JP3278945B2 - Method for producing parafluorophenol - Google Patents
Method for producing parafluorophenolInfo
- Publication number
- JP3278945B2 JP3278945B2 JP00655293A JP655293A JP3278945B2 JP 3278945 B2 JP3278945 B2 JP 3278945B2 JP 00655293 A JP00655293 A JP 00655293A JP 655293 A JP655293 A JP 655293A JP 3278945 B2 JP3278945 B2 JP 3278945B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- parafluorophenol
- parabromofluorobenzene
- mol
- 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 - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- 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、医農薬の中間体として
有用なパラフルオロフェノールの製造方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing parafluorophenol useful as an intermediate for medical and agricultural chemicals.
【０００２】[0002]
【従来の技術】パラハロゲノフルオロベンゼンを加水分
解してパラフルオロフェノールを得る方法としては銅系
またはコバルト系触媒を使用する方法が知られている。
例えば、パラブロムフルオロベンゼンを銅塩、銅粉末
またはナフテン酸コバルトを触媒として使用し、水酸化
カルシウム水溶液と反応させる製法（J.Org.Chem.,26,4
641(1961)). パラクロロフルオロベンゼンを銅塩を触
媒として、リン酸緩衝液を用いて酸性条件下で反応させ
る製法( 米国特許第4,940,821 号およびJ.Fluorine Che
m.,50,377,(1990)) などがある。しかしながらいづれの
製法も目的とする化合物の選択率が80% 未満とひくく、
しかも副生するフェノール類の物性が目的物の性質と近
いためその分離に困難を来していた。また銅化合物と
4 級アンモニウム塩を触媒として、塩基として作用する
バリウム化合物を用いる方法が知られていた( ドイツ国
特許第3,430,554)。しかしながら、この方法は、その再
現性に問題があるため工業的製法としては必ずしも十分
なものとは言いがたいものであった。2. Description of the Related Art As a method for obtaining parafluorophenol by hydrolyzing parahalogenofluorobenzene, a method using a copper-based or cobalt-based catalyst is known.
For example, a production method in which parabromofluorobenzene is reacted with an aqueous solution of calcium hydroxide using copper salt, copper powder or cobalt naphthenate as a catalyst (J. Org. Chem., 26, 4)
641 (1961)). A process in which parachlorofluorobenzene is reacted under acidic conditions using a copper salt as a catalyst and a phosphate buffer (US Pat. No. 4,940,821 and J. Fluorine Che
m., 50, 377, (1990)). However, in any case, the selectivity of the target compound is less than 80%,
In addition, the physical properties of the by-produced phenols are close to the properties of the desired product, which makes separation difficult. Also with copper compounds
A method using a barium compound acting as a base using a quaternary ammonium salt as a catalyst has been known (German Patent No. 3,430,554). However, this method is not necessarily satisfactory as an industrial production method because of its reproducibility.
【０００３】[0003]
【発明が解決しようとする課題】このような状況に鑑
み、本発明者らはパラブロムフルオロベンゼンからパラ
フルオロフェノールを得る方法を検討した結果、８−ヒ
ドロキシキノリン類の銅塩類の存在下、アルカリ金属水
酸化物などのアルカリを作用せしめるだけで目的とする
パラフルオロフェノールを選択的に収率よく得る工業的
に優れた方法を見いだし本発明を完成した。In view of such a situation, the present inventors have studied a method for obtaining parafluorophenol from parabromofluorobenzene. As a result, the present inventors have found that in the presence of copper salts of 8-hydroxyquinolines, alkalis are obtained. The present invention has been completed by finding an industrially excellent method for selectively obtaining a desired parafluorophenol with a high yield only by allowing an alkali such as a metal hydroxide to act.
【０００４】[0004]
【課題を解決するための手段】本発明は、パラブロムフ
ルオロベンゼンを、ビス（８−キノリノラト）銅または
ビス（５−ヒドロキシスルホニル−８−キノリノラト）
銅の存在下、アルカリと反応させることを特徴とするパ
ラフルオロフェノールの製造方法を提供するものであ
る。According to the present invention, parabromofluorobenzene is converted to bis (8-quinolinolato) copper or bis (5-hydroxysulfonyl-8-quinolinolato).
An object of the present invention is to provide a method for producing parafluorophenol, which comprises reacting with an alkali in the presence of copper.
【０００５】以下本発明について詳細に説明する。本発
明においてはビス（８−キノリノラト）銅またはビス
（５−ヒドロキシスルホニル−８−キノリノラト）銅お
よびその混合物が使用される。これら銅化合物の使用量
は、触媒量であり、通常パラブロムフルオロベンゼンに
対して0.001 〜0.3 倍モルである。Hereinafter, the present invention will be described in detail. In the present invention, bis (8-quinolinolato) copper or bis (5-hydroxysulfonyl-8-quinolinolato) copper and a mixture thereof are used. The amount of the copper compound used is a catalytic amount, usually 0.001 to 0.3 times mol of parabromofluorobenzene.
【０００６】また本発明は、パラブロムフルオロベンゼ
ンを一価または二価の銅塩と８−ヒドロキシキノリンま
たは５−ヒドロキシスルホニル−８−ヒドロキシキノリ
ンの存在下、アルカリと反応させることによって実施す
ることもできる。使用される一価の銅塩としては、亜酸
化銅、塩化第一銅、臭化第一銅、沃化第一銅、シアン化
銅またはチオシアン化銅等があり、二価の銅塩としては
酸化銅、硫化第二銅、塩化第二銅、臭化第二銅、硫酸
銅、硝酸銅、酢酸銅、炭酸銅、リン酸銅、過塩素酸銅、
水酸化銅およびその混合物を挙げることができる。これ
ら銅塩の使用量は触媒量であり、通常、通常パラブロム
フルオロベンゼンに対して0.001 〜0.3 倍モルである。The present invention can also be carried out by reacting parabromofluorobenzene with a monovalent or divalent copper salt and an alkali in the presence of 8-hydroxyquinoline or 5-hydroxysulfonyl-8-hydroxyquinoline. it can. Examples of the monovalent copper salt used include cuprous oxide, cuprous chloride, cuprous bromide, cuprous iodide, copper cyanide or copper thiocyanate, and the like. Copper oxide, cupric sulfide, cupric chloride, cupric bromide, copper sulfate, copper nitrate, copper acetate, copper carbonate, copper phosphate, copper perchlorate,
Copper hydroxide and mixtures thereof can be mentioned. The amount of these copper salts used is a catalytic amount, and is usually 0.001 to 0.3 times the molar amount of parabromofluorobenzene.
【０００７】この実施態様においては８−ヒドロキシキ
ノリン、５−ヒドロキシスルホニル−８−ヒドロキシキ
ノリンが挙げられる。これら化合物の使用量は通常使用
する銅塩に対して0.1 〜10モル倍である。In this embodiment, 8-hydroxyquinoline and 5-hydroxysulfonyl-8-hydroxyquinoline are exemplified. The amount of these compounds used is 0.1 to 10 moles per mole of the copper salt usually used.
【０００８】使用されるアルカリとしては、水酸化ナト
リウム、水酸化カリウム、水酸化リチウムなどのアルカ
リ金属水酸化物または水酸化カルシウム、水酸化バリウ
ム等のアルカリ土類金属水酸化物があげられる。これら
アルカリの使用量は、通常パラブロムフルオロベンゼン
に対して1 〜5倍モルであり、その濃度は通常2 〜50％
の範囲である。反応は、通常、反応温度160 〜220 ℃(
自生圧力約5 〜25Kg/cm 2 ) で行われ、通常オートクレ
ーブのような耐圧反応容器中で実施される。Examples of the alkali used include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide. The amount of the alkali used is usually 1 to 5 times the molar amount of parabromofluorobenzene, and the concentration is usually 2 to 50%.
Range. The reaction is usually carried out at a reaction temperature of 160 to 220 ° C (
It is carried out at a autogenous pressure of about 5 to 25 kg / cm 2 ) and is usually carried out in a pressure-resistant reaction vessel such as an autoclave.
【０００９】反応終了後、反応溶液は塩酸や硫酸などの
鉱酸を用いて中和し、必要により濾過、分液、抽出等の
通常の後処理を行って目的物を得ることができる。After the completion of the reaction, the reaction solution is neutralized with a mineral acid such as hydrochloric acid or sulfuric acid, and if necessary, subjected to ordinary post-treatments such as filtration, liquid separation and extraction to obtain the desired product.
【００１０】[0010]
【発明の効果】本発明によれば、選択的にしかも再現性
よくパラフルオロフェノールを製造することができる。According to the present invention, parafluorophenol can be produced selectively and with good reproducibility.
【００１１】[0011]
【実施例】以下、本発明を実施例により詳細に説明する
が、本発明はこれら実施例にのみ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, but the present invention is not limited to these examples.
【００１２】実施例１ ３００ｃｃのオートクレーブにパラブロムフルオロベン
ゼン20.0g(0.11モル)、15.7% 水酸化カリウム水溶液86g
(0.24モル）およびビス(8−キノリノラト) 銅1.0g(2.8
ミリモル) を仕込み、系内を窒素置換後、180 ℃で４時
間加圧下に反応させた。反応圧力は反応初期9.8Kg/c
m2 、反応後期8.1Kg/cm2 であった。反応終了後、放冷
した反応混合物を濃塩酸で中和した。中和反応液をセラ
イト濾過し、さらに水50g 、ジクロロメタン50g で容器
およびセライトを洗浄した。得られた濾液にジクロロメ
タン150gを加え抽出を行った。分液した水層をジクロロ
メタン200gで3 回抽出後、有機層を合わせて無水硫酸ソ
ーダで乾燥した。ガスクロマトグラフィーで分析を行い
収率、組成を求めた。パラブロムフルオロベンゼンの転
化率99% であり、パラフルオロフェノールの選択率97%
、収率は96% であった。フェノールの生成量は0.1%未
満（ガスクロマトグラフィー分析でのパラフルオロフェ
ノールに対する面積比）であった。Example 1 In a 300 cc autoclave, 20.0 g (0.11 mol) of parabromofluorobenzene, 86 g of 15.7% aqueous potassium hydroxide solution
(0.24 mol) and bis (8-quinolinolato) copper 1.0 g (2.8
), And the system was purged with nitrogen and reacted at 180 ° C under pressure for 4 hours. The reaction pressure is 9.8Kg / c at the beginning of the reaction
m 2 , which was 8.1 kg / cm 2 at the latter stage of the reaction. After the completion of the reaction, the cooled reaction mixture was neutralized with concentrated hydrochloric acid. The neutralized reaction solution was filtered through celite, and the vessel and celite were washed with 50 g of water and 50 g of dichloromethane. 150 g of dichloromethane was added to the obtained filtrate to perform extraction. After the separated aqueous layer was extracted three times with 200 g of dichloromethane, the organic layers were combined and dried over anhydrous sodium sulfate. Analysis was performed by gas chromatography to determine the yield and composition. The conversion of parabromofluorobenzene is 99%, and the selectivity of parafluorophenol is 97%.
The yield was 96%. The amount of phenol produced was less than 0.1% (area ratio to parafluorophenol in gas chromatography analysis).
【００１３】実施例２ ３００ｃｃのオートクレーブにパラブロムフルオロベン
ゼン20.0g(0.11モル)、16.0% 水酸化カリウム水溶液86g
(0.245 モル）、８−ヒドロキシキノリン0.83g(5.7 ミ
リモル) および硝酸銅３水和物0.69g(2.9 ミリモル) を
仕込み、実施例１と同様に反応を行った。ガスクロマト
グラフィーで分析を行い収率、組成を求めた。パラブロ
ムフルオロベンゼンの転化率97% であり、パラフルオロ
フェノールの選択率98% 、収率は95% であった。フェノ
ールの生成量は0.1%未満（ガスクロマトグラフィー分析
でのパラフルオロフェノールに対する面積比）であっ
た。Example 2 In a 300 cc autoclave, 20.0 g (0.11 mol) of parabromofluorobenzene and 86 g of a 16.0% aqueous potassium hydroxide solution were added.
(0.245 mol), 0.83 g (5.7 mmol) of 8-hydroxyquinoline and 0.69 g (2.9 mmol) of copper nitrate trihydrate were charged and reacted in the same manner as in Example 1. Analysis was performed by gas chromatography to determine the yield and composition. The conversion of parabromofluorobenzene was 97%, the selectivity for parafluorophenol was 98%, and the yield was 95%. The amount of phenol produced was less than 0.1% (area ratio to parafluorophenol in gas chromatography analysis).
【００１４】実施例３ ３００ｃｃのオートクレーブにパラブロムフルオロベン
ゼン20.0g(0.11モル)、16.0% 水酸化カリウム水溶液86g
(0.245 モル）、５−ヒドロキシスルホニル−８−ヒド
ロキシキノリン1.39g(5.7 ミリモル) および硝酸銅３水
和物0.69g(2.9ミリモル) を仕込み、実施例１と同様に
反応を行った。ガスクロマトグラフィーで分析を行い収
率、組成を求めた。パラブロムフルオロベンゼンの転化
率98% であり、パラフルオロフェノールの選択率94% 、
収率は92% であった。フェノールの生成量は0.1%未満
（ガスクロマトグラフィー分析でのパラフルオロフェノ
ールに対する面積比）であった。Example 3 In a 300 cc autoclave, 20.0 g (0.11 mol) of parabromofluorobenzene and 86 g of a 16.0% aqueous potassium hydroxide solution were added.
(0.245 mol), 1.39 g (5.7 mmol) of 5-hydroxysulfonyl-8-hydroxyquinoline and 0.69 g (2.9 mmol) of copper nitrate trihydrate were charged and reacted in the same manner as in Example 1. Analysis was performed by gas chromatography to determine the yield and composition. The conversion of parabromofluorobenzene is 98%, the selectivity of parafluorophenol is 94%,
The yield was 92%. The amount of phenol produced was less than 0.1% (area ratio to parafluorophenol in gas chromatography analysis).
【００１５】比較例１ ３００ｃｃのオートクレーブにパラブロムフルオロベン
ゼン20.0g(0.11モル)、16.0% 水酸化カリウム水溶液86g
(0.245 モル）および硝酸銅３水和物0.69g(2.9 ミリモ
ル) を仕込み、実施例１と同様に反応を行った。ガスク
ロマトグラフィーで分析を行い収率、組成を求めた。パ
ラブロムフルオロベンゼンの転化率35% であり、パラフ
ルオロフェノールの選択率79% 、収率は28% であった。Comparative Example 1 In a 300 cc autoclave, 20.0 g (0.11 mol) of parabromofluorobenzene and 86 g of a 16.0% aqueous potassium hydroxide solution were added.
(0.245 mol) and 0.69 g (2.9 mmol) of copper nitrate trihydrate were charged and reacted in the same manner as in Example 1. Analysis was performed by gas chromatography to determine the yield and composition. The conversion of parabromofluorobenzene was 35%, the selectivity for parafluorophenol was 79%, and the yield was 28%.
【００１６】比較例２ ３００ｃｃのオートクレーブにパラブロムフルオロベン
ゼン26.3g(0.15モル)、98% 水酸化バリウム８水和物64.
4g(0.200 モル）、銅粉末0.25g(3.9 ミリモル)9および
塩化ステアリルトリメチルアンモニウム0.053g(0.15 ミ
リモル) および水46g を仕込み、系内を窒素置換し、加
圧下、190 ℃で6 時間反応させた。実施例１と同様に後
処理を行い、容器層をロータリーエバポレーターで濃縮
し油状物21.2g を得た。ガスクロマトグラフィーで分析
を行った結果、パラブロムフルオロベンゼン98% 、パラ
フルオロフェノール1%未満（面積百分率）であった。Comparative Example 2 In a 300 cc autoclave, 26.3 g (0.15 mol) of parabromofluorobenzene, 98% barium hydroxide octahydrate 64.
4 g (0.200 mol), copper powder 0.25 g (3.9 mmol) 9, stearyltrimethylammonium chloride 0.053 g (0.15 mmol) and water 46 g were charged, and the system was purged with nitrogen and reacted at 190 ° C. under pressure for 6 hours. . Post-treatment was performed in the same manner as in Example 1, and the container layer was concentrated using a rotary evaporator to obtain 21.2 g of an oily substance. As a result of analysis by gas chromatography, it was found that parabromofluorobenzene was 98% and parafluorophenol was less than 1% (area percentage).
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−39240（ＪＰ，Ａ) 特開 平４−208241（ＪＰ，Ａ) 特開 平４−29950（ＪＰ，Ａ) 特開 平３−2134（ＪＰ，Ａ) 特開 昭60−4144（ＪＰ，Ａ) 特開 昭57−135048（ＪＰ，Ａ) 特開 昭57−42652（ＪＰ，Ａ) 特公 昭42−14531（ＪＰ，Ｂ１) 特公 昭38−1626（ＪＰ，Ｂ１) 特公 昭37−12669（ＪＰ，Ｂ１) 西独国特許出願公開3430554（ＤＥ, Ａ１) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 39/27 C07C 37/02 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-39240 (JP, A) JP-A-4-208241 (JP, A) JP-A-4-29950 (JP, A) JP-A-3-29950 2134 (JP, A) JP-A-60-4144 (JP, A) JP-A-57-135048 (JP, A) JP-A-57-42652 (JP, A) JP-B-42-14531 (JP, B1) JP-B-38-1626 (JP, B1) JP-B-37-12669 (JP, B1) West German Patent Application Publication 3430554 (DE, A1) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 39/27 C07C 37/02
Claims (2)
−キノリノラト）銅またはビス（５−ヒドロキシスルホ
ニル−８−キノリノラト）銅の存在下、アルカリと反応
させることを特徴とするパラフルオロフェノールの製造
方法。(1) Parabromofluorobenzene is converted to bis (8
A process for producing parafluorophenol, comprising reacting with an alkali in the presence of (quinolinolato) copper or bis (5-hydroxysulfonyl-8-quinolinolato) copper.
二価の銅塩と８−ヒドロキシキノリンまたは５−ヒドロ
キシスルホニル−８−ヒドロキシキノリンの存在下、ア
ルカリと反応させることを特徴とするパラフルオロフェ
ノールの製造方法。2. A method for producing parafluorophenol, which comprises reacting parabromofluorobenzene with a monovalent or divalent copper salt and an alkali in the presence of 8-hydroxyquinoline or 5-hydroxysulfonyl-8-hydroxyquinoline. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00655293A JP3278945B2 (en) | 1993-01-19 | 1993-01-19 | Method for producing parafluorophenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00655293A JP3278945B2 (en) | 1993-01-19 | 1993-01-19 | Method for producing parafluorophenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06211716A JPH06211716A (en) | 1994-08-02 |
| JP3278945B2 true JP3278945B2 (en) | 2002-04-30 |
Family
ID=11641500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00655293A Expired - Fee Related JP3278945B2 (en) | 1993-01-19 | 1993-01-19 | Method for producing parafluorophenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3278945B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2440511B1 (en) * | 2009-06-08 | 2018-10-17 | Centre National de la Recherche Scientifique (CNRS) | Method for the hydroxylation of halogenated aryl compounds |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL121253A0 (en) * | 1997-07-07 | 1998-01-04 | Bromine Compounds Ltd | A process for the preparation of para-fluorophenol |
-
1993
- 1993-01-19 JP JP00655293A patent/JP3278945B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2440511B1 (en) * | 2009-06-08 | 2018-10-17 | Centre National de la Recherche Scientifique (CNRS) | Method for the hydroxylation of halogenated aryl compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06211716A (en) | 1994-08-02 |
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