JP4826891B2 - Purification method of 1,6-dihydroxynaphthalene - Google Patents
Purification method of 1,6-dihydroxynaphthalene Download PDFInfo
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- JP4826891B2 JP4826891B2 JP2005380868A JP2005380868A JP4826891B2 JP 4826891 B2 JP4826891 B2 JP 4826891B2 JP 2005380868 A JP2005380868 A JP 2005380868A JP 2005380868 A JP2005380868 A JP 2005380868A JP 4826891 B2 JP4826891 B2 JP 4826891B2
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- dihydroxynaphthalene
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Description
本発明は、染料中間体や医薬中間体として有用な、１，６−ジヒドロキシナフタレンの精製法に関するものである。 The present invention relates to a method for purifying 1,6-dihydroxynaphthalene which is useful as a dye intermediate or a pharmaceutical intermediate.
１，６−ジヒドロキシナフタレンは、次の非特許文献１に記載されているように１−ナフトール−６−スルホン酸カリウムと水酸化カリウムをアルカリ溶融反応することで得られる。 1,6-dihydroxynaphthalene is obtained by subjecting potassium 1-naphthol-6-sulfonate and potassium hydroxide to an alkali melting reaction as described in Non-Patent Document 1 below.
本発明は、粗製の１，６−ジヒドロキシナフタレンの水溶液から結晶水を持たない１，６−ジヒドロキシナフタレンを得る方法を提供せんとするものである。 The present invention is intended to provide a method for obtaining 1,6-dihydroxynaphthalene having no water of crystallization from an aqueous solution of crude 1,6-dihydroxynaphthalene.
結晶水を含んだ１，６−ジヒドロキシナフタレンの融点は６０℃である。本発明者は、粗製の１，６−ジヒドロキシナフタレンの熱水溶液から冷却して１，６−ジヒドロキシナフタレンの結晶を析出させる際に、少なくとも融点付近の温度で結晶の析出を開始させる必要があると考え、検討の結果、本発明に到達したものである。
即ち本発明は粗製の１，６−ジヒドロキシナフタレンを含む熱水溶液を冷却して１，６−ジヒドロキシナフタレンの結晶を析出させるにあたり、前記熱水溶液にその３〜５０重量％に相当する無機塩類を添加し、４０℃以上の温度で結晶の析出を開始させるようにしたことを特徴とする１，６−ジヒドロキシナフタレンの精製法。The melting point of 1,6-dihydroxynaphthalene containing crystal water is 60 ° C. When the present inventors cool a crude 1,6-dihydroxynaphthalene aqueous solution to precipitate 1,6-dihydroxynaphthalene crystals, it is necessary to start crystal precipitation at a temperature at least near the melting point. As a result of consideration and examination, the present invention has been achieved.
That is, in the present invention, when a hot aqueous solution containing crude 1,6-dihydroxynaphthalene is cooled to precipitate 1,6-dihydroxynaphthalene crystals, inorganic salts corresponding to 3 to 50% by weight are added to the hot aqueous solution. And a method for purifying 1,6-dihydroxynaphthalene, wherein the precipitation of crystals is started at a temperature of 40 ° C. or higher.
無機塩類を添加することなく従来知られている方法で、１，６−ジヒドロキシナフタレンを熱水から冷却して再結晶する場合には、３０℃付近の温度で結晶の析出を開始させることができるが、４０℃以上の温度で結晶を析出させることが事実上困難で、結晶水を含んだ不安定な結晶しか得られず、ろ液中への溶解損失も大きかった。本発明によれば結晶水を持たない安定した結晶が得られ、またろ液への溶解損失も少ない。 When 1,6-dihydroxynaphthalene is cooled from hot water and recrystallized by a conventionally known method without adding inorganic salts, crystal precipitation can be started at a temperature around 30 ° C. However, it was practically difficult to precipitate crystals at a temperature of 40 ° C. or higher, and only unstable crystals containing water of crystallization were obtained, and the dissolution loss in the filtrate was large. According to the present invention, stable crystals having no water of crystallization are obtained, and the dissolution loss in the filtrate is small.
粗製の１，６−ジヒドロキシナフタレンを含む熱水溶液から再結晶する場合、無機塩類の量は、好ましくは前記熱水溶液の５〜２５重量％に相当する量である。
また、無機塩類としては塩化ナトリウム、塩化カリウム、塩化アンモニウム、ボウ硝等を単独、或いは幾つかを混合して使用することができる。より好ましくは塩化ナトリウム、塩化カリウムである。
結晶の析出を開始させる温度は好ましくは５０℃以上であり、より好ましくは６０℃以上である。In the case of recrystallization from a hot aqueous solution containing crude 1,6-dihydroxynaphthalene, the amount of inorganic salts is preferably an amount corresponding to 5 to 25% by weight of the hot aqueous solution.
As the inorganic salts, sodium chloride, potassium chloride, ammonium chloride, bow glass and the like can be used alone or in combination. More preferred are sodium chloride and potassium chloride.
The temperature at which the precipitation of crystals starts is preferably 50 ° C. or higher, more preferably 60 ° C. or higher.
鉄製容器に１−ナフトール−６−スルホン酸カリウム ５２．４ｇを固体の水酸化カリウム ２８ｇ、水１０ｃｃと共に加えて、２６０〜２７０℃で１５分間加熱した。これを室温まで冷却したのち、反応物を水５００ｃｃに溶解した。この溶解液にｐＨ７．０となるまで塩酸を加えた。析出した結晶をクロロホルム２００ｃｃを加えて抽出後、濃縮乾固すると黒褐色樹脂状の粗製１，６−ジヒドロキシナフタレン２２ｇを得た。
得られた粗製１，６−ジヒドロキシナフタレン １２．５ｇを７０℃の温水２００ｃｃに溶解し、活性炭３ｇを加えて清澄ろ過をおこなった。この７０℃の清澄ろ過液に４０ｇの食塩を加えると、直ちに結晶が析出した。５℃まで冷却、ろ別して得られた無色結晶を、５０℃で一夜乾燥すると無色の１，６−ジヒドロキシナフタレン１０．８ｇ（融点１３６℃、固形分収率８６．４％）を得た。ＨＰＬＣ分析で純度９９．８％であった。含水率をカールフィッシャー水分計で測定したところ０．１％であった。また島津製作所製熱天秤ＴＧＡ５０で測定したところ、１５０℃付近までまったく減量を認めなかった。To an iron container, 52.4 g of potassium 1-naphthol-6-sulfonate was added together with 28 g of solid potassium hydroxide and 10 cc of water, and heated at 260 to 270 ° C. for 15 minutes. After cooling to room temperature, the reaction product was dissolved in 500 cc of water. Hydrochloric acid was added to the solution until pH 7.0 was reached. The precipitated crystals were extracted by adding 200 cc of chloroform and then concentrated to dryness to obtain 22 g of crude 1,6-dihydroxynaphthalene as a black brown resin.
12.5 g of the obtained crude 1,6-dihydroxynaphthalene was dissolved in 200 cc of warm water at 70 ° C., and 3 g of activated carbon was added to perform clarification filtration. When 40 g of sodium chloride was added to the clarified filtrate at 70 ° C., crystals immediately precipitated. The colorless crystals obtained by cooling to 5 ° C. and filtration were dried overnight at 50 ° C. to obtain 10.8 g of colorless 1,6-dihydroxynaphthalene (melting point 136 ° C., solid content yield 86.4%). The purity was 99.8% by HPLC analysis. The water content was measured with a Karl Fischer moisture meter and found to be 0.1%. Moreover, when measured with a Shimadzu thermobalance TGA50, no weight loss was observed up to about 150 ° C.
比較例
実施例１と同様の操作で得た粗製結晶１２．５ｇを７０℃の温水２００ｃｃに溶解し、活性炭３ｇを加えて清澄ろ過をおこなった。この清澄ろ過液を冷却すると３０℃付近で結晶が析出し始めた。５℃まで冷却、ろ別して得られた無色結晶を、５０℃で一夜乾燥すると灰黒色の１，６−ジヒドロキシナフタレン７．５ｇ（融点６０℃、固形分収率６０．０％）を得たが、ろ液中への溶解損失が著しかった。ＨＰＬＣ分析で純度９３．７％であった。含水率をカールフィッシャー水分計で測定したところ５．５％であった。また島津製作所製熱天秤ＴＧＡ５０で測定したところ、６０℃付近に明瞭な５．４％の減量を認めたことから、明らかに結晶水を含んでいる。Comparative Example 12.5 g of a crude crystal obtained by the same operation as in Example 1 was dissolved in 200 cc of warm water at 70 ° C., and 3 g of activated carbon was added for clarification filtration. When this clarified filtrate was cooled, crystals began to precipitate around 30 ° C. The colorless crystals obtained by cooling to 5 ° C. and filtration were dried at 50 ° C. overnight to obtain 7.5 g of gray-black 1,6-dihydroxynaphthalene (melting point 60 ° C., solid content yield 60.0%). The dissolution loss in the filtrate was remarkable. The purity was 93.7% by HPLC analysis. The water content was measured with a Karl Fischer moisture meter and found to be 5.5%. Moreover, when it measured with Shimadzu Corporation thermobalance TGA50, the clear weight loss of 5.4% was recognized at 60 degreeC vicinity, Therefore Crystal water is contained clearly.
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| JP4826891B2 true JP4826891B2 (en) | 2011-11-30 |
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| US2665313A (en) * | 1951-10-02 | 1954-01-05 | Allied Chem & Dye Corp | Production of 1, 6-naphthalenediol |
| DE3840618C1 (en) * | 1988-12-02 | 1990-03-15 | Bayer Ag, 5090 Leverkusen, De |
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