JPS5931502B2 - Production method of pyridine-based compounds - Google Patents
Production method of pyridine-based compoundsInfo
- Publication number
- JPS5931502B2 JPS5931502B2 JP52041003A JP4100377A JPS5931502B2 JP S5931502 B2 JPS5931502 B2 JP S5931502B2 JP 52041003 A JP52041003 A JP 52041003A JP 4100377 A JP4100377 A JP 4100377A JP S5931502 B2 JPS5931502 B2 JP S5931502B2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
- C07D213/85—Nitriles in position 3
-
- 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
- C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
- C09B29/3621—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring
- C09B29/3639—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more amino groups
-
- 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
- C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
- C09B31/02—Disazo dyes
- C09B31/12—Disazo dyes from other coupling components "C"
- C09B31/14—Heterocyclic components
- C09B31/153—Heterocyclic components containing a six-membered ring with one nitrogen atom as the only ring hetero-atom
-
- 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
- C09B43/00—Preparation of azo dyes from other azo compounds
-
- 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
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/18—Preparation of azo dyes from other azo compounds by acylation of hydroxyl group or of mercapto group
- C09B43/20—Preparation of azo dyes from other azo compounds by acylation of hydroxyl group or of mercapto group with monocarboxylic acids, carbamic acid esters or halides, mono- isocyanates or haloformic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Coloring (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
【発明の詳細な説明】
本発明は、一般式
で表わされる新規なピリジン系化合物の製法に関する．
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel pyridine compound represented by the general formula.
.
この式中Ｒ及びＲ２は互いに無関係に水素原子；アリル
基；１〜８個の炭素原子を有するアルキル基：酸素原子
により中断されていてもよくかつ水酸基、カルボキシル
基もしくは１〜８個の炭素原子を有するアルコキシ基に
より置換された１〜８個の炭素原子を有するアルキル基
；シクロヘキシル基：ヒドロキシシクロヘキシル基；ベ
ンジル基；フエニルエチル基：メチル基もしくはメトキ
シ基により置換されていてもよいフエニル基：ＣＨ２意
味し、Ｒ１及びＲ３は互いに無関係に水素原子又は１〜
８個の炭素原子を有するアルキル基を意味する。In this formula, R and R2 are independently a hydrogen atom; an allyl group; an alkyl group having 1 to 8 carbon atoms; a hydroxyl group, a carboxyl group, or a hydroxyl group, which may be interrupted by an oxygen atom; an alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group having the following; cyclohexyl group: hydroxycyclohexyl group; benzyl group; phenylethyl group: a phenyl group optionally substituted with a methyl group or a methoxy group: CH2 meaning However, R1 and R3 are independently a hydrogen atom or 1-
means an alkyl group having 8 carbon atoms.
基Ｒ及びＲ１は前記のもののほか、個々にはたとえば次
のものである。In addition to the above groups, R and R1 are individually, for example, as follows.
メチル基、エチル基、プロピル基、ブチル基、ヘキシル
基、β一エチルヘキシル基、β−ヒドロキシエチル基も
しくは−プロピル基、γ−ヒドロキシプロピル基、ω−
ヒドロキシヘキシル基、β−メトキシエチル基、γ−メ
トキシプロピル基、β一エトキシエチル基、γエトキシ
プロピル基、γ−イソプロポキシプロピル基、γ−ブト
キシプロピル基、ならびに次式基Ｒ１及びＲ３は水素原
子のほか、たとえばメチル基、エチル基、プロピル基、
ブチル基、ヘキシル基又はβ一エチルヘキシル基である
。式１の化合物は、アゾ染料の製造のための価値あるカ
ツプリング成分である。Methyl group, ethyl group, propyl group, butyl group, hexyl group, β-ethylhexyl group, β-hydroxyethyl group or -propyl group, γ-hydroxypropyl group, ω-
Hydroxyhexyl group, β-methoxyethyl group, γ-methoxypropyl group, β-ethoxyethyl group, γ-ethoxypropyl group, γ-isopropoxypropyl group, γ-butoxypropyl group, and the following formula groups R1 and R3 are hydrogen atoms In addition, for example, methyl group, ethyl group, propyl group,
It is a butyl group, a hexyl group, or a β-ethylhexyl group. Compounds of formula 1 are valuable coupling components for the production of azo dyes.
本カツプリング成分の製造は、一般式
で表わされる２・６−ジクロル−３−シアン−４一メチ
ルピリジンを一般式で表わされるアミン（これらの式中
の記号は前記の意味を有する）と反応させることにより
行われる。The coupling component is produced by reacting 2,6-dichloro-3-cyan-4-methylpyridine represented by the general formula with an amine represented by the general formula (the symbols in these formulas have the meanings given above). This is done by
この際一級又は二級のアミンを用いることができる。反
応条件を適宜に選択することによつて、２・６−ジクロ
ル−３−シアン−４−メチルピリジンの塩素原子を段階
的に置換して、モノ置換体及びジ置換体を単離すること
もできる。In this case, primary or secondary amines can be used. By appropriately selecting reaction conditions, the chlorine atom of 2,6-dichloro-3-cyan-4-methylpyridine can be replaced stepwise to isolate mono-substituted products and di-substituted products. can.
塩素原子の置換に影響を与える反応条件は温度、アミン
成分、反応物質のモル比ならびに希釈剤又は溶剤である
。第１の反応段階では、主として６−アミノ−３−シア
ン−４−メチル−２−クロルピリジンが得られると思わ
れる。次いでこれを中間で単離して又は単離することな
く反応させて、同一の又は異なるアミン残基を有する２
・６−ジアミノ−３−シアン−４−メチルピリジン誘導
体を生成することができる。続いてシアン基を常法によ
りカルボンアミド基に変えることができる。２・６−ジ
クロル−３−シアン−４−メチルピリジンを種々のアミ
ンの混合物と反応させて塩素原子を完全に置換すると、
カツプリング成分の混合物が得られる。The reaction conditions that influence the displacement of chlorine atoms are temperature, amine component, molar ratio of reactants, and diluent or solvent. The first reaction step appears to yield primarily 6-amino-3-cyan-4-methyl-2-chloropyridine. This is then reacted with or without intermediate isolation to form two molecules with identical or different amine residues.
- A 6-diamino-3-cyan-4-methylpyridine derivative can be produced. Subsequently, the cyan group can be converted into a carbonamide group by conventional methods. When 2,6-dichloro-3-cyan-4-methylpyridine is reacted with a mixture of various amines to completely replace the chlorine atoms,
A mixture of coupling components is obtained.
すなわち２種のアミンを用いる場合にぱたとえば４種の
カツプリング成分の混合物が得られ、３種のアミンの混
合物を用いると９種のカツプリング成分の混合物が得ら
れる。２・６−ジアミノ−３−シアン−４−メチルピリ
ジン誘導体を製造するために、アミン成分としてアンモ
ニア又は易揮発性アミンたとえばメチルアミン又はエチ
ルアミンを用いる場合には、反応条件下で不活性な溶剤
中のこれらアミン又はアンモニアの溶液を使用すること
が推奨される。That is, when two amines are used, a mixture of four coupling components is obtained, and when a mixture of three amines is used, a mixture of nine coupling components is obtained. If ammonia or a readily volatile amine such as methylamine or ethylamine is used as the amine component for the preparation of the 2,6-diamino-3-cyan-4-methylpyridine derivative, it may be used in a solvent that is inert under the reaction conditions. It is recommended to use solutions of these amines or ammonia.
約１５０℃までの反応温度に関しては、不活性な溶剤と
しては、たとえばアルコールたとえばメタノール、−エ
タノール又はβ−メトキシエタノールがあげられる。こ
れらの成分をより高い温度で反応させる場合には、たと
えばジメチルホルムアミド、Ｎ−メチルピロリドン、グ
リコール又はグリコールエーテルたとえばエチレングリ
コールジメチルエーテルが適している。液化したアミン
を加圧下に用いることもできる。反応に際して遊離する
ＨＣｌを結合するために、過剰のアミンならびに普通に
使用される酸結合剤たとえば三級アミン、酸化マグネシ
ウム、アルコラード又はアルカリを用いることができる
。For reaction temperatures of up to about 150 DEG C., inert solvents include, for example, alcohols such as methanol, -ethanol or β-methoxyethanol. For example, dimethylformamide, N-methylpyrrolidone, glycols or glycol ethers such as ethylene glycol dimethyl ether are suitable if these components are reacted at higher temperatures. Liquefied amines can also be used under pressure. To bind the HCl liberated during the reaction, an excess of amine as well as the commonly used acid binders such as tertiary amines, magnesium oxide, alcoholades or alkalis can be used.
式のアミンは、たとえば次のものである。アンモニア、
アリルアミン、メチルアミン、エチルアミン、ｎ−もし
くはイソプロピルアミン、ｎ−もしくはイソブチルアミ
ン、三級ブチルアミン、イソアミルアミン、ｎ−もしく
はイソヘキシルアミン、ｎ−もしくはイソオクチルアミ
ン、２−エチルブチルアミン、２−エチルヘキシルアミ
ン、シクロヘキシルアミン、β−ヒドロキシエチルアミ
ン、β−ヒドロキシプロピルアミン、γ−ヒドロキシプ
ロピルアミン、ω−ヒドロキシヘキシルアミン、β−メ
トキシエチルアミン、β一エトキシエチルアミン、β−
ブトキシエチルアミン、γ（β７ーエチルヘキソキシ）
−プロピルアミン、β一（β７ーヒドロキシエトキシ）
一エチルアミン、γ一エトキシプロピルアミン、γ−メ
トキシプロピルアミン、γ−イソプロポキシプロピルア
ミン、β−アミノ−β一エチル一α・γ−プロパンジオ
ール、β−アミノ−β−メチルプロパノール、Ｎ−エチ
ル−Ｎ−（β−ヒドロキシエチル）−アミン、ジエタノ
ールアミン、ジメチルアミン、ジエチルアミン、ジプロ
ピルアミン、Ｎ−メチル−Ｎ−（β−ヒドロキシエチル
）−アミン、アニリン、０−、ｍ−もしくはｐ−トルイ
ジン、ｏ−、ｍ−もしくはｐ−メトキシアニリン、Ｎ−
メチルアニリン、ベンジルアミン、β−フエニルエチル
アミン好ましい基Ｒ及びＲ２は、たとえば次のものであ
る。An amine of the formula is, for example: ammonia,
Allylamine, methylamine, ethylamine, n- or isopropylamine, n- or isobutylamine, tertiary butylamine, isoamylamine, n- or isohexylamine, n- or isooctylamine, 2-ethylbutylamine, 2-ethylhexylamine, Cyclohexylamine, β-hydroxyethylamine, β-hydroxypropylamine, γ-hydroxypropylamine, ω-hydroxyhexylamine, β-methoxyethylamine, β-monoethoxyethylamine, β-
Butoxyethylamine, γ(β7-ethylhexoxy)
-Propylamine, β-(β7-hydroxyethoxy)
Monoethylamine, γ-ethoxypropylamine, γ-methoxypropylamine, γ-isopropoxypropylamine, β-amino-β-ethyl-α,γ-propanediol, β-amino-β-methylpropanol, N-ethyl- N-(β-hydroxyethyl)-amine, diethanolamine, dimethylamine, diethylamine, dipropylamine, N-methyl-N-(β-hydroxyethyl)-amine, aniline, o-, m- or p-toluidine, o -, m- or p-methoxyaniline, N-
Methylaniline, benzylamine, β-phenylethylamine Preferred groups R and R2 are, for example, as follows.
エチル基、ｎ−もしくはイソプロピル基、ｎ−もしくは
イソブチル基、ｎ−ヘキシル基、β一エチルヘキシル基
、β−ヒドロキシエチル基、γ−ヒドロキシプロピル基
、ω−ヒドロキシヘキシル基、β−メトキシエチル基も
しくは−プロピル基、γ−メトキシプロピル基、γ−イ
ソプロポキシプロピル基、シクロヘキシル基、ベンジル
基、フエニルエチル基、フエニル基又はトリル基、なら
びに次式の残基。（ＣＨ２）２０（ＣＨ２）２０Ｈ、式
１のカツプリング成分においては、基ＲとＲ２の炭素原
子の合計が約７〜１４個のものが優れており、その際エ
ーテル基特に水酸基が存在することが好ましい。下記例
中の部及び％は特に指示しない限り重量に関する。Ethyl, n- or isopropyl, n- or isobutyl, n-hexyl, β-ethylhexyl, β-hydroxyethyl, γ-hydroxypropyl, ω-hydroxyhexyl, β-methoxyethyl or - Propyl group, γ-methoxypropyl group, γ-isopropoxypropyl group, cyclohexyl group, benzyl group, phenylethyl group, phenyl group or tolyl group, and residues of the following formula. In the coupling component of (CH2)20(CH2)20H, formula 1, it is preferable that the groups R and R2 have a total of about 7 to 14 carbon atoms, in which case the presence of an ether group, especially a hydroxyl group, is preferable. preferable. Parts and percentages in the examples below relate to weight unless otherwise indicated.
例１
２・６−ジクロル−３−シアン−４−メチルピリジン５
４部を２０〜３８℃で、β−メトキシエチルアミン９０
部及びメタノール７０部の混合物中に入れる。Example 1 2,6-dichloro-3-cyan-4-methylpyridine 5
4 parts at 20-38°C, β-methoxyethylamine 90%
1 part and 70 parts of methanol.
混合物を３時間４０℃で撹拌し、次いで氷水１０００部
を添加する。塩酸でＰＨ４〜５に酸性化したのち析出す
る沈殿を吸引沢過し、水洗する。生成物５０部にβ−ヒ
ドロキシエチルアミン１２０部を添加したのち混合物を
３〜４時間１６０〜１７０℃で攪拌する。次いで１２０
℃に冷却し、混合物を撹拌下に氷５００部及び水５００
部上に注ぎ、塩酸でＰＨ５〜６に酸性化すると、暗緑色
の油約５０部が得られ、これは徐々に固化する。粗生成
物の融点は１０８〜１１ＰＣである。推定構造式は下記
のとおりである。この生成物は下記の推定構造を有する
カツプリング成分を少量含有する。例２
２−６−ジクロル−３−シアン− ４ −メチルピリジ
ン１８７部を２０〜３０℃で徐々に、β−ヒドロキシエ
チルアミン２５０容量部及びメタノール２００容量部か
らの混合物に添加する。The mixture is stirred for 3 hours at 40° C. and then 1000 parts of ice water are added. After acidifying with hydrochloric acid to pH 4-5, the precipitate that precipitates is filtered off with suction and washed with water. After adding 120 parts of β-hydroxyethylamine to 50 parts of the product, the mixture is stirred for 3-4 hours at 160-170°C. then 120
℃ and stirred the mixture into 500 parts of ice and 500 parts of water.
After acidification to pH 5-6 with hydrochloric acid, approximately 50 parts of a dark green oil is obtained, which gradually solidifies. The melting point of the crude product is 108-11 PC. The estimated structural formula is as follows. This product contains a small amount of a coupling component with the deduced structure below. Example 2 187 parts of 2-6-dichloro-3-cyan-4-methylpyridine are added slowly at 20-30° C. to a mixture of 250 parts by volume of β-hydroxyethylamine and 200 parts by volume of methanol.
４〜５時間４０℃で撹拌し、次いで混合物をよく撹拌し
ながら氷水３０００部中に加え、そして塩酸でＰＨ６〜
４に酸性化する。Stir at 40° C. for 4-5 hours, then add the mixture to 3000 parts of ice water with good stirring and adjust the pH to 6-6 with hydrochloric acid.
Acidify to 4.
析出する沈殿を沢別し、水洗して乾燥すると、無色粉末
２０２部が得られる。この粉末１００部をβ−メトキシ
エチルアミン３００容量部と共に１２時間還流冷却下に
加熱する。次いで過剰のアミンを留去し、残査を氷水１
５００部中で攪拌し、そして塩酸でＰＨ６〜７に調整す
る。析出する沈殿を沢別し、水洗して乾燥すると、下記
の推定構造を有する褐色ないし無色の粉末約１００〜１
１０部が得られる。この物質は７８〜８１℃で溶融する
。The precipitate is separated, washed with water, and dried to obtain 202 parts of colorless powder. 100 parts of this powder are heated under reflux cooling for 12 hours with 300 parts by volume of β-methoxyethylamine. Then, excess amine was distilled off, and the residue was poured into ice water for 1 hour.
Stir in 500 parts and adjust the pH to 6-7 with hydrochloric acid. When the precipitate is separated, washed with water, and dried, a brown to colorless powder having the estimated structure shown below is obtained.
10 parts are obtained. This material melts at 78-81°C.
この生成物は下記の推定構造を有するカツプリング成分
を少量含有する。例３
２・６−ジクロル− ３ −シアン−４−メチルピリジ
ン９３部にβ−ヒドロキシエチルアミン２２０容量部を
添加し、注意深く１６５〜１７０℃に加熱する。This product contains a small amount of a coupling component with the deduced structure below. Example 3 220 parts by volume of β-hydroxyethylamine are added to 93 parts of 2,6-dichloro-3-cyan-4-methylpyridine and carefully heated to 165-170°C.
この瀧度で２〜３時間撹拌したのち１２０℃に冷却し、
混合物を氷水７００部に添加し、そしてＰＨ７〜 ６に
調整する。沈殿を吸引Ｐ過しで乾燥したのち、融点１５
６℃の次式の無色粉末９７部が得られる。例４
２・６−ジクロル−３−シアン−４−メチルピリジン５
４部を１５〜３５℃で冷却下に、ジエチルアミン８０部
及びメタノール１３０容量部からの混合物中に徐々に加
える。After stirring at this temperature for 2 to 3 hours, it was cooled to 120°C.
The mixture is added to 700 parts of ice water and adjusted to pH 7-6. After drying the precipitate by suction P filtration, the melting point was 15.
97 parts of a colorless powder of the following formula are obtained at 6°C. Example 4 2,6-dichloro-3-cyan-4-methylpyridine 5
4 parts are slowly added under cooling at 15 DEG to 35 DEG C. into a mixture of 80 parts of diethylamine and 130 parts by volume of methanol.
混合物を４時間３５℃で攪拌し、次いでこれを水１００
０部に注入する。塩酸でＰＨ６に酸性化したのち吸引沢
過し、得られた生成物を水洗する。メタノールから再結
晶したのち、融点８８〜９０℃の下記の推定構造を有す
る無色粉末５０部が得られる。例５
次式
の生成物５４部にβ−ヒドロキシエチルアミン１２０容
量部を添加し、１６５℃で３時間攪拌する。The mixture was stirred for 4 hours at 35°C, then it was diluted with 100% water.
Inject into 0 parts. After acidification to pH 6 with hydrochloric acid, it is filtered with suction and the product obtained is washed with water. After recrystallization from methanol, 50 parts of a colorless powder with a melting point of 88-90 DEG C. and the deduced structure below are obtained. Example 5 120 parts by volume of β-hydroxyethylamine are added to 54 parts of a product of the following formula and stirred at 165° C. for 3 hours.
次いで１１０℃に冷却し、そして水１００部を添加し、
ＰＨが６〜７になるまで塩酸を添加す８８る。室温に冷
却したのち得られる下記の推定構造を有する油状の生成
物を、常法により水相から分′ 離する。この生成物を
徐々に固化し、１０６〜１０８℃で溶融する。θ例６
次式
ノ
の生成物（融点１１８〜１２０℃）１００部に、３−メ
トキシ−プロピルアミン１２０容量部及びｎ−ヘキシル
アミン１２０容量部からの混合物を添加する。Then cool to 110°C and add 100 parts of water,
Add hydrochloric acid until the pH is 6-7. After cooling to room temperature, the resulting oily product having the deduced structure shown below is separated from the aqueous phase by conventional methods. The product gradually solidifies and melts at 106-108°C. θ Example 6 To 100 parts of a product of the following formula (melting point 118-120° C.) is added a mixture of 120 parts by volume of 3-methoxy-propylamine and 120 parts by volume of n-hexylamine.
混合物を１２時間還流冷却下に加熱したのち過剰のアミ
ンを留去し、残査に水１５００部を添加し、そしてＰＨ
６〜７になるまで塩酸を添加する。析出する油状物を常
法により水相から分離すると、暗色の油状物１９０〜２
２０部が得られる。このものは次式及び
のカツプリング成分から成る。After heating the mixture under reflux cooling for 12 hours, the excess amine was distilled off, 1500 parts of water were added to the residue, and the PH
Add hydrochloric acid until it reaches 6-7. When the precipitated oil is separated from the aqueous phase by a conventional method, a dark-colored oil 190-2
20 parts are obtained. This consists of the following coupling components:
例７
２・６−ジクロル−３−シアン−４−メチルピリジン１
０８部及びＮ−メチルピロリドン１３０部からの混合物
中に、６０〜１００℃でβ−メトキシエチルアミン５０
部、β−ヒドロキシエチルアミン５０部及びｎ−ブチル
アミン２５部からの混合物を流入する。Example 7 2,6-dichloro-3-cyan-4-methylpyridine 1
08 parts of β-methoxyethylamine and 130 parts of N-methylpyrrolidone at 60-100°C.
1 part, 50 parts of β-hydroxyethylamine and 25 parts of n-butylamine.
次いで混合物を１０時間還流冷却下に撹拌したのち、過
剰のアミンを留去する。残査に水２０００部を添加し、
そしてＰＨ６になるまで塩酸を添加する。析出する油状
物を分離すると、次式のアミンの混合物約１００〜１１
５部が得られる。式中Ｒ１及びＲ２は基−ＣＨ２ＣＨ２
ＯＨ、ＣＨ２ＣＨ２ＯＣＨ３又は一（ＣＨ２）３ＣＨ３
を意味し、その際Ｒ１とＲ２ぱ同一でも異なつてもよい
。The mixture is then stirred for 10 hours under reflux cooling, after which excess amine is distilled off. Add 2000 parts of water to the residue,
Then, add hydrochloric acid until the pH becomes 6. Separation of the precipitated oil yields a mixture of amines of the formula approximately 100 to 11
5 parts are obtained. In the formula, R1 and R2 are groups -CH2CH2
OH, CH2CH2OCH3 or one (CH2)3CH3
In this case, R1 and R2 may be the same or different.
例８２・６−ジクロル−３−シアン−４−メチルピリジ
ン５４部を３５〜４０℃で冷却下に、β−ヒドロキシエ
チルアミン３０部及びβ−メトキシエチルアミン３０部
のＮ−メチルピロリドン１００部中の混合物に徐々に添
加する。Example 8 54 parts of 2.6-dichloro-3-cyan-4-methylpyridine are mixed with 30 parts of β-hydroxyethylamine and 30 parts of β-methoxyethylamine in 100 parts of N-methylpyrrolidone with cooling at 35-40°C. Add gradually.
４０℃で４〜５時間撹拌したのちｎ−ヘキシルアミン４
０部を添加し、そして混合物を更に１０〜１２時間還流
冷却下に加熱する。After stirring at 40°C for 4 to 5 hours, n-hexylamine 4
0 parts are added and the mixture is heated under reflux cooling for a further 10-12 hours.
次いで過剰のアミンを留去し、残査に水１０００部を添
加する。塩酸でＰＨ６〜５に酸性化したのち暗色の油状
物５４部が得られ、これは常法により水相から分離され
る。この生成物ぱ次式の構造を有する。式中Ｒ１及びＲ
２は基−ＣＨ２ＣＨ２ＯＨ、一ＣＨ２ＣＨ２ＯＣＨ３又
は一（ＣＨ２）５ＣＨ３を意味し、その際Ｒ１とＲ２は
同一でも異なつてもよい。Excess amine is then distilled off, and 1000 parts of water are added to the residue. After acidification to pH 6-5 with hydrochloric acid, 54 parts of a dark oil are obtained, which is separated from the aqueous phase in the usual manner. This product has the following structure: In the formula R1 and R
2 means the group -CH2CH2OH, -CH2CH2OCH3 or -(CH2)5CH3, R1 and R2 can be the same or different.
この混合物から単離されたＲ１−Ｒ２−一ＣＨ２ＣＨ２
ＯＨである化合物の融点は１５６℃である。例９
２・６−ジクロル−３−シアン−４−メチルピリジン５
６部、β−ヒドロキシエチルアミン２７部、β−メトキ
シエチルアミン３３部及びβ−ヒドロキシプロピルアミ
ン３３部からの混合物を、２時間１５０℃で攪拌する。R1-R2-1CH2CH2 isolated from this mixture
The melting point of the compound that is OH is 156°C. Example 9 2,6-dichloro-3-cyan-4-methylpyridine 5
A mixture of 6 parts of β-hydroxyethylamine, 27 parts of β-hydroxyethylamine, 33 parts of β-methoxyethylamine and 33 parts of β-hydroxypropylamine is stirred at 150° C. for 2 hours.
反応混合物を氷水１０００部及び１０Ｎ塩酸１００容量
部の混合物に注入し、次いで５５％酢酸ナトリウム溶液
１５０容量部を添加することによりＰＨ値を３．５〜４
−に調整し、そして水相を酢酸エチルエステル５００容
量部ずつで３回振出する。エステル抽出液を合わせて水
不含の硫酸ナトリウムで乾燥し、沢液からエステルを留
去すると、粘稠な油状物６６部が残留する。この生成物
は次式の化合物の混合物である。い。The reaction mixture is poured into a mixture of 1000 parts of ice water and 100 parts by volume of 10N hydrochloric acid, and then the pH value is brought to 3.5-4 by adding 150 parts by volume of 55% sodium acetate solution.
- and the aqueous phase is shaken out three times with 500 parts by volume of ethyl acetate. The ester extracts were combined and dried over water-free sodium sulfate, and the ester was distilled off from the sap, leaving 66 parts of a viscous oil. The product is a mixture of compounds of the formula: stomach.
例１０
２・６−ジクロル−３−シアン−４−メチルピリジン９
４部を２５％アンモニア２０００容量部とオートクレー
ブ沖１８０℃で５時間反応させると、融点２２６〜２２
７℃の次式の化合物が得られる。Example 10 2,6-dichloro-3-cyan-4-methylpyridine 9
When 4 parts are reacted with 2000 volume parts of 25% ammonia at 180°C off the coast of an autoclave for 5 hours, the melting point is 226-22.
A compound of the following formula is obtained at 7°C.
☆▲▲
Ｚ↓１例１〜１０と同様にして、次表に示す化合物がひ
られる。☆▲▲
Z↓1 In the same manner as Examples 1 to 10, the compounds shown in the following table were prepared.
例５５
２・６−ジクロル−３−シアン−４−メチルピリジン４
７部を、メタノール１００゛容量部、アミノカプロン酸
６７部及びトリエチルアミン１１０部と共に沸騰冷却下
に２４時間撹拌する。Example 55 2,6-dichloro-3-cyan-4-methylpyridine 4
7 parts are stirred with 100 parts by volume of methanol, 67 parts of aminocaproic acid and 110 parts of triethylamine under boiling cooling for 24 hours.
続いてメタノール及びトリエチルアミンを大部分留去し
、そして残査に水約２５０部を加える。塩酸を用いてＰ
ＨＯ．５〜１．５に酸性化したのち、生成した沈殿を沢
別し、冷水で洗浄して乾燥すると、融点７５℃の次式の
生成物６７部が得られる。この生成物は２種の異性体の
混合物である。Subsequently, most of the methanol and triethylamine are distilled off, and approximately 250 parts of water are added to the residue. P using hydrochloric acid
HO. After acidification to 5 to 1.5, the precipitate formed is separated, washed with cold water and dried to give 67 parts of a product of the following formula having a melting point of 75 DEG C. This product is a mixture of two isomers.
その１４部をエチレングリコールジメチルエーテル１５
０容量部、アミノカプロン酸１５部及びトリエチルアミ
ン２５部と共に、１５０℃で５時間オートクレーブ中で
撹拌する。冷後に次式の生成物１８．５部の溶液が得ら
れる。 ずこの化合物は沈殿させるこ
とができないので、そのままカツプリングに用いられる
。たとえばジアゾ化された２−アミノジフエニルスルホ
ンとカツプリングさせると、帯赤黄色の染料が得られ、
この染料はポリカプロラクタムを帯赤黄色の色調に染色
する。例５５と同様にして、次表に示す化合物が製造さ
れる。Add 14 parts of it to 15 parts of ethylene glycol dimethyl ether.
Stir in an autoclave at 150° C. for 5 hours with 0 parts by volume, 15 parts of aminocaproic acid and 25 parts of triethylamine. After cooling, a solution of 18.5 parts of a product of the following formula is obtained. Since Zuko's compound cannot be precipitated, it is used as is for coupling. For example, when coupled with diazotized 2-aminodiphenylsulfone, a reddish-yellow dye is obtained.
This dye dyes polycaprolactam in a reddish-yellow shade. Analogously to Example 55, the compounds shown in the following table are prepared.
Claims (1)
、表等があります▼で表わされるアミン（これらの式中
Ｒ、Ｒ＾１、Ｒ＾２及びＲ＾３は後記の意味を有する）
と反応させることを特徴とする、一般式▲数式、化学式
、表等があります▼ （式中Ｒ及びＲ＾２は互いに無関係に水素原子；アリル
基；１〜８個の炭素原子を有するアルキル基；酸素原子
により中断されていてもよくかつ水酸基、カルボキシル
基もしくは１〜８個の炭素原子を有するアルコキシ基に
より置換された１〜８個の炭素原子を有するアルキル基
；シクロヘキシル基；ヒドロキシシクロヘキシル基；ベ
ンジル基；フェニルエチル基；メチル基もしくはメトキ
シ基により置換されていてもよいフェニル基；▲数式、
化学式、表等があります▼−Ｃ＿６Ｈ＿５又は（ＣＨ＿
２）＿３ＯＣ＿２Ｈ＿４ＯＣ＿６Ｈ＿５を意味し、Ｒ＾
１及びＲ＾３は互いに無関係に水素原子又は１〜８個の
炭素原子を有するアルキル基を意味する）で表わされる
ピリジン系化合物の製法。[Claims] 1. A compound represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A compound represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Amine (in these formulas, R, R^1, R^2 and R^3 have the meanings given below)
There are general formulas ▲mathematical formulas, chemical formulas, tables, etc., which are characterized by reacting with ; an alkyl group having 1 to 8 carbon atoms optionally interrupted by an oxygen atom and substituted by a hydroxyl group, a carboxyl group or an alkoxy group having 1 to 8 carbon atoms; a cyclohexyl group; a hydroxycyclohexyl group; Benzyl group; Phenylethyl group; Phenyl group optionally substituted with methyl group or methoxy group; ▲ Formula,
There are chemical formulas, tables, etc. ▼-C_6H_5 or (CH_
2) Means _3OC_2H_4OC_6H_5, R^
1 and R^3 independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE000P20627172 | 1970-12-19 | ||
| DE19702062717 DE2062717C3 (en) | 1970-12-19 | 1970-12-19 | Azo dyes from 2,6-diaminopyridine derivatives, process for their preparation and use |
| DE000P21565457 | 1971-11-15 | ||
| DE19712156545 DE2156545A1 (en) | 1971-11-15 | 1971-11-15 | Azo dyes - from 2,6-diaminopyridine derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5373568A JPS5373568A (en) | 1978-06-30 |
| JPS5931502B2 true JPS5931502B2 (en) | 1984-08-02 |
Family
ID=25760209
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP46102785A Granted JPS605618B1 (en) | 1970-12-19 | 1971-12-20 | |
| JP52041003A Expired JPS5931502B2 (en) | 1970-12-19 | 1977-04-12 | Production method of pyridine-based compounds |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP46102785A Granted JPS605618B1 (en) | 1970-12-19 | 1971-12-20 |
Country Status (9)
| Country | Link |
|---|---|
| JP (2) | JPS605618B1 (en) |
| BE (1) | BE776859A (en) |
| CH (1) | CH582215A5 (en) |
| CS (1) | CS166298B2 (en) |
| FR (1) | FR2118075B1 (en) |
| GB (2) | GB1377505A (en) |
| IT (1) | IT945532B (en) |
| NL (1) | NL7117139A (en) |
| SU (1) | SU458133A3 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH596263A5 (en) * | 1972-03-10 | 1978-03-15 | Basf Ag | |
| DE2222099A1 (en) * | 1972-05-05 | 1973-11-22 | Hoechst Ag | BASIC AZO DYES, THEIR PRODUCTION AND USE |
| DE2230392A1 (en) * | 1972-06-22 | 1974-01-31 | Cassella Farbwerke Mainkur Ag | SUBSTITUTED PYRIDINE COMPOUNDS AND PROCESS FOR THEIR PRODUCTION |
| US4070449A (en) | 1972-10-24 | 1978-01-24 | Wilkinson Sword Limited | Compounds having a physiological cooling effect and compositions containing them |
| CH592722A5 (en) * | 1973-06-25 | 1977-11-15 | Ciba Geigy Ag | |
| US4055649A (en) | 1976-02-05 | 1977-10-25 | Sandoz, Inc. | 4-Alkyl-2,6-di-(secondary or tertiary alkyl)amino-3-formylpyridines pharmaceutical compositions thereof and their use in the treatment of obesity and diabetes |
| DE2832020C2 (en) * | 1978-07-21 | 1982-12-23 | Basf Ag, 6700 Ludwigshafen | Disazo dyes with pyridine coupling components, their preparation and use |
| JPS61126915U (en) * | 1985-01-28 | 1986-08-09 | ||
| DE3528759A1 (en) * | 1985-08-10 | 1987-02-19 | Basf Ag | HETEROCYCLIC AZO DYES |
| JP3234004B2 (en) * | 1991-12-13 | 2001-12-04 | ダイスタージャパン株式会社 | Disperse dye mixture |
| ES2126638T3 (en) * | 1992-07-23 | 1999-04-01 | Ciba Geigy Ag | REACTIVE DYES, PROCEDURE FOR THEIR OBTAINING AND USE THEREOF. |
| EP0581730B1 (en) * | 1992-07-23 | 1999-01-20 | Ciba SC Holding AG | Reactive dyes, process for their manufacture and their use |
| ES2146221T3 (en) * | 1992-07-23 | 2000-08-01 | Ciba Sc Holding Ag | COLORING MIXTURES, PROCEDURE FOR THEIR OBTAINING AND USE. |
| US5403363A (en) * | 1992-12-07 | 1995-04-04 | Basf Aktiengesellschaft | Dye mixtures containing azo dyes having a coupling component from the diaminopyridine series |
| WO2000076980A1 (en) * | 1999-06-10 | 2000-12-21 | Yamanouchi Pharmaceutical Co., Ltd. | Novel nitrogen-contaiing heterocyclic derivatives or salts thereof |
| EP1487922B1 (en) * | 2002-03-22 | 2012-02-08 | Huntsman Advanced Materials (Switzerland) GmbH | Azo dyes |
| US20080010756A1 (en) * | 2004-09-03 | 2008-01-17 | Huntsman International Llc | Cyanopyridine-Based Azo Dyes |
| JP2010235527A (en) * | 2009-03-31 | 2010-10-21 | Fujifilm Corp | Method for producing 2,6-diaminopyridine compound |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2108824A (en) * | 1936-09-01 | 1938-02-22 | Eastman Kodak Co | Azo compounds and process for dyeing therewith |
| JPS5246230B2 (en) * | 1972-12-16 | 1977-11-22 | ||
| DE2260827C3 (en) * | 1972-12-13 | 1980-11-13 | Basf Ag, 6700 Ludwigshafen | 2,6-Diaminopyridines, process for their preparation and their use as coupling components for azo dyes |
| DE2230392A1 (en) * | 1972-06-22 | 1974-01-31 | Cassella Farbwerke Mainkur Ag | SUBSTITUTED PYRIDINE COMPOUNDS AND PROCESS FOR THEIR PRODUCTION |
| DK142675A (en) * | 1974-04-12 | 1975-10-13 | Sandoz Ag |
-
1971
- 1971-12-14 FR FR7144837A patent/FR2118075B1/fr not_active Expired
- 1971-12-14 NL NL7117139A patent/NL7117139A/xx unknown
- 1971-12-15 CH CH1830571A patent/CH582215A5/xx not_active IP Right Cessation
- 1971-12-16 SU SU1726602A patent/SU458133A3/en active
- 1971-12-17 CS CS879671A patent/CS166298B2/cs unknown
- 1971-12-17 BE BE776859A patent/BE776859A/en unknown
- 1971-12-17 GB GB5865371A patent/GB1377505A/en not_active Expired
- 1971-12-17 GB GB1692474A patent/GB1377506A/en not_active Expired
- 1971-12-18 IT IT5484871A patent/IT945532B/en active
- 1971-12-20 JP JP46102785A patent/JPS605618B1/ja active Granted
-
1977
- 1977-04-12 JP JP52041003A patent/JPS5931502B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| SU458133A3 (en) | 1975-01-25 |
| BE776859A (en) | 1972-06-19 |
| NL7117139A (en) | 1972-06-21 |
| JPS5373568A (en) | 1978-06-30 |
| IT945532B (en) | 1973-05-10 |
| FR2118075A1 (en) | 1972-07-28 |
| JPS605618B1 (en) | 1985-02-13 |
| CH582215A5 (en) | 1976-11-30 |
| CS166298B2 (en) | 1976-02-27 |
| GB1377506A (en) | 1974-12-18 |
| FR2118075B1 (en) | 1976-04-30 |
| GB1377505A (en) | 1974-12-18 |
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