JP2759088B2 - Method for producing aryl 1,4-dihydroxy-2-naphthoate - Google Patents
Method for producing aryl 1,4-dihydroxy-2-naphthoateInfo
- Publication number
- JP2759088B2 JP2759088B2 JP18764689A JP18764689A JP2759088B2 JP 2759088 B2 JP2759088 B2 JP 2759088B2 JP 18764689 A JP18764689 A JP 18764689A JP 18764689 A JP18764689 A JP 18764689A JP 2759088 B2 JP2759088 B2 JP 2759088B2
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- Prior art keywords
- dihydroxy
- acid
- reaction
- naphthoic acid
- water
- Prior art date
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Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は、写真薬、染料、顔料の中間体として有用な
1,4−ジヒドロキシ−２−ナフトエ酸アリールエステル
の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention is useful as an intermediate for photographic drugs, dyes and pigments.
The present invention relates to a method for producing an aryl 1,4-dihydroxy-2-naphthoate.
＜従来技術＞ 多環式オキシカルボン酸アリールエステルの製造法と
しては、多環式オキシカルボン酸とフェノール類又はア
ルコール類とを脱水反応させることにより得られるが、
通常のエステル類合成法である強酸を触媒とする方法
は、カルボン酸の分解を伴うため使用できず、脱水剤と
して、三塩化燐、オキシ塩化燐、五塩化燐などを使用す
る方法が行われている。しかしながら、これらの公知の
方法では製品に着色がみられ、製造工程に手間を要し、
またフェノール類を溶媒をかねて大過剰に使用するた
め、廃水中のフェノール類の除去など反応後の処理が極
めて煩雑であり、工業的に有利な方法とは言えない。<Prior Art> As a method for producing a polycyclic oxycarboxylic acid aryl ester, it can be obtained by a dehydration reaction between a polycyclic oxycarboxylic acid and a phenol or alcohol.
The method of using a strong acid as a catalyst, which is a usual method for synthesizing esters, cannot be used because it involves decomposition of carboxylic acid, and a method using phosphorus trichloride, phosphorus oxychloride, phosphorus pentachloride, or the like as a dehydrating agent is performed. ing. However, in these known methods, the product is colored, and the production process requires time,
Further, since phenols are used in a large excess in the presence of a solvent, post-reaction treatments such as removal of phenols in wastewater are extremely complicated, and cannot be said to be an industrially advantageous method.
上記問題を解決する方法として特公昭58−22021号公
報、特開昭64−45341号公報において、反応剤としてト
リアリール亜リン酸エステルを用いる方法が提案されて
いるが、これら公知の方法では、相当量の副生成物の生
成が起因し、目的物を高純度で製造することは困難であ
った。As a method for solving the above-mentioned problem, Japanese Patent Publication No. 58-2221, Japanese Patent Application Laid-Open No. 64-45341, a method using a triaryl phosphite as a reactant has been proposed, but in these known methods, Due to the generation of a considerable amount of by-products, it was difficult to produce the target product with high purity.
＜発明が解決しようとする課題＞ 本発明の目的は、1,4−ジヒドロキシ−２−ナフトエ
酸アリールエステルを、工業的に有利な方法によって、
高純度・高収率で製造する方法を提供することである。<Problem to be Solved by the Invention> An object of the present invention is to provide an aryl ester of 1,4-dihydroxy-2-naphthoic acid by an industrially advantageous method.
An object of the present invention is to provide a method for producing a compound with high purity and high yield.
＜課題を解決するための手段＞ 本発明は、1,4−ジヒドロキシ−２−ナフトエ酸とト
リアリール亜リン酸エステルとを反応させて得られる下
記一般式（Ｉ） （R1、R2はそれぞれ独立に、水素原子、低級アルキル基
又はハロゲン原子を表わす） で表される1,4−ジヒドロキシ−２−ナフトエ酸アリー
ルエステルを主反応生成物として含む反応マスを、低級
アルコール及び水との混合溶媒から晶出させることを特
徴とする1,4−ジヒドロキシ−２−ナフトエ酸アリール
エステルの製造法である。<Means for Solving the Problems> The present invention provides a compound represented by the following general formula (I) obtained by reacting 1,4-dihydroxy-2-naphthoic acid with a triaryl phosphite. (Wherein R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a halogen atom), a reaction mass containing a 1,4-dihydroxy-2-naphthoic acid aryl ester as a main reaction product, A process for producing aryl 1,4-dihydroxy-2-naphthoic acid, characterized by crystallization from a mixed solvent of lower alcohol and water.
以下本発明の方法を詳しく説明する。 Hereinafter, the method of the present invention will be described in detail.
本発明に使用される低級アルコールとしては、具体的
には炭素数１〜４までの脂肪族低級アルコールであり、
具体的にはメタノール、エタノール、ｎ−プロピルアル
コール、イソプロピルアルコール、ｎ−ブチルアルコー
ルが挙げられる。中でもメタノールが好ましく用いられ
る。The lower alcohol used in the present invention is specifically an aliphatic lower alcohol having 1 to 4 carbon atoms,
Specific examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol. Among them, methanol is preferably used.
これらの低級アルコールと水との混合溶媒の組成は、
アルコール濃度５〜50容量％、好ましくは10〜30容量％
の低級アルコール−水混合溶媒が用いられる。The composition of the mixed solvent of these lower alcohols and water is
Alcohol concentration 5-50% by volume, preferably 10-30% by volume
The lower alcohol-water mixed solvent is used.
また、該混合溶媒の使用量は、反応マスに対して１〜
10重量倍、好ましくは２〜８重量倍使用される。In addition, the amount of the mixed solvent used is 1 to the reaction mass.
It is used 10 times by weight, preferably 2 to 8 times by weight.
該混合溶媒から晶出させる温度は、０〜80℃、好まし
くは20〜55℃の範囲で行われる。The temperature for crystallization from the mixed solvent is in the range of 0 to 80 ° C, preferably 20 to 55 ° C.
本発明の特徴は、前記のとおり、1,4−ジヒドロキシ
−２−ナフトエ酸アリールエステルを主反応生成物とし
て含む反応マスから、目的物を効率よく単離することに
ある。As described above, a feature of the present invention is to efficiently isolate a target product from a reaction mass containing 1,4-dihydroxy-2-naphthoic acid aryl ester as a main reaction product.
本発明に適用される目的とする1,4−ジヒドロキシ−
２−ナフトエ酸アリールエステルの製造方法は、従来公
知の方法が適用される。具体的には、特公昭58−22021
号公報或いは特開昭64−45341号公報に記載された公知
の方法によって製造することができる。1,4-dihydroxy- which is intended to be applied to the present invention
As a method for producing the aryl 2-naphthoate, a conventionally known method is applied. Specifically, Japanese Patent Publication No. 58-2221
And JP-A-64-45341.
なお、本発明者らは先に1,4−ジヒドロキシ−２−ナ
フトエ酸とトリアリール亜リン酸エステルとを反応させ
るに当たり、触媒として有機酸又は無機酸を用いること
が好ましいことを見出したが、該方法を本発明に適用す
ると更に好ましい結果が得られる。In addition, the present inventors have previously found that it is preferable to use an organic acid or an inorganic acid as a catalyst when reacting 1,4-dihydroxy-2-naphthoic acid with a triaryl phosphite, More favorable results are obtained when the method is applied to the present invention.
ここで、使用される有機酸又は無機酸触媒としては、
具体的にはベンゼンスルホン酸、ベンゼンジスルホン
酸、トルエンスルホン酸、キシレンスルホン酸等の炭素
数１〜10までのアルキルベンゼンスルホン酸、炭素数１
〜10までのアルキルベンゼンジスルホン酸、ナフタレン
スルホン酸、ナフタレンジスルホン酸及び炭素数１〜10
までのアルキル置換ナフタレンスルホン酸、炭素数１〜
10までのアルキル置換ナフタレンジスルホン酸などの芳
香族スルホン酸類、メタンスルホン酸、エタンスルホン
酸等の炭素数１〜10までの脂肪族スルホン酸類等の有機
酸及び硫酸、硝酸等の無機酸が挙げられる。中でも、ｐ
−トルエンスルホン酸が、好ましく用いられる。Here, as the organic acid or inorganic acid catalyst used,
Specifically, alkylbenzenesulfonic acid having 1 to 10 carbon atoms such as benzenesulfonic acid, benzenedisulfonic acid, toluenesulfonic acid, xylenesulfonic acid, etc .;
Up to 10 alkylbenzene disulfonic acid, naphthalene sulfonic acid, naphthalenedisulfonic acid and 1 to 10 carbon atoms
Alkyl-substituted naphthalenesulfonic acids up to 1 to 1 carbon atoms
Aromatic sulfonic acids such as alkyl-substituted naphthalenedisulfonic acid up to 10; organic acids such as aliphatic sulfonic acids having 1 to 10 carbon atoms such as methanesulfonic acid and ethanesulfonic acid; and inorganic acids such as sulfuric acid and nitric acid. . Among them, p
-Toluenesulfonic acid is preferably used.
これらの触媒の使用量は、1,4−ジヒドロキシー２−
ナフトエ酸に対し、0.01〜0.5モル比、好ましくは、0.0
5〜0.3モル比で使用される。The amount of these catalysts used is 1,4-dihydroxy-2-
0.01 to 0.5 molar ratio to naphthoic acid, preferably 0.0
Used in a 5-0.3 molar ratio.
また、反応試剤となるトリアリール亜リン酸エステル
類は1,4−ジヒドロキシー２−ナフトエ酸に対して、0.9
〜3.5モル比、好ましくは、1.5〜3.0モル比の範囲で使
用される。In addition, triaryl phosphites used as reaction reagents are 0.9 to 0.9% of 1,4-dihydroxy-2-naphthoic acid.
3.53.5 molar ratio, preferably in the range of 1.5-3.0 molar ratio.
反応温度は、30〜130℃、好ましくは90℃以下、更に
好ましくは70〜85℃の範囲で実施される。The reaction is carried out at a temperature of 30 to 130 ° C, preferably 90 ° C or lower, more preferably 70 to 85 ° C.
本反応は、無溶媒系が好ましいが、有機溶媒等の存在
下でも好適に反応することができる。用いることのでき
る溶媒の具体例としては、フェノール類、クレゾール
類、トルエン、キシレン等の芳香族炭化水素類、クロル
ベンゼン等のハロゲン化炭化水素類、メチル−ｎ−プロ
ピルケトン、メチル−ｎ−ブチルケトン、メチル−イソ
ブチルケトン、ジイソブチルケトン等のケトン類が例示
される。This reaction is preferably a solventless system, but can be suitably performed even in the presence of an organic solvent or the like. Specific examples of the solvent that can be used include phenols, cresols, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, methyl-n-propyl ketone, and methyl-n-butyl ketone. And ketones such as methyl-isobutyl ketone and diisobutyl ketone.
本発明の方法になる1,4−ジヒドロキシー２−ナフト
エ酸アリールエステルを主反応生成物として含む反応マ
スから目的物を取り出すための晶出処理は、通常、前記
反応マスを低級アルコール及び水との混合溶媒に排出・
希釈し、必要により加温撹拌及び／又は冷却処理によっ
て晶出させ、後は通常の方法によって濾過、洗滌、乾燥
等の手段が採られる。In the method of the present invention, the crystallization treatment for extracting a target substance from a reaction mass containing 1,4-dihydroxy-2-naphthoic acid aryl ester as a main reaction product is usually performed by reacting the reaction mass with a lower alcohol and water. To the mixed solvent of
After diluting and, if necessary, crystallization by heating, stirring and / or cooling, filtration, washing, drying and the like are carried out by a usual method.
＜発明の効果＞ 本発明の方法によれば、晶出の時間を短縮し、また濾
過時間も著しく短縮され、しかも高純度、高収率で目的
とするエステルを工業的に有利に製造することができ
る。<Effects of the Invention> According to the method of the present invention, the crystallization time is reduced, and the filtration time is also significantly reduced, and the desired ester can be industrially advantageously produced with high purity and high yield. Can be.
＜実施例＞ 以下実施例及び比較例により本発明をさらに詳しく説
明するが、本発明は、以下の実施例によって限定される
ものではない。<Examples> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
実施例１ 撹拌機付き容量１の反応器に、トリフェニルホスフ
ァイト（以下、TPPと称す）241gと1,4−ジヒドロキシ−
２−ナフトエ酸（以下、AOHと称す）59.5g、Ｐ−トルエ
ンスルホン酸（以下PTSと称す）6.6gを仕込み、80℃ま
で加熱昇温し、この温度で、５時間反応を行った。内容
物は、褐色透明の液状となり、反応は完結した。この
間、液体クロマトグラフによる未反応AOH分析を実施
し、反応終点を判定した。Example 1 In a reactor having a capacity of 1 with a stirrer, 241 g of triphenylphosphite (hereinafter referred to as TPP) and 1,4-dihydroxy-
59.5 g of 2-naphthoic acid (hereinafter, referred to as AOH) and 6.6 g of P-toluenesulfonic acid (hereinafter, referred to as PTS) were charged, heated to 80 ° C., and reacted at this temperature for 5 hours. The content became a brown transparent liquid, and the reaction was completed. During this time, unreacted AOH analysis by liquid chromatography was performed to determine the end point of the reaction.
次いで、内容物を80℃で、1200gのメタノール−水混
合液（メタノール濃度16.7重量％）に滴下し、50℃で３
時間撹拌後、室温まで冷却し、折出物を濾別し、さらに
水洗後乾燥し、目的とする1,4−ジヒドロキシ−２−ナ
フトエ酸フェニルエステル（以下ONHと称す）80g（収
率;97.9％）を得た。液体クロトマトグラフによる組成
分析の結果はONHの純度は92.5％であり、副生成物（４
−（１′,4′−ジヒドロキシ−２′−ナフトイル）−オ
キシ−１−ヒドロキシ−２−ナフトエ酸フェニルエステ
ル）は7.5％であった。Next, the content was added dropwise to 80Og of a methanol-water mixture (methanol concentration: 16.7% by weight) at 80 ° C.
After stirring for an hour, the mixture was cooled to room temperature, and the precipitate was separated by filtration, washed with water and dried, and 80 g of the objective 1,4-dihydroxy-2-naphthoic acid phenyl ester (hereinafter referred to as ONH) (yield: 97.9) %). The result of composition analysis by liquid chromatography showed that the purity of ONH was 92.5%, and that the by-product (4
-(1 ', 4'-dihydroxy-2'-naphthoyl) -oxy-1-hydroxy-2-naphthoic acid phenyl ester) was 7.5%.
実施例２ 実施例１と同様に反応を行ない、反応終点を確認した
後、反応マスを1200gのエタノール−水混合溶媒（エタ
ノール濃度16.7重量％）に排出し、以下実施例１と同様
に実施し、ONH78g（収率95.45％）を得た。Example 2 The reaction was carried out in the same manner as in Example 1, and after confirming the end point of the reaction, the reaction mass was discharged into 1200 g of a mixed solvent of ethanol and water (ethanol concentration: 16.7% by weight). 78g of ONH (95.45% yield).
実施例３ 実施例１と同様に反応を行ない、反応終点を確認した
後、反応マスを1200gのイソプロピルアルコール−水混
合溶媒（イソプロピルアルコール濃度16.7重量％）に排
出し、以下実施例１と同様に実施し、ONH79g（収率96.7
5％）を得た。Example 3 The reaction was carried out in the same manner as in Example 1, and after confirming the end point of the reaction, the reaction mass was discharged into 1200 g of a mixed solvent of isopropyl alcohol-water (isopropyl alcohol concentration: 16.7% by weight). Was carried out and ONH 79 g (yield 96.7
5%).
実施例４ 実施例１と同様に反応を行ない、反応終点を確認した
後、反応マスを750gのメタノール−水混合溶媒（メタノ
ール濃度25重量％）に排出し、以下実施例１と同様に実
施し、ONH77g（収率94.3％）を得た。Example 4 The reaction was carried out in the same manner as in Example 1, and after confirming the end point of the reaction, the reaction mass was discharged into 750 g of a methanol-water mixed solvent (methanol concentration: 25% by weight). 77 g of ONH (94.3% yield).
実施例５ 実施例１と同様に反応を行ない、反応終点を確認した
後、反応マスを1600gのメタノール−水混合溶媒（メタ
ノール濃度５重量％）に排出し、以下実施例１と同様に
実施し、ONH80g（収率97.9％）を得た。Example 5 The reaction was carried out in the same manner as in Example 1, and after confirming the end point of the reaction, the reaction mass was discharged into 1600 g of a methanol-water mixed solvent (methanol concentration: 5% by weight). ONH80g (yield 97.9%) was obtained.
実施例６ 撹拌機付き容量１の反応器に、トリフェニルホスフ
ァイト（以下、TPPと称す）241gと1,4−ジヒドロキシ−
２−ナフトエ酸（以下、AOHと称す）59.5g、110℃まで
加熱昇温し、この温度で、５時間反応を行った。内容物
は、褐色透明の液状となり、反応は完結した。この間、
液体クロマトグラフによる未反応AOH分析を実施し、反
応終点を判定した。Example 6 In a reactor having a capacity of 1 with a stirrer, 241 g of triphenylphosphite (hereinafter referred to as TPP) and 1,4-dihydroxy-
59.5 g of 2-naphthoic acid (hereinafter referred to as AOH) was heated to 110 ° C., and the reaction was carried out at this temperature for 5 hours. The content became a brown transparent liquid, and the reaction was completed. During this time,
Unreacted AOH analysis by liquid chromatography was performed to determine the end point of the reaction.
次いで、内容物を80℃で、1200gのメタノール−水混
合液（メタノール濃度16.7重量％）に滴下し、50℃で３
時間撹拌後、室温まで冷却し、折出物を濾別し、さらに
水洗後乾燥し、目的とする1,4−ジヒロドキシ−２−ナ
フトエ酸フェニルエステル（以下ONHと称す）72g（収
率;88％）を得た。液体クロトマトグラフによる組成分
析の結果はONHの純度は65.5％であり、副生成物（４−
（１′,4′−ジヒドロキシ−２′−ナフトイル）−オキ
シ−１−ヒドロキシ−２−ナフトエ酸フェニルエステ
ル）は34.5％であった。Next, the content was added dropwise to 80Og of a methanol-water mixture (methanol concentration: 16.7% by weight) at 80 ° C.
After stirring for an hour, the mixture was cooled to room temperature, and the precipitate was separated by filtration, washed with water and dried, and 72 g of the objective phenyl 1,4-dihydroxy-2-naphthoate (hereinafter referred to as ONH) (yield: 88 %). The result of composition analysis by liquid chromatography showed that the purity of ONH was 65.5%, and that the by-product (4-
(1 ', 4'-dihydroxy-2'-naphthoyl) -oxy-1-hydroxy-2-naphthoic acid phenyl ester) was 34.5%.
実施例７ 撹拌機付き容量１の反応器に、トリフェニルホスフ
ァイト（以下、TPPと称す）241gと1,4−ジヒドロキシ−
７−メチル−２−ナフトエ酸（以下、メチル−AOHと称
す）63.6g、Ｐ−トルエンスルホン酸（以下PTSと称す）
6.6gを仕込み、80℃まで加熱昇温し、この温度で、５時
間反応を行った。内容物は、褐色透明の液状となり、反
応は完結した。この間、液体クロマトグラフによる未反
応メチル−AOH分析を実施し、反応終点を判定した。Example 7 In a reactor having a capacity of 1 with a stirrer, 241 g of triphenylphosphite (hereinafter, referred to as TPP) and 1,4-dihydroxy-
63.6 g of 7-methyl-2-naphthoic acid (hereinafter, referred to as methyl-AOH), P-toluenesulfonic acid (hereinafter, referred to as PTS)
6.6 g was charged and heated to 80 ° C., and the reaction was carried out at this temperature for 5 hours. The content became a brown transparent liquid, and the reaction was completed. During this time, unreacted methyl-AOH analysis by liquid chromatography was performed to determine the end point of the reaction.
次いで、内容物を80℃で、1200gのメタノール−水混
合液（メタノール濃度16.7重量％）に滴下し、50℃で３
時間撹拌後、室温まで冷却し、折出物を濾別し、さらに
水洗後乾燥し、目的とする1,4−ジヒドロキシ−７−メ
チル−２−ナフトエ酸フェニルエステル（以下メチル−
ONHと称す）82.3g（収率;96.0％）を得た。液体クロト
マトグラフによる組成分析の結果はメチル−ONHの純度
は92.0％であった。Next, the content was added dropwise to 80Og of a methanol-water mixture (methanol concentration: 16.7% by weight) at 80 ° C.
After stirring for an hour, the mixture was cooled to room temperature, and the deposit was filtered off, washed with water and dried to obtain the desired 1,4-dihydroxy-7-methyl-2-naphthoic acid phenyl ester (hereinafter referred to as methyl-
82.3 g (yield; 96.0%) of ONH) was obtained. The result of composition analysis by liquid chromatography showed that the purity of methyl-ONH was 92.0%.
比較例１ 実施例６と同様に反応を行ない、反応終点を確認した
後、反応マスを1200gの水に排出した。これを温度50℃
で10時間撹拌を続けたが、ダンゴ状であった。デカンテ
ーションにより水溶液を除去し、再度1200gの温水を加
え、50℃で更に５時間撹拌し、析出物を濾別し、水洗、
乾燥した。目的とするONH72g（収率88％）を得た。液体
クロトマトグラフによる組成分析の結果はONHの純度は6
5.5％であり、副生成物（４−（１′,4′−ジヒドロキ
シ−２′−ナフトイル）−オキシ−１−ヒドロキシ−２
−ナフトエ酸フェニルエステル）は34.5％であった。Comparative Example 1 The reaction was carried out in the same manner as in Example 6, and after confirming the end point of the reaction, the reaction mass was discharged into 1200 g of water. This at a temperature of 50 ° C
The stirring was continued for 10 hours. The aqueous solution was removed by decantation, 1200 g of warm water was added again, and the mixture was further stirred at 50 ° C. for 5 hours. The precipitate was separated by filtration, washed with water,
Dried. 72 g (88% yield) of the desired ONH was obtained. Liquid chromatograph composition analysis shows ONH purity of 6
5.5% and the by-product (4- (1 ', 4'-dihydroxy-2'-naphthoyl) -oxy-1-hydroxy-2
-Phenyl naphthoate) was 34.5%.
比較例２ 実施例１と同様に反応を行ない、反応終点を確認した
後、反応マスを1200gの水に排出した。これを温度50℃
で10時間撹拌を続けたが、ダンゴ状であった。デカンテ
ーションにより水溶液を除去し、再度1200gの温水を加
え、50℃で更に５時間撹拌し、析出物を濾別し、水洗、
乾燥した。目的とするONH79g（収率88％）を得た。液体
クロトマトグラフによる組成分析の結果はONHの純度は9
0.5％であり、副生成物（４−（１′,4′−ジヒドロキ
シ−２′−ナフトイル）−オキシ−１−ヒドロキシ−２
−ナフトエ酸フェニルエステル）は8.5％であった。Comparative Example 2 The reaction was carried out in the same manner as in Example 1, and after confirming the end point of the reaction, the reaction mass was discharged into 1200 g of water. This at a temperature of 50 ° C
The stirring was continued for 10 hours. The aqueous solution was removed by decantation, 1200 g of warm water was added again, and the mixture was further stirred at 50 ° C. for 5 hours. The precipitate was separated by filtration, washed with water,
Dried. 79 g of the desired ONH (88% yield) was obtained. Liquid chromatograph composition analysis shows ONH purity of 9
0.5% and the by-product (4- (1 ', 4'-dihydroxy-2'-naphthoyl) -oxy-1-hydroxy-2
-Naphthoic acid phenyl ester) was 8.5%.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−52847（ＪＰ，Ａ) 特開 昭64−45343（ＪＰ，Ａ) 特開 昭64−45341（ＪＰ，Ａ) 特開 昭53−28139（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-52847 (JP, A) JP-A-64-45343 (JP, A) JP-A-64-45341 (JP, A) JP-A-53-453 28139 (JP, A)
Claims (10)
リアリール亜リン酸エステルとを反応させて得られる下
記一般式（Ｉ） （R1、R2はそれぞれ独立に、水素原子、低級アルキル基
又はハロゲン原子を表わす） で表される1,4−ジヒドロキシ−２−ナフトエ酸アリー
ルエステルを主反応生成物として含む反応マスを、低級
アルコール及び水との混合溶媒から晶出させることを特
徴とする1,4−ジヒドロキシ−２−ナフトエ酸アリール
エステルの製造法。1. A compound represented by the following general formula (I) obtained by reacting 1,4-dihydroxy-2-naphthoic acid with a triaryl phosphite. (Wherein R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a halogen atom), a reaction mass containing a 1,4-dihydroxy-2-naphthoic acid aryl ester as a main reaction product, A process for producing aryl 1,4-dihydroxy-2-naphthoate, characterized by crystallization from a mixed solvent of lower alcohol and water.
５〜50容量％の低級アルコールである請求項（１）に記
載の方法。2. The method according to claim 1, wherein the mixed solvent of lower alcohol and water is a lower alcohol having a concentration of 5 to 50% by volume.
が、反応マスに対して１〜10重量倍である請求項（１）
又は（２）のいずれかに記載の方法。3. The use amount of the mixed solvent of lower alcohol and water is 1 to 10 times by weight of the reaction mass.
Or the method according to any one of (2).
（１）〜（３）のいずれかに記載の方法。4. The method according to claim 1, wherein the lower alcohol is methanol.
（１）〜（４）のいずれかに記載の方法。5. The method according to claim 1, wherein the crystallization temperature is from 0 to 80 ° C.
リアリール亜リン酸エステルとの反応を、有機酸又は無
機酸から選ばれた酸触媒の存在下に行うことを特徴とす
る請求項（１）〜（５）のいずれかに記載の方法。6. The reaction of 1,4-dihydroxy-2-naphthoic acid with a triaryl phosphite in the presence of an acid catalyst selected from organic acids and inorganic acids. The method according to any one of (1) to (5).
ルホン酸から選ばれる請求項（６）に記載の方法。7. The method according to claim 6, wherein the acid catalyst is selected from aromatic sulfonic acids and aliphatic sulfonic acids.
求項（７）に記載の方法。8. The method according to claim 7, wherein the catalyst is p-toluenesulfonic acid.
して、トリアリール亜リン酸エステルを0.9〜3.5モル比
用いる請求項（６）〜（８）のいずれかに記載の方法。9. The method according to any one of claims (6) to (8), wherein the triaryl phosphite is used in a molar ratio of 0.9 to 3.5 based on 1,4-dihydroxy-2-naphthoic acid.
対して、触媒を0.01〜0.5モル比用いる請求項（６）〜
（９）のいずれかに記載の方法。10. The method according to claim 6, wherein the catalyst is used in a molar ratio of 0.01 to 0.5 with respect to 1,4-dihydroxy-2-naphthoic acid.
The method according to any one of (9).
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18764689A JP2759088B2 (en) | 1989-07-19 | 1989-07-19 | Method for producing aryl 1,4-dihydroxy-2-naphthoate |
| US07/542,440 US5162570A (en) | 1989-06-27 | 1990-06-22 | Process for producing 1,4-dihydroxy-2-arylnaphthoate |
| DE69011996T DE69011996T2 (en) | 1989-06-27 | 1990-06-26 | Process for the preparation of 1,4-dihydroxy-2-arylnaphthoate. |
| EP90306998A EP0405928B1 (en) | 1989-06-27 | 1990-06-26 | Process for producing 1,4-dihydroxy-2-arylnaphthoate |
| US07/931,068 US5241103A (en) | 1989-06-27 | 1992-08-17 | Process for producing 1,4-dihydroxy-2-arylnaphthoate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18764689A JP2759088B2 (en) | 1989-07-19 | 1989-07-19 | Method for producing aryl 1,4-dihydroxy-2-naphthoate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0352848A JPH0352848A (en) | 1991-03-07 |
| JP2759088B2 true JP2759088B2 (en) | 1998-05-28 |
Family
ID=16209757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18764689A Expired - Fee Related JP2759088B2 (en) | 1989-06-27 | 1989-07-19 | Method for producing aryl 1,4-dihydroxy-2-naphthoate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2759088B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4592158B2 (en) * | 2000-07-19 | 2010-12-01 | 城北化学工業株式会社 | Method for producing carboxylic acid aryl ester |
-
1989
- 1989-07-19 JP JP18764689A patent/JP2759088B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0352848A (en) | 1991-03-07 |
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