JP2011074012A - New aromatic compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new aromatic compound having characteristics such as high heat resistance and high refractive index. <P>SOLUTION: The method for producing the new aromatic compound represented by formula (1) includes reacting a compound represented by formula (2) with a compound represented by formula (3) in the presence of an acid catalyst to synthesize the aromatic compound. In the formulas, ring X is an aromatic ring; ring Y is a ring obtained by removing two oxo groups from the o-quinone of the aromatic ring X; R<SP>1</SP>is a substituent; p is an integer of ≥0; ring Z is an aromatic hydrocarbon ring; R<SP>2</SP>is alkylene; q is an integer of ≥0; r is an integer of ≥1; R<SP>3</SP>is a substituent; and s is an integer of ≥0. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel aromatic compound having a structure in which two specific aromatic ring groups are substituted with an aromatic ring in the ortho position, and a method for producing the same.

  Aromatic polyols (such as diols) have excellent properties such as heat resistance and are therefore used as monomers for various polymers. For example, a diol having a fluorene skeleton such as 9,9-bis (hydroxyphenyl) fluorene has characteristics such as high heat resistance, high refractive index, and low birefringence, and is used as a raw material for optical materials. Useful.

  Thus, development of a novel aromatic polyol is expected for use as a monomer.

  JP-A-2005-326838 (Patent Document 1) discloses a radiation-sensitive resist composition containing a specific polyphenol compound, a specific acid generator, and an acid crosslinking agent. As an example, a compound represented by the following formula is disclosed.

JP 2005-326838 A (claims, paragraph numbers [0269], [0281])

  Accordingly, an object of the present invention is to provide a novel aromatic compound having characteristics such as high heat resistance and a high refractive index, and a method for producing the same.

  Another object of the present invention is to provide a method for efficiently producing such a novel aromatic compound.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have reacted quinones with hydroxyarenes or hydroxy (poly) alkoxyarenes to produce hydroxyarenes or hydroxy (poly) alkoxyarenes. A novel aromatic compound in which two corresponding aromatic ring groups are substituted with an aromatic ring corresponding to the quinones in the ortho-position is obtained, and the resulting aromatic compound (ring assembled aromatic compound) ) Was found to have characteristics such as high heat resistance and high refractive index, and the present invention was completed.

  That is, the novel aromatic compound of the present invention is a compound represented by the following formula (1).

(In the formula, ring X is an aromatic ring, R ¹ is a substituent, p is an integer of 0 or more, ring Z is an aromatic hydrocarbon ring, R ² is an alkylene group, q is an integer of 0 or more, and r is 1 or more. An integer, R ³ represents a substituent, and s represents an integer of 0 or more.)
In the formula (1), X may be a condensed polycyclic aromatic hydrocarbon ring (for example, acenaphthylene, acanthrylene, phenanthrene, etc.). In particular, the compound represented by the formula (1) is Or a compound represented by the following formula (1A) or (1B).

(In the formula, p1 represents an integer of 0 to 3, p2 represents an integer of 0 to 4, and R ¹ , Z, R ² , q, r, R ³ , and s are the same as described above.)
In the formula (1) (including the formulas (1A) and (1B), the same applies hereinafter), typically, the ring Z is a benzene ring or a naphthalene ring, q is 0 to 4, and r is 1. It may be ~ 3.

  The present invention also includes a method for producing the novel aromatic compound. In such a production method, for example, in the presence of an acid catalyst, a compound represented by the following formula (2) and a compound represented by the following formula (3) are reacted to form the compound (formula (1) The compound represented by this may be used.

(In the formula, ring Y represents a ring obtained by removing two oxo groups from o-quinone of the aromatic ring X, and R ¹ , p, Z, R ² , q, r, R ³ , and s are the same as above. .)
In the method, the acid catalyst may be composed of sulfonic acid (particularly haloalkanesulfonic acid). When an acid catalyst is comprised with a sulfonic acid, reaction with the compound represented by the said Formula (2) and the compound represented by the said Formula (3) can be advanced still more efficiently.

  In the method, in addition to the acid catalyst, the reaction may be performed in the presence of thiols. In such a method using thiols in combination, typically, the acid catalyst is composed of a haloalkanesulfonic acid (particularly, fluoroalkanesulfonic acid), and the thiols are composed of an alkyl mercaptan. Good.

  The novel aromatic compound of the present invention has characteristics such as high heat resistance and high refractive index. Such aromatic compounds are applicable to uses such as resin raw materials, antioxidants, and curing agents. For example, since the aromatic compound of the present invention has a plurality of hydroxyl groups, it can be used as a polyol component (for example, a diol component) of a resin (for example, a polyester resin), and the resin has a high heat resistance as described above. And the effect of imparting high refractive index can be expected. In particular, since the compound of the present invention is a high-performance material having a conjugated structure, it can be expected to be used as a material for light-emitting elements such as organic EL elements. Moreover, in the method of this invention, the above novel aromatic compounds can be manufactured efficiently.

[Aromatic compounds]
The novel aromatic compound of the present invention is represented by the following formula (1).

(In the formula, ring X is an aromatic ring, R ¹ is a substituent, p is an integer of 0 or more, ring Z is an aromatic hydrocarbon ring, R ² is an alkylene group, q is an integer of 0 or more, and r is 1 or more. An integer, R ³ represents a substituent, and s represents an integer of 0 or more.)
In the above formula (1), the aromatic ring X may be an aromatic heterocyclic ring (such as phenanthroline), but may usually be an aromatic hydrocarbon (ring). Examples of the aromatic hydrocarbon (ring) include a benzene ring, a condensed polycyclic aromatic hydrocarbon (ring) (for example, indene, naphthalene, indacene, acenaphthylene, fluorene, anthracene, phenanthrene, fluoranthene, acanthrylene, aceto Condensed 2- to 10-ring aromatic hydrocarbons (rings) such as phenanthrylene, pyrene, triphenylene, naphthacene, chrysene, perylene, pentaphene, dibenzophenanthrene, hexaphene, preferably condensed 2- to 6-ring aromatic hydrocarbons, Preferably, condensed 3 or 4-cyclic aromatic hydrocarbons and the like are used.

  Among these, preferred aromatic rings X are condensed polycyclic aromatic hydrocarbons (for example, condensed 2- to 6-ring aromatic hydrocarbons such as acenaphthylene, aceanthrylene, phenanthrene), and particularly acenaphthylene, phenanthrene, and the like. The condensed 3 or 4-cyclic aromatic hydrocarbons are preferred.

Examples of the substituent R ¹ for ring X include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), amino group, carbamoyl group, nitro group, cyano group, sulfonyl group, hydrocarbon group {for example, Alkyl group (C _1-20 alkyl group such as methyl, ethyl, butyl, t-butyl group, pentyl group, etc., preferably C _1-10 alkyl group, more preferably C _1-6 alkyl group, especially C _1-4 alkyl Group), a cycloalkyl group (C _5-10 cycloalkyl group such as cyclopentyl group and cyclohexyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group etc.), aryl group [ Phenyl group, alkylphenyl group (methylphenyl group (or tolyl group, 2-methylphenyl group, 3-methylphenyl group etc.), dimethyl group, Butylphenyl group (xylyl), etc.), _{C 6-14} aryl group such as a naphthyl group, preferably a _{C 6-10} aryl group, more preferably a _{C 6-8} aryl group, an aralkyl group (benzyl group, a phenethyl group C _6-10 aryl-C _1-4 alkyl group, etc.)}, hydroxyl group, mercapto group, alkoxy group (methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, t-butoxy group, etc.) _1-6 alkoxy group, preferably C _1-4 alkoxy group), alkylthio group (for example, C _1-6 alkylthio group such as methylthio group), acyl group [formyl group, alkylcarbonyl group (for example, acetyl, propionyl group) C _1-6 alkyl-carbonyl group such as, aroyl group (for example, benzoyl group, etc.)] A carboxyl group, an alkoxycarbonyl group (for example, a C _1-6 alkoxy-carbonyl group such as a methoxycarbonyl, ethoxycarbonyl, or butoxycarbonyl group), a substituent in which these substituents are bonded to each other [for example, an alkoxyaryl group (for example, C _1-4 alkoxy C _6-10 aryl group such as methoxyphenyl group), alkoxycarbonylaryl group (for example, C _1-4 alkoxy-carbonyl C _6-10 aryl group such as methoxycarbonylphenyl group, ethoxycarbonylphenyl group, etc.) )] And the like. Ring X may have these substituents alone or in combination.

Typical R ¹ includes a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [eg, alkyl group, aryl group (C _6-10 aryl group such as phenyl group), etc.] In particular, a halogen atom, a cyano group, an alkyl group (such as a C _1-4 alkyl group), an alkoxy group (such as a C _1-4 alkoxy group), and an aryl group (such as a C _6-8 aryl group). May be.

The substitution number p of the substituent R ¹ may be an integer of 0 or more, and is, for example, 0 to 8, preferably 0 to 6, and more preferably about 0 to 3, depending on the type of the ring X. In particular, it may be 0.

Examples of the aromatic hydrocarbon ring Z include the aromatic hydrocarbon rings exemplified in the paragraph of the aromatic ring Z. Representative aromatic hydrocarbon rings include benzene rings, condensed polycyclic hydrocarbon rings [for example, condensed bicyclic hydrocarbon rings (for example, C _8-20 condensed bicyclic hydrocarbon rings such as indene, naphthalene, etc., C _10-16 condensed bicyclic hydrocarbon ring), condensed tricyclic hydrocarbon rings (for example, condensed 2 to 4 cyclic hydrocarbon rings such as anthracene, phenanthrene, etc.), etc., and benzene ring or naphthalene A ring (particularly a benzene ring) is preferred. The two rings Z may be the same or different rings, and may usually be the same ring.

  The substitution position of the two rings Z (or the unit containing the ring Z) with respect to the aromatic ring X may be any carbon atom constituting the aromatic ring X and adjacent to each other. For example, (a) Ring X is a naphthalene ring In this case, it may be the 1st, 2nd, 2nd and 3rd positions of the naphthalene ring. (B) When the ring X is an acenaphthylene ring, it may be the 1st and 2nd positions of the acenaphthylene ring. , (C) when ring X is an anthracene ring, it may be the 1- and 2-positions of the anthracene ring, and (d) when ring X is an asanthrylene ring, 1 and 2 positions, etc. (e) When ring X is a phenanthrene ring, it may be positions 9 and 10 of the phenanthrene ring, and (f) When ring X is a chrysene ring Includes chrysene rings 5 and 6 Or the like may be used.

In the formula (1), examples of the alkylene group represented by the group R ² include an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butanediyl group, and a tetramethylene group. A C _2-10 alkylene group (for example, a C _2-6 alkylene group) such as a group, preferably a C _2-4 alkylene group, and more preferably a C _2-3 alkylene group (particularly an ethylene group). When q is 2 or more, the alkylene group may be composed of different alkylene groups, and usually may be composed of the same alkylene group. In the two aromatic hydrocarbon rings Z, the groups R ² may be the same or different, and may usually be the same.

The number (addition molar number) q oxyalkylene groups (OR ²⁾ may be any of 0 or more (e.g., 0-10), for example, 0-8 (e.g., 1-8), preferably 0 to 4 ( For example, it may be 1 to 4), more preferably 0 to 3 (for example, 1 to 3), particularly 0 to 1. q may be the same or different for different rings Z.

In the formula (1), the number of substitutions r for the ring Z of the hydroxyl group or hydroxy (poly) alkoxy group [ie, — (R ² O) q—OH] may be 1 or more. Depending on the type, for example, 1 to 6 (for example, 1 to 4), preferably 1 to 3, more preferably 1 to 2, particularly 1 may be used. In addition, the substitution position of a hydroxyl group or a hydroxy (poly) alkoxy group is not specifically limited, What is necessary is just to substitute to the suitable substitution position of the ring Z. For example, when the ring Z is a benzene ring, the hydroxyl group or the hydroxy (poly) alkoxy group may be substituted at the 2-6 position of the phenyl group (for example, the 3-position, 4-position, etc. of the phenyl group) Preferably it may be substituted at the 4-position. In addition, when the ring Z is a condensed polycyclic hydrocarbon ring, the hydroxyl group or the hydroxy (poly) alkoxy group is a hydrocarbon different from the hydrocarbon ring bonded to the ring X in the condensed polycyclic hydrocarbon ring. In many cases, the ring (for example, the 5-position, 6-position, etc. of the naphthalene ring) is substituted at least.

Examples of the substituent R ³ of the ring Z include the substituents exemplified in the above R ¹ section. Typically, the group R ³ is a hydrocarbon group (eg, alkyl group, aryl group, etc.), alkoxy group, alkylthio group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, substituted amino group, etc. It may be. Preferable R ³ is a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _6-10 aryl] Group), an aralkyl group (for example, a C _6-8 aryl-C _1-2 alkyl group), an alkoxy group (C _1-4 alkoxy group, etc.), and the like. In particular, R ³ is preferably an alkyl group [C _1-4 alkyl group (particularly a methyl group)], an aryl group [eg C _6-10 aryl group (particularly a phenyl group)], or the like.

In the same ring Z, when s is plural (two or more), the groups R ³ may be different from each other or the same. In the two rings Z, the groups R ³ may be the same or different. The preferred substitution number s may be 0 to 8, preferably 0 to 4 (for example, 0 to 3), more preferably 0 to 2. In different rings Z, the number of substitutions s may be the same or different from each other, and may usually be the same.

  Representative compounds represented by the formula (1) include, for example, compounds represented by the following formula (1A) (in the formula (1), X represents an acenaphthylene ring, and 1 and 2 of the acenaphthylene ring). A compound in which ring Z is substituted at the position), a compound represented by the following formula (1B) (in the formula (1), X is a phenanthrene ring, and a compound in which ring Z is substituted at positions 9 and 10 of this phenanthrene ring) ) Etc. are included.

(In the formula, p1 represents an integer of 0 to 3, p2 represents an integer of 0 to 4, and R ¹ , Z, R ² , q, r, R ³ , and s are the same as described above.)
In the above formula, p1 may be preferably 0 to 1, more preferably 0. Two p1 may be the same or different. Further, p2 is preferably 0 to 2, more preferably 0 to 1, particularly 0. Two p2 may be the same or different. In the above formula (1), R ¹ , Z, R ² , q, r, R ³ and s are the same as described above. In the above formula (1A), the substitution position of R ¹ may be any of 3 to 8 positions, preferably 3 or 5 positions, particularly 5 positions. In the formula (1B), the substitution position of R ¹ may be any of 1 to 8 positions, but preferably 2 or 5 positions.

Specific examples of the compound represented by the formula (1A) include 1,2-bis (hydroxyphenyl) acenaphthylene [eg 1,2-bis (4-hydroxyphenyl) acenaphthylene], 1,2- Bis (alkyl-hydroxyphenyl) acenaphthylene [for example, 1,2-bis (4-hydroxy-3-methylphenyl) acenaphthylene, 1,2-bis (4-hydroxy-3,5-dimethylphenyl) acenaphthylene, etc. 2-bis (C _1-10 alkyl-hydroxyphenyl) acenaphthylene, preferably 1,2-bis (C _1-6 alkyl-hydroxyphenyl) acenaphthylene, more preferably 1,2-bis (C _1-4 alkyl-hydroxy) Phenyl) acenaphthylene], 1,2-bis (aryl-hydroxyphenyl) acena Styrene [e.g., 1,2-bis (4-hydroxy-3-phenylphenyl) acenaphthylene such as 1,2-bis _{(C 6-14} aryl - hydroxyphenyl) acenaphthylene, preferably 1,2-bis _{(C 6- 10} aryl-hydroxyphenyl) acenaphthylene, more preferably 1,2-bis (C _6-8 aryl-hydroxyphenyl) acenaphthylene], 1,2-bis (di- or trihydroxyphenyl) acenaphthylene [eg 1,2-bis (3,4-dihydroxyphenyl) acenaphthylene, etc.], 1,2-bis (hydroxynaphthyl) acenaphthylene {eg, 1,2-bis [1- (5-hydroxynaphthyl)] acenaphthylene, 1,2-bis [2- (6-hydroxynaphthyl)] acenaphthylene, etc.} Wherein the ring Z is a benzene ring or a naphthalene ring, s = 0 to 4, q = 0, and r = 1 to 3 (provided that when the ring Z is a benzene ring, s + r ≦ 5); 1,2- Bis (hydroxyalkoxyphenyl) acenaphthylene {eg, 1,2-bis (hydroxyC _2-4 alkoxyphenyl) acenaphthylene such as 1,2-bis [4- (2-hydroxyethoxy) phenyl] acenaphthylene}, 1,2- Bis (alkyl-hydroxyalkoxyphenyl) acenaphthylene {eg, 1,2-bis [4- (2-hydroxyethoxy) -3-methylphenyl] acenaphthylene, 1,2-bis [4- (2-hydroxyethoxy) -3 , 5-dimethylphenyl] acenaphthylene, etc. 1,2-bis (C _1-10 alkyl-hydroxy C _2-4 alkoxy Phenyl) acenaphthylene, preferably 1,2-bis (C _1-6 alkyl-hydroxy C _2-4 alkoxyphenyl) acenaphthylene, more preferably 1,2-bis (C _1-4 alkyl-hydroxy C _2-4 alkoxyphenyl) ) Acenaphthylene}, 1,2-bis (aryl-hydroxyalkoxyphenyl) acenaphthylene {eg, 1,2-bis (C, eg 1,2-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] acenaphthylene) _6-14 alkyl-hydroxy C _2-4 alkoxyphenyl) acenaphthylene, preferably 1,2-bis (C _6-10 aryl-hydroxy C _2-4 alkoxyphenyl) acenaphthylene, more preferably 1,2-bis (C _{6 -8} aryl-hydroxy _C2-4 alkoxypheny Le) acenaphthylene}, 1,2-bis [di or tri (hydroxyalkoxy) phenyl] acenaphthylene {e.g., 1,2-bis [3,4-di (hydroxy _{C 2-4} alkoxy) phenyl)] acenaphthylene, etc.}, 1,2-bis [(hydroxyalkoxy) naphthyl] acenaphthylene {eg, 1,2-bis {1- [5- (2-hydroxyethoxy) naphthyl]} acenaphthylene, 1,2-bis {2- [6- ( 2-hydroxyethoxy) naphthyl]} 1,2-bis [(hydroxyC _2-4 alkoxy) naphthyl] acenaphthylene} such as acenaphthylene}, wherein the ring Z is a benzene ring or a naphthalene ring, s = 0 -4, q is 1 or more (for example, 1-4), r = 1-3 (however, when ring Z is a benzene ring, s + r≤5) Etc. a compound.

Specific examples of the compound represented by the formula (1B) include 9,10-bis (hydroxyphenyl) phenanthrene [eg, 9,10-bis (4-hydroxyphenyl) phenanthrene], 9, 10-bis (alkyl-hydroxyphenyl) phenanthrene [for example, 9,10-bis (4-hydroxy-3-methylphenyl) phenanthrene, 9,10-bis (4-hydroxy-3,5-dimethylphenyl) phenanthrene, etc. 9,10-bis (C _1-10 alkyl-hydroxyphenyl) phenanthrene, preferably 9,10-bis (C _1-6 alkyl-hydroxyphenyl) phenanthrene, more preferably 9,10-bis (C _1-4 alkyl) -Hydroxyphenyl) phenanthrene], 9,10-bis (aryl-hi Rokishifeniru) phenanthrene [e.g., 9,10-bis (4-hydroxy-3-phenyl-phenyl) phenanthrene 9,10-bis _{(C 6-14} aryl - hydroxyphenyl) phenanthrene, preferably 9,10-bis ( C _6-10 aryl-hydroxyphenyl) phenanthrene, more preferably 9,10-bis (C _6-8 aryl-hydroxyphenyl) phenanthrene], 9,10-bis (di or trihydroxyphenyl) phenanthrene [eg, 9, 10-bis (3,4-dihydroxyphenyl) phenanthrene, etc.], 9,10-bis (hydroxynaphthyl) phenanthrene {eg, 9,10-bis [1- (5-hydroxynaphthyl)] phenanthrene, 9,10-bis [2- (6-Hydroxynaphthyl In the formula (1B) such as phenanthrene}, ring Z is a benzene ring or naphthalene ring, s = 0 to 4, q = 0, r = 1 to 3 (provided that when ring Z is a benzene ring, s + r ≦ 5), compound; 9,10-bis (hydroxyalkoxy phenyl) phenanthrene {e.g., 9,10-bis [4- (2-hydroxyethoxy) phenyl] phenanthrene such as 9,10-bis (hydroxy _{C 2 4-} alkoxyphenyl) phenanthrene}, 9,10-bis (alkyl-hydroxyalkoxyphenyl) phenanthrene {eg, 9,10-bis [4- (2-hydroxyethoxy) -3-methylphenyl] phenanthrene, 9,10-bis 9,10 such as [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] phenanthrene Bis _{(C 1-10} alkyl - hydroxy _{C 2-4} alkoxyphenyl) phenanthrene, preferably 9,10-bis _{(C 1-6} alkyl - hydroxy _{C 2-4} alkoxyphenyl) phenanthrene, more preferably 9,10-bis (C _1-4 alkyl-hydroxy C _2-4 alkoxyphenyl) phenanthrene}, 9,10-bis (aryl-hydroxyalkoxyphenyl) phenanthrene {eg, 9,10-bis [4- (2-hydroxyethoxy) -3 9,10-bis (C _6-14 alkyl-hydroxy C _2-4 alkoxyphenyl) phenanthrene, such as -phenylphenyl] phenanthrene, preferably 9,10-bis (C _6-10 aryl-hydroxy C _2-4 alkoxyphenyl) ) Phenanthrene, more preferred 9,10-bis _{(C 6-8} aryl - hydroxy _{C 2-4} alkoxyphenyl) phenanthrene}, 9,10-bis [di or tri (hydroxyalkoxy) phenyl] phenanthrene {e.g., 9,10-bis [3, 4-di (hydroxy _{C 2-4} alkoxy) phenyl)] phenanthrene, etc.}, 9,10-bis [(hydroxyalkoxy) naphthyl] phenanthrene {e.g., 9,10-bis {1- [5- (2-hydroxyethoxy ) Naphthyl]} phenanthrene, 9,10-bis {2- [6- (2-hydroxyethoxy) naphthyl]} phenanthrene and the like, such as 9,10-bis [(hydroxyC _2-4 alkoxy) naphthyl] phenanthrene} and the like. In the formula (1B), the ring Z is a benzene ring or a naphthalene ring, s = 0 to 4, and q is 1 or more. (E.g., 1 to 4), r = 1 to 3 (provided that when ring Z is a benzene ring, s + r ≦ 5), and the like compounds wherein.

[Production method]
Although it does not specifically limit as a manufacturing method of the novel aromatic compound of this invention, Usually, the compound (o-quinone compound) represented by following formula (2), and the compound represented by following formula (3) Can be made to react.

(In the formula, ring Y represents a ring obtained by removing two oxo groups from o-quinone of the aromatic ring X, and R ¹ , p, Z, R ² , q, r, R ³ , and s are the same as above. .)
In the above formula (2), ring Y is a ring obtained by removing two oxo groups (dione skeleton, ═O) from o-quinone of aromatic ring X (ring corresponding to o-quinone of aromatic ring X). is there. Examples of the compound represented by the formula (2) (o-quinone compound) include o-quinone of the aromatic ring X described in the section of the compound represented by the formula (1) [for example, o-benzoquinone. O-quinones of condensed polycyclic aromatic hydrocarbons (for example, o-naphthoquinone, acenaphthenequinone, o-aceanthrenequinone (1,2-aceanthrenequinone, etc.), o-phenanthrenequinone (9,10-phenanthrene) O-quinones of condensed 2- to 10-ring aromatic hydrocarbons such as quinone, etc., preferably o-quinones of condensed 2- to 6-ring aromatic hydrocarbons, more preferably condensed 3- or 4-ring aromatic hydrocarbons O-quinone compounds such as 5-bromoacenaphthenequinone and the like corresponding to these o-quinones and having a p of 1 or more. It is below.

  In addition, when manufacturing the compound represented by the said Formula (1A), as a compound represented by the said Formula (2), the compound (acenaphthenequinone compound) represented by the following formula (2A), the said formula When producing the compound represented by (1B), a compound represented by the following formula (2B) (9,10-phenanthrenequinone compound) may be used.

(In the formula, R ¹ , p ¹ and p 2 are the same as above.)
The purity of the o-quinone compound to be used is not particularly limited, but may be usually 95% by weight or more, preferably 99% by weight or more.

The compound represented by the formula (3) (the aromatic hydrocarbon compound having a hydroxyl group) corresponds to the aromatic hydrocarbon ring having a hydroxyl group in the formula (1). That is, in the formula (3), the ring Z corresponds to the ring Z in the formula (1), and examples thereof include the aromatic hydrocarbon rings exemplified above (for example, a benzene ring and a naphthalene ring). In the formula (3), R ² , R ³ , q, r and s are the same as those described above, and preferred embodiments are also the same.

  The compounds represented by the formula (3) can be broadly classified into (i) compounds in which q is 0 and (ii) compounds in which q is 1 or more.

(I) Compound in which q is 0 As a typical compound in which q is 0 in the formula (3), a compound in which ring Z is a benzene ring and a compound in which ring Z is a naphthalene ring are exemplified.

Examples of the compound in which ring Z is a benzene ring include phenols {for example, phenol, phenol having a substituent [for example, alkylphenol (for example, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2 , 5-dimethylphenol, mono- or di-C _1-4 alkyl-phenols such as 2,6-dimethylphenol), cycloalkylphenols (eg C _5-8 cycloalkyl-phenols such as 2-cyclohexylphenol), arylphenols (For example, C _6-10 aryl-phenol such as o-phenylphenol), alkoxyphenol (such as C _1-4 alkoxy-phenol such as o-methoxyphenol), etc.], polyhydroxybenzenes {for example, dihydroxybenzene (carbon Dihydroxybenzenes such as techol, resorcinol, hydroquinone), alkyl-dihydroxybenzene [mono- or di-C _1-4 alkyl-dihydroxybenzene such as dihydroxytoluene, dihydroxyxylene, etc.]; trihydroxybenzene (hydroxyhydroquinone, phloroglucinol, etc.) Di- or trihydroxybenzenes such as trihydroxybenzenes} and the like.

In addition, examples of the compound in which the ring Z is a naphthalene ring include naphthols {that is, a compound in which the ring Z in the formula (3) is a naphthalene ring and r is 1, such as naphthol (1-naphthol, 2-naphthol), substituted Naphthol having a group [for example, alkyl naphthol such as methyl naphthol, ethyl naphthol and dimethyl naphthol (for example, C _1-4 alkyl naphthol)], alkoxy naphthol (for example, C _1-4 alkoxy naphthol such as ethoxy naphthol), etc. }, Polyhydroxynaphthalenes corresponding to these naphthols (or monohydroxynaphthalenes) (that is, compounds in which ring Z is a naphthalene ring and r is 2 or more in formula (3), for example, 1,3-dihydroxynaphthalene 1,4-dihydroxynaphthalene 2,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,2,4-tri And di- or trihydroxynaphthalenes such as hydroxynaphthalene and 1,3,8-trihydroxynaphthalene).

(Ii) Compound in which q is 1 or more Representative compounds in which q is 1 or more in the formula (3) include alkylene glycol monophenyl ethers [for example, alkylene glycol monophenyl ether (for example, 2-phenoxyethanol ( Ethylene glycol monophenyl ether), propylene glycol monophenyl ether, _C2-4 alkylene glycol monophenyl ether such as tetraethylene glycol monophenyl ether), alkylene glycol monoalkyl phenyl ether (for example, 2- (2-methylphenoxy) ethanol) , C _2-4 alkylene glycol mono (mono or di C _1-4 alkylphenyl) ether) such as 2- (2,6-dimethylphenoxy) ethanol, alkylene glycol mono (ali Ether phenyl) ether (for example, C _2-4 alkylene glycol mono (mono or di C _6-10 arylphenyl) ether such as ethylene glycol monobiphenylyl ether (such as ethylene glycol mono (2-biphenylyl) ether)), alkylene glycol mono C _2-4 alkylene glycol mono (mono or di C _1-4 alkyl-mono or di C _6-10 aryl such as (alkyl-arylphenyl) ether (eg ethylene glycol mono (3-methyl-2-biphenylyl) ether) -Phenyl) ether) etc.] in the above formula (3); q and r are both 1; dialkylene glycol monophenyl ethers [eg dialkylene glycol monophenyl ether (eg diethyl) Glycol monophenyl ether, alcohols q such dipropylene glycol di C _2-4 alkylene glycol monophenyl ether, such as monophenyl ether), etc.] is 1, r is 2 or more; response to these, q is 3 Corresponding to these alcohols in which ring Z is a naphthalene ring (for example, alkylene glycol mononaphthyl ethers such as 1- (2-hydroxyethoxy) naphthalene and 2- (2-hydroxyethoxy) naphthalene) Etc.).

  These compounds represented by the formula (3) may be used alone or in combination of two or more.

  The purity of the compound represented by the formula (3) used as a raw material (for example, phenols, naphthols, alkylene glycol monophenyl ethers, etc.) is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight or more.

  In the reaction, the ratio (use ratio) of the compound represented by the formula (3) is about 2 to 100 mol (for example, 2 to 80 mol) with respect to 1 mol of the compound represented by the formula (2). For example, 2 to 50 mol (for example, 2.1 to 40 mol), preferably 2 to 30 mol (for example, 2.2 to 25 mol), more preferably 2 to 20 mol (for example, 2.3 to 15 mol), in particular, about 2 to 12 mol (for example, 2.5 to 10 mol), and usually 3 to 30 mol (for example, 4 to 25 mol, preferably 5 to 20 mol). It may be a degree.

The reaction between the compound represented by the formula (2) and the compound represented by the formula (3) is not particularly limited, but can usually be performed in the presence of an acid catalyst. Examples of the acid catalyst include inorganic acids {for example, sulfuric acid, hydrogen halide (hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.), hydrohalic acid [for example, hydrochloric acid (for example, 5-36% by weight, preferably 20- About 36% by weight of an aqueous solution of hydrogen chloride, etc.), hydrobromic acid, hydroiodic acid, etc.], phosphoric acid, etc.}, organic acid {eg, carboxylic acid, sulfonic acid [eg, alkanesulfonic acid (eg, methanesulfone, etc.) C _1-4 alkane sulfonic acid such as acid), arene sulfonic acid (eg C _6-10 arene sulfonic acid such as benzene sulfonic acid, toluene sulfonic acid (p-toluene sulfonic acid etc.)), haloalkane sulfonic acid (eg And halo C _1-4 alkanesulfonic acid such as trifluoromethanesulfonic acid)] and the like]. The sulfuric acid includes dilute sulfuric acid (for example, sulfuric acid having a concentration of about 30 to 90% by weight), concentrated sulfuric acid (for example, sulfuric acid having a concentration of 90% by weight or more), fuming sulfuric acid, and the like, and can be converted into sulfuric acid in the reaction system. If present, sulfur trioxide may be used as the sulfuric acid precursor. Usually, as sulfuric acid, 80 to 99% by weight (for example, 85 to 98% by weight), preferably about 90 to 97.5% by weight sulfuric acid (concentrated sulfuric acid) may be used in terms of H ₂ SO ₄ .

Moreover, a solid acid can also be used as an acid catalyst. Examples of the solid acid include inorganic solid acids [metal compounds (SiO ₂ , Al ₂ O ₃ , TiO ₂ , Fe ₂ O ₃ , ZrO ₂ , SnO ₂ , V ₂ O ₅ and other oxides, SiO ₂ —Al ₂ O _3]. , SiO ₂ —TiO ₂ , TiO ₂ —ZrO ₂ , SiO ₂ —ZrO ₂ and other complex oxides, sulfides such as ZnS, CaSO ₄ , Fe ₂ (SO ₄ ) ₃ , CuSO ₄ , NiSO ₄ , Al ₂ ( SO ₄ ) ₃ , MnSO ₄ , BaSO ₄ , CoSO ₄ , ZnSO ₄ and other sulfates, P, Mo, V, W, Si and other polyacids (AlPO ₄ , Ti phosphates, etc.) salt, etc.), _etc.); clay minerals (acid clay, montmorillonite, etc.);; _{(NH 4)} 2 SO ₄ nonmetal sulfates such as zeolite (Y-type having an acidic OH group, X type, a type, ZSM , _Mordenite, VIPI _5, AlPO 4 _-5, including AlPO ₄ -11); kaolin, etc.], can be exemplified an organic solid acid (such as ion-exchange resins). The solid acid may be porous or non-porous depending on the type of solid acid.

The ion exchange resin mainly includes strong acid cation exchange resin [for example, ion exchange resin having sulfonic acid group [sulfonated product of crosslinked polystyrene such as styrene-divinylbenzene copolymer, sulfonic acid group (or —CF ₂ CF _2]. A fluorine-containing resin having a SO ₃ H group (for example, a block copolymer of [2- (2-sulfotetrafluoroethoxy) hexafluoropropoxy] trifluoroethylene and tetrafluoroethylene (Nafion manufactured by DuPont), etc. Fluorine-containing ion exchange resins, etc.], weak acid cation exchange resins [for example, ion exchange resins having a carboxylic acid group (methacrylic acid-divinylbenzene copolymer, etc.), etc.] ), Etc. In addition, heat resistance with bromine introduced into the molecule Can also be used in the ion exchange resin. Among these solid acid cation exchange resin is preferred.

The ion exchange resin may be a gel type ion exchange resin, but usually, from the viewpoint of catalytic activity, a porous ion exchange resin [in addition to micropores, macropores (for example, pores having a pore diameter of about 50 to 1000 mm) are used. Having an ion exchange resin]. Among porous ion exchange resins, for example, an ion exchange resin based on a styrene-divinylbenzene copolymer having a high divinylbenzene ratio (crosslinking degree) is called a high porous resin. The porosity of the porous ion exchange resin is usually about 0.03 to 0.6 cm ³ / g, for example, 0.05 to 0.55 cm ³ / g, preferably 0.1 to 0.5 cm ³ / g. g, more preferably about 0.15 to 0.45 cm ³ / g (particularly 0.2 to 0.4 cm ³ / g). The nitrogen adsorption specific surface area of the ion exchange resin is usually about 10 to 90 m ² / g, for example, 15 to 80 m ² / g, preferably 20 to 70 m ² / g, more preferably 25 to 60 m ² / g ( In particular, it may be about 30 to 50 m ² / g). Commercially available ion exchanges such as “Levacit K2649” manufactured by Bayer; “Amberlist 31”, “Amberlist 131”, “Amberlist 121” manufactured by Organo; “Nafion” manufactured by DuPont, etc. A resin may be used.

  There is no restriction | limiting in particular in the form of a solid acid, Although a film form may be sufficient, Usually, it is granular and fine particle may be sufficient.

Preferred acid catalysts include hydrohalic acid (such as hydrochloric acid), sulfuric acid, and sulfonic acid, although depending on the type of compound represented by the formula (3). Particularly preferred acid catalysts are sulfonic acids such as haloalkane sulfonic acids (eg, halo C _1-4 alkane sulfonic acids such as trifluoromethane sulfonic acid, especially fluoro C _1-4 alkane sulfonic acids). As described later, the compound represented by the formula (1) may be produced by a stepwise reaction through a precursor (compound (4) described later), but sulfonic acid (particularly, haloalkanesulfonic acid). Can be used to obtain the compound represented by the above formula (1) as a product even in a one-step reaction (or even in a stepwise reaction via a precursor). Therefore, the acid catalyst may be composed of at least haloalkanesulfonic acid.

  In general, the compound represented by the formula (3) is a compound in which q = 0 (that is, a compound having a phenolic hydroxyl group) and a compound in which q is 1 or more (that is, having an alcoholic hydroxyl group). In many cases, the reactivity of the compound) with the compound represented by the formula (2) is greatly different. For example, a compound in which q = 0 in the formula (3) (for example, phenol, cresol, naphthol, etc.) can be obtained from the compound represented by the formula (2) even if sulfuric acid or hydrochloric acid is used as an acid catalyst. The reaction proceeds. On the other hand, a compound in which q is 1 or more in the formula (3) (for example, phenoxyethanol) does not proceed at all with the compound represented by the formula (2) when sulfuric acid or hydrochloric acid is used as an acid catalyst. However, even if it proceeds, the reactivity is significantly lowered. However, when sulfonic acid or the like is used as the acid catalyst, the reaction with the compound represented by the formula (2) often proceeds efficiently.

  For this reason, among the compounds represented by the formula (3), particularly when a compound having q of 1 or more is used, the acid catalyst is a sulfonic acid (for example, alkane sulfonic acid such as methanesulfonic acid, trifluoro It may be composed of haloalkanesulfonic acid such as romethanesulfonic acid). The reason why the catalytic activity is improved by the use of sulfonic acid is not clear, but it is considered that the high solubility of the compound represented by the formula (3) in sulfonic acid is also affected.

  The acid catalysts may be used alone or in combination of two or more.

  Although the usage-amount of an acid catalyst (for example, the said inorganic acid or the said organic acid) can be selected according to the kind of acid catalyst, for example with respect to 100 weight part of compounds represented by the said Formula (2), 0. It may be about 001 to 150 parts by weight, preferably 0.01 to 100 parts by weight, and more preferably about 0.5 to 25 parts by weight. Moreover, the usage-amount of an acid catalyst is 0.1-200 mol (for example, 0.5-150 mol) with respect to 1 mol of compounds represented by the said Formula (2), Preferably it is 1-120 mol (for example, 2 to 100 mol), more preferably 3 to 100 mol (for example, 4 to 80 mol), particularly about 5 to 70 mol (for example, 8 to 50 mol), and usually 5 to 100 mol (for example, 10 to 80 mol, preferably 15 to 60 mol). The reason why the production of the compound represented by the formula (1) is advantageous by using a relatively large amount of an acid catalyst (such as sulfonic acid) as described above is not clear, but with a large amount of acid catalyst, It is also considered that the dehydration from the reaction system of water produced as a by-product in the process of producing the compound represented by the formula (1) easily proceeds. In addition, when using the compound whose q is 1 or more in the said Formula (2), the ratio of an acid catalyst (sulfonic acid etc.) is comparatively much with respect to 1 mol of compounds represented by the said Formula (2). Ratio [e.g. 1 to 200 mol, preferably 2 to 150 mol, more preferably 3 to 120 mol (e.g. 4 to 100 mol), in particular 5 to 80 mol (e.g. 8 to 60 mol), usually 5 to 100 Mol (for example, 10 to 80 mol, preferably 15 to 60 mol)].

  In general, the reaction may be carried out in combination with a thiol as a co-catalyst in addition to the acid catalyst. When the acid catalyst and thiols are combined, the reaction can proceed effectively. In addition, by such a combination, a high-purity product with a low residual sulfur content can be obtained in a high yield simply and efficiently. Therefore, these combinations enable industrial production of the compound of the present invention at low cost.

Examples of thiols include conventional thiols that function as promoters, such as mercaptocarboxylic acids (thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid. Etc.), alkyl mercaptans (for example, C _1-20 alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, dodecyl mercaptan, preferably C _1-16 alkyl mercaptan), aralkyl mercaptans ( Benzyl mercaptan etc.). Among these thiols, mercapto C _2-6 carboxylic acid (for example, β-mercaptopropionic acid) and alkyl mercaptan (for example, C _1-16 alkyl mercaptan) are preferable, and in particular, alkyl mercaptan having 4 or more carbon atoms (for example, And alkyl mercaptans such as C _6-20 alkyl mercaptans such as dodecanethiol, preferably C _8-18 alkyl mercaptans, and more preferably C _10-16 alkyl mercaptans. Thiols can be used alone or in combination of two or more.

  When using thiols, the usage-amount of thiols can be selected from the range of about 0.1-1 weight part with respect to 1 weight part of compounds represented by said Formula (2), for example, 0.005 It may be about -0.8 parts by weight, preferably 0.01-0.7 parts by weight, more preferably about 0.05-0.5 parts by weight. Moreover, the usage-amount of thiols is 0.1-100 mol with respect to 100 mol of compounds represented by said Formula (2), Preferably it is 0.5-70 mol, More preferably, it is 1-60 mol. About (for example, 1.5-50 mol) may be sufficient.

  Moreover, the usage-amount of thiols can be selected from the range of about 0.01-50 weight part with respect to 1 weight part of acid catalysts, for example, 0.015-40 weight part, Preferably it is 0.02-30 weight part. Part, more preferably about 0.03 to 20 parts by weight. Furthermore, the usage-amount of thiols can be selected from the range of about 0.001-20 mol with respect to 100 mol of acid catalysts, for example, 0.05-15 mol, Preferably it is 0.1-10 mol, More preferably May be about 0.2 to 8 mol, particularly about 0.3 to 5 mol (for example, 0.4 to 3 mol).

  The reaction may be performed in the absence of a solvent or in a solvent. In the present invention, the reaction between the compound represented by the formula (2) and the compound represented by the formula (3) can be efficiently performed without using a solvent (or substantially without using a solvent). Can be advanced. When a solvent is used as necessary, the solvent is non-reactive with the acid catalyst and can dissolve the compound represented by the formula (2) and the compound represented by the formula (3). If it is, it will not specifically limit, It can use in the wide range. Typical organic solvents include ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane), halogenated solvents (halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride). Etc.), aromatic solvents (aromatic hydrocarbons such as benzene, toluene and xylene, anisole and the like). The solvents may be used alone or in combination of two or more.

  The usage-amount of a solvent can be selected from the range of about 0.1-25 weight part with respect to 1 weight part of compounds represented by said Formula (2), for example, 1-15 weight part, Preferably it is 3-10. It may be about parts by weight.

  The reaction temperature can be selected according to the type of the compound represented by the formula (2) to be used, the compound represented by the formula (3), the acid catalyst, the thiols, and the like. Preferably, it is often performed at about 20 to 120 ° C. The reaction time can be adjusted according to the type of raw material, the reaction temperature, the concentration in the solvent, etc., for example, 30 minutes to 48 hours, preferably 1 to 36 hours, more preferably about 2 to 24 hours. Also good.

  The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed at normal pressure or under pressure. The progress of the reaction can be confirmed (or traced) by high performance liquid chromatography (HPLC), thin layer chromatography (TLC), or the like.

  The compound represented by the formula (1) can be obtained by the steps as described above, but the precursor of the compound represented by the formula (1) (depending on the catalyst used, reaction conditions, etc.) A compound represented by the following formula (4) may be produced. When such a precursor (or intermediate) is produced, (a) the reaction may be continued as it is to produce the compound represented by the formula (1) as a final product, (b) The compound represented by the formula (1) may be generated from the isolated precursor. In the method (a), if necessary, the reaction may be continued while dehydrating the reaction system by a conventional method (for example, azeotropic dehydration using a solvent). The reason why the precursor is generated is not clear, but water generated by the reaction between the compound represented by the formula (2) and the compound represented by the formula (3) is converted from the precursor into the formula. It is considered that one of the causes is to reduce the reaction rate and reaction activity of the reaction step to the compound represented by (1).

(Wherein, X, R ¹ , p, Z, R ² , q, r, R ³ , and s are the same as described above.)
In addition, when obtaining the compound represented by said Formula (1A) as a compound represented by said Formula (1), the compound represented by following formula (4A) is represented by said Formula (1B). In the case of obtaining a compound, a compound represented by the following formula (4B) is obtained as a precursor.

(In the formula, R ¹ , p ¹ , p 2, Z, R ² , q, r, R ³ , and s are the same as above.)
In the above method (b), isolation (purification) of the precursor (compound represented by the formula (4)) from the reaction mixture can be performed by a conventional method such as filtration, concentration, extraction, crystallization, recrystallization, and the like. Separation means such as crystals and column chromatography, or a separation means combining them can be used.

  In the method (b), as a method for producing the compound represented by the formula (1) from the isolated precursor, (b1) the precursor is treated with an acid catalyst (the precursor and the acid catalyst are mixed). And (b2) a method of treating a precursor with a reducing agent, and the like. A typical method is a method (b1) of treating with an acid catalyst. Examples of the acid catalyst include the acid catalysts exemplified above, and preferred acid catalysts are the same as described above. The amount of the acid catalyst used can also be selected from the same range as above (that is, if the compound represented by the formula (4) is used in a predetermined ratio instead of the compound represented by the formula (2). Good, the same applies below).

  Moreover, if necessary, thiols may be used in combination with the acid catalyst in the same manner as described above, and preferred thiols and ratios of thiols can be selected from the same range as described above.

  Furthermore, you may use the compound represented by said Formula (3) with an acid catalyst (and thiols) as needed. As the compound represented by the formula (3), it is preferable to use the same compound as the compound used for the precursor, and the ratio thereof can be selected from the same range as described above.

  The treatment temperature (reaction temperature) and the treatment time (reaction time) can also be selected from the same ranges as described above. Further, the treatment (reaction) with the acid catalyst may be performed while stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), and may be performed under normal pressure or under pressure.

  In addition, in the reaction mixture after completion | finish of reaction, in addition to the compound represented by the said Formula (1) produced | generated normally, the compound represented by the said unreacted said Formula (2), the said unreacted Formula (3) The compound represented by these, a catalyst (acid catalyst, thiols), a side reaction product, etc. are contained. Therefore, it can be separated and purified by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.

Examples of the crystallization solvent include hydrocarbons [aliphatic hydrocarbons (hexane, heptane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, etc. ), Etc.], water, alcohols [lower aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol ( _C1-3 alkanols, etc.)], ketones [acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, ethylpropyl Examples include ketones, lower aliphatic ketones (such as C _3-7 dialkyl ketones) such as di-n-propyl ketone and diisopropyl ketone, cyclohexanones, etc., ethers (such as dialkyl ethers such as diethyl ether and diisopropyl ether), and the like. The crystallization solvents may be used alone or in combination of two or more.

  The amount of the crystallization solvent used is not particularly limited, and is 0.5 to 50 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 1 part by weight of the reaction mixture (solid content conversion). It may be about a part. Such a crystallization operation may be performed once or may be repeated a plurality of times.

As described above, the compound represented by the formula (1) can be obtained. In addition, in the said Formula (1), in order to make it react efficiently, the compound whose q is 1 or more is preferable to manufacture by the said method, However, q is represented as the compound represented by the said Formula (3). A compound in which q is 0 in the formula (1) is generated using a compound in which the compound is 0, and then the compound (a compound in which q is 0 in the formula (1)) and an alkylene group R ² ( Alternatively, it can also be produced by reacting a compound corresponding to the oxyalkylene group OR ² ).

Examples of the compound corresponding to the alkylene group R ⁴ include alkylene oxide (C _2-4 alkylene oxide such as ethylene oxide, propylene oxide and butylene oxide, particularly C _2-3 alkylene oxide) and alkylene carbonate (ethylene carbonate, propylene carbonate and butylene). _{C 2-4} alkylene carbonates such as carbonates, such as especially _{C 2-3} alkylene carbonate), halo alkanol (e.g., 3-reaction with a halo _{C 2-6} alkanol, etc.), such as chloropropanol (or addition) products such as Is mentioned. These compounds may be used alone or in combination of two or more. When alkylene oxide or alkylene carbonate is reacted, a (poly) oxyalkylene unit can be introduced through the hydroxyl group of the compound represented by the formula (1) (a compound in which q is 0). When using an alkylene carbonate, an oxyalkylene unit (alkoxy unit) is introduced by decarboxylation after the addition of the alkylene carbonate.

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

  In the examples, the properties of the compounds were measured by the following methods.

(1) Thermogravimetric analysis Thermogravimetric analysis was performed at a heating rate of 10 ° C / min in a nitrogen atmosphere (flow rate 20 ml / min) using "EXSTAR TG / DTA 6200" manufactured by SII Nano Technology. The thermal decomposition temperature (Td (5%)) at which the weight decreases by 5% was measured.

Example 1
A three-necked flask equipped with a condenser tube connected with a three-way cock with a balloon inflated with nitrogen was added to a stirrer, acenaphthalenequinone 1.81 g (9.94 mmol), phenol 3.85 g (40.9 mmol), 1 -Dodecanethiol 0.04g (0.20mmol) was added, nitrogen substitution was carried out, and it heated to 75 degreeC. 2 ml of methanesulfonic acid was added and stirred at 75 ° C. for 4 hours. After cooling, ethyl acetate and distilled water were added for extraction, and the organic layer was washed with saturated brine, dried over sodium sulfate, the desiccant was filtered, and concentrated with an evaporator. After purification by silica gel chromatography (ethyl acetate: toluene = 1: 4), toluene was added, and the crystals were filtered and dried to obtain 1.73 g of pale yellow crystals (yield 49%).

The chemical formula, ¹ H-NMR, and ¹³ C-NMR spectrum data of the product 2,2-bis (4-hydroxyphenyl) acenaphthen-1 (2H) -one are shown below.

¹ H-NMR (CDCl ₃ ) ppm; 6.65 (d, 4H), 6.92 (d, 4H), 7.48 (d, 1H), 7.72 (t, 1H), 7.86 ( t, 1H), 7.97 (d, 1H), 8.02 (d, 1H), 8.32 (d, 1H), 9.40 (d, 2H)
¹³ C-NMR (CDCl ₃ ) ppm; 65.5, 114.9, 122.4, 122.5, 124.0, 128.7, 128.9, 129.1, 130.3, 131.5, 132.1, 132.5, 139.9, 143.2, 156.1, 203.6.

Then, in a eggplant flask equipped with a three-way cock with a balloon inflated with nitrogen, a stirrer, 2,2-bis (4-hydroxyphenyl) acenaphthene-1- (2H) -on 0 obtained by the above process .35 g (0.99 mmol), phenol 0.73 g (7.8 mmol), and 1-dodecanethiol 0.085 g (0.42 mmol) were added, the atmosphere was replaced with nitrogen, and the mixture was heated to 75 ° C. 2 mL of trifluoromethanesulfonic acid was added, and the mixture was stirred at 75 ° C. for 7 hours to be reacted. After cooling the reaction mixture, extraction was performed by adding ethyl acetate and distilled water, and the organic layer was washed with distilled water, dried over sodium sulfate, the desiccant was filtered, and concentrated with an evaporator. The concentrated solution is purified by silica gel column chromatography (toluene: ethyl acetate = 6: 1), then crystallized by adding hexane and a small amount of toluene, filtered and dried to obtain 0.16 g of product (orange crystals). Obtained. The yield was 48%. The product had a melting point of 245.5 ° C and Td (5%) of 320.9 ° C.
The chemical formula, ¹ H-NMR, and ¹³ C-NMR spectral data of the product 1,2-bis (4-hydroxyphenyl) acenaphthylene are shown below.

¹ H-NMR (CDCl ₃ ) ppm; 9.56 (d, 2H), 7.91 (d, 2H), 7.65 (m, 4H), 7.20 (m, 4H) 6.80 (m , 4H)
¹³ C-NMR (CDCl ₃ ) ppm; 156.5, 139.5, 136.0, 130.7, 129.2, 128.7, 128.0, 127.9, 128.0, 127.9, 127.8, 126.8, 125.2, 123.3, 118.6, 115.4, 115.1.

  The novel aromatic compound of the present invention has characteristics such as a high refractive index and high heat resistance, and can be used as a resin monomer, an antioxidant, a curing agent, and the like. For example, since the aromatic compound of the present invention has a plurality of hydroxyl groups, a polyol of a resin (for example, a polyester resin, a polyurethane resin, an epoxy resin, a heat or photocurable (meth) acrylic resin, etc.) It can be used as a component (for example, a diol component).

Claims (9)

A compound represented by the following formula (1).

(In the formula, ring X is an aromatic ring, R ¹ is a substituent, p is an integer of 0 or more, ring Z is an aromatic hydrocarbon ring, R ² is an alkylene group, q is an integer of 0 or more, and r is 1 or more. An integer, R ³ represents a substituent, and s represents an integer of 0 or more.)   The compound according to claim 1, wherein X in the formula (1) is a condensed polycyclic aromatic hydrocarbon ring. The compound according to claim 1 or 2, which is a compound represented by the following formula (1A) or (1B).

(In the formula, p1 represents an integer of 0 to 3, p2 represents an integer of 0 to 4, and R ¹ , Z, R ² , q, r, R ³ , and s are the same as described above.)   Ring Z is a benzene ring or a naphthalene ring, q is 0-4, r is 1-3, The compound in any one of Claims 1-3. The method to manufacture the compound in any one of Claims 1-4 by making the compound represented by following formula (2) and the compound represented by following formula (3) react in presence of an acid catalyst.

(In the formula, ring Y represents a ring obtained by removing two oxo groups from o-quinone of the aromatic ring X, and R ¹ , p, Z, R ² , q, r, R ³ , and s are the same as above. .)   The production method according to claim 5, wherein the acid catalyst is composed of sulfonic acid.   The production method according to claim 5 or 6, wherein the acid catalyst is composed of a haloalkanesulfonic acid.   The production method according to any one of claims 5 to 7, further comprising reacting in the presence of a thiol in addition to the acid catalyst.   The production method according to claim 8, wherein the acid catalyst is composed of fluoroalkanesulfonic acid and the thiols are composed of alkyl mercaptan.