JPH0655695B2 - Method for producing 2-fluoro-5-nitrobenzotrifluoride - Google Patents
Method for producing 2-fluoro-5-nitrobenzotrifluorideInfo
- Publication number
- JPH0655695B2 JPH0655695B2 JP63292443A JP29244388A JPH0655695B2 JP H0655695 B2 JPH0655695 B2 JP H0655695B2 JP 63292443 A JP63292443 A JP 63292443A JP 29244388 A JP29244388 A JP 29244388A JP H0655695 B2 JPH0655695 B2 JP H0655695B2
- Authority
- JP
- Japan
- Prior art keywords
- nitrobenzotrifluoride
- potassium fluoride
- fluoro
- producing
- spray
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- 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、医薬および農薬等の中間体として有用な２−
フルオロ−５−ニトロベンゾトリフルオライドの製造法
に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is useful as an intermediate for pharmaceuticals, agricultural chemicals, and the like.
It relates to a method for producing fluoro-5-nitrobenzotrifluoride.
（従来の技術） フルオロニトロベンゼン類の製造法として、対応するク
ロロもしくはブロモニトロベンゼン類にフッ化カリウム
をジメチルホルムアミド（以下ＤＭＦと略す）、ジメチ
ルスルホキシド（以下ＤＭＳＯと略す）のような非プロ
トン性極性有機溶媒中で反応させることにより、得られ
ることが知られている［Ｊ．Am.Chem.Soc.,78,6034(195
6)：有合化、25,808(1967)］。(Prior Art) As a method for producing fluoronitrobenzenes, aprotic polar organic compounds such as dimethylformamide (hereinafter abbreviated as DMF) and dimethylsulfoxide (hereinafter abbreviated as DMSO) are added to corresponding chloro or bromonitrobenzenes with potassium fluoride. It is known to be obtained by reacting in a solvent [J. Am.Chem.Soc., 78 , 6034 (195
6): Yugoka, 25, 808 (1967)].
この方法によると、６０〜８０％の収率で目的のフルオ
ロニトロベンゼン類が得られるが、しかし、一般に反応
速度が小さいため、過酷な条件下で長時間にわたって反
応させなければならないという欠点を有している。また
副生物の生成および反応装置の腐蝕などの点でも好まし
い方法ではない。更に、フッ素置換の転化率を上げるた
めに、高価なフッ化カリウムを基質に対して２当量以上
更には大過剰使用したり、フッ化カリウムの脱水など工
業的な方法としては満足すべきものとはいえない。又、
基質により反応性がかなり異なり、類似の化合物を用い
て反応を行なっても良い結果が得られないことはしばし
ばである。According to this method, the desired fluoronitrobenzenes can be obtained in a yield of 60 to 80%, however, the reaction rate is generally low, so that it has a drawback that the reaction must be performed for a long time under severe conditions. ing. Further, it is not a preferable method in terms of generation of by-products and corrosion of the reaction device. Further, in order to increase the conversion rate of fluorine substitution, expensive potassium fluoride should be used in an equivalent amount of 2 equivalents or more with respect to the substrate, or it should be satisfied as an industrial method such as dehydration of potassium fluoride. I can't say. or,
The reactivity varies considerably depending on the substrate, and it is often the case that good results are not obtained even if the reaction is performed using a similar compound.
（発明が解決しようとする課題） 本発明の目的は、選択率も転化率も良く、工業的に安価
な方法で、２−フルオロ−５−ニトロベンゾトリフルオ
ライドを製造する方法を提供することである。(Problems to be Solved by the Invention) An object of the present invention is to provide a method for producing 2-fluoro-5-nitrobenzotrifluoride by an industrially inexpensive method having both good selectivity and good conversion. is there.
（発明の構成） 本発明の要旨は、２−クロロ又は２−ブロモ−５−ニト
ロベンゾトリフルオライドに、フッ化カリウムを非プロ
トン性極性溶媒中で反応させて、２−フルオロ−５−ニ
トロベンゾトリフルオライドを製造する方法において、
フッ化カリウムとしてスプレー乾燥フッ化カリウムを使
用することを特徴とするフルオロニトロベンゼン類の製
造方法である。(Structure of Invention) The gist of the present invention is to react 2-chloro or 2-bromo-5-nitrobenzotrifluoride with potassium fluoride in an aprotic polar solvent to give 2-fluoro-5-nitrobenzoate. In the method for producing trifluoride,
A method for producing fluoronitrobenzenes, characterized in that spray-dried potassium fluoride is used as potassium fluoride.
本発明は、スプレー乾燥フッ化カリウムをハロゲン交換
によるフッ素化剤として使用することを特徴としてい
る。本発明で用いるスプレー乾燥フッ化カリウムはスプ
レー乾燥法によって合成したフッ化カリウムであり、既
に市販されている。そして、それは従来の湿式合成法で
合成したフッ化カリウム（例えば、粒子径は１００〜３
００μｍ、比表面積は０．１ｍ３／ｇ、嵩比重は１．４
〜１．６ｇ／ml）に比べて、平均粒子径が極めて小さく
（１〜５０μ）、水分含量が小さく（０．０５〜０．１
％）、極めて嵩高い白色微粉体で（嵩比重０．３〜０．
７ｇ／ml、粒子径１０〜５０μ）、比表面積も大きい
（１．０〜２．０ｍ３／ｇ、ＢＥＴ法）ものである。The invention is characterized in that spray-dried potassium fluoride is used as a fluorinating agent by halogen exchange. The spray-dried potassium fluoride used in the present invention is potassium fluoride synthesized by a spray-drying method and is already commercially available. And, it is potassium fluoride synthesized by a conventional wet synthesis method (for example, the particle size is 100 to 3).
00 μm, specific surface area 0.1 m 3 / g, bulk specific gravity 1.4
~ 1.6g / ml), the average particle size is very small (1-50μ) and the water content is small (0.05-0.1).
%), Which is an extremely bulky white fine powder (bulk specific gravity 0.3 to 0.
7 g / ml, particle diameter 10 to 50 μ), and large specific surface area (1.0 to 2.0 m 3 / g, BET method).
本発明の方法を実施するにさいして、スプレー乾燥フッ
化カリウムは基質に対して１当量から１．５当量でよ
く、好ましくは１．２当量から１．５当量がよい。溶媒
として用いる非プロトン性極性溶媒はＤＭＦ、ＤＭＳ
Ｏ、１，３−ジメチル−２−イミダゾリジノン（ＤＭ
Ｉ）などが上げられ、その使用料は２−クロロ又は２−
ブロモ−５−ニトロベンゾトリフルオライドに対して
０．５〜５重量部であり、好ましくは０．８〜２．５重
量部である。また、反応温度は１２０〜１６０゜Cが好ま
しく、反応時間も２〜６時間と短時間で反応が完結す
る。In carrying out the method of the present invention, the spray-dried potassium fluoride may be 1 equivalent to 1.5 equivalents, preferably 1.2 equivalents to 1.5 equivalents, relative to the substrate. The aprotic polar solvent used as the solvent is DMF or DMS.
O, 1,3-dimethyl-2-imidazolidinone (DM
I) etc. are raised, and the usage fee is 2-chloro or 2-
The amount is 0.5 to 5 parts by weight, preferably 0.8 to 2.5 parts by weight, based on bromo-5-nitrobenzotrifluoride. The reaction temperature is preferably 120 to 160 ° C., and the reaction time is 2 to 6 hours, so that the reaction is completed in a short time.
（実施例） 以下、実施例を挙げて本発明を説明するが、これらの例
は何ら本発明を拘束するものではない。(Examples) Hereinafter, the present invention will be described with reference to examples, but these examples do not limit the present invention.
実施例１ ２−クロロ−５−ニトロベンゾトリフルオライド６０
ｇ、スプレー乾燥フッ化カリウム（森田化学工業製、そ
の粒子径は１０〜５０μｍ、比表面積はＢＥＴ法で１．
２〜２．０ｍ３／ｇ、嵩比重は０．３〜０．７ｇ／ml）
２０ｇおよびＤＭＦ７１ｇを、１５０゜Cで６時間加熱攪
拌反応させた。反応液を室温まで冷却し、水５００mlに
添加し、トルエンで抽出した。無水硫酸マグネシウムで
乾燥し、減圧下濃縮後、減圧蒸留を行なって沸点７６〜
８２゜C／１２〜７mmHgの２−フルオロ−５−ニトロベン
ゾトリフルオライド５２ｇ（収率９３％）を得た。Example 1 2-Chloro-5-nitrobenzotrifluoride 60
g, spray-dried potassium fluoride (manufactured by Morita Chemical Industry Co., Ltd., particle size is 10 to 50 μm, specific surface area is 1.
2 to 2.0 m 3 / g, bulk specific gravity 0.3 to 0.7 g / ml)
20 g of DMF and 71 g of DMF were reacted by heating and stirring at 150 ° C. for 6 hours. The reaction solution was cooled to room temperature, added to 500 ml of water, and extracted with toluene. Dry over anhydrous magnesium sulfate, concentrate under reduced pressure, and then distill under reduced pressure to give a boiling point of 76-
52 g (yield 93%) of 2-fluoro-5-nitrobenzotrifluoride at 82 ° C / 12-7 mmHg was obtained.
実施例２ ２−クロロ−５−ニトロベンゾトリフルオライド２０
ｇ、実施例１で用いたのと同じスプレー乾燥フッ化カリ
ウム６．２ｇおよびＤＭＳＯ３０ｇを１５０゜Cで３時間
加熱攪拌した。反応液を室温まで冷却し、水２００mlに
添加し、トルエンで抽出した。無水硫酸ナトリウムで乾
燥し、減圧化濃縮後、減圧蒸留を行なって２−フルオロ
−５−ニトロベンゾトリフルオライド１６．６ｇ（収率
９０％）を得た。Example 2 2-Chloro-5-nitrobenzotrifluoride 20
g, 6.2 g of the same spray-dried potassium fluoride as used in Example 1 and 30 g of DMSO were heated and stirred at 150 ° C. for 3 hours. The reaction solution was cooled to room temperature, added to 200 ml of water, and extracted with toluene. The extract was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then distilled under reduced pressure to obtain 16.6 g (yield 90%) of 2-fluoro-5-nitrobenzotrifluoride.
実施例３ ２−クロロ−５−ニトロベンゾトリフルオライド２０
ｇ、スプレー乾燥フッ化カリウム６．７ｇおよびＤＭＳ
Ｏ３０ｇを１３０゜Cで４時間加熱攪拌した。反応液を室
温まで冷却し、水３００mlに添加し、トルエンで抽出を
した。無水硫酸マグネシウムで乾燥し、減圧下濃縮後、
減圧蒸留を行なって２−フルオロ−５−ニトロベンゾト
リフルオライド１６．３ｇ（収率８８％）を得た。Example 3 2-Chloro-5-nitrobenzotrifluoride 20
g, spray dried potassium fluoride 6.7 g and DMS
30 g of O was heated and stirred at 130 ° C for 4 hours. The reaction solution was cooled to room temperature, added to 300 ml of water, and extracted with toluene. After drying over anhydrous magnesium sulfate and concentrating under reduced pressure,
Distillation under reduced pressure gave 16.3 g (yield 88%) of 2-fluoro-5-nitrobenzotrifluoride.
比較例１ ［J.Am.Chem/Soc.,78,6034(1956)記載の方法］ 湿式合成フッ化カリウム（粒子径は１００〜３００μ
ｍ、比表面積は０．１ｍ３／ｇ、嵩比重は１．４〜１．
６ｇ／ml）を予め焼成して無水物としたもの２３．２
ｇ、２−クロロ−５−ニトロベンゾトリフルオライド４
５ｇ、およびＤＭＦ５５mlを１６０゜Cで４時間加熱攪拌
した。反応液を室温まで冷却し、水で希釈後トルエンで
抽出した。無水硫酸ナトリウムで乾燥し、減圧下濃縮
後、減圧蒸留を行なって、２−フルオロ−５−ニトロベ
ンゾトリフルオライド３４ｇ（収率８１％）を得た。Comparative Example 1 [Method described in J. Am. Chem / Soc., 78 , 6034 (1956)] Wet synthetic potassium fluoride (particle size: 100 to 300 μm)
m, the specific surface area is 0.1 m 3 / g, and the bulk specific gravity is 1.4 to 1.
6g / ml) previously calcined to give an anhydride 23.2
g, 2-chloro-5-nitrobenzotrifluoride 4
5 g and DMF (55 ml) were heated with stirring at 160 ° C. for 4 hours. The reaction solution was cooled to room temperature, diluted with water and extracted with toluene. The extract was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then distilled under reduced pressure to obtain 34 g (yield 81%) of 2-fluoro-5-nitrobenzotrifluoride.
（発明の効果） 本発明の方法は、スプレー乾燥フッ化カリウムを用いる
ことを特徴とし、上記実施例と比較例とを比べて明らか
なように、通常のフッ化カリウムを用いる場合に比べて
少量、短時間でクロル又はブロモをフルオロに置換し、
目的の２−フルオロ−５−ニトロベンゾトリフルオライ
ドが高収率、高純度で得られる。(Effect of the invention) The method of the present invention is characterized by using spray-dried potassium fluoride. , Replacing chloro or bromo with fluoro in a short time,
The desired 2-fluoro-5-nitrobenzotrifluoride can be obtained in high yield and high purity.
Claims (1)
ロベンゾトリフルオライドに、フッ化カリウムを非プロ
トン性極性溶媒中で反応させて、２−フルオロ−５−ニ
トロベンゾトリフルオライドを製造する方法において、
フッ化カリウムとしてスプレー乾燥フッ化カリウムを使
用することを特徴とするフルオロニトロベンゼン類の製
造方法。1. A method for producing 2-fluoro-5-nitrobenzotrifluoride by reacting 2-chloro or 2-bromo-5-nitrobenzotrifluoride with potassium fluoride in an aprotic polar solvent. At
A method for producing fluoronitrobenzenes, characterized in that spray-dried potassium fluoride is used as potassium fluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63292443A JPH0655695B2 (en) | 1988-11-21 | 1988-11-21 | Method for producing 2-fluoro-5-nitrobenzotrifluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63292443A JPH0655695B2 (en) | 1988-11-21 | 1988-11-21 | Method for producing 2-fluoro-5-nitrobenzotrifluoride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02138154A JPH02138154A (en) | 1990-05-28 |
| JPH0655695B2 true JPH0655695B2 (en) | 1994-07-27 |
Family
ID=17781863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63292443A Expired - Lifetime JPH0655695B2 (en) | 1988-11-21 | 1988-11-21 | Method for producing 2-fluoro-5-nitrobenzotrifluoride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0655695B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07233097A (en) * | 1994-02-23 | 1995-09-05 | Chichibu Onoda Cement Corp | Production of electrophilic fluorination agent |
| JP4990444B2 (en) * | 2001-04-25 | 2012-08-01 | コンビ株式会社 | Beverage container with straw |
| JP5250997B2 (en) * | 2006-04-27 | 2013-07-31 | 住友化学株式会社 | Potassium fluoride dispersion and method for producing fluorine-containing organic compound using the same |
-
1988
- 1988-11-21 JP JP63292443A patent/JPH0655695B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02138154A (en) | 1990-05-28 |
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