JP2022104623A - Method for producing fluorene derivatives and raw materials thereof - Google Patents

Abstract

To produce fluorene derivatives having a 9,9-bis(hydroxyethoxy condensed polycyclic aryl)fluorene skeleton in high reaction conversion.SOLUTION: In a method for producing fluorene derivatives by reacting alcohols represented by the following formulas (1) and (2) with specific fluorenones in the presence of an acid catalyst and thiols, the reaction conversion is improved by adjusting a ratio of diols represented by the following formula (5) to 1 pt.mass or less relative to a total of 100 pts.mass of the alcohols. (In the formulas, rings Z1 to Z3 represent condensed polycyclic arene rings; A1 to A4 represent linear or branched-chain C2-4 alkylene group; R1, R2, and R4 represent substituents; and m1, m2, and k represent integers of 0 or more.)SELECTED DRAWING: None

Description

The present invention relates to a method for producing a fluorene derivative having a 9,9-bis (hydroxyalkoxy fused polycyclic aryl) fluorene skeleton and a raw material thereof.

Compounds having a 9,9-bis (hydroxyalkoxy fused polycyclic aryl) fluorene skeleton (hereinafter, may be simply referred to as "fluorene derivative") have various optical properties, thermal properties, mechanical properties, and the like. Due to its excellent properties, it is used in various fields as a raw material (or monomer) for resins for optical members and as an additive such as a resin modifier.

As a method for producing such a fluorene derivative, for example, fluorenones and a hydroxy-fused polycyclic arene are reacted in the presence of an acid catalyst such as hydrogen chloride gas or concentrated sulfuric acid or a co-catalyst such as thiols. Later, a method of addition-reacting an alkylene oxide (alkylene carbonate or haloalkanol) is known, but an excessively added addition such as a 3-molecule addition or a 4-molecule addition or a raw material of 9,9-bis is known. (Hydroxyaryl) fluorene tends to remain as an impurity. The residual impurities not only lead to a decrease in the purity of the target fluorene derivative, but also become a factor leading to coloring at the time of heating and melting. Coloring causes difficulty in application to optical materials, and in particular, there is a risk that it will be difficult to use as a resin raw material for polyester resins and polycarbonate resins having a high polymerization temperature.

As another production method, a method of reacting fluorenones with a hydroxyethoxy-condensed polycyclic arene in the presence of an acid catalyst such as hydrogen chloride gas or concentrated sulfuric acid or a co-catalyst such as thiols is known. .. However, since the fluorene derivative obtained by this method is also colored yellow by impurities such as sulfonates, it needs to be strictly purified in order to be used in applications requiring high transparency such as optical materials. Therefore, a method for easily producing a fluorene derivative having a low degree of coloring and excellent transparency has been further studied.

In JP-A-2018-168124 (Patent Document 1), fluorenones and hydroxy (poly) alkoxyarenes are selected from 2-mercaptoalkanoic acid, aminoalkanethiols and salts thereof in addition to an acid catalyst. A method for producing a fluorenone derivative by reacting in the presence of at least one kind of thiol is disclosed.

Further, in JP-A-2020-75904 (Patent Document 2), fluorenones and hydroxy (poly) alkoxyarenes are contained in a solvent containing at least an aprotic polar solvent in the presence of an acid catalyst and thiols. Disclosed is a method for producing a fluorenone derivative by reacting with.

Japanese Unexamined Patent Publication No. 2018-168124 Japanese Unexamined Patent Publication No. 2020-75904

However, even with the methods of Patent Documents 1 and 2, the reaction conversion rate of the fluorene derivative is not sufficient. Further, when the reaction conversion rate is lowered, not only the yield is lowered, but also the hue is lowered due to the residual of yellow fluorenone which is a raw material, and when it is used as a raw material for an optical resin, the optical performance is lowered.

Therefore, an object of the present invention is to provide a method for producing a fluorene derivative capable of producing a fluorene derivative having a 9,9-bis (hydroxyalkoxy fused polycyclic aryl) fluorene skeleton at a high reaction conversion rate, and a raw material thereof. ..

As a result of diligent studies to achieve the above problems, the present inventors have found that a trace amount of hydroxyalkoxy-hydroxyalkyl fused polycyclic arenes inevitably contained as an impurity in the raw material hydroxyethoxy fused polycyclic arenes. A 9,9-bis (hydroxyalkoxy-fused polycyclic aryl) fluorene skeleton by finding that it exerts a strong reaction-inhibiting effect even in a trace amount and reducing the ratio of the unavoidable impurities to a certain ratio or less. The present invention has been completed by finding that a fluorene derivative having a high reaction conversion rate can be produced.

That is, the production method of the present invention has the following formulas (1) and (2) in the presence of an acid catalyst and thiols.

(During the ceremony,
Rings Z ¹ and Z ² represent fused polycyclic arene rings that are identical or different from each other.
A ¹ and A ² represent linear or branched C _2-4 alkylene groups that are identical or different from each other.
R ¹ and R ² indicate substituents that are the same or different from each other.
m1 and m2 are the same or different from each other and indicate integers greater than or equal to 0)
Alcohols represented by and the following formula (3)

(In the formula, R ³ indicates a substituent and n indicates an integer of 0 to 8).
By reacting with fluorenones represented by the following formula (4)

(In the formula, ring Z ¹ , ring Z ² , A ¹ , A ² , R ¹ , R ² , R ³ , m1, m2 and n are in formula (1), formula (2) or formula (3), respectively. same)
It is a method for producing a fluorene derivative represented by.
The following formula (5)

(During the ceremony,
Ring Z ³ represents a condensed polycyclic arene ring.
A ³ and A ⁴ represent linear or branched C _2-4 alkylene groups that are identical or different from each other.
^R4 indicates a substituent and represents a substituent.
k indicates an integer greater than or equal to 0)
The ratio of the diols represented by is 1 part by mass or less with respect to 100 parts by mass in total of the alcohols.

In the formulas (1), (2), ( ⁴ ) and (5), examples of the preferred embodiments of the rings ^Z1 to Z3 include naphthalene rings ^, and the preferred embodiments of the groups A1 to ^A4 include, for example, naphthalene rings. Examples include linear or branched _C2-3 alkylene groups. Preferable embodiments of the alcohols represented by the formulas (1) and (2) include, for example, the following formulas (1a) and (2a).

(In the equation, m1 and m2 indicate integers of 0 to 6 which are the same as or different from each other, and ^R1 and ^R2 are the same as the equation (1) or the equation (2), respectively).
Examples include alcohols represented by. Further, in this case, as a preferred embodiment of the diol represented by the above formula (5), for example, the following formula (5a)

(In the equation, k indicates an integer from 0 to 6, and ^R4 is the same as equation (5)).
Examples thereof include diols represented by. The alcohols represented by the formulas (1) and (2) are 2- (2-naphthoxy) ethanol, and the diols represented by the formula (5) are 2- (2-hydroxyethoxy). It may be -3- (2-hydroxyethyl) naphthalene. In the above-mentioned production method, the ratio of 2- (1-naphthoxy) ethanol may be 1 part by mass or less with respect to 100 parts by mass of 2- (2-naphthoxy) ethanol.

In the present invention, the raw material composition for producing the fluorene derivative represented by the formula (4) is the alcohols represented by the formulas (1) and (2) and the formula (3). Also included is a raw material composition containing the fluorenones represented and the proportion of the diols represented by the formula (5) to be 1 part by mass or less with respect to 100 parts by mass in total of the alcohols. Preferable embodiments of the alcohols represented by the formulas (1) and (2) include alcohols represented by the above formulas (1a) and (2a), and these alcohols are 2-( 2-Naftoxy) Ethanol may be used. The diols represented by the formula (5) may be 2- (2-hydroxyethoxy) -3- (2-hydroxyethyl) naphthalene. In the raw material composition, the ratio of 2- (1-naphthoxy) ethanol may be 1 part by mass or less with respect to 100 parts by mass of the 2- (2-naphthoxy) ethanol.

In the present invention, in the presence of an acid catalyst and thiols, the alcohols represented by the formulas (1) and (2) are reacted with the fluorenones represented by the formula (3), and the formula is described. In the method for producing the fluorene derivative represented by (4), the ratio of the diols represented by the formula (5) is adjusted to 1 part by mass or less with respect to 100 parts by mass of the total of the alcohols. Also included are methods of improving the reaction conversion rate.

The present invention also includes novel diols represented by the above formula (5).

In the present specification and claims, the number of carbon atoms of the substituent may be indicated by C ₁ , C ₆ , C ₁₀ , or the like. For example, "C ₁ alkyl group" means an alkyl group having 1 carbon atom, and "C _6-10 aryl group" means an aryl group having 6 to 10 carbon atoms.

In the present invention, the proportion of trace amounts of hydroxyalkoxy-hydroxyalkyl fused polycyclic arenes, which are unavoidable impurities contained in the raw materials hydroxyalkoxy fused polycyclic arenes, is reduced to a certain proportion or less. A fluorene derivative having a 9-bis (hydroxyalkoxy fused polycyclic aryl) fluorene skeleton can be produced at a high reaction conversion rate. Therefore, deterioration of hue due to residual yellow fluorenone, which is a raw material, can be suppressed, and when used as a raw material for an optical resin, optical performance can be improved. Further, when the hydroxyalkoxy fused polycyclic arenes are 2- (2-naphthoxy) ethanol, the yield can be improved by adjusting the ratio of 2- (1-naphthoxy) ethanol to a specific ratio.

FIG. 1 is a ¹ H-NMR spectrum of the diols isolated in Example 1. FIG. 2 is a GC-MS spectrum of the diols isolated in Example 1. FIG. 3 is a graph showing the relationship between the content of diols and the reaction conversion rate in Example 1. FIG. 4 is a graph showing the relationship between the presence / absence of addition of diols and the transition of the reaction conversion rate in Example 3.

In the method of the present invention, the alcohols represented by the formulas (1) and (2) are reacted with the fluorenones represented by the formula (3) in the presence of an acid catalyst and thiols, and the above is described. In the method for producing the fluorene derivative represented by the formula (4), the ratio of the diols represented by the formula (5) is adjusted to 1 part by mass or less with respect to 100 parts by mass of the total of the alcohols.

[Alcohol]
In the formulas (1) and (2), the fused polycyclic arene ring represented by the rings Z ¹ and Z ² (condensed polycyclic aromatic hydrocarbon ring) includes a fused bicyclic arene ring and a condensed. Condensation of a tricyclic arene ring or the like. Examples thereof include a two- to four-cyclic arene ring.

Examples of the fused bicyclic arene ring include a fused bicyclic C _10-16 arene ring such as a naphthalene ring and an indene ring. Examples of the fused tricyclic arene ring include an anthracene ring and phenanthrene ring. These fused polycyclic arene rings can be used alone or in combination of two or more.

The types of the two rings Z ¹ and Z ² may be the same or different from each other, but are preferably the same. Of these, a fused polycyclic C _10-16 arene ring such as a naphthalene ring or an anthracene ring is preferable, a fused polycyclic C _10-14 arene ring is more preferable, and a naphthalene ring is most preferable.

The linear or branched C _2-4 alkylene group represented by the groups A ¹ and A ² includes an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group and a 1,2-butanediyl group. , Tetramethylene group and the like. These alkylene groups can be used alone or in combination of two or more.

The types of the two groups A ¹ and A ² may be the same or different from each other and are usually the same. Of these, a linear or branched C _2-3 alkylene group is preferable, and an ethylene group is particularly preferable.

In the formulas (1) and (2), the substitution positions of the HO-A ¹ O- group and the HO-A ² O- group can be appropriately selected depending on the type of the rings Z ¹ and Z ² , and are not particularly limited. For example, when the rings Z ¹ and Z ² are naphthalene rings, they may be either 1-position or 2-position, but 2-position is preferable. The substitution positions of the HO-A ¹ O- group and the HO-A ² O- group may be different, but are preferably the same.

The substituent represented by the groups R ¹ and R ² may be any group other than the hydroxy C _2-4 alkyl group (hydroxyl group-free group), and may be a halogen atom, a hydrocarbon group, an alkoxy group, or a cycloalkyloxy. Examples thereof include a group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group and a cyano group.

Among these substituents, a halogen atom; an alkyl group, a cycloalkyl group, an aryl group, a hydrocarbon group such as an aralkyl group; an alkoxy group; an acyl group; a nitro group; a cyano group; a substituted amino group and the like are typically used. Can be mentioned. Preferred R ¹ and R ² include an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group and the like, and examples of the alkyl group include a linear or branched C _1-6 alkyl group such as a methyl group. Examples of the cycloalkyl group include a C _5-8 cycloalkyl group such as a cyclohexyl group, examples of the aryl group include a C _6-14 aryl group such as a phenyl group, and examples of the alkoxy group include a C 6-14 aryl group such as a phenyl group. Examples thereof include a linear or branched C _1-4 alkoxy group such as a methoxy group. The types of substituents R ¹ and R ² may be the same or different from each other, but are preferably the same. Of these, an alkyl group is preferable, and a linear or branched C _1-4 alkyl group such as a methyl group is particularly preferable.

The substitution numbers m1 and ^m2 of ^R1 and ^R2 may be integers of 0 or more, and may be appropriately selected depending on the type of ring Z1 and ring Z2, and may be integers of ⁰ to 8, for example. Often, the preferred substitution numbers m1 and m2 are, step by step, an integer of 0 to 6, an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, 0 or 1, with 0 being most preferred. The number of substitutions m1 and the number of substitutions m2 may be different, but the same number of substitutions is preferable. Further, when the substitution numbers m1 and m2 are 2 or more, the types of ^R1 or R2 having ² or more may be the same or different.

Typical alcohols represented by the formulas (1) and (2) are 2- (2-hydroxyethoxy) naphthalene (also known as 2- (2-naphthoxy) ethanol) and 2- (2- (2-). Examples thereof include hydroxypropoxy) naphthalene, 2- (3-hydroxypropoxy) naphthalene, 1- (2-hydroxyethoxy) naphthalene (also known as 2- (1-naphthoxy) ethanol) and the like. As the alcohols represented by the formulas (1) and (2), the alcohols represented by the formulas (1a) and (2a) are preferable, and 2- (2-naphthoxy) ethanol is particularly preferable.

The alcohols represented by the formula (1) and the alcohols represented by the formula (2) may be different compounds, but are preferably the same compound.

In the reaction, the total usage ratio of the alcohols represented by the formulas (1) and (2) is in the range of, for example, about 2 to 20 mol with respect to 1 mol of the fluorenones represented by the formula (3) described later. The preferred range is 2 to 10 mol, 2 to 8 mol, 2 to 6 mol, 2 to 5 mol, 2 to 4 mol, and 2.5 to 3.5 mol in a stepwise manner. If the proportion of the alcohols is too small, the conversion rate (reaction rate) of fluorenones may decrease.

[Glycols]
In the present invention, the alcohols are reacted with the fluorenones represented by the formula (3) to produce a fluorene derivative represented by the formula (4), which includes the alcohols and the fluorenone. By adjusting the ratio of the diols represented by the formula (5) to 1 part by mass or less with respect to 100 parts by mass of the total of the alcohols in the raw material composition, the reaction conversion rate of the fluorenones can be adjusted. Can be improved.

In the above formula (5), examples of the fused polycyclic arene ring represented by ring Z ³ include fused bicyclic arene rings, condensed bicyclic arene rings such as fused tricyclic arene rings, and the like. ..

Examples of the fused bicyclic arene ring include a fused bicyclic C _10-16 arene ring such as a naphthalene ring and an indene ring. Examples of the fused tricyclic arene ring include an anthracene ring and phenanthrene ring. These fused polycyclic arene rings can be used alone or in combination of two or more. Of these, a fused polycyclic C _10-16 arene ring such as a naphthalene ring or an anthracene ring is preferable, a fused polycyclic C _10-14 arene ring is more preferable, and a naphthalene ring is most preferable.

The linear or branched C ^2-4 alkylene group represented by the groups A3 and _A4 includes an ethylene group ^, a propylene group (1,2-propanediyl group), a trimethylene group and a 1,2-butanediyl group. , Tetramethylene group and the like. These alkylene groups can be used alone or in combination of two or more.

The types of the ^two groups A3 and A4 may be the same or different from ^each other, but are preferably the same. Of these, a linear or branched C _2-3 alkylene group is preferable, and an ethylene group is particularly preferable.

In the above formula (5), the substitution positions of the HO-A ³ O- group and the HO-A ^4- group can be appropriately selected depending on the type of the ring Z ³ , and are not particularly limited, but for example, the ring Z ³ is naphthalene. In the case of a ring, the substitution position of the HO- ^A3O -group may be either the 1-position or the 2-position, but the 2-position is preferable. The substitution position of the HO-A ⁴ -group may be any other than the substitution position of the HO-A ³ O- group, but when the HO-A ³ O-group is the 2-position, the 3-position is preferable.

In the formula (5), the substituent ^R4 and its substitution number k are the substituent R1 of the formula ( ¹ ) and its substitution number m1 exemplified in the section of the alcohols, or the substitution number m1 of the above formula (2). It is the same including the substituent ^R2 and the number of substitutions m2 thereof, and their preferred embodiments.

The ratio of the diols may be 1 part by mass or less with respect to 100 parts by mass of the total of the alcohols, but the preferred range is 0.5 parts by mass or less and 0.3 parts by mass in a stepwise manner. Hereinafter, it is 0.2 parts by mass or less, 0.1 parts by mass or less, and 0.09 parts by mass or less. The proportion of the diols is preferably as small as possible in order to improve the reaction conversion rate. If the proportion of the diol is too high, the reaction conversion rate will decrease. The total amount of the alcohols is usually the amount of alcohols as a raw material.

Typical examples of the diols represented by the formula (5) are 2- (2-hydroxyethoxy) -3- (2-hydroxyethyl) naphthalene and 2- (2-hydroxypropoxy) -3-(. 2-Hydroxypropoxy) Naphthalene and the like can be mentioned. As the diols represented by the formula (5), the diols represented by the formula (5a) are preferable, and 2- (2-hydroxyethoxy) -3- (2-hydroxyethyl) naphthalene is particularly preferable. The diols represented by the formula (5) are easily mixed as unavoidable impurities in the manufacturing process of the alcohols, and in particular, 2- (2-hydroxyethoxy) -3- (2-hydroxyethyl) naphthalene is used. Since the molecular weight is the same as that of the adduct in which 2 mol of ethylene oxide is added to 1 mol of 2-naphthol, it is difficult to separate and identify it, and it can be inferred that its existence was unknown.

The diols represented by the formula (5) are novel compounds and have a high reaction inhibitory effect in the method for producing the fluorene derivative. Therefore, the diols can be used as a reaction modifier or a reaction terminator in the reaction between alcohols and ketones. Among them, the diols represented by the above formula (5a) are preferable as the reaction modifier and the reaction terminator, and 2- (2-hydroxyethoxy) -3- (2-hydroxyethyl) naphthalene is particularly preferable.

The diols represented by the formula (5) may be used as a reaction modifier or a reaction terminator in a method for producing a fluorene derivative using, for example, alcohols and fluorenones.

When used as a reaction modifier in the above method, the ratio of the diols is, for example, 0.1 to 10 parts by mass, preferably 0.15 to 5 parts by mass, more preferably 0.1 part by mass with respect to 100 parts by mass of the alcohol. It is 0.5 to 3 parts by mass, more preferably 1 to 2 parts by mass.

When used as a reaction terminator in the above method, the ratio of the diols may be, for example, 0.15 parts by mass or more, for example 0.2 to 30 parts by mass, with respect to 100 parts by mass of the alcohol. It is preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass, and more preferably 2 to 5 parts by mass.

[Other hydroxyl group-containing condensed polycyclic arenes]
In addition to the alcohols, other hydroxyl group-containing fused polycyclic arenes (condensed polycyclic arene skeleton containing a hydroxyl group) are used as raw materials for producing the fluorene derivative represented by the formula (4). However, it is preferable that the proportion of other hydroxyl group-containing fused polycyclic arenes is small. Examples of other hydroxyl group-containing condensed polycyclic arenes include 1-methyl-2- (2-hydroxyethoxy) naphthalene and the like.

The total ratio of the alcohols represented by the formulas (1) and (2) may be 97% by mass or more, preferably 97.5% by mass, based on the total hydroxyl group-containing condensed polycyclic arenes. % Or more, more preferably 98% by mass or more. The higher the total ratio of the alcohols is, the more preferable it is for improving the reaction conversion rate. In particular, by lowering the content ratio of a specific impurity, the decrease in the reaction conversion rate can be greatly suppressed.

In particular, the alcohols represented by the formulas (1) and (2) are 2- (2-naphthoxy) ethanol, and the diols represented by the formula (5) are 2- (2-hydroxyethoxy). ) -3- (2-Hydroxyethyl) naphthalene, 2- (1-naphthoxy) ethanol (also known as 1- (2-hydroxyethoxy) naphthalene) as another hydroxyl group-containing fused polycyclic allene. The ratio is preferably 1 part by mass or less, more preferably 0.95 parts by mass or less, and even more preferably 0.9 parts by mass or less with respect to 100 parts by mass of 2- (2-naphthoxy) ethanol. The smaller the ratio of 2- (1-naphthoxy) ethanol is, the more preferable it is in order to improve the yield of the fluorene derivative.

[Fluorenones]
In the above formula (3), examples of the substituent represented by R ³ include a hydrocarbon group, a cyano group, a halogen atom and the like. Examples of the hydrocarbon group include an alkyl group and an aryl group. Examples of the alkyl group include a linear or branched C _1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and a t-butyl group. Examples of the aryl group include a _C6-10 aryl group such as a phenyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like. These substituents can be used alone or in combination of two or more.

Of these groups R ³ , alkyl groups, cyano groups and halogen atoms are preferable, alkyl groups are more preferable, linear or branched C _1-4 alkyl groups such as methyl groups are more preferable, and C _1-2 . Alkyl groups are most preferred.

The substitution number n of the group R ³ may be an integer of 0 to 8, and the preferable range is as follows, in a stepwise manner, an integer of 0 to 6, an integer of 0 to 5, an integer of 0 to 4, and an integer of 0 to 4. It is an integer of 3, an integer of 0 to 2, 0 or 1, with 0 being most preferred. In the two different benzene rings constituting the fluorene ring, the number of substitutions thereof may be the same or different from each other. Further ^, the types of the groups R3 to be substituted with the different benzene rings may be different from each other, but the same is preferable. When n is 2 or more, the types of the ^two or more groups R3 that are substituted with the same or different benzene rings may be the same or different from each other. The substitution position of the group R ³ is not particularly limited, and may be, for example, the 2-position to the 7-position of the fluorene ring, preferably the 2-position, the 3-position, and the 7-position.

[Raw material composition]
The raw material composition of the present invention is a raw material composition for producing a fluorene derivative represented by the formula (4), and contains the alcohols and the fluorenones, and the proportion of the diols is that of the alcohols. It is 1 part by mass or less with respect to 100 parts by mass in total. In the present invention, the reaction conversion rate of fluorenones can be improved by using such a raw material composition.

Further, in the raw material composition of the present invention, the alcohols represented by the formulas (1) and (2) are 2- (2-naphthoxy) ethanol, and the diols represented by the formula (5) are used. In the case of 2- (2-hydroxyethoxy) -3- (2-hydroxyethyl) naphthalene, the ratio of 2- (1-naphthoxy) ethanol is based on 100 parts by mass of the 2- (2-naphthoxy) ethanol. It is preferably 1 part by mass or less. In the present invention, the yield of the fluorene derivative can be improved by using this raw material.

[Acid catalyst]
Examples of the acid catalyst include inorganic acids, organic acids, solid acids and the like.

Examples of the inorganic acid include sulfuric acid, hydrogen chloride and phosphoric acid. The inorganic acid may be in the form of an aqueous solution, for example, hydrochloric acid, and the concentration of the hydrochloric acid is, for example, 5 to 36% by mass, preferably 20 to 36% by mass.

Examples of the organic acid include sulfonic acid. Examples of the sulfonic acid include (halo) alkane sulfonic acid such as methane sulfonic acid and trifluoromethane sulfonic acid; and allene sulfonic acid such as p-toluene sulfonic acid.

Examples of the solid acid include an inorganic solid acid and an organic solid acid. Examples of the inorganic solid acid include metal compounds such as metal oxides, composite metal oxides, metal sulfides, metal sulfates and polyacids; non-metal sulfates; clay minerals such as zeolites and kaolin. Examples of the organic solid acid include cation exchange resins such as a strongly acidic cation exchange resin and a weakly acidic cation exchange resin. Examples of the strongly acidic cation exchange resin include an ion exchange resin having a sulfonic acid group such as Nafion manufactured by DuPont. Examples of the weakly acidic cation exchange resin include an ion exchange resin having a carboxylic acid group such as a (meth) acrylic acid-divinylbenzene copolymer.

These acid catalysts can also be used alone or in combination of two or more. Preferred acid catalysts are inorganic acids such as sulfuric acid and cation exchange resins, and sulfuric acid is more preferable, and concentrated sulfuric acid is more preferable, because it also acts as a dehydrating agent for water produced by the progress of the reaction.

The sulfuric acid contains dilute sulfuric acid having a concentration of about 30 to 90% by mass, concentrated sulfuric acid having a concentration of 90% by mass or more, fuming sulfuric acid, and the like, and if it can be converted to sulfuric acid in the reaction system, it is trioxidized as a sulfuric acid precursor. Sulfuric acid may be used. Usually, the sulfuric acid may be selected from the range of 80 to 99% by mass in terms of _{H2 SO4} , and the preferable range is 90 to 99% by mass and 93 to 99% by mass in the following steps. %, 96 to 99% by mass, 97 to 98.5% by mass of concentrated sulfuric acid, and 98% by mass of concentrated sulfuric acid is particularly preferable.

The ratio of the acid catalyst can be selected from, for example, about 10 to 1000 parts by mass with respect to 100 parts by mass of the fluorenones, and the preferred range is 50 to 700 parts by mass and 100 to 500 parts by mass in the following steps. , 150 to 400 parts by mass, 200 to 350 parts by mass, most preferably 250 to 300 parts by mass. If the proportion of the acid catalyst is too small, the reaction may not proceed efficiently (or the reaction rate may be significantly reduced).

[Thiols]
It can be presumed that the thiols are compounded to promote the reaction and act as a co-catalyst or co-catalyst of the acid catalyst to promote the reaction.

The thiols are not particularly limited, and are not particularly limited as long as they have a thiol group (sulfanyl group), but 2-mercaptoalkanoic acid, aminoalkanethiols and these are used from the viewpoint that coloring due to heating and melting can be effectively reduced. It is preferable to contain at least one first thiol selected from the salts of the above. When thiols are used, the obtained fluorene derivative contains a large amount of sulfur components (or sulfur-containing components) as impurities, and even if it is purified by a conventional purification method such as strong base treatment, its removal is limited, and the above-mentioned The fluorene derivative is easily colored by heating and melting probably due to the influence of the sulfur component and / or the strong base treatment, but the total sulfur content of the fluorene derivative can be efficiently reduced by containing the first thiol.

Examples of 2-mercaptoalkanoic acid include thioglycolic acid (also known as mercaptoacetic acid or mercaptoethaneic acid), thiolactic acid (also known as α-mercaptopropionic acid), and 2-mercaptobutyric acid (also known as 2-mercapto-n-butanoic acid). , 2-Mercapto C _2-6 alkanoic acid such as 2-mercaptoisobutyric acid (also known as 2-mercapto-isobutyric acid) and the like. Of these, 2-mercapto C _2-3 alkanoic acid is preferable, and 2-mercapto C _2-3 alkanoic acid such as thioglycolic acid and thiolactic acid is more preferable.

Examples of the aminoalkanethiol include 2-aminoethanethiol (also known as cysteamine), 2-aminopropanethiol, 3-aminopropanethiol, 2-aminobutanethiol, 3-aminobutanethiol, 4-aminobutanethiol, 6 Examples thereof include amino C _2-20 alkanethiols such as -aminohexanethiol, 8-aminooctanethiol, 11-aminoundecanethiol and 16-aminohexadecanethiol. The preferred aminoalkanethiol is amino C _2-16 alkanethiol.

Typical salts include inorganic acid salts such as hydrochlorides and sulfates; organic acid salts such as acetates; alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts and magnesium salts; Tetraalkylammonium salts such as ammonium salts, tetramethylammonium salts; or compound salts thereof and the like can be mentioned.

These first thiols may be used alone or in combination of two or more. Of these first thiols, 2-mercaptoalkanoic acid or a salt thereof is preferable, and thioglycolic acid, thiolactic acid or a salt thereof is further used, from the viewpoint of effectively reducing the hue (YI) after heating and melting. Preferably, thiolactic acid or a salt thereof is preferable. Further, from the viewpoint that the total sulfur content can be significantly reduced and the yield can be further improved, it is preferable to contain at least aminoalkanethiol or a salt thereof. Among these first thiols, amino alkane thiols or salts thereof are particularly preferable, and preferred amino alkane thiols are amino C _2-12 alkane thiols, amino C _2-8 alkane thiols, and amino C in stages. _2-6 alkanethiols, amino C _2-4 alkanethiols and amino C _2-3 alkanethiols, with systemamine being the most preferred.

If necessary, the thiols may further contain other thiols other than the first thiol (simply referred to as a second thiol). Examples of the second thiol include thiocarboxylic acid, mercaptocarboxylic acid (excluding 2-mercaptoalkanoic acid), alkyl mercaptan, aralkyl mercaptan or salts thereof.

Examples of the thiocarboxylic acid include thioacetic acid and thioshuic acid.

Examples of the mercaptocarboxylic acid (excluding 2-mercaptoalkanoic acid) include β-mercaptopropionic acid, mercaptosuccinic acid, and mercaptobenzoic acid.

Examples of the alkyl mercaptan include C _1-16 alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, and dodecyl mercaptan. The preferred alkyl mercaptan is C _1-4 alkyl mercaptan.

Examples of the aralkyl mercaptan include benzyl mercaptan.

Examples of these salts include the above-mentioned alkali metal salts, typically sodium salts, and specific compounds include, for example, methyl mercaptan sodium and ethyl mercaptan sodium.

These second thiols may be used alone or in combination of two or more.

The ratio of the first thiols can be selected from the range of, for example, about 10% by mass or more (for example, 10 to 100% by mass) with respect to the whole thiols, and the preferable range is 30% by mass or more in the following steps. , 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and 100% by mass (thiols are substantially only the first thiols). Aspects including) are most preferable. If the proportion of the first thiol is too small, the total sulfur content and the hue (YI) after heating and melting may not be effectively reduced. When the thiols contain the second thiols, the ratio of the first thiols may be selected from the range of, for example, about 60 to 99.9% by mass with respect to the whole thiols, which is preferable. Is 80 to 99% by mass, more preferably 90 to 98% by mass.

The ratio of thiols is, for example, 0.1 part by mass or more with respect to 100 parts by mass of the fluorenone, and specifically, it may be selected from the range of about 1 to 50 parts by mass, preferably 2 to 30 parts. It is by mass, more preferably 3 to 20 parts by mass, more preferably 5 to 15 parts by mass, and most preferably 6 to 10 parts by mass. The ratio of thiols is, for example, 0.01 to 0.5 mol, preferably 0.05 to 0.4 mol, more preferably 0.08 to 0.3 mol, based on 1 mol of the fluorenones. It is more preferably 0.1 to 0.25 mol, and most preferably 0.15 to 0.2 mol. The ratio of thiols can be selected from, for example, 0.01 parts by mass or more, specifically about 0.1 to 50 parts by mass, preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the acid catalyst. Parts, more preferably 1 to 20 parts by mass, more preferably 1.5 to 10 parts by mass, and most preferably 2 to 5 parts by mass. If the proportion of thiols is too small, not only the reaction may not proceed efficiently, but also impurities such as unreacted components may cause coloring. If it is too much, thiols may remain as impurities such as sulfur components.

[solvent]
In the present invention, the reaction may be carried out in the presence or absence of a solvent, but is carried out in the presence of a solvent containing at least an aprotic polar solvent from the viewpoint of efficiently producing a highly pure fluorene derivative. Is preferable.

Examples of the aprotonic polar solvent include ethers, ketones, esters, carbonates, amides, ureas, nitriles, nitrated hydrocarbons, phosphoramides, sulfonates, sulfoxides and the like. These aprotic polar solvents can be used alone or in combination of two or more.

Of the aprotonic polar solvents, at least one selected from ethers, sulfones, sulfoxides, ureas and amides is preferable, and at least one selected from ethers, sulfones, ureas and amides. It is more preferable to contain a seed, and it is more preferable to contain at least a cyclic compound having a cyclic structure in the molecule (aprotonic polar solvent having a cyclic structure), cyclic ethers, cyclic sulfones, cyclic ureas and cyclics. Most preferably, it contains at least one selected from amides.

Examples of the cyclic ethers include tetrahydrofurans or dioxanes which may have a C _1-4 alkyl group such as tetrahydrofuran (THF) and 1,4-dioxane, and among them, a _C1-3 alkyl group. , 1,4-dioxane and the like, which may have a _C1-2 alkyl group, are more preferable, and 1,4-dioxane is most preferable. ..

Examples of the cyclic sulfones include tetra to pentamethylene sulfones which may have a C _1-4 alkyl group such as sulfolanes, and sulfolanes which may have a C _1-3 alkyl group are preferable. , Sulfolanes which may have a _C1-2 alkyl group are more preferable, and sulfolanes are most preferable.

The cyclic ureas may have a C _1-4 alkyl group such as DMI, N, N'-dimethyl-N, N'-trimethylene urea, and N, N'-di C _1-6 alkyl-. Examples thereof include N, N'-di to trimethylene ureas, and N, N'-di C _1-4 alkyl-ethylene ureas which may have a C _1-3 alkyl group are preferable, and C _1-2 alkyl is preferable. N, N'-di C _1-3 alkyl-ethylene ureas which may have a group are more preferable, and DMI is most preferable.

Examples of the cyclic amides include 5- to 7-membered ring lactams which may have a C _1-4 alkyl group such as NMP, and 5 to 6-membered which may have a C _1-3 alkyl group. Ring lactams are preferred, 5-membered ring lactams which may have a _C1-2 alkyl group are more preferred, and NMPs are most preferred.

The solvent may be composed of only the aprotonic polar solvent, but from the viewpoint of further improving the reactivity, usually, in addition to the aprotonic polar solvent (also referred to as a first solvent), further It often contains a second solvent selected from hydrocarbons and halogenated hydrocarbons.

Examples of the hydrocarbons include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and the like. Examples of the aliphatic hydrocarbons include linear or branched C _5-12 alkanes such as hexane, heptane, octane, and decane. Examples of alicyclic hydrocarbons include C _5-10 cycloalkanes such as cyclohexane. Examples of aromatic hydrocarbons include benzene; mono- or tri-C _1-6 alkyl-benzene such as toluene, xylene and ethylbenzene.

Examples of the halogenated hydrocarbons include halo C _1-6 alkanes such as methylene chloride, chloroform, carbon tetrachloride and 1,2-dichloroethane; and halobenzenes such as chlorobenzene and dichlorobenzene.

These second solvents can be used alone or in combination of two or more. Of these second solvents, aromatic hydrocarbons are preferred, mono- or tri-C _1-4 alkyl-benzenes are more preferred, and mono- or di-C _1-2 alkyl-benzenes such as toluene, xylene and ethylbenzene are more preferred. Good preferred, toluene most preferred.

The ratio of the total amount of the aprotonic polar solvent (first solvent) to the second solvent can be selected from the range of, for example, about 10% by mass or more (that is, 10 to 100% by mass) with respect to the entire solvent. The preferred range is, stepwise, 30% by mass or more, 50% by mass or more, 70% by mass or more, 90% by mass or more, 95% by mass or more, and 100% by mass, that is, substantially aprotonic polarity. Most preferably, it is composed of only a solvent and a second solvent. When a substantially aprotic polar solvent and a solvent other than the second solvent (also referred to as a third solvent) are contained, the ratio of the total amount of the aprotic polar solvent to the second solvent is, for example, It may be selected from the range of about 60 to 99% by mass, preferably 80 to 95% by mass.

When the solvent contains both an aprotonic polar solvent (first solvent) and a second solvent, the mass ratio of the aprotonic polar solvent to the second solvent such as aromatic hydrocarbons is. For example, the former / the latter can be selected from the range of about 0.01 / 99.99 to 50/50, and the preferable range is 0.05 / 99.95 to 30/70, 0.1 / in the following steps. It is 99.9 to 20/80, 0.5 / 99.5 to 18/82, 0.8 / 99.2 to 15/85, and most preferably 1/99 to 10/90. If the proportion of the aprotonic polar solvent is too large, the reactivity (reaction rate or reaction rate) may decrease, and if it is too small, the reactivity may not be reduced and the reactivity may decrease.

Specifically, the mass ratio of ethers, preferably cyclic ethers such as 1,4-dioxane, and aromatic hydrocarbons such as toluene is, for example, the former / the latter = 0.01 / 99.99 to 50. It can be selected from a range of about / 50, and the preferred range is 0.05 / 99.95 to 30/70, 0.1 / 99.9 to 10/90, 0.3 / 99.7 in stages. It is ~ 8/92, 0.5 / 99.5 to 5/95, 0.8 / 99.2 to 3/97, and most preferably 1/99 to 2/98.

The mass ratio of sulfones, preferably cyclic sulfones such as sulfolane, and aromatic hydrocarbons such as toluene can be selected from, for example, the former / the latter = 0.1 / 99.9 to 50/50. The preferred range is 0.5 / 99.5 to 30/70, 1/99 to 20/80, 3/97 to 15/85, 4/96 to 12/88, 5/95 in the following steps. It is ~ 10/90, most preferably 6/94 ~ 8/92.

The mass ratio of ureas, preferably cyclic ureas such as DMI, and aromatic hydrocarbons such as toluene can be selected from, for example, the former / the latter = 0.1 / 99.9 to 50/50. The preferred range is 0.5 / 99.5 to 30/70, 1/99 to 20/80, 3/97 to 15/85, 4/96 to 12/88, 5/95 in the following steps. It is about 10/90, and most preferably 6/94 to 8/92.

The mass ratio of amides, preferably cyclic amides such as NMP, and aromatic hydrocarbons such as toluene can be selected from, for example, the former / the latter = 0.1 / 99.9 to 50/50. The preferred range is 0.5 / 99.5 to 30/70, 1/99 to 20/80, 3/97 to 15/85, 5/95 to 12/88, 6/94 in the following steps. It is -10/90, most preferably 7/93 to 8/92.

The ratio of the solvent may be selected from the range of, for example, about 100 to 1000 parts by mass with respect to 100 parts by mass of fluorenone, and the preferable range is 150 to 700 parts by mass and 200 to 500 parts by mass in the following steps. Parts, more preferably 250 to 450 parts by mass, 280 to 400 parts by mass, and most preferably 300 to 350 parts by mass. If the proportion of the solvent is too large, the concentration of the raw material may be too low and the reactivity may be lowered, and if the proportion of the solvent is too small, the viscosity may be too high and the reactivity may be lowered.

In the present specification and the scope of patent claims, when an acid catalyst such as sulfuric acid or hydrochloric acid contains water, the water contained as the acid catalyst is treated as an acid catalyst instead of a solvent, and the ratio of the above solvent is used. It shall not be added.

[Reaction conditions]
The reaction temperature is not particularly limited, but can be selected from, for example, a range of about 0 to 200 ° C., and the preferred range is 5 to 150 ° C., 10 to 100 ° C., 15 to 80 ° C., 20 to 60 ° C. in a stepwise manner. Is. Above all, the reaction temperature is preferably 50 ° C. or lower, more preferably 20 to 50 ° C., and even more preferably, from the viewpoint of efficiently producing a fluorene derivative having a higher purity and suppressing coloring due to melting. The temperature is 25 to 45 ° C, most preferably 30 to 40 ° C. In the present invention, even if the reaction temperature is relatively low, not only the uniformity of the reaction system is high, but also the viscosity of the reaction system is low, so that the reaction proceeds efficiently. Therefore, by reducing the reaction temperature and suppressing side reactions, both high purity and high manufacturing efficiency can be achieved.

The reaction time is not particularly limited and can be selected from a range of, for example, about 30 minutes to 48 hours, and the preferred range is 1 to 24 hours, 2 to 12 hours, and 4 to 8 hours in a stepwise manner. ..

The reaction may be carried out with stirring, in air or in an inert atmosphere such as nitrogen gas or noble gas, or under normal pressure or pressure. Further, the reaction may be carried out while dehydrating.

In the method of the present invention, the fluorenones can be reacted at a high reaction conversion rate by carrying out the reaction under specific conditions using the raw material composition. Therefore, the reaction conversion rate of the fluorenones is usually 90 mol% or more, and by adjusting the composition of the raw material composition, for example, 92 mol% or more, preferably 93 mol% or more, still more preferably 95 mol% or more. , Most preferably 96 mol% or more, and by adjusting the raw material composition and reaction conditions, for example, 99 mol% or more, preferably 99.5 mol% or more, still more preferably 99.8 mol% or more. , More preferably 99.9 mol% or more, and most preferably 99.95 mol% or more.

In the present specification and claims, the conversion rate (reaction conversion rate) can be measured by the method described in Examples described later (method using HPLC) or the like.

[Separation / purification processing]
After the reaction is completed, the reaction mixture (reaction solution or reaction mixture) contains unreacted hydroxyl group-containing condensed polycyclic allenes, acid catalysts, thiols, in addition to the target product or the fluorene derivative which is the reaction product. Includes solvents, water, etc. Separation (or purification) of the fluorene derivative from such a reaction mixture is performed by conventional methods, for example, purification or separation means such as filtration, concentration, extraction, neutralization, washing, crystallization, recrystallization, column chromatography and the like. Alternatively, a purification or separation means combining these can be used. For example, the acid catalyst (and thiols) may be removed by a method of adding an alkaline aqueous solution for neutralization, and then the fluorene derivative may be crystallized and separated (purified).

In the method of the present invention, although the obtained fluorene derivative has high purity, it can be produced in a high yield, and the yield in the reaction may be 40 mol% or more with respect to the fluorenones used. However, it is preferably 50 mol% or more (50 to 100 mol%), and the preferable range is 53 mol% or more, 54 mol% or more, 55 mol% or more, 56 mol% or more in a stepwise manner. Most preferably, it is 57 mol% or more. The yield in the method of the present invention is usually about 53 to 100 mol%, and is stepwise 54 to 90 mol%, 55 to 80 mol%, 56 to 70 mol%, and most preferably 57 to 65. It is mol%.

[Fluorene derivative]
In the present invention, the fluorene derivative represented by the above formula (4) can be obtained by such a production method. In the formula (4), rings Z ¹ , ring Z ² , A ¹ , A ² , R ¹ , R ² , R ³ , m 1, m 2 and n are exemplified in the section of the alcohols and fluorenones, respectively. It is the same as rings Z ¹ , ring Z ² , A ¹ , A ² , R ¹ , R ² , R ³ , m1, m 2 and n in the formulas (1) to (3), including preferable embodiments.

In the above formula (4), the substitution position of the rings Z ¹ and Z ² bonded to the 9-position of the fluorene ring can be appropriately selected depending on the type of the rings Z ¹ and Z ² , and is not particularly limited. For example, when the rings Z ¹ and Z ² are naphthalene rings, they may be in either the 1-position or the 2-position, and are preferably in the 2-position.

The substitution positions of the HO-A ¹ O- group and the HO-A ² O- group can be appropriately selected depending on the type of the rings Z ¹ and Z ² , and are not particularly limited. For example, the rings Z ¹ and Z ² are naphthalene. In the case of a ring, it is usually substituted at any of the 5th to 8th positions of the naphthyl group bonded at the 1st or 2nd position with respect to the 9th position of the fluorene ring, and the 9th position of the fluorene ring is usually substituted. However, the 1-position or 2-position of the naphthalene ring is substituted (substituted in the relation of 1-naphthyl or 2-naphthyl), and the HO-A ¹ O- group and the HO-A ² O are substituted for this substitution position. -It is preferable that the group is substituted in the relationship of 1,5 or 2,6, and in particular, it is preferably substituted in the relationship of 2,6.

Typical examples of the fluorene derivative represented by the formula (4) are 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene and 9,9-bis [6- (2). -Hydroxypropoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene and the like can be mentioned. Of these, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene is preferable.

The fluorene derivative has a high purity, and the purity (HPLC purity) measured by HPLC (high performance liquid chromatography) can be selected from, for example, about 95% or more, and the preferable range is as follows. In addition, it is 96% or more, 97% or more, 97.5% or more, 98% or more, and most preferably 98.5% or more. The HPLC purity can usually be selected from the range of about 96 to 100%, preferably 98.5 to 99.99%, and more preferably 98.7 to 99.9%.

The fluorene derivative has a low total sulfur content and can effectively suppress coloring in a molten state. The total sulfur content can be selected from, for example, 150 ppm or less, specifically, 0 (or less than the lower limit of detection) to 120 ppm on a mass basis, and the preferable range is 0.001 in stages below. ~ 100ppm, 0.005 ~ 80ppm, 0.01 ~ 50ppm, 0.05 ~ 30ppm, 0.1 ~ 20ppm, 0.5 ~ 15ppm, 0.8 ~ 10ppm, 1 ~ 8ppm, 1.2 ~ 5ppm. , Most preferably 1.5 to 3 ppm.

The fluorene derivative has a small yellowness, and has a hue (YI) [or yellowness (YI)] of, for example, 0 in a molten state, typically, in a state of being melted by heating at 280 ° C. for 2 hours in a nitrogen atmosphere. It can be selected from a range of about 80 to 80, and the preferred range is 0.1 to 70, 0.5 to 65, 1 to 60, 5 to 55, 10 to 50, 15 to 45, 20 to 40 in stages. It is most preferably 25 to 35.

The HPLC purity, total sulfur content, hue (YI) at the time of melting, and yield can be measured by the methods described in Examples described later.

Since the fluorene derivative has a specific fluorene skeleton, it has various properties such as optical properties, heat resistance, water resistance, moisture resistance, chemical resistance, electrical properties, mechanical properties, dimensional stability, and the like. It is excellent and is useful for imparting (improving or improving) these properties in various applications. For example, since the fluorene derivative also has a high refractive index due to the skeleton, it can be used as a functional material, typically an additive for a resist, an additive for a resin, a curing agent (a curing agent for a resin), or the like. It can be suitably used as an additive or a raw material or intermediate thereof; a raw material or intermediate for pharmaceuticals, pesticides, etc .; a resin raw material such as a monomer, and is used as a compound for efficiently imparting the above-mentioned excellent properties. be able to. Among these uses, the fluorene derivative can significantly suppress (or reduce) coloring, especially coloring in a molten state, and is therefore synthesized (reaction or polymerization) at a high temperature of about 100 to 300 ° C. as a resin raw material. It can be suitably used as a raw material (or monomer) for a resin to be used, specifically, a polyester resin, a polycarbonate resin, or the like.

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

[Evaluation method]
( ^{1 1} H-NMR)
¹ H-NMR using a nuclear magnetic resonance apparatus (“ULTRA SHIELD® 300” manufactured by BRUKER), using deuterated chloroform (CDCl ₃ ) as a solvent and tetramethylsilane (TMS) as a standard substance. The spectrum was measured.

(GCMS)
Mass spectrometry (GCMS) was performed based on the following measuring devices and conditions.

Equipment: "7890GC / 5975MSD" manufactured by Agilent Technologies
Column temperature: 40 ° C-290 ° C (10 ° C / min) -290 ° C (20 minutes)
Ionization: EI method.

(HPLC purity)
The HPLC purity (% of area) of the sample was calculated by high performance (or high performance) liquid chromatography (HPLC) based on the following measuring devices and conditions.

Equipment: "LC-2010A HT" manufactured by Shimadzu Corporation
Column: "TSKgel ODS-80TM" manufactured by Tosoh Corporation
Detection method: UV, detection wavelength 254 nm
Eluent (volume ratio): Flow rate: 1.0 ml / min, acetonitrile / 0.1% by mass phosphoric acid aqueous solution = 55/45 → 95/5 (gradient).

(Total sulfur content)
The total sulfur content of the sample was measured by the oxidative decomposition-ultraviolet fluorescence method using "TS-2100H" manufactured by Mitsubishi Chemical Analytech Co., Ltd.

(Hue (YI))
The hue (YI) [or yellowness (YI)] of the sample is melted at 280 ° C for 2 hours under a nitrogen stream, and the color and turbidity simultaneous measuring instrument (“COH-400” manufactured by Nippon Denshoku Kogyo Co., Ltd.” ) Was measured.

[Extraction and identification of diol components]
2- (2-Hydroxynaphthoxy) From the raw material alcohol component containing ethanol (β-NEO) as the main component, use a silica gel column (eluent: toluene / ethyl acetate) as the diol component shown below 2- (2). -Hydroxyethoxy) -3- (2-hydroxyethyl) naphthalene was isolated.

The measurement results of ¹ H-NMR of 2- (2-hydroxyethoxy) -3- (2-hydroxyethyl) naphthalene are shown below, and the chart is shown in FIG.

^{1 1} H-NMR (CDCl ₃ ): δ (ppm) 2.5 (1H), 3.4 (2H), 3.6 (1H), 3.9 (4H), 4.2 (2H), 7. 2 (1H), 7.3 (1H), 7.4 (1H), 7.5 (3H)

The measurement results of GCMS of 2- (2-hydroxyethoxy) -3- (2-hydroxyethyl) naphthalene are shown below, and the chart is shown in FIG.

GC-MS: m / z = 232 (M), 201 (M-31, primary alcohol)

Further, the ratio of the diol component in the raw material alcohol component was quantified by HPLC analysis (internal standard method) using the isolated and purified diol component as a standard.

[Example 1]
9-Fluorenone (manufactured by Osaka Gas Chemical Co., Ltd., 99.0% or more) 90.1 g (0.500 mol) in a 2 L separable flask, raw material alcohol component containing β-NEO as the main component shown in Table 1. 282.0 g (1.50 mol in β-NEO conversion), 281.3 g of toluene and systemamine (manufactured by Tokyo Kasei Kogyo Co., Ltd., 95.0% or more) 6.6 g (0.085 mol), 1,4- 4.41 g of dioxane (manufactured by Kanto Chemical Co., Ltd., 99.0% or more, 0.10 mol) was added, and the temperature was raised to 40 ° C. to dissolve. After dissolution, 245.0 g of concentrated sulfuric acid (manufactured by Kanto Chemical Co., Inc., 98% by mass) was added dropwise in a temperature range of 30 to 40 ° C., and then the mixture was stirred at 30 to 40 ° C. for 3 hours. The results of confirming the reaction conversion rate of 9-fluorenone using HPLC are shown in Table 1 and FIG. Next, 69.1 g (0.500 mol) of 2-phenoxyethanol (manufactured by Kanto Chemical Co., Inc., 99.0% or more) was added, and the mixture was further stirred for 3 hours to obtain the desired product [9,9-bis [6-( 2-Hydroxyethoxy) -2-naphthyl] fluorene (BNEF)] was obtained.

From the results of Table 1 and FIG. 3, the ratio of diols [2- (2-hydroxyethoxy) -3- (2-hydroxyethyl) naphthalene] is 0.99% by mass or less (particularly 0.15% by mass) in the raw material alcohol component. % Or less), it was confirmed that the reaction conversion rate of 9-fluorenone was high.

[Example 2]
Using the raw material alcohol component containing 1- (2-hydroxynaphthoxy) ethanol (α-NEO) shown below in addition to β-NEO at the ratio shown in Table 2, the reaction solution was prepared in the same manner as in Example 1. Manufactured. The reaction conversion rate and yield are shown in Table 2.

To the obtained reaction solution, 281.3 g of methyl isobutyl ketone and 294.0 g of distilled water were added at 70 ° C. or lower, the temperature was raised to 70 ° C. and the mixture was sufficiently stirred to remove the aqueous phase, and the obtained organic phase was obtained. Further, 392.0 g of a 10 mass% sodium hydroxide aqueous solution was added while paying attention to the temperature rise. After stirring for 30 minutes, the organic phase obtained by removing the aqueous phase was sufficiently washed with distilled water and subjected to cooling crystallization.

In the cooling crystallization, seed crystals were added to the solution (organic phase) obtained at 40 ° C., and the crystals were aged for 3 hours to precipitate crystals, and then cooled to 10 ° C. or lower at a rate of 10 ° C./hour. After reaching 10 ° C. or lower, it was aged for another 4 hours, and coarse crystals were obtained by filtration. The target product (BNEF) was obtained by heating and washing the crude crystals at 60 ° C. using methanol having a mass three times that of the obtained crude crystals.

The evaluation results of the obtained BNEF are shown in Table 2.

From the results in Table 2, it was confirmed that the yield was greatly improved when the ratio of 1- (2-hydroxynaphthoxy) ethanol (α-NEO) in the raw material alcohol component was 0.90% by mass or less.

[Example 3]
Concentrated sulfuric acid was added dropwise by the same method as the production method using the raw material alcohol component 8 of Example 1 except that the synthetic scale was reduced to 1/20. After the dropping, 2- (2-hydroxyethoxy) -3- (2-hydroxyethyl) naphthalene is added to 1% by mass in the raw material composition at the reaction conversion rate of 80% while stirring at 30 to 40 ° C. Was added to. The result of confirming the reaction conversion rate every hour after the addition is shown in FIG. FIG. 4 shows the results of confirming the reaction conversion rate without adding 2- (2-hydroxyethoxy) -3- (2-hydroxyethyl) naphthalene. As is clear from FIG. 4, reaction inhibition was observed by the addition of 2- (2-hydroxyethoxy) -3- (2-hydroxyethyl) naphthalene, and 2- (2-hydroxyethoxy) -3- (2-hydroxy) was observed. It was confirmed that ethyl) naphthalene functions as a reaction regulator and reaction inhibitor.

The fluorene derivative obtained by the method of the present invention has reduced coloring and various properties such as optical properties, heat resistance, water resistance, moisture resistance, chemical resistance, electrical properties, mechanical properties, and dimensional stability. Excellent in sex. Therefore, the fluorene derivative is a resin raw material, for example, a raw material for a light or thermosetting resin such as an epoxy resin or a (meth) acrylic resin such as di (meth) acrylate, or a thermoplastic such as a polyester resin or a polycarbonate resin. Raw material for resin; It can be suitably used as a resin curing agent, for example, a curing agent for the light or heat-curable resin such as a curing agent for an epoxy-based resin.

In particular, since the fluorene derivative is excellent in optical properties, it is useful for forming (or forming) a molded body (optical molded body or optical member) for optical use. Examples of such an optical molded body include an optical film (or an optical sheet), an optical lens, and the like.

Further, the novel diols of the present invention can be used as a reaction modifier or a reaction terminator.

Claims (9)

In the presence of acid catalysts and thiols, the following formulas (1) and (2)

(During the ceremony,
Rings Z ¹ and Z ² represent fused polycyclic arene rings that are identical or different from each other.
A ¹ and A ² represent linear or branched C _2-4 alkylene groups that are identical or different from each other.
R ¹ and R ² indicate substituents that are the same or different from each other.
m1 and m2 are the same or different from each other and indicate integers greater than or equal to 0)
Alcohols represented by and the following formula (3)

(In the formula, R ³ indicates a substituent and n indicates an integer of 0 to 8).
By reacting with fluorenones represented by the following formula (4)

(In the formula, ring Z ¹ , ring Z ² , A ¹ , A ² , R ¹ , R ² , R ³ , m1, m2 and n are in formula (1), formula (2) or formula (3), respectively. same)
It is a method for producing a fluorene derivative represented by.
The following formula (5)

(During the ceremony,
Ring Z ³ represents a condensed polycyclic arene ring.
A ³ and A ⁴ represent linear or branched C _2-4 alkylene groups that are identical or different from each other.
^R4 indicates a substituent and represents a substituent.
k indicates an integer greater than or equal to 0)
A method in which the ratio of the diols represented by is 1 part by mass or less with respect to 100 parts by mass in total of the alcohols. In the formulas (1), (2), ( ⁴ ) and (5), the rings ^Z1 to Z3 ^are naphthalene rings, and the groups A1 to A4 are ^linear or branched _C2 . _-3 . The method according to claim 1, which is an alkylene group. The alcohols represented by the formulas (1) and (2) are the following formulas (1a) and (2a).

(In the equation, m1 and m2 indicate integers of 0 to 6 which are the same as or different from each other, and ^R1 and ^R2 are the same as the equation (1) or the equation (2), respectively).
The alcohols represented by the following formula (5a) and the diols represented by the above formula (5) are the alcohols represented by the following formula (5a).

(In the equation, k indicates an integer from 0 to 6, and ^R4 is the same as equation (5)).
The method according to claim 1 or 2, which is a diol represented by. The alcohols represented by the formulas (1) and (2) are 2- (2-naphthoxy) ethanol, and the diols represented by the formula (5) are 2- (2-hydroxyethoxy). The method according to any one of claims 1 to 3, which is -3- (2-hydroxyethyl) naphthalene. The method according to claim 4, wherein the ratio of 2- (1-naphthoxy) ethanol is 1 part by mass or less with respect to 100 parts by mass of 2- (2-naphthoxy) ethanol. A raw material composition for producing a fluorene derivative represented by the formula (4), which is an alcohol represented by the formulas (1) and (2) and a fluorenone represented by the formula (3). A raw material composition containing, and the ratio of the diols represented by the formula (5) is 1 part by mass or less with respect to 100 parts by mass in total of the alcohols. The alcohols represented by the formulas (1) and (2) are 2- (2-naphthoxy) ethanol, and the diols represented by the formula (5) are 2- (2-hydroxyethoxy)-. The sixth aspect of claim 6 is a 3- (2-hydroxyethyl) naphthalene and the ratio of 2- (1-naphthoxy) ethanol is 1 part by mass or less with respect to 100 parts by mass of the 2- (2-naphthoxy) ethanol. Raw material composition. In the presence of an acid catalyst and thiols, the alcohols represented by the formulas (1) and (2) are reacted with the fluorenones represented by the formula (3), and the formula (4) is used. In the method for producing the fluorene derivative to be prepared, the reaction conversion rate is adjusted by adjusting the ratio of the diols represented by the formula (5) to 1 part by mass or less with respect to 100 parts by mass of the total of the alcohols. How to improve. The diol represented by the above formula (5) according to claim 1.

Images