 to 25 mol, further preferably 5 to 20 mol, more preferably 8 to 15 mol, and most preferably 10 to 12 mol, relative to 1 mol of the dinaphthofuran derivative (2b).

[0222] The etherification step may be carried out in the presence of a solvent. Examples of the solvent include the solvents exemplified in the section on the production method of the dinaphthofuran derivative (2a) and water. These solvents may be used alone or in combination of two or more. Among the above solvents, water, cyclic ethers such as THF, and aromatic hydrocarbons such as toluene are preferred, and a mixed solvent of water and cyclic ethers or aromatic hydrocarbons is particularly preferred.

[0223] The proportion of the solvent is, for example, 10 to 3000 parts by mass, preferably 100 to 1000 parts by mass, more preferably 150 to 500 parts by mass, and even more preferably 200 to 400 parts by mass, relative to 100 parts by mass of the dinaphthofuran derivative (2b).

[0224] The reaction temperature is, for example, 0 to 80°C, preferably 10 to 60°C, further preferably 20 to 50°C, and further preferably 30 to 45°C.

[0225] The reaction may be carried out in an inert gas (e.g., nitrogen; rare gases such as argon and helium, etc.). The reaction may be carried out under normal pressure or under pressure. After completion of the reaction, the reaction product may be separated and purified by a conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, etc., or a combination of these methods.

[0226] (Method for producing dinaphthofuran derivative represented by formula (2d)) The dinaphthofuran derivative (2d) can be produced by a production method including the acyl group substitution step, the reduction step, and a dehydration step of reacting the dinaphthofuran derivative obtained in the reduction step with a dehydrating agent to obtain the dinaphthofuran derivative (2d). For example, as shown in the following reaction formula, the dinaphthofuran derivative (2b) can be produced via a dehydration step (first dehydration step) of reacting the dinaphthofuran derivative (2b) obtained in the reduction step with a dehydrating agent to obtain the dinaphthofuran derivative (2d).

[0227] [ka]

[0228] [In the formula, R 3 , R 4 , m, and k are the same as those in formula (1), and X 2 , X 4 , X 5 are the same as formulas (1b) and (1c) above.

[0229] Representative dinaphthofuran derivatives (2b) include, for example, those in which both m and k are 0 and 2 is a methyl group, i.e., 5-(hydroxyethyl)dinaphthofuran, etc.

[0230] As the dehydrating agent, a conventional dehydrating agent can be used, and examples thereof include an acid catalyst.

[0231] Examples of the acid catalyst include sulfonic acids such as sulfuric acid, trifluoroacetic acid, trifluoroacetic anhydride, methanesulfonic acid, trifluoromethanesulfonic acid, trimethylsilyl trifluoromethanesulfonate, benzenesulfonic acid, p-toluenesulfonic acid, and 10-camphorsulfonic acid; aluminum chloride, titanium(IV) chloride, tin(IV) chloride, triphenylmethyl perchlorate, bismuth triflate, ytterbium triflate, scandium triflate, and diphosphorus pentoxide.

[0232] These acid catalysts can be used alone or in combination of two or more. Among these, sulfonic acids such as toluenesulfonic acid are preferred.

[0233] The proportion of the dehydrating agent (particularly, the acid catalyst) is, for example, 0.1 to 10 mol, preferably 0.2 to 4 mol, further preferably 0.3 to 2 mol, more preferably 0.6 to 1 mol, and most preferably 0.7 to 0.8 mol, relative to 1 mol of the dinaphthofuran derivative (2b).

[0234] The reaction may be carried out in the presence or absence of a polymerization inhibitor. Examples of the polymerization inhibitor include phenol-based polymerization inhibitors (e.g., methoquinone, hydroquinone, etc.). The proportion of the polymerization inhibitor is, for example, 0.01 to 5 parts by mass, preferably 0.05 to 1 part by mass, and more preferably 0.1 to 0.5 parts by mass, relative to 100 parts by mass of the dinaphthofuran derivative (2b).

[0235] The dehydration step may be carried out in the presence of a solvent. Examples of the solvent include those exemplified in the section on the production method of the dinaphthofuran derivative (2a). The solvents may be used alone or in combination of two or more. Among the solvents, solvents immiscible with water, for example, aliphatic hydrocarbons such as hexane and cyclohexane, and aromatic hydrocarbons such as benzene and toluene, are preferred, and from the viewpoint of operability, aromatic hydrocarbons such as toluene are more preferred.

[0236] The proportion of the solvent is, for example, 1,000 to 10,000 parts by mass, preferably 1,500 to 8,000 parts by mass, further preferably 2,000 to 6,000 parts by mass, and further preferably 2,500 to 5,000 parts by mass, relative to 100 parts by mass of the dinaphthofuran derivative (2b).

[0237] The reaction temperature is, for example, 70 to 150°C, preferably 80 to 140°C, further preferably 90 to 130°C, and further preferably 100 to 115°C.

[0238] The reaction may be carried out in an inert gas (e.g., nitrogen; rare gases such as argon and helium, etc.). The reaction may be carried out under normal pressure or under pressure. After completion of the reaction, the reaction product may be separated and purified by a conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, etc., or a combination of these methods.

[0239] (Method for producing dinaphthofuran derivative represented by formula (2e)) The dinaphthofuran derivative (2e) can be obtained via the acyl group substitution step. For example, as shown in the reaction formula below, it can be produced via a second acyl group substitution step in which a dinaphthofuran compound represented by the following formula (2) [dinaphthofuran compound (2) unsubstituted at the 6-position] is reacted with an organolithium compound and an acylating agent to obtain the dinaphthofuran derivative (2e).

[0240] [ka]

[0241] [In the formula, R 3 , R 4 , m, and k are the same as those in formula (1), and X 1 is the same as formula (1a) above.

[0242] Representative examples of the dinaphthofuran compound (2) include a compound in which both m and k are 0, that is, dinaphthofuran.

[0243] In the second acyl group substitution step, the dinaphthofuran compound (2) may be reacted with an organolithium compound and an acylating agent, and it is preferable to react the dinaphthofuran compound (2) with an organolithium compound and then react the dinaphthofuran compound with an acylating agent.

[0244] Examples of the organolithium compound include alkyllithium (e.g., methyllithium, ethyllithium, propyllithium, butyllithium, pentyllithium, hexyllithium, and other C 1-6Alkyl lithium, etc.; alkoxyalkyl lithium (e.g., methoxymethyl lithium, ethoxymethyl lithium, etc.) 1-3 Alkoxy C 1-6 Alkyl lithium, etc.; alkenyl lithium (e.g., vinyl lithium, allyl lithium, propenyl lithium, butenyl lithium, etc.) 2-6 Alkenyl lithium, etc.; alkynyl lithium (e.g., ethynyl lithium, butynyl lithium, pentynyl lithium, hexynyl lithium, etc. C 2-6 Alkynyl lithium, etc.; aralkyl lithium (benzyl lithium, phenylethyl lithium, etc. C 6-10 Aryl C 1-3 alkyllithium, etc.); aryllithium (for example, phenyllithium, etc.); and the like.

[0245] These organolithium compounds can be used alone or in combination of two or more. Among these, C butyllithium such as n-butyllithium, s-butyllithium, and t-butyllithium are preferred from the viewpoint of operability. 3-5 Alkyllithium is preferred.

[0246] The proportion of the organolithium compound may be, for example, 0.3 mol or more, for example, 0.3 to 5 mol, preferably 0.5 to 2 mol, and more preferably 1 to 1.5 mol, per mol of the dinaphthofuran derivative (2).

[0247] As the acylating agent, a conventional acylating agent can be used. A preferred acylating agent is an acyldialkylamine. The acyldialkylamine is preferably an acyldialkylamine represented by the formula: X 1 Correspondingly, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylbutyrylamide, N,N-dimethylvalerylamide, etc. 1-13 Acyl-N,N-diC 1-12 Alkylamines and the like.

[0248] These acyldialkylamines can be used alone or in combination of two or more. 1-7 Acyl-N,N-diC 1-6 Alkylamines are preferred, C 1-4 Acyl-N,N-diC 1-3 Alkylamines are more preferred, C 1-3 Acyl-N,N-diC 1-2 Alkylamines are more preferred.

[0249] The proportion of the acylating agent (particularly, acyldialkylamine) may be, for example, 0.5 mol or more, for example, 0.5 to 10 mol, preferably 1 to 8 mol, and more preferably 2 to 6 mol, per mol of the dinaphthofuran derivative (2).

[0250] The dehydration step may be carried out in the presence of a solvent. Examples of the solvent include those exemplified in the section on the production method of the dinaphthofuran derivative (2a). The solvent may be used alone or in combination of two or more. Among the solvents, ethers such as tetrahydrofuran and diethyl ether are preferred because they can break up the association state of the organolithium compound, increase the reactivity, and dissolve the substrate and the organolithium compound.

[0251] The proportion of the solvent is, for example, 100 to 2000 parts by mass, preferably 500 to 1800 parts by mass, more preferably 600 to 1500 parts by mass, and even more preferably 800 to 1200 parts by mass, relative to 100 parts by mass of the dinaphthofuran derivative (2).

[0252] The reaction temperature is, for example, -30°C to 10°C, preferably -25°C to 5°C, further preferably -20°C to 0°C, and further preferably -15°C to -5°C.

[0253] The reaction may be carried out in an inert gas (e.g., nitrogen; rare gases such as argon and helium, etc.). The reaction may be carried out under normal pressure or under pressure. After completion of the reaction, the reaction product may be separated and purified by a conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, etc., or a combination of these methods.

[0254] (Method for producing dinaphthofuran derivative represented by formula (2f)) The dinaphthofuran derivative represented by the following formula (2f) [dinaphthofuran derivative (2f)] can be produced by a production method including the acyl group substitution step and a reduction step of reducing the dinaphthofuran derivative obtained in the acyl group substitution step. For example, as shown in the following reaction formula, the dinaphthofuran derivative can be produced via a reduction step (second reduction step) of reducing the dinaphthofuran derivative (2e) obtained in the second acyl group substitution step with a reducing agent to obtain the dinaphthofuran derivative (2f).

[0255] [ka]

[0256] [In the formula, R 3 and R 4 , m, and k are the same as those in formula (1), and X 1 , X 2 are the same as formulas (1a) and (1b) above.

[0257] Representative dinaphthofuran derivatives (2e) include, for example, those in which both m and k are 0 and 1 is a hydrogen atom, i.e., 6-formyldinaphthofuran, etc.

[0258] In the second reduction step, the reduction treatment may be any of the reduction treatments exemplified in the section on the production method of the dinaphthofuran derivative (2b). Among the reduction treatments, reduction treatment using hydrogen gas is preferred.

[0259] In any reduction treatment, after completion of the reaction, the reaction product may be separated and purified by a conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, or a combination of these means.

[0260] (In formula (2g), X 3a (Method for producing dinaphthofuran derivatives in which the acyl group is In the following formula (2g), X 3a The dinaphthofuran derivative in which R is an acyl group [first dinaphthofuran derivative (2g)] can be produced by a production method including the acyl group substitution step, the reduction step, and an esterification step of reacting the dinaphthofuran derivative obtained in the reduction step with an esterifying agent to obtain the dinaphthofuran derivative (2g). For example, as shown in the following reaction formula, the dinaphthofuran derivative can be produced via an esterification step (second esterification step) of reacting the dinaphthofuran derivative (2f) obtained in the second reduction step with an esterifying agent in the presence of a catalyst to obtain the first dinaphthofuran derivative (2g).

[0261] [ka]

[0262] [In the formula, X 3a represents an acyl group, and R 3 , R 4 , m, and k are the same as those in formula (1), and X 2 is the same as formula (1b) above.

[0263] Representative dinaphthofuran derivatives (2f) include, for example, those in which both m and k are 0 and 2 is a hydrogen atom, i.e., 6-(hydroxymethyl)dinaphthofuran, etc.

[0264] In the second esterification step, reaction conditions such as an esterifying agent, a catalyst, and a solvent can be appropriately selected depending on the target compound, and can be selected from the reaction conditions described in the section on the production method of the first dinaphthofuran derivative (2c), including preferred embodiments.

[0265] After completion of the reaction, the reaction product may be separated and purified by a conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, or a combination of these.

[0266] (In formula (2g), X 3a (Method for producing a dinaphthofuran derivative in which the alkyl group is a chain hydrocarbon group which may have a substituent) In the formula (2g), X 3a The dinaphthofuran derivative (2g) in which R is a chain hydrocarbon group which may have a substituent can be produced by a production method including the acyl group substitution step, the reduction step, and an etherification step of reacting the dinaphthofuran derivative obtained in the reduction step with a halogenated chain hydrocarbon to obtain the dinaphthofuran derivative (2g). For example, as shown in the following reaction formula, the dinaphthofuran derivative (2f) can be produced via an etherification step (second etherification step) of reacting the dinaphthofuran derivative (2f) obtained in the reduction step with an etherification agent in the presence of a catalyst to obtain the second dinaphthofuran derivative (2g).

[0267] [ka]

[0268] [In the formula, X 3a represents a chain hydrocarbon group which may have a substituent, R 3 , R 4 , m, and k are the same as those in formula (1), and X 2 is the same as formula (1b) above.

[0269] Representative dinaphthofuran derivatives (2f) include, for example, those in which both m and k are 0 and 2is a hydrogen atom, i.e., 6-(hydroxymethyl)dinaphthofuran, etc.

[0270] In the second etherification step, reaction conditions such as an etherification agent, a catalyst, and a solvent can be appropriately selected depending on the target compound, and can be selected from the reaction conditions described in the section on the production method of the second dinaphthofuran derivative (2c), including preferred embodiments.

[0271] After completion of the reaction, the reaction product may be separated and purified by a conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, or a combination of these.

[0272] (Method for producing dinaphthofuran derivative represented by formula (2h)) The dinaphthofuran derivative represented by the following formula (2h) [dinaphthofuran derivative (2h)] can be produced by a production method including the acyl group substitution step, the reduction step, and a dehydration step of reacting the dinaphthofuran derivative obtained in the reduction step with a dehydrating agent to obtain the dinaphthofuran derivative (2h). For example, as shown in the following reaction formula, it can be produced via a dehydration step (second dehydration step) of reacting the dinaphthofuran derivative (2f) obtained in the reduction step with a dehydrating agent to obtain the dinaphthofuran derivative (2h).

[0273] [ka]

[0274] [In the formula, R 3 , R 4 , m, and k are the same as those in formula (1), and X 2 , X 4 , X 5 are the same as formulas (1b) and (1c) above.

[0275] Representative dinaphthofuran derivatives (2f) include, for example, those in which both m and k are 0 and 2is a hydrogen atom, i.e., 6-(hydroxymethyl)dinaphthofuran, etc.

[0276] In the second dehydration step, reaction conditions such as a dehydrating agent, a polymerization inhibitor, and a solvent can be appropriately selected depending on the target compound, and can be selected from the reaction conditions described in the section on the production method of the dinaphthofuran derivative (2d) above.

[0277] After completion of the reaction, the reaction product may be separated and purified by a conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, or a combination of these.

[0278] In the present invention, a liquid composition containing the dinaphthofuran derivative represented by formula (1) and an organic solvent may be formed. A resin can also be prepared by polymerizing the dinaphthofuran derivative represented by formula (1) having a polymerizable group (α,β-ethylenically unsaturated bond) such as a (meth)acryloyl group, an allyl group, or a vinyl group by a conventional method. EXAMPLES

[0279] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Evaluation methods are described below.

[0280] [ 1 H-NMR] Measurements were performed using a JEOL Ltd. "JNM-ECZ400 (400 MHz)" or a JEOL Ltd. "JNM-ECA600 (600 MHz)" with chloroform-d (CDCl3) as the deuterated solvent and tetramethylsilane (TMS) as the standard substance.

[0281] [Refractive index] Using an Abbe refractometer (Atago Co., Ltd., "NAR-2T·HI"), samples were dissolved in 1,3-dimethyl-2-imidazolidinone (DMI) to prepare multiple solutions with different concentrations, and the refractive index of each solution was measured at a temperature of 25°C and a wavelength of 589 nm. The refractive index was determined by extrapolating the refractive index results at each concentration to 100% by mass.

[0282] [Solubility] The solubility of the sample was confirmed by mixing the sample with a predetermined solvent shown in the table below at a temperature of 25° C. In detail, the sample was added to a predetermined amount of solvent until it was no longer completely dissolved, and the liquid layer (solvent layer) of the obtained mixture was subjected to content analysis using HPLC (Shimadzu Corporation's "SPD-20A"), and the concentration of the sample in the liquid layer (solvent layer) (the maximum concentration that could be dissolved) was taken as the solubility.

[0283] [Synthesis Example 1] Synthesis of DNF

[0284] [ka]

[0285] Under a nitrogen atmosphere, 150 g of xylene, 60.0 g (209.6 mmol) of 1,1'-bi-2-naphthol, and 14 g (0.35 mol ratio) of p-toluenesulfonic acid monohydrate were placed in a 500 mL flask, and the temperature was raised to 140°C.

[0286] The temperature after heating was 135 to 145° C., and the mixture was kept at this temperature in a thermostatic bath to carry out the reaction for 17 hours.

[0287] After the reaction, 60 g of water and 12.9 g (0.49 molar ratio) of 32% by mass aqueous sodium hydroxide solution were added to the liquid cooled to 80°C, and the mixture was stirred for 10 minutes while keeping the temperature at 75 to 80°C in a thermostatic bath. After allowing to stand at 75 to 80°C, the lower aqueous layer was separated and removed.

[0288] To the obtained organic layer, 60 g of water was added, and the mixture was stirred for 10 minutes while keeping the temperature at 75 to 80° C. in a thermostatic bath, and then allowed to stand at 75 to 80° C., and the lower aqueous layer was separated and removed.

[0289] 150 g of xylene and 10 g of activated carbon were added to the obtained organic layer, and the mixture was stirred for 30 minutes while keeping the temperature at 75 to 80°C in a thermostatic bath, and then filtered. The filtration residue was washed with 90 g of xylene kept at 90°C.

[0290] The filtrate and the washings were combined and the solvent was removed under reduced pressure at 65°C or less to obtain 108 g of a concentrated solution. The temperature of the concentrated solution was adjusted to 60-65°C, 119 g of methanol was added, and the mixture was stirred for 1 hour while being kept at 60-65°C in a thermostatic bath, cooled to 5°C, and stirred for 30 minutes while being kept at 0-5°C in a thermostatic bath, and then filtered.

[0291] The obtained wet crystals were dried to obtain 51.4 g of dinaphthofuran (DNF) as a solid (purity by HPLC: 99%, theoretical yield: 91 mol%).

[0292] 1 H-NMR (CDCl3): δ(ppm)7.59(t,J 7.2,2H), 7.73(t,J 7.2,2H), 7.84(d,J 9.2,2H), 7.96(d,J 9.2,2H), 8.07(d,J 8.8,2H), 9.16(d,J 8.2,2H).

[0293] The refractive index and solubility of the obtained DNF were evaluated, and the results are shown in Table 1. Note that, as Reference Example 1, the evaluation results of dinaphthothiophene (DNT) are also shown in Table 1.

[0294] [Table 1]

[0295] [Example 1] Synthesis of 5AcDNF

[0296] [ka]

[0297] Under a nitrogen atmosphere, 321 g of dichloromethane and 80.5 g (300.0 mmol) of dinaphthofuran (DNF) were placed in a 500 mL flask and cooled to 5°C.

[0298] After cooling, the mixture was kept at 0 to 5°C in a thermostatic bath, 90.0g of aluminum chloride (2.25 molar ratio) was added, and 37.4g of acetic anhydride (1.22 molar ratio) was added dropwise. After the dropwise addition, the mixture was kept at 0 to 5°C and reacted for 1 hour, yielding 527g of a reaction liquid.

[0299] Separately, under a nitrogen atmosphere, 725 g of methanol was charged into a 1 L flask, cooled to 0 to 10°C, and the reaction liquid was added at 0 to 10°C. The mixture was stirred in a thermostatic bath at 0 to 10°C for 30 minutes, filtered, and the filtration residue was washed with 322 g of methanol.

[0300] The obtained wet crystals were dried to obtain 75.3 g of 5-acetyldinaphthofuran (5AcDNF) as a solid (purity by HPLC: 95%, theoretical yield: 77 mol%).

[0301] 1 H-NMR (CDCl3): δ(ppm)2.87(s,3H), 7.62(t,J 7.4,1H), 7.69(t,J 7.8,1H), 7.75-7.80(m,2H), 7.85(d,J 8.8,1H), 8.03(d,J 8.8,1H), 8.09(d,J 8.8,1H), 8.28(s,1H), 8.92(d,J 8.6,1H), 9.12(d,J 8.8,1H), 9.18(d,J 8.8,1H).

[0302] The refractive index and solubility of the obtained 5AcDNF (5-acetyl compound) were evaluated, and the results are shown in Table 2.

[0303] [Table 2]

[0304] [Example 2] Synthesis of 5HEDNF

[0305] [ka]

[0306] Under a nitrogen atmosphere, 160 g of tetrahydrofuran, 20.0 g (64.4 mmol) of 5-acetyldinaphthofuran (5AcDNF), and 20 g of methanol were charged into a 300 mL flask, and then 2.9 g (1.2 mol ratio) of sodium borohydride was added over a period of 1 hour.

[0307] The mixture was kept at 20 to 30° C. in a thermostatic chamber and reacted for 1 hour to obtain 193 g of a reaction liquid.

[0308] To the reaction mixture, 50 g of toluene and 84 g of water were added, and the mixture was stirred for 15 minutes, then allowed to stand and the lower aqueous layer was separated and removed.

[0309] To the resulting organic layer, 10.3 g (3.0 molar ratio) of ammonium chloride and 60 g of water were added, and after stirring for 15 minutes, the mixture was allowed to stand and the lower aqueous layer was separated and removed.

[0310] The resulting organic layer was subjected to removal of the solvent under reduced pressure at 40° C. to obtain 25 g of a concentrated liquid.

[0311] To the resulting concentrated liquid, 60 g of dichloromethane and 40 g of methanol were added, and the solvent was removed under reduced pressure at 40°C. By drying, 19.2 g of 5-(1-hydroxyethyl)dinaphthofuran (5HEDNF) was obtained as a solid (purity by HPLC: 97%, theoretical yield: 95 mol%).

[0312] 1 H-NMR (CDCl3): δ(ppm)1.75(d,J 3.6,3H), 2.07(d,J 1.8,1H), 5.81(q,J 4.0 6.4,1H), 7.56-7.62(m,2H), 7.72(t,J 7.6,2H), 7.81(d,J 8.8,1H), 7.93(d,J 8.0,1H), 8.06(t,J 3.8,2H), 8.25(d,J 8.25,1H), 9.09(d,J 4.4,1H), 9.16(d,J 4.2,1H).

[0313] The refractive index and solubility of the obtained 5HEDNF (5-hydroxyethyl compound) were evaluated, and the results are shown in Table 3.

[0314] [Table 3]

[0315] [Example 3] Synthesis of 5EDNFA

[0316] [ka]

[0317] Under a nitrogen atmosphere, 45 g of tetrahydrofuran, 9.0 g (28.8 mmol) of 5-(1-hydroxyethyl)dinaphthofuran (5HEDNF), and 4.1 g (1.4 mol ratio) of triethylamine were charged into a 100 mL flask, and the mixture was kept at 15 to 25°C. Then, 3.5 g (1.34 mol ratio) of acrylic acid chloride was added dropwise over 20 minutes.

[0318] The mixture was kept at 15 to 25° C. in a thermostatic bath and reacted for 1 hour, then heated to 45 to 55° C. and reacted at that temperature for 5 hours to obtain 61 g of a reaction liquid.

[0319] To the reaction mixture, 21 g of toluene and 14 g of water were added, and the mixture was stirred for 15 minutes, then allowed to stand and the lower aqueous layer was separated and removed.

[0320] To the resulting organic layer was added 14 g of water, and the mixture was stirred for 15 minutes, then allowed to stand and the lower aqueous layer was separated and removed.

[0321] The obtained organic layer was treated with activated carbon and separated and purified by column chromatography (MDC / heptane (volume ratio) = 1 / 2) to obtain 6.5 g of 5-(1-acryloyloxyethyl)dinaphthofuran as a pale yellowish white solid (HPLC purity: 99%, theoretical yield: 62 mol%).

[0322] 1H-NMR(CDCl3): δ(ppm)1.85(d,J 3.2, 3H), 5.90-5.92(m,1H), 6.23-6.30(m,1H), 6.50-6.55(m,1H), 6.90(q,J 6.4,1H), 7.59(t,J 7.4,1H), 7.65(t,J 7.4,1H), 7.75(m,2H), 7.83(d,J 8.8,1H), 7.96(d,J 8.8,1H), 8.01(s,1H), 8.07(d,J 8.4,1H), 8.28(d,J 8.4,1H), 9.12(d,J 8.4,1H), 9.21(d,J 8.0,1H).

[0323] The refractive index and solubility of the obtained 5EDNFA (5-ethyl acrylate compound) were evaluated, and the results are shown in Table 4. Note that, as Reference Example 2, the evaluation results of 5-[1-(acryloyloxy)ethyl]dinaphthothiophene (5EDNTA) are also shown in Table 4.

[0324] [Table 4]

[0325] [Example 4] Synthesis of 5EDNFMA

[0326] [ka]

[0327] Under a nitrogen atmosphere, 45 g of tetrahydrofuran, 9.0 g (28.8 mmol) of 5-(1-hydroxyethyl)dinaphthofuran (5HEDNF), 1.06 g (0.30 mol ratio) of 4-dimethylaminopyridine, and 5.5 g (1.89 mol ratio) of triethylamine were charged into a 100 mL flask, and the mixture was kept at 15 to 25°C. Then, 5.24 g (1.74 mol ratio) of methacryloyl chloride was added dropwise over 30 minutes.

[0328] The mixture was kept at 15 to 25° C. in a thermostatic chamber and reacted for 20 hours to obtain 65 g of a reaction liquid.

[0329] To the reaction mixture, 21 g of toluene and 14 g of water were added, and the mixture was stirred for 15 minutes, then allowed to stand and the lower aqueous layer was separated and removed.

[0330] To the resulting organic layer was added 14 g of water, and the mixture was stirred for 15 minutes, then allowed to stand and the lower aqueous layer was separated and removed.

[0331] The obtained organic layer (76 g) was treated with activated carbon and separated and purified by column chromatography [ethyl acetate / heptane (volume ratio) = 1 / 2] to obtain 5.1 g of 5-(1-methacryloyloxyethyl)dinaphthofuran as a pale yellowish white solid (HPLC purity: 99%, theoretical yield: 47 mol%).

[0332] 1 H-NMR(CDCl3): δ(ppm)1.84(d,J 6.4,3H), 2.04(s,3H), 5.66(s,1H), 6.28(s,1H), 6.87(q,J 6.7,1H), 7.59(t,J 7.6,1H), 7.66(t,J 7.6,1H), 7.76(q,J 7.9,2H), 7.84(d,J 9.2,1H), 7.97(d,J 9.2,1H), 8.00(s,1H), 8.08(d,J 7.2,1H), 8.30(d,J 8.8,1H), 9.13(d,J 8.8,1H), 9.22(d,J 8.0,1H).

[0333] The refractive index and solubility of the obtained 5EDNFMA (5-ethyl methacrylate compound) were evaluated, and the results are shown in Table 5. Note that, as Reference Example 3, the evaluation results of 5-[1-(methacryloyloxy)ethyl]dinaphthothiophene (5EDNTMA) are also shown in Table 5.

[0334] [Table 5]

[0335] [Example 5] Synthesis of 5EDNFM

[0336] [ka]

[0337] Under a nitrogen atmosphere, 4.8g of tetrahydrofuran, 5-(1-hydroxyethyl)dinaphthofuran (5HEDNF) 5.0g (16.0mmol), 1.47g (0.15mol ratio) of 51% by mass aqueous solution of benzyltributylammonium chloride, and 12.6g (10mol ratio) of 51% by mass aqueous solution of sodium hydroxide were charged in a 50mL flask, and 4.5g (2.0mol ratio) of methyl iodide was added dropwise over 30 minutes at 0-40°C. After the dropwise addition, the temperature was raised to 40-45°C, and the reaction was carried out at the same temperature for 40 hours, obtaining 26g of reaction liquid.

[0338] To the reaction mixture, 53 g of toluene and 24 g of water were added, and the mixture was stirred for 10 minutes, then allowed to stand and the lower aqueous layer was separated and removed.

[0339] 20 g of water was added to the obtained organic layer, and the pH was adjusted to 6 to 8 with 36% by mass hydrochloric acid, and then the mixture was allowed to stand, and the lower aqueous layer was separated and removed.

[0340] To the resulting organic layer was added 20 g of water, and the mixture was stirred for 10 minutes, then allowed to stand and the lower aqueous layer was separated and removed.

[0341] 1 g of activated carbon was added to the obtained organic layer, and the mixture was stirred at 0 to 40° C. for 30 minutes, filtered, and the filtration residue was washed with 1 g of toluene.

[0342] The resulting filtrate was subjected to solvent removal under reduced pressure at 40° C. to obtain 26.0 g of a concentrated liquid.

[0343] To the concentrated liquid, 52 g of methanol was added dropwise over 30 minutes at 10 to 40° C., and the mixture was stirred for 30 minutes.Then, the mixture was cooled to 0 to 10° C., stirred at the same temperature for 30 minutes, and then filtered.

[0344] The obtained wet crystals were dried to obtain 2.77 g of 5-(1-methoxyethyl)dinaphthofuran (5EDNFM) as a slightly yellowish white solid (purity by HPLC: 99%, theoretical yield: 53 mol%).

[0345] 1H-NMR(CDCl3): δ(ppm)1.71(d,J 6.4,3H), 3.42(s,3H), 5.25(q,J 6.4,1H), 7.61(m,2H), 7.75(q,J 7.2,2H), 7.85(d,J 9.2,1H), 7.96(d,J 8.4,1H), 8.0(s,1H), 8.08(d,J 8.4,1H), 8.32(d,J 8.8,1H), 9.14(d,J 8.4,1H), 9.23(d,J 8.8,1H).

[0346] The refractive index and solubility of the obtained 5EDNFM (5-methoxyethyl compound) were evaluated, and the results are shown in Table 6.

[0347] [Table 6]

[0348] [Example 6] Synthesis of 5AEODNF

[0349] [ka]

[0350] Under a nitrogen atmosphere, 23.7 g of 50% by mass aqueous sodium hydroxide solution, 3.7 g (0.20 mol ratio) of 50% by mass benzyltributylammonium chloride, 9.2 g (4.0 mol ratio) of allyl chloride, 19 g of toluene, and 9.4 g (30.0 mmol) of 5-(1-hydroxyethyl)dinaphthofuran (5HEDNF) were charged into a 50 mL flask, and the temperature was then raised to 30°C.

[0351] The mixture was kept at 30 to 40° C. in a thermostatic chamber and reacted for 3 hours to obtain 64 g of a reaction liquid.

[0352] 15 g of water was added to the reaction solution, stirred for 10 minutes, and then allowed to stand to separate and remove the lower aqueous layer. 15 g of water was added to the resulting organic layer, stirred for 10 minutes, and then allowed to stand to separate and remove the lower aqueous layer.

[0353] The resulting organic layer (35 g) was separated and purified by column chromatography (dichloromethane) to obtain 10.0 g of 5-(1-allyloxy-ethyl)dinaphthofuran (5AEODNF) as a red liquid (purity by HPLC: 99%, theoretical yield: 95 mol%).

[0354] 1 H-NMR (CDCl3): δ(ppm)1.72(d,J 6.4,3H), 3.95-4.00(m,1H), 4.09-4.14(m,1H), 5.20-5.24(m,1H), 5.30-5.35(m,1H), 5.41(q,J 6.4,1H), 5.97-6.06(m,1H), 7.56-7.64(m,2H), 7.72-7.77(m,2H), 7.85(d,J 8.8,1H), 7.96(d,J 8.8,1H), 8.03(s,1H), 8.07(d,J 8.8,1H), 8.32(d,J 8.4,1H), 9.14(d,J 8.8,1H), 9.22(d,J 8.4,1H).

[0355] The refractive index and solubility of the obtained 5AEODNF (5-allyl ethyl ether compound) were evaluated, and the results are shown in Table 7.

[0356] [Table 7]

[0357] [Example 7] Synthesis of 5VDNF

[0358] [ka]

[0359] Under a nitrogen atmosphere, 426 g of toluene, 8.7 g (27.7 mmol) of 5-(1-hydroxyethyl)dinaphthofuran (5HEDNF), 40 mg (0.75 mol ratio) of p-toluenesulfonic acid monohydrate, and 26 mg of methoquinone were placed in a 500 mL flask, and the temperature was then raised to 110° C. while blowing air into the liquid.

[0360] The mixture was kept at 110° C. in a thermostatic bath and reacted for 3 hours under reflux while dehydrating using a Dean-Stark tube, to obtain 430 g of a reaction liquid.

[0361] To the reaction liquid, 87 g of a 0.1% by mass aqueous solution of sodium hydroxide was added, and after stirring for 5 minutes, the mixture was allowed to stand and the lower aqueous layer was separated and removed.

[0362] The solvent was removed from the resulting organic layer under reduced pressure at 35° C. to obtain 9 g of a concentrated liquid.

[0363] The obtained concentrated liquid was separated and purified by column chromatography (dichloromethane / heptane (volume ratio) = 1 / 9) to obtain 5.0 g of 5-vinyldinaphthofuran (5VDNF) as a pale yellow solid (purity by HPLC: 97%, theoretical yield: 61 mol%).

[0364] 1 H-NMR(CDCl3): δ(ppm)5.59(dd,J 10.8 1.2,1H), 5.92(dd,J 17.4 1.4,1H), 7.57-7.65(m,3H), 7.73(dd,J 6.8 1.2,1H), 7.77(dd,J 6.8 1.2,1H), 7.84(d,J 8.0,1H), 7.96(d,J 10.0,2H), 8.07(d,J 8.4,1H), 8.33(d,J 8.8,1H), 9.13(d,J 8.8,1H), 9.18(d,J 8.8,1H).

[0365] The refractive index and solubility of the obtained 5VDNF (5-vinyl compound) were evaluated, and the results are shown in Table 8.

[0366] [Table 8]

[0367] [Example 8] Synthesis of 6FDNF

[0368] [ka]

[0369] Under a nitrogen atmosphere, 134 g of tetrahydrofuran and 13.4 g (50.0 mmol) of dinaphthofuran (DNF) were placed in a 300 mL flask and cooled to -10°C.

[0370] After cooling, the mixture was kept at −15° C. to −5° C. in a thermostatic bath, and 37.5 mL of a 1.6 mol / L n-butyllithium / hexane solution (1.2 molar ratio) was added dropwise over 1 hour, followed by reaction at the same temperature for 30 minutes.

[0371] After the reaction, the mixture was kept at −15° C. to −5° C. in a thermostatic bath, and 11.0 g (3.0 mol ratio) of N,N-dimethylformamide was added dropwise over 1 hour, followed by reacting at the same temperature for 1 hour.

[0372] After the reaction, 1.1 g of water (1.2 molar ratio) and 12.2 g of 36 mass % aqueous hydrogen chloride solution (2.4 molar ratio) were added and stirred for 30 minutes, and then the solvent was removed under reduced pressure at 40° C. to obtain 74 g of a concentrated liquid.

[0373] After adding 10 g of methanol and 25 g of water to the concentrated liquid, the mixture was cooled to 5°C, kept at 0 to 5°C in a thermostatic bath, stirred for 1 hour, filtered, and the obtained wet crystals were washed with 21 g of toluene and 14 g of water.

[0374] The obtained wet crystals were dried to obtain 12.7 g of 6-formyldinaphthofuran (6FDNF) as a yellow solid (purity by HPLC: 92%, theoretical yield: 86 mol%).

[0375] 1 H-NMR (CDCl3): δ(ppm)7.59-7.66(m,2H), 7.75(t,J 5.2,1H), 7.85(t,J 5.1,1H), 7.92(d,J 9.2,1H), 8.00(d,J 9.2,1H), 8.08(d,J 8.0,1H), 8.18(d,J 8.0,1H), 8.45(s,1H), 9.04(d,J 8.4,1H), 9.12(d,J 8.4,1H), 10.68(s,1H).

[0376] The refractive index and solubility of the obtained 6FDNF (6-formyl compound) were evaluated, and the results are shown in Table 9.

[0377] [Table 9]

[0378] [Example 9] Synthesis of 6HMDNF

[0379] [ka]

[0380] Under a nitrogen atmosphere, 90 g of tetrahydrofuran, 10.0 g (37.8 mmol) of 6-formyldinaphthofuran (6FDNF), and 1.0 g of Raney nickel were placed in a 200 mL autoclave and then sealed.

[0381] After sealing, the gas layer was replaced with hydrogen, the temperature was raised to 75 to 85° C., hydrogen was charged up to 0.5 MPa, and the mixture was stirred at the same temperature for 10 hours.

[0382] After stirring, the mixture was cooled to 20 to 30° C., the pressure was released, and the catalyst was separated by filtration.

[0383] The resulting filtrate was subjected to solvent removal under reduced pressure at 50° C. to obtain 39 g of a concentrated liquid.

[0384] The concentrated solution was filtered, and the obtained wet crystals were dried to obtain 6.8 g of 6-(hydroxymethyl)dinaphthofuran (6HMDNF) as a white solid (purity by HPLC: 99%, theoretical yield: 60 mol%).

[0385] 1H-NMR (CDCl3): δ(ppm)2.18(t,J 4.3,1H), 5.29(d,J 6.4,2H), 7.58-7.62(m,2H), 7.73-7.76(m,2H), 7.87(d,J 8.8,1H), 7.98(d,J 8.8,2H), 8.08(d,J 8.4,2H), 9.14-9.17(m,2H).

[0386] The refractive index and solubility of the obtained 6HMDNF (6-hydroxymethyl compound) were evaluated, and the results are shown in Table 10. Note that, as Reference Example 4, the evaluation results of 6-(hydroxymethyl)dinaphthothiophene (6HMDNT) are also shown in Table 10.

[0387] [Table 10]

[0388] [Example 10] Synthesis of 6MDNFA

[0389] [ka]

[0390] Under a nitrogen atmosphere, 25 g of tetrahydrofuran, 5.0 g (16.8 mmol) of 6-(hydroxymethyl)dinaphthofuran (6HMDNF), and 2.15 g (1.25 mol ratio) of triethylamine were charged into a 50 mL flask and kept at 15 to 25°C. Then, 1.82 g (1.20 mol ratio) of acryloyl chloride was added dropwise over 50 minutes.

[0391] The mixture was kept at 15 to 25° C. in a thermostatic bath and reacted for 1 hour, then heated to 45 to 55° C. and reacted at that temperature for 5 hours to obtain 33 g of a reaction liquid.

[0392] The reaction solution was cooled to 20-30°C, 1 g of methanol was added at the same temperature, and then 12 g of heptane was added dropwise at the same temperature over 1 hour. After filtering off the insoluble matter, the filtrate was desolvated at 40°C under reduced pressure and dried to obtain 5.7 g of crude crystals.

[0393] To the crude crystals were added 51 g of toluene and 18 g of water, and the mixture was stirred for 15 minutes and then allowed to stand, after which the lower aqueous layer was separated and removed.

[0394] The resulting organic layer was treated with activated carbon, and the activated carbon was separated by filtration.

[0395] The obtained filtrate was desolvated under reduced pressure at 40°C, and then 34 g of toluene was added to the obtained concentrated liquid, followed by dropwise addition of 84 g of methanol at 20 to 30°C over 1 hour. After stirring at the above temperature for 30 minutes, the mixture was cooled to 0 to 5°C, kept at 0 to 5°C in a thermostatic bath and stirred for 1 hour. The wet crystals obtained by filtration were washed with 18 g of methanol and dried to obtain 2.34 g of 6-(acryloyloxymethyl)dinaphthofuran (6MDNFA) as a white solid (purity by HPLC: 98%, theoretical yield: 40 mol%).

[0396] 1 H-NMR (CDCl3): δ(ppm)5.80(s,2H), 5.90(dd,J 10.4 1.2,1H), 6.25(dd,J 17.2 10.4,1H), 6.53(dd,J 17.2 1.2,1H), 7.60(t,J 7.4,2H), 7.76(t,J 7.8,2H), 7.88(d,J 8.8,1H), 7.99(d,J 11.6,2H), 8.08(d,J 8.0,2H), 9.15(d,J 8.8,2H).

[0397] The refractive index and solubility of the obtained 6MDNFA (6-methyl acrylate compound) were evaluated, and the results are shown in Table 11. Note that, as Reference Example 5, the evaluation results of 6-(acryloyloxymethyl)dinaphthothiophene (6MDNTA) are also shown in Table 11.

[0398] [Table 11]

[0399] [Example 11] Synthesis of 6MDNFMA

[0400] [ka]

[0401] Under a nitrogen atmosphere, 29 g of toluene, 5.8 g (19.4 mmol) of 6-(hydroxymethyl)dinaphthofuran (6HMDNF), 0.05 g (0.02 mol ratio) of 4-dimethylaminopyridine, and 2.6 g (1.31 mol ratio) of triethylamine were charged into a 100 mL flask, and the mixture was kept at 15 to 25°C. After that, 2.64 g (1.30 mol ratio) of methacryloyl chloride was added dropwise over 40 minutes. The mixture was then heated to 35 to 45°C and kept at 35 to 45°C in a thermostatic bath for 5 hours to give 40 g of reaction liquid.

[0402] To the reaction liquid, 1 g of methanol, 6 g of toluene, and 6 g of water were added, and after stirring for 15 minutes, the mixture was allowed to stand and the lower aqueous layer was separated and removed.

[0403] Further, 12 g of water was added to the obtained organic layer, and after stirring for 15 minutes, the mixture was allowed to stand and the lower aqueous layer was separated and removed.

[0404] The resulting organic layer (40 g) was treated with activated carbon, and the activated carbon was separated by filtration.

[0405] The obtained filtrate was desolvated under reduced pressure at 40°C, and then 25 g of methanol was added dropwise to the obtained concentrated liquid at 20 to 30°C over 1 hour. After stirring at the same temperature for 30 minutes, the obtained wet crystals were filtered and washed with 5 g of toluene to obtain 6.8 g of crude crystals.

[0406] The crude crystals were dissolved in 30 g of dichloromethane and 15 g of toluene, and the solvent was removed under reduced pressure at 40° C. 19 g of methanol was added to the resulting concentrated liquid, which was then stirred at 10 to 30° C. for 30 minutes. The wet crystals obtained by filtration were washed with 5 g of toluene and dried to obtain 4.21 g of 6-(methacryloyloxymethyl)dinaphthofuran (6MDNFMA) as a light brown solid (purity by HPLC: 95%, theoretical yield: 59 mol%).

[0407] 1 H-NMR (CDCl3): δ(ppm)2.02(s,3H), 5.63(t,J 1.4,1H), 5.79(s,2H), 6.24(s,1H), 7.60(t,J 7.6,2H), 7.76(t,J 7.76,2H), 7.87(d,J 9.2,1H), 7.98(d,J 7.6,2H), 8.08(d,J 8.8,2H), 9.15(d,J 8.0,2H).

[0408] The refractive index and solubility of the obtained 6MDNFMA (6-methyl methacrylate compound) were evaluated, and the results are shown in Table 12. Note that, as Reference Example 6, the evaluation results of 6-(methacryloyloxymethyl)dinaphthothiophene (6MDNTMA) are also shown in Table 12.

[0409] [Table 12] [Industrial Applicability]

[0410] The dinaphthofuran derivative of the present invention can be used as a reagent, an optical material [for example, a display material such as an anti-reflection film (for example, an index matching film), a refractive index enhancer, etc.], a resin raw material, an additive, etc.

Claims

1. A dinaphthofuran derivative represented by the following formula (1): 【Chemistry 1】 [In the formula, R １ and R ２ represents a chain hydrocarbon group having an oxygen atom and / or an unsaturated carbon bond, R ３ and R ４ is independently R １ and R ２ represents a substituent different from n represents 0 or 1; m represents an integer of 0 to 5; k represents an integer of 0 to 6.

2. In the formula (1), R １ Or R ２ The dinaphthofuran derivative according to claim 1, wherein represents any one of groups selected from the following formulas (1a), (1b) and (1c): 【Chemistry 2】 [In the formula, X １ , X ２ , X ４ , X ５ each independently represents a hydrogen atom or an aliphatic hydrocarbon group; ３ represents a hydrogen atom, an optionally substituted chain hydrocarbon group, or an acyl group.

3. 3. The dinaphthofuran derivative according to claim 1, wherein in the formula (1), n ​​is 1.

4. In the formulas (1a), (1b) and (1c), X １ and X ２ represents a hydrogen atom or an alkyl group; ３ represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkenoyl group; X ４ and X ５ The dinaphthofuran derivative according to claim 3, wherein represents a hydrogen atom.

5. In the formula (1b), X ３ The dinaphthofuran derivative according to claim 3, wherein represents an alkenyl group or a (meth)acryloyl group.

6. In the formulas (1a) and (1b), X １ and X ２ represents a hydrogen atom, and X ３ The dinaphthofuran derivative according to claim 3, wherein represents a hydrogen atom, an alkenyl group or a (meth)acryloyl group.

7. 3. The dinaphthofuran derivative according to claim 1 or 2, represented by the following formula (2c): 【Chemistry 3】 [In the formula, R ３ and R ４ each independently represents a group [—CHX ２ (O.X. ３ａ ) ], and X ２ represents a hydrogen atom or an aliphatic hydrocarbon group; X ３ａ represents an alkenyl group or a (meth)acryloyl group, m represents an integer of 0 to 5, and k represents an integer of 0 to 6.

8. 3. A method for producing a dinaphthofuran derivative according to claim 1 or 2, comprising an acyl group substitution step of reacting a dinaphthofuran compound represented by the following formula (2) with an acylating agent to substitute an acyl group at the 5-position or 6-position of the dinaphthofuran compound: 【Chemistry 4】 [In the formula, R ３ and R ４ are independently R １ and R ２ m represents an integer of 0 to 5; k represents an integer of 0 to 6; and at least one of the 5-position and the 6-position is a group R ３ not replaced by

9. The method according to claim 8, wherein in the acyl group substitution step, the dinaphthofuran compound is reacted with the acylating agent in the presence of an acid catalyst to substitute an acyl group at the 5-position of the dinaphthofuran compound represented by formula (2).

10. The method according to claim 8, wherein in the acyl group substitution step, the dinaphthofuran compound is reacted with an organolithium compound and the acylating agent to substitute an acyl group at the 6-position of the dinaphthofuran compound represented by formula (2).

11. A method for producing a dinaphthofuran derivative represented by the following formula (2c): an acyl group substitution step of reacting a dinaphthofuran compound represented by the following formula (2) with an acylating agent to substitute an acyl group at the 5-position of the dinaphthofuran compound to obtain an acyl-substituted product; a reduction step of reducing the acyl-substituted product to obtain a hydroxyl-containing dinaphthofuran derivative; and The production method includes an etherification step of reacting the hydroxyl group-containing dinaphthofuran derivative with an etherification agent to obtain the dinaphthofuran derivative represented by the formula (2c). 【Chemistry 5】 [In the formula, R ３ and R ４ each independently represents a group [—CHX ２ (O.X. ３ａ ) ], and X ２ represents a hydrogen atom or an aliphatic hydrocarbon group; X ３ａ represents an alkenyl group or a (meth)acryloyl group, m represents an integer of 0 to 5, and k represents an integer of 0 to 6. 【Chemistry 6】 [In the formula, R ３ and R ４ are independently a group [—CHX ２ (O.X. ３ａ m represents an integer of 0 to 5; k represents an integer of 0 to 6; and at least one of the 5-position and the 6-position is a group R ３ not replaced by

12. A method for producing a dinaphthofuran derivative represented by the following formula (2c): an acyl group substitution step of reacting a dinaphthofuran compound represented by the following formula (2) with an acylating agent to substitute an acyl group at the 5-position of the dinaphthofuran compound to obtain an acyl-substituted product; a reduction step of reducing the acyl-substituted product to obtain a hydroxyl-containing dinaphthofuran derivative; and The production method includes an esterification step of reacting the hydroxyl group-containing dinaphthofuran derivative with an esterifying agent to obtain the dinaphthofuran derivative represented by the formula (2c). 【Chemistry 7】 [In the formula, R ３ and R ４ each independently represents a group [—CHX ２ (O.X. ３ａ ) ], and X ２ represents a hydrogen atom or an aliphatic hydrocarbon group; X ３ａ represents a (meth)acryloyl group, m represents an integer of 0 to 5, and k represents an integer of 0 to 6. 【Chemistry 8】 [In the formula, R ３ and R ４ are independently a group [—CHX ２ (O.X. ３ａ m represents an integer of 0 to 5; k represents an integer of 0 to 6; and at least one of the 5-position and the 6-position is a group R ３ not replaced by

13. A liquid composition comprising the dinaphthofuran derivative according to claim 1 or 2 and an organic solvent.

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