JP2547100B2 - Process for producing 2,4,5-trifluoro-3-alkoxybenzoic acid - Google Patents
Process for producing 2,4,5-trifluoro-3-alkoxybenzoic acidInfo
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- JP2547100B2 JP2547100B2 JP1264956A JP26495689A JP2547100B2 JP 2547100 B2 JP2547100 B2 JP 2547100B2 JP 1264956 A JP1264956 A JP 1264956A JP 26495689 A JP26495689 A JP 26495689A JP 2547100 B2 JP2547100 B2 JP 2547100B2
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- trifluoro
- acid
- alkoxybenzoic
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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、2,4,5−トリフルオロ−３−アルコキシ安
息香酸の製造法に関するものであり、本発明によって製
造される2,4,5−トリフルオロ−３−アルコキシ安息香
酸は、農薬、医薬、特にキノロンカルボン酸系抗菌剤の
製造原料として有用である。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing 2,4,5-trifluoro-3-alkoxybenzoic acid, which is produced by the present invention. 5-Trifluoro-3-alkoxybenzoic acid is useful as a raw material for producing agricultural chemicals, pharmaceuticals, especially quinolonecarboxylic acid antibacterial agents.
従来の2,4,5−トリフルオロ−３−アルコキシ安息香
酸の製造方法としては、例えば特開昭63−198664号公報
〔明細書14頁右下欄（経路Ｆ）参照〕の記載に準じて、
2,3,4,5,6−ペンタフルオロベンゾニトリルを原料とし
て製造する方法がある。しかし、この製造方法は、７工
程もの長い工程を必要とする工程であり、また、収率も
10％程度と低いことなどの点で工業的に満足できる方法
ではなかった。As a conventional method for producing 2,4,5-trifluoro-3-alkoxybenzoic acid, for example, according to the description in JP-A-63-198664 [see page 14, lower right column (route F) of the specification]. ,
There is a method of producing using 2,3,4,5,6-pentafluorobenzonitrile as a raw material. However, this manufacturing method requires a long process of 7 steps, and the yield is also high.
It was not an industrially satisfactory method in that it was as low as 10%.
発明者らは、前記のような問題点を解決すべく、鋭意
検討した結果、2,4,5−トリフルオロ−３−ヒドロキシ
安息香酸（特開昭63−264440号公報参照）を出発物質と
して用いることにより、簡便に、高収率で2,4,5−トリ
フルオロ−３−アルコキシ安息香酸を製造できることを
見出して本発明を完成した。本発明の目的は、簡便で、
高収率で2,4,5−トリフルオロ−３−アルコキシ安息香
酸を製造する工業的な製造方法を提供することにある。As a result of intensive studies to solve the above problems, the inventors have used 2,4,5-trifluoro-3-hydroxybenzoic acid (see JP-A-63-264440) as a starting material. The present invention has been completed by finding that by using it, 2,4,5-trifluoro-3-alkoxybenzoic acid can be easily produced in high yield. The purpose of the present invention is simple,
An object of the present invention is to provide an industrial production method for producing 2,4,5-trifluoro-3-alkoxybenzoic acid in high yield.
本発明は、 式 で表わされる2,4,5−トリフルオロ−３−ヒドロキシ安
息香酸をアルキル化し、生成する一般式（II） （式中、R1は低級アルキル基を示す）で表わされる2,4,
5−トリフルオロ−３−アルコキシ安息香酸アルキルエ
ステルを分離する工程１と、2,4,5−トリフルオロ−３
−アルコキシ安息香酸アルキルエステルを加水分解する
工程２よりなることを特徴とする一般式（Ｉ） （式中、R1は前記と同じ意味を示す）で表わされる2,4,
5−トリフルオロ−３−アルコキシ安息香酸の製造法に
関する。The present invention has the formula A general formula (II) produced by alkylating 2,4,5-trifluoro-3-hydroxybenzoic acid represented by (Wherein R 1 represents a lower alkyl group) 2,4,
Step 1, separating the 5-trifluoro-3-alkoxybenzoic acid alkyl ester, and 2,4,5-trifluoro-3
A general formula (I), characterized in that it comprises a step 2 of hydrolysing an alkoxyalkoxybenzoic acid alkyl ester. (Wherein R 1 has the same meaning as described above) 2,4,
The present invention relates to a method for producing 5-trifluoro-3-alkoxybenzoic acid.
この製造法は、2,4,5−トリフルオロ−３−メトキシ
安息香酸を製造する方法として特に好ましい。This production method is particularly preferable as a method for producing 2,4,5-trifluoro-3-methoxybenzoic acid.
本発明の製法は、2,4,5−トリフルオロ−３−ヒドロ
キシ安息香酸のアルキル化反応により、３位の水酸基を
アルキル化すると同時に１位のカルボン酸もエステル化
して、一般式（II）で表わされる2,4,5−トリフルオロ
−３−アルコキシ安息香酸アルキルエステルを生成させ
るアルキル化反応工程（工程１）と、さらに加水分解し
て2,4,5−トリフルオロ−３−アルコキシ安息香酸を得
る加水分解反応工程（工程２）よりなる。According to the production method of the present invention, a hydroxyl group at the 3-position is alkylated by an alkylation reaction of 2,4,5-trifluoro-3-hydroxybenzoic acid, and at the same time, a carboxylic acid at the 1-position is esterified to give a compound represented by the general formula (II): And an alkylation reaction step (step 1) for forming a 2,4,5-trifluoro-3-alkoxybenzoic acid alkyl ester represented by It comprises a hydrolysis reaction step (step 2) of obtaining an acid.
本発明において、出発物質として用いられる2,4,5−
トリフルオロ−３−ヒドロキシ安息香酸は、特開昭63−
264440号公報に記載の方法に準じて製造されるが、詳し
くは参考例で示す。In the present invention, 2,4,5-used as a starting material
Trifluoro-3-hydroxybenzoic acid is disclosed in JP-A-63-
It is produced according to the method described in Japanese Patent No. 264440, but details will be shown in Reference Examples.
アルキル化反応工程（工程１） 本発明の工程１は、フェノール性水酸基をアルキル化
する際の常法に従い、溶媒中、2,4,5−トリフルオロ−
３−ヒドロキシ安息香酸に、ジメチル硫酸等のジアルキ
ル硫酸類や塩化メチル等のアルキルハライド類などのア
ルキル化剤を、アルキル金属の炭酸塩、水酸化物、炭酸
水素塩等のアルカリ性化合物の存在下に反応させる工程
である。この工程は、炭素数１〜４程度の低級アルキル
基を導入するのに好適であり、特にメチル基を導入する
のに好適である。Alkylation reaction step (step 1) In the step 1 of the present invention, 2,4,5-trifluoro-in a solvent is used according to a conventional method for alkylating a phenolic hydroxyl group.
In addition to 3-hydroxybenzoic acid, an alkylating agent such as dialkyl sulfates such as dimethyl sulfate and alkyl halides such as methyl chloride in the presence of an alkaline compound such as an alkyl metal carbonate, hydroxide or hydrogen carbonate. This is a step of reacting. This step is suitable for introducing a lower alkyl group having about 1 to 4 carbon atoms, and particularly suitable for introducing a methyl group.
前記のアルキル化剤およびアルカリ性化合物は、2,4,
5−トリフルオロ−３−ヒドロキシ安息香酸１モルに対
して理論量である２当量または２当量以上使用すること
が好ましい。The alkylating agent and the alkaline compound are 2,4,
It is preferable to use a theoretical amount of 2 equivalents or 2 equivalents or more per 1 mol of 5-trifluoro-3-hydroxybenzoic acid.
前記の有機溶媒としては、2,4,5−トリフルオロ−３
−ヒドロキシ安息香酸を反応に十分な程度に溶解し、本
反応に不活性な溶媒であればよく、例えばメタノール等
のアルコール系溶媒、アセトン等のケトン系溶媒を挙げ
ることができる。Examples of the organic solvent include 2,4,5-trifluoro-3
A solvent that dissolves -hydroxybenzoic acid in a sufficient amount for the reaction and is inert to the reaction may be used, and examples thereof include alcohol solvents such as methanol and ketone solvents such as acetone.
反応温度は、反応を促進するために、使用する有機溶
媒の沸点付近に加熱し、還流状態で反応させることが好
ましい。In order to accelerate the reaction, it is preferable to heat the reaction temperature to around the boiling point of the organic solvent used and carry out the reaction in the reflux state.
本発明の工程１における反応時間としては、使用する
反応温度によっても異なるが、２〜６時間が好ましい。The reaction time in step 1 of the present invention varies depending on the reaction temperature used, but is preferably 2 to 6 hours.
このようにして得られる、2,4,5−トリフルオロ−３
−アルコキシ安息香酸アルキルエステルは、アルキル化
剤により規定されるが、具体例としては、例えば2,4,5
−トリフルオロ−３−メトキシ安息香酸メチルエステ
ル、2,4,5−トリフルオロ−３−エトキシ安息香酸エチ
ルエステル、2,4,5−トリフルオロ−３−プロポキシ安
息香酸プロピルエステル、2,4,5−トリフルオロ−３−
ブトキシ安息香酸ブチルエステルなどを挙げることがで
き、好ましくは2,4,5−トリフルオロ−３−メトキシ安
息香酸メチルエステルである。2,4,5-trifluoro-3 thus obtained
-Alkoxybenzoic acid alkyl ester is defined by an alkylating agent, and specific examples thereof include 2,4,5
-Trifluoro-3-methoxybenzoic acid methyl ester, 2,4,5-trifluoro-3-ethoxybenzoic acid ethyl ester, 2,4,5-trifluoro-3-propoxybenzoic acid propyl ester, 2,4, 5-trifluoro-3-
Butoxybenzoic acid butyl ester and the like can be mentioned, and 2,4,5-trifluoro-3-methoxybenzoic acid methyl ester is preferable.
本発明の工程１で得られる2,4,5−トリフルオロ−３
−アルコキシ安息香酸アルキルエステルを含む反応混合
物１から2,4,5−トリフルオロ−３−アルコキシ安息香
酸アルキルエステルを得る方法は、通常の分離操作を組
合わせて行えばよく、例えば反応混合物１を中和して減
圧濃縮により有機溶媒を除いた後、溶媒抽出に適した有
機溶媒による溶媒抽出、減圧濃縮、減圧蒸留を用いる方
法などで2,4,5−トリフルオロ−３−アルコキシ安息香
酸アルキルエステルを得ることが好ましい。2,4,5-Trifluoro-3 obtained in step 1 of the present invention
The method for obtaining the 2,4,5-trifluoro-3-alkoxybenzoic acid alkyl ester from the reaction mixture 1 containing the -alkoxybenzoic acid alkyl ester may be carried out by combining ordinary separation operations. After removing the organic solvent by neutralization and concentration under reduced pressure, a method such as solvent extraction with an organic solvent suitable for solvent extraction, concentration under reduced pressure, distillation under reduced pressure, etc. is used to alkyl 2,4,5-trifluoro-3-alkoxybenzoate. Preference is given to obtaining esters.
加水分解反応工程（工程２） 本願の発明における工程２は、前記工程１で生成した
2,4,5−トリフルオロ−３−アルコキシ安息香酸アルキ
ルエステルを加水分解して2,4,5−トリフルオロ−３−
アルコキシ安息香酸を得る工程である。Hydrolysis reaction step (step 2) The step 2 in the invention of the present application was generated in the above step 1.
2,4,5-Trifluoro-3-alkoxybenzoic acid alkyl ester is hydrolyzed to give 2,4,5-trifluoro-3-
This is a step of obtaining alkoxybenzoic acid.
この加水分解工程は通常のカルボン酸エステルの加水
分解反応を適用すればよく、加水分解剤としては、強ア
ルカリ物質または強酸物質であればよい。アルカリ性の
方が反応が早いので強アルカリ物質であることが好まし
い。In this hydrolysis step, a usual hydrolysis reaction of carboxylic acid ester may be applied, and the hydrolyzing agent may be a strong alkaline substance or a strong acid substance. It is preferable that the substance is a strong alkaline substance because the alkaline substance reacts faster.
強アルカリ物質としては、例えば前記の本発明の工程
１において用いられるアルカリ性化合物を挙げることが
できる。Examples of the strong alkaline substance include the alkaline compounds used in the above-mentioned step 1 of the present invention.
工程２において用いられる溶媒は、本反応に不活性な
溶媒であればよく、例えば水またはメタノールなどのア
ルコール系有機溶媒と水との混合物を挙げることができ
る。The solvent used in step 2 may be any solvent inert to this reaction, and examples thereof include a mixture of water or an alcohol organic solvent such as methanol and water.
反応温度としては、室温でも反応は進行するため加熱
は必ずしも必要としないが、加熱により反応時間が短縮
する傾向がある。As for the reaction temperature, heating is not always necessary because the reaction proceeds even at room temperature, but heating tends to shorten the reaction time.
このようにして得られる、2,4,5−トリフルオロ−３
−アルコキシ安息香酸は、2,4,5−トリフルオロ−３−
アルコキシ安息香酸アルキルエステルによって規定され
るが、具体例としては、例えば2,4,5−トリフルオロ−
３−メトキシ安息香酸、2,4,5−トリフルオロ−３−エ
トキシ安息香酸、2,4,5−トリフルオロ−３−プロポキ
シ安息香酸、2,4,5−トリフルオロ−３−ブトキシ安息
香酸などを挙げることができ、好ましくは2,4,5−トリ
フルオロ−３−メトキシ安息香酸である。2,4,5-trifluoro-3 thus obtained
-Alkoxybenzoic acid is 2,4,5-trifluoro-3-
It is defined by an alkoxy benzoic acid alkyl ester, and specific examples include 2,4,5-trifluoro-
3-methoxybenzoic acid, 2,4,5-trifluoro-3-ethoxybenzoic acid, 2,4,5-trifluoro-3-propoxybenzoic acid, 2,4,5-trifluoro-3-butoxybenzoic acid And the like, and preferably 2,4,5-trifluoro-3-methoxybenzoic acid.
工程２で得られる2,4,5−トリフルオロ−３−アルコ
キシ安息香酸を含む反応混合物２から2,4,5−トリフル
オロ−３−アルコキシ安息香酸を得る方法は、強アルカ
リ性物質で加水分解を行った場合、反応混合物２に塩
酸、硫酸などの鉱酸を加えて、酸性とした後に、通常の
抽出操作、分離操作を組合わせて行えばよく、例えば反
応混合物２に、濃塩酸を加えてpHを２付近とし、析出す
る結晶を採集するか、有機溶媒で抽出し減圧濃縮を用い
る方法などで2,4,5−トリフルオロ−３−アルコキシ安
息香酸を得ることが好ましい。The method for obtaining 2,4,5-trifluoro-3-alkoxybenzoic acid from the reaction mixture 2 containing 2,4,5-trifluoro-3-alkoxybenzoic acid obtained in step 2 is as follows. In the case of carrying out, the reaction mixture 2 may be added with a mineral acid such as hydrochloric acid or sulfuric acid to make it acidic, and then a combination of ordinary extraction operation and separation operation may be performed. For example, concentrated hydrochloric acid may be added to the reaction mixture 2. It is preferable to adjust the pH to about 2 and collect the precipitated crystals, or to obtain 2,4,5-trifluoro-3-alkoxybenzoic acid by a method such as extraction with an organic solvent and concentration under reduced pressure.
以下本発明を実施例および参考例により具体的に説明
するが、本発明はこれらに限定されるものではない。Hereinafter, the present invention will be specifically described with reference to Examples and Reference Examples, but the present invention is not limited thereto.
〔実施例１〕 2,4,5−トリフルオロ−３−ヒドロキシ安息香酸5.76g
（0.03モル）をアセトン50mlに溶解し、炭酸カリウム9.
11g（0.066モル）とジメチル硫酸8.32g（0.066モル）を
加え、２時間加熱還流した。反応液に1N−塩酸水溶液30
ml（0.05モル）を加えてアセトンを減圧留去した後クロ
ロホルムで抽出した。抽出したクロロホルム層を乾燥後
濃縮し、残渣を減圧蒸留して、2,4,5−トリフルオロ−
３−メトキシ安息香酸メチルを6.0g得た。[Example 1] 2,4,5-trifluoro-3-hydroxybenzoic acid 5.76 g
(0.03 mol) dissolved in 50 ml of acetone, potassium carbonate 9.
11 g (0.066 mol) and 8.32 g (0.066 mol) of dimethylsulfate were added, and the mixture was heated under reflux for 2 hours. 1N hydrochloric acid solution in the reaction solution 30
ml (0.05 mol) was added and acetone was distilled off under reduced pressure, followed by extraction with chloroform. The extracted chloroform layer was dried and concentrated, and the residue was distilled under reduced pressure to give 2,4,5-trifluoro-
6.0 g of methyl 3-methoxybenzoate was obtained.
沸点95〜97℃/4mmHg。Boiling point 95-97 ℃ / 4mmHg.
収率 91％。Yield 91%.
マススペクトル:m/z 220（M+） プロトンNMRスペクトル（CDCl3、δppm） 7.48（m,1H,3JHF 10.25Hz,4JHF 8.43Hz,4JHF 6.11H
z,芳香族プロトン）、4.05（m,フッ素との小さなカップ
リングが認められる,3H,OCH3）、3.94（s,3H,CO2CH3） 上記の2,4,5−トリフルオロ−３−メトキシ安息香酸
メチル6.0g（0.027モル）に1N−水酸化ナトリウム水溶
液30mlを加え６時間室温で撹拌した。この溶液に濃塩酸
6mlを加え、析出した結晶を濾過し、水洗後減圧乾燥し
て2,4,5−トリフルオロ−３−メトキシ安息香酸5.3gを
無色粉末として得た。Mass spectrum: m / z 220 (M + ) Proton NMR spectrum (CDCl 3 , δppm) 7.48 (m, 1H, 3JHF 10.25Hz, 4JHF 8.43Hz, 4JHF 6.11H
z, aromatic protons), 4.05 (m, small coupling with fluorine is permitted, 3H, OCH 3), 3.94 (s, 3H, CO 2 CH 3) The above 2,4,5 -3 To 6.0 g (0.027 mol) of methyl methoxybenzoate was added 30 ml of a 1N sodium hydroxide aqueous solution, and the mixture was stirred at room temperature for 6 hours. Concentrated hydrochloric acid in this solution
6 ml was added, and the precipitated crystals were filtered, washed with water and dried under reduced pressure to obtain 5.3 g of 2,4,5-trifluoro-3-methoxybenzoic acid as a colorless powder.
融点113〜116℃。Melting point 113-116 [deg.] C.
収率95％。95% yield.
マススペクトル:m/z 206（M+）。Mass spectrum: m / z 206 (M + ).
プロトンNMRスペクトル（CDCl3、δppm） 7.50（m,3JHF 10.2Hz,4JHF 8.5Hz,4JHF 6.1Hz,1H,芳
香族プロトン）、5.00（br,1H,CO2H）、4.03（m,3H,OCH
3） 〔参考例１〕 200mlのガラスオートクレーブ中で86％水酸化カリウ
ム18.16g（0.28モル）を水50mlに溶解し80℃に加熱した
後、テトラフルオロフタル酸10.0g（0.042モル）を反応
温度が85〜90℃に維持されるように分割添加した。Proton NMR spectrum (CDCl 3 , δppm) 7.50 (m, 3JHF 10.2Hz, 4JHF 8.5Hz, 4JHF 6.1Hz, 1H, aromatic proton), 5.00 (br, 1H, CO 2 H), 4.03 (m, 3H, OCH
3 ) [Reference Example 1] In a 200 ml glass autoclave, 18.16 g (0.28 mol) of 86% potassium hydroxide was dissolved in 50 ml of water and heated to 80 ° C, and then 10.0 g (0.042 mol) of tetrafluorophthalic acid was added at the reaction temperature. Was added in portions so that the temperature was maintained at 85-90 ° C.
添加終了後90〜95℃で３時間撹拌し、濃塩酸20ml（0.
24モル）を添加して140℃で３時間撹拌した。この間、
発生する炭酸ガスによって反応器内の圧力が上昇するた
め、時々ガスを抜いて圧力を3kg/cm2になるように調整
した。After the addition was completed, the mixture was stirred at 90 to 95 ° C for 3 hours, and concentrated hydrochloric acid 20 ml (0.
24 mol) was added and the mixture was stirred at 140 ° C. for 3 hours. During this time,
Since the pressure in the reactor rises due to the generated carbon dioxide gas, the gas was occasionally vented to adjust the pressure to 3 kg / cm 2 .
反応終了後、反応液を室温まで冷却し濃塩酸10mlを加
えてpH2以下とし、酢酸エチルで抽出した。有機層を水
洗、乾燥後、減圧濃縮して、2,4,5−トリフルオロ−３
−ヒドロキシ安息香酸6.93gを無色粉末として得た。After completion of the reaction, the reaction solution was cooled to room temperature, adjusted to pH 2 or less with 10 ml of concentrated hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with water, dried, and concentrated under reduced pressure to give 2,4,5-trifluoro-3.
-6.93 g of hydroxybenzoic acid was obtained as a colorless powder.
融点142〜145℃。Melting point 142-145 [deg.] C.
マススペクトル： m/z 192（M+） 〔発明の効果〕 本発明の製法を用いると、抗菌剤として用いられるキ
ノロンカルボン酸誘導体の合成中間体として有用な2,4,
5−トリフルオロ−３−アルコキシ安息香酸を、簡便
に、高収率で製造することができる。Mass spectrum: m / z 192 (M + ) [Effect of the invention] The production method of the present invention is useful as a synthetic intermediate for a quinolonecarboxylic acid derivative used as an antibacterial agent.
5-Trifluoro-3-alkoxybenzoic acid can be easily produced in high yield.
Claims (2)
息香酸をアルキル化し、生成する一般式（II） （式中、R1は低級アルキル基を示す）で表わされる2,4,
5−トリフルオロ−３−アルコキシ安息香酸アルキルエ
ステルを分離する工程１と、2,4,5−トリフルオロ−３
−アルコキシ安息香酸アルキルエステルを加水分解する
工程２よりなることを特徴とする一般式（Ｉ） （式中、R1は前記と同じ意味を示す）で表わされる2,4,
5−トリフルオロ−３−アルコキシ安息香酸の製造法。1. A formula A general formula (II) produced by alkylating 2,4,5-trifluoro-3-hydroxybenzoic acid represented by (Wherein R 1 represents a lower alkyl group) 2,4,
Step 1, separating the 5-trifluoro-3-alkoxybenzoic acid alkyl ester, and 2,4,5-trifluoro-3
A general formula (I), characterized in that it comprises a step 2 of hydrolysing an alkoxyalkoxybenzoic acid alkyl ester. (Wherein R 1 has the same meaning as described above) 2,4,
Process for producing 5-trifluoro-3-alkoxybenzoic acid.
息香酸をメチル化して、生成する2,4,5−トリフルオロ
−３−メトキシ安息香酸メチルエステルを分離する工程
１と、2,4,5−トリフルオロ−３−メトキシ安息香酸メ
チルエステルを加水分解する工程２よりなることを特徴
とする2,4,5−トリフルオロ−３−メトキシ安息香酸の
製造法。2. Steps 1 and 2 in which 2,4,5-trifluoro-3-hydroxybenzoic acid is methylated to separate the resulting 2,4,5-trifluoro-3-methoxybenzoic acid methyl ester. A method for producing 2,4,5-trifluoro-3-methoxybenzoic acid, which comprises the step 2 of hydrolyzing methyl 4,4,5-trifluoro-3-methoxybenzoate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1264956A JP2547100B2 (en) | 1989-10-13 | 1989-10-13 | Process for producing 2,4,5-trifluoro-3-alkoxybenzoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1264956A JP2547100B2 (en) | 1989-10-13 | 1989-10-13 | Process for producing 2,4,5-trifluoro-3-alkoxybenzoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03127755A JPH03127755A (en) | 1991-05-30 |
| JP2547100B2 true JP2547100B2 (en) | 1996-10-23 |
Family
ID=17410540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1264956A Expired - Lifetime JP2547100B2 (en) | 1989-10-13 | 1989-10-13 | Process for producing 2,4,5-trifluoro-3-alkoxybenzoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2547100B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5233082A (en) * | 1982-11-16 | 1993-08-03 | Occidental Chemical Corporation | Method of making 3-hydroxy-2,4,5-trifluorobenzoic acid |
| WO2008093837A1 (en) | 2007-02-02 | 2008-08-07 | Ube Industries, Ltd. | Ester compound, and non-aqueous electrolyte solution and lithium secondary battery each using the ester compound |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0696545B2 (en) * | 1986-12-08 | 1994-11-30 | 宇部興産株式会社 | Process for producing 3,5,6-trifluoro-4-hydroxyphthalic acid |
| JP2725179B2 (en) * | 1988-04-21 | 1998-03-09 | 日本カーバイド工業株式会社 | Method for producing 2,4,5-trifluoro-3-hydroxybenzoic acid |
-
1989
- 1989-10-13 JP JP1264956A patent/JP2547100B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03127755A (en) | 1991-05-30 |
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