JPH0643377B2 - Method for producing N-monoalkylaniline derivative - Google Patents
Method for producing N-monoalkylaniline derivativeInfo
- Publication number
- JPH0643377B2 JPH0643377B2 JP60135719A JP13571985A JPH0643377B2 JP H0643377 B2 JPH0643377 B2 JP H0643377B2 JP 60135719 A JP60135719 A JP 60135719A JP 13571985 A JP13571985 A JP 13571985A JP H0643377 B2 JPH0643377 B2 JP H0643377B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- group
- hydrogen
- monoalkylaniline
- same
- 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
-
- 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 本発明は一般式(I) （式中、Ｒ１およびＲ２は同一または相異なって、水素
原子、ハロゲン原子、アルキル基、アルコキシル基、ヒ
ドロキシル基またはスルホン基を示す。また、Ｒ１およ
びＲ２が核ａと一緒になってナフタリン核を示すことも
ある。Ｒ２は炭素数３以下のアルキル基を示す。） で示されるＮ−モノアルキルアニリン誘導体の製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention has the general formula (I) (In the formula, R 1 and R 2 are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, a hydroxyl group or a sulfone group. Further, R 1 and R 2 are combined with the nucleus a. May also represent a naphthalene nucleus. R 2 represents an alkyl group having a carbon number of 3 or less.).
前記一般式(I)で示されるＮ−モノアルキルアニリン誘
導体は医・農薬あるいは各種工業薬品の中間体あるいは
最終製品として重要であり、従来よりその製造法として
は、たとえばアニリン化合物と脂肪族アルデヒドを、金
属触媒の存在下に水素とともに反応させる方法（特公昭
４２−２６２９０号公報）が知られている。The N-monoalkylaniline derivative represented by the above general formula (I) is important as an intermediate or final product of medical and agricultural chemicals or various industrial chemicals. Conventionally, for example, an aniline compound and an aliphatic aldehyde have been used as production methods. , A method of reacting with hydrogen in the presence of a metal catalyst (Japanese Patent Publication No. 42-26290).
しかし、この方法は炭素数の多いアルデヒドをアルキル
化剤とする場合には有効であっても、炭素数が３以下の
アルデヒドを使用した場合にはジアルキル体の生成が多
くなり、Ｎ−モノ低級アルキルアニリン誘導体の工業的
製造法としては不満足なものであった。However, even though this method is effective when an aldehyde having a large number of carbon atoms is used as an alkylating agent, when an aldehyde having a carbon number of 3 or less is used, the dialkyl product is often produced, and N-mono-lower It was unsatisfactory as an industrial method for producing an alkylaniline derivative.
このようなことから、本発明者らはＮ−置換アルキル基
の炭素数が３以下のＮ−モノ置換アルキルアニリン誘導
体を、高純度、高収率でかつ実施容易に製造する方法に
ついて種々検討の結果、炭素数３以下のアルデヒドをア
ルキル化剤とし、しかも該アルデヒドを反応系に逐次的
に添加して還元アルキル化することにより上記目的が達
せられることを見出し、本発明に至った。Therefore, the present inventors have made various studies on a method for easily producing an N-monosubstituted alkylaniline derivative having an N-substituted alkyl group having 3 or less carbon atoms with high purity and high yield. As a result, they have found that the above object can be achieved by using an aldehyde having 3 or less carbon atoms as an alkylating agent, and by sequentially adding the aldehyde to the reaction system to carry out reductive alkylation, the present invention has been accomplished.
すなわち本発明は、一般式(II) （式中、Ｒ１およびＲ２は前記と同じ意味を有する） で示されるアニリン化合物に、周期律表第VIII族に属す
る金属触媒の存在下、炭素数３以下のアルデヒドを逐次
的に添加しながら水素とともに反応させて還元的にモノ
アルキル化せしめることからなる前記一般式(I)で示さ
れるＮ−モノアルキルアニリン誘導体の製造方法を提供
するものである。That is, the present invention is represented by the general formula (II) (Wherein R 1 and R 2 have the same meaning as described above), an aldehyde having 3 or less carbon atoms is sequentially added in the presence of a metal catalyst belonging to Group VIII of the periodic table. However, the present invention provides a method for producing an N-monoalkylaniline derivative represented by the general formula (I), which comprises reacting with hydrogen to reductively monoalkylate.
本発明において、原料として用いられるアニリン化合物
は前記一般式(II)で示されるとおりであるが、該式にお
ける置換基Ｒ１およびＲ２におけるアルキル基、アルコ
キシル基は低級アルキル基、低級アルコキシル基である
ことが好ましい。In the present invention, the aniline compound used as a raw material is as shown by the general formula (II), and the alkyl group and alkoxyl group in the substituents R 1 and R 2 in the formula are lower alkyl groups and lower alkoxyl groups. Preferably there is.
このようなアニリン化合物として、たとえばアニリン、
クロルアニリン、ブロムアニリン、ジクロルアニリン、
トルイジン、プロピルアニリン、アニシジン、フェネチ
ジン、アミノフェノール、アミノフェノールスルホン
酸、アニリン（モノまたはジ）スルホン酸、キシリジ
ン、アミノクレゾール、ナフチルアミンなどが挙げられ
る。As such an aniline compound, for example, aniline,
Chloraniline, bromaniline, dichloroaniline,
Examples include toluidine, propylaniline, anisidine, phenetidine, aminophenol, aminophenolsulfonic acid, aniline (mono or di) sulfonic acid, xylidine, aminocresol, naphthylamine and the like.
また、もう一方の原料である炭素数３以下のアルデヒド
とは、具体的にはホルムアルデヒド、アセトアルデヒ
ド、プロピオンアルデヒドであり、その使用量は上記ア
ニリン化合物に対して通常１〜1.2モル倍である。The other raw material, aldehyde having 3 or less carbon atoms, is specifically formaldehyde, acetaldehyde, or propionaldehyde, and the amount thereof is usually 1 to 1.2 mol times that of the aniline compound.
この反応における触媒としては周期律表第VIII族に属す
る金属触媒が用いられ、好ましくは白金、パラジウム、
ロジウム、ルテニウム、コバルト、ニッケルまたはこれ
らの硫化物であり、最も好ましくは白金であって、通常
これらは支持担体たとえば炭素などに担持されている。As the catalyst in this reaction, a metal catalyst belonging to Group VIII of the Periodic Table is used, preferably platinum, palladium,
Rhodium, ruthenium, cobalt, nickel or their sulfides, most preferably platinum, usually on a support such as carbon.
また、かかる触媒は一般的にはこれらの内の１種が単独
で使用されるが、２種以上を組合わせて使用することも
できる。Further, such a catalyst is generally used alone as one of these, but it is also possible to use two or more kinds in combination.
触媒の使用量は、一般的には金属量としてアニリン化合
物に対して0.001〜0.2重量％、好ましくは0.005〜0.1重
量％である。The amount of the catalyst used is generally 0.001 to 0.2% by weight, preferably 0.005 to 0.1% by weight, based on the aniline compound, as a metal amount.
反応は溶媒中で行われ、溶媒としては水またはｎ−ヘキ
サン、ベンゼン、トルエン、メタノールなどの反応に不
活性な有機溶媒が使用され、これらは水−有機溶媒の混
合系であってもよい。The reaction is carried out in a solvent, and as the solvent, water or an organic solvent inert to the reaction such as n-hexane, benzene, toluene and methanol is used, and these may be a water-organic solvent mixed system.
かかる溶媒の使用量は、好ましくは原料が完全に溶解す
るに足る量であるが、本反応は懸濁状においても進行す
るため特に制限されない。The amount of such a solvent used is preferably an amount sufficient to completely dissolve the raw materials, but this reaction is not particularly limited because it proceeds even in a suspended state.
一般的にはアニリン化合物に対して0.3〜３０倍重量、
好ましくは１〜１５倍重量である。Generally, 0.3 to 30 times the weight of aniline compound,
The weight is preferably 1 to 15 times.
反応温度は０〜２００℃、好ましくは１５〜１２０℃で
ある。０℃未満においても反応の進行は認められるが、
著しく長時間を要する。水素圧力は１〜１００kg／c
m2、好ましくは１０〜５０kg／cm2である。The reaction temperature is 0 to 200 ° C, preferably 15 to 120 ° C. Although the reaction progress is observed below 0 ° C,
Remarkably takes a long time. Hydrogen pressure is 1 to 100 kg / c
m 2 is preferably 10 to 50 kg / cm 2 .
本発明の方法において、炭素数３以下のアルデヒドはそ
の一部を逐次的に反応系に添加することが重要であり、
その全量を用いて反応を開始したのでは良好な結果が得
られない。In the method of the present invention, it is important that a part of the aldehyde having 3 or less carbon atoms is sequentially added to the reaction system,
If the reaction is started using the whole amount, good results cannot be obtained.
すなわち、本発明においては、その反応において使用さ
れるアニリン化合物の全量および全アルデヒド量の内の
約２０〜８０重量％を用いて、触媒の存在下、水素を供
給しながら反応を開始し、水素吸収が止まったのち、ア
ルデヒドの残量を反応終了時まで連続的または断続的に
系内に添加しながら反応を継続することにより行われ
る。That is, in the present invention, about 20 to 80% by weight of the total amount of aniline compound and total aldehyde used in the reaction is used to start the reaction while supplying hydrogen in the presence of a catalyst, After absorption is stopped, the reaction is continued by continuously or intermittently adding the remaining amount of aldehyde into the system until the end of the reaction.
反応の終了は、停止する水素吸収によって確認できる
が、反応液の分析たとえばガスクロマトグラフィーによ
る反応液中の原料アニリン化合物の消失などによっても
確認することができる。The completion of the reaction can be confirmed by stopping hydrogen absorption, but can also be confirmed by analysis of the reaction solution, for example, disappearance of the starting aniline compound in the reaction solution by gas chromatography.
反応終了後、反応液からの目的化合物の取出しは、通常
の手段で行われ、必要に応じて精留等による精製が行わ
れる。After the completion of the reaction, the target compound is taken out from the reaction solution by an ordinary means, and if necessary, purified by rectification or the like.
かくして、本発明の方法によればＮ−ジアルキル体を殆
ど生成せしめることなく、短時間で好収率で、容易に高
純度の一般式(I)で示されるＮ−モノアルキルアニリン
誘導体を得ることができる。Thus, according to the method of the present invention, a highly pure N-monoalkylaniline derivative represented by the general formula (I) can be easily obtained in a short time in a good yield with almost no formation of an N-dialkyl derivative. You can
以下、実施例により本発明を説明する。Hereinafter, the present invention will be described with reference to examples.
実施例１ ５００ml容オートクレーブにアニリン18.6ｇ、シクロヘ
キサン１３０ｇ、３６％ホルムアルデヒド水溶液6.7ｇ
および５重量％の炭素上白金９８mgを仕込み、密封す
る。容器内を窒素および水素ガスで順次置換したのち、
水素圧が４０kg／cm2となるまで水素を加える。Example 1 18.6 g of aniline, 130 g of cyclohexane and 6.7 g of 36% aqueous formaldehyde solution were placed in a 500 ml autoclave.
And 98 mg of 5% by weight platinum on carbon are charged and sealed. After sequentially replacing the inside of the container with nitrogen and hydrogen gas,
Hydrogen is added until the hydrogen pressure is 40 kg / cm 2 .
反応混合物を撹拌しながら、水素圧３５〜４５kg／c
m2、温度約４０℃に保持する。While stirring the reaction mixture, hydrogen pressure is 35-45 kg / c
Hold at m 2 and temperature about 40 ° C.
1.5時間後、水素吸収の停止が認められたため、その後
３時間を要して３６％ホルムアルデヒド水溶液10.8ｇを
均等に添加した。この間温度および水素圧はそれぞれ４
０℃、約４０kg／cm2を維持した。After 1.5 hours, it was confirmed that the absorption of hydrogen was stopped. Therefore, 10.8 g of 36% formaldehyde aqueous solution was uniformly added over 3 hours thereafter. During this time, the temperature and hydrogen pressure were 4
The temperature was maintained at 0 ° C. and about 40 kg / cm 2 .
添加終了後も水素吸収が停止するまで同条件を維持し
た。After the addition was completed, the same conditions were maintained until the hydrogen absorption stopped.
反応終了後、オートクレーブを冷却・減圧し、反応液を
取り出した。触媒を過によって除去した後、シクロヘ
キサン等の低沸分を留去し、分液を行なった。有機層を
さらに１０mmHgの減圧下で蒸留してＮ−メチルアニリン
20.3ｇ（収率93.3％）を得た。純度98.5％、沸点７７〜
８１℃／１０mmHg。After completion of the reaction, the autoclave was cooled and depressurized, and the reaction solution was taken out. After the catalyst was removed by filtration, low boiling components such as cyclohexane were distilled off, and liquid separation was performed. The organic layer was further distilled under reduced pressure of 10 mmHg to obtain N-methylaniline.
20.3 g (yield 93.3%) was obtained. Purity 98.5%, boiling point 77-
81 ° C / 10 mmHg.
比較例１ ３６％ホルムアルデヒド水溶液を分割使用することな
く、その全量を用いて反応を開始する以外は実施例１と
同様にして反応および後処理を行ったところ、Ｎ−メチ
ルアニリンの収率は61.4％であり、Ｎ，Ｎ−ジメチルア
ニリンが21.0％の副生率で生成した。Comparative Example 1 The reaction and the post-treatment were carried out in the same manner as in Example 1 except that the whole amount of the 36% formaldehyde aqueous solution was used to start the reaction, and the yield of N-methylaniline was 61.4. %, And N, N-dimethylaniline was produced at a by-product rate of 21.0%.
実施例２ 実施例１における３６％ホルムアルデヒド溶液の代わり
にアセトアルデヒドを反応開始時に7.0ｇ、反応途中添
加時に2.2ｇ使用する以外は実施例１と同様の反応およ
び後処理を行ない、Ｎ−エチルアニリン24.0ｇ（収率9
8.1％）を得た。純度99.1％、沸点８１〜８４℃／１０m
mHg。Example 2 The same reaction and post-treatment as in Example 1 were carried out except that acetaldehyde was used in place of the 36% formaldehyde solution in Example 1 at 7.0 g at the start of the reaction and 2.2 g at the time of addition during the reaction, and N-ethylaniline 24.0 was used. g (yield 9
8.1%). Purity 99.1%, boiling point 81-84 ° C / 10m
mHg.
比較例２ アセトアルデヒドを分割使用することなく、その全量を
用いて反応を開始する以外は実施例２と同様にして反応
および後処理を行ったところ、Ｎ−エチルアニリンの収
率は75.6％であり、Ｎ，Ｎ−ジエチルアニリンが13.0％
の副生率で生成した。Comparative Example 2 The reaction and post-treatment were carried out in the same manner as in Example 2 except that the reaction was started using the total amount of acetaldehyde without split use, and the yield of N-ethylaniline was 75.6%. , N, N-diethylaniline 13.0%
Produced with a by-product rate of.
実施例３ ５００ml容オートクレーブにＯ−クロルアニリン25.5
ｇ、水１０２ｇ、メタノール５１ｇ、３６％ホルムアル
デヒド溶液13.3ｇ及び５重量％の炭素上白金１２８mgを
仕込み、密封する。容器内を窒素および水素ガスで順次
置換したのち、水素圧が３０kg／cm2となるまで水素を
加える。Example 3 O-chloroaniline 25.5 was added to a 500 ml autoclave.
g, 102 g of water, 51 g of methanol, 13.3 g of 36% formaldehyde solution and 128 mg of 5% by weight platinum on carbon are charged and sealed. After the inside of the container was replaced with nitrogen and hydrogen gas in sequence, hydrogen was added until the hydrogen pressure reached 30 kg / cm 2 .
反応混合物を撹拌しながら、水素圧２５〜３０kg／c
m2、温度約２５℃に保持する。４時間後、水素吸収の停
止が認められたため、水素の圧力を３０kg／cm2に維持
したまま、３６％ホルムアルデヒド溶液5.0ｇを反応混
合物をかきまぜながら２５℃で３時間要して均等に添加
した。その後、水素吸収が停止するまで反応を行なっ
た。オートクレーブを冷却・減圧し、反応液を取り出し
た。触媒を過によって除去した後、濃縮を行ない、メ
タノールを留去し、分液を行なった。有機層をさらに２
０mmHgの減圧下で蒸留し、Ｏ−クロル−Ｎ−メチルアニ
リン26.5ｇ（収率91.6％）を得た。純度97.9％、沸点１
０８〜１１１℃／２０mmHg 実施例４ ５００ml容オートクレーブに４−メチルアニリン21.4
ｇ、トルエン１３０ｇ、３６％ホルムアルデヒド水溶液
13.3ｇおよび５重量％の炭素上ロジウム２１４mgを仕込
み、以下実施例３と同様に反応、後処理を行ってＮ−メ
チル−４−メチルアニリン22.7ｇ（収率91.9％）を得
た。While stirring the reaction mixture, hydrogen pressure is 25 to 30 kg / c
Hold at m 2 and temperature about 25 ° C. After 4 hours, it was confirmed that the absorption of hydrogen had stopped, so 5.0 g of 36% formaldehyde solution was added uniformly while stirring the reaction mixture for 3 hours at 25 ° C. while maintaining the hydrogen pressure at 30 kg / cm 2 . . Then, the reaction was carried out until the hydrogen absorption stopped. The autoclave was cooled and depressurized, and the reaction solution was taken out. After the catalyst was removed by filtration, concentration was performed, methanol was distilled off, and liquid separation was performed. 2 more organic layers
Distillation under reduced pressure of 0 mmHg gave O-chloro-N-methylaniline 26.5 g (yield 91.6%). Purity 97.9%, boiling point 1
08-111 ° C / 20 mmHg Example 4 4-methylaniline 21.4 in a 500 ml autoclave.
g, 130 g of toluene, 36% formaldehyde aqueous solution
13.3 g and 5% by weight of 214 mg of rhodium on carbon were charged, and the same reaction and post-treatment were carried out as in Example 3 to obtain 22.7 g of N-methyl-4-methylaniline (yield 91.9%).
純度98.1％、沸点９８〜１０１℃／２０mmHg 実施例５ ５００ml容オートクレーブに２，４−ジクロルアニリン
32.4ｇ、水１３０ｇ、メタノール６５ｇ、３６％ホルム
アルデヒド溶液13.3ｇ及び５重量％の炭素上硫化白金６
４８mgを仕込み、以下、実施例３と同様に反応、後処理
を行なって、２，４−ジクロル−Ｎ−メチルアニリン3
2.5ｇ（収率91.0％）を得た。純度98.6％、融点24.5
℃。Purity 98.1%, boiling point 98-101 ° C./20 mmHg Example 5 2,4-dichloroaniline in a 500 ml autoclave.
32.4 g, 130 g of water, 65 g of methanol, 13.3 g of 36% formaldehyde solution and 5% by weight of platinum sulfide on carbon 6
After charging 48 mg, the reaction and post-treatment were carried out in the same manner as in Example 3 to obtain 2,4-dichloro-N-methylaniline 3
2.5 g (yield 91.0%) was obtained. Purity 98.6%, melting point 24.5
° C.
実施例６ 実施例１におけるアニリンの代わりに等モル量のｍ−ア
ニシジンを使用し、５重量％の炭素上白金９３mgの代わ
りに５重量％の炭素上ルテニウム１８５mgを使用する以
外は実施例１と同様に反応および後処理を行ない、３−
メトキシ−Ｎ−メチルアニリン25.7ｇ（収率91.7％）を
得た。Example 6 As Example 1 except that an equimolar amount of m-anisidine was used in place of the aniline in Example 1 and 5 wt% of Ruthenium on carbon was 185 mg instead of 5 wt% of platinum on carbon. Similarly, the reaction and post-treatment are carried out, and 3-
25.7 g (yield 91.7%) of methoxy-N-methylaniline was obtained.
純度97.9％、沸点１１８〜１２１℃／１０mmHg 実施例７ 実施例１における３６％ホルムアルデヒド水溶液の代わ
りにプロピオンアルデヒドを反応開始時に10.0ｇ、反応
途中添加時に1.6ｇ使用し、５重量％の炭素上白金の代
わりに５重量％の炭素上パラジウム１８６mgを使用する
以外は実施例１と同様に反応および後処理を行ない、Ｎ
−プロピルアニリン26.8ｇ（収率98.6％）を得た。Purity 97.9%, boiling point 118-121 ° C / 10 mmHg Example 7 Instead of the 36% formaldehyde aqueous solution in Example 1, 10.0 g of propionaldehyde was used at the start of the reaction and 1.6 g was added during the reaction, and 5% by weight of platinum on carbon was used. Was reacted and worked up in the same manner as in Example 1 except that 186 mg of 5% by weight palladium on carbon was used instead of N.
26.8 g (yield 98.6%) of propylaniline was obtained.
純度99.3％、沸点９８〜１００℃／１０mmHg 比較例３ プロピオンアルデヒドを分割使用することなく、その全
量を用いて反応を開始する以外は実施例７と同様に反応
および後処理を行ったところ、Ｎ−プロピルアニリンの
収率は84.3％であり、Ｎ，Ｎ−ジプロピルアニリンが8.
1％の副生率で生成した。Purity 99.3%, boiling point 98-100 ° C / 10 mmHg Comparative Example 3 The reaction and post-treatment were carried out in the same manner as in Example 7 except that the reaction was started using the total amount of propionaldehyde without using it in a divided manner. The yield of propylaniline was 84.3%, and the yield of N, N-dipropylaniline was 8.4.3%.
Produced with a by-product rate of 1%.
実施例８〜１３ 実施例１におけるアニリンの代わりに表−１に記載の置
換基Ｒ１，Ｒ２を有するアニリン化合物を等モル量使用
し、５重量％の炭素上白金をアニリンに対する重量割合
と等しくなるように使用する以外は実施例１と同様の反
応および後処理を行い、表−１に示す結果を得た。Examples 8 to 13 Instead of aniline in Example 1, an aniline compound having the substituents R 1 and R 2 shown in Table 1 was used in an equimolar amount, and 5% by weight of platinum on carbon was used as a weight ratio to aniline. The same reaction and post-treatment as in Example 1 were carried out except that they were used in the same amount, and the results shown in Table 1 were obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 213/02 215/76 7457−4Ｈ 217/84 7457−4Ｈ 303/22 309/46 7419−4Ｈ 309/49 7419−4Ｈ // Ｂ０１Ｊ 23/40 27/045 Ｃ０７Ｂ 61/00 ３００ (72)発明者 多田 和弘 大阪府大阪市此花区春日出中３丁目１番98 号 住友化学工業株式会社内 (56)参考文献 特開 昭57−123148（ＪＰ，Ａ) 特開 昭57−35545（ＪＰ，Ａ)─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical indication C07C 213/02 215/76 7457-4H 217/84 7457-4H 303/22 309/46 7419-4H 309/49 7419-4H // B01J 23/40 27/045 C07B 61/00 300 (72) Inventor Kazuhiro Tada 3-98 Kasugadenaka, Konohana-ku, Osaka City, Osaka Prefecture Sumitomo Chemical Co., Ltd. (56 ) Reference JP-A-57-123148 (JP, A) JP-A-57-35545 (JP, A)
Claims (2)
子、ハロゲン原子、アルキル基、アルコキシル基、ヒド
ロキシル基またはスルホン基を示す。また、Ｒ１および
Ｒ２が核ａと一緒になってナフタリン核を示すこともあ
る） で示されるアニリン化合物に、周期律表第VIII族に属す
る金属触媒の存在下、炭素数３以下のアルデヒドを逐次
的に添加しながら水素とともに反応させて還元的にモノ
アルキル化することを特徴とする一般式 （式中、Ｒ１およびＲ２は前記と同じ意味を有し、Ｒ３
は炭素数３以下のアルキル基を示す） で示されるＮ−モノアルキルアニリン誘導体の製造法1. A general formula (In the formula, R 1 and R 2 are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, a hydroxyl group or a sulfone group. Further, R 1 and R 2 are the same as the nucleus a. In the presence of a metal catalyst belonging to Group VIII of the Periodic Table, an aldehyde having 3 or less carbon atoms is sequentially added to an aniline compound represented by General formula characterized by selective monoalkylation (In the formula, R 1 and R 2 have the same meanings as described above, and R 3
Represents an alkyl group having 3 or less carbon atoms) and a method for producing an N-monoalkylaniline derivative represented by
ルテニウム、コバルトおよびニッケルまたはこれらの硫
化物から選ばれる少くとも１種である特許請求の範囲第
１項に記載の方法2. The metal catalyst is palladium, platinum, rhodium,
A method according to claim 1 which is at least one selected from ruthenium, cobalt and nickel or their sulphides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60135719A JPH0643377B2 (en) | 1985-06-20 | 1985-06-20 | Method for producing N-monoalkylaniline derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60135719A JPH0643377B2 (en) | 1985-06-20 | 1985-06-20 | Method for producing N-monoalkylaniline derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6247A JPS6247A (en) | 1987-01-06 |
| JPH0643377B2 true JPH0643377B2 (en) | 1994-06-08 |
Family
ID=15158279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60135719A Expired - Lifetime JPH0643377B2 (en) | 1985-06-20 | 1985-06-20 | Method for producing N-monoalkylaniline derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643377B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2579549B1 (en) * | 1985-04-02 | 1990-07-27 | Bendix France | POWER STEERING SYSTEM FOR MOTOR VEHICLE |
| JP2569575B2 (en) * | 1987-07-27 | 1997-01-08 | トヨタ自動車株式会社 | Automatic warehouse equipment |
| JPH0423705A (en) * | 1990-05-16 | 1992-01-28 | Honda Motor Co Ltd | Goods issue management system |
| JPH04260503A (en) * | 1991-02-13 | 1992-09-16 | Sekisui Jushi Co Ltd | Picking system |
| KR980009227A (en) * | 1996-07-24 | 1998-04-30 | 성재갑 | Preparation of alkyl substituted dialkyl aniline derivatives |
| CN110627654B (en) * | 2019-09-28 | 2022-05-06 | 四川之江高新材料股份有限公司 | Methods for the methylation of amines |
| CN114130416A (en) * | 2021-12-16 | 2022-03-04 | 浙江微通催化新材料有限公司 | Preparation method of carbon-supported multi-metal catalyst and application of carbon-supported multi-metal catalyst in N-alkylation reaction |
-
1985
- 1985-06-20 JP JP60135719A patent/JPH0643377B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6247A (en) | 1987-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4085141A (en) | Process for the preparation of anilines meta-substituted by chlorine | |
| RU93056851A (en) | METHOD FOR PRODUCING 2-ALKYL-6-METHYL-N- (1'-METOXY-2'-PROPYL) ANILINE AND METHOD FOR PRODUCING THEIR CHLOROCETANANIDES | |
| PL177669B1 (en) | Method of obtaining 2-alkyl-6-methyl-n-(1-methoxypropyl-2)anilines and method of obtaining chloroacetanilides | |
| JPH0643377B2 (en) | Method for producing N-monoalkylaniline derivative | |
| JPH07112987B2 (en) | Method for producing aromatic dialkyldiamines | |
| KR910007939B1 (en) | Process for the preparation of tertiary amines | |
| US3435074A (en) | Process for producing nitrodiarylamines | |
| SE462094B (en) | PREPARATION PROCEDURE FOR 4-ALCOXIANILINES | |
| JPS6042231B2 (en) | Improved production method of diarylamine | |
| JP2702262B2 (en) | Method for producing bis (3-aminophenoxy) compound | |
| CN103906728B (en) | Method for preparing tertiary aminoalcohol compound | |
| JPH04149160A (en) | Production of 1-amino-4-alkoxybenzene compounds | |
| CN100364959C (en) | Process for preparing diamines and polyamines of the diphenylmethane series | |
| EP0006590B1 (en) | Process for the preparation of n-alkylaryl amines | |
| CN1065858C (en) | Preparation of N-monoalkyl arylamine by nitro-compound reduction-alkylation | |
| JPS6391351A (en) | Production of n-alkylated aromatic amines | |
| JPH07258229A (en) | Production of 2-phenylbenzotriazole compound | |
| JPH05255210A (en) | Preparation of tetramethyl diamino-polyoxyethylene | |
| JP2813465B2 (en) | Method for producing 1-phenoxy-2-aminopropane | |
| JPS598262B2 (en) | Method for producing P-phenylenediamine | |
| KR930009039B1 (en) | Process for the preparation of aromatic urea | |
| CN1399625A (en) | Preparation of halogenated primary amines | |
| US3225097A (en) | Method of preparing poly(gamma-aminopropyl)indene | |
| JP3855513B2 (en) | Method for producing 3,4-lower alkylenedioxy-N-alkylaniline | |
| JPS6112653A (en) | Production of aminobenzoic acids |