JPS604159A - Production of fluorobenzonitrile compound - Google Patents
Production of fluorobenzonitrile compoundInfo
- Publication number
- JPS604159A JPS604159A JP11348083A JP11348083A JPS604159A JP S604159 A JPS604159 A JP S604159A JP 11348083 A JP11348083 A JP 11348083A JP 11348083 A JP11348083 A JP 11348083A JP S604159 A JPS604159 A JP S604159A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- chlorobenzonitrile
- solvent
- potassium fluoride
- fluorobenzonitrile
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、クロロベンゾニトリル系化合物とフン化カリ
ウムとを無溶媒、加圧下で反応させて、各種農薬、医薬
或いは染料などの中間原料として有用なフルオロベンゾ
ニトリル系化合物を製造する方法に関する。Detailed Description of the Invention The present invention produces a fluorobenzonitrile compound useful as an intermediate raw material for various agricultural chemicals, medicines, dyes, etc. by reacting a chlorobenzonitrile compound and potassium fluoride without a solvent and under pressure. Relating to a method of manufacturing.
従来、２，４又は６位に少なくとも１ケの塩素原子を有
するりＣ７σベンゾニトリル系化合）＃ｌＪ（以下ＣＢ
Ｎ系化合物と略す）の２．４又は６位の総ての塩素原子
をフッ素原子に置換したフルオロベンゾニトリル系化合
物（以下ＦＢＮ系化合物と略す）を製造する方法として
は、例えばＪ 、 Ｃｈｅｍ。Conventionally, C7σ benzonitrile compounds having at least one chlorine atom at the 2, 4 or 6 position) #lJ (hereinafter CB
As a method for producing a fluorobenzonitrile compound (hereinafter abbreviated as an FBN compound) in which all chlorine atoms at the 2.4 or 6-positions of the N-based compound are replaced with fluorine atoms, for example, J. Chem.
Ｓｏｃ、、−ＣＩ＋ｅｍ、 ＣｏＬＩＩＩ＋＋、ｔｌ
９６５，４３０−４３１頁及び有機合成化学部会誌、第
２７巻、１７５頁（１，９６９）に記載された方法が知
られている。これらの方法は、ツメチルスルホン或いは
ジメチルスルホキシドなどの溶媒の存在下を条件とする
製法に関するものであって、そのため溶媒の分解により
分離し難い生成物が多量に存在するので後処理上難点が
あり、更には溶媒を多量に用いる必要があるが利用した
溶媒の回収は、実質的には不可能な状態であるので、経
済的に不利であり、これら従来の方法に脅わるより工業
的有利な方法の出現がめられている。Soc, -CI+em, CoLIII++, tl
965, pp. 430-431 and Journal of the Society of Organic Synthetic Chemistry, Vol. 27, p. 175 (1,969) are known. These methods involve production methods that require the presence of a solvent such as trimethyl sulfone or dimethyl sulfoxide, and as a result, there are many products that are difficult to separate due to decomposition of the solvent, which poses difficulties in post-processing. Furthermore, although it is necessary to use a large amount of solvent, it is virtually impossible to recover the used solvent, which is economically disadvantageous. A new method is expected to emerge.
本発明者達は、前述の方法を改良すべく検討を重ねた結
果、加圧下で反応させる二よによって、無溶媒でも高収
率で目的物が得られることの知見を得、新規でかつ工業
的有利な製造方法として本発明を完成するに至った。As a result of repeated studies to improve the above-mentioned method, the present inventors discovered that the desired product can be obtained in high yield even without a solvent by reacting under pressure, and have discovered that the desired product can be obtained in high yield even without a solvent. The present invention has been completed as an advantageous manufacturing method.
すなわち本発明は、２，４又は６位に少なくとも１ケの
塩素原子を有するクロロベンゾニトリル系化合物と７７
化カリウムとを反応させで、２，４又Ｃ土６位の総ての
塩素原子をフッ素原子に置換したフルオロベンゾニトリ
ル系化合物を製造する方法におい一〇前記りロロベンゾ
ニ） ｌ）ル系化合物とフッ化カリウムとを無溶媒で、
加圧下、２００〜・４５０℃で反応させることを特徴と
するフルオロベンゾニトリル系化合物の製造方法である
。That is, the present invention provides a chlorobenzonitrile compound having at least one chlorine atom at the 2, 4 or 6 position,
In the method for producing a fluorobenzonitrile compound in which all the chlorine atoms at the 2,4 or 6-position are replaced with fluorine atoms by reacting the fluorobenzonitrile compound with potassium chloride, potassium fluoride without solvent,
This is a method for producing a fluorobenzonitrile compound, characterized in that the reaction is carried out at 200 to 450°C under pressure.
本発明で用いる原料物質のＣＢＮ系化合物は、次の一般
ｍ及びｎはＯ又は１であり、ρ、ｍ又は口の少なくとも
１ケは１である。）で表わされ、従って本発明で得られ
るＦＢＮ系例えば、ＣＢＮ系化合物として２−クロロベ
ンゾニトリル、２．４−ジクロロベンゾニトリル、２．
６−ジクロロベンゾニトリル、２，４．６−）ジクロロ
ベンゾニトリル、２，３．６−ドリクロロベンゾニトリ
ル、２，３，５．６−チトラクロロベンゾ二トリル、或
いは２．３，４．５．Ｇ−ペンタクロロベンゾニトリル
などを用い、所定のフッ素置換反応を実施すると、ＦＢ
Ｎ系化合物としては、２−フルオロベンゾニ） Ｕル（
Ｂ、Ｐ、１０３°Ｃ／ ３５ ｗ）（ｇ）、２．４＝ジ
フルオロベンゾニトリル（Ｍ、Ｐ、４６〜４７℃）、２
，６−リフルオロベンゾニトリル（Ｂ、Ｐ、８１−８３
℃／ １３ ｍｍＨｇ）、２ 、４’、 ６−トリアル
オロベンゾニトリル（Ｂ、Ｐ、１０６〜１０８°Ｃ／７
Ｓｕｕｎｌ（ｇ）、 ３−クロロ−２，６−リフルオ
ロベンゾニトリル（Ｂ、Ｐ、９５°Ｃ／１１ｍｍＨｇ）
、３．５−ジクロロ−２，６−リフルオロベンゾニトリ
ル（Ｂ、Ｐ、１００℃７１０ｐＱｍＨｇ）或いは３．５
−：）クロロ−２，４，６−）リフルオロベンゾニトリ
ル（Ｂ、Ｐ、２２１℃）などが好適に得られる。In the CBN-based compound as a raw material used in the present invention, the following general m and n are O or 1, and at least one of ρ, m, or Λ is 1. ), and therefore, the FBN-based compounds obtained in the present invention include, for example, 2-chlorobenzonitrile, 2.4-dichlorobenzonitrile, 2.
6-dichlorobenzonitrile, 2,4.6-)dichlorobenzonitrile, 2,3.6-dolichlorobenzonitrile, 2,3,5.6-titrachlorobenzonitrile, or 2.3,4.5 ．． When a specified fluorine substitution reaction is performed using G-pentachlorobenzonitrile etc., FB
Examples of N-based compounds include 2-fluorobenzoni) U(
B, P, 103 °C / 35 w) (g), 2.4 = difluorobenzonitrile (M, P, 46-47 °C), 2
,6-lifluorobenzonitrile (B, P, 81-83
°C/13 mmHg), 2,4',6-trialobenzonitrile (B, P, 106-108 °C/7
Suunl (g), 3-chloro-2,6-lifluorobenzonitrile (B, P, 95°C/11mmHg)
, 3.5-dichloro-2,6-lifluorobenzonitrile (B, P, 100°C 710pQmHg) or 3.5
-:)chloro-2,4,6-)lifluorobenzonitrile (B, P, 221°C) and the like can be suitably obtained.
本発明方法の実施に当っては、オートクレーブなどの密
閉容器中にＣＢＮ系化合物と７フ化カリウムとを投入し
、加熱、攪拌することによって行なわれる。In carrying out the method of the present invention, a CBN compound and potassium heptafluoride are placed in a closed container such as an autoclave, and the mixture is heated and stirred.
ここで用いられるフッ化カリウムは、通常の市販品或い
は極微粒物などいずれのものでも用いることができ、そ
の使用量は、ＣＢＮ系化合物の２．４又は６位の総ての
塩素原子をフッ素原子に置換する反応理論量め０．８〜
２．（）倍、望ましくは１〜１．５倍である。一般に反
応温度は２００〜４５０℃、望ましくは３００〜４００
’Ｃであり、反応時間は０．５〜３０時間である。密
閉容器中の圧力は、密閉加熱による自然加圧でよく、そ
の場合圧力は大凡３ Ｋｇ／ｃｍｔ〜２５ ｋｇ／ ｃ
＋＋１２程度である。尚、不活性気体により密閉容器中
の空気を置換したり或いは、前記圧力範囲以上に加圧し
ても良く、この場合酸化或いは重合等を防止することも
できる。The potassium fluoride used here can be either a normal commercial product or an ultrafine powder, and the amount used is such that all chlorine atoms at the 2.4 or 6 position of the CBN compound are replaced with fluorine. Theoretical amount of reaction to replace an atom is 0.8~
2. ( ) times, preferably 1 to 1.5 times. Generally the reaction temperature is 200-450°C, preferably 300-400°C.
'C, and the reaction time is 0.5 to 30 hours. The pressure in the sealed container may be natural pressure due to sealed heating, in which case the pressure is approximately 3 Kg/cmt to 25 kg/c.
It is about ++12. Note that the air in the closed container may be replaced with an inert gas, or the pressure may be increased above the above pressure range, and in this case, oxidation, polymerization, etc. can be prevented.
この様にして得られた反応生成物は、通常の分離、精製
手段を施すことによって、或いは施さずして目的物であ
るＦＢＮ系化合物を高純度、高収亨で得ることができる
。尚、未反応原料や未反応生成物が反応生成物中に存在
する場合には、例えば蒸留などの分離手段を施して未反
応物を回収し、循環使用することがでとる。The reaction product thus obtained can be subjected to conventional separation and purification means, or the target FBN compound can be obtained with high purity and high yield. Incidentally, if unreacted raw materials or unreacted products are present in the reaction product, the unreacted materials can be recovered by performing a separation means such as distillation, and recycled for use.
次に本発明の実施例を記載する。Next, examples of the present invention will be described.
実施例１
圧力計、攪拌機及び温度計を備えた５００Ｉｎρのオー
トクレーブに、２，６−シクロロベンゾニｉ・リルｉ１
１．８ｇ（純度９６％）及び７フ化カリウム１０８，８
．を投入し、オートクレーブを密閉した。次に乾燥窒素
ガスでオートクレーブ中の空気を置換し、攪拌下栓々に
昇温して内温が３５０℃になった時点から３時間反応さ
せた。尚、この間の最大圧力は１４ 、３ ｋｇ／ａｍ
２であった。反応終了後、冷却降温し、２００℃近辺よ
り予めオートクレーブに付設した蒸留回収装置を用い生
成物を採集し、７３．０ｇの油状物を得た。Example 1 In a 500 Inρ autoclave equipped with a pressure gauge, a stirrer, and a thermometer, 2,6-cyclobenzoni i.
1.8g (96% purity) and potassium heptafluoride 108,8
．． was added and the autoclave was sealed. Next, the air in the autoclave was replaced with dry nitrogen gas, and the temperature was raised under stirring with stoppers, and the reaction was allowed to proceed for 3 hours from the time when the internal temperature reached 350°C. The maximum pressure during this period is 14.3 kg/am.
It was 2. After the reaction was completed, the temperature was lowered and the product was collected from around 200° C. using a distillation recovery device previously attached to the autoclave to obtain 73.0 g of oil.
二の油状物質をガスクロマトグラフィーで分析した結果
、２．６−シ゛フルオロベンゾ＝ｌル６Ｌ２率は９９％
であった。（収率８３％）
実施例２〜６
前記実施例１の場合と同様にして反応させ、次表の結果
を得た。As a result of gas chromatography analysis of the second oily substance, the 2,6-difluorobenzoyl 6L2 ratio was 99%.
Met. (Yield: 83%) Examples 2 to 6 The reaction was carried out in the same manner as in Example 1, and the results shown in the following table were obtained.
Claims (1)
ロロベンゾニトリル系化合物と７フ化カリウムとを反応
させて、２，４又は６位の総ての塩素原子をフッ素原子
に置換したフルオロベンゾニトリル系化合物を製造する
方法において、前記クロロベンゾニトリル系化合物と７
フ化カリウムとを無溶媒で、加圧下、２００〜４５０
”（：で反応させることを特徴とするフルオロベンゾニ
Ｉ・リル系化合物の製造方法。2. A fluorobenzonitrile compound having at least one chlorine atom at the 4 or 6 position is reacted with potassium heptafluoride to produce a fluorocarbon compound in which all chlorine atoms at the 2, 4 or 6 positions are replaced with fluorine atoms. In the method for producing a benzonitrile compound, the chlorobenzonitrile compound and 7
Potassium fluoride without solvent, under pressure, 200-450
``(: A method for producing a fluorobenzoni-I-lyl compound, which is characterized by reacting with:.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11348083A JPS604159A (en) | 1983-06-23 | 1983-06-23 | Production of fluorobenzonitrile compound |
| GB08415348A GB2142018B (en) | 1983-06-23 | 1984-06-15 | Method for producing 2,6-difluorobenzonitrile |
| DE19843422936 DE3422936A1 (en) | 1983-06-23 | 1984-06-20 | METHOD FOR PRODUCING 2,6-DIFLUORBENZONITRILE |
| FR8409817A FR2549048B1 (en) | 1983-06-23 | 1984-06-22 | PROCESS FOR THE PREPARATION OF 2,6-DIFLUOROBENZONITRILE FROM 2,6-DICHLOROBENZONITRILE |
| CH303784A CH660361A5 (en) | 1983-06-23 | 1984-06-22 | METHOD FOR PRODUCING 2,6-DIFLUORBENZONITRILE. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11348083A JPS604159A (en) | 1983-06-23 | 1983-06-23 | Production of fluorobenzonitrile compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS604159A true JPS604159A (en) | 1985-01-10 |
| JPH0216746B2 JPH0216746B2 (en) | 1990-04-18 |
Family
ID=14613344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11348083A Granted JPS604159A (en) | 1983-06-23 | 1983-06-23 | Production of fluorobenzonitrile compound |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS604159A (en) |
| CH (1) | CH660361A5 (en) |
| DE (1) | DE3422936A1 (en) |
| FR (1) | FR2549048B1 (en) |
| GB (1) | GB2142018B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6023358A (en) * | 1983-07-19 | 1985-02-05 | Ishihara Sangyo Kaisha Ltd | 2,4,6-trifluorobenzonitrile |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5200548A (en) * | 1984-06-04 | 1993-04-06 | Bayer Aktiengesellschaft | 2,4,5-Trihalogeno- and 2,3,4,5-tetrahalogenobenzene derivatives |
| US5530158A (en) * | 1984-06-04 | 1996-06-25 | Bayer Aktiengesellschaft | 2,4,5-trihalogeno- and 2,3,4,5-tetrahalogenobenzene derivatives |
| US5502235A (en) * | 1994-12-28 | 1996-03-26 | Dowelanco | Solventless process for making 2,6 difluorobenzonitrile |
| US6437168B1 (en) | 2000-09-05 | 2002-08-20 | Nippon Shokubai Co., Ltd. | Method for production of aromatic fluorine compound |
| CN104387289B (en) * | 2014-10-30 | 2017-09-01 | 天津河清化学工业有限公司 | The method of catalyst amount is reduced in difluorobenzonilyile production |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1026290A (en) * | 1964-03-17 | 1966-04-14 | Robert Neville Haszeldine | Aromatic fluorine compounds |
| US3240824A (en) * | 1965-01-28 | 1966-03-15 | Olin Mathieson | Process for preparing fluoronitrobenzenes |
-
1983
- 1983-06-23 JP JP11348083A patent/JPS604159A/en active Granted
-
1984
- 1984-06-15 GB GB08415348A patent/GB2142018B/en not_active Expired
- 1984-06-20 DE DE19843422936 patent/DE3422936A1/en active Granted
- 1984-06-22 CH CH303784A patent/CH660361A5/en not_active IP Right Cessation
- 1984-06-22 FR FR8409817A patent/FR2549048B1/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6023358A (en) * | 1983-07-19 | 1985-02-05 | Ishihara Sangyo Kaisha Ltd | 2,4,6-trifluorobenzonitrile |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0216746B2 (en) | 1990-04-18 |
| GB2142018B (en) | 1986-12-10 |
| GB2142018A (en) | 1985-01-09 |
| DE3422936C2 (en) | 1989-11-16 |
| FR2549048B1 (en) | 1987-12-24 |
| CH660361A5 (en) | 1987-04-15 |
| DE3422936A1 (en) | 1985-01-03 |
| GB8415348D0 (en) | 1984-07-18 |
| FR2549048A1 (en) | 1985-01-18 |
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