JP2015093862A - Fluorene-based diol compound and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorene-based diol compound which has a fluorene skeleton and a benzofuran skeleton which has not been known in the skeleton, and a manufacturing method therefor.SOLUTION: It is found that a fluorene-based diol compound having a novel benzofuran skeleton by reacting fluorene and a benzofuran derivative represented by the following formula (2) in a presence of acid. It is further found that the fluorene-based diol compound having the novel benzofuran skeleton has a specific structure where the position of a hydroxyl group is 3-position (meta-position from a coupling point with the fluorene skeleton).

Description

The present invention relates to a novel fluorene-based diol compound that is suitable as a raw material for polyester, polyurethane, polycarbonate, epoxy resin, modified acrylic resin, and the like, and a method for producing the same.

In recent years, diol compounds having a fluorene skeleton are promising as polymer raw materials with excellent heat resistance and transparency and a high refractive index, such as optical lenses, films, plastic optical fibers, optical disk bases, heat resistant resins and engineering plastics. Expected as a raw material.

  For example, Japanese Patent Laid-Open No. 06-025398 (Patent Document 1) discloses a polycarbonate resin using 9,9-bis (4-hydroxyphenyl) fluorenes. Japanese Patent Laid-Open No. 11-035815 (Patent Document 2) discloses a polycarbonate resin using 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. Japanese Patent Application Laid-Open No. 2002-161061 (Patent Document 3) discloses a resin component raw material for photoresist material, a raw material for photosensitive agent, a raw material for dissolution inhibitor and an additive, or a polymer monomer having a nonlinear structure or a crosslinked structure. An invention relating to 9,9-bis (1-hydroxy-2-ethylphenyl) fluorene, which is intended to be used in the field, is disclosed.

Japanese Patent Application Laid-Open No. 06-025398 Japanese Patent Laid-Open No. 11-035815 JP 2002-161061 A

  An object of the present invention is to provide a diol compound having a fluorene skeleton, a fluorene diol compound having a benzofuran skeleton that has not been known in the skeleton, and a method for producing the same.

  The present invention includes the following.

  [1] The following formula (1):

で表されるフルオレン系ジオール化合物。

A fluorene-based diol compound represented by:

  [2] In the presence of an acid, fluorenone and the following formula (2)

で表されるベンゾフラン誘導体を反応させることを特徴とする［１］記載のフルオレン系ジオール化合物の製造方法。

A process for producing a fluorene-based diol compound according to [1], wherein a benzofuran derivative represented by the formula:

  The fluorene-based diol compound represented by the above formula (1) has a benzofuran skeleton, and when the fluorene-based diol compound represented by the above formula (1) is produced by the method described in the present application, the reaction for producing various polymers. Since it has a specific structure in which the position of the hydroxyl group that becomes a point is the 3rd position (meta position as viewed from the point of attachment to the fluorene skeleton), it is a raw material for polyester, polyurethane, polycarbonate, epoxy resin, modified acrylic resin, etc. It is expected that it will exhibit specific properties when used as an optical member, such as optical lenses, optical films, plastic optical fibers, optical disk substrates, or non-optical resins such as heat-resistant resins and engineering plastics. The

2 is a ¹ H-NMR spectrum of a fluorene-based diol compound represented by the above formula (1). It is a ¹³ C-NMR spectrum of a fluorene diol compound represented by the above formula (1). It is a two-dimensional NMR (H-H COSY) spectrum of the fluorene-type diol compound represented by the said Formula (1). It is a mass spectrometry chart of the fluorene type diol compound represented by the said Formula (1).

<Method for producing fluorene-based diol compound>
The fluorene-based diol compound represented by the above formula (1) in the present invention can be obtained by reacting fluorenone with a compound represented by the above formula (2) in the presence of an acid. The raw material fluorenone and the compound represented by the above formula (2) in this reaction are industrially readily available compounds, and any quality can be used in the present invention. Moreover, the compound represented by the said Formula (2) is normally used 2-15 times mole with respect to 1 mol of fluorenone, Preferably it is used 4-10 times mole. When the amount is less than 2 times mol, the reaction is not completed, the yield of the resulting fluorene-based diol compound represented by the above formula (1) is lowered, and even if it is used more than 15 times mol, the reaction is not affected. However, since it is not possible to expect a yield improvement corresponding to the amount used, it is not preferable because the fluorene diol compound represented by the above formula (1) cannot be obtained economically.

In the present invention, the reaction is carried out in the presence of an acid. Examples of the acid include inorganic acids such as sulfuric acid and hydrochloric acid, sulfonic acids such as p-toluenesulfonic acid and p-phenylsulfonic acid, phosphomolybdic acid, phosphotungstic acid and silica. Of these, heteropolyacids such as molybdic acid, silicotungstic acid, and phosphovanadmolybdic acid, and Lewis acids such as zinc chloride, iron chloride, and aluminum chloride are used. Among these, sulfonic acids and Lewis acids are preferred because of their high reactivity. Furthermore, p-toluenesulfonic acid and zinc chloride are more preferable from the viewpoint of reactivity and handling. In addition, these acids can be used in the form of solids, and those diluted with solvents such as aqueous solutions and alcohols can be used as they are.

These acids are used in an amount of usually 0.1 to 5 moles, preferably 0.5 to 2 moles per mole of the raw material fluorenone. If the amount is less than 0.1 mol, the reaction may not proceed. If it is used more than 5 mol, the reaction will not be affected, but it may be difficult to remove the acid after the reaction. It is not preferable.

In the present invention, thiols can be added and reacted as necessary. Known thiols can be used as the thiols that can be used in the present invention. For example, mercaptocarboxylic acids such as thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid, methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan , Alkyl mercaptans such as butyl mercaptan, octyl mercaptan, decyl mercaptan, dodecyl mercaptan, aralkyl mercaptans such as benzyl mercaptan, and alkali metal salts thereof. Thiols can be used alone or in combination of two or more. Of these, alkyl mercaptans are preferred. Although the usage-amount of thiols is not specifically limited, Usually, 0.01-0.3 mol is used with respect to 1 mol of fluorenones, Preferably 0.01-0.1 mol is used.

In the present invention, the reaction can be carried out in the presence of an organic solvent if necessary. As the organic solvent that can be used in the present invention, aromatic hydrocarbons such as toluene and xylene, and halogen-containing aromatic hydrocarbons such as chlorobenzene and dichlorobenzene can be used. When an organic solvent is used, it is usually used in an amount of 2 to 20 times by weight, preferably 2 to 10 times by weight with respect to 1 time by weight of fluorenone.

Although the temperature which implements this invention is not specifically limited, Usually, 40-140 degreeC, Preferably it implements at 65-85 degreeC. When the temperature is lower than 40 ° C., the reaction may not proceed sufficiently. When the temperature is higher than 140 ° C., a large amount of tar may be generated and purification may be difficult.

After completion of the reaction, an alkali solution such as an aqueous alkali metal hydroxide solution is added to the obtained reaction mixture to neutralize the acid catalyst, and then the desired reaction is represented by the above formula (1) by cooling crystallization. Crude crystals of a fluorene diol compound can be obtained. The fluorene-based diol compounds represented by the above formula (1) thus obtained may be used as a product as they are, but may be purified as necessary to obtain a high-purity product. In the purification method, for example, a mixture of a crystallization solvent, for example, an aromatic hydrocarbon such as toluene and water is added to the crude crystal, and the mixture is separated, and the target product is crystallized again from the remaining oil layer. Is separated by filtration and dried to obtain fluorene-based diol compounds represented by the above formula (1) with high purity.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

  Each measurement value measured about a fluorene type diol compound and a fluorene type polymer followed the following method and measurement conditions.

[1] HPLC purity Area percentage values when HPLC measurement was performed under the following measurement conditions were defined as a residual ratio and HPLC purity.

・ Device: “LC-2010AHT” manufactured by Shimadzu Corporation
Column: YMC-Pack ODS-A manufactured by YMC Co., Ltd.
(5 μm, 4.6 mmφ × 250 mm),
Column temperature: 40 ° C
・ Detection wavelength: UV 240 nm,
-Mobile phase: A liquid = 30% methanol water, B liquid = methanol-Mobile phase flow rate: 1.0 ml / min,
Mobile phase gradient: Liquid B concentration: 30% (0 minutes) → 100% (after 25 minutes) → 100% (after 35 minutes).

[2] Melting point The melting point was measured using a differential scanning calorimeter (“EXSTAR DSC 7020” manufactured by SII Nano Technology Co., Ltd.) at a heating rate of 10 ° C./min.

[3] NMR measurement
¹ H-NMR and ¹³ C-NMR were recorded on a JEOL-ESC400 spectrometer using acetone-d6 as the solvent.

[4] LC-MS Measurement LC-MS was separated and mass analyzed under the following measurement conditions to identify the target product.

・ Device: “Xevo G2 Q-Tof” manufactured by Waters Co., Ltd.
Column: “ACQUITY UPLC BEH C18” manufactured by Waters Co., Ltd.
(1.7μm, 2.1mmφ × 100mm)
-Column temperature: 40 ° C
・ Detection wavelength: UV 210-500nm
-Mobile phase: Liquid A = 0.05% aqueous formic acid, Liquid B = 0.05% formic acid acetonitrile-Mobile phase flow rate: 0.3 ml / min-Mobile phase gradient: Liquid B concentration: 60% (0 min)-> 100 % (After 10 minutes) → 100% (after 15 minutes)
・ Detection method: Q-Tof
・ Ionization method: ESI (−) method ・ Ion Source: Voltage (−) 2.0 kV, temperature 120 ° C.
Sampling Cone: voltage 10V, gas flow 50L / h
Desolvation Gas: Temperature 500 ° C., Gas flow 1000 L / h

<Example 1>
In a glass test tube, 9-fluorenone 0.20 g (0.001 mol), 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran 0.73 g (0.004 mol), β-mercaptopropionic acid 0. 01 g (0.0001 mol), p-toluenesulfonic acid monohydrate 0.21 g (0.001 mol) and toluene (1.20 g) were added, the temperature was raised to 85 ° C., and the mixture was stirred at the same temperature for 5 hours. When the reaction mixture was analyzed by HPLC when the mixture was stirred for 5 hours, the residual ratio of 9-fluorenone was 1.0% or less.

The obtained reaction mixture was neutralized by adding 24% by weight sodium hydroxide, and the precipitated solid was collected. Next, the collected solid was washed three times with toluene and three times with water, and then dried under reduced pressure, whereby the compound of the above general formula (1) [9,9-bis (2,3-dihydro-2, White crystals of 2-dimethyl-7-hydroxybenzofuran-5-yl) fluorene] were obtained. The HPLC purity of the white crystals was 97.6%. About the fluorene type diol compound represented by the said Formula (1) obtained, the measurement result of < ¹ > H-NMR, < ¹³ > C-NMR, and LC-MS is shown below.

¹ H-NMR (Acetone-D6, 400 MHz) δ (ppm): 1.33 (s, 12H), 2.83 (s, 4H), 6.41 (s, 2H), 6.57 (s, 2H) ), 7.24 (dd, J = 6.46, 2H), 7.31 (dd, J = 6.46, 2H), 7.40 (d, J = 6.12, 2H), 7.65 (S, 2H), 7.79 (d, J = 6.46, 2H).

¹³ C-NMR (CDCl ₃ , 400 MHz) δ (ppm): 28.07, 43.54, 65.24, 87.06, 116.15, 120.46, 126.80, 127.65, 127.89 128.14, 139.19, 140.38, 141.20, 145.63, 152.75.

  Moreover, the HH COSY spectrum of the fluorene-type diol compound represented by the said Formula (1) is shown in FIG. 3, respectively. From these two-dimensional NMR spectra, the fluorene-based diol compound represented by the above formula (1) has a structure as represented by the above formula (1), and in particular, fluorene at the 5-position of the benzofuran ring. It was confirmed that it was bonded to the 9th position.

The results of mass spectrometry obtained using LC-MS are shown in FIG. The calculated value of fluorene-based diol compound (TOF MS ESI ⁻ ; C ₃₃ H ₃₄ O ₆ —H) in this analysis was 489.0206, and the actually measured value was 489.2061.

Claims (2)

Following formula (1):

A fluorene-based diol compound represented by: In the presence of acid, fluorenone and the following formula (2)

The method for producing a fluorene-based diol compound according to claim 1, wherein the benzofuran derivative represented by the formula is reacted.

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