JP2019077672A - Bisaryl alcohols having naphthalene skeleton and method for producing the same - Google Patents

Abstract

To provide a resin raw material capable of exhibiting a high refractive index and high heat resistance.SOLUTION: A compound is represented by the following formula. In formula, ring Z, ring Zand ring Zare aromatic rings; at least one of the ring Z, the ring Zand the ring Zis a naphthalene ring; Ris H, 1-6C alkyl group which may have a branch, 5-12C cycloalkyl group or 6-12C aryl group; R, Rand Rare each independently 1-6C alkyl group which may have a branch, 6-12C aryl group or a halogen atom; Rand Rare 2-4C alkylene group which may have a branch; m1, m2 and m3 are an integer of 0-3; and n1 and n2 are each an integer of 1 or more.SELECTED DRAWING: None

Description

  The present invention relates to a bisaryl alcohol having a naphthalene skeleton which can be used for polyester, polycarbonate, polyacrylate, polyurethane, epoxy resin and the like, and a method for producing the same.

  Bisaryl alcohols represented by bisphenol A, which have high refractive index, transparency, heat resistance, water resistance, etc., are widely used as resin raw materials for polyesters, polycarbonates, polyacrylates, polyurethanes, epoxy resins, etc. [For example, Japanese Patent Application Laid-Open No. 60-063214 (Patent Document 1)].

  For example, it is described in the literature that the refractive index of the 2,2-bis (4-methacryloxyethoxy-3,5-dibromophenyl) propane polymer described in Patent Document 1 is 1.61. However, the required performance in recent years has not been fully satisfied. Therefore, in order to solve such a problem in JP 02-111742 A (patent document 2), bis [4- (2-hydroxyethoxy) phenyl] -diphenylmethane may be used as a dihydroxy compound which can be expected to have a higher refractive index. It has been proposed in the literature that the refractive index of the copolymer of its acrylic acid derivative and styrene is 1.63.

  Moreover, as a dihydroxy compound which comprises a polyester copolymer, in Unexamined-Japanese-Patent No. 06-145320 (patent document 3), 1, 1-bis (4-hydroxy ethoxy phenyl) 1-phenyl- ethane and 1, 1- bis (4 -Hydroxyethoxyphenyl) -1,1-diphenyl-methane and the like are proposed, and it is described in the literature that polyester copolymers of these dihydroxy compounds and naphthalenedicarboxylic acid are resin materials having excellent optical properties and heat resistance. It is done.

  In addition, bisaryl alcohols having a fluorene skeleton are known as resin raw materials having high refractive index and high heat resistance, and, for example, refraction of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene The refractive index is relatively high at 1.63. However, in recent years, it can not be said that the refractive index is sufficient as a high refractive index material required as an optical member, and development of a material having a further higher refractive index has been required.

Japanese Patent Application Laid-Open No. 60-063214 JP 02-111742 A Japanese Patent Application Publication No. 06-145320

  An object of the present invention is to provide a resin raw material that can exhibit high refractive index and high heat resistance.

  The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, alcohols represented by the following general formula (1) show high refractive index and high melting point, and further an index of chemical stability. It has been found that the 5% weight loss temperature, which is Specifically, the present invention includes the following inventions.

[1]
Alcohols represented by the following general formula (1).

（式中、環Ｚ_１、環Ｚ_２及び環Ｚ_３は芳香環を表す。但し、環Ｚ_１、環Ｚ_２及び環Ｚ_３の内、少なくとも一つはナフタレン環である。Ｒ^１は水素原子、分岐を有してもよい炭素数１〜６のアルキル基、炭素数５〜１２のシクロアルキル基又は炭素数６〜１２のアリール基を表す。Ｒ^２ａ、Ｒ^２ｂ及びＲ^２ｃはそれぞれ同一又は異なって分岐を有してもよい炭素数１〜６のアルキル基、炭素数６〜１２のアリール基又はハロゲン原子を表す。Ｒ^３ａ及びＲ^３ｂは分岐を有してもよい炭素数２〜４のアルキレン基を表す。ｍ１、ｍ２及びｍ３は０〜３の整数を表し、ｎ１及びｎ２は１以上の整数を表す。ｍ１、ｍ２及びｍ３の内、少なくとも一つが２以上である場合、それぞれ対応するＲ^２ａ、Ｒ^２ｂ又はＲ^２ｃは同一であっても異なってもよい。）
〔２〕
環Ｚ_１及び環Ｚ_２がともにナフタレン環である、〔１〕に記載のアルコール類。
〔３〕
環Ｚ_３がナフタレン環である、〔１〕又は〔２〕に記載のアルコール類。
〔４〕
以下一般式（２）：

(Wherein, ring Z ₁ , ring Z ₂ and ring Z ₃ represent an aromatic ring, provided that at least one of ring Z ₁ , ring Z ₂ and ring Z ₃ is a naphthalene ring. R ¹ is hydrogen atoms, branched may have an alkyl group having 1 to 6 carbon atoms, ^.R 2a to a cycloalkyl group or an aryl group having 6 to 12 carbon atoms 5 to 12 carbon ^{atoms, R 2b} and ^{R 2c} each identical Or an alkyl group having 1 to 6 carbon atoms which may have a branch, an aryl group having 6 to 12 carbon atoms, or a halogen atom, R ^3a and R ^3b each may have a branch and have 2 to 2 carbon atoms. And m1, m2 and m3 each represents an integer of 0 to 3, and n1 and n2 each represent an integer of 1 or more, provided that at least one of m1, m2 and m3 is 2 or more, The corresponding R ^2a , R ^2b or R ^2c are identical or different May be
[2]
The alcohols according to [1], wherein ring Z ₁ and ring Z ₂ are both naphthalene rings.
[3]
Alcohols described in [1] or [2], wherein ring Z ₃ is a naphthalene ring.
[4]
The following general formula (2):

（式中、環Ｚ_３及びＲ^１は上述の通りである。また、Ｒ^４は分岐を有してもよい炭素数１〜６のアルキル基、炭素数６〜１２のアリール基又はハロゲン原子を表し、ｐは０〜３の整数を表す。ｐが２以上である場合、対応するＲ^４は同一であっても異なってもよい。）
で表されるカルボニル化合物類と、
以下一般式（３）：

(Wherein the ring Z ₃ and R ¹ are as described above. Also, R ⁴ is an alkyl group having 1 to 6 carbon atoms which may have a branch, an aryl group having 6 to 12 carbon atoms or a halogen atom And p represents an integer of 0 to 3. When p is 2 or more, corresponding R ⁴ may be the same or different.)
And carbonyl compounds represented by
The following general formula (3):

（式中、環Ｚは芳香環を表す。また、Ｒ^５は分岐を有してもよい炭素数１〜６のアルキル基、炭素数６〜１２のアリール基又はハロゲン原子を表し、ｑは０〜３の整数を表す。ｑが２以上である場合、対応するＲ^５は同一であっても異なってもよい。）
で表されるアリールアルコール類とを反応させ、以下一般式（４）：

(Wherein, ring Z represents an aromatic ring, and R ⁵ represents an alkyl group having 1 to 6 carbon atoms which may have a branch, an aryl group having 6 to 12 carbon atoms, or a halogen atom, and q is 0) Represents an integer of to 3. When q is 2 or more, corresponding R ⁵ may be the same or different.)
The aryl alcohol represented by is reacted with a compound represented by the general formula (4):

（式中、環Ｚ_１、環Ｚ_２、環Ｚ_３、Ｒ^１、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^２ｃ、ｍ１、ｍ２及びｍ３は上述の通りである。）
で表されるビスアリールアルコール類を得る工程、及び
上記一般式（４）で表されるビスアリールアルコール類とアルキレンカーボネートとを反応させる工程、
をこの順で含む、〔１〕〜〔３〕いずれかに記載のアルコール類の製造方法。

(Wherein, ring Z ₁ , ring Z ₂ , ring Z ₃ , R ¹ , R ^2a , R ^2b , R ^2c , m 1, m 2 and m 3 are as described above).
Obtaining a bisaryl alcohol represented by: and reacting the bisaryl alcohol represented by the above general formula (4) with an alkylene carbonate;
The method for producing alcohols according to any one of [1] to [3], comprising

  According to the present invention, it is possible to provide an alcohol which can be a raw material of a resin exhibiting high refractive index and high heat resistance. In particular, the alcohol of the present invention has a high refractive index and a high melting point specifically despite having no phenolic hydroxyl group or fluorene skeleton, and further a 5% weight reduction as an indicator of chemical stability. Since it exhibits such a feature that the temperature is also high, it can be used as a raw material of a resin that exhibits characteristics equivalent to or better than various resins produced from bisaryl alcohols having a fluorene skeleton.

It is a < ¹ > H-NMR spectrum of an alcohol compound represented by the following formula (1-1) among the alcohols represented by the said General formula (1) manufactured in Example 1. FIG. It is a < ¹³ > C-NMR spectrum of the alcohol compound represented by the following formula (1-1) among the alcohols represented by the said General formula (1) manufactured in Example 1. FIG. It is a mass spectrum of the alcohol compound represented by following formula (1-1) among the alcohols represented by the said General formula (1) manufactured in Example 1. FIG.

Alcohols of the Present Invention
The alcohol of the present invention is represented by the above general formula (1). In the above general formula (1), the ring Z ₁ , the ring Z ₂ and the ring Z ₃ represent an aromatic ring, and at least one of them contains a naphthalene ring. Both the ring Z ₁ and the ring Z ₂ are preferably naphthalene rings, since the alcohol represented by the above general formula (1) has a higher melting point and a higher refractive index, and in particular, the ring Z ₁ and the ring Z ₂ And all of the rings Z ₃ are naphthalene rings.
With regard to the ring Z ₁ , the ring Z ₂ and the ring Z ₃ , examples of the aromatic ring other than the naphthalene ring include, for example, a benzene ring, and polycyclic aromatic rings such as anthracene ring, phenanthrene ring and pyrene ring. At least ring Z ₃ is preferably an aromatic ring other than a fluorene ring, ring Z _1, and more preferably all ring Z ₂ and Ring Z ₃ is an aromatic ring other than a fluorene ring.
As a C1-C6 alkyl group which may have a branch in substituent R ^1, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group And a linear or branched alkyl group such as pentyl group and hexyl group. Examples of the cycloalkyl group having 5 to 12 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and adamantyl. Group, norbornyl group, bicyclohexyl group and the like, and examples of the aryl group having 6 to 12 carbon atoms include phenyl group, alkyl (for example, alkyl having 1 to 4 carbon atoms) substituted phenyl group, biphenyl group, naphthyl group and the like It can be mentioned. Among these substituents R ¹ , preferred is a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, or a phenyl group, and more preferred is a hydrogen atom, a methyl group or a phenyl group.
As the ^optionally branched alkyl group having 1 to 6 carbon atoms for the substituents R ^2a , R ^2b and R ^2c , for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s- And a linear or branched alkyl group such as butyl group, t-butyl group, pentyl group, hexyl group, etc., and examples of the aryl group having 6 to 12 carbon atoms include phenyl group, alkyl (eg, 1 to 4 carbon atoms) Alkyl) substituted phenyl group, biphenyl group, naphthyl group etc. are mentioned, and fluorine, chlorine, bromine etc. are mentioned as a halogen atom. Among these substituents, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms is preferable, and a methyl group is particularly preferable.
Examples of the optionally branched alkylene group having 2 to 4 carbon atoms as R ^3a and R ^3b include ethylene, n-propylene, isopropylene, n-butylene, s-butylene and t-butylene It can be mentioned. Among these alkylene groups, ethylene group or isopropylene group is preferable.

In the above general formula (1), m1 to m3 representing the number of substituents represent an integer of 0 to 3, preferably 0 or 1, particularly preferably 0. When at least one of m1 to m3 is 2 or more, the corresponding substituents R ^2a , R ^2b or R ^2c may be the same or different. N1 and n2 representing the number of oxyalkylenes represent an integer of 1 or more, preferably 1 or 2, particularly 1.

  The alcohol represented by the above general formula (1) of the present invention is known as a material exhibiting a high refractive index since the refractive index measured under the conditions described later is usually 1.63 or more, particularly 1.65 or more. It can exhibit a refractive index comparable to or higher than that of bisaryl alcohols having a fluorene skeleton.

  In addition, the alcohol represented by the above general formula (1) of the present invention has a melting point of 200 ° C. or more, particularly 230 ° C. or more, and therefore generally has a high melting point and high heat resistance when used as a resin. It may exhibit a higher melting point as compared to bisaryl alcohols having a fluorene skeleton which is said to exhibit.

  Further, the alcohol represented by the above general formula (1) of the present invention is considered to exhibit high heat resistance when made into a resin, since the 5% weight loss temperature is 300 ° C. or more, particularly 340 ° C. or more. It may exhibit a 5% weight loss temperature comparable to or higher than bisaryl alcohols having a fluorene backbone.

  As described in detail above, the alcohol represented by the above general formula (1) of the present invention has a refractive index, melting point and 5% weight reduction equal to or higher than those of bisaryl alcohols having a fluorene skeleton. Because it has a temperature, it is of course suitably used as a monomer for thermoplastic resins such as polycarbonate, polyester, polyester polycarbonate, etc., but also with monomers for acrylic resins and epoxy resins by performing acrylateation and epoxidation according to a conventional method. It is also possible. In particular, since the refractive index is high, it can be suitably used as a monomer for resin that constitutes an optical member represented by an optical lens or an optical film.

<Method of producing alcohol of the present invention>
The alcohol represented by the above general formula (1) is, for example, a carbonyl compound represented by the above general formula (2) in the presence of a base or an acid, and an aryl alcohol represented by the above general formula (3) To obtain the bisaryl alcohols represented by the above general formula (4), which are obtained by reacting the bisaryl alcohols with an alkylene carbonate. Among the carbonyl compounds represented by the above general formula (2), when the substituent R ¹ is a carbonyl compound (aldehyde) which is a hydrogen atom, a base may be used from the viewpoint of reactivity and regioselectivity preferable. In addition, when the substituent R ¹ is a carbonyl compound (ketone) other than a hydrogen atom, it is preferable to use an acid from the viewpoint of reactivity.

In the above general formula (2), the alkyl group having 1 to 6 carbon atoms which may have a branch in substituent R ⁴ is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Examples thereof include linear or branched alkyl groups such as s-butyl group, t-butyl group, pentyl group and hexyl group, and examples of the aryl group having 6 to 12 carbon atoms include phenyl group, alkyl (for example, 1 to 6 carbon atoms) 4 alkyl) substituted phenyl group, biphenyl group, naphthyl group and the like, and examples of the halogen atom include fluorine, chlorine, bromine and the like. Among these substituents, an alkyl group having 1 to 4 carbon atoms or an aryl group is preferable, and a methyl group is particularly preferable.
In the above general formula (2), p representing the number of substituents represents 0 or an integer of 1 to 3, preferably 0 or 1, and particularly preferably 0.

  Specific examples of the carbonyl compounds represented by the above general formula (2) include benzaldehyde, 2-methyl benzaldehyde, 3-methyl benzaldehyde, 4-methyl benzaldehyde, 2,3-dimethyl benzaldehyde, 2,4-dimethyl benzaldehyde, 2,5-Dimethyl benzaldehyde, 2,6-dimethyl benzaldehyde, 2,4,5-trimethyl benzaldehyde, 2,4,6-trimethyl benzaldehyde, 4-ethyl benzaldehyde, 4-butyl benzaldehyde, 4-t-butyl benzaldehyde, 4 -Isopropyl benzaldehyde, 4-isobutyl benzaldehyde, 4-fluoro benzaldehyde, 2,4-difluoro benzaldehyde, 3,4- difluoro benzaldehyde, 4-chloro benzaldehyde 2,4-Dichlorobenzaldehyde, 3,4-dichlorobenzaldehyde, 4-bromobenzaldehyde, biphenyl-3-carboxaldehyde, biphenyl-4-carboxaldehyde, acetophenone, 4'-methylacetophenone, 4'-ethylacetophenone, 4'- Isopropylacetophenone, 2,4,6-trimethylacetophenone, ethyl phenyl ketone, 4'-t-butylpropiophenone, 4'-ethylpropiophenone, 4'-methylpropiophenone, isobutyrophenone, butyrophenone, hexanophenone , Isobutyl phenyl ketone, butyl phenyl ketone, hexyl phenyl ketone, cyclopropyl phenyl ketone, cyclobutyl phenyl ketone, cyclopentyl phenyl ketone, cyclohexyl phenyl ketone Ketone, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 3,4-dimethylbenzophenone, 4,4'-dimethylbenzophenone, 4,4'-di-t-butylbenzophenone, 1-naphthaldehyde 4-Methyl-1-acetonaphthone, 2-naphthoaldehyde, 1-bromo-2-naphthaldehyde, 6-bromo-2-naphthaldehyde, 1′-acetonaphthone, 4-methyl-1-acetonaphthone, 2′-acetonaphthone, 2-naphthyl phenyl ketone, 9-anthracene carboxaldehyde etc. are mentioned.

In the above general formula (3), the alkyl group having 1 to 6 carbon atoms which may have a branch in substituent R ⁵ is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Examples thereof include linear or branched alkyl groups such as s-butyl group, t-butyl group, pentyl group and hexyl group, and examples of the aryl group having 6 to 12 carbon atoms include phenyl group, alkyl (for example, 1 to 6 carbon atoms) 4 alkyl) substituted phenyl group, biphenyl group, naphthyl group and the like, and examples of the halogen atom include fluorine, chlorine, bromine and the like. Among these substituents, an alkyl group having 1 to 4 carbon atoms or an aryl group is preferable, and a methyl group is particularly preferable.
In the above general formula (3), q representing the number of substituents represents an integer of 0 or 1 to 3, preferably 0 or 1, and particularly preferably 0.
In the general formula (3), the ring Z corresponds to the ring Z ₁ and the ring Z ₂ in the general formula (1).

  Specific examples of the aryl alcohols represented by the above general formula (3) include phenol, orthocresol, metacresol, paracresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, 2-tert- Butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 4-tert-amylphenol, 4-hexylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 2,6-diphenylphenol, 4 -Chlorophenol, 4-bromophenol, 1-naphthol, 2,4-dibromo-1-naphthol, 2-naphthol, 6-bromo-2-naphthol, 7-bromo-2-naphthol, 1-chloro-2-naphthol , 1-bromo-2-naphthol 3-bromo-2-naphthol, 1,6-dibromo-2-naphthol.

  The amount of use of the aryl alcohol represented by the above general formula (3) is usually 2 to 5 moles per 1 mole of the carbonyl compound represented by the above general formula (2), and more economically the above general formula From the viewpoint of obtaining the bisaryl alcohol represented by (4), preferably 2 to 3 moles are used. The aryl alcohols represented by the above general formula (3) may be used alone or in combination of two or more as required. By using two or more kinds in combination, it is possible to produce an asymmetric bisaryl alcohol represented by the above general formula (4) or an alcohol represented by the above general formula (1).

  Examples of the base used in this reaction include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal carbonates such as potassium carbonate and sodium carbonate, and alkali metal salts of organic acids such as sodium acetate Etc. The amount of the base used is usually 0.1 to 3.0 moles relative to 1 mole of the aryl alcohol represented by the above general formula (3), and from the viewpoint of obtaining a sufficient reaction rate and the viewpoint of the ease of post-treatment Preferably, 0.3 to 1.0 mol is used per 1 mol of the aryl alcohol. One of these bases may be used alone, or two or more of these bases may be used in combination as needed.

  As the acid used in this reaction, various acids such as inorganic acids and organic acids can be used. Specifically, inorganic acids such as sulfuric acid, hydrogen chloride, hydrochloric acid, phosphoric acid, heteropoly acid, zeolite, clay mineral etc. It is exemplified, and examples of the organic acid include methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, ion exchange resin and the like. The amount of the acid used is usually 0.1 to 5.0 moles relative to 1 mole of the carbonyl compounds represented by the above general formula (2), and from the viewpoint of obtaining a sufficient reaction rate and the ease of post-treatment From 0.5 to 1.0 mol is preferably used per 1 mol of the carbonyl compounds. These acids may be used alone or in combination of two or more as needed.

When using an acid, it is preferable to coexist a sulfur-containing compound from the viewpoint of improving the reaction rate. Examples of sulfur-containing compounds usable in this reaction include sulfur-containing carboxylic acids, alkyl mercaptans, aralkyl mercaptans and salts thereof.
Examples of sulfur-containing carboxylic acids include thioacetic acid, mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid and the like, and alkyl alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n _-C1-16 alkyl mercaptans, such as-butyl mercaptan and dodecyl mercaptan, are illustrated. Among these sulfur-containing compounds, dodecyl mercaptan is preferably used in terms of industrial handling.
The amount of use of these sulfur-containing compounds is usually from 0.01 to 1.0 parts by weight, based on 1 part by weight of the carbonyl compounds represented by the general formula (2), from the viewpoint of obtaining a sufficient reaction rate and From the viewpoint of easiness of post-treatment, preferably 0.01 to 0.50 parts by weight is used with respect to 1 part by weight of the carbonyl compounds. These sulfur-containing compounds may be used alone or in combination of two or more as required.

When the carbonyl compounds represented by the general formula (2) and the aryl alcohol represented by the general formula (3) are reacted, the reaction may be carried out in the presence of a solvent, if necessary. Examples of usable solvents include aliphatic hydrocarbons, aromatic hydrocarbons, ethers, halogenated hydrocarbons, aprotic polar solvents and the like.
Examples of aliphatic hydrocarbons include hexane, heptane, octane, decane and the like. Examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene and the like. Ethers such as dialkyl ethers such as diethyl ether, Examples thereof include cyclic ethers such as tetrahydrofuran and dioxane, and examples of halogenated hydrocarbons include aliphatic halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, and aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene. As an aprotic polar solvent, for example, dimethylsulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like are exemplified. Be done. Among these solvents, aromatic hydrocarbons such as toluene and xylene are preferably used in view of availability and good handleability.
The amount used in the case of using these solvents is usually 0.1 to 10 parts by weight with respect to 1 part by weight of the carbonyl compounds represented by the above general formula (2), from the viewpoint of obtaining a sufficient reaction rate and economic viewpoint Preferably, it is used in an amount of 0.5 to 5.0 parts by weight with respect to 1 part by weight of the carbonyl compounds. These solvents may be used alone or in combination of two or more as needed.

  The reaction of the carbonyl compound represented by the general formula (2) and the aryl alcohol represented by the general formula (3) is carried out usually at 50 to 200 ° C., preferably 80 to 140 ° C. The reaction may be carried out while dehydrating under normal pressure or reduced pressure reflux, as needed, from the viewpoint of obtaining a sufficient reaction rate.

  After completion of the reaction described above, even if the bisaryl alcohol represented by the above general formula (4) is taken out by a conventional method such as neutralization, water washing, concentration, crystallization, filtration, etc., as necessary. Good. Moreover, you may use for reaction of this bisaryl alcohol and alkylene carbonate which are mentioned later, without taking out the bisaryl alcohol represented by the said General formula (4). Furthermore, the bisaryl alcohols represented by the above general formula (4) once taken out may be purified by ordinary methods such as recrystallization, distillation, adsorption, column chromatography etc. before being subjected to the reaction with the alkylene carbonate. Good.

  Subsequently, the reaction of the bisaryl alcohol represented by the general formula (4) with the alkylene carbonate will be described in detail.

  Examples of the alkylene carbonate used in the present invention include ethylene carbonate, propylene carbonate and butylene carbonate. The amount of use of the alkylene carbonate can be appropriately adjusted according to n1 and n2 representing the number of oxyalkylenes in the above general formula (1), for example, the alcohol represented by the above general formula (1) in which n1 = n2 = 1 When a group is produced as a main product, the amount thereof to be used is generally 2 to 5 mol, preferably 2 to 3 mol, per 1 mol of the bisaryl alcohol represented by the above general formula (4).

When the bisaryl alcohols represented by the above general formula (4) are reacted with an alkylene carbonate, they may be reacted in the presence of a base. Examples of usable bases include carbonates, bicarbonates, hydroxides, organic bases and the like. More specifically, potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate etc. as carbonates, potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, lithium hydrogen carbonate etc. as hydrogen carbonates, hydroxides Sodium hydroxide, potassium hydroxide, lithium hydroxide and the like are exemplified, and as organic bases, triethylamine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, tetramethylammonium chloride and the like are exemplified. Among these bases, potassium carbonate, sodium carbonate or triphenylphosphine is preferably used from the viewpoint of good handling. One of these bases may be used alone, or two or more of these bases may be used in combination as needed.
The amount of these bases to be used is generally 0.01 to 1.0 mol, preferably 0.03 to 0.5 times, per 1 mol of the bisaryl alcohol represented by the above general formula (4). It is a mole.

When the bisaryl alcohols represented by the above general formula (4) are reacted with an alkylene carbonate, the reaction may be performed in the presence of an organic solvent. As such organic solvents, ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, aliphatic nitriles, amides, sulfoxides Etc. are illustrated. More specifically, as ketones, acetone, methyl ethyl ketone, butyl methyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, 2-octanone, cyclohexanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone Nonene, cyclodecanone, cycloundecanone, etc., aromatic hydrocarbons such as toluene, xylene, mesitylene, etc., halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene etc., aliphatic hydrocarbons such as pentane, hexane, heptane etc. And halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane; ethers such as diethyl ether, di-iso-propyl ether, methyl-tert-butyl ether; Ropentyl methyl ether, diphenyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol Dimethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, etc., and aliphatic nitriles such as acetonitrile, and amides such as N, N-dimethylformamide, , N- dimethylacetamide, N- methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and the like as sulfoxides. Among these organic solvents, aromatic hydrocarbons having a boiling point of 110 ° C. or higher, ketones, esters or ethers are preferably used in view of availability and good handleability. These organic solvents may be used alone or in combination of two or more as needed.
The amount of use of these organic solvents is usually 0.1 to 10 times by weight, preferably 0.5 to 3 times by weight the amount by weight of the bisaryl alcohol represented by the general formula (4). It is.

  The reaction of the bisaryl alcohols represented by the above general formula (4) with the alkylene carbonate is usually carried out at 30 to 150 ° C, preferably 100 to 130 ° C.

  After completion of the reaction described above, the alcohol represented by the above general formula (1) may be taken out by a conventional method such as neutralization, water washing, concentration, crystallization, filtration and the like, as necessary. Further, the obtained alcohol represented by the above general formula (1) may be purified by a conventional method such as recrystallization, distillation, adsorption, column chromatography and the like.

  EXAMPLES Although an Example is given to the following and this invention is concretely demonstrated to it, this invention is not limited to this at all. In the examples, various measurements were carried out by the following methods. Moreover, the production | generation rate (remaining rate) and purity of each component described in the following Example are the area percentage of HPLC measured on the following conditions.

[1] HPLC analysis device: Shimadzu LC-20A
Column: YMC-Pack ODS-A (5 μm, 4.6 mmφ × 250 mm)
Mobile phase: A liquid pure water, B liquid acetonitrile. The analysis was carried out by changing the concentration as described below according to the B liquid concentration.
Liquid B concentration: 70% (5 minutes) → (5 minutes) → 90% → (5 minutes) → 100% (15 minutes)
Flow rate: 1.0 ml / min, column temperature: 40 ° C., detection wavelength: UV 254 nm

[2] Melting point (melting endotherm maximum temperature by differential scanning calorimetry (DSC)
Using a differential scanning calorimeter (SII Nano Technology Co., Ltd .: DSC 7020), 5 mg of crystals of the compounds described in the following Examples and Reference Examples are precisely weighed in an aluminum pan, and aluminum oxide is used as a control under the following operating conditions The melting endothermic maximum temperature measured and detected was taken as the melting point.
(Operating conditions)
Heating rate: 10 ° C / min
Measurement range: 30-300 ° C
Atmosphere: Open, nitrogen 40 ml / min

[3] NMR measurement
¹ H-NMR and ¹³ C-NMR were recorded by JEOL-ESC 400 spectrometer using tetramethylsilane as internal standard and CDCl ₃ as solvent.

[4] LC-MS Measurement The LC-MS was separated and mass analyzed under the following measurement conditions to identify the desired product.
Device: "Xevo G2 Q-Tof" manufactured by Waters Co., Ltd.
Column: "YMC-UltraHT Pro C18" manufactured by YMC
(2 μm, 2.0 mmφ × 100 mm)
Column temperature: 40 ° C
Detection wavelength: UV 220-500 nm
Mobile phase: A liquid = 10 mM ammonium acetate water, B liquid = acetonitrile Mobile phase flow rate: 0.3 ml / min Mobile phase gradient: B liquid concentration: 70% → (2 minutes) → 90% → (2 minutes) → 100% (6 minutes)
Detection method: Q-Tof
Ionization method: ESI (+) method Ion Source: Voltage (+) 2.0 kV, temperature 120 ° C.
Sampling Cone: Voltage 30 V, gas flow 50 L / h
Desolvation Gas: Temperature 500 ° C, gas flow 1000 L / h

[5] Refractive index The refractive index measured as follows was made into the refractive index of each compound.
The compounds obtained in the examples were dissolved in dimethylsulfoxide to prepare 5 wt%, 10 wt% and 15 wt% solutions, and the refractive index of each solution was measured under the following apparatus and conditions. Next, an approximate straight line was derived from the measured values at three points obtained, and the value obtained by extrapolating this to 100% by weight was taken as the refractive index of each compound.
<Conditions for measuring refractive index of each solution>
Device: Abbe refractometer ("Multi-wavelength Abbe refractometer DR-2M" manufactured by Atago Co., Ltd.)
Measurement wavelength: 589 nm (20 ° C.)

[6] 5% Weight Loss Temperature The temperature was raised from room temperature to 500 ° C. at a rate of 10 ° C./minute using a thermogravimeter (manufactured by Shimadzu Corporation TGA-50), and measured.

  <Example 1> Among the alcohols represented by the above general formula (1), a production example of an alcohol compound represented by the following formula (1-1)>

In a glass reactor equipped with a stirrer, a heating condenser, a Dean-Stark tube, and a thermometer, 100 g (0.640 mol) of 1-naphthaldehyde, 200 g (1.387 mol) of 2-naphthol, 24% hydroxylated After charging 120 g (0.720 mol) of an aqueous sodium solution and 300 g of toluene, the internal pressure was reduced to 53 kPa, and the temperature was raised to 100 ° C. After stirring for 40 hours while dehydrating at the same temperature, the reaction solution was analyzed by high performance liquid chromatography, and it was found that the formation rate of the bisaryl alcohol compound was 85.4%.
After the reaction, toluene is added to the obtained reaction liquid, and after neutralization with 35% aqueous hydrochloric acid, the reaction liquid is cooled to 20 ° C. to precipitate crystals, and the precipitated crystals are separated by filtration and dried. There were obtained 239 g of crystals of the bisaryl alcohol compound (purity 95%, yield 88%).

In a glass reactor equipped with a stirrer, a heating condenser, and a thermometer, 100 g (0.234 mol) of crystals of the obtained bisaryl alcohol compound, 43.6 g (0.495 mol) of ethylene carbonate, potassium carbonate After charging 2.70 g (0.0195 mol) and 200 g of toluene, the temperature is raised to 120 ° C., and after stirring for 22 hours at the same temperature, the reaction solution is analyzed by high performance liquid chromatography, and the above formula The production rate of the alcohol compound represented by (1-1) was 91.6%.
After the reaction, 800 g of N-methyl-2-pyrrolidone is added to the obtained reaction solution and stirred at 90 ° C. for 1 hour to obtain a uniform solution, then ion-exchanged water is slowly added dropwise and stirred at the same temperature for 1 hour. After precipitating crystals, the crystals were further precipitated by cooling to 20.degree. Thereafter, the precipitated crystals were separated by filtration and dried to obtain 70 g of crystals of the alcohol compound represented by the above formula (1-1) (purity 99%, yield 67%).
The melting point, the refractive index and the 5% weight loss temperature of the obtained alcohol compound represented by the above formula (1-1) were measured by the above method. In addition, by measuring the obtained crystal by ¹ H-NMR, ¹³ C-NMR and LC-MS, it was confirmed that the crystal is an alcohol compound represented by the above formula (1-1). The measurement charts of ¹ H-NMR, ¹³ C-NMR and LC-MS are shown in FIG. 1, FIG. 2 and FIG. 3 respectively, and the measurement results are described below.

¹ H-NMR (CDCl ₃ )
δ 2.56-2.74 ppm (3 H, m), 3.00 (1 H, d), 3.38-3. 40 (2 H, m), 3.59-3. 62 (1 H, m), 73 (1 H, t), 3.92-3.97 (1 H, m), 7.09-7.19 (4 H, m), 7.22-7.35 (5 H, m), 7.42 ( 1H, t), 7.52 (1H, s), 7.73-7.89 (9H, m)

¹³ C-NMR (CDCl ₃ )
δ 42.09 ppm, 60.96 ppm, 70.42 ppm, 71.86 ppm, 114.56 ppm, 116.85 ppm, 122.90 ppm, 123.64 ppm, 123.78 ppm, 123.93 ppm, 125.64 ppm, 125.94 ppm, 126. 14 ppm, 126.79 ppm, 127.01 ppm, 127.51 ppm, 128.79 ppm, 128.93 ppm, 129.10 ppm, 129.10 ppm, 129.63 ppm, 129.81 ppm, 130.23 ppm, 131.97 ppm, 133.22 ppm, 133.30 ppm, 133.86 ppm, 140.46 ppm, 155.62 ppm

  Mass spectrum value (M + Na) +: 537.20

Refractive index: 1.67
Melting point: 262 ° C
5% weight loss temperature: 340 ° C.

<Reference example>
The melting point, the refractive index and the 5% weight loss temperature of the fluorene compound represented by the following formula (5) were measured by the above-mentioned method. The results are shown below.

Refractive index: 1.63
Melting point: 161 ° C
5% weight loss temperature: 320 ° C.

Claims (4)

Alcohols represented by the following general formula (1).

(Wherein, ring Z ₁ , ring Z ₂ and ring Z ₃ represent an aromatic ring, provided that at least one of ring Z ₁ , ring Z ₂ and ring Z ₃ is a naphthalene ring. R ¹ is hydrogen atoms, branched may have an alkyl group having 1 to 6 carbon atoms, ^.R 2a to a cycloalkyl group or an aryl group having 6 to 12 carbon atoms 5 to 12 carbon ^{atoms, R 2b} and ^{R 2c} each identical Or an alkyl group having 1 to 6 carbon atoms which may have a branch, an aryl group having 6 to 12 carbon atoms, or a halogen atom, R ^3a and R ^3b each may have a branch and have 2 to 2 carbon atoms. And m1, m2 and m3 each represents an integer of 0 to 3, and n1 and n2 each represent an integer of 1 or more, provided that at least one of m1, m2 and m3 is 2 or more, The corresponding R ^2a , R ^2b or R ^2c are identical or different May be The alcohols according to claim 1, wherein ring Z ₁ and ring Z ₂ are both naphthalene rings. Ring Z ₃ is a naphthalene ring, an alcohol according to claim 1 or 2. The following general formula (2):

(Wherein the ring Z ₃ and R ¹ are as described above. Also, R ⁴ is an alkyl group having 1 to 6 carbon atoms which may have a branch, an aryl group having 6 to 12 carbon atoms or a halogen atom And p represents an integer of 0 to 3. When p is 2 or more, corresponding R ⁴ may be the same or different.)
And carbonyl compounds represented by
The following general formula (3):

(Wherein, ring Z represents an aromatic ring, and R ⁵ represents an alkyl group having 1 to 6 carbon atoms which may have a branch, an aryl group having 6 to 12 carbon atoms, or a halogen atom, and q is 0) Represents an integer of to 3. When q is 2 or more, corresponding R ⁵ may be the same or different.)
The aryl alcohol represented by is reacted with a compound represented by the general formula (4):

(Wherein, ring Z ₁ , ring Z ₂ , ring Z ₃ , R ¹ , R ^2a , R ^2b , R ^2c , m 1, m 2 and m 3 are as described above).
Obtaining a bisaryl alcohol represented by: and reacting the bisaryl alcohol represented by the general formula (4) with an alkylene carbonate;
The manufacturing method of alcohol as described in any one of Claims 1-3 which contains in order of this.

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