JPS59212449A - Method for alkylating aromatic amine - Google Patents
Method for alkylating aromatic amineInfo
- Publication number
- JPS59212449A JPS59212449A JP58086609A JP8660983A JPS59212449A JP S59212449 A JPS59212449 A JP S59212449A JP 58086609 A JP58086609 A JP 58086609A JP 8660983 A JP8660983 A JP 8660983A JP S59212449 A JPS59212449 A JP S59212449A
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- 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
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- 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】
不発す」は、一般式（１）
ノ基、低級アルコキシ基、フェニル基で置換されていて
もよい低級アルキル基を表わし、ベンゼン項八は、さら
に低級アルキル基、低級アルコキシ基、ハロゲン原子、
もしくはアシルアミノ基で置換されていてもよい。〕
で示されるベンゼン系アミンを、一般式（ＩＩ）（Ｒ“
）、ｓｏ、 、 Ｃ亘り〔式（ＴＩ）中
、ｗ′は炭素数１〜４の飽和アルギル基を表わす。〕
で示されるジアルキル硫酸を用いて、水溶媒中で酸化マ
グネシウムまたは水酸化マグネシウムの存在下に、６０
〜１００℃の温度で反応させ、一般式（１旧〔弐〇１中
、Ｒは、式（Ｉ）中のＲ′または式（ＩＩ）中のＲ“と
同一の意味を表わし、Ｗは式（１］）中の「と同一の意
味を表わす。またベンゼンｍＡは式（υと同一の意味を
表わす。〕
で示される芳香族アミンの７２ルキル化方法に関する。[Detailed Description of the Invention] "Unexploded" refers to a lower alkyl group optionally substituted with a group of general formula (1), a lower alkoxy group, or a phenyl group, and benzene term 8 refers to a lower alkyl group, a lower alkyl group, or a phenyl group. Alkoxy group, halogen atom,
Alternatively, it may be substituted with an acylamino group. ] The benzene-based amine represented by the general formula (II) (R“
), so, , C [In formula (TI), w' represents a saturated argyl group having 1 to 4 carbon atoms. ] Using a dialkyl sulfate represented by
The reaction is carried out at a temperature of ~100°C, and R represents the same meaning as R' in formula (I) or R'' in formula (II), and W represents the formula Benzene mA has the same meaning as ``in (1]). Also, benzene mA has the same meaning as υ in formula (1).
一般式（ｉｌｌ ）で示されるＮ−アルキルアミン類Ｏ
Ｌアゾ系分散染料のＭ要なカップリンク成分であり、従
来、一般式（Ｉ）で示される化合物に錘々のアルキル化
剤を、ソーダ灰、炭酸カリウド、酸化マグネシウムなど
の酸結合剤の存在下または不存在下反応さ（スで得られ
ている０
とＡ１らの方法では、４１機溶媒のイＪ在下−ご行われ
ていたが、有機溶剤を使用した場合は、アルキル化反応
後の目的生成物の後処理や、ＪＩＪＩ水の面で問題力９
．令。N-alkylamines O represented by the general formula (ill)
L is an important coupling component of azo disperse dyes, and conventionally, the compound represented by the general formula (I) is combined with a number of alkylating agents, and the presence of acid binders such as soda ash, potassium carbonate, and magnesium oxide. In the method of A1 et al., the reaction was carried out in the presence or absence of the alkylation reaction.However, when an organic solvent is used, the Problem 9 in terms of post-processing of target products and JIJI water
．． Order.
つた〇
このため不穏溶剤を使用せず、酸結合剤を用いて１ｏｏ
’ｃ以下で水溶媒中でアルキル化反応６行５方法も知ら
れている。〇For this reason, 1oo
A 6-line 5-method for alkylation reaction in an aqueous solvent below 'c is also known.
特公昭５３−２ＱＱ１７号公報には、アルキル化剤とし
て芳香族スルホン酸エステルヶ使用して、水浴媒中で酸
結合剤としてソーダ灰、炭酸カリウム、酸化マグネシウ
ムなどを用い、１００℃以下の比較的低流で実施さ第１
ている。Japanese Patent Publication No. 53-2QQ17 discloses that an aromatic sulfonic acid ester is used as an alkylating agent, soda ash, potassium carbonate, magnesium oxide, etc. are used as an acid binder in a water bath medium, and a relatively low temperature of 100°C or less is used. 1st carried out in flow
ing.
しかしながら、前記舶公昭５３−２００１７号公報ｉ記
載のアルキル化剤を用いた場合は、３・１００ ”Ｑ近
くまで外淵して、式（Ｉ）のアミンが水に溶解し難いの
で長時間水と共存させて反応を行うため、反応中にアル
−）−ル化剤の一部が加水分解される。さらには、水溶
媒中でアルキル化反応を実施した場合は、通常、アルキ
ル化反応物を分前づ−ることなくそのままカプラーに用
いてアゾ染料の合成に供されるが、その場合生成した染
料がタール状となったり、染料の色相が暗色になるなど
製品の品質を落すことがわかった。However, when the alkylating agent described in the above-mentioned Japanese Publication No. Sho 53-20017 i is used, the amine of formula (I) is difficult to dissolve in water, and the amine of formula (I) is difficult to dissolve in water. During the reaction, a part of the alkylation agent is hydrolyzed.Furthermore, when the alkylation reaction is carried out in an aqueous solvent, the alkylation reactant is usually It is used as a coupler without any preparation to synthesize azo dyes, but in this case the resulting dye may become tar-like or the hue of the dye may become dark, resulting in a deterioration in the quality of the product. Understood.
その原因は、アルキル化剤の芳香族スルホン酸エステル
が、アルキル化反応後芳香族スルホン酸塩となって反応
水溶液中に残存し、こ第１とジアゾ成分の一部とが反応
した不純物となり、アゾ染料中に含まれるものと推定さ
２する。The reason for this is that the aromatic sulfonic acid ester of the alkylating agent becomes an aromatic sulfonic acid salt after the alkylation reaction and remains in the reaction aqueous solution, and this first reacts with a part of the diazo component, resulting in an impurity. It is estimated that it is contained in azo dyes2.
また芳香族ヌルホン酸ニスアルを用いた場合（ｔ１Ｊ１
１水中のＣＯＤも高く、公害対策−にも好ましくない。In addition, when aromatic nulfonic acid Nisual is used (t1J1
1 The COD in water is also high, making it unfavorable as a pollution control measure.
本発明者らばこオ′シらの点を鋭意倹よ」の結果、本発
明に到達し１こ（、のであり、アルキル化剤に、低級ジ
アルキル硫酸を選択することにより、アルキル化反応後
得られるカップリング成分乞そのＪ：まアゾ染イ′１製
造に用いた場合に鮮明な染λ（が得Ｃ）汎、しかも１０
０℃近くの高温で長ｆｌｙ間アル−）−ル化反応を行っ
ても、酸結合剤に特定のマクネシウｊ、化合物化使用す
る限りにおいてはアルギル化剤の分解ンｌ上することも
なく、芳香族スルポン酸エステルを用いＴこ場合より反
応速度・ｂ早く、工業的に非’７６１こイ」利な製造方
法であることがわかった。As a result of the inventor's careful consideration of the points of Rabakooshi et al., we have arrived at the present invention. By selecting lower dialkyl sulfuric acid as the alkylating agent, The coupling component obtained is J: When used in the production of azo dye A'1, a clear dye λ (gain C) is obtained, and 10
Even if the algylation reaction is carried out for a long time at a high temperature near 0°C, there will be no decomposition of the algylating agent as long as the acid binder is used as a compound. It has been found that the reaction rate is faster than in the case of using an aromatic sulfonic acid ester, and that this is a manufacturing method that is not industrially advantageous.
本発明方法においては、アルキル化剤にジアルキル硫酸
を用いて、水溶媒中で反応を行うので、酸結合剤として
、酸化マグネシウムまたは水酸化マグネシウムを用いる
必要がある。本発明方法では酸結合剤に、炭酸カリウム
やソーダ灰なと水に容易に溶けて一強アルカリを呈する
ものは好ましくない。有機溶媒を併用する場合にこれら
の酸結合剤の溶解度の小さい有機溶剤を選択、使用する
通常の方法により制御できるが、本発明方法では水溶媒
のみであるので酸結合剤を選択して反応を少くとも弱ア
ルカリ以下の中性に＃！ｌ持された水溶婬中で行う必要
があり、強アルカリ媒体中で行えば、ジアルキル硫ｅは
容易に相応するアルコールへ加水分解さ１１る傾向にあ
り、収率が低下する。Ｉ−たがって本発明方法では、水
難宿性であり、しかも酸とは容易に反応づ−る酸化マグ
ネシウムまたは水酸化マグネシウムを酸結合剤・に用い
、反応系をほぼ中性に保ってアルキ７１／化反応を行う
。In the method of the present invention, dialkyl sulfuric acid is used as an alkylating agent and the reaction is carried out in an aqueous solvent, so it is necessary to use magnesium oxide or magnesium hydroxide as an acid binder. In the method of the present invention, acid binders such as potassium carbonate and soda ash which easily dissolve in water and exhibit strong alkali properties are not preferred. When an organic solvent is used in combination, the reaction can be controlled by the usual method of selecting and using an organic solvent with low solubility for these acid binders, but since the method of the present invention uses only an aqueous solvent, it is difficult to select an acid binder and carry out the reaction. # Neutral to at least weakly alkaline or less! It is necessary to carry out the reaction in an aqueous solution, and if it is carried out in a strongly alkaline medium, the dialkyl sulfur tends to be easily hydrolyzed into the corresponding alcohol, resulting in a lower yield. Therefore, in the method of the present invention, magnesium oxide or magnesium hydroxide, which is water-resistant and easily reacts with acids, is used as an acid binder, and the reaction system is kept almost neutral, and the alkyl 71 /Carry out a chemical reaction.
これによりジアルキル硫酸な用９１１ ＜Ｊ ｌジｈル
キル遂次副生ずる硫酸またはモノアルキル硫酸はと１１
らの酸結合剤と容易に反応して反応を促進させる。This results in dialkyl sulfuric acid.
It easily reacts with other acid binders and promotes the reaction.
本発明では、こ１１らのマグネシウｊ＼化合物を式（Ｉ
）化合物に対し、０．８〜２０肖量用い、水溶媒中で、
６０〜Ｊ ００ ’Ｃ。In the present invention, these 11 magnesium compounds have the formula (I
) Using 0.8 to 20 parts per compound in an aqueous solvent,
60~J00'C.
好ましくは９０〜９５゛Ｃで実施１−る。It is preferably carried out at 90-95°C.
本発明の出発原料である一般式（Ｉ）で表わさ第１る化
合物としては、例えば次のものがあげら２する〇アニリ
ン、１几−１−ルイジン、ｍ−り１コルアニリン、ｍ−
アセデルアミノアニリン、２−メ１ヘキシー５−アセチ
ルアミノアニリン ｎＬ−ヘンシイルアミノアニリン
ＩＩＬ−ソ′ロビオニルアミノアニリン、２−工）−キ
シ−５−アセデルアミノアニリン、２．５−シメト・キ
シアニリン、Ｎ−エチルアニリン、。Examples of the first compound represented by the general formula (I), which is a starting material of the present invention, include the following: 〇aniline, ㇠-1-luidine, m-ri-1-coaniline, m-
Acedelaminoaniline, 2-Me1hexy5-acetylaminoaniline nL-hensyylaminoaniline
IIL-so'lobionylaminoaniline, 2-ethyl)-xy-5-acedelaminoaniline, 2,5-cymethoxyaniline, N-ethylaniline.
Ｎ−シア／エチルアニリン、〜−（β−メトキシエヂル
ファニリン、Ｎ−エチル−ｍ−”５ルイシン、Ｎ−シア
ノエチル−１ｎ−トルイジン、Ｎ−（β−工１ヘキシエ
チル）−アニリン、Ｎ−（β−アセトキシエヂルノーア
ニリン、Ｎ−プヂルーアニリン、Ｎ−フェネヂルアニソ
ン、Ｎ−ブヂルーｙｎ −１＋ルイジン、Ｎ−フェネチ
ル−扉−トルイジン、Ｎ−（β−メトキシエチ）し）−
ｍ−ｌ〜ルイジン、Ｎ−（β−工１−キシエチルン−ｍ
−ｌ−ルイジン、Ｎ−（β−アセトギシエチル）−ｎ
ｌ、 −１−ルイジン、Ｎ−エチル−ｍ−クロルアニリ
ン、Ｎ−ブチル−ｍ−クロルアニリン、Ｎ−シアンエチ
ル−ｍ−クロルアニリン、Ｎ−（β−メ）−キシエチル
）−−−クロルアニリン、Ｎ−Ｃβ−工トギシエヂル）
−ｎ＝−クロルアニリン、Ｎ−（β−アセ１− キシ
エチル） −ｎＬ−クロルアニリン、Ｎ−フェネチル−
ｍ−クロルアニリン、３−（Ｎ−エヂルアミ／ノーアセ
トアニリド 、３−（Ｎ−シアンエチル７′ミノンーア
セ１−アニリド、３−（Ｎ−フェネチルアミノ〕−アセ
トアニリ１〜、Ｎ−アリルアニリン、Ｎ−アリル−ｒｒ
＝−１−ルイジン−に３．−（Ｎ−アリルアミノツーア
セトアニリド、３−（Ｎ−メトキシエチルアミノ）−ア
セ１−アニリド、３−（Ｎ−エトキシエチルアミノ）−
アセトアニリ１−１３ （Ｎ ｉｓ。N-cya/ethylaniline, ~-(β-methoxyedylphaniline, N-ethyl-m-”5 leucine, N-cyanoethyl-1n-toluidine, N-(β-ethylhexyl)-aniline, N-( β-Acetoxyedylnoaniline, N-Pudiruaniline, N-Phenedylanisone, N-Butyruyn-1+luidine, N-Phenethyl-toluidine, N-(β-methoxyethyl)-
m-l~luidine, N-(β-1-xyethyln-m
-l-luidine, N-(β-acetogyethyl)-n
l, -1-luidine, N-ethyl-m-chloroaniline, N-butyl-m-chloroaniline, N-cyanoethyl-m-chloroaniline, N-(β-me)-xyethyl)---chloroaniline , N-Cβ-togishiedil)
-n=-Chloraniline, N-(β-ace1-xyethyl) -nL-Chloraniline, N-Phenethyl-
m-Chloraniline, 3-(N-edylamino/noacetanilide, 3-(N-cyanoethyl 7'minone-acetanilide, 3-(N-phenethylamino)-acetanilide 1~, N-allylaniline, N-allyl -rr
=-1-Luidine-3. -(N-allylaminotoacetanilide, 3-(N-methoxyethylamino)-ace1-anilide, 3-(N-ethoxyethylamino)-
Acetanili 1-13 (N is.
−ブロボキシエヂルアミン）−アセＩ〜アニリ１〜．３
−（Ｎ−ブヂルアミノンーアセＩ〜７′ニリｌ−１３−
（Ｎ−エヂルアミノ）−ブロビオニルアニリ＋＝、３−
（Ｎ−シアンエチルアミノラープロビオニルアニリ）−
３−（Ｎ−エヂルアミノンーペンゾイルアニリＩ−など
であり、また式（１１）で示さ第１るシアル−Ｖル硫酸
としてはジメチル硫酸、ジエチル硫酸、ジブチル硫酸、
などが誉げら２１る。-broboxyedylamine)-aceI~anili1~. 3
-(N-butylaminone-aceI~7'nilyl-13-
(N-edylamino)-brobionylanili+=, 3-
(N-Cyanethylaminolerprobionylanili)-
3-(N-edylaminone-penzoylanili I-), and the first sial-V sulfuric acid represented by formula (11) includes dimethyl sulfate, diethyl sulfate, dibutyl sulfate,
There are 21 such things.
次に実施例をあげて本発明をさらに肛門に説明するが、
木兄り」ばこれらに駆足さ第１るものではない。Next, the present invention will be further explained with reference to Examples.
If you're a big brother, these things are not the first thing you need to do.
実施例中、部とあるのは重量部￥熱、味１−る。In the examples, parts are parts by weight, parts by heat, and taste.
〔実施例１〕
水４５２部に、ｍ−アミンーブ［Ｊピオニルアニリド９
０５部と酸化マグネシウム３３部を加λ、９０℃に昇温
し、９０〜９５”Ｃてジエチル硫酸２５４］γＸシを２
０分間で加えた。さらに５９０〜９５℃で１時間反応を
続は反応を終了した。室温に冷却し、３−（Ｎ、Ｎ、−
シエヂルアミノ）−プロピオニルアニリ）−１１３５部
（収率９４％）を含む水溶液を得た。[Example 1] To 452 parts of water, m-amine [J pionylanilide 9
05 parts of magnesium oxide and 33 parts of magnesium oxide were heated to 90°C, and diethyl sulfate 254]γX was heated to 90-95"C.
Added in 0 minutes. The reaction was further continued at 590 to 95°C for 1 hour, and then the reaction was completed. Cool to room temperature and add 3-(N,N,-
An aqueous solution containing 1135 parts (yield: 94%) of (cyedylamino)-propionylanili) was obtained.
この水溶液に、２−シアン−４−二１へロー６−ブロム
アニリン１２４．９部を１３％二１〜ロシル硫酸５０４
部にてジアゾ化したジアゾニウム塩を一５°Ｃから０℃
にて加λ同温度で１時間反応させ、濾過、水洗、乾燥を
して、Ｃ，１，ディスパースブルー１８３この染料原末
の状態は、非′Ｗ；（こよく、助剤としてチモールＮ（
花王アトラス社の製品〕を用いて製品化をすると、微粒
化するための製品化時間は１時間でよく、この染料で染
色した染色布は、＃明な青色であった。To this aqueous solution, 124.9 parts of 2-cyan-4-2-2-6-bromoaniline was added at 13% 21-504% of rosyl sulfate.
The diazotized diazonium salt was heated from -5°C to 0°C.
The state of the raw dye powder is C, 1, Disperse Blue 183. (
When commercialized using Kao Atlas Co., Ltd.'s product, it took only one hour to make the product into fine particles, and the dyed fabric dyed with this dye had a bright blue color.
アルキル化剤として、ジエチル硫酸に替えて、Ｐ−１−
ルエンスルホン酸エチルエステルを３３０ 部用いて２
０分で添加後、さらに９０〜９５′Ｃで６時間反応させ
た夕１は、実施例１と全く同じ方法で行い、３− （Ｎ
、Ｎ、−シエヂルアミ７ンープＬ１ピオニルアニリド１
０５部（収率８７％）な含む水／６−液を得た。As an alkylating agent, P-1-
2 using 330 parts of luenesulfonic acid ethyl ester.
After addition at 0 min, reaction was further carried out at 90 to 95'C for 6 hours.
,N,-Shiedylamine 7-P L1 pionylanilide 1
A water/6-liquid containing 0.5 parts (yield: 87%) was obtained.
、と・の水溶液に、実施例１と同様に、２−シアノ−４
−二１−ロー６−ブロムアニリン１１５５部を１３％二
１−ロシル硫１！ｉ！２４６６部にてジアゾ化したジア
ゾニウム塩ｔ、−５°ＣからＯ′Ｃにて加え、同温度で
１時間反応させ、かｉ過、水洗、乾燥をして、ｃ、ｒ。, and 2-cyano-4 in the same manner as in Example 1.
-21-Rho 6-bromoaniline 1155 parts 13% 21-Rho sulfur 1! i! 2466 parts of diazonium salt t was added at -5°C to O'C, reacted at the same temperature for 1 hour, filtered, washed with water and dried to give c and r.
ディスパースブルー１８３を２０１ドＩＸ得た。I got 201 de IX of Disperse Blue 183.
この染料原末は、少しべたつき助剤としてチモールＮ（
花王アトラス社の製品）を用いて製品化をづ−ると微粒
化の製品化時間に５時間かかつ、この染料で染色した染
色布は少し暗色がかった青色であった。This dye powder is used as a slightly sticky agent, thymol N (
When commercialization was carried out using Kao Atlas Co., Ltd.'s product, it took 5 hours to produce the product after atomization, and the dyed fabric dyed with this dye had a slightly dark blue color.
〔実施例２〕
水４５２部に、３−（Ｎ−イソプロポキシエチルアミノ
）−ンロビオニルアニリ１〜１３７５部と酸化マグネシ
ウム１６７部を加え、９０”Ｃに昇温し、９０°Ｃから
９５”Ｃでジエチル硫酸１２７部を加ンた。[Example 2] To 452 parts of water, 1 to 1375 parts of 3-(N-isopropoxyethylamino)-nibrobionylaniline and 167 parts of magnesium oxide were added, and the temperature was raised to 90"C. 127 parts of diethyl sulfate were added at C.
さらに９０〜す５ ’Ｏにて１時間反応させ、室温に冷
却し、３−（Ｎ−エヂルーＮ−イソブロポキシエヂルア
ミノフーブロビオニルアニリｌ−１４０，７部（収＊９
２％）を含む水溶液を得た。The reaction was further carried out for 1 hour at 90 to 5'O, cooled to room temperature, and 140.7 parts of 3-(N-edyl-N-isopropoxyedylaminofubrobionylaniline) (yield: 9
An aqueous solution containing 2%) was obtained.
この水溶液（工、そのままアゾ染料合成時のカップラー
溶液として使用できた。This aqueous solution could be used as it is as a coupler solution during azo dye synthesis.
〔実施例３〕
水３００部に、Ｎ−シア／エチルアニリン１４６部と酸
化マグネシウム３０部を加え、９０℃に昇ｆ）＋Ｉｉし
１こ。９０〜９５′（じにてジエチル硫酸１５４部を３
０分間で加え、さらに８５〜９５°Ｃで２時間反応した
。室温に冷却し、Ｎ−エチル−Ｎ−シアノエチル−アニ
リン１６５部（収率９５％）を含む水溶液を得た。[Example 3] 146 parts of N-cya/ethylaniline and 30 parts of magnesium oxide were added to 300 parts of water, and the temperature was raised to 90°C. 90-95' (at the same time, add 154 parts of diethyl sulfate to 3
The mixture was added for 0 minutes and further reacted at 85-95°C for 2 hours. The mixture was cooled to room temperature to obtain an aqueous solution containing 165 parts of N-ethyl-N-cyanoethyl-aniline (yield 95%).
この水溶液（工、そのままアゾ染料合成１１・５のカッ
プラー溶液として使用−〇さた。This aqueous solution was used as it is as a coupler solution in Azo Dye Synthesis 11.5.
〔実施例４〕
７Ｊ（４２０部に、Ｎ−フェニルエチル−１ｌＬｌ〜ル
イシン２Ｊ １０都と酸化マクネシウｊ＼、３０都を加
；イ、！ｌ Ｏ”Ｃに昇７局した。９０〜９５゛Ｃに−
Ｃ１ジエチル硫酸」５４部を３０分間で加ジ、さらに８
５〜９５ ”Ｑで２時間反応しに。室温に冷却し、Ｎ−
エチル−Ｎ−？−
−フエネクルーｎＬ−トルイジン２１７部（収率５）１
％）を含む水溶波を得た。[Example 4] 7J (to 420 parts, add 10 parts of N-phenylethyl-11Ll~Leucine 2J and 30 parts of magnesium oxide); 7J (!l) was added to O"C. 90-95゛to C-
Add 54 parts of ``C1 diethyl sulfate'' over 30 minutes, and add 8 parts of
React for 2 hours at 5-95"Q. Cool to room temperature and reduce to N-
Ethyl-N-? - -Fenecru nL-toluidine 217 parts (yield 5) 1
%) was obtained.
この水浴液は、そのまＪニアゾ染旧合成Ｉ１．′１′の
カップラー溶液とし−Ｃ使用できた。This water bath solution was directly used as J niazo dye old synthesis I1. -C could be used as the coupler solution for '1'.
〔実施例５〕
水９００部に、２−メトキシ−５−アぜチルアミノ−ア
ニリン１８０部と酸化マグネシウム９０部ケ加え、９０
℃に昇温した。９０〜９５°Ｃにて、ジエチル硫酸、３
０８部を３０分間で加えた。さらに９０〜９５”Ｃにて
３時間反応した後、室〃、に冷却しＮ、 Ｎ、−ジエチ
ル−２−メトキシ−５−アセチルアミン−アニリン２２
４部（収率９５％）を含む水溶液を得た。[Example 5] 180 parts of 2-methoxy-5-azethylamino-aniline and 90 parts of magnesium oxide were added to 900 parts of water.
The temperature was raised to ℃. At 90-95°C, diethyl sulfate, 3
08 parts were added over 30 minutes. After further reacting at 90-95"C for 3 hours, it was cooled to room temperature and N,N,-diethyl-2-methoxy-5-acetylamine-aniline 22
An aqueous solution containing 4 parts (95% yield) was obtained.
この水溶液に、そのままアゾ染料合成時のカップラー溶
液として使用できた。This aqueous solution could be used directly as a coupler solution during azo dye synthesis.
その結果を次表に示す。The results are shown in the table below.
Claims (1)
アノ基、低級アルコキシ基、フェニル基で置換さ第１て
いてもよい低級アルキル基を表わし、ベンゼンＪ貸Ａは
、さらに低級アルキル基、低級アルコニ）−シ基、ハロ
ゲン原子、もしくはアシルアミ ３ノ基で置換さ汎でぃ
てもよい。〕 で示さノするベンゼン系アミンを一般式（１［）％式％
（） 〔式（６）中、Ｒ’！Ｘ炭素数１〜４の飽和アルキル基
を表わす。〕 でぶさ１１るジアルキル硫酸を月１いて、水溶媒中で、
酸化マグネシウムよたは水酸化マクネシウムの存在下に
、６０〜１０００の６１請度て反応さ−１１ることを牛
〒′ｅとする、一般式（１，１１）〔式（ＩＩ）中、Ｒ
’ｆ：Ｃ１式（Ｉ）中のＲ’ 、−ｔミたは式（１１）
中のＲ′と同一 の意味を表わし、ｘｌは式（ＩＩ）中
のぜと同一の意味な表わ−う−６またベンゼンにＨＡ
＋；１．式（ＩＩ）と同一の意味を表わす。〕 で示さ２′しる芳香族アミンのアルキル化方法。[Claims] General formula (I) 'ti, tt 0 In formula (I), R' is a hydrogen atom, 'allyl group, etc.; Benzene may be further substituted with a lower alkyl group, a lower alkoxy group, a halogen atom, or an acylamino group. ] The benzene-based amine represented by the general formula (1[)% formula%
() [In formula (6), R'! X represents a saturated alkyl group having 1 to 4 carbon atoms. ] Add a large amount of dialkyl sulfuric acid once a month in an aqueous solvent,
In the presence of magnesium oxide or magnesium hydroxide, the general formula (1,11) [in formula (II), R
'f: R' in C1 formula (I), -tmi or formula (11)
xl has the same meaning as R' in formula (II), and xl has the same meaning as R' in formula (II).
+;1. It has the same meaning as formula (II). ] A method for alkylating an aromatic amine represented by 2'.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58086609A JPS59212449A (en) | 1983-05-19 | 1983-05-19 | Method for alkylating aromatic amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58086609A JPS59212449A (en) | 1983-05-19 | 1983-05-19 | Method for alkylating aromatic amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59212449A true JPS59212449A (en) | 1984-12-01 |
| JPS6240349B2 JPS6240349B2 (en) | 1987-08-27 |
Family
ID=13891753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58086609A Granted JPS59212449A (en) | 1983-05-19 | 1983-05-19 | Method for alkylating aromatic amine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59212449A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02180375A (en) * | 1988-12-30 | 1990-07-13 | Aisin Aw Co Ltd | Actuator for friction engaging device |
| JPH0396471A (en) * | 1989-09-06 | 1991-04-22 | Daifuku Co Ltd | Electric car for carriage |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5320017A (en) * | 1976-08-05 | 1978-02-23 | Nissan Motor Co Ltd | Exhaust reflux controller |
| JPS5738755A (en) * | 1980-08-14 | 1982-03-03 | Mitsubishi Chem Ind Ltd | Alkylating method of aniline |
-
1983
- 1983-05-19 JP JP58086609A patent/JPS59212449A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5320017A (en) * | 1976-08-05 | 1978-02-23 | Nissan Motor Co Ltd | Exhaust reflux controller |
| JPS5738755A (en) * | 1980-08-14 | 1982-03-03 | Mitsubishi Chem Ind Ltd | Alkylating method of aniline |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6240349B2 (en) | 1987-08-27 |
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