JP2931689B2 - Method for producing anthraquinone-2-carboxylic acid - Google Patents
Method for producing anthraquinone-2-carboxylic acidInfo
- Publication number
- JP2931689B2 JP2931689B2 JP3107891A JP10789191A JP2931689B2 JP 2931689 B2 JP2931689 B2 JP 2931689B2 JP 3107891 A JP3107891 A JP 3107891A JP 10789191 A JP10789191 A JP 10789191A JP 2931689 B2 JP2931689 B2 JP 2931689B2
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- sulfuric acid
- dinitrile
- anthraquinone
- general formula
- 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 - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- ASDLSKCKYGVMAI-UHFFFAOYSA-N 9,10-dioxoanthracene-2-carboxylic acid Chemical compound C1=CC=C2C(=O)C3=CC(C(=O)O)=CC=C3C(=O)C2=C1 ASDLSKCKYGVMAI-UHFFFAOYSA-N 0.000 title description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- WONPUYDAAHCRKZ-UHFFFAOYSA-N 9,10-dioxoanthracene-1,2-dicarbonitrile Chemical compound C1=CC(C#N)=C(C#N)C2=C1C(=O)C1=CC=CC=C1C2=O WONPUYDAAHCRKZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- -1 1,4-diamino-4-hydroxyanthraquinone- 2,3-dinitrile Chemical compound 0.000 description 8
- 239000005457 ice water Substances 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- PLDISGVCDWLKQC-UHFFFAOYSA-N 1,3-dihydroxy-9,10-dioxoanthracene-2-carboxylic acid Chemical compound C1=CC=C2C(=O)C3=C(O)C(C(=O)O)=C(O)C=C3C(=O)C2=C1 PLDISGVCDWLKQC-UHFFFAOYSA-N 0.000 description 1
- BXKMOYFSOOHUIN-UHFFFAOYSA-N 1,4,5,8-tetraamino-9,10-dioxoanthracene-2,3-dicarbonitrile Chemical compound O=C1C2=C(N)C(C#N)=C(C#N)C(N)=C2C(=O)C2=C1C(N)=CC=C2N BXKMOYFSOOHUIN-UHFFFAOYSA-N 0.000 description 1
- QUZJFTXRXJQLBH-UHFFFAOYSA-N 1,4-diamino-9,10-dioxoanthracene-2,3-dicarbonitrile Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(C#N)C(C#N)=C2N QUZJFTXRXJQLBH-UHFFFAOYSA-N 0.000 description 1
- DNIHCFWMWZCKCQ-UHFFFAOYSA-N 1,4-diamino-9,10-dioxoanthracene-2-carboxylic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(C(O)=O)C=C2N DNIHCFWMWZCKCQ-UHFFFAOYSA-N 0.000 description 1
- VCEQTPJIVOSEJJ-UHFFFAOYSA-N 5,6,7,8-tetrachloro-9,10-dioxoanthracene-2-carboxylic acid Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)C3=CC(C(=O)O)=CC=C3C(=O)C2=C1Cl VCEQTPJIVOSEJJ-UHFFFAOYSA-N 0.000 description 1
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- UGOABQVUDBNSOX-UHFFFAOYSA-N 9,10-dioxoanthracene-2,3-dicarbonitrile Chemical compound N#CC1=C(C#N)C=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 UGOABQVUDBNSOX-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、分散染料、近赤外線吸
収剤、カラー液晶用、２色性色素、昇華転写記録用色素
などに用いられるアントラキノン−２−カルボン酸の製
造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing anthraquinone-2-carboxylic acid for use in disperse dyes, near-infrared absorbing agents, color liquid crystal, dichroic dyes, dyes for sublimation transfer recording, and the like.
【０００２】[0002]
【従来の技術】アントラキノン−２−カルボン酸の製造
方法として、下式（Ａ）（化３）の方法が”染料化学”
細田豊著；技報堂刊の５５４項に記載されている。2. Description of the Related Art As a method for producing anthraquinone-2-carboxylic acid, a method represented by the following formula (A) (formula 3) is referred to as "dye chemistry".
It is described in Yuho Hosoda, 554, published by Gihodo.
【０００３】[0003]
【化３】 しかし、式（Ａ）の方法は多工程数を要し、またアント
ラキノン骨格２位にカルボン酸基を導入するために、メ
チル基を人体に有害な重金属を使用してカルボン酸へ酸
化する必要があり、工業的に利用する一般的合成法とし
ては問題があった。そのため高収率で簡便な新しい製造
法を検討する必要があった。Embedded image However, the method of the formula (A) requires a large number of steps, and in order to introduce a carboxylic acid group at the 2-position of the anthraquinone skeleton, it is necessary to oxidize the methyl group to a carboxylic acid using a heavy metal harmful to the human body. There is a problem as a general synthetic method used industrially. Therefore, it was necessary to study a new production method which was simple and high yield.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、工業
的に入手容易なアントラキノン−２，３−ジニトリルを
原料として、より簡便な方法で、しかも高收率、かつ高
純度でアントラキノン−２−カルボン酸を製造する方法
を提供することである。An object of the present invention is to use anthraquinone-2,3-dinitrile, which is industrially easily available, as a raw material, in a simpler method, at a high yield and high purity. -To provide a method for producing carboxylic acids.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記課題
を解決するために鋭意検討した結果、驚くべきことに、
特定のジニトリルを原料として選択することにより目的
のモノカルボン酸を得る反応を見出し、本発明を達成し
たものである。The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, surprisingly,
The present invention has been accomplished by finding a reaction for obtaining a target monocarboxylic acid by selecting a specific dinitrile as a raw material.
【０００６】すなわち、本発明の方法は、一般式（Ｉ）
（化４）That is, the method of the present invention comprises a compound represented by the general formula (I)
(Formula 4)
【０００７】[0007]
【化４】 （式中、R1、R2、R3およびR4は各々独立に水素原子、ハ
ロゲン原子、水酸基、アミノ基を表す）で示されるアン
トラキノンジニトリルを濃度６０〜１００％の硫酸中、
５０〜２００℃で処理することを特徴とする下記一般式
（II）（化５）Embedded image (Wherein R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or an amino group) in sulfuric acid having a concentration of 60 to 100%,
The following general formula (II) characterized in that the treatment is carried out at 50 to 200 ° C.
【０００８】[0008]
【化５】 （式中、R1、R2、R3およびR4は各々独立に水素原子、ハ
ロゲン原子、水酸基、アミノ基を表す）で示されるアン
トラキノン−２−カルボン酸の製造方法である。Embedded image (Wherein, R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or an amino group).
【０００９】本発明で用いられる一般式（Ｉ）で示され
るアントラキノンジニトリルとしては、具体的には１，
４−ジアミノアントラキノン−２，３−ジニトリル、
１，４−ジアミノ−４−ヒドロキシアントラキノン−
２，３−ジニトリル、１，４，５−トリアミノアントラ
キノン−２，３−ジニトリル、１，４−ジアミノ−５−
ヒドロキシアントラキノン−２，３−ジニトリル、１，
４−ジアミノ−５，８−ジヒドロキシアントラキノン−
２，３−ジニトリル、１，４，５、８−テトラアミノア
ントラキノン−２，３−ジニトリル、１，４−ジアミノ
−５，８−ジクロルアントラキノン−２，３−ジニトリ
ル、１，４−ジアミノ−５，６，７，８−テトラクロル
アントラキノン−２，３−ジニトリル等が挙げられる。As the anthraquinone dinitrile represented by the general formula (I) used in the present invention, specifically,
4-diaminoanthraquinone-2,3-dinitrile,
1,4-diamino-4-hydroxyanthraquinone-
2,3-dinitrile, 1,4,5-triaminoanthraquinone-2,3-dinitrile, 1,4-diamino-5-
Hydroxyanthraquinone-2,3-dinitrile, 1,
4-diamino-5,8-dihydroxyanthraquinone-
2,3-dinitrile, 1,4,5,8-tetraaminoanthraquinone-2,3-dinitrile, 1,4-diamino-5,8-dichloroanthraquinone-2,3-dinitrile, 1,4-diamino- 5,6,7,8-tetrachloroanthraquinone-2,3-dinitrile and the like.
【００１０】本発明で使用する硫酸の濃度は６０〜１０
０％の範囲であり、好ましくは８０〜９５％が良い。６
０％以下の硫酸濃度では一般式（Ｉ）の化合物の硫酸に
対する溶解度が不足し反応が進行しない。The concentration of sulfuric acid used in the present invention is 60 to 10
It is in the range of 0%, preferably 80 to 95%. 6
At a sulfuric acid concentration of 0% or less, the solubility of the compound of the general formula (I) in sulfuric acid is insufficient and the reaction does not proceed.
【００１１】硫酸の使用量は、反応原料である一般式
（Ｉ）で表されるアントラキノンジニトリルの３〜５０
倍重量であり、好ましくは５〜２０倍重量が良い。３倍
未満の場合では反応が完結せず、低純度の一般式（II）
で表されるアントラキノン−２−カルボン酸が得られる
のみである。なお、５０倍を越える硫酸を使用しても特
に問題は無いが、無闇に多量を使用することは反応器の
容積効率を低下させるのみであり、３〜５０倍重量の硫
酸を使用した場合と比較して特に効果は見られない。The amount of sulfuric acid used is 3 to 50% of the amount of the anthraquinone dinitrile represented by the general formula (I) as a reaction raw material.
Double weight, preferably 5 to 20 times weight. If the amount is less than 3 times, the reaction is not completed and the low-purity general formula (II)
Only anthraquinone-2-carboxylic acid represented by In addition, although there is no particular problem even if sulfuric acid exceeding 50 times is used, the use of a large amount in vain only lowers the volumetric efficiency of the reactor, and the case where 3 to 50 times by weight sulfuric acid is used. No particular effect is seen in comparison.
【００１２】反応温度は５０〜２００℃の範囲であり、
好ましくは１１０〜１４０℃の範囲が良い。５０℃未満
の温度では反応が進行せず、一方２００℃を超える温度
では不純物が生成し、純度が低下する。又、反応時間は
１〜２０時間の範囲であり、好ましくは３〜１０時間程
度である。The reaction temperature ranges from 50 to 200 ° C.
Preferably, the range of 110 to 140 ° C. is good. At a temperature lower than 50 ° C., the reaction does not proceed, while at a temperature higher than 200 ° C., impurities are generated and the purity is reduced. The reaction time is in the range of 1 to 20 hours, preferably about 3 to 10 hours.
【００１３】以上のように反応させた後、反応液を室温
まで冷却した後、氷水に排出し、濾過、洗浄、乾燥する
ことにより高収率、高純度で一般式（II）で表されるア
ントラキノン−２−カルボン酸を得ることができる。After the reaction as described above, the reaction solution is cooled to room temperature, discharged into ice water, filtered, washed and dried to be represented by the general formula (II) in high yield and high purity. Anthraquinone-2-carboxylic acid can be obtained.
【００１４】[0014]
【実施例】以下、実施例により本発明を詳しく説明す
る。 実施例１ ８０％の硫酸１００ｇに１，４−ジアミノアントラキノ
ン−２，３−ジニトリル１０ｇを装入し、１３０℃で９
時間加熱攪拌した。反応液を室温に冷却した後氷水２０
０ｇに排出し、析出した固体を濾過、水洗し乾燥して、
１，４−ジアミノアントラキノン−２−カルボン酸９．
５ｇを得た。液体クロマトグラフにより純度９５．８％
であった。The present invention will be described below in detail with reference to examples. Example 1 To 100 g of 80% sulfuric acid was charged 10 g of 1,4-diaminoanthraquinone-2,3-dinitrile, and at 130 ° C., 9 g
The mixture was heated and stirred for hours. After cooling the reaction solution to room temperature, ice water 20
0 g, the precipitated solid was filtered, washed with water and dried,
1,4-diaminoanthraquinone-2-carboxylic acid9.
5 g were obtained. 95.8% purity by liquid chromatography
Met.
【００１５】実施例２ ９０％の硫酸２００ｇに１，４，５−トリアミノアント
ラキノン−２，３−ジニトリル１０ｇを装入し、１００
℃で５時間加熱攪拌した。反応液を室温に冷却した後、
氷水４００ｇに排出し、析出した固体を濾過、水洗し乾
燥して、１，４，５−トリアミノアントラキノン−２−
カルボン酸９．４ｇを得た。液体クロマトグラフにより
純度９３％であった。Example 2 To 200 g of 90% sulfuric acid was charged 10 g of 1,4,5-triaminoanthraquinone-2,3-dinitrile,
The mixture was heated and stirred at 5 ° C. for 5 hours. After cooling the reaction to room temperature,
The mixture was discharged into 400 g of ice water, and the precipitated solid was filtered, washed with water, and dried to obtain 1,4,5-triaminoanthraquinone-2-.
9.4 g of carboxylic acid were obtained. The purity by liquid chromatography was 93%.
【００１６】実施例３ ６０％の硫酸３００ｇに１，４−ジアミノ−５，８−ジ
ヒドロキシアントラキノン−２，３−ジニトリル１０ｇ
を装入し、１５０℃で１０時間加熱攪拌した。反応液を
室温に冷却した後、氷水６００ｇに排出、析出した固体
を濾過、水洗し乾燥して、１，４−ジアミノ−５，８−
ジヒドロキシアントラキノン−２−カルボン酸９ｇを得
た。液体クロマトグラフにより純度９４．５％であっ
た。Example 3 10 g of 1,4-diamino-5,8-dihydroxyanthraquinone-2,3-dinitrile in 300 g of 60% sulfuric acid
And heated and stirred at 150 ° C. for 10 hours. After the reaction solution was cooled to room temperature, it was discharged into 600 g of ice water, and the precipitated solid was filtered, washed with water and dried to obtain 1,4-diamino-5,8-.
9 g of dihydroxyanthraquinone-2-carboxylic acid were obtained. The purity by liquid chromatography was 94.5%.
【００１７】実施例４ ９５％の硫酸１００ｇに１，４−ジアミノ−５，６，
７，８−テトラクロルアントラキノン−２，３−ジニト
リル１０ｇを装入し、１８０℃で３時間加熱攪拌した。
反応液を室温に冷却した後、氷水２００ｇに排出、析出
した固体を濾過、水洗し乾燥して、１，４−ジアミノ−
５，６，７，８−テトラクロルアントラキノン−２−カ
ルボン酸９．０ｇを得た。液体クロマトグラフにより純
度９１％であった。EXAMPLE 4 1,4-Diamino-5,6,100 g in 95 g of 95% sulfuric acid
10 g of 7,8-tetrachloroanthraquinone-2,3-dinitrile was charged and heated and stirred at 180 ° C. for 3 hours.
After the reaction solution was cooled to room temperature, it was discharged into 200 g of ice water, and the precipitated solid was filtered, washed with water and dried to give 1,4-diamino-
9.0 g of 5,6,7,8-tetrachloroanthraquinone-2-carboxylic acid was obtained. The purity was 91% according to liquid chromatography.
【００１８】[0018]
【発明の効果】本発明の方法は、入手容易な原料をもと
に簡便な操作により高収率、高純度でアントラキノン−
２−カルボン酸を得ることができ、工業的にも容易に実
施しうる方法である。According to the method of the present invention, anthraquinone-
This is a method which can obtain 2-carboxylic acid and can be easily carried out industrially.
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 229/74 C07C 227/26 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)Continuation of the front page (58) Field surveyed (Int. Cl. 6 , DB name) C07C 229/74 C07C 227/26 CA (STN) REGISTRY (STN)
Claims (3)
ロゲン原子、水酸基、アミノ基を表す）で示されるアン
トラキノンジニトリルを濃度６０〜１００％の硫酸中、
５０〜２００℃で処理することを特徴とする下記一般式
（II）（化２） 【化２】 （式中、R1、R2、R3およびR4は各々独立に水素原子、ハ
ロゲン原子、水酸基、アミノ基を表す）で示されるアン
トラキノン−２−カルボン酸の製造方法。1. A compound of the general formula (I) (Wherein R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or an amino group) in sulfuric acid having a concentration of 60 to 100%,
The following general formula (II) characterized in that the treatment is carried out at 50 to 200 ° C. (Wherein, R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or an amino group).
使用量が一般式(I）で表されるアントラキノンジニトリ
ルの３〜５０倍量である請求項１記載の製造方法。2. The process according to claim 1, wherein the sulfuric acid concentration is 80 to 95% and the amount of sulfuric acid used is 3 to 50 times the amount of the anthraquinone dinitrile represented by the general formula (I).
項２記載の製造方法。3. The production method according to claim 2, wherein the treatment temperature is 110 to 180 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3107891A JP2931689B2 (en) | 1991-05-14 | 1991-05-14 | Method for producing anthraquinone-2-carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3107891A JP2931689B2 (en) | 1991-05-14 | 1991-05-14 | Method for producing anthraquinone-2-carboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04338368A JPH04338368A (en) | 1992-11-25 |
| JP2931689B2 true JP2931689B2 (en) | 1999-08-09 |
Family
ID=14470696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3107891A Expired - Lifetime JP2931689B2 (en) | 1991-05-14 | 1991-05-14 | Method for producing anthraquinone-2-carboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2931689B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112500717B (en) * | 2020-09-21 | 2022-08-05 | 浙江龙盛染料化工有限公司 | Disperse blue dye composition and dye product thereof |
| CN112048190B (en) * | 2020-09-21 | 2021-10-15 | 浙江龙盛染料化工有限公司 | Disperse blue to black dye composition and dye product thereof |
-
1991
- 1991-05-14 JP JP3107891A patent/JP2931689B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04338368A (en) | 1992-11-25 |
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