JPS61254550A - Production of azo compound - Google Patents
Production of azo compoundInfo
- Publication number
- JPS61254550A JPS61254550A JP9592985A JP9592985A JPS61254550A JP S61254550 A JPS61254550 A JP S61254550A JP 9592985 A JP9592985 A JP 9592985A JP 9592985 A JP9592985 A JP 9592985A JP S61254550 A JPS61254550 A JP S61254550A
- Authority
- JP
- Japan
- Prior art keywords
- naphthol
- diazo
- beta
- reaction
- solution
- 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
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明はアゾ化合物の製造法の改良に関する。[Detailed description of the invention] Industrial applications The present invention relates to an improvement in a method for producing an azo compound.
より詳細には、一般式（［［）
（式中、Ｘは水素またはニトロ基を示す。）で表わされ
るアゾ化合物の製造法に関する。一般式但）で表わされ
るアゾ化合物は、酸性媒染染料として、またさらに金属
錯塩化して金属錯塩染料として実用されている。More specifically, the present invention relates to a method for producing an azo compound represented by the general formula ([[) (wherein, X represents hydrogen or a nitro group). The azo compound represented by the general formula (2) is used as an acidic mordant dye, and also as a metal complex dye after being converted into a metal complex salt.
従来の技術
前記一般式σ）で表わされるアゾ化合物は、従来つぎの
方法で製造されていた。BACKGROUND ART The azo compound represented by the general formula σ) has conventionally been produced by the following method.
すなわち、ｌ−ジアゾ−２−ナフトール−４−スルホン
酸、または１−ジアゾ−６−ニトロ−２−ナフトール−
４−スルホン酸のアルカリ水溶液に、β−ナフトールの
アルカリ水溶液を加え４０〜６０℃で所要時間カップリ
ング反応を行い、ついで酸史中和して生成物を乾燥して
アゾ化合物を得る。That is, 1-diazo-2-naphthol-4-sulfonic acid, or 1-diazo-6-nitro-2-naphthol-
An aqueous alkali solution of β-naphthol is added to an aqueous alkaline solution of 4-sulfonic acid, a coupling reaction is carried out at 40 to 60° C. for a required time, and then an azo compound is obtained by neutralizing the acid solution and drying the product.
上記の従来法で得られるアゾ化合物を酸性媒染染料また
は、これをさらに金属錯塩化した金属錯塩染料をポリア
ミド繊維の染色に用いた場合、副生物が染料操作上引き
起す問題、または染色や堅牢度の低下等の問題がありだ
。When acid mordant dyes obtained from the azo compounds obtained by the above conventional methods or metal complex dyes obtained by further converting these into metal complex salts are used for dyeing polyamide fibers, by-products may cause problems during dye operation, or dyeing and fastness problems may occur. There are problems such as a decline in
これらの問題は、前記アゾ化合物（６）を生成するカッ
プリング反応時、次式（ｍ）で表わされるような推定構
造の副生物が生ずるためと考えられる。These problems are thought to be due to the production of by-products having the presumed structure represented by the following formula (m) during the coupling reaction to produce the azo compound (6).
（ｍ）
本発明の課題は、前記一般式（Ｉ）で表わされるジアゾ
化合物とβ−ナフトールのカップリング反応において副
生物の生成を抑制する方法を提供することである。(m) An object of the present invention is to provide a method for suppressing the production of by-products in the coupling reaction between the diazo compound represented by the general formula (I) and β-naphthol.
問題点を解決するための手段
本発明者らは、上記の課題を解決するため鋭意検討した
。Means for Solving the Problems The present inventors have made extensive studies to solve the above problems.
その結果、カップリング反応を窒素雰囲気下で実施して
得られたアゾ化合物を用いた染料によるポリアミド繊維
の染色において、上記染色操作上または染色物での問題
が解消しうることを見い出し、本発明を完成した。As a result, it has been found that the above-mentioned problems in the dyeing operation or in the dyed product can be solved in dyeing polyamide fibers with a dye using an azo compound obtained by carrying out the coupling reaction in a nitrogen atmosphere, and the present invention has been made. completed.
すなわち、本発明は一般式（Ｉ）
（式中、Ｘは水素またはニトロ基を示す。）で表わされ
るジアゾ化合物とβ−ナフトールとをカップリング反応
させて一般式叫
（式中、Ｘは一般式α）と同様の意味を示す。）で表わ
されるアゾ化合物を製造するに際し、窒素雰囲気下にカ
ップリング反応させることを特徴とするアゾ化合物の製
造法である。That is, the present invention provides a coupling reaction between a diazo compound represented by the general formula (I) (wherein, X represents hydrogen or a nitro group) and β-naphthol, It has the same meaning as formula α). ) is a method for producing an azo compound characterized by carrying out a coupling reaction in a nitrogen atmosphere.
本発明の方法に用いるジアゾ化合物は、１−ジアゾ−２
−ナフトール−４−スルホン酸、または１−ジアゾ−６
−ニトロ−２−ナフトール−４−スルホン酸である。The diazo compound used in the method of the present invention is 1-diazo-2
-naphthol-4-sulfonic acid, or 1-diazo-6
-nitro-2-naphthol-4-sulfonic acid.
これらの化合物はｌ−アミノ−２−ナフトール−４−ス
ルホン酸１．・予≦啄１−アｊ／−゛ｌ−エμロー２ア
すブト・−ル−４−スｌし木工酢玉９１紫＾］−殊て°
ミ゛アｙｌヒレｚｑｉａｐ矛りる・１゜
本発明の方法において、原料化合物の使用量は。These compounds include l-amino-2-naphthol-4-sulfonic acid 1.・Pre-order≦1-Aj/-゛l-Eμlow2Asbut--Rules-4-Slshi Woodworking Vinegar 91 Purple^]-Special °
1. In the method of the present invention, what is the amount of the raw material compound used?
ジアゾ化合物１モルに対して、β−ナフトールを１モル
以上ないし少過剰量１通常１．２モル以下用いれば十分
である。It is sufficient to use β-naphthol in an amount of 1 mol or more to a slight excess of 1 usually 1.2 mol or less per 1 mol of the diazo compound.
本発明の方法を実施するには、通常、まずジアゾ化合物
およびβ−ナフトールを、それぞれ別に。To carry out the process of the invention, the diazo compound and the β-naphthol are usually first prepared separately.
所定量を水酸化ナトリウム、炭酸ナトリウム等のアルカ
リ水溶液に溶解させる。A predetermined amount is dissolved in an alkaline aqueous solution such as sodium hydroxide or sodium carbonate.
ついでジアゾ化合物のアルカリ水溶液に、硫安を添加し
た後、窒素ガスを吹き込みながら、別に調整したβ−す
７トールのアルカリ水溶液を添加する。Next, ammonium sulfate is added to the alkaline aqueous solution of the diazo compound, and then a separately prepared alkaline aqueous solution of β-7 torr is added while blowing nitrogen gas.
本発明の方法において窒素雰囲気下のカップリング反応
とは、窒素ガスをジアゾ化合物の水溶液に直接吹き込み
、バブリングさせるのが好ましい。In the method of the present invention, the coupling reaction under a nitrogen atmosphere preferably involves bubbling nitrogen gas by directly blowing it into the aqueous solution of the diazo compound.
すなわち、反応器内を窒素雰囲気下におき、かつ反応液
中に、カップリング反応を通じて、窒素を通気させる。That is, the interior of the reactor is placed under a nitrogen atmosphere, and nitrogen is bubbled into the reaction solution through the coupling reaction.
β−ナフトールのアルカリ水溶液は、窒素ガスを通気中
のジアゾ化合物のアルカリ水溶液に連続的または間欠的
に添加する。好ましくは短時間に装入する。To prepare the alkaline aqueous solution of β-naphthol, nitrogen gas is continuously or intermittently added to the alkaline aqueous solution of the diazo compound during ventilation. Preferably, it is charged in a short period of time.
カップリング反応の温度は、通常、３０〜７０℃の範囲
であり、反応液のＰＨは９．５〜１１．０の範囲に保持
する。反応時間は反応条件により異なリ、必ずしも限定
されないが、通常数分〜数時間で終了する。The temperature of the coupling reaction is usually in the range of 30 to 70°C, and the pH of the reaction solution is maintained in the range of 9.5 to 11.0. Although the reaction time varies depending on the reaction conditions and is not necessarily limited, the reaction is usually completed within several minutes to several hours.
カップリング反応終了後、塩析して析出させ、ｐ別、乾
燥して目的のアゾ化合物を得ることができる。After the coupling reaction is completed, the desired azo compound can be obtained by salting out, precipitating, separating p and drying.
作用および効果
本発明の方法のように、一般式α）で表わされるジアゾ
化合物とβ−ナフトールとのカップリング反応を、窒素
雰囲気下に実施することによって、副生物の生成が抑制
される。Actions and Effects As in the method of the present invention, by carrying out the coupling reaction between the diazo compound represented by the general formula α) and β-naphthol under a nitrogen atmosphere, the production of by-products is suppressed.
したがって、本発明の方法で得られるアゾ化合物を酸性
媒染染料、また、これを金属錯塩化した金属錯塩染料を
用いた、ポリアミド繊維の染色において、染色操作上、
および染色物での問題が解消される。Therefore, in dyeing polyamide fibers using an acid mordant dye using the azo compound obtained by the method of the present invention, or a metal complex dye obtained by converting the azo compound into a metal complex salt, there are
and problems with dyeing are eliminated.
すなわち、本発明の方法は、酸性媒染染料および金属錯
塩染料中間体として有用なアゾ化合物の有効な製造法を
提供するものである。That is, the method of the present invention provides an effective method for producing an azo compound useful as an intermediate for acidic mordant dyes and metal complex dyes.
実施例 以下、実施例で本発明を説明する。Example The present invention will be explained below with reference to Examples.
実施例−１
１−ジアゾ−２−ナフトール−４−スルホン酸（純度１
００％品として）３００部を水５００部に装入し、４５
チ苛性ソ一ダ１１４部を加え、ＰＨを６８０に調整して
溶解した。この溶液を４０００部容積のガラス製反応機
に移液し、硫安２５部を加えた。Example-1 1-diazo-2-naphthol-4-sulfonic acid (purity 1
00% product) was charged into 500 parts of water, and 45
114 parts of caustic soda was added, the pH was adjusted to 680, and the mixture was dissolved. This solution was transferred to a glass reactor having a capacity of 4000 parts, and 25 parts of ammonium sulfate was added thereto.
別に７５０部の水に４５チ苛性ソ一ダ１３３部を加え、
４０°Ｃに昇温し、この中にβ−ナフトール２．８２．
５部を装入し撹拌溶解した。Separately, add 133 parts of 45% caustic soda to 750 parts of water,
The temperature was raised to 40°C, and 2.82% of β-naphthol was added thereto.
5 parts were charged and dissolved with stirring.
１−ジアゾ−２−ナフトール−４−スルホン酸溶解液に
、窒素ガスを約１０ｍ？／時、の割合で吹き込み、この
中にβ−ナフトール溶解液を約５分を要して加えた。About 10 m of nitrogen gas is added to the 1-diazo-2-naphthol-4-sulfonic acid solution. /hour, and the β-naphthol solution was added thereto over a period of about 5 minutes.
次いで工業塩１７９部加え、４０’Ｃで３０分保温し、
その後、１時間を要して６０’Ｃに昇温し、同温度で１
時間反応を行った。Next, 179 parts of industrial salt was added and kept at 40'C for 30 minutes.
After that, it took 1 hour to raise the temperature to 60'C, and at the same temperature
A time reaction was performed.
反応終了後、窒素ガスの吹き込みを中止した。After the reaction was completed, blowing of nitrogen gas was stopped.
得られたカップリング反応混合物に工業塩を加えて、塩
析し、ついで塩酸で中和し、濾過した後、洗浄した炉塊
を乾燥して次式
で表わされるアゾ化合物を得た。物質収率は３００チで
あった。Industrial salt was added to the resulting coupling reaction mixture for salting out, followed by neutralization with hydrochloric acid, filtration, and the washed furnace block was dried to obtain an azo compound represented by the following formula. The material yield was 300 cm.
※物質収率とは１−ジアゾ−２−ナフトール−４−スル
ホン酸１００部よりアゾ化合物の得られた部数の百分率
を示す。*Material yield refers to the percentage of the azo compound obtained from 100 parts of 1-diazo-2-naphthol-4-sulfonic acid.
得られた化合物を、温水７５０部に装入し、４５係苛性
ソ一ダ約１０部を加えＰＨを１１〜１１．５に調整する
。The obtained compound is charged into 750 parts of warm water, and about 10 parts of 45% caustic soda is added to adjust the pH to 11 to 11.5.
クロムサリチル酸溶液（１００％サリチル酸として）１
８２部を装入し、Ｚｏｏ℃迄約２特約２時間て昇温し、
同温度で５時間反応を行なった。Chromium salicylic acid solution (as 100% salicylic acid) 1
Charge 82 parts and raise the temperature to Zoo℃ for about 2 hours.
The reaction was carried out at the same temperature for 5 hours.
々ロムｌｌ／ｊｌ！ｌｃ′Ｔ披ルマＩル々−ゴし１プ軌
植Ｊ＋。tromll/jl! lc'Talma I Lulugoshi 1P Orbit J+.
不要物を除き、ｐ液を中和槽にて４０係硫酸をＤ口えて
ＰＨを６〜６．５迄中和する。After removing unnecessary substances, the pH of the p solution is neutralized to 6 to 6.5 by adding 40% sulfuric acid in a neutralization tank.
中和液に塩化カルシウム５５．５部、工業塩３９０部を
加えて、スプレードライヤーで乾燥して染料を得た。55.5 parts of calcium chloride and 390 parts of industrial salt were added to the neutralized solution and dried with a spray dryer to obtain a dye.
この染料を用いて、デ杯−ｙｒｔＩＣｔダ重簀〆ＸＶ１
ｇ＊＊ｉ＆−２ナイロン糸を下記条件で染色した。Use this dye to
g**i&-2 nylon yarn was dyed under the following conditions.
染色時に同浴で、アセラードを処理し、この試験白布に
対する汚染を調べた所、黄色汚染が全くなかった。染色
物は鮮明な青色であった。Acerard was treated in the same bath during dyeing, and staining of this test white fabric was examined, and no yellow staining was found. The dyed material was a bright blue color.
染色条件：染色濃度 ＣＩＡ Ｂｌｕｅ ２０７４％
（５ＮＦ浴 比 １：５０
染色温度 ９７〜９８℃
時 間 ４５分
比較例
実施例−１で窒素ガスを吹き込まずに反応させ、を染色
し、同浴でアセテートへの汚染を調べた・この試験白布
へはかなり黄色に汚染（３〜４級）した。Staining conditions: Staining concentration CIA Blue 2074%
(5NF bath Ratio 1:50 Dyeing temperature 97-98℃ Time 45 minutes Comparative example Example-1 was reacted without blowing nitrogen gas, and the contamination to acetate was investigated in the same bath.・This test The white cloth was heavily stained yellow (grade 3 to 4).
Claims (1)
るジアゾ化合物とβ−ナフトールとをカップリング反応
させて一般式（II） ▲数式、化学式、表等があります▼（II） 〔式中、Ｘは一般式（ I ）と同様の意味を示す。〕で
表わされるアゾ化合物を製造するに際し、窒素雰囲気下
でカップリング反応させることを特徴とするアゾ化合物
の製造方法。[Claims] 1) General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X represents hydrogen or a nitro group. ] The diazo compound represented by the formula and β-naphthol are subjected to a coupling reaction to form the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, X has the same meaning as in the general formula (I) shows. ] A method for producing an azo compound, which comprises carrying out a coupling reaction in a nitrogen atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9592985A JPS61254550A (en) | 1985-05-08 | 1985-05-08 | Production of azo compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9592985A JPS61254550A (en) | 1985-05-08 | 1985-05-08 | Production of azo compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61254550A true JPS61254550A (en) | 1986-11-12 |
Family
ID=14150958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9592985A Pending JPS61254550A (en) | 1985-05-08 | 1985-05-08 | Production of azo compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61254550A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0307357A2 (en) * | 1987-09-08 | 1989-03-15 | Ciba-Geigy Ag | Process for the preparation of azo dyes capable of being metallized |
| EP0320447A2 (en) * | 1987-12-07 | 1989-06-14 | Ciba-Geigy Ag | Process for the preparation of metallisable azo dyes |
| EP0320446A2 (en) * | 1987-12-07 | 1989-06-14 | Ciba-Geigy Ag | Process for the preparation of metallizable azo dyes |
| US4996303A (en) * | 1987-12-04 | 1991-02-26 | Ciba-Geigy Corporation | Preparation of 1:2 metal complex dyes by coupling in the presence of a metal donor in an inert gas atmosphere |
| JPH0770457A (en) * | 1993-05-27 | 1995-03-14 | Taoka Chem Co Ltd | Production of 1:2-chromium complex azo dye solution |
-
1985
- 1985-05-08 JP JP9592985A patent/JPS61254550A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0307357A2 (en) * | 1987-09-08 | 1989-03-15 | Ciba-Geigy Ag | Process for the preparation of azo dyes capable of being metallized |
| JPH01101376A (en) * | 1987-09-08 | 1989-04-19 | Ciba Geigy Ag | Production of metallizable azo dye |
| US5026830A (en) * | 1987-09-08 | 1991-06-25 | Ciba-Geigy Corporation | Process for the preparation of azo dyes by carrying out coupling in the presence of an alkali metal chloride and ammonium chloride |
| US5196518A (en) * | 1987-09-08 | 1993-03-23 | Ciba-Geigy Corporation | Process for the preparation of metallizable azo dyes by carrying out the coupling in the presence of a buffer mixture |
| US4996303A (en) * | 1987-12-04 | 1991-02-26 | Ciba-Geigy Corporation | Preparation of 1:2 metal complex dyes by coupling in the presence of a metal donor in an inert gas atmosphere |
| EP0320447A2 (en) * | 1987-12-07 | 1989-06-14 | Ciba-Geigy Ag | Process for the preparation of metallisable azo dyes |
| EP0320446A2 (en) * | 1987-12-07 | 1989-06-14 | Ciba-Geigy Ag | Process for the preparation of metallizable azo dyes |
| DE3841037A1 (en) * | 1987-12-07 | 1989-06-15 | Ciba Geigy Ag | METHOD FOR PRODUCING METALIZABLE AZOFINES |
| US4994561A (en) * | 1987-12-07 | 1991-02-19 | Ciba-Geigy Corporation | Process for the preparation of metallizable azo dyes carrying out coupling in an inert gas atmosphere in the presence of an ammonium salt |
| US5126435A (en) * | 1987-12-07 | 1992-06-30 | Ciba-Geigy Corporation | Process for the preparation of metallisable azo dyes |
| JPH0770457A (en) * | 1993-05-27 | 1995-03-14 | Taoka Chem Co Ltd | Production of 1:2-chromium complex azo dye solution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR850001475B1 (en) | Manufacturing method of azodyes for cellulose fibers | |
| GB1491697A (en) | Process for the production of ferrocyanide blue | |
| JPS61254550A (en) | Production of azo compound | |
| CN103205134B (en) | Method for synthesizing DSD (4, 4'-diaminostilbene-2, 2'-disulfonic) acid-triazine fluorescent brightening agents | |
| DE2924228C2 (en) | ||
| KR100270403B1 (en) | Reactive red dyes containing monochlorotriazine and acetoxyethyl sulfone groups | |
| KR960001064B1 (en) | Process for the preparation of the lithium salt of a | |
| US1941285A (en) | Titanium sulphate compounds | |
| JP3567136B2 (en) | Blue reactive dye having monochlorotriazine group and acetoxyethyl sulfone group | |
| CH688281A5 (en) | A process for producing 1: 2-Metallkomplexazofarbstoffen. | |
| KR100270401B1 (en) | Reactive black dyes containing acetoxyethylsulfone moiety | |
| KR950007220B1 (en) | Process for the manufacture of copper complex disazo compounds | |
| KR100288121B1 (en) | Reactive red dyes containing monochlorotriazine and acetoxyethyl sulfone groups | |
| KR100288120B1 (en) | Reactive blue dyes containing monochlorotriazine and acetoxyethyl sulfone groups | |
| US1594547A (en) | Production of alpha-nitronaphthalene-beta-sulphonic acids | |
| JP3589700B2 (en) | Production method and dyeing method of liquid composition of reactive dye | |
| JPH056588B2 (en) | ||
| JPS6269889A (en) | Dyeing of polyester/cellulose blended spun/interlaced product | |
| JPH0770457A (en) | Production of 1:2-chromium complex azo dye solution | |
| US597401A (en) | Carl dreher | |
| SU1578162A1 (en) | Method of obtaining active copper-containing vinylsulfonic azodyes | |
| DE2618670A1 (en) | NEW AZO DYES, METHODS FOR THEIR MANUFACTURING AND USE | |
| DE897899C (en) | Process for the preparation of dyes of the anthraquinone series | |
| JPH07109424A (en) | Liquid composition of reactive dye and method for dyeing by using the same | |
| RO85610B1 (en) | Process for preparing chromatable acid black dyestuff |