JP2018083774A - Dinaphthothiophene derivative and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel dinaphthothiophene derivative that can achieve both of solubility in solvent and high refractive indexes, and a method for producing the same.SOLUTION: The present invention provides a compound represented by formula (1) or a salt thereof [X is S or a sulfonyl group; Ris the group -SOY; Y is a hydroxyl group, a (poly) alkoxy group, an amino group or a substituted amino group; k is 0 or 1; Rindependently represents an alkyl group or an alkoxy group; m1 and m2 independently represent 0 or 1; n1 and n2 independently represent an integer of 0-4; p1 and p2 independently represent 0 or 1; the number 1-13 are position numbers; n1+p1 and n2+p2 independently represent an integer of 0-4].SELECTED DRAWING: None

Description

  The present invention relates to a novel dinaphthothiophene derivative and a method for producing the same.

  Dinaphtho [2,1-b: 1 ′, 2′-d] thiophene (also simply referred to as dinaphthothiophene) is known to exhibit a high refractive index because it contains a sulfur atom and an aromatic ring.

  For example, Japanese Patent No. 5240798 (Patent Document 1) describes a refractive index improver containing a dinaphthothiophene compound or a polymer having a dinaphthothiophene skeleton in the main chain or side chain. However, since dinaphthothiophene compounds have extremely low solubility in solvents (particularly aqueous solvents), their use is significantly limited.

  In addition, although it is described in Patent Document 1 that the dinaphthothiophene compound may have various substituents such as a sulfo group (or sulfonic acid group), the dinaphtho having a sulfonic acid group There is no specific description of thiophene derivatives, in particular dinaphthothiophene derivatives having a sulfonic acid group at a given substitution position, and methods for producing the same.

Japanese Patent No. 5240798 (claims, [0031] [0038], Examples)

  Accordingly, an object of the present invention is to provide a novel dinaphthothiophene derivative that can achieve both a solubility in a solvent and a high refractive index, and a method for producing the same.

  Another object of the present invention is to provide a novel dinaphthothiophene derivative excellent in solubility in an aqueous solvent and a method for producing the same.

  Still another object of the present invention is to provide a method capable of producing a specific dinaphthothiophene derivative with a high production rate [conversion rate (or reaction rate) and selectivity].

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a novel dinaphthothiophene derivative having a specific substituent at a specific substitution position of dinaphthothiophene has solubility in a solvent (particularly an aqueous solvent). It was found that a high refractive index can be achieved at the same time, and that it can be prepared with a high conversion and selectivity by sulfonation by a specific method, thereby completing the present invention.

  That is, the dinaphthothiophene derivative of the present invention is a compound represented by the following formula (1) or a salt thereof.

[Wherein, X is a sulfur atom or a sulfonyl group, R ¹ is a group —SO ₂ Y (where Y represents a hydroxyl group, a (poly) alkoxy group, an amino group or a substituted amino group), and k is 0 or 1 , R ² is an alkyl group or an alkoxy group, m1 and m2 are each 0 or 1, n1 and n2 are each an integer of 0 to 4, p1 and p2 are each 0 or 1, numerals 1 to 13 are position numbers, n1 + p1 and n2 + p2 are each an integer of 0 to 4].

In the formula (1), X is a sulfur atom, Y in each R ¹ is a hydroxyl group, a C _1-4 alkoxy group, an amino group, a (mono or di) C _1-4 alkylamino group, or (mono or di). A C _6-12 arylamino group (particularly a hydroxyl group, a C _1-2 alkoxy group, an amino group, a (mono or di) C _1-2 alkylamino group or a (mono or di) C _6-10 arylamino group), Each R ² is a C _1-4 alkyl group or a C _1-4 alkoxy group, m1 and m2 are each 0, n1 and n2 are each an integer of 0 to 2 (particularly 0), and p1 and p2 are each 0. May be. The compound or a salt thereof may be soluble in an aqueous solvent, and may have a refractive index of 1.63 to 1.77 at a temperature of 25 ° C. and a wavelength of 633 nm.

In the present invention, the dinaphthothiophene compound and the sulfonating agent are reacted in a solvent containing at least one selected from sulfones (particularly sulfolane), nitriles and carboxylic acids, and the above formula ( In 1), the method of manufacturing the compound or its salt whose Y in each R < ¹ > is a hydroxyl group is also included. The sulfonating agent may contain chlorosulfonic acid and / or fuming sulfuric acid. The ratio of the dinaphthothiophene compound and the sulfonating agent may be the former / the latter (molar ratio) = 1 / 0.7 to 1/20.

The present invention comprises reacting a compound produced by the above-described method (a compound in which Y is a hydroxyl group in the formula (1)) with an esterifying agent (for example, orthoformate triester). , A method for producing a compound in which Y in each R ¹ is a (poly) alkoxy group; and a compound produced by the method (a compound in which Y is a hydroxyl group in the formula (1)) and a thionyl halide. In the formula (1), a compound in which Y is a halogen atom is formed, and this compound is reacted with an amine. In the formula (1), Y in each R ¹ is an amino group or a substituted amino group. Also included are methods of making the compounds.

  In the present specification and claims, “dinaphthothiophene” is used to mean dinaphtho [2,1-b: 1 ′, 2′-d] thiophene. Further, “amines” is used to mean including ammonia. Furthermore, “(poly) alkoxy” is used to mean including both an alkoxy group and a polyalkoxy group.

  In the present invention, since the novel dinaphthothiophene derivative has a specific substituent at a specific position, both solubility in a solvent (particularly an aqueous solvent) and a high refractive index can be achieved. Such a novel dinaphthothiophene derivative can be produced in a high yield because it can be produced with a high conversion (or reaction rate) and selectivity by reacting a dinaphthothiophene compound with a sulfonating agent in a specific solvent. be able to.

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

[Wherein, X represents a sulfur atom or a sulfonyl group, R ¹ represents a group —SO ₂ Y (wherein Y represents a hydroxyl group, a (poly) alkoxy group, an amino group, a substituted amino group, a halogen atom), and k represents 0 or 1, R ² is a substituent, m1 and m2 are each 0 or 1, n1 and n2 are each an integer of 0 to 4, p1 and p2 are each 0 or 1, numerals 1 to 13 are position numbers, n1 + p1 and n2 + p2 are each an integer of 0 to 4].

  In the formula (1), X is preferably a sulfur atom from the viewpoint of having a high refractive index and suppressing coloring (or yellowing), and from the viewpoint of improving solubility, X is sulfonyl. A group is preferred. Usually, X may be a sulfur atom.

In the group —SO ₂ Y represented by the group R ¹ , the (poly) alkoxy group of the group Y is, for example, a straight chain such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, or a t-butoxy group. Or a branched C _1-6 alkoxy group; and a poly C _2-6 alkoxy group such as a polyethoxy group. Preferred (poly) alkoxy groups include alkoxy groups, preferably C _1-4 alkoxy groups, and more preferably C _1-2 alkoxy groups (particularly methoxy groups).

The substituted amino group of the group Y can be roughly classified into an N-monosubstituted amino group and an N, N-disubstituted amino group. Examples of the N-monosubstituted amino group include N—C _1-6 alkylamino groups such as a methylamino group and an ethylamino group (preferably an N—C _1-4 alkylamino group, more preferably N—C _{1— 2} alkylamino group); phenylamino group, (alkylphenyl) amino group [for example, tolylamino group (for example, p-tolylamino group), xylylamino group, etc.], biphenylylamino group, naphthylamino group (for example, 1-naphthyl group) N—C _6-12 arylamino group (preferably N—C _6-10 arylamino group, more preferably N—C _6-8 arylamino group) such as amino group, 2-naphthylamino group and the like. It is done.

Examples of the N, N-disubstituted amino group include N, N-diC _1-6 alkylamino groups such as dimethylamino group and diethylamino group (preferably N, N-diC _1-4 alkylamino group, Preferably N, N-diC _1-2 alkylamino group); diphenylamino group, di (alkylphenyl) amino group (for example, ditolylamino group, dixylylamino group, etc.), dibiphenylylamino group, dinaphthylamino group N, N-diC _6-12 arylamino group (preferably N, N-diC _6-10 arylamino group, more preferably N, N-diC _6-8 arylamino group) and the like. . In the N-monosubstituted amino group and the N, N-disubstituted amino group, the aryl group substituted on the amino group is an alkyl group (for example, a linear or branched C _1-4 alkyl group such as a methyl group). , Preferably a C _1-2 alkyl group or the like).

  Examples of the halogen atom of the group Y include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and may preferably be a chlorine atom.

These groups Y may be used alone or in combination of two or more. Of these groups Y, a hydroxyl group, an alkoxy group, an amino group or a substituted amino group is preferable, and among them, a hydroxyl group, a C _1-4 alkoxy group, an amino group, a (mono or di) C _1-4 alkylamino group. Or (mono or di) C _6-12 arylamino group (especially hydroxyl group, C _1-2 alkoxy group, amino group, (mono or di) C _1-2 alkylamino group or (mono or di) C _{6 10} arylamino group) is preferred. The group Y may be selected according to the properties required for the dinaphthothiophene derivative. For example, in applications that require solubility in an aqueous solvent, a hydroxyl group is preferable, and in applications that require a high refractive index. An alkoxy group, an amino group, or a substituted amino group (preferably an alkoxy group or an amino group, particularly an amino group) is preferable from the viewpoint of effectively suppressing a decrease in refractive index. In general, when the number of substituents increases, the refractive index tends to decrease. However, when the group Y is an alkoxy group, the refractive index may be improved unexpectedly when the number of substituents increases. Furthermore, when the dinaphthothiophene derivative has a plurality of groups —SO ₂ Y (when at least one of k, p1 and p2 is 1), the plurality of groups Y may be the same or different, Are the same.

In the case group Y is a hydroxyl group, a group -SO 2 Y _(sulfo group or a sulfonic acid group) may form a salt (or sulfonate). Representative salts include, for example, alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (calcium salt, magnesium salt, etc.), heavy metal salts, ammonium salts, and other inorganic salts; A tertiary amine salt such as a trimethylamine salt, an aniline salt), an organic salt such as a quaternary ammonium salt (for example, a tetraalkylammonium salt such as a tetramethylammonium salt), or a double salt thereof. Of these salts, alkali metal salts such as sodium salts, ammonium salts, and amine salts are preferable from the viewpoint of handleability. When a salt is formed, the refractive index may decrease, but the solubility in a solvent may be improved.

  k is 0 or 1, and may be selected according to the characteristics required for the dinaphthothiophene derivative. For example, in applications that require solubility in a solvent, k = 1 is preferable and a high refractive index is required. For such applications, it is preferred that k = 0.

p1 and p2 are each 0 or 1, and preferably 1 from the viewpoint of enhancing the solubility. When p1 and / or p2 is 1, the group R ¹ may be substituted at any of positions 1 to 4 and 10 to 13 of dinaphthothiophene. Often substituted at the position and / or 11-position. From the viewpoint of increasing the refractive index, p1 and p2 are each preferably 0, and are usually 0 in many cases.

Each of the groups R ² is a substituent, and examples of the substituent include an alkyl group (for example, a linear or branched C _1-6 alkyl group such as a methyl group); a cycloalkyl group (for example, a cyclohexyl group). Aryl groups (eg, phenyl groups); aralkyl groups (eg, benzyl groups); alkoxy groups (eg, linear or branched C _1-6 alkoxy groups such as methoxy groups); cycloalkyl Oxy group (for example, cyclohexyloxy group); aryloxy group (for example, phenoxy group); aralkyloxy group (for example, benzyloxy group); alkoxyalkyl group (for example, methoxymethyl group); cycloalkoxyalkyl group (For example, cyclohexyloxymethyl group); aryloxyalkyl group (for example, An aralkyloxyalkyl group (for example, benzyloxymethyl group); a vinyl group; an allyl group; an allyloxy group; a (meth) acryloyloxyalkyl group [for example, a (meth) acryloyloxymethyl group]; ) Acryloyloxyalkoxy group [for example, 2-[(meth) acryloyloxy] ethoxy group, etc.]; styryl group; glycidyloxy group; hydroxyl group; hydroxyalkyl group [for example, hydroxymethyl group, etc.]; hydroxyalkoxy group (for example, 2-hydroxyethoxy group); formyl group; carboxyl group; alkylcarbonyl group (for example, methylcarbonyl group); alkoxycarbonyl group (for example, methoxycarbonyl group); N-alkylaminocarbonyl group (for example, Such as N- ethylaminocarbonyl group); an amino group; a nitro group; a cyano group; a thiol group, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom); and the like.

Of these substituents, an alkyl group or an alkoxy group, among them, a C _1-4 alkyl group or a C _1-4 alkoxy group (for example, a C _1-2 alkyl group or a C _1-2 alkoxy group) is preferable.

The substitution numbers m1 and m2 of the group R ² are each 0 or 1, in particular 0. m1 and m2 may be the same or different from each other. The substitution number n1 and n2 of the radicals ^{R 2} may be any integer of 0 to 4, for example, an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1 (in particular, 0 ). n1 and n2 may be the same or different from each other. If n1 and n2 is 1 or more, the substitution position of the group R ² is not particularly limited, it is substituted on any position of Gina shift thiophene skeleton 1～4- position and / or 10～13- position Good. When a plurality (or two or more) groups R ² are substituted, the types of the groups R ² may be the same as or different from each other. When the values of m1 and m2 and n1 and n2 are small (especially, both m1 and m2 are 0 and both n1 and n2 are 0), the refractive index is effectively prevented from decreasing and high refraction is achieved. This is preferable because it is easy to balance (or improve) the rate and solubility in a solvent (such as an aqueous solvent) in a balanced manner.

  N1 + p1 and n2 + p2 are each an integer of 0 to 4, for example, an integer of 0 to 3 (for example, 1 to 3), preferably an integer of 0 to 2, more preferably 0 or 1 (particularly 0). Also good.

  Representative compounds represented by the formula (1) include, for example, compounds in which m1 and m2, n1 and n2, and p1 and p2 are each 0. Depending on the type, sulfonic acids (Y is a hydroxyl group) or a salt thereof, sulfonic acid esters (Y is an alkoxy group), sulfonylamides (Y is an amino group), N-substituted sulfonylamides (Y is a substituted amino group), sulfonyl It can be roughly divided into halides (Y is a halogen atom).

  Examples of the sulfonic acids or salts thereof include 5-sulfo-dinaphthothiophene; 5,9-disulfo-dinaphthothiophene; and salts corresponding to these sulfonic acids (for example, sodium salt, ammonium salt, amine salt, etc.) And S, S-dioxides corresponding to these sulfonic acids or salts thereof [that is, a compound wherein X is a sulfonyl group in the formula (1)] and the like.

Examples of the sulfonic acid esters include a sulfo group of the compounds exemplified in the sulfonic acids or salts thereof as an alkoxysulfonyl group [for example, a C _1-6 alkoxysulfonyl group such as a methoxysulfonyl group or an ethoxysulfonyl group (preferably C _1-4). alkoxysulfonyl group, further compounds preferably C _1-2 alkoxy sulfonyl group), etc.], for example, 5-alkoxysulfonyl - Gina shift thiophene (e.g., 5-methoxy-sulfonyl - Gina shift thiophene, 5-ethoxy-sulfonyl - dinaphtho 5-C _1-6 alkoxysulfonyl-dinaphthothiophene such as thiophene); 5,9-bis (alkoxysulfonyl) -dinaphthothiophene [eg, 5,9-bis (methoxysulfonyl) -dinaphthothiophene, 5, 9-bis (d 5,9-bis (C _1-6 alkoxysulfonyl) -dinaphthothiophene etc.] such as toxisulfonyl) -dinaphthothiophene]; and S, S-dioxides corresponding to these compounds.

  Examples of the sulfonylamides include compounds in which the sulfo group of the compounds exemplified in the sulfonic acids or salts thereof is a sulfamoyl group, such as 5-sulfamoyl-dinaphthothiophene 5,9-disulfamoyl-dinaphthothiophene, and these compounds. Corresponding S, S-dioxide compounds and the like can be mentioned.

As N-substituted sulfonylamides, the sulfo group of the compounds exemplified in the sulfonic acids or salts thereof is an N-substituted sulfamoyl group [for example, N—C ₁ such as N-methylsulfamoyl group, N-ethylsulfamoyl group, etc. _-6 alkylsulfamoyl group (preferably N—C _1-4 alkylsulfamoyl group, more preferably N—C _1-2 alkylsulfamoyl group); N, N-dimethylsulfamoyl group, N, N, N-diC _1-6 alkylsulfamoyl group such as N-diethylsulfamoyl group (preferably N, N-diC _1-4 alkylsulfamoyl group, more preferably N, N-diC _1-2 alkylsulfamoyl group); N-phenyl sulfamoyl group, N- tolyl sulfamoyl group (e.g., N-p-tolyl sulfamoyl group) N- xylylene Rusuru sulfamoyl group, N- biphenylyl sulfamoyl group, N- (1-naphthyl) sulfamoyl group, N- (2-naphthyl) _{N-C 6-12} aryl sulfamoyl group such as sulfamoyl groups ( Preferably N—C _6-10 arylsulfamoyl group, more preferably N—C _6-8 arylsulfamoyl group); N, N-diphenylsulfamoyl group, N, N-ditolylsulfamoyl group ( For example, N, N-di (p-tolyl) sulfamoyl group, etc.), N, N-dixylylsulfamoyl group, N, N-dibiphenylylsulfamoyl group, N, N-di (1-naphthyl) a sulfamoyl group, N, N- di (2-naphthyl) N, such as sulfamoyl groups, N- di _{C 6-12} aryl sulfamoyl group (preferably N, N- di _{C 6-10} a And the like, and more preferably an N, N-diC _6-8 arylsulfamoyl group). Typically, for example, N-alkylsulfamoyl-dinaphthothiophenes [for example, 5- (N-methylsulfamoyl) -dinaphthothiophene, 5- (N-ethylsulfamoyl) -dinaphthothiophene 5- (N—C _1-6 alkylsulfamoyl) -dinaphthothiophene; 5,9-bis (N-methylsulfamoyl) -dinaphthothiophene, 5,9-bis (N-ethylsulfa) Moyl) -5,9-bis (N—C _1-6 alkylsulfamoyl) -dinaphthothiophene such as dinaphthothiophene; and S, S-dioxides corresponding to these compounds]; N, N— Dialkylsulfamoyl-dinaphthothiophenes [for example, 5- (N, N-dimethylsulfamoyl) -dinaphthothiophene, 5- (N, N-diethylsulfa Yl) - Ah shift thiophene such as 5-(N, _{N-di-C 1-6} alkylsulfamoyl) - Ah shift thiophene; 5,9-bis (N, N- dimethylsulfamoyl) - Gina shift thiophene, 5,9-bis (N, N-diC _1-6 alkylsulfamoyl) -dinaphthothiophene such as 5,9-bis (N, N-diethylsulfamoyl) -dinaphthothiophene; and compounds thereof N-arylsulfamoyl-dinaphthothiophenes {for example, 5- (N-phenylsulfamoyl) -dinaphthothiophene, 5- [N- (p-tolyl) ) Sulfamoyl] -dinaphthothiophene, 5- [N- (2,4-xylyl) sulfamoyl] -dinaphthothiophene, 5- [N- (4-biphenylyl) sulfamoyl - Gina shift thiophene, 5- [N- (1- naphthyl) sulfamoyl] - Gina shift thiophene, 5- [N- (2- naphthyl) sulfamoyl] - Ah shift thiophene such as 5- _{(N-C 6-12} aryl Sulfamoyl) -dinaphthothiophene; 5,9-bis (N-phenylsulfamoyl) -dinaphthothiophene, 5,9-bis [N- (p-tolyl) sulfamoyl] -dinaphthothiophene, 5,9 -Bis [N- (2,4-xylyl) sulfamoyl] -dinaphthothiophene, 5,9-bis [N- (4-biphenylyl) sulfamoyl] -dinaphthothiophene, 5,9-bis [N- (1- 5,9-Bi such as naphthyl) sulfamoyl] -dinaphthothiophene, 5,9-bis [N- (2-naphthyl) sulfamoyl] -dinaphthothiophene _{(N-C 6-12} aryl sulfamoyl) - Ah shift thiophene; and S corresponding to these compounds, S- dioxide thereof, etc.}; N, N-diaryl sulfamoyl - Gina shift thiophenes {e.g., 5 -(N, N-diphenylsulfamoyl) -dinaphthothiophene, 5- [N, N-di (p-tolyl) sulfamoyl] -dinaphthothiophene, 5- [N, N-di (2,4-xylyl) ) Sulfamoyl] -dinaphthothiophene, 5- [N, N-di (4-biphenylyl) sulfamoyl] -dinaphthothiophene, 5- [N, N-di (1-naphthyl) sulfamoyl] -dinaphthothiophene, 5- 5- (N, N-diC _6-12 arylsulfamoyl) -dinaphtho such as [N, N-di (2-naphthyl) sulfamoyl] -dinaphthothiophene Thiophene; 5,9-bis (N, N-diphenylsulfamoyl) -dinaphthothiophene, 5,9-bis [N, N-di (p-tolyl) sulfamoyl] -dinaphthothiophene, 5,9-bis [N, N-di (2,4-xylyl) sulfamoyl] -dinaphthothiophene, 5,9-bis [N, N-di (4-biphenylyl) sulfamoyl] -dinaphthothiophene, 5,9-bis [N , N-di (1-naphthyl) sulfamoyl] -dinaphthothiophene, 5,9-bis [N, N-di (2-naphthyl) sulfamoyl] -dinaphthothiophene, etc., 5,9-bis (N, N- _{DiC 6-12} arylsulfamoyl) -dinaphthothiophene; and S, S-dioxides corresponding to these compounds} and the like.

  Examples of the sulfonyl halides include compounds in which the sulfo group of the compounds exemplified in the sulfonic acids or salts thereof is a halosulfonyl group [eg, chlorosulfonyl group, bromosulfonyl group (preferably halosulfonyl group)], for example, 5- 5-halosulfonyl-dinaphthothiophene such as chlorosulfonyl-dinaphthothiophene, 5-bromosulfonyl-dinaphthothiophene; 5,9-bis (chlorosulfonyl) -dinaphthothiophene, 5,9-bis (bromosulfonyl)- 5,9-bis (halosulfonyl) -dinaphthothiophene such as dinaphthothiophene; and S, S-dioxides corresponding to these compounds).

Among these compounds, sulfonic acids or salts thereof, sulfonic acid esters [for example, 5-C _1-4 alkoxysulfonyl - Gina shift thiophene (e.g., 5-methoxy-sulfonyl - Gina shift thiophene 5-C _1-2, such as Alkoxysulfonyl-dinaphthothiophene etc.) and S, S-dioxides corresponding to these compounds], sulfonylamides, N-substituted sulfonylamides (eg N-arylsulfamoyl-dinaphthothiophenes etc.), etc. Is preferred.

Particularly, among the above compounds, 5-sulfo-dinaphthothiophene or a salt thereof, 5,9-disulfo-dinaphthothiophene or a salt thereof, among the above compounds, from the viewpoint of excellent solubility in a solvent (particularly an aqueous solvent described later), 9,9-bis (N—C _6-10 arylsulfamoyl) -dinaphthothiophene [eg, 5,9-bis [N- (p-tolyl) sulfamoyl] -dinaphthothiophene -C _6-8 arylsulfamoyl) -dinaphthothiophene etc.] (particularly 5,9-disulfo-dinaphthothiophene or a salt thereof) and S, S-dioxides corresponding to these compounds are preferred.

From the viewpoint of having a high refractive index, in a dinaphthothiophene derivative having one group —SO ₂ Y (simply referred to as “monosubstituted”), the group Y is an amino group or a substituted amino group (particularly an amino group). Certain compounds, such as 5-sulfamoyl-dinaphthothiophene, 5- (N—C _6-10 arylsulfamoyl) -dinaphthothiophene [eg, 5- [N- (p-tolyl) sulfamoyl] -dinaphthothiophene Preferred are 5- (NC _6-8 arylsulfamoyl) -dinaphthothiophene etc.] (particularly 5-sulfamoyl-dinaphthothiophene), and S, S-dioxides corresponding to these compounds, two groups Gina shift thiophene derivative having -SO 2 _Y (also simply referred to as 2 substituents), the compound group Y is an alkoxy group, for example , 5,9-bis _{(C 1-4} alkoxy sulfonyl) - Ah shift thiophene (e.g., 5,9-bis (methoxy-benzenesulfonyl) - such as Gina shift thiophene 5,9-bis _{(C 1-2} alkoxy sulfonyl) - Dinaphthothiophene etc.) and S, S-dioxides corresponding to these compounds are preferred.

Such a novel dinaphthothiophene derivative is superior in solubility in a solvent (particularly, an aqueous solvent described later) as compared with a conventional dinaphthothiophene derivative. Representative solvents include, for example, water; alcohols (eg, C _1-4 alkane monools such as methanol, ethanol, 1-propanol, 2-propanol; C _2-4 alkane diols such as ethylene glycol); Ethers (eg, chain ethers such as dimethyl ether, cyclic ethers such as tetrahydrofuran and 1,4-dioxane); glycol ethers [eg, cellosolves (eg, C _1-4 such as methyl cellosolve, ethyl cellosolve, etc.) Alkyl cellosolve, etc.), carbitols (eg, _C1-4 alkyl carbitol such as methyl carbitol, ethyl carbitol, etc.), triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol (Poly) C _2-4 alkylene glycol mono C _1-4 alkyl ether such as _nomethyl ether; (poly) C _2-4 alkylene glycol di C such as ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether _1-4 alkyl ethers and the like]; glycol ether acetates [eg, cellosolve acetates (eg, C _1-4 alkyl cellosolve acetate such as methyl cellosolve acetate), carbitol acetates (eg, C such as methyl carbitol acetate) _1-4, such as alkyl carbitol acetate), propylene glycol monomethyl ether acetate, dipropylene glycol monobutyl Agent Etc. _{(poly) C 2-4} alkylene glycol mono _{C 1-4} alkyl ether acetates such as Le acetate]; ketones (e.g., acetone, methyl ethyl ketone, etc.), esters (e.g., methyl acetate, ethyl acetate, etc.); carbonates (Dimethyl carbonate, propylene carbonate, etc.); carboxylic acids (eg, acetic acid, propionic acid, etc.); nitriles (eg, acetonitrile, propionitrile, etc.); amides (eg, N, N-dimethylformamide, N, N— Dimethylacetamide, N-methyl-2-pyrrolidone, etc.); sulfoxides (eg, dimethylsulfoxide, etc.); halogenated hydrocarbons (eg, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, etc.); and mixtures thereof Examples thereof include a mixed solvent.

Among these solvents, water and / or water-soluble organic solvents (eg, alcohols (eg, C _1-3 alkane monool; C _2-4 alkane diol, etc.); cyclic ethers (eg, tetrahydrofuran, 1, 4) Glycol ethers [eg (poly) C _2-4 alkylene glycol mono C _1-4 alkyl ether; (poly) C _2-4 alkylene glycol di C _1-4 alkyl ether etc.]; glycol ether acetate [For example, (poly) C _2-4 alkylene glycol mono C _1-4 alkyl ether acetate etc.]; acetone; organic acids (eg acetic acid, propionic acid etc.); nitriles (eg acetonitrile, propionitrile etc.) Amides (eg, N, N-dimethylformamide, N N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.): Aqueous solvents containing sulfoxides (for example, dimethyl sulfoxide, etc.) are preferable These aqueous solvents are used alone or as a mixed solvent of two or more. Of these aqueous solvents, water and alcohols are particularly preferable from the viewpoint of handleability.

Moreover, since the novel dinaphthothiophene derivative of the present invention has a high refractive index despite its high solubility, it may be used as a refractive index improver. The refractive index of the novel dinaphthothiophene derivative can be selected from the range of, for example, about 1.6 to 1.81 at a temperature of 25 ° C. and a wavelength of 633 nm, for example, 1.61 to 1.8 (for example, 1.62 to 1.62). 1.79), preferably 1.625 to 1.78 (eg, 1.63 to 1.77), more preferably about 1.635 to 1.765 (eg, 1.64 to 1.76). May be. In particular, in a dinaphthothiophene derivative having one group —SO ₂ Y, for example, 1.68 to 1.8, preferably 1.7 to 1.79 (eg, 1.72 to 1.78), more preferably May be about 1.74 to 1.77 (for example, 1.75 to 1.765). When the group Y is an amino group or a substituted amino group (particularly an amino group), the refractive index seems to be high. It is. Further, in the dinaphthothiophene derivative having _two groups —SO ₂ Y, for example, 1.61 to 1.76, preferably 1.64 to 1.755 (eg, 1.67 to 1.75), more preferably May be about 1.7 to 1.745 (for example, 1.72 to 1.74), and when the group Y is an alkoxy group, the refractive index seems to be high. The refractive index may be measured at a measurement wavelength of 633 nm for a film formed by spin coating. In addition, when it is difficult to form a film, a plurality of solutions having different concentrations are prepared, the refractive index of each solution is measured at a measurement wavelength of 589 nm, and an approximate expression representing the relationship between the refractive index and the concentration is obtained from the obtained results. The value calculated and extrapolated to 100% density may be used as the refractive index. Specifically, for example, the measurement may be performed by a method described in Examples described later.

  The dinaphthothiophene derivative of the present invention may form a composition (a coating composition or a solution) containing the above-exemplified solvent (in particular, an aqueous solvent such as water and alcohols). A homogeneous high-refractive-index film can be easily formed by applying such a composition on a substrate and drying it, because it is more soluble in a solvent than conventional dinaphthothiophene derivatives. In particular, an aqueous composition containing at least an aqueous solvent (preferably water, alcohols, particularly water) has a low environmental load and is easy to handle, and has low resistance to organic solvents (or swelling resistance). Even on the substrate, it is easy to form a high refractive index film. Therefore, it can be effectively used for an antireflection film (for example, an index matching film (or index matching layer)).

  In addition, the composition may be mixed with other resin as a binder (for example, transparent resin such as polycarbonate resin, methacrylic resin, styrene resin, etc.) as necessary to form a film with a high refractive index film. Mechanical characteristics and the like may be improved. As long as the effects of the present invention are not impaired, the composition further contains conventional additives (for example, plasticizers, stabilizers (thermal stabilizers, antioxidants, ultraviolet absorbers, etc.), fillers, and the like. , An antistatic agent, a flame retardant, a surfactant, a colorant, an antifoaming agent, and the like. The proportion of the dinaphthothiophene derivative in the composition may be, for example, about 0.1 to 80% by weight, preferably about 1 to 50% by weight.

  Moreover, the dinaphthothiophene derivative of the present invention may form a polymer (or oligomer) by using it as a monomer. Examples of the polymer (or oligomer) include a polymer in which a dinaphthothiophene skeleton is connected by a methylene group, polysulfone, or polyethersulfone.

These polymers (or oligomers) can be prepared by a conventional polymerization method. For example, a polymer in which a dinaphthothiophene skeleton is connected by a methylene group is a method described in paragraph [0048] of Patent Document 1, Example 4 and the like. That is, it may be prepared by a method of reacting paraformaldehyde in the presence of boron trifluoride diethyl ether complex. In addition, polysulfone or polyethersulfone, for example, a compound obtained by sulfonylating _two groups -SO2Y of a novel dinaphthothiophene derivative and an aromatic compound (for example, diphenyl ether) in the presence of a Lewis acid catalyst. Alternatively, it may be prepared by a method of polymerizing by Friedel-Crafts reaction. The polymer thus obtained may be used as an optical member such as an optical film (high refractive index film) or a lens. As a polymer type refractive index improver, other resins (for example, the above-described transparent resin) are used. You may mix and use.

[Method for producing novel dinaphthothiophene derivative]
(Compound wherein Y is a hydroxyl group)
Among the novel dinaphthothiophene derivatives of the present invention, in the group R ¹ of the formula (1), Y is a hydroxyl group (compound represented by the following formula (1a)) or a salt thereof is represented by the following formula (2 ) (A dinaphthothiophene compound not having a sulfonic acid group) and a sulfonating agent can be easily produced in a specific solvent (sulfonation step).

[Wherein, X, k, R ² , m 1 and m ² , n 1 and n 2, p 1 and p 2 are the same as those in the above formula (1), and n 1 + p 1 and n 2 + p 2 are each an integer of 0 to 4].

  Representative examples of the compound represented by the formula (2) include compounds in which both m1 and m2 are 0 and both n1 and n2 are 0, that is, dinaphthothiophene, dinaphthothiophene- S, S-dioxide etc. are mentioned. Dinaphthothiophene is a conventional method, for example, the method described in Patent Document 1, that is, 1,1′-binaphthol and dimethylthiocarbamoyl chloride are reacted in the presence of a base to produce a dimethylthiocarbamate. It may be synthesized by a method in which a dimethylthiocarbamate is heated to reflux in sulfolane; a method in which dinaphthothiophene contained in a petroleum residue is separated and purified. Moreover, you may prepare a S, S-dioxide body by the method etc. which are mentioned later.

  As the sulfonating agent, for example, chlorosulfonic acid, fuming sulfuric acid, sulfur trioxide and the like can be used. These sulfonating agents may be used alone or in combination of two or more. Among these sulfonating agents, when combined with a specific solvent described later, the conversion rate (or reaction rate) of the sulfonation reaction and the selectivity (to the 5-position and / or 9-position of dinaphthothiophene) From the viewpoint of excellent substitution selectivity, chlorosulfonic acid is preferred.

  The inventors of the present invention are not sure why the compound represented by the formula (1a) cannot be isolated by simply reacting a dinaphthothiophene compound with a conventional sulfonating agent. However, by reacting in the presence of the specific solvent that is not used in a general sulfonation reaction, a sulfonic acid group-containing compound represented by the formula (1a) can be obtained with an unexpectedly high reaction rate and selectivity. And was able to be isolated.

  In the present invention, examples of the specific solvent include sulfones (for example, sulfolane and 2,4-dimethylsulfolane), nitriles (for example, acetonitrile and propionitrile), carboxylic acids (for example, acetic acid and propion). Acid, etc.). Moreover, these solvents can also be used individually or in combination of 2 or more types. Of these solvents, sulfones (especially sulfolane) are preferable because they are excellent in the conversion rate and selectivity of the sulfonation reaction. The reaction is carried out in such a manner that a small amount of other solvent (for example, halogenated hydrocarbons such as methylene chloride, etc.) is 0.1 to 30 wt. %, Preferably about 1 to 5% by weight), but it is usually preferable to use a single solvent from the viewpoint of easy recovery and reuse of the solvent and high economic efficiency.

  The ratio of the dinaphthothiophene compound (for example, the compound represented by the formula (2)) and the sulfonating agent is, for example, the former / the latter (molar ratio) = 1 / 0.5 to 1/50, preferably 1. /0.7 to 1/20, more preferably about 1 / 0.9 to 1/3. In particular, when a compound having a sulfonic acid group at the 5-position is selectively prepared, for example, the former / the latter (molar ratio) = 1/1 to 1/2 (for example, 1/1 to 1 / 1.8) , Preferably 1 / 1.05 to 1 / 1.7 (for example, 1 / 1.1-1 / 1.6), more preferably 1 / 1.15 to 1 / 1.5 (for example, 1/1). In the case of selectively preparing a compound having a sulfonic acid group at the 5,9-position, for example, the former / the latter (molar ratio) = 1/2 to It may be about 1/20, preferably 1 / 2.2-1 / 10, more preferably about 1 / 2.3-1 / 5 (for example, 1 / 2.5-1 / 3). When the sulfonating agent is fuming sulfuric acid, the total number of moles of sulfuric acid and sulfur trioxide constituting the fuming sulfuric acid may be the number of moles of the sulfonating agent.

  The use ratio of the solvent is, for example, 100 to 1000 parts by weight, preferably 200 to 900 parts by weight, more preferably 100 parts by weight of the dinaphthothiophene compound (for example, the compound represented by the formula (2)). About 300-800 weight part may be sufficient. If the amount of the solvent is too large, the conversion rate may decrease.

  The reaction temperature may be, for example, 25 to 100 ° C, preferably 35 to 70 ° C, more preferably about 35 to 45 ° C. If the temperature is too high, the conversion rate and yield may decrease due to side reactions.

  The reaction may be performed in air or in an inert gas (for example, nitrogen; a rare gas such as argon or helium). The reaction may be performed under normal pressure, increased pressure, or reduced pressure. After completion of the reaction, the reaction product is separated and purified by conventional separation and purification means such as washing, extraction, concentration, filtration, reprecipitation, centrifugation, crystallization, recrystallization, column chromatography, or a combination of these. May be.

  In the present invention, since the sulfonation reaction is performed in the presence of the specific solvent, a high conversion rate (or reaction rate) and a high selectivity (dinaphthothiophene substitution selectivity to the 5-position and / or 9-position). ) Can generate the compound represented by the formula (1a). Therefore, the production rate (or conversion rate × selectivity) of the compound represented by the formula (1a) is, for example, 20 mol% or more (for example, with respect to the amount of the compound represented by the formula (2)). For example, 30 mol% or more (for example, 35 to 98 mol%), preferably 40 mol% or more (for example, 50 to 95 mol%), and more preferably 60 mol% or more (for example, 70 mol%). (About 90 mol%).

(Compound wherein Y is a (poly) alkoxy group)
Among the novel dinaphthothiophene derivatives of the present invention, in the formula (1), the compound in which Y of the group R ¹ is a (poly) alkoxy group (compound represented by the following formula (1b)) is, for example, the following reaction According to the process formula, it can be produced by reacting the compound represented by the formula (1a) with an esterifying agent (for example, orthoformate triester represented by the following formula (3)) (esterification process). .

[Wherein R ³ represents an alkyl group or a (poly) alkoxyalkyl group, and X, k, R ² , m1 and m2, n1 and n2, p1 and p2 are the same as those in the formula (1), and n1 + p1 and n2 + p2 are each an integer of 0-4].

In the formula (3), the alkyl group or (poly) alkoxyalkyl group represented by the group R ³ is an alkyl group or (poly) alkoxyalkyl group corresponding to the (poly) alkoxy group exemplified in the section of the group Y. It may be the same including a preferable aspect.

Typical orthoformate represented by the formula (3) includes orthoformate corresponding to the group R ³ , such as trimethyl orthoformate, triethyl orthoformate, tri-n-propyl orthoformate, orthoformate. Tri-orthoformate linear or branched C _1-6 alkyl ester such as triisopropyl, tri-n-butyl orthoformate, tri-sec-butyl orthoformate, tri-t-butyl orthoformate; tri (2-ethoxy orthoformate) Ethyl), and orthoformate tri [(poly) C _2-4 alkoxy C _2-4 alkyl ester] such as tri [2- (2-ethoxyethoxy) ethyl] orthoformate. Jo or branched chain C _1-4 alkyl ester, more preferably orthoformic Sainte such trimethyl orthoformate Such as C _1-2 alkyl esters.

  The ratio of 1 mol of the sulfonic acid group of the compound represented by the formula (1a) to the orthoformate triester is, for example, the former / the latter (molar ratio) = 1/1 to 1/100, preferably 1/5. It may be about 1/50, more preferably about 1/10 to 1/30.

  The reaction may be carried out in the presence of a solvent inert to the reaction (for example, ethers, halogenated hydrocarbons, etc.). The use ratio of the solvent is, for example, about 1 to 1000 parts by weight, preferably about 10 to 500 parts by weight, and more preferably about 50 to 100 parts by weight with respect to 100 parts by weight of the compound represented by the formula (1a). May be.

  The reaction temperature may be, for example, about 50 to 200 ° C., preferably about 70 to 150 ° C. (for example, 80 to 110 ° C.). The reaction may be performed while refluxing.

  The reaction may be performed in air or in an inert gas (for example, nitrogen; a rare gas such as argon or helium). The reaction may be performed under normal pressure, increased pressure, or reduced pressure. After completion of the reaction, the reaction product may be separated and purified by the conventional separation and purification means or a method combining these.

(Compound wherein Y is an amino group or a substituted amino group)
Among the novel dinaphthothiophene derivatives of the present invention, in the formula (1), a compound in which Y of the group R ¹ is an amino group or a substituted amino group (a compound represented by the following formula (1d)) is represented by the following reaction step: For example, the compound represented by the formula (1a) can be reacted with a sulfinyl halide (or thionyl halide) represented by the formula SOY ¹ ₂ (wherein Y ¹ represents a halogen atom). And a compound represented by the following formula (1c) (in the formula (1), Y in the group R ¹ is Y ¹ , that is, a sulfonyl halide compound which is a halogen atom) (halogenation step). It can manufacture by making a compound and amines represented by following formula (4) react (amidation process).

[Wherein Y ¹ represents a halogen atom, R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group or an aryl group, respectively, X, k, R ² , m1 and m2, n1 and n2, p1 and p2 represent the above formula ( 1), and n1 + p1 and n2 + p2 are each an integer of 0 to 4].

(Halogenation process)
_{1 2} (in the formula, ^{Y 1} is a halogen atom) wherein ^SOY sulfinyl halide represented by (or the formula (1c)) in, a halogen atom represented by group ^{Y 1} is a fluorine atom, a chlorine atom, a bromine An atom etc. are mentioned, It is preferable that it is a chlorine atom.

Specific sulfinyl halide compound corresponding to the group Y ^1, i.e., fluoride sulfinyl, sulfinyl chloride (or thionyl chloride), etc. bromide sulfinyl and the like, thionyl chloride is preferred.

  The use ratio of the sulfinyl halide is, for example, 1 to 200 mol, preferably 30 to 150 mol, and more preferably about 70 to 110 mol, with respect to 1 mol of the sulfonic acid group of the compound represented by the formula (1a). It may be.

  The reaction may be performed in the presence of a reaction accelerator (dehydrochlorinating agent or reactive intermediate forming agent). Examples of the reaction accelerator include organic compounds such as tertiary amines (for example, trialkylamines such as triethylamine, aromatic tertiary amines such as benzyldimethylamine, and heterocyclic tertiary amines such as pyridine). Examples include bases and amides such as N, N-dimethylformamide (also simply referred to as DMF). These reaction accelerators may be used alone or in combination of two or more. Of these reaction accelerators, amides such as N, N-dimethylformamide are preferred. The reaction promoter may be used in an amount of, for example, 0.01 to 0.5 mol, preferably about 0.1 to 0.3 mol, relative to 1 mol of the compound represented by the formula (1a). Good.

  The reaction may be carried out in the presence of a solvent inert to the reaction (for example, ethers, ketones, nitriles, sulfoxides, halogenated hydrocarbons, etc.). These solvents can be used alone or in combination of two or more. The use ratio of the solvent is, for example, 1 to 1000 parts by weight, preferably 10 to 500 parts by weight, more preferably 100 parts by weight of the dinaphthothiophene compound (for example, the compound represented by the formula (1a)). It may be about 50 to 100 parts by weight.

  The reaction temperature may be, for example, about 60 to 100 ° C., preferably about 65 to 80 ° C. (for example, 70 to 78 ° C.). The reaction may be performed while refluxing.

  The reaction may be performed in air or in an inert gas (for example, nitrogen; a rare gas such as argon or helium). The reaction may be performed under normal pressure, increased pressure, or reduced pressure. After completion of the reaction, the reaction product may be separated and purified by the conventional separation and purification means or a method combining these. In addition, after completion | finish of a halogenation process, you may perform an amidation process, without isolate | separating and purifying a product.

(Amidation process)
In the formula (4), the groups R ⁴ and R ⁵ are each a hydrogen atom, an alkyl group or an aryl group, and the alkyl group and the aryl group are alkyl groups corresponding to the substituted amino group exemplified in the section of the group Y. And aryl groups and preferred embodiments may be the same. Of these groups R ⁴ and R ⁵ , a hydrogen atom, a C _1-2 alkyl group, an alkyl group (for example, a linear or branched C _1-4 alkyl group, preferably a C _1-2 alkyl group). A C _6-10 aryl group which may be substituted with is preferably a hydrogen atom or a C _6-8 aryl group (for example, a tolyl group such as a p-tolyl group). Further, it is preferable that at least one of the groups R ⁴ and R ⁵ is a hydrogen atom. The groups R ⁴ and R ⁵ may be the same or different from each other.

Representative amines represented by the formula (4) include amines corresponding to the groups R ⁴ and R ⁵ , such as ammonia; primary amine (or N-monosubstituted amine) [for example, methylamine, Linear or branched primary C _1-6 alkyl amines such as ethylamine (preferably linear or branched primary C _1-4 alkyl amines, more preferably primary C _1-2 alkyl amines); Alkylphenyl) amine [e.g. toluidine (e.g. p-toluidine etc.), xylidine etc.], aminobiphenyl, naphthylamine etc. primary C _6-12 arylamine (preferably primary C _6-10 arylamine, more preferably primary C _6-8 arylamine), etc.]; secondary amine (or N, N-di-substituted amines) [e.g., dimethylamine Linear or branched secondary C _1-6 alkyl amine (preferably a linear or branched chain secondary C _1-4 alkyl amine, more preferably di-C _1-2 alkyl amines), such as diethylamine; diphenylamine , Di (alkylphenyl) amine [eg, ditolylamine (eg, di-p-tolylamine, etc.)], secondary C _6-12 arylamine (preferably secondary C _6-10 arylamine, etc.), and more preferably _Are secondary C _6-8 arylamines). Among these amines, ammonia, primary _C1-4 alkylamine, secondary _C1-4 alkylamine, and primary _C6-10 arylamine are preferable, and ammonia or toluidine (for example, p-toluidine etc.) is particularly preferable. preferable.

1 mol of the group SO ₂ Y ¹ (or halosulfonyl group, particularly chlorosulfonyl group) of the compound represented by the formula (1c) [or the sulfonic acid group of the compound represented by the formula (1a)], amines, The ratio of the former is, for example, the former / the latter (molar ratio) = 1/1 to 1/200, preferably 1 / 1.1-1 / 100, more preferably 1/1/2 to 1/20. Also good.

  The reaction may be performed in the presence of a reaction accelerator (dehydrochlorinating agent or reactive intermediate forming agent). Examples of the reaction accelerator include the same compounds as those exemplified in the halogenation step. Among these reaction accelerators, for example, organic bases such as tertiary amines (for example, heterocyclic tertiary amines such as pyridine) and amides such as DMF are preferable. The reaction accelerators may be used alone or in combination of two or more. For example, amides such as DMF may be used alone, and the amides and tertiary amines such as pyridine (for example, complex). A cyclic tertiary amine).

The proportion of the reaction accelerator used is the group SO ₂ Y ¹ (or halosulfonyl group, particularly chlorosulfonyl group) of the compound represented by the formula (1c) [or the sulfonic acid group of the compound represented by the formula (1a). ] For example, it may be about 0.01 to 300 mol, preferably about 50 to 250 mol (for example, 90 to 210 mol) with respect to 1 mol.

  The reaction may be carried out in the presence or absence of a solvent inert to the reaction. Specific examples of the solvent include ethers, ketones, nitriles, sulfoxides, halogenated hydrocarbons and the like. Can be mentioned. Moreover, when amines and reaction accelerators (for example, amides, such as DMF), are liquid, you may use these as a solvent. These solvents can be used alone or in combination of two or more. Preferable solvents include amides such as DMF.

  The proportion of the solvent used is, for example, 100 to 5000 parts by weight, preferably 200 to 4000 parts by weight, based on 100 parts by weight of the compound represented by the formula (1c) [or the compound represented by the formula (1a)]. More preferably, it may be about 2000-3500 parts by weight.

  The reaction temperature may be, for example, about 20 to 120 ° C, preferably about 25 to 100 ° C. The reaction may be performed while refluxing.

  The reaction may be performed in air or in an inert gas (for example, nitrogen; a rare gas such as argon or helium). The reaction may be performed under normal pressure or under pressure. After completion of the reaction, the product may be separated and purified by the conventional separation and purification means or a method combining these.

(Compound wherein X is a sulfonyl group)
In the formula (1), the compound in which X is a sulfonyl group, that is, the S, S-dioxide form, oxidizes the corresponding compound in which X is a sulfur atom with a conventional oxidizing agent (for example, hydrogen peroxide). May be prepared. In the present specification and claims, the preparation of the S, S-dioxide body (or oxidation of the dinaphthothiophene skeleton) may be performed at any stage. For example, before the sulfonation step, In the formula (2), a compound in which X is a sulfur atom may be oxidized. In the formula (1), a compound in which X is a sulfur atom (for example, the formula (1a), (1b), (1c) or The compound (such as a compound in which X is a sulfur atom in (1d)) may be prepared and then oxidized.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The evaluation method is shown below.

⁽¹ H NMR and ¹³ C NMR)
Use Bruker (KK) to "Ascend 500" or Bruker (KK) "Avance III HD 400 MHz", dimethylsulfoxide _{-d 6 (DMSO-d} 6) or chloroform -d (CDCl ₃₎ as solvent, as a standard Measurement was performed using tetramethylsilane (TMS).

(Refractive index)
Samples prepared in Examples or Comparative Examples were dissolved in methanol, chloroform, dichloromethane, or tetrahydrofuran (THF), and a film having a thickness of about 100 nm formed by spin coating was used as an evaluation sample, and an ellipsometer (manufactured by Mizojiri Optical Co., Ltd.) Using “DHA-OLX / S6”), the refractive index at a temperature of 25 ° C. and a wavelength of 633 nm was measured.

  Since 5-sulfo-dinaphthothiophene (DNT-5-SA) was difficult to form a film, 6 types of dimethyl sulfoxide (DMSO) solutions having different concentrations in the range of 0 to 28% by weight were prepared. The refractive index of each solution at a temperature of 26 ° C. and a wavelength of 589 nm was measured using an Abbe refractometer (“NAR-3T” manufactured by Atago Co., Ltd.). From the obtained refractive index results, good concentration dependence was recognized, an approximate expression representing a refractive index-concentration relationship (proportional relationship) was calculated, and a value obtained by extrapolating the concentration to 100% by weight was DNT-5. -The refractive index of SA.

(Melting point)
The melting point was measured in accordance with JIS K 4101 (1993) [5.1 Visual method] using a melting point measuring device (“535” manufactured by Büch).

(Solubility)
1 mg of a sample was mixed with a solvent, the solubility at a temperature of 25 ° C. was visually confirmed, and the following criteria were evaluated. Note that water, methanol, acetone, N, N-dimethylformamide (DMF), DMSO, THF, ethyl acetate and chloroform were used as the solvent.

○: Dissolved in less than 0.03 mL of solvent Δ: Dissolved in less than 0.03 to 1 mL of solvent ×: Dissolved in or not dissolved in 1 mL or more of solvent.

Example 1
A 500 mL flask was charged with 50 g (175.8 mmol) of dinaphthothiophene and 350 g of sulfolane and heated to 30 ° C. After the temperature increase, 26.5 g (1.3 molar ratio) of chlorosulfonic acid was added dropwise over 20 minutes. The temperature after dripping is 40-44 degreeC, it was made to react for 14 hours, keeping at the said temperature with a thermostat. After the reaction, the reaction mixture was cooled to 10 ° C. or lower, 50 g of water as a quenching agent and 50 g of methanol for dissolving the product were added, and the temperature was raised to 55 ° C. After the temperature rise, hot filtration was performed, and the residue was washed with 50 g of methanol. When the filtrate was analyzed by high performance (or high performance) liquid chromatography (HPLC), dinaphtho [2,1-b: 1 ′, 2′-d] thiophene-5-disulfonic acid (DNT-5-SA or 5- The production rate of sulfo-dinaphthothiophene) was 81 mol%. The obtained filtrate was heated to 52 ° C., 200 g of water was added, and the filtrate was concentrated until the temperature of the distillation head reached 100 ° C. Thereafter, 600 g of water was added, and the mixture was cooled to 10 ° C. or lower and filtered. The obtained wet crystals were washed with 150 mL of water and dried to obtain 40.7 g of DNT-5-SA as a pale yellow solid (purity by HPLC: 97%, theoretical yield: 61 mol%). The substitution position of the sulfonic acid group was determined by comparing with the spectrum data of the related compound. The refractive index of the obtained compound was 1.720.

¹ H NMR (DMSO-d ₆ , 400 MHz): δ (ppm) 5.61 (brs, 1H), 7.62-7.69 (m, 4H), 8.10 (1H, d, J = 8. 7 Hz), 8.16-8.18 (1 H, m), 8.22 (1 H, d, J = 8.7 Hz), 8.60 (1 H, s), 8.72-8.75 (m, 2H), 9.13-9.15 (m, 1H).

¹³ C NMR (DMSO-d ₆ , 100 MHz): δ (ppm) 119.8, 121.2, 124.7, 125.09, 125.11, 125.2, 125.3, 125.6, 127. 9, 128.0, 125.5, 128.9, 129.1, 129.5, 130.2, 131.3, 131.9, 136.6, 139.1, 143.1.

(Example 2)
A 500 mL flask was charged with 50 g (175.8 mmol) of dinaphthothiophene and 350 g of acetonitrile, and the temperature was raised to 30 ° C. After the temperature increase, 20.5 g (1 molar ratio) of chlorosulfonic acid was added dropwise over 20 minutes. The temperature after dripping is 40-44 degreeC, it was made to react for 3 hours, keeping at the said temperature with a thermostat. After the reaction, the mixture was cooled to 10 ° C. or lower, 50 g of water and 50 g of methanol were added, and the temperature was raised to 55 ° C. After the temperature rise, hot filtration was performed, and the residue was washed with 50 g of methanol. When the filtrate was analyzed by HPLC, the production rate of DNT-5-SA was 30 mol%.

(Example 3)
A 500 mL flask was charged with 50 g (175.8 mmol) of dinaphthothiophene and 175 g of sulfolane, and 55.3 g (2.7 molar ratio) of chlorosulfonic acid was added dropwise over 21 minutes. The temperature after dropping was 40 ° C., and the temperature was kept at the above temperature in a thermostatic bath, and the reaction was performed for 7 hours. After the reaction, the mixture was cooled to 10 ° C. or lower, 145 g of water and 100 g of toluene were added, the temperature was raised to 90 ° C., and hot filtration was performed. When the aqueous layer of the filtrate was analyzed by HPLC, dinaphtho [2,1-b: 1 ′, 2′-d] thiophene-5,9-disulfonic acid (DNT-5,9-SA or 5,9-disulfo- The production rate of dinaphthothiophene) was 81 mol%. DNT-5,9-SA contained in the aqueous layer was purified by salting out and dechlorinated using an ion exchange resin to obtain 1530 g of a DNT-5,9-SA aqueous solution as a yellow liquid (concentration: 3.9 wt%, theoretical yield: 76 mol%). The substitution positions of the two sulfonic acid groups were determined by comparison with two-dimensional NMR (HMQC, HMBC) and spectrum data of related compounds. The refractive index of the obtained compound was 1.641.

¹ H NMR (DMSO-d ₆ , 400 MHz): δ (ppm) 7.61-7.69 (m, 8H), 8.60 (2H, s), 8.71-8.73 (4H, m) , 9.11-9.13 (m, 2H).

¹³ C NMR (DMSO-d ₆ , 100 MHz): δ (ppm) 119.8, 124.9, 125.1, 125.2, 128.0, 125.5, 129.6, 131.1, 137. 4, 143.2.

Example 4
A 500 mL flask was charged with 50 g (175.8 mmol) of dinaphthothiophene and 350 g of sulfolane, and 225.1 g (13.2 molar ratio) of 5% fuming sulfuric acid was added dropwise over 21 minutes. After dropping, the temperature was raised to 100 ° C., the temperature was kept in a constant temperature bath, and the reaction was performed for 2 hours. After the reaction, the mixture was cooled to 10 ° C. or lower, 145 g of water and 100 g of toluene were added, the temperature was raised to 90 ° C., and hot filtration was performed. When the aqueous layer of the filtrate was analyzed by HPLC, the production rate of DNT-5,9-SA was 40 mol%.

(Example 5)
A 500 mL flask was charged with 50 g (175.8 mmol) of dinaphthothiophene and 350 g of acetic acid, and 225.1 g (13.2 molar ratio) of 5% fuming sulfuric acid was added dropwise over 21 minutes. After dropping, the temperature was raised to 100 ° C., kept at the above temperature in a thermostatic bath, and reacted for 3 hours. After the reaction, the mixture was cooled to 10 ° C. or lower, 145 g of water and 100 g of toluene were added, the temperature was raised to 90 ° C., and hot filtration was performed. When the aqueous layer of the filtrate was analyzed by HPLC, the production rate of DNT-5,9-SA was 37 mol%.

(Reference Example 1)
To a 500 mL flask, 50 g (175.8 mmol) of dinaphthothiophene was charged, and 703.9 g (40 mole ratio) of 98% sulfuric acid was added dropwise over 20 minutes, and reacted at 100 ° C. for 3 hours. After the reaction, the mixture was cooled to 10 ° C. or lower, 50 g of water and 50 g of methanol were added, the temperature was raised to 55 ° C., hot filtration was performed, and the residue was washed with 50 g of methanol. When the filtrate was analyzed by HPLC, various sulfonated products and by-products were detected, and among the various sulfonated products, the presence of DNT-5-SA and DNT-5,9-SA was confirmed. Any sulfonated product was too small to be isolated.

(Example 6)
Into a 50 mL flask was charged 0.270 g (0.74 mmol) of DNT-5-SA, 2 ml (18.3 mmol) of trimethyl orthoformate was added, and the mixture was heated to reflux for 3 hours while stirring. After the reaction, excess trimethyl orthoformate was distilled off under reduced pressure, the residue was dissolved in chloroform, and the insoluble part was filtered off. The resulting filtrate was desolvated and dried under reduced pressure to give dinaphtho [2,1-b: 1 ′, 2′-d] thiophene-5-sulfonic acid methyl ester (DNT-5-SAM or 5-methoxysulfonyl- 0.268 g of dinaphthothiophene) was obtained (purity by HPLC: 98.4%, theoretical yield: 94.7 mol%). The obtained compound had a refractive index of 1.705 and a melting point of 203.0 ° C.

¹ H NMR (CDCl ₃ , 500 MHz): δ (ppm) 3.82 (s, 3H), 7.59-7.77 (m, 4H), 7.97-8.08 (m, 3H), 8 .77-8.81 (m, 4H), 8.81 (s, 1H), 8.96 (d, J = 8.3 Hz, 1H).

¹³ C NMR (CDCl ₃ , 125 MHz): δ (ppm) 56.7, 120.7, 125.6, 125.7, 125.9, 126.0, 126.6, 126.7, 127.3, 128.3, 129.0, 129.5, 130.0, 130.3, 130.4, 132.2, 135.2, 136.5, 141.6.

(Example 7)
In a 50 mL flask, 0.500 g (1.1249 mmol) of DNT-5,9-SA was charged, 3 ml (27.4 mmol) of trimethyl orthoformate was added, and the mixture was heated to reflux with stirring for 3 hours. After the reaction, excess trimethyl orthoformate was distilled off under reduced pressure, the residue was dissolved in chloroform, and the insoluble part was filtered off. The obtained filtrate was desolvated and dried under reduced pressure, and dinaphtho [2,1-b: 1 ′, 2′-d] thiophene-5,9-disulfonic acid methyl ester (DNT-5,9-SAM or 5 , 9-bis (methoxysulfonyl) -dinaphthothiophene) was obtained (purity by HPLC: 98.1%, theoretical yield: 93.0 mol%). The obtained compound had a refractive index of 1.730 and a melting point of 259.2 ° C.

¹ H NMR (CDCl ₃ , 500 MHz): δ (ppm) 3.86 (s, 6H), 7.68-7.72 (m, 2H), 7.78-7.82 (m, 2H), 8 .80-8.88 (m, 6H).

¹³ C NMR (CDCl ₃ , 125 MHz): δ (ppm) 57.0, 126.1, 126.3, 126.4, 126.8, 126.9, 128.1, 130.6, 130.9, 135.3, 138.2.

(Example 8)
A 50 mL flask was charged with 0.5 g (1.37 mmol) of DNT-5-SA, 15 g of thionyl chloride (30 times by weight, 92 mol ratio) and 0.2 g of DMF (0.2 mol ratio), respectively, and refluxed (76 ° C.). The temperature was raised until After raising the temperature, the reaction was carried out for 2 hours. After the reaction, the reaction mixture was cooled to 10 ° C. or lower, and thionyl chloride was distilled off under reduced pressure. Then, 5 mL of DMF and 5 mL of aqueous ammonia (30 wt%) were added to the residue, and the mixture was stirred at room temperature for 5 hours. After the reaction, the reaction solution was dropped into 50 mL of water, and the precipitated solid was collected by filtration to give 0.45 g of dinaphtho [2,1-b: 1 ′, 2′-d] thiophene-5-sulfonamide (DNT). 0.45 g of -5-SAm or 5-sulfamoyl-dinaphthothiophene) was obtained as a light brown solid (purity by ¹ H NMR: 94%, theoretical yield 85.0 mol%). The obtained compound had a refractive index of 1.758 and a melting point of 262.7 ° C.

¹ H NMR (DMSO-d ₆ , 500 MHz): δ (ppm) 7.65-7.82 (m, 4H), 7.83 (br, 2H), 8.15-8.22 (m, 2H) 8.27 (d, J = 8.7 Hz, 1H), 8.67-8.71 (m, 1H), 8.82-8.88 (m, 3H).

¹³ C NMR (DMSO-d ₆ , 125 MHz): δ (ppm) 121.7, 122.8, 125.5, 126.1, 126.2, 126.3, 126.4, 126.5, 126. 6, 127.0, 129.4, 129.5, 130.0, 130.1, 132.4, 134.0, 136.2, 138.4, 141.0.

Example 9
A 50 mL flask was charged with 0.61 g (1.37 mmol) of DNT-5,9-SA, 15 g of thionyl chloride (30 times by weight, 92 mol ratio) and 0.2 g of DMF (0.2 mol ratio), respectively, and refluxed (76 Temperature). After raising the temperature, the reaction was carried out for 2 hours. After the reaction, the reaction mixture was cooled to 10 ° C. or lower and thionyl chloride was distilled off under reduced pressure. Then, 20 mL of DMF, 0.36 g (3.39 mmol) of p-toluidine and 0.045 mL (0.56 mmol) of pyridine were added to the residue. Stir at 0 ° C. for 2 hours. After the reaction, the reaction solution is added dropwise to 50 mL of water, and the precipitated solid is collected by filtration, dried, purified by a silica gel column (developing solvent: ethyl acetate), and 0.50 g of N, N′-bis (p-tolyl). Dinaphtho [2,1-b: 1 ′, 2′-d] thiophene-5,9-disulfonamide (DNT-5,9-SAmT or 5,9-bis [N- (p-tolyl) sulfamoyl] -di Naphthothiophene) was obtained as a light brown solid (purity by ¹ H NMR: 99%, theoretical yield: 58.0 mol%). The obtained compound had a refractive index of 1.684 and a melting point of 145.0 ° C.

¹ H NMR (DMSO-d ₆ , 500 MHz): δ (ppm) 2.06 (s, 6H), 6.90-6.97 (m, 8H), 7.67-7.73 (m, 4H) , 7.76-7.84 (m, 4H), 8.15-8.22 (m, 2H), 8.70 (d, J = 8.7 Hz, 2H), 8.93 (d, J = 8.7, 2H), 9.01 (s, 2H), 10.71 (s, 2H).

¹³ C NMR (DMSO-d ₆ , 125 MHz): δ (ppm) 20.1, 119.8, 125.3, 125.9, 126.0, 126.1, 126.3, 127.2, 129. 5, 129.6, 133.2, 133.4, 134.3, 134.5, 138.3.

(Comparative Example 1)
Dinaphthothiophene (DNpTh) was prepared according to the method described in Example 1 of Patent Document 1. The refractive index of the obtained compound was 1.808.

  Table 1 shows the refractive index and solubility evaluation results of the compounds obtained in Examples 1, 3 and 6 to 9 and Comparative Example 1.

  As is clear from the results in Table 1, it can be seen that the novel dinaphthothiophene derivatives of the examples have higher solubility in the solvent than Comparative Example 1. In particular, in Examples 1, 3 and 8-9, although having a highly hydrophobic dinaphthothiophene skeleton, the solubility in aqueous solvents such as water and methanol was improved. Then, the solubility with respect to chloroform improved.

  In addition, the examples have a surprisingly high refractive index despite having a substituent. In particular, Example 8 having a sulfamoyl group in the mono-substituted product and Example 7 having two methoxysulfonyl groups in the 2-substituted product had a relatively high refractive index. In addition, even if Example 7 was a 2 substituted body, compared with Example 6 of 1 substituted body, the refractive index improved unexpectedly.

  In the present invention, since the solubility in a solvent (particularly an aqueous solvent) and a high refractive index can be compatible, the novel dinaphthothiophene derivative is an optical material [for example, an antireflection film (for example, an index matching film) or the like. Display materials, refractive index improvers, etc.]. The novel dinaphthothiophene derivative of the present invention can also be used as a monomer component (a monomer component having a high refractive index) useful for preparing polysulfone, polyethersulfone and the like.

Claims (10)

The compound or its salt represented by following formula (1).

[Wherein, X is a sulfur atom or a sulfonyl group, R ¹ is a group —SO ₂ Y (where Y represents a hydroxyl group, a (poly) alkoxy group, an amino group or a substituted amino group), and k is 0 or 1 , R ² is an alkyl group or an alkoxy group, m1 and m2 are each 0 or 1, n1 and n2 are each an integer of 0 to 4, p1 and p2 are each 0 or 1, numerals 1 to 13 are position numbers, n1 + p1 and n2 + p2 are each an integer of 0-4. ] In Formula (1), Y in each R ¹ is a hydroxyl group, a C _1-4 alkoxy group, an amino group, a (mono or di) C _1-4 alkylamino group or a (mono or di) C _6-12 arylamino, respectively. The compound or a salt thereof according to claim 1, wherein the group, R ² is a C _1-4 alkyl group or a C _1-4 alkoxy group, and n1 and n2 are each an integer of 0-2. In the formula (1), X is a sulfur atom, Y in each R ¹ is a hydroxyl group, a C _1-2 alkoxy group, an amino group, a (mono or di) C _1-2 alkylamino group, or a (mono or di) C. The compound or a salt thereof according to claim 1 or 2, wherein a _6-10 arylamino group, m1 and m2 are each 0, n1 and n2 are each 0, and p1 and p2 are each 0.   The compound or salt thereof according to any one of claims 1 to 3, which is soluble in an aqueous solvent and has a refractive index of 1.63 to 1.77 at a temperature of 25 ° C and a wavelength of 633 nm. The dinaphthothiophene compound and the sulfonating agent are reacted in a solvent containing at least one selected from sulfones, nitriles, and carboxylic acids, and each R ¹ in formula (1) according to claim 1 is reacted. A method for producing a compound or a salt thereof, wherein Y is a hydroxyl group.   The method according to claim 5, wherein the sulfonating agent comprises chlorosulfonic acid and / or fuming sulfuric acid.   The method according to claim 5 or 6, wherein the ratio of the dinaphthothiophene compound and the sulfonating agent is the former / the latter (molar ratio) = 1 / 0.7 to 1/20.   The method according to any one of claims 5 to 7, wherein the sulfones comprise sulfolane. A method for producing a compound in which Y in each R ¹ is a (poly) alkoxy group in the formula (1) by reacting the compound produced by the method according to claim 5 with an esterifying agent. A compound produced by the method according to any one of claims 5 to 8 is reacted with thionyl halide to produce a compound in which Y is a halogen atom in formula (1), and this compound is reacted with an amine. A method for producing a compound in which, in formula (1), Y in each R ¹ is an amino group or a substituted amino group.