JPH02138154A - Production of 2-fluoro-5-nitrobenzotrifluoride - Google Patents
Production of 2-fluoro-5-nitrobenzotrifluorideInfo
- Publication number
- JPH02138154A JPH02138154A JP63292443A JP29244388A JPH02138154A JP H02138154 A JPH02138154 A JP H02138154A JP 63292443 A JP63292443 A JP 63292443A JP 29244388 A JP29244388 A JP 29244388A JP H02138154 A JPH02138154 A JP H02138154A
- Authority
- JP
- Japan
- Prior art keywords
- potassium fluoride
- spray
- chloro
- nitrobenzotrifluoride
- bromo
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- DNTHMWUMRGOJRY-UHFFFAOYSA-N 1-fluoro-4-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(F)C(C(F)(F)F)=C1 DNTHMWUMRGOJRY-UHFFFAOYSA-N 0.000 title claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 48
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 24
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 24
- HQROXDLWVGFPDE-UHFFFAOYSA-N 1-chloro-4-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(C(F)(F)F)=C1 HQROXDLWVGFPDE-UHFFFAOYSA-N 0.000 claims abstract description 7
- SXEQQBBOAMHOID-UHFFFAOYSA-N 1-bromo-4-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C(C(F)(F)F)=C1 SXEQQBBOAMHOID-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002798 polar solvent Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 abstract description 4
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000012025 fluorinating agent Substances 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000005484 gravity Effects 0.000 description 4
- WHNAMGUAXHGCHH-UHFFFAOYSA-N 1-nitro-3-(trifluoromethyl)benzene Chemical group [O-][N+](=O)C1=CC=CC(C(F)(F)F)=C1 WHNAMGUAXHGCHH-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- NDZJSUCUYPZXPR-UHFFFAOYSA-N 1-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C(F)(F)F NDZJSUCUYPZXPR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
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 provides 2-
The present invention 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、 Ｃｈｅｗ、 Ｓ
ｏｃ、、 ？８．６Ｑ３４（１９５６） ；有合化、２
５．８０８ ｆ１９６７＋］ 。(Prior art) As a method for producing fluoronitrobenzenes, potassium fluoride is added to the corresponding chloro or bromonitrobenzene using an aprotic polar organic compound such as dimethylformamide (hereinafter abbreviated as DMF) or dimethyl sulfoxide (hereinafter abbreviated as DMSO). It is known that it can be obtained by reacting in a solvent [J, Am, Chew, S
oc...? 8.6Q34 (1956); Consolidation, 2
5.808 f1967+].
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１ましば
しばである。According to this method, the desired fluoronitrobenzenes can be obtained with a yield of 60 to 80%, but the reaction rate is generally low, so it has the disadvantage that the reaction must be carried out for a long time under harsh conditions. ing. It is also not a preferable method due to the generation of by-products and corrosion of the reaction equipment.Furthermore, in order to increase the conversion rate of fluorine substitution, expensive potassium fluoride is used in an amount of 2 equivalents or more relative to the substrate, and even in large excess. However, it is not satisfactory as an industrial method, such as dehydration of potassium fluoride.
Reactivity varies considerably depending on the substrate, and it is often the case that good results cannot be obtained even when reactions are performed using similar compounds.
（発明が解決しようとする課題）
本発明の目的は１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) The purpose of the present invention is to provide a method for producing 2-fluoro-5-nitrobenzotrifluoride with good monoselectivity and conversion rate, and by an industrially inexpensive method. be.
（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 the 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 produce 2-fluoro-5-nitrobenzotrifluoride. In a method for producing trifluoride,
This is 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どしている
０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。The present invention is characterized in that spray-dried potassium fluoride is used as a fluorination agent by halogen exchange.The spray-dried potassium fluoride used in the present invention is potassium fluoride synthesized by a spray drying method, and has already been It is commercially available.
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１００〜３００戸、比表面積は
０．１ｍ’／ｇ、嵩比重は１．４〜１ 、６ ｇ／ｄ）
に比べて、平均粒子径が極めて小さく（１〜５０ｕ）、
水分含量が小さく（０，０５〜Ｏ１％）、極めて嵩高い
白色微粉体で（嵩比重０．３〜０．７ｇ／ｌＲ１、粒子
径１０〜５０μ）、比表面積も大きい（１０〜２．０ｍ
”７ｇ、ＢＥＴ法）ものである。And, it is potassium fluoride synthesized by conventional wet synthesis method (for example, particle size is 100 to 300 particles, specific surface area is 0.1 m'/g, bulk specific gravity is 1.4 to 1.6 g/d).
The average particle size is extremely small (1 to 50 u) compared to
It is an extremely bulky white fine powder with a low water content (0.05~01%) (bulk specific gravity 0.3~0.7g/lR1, particle size 10~50μ), and a large specific surface area (10~2.0m
“7g, 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１２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、ＤＭＳＯｌｌ
、３−ジメチル−２−イミダゾリジノン（ＤＭＩ）など
が挙げられ、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℃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 used in an amount of 1 to 1.5 equivalents, preferably 12 to 1.5 equivalents, based on the substrate. Solvent: DMF, DMSOll
, 3-dimethyl-2-imidazolidinone (DMI), etc., and the usage fee is 2-chloro or 2-bromo-
0.5-5 for 5-nitrobenzotrifluoride
Parts by weight, preferably 0.8 to 2.5 parts by weight. Further, the reaction temperature is preferably 120 to 160°C, and the reaction time is 2 to 6 hours, which is a short time to complete the reaction.
（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 explained with reference to Examples, but these examples do not restrict the present invention in any way.
実施例１
２−クロロ−５−ニトロベンゾトリフルオライド６０ｇ
、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１０〜５０Ｆ、比表面積はＢＥＴ法で１．２〜
２．００１″／ｇ、嵩比重は０．３〜０．７ｇ／ｌａ１
）２０ｇおよびＤＭＦ７１ｇを、１５０℃で６時間加熱
撹拌反応させた０反応液を室温まで冷却し、水５００−
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、減圧上濃縮後、減圧蒸留を行なって沸点７６
〜８２℃／１２〜７ ｍｏ＋Ｈｇ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 60 g of 2-chloro-5-nitrobenzotrifluoride
, spray-dried potassium fluoride (manufactured by Morita Chemical Industries, its particle size is 10-50F, and its specific surface area is 1.2-1.2 by BET method)
2.001″/g, bulk specific gravity 0.3-0.7g/la1
) and 71 g of DMF were heated and stirred at 150°C for 6 hours. The reaction solution was cooled to room temperature and mixed with 500 g of water.
and extracted with toluene. Dry over anhydrous magnesium sulfate, concentrate under reduced pressure, and then perform vacuum distillation to reduce the boiling point to 76.
2-Fluoro-5- at ~82°C/12-7 mo+Hg
52 g (yield 93%) of nitrobenzotrifluoride 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２０ｇ
、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℃で３時間加
熱撹拌した１反応液を室温まで冷却し、水２００−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９
０％）を得た。Example 2 2-chloro-5-nitrobenzotrifluoride 20g
A reaction solution prepared by heating and stirring 6.2 g of the same spray-dried potassium fluoride used in Example 1 and 30 g of DMSO at 150° C. for 3 hours was cooled to room temperature, added to 200 μm of water, and extracted with toluene. After drying over anhydrous sodium sulfate, concentration under reduced pressure, and distillation under reduced pressure to obtain 2-fluoro-
16.6 g of 5-nitrobenzotrifluoride (yield: 9
0%) was obtained.
実施例３
２−クロロ−５−ニトロベンゾトリフルオライド２０ｇ
、スプレー乾燥フッ化カリウム６．７ｇおよびＤＭＳ０
３０ｇを１３０℃で４時間加熱攪拌した１反応液を室温
まで冷却し、水３００−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、減圧上濃縮後、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 20g
, spray dried potassium fluoride 6.7g and DMS0
A reaction solution obtained by heating and stirring 30 g at 130° C. for 4 hours was cooled to room temperature, added to 300 g of water, and extracted with toluene. The residue was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and then distilled under reduced pressure to obtain 16.3 g (yield: 88%) of 2-fluoro-5-nitrobenzotrifluoride.
比較例１
［Ｊ、Ａｍ、 Ｃｈｅｍ、 Ｓｏｃ、 、 ７８．６０
３４ ｆ１９５６１記載の方法］湿式合成フッ化カリウ
ム（粒子径は１００〜３００Ｆ、比表面積はＯ，１ｍ”
７ｇ、嵩比重は１．４〜１．６ｇ／ｍ）を予め焼成して
無水物としたもの２３．２ｇ、２−クロロ−５−ニトロ
ベンゾトリフルオライド４５ｇ、およびＤＭＦ ５５−
を１６０℃で４時間加熱攪拌した４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。Comparative Example 1 [J, Am, Chem, Soc, , 78.60
34 f19561 method] Wet synthetic potassium fluoride (particle size is 100-300F, specific surface area is O, 1m"
7 g, bulk specific gravity 1.4-1.6 g/m), 23.2 g of pre-calcined anhydride, 45 g of 2-chloro-5-nitrobenzotrifluoride, and DMF 55-
The four reaction solutions were heated and stirred at 160° C. for 4 hours, cooled to room temperature, diluted with water, and extracted with toluene.
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。The residue 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１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。(Effects of the Invention) The method of the present invention is characterized by using spray-dried potassium fluoride, and as is clear from comparing the above examples and comparative examples, 1. , replacing chloro or bromo with fluoro in a short time,
The desired 2-fluoro-5-nitrobenzotrifluoride is obtained in high yield and purity.
Claims (1)
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。In 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, potassium fluoride A method for producing fluoronitrobenzenes, characterized in that spray-dried potassium fluoride is used as a method of producing fluoronitrobenzenes.
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 true JPH02138154A (en) | 1990-05-28 |
| JPH0655695B2 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) |
Cited By (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 |
| JP2002321760A (en) * | 2001-04-25 | 2002-11-05 | Combi Corp | Beverage container with straw |
| JP2008031028A (en) * | 2006-04-27 | 2008-02-14 | Sumitomo Chemical Co Ltd | Potassium fluoride dispersion solution and process for production of fluorine-containing organic compound using the same |
-
1988
- 1988-11-21 JP JP63292443A patent/JPH0655695B2/en not_active Expired - Lifetime
Cited By (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 |
| JP2002321760A (en) * | 2001-04-25 | 2002-11-05 | Combi Corp | Beverage container with straw |
| JP2008031028A (en) * | 2006-04-27 | 2008-02-14 | Sumitomo Chemical Co Ltd | Potassium fluoride dispersion solution and process for production of fluorine-containing organic compound using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0655695B2 (en) | 1994-07-27 |
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