JPS5910342B2 - Method for producing 3,3'-diindolenylidene - Google Patents
Method for producing 3,3'-diindolenylideneInfo
- Publication number
- JPS5910342B2 JPS5910342B2 JP49091735A JP9173574A JPS5910342B2 JP S5910342 B2 JPS5910342 B2 JP S5910342B2 JP 49091735 A JP49091735 A JP 49091735A JP 9173574 A JP9173574 A JP 9173574A JP S5910342 B2 JPS5910342 B2 JP S5910342B2
- Authority
- JP
- Japan
- Prior art keywords
- pyridine
- producing
- cupric acetate
- reaction
- solvent
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Indole Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は３ ・ ３’−ジインドレニニリデンの製造方
法に関するものであり、更に詳しくは、酢酸第二銅−ピ
リジン錯体の存在下に３ ・３’−ジイソドリルを反応
せしめて３ ・ ３’−ジインドレニニリデンの全く新
規な製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 3,3'-diindoleninylidene, and more specifically, a process for producing 3,3'-diisodolyl in the presence of a cupric acetate-pyridine complex. The present invention relates to a completely new method for producing 3.3'-diindolenylidene by reaction.
従来、３ ・ ３’−ジインドレニニリデンは例えば「
ジャーナル・オブ・ザ・ケミカル・ソサイアテイ（Ｊｏ
ｕｒｎａｌｏｆＴｈｅＣｈｅｍｉｃａｌＳｏｃｉｅｔｙ
ル１９５７年、４１４１頁に記載されている方法によつ
て合成されることが知られている。すなわち、例えば、
「ガゼツタ・キミカ・イタリアーナ（Ｇａ２２ｅｔｔａ
Ｃｈｉｍｉｃａｉｔａｌｉａｎａ）」、１９３９年、６
９巻、５６２頁に記載されている方法によつて合成され
る３ ・ ３’−ジイソドリルを酢酸エチルを溶媒とし
て、二酸化鉛と反応せしめて３ ・３’−ジインドレニ
ニリデンを得るという方法が採られてきた。しかるに上
記方法は、二酸化鉛が溶媒として使用する酢酸エチルに
不溶であるため反応系が不均一になるので大量の二酸化
鉛を使う必要がある。Conventionally, 3.3'-diindoleninylidene is, for example,
Journal of the Chemical Society (Jo
urnalofTheChemicalSociety
It is known that the compound can be synthesized by the method described in 1957, p. 4141. That is, for example,
``Gazetta Quimica Italiana (Ga22etta
Chimicaitaliana), 1939, 6
A method in which 3 3'-diisodolyl synthesized by the method described in Volume 9, page 562 is reacted with lead dioxide using ethyl acetate as a solvent to obtain 3 3'-diindoleninylidene. has been adopted. However, in the above method, since lead dioxide is insoluble in ethyl acetate used as a solvent, the reaction system becomes non-uniform, so it is necessary to use a large amount of lead dioxide.
それ故に大量の廃棄物が発生するという欠点を有するも
のであつた。本発明者らは上記欠点を解消せんとして鋭
意検討した結果、酢酸第二銅−ピリジン錯体を用いると
均一系の反応で効率よく３ ・ ３’−ジイソドリルか
ら３ ・３’−ジインドレニニリデンが得られるという
全く新規な製造法を見い出し本発明に到達した。Therefore, it had the disadvantage of generating a large amount of waste. The inventors of the present invention made extensive studies to solve the above drawbacks and found that using a cupric acetate-pyridine complex efficiently converts 3.3'-diisodolyl to 3.3'-diindoleninylidene in a homogeneous reaction. The present invention has been achieved by discovering a completely new manufacturing method that yields the following.
以下、本発明を詳細に説明する。The present invention will be explained in detail below.
本発明に用いられる溶媒としては、ピリジン、ベンゼン
、エタノール、メタノール等の各種溶媒を任意に選択し
て単独または混合物で用いることが出来る。As the solvent used in the present invention, various solvents such as pyridine, benzene, ethanol, and methanol can be arbitrarily selected and used alone or in a mixture.
溶媒は一義的に決めることは出来ないが、３ ・ ３’
−ジイソドリルおよび酢酸第二銅−ピリジン錯体の溶解
性、溶媒の沸点等々を考慮するとピリジンを用いるのが
好適である。酢酸第二銅の３ ・ ３’−ジイソドリル
に対する仕込重量比は任意であるが、例えば溶媒にピリ
ジンを採用する場合は１〜１５０重量％までの広い範囲
を採用できる。Although the solvent cannot be determined unambiguously, 3 ・ 3'
- Considering the solubility of the diisodolyl and cupric acetate-pyridine complex, the boiling point of the solvent, etc., it is preferable to use pyridine. The weight ratio of cupric acetate to 3.3'-diisodolyl is arbitrary, but for example, when pyridine is used as the solvent, a wide range of 1 to 150% by weight can be adopted.
また、反応を均一系で実施するには酢酸第二銅のピリジ
ンに対する仕込重量比はつ １〜４重量％が好ましい。
反応温度は反応時間との関連から一義的に決めることは
出来ないが、室温から１１５℃、好ましくは６０℃から
１１５℃までの広い範囲を採用できる。反応生成物から
３ ・ ３’−ジインドレニニリデン５ を単離精製す
るには次の様にして行なう。In order to carry out the reaction in a homogeneous system, the weight ratio of cupric acetate to pyridine is preferably 1 to 4% by weight.
Although the reaction temperature cannot be determined uniquely in relation to the reaction time, a wide range from room temperature to 115°C, preferably from 60°C to 115°C can be adopted. Isolation and purification of 3.3'-diindolenylidene 5 from the reaction product is carried out as follows.
すなわち、反応の際に用いた溶媒を減圧下において濃縮
した後、更に反応生成物中の酢酸第二銅−ピリジノ錯体
を除去するため、水洗するか、あるいは、適当な溶媒を
用いて抽出するかの方法が採用される。更に高純度の製
品が所望なら再結晶法および／またはカラムクロマトグ
ラフイーによつて精製が繰り返えされる。本発明の方法
により得られた目的物は、ハロゲン化ビニル単量体また
はハロゲン化ビニル単量体およびこれと共重合可能なビ
ニル系単量体混合物の懸濁重合もしくは乳化重合に際し
、重合機械壁等に生ずる重合体スケールの付着を皆無に
するための塗布剤として著効を有するものである。That is, after concentrating the solvent used in the reaction under reduced pressure, in order to further remove the cupric acetate-pyridino complex in the reaction product, it is either washed with water or extracted using an appropriate solvent. method will be adopted. If a product of even higher purity is desired, purification is repeated by recrystallization and/or column chromatography. The target product obtained by the method of the present invention can be obtained from the polymerization machine wall during suspension polymerization or emulsion polymerization of a halogenated vinyl monomer or a mixture of a halogenated vinyl monomer and a vinyl monomer copolymerizable therewith. It is highly effective as a coating agent for completely eliminating the adhesion of polymer scale that occurs on other surfaces.
以下、実施例を挙げて更に詳細に説明するが、本発明は
これらに限定されるものではない。実施例 １かきまぜ
機、温度計、還流冷却器および試料注入口を有する四つ
ロフラスコにピリジン２０ｍ１！を入れておき、その中
に酢酸第二銅０．３ｆを加える。Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 20 ml of pyridine in a four-loop flask with stirrer, thermometer, reflux condenser and sample inlet! and add 0.3f of cupric acetate to it.
内容物は発熱し濃青色となつて酢酸第二銅−ピリ〉ジｙ
錯体が生成する。更に、３ ・ ３’−ジインドリル１
ｔをピリジン２０“に溶解し、上記四つロフラスコに追
加する。８０℃、８時間反応せしめた後、反応生成物を
減圧下にピリジンを濃縮した。The contents generate heat and turn dark blue, turning into cupric acetate.
A complex is formed. Furthermore, 3.3'-diindolyl 1
t was dissolved in 20" of pyridine and added to the above-mentioned four-walled flask. After reacting at 80° C. for 8 hours, the pyridine of the reaction product was concentrated under reduced pressure.
得られた生成物をアセトン１００ｍ１で抽出した後、ア
セトン抽出液を濃縮、更に生成物を酢酸エチルから再結
晶を繰り返えし３ ・ ３’−ジインドレニニリデン２
００ｍ９を得た゜生成物の構造の確認は薄層クロマトグ
ラフイー、融点によつてジヤーナル・オブ・ザ・ケミカ
ル・ソサイアテイ、１９５７年、４１４１頁に記載され
ている方法によつて得られる３ ・３’−ジインドレニ
ニリデンのそれらと比較して行つた。After extracting the obtained product with 100 ml of acetone, the acetone extract was concentrated, and the product was repeatedly recrystallized from ethyl acetate to obtain 3.3'-diindoleninylidene 2
00m9 was obtained. The structure of the product was confirmed by thin layer chromatography and melting point by the method described in Journal of the Chemical Society, 1957, p. 4141.3.3 '-diindoleninylidene.
吸着剤としてシリカゲル（ワコーゲルＢ−５Ｆ）、展開
溶媒としてエタノールリベンゼン＝ １：９を用いて行
つたときの薄層クロマトグラフイーのＲｆ値および融点
を表−１に示した。上記結果から、３ ・ ３’−ジイ
ンドレニニリデンが生成していることが確認された。Table 1 shows the Rf value and melting point of thin layer chromatography performed using silica gel (Wako Gel B-5F) as an adsorbent and ethanol-livenzene=1:9 as a developing solvent. From the above results, it was confirmed that 3.3'-diindoleninylidene was produced.
実施例 ２
実施例１と同様の四つロフラスコにあらかじめ酢酸第二
銅ＩＶとピリジン３“とから酢酸第二銅一ビリジｙ錯体
を合成しておき、その中にエタノール２０ゴを加える。Example 2 A cupric acetate-viridiy complex was synthesized in advance from cupric acetate IV and pyridine 3'' in a four-bottle flask similar to that in Example 1, and 20 g of ethanol was added thereto.
更に、３ ・ ３’−ジインドリル１ｔをエタノール２
０ゴに溶解し、上記四つ口フラスコに追加する。８０℃
、１２時間反応せしめた後、反応生成物を実施例１と同
様に処理し、精製を繰り返えし３・イージインドレニニ
リデン１００Ｗ１ｆ７を得た。Furthermore, 1 t of 3-3'-diindolyl was added to 2 t of ethanol.
Dissolve in 0.0 g and add to the four-necked flask. 80℃
After reacting for 12 hours, the reaction product was treated in the same manner as in Example 1, and the purification was repeated to obtain 3-Ediindoleninylidene 100W1f7.
実施例１と同様に行つた薄層クロマトグラフイーおよび
融点の測定結果を表−２に示した。The results of thin layer chromatography and melting point measurements conducted in the same manner as in Example 1 are shown in Table 2.
Claims (1)
−ジインドレニニリデンを製造するにあたり、触媒とし
て酢酸第二銅−ピリジン錯体を用いることを特徴とする
３・３′−ジインドレニニリデンの製造法。1 3.3' using 3.3'-diisodolyl as a starting material
- A method for producing 3,3'-diindolenylidene, which comprises using a cupric acetate-pyridine complex as a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP49091735A JPS5910342B2 (en) | 1974-08-09 | 1974-08-09 | Method for producing 3,3'-diindolenylidene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP49091735A JPS5910342B2 (en) | 1974-08-09 | 1974-08-09 | Method for producing 3,3'-diindolenylidene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5119763A JPS5119763A (en) | 1976-02-17 |
| JPS5910342B2 true JPS5910342B2 (en) | 1984-03-08 |
Family
ID=14034762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP49091735A Expired JPS5910342B2 (en) | 1974-08-09 | 1974-08-09 | Method for producing 3,3'-diindolenylidene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5910342B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5877055A (en) * | 1981-10-30 | 1983-05-10 | Ozen Corp | Multiplex audio reproducer having record disk driven by cord wind-up constant torque spring and started by start selecting lever |
-
1974
- 1974-08-09 JP JP49091735A patent/JPS5910342B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5119763A (en) | 1976-02-17 |
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