JP2009274966A - Method for producing diaryloxybiphenyltetracarboxylic dianhydride - Google Patents
Method for producing diaryloxybiphenyltetracarboxylic dianhydride Download PDFInfo
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Abstract
Description
本発明は耐熱性の高分子であるポリイミドなどの合成において有用な原料であるジアリールオキシビフェニルテトラカルボン酸二無水物の新規な製造方法に関する。 The present invention relates to a novel method for producing diaryloxybiphenyltetracarboxylic dianhydride, which is a raw material useful in the synthesis of polyimide, which is a heat-resistant polymer.
これまでに、ジアリールオキシビフェニルテトラカルボン酸二無水物の製造方法として、ビフェニルテトラカルボン酸二無水物をメチルアミンと反応させてビス（Ｎ−メチルフタルイミド）とし、これをニトロ化してビス（ジニトロ−Ｎ−メチルフタルイミド）とした後にこれをフェノールと反応させてビス（ジフェノキシ−Ｎ−メチルフタルイミド）とし、次にこれをアルカリ水溶液中で加水分解してテトラカルボン酸にした後に脱水環化してジフェノキシビフェニルテトラカルボン酸二無水物を得る方法が開示されている（ 非特許文献１参照）。しかし、この手法では各工程で得られた化合物を精製せずに次工程の原料として使用しているため、工程を重ねるごとに多種多量の不純物が副生し、最終的に得られるジフェノキシビフェニルテトラカルボン酸二無水物の純度が低くなってしまうという問題点があった。
本発明は従来技術の課題を背景になされたもので、ポリイミド等の耐熱性縮合系ポリマーを高重合度で合成し得るだけの充分な純度を有するジアリールオキシビフェニルテトラカルボン酸二無水物を工業的に効率よく製造することを課題とするものである。 The present invention has been made against the background of the problems of the prior art. Industrially, diaryloxybiphenyltetracarboxylic dianhydride having sufficient purity to synthesize a heat-resistant condensation polymer such as polyimide with a high degree of polymerization is industrially used. Therefore, it is an object of the present invention to manufacture efficiently.
すなわち本発明は、以下の構成による。
１． 一般式（化１）で示されるビス（Ｎ−アルキルフタルイミド）をニトロ化する第一の工程と、第一の工程で得られた一般式（化２）で示されるビス（ジニトロ−Ｎ−アルキルフタルイミド）をフェノール類と反応させる第二の工程と、第二の工程で得られた一般式（化３）で示されるビス（ジアリールオキシ−Ｎ−アルキルフタルイミド）をアルカリ水溶液中で加水分解してテトラカルボン酸にする第三の工程と、第三の工程で得られた一般式（化４）で示されるジアリールオキシビフェニルテトラカルボン酸を脱水環化して酸二無水物にする第四の工程を経由して一般式（化５）で示されるジアリールオキシビフェニルテトラカルボン酸二無水物を製造する方法であって、第一の工程に有機溶媒を用いて再結晶する工程を含むことを特徴とするジアリールオキシビフェニルテトラカルボン酸二無水物の製造方法。
２． 第二の工程に有機溶媒を用いて再結晶する工程を含むことを特徴とする１．のジアリールオキシビフェニルテトラカルボン酸二無水物の製造方法。
３． 第三の工程にアルカリ水溶液還流下で３０時間以上反応させる工程を含むことを特徴とする１．〜２．いずれかのジアリールオキシビフェニルテトラカルボン酸二無水物の製造方法。
４． 第三の工程にアルカリ水溶液還流下で３０時間以上反応させた後に酸析して得られた固体を再びアルカリ水溶液還流下で１０時間以上反応させる工程を含むことを特徴とする１．〜３．いずれかのジアリールオキシビフェニルテトラカルボン酸二無水物の製造方法。
That is, the present invention has the following configuration.
1. First step of nitrating bis (N-alkylphthalimide) represented by the general formula (Chemical Formula 1), and bis (dinitro-N-alkyl represented by the general formula (Chemical Formula 2) obtained in the first step Phthalimide) is reacted with phenols, and bis (diaryloxy-N-alkylphthalimide) represented by the general formula (chemical formula 3) obtained in the second step is hydrolyzed in an aqueous alkaline solution. A third step of converting to tetracarboxylic acid, and a fourth step of dehydrating and cyclizing the diaryloxybiphenyltetracarboxylic acid represented by the general formula (chemical formula 4) obtained in the third step to form an acid dianhydride. A method for producing a diaryloxybiphenyltetracarboxylic dianhydride represented by the general formula (Chemical Formula 5), wherein the first step includes a step of recrystallization using an organic solvent, Method of manufacturing that diaryloxy-biphenyl tetracarboxylic dianhydride.
2. The second step includes a step of recrystallization using an organic solvent. A process for producing diaryloxybiphenyltetracarboxylic dianhydride.
3. The third step includes a step of reacting for 30 hours or more under reflux of an alkaline aqueous solution. ~ 2. A method for producing any one of diaryloxybiphenyltetracarboxylic dianhydrides.
4). The third step includes a step of reacting a solid obtained by acid precipitation after refluxing in an alkaline aqueous solution for 30 hours or longer and then reacting again for 10 hours or longer in an alkaline aqueous solution reflux. ~ 3. A method for producing any one of diaryloxybiphenyltetracarboxylic dianhydrides.
本発明による一般式（化１）で示されるビス（Ｎ−アルキルフタルイミド）をニトロ化する第一の工程と、第一の工程で得られた一般式（化２）で示されるビス（ジニトロ−Ｎ−アルキルフタルイミド）をフェノール類と反応させる第二の工程と、第二の工程で得られた一般式（化３）で示されるビス（ジアリールオキシ−Ｎ−アルキルフタルイミド）をアルカリ水溶液中で加水分解してテトラカルボン酸にする第三の工程と、第三の工程で得られた一般式（化４）で示されるジアリールオキシビフェニルテトラカルボン酸を脱水環化して酸二無水物にする第四の工程を経由して一般式（化５）で示されるジアリールオキシビフェニルテトラカルボン酸二無水物を製造する方法であって、第一の工程にアミド系の有機溶媒を用いて再結晶する工程を含むことを特徴とするジアリールオキシビフェニルテトラカルボン酸二無水物の製造方法は、第一の工程において得られる一般式（化２）で示されるビス（ジニトロ−Ｎ−アルキルイミド）をアミド系の有機溶媒を用いて再結晶することによって、第二工程以降での副生物の量を抑制でき、最終的に得られるジアリールオキシビフェニルテトラカルボン酸二無水物の純度が向上し、ポリイミド等の耐熱性縮合系ポリマーを高重合度で合成し得るだけの充分な純度を有するジアリールオキシビフェニルテトラカルボン酸二無水物を工業的に効率よく製造できる。 A first step of nitrating bis (N-alkylphthalimide) represented by the general formula (Chemical Formula 1) according to the present invention, and a bis (dinitro-) represented by the general formula (Chemical Formula 2) obtained in the first step. N-alkylphthalimide) is reacted with phenols, and bis (diaryloxy-N-alkylphthalimide) represented by the general formula (chemical formula 3) obtained in the second step is hydrolyzed in an aqueous alkaline solution. A third step of decomposing into a tetracarboxylic acid, and a fourth step of dehydrating the diaryloxybiphenyltetracarboxylic acid represented by the general formula (chemical formula 4) obtained in the third step into an acid dianhydride. A method for producing a diaryloxybiphenyltetracarboxylic dianhydride represented by the general formula (Chemical Formula 5) through the step of recrystallization using an amide-based organic solvent in the first step A process for producing a diaryloxybiphenyltetracarboxylic dianhydride characterized by comprising a bis (dinitro-N-alkylimide) represented by the general formula (Chemical Formula 2) obtained in the first step By recrystallizing using an organic solvent, the amount of by-products in the second and subsequent steps can be suppressed, the purity of the finally obtained diaryloxybiphenyltetracarboxylic dianhydride is improved, and heat resistance such as polyimide Diaryloxybiphenyltetracarboxylic dianhydride having sufficient purity to synthesize a functional condensation polymer at a high degree of polymerization can be industrially efficiently produced.
以下、本発明を詳述する。
本発明における、一般式（化１）で示されるビス（Ｎ−アルキルフタルイミド）は、上述の非特許文献１記載のビフェニルテトラカルボン酸二無水物とアルキルアミンとを用いた手法により合成できるが、この手法に特に限定されるわけではなく、合成のし易さ、生成効率などを勘案して別の合成手法を適用することもできる。
ビス（Ｎ−アルキルフタルイミド）としては、具体的には、ビス（Ｎ−メチルフタルイミド）、ビス（Ｎ−エチルフタルイミド）、ビス（Ｎ−ｎ−プロピルフタルイミド）、ビス（Ｎ−ｎ−ブチルフタルイミド）、ビス（Ｎ−ｔ−ブチルフタルイミド）、ビス（Ｎ−ｎ−ヘキシルフタルイミド）などが挙げられるが、生成の容易さ、再結晶のし易さ、生成効率などを勘案して選択使用すればよい。
ビス（Ｎ−アルキルフタルイミド）はニトロ化してビス（Ｎ−アルキルニトロフタルイミド）が製造される。Ｎ−アルキルフタルイミドは公知の種々の方法により、又は本発明に従うニトロ化法によってニトロ化される。公知のいくつかのニトロ化方法が米国特許第４，９０２，８０９号及び同第４，５９９，４２９号公報に記述されているが、これらの方法に限定されるものではない。
The present invention is described in detail below.
In the present invention, bis (N-alkylphthalimide) represented by the general formula (Chemical Formula 1) can be synthesized by a technique using biphenyltetracarboxylic dianhydride and alkylamine described in Non-Patent Document 1, The method is not particularly limited, and another synthesis method can be applied in consideration of easiness of synthesis, generation efficiency, and the like.
Specific examples of bis (N-alkylphthalimide) include bis (N-methylphthalimide), bis (N-ethylphthalimide), bis (Nn-propylphthalimide), and bis (Nn-butylphthalimide). Bis (Nt-butylphthalimide), bis (Nn-hexylphthalimide), etc., but may be selected and used in consideration of ease of production, ease of recrystallization, production efficiency, and the like. .
Bis (N-alkyl phthalimide) is nitrated to produce bis (N-alkyl nitrophthalimide). N-alkylphthalimides are nitrated by various known methods or by the nitration method according to the present invention. Several known nitration methods are described in US Pat. Nos. 4,902,809 and 4,599,429, but are not limited to these methods.
第一の工程で得られた一般式（化２）で示されるビス（ジニトロ−Ｎ−アルキルイミド）をフェノール類と反応させる第二の工程、第二の工程で得られた一般式（３）で示されるビス（ジアリールオキシ−Ｎ−アルキルフタルイミド）をアルカリ水溶液中で加水分解してテトラカルボン酸にする第三の工程、第三の工程で得られた一般式（４）で示されるジアリールオキシビフェニルテトラカルボン酸を脱水環化して酸二無水物にする第四の工程それぞれにおける処方は、公知の種々の方法により、又は本発明に従う方法によって開示する方法が採用できる。
本発明においては、Ｎ−アルキルフタルイミドをニトロ化して得られるＮ−アルキルニトロフタルイミドすなわちビス（ジニトロ−Ｎ−アルキルイミド）を有機溶媒を用いて再結晶する工程が必須となるものである。有機溶媒としては、効率よく再結晶でき得るものであれば特に限定されるものではないが、ビス（ジニトロ−Ｎ−アルキルイミド）を効率よく溶解させるという観点でアミド系の有機溶媒の使用が好ましい。
また、第二の工程に有機溶媒を用いて再結晶する工程を含むジアリールオキシビフェニルテトラカルボン酸二無水物の製造方法が本発明の好ましい実施態様であり、また第三の工程にアルカリ水溶液還流下で３０時間以上反応させる工程を含むジアリールオキシビフェニルテトラカルボン酸二無水物の製造方法が本発明の好ましい実施態様であり、さらに第三の工程にアルカリ水溶液還流下で３０時間以上反応させた後に酸析して得られた固体を再びアルカリ水溶液還流下で１０時間以上反応させる工程を含むジアリールオキシビフェニルテトラカルボン酸二無水物の製造方法が本発明の好ましい実施態様である。
これらの好ましい実施態様を採用することで、本発明の目的の達成効果が一層向上する。
The second step in which the bis (dinitro-N-alkylimide) represented by the general formula (Chemical Formula 2) obtained in the first step is reacted with phenols, and the general formula (3) obtained in the second step The diaryloxy represented by the general formula (4) obtained in the third step and the third step obtained by hydrolyzing the bis (diaryloxy-N-alkylphthalimide) represented by formula (1) by hydrolysis in an aqueous alkali solution. The formulation disclosed in each of the fourth steps of dehydrating and cyclizing biphenyltetracarboxylic acid to form an acid dianhydride can employ the methods disclosed by various known methods or by the method according to the present invention.
In the present invention, a step of recrystallizing N-alkylnitrophthalimide obtained by nitrating N-alkylphthalimide, that is, bis (dinitro-N-alkylimide), using an organic solvent is essential. The organic solvent is not particularly limited as long as it can be efficiently recrystallized, but use of an amide-based organic solvent is preferable from the viewpoint of efficiently dissolving bis (dinitro-N-alkylimide). .
In addition, a method for producing a diaryloxybiphenyltetracarboxylic dianhydride including a step of recrystallization using an organic solvent in the second step is a preferred embodiment of the present invention, and the third step is performed under reflux of an alkaline aqueous solution. The method for producing a diaryloxybiphenyltetracarboxylic dianhydride comprising a step of reacting for 30 hours or more in the above is a preferred embodiment of the present invention, and further, in the third step, after reacting for 30 hours or more under reflux of an alkaline aqueous solution, the acid is reacted. A preferred embodiment of the present invention is a method for producing a diaryloxybiphenyltetracarboxylic dianhydride, which comprises a step of reacting the solid obtained by precipitation again with an alkaline aqueous solution reflux for 10 hours or more.
By adopting these preferred embodiments, the effect of achieving the object of the present invention is further improved.
（実施例１）
攪拌装置、温度計、冷却管、滴下漏斗を取り付けた５００ｍｌの容器に、６２．０ｇ（１９４ｍｍｏｌ）の４、４′−ビス（N−メチルフタルイミド）と９０ｍｌの濃硫酸 を導入した。続いて、滴下漏斗にて１２０ｇの発煙硝酸を反応系内の温度が８０℃〜９０℃の範囲に落ち着くような速度でゆっくりと導入し、滴下導入が完了した後に８０℃で２時間攪拌した。続いて、反応系を空冷した後に反応混合物を氷の上に注ぎ落とし、水を加えて攪拌した。
続いて、沈殿物を吸引ろ過によりろ別し、水で2回洗浄した後に減圧下１２０℃で12時間乾燥し、黄色の固体を得た。続いて、この固体の全量を７００ｍｌのＮ，Ｎ−ジメチルアセトアミドに１３０℃で溶かし、再び室温に冷却することにより黄色の結晶を得た。得られた黄色個体を赤外分光法（ＫＢｒ法）で分析したところ、１３４６、１５３７、１７１２、１７７２ｃｍ−１に吸収ピークを観測した。また、得られた黄色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト８．１３、８．６１の位置にそれぞれピークを観測した。以上により、この化合物が４，４′−ビス（２，２′−ジニトロ−Ｎ−メチルフタルイミド）であることを確認した。
Example 1
62.0 g (194 mmol) of 4,4′-bis (N-methylphthalimide) and 90 ml of concentrated sulfuric acid were introduced into a 500 ml container equipped with a stirrer, a thermometer, a condenser, and a dropping funnel. Subsequently, 120 g of fuming nitric acid was slowly introduced with a dropping funnel at such a rate that the temperature in the reaction system settled in the range of 80 ° C. to 90 ° C., and stirred for 2 hours at 80 ° C. after completion of the dropwise introduction. Subsequently, after the reaction system was air-cooled, the reaction mixture was poured onto ice, and water was added and stirred.
Subsequently, the precipitate was separated by suction filtration, washed twice with water, and then dried under reduced pressure at 120 ° C. for 12 hours to obtain a yellow solid. Subsequently, the total amount of this solid was dissolved in 700 ml of N, N-dimethylacetamide at 130 ° C., and cooled to room temperature again to obtain yellow crystals. When the obtained yellow solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 1346, 1537, 1712, and 1772 cm −1 . Further, when the obtained yellow solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR, peaks were observed at chemical shifts 8.13 and 8.61, respectively. From the above, it was confirmed that this compound was 4,4′-bis (2,2′-dinitro-N-methylphthalimide).
次に、攪拌装置、ディーンスタークトラップ、窒素導入用毛細管、玉栓を取り付けた３００ｍｌの容器に、５．２ｇ（５５．０ｍｍｏｌ）のフェノール、５０ｍｌのＮ，Ｎ−ジメチルアセトアミド、２．３ｇ（５７．５ｍｍｏｌ）の水酸化ナトリウム、２０ｍｌのトルエンを導入し、窒素をバブリングさせながら室温で1時間攪拌した。続いて、窒素導入用毛細管を取り外し、窒素導入管を取り付け、窒素気流下で１００−１２０℃の温度範囲で、水を共沸させながら、系中のトルエンが目視で確認できなくなるまで攪拌した。続いて、ディーンスタークトラップを取り外し、温度計を取り付け、内温が８０℃になるまで空冷した。続いて、１０．３ｇ（２５ｍｍｏｌ）の４，４′−ビス（２，２′−ジニトロ−Ｎ−メチルフタルイミド）を導入し、８０℃で2時間攪拌した。続いて、反応混合物を２００ｍｌの水に導入し、得られた沈殿物を吸引ろ過によりろ別し、2回水洗した後、減圧下、１００℃で、１２時間乾燥することにより、薄黄色の固体を得た。得られた薄黄色の個体を赤外分光法（ＫＢｒ法）で分析したところ、７３９、１０４０，１２５０、１３８６、１５３７、１７１３、１７７２ｃｍ−１に吸収ピークを観測した。また、得られた白色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト７．０１−７．０５、７．１９−７．２６、７．３６−７．４５、８．０１の位置にそれぞれピークを観測した。以上により、この化合物が４，４′−ビス（２，２′−ジフェノキシ−Ｎ−メチルフタルイミド）であることを確認した。 Next, 5.2 g (55.0 mmol) of phenol, 50 ml of N, N-dimethylacetamide, 2.3 g (57 g) were added to a 300 ml container equipped with a stirrer, a Dean Stark trap, a capillary tube for introducing nitrogen, and a ball stopper. 0.5 mmol) sodium hydroxide and 20 ml of toluene were introduced and stirred at room temperature for 1 hour while bubbling nitrogen. Subsequently, the capillary tube for nitrogen introduction was removed, a nitrogen introduction tube was attached, and the mixture was stirred until toluene in the system could not be visually confirmed in a temperature range of 100 to 120 ° C. under nitrogen flow while water was azeotroped. Subsequently, the Dean Stark trap was removed, a thermometer was attached, and air cooling was performed until the internal temperature reached 80 ° C. Subsequently, 10.3 g (25 mmol) of 4,4′-bis (2,2′-dinitro-N-methylphthalimide) was introduced and stirred at 80 ° C. for 2 hours. Subsequently, the reaction mixture was introduced into 200 ml of water, and the resulting precipitate was filtered by suction filtration, washed twice with water, and then dried at 100 ° C. under reduced pressure for 12 hours to obtain a pale yellow solid. Got. When the obtained pale yellow solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 739, 1040, 1250, 1386, 1537, 1713, and 1772 cm −1 . Moreover, when the obtained white solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR, chemical shifts 7.01-7.05, 7.19-7.26, 7.36-7.45, A peak was observed at a position of 8.01. From the above, it was confirmed that this compound was 4,4′-bis (2,2′-diphenoxy-N-methylphthalimide).
次に、攪拌装置、冷却管、玉栓を取り付けた１００ｍｌの容器に、３．２０ｇの４，４′−ビス（２，２′−ジフェノキシ−N−メチルフタルイミド）、１５ｍｌの水、２．１３ｇの水酸化カリウムを導入し、還流下で２４時間、攪拌を行った。続いて、反応溶液を空冷した後に６．６Ｎの塩酸を導入してｐＨ１．０にしてよく攪拌した。得られた沈殿を吸引ろ過によりろ別し、2回水洗後、１００℃で、１２時間減圧乾燥し、白色固体を得た。続いて、攪拌装置、冷却管、玉栓を取り付けた１００ｍｌの容器に、得られた白色個体と１０ｍｌの無水酢酸を導入し、還流下で４時間攪拌した。空冷後、析出した固体を吸引ろ過によりろ別し、減圧下、１２０℃で、１２時間乾燥し、白色固体を得た。得られた白色個体の融点は２３２℃であった。また、得られた白色個体を赤外分光法（ＫＢｒ法）で分析したところ、 １７７８、１８４０ｃｍ−１に吸収ピークを観測した。また、得られた白色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト ７．０６−７．１１、７．１７、７．２６−７．３３、７．４２−７．５０、８．３４の位置にそれぞれピークを観測した。以上により、この化合物が２，２′−ジフェノキシ−４，４′，５，５′−ビフェニルテトラカルボン酸二無水物であることを確認した。さらに、得られた２，２′−ジフェノキシ−３，３′，４，４′−ビフェニルテトラカルボン酸二無水物を水酸化ナトリウム水溶液で処理後に塩酸で処理してテトラカルボン酸に変換してから高速液体クロマトフィー（ＨＰＬＣ）で分析したところ、ＨＰＬＣ純度は９９．０％であった。 Next, in a 100 ml container equipped with a stirrer, a condenser tube and a ball plug, 3.20 g of 4,4′-bis (2,2′-diphenoxy-N-methylphthalimide), 15 ml of water, 2.13 g Of potassium hydroxide was introduced and stirred under reflux for 24 hours. Subsequently, after the reaction solution was air-cooled, 6.6N hydrochloric acid was introduced to adjust the pH to 1.0, and the mixture was stirred well. The obtained precipitate was separated by suction filtration, washed twice with water, and then dried under reduced pressure at 100 ° C. for 12 hours to obtain a white solid. Subsequently, the obtained white solid and 10 ml of acetic anhydride were introduced into a 100 ml container equipped with a stirrer, a cooling tube and a ball stopper, and stirred for 4 hours under reflux. After air cooling, the precipitated solid was separated by suction filtration and dried at 120 ° C. under reduced pressure for 12 hours to obtain a white solid. The melting point of the obtained white solid was 232 ° C. Further, when the obtained white solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 1778 and 1840 cm −1 . Moreover, when the obtained white solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR, chemical shifts 7.06-7.11, 7.17, 7.26-7.33, 7.42- Peaks were observed at positions 7.50 and 8.34, respectively. From the above, it was confirmed that this compound was 2,2′-diphenoxy-4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride. Further, the obtained 2,2'-diphenoxy-3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was treated with an aqueous sodium hydroxide solution and then treated with hydrochloric acid to convert it to a tetracarboxylic acid. When analyzed by high performance liquid chromatography (HPLC), the HPLC purity was 99.0%.
（実施例２）
攪拌装置、温度計、冷却管、滴下漏斗を取り付けた５００ｍｌの容器に、６２．０ｇ（１９４ｍｍｏｌ）の４、４′−ビス（N−メチルフタルイミド）と９０ｍｌの濃硫酸 を導入した。続いて、滴下漏斗にて１２０ｇの発煙硝酸を反応系内の温度が８０℃〜９０℃の範囲に落ち着くような速度でゆっくりと導入し、滴下導入が完了した後に８０℃で２時間攪拌した。続いて、反応系を空冷した後に反応混合物を氷の上に注ぎ落とし、水を加えて攪拌した。
続いて、沈殿物を吸引ろ過によりろ別し、水で2回洗浄した後に減圧下１２０℃で１２時間乾燥し、黄色の固体を得た。続いて、この固体の全量を７００ｍｌのＮ，Ｎ−ジメチルアセトアミドに１３０℃で溶かし、再び室温に冷却することにより黄色の結晶を得た。得られた黄色個体を赤外分光法（ＫＢｒ法）で分析したところ、１３４６、１５３７、１７１２、１７７２ｃｍ−１に吸収ピークを観測した。また、得られた黄色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト８．１３、８．６１の位置にそれぞれピークを観測した。以上により、この化合物が４，４′−ビス（２，２′−ジニトロ−Ｎ−メチルフタルイミド）であることを確認した。
(Example 2)
62.0 g (194 mmol) of 4,4′-bis (N-methylphthalimide) and 90 ml of concentrated sulfuric acid were introduced into a 500 ml container equipped with a stirrer, a thermometer, a condenser, and a dropping funnel. Subsequently, 120 g of fuming nitric acid was slowly introduced with a dropping funnel at such a rate that the temperature in the reaction system settled in the range of 80 ° C. to 90 ° C., and stirred for 2 hours at 80 ° C. after completion of the dropwise introduction. Subsequently, after the reaction system was air-cooled, the reaction mixture was poured onto ice, and water was added and stirred.
Subsequently, the precipitate was separated by suction filtration, washed twice with water, and then dried under reduced pressure at 120 ° C. for 12 hours to obtain a yellow solid. Subsequently, the total amount of this solid was dissolved in 700 ml of N, N-dimethylacetamide at 130 ° C., and cooled to room temperature again to obtain yellow crystals. When the obtained yellow solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 1346, 1537, 1712, and 1772 cm −1 . Further, when the obtained yellow solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR, peaks were observed at chemical shifts 8.13 and 8.61, respectively. From the above, it was confirmed that this compound was 4,4′-bis (2,2′-dinitro-N-methylphthalimide).
次に、攪拌装置、ディーンスタークトラップ、窒素導入用毛細管、玉栓を取り付けた３００ｍｌの容器に、５．２ｇ（５５．０ｍｍｏｌ）のフェノール、５０ｍｌのＮ，Ｎ−ジメチルアセトアミド、２．３ｇ（５７．５ｍｍｏｌ）の水酸化ナトリウム、２０ｍｌのトルエンを導入し、窒素をバブリングさせながら室温で1時間攪拌した。続いて、窒素導入用毛細管を取り外し、窒素導入管を取り付け、窒素気流下で１００−１２０℃の温度範囲で、水を共沸させながら、系中のトルエンが目視で確認できなくなるまで攪拌した（およそ３時間）。続いて、ディーンスタークトラップを取り外し、温度計を取り付け、内温が８０℃になるまで空冷した。続いて、１０．３ｇ（２５ｍｍｏｌ）の４，４′−ビス（２，２′−ジニトロ−Ｎ−メチルフタルイミド）を導入し、８０℃で2時間攪拌した。続いて、反応混合物を２００ｍｌの水に導入し、得られた沈殿物を吸引ろ過によりろ別し、2回水洗した後、減圧下、１００℃で、１２時間乾燥することにより、薄黄色の固体を得た。続いて、この固体をテトラヒドロフランに６５℃で溶かし、再び室温に冷却することにより白色の固体を得た。得られた白色個体を赤外分光法（ＫＢｒ法）で分析したところ、７３９、１０４０，１２５０、１３８６、１５３７、１７１３、１７７２ｃｍ−１に吸収ピークを観測した。また、得られた白色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト７．０１−７．０５、７．１９−７．２６、７．３６−７．４５、８．０１の位置にそれぞれピークを観測した。以上により、この化合物が４，４′−ビス（２，２′−ジフェノキシ−Ｎ−メチルフタルイミド）であることを確認した。 Next, 5.2 g (55.0 mmol) of phenol, 50 ml of N, N-dimethylacetamide, 2.3 g (57 g) were added to a 300 ml container equipped with a stirrer, a Dean Stark trap, a capillary tube for introducing nitrogen, and a ball stopper. 0.5 mmol) sodium hydroxide and 20 ml of toluene were introduced and stirred at room temperature for 1 hour while bubbling nitrogen. Subsequently, the capillary for nitrogen introduction was removed, a nitrogen introduction tube was attached, and stirring was performed while azeotroping water in a temperature range of 100-120 ° C. under a nitrogen stream until toluene in the system could not be visually confirmed ( About 3 hours). Subsequently, the Dean Stark trap was removed, a thermometer was attached, and air cooling was performed until the internal temperature reached 80 ° C. Subsequently, 10.3 g (25 mmol) of 4,4′-bis (2,2′-dinitro-N-methylphthalimide) was introduced and stirred at 80 ° C. for 2 hours. Subsequently, the reaction mixture was introduced into 200 ml of water, and the resulting precipitate was filtered by suction filtration, washed twice with water, and then dried at 100 ° C. under reduced pressure for 12 hours to obtain a pale yellow solid. Got. Subsequently, this solid was dissolved in tetrahydrofuran at 65 ° C. and cooled to room temperature again to obtain a white solid. When the obtained white solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 739, 1040, 1250, 1386, 1537, 1713, and 1772 cm −1 . Moreover, when the obtained white solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR, chemical shifts 7.01-7.05, 7.19-7.26, 7.36-7.45, A peak was observed at a position of 8.01. From the above, it was confirmed that this compound was 4,4′-bis (2,2′-diphenoxy-N-methylphthalimide).
次に、攪拌装置、冷却管、玉栓を取り付けた１００ｍｌの容器に、３．２０ｇの４，４′−ビス（２，２′−ジフェノキシ−N−メチルフタルイミド）、１５ｍｌの水、２．１３ｇの水酸化カリウムを導入し、還流下で２４時間、攪拌を行った。続いて、反応溶液を空冷した後に６．６Ｎの塩酸を導入してｐＨ１．０にしてよく攪拌した。続いて、得られた沈殿を吸引ろ過によりろ別し、2回水洗して白色固体を得た。得られた沈殿を吸引ろ過によりろ別し、2回水洗後、１００℃で、１２時間減圧乾燥し、白色固体を得た。続いて、攪拌装置、冷却管、玉栓を取り付けた１００ｍｌの容器に、得られた白色個体と１０ｍｌの無水酢酸を導入し、還流下で４時間攪拌した。空冷後、析出した固体を吸引ろ過によりろ別し、減圧下、120℃で、12時間乾燥し、白色固体を得た。得られた白色個体の融点は２３２ ℃であった。また、得られた白色個体を赤外分光法（ＫＢｒ法）で分析したところ、１７７８、１８４０ｃｍ−１に吸収ピークを観測した。また、得られた白色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト ７．０６−７．１１、７．１７、７．２６−７．３３、７．４２−７．５０、８．３４の位置にそれぞれピークを観測した。以上により、この化合物が２，２′−ジフェノキシ−４，４′，５，５′−ビフェニルテトラカルボン酸二無水物であることを確認した。さらに、得られた２，２′−ジフェノキシ−３，３′，４，４′−ビフェニルテトラカルボン酸二無水物を水酸化ナトリウム水溶液で処理後に塩酸で処理してテトラカルボン酸に変換してから高速液体クロマトフィー（ＨＰＬＣ）で分析したところ、ＨＰＬＣ純度は９９．２％であった。 Next, in a 100 ml container equipped with a stirrer, a condenser tube and a ball plug, 3.20 g of 4,4′-bis (2,2′-diphenoxy-N-methylphthalimide), 15 ml of water, 2.13 g Of potassium hydroxide was introduced and stirred under reflux for 24 hours. Subsequently, after the reaction solution was air-cooled, 6.6N hydrochloric acid was introduced to adjust the pH to 1.0, and the mixture was stirred well. Subsequently, the obtained precipitate was filtered by suction filtration and washed twice with water to obtain a white solid. The obtained precipitate was separated by suction filtration, washed twice with water, and then dried under reduced pressure at 100 ° C. for 12 hours to obtain a white solid. Subsequently, the obtained white solid and 10 ml of acetic anhydride were introduced into a 100 ml container equipped with a stirrer, a cooling tube and a ball stopper, and stirred for 4 hours under reflux. After air cooling, the precipitated solid was separated by suction filtration and dried at 120 ° C. under reduced pressure for 12 hours to obtain a white solid. The melting point of the obtained white solid was 232 ° C. Further, when the obtained white solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 1778 and 1840 cm −1 . Moreover, when the obtained white solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR, chemical shifts 7.06-7.11, 7.17, 7.26-7.33, 7.42- Peaks were observed at positions 7.50 and 8.34, respectively. From the above, it was confirmed that this compound was 2,2′-diphenoxy-4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride. Further, the obtained 2,2'-diphenoxy-3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was treated with an aqueous sodium hydroxide solution and then treated with hydrochloric acid to convert it to a tetracarboxylic acid. When analyzed by high performance liquid chromatography (HPLC), the HPLC purity was 99.2%.
（実施例３）
攪拌装置、温度計、冷却管、滴下漏斗を取り付けた５００ｍｌの容器に、６２．０ｇ（１９４ｍｍｏｌ）の４、４′−ビス（N−メチルフタルイミド）と９０ｍｌの濃硫酸 を導入した。続いて、滴下漏斗にて１２０ｇの発煙硝酸を反応系内の温度が８０℃〜９０℃の範囲に落ち着くような速度でゆっくりと導入し、滴下導入が完了した後に８０℃で２時間攪拌した。続いて、反応系を空冷した後に反応混合物を氷の上に注ぎ落とし、水を加えて攪拌した。
続いて、沈殿物を吸引ろ過によりろ別し、水で2回洗浄した後に減圧下１２０℃で12時間乾燥し、黄色の固体を得た。続いて、この固体の全量を７００ｍｌのＮ，Ｎ−ジメチルアセトアミドに１３０℃で溶かし、再び室温に冷却することにより黄色の結晶を得た。得られた黄色個体を赤外分光法（ＫＢｒ法）で分析したところ、１３４６、１５３７、１７１２、１７７２ｃｍ−１に吸収ピークを観測した。また、得られた黄色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト８．１３、８．６１の位置にそれぞれピークを観測した。以上により、この化合物が４，４′−ビス（２，２′−ジニトロ−Ｎ−メチルフタルイミド）であることを確認した。
(Example 3)
62.0 g (194 mmol) of 4,4′-bis (N-methylphthalimide) and 90 ml of concentrated sulfuric acid were introduced into a 500 ml container equipped with a stirrer, a thermometer, a condenser, and a dropping funnel. Subsequently, 120 g of fuming nitric acid was slowly introduced with a dropping funnel at such a rate that the temperature in the reaction system settled in the range of 80 ° C. to 90 ° C., and stirred for 2 hours at 80 ° C. after completion of the dropwise introduction. Subsequently, after the reaction system was air-cooled, the reaction mixture was poured onto ice, and water was added and stirred.
Subsequently, the precipitate was separated by suction filtration, washed twice with water, and then dried under reduced pressure at 120 ° C. for 12 hours to obtain a yellow solid. Subsequently, the total amount of this solid was dissolved in 700 ml of N, N-dimethylacetamide at 130 ° C., and cooled to room temperature again to obtain yellow crystals. When the obtained yellow solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 1346, 1537, 1712, and 1772 cm −1 . Further, when the obtained yellow solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR, peaks were observed at chemical shifts 8.13 and 8.61, respectively. From the above, it was confirmed that this compound was 4,4′-bis (2,2′-dinitro-N-methylphthalimide).
次に、攪拌装置、ディーンスタークトラップ、窒素導入用毛細管、玉栓を取り付けた３００ｍｌの容器に、５．２ｇ（５５．０ｍｍｏｌ）のフェノール、５０ｍｌのＮ，Ｎ−ジメチルアセトアミド、２．３ｇ（５７．５ｍｍｏｌ）の水酸化ナトリウム、２０ｍｌのトルエンを導入し、窒素をバブリングさせながら室温で1時間攪拌した。続いて、窒素導入用毛細管を取り外し、窒素導入管を取り付け、窒素気流下で１００−１２０℃の温度範囲で、水を共沸させながら、系中のトルエンが目視で確認できなくなるまで攪拌した（およそ３時間）。続いて、ディーンスタークトラップを取り外し、温度計を取り付け、内温が８０℃になるまで空冷した。続いて、１０．３ｇ（２５ｍｍｏｌ）の４，４′−ビス（２，２′−ジニトロ−Ｎ−メチルフタルイミド）を導入し、８０℃で2時間攪拌した。続いて、反応混合物を２００ｍｌの水に導入し、得られた沈殿物を吸引ろ過によりろ別し、2回水洗した後、減圧下、１００℃で、１２時間乾燥することにより、薄黄色の固体を得た。続いて、この固体をテトラヒドロフランに６５℃で溶かし、再び室温に冷却することにより白色の固体を得た。得られた白色個体を赤外分光法（ＫＢｒ法）で分析したところ、７３９、１０４０，１２５０、１３８６、１５３７、１７１３、１７７２ｃｍ−１に吸収ピークを観測した。また、得られた白色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト７．０１−７．０５、７．１９−７．２６、７．３６−７．４５、８．０１の位置にそれぞれピークを観測した。以上により、この化合物が４，４′−ビス（２，２′−ジフェノキシ−Ｎ−メチルフタルイミド）であることを確認した。 Next, 5.2 g (55.0 mmol) of phenol, 50 ml of N, N-dimethylacetamide, 2.3 g (57 g) were added to a 300 ml container equipped with a stirrer, a Dean Stark trap, a capillary tube for introducing nitrogen, and a ball stopper. 0.5 mmol) sodium hydroxide and 20 ml of toluene were introduced and stirred at room temperature for 1 hour while bubbling nitrogen. Subsequently, the capillary for nitrogen introduction was removed, a nitrogen introduction tube was attached, and stirring was performed while azeotroping water in a temperature range of 100-120 ° C. under a nitrogen stream until toluene in the system could not be visually confirmed ( About 3 hours). Subsequently, the Dean Stark trap was removed, a thermometer was attached, and air cooling was performed until the internal temperature reached 80 ° C. Subsequently, 10.3 g (25 mmol) of 4,4′-bis (2,2′-dinitro-N-methylphthalimide) was introduced and stirred at 80 ° C. for 2 hours. Subsequently, the reaction mixture was introduced into 200 ml of water, and the resulting precipitate was filtered by suction filtration, washed twice with water, and then dried at 100 ° C. under reduced pressure for 12 hours to obtain a pale yellow solid. Got. Subsequently, this solid was dissolved in tetrahydrofuran at 65 ° C. and cooled to room temperature again to obtain a white solid. When the obtained white solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 739, 1040, 1250, 1386, 1537, 1713, and 1772 cm −1 . Moreover, when the obtained white solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR, chemical shifts 7.01-7.05, 7.19-7.26, 7.36-7.45, A peak was observed at a position of 8.01. From the above, it was confirmed that this compound was 4,4′-bis (2,2′-diphenoxy-N-methylphthalimide).
次に、攪拌装置、冷却管、玉栓を取り付けた１００ｍｌの容器に、３．２０ｇの４，４′−ビス（２，２′−ジフェノキシ−N−メチルフタルイミド）、１５ｍｌの水、２．１３ｇの水酸化カリウムを導入し、還流下で４８時間、攪拌を行った。続いて、反応溶液を空冷した後に６．６Ｎの塩酸を導入してｐＨ１．０にしてよく攪拌した。得られた沈殿を吸引ろ過によりろ別し、2回水洗後、１００℃で、１２時間減圧乾燥し、白色固体を得た。続いて、攪拌装置、冷却管、玉栓を取り付けた１００ｍｌの容器に、得られた白色個体と１０ｍｌの無水酢酸を導入し、還流下で４時間攪拌した。空冷後、析出した固体を吸引ろ過によりろ別し、減圧下、１２０℃で、１２時間乾燥し、白色固体を得た。得られた白色個体の融点は２３２℃であった。また、得られた白色個体を赤外分光法（ＫＢｒ法）で分析したところ、 １７７８、１８４０ｃｍ−１に吸収ピークを観測した。また、得られた白色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト ７．０６−７．１１、７．１７、７．２６−７．３３、７．４２−７．５０、８．３４の位置にそれぞれピークを観測した。以上により、この化合物が２，２′−ジフェノキシ−４，４′，５，５′−ビフェニルテトラカルボン酸二無水物であることを確認した。さらに、得られた２，２′−ジフェノキシ−３，３′，４，４′−ビフェニルテトラカルボン酸二無水物を水酸化ナトリウム水溶液で処理後に塩酸で処理してテトラカルボン酸に変換してから高速液体クロマトフィー（ＨＰＬＣ）で分析したところ、ＨＰＬＣ純度は９９．２％であった。 Next, in a 100 ml container equipped with a stirrer, a condenser tube and a ball plug, 3.20 g of 4,4′-bis (2,2′-diphenoxy-N-methylphthalimide), 15 ml of water, 2.13 g Of potassium hydroxide was introduced and stirred for 48 hours under reflux. Subsequently, after the reaction solution was air-cooled, 6.6N hydrochloric acid was introduced to adjust the pH to 1.0, and the mixture was stirred well. The obtained precipitate was separated by suction filtration, washed twice with water, and then dried under reduced pressure at 100 ° C. for 12 hours to obtain a white solid. Subsequently, the obtained white solid and 10 ml of acetic anhydride were introduced into a 100 ml container equipped with a stirrer, a cooling tube and a ball stopper, and stirred for 4 hours under reflux. After air cooling, the precipitated solid was separated by suction filtration and dried at 120 ° C. under reduced pressure for 12 hours to obtain a white solid. The melting point of the obtained white solid was 232 ° C. Further, when the obtained white solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 1778 and 1840 cm −1 . Moreover, when the obtained white solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR, chemical shifts 7.06-7.11, 7.17, 7.26-7.33, 7.42- Peaks were observed at positions 7.50 and 8.34, respectively. From the above, it was confirmed that this compound was 2,2′-diphenoxy-4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride. Further, the obtained 2,2'-diphenoxy-3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was treated with an aqueous sodium hydroxide solution and then treated with hydrochloric acid to convert it to a tetracarboxylic acid. When analyzed by high performance liquid chromatography (HPLC), the HPLC purity was 99.2%.
（実施例４）
攪拌装置、温度計、冷却管、滴下漏斗を取り付けた５００ｍｌの容器に、６２．０ｇ（１９４ｍｍｏｌ）の４、４′−ビス（N−メチルフタルイミド）と９０ｍｌの濃硫酸 を導入した。続いて、滴下漏斗にて１２０ｇの発煙硝酸を反応系内の温度が８０℃〜９０℃の範囲に落ち着くような速度でゆっくりと導入し、滴下導入が完了した後に８０℃で２時間攪拌した。続いて、反応系を空冷した後に反応混合物を氷の上に注ぎ落とし、水を加えて攪拌した。
続いて、沈殿物を吸引ろ過によりろ別し、水で2回洗浄した後に減圧下１２０℃で12時間乾燥し、黄色の固体を得た。続いて、この固体の全量を７００ｍｌのＮ，Ｎ−ジメチルアセトアミドに１３０℃で溶かし、再び室温に冷却することにより黄色の結晶を得た。得られた黄色個体を赤外分光法（ＫＢｒ法）で分析したところ、１３４６、１５３７、１７１２、１７７２ｃｍ−１に吸収ピークを観測した。また、得られた黄色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト８．１３、８．６１の位置にそれぞれピークを観測した。以上により、この化合物が４，４′−ビス（２，２′−ジニトロ−Ｎ−メチルフタルイミド）であることを確認した。
Example 4
62.0 g (194 mmol) of 4,4′-bis (N-methylphthalimide) and 90 ml of concentrated sulfuric acid were introduced into a 500 ml container equipped with a stirrer, a thermometer, a condenser, and a dropping funnel. Subsequently, 120 g of fuming nitric acid was slowly introduced with a dropping funnel at such a rate that the temperature in the reaction system settled in the range of 80 ° C. to 90 ° C., and stirred for 2 hours at 80 ° C. after completion of the dropwise introduction. Subsequently, after the reaction system was air-cooled, the reaction mixture was poured onto ice, and water was added and stirred.
Subsequently, the precipitate was separated by suction filtration, washed twice with water, and then dried under reduced pressure at 120 ° C. for 12 hours to obtain a yellow solid. Subsequently, the total amount of this solid was dissolved in 700 ml of N, N-dimethylacetamide at 130 ° C., and cooled to room temperature again to obtain yellow crystals. When the obtained yellow solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 1346, 1537, 1712, and 1772 cm −1 . Further, when the obtained yellow solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR, peaks were observed at chemical shifts 8.13 and 8.61, respectively. From the above, it was confirmed that this compound was 4,4′-bis (2,2′-dinitro-N-methylphthalimide).
次に、攪拌装置、ディーンスタークトラップ、窒素導入用毛細管、玉栓を取り付けた３００ｍｌの容器に、５．２ｇ（５５．０ｍｍｏｌ）のフェノール、５０ｍｌのＮ，Ｎ−ジメチルアセトアミド、２．３ｇ（５７．５ｍｍｏｌ）の水酸化ナトリウム、２０ｍｌのトルエンを導入し、窒素をバブリングさせながら室温で1時間攪拌した。続いて、窒素導入用毛細管を取り外し、窒素導入管を取り付け、窒素気流下で１００−１２０℃の温度範囲で、水を共沸させながら、系中のトルエンが目視で確認できなくなるまで攪拌した（およそ３時間）。続いて、ディーンスタークトラップを取り外し、温度計を取り付け、内温が８０℃になるまで空冷した。続いて、１０．３ｇ（２５ｍｍｏｌ）の４，４′−ビス（２，２′−ジニトロ−Ｎ−メチルフタルイミド）を導入し、８０℃で2時間攪拌した。続いて、反応混合物を２００ｍｌの水に導入し、得られた沈殿物を吸引ろ過によりろ別し、2回水洗した後、減圧下、１００℃で、１２時間乾燥することにより、薄黄色の固体を得た。続いて、この固体をテトラヒドロフランに６５℃で溶かし、再び室温に冷却することにより白色の固体を得た。得られた白色個体を赤外分光法（ＫＢｒ法）で分析したところ、７３９、１０４０，１２５０、１３８６、１５３７、１７１３、１７７２ｃｍ−１に吸収ピークを観測した。また、得られた白色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト７．０１−７．０５、７．１９−７．２６、７．３６−７．４５、８．０１の位置にそれぞれピークを観測した。以上により、この化合物が４，４′−ビス（２，２′−ジフェノキシ−Ｎ−メチルフタルイミド）であることを確認した。 Next, 5.2 g (55.0 mmol) of phenol, 50 ml of N, N-dimethylacetamide, 2.3 g (57 g) were added to a 300 ml container equipped with a stirrer, a Dean Stark trap, a capillary tube for introducing nitrogen, and a ball stopper. 0.5 mmol) sodium hydroxide and 20 ml of toluene were introduced and stirred at room temperature for 1 hour while bubbling nitrogen. Subsequently, the capillary for nitrogen introduction was removed, a nitrogen introduction tube was attached, and stirring was performed while azeotroping water in a temperature range of 100-120 ° C. under a nitrogen stream until toluene in the system could not be visually confirmed ( About 3 hours). Subsequently, the Dean Stark trap was removed, a thermometer was attached, and air cooling was performed until the internal temperature reached 80 ° C. Subsequently, 10.3 g (25 mmol) of 4,4′-bis (2,2′-dinitro-N-methylphthalimide) was introduced and stirred at 80 ° C. for 2 hours. Subsequently, the reaction mixture was introduced into 200 ml of water, and the resulting precipitate was filtered by suction filtration, washed twice with water, and then dried at 100 ° C. under reduced pressure for 12 hours to obtain a pale yellow solid. Got. Subsequently, this solid was dissolved in tetrahydrofuran at 65 ° C. and cooled to room temperature again to obtain a white solid. When the obtained white solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 739, 1040, 1250, 1386, 1537, 1713, and 1772 cm −1 . Moreover, when the obtained white solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR, chemical shifts 7.01-7.05, 7.19-7.26, 7.36-7.45, A peak was observed at a position of 8.01. From the above, it was confirmed that this compound was 4,4′-bis (2,2′-diphenoxy-N-methylphthalimide).
次に、攪拌装置、冷却管、玉栓を取り付けた１００ｍｌの容器に、３．２０ｇの４，４′−ビス（２，２′−ジフェノキシ−N−メチルフタルイミド）、１５ｍｌの水、２．１３ｇの水酸化カリウムを導入し、還流下で４８時間、攪拌を行った。続いて、反応溶液を空冷した後に６．６Ｎの塩酸を導入してｐＨ１．０にしてよく攪拌した。続いて、得られた沈殿を吸引ろ過によりろ別し、2回水洗して白色固体を得た。続いて、攪拌装置、冷却管、玉栓を取り付けた１００ｍｌの容器に、得られた白色個体、１５ｍｌの水、２．１３ｇの水酸化カリウムを導入し、還流下で２４時間、攪拌を行った。空冷後、６．５Ｎの塩酸を導入し、Ｈ１．０にしてよく攪拌した。得られた沈殿を吸引ろ過によりろ別し、2回水洗後、１００℃で、１２時間減圧乾燥し、白色固体を得た。続いて、攪拌装置、冷却管、玉栓を取り付けた１００ｍｌの容器に、得られた白色個体と１０ｍｌの無水酢酸を導入し、還流下で４時間攪拌した。空冷後、析出した固体を吸引ろ過によりろ別し、減圧下、１２０℃で、１２時間乾燥し、白色固体を得た。得られた白色個体の融点は２３２℃であった。また、得られた白色個体を赤外分光法（ＫＢｒ法）で分析したところ、 １７７８、１８４０ｃｍ−１に吸収ピークを観測した。また、得られた白色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト ７．０６−７．１１、７．１７、７．２６−７．３３、７．４２−７．５０、８．３４の位置にそれぞれピークを観測した。以上により、この化合物が２，２′−ジフェノキシ−４，４′，５，５′−ビフェニルテトラカルボン酸二無水物であることを確認した。さらに、得られた２，２′−ジフェノキシ−３，３′，４，４′−ビフェニルテトラカルボン酸二無水物を水酸化ナトリウム水溶液で処理後に塩酸で処理してテトラカルボン酸に変換してから高速液体クロマトフィー（ＨＰＬＣ）で分析したところ、ＨＰＬＣ純度は９９．９％であった。 Next, in a 100 ml container equipped with a stirrer, a condenser tube and a ball plug, 3.20 g of 4,4′-bis (2,2′-diphenoxy-N-methylphthalimide), 15 ml of water, 2.13 g Of potassium hydroxide was introduced and stirred for 48 hours under reflux. Subsequently, after the reaction solution was air-cooled, 6.6N hydrochloric acid was introduced to adjust the pH to 1.0, and the mixture was stirred well. Subsequently, the obtained precipitate was filtered by suction filtration and washed twice with water to obtain a white solid. Subsequently, the obtained white solid, 15 ml of water and 2.13 g of potassium hydroxide were introduced into a 100 ml container equipped with a stirrer, a cooling tube and a ball plug, and stirred for 24 hours under reflux. . After air cooling, 6.5N hydrochloric acid was introduced, and the mixture was thoroughly stirred at H1.0. The obtained precipitate was separated by suction filtration, washed twice with water, and then dried under reduced pressure at 100 ° C. for 12 hours to obtain a white solid. Subsequently, the obtained white solid and 10 ml of acetic anhydride were introduced into a 100 ml container equipped with a stirrer, a cooling tube and a ball stopper, and stirred for 4 hours under reflux. After air cooling, the precipitated solid was separated by suction filtration and dried at 120 ° C. under reduced pressure for 12 hours to obtain a white solid. The melting point of the obtained white solid was 232 ° C. Further, when the obtained white solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 1778 and 1840 cm −1 . Moreover, when the obtained white solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR, chemical shifts 7.06-7.11, 7.17, 7.26-7.33, 7.42- Peaks were observed at positions 7.50 and 8.34, respectively. From the above, it was confirmed that this compound was 2,2′-diphenoxy-4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride. Further, the obtained 2,2'-diphenoxy-3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was treated with an aqueous sodium hydroxide solution and then treated with hydrochloric acid to convert it to a tetracarboxylic acid. When analyzed by high performance liquid chromatography (HPLC), the HPLC purity was 99.9%.
（比較例）
攪拌装置、温度計、冷却管、滴下漏斗を取り付けた５００ｍｌの容器に、６２．０ｇ（１９４ｍｍｏｌ）の４、４′−ビス（N−メチルフタルイミド）と９０ｍｌの濃硫酸 を導入した。続いて、滴下漏斗にて１２０ｇの発煙硝酸を反応系内の温度が８０℃〜９０℃の範囲に落ち着くような速度でゆっくりと導入し、滴下導入が完了した後に８０℃で２時間攪拌した。続いて、反応系を空冷した後に反応混合物を氷の上に注ぎ落とし、水を加えて攪拌した。続いて、沈殿物を吸引ろ過によりろ別し、水で2回洗浄した後に減圧下120℃で12時間乾燥し、黄色の固体を得た。得られた黄色個体を赤外分光法（ＫＢｒ法）で分析したところ、１３４６、１５３７、１７１２、１７７２ｃｍ−１に吸収ピークを観測した。また、得られた黄色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト８．１３、８．６１の位置に４，４′−ビス（２，２′−ジニトロ−Ｎ−メチルフタルイミド）に由来するピークを観測した他に、７．８２−８．０７、８．１５−８．２１、８．５１−８．５９の位置にもそれぞれピークを観測した。
(Comparative example)
62.0 g (194 mmol) of 4,4′-bis (N-methylphthalimide) and 90 ml of concentrated sulfuric acid were introduced into a 500 ml container equipped with a stirrer, a thermometer, a condenser, and a dropping funnel. Subsequently, 120 g of fuming nitric acid was slowly introduced with a dropping funnel at such a rate that the temperature in the reaction system settled in the range of 80 ° C. to 90 ° C., and stirred for 2 hours at 80 ° C. after completion of the dropwise introduction. Subsequently, after the reaction system was air-cooled, the reaction mixture was poured onto ice, and water was added and stirred. Subsequently, the precipitate was separated by suction filtration, washed twice with water, and then dried at 120 ° C. under reduced pressure for 12 hours to obtain a yellow solid. When the obtained yellow solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 1346, 1537, 1712, and 1772 cm −1 . The obtained yellow solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR. As a result, 4,4′-bis (2,2′-dinitro- In addition to observing peaks derived from (N-methylphthalimide), peaks were also observed at positions 7.82-8.07, 8.15-8.21, 8.51-8.59.
次に、攪拌装置、ディーンスタークトラップ、窒素導入用毛細管、玉栓を取り付けた３００ｍｌの容器に、５．２ｇ（５５．０ｍｍｏｌ）のフェノール、５０ｍｌのＮ，Ｎ−ジメチルアセトアミド、２．３ｇ（５７．５ｍｍｏｌ）の水酸化ナトリウム、２０ｍｌのトルエンを導入し、窒素をバブリングさせながら室温で1時間攪拌した。続いて、窒素導入用毛細管を取り外し、窒素導入管を取り付け、窒素気流下で１００−１２０℃の温度範囲で、水を共沸させながら、系中のトルエンが目視で確認できなくなるまで攪拌した（およそ３時間）。続いて、ディーンスタークトラップを取り外し、温度計を取り付け、内温が８０℃になるまで空冷した。続いて、１０．３ｇ（２５ｍｍｏｌ）の４，４′−ビス（２，２′−ジニトロ−Ｎ−メチルフタルイミド）を導入し、８０℃で2時間攪拌した。続いて、反応混合物を２００ｍｌの水に導入し、得られた沈殿物を吸引ろ過によりろ別し、2回水洗した後、減圧下、１００℃で、１２時間乾燥することにより、薄黄色の固体を得た。得られた薄黄色の個体を赤外分光法（ＫＢｒ法）で分析したところ、７３９、１０４０，１２５０、１３８６、１５３７、１７１３、１７７２ｃｍ−１に吸収ピークを観測した。また、得られた白色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト７．０１−７．０５、７．１９−７．２６、７．３６−７．４５、８．０１の位置に４，４′−ビス（２，２′−ジフェノキシ−N−メチルフタルイミド）に由来するピークを観測した他に、６．９０、６．９６、７．１２、７．８２、７．８６、８．１４、８．１９、８．４６の位置にもそれぞれピークを観測した。 Next, 5.2 g (55.0 mmol) of phenol, 50 ml of N, N-dimethylacetamide, 2.3 g (57 g) were added to a 300 ml container equipped with a stirrer, a Dean Stark trap, a capillary tube for introducing nitrogen, and a ball stopper. 0.5 mmol) sodium hydroxide and 20 ml of toluene were introduced and stirred at room temperature for 1 hour while bubbling nitrogen. Subsequently, the capillary for nitrogen introduction was removed, a nitrogen introduction tube was attached, and stirring was performed while azeotroping water in a temperature range of 100-120 ° C. under a nitrogen stream until toluene in the system could not be visually confirmed ( About 3 hours). Subsequently, the Dean Stark trap was removed, a thermometer was attached, and air cooling was performed until the internal temperature reached 80 ° C. Subsequently, 10.3 g (25 mmol) of 4,4′-bis (2,2′-dinitro-N-methylphthalimide) was introduced and stirred at 80 ° C. for 2 hours. Subsequently, the reaction mixture was introduced into 200 ml of water, and the resulting precipitate was filtered by suction filtration, washed twice with water, and then dried at 100 ° C. under reduced pressure for 12 hours to obtain a pale yellow solid. Got. When the obtained pale yellow solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 739, 1040, 1250, 1386, 1537, 1713, and 1772 cm −1 . Moreover, when the obtained white solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR, chemical shifts 7.01-7.05, 7.19-7.26, 7.36-7.45, In addition to observing a peak derived from 4,4′-bis (2,2′-diphenoxy-N-methylphthalimide) at the 8.01 position, 6.90, 6.96, 7.12, 7.82 , 7.86, 8.14, 8.19, and 8.46 were also observed.
次に、攪拌装置、冷却管、玉栓を取り付けた１００ｍｌの容器に、３．２０ｇの４，４′−ビス（２，２′−ジフェノキシ−N−メチルフタルイミド）、１５ｍｌの水、２．１３ｇの水酸化カリウムを導入し、還流下で２４時間、攪拌を行った。続いて、反応溶液を空冷した後に６．６Ｎの塩酸を導入してｐＨ１．０にしてよく攪拌することにより、白色の沈殿物を得た。得られた沈殿物を吸引ろ過によりろ別し、2回水洗して白色固体を得た。続いて、攪拌装置、冷却管、玉栓を取り付けた１００ｍｌの容器に、得られた白色個体と１０ｍｌの無水酢酸を導入し、還流下で４時間攪拌した。空冷後、析出した固体を吸引ろ過によりろ別し、減圧下、120℃で、12時間乾燥し、白色固体を得た。得られた白色個体の融点は２２９−２３１℃であった。また、得られた白色個体を赤外分光法（ＫＢｒ法）で分析したところ、１８４０、１７７８ｃｍ−１に吸収ピークを観測した。また、得られた白色個体をDMSO-d6に溶かし、1H−ＮＭＲで分析したところ、ケミカルシフト ７．０６−７．１１、７．１７、７．２５−７．３４、７．４１−７．５２、８．３４の位置にピークを観測した。以上により、この化合物が２，２′−ジフェノキシ−４，４′，５，５′−ビフェニルテトラカルボン酸二無水物であることを確認した。さらに、得られた２，２′−ジフェノキシ−３，３′，４，４′−ビフェニルテトラカルボン酸二無水物を水酸化ナトリウム水溶液で処理後に塩酸で処理してテトラカルボン酸に変換してから高速液体クロマトフィー（ＨＰＬＣ）で分析したところ、ＨＰＬＣ純度は９６．７％であった。 Next, in a 100 ml container equipped with a stirrer, a condenser tube and a ball plug, 3.20 g of 4,4′-bis (2,2′-diphenoxy-N-methylphthalimide), 15 ml of water, 2.13 g Of potassium hydroxide was introduced and stirred under reflux for 24 hours. Subsequently, the reaction solution was air-cooled, 6.6 N hydrochloric acid was introduced to pH 1.0, and the mixture was stirred well to obtain a white precipitate. The obtained precipitate was separated by suction filtration and washed twice with water to obtain a white solid. Subsequently, the obtained white solid and 10 ml of acetic anhydride were introduced into a 100 ml container equipped with a stirrer, a cooling tube and a ball stopper, and stirred for 4 hours under reflux. After air cooling, the precipitated solid was separated by suction filtration and dried at 120 ° C. under reduced pressure for 12 hours to obtain a white solid. The melting point of the obtained white solid was 229-231 ° C. Further, when the obtained white solid was analyzed by infrared spectroscopy (KBr method), absorption peaks were observed at 1840 and 1778 cm −1 . The obtained white solid was dissolved in DMSO-d 6 and analyzed by 1 H-NMR. As a result, chemical shifts 7.06-7.11, 7.17, 7.25-7.34, 7.41- Peaks were observed at positions 7.52 and 8.34. From the above, it was confirmed that this compound was 2,2′-diphenoxy-4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride. Further, the obtained 2,2'-diphenoxy-3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was treated with an aqueous sodium hydroxide solution and then treated with hydrochloric acid to convert it to a tetracarboxylic acid. When analyzed by high performance liquid chromatography (HPLC), the HPLC purity was 96.7%.
本発明により、第一の工程にアミド系の有機溶媒を用いて再結晶する工程を含むジアリールオキシビフェニルテトラカルボン酸二無水物の製造方法は、第一の工程において得られる一般式（化２）で示されるビス（ジニトロ−Ｎ−アルキルイミド）をアミド系の有機溶媒を用いて再結晶することによって、第二工程以降での副生物の量を抑制でき、最終的に得られるジアリールオキシビフェニルテトラカルボン酸二無水物の純度が向上し、ポリイミド等の耐熱性縮合系ポリマーを高重合度で合成し得るだけの充分な純度を有するジアリールオキシビフェニルテトラカルボン酸二無水物を工業的に効率よく製造できることができ、ポリイミド等の耐熱性縮合系ポリマーを高重合度で合成し得るだけの充分な純度を有するジアリールオキシビフェニルテトラカルボン酸二無水物を工業的に効率よく製造でき、産業界に大きく寄与することが期待される。 According to the present invention, a method for producing a diaryloxybiphenyltetracarboxylic dianhydride including a step of recrystallization using an amide-based organic solvent in the first step is represented by the general formula (Formula 2) obtained in the first step: By recrystallizing the bis (dinitro-N-alkylimide) represented by formula (2) using an amide-based organic solvent, the amount of by-products in the second step and thereafter can be suppressed, and the finally obtained diaryloxybiphenyltetra The purity of carboxylic dianhydride is improved, and industrially efficient production of diaryloxybiphenyltetracarboxylic dianhydride having sufficient purity to synthesize heat-resistant condensation polymers such as polyimide with a high degree of polymerization A diaryloxy biphenyl having a purity sufficient to synthesize a heat-resistant condensation polymer such as polyimide with a high degree of polymerization. Le tetracarboxylic acid dianhydride can be produced industrially efficiently, it is expected to contribute greatly to the industry.
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