JPH10245352A - Purification of biscresol compounds - Google Patents
Purification of biscresol compoundsInfo
- Publication number
- JPH10245352A JPH10245352A JP5064697A JP5064697A JPH10245352A JP H10245352 A JPH10245352 A JP H10245352A JP 5064697 A JP5064697 A JP 5064697A JP 5064697 A JP5064697 A JP 5064697A JP H10245352 A JPH10245352 A JP H10245352A
- Authority
- JP
- Japan
- Prior art keywords
- bcf
- lower aliphatic
- solvent
- fluorene
- crystals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、フルオレン誘導品
の精製方法に関する。より詳しくは、低級脂肪族アルコ
ール及び低級脂肪族ケトンを含む混合溶媒を用い、９，
９−ビス（３−メチル−４−ヒドロキシフェニル）フル
オレン（以下「ＢＣＦ」と略す）の晶析等を行うことに
よって精製する方法に関する。[0001] The present invention relates to a method for purifying a fluorene derivative. More specifically, using a mixed solvent containing a lower aliphatic alcohol and a lower aliphatic ketone,
The present invention relates to a method for purification by crystallization of 9-bis (3-methyl-4-hydroxyphenyl) fluorene (hereinafter abbreviated as “BCF”).
【０００２】[0002]
【従来の技術】ＢＣＦは、下記構造を有するフルオレン
誘導品であり、例えばエポキシ樹脂、ポリエステル等の
製造原料、感熱紙の保存安定剤、顕色剤、酸化防止剤、
ゴムの劣化防止剤等として有用な化合物である。2. Description of the Related Art BCF is a fluorene derivative having the following structure, for example, raw materials for producing epoxy resins and polyesters, storage stabilizers for thermal paper, color developers, antioxidants, and the like.
It is a compound useful as a rubber deterioration inhibitor.
【０００３】[0003]
【化１】 Embedded image
【０００４】ＢＣＦを精製する方法として例えば晶析法
が知られている（特開平４−４１４５０号）。この方法
ではメタノール及び水が晶析溶媒として用いられる。具
体的には、反応後において、未反応のｏ−クレゾールを
少なくとも一部残した状態で反応混合物に低級脂肪族ア
ルコール（メタノール等）を混合して均質溶液とした
後、水を添加して結晶を析出するものである。[0004] As a method for purifying BCF, for example, a crystallization method is known (JP-A-4-41450). In this method, methanol and water are used as crystallization solvents. Specifically, after the reaction, a lower aliphatic alcohol (such as methanol) is mixed with the reaction mixture in a state where at least a part of unreacted o-cresol is left, and then a homogeneous solution is added. Is deposited.
【０００５】しかしながら、上記方法によれば、ＢＣＦ
と溶媒（特にアルコール類）との間で包接化合物を形成
し、その結果としてＢＣＦ結晶中に溶媒が約１：１の割
合で内包されることとなる。しかも、内包された溶媒
は、減圧乾燥によって除去しようとしても、高温で、か
つ、多大な時間を要するため、上記方法を工業的規模で
適用することは困難である。溶媒が内包されたＢＣＦ
は、当然ながらエポキシ樹脂、ポリエステル等の製造原
料その他の用途において工業的に使用するには問題があ
る。However, according to the above method, the BCF
And a solvent (particularly, alcohols) forms an inclusion compound. As a result, the solvent is included in the BCF crystal at a ratio of about 1: 1. Moreover, even if the encapsulated solvent is to be removed by drying under reduced pressure, it is difficult to apply the above method on an industrial scale because it requires a high temperature and a long time. BCF containing solvent
Of course, there is a problem in industrial use in raw materials such as epoxy resins and polyesters and other uses.
【０００６】一方、トルエン、ｎ−ヘキサン等を晶析溶
媒として用いると、これら溶媒は結晶中に内包されない
が、粗結晶に対して１０〜２０倍重量もの大量の溶媒を
必要とし、また晶析収率が低い等の問題点がある。On the other hand, when toluene, n-hexane, or the like is used as a crystallization solvent, these solvents are not included in the crystal, but require a large amount of a solvent as large as 10 to 20 times the weight of the crude crystal. There are problems such as a low yield.
【０００７】[0007]
【発明が解決しようとする課題】従って、本発明は、特
に、溶媒が内包されていない結晶を高収率で得られるビ
スクレゾール類の精製方法を提供することを主な目的と
する。SUMMARY OF THE INVENTION Accordingly, it is a main object of the present invention to provide a method for purifying biscresols, in which crystals containing no solvent are obtained in high yield.
【０００８】[0008]
【課題を解決するための手段】本発明は、上記従来技術
の問題点に鑑み、鋭意研究した結果、特定の組合せを含
む混合溶媒を用いて一定方法で精製処理を行う場合に
は、予想外にも溶媒が内包されないＢＣＦが比較的高収
率で得られることを見出し、本発明を完成するに至っ
た。The present invention has been made in view of the above-mentioned problems of the prior art, and as a result of intensive studies, it has been found that, when the purification treatment is carried out by a certain method using a mixed solvent containing a specific combination, unexpected results are obtained. The present inventors have found that BCF containing no solvent can be obtained in a relatively high yield, and have completed the present invention.
【０００９】すなわち、本発明は、炭素数１〜３の低級
脂肪族アルコール及び炭素数３〜７の低級脂肪族ケトン
を含む混合溶媒を用いて晶析を行うことを特徴とする
９，９−ビス（３−メチル−４−ヒドロキシフェニル）
フルオレンの精製方法に係るものである。That is, the present invention is characterized in that crystallization is carried out using a mixed solvent containing a lower aliphatic alcohol having 1 to 3 carbon atoms and a lower aliphatic ketone having 3 to 7 carbon atoms. Bis (3-methyl-4-hydroxyphenyl)
The present invention relates to a method for purifying fluorene.
【００１０】[0010]
【発明の実施の形態】以下、本発明をその実施の形態と
ともに説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described together with its embodiments.
【００１１】本発明において、精製の対象となるＢＣＦ
は、特に制限されず、あらゆるものを使用できる。例え
ば、ＢＣＦ製造のための反応によって得られた反応液
（ＢＣＦを含む混合液）をそのまま用いることもでき
る。In the present invention, the BCF to be purified is
Is not particularly limited, and any can be used. For example, a reaction solution (mixture containing BCF) obtained by a reaction for producing BCF can be used as it is.
【００１２】また、ＢＣＦは、例えば純度の低いＢＣＦ
結晶（粗結晶）でも、純度の高いＢＣＦ結晶であっても
良い。すなわち、本発明の精製方法は、再結晶において
も適用することができる。BCF is, for example, BCF of low purity.
It may be a crystal (coarse crystal) or a highly pure BCF crystal. That is, the purification method of the present invention can be applied to recrystallization.
【００１３】さらに、ＢＣＦは、いずれの製造方法によ
って得られたものでも良く、例えば塩酸ガスとβ−メル
カプトプロピオン酸を触媒とし、フルオレノンとｏ−ク
レゾールとを反応させて得られたものも使用することが
できる。Further, BCF may be obtained by any production method. For example, BCF obtained by reacting fluorenone with o-cresol using hydrochloric acid gas and β-mercaptopropionic acid as a catalyst is also used. be able to.
【００１４】なお、使用するＢＣＦ結晶の純度は、より
高純度のＢＣＦを得るという観点からみれば、当初より
できるだけ高い純度のものを用いることが望ましく、こ
の場合には特に純度５０％以上のものが好ましい。From the viewpoint of obtaining a higher purity BCF, it is desirable to use a BCF crystal having a purity as high as possible from the beginning. In this case, it is particularly preferable to use a crystal having a purity of 50% or more. Is preferred.
【００１５】精製では、精製すべきＢＣＦ（ＢＣＦを含
む混合液等）を、炭素数１〜３の低級脂肪族アルコール
及び炭素数３〜７の低級脂肪族ケトンを含む混合溶媒に
加え、この溶液からＢＣＦを晶析させる。上記ＢＣＦと
してＢＣＦ結晶（粗結晶）を用いる場合も、これを上記
混合溶媒に溶解させ、同様にこの溶液からＢＣＦの再結
晶を行えば良い。In the purification, BCF to be purified (a mixed solution containing BCF, etc.) is added to a mixed solvent containing a lower aliphatic alcohol having 1 to 3 carbon atoms and a lower aliphatic ketone having 3 to 7 carbon atoms, and From which BCF is crystallized. When a BCF crystal (coarse crystal) is used as the BCF, the BCF may be dissolved in the mixed solvent, and the BCF may be recrystallized from the solution in the same manner.
【００１６】上記低級脂肪族アルコールとしては、例え
ばメタノール、エタノール、ｎ−プロパノール、イソプ
ロパノール等が挙げられる。上記低級脂肪族ケトンとし
ては、例えばアセトン、メチルエチルケトン、ジエチル
ケトン、エチルプロピルケトン、ジ−ｎ−プロピルケト
ン、ジイソプロピルケトン等が挙げられる。これら低級
脂肪族アルコール及び低級脂肪族ケトンは、それぞれ１
種又は２種以上で用いることができる。これらの中で
も、特にメタノール及びアセトンの組合せを含むように
用いることが好ましい。The lower aliphatic alcohol includes, for example, methanol, ethanol, n-propanol, isopropanol and the like. Examples of the lower aliphatic ketone include acetone, methyl ethyl ketone, diethyl ketone, ethyl propyl ketone, di-n-propyl ketone, diisopropyl ketone, and the like. These lower aliphatic alcohols and lower aliphatic ketones each have 1
Species or two or more can be used. Among these, it is particularly preferable to use a combination of methanol and acetone.
【００１７】混合溶媒の混合比（重量比）は、通常は上
記低級脂肪族アルコール：上記低級脂肪族ケトン＝１：
９〜９：１程度、好ましくは４：６〜６：４とする。ま
た、混合溶媒の使用量は、ＢＣＦ１モルに対し、通常５
０〜４０００ｇ程度、特に５００〜２０００ｇとするこ
とが好ましい。なお、混合溶媒中には、本発明の効果を
損なわない範囲内で他の成分が含まれていても良い。The mixing ratio (weight ratio) of the mixed solvent is usually lower aliphatic alcohol: lower aliphatic ketone = 1: 1.
The ratio is about 9 to 9: 1, preferably 4: 6 to 6: 4. The amount of the mixed solvent used is usually 5 to 1 mol of BCF.
It is preferably about 0 to 4000 g, particularly preferably 500 to 2000 g. The solvent mixture may contain other components as long as the effects of the present invention are not impaired.
【００１８】上記の溶液は、必要に応じて加熱すること
ができる。この場合、ＢＣＦ側及び混合溶媒側の少なく
とも一方を予め加熱しておいても良い。加熱された溶液
の温度は、ＢＣＦがほぼ完全に溶解する温度であれば特
に制限されず、溶媒の混合比及び使用量等の条件により
適宜設定することができる。通常は５０℃〜溶媒の還流
温度とすれば良い。なお、条件等によっては、ＢＣＦが
完全に溶解しない場合もあるが、本発明の効果を損なわ
ない限り特に差し支えない。The above solution can be heated if necessary. In this case, at least one of the BCF side and the mixed solvent side may be heated in advance. The temperature of the heated solution is not particularly limited as long as it is a temperature at which BCF is almost completely dissolved, and can be appropriately set according to conditions such as the mixing ratio of the solvent and the amount used. Usually, the temperature may be 50 ° C. to the reflux temperature of the solvent. Depending on conditions and the like, BCF may not be completely dissolved, but it does not matter as long as the effects of the present invention are not impaired.
【００１９】保持時間は、ＢＣＦがほぼ完全に溶解する
のに十分な時間であれば特に制限されない。おおよその
保持時間は、通常１分〜２時間程度である。保持時間が
短かすぎると精製効果があまり得られない。保持時間が
長すぎくても精製効果に大きな差はみられず経済上有利
ではない。The holding time is not particularly limited as long as the time is sufficient for the BCF to be almost completely dissolved. The approximate holding time is usually about 1 minute to 2 hours. If the retention time is too short, the purification effect will not be obtained much. If the retention time is too long, there is no significant difference in the purification effect, which is not economically advantageous.
【００２０】上記温度で一定時間保持した後は、冷却を
行う。冷却温度は、十分晶析できる限り特に制限されな
いが、通常は４０℃〜−１０℃程度、好ましくは３０〜
０℃とすれば良い。温度が高すぎると、析出が不十分と
なるため、収率の面で有利ではない。また、冷却温度は
低くても良いが、冷却に要する労力に比して精製効果が
得られないので経済的に有利ではない。After holding at the above temperature for a certain period of time, cooling is performed. The cooling temperature is not particularly limited as long as it can be sufficiently crystallized, but is usually about 40 ° C to -10 ° C, preferably 30 to
The temperature may be set to 0 ° C. If the temperature is too high, precipitation will be insufficient, which is not advantageous in terms of yield. Although the cooling temperature may be low, it is not economically advantageous because the purification effect cannot be obtained as compared with the labor required for cooling.
【００２１】晶析した結晶は、公知の結晶回収手段に従
って、回収すれば良い。例えば、濾過、遠心分離等によ
り固液分離して、結晶を回収することができる。得られ
たＢＣＦ結晶は、必要に応じてさらに本発明による精製
方法のいずれかを繰り返して行うこともできる。この場
合の条件は上記と同様にして行えば良い（洗浄による方
法については後記に示す）。The crystallized crystals may be recovered according to known crystal recovery means. For example, crystals can be collected by solid-liquid separation by filtration, centrifugation, or the like. The obtained BCF crystal can be further subjected to any of the purification methods according to the present invention, if necessary. The conditions in this case may be performed in the same manner as described above (the cleaning method will be described later).
【００２２】本発明は、ＢＣＦの粗結晶を、前記の低級
脂肪族アルコール及び低級脂肪族ケトンを含む混合溶媒
で洗浄することによって精製する方法も包含する。The present invention also includes a method of purifying crude BCF crystals by washing with a mixed solvent containing the above-mentioned lower aliphatic alcohol and lower aliphatic ketone.
【００２３】本発明における洗浄は、ＢＣＦ粗結晶が完
全に溶解しない条件下（温度、溶媒量等）で上記混合溶
媒を用いて処理することにより実施できる。例えば、Ｂ
ＣＦ粗結晶が完全に溶解しないように、室温（約２０
℃）下において上記混合溶媒をＢＣＦ粗結晶に加え、攪
拌した後、結晶を回収すれば良い。また、例えば完全溶
解に至らないような量の上記混合溶媒を加え、室温〜溶
媒の沸点の温度範囲内で粗結晶を部分的に溶解させた
後、必要に応じて通常１０℃〜室温程度まで冷却し、次
いで前記と同様にして結晶を回収すれば良い。なお、本
発明の洗浄による精製においても、混合溶媒中には、本
発明の効果を損なわない範囲内で他の成分が含まれてい
ても良い。The washing in the present invention can be carried out by treating with the above-mentioned mixed solvent under conditions (temperature, amount of solvent, etc.) under which the BCF crude crystals are not completely dissolved. For example, B
At room temperature (approximately 20
C), the above mixed solvent is added to the BCF crude crystals, and after stirring, the crystals may be recovered. Also, for example, after adding the mixed solvent in an amount that does not result in complete dissolution and partially dissolving the crude crystals within the temperature range from room temperature to the boiling point of the solvent, if necessary, usually from about 10 ° C. to about room temperature After cooling, the crystals may be recovered in the same manner as described above. In the purification by washing of the present invention, other components may be contained in the mixed solvent as long as the effects of the present invention are not impaired.
【００２４】[0024]
【発明の効果】本発明の精製方法によれば、結晶中に溶
媒が内包されていないＢＣＦを比較的高収率で得ること
ができる。また、使用する溶媒量も少なくて済み、操作
上、経済上等の点でも有利である。According to the purification method of the present invention, BCF in which a solvent is not included in the crystal can be obtained in a relatively high yield. Further, the amount of the solvent to be used is small, which is advantageous in terms of operation and economy.
【００２５】このような本発明の精製方法は、工業的規
模で高品質のＢＣＦを生産する上で非常に有用である。Such a purification method of the present invention is very useful for producing high-quality BCF on an industrial scale.
【００２６】[0026]
【実施例】以下、実施例及び比較例を示し、本発明の特
徴をより一層明確にする。EXAMPLES Examples and comparative examples are shown below to further clarify the features of the present invention.
【００２７】なお、本実施例において、純度はＨＰＬＣ
で分析し面積百分率で表示した。溶媒の含有率はＴＧ
（熱分析）により分析した。収率は［ＢＣＦのモル数／
原料フルオレノンのモル数］により計算した。また、内
包する溶媒はＮＭＲ分析を行った。In this example, the purity was determined by HPLC.
And expressed as area percentage. Solvent content is TG
(Thermal analysis). The yield is [moles of BCF /
Number of moles of raw material fluorenone]. The solvent included therein was subjected to NMR analysis.
【００２８】実施例１ 攪拌機、冷却管及びガス吹き込み管を備えた内容積１０
００ｍｌの容器に純度９９．５重量％のフルオレノン９
０ｇ（０．５ｍｏｌ）とｏ−クレゾール４３２ｇ（４．
０ｍｏｌ）を仕込み、β−メルカプトプロピオン酸３ｍ
ｌを加えて、反応温度を５０℃に保ち、塩酸ガスを２０
０ｍｌ／分の割合で吹き込みながら、４時間かけて反応
を完結させ、反応液を得た。Example 1 Internal volume 10 equipped with stirrer, cooling pipe and gas blowing pipe
Fluorenone 9 having a purity of 99.5% by weight in a 00 ml container.
0 g (0.5 mol) and 432 g of o-cresol (4.
0 mol), and β-mercaptopropionic acid 3m
The reaction temperature is kept at 50 ° C.
The reaction was completed over 4 hours while blowing at a rate of 0 ml / min to obtain a reaction solution.
【００２９】得られた反応液に、メタノール：アセトン
＝１：１（重量比）の混合溶媒を３６０ｇを加え、７０
℃まで加熱し、攪拌しながらその温度を１５分間保持し
た。その後、攪拌しながら１０℃まで冷却した。析出し
た結晶を濾過により分離し、乾燥させた。得られた結晶
の純度は９６．９％であり、溶媒の含有率は０％であっ
た。収率は９１％であった。360 g of a mixed solvent of methanol: acetone = 1: 1 (weight ratio) was added to the obtained reaction solution,
C. and held at that temperature for 15 minutes with stirring. Then, it cooled to 10 degreeC, stirring. The precipitated crystals were separated by filtration and dried. The purity of the obtained crystal was 96.9%, and the content of the solvent was 0%. The yield was 91%.
【００３０】実施例２ 実施例１と同様にして得られた反応液に、メタノール：
アセトン＝２：１（重量比）に混合溶媒を４５０ｇを加
え、６５℃まで加熱し、攪拌しながらその温度を１５分
間保持した。その後、攪拌しながら１０℃まで冷却し
た。析出した結晶を濾過により分離し、乾燥させた。得
られた結晶の純度は９７．２％であり、溶媒の含有率は
０％であった。収率は９０％であった。Example 2 A reaction solution obtained in the same manner as in Example 1 was added with methanol:
450 g of the mixed solvent was added to acetone = 2: 1 (weight ratio), heated to 65 ° C., and the temperature was maintained for 15 minutes while stirring. Then, it cooled to 10 degreeC, stirring. The precipitated crystals were separated by filtration and dried. The purity of the obtained crystals was 97.2%, and the content of the solvent was 0%. The yield was 90%.
【００３１】実施例３ 実施例１と同様にして得られた結晶を再結晶することに
より精製した。Example 3 A crystal obtained in the same manner as in Example 1 was purified by recrystallization.
【００３２】実施例１で得られた結晶に、メタノール：
アセトン＝１：１（重量比）に混合溶媒を４５０ｇを加
え、７０℃まで加熱して攪拌しながらその温度を１５分
間保持した。その後、攪拌しながら１０℃まで冷却し
た。析出した結晶を濾過により分離し、乾燥させた。得
られた結晶の純度は９９．２％であり、溶媒の含有率は
０％であった。収率は８１％であった。In the crystals obtained in Example 1, methanol:
450 g of the mixed solvent was added to acetone = 1: 1 (weight ratio), and the temperature was maintained for 15 minutes while heating to 70 ° C. and stirring. Then, it cooled to 10 degreeC, stirring. The precipitated crystals were separated by filtration and dried. The purity of the obtained crystals was 99.2%, and the content of the solvent was 0%. The yield was 81%.
【００３３】実施例４ 実施例１で得られた結晶を洗浄することにより精製し
た。Example 4 The crystals obtained in Example 1 were purified by washing.
【００３４】実施例１で得られた結晶に、メタノール：
アセトン＝１：１（重量比）に混合溶媒を４５０ｇを加
え、室温で１５分攪拌した後、濾過により分離し、乾燥
させた。得られた結晶の純度は９８．３％であり、溶媒
の含有率は０％であった。収率は８６％であった。In the crystals obtained in Example 1, methanol:
450 g of the mixed solvent was added to acetone = 1: 1 (weight ratio), and the mixture was stirred at room temperature for 15 minutes, then separated by filtration and dried. The purity of the obtained crystals was 98.3%, and the content of the solvent was 0%. The yield was 86%.
【００３５】実施例５ エタノール：アセトン＝１：１（重量比）である混合溶
媒を用いたほかは実施例１と同様にして精製を行った。
得られた結晶の純度は９７．１％であり、溶媒の含有率
は０％であった。収率は８９％であった。Example 5 Purification was carried out in the same manner as in Example 1 except that a mixed solvent of ethanol: acetone = 1: 1 (weight ratio) was used.
The purity of the obtained crystals was 97.1%, and the content of the solvent was 0%. The yield was 89%.
【００３６】実施例６ プロパノール：アセトン＝１：１（重量比）である混合
溶媒を用いたほかは実施例１と同様にして精製を行っ
た。得られた結晶の純度は９７．２％であり、溶媒の含
有率は０％であった。収率は８５％であった。Example 6 Purification was carried out in the same manner as in Example 1 except that a mixed solvent of propanol: acetone = 1: 1 (weight ratio) was used. The purity of the obtained crystals was 97.2%, and the content of the solvent was 0%. The yield was 85%.
【００３７】実施例７ メタノール：メチルエチルケトン＝１：１（重量比）で
ある混合溶媒を用いたほかは実施例１と同様にして精製
を行った。得られた結晶の純度は９７．４％であり、溶
媒の含有率は０％であった。収率は８５％であった。Example 7 Purification was carried out in the same manner as in Example 1 except that a mixed solvent of methanol: methyl ethyl ketone = 1: 1 (weight ratio) was used. The purity of the obtained crystals was 97.4%, and the content of the solvent was 0%. The yield was 85%.
【００３８】実施例８ メタノール：エタノール：アセトン＝１：１：２（重量
比）である混合溶媒を用いたほかは実施例１と同様にし
て精製を行った。得られた結晶の純度は９７．３％であ
り、溶媒の含有率は０％であった。収率は８２％であっ
た。Example 8 Purification was carried out in the same manner as in Example 1 except that a mixed solvent of methanol: ethanol: acetone = 1: 1: 2 (weight ratio) was used. The purity of the obtained crystals was 97.3%, and the content of the solvent was 0%. The yield was 82%.
【００３９】比較例１ 実施例１で得られた反応液に、メタノール９００ｇを加
え、６４℃まで加熱し、攪拌しながらその温度を１５分
間保持した。その後、攪拌しながら１０℃まで冷却し
た。析出した結晶を濾過により分離し、乾燥させた。得
られた結晶の純度は９６．５％であり、溶媒の含有率は
９．８％であった。ＮＭＲ分析より含有されている溶媒
はメタノールのみであった。収率は８２％であった。Comparative Example 1 To the reaction solution obtained in Example 1, 900 g of methanol was added, heated to 64 ° C., and the temperature was maintained for 15 minutes while stirring. Then, it cooled to 10 degreeC, stirring. The precipitated crystals were separated by filtration and dried. The purity of the obtained crystals was 96.5%, and the content of the solvent was 9.8%. From NMR analysis, the contained solvent was only methanol. The yield was 82%.
【００４０】比較例２ 実施例１で得られた反応液に、アセトン３６０ｇを加
え、６５℃まで加熱し、攪拌しながらその温度を１５分
間保持した。その後、攪拌しながら１０℃まで冷却し
た。析出した結晶を濾過により分離し、乾燥させた。得
られた結晶の純度は９４．６％であり、溶媒の含有率は
２２％であった。ＮＭＲ分析より含有されている溶媒は
メタノールのみであった。収率は８８％であった。Comparative Example 2 360 g of acetone was added to the reaction solution obtained in Example 1, heated to 65 ° C., and the temperature was maintained for 15 minutes while stirring. Then, it cooled to 10 degreeC, stirring. The precipitated crystals were separated by filtration and dried. The purity of the obtained crystals was 94.6%, and the content of the solvent was 22%. From NMR analysis, the contained solvent was only methanol. The yield was 88%.
【００４１】比較例３ 実施例１で得られた反応液に、アセトン：アセトニトリ
ル＝６：１の混合溶媒１２６０ｇを加え、６４℃まで加
熱し、攪拌しながらその温度を１５分間保持した。その
後、攪拌しながら１０℃まで冷却した。析出した結晶を
濾過により分離し、乾燥させた。得られた結晶の純度は
９７．５％であり、溶媒の含有率は１９％であった。Ｎ
ＭＲ分析より含有されている溶媒はアセトンのみであっ
た。収率は８４％であった。Comparative Example 3 To the reaction solution obtained in Example 1, 1260 g of a mixed solvent of acetone: acetonitrile = 6: 1 was added, heated to 64 ° C., and the temperature was maintained for 15 minutes while stirring. Then, it cooled to 10 degreeC, stirring. The precipitated crystals were separated by filtration and dried. The purity of the obtained crystals was 97.5%, and the content of the solvent was 19%. N
From the MR analysis, the solvent contained was only acetone. The yield was 84%.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 下川床 隆幸 大阪府大阪市中央区平野町四丁目１番２号 大阪瓦斯株式会社内 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Takayuki Shimokawadoko Osaka Gas Co., Ltd. 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka
Claims (4)
炭素数３〜７の低級脂肪族ケトンを含む混合溶媒を用い
て晶析を行うことを特徴とする９，９−ビス（３−メチ
ル−４−ヒドロキシフェニル）フルオレンの精製方法。A crystallization is carried out using a mixed solvent containing a lower aliphatic alcohol having 1 to 3 carbon atoms and a lower aliphatic ketone having 3 to 7 carbon atoms. A method for purifying methyl-4-hydroxyphenyl) fluorene.
シフェニル）フルオレンを含む混合液を、炭素数１〜３
の低級脂肪族アルコール及び炭素数３〜７の低級脂肪族
ケトンを含む混合溶媒に加えた後、９，９−ビス（３−
メチル−４−ヒドロキシフェニル）フルオレンの晶析を
行うことを特徴とする請求項１記載の精製方法。2. A mixed solution containing 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene is mixed with a mixture having 1 to 3 carbon atoms.
After addition to a mixed solvent containing a lower aliphatic alcohol and a lower aliphatic ketone having 3 to 7 carbon atoms, and then adding 9,9-bis (3-
The purification method according to claim 1, wherein crystallization of (methyl-4-hydroxyphenyl) fluorene is performed.
シフェニル）フルオレンの粗結晶を、炭素数１〜３の低
級脂肪族アルコール及び炭素数３〜７の低級脂肪族ケト
ンを含む混合溶媒に溶解させた後、９，９−ビス（３−
メチル−４−ヒドロキシフェニル）フルオレンの再結晶
を行うことを特徴とする請求項１記載の精製方法。3. A mixture of crude crystals of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene containing a lower aliphatic alcohol having 1 to 3 carbon atoms and a lower aliphatic ketone having 3 to 7 carbon atoms. After dissolving in a solvent, 9,9-bis (3-
The purification method according to claim 1, wherein recrystallization of (methyl-4-hydroxyphenyl) fluorene is performed.
シフェニル）フルオレンの粗結晶を、炭素数１〜３の低
級脂肪族アルコール及び炭素数３〜７の低級脂肪族ケト
ンを含む混合溶媒で洗浄することを特徴とする９，９−
ビス（３−メチル−４−ヒドロキシフェニル）フルオレ
ンの精製方法。4. A mixture comprising crude crystals of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene containing a lower aliphatic alcohol having 1 to 3 carbon atoms and a lower aliphatic ketone having 3 to 7 carbon atoms. 9.9- characterized by washing with a solvent
A method for purifying bis (3-methyl-4-hydroxyphenyl) fluorene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05064697A JP3521242B2 (en) | 1997-03-05 | 1997-03-05 | Purification method of biscresols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05064697A JP3521242B2 (en) | 1997-03-05 | 1997-03-05 | Purification method of biscresols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10245352A true JPH10245352A (en) | 1998-09-14 |
| JP3521242B2 JP3521242B2 (en) | 2004-04-19 |
Family
ID=12864720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05064697A Expired - Lifetime JP3521242B2 (en) | 1997-03-05 | 1997-03-05 | Purification method of biscresols |
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| Country | Link |
|---|---|
| JP (1) | JP3521242B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006193505A (en) * | 2004-12-14 | 2006-07-27 | Osaka Gas Co Ltd | Method for producing fluorene derivative |
| JP2010248176A (en) * | 2009-03-23 | 2010-11-04 | Honshu Chem Ind Co Ltd | Process for producing 9,9-bis (4-hydroxyphenyl) fluorenes |
| WO2011016357A1 (en) * | 2009-08-05 | 2011-02-10 | 田岡化学工業株式会社 | Non-crystalline form of fluorene derivative and process for preparation thereof |
| JP2018048086A (en) * | 2016-09-21 | 2018-03-29 | 田岡化学工業株式会社 | Crystal of alcohol compound having fluorene skeleton and method for producing the same |
| JP2019108408A (en) * | 2019-04-16 | 2019-07-04 | 田岡化学工業株式会社 | Crystal of alcohol compound having fluorene skeleton and method for producing the same |
| KR20210025010A (en) | 2018-06-27 | 2021-03-08 | 혼슈우 카가쿠고교 가부시키가이샤 | Crystalline of 9,9-bis(4-hydroxyphenyl)-2,3-benzofluorene |
-
1997
- 1997-03-05 JP JP05064697A patent/JP3521242B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006193505A (en) * | 2004-12-14 | 2006-07-27 | Osaka Gas Co Ltd | Method for producing fluorene derivative |
| JP2010248176A (en) * | 2009-03-23 | 2010-11-04 | Honshu Chem Ind Co Ltd | Process for producing 9,9-bis (4-hydroxyphenyl) fluorenes |
| WO2011016357A1 (en) * | 2009-08-05 | 2011-02-10 | 田岡化学工業株式会社 | Non-crystalline form of fluorene derivative and process for preparation thereof |
| JP5568558B2 (en) * | 2009-08-05 | 2014-08-06 | 田岡化学工業株式会社 | Amorphous form of fluorene derivative and method for producing the same |
| JP2018048086A (en) * | 2016-09-21 | 2018-03-29 | 田岡化学工業株式会社 | Crystal of alcohol compound having fluorene skeleton and method for producing the same |
| KR20210025010A (en) | 2018-06-27 | 2021-03-08 | 혼슈우 카가쿠고교 가부시키가이샤 | Crystalline of 9,9-bis(4-hydroxyphenyl)-2,3-benzofluorene |
| JP2019108408A (en) * | 2019-04-16 | 2019-07-04 | 田岡化学工業株式会社 | Crystal of alcohol compound having fluorene skeleton and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3521242B2 (en) | 2004-04-19 |
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