JP2000248188A - Manufacture of azo compound - Google Patents
Manufacture of azo compoundInfo
- Publication number
- JP2000248188A JP2000248188A JP11056213A JP5621399A JP2000248188A JP 2000248188 A JP2000248188 A JP 2000248188A JP 11056213 A JP11056213 A JP 11056213A JP 5621399 A JP5621399 A JP 5621399A JP 2000248188 A JP2000248188 A JP 2000248188A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- compound represented
- group
- 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.)
- Pending
Links
- -1 azo compound Chemical class 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 12
- 239000013078 crystal Substances 0.000 abstract description 8
- 125000005842 heteroatom Chemical group 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001786 isothiazolyl group Chemical group 0.000 abstract description 2
- 125000003226 pyrazolyl group Chemical group 0.000 abstract description 2
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001544 thienyl group Chemical group 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- 125000004442 acylamino group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 150000008049 diazo compounds Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000004421 aryl sulphonamide group Chemical group 0.000 description 1
- 238000006149 azo coupling reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical compound CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C09B41/00—Special methods of performing the coupling reaction
- C09B41/006—Special methods of performing the coupling reaction characterised by process features
- C09B41/009—Diazotising and coupling in one step
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ヘテロ環基をジア
ゾ成分に有するアゾ化合物の製造方法に関する。更に詳
しくは拡散転写法カラー写真に用いる色素放出化合物の
合成中間体として有用なアゾ化合物の製造方法に関す
る。TECHNICAL FIELD The present invention relates to a method for producing an azo compound having a heterocyclic group in a diazo component. More specifically, the present invention relates to a method for producing an azo compound useful as a synthetic intermediate of a dye-releasing compound used in a color transfer method by a diffusion transfer method.
【０００２】[0002]
【従来の技術】一般的にジアゾカップリング反応は、条
件によっては副生物が多くなり、収率が低下することは
よく知られているところである。また、芳香族オキシ化
合物をヘテロ環基を有するジアゾ化合物とカップリング
反応させる場合は、ジアゾニウム塩が不安定で目的物の
反応生成率が低く収率が低下するという問題があった。2. Description of the Related Art It is well known that a diazo coupling reaction generally has an increase in by-products depending on conditions and a decrease in yield. In addition, when an aromatic oxy compound is subjected to a coupling reaction with a diazo compound having a heterocyclic group, there is a problem that the diazonium salt is unstable, the reaction generation rate of the target product is low, and the yield is reduced.
【０００３】[0003]
【発明が解決しようとする課題】したがって、本発明の
目的は収率良いアゾ化合物の製造方法を提供することに
ある。さらに、本発明の他の目的は温和な条件でヘテロ
環基を有するアゾ化合物を収率良く製造しうる方法を提
供することにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing an azo compound with a high yield. Still another object of the present invention is to provide a method capable of producing an azo compound having a heterocyclic group with good yield under mild conditions.
【０００４】[0004]
【課題を解決するための手段】本発明者らはヘテロ環ア
ミノ化合物からアゾ化合物を収率良く製造しうる方法に
ついて鋭意研究を重ねた結果、ジアゾ化反応の際に、カ
ップリング成分の芳香族オキシ化合物を存在させること
により目的の反応が効率的に進行し、副生物の生成を抑
制されることを見い出し、この知見に基づき本発明をな
すに至った。すなわち本発明は、下記一般式（１）で表
される化合物の存在下で、一般式（２）で表されるヘテ
ロ環化合物をジアゾ化し、反応させることを特徴とす
る、一般式（３）で表されるアゾ化合物の製造方法、 一般式（１） ＨＯ−Ｘ 一般式（２） Ｈ２Ｎ−Ｙ 一般式（３） ＨＯ−Ｘ−Ｎ＝Ｎ−Ｙ （式中、Ｘはアリール基を、Ｙはへテロ環を有する残基
を示す）を提供するものである。Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a method capable of producing an azo compound from a heterocyclic amino compound in good yield. As a result, the aromatic component of the coupling component was found to be present during the diazotization reaction. It has been found that the objective reaction proceeds efficiently by the presence of the oxy compound, and the production of by-products is suppressed, and the present invention has been accomplished based on this finding. That is, the present invention is characterized in that a heterocyclic compound represented by the general formula (2) is diazotized and reacted in the presence of a compound represented by the following general formula (1), method for producing in represented by azo compounds, the general formula (1) HO-X formula (2) H 2 N-Y formula (3) HO-X-N = N-Y ( wherein, X is an aryl group And Y represents a residue having a hetero ring).
【０００５】[0005]
【発明の実施の形態】本発明に用いられる一般式（１）
で表される化合物中において、Ｘはアリール基を表し、
単環であっても縮合環であっても良く、無置換であって
も置換基を有していても良い。好ましくは置換基を有し
ていても良い炭素数３５以下、より好ましくは炭素数２
０以下のフェニル基、ナフチル基を表し、更に好ましく
は置換基としてアシルアミノ基、カルバモイル基、スル
ファモイル基、スルホニル基を有するフェニル基、ナフ
チル基を表す。一般式（２）で表される化合物におい
て、Ｙはヘテロ環を有する残基を表し、ヘテロ環内にヘ
テロ原子（窒素原子、イオウ原子、酸素原子等）を持つ
ものであり、飽和環であっても、不飽和環であっても良
く、単環であっても縮合環であっても良く、無置換であ
っても置換基を有していても良い。このヘテロ環は芳香
性であってもよい。好ましくは置換基を有していても良
い炭素数２０以下、より好ましくは炭素数１０以下の芳
香族ヘテロ環基を表す。好ましくは、一般式（２）で表
わされる化合物中Ｙにおいてヘテロ環は、アミノ基と直
接結合していることが好ましいが、これに限定されな
い。DESCRIPTION OF THE PREFERRED EMBODIMENTS The general formula (1) used in the present invention
In the compound represented by X represents an aryl group,
It may be a single ring or a condensed ring, and may be unsubstituted or have a substituent. Preferably it has 35 or less carbon atoms which may have a substituent, more preferably 2 carbon atoms.
It represents a phenyl group or naphthyl group of 0 or less, more preferably a phenyl group having an acylamino group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, or a naphthyl group as a substituent. In the compound represented by the general formula (2), Y represents a residue having a hetero ring, which has a hetero atom (nitrogen atom, sulfur atom, oxygen atom, etc.) in the hetero ring, and is a saturated ring. Or an unsaturated ring, a single ring or a condensed ring, and may be unsubstituted or have a substituent. This heterocycle may be aromatic. It preferably represents an aromatic heterocyclic group having 20 or less carbon atoms, more preferably 10 or less carbon atoms, which may have a substituent. Preferably, the hetero ring in Y in the compound represented by the general formula (2) is preferably directly bonded to an amino group, but is not limited thereto.
【０００６】次に、本発明で用いられる一般式（１）及
び（２）で表される化合物を更に詳しく述べる。まず、
一般式（１）で表される化合物について述べると、下記
式（Ａ）及び（Ｂ）で表される化合物が好ましい。Next, the compounds represented by formulas (1) and (2) used in the present invention will be described in more detail. First,
As for the compound represented by the general formula (1), compounds represented by the following formulas (A) and (B) are preferable.
【０００７】[0007]
【化１】 Embedded image
【０００８】式（Ａ）、（Ｂ）においてＲ１〜Ｒ
１０は、それぞれ水素原子又は置換可能な置換基を表
す。Ｒ１〜Ｒ１０として好ましくはアシル基、アシルオ
キシ基、アシルアミノ基、脂肪族オキシカルボニル基、
アリールオキシカルボニル基、スルファモイル基、脂肪
族スルホンアミド基、アリールスルホンアミド基、カル
バモイル基、ハロゲン原子又は水素原子である。本発明
に用いられる一般式（１）で表される化合物のうち、更
に好ましい化合物としては、下記式（Ｃ）〜（Ｆ）で表
される化合物が挙げられる。In the formulas (A) and (B), R 1 to R
10 represents a hydrogen atom or a substitutable substituent. R 1 to R 10 are preferably an acyl group, an acyloxy group, an acylamino group, an aliphatic oxycarbonyl group,
It is an aryloxycarbonyl group, a sulfamoyl group, an aliphatic sulfonamide group, an arylsulfonamide group, a carbamoyl group, a halogen atom or a hydrogen atom. Among the compounds represented by formula (1) used in the present invention, more preferred compounds include compounds represented by the following formulas (C) to (F).
【０００９】[0009]
【化２】 Embedded image
【００１０】式（Ｃ）〜（Ｆ）においてＲ４、Ｒ７及び
Ｒ２１〜Ｒ２６は、それぞれ水素原子又は置換可能な置
換基を表す。Ｒ４及びＲ７の好ましい基は式（Ａ）、
（Ｂ）について述べたものと同様である。Ｒ２１〜Ｒ
２６として好ましくは脂肪族基、アリール基又は水素原
子である。これらの中で更に好ましくは、式（Ｃ）、
（Ｄ）及び（Ｅ）で表される化合物であり、式（Ｃ）、
（Ｄ）で表される化合物が最も好ましい。次に本発明に
用いられる一般式（１）で表される化合物の具体例を示
す。In the formulas (C) to (F), R 4 , R 7 and R 21 to R 26 each represent a hydrogen atom or a substitutable substituent. Preferred groups for R 4 and R 7 are those of formula (A):
This is the same as that described for (B). R 21 to R
26 is preferably an aliphatic group, an aryl group or a hydrogen atom. Among these, more preferably, formula (C),
Compounds represented by (D) and (E), wherein
The compound represented by (D) is most preferred. Next, specific examples of the compound represented by Formula (1) used in the present invention are shown.
【００１１】[0011]
【化３】 Embedded image
【００１２】次に本発明に用いられる一般式（２）で表
される化合物におけるＹについて述べる。Ｙとしては芳
香族ヘテロ環が挙げられ、例えばピラゾリル、イソチア
ゾリル、ベンゾイソチアゾリル、チアゾリン、チオフェ
ニル、インダゾリニル等が好ましい。本発明では一般式
（２）で表される化合物のうち、更に好ましい化合物と
しては、次に示す式（Ｇ）〜（Ｉ）で表される化合物で
ある。Next, Y in the compound represented by formula (2) used in the present invention will be described. Examples of Y include an aromatic heterocyclic ring, such as pyrazolyl, isothiazolyl, benzoisothiazolyl, thiazoline, thiophenyl, and indazolinyl. In the present invention, among the compounds represented by the general formula (2), more preferred compounds are the compounds represented by the following formulas (G) to (I).
【００１３】[0013]
【化４】 Embedded image
【００１４】一般式（Ｇ）〜（Ｉ）においてＲ３１〜Ｒ
３９は、それぞれ水素原子又は置換可能な置換基を示
す。Ｒ３１〜Ｒ３９として好ましくは脂肪族、アリール
基、シアノ基、ニトロ基、スルホ基、脂肪族スルホニル
基、ハロゲン原子又は水素原子である。これらの中で更
に好ましくは、式（Ｇ）及び（Ｉ）で表される化合物で
ある。次に本発明に用いられる一般式（２）で表される
化合物の具体例を示す。In the general formulas (G) to (I), R 31 to R
39 represents a hydrogen atom or a substitutable substituent. R 31 to R 39 are preferably an aliphatic group, an aryl group, a cyano group, a nitro group, a sulfo group, an aliphatic sulfonyl group, a halogen atom or a hydrogen atom. Of these, the compounds represented by formulas (G) and (I) are more preferred. Next, specific examples of the compound represented by formula (2) used in the present invention are shown.
【００１５】[0015]
【化５】 Embedded image
【００１６】次に本発明により製造される一般式（３）
で表されるアゾ化合物の具体例を示すが、本発明はこれ
に限定されるものではない。Next, the general formula (3) produced by the present invention
Specific examples of the azo compound represented by are shown below, but the present invention is not limited thereto.
【００１７】[0017]
【化６】 Embedded image
【００１８】[0018]
【化７】 Embedded image
【００１９】[0019]
【化８】 Embedded image
【００２０】本発明においては、一般式（２）の化合物
から生成するジアゾ化合物と反応させる一般式（１）の
芳香族オキシ化合物の存在下で一般式（２）の化合物の
ジアゾ化を行う。本発明の製造方法を実施するに当り、
一般式（２）の化合物を溶剤に溶解もしくは懸濁し、所
定温度範囲で一般式（１）の化合物の溶液を投入し、混
合溶液の温度が所定温度範囲を越えないように調節して
ジアゾ化剤を滴下することが好ましい。本発明における
反応溶剤としては、例えば、水、酢酸、メタノール、ア
セトニトリル、燐酸が挙げられるが、好ましくは燐酸で
あり、燐酸の使用量は一般式（１）で表される化合物及
び一般式（２）で表される化合物の合計１グラム当り、
特に限定しないが、通常１〜１００ｍｌ用いられ、好ま
しくは１０〜３０ｍｌ用いられる。In the present invention, the compound of the general formula (2) is diazotized in the presence of an aromatic oxy compound of the general formula (1) to be reacted with a diazo compound formed from the compound of the general formula (2). In carrying out the production method of the present invention,
The compound of the general formula (2) is dissolved or suspended in a solvent, a solution of the compound of the general formula (1) is charged in a predetermined temperature range, and the temperature of the mixed solution is adjusted so that the temperature does not exceed the predetermined temperature range. It is preferable to drop the agent. The reaction solvent in the present invention includes, for example, water, acetic acid, methanol, acetonitrile and phosphoric acid, and is preferably phosphoric acid. Per gram of the compound represented by
Although not particularly limited, 1 to 100 ml is usually used, preferably 10 to 30 ml.
【００２１】ジアゾ化剤としては亜硝酸塩、亜硝酸アル
キル等が挙げられるが、好ましくは亜硝酸アルキルであ
り、炭素数５以下のアルキル基を有する亜硝酸アルキル
がより好ましい。具体的には例えば亜硝酸ソーダ、亜硝
酸カリ、亜硝酸イソアミル、亜硝酸イソペンチル、亜硝
酸ブチル、亜硝酸ｔ−ブチル、亜硝酸３−メチルブチル
等が挙げられ、更に好ましくは亜硝酸イソアミル、亜硝
酸ブチルであり、一般式（１）で表される化合物に対し
て、特に限定しないが、通常１当量〜５当量用いられ、
好ましくは１当量〜２当量用いられる。一般式（２）で
表される化合物は一般式（１）で表される化合物に対し
１当量〜２当量用いられ、好ましくは１当量〜１．５当
量用いられる。反応温度は通常−１０℃〜４０℃が用い
られるが、−５℃〜２０℃で反応させるのが好ましい。
反応終了後は、特に限定しないが、通常、反応液を食塩
水、アルコール等に注ぎ、析出した結晶を濾取する。必
要であれば食塩水等で洗浄することもできる。Examples of the diazotizing agent include nitrite, alkyl nitrite and the like, preferably alkyl nitrite, and more preferably alkyl nitrite having an alkyl group having 5 or less carbon atoms. Specific examples include sodium nitrite, potassium nitrite, isoamyl nitrite, isopentyl nitrite, butyl nitrite, t-butyl nitrite, 3-methylbutyl nitrite, etc., and more preferably isoamyl nitrite, nitrite Butyl, and is not particularly limited with respect to the compound represented by the general formula (1), but is usually used in an amount of 1 equivalent to 5 equivalents,
Preferably, 1 to 2 equivalents are used. The compound represented by the general formula (2) is used in an amount of 1 equivalent to 2 equivalents, preferably 1 equivalent to 1.5 equivalents, relative to the compound represented by the general formula (1). The reaction temperature is usually −10 ° C. to 40 ° C., but the reaction is preferably performed at −5 ° C. to 20 ° C.
After completion of the reaction, the reaction solution is usually, but not particularly limited to, poured into a saline solution, alcohol, or the like, and the precipitated crystals are collected by filtration. If necessary, it can be washed with a saline solution or the like.
【００２２】[0022]
【実施例】以下に実施例をもって本発明を説明するが、
これによって本発明が限定されるものではない。 実施例１ 下記スキーム１に従う化合物（ｃ）の製造法を述べる。The present invention will be described below with reference to examples.
This does not limit the present invention. Example 1 A method for producing a compound (c) according to the following Scheme 1 will be described.
【００２３】[0023]
【化９】 Embedded image
【００２４】化合物（ａ）５９．０ｇを燐酸３７５ｍｌ
に懸濁し溶解した。その後−５℃まで冷却し、化合物
（ｂ）２５．８ｇと燐酸１７０ｍｌの溶液を内温−５〜
０℃の範囲で投入した。更に亜硝酸イソアミル１８．３
ｍｌを内温−５〜０℃の範囲で投入した。０℃で更に６
０分間撹拌した後イソプロピルアルコール５５０ｍｌで
希釈し、食塩３００ｇを水２０００ｍｌに溶解した液に
撹拌下４５℃で注入した。その後室温まで冷却し析出し
た結晶を濾取し、食塩５０ｇを水５００ｍｌで溶解した
液で洗浄した。結晶を乾燥し化合物（ｃ）を得た。収量
６２．９ｇ、収率８６．０％、融点２４０℃。Compound (a) (59.0 g) was added to 375 ml of phosphoric acid.
And dissolved. Thereafter, the mixture was cooled to −5 ° C., and a solution of 25.8 g of compound (b) and 170 ml of phosphoric acid was added at an internal temperature of -5 to
Charged in the range of 0 ° C. Further, isoamyl nitrite 18.3
ml was charged at an internal temperature of -5 to 0 ° C. 6 more at 0 ° C
After stirring for 0 minutes, the mixture was diluted with 550 ml of isopropyl alcohol and poured into a solution of 300 g of sodium chloride dissolved in 2000 ml of water at 45 ° C. with stirring. After cooling to room temperature, the precipitated crystals were collected by filtration and washed with a solution of 50 g of sodium chloride dissolved in 500 ml of water. The crystals were dried to obtain a compound (c). Yield 62.9 g, yield 86.0%, melting point 240 ° C.
【００２５】実施例２ 下記スキーム２に示す化合物（ｆ）の合成法を述べる。Example 2 A method for synthesizing the compound (f) shown in the following scheme 2 will be described.
【００２６】[0026]
【化１０】 Embedded image
【００２７】化合物（ｅ）２８．３ｇを燐酸２００ｍｌ
に溶解し、その後−５℃まで冷却した。化合物（ｄ）４
０．７ｇを燐酸２５０ｍｌに溶解し、化合物（ｅ）の溶
液に内温−５〜０℃の範囲で投入した。更に亜硝酸イソ
アミル１３．５ｍｌを内温−５〜０℃の範囲で投入し
た。０℃で更に６０分間撹拌した後イソプロピルアルコ
ール４５０ｍｌで希釈し、食塩２５０ｇを水１７００ｍ
ｌに溶解した液に撹拌下４５℃で注入した。その後室温
まで冷却し析出した結晶を濾取し、食塩５０ｇを水５０
０ｍｌで溶解した液で洗浄した。結晶を乾燥し化合物
（ｆ）を得た。収量５３．６ｇ、収率８５．０％、融点
２２０℃以上。化合物（ｄ）の他、一般式（１）の具体
例で挙げた化合物においても同様の結果を得た。化合物
（ｅ）の他、一般式（２）の具体例で挙げた化合物にお
いても同様の結果を得た。また、亜硝酸イソアミルにか
えて、亜硝酸ソーダを用いた以外は、上記と全く同様に
して製造を行ったところ、収率は６８．０％であった。28.3 g of the compound (e) was added to 200 ml of phosphoric acid.
And then cooled to -5 ° C. Compound (d) 4
0.7 g was dissolved in 250 ml of phosphoric acid, and the solution was charged into the solution of compound (e) at an internal temperature of -5 to 0 ° C. Further, 13.5 ml of isoamyl nitrite was charged at an internal temperature of -5 to 0 ° C. After stirring at 0 ° C. for another 60 minutes, the mixture was diluted with 450 ml of isopropyl alcohol, and 250 g of sodium chloride was added to 1700 m of water.
The solution dissolved in 1 was poured at 45 ° C. with stirring. Then, the mixture was cooled to room temperature, and the precipitated crystals were collected by filtration.
It was washed with a solution dissolved in 0 ml. The crystals were dried to obtain compound (f). Yield 53.6 g, 85.0%, melting point 220 ° C. or higher. Similar results were obtained with the compounds listed in the specific examples of the general formula (1) in addition to the compound (d). Similar results were obtained with the compounds listed in the specific examples of the general formula (2) in addition to the compound (e). The production was carried out in exactly the same manner as above except that sodium nitrite was used in place of isoamyl nitrite, and the yield was 68.0%.
【００２８】比較例１ 上記スキーム２に示す化合物（ｆ）の合成法において、
以下の場合は実施例２に比較し収率が低下する。化合物
（ｅ）２８．３ｇを燐酸２００ｍｌに溶解し、その後−
５℃まで冷却した。次に亜硝酸イソアミル１３．５ｍｌ
を内温−５〜０℃の範囲で投入した。一方、化合物
（ｄ）４０．７ｇを燐酸２５０ｍｌに溶解し、−５℃に
冷却した。この液に先の化合物（ｅ）の溶液を内温−５
〜０℃の範囲で投入した。０℃で更に６０分間撹拌した
後イソプロピルアルコール４５０ｍｌで希釈し、食塩２
５０ｇを水１７００ｍｌに溶解した液に撹拌下４５℃で
注入した。その後室温まで冷却し析出した結晶を濾取
し、食塩５０ｇを水５００ｍｌで溶解した液で洗浄し
た。結晶を乾燥し化合物（ｆ）を得た。収量４１．０
ｇ、収率６５．０％。なお、上記の亜硝酸イソアミルに
かえて、亜硝酸ソーダを相当量使用した場合の収率は６
３．０％であった。Comparative Example 1 In the method for synthesizing compound (f) shown in Scheme 2 above,
In the following cases, the yield is lower than in Example 2. Dissolve 28.3 g of compound (e) in 200 ml of phosphoric acid,
Cooled to 5 ° C. Next, 13.5 ml of isoamyl nitrite
At an internal temperature of -5 to 0 ° C. On the other hand, 40.7 g of compound (d) was dissolved in 250 ml of phosphoric acid and cooled to -5 ° C. The solution of the compound (e) was added to this solution at an internal temperature of -5.
It was charged in the range of ０0 ° C. After stirring at 0 ° C. for another 60 minutes, the mixture was diluted with 450 ml of isopropyl alcohol,
50 g was poured into a solution of 1700 ml of water at 45 ° C. with stirring. After cooling to room temperature, the precipitated crystals were collected by filtration and washed with a solution of 50 g of sodium chloride dissolved in 500 ml of water. The crystals were dried to obtain compound (f). Yield 41.0
g, yield 65.0%. In addition, when a considerable amount of sodium nitrite is used in place of the above-described isoamyl nitrite, the yield is 6%.
3.0%.
【００２９】比較例２ 下記スキーム３に従い化合物（ｉ）を製造した。Comparative Example 2 Compound (i) was produced according to Scheme 3 below.
【００３０】[0030]
【化１１】 Embedded image
【００３１】化合物（ｈ）７．４ｇを燐酸１００ｍｌに
溶解し、その後−５℃まで冷却した。化合物（ｇ）２
０．０ｇを燐酸１５０ｍｌに溶解し、化合物（ｈ）の溶
液に内温−５〜０℃の範囲で投入した。更に亜硝酸イソ
アミル５．７ｍｌを内温−５〜０℃の範囲で投入した。
０℃で更に６０分間撹拌した後、目的物の反応生成率を
調べたところ目的物（ｉ）の生成はわずかしか確認でき
ず、多数の副生成物が認められた。Compound (h) (7.4 g) was dissolved in phosphoric acid (100 ml) and then cooled to -5 ° C. Compound (g) 2
0.0 g was dissolved in 150 ml of phosphoric acid, and charged to the solution of compound (h) at an internal temperature of -5 to 0 ° C. Further, 5.7 ml of isoamyl nitrite was charged at an internal temperature of -5 to 0 ° C.
After further stirring at 0 ° C. for 60 minutes, the reaction product of the target product was examined. As a result, only a small amount of the target product (i) could be confirmed, and many by-products were observed.
【００３２】[0032]
【発明の効果】本発明方法によれば、一般式（１）で表
される化合物の存在下で、一般式（２）で表されるヘテ
ロ環化合物をジアゾ化させ同時に反応させることがで
き、対応のアゾ化合物を温和な条件で、収率良く合成す
ることができる。本発明方法によれば、副生物の生成の
抑制も実現できる。According to the method of the present invention, the heterocyclic compound represented by the general formula (2) can be diazotized and reacted simultaneously in the presence of the compound represented by the general formula (1), The corresponding azo compound can be synthesized under mild conditions with good yield. According to the method of the present invention, generation of by-products can be suppressed.
Claims (1)
在下で、一般式（２）で表されるヘテロ環化合物をジア
ゾ化し、反応させることを特徴とする、一般式（３）で
表されるアゾ化合物の製造方法。 一般式（１） ＨＯ−Ｘ 一般式（２） Ｈ２Ｎ−Ｙ 一般式（３） ＨＯ−Ｘ−Ｎ＝Ｎ−Ｙ 式中、Ｘはアリール基を、Ｙはへテロ環を有する残基を
示す。1. A compound represented by the general formula (3), wherein a heterocyclic compound represented by the general formula (2) is diazotized and reacted in the presence of a compound represented by the following general formula (1). A method for producing an azo compound represented by the formula: In the general formula (1) HO-X Formula (2) H 2 N-Y Formula (3) HO-X-N = N-Y -type, X is an aryl group, residue Y has the heterocycle Is shown.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11056213A JP2000248188A (en) | 1999-03-03 | 1999-03-03 | Manufacture of azo compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11056213A JP2000248188A (en) | 1999-03-03 | 1999-03-03 | Manufacture of azo compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000248188A true JP2000248188A (en) | 2000-09-12 |
Family
ID=13020838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11056213A Pending JP2000248188A (en) | 1999-03-03 | 1999-03-03 | Manufacture of azo compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000248188A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016051869A1 (en) * | 2014-09-30 | 2016-04-07 | 富士フイルム株式会社 | Method for producing azo dye, organic amine salt, method for producing organic amine salt, azo compound and method for producing azo compound |
| JP2016088966A (en) * | 2014-10-30 | 2016-05-23 | 富士フイルム株式会社 | Method for producing azo compound |
-
1999
- 1999-03-03 JP JP11056213A patent/JP2000248188A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016051869A1 (en) * | 2014-09-30 | 2016-04-07 | 富士フイルム株式会社 | Method for producing azo dye, organic amine salt, method for producing organic amine salt, azo compound and method for producing azo compound |
| JPWO2016051869A1 (en) * | 2014-09-30 | 2017-04-27 | 富士フイルム株式会社 | Production method of azo dye, organic amine salt and production method thereof, and azo compound and production method thereof |
| CN106687532A (en) * | 2014-09-30 | 2017-05-17 | 富士胶片株式会社 | Method for producing azo dye, organic amine salt, method for producing organic amine salt, azo compound and method for producing azo compound |
| CN106687532B (en) * | 2014-09-30 | 2019-10-25 | 富士胶片株式会社 | Method for producing azo pigment, organic amine salt and method for producing organic amine salt, and azo compound and method for producing azo compound |
| JP2016088966A (en) * | 2014-10-30 | 2016-05-23 | 富士フイルム株式会社 | Method for producing azo compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4503234A (en) | Production of 2-(2-aminothiazole-4-yl)-2-(syn)-methoxyimino acetic esters | |
| JP2000248188A (en) | Manufacture of azo compound | |
| JP2006131568A (en) | Hydroxynaphthoic acid hydrazide, derivative thereof and method for producing the same | |
| JPS6326785B2 (en) | ||
| JP4452420B2 (en) | New compounds | |
| JP4021663B2 (en) | Method for producing triphenylene compound | |
| JP2003506444A (en) | Preparation of thiazole derivatives | |
| US4187225A (en) | Novel synthesis of bis pyrazolone oxonol dyes | |
| KR950007218B1 (en) | Process for the production of arylaminonitro-phenyl-hydroxyethyl sulphones | |
| JPH1160977A (en) | Synthesis of sulfonyl chloride of azo compound | |
| JP4162320B2 (en) | Process for producing benzoisothiazole derivative | |
| JPS6231701B2 (en) | ||
| US7329780B2 (en) | Method of preparing optically pure phenethylamine derivatives | |
| JP2005508385A (en) | Method for producing cephalosporin side chain | |
| JP4201511B2 (en) | Process for producing (Z) -2-aminothiazole compound | |
| JP4242937B2 (en) | Method for producing 1H-1,2,4-triazole derivative | |
| JPS6242989A (en) | Production of 7alpha-methoxycephalosporin compound | |
| JPH0136612B2 (en) | ||
| JP3010383B2 (en) | Method for synthesizing 3-carboxy-5-acyloxypyrazole | |
| JP4031156B2 (en) | Preferential production method of Z form of 2-aminothiazole derivative | |
| JP2002255914A (en) | Method for producing cis-4-amino-2-cyclopentenecarboxylic acid mineral acid salt | |
| JP2001316350A (en) | Carbonic acid ester compound of hydroxyguanidine and method for producing the same | |
| JPH05246961A (en) | Production of aromatic amine derivative | |
| JPH0128742B2 (en) | ||
| JP2001261604A (en) | Method for producing halogenopropyl ethers |