JPS61161251A - Production of aromatic nitrile having no2, cl or ch3o as substituent group - Google Patents
Production of aromatic nitrile having no2, cl or ch3o as substituent groupInfo
- Publication number
- JPS61161251A JPS61161251A JP60002397A JP239785A JPS61161251A JP S61161251 A JPS61161251 A JP S61161251A JP 60002397 A JP60002397 A JP 60002397A JP 239785 A JP239785 A JP 239785A JP S61161251 A JPS61161251 A JP S61161251A
- Authority
- JP
- Japan
- Prior art keywords
- ch3o
- benzoic acid
- substituent group
- nitrile
- catalyst
- 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.)
- Pending
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)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は置換基としてＮ０２、Ｃ６或いはＣＨ３Ｏを有
する芳香族ニトリルの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing aromatic nitriles having N02, C6 or CH3O as substituents.
本発明で得られる、置換基としてＮＯ２、Ｃｔ 或いは
ＣＨ３Ｏを有する芳香族ニトリル（以下置換ベンゾニト
リルという）は農薬、染料等の合成中間体として重要な
化合物である。The aromatic nitrile (hereinafter referred to as substituted benzonitrile) having NO2, Ct, or CH3O as a substituent obtained by the present invention is an important compound as a synthetic intermediate for agricultural chemicals, dyes, and the like.
従来、置換ベンジエ） ＩＪルは４ｒ１それぞれの置換
基に対応し危置換基を有する安息香酸とアンモニアで置
換安息香酸アミドを合成した後、さらに脱水して置換ベ
ンゾニトリルを得る方法等があるが工程が長く、収率も
低く有利な方法ではなかった。Conventionally, substituted benzonitrile) IJ has a method of synthesizing substituted benzoic acid amide with benzoic acid and ammonia which have a vulnerable substituent corresponding to each substituent of 4r1, and then further dehydrating to obtain substituted benzonitrile. This method was not advantageous because it took a long time and the yield was low.
本発明者等は従来の方法に勝る置換ベンゾニトリルの製
造法について、Ｐ−ニトロベンゾニトリルを代表として
研究を行ない、Ｔ１ 内張シのオートクレプを用いＰ−
ニトロ安息香酸とベンゾニトリルとを塩化アンモニウム
を触媒として反応させると、収率よ（、Ｐ−ニトロベン
ゾニトリルが得られることがわかった。しかし、この方
法は、通常のＳＵＳ 製オドクレープを用いると収率は
極端に低下し、黒色の沈＃を生ずる。したがって高価な
Ｔ１ 内張のオートクレーブを使用しなければならず、
実用的でない。The present inventors conducted research on a method for producing substituted benzonitriles that is superior to conventional methods, using P-nitrobenzonitrile as a representative, and used P-nitrobenzonitrile using a T1-lined autocrete.
It was found that when nitrobenzoic acid and benzonitrile are reacted using ammonium chloride as a catalyst, P-nitrobenzonitrile can be obtained in a relatively high yield. The rate is extremely low and a black precipitate is formed.Therefore, an expensive T1 lined autoclave must be used.
Not practical.
本発明は上記の事情に鑑み、触媒を用いて置換安息香酸
と二） ＋１ルとをＳＵＳ ｍオートクレーブ内で反
応させ、置換ベンジエ） ｌルを収率よ〈得ることが出
来る製造法を提供することを目的とする。In view of the above circumstances, the present invention provides a production method that allows substituted benzoic acid to react with 2)l in a SUS m autoclave using a catalyst to obtain substituted benzoic acid in a high yield. The purpose is to
本発明は、上記の問題を解決するためになされたもので
、その手段は、置換基としてＮＯ２、Ｃｔ或いはＣＨ３
Ｏを有する安息香酸と二） ｌルとをフッ化チタンアン
モニウム、フッ化アンモニウム、フッ化チタンカＩＪウ
ムのうちの一種、又はこれらのうちの一種および塩化ア
ンモニウムを触媒として反応させる、置換基としてＮＯ
□、Ｃ４或いはＣＨ３Ｏを有する芳香族二） ＩＪルの
製造法である。The present invention was made in order to solve the above problems, and the means thereof is to use NO2, Ct or CH3 as a substituent.
NO as a substituent, by reacting benzoic acid with O and 2) with ammonium titanium fluoride, ammonium fluoride, one type of titanium fluoride, or one of these and ammonium chloride.
□, a method for producing an aromatic compound having C4 or CH3O.
本発明に使用する触媒は、（１１フツ化チタンアンモニ
ウム（（ＮＨ４１２ＴｉＦ６に以下ＡＦＴ と記す）
、（２レツ化“アンモニウム（ＮＨ４Ｆ＝以下ＡＦと配
す、（３１フツ化チタンカリウム（Ｋ２ＴｉＦ、 ：以
下ＴＰＦと記す）のうちから選ばれた１種、或いはこれ
らのうちの１種に塩化アンモニウム（Ｎ）（４Ｃ／−：
以下ＡＣと記す）を共存させたものである。The catalyst used in the present invention is (ammonium titanium 11 fluoride (NH412TiF6 is hereinafter referred to as AFT).
, (ammonium chloride (NH4F = hereinafter referred to as AF), (31 titanium potassium fluoride (K2TiF, hereinafter referred to as TPF), or ammonium chloride in one of these) (N) (4C/-:
(hereinafter referred to as AC) coexist.
主原料の置換安息香酸としては、ニトロ安息香酸、クロ
ロ安息香酸、メトキシ安息香酸を用いＩＣ稍ヤ力曹令が
、その池の置換基を有する安息香酸も、対応する置換ベ
ンゾニトリルの製造に使用出来ることが予想される。As substituted benzoic acid as the main raw material, nitrobenzoic acid, chlorobenzoic acid, and methoxybenzoic acid were used by IC Koya Rikiso, and benzoic acid with substituents was also used in the production of the corresponding substituted benzonitrile. It is expected that it will be possible.
また、副原料のニトリルとしては、種々なニド１フルが
開用出来る。例えば、芳香族では、ベンゾニド１１ル、
イソフタロニド】Ｊル、テレフタロニトリル、フタロニ
ド１１ル、脂肪族ではアセトニ） ＋フル、プロピオニ
） ＋１ル等が好適である。Furthermore, as the nitrile as an auxiliary raw material, various types of nitrile can be used. For example, for aromatics, benzonide 11,
Preferred are isophthalonide], terephthalonitrile, phthalonide (11), and for aliphatic compounds, acetonyl (acetonyl) + fluor, propioni) (propionyl) +1, etc.
本発明において、通常、二） ＋１ルは溶媒を兼ねるが
、ニドＩＪルがテレフタロニトリルのように固体の場什
には、ベンゼン、トルエン、キシレン等を牌媒として使
用する。In the present invention, 2) +1 usually also serves as a solvent, but when the nido IJ is a solid such as terephthalonitrile, benzene, toluene, xylene, etc. are used as a solvent.
次に本発明の方法を実施する場合の反応条件について説
明する。反応温間は１８０〜３Ｏ０’０、さらに好まし
くは２１０〜２５０℃がよい。また反応時間は、反応温
度によって変るが、通常２〜．６時間、で好゛ましくは
４時間程度である。使用するニトリルの量は、反応の対
称となる置換安息香酸によシ異るが、通常、置換安息香
酸ｗｔ／二゛トリルｗｔが１０〜１００、好ましくＦｉ
２０〜３５である。また、ＡＦＴ ＳＡＦ、ＴＰＦ
（以下含Ｆ触媒と記す）の使用量は、置換安息香酸ｍ、
ＯＬ ／ 含Ｆ触媒ｍｏｌ が１１０．０５〜１／１
の範囲で添加される。反応雰囲気、圧力は、Ｎ２ 加圧
で３Ｏ〜１００〜／ｃｌｎ２の範囲である。溶媒は上記
したようにニトリルが溶媒を兼ねるが、必要に応じてベ
ンゼン、トルエン、キシレン等が使用される。Next, reaction conditions for carrying out the method of the present invention will be explained. The reaction temperature is preferably 180 to 300'0, more preferably 210 to 250°C. The reaction time varies depending on the reaction temperature, but is usually 2 to 30 minutes. The duration is 6 hours, preferably about 4 hours. The amount of nitrile used varies depending on the substituted benzoic acid to be used in the reaction, but usually the ratio wt substituted benzoic acid/wt ditrile is 10 to 100, preferably Fi
It is 20-35. Also, AFT SAF, TPF
The amount of (hereinafter referred to as F-containing catalyst) used is substituted benzoic acid m,
OL/F-containing catalyst mol is 110.05 to 1/1
It is added within the range of The reaction atmosphere and pressure are in the range of 30 to 100/cln2 under N2 pressure. As described above, nitrile also serves as the solvent, but benzene, toluene, xylene, etc. may be used as necessary.
次にｌｊ！施例を示して本発明の詳細な説明する。 Next lj! The present invention will be explained in detail by way of examples.
薬品は、ＡＦＴ （森田化学製−級）、ＡＰ、ＴＰＦ（
共冗ギンメイヒ学Ａ）：、その他はすべて特級を使用し
た。Chemicals include AFT (Morita Chemical grade), AP, TPF (
Cooperative Ginmeichaku A): All others used special grades.
また、装置はＳＵＳ ３１６Ｍ、 ０．Ｉ Ｌのオー
トクレーブを用い、反応は攪拌下で行ない、反応時間Ｖ
！４時間とした。The device is made of SUS 316M, 0. The reaction was carried out under stirring using an IL autoclave, and the reaction time was V.
! It was set as 4 hours.
反応終了後、Ｎ２ をパージし、反応液をガスクロマト
グラフ、液体クロマトグラフで分析し、置換安息香酸を
基準とした置換ベンゾニトリルの収率を求めた。さらに
、反応液を濃縮および有機溶剤洗浄により製品を精製回
収し、ガスクロマトグラフ、液１本クロマトグラフ、融
点測定、赤外線スペクトル、元素分析によって物質の確
認を行なった。After the reaction was completed, N2 was purged, and the reaction solution was analyzed by gas chromatography and liquid chromatography to determine the yield of substituted benzonitrile based on substituted benzoic acid. Furthermore, the product was purified and recovered by concentrating the reaction solution and washing with an organic solvent, and the substance was confirmed by gas chromatography, single-liquid chromatography, melting point measurement, infrared spectrum, and elemental analysis.
実施例１〜１】および触媒としてＮＨ２Ｃｌ のみを
使用した場合の比較例１〜４の結果を第１表に示した。Table 1 shows the results of Examples 1 to 1 and Comparative Examples 1 to 4 in which only NH2Cl was used as a catalyst.
以上述べｔように、本発明の方法はＮｏ２、ＣＬ或いは
ｃＨ３Ｏの置換基を有するベンジエ） ＩＪルを収率よ
（一段の工稈で合成出来、ま文、必要（二応じて連続合
成も可能であるので、工業的ｌ二極めて優れ友方法であ
る。As mentioned above, the method of the present invention can synthesize benzenes having No2, CL, or cH3O substituents in a high yield in a single process, and continuous synthesis is also possible if necessary. Therefore, it is an extremely good method for industrial use.
Claims (1)
安息香酸とニトリルとを、フッ化チタンアンモニウム、
フッ化アンモニウム、フッ化チタンカリウムのうちの一
種、又はこれらのうちの一種および塩化アンモニウムを
触媒として反応させることを特徴とした置換基としてＮ
Ｏ＿２、Ｃｌ或いはＣＨ＿３Ｏを有する芳香族ニトリル
の製造法。Benzoic acid and nitrile having NO_2, Cl or CH_3O as a substituent, titanium ammonium fluoride,
N as a substituent characterized by reacting with ammonium fluoride, potassium titanium fluoride, or one of these and ammonium chloride as a catalyst.
A method for producing an aromatic nitrile containing O_2, Cl or CH_3O.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60002397A JPS61161251A (en) | 1985-01-10 | 1985-01-10 | Production of aromatic nitrile having no2, cl or ch3o as substituent group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60002397A JPS61161251A (en) | 1985-01-10 | 1985-01-10 | Production of aromatic nitrile having no2, cl or ch3o as substituent group |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61161251A true JPS61161251A (en) | 1986-07-21 |
Family
ID=11528103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60002397A Pending JPS61161251A (en) | 1985-01-10 | 1985-01-10 | Production of aromatic nitrile having no2, cl or ch3o as substituent group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61161251A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01125360A (en) * | 1987-11-11 | 1989-05-17 | Idemitsu Kosan Co Ltd | Purification of dihalogenated benzonitrile |
| JPH0568582U (en) * | 1991-11-14 | 1993-09-17 | 有限会社ライオンベースボールプロショップ | A baseball glove's leather strap unwinding prevention tool |
| CN103864644A (en) * | 2014-04-04 | 2014-06-18 | 武汉大学 | Method for preparing cyanobenzene by ammonifying benzoic acid gaseous phase |
-
1985
- 1985-01-10 JP JP60002397A patent/JPS61161251A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01125360A (en) * | 1987-11-11 | 1989-05-17 | Idemitsu Kosan Co Ltd | Purification of dihalogenated benzonitrile |
| JPH0568582U (en) * | 1991-11-14 | 1993-09-17 | 有限会社ライオンベースボールプロショップ | A baseball glove's leather strap unwinding prevention tool |
| CN103864644A (en) * | 2014-04-04 | 2014-06-18 | 武汉大学 | Method for preparing cyanobenzene by ammonifying benzoic acid gaseous phase |
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