WO2018230394A1

WO2018230394A1 - Method for producing alcohols having fluorene skeleton

Info

Publication number: WO2018230394A1
Application number: PCT/JP2018/021539
Authority: WO
Inventors: 康春半田; 松浦　隆; 秀樹河井
Original assignee: 田岡化学工業株式会社
Priority date: 2017-06-15
Filing date: 2018-06-05
Publication date: 2018-12-20
Also published as: KR20200018392A; CN110461807A; CN110461807B; JP2019001780A; JP7128581B2

Abstract

Provided is a method for producing alcohols represented by formula (1), which sequentially comprises in the following order: a step (i) for obtaining a bisnaphthol compound represented by formula (2) by reacting 9-fluorenone and naphthol with each other in the presence of a solid acid; and a step (ii) for reacting the bisnaphthol compound represented by formula (2) with ethylene carbonate without taking out the bisnaphthol compound from the reaction system. (In the formulae, n1 and n2 may be the same or different, and each represents an integer of 1 or more.)

Description

Method for producing alcohol having fluorene skeleton

The present invention relates to a method for producing alcohols having a fluorene skeleton.

The following formula (1):

(In the formula, n ₁ and n ₂ are the same or different and each represents an integer of 1 or more.)
The alcohols represented by the formulas are particularly suitable as raw materials for optical resins because the resins produced from the alcohols and their derivatives are excellent in optical properties such as light transmittance, refractive index, and thermal properties such as heat resistance. [For example, International Publication No. 2016/047766 (Patent Literature 1), International Publication No. 2016/147847 (Patent Literature 2), Japanese Unexamined Patent Publication No. 2011-168723 (Patent Literature 3), Japanese Unexamined Patent Publication No. 2011-068624 Publication (Patent Document 4)].

On the other hand, almost no method for producing alcohols represented by the above formula (1) is known, and only the following two synthetic routes are known.
Method 1
In the presence of 1-methylimidazole and diethylene glycol, the following formula (2-1):

(For example, Patent Document 3 Synthesis Example 2, Patent Document 4 Reference Example 11)
Method 2
In the presence of sulfuric acid and 3-mercaptopropionic acid, 9-fluorenone and the following formula (3):

(For example, Patent Document 4 Examples 13 to 16)

International Publication No. 2016/047766 International Publication No. 2016/147847 JP 2011-168723 A JP 2011-068624 A

Method 1 describes that the purity of the alcohol represented by the above formula (1) is very low when the yield is very low or high.
In Method 2, although the yield and the purity of the alcohol represented by Formula (1) obtained by the method are relatively high, the alcohol represented by Formula (3) is generally difficult to obtain. Therefore, it is necessary to separately produce an alcohol represented by the formula (3), and since sulfuric acid is used in a large amount as a solvent and catalyst, it is not necessarily a method suitable for industrial implementation. .

An object of the present invention is to provide a production method suitable for industrial implementation of alcohols represented by the above formula (1).

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the bisnaphthol compound represented by the following formula (2) is unstable, and it is necessary to produce the compound under the specific conditions described below. It was also found that the alcohol represented by the above formula (1) having a high purity can be obtained in a high yield by reacting with ethylene carbonate without taking out the compound after the reaction. The present invention includes the following manufacturing methods.

[1]
The following formula (1):

(In the formula, n ₁ and n ₂ are the same or different and each represents an integer of 1 or more.)
A process for producing alcohols represented by:
In the presence of a solid acid, 9-fluorenone and naphthol are reacted to form the following formula (2):

A step (i) of obtaining a bisnaphthol compound represented by:
A step (ii) of reacting the bisnaphthol compound represented by the formula (2) with ethylene carbonate without taking it out;
In this order.

[2]
The production method according to [1], wherein the solid acid is a heteropolyacid and / or a cation exchange resin.

[3]
The production method according to [1] or [2], wherein the step (i) is performed in the presence of an aliphatic chain ester and / or an aliphatic cyclic ester.

According to the present invention, a highly pure alcohol represented by the above formula (1) can be obtained in high yield from 9-fluorenone and naphthol, which are generally available raw materials.
Since the alcohol represented by the above formula (1) can be produced without taking out the compound represented by the above formula (2) and the number of production steps can be greatly reduced, it is particularly advantageous for industrial implementation. It can be said that it is a manufacturing method.

As described above, the present invention includes the steps (i) and (ii) in this order in the production of the alcohol represented by the above formula (1).

Step (i)
A step of reacting 9-fluorenone with naphthol in the presence of a solid acid to obtain a bisnaphthol compound represented by the above formula (2).
Step (ii)
The step of reacting the bisnaphthol compound represented by the above formula (2) with ethylene carbonate without taking it out.
Hereinafter, the steps (i) and (ii) will be described in detail.

The solid acid used in the present invention may be an inorganic solid acid or an organic solid acid.
Examples of the inorganic solid acid include metal compounds; non-metal sulfates; clay minerals; zeolites; kaolin and the like.
Examples of the metal compound include oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ , Fe ₂ O ₃ , ZrO ₂ , SnO ₂ , and V ₂ O ₅ ; SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , Composite oxides such as TiO ₂ —ZrO ₂ and SiO ₂ —ZrO ₂ ; sulfides such as ZnS; CaSO ₄ , Fe ₂ (SO ₄ ) ₃ , CuSO ₄ , NiSO ₄ , Al ₂ (SO ₄ ) ₃ , MnSO ₄ Sulfates such as BaSO ₄ , CoSO ₄ , ZnSO ₄ ; polyacids containing elements such as P, Mo, V, W, Si, etc. (phosphates such as phosphates of AlPO ₄ , Ti, etc.); different 2 Composite oxide acids composed of more than one kind of oxide complex; and heteropolyacids in which part or all of the protons of the acid of the polyacid or complex oxide acid are replaced with other cations) It is.
Examples of the nonmetal sulfate include (NH ₄ ) ₂ SO ₄ .
Examples of clay minerals include acid clay and montmorillonite.
Zeolite, Y-type having an acidic OH group, X type, A type, ZSM5, _mordenite, VIPI _{_5,} AlPO 4 _-5, and the like AlPO ₄ -11.
Examples of the organic solid acid include a cation exchange resin.
The solid acid may be porous or non-porous depending on the type of the solid acid, and only one kind may be used as necessary, or two or more kinds may be used in combination. Among these solid acids, a heteropolyacid or a cation exchange resin is preferred because of its excellent handleability and availability, and a heteropolyacid is more preferred.
Hereinafter, preferred embodiments of the heteropolyacid and the cation exchange resin will be described in detail.

Heteropolyacids include, for example, oxyacid ions of elements such as phosphorus, arsenic, tin, silicon, titanium, and zirconium (eg, phosphoric acid and silicic acid) and oxyacid ions of elements such as molybdenum, tungsten, vanadium, niobium, and tantalum. (For example, vanadic acid, molybdic acid, tungstic acid), and various heteropolyacids can be selected depending on the combination thereof.

Examples of the elements contained in the oxygen acid constituting the heteropolyacid include copper, beryllium, boron, aluminum, carbon, silicon, germanium, tin, titanium, zirconium, cerium, thorium, nitrogen, phosphorus, arsenic, antimony, vanadium, Examples include niobium, tantalum, chromium, molybdenum, tungsten, uranium, selenium, tellurium, manganese, iodine, iron, cobalt, nickel, rhodium, osmium, iridium, platinum, and the like.
Among them, from the viewpoint of availability, a heteropolyacid containing at least one element selected from silicon, vanadium, molybdenum and tungsten is preferable, and phosphorus or silicon and at least one element selected from vanadium, molybdenum and tungsten The heteropolyacid containing is more preferable. Specifically, preferred examples of the heteropolyacid include phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, and phosphovanadomolybdic acid.

The heteropolyacid that can be used in the present invention may be a heteropolyacid salt in which a part or all of protons are replaced with other cations. Examples of cations that can replace protons include ammonium cations, alkali metal cations, alkaline earth metal cations, and the like. In addition, the heteropolyacid may be an anhydride or a crystal water-containing material.

Examples of the cation exchange resin (cationic ion exchange resin, acid ion exchange resin) that can be used in the present invention include strong acid cation exchange resins and weak acid cation exchange resins.
Examples of the strongly acidic cation exchange resin include an ion exchange resin having a sulfonic acid group.
As an ion exchange resin having a sulfonic acid group, for example,
Sulfonated products of crosslinked polystyrene such as styrene-divinylbenzene copolymer,
Examples thereof include a fluorine-containing resin having a sulfonic acid group (or —CF ₂ CF ₂ SO ₃ H group).
Examples of the fluorine-containing resin include fluorine-containing ion exchange resins such as a block copolymer of [2- (2-sulfotetrafluoroethoxy) hexafluoropropoxy] trifluoroethylene and tetrafluoroethylene.
Examples of the block copolymer include Nafion manufactured by DuPont.
Examples of the weakly acidic cation exchange resin include an ion exchange resin having a carboxylic acid group.
Examples of the ion exchange resin having a carboxylic acid group include methacrylic acid-divinylbenzene copolymer and acrylic acid-divinylbenzene copolymer.
Among the above cation exchange resins, strong acid cation exchange resins, in particular, strong acid cation exchange resins having a styrene-divinylbenzene copolymer as a base (or base) are preferably used.

The amount of the solid acid used is, for example, 0.0001 parts by weight or more, preferably 0.001 to 30 parts by weight, more preferably 0.01 to 5 parts by weight with respect to 1 part by weight of 9-fluorenone.

When carrying out step (i), the above-mentioned solid acid may be dispersed or dissolved in water or the organic solvent described below and then used in step (i). When liquid inorganic acid (sulfuric acid, hydrochloric acid, etc.) and organic acid (methanesulfonic acid, etc.) are used instead of solid acid, the bisnaphthol compound represented by the above formula (2) is reacted with ethylene carbonate without taking it out. However, it may be difficult to obtain a high-purity alcohol represented by the above formula (1) in a high yield even if it can be reacted.

In carrying out the present invention, the reaction rate can be improved by using a compound having an SH group together with a solid acid. Examples of the compound having an SH group that may be used in the present invention include mercaptocarboxylic acid, alkyl mercaptan, aralkyl mercaptan, and salts thereof.
Examples of the mercaptocarboxylic acid include thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, and mercaptobenzoic acid.
Examples of alkyl mercaptans include C _1-16 alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, and dodecyl mercaptan.
Examples of aralkyl mercaptan include benzyl mercaptan.
Examples of the salt include alkali metal salts (for example, sodium salts such as methyl mercaptan sodium and ethyl mercaptan sodium).
Among the compounds having an SH group, β-mercaptopropionic acid and dodecyl mercaptan are preferable because they are available at low cost. These SH group-containing compounds may be used alone or in combination of two or more if necessary.

When a compound having an SH group is used, the amount of the compound having an SH group is, for example, 0.0001 parts by weight or more, preferably 0.001 to 30 parts by weight, more preferably 1 part by weight of 9-fluorenone. 0.01 to 3 parts by weight.

The naphthol used in the present invention may be either 1-naphthol (α-naphthol) or 2-naphthol (β-naphthol).
The amount of naphthol to be used is, for example, usually 2 to 20 mol, preferably 2.1 to 5 mol, per 1 mol of 9-fluorenone. By using 2 mol or more, it becomes possible to produce the bisnaphthol compound represented by the above formula (2) with a higher yield, and by reducing the amount used to 20 mol or less, unreacted naphthol can be reduced. Is possible.

When carrying out step (i), an organic solvent may be used, or an organic solvent may not be used, but it is preferable to use an organic solvent in order to carry out step (i) more efficiently. .
Usable organic solvents include, for example, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, esters, aliphatic nitriles, and the like. Can be mentioned.
Aromatic hydrocarbons include toluene, xylene, mesitylene and the like.
Examples of halogenated aromatic hydrocarbons include chlorobenzene and dichlorobenzene.
Examples of the aliphatic hydrocarbons include pentane, hexane, heptane and the like.
Examples of halogenated aliphatic hydrocarbons include dichloromethane and 1,2-dichloroethane.
Examples of ethers include diethyl ether, diisopropyl ether, methyl tert-butyl ether, cyclopentyl 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 Le, and the like.
Esters include ethyl acetate, butyl acetate, cellosolve acetate, methyl lactate, butyl lactate, ethyl lactate, γ-butyrolactone, δ-valerolactone, butyl benzoate, methyl benzoate, phenyl acetate, ethylene carbonate, propylene carbonate, etc. Can be mentioned.
Examples of aliphatic nitriles include acetonitrile.
Only one organic solvent may be used, or two or more organic solvents may be mixed and used as necessary.

Among the above organic solvents, the solubility of the bisnaphthol compound represented by the above formula (2) is high, and the step (ii) is more efficiently performed when the step (ii) is performed without taking out the compound. Since it becomes possible, aliphatic chain esters (ethyl acetate, butyl acetate, cellosolve acetate, methyl lactate, butyl lactate, ethyl lactate, etc.) and / or aliphatic cyclic esters (γ-butyrolactone, δ-valerolactone, It is preferable to use an organic solvent containing ethylene carbonate, propylene carbonate and the like.

In the case of using an organic solvent, the amount of use should be such that 9-fluorenone and naphthol as raw materials and part or all of the bisnaphthol compound represented by the above formula (2) as a product are dissolved in the organic solvent. Specifically, for example, it is usually 1 to 30 parts by weight, preferably 2 to 5 parts by weight per 1 part by weight of 9-fluorenone.

Step (i) is usually performed at 70 to 130 ° C, preferably 80 to 100 ° C. During the reaction, it is preferable that the internal pressure is lower than 101.3 kPa, more preferably 49.3 kPa or less, and the reaction is carried out while removing by-product water from the system because the reaction proceeds more efficiently.

After step (i), the solid acid used in step (i) may be removed by filtration or neutralized as necessary. Examples of bases that can be used for neutralization include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide, potassium carbonate, calcium carbonate, sodium carbonate, and sodium bicarbonate. Examples include alkali metal or alkaline earth metal carbonates (hydrogen carbonates), amines, and the like.

Usually, the reaction solution after neutralization can be used in step (ii) without removing the salt produced by neutralization. Further, if necessary, the salt generated by neutralization is removed by filtration, or water is added to the reaction solution, stirred and allowed to stand, and then the aqueous layer is removed (hereinafter also referred to as a water washing step). In some cases, the salt produced by neutralization may be removed from the reaction solution. The water washing step may be repeated a plurality of times as necessary.

After step (i), it is necessary to react with ethylene carbonate without taking out the bisnaphthol compound represented by the above formula (2). When the bisnaphthol compound represented by the above formula (2) is taken out by a conventional method such as concentration and crystallization, the alcohols represented by the above formula (1) as shown in the section of the following [Example] and the like. In some cases, the yield of the alcohol represented by the above formula (1) may be reduced.

In carrying out the step (ii), the bisnaphthol compound represented by the above formula (2) contained in the reaction solution is in a completely dissolved state even in a state where crystals are partially precipitated (slurry state). However, in carrying out step (ii), step (ii) can be carried out more efficiently when the crystals of the bisnaphthol compound represented by formula (2) are completely dissolved. This is preferable.

In step (ii), ethylene carbonate is usually used in an amount of 2 to 10 mol, preferably 2 to 4 mol, per 1 mol of 9-fluorenone used in step (i).

When carrying out step (ii), the reaction may be carried out in the presence of a basic compound as necessary. When the reaction is performed in the presence of a basic compound, it is preferable to remove or neutralize the solid acid used in step (i) by filtration before performing step (ii).
Examples of basic compounds that can be used in step (ii) include carbonates, bicarbonates, hydroxides, organic bases, and the like.
Examples of carbonates include potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate and the like.
Examples of the hydrogen carbonates include potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate and the like.
Examples of hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like.
Examples of organic bases include triethylamine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, tetramethylammonium chloride and the like.
Among the above basic compounds, potassium carbonate, sodium carbonate and triphenylphosphine are preferably used from the viewpoint of good handleability.
Only 1 type may be used for a basic compound, or 2 or more types may be mixed and used as needed.
When a basic compound is used, the amount used is usually 0.01 to 1.0 mol, preferably 0.03 to 0.5 mol, relative to 1 mol of 9-fluorenone used in step (i). .

In carrying out step (ii), by using an excessive amount of ethylene carbonate, the reaction may be carried out using ethylene carbonate as a solvent, or in the presence of other organic solvents.
Examples of the organic solvent include ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, esters, aliphatic nitriles, amides, Examples include sulfoxides.
Ketones include acetone, methyl ethyl ketone, butyl methyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, 2-octanone, cyclohexanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclodecanone, Examples include cycloundecanone.
Aromatic hydrocarbons include toluene, xylene, mesitylene and the like.
Examples of halogenated aromatic hydrocarbons include chlorobenzene and dichlorobenzene.
Examples of the aliphatic hydrocarbons include pentane, hexane, heptane and the like.
Examples of halogenated aliphatic hydrocarbons include dichloromethane and 1,2-dichloroethane.
Examples of ethers include diethyl ether, diisopropyl ether, methyl tert-butyl ether, cyclopentyl 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 Le, and the like.
Examples of the esters include ethyl acetate, butyl acetate, γ-butyrolactone, and δ-valerolactone.
Examples of aliphatic nitriles include acetonitrile.
Examples of amides include dimethylformamide and dimethylacetamide.
Examples of the sulfoxides include dimethyl sulfoxide.
Among the above organic solvents, an organic solvent having a boiling point of 110 ° C. or higher and an organic solvent selected from aromatic hydrocarbons, ketones, esters and ethers is preferably used because of its availability and ease of handling. It is done.
Only one type of organic solvent may be used, or two or more types may be used in combination as required.
When an organic solvent is used, the amount used is usually 0.1 to 10 parts by weight, preferably 0.5 to 3 parts by weight, based on 1 part by weight of 9-fluorenone used in step (i).

Step (ii) is usually carried out at 30 to 150 ° C., preferably 100 to 130 ° C.

After the step (ii) is completed, the basic compound used in the step (ii) is neutralized as necessary, and then the alcohol represented by the above formula (1) is taken out by a conventional method such as concentration and crystallization. be able to. In addition, since the alcohol represented by the above formula (1) having a high purity can be obtained in a high yield as compared with the known method, the reaction solution obtained after the completion of the step (ii) is obtained by the above formula (1). ) Can be used as it is as a resin raw material without taking out the alcohol represented by

Hereinafter, the present invention will be specifically described with reference to examples and the like, but the present invention is not limited to these examples. Further, the production rate (residual rate) and purity of each component described in Examples and Comparative Examples are HPLC area percentage values measured under the following conditions, and the yield is solid with respect to 9-fluorenone unless otherwise specified. Yield.

(1) HPLC analysis conditions Apparatus: LC-2010AHT manufactured by Shimadzu Corporation
Column: XBridge Shield RP18 (3.5 μm, 4.6 mmφ × 250 mm) manufactured by Waters
Mobile phase: pure water / acetonitrile (acetonitrile 65% (10 min) → 100% (10 min) → 65% (10 min)

<Example 1>
To a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer, 9-fluorenone 30.0 g (0.17 mol), 2-naphthol 57.6 g (0.40 mol), n-dodecyl mercaptan 1.79 g (0.008 mol), 45.0 g of toluene, 14.8 g of γ-butyrolactone and 0.8 g of phosphotungstic acid were added, the pressure was reduced to 49.3 kPa, the temperature was raised to 100 ° C., and the mixture was stirred at the same temperature for 7 hours, followed by HPLC It was confirmed that the residual ratio of 9-fluorenone was 0.2% or less.
Next, 0.9 g of a 24% aqueous solution of sodium hydroxide (hereinafter sometimes referred to as caustic water) was added to the resulting reaction solution to neutralize phosphotungstic acid, and then the temperature was raised to 120 ° C. to maintain the water. I made it come out.
Thereafter, 1.2 g of potassium carbonate, 36.6 g of ethylene carbonate, and 1.5 g of toluene were added to the reaction liquid, and the temperature was raised to 110 ° C., followed by stirring at the same temperature for 13 hours. The disappearance of the bisnaphthol compound represented was confirmed.
After completion of the reaction, 7.5 g of water and 26.3 g of 24% caustic water were added to the resulting reaction solution, and the temperature was raised to 75 to 85 ° C. and stirred at the same temperature for 4 hours. After stirring, the aqueous layer is separated and removed, and the following formula (1-1):

An organic layer containing an alcohol compound represented by the following was recovered. Next, the recovered organic layer was cooled to 20 ° C. to precipitate crystals, and the precipitated crystals were separated by filtration. The crystals separated by filtration were washed with water and then dried at 120 ° C. under reduced pressure of 1.3 kPa for 8 hours to obtain an alcohol compound represented by the above formula (1-1). The yield, yield and purity of the alcohol compound represented by the above formula (1-1) are shown below.

Weight of the obtained crystal: 81.1 g (Yield: 90.4%)
HPLC purity: 95.8%

<Example 2>
To a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer, 9-fluorenone 30.0 g (0.17 mol), 2-naphthol 57.6 g (0.40 mol), n-dodecyl mercaptan 1.79 g (0.008 mol), 30.0 g of toluene, 30.0 g of ethyl acetate and 0.8 g of phosphotungstic acid were charged, the pressure was reduced to 56.7 kPa, the temperature was raised to 100 ° C., and the mixture was stirred at the same temperature for 4 hours. It was confirmed that the residual ratio of 9-fluorenone was 0.2% or less.
Next, 0.9 g of 24% caustic water was added to the obtained reaction liquid to neutralize phosphotungstic acid, and then the temperature was raised to 120 ° C. to distill water.
Thereafter, 1.2 g of potassium carbonate, 36.6 g of ethylene carbonate, and 1.5 g of toluene were added to the reaction solution, the temperature was raised to 110 ° C., and the mixture was stirred at the same temperature for 16 hours. The disappearance of the bisnaphthol compound represented was confirmed.
After completion of the reaction, 7.5 g of water and 26.3 g of 24% caustic water were added to the obtained reaction solution, and the temperature was raised to 75 to 85 ° C. and stirred at the same temperature for 2 hours. After stirring, the aqueous layer was separated and removed, and the organic layer containing the alcohol compound represented by the above formula (1-1) was recovered. Next, the recovered organic layer was cooled to 20 ° C. to precipitate crystals, and the precipitated crystals were separated by filtration. The crystals separated by filtration were washed with water and then dried at 120 ° C. under reduced pressure of 1.3 kPa for 8 hours to obtain an alcohol compound represented by the above formula (1-1). The yield, yield and purity of the alcohol compound represented by the above formula (1-1) are shown below.

Weight of the obtained crystal: 80.6 g (Yield: 89.9%)
HPLC purity: 94.1%

<Example 3>
The alcohol compound represented by the above formula (1-1) was obtained in the same manner as in Example 2 except that ethyl acetate was changed to butyl acetate. The yield, yield and purity of the alcohol compound represented by the above formula (1-1) are shown below.

Weight of the obtained crystal: 80.9 g (Yield: 90.2%)
HPLC purity: 94.6%

<Example 4>
The same procedure as in Example 1 was carried out except that phosphotungstic acid was changed to silicotungstic acid to obtain an alcohol compound represented by the above formula (1-1). The yield, yield and purity of the alcohol compound represented by the above formula (1-1) are shown below.

Weight of the obtained crystal: 79.8 g (Yield: 89.0%)
HPLC purity: 96.3%

<Example 5>
The same procedure as in Example 1 was carried out except that the amount of toluene used was changed from 45.0 g to 90.0 g and the amount of γ-butyrolactone was changed from 14.8 g to 30.0 g. The alcohol compound shown by was obtained. The yield, yield and purity of the alcohol compound represented by the above formula (1-1) are shown below.

Weight of the obtained crystal: 80.0 g (Yield: 89.2%)
HPLC purity: 96.1%

<Example 6>
The alcohol compound represented by the above formula (1-1) was obtained in the same manner as in Example 1, except that n-dodecyl mercaptan was changed to β-mercaptopropionic acid. The yield, yield and purity of the alcohol compound represented by the above formula (1-1) are shown below.

Weight of the obtained crystal: 79.5 g (Yield: 88.7%)
HPLC purity: 95.6%

<Example 7>
In a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer, 9-fluorenone 20.0 g (0.11 mol), 2-naphthol 38.4 g (0.27 mol), β-mercaptopropionic acid 0. 58 g (0.012 mol), 35.0 g of toluene, 5.0 g of γ-butyrolactone and 1.0 g of phosphotungstic acid were charged, the temperature was raised to 120 ° C., and the mixture was stirred at the same temperature for 2 hours. It was confirmed that the residual rate was 0.2% or less.
Subsequently, 1.3 g of 24% caustic water was added to the obtained reaction liquid to neutralize phosphotungstic acid, and then the temperature was raised to 120 ° C. to distill off the water.
Thereafter, 0.3 g of potassium carbonate and 14.7 g of ethylene carbonate were added to the reaction solution, the temperature was raised to an internal temperature of 110 ° C., and the mixture was stirred at the same temperature for 11 hours, and represented by the above formula (2-1) by HPLC. The disappearance of the bisnaphthol compound was confirmed.
After completion of the reaction, 10 g of water and 17.5 g of 24% caustic water were added to the resulting reaction solution, and then the temperature was raised to 75 to 85 ° C. and stirred at the same temperature for 4 hours. After stirring, the aqueous layer was separated and removed, and the organic layer containing the alcohol compound represented by the above formula (1-1) was recovered. Next, the recovered organic layer was cooled to 20 ° C. to precipitate crystals, and the precipitated crystals were separated by filtration. The crystals separated by filtration were dried at 120 ° C. under reduced pressure of 1.3 kPa for 8 hours to obtain an alcohol compound represented by the above formula (1-1). The yield, yield and purity of the alcohol compound represented by the above formula (1-1) are shown below.

Weight of the obtained crystal: 47.7 g (yield: 79.8%)
HPLC purity: 95.1%

<Example 8>
In a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer, 9-fluorenone 20.0 g (0.11 mol), 2-naphthol 38.4 g (0.27 mol), β-mercaptopropionic acid 0. 58 g (0.012 mol), 35.0 g of toluene, 5.0 g of γ-butyrolactone and 4.0 g of Amberlyst 15DRY (manufactured by Organo) were charged, the temperature was raised to 120 ° C., and the mixture was stirred at the same temperature for 6 hours. It was confirmed that the residual ratio of 9-fluorenone was 0.2% or less.
Next, Amberlyst 15DRY was filtered off from the obtained reaction solution. Thereafter, 0.3 g of potassium carbonate and 14.7 g of ethylene carbonate were added to the reaction solution, the temperature was raised to an internal temperature of 110 ° C., and the mixture was stirred at the same temperature for 6 hours, and represented by the above formula (2-1) by HPLC. The disappearance of the bisnaphthol compound was confirmed.
After completion of the reaction, 10 g of water and 17.5 g of 24% caustic water were added to the resulting reaction solution, and then the temperature was raised to 75 to 85 ° C. and stirred at the same temperature for 4 hours. After stirring, the aqueous layer was separated and removed, and the organic layer containing the alcohol compound represented by the above formula (1-1) was recovered. Next, the recovered organic layer was cooled to 20 ° C. to precipitate crystals, and the precipitated crystals were separated by filtration. The crystals separated by filtration were dried at 120 ° C. under reduced pressure of 1.3 kPa for 8 hours to obtain an alcohol compound represented by the above formula (1-1). The yield, yield and purity of the alcohol compound represented by the above formula (1-1) are shown below.

Weight of the obtained crystal: 51.1 g (Yield: 85.5%)
HPLC purity: 96.7%

<Comparative Example 1>
In Example 1, step (i) was carried out in the same manner except that 0.8 g of phosphotungstic acid was changed to 25.8 g of 98% sulfuric acid. As a result, the residual ratio of 9-fluorenone was 0.2% or less. It took 15 hours. Thereafter, the same procedure as in Example 1 was performed to obtain an alcohol compound represented by the above formula (1-1). The yield, yield and purity of the alcohol compound represented by the above formula (1-1) are shown below.

Weight of the obtained crystal: 34.5 g (Yield: 38.5%)
HPLC purity: 41.0%

<Comparative example 2>
In Example 1, step (i) was carried out in the same manner except that 0.8 g of phosphotungstic acid was changed to 6.0 g of methanesulfonic acid. As a result, the residual ratio of 9-fluorenone was 0.2% or less. It took 20 hours. Thereafter, the same procedure as in Example 1 was performed to obtain an alcohol compound represented by the above formula (1-1). The yield, yield and purity of the alcohol compound represented by the above formula (1-1) are shown below.

Weight of the obtained crystal: 30.1 g (Yield: 33.6%)
HPLC purity: 35.1%

<Comparative Example 3>
In a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer, 9-fluorenone 60.0 g (0.33 mol), 2-naphthol 115.3 g (0.80 mol), β-mercaptopropionic acid 1. 79 g (0.012 mol), 120 g of toluene, and 1.5 g of phosphotungstic acid were added, the temperature was raised to 120 ° C., and the mixture was stirred at the same temperature for 4 hours. The residual ratio of 9-fluorenone was 0.2% or less by HPLC. It was confirmed that.
To the obtained reaction solution, 120 g of toluene, 90 g of water, 3.6 g of 24% caustic water were added to neutralize phosphotungstic acid, and then cooled to 40 ° C. and stirred at the same temperature for 1 hour to precipitate crystals. After further cooling to 20 ° C., 93.4 g of crystals of the bisnaphthol compound represented by the above formula (2-1) were obtained.
The obtained bisnaphthol compound crystal represented by the above formula (2-1) 30.0 g, 45 g of toluene, 0.7 g of potassium carbonate and 14.8 g of ethylene carbonate were charged, and the temperature was raised to 110 ° C. After stirring for 8 hours, disappearance of the bisnaphthol compound represented by the above formula (2-1) was confirmed by HPLC.
After 7.5 g of water and 7.6 g of 24% caustic water were added to the obtained reaction liquid, the temperature was raised to 75 to 85 ° C. and the mixture was stirred at the same temperature for 4 hours. After stirring, the aqueous layer was separated and removed, and the organic layer containing the alcohol compound represented by the above formula (1-1) was recovered. Next, the recovered organic layer was cooled to 20 ° C. to precipitate crystals, and the precipitated crystals were separated by filtration. The crystals separated by filtration were dried at 120 ° C. under reduced pressure of 1.3 kPa for 8 hours to obtain an alcohol compound represented by the above formula (1-1). The yield, yield and purity of the alcohol compound represented by the above formula (1-1) are shown below.

Weight of the obtained crystal: 30.4 g (Yield: 52.7%)
HPLC purity: 88.5%

Claims

The following formula (1):

(In the formula, n 1 and n 2 are the same or different and each represents an integer of 1 or more.)
A process for producing alcohols represented by:
In the presence of a solid acid, 9-fluorenone and naphthol are reacted to form the following formula (2):

A step (i) of obtaining a bisnaphthol compound represented by:
A step (ii) of reacting the bisnaphthol compound represented by the formula (2) with ethylene carbonate without taking it out;
In this order.
The production method according to claim 1, wherein the solid acid is a heteropolyacid and / or a cation exchange resin.
The production method according to claim 1 or 2, wherein step (i) is carried out in the presence of aliphatic chain esters and / or aliphatic cyclic esters.