JP2664761B2 - Method for producing aminobenzanthrones - Google Patents
Method for producing aminobenzanthronesInfo
- Publication number
- JP2664761B2 JP2664761B2 JP1062203A JP6220389A JP2664761B2 JP 2664761 B2 JP2664761 B2 JP 2664761B2 JP 1062203 A JP1062203 A JP 1062203A JP 6220389 A JP6220389 A JP 6220389A JP 2664761 B2 JP2664761 B2 JP 2664761B2
- Authority
- JP
- Japan
- Prior art keywords
- aminobenzanthrones
- reaction
- copper
- present
- producing
- 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
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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はアミノベンザントロン類を製造方法に関す
る。アミノベンザントロン類はバット染料、有機光電材
料等の中間体として、工業的に重要な化合物である。Description: TECHNICAL FIELD The present invention relates to a method for producing aminobenzanthrones. Aminobenzanthrones are industrially important compounds as intermediates such as vat dyes and organic photoelectric materials.
従来、アミノベンザントロン類の合成法として ベンザントロンをニトロ化して得られたニトロベンザ
ントロンを還元して得る方法、 ハロゲノベンザントロンをｐ−トルエンスルホン酸ア
ミドで置換後、加水分解して得る方法、 等が知られている。Conventionally, as a method for synthesizing aminobenzanthrones, a method in which nitrobenzanthrone obtained by nitrating benzanthrone is obtained, and a method in which halogenobenzanthrone is substituted with p-toluenesulfonic acid amide and then hydrolyzed Methods, etc. are known.
しかしながら、の方法はニトロ化反応で副生物が多
く、純度の良いアミノベンザントロンを得るにはニトロ
ベンザントロンの精製が必要になり収率も低く、又多量
の廃酸が発生して、工業的には極めて魅力に乏しい方法
である。更に、このニトロベンザントロンは、皮膚感作
性が強く、人体に悪影響を及ぼすことがある。However, this method has many by-products in the nitration reaction, and in order to obtain aminobenzanthrone with high purity, purification of nitrobenzanthrone is required, the yield is low, and a large amount of waste acid is generated. This is a very unattractive method industrially. Furthermore, this nitrobenzanthrone has a strong skin sensitization, and may have a bad influence on the human body.
の方法はアミノ置換であるが、工程も長く副生物が
多い。又反応に有機溶媒を使用するため、有機溶媒の回
収が必要であり、さらに加水分解後に高COD廃水が発生
することで、工程がかなり煩雑になり、工業的に実施す
る場合困難である。Is an amino substitution, but the process is long and has many by-products. In addition, since an organic solvent is used in the reaction, it is necessary to recover the organic solvent. Further, since high COD wastewater is generated after hydrolysis, the process becomes considerably complicated, and it is difficult to carry out the process industrially.
本発明は、これら従来の技術の欠点、すなわち副生物
の生成、多量の廃酸、廃水の処理等の諸問題を解決し、
しかも従来にない高品位のアミノベンザントロン類を高
収率で得る方法を提供するものである。The present invention solves the drawbacks of these conventional technologies, namely, problems such as generation of by-products, a large amount of waste acid, and treatment of wastewater.
In addition, the present invention provides a method for obtaining unprecedented high-quality aminobenzanthrones in a high yield.
本発明者らは従来法に代わるアミノベンザントロン類
の新しい製法について、鋭意検討した結果ハロゲノベン
ザントロンを銅触媒の存在下、加圧下、アンモニアを添
加して、アミノ置換させることにより、工業的に極めて
有利に収率良く、高品位のアミノベンザントロンが得ら
れることを見出し本発明を完成させた。The present inventors have conducted intensive studies on a new production method of aminobenzanthrones which can replace the conventional method.As a result, the halogenobenzanthrone is subjected to amino substitution by adding ammonia under pressure and in the presence of a copper catalyst to obtain an amino-substituted product. It has been found that a high-quality aminobenzanthrone can be obtained very advantageously in good yield and the present invention has been completed.
即ち、本発明はハロゲノベンザントロンを銅触媒の存
在下、アンモニアを添加し、アミノ置換させることを特
徴とするアミノベンザントロン類の製造方法である。That is, the present invention is a method for producing aminobenzanthrones, which comprises subjecting halogenobenzanthrone to amino substitution by adding ammonia in the presence of a copper catalyst.
以下に本発明を具体的に詳述する。 Hereinafter, the present invention will be described in detail.
本発明のハロゲノベンザントロン類とは具体的には３
−クロロベンザントロン、３−ブロムベンザントロン、
3,9−ジクロロベンザントロン、3,9−ジブロムベンザン
トロン等であり、特に３−ブロムベンザントロン、3,9
−ジブロムベンザントロンが好ましい。The halogenobenzanthrones of the present invention specifically include 3
-Chlorobenzantron, 3-bromobenzantron,
3,9-dichlorobenzanthrone, 3,9-dibromobenzanthrone and the like, in particular, 3-bromobenzanthrone, 3,9
Dibrombenzanthrone is preferred.
本発明で使用する銅触媒としては、電解銅、酸化第１
銅、酸化第２銅、塩化銅、酢酸銅、ブチルフタレート銅
等が挙げられる。The copper catalyst used in the present invention includes electrolytic copper, oxidized copper
Copper, cupric oxide, copper chloride, copper acetate, butyl phthalate copper and the like can be mentioned.
銅触媒の量は、ハロゲノベンザントロン類１重量部に
対して通常0.05〜0.5重量部である。The amount of the copper catalyst is usually 0.05 to 0.5 part by weight based on 1 part by weight of the halogeno benzantrone.
反応温度は150〜250℃で、好ましくは200〜210℃であ
る。反応圧力は、アンモニア水の濃度と、反応温度によ
って決定されるが通常５〜約70kg/cm2の間である。The reaction temperature is 150-250 ° C, preferably 200-210 ° C. The reaction pressure is determined by the concentration of aqueous ammonia and the reaction temperature, but is usually between 5 and about 70 kg / cm 2 .
アンモニアの使用量は、ハロゲノベンザントロン類１
モルに対し、通常４倍モル量以上でである。The amount of ammonia used is the halogenobenzanthrones 1
It is usually at least 4 times the molar amount to the molar amount.
反応に用いるアンモニアはアンモニア水溶液で良く、
その濃度は５重量％以上であれば良いが、好ましくは15
重量％以上で用いられる。The ammonia used for the reaction may be an aqueous ammonia solution,
The concentration may be 5% by weight or more, preferably 15% by weight.
Used in weight percent or more.
アンモニア水は反応溶媒でもあり、更に溶媒として反
応に不活性な有機溶媒、例えばトルエン、キシレン等を
混合して使用しても良い。その量はアンモニア水に対し
て通常、多くとも50重量％までである。Ammonia water is also a reaction solvent, and an organic solvent inert to the reaction, for example, toluene, xylene, or the like may be mixed and used as a solvent. The amount is usually at most 50% by weight with respect to the aqueous ammonia.
又、アンモニア水のみ使用する場合は、該ベンザント
ロンの分散を良くするためアンモニア及び該ベンザント
ロン類に不活性な界面活性剤、例えば、テトラエチルア
ンモニウムクロライド、オクチルトリメチルアンモニウ
ムクロライド等を混合して使用しても良い。その量はア
ンモニア水に対して通常10重量％以下である。When only aqueous ammonia is used, a surfactant inactive to ammonia and the benzantrone, for example, tetraethylammonium chloride, octyltrimethylammonium chloride or the like may be used in combination to improve the dispersion of the benzantrone. good. The amount is usually 10% by weight or less based on the amount of ammonia water.
これらの操作で得られたアミノベンザントロンは濾過
後、結晶として分離し、触媒銅は硫酸に溶解する通常の
方法で脱銅処理することによって、収率良く高純度のア
ミノベンザントロンを収得できる。有機光電材料等の中
間体に使用するために、更に純度を高めるためには、有
機溶媒による再結晶を行えば良い。有機溶媒としては例
えば、ジメチルホルムアミド、モノクロロベンゼン、1,
3−ジメチル−２−イミダゾリジノン、トルエン、キシ
レン等が挙げられる。The aminobenzantrone obtained by these operations is separated as crystals after filtration, and the copper catalyst is subjected to a decoppering treatment in a usual method of dissolving in sulfuric acid to obtain a high-purity aminobenzantrone in good yield. it can. In order to further increase the purity for use as an intermediate such as an organic photoelectric material, recrystallization with an organic solvent may be performed. As the organic solvent, for example, dimethylformamide, monochlorobenzene, 1,
3-dimethyl-2-imidazolidinone, toluene, xylene and the like.
アミノベンザントロン類を得る従来の方法は副生物が
多く、収率も低く、廃酸の発生、工程の煩雑さ、更には
ニトロベンザントロンのような皮膚感作性の強い化合物
を生成する等、工業的には種々問題の多い方法であっ
た。Conventional methods for obtaining aminobenzanthrones have many by-products, low yield, generation of waste acid, complicated processes, and formation of compounds having strong skin sensitization such as nitrobenzanthrone. For example, the method has many problems in industry.
しかし本発明の方法は、上記のような問題点がなく、
高純度品を得ることのできる実用的に優れた方法であ
る。However, the method of the present invention does not have the above problems,
This is a practically excellent method that can obtain a high-purity product.
次に実施例を挙げて、本発明をさらに詳細に説明する
が、本発明はこれに限定されるものではない。Next, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
実施例１ 撹拌機付SUS製500mlのオートクレーブに25重量％アン
モニア水300g、３−ブロムベンザントロン50g、触媒と
して酸化銅3gを仕込み、昇温し200〜210℃に保温し、同
温度で15時間反応させアミノ置換反応を行った。反応圧
力は55kg/cm2であった。その後、100℃まで冷却し、水
に排出し、得られた結晶を濾別、水洗浄、乾燥させた。Example 1 A 300 ml autoclave made of SUS with a stirrer was charged with 300 g of 25% by weight aqueous ammonia, 50 g of 3-bromobenzanthrone, and 3 g of copper oxide as a catalyst, and the temperature was raised and kept at 200 to 210 ° C. The reaction was carried out for an hour to carry out an amino substitution reaction. The reaction pressure was 55 kg / cm 2 . Thereafter, the mixture was cooled to 100 ° C., discharged into water, and the obtained crystals were separated by filtration, washed with water, and dried.
次に濃硫酸600gに40℃以下で溶解させ、水に排出し、
濾過、水洗浄、乾燥させ、脱銅処理を行つて３−アミノ
ベンザントロン38.3gを得た。高速液体クロマトグラフ
ィーによる分析で純度93％、収率89.8％であった。Next, it is dissolved in 600 g of concentrated sulfuric acid at a temperature of 40 ° C or less, and discharged into water.
Filtration, washing with water, drying and decopperization were performed to obtain 38.3 g of 3-aminobenzanthrone. Analysis by high performance liquid chromatography revealed a purity of 93% and a yield of 89.8%.
実施例２ 実施例１のオートクレーブに25重量％アンモニア水30
0g、3,9−ジブロムベンザントロン50g、触媒として電解
銅粉3gを仕込み、昇温し200〜210℃に保温し、同温度で
20時間反応させアミノ置換反応を行った。反応圧力55kg
/cm2であった。その後冷却し、水に排出し得られた結晶
を濾別、水洗浄、乾燥させた。実施例１と同様な方法で
脱銅処理して3,9−ジアミノベンザントロン32.2gを得
た。高速液体クロマトグラフィーによる分析で純度94
％、収率96.3％であった。Example 2 25% by weight of aqueous ammonia 30 was added to the autoclave of Example 1.
0 g, 50 g of 3,9-dibromobenzanthrone, and 3 g of electrolytic copper powder as a catalyst, the temperature was raised and the temperature was kept at 200 to 210 ° C.
The reaction was carried out for 20 hours to carry out an amino substitution reaction. Reaction pressure 55kg
/ cm 2 . Thereafter, the mixture was cooled, discharged into water, and the obtained crystals were separated by filtration, washed with water, and dried. Copper removal treatment was carried out in the same manner as in Example 1 to obtain 32.2 g of 3,9-diaminobenzanthrone. 94 purity by high performance liquid chromatography
% And the yield was 96.3%.
実施例３ 実施例１のオートクレーブに20重量％アンモニア水25
0g、キシレン50g、３−ブロムベンザントロン50g、触媒
として酸化銅3gを仕込み昇温し、210〜220℃に保温し、
同温度で18時間反応させた。反応圧力は55kg/cm2であっ
た。冷却後、反応液を取り出し、水蒸気蒸留でキシレン
を留去させて得られた結晶を濾別、水洗浄、乾燥させ
た。実施例１と同様な方法で脱銅処理して、３−アミノ
ベンザントロン37.8gを得た。高速液体クロマトグラフ
ィーによる分析で純度94％、収率89.6％であった。Example 3 In the autoclave of Example 1, 20% by weight aqueous ammonia 25
0 g, xylene 50 g, 3-bromobenzanthrone 50 g, 3 g of copper oxide as a catalyst were charged and heated, and kept at 210 to 220 ° C.,
The reaction was carried out at the same temperature for 18 hours. The reaction pressure was 55 kg / cm 2 . After cooling, the reaction solution was taken out, and xylene was distilled off by steam distillation, and the obtained crystals were separated by filtration, washed with water, and dried. Copper removal treatment was performed in the same manner as in Example 1 to obtain 37.8 g of 3-aminobenzanthrone. Analysis by high performance liquid chromatography revealed a purity of 94% and a yield of 89.6%.
Claims (1)
下、アンモニアを添加してアミノ置換させることを特徴
とするアミノベンザントロン類の製造方法。1. A process for producing aminobenzanthrones, comprising subjecting halogenobenzanthrone to amino substitution by adding ammonia in the presence of a copper catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1062203A JP2664761B2 (en) | 1989-03-16 | 1989-03-16 | Method for producing aminobenzanthrones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1062203A JP2664761B2 (en) | 1989-03-16 | 1989-03-16 | Method for producing aminobenzanthrones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02243662A JPH02243662A (en) | 1990-09-27 |
| JP2664761B2 true JP2664761B2 (en) | 1997-10-22 |
Family
ID=13193356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1062203A Expired - Fee Related JP2664761B2 (en) | 1989-03-16 | 1989-03-16 | Method for producing aminobenzanthrones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2664761B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU4946697A (en) * | 1996-10-28 | 1998-05-22 | Merck Patent Gmbh | Dihydrobenzoanthracenone, -pyrimidinone or dihydronaphtoquinolinone |
-
1989
- 1989-03-16 JP JP1062203A patent/JP2664761B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02243662A (en) | 1990-09-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |