JP3219256B2 - Method for producing bis (p-hydroxyphenyl) acetic acid - Google Patents
Method for producing bis (p-hydroxyphenyl) acetic acidInfo
- Publication number
- JP3219256B2 JP3219256B2 JP35158692A JP35158692A JP3219256B2 JP 3219256 B2 JP3219256 B2 JP 3219256B2 JP 35158692 A JP35158692 A JP 35158692A JP 35158692 A JP35158692 A JP 35158692A JP 3219256 B2 JP3219256 B2 JP 3219256B2
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- Prior art keywords
- acid
- hydroxyphenyl
- acetic acid
- bis
- sulfuric acid
- Prior art date
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はビス（ｐ−ヒドロキシフ
ェニル）酢酸の製造方法に関する。The present invention relates to a process for producing bis (p-hydroxyphenyl) acetic acid.
【０００２】[0002]
【従来の技術】ビス（ｐ−ヒドロキシフェニル）酢酸
は、農薬、医薬、感熱紙の顕色剤の中間体、エポキシ樹
脂やポリカーボネート等のポリマー原料や改質剤として
使用される化合物である。しかしながら、該化合物の工
業的な製造方法については従来殆ど報告がなされてい
ず、わずかにその合成方法が、２−３見出されるにすぎ
ない。例えば、Ｊ．Ｏｒｇ．Ｃｈｅｍ．２４，１９４９
−５１（１９５９）にＨｕｂａｃｈｅｒがフェノールと
グリオキシル酸を硫酸存在下に反応させて該化合物を得
たことを発表している。また日本公開特許公報 昭５６
−５５３３７にグリオキシル酸１モルと２モル以上のフ
ェノールとを４０℃以上の温度で、且つグリオキシル酸
１モルに対して０．５モル以上の鉱酸及び１−５モルの
脂肪族カルボン酸の共存下で反応させることを特徴とす
るビス（ｐ−ヒドロキシフェニル）酢酸の製造方法が提
案されている。しかし、この二つの方法は、反応時間が
３０−６４時間と長く、しかも、副反応が多く起こり、
純度の高い該化合物を得ようとすれば、煩雑な操作が必
要となり、収率が低くなって、工業的に価値の少ない方
法である。Ｊ．Ｏｒｇ．Ｃｈｅｍ．２６，１４２０−２
（１９６１）にＮａｔｈａｎｓｏｈｎがｐ−ＭｅＯＣ6
Ｈ4 ＣＨ（ＯＨ）ＣＮとフェノールを７３％硫酸中で反
応させ、４−ヒドロキシ−４−メトキシジフェニルアセ
トニトリルを得、これを加水分解してビス（ｐ−ヒドロ
キシフェニル）酢酸を得たことを発表している。この方
法もまた、原料が高価であり、且つ加水分解の工程が必
要なこと等、工業的な方法とは、言いがたい。2. Description of the Related Art Bis (p-hydroxyphenyl) acetic acid is a compound used as an intermediate of a developer for agricultural chemicals, medicines, and thermal paper, as a raw material for polymers such as epoxy resins and polycarbonates, and as a modifier. However, there have been few reports on industrial production methods of the compound, and only a few synthesis methods have been found. For example, J. Org. Chem. 24, 1949
No.-51 (1959) reports that Hubacher obtained the compound by reacting phenol and glyoxylic acid in the presence of sulfuric acid. Also, Japanese Unexamined Patent Publication No. 56
-55337, coexistence of 1 mol of glyoxylic acid and 2 mol or more of phenol at a temperature of 40 ° C. or more, and 0.5 mol or more of mineral acid and 1-5 mol of aliphatic carboxylic acid per 1 mol of glyoxylic acid. A method for producing bis (p-hydroxyphenyl) acetic acid, which is characterized by reacting under the following conditions, has been proposed. However, these two methods have a long reaction time of 30 to 64 hours, and many side reactions occur.
In order to obtain the compound having a high purity, a complicated operation is required, the yield is reduced, and this is a method of low industrial value. J. Org. Chem. 26,1420-2
(1961) Nathansohn added p-MeOC 6
H 4 CH (OH) CN and phenol were reacted in 73% sulfuric acid to give 4-hydroxy-4-methoxydiphenylacetonitrile, which was hydrolyzed to give bis (p-hydroxyphenyl) acetic acid. are doing. This method cannot be said to be an industrial method because the raw materials are expensive and a hydrolysis step is required.
【０００３】[0003]
【発明が解決しようとする課題】以上のように、従来の
合成方法では、副反応物が多量に生成するので、高純度
のビス（ｐ−ヒドロキシフェニル）酢酸を得ようとすれ
ば、煩雑な操作を必要とし、収率も高くなく、廃液処理
費が高くなり、コストが上昇するという欠点がある。従
って、安価な原料を使用し、副反応の少ない反応方法に
より、ビス（ｐ−ヒドロキシフェニル）酢酸を得る方法
の開発が、望まれている。As described above, in the conventional synthesis method, since a large amount of by-products is produced, it is complicated to obtain high-purity bis (p-hydroxyphenyl) acetic acid. There are drawbacks that require operation, the yield is not high, the waste liquid treatment cost is high, and the cost is high. Therefore, development of a method for obtaining bis (p-hydroxyphenyl) acetic acid using an inexpensive raw material and a reaction method with few side reactions is desired.
【０００４】[0004]
【課題を解決するための手段】フェノールとグリオキシ
ル酸を硫酸の存在下、反応させて、ビス（ｐ−ヒドロキ
シフェニル）酢酸を合成する方法は、原料が安価なの
で、収率が良好で、しかも、副反応物の除去が容易であ
れば、工業的な製造方法になる可能性があると考えられ
たが、検討の結果、この方法は副反応物が多く、しかも
生成物の精製が困難であり、工業的な製造方法とは言え
ないことが判かった。他方、フェノールとグリオキシル
酸を水酸化ナトリウムの存在下、反応させると、ｐ−ヒ
ドロキシマンデル酸Ｎａ塩が、簡単な、分離操作で高純
度、高収率で得られることが、公知になっているので、
このｐ−ヒドロキシマンデル酸Ｎａ塩を出発物質とし
て、フェノールと反応させる条件を検討したところ、触
媒として使用する酸の濃度と、反応温度をコントロール
することにより、ビス（ｐ−ヒドロキシフェニル）酢酸
が、高純度、高収率で得られることが分かり、本発明を
完成した。The method of synthesizing bis (p-hydroxyphenyl) acetic acid by reacting phenol and glyoxylic acid in the presence of sulfuric acid has a good yield because the raw materials are inexpensive. It was thought that if the removal of by-products was easy, it could be an industrial production method, but as a result of examination, this method had many by-products and it was difficult to purify the product. It was found that this was not an industrial production method. On the other hand, it has been known that when phenol and glyoxylic acid are reacted in the presence of sodium hydroxide, a sodium salt of p-hydroxymandelic acid can be obtained in a simple separation operation with high purity and high yield. So
By examining the conditions for reacting with phenol using the sodium salt of p-hydroxymandelic acid as a starting material, bis (p-hydroxyphenyl) acetic acid was converted to a compound by controlling the concentration of the acid used as a catalyst and the reaction temperature. It was found that high purity and high yield were obtained, and the present invention was completed.
【０００５】すなわち、本発明は、 （１）ｐ−ヒドロキシマンデル酸を、酸の存在下、フェ
ノールと反応させることを特徴とするビス（ｐ−ヒドロ
キシフェニル）酢酸の製造方法 （２）酸が、硫酸である前項１記載のビス（ｐ−ヒドロ
キシフェニル）酢酸の製造方法 （３）硫酸水溶液とフェノールの混合物中にｐ−ヒドロ
キシマンデル酸Ｎａ塩を添加することを特徴とするビス
（ｐ−ヒドロキシフェニル）酢酸の製造方法 （４）硫酸水溶液の濃度が１０−９０％である前項３記
載のビス（ｐ−ドロキシフェニル）酢酸の製造方法 である。That is, the present invention provides: (1) a method for producing bis (p-hydroxyphenyl) acetic acid, which comprises reacting p-hydroxymandelic acid with phenol in the presence of an acid; 2. The method for producing bis (p-hydroxyphenyl) acetic acid according to the above item 1, which is sulfuric acid. (3) Bis (p-hydroxyphenyl) acid salt is added to a mixture of an aqueous sulfuric acid solution and phenol. ) Method for producing acetic acid (4) The method for producing bis (p-droxyphenyl) acetic acid according to item 3, wherein the concentration of the aqueous sulfuric acid solution is 10 to 90%.
【０００６】以下、本発明を詳細に説明する。本発明で
使用されるｐ−ヒドロキシマンデル酸は、乾燥品でも、
含水品でもよく、塩になっていてもよい。むしろ、でき
るだけ、低価格の原料を使用したほうが、工業的に有利
なので、含水のｐ−ヒドロキシマンデル酸Ｎａ塩が、好
ましい。ただ、あまり、水が多すぎると、硫酸の濃度を
容易にコントロールできなくなるので、含水量として
は、０−５０％、好ましくは０−２０％、特に好ましく
は０−１０％である。塩としては、Ｎａ塩、Ｋａ塩、Ｌ
ｉ塩等が好ましく、特にＮａ塩が好ましい。Hereinafter, the present invention will be described in detail. The p-hydroxymandelic acid used in the present invention may be a dried product,
It may be a water-containing product or a salt. Rather, it is industrially advantageous to use raw materials that are as inexpensive as possible, so that hydrous sodium p-hydroxymandelic acid salt is preferred. However, if the amount of water is too large, the concentration of sulfuric acid cannot be easily controlled. Therefore, the water content is 0 to 50%, preferably 0 to 20%, and particularly preferably 0 to 10%. As the salt, Na salt, Ka salt, L
i-salts and the like are preferred, and Na salts are particularly preferred.
【０００７】溶媒としては、水が最も好ましいが、メタ
ノール、エタノール、イソプロピルアルコール等のアル
コール類、酢酸メチルエステル、酢酸エチルエステル、
酢酸ブチルエステル等の酢酸エステル類、ベンゼン、ト
ルエン、キシレン等の芳香族化合物類等の有機溶剤を水
に添加しても良い。触媒としては、硫酸、塩酸、燐酸等
の無機酸、ｐ−トルエンスルフォン酸、蓚酸等の有機酸
が好ましいが、特に硫酸が好ましい。以下水を溶媒とし
て硫酸を触媒に使用した場合について説明する。反応容
器に仕込む硫酸の濃度は１０−９０％が好ましい。使用
されるｐ−ヒドロキシマンデル酸は、アルカリ金属塩で
も、含水品でも良く、また、縮合反応の結果、水が生成
するため、反応中の硫酸濃度は、仕込み硫酸濃度より低
下する。従って、反応中の硫酸濃度が、１０−９０％、
好ましくは、１０−７０％、特に好ましくは、２０−５
０％になるよう、仕込み硫酸濃度を選択する。仕込み硫
酸水溶液の量は、ビス（ｐ−ドロキシフェニル）酢酸の
理論得量１００重量部あたり、１００〜２０００重量
部、好ましくは、１５０〜１０００重量部、特に好まし
くは、２００〜５００重量部が使用される。１００重量
部未満では、反応の結果生じるビス（ｐ−ヒドロキシフ
ェニル）酢酸が析出して来て、撹はんが困難になり、反
応が完結しなかったり、副反応が起こったり、収率が低
下する。２０００重量部を越えると、製造効率が悪くな
り経済的でない。As the solvent, water is most preferred, but alcohols such as methanol, ethanol and isopropyl alcohol, methyl acetate, ethyl acetate,
Organic solvents such as acetates such as butyl acetate and aromatics such as benzene, toluene and xylene may be added to water. As the catalyst, inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as p-toluenesulfonic acid and oxalic acid are preferable, and sulfuric acid is particularly preferable. Hereinafter, a case where sulfuric acid is used as a catalyst with water as a solvent will be described. The concentration of sulfuric acid charged in the reaction vessel is preferably 10-90%. The p-hydroxymandelic acid used may be an alkali metal salt or a water-containing product, and water is generated as a result of the condensation reaction, so that the sulfuric acid concentration during the reaction is lower than the charged sulfuric acid concentration. Therefore, the sulfuric acid concentration during the reaction is 10-90%,
Preferably, 10-70%, particularly preferably 20-5
Select the concentration of the supplied sulfuric acid so as to be 0%. The amount of the aqueous sulfuric acid solution charged is 100 to 2,000 parts by weight, preferably 150 to 1000 parts by weight, particularly preferably 200 to 500 parts by weight, per 100 parts by weight of the theoretical amount of bis (p-droxyphenyl) acetic acid. used. If the amount is less than 100 parts by weight, bis (p-hydroxyphenyl) acetic acid generated as a result of the reaction will precipitate, making it difficult to stir, the reaction will not be completed, side reactions will occur, and the yield will decrease. I do. If the amount exceeds 2,000 parts by weight, the production efficiency deteriorates, which is not economical.
【０００８】原料の使用モル比は、ｐ−ヒドロキシマン
デル酸／フェノールが、０．７−１．２、好ましくは、
０．８−１．１、特に好ましくは、０．９−１．０であ
る。モル比が０．７未満だと、フェノールが過剰に残
り、生成物の精製操作が必要になり経済的でない。又モ
ル比が１．２を越えると、副反応物が多く生じ、収率が
低下し、精製操作も必要になる。The molar ratio of the raw materials used is such that p-hydroxymandelic acid / phenol is 0.7-1.2, preferably
0.8-1.1, particularly preferably 0.9-1.0. If the molar ratio is less than 0.7, phenol remains excessively, and a purification operation of the product is required, which is not economical. On the other hand, when the molar ratio exceeds 1.2, many by-products are generated, the yield is reduced, and a purification operation is required.
【０００９】反応温度は、−１０−１００℃、好ましく
は、１０−７０℃、特に好ましくは、３０−６０℃であ
る。−１０℃未満だと、反応速度が遅く、１００℃越え
ると副反応物が多くなる。反応時間は、硫酸水溶液の濃
度、温度により、相当変化するが、１−２０時間、好ま
しくは、２−１０時間、特に好ましくは、３−８時間で
ある。[0009] The reaction temperature is -10-100 ° C, preferably 10-70 ° C, particularly preferably 30-60 ° C. If the temperature is lower than −10 ° C., the reaction rate is low. The reaction time varies considerably depending on the concentration and temperature of the aqueous sulfuric acid solution, but is 1 to 20 hours, preferably 2 to 10 hours, particularly preferably 3 to 8 hours.
【００１０】液体クロマトグラフィーで、ｐ−ヒドロキ
シマンデル酸が０．５％以下になったら、必要に応じ
て、水を加え、析出しているビス（ｐ−ヒドロキシフェ
ニル）酢酸の流動状態を良好にする。１０−２０℃まで
冷却し、減圧濾過し、濾液の硫酸は、次の反応に使用す
る。さらに、冷水で洗浄し、硫酸、硫酸ナトリウムを除
去する。次に、５０−６０℃で乾燥して目的物を得る。When p-hydroxymandelic acid is reduced to 0.5% or less by liquid chromatography, water is added as necessary to improve the flow state of the precipitated bis (p-hydroxyphenyl) acetic acid. I do. Cool to 10-20 ° C, filter under reduced pressure, and use the sulfuric acid in the filtrate for the next reaction. Further, it is washed with cold water to remove sulfuric acid and sodium sulfate. Next, it is dried at 50-60 ° C. to obtain the desired product.
【００１１】[0011]
【実施例】実施例によって本発明を更に具体的に説明す
るが、本発明がこれらの実施例のみに限定されるもので
ない。EXAMPLES The present invention will be described more specifically with reference to examples, but the present invention is not limited to only these examples.
【００１２】実施例１ 撹はん器、温度計を備えた３００ＣＣフラスコに、フェ
ノール ２０．７ｇ（０．２２モル）、４５％硫酸 ９
６ｇを加え、４５−５０℃に加熱、撹はんした。次に、
８９％の純度のｐ−ヒドロキシマンデル酸Ｎａの１水和
物 ４７ｇ（０．２０１モル）を２０−２５分かけて加
えた。２．５時間後に、４５％硫酸 ９６ｇを加え、析
出してきたビス（ｐ−ヒドロキシフェニル）酢酸の流動
性を向上させた。４５−５０℃、６．５時間反応し、水
７０ｇ加え、反応を終了した。１０−２０℃に冷却し
て、水流アスピレイターで、減圧濾過した。濾液の硫酸
水溶液は、２２０ｇで次回の反応に使用した。フィルタ
ーケーキを、冷水３００ｇで洗浄し、硫酸、硫酸ナトリ
ウムを除去した。５０−６０℃で２日間乾燥して、ビス
（ｐ−ヒドロキシフェニル）酢酸 ４９ｇを得た。液体
クロマトグラフィーで、安息香酸を標準物質として、定
量した結果、純度は９７．２％であった。Example 1 A 300 CC flask equipped with a stirrer and a thermometer was charged with 20.7 g (0.22 mol) of phenol and 45% sulfuric acid 9
6 g was added, and the mixture was heated and stirred at 45-50 ° C. next,
47 g (0.201 mol) of 89% pure sodium p-hydroxymandelic acid were added over 20-25 minutes. After 2.5 hours, 96 g of 45% sulfuric acid was added to improve the fluidity of the precipitated bis (p-hydroxyphenyl) acetic acid. The reaction was carried out at 45-50 ° C. for 6.5 hours, and 70 g of water was added to terminate the reaction. After cooling to 10-20 ° C, the mixture was filtered under reduced pressure with a water jet aspirator. 220 g of the aqueous sulfuric acid solution of the filtrate was used for the next reaction. The filter cake was washed with 300 g of cold water to remove sulfuric acid and sodium sulfate. After drying at 50-60 ° C for 2 days, 49 g of bis (p-hydroxyphenyl) acetic acid was obtained. As a result of quantification by liquid chromatography using benzoic acid as a standard substance, the purity was 97.2%.
【００１３】実施例２ 撹はん器、温度計を備えた３００ＣＣフラスコに、フェ
ノール ２０．７ｇ（０．２２モル）、４５％硫酸 ９
６ｇを加え、４５−５０℃に加熱、撹はんした。次に、
８９％の純度のｐ−ヒドロキシマンデル酸Ｎａの１水和
物 ４７ｇ（０．２０１モル）を２０−２５分かけて加
えた。２．５時間後に、４５％硫酸 ９６ｇを加え、析
出してきたビス（ｐ−ヒドロキシフェニル）酢酸の流動
性を向上させた。更に、ｐ−ヒドロキシマンデル酸Ｎａ
の１水和物 ２．１ｇを反応開始、３時間後、４時間後
に加えた。ｐ−ヒドロキシマンデル酸Ｎａの１水和物は
合計５１．２ｇ（０．２２モル）加えたことになる。
５．５時間後、水 ７０ｇ加え、反応を終了した。１０
−２０℃に冷却して、水流アスピレイターで、減圧濾過
した。濾液の硫酸水溶液は、２２０ｇで次回の反応に使
用した。フィルターケーキを、冷水３００ｇで洗浄し、
硫酸、硫酸ナトリウムを除去した。５０−６０℃で２日
間乾燥して、ビス（ｐ−ヒドロキシフェニル）酢酸 ５
７ｇを得た。液体クロマトグラフィーで、安息香酸を標
準物質として、定量した結果、純度は９７．２％であっ
た。Example 2 A 300 CC flask equipped with a stirrer and a thermometer was charged with 20.7 g (0.22 mol) of phenol and 45% sulfuric acid 9
6 g was added, and the mixture was heated and stirred at 45-50 ° C. next,
47 g (0.201 mol) of 89% pure sodium p-hydroxymandelic acid were added over 20-25 minutes. After 2.5 hours, 96 g of 45% sulfuric acid was added to improve the fluidity of the precipitated bis (p-hydroxyphenyl) acetic acid. Further, p-hydroxymandelic acid Na
The monohydrate 2.1 g was added 3 hours and 4 hours after the start of the reaction. This means that a total of 51.2 g (0.22 mol) of sodium monohydrate of p-hydroxymandelic acid was added.
After 5.5 hours, 70 g of water was added to terminate the reaction. 10
After cooling to −20 ° C., the mixture was filtered under reduced pressure with a water jet aspirator. 220 g of the aqueous sulfuric acid solution of the filtrate was used for the next reaction. Wash the filter cake with 300 g of cold water,
Sulfuric acid and sodium sulfate were removed. After drying at 50-60 ° C. for 2 days, bis (p-hydroxyphenyl) acetic acid 5
7 g were obtained. As a result of quantification by liquid chromatography using benzoic acid as a standard substance, the purity was 97.2%.
【００１４】実施例３ 撹はん器、温度計を備えた３００ＣＣフラスコに、フェ
ノール ２０．７ｇ（０．２２モル）、３６．２％硫酸
９６ｇを加え、４５−５０℃に加熱、撹はんした。次
に、８９％の純度のｐ−ヒドロキシマンデル酸Ｎａの１
水和物 ４７ｇ（０．２０１モル）を２０−２５分かけ
て加えた。反応開始７．５時間後に、２２．５％硫酸
９６ｇを加え、析出してきたビス（ｐ−ヒドロキシフェ
ニル）酢酸の流動性を向上させた。４５−５０℃、９．
５時間反応し、更に７０−７３℃４時間反応した。１０
−２０℃に冷却して、水流アスピレイターで、減圧濾過
した。濾液の硫酸水溶液は、１４５ｇで次回の反応に使
用した。フィルターケーキを、冷水２００ｇで洗浄し、
硫酸、硫酸ナトリウムを除去した。５０−６０℃で２日
間乾燥して、ビス（ｐ−ヒドロキシフェニル）酢酸 ５
１．３ｇを得た。液体クロマトグラフィーで、安息香酸
を標準物質として、定量した結果、純度は９４．７％で
あった。Example 3 To a 300 CC flask equipped with a stirrer and a thermometer, 20.7 g (0.22 mol) of phenol and 96 g of 36.2% sulfuric acid were added, and the mixture was heated to 45-50 ° C. and stirred. did. Next, 1% of 89% pure p-hydroxymandelic acid Na
47 g (0.201 mol) of the hydrate were added over 20-25 minutes. 7.5 hours after the start of the reaction, 22.5% sulfuric acid
96 g was added to improve the fluidity of the precipitated bis (p-hydroxyphenyl) acetic acid. 45-50 ° C, 9.
The reaction was carried out for 5 hours, and further for 4 hours at 70-73 ° C. 10
After cooling to −20 ° C., the mixture was filtered under reduced pressure with a water jet aspirator. 145 g of the aqueous sulfuric acid solution of the filtrate was used for the next reaction. Wash the filter cake with 200 g of cold water,
Sulfuric acid and sodium sulfate were removed. After drying at 50-60 ° C. for 2 days, bis (p-hydroxyphenyl) acetic acid 5
1.3 g were obtained. As a result of quantification by liquid chromatography using benzoic acid as a standard substance, the purity was 94.7%.
【００１５】[0015]
【発明の効果】副反応物の生成が少なく、再結晶等の精
製操作を必要とせず、収率が高く、廃液負荷が少なく、
経済的なビス（ｐ−ヒドロキシフェニル）酢酸の製法が
確立された。EFFECTS OF THE INVENTION The amount of by-products is small, the purification operation such as recrystallization is not required, the yield is high, the waste liquid load is small,
An economical process for preparing bis (p-hydroxyphenyl) acetic acid has been established.
Claims (4)
下、フェノールと反応させることを特徴とするビス（ｐ
−ヒドロキシフェニル）酢酸の製造方法1. Bis (p) characterized in that p-hydroxymandelic acid is reacted with phenol in the presence of an acid.
Method for producing (hydroxyphenyl) acetic acid
−ヒドロキシフェニル）酢酸の製造方法2. The bis (p) according to claim 1, wherein the acid is sulfuric acid.
Method for producing (hydroxyphenyl) acetic acid
ヒドロキシマンデル酸Ｎａ塩を添加することを特徴とす
るビス（ｐ−ヒドロキシフェニル）酢酸の製造方法3. A mixture of an aqueous sulfuric acid solution and phenol in a mixture of p-
A method for producing bis (p-hydroxyphenyl) acetic acid, comprising adding a sodium hydroxymandelic acid salt.
求項３記載のビス（ｐ−ドロキシフェニル）酢酸の製造
方法4. The method for producing bis (p-droxyphenyl) acetic acid according to claim 3, wherein the concentration of the aqueous sulfuric acid solution is 10-90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35158692A JP3219256B2 (en) | 1992-12-09 | 1992-12-09 | Method for producing bis (p-hydroxyphenyl) acetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35158692A JP3219256B2 (en) | 1992-12-09 | 1992-12-09 | Method for producing bis (p-hydroxyphenyl) acetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06172257A JPH06172257A (en) | 1994-06-21 |
| JP3219256B2 true JP3219256B2 (en) | 2001-10-15 |
Family
ID=18418277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35158692A Expired - Fee Related JP3219256B2 (en) | 1992-12-09 | 1992-12-09 | Method for producing bis (p-hydroxyphenyl) acetic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3219256B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1817354A1 (en) | 2004-12-02 | 2007-08-15 | DSMIP Assets B.V. | Hydroxy-aromatic compound, process for the preparation thereof, and use of the compound |
| KR20090024136A (en) * | 2006-06-02 | 2009-03-06 | 디에스엠 아이피 어셋츠 비.브이. | Process for the preparation of a hydroxy-aromatic resin; hydroxy-aromatic resin, and modification thereof |
-
1992
- 1992-12-09 JP JP35158692A patent/JP3219256B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06172257A (en) | 1994-06-21 |
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