JP3148484B2 - Method for producing 1-amino-5-benzoylaminoanthraquinone - Google Patents
Method for producing 1-amino-5-benzoylaminoanthraquinoneInfo
- Publication number
- JP3148484B2 JP3148484B2 JP31948493A JP31948493A JP3148484B2 JP 3148484 B2 JP3148484 B2 JP 3148484B2 JP 31948493 A JP31948493 A JP 31948493A JP 31948493 A JP31948493 A JP 31948493A JP 3148484 B2 JP3148484 B2 JP 3148484B2
- Authority
- JP
- Japan
- Prior art keywords
- benzoylaminoanthraquinone
- amino
- diaminoanthraquinone
- temperature
- dmi
- 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
- FWEQPMZEKHHFTB-UHFFFAOYSA-N n-(5-amino-9,10-dioxoanthracen-1-yl)benzamide Chemical compound C1=CC=C2C(=O)C=3C(N)=CC=CC=3C(=O)C2=C1NC(=O)C1=CC=CC=C1 FWEQPMZEKHHFTB-UHFFFAOYSA-N 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- VWBVCOPVKXNMMZ-UHFFFAOYSA-N 1,5-diaminoanthracene-9,10-dione Chemical compound O=C1C2=C(N)C=CC=C2C(=O)C2=C1C=CC=C2N VWBVCOPVKXNMMZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 5
- -1 benzoyl halide Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- PZNXLZZWWBSQQK-UHFFFAOYSA-N n-(5-benzamido-9,10-dioxoanthracen-1-yl)benzamide Chemical compound C=1C=CC=CC=1C(=O)NC(C=1C(=O)C2=CC=C3)=CC=CC=1C(=O)C2=C3NC(=O)C1=CC=CC=C1 PZNXLZZWWBSQQK-UHFFFAOYSA-N 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 3
- 238000006480 benzoylation reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 2
- AQIHMSVIAGNIDM-UHFFFAOYSA-N benzoyl bromide Chemical compound BrC(=O)C1=CC=CC=C1 AQIHMSVIAGNIDM-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- VHIODVHPCLGSRM-UHFFFAOYSA-N 1,5-dibenzoylanthracene-9,10-dione Chemical compound C(C1=CC=CC=C1)(=O)C1=CC=CC=2C(C3=C(C=CC=C3C(C1=2)=O)C(C1=CC=CC=C1)=O)=O VHIODVHPCLGSRM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YWGOEAQPMPNQMZ-UHFFFAOYSA-N NC1(C2C(C=3C=CC=CC3C(C2=CC=C1)=O)=O)N Chemical compound NC1(C2C(C=3C=CC=CC3C(C2=CC=C1)=O)=O)N YWGOEAQPMPNQMZ-UHFFFAOYSA-N 0.000 description 1
- HPMLGNIUXVXALD-UHFFFAOYSA-N benzoyl fluoride Chemical compound FC(=O)C1=CC=CC=C1 HPMLGNIUXVXALD-UHFFFAOYSA-N 0.000 description 1
- WPCXDBCEDWUSOU-UHFFFAOYSA-N benzoyl iodide Chemical compound IC(=O)C1=CC=CC=C1 WPCXDBCEDWUSOU-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- KOJOUCAVSDKDPR-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)benzamide Chemical compound C=1C=CC=2C(=O)C3=CC=CC=C3C(=O)C=2C=1NC(=O)C1=CC=CC=C1 KOJOUCAVSDKDPR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、染料、顔料及びそれら
の中間体として有用な１−アミノ−５−ベンゾイルアミ
ノアントラキノンの新規な製造方法に関する。FIELD OF THE INVENTION The present invention relates to a novel process for producing 1-amino-5-benzoylaminoanthraquinone which is useful as a dye, a pigment and an intermediate thereof.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】文献
（ＦＩＡＴ １０１６；１３１３）には、１，５−ジア
ミノアントラキノンをニトロベンゼン溶媒中、炭酸ソー
ダの存在下、塩化ベンゾイルでベンゾイル化する製造法
が知られているが、収率が６０％と低い。また、使用す
るニトロベンゼン溶媒および塩化ベンゾイルの量が多
く、さらに反応物の分離に高温濾過（１５０℃）を必要
とし、作業性および製造コスト上の問題がある。2. Description of the Related Art The literature (FIAT 1016; 1313) discloses a method for producing 1,5-diaminoanthraquinone by benzoylation with benzoyl chloride in a nitrobenzene solvent in the presence of sodium carbonate. However, the yield is as low as 60%. In addition, the amounts of the nitrobenzene solvent and benzoyl chloride used are large, and high-temperature filtration (150 ° C.) is required for separating the reactants, which causes problems in workability and production cost.
【０００３】[0003]
【課題を解決するための手段】本発明者らはこれらの課
題を解決し、工業的に安全性がすぐれていて、しかも高
収率、高純度の１−アミノ−５−ベンゾイルアミノアン
トラキノンを得る方法を鋭意検討した結果、本発明を完
成した。Means for Solving the Problems The present inventors have solved these problems and obtained 1-amino-5-benzoylaminoanthraquinone which is industrially safe and has a high yield and a high purity. As a result of intensive studies on the method, the present invention has been completed.
【０００４】すなわち、本発明は１，５−ジアミノアン
トラキノンを、１，３−ジメチル−２−イミダゾリジノ
ン（以下「ＤＭＩ」と略す）溶媒中、ハロゲン化ベンゾ
イルと反応させることを特徴とする、１−アミノ−５−
ベンゾイルアミノアントラキノンの製造法である。That is, the present invention is characterized in that 1,5-diaminoanthraquinone is reacted with benzoyl halide in 1,3-dimethyl-2-imidazolidinone (hereinafter abbreviated as "DMI") solvent. 1-amino-5-
This is a method for producing benzoylaminoanthraquinone.
【０００５】本発明に用いるハロゲン化ベンゾイルは、
フッ化ベンゾイル、塩化ベンゾイル、臭化ベンゾイル、
あるいはヨウ化ベンゾイルであり、その使用量は、通
常、１，５−ジアミノアントラキノンに対して１．０〜
２．０モル、好ましくは１．２〜１．４モルである。The benzoyl halide used in the present invention is
Benzoyl fluoride, benzoyl chloride, benzoyl bromide,
Alternatively, benzoyl iodide is used in an amount of usually 1.0 to 1,5-diaminoanthraquinone.
2.0 moles, preferably 1.2-1.4 moles.
【０００６】ベンゾイル化温度は２０〜１００℃、好ま
しくは３５〜６０℃である。反応温度が３５℃未満では
反応が遅く、また６０℃を越えると１，５−ジベンゾイ
ルアミノアントラキノンの副生が多くなり、収率が低下
する傾向にある。[0006] The benzoylation temperature is between 20 and 100 ° C, preferably between 35 and 60 ° C. If the reaction temperature is lower than 35 ° C., the reaction is slow, and if it exceeds 60 ° C., the amount of 1,5-dibenzoylaminoanthraquinone by-produced increases, and the yield tends to decrease.
【０００７】本発明に用いる溶媒のＤＭＩの量は、通
常、原料である１，５−ジアミノアントラキノンの５〜
２０重量倍、好ましくは１０〜１３重量倍であり、使用
したＤＭＩは反応物を分離した濾液から蒸留により高収
率で回収し、再使用できる。[0007] The amount of DMI of the solvent used in the present invention is usually from 5 to 5,5-diaminoanthraquinone as a raw material.
It is 20 times by weight, preferably 10 to 13 times by weight, and the DMI used can be recovered in high yield from the filtrate from which the reaction product has been separated by distillation and reused.
【０００８】ベンゾイル化反応の終点は、反応マス中の
未反応の１，５−ジアミノアントラキノンの残存量が２
％〜３％となる時点とするのがよい。残存量をそれより
少なくしようとして更に反応すると１，５−ジベンゾイ
ルアントラキノンの副生が多くなり、また多すぎると分
離が困難になる。[0008] The end point of the benzoylation reaction is that the residual amount of unreacted 1,5-diaminoanthraquinone in the reaction mass is 2%.
It is preferable to set the time point when it becomes% to 3%. When the reaction is further performed to reduce the remaining amount, the amount of 1,5-dibenzoylanthraquinone by-produced increases, and when the amount is too large, separation becomes difficult.
【０００９】生成物の分離については、反応マスを１０
０〜１５０℃、好ましくは１１５〜１２０℃まで昇温
し、熱濾過して少量の副生した１，５−ジベンゾイルア
ミノアントラキノンを濾塊として分離した後、濾液を水
で希釈してＤＭＩ濃度を６０〜７０重量％濃度に調整
し、晶出した１−アミノ−５−ベンゾイルアミノアント
ラキノンを濾過、水洗、乾燥することにより、反応マス
から１−アミノ−５−ベンゾイルアミノアントラキノン
を分離することができる。For the separation of the products, the reaction mass is
The temperature was raised to 0 to 150 ° C., preferably 115 to 120 ° C., and after hot filtration to separate a small amount of by-produced 1,5-dibenzoylaminoanthraquinone as a filter cake, the filtrate was diluted with water to obtain a DMI concentration. Is adjusted to a concentration of 60 to 70% by weight, and the crystallized 1-amino-5-benzoylaminoanthraquinone is filtered, washed with water and dried to separate 1-amino-5-benzoylaminoanthraquinone from the reaction mass. it can.
【００１０】反応にはアルカリ塩を添加することができ
る。添加しなくても反応は進行するが、反応速度が遅く
なるので、添加する方が好ましい。用いるアルカリ塩の
例としては炭酸ナトリウム、炭酸カリウムおよび炭酸水
素ナトリウム等が挙げられ、これらは１，５−ジアミノ
アントラキノン１モルに対し１．０〜３．０モル使用す
ればよく、好ましくは炭酸水素ナトリウムを１．５〜
１．７モル使用する。[0010] An alkali salt can be added to the reaction. The reaction proceeds without the addition, but the reaction rate is slowed down, so that the addition is preferred. Examples of the alkali salt to be used include sodium carbonate, potassium carbonate and sodium hydrogen carbonate. These may be used in an amount of 1.0 to 3.0 mol per 1 mol of 1,5-diaminoanthraquinone, preferably hydrogen carbonate. Sodium 1.5 ~
1.7 moles are used.
【００１１】[0011]
【実施例】以下、実施例をあげて本発明を具体的に説明
する。尚、「％」は重量％を表す。 実施例１ 攪拌装置、温度計、滴下ロートを備えた１リットルの四
ツ口フラスコにＤＭＩ５００ｇ、１，５−ジアミノアン
トラキノン（純度９６．５％）５０ｇを仕込み、４０℃
に昇温し、４０〜４５℃で１時間攪拌した。そこへ炭酸
水素ナトリウム２９．８ｇを添加し、同温で０．５時間
攪拌したのち、塩化ベンゾイル４１．５ｇを４０〜４５
℃で３時間かけて滴下した。さらに４０〜４５℃で１時
間攪拌したのち１２０℃まで昇温し、この温度で熱濾過
を行い、残渣を１２０℃のＤＭＩ１５０ｇで洗浄した。
得られた濾液を攪拌しながら水３５０ｇを室温で滴下し
てＤＭＩ濃度６５％に調整し晶析を行った。析出した結
晶を濾過、水洗、乾燥して１−アミノ−５−ベンゾイル
アミノアントラキノン５４．０ｇを得た。収率７５％、
純度９７．５％で、含有する１，５−ジアミノアントラ
キノンは０．５％であった。なお、熱濾過、洗浄した濾
塊を湯洗、乾燥したところ、１，５−ジベンゾイルアミ
ノアントラキノン２５．１ｇが得られた。The present invention will be described below in detail with reference to examples. In addition, "%" represents weight%. Example 1 500 g of DMI and 50 g of 1,5-diaminoanthraquinone (purity 96.5%) were charged into a 1-liter four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and heated at 40 ° C.
And stirred at 40 to 45 ° C. for 1 hour. 29.8 g of sodium hydrogencarbonate was added thereto, and the mixture was stirred at the same temperature for 0.5 hour.
The solution was added dropwise at 3 ° C. over 3 hours. After stirring at 40 to 45 ° C. for 1 hour, the temperature was raised to 120 ° C., hot filtration was performed at this temperature, and the residue was washed with 150 g of DMI at 120 ° C.
While stirring the obtained filtrate, 350 g of water was added dropwise at room temperature to adjust the DMI concentration to 65%, and crystallization was performed. The precipitated crystals were filtered, washed with water and dried to obtain 54.0 g of 1-amino-5-benzoylaminoanthraquinone. 75% yield,
The purity was 97.5%, and the contained 1,5-diaminoanthraquinone was 0.5%. In addition, 25.1 g of 1,5-dibenzoylaminoanthraquinone was obtained when hot filtration and the washed cake were washed with hot water and dried.
【００１２】実施例２ 実施例１で用いたのと同じ１リットルの四ツ口フラスコ
にＤＭＩ５２８ｇ、１，５−ジアミノアントラキノン
（純度９６．５％）４０ｇを仕込み、４０℃に昇温し、
４０〜４５℃で１時間攪拌した。そこへ炭酸ナトリウム
３２．０ｇを添加し、同温で０．５時間攪拌したのち臭
化ベンゾイル４３．７ｇを４０〜４５℃で３時間かけて
滴下した。４０〜４５℃で１時間攪拌したのち１２０℃
まで昇温し、この温度で熱濾過を行い、残渣を１２０℃
のＤＭＩ１２６ｇで洗浄した。得られた濾液を攪拌しな
がら水３５２ｇを室温で滴下してＤＭＩ濃度６０％に調
整し晶析を行った。以下実施例１の処方で処理し１−ア
ミノ−５−ベンゾイルアミノアントラキノン４２．０ｇ
を得た。収率７３．０％、純度９７．７％で、含有する
１，５−ジアミノアントラキノンは０．６％であった。
なお、熱濾過、洗浄した濾塊を湯洗、乾燥したところ、
１，５−ジベンゾイルアミノアントラキノン２５．２ｇ
が得られた。Example 2 528 g of DMI and 40 g of 1,5-diaminoanthraquinone (purity: 96.5%) were charged into the same one-liter four-necked flask used in Example 1, and the temperature was raised to 40 ° C.
Stirred at 40-45 ° C for 1 hour. 32.0 g of sodium carbonate was added thereto, and the mixture was stirred at the same temperature for 0.5 hour, and then 43.7 g of benzoyl bromide was added dropwise at 40 to 45 ° C. over 3 hours. After stirring at 40-45 ° C for 1 hour, 120 ° C
Temperature, and hot filtration was performed at this temperature.
Was washed with 126 g of DMI. While stirring the obtained filtrate, 352 g of water was added dropwise at room temperature to adjust the DMI concentration to 60%, and crystallization was performed. Thereafter, the mixture was treated in the same manner as in Example 1 and 12.0 g of 1-amino-5-benzoylaminoanthraquinone
I got The yield was 73.0%, the purity was 97.7%, and the contained 1,5-diaminoanthraquinone was 0.6%.
In addition, hot filtration, when the washed lump was washed with hot water and dried,
15.2 g of 1,5-dibenzoylaminoanthraquinone
was gotten.
【００１３】[0013]
【発明の効果】本発明により、１−アミノ−５−ベンゾ
イルアミノアントラキノンを高純度かつ高収率で得る、
工業的に有利な製法を提供することができた。According to the present invention, 1-amino-5-benzoylaminoanthraquinone can be obtained in high purity and high yield.
An industrially advantageous production method could be provided.
Claims (1)
１，３−ジメチル−２−イミダゾリジノン溶媒中、ハロ
ゲン化ベンゾイルと反応させることを特徴とする、１−
アミノ−５−ベンゾイルアミノアントラキノンの製造
法。1. A method according to claim 1, wherein the 1,5-diaminoanthraquinone is
Reacting with a benzoyl halide in a 1,3-dimethyl-2-imidazolidinone solvent,
A method for producing amino-5-benzoylaminoanthraquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31948493A JP3148484B2 (en) | 1993-12-20 | 1993-12-20 | Method for producing 1-amino-5-benzoylaminoanthraquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31948493A JP3148484B2 (en) | 1993-12-20 | 1993-12-20 | Method for producing 1-amino-5-benzoylaminoanthraquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07173117A JPH07173117A (en) | 1995-07-11 |
| JP3148484B2 true JP3148484B2 (en) | 2001-03-19 |
Family
ID=18110728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31948493A Expired - Fee Related JP3148484B2 (en) | 1993-12-20 | 1993-12-20 | Method for producing 1-amino-5-benzoylaminoanthraquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3148484B2 (en) |
-
1993
- 1993-12-20 JP JP31948493A patent/JP3148484B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07173117A (en) | 1995-07-11 |
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