JP2001002661A - Nitrile compound and its production - Google Patents
Nitrile compound and its productionInfo
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- JP2001002661A JP2001002661A JP11175234A JP17523499A JP2001002661A JP 2001002661 A JP2001002661 A JP 2001002661A JP 11175234 A JP11175234 A JP 11175234A JP 17523499 A JP17523499 A JP 17523499A JP 2001002661 A JP2001002661 A JP 2001002661A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電子輸送材料、電
荷発生材料、光学記録材料、光電変換材料あるいはそれ
らの中間体等として有用な、新規ニトリル誘導体および
その製造方法に関する。The present invention relates to a novel nitrile derivative useful as an electron transporting material, a charge generating material, an optical recording material, a photoelectric conversion material or an intermediate thereof, and a method for producing the same.
【０００２】[0002]
【従来の技術】ニトリル誘導体はこれまで数多くの化合
物が合成されている（フタロシアニン−化学と機能−白
井・小林著）。特にフタロニトリル誘導体については、
主にフタロシアニンを初めとするアザアヌレン化合物の
原料として有効であることから、置換基、置換位置の異
なる化合物が多く合成されている。ピラジン環を有する
ニトリル誘導体としては、例えば、Journal of Chemica
lSociety，911（1937）；Journal of the American Che
mical Society，85,668（1963）、特開平９−２４１２
４６に記述されており、またこれらピラジン環を有する
ニトリル誘導体の、アザアヌレン化合物の原料としての
応用例として、例えば、特許公報２６３７４８７号、特
開平２−１４４５４７、特開昭６４−３４７９１を挙げ
られる。2. Description of the Related Art Many nitrile derivatives have been synthesized so far (phthalocyanine-chemistry and function-by Shirai and Kobayashi). Especially for phthalonitrile derivatives,
Since it is mainly effective as a raw material for azaannulene compounds such as phthalocyanine, many compounds having different substituents and substitution positions have been synthesized. Examples of the nitrile derivative having a pyrazine ring include, for example, Journal of Chemica
lSociety, 911 (1937); Journal of the American Che
mical Society, 85,668 (1963), JP-A-9-2412
46, and examples of application of these nitrile derivatives having a pyrazine ring as starting materials for azaannulene compounds include, for example, JP-A-2637487, JP-A-2-14447, and JP-A-64-34791.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、電子
輸送材料、電荷発生材料、光学記録材料、光電変換材料
あるいはそれらの中間体等として有用な、新規ニトリル
誘導体の提供、及び該新規ニトリル誘導体を簡便に、且
つ高収率で製造できる製造方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel nitrile derivative useful as an electron transporting material, a charge generating material, an optical recording material, a photoelectric conversion material or an intermediate thereof, and the novel nitrile. It is an object of the present invention to provide a method for producing a derivative in a simple and high yield.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、ニトリル
誘導体及びその製造方法について鋭意検討した結果、新
規ニトリル誘導体、及び、その簡便かつ高収率な製造方
法を見出すに至り、本発明を完成させた。Means for Solving the Problems As a result of intensive studies on the nitrile derivative and the production method thereof, the present inventors have found a novel nitrile derivative and a simple and high-yield production method thereof. Completed.
【０００５】第一の発明は、下記一般式（１）で示され
るニトリル誘導体である。[0005] The first invention is a nitrile derivative represented by the following general formula (1).
【化５】 （式中、Ｒ1は水素原子、置換もしくは無置換の低級ア
ルキル基又は置換もしくは無置換のアリール基を表し、
ｎは１又は２を表す。）Embedded image (Wherein, R 1 represents a hydrogen atom, a substituted or unsubstituted lower alkyl group or a substituted or unsubstituted aryl group,
n represents 1 or 2. )
【０００６】第２の発明は、下記（３）式で表される化
合物である第１の発明のニトリル誘導体である。The second invention is a nitrile derivative according to the first invention, which is a compound represented by the following formula (3).
【化６】 （式中、ｎは１又は２を表す。）Embedded image (In the formula, n represents 1 or 2.)
【０００７】第３の発明は、下記（４）式で表される化
合物である第１の発明のニトリル誘導体である。A third invention is a nitrile derivative according to the first invention, which is a compound represented by the following formula (4).
【化７】 （式中、ｎは１又は２を表す。） 第４の発明は、下記一般式（２）で示されるケトン化合
物と、ジアミノマレオニトリルを反応させることを特徴
とする、第１の発明のニトリル化合物の製造方法であ
る。Embedded image (In the formula, n represents 1 or 2.) A fourth invention is a nitrile according to the first invention, wherein a ketone compound represented by the following general formula (2) is reacted with diaminomaleonitrile. This is a method for producing a compound.
【化８】 （式中、Ｒ1は水素原子、置換もしくは無置換の低級ア
ルキル基又は置換もしくは無置換のアリール基を表し、
ｎは１又は２を表す。） 本発明のニトリル誘導体を、例えばフタロニトリル化合
物又は１，３−ジイミノイソインドリン化合物と反応さ
せることにより、例えば電子輸送材料、電荷発生材料、
光学記録材料、光電変換材料として有用なテトラアザポ
ルフィリン誘導体混合物を得ることができる。Embedded image (Wherein, R 1 represents a hydrogen atom, a substituted or unsubstituted lower alkyl group or a substituted or unsubstituted aryl group,
n represents 1 or 2. By reacting the nitrile derivative of the present invention with, for example, a phthalonitrile compound or a 1,3-diiminoisoindoline compound, for example, an electron transport material, a charge generation material,
A tetraazaporphyrin derivative mixture useful as an optical recording material and a photoelectric conversion material can be obtained.
【０００８】[0008]
【発明の実施の形態】本発明に使用されるニトリル誘導
体及び、その製造方法について更に詳細に述べる。一般
式（１）で示される新規ニトリル化合物において、Ｒ1
は水素原子、置換もしくは無置換の低級アルキル基、又
は置換もしくは無置換のアリール基である。置換又は無
置換の低級アルキル基としては例えばメチル基、エチル
基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｔｅｒｔ−
ブチル基、ｓｅｃ−ブチル基、ｎ−ブチル基、ｉｓｏ−
ブチル基、トリフルオロメチル基等が挙げられ、置換又
は無置換のアリール基としてはフェニル基、ナフチル
基、ビフェニリル基等が挙げられ、これらは上記の置換
又は無置換の低級アルキル基を有しても良い。本発明で
使用する新規ニトリル誘導体は、例えば、下記の反応式
に従って製造することができる。BEST MODE FOR CARRYING OUT THE INVENTION The nitrile derivative used in the present invention and a method for producing the same will be described in more detail. In the novel nitrile compound represented by the general formula (1), R 1
Is a hydrogen atom, a substituted or unsubstituted lower alkyl group, or a substituted or unsubstituted aryl group. Examples of the substituted or unsubstituted lower alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group and a tert-
Butyl group, sec-butyl group, n-butyl group, iso-
Butyl group, trifluoromethyl group and the like, and the substituted or unsubstituted aryl group include a phenyl group, a naphthyl group, a biphenylyl group and the like, which have the above-mentioned substituted or unsubstituted lower alkyl group. Is also good. The novel nitrile derivative used in the present invention can be produced, for example, according to the following reaction formula.
【化９】 （式中、ｎは１又は２である。ｎが２の場合はジフェニ
レン基を表す）Embedded image (In the formula, n is 1 or 2. When n is 2, it represents a diphenylene group.)
【０００９】反応は通常無溶媒か、エタノール、ブタノ
ール等のアルコール系溶媒、ベンゼン、トルエン、ニト
ロベンゼン等の芳香族系溶媒、ジクロロベンゼン、トリ
クロロベンゼン等のハロゲン系溶剤、ジオキサン、テト
ラヒドロフラン等のエーテル系溶剤、酢酸等の酸性溶媒
の存在下で加熱することにより得ることができる。反応
収率、原料の溶解性向上の目的で、酢酸、硫酸、塩酸又
はｐ−トルエンスルホン酸等の酸性触媒の存在下で反応
させることが好ましい。反応温度は通常室温〜３００℃
で行い、特に４０℃〜２００℃で行うことが、反応収率
の点から好ましい。表１に、本発明で使用される具体的
なニトリル誘導体の構造を示すが、本発明はこれらに限
定されるものではない。The reaction is usually carried out without solvent, alcoholic solvents such as ethanol and butanol, aromatic solvents such as benzene, toluene and nitrobenzene, halogen solvents such as dichlorobenzene and trichlorobenzene, ether solvents such as dioxane and tetrahydrofuran. , Acetic acid or the like, by heating in the presence of an acidic solvent. For the purpose of improving the reaction yield and the solubility of the raw materials, the reaction is preferably performed in the presence of an acidic catalyst such as acetic acid, sulfuric acid, hydrochloric acid or p-toluenesulfonic acid. Reaction temperature is usually from room temperature to 300 ° C
The reaction is preferably performed at 40 ° C. to 200 ° C. from the viewpoint of the reaction yield. Table 1 shows the structures of specific nitrile derivatives used in the present invention, but the present invention is not limited to these.
【００１０】[0010]
【表１】 [Table 1]
【００１１】[0011]
【実施例】以下、本発明を実施例により説明するが、こ
れにより本発明の態様が限定されるものではない。EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.
【００１２】実施例１ 下記（５）式のニトリル誘導体の合成Example 1 Synthesis of a nitrile derivative represented by the following formula (5)
【化１０】 １，４−ビスベンジル０．１ｍｏｌ、ジアミノマレオニ
トリル０．２ｍｏｌ、酢酸を、還流下で、６時間攪拌し
た。室温まで自然冷却した後、析出した結晶をろ取し
た。これをカラムクロマトグラフィーにより単離し、粗
生成物を得た。展開溶媒としてはクロロホルムを使用し
た。これに再結晶溶媒トルエンを用いて、再結晶を行な
い、収率８０％でニトリル誘導体（５）を得た。融点は
２７２〜２７８℃であった。図１に、実施例１で得たニ
トリル誘導体の赤外吸収スペクトルを示す。元素分析結
果を表２に示す。Embedded image 0.1 mol of 1,4-bisbenzyl, 0.2 mol of diaminomaleonitrile and acetic acid were stirred under reflux for 6 hours. After naturally cooling to room temperature, the precipitated crystals were collected by filtration. This was isolated by column chromatography to obtain a crude product. Chloroform was used as a developing solvent. This was recrystallized using a recrystallization solvent toluene to obtain a nitrile derivative (5) with a yield of 80%. Melting point was 272-278 ° C. FIG. 1 shows an infrared absorption spectrum of the nitrile derivative obtained in Example 1. Table 2 shows the results of the elemental analysis.
【００１３】[0013]
【表２】 [Table 2]
【００１４】実施例２ 下記（６）式のニトリル誘導体の合成Example 2 Synthesis of a nitrile derivative represented by the following formula (6)
【化１１】 式（６）で示すニトリル誘導体を、以下に示す合成路に
従い合成した。（下記反応式中ＤＡＭＮはジアミノマレ
オニトリルを表す。）Embedded image The nitrile derivative represented by the formula (6) was synthesized according to the following synthetic route. (In the following reaction formula, DAMN represents diaminomaleonitrile.)
【化１２】 Embedded image
【００１５】反応器中に、ＳｅＯ2を０．１５ｍｏｌ、
ジオキサンを１２０ｍｌ、水を５ｍｌ取り、１時間５０
℃で加熱攪拌した後、あらかじめジオキサン２０ｍｌに
（ａ）０．０５ｍｏｌを加えた溶液を滴下した。その後
還流下で８時間加熱反応した後、熱時ろ過により不溶部
を除去し、ろ液中の溶媒を留去し（ｂ）を得た。ここで
得た（ｂ）に、ジアミノマレオニトリル０．１ｍｏｌ、
ジオキサン２００ｍｌ、ｐ−トルエンスルホン酸０．０
１ｍｏｌを加え、ｒｅｆｌｕｘ下で２時間加熱反応した
後に放冷し、溶媒を留去した。これにメタノール２００
ｍｌを加えて攪拌し、ろ過する事により結晶をろ取し
た。この結晶をメタノールで数回洗浄した後乾燥した。
この結晶をカラムクロマトグラフィーにより単離し、粗
生成物を得た。展開溶媒としてはジクロロメタンを使用
した。これに再結晶溶媒ジオキサンを用いて、再結晶を
行ない、収率６０％でニトリル誘導体（６）を得た。融
点は３３０〜３３７℃であった。図２に、実施例２で得
たニトリル誘導体の赤外吸収スペクトルを示す。元素分
析結果を表３に示す。In a reactor, 0.15 mol of SeO 2 was added.
Take 120 ml of dioxane and 5 ml of water for 1 hour 50
After heating and stirring at ℃, a solution of (a) 0.05 mol previously added to 20 ml of dioxane was added dropwise. Thereafter, the mixture was heated and reacted under reflux for 8 hours. Then, the insoluble portion was removed by hot filtration, and the solvent in the filtrate was distilled off to obtain (b). In the obtained (b), 0.1 mol of diaminomaleonitrile,
Dioxane 200 ml, p-toluenesulfonic acid 0.0
After adding 1 mol, the mixture was heated and reacted under reflux for 2 hours, and then allowed to cool, and the solvent was distilled off. 200 ml of methanol
The mixture was stirred, filtered, and the crystals were collected by filtration. The crystals were washed several times with methanol and dried.
The crystals were isolated by column chromatography to obtain a crude product. Dichloromethane was used as a developing solvent. This was recrystallized using a recrystallization solvent dioxane to obtain a nitrile derivative (6) in a yield of 60%. Melting point was 330-337 ° C. FIG. 2 shows an infrared absorption spectrum of the nitrile derivative obtained in Example 2. Table 3 shows the results of the elemental analysis.
【００１６】[0016]
【表３】 [Table 3]
【００１７】実施例３ 下記（７）式のニトリル誘導体の合成Example 3 Synthesis of a nitrile derivative represented by the following formula (7)
【化１３】 Embedded image
【００１８】反応器中に、ＳｅＯ2を０．１２ｍｏｌ、
ジオキサンを１２０ｍｌ、水を４ｍｌ取り、１時間５０
℃で加熱攪拌した後、あらかじめジオキサン２０ｍｌに
（ｃ）０．０５ｍｏｌを加えた溶液を滴下した。その後
還流下で８時間加熱反応した後、熱時ろ過により不溶部
を除去し、ろ液中の溶媒を除去し(ｄ)を得た。ここで得
た（ｄ）に、ジアミノマレオニトリル０．１ｍｏｌ、ジ
オキサン２００ｍｌ、ｐ−トルエンスルホン酸０．０１
ｍｏｌを加え、還流下で２時間加熱反応した後に放冷
し、溶媒を留去した。これにメタノール２００ｍｌを加
えて攪拌し、ろ過する事により結晶をろ取した。この結
晶をメタノールで数回洗浄した後乾燥した。この結晶を
カラムクロマトグラフィーにより単離し、粗生成物を得
た。展開溶媒としてはジクロロメタンを使用した。これ
に再結晶溶媒ジオキサンを用いて、再結晶を行い、収率
５５％でニトリル誘導体(７)を得た。融点は２７９〜２
８４℃であった。図３に、実施例３で得たニトリル誘導
体の赤外吸収スペクトルを示す。In a reactor, 0.12 mol of SeO 2 was added.
Take 120 ml of dioxane and 4 ml of water for 1 hour 50
After heating and stirring at ℃, a solution in which 0.05 mol of (c) was previously added to 20 ml of dioxane was added dropwise. Then, after performing a heating reaction under reflux for 8 hours, the insoluble portion was removed by hot filtration, and the solvent in the filtrate was removed to obtain (d). To the obtained (d), 0.1 mol of diaminomaleonitrile, 200 ml of dioxane, 0.01 p-toluenesulfonic acid
The reaction mixture was heated under reflux for 2 hours, allowed to cool, and the solvent was distilled off. To this, 200 ml of methanol was added, and the mixture was stirred and filtered to collect crystals. The crystals were washed several times with methanol and dried. The crystals were isolated by column chromatography to obtain a crude product. Dichloromethane was used as a developing solvent. This was recrystallized using a recrystallization solvent dioxane to obtain a nitrile derivative (7) with a yield of 55%. Melting point 279-2
84 ° C. FIG. 3 shows an infrared absorption spectrum of the nitrile derivative obtained in Example 3.
【００１９】[0019]
【表４】 [Table 4]
【００２０】[0020]
【発明の効果】実施例に示すように、本発明によれば、
簡便な製造方法により、高収率で新規ニトリル誘導体の
提供が可能となる。As shown in the embodiments, according to the present invention,
By a simple production method, a novel nitrile derivative can be provided in high yield.
【図１】 実施例１で得たテニトリル誘導体の赤外吸収
スペクトルを示す。FIG. 1 shows an infrared absorption spectrum of the tenitrile derivative obtained in Example 1.
【図２】 実施例２で得たテニトリル誘導体の赤外吸収
スペクトルを示す。FIG. 2 shows an infrared absorption spectrum of the tenitrile derivative obtained in Example 2.
【図３】 実施例３で得たテニトリル誘導体の赤外吸収
スペクトルを示す。FIG. 3 shows an infrared absorption spectrum of the tenitrile derivative obtained in Example 3.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 南場 道彦 東京都大田区中馬込１丁目３番６号 株式 会社リコー内 (72)発明者 島田 知幸 東京都大田区中馬込１丁目３番６号 株式 会社リコー内 (72)発明者 田中 千秋 東京都大田区中馬込１丁目３番６号 株式 会社リコー内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Michihiko Nanba 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Tomoyuki Shimada 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Chiaki Tanaka 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd.
Claims (4)
導体。 【化１】 （式中、Ｒ1は水素原子、置換もしくは無置換の低級ア
ルキル基又は置換もしくは無置換のアリール基を表し、
ｎは１又は２を表す）1. A nitrile derivative represented by the following general formula (1). Embedded image (Wherein, R 1 represents a hydrogen atom, a substituted or unsubstituted lower alkyl group or a substituted or unsubstituted aryl group,
n represents 1 or 2)
求項１記載のニトリル誘導体。 【化２】 （式中、ｎは１又は２を表す。）2. The nitrile derivative according to claim 1, which is a compound represented by the following formula (3). Embedded image (In the formula, n represents 1 or 2.)
求項１記載のニトリル誘導体。 【化３】 （式中、ｎは１又は２を表す。）3. The nitrile derivative according to claim 1, which is a compound represented by the following formula (4). Embedded image (In the formula, n represents 1 or 2.)
物と、ジアミノマレオニトリルを反応させることを特徴
とする、請求項１のニトリル化合物の製造方法。 【化４】 （式中、Ｒ1は水素原子、置換もしくは無置換の低級ア
ルキル基又は置換もしくは無置換のアリール基を表し、
ｎは１又は２を表す。）4. The method for producing a nitrile compound according to claim 1, wherein a ketone compound represented by the following general formula (2) is reacted with diaminomaleonitrile. Embedded image (Wherein, R 1 represents a hydrogen atom, a substituted or unsubstituted lower alkyl group or a substituted or unsubstituted aryl group,
n represents 1 or 2. )
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|---|---|---|---|
| JP11175234A JP2001002661A (en) | 1999-06-22 | 1999-06-22 | Nitrile compound and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11175234A JP2001002661A (en) | 1999-06-22 | 1999-06-22 | Nitrile compound and its production |
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| Publication Number | Publication Date |
|---|---|
| JP2001002661A true JP2001002661A (en) | 2001-01-09 |
Family
ID=15992617
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180080197A (en) | 2015-11-10 | 2018-07-11 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Dicyanopyrazine compound, luminescent material, luminescent device using the same, and production method of 2,5-dicyano-3,6-dihalogenopyrazine |
| KR20190085138A (en) | 2017-01-13 | 2019-07-17 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Dicyano N-heterocyclic compound, luminescent material and luminescent element using the same |
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| US10774071B2 (en) | 2018-07-13 | 2020-09-15 | Gilead Sciences, Inc. | PD-1/PD-L1 inhibitors |
| US10899735B2 (en) | 2018-04-19 | 2021-01-26 | Gilead Sciences, Inc. | PD-1/PD-L1 inhibitors |
| US11236085B2 (en) | 2018-10-24 | 2022-02-01 | Gilead Sciences, Inc. | PD-1/PD-L1 inhibitors |
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1999
- 1999-06-22 JP JP11175234A patent/JP2001002661A/en active Pending
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| EP3882236A1 (en) | 2015-11-10 | 2021-09-22 | Kyushu University National University Corporation | Production method for 2,5-dicyano-3,6-dihalogenopyrazine |
| EP3882243A1 (en) | 2015-11-10 | 2021-09-22 | Kyushu University National University Corporation | Dicyanopyrazine compound, luminescent material and light transmitter using same |
| US10399960B2 (en) | 2015-11-10 | 2019-09-03 | Kyushu University, National University Corporation | Dicyanopyrazine compound, luminescent material, luminescence device using the same, and method for producing 2,5-dicyano-3,6-dihalogenopyrazine |
| US10497878B2 (en) | 2015-11-10 | 2019-12-03 | Kyushu University, National University Corporation | Dicyanopyrazine compound, luminescent material, luminescence device using the same, and method for producing 2,5-dicyano-3,6-dihalogenopyrazine |
| US10522763B2 (en) | 2015-11-10 | 2019-12-31 | Kyushu University, National Universit Corporation | Dicyanopyrazine compound, luminescent material, luminescence device using the same, and method for producing 2,5-dicyano-3,6-dihalogenopyrazine |
| KR20230093541A (en) | 2015-11-10 | 2023-06-27 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Dicyanopyrazine compound, luminescent material, light transmitter using same, and production method for 2,5-dicyano-3,6-dihalogenopyrazine |
| KR20180080197A (en) | 2015-11-10 | 2018-07-11 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Dicyanopyrazine compound, luminescent material, luminescent device using the same, and production method of 2,5-dicyano-3,6-dihalogenopyrazine |
| KR20190085138A (en) | 2017-01-13 | 2019-07-17 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Dicyano N-heterocyclic compound, luminescent material and luminescent element using the same |
| US11279680B2 (en) | 2017-01-13 | 2022-03-22 | Kyushu University, National University Corporation | Dicyano N-heterocyclic compound, light-emitting material, and light-emitting element in which same is used |
| US11555029B2 (en) | 2018-02-13 | 2023-01-17 | Gilead Sciences, Inc. | PD-1/PD-L1 inhibitors |
| US10710986B2 (en) | 2018-02-13 | 2020-07-14 | Gilead Sciences, Inc. | PD-1/PD-L1 inhibitors |
| US10899735B2 (en) | 2018-04-19 | 2021-01-26 | Gilead Sciences, Inc. | PD-1/PD-L1 inhibitors |
| US10774071B2 (en) | 2018-07-13 | 2020-09-15 | Gilead Sciences, Inc. | PD-1/PD-L1 inhibitors |
| US11236085B2 (en) | 2018-10-24 | 2022-02-01 | Gilead Sciences, Inc. | PD-1/PD-L1 inhibitors |
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