JP3270673B2 - Process for producing 4,4'-diamino-1,1'-dianthraquinonyl-3,3'-disulfonic acid or salts thereof - Google Patents
Process for producing 4,4'-diamino-1,1'-dianthraquinonyl-3,3'-disulfonic acid or salts thereofInfo
- Publication number
- JP3270673B2 JP3270673B2 JP33663295A JP33663295A JP3270673B2 JP 3270673 B2 JP3270673 B2 JP 3270673B2 JP 33663295 A JP33663295 A JP 33663295A JP 33663295 A JP33663295 A JP 33663295A JP 3270673 B2 JP3270673 B2 JP 3270673B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- acid
- diamino
- dianthraquinonyl
- amino
- 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
- 239000002253 acid Substances 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 18
- 150000003839 salts Chemical class 0.000 title claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000012065 filter cake Substances 0.000 description 14
- 239000011780 sodium chloride Substances 0.000 description 14
- QZZSAWGVHXXMID-UHFFFAOYSA-N 1-amino-4-bromo-9,10-dioxoanthracene-2-sulfonic acid Chemical compound C1=CC=C2C(=O)C3=C(Br)C=C(S(O)(=O)=O)C(N)=C3C(=O)C2=C1 QZZSAWGVHXXMID-UHFFFAOYSA-N 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- TXMRAEGWZZVGIH-UHFFFAOYSA-M sodium;1-amino-4-bromo-9,10-dioxoanthracene-2-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C(Br)=CC(S([O-])(=O)=O)=C2N TXMRAEGWZZVGIH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Landscapes
- 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、４，４’−ジアミ
ノ−１，１’−ジアントラキノニル−３，３’−ジスル
ホン酸類またはその塩類の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing 4,4'-diamino-1,1'-dianthraquinonyl-3,3'-disulfonic acid or a salt thereof.
【０００２】[0002]
【従来の技術】４，４’−ジアミノ−１，１’−ジアン
トラキノニル−３，３’−ジスルホン酸類またはその塩
類は、４，４’−ジアミノ−１，１’−ジアントラキノ
ニル系赤色顔料の中間体として有用であり、例えば特公
昭３８−２５８４２号公報に記載のように、１−アミノ
−４−ハロゲノアントラキノンスルホン酸を酸性媒質中
で、銅と一緒にまたはハロゲンを脱離させることのでき
る銅化合物と一緒に加熱することにより、製造されるこ
とが知られている。2. Description of the Related Art 4,4'-Diamino-1,1'-dianthraquinonyl-3,3'-disulfonic acid and salts thereof are 4,4'-diamino-1,1'-dianthraquinonyl red. It is useful as an intermediate of a pigment, for example, as described in JP-B-38-25842, by removing 1-amino-4-halogenoanthraquinone sulfonic acid together with copper or removing halogen in an acidic medium. It is known to be produced by heating together with a copper compound which can be produced.
【０００３】また、特公昭４５−３４９５１号公報に示
されるように、１−アミノ−４−ハロゲノアントラキノ
ン−２−スルホン酸類を銅または銅化合物の触媒量の存
在のもとで、水性媒質中でヒドロキノン等の還元剤と加
熱することにより製造できることも知られている。[0003] Further, as shown in JP-B-45-34951, 1-amino-4-halogenoanthraquinone-2-sulfonic acid is prepared in an aqueous medium in the presence of a catalytic amount of copper or a copper compound. It is also known that it can be produced by heating with a reducing agent such as hydroquinone.
【０００４】更に、最近特開平５−１９４８６４号公報
では、比表面積が０．２５ｍ2／ｇ以上である銅粉と共
に加熱する方法も提案されている。Further, recently, Japanese Patent Application Laid-Open No. 5-194864 has proposed a method of heating together with copper powder having a specific surface area of 0.25 m 2 / g or more.
【０００５】しかしながら、これら従来技術は、すべて
中間体の１−アミノ−４−ハロゲノアントラキノン−２
−スルホン酸のアルカリ金属塩を製造、単離して４，
４’−ジアミノ−１，１’−ジアントラキノニル−３，
３’ジスルホン酸類またはその塩類を合成するものであ
り、原料の１−アミノ−４−ハロゲノアントラキノン−
２−スルホン酸から一段階で合成できる方法は知られて
いなかった。However, these prior arts all use the intermediate 1-amino-4-halogenoanthraquinone-2.
Producing and isolating an alkali metal salt of sulfonic acid,
4'-diamino-1,1'-dianthraquinonyl-3,
3′-disulfonic acid or a salt thereof is synthesized, and the starting 1-amino-4-halogenoanthraquinone-
A method that can be synthesized in one step from 2-sulfonic acid was not known.
【０００６】更に、これらの方法では１−アミノ−２−
スルホン酸−アントラキノン、１−アミノ−２−スルホ
ン酸−４−ヒドロキシ−アントラキノン等の不純物が生
成し、収率及び純度は満足できるものではなかった。Further, in these methods, 1-amino-2-
Impurities such as sulfonic acid-anthraquinone and 1-amino-2-sulfonic acid-4-hydroxy-anthraquinone were generated, and the yield and purity were not satisfactory.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、上記従来技
術の問題点、即ち、１−アミノ−４−ハロゲノアントラ
キノン−２−スルホン酸から１−アミノ−４−ハロゲノ
アントラキノン−２−スルホン酸塩を取り出さずに、不
純物の少ない４，４’−ジアミノ−１，１’−ジアント
ラキノニル−３，３’−ジスルホン酸類または、その塩
類の製造方法を見出すことを課題とする。SUMMARY OF THE INVENTION The present invention relates to the above-mentioned problems of the prior art, namely, from 1-amino-4-halogenoanthraquinone-2-sulfonic acid to 1-amino-4-halogenoanthraquinone-2-sulfonate. It is an object of the present invention to find a method for producing 4,4′-diamino-1,1′-dianthraquinonyl-3,3′-disulfonic acid or a salt thereof having a small amount of impurities without taking out.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討の結果、ｐＨの調整方法を工
夫することにより、１−アミノ−４−ハロゲノアントラ
キノン−２−スルホン酸から１−アミノ−４−ハロゲノ
アントラキノン−２−スルホン酸塩類を取り出すことな
く、一段階で、不純物の少ない４，４’−ジアミノ−
１，１’−ジアントラキノニル−３，３’−ジスルホン
酸類またはその塩類を製造する方法を見出した。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have devised a method for adjusting the pH to obtain 1-amino-4-halogenoanthraquinone-2-sulfonic acid. Without taking out 1-amino-4-halogenoanthraquinone-2-sulfonates from the reaction mixture in a single step to obtain 4,4′-diamino-
A method for producing 1,1′-dianthraquinonyl-3,3′-disulfonic acid or a salt thereof has been found.
【０００９】即ち、本発明は、１−アミノ−４−ハロゲ
ノアントラキノン−２−スルホン酸を水性媒質中、銅触
媒と共に反応させて４，４’−ジアミノ−１，１’−ジ
アントラキノニル−３，３’−ジスルホン酸類またはそ
の塩類を製造する方法において、反応前に、アルカリで
ｐＨを２〜５に調整し、その後、銅粉を装入して反応さ
せ、その反応中及び反応後に酸でｐＨを２〜５に維持す
ることにより、１−アミノ−４−ハロゲノアントラキノ
ン−２−スルホン酸の塩を取り出すことなく、一段階で
製造することを特徴とする４，４’−ジアミノ−１，
１’−ジアントラキノニル−３，３’−ジスルホン酸類
またはその塩類の製造方法に関するものである。That is, according to the present invention, 1-amino-4-halogenoanthraquinone-2-sulfonic acid is reacted with a copper catalyst in an aqueous medium to produce 4,4'-diamino-1,1'-dianthraquinonyl-3. In the process for producing 3,3'-disulfonic acids or salts thereof, the pH is adjusted to 2 to 5 with an alkali before the reaction, and then copper powder is charged and reacted, and during and after the reaction, an acid is used. By maintaining the pH at 2 to 5, it is possible to prepare 4,4′-diamino-1,4,4′-diamino-1,4 in one step without removing the salt of 1-amino-4-halogenoanthraquinone-2-sulfonic acid
The present invention relates to a method for producing 1'-dianthraquinonyl-3,3'-disulfonic acid or a salt thereof.
【００１０】[0010]
【発明の実施の形態】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操作方法を示せば、１−
アミノ−４−ハロゲノアントラキノン−２−スルホン酸
のウエットケーキを３０〜１００℃の温水中に装入する
か、又は装入後３０〜１００℃に昇温する。次いで、５
〜４５％ＮａＯＨ等のアルカリを装入し、反応液をｐＨ
２〜５に調整する。銅粉を加え、窒素気流下で反応開始
する。反応中に鉱酸等の酸を滴下して、ｐＨを２〜５に
保ちながら３０〜１００℃で１〜２５時間反応させる。
その後、通常のＮａＯＨ、ＮａＣｌ等による塩析操作に
より、４，４’−ジアミノ−１，１’−ジアントラキノ
ニル−３，３’−ジスルホン酸類またはその塩を製造す
ることができる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the method of the present invention, if a specific operation method is shown, 1-
Amino-4-halogeno-anthraquinone-2-sulfonic acid wet cake or charging in hot water of 30 to 100 ° C., or heated to SoIrigo 30 to 100 ° C.. Then 5
~ 45% NaOH or other alkali is charged and the reaction solution is adjusted to pH
Adjust to 2-5. Copper powder is added and the reaction is started under a nitrogen stream. An acid such as a mineral acid is added dropwise during the reaction, and the reaction is carried out at 30 to 100 ° C. for 1 to 25 hours while maintaining the pH at 2 to 5.
Thereafter, 4,4′-diamino-1,1′-dianthraquinonyl-3,3′-disulfonic acid or a salt thereof can be produced by a common salting out operation using NaOH, NaCl or the like.
【００１１】本発明方法において、原料の１−アミノ−
４−ハロゲノアントラキノン−２−スルホン酸の装入温
度及び装入後の昇温温度は、３０〜１００℃であり、好
ましくは３０〜５０℃である。In the method of the present invention, the starting 1-amino-
The charging temperature of 4-halogenoanthraquinone-2-sulfonic acid and the temperature increase after charging are 30 to 100 ° C, and preferably 30 to 50 ° C.
【００１２】本発明方法において、使用するアルカリと
しては、ｐＨを２〜５に調整でき、反応に悪影響を及ぼ
さないものならば特に制限はなく、例として水酸化ナト
リウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウ
ム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸リチ
ウム、水酸化リチウム、水酸化カルシウム、水酸化バリ
ウム等が挙げられ、好ましくは水酸化ナトリウム、水酸
化カリウムを使用する。尚、これらは、単独でもまた２
種以上を混合して使用してもよい。In the method of the present invention, the alkali used is not particularly limited as long as it can adjust the pH to 2 to 5 and does not adversely affect the reaction. Examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, and the like. Examples thereof include potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium carbonate, lithium hydroxide, calcium hydroxide, and barium hydroxide. Preferably, sodium hydroxide and potassium hydroxide are used. These may be used alone or in two.
A mixture of more than one species may be used.
【００１３】使用するアルカリが、水酸化ナトリウムの
場合の濃度は、通常５〜４５重量％であり、好ましくは
１０〜３０重量％である。When the alkali used is sodium hydroxide, the concentration is usually 5 to 45% by weight, preferably 10 to 30% by weight.
【００１４】本発明方法において、原料の溶液は、アル
カリを装入してｐＨを２〜５に調整する。好ましくはｐ
Ｈ２．５〜３．５に調整する。In the method of the present invention, the pH of the raw material solution is adjusted to 2 to 5 by charging an alkali. Preferably p
Adjust to H2.5-3.5.
【００１５】本発明方法において、銅粉を加えた後、ｐ
Ｈ調整のために使用する酸としては、例として硫酸、塩
酸、燐酸等の鉱酸、酢酸、シュウ酸、プロピオン酸等の
有機酸が挙げられる。好ましくは、硫酸、塩酸を使用す
る。In the method of the present invention, after adding the copper powder, p
Examples of the acid used for adjusting H include mineral acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as acetic acid, oxalic acid, and propionic acid. Preferably, sulfuric acid or hydrochloric acid is used.
【００１６】酸を添加して、ｐＨを２〜５、好ましくは
２〜４、さらに好ましくは２．５〜３．５に調整する。The pH is adjusted to 2 to 5, preferably 2 to 4, more preferably 2.5 to 3.5, by adding an acid.
【００１７】本発明方法の反応温度は、通常３０〜１０
０℃であり、好ましくは５０〜１００℃、さらに好まし
くは５０〜８０℃である。反応時間は、通常１〜２５時
間であり、好ましい温度の５０〜８０℃で行った場合
は、１〜３時間程度でよい。The reaction temperature of the method of the present invention is usually from 30 to 10.
0 ° C., preferably 50 to 100 ° C., and more preferably 50 to 80 ° C. The reaction time is generally 1 to 25 hours, and when the reaction is carried out at a preferable temperature of 50 to 80 ° C., it may be about 1 to 3 hours.
【００１８】その後、通常のＮａＯＨ、ＮａＣｌ等の装
入による一般的な塩析操作により、目的化合物を得るこ
とができる。Thereafter, the target compound can be obtained by a general salting-out operation by charging ordinary NaOH, NaCl or the like.
【００１９】[0019]
【実施例】実施例中の「部」および「％」は、重量部お
よび重量％を表す。 実施例１ 水４５００部中に１−アミノ−４−ブロモアントラキノ
ン−２−スルホン酸ウエットケーキ３１７部（ブロマミ
ン酸含有８３．６％）を２５℃で装入する。５５℃まで
昇温し、２５％水酸化ナトリウム１８０部を装入し、ｐ
Ｈを２．８に調整する。同温度で銅粉１００部を装入
し、反応器に窒素を流す。４％硫酸６０部を均一に滴下
しながら、ｐＨを２．５〜３．０に保ち、５５℃で３時
間保温する。同温度でろ過し、６０℃温水１５００部で
洗浄する。ろ洗液に２５％ＮａＯＨ２５９部を加え、７
５℃まで昇温し、１時間保温する。３０℃まで冷却し、
ＮａＣｌ２４０部を加え、同温度で１時間保温する。同
温度でろ過し、１％ＮａＯＨ３０００部でろ塊を洗浄す
る。さらに、１％ＮａＣｌ水３０００部で洗浄、ろ塊を
取り出し乾燥して、４，４’−ジアミノ−１，１’−ジ
アントラキノニル−３，３’−ジスルホン酸２０６部
（純度９９％）を得る。EXAMPLES "Parts" and "%" in the examples represent parts by weight and% by weight. Example 1 317 parts of 1-amino-4-bromoanthraquinone-2-sulfonic acid wet cake (83.6% containing bromamic acid) are charged at 25 ° C. in 4500 parts of water. The temperature was raised to 55 ° C., and 180 parts of 25% sodium hydroxide was charged.
Adjust H to 2.8. At the same temperature, 100 parts of copper powder are charged, and nitrogen is flowed into the reactor. The pH is maintained at 2.5 to 3.0 while uniformly adding 60 parts of 4% sulfuric acid, and the temperature is maintained at 55 ° C. for 3 hours. Filter at the same temperature and wash with 1500 parts of hot water at 60 ° C. 259 parts of 25% NaOH was added to the filtrate, and 7
The temperature is raised to 5 ° C and kept for 1 hour. Cool to 30 ° C,
Add 240 parts of NaCl and keep at the same temperature for 1 hour. Filter at the same temperature and wash the filter cake with 3000 parts of 1% NaOH. Further, the solid was washed with 3000 parts of 1% aqueous NaCl, and the filter cake was taken out and dried to obtain 206 parts of 4,4′-diamino-1,1′-dianthraquinonyl-3,3′-disulfonic acid (purity: 99%). obtain.
【００２０】実施例２ 水４５００部中に１−アミノ−４−ブロモアントラキノ
ン−２−スルホン酸ウェットケーキ３１７部（ブロマミ
ン酸含有８３．６％）を２５℃で装入する。５５℃まで
昇温し、２５％ＮａＯＨ１８０部を装入し、ｐＨを２．
８に調整する。同温度で銅粉１００部を装入し、反応器
に空気を流す。４％硫酸６０部を均一に滴下しながら、
ｐＨを２．５〜３．０に保ち、５５℃で３時間保温す
る。同温度でろ過し、６０℃温水１５００部で洗浄す
る。ろ洗液に２５％ＮａＯＨ２５９部を加え、７５℃ま
で昇温し、１時間保温する。３０℃まで冷却し、ＮａＣ
ｌ２４０部を加え同温度で１時間保温する。同温度でろ
過し１％ＮａＯＨ３０００部でろ塊を洗浄する。さら
に、１％ＮａＣｌ水３０００部で洗浄、ろ塊を取り出し
乾燥して４，４’−ジアミノ−１，１’−ジアントラキ
ノニル−３，３’−ジスルホン酸１７０部（純度９９
％）を得る。Example 2 317 parts of 1-amino-4-bromoanthraquinone-2-sulfonic acid wet cake (83.6% containing bromamic acid) are charged at 25 ° C. in 4500 parts of water. The temperature was raised to 55 ° C, 180 parts of 25% NaOH was charged, and the pH was adjusted to 2.
Adjust to 8. At the same temperature, 100 parts of copper powder are charged, and air is flowed into the reactor. While uniformly dropping 60 parts of 4% sulfuric acid,
Keep the pH at 2.5-3.0 and keep at 55 ° C for 3 hours. Filter at the same temperature and wash with 1500 parts of hot water at 60 ° C. 259 parts of 25% NaOH is added to the filtrate, the temperature is raised to 75 ° C., and the temperature is kept for 1 hour. Cool to 30 ° C and add NaC
Add 1240 parts and keep at the same temperature for 1 hour. Filter at the same temperature, and wash the filter cake with 3000 parts of 1% NaOH. Further, it was washed with 3000 parts of 1% aqueous NaCl, the filter cake was taken out and dried, and 170 parts of 4,4′-diamino-1,1′-dianthraquinonyl-3,3′-disulfonic acid (purity: 99 parts)
%).
【００２１】実施例３ 水４５００部中に１−アミノ−４−ブロモアントラキノ
ン−２−スルホン酸ウェットケーキ３１７部（ブロマミ
ン酸含有８３．６％）を２５℃で装入する。５５℃まで
昇温し、２５％ＫＯＨ１７０部を装入し、ｐＨを２．８
に調整する。同温度で銅粉１００部を装入し、反応器に
窒素を流す。４％塩酸７０部を均一に滴下しながら、ｐ
Ｈを２．５〜３．０に保ち、５５℃で３時間保温する。
同温度でろ過し、６０℃温水１５００部で洗浄する。ろ
洗液に２５％ＮａＯＨ２５９部を加え、７５℃まで昇温
し、１時間保温する。３０℃まで冷却し、ＮａＣｌ２４
０部を加え同温度で１時間保温する。同温度でろ過し、
１％ＮａＯＨ３０００部でろ塊を洗浄する。さらに、１
％ＮａＣｌ水３０００部で洗浄、ろ塊を取り出し乾燥し
て４，４’−ジアミノ−１，１’−ジアントラキノニル
−３，３’−ジスルホン酸２０４部（純度９９％）を得
る。Example 3 317 parts of 1-amino-4-bromoanthraquinone-2-sulfonic acid wet cake (83.6% containing bromamic acid) are charged at 25 ° C. in 4500 parts of water. The temperature was raised to 55 ° C., 170 parts of 25% KOH was charged, and the pH was increased to 2.8.
Adjust to At the same temperature, 100 parts of copper powder are charged, and nitrogen is flowed into the reactor. While uniformly dropping 70 parts of 4% hydrochloric acid, p
Keep H at 2.5-3.0 and keep at 55 ° C for 3 hours.
Filter at the same temperature and wash with 1500 parts of hot water at 60 ° C. 259 parts of 25% NaOH is added to the filtrate, the temperature is raised to 75 ° C., and the temperature is kept for 1 hour. Cool to 30 ° C. and add NaCl 24
Add 0 parts and keep at the same temperature for 1 hour. Filter at the same temperature,
The filter cake is washed with 3000 parts of 1% NaOH. In addition, 1
The filtrate was washed with 3000 parts of an aqueous solution of NaCl, and the filter cake was taken out and dried to obtain 204 parts of 4,4′-diamino-1,1′-dianthraquinonyl-3,3′-disulfonic acid (purity: 99%).
【００２２】比較例１ 水２５００部中に１−アミノ−４−ブロモアントラキノ
ン−２−スルホン酸ウェットケーキ５９８部（ブロマミ
ン酸含有８３．６％）を９０℃で装入する。３２％Ｎａ
ＯＨ２２４部を装入し、ｐＨを７．２に調整する９０℃
まで昇温し、同温度１時間保温する。６０℃まで冷却
し、硫酸ナトリウム１９３部を装入する。６０℃で１時
間保温し、その後ろ過して１−アミノ−４−ブロモアン
トラキノン−２−スルホン酸ナトリウムのウェットケー
キを単離する。１−アミノ−４−ブロモアントラキノン
−２−スルホン酸ナトリウムのウェットケーキ３２９部
を水４５００部中に装入し、５５℃まで昇温する。反応
器に窒素を流し、４％硫酸３５部を装入し、ｐＨを３．
０に調整する。銅粉１０９部を装入し、４％硫酸６０部
を均一滴下しながら、ｐＨを２．５〜３．０に調整しな
がら５５℃で７時間反応する。同温度でろ過し、６０℃
温水１５００部で洗浄する。ろ洗液に２５％ＮａＯＨ２
５９部を加え、７５℃まで昇温し、１時間保温する。３
０℃まで冷却し、ＮａＣｌ２４０部を加え同温度で１時
間保温する。同温度でろ過し、１％ＮａＯＨ３０００部
でろ塊を洗浄する。さらに、１％ＮａＣｌ水３０００部
で洗浄、ろ塊を取り出し乾燥して、４，４’−ジアミノ
−１，１’−ジアントラキノニル−３，３’−ジスルホ
ン酸１８３部（純度９９％）を得る。Comparative Example 1 In 2,500 parts of water, 598 parts of a 1-amino-4-bromoanthraquinone-2-sulfonic acid wet cake (83.6% containing bromamic acid) are charged at 90 ° C. 32% Na
Charge 224 parts of OH and adjust the pH to 7.2 90 ° C
And heat it for 1 hour. Cool to 60 ° C. and charge 193 parts of sodium sulfate. Incubate at 60 ° C. for 1 hour and then filter to isolate a 1-amino-4-bromoanthraquinone-2-sodium sulfonate wet cake. 329 parts of a wet cake of sodium 1-amino-4-bromoanthraquinone-2-sulfonate are charged into 4500 parts of water, and the temperature is raised to 55 ° C. The reactor was flushed with nitrogen, charged with 35 parts of 4% sulfuric acid, and adjusted to pH 3.
Adjust to 0. 109 parts of copper powder is charged and reacted at 55 ° C. for 7 hours while adjusting the pH to 2.5 to 3.0 while uniformly dropping 60 parts of 4% sulfuric acid. Filter at the same temperature, 60 ° C
Wash with 1500 parts of warm water. 25% NaOH2
Add 59 parts, raise the temperature to 75 ° C, and keep it warm for 1 hour. 3
After cooling to 0 ° C., 240 parts of NaCl is added and the mixture is kept at the same temperature for 1 hour. Filter at the same temperature and wash the filter cake with 3000 parts of 1% NaOH. Further, it was washed with 3000 parts of 1% aqueous NaCl, the filter cake was taken out and dried to obtain 183 parts (purity 99%) of 4,4'-diamino-1,1'-dianthraquinonyl-3,3'-disulfonic acid. obtain.
【００２３】比較例２ 水４５００部中に１−アミノ−４−ブロモアントラキノ
ン−２−スルホン酸ウェットケーキ３１７部（ブロマミ
ン酸含有８３．６％）を２５℃で装入する。８０℃まで
昇温し、２５％ＮａＯＨ１００部を装入し、ｐＨを１．
５に調整する。同温度で銅粉１００部を装入し、反応器
に窒素を流す。４％硫酸１００部を均一に滴下しながら
ｐＨを１．５に保ち、８０℃で２時間保温する。同温度
でろ過し、８０℃温水１５００部で洗浄する。ろ洗液に
２５％ＮａＯＨ２５９部を加え、７５℃まで昇温し、１
時間保温する。３０℃まで冷却し、ＮａＣｌ２４０部を
加え、同温度で１時間保温する。同温度でろ過し、１％
ＮａＯＨ３０００部でろ塊を洗浄する。さらに、１％Ｎ
ａＣｌ水３０００部で洗浄、ろ塊を取り出し、乾燥して
４，４’−ジアミノ−１，１’−ジアントラキノニル−
３，３’−ジスルホン酸２０１部（純度７０％）を得
る。COMPARATIVE EXAMPLE 2 317 parts of a 1-amino-4-bromoanthraquinone-2-sulfonic acid wet cake (83.6% containing bromamic acid) are charged at 25 ° C. in 4500 parts of water. The temperature was raised to 80 ° C., 100 parts of 25% NaOH was charged, and the pH was adjusted to 1.
Adjust to 5. At the same temperature, 100 parts of copper powder are charged, and nitrogen is flowed into the reactor. The pH is maintained at 1.5 while uniformly dropping 100 parts of 4% sulfuric acid, and the temperature is maintained at 80 ° C. for 2 hours. Filter at the same temperature and wash with 1500 parts of 80 ° C. hot water. 259 parts of 25% NaOH was added to the filtrate, and the temperature was raised to 75 ° C.
Insulate for hours. Cool to 30 ° C., add 240 parts of NaCl, and keep at the same temperature for 1 hour. Filter at the same temperature, 1%
The filter cake is washed with 3000 parts of NaOH. In addition, 1% N
The residue was washed with 3000 parts of aCl water, and the filter cake was taken out and dried to obtain 4,4'-diamino-1,1'-dianthraquinonyl-
201 parts of 3,3′-disulfonic acid (purity 70%) are obtained.
【００２４】比較例３ 水４５００部中に１−アミノ−４−ブロモアントラキノ
ン−２−スルホン酸ウェットケーキ３１７部（ブロマミ
ン酸含有８３．６％）を２５℃で装入する。５５℃まで
昇温し、２５％ＮａＯＨ１８０部を装入し、ｐＨを２．
８に調整する。同温度で銅粉１００部を装入し、反応器
に窒素を流す。そのまま５５℃で３時間保温する。同温
度でろ過し、６０℃温水１５００部で洗浄する。ろ洗液
に２５％ＮａＯＨ２５９部を加え、７５℃まで昇温し、
１時間保温する。３０℃まで冷却し、ＮａＣｌ２４０部
を加え、同温度で１時間保温する。同温度でろ過し、１
％ＮａＯＨ３０００部でろ塊を洗浄する。さらに、１％
ＮａＣｌ水３０００部で洗浄、ろ塊を取り出し、乾燥し
て４，４’−ジアミノ−１，１’−ジアントラキノニル
−３，３’−ジスルホン酸２０３部（純度７０％）を得
る。COMPARATIVE EXAMPLE 3 317 parts of 1-amino-4-bromoanthraquinone-2-sulfonic acid wet cake (83.6% containing bromamic acid) are charged at 25 ° C. in 4500 parts of water. The temperature was raised to 55 ° C, 180 parts of 25% NaOH was charged, and the pH was adjusted to 2.
Adjust to 8. At the same temperature, 100 parts of copper powder are charged, and nitrogen is flowed into the reactor. Incubate at 55 ° C for 3 hours. Filter at the same temperature and wash with 1500 parts of hot water at 60 ° C. 259 parts of 25% NaOH was added to the filtrate, and the temperature was raised to 75 ° C.
Incubate for 1 hour. Cool to 30 ° C., add 240 parts of NaCl, and keep at the same temperature for 1 hour. Filter at the same temperature, 1
The filter cake is washed with 3000 parts of NaOH. In addition, 1%
After washing with 3000 parts of NaCl aqueous solution, the filter cake is taken out and dried to obtain 203 parts of 4,4′-diamino-1,1′-dianthraquinonyl-3,3′-disulfonic acid (purity: 70%).
【００２５】比較例４ 水４５００部中に１−アミノ−４−ブロモアントラキノ
ン−２−スルホン酸ウェットケーキ３１７部（ブロマミ
ン酸含有８３．６％）を２５℃で装入する。５０℃まで
昇温し、３２％ＮａＯＨ２００部を装入し、ｐＨを７．
０に調整する。同温度で銅粉１００部を装入し、反応器
に窒素を流す。５０℃で２時間保温する。８０℃でろ過
し、８０℃温水１５００部で洗浄する。ろ洗液に２５％
ＮａＯＨ２５９部を加え、７５℃まで昇温し、１時間保
温する。３０℃まで冷却し、ＮａＣｌ２４０部を加え、
同温度で１時間保温する。同温度でろ過し、１％ＮａＯ
Ｈ３０００部でろ塊を洗浄する。さらに、１％ＮａＣｌ
水３０００部で洗浄、ろ塊を取り出し、乾燥して４，
４’−ジアミノ−１，１’−ジアントラキノニル−３，
３’−ジスルホン酸２００部（純度７０％）を得る。COMPARATIVE EXAMPLE 4 317 parts of 1-amino-4-bromoanthraquinone-2-sulfonic acid wet cake (83.6% containing bromamic acid) are charged at 25 ° C. in 4500 parts of water. The temperature was raised to 50 ° C., and 200 parts of 32% NaOH was charged.
Adjust to 0. At the same temperature, 100 parts of copper powder are charged, and nitrogen is flowed into the reactor. Incubate at 50 ° C for 2 hours. Filter at 80 ° C and wash with 1500 parts of 80 ° C warm water. 25% in the washing solution
Add 259 parts of NaOH, raise the temperature to 75 ° C., and keep the temperature for 1 hour. Cool to 30 ° C., add 240 parts of NaCl,
Incubate at the same temperature for 1 hour. Filter at the same temperature, 1% NaO
The filter cake is washed with 3000 parts of H. Further, 1% NaCl
Wash with 3000 parts of water, take out the filter cake, dry and
4'-diamino-1,1'-dianthraquinonyl-3,
200 parts of 3'-disulfonic acid (purity 70%) are obtained.
【００２６】[0026]
【発明の効果】本発明の方法によれば１−アミノ−４−
ハロゲノアントラキノン−２−スルホン酸の塩類を取り
出すことなく、高収率で高純度の４，４’−ジアミノ−
１，１’−ジアントラキノニル−３，３’−ジスルホン
酸類またはその塩類を得ることができる。即ち本発明
は、工業的に効率の良い、極めて価値のある方法であ
る。According to the method of the present invention, 1-amino-4-
Without removing salts of halogenoanthraquinone-2-sulfonic acid, high yield and high purity 4,4'-diamino-
1,1′-Dianthraquinonyl-3,3′-disulfonic acid or a salt thereof can be obtained. That is, the present invention is an industrially efficient and extremely valuable method.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 309/00 C07C 303/00 C09B 1/00 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. 7 , DB name) C07C 309/00 C07C 303/00 C09B 1/00 CA (STN) REGISTRY (STN)
Claims (3)
ン−２−スルホン酸を水性媒質中、銅触媒と共に反応さ
せて４，４’−ジアミノ−１，１’−ジアントラキノニ
ル−３，３’−ジスルホン酸類またはその塩類を製造す
る方法において、反応前に、アルカリでｐＨを２〜５に
調整し、その後、銅粉を装入して反応させ、その反応中
及び反応後に酸でｐＨを２〜５に維持することにより、
１−アミノ−４−ハロゲノアントラキノン−２−スルホ
ン酸の塩を取り出すことなく、一段階で製造することを
特徴とする４，４’−ジアミノ−１，１’−ジアントラ
キノニル−３，３’−ジスルホン酸類またはその塩類の
製造方法。1. A reaction of 1-amino-4-halogenoanthraquinone-2-sulfonic acid with a copper catalyst in an aqueous medium to give 4,4′-diamino-1,1′-dianthraquinonyl-3,3′-. In the method for producing disulfonic acids or salts thereof, the pH is adjusted to 2 to 5 with an alkali before the reaction, and then copper powder is charged and reacted, and the pH is adjusted to 2 to 2 with an acid during and after the reaction. By maintaining at 5,
4,4′-diamino-1,1′-dianthraquinonyl-3,3 ′, which is prepared in one step without removing a salt of 1-amino-4-halogenoanthraquinone-2-sulfonic acid. -A method for producing disulfonic acids or salts thereof.
る請求項１記載の方法。2. The method according to claim 1, wherein the reaction is carried out under a nitrogen stream.
カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナ
トリウムから選ばれたものであり、酸が塩酸、硫酸、燐
酸から選ばれるものである請求項１または請求項２記載
の方法。3. The method according to claim 1, wherein the alkali is selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydrogencarbonate, and the acid is selected from hydrochloric acid, sulfuric acid, and phosphoric acid. The method of claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33663295A JP3270673B2 (en) | 1995-12-25 | 1995-12-25 | Process for producing 4,4'-diamino-1,1'-dianthraquinonyl-3,3'-disulfonic acid or salts thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33663295A JP3270673B2 (en) | 1995-12-25 | 1995-12-25 | Process for producing 4,4'-diamino-1,1'-dianthraquinonyl-3,3'-disulfonic acid or salts thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09176108A JPH09176108A (en) | 1997-07-08 |
| JP3270673B2 true JP3270673B2 (en) | 2002-04-02 |
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ID=18301174
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|---|---|---|---|
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| Country | Link |
|---|---|
| JP (1) | JP3270673B2 (en) |
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1995
- 1995-12-25 JP JP33663295A patent/JP3270673B2/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| チェコスロバキア国特許第２１７２５２号明細書 |
| チェコスロバキア国特許第２７３４２８号明細書 |
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| Publication number | Publication date |
|---|---|
| JPH09176108A (en) | 1997-07-08 |
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| Date | Code | Title | Description |
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| LAPS | Cancellation because of no payment of annual fees |