JPH06510054A - Method for producing 5,6-dihydroxyindoline - Google Patents

Method for producing 5,6-dihydroxyindoline

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Publication number
JPH06510054A
JPH06510054A JP5504893A JP50489393A JPH06510054A JP H06510054 A JPH06510054 A JP H06510054A JP 5504893 A JP5504893 A JP 5504893A JP 50489393 A JP50489393 A JP 50489393A JP H06510054 A JPH06510054 A JP H06510054A
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hydrogen
group
alkyl group
dihydroxyindoline
producing
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クニューベル、ゲオルグ
コンラート、ギュンター
ミヒェル、ロスヴィタ
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ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン
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Priority claimed from PCT/EP1992/001939 external-priority patent/WO1993005017A1/en
Publication of JPH06510054A publication Critical patent/JPH06510054A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/16—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
    • B05B7/20—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed by flame or combustion
    • B05B7/201—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed by flame or combustion downstream of the nozzle
    • B05B7/205—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed by flame or combustion downstream of the nozzle the material to be sprayed being originally a particulate material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/16—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
    • B05B7/22—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc
    • B05B7/222—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc using an arc
    • B05B7/226—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc using an arc the material being originally a particulate material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/08—Flame spraying
    • B05D1/10—Applying particulate materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/30—Change of the surface
    • B05D2350/33—Roughening
    • B05D2350/40—Roughening by adding a porous layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2451/00—Type of carrier, type of coating (Multilayers)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2507/00—Polyolefins
    • B05D2507/01—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2601/00—Inorganic fillers
    • B05D2601/20—Inorganic fillers used for non-pigmentation effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers

Abstract

A process for coating substrates with heat-resistant polymers is proposed, which polymers are applied by thermal spraying processes with high jet velocity. The polymer is introduced into the relatively cold jet region. As thermal spraying processes, high-velocity flame spraying or atmospheric, vacuum or inert gas plasma spraying processes, in each case modified for high jet velocity, can be used. <IMAGE>

Description

【発明の詳細な説明】 ５．６−ノヒドロキシインドリンの製法本発明は、対応するエーテル先駆物質を 臭化水素でエーテル開裂した後、その水性反応混合物から直接、結晶化すること による、５．６−シヒドロキシインドリンの製法に関する。[Detailed description of the invention] 5. Preparation of 6-nohydroxyindoline The present invention describes the preparation of the corresponding ether precursor. Crystallization directly from the aqueous reaction mixture after ether cleavage with hydrogen bromide A method for producing 5,6-cyhydroxyindoline.

文献中、ンクロドーパミンおよびロイコノルエピツクロムという名でも知られて いる５、６−シヒドロキシインドリン、並びに２−カルボキシ−５，６−シヒド ロキシインドリン（同義語・ンクロドーバおよびロイコドーパクロム）は、医薬 および薬学の分野並びに染髪料において大変重要である。Also known in the literature as ncrodopamine and leuconolepituchrome. 5,6-cyhydroxyindoline, and 2-carboxy-5,6-cyhydro Roxiindoline (synonyms ncrodova and leucodopachrome) is a pharmaceutical It is of great importance in the field of pharmaceutics and hair dyes.

例えば、天然染髪料、いわゆるメラニンは、５．６−ンヒドロキジインドールの 酸化重合による生合成中に生成する。従って、髪を染める際、反応性染料先駆物 質として５．６−ンヒドロキシインドールを使用するという試みが、過去には多 くなされた。あいに（，５，６−シヒドロキシインドールは、水溶液中、その遊 離型およびその塩の形のどちらをとっても非常に不安定で、空中酸素が存在する と、不溶性で、着色した酸化物並びに重合物を生成し、そのものでは、髪を染色 固定することはできない。従って、染色剤中、５．６−シヒドロキシインドール そのもの、またはその塩を使用するという試みには、多大なる困難が伴う。For example, natural hair dye, so-called melanin, contains 5,6-hydroxydiindole. Produced during biosynthesis by oxidative polymerization. Therefore, when dyeing hair, reactive dye precursors There have been many attempts in the past to use 5,6-hydroxyindole as a It was destroyed. Unfortunately, in aqueous solution, 5,6-cyhydroxyindole Extremely unstable, both in demolding and in its salt form, in the presence of atmospheric oxygen produces insoluble, colored oxides and polymers, which by themselves do not dye hair. It cannot be fixed. Therefore, in the dye, 5,6-cyhydroxyindole Attempts to use it or its salts are fraught with great difficulties.

これとは対照的に、生擬態的に髪を染める際、顔料先駆物質として５．６−シヒ ドロキシインドリンを使用するということが提唱された。この方法では、既知で ある５、６−ンヒドロキシイントールの安定性問題に起因する不利益を全く受け ることなく生成する５、６−ノヒドロキシインドールから、メラニン染料と共に 天然染髪剤が得られる。In contrast, 5.6-SiH is used as a pigment precursor when dyeing hair biomimically. It has been proposed to use droxyindoline. This method uses the known There are no disadvantages due to stability issues with certain 5,6-hydroxy intole. From 5,6-nohydroxyindole, which is produced without A natural hair dye is obtained.

５．６−７ヒドロキシインドリンの調製は、Ｓ、Ｎ、ミノニラ（Ｍｉｓｈｒａ） とＧ、　Ａ。5. Preparation of 6-7 Hydroxyindoline S,N,Mishra and G, A.

スワン（Ｓｗａｎ）のジャーナル・オブ・ケミカル・ソサイエティ　［（Ｊ　、 　Ｃｈｅｗ、　Ｓｏｃ、　）Ｃ１１９６７，１４２４］に初めて記載された。著 者は、オートクレーブ中、１５０℃で、５．６−ンメトキシインドリンをエーテ ル開裂することにより、５゜６−シヒドロキシインドリンの塩酸溶液を得た。次 に、その溶液を蒸発させることにより濃縮して、その結果得られた粗原料物をエ ーテル／エタノールより精製した。あいにく、この方法では、幾つかの不利益が 伴う。Swan's Journal of Chemical Society [(J, Chew, Soc, ) C11967, 1424]. Author 5.6-ene methoxyindoline was etherified at 150°C in an autoclave. A hydrochloric acid solution of 5°6-dihydroxyindoline was obtained by cleavage. Next Then, the solution is concentrated by evaporation and the resulting crude material is evaporated. Purified from ether/ethanol. Unfortunately, this method has several disadvantages. Accompany.

（１）　オートクレーブ中でのエーテル開裂は、比較的大きなバッチを使用する 際に多大なる努力が必要であり、 （２）　粗原料物を回収するため、反応溶液を蒸発させることにより完全に濃縮 しなければならないので、多大なるエネルギー費を要し、また体積／時間収率は 減少し、また （３）　使用する際の安全性という点では、易燃性の有機溶媒からの再結晶化は 、重大な危険を冒す。(1) Ether cleavage in an autoclave uses a relatively large batch It requires a great deal of effort, (2) Completely concentrate by evaporating the reaction solution to recover the crude raw materials This requires a large amount of energy, and the volume/time yield is low. decrease and also (3) In terms of safety during use, recrystallization from flammable organic solvents is , taking serious risks.

Ｓ、Ｎ　ミノニラとＧ、　Ａ、スワンの方法による５、６−シヒドロキシインド リンの合成を基にして、Ｍピアテリー（Ｐ　１ａｔｅｌｌｉ）らは別の合成法を 開発したが、この合成法では、まず初めに、ドーパミンをノルエピクロムに酸化 し、そのノルエピクロムをロイコ化合物に還元して、そのロイコ化合物をトリア セチルジヒドロキ／インドリンに変換する。アセチル基が脱離した後、トリアセ チルジヒドロキシインドリンより、５．６−７ヒトロキシインドリンが粗原料の 形で得られる。S, N Minonilla and G, A, 5,6-cyhydroxyindo by the method of Swan Based on the synthesis of phosphorus, Piatelli et al. proposed another synthesis method. However, this synthesis method first oxidizes dopamine to norepicchrome. Then, the norepichrome is reduced to a leuco compound, and the leuco compound is converted into tria. Convert to cetyl dihydroxy/indoline. After the acetyl group is removed, triacetyl From tildihydroxyindoline, 5.6-7 hydroxyindoline is the crude raw material. Obtained in form.

精製は、Ｓ、ＮミノニラとＧ、　Ａ、スワンの方法に記載されている精製に準す る。Purification was carried out in accordance with the purification described in the methods of S, N Minonilla and G, A, Swan. Ru.

複雑な精製段階の他に、この方法にはまた、工業規模で適用できないものとする 多くの不利益がある。Besides the complex purification steps, this method also has some limitations that make it inapplicable on an industrial scale. There are many disadvantages.

（１）　酸化段階は、かなり稀釈した溶液（ドーパミン約０．５　ｇ／７りを用 いて行わなければならず、また （２）　中間体であるトリアセチルジヒドロキンキノリンをカラムクロマトグラ フィーで精製しなければならない。(1) The oxidation step uses a highly diluted solution (approximately 0.5 g/7ml of dopamine). must be carried out in accordance with (2) Column chromatography of the intermediate triacetyldihydroquine quinoline It must be refined with fees.

これに酷似している方法として、２−カルボキシー５．６−シヒドロキシイント リンの合成が、Ｈウィラー（Ｗｙｌｅｒ）とＪ、チョイヒ＝　−（Ｃｈｏｉｖｉ ｎｉ）のへルベチ力・ヒミカ・アクタ［（Ｈｅｌｖ、　Ｃｈｉｍ、　Ａｃｔａ） 、１９６１、（５１）１４７６コに記載された。ここでは、高稀薄溶液の状態に あるドーパメチルエステルを酸化して、ドーパクロムメチルエステルを生成し、 そのドーパクロムメチルエステルを還元して、ロイコドーパクロムメチルエステ ルを生成した後、これらをトリアセチル誘導体として単離した。次に、そのトリ アセチル誘導体を酸水解して、２−力ルホキンー５．６−シヒドロキシインドリ ン（ロイコドーパクロム）を生成した。しかし、この方法では、上記の不利益を 伴う。従って、著者は、分光特性決定に使用する数ミリグラムの生成物しか得ら れなかった。As a method very similar to this, 2-carboxy5,6-cyhydroxyinto The synthesis of phosphorus was carried out by H. Wyler and J. Choivi. ni)'s Helveti Power Himika Acta [(Helv, Chim, Acta) , 1961, (51) 1476. Here, in the state of a highly dilute solution Oxidize some dopa methyl ester to produce dopachrome methyl ester, The dopachrome methyl ester is reduced to leucodopachrome methyl ester. After producing the compounds, they were isolated as triacetyl derivatives. Then the tri Acid hydrolysis of acetyl derivatives yields 2-hydroxy-5,6-hydroxyindoly (leucodopachrome). However, this method does not have the above disadvantages. Accompany. Therefore, the authors obtained only a few milligrams of product for use in spectroscopic characterization. I couldn't.

欧州特許出願公開第４６２８５７号によれば、５．６−シヒドロキシインドリン は、５，６−シメトキシインドリンを臭化水素酸（ａｑｕｅｏｕｓ　ＨＢｒ）と 反応させることにより、調製することができる。反応後、臭化水素酸を留去し、 残渣をエタノール中に溶解し、活性炭で処理して、セライトを通してろ過する。According to European Patent Application No. 462,857, 5,6-cyhydroxyindoline is 5,6-simethoxyindoline with hydrobromic acid (aqueous HBr). It can be prepared by reacting. After the reaction, hydrobromic acid is distilled off, The residue is dissolved in ethanol, treated with activated carbon and filtered through Celite.

次に、エチルエーテルを添加して、５．６−シヒドロキシインドリンを結晶化す る。この方法は、工業的応用を非常に複雑なものとする。Next, add ethyl ether to crystallize the 5,6-cyhydroxyindoline. Ru. This method makes industrial application very complicated.

従って、５．６−ンヒトロキシインドリンの製法を改良する必要があり、特に、 比較的大規模で行うこともてきる５、６−シヒドロキシインドリンの製法が必要 である。Therefore, it is necessary to improve the method for producing 5.6-hydroxyindoline, and in particular, A method for producing 5,6-cyhydroxyindoline that can be carried out on a relatively large scale is required. It is.

ところで驚いたことに、対応するエーテル先駆物質を臭化水素酸と反応させて、 その水性反応混合物から直接、５．６−シヒドロキシインドリンを再結晶化する ことにより、５．６−ンヒドロキシインドリンが容易に得られるということが見 従って、本発明は、一般式（Ｉ）： ［式中、Ｒ１とＲ３は互いに独立して水素またはＣ１−４アルキル基を表し、Ｒ ２は水素、Ｃ１−４アルキル基またはカルボキシル基であるって示される５、６ −シヒドロキシインドリンの製法であって、一般式（Ｉ［）［式中、Ｒ１とＲ３ は互いに独立して水素またはＣ１−４アルキル基を表し、Ｒ４とＲ５はＣ１−４ アルキル基を表すか、またはそれらが結合している酸素原子と共にＣｌ−４アル キレンジオキシ基を形成しており、またＲ６は水素、Ｃ１−４アルキル基または Ｃ０ＯＲ’基あるいはＣ０ＮＲ’Ｒ’であり、Ｒ７とＲ８は水素またはＣ１−４ アルキル基である］で示されるインドリンエーテルを臭化水素酸と反応させて、 その水性反応混合物から直接、５．６−シヒドロキシインドリンを結晶化するこ とによる、５．６−シヒドロキシインドリンの製法に関する。By the way, surprisingly, by reacting the corresponding ether precursor with hydrobromic acid, Recrystallize 5,6-cyhydroxyindoline directly from its aqueous reaction mixture It has been found that 5,6-hydroxyindoline can be easily obtained by Therefore, the present invention provides general formula (I): [In the formula, R1 and R3 independently represent hydrogen or a C1-4 alkyl group, and R 5, 6 where 2 is hydrogen, C1-4 alkyl group or carboxyl group - A method for producing hydroxyindoline of the general formula (I[) [wherein R1 and R3 independently represent hydrogen or a C1-4 alkyl group, and R4 and R5 are C1-4 Cl-4alk represents an alkyl group or together with the oxygen atom to which they are attached It forms a kylenedioxy group, and R6 is hydrogen, a C1-4 alkyl group, or C0OR' group or C0NR'R', R7 and R8 are hydrogen or C1-4 is an alkyl group] is reacted with hydrobromic acid, Crystallizing 5,6-cyhydroxyindoline directly from the aqueous reaction mixture and a method for producing 5,6-cyhydroxyindoline.

本発明の好ましい一態様においては、式（Ｉ）および式（ＩＩ）におけるＲｓが 水素である。別の好ましい態様においては、式（Ｉ）および式（ＩＩ）における Ｒ１が水素またはメチル基であり、とりわけ水素である。In a preferred embodiment of the present invention, Rs in formula (I) and formula (II) is It is hydrogen. In another preferred embodiment, in formula (I) and formula (II) R1 is hydrogen or a methyl group, especially hydrogen.

本発明の製法において、通常、Ｒ４とＲ５がＣ１−４アルキル基であるインドリ ンエーテル（ＩＩ）を使用する。メチル基である場合には、エーテル開裂中、そ れらから臭化メチルが生成する。従って、互いに酸素原子が結合しているＲ４と Ｒ５がＣ５−４アルキレンジオキシ基（例えば、メチレンジオキシ基またはイソ プロピリデンジオキシ基）を形成しているインドリンエーテル（ｎ）を使用する のが有利な場合がある。この場合、エーテル開裂中に生成するプロミドは揮発性 が少なく、使用する際の安全性がより高いので好ましい。In the production method of the present invention, usually, indoline in which R4 and R5 are C1-4 alkyl groups ether (II) is used. If it is a methyl group, its Methyl bromide is produced from these. Therefore, R4 and R4, which have oxygen atoms bonded to each other, R5 is a C5-4 alkylenedioxy group (e.g., methylenedioxy group or iso using indoline ether (n) forming a propylidene dioxy group) may be advantageous. In this case, the bromide formed during ether cleavage is volatile It is preferable because it has less oxidation and is safer to use.

使用するインドリンエーテル（ＩＩ）は、遊離型あるいは塩の形（例えば、塩酸 塩）のどちらでも使用することができる。The indoline ether (II) used can be in free or salt form (e.g. hydrochloric acid salt) can be used.

本発明の製法は、臭化水素酸中、インドリンエーテル（ＩＩ）を加熱することに より、容易に行うことができる。基本的には、臭化水素酸の濃度に対して特に制 限はないが、４０〜６２％の溶液が好ましい。臭化水素とインドリンエーテル（ ■）のモル比は、３：１ないし３０：１、好ましくは５：１ないし１５：１の値 に調節する。次に、その反応混合物を還流しながら数時間加熱する。その反応混 合物を冷却するだけで、所望の５，６−シヒドロキシインドリン（Ｉ）の結晶が 析出する。吸引ろ過した後、乾燥すると、高純度の状態で５．６−シヒドロキシ インドリンが得られる。The production method of the present invention involves heating indoline ether (II) in hydrobromic acid. It can be done more easily. Basically, there are special controls on the concentration of hydrobromic acid. Although not limited, a 40-62% solution is preferred. Hydrogen bromide and indoline ether ( The molar ratio of (ii) is 3:1 to 30:1, preferably 5:1 to 15:1. Adjust to The reaction mixture is then heated under reflux for several hours. The reaction mixture Just by cooling the compound, the desired crystals of 5,6-cyhydroxyindoline (I) can be obtained. Precipitate. After suction filtration and drying, 5,6-cyhydroxy Indoline is obtained.

本発明の製法で得られる５、６−シヒドロキシインドリンは、ケラチン繊維、特 にヒトの頭髪の酸化着色剤に使用するタイプの酸化染料の先駆初雪として適当で ある。The 5,6-cyhydroxyindoline obtained by the production method of the present invention is suitable for use in keratin fibers, It is suitable as a pioneer of the type of oxidative dye used as an oxidative coloring agent for human hair. be.

本発明を何ら制限することなく、以下の実施例で説明する。The invention is illustrated by the following examples without any limitation.

窒素雰囲気下、５．６−ジメトキンインドリン１００　ｇ　（０，６ｍｏｌ）を 撹拌機付き容器に入れた後、６２％の臭化水素酸５００ｍ１（臭化水素６．６ｍ ｏｌ）を添加した。注意して加熱した後、その反応混合物を５時間還流した。６ ０℃まで冷却した後、その反応混合物をろ過して、−晩水冷すると、５．６−シ ヒドロキシインドリンの結晶が析出した。生成物を吸引ろ過し、減圧下で乾燥し た。Under a nitrogen atmosphere, add 100 g (0.6 mol) of 5.6-dimethquine indoline. After placing in a container with a stirrer, add 500 ml of 62% hydrobromic acid (6.6 ml of hydrogen bromide) ol) was added. After careful heating, the reaction mixture was refluxed for 5 hours. 6 After cooling to 0°C, the reaction mixture was filtered and cooled with water overnight to give 5.6-Si Crystals of hydroxyindoline were precipitated. The product was filtered with suction and dried under reduced pressure. Ta.

窒素雰囲気下、５．６−ノメトキシインドリン］、　Ｏｇを撹拌機付き容器に入 れて、濃塩酸（ＨＣＩ）５０＋＋１！を添加した。注意して加熱した後、その反 応混合物を５時間還流した。その反応混合物の薄層クロマトグラフィーでは、５ ．６−シメトキシインドリン領域または５．６−シヒドロキシインドリン領域の いずれも示窒素雰囲気下、５．６−ンメトキシインドリン１０ｇを撹拌機付き容 器に入れて、６７％のヨウ化水素酸５０ｍ１！を添加した。注意して加熱した後 、その反応混合物を５時間還流した。その反応混合物の薄層クロマトグラフィー では、５．６−シメトキシインドリン領域または５．６−シヒドロキシインドリ ン領域のいずれも示さなかった。Under a nitrogen atmosphere, put 5.6-nomethoxyindoline], Og into a container with a stirrer. Concentrated hydrochloric acid (HCI) 50++1! was added. After heating carefully, The reaction mixture was refluxed for 5 hours. Thin layer chromatography of the reaction mixture revealed that 5 ．． 6-simethoxyindoline region or 5.6-cyhydroxyindoline region In each case, 10 g of 5.6-n methoxyindoline was added in a container equipped with a stirrer under a nitrogen atmosphere. Pour into a container and add 50ml of 67% hydroiodic acid! was added. After careful heating , the reaction mixture was refluxed for 5 hours. Thin layer chromatography of the reaction mixture Then, the 5.6-cymethoxyindoline region or the 5.6-cyhydroxyindoline region None of these areas were shown.

比較例は、５．６−ジメトキンインドリンと臭化水素酸のみから、５．６−シヒ ドロキシインドリンが十分調製できるということを明確に示している。In the comparative example, 5.6-dimethquine indoline and hydrobromic acid were used alone. This clearly shows that droxyindoline can be adequately prepared.

フロントページの続き （７２）発明者　ミヒエル、ロスヴイタドイツ連邦共和国　デー−４０００デュ ッセルドルフ　１３、アードルフーコルビンクーシュトラアセ　２幡Continuation of front page (72) Inventor Michiel, Roswita Federal Republic of Germany Day-4000 Du Isseldorf 13, Adolf Colvin Kustraasse 2 Hata

Claims (4)

【特許請求の範囲】[Claims] １．一般式（Ｉ） ▲数式、化学式、表等があります▼（Ｉ）［式中、Ｒ１とＲ３は互いに独立して 水素またはＣ１−４アルキル基を表し、Ｒ２は水素、Ｃ１−４アルキル基または カルボキシル基である］で示される５，６−ジヒドロキシインドリンの製法であ って、一般式（ＩＩ）：▲数式、化学式、表等があります▼（ＩＩ）［式中、Ｒ １とＲ３は互いに独立して水素またはＣ１−４アルキル基を表し、Ｒ４とＲ５は Ｃ１−４イアルキル基を表すか、またはそれらが結合している酸素原子と共にＣ １−４アルキレンジオキシ基を形成しており、またＲ６は水素、Ｃ１−４アルキ ル基またはＣＯＯＲ７基あるいはＣＯＮＲ７Ｒａ８あり、Ｒ７とＲ８は水素また はＣ１−４アルキル基である］で示されるインドリンエーテルを臭化水素酸と反 応させて、その水性反応混合物から直接、５，６−ジヒドロキシインドリンを結 晶化することによる、５，６−ジヒドロキシインドリンの製法。1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R1 and R3 are independent of each other. Represents hydrogen or a C1-4 alkyl group, R2 is hydrogen, a C1-4 alkyl group, or This is a method for producing 5,6-dihydroxyindoline, which is a carboxyl group. So, general formula (II): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, R 1 and R3 independently represent hydrogen or a C1-4 alkyl group, and R4 and R5 represent represents a C1-4 alkyl group or together with the oxygen atom to which they are bonded 1-4 alkylene dioxy group is formed, and R6 is hydrogen, C1-4 alkyl or COOR7 group or CONR7Ra8, R7 and R8 are hydrogen or is a C1-4 alkyl group] is reacted with hydrobromic acid. In response, 5,6-dihydroxyindoline was directly synthesized from the aqueous reaction mixture. A method for producing 5,6-dihydroxyindoline by crystallization. ２．Ｒ３が水素である、請求項１に記載の製法。2. The method according to claim 1, wherein R3 is hydrogen. ３．Ｒ１が水素またはメチル基である、請求項１または２に記載の製法。3. The method according to claim 1 or 2, wherein R1 is hydrogen or a methyl group. ４．Ｒ１が水素である、請求項１〜３のいずれかに記載の製法。4. The method according to any one of claims 1 to 3, wherein R1 is hydrogen.
JP5504893A 1991-09-02 1992-08-24 Method for producing 5,6-dihydroxyindoline Pending JPH06510054A (en)

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Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5573682A (en) * 1995-04-20 1996-11-12 Plasma Processes Plasma spray nozzle with low overspray and collimated flow
DE19705671A1 (en) * 1997-02-14 1998-08-20 Heidelberger Druckmasch Ag Printing machine with a corrosion-protected printing unit cylinder
EP0897019B1 (en) * 1997-07-18 2002-12-11 ANSALDO RICERCHE S.r.l. Method and device for forming porous ceramic coatings, in particular thermal barrier coatings, on metal substrates
EP0939142A1 (en) 1998-02-27 1999-09-01 Ticona GmbH Thermal spray powder incorporating an oxidised polyarylene sulfide
EP0939143A1 (en) * 1998-02-27 1999-09-01 Ticona GmbH Thermal spray powder incorporating a particular high temperature polymer
US6406756B1 (en) 1999-06-24 2002-06-18 Ford Global Technologies, Inc. Thermally sprayed articles and method of making same
US6270849B1 (en) * 1999-08-09 2001-08-07 Ford Global Technologies, Inc. Method of manufacturing a metal and polymeric composite article
DE19959515A1 (en) * 1999-12-09 2001-06-13 Dacs Dvorak Advanced Coating S Process for plastic coating by means of a spraying process, a device therefor and the use of the layer
US20030165689A1 (en) * 2001-12-14 2003-09-04 Miller Edward A. Articles spray coated with non-melting polymer
US20030209610A1 (en) * 2001-12-14 2003-11-13 Edward Miller High velocity oxygen fuel (HVOF) method for spray coating non-melting polymers
FR2854086B1 (en) * 2003-04-23 2007-03-30 Saint Gobain Pont A Mousson FLAME COATING METHOD AND CORRESPONDING DEVICE
DE10319481A1 (en) 2003-04-30 2004-11-18 Linde Ag Laval nozzle use for cold gas spraying, includes convergent section and divergent section such that portion of divergent section of nozzle has bell-shaped contour
PL1506816T3 (en) * 2003-04-30 2013-06-28 Sulzer Metco Ag Laval nozzle for thermal or kinetical spraying
BR112012003369A2 (en) * 2009-08-14 2016-02-16 Univ Michigan direct thermal spray synthesis of lithium-ion battery components.
US8692150B2 (en) * 2011-07-13 2014-04-08 United Technologies Corporation Process for forming a ceramic abrasive air seal with increased strain tolerance
CN104008947B (en) * 2014-06-11 2016-01-13 北京大学 A kind of based on Secondary-emission multipbcation from current stabilization micro-coiled carbon fibers
CN106733283B (en) * 2016-12-03 2019-10-11 天长市金陵电子有限责任公司 A kind of energy-saving plastic spraying gum
EP3640229B1 (en) 2018-10-18 2023-04-05 Rolls-Royce Corporation Cmas-resistant barrier coatings
DE102021118093A1 (en) 2021-04-14 2022-10-20 MTU Aero Engines AG Powder injector holder and plasma torch to create a thermal spray coating

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB777984A (en) * 1954-01-26 1957-07-03 Montedison Spa Method for assuring the adhesion of polyethylene coatings to surfaces
FR1423539A (en) * 1964-02-06 1966-01-03 Basf Ag Coating of substrates with plastics
BE804524A (en) * 1973-09-06 1974-01-02 Soudure Autogene Elect PROCESS AND TORCH FOR COATING SURFACES WITH POWDERS IN PLASTIC MATERIAL BY MEANS OF PLASMA TORCH WITH INTERNAL ARC
US3958097A (en) * 1974-05-30 1976-05-18 Metco, Inc. Plasma flame-spraying process employing supersonic gaseous streams
US4386112A (en) * 1981-11-02 1983-05-31 United Technologies Corporation Co-spray abrasive coating
FR2550467B1 (en) * 1983-08-08 1989-08-04 Aerospatiale METHOD AND DEVICE FOR INJECTING A FINELY DIVIDED MATERIAL INTO A HOT GAS FLOW AND APPARATUS USING THE SAME
US4604306A (en) * 1985-08-15 1986-08-05 Browning James A Abrasive blast and flame spray system with particle entry into accelerating stream at quiescent zone thereof

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