WO2021182238A1 - 1,1'-bi-2-naphthol composition - Google Patents

1,1'-bi-2-naphthol composition Download PDF

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WO2021182238A1
WO2021182238A1 PCT/JP2021/008179 JP2021008179W WO2021182238A1 WO 2021182238 A1 WO2021182238 A1 WO 2021182238A1 JP 2021008179 W JP2021008179 W JP 2021008179W WO 2021182238 A1 WO2021182238 A1 WO 2021182238A1
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naphthol
mass
toluene
chlorotoluene
ethyl acetate
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PCT/JP2021/008179
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French (fr)
Japanese (ja)
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紀明 小森
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第一工業製薬株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/06—Toluene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/02—Monocyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/14—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with at least one hydroxy group on a condensed ring system containing two rings

Definitions

  • the present invention relates to a 1,1'-bi-2-naphthol composition.
  • 1,1'-bi-2-naphthol and its derivatives are used as raw materials for metal complex catalysts and optical materials, and 1,1'-bi-2-naphthol obtained by various production methods. Is provided (see Patent Documents 1 and 2).
  • the reaction is generally carried out by dissolving 1,1'-bi-2-naphthol in an organic solvent.
  • 1,1'-bi-2-naphthol has a problem that it takes a long time to dissolve in ethyl acetate.
  • an embodiment of the present invention aims to improve the dissolution rate of 1,1'-bi-2-naphthol in ethyl acetate.
  • the present inventor has made various studies on the acetate of 1,1'-bi-2-naphthol by adding toluene and / or chlorotoluene to the racemic 1,1'-bi-2-naphthol. It has been found that the rate of dissolution in ethyl is improved.
  • Embodiments of the present invention contain racemic 1,1'-bi-2-naphthol, toluene and / or chlorotoluene, and acetic acid containing 5% by mass of racemic 1,1'-bi-2-naphthol.
  • a 1,1'-bi-2-naphthol composition having a Hazen color number APHA of 40 or less when prepared as an ethyl solution.
  • racemic mixture is used as 1,1'-bi-2-naphthol, and 1,1'-bi-2-naphthol is dissolved in ethyl acetate by adding toluene and / or chlorotoluene.
  • the speed can be improved.
  • deterioration of the hue of 1,1'-bi-2-naphthol in an ethyl acetate solution can be suppressed.
  • the 1,1'-bi-2-naphthol composition according to the present embodiment contains racemic 1,1'-bi-2-naphthol, toluene and / or chlorotoluene.
  • 1,1'-bi-2-naphthol also called BINOL
  • BINOL has two optical isomers (ie, (R) -1,1'-bi-2-naphthol, (S) -1,1'-bi- 2-Naftor).
  • a racemic mixture that is, (RS) -1,1'-bi-2-naphthol
  • the dissolution rate in ethyl acetate can be increased as compared with the case where the R-form or S-form is used.
  • toluene and / or chlorotoluene is contained together with racemic 1,1'-bi-2-naphthol.
  • 1,1'-bi-2-naphthol does not dissolve in toluene or chlorotoluene at room temperature, but by adding toluene or chlorotoluene, the dissolution rate of 1,1'-bi-2-naphthol in ethyl acetate Can be raised. The reason is not clear, but it is thought that toluene and chlorotoluene act as co-solvents at room temperature.
  • Examples of chlorotoluene include 2-chlorotoluene, 3-chlorotoluene, and 4-chlorotoluene, and 2-chlorotoluene is preferably used.
  • the content of toluene and / or chlorotoluene (that is, the content of toluene in the case of toluene alone, the content of chlorotoluene in the case of chlorotoluene alone, the total content of both in the case of combined use of toluene and chlorotoluene) , 500 mass ppm or more with respect to the mass of the rasemi form 1,1'-bi-2-naphthol is preferable in order to enhance the effect of improving the dissolution rate in ethyl acetate.
  • This content is more preferably 1000 mass ppm or more, and may be 1 mass% or more.
  • the upper limit of the content of toluene and / or chlorotoluene is not particularly limited, and may be, for example, 50% by mass or less, or 25% by mass or less, based on the mass of racemic 1,1'-bi-2-naphthol. , 15% by mass or less.
  • the content of toluene and / or chlorotoluene can be quantified by GC (gas chromatograph).
  • the 1,1'-bi-2-naphthol composition according to the present embodiment is Hazen when dissolved in ethyl acetate to prepare a ethyl acetate solution containing 5% by mass of racemic 1,1'-bi-2-naphthol.
  • the number of colors APHA is 40 or less. This makes it possible to suppress the deterioration of the hue of 1,1'-bi-2-naphthol in the ethyl acetate solution.
  • the Hazen color number APHA is preferably 35 or less, more preferably 30 or less.
  • the Hazen color number APHA means that the closer to 0, the less the coloring, and the closer 1,1'-bi-2-naphthol is to white. Therefore, the lower limit of the Hazen color number APHA is not particularly limited, but may be, for example, 5 or more, or 10 or more.
  • the Hazen color number APHA is measured by a photoelectric colorimeter compliant with JIS K0071-1: 2017.
  • the Hagen color number APHA can be reduced, for example, by reducing the amount of metal contained in the 1,1'-bi-2-naphthol composition.
  • the 1,1'-bi-2-naphthol composition has a racemic 1,1'-content of Cu (copper), Fe (iron), Ni (nickel) and V (vanadium). It is preferably 3 mass ppm or less with respect to the mass of bi-2-naphthol. Since these metals cause coloring of 1,1'-bi-2-naphthol, deterioration of hue in an ethyl acetate solution can be suppressed by reducing the content.
  • each of these metals is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, and further preferably 0.3 mass ppm or less. At least one selected from the group consisting of Cu, Fe, Ni and V need not be contained in the 1,1'-bi-2-naphthol composition, that is, the content of each of these metals is 0 mass ppm. (Ie, less than the detection limit) may be used.
  • the contents of Cu, Fe, Ni and V are the contents as these elements.
  • the content form of these metals in the 1,1'-bi-2-naphthol composition may be contained as a compound such as copper chloride, and even in that case, the above content is the content as a metal element. ..
  • these metals are included in the 1,1'-bi-2-naphthol composition because the reaction catalyst for synthesizing 1,1'-bi-2-naphthol remains after purification. It may be a catalyst.
  • the contents of Cu, Fe, Ni and V can be quantified by ICP emission spectroscopic analysis.
  • ICP Induction Bonded Plasma
  • the component elements (atoms) contained in the sample are excited by giving the energy of argon plasma to the sample from the outside, and the excited atoms return to the low energy level. It is a method of measuring the emission line (spectral line) emitted from time to time, and the type of a component element can be determined from the position (wavelength) of the emission line, and the content of each element can be obtained from the intensity thereof.
  • the form of the 1,1'-bi-2-naphthol composition according to the present embodiment is not particularly limited, and may be in the form of a dry powder, for example, in the form of a sherbet or a slurry depending on the content of toluene and / or chlorotoluene. It may be in the form.
  • the 1,1'-bi-2-naphthol composition according to the present embodiment contains other components such as an organic solvent other than toluene and chlorotoluene in addition to the above-mentioned components as long as the effect is not impaired. May be included.
  • the method for producing the 1,1'-bi-2-naphthol composition according to the present embodiment is not particularly limited.
  • a method including a step of obtaining racemic 1,1'-bi-2-naphthol by a reaction between ⁇ -naphthols dissolved in a solvent in a solution of ⁇ -naphthol may be used.
  • Examples of the solvent used in this step include various organic solvents such as aromatic compounds, alicyclic compounds, and aliphatic compounds. Even if any one of these is used, two or more of them may be used in combination. You may.
  • examples of the aromatic compound include aromatic hydrocarbons such as benzene, toluene, xylene and methylnaphthalene, and chlorotoluene.
  • examples of the alicyclic compound include cyclohexane, cyclohexanol, and methylcyclohexane.
  • aliphatic compound examples include aliphatic monohydric alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol and isobutyl alcohol, aliphatic ethers such as ethyl ether and ethylene glycol monoethyl ether, chloroform, methylene chloride and tetrachloride.
  • aliphatic ethers such as ethyl ether and ethylene glycol monoethyl ether, chloroform, methylene chloride and tetrachloride.
  • halogenated hydrocarbons such as carbon and alkanes such as hexane and heptane.
  • solvents at least one selected from the group consisting of aromatic compounds and aliphatic compounds is preferable, and at least one selected from the group consisting of toluene, xylene and isobutyl alcohol is more preferable.
  • Examples of the method for synthesizing racemic 1,1'-bi-2-naphthol by the reaction between ⁇ -naphthols include the oxidation coupling reaction of ⁇ -naphthols.
  • Examples of the method of oxidatively coupling ⁇ -naphthols include a method of dissolving ⁇ -naphthol in an organic solvent and stirring the reaction solution at a reaction temperature of 0 to 100 ° C. in the presence of a reaction catalyst.
  • a reaction catalyst a transition metal catalyst is preferable, and for example, copper nitrate, copper chloride, copper bromide, iron chloride, or the like may be used alone or in combination of two or more.
  • the 1,1'-bi-2-naphthol produced by the reaction is a solution. It is preferable to carry out the reaction under the condition of precipitating from the above in order to reduce the number of Hazen colors APHA. By carrying out the reaction while precipitating the 1,1'-bi-2-naphthol thus produced from the reaction solution, it is possible to easily obtain 1,1'-bi-2-naphthol with less coloring and good hue. Can be done.
  • the conditions for precipitating 1,1'-bi-2-naphthol can be adjusted by the solvent, temperature, and concentration in the system.
  • the temperature T is set to a temperature at which 1,1'-bi-2-naphthol produced by the reaction precipitates from the reaction solution.
  • the reaction may be carried out. If the concentration of 1,1'-bi-2-naphthol produced in the system is higher than the solubility of 1,1'-bi-2-naphthol, then 1,1'-bi-2- Naftor is saturated and precipitated from the solution. Therefore, depending on the solvent, the temperature T is set so that the solubility of 1,1'-bi-2-naphthol becomes lower than the concentration of 1,1'-bi-2-naphthol produced in the system. do it.
  • the above oxidation coupling reaction is preferably carried out in a system in which ⁇ -naphthol that cannot be completely dissolved in the solvent is present. That is, ⁇ -naphthol may react with each other in a heterogeneous system in which ⁇ -naphthol is saturated and ⁇ -naphthol that cannot be completely dissolved and is liberated from the solution exists together with the solution. The liberated ⁇ -naphthol can be consumed by continuing the above reaction. That is, by continuing the above reaction, ⁇ -naphthol that is not completely dissolved in the solvent is sequentially dissolved in the solvent and used in the above reaction.
  • the 1,1'-bi-2-naphthol precipitated by the oxidation-coupling reaction may be separated from the reaction solution by filtration or the like, and then subjected to a purification step for removing residual impurities such as a reaction catalyst.
  • 1,1'-bi-2-naphthol such as ethyl acetate is dissolved by adding the reaction precipitate separated from the above reaction solution to a solvent capable of dissolving the solution, and an aqueous solution containing a chelating agent or an acid is dissolved.
  • impurities such as a reaction catalyst can be removed.
  • the solvent is removed using an evaporator or the like, and the mixture is further dried to obtain racemic 1,1'-bi-2-naphthol.
  • the 1,1'-bi-2-naphthol composition according to the embodiment is obtained.
  • purification and drying are carried out under the condition that toluene and / or chlorotoluene as a solvent used in the 1,1'-bi-2-naphthol production process such as an oxidation coupling reaction remains.
  • a 1,1'-bi-2-naphthol composition may be obtained.
  • solvent content content of toluene, chlorotoluene, and hexane
  • the GC analysis conditions are as follows. Column: Agilent Technologies, J & W Colon DB-1, 15m x 0.53mm x 0.15 ⁇ m Temperature program: 40 ° C (5 minutes)-(10 ° C / minute) -300 ° C (10 minutes) Injection port temperature: 300 ° C Detector temperature: 300 ° C Carrier gas: N 2
  • Metal content content of Cu, Fe, Ni, V
  • Example 1 A glass reactor equipped with a stirrer, a cooler, an air introduction tube and a thermometer was charged with 50 g of ⁇ -naphthol, 0.4 g of copper (II) chloride, 0.6 g of TMEDA (tetramethylethylenediamine) and 150 g of toluene. ⁇ -naphthol was dissolved by stirring at 50 ° C. Since the solubility of ⁇ -naphthol in toluene at 50 ° C. is 9% by mass, about 70% by mass of ⁇ -naphthol is not dissolved.
  • the reaction system was a heterogeneous system in which undissolved ⁇ -naphthol was present together with a saturated solution of ⁇ -naphthol. Then, while maintaining the temperature at 50 ° C. and stirring, air was blown at a rate of 300 ml / min for 12 hours to carry out an oxidation coupling reaction to obtain racemic 1,1'-bi-2-naphthol (racemic BINOL). Synthesized. Since the solubility of 1,1'-bi-2-naphthol in toluene at 50 ° C. is 1% by mass, the oxidation coupling reaction is carried out under the condition that 1,1'-bi-2-naphthol is precipitated. That is, the oxidation coupling reaction was carried out while precipitating 1,1'-bi-2-naphthol from the reaction solution.
  • the reaction precipitate was collected by filtering from the obtained reaction solution and purified. Specifically, the reaction precipitate was dissolved in 150 g of ethyl acetate, and 150 g of a 10 mass% EDTA-4 sodium aqueous solution was added to this solution to wash the organic solvent layer. Further, the organic solvent layer was washed in the same manner with 150 g of 1N hydrochloric acid in this solution. Subsequently, washing with water was repeated with 150 g of water. After washing with water, the solvent was distilled off from the organic solvent layer using an evaporator, and the obtained crystals were dried under reduced pressure at 70 ° C. for 6 hours. Copper chloride was added to the obtained crystals.
  • Example 2 The amount of toluene added after the addition of copper chloride was 1 part by mass in Example 2, 0.1 part by mass in Example 3, and 0.1 part by mass in Example 4 with respect to 100 parts by mass of 1,1'-bi-2-naphthol.
  • a powdery 1,1'-bi-2-naphthol composition was obtained in the same manner as in Example 1 except for 0.05 parts by mass.
  • Example 5 After the addition of copper chloride, 2-chlorotoluene was added instead of the toluene, and the amount of 2-chlorotoluene added was 1 in Example 5 with respect to 100 parts by mass of 1,1'-bi-2-naphthol. The mass amount was 0.1 parts by mass in Example 6, and the other parts were the same as in Example 1 to obtain a powdery 1,1'-bi-2-naphthol composition.
  • 1,1'-bi-2-naphthol compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were subjected to a dissolution rate test to measure the dissolution time, and when dissolved in an ethyl acetate solution. Hue (Hazen color number APHA) was measured. The results are shown in Table 1 below.
  • the dissolution rate in ethyl acetate was increased by adding toluene or chlorotoluene to the racemic 1,1'-bi-2-naphthol.
  • Such an increase in the dissolution rate leads to an improvement in the production efficiency of the target compound using 1,1'-bi-2-naphthol as a raw material by shortening the dissolution time.
  • toluene or chlorotoluene can replace a part of ethyl acetate as a co-solvent, and by reducing the amount of high-cost ethyl acetate, the production cost of the target compound can be reduced. Therefore, it is industrially advantageous.
  • Example 1 the copper content was low, and the deterioration of hue in the ethyl acetate solution was small.
  • Comparative Example 5 in which the copper content was high, the Hazen color number APHA when dissolved in the ethyl acetate solution was high, and the deterioration of the hue in the ethyl acetate solution was large.
  • the 1,1'-bi-2-naphthol composition according to the embodiment of the present invention can be used as a raw material for an optical material, for example.

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Abstract

The present invention improves the dissolution rate of 1,1'-bi-2-naphthol in ethyl acetate. The 1,1'-bi-2-naphthol composition according to an embodiment includes racemic 1,1'-bi-2-naphthol, and toluene and/or chlorotoluene, the Hazen color number APHA being 40 or lower when an ethyl acetate solution including 5 mass% of racemic 1,1'-bi-2-naphthol is prepared.

Description

１，１’－ビ－２－ナフトール組成物1,1'-bi-2-naphthol composition
　本発明は、１，１’－ビ－２－ナフトール組成物に関する。 The present invention relates to a 1,1'-bi-2-naphthol composition.
　１，１’－ビ－２－ナフトールやこれを原料とした誘導体は金属錯体触媒や光学材料の原料として用いられており、様々な製造方法により得られた１，１’－ビ－２－ナフトールが提供されている（特許文献１，２参照）。 1,1'-bi-2-naphthol and its derivatives are used as raw materials for metal complex catalysts and optical materials, and 1,1'-bi-2-naphthol obtained by various production methods. Is provided (see Patent Documents 1 and 2).
特開２００３－１７１３２７号公報Japanese Unexamined Patent Publication No. 2003-171327 特開２０００－２４７９２０号公報Japanese Unexamined Patent Publication No. 2000-247920
　ところで、１，１’－ビ－２－ナフトールを原料として用いて目的化合物の合成を行う場合、一般に１，１’－ビ－２－ナフトールを有機溶媒に溶解させて反応を行う。その際、例えば有機溶媒として酢酸エチルを用いる場合に、１，１’－ビ－２－ナフトールは酢酸エチルへの溶解に時間がかかるという問題がある。 By the way, when synthesizing the target compound using 1,1'-bi-2-naphthol as a raw material, the reaction is generally carried out by dissolving 1,1'-bi-2-naphthol in an organic solvent. At that time, for example, when ethyl acetate is used as the organic solvent, 1,1'-bi-2-naphthol has a problem that it takes a long time to dissolve in ethyl acetate.
　本発明の実施形態は、以上の点に鑑み、１，１’－ビ－２－ナフトールの酢酸エチルへの溶解速度を向上することを目的とする。 In view of the above points, an embodiment of the present invention aims to improve the dissolution rate of 1,1'-bi-2-naphthol in ethyl acetate.
　本発明者は、種々検討していく中で、ラセミ体１，１’－ビ－２－ナフトールにトルエン及び／又はクロロトルエンを含ませることにより、１，１’－ビ－２－ナフトールの酢酸エチルへの溶解速度が向上することを見い出した。 The present inventor has made various studies on the acetate of 1,1'-bi-2-naphthol by adding toluene and / or chlorotoluene to the racemic 1,1'-bi-2-naphthol. It has been found that the rate of dissolution in ethyl is improved.
　本発明の実施形態は、ラセミ体１，１’－ビ－２－ナフトールと、トルエン及び／又はクロロトルエンと、を含み、ラセミ体１，１’－ビ－２－ナフトールを５質量％含む酢酸エチル溶液としたときのハーゼン色数ＡＰＨＡが４０以下である１，１’－ビ－２－ナフトール組成物である。 Embodiments of the present invention contain racemic 1,1'-bi-2-naphthol, toluene and / or chlorotoluene, and acetic acid containing 5% by mass of racemic 1,1'-bi-2-naphthol. A 1,1'-bi-2-naphthol composition having a Hazen color number APHA of 40 or less when prepared as an ethyl solution.
　本実施形態であると、１，１’－ビ－２－ナフトールとしてラセミ体を用い、トルエン及び／又はクロロトルエンを加えることにより、１，１’－ビ－２－ナフトールの酢酸エチルへの溶解速度を向上することができる。本実施形態であると、また、酢酸エチル溶液中での１，１’－ビ－２－ナフトールの色相の悪化を抑制することができる。 In the present embodiment, racemic mixture is used as 1,1'-bi-2-naphthol, and 1,1'-bi-2-naphthol is dissolved in ethyl acetate by adding toluene and / or chlorotoluene. The speed can be improved. In the present embodiment, deterioration of the hue of 1,1'-bi-2-naphthol in an ethyl acetate solution can be suppressed.
　本実施形態に係る１，１’－ビ－２－ナフトール組成物は、ラセミ体１，１’－ビ－２－ナフトールと、トルエン及び／又はクロロトルエンと、を含むものである。 The 1,1'-bi-2-naphthol composition according to the present embodiment contains racemic 1,1'-bi-2-naphthol, toluene and / or chlorotoluene.
　１，１’－ビ－２－ナフトールはＢＩＮＯＬとも称され、２つの光学異性体（即ち、（Ｒ）－１，１’－ビ－２－ナフトール、（Ｓ）－１，１’－ビ－２－ナフトール）がある。本実施形態では、１，１’－ビ－２－ナフトールとしてラセミ体（即ち、（ＲＳ）－１，１’－ビ－２－ナフトール）を用いる。ラセミ体を用いることにより、Ｒ体やＳ体を用いた場合と比べて酢酸エチルへの溶解速度を上昇させることができる。 1,1'-bi-2-naphthol, also called BINOL, has two optical isomers (ie, (R) -1,1'-bi-2-naphthol, (S) -1,1'-bi- 2-Naftor). In this embodiment, a racemic mixture (that is, (RS) -1,1'-bi-2-naphthol) is used as 1,1'-bi-2-naphthol. By using the racemate, the dissolution rate in ethyl acetate can be increased as compared with the case where the R-form or S-form is used.
　本実施形態では、ラセミ体１，１’－ビ－２－ナフトールとともに、トルエン及び／又はクロロトルエンを含有させる。１，１’－ビ－２－ナフトールは常温ではトルエンやクロロトルエンには溶解しないが、トルエンやクロロトルエンを含有させることにより、１，１’－ビ－２－ナフトールの酢酸エチルへの溶解速度を上昇させることができる。その理由は明らかではないが、トルエンやクロロトルエンが常温において助溶媒として作用するためと考えられる。クロロトルエンとしては、２－クロロトルエン、３－クロロトルエン、４－クロロトルエンが挙げられ、好ましくは２－クロロトルエンを用いることである。 In this embodiment, toluene and / or chlorotoluene is contained together with racemic 1,1'-bi-2-naphthol. 1,1'-bi-2-naphthol does not dissolve in toluene or chlorotoluene at room temperature, but by adding toluene or chlorotoluene, the dissolution rate of 1,1'-bi-2-naphthol in ethyl acetate Can be raised. The reason is not clear, but it is thought that toluene and chlorotoluene act as co-solvents at room temperature. Examples of chlorotoluene include 2-chlorotoluene, 3-chlorotoluene, and 4-chlorotoluene, and 2-chlorotoluene is preferably used.
　トルエン及び／又はクロロトルエンの含有量（即ち、トルエン単独の場合はトルエンの含有量、クロロトルエン単独の場合はクロロトルエンの含有量、トルエンとクロロトルエンの併用の場合は両者の合計含有量）は、ラセミ体１，１’－ビ－２－ナフトールの質量に対して、５００質量ｐｐｍ以上であることが、酢酸エチルへの溶解速度の向上効果を高める上で好ましい。この含有量は、より好ましくは１０００質量ｐｐｍ以上であり、１質量％以上でもよい。トルエン及び／又はクロロトルエンの含有量の上限は、特に限定されず、ラセミ体１，１’－ビ－２－ナフトールの質量に対して、例えば５０質量％以下でもよく、２５質量％以下でもよく、１５質量％以下でもよい。 The content of toluene and / or chlorotoluene (that is, the content of toluene in the case of toluene alone, the content of chlorotoluene in the case of chlorotoluene alone, the total content of both in the case of combined use of toluene and chlorotoluene) , 500 mass ppm or more with respect to the mass of the rasemi form 1,1'-bi-2-naphthol is preferable in order to enhance the effect of improving the dissolution rate in ethyl acetate. This content is more preferably 1000 mass ppm or more, and may be 1 mass% or more. The upper limit of the content of toluene and / or chlorotoluene is not particularly limited, and may be, for example, 50% by mass or less, or 25% by mass or less, based on the mass of racemic 1,1'-bi-2-naphthol. , 15% by mass or less.
　トルエン及び／又はクロロトルエンの含有量は、ＧＣ（ガスクロマトグラフ）により定量することができる。 The content of toluene and / or chlorotoluene can be quantified by GC (gas chromatograph).
　本実施形態に係る１，１’－ビ－２－ナフトール組成物は、酢酸エチルに溶解させてラセミ体１，１’－ビ－２－ナフトールを５質量％含む酢酸エチル溶液としたときのハーゼン色数ＡＰＨＡが４０以下である。これにより、酢酸エチル溶液中での１，１’－ビ－２－ナフトールの色相の悪化を抑制することができる。ハーゼン色数ＡＰＨＡは、３５以下であることが好ましく、より好ましくは３０以下である。ハーゼン色数ＡＰＨＡは、０に近いほど着色が少なく、１，１’－ビ－２－ナフトールが白色に近いことを意味する。そのため、ハーゼン色数ＡＰＨＡの下限は、特に限定されないが、例えば５以上でもよく、１０以上でもよい。 The 1,1'-bi-2-naphthol composition according to the present embodiment is Hazen when dissolved in ethyl acetate to prepare a ethyl acetate solution containing 5% by mass of racemic 1,1'-bi-2-naphthol. The number of colors APHA is 40 or less. This makes it possible to suppress the deterioration of the hue of 1,1'-bi-2-naphthol in the ethyl acetate solution. The Hazen color number APHA is preferably 35 or less, more preferably 30 or less. The Hazen color number APHA means that the closer to 0, the less the coloring, and the closer 1,1'-bi-2-naphthol is to white. Therefore, the lower limit of the Hazen color number APHA is not particularly limited, but may be, for example, 5 or more, or 10 or more.
　ハーゼン色数ＡＰＨＡは、ＪＩＳ　Ｋ００７１－１：２０１７に準拠した光電色彩計により測定される。 The Hazen color number APHA is measured by a photoelectric colorimeter compliant with JIS K0071-1: 2017.
　ハーゲン色数ＡＰＨＡは、例えば１，１’－ビ－２－ナフトール組成物に含まれる金属の量を減らすことにより小さくすることができる。一実施形態において、１，１’－ビ－２－ナフトール組成物は、Ｃｕ（銅）、Ｆｅ（鉄）、Ｎｉ（ニッケル）及びＶ（バナジウム）の含有量が、ラセミ体１，１’－ビ－２－ナフトールの質量に対して、それぞれ３質量ｐｐｍ以下であることが好ましい。これらの金属は１，１’－ビ－２－ナフトールの着色を引き起こすため、含有量を削減することにより、酢酸エチル溶液中での色相の悪化を抑制することができる。 The Hagen color number APHA can be reduced, for example, by reducing the amount of metal contained in the 1,1'-bi-2-naphthol composition. In one embodiment, the 1,1'-bi-2-naphthol composition has a racemic 1,1'-content of Cu (copper), Fe (iron), Ni (nickel) and V (vanadium). It is preferably 3 mass ppm or less with respect to the mass of bi-2-naphthol. Since these metals cause coloring of 1,1'-bi-2-naphthol, deterioration of hue in an ethyl acetate solution can be suppressed by reducing the content.
　これらの金属の含有量は、それぞれ１質量ｐｐｍ以下であることが好ましく、より好ましくはそれぞれ０．５質量ｐｐｍ以下であり、更に好ましくは０．３質量ｐｐｍ以下である。Ｃｕ、Ｆｅ、Ｎｉ及びＶからなる群から選択される少なくとも一種は、１，１’－ビ－２－ナフトール組成物に含まれていなくてもよく、即ちこれら金属の含有量はそれぞれ０質量ｐｐｍ（即ち、検出限界未満）でもよい。 The content of each of these metals is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, and further preferably 0.3 mass ppm or less. At least one selected from the group consisting of Cu, Fe, Ni and V need not be contained in the 1,1'-bi-2-naphthol composition, that is, the content of each of these metals is 0 mass ppm. (Ie, less than the detection limit) may be used.
　ここで、Ｃｕ、Ｆｅ、Ｎｉ及びＶの含有量は、これらの元素としての含有量である。１，１’－ビ－２－ナフトール組成物におけるこれら金属の含有形態としては、例えば塩化銅などの化合物として含まれてもよく、その場合も、上記含有量は金属元素としての含有量である。一実施形態において、これらの金属は、１，１’－ビ－２－ナフトールを合成する際の反応触媒が、精製後に残留することで１，１’－ビ－２－ナフトール組成物に含まれたものであってもよい。 Here, the contents of Cu, Fe, Ni and V are the contents as these elements. The content form of these metals in the 1,1'-bi-2-naphthol composition may be contained as a compound such as copper chloride, and even in that case, the above content is the content as a metal element. .. In one embodiment, these metals are included in the 1,1'-bi-2-naphthol composition because the reaction catalyst for synthesizing 1,1'-bi-2-naphthol remains after purification. It may be a catalyst.
　Ｃｕ、Ｆｅ、Ｎｉ及びＶの含有量は、ＩＣＰ発光分光分析により定量することができる。ここで、ＩＣＰ（誘導結合プラズマ）発光分光分析は、試料にアルゴンプラズマのエネルギーを外部から与えることにより試料に含まれる成分元素（原子）を励起し、励起された原子が低いエネルギー準位に戻るときに放出される発光線（スペクトル線）を測定する方法であり、発光線の位置（波長）から成分元素の種類を判定し、その強度から各元素の含有量を求めることができる。 The contents of Cu, Fe, Ni and V can be quantified by ICP emission spectroscopic analysis. Here, in ICP (Induction Bonded Plasma) emission spectroscopic analysis, the component elements (atoms) contained in the sample are excited by giving the energy of argon plasma to the sample from the outside, and the excited atoms return to the low energy level. It is a method of measuring the emission line (spectral line) emitted from time to time, and the type of a component element can be determined from the position (wavelength) of the emission line, and the content of each element can be obtained from the intensity thereof.
　本実施形態に係る１，１’－ビ－２－ナフトール組成物の形態は、特に限定されず、例えば乾燥した粉体状でもよく、トルエン及び／又はクロロトルエンの含有量によってはシャーベット状やスラリー状であってもよい。 The form of the 1,1'-bi-2-naphthol composition according to the present embodiment is not particularly limited, and may be in the form of a dry powder, for example, in the form of a sherbet or a slurry depending on the content of toluene and / or chlorotoluene. It may be in the form.
　本実施形態に係る１，１’－ビ－２－ナフトール組成物には、その効果が損なわれない範囲で、上記した各成分の他に、トルエン及びクロロトルエン以外の有機溶媒などの他の成分が含まれてもよい。 The 1,1'-bi-2-naphthol composition according to the present embodiment contains other components such as an organic solvent other than toluene and chlorotoluene in addition to the above-mentioned components as long as the effect is not impaired. May be included.
　本実施形態に係る１，１’－ビ－２－ナフトール組成物の製造方法は、特に限定されない。例えば、β－ナフトールの溶液中で溶媒に溶解したβ－ナフトール同士の反応によりラセミ体１，１’－ビ－２－ナフトールを得る工程を含む方法でもよい。 The method for producing the 1,1'-bi-2-naphthol composition according to the present embodiment is not particularly limited. For example, a method including a step of obtaining racemic 1,1'-bi-2-naphthol by a reaction between β-naphthols dissolved in a solvent in a solution of β-naphthol may be used.
　該工程で使用する溶媒としては、例えば、芳香族化合物、脂環族化合物、脂肪族化合物などの各種有機溶媒を挙げることができ、これらはいずれか１種用いても、２種類以上を併用してもよい。ここで、芳香族化合物としては、例えば、ベンゼン、トルエン、キシレン、メチルナフタレンなどの芳香族炭化水素、クロロトルエンなどが挙げられる。脂環族化合物としては、例えば、シクロヘキサン、シクロヘキサノール、及びメチルシクロヘキサンが挙げられる。脂肪族化合物としては、例えば、メタノール、エタノール、プロパノール、イソプロピルアルコール、ブタノール、イソブチルアルコールなどの脂肪族一価アルコール、エチルエーテル、エチレングリコールモノエチルエーテルなどの脂肪族エーテル、クロロホルム、塩化メチレン、四塩化炭素などのハロゲン化炭化水素、ヘキサン、ヘプタンなどのアルカンが挙げられる。これらの溶媒のうち、芳香族化合物及び脂肪族化合物からなる群から選択される少なくとも一種が好ましく、より好ましくはトルエン、キシレン及びイソブチルアルコールからなる群から選択される少なくとも一種である。 Examples of the solvent used in this step include various organic solvents such as aromatic compounds, alicyclic compounds, and aliphatic compounds. Even if any one of these is used, two or more of them may be used in combination. You may. Here, examples of the aromatic compound include aromatic hydrocarbons such as benzene, toluene, xylene and methylnaphthalene, and chlorotoluene. Examples of the alicyclic compound include cyclohexane, cyclohexanol, and methylcyclohexane. Examples of the aliphatic compound include aliphatic monohydric alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol and isobutyl alcohol, aliphatic ethers such as ethyl ether and ethylene glycol monoethyl ether, chloroform, methylene chloride and tetrachloride. Examples thereof include halogenated hydrocarbons such as carbon and alkanes such as hexane and heptane. Among these solvents, at least one selected from the group consisting of aromatic compounds and aliphatic compounds is preferable, and at least one selected from the group consisting of toluene, xylene and isobutyl alcohol is more preferable.
　β－ナフトール同士の反応によりラセミ体１，１’－ビ－２－ナフトールを合成する方法としては、例えば、β－ナフトールの酸化カップリング反応が挙げられる。β－ナフトール同士を酸化カップリングする方法としては、例えば、β－ナフトールを有機溶媒に溶解し、反応触媒の存在下、反応温度０～１００℃で、反応溶液を攪拌する方法が挙げられる。反応触媒としては、遷移金属触媒が好ましく、例えば、硝酸銅、塩化銅、臭化銅、塩化鉄などをいずれか１種又は２種以上組み合わせて用いてもよい。酸化カップリング反応においては、β－ナフトールを溶解した溶液に対して空気などの酸素含有気体を接触させること、例えば系内に酸素含有気体を導入して反応を行うことが好ましい。 Examples of the method for synthesizing racemic 1,1'-bi-2-naphthol by the reaction between β-naphthols include the oxidation coupling reaction of β-naphthols. Examples of the method of oxidatively coupling β-naphthols include a method of dissolving β-naphthol in an organic solvent and stirring the reaction solution at a reaction temperature of 0 to 100 ° C. in the presence of a reaction catalyst. As the reaction catalyst, a transition metal catalyst is preferable, and for example, copper nitrate, copper chloride, copper bromide, iron chloride, or the like may be used alone or in combination of two or more. In the oxidation coupling reaction, it is preferable to bring an oxygen-containing gas such as air into contact with the solution in which β-naphthol is dissolved, for example, to introduce an oxygen-containing gas into the system to carry out the reaction.
　一実施形態において、β－ナフトールの溶液中でβ－ナフトール同士の反応により１，１’－ビ－２－ナフトールを得る際に、反応により生成する１，１’－ビ－２－ナフトールが溶液から析出する条件で当該反応を行うことが、ハーゼン色数ＡＰＨＡの低減を図る上で好ましい。このように生成した１，１’－ビ－２－ナフトールを反応溶液から析出させつつ反応を行うことにより、着色が少なく色相が良好な１，１’－ビ－２－ナフトールを簡便に得ることができる。 In one embodiment, when 1,1'-bi-2-naphthol is obtained by the reaction between β-naphthols in a solution of β-naphthol, the 1,1'-bi-2-naphthol produced by the reaction is a solution. It is preferable to carry out the reaction under the condition of precipitating from the above in order to reduce the number of Hazen colors APHA. By carrying out the reaction while precipitating the 1,1'-bi-2-naphthol thus produced from the reaction solution, it is possible to easily obtain 1,1'-bi-2-naphthol with less coloring and good hue. Can be done.
　１，１’－ビ－２－ナフトールを析出させる条件は、溶媒と温度と系中濃度とにより調整可能である。例えば、溶媒に溶解したβ－ナフトール同士を温度Ｔで反応させる方法において、該温度Ｔを、反応により生成される１，１’－ビ－２－ナフトールが反応溶液から析出する温度に設定して、当該反応を行えばよい。生成される１，１’－ビ－２－ナフトールの系中の濃度が、１，１’－ビ－２－ナフトールの溶解度よりも高くなれば、反応中に１，１’－ビ－２－ナフトールは飽和状態となって溶液から析出される。そのため、溶媒に応じて、１，１’－ビ－２－ナフトールの溶解度が、生成される１，１’－ビ－２－ナフトールの系中の濃度よりも低くなるように、温度Ｔを設定すればよい。 The conditions for precipitating 1,1'-bi-2-naphthol can be adjusted by the solvent, temperature, and concentration in the system. For example, in a method of reacting β-naphthols dissolved in a solvent with each other at a temperature T, the temperature T is set to a temperature at which 1,1'-bi-2-naphthol produced by the reaction precipitates from the reaction solution. , The reaction may be carried out. If the concentration of 1,1'-bi-2-naphthol produced in the system is higher than the solubility of 1,1'-bi-2-naphthol, then 1,1'-bi-2- Naftor is saturated and precipitated from the solution. Therefore, depending on the solvent, the temperature T is set so that the solubility of 1,1'-bi-2-naphthol becomes lower than the concentration of 1,1'-bi-2-naphthol produced in the system. do it.
　上記酸化カップリング反応は、溶媒に溶解しきれないβ－ナフトールが存在する系で行われることが好ましい。すなわち、β－ナフトールが飽和状態にあり、溶解しきれず溶液から遊離したβ－ナフトールが溶液とともに存在する不均一系で、β－ナフトール同士の反応を行ってもよい。なお、遊離したβ－ナフトールは上記反応を継続させることにより消費することができる。すなわち、上記反応を継続させることにより、溶媒に溶解しきれずに存在するβ－ナフトールが溶媒に逐次溶解して上記反応に用いられる。 The above oxidation coupling reaction is preferably carried out in a system in which β-naphthol that cannot be completely dissolved in the solvent is present. That is, β-naphthol may react with each other in a heterogeneous system in which β-naphthol is saturated and β-naphthol that cannot be completely dissolved and is liberated from the solution exists together with the solution. The liberated β-naphthol can be consumed by continuing the above reaction. That is, by continuing the above reaction, β-naphthol that is not completely dissolved in the solvent is sequentially dissolved in the solvent and used in the above reaction.
　上記酸化カップリング反応により析出した１，１’－ビ－２－ナフトールは、濾過などにより反応溶液から分離した後、反応触媒などの残存する不純物を除去するための精製工程を行ってもよい。詳細には、例えば、酢酸エチルなどの１，１’－ビ－２－ナフトールを溶解可能な溶媒に、上記の反応溶液から分離した反応析出物を加えて溶解させ、キレート剤を含む水溶液や酸を含む水溶液などを用いて洗浄することにより、反応触媒などの不純物を除去することができる。その後、例えばエバポレータなどを用いて溶媒を除去し、更に乾燥することでラセミ体１，１’－ビ－２－ナフトールを得ることができる。 The 1,1'-bi-2-naphthol precipitated by the oxidation-coupling reaction may be separated from the reaction solution by filtration or the like, and then subjected to a purification step for removing residual impurities such as a reaction catalyst. Specifically, for example, 1,1'-bi-2-naphthol such as ethyl acetate is dissolved by adding the reaction precipitate separated from the above reaction solution to a solvent capable of dissolving the solution, and an aqueous solution containing a chelating agent or an acid is dissolved. By washing with an aqueous solution containing the above, impurities such as a reaction catalyst can be removed. Then, the solvent is removed using an evaporator or the like, and the mixture is further dried to obtain racemic 1,1'-bi-2-naphthol.
　このようにして得られたラセミ体１，１’－ビ－２－ナフトールにトルエン及び／又はクロロトルエンを添加することにより、実施形態に係る１，１’－ビ－２－ナフトール組成物を得ることができる。あるいはまた、酸化カップリング反応等の１，１’－ビ－２－ナフトール製造過程で用いた溶媒としてのトルエン及び／又はクロロトルエンが残存する条件で精製、乾燥を行うことにより、実施形態に係る１，１’－ビ－２－ナフトール組成物を得てもよい。 By adding toluene and / or chlorotoluene to the racemic 1,1'-bi-2-naphthol thus obtained, the 1,1'-bi-2-naphthol composition according to the embodiment is obtained. be able to. Alternatively, according to the embodiment, purification and drying are carried out under the condition that toluene and / or chlorotoluene as a solvent used in the 1,1'-bi-2-naphthol production process such as an oxidation coupling reaction remains. A 1,1'-bi-2-naphthol composition may be obtained.
　以下、実施例および比較例に基づいてより詳細に説明するが、本発明はこれによって限定されるものではない。なお、測定・評価方法は以下のとおりである。 Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited thereto. The measurement / evaluation method is as follows.
［溶媒含有量］
　実施例および比較例の各１，１’－ビ－２－ナフトール組成物中の溶媒含有量（トルエン、クロロトルエン、ヘキサンの含有量）は、ＧＣ測定により求めた。ＧＣ分析条件は以下のとおりである。
　カラム：Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ，Ｊ＆Ｗ　Ｃｏｌｕｍｎ　ＤＢ－１，１５ｍ×０．５３ｍｍ×０．１５μｍ
　温度プログラム：４０℃（５分間）－（１０℃／分間）－３００℃（１０分間）
　注入口温度：３００℃
　検出器温度：３００℃
　キャリアガス：Ｎ２ [Solvent content]
The solvent content (contents of toluene, chlorotoluene, and hexane) in each of the 1,1'-bi-2-naphthol compositions of Examples and Comparative Examples was determined by GC measurement. The GC analysis conditions are as follows.
Column: Agilent Technologies, J & W Colon DB-1, 15m x 0.53mm x 0.15μm
Temperature program: 40 ° C (5 minutes)-(10 ° C / minute) -300 ° C (10 minutes)
Injection port temperature: 300 ° C
Detector temperature: 300 ° C
Carrier gas: N 2
［金属含有量］
　実施例および比較例の各１，１’－ビ－２－ナフトール組成物中の金属含有量（Ｃｕ、Ｆｅ、Ｎｉ、Ｖの含有量）は、アジレントテクノロジー社製のＩＣＰ発光分光分析装置（Ａｇｉｌｅｎｔ５１００）を用いて測定した。その際、１，１’－ビ－２－ナフトール組成物の試料１．２５ｇを採取し、ＤＭＦに溶解させ、この溶液を用いて測定を行った。 [Metal content]
The metal content (content of Cu, Fe, Ni, V) in each of the 1,1'-bi-2-naphthol compositions of Examples and Comparative Examples was determined by an ICP emission spectrophotometer (Agient 5100) manufactured by Agilent Technologies. ) Was used for measurement. At that time, 1.25 g of a sample of 1,1'-bi-2-naphthol composition was collected, dissolved in DMF, and measured using this solution.
［溶解速度試験：溶解時間］
　実施例および比較例の各１，１’－ビ－２－ナフトール組成物について、１，１’－ビ－２－ナフトールとして３ｇに相当する量の当該組成物を量り取り、攪拌子とともに１００ｍＬビーカーに入れ、酢酸エチル１７ｇを加えてからマグネチックスターラーを用いて攪拌を開始した。３０℃の雰囲気下で、攪拌開始から１，１’－ビ－２－ナフトールが均一溶解するまでの時間を計測した。 [Dissolution rate test: dissolution time]
For each of the 1,1'-bi-2-naphthol compositions of Examples and Comparative Examples, weigh the composition in an amount corresponding to 3 g as 1,1'-bi-2-naphthol, and weigh it together with a stirrer in a 100 mL beaker. After adding 17 g of ethyl acetate to the mixture, stirring was started using a magnetic stirrer. The time from the start of stirring to the uniform dissolution of 1,1'-bi-2-naphthol was measured in an atmosphere of 30 ° C.
［色相：ハーゼン色数ＡＰＨＡ］
　実施例および比較例の各１，１’－ビ－２－ナフトール組成物について、酢酸エチルに溶解させて１，１’－ビ－２－ナフトールを５質量％含む酢酸エチル溶液を作製した。得られた酢酸エチル溶液のハーゼン色数ＡＰＨＡを、日本電色工業社製の分光色彩計（ＳＥ６０００）により測定した。 [Hue: Hazen color number APHA]
Each of the 1,1'-bi-2-naphthol compositions of Examples and Comparative Examples was dissolved in ethyl acetate to prepare an ethyl acetate solution containing 5% by mass of 1,1'-bi-2-naphthol. The Hazen color number APHA of the obtained ethyl acetate solution was measured by a spectrocolorimeter (SE6000) manufactured by Nippon Denshoku Kogyo Co., Ltd.
［実施例１］
　攪拌器、冷却器、空気導入管および温度計を備えたガラス製反応器に、β－ナフトール５０ｇ、塩化銅（II）０．４ｇ、ＴＭＥＤＡ（テトラメチルエチレンジアミン）０．６ｇおよびトルエン１５０ｇを仕込み、５０℃で攪拌してβ－ナフトールを溶解させた。５０℃のトルエンに対するβ－ナフトールの溶解度は９質量％であるため、約７０質量％のβ－ナフトールは溶解していない。そのため、反応系は、β－ナフトールの飽和溶液とともに、溶解していないβ－ナフトールが存在する不均一系であった。その後、５０℃に維持して攪拌しながら、空気を３００ｍｌ／分の速度で１２時間吹き込み、酸化カップリング反応を行って、ラセミ体１，１’－ビ－２－ナフトール（ラセミ体ＢＩＮＯＬ）を合成した。５０℃のトルエンに対する１，１’－ビ－２－ナフトールの溶解度は１質量％であるため、１，１’－ビ－２－ナフトールが析出する条件で酸化カップリング反応が行われており、すなわち、１，１’－ビ－２－ナフトールを反応溶液から析出させつつ酸化カップリング反応が行われた。 [Example 1]
A glass reactor equipped with a stirrer, a cooler, an air introduction tube and a thermometer was charged with 50 g of β-naphthol, 0.4 g of copper (II) chloride, 0.6 g of TMEDA (tetramethylethylenediamine) and 150 g of toluene. Β-naphthol was dissolved by stirring at 50 ° C. Since the solubility of β-naphthol in toluene at 50 ° C. is 9% by mass, about 70% by mass of β-naphthol is not dissolved. Therefore, the reaction system was a heterogeneous system in which undissolved β-naphthol was present together with a saturated solution of β-naphthol. Then, while maintaining the temperature at 50 ° C. and stirring, air was blown at a rate of 300 ml / min for 12 hours to carry out an oxidation coupling reaction to obtain racemic 1,1'-bi-2-naphthol (racemic BINOL). Synthesized. Since the solubility of 1,1'-bi-2-naphthol in toluene at 50 ° C. is 1% by mass, the oxidation coupling reaction is carried out under the condition that 1,1'-bi-2-naphthol is precipitated. That is, the oxidation coupling reaction was carried out while precipitating 1,1'-bi-2-naphthol from the reaction solution.
　得られた反応溶液から反応析出物をろ過して採取し、精製を行った。詳細には、反応析出物を酢酸エチル１５０ｇに溶解させ、この溶液に１０質量％ＥＤＴＡ－４ナトリウム水溶液１５０ｇを加えて有機溶媒層を洗浄した。さらにこの溶液に１規定塩酸１５０ｇを用いて同様に有機溶媒層を洗浄した。つづいて、水１５０ｇを用いて水洗を繰り返した。水洗後、エバポレータを用いて有機溶媒層から溶媒を留去して得られた結晶を、減圧下、７０℃で６時間乾燥させた。得られた結晶に塩化銅を添加した。塩化銅は、銅が残存する影響を調べるために添加したものであり、１，１’－ビ－２－ナフトール５０ｇに対して０．０１ｍｇ（銅として約０．００５ｍｇ）を添加した。次いで、トルエンを１，１’－ビ－２－ナフトール１００質量部に対して１０質量部添加することにより、トルエンで湿った粉体状（ウェット粉体状）の１，１’－ビ－２－ナフトール組成物を得た。 The reaction precipitate was collected by filtering from the obtained reaction solution and purified. Specifically, the reaction precipitate was dissolved in 150 g of ethyl acetate, and 150 g of a 10 mass% EDTA-4 sodium aqueous solution was added to this solution to wash the organic solvent layer. Further, the organic solvent layer was washed in the same manner with 150 g of 1N hydrochloric acid in this solution. Subsequently, washing with water was repeated with 150 g of water. After washing with water, the solvent was distilled off from the organic solvent layer using an evaporator, and the obtained crystals were dried under reduced pressure at 70 ° C. for 6 hours. Copper chloride was added to the obtained crystals. Copper chloride was added to investigate the effect of residual copper, and 0.01 mg (about 0.005 mg as copper) was added to 50 g of 1,1'-bi-2-naphthol. Next, by adding 10 parts by mass of toluene with respect to 100 parts by mass of 1,1'-bi-2-naphthol, 1,1'-bi-2 in the form of a powder (wet powder) moistened with toluene was added. -A naphthol composition was obtained.
［実施例２～４］
　塩化銅添加後のトルエンの添加量を、１，１’－ビ－２－ナフトール１００質量部に対して、実施例２では１質量部、実施例３では０．１質量部、実施例４では０．０５質量部とし、その他は実施例１と同様にして、粉体状の１，１’－ビ－２－ナフトール組成物を得た。 [Examples 2 to 4]
The amount of toluene added after the addition of copper chloride was 1 part by mass in Example 2, 0.1 part by mass in Example 3, and 0.1 part by mass in Example 4 with respect to 100 parts by mass of 1,1'-bi-2-naphthol. A powdery 1,1'-bi-2-naphthol composition was obtained in the same manner as in Example 1 except for 0.05 parts by mass.
［実施例５，６］
　塩化銅添加後に、トルエンを添加する代わりに２－クロロトルエンを添加し、２－クロロトルエンの添加量を、１，１’－ビ－２－ナフトール１００質量部に対して、実施例５では１質量部、実施例６では０．１質量部とし、その他は実施例１と同様にして、粉体状の１，１’－ビ－２－ナフトール組成物を得た。 [Examples 5 and 6]
After the addition of copper chloride, 2-chlorotoluene was added instead of the toluene, and the amount of 2-chlorotoluene added was 1 in Example 5 with respect to 100 parts by mass of 1,1'-bi-2-naphthol. The mass amount was 0.1 parts by mass in Example 6, and the other parts were the same as in Example 1 to obtain a powdery 1,1'-bi-2-naphthol composition.
［比較例１］
　反応溶媒としてトルエンの代わりに塩化メチレンを用い、その他は実施例１と同様に酸化カップリング反応を行った。反応溶液から反応析出物をろ過して採取した後に、シリカカラムクロマトグラフィー（展開溶媒はヘキサン：ジエチルエーテル＝９：１（体積比））を用いて精製した。精製後の結晶に実施例１と同様にして塩化銅を添加し、減圧・常温で２４時間乾燥して、粉体状の１，１’－ビ－２－ナフトール組成物を得た。 [Comparative Example 1]
Methylene chloride was used as the reaction solvent instead of toluene, and the oxidation coupling reaction was carried out in the same manner as in Example 1 for the others. The reaction precipitate was collected by filtration from the reaction solution, and then purified by silica column chromatography (developing solvent was hexane: diethyl ether = 9: 1 (volume ratio)). Copper chloride was added to the purified crystals in the same manner as in Example 1, and the crystals were dried under reduced pressure at room temperature for 24 hours to obtain a powdery 1,1'-bi-2-naphthol composition.
［比較例２］
　反応溶媒としてトルエンの代わりにヘキサンを用い、また、塩化銅添加後にトルエンを添加する代わりにヘキサンを添加し、ヘキサンの添加量は１，１’－ビ－２－ナフトール１００質量部に対して０．０５質量部とし、その他は実施例１と同様にして、粉体状の１，１’－ビ－２－ナフトール組成物を得た。 [Comparative Example 2]
Hexane was used as the reaction solvent instead of toluene, and hexane was added instead of toluene after adding copper chloride. The amount of hexane added was 0 with respect to 100 parts by mass of 1,1'-bi-2-naphthol. A powdery 1,1'-bi-2-naphthol composition was obtained in the same manner as in Example 1 except that the amount was 0.05 parts by mass.
［比較例３］
　（Ｒ）－１，１’－ビ－２－ナフトール（（Ｒ）－ＢＩＮＯＬ、富士フイルム和光純薬製）にトルエンと塩化銅を添加し、固形分濃度８５質量％に調製した。ここで、塩化銅は１，１’－ビ－２－ナフトール５０ｇに対して０．１ｍｇ（銅として約０．０５ｍｇ）を添加した。次いで、常温にて減圧乾燥を行ってトルエンを留去して、粉体状の１，１’－ビ－２－ナフトール組成物を得た。 [Comparative Example 3]
Toluene and copper chloride were added to (R) -1,1'-bi-2-naphthol ((R) -BINOL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to prepare a solid content concentration of 85% by mass. Here, 0.1 mg (about 0.05 mg as copper) of copper chloride was added to 50 g of 1,1'-bi-2-naphthol. Then, it was dried under reduced pressure at room temperature to distill off toluene to obtain a powdery 1,1'-bi-2-naphthol composition.
［比較例４］
　（Ｓ）－１，１’－ビ－２－ナフトール（（Ｓ）－ＢＩＮＯＬ、富士フイルム和光純薬製）にトルエンと塩化銅を添加し、固形分濃度８５質量％に調製した。ここで、塩化銅は１，１’－ビ－２－ナフトール５０ｇに対して０．１ｍｇ（銅として約０．０５ｍｇ）を添加した。次いで、常温にて減圧乾燥を行ってトルエンを留去して、粉体状の１，１’－ビ－２－ナフトール組成物を得た。 [Comparative Example 4]
Toluene and copper chloride were added to (S) -1,1'-bi-2-naphthol ((S) -BINOL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to prepare a solid content concentration of 85% by mass. Here, 0.1 mg (about 0.05 mg as copper) of copper chloride was added to 50 g of 1,1'-bi-2-naphthol. Then, it was dried under reduced pressure at room temperature to distill off toluene to obtain a powdery 1,1'-bi-2-naphthol composition.
［比較例５］
　精製時に水洗をせずにエバポレータを用いて溶媒を留去して得られた結晶を乾燥させ、得られた結晶にトルエンを１，１’－ビ－２－ナフトール１００質量部に対して１０質量部添加し、その他は実施例１と同様にして、ウェット粉体状の１，１’－ビ－２－ナフトール組成物を得た。 [Comparative Example 5]
During purification, the solvent was distilled off using an evaporator without washing with water, and the obtained crystals were dried. Toluene was added to the obtained crystals by 10 parts by mass with respect to 100 parts by mass of 1,1'-bi-2-naphthol. A wet powdery 1,1'-bi-2-naphthol composition was obtained in the same manner as in Example 1 except for the partial addition.
　上記で得られた実施例１～６および比較例１～５の１，１’－ビ－２－ナフトール組成物について、溶媒含有量（ＢＩＮＯＬに対する質量％）と金属含有量（ＢＩＮＯＬに対する質量ｐｐｍ）を測定した。結果を下記表１に示す。なお、金属含有量については、Ｃｕの含有量は表１に示すとおりであり、Ｆｅ、Ｎｉ及びＶについてはいずれも検出限界未満、即ち０質量ｐｐｍであった。 For the 1,1'-bi-2-naphthol compositions of Examples 1 to 6 and Comparative Examples 1 to 5 obtained above, the solvent content (mass% with respect to BINOL) and the metal content (mass ppm with respect to BINOL). Was measured. The results are shown in Table 1 below. Regarding the metal content, the Cu content was as shown in Table 1, and Fe, Ni and V were all below the detection limit, that is, 0 mass ppm.
　また、実施例１～６および比較例１～５の１，１’－ビ－２－ナフトール組成物について、溶解速度試験を行って溶解時間を計測するとともに、酢酸エチル溶液に溶解させたときの色相（ハーゼン色数ＡＰＨＡ）を測定した。結果を下記表１に示す。 Further, the 1,1'-bi-2-naphthol compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were subjected to a dissolution rate test to measure the dissolution time, and when dissolved in an ethyl acetate solution. Hue (Hazen color number APHA) was measured. The results are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、比較例１では、１，１’－ビ－２－ナフトールにトルエン等の溶媒を含有させていないため、酢酸エチルへの溶解時間が長かった。比較例２では、溶媒としてヘキサンが含まれていたが、ヘキサンでは酢酸エチルへの溶解速度の上昇は見られなかった。 As shown in Table 1, in Comparative Example 1, since 1,1'-bi-2-naphthol did not contain a solvent such as toluene, the dissolution time in ethyl acetate was long. In Comparative Example 2, hexane was contained as a solvent, but hexane did not show an increase in the dissolution rate in ethyl acetate.
　これに対し、実施例１～６では、ラセミ体１，１’－ビ－２－ナフトールにトルエン又はクロロトルエンを含有させたことにより、酢酸エチルへの溶解速度が上昇していた。このように溶解速度が上昇することは、溶解時間の短縮により、１，１’－ビ－２－ナフトールを原料として用いる目的化合物の生産効率向上につながる。また、トルエン又はクロロトルエンが助溶媒として酢酸エチルの一部を置き換えることができ、コストの高い酢酸エチルの量を減らすことで、目的化合物の製造コストの低減につながる。そのため、工業的に有利である。 On the other hand, in Examples 1 to 6, the dissolution rate in ethyl acetate was increased by adding toluene or chlorotoluene to the racemic 1,1'-bi-2-naphthol. Such an increase in the dissolution rate leads to an improvement in the production efficiency of the target compound using 1,1'-bi-2-naphthol as a raw material by shortening the dissolution time. Further, toluene or chlorotoluene can replace a part of ethyl acetate as a co-solvent, and by reducing the amount of high-cost ethyl acetate, the production cost of the target compound can be reduced. Therefore, it is industrially advantageous.
　一方、比較例３，４では、溶媒としてトルエンが含まれていたが、１，１’－ビ－２－ナフトールがラセミ体ではなく、Ｒ体又はＳ体であったため、酢酸エチルへの溶解速度の上昇効果が小さかった。このように１，１’－ビ－２－ナフトールとしてラセミ体を用いることにより、Ｒ体やＳ体を用いた場合と比べて酢酸エチルへの溶解速度を大きく上昇させることができた。 On the other hand, in Comparative Examples 3 and 4, toluene was contained as a solvent, but since 1,1'-bi-2-naphthol was not a racemate but an R-form or an S-form, the dissolution rate in ethyl acetate. The effect of increasing was small. By using the racemic mixture as 1,1'-bi-2-naphthol in this way, the dissolution rate in ethyl acetate could be significantly increased as compared with the case where the R-form or S-form was used.
　また、実施例１～６であると、銅の含有量が少なく、酢酸エチル溶液中での色相の悪化が小さかった。これに対し、銅の含有量が多い比較例５では、酢酸エチル溶液に溶解させたときのハーゼン色数ＡＰＨＡが高く、酢酸エチル溶液中での色相の悪化が大きかった。 Further, in Examples 1 to 6, the copper content was low, and the deterioration of hue in the ethyl acetate solution was small. On the other hand, in Comparative Example 5 in which the copper content was high, the Hazen color number APHA when dissolved in the ethyl acetate solution was high, and the deterioration of the hue in the ethyl acetate solution was large.
　以上、本発明のいくつかの実施形態を説明したが、これら実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその省略、置き換え、変更などは、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれるものである。 Although some embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments, omissions, replacements, modifications, etc. thereof are included in the scope and gist of the invention, as well as in the scope of the invention described in the claims and the equivalent scope thereof.
　本発明の実施形態に係る１，１’－ビ－２－ナフトール組成物は、例えば、光学材料の原料に利用することができる。 The 1,1'-bi-2-naphthol composition according to the embodiment of the present invention can be used as a raw material for an optical material, for example.

Claims (3)

  1. 　ラセミ体１，１’－ビ－２－ナフトールと、トルエン及び／又はクロロトルエンと、を含み、ラセミ体１，１’－ビ－２－ナフトールを５質量％含む酢酸エチル溶液としたときのハーゼン色数ＡＰＨＡが４０以下である、１，１’－ビ－２－ナフトール組成物。 Hazen when prepared as an ethyl acetate solution containing racemic 1,1'-bi-2-naphthol, toluene and / or chlorotoluene, and containing 5% by mass of racemic 1,1'-bi-2-naphthol. A 1,1'-bi-2-naphthol composition having an APHA of 40 or less colors.
  2. 　トルエン及び／又はクロロトルエンの含有量がラセミ体１，１’－ビ－２－ナフトールの質量に対して５００質量ｐｐｍ以上である、請求項１に記載の１，１’－ビ－２－ナフトール組成物。 The 1,1'-bi-2-naphthol according to claim 1, wherein the content of toluene and / or chlorotoluene is 500 mass ppm or more with respect to the mass of the racemic 1,1'-bi-2-naphthol. Composition.
  3. 　Ｃｕ、Ｆｅ、Ｎｉ及びＶの含有量がラセミ体１，１’－ビ－２－ナフトールの質量に対してそれぞれ３質量ｐｐｍ以下である、請求項１又は２に記載の１，１’－ビ－２－ナフトール組成物。 The 1,1'-bi according to claim 1 or 2, wherein the contents of Cu, Fe, Ni and V are 3% by mass or less with respect to the mass of the racemic 1,1'-bi-2-naphthol, respectively. -2-Naftor composition.
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JP2001039913A (en) * 1999-07-29 2001-02-13 Dainippon Ink & Chem Inc Purification of binaphthol
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CN108083985A (en) * 2017-12-08 2018-05-29 和夏化学(太仓)有限公司 A kind of preparation method of electron level 2,2 '-dinaphthol

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