JPS6157A - Preparation of halogenated p-aminobenzene - Google Patents
Preparation of halogenated p-aminobenzeneInfo
- Publication number
- JPS6157A JPS6157A JP11938184A JP11938184A JPS6157A JP S6157 A JPS6157 A JP S6157A JP 11938184 A JP11938184 A JP 11938184A JP 11938184 A JP11938184 A JP 11938184A JP S6157 A JPS6157 A JP S6157A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- benzene ring
- halogenated
- hydrogen peroxide
- aminobenzene
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、一般式（Ｉ）
（但し式（９）中のベンゼン環Ａは、低級アルキル基、
低級アルコキシ基、ニトロ基、低級アルコキシカルボニ
ル基、ハロゲン原子により置換されていてもよい。）
で示されるＰ−アミノアゾベンゼン類を式（ＩＩ）Ｈ−
Ｘ （ＩＩ）（式（ＩＩ）中
Ｘは塩素原子、臭素原子又は沃素原子を表わす。）
で示されるハロゲン化水素酸水溶液中、過酸化水素の存
在下にハロゲン化することを特徴とする式（式（ｎＤ中
のベンゼン環Ａは、式（Ｉ）のベンゼン環Ａと同一の意
味を表わし、Ｘは式（ＩＩ）と同一の意味を表わす。）
（式（ＩＶ）中のベンゼン原人は、式（Ｉ）のベンゼン
原人と同一の意味を表わし、又は式（ＴＩ）のＸと同一
の意味を表わす。）
で示されるハロゲン化アゾベンゼンの製造）ｊ法に関す
る。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to the general formula (I) (wherein benzene ring A in formula (9) is a lower alkyl group,
It may be substituted with a lower alkoxy group, a nitro group, a lower alkoxycarbonyl group, or a halogen atom. ) P-aminoazobenzenes represented by the formula (II) H-
A formula characterized by halogenation in the presence of hydrogen peroxide in an aqueous solution of hydrohalic acid represented by X (II) (X in formula (II) represents a chlorine atom, a bromine atom, or an iodine atom) (Benzene ring A in formula (nD) has the same meaning as benzene ring A in formula (I), and X has the same meaning as in formula (II).) (Benzene ring A in formula (IV) represents the same meaning as the benzene progenitor of formula (I), or represents the same meaning as X of formula (TI).
式（Ｉ［Ｉ）又は式（■）で示されるモノまたはジハロ
ゲン化アゾベンゼンは、ジスアゾ染料の中間体として重
要な化合物である。Mono- or dihalogenated azobenzene represented by formula (I [I) or formula (■)] is an important compound as an intermediate for disazo dyes.
従来の技術
式（ｍ）又は式悄）で示されるハロゲン化Ｐ−アミノア
ゾベンゼン類の製造方法は、たとえば特開昭５５−５２
３７５号公報に記載されているように、式（Ｉ）で示さ
れるＰ−アミノアゾベンゼン類を、酢酸又はアルコール
のような有機溶媒中にて、ハロゲンと反応させることに
より、ハロゲン化Ｐ−アミノアゾベンゼン類を製造して
いた。Conventional methods for producing halogenated P-aminoazobenzenes represented by the technical formula (m) or formula (2) are described, for example, in JP-A-55-52.
As described in Japanese Patent No. 375, halogenated P-aminoazobenzene is produced by reacting P-aminoazobenzenes represented by formula (I) with a halogen in an organic solvent such as acetic acid or alcohol. were manufacturing types.
発明が解決しようとする問題点
特開昭５５−５２３７５記載のにうなハロゲン化反応に
有機溶媒を用いることは、製造コス１−が高くなったり
、臭気や排水の高負荷化など環境汚染上の問題も大きい
。Problems to be Solved by the Invention The use of organic solvents in the halogenation reaction described in JP-A-55-52375 increases production costs and causes environmental pollution such as high odor and wastewater load. The problem is also big.
問題点を解決するだめの手段
そこで発明者らは鋭意検討の結果、式（Ｉ）で示される
Ｐ−アミノアゾベンゼン類９を、水性媒体中過酸化水素
存在下、式（ＴＩ）で示されるノ１０ゲン化水素酸水溶
液にてハロゲン化をする方法を見０出した。Means to Solve the Problem Therefore, as a result of intensive studies, the inventors found that P-aminoazobenzenes 9 represented by formula (I) were treated with P-aminoazobenzenes 9 represented by formula (TI) in an aqueous medium in the presence of hydrogen peroxide. We have discovered a method for halogenation using an aqueous solution of 10-hydrogenic acid.
すなわち、本発明方法はハロゲン化水素酸水溶液、好ま
しくは１チ〜１０係水溶液にＰ−アミノアゾベンゼン類
を加え、溶解又は懸濁させながら、過酸化水素を加え、
ハロゲン化反応を行う。反応終了後は、炉別することに
より、式（ＴＲＩ）又は式（ＩＶ）で示されるハロゲン
化Ｐ−アミノアゾベンゼン類を高純度高収率で得るもの
である。That is, the method of the present invention involves adding P-aminoazobenzenes to a hydrohalic acid aqueous solution, preferably a 1-10 aqueous solution, and adding hydrogen peroxide while dissolving or suspending the compound.
Perform a halogenation reaction. After the reaction is completed, the halogenated P-aminoazobenzene represented by formula (TRI) or formula (IV) is obtained with high purity and high yield by separating the reaction mixture into a furnace.
本発明において使用するハロゲン化水素水溶液の量は、
Ｐ−アミノアゾベンゼン類の５・〜３０重量倍が好まし
し３゜又、式（ｍ）のモノハロゲン化Ｐ−アミノアゾベ
ンゼン類を得るには、Ｐ−アミノアゾベンゼンに対して
、Ａロダン化水素酸０９〜１４モル比と、過酸化水素０
．９〜．１２モル比を用いるのが好ましく、文武（ＩＶ
）のジノ＼ロゲン化Ｐ−アミノアゾベンゼン類を得るに
は、 Ａロゲン化水素酸０２〜４．０モル比、過酸化水
素２０〜３．０モル比を用いるのが好ましい。反応温度
としては３０〜９０°Ｃがよい。The amount of hydrogen halide aqueous solution used in the present invention is
Preferably, the amount is 5 to 30 times the weight of P-aminoazobenzenes, and in order to obtain monohalogenated P-aminoazobenzenes of formula (m), A-hydrodanide is added to P-aminoazobenzene. Acid 09-14 molar ratio and hydrogen peroxide 0
．． 9~. Preferably, a molar ratio of 12 is used, and Wenmu (IV
), it is preferable to use a molar ratio of 02 to 4.0 molar ratio of A halogenated acid and 20 to 3.0 molar ratio of hydrogen peroxide. The reaction temperature is preferably 30 to 90°C.
本発明の式（Ｉ）で示されるＰ−アミノアゾベンゼン類
の具体的な例としては、次のものがハロゲン化反応の原
料に用いられる。As specific examples of P-aminoazobenzenes represented by formula (I) of the present invention, the following are used as raw materials for the halogenation reaction.
作用及び効果
本発明の特徴とするところは、水性溶媒中で前記式（Ｉ
）で示されるＰ−アミノアゾベンゼン類を、過酸化水素
酸の存在下ハロゲン化することにより、式≦Ｉｎ）又は
式（ＩＶ）で示されるハロゲン化Ｐ−アミノアゾベンゼ
ン類を製造する方法であり、高価な有機溶媒を使用しな
いので工業的に安価に実施出来、かつその取り扱いも容
易であり、排水面や息気面から公害対策上、極めて良好
な製造方法であるという利点を有し、さらに原料とする
Ｐ−アミノアゾベンゼン類は、前工程における湿炉塊を
乾燥することなくそのまま原料として使用出来るなど本
発明の工業的価値は大きい。Actions and Effects The present invention is characterized in that the above formula (I
) is a method for producing halogenated P-aminoazobenzenes represented by the formula ≦In) or formula (IV) by halogenating the P-aminoazobenzenes represented by the formula (IV) in the presence of hydrogen peroxide, It does not use expensive organic solvents, so it can be carried out industrially at low cost, and it is easy to handle.It has the advantage of being an extremely good manufacturing method in terms of pollution prevention from the drainage and breath surfaces. The industrial value of the present invention is great because the P-aminoazobenzenes can be used as raw materials without drying the wet furnace mass in the previous step.
本発明の工業的利点をまとめれば次表のとおりである。The industrial advantages of the present invention are summarized in the following table.
以下に実施例を用しって、本発明を更に詳しく説□明す
るが、本発明は実施例に限定されるものではない。The present invention will be explained in more detail below using Examples, but the present invention is not limited to the Examples.
実施例中「部」、「チ」とあるのは「重量部」または「
重量部」を示す。In the examples, "parts" and "chi" refer to "parts by weight" or "parts by weight".
Parts by weight.
〔実施例−１〕
水８５０部に、Ｐ−アミノアゾベンゼン５７部を懸濁し
た。４７％臭化水素酸１ｉ ４部を加え、７０℃に昇温
した０７０〜７５℃にて、３〔１チ過酸化水素水３３部
を加え、７０〜７５℃にて４時間反応した。室温に冷却
し濾過４乾燥し１、 収量７７部の粗生成物を得、これ
をカラムクロマ１−グラフィーにより精製し、２−プロ
モー４−フェニルアゾアニリン５２部を得た。収率６５
チ。[Example-1] 57 parts of P-aminoazobenzene was suspended in 850 parts of water. 4 parts of 47% hydrobromic acid 1i were added, the temperature was raised to 70°C, 070-75°C, 33 parts of 3[1-thihydrogen peroxide solution was added, and the mixture was reacted at 70-75°C for 4 hours. The mixture was cooled to room temperature, filtered and dried to obtain 77 parts of a crude product, which was purified by column chromatography to obtain 52 parts of 2-promo-4-phenylazoaniline. Yield 65
blood.
〔実施例２〜６〕
実施例−１と同様にして、表−１の化合物を得た０
〔実施例−７〕
水８５０部と４７チ臭化水素酸１２８部を混合り、Ｐ−
７ミノアゾベンゼン５７部を加えた後、７０℃に昇温し
た。３０％過酸化水素６５部を７０〜８０℃にて加えた
。７０〜８０°Ｃにて２時間反応した。７０℃にて濾過
し、濾過ケーキを乾燥し、２．６−ジプロムー４−フェ
ニルアゾアニリン９８部を得た。収率９６％。[Examples 2 to 6] Compounds shown in Table 1 were obtained in the same manner as in Example 1. [Example 7] 850 parts of water and 128 parts of 47 hydrobromic acid were mixed, and P-
After adding 57 parts of 7-minoazobenzene, the temperature was raised to 70°C. 65 parts of 30% hydrogen peroxide was added at 70-80°C. The reaction was carried out at 70-80°C for 2 hours. The mixture was filtered at 70°C and the filter cake was dried to obtain 98 parts of 2,6-dipromo-4-phenylazoaniline. Yield 96%.
〔実施例８〜１３〕 実施例−７と同様にして、表−２の化合物を得た。[Examples 8 to 13] The compounds shown in Table 2 were obtained in the same manner as in Example 7.
Claims (1)
低級アルコキシ基、ニトロ基、低級アルコキシカルボニ
ル基、ハロゲン原子により置換されていてもよい。） で示されるＰ−アミノアゾベンゼン類を、水性媒体中で
式（II） Ｈ−Ｘ（II） （式（II）中Ｘは塩素原子、臭素原子及び沃素原子を表
わす。） で示されるハロゲン化水素酸水溶液を用いて過酸化水素
存在下にハロゲン化することを特徴とする式（III） ▲数式、化学式、表等があります▼（III） （式（III）中のベンゼン環Ａは、式（ I ）のベンゼン
環Ａと同一の意味を表わし、Ｘは式（II）のＸと同一。 ） 又は、式（IV） ▲数式、化学式、表等があります▼（IV） （式（IV）中のベンゼン環Ａは、式（ I ）のベンゼン
環Ａと同一の意味を表わし、Ｘは式（II）のＸと同一。 ） で示されるハロゲン化アゾベンゼン類の製造方法。[Claims] Formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (However, benzene ring A in (I) is a lower alkyl group,
It may be substituted with a lower alkoxy group, a nitro group, a lower alkoxycarbonyl group, or a halogen atom. ) P-aminoazobenzenes represented by the formula (II) H-X (II) (X in the formula (II) represents a chlorine atom, a bromine atom, and an iodine atom) are halogenated in an aqueous medium. Formula (III) characterized by halogenation in the presence of hydrogen peroxide using an aqueous hydrogen acid solution ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (Benzene ring A in formula (III) is Expresses the same meaning as benzene ring A in (I), and X is the same as X in formula (II).) Or formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (Formula (IV) Benzene ring A has the same meaning as benzene ring A in formula (I), and X has the same meaning as X in formula (II).) A method for producing a halogenated azobenzene represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11938184A JPS6157A (en) | 1984-06-11 | 1984-06-11 | Preparation of halogenated p-aminobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11938184A JPS6157A (en) | 1984-06-11 | 1984-06-11 | Preparation of halogenated p-aminobenzene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6157A true JPS6157A (en) | 1986-01-06 |
Family
ID=14760098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11938184A Pending JPS6157A (en) | 1984-06-11 | 1984-06-11 | Preparation of halogenated p-aminobenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6157A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011075210A2 (en) * | 2009-12-18 | 2011-06-23 | The Scripps Research Institute | Small molecules that covalently modify transthyretin |
-
1984
- 1984-06-11 JP JP11938184A patent/JPS6157A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011075210A2 (en) * | 2009-12-18 | 2011-06-23 | The Scripps Research Institute | Small molecules that covalently modify transthyretin |
| WO2011075210A3 (en) * | 2009-12-18 | 2011-10-20 | The Scripps Research Institute | Small molecules that covalently modify transthyretin |
| US8703815B2 (en) | 2009-12-18 | 2014-04-22 | The Scripps Research Institute | Small molecules that covalently modify transthyretin |
| US9771321B2 (en) | 2009-12-18 | 2017-09-26 | The Scripps Research Institute | Small molecules that covalently modify transthyretin |
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