TW201706238A - Crystals of alcohol having fluorene skeleton, and method for producing same - Google Patents

Crystals of alcohol having fluorene skeleton, and method for producing same Download PDF

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TW201706238A
TW201706238A TW105121116A TW105121116A TW201706238A TW 201706238 A TW201706238 A TW 201706238A TW 105121116 A TW105121116 A TW 105121116A TW 105121116 A TW105121116 A TW 105121116A TW 201706238 A TW201706238 A TW 201706238A
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alcohol
anthracene skeleton
crystal
skeleton represented
above formula
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TWI636038B (en
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Hiroyuki Kato
Takafumi Saiki
Yuji Nishida
Katsuhiro Fujii
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Taoka Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation

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  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Provided are: crystals of an alcohol having a fluorene skeleton represented by formula (1) in which the melt endotherm maximum temperature by differential scanning calorimetry is 148-151 DEG C; and a method for producing the crystals, the method including, in order, a step for obtaining a reaction solution that includes an alcohol having a fluorene skeleton represented by formula (1), a step for preparing a crystallization solution that includes aromatic hydrocarbons and methanol and that has a water content of 1 wt% or less, a step for precipitating crystals from the crystallization solution at 25 DEG C or higher and separating the precipitated crystals, and a step for bringing the crystals to 60 DEG C or higher and removing the methanol.

Description

具有茀骨架之醇之結晶及其製造方法 Crystal of alcohol having an anthracene skeleton and method for producing the same

本發明係關於一種作為形成構成以光學透鏡或光學膜為代表之光學構件之樹脂(光學樹脂)之單體較佳，且加工性、生產性優異之新穎之具有茀骨架之醇之結晶及其製造方法。 The present invention relates to a novel crystal having an anthracene skeleton which is preferably a monomer which is a resin (optical resin) constituting an optical member typified by an optical lens or an optical film, and which is excellent in workability and productivity. Production method.

以具有茀骨架之醇為原料單體之聚碳酸酯、聚酯、聚丙烯酸酯、聚胺基甲酸酯、環氧樹脂等樹脂材料由於光學特性、耐熱性等優異，故而近年來作為光學透鏡或光學片材等新光學材料受到關注。其中，具有下述式(1)： A resin material such as polycarbonate, polyester, polyacrylate, polyurethane, or epoxy resin having an anthracene skeleton as a raw material monomer is excellent in optical properties, heat resistance, and the like, and has been used as an optical lens in recent years. Or new optical materials such as optical sheets are attracting attention. Among them, there is the following formula (1):

所表示之結構且具有苯基及茀骨架之醇及由該醇類製造之樹脂以折射率等光學特性、耐熱性、耐水性、耐化學品性、電特性、機械特性、溶解性等各特性優異而受到關注(例如，日本專利特開平07-149881號公報(專利文獻1)、日本專利特開2001-122828號公報(專利文獻2)、日本專利特開2001-206863號公報(專利文獻3)、日本專利特開2009-256342號公報(專利文獻4))。 The alcohol having a phenyl group and an anthracene skeleton and the resin produced from the alcohol have optical properties such as refractive index, heat resistance, water resistance, chemical resistance, electrical properties, mechanical properties, solubility, and the like. In the case of the Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2001-122828 (Patent Document 2), Japanese Patent Laid-Open No. 2001-122828 (Patent Document 2), and Japanese Patent Laid-Open No. 2001-206863 (Patent Document 3) Japanese Patent Laid-Open Publication No. 2009-256342 (Patent Document 4)).

作為上述式(1)所表示之具有茀骨架之醇之製造方法，已知有於鹼性觸媒之存在下，使下述式(2)： The method for producing an alcohol having an anthracene skeleton represented by the above formula (1) is known to have the following formula (2) in the presence of a basic catalyst:

所表示之具有茀骨架之酚化合物與環氧乙烷反應之方法(專利文獻2)。然而，利用本方法所獲得之上述式(1)所表示之具有茀骨架之醇其純度較低，且會大量地副生成環氧乙烷與3、4分子加成而成之化合物，從而難以高純度獲得上述式(1)所表示之具有茀骨架之醇。 A method of reacting a phenol compound having an anthracene skeleton with ethylene oxide (Patent Document 2). However, the alcohol having an anthracene skeleton represented by the above formula (1) obtained by the present method has a low purity, and a large amount of a compound which is formed by addition of ethylene oxide and 3 or 4 molecules is submerged, which is difficult. The alcohol having an anthracene skeleton represented by the above formula (1) is obtained in a high purity.

另一方面，作為改善專利文獻2中記載之製法之方法，提出有於酸觸媒及硫醇類之存在下，使下述式(3)： On the other hand, as a method for improving the production method described in Patent Document 2, it is proposed to have the following formula (3) in the presence of an acid catalyst and a mercaptan:

所表示之醇類與9-茀酮反應，而獲得上述式(1)所表示之具有茀骨架之醇之方法(專利文獻3、4)。然而，專利文獻4中記載了如下主旨等，即，若藉由專利文獻3中記載之方法製造上述式(1)所表示之具有茀骨架之醇，則根據光學用途等用途而存在尤其要回避般之著色，進而，該著色即便實施精製操作亦無法去除。 A method of reacting the alcohol represented by the above with 9-fluorenone to obtain an alcohol having an anthracene skeleton represented by the above formula (1) (Patent Documents 3 and 4). However, Patent Document 4 describes that the alcohol having an anthracene skeleton represented by the above formula (1) is produced by the method described in Patent Document 3, and is particularly evasable depending on the use such as optical use. The coloration is uniform, and further, the coloring cannot be removed even if a refining operation is performed.

又，專利文獻4中以改善專利文獻2及3中所記載之製造方法為目 的，提出有如下方法：於酸觸媒及相對於9-茀酮類100重量份為3重量份以上之硫醇類之存在下，使上述式(3)所表示之醇類與9-茀酮反應，而獲得上述式(1)所表示之具有茀骨架之醇。然而，雖然利用該方法獲得之上述式(1)所表示之具有茀骨架之醇較利用專利文獻3之方法獲得者著色更少，但其著色之改善並不充分。又，由於在反應時需要大量之硫醇類，故而存在如下等問題：難以將硫醇類自上述式(1)所表示之具有茀骨架之醇完全地去除，於將該醇用作樹脂原料時，源自硫醇類之硫部分會導致樹脂之更進一步著色。 Further, Patent Document 4 proposes to improve the manufacturing methods described in Patent Documents 2 and 3. In the presence of an acid catalyst and a thiol having 3 parts by weight or more relative to 100 parts by weight of 9-fluorenone, the alcohol represented by the above formula (3) and 9-anthracene are proposed. The ketone is reacted to obtain an alcohol having an anthracene skeleton represented by the above formula (1). However, although the alcohol having an anthracene skeleton represented by the above formula (1) obtained by the method is less colored than the one obtained by the method of Patent Document 3, the improvement in coloring is not sufficient. In addition, since a large amount of mercaptans are required in the reaction, there is a problem in that it is difficult to completely remove the mercaptan from the alcohol having an anthracene skeleton represented by the above formula (1), and use the alcohol as a resin material. At the time, the sulfur moiety derived from the mercaptan causes further coloration of the resin.

進而，本案發明者等人對上述專利文獻2~4中記載之方法進行追加試驗，結果以專利文獻3中記載之方法，反應不會進行，或即便反應得以進行，亦僅獲得包含上述式(1)所表示之具有茀骨架之醇之油狀物，而並未獲得結晶狀之上述式(1)所表示之具有茀骨架之醇。另一方面，於專利文獻2及4之追加試驗中，判明雖然獲得結晶狀之上述式(1)所表示之具有茀骨架之醇，但反應或反應後之提取操作(晶析操作)中所使用之溶劑(芳香族烴類)包接於上述式(1)所表示之具有茀骨架之醇，而成為包接體。 Furthermore, the inventors of the present invention conducted additional tests on the methods described in Patent Documents 2 to 4, and as a result, the reaction described in Patent Document 3 does not proceed, or even if the reaction proceeds, only the above formula (including the above formula) is obtained. 1) An oil having an alcohol having an anthracene skeleton, and an alcohol having an anthracene skeleton represented by the above formula (1) in a crystalline form is not obtained. On the other hand, in the additional tests of Patent Documents 2 and 4, it was found that although the alcohol having the anthracene skeleton represented by the above formula (1) in a crystalline form was obtained, the extraction operation (crystallization operation) after the reaction or the reaction was carried out. The solvent (aromatic hydrocarbon) to be used is encapsulated in the alcohol having an anthracene skeleton represented by the above formula (1) to form an inclusion body.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開平07-149881號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 07-149881

[專利文獻2]日本專利特開2001-122828號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-122828

[專利文獻3]日本專利特開2001-206863號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-206863

[專利文獻4]日本專利特開2009-256342號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-256342

本發明之目的在於提供一種不使用硫醇類而高純度且著色較少，進而並非為包接體之上述式(1)所表示之具有茀骨架之醇之結 晶。 An object of the present invention is to provide an alcohol having an anthracene skeleton represented by the above formula (1) which is not high in purity and which is less colored without using a mercaptan. crystal.

為了解決上述問題，本發明者等人重複進行努力研究，結果發現，藉由於特定之條件下製造上述式(1)所表示之具有茀骨架之醇，並於特定條件下使所獲得之該醇類晶析，可製造高純度且著色較少，進而並非為包接體之上述式(1)所表示之具有茀骨架之醇之結晶。具體而言，包括以下之發明。 In order to solve the above problems, the inventors of the present invention have repeatedly conducted diligent research, and as a result, have found that the alcohol having an anthracene skeleton represented by the above formula (1) is produced under specific conditions, and the obtained alcohol is obtained under specific conditions. The crystallization is such that high purity and less coloration can be produced, and the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) of the inclusion body is not obtained. Specifically, the following inventions are included.

[1]一種下述式(1)所表示之具有茀骨架之醇之結晶， [1] A crystal of an alcohol having an anthracene skeleton represented by the following formula (1),

其利用示差掃描熱量分析所得之熔解吸熱最大溫度為148~151℃。 The melting endothermic maximum temperature obtained by differential scanning calorimetry is 148 to 151 °C.

[2]一種下述式(1)所表示之具有茀骨架之醇之結晶， [2] a crystal of an alcohol having an anthracene skeleton represented by the following formula (1),

其於利用Cu-Kα射線所得之粉末X射線繞射圖案中，於繞射角2θ=7.1±0.2°、14.3±0.2°、15.2±0.2°、15.8±0.2°、17.1±0.2°及22.3±0.2°處具有峰。 It is in the powder X-ray diffraction pattern obtained by using Cu-Kα ray at diffraction angles 2θ=7.1±0.2°, 14.3±0.2°, 15.2±0.2°, 15.8±0.2°, 17.1±0.2° and 22.3± There is a peak at 0.2°.

[3]一種下述式(1)所表示之具有茀骨架之醇之結晶， [3] a crystal of an alcohol having an anthracene skeleton represented by the following formula (1),

其於利用Cu-Kα射線所得之粉末X射線繞射圖案中，於繞射角2θ=8.1±0.2°、15.4±0.2°、16.6±0.2°、18.0±0.2°、20.4±0.2°、21.1±0.2°及22.7±0.2°處具有峰。 It is in the powder X-ray diffraction pattern obtained by using Cu-Kα ray at diffraction angles 2θ=8.1±0.2°, 15.4±0.2°, 16.6±0.2°, 18.0±0.2°, 20.4±0.2°, 21.1± There are peaks at 0.2° and 22.7±0.2°.

[4]如[2]或[3]記載之具有茀骨架之醇之結晶，其中利用示差掃描熱量分析所得之熔解吸熱最大溫度為148~151℃。 [4] The crystal of an alcohol having an anthracene skeleton as described in [2] or [3], wherein the maximum melting endothermic temperature obtained by differential scanning calorimetry is 148 to 151 °C.

[5]如[1]至[4]中任一項所記載之具有茀骨架之醇之結晶，其並非為包接體。 [5] The crystal of an alcohol having an anthracene skeleton according to any one of [1] to [4], which is not an inclusion body.

[6]如[1]至[5]中任一項所記載之具有茀骨架之醇之結晶，其中將上述式(1)所表示之具有茀骨架之醇12g溶解於純度99重量%以上之N,N-二甲基甲醯胺30mL而成之溶液之黃度(YI值)成為10以下。 [6] The crystal of an alcohol having an anthracene skeleton according to any one of [1] to [5], wherein 12 g of the alcohol having an anthracene skeleton represented by the above formula (1) is dissolved in a purity of 99% by weight or more. The yellowness (YI value) of the solution of N,N-dimethylformamide 30 mL was 10 or less.

[7]如[1]至[6]中任一項所記載之具有茀骨架之醇之結晶，其中芳香族烴類之含量為1重量%以下。 [7] The crystal of an alcohol having an anthracene skeleton according to any one of [1] to [6] wherein the content of the aromatic hydrocarbon is 1% by weight or less.

[8]一種如[1]至[7]中任一項所記載之具有茀骨架之醇之結晶之製造方法，其依序包括以下(i)~(iv)之步驟：(i)於對稱乙二醇二醚之存在下，使下述式(2)：[化7] [8] A method for producing a crystal of an alcohol having an anthracene skeleton according to any one of [1] to [7], which comprises the following steps (i) to (iv): (i) symmetry In the presence of ethylene glycol diether, the following formula (2) is made: [Chemical 7]

所表示之具有茀骨架之酚化合物與碳酸乙烯酯反應，而獲得包含上述式(1)所表示之具有茀骨架之醇之反應液之步驟；(ii)將芳香族烴類及甲醇添加至上述反應液中，而製備包含芳香族烴類及甲醇之溶液且該溶液中之水之含量成為1重量%以下之晶析溶液之步驟；(iii)於25℃以上使結晶自上述晶析溶液析出，並將所析出之結晶分離之步驟；(iv)將上述結晶設為60℃以上，而去除甲醇之步驟。 a step of reacting a phenol compound having an anthracene skeleton with ethylene carbonate to obtain a reaction liquid containing an alcohol having an anthracene skeleton represented by the above formula (1); (ii) adding an aromatic hydrocarbon and methanol to the above a step of preparing a crystallization solution containing a solution of an aromatic hydrocarbon and methanol and having a water content of 1% by weight or less in the reaction solution; (iii) precipitating crystals from the crystallization solution at 25 ° C or higher And the step of separating the precipitated crystals; (iv) the step of removing the methanol by setting the above crystals to 60 ° C or higher.

根據本發明，可提供一種高純度且著色較少，進而並非為包接體之上述式(1)所表示之具有茀骨架之醇之結晶。 According to the present invention, it is possible to provide a crystal of an alcohol having an anthracene skeleton represented by the above formula (1) which is high in purity and which is less colored and which is not an inclusion body.

尤其於上述式(1)所表示之具有茀骨架之醇之結晶為包接體之情形時，使丙烯酸等與該包接體反應而製成其他化合物時，包接體所包接之化合物(以下，有時亦稱為客體分子)阻礙反應，而存在視反應而無法使用等問題，又，於直接進行熔融等而用作樹脂原料時，存在亦必須將熔融中所產生之源自客體分子之蒸氣去除至反應系外，或者因客體分子之影響，而引起所獲得之樹脂之品質變得不固定等問題之情況。進而，由於可能包接引火點較低之客體分子(於上述引例之情形時，為芳香族烴類)，故而亦存在保管或輸送上述式(1)所表示之具有茀骨架之醇時，容易引起火災等防災上之擔憂。 In particular, when the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) is an inclusion body, when an acrylic acid or the like is reacted with the inclusion body to form another compound, the compound enclosed by the inclusion body ( Hereinafter, the guest molecule may be hindered from reacting, and there is a problem that it may not be used depending on the reaction. When it is directly used for melting or the like as a resin material, it is necessary to also produce a guest molecule derived from melting. The vapor is removed to the outside of the reaction system, or the quality of the obtained resin is not fixed due to the influence of the guest molecule. Further, since it is possible to include a guest molecule having a lower ignition point (in the case of the above-mentioned example, it is an aromatic hydrocarbon), it is easy to store or transport the alcohol having an anthracene skeleton represented by the above formula (1). Causes fire and other disaster prevention concerns.

然而，如上所述，欲基於公知之方法而以結晶之形式獲得上述 式(1)所表示之具有茀骨架之醇之情形時，以包接有客體分子之包接體之形式獲得，而獲得並非為包接體之上述式(1)所表示之具有茀骨架之醇之結晶之方法尚屬未知。另一方面，包含於包接體之客體分子通常難以藉由在客體分子之沸點以上之溫度下使結晶乾燥等一般實施之方法而去除，並且必須利用暫且將結晶加熱至熔點以上而使之熔融之後將客體分子去除等於工業上實施困難、或非常耗費成本之方法，因此，已研究出並非為包接體之上述式(1)所表示之具有茀骨架之醇之結晶及其製造方法之本發明尤其於工業性規模方面製造、使用上述式(1)所表示之具有茀骨架之醇之結晶時，可以說非常有意義。 However, as described above, the above is obtained in the form of crystals based on a known method. In the case of the alcohol having an anthracene skeleton represented by the formula (1), it is obtained in the form of an inclusion body in which a guest molecule is encapsulated, and an anthracene skeleton represented by the above formula (1) which is not an inclusion body is obtained. The method of crystallization of alcohol is unknown. On the other hand, the guest molecule contained in the inclusion body is usually difficult to remove by a general method such as drying the crystal at a temperature higher than the boiling point of the guest molecule, and it is necessary to melt the crystal by heating it to a melting point or more. Subsequent removal of the guest molecule is equivalent to an industrially difficult or very costly method. Therefore, it has been studied that the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) which is not the inclusion body and the method for producing the same have been studied. The invention is particularly useful in the production and use of the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) in terms of industrial scale.

圖1係表示實施例1中所獲得之結晶(本發明之結晶)之示差掃描熱量測定(DSC)曲線之圖。 Fig. 1 is a graph showing a differential scanning calorimetry (DSC) curve of the crystal obtained in Example 1 (crystal of the present invention).

圖2係表示比較例1中所獲得之結晶(包接體)之示差掃描熱量測定(DSC)曲線之圖。 Fig. 2 is a graph showing a differential scanning calorimetry (DSC) curve of a crystal (encapsulated body) obtained in Comparative Example 1.

圖3係表示比較例9中所獲得之結晶(包接體)之示差掃描熱量測定(DSC)曲線之圖。 Fig. 3 is a graph showing a differential scanning calorimetry (DSC) curve of a crystal (encapsulated body) obtained in Comparative Example 9.

圖4係表示實施例1中所獲得之結晶(本發明之結晶)之粉末X射線繞射圖案之圖。 Fig. 4 is a view showing a powder X-ray diffraction pattern of the crystal obtained in Example 1 (crystal of the present invention).

圖5係表示比較例1中所獲得之結晶(包接體)之粉末X射線繞射圖案之圖。 Fig. 5 is a view showing a powder X-ray diffraction pattern of the crystal (encapsulated body) obtained in Comparative Example 1.

圖6係表示比較例9中所獲得之結晶(包接體)之粉末X射線繞射圖案之圖。 Fig. 6 is a view showing a powder X-ray diffraction pattern of the crystal (encapsulated body) obtained in Comparative Example 9.

圖7係比較例1中所獲得之結晶(包接體)之TG-DTA線圖。 Fig. 7 is a TG-DTA line diagram of the crystal (inclusion body) obtained in Comparative Example 1.

圖8係表示實施例7中所獲得之結晶(本發明之結晶)之示差掃描熱量測定(DSC)曲線之圖。 Fig. 8 is a graph showing a differential scanning calorimetry (DSC) curve of the crystal obtained in Example 7 (crystal of the present invention).

圖9係表示實施例7中所獲得之結晶(本發明之結晶)之粉末X射線 繞射圖案之圖。 Figure 9 is a diagram showing the powder X-ray of the crystal obtained in Example 7 (crystal of the present invention) A diagram of the diffraction pattern.

<上述式(1)所表示之具有茀骨架之醇之結晶之製造方法> <Method for Producing Crystal of Alcohol Having An Anthracene Structure represented by the above formula (1)>

具有上述特徵之本發明之上述式(1)所表示之具有茀骨架之醇之結晶係藉由以下(i)~(iv)之步驟而製造。 The crystal of the alcohol having an anthracene skeleton represented by the above formula (1) of the present invention having the above characteristics is produced by the following steps (i) to (iv).

(i)於對稱乙二醇二醚之存在下，使上述式(2)所表示之具有茀骨架之酚化合物與碳酸乙烯酯反應，而獲得包含上述式(1)所表示之具有茀骨架之醇之反應液之步驟(以下，有時亦稱為反應步驟)。 (i) reacting a phenol compound having an anthracene skeleton represented by the above formula (2) with ethylene carbonate in the presence of a symmetrical ethylene glycol diether to obtain an anthracene skeleton represented by the above formula (1) The step of reacting the alcohol (hereinafter sometimes referred to as the reaction step).

(ii)將芳香族烴類及甲醇添加至反應液中，而製備包含芳香族烴類及甲醇之溶液且該溶液中之水之含量成為1重量%以下之晶析溶液之步驟(以下，有時亦稱為晶析溶液製備步驟)。 (ii) a step of preparing a crystallization solution containing a solution of an aromatic hydrocarbon and methanol and a water content of the solution of 1% by weight or less or less by adding an aromatic hydrocarbon and methanol to the reaction liquid (hereinafter, Also referred to as the crystallization solution preparation step).

(iii)於25℃以上使結晶自上述晶析溶液析出，並將所析出之結晶分離之步驟(以下，有時亦稱為晶析步驟)。 (iii) a step of separating crystals from the crystallization solution at 25 ° C or higher and separating the precipitated crystals (hereinafter sometimes referred to as a crystallization step).

(iv)將上述結晶設為60℃以上，而去除甲醇之步驟(以下，有時亦稱為乾燥步驟)。 (iv) A step of removing methanol by removing the above-mentioned crystals at 60 ° C or higher (hereinafter, also referred to as a drying step).

以下，對上述(i)~(iv)之步驟進行詳細敍述。 Hereinafter, the steps (i) to (iv) above will be described in detail.

<反應步驟> <Reaction step>

本發明之上述式(1)所表示之具有茀骨架之醇必須於對稱乙二醇二醚之存在下，使上述式(2)所表示之具有茀骨架之酚化合物與碳酸乙烯酯反應而製造。作為上述式(1)所表示之具有茀骨架之醇之製造方法，已知有上述專利文獻2~4之方法，但於利用該等製造法而製造之情形時，因源自該等製法之雜質之影響，而無法製造具有下述特徵之上述式(1)所表示之具有茀骨架之醇之結晶(以下，有時亦將該結晶稱為本發明之結晶)。 The alcohol having an anthracene skeleton represented by the above formula (1) of the present invention is produced by reacting a phenol compound having an anthracene skeleton represented by the above formula (2) with ethylene carbonate in the presence of a symmetrical ethylene glycol diether. . The method of the above-mentioned Patent Documents 2 to 4 is known as a method for producing an alcohol having an anthracene skeleton represented by the above formula (1). However, when it is produced by such a production method, it is derived from such a method. The crystal of the alcohol having an anthracene skeleton represented by the above formula (1) having the following characteristics (hereinafter, the crystal is sometimes referred to as the crystal of the present invention) cannot be produced by the influence of impurities.

本發明中所使用之上述式(2)所表示之具有茀骨架之酚化合物可使用市售品，又，亦可於酸觸媒之存在下，使茀酮與2-苯基苯酚反應 而製造。 The phenol compound having an anthracene skeleton represented by the above formula (2) used in the present invention may be a commercially available product, or may be reacted with 2-phenylphenol in the presence of an acid catalyst. And manufacturing.

本發明中所使用之對稱乙二醇二醚具有下述式(4)：R-O(CH2CH2O)n-R (4) The symmetrical ethylene glycol diether used in the present invention has the following formula (4): RO(CH 2 CH 2 O) n -R (4)

(式中，R表示碳數1~4之烷基，n表示1~4之整數) (wherein R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4)

所表示之結構。作為此種對稱乙二醇二醚，具體而言，例如例示有四乙二醇二甲醚、二乙二醇二丁醚、三乙二醇二甲醚、二乙二醇二***、乙二醇二甲醚、單乙二醇二***、單乙二醇二甲醚等。 The structure represented. Specific examples of such a symmetrical ethylene glycol diether include tetraethylene glycol dimethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, and ethylene. Alcohol dimethyl ether, monoethylene glycol diethyl ether, monoethylene glycol dimethyl ether and the like.

本發明中所使用之對稱乙二醇二醚相對於上述式(2)所表示之具有茀骨架之酚化合物1重量倍，通常使用0.05~3重量倍，較佳為使用0.08~1重量倍。藉由使用0.05重量倍以上，可實現更高純度，尤其可抑制加成有碳酸乙烯酯3分子以上之雜質之生成，藉由將使用量設為3重量倍以下，可減少昂貴之對稱乙二醇二醚之使用量，因此，可更經濟地製造上述式(1)所表示之具有茀骨架之醇。 The symmetrical ethylene glycol diether used in the present invention is usually used in an amount of 0.05 to 3 times by weight, preferably 0.08 to 1 part by weight, based on 1 part by weight of the phenol compound having an anthracene skeleton represented by the above formula (2). By using 0.05 times or more, higher purity can be achieved, and in particular, formation of impurities of 3 or more molecules of ethylene carbonate can be suppressed, and by using the amount of 3 times or less, the expensive symmetrical ethylene can be reduced. Since the amount of the alcohol diether used is such that the alcohol having an anthracene skeleton represented by the above formula (1) can be produced more economically.

本發明中所使用之碳酸乙烯酯相對於上述式(2)所表示之具有茀骨架之酚化合物1莫耳，通常使用2~10莫耳，較佳為使用2~4莫耳。藉由使用2莫耳以上，可獲得充分之反應速度，藉由將使用量設為10莫耳以下，可更經濟地製造上述式(2)所表示之具有茀骨架之醇。 The ethylene carbonate used in the present invention is usually 2 to 10 moles, preferably 2 to 4 moles, based on the phenol compound 1 mole having an anthracene skeleton represented by the above formula (2). By using 2 mol or more, a sufficient reaction rate can be obtained, and by using the amount of 10 mol or less, the alcohol having an anthracene skeleton represented by the above formula (2) can be produced more economically.

使上述式(2)所表示之具有茀骨架之酚化合物與碳酸乙烯酯反應時，視需要於鹼性化合物之存在下進行反應。作為反應步驟中所使用之鹼性化合物，例如例示有碳酸鹽類、碳酸氫鹽類、氫氧化物類、有機鹼類等。更具體而言，作為碳酸鹽類，例示有碳酸鉀、碳酸鈉、碳酸鋰、碳酸銫等，作為碳酸氫鹽類，例示有碳酸氫鉀、碳酸氫鈉、碳酸氫鋰、碳酸氫銫等，作為氫氧化物類，例示有氫氧化鈉、氫氧化鉀、氫氧化鋰等，作為有機鹼類，例示有三乙胺、二甲胺基吡啶、三苯基膦、溴化四甲基銨、氯化四甲基銨等。該等鹼性化合物之中，就操作性良好之方面而言，較佳地使用碳酸鉀、碳酸鈉、三苯基膦。使 用該等鹼性化合物時之使用量相對於上述式(2)所表示之具有茀骨架之酚化合物1莫耳，通常為0.01~1.0莫耳，較佳為0.03~0.2倍莫耳。 When the phenol compound having an anthracene skeleton represented by the above formula (2) is reacted with ethylene carbonate, the reaction is carried out in the presence of a basic compound as necessary. Examples of the basic compound used in the reaction step include carbonates, hydrogencarbonates, hydroxides, and organic bases. More specifically, examples of the carbonates include potassium carbonate, sodium carbonate, lithium carbonate, and cesium carbonate. Examples of the hydrogencarbonate include potassium hydrogencarbonate, sodium hydrogencarbonate, lithium hydrogencarbonate, and cesium hydrogencarbonate. Examples of the hydroxides include sodium hydroxide, potassium hydroxide, and lithium hydroxide. Examples of the organic bases include triethylamine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, and chlorine. Tetramethylammonium and the like. Among these basic compounds, potassium carbonate, sodium carbonate, and triphenylphosphine are preferably used in terms of good handleability. Make When the basic compound is used, the amount of the phenol compound having a fluorene skeleton represented by the above formula (2) is usually 0.01 to 1.0 mol, preferably 0.03 to 0.2 mol.

實施反應步驟時，可視需要與對稱乙二醇二醚一併使用有機溶劑。作為可並用之有機溶劑，只要為對於上述式(2)所表示之具有茀骨架之酚化合物及碳酸乙烯酯為惰性者即可，例示有酮類、芳香族烴類、鹵化芳香族烴類、脂肪族烴類、鹵化脂肪族烴類、醚類、酯類、脂肪族腈類、醯胺類、亞碸類等。更具體而言，作為酮類，例示有丙酮、甲基乙基酮、丁基甲基酮、二異丁基酮、甲基異丁基酮、甲基異戊酮、2-庚酮、2-辛酮、環己酮等，作為芳香族烴類，例示有甲苯、二甲苯、均三甲苯等，作為鹵化芳香族烴，例示有氯苯、二氯苯等，作為脂肪族烴，例示有戊烷、己烷、庚烷等，作為鹵化脂肪族烴類，例示有二氯甲烷、1,2-二氯乙烷等，作為醚類，例示有二***、二異丙醚、甲基第三丁醚、環戊基甲醚、二苯醚等，作為酯類，例示有乙酸乙酯、乙酸丁酯等，作為脂肪族腈類，例示有乙腈等，作為醯胺類，例示有二甲基甲醯胺、二甲基乙醯胺等，作為亞碸類，例示有二甲基亞碸等。該等可併用之有機溶劑之中，就可獲得性或操作性良好之方面而言，可較佳地使用101.3kPa下之沸點為110℃以上之芳香族烴類、酮類或醚類。該等有機溶劑可使用1種，或視需要混合2種以上而使用。併用該等有機溶劑時之使用量相對於上述式(2)所表示之具有茀骨架之酚化合物1重量倍，通常為0.1~5重量倍，較佳為0.5~3重量倍。 When the reaction step is carried out, an organic solvent may be used together with the symmetrical ethylene glycol diether as needed. The organic solvent which can be used in combination with the phenol compound having an anthracene skeleton represented by the above formula (2) and ethylene carbonate is exemplified, and examples thereof include ketones, aromatic hydrocarbons, and halogenated aromatic hydrocarbons. Aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, esters, aliphatic nitriles, guanamines, anthraquinones, and the like. More specifically, examples of the ketones include acetone, methyl ethyl ketone, butyl methyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, and 2-octane. Examples of the aromatic hydrocarbons include toluene, xylene, and mesitylene. Examples of the halogenated aromatic hydrocarbons include chlorobenzene and dichlorobenzene. Examples of the aliphatic hydrocarbons include pentane. Examples of the halogenated aliphatic hydrocarbons include dichloromethane and 1,2-dichloroethane. Examples of the ethers include diethyl ether, diisopropyl ether and methyl third. Examples of the esters include ethyl acetate and butyl acetate. Examples of the esters include acetonitrile and the like, and examples of the guanamines include dimethylamine. Amidoxime, dimethylacetamide, etc., as an anthraquinone, a dimethyl hydrazine etc. are illustrated. Among these organic solvents which can be used together, aromatic hydrocarbons, ketones or ethers having a boiling point of 110 ° C or more at 101.3 kPa can be preferably used in terms of availability or workability. These organic solvents may be used alone or in combination of two or more kinds as needed. The amount of the organic solvent to be used is usually 0.1 to 5 times by weight, preferably 0.5 to 3 times by weight, based on 1 part by weight of the phenol compound having an anthracene skeleton represented by the above formula (2).

反應步驟係將對稱乙二醇二醚、及視需要之鹼性化合物、可併用之有機溶劑添加至反應容器，且通常於30~150℃實施，較佳為於100~130℃實施。 The reaction step is carried out by adding a symmetric ethylene glycol diether, an optional basic compound, and an organic solvent which can be used in combination to a reaction vessel, and is usually carried out at 30 to 150 ° C, preferably at 100 to 130 ° C.

包含以此方式獲得之上述式(1)所表示之具有茀骨架之醇之反應液可直接於濃縮、乾燥之後，於晶析溶液製備步驟中使用，亦可藉由 水洗、吸附處理等後處理、或晶析、管柱精製等慣例進行精製，但於實施下述水洗步驟及/或濃縮步驟之後，於本發明之晶析溶液製備步驟中使用能夠進一步提高上述式(1)所表示之具有茀骨架之醇之純度，故而較佳。以下，對水洗步驟及濃縮步驟進行詳細敍述。 The reaction liquid containing the alcohol having an anthracene skeleton represented by the above formula (1) obtained in this manner may be used directly in the preparation step of the crystallization solution after concentration and drying, or may be used by Purification by post-treatment such as water washing or adsorption treatment, or crystallization, column purification, etc., but after the following water washing step and/or concentration step, the use of the crystallization solution preparation step of the present invention can further improve the above formula. (1) It is preferred that the purity of the alcohol having an anthracene skeleton is represented. Hereinafter, the water washing step and the concentration step will be described in detail.

水洗步驟係藉由如下方式實施，即，將相對於反應中使用之上述式(2)所表示之具有茀骨架之酚化合物1重量倍為0.1~10重量倍、較佳為0.5~5重量倍之水添加至所獲得之反應液，並於60~95℃、較佳為75~90℃下進行攪拌，其後，將其靜置，並將水層分離。藉由使用0.1重量倍以上之水，進一步顯現水洗步驟之效果，藉由將使用量設為10重量倍以下，而可改善容積效率。又，藉由將水洗溫度設為60℃以上，靜置時之分液速度變得更快，藉由設為95℃以下，可抑制水洗時之上述式(1)所表示之具有茀骨架之醇之分解。 The water washing step is carried out by using 0.1 to 10 times by weight, preferably 0.5 to 5 times by weight, based on 1 part by weight of the phenol compound having an anthracene skeleton represented by the above formula (2) used in the reaction. The water is added to the obtained reaction liquid, and stirred at 60 to 95 ° C, preferably 75 to 90 ° C, after which it is allowed to stand and the aqueous layer is separated. The effect of the water washing step is further exhibited by using 0.1 times by weight or more of water, and the volumetric efficiency can be improved by setting the amount used to 10 times or less. In addition, when the water washing temperature is 60° C. or higher, the liquid separation speed at the time of standing is increased, and when it is 95° C. or lower, the ruthenium skeleton represented by the above formula (1) at the time of water washing can be suppressed. Decomposition of alcohol.

水洗步驟亦可視需要實施複數次。又，實施水洗步驟時，亦可與水一併添加鹼或酸，而將副產物等分解、去除至水層。 The washing step can also be carried out as many times as needed. Further, when the water washing step is carried out, a base or an acid may be added together with water, and by-products or the like may be decomposed and removed to the water layer.

繼而，對濃縮步驟進行詳細敍述。濃縮步驟係藉由如下方式實施，即，對於水洗步驟結束之後、或並未實施水洗步驟之反應液，於常壓、或減壓下，將上述反應步驟中使用之對稱乙二醇二醚或可併用之有機溶劑之一部分或全部去除至反應系外。 Next, the concentration step will be described in detail. The concentrating step is carried out by using the symmetrical ethylene glycol diether used in the above reaction step at normal pressure or under reduced pressure for the reaction liquid after the completion of the water washing step or without the water washing step. Part or all of the organic solvent that can be used in combination is removed to the outside of the reaction system.

<晶析溶液製備步驟及晶析步驟> <Cleavage solution preparation step and crystallization step>

於本發明之結晶之製造方法中，藉由將芳香族烴類及甲醇添加至包含上述式(1)所表示之具有茀骨架之醇之反應液、或上述式(1)所表示之具有茀骨架之醇之結晶等，而製備晶析溶液。再者，於該晶析溶液中包含1重量%以上之水分之情形時，必須使水之含量為1重量%以下。於調製晶析溶液之後，溶液中結晶並未完全溶解之情形時，必須使結晶完全溶解，其後進行冷卻而使上述式(1)所表示之具有茀骨架之醇之結晶析出之後，進行分離。 In the method for producing a crystal of the present invention, an aromatic hydrocarbon and methanol are added to a reaction liquid containing an alcohol having an anthracene skeleton represented by the above formula (1), or a hydrazine represented by the above formula (1) A crystallization solution is prepared by crystallizing the alcohol of the skeleton or the like. In addition, when the crystallization solution contains 1% by weight or more of water, the content of water must be 1% by weight or less. After the crystallization solution is prepared, when the crystals in the solution are not completely dissolved, the crystals must be completely dissolved, and then the crystals of the alcohol having the anthracene skeleton represented by the above formula (1) are precipitated and then separated. .

作為本發明中可使用之芳香族烴類，例示有甲苯、二甲苯、均三甲苯等。又，於僅使用芳香族烴類實施晶析步驟之情形時，會成為包接有該芳香族烴類之包接體，因此，必須併用甲醇。再者，於使用除甲醇以外之醇之情形時，與單獨使用芳香族烴類實施晶析步驟之情形同樣地，會成為包接有該芳香族烴類之包接體，從而無法獲得本發明之結晶。 Examples of the aromatic hydrocarbons usable in the present invention include toluene, xylene, and mesitylene. Further, when the crystallization step is carried out using only aromatic hydrocarbons, the inclusion of the aromatic hydrocarbons is included, and therefore, it is necessary to use methanol in combination. In the case where an alcohol other than methanol is used, as in the case where the crystallization step is carried out using an aromatic hydrocarbon alone, the inclusion of the aromatic hydrocarbon may be included, and the present invention cannot be obtained. Crystallization.

晶析溶液中之芳香族烴類與甲醇之比率例如以重量基準計，芳香族烴類：甲醇=1：0.3~1：5，較佳為1：0.5~1：4。藉由將甲醇之比率設為相對於芳香族烴類0.3重量倍以上，可抑制成為包含芳香族烴類之包接體，藉由設為5重量倍以下，變得容易溶解上述式(1)所表示之具有茀骨架之醇，故而晶析操作變得更容易，又，易於改善上述式(1)所表示之具有茀骨架之醇之純度或色調，故而較佳。該等比率例如可藉由利用氣相層析法對包含於反應液等之芳香族烴類或甲醇之含量進行定量之後，以成為所期望之比率之方式添加芳香族烴類及甲醇而進行調整。 The ratio of the aromatic hydrocarbon to the methanol in the crystallization solution is, for example, on a weight basis, and the aromatic hydrocarbon: methanol = 1:0.3 to 1:5, preferably 1:0.5 to 1:4. By setting the ratio of methanol to 0.3 times by weight or more with respect to the aromatic hydrocarbon, it is possible to suppress inclusion of an inclusion body containing an aromatic hydrocarbon, and it is easy to dissolve the above formula (1) by setting it to 5 times by weight or less. Since the alcohol having an anthracene skeleton is represented, the crystallization operation becomes easier, and the purity or color tone of the alcohol having an anthracene skeleton represented by the above formula (1) is easily improved, which is preferable. These ratios can be adjusted by, for example, adding a content of an aromatic hydrocarbon or methanol contained in a reaction liquid by gas chromatography, and adding an aromatic hydrocarbon and methanol so as to have a desired ratio. .

晶析溶液亦可包含除芳香族烴類、甲醇以外之其他溶劑。作為亦可包含之溶劑，例如，除上述反應中所使用之對稱乙二醇二醚以外，可列舉脂肪族烴類(例如戊烷、己烷、庚烷等)、鏈狀酮類(例如丙酮、甲基乙基酮、甲基異丁基酮等)等。包含其他溶劑之情形時之其溶劑量相對於晶析溶液中之芳香族烴類與甲醇之合計量，通常設為0.5重量倍以下，較佳為設為0.3重量倍以下。藉由設為0.5重量倍以下，可經濟且更穩定地獲得本發明之結晶。 The crystallization solution may also contain other solvents than aromatic hydrocarbons and methanol. Examples of the solvent which may be contained include, in addition to the symmetrical ethylene glycol diether used in the above reaction, aliphatic hydrocarbons (for example, pentane, hexane, heptane, etc.) and chain ketones (for example, acetone). , methyl ethyl ketone, methyl isobutyl ketone, etc.). In the case of containing another solvent, the amount of the solvent is usually 0.5 times by weight or less, preferably 0.3 times by weight or less, based on the total amount of the aromatic hydrocarbons and methanol in the crystallization solution. The crystal of the present invention can be obtained economically and more stably by setting it to 0.5 weight times or less.

包含於晶析溶液之溶劑之總量相對於包含於晶析溶液之上述式(1)所表示之具有茀骨架之醇1重量倍，通常為0.5~20重量倍，較佳為1~10重量倍。藉由使用0.5重量倍以上，進一步顯現利用晶析操作獲得之精製效果，藉由設為20重量倍以下，可產率良好地獲得上述式 (1)所表示之具有茀骨架之醇。 The total amount of the solvent contained in the crystallization solution is usually 0.5 to 20 times by weight, preferably 1 to 10 parts by weight, based on 1 part by weight of the alcohol having an anthracene skeleton represented by the above formula (1) contained in the crystallization solution. Times. By using 0.5 times by weight or more, the purification effect obtained by the crystallization operation is further exhibited, and by setting it to 20 weight times or less, the above formula can be obtained with good yield. (1) An alcohol having an anthracene skeleton.

於晶析溶液中含有多於1重量%之水之情形時，存在無法獲得結晶狀之上述式(1)所表示之具有茀骨架之醇之情況。又，即便於可獲得結晶狀之上述式(1)所表示之具有茀骨架之醇之情形時，亦無法成為具有下述特徵之本發明之結晶，且純度或色調並未充分地提高。作為使晶析溶液中之水分為1重量%以下之方法，例如可列舉如下方法：於添加甲醇之前，先添加芳香族烴溶劑，並於常壓或減壓下藉由共沸脫水而將水分去除之後，添加不含水分之甲醇。 When the crystallization solution contains more than 1% by weight of water, there is a case where an alcohol having an anthracene skeleton represented by the above formula (1) in a crystalline form cannot be obtained. Further, even in the case where an alcohol having an anthracene skeleton represented by the above formula (1) in a crystalline form can be obtained, the crystal of the present invention having the following characteristics cannot be obtained, and the purity or color tone is not sufficiently improved. As a method of making the water content in the crystallization solution 1% by weight or less, for example, an aromatic hydrocarbon solvent is added before the addition of methanol, and the water is removed by azeotropic dehydration under normal pressure or reduced pressure. After removal, add moisture-free methanol.

繼而，對晶析步驟進行詳細敍述。藉由上述方法而製備之晶析溶液通常加熱至40℃以上、晶析溶液之沸點以下之溫度而使結晶完全溶解之後進行冷卻，並於25℃以上、較佳為於25~60℃、進而較佳為於40~50℃下使結晶析出。在於低於25℃之溫度使結晶析出之情形時，存在無法獲得本發明之結晶，且成為包接有芳香族烴類之包接體之情況。又，在於高於60℃之溫度使結晶析出之情形時，存在因溶劑之沸點相近，而操作性成為問題之情況。作為於上述溫度範圍內使結晶析出之方法，例示有：於上述溫度範圍內保持晶析溶液之溫度直至結晶析出之方法、於上述溫度範圍內接種籽晶之方法等。再者，結晶析出之後，於同一溫度保持一定時間而使結晶成長之方法可更確實地獲得本發明之結晶，故而較佳。 Next, the crystallization step will be described in detail. The crystallization solution prepared by the above method is usually heated to a temperature of 40 ° C or higher and a boiling point or lower of the crystallization solution to completely dissolve the crystal, followed by cooling, and at 25 ° C or higher, preferably at 25 to 60 ° C, and further It is preferred to precipitate crystals at 40 to 50 °C. When the crystal is precipitated at a temperature lower than 25 ° C, there is a case where the crystal of the present invention cannot be obtained and the inclusion of an aromatic hydrocarbon is contained. Further, in the case where the crystal is precipitated at a temperature higher than 60 ° C, the boiling point of the solvent is similar, and workability is a problem. The method of precipitating crystals in the above temperature range is exemplified by a method of maintaining the temperature of the crystallization solution in the above temperature range until crystallization is precipitated, a method of inoculating the seed crystal in the above temperature range, and the like. Further, after the crystallization is carried out, the method of growing the crystal at the same temperature for a certain period of time can more reliably obtain the crystal of the present invention, which is preferable.

結晶析出之後，視需要進而進行冷卻，並將所析出之結晶分離。如此所分離之結晶雖然包含晶析步驟中所使用之溶劑(芳香族烴、甲醇等)，但是與包接有芳香族烴類之結晶不同，即便不設為結晶熔解之溫度(熔點)以上，而藉由設為60℃以上，亦可將晶析步驟中所使用之溶劑去除，故而可製造並非為包接體之本發明之結晶。 After the crystallization is precipitated, it is further cooled as necessary, and the precipitated crystals are separated. The crystals thus separated include the solvent (aromatic hydrocarbon, methanol, etc.) used in the crystallization step, but unlike the crystal in which the aromatic hydrocarbon is encapsulated, even if it is not set to the temperature (melting point) of the crystal melting, Further, by setting the temperature to 60 ° C or higher, the solvent used in the crystallization step can be removed, so that the crystal of the present invention which is not an inclusion body can be produced.

<乾燥步驟> <drying step>

藉由實施乾燥步驟，可將包含甲醇之晶析步驟中所使用之溶劑 去除。乾燥步驟係藉由將所獲得之結晶設為60℃以上、結晶之熔點以下，較佳為設為60℃~110℃而實施。於低於60℃之情形時，無法去除晶析步驟中所使用之溶劑中之甲醇，或者即便能夠去除，亦需要大量之時間，就工業性之觀點而言，效率較低。實施乾燥步驟時，可為常壓下，亦可為減壓下，但工業上實施時，設為減壓下可更有效率地將包含甲醇之晶析步驟中所使用之溶劑去除，故而較佳。 By using a drying step, the solvent used in the crystallization step containing methanol can be used. Remove. The drying step is carried out by setting the obtained crystal to 60 ° C or higher and the melting point of the crystal or lower, preferably 60 ° C to 110 ° C. When the temperature is lower than 60 ° C, the methanol in the solvent used in the crystallization step cannot be removed, or even if it can be removed, a large amount of time is required, and from the viewpoint of industrial efficiency, the efficiency is low. When the drying step is carried out, it may be under normal pressure or under reduced pressure. However, when it is industrially carried out, the solvent used in the crystallization step containing methanol can be removed more efficiently under reduced pressure. good.

以此方式獲得之本發明之結晶亦可視需要重複進行吸附、水蒸氣蒸餾、再結晶等通常之精製操作，但即便不實施此種操作，亦為充分之高純度，又，結晶中亦不包接客體分子，因此，可較佳地用作聚碳酸酯、聚酯、聚丙烯酸酯、聚胺基甲酸酯、環氧樹脂等樹脂材料自不待言，亦可較佳地用於客體分子成為問題之領域，例如用作醫農藥用之原料(中間物)。 The crystal of the present invention obtained in this manner can be repeatedly subjected to usual purification operations such as adsorption, steam distillation, recrystallization, etc., but even if such an operation is not carried out, it is sufficiently high in purity, and the crystal is not included. The guest molecule is used, and therefore, it can be preferably used as a resin material such as polycarbonate, polyester, polyacrylate, polyurethane, epoxy resin, etc., and can be preferably used for guest molecules. The field of the problem is, for example, used as a raw material (intermediate) for medical pesticides.

<上述式(1)所表示之具有茀骨架之醇之結晶> <Crystal of an alcohol having an anthracene skeleton represented by the above formula (1)>

上述式(1)所表示之具有茀骨架之醇之結晶(本發明之結晶)具有利用示差掃描熱量分析(DSC)所得之熔解吸熱最大溫度、及粉末X射線繞射圖案中之繞射角2θ中之至少1個特徵。 The crystal of the alcohol having an anthracene skeleton represented by the above formula (1) (crystal of the present invention) has a melting endothermic maximum temperature obtained by differential scanning calorimetry (DSC), and a diffraction angle 2θ in a powder X-ray diffraction pattern. At least one feature in the middle.

具體而言，本發明之結晶之利用示差掃描熱量分析所得之熔解吸熱最大溫度為148~151℃。本發明中之利用示差掃描熱量分析所得之熔解吸熱最大溫度係於下述條件下實施示差掃描熱量分析時，觀測到最大吸熱峰之溫度。再者，本發明之結晶所顯示之熔解吸熱最大溫度存在因若干主要因素而上下地變動之情況。作為導致此種偏差之主要因素，有實施分析時之試樣之加熱速度、試樣量、所使用之校正標準、機器之校正方法、分析環境之相對濕度及試樣之化學純度。針對所提供之試樣而觀察到之熔解吸熱最大溫度存在根據每個裝置而不同之情況，但一般而言，只要適當地校正裝置，則成為本案所定義之範圍內。 Specifically, the melting endothermic maximum temperature obtained by the differential scanning calorimetry of the crystal of the present invention is 148 to 151 °C. In the present invention, the maximum temperature of melting endotherm obtained by differential scanning calorimetry is observed when the differential scanning calorimetry is carried out under the following conditions, and the temperature of the maximum endothermic peak is observed. Further, the maximum temperature of melting endotherm exhibited by the crystal of the present invention may vary up and down due to a number of major factors. As the main factors causing such deviation, there are the heating rate of the sample, the amount of the sample, the calibration standard used, the calibration method of the machine, the relative humidity of the analysis environment, and the chemical purity of the sample. The maximum temperature of melting endotherm observed for the supplied sample may vary depending on each device, but in general, it is within the scope defined by the present invention as long as the device is properly calibrated.

本發明之結晶為如下結晶：根據上述乾燥步驟中之乾燥溫度之差異，於利用Cu-Kα射線所得之粉末X射線繞射圖案中，於繞射角2θ=7.1±0.2°、14.3±0.2°、15.2±0.2°、15.8±0.2°、17.1±0.2°及22.3±0.2°處具有特徵性之峰，或者於8.1±0.2°、15.4±0.2°、16.6±0.2°、18.0±0.2°、20.4±0.2°、21.1±0.2°及22.7±0.2°處具有特徵性之峰。另一方面，包接有作為公知之客體分子之芳香族烴類之上述式(1)所表示之具有茀骨架之醇之結晶(包接體)於繞射角2θ=7.6±0.2°、15.6±0.2°、16.4±0.2°、18.7±0.2°、19.0±0.2°、20.5±0.2°及23.6±0.2°處具有特徵性之峰。藉由確認該等包接體之特徵性之峰中，是否具有本發明之結晶所具有之能夠與其他峰明確地區別之7.6±0.2°之峰，而亦可區別所獲得之結晶是否為包接體。 The crystal of the present invention is a crystal having a diffraction angle of 2θ = 7.1 ± 0.2° and 14.3 ± 0.2° in a powder X-ray diffraction pattern obtained by Cu-Kα ray according to the difference in drying temperature in the above drying step. Characteristic peaks at 15.2±0.2°, 15.8±0.2°, 17.1±0.2°, and 22.3±0.2°, or 8.1±0.2°, 15.4±0.2°, 16.6±0.2°, 18.0±0.2°, 20.4 Characteristic peaks at ±0.2°, 21.1±0.2°, and 22.7±0.2°. On the other hand, a crystal (inclusion body) of an alcohol having an anthracene skeleton represented by the above formula (1), which is an aromatic hydrocarbon of a known guest molecule, is coated at a diffraction angle of 2θ=7.6±0.2°, 15.6. Characteristic peaks at ±0.2°, 16.4±0.2°, 18.7±0.2°, 19.0±0.2°, 20.5±0.2°, and 23.6±0.2°. By confirming whether the characteristic peaks of the inclusions have a peak of 7.6±0.2° which can be clearly distinguished from other peaks by the crystal of the present invention, it is also possible to distinguish whether the obtained crystal is a package. Connector.

關於本發明之結晶之純度，藉由下述方法而決定之HPLC(High Performance Liquid Chromatography，高效液相層析法)純度通常為90%以上，較佳為95%以上，更佳為98%以上。又，本發明之結晶之利用下述方法而測定之YI值通常為10以下，較佳為7以下，因此，可尤佳地用於光學用途等著色可能成為問題之領域。 Regarding the purity of the crystal of the present invention, HPLC (High Performance Liquid Chromatography) purity determined by the following method is usually 90% or more, preferably 95% or more, and more preferably 98% or more. . Further, the YI value measured by the following method in the crystal of the present invention is usually 10 or less, preferably 7 or less. Therefore, it can be preferably used in a field where coloring such as optical use may become a problem.

進而，本發明之結晶可具有並非為包接體(並未包接客體分子)之特徵。因此，例如，利用上述文獻中所記載之方法而獲得之包接作為客體分子之芳香族烴類之上述式(1)所表示之具有茀骨架之醇之結晶中之芳香族烴類含量為3~6重量%，與此相對，包含於本發明之結晶之芳香族烴類之含量通常可設為1重量%以下，較佳為設為0.5重量%以下，進而較佳為設為0.1重量%以下。又，根據上述本發明之結晶之乾燥方法，亦可將101.3kPa下之沸點為150℃以下之有機溶劑之含量通常設為1重量%以下，較佳為設為0.5重量%以下，進而較佳為設為0.1重量%以下。因此，可減少保管或輸送上述式(1)所表示之具有茀骨架之醇時容易引起火災等防災上之擔憂，故而可較佳地用作聚碳酸 酯、聚酯、聚丙烯酸酯、聚胺基甲酸酯、環氧樹脂等樹脂材料自不待言，亦可較佳地用於所包接之客體分子成為問題之領域，例如用作醫農藥用之原料(中間物)。 Further, the crystal of the present invention may have characteristics that are not inclusion bodies (not including guest molecules). Therefore, for example, the content of the aromatic hydrocarbon in the crystal of the alcohol having an anthracene skeleton represented by the above formula (1), which is obtained by the method described in the above-mentioned literature, is 3 6% by weight, the content of the aromatic hydrocarbons contained in the crystal of the present invention is usually 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0.1% by weight. the following. Further, according to the method for drying the crystal of the present invention, the content of the organic solvent having a boiling point of 150 ° C or less at 101.3 kPa is usually 1% by weight or less, preferably 0.5% by weight or less, more preferably further. It is set to 0.1% by weight or less. Therefore, it is possible to reduce the fear of fire and the like when storing or transporting the alcohol having an anthracene skeleton represented by the above formula (1), and thus it is preferably used as a polycarbonate. Resin materials such as esters, polyesters, polyacrylates, polyurethanes, and epoxy resins are self-evident, and can also be preferably used in the field where the encapsulated guest molecules become a problem, for example, for medical pesticides. Raw materials (intermediate).

關於是否為包接體，例如，除TG-DTA(示差熱-熱重量同步測定)分析、X射線解析、NMR(Nuclear Magnetic Resonance，核磁共振)分析等方法以外，可使所獲得之結晶於成為客體分子之沸點以上之條件下無重量變化之程度進行充分地乾燥之後，使所獲得之結晶溶解於溶劑，並使用氣相層析法或高效液相層析法進行分析，而判斷是否存在相當於客體分子之峰。又，於使用上述TG-DTA分析之方法中，可測定使測定樣本以一定之速度升溫時之重量變化、及伴隨其之吸熱、發熱行為，亦可判斷於同時觀測到重量變化及吸熱(或發熱)之時間點，客體分子被釋出。 Regarding whether or not the inclusion body is, for example, in addition to methods such as TG-DTA (differential heat-thermal weight synchronization measurement) analysis, X-ray analysis, and NMR (Nuclear Magnetic Resonance) analysis, the obtained crystal can be obtained. After the guest molecule is sufficiently dried without any change in weight under the conditions of the boiling point of the guest molecule, the obtained crystal is dissolved in a solvent, and analyzed by gas chromatography or high performance liquid chromatography to determine whether or not there is a considerable amount. At the peak of the guest molecule. Further, in the method using the TG-DTA analysis described above, it is possible to measure the change in weight when the measurement sample is heated at a constant rate, and the heat absorption and heat generation behavior accompanying the measurement, and it is also judged that the weight change and the endotherm are simultaneously observed (or At the time of fever, the guest molecules are released.

[實施例] [Examples]

以下，列舉實施例等，對本發明具體地進行說明，但本發明並不受到任何限制。再者，於例中，各種測定係利用下述方法而實施。又，以下，實施例、比較例、參考例中所記載之各成分之生成率(殘存率)及純度係於下述條件下測得之HPLC之面積百分率值(反應液中之溶劑及客體分子之峰除外之修正面積百分率值)，實施例、比較例中之「多聚體」係表示對上述式(1)所表示之具有茀骨架之醇進而加成碳酸乙烯酯1分子以上而成之化合物類。 Hereinafter, the present invention will be specifically described by way of examples and the like, but the present invention is not limited at all. Further, in the examples, various measurement systems were carried out by the following methods. In addition, the production ratio (residual ratio) and purity of each component described in the examples, the comparative examples, and the reference examples are the area percentage values of HPLC measured under the following conditions (solvent and guest molecules in the reaction solution) In the examples and the comparative examples, the "multimer" is a mixture of the alcohol having an anthracene skeleton represented by the above formula (1) and further adding one or more ethylene carbonates. Compound class.

(1)HPLC純度 (1) HPLC purity

裝置：島津製作所製造之LC-2010A，管柱：SUMIPAX ODS A-211(5μm，4.6mm ×250mm)，流動相：純水/乙腈(乙腈30%→100%)，流量：1.0ml/min，管柱溫度：40℃，檢測波長：UV 254nm。 Device: LC-2010A manufactured by Shimadzu Corporation, column: SUMIPAX ODS A-211 (5μm, 4.6mm ×250 mm), mobile phase: pure water/acetonitrile (acetonitrile 30%→100%), flow rate: 1.0 ml/min, column temperature: 40 ° C, detection wavelength: UV 254 nm.

(2)殘存溶劑量、包接溶劑量之分析 (2) Analysis of the amount of residual solvent and the amount of solvent

對於溶劑之殘存量、或包接於上述式(1)所表示之具有茀骨架之醇之客體分子(芳香族烴類等)之含量，藉由基於下述條件之氣相層析法而進行定量。 The residual amount of the solvent or the content of the guest molecule (aromatic hydrocarbon or the like) which is encapsulated in the alcohol having an anthracene skeleton represented by the above formula (1) is carried out by gas chromatography based on the following conditions. Quantitative.

裝置：島津製作所製造之GC-2014，管柱：DB-1(0.25μm，0.25mmID×30m)，升溫：40℃(保持5分鐘)→20℃/min→250℃(保持10分鐘)，進料口(Inj)溫度：250℃，檢測器(Det)溫度：300℃，分流比1：10，載子：氮氣54.4kPa(固定)，樣本製備方法：於10ml量瓶，量取經充分乾燥之上述式(1)所表示之具有茀骨架之醇之結晶100mg，利用全移液管向其中加入預先製備之1,2-二甲氧基乙烷之乙腈溶液(將1,2-二甲氧基乙烷400mg溶解於乙腈200ml而成者)5ml，利用乙腈進行定容並將溶解者作為試樣溶液。 Device: GC-2014 manufactured by Shimadzu Corporation, column: DB-1 (0.25 μm, 0.25 mm ID × 30 m), temperature rise: 40 ° C (for 5 minutes) → 20 ° C / min → 250 ° C (for 10 minutes), Feed port (Inj) temperature: 250 ° C, detector (Det) temperature: 300 ° C, split ratio 1:10, carrier: nitrogen 54.4 kPa (fixed), sample preparation method: in a 10 ml volumetric flask, the amount is fully dried 100 mg of the crystal of the alcohol having an anthracene skeleton represented by the above formula (1), and a previously prepared 1,2-dimethoxyethane acetonitrile solution (1,2-dimethoxygen) is added thereto by a full pipette 400 mg of ethyl ethane was dissolved in 200 ml of acetonitrile (5 ml), and the solution was made up to volume with acetonitrile and dissolved.

另一方面，於10ml量瓶，量取欲測定殘存量(包接量)之化合物10mg，並加入與上述同量之1,2-二甲氧基乙烷之乙腈溶液，利用乙腈進行定容並將溶解者作為標準溶液。 On the other hand, in a 10 ml volumetric flask, 10 mg of the compound to be measured for the residual amount (package amount) was weighed, and a solution of the same amount of 1,2-dimethoxyethane in acetonitrile was added thereto to make a constant volume using acetonitrile. The dissolver was used as a standard solution.

於上述條件下對試樣溶液及標準溶液進行分析，並利用資料處理裝置求出所獲得之各成分之峰面積，從而算出各成分之含量(%)(內部標準法)。 The sample solution and the standard solution were analyzed under the above conditions, and the peak area of each component obtained was determined by a data processing device to calculate the content (%) of each component (internal standard method).

(3)用以確認為包接體之分析 (3) Analysis to confirm the inclusion

精確地稱取上述式(1)所表示之具有茀骨架之醇之結晶5mg置於鋁鍋中，並使用Rigaku(股)公司製造之示差熱天平TG-DTA8121，於下述操作條件下進行測定。 5 mg of the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) was accurately weighed and placed in an aluminum pan, and measured using the differential thermal balance TG-DTA8121 manufactured by Rigaku Co., Ltd. under the following operating conditions. .

(操作條件) (Operating conditions)

升溫速度：10℃/min， 測定範圍：30-250℃，氣體氛圍：開放，氮氣250ml/min。 Heating rate: 10 ° C / min, Measuring range: 30-250 ° C, gas atmosphere: open, nitrogen 250 ml / min.

(4)示差掃描熱量測定(DSC) (4) Differential Scanning Calorimetry (DSC)

精確地稱取上述式(1)所表示之具有茀骨架之醇之結晶5mg置於鋁鍋中，並使用示差掃描熱量計(SII NanoTechnology股份有限公司：DSC7020)，以氧化鋁為對照，於下述操作條件下進行測定。 5 mg of the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) was accurately weighed and placed in an aluminum pan, and a differential scanning calorimeter (SII NanoTechnology Co., Ltd.: DSC7020) was used, and alumina was used as a control. The measurement was carried out under the operating conditions described.

(操作條件) (Operating conditions)

升溫速度：10℃/min，測定範圍：30-250℃，氣體氛圍：開放，氮氣40ml/min。 Heating rate: 10 ° C / min, measuring range: 30-250 ° C, gas atmosphere: open, nitrogen 40 ml / min.

(5)粉末X射線繞射 (5) Powder X-ray diffraction

將上述式(1)所表示之具有茀骨架之醇之結晶150mg填充於玻璃試板之試樣填充部，並使用粉末X射線繞射裝置(Spectris公司製造：X'PertPRO)，於下述條件下進行測定。 150 mg of the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) was filled in a sample filling portion of a glass test plate, and a powder X-ray diffraction apparatus (manufactured by Spectris: X'PertPRO) was used under the following conditions. The measurement was carried out.

X射線源：CuKα，輸出：1.8kW(45kV-40mA)，測定範圍：2θ=5°~70°，掃描速度：2θ=2°/min，狹縫：DS=1°，遮罩=15mm，RS=可變(0.1mm~)。 X-ray source: CuKα, output: 1.8kW (45kV-40mA), measuring range: 2θ=5°~70°, scanning speed: 2θ=2°/min, slit: DS=1°, mask=15mm, RS = variable (0.1mm~).

(6)YI值 (6) YI value

使上述式(1)所表示之具有茀骨架之醇之結晶12g溶解於純度99重量%以上之N,N-二甲基甲醯胺30ml，並於以下條件下測定所獲得之N,N-二甲基甲醯胺溶液之YI值(黃度)。 12 g of the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) was dissolved in 30 ml of N,N-dimethylformamide having a purity of 99% by weight or more, and the obtained N,N- was measured under the following conditions. YI value (yellowness) of dimethylformamide solution.

裝置：色差計(日本電色工業公司製造，SE6000)，使用槽：光程長度33mm之石英槽。 Device: Color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., SE6000), using a groove: a quartz tank having an optical path length of 33 mm.

再者，事前測定N,N-二甲基甲醯胺之色相並進行修正(空白測 定)，以防用於測定之N,N-二甲基甲醯胺本身之著色對測定值造成影響。於實施該空白測定之基礎上，將測定樣本而得之值作為本發明中之YI值。 Furthermore, the hue of N,N-dimethylformamide was measured beforehand and corrected (blank test) In order to prevent the coloring of the N,N-dimethylformamide itself used for the measurement, it has an influence on the measured value. Based on the calculation of the blank measurement, the value obtained by measuring the sample is taken as the YI value in the present invention.

(7)水分值 (7) Water value

晶析溶液中之水分值係藉由依據JIS-K0068之方法(卡氏容量滴定法)進行測定。 The water content in the crystallization solution was measured by a method according to JIS-K0068 (Carthalometric titration).

<實施例1> <Example 1>

將上述式(2)所表示之具有茀骨架之酚化合物(9,9'-雙(4-羥基-3-苯基苯基)茀)150g(0.298mol)、碳酸鉀3.4g(0.025mol)、碳酸乙烯酯60.1g(0.682mol)、甲苯225g、及三乙二醇二甲醚15g添加至具備攪拌器、加熱冷卻器、及溫度計之玻璃製反應器中，並升溫至115℃，於相同溫度下攪拌8小時之後，藉由HPLC確認原料已消失。反應結束時間點之多聚體之生成率約為1%。 A phenol compound having an anthracene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylphenyl)fluorene) 150 g (0.298 mol), potassium carbonate 3.4 g (0.025 mol) 60.1 g (0.682 mol) of ethylene carbonate, 225 g of toluene, and 15 g of triethylene glycol dimethyl ether were added to a glass reactor equipped with a stirrer, a heating cooler, and a thermometer, and the temperature was raised to 115 ° C. After stirring at the temperature for 8 hours, it was confirmed by HPLC that the starting material had disappeared. The rate of formation of the polymer at the end of the reaction was about 1%.

將所獲得之反應液冷卻至90℃之後，加入水225g，並於80~85℃下攪拌30分鐘，靜置之後，將水層分離。重複進行相同之操作3次之後，藉由將所獲得之有機溶劑層濃縮，而將溶劑去除，從而獲得濃縮物。將甲苯49g、甲醇188g添加至所獲得之濃縮物，而獲得晶析溶液。所獲得之晶析溶液中之水分為0.1%。 After cooling the obtained reaction liquid to 90 ° C, 225 g of water was added, and the mixture was stirred at 80 to 85 ° C for 30 minutes, and after standing, the aqueous layer was separated. After repeating the same operation three times, the solvent was removed by concentrating the obtained organic solvent layer, thereby obtaining a concentrate. 49 g of toluene and 188 g of methanol were added to the obtained concentrate to obtain a crystallization solution. The moisture in the obtained crystallization solution was 0.1%.

將所獲得之晶析溶液升溫至65℃，並於相同溫度下攪拌1小時而使結晶完全溶解之後，藉由以0.1℃/min進行冷卻而於45℃使結晶析出，析出之後，於相同溫度下攪拌2小時。攪拌之後，進而冷卻至22℃之後進行過濾，從而獲得結晶。 After the obtained crystallization solution was heated to 65 ° C and stirred at the same temperature for 1 hour to completely dissolve the crystal, the crystal was precipitated at 45 ° C by cooling at 0.1 ° C / min, and after precipitation, at the same temperature. Stir under 2 hours. After stirring, it was further cooled to 22 ° C and then filtered to obtain crystals.

將所獲得之結晶於內壓1.3kPa之減壓下、於內溫55~59℃下乾燥3小時，並利用氣相層析法對結晶之一部分進行分析，結果可確認，晶析步驟中所使用之溶劑中含有甲醇4重量%。進而，即便於相同條件下繼續乾燥3小時而進行分析，甲醇之含量亦為4重量%，並無 變化，故而於內壓1.3kPa之減壓下，將內溫升溫至68℃~73℃，進而乾燥3小時，結果甲醇之含量變為0.2重量%，故而以此作為乾燥結束。 The obtained crystal was dried under an internal pressure of 1.3 kPa under reduced pressure at an internal temperature of 55 to 59 ° C for 3 hours, and a part of the crystal was analyzed by gas chromatography. As a result, it was confirmed that the crystallization step was carried out. The solvent used contained 4% by weight of methanol. Further, even if the analysis was continued for 3 hours under the same conditions, the methanol content was also 4% by weight, and there was no As a result of the change, the internal temperature was raised to 68 ° C to 73 ° C under a reduced pressure of 1.3 kPa, and further dried for 3 hours. As a result, the content of methanol was 0.2% by weight, so that the drying was completed.

所獲得之上述式(1)所表示之具有茀骨架之醇之結晶之各分析值為如下所示。 The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are shown below.

所獲得之結晶之重量：139g(產率：79%)，HPLC純度：98.5%(多聚體含量：1.1%)，甲苯含量：0.03重量%，101.3kPa下之沸點為150℃以下之有機溶劑之含量：0.25重量%，YI值：0.7，DSC熔解吸熱最大溫度：150℃。 Weight of crystal obtained: 139 g (yield: 79%), HPLC purity: 98.5% (polymer content: 1.1%), toluene content: 0.03 wt%, organic solvent having a boiling point of 150 ° C or less at 101.3 kPa Content: 0.25 wt%, YI value: 0.7, maximum temperature of DSC melting endotherm: 150 °C.

將DSC分析圖列舉於圖1中，將粉末X射線之圖案列舉於圖4中，將粉末X射線之主峰(具有超過5%之相對強度者)列舉於表3中。如表3所示，本實施例中所獲得之上述式(1)所表示之具有茀骨架之醇於繞射角2θ=7.1±0.2°、14.3±0.2°、15.2±0.2°、15.8±0.2°、17.1±0.2°及22.3±0.2°處顯示出特徵性之繞射峰。又，於作為包接體之典型之峰之7.6±0.2°處，並未觀察到峰(以下，有時將與本圖案具有同樣之X射線峰者稱為「圖案A」)。 The DSC analysis chart is shown in Fig. 1, and the powder X-ray pattern is shown in Fig. 4, and the main peak of the powder X-ray (having a relative strength of more than 5%) is shown in Table 3. As shown in Table 3, the alcohol having an anthracene skeleton represented by the above formula (1) obtained in the present example has a diffraction angle of 2θ=7.1±0.2°, 14.3±0.2°, 15.2±0.2°, and 15.8±0.2. Characteristic, diffraction peaks are shown at °, 17.1 ± 0.2 ° and 22.3 ± 0.2 °. Further, no peak was observed at 7.6 ± 0.2° which is a typical peak of the inclusion body (hereinafter, a person who has the same X-ray peak as the present pattern may be referred to as "pattern A").

<實施例2> <Example 2>

將上述式(2)所表示之具有茀骨架之酚化合物(9,9'-雙(4-羥基-3-苯基苯基)茀)150g(0.298mol)、碳酸鉀3.4g(0.025mol)、碳酸乙烯酯60.1g(0.682mol)、甲苯225g、及二乙二醇二甲醚150g添加至具備攪拌器、加熱冷卻器、及溫度計之玻璃製反應器中，並升溫至115℃，於相同溫度下攪拌13小時之後，藉由HPLC確認原料已消失。反應結束時間點之多聚體之生成率約為0.5%。 A phenol compound having an anthracene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylphenyl)fluorene) 150 g (0.298 mol), potassium carbonate 3.4 g (0.025 mol) 60.1 g (0.682 mol) of ethylene carbonate, 225 g of toluene, and 150 g of diethylene glycol dimethyl ether were added to a glass reactor equipped with a stirrer, a heating cooler, and a thermometer, and the temperature was raised to 115 ° C. After stirring at the temperature for 13 hours, it was confirmed by HPLC that the starting material had disappeared. The rate of formation of the polymer at the end of the reaction was about 0.5%.

將所獲得之反應液冷卻至85℃之後，加入水225g，並於80~85℃下攪拌30分鐘，靜置之後，將水層分離。重複進行相同之操作3次之後，將所獲得之有機溶劑層一部分濃縮，從而獲得包含上述式(1)所表示之具有茀骨架之醇、甲苯及二乙二醇二甲醚之溶液。 After cooling the obtained reaction liquid to 85 ° C, 225 g of water was added, and the mixture was stirred at 80 to 85 ° C for 30 minutes, and after standing, the aqueous layer was separated. After repeating the same operation three times, a part of the obtained organic solvent layer was concentrated to obtain a solution containing an alcohol having an anthracene skeleton represented by the above formula (1), toluene, and diethylene glycol dimethyl ether.

將甲苯54g、甲醇84g添加至該溶液而獲得晶析溶液。所獲得之晶析溶液中之水分為0.1%，包含於該溶液中之甲苯為173g，甲醇為84g，二乙二醇二甲醚為61g。 54 g of toluene and 84 g of methanol were added to the solution to obtain a crystallization solution. The obtained crystallization solution had a water content of 0.1%, and the toluene contained in the solution was 173 g, methanol was 84 g, and diethylene glycol dimethyl ether was 61 g.

將所獲得之晶析溶液升溫至65℃，並於相同溫度下攪拌1小時而使結晶完全溶解之後，以0.1℃/min進行冷卻而使之為50℃之時間點，添加實施例1中所獲得之結晶0.01g作為籽晶，結果析出了結晶。其後，於相同溫度下攪拌1小時。攪拌之後，進而冷卻至25℃之後進行過濾，從而獲得結晶。 The obtained crystallization solution was heated to 65 ° C, and stirred at the same temperature for 1 hour to completely dissolve the crystal, and then cooled at 0.1 ° C / min to make it 50 ° C, and the addition of Example 1 was added. 0.01 g of the obtained crystal was used as a seed crystal, and as a result, crystals were precipitated. Thereafter, it was stirred at the same temperature for 1 hour. After stirring, it was further cooled to 25 ° C and then filtered to obtain crystals.

將所獲得之結晶於內壓1.1kPa之減壓下且將內溫設為68℃~73℃下乾燥3小時，結果甲醇之含量變為0.2重量%，故而以此作為乾燥結束。 The obtained crystal was dried under reduced pressure of an internal pressure of 1.1 kPa and the internal temperature was set to 68 ° C to 73 ° C for 3 hours. As a result, the content of methanol became 0.2% by weight, and thus the drying was completed.

所獲得之上述式(1)所表示之具有茀骨架之醇之結晶之各分析值為如下所示。 The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are shown below.

所獲得之結晶之重量：123g(產率：70%)，HPLC純度：98.0%(多聚體含量：0.10%)，甲苯含量：0.05重量%，101.3kPa下之沸點為150℃以下之有機溶劑之含量：0.26重量%，YI值：0.7，DSC熔解吸熱最大溫度：150℃，X射線繞射圖案：圖案A。 Weight of crystal obtained: 123 g (yield: 70%), HPLC purity: 98.0% (polymer content: 0.10%), toluene content: 0.05% by weight, organic solvent having a boiling point of 150 ° C or less at 101.3 kPa Content: 0.26% by weight, YI value: 0.7, DSC melting endothermic maximum temperature: 150 ° C, X-ray diffraction pattern: pattern A.

<實施例3-6> <Example 3-6>

與實施例1同樣地進行反應、後處理而獲得濃縮物。將所獲得之濃縮物進行4等分，並以成為下述表1所示之比率之方式分別添加甲苯、甲醇，並與實施例1中所記載之方法同樣地進行晶析、乾燥操作，從而獲得上述式(1)所表示之具有茀骨架之醇之結晶。將各結晶之各分析值示於以下表1中。再者，表1中之甲苯、甲醇之添加量係相對於包含於各個濃縮物之上述式(1)所表示之具有茀骨架之醇之比率(重量倍)。 The reaction and the post treatment were carried out in the same manner as in Example 1 to obtain a concentrate. The obtained concentrate was subjected to four equal parts, and toluene and methanol were respectively added so as to have the ratio shown in the following Table 1, and the crystallization and drying operations were carried out in the same manner as in the method described in Example 1. A crystal of an alcohol having an anthracene skeleton represented by the above formula (1) is obtained. The respective analysis values of the respective crystals are shown in Table 1 below. In addition, the addition amount of the toluene and methanol in Table 1 is the ratio (weight-weight) with respect to the alcohol which has the oxime skeleton represented by the above formula (1) of each concentrate.

<比較例1> <Comparative Example 1>

將上述式(2)所表示之具有茀骨架之酚化合物(9,9'-雙(4-羥基-3-苯基苯基)茀)40.0g(0.080mol)、碳酸乙烯酯16.1g(0.183mol)、碳酸鉀0.8g(0.006mol)及甲苯40.0g添加至具備攪拌器、加熱冷卻器、及溫度計之玻璃製反應器中，於110℃下攪拌11小時，並藉由HPLC確認原料峰為1%以下。又，確認於反應液中，副生成了約3%之多聚體。 The phenolic compound having the anthracene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylphenyl)fluorene) 40.0 g (0.080 mol), and ethylene carbonate 16.1 g (0.183) Mol), 0.8 g (0.006 mol) of potassium carbonate and 40.0 g of toluene were added to a glass reactor equipped with a stirrer, a heating cooler, and a thermometer, and stirred at 110 ° C for 11 hours, and the peak of the raw material was confirmed by HPLC. 1% or less. Further, it was confirmed that about 3% of the polymer was produced in the reaction liquid.

將所獲得之反應液冷卻至85℃之後，加入水68g，並於80~85℃下攪拌30分鐘，靜置之後，將水層分離。重複進行相同之操作3次之後，使用迪安-斯塔克裝置，於回流狀態下對所獲得之有機溶劑層進行脫水，從而獲得溶解有上述式(1)所表示之具有茀骨架之醇之晶析溶液。該晶析溶液中之水分為0.1%。 After cooling the obtained reaction liquid to 85 ° C, 68 g of water was added, and the mixture was stirred at 80 to 85 ° C for 30 minutes, and after standing, the aqueous layer was separated. After the same operation was repeated three times, the obtained organic solvent layer was dehydrated under reflux using a Dean-Stark apparatus to obtain an alcohol having an anthracene skeleton represented by the above formula (1). Crystallization solution. The moisture in the crystallization solution was 0.1%.

將所獲得之晶析溶液以0.3℃/min進行冷卻，結果於65℃析出了結晶，並於相同溫度下攪拌2小時。攪拌之後，進而冷卻至26℃之後進行過濾，從而獲得結晶。 The obtained crystallization solution was cooled at 0.3 ° C / min, and as a result, crystals were precipitated at 65 ° C and stirred at the same temperature for 2 hours. After stirring, it was further cooled to 26 ° C and then filtered to obtain crystals.

將所獲得之結晶於內壓1.1kPa之減壓下且將內溫設為68℃~73℃下乾燥3小時，但由於包含甲苯4重量%，故而雖將內溫升溫至110℃，並於相同溫度進而乾燥3小時，但甲苯之含量仍為4重量%不變。 The obtained crystal was dried under reduced pressure of an internal pressure of 1.1 kPa and the internal temperature was set to 68 ° C to 73 ° C for 3 hours. However, since the toluene was contained in an amount of 4% by weight, the internal temperature was raised to 110 ° C. The same temperature was further dried for 3 hours, but the toluene content was still 4% by weight.

所獲得之上述式(1)所表示之具有茀骨架之醇之結晶之各分析值為如下所示。 The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are shown below.

所獲得之結晶之重量：39.3g，HPLC純度：97.5%(多聚體含量：2.6%)，甲苯含量：4.1重量%，DSC熔解吸熱最大溫度：151℃。 The weight of the obtained crystal: 39.3 g, HPLC purity: 97.5% (polymer content: 2.6%), toluene content: 4.1% by weight, DSC melting endothermic maximum temperature: 151 °C.

將DSC分析圖列舉於圖2中，將粉末X射線之圖案列舉於圖5中，將粉末X射線之主峰(具有超過5%之相對強度者)列舉於表4中，將TG-DTA之分析圖列舉於圖7。如表4所示，本比較例1中所獲得之上述式(1)所表示之具有茀骨架之醇於繞射角2θ=7.6±0.2°、15.6±0.2°、16.4±0.2°、18.7±0.2°、19.0±0.2°、20.5±0.2°及23.6±0.2°處顯示出特徵性之繞射峰(以下，有時將與本圖案具有同樣之X射線圖案者稱為「包接體圖案」)。 The DSC analysis chart is listed in Fig. 2, and the powder X-ray pattern is listed in Fig. 5. The main peak of the powder X-ray (with a relative intensity exceeding 5%) is listed in Table 4, and the analysis of TG-DTA is performed. The figure is listed in Figure 7. As shown in Table 4, the alcohol having an anthracene skeleton represented by the above formula (1) obtained in Comparative Example 1 was at a diffraction angle of 2θ=7.6±0.2°, 15.6±0.2°, 16.4±0.2°, 18.7±. A characteristic diffraction peak is exhibited at 0.2°, 19.0±0.2°, 20.5±0.2°, and 23.6±0.2° (hereinafter, the X-ray pattern having the same pattern as the pattern is sometimes referred to as a “package pattern”. ).

又，即便於高溫、減壓下進行乾燥，甲苯之殘存量亦不會減少，故而進行TG-DTA分析而確認是否為包接體，結果於為甲苯之沸點以上之溫度之約139℃，重量開始減少，繼而，約於150℃觀測到吸熱峰，因此，支持本比較例1中所獲得之上述式(1)所表示之具有茀骨架之醇為包接體的事實。 In addition, even if it is dried at a high temperature and under reduced pressure, the residual amount of toluene does not decrease. Therefore, it is confirmed by TG-DTA analysis whether or not it is an inclusion body. As a result, it is about 139 ° C at a temperature higher than the boiling point of toluene. The decrease was started, and an endothermic peak was observed at about 150 ° C. Therefore, the fact that the alcohol having an anthracene skeleton represented by the above formula (1) obtained in Comparative Example 1 was an inclusion body was supported.

<比較例2> <Comparative Example 2>

於晶析步驟中使用乙醇代替甲醇，且將最終乾燥溫度設為90 ℃，除此以外，進行與實施例1同樣之操作，從而獲得上述式(1)所表示之具有茀骨架之醇之結晶。所獲得之結晶之各分析值為如下所示。 Ethanol was used instead of methanol in the crystallization step, and the final drying temperature was set to 90. In the same manner as in Example 1, except that the above, the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) was obtained. The respective analysis values of the obtained crystals are as follows.

所獲得之結晶之重量：127g，HPLC純度：98.0%(多聚體含量：0.8%)，甲苯含量：4.1重量%，DSC熔解吸熱最大溫度：150℃，X射線繞射圖案：包接體圖案。 Weight of crystal obtained: 127 g, HPLC purity: 98.0% (polymer content: 0.8%), toluene content: 4.1% by weight, DSC melting endothermic maximum temperature: 150 ° C, X-ray diffraction pattern: inclusion pattern .

<比較例3~6> <Comparative Examples 3 to 6>

與實施例1同樣地進行反應、後處理而獲得濃縮物。將所獲得之濃縮物進行4等分，並以成為下述表2所示之比率之方式分別添加各溶劑，並且將最終乾燥溫度設為90℃，除此以外，與實施例1中所記載之方法同樣地進行晶析、乾燥操作，從而獲得上述式(1)所表示之具有茀骨架之醇之結晶。將各結晶之各分析值示於以下表2中。再者，表2中之各溶劑之添加量係相對於包含於各個濃縮物之上述式(1)所表示之具有茀骨架之醇之比率(重量倍)。 The reaction and the post treatment were carried out in the same manner as in Example 1 to obtain a concentrate. The obtained concentrate was divided into four equal portions, and each solvent was added so as to have a ratio shown in the following Table 2, and the final drying temperature was 90 ° C, and the contents described in Example 1 were recorded. In the same manner, a crystallization and a drying operation are carried out to obtain a crystal of an alcohol having an anthracene skeleton represented by the above formula (1). The respective analysis values of the respective crystals are shown in Table 2 below. The amount of each solvent added in Table 2 is a ratio (weight ratio) of the alcohol having an anthracene skeleton represented by the above formula (1) contained in each concentrate.

如上述表2所示，判明上述式(1)所表示之具有茀骨架之醇形成芳香族烴類及包接體，於單獨使用二甲苯之情形時，或即便混合甲醇以外之溶劑而使之晶析，亦會成為包接有芳香族烴類之包接體。 As shown in the above Table 2, it was found that the alcohol having an anthracene skeleton represented by the above formula (1) forms an aromatic hydrocarbon and an inclusion body, and when xylene is used alone, or by mixing a solvent other than methanol, Crystallization also becomes an inclusion body containing aromatic hydrocarbons.

<比較例7> <Comparative Example 7>

將上述式(2)所表示之具有茀骨架之酚化合物(9,9'-雙(4-羥基-3-苯基苯基)茀)30.0g(0.060mol)、碳酸乙烯酯12.0g(0.136mol)、碳酸鉀0.7g(0.005mol)、及環己酮30.0g添加至具備攪拌器、加熱冷卻器、及溫度計之玻璃製反應器中，於140℃下攪拌7小時，並藉由HPLC確認原料峰為1%以下。反應結束時間點之多聚體之生成率約為1.2%。 The phenolic compound having the anthracene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylphenyl)fluorene) 30.0 g (0.060 mol), and ethylene carbonate 12.0 g (0.136) Mol), 0.7 g (0.005 mol) of potassium carbonate, and 30.0 g of cyclohexanone were added to a glass reactor equipped with a stirrer, a heating cooler, and a thermometer, and stirred at 140 ° C for 7 hours, and confirmed by HPLC. The raw material peak is 1% or less. The rate of formation of the polymer at the end of the reaction was about 1.2%.

將所獲得之反應液冷卻至90℃之後，加入環己酮23g、正庚烷27g，一面將有機溶劑層保持為90℃，一面進行水洗至洗淨水成為中性。水洗後，使用迪安-斯塔克裝置，於回流狀態下對所獲得之有機溶劑層進行脫水，從而獲得溶解有上述式(1)所表示之具有茀骨架之醇之晶析溶液。該晶析溶液中之水分為0.1%。 After the obtained reaction liquid was cooled to 90° C., 23 g of cyclohexanone and 27 g of n-heptane were added, and the organic solvent layer was kept at 90° C., and washed with water until the washing water became neutral. After washing with water, the obtained organic solvent layer was dehydrated under reflux using a Dean-Stark apparatus to obtain a crystallization solution in which the alcohol having an anthracene skeleton represented by the above formula (1) was dissolved. The moisture in the crystallization solution was 0.1%.

其後，冷卻至70℃，藉由於70℃保溫1小時而使結晶析出之後，於相同溫度下攪拌2小時。攪拌後，進而冷卻至19℃之後進行過濾，從而獲得結晶。 Thereafter, the mixture was cooled to 70 ° C, and crystals were precipitated by holding at 70 ° C for 1 hour, and then stirred at the same temperature for 2 hours. After stirring, it was further cooled to 19 ° C and then filtered to obtain crystals.

將所獲得之結晶於內壓1.1kPa之減壓下且將內溫設為90℃下乾燥3小時，但包含環己酮14重量%。 The obtained crystal was dried under reduced pressure of an internal pressure of 1.1 kPa and the internal temperature was set to 90 ° C for 3 hours, but contained 14% by weight of cyclohexanone.

所獲得之上述式(1)所表示之具有茀骨架之醇之結晶之各分析值為如下所示。 The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are shown below.

所獲得之結晶之重量：33.0g，HPLC純度：97.8%(多聚體含量：0.8%)，環己酮含量：14重量%，DSC熔解吸熱最大溫度：114℃。 The weight of the obtained crystal: 33.0 g, HPLC purity: 97.8% (polymer content: 0.8%), cyclohexanone content: 14% by weight, DSC melting endothermic maximum temperature: 114 °C.

<比較例8> <Comparative Example 8>

除將標度設為十分之一以外，利用日本專利特開2001-206863號之實施例6中所記載之方法進行添加、反應，並於65℃下攪拌1小時之階段，利用高效液相層析法對反應液進行分析，但幾乎並未生成上述 式(2)所表示之具有茀骨架之醇，而殘存98%之原料之9-茀酮。因此，進而於相同溫度下繼續攪拌7小時，並利用高效液相層析法對反應液進行分析，但同樣地反應幾乎未進行，而殘存97%之原料之9-茀酮。 In addition to setting the scale to one tenth, the addition and reaction were carried out by the method described in Example 6 of JP-A-2001-206863, and the mixture was stirred at 65 ° C for 1 hour, using a high-performance liquid phase. Chromatography analysis of the reaction solution, but almost did not generate the above The alcohol having an anthracene skeleton represented by the formula (2), and 9-fluorenone remaining as a raw material of 98%. Therefore, the stirring was further continued at the same temperature for 7 hours, and the reaction liquid was analyzed by high performance liquid chromatography. However, the reaction was hardly carried out in the same manner, and 97% of the starting material 9-fluorenone remained.

因此，基於日本專利特開2001-206863號〔0019〕之記載，將反應溫度自65℃變更至100℃，並於相同溫度下繼續進行攪拌，結果需要73小時直至作為原料之9-茀酮之消失。 Therefore, based on the description of Japanese Patent Laid-Open Publication No. 2001-206863 [0019], the reaction temperature was changed from 65 ° C to 100 ° C, and stirring was continued at the same temperature, and it took 73 hours until the 9-fluorenone as a raw material. disappear.

為了實施基於該文獻記載之後處理，將所獲得之反應液分成2份，於一份加入甲醇10g，於另一份加入異丙醇10g，並加溫至60℃，連續攪拌1小時之後，分別加入純水30g，並冷卻至30℃，但兩者均未析出結晶，分別獲得與水分離之焦油狀之液體。 In order to carry out the treatment based on the document, the obtained reaction liquid was divided into 2 portions, 10 g of methanol was added in one portion, 10 g of isopropanol was added in another portion, and the mixture was heated to 60 ° C, and continuously stirred for 1 hour, respectively. 30 g of pure water was added and cooled to 30 ° C, but neither of them precipitated crystals, and a tar-like liquid separated from water was obtained, respectively.

<比較例9> <Comparative Example 9>

將9-茀酮之使用量設為18g，對日本專利特開2009-256342號之實施例1中所記載之方法加以追加試驗，結果獲得上述式(1)所表示之具有茀骨架之醇34.2g(純度85.1%)。所獲得之上述式(1)所表示之具有茀骨架之醇之結晶之各分析值為如下所示。 The method of the method described in Example 1 of JP-A-2009-256342 was additionally tested, and the alcohol having an anthracene skeleton represented by the above formula (1) was obtained. g (purity 85.1%). The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are shown below.

二甲苯含量：4.8重量%，YI值：51，DSC熔解吸熱最大溫度：141℃。 Xylene content: 4.8% by weight, YI value: 51, DSC melting endothermic maximum temperature: 141 °C.

將DSC分析圖列舉於圖3中，將粉末X射線之圖案列舉於圖6中，將粉末X射線之主峰(具有超過5%之相對強度者)列舉於表5中。如表5所示，本比較例9中所獲得之包接二甲苯之上述式(1)所表示之具有茀骨架之醇於繞射角2θ=7.6±0.2°、15.6±0.2°、16.4±0.2°、18.7±0.2°、19.0±0.2°、20.5±0.2°及23.6±0.2°處顯示出特徵性之繞射峰。 The DSC analysis chart is shown in Fig. 3, and the powder X-ray pattern is shown in Fig. 6, and the main peak of the powder X-ray (having a relative strength of more than 5%) is shown in Table 5. As shown in Table 5, the alcohol having an anthracene skeleton represented by the above formula (1) obtained by the present invention in Comparative Example 9 was at a diffraction angle of 2θ=7.6±0.2°, 15.6±0.2°, 16.4±. Characteristic diffraction peaks are shown at 0.2°, 18.7±0.2°, 19.0±0.2°, 20.5±0.2°, and 23.6±0.2°.

<比較例10> <Comparative Example 10>

將9-茀酮之使用量設為9g，對日本專利特開2009-256342號之實施例2中所記載之方法加以追加試驗，結果獲得上述式(1)所表示之具 有茀骨架之醇13.5g(純度74.7%)。所獲得之上述式(1)所表示之具有茀骨架之醇之結晶之各分析值為如下所示。 When the amount of the 9-fluorenone used is 9 g, the method described in the second embodiment of JP-A-2009-256342 is additionally tested, and as a result, the product represented by the above formula (1) is obtained. 13.5 g of alcohol having an anthracene skeleton (purity of 74.7%). The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are shown below.

甲苯含量：3.0重量%，YI值：83，DSC熔解吸熱最大溫度：126℃。 Toluene content: 3.0% by weight, YI value: 83, DSC melting endothermic maximum temperature: 126 °C.

將粉末X射線之主峰(具有超過5%之相對強度者)示於表6中。如表6所示，本比較例10中所獲得之包接甲苯之上述式(1)所表示之具有茀骨架之醇於繞射角2θ=7.6±0.2°、15.6±0.2°、16.4±0.2°、18.7±0.2°、19.0±0.2°、20.5±0.2°及23.6±0.2°處顯示出特徵性之繞射峰。 The main peak of powder X-rays (having a relative strength of more than 5%) is shown in Table 6. As shown in Table 6, the alcohol having an anthracene skeleton represented by the above formula (1) obtained by the present invention in Comparative Example 10 was at a diffraction angle of 2θ = 7.6 ± 0.2 °, 15.6 ± 0.2 °, and 16.4 ± 0.2. Characteristic, diffraction peaks are shown at °, 18.7 ± 0.2 °, 19.0 ± 0.2 °, 20.5 ± 0.2 °, and 23.6 ± 0.2 °.

<比較例11> <Comparative Example 11>

將9-茀酮之使用量設為18g，對日本專利特開2009-256342號之實施例3中所記載之方法加以追加試驗，結果獲得上述式(1)所表示之具有茀骨架之醇23.6g(純度91.2%)。所獲得之上述式(1)所表示之具有第骨架之醇之結晶之各分析值為如下所示。 The method of the method described in Example 3 of JP-A-2009-256342 was additionally tested, and the alcohol having the anthracene skeleton represented by the above formula (1) was obtained. g (purity 91.2%). The respective analysis values of the obtained crystal of the alcohol having the first skeleton represented by the above formula (1) are shown below.

二甲苯含量：5.0重量%，YI值：18，DSC熔解吸熱最大溫度：147℃。 Xylene content: 5.0% by weight, YI value: 18, DSC melting endothermic maximum temperature: 147 °C.

將粉末X射線之主峰(具有超過5%之相對強度者)示於表7中。如表7所示，本比較例11中所獲得之包接二甲苯之上述式(1)所表示之具有茀骨架之醇於繞射角2θ=7.6±0.2°、15.6±0.2°、16.4±0.2°、18.7±0.2°、19.0±0.2°、20.5±0.2°及23.6±0.2°處顯示出特徵性之繞射峰。 The main peak of powder X-rays (having a relative strength of more than 5%) is shown in Table 7. As shown in Table 7, the alcohol having an anthracene skeleton represented by the above formula (1) obtained by the present invention in Comparative Example 11 has a diffraction angle of 2θ=7.6±0.2°, 15.6±0.2°, 16.4±. Characteristic diffraction peaks are shown at 0.2°, 18.7±0.2°, 19.0±0.2°, 20.5±0.2°, and 23.6±0.2°.

<比較例12> <Comparative Example 12>

將9-茀酮之使用量設為18g，對日本專利特開2009-256342號之實施例4中所記載之方法加以追加試驗，結果獲得上述式(1)所表示之具有茀骨架之醇20.7g(純度88.6%)。所獲得之上述式(1)所表示之具有茀骨架之醇之結晶之各分析值為如下所示。 When the amount of 9-fluorenone used was 18 g, an additional test was carried out on the method described in Example 4 of JP-A-2009-256342, and as a result, an alcohol having an anthracene skeleton represented by the above formula (1) was obtained. g (purity 88.6%). The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are shown below.

二甲苯含量：5.2重量%，YI值：46，DSC熔解吸熱最大溫度：146℃。 Xylene content: 5.2% by weight, YI value: 46, DSC melting endothermic maximum temperature: 146 °C.

將粉末X射線之主峰(具有超過5%之相對強度者)示於表8中。如表8所示，本比較例11中所獲得之包接二甲苯之上述式(1)所表示之具有茀骨架之醇於繞射角2θ=7.6±0.2°、15.6±0.2°、16.4±0.2°、18.7±0.2°、19.0±0.2°、20.5±0.2°及23.6±0.2°處顯示出特徵性之繞射峰。 The main peak of powder X-rays (having a relative strength of more than 5%) is shown in Table 8. As shown in Table 8, the alcohol having an anthracene skeleton represented by the above formula (1) obtained by the present invention in Comparative Example 11 was at a diffraction angle of 2θ=7.6±0.2°, 15.6±0.2°, 16.4±. Characteristic diffraction peaks are shown at 0.2°, 18.7±0.2°, 19.0±0.2°, 20.5±0.2°, and 23.6±0.2°.

<實施例7> <Example 7>

將上述式(2)所表示之具有茀骨架之酚化合物(9,9'-雙(4-羥基-3-苯基苯基)茀)150g(0.298mol)、碳酸鉀1.2g(0.009mol)、碳酸乙烯酯65.6g(0.745mol)、甲苯150g、及三乙二醇二甲醚90g添加至具備攪拌器、加熱冷卻器、及溫度計之玻璃製反應器中，並升溫至115℃，於相同溫度下攪拌5小時之後，藉由HPLC確認原料已消失。反應結束時間點之多聚體之生成率約為0.7%。 A phenol compound having an anthracene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylphenyl)fluorene) 150 g (0.298 mol) and potassium carbonate 1.2 g (0.009 mol) 65.6 g (0.745 mol) of ethylene carbonate, 150 g of toluene, and 90 g of triethylene glycol dimethyl ether were added to a glass reactor equipped with a stirrer, a heating cooler, and a thermometer, and the temperature was raised to 115 ° C, which was the same. After stirring at a temperature for 5 hours, it was confirmed by HPLC that the starting material had disappeared. The rate of formation of the polymer at the end of the reaction was about 0.7%.

將所獲得之反應液冷卻至90℃之後，加入水225g、甲苯225g，並於80~85℃下攪拌30分鐘，靜置之後，將水層分離。重複進行相同之操作3次之後，將所獲得之有機溶劑層一部分濃縮，從而獲得包含上述式(1)所表示之具有茀骨架之醇、甲苯及三乙二醇二甲醚之溶液。 After cooling the obtained reaction liquid to 90 ° C, 225 g of water and 225 g of toluene were added, and the mixture was stirred at 80 to 85 ° C for 30 minutes, and after standing, the aqueous layer was separated. After repeating the same operation three times, a part of the obtained organic solvent layer was concentrated to obtain a solution containing an alcohol having an anthracene skeleton represented by the above formula (1), toluene, and triethylene glycol dimethyl ether.

將甲苯18g、甲醇225g添加至該溶液而獲得晶析溶液。所獲得之晶析溶液中之水分為0.1%，包含於該溶液中之甲苯為150g，甲醇為225g，三乙二醇二甲醚為76g。 18 g of toluene and 225 g of methanol were added to the solution to obtain a crystallization solution. The obtained crystallization solution had a water content of 0.1%, and the toluene contained in the solution was 150 g, methanol was 225 g, and triethylene glycol dimethyl ether was 76 g.

將所獲得之晶析溶液升溫至65℃，並於相同溫度下攪拌1小時而使結晶完全溶解之後，藉由以0.1℃/min進行冷卻而於48℃使結晶析出，析出之後，於相同溫度下攪拌2小時。攪拌之後，進而冷卻至20℃之後進行過濾，從而獲得結晶。 After the obtained crystallization solution was heated to 65 ° C and stirred at the same temperature for 1 hour to completely dissolve the crystal, the crystal was precipitated at 48 ° C by cooling at 0.1 ° C / min, and after precipitation, at the same temperature. Stir under 2 hours. After stirring, it was further cooled to 20 ° C and then filtered to obtain crystals.

將所獲得之結晶於內壓1.3kPa之減壓下且內溫100~105℃下乾燥12小時，結果甲醇之含量成為0.1重量%，故而以此作為乾燥結束。 The obtained crystal was dried under reduced pressure of 1.3 kPa at an internal pressure and at an internal temperature of 100 to 105 ° C for 12 hours. As a result, the content of methanol was 0.1% by weight, and thus the drying was completed.

所獲得之上述式(1)所表示之具有茀骨架之醇之結晶之各分析值為如下所示。 The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are shown below.

所獲得之結晶之重量：145g(產率：82%)，HPLC純度：98.2%(多聚體含量：0.7%)，甲苯含量：0.02重量%，101.3kPa下之沸點為150℃以下之有機溶劑之含量：0.1重量%，YI值：0.8，DSC熔解吸熱最大溫度：150℃。 Weight of crystal obtained: 145 g (yield: 82%), HPLC purity: 98.2% (polymer content: 0.7%), toluene content: 0.02% by weight, organic solvent having a boiling point of 150 ° C or less at 101.3 kPa Content: 0.1% by weight, YI value: 0.8, DSC melting endothermic maximum temperature: 150 °C.

將DSC分析圖列舉於圖8中，將粉末X射線之圖案列舉於圖9中，將粉末X射線之主峰(具有超過5%之相對強度者)列舉於表9中。如表9所示，本實施例中所獲得之上述式(1)所表示之具有茀骨架之醇於繞射角2θ=8.1±0.2°、15.4±0.2°、16.6±0.2°、18.0±0.2°、20.4±0.2°、21.1±0.2°及22.7±0.2°處顯示出特徵性之繞射峰。又，於作為包接體之典型之峰之7.6±0.2°處，並未觀察到峰。 The DSC analysis chart is shown in Fig. 8, and the powder X-ray pattern is shown in Fig. 9, and the main peak of the powder X-ray (having a relative strength of more than 5%) is shown in Table 9. As shown in Table 9, the alcohol having an anthracene skeleton represented by the above formula (1) obtained in the present example has a diffraction angle of 2θ=8.1±0.2°, 15.4±0.2°, 16.6±0.2°, and 18.0±0.2. Characteristic, diffraction peaks are shown at °, 20.4 ± 0.2 °, 21.1 ± 0.2 °, and 22.7 ± 0.2 °. Further, no peak was observed at 7.6 ± 0.2 ° which is a typical peak of the inclusion body.

<比較例13> <Comparative Example 13>

與實施例2同樣地進行反應、後處理之後，藉由去除溶劑而獲得濃縮物171g。將甲苯228g、甲醇114g添加至所獲得之濃縮物之後，升溫至65℃，並藉由於相同溫度下攪拌1小時而使結晶完全溶解。其後，藉由以1.5℃/min進行冷卻而於21℃下使結晶析出，析出之後，於相同溫度下攪拌2小時。攪拌之後，進行過濾，從而獲得結晶。 After the reaction and the post treatment were carried out in the same manner as in Example 2, 171 g of a concentrate was obtained by removing the solvent. After adding 228 g of toluene and 114 g of methanol to the obtained concentrate, the temperature was raised to 65 ° C, and the crystals were completely dissolved by stirring at the same temperature for 1 hour. Thereafter, the crystals were precipitated at 21 ° C by cooling at 1.5 ° C / min, and after the precipitation, the mixture was stirred at the same temperature for 2 hours. After stirring, filtration was carried out to obtain crystals.

將所獲得之結晶於內壓1.1kPa之減壓下且將內溫設為68℃~73℃下乾燥3小時，但由於包含甲苯4重量%，故而雖將內溫升溫至110℃，並於相同溫度進而乾燥3小時，但甲苯之含量仍為4重量%不變。 The obtained crystal was dried under reduced pressure of an internal pressure of 1.1 kPa and the internal temperature was set to 68 ° C to 73 ° C for 3 hours. However, since the toluene was contained in an amount of 4% by weight, the internal temperature was raised to 110 ° C. The same temperature was further dried for 3 hours, but the toluene content was still 4% by weight.

Claims (9)

一種下述式(1)所表示之具有茀骨架之醇之結晶， 其利用示差掃描熱量分析所得之熔解吸熱最大溫度為148~151℃。 a crystal of an alcohol having an anthracene skeleton represented by the following formula (1), The melting endothermic maximum temperature obtained by differential scanning calorimetry is 148 to 151 °C. 一種下述式(1)所表示之具有茀骨架之醇之結晶， 其於利用Cu-Kα射線所得之粉末X射線繞射圖案中，於繞射角2θ=7.1±0.2°、14.3±0.2°、15.2±0.2°、15.8±0.2°、17.1±0.2°及22.3±0.2°處具有峰。 a crystal of an alcohol having an anthracene skeleton represented by the following formula (1), It is in the powder X-ray diffraction pattern obtained by using Cu-Kα ray at diffraction angles 2θ=7.1±0.2°, 14.3±0.2°, 15.2±0.2°, 15.8±0.2°, 17.1±0.2° and 22.3± There is a peak at 0.2°. 一種下述式(1)所表示之具有茀骨架之醇之結晶， 其於利用Cu-Kα射線所得之粉末X射線繞射圖案中，於繞射角2θ=8.1±0.2°、15.4±0.2°、16.6±0.2°、18.0±0.2°、20.4±0.2°、21.1±0.2°及22.7±0.2°處具有峰。 a crystal of an alcohol having an anthracene skeleton represented by the following formula (1), It is in the powder X-ray diffraction pattern obtained by using Cu-Kα ray at diffraction angles 2θ=8.1±0.2°, 15.4±0.2°, 16.6±0.2°, 18.0±0.2°, 20.4±0.2°, 21.1± There are peaks at 0.2° and 22.7±0.2°. 如請求項2之具有茀骨架之醇之結晶，其中利用示差掃描熱量分析所得之熔解吸熱最大溫度為148~151℃。 The crystallization of an alcohol having an anthracene skeleton according to claim 2, wherein the maximum melting endothermic temperature obtained by differential scanning calorimetry is 148 to 151 °C. 如請求項3之具有茀骨架之醇之結晶，其中利用示差掃描熱量分析所得之熔解吸熱最大溫度為148~151℃。 The crystallization of an alcohol having an anthracene skeleton according to claim 3, wherein the maximum melting endothermic temperature obtained by differential scanning calorimetry is 148 to 151 °C. 如請求項1至5中任一項之具有茀骨架之醇之結晶，其並非為包接體。 The crystal of an alcohol having an anthracene skeleton according to any one of claims 1 to 5, which is not an inclusion body. 如請求項1至5中任一項之具有茀骨架之醇之結晶，其中將上述式(1)所表示之具有茀骨架之醇12g溶解於純度99重量%以上之N,N-二甲基甲醯胺30ml而成之溶液之黃度(YI值)為10以下。 The crystal of an alcohol having an anthracene skeleton according to any one of claims 1 to 5, wherein 12 g of the alcohol having an anthracene skeleton represented by the above formula (1) is dissolved in N,N-dimethyl group having a purity of 99% by weight or more. The yellowness (YI value) of the solution of meglumine 30 ml is 10 or less. 如請求項1至5中任一項之具有茀骨架之醇之結晶，其中芳香族烴類之含量為1重量%以下。 The crystal of an alcohol having an anthracene skeleton according to any one of claims 1 to 5, wherein the content of the aromatic hydrocarbon is 1% by weight or less. 一種如請求項1至8中任一項之具有茀骨架之醇之結晶之製造方法，其依序包括下述(i)~(iv)之步驟：(i)於對稱乙二醇二醚之存在下，使下述式(2)： 所表示之具有茀骨架之酚化合物與碳酸乙烯酯反應，而獲得包含上述式(1)所表示之具有茀骨架之醇之反應液之步驟； (ii)將芳香族烴類及甲醇添加至上述反應液中，而製備包含芳香族烴類及甲醇之溶液且該溶液中之水之含量為1重量%以下之晶析溶液之步驟；(iii)於25℃以上使結晶自上述晶析溶液析出，並將所析出之結晶分離之步驟；(iv)將上述結晶設為60℃以上，而去除甲醇之步驟。 A method for producing a crystal of an alcohol having an anthracene skeleton according to any one of claims 1 to 8, which comprises the following steps (i) to (iv): (i) in symmetrical ethylene glycol diether In the presence, let the following formula (2): a step of reacting a phenol compound having an anthracene skeleton with ethylene carbonate to obtain a reaction liquid containing an alcohol having an anthracene skeleton represented by the above formula (1); (ii) adding an aromatic hydrocarbon and methanol to the above a step of preparing a crystallization solution containing a solution of an aromatic hydrocarbon and methanol and having a water content of 1% by weight or less in the reaction solution; (iii) precipitating the crystal from the crystallization solution at 25 ° C or higher And the step of separating the precipitated crystals; (iv) the step of removing the methanol by setting the above crystals to 60 ° C or higher.
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