JPH0610159B2 - Process for producing 3-hydroxy-2,4,5-trifluorobenzoic acid - Google Patents
Process for producing 3-hydroxy-2,4,5-trifluorobenzoic acidInfo
- Publication number
- JPH0610159B2 JPH0610159B2 JP62159712A JP15971287A JPH0610159B2 JP H0610159 B2 JPH0610159 B2 JP H0610159B2 JP 62159712 A JP62159712 A JP 62159712A JP 15971287 A JP15971287 A JP 15971287A JP H0610159 B2 JPH0610159 B2 JP H0610159B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- hydroxy
- reaction
- trifluorobenzoic
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- YYAFUGSJSHXYNK-UHFFFAOYSA-N 2,4,5-trifluoro-3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC(F)=C(F)C(O)=C1F YYAFUGSJSHXYNK-UHFFFAOYSA-N 0.000 title claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 20
- BYXIMXYJZPMWAX-UHFFFAOYSA-N 3,4,6-trifluoro-5-hydroxyphthalic acid Chemical compound OC(=O)C1=C(F)C(O)=C(F)C(F)=C1C(O)=O BYXIMXYJZPMWAX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 238000006114 decarboxylation reaction Methods 0.000 claims description 3
- AKAMNXFLKYKFOJ-UHFFFAOYSA-N 2,4,5-trifluorobenzoic acid Chemical compound OC(=O)C1=CC(F)=C(F)C=C1F AKAMNXFLKYKFOJ-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 15
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 9
- YJLVXRPNNDKMMO-UHFFFAOYSA-N 3,4,5,6-tetrafluorophthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(F)C(F)=C1C(O)=O YJLVXRPNNDKMMO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- YVZFWLVZIITCSM-UHFFFAOYSA-N 3,4,5-trifluorophthalic acid Chemical compound OC(=O)C1=CC(F)=C(F)C(F)=C1C(O)=O YVZFWLVZIITCSM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- -1 for example Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WEPXLRANFJEOFZ-UHFFFAOYSA-N 2,3,4-trifluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C(F)=C1F WEPXLRANFJEOFZ-UHFFFAOYSA-N 0.000 description 1
- SSEYCYSXJAYOSV-UHFFFAOYSA-N 4,4,5-trifluorocyclohexa-1,5-diene-1-carboxylic acid Chemical compound FC1(CC=C(C(=O)O)C=C1F)F SSEYCYSXJAYOSV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- TXHIDIHEXDFONW-UHFFFAOYSA-N benzene;propan-2-one Chemical compound CC(C)=O.C1=CC=CC=C1 TXHIDIHEXDFONW-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は式（Ｉ）で示される３−ヒドロキシ−２，４，
５−トリフルオロ安息香酸の製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to 3-hydroxy-2,4 represented by the formula (I).
The present invention relates to a method for producing 5-trifluorobenzoic acid.
本発明によって提供される新規な３−ヒドロキシ−2,4,
5−トリフルオロ安息香酸は高分子材料、医薬品および
農薬における原料として有用なものである。 The novel 3-hydroxy-2,4, provided by the present invention,
5-Trifluorobenzoic acid is useful as a raw material in polymer materials, pharmaceuticals and agricultural chemicals.
〈従来の技術〉 本発明における３−ヒドロキシ−2,4,5−トリフルオロ
安息香酸及びその製法は、今まで全く報告されていな
い。<Prior Art> 3-Hydroxy-2,4,5-trifluorobenzoic acid and a method for producing the same in the present invention have not been reported at all until now.
〈発明の構成〉 本発明者らは新規な３−ヒドロキシ−2,4,5−トリフル
オロ安息香酸の製造方法を検討した結果、当該化合物は
４−ヒドロキシ−3,5,6−トリフルオロフタル酸を酸あ
るいはアルカリ性物質等の触媒の存在下で加熱すること
によって脱炭酸反応をおこなわせしめ製造できることを
見いだした。酸性物質としては、例えば硫酸、塩酸等の
鉱酸などを使用することができるが、特に硫酸の使用が
好ましい。アルカリ性物質としては、例えばナトリウ
ム、カリウム、カルシウムの水酸化物、炭酸塩等を使用
することができるが、特に水酸化カルシウムの使用が好
ましい。<Structure of Invention> As a result of studying a novel method for producing 3-hydroxy-2,4,5-trifluorobenzoic acid, the present inventors have found that the compound is 4-hydroxy-3,5,6-trifluorophthalic acid. It was found that the decarboxylation reaction can be carried out by heating an acid in the presence of a catalyst such as an acid or an alkaline substance to produce the compound. As the acidic substance, for example, mineral acids such as sulfuric acid and hydrochloric acid can be used, and the use of sulfuric acid is particularly preferable. As the alkaline substance, for example, hydroxides, carbonates, etc. of sodium, potassium and calcium can be used, but calcium hydroxide is particularly preferable.
本発明の製造方法を具体的に示せば４−ヒドロキシトリ
フルオロフタル酸を水性媒体中９０〜２００℃の温度範
囲で酸あるいはアルカリ性物質等の触媒の存在下に加熱
することによって、脱炭酸反応を行なわせしめ、新規な
３−ヒドロキシ−2,4,5−トリフルオロ安息香酸を高い
収率で製造できる。More specifically, the production method of the present invention is carried out by heating 4-hydroxytrifluorophthalic acid in an aqueous medium in the temperature range of 90 to 200 ° C. in the presence of a catalyst such as an acid or an alkaline substance to effect the decarboxylation reaction. The new 3-hydroxy-2,4,5-trifluorobenzoic acid can be produced in high yield.
本発明で触媒として特に硫酸を使用する場合、反応に供
する硫酸濃度は２０〜９０重量％の範囲の濃度で行なう
のがよいが、好ましくは５０〜８０重量％の範囲がよ
い。仕込み濃度は４−ヒドロキシ−3,5,6−トリフルオ
ロフタル酸１００部に対し、硫酸水溶液１００〜１００
０部の範囲で仕込むのが望ましいが、好ましくは３００
〜７００部の範囲で仕込むのがよい。また触媒として特
にアルカリ性物質を使用する場合、反応に供するアルカ
リ量は、４−ヒドロキシ−3,5,6−トリフルオロフタル
酸１モルに対し、0.０１〜0.４モルの範囲で仕込むのが
よい。仕込み濃度は４−ヒドロキシ−3,5,6−トリフル
オロフタル酸１００部に対し、水１００〜１０００部で
仕込むのが望ましいが、好ましくは３００〜７００部の
範囲で仕込むのがよい。When sulfuric acid is used as a catalyst in the present invention, the concentration of sulfuric acid used for the reaction is preferably 20 to 90% by weight, preferably 50 to 80% by weight. The charged concentration is 100 to 100 parts of 4-hydroxy-3,5,6-trifluorophthalic acid, and the sulfuric acid aqueous solution is 100 to 100.
It is desirable to charge in the range of 0 part, but preferably 300
It is recommended to prepare the mixture in the range of up to 700 parts. When an alkaline substance is used as a catalyst, the amount of alkali to be used in the reaction is 0.01 to 0.4 mol per 1 mol of 4-hydroxy-3,5,6-trifluorophthalic acid. Is good. It is preferable that 100-1000 parts of water be added to 100 parts of 4-hydroxy-3,5,6-trifluorophthalic acid, and preferably 300-700 parts.
反応温度は９０〜２００℃の温度範囲で選ぶのが好まし
いが、特に１３０〜１７０℃の範囲が好ましい。The reaction temperature is preferably selected in the temperature range of 90 to 200 ° C, and particularly preferably in the range of 130 to 170 ° C.
反応温度が高い場合、急激な反応が起こり、発熱反応の
為危険であり、また反応温度が低い場合、反応速度が低
下して生産性が落ちるので好ましくない。If the reaction temperature is high, a rapid reaction occurs and the reaction is exothermic, which is dangerous, and if the reaction temperature is low, the reaction rate decreases and the productivity decreases, which is not preferable.
本発明において、反応は常圧下、加圧下または減圧下の
いずれで行なってもよいが、特に硫酸を使用する場合、
反応は還流下、常圧で行なうのが望ましい。また特にア
ルカリ性物質を使用する場合、反応は加圧下で行なうの
が望ましく、その場合発生する炭酸ガスを例えば背圧弁
等を用いて系外から逐次抜きながら反応してもよいし、
あるいは系内にそのまま炭酸ガスを封じ込めたまま反応
してもよい。反応時間は特に制限はないが、１〜２０時
間の範囲で行なうのが望ましい。In the present invention, the reaction may be carried out under normal pressure, under pressure or under reduced pressure, but particularly when sulfuric acid is used,
The reaction is preferably carried out under reflux and normal pressure. Further, particularly when an alkaline substance is used, it is desirable to carry out the reaction under pressure, and in that case the carbon dioxide gas generated may be reacted while being successively withdrawn from the outside of the system using, for example, a back pressure valve,
Alternatively, the reaction may be carried out while keeping carbon dioxide in the system. The reaction time is not particularly limited, but it is preferably carried out within the range of 1 to 20 hours.
本発明の出発原料である４−ヒドロキシ−3,5,6−トリ
フルオロフタル酸は例えば、テトラフルオロフタル酸と
テトラフルオロフタル酸１モルに対し３倍モル以上の苛
性ソーダで例示されるアルカリ金属の水酸化物または炭
酸塩存在下水性媒体中で加熱することによって容易に得
ることができる。4-hydroxy-3,5,6-trifluorophthalic acid, which is a starting material of the present invention, is, for example, tetrafluorophthalic acid and tetrafluorophthalic acid, which is an alkali metal exemplified by ca. It can be easily obtained by heating in an aqueous medium in the presence of a hydroxide or carbonate.
以下、本発明における新規物質の製造方法を実施例によ
り具体的に説明し、得られた新規物質を同定するための
分析結果もあわせて示す。Hereinafter, the method for producing a novel substance according to the present invention will be specifically described with reference to Examples, and the analysis results for identifying the obtained novel substance are also shown.
なお、本発明の３−ヒドロキシ−2,4,5−トリフルオロ
安息香酸の製造方法が下記のものに限定されないことは
勿論である。Needless to say, the method for producing 3-hydroxy-2,4,5-trifluorobenzoic acid of the present invention is not limited to the following.
実史例 １ 撹拌機、温度計及びジムロート型冷却器を備えた容量２
００mの４つ口セパラブルフラスコに７０重量％の硫
酸水溶液１３０ｇを入れ、ついで４−ヒドロキシ−3,5,
6−トリフルオロフタル酸２０ｇ（８4.７５mmol）を仕
込んだ後昇温し、充分撹拌しながら還流下１４８〜１５
３℃で3.５時間反応した。次に冷却後反応液を氷水中に
あけ、ついで３−ヒドロキシ−2,4,5−トリフルオロ安
息香酸を含む水溶液から５００mのイソプロピルエー
テルで２回抽出操作することにより、３−ヒドロキシ−
2,4,5−トリフルオロ安息香酸を抽出した。得られたイ
ソプロピルエーテル層は無水硫酸マグネシウムで乾燥
し、ついでイソプロピルエーテルを蒸発乾固して３−ヒ
ドロキシ−2,4,5−トリフルオロ安息香酸１5.６ｇ（８
1.２５mmol、対４−ヒドロキシ−3,5,6−トリフルオロ
フタル酸収率９5.９モル％）が得られた。Case example 1 Capacity 2 with stirrer, thermometer and Dimroth type cooler
Into a 00m 4-neck separable flask, 130g of 70% by weight sulfuric acid aqueous solution was put, and then 4-hydroxy-3,5,
After charging 20 g (84.75 mmol) of 6-trifluorophthalic acid, the temperature was raised and 148 to 15 under reflux with sufficient stirring.
The reaction was carried out at 3 ° C for 3.5 hours. Next, after cooling, the reaction solution is poured into ice water, and then extracted from an aqueous solution containing 3-hydroxy-2,4,5-trifluorobenzoic acid twice with 500 m of isopropyl ether to give 3-hydroxy-
2,4,5-Trifluorobenzoic acid was extracted. The obtained isopropyl ether layer was dried over anhydrous magnesium sulfate, and then isopropyl ether was evaporated to dryness to give 3-hydroxy-2,4,5-trifluorobenzoic acid 15.6 g (8
1.25 mmol, and 4-hydroxy-3,5,6-trifluorophthalic acid yield 95.9 mol%) were obtained.
さらに、このものをベンゼン−アセトンの混合溶媒で再
結晶することによって精製し、この精製した３−ヒドロ
キシ−2,4,5−トリフルオロ安息香酸について次の物性
値を得て３−ヒドロキシ−2,4,5−トリフルオロ安息香
酸の構造を決定した。Further, this product was purified by recrystallization from a mixed solvent of benzene-acetone, and the following physical property values were obtained for the purified 3-hydroxy-2,4,5-trifluorobenzoic acid to obtain 3-hydroxy-2 The structure of 4,4,5-trifluorobenzoic acid was determined.
融 点 １３8.５〜１３9.５℃ 元素分析値 C (%) H(%) F (%) 理論値 ４3.７７ 1.５７ ２9.６７ 分析値 ４3.６４ 1.６８ ２9.５３ 赤外吸収スペクトル（ＫＢｒ錠剤、単位cm-1） 2800〜3500 （ヒドロキシ ν−Ｏ−Ｈ） 1710 （カルボニル ν＞Ｃ＝Ｏ） （尚、赤外吸収スペクトル図を第１図に示した。）19 Ｆ ＮＭＲ （溶媒；アセトン−ｄ６、内部標準物
質；CF3 COOH）ppm Ｆ２ δ −５7.２６、ｄｄｄ （Ｊ＝１4.３、１4.０、6.０） Ｆ４ δ −７3.７１、ｄｄｄ （Ｊ＝２1.２、１4.０、8.５） Ｆ５ δ −６6.２６、ｄｄｄ （Ｊ＝２1.２、１4.３、１1.０） 実施例 ２ １００mのオートクレーブに４−ヒドロキシ−3,5,6−
トリフルオロフタル酸１５ｇ（６3.５６mmol）、水酸化
カルシウム0.７５ｇ（１0.１７mmol）および水５０ｇを
仕込み、その後１５０℃で1.5時間撹拌下反応した。最
終圧力は３5.５kg/cm2・Ｇを示した。反応終了後、冷却
し３０％硫酸４ｇを加え、中和し、過で硫酸カルシウ
ム等の固形物を除去した。液を２００mのイソプロ
ピルエーテルで２回抽出し、３−ヒドロキシ−2,4,5−
トリフルオロ安息香酸を抽出した。得られたイソプロピ
ルエーテル層は無水硫酸マグネシウムで乾燥し、ついで
イソプロピルエーテルを蒸発乾固して３−ヒドロキシ−
2,4,5−トリフルオロ安息香酸１1.４７ｇ（５9.７５mmo
l、対４−ヒドロキシ−3,5,6−トリフルオロフタル酸収
率９４モル％）が得られた。Melting point 138.5-139.5 ° C Elemental analysis value C (%) H (%) F (%) Theoretical value 43.77 1.57 29.67 Analytical value 43.64 1.68 29.53 Infrared absorption Spectrum (KBr tablet, unit cm -1 ) 2800 to 3500 (hydroxy ν-O-H) 1710 (carbonyl ν> C = O) (Infrared absorption spectrum is shown in Fig. 1) 19 F NMR (solvent: acetone -d 6, internal standard; CF 3 COOH) ppm F 2 δ-57.26, ddd (J = 14.3, 14.0, 6.0) F 4 δ-73.71, ddd (J = 21.2, 14.0, 8.5) F 5 δ-6.26, ddd (J = 21.2, 14.3, 11.0) Example 2 4-hydroxy-3,5,6-in a 100 m autoclave.
15 g (63.56 mmol) of trifluorophthalic acid, 0.75 g (10.17 mmol) of calcium hydroxide and 50 g of water were charged, and the mixture was reacted at 150 ° C. for 1.5 hours with stirring. The final pressure was 35.5 kg / cm 2 · G. After completion of the reaction, the mixture was cooled and neutralized by adding 4 g of 30% sulfuric acid, and excessively removed solid substances such as calcium sulfate. The liquid was extracted twice with 200 m of isopropyl ether to give 3-hydroxy-2,4,5-
Trifluorobenzoic acid was extracted. The obtained isopropyl ether layer was dried over anhydrous magnesium sulfate, and then isopropyl ether was evaporated to dryness to give 3-hydroxy-
2,4,5-Trifluorobenzoic acid 11.47 g (59.75 mmo
1, 4-hydroxy-3,5,6-trifluorophthalic acid (yield: 94 mol%) was obtained.
このものは、実施例１と同様に精製さらには分析するこ
とにより、３−ヒドロキシ−2,4,5−トリフルオロ安息
香酸であることを確認した。This product was confirmed to be 3-hydroxy-2,4,5-trifluorobenzoic acid by the same purification and analysis as in Example 1.
実施例 ３ ４−ヒドロキシ−3,5,6−トリフルオロフタル酸の
合成 １００mの４つ口フラスコに、水酸化ナトリウム１1.
７６ｇ（２９４ｍｍｏｌ）を水５０ｇに溶解し、そこに
３，４，５，６−テトラフルオロフタル酸１０ｇ（４２
ｍｍｏｌ）を徐々に加えた後、還流下にて４時間撹拌下
反応した。反応後冷却し、硫酸を加えてｐＨ１にし、イ
ソプロピルエーテルで２回抽出した。得られた抽出液を
無水硫酸マグネシウムで乾燥した後、蒸発乾固して、４
−ヒドロキシ−３，５，６−トリフルオロフタル酸9.３
ｇ（対３，４，５，６−テトラフルオロフタル酸収率:
９４モル％）を得た。Example 3 Synthesis of 4-Hydroxy-3,5,6-trifluorophthalic acid Sodium hydroxide 11
76 g (294 mmol) was dissolved in 50 g of water, and 10 g (42%) of 3,4,5,6-tetrafluorophthalic acid was dissolved therein.
(mmol) was gradually added, and the mixture was reacted under reflux for 4 hours with stirring. After the reaction, the mixture was cooled, sulfuric acid was added to adjust the pH to 1, and the mixture was extracted twice with isopropyl ether. The obtained extract was dried over anhydrous magnesium sulfate and then evaporated to dryness to obtain 4
-Hydroxy-3,5,6-trifluorophthalic acid 9.3
g (vs. 3,4,5,6-tetrafluorophthalic acid yield:
94 mol%) was obtained.
３−ヒドロキシ−２，４，５−トリフルオロ安息香
酸の合成 上記の様にして合成した４−ヒドロキシ−３，５，６−
トリフルオロフタル酸５ｇ（２1.２ｍｍｏｌ）、水酸化
ナトリウム1.７ｇ（４2.４ｍｍｏｌ）及び水１５ｇを５
０ｍ三つ口フラスコに仕込み、還流下にて２７時間撹
拌下反応した。反応後冷却し、硫酸を加えてｐＨ１に
し、イソプロピルエーテルにて２回抽出した。得られた
抽出液を無水硫酸マグネシウムで乾燥した後、蒸発乾固
して、目的物の３−ヒドロキシ−２，４，５−トリフル
オロ安息香酸3.９ｇ（対４−ヒドロキシ−３，５，６−
テトラフルオロフタル酸収率: ９６モル％）を得た。Synthesis of 3-hydroxy-2,4,5-trifluorobenzoic acid 4-hydroxy-3,5,6-synthesized as described above
5 g (21.2 mmol) of trifluorophthalic acid, 1.7 g (42.4 mmol) of sodium hydroxide and 15 g of water were added.
The mixture was placed in a 0 m three-necked flask and reacted under reflux for 27 hours with stirring. After the reaction, the mixture was cooled, sulfuric acid was added to adjust the pH to 1, and the mixture was extracted twice with isopropyl ether. The obtained extract was dried over anhydrous magnesium sulfate and then evaporated to dryness to give 3.9 g of the target compound, 3-hydroxy-2,4,5-trifluorobenzoic acid (vs. 4-hydroxy-3,5,5). 6-
Tetrafluorophthalic acid yield: 96 mol%) was obtained.
実施例 ４ １００ｍの４つ口フラスコに、水酸化ナトリウム8.５
ｇ（２１２ｍｍｏｌ）を水５０ｇに溶解し、そこに３，
４，５，６−テトラフルオロフタル酸１０ｇ（４2.４ｍ
ｍｏｌ）を徐々に加えた後、還流下にて４時間撹拌下反
応した。反応後冷却し、水酸化カルシウム1.７１ｇ（２
3.１ｍｍｏｌ）を加え、１時間撹拌し１晩放置した。次
いで、乳白色のケーキを濾別し、その濾液に硫酸8.３ｇ
（８4.８ｍｍｏｌ）を加え還流下にて、３２時間反応し
た。反応後冷却し、硫酸を加えてｐＨ１にし、イソプロ
ピルエーテルで２回抽出した。得られた抽出液を無水硫
酸マグネシウムで乾燥した後、蒸発乾固して、３−ヒド
ロキシ−２，４，５−トリフルオロ安息香酸7.３ｇ（対
３，４，５，６−テトラフルオロフタル酸収率: ９０
モル％）を得た。Example 4 Sodium hydroxide 8.5 was added to a 100 m four-necked flask.
g (212 mmol) is dissolved in 50 g of water, and then, 3,
4,5,6-Tetrafluorophthalic acid 10g (42.4m
(mol) was gradually added, and the mixture was reacted under reflux for 4 hours with stirring. After the reaction, the mixture was cooled and 1.71 g of calcium hydroxide (2
3.1 mmol) was added and the mixture was stirred for 1 hour and left overnight. Next, the milky white cake was filtered off, and the filtrate had 8.3 g of sulfuric acid.
(84.8 mmol) was added and the mixture was reacted under reflux for 32 hours. After the reaction, the mixture was cooled, sulfuric acid was added to adjust the pH to 1, and the mixture was extracted twice with isopropyl ether. The obtained extract was dried over anhydrous magnesium sulfate and then evaporated to dryness to give 7.3 g of 3-hydroxy-2,4,5-trifluorobenzoic acid (vs. 3,4,5,6-tetrafluorophthalic acid). Acid yield: 90
Mol%) was obtained.
第１図は実施例１で得られた３−ヒドロキシ−2,4,5−
トリフルオロ安息香酸の赤外吸収スペクトル図である。FIG. 1 shows 3-hydroxy-2,4,5-obtained in Example 1.
It is an infrared absorption spectrum figure of trifluoro benzoic acid.
Claims (1)
ロフタル酸を水性媒体中で加熱脱炭酸反応して、３−ヒ
ドロキシ−２，４，５−トリフルオロ安息香酸を製造す
るに際して、触媒としての酸又はアルカリ性物質の存在
下に、該反応を行うことを特徴とする３−ヒドロキシ−
２，４，５−トリフルオロ安息香酸の製造方法。1. When producing 4-hydroxy-3,5,6-trifluorophthalic acid by heating decarboxylation in an aqueous medium to produce 3-hydroxy-2,4,5-trifluorobenzoic acid, 3-hydroxy-characterized in that the reaction is carried out in the presence of an acid or an alkaline substance as a catalyst.
A method for producing 2,4,5-trifluorobenzoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62159712A JPH0610159B2 (en) | 1987-06-29 | 1987-06-29 | Process for producing 3-hydroxy-2,4,5-trifluorobenzoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62159712A JPH0610159B2 (en) | 1987-06-29 | 1987-06-29 | Process for producing 3-hydroxy-2,4,5-trifluorobenzoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS646235A JPS646235A (en) | 1989-01-10 |
| JPH0610159B2 true JPH0610159B2 (en) | 1994-02-09 |
Family
ID=15699640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62159712A Expired - Lifetime JPH0610159B2 (en) | 1987-06-29 | 1987-06-29 | Process for producing 3-hydroxy-2,4,5-trifluorobenzoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0610159B2 (en) |
Families Citing this family (4)
| 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 |
| US4948249A (en) * | 1987-06-23 | 1990-08-14 | Hopkins Manufacturing Corporation | Headlight aiming and light pattern testing apparatus and method |
| 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 |
| US5380926A (en) * | 1994-03-28 | 1995-01-10 | Occidental Chemical Corporation | Method of making 3-methoxy-2,4,5-trifluorobenzoic acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0778033B2 (en) * | 1986-12-04 | 1995-08-23 | 宇部興産株式会社 | 2,4,5-Trifluoro-3-hydroxybenzoic acid and method for producing the same |
-
1987
- 1987-06-29 JP JP62159712A patent/JPH0610159B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS646235A (en) | 1989-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR980009222A (en) | Method of manufacturing lane and dias lane | |
| JPH0610159B2 (en) | Process for producing 3-hydroxy-2,4,5-trifluorobenzoic acid | |
| JPS6222740A (en) | Isolation of p-hydroxybenzaldehyde | |
| EP0240138B1 (en) | Preparation of cinnamic acids | |
| JPS6185350A (en) | Manufacture of 2,4-dichloro-5-fluorobenzoic acid | |
| JP2552319B2 (en) | 3-amino-2,4,5-trifluorobenzoic acid | |
| JP3684546B2 (en) | Production of α, α-dimethylphenylacetic acid from α, α-dimethylbenzyl cyanide under normal pressure | |
| JPH0696545B2 (en) | Process for producing 3,5,6-trifluoro-4-hydroxyphthalic acid | |
| US4061668A (en) | Process for the preparation of 2-(4-isobutylphenyl)-propiohydroxamic acid | |
| CN114478229B (en) | Preparation method of azelaic acid | |
| JPH02255639A (en) | Method for producing 4,4'-(1,6-hexamethylenedioxy)-bis-benzoic acid | |
| JP2504390B2 (en) | Process for producing 3-amino-2,4,5-trifluorobenzoic acid | |
| SU915423A1 (en) | METHOD OF OBTAINING 1-AMINOTHETHRAZOLE1 | |
| JPH078816B2 (en) | Method for producing dibenzoylmethane | |
| JPH03275641A (en) | Hydroxybiphenyl compound and its manufacturing method | |
| CA1062728A (en) | Process for the preparation of 2-(4-isobutylphenyl)-propiohydroxamic acid | |
| RU2033413C1 (en) | Method of synthesis of n-methylenecarboxy-9-acridone esters | |
| JPH0229672B2 (en) | 11CHIKANN55MERUKAPUTOOTETORAZOORUNOSEIZOHO | |
| JPH0158A (en) | 3-Amino-2,4,5-trifluorobenzoic acid and its production method | |
| JP3199618B2 (en) | Method for producing 1,4-dihydroxy-2-naphthoic acid | |
| SU206436A1 (en) | METHOD OF OBTAINING 5-SUBSTITUTED-2,4-OXAZOLIDINDION | |
| SU1625866A1 (en) | Method of producing 5-chloropentanoic acid | |
| JPH09208510A (en) | Production of 4,4'-bis(hydroxymethyl)diphenyl | |
| RU396999C (en) | Method of obtaining phenylhydrazone of phenylglyoxyl | |
| JPH07233122A (en) | Lactic acid ester manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080209 Year of fee payment: 14 |