JPS6110541A - Production of 1-amino-2-bromo-4-hydroxyanthraquinone - Google Patents
Production of 1-amino-2-bromo-4-hydroxyanthraquinoneInfo
- Publication number
- JPS6110541A JPS6110541A JP60106888A JP10688885A JPS6110541A JP S6110541 A JPS6110541 A JP S6110541A JP 60106888 A JP60106888 A JP 60106888A JP 10688885 A JP10688885 A JP 10688885A JP S6110541 A JPS6110541 A JP S6110541A
- Authority
- JP
- Japan
- Prior art keywords
- aminoanthraquinone
- amino
- hydroxyanthraquinone
- sulfuric acid
- bromo
- 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.)
- Granted
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】
ｊＪ」ρ１１すＪＬ
本発明は１−アミノ−２−ブロム−４−ヒドロキシアン
トラキノンの製造方法に関するものである。１−アミノ
−２−ブロム−４−ヒドロキシアントラキノンはアント
ラキノン系染料の中間体として古くから用いられている
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 1-amino-2-bromo-4-hydroxyanthraquinone. 1-Amino-2-bromo-4-hydroxyanthraquinone has long been used as an intermediate for anthraquinone dyes.
ぶＪ肇凶１阪
従来、その製造法は１−アミノアントラキノンを臭素化
１ノで１−アミノ−２，４−ジブロムアントラキノンと
して単離したのち、４−位の臭素を水酸基で置換させて
１−アミノ−２−ブロム−４−ヒドロキシアントラキノ
ンとする２段階法である。Traditionally, the production method involves brominating 1-aminoanthraquinone to isolate it as 1-amino-2,4-dibromanthraquinone, and then substituting the bromine at the 4-position with a hydroxyl group. This is a two-step process to produce 1-amino-2-bromo-4-hydroxyanthraquinone.
その工業的に行なわれている方法は、例えばＰＢレポー
ト時代からの方法として、１−アミノアントラキノンを
濃硫酸又は発煙硫酸に溶著したのち大数の水に注いで１
−アミノアントラキノンの微細粒子を含む酸性の懸濁液
とし、続いて塩素あるいは塩素酸ナトリウムと塩酸の存
在下に臭素を作用させ、反応物をヂ別したのち水洗、乾
燥して１−アミノ−２，４−ジブロムアントラキノンを
得る。これを硫酸あるいは発煙硫酸中でホウ酸の存在下
にカロ熱し加水分解して４・−ヒドロキシ体としたのち
水に排出し濾過、水洗、乾燥して１−アミノ−２−ブロ
ム−４−ヒドロキシアントラキノンを得る方法である（
例えば細田豊著「染料化学」第５７２ページ）。The method used industrially, for example, dates back to the PB report era, is to dissolve 1-aminoanthraquinone in concentrated sulfuric acid or fuming sulfuric acid, and then pour it into a large amount of water.
- Create an acidic suspension containing fine particles of aminoanthraquinone, then react with bromine in the presence of chlorine or sodium chlorate and hydrochloric acid, separate the reactants, wash with water, and dry to obtain 1-amino-2 , 4-dibromoanthraquinone is obtained. This is heated in sulfuric acid or fuming sulfuric acid in the presence of boric acid and hydrolyzed to form a 4-hydroxy compound, which is then drained into water, filtered, washed with water, and dried to 1-amino-2-bromo-4-hydroxy. This is how to obtain anthraquinone (
For example, "Dye Chemistry" by Yutaka Hosoda, page 572).
王妃の方法では臭素化を円滑に進行させるために１−ア
ミノアントラキノンを一旦硫酸に溶解させ、大量の水に
排出して分散させているので、反応に必須ではない硫酸
を使用しており、また加水分解を濃硫酸もしくは発煙硫
酸中で行なうため中間生成物である１−アミノ−２，４
−ジブロムアントラキノンを炉別し、乾燥さらに場合に
よっては粉砕する工程が必要で工業的に大ぎ５な負担と
なっている。In the Queen's method, 1-aminoanthraquinone is dissolved in sulfuric acid and then discharged into a large amount of water to be dispersed in order to proceed with the bromination smoothly, so sulfuric acid, which is not essential for the reaction, is used. Since the hydrolysis is carried out in concentrated sulfuric acid or fuming sulfuric acid, the intermediate product 1-amino-2,4
- The process of separating dibromoanthraquinone in a furnace, drying it, and in some cases crushing it is necessary, which is an enormous burden on the industry.
また１−アミノアントラキノンの臭素化反応はニトロベ
ンゼンなどの有機溶媒中で容易に進行することも知られ
ているがこの方法も作業環境、溶媒回収、排液処理など
工業的には問題点が多い。It is also known that the bromination reaction of 1-aminoanthraquinone proceeds easily in an organic solvent such as nitrobenzene, but this method also has many problems from an industrial perspective, such as the working environment, solvent recovery, and wastewater treatment.
従来濃硫酸中での１−アミノアントラキノンの臭素化は
、水懸濁液中あるいは有機溶媒中での臭素化に近い反応
条件の下では反応の進行が遅く、他の方法に比べて不利
であると考えられていたため文献例も見当らない。Conventionally, the bromination of 1-aminoanthraquinone in concentrated sulfuric acid is disadvantageous compared to other methods because the reaction progresses slowly under reaction conditions similar to bromination in an aqueous suspension or an organic solvent. Since it was thought that
問題点を解 するための手段
本発明者らは１−アミノアントラキノンの臭素化につい
て検討の結果、適切な条件を選べば発煙硫酸中でも臭素
化反応は円滑に進行し、中間生成物の１−アミノ−２，
４−ジブロムアントラキノンを単離することなく加水分
解工程への接続も可能であることを見出し本方法を完成
した。Means for Solving the Problem The present inventors investigated the bromination of 1-aminoanthraquinone and found that if appropriate conditions are chosen, the bromination reaction proceeds smoothly even in fuming sulfuric acid, and the intermediate product 1-aminoanthraquinone is -2,
The present method was completed by discovering that 4-dibromoanthraquinone can be connected to the hydrolysis step without being isolated.
すなわち、本発明の方法は、１−アミノアントラキノン
を１０係以下の発煙破袋中で臭素と反応させて１−アミ
ノ−２，４−ジブロムアントラキノンとし、続いて必要
ならば硫酸の量及び濃度を調整したのち、生成物を単離
することなく、ホウ酸の存在下に加熱して加水分解を行
なうことを特徴とする１−アミノ−２−ブロム−４−ヒ
ドロキシアントラキノンの製造方法である。That is, the method of the present invention involves reacting 1-aminoanthraquinone with bromine in a fuming bag of 10 parts or less to form 1-amino-2,4-dibromuanthraquinone, and then, if necessary, reducing the amount and concentration of sulfuric acid. This is a method for producing 1-amino-2-bromo-4-hydroxyanthraquinone, which is characterized in that the product is hydrolyzed by heating in the presence of boric acid without isolating the product.
本発明の方法は好ましくは次のように実施されるＯｌ−
アミノアントラキノンとこれに対し１５〜１０＠量の１
０％以下の発煙硫酸を反応容器に仕込む口これに１−ア
ミノアントラキノン１モルに対し２〜１５モルの臭素を
加えてかきまぜながら昇温し反応させる〇
最終的には６０〜７０℃で５〜１０時間程度の保温によ
り臭素化は完結する。続いて過剰の臭素の大部分を蒸留
回収したのち１−アミノアントラキノン１モルに対し０
．５〜５モルのホウ酸を加え、。The method of the invention is preferably carried out as follows:
Aminoanthraquinone and 15 to 10 @ amount of 1
Pour 0% or less fuming sulfuric acid into the reaction vessel. Add 2 to 15 moles of bromine per mole of 1-aminoanthraquinone and raise the temperature while stirring to react.Finally, 5 to 70 degrees Celsius is heated to 60 to 70℃. Bromination is completed by keeping it warm for about 10 hours. Subsequently, most of the excess bromine is distilled and recovered, and then 0% per mole of 1-aminoanthraquinone is
．． Add 5-5 moles of boric acid.
さらに通常の加水分解条件に合わせるため必要な場合に
は硫酸の濃度および量を調節し、１００〜１４０°Ｃで
１〜２０時間かきまぜて加水分解する。Further, the concentration and amount of sulfuric acid are adjusted as necessary to match the usual hydrolysis conditions, and the mixture is stirred at 100 to 140°C for 1 to 20 hours for hydrolysis.
臭素の回収は加水分解反応と同時に行なってもよい。反
応終了後反応液を水で希釈して生成した目的物を析出さ
せたのち炉別して１−アミノ−２−ブロム−４−ヒドロ
キシアントラキノンを得る。Bromine recovery may be performed simultaneously with the hydrolysis reaction. After the reaction is completed, the reaction solution is diluted with water to precipitate the desired product, which is then separated in a furnace to obtain 1-amino-2-bromo-4-hydroxyanthraquinone.
本方法により製造される１−アミノ−２−ブロム−４−
ヒドロキシアントラキノンは極めて高純度であり、何等
の精製操作も必要とせずそのまま染料等の中間体として
使用できるものである。1-Amino-2-bromo-4- produced by this method
Hydroxyanthraquinone has extremely high purity and can be used as an intermediate for dyes and the like without any purification operations.
作用および効果
本発明の方法によれば、発煙硫酸中で１−アミノアント
ラキノンを臭素化し、続いて中間生成物であるｌ−アミ
ノ−２，４−ジブロムアントラキノンを単離することな
く、同一反応容器中でホウ酸を加えて加水分解反応を行
なうことができるので工程的に非常に簡略になる。また
従来の方法で用いられていた有機溶媒も必要としないの
で工業的に非常に有利である、
実施例
以下、本発明を実施例で具体的に説明する。Effects and Effects According to the method of the present invention, 1-aminoanthraquinone is brominated in oleum, and the same reaction is then carried out without isolating the intermediate product 1-amino-2,4-dibromanthraquinone. Since the hydrolysis reaction can be carried out by adding boric acid in a container, the process is very simple. Further, since the organic solvent used in the conventional method is not required, it is very advantageous industrially.Examples The present invention will be specifically explained below using Examples.
実施例１
撹拌機、温度計及びコンデンサーを取付けた内容３００
ｍｌの４ツロフラスコに５チ発煙硫酸５０ｇを仕込み
、次いで純度９８チの１−アミノアントラキノン２０ｇ
を装入した。３０〜４０°Ｃで１時間かきまぜたのち臭
素１００１を装入して徐々【こ昇温し５０°Ｃで２時間
、さらに昇温し６０〜６２°Ｃで１０時間かきまぜ臭素
化した。Example 1 Contents 300 with stirrer, thermometer and condenser installed
Pour 50g of oleum into a 4ml flask, then add 20g of 1-aminoanthraquinone with a purity of 98ml.
was loaded. After stirring at 30 to 40°C for 1 hour, bromine 1001 was charged and the temperature was gradually raised to 50°C for 2 hours, then further heated to 60 to 62°C for 10 hours to effect bromination.
５０°Ｃに冷却し５チ発煙硫酸２９０Ｉを追加し、さら
にホウ酸１７．ムＳを加えて５０°Ｃで１時間かきまぜ
溶解させた。過剰の臭素を回収しながら徐々に昇温し８
０℃で１時間、１００℃で２時間、次いで１２０°Ｃで
４時間かきまぜ加水分解した。Cool to 50°C, add 5 ml of fuming sulfuric acid, and add 17 ml of boric acid. Mu S was added and stirred at 50°C for 1 hour to dissolve. Gradually raise the temperature while recovering excess bromine.8
Hydrolysis was carried out by stirring at 0°C for 1 hour, at 100°C for 2 hours, and then at 120°C for 4 hours.
冷却後内容物を水８５０ｍ１に排出して結晶を析出させ
て炉別したのち洗液が中性になるまで水洗した。枦塊を
乾燥し１−アミノ−２−ブロム−４−ヒドロキシアント
ラキノン２７．８ ｇを得た。融点２３３〜２３５°Ｃ
０純度９７５チ。１−アミノアントラキノンからの理論
収率は９７．０ ％であった。After cooling, the contents were discharged into 850 ml of water to precipitate crystals, which were separated in a furnace and then washed with water until the washing liquid became neutral. The strawberry mass was dried to obtain 27.8 g of 1-amino-2-bromo-4-hydroxyanthraquinone. Melting point 233-235°C
0 purity 975chi. The theoretical yield from 1-aminoanthraquinone was 97.0%.
実施例２
１１の４ツロフラスコに８チ発煙硫酸２００ｇを仕込み
、つぎに純度９８チの１−アミノアントラキノン８０ｇ
を装入した。３０〜４０℃で１時間かきまぜ、その後臭
素２８７ｇを装入して、徐々に昇温し、５０°Ｃ，２時
間昇温し６０〜６２°Ｃで１０時間かきまぜ臭素化した
。Example 2 200g of 8T fuming sulfuric acid was charged into a 4-ton flask, and then 80g of 1-aminoanthraquinone with a purity of 98T was charged.
was loaded. The mixture was stirred at 30 to 40°C for 1 hour, then 287 g of bromine was charged, and the temperature was gradually raised to 50°C for 2 hours, followed by stirring at 60 to 62°C for 10 hours for bromination.
５０℃に冷却し、９８チ硫酸７５６ｇを追加し、さらに
ホウ酸４８．９を加えて５０℃で１時間かきまぜ溶解さ
せた。過剰の臭素を回収しながら徐々に昇温し、８０°
Ｃで１時間、１００°Ｃで２時間、次いで１２０℃で６
時間かきまぜ加水分解した。The mixture was cooled to 50° C., and 756 g of 98-thiosulfuric acid was added, followed by 48.9 g of boric acid, and the mixture was stirred at 50° C. for 1 hour to dissolve. While recovering excess bromine, gradually raise the temperature to 80°
C for 1 hour, 100°C for 2 hours, then 120°C for 6 hours.
Stir for hours to hydrolyze.
冷却後、水４２０ｍ１を１時間かけ反応液に滴下する。After cooling, 420 ml of water was added dropwise to the reaction solution over 1 hour.
次に希釈された反応液を８０°Ｃ温水１８００ｍｌに排
出して結晶を析出させて炉別したのち、洗液が中性にな
るまで水洗した。ｆ塊を乾燥し、１−アミノ−２−ブロ
ム−４＠ヒドロキシアントラキノン１１１．３ｇを得た
。融点２２９〜２３２°Ｃ０純度９７０チ。１−アミノ
アントラキノンからの理論収率は９７．５ ％であった
。Next, the diluted reaction solution was discharged into 1800 ml of 80° C. hot water to precipitate crystals, which were then separated in a furnace and washed with water until the washing solution became neutral. The f mass was dried to obtain 111.3 g of 1-amino-2-bromo-4@hydroxyanthraquinone. Melting point: 229-232°C; purity: 970°C. The theoretical yield from 1-aminoanthraquinone was 97.5%.
比較例
純度９８チの１−アミノアントラキノンｚ（１を１％発
煙硫酸６２．９とかきまぜて溶解させた。Comparative Example 1-Aminoanthraquinone Z (1) with a purity of 98% was stirred and dissolved in 62.9% of 1% oleum.
撹拌機、温度計及びコンデンサーを取けけた６００’ｍ
Ａ！容４ツロフラスコに水３２０ｍＡ！を仕込み、かき
まぜながら上記の１−アミノアントラキノンの１チ発煙
硫酸溶液を滴下し、１−アミノアントラキノンの分散液
とし臭素１６！ｉを滴下装入した。600'm with stirrer, thermometer and condenser installed
A! 320mA of water in a 4-volume flask! was prepared, and while stirring, the above 1% oleum solution of 1-aminoanthraquinone was added dropwise to form a dispersion of 1-aminoanthraquinone with 16% bromine. i was added dropwise.
次いで、塩素６５ｇを２時間で加えたのち３時間で５０
℃に上げ同温度で２時間かきまぜた。さらに２時間で８
０°Ｃとし同温度で１時間かきまぜ臭素化した。臭素化
終了後、濾過、水洗、乾燥して１−アミン−２＋４−ジ
ブロムアントラキノン３３２ｇを得た。Next, 65g of chlorine was added over 2 hours, and 50g of chlorine was added over 3 hours.
℃ and stirred at the same temperature for 2 hours. 8 in another 2 hours
The mixture was brought to 0°C and stirred for 1 hour at the same temperature for bromination. After the bromination was completed, it was filtered, washed with water, and dried to obtain 332 g of 1-amine-2+4-dibromoanthraquinone.
別に撹拌機、温度計及びコンデンサーを取付けた５００
ｍ１！容フラスコに４チ発煙硫酸３３２ｇを仕込み、ホ
ウ酸１１．０ｇを加えてかきまぜ溶解させた。これに上
記の１−アミノ−２，４−ジブロムアントラキノン３３
．２ 、ｌｉ’を加え徐々に昇温し１００°Ｃで１時間
、さらに昇温し１２０°Ｃで７時間かきまぜ加水分解し
たのち６０℃に冷却し、水７５０ｍ１１′に排出後濾過
、水洗し１−アミノ−２−プロムー４−ヒドロキシアン
トラキノン２７．５ ｇを得た。融点２２９〜２３２°
Ｃ０純度９６チ。１−アミノアントラキノンな対する理
論収率は９４．５チであった。500 with separate stirrer, thermometer and condenser
m1! A volumetric flask was charged with 332 g of oleum, and 11.0 g of boric acid was added and stirred to dissolve. To this, the above 1-amino-2,4-dibromoanthraquinone 33
．． 2. Add li' and gradually raise the temperature to 100°C for 1 hour, further raise the temperature and stir at 120°C for 7 hours for hydrolysis, then cool to 60°C, drain into 750 ml of water, filter, wash with water 1 27.5 g of -amino-2-promo-4-hydroxyanthraquinone was obtained. Melting point 229-232°
C0 purity 96chi. The theoretical yield for 1-aminoanthraquinone was 94.5%.
Claims (1)
中で臭素と反応させて１−アミノ−２，４−ジブロムア
ントラキノンとし、続いて必要ならば硫酸の量及び濃度
を調整したのち、生成物を単離することなく、ホウ酸の
存在下に加熱して加水分解を行なうことを特徴とする１
−アミノ−２−ブロム−４−ヒドロキシアントラキノン
の製造方法。1) Reacting 1-aminoanthraquinone with bromine in up to 10% fuming sulfuric acid to give 1-amino-2,4-dibromuanthraquinone, followed by adjusting the amount and concentration of sulfuric acid if necessary, to form the product. 1, characterized in that the hydrolysis is carried out by heating in the presence of boric acid without isolating the
-A method for producing amino-2-bromo-4-hydroxyanthraquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60106888A JPS6110541A (en) | 1985-05-21 | 1985-05-21 | Production of 1-amino-2-bromo-4-hydroxyanthraquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60106888A JPS6110541A (en) | 1985-05-21 | 1985-05-21 | Production of 1-amino-2-bromo-4-hydroxyanthraquinone |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4841477A Division JPS53135962A (en) | 1977-04-28 | 1977-04-28 | Preparation of 1-amino-2-bromo-4-hydroxyanthraquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6110541A true JPS6110541A (en) | 1986-01-18 |
| JPS638113B2 JPS638113B2 (en) | 1988-02-19 |
Family
ID=14445024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60106888A Granted JPS6110541A (en) | 1985-05-21 | 1985-05-21 | Production of 1-amino-2-bromo-4-hydroxyanthraquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6110541A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53133231A (en) * | 1977-04-26 | 1978-11-20 | Sumitomo Chem Co Ltd | Preparation of anthraquinone intermediate |
| JPS53133230A (en) * | 1977-04-25 | 1978-11-20 | Sumitomo Chem Co Ltd | Preparation of anthraquinone intermediate |
-
1985
- 1985-05-21 JP JP60106888A patent/JPS6110541A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53133230A (en) * | 1977-04-25 | 1978-11-20 | Sumitomo Chem Co Ltd | Preparation of anthraquinone intermediate |
| JPS53133231A (en) * | 1977-04-26 | 1978-11-20 | Sumitomo Chem Co Ltd | Preparation of anthraquinone intermediate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS638113B2 (en) | 1988-02-19 |
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