JP3244622B2 - Benzanthrone bromination method - Google Patents
Benzanthrone bromination methodInfo
- Publication number
- JP3244622B2 JP3244622B2 JP23711595A JP23711595A JP3244622B2 JP 3244622 B2 JP3244622 B2 JP 3244622B2 JP 23711595 A JP23711595 A JP 23711595A JP 23711595 A JP23711595 A JP 23711595A JP 3244622 B2 JP3244622 B2 JP 3244622B2
- Authority
- JP
- Japan
- Prior art keywords
- bromine
- hours
- present
- benzanthrone
- sulfuric acid
- 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 - Fee Related
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、下記式（１）TECHNICAL FIELD The present invention relates to the following formula (1)
【化３】 のベンザンスロンの臭素化物である下記式（２）Embedded image The following formula (2) which is a bromide of benzanthrone
【化４】 の３，９−ジブロモベンザンスロンを製造する方法に関
する。Embedded image To a method for producing 3,9-dibromobenzanthrone.
【０００２】[0002]
【従来の技術】本発明の目的化合物３，９−ジブロモベ
ンザンスロン（以下、ＤＢＢｚと略す）は、古くから染
料等の精密化学品中間体として重要な化合物である。BACKGROUND OF THE INVENTION The target compound 3,9-dibromobenzanthrone (hereinafter abbreviated as DBBz) of the present invention has been an important compound as a fine chemical intermediate such as a dye since ancient times.
【０００３】このＤＢＢｚを製造する方法としてこれま
でに種々の方法が開示されている。一般的には、水ある
いは鉱酸中で原料のベンザンスロン（以下、Ｂｚと略
す）を溶解あるいは懸濁させ、臭素と反応させる方法が
知られている（ＤＲＰ １９３９５９）。[0003] Various methods have been disclosed as methods for producing DBBz. In general, a method is known in which benzanthrone (hereinafter, abbreviated as Bz) as a raw material is dissolved or suspended in water or a mineral acid and reacted with bromine (DRP 193959).
【０００４】しかしながら、硫酸以外の鉱酸及び水中で
の臭素化は、Ｂｚ及び中間体であるブロモベンザンスロ
ン（以下、ＢＢｚと略す）の溶解度がほとんどないため
に懸濁状態で反応が進行する。そのため、反応速度が極
めて遅く、ＤＢＢｚの収率を高くするためには、反応時
間を極力長くするか、大過剰の臭素を用いる必要があ
り、工業的に適した方法とは言い難い。However, bromination in mineral acids other than sulfuric acid and in water proceeds in a suspended state because Bz and bromobenzanthrone (hereinafter abbreviated as BBz) as an intermediate have almost no solubility. . Therefore, the reaction rate is extremely slow, and in order to increase the yield of DBBz, it is necessary to extend the reaction time as much as possible or use a large excess of bromine, which is not industrially suitable.
【０００５】また、硫酸中での臭素化反応も知られてい
る。しかし、反応が遅く、大過剰の臭素を用いることで
ようやく反応が進行する。更に、工業的には臭素回収が
不可避である。そのため、６０℃以上に加熱し、気体と
なった臭素を凝縮させることで回収する。その際、ＤＢ
Ｂｚの分解が進行し、ＤＢＢｚの収率及び純度低下を招
き、必ずしも工業的に適した方法とは言い難い。[0005] A bromination reaction in sulfuric acid is also known. However, the reaction is slow, and the reaction proceeds only by using a large excess of bromine. Further, industrially, bromine recovery is inevitable. Therefore, it is heated to 60 ° C. or higher, and the bromine which has become a gas is recovered by condensation. At that time, DB
Decomposition of Bz proceeds, resulting in a decrease in the yield and purity of DBBz, and is not necessarily an industrially suitable method.
【０００６】ｏ−ジクロロベンゼン、ニトロベンゼン等
の有機溶剤中での反応も知られている（ＵＳＰ２１８０
８３５、ＵＳＰ２３５３０４９、ＳＵ５９５２８３、Ｓ
Ｕ３５５１５０）。しかしながら、これらの場合、有機
溶剤の回収工程が不可避であり、工程を煩雑化するた
め、必ずしも工業的に適した方法とは言い難い。A reaction in an organic solvent such as o-dichlorobenzene and nitrobenzene is also known (US Pat. No. 2,180,180).
835, USP 2,530,049, SU595283, S
U355150). However, in these cases, the step of recovering the organic solvent is inevitable, and the steps are complicated. Therefore, the method is not necessarily industrially suitable.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、これら従来
技術を更に改良し、理論量に近い臭素を用いて効率的に
反応を行い、高収率で高品質のＤＢＢｚを得る方法を提
供するものである。SUMMARY OF THE INVENTION The present invention further improves these prior arts and provides a method for efficiently performing a reaction using bromine having a stoichiometric amount to obtain high-quality DBBz in high yield. Things.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記問題
を解決するために鋭意検討した結果、工業的に極めて価
値のある方法を見出し、本発明を完成した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found an industrially extremely valuable method, and have completed the present invention.
【０００９】即ち、本発明は、硫酸中で下記式（１）That is, the present invention provides the following compound (1) in sulfuric acid:
【化５】 のベンザンスロンを臭素と反応させ、下記式（２）Embedded image Is reacted with bromine to obtain the following formula (2)
【化６】 の３，９−ジブロモベンザンスロンを製造する方法にお
いて、ニトロシル硫酸存在下で反応を行うことを特徴と
する３，９−ジブロモベンザンスロンの製造方法であ
る。Embedded image 3. The method for producing 3,9-dibromobenzanthrone according to the above, wherein the reaction is carried out in the presence of nitrosylsulfuric acid.
【００１０】[0010]
【発明の実施形態】以下、本発明を詳細に説明する。本
発明の方法において、具体的な方法の一例を示せば、ま
ず９８％硫酸に亜硝酸ナトリウムを添加し、ニトロシル
硫酸を調製する。次いで、Ｂｚを添加し、所定温度に昇
温後、臭素を滴下する。更に、所定時間撹拌し、脱ガス
後、水に排出する。固形物を濾過、水洗することによ
り、目的のＤＢＢｚが得られる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the method of the present invention, a specific example of the method is as follows. First, sodium nitrite is added to 98% sulfuric acid to prepare nitrosyl sulfuric acid. Next, Bz is added, and after raising the temperature to a predetermined temperature, bromine is added dropwise. Further, the mixture is stirred for a predetermined time and discharged into water after degassing. The target DBBz is obtained by filtering and washing the solid substance with water.
【００１１】本発明方法において、用いるニトロシル硫
酸の使用量は、Ｂｚに対して０．０１〜５モル比、好ま
しくは０．１〜２モル比である。このニトロシル硫酸
は、反応溶媒である硫酸中に、亜硝酸ナトリウムや亜硝
酸カリウム等の亜硝酸塩を添加することで簡単に得られ
る。また、発煙硝酸や発煙硫酸と硫黄を反応させること
でも得られることが知られており、いずれの場合でも、
臭素添加時に反応系中にニトロシル硫酸が存在すればよ
い。In the method of the present invention, the amount of nitrosylsulfuric acid used is 0.01 to 5 mole ratio, preferably 0.1 to 2 mole ratio, relative to Bz. This nitrosylsulfuric acid can be easily obtained by adding a nitrite such as sodium nitrite or potassium nitrite to sulfuric acid as a reaction solvent. It is also known to be obtained by reacting fuming nitric acid or fuming sulfuric acid with sulfur, and in any case,
It is sufficient that nitrosylsulfuric acid is present in the reaction system at the time of adding bromine.
【００１２】本発明方法において、用いる硫酸の濃度
は、８０重量％以上、好ましくは９３〜１００重量％、
更に好ましくは、９５〜１００重量％である。又、使用
する硫酸の量は、原料であるＢｚに対して２〜２０重量
比、好ましくは３〜１５重量比用いる。In the method of the present invention, the concentration of sulfuric acid used is 80% by weight or more, preferably 93 to 100% by weight,
More preferably, it is 95 to 100% by weight. The amount of sulfuric acid used is 2 to 20 weight ratio, preferably 3 to 15 weight ratio, relative to the raw material Bz.
【００１３】本発明の方法において、用いる臭素のモル
比は、原料のＢｚに対して０．８モル比以上であり、好
ましくは０．９〜３．０モル比である。In the method of the present invention, the molar ratio of bromine used is at least 0.8 molar ratio, preferably 0.9 to 3.0 molar ratio, relative to the starting material Bz.
【００１４】本発明方法において、臭素の滴下温度は、
１０〜８０℃、好ましくは４０〜６０℃が良い。また、
１０時間以内、好ましくは２〜８時間で滴下する。In the method of the present invention, the temperature at which bromine is dropped is:
The temperature is preferably 10 to 80C, more preferably 40 to 60C. Also,
The solution is dropped within 10 hours, preferably 2 to 8 hours.
【００１５】本発明方法において、臭素滴下後の撹拌温
度は２０〜１００℃、好ましくは５０〜９０℃が良い。
撹拌時間は、温度にもよるが２０時間以内、好ましくは
１５時間以内が工業的に効率的であり、高収率で高純度
のＤＢＢｚが得られる。In the method of the present invention, the stirring temperature after the dropping of bromine is preferably from 20 to 100 ° C, more preferably from 50 to 90 ° C.
Although the stirring time depends on the temperature, it is industrially efficient within 20 hours, preferably within 15 hours, and DBBz with high yield and high purity can be obtained.
【００１６】[0016]
【実施例】以下、実施例により本発明を更に説明する
が、本発明はその要旨を越えない限り、以下の実施例に
限定されるものではない。また、文中「収率」とあるの
は、Ｂｚに対するＤＢＢｚの収率を示す。又、純度分析
はガスクロマトグラフィーで行った。EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. The term “yield” in the text indicates the yield of DBBz with respect to Bz. Purity analysis was performed by gas chromatography.
【００１７】実施例１ ９８％硫酸２００ｇに亜硝酸ナトリウム９．０ｇ加え、
２５℃で５分間撹拌する。次いで、Ｂｚ３０．０ｇを装
入し、５５℃に昇温する。臭素２９．３ｇ（Ｂｚに対し
て１．４モル比）を６．５時間かけて滴下する。そのま
ま２時間撹拌後、８０℃に昇温する。８０℃で４．５時
間撹拌後、３０℃に冷却し、氷水７５０ｇにゆっくりと
排出する。サルファイト１１ｇを加え、室温で２時間撹
拌し、濾過する。水洗後、ウェットケーキを乾燥させる
と、目的のＤＢＢｚ５０．２ｇが得られる。純度９０
％、収率８９％であった。Example 1 To 200 g of 98% sulfuric acid was added 9.0 g of sodium nitrite.
Stir at 25 ° C. for 5 minutes. Next, 30.0 g of Bz is charged, and the temperature is raised to 55 ° C. 29.3 g of bromine (1.4 molar ratio to Bz) are added dropwise over 6.5 hours. After stirring for 2 hours as it is, the temperature is raised to 80 ° C. After stirring at 80 ° C. for 4.5 hours, cool to 30 ° C. and slowly drain into 750 g of ice water. Add 11 g of sulfite, stir at room temperature for 2 hours and filter. After washing with water, the wet cake is dried to obtain 50.2 g of the target DBBz. Purity 90
% And the yield was 89%.
【００１８】実施例２ ９８％硫酸１４００ｇに亜硝酸ナトリウム２０．０ｇ加
え、１５℃で５分間撹拌する。次いで、Ｂｚ２００ｇを
装入し、そのまま１時間撹拌する。臭素２００ｇ（Ｂｚ
に対して１．４モル比）を１０分間で滴下し、５５℃に
４時間かけて昇温する。そのまま２時間撹拌後、８５℃
に昇温する。８５℃で４時間撹拌後、３０℃に冷却し、
氷水７５０ｇにゆっくりと排出する。サルファイト１１
ｇを加え、室温で２時間撹拌し、濾過する。水洗後、ウ
ェットケーキを乾燥させると、目的のＤＢＢｚ３３５ｇ
が得られる。純度９３％、収率９２％であった。Example 2 To 1400 g of 98% sulfuric acid was added 20.0 g of sodium nitrite, and the mixture was stirred at 15 ° C. for 5 minutes. Next, 200 g of Bz is charged and the mixture is stirred for 1 hour. 200 g of bromine (Bz
(1.4 mole ratio to the same) over 10 minutes, and the temperature was raised to 55 ° C. over 4 hours. After stirring for 2 hours, 85 ° C
Temperature. After stirring at 85 ° C for 4 hours, it was cooled to 30 ° C,
Drain slowly into 750 g of ice water. Sulfite 11
g, stir at room temperature for 2 hours and filter. After washing with water and drying the wet cake, the target DBBz 335 g
Is obtained. The purity was 93% and the yield was 92%.
【００１９】比較例１ ９２％硫酸２４４．８ｇにヨウ素０．２ｇとＢｚ２２．
３ｇを加え、２５℃で５分間撹拌する。次いで、１００
℃に昇温し、臭素３０．４ｇ（Ｂｚに対して２．０モル
比）を５．５時間で滴下する。そのまま３０分間撹拌
後、３０℃に冷却し、８％サルファイト水１３００ｇに
ゆっくりと排出する。室温で２時間撹拌し、濾過する。
水洗後、ウェットケーキを乾燥させると、目的のＤＢＢ
ｚ３２．８ｇが得られる。純度２８％、収率２５％であ
った。Comparative Example 1 To 244.8 g of 92% sulfuric acid was added 0.2 g of iodine and 22 g of Bz22.
Add 3 g and stir at 25 ° C. for 5 minutes. Then 100
The temperature was raised to 0 ° C, and 30.4 g of bromine (2.0 mol ratio to Bz) was added dropwise over 5.5 hours. After stirring for 30 minutes as it is, it is cooled to 30 ° C. and slowly discharged into 1300 g of 8% sulfite water. Stir at room temperature for 2 hours and filter.
After washing, the wet cake is dried and the target DBB
32.8 g of z are obtained. The purity was 28% and the yield was 25%.
【００２０】比較例２ ９２％硫酸５９９ｇにヨウ素０．５ｇとＢｚ６０．５ｇ
を加え、１０℃で５分間撹拌する。次いで、１０〜１５
℃で臭素２２０ｇ（Ｂｚに対して５．２モル比）を２時
間で滴下する。撹拌しながら、２２時間かけて温度を５
５℃に昇温し、５５℃で３時間撹拌する。更に内温を８
０℃までゆっくりと加熱し、未反応臭素を留去する。３
０℃に冷却し、８％サルファイト水２５００ｇにゆっく
りと排出する。室温で１時間撹拌し、濾過する。水洗
後、ウェットケーキを乾燥させると、目的のＤＢＢｚ９
６．８ｇが得られる。純度８５％、収率８１％であっ
た。Comparative Example 2 0.5 g of iodine and 60.5 g of Bz were added to 599 g of 92% sulfuric acid.
And stir at 10 ° C. for 5 minutes. Then 10-15
At 220 ° C., 220 g of bromine (5.2 mol ratio to Bz) are added dropwise over 2 hours. While stirring, raise the temperature to 5 over 22 hours.
Heat to 5 ° C. and stir at 55 ° C. for 3 hours. In addition, the internal temperature
Heat slowly to 0 ° C. and distill off unreacted bromine. 3
Cool to 0 ° C. and slowly drain into 2500 g of 8% sulfite water. Stir at room temperature for 1 hour and filter. After washing with water and drying the wet cake, the target DBBz9
6.8 g are obtained. The purity was 85% and the yield was 81%.
【００２１】[0021]
【発明の効果】本発明の方法によれば、染料中間体とし
て工業上極めて有用な化合物である３，９−ジブロモベ
ンザンスロンをベンザンスロンから高収率で得ることが
できる。更に得られた３，９−ジブロモベンザンスロン
は臭素回収操作を行うことなく単離でき、しかも高品質
である。According to the method of the present invention, 3,9-dibromobenzanthrone, which is a very industrially useful compound as a dye intermediate, can be obtained from benzanthrone in high yield. Further, the obtained 3,9-dibromobenzanthrone can be isolated without performing a bromine recovery operation, and is of high quality.
Claims (3)
いて、ニトロシル硫酸存在下で反応を行うことを特徴と
する３，９−ジブロモベンザンスロンの製造方法。(1) In sulfuric acid, the following formula (1): Is reacted with bromine to give the following formula (2): The method for producing 3,9-dibromobenzanthrone according to the above, wherein the reaction is carried out in the presence of nitrosylsulfuric acid.
ンザンスロンに対して０．０１〜５．０である請求項１
記載の方法。2. The molar ratio of nitrosylsulfuric acid used is 0.01 to 5.0 with respect to benzanthrone.
The described method.
ンに対して０．９〜３．０であることを特徴とする請求
項１又は請求項２記載の方法。3. The process according to claim 1, wherein the molar ratio of bromine used is from 0.9 to 3.0 with respect to benzanthrone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23711595A JP3244622B2 (en) | 1995-09-14 | 1995-09-14 | Benzanthrone bromination method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23711595A JP3244622B2 (en) | 1995-09-14 | 1995-09-14 | Benzanthrone bromination method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0977715A JPH0977715A (en) | 1997-03-25 |
| JP3244622B2 true JP3244622B2 (en) | 2002-01-07 |
Family
ID=17010641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23711595A Expired - Fee Related JP3244622B2 (en) | 1995-09-14 | 1995-09-14 | Benzanthrone bromination method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3244622B2 (en) |
-
1995
- 1995-09-14 JP JP23711595A patent/JP3244622B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0977715A (en) | 1997-03-25 |
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