JP2014005224A - Method of producing aromatic dialdehyde compound and oligovinylenephenylene compound - Google Patents

Method of producing aromatic dialdehyde compound and oligovinylenephenylene compound Download PDF

Info

Publication number
JP2014005224A
JP2014005224A JP2012140942A JP2012140942A JP2014005224A JP 2014005224 A JP2014005224 A JP 2014005224A JP 2012140942 A JP2012140942 A JP 2012140942A JP 2012140942 A JP2012140942 A JP 2012140942A JP 2014005224 A JP2014005224 A JP 2014005224A
Authority
JP
Japan
Prior art keywords
group
carbon atoms
reaction
compound
compound represented
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
Application number
JP2012140942A
Other languages
Japanese (ja)
Inventor
Asako Kondo
あさ子 近藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to JP2012140942A priority Critical patent/JP2014005224A/en
Publication of JP2014005224A publication Critical patent/JP2014005224A/en
Pending legal-status Critical Current

Links

Abstract

PROBLEM TO BE SOLVED: To provide a more inexpensive and simpler method of producing an aromatic dialdehyde than conventional methods which use expensive agents unfavorable for the large scale production because it is unstable at room temperature and cannot be used in water, and have complex procedures including 3 processes such as pretreatment, main reaction, and posttreatment.SOLUTION: A method of producing an aromatic dialdehyde compound includes introducing a bromomethyl group to a compound represented by the formula (A), where R, Rare each independently a hydrogen atom, a 1-36C alkyl group, a 1-36C alkoxy group, a 1-36C hydroxyalkylene group, a hydroxy group, a halogen atom, a phenylenevinylene group, or a cyano group, then subjecting the resultant to a reaction using a hexamethylene tetramine.

Description

本発明は、一般的に製造が難しく色素等の製造の重要中間体となる芳香族ジアルデヒド化合物の製造に当たって安定的な収率で製造することができる方法に関する。更に、該芳香族ジアルデヒド化合物を用いたフォトルミネッセンス染料として使用可能なオリゴビニレンフェニレン化合物の製造方法に関する。   The present invention relates to a method that can be produced in a stable yield in producing an aromatic dialdehyde compound that is generally difficult to produce and is an important intermediate in the production of pigments and the like. Furthermore, it is related with the manufacturing method of the oligo vinylene phenylene compound which can be used as a photo-luminescence dye using this aromatic dialdehyde compound.

芳香族ジアルデヒド化合物は、例えば、オリゴビニレンフェニレン化合物類の合成の中間体として有用である。オリゴビニレンフェニレン化合物類は、下記一般式（Ｃ）で表される化合物であり、高い平面性を持つことから濃縮された状態（固体）においてでも分子間力によりモノマーからエキシマーとなる性質を有している。この性質により、分散された状態（溶液）と濃縮された状態（固体）とでは見える色が変化するので、現在、それを利用した用途の開発が進められている（特許文献１、非特許文献３参照）。

Figure 2014005224
（式中、Ｒ１、Ｒ２、Ｒ５はそれぞれ独立に水素原子、炭素数１〜３６のアルキル基、炭素数１〜３６のアルコキシ基、炭素数１〜３６のヒドロキシアルキル基、ヒドロキシ基、ハロゲン原子、フェニルビニル基若しくはシアノ基を示し、Ｒ３、Ｒ４、Ｒ６、Ｒ７はそれぞれ独立に水素原子、炭素数１〜３６のアルキル基、炭素数１〜３６のアルコキシ基、炭素数１〜３６のヒドロキシアルキル基、ヒドロキシ基、ハロゲン原子若しくはシアノ基を示す。） Aromatic dialdehyde compounds are useful, for example, as intermediates in the synthesis of oligovinylene phenylene compounds. Oligovinylene phenylene compounds are compounds represented by the following general formula (C), and have a property of becoming a monomer to an excimer by intermolecular force even in a concentrated state (solid) because of its high planarity. ing. Because of this property, the visible color changes between the dispersed state (solution) and the concentrated state (solid), and therefore, development of applications using the same is currently underway (Patent Document 1, Non-Patent Document). 3).
Figure 2014005224
 (Wherein R 1 , R 2 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, a hydroxyalkyl group having 1 to 36 carbon atoms, a hydroxy group, A halogen atom, a phenylvinyl group or a cyano group, wherein R 3 , R 4 , R 6 and R 7 are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, and a carbon number; 1 to 36 hydroxyalkyl groups, hydroxy groups, halogen atoms or cyano groups are shown.)

芳香族ジアルデヒド化合物の合成方法としては、ｎ−ブチルリチウムを使用する方法（非特許文献１）や単離するために複数の段階を経る方法（非特許文献２）等が知られていた。   As a method for synthesizing an aromatic dialdehyde compound, a method using n-butyllithium (Non-Patent Document 1), a method of passing through a plurality of steps for isolation (Non-Patent Document 2), and the like have been known.

特開２００９−３００９８６号公報JP 2009-3000986 A

Ｋ．Ｎａｋａ，Ｓ．Ｉｎａｇｉ ＆ Ｙ．Ｃｈｕｊｏ，Ｊｏｕｒｎａｌ ｏｆ Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ；Ｐａｒｔ Ａ：Ｐｏｌｙｍｅｒ Ｃｈｅｍｉｓｔｒｙ，Ｖｏｌ．４３，４６００−４６０８（２００５）K. Naka, S .; Inagi & Y. Chujo, Journal of Polymer Science; Part A: Polymer Chemistry, Vol. 43, 4600-4608 (2005) Ａ．Ｒｏｖｉｅｌｌｏ ｅｔ ａｌ．，Ｊｏｕｒｎａｌ ｏｆ Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ；Ｐａｒｔ Ａ：Ｐｏｌｙｍｅｒ Ｃｈｅｍｉｓｔｒｙ，Ｖｏｌ．４７，２６７７−２６８９（２００９）A. Roviello et al. , Journal of Polymer Science; Part A: Polymer Chemistry, Vol. 47, 2677-2689 (2009) Ｍ．Ｋｉｎａｍｉ ｅｔ ａｌ．，Ｃｈｅｍ．Ｍａｔｅｒ．，Ｖｏｌ．１８，９４６−９５５（２００６）M.M. Kinami et al. , Chem. Mater. , Vol. 18, 946-955 (2006)

公知の芳香族ジアルデヒド化合物の製造方法は、常温で不安定で水中では使用できず大量生産に向かない高価な試薬を使っていたり、又、前処理、主反応、後処理と工程が３つに渡っており煩雑な手順となっていた。そして、それを用いるオリゴビニレンフェニレン化合物の製造について経済的で大量生産に向く方法は知られていなかった。   Known methods for producing aromatic dialdehyde compounds use expensive reagents that are unstable at room temperature and cannot be used in water and are not suitable for mass production, and there are three pretreatment, main reaction, and posttreatment steps. It was a complicated procedure. And the method of economical and suitable for mass production was not known about manufacture of the oligo vinylene phenylene compound using it.

本発明者は前記課題を解決すべく鋭意研究を重ねた結果、安価な原料を使い且つ簡便な芳香族アルデヒド化合物の製造方法を見出し、それを用いるオリゴビニレンフェニレン化合物の経済的で大量生産に向く製造方法を見出して本発明を完成させた。   As a result of intensive studies to solve the above problems, the present inventor has found a simple method for producing an aromatic aldehyde compound using an inexpensive raw material and is suitable for economical and mass production of an oligovinylene phenylene compound using the same. The manufacturing method was found and the present invention was completed.

即ち、本発明は以下の（１）〜（４）に関する。
（１）下記一般式（Ａ）で表される化合物にブロモメチル基を導入し、次いでヘキサメチレンテトラミンを用いる反応に付することを特徴とする下記一般式（Ｂ）で表される芳香族ジアルデヒド化合物の製造方法。

Figure 2014005224
（式中、Ｒ１、Ｒ２はそれぞれ独立に水素原子、炭素数１〜３６のアルキル基、炭素数１〜３６のアルコキシ基、炭素数１〜３６のヒドロキシアルキル基、ヒドロキシ基、ハロゲン原子、フェニルビニル基若しくはシアノ基を示す。） That is, the present invention relates to the following (1) to (4).
(1) An aromatic dialdehyde represented by the following general formula (B), wherein a bromomethyl group is introduced into the compound represented by the following general formula (A) and then subjected to a reaction using hexamethylenetetramine. Compound production method.
Figure 2014005224
 (Wherein R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, a hydroxyalkyl group having 1 to 36 carbon atoms, a hydroxy group, a halogen atom, (A phenyl vinyl group or a cyano group is shown.)

（２）Ｒ１が炭素数１〜４のアルコキシ基、Ｒ２が水素原子である前記（１）記載の芳香族ジアルデヒド化合物の製造方法。 (2) The method for producing an aromatic dialdehyde compound according to (1), wherein R 1 is an alkoxy group having 1 to 4 carbon atoms, and R 2 is a hydrogen atom.

（３）上記一般式（Ａ）で表される化合物にブロモメチル基を導入し、次いでヘキサメチレンテトラミンを用いる反応に付し、更にシアノメチルベンゼン誘導体をアルカリ条件下で反応させることを特徴とする下記一般式（Ｃ）で表されるオリゴビニレンフェニレン化合物の製造方法。

Figure 2014005224
（式中、Ｒ１、Ｒ２、Ｒ５はそれぞれ独立に水素原子、炭素数１〜３６のアルキル基、炭素数１〜３６のアルコキシ基、炭素数１〜３６のヒドロキシアルキル基、ヒドロキシ基、ハロゲン原子、フェニルビニル基若しくはシアノ基を示し、Ｒ３、Ｒ４、Ｒ６、Ｒ７はそれぞれ独立に水素原子、炭素数１〜３６のアルキル基、炭素数１〜３６のアルコキシ基、炭素数１〜３６のヒドロキシアルキル基、ヒドロキシ基、ハロゲン原子若しくはシアノ基を示す。） (3) A bromomethyl group is introduced into the compound represented by the general formula (A), then subjected to a reaction using hexamethylenetetramine, and further reacted with a cyanomethylbenzene derivative under alkaline conditions. The manufacturing method of the oligo vinylene phenylene compound represented by general formula (C).
Figure 2014005224
 (Wherein R 1 , R 2 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, a hydroxyalkyl group having 1 to 36 carbon atoms, a hydroxy group, A halogen atom, a phenylvinyl group or a cyano group, wherein R 3 , R 4 , R 6 and R 7 are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, and a carbon number; 1 to 36 hydroxyalkyl groups, hydroxy groups, halogen atoms or cyano groups are shown.)

（４）Ｒ１が同一で炭素数１〜４のアルコキシ基、Ｒ５が同一で炭素数１〜３６のアルキル基、炭素数１〜３６のアルコキシ基、炭素数１〜３６のヒドロキシアルキル基若しくはフェニルビニル基、Ｒ２、Ｒ３、Ｒ４、Ｒ６、Ｒ７が水素原子である前記（３）記載のオリゴビニレンフェニレン化合物の製造方法。 (4) R 1 is the same and an alkoxy group having 1 to 4 carbon atoms, R 5 is the same and an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, a hydroxyalkyl group having 1 to 36 carbon atoms, or The method for producing an oligovinylenephenylene compound according to the above (3), wherein the phenylvinyl group, R 2 , R 3 , R 4 , R 6 and R 7 are hydrogen atoms.

本発明を用いることにより、一般的に製造が容易でない芳香族ジアルデヒド化合物の安価な原料を使い且つ少ない工程で精製工程も必要のない工業化可能で安定的に簡便な製造方法を提供することができ、更に、オリゴビニレンフェニレン化合物の経済的で大量生産に向く製造方法を提供することが可能となった。   By using the present invention, it is possible to provide an industrially stable and simple production method that uses an inexpensive raw material of an aromatic dialdehyde compound that is generally not easy to produce and does not require a purification step with a small number of steps. In addition, it has become possible to provide a method for producing an oligovinylenephenylene compound that is economical and suitable for mass production.

本発明を詳細に説明する。
本発明の芳香族ジアルデヒド化合物の製造方法は、前記一般式（Ａ）（式中、Ｒ１、Ｒ２はそれぞれ独立に水素原子、炭素数１〜３６のアルキル基、炭素数１〜３６のアルコキシ基、炭素数１〜３６のヒドロキシアルキル基、ヒドロキシ基、ハロゲン原子、フェニルビニル基若しくはシアノ基を示す）で表される化合物にブロモメチル基を導入する第１工程、次いでヘキサメチレンテトラミンを用いる反応に付する第２工程を特徴とする。 The present invention will be described in detail.
The method for producing an aromatic dialdehyde compound of the present invention is the above general formula (A) (wherein R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, and having 1 to 36 carbon atoms). A first step of introducing a bromomethyl group into a compound represented by an alkoxy group, a hydroxyalkyl group having 1 to 36 carbon atoms, a hydroxy group, a halogen atom, a phenylvinyl group or a cyano group, followed by a reaction using hexamethylenetetramine It is characterized by the second step attached to.

本発明において炭素数１〜３６のアルキル基としては直鎖又は分岐鎖のアルキル基が挙げられ、炭素数１〜２０の直鎖アルキル基が好ましい。
本発明において炭素数１〜３６のアルコキシ基としては直鎖又は分岐鎖のアルコキシ基が挙げられ、炭素数１〜２０の直鎖アルコキシ基が好ましい。
本発明において炭素数１〜３６のヒドロキシアルキル基としてはヒドロキシ基が末端に結合した直鎖のアルキル基が挙げられ、炭素数１〜２０のヒドロキシアルキル基が好ましい。
本発明においてハロゲン原子としては、例えば、塩素原子、臭素原子、沃素原子等が挙げられる。
本発明においてフェニルビニル基とはフェニル基が結合し炭素数１〜３のアルキル基が置換していてもよいビニル基が挙げられ、フェニル基が結合した無置換のビニル基が好ましい。 In the present invention, the alkyl group having 1 to 36 carbon atoms includes a linear or branched alkyl group, and a linear alkyl group having 1 to 20 carbon atoms is preferable.
In the present invention, the alkoxy group having 1 to 36 carbon atoms includes a linear or branched alkoxy group, and a linear alkoxy group having 1 to 20 carbon atoms is preferable.
In the present invention, examples of the hydroxyalkyl group having 1 to 36 carbon atoms include a straight chain alkyl group having a hydroxy group bonded to the terminal, and a hydroxyalkyl group having 1 to 20 carbon atoms is preferable.
In the present invention, examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.
In the present invention, the phenyl vinyl group includes a vinyl group to which a phenyl group is bonded and an alkyl group having 1 to 3 carbon atoms may be substituted, and an unsubstituted vinyl group to which a phenyl group is bonded is preferable.

Ｒ１として特に好ましくは水素原子又は炭素数１〜３６のアルコキシ基が挙げられ、炭素数１〜４のアルコキシ基が殊更好ましい。同一分子中に存在する複数のＲ１は異なっていてもよいが、同一であるのが好ましい。
Ｒ２として特に好ましくは水素原子又はヒドロキシ基が挙げられ、水素原子が殊更好ましい。同一分子中に存在する複数のＲ２は異なっていてもよいが、同一であるのが好ましい。 R 1 is particularly preferably a hydrogen atom or an alkoxy group having 1 to 36 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms is particularly preferable. A plurality of R 1 present in the same molecule may be different, but is preferably the same.
R 2 is particularly preferably a hydrogen atom or a hydroxy group, and a hydrogen atom is particularly preferred. A plurality of R 2 present in the same molecule may be different, but is preferably the same.

第１工程では、一般式（Ａ）で表わされる原料化合物を酢酸中、パラホルムアルデヒドと臭化水素と反応させ生成した固体をろ取する。臭化水素は酢酸等の溶液として使用してもよい。
酢酸は原料化合物に対して質量比で０．１〜１００倍量、好ましくは１〜５０倍量、更に好ましくは１〜１０倍量、パラホルムアルデヒドは原料化合物に対して質量比で０．１〜１０倍量、好ましくは０．２〜１倍量、更に好ましくは０．３〜０．６倍量、臭化水素は原料化合物に対して２〜１０モル当量、好ましくは２〜４モル当量、更に好ましくは２〜２．５モル当量使用すればよい。 In the first step, the raw material compound represented by formula (A) is reacted with paraformaldehyde and hydrogen bromide in acetic acid, and the resulting solid is collected by filtration. Hydrogen bromide may be used as a solution of acetic acid or the like.
Acetic acid is 0.1 to 100 times by mass, preferably 1 to 50 times, more preferably 1 to 10 times, and paraformaldehyde is 0.1 to 0.1 by mass with respect to the raw material compound. 10 times the amount, preferably 0.2 to 1 times the amount, more preferably 0.3 to 0.6 times the amount, hydrogen bromide is 2 to 10 molar equivalents, preferably 2 to 4 molar equivalents relative to the starting compound, More preferably, 2-2.5 molar equivalents may be used.

反応温度は０〜１００℃の範囲で適宜選択することができるが、好ましくは１０〜７０℃であり、更に好ましくは４０〜６０℃である。
又、該反応は発熱反応であるため、安全性も考慮して反応初期は１０〜４０℃、後に４０〜７０℃に昇温するのが好ましい。更に好ましくは反応初期が２０〜４０℃、昇温後が４０〜６０℃、殊更に好ましくは反応初期が３０〜４０℃、昇温後が５０〜６０℃である。更に、反応初期温度まで一定時間をかけて昇温し、反応後に続けて一定時間をかけて昇温し反応を完結する方法を取ってもよい。この場合、反応初期の昇温速度としては０．０１〜１℃／分、好ましくは０．１〜０．７℃／分、更に好ましくは０．２〜０．４℃／分である。続いて昇温する場合の昇温速度も、０．０１〜１℃／分、好ましくは０．１〜０．７℃／分、更に好ましくは０．２〜０．４分／分である。 Although reaction temperature can be suitably selected in the range of 0-100 degreeC, Preferably it is 10-70 degreeC, More preferably, it is 40-60 degreeC.
In addition, since the reaction is an exothermic reaction, it is preferable to raise the temperature to 10 to 40 ° C. in the initial stage of reaction and to 40 to 70 ° C. later in consideration of safety. More preferably, the initial reaction is 20 to 40 ° C., the temperature is 40 to 60 ° C., particularly preferably 30 to 40 ° C. and the temperature is 50 to 60 ° C. Further, a method may be employed in which the temperature is raised over a certain time to the initial reaction temperature, and then the temperature is raised over a certain time after the reaction to complete the reaction. In this case, the temperature rising rate at the initial stage of the reaction is 0.01 to 1 ° C / min, preferably 0.1 to 0.7 ° C / min, and more preferably 0.2 to 0.4 ° C / min. When the temperature is subsequently raised, the rate of temperature rise is also 0.01 to 1 ° C./min, preferably 0.1 to 0.7 ° C./min, and more preferably 0.2 to 0.4 min / min.

該反応工程において、昇温時間を含めない反応時間は０．５〜１０時間の範囲で適宜選択することができるが、好ましくは１〜７時間、更に好ましくは２〜５時間である。反応初期は低温、その後昇温して反応完結する方法をとる場合、反応初期は０．５〜５時間、昇温後は０．１〜５時間の範囲から適宜選択することができるが、好ましくは反応初期が０．５〜３時間、昇温後が１〜４時間であり、更に好ましくは反応初期が１〜２時間、昇温後が２〜３時間である。   In the reaction step, the reaction time not including the temperature raising time can be appropriately selected within the range of 0.5 to 10 hours, preferably 1 to 7 hours, more preferably 2 to 5 hours. In the case of adopting a method of completing the reaction by raising the temperature at the initial stage of the reaction and then raising the temperature, the initial stage of the reaction can be appropriately selected from the range of 0.5 to 5 hours, and after the temperature rise, it can be suitably selected from the range of 0.1 to 5 hours. The initial reaction time is 0.5 to 3 hours, the temperature is 1 to 4 hours, and more preferably the reaction time is 1 to 2 hours and the temperature is 2 to 3 hours.

第２工程では、第１工程で得られたブロモメチル基の導入された固体を単離精製することなく、溶媒中ヘキサメチレンテトラミンと酸の存在下で加熱して反応させ、生成する固体をろ取して一般式（Ｂ）で表される芳香族ジアルデヒド化合物を得る。   In the second step, the solid introduced with the bromomethyl group obtained in the first step is reacted by heating in the presence of hexamethylenetetramine and an acid in a solvent without isolation and purification, and the resulting solid is collected by filtration. Thus, an aromatic dialdehyde compound represented by the general formula (B) is obtained.

第２工程において、一般式（Ａ）で表わされる化合物に対してヘキサメチレンテトラミンは１〜１０モル当量、好ましくは２〜８モル当量、更に好ましくは２〜５モル当量使用する。酸としては蟻酸、酢酸、塩酸、硫酸等が挙げられ、その中から一つ以上を選択して使用することができ、酢酸若しくは塩酸を単独又は併用するのが好ましい。その使用量は一般式（Ａ）で表わされる化合物に対して０．１〜１００モル当量の範囲から適宜選択することができ、好ましくは１〜５０モル当量、更に好ましくは５〜１５モル当量である。   In the second step, hexamethylenetetramine is used in an amount of 1 to 10 molar equivalents, preferably 2 to 8 molar equivalents, more preferably 2 to 5 molar equivalents, relative to the compound represented by the general formula (A). Examples of the acid include formic acid, acetic acid, hydrochloric acid, sulfuric acid and the like. One or more of them can be selected and used, and acetic acid or hydrochloric acid is preferably used alone or in combination. The amount used can be appropriately selected from the range of 0.1 to 100 molar equivalents relative to the compound represented by the general formula (A), preferably 1 to 50 molar equivalents, more preferably 5 to 15 molar equivalents. is there.

第２工程において、一般式（Ａ）で表わされる化合物にブロモメチル基の導入された固体と各反応試薬の投入順序と加熱のタイミングは適宜選択することができるが、一般式（Ａ）で表わされる化合物にブロモメチル基の導入された固体とヘキサメチレンテトラミンを後記溶媒中に添加した後に加熱して酸を加えて反応させるのが好ましい。
該溶媒としては水、メタノール、エタノール、ＤＭＦ（Ｎ，Ｎ−ジメチルホルムアミド）、ＤＭＳＯ（ジメチルスルホキシド）の中から適宜選択することができるが、好ましくは水、エタノールであり、更に好ましくは水である。 In the second step, the order in which the solid having the bromomethyl group introduced into the compound represented by the general formula (A) and each reaction reagent and the timing of heating can be selected as appropriate, but are represented by the general formula (A). It is preferable to add the solid into which the bromomethyl group has been introduced to the compound and hexamethylenetetramine in a solvent described later, and then to react by adding an acid by heating.
The solvent can be appropriately selected from water, methanol, ethanol, DMF (N, N-dimethylformamide) and DMSO (dimethyl sulfoxide), preferably water and ethanol, more preferably water. .

第２工程の反応温度としては４０〜１１０℃の範囲から適宜選択することができ、好ましくは５０〜１００℃、更に好ましくは８０〜１００℃である。反応時間は０．５〜５時間の範囲から適宜選択することができ、好ましくは１〜４時間、更に好ましくは２〜３時間である。   The reaction temperature in the second step can be appropriately selected from the range of 40 to 110 ° C, preferably 50 to 100 ° C, more preferably 80 to 100 ° C. The reaction time can be appropriately selected from the range of 0.5 to 5 hours, preferably 1 to 4 hours, more preferably 2 to 3 hours.

本発明には前記の製造方法で得られる芳香族ジアルデヒド化合物を使用する前記のオリゴビニレンフェニレン化合物の製造方法も含まれる。即ち、下記反応式に示すように、該芳香族ジアルデヒド化合物にシアノメチルベンゼン誘導体（Ｄ）をアルカリ条件下で反応させることを特徴とする。

Figure 2014005224
The present invention also includes a method for producing the above oligovinylenephenylene compound using the aromatic dialdehyde compound obtained by the above production method. That is, as shown in the following reaction formula, the aromatic dialdehyde compound is reacted with a cyanomethylbenzene derivative (D) under alkaline conditions.
Figure 2014005224

Ｒ３、Ｒ４、Ｒ６、Ｒ７として特に好ましくは水素原子又はヒドロキシ基が挙げられ、水素原子が殊更好ましい。一般式（Ｃ）で表される化合物中、Ｒ３同士、Ｒ４同士、Ｒ６同士、Ｒ７同士は異なっていてもよいが、同一であるのが好ましい。 R 3 , R 4 , R 6 and R 7 are particularly preferably a hydrogen atom or a hydroxy group, and a hydrogen atom is particularly preferred. In the compound represented by the general formula (C), R 3 s , R 4 s , R 6 s , and R 7 s may be different, but are preferably the same.

Ｒ５として特に好ましくは水素原子又は炭素数１〜３６のアルコキシ基が挙げられ、炭素数１５〜３６のアルコキシ基が殊更好ましい。同一分子中に存在する複数のＲ５は異なっていてもよいが、同一であるのが好ましい。
生成するビニレン基についてＺ体を便宜的に記載しているが、Ｅ体でも、Ｚ体とＥ体の混合物であってもよい。 R 5 is particularly preferably a hydrogen atom or an alkoxy group having 1 to 36 carbon atoms, more preferably an alkoxy group having 15 to 36 carbon atoms. A plurality of R 5 present in the same molecule may be different but are preferably the same.
Although the Z-form is described for convenience with respect to the vinylene group to be produced, it may be an E-form or a mixture of the Z-form and the E-form.

本製造方法は特に限定されないが、有機溶剤中、一般式（Ｂ）で表される化合物と一般式（Ｄ）で表される化合物の混合物にアルカリを添加して行うことができる。この時、必要に応じて加熱する。ここで、一般式（Ｂ）で表される化合物１モルに対し、一般式（Ｄ）で表される化合物を１．５〜５．０モル、好ましくは２．０〜３．０モル、更に好ましくは２．０〜２．５モル使用する。一般式（Ｃ）で表される目的化合物は、反応液をろ過するだけで純度のよい固体として得られる。   Although this manufacturing method is not specifically limited, In an organic solvent, it can carry out by adding an alkali to the mixture of the compound represented by general formula (B), and the compound represented by general formula (D). At this time, heating is performed as necessary. Here, with respect to 1 mol of the compound represented by the general formula (B), the compound represented by the general formula (D) is 1.5 to 5.0 mol, preferably 2.0 to 3.0 mol, Preferably, 2.0 to 2.5 mol is used. The target compound represented by the general formula (C) can be obtained as a pure solid simply by filtering the reaction solution.

該アルカリとしては炭酸カリウム、炭酸ナトリウム、水酸化ナトリウム、ナトリウムメトキシド、ｔ−ブトキシカリウム等の中から一つ以上を選択して使用することができ、取り扱いの点でナトリウムメトキシドが好ましい。その使用量は一般式（Ｂ）で表される化合物に対して０．００１〜１０当量程度、好ましくは０．０５〜３当量程度、更に好ましくは０．１〜１．１当量程度でよい。   As the alkali, one or more selected from potassium carbonate, sodium carbonate, sodium hydroxide, sodium methoxide, t-butoxypotassium and the like can be used, and sodium methoxide is preferable in terms of handling. The amount used may be about 0.001 to 10 equivalents, preferably about 0.05 to 3 equivalents, and more preferably about 0.1 to 1.1 equivalents with respect to the compound represented by formula (B).

該有機溶剤としてはアセトン、メタノール、エタノール、テトラヒドロフラン、ｔ−ブチルアルコール、ＤＭＦ、クロロホルム等から一つ以上を選択して使用することができるが、中でもメタノール、エタノール、テトラヒドロフラン、ｔ−ブチルアルコールの中から一つ以上選択するのが好ましい。   As the organic solvent, one or more selected from acetone, methanol, ethanol, tetrahydrofuran, t-butyl alcohol, DMF, chloroform and the like can be used. Among them, methanol, ethanol, tetrahydrofuran, t-butyl alcohol, and the like can be used. It is preferable to select one or more from.

反応温度としては０〜１００℃の範囲から適宜選択することができ、好ましくは３０〜８０℃、更に好ましくは６０〜７０℃である。反応時間としては０．２〜５時間の範囲から適宜選択することができ、好ましくは０．５〜３時間、更に好ましくは０．８〜１．５時間である。   The reaction temperature can be appropriately selected from the range of 0 to 100 ° C, preferably 30 to 80 ° C, more preferably 60 to 70 ° C. The reaction time can be appropriately selected from the range of 0.2 to 5 hours, preferably 0.5 to 3 hours, and more preferably 0.8 to 1.5 hours.

以下、実施例により本発明を更に詳細に説明するが、これらの実施例により本発明が限定されるものではない。実施例において特に断りがない限り、部は質量部を、％は質量％をそれぞれ意味する。   EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. Unless otherwise specified in the examples, “part” means “part by mass” and “%” means “% by mass”.

［実施例１］２，５−ジメトキシテレフタルアルデヒドの製造

Figure 2014005224
温度を２０〜２５℃に保ちながら、酢酸（５０ｇ）に２，５−ジメトキシベンゼン（１０部、０．０７２ｍｏｌ：東京化成（株）製）とパラホルムアルデヒド（４．４部）と２０％臭化水素酢酸溶液（６０部、０．１５２ｍｏｌ：Ａｌｄｒｉｃｈ製）を加えた後、湯浴にて３５℃に加温した。同温で１時間反応させた後、更に湯浴にて５５℃まで加熱して３時間反応させた。その後、４０℃以下まで冷却して水１００部を添加し、苛性ソーダを用いてｐＨ４に調節した。その懸濁液をろ過し、固体を水でよく洗浄し、ブロモメチル基の導入された反応中間体を得た。続いて、得られた中間体を水１７５部に添加し、よく懸濁後、テトラメチレンヘキサミン（４１部、０．２８９ｍｏｌ）を添加し９０〜９５℃に加熱した。次いで、温度を９０℃〜９５℃に保ちながら５０％酢酸水溶液（９５部）を滴下し、その後２時間反応させ、引き続き３５％塩酸２０部を添加し、更に１時間反応させた。この溶液を４０℃以下まで冷却し、水２５０部を添加してろ過し、２，５−ジメトキシテレフタルアルデヒド（７部、純度７２％、収率３６％）を得た。 [Example 1] Production of 2,5-dimethoxyterephthalaldehyde
Figure 2014005224
 While maintaining the temperature at 20 to 25 ° C., 2,5-dimethoxybenzene (10 parts, 0.072 mol: manufactured by Tokyo Chemical Industry Co., Ltd.), paraformaldehyde (4.4 parts) and 20% bromide were added to acetic acid (50 g). A hydrogen acetic acid solution (60 parts, 0.152 mol: manufactured by Aldrich) was added, and the mixture was heated to 35 ° C. in a hot water bath. After reacting at the same temperature for 1 hour, it was further heated to 55 ° C. in a hot water bath and reacted for 3 hours. Then, it cooled to 40 degrees C or less, 100 parts of water was added, and it adjusted to pH4 using caustic soda. The suspension was filtered, and the solid was washed well with water to obtain a reaction intermediate having a bromomethyl group introduced. Subsequently, the obtained intermediate was added to 175 parts of water, and after well suspending, tetramethylenehexamine (41 parts, 0.289 mol) was added and heated to 90 to 95 ° C. Next, 50% aqueous acetic acid solution (95 parts) was added dropwise while maintaining the temperature at 90 ° C. to 95 ° C., followed by reaction for 2 hours, followed by addition of 20 parts of 35% hydrochloric acid and further reaction for 1 hour. The solution was cooled to 40 ° C. or lower, 250 parts of water was added and filtered to obtain 2,5-dimethoxyterephthalaldehyde (7 parts, purity 72%, yield 36%).

［参考例］

Figure 2014005224
４−ヒドロキシベンジルシアニド（７．５部、０．０５６ｍｏｌ：東京化成（株）製）、ステアリルブロマイド（２２部、０．０６８ｍｏｌ）、炭酸カリウム（９．７部、０．０７０ｍｏｌ）をＤＭＦ（６０部）中で混合し、７０℃に加熱して５時間反応させた。この混合液を水５００部のなかにゆっくり撹拌しながら注ぎ晶析させ、固体をろ過して水でよく洗い、乾燥させて４−ステアリルオキシベンジルシアニド（２１部、１００％）を得た。 [Reference example]
Figure 2014005224
 4-hydroxybenzyl cyanide (7.5 parts, 0.056 mol: manufactured by Tokyo Chemical Industry Co., Ltd.), stearyl bromide (22 parts, 0.068 mol), potassium carbonate (9.7 parts, 0.070 mol) were added to DMF ( 60 parts), heated to 70 ° C. and reacted for 5 hours. The mixed solution was poured into 500 parts of water while slowly stirring and crystallized, and the solid was filtered, washed well with water, and dried to give 4-stearyloxybenzyl cyanide (21 parts, 100%).

［実施例２］

Figure 2014005224
実施例１で得られた２，５−ジメトキシテレフタルアルデヒド（７部、純度７２％、０．０２６ｍｏｌ）と、参考例で得られた４−ステアリルオキシベンジルシアニド（２１部、０．０６０ｍｏｌ）とを、変性エタノール（メタノールを１１％含むエタノール、２００部）中に懸濁し６０〜６５℃に加熱した。そこに、２８％ナトリウムメトキシド（１部、０．０２６ｍｏｌ：和光純薬工業（株）製）を添加し反応させた。３５℃以下に冷却し、析出した橙色の結晶をろ過して、変性エタノール、水でよく洗い、目的とするオリゴビニレンフェニレン化合物（２４部、１００％）を得た。 [Example 2]
Figure 2014005224
 2,5-dimethoxyterephthalaldehyde obtained in Example 1 (7 parts, purity 72%, 0.026 mol) and 4-stearyloxybenzyl cyanide obtained in Reference Example (21 parts, 0.060 mol) Was suspended in denatured ethanol (ethanol containing 11% of methanol, 200 parts) and heated to 60 to 65 ° C. 28% sodium methoxide (1 part, 0.026 mol: manufactured by Wako Pure Chemical Industries, Ltd.) was added and reacted therewith. The mixture was cooled to 35 ° C. or lower, and the precipitated orange crystals were filtered and washed thoroughly with denatured ethanol and water to obtain the desired oligovinylenephenylene compound (24 parts, 100%).

［比較例１］２，５−ジメトキシテレフタルアルデヒドの製造

Figure 2014005224
温度を２０〜２５℃に保ちながら、酢酸（５０ｇ）に２，５−ジメトキシベンゼン（１０部、０．０７２ｍｏｌ）とパラホルムアルデヒド（４．４部）と２０％臭化水素酢酸溶液（６０部、０．１５２ｍｏｌ）を加えた後、湯浴にて３５℃に加温した。同温で１時間反応させた後、更に湯浴にて５５℃まで加熱し３時間反応させた。その後、４０℃以下まで冷却し、水１００部を添加し苛性ソーダを用いてｐＨ４に調節した。その懸濁液をろ過し、固体を水でよく洗浄し乾燥してブロモメチル基の導入された反応中間体（２８部）を得た。この中間体に、メタノール（１００部）とピリジン（１７部）を添加し、７８℃で３時間還流し、室温まで冷却した後、反応系内を減圧して容器を加熱しエタノールと未反応ピリジンを除去した。残った固体にメタノール（１００部）を添加し４℃に冷却した。ここに、Ｎ，Ｎ−ジメチルニトロソアニリン（３０部）を添加し１時間撹拌した。次いで、２５％苛性ソーダ水溶液（２００部）を滴下し０．５時間撹拌した後、更に水（２００部）を添加し、酢酸を用いてｐＨを５〜６に調整しろ過した。得られた固体を１０％硫酸水溶液（２００ｍｌ）に懸濁して１５分撹拌し、再度ろ過した。得られた固体を１０％硫酸水溶液と水でよく洗浄し、乾燥させて結晶を得た。この結晶を、ＤＭＦを用いて再結晶し、目的の２，５−ジメトキシテレフタルアルデヒド（１１部、純度３９％、収率３０％）を得た。 [Comparative Example 1] Production of 2,5-dimethoxyterephthalaldehyde
Figure 2014005224
While maintaining the temperature at 20-25 ° C., 2,5-dimethoxybenzene (10 parts, 0.072 mol), paraformaldehyde (4.4 parts) and a 20% hydrobromic acetic acid solution (60 parts, 0.152 mol) was added, and the mixture was heated to 35 ° C. in a hot water bath. After reacting at the same temperature for 1 hour, it was further heated to 55 ° C. in a hot water bath and reacted for 3 hours. Then, it cooled to 40 degrees C or less, 100 parts of water was added, and it adjusted to pH4 using caustic soda. The suspension was filtered, and the solid was washed well with water and dried to obtain a reaction intermediate (28 parts) into which a bromomethyl group was introduced. Methanol (100 parts) and pyridine (17 parts) were added to this intermediate, refluxed at 78 ° C. for 3 hours, cooled to room temperature, the reaction system was depressurized, and the vessel was heated to add ethanol and unreacted pyridine. Was removed. Methanol (100 parts) was added to the remaining solid and cooled to 4 ° C. N, N-dimethylnitrosoaniline (30 parts) was added thereto and stirred for 1 hour. Subsequently, 25% aqueous sodium hydroxide solution (200 parts) was added dropwise and stirred for 0.5 hour, and then water (200 parts) was further added, and the pH was adjusted to 5-6 with acetic acid and filtered. The obtained solid was suspended in a 10% aqueous sulfuric acid solution (200 ml), stirred for 15 minutes, and filtered again. The obtained solid was thoroughly washed with 10% aqueous sulfuric acid and water and dried to obtain crystals. The crystals were recrystallized using DMF to obtain the desired 2,5-dimethoxyterephthalaldehyde (11 parts, purity 39%, yield 30%).

反応についてはＨＰＬＣ分析により反応追跡を行った。
ＨＰＬＣ分析条件
モデル：島津 Ｐｒｏｍｉｎｅｎｃｅ
カラム：Ｉｎｅｒｔｓｉｌ ＯＤＳ−３（５μｍ） φ４．６ｘ１５０ｍｍ （４０℃）
検出器：ＵＶ２１０ｎｍ
移動相及び分離条件：
Ａ：アセトニトリル／テトラヒドロフラン（５０：５０） Ｂ：水
Ａ液３０％→（１５分）→１００％→（５分） The reaction was traced by HPLC analysis.
HPLC analysis condition model: Shimazu Prominence
Column: Inertsil ODS-3 (5 μm) φ4.6 × 150 mm (40 ° C.)
Detector: UV210nm
Mobile phase and separation conditions:
A: Acetonitrile / tetrahydrofuran (50:50) B: Water A solution 30% → (15 minutes) → 100% → (5 minutes)

得られた２，５−ジメトキシテレフタルアルデヒドについては、ＯＤ測定を行って純度を決定した。
ＯＤ測定条件
試料０．０５部をクロロホルムで２５００倍希釈し、得られた溶液を分光光度計ＵＶ−２５５０（島津（株）製）にて測定した。精製済の標品のＯＤを用いて比較して純度を求めた。 About the obtained 2, 5- dimethoxy terephthalaldehyde, OD measurement was performed and purity was determined.
OD Measurement Conditions 0.05 part of a sample was diluted 2500 times with chloroform, and the resulting solution was measured with a spectrophotometer UV-2550 (manufactured by Shimadzu Corporation). The purity was determined by comparison using the OD of the purified sample.

本発明の２，５−ジメトキシテレフタルアルデヒドの製造方法（実施例１）は、従来の製造方法（比較例１）に比べて高純度の化合物を比較的収率よく簡便に得られることが明らかである。   It is clear that the method for producing 2,5-dimethoxyterephthalaldehyde of the present invention (Example 1) can easily obtain a high-purity compound in a relatively high yield as compared with the conventional production method (Comparative Example 1). is there.

Claims (4)

下記一般式（Ａ）で表される化合物にブロモメチル基を導入し、次いでヘキサメチレンテトラミンを用いる反応に付することを特徴とする下記一般式（Ｂ）で表される芳香族ジアルデヒド化合物の製造方法。
Figure 2014005224
 （式中、Ｒ１、Ｒ２はそれぞれ独立に水素原子、炭素数１〜３６のアルキル基、炭素数１〜３６のアルコキシ基、炭素数１〜３６のヒドロキシアルキル基、ヒドロキシ基、ハロゲン原子、フェニルビニル基若しくはシアノ基を示す。） Production of an aromatic dialdehyde compound represented by the following general formula (B), wherein a bromomethyl group is introduced into the compound represented by the following general formula (A) and then subjected to a reaction using hexamethylenetetramine Method.
Figure 2014005224
 (Wherein R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, a hydroxyalkyl group having 1 to 36 carbon atoms, a hydroxy group, a halogen atom, (A phenyl vinyl group or a cyano group is shown.) Ｒ１が炭素数１〜４のアルコキシ基、Ｒ２が水素原子である請求項１記載の芳香族ジアルデヒド化合物の製造方法。 The method for producing an aromatic dialdehyde compound according to claim 1, wherein R 1 is an alkoxy group having 1 to 4 carbon atoms and R 2 is a hydrogen atom. 上記一般式（Ａ）で表される化合物にブロモメチル基を導入し、次いでヘキサメチレンテトラミンを用いる反応に付し、更にシアノメチルベンゼン誘導体をアルカリ条件下で反応させることを特徴とする下記一般式（Ｃ）で表されるオリゴビニレンフェニレン化合物の製造方法。
Figure 2014005224
 （式中、Ｒ１、Ｒ２、Ｒ５はそれぞれ独立に水素原子、炭素数１〜３６のアルキル基、炭素数１〜３６のアルコキシ基、炭素数１〜３６のヒドロキシアルキル基、ヒドロキシ基、ハロゲン原子、フェニルビニル基若しくはシアノ基を示し、Ｒ３、Ｒ４、Ｒ６、Ｒ７はそれぞれ独立に水素原子、炭素数１〜３６のアルキル基、炭素数１〜３６のアルコキシ基、炭素数１〜３６のヒドロキシアルキル基、ヒドロキシ基、ハロゲン原子若しくはシアノ基を示す。） A bromomethyl group is introduced into the compound represented by the above general formula (A), then subjected to a reaction using hexamethylenetetramine, and further reacted with a cyanomethylbenzene derivative under an alkaline condition. C) The manufacturing method of the oligo vinylene phenylene compound represented.
Figure 2014005224
 (Wherein R 1 , R 2 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, a hydroxyalkyl group having 1 to 36 carbon atoms, a hydroxy group, A halogen atom, a phenylvinyl group or a cyano group, wherein R 3 , R 4 , R 6 and R 7 are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, and a carbon number; 1 to 36 hydroxyalkyl groups, hydroxy groups, halogen atoms or cyano groups are shown.) Ｒ１が同一で炭素数１〜４のアルコキシ基、Ｒ５が同一で炭素数１〜３６のアルキル基、炭素数１〜３６のアルコキシ基、炭素数１〜３６のヒドロキシアルキル基若しくはフェニルビニル基、Ｒ２、Ｒ３、Ｒ４、Ｒ６、Ｒ７が水素原子である請求項３記載のオリゴビニレンフェニレン化合物の製造方法。 R 1 is the same and is an alkoxy group having 1 to 4 carbon atoms, R 5 is the same and is an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, a hydroxyalkyl group having 1 to 36 carbon atoms, or a phenyl vinyl group The method for producing an oligovinylene phenylene compound according to claim 3 , wherein R 2 , R 3 , R 4 , R 6 , and R 7 are hydrogen atoms.
JP2012140942A 2012-06-22 2012-06-22 Method of producing aromatic dialdehyde compound and oligovinylenephenylene compound Pending JP2014005224A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012140942A JP2014005224A (en) 2012-06-22 2012-06-22 Method of producing aromatic dialdehyde compound and oligovinylenephenylene compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2012140942A JP2014005224A (en) 2012-06-22 2012-06-22 Method of producing aromatic dialdehyde compound and oligovinylenephenylene compound

Publications (1)

Publication Number Publication Date
JP2014005224A true JP2014005224A (en) 2014-01-16

Family

ID=50103311

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2012140942A Pending JP2014005224A (en) 2012-06-22 2012-06-22 Method of producing aromatic dialdehyde compound and oligovinylenephenylene compound

Country Status (1)

Country Link
JP (1) JP2014005224A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106189344A (en) * 2016-06-28 2016-12-07 西北农林科技大学 A kind of fluorescent dye and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5080316A (en) * 1973-11-21 1975-06-30
US20060108564A1 (en) * 2002-06-21 2006-05-25 Christiane Lowe Color tunable photoluminescent blends
WO2010101224A1 (en) * 2009-03-06 2010-09-10 国立大学法人九州工業大学 Organic semiconductor material and organic thin film transistor
JP2011057638A (en) * 2009-09-11 2011-03-24 Tokyo Institute Of Technology Phenylenevinylene compound, and field-effect transistor containing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5080316A (en) * 1973-11-21 1975-06-30
US20060108564A1 (en) * 2002-06-21 2006-05-25 Christiane Lowe Color tunable photoluminescent blends
WO2010101224A1 (en) * 2009-03-06 2010-09-10 国立大学法人九州工業大学 Organic semiconductor material and organic thin film transistor
JP2011057638A (en) * 2009-09-11 2011-03-24 Tokyo Institute Of Technology Phenylenevinylene compound, and field-effect transistor containing the same

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
HERMANN IRNGARTINGER, ET AL.: "Synthesis and topochemistry of 2,5-bisacrylate-substituted 1,4-benzoquinones", EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, JPN6015030668, 1998, pages 595 - 604, ISSN: 0003127531 *
JING-YI JIN, ET AL.: "Design and synthesis of 1,4-bis[4-(1,1-dicyanovinyl)styryl]-2,5-bis(alkoxy)benzenes as red organic e", POLYMER, vol. 48, JPN6015030672, 2007, pages 4028 - 4033, XP022126278, ISSN: 0003127533 *
K. ANUCHAI, ET AL.: "Strain sensitive photonic natural rubber", PLASTICS, RUBBER AND COMPOSITES, vol. Vol.37, No.5/6, JPN6015030670, 2008, pages 281 - 287, ISSN: 0003127532 *
MU JIE YANG, ET AL.: "Novel poly(thienylene ethynylene)s with electron-accepting groups", CHINESE CHEMICAL LETTERS, vol. 17, no. 10, JPN6015030674, 2006, pages 1381 - 1384, ISSN: 0003127534 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106189344A (en) * 2016-06-28 2016-12-07 西北农林科技大学 A kind of fluorescent dye and application thereof
CN106189344B (en) * 2016-06-28 2017-09-19 西北农林科技大学 A kind of fluorescent dye and its application

Similar Documents

Publication Publication Date Title
JP5752256B2 (en) Method for producing 2-methoxymethyl-1,4-benzenediamine
JP6948419B2 (en) New manufacturing method for chromanon derivatives
WO2007125736A1 (en) Process for production of methylene disulfonate compound
KR101771997B1 (en) Method for producing a methylene disulfonate compound
WO2010122794A1 (en) Process for production of pyrazinecarboxylic acid derivative, and intermediate for the production
CA3058686C (en) Method for preparing 2-aryl malonamide and applications thereof
JP5008404B2 (en) Method for producing methylene disulfonate compound
JP2014005224A (en) Method of producing aromatic dialdehyde compound and oligovinylenephenylene compound
JP3919215B2 (en) Process for producing carboxyarene sulfonic acid and its carboxylic acid derivative
JP2017160185A (en) Method for preparing aromatic sulfide or salt thereof
WO2016035405A1 (en) Azo dye composition and method for producing same
JP4712320B2 (en) Process for producing 2-oxo-1-phenyl-3-oxabicyclo [3.1.0] hexane
KR20090064456A (en) Process for the preparation of trifluoroethoxytoluenes
JP4968066B2 (en) Process for producing 4-amino-2-alkylthio-5-pyrimidinecarbaldehyde
JP2007211185A (en) Phenazine compound
CN109553629A (en) A kind of preparation method of Cefuroxime Sodium intermediate E type impurity compound
JP2020537680A (en) Process for producing herbicidal pyridadinone compounds
JP4582286B2 (en) Sulfooxyalkynylthiophene compound and process for producing the same
BR112013018809A2 (en) production process of aromatic amide carboxylic acid derivative
JP5026104B2 (en) Carbazole compounds
RU2318799C1 (en) Method for preparing 3,4'-diamino-4-r-benzophenones
JP4531610B2 (en) Method for producing croconic acid or a salt thereof
JP2008037772A (en) Method for producing 2, 2-bis (4-amino-3-hydroxyphenyl) propane compound
KR101411359B1 (en) Method of mono ｎ-alkylation of aniline compounds
JP2022529916A (en) Method for Producing Substituted 2- [2- (Phenyl) Ethylamino] Alkaneamide Derivative

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20150213

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20150727

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20150825

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20151217