JPH0529219B2 - - Google Patents
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- Publication number
- JPH0529219B2 JPH0529219B2 JP61085900A JP8590086A JPH0529219B2 JP H0529219 B2 JPH0529219 B2 JP H0529219B2 JP 61085900 A JP61085900 A JP 61085900A JP 8590086 A JP8590086 A JP 8590086A JP H0529219 B2 JPH0529219 B2 JP H0529219B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- water
- formula
- grams
- dissolved
- 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
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
〔産業上の利用分野〕
本発明は新規なアゾ化合物に関し、この化合物
は種々の医薬活性物質等と共に複合体を形成して
有用な医薬を提供することができる。
〔従来の技術〕
医薬活性物質等と共に容易に複合体を形成する
ことができる本発明の化合物のようなアゾ化合物
は従来知られていない。
〔発明が解決しようとする課題〕
従つて本発明は、医薬活性物質等種々の物質と
容易に結合して複合体を形成することができるア
ゾ化合物を提供しようとするものである。
〔課題を解決するための手段〕
上記の課題は、次の一般式（）：
（式中、
R1は、−CH3，−CO2C2H5，
[Industrial Application Field] The present invention relates to a novel azo compound, which can form a complex with various pharmaceutically active substances to provide useful medicines. [Prior Art] Azo compounds such as the compound of the present invention that can easily form complexes with pharmaceutically active substances and the like have not been known so far. [Problems to be Solved by the Invention] Therefore, the present invention aims to provide an azo compound that can easily bind to various substances such as pharmaceutically active substances to form a complex. [Means for solving the problem] The above problem can be solved by the following general formula (): (In the formula, R 1 is -CH 3 , -CO 2 C 2 H 5 ,
【式】又 は【Formula】Also teeth
【式】であり； R2は、−CH3，−CO2C2H5，[Formula]; R 2 is -CH 3 , -CO 2 C 2 H 5 ,
【式】又 は【Formula】Also teeth
【式】であり；
R3は、−Ｈ又は−CO−NH2であり；
Ｒは、−C2H4OH，−C2H4Cl，−CO−NH−
C2H4Cl，[Formula]; R 3 is -H or -CO-NH 2 ; R is -C 2 H 4 OH, -C 2 H 4 Cl, -CO-NH-
C 2 H 4 Cl,
【式】又は[Formula] or
本発明の化合物は、例えば、次の合成ルートに
より合成することができる。
上記式において、Ｒ，R′，R1，R2及びR3はそ
れぞれ前記の意味を有する。
本発明のアゾ化合物は、他の有用な物質と複合
体を形成させることにより、該他の有用な化合物
の水溶性の増加、消色、消味、消臭等を行うこと
ができる。例えば、1896年にMosetigにより悪性
腫瘍に対して有効であることが報告された濃紫色
のアニリン色素であるメチルバイオレツトは比較
的水に溶けにくいが本発明のアゾ化合物とメチル
バイオレツトとの複合体は水に極めてよく溶解す
る。また、メチルバイオレツトと本発明のアゾ化
合物との複合体を水溶液にした場合、ほとんど無
色の水溶液が得られ、メチルバイオレツトそれ自
体の水溶液が濃い紫色を呈するのと対象的であ
る。同様に、本発明のアゾ化合物を用いて有色性
の味を隠すことができ、従つて患者に不快な感情
を起こさせることなく投与することができる。例
えば、メチルバイオレツトはアニリン臭及び渋味
のある辛さと苦味を有するが本発明のアゾ化合物
と複合体を形成することによりほとんど無味無臭
となる。
また、実施例３に示すごとく、免疫抑制作用及
び抗炎症作用を有するブレドニゾロンは水に溶け
にくく渋味を有するが、本発明のアゾ化合物との
複合体は水に溶けやすく、無味となり、水性溶液
の形で投与することができる。
〔発明の効果〕
以上のごとく、本発明のアゾ化合物は、他の有
用な化合物、例えば医薬活性物質等、と複合体を
形成することができ、それによつて該有用化合物
の水溶性の増加、消色、消味、消臭等を行うこと
ができ、他方本発明のアゾ化合物の毒性は極めて
低い。
次に、本発明の化合物の製造方法を実施例によ
り具体的に説明する。
実施例 １
1.6グラムの５−アミノ−１−ナフトールを50
c.c.のピリジンに溶解し、10℃以下で１分子量のト
リクロロアセチルクロライドを滴下し化合せし
む。次にこれを一夜放置し翌日氷上に注ぐときは
黒い沈渣として化合物が得られる。このものを僅
かに過剰のメチルフオルムアルデヒドと閉管中で
130℃に１−３時間加熱する。
ここに生成した化合物を適量のアルコールに溶
解し別に公知の方法でヂアゾ化した２分子量のエ
チルウレタン水溶液に注加する。つづいて５グラ
ムの酢酸ソーダを水に溶かして、これに加えると
嵩の多い沈渣が出来る。これを数時間又は一夜放
置しておいてから濾過乾燥すると暗黒色の水及び
アルコールに溶けない次式（ａ）で表わされる
化合物の粉末が得られる。
中途に於いて閉管中メチルフオルムアルデヒド
の代りにエチレンイミンを加える。130℃に加熱
し、同一の操作をするときは次式（ｂ）の化合
物が得られる。
上記の工程により得られたFormａの化合物
及びその等量のピオクタニン（メチルヴイオレツ
ト）とを２メトキシエタノールに溶解し、それに
硫酸マグネシウム液を除々に滴下するときは溶液
は粥状になり、ついに固化するに至る。この時点
で複合は完結したものである。ここに生成した化
合物は水及びアルコールに甚だよく溶解し、200
℃に於いて炭化し、次式の構造式を有する。
実施例 ２
1.6グラムの５−アミノ−１−ナフトールとベ
ンゼン５mlを２−クロルエチルエソシアナート５
mlに加え化合せしむるときは直に化合し次式の化
合物が得られる。
ここに生成した化合物を分離し、６グラムのシ
アン酸加里とよく混合し、それに塩酸を撹拌しな
がら滴下する。そして泡立ちがなくなるまで滴下
し、一夜放置しておく。それから反応物を水で処
理して生成物を濾過乾燥する。その化合物の構造
式は次のとおりである。
ここに生成した化合物を150mlのアルコールに
溶解する。これを公知の方法でヂアゾ化した２分
子量のスルフアチトシン液中に注ぐ。これにつづ
いて５グラムの酢酸ソーダを水に溶かして、これ
に加えると嵩の多い沈渣が出来る。これを数時間
又は一夜放置したのち濾過乾燥する。その生成物
は次の構造式を有する。
次にこの生成物の適量の２−メトキシエタノー
ルに溶かしそれに１分子量のピオクタニンを加え
て溶解せしむ。そしてこれに除々に苛性ソーダ液
を滴下するときは、ワイン色にかかる。その時点
で複合反応は終る。ここに生成した化合物を分離
乾燥する。このものは水、アルコールに溶解し、
200℃において炭化分解する。その構造式は次式
のごとくである。
実施例 ３
３グラムの５−アミノ−１−ナフトール、20ml
のヂオキサン、６mlの水、及び６グラムのエチレ
ンオキシードを閉管中に於いて２時間、30℃から
40℃に加熱する。ここに生成した化合物は次式の
構造式を有する。
ここに生成した化合物を公知の方法でヂアゾ化
したスルフアメチルアミン液に注ぐ、そしてつづ
いて10グラムの酢酸ソーダを水に溶かし、これに
加えるときは嵩の多い沈渣が出来る。それを濾過
乾燥する。その構造式は次のとおりである。
ここに生成した化合物をピリジン２mlを加えた
ベンゼン50mlに溶解し、10mlのチオニールクロラ
イドをこれに滴下し化合せしむ。２時間の加熱で
置換反応は終る。ここに生成した化合物は次式の
構造式を有する。
更にここに生成した化合物を適量の２−メトキ
シエタノールに溶解し等量のプレードニゾロンを
加える。それから硫酸銅溶液を除々に滴下すると
きは溶液は粥状になる。この結晶生成が終つたと
き複合反応は終了する。ここに得られた生成物は
水、アルコールに溶けやすく、200℃に於いて炭
化分解する。その構造式は次ごとくである。
実施例 ４
1.6グラムの５−アミノ−１−ナフトールに５
mlのベンゼンと５mlの２−クロロエチルエソシア
ナートを加え化合せしむるときは直ちに化合し、
次のごとき化合物が得られる。
この化合物を分離し、６グラムのシアン酸加里
を加え、よく混合する。それを攪拌しながら塩酸
を滴下し、そして泡立ちがなくなるまで除々に塩
酸を滴下する。このものを一夜放置する。この反
応物を水で処理し、沈澱物を濾過乾燥する。ここ
に生成せられた化合物は次式のごとき構造式を有
す。
ここに生成した化合物を150mlのアルコールに
溶解し、これを２分子量の公知の方法によりヂア
ゾ化したスルフアイソシジン液に加え化合せし
め、つづいて５グラムの酢酸ソーダを水に溶か
し、これに加えると直ちに嵩の多い沈渣が出来
る。これを濾過乾燥する。その化合物の構造式は
次式のごとくである。
以上によつて得られた物質を２−メトキシエタ
ノールに溶かし、これにピオクタニン、ピレドニ
ゾロン、アブシジン酸の等量を加え、これに硫酸
マグネシウム液を除々に滴下するときは粥状にな
り、ついに凝固するに至つた。この時点で複合反
応は終了する。ここに於いて生成した化合物を分
離乾燥にする。このものは水溶性で200℃で分解
炭化する。その構造式は次式のごとくである。
The compound of the present invention can be synthesized, for example, by the following synthetic route. In the above formula, R, R', R 1 , R 2 and R 3 each have the above meaning. By forming a complex with other useful substances, the azo compound of the present invention can increase the water solubility of the other useful compounds, and can erase color, taste, and deodorize the other useful compounds. For example, methyl violet, a deep purple aniline dye reported by Mosetig in 1896 to be effective against malignant tumors, is relatively insoluble in water, but the combination of the azo compound and methyl violet of the present invention The body is extremely soluble in water. Furthermore, when the complex of methyl violet and the azo compound of the present invention is made into an aqueous solution, an almost colorless aqueous solution is obtained, which is in contrast to the deep purple color of an aqueous solution of methyl violet itself. Similarly, the azo compounds of the present invention can be used to mask colored tastes and thus can be administered without causing discomfort to the patient. For example, methyl violet has an aniline odor and an astringent pungent and bitter taste, but by forming a complex with the azo compound of the present invention, it becomes almost tasteless and odorless. Furthermore, as shown in Example 3, brednisolone, which has immunosuppressive and anti-inflammatory effects, is difficult to dissolve in water and has an astringent taste, but the complex with the azo compound of the present invention is easily soluble in water, becomes tasteless, and dissolves in aqueous solution. It can be administered in the form of [Effects of the Invention] As described above, the azo compound of the present invention can form a complex with other useful compounds, such as pharmaceutically active substances, thereby increasing the water solubility of the useful compound, The azo compound of the present invention can be used to remove color, taste, and deodorize, and on the other hand, the toxicity of the azo compound of the present invention is extremely low. Next, the method for producing the compound of the present invention will be specifically explained with reference to Examples. Example 1 1.6 grams of 5-amino-1-naphthol
Dissolve the solution in cc of pyridine, and add 1 molecular weight trichloroacetyl chloride dropwise at 10°C or below to combine. Next, when this is left overnight and poured on ice the next day, the compound is obtained as a black precipitate. This was mixed with a slight excess of methyl formaldehyde in a closed tube.
Heat to 130°C for 1-3 hours. The compound thus produced is dissolved in an appropriate amount of alcohol and poured into an aqueous solution of 2 molecular weight ethyl urethane which has been separately diazotized by a known method. Next, dissolve 5 grams of sodium acetate in water and add it to this to form a bulky precipitate. This is allowed to stand for several hours or overnight and then filtered and dried to obtain a dark black powder of a compound represented by the following formula (a) that is insoluble in water and alcohol. During the process, ethyleneimine is added in place of methyl formaldehyde while the tube is closed. When heated to 130°C and performed the same operation, a compound of the following formula (b) is obtained. When the Forma compound obtained by the above process and its equivalent amount of pioctanine (methyl violet) are dissolved in 2-methoxyethanol and the magnesium sulfate solution is gradually added dropwise thereto, the solution becomes porridge-like and finally It solidifies. At this point, the combination is complete. The compound produced here is highly soluble in water and alcohol, and is highly soluble in water and alcohol.
It carbonizes at ℃ and has the following structural formula. Example 2 1.6 grams of 5-amino-1-naphthol and 5 ml of benzene were mixed with 2-chloroethyl esocyanate 5
When added to ml and combined, it is combined directly to obtain the compound of the following formula. The compound thus formed is separated and mixed well with 6 grams of potassium cyanate, to which hydrochloric acid is added dropwise with stirring. Then, add the drops until the foaming stops and leave it overnight. The reaction is then treated with water and the product is filtered and dried. The structural formula of the compound is as follows. The compound thus produced is dissolved in 150 ml of alcohol. This is poured into a 2-molecular-weight sulfacytosine solution that has been diazotized by a known method. This is followed by 5 grams of sodium acetate dissolved in water and added to this to form a bulky precipitate. This is left for several hours or overnight and then filtered and dried. The product has the following structural formula. Next, this product is dissolved in an appropriate amount of 2-methoxyethanol and 1 molecular weight of pioctanine is added thereto to dissolve it. Then, when the caustic soda solution is gradually added dropwise, the color turns wine-colored. At that point, the complex reaction ends. The compound produced here is separated and dried. This substance dissolves in water and alcohol,
Carbonized and decomposed at 200℃. Its structural formula is as shown below. Example 3 3 grams of 5-amino-1-naphthol, 20 ml
dioxane, 6 ml of water, and 6 grams of ethylene oxide in a closed tube for 2 hours at 30°C.
Heat to 40°C. The compound thus produced has the following structural formula. When the compound thus produced is poured into a solution of sulfamethylamine which has been diazotized in a known manner, and then 10 grams of sodium acetate dissolved in water is added, a bulky precipitate is formed. Filter and dry it. Its structural formula is as follows. The compound thus produced is dissolved in 50 ml of benzene to which 2 ml of pyridine has been added, and 10 ml of thionyl chloride is added dropwise thereto to form a compound. The substitution reaction is completed by heating for 2 hours. The compound thus produced has the following structural formula. Furthermore, the compound thus produced is dissolved in an appropriate amount of 2-methoxyethanol, and an equal amount of prednisolone is added. When the copper sulfate solution is then added dropwise, the solution becomes porridge-like. When this crystal formation ends, the complex reaction ends. The product obtained here is easily soluble in water and alcohol, and is carbonized and decomposed at 200℃. Its structural formula is as follows. Example 4 1.6 grams of 5-amino-1-naphthol
ml of benzene and 5 ml of 2-chloroethyl esocyanate are added and combined immediately.
The following compounds are obtained. Separate this compound, add 6 grams of potassium cyanate and mix well. Hydrochloric acid is added dropwise to the mixture while stirring, and the hydrochloric acid is gradually added dropwise until the bubbling stops. Leave this thing overnight. The reaction is treated with water and the precipitate is filtered and dried. The compound thus produced has a structural formula as shown below. The compound thus produced is dissolved in 150 ml of alcohol, and this is added to a diazotized sulfisosidine solution of 2 molecular weight by a known method to form a compound, and then 5 grams of sodium acetate is dissolved in water and added to this. A bulky sediment is formed immediately. This is filtered and dried. The structural formula of the compound is as shown below. The substance obtained above is dissolved in 2-methoxyethanol, equal amounts of pyoctanine, pyrednisolone, and abscisic acid are added thereto, and when the magnesium sulfate solution is gradually added dropwise, it becomes porridge-like and finally coagulates. It came to this. At this point, the combined reaction is complete. The compound produced here is separated and dried. This material is water-soluble and decomposes and carbonizes at 200℃. Its structural formula is as shown below.
１ 一般式
〔式中R1は置換基として低級アルキル基、ハ
ロゲン原子、カルボキシル基、低級アルコキシカ
ルボニル基、ヒドロキシ低級アルキル基、カルボ
キシ低級アルキル基、低級アルコキシカルボニル
低級アルキル基、基
1 General formula [In the formula, R 1 is a substituent such as a lower alkyl group, a halogen atom, a carboxyl group, a lower alkoxycarbonyl group, a hydroxy lower alkyl group, a carboxy lower alkyl group, a lower alkoxycarbonyl lower alkyl group, or a group
Claims (1)
C2H4Cl，【式】又は 【式】であり；そして R′は−Ｈ，−C2H4OH，−C2H4Cl、又は−CO−
NH−C2H4Clである） で表わされる化合物、及びその塩。is [Formula]; R 3 is -H or -CO-NH 2 ; R is -C 2 H 4 OH, -C 2 H 4 Cl, -CO-NH-
C 2 H 4 Cl, [formula] or [formula]; and R' is -H, -C 2 H 4 OH, -C 2 H 4 Cl, or -CO-
NH-C 2 H 4 Cl) and salts thereof.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61085900A JPS62242658A (en) | 1986-04-16 | 1986-04-16 | Production of azo complex |
| JP3100893A JPH0776206B2 (en) | 1986-04-16 | 1991-05-02 | Azo compound complex |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61085900A JPS62242658A (en) | 1986-04-16 | 1986-04-16 | Production of azo complex |
| JP3100893A JPH0776206B2 (en) | 1986-04-16 | 1991-05-02 | Azo compound complex |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3100893A Division JPH0776206B2 (en) | 1986-04-16 | 1991-05-02 | Azo compound complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62242658A JPS62242658A (en) | 1987-10-23 |
| JPH0529219B2 true JPH0529219B2 (en) | 1993-04-28 |
Family
ID=26426907
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61085900A Granted JPS62242658A (en) | 1986-04-16 | 1986-04-16 | Production of azo complex |
| JP3100893A Expired - Lifetime JPH0776206B2 (en) | 1986-04-16 | 1991-05-02 | Azo compound complex |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3100893A Expired - Lifetime JPH0776206B2 (en) | 1986-04-16 | 1991-05-02 | Azo compound complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JPS62242658A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1284780B1 (en) * | 2000-05-10 | 2008-05-07 | Ash Access Technology, Inc. | A catheter lock solution including a photo-oxidant |
| RU2354384C1 (en) * | 2007-12-28 | 2009-05-10 | Михаил Владимирович Кутушов | Application of organic dyes as means for treatment of oncological diseases |
| CN104327546A (en) * | 2014-10-16 | 2015-02-04 | 天津德凯化工股份有限公司 | Dye reactive brown and preparation method thereof |
-
1986
- 1986-04-16 JP JP61085900A patent/JPS62242658A/en active Granted
-
1991
- 1991-05-02 JP JP3100893A patent/JPH0776206B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0680623A (en) | 1994-03-22 |
| JPH0776206B2 (en) | 1995-08-16 |
| JPS62242658A (en) | 1987-10-23 |
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