JPS5817769B2 - Azo compounds and their manufacturing method - Google Patents
Azo compounds and their manufacturing methodInfo
- Publication number
- JPS5817769B2 JPS5817769B2 JP54097058A JP9705879A JPS5817769B2 JP S5817769 B2 JPS5817769 B2 JP S5817769B2 JP 54097058 A JP54097058 A JP 54097058A JP 9705879 A JP9705879 A JP 9705879A JP S5817769 B2 JPS5817769 B2 JP S5817769B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- azo compound
- added
- water
- stirred
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/88—Nitrogen atoms, e.g. allantoin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P7/00—Drugs for disorders of the blood or the extracellular fluid
- A61P7/10—Antioedematous agents; Diuretics
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P9/00—Drugs for disorders of the cardiovascular system
- A61P9/02—Non-specific cardiovascular stimulants, e.g. drugs for syncope, antihypotensives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P9/00—Drugs for disorders of the cardiovascular system
- A61P9/04—Inotropic agents, i.e. stimulants of cardiac contraction; Drugs for heart failure
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3647—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Cardiology (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Heart & Thoracic Surgery (AREA)
- Veterinary Medicine (AREA)
- Diabetes (AREA)
- Hematology (AREA)
- Hospice & Palliative Care (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
【発明の詳細な説明】
本発明は新規アゾ化合物及びその製造法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel azo compound and a method for producing the same.
即ち、本発明は分散染料、塩基性染料の前駆体および医
薬用として、特に医薬用として有用な、特定のアゾ化合
物を創製し、かつその有利な製造法を提供するものであ
る。That is, the present invention creates a specific azo compound useful for disperse dyes, basic dye precursors, and medicines, particularly for medicines, and provides an advantageous method for producing the same.
本発明の式１： （式中、Ｘはハロゲン原子を表わす。Formula 1 of the invention: (In the formula, X represents a halogen atom.
）で表わされるアゾ化合物は、水と鉱酸との存在下に、
４−ハロゲノ−２−アミノアニソールをジアゾ化し、と
のジアゾ成分に対し、５〜１０倍モルのイミダゾールを
カップリングさせることにより得られる。) in the presence of water and mineral acid,
It is obtained by diazotizing 4-halogeno-2-aminoanisole and coupling imidazole in an amount of 5 to 10 times the mole of the diazo component.
この場合、イミダゾールの使用モル数を１〜１．５倍と
したときには、下記の式：
で表わされる異性体の副生を阻止することができず、純
品を得ることが困難である。In this case, when the number of moles of imidazole used is increased from 1 to 1.5 times, it is impossible to prevent the by-product of the isomer represented by the following formula: and it is difficult to obtain a pure product.
本発明の方法によれば、このような問題点を解決し、純
品を高収率で得ることができる。According to the method of the present invention, such problems can be solved and pure products can be obtained in high yield.
次に実施例をあげて本発明を説明する。Next, the present invention will be explained with reference to Examples.
尚文中の部及び係は、重量部及び重量部を意味する。The terms ``part'' and ``kita'' in Naobun mean parts by weight.
実施例 １
５０部の水に４−クロロ−２−アミノアニソール５．１
部と３５％塩酸７．６部とを加え、０〜５℃で亜硝酸ナ
トリウム２．２部を含む水１５部を加え１時間攪拌しジ
アゾ化した。Example 1 5.1 4-chloro-2-aminoanisole in 50 parts of water
1 part and 7.6 parts of 35% hydrochloric acid were added thereto, and 15 parts of water containing 2.2 parts of sodium nitrite were added at 0 to 5°C, followed by stirring for 1 hour to diazotize.
次に１５０部の水にイミダゾール２０．４部、水酸化ナ
トリウム１．７部及び酢酸す） ＩＪウム２．５部を加
え、かきまぜて溶解後、０〜５°Ｃで前記アアゾニウム
塩溶液を加え１時間攪拌してカップリングした。Next, add 20.4 parts of imidazole, 1.7 parts of sodium hydroxide, and 2.5 parts of acetic acid to 150 parts of water, stir to dissolve, and then add the azonium salt solution at 0 to 5°C. The mixture was stirred for 1 hour and coupled.
次いで析出した黄橙色のアゾ化合物をｆ別、水洗し、６
０°Ｃで乾燥して粗製の前言試１で表わされる化合物７
．６部を得だ。Next, the precipitated yellow-orange azo compound was separated by f and washed with water.
Dry at 0°C to obtain the crude compound 7 represented by Preparation Test 1
．． I got 6 copies.
上記粗製のアゾ化合物７部をｎ−プロピルアルコールか
ら再結晶して黄橙色のアゾ化合物４．９部を得た。7 parts of the above crude azo compound were recrystallized from n-propyl alcohol to obtain 4.9 parts of a yellow-orange azo compound.
このものの融点を日本薬局方に定められた方法で測定す
ると２０５℃（分解）であった。The melting point of this product was determined to be 205°C (decomposition) using the method specified in the Japanese Pharmacopoeia.
このアゾ化合物はアルコールでλｍａｘ ３８４ｍμを
示し、元素分析値は下記の通りであった。This azo compound showed a λmax of 384 mμ in alcohol, and the elemental analysis values were as follows.
ＣＨＮ Ｃ７
計算値（’＄＞ ５０．７５ ３．８３ ２３．６８
１４．９８実測値（係） ６．０，５５ ４．０１
２４゜１０ １５．０５実施例 ２
５０部の水に４−フルオロ−２−アミノアニソール２．
８２部と３５係塩酸５．２部とを加え、０〜・５°Ｃで
亜硝酸ナトリウム１．３８部を含む水１０部を加えて１
時間攪拌しジアゾ化した。CHN C7 Calculated value ('$> 50.75 3.83 23.68
14.98 Actual value (related) 6.0,55 4.01
24°10 15.05 Example 2 4-fluoro-2-aminoanisole in 50 parts of water2.
82 parts and 5.2 parts of 35% hydrochloric acid were added, and at 0 to 5°C, 10 parts of water containing 1.38 parts of sodium nitrite was added.
The mixture was stirred for an hour and diazotized.
次に１００部の水にイミダゾール１３．６部、水酸化ナ
トリウム１．２部及び酢酸ナトリウム１．６４部を加え
、かきまぜて溶解後、０〜５℃で前記ジアゾニウム塩・
溶液を加え１時間攪拌してカップリングした。Next, 13.6 parts of imidazole, 1.2 parts of sodium hydroxide, and 1.64 parts of sodium acetate were added to 100 parts of water, and after stirring and dissolving, the diazonium salt.
The solution was added and stirred for 1 hour for coupling.
次いで析出した黄橙色のアゾ化合物を沢別、水洗し６０
’Ｃで乾燥して粗製のアゾ化合物４．３部を得へ上記粗
製のアゾ化合物４部をｎ−ブチルアルコールから再結晶
して黄橙色のアゾ化合物２．９部を“得た。Next, the precipitated yellow-orange azo compound was separated and washed with water for 60 minutes.
4 parts of the crude azo compound were recrystallized from n-butyl alcohol to obtain 2.9 parts of a yellow-orange azo compound.
このものの融点を日本薬局方に定められた方法で測定す
ると２０４°Ｃ（分解）であった。The melting point of this product was measured by the method specified in the Japanese Pharmacopoeia and was 204°C (decomposition).
このアゾ化合物はアルコール中で、λｍａｘ３８８ｍμ
を示し、またその元素分析値は下記の通りであつだ。This azo compound has a λmax of 388 mμ in alcohol.
The elemental analysis values are as follows.
ＣＨＮ Ｆ
計算値（係） ５４，５５ ４．０９ ２５．４５
８．６４実測値（倦） ５４．６０ ４．１２ ２５
．５８ ８．６９実施例 ３
６０部の水に４−プロモー２−アミノアニソール４０４
部と３５％塩酸５．２部とを加え、０〜５℃で亜硝酸ナ
トリウム１．３８部を含む水１０部を加え１時間攪拌し
てジアゾ化した。CHN F Calculated value (related) 54,55 4.09 25.45
8.64 Actual value (〦) 54.60 4.12 25
．． 58 8.69 Example 3 4-promo-2-aminoanisole 404 in 60 parts of water
1 part and 5.2 parts of 35% hydrochloric acid were added thereto, and 10 parts of water containing 1.38 parts of sodium nitrite were added at 0 to 5[deg.] C., and the mixture was stirred for 1 hour to effect diazotization.
次に８０部の水にイミダゾール９．５３部、水酸化ナト
リウム１．２部及び酢酸ナトリウム１．６４部を加え、
かきまぜて溶解後、０〜５°Ｃで前記ジアゾニウム塩溶
液を加え１時間攪拌してカップリングした。Next, 9.53 parts of imidazole, 1.2 parts of sodium hydroxide and 1.64 parts of sodium acetate were added to 80 parts of water.
After stirring and dissolving, the diazonium salt solution was added at 0 to 5°C, and the mixture was stirred for 1 hour for coupling.
次いで析出した黄橙色のアゾ化合物をｒ別、水洗し、６
０℃で乾燥して粗製のアゾ化合物５．１部を得九上記粗
製のアゾ化合物４部を酢酸エチルから再結晶して黄橙色
のアゾ化合物３．２部を得だ。Next, the precipitated yellow-orange azo compound was separated and washed with water.
It was dried at 0° C. to obtain 5.1 parts of a crude azo compound. 4 parts of the above crude azo compound were recrystallized from ethyl acetate to obtain 3.2 parts of a yellow-orange azo compound.
このものの融点を日本薬局方に定められた方法で測定す
ると２２４．５°Ｃ（分解）であった。The melting point of this product was determined to be 224.5°C (decomposition) using the method specified in the Japanese Pharmacopoeia.
このアゾ化合物はアルコール中でλｍａｘ３８７ｍμを
示し、またその元素分析値は下記のとうりであった。This azo compound exhibited a λmax of 387 mμ in alcohol, and its elemental analysis values were as follows.
ＣＨＮ Ｂｒ
計算値＄） ４２，７０ ３．２０ １９．９３ ２
８．４４実測値鍾） ４２．７１ ３．２７ １９．
９０ ２８．３９実施例 ４
７０部の水に４−ヨード−２−アミノアニソール４．９
８部と３５係塩酸５，２部とを加オ、０〜５℃で亜硝酸
ナトリウム１．３８部を含む水１０部を加え、１時間攪
拌してジアゾ化した。CHN Br Calculated value $) 42,70 3.20 19.93 2
8.44 actual measurement value) 42.71 3.27 19.
90 28.39 Example 4 4-iodo-2-aminoanisole in 70 parts of water 4.9
8 parts and 5.2 parts of 35% hydrochloric acid were added, 10 parts of water containing 1.38 parts of sodium nitrite was added at 0 to 5°C, and the mixture was stirred for 1 hour to diazotize.
次に８０部の水にイミダゾール１０．８９部、水酸化ナ
トリウム１．２部及び酢酸ナトリウム）、６４部を加え
かきまぜて溶解後、０〜５°Ｃで前記ジアゾニウム塩溶
液を加え１時間攪拌してカップリングした。Next, 10.89 parts of imidazole, 1.2 parts of sodium hydroxide, and 64 parts of sodium acetate were added to 80 parts of water and stirred to dissolve.Then, the diazonium salt solution was added at 0 to 5°C and stirred for 1 hour. I coupled it.
次いで、析出した黄橙色のアゾ化合物をｒ別、水洗し、
６０℃で乾燥して粗製のアゾ化合物５．９部を得九上記
粗製のアゾ化合物４．５部をシリカゲルカラムクロマト
グラフィーにより精製して結晶化し、黄橙色のアゾ化合
物３．５部を得た。Next, the precipitated yellow-orange azo compound was separated and washed with water.
4.5 parts of the above crude azo compound was purified and crystallized by silica gel column chromatography to obtain 3.5 parts of a yellow-orange azo compound. .
このものの融点を日本薬局方に定められた方法で測定す
ると′２１７．５°Ｃ（分解）であった。The melting point of this product was determined by the method specified in the Japanese Pharmacopoeia and was 217.5°C (decomposition).
このアゾ化合物はメタノール中でλｍａｘ ３８５ ｍ
μを示し、まだ元素分析値は下記の通りであった。This azo compound has a λmax of 385 m in methanol.
μ, and the elemental analysis values were as follows.
ＨＮＩ
計算値（動 ３６．５９ ２．７４ １７．０７ ３８
．６９ＣＨＮＩ
実測値（（５） ３６．６１ ２．７０ １７．０９
３８．６１本発明の化合物は、優れた利尿作用を持ち、
更に血圧上昇作用、強心作甲等を有する。HNI Calculated value (Dynamic 36.59 2.74 17.07 38
．． 69CHNI Actual value ((5) 36.61 2.70 17.09
38.61 The compounds of the present invention have excellent diuretic effects,
It also has blood pressure increasing effects and cardiotonic effects.
その利尿作用について、実施例１及び実施例２によって
得られた化合物に即して述べると、ラットについての試
験によれば、対照薬剤であるフロセマイドの約１０倍の
利尿作用を示しだ。Regarding its diuretic effect, referring to the compounds obtained in Examples 1 and 2, a test on rats showed that it had a diuretic effect about 10 times that of furosemide, a control drug.
またその急性毒性は、通常の使用量では全く問題がない
ことも確認している。It has also been confirmed that there is no problem with its acute toxicity at normal doses.
Claims (1)
ウム塩１モルに対して、５ないし１０倍モルのイミダゾ
ールを使用してカップリングすることを特徴とする式１
： （式中、Ｘはハロゲン原子を表わす。 ）で表わされるアゾ化合物の製造法。[Scope of Claims] An azone compound represented by the following formula 1: (wherein, X represents a halogen atom).・Formula 1 characterized in that coupling is carried out using 5 to 10 times the mole of imidazole per mole of the diazonium salt of 2,4-halogeno-2-aminoanisole.
A method for producing an azo compound represented by: (wherein, X represents a halogen atom).
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54097058A JPS5817769B2 (en) | 1979-07-30 | 1979-07-30 | Azo compounds and their manufacturing method |
| GB8024325A GB2060671B (en) | 1979-07-30 | 1980-07-24 | Azo compounds |
| FR8016790A FR2462460B1 (en) | 1979-07-30 | 1980-07-30 | NOVEL AZO COMPOUNDS AND PROCESS FOR THEIR PREPARATION |
| DE3028928A DE3028928C2 (en) | 1979-07-30 | 1980-07-30 | New azo compounds and processes for their preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54097058A JPS5817769B2 (en) | 1979-07-30 | 1979-07-30 | Azo compounds and their manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5620060A JPS5620060A (en) | 1981-02-25 |
| JPS5817769B2 true JPS5817769B2 (en) | 1983-04-09 |
Family
ID=14182046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP54097058A Expired JPS5817769B2 (en) | 1979-07-30 | 1979-07-30 | Azo compounds and their manufacturing method |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS5817769B2 (en) |
| DE (1) | DE3028928C2 (en) |
| FR (1) | FR2462460B1 (en) |
| GB (1) | GB2060671B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2864075B2 (en) * | 1991-12-04 | 1999-03-03 | 富士写真フイルム株式会社 | Imidazole azo dye and thermal transfer dye-providing material containing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4079130A (en) * | 1976-12-27 | 1978-03-14 | The Dow Chemical Company | Antidepressant phenylazoimidazoles |
| US4067973A (en) * | 1976-12-27 | 1978-01-10 | The Dow Chemical Company | 2-((2-chlorophenyl)azo)imidazoles and their use as an anthelmintic |
-
1979
- 1979-07-30 JP JP54097058A patent/JPS5817769B2/en not_active Expired
-
1980
- 1980-07-24 GB GB8024325A patent/GB2060671B/en not_active Expired
- 1980-07-30 FR FR8016790A patent/FR2462460B1/en not_active Expired
- 1980-07-30 DE DE3028928A patent/DE3028928C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5620060A (en) | 1981-02-25 |
| FR2462460B1 (en) | 1986-11-28 |
| FR2462460A1 (en) | 1981-02-13 |
| GB2060671A (en) | 1981-05-07 |
| GB2060671B (en) | 1983-05-25 |
| DE3028928C2 (en) | 1984-10-31 |
| DE3028928A1 (en) | 1981-02-26 |
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