JP3204538B2 - Purification method of keto acid - Google Patents
Purification method of keto acidInfo
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- JP3204538B2 JP3204538B2 JP15250192A JP15250192A JP3204538B2 JP 3204538 B2 JP3204538 B2 JP 3204538B2 JP 15250192 A JP15250192 A JP 15250192A JP 15250192 A JP15250192 A JP 15250192A JP 3204538 B2 JP3204538 B2 JP 3204538B2
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- Prior art keywords
- keto acid
- acid derivative
- reaction
- keto
- reaction solution
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明はケト酸の精製方法に関す
る。The present invention relates to a method for purifying keto acids.
【０００２】[0002]
【従来の技術】例えば、N,Ｎ−ジアルキル−ｍ−アミノ
フエノールを無水フタル酸と反応させて得られるケト酸
は、感圧記録用又は感熱記録用の色素として有用なフル
オラン化合物の製造中間体として重要である。従来、上
記ケト酸は、トルエン、キシレン等の不活性反応溶剤中
でN,Ｎ−ジアルキル−ｍ−アミノフエノール１モルに対
して無水フタル酸0.５〜２モルを８０〜１５０℃の温度
で反応させることによつて製造されている。このような
方法によれば、通常、生成したケト酸が更にN,Ｎ−ジア
ルキル−ｍ−アミノフエノールと反応して、赤色染料で
あるローダミン系化合物等の着色物を副生する。従つ
て、得られたケト酸を感熱染料に誘導する前に、これら
ローダミン系副生物等を含む着色物質をケト酸から除去
することが必要である。2. Description of the Related Art For example, keto acid obtained by reacting N, N-dialkyl-m-aminophenol with phthalic anhydride is an intermediate for producing a fluoran compound useful as a dye for pressure-sensitive recording or heat-sensitive recording. As important. Conventionally, the above keto acid is prepared by adding 0.5 to 2 mol of phthalic anhydride to 1 mol of N, N-dialkyl-m-aminophenol in an inert reaction solvent such as toluene or xylene at a temperature of 80 to 150 ° C. It is manufactured by reacting. According to such a method, usually, the generated keto acid further reacts with N, N-dialkyl-m-aminophenol to produce a colored substance such as a rhodamine compound as a red dye by-product. Therefore, it is necessary to remove coloring substances containing these rhodamine by-products from the keto acid before introducing the obtained keto acid into the thermal dye.
【０００３】そこで、例えば、特開昭６２−７０３５０
号公報には、反応終了後に反応混合物にアルカリ水溶液
を加え、加熱して、副生したローダミン系化合物をケト
酸に変換した後、ケト酸のアルカリ塩を晶析させ、更に
水に溶解させた後、中和して、ケト酸を精製、取得する
方法が提案されている。しかし、このような方法によれ
ば、工程数が増加するのみならず、大量の中和排水が生
成する。[0003] For example, Japanese Patent Application Laid-Open No. 62-70350
In the gazette, an alkaline aqueous solution was added to the reaction mixture after the reaction was completed, and the mixture was heated to convert the by-produced rhodamine-based compound into keto acid, and then the alkali salt of keto acid was crystallized and further dissolved in water. Thereafter, a method of purifying and obtaining a keto acid by neutralization has been proposed. However, such a method not only increases the number of steps but also generates a large amount of neutralized wastewater.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、従来のケト
酸の精製方法における上記したような問題を解決するた
めになされたものであつて、副生したローダミン系化合
物等の着色物質を工業的に有利に且つ有効に除去する方
法を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the conventional method for purifying keto acid, and is intended to produce a colored substance such as a rhodamine compound produced as a by-product. It is an object of the present invention to provide a method for effectively and effectively removing.
【０００５】[0005]
【課題を解決するための手段】本発明は、N,Ｎ−ジアル
キル−ｍ−アミノフェノールと無水フタル酸との反応に
よつて得られる一般式（Ｉ）The present invention relates to a compound of the formula (I) obtained by reacting N, N-dialkyl-m-aminophenol with phthalic anhydride.
【０００６】[0006]
【化２】 Embedded image
【０００７】（式中、R1及びR2はそれぞれ独立に炭素数
１〜６のアルキル基を示す。）で表わされるケト酸誘導
体の精製方法において、このケト酸誘導体を反応溶剤中
にて水添触媒の存在下に水添し、得られた反応液からケ
ト酸誘導体を回収することを特徴とする。本発明の方法
においては、上記ケト酸誘導体として、N,Ｎ−ジメチル
ケト酸、N,Ｎ−ジエチルケト酸、N,Ｎ−ジ−ｎ−プロピ
ルケト酸、N,Ｎ−ジイソプロピルケト酸、N,Ｎ−ジ−ｎ
−ブチルケト酸、Ｎ−メチル−Ｎ−エチルケト酸、Ｎ−
エチル−Ｎ−イソプロピルケト酸、Ｎ−エチル−Ｎ−ｎ
−ブチルケト酸、Ｎ−エチル−Ｎ−イソアミルケト酸、
Ｎ−エチル−Ｎ−ヘキシルケト酸等のケト酸誘導体を挙
げることができる。(Wherein R 1 and R 2 each independently represent an alkyl group having 1 to 6 carbon atoms). In a method for purifying a keto acid derivative represented by the formula: It is characterized in that it is hydrogenated in the presence of an auxiliary catalyst, and the keto acid derivative is recovered from the obtained reaction solution. In the method of the present invention, as the keto acid derivative, N, N-dimethyl keto acid, N, N-diethyl keto acid, N, N-di-n-propyl keto acid, N, N-diisopropyl keto acid, N, N- Di-n
-Butylketo acid, N-methyl-N-ethylketo acid, N-
Ethyl-N-isopropylketo acid, N-ethyl-Nn
-Butyl keto acid, N-ethyl-N-isoamyl keto acid,
Keto acid derivatives such as N-ethyl-N-hexyl keto acid can be mentioned.
【０００８】また、一般式（Ｉ）において、R1及びR
2は、アルキル基に加えて、炭素数４〜８、好ましくは
５〜７のシクロアルキル基であつてもよい。このような
ケト酸誘導体としては、例えば、Ｎ−エチル−Ｎ−シク
ロヘキシルケト酸を挙げることができる。本発明によれ
ば、ローダミン等の着色物質を少量含み、着色（通常、
薄い桃色に着色）した上記ケト酸誘導体を反応溶剤に溶
解させ、水添触媒を加え、反応溶剤中にて水添反応を行
なつた後、例えば、得られた反応液から晶析等によつて
ケト酸誘導体を回収することによつて、極めて色相の良
好なケト酸を容易に得ることができる。更に、本発明に
よれば、例えば、N,Ｎ−ジアルキル−ｍ−アミノフェノ
ールと無水フタル酸との反応によつてケト酸誘導体を製
造する場合に、ケト酸誘導体を単離することなく、ケト
酸誘導体を含む反応液を上記したように水添処理しても
よい。In the general formula (I), R 1 and R
2 may be a cycloalkyl group having 4 to 8, preferably 5 to 7 carbon atoms in addition to the alkyl group. Such keto acid derivatives include, for example, N-ethyl-N-cyclohexyl keto acid. According to the present invention, a small amount of a coloring substance such as rhodamine is contained and coloring (usually,
After dissolving the above keto acid derivative (lightly colored pink) in a reaction solvent, adding a hydrogenation catalyst and performing a hydrogenation reaction in the reaction solvent, for example, crystallization or the like is performed from the obtained reaction solution. By recovering the keto acid derivative, a keto acid having an extremely good hue can be easily obtained. Further, according to the present invention, for example, when producing a keto acid derivative by reacting N, N-dialkyl-m-aminophenol with phthalic anhydride, the keto acid derivative can be isolated without isolating the keto acid derivative. The reaction solution containing the acid derivative may be hydrogenated as described above.
【０００９】本発明において、上記水添反応の溶剤とし
ては、一般に、メタノール、エタノール等のアルコール
類、テトラヒドロフラン、ジオキサン等のエーテル類、
酢酸等のカルボン酸類、酢酸エチル等のエステル類、ト
ルエン、キシレン等の芳香族炭化水素類、シクロヘキサ
ン、オクタン等の飽和炭化水素類等を好ましい反応溶剤
として挙げることができるが、これらに限定されるもの
ではなく、通常の水添反応に用いられる溶剤であれば、
如何なるものでもよい。しかし、上記したうちでは、特
に、メタノール、エタノール等のアルコール類、テトラ
ヒドロフラン、ジオキサン等のエーテル類が反応溶剤と
して好ましく用いられる。In the present invention, as the solvent for the hydrogenation reaction, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and dioxane;
Preferred examples of the reaction solvent include carboxylic acids such as acetic acid, esters such as ethyl acetate, aromatic hydrocarbons such as toluene and xylene, and saturated hydrocarbons such as cyclohexane and octane. Rather, if it is a solvent used for normal hydrogenation reaction,
Anything is possible. However, among the above, alcohols such as methanol and ethanol, and ethers such as tetrahydrofuran and dioxane are particularly preferably used as reaction solvents.
【００１０】かかる反応溶剤は、ケト酸の溶剤に対する
溶解度にもよるが、通常、ケト酸１重量部に対して、１
〜２０重量部、好ましくは、1.５〜１０重量部の範囲に
て用いられる。また、水添反応は、通常、常圧乃至１０
Kg／cm2 の水素圧下、２０〜１５０℃の温度にて行なわ
れ、反応時間は0.１〜１０時間の範囲にわたつてよい
が、水添条件を厳しくすれば、ケト酸自身の水添反応も
併発するので、好ましくは、反応温度は２０〜８０℃、
水素圧は常圧乃至５Kg／cm2 の範囲である。The reaction solvent depends on the solubility of the keto acid in the solvent, but is usually 1 to 1 part by weight of the keto acid.
To 20 parts by weight, preferably 1.5 to 10 parts by weight. In addition, the hydrogenation reaction is usually performed at normal pressure to 10
The reaction is carried out at a temperature of 20 to 150 ° C. under a hydrogen pressure of Kg / cm 2 , and the reaction time may be in a range of 0.1 to 10 hours. Since the reaction also occurs simultaneously, preferably, the reaction temperature is 20 to 80 ° C,
The hydrogen pressure ranges from normal pressure to 5 kg / cm 2 .
【００１１】本発明において用いる水添触媒は、均一
系、不均一系いずれの触媒でもよいが、水添後の触媒分
離の容易性等を考慮すると、不均一系触媒が好ましい。
なかでも、白金／カーボン（Ｐｔ／Ｃ）等の白金系担持
触媒、パラジウム／カーボン（Ｐｄ／Ｃ）等のパラジウ
ム系担持触媒、ラネーニツケル等を好ましい触媒として
挙げることができる。かかる水添触媒は、その活性、水
添反応の温度、水素圧等によつて、その最適の使用量が
適宜に決められるが、通常、ケト酸に対して、0.００１
〜１０重量％、好ましくは0.０１〜２重量％の範囲で用
いられる。The hydrogenation catalyst used in the present invention may be either a homogeneous catalyst or a heterogeneous catalyst, but a heterogeneous catalyst is preferable in consideration of the ease of separation of the catalyst after hydrogenation.
Of these, preferred are platinum-based supported catalysts such as platinum / carbon (Pt / C), palladium-based supported catalysts such as palladium / carbon (Pd / C), and Raney nickel. The optimum amount of such a hydrogenation catalyst can be appropriately determined depending on its activity, temperature of the hydrogenation reaction, hydrogen pressure, etc., but usually 0.0001 to keto acid.
It is used in the range of 10 to 10% by weight, preferably 0.01 to 2% by weight.
【００１２】本発明によれば、上述したような水添反応
の後、得られた反応液から触媒を濾別し、そのままケト
酸を晶析させるか、又は反応液中の溶剤を、例えば、ト
ルエン、キシレン等のような芳香族炭化水素類やイソプ
ロピルエーテル、ブチルエーテル等のような嵩高いエー
テル類のような晶析溶剤に交換した後、晶析を行なうこ
とによつて、反応液からケト酸を回収するのが好まし
い。しかし、別の方法として、水添反応の後、反応液か
ら触媒を濾別し、溶剤交換を行なうことなく、ケト酸に
対する貧溶剤を反応液に添加し、ケト酸を晶析すること
によつても、ケト酸を回収することができる。According to the present invention, after the above-mentioned hydrogenation reaction, the catalyst is filtered off from the obtained reaction solution, and the keto acid is crystallized as it is, or the solvent in the reaction solution is, for example, After exchanging with a crystallization solvent such as an aromatic hydrocarbon such as toluene or xylene or a bulky ether such as isopropyl ether or butyl ether, crystallization is carried out, whereby keto acid is obtained from the reaction solution. Is preferably recovered. However, as another method, after the hydrogenation reaction, the catalyst is filtered off from the reaction solution, and a poor solvent for the keto acid is added to the reaction solution without performing solvent exchange to crystallize the keto acid. Also, keto acid can be recovered.
【００１３】例えば、本発明によれば、水添反応の溶剤
として、メタノール、エタノール等の低級アルコール
類、酢酸等の低級カルボン酸類、又はテトラヒドロフラ
ン、ジオキサン等の水可溶性溶剤を用いた場合は、水添
反応の終了後、反応混合物に水を投入し、直ちにケト酸
を再沈又は晶析させることによつて、極めて色相の良好
なケト酸を容易に得ることができる。For example, according to the present invention, when a solvent for the hydrogenation reaction is a lower alcohol such as methanol or ethanol, a lower carboxylic acid such as acetic acid, or a water-soluble solvent such as tetrahydrofuran or dioxane, After completion of the addition reaction, water is added to the reaction mixture, and the keto acid is immediately reprecipitated or crystallized, whereby a keto acid having an extremely good hue can be easily obtained.
【００１４】このように、本発明によれば、ケト酸中に
含まれるローダミン系化合物等の着色物質を水添反応に
よつて脱色した後、例えば、晶析することによって、ア
ルカリ等を用いることなく、従って、中和排水等を生じ
ることなく、工業的に有利に極めて色相の良好なケト酸
を容易に得ることができる。As described above, according to the present invention, after a coloring substance such as a rhodamine compound contained in a keto acid is decolorized by a hydrogenation reaction, for example, crystallization is performed to use an alkali or the like. Therefore, a keto acid having a very good hue can be easily obtained industrially advantageously without producing neutralized wastewater or the like.
【００１５】[0015]
【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれら実施例により何ら限定されるものではな
い。EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples.
【００１６】実施例１ ローダミンに由来する５５０ｎｍの吸光度が0.３１（１
ｇ／メタノール１００ml）である４−N,Ｎ−ジ−エチル
アミノ−２−ヒドロキシ−2'−カルボキシベンゾフェノ
ン（ジエチルケト酸）５ｇをテトラヒドロフラン４５ｇ
に溶解させた後、これに水添触媒としてＰｔ／Ｃ（Ｐｔ
２％担持）0.４ｇを加えた。かかるジエチルケト酸に水
素下、密閉系にて、温度３５℃で0.５時間、水添反応を
行なつた。反応液の色は、当初は薄桃色であつたが、水
添反応の終了後には、鶯色であつた。窒素下に触媒を濾
別した後、窒素下、反応液を５０℃まで加熱し、これに
水４０mlを加えた後、冷却して再結晶を行なつた結果、
鶯色のジエチルケト酸を９２％の回収率で得た。このジ
エチルケト酸の５５０ｎｍにおける吸光度は0.０１であ
つた。Example 1 The absorbance at 550 nm derived from rhodamine was 0.31 (1
g / methanol 100 ml) and 5 g of 4-N, N-di-ethylamino-2-hydroxy-2'-carboxybenzophenone (diethylketo acid) in 45 g of tetrahydrofuran.
And dissolved in Pt / C (Pt / C) as a hydrogenation catalyst.
0.4 g (2% loading) was added. A hydrogenation reaction was performed on the diethylketoacid under hydrogen at a temperature of 35 ° C. for 0.5 hours in a closed system. The color of the reaction solution was light pink at the beginning, but was yellowish after the hydrogenation reaction was completed. After filtering off the catalyst under nitrogen, the reaction solution was heated to 50 ° C. under nitrogen, 40 ml of water was added thereto, and the mixture was cooled and recrystallized.
Yellow-colored diethylketoacid was obtained with a recovery of 92%. The absorbance at 550 nm of this diethyl keto acid was 0.01.
【００１７】実施例２ ローダミンに由来する５５０ｎｍの吸光度が0.１７（１
ｇ／メタノール１００ml）である４−Ｎ−エチル−Ｎ−
イソアミル−２−ヒドロキシ−2'−カルボキシベンゾフ
ェノン（エチルイソアミルケト酸）５ｇをメタノール１
５ｇに溶解させた後、これに水添触媒としてＰｔ／Ｃ
（Ｐｔ２％担持）0.４ｇを加えた。かかるエチルイソア
ミルケト酸に水素下、密閉系にて、温度３５℃で0.５時
間、水添反応を行なつた。反応液の色は、当初は薄桃色
であつたが、水添反応の終了後には、鶯色であつた。窒
素下に触媒を濾別した後、反応液に水７mlを加え、その
まま室温で攪拌し、種晶を添加して、結晶化させ、窒素
下にケト酸をろ過した。その結果、５５０ｎｍにおける
吸光度が0.０２５であるエチルイソアミルケト酸を回収
率８８％にて得た。Example 2 The absorbance at 550 nm derived from rhodamine was 0.17 (1
g / methanol 100 ml) 4-N-ethyl-N-
5 g of isoamyl-2-hydroxy-2'-carboxybenzophenone (ethyl isoamylketo acid) was added to methanol 1
After dissolving in 5 g, Pt / C was added as a hydrogenation catalyst.
(2% Pt loading) was added. A hydrogenation reaction was carried out on the ethylisoamylketoacid under hydrogen at a temperature of 35 ° C. for 0.5 hours in a closed system. The color of the reaction solution was light pink at the beginning, but was yellowish after the hydrogenation reaction was completed. After filtering off the catalyst under nitrogen, 7 ml of water was added to the reaction solution, the mixture was stirred at room temperature as it was, seed crystals were added to allow crystallization, and the keto acid was filtered under nitrogen. As a result, ethylisoamylketoacid having an absorbance at 550 nm of 0.025 was obtained at a recovery of 88%.
【００１８】実施例３ 実施例２において、原料の吸光度が0.３７のものを用い
た以外は、実施例２と全く同様に行なつた。その結果、
５５０ｎｍにおける吸光度が0.０２８であるエチルイソ
アミルケト酸を９２％の回収率で得た。Example 3 The procedure of Example 2 was repeated, except that the raw material used had an absorbance of 0.37. as a result,
Ethyl isoamyl keto acid having an absorbance at 550 nm of 0.028 was obtained with a recovery of 92%.
【００１９】実施例４ 実施例２において、水添触媒として、Ｐｔ／Ｃの代わり
に、Ｐｄ／Ｃ（Ｐｄ５％含有）を0.０８ｇ用いた以外
は、実施例２と全く同様に行なつた。その結果、５５０
ｎｍにおける吸光度が0.００６であるエチルイソアミル
ケト酸を９１％の回収率で得た。Example 4 Example 2 was carried out in the same manner as in Example 2, except that 0.08 g of Pd / C (containing 5% of Pd) was used instead of Pt / C as the hydrogenation catalyst. . As a result, 550
Ethyl isoamyl keto acid having an absorbance in nm of 0.006 was obtained with a recovery of 91%.
【００２０】実施例５ 実施例２において、Ｐｔ／Ｃの代わりに、ラネーニツケ
ル（川研ファインケミカル製ラネーＮＤＴ−６５）のメ
タノール懸濁液約５mlを用いた以外は、実施例１と全く
同様に行なつた。その結果、５５０ｎｍにおける吸光度
が0.０２５であるエチルイソアミルケト酸を８７％の回
収率で得た。Example 5 The procedure of Example 1 was repeated, except that about 5 ml of a methanol suspension of Raney Nickel (Raney NDT-65 manufactured by Kawaken Fine Chemicals) was used instead of Pt / C. Natsuta As a result, ethylisoamylketoacid having an absorbance at 550 nm of 0.025 was obtained with a recovery of 87%.
【００２１】実施例６ 実施例５において、ケト酸の吸光度が2.３のものを用い
た以外は、実施例５と全く同様に行なつた。その結果、
５５０ｎｍにおける吸光度が0.０２であるエチルイソア
ミルケト酸を８８％の回収率で得た。Example 6 The procedure of Example 5 was repeated except that the keto acid had an absorbance of 2.3. as a result,
Ethyl isoamyl keto acid having an absorbance at 550 nm of 0.02 was obtained with a recovery of 88%.
【００２２】実施例７ 実施例２において、Ｐｔ／Ｃに代えて、亜鉛末２００mg
を用いると共に、反応溶剤として、メタノールに代え
て、酢酸を用いた以外は、実施例１と同様に行なつた。
その結果、５５０ｎｍにおける吸光度が0.０４８のエチ
ルイソアミルケト酸を８５％の回収率で得た。Example 7 In Example 2, 200 mg of zinc dust was used instead of Pt / C.
Was carried out in the same manner as in Example 1 except that acetic acid was used instead of methanol as a reaction solvent.
As a result, ethyl isoamylketo acid having an absorbance at 550 nm of 0.048 was obtained at a recovery of 85%.
【００２３】実施例８ Ｎ−エチル−Ｎ−イソアミル−ｍ−アミノフェノール
（１0.３５ｇ）と無水フタル酸（１4.８ｇ）を酢酸溶剤
５ml中、８０℃で９時間反応させた後、メタノールを５
０ｇ、Ｐｔ／Ｃを1.５ｇ添加し、４５℃で５時間、水添
反応を行なつた。この後、窒素下で触媒を濾別した後、
反応液に水３０mlを加え、窒素下で６０℃まで加熱した
後、冷却して、エチルイソアミルケト酸を析出させ、こ
れを窒素下に濾過した。その結果、５５０ｎｍにおける
吸光度が0.０５のケト酸を原料アミノフェノール基準に
て７５％の収率で得ることができた。Example 8 N-ethyl-N-isoamyl-m-aminophenol (10.35 g) and phthalic anhydride (14.8 g) were reacted in 5 ml of an acetic acid solvent at 80 ° C. for 9 hours, and then methanol was added. 5
0 g and 1.5 g of Pt / C were added, and a hydrogenation reaction was carried out at 45 ° C. for 5 hours. Then, after filtering off the catalyst under nitrogen,
30 ml of water was added to the reaction solution, which was heated to 60 ° C. under nitrogen, and then cooled to precipitate ethyl isoamylketoacid, which was filtered under nitrogen. As a result, a keto acid having an absorbance at 550 nm of 0.05 was obtained in a yield of 75% based on the starting aminophenol.
【００２４】実施例９ 実施例２において、５５０ｎｍの吸光度が0.７５のジブ
チルケト酸を用いた以外は、実施例２と全く同様に行な
つた。その結果、５５０ｎｍにおける吸光度が0.０３４
のジブチルケト酸を８９％の回収率で得た。Example 9 The procedure of Example 2 was repeated, except that dibutylketo acid having an absorbance at 550 nm of 0.75 was used. As a result, the absorbance at 550 nm was 0.034.
Of dibutyl keto acid with a recovery of 89%.
【００２５】実施例１０ ローダミンに由来する５５０ｎｍの吸光度が4.５である
エチルイソアミルケト酸５ｇをトルエン１５ｇに溶解さ
せた後、これに水添触媒としてラネーニッケル1.２ｇを
加え、７０℃まで加温した後、水添反応を行なつた。反
応終了後、触媒を熱時濾過し、得られた濾液をそのま
ま、冷却して、ケト酸を晶析させ、濾過した。その結
果、５５０ｎｍにおける吸光度が0.００５であるケト酸
を回収率９５％にて得た。Example 10 5 g of ethylisoamylketoacid derived from rhodamine and having an absorbance at 550 nm of 4.5 was dissolved in 15 g of toluene, and 1.2 g of Raney nickel as a hydrogenation catalyst was added thereto. After warming, a hydrogenation reaction was performed. After completion of the reaction, the catalyst was filtered while hot, and the obtained filtrate was cooled as it was to crystallize the keto acid and filtered. As a result, keto acid having an absorbance at 550 nm of 0.005 was obtained at a recovery of 95%.
【００２６】[0026]
【発明の効果】以上のように、本発明の方法によれば、
ローダミン等の着色物質を含有するケト酸を水添処理す
ることによつて、極めて色相の良好なケト酸誘導体を容
易に得ることができる。このように、本発明の方法によ
れば、アルカリ等を用いることなく、従つて、中和排水
等を排出することなく、工業的に有利にケト酸を精製す
ることができる。As described above, according to the method of the present invention,
By hydrogenating a keto acid containing a coloring substance such as rhodamine, a keto acid derivative having an extremely good hue can be easily obtained. As described above, according to the method of the present invention, keto acids can be industrially advantageously purified without using an alkali or the like, and thus without discharging neutralized wastewater or the like.
【００２７】更に、本発明の方法によれば、たとえば、
N,Ｎ−ジアルキル−ｍ−アミノフェノールと無水フタル
酸との反応によつてケト酸誘導体を製造する場合、反応
によつて得られたケト酸を単離することなく、ケト酸を
含む反応液を直接に水添処理することによつて、簡単な
プロセスにて色相の良好なケト酸誘導体を得ることがで
きる。Further, according to the method of the present invention, for example,
When producing a keto acid derivative by reacting N, N-dialkyl-m-aminophenol with phthalic anhydride, the reaction solution containing keto acid can be obtained without isolating the keto acid obtained by the reaction. By directly hydrogenating the compound, a keto acid derivative having a good hue can be obtained by a simple process.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−70350（ＪＰ，Ａ) 特開 平３−261756（ＪＰ，Ａ) 特開 昭50−13310（ＪＰ，Ａ) 特開 昭48−52708（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 229/52 C07C 227/40 C07C 227/42 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-70350 (JP, A) JP-A-3-261756 (JP, A) JP-A-50-13310 (JP, A) JP-A 48-48 52708 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 229/52 C07C 227/40 C07C 227/42 CA (STN) REGISTRY (STN)
Claims (5)
ールと無水フタル酸との反応によつて得られる一般式
（Ｉ） 【化１】 （式中、R1及びR2はそれぞれ独立に炭素数１〜６のアル
キル基を示す。）で表わされるケト酸誘導体の精製方法
において、このケト酸誘導体を反応溶剤中にて水添触媒
の存在下に水添し、得られた反応液からケト酸誘導体を
回収することを特徴とするケト酸の精製方法。1. A compound of the general formula (I) obtained by reacting N, N-dialkyl-m-metaaminophenol with phthalic anhydride. (Wherein R 1 and R 2 each independently represent an alkyl group having 1 to 6 carbon atoms). In a method for purifying a keto acid derivative represented by the formula: A method for purifying a keto acid, comprising hydrogenating in the presence of the compound and recovering a keto acid derivative from the obtained reaction solution.
ト酸誘導体を晶析によつて回収することを特徴とする請
求項１に記載のケト酸の精製方法。2. The method for purifying a keto acid according to claim 1, wherein the keto acid derivative is recovered from the reaction solution by crystallization after hydrogenating the keto acid derivative.
に対する貧溶剤を反応液に加え、ケト酸誘導体を晶析に
よつて回収することを特徴とする請求項１に記載のケト
酸の精製方法。3. The keto acid according to claim 1, wherein after the hydrogenation of the keto acid derivative, a poor solvent for the keto acid derivative is added to the reaction solution, and the keto acid derivative is recovered by crystallization. Purification method.
とする請求項１に記載のケト酸誘導体の精製方法。4. The method for purifying a keto acid derivative according to claim 1, wherein the reaction solvent is a water-soluble solvent.
加えて、ケト酸誘導体を晶析によつて回収することを特
徴とする請求項１乃至４のいずれかに記載のケト酸の精
製方法。5. The keto acid according to claim 1, wherein after the keto acid derivative is hydrogenated, water is added to the reaction solution, and the keto acid derivative is recovered by crystallization. A method for purifying an acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15250192A JP3204538B2 (en) | 1992-06-11 | 1992-06-11 | Purification method of keto acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15250192A JP3204538B2 (en) | 1992-06-11 | 1992-06-11 | Purification method of keto acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05339220A JPH05339220A (en) | 1993-12-21 |
| JP3204538B2 true JP3204538B2 (en) | 2001-09-04 |
Family
ID=15541847
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15250192A Expired - Lifetime JP3204538B2 (en) | 1992-06-11 | 1992-06-11 | Purification method of keto acid |
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| Country | Link |
|---|---|
| JP (1) | JP3204538B2 (en) |
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|---|---|
| JPH05339220A (en) | 1993-12-21 |
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