JPH10251259A - 1,4,6,9-tetraza-5,10-dehydrophenazine derivative and its production - Google Patents
1,4,6,9-tetraza-5,10-dehydrophenazine derivative and its productionInfo
- Publication number
- JPH10251259A JPH10251259A JP7266797A JP7266797A JPH10251259A JP H10251259 A JPH10251259 A JP H10251259A JP 7266797 A JP7266797 A JP 7266797A JP 7266797 A JP7266797 A JP 7266797A JP H10251259 A JPH10251259 A JP H10251259A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- chloro
- formula
- dicyano
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000002904 solvent Substances 0.000 abstract description 20
- 150000001875 compounds Chemical class 0.000 abstract description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 238000009835 boiling Methods 0.000 abstract description 3
- 238000006471 dimerization reaction Methods 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 2
- CDKQWBZSAPRZNS-UHFFFAOYSA-N 5-amino-6-chloropyrazine-2,3-dicarbonitrile Chemical compound NC1=NC(C#N)=C(C#N)N=C1Cl CDKQWBZSAPRZNS-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 abstract 1
- 230000004043 responsiveness Effects 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 10
- 238000000746 purification Methods 0.000 description 10
- -1 nitrobenzene Chemical compound 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002988 phenazines Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C09B17/00—Azine dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
【発明の属する技術分野】本発明は、１００ｎｍを超え
る大きなストークスシフト値を有する蛍光性化合物であ
る、有機機能性色素として光波長変換材料や蛍光顔料分
野への応用のみならず、電気化学的安定なレドックス応
答性を示すことからエレクトロクロミズムやエレクトロ
ルミネッセンス用の有機電界発光素子としての利用が可
能である５，１０−デヒドロフェナジン誘導体に関す
る。[0001] The present invention relates to a fluorescent compound having a large Stokes shift value exceeding 100 nm. The present invention relates not only to the application to the field of light wavelength conversion materials and fluorescent pigments as an organic functional dye, but also to the electrochemical stability. The present invention relates to a 5,10-dehydrophenazine derivative which exhibits an excellent redox response and can be used as an organic electroluminescent device for electrochromism and electroluminescence.
【従来の技術】５，１０−デヒドロフェナジンは下記反
応式に従って製造された１化合物が知られているが収率
が５％以下と極端に悪く実質的には全く知られていない
化合物群である。2. Description of the Related Art 5,10-Dehydrophenazine is known as one compound produced according to the following reaction formula, but the yield is extremely low at 5% or less, and is a group of compounds which are substantially unknown at all. .
【化６】 Embedded image
【発明が解決しようとする課題】本発明の目的は機能性
色素として新規な５，１０−デヒドロフェナジン誘導体
及びその簡便で収率の良い合成法を提供することであ
る。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel 5,10-dehydrophenazine derivative as a functional dye and a simple and high-yield synthesis method thereof.
【課題を解決するための手段】簡便な合成法を鋭意検討
した結果、合成出発物質として２−アミノ−３−クロル
−５，６−ジシアノピラジンの塩基存在下における二量
化反応により目的物のジヒドロフェナジン類が収率良く
得られることを見出し（方法１）、また、２，３−ジク
ロロ−６，７−ジシアノ−１，４，５，８−テトラアザ
ナフタレンをジアミノマレオノニトリル（ＤＡＭＮ）と
反応させることにより得られることを見出し（方法２）
本発明を完成するに至った。即ち、本発明は一般式
［１］As a result of diligent studies on a simple synthesis method, dimerization of 2-amino-3-chloro-5,6-dicyanopyrazine in the presence of a base as a synthesis starting material is carried out to obtain the desired product, dihydrogen. It has been found that phenazines can be obtained in good yield (method 1). Finding out by reacting (Method 2)
The present invention has been completed. That is, the present invention relates to the general formula [1]
【化７】 （式中Ｒは水素原子、アリル基、置換基を有していても
よいアルキル基、置換基を有していてもよいアラルキル
基または置換基を有していてもよいアリール基を示
す。）で表わされる化合物及びその製造方法である。Embedded image (In the formula, R represents a hydrogen atom, an allyl group, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent.) And a method for producing the compound.
【発明の実施の形態】前記方法１を反応式で示すと以下
のとおりである。BEST MODE FOR CARRYING OUT THE INVENTION The above method 1 is represented by the following reaction formula.
【化８】 反応は、適当な溶媒中塩基存在下、室温から溶媒の沸点
の温度で、必要によっては窒素のような不活性ガス雰囲
気下で行われる。用いられる溶媒は通常ＤＭＦが使用さ
れるが、これに限定されるものではない。即ち、Ｎ−ジ
メチルアセトアミド、Ｎ−メチルピロリドン等のアミド
系の溶媒、クロルベンゼン、トルエン、キシレン、ニト
ロベンゼン等の芳香族系溶媒、ＴＨＦやジオキサンのよ
うなエーテル系溶媒が使用でき場合によっては混合して
もよい。塩基としてはトリエチルアミン、ピリジンのよ
うな有機塩基、炭酸ナトリウム、炭酸カリウムのような
炭酸塩、水酸化ナトリウム、水酸化カリウムのような水
酸化物等が使用できる。前記方法２を反応式で示すと以
下のとおりである。Embedded image The reaction is carried out in a suitable solvent in the presence of a base, at a temperature from room temperature to the boiling point of the solvent, and optionally under an atmosphere of an inert gas such as nitrogen. The solvent used is usually DMF, but is not limited thereto. That is, amide solvents such as N-dimethylacetamide and N-methylpyrrolidone, aromatic solvents such as chlorobenzene, toluene, xylene and nitrobenzene, and ether solvents such as THF and dioxane can be used and mixed in some cases. You may. Examples of the base include organic bases such as triethylamine and pyridine, carbonates such as sodium carbonate and potassium carbonate, and hydroxides such as sodium hydroxide and potassium hydroxide. The method 2 is represented by the following reaction formula.
【化９】 （式中、Ｘはハロゲン原子を示す。） 反応は、適当な溶媒中塩基存在下、室温から溶媒の沸点
の温度で、必要によっては窒素のような不活性ガス雰囲
気下で行われる。用いられる溶媒は通常Ｎ−ジメチルア
セトアミドが使用されるが、これに限定されるものでは
ない。即ち、ＤＭＦ、Ｎ−メチルピロリドン等のアミド
系の溶媒、ニトロベンゼン等の芳香族系溶媒、ＴＨＦや
ジオキサンのようなエーテル系溶媒が使用でき場合によ
っては混合して使用してもよい。方法１、方法２いずれ
の方法で反応させた場合も反応終了後は通常の処理を行
うことにより目的物を得ることが出来る。得られた化合
物の構造は、機器分析により同定した。Embedded image (In the formula, X represents a halogen atom.) The reaction is carried out in a suitable solvent in the presence of a base at a temperature from room temperature to the boiling point of the solvent, if necessary, in an atmosphere of an inert gas such as nitrogen. The solvent used is usually N-dimethylacetamide, but is not limited thereto. That is, amide solvents such as DMF and N-methylpyrrolidone, aromatic solvents such as nitrobenzene, and ether solvents such as THF and dioxane can be used. When the reaction is carried out by any of the methods 1 and 2, after completion of the reaction, the desired product can be obtained by performing a usual treatment. The structure of the obtained compound was identified by instrumental analysis.
【実施例】次に実施例を挙げて本発明を更に詳細に説明
する。 ［方法１］ 実施例１（化合物番号１） ２−アミノ−３−クロロ−４，５−ジシアノ−ピラジン
（０．３６ｇ、２ｍｍｏｌ）とトリエチルアミン（４．
５ｇ、４．４ｍｍｏｌ）をジメチルホルムアミド（ＤＭ
Ｆ）（１０ｍｌ）に混ぜた溶液を１０時間加熱還流した
後１Ｍ塩酸水溶液にあけた。生成した結晶を濾過し、水
及びエチルアルコールで洗浄した。洗浄した結晶を展開
溶媒として酢酸エチルを用いシリカゲルカラムクロマト
を行いオレンジの蛍光を有する目的物を０．２３ｇ（収
率７８％）得た。ｍｐ＞３００℃ 実施例２（化合物番号２） ２−メチルアミノ−３−クロロ−４，５−ジシアノ−ピ
ラジンとトリエチルアミンをＤＭＦ中に混合し実施例１
と同様な反応条件で行った。展開溶媒として酢酸エチル
／ｎ−ヘキサン（３／２）を用いカラムクロマトで分離
精製した。収率４３％、ｍｐ＞３００℃ 実施例３（化合物番号３） ２−ｎ−ブチルアミノ−３−クロロ−４，５−ジシアノ
−ピラジンとトリエチルアミンをＤＭＦ中に混合し実施
例１と同様な反応条件で行った。展開溶媒として酢酸エ
チル／ｎ−ヘキサン（６／１）を用いカラムクロマトで
分離精製した。収率３７％、ｍｐ：２６８〜２６９℃ 実施例４（化合物番号４） ２−ベンジルアミノ−３−クロロ−４，５−ジシアノ−
ピラジンとトリエチルアミンをＤＭＦ中に混合し実施例
１と同様な反応条件で行った。展開溶媒として酢酸エチ
ル／ｎ−ヘキサン（２／１）を用いカラムクロマトで分
離精製した。収率４６％、ｍｐ＞３００℃ 実施例５（化合物番号５） ２−アニリノ−３−クロロ−４，５−ジシアノ−ピラジ
ンとトリエチルアミンをＤＭＦ中に混合し実施例１と同
様な反応条件で行った。展開溶媒として酢酸エチル／ｎ
−ヘキサン（１／１）を用いカラムクロマトで分離精製
した。収率３８％、ｍｐ＞３００℃ 実施例６（化合物番号６） ２−ｐ−メチルアニリノ−３−クロロ−４，５−ジシア
ノ−ピラジンとトリエチルアミンをジメチルホルムアミ
ド中に混合し実施例１と同様な反応条件で行った。展開
溶媒としてトルエン／クロロフォルム（１／１）を用い
カラムクロマトで分離精製した。収率４９％、ｍｐ＞３
００℃ 実施例７（化合物番号７） ２−ｐ−ブチルアニリノ−３−クロロ−４，５−ジシア
ノ−ピラジンとトリエチルアミンをＤＭＦ中に混合し実
施例１と同様な反応条件で行った。展開溶媒として酢酸
エチル／ｎ−ヘキサン（１／１）を用いカラムクロマト
で分離精製した。収率６１％、ｍｐ：２９５〜２９７℃ 実施例８（化合物番号８） ２−ｐ−ブトキシアニリノ−３−クロロ−４，５−ジシ
アノ−ピラジンとトリエチルアミンをＤＭＦ中に混合し
実施例１と同様な反応条件で行った。展開溶媒として酢
酸エチル／ｎ−ヘキサン（１／１）を用いカラムクロマ
トで分離精製した。収率６１％、ｍｐ＞３００℃ 実施例９（化合物番号９） ２−ｐ−アセトアミドアニリノ−３−クロロ−４，５−
ジシアノ−ピラジンとトリエチルアミンをＤＭＦ中に混
合し実施例１と同様な反応条件で行った。展開溶媒とし
て酢酸エチルを用いカラムクロマトで分離精製した。収
率４５％、ｍｐ＞３００℃ 実施例１０（化合物番号１０） ２−ｐ−フェニルアゾアニリノ−３−クロロ−４，５−
ジシアノ−ピラジンとトリエチルアミンをＤＭＦ中に混
合し実施例１と同様な反応条件で行った。展開溶媒とし
て酢酸エチルを用いカラムクロマトで分離精製した。収
率２６％、ｍｐ＞３００℃ ［方法２］ 実施例１１（化合物番号１） ２，３−ジクロロ−６，７−ジシアノ−１，４，５，８
−テトラアザナフタレン（０．４６ｇ、２ｍｍｏｌ）と
ＤＡＭＮ（０．２ｇ、２ｍｍｏｌ）をジメチルアセトア
ミド（１０ｍｌ）に溶かした溶液を４８時間室温で撹拌
した。反応混合物を水中に注ぎ、析出した結晶を濾過し
水洗し乾燥した。カラムクロマトで精製し０．１ｇの結
晶を得た。この結晶は実施例１で得たものと同一物であ
った。前記実施例により製造した本発明化合物のスペク
トルデータを第１表に示す。Next, the present invention will be described in more detail with reference to examples. [Method 1] Example 1 (Compound No. 1) 2-amino-3-chloro-4,5-dicyano-pyrazine (0.36 g, 2 mmol) and triethylamine (4.
5 g, 4.4 mmol) in dimethylformamide (DM
The solution mixed in F) (10 ml) was heated under reflux for 10 hours and then poured into a 1M aqueous hydrochloric acid solution. The formed crystals were filtered and washed with water and ethyl alcohol. The washed crystals were subjected to silica gel column chromatography using ethyl acetate as a developing solvent to obtain 0.23 g (yield 78%) of an orange fluorescent target product. mp> 300 ° C. Example 2 (Compound No. 2) Example 1 by mixing 2-methylamino-3-chloro-4,5-dicyano-pyrazine and triethylamine in DMF.
The reaction was performed under the same reaction conditions as described above. Separation and purification were performed by column chromatography using ethyl acetate / n-hexane (3/2) as a developing solvent. Example 3 (Compound No. 3) 2-n-butylamino-3-chloro-4,5-dicyano-pyrazine and triethylamine were mixed in DMF, and the same reaction as in Example 1 was carried out. Performed under conditions. Separation and purification were performed by column chromatography using ethyl acetate / n-hexane (6/1) as a developing solvent. Yield 37%, mp: 268-269 ° C. Example 4 (Compound No. 4) 2-benzylamino-3-chloro-4,5-dicyano-
Pyrazine and triethylamine were mixed in DMF, and the reaction was performed under the same reaction conditions as in Example 1. Separation and purification were performed by column chromatography using ethyl acetate / n-hexane (2/1) as a developing solvent. Yield 46%, mp> 300 ° C. Example 5 (Compound No. 5) 2-anilino-3-chloro-4,5-dicyano-pyrazine and triethylamine were mixed in DMF, and the reaction was carried out under the same reaction conditions as in Example 1. Was. Ethyl acetate / n as developing solvent
Separation and purification were performed by column chromatography using -hexane (1/1). Yield 38%, mp> 300 ° C. Example 6 (Compound No. 6) 2-P-methylanilino-3-chloro-4,5-dicyano-pyrazine and triethylamine were mixed in dimethylformamide and reacted in the same manner as in Example 1. Performed under conditions. Separation and purification were performed by column chromatography using toluene / chloroform (1/1) as a developing solvent. Yield 49%, mp> 3
00 ° C. Example 7 (Compound No. 7) 2-p-butylanilino-3-chloro-4,5-dicyano-pyrazine and triethylamine were mixed in DMF, and the reaction was carried out under the same reaction conditions as in Example 1. Separation and purification were performed by column chromatography using ethyl acetate / n-hexane (1/1) as a developing solvent. Example 8 (Compound No. 8) 2-p-butoxyanilino-3-chloro-4,5-dicyano-pyrazine and triethylamine were mixed in DMF to give a yield of 61%. Performed under similar reaction conditions. Separation and purification were performed by column chromatography using ethyl acetate / n-hexane (1/1) as a developing solvent. Example 61 (Compound No. 9) 2-p-acetamidoanilino-3-chloro-4,5-
Dicyano-pyrazine and triethylamine were mixed in DMF and reacted under the same reaction conditions as in Example 1. Separation and purification were performed by column chromatography using ethyl acetate as a developing solvent. Example 10 (Compound No. 10) 2-p-phenylazoanilino-3-chloro-4,5-
Dicyano-pyrazine and triethylamine were mixed in DMF and reacted under the same reaction conditions as in Example 1. Separation and purification were performed by column chromatography using ethyl acetate as a developing solvent. Yield 26%, mp> 300 ° C. [Method 2] Example 11 (Compound No. 1) 2,3-dichloro-6,7-dicyano-1,4,5,8
-A solution of tetraazanaphthalene (0.46 g, 2 mmol) and DAMN (0.2 g, 2 mmol) dissolved in dimethylacetamide (10 ml) was stirred at room temperature for 48 hours. The reaction mixture was poured into water, and the precipitated crystals were filtered, washed with water and dried. Purification by column chromatography gave 0.1 g of crystals. The crystals were identical to those obtained in Example 1. Table 1 shows the spectrum data of the compound of the present invention produced according to the above Examples.
【表１】 [Table 1]
【発明の効果】本発明の新規なテトラアザデヒドロフェ
ナジン誘導体は、容易に製造でき光波長変換、電界発光
素子の材料あるいは蛍光色素として、また農医薬あるい
はその中間体として有用である。Industrial Applicability The novel tetraazadehydrophenazine derivative of the present invention can be easily produced and is useful as a material for light wavelength conversion and electroluminescent devices or as a fluorescent dye, or as an agricultural drug or an intermediate thereof.
Claims (3)
アルキル基、置換基を有してもよいアラルキル基または
置換基を有してもよいアリール基を示す］で表わされる
化合物。1. A compound of the general formula [1] [Wherein R represents a hydrogen atom, an allyl group, an alkyl group which may have a substituent, an aralkyl group which may have a substituent or an aryl group which may have a substituent] .
アミノ−３−クロル−５，６−ジシアノピラジンを塩基
で処理することを特徴とする一般式［１］ 【化３】 （式中、Ｒは前記と同じ意味を示す。）で表される化合
物の製造法。2. A compound of the general formula [2] (Wherein, R has the same meaning as described above).
General formula [1] wherein amino-3-chloro-5,6-dicyanopyrazine is treated with a base. (Wherein, R has the same meaning as described above).
−ジハロ−６，７−ジシアノ−１，４，５，８−テトラ
アザナフタレンとジアミノマレオノニトリルを反応させ
ることを特徴とする式［１′］ 【化５】 で表される化合物の製造法。3. A compound of the general formula [3] (Wherein, X represents a halogen atom)
-Dihalo-6,7-dicyano-1,4,5,8-tetraazanaphthalene and diaminomaleononitrile, wherein the compound is reacted with diaminomaleononitrile. A method for producing a compound represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7266797A JPH10251259A (en) | 1997-03-10 | 1997-03-10 | 1,4,6,9-tetraza-5,10-dehydrophenazine derivative and its production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7266797A JPH10251259A (en) | 1997-03-10 | 1997-03-10 | 1,4,6,9-tetraza-5,10-dehydrophenazine derivative and its production |
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|---|---|
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Family
ID=13495955
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7266797A Pending JPH10251259A (en) | 1997-03-10 | 1997-03-10 | 1,4,6,9-tetraza-5,10-dehydrophenazine derivative and its production |
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| JP (1) | JPH10251259A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010050496A1 (en) * | 2008-10-28 | 2010-05-06 | 出光興産株式会社 | Nitrogen-containing heterocyclic derivative and organic electroluminescence element using nitrogen-containing heterocyclic derivative |
| US8080327B1 (en) | 2011-06-27 | 2011-12-20 | Vinazene, Inc. | Electrical storage device utilizing pyrazine-based cyanoazacarbons and polymers derived therefrom |
-
1997
- 1997-03-10 JP JP7266797A patent/JPH10251259A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010050496A1 (en) * | 2008-10-28 | 2010-05-06 | 出光興産株式会社 | Nitrogen-containing heterocyclic derivative and organic electroluminescence element using nitrogen-containing heterocyclic derivative |
| US20110248251A1 (en) * | 2008-10-28 | 2011-10-13 | Idemitsu Kosan Co., Ltd. | Nitrogen-containing heterocyclic derivative and organic electroluminescence element using nitrogen-containing heterocyclic derivative |
| US8080327B1 (en) | 2011-06-27 | 2011-12-20 | Vinazene, Inc. | Electrical storage device utilizing pyrazine-based cyanoazacarbons and polymers derived therefrom |
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