JP2009209073A - Polycyano oligo phenylene ethynylene compound having electron-donating group introduced to its molecular terminal - Google Patents

Polycyano oligo phenylene ethynylene compound having electron-donating group introduced to its molecular terminal Download PDF

Info

Publication number
JP2009209073A
JP2009209073A JP2008052688A JP2008052688A JP2009209073A JP 2009209073 A JP2009209073 A JP 2009209073A JP 2008052688 A JP2008052688 A JP 2008052688A JP 2008052688 A JP2008052688 A JP 2008052688A JP 2009209073 A JP2009209073 A JP 2009209073A
Authority
JP
Japan
Prior art keywords
compound
formula
group
cdcl
nmr
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.)
Granted
Application number
JP2008052688A
Other languages
Japanese (ja)
Other versions
JP5540342B2 (en
Inventor
Hitohiro Yamaguchi
仁宏 山口
Takeaki Wakamiya
建昭 若宮
Zenichi Yoshida
善一 吉田
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.)
Kinki University
Original Assignee
Kinki University
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 Kinki University filed Critical Kinki University
Priority to JP2008052688A priority Critical patent/JP5540342B2/en
Publication of JP2009209073A publication Critical patent/JP2009209073A/en
Application granted granted Critical
Publication of JP5540342B2 publication Critical patent/JP5540342B2/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new light-emitting material which emits lights from a bluish purple color region to a red color region in high light-emitting efficiency as a light-emitting material. <P>SOLUTION: A polycyano oligo phenylene ethynylene compound is obtained by introducing an electron-donating group to its molecular terminal represented by general formula (1), wherein D is an aromatic electron-donating group containing one or more of nitrogen, oxygen, sulfur, iron, cobalt and nickel; (m) is an integer of 1 to 4; (n) is 0 or an integer of 1 to 4. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、新規な有機π共役系化合物、さらに詳述すると、有機強発光材料に加え、有機エレクトロルミネッセンス素子用の発光材料、オプトエレクトロニクス用材料およびバイオセンサーなどとして用いることができる、分子末端に電子供与基を導入したポリシアノオリゴフェニレンエチニレン化合物に関する。   The present invention is a novel organic π-conjugated compound, more specifically, in addition to a strong organic luminescent material, it can be used as a luminescent material for organic electroluminescence elements, an optoelectronic material, a biosensor, etc. The present invention relates to a polycyano oligophenylene ethynylene compound into which an electron donating group is introduced.

有機材料に関する電解発光(EL)は、蛍光性有機化合物としてのアントラセン結晶において初めて発見された(非特許文献１)。実用的なデバイス開発は、1987年にTangとVanSlyke がトリス（８−ヒドロキシキノリン）アルミニウムを用いて強いEL発光を観測したことにはじまる（非特許文献２）。ポリマー材料については、1990年にFriendらがポリフェニレンビニレンを用いたEL素子を試作したのが最初である（非特許文献３）。これらのTangとFriendによる発明以来、産業界および学会において有機エレクトロルミネッセンスデバイスの研究開発は大きな進展を見せた。   Electroluminescence (EL) for organic materials was first discovered in anthracene crystals as fluorescent organic compounds (Non-Patent Document 1). Practical device development began in 1987 when Tang and VanSlyke observed strong EL emission using tris (8-hydroxyquinoline) aluminum (Non-patent Document 2). Regarding polymer materials, Friend et al. First made an EL element using polyphenylene vinylene in 1990 (Non-patent Document 3). Since these inventions by Tang and Friend, research and development of organic electroluminescent devices has made great progress in industry and academic societies.

ところで、フルカラーディスプレィ用の場合、三原色を構成する赤、緑、青それぞれの発光材料が必要となるうえ、それらの色純度が問題となるが、現在知られている有機エレクトロルミネッセンス素子の赤色発光効率は不十分である。   By the way, in the case of a full-color display, red, green, and blue light-emitting materials constituting the three primary colors are required and their color purity is a problem, but the red emission efficiency of currently known organic electroluminescence elements Is insufficient.

このため、青紫領域の光を発生する有機発光材料と、青紫領域の光を吸収し、赤色の蛍光をもつ色素と組み合わせた有機エレクトロルミネッセンス素子が開発されている（特許文献１）。しかしながら、この方法は青紫領域の光を吸収して、赤色への色変換をおこなうものであり、この方法では発光効率が低下してしまう。   For this reason, an organic electroluminescent element combined with an organic light emitting material that generates light in the blue-violet region and a dye that absorbs light in the blue-violet region and has red fluorescence has been developed (Patent Document 1). However, this method absorbs light in the blue-violet region and performs color conversion to red, and this method decreases the light emission efficiency.

この点に鑑み、本発明者らは、分子末端に電子供与基を導入した2-シアノフェニレンエチニレン3量体を合成し、該化合物が青紫から黄色の領域で高い発光効率で発光することを見出した（非特許文献４）。しかし、赤色発光体としては不十分であった。
M. Pope, H. P. Kallman, P. Magnante, J. Chem. Phys., 38, 2042 (1968) C. W. Tang, S. A. VanSlyke, Appl. Phys. Lett., 51, 913 (1987) J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns, A. B. Holmes, Nature, 347, 539 (1990) Y. Yamaguchi, T. Ochi, Z. Yoshida et al, Org, Lett., 8, 717 (2006) 欧州特許第1067165公開公報 In view of this point, the present inventors synthesized a 2-cyanophenylene ethynylene trimer in which an electron donating group is introduced at the molecular end, and that the compound emits light with high luminous efficiency in a blue-violet to yellow region. (Non-Patent Document 4). However, it was insufficient as a red light emitter.
M. Pope, HP Kallman, P. Magnante, J. Chem. Phys., 38, 2042 (1968) CW Tang, SA VanSlyke, Appl. Phys. Lett., 51, 913 (1987) JH Burroughes, DDC Bradley, AR Brown, RN Marks, K. Mackay, RH Friend, PL Burns, AB Holmes, Nature, 347, 539 (1990) Y. Yamaguchi, T. Ochi, Z. Yoshida et al, Org, Lett., 8, 717 (2006) European Patent No. 1067165

本発明は、青紫色領域から赤色領域の発光材料として高い発光効率で発光し有機エレクトロルミネッセンス素子として有用であるばかりでなく、オプトエレクトロニクス、バイオセンサーなどにも適用できる、新規な有機π共役化合物を提供することを目的とする。   The present invention provides a novel organic π-conjugated compound that not only emits light with high luminous efficiency as a light emitting material from the blue-violet region to the red region but is useful as an organic electroluminescence device, and can also be applied to optoelectronics, biosensors, and the like. The purpose is to provide.

本発明者らは、上記目的を達成するために鋭意検討を重ねた結果、分子末端に電子供与基を導入した特定のポリシアノオリゴフェニレンエチニレン化合物が、広範な可視領域で高い発光効率で発光することを見出し、発明を完成した。本発明の化合物は、有機エレクトロルミネッセンス用素子として好適に利用されるばかりでなく、オプトエレクトロニクス、バイオセンサーなどにも適用できる。   As a result of intensive studies to achieve the above object, the present inventors have found that a specific polycyano oligophenylene ethynylene compound having an electron donating group introduced at the molecular end emits light with high luminous efficiency in a wide visible region. We found out and completed the invention. The compound of the present invention is not only suitably used as an organic electroluminescence device, but can also be applied to optoelectronics, biosensors, and the like.

すなわち、本発明は、式（１）で表されることを特徴とする分子末端に電子供与基を導入したポリシアノオリゴフェニレンエチニレン化合物である。   That is, this invention is a polycyano oligo phenylene ethynylene compound which introduce | transduced the electron-donating group into the molecular terminal characterized by being represented by Formula (1).

上記式（１）において、Dは窒素、酸素、硫黄、鉄、コバルト、ニッケルの1種もしくは2種以上を含む芳香族電子供与性基を示し、mは1から4の整数を示し、nは0もしくは1から5の整数を示す。好ましくはmは１もしくは２であり、nは０、１もしくは２である。   In the above formula (1), D represents an aromatic electron donating group containing one or more of nitrogen, oxygen, sulfur, iron, cobalt and nickel, m represents an integer of 1 to 4, and n represents 0 or an integer from 1 to 5 is indicated. Preferably m is 1 or 2, and n is 0, 1 or 2.

さらに、上記式（１）においてDが式（２）で表されることを特徴とする分子末端に電子供与基を導入したポリシアノオリゴフェニレンエチニレン化合物である。   Furthermore, it is a polycyano oligo phenylene ethynylene compound in which an electron donating group is introduced into a molecular terminal, wherein D in the above formula (1) is represented by the formula (2).

上記式（２）において、Xは、OR、SRもしくはNR2を示し、ここでRは炭素数１〜１４の置換もしくは無置換のアルキル基、アリール基もしくはアラルキル基を示す。 In the above formula (2), X represents OR, SR or NR 2 , wherein R represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group having 1 to 14 carbon atoms.

さらに、上記式(1)記載のDの電子供与基の具体的な例を下記に示す。   Further, specific examples of the electron donating group of D described in the above formula (1) are shown below.

上記式（３）において、RおよびQは炭素数１〜１４の置換もしくは無置換のアルキル基、アリール基もしくはアラルキル基を示す。   In said formula (3), R and Q show a C1-C14 substituted or unsubstituted alkyl group, an aryl group, or an aralkyl group.

上記式（５）において、Rは炭素数１〜１４の置換もしくは無置換のアルキル基、アリール基もしくはアラルキル基を示す。   In said formula (5), R shows a C1-C14 substituted or unsubstituted alkyl group, an aryl group, or an aralkyl group.

上記式（６）において、Rは炭素数１〜１４の置換もしくは無置換のアルキル基、アリール基もしくはアラルキル基を示す。   In the above formula (6), R represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group having 1 to 14 carbon atoms.

上記式（７）において、RおよびQは炭素数１〜１４の置換もしくは無置換のアルキル基、アリール基もしくはアラルキル基を示す。   In said formula (7), R and Q show a C1-C14 substituted or unsubstituted alkyl group, an aryl group, or an aralkyl group.

本発明に係わる有機エレクトロルミネッセンス素子は、陽極と陰極とこれら両極間に介在させた有機薄膜層からなる有機エレクトロルミネッセンス素子であって、有機薄膜層として上記の分子末端に電子供与性基を導入したポリシアノオリゴフェニレンエチニレン化合物を含んで構成されるものであって、分子末端に電子供与性基を導入したポリシアノオリゴフェニレンエチニレン化合物以外は公知の有機エレクトロルミネッセンス素子用の材料を用いることができる。   The organic electroluminescence device according to the present invention is an organic electroluminescence device comprising an anode, a cathode, and an organic thin film layer interposed between the two electrodes, and an electron donating group is introduced at the molecular end as the organic thin film layer. It is composed of a polycyano-oligophenylene ethynylene compound, and a known material for an organic electroluminescence element can be used except for the polycyano-oligophenylene ethynylene compound having an electron-donating group introduced at the molecular end. it can.

本発明の分子末端に電子供与基を導入したポリシアノオリゴフェニレンエチニレン化合物は、上記式（１）で示されるような棒状の構造を有しており、比較的安定性に優れたものである。電子供与性基の種類によっては、青紫色から赤色の発光効率の優れた発光を有する。   The polycyano oligophenylene ethynylene compound in which an electron donating group is introduced at the molecular end of the present invention has a rod-like structure as shown by the above formula (1) and is relatively excellent in stability. . Depending on the type of the electron-donating group, the light emission has excellent emission efficiency from blue purple to red.

このことから、本発明の分子末端に電子供与基を導入したポリシアノオリゴフェニレンエチニレン化合物は、有機エレクトロルミネッセンス素子として好適に用いられるのみならず、バイオセンサーやオプトエレクトロニクス用の材料としても適用できる。   Thus, the polycyano oligophenylene ethynylene compound having an electron donating group introduced at the molecular end of the present invention can be used not only suitably as an organic electroluminescence device but also as a material for biosensors or optoelectronics. .

式（１）で表される分子末端に電子供与基を導入したポリシアノオリゴフェニレンエチニレン化合物において、電子供与基Dの好ましい官能基として式（２）の中で、XがOCH3、SCH3、N(CH3)2、N(C6H5)2、およびN(C6H5)2のベンゼン環の窒素原子のパラ位にCN基、OCH3基、フェニル基、4-メトキシフェニル基、4-シアノフェニル基を導入した場合に特に好ましい。 In the polycyano oligo phenylene ethynylene compound in which an electron donating group is introduced at the molecular end represented by the formula (1), X is OCH 3 , SCH 3 in the formula (2) as a preferable functional group of the electron donating group D. , N (CH 3 ) 2 , N (C 6 H 5 ) 2 , and CN (OCH 3 group, phenyl group, 4-methoxyphenyl) at the para position of the nitrogen atom of the benzene ring of N (C 6 H 5 ) 2 Particularly preferred is the introduction of a 4-cyanophenyl group.

さらに、電子供与基Dの具体的な例として挙げた式（３）ではRがC8H17−、Qがフェニル基の場合、式（５）ではRがC6H13−の場合、式（６）ではRが3,5-ジ(tert-ブチル)フェニル基の場合、式（７）ではRが3,5-ジ(tert-ブチル)フェニル基、Qがフェニル基の場合に特に好ましい。 Further, in the formula (3) given as a specific example of the electron donating group D, when R is C 8 H 17 -and Q is a phenyl group, when R is C 6 H 13-in the formula (5), the formula In (6), when R is 3,5-di (tert-butyl) phenyl group, in formula (7), R is particularly preferable when R is 3,5-di (tert-butyl) phenyl group and Q is phenyl group. .

分子末端に電子供与基を導入したポリシアノオリゴフェニレンエチニレン化合物の製造法としては、パラジウムを用いたクロスカップリング反応において、ヨウ素基が臭素基よりも反応性が高いことを利用して、分子の方向性を決定する方法が好ましい。   As a method for producing a polycyano oligophenylene ethynylene compound in which an electron donating group is introduced at the molecular end, in the cross-coupling reaction using palladium, the iodine group is more reactive than the bromine group. A method of determining the directionality of is preferable.

即ち、まず、分子末端を形成する電子供与基を含む芳香族置換アセチレン誘導体とヨウ素および臭素で置換したシアノ基含有ベンゼン誘導体の反応において、パラジウムを用いるクロスカップリング反応で中間体を合成する。次いで、該中間体をシアノ基含有もしくは含有しないフェニル基置換アセチレン誘導体を同様のパラジウムを用いるクロスカップリング反応で反応させ目的物を得る。   That is, first, an intermediate is synthesized by a cross-coupling reaction using palladium in a reaction of an aromatic substituted acetylene derivative containing an electron donating group that forms a molecular end and a cyano group-containing benzene derivative substituted with iodine and bromine. Next, a phenyl group-substituted acetylene derivative containing or not containing a cyano group is reacted in the same cross-coupling reaction using palladium to obtain the desired product.

以下、本発明について実施例をもちいてさらに詳しく説明するが、本発明は以下の実施例に限定されるものではない。なお、実施例にて採用した分析条件等は下記のとおりである。
1H NMR (300 MHz) および13C NMR (75 MHz) 測定条件：
装置：VARIAN Mercury 300 （バリアン）
測定溶媒：CDCl3
基準物質：テトラメチルシラン（TMS）(δ0.0 ppm for 1H )
CDCl3 (δ77.0 ppm for 13C)
質量分析装置：JEOL JMS-700 TKM （日本電子データム） EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this invention is not limited to a following example. In addition, the analysis conditions etc. which were employ | adopted in the Example are as follows.
1 H NMR (300 MHz) and 13 C NMR (75 MHz) Measurement conditions:
Equipment: VARIAN Mercury 300 (Varian)
Measuring solvent: CDCl 3
Reference substance: Tetramethylsilane (TMS) (δ0.0 ppm for 1 H)
CDCl 3 (δ77.0 ppm for 13 C)
Mass spectrometer: JEOL JMS-700 TKM (JEOL Datum)

式（1‐1〜4）および（2‐1〜4）で表される化合物の製造例   Examples of production of compounds represented by formulas (1-1 to 4) and (2-1 to 4)

上記式（1‐1〜4）で表される化合物の製造例について説明する。
反応（1）：化合物（1‐1'〜4'）の合成
アルゴン雰囲気下、５−ブロモ−2−ヨードベンゾニトリル（900 mg、1 eq.）のEt3N / THF = 1 / 1（体積比）（20 ml）溶液に Pd(PPh3)2Cl4（82 mg、0.04 eq.）とCuI（11 mg、0.02 eq.）を室温で加え、5分攪拌した。この溶液に化合物（1‐1''）（387 mg、1.5 eq.）のTHF溶液（10 ml）を室温で加え、室温にて1時間攪拌した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ヘキサン / ベンゼン = 1 : 1）で精製することにより、目的化合物（1‐1'） 894 mg（収率98％）を得た。 Production examples of the compounds represented by the above formulas (1-1 to 4) will be described.
Reaction (1): Synthesis of Compound (1-1 ′ to 4 ′) Et 3 N / THF = 1/1 (volume) of 5-bromo-2-iodobenzonitrile (900 mg, 1 eq.) Under argon atmosphere Ratio) (20 ml), Pd (PPh 3 ) 2 Cl 4 (82 mg, 0.04 eq.) And CuI (11 mg, 0.02 eq.) Were added at room temperature and stirred for 5 minutes. To this solution was added a THF solution (10 ml) of compound (1-1 ″) (387 mg, 1.5 eq.) At room temperature, and the mixture was stirred at room temperature for 1 hour, and then the solvent was distilled off under reduced pressure. The obtained mixture was purified by silica gel column chromatography (hexane / benzene = 1: 1) to obtain 894 mg (yield 98%) of the target compound (1-1 ′).

上述した化合物（1‐1''）の代わりに（1‐2''）、（1‐3''）および（1‐4''）を使用する以外は同様の操作を行い、シリカゲルカラムクロマトグラフィー（ヘキサン / ベンゼン = 1 : 1）で精製することにより、目的化合物（1‐2'）903 mg（収率94％）、目的化合物（1‐3'）748 mg（収率79％）および目的化合物（1‐4'）1.06 g（収率81％）を得た。   Perform the same procedure except for using (1-2 ''), (1-3 '') and (1-4 '') instead of the above compound (1-1 ''). The target compound (1-2 ') 903 mg (yield 94%), target compound (1-3') 748 mg (yield 79%) and purified by chromatography (hexane / benzene = 1: 1) 1.06 g (yield 81%) of the target compound (1-4 ′) was obtained.

反応（2）：上記式（1‐1〜4）で表される化合物の合成
アルゴン雰囲気下、化合物（1‐1'）（246 mg、1 eq.）のEt3N / THF = 1 / 1（体積比）（10 ml）溶液に Pd(PPh3)2Cl4（22 mg、0.04 eq.）とCuI（3 mg、0.02 eq.）を室温で加え、5分攪拌した。この溶液に2−エチニルベンゾニトリル（200 mg、2.0 eq.）のTHF溶液（5 ml）を室温で加え、12時間加熱還流した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ヘキサン / ベンゼン = 1 : 2）で精製することにより、目的化合物（1‐1） 243 mg（収率86％）を得た。 Reaction (2): Synthesis of the compound represented by the above formula (1-1 to 4) Et 3 N / THF = 1/1 of the compound (1-1 ′) (246 mg, 1 eq.) Under an argon atmosphere (Volume ratio) (10 ml) To the solution, Pd (PPh 3 ) 2 Cl 4 (22 mg, 0.04 eq.) And CuI (3 mg, 0.02 eq.) Were added at room temperature and stirred for 5 minutes. To this solution was added 2-ethynylbenzonitrile (200 mg, 2.0 eq.) In THF (5 ml) at room temperature, and the mixture was heated to reflux for 12 hours. The solvent was evaporated under reduced pressure. The resulting mixture was purified by silica gel column chromatography (hexane / benzene = 1: 2) to obtain 243 mg (yield 86%) of the target compound (1-1).

上述した化合物（1‐1'）の代わりに（1‐2'）、（1‐3'）および（1‐4'）を使用する以外は同様の操作を行い、目的化合物（1‐2）221 mg（収率75％）、目的化合物（1‐3）190 mg（収率65％）および目的化合物（1‐4）265 mg（収率68％）を得た。   Perform the same operation except that (1-2 '), (1-3') and (1-4 ') are used in place of the above compound (1-1') to obtain the target compound (1-2). There were obtained 221 mg (yield 75%), target compound (1-3) 190 mg (yield 65%) and target compound (1-4) 265 mg (yield 68%).

このようにして得られた式（1‐1〜4）で表される化合物のスペクトル特性は以下の通りであった。
（1‐1）：アイボリー色固体、1H NMR (CDCl3): d 3.85 (s, 3H), 6.91 and 7.57 (AA'XX', 4H), 7.47 (tdd, J = 0.6, 1.8, 7.5 Hz, 1H), 7.53-7.67 (m, 3H), 7.71 (ddd, J = 0.6, 1.2, 7.8 Hz, 1H), 7.76 (dd, J = 1.5, 8.1 Hz, 1H), 7.87 (d, J = 1.5 Hz, 1H); 13C NMR (CDCl3): d 55.37, 84.73, 88.80, 93.18, 98.97, 113.75, 114.19, 115.45, 115.52, 116.80, 117.32, 121.87, 126.15, 127.91, 129.02, 131.88, 132.23, 132.54, 132.77, 133.76, 135.47, 135.53, 160.64; HR MS (FAB, 正イオンモード) [M]+(C25H14N2O): 計算値 358.1106, 実測値 358.1125.
（1‐2）：淡黄色固体、1H NMR (CDCl3): d 2.51 (s, 3H), 7.23 and 7.52 (AA'XX', 4H), 7.48 (tdd, J = 0.6, 1.8, 7.5 Hz, 1H), 7.57-7.68 (m, 3H), 7.71 (ddd, J = 0.6, 1.5, 8.1 Hz, 1H), 7.77 (dd, J = 1.5, 8.1 Hz, 1H), 7.87 (d, J = 1.5 Hz, 1H); 13C NMR (CDCl3): d 15.13, 85.77, 88.97, 93.10, 98.52, 115.55, 115.61, 116.71, 117.29, 117.73, 122.21, 125.62, 126.10, 127.53, 129.07, 132.03, 132.25, 132.32, 132.54, 133.21, 135.50, 135.55, 141.36; HR MS (FAB, 正イオンモード) [M]+(C25H14N2S): 計算値374.0878, 実測値374.0887.
（1‐3）：黄土色固体、1H NMR (CDCl3): d 3.02 (s, 6H), 6.66 and 7.50 (AA'XX', 4H), 7.46 (td, J = 1.8, 7.5 Hz, 1H), 7.54-7.66 (m, 3H), 7.70 (dd, J = 1.5, 8.7 Hz, 1H), 7.72 (dd, J = 1.8, 8.4 Hz, 1H), 7.84 (d, J = 1.5 Hz, 1H); 13C NMR (CDCl3): d 39.65, 84.68, 88.48, 93.49, 101.09, 108.04, 111.40, 111.88, 114.95, 115.45, 116.99, 117.35, 121.04, 126.29, 128.61, 131.15, 132.49, 133.46, 133.99, 135.83, 136.35, 136.54, 150.90; HR MS (FAB, 正イオンモード) [M]+(C26H17N3): 計算値371.1422, 実測値371.1398.
（1‐4）：黄色固体、1H NMR (CDCl3): d 7.00 and 7.45 (AA'XX', 4H), 7.07-7.26 (m, 6H), 7.27-7.33 (m, 4H), 7.50 (td, J = 1.5, 7.8 Hz, 1H), 7.56-7.67 (m, 3H), 7.71 (dd, J = 1.5, 8.7 Hz, 1H), 7.75 (dd, J = 1.5, 8.4 Hz, 1H), 7.85 (d, J = 1.5 Hz, 1H); 13C NMR (CDCl3): d 85.15, 88.77, 93.12, 99.44, 113.78, 115.34, 115.46, 116.80, 117.32, 124.44, 123.99, 125.34, 126.14, 127.92, 128.99, 129.46, 131.83, 132.21, 132.54, 132.75, 133.12, 134.06, 135.44, 135.52, 146.77, 149.03; HR MS (FAB, 正イオンモード) [M]+(C36H21N3): 計算値495.1735, 実測値495.1761. The spectral characteristics of the compounds represented by the formulas (1-1 to 4) thus obtained were as follows.
(1-1): Ivory solid, 1 H NMR (CDCl 3 ): d 3.85 (s, 3H), 6.91 and 7.57 (AA'XX ', 4H), 7.47 (tdd, J = 0.6, 1.8, 7.5 Hz , 1H), 7.53-7.67 (m, 3H), 7.71 (ddd, J = 0.6, 1.2, 7.8 Hz, 1H), 7.76 (dd, J = 1.5, 8.1 Hz, 1H), 7.87 (d, J = 1.5 Hz, 1H); 13 C NMR (CDCl 3 ): d 55.37, 84.73, 88.80, 93.18, 98.97, 113.75, 114.19, 115.45, 115.52, 116.80, 117.32, 121.87, 126.15, 127.91, 129.02, 131.88, 132.23, 132.54, 132.77, 133.76, 135.47, 135.53, 160.64; HR MS (FAB, positive ion mode) [M] + (C 25 H 14 N 2 O): calculated value 358.1106, actual value 358.1125.
(1-2): pale yellow solid, 1 H NMR (CDCl 3 ): d 2.51 (s, 3H), 7.23 and 7.52 (AA'XX ', 4H), 7.48 (tdd, J = 0.6, 1.8, 7.5 Hz , 1H), 7.57-7.68 (m, 3H), 7.71 (ddd, J = 0.6, 1.5, 8.1 Hz, 1H), 7.77 (dd, J = 1.5, 8.1 Hz, 1H), 7.87 (d, J = 1.5 13C NMR (CDCl 3 ): d 15.13, 85.77, 88.97, 93.10, 98.52, 115.55, 115.61, 116.71, 117.29, 117.73, 122.21, 125.62, 126.10, 127.53, 129.07, 132.03, 132.25, 132.32, 132.54 , 133.21, 135.50, 135.55, 141.36; HR MS (FAB, positive ion mode) [M] + (C 25 H 14 N 2 S): calculated value 374.0878, actual value 374.0887.
(1-3): Ocher solid, 1 H NMR (CDCl 3 ): d 3.02 (s, 6H), 6.66 and 7.50 (AA'XX ', 4H), 7.46 (td, J = 1.8, 7.5 Hz, 1H ), 7.54-7.66 (m, 3H), 7.70 (dd, J = 1.5, 8.7 Hz, 1H), 7.72 (dd, J = 1.8, 8.4 Hz, 1H), 7.84 (d, J = 1.5 Hz, 1H) ; 13 C NMR (CDCl 3 ): d 39.65, 84.68, 88.48, 93.49, 101.09, 108.04, 111.40, 111.88, 114.95, 115.45, 116.99, 117.35, 121.04, 126.29, 128.61, 131.15, 132.49, 133.46, 133.99, 135.83, 136.35, 136.54, 150.90; HR MS (FAB, positive ion mode) [M] + (C 26 H 17 N 3 ): calculated value 371.1422, actual value 371.1398.
(1-4): Yellow solid, 1 H NMR (CDCl 3 ): d 7.00 and 7.45 (AA'XX ', 4H), 7.07-7.26 (m, 6H), 7.27-7.33 (m, 4H), 7.50 ( td, J = 1.5, 7.8 Hz, 1H), 7.56-7.67 (m, 3H), 7.71 (dd, J = 1.5, 8.7 Hz, 1H), 7.75 (dd, J = 1.5, 8.4 Hz, 1H), 7.85 (d, J = 1.5 Hz, 1H); 13 C NMR (CDCl 3 ): d 85.15, 88.77, 93.12, 99.44, 113.78, 115.34, 115.46, 116.80, 117.32, 124.44, 123.99, 125.34, 126.14, 127.92, 128.99, 129.46, 131.83, 132.21, 132.54, 132.75, 133.12, 134.06, 135.44, 135.52, 146.77, 149.03; HR MS (FAB, positive ion mode) [M] + (C 36 H 21 N 3 ): calculated 495.1735, actual 495.1761.

反応（3）：上記式（2‐1〜4）で表される化合物の合成
アルゴン雰囲気下、化合物（1‐1'）（246 mg、1 eq.）のEt3N / THF = 1 / 1（体積比）（10 ml）溶液に Pd(PPh3)2Cl4（22 mg、0.04 eq.）とCuI（3 mg、0.02 eq.）を室温で加え、5分攪拌した。この溶液に2−エチニルテレフタロニトリル（239 mg、2.0 eq.）のTHF溶液（5 ml）を室温で加え、12時間加熱還流した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ヘキサン / ベンゼン = 1 : 2）で精製することにより、目的化合物（2‐1） 217 mg（収率72％）を得た。 Reaction (3): Synthesis of compound represented by formula (2-1-4) above Et 3 N / THF = 1/1 of compound (1-1 ′) (246 mg, 1 eq.) Under argon atmosphere (Volume ratio) (10 ml) To the solution, Pd (PPh 3 ) 2 Cl 4 (22 mg, 0.04 eq.) And CuI (3 mg, 0.02 eq.) Were added at room temperature and stirred for 5 minutes. To this solution was added 2-ethynyl terephthalonitrile (239 mg, 2.0 eq.) In THF (5 ml) at room temperature, and the mixture was heated to reflux for 12 hours. The solvent was evaporated under reduced pressure. The resulting mixture was purified by silica gel column chromatography (hexane / benzene = 1: 2) to obtain 217 mg (yield 72%) of the target compound (2-1).

上述した化合物（1‐1'）の代わりに（1‐2'）、（1‐3'）および（1‐4'）を使用する以外は同様の操作を行い、目的化合物（2‐2）175 mg（収率59％）、目的化合物（2‐3）162 mg（収率52％）および目的化合物（2‐4）266 mg（収率65％）を得た。   Perform the same operation except that (1-2 ′), (1-3 ′) and (1-4 ′) are used in place of the compound (1-1 ′) described above to obtain the target compound (2-2). 175 mg (59% yield), 162 mg (52% yield) of the target compound (2-3) and 266 mg (65% yield) of the target compound (2-4) were obtained.

このようにして得られた式（2‐1〜4）で表される化合物のスペクトル特性は以下の通りであった。
（2‐1）：黄色固体、1H NMR (CDCl3): d 3.85 (s, 3H), 6.92 and 7.57 (AA'XX', 4H), 7.62 (dd, J = 0.6, 8.1 Hz, 1H), 7.73 (dd, J = 1.5, 7.5 Hz, 1H), 7.76 (dd, J = 1.8, 8.1 Hz, 1H), 7.83 (dd, J = 0.6, 8.1 Hz, 1H), 7.87 (d, J = 1.5 Hz, 1H), 7.92 (d, J = 1.8 Hz, 1H); 13C NMR (CDCl3): d 55.37, 84.68, 86.59, 95.94, 99.73, 113.59, 114.25, 115.65, 115.81, 116.30, 116.58, 116.86, 119.28, 120.73, 127.64, 128.79, 131.72, 131.99, 133.41, 133.84, 135.26, 135.55, 135.74, 160.80; HR MS (FAB, 正イオンモード) [M]+(C26H13N3O): 計算値383.1059, 実測値383.1072.
（2‐2）：黄色固体、1H NMR (CDCl3): d 2.52 (s, 3H), 7.23 and 7.53 (AA'XX', 4H), 7.64 (d, J = 8.4 Hz, 1H), 7.74 (d, J = 1.5, 8.1 Hz, 1H), 7.78 (dd, J = 1.5, 8.4 Hz, 1H), 7.83 (d, J = 7.5 Hz, 1H), 7.89 (d, J = 1.5 Hz, 1H), 7.93 (d, J = 1.5 Hz, 1H); 13C NMR (CDCl3): d 15.06, 85.66, 86.72, 95.82, 99.21, 115.77, 115.81, 116.30, 116.51, 116.83, 117.47, 119.27, 121.02, 125.52, 127.55, 128.38, 131.77, 132.12, 132.35, 133.41, 135.26, 135.59, 135.75, 141.62; HR MS (FAB, 正イオンモード) [M]+(C26H13N3S): 計算値399.0830, 実測値399.0854.
（2‐3）：橙色固体、1H NMR (CDCl3): d 3.03 (s, 6H), 6.66 and 7.50 (AA'XX', 4H), 7.58 (dd, J = 0.6, 8.1 Hz, 1H), 7.72 (dd, J = 1.8, 8.4 Hz, 1H), 7.72 (dd, J = 1.8, 8.1 Hz, 1H), 7.82 (dd, J = 0.6, 8.4 Hz, 1H), 7.84 (d, J = 1.2 Hz, 1H), 7.92 (d, J = 1.2 Hz, 1H); 13C NMR (CDCl3): d 40.09, 84.71, 86.31, 96.27, 101.93, 107.73, 111.58, 115.00, 115.85, 116.35, 116.77, 116.82, 119.16, 119.78, 127.73, 129.45, 131.55(x2), 133.37, 133.58, 135.20, 135.44, 135.74, 150.90; HR MS (FAB, 正イオンモード) [M]+(C27H16N4): 計算値396.1375, 実測値396.1392
（2‐4）：黄色固体、1H NMR (CDCl3): d 7.01 and 7.45 (AA'XX', 4H), 7.06-7.16 (m, 6H), 7.27-7.33 (m, 4H), 7.60 (d, J = 8.1 Hz, 1H), 7.73 (dd, J = 1.8, 6.6 Hz, 1H), 7.76 (dd, J = 1.5, 6.9 Hz, 1H), 7.83 (d, J = 8.4 Hz, 1H), 7.87 (d, J = 1.5 Hz, 1H), 7.93 (d, J = 1.5 Hz, 1H); 13C NMR (CDCl3): d 85.10, 86.56, 96.00, 100.24, 113.49, 115.51, 115.82, 116.31, 116.61, 116.80, 119.22, 120.52, 121.31, 124.08, 125.40, 127.62, 128.81, 129.49, 131.69, 131.92, 133.19, 133.40, 135.24, 135.51, 135.74, 146.71, 149.18; HR MS (FAB, 正イオンモード) [M]+(C37H20N4): 計算値520.1688, 実測値520.1672. The spectral characteristics of the compounds represented by the formulas (2-1 to 4) thus obtained were as follows.
(2-1): yellow solid, 1 H NMR (CDCl 3 ): d 3.85 (s, 3H), 6.92 and 7.57 (AA'XX ', 4H), 7.62 (dd, J = 0.6, 8.1 Hz, 1H) , 7.73 (dd, J = 1.5, 7.5 Hz, 1H), 7.76 (dd, J = 1.8, 8.1 Hz, 1H), 7.83 (dd, J = 0.6, 8.1 Hz, 1H), 7.87 (d, J = 1.5 Hz, 1H), 7.92 (d, J = 1.8 Hz, 1H); 13 C NMR (CDCl 3 ): d 55.37, 84.68, 86.59, 95.94, 99.73, 113.59, 114.25, 115.65, 115.81, 116.30, 116.58, 116.86, 119.28, 120.73, 127.64, 128.79, 131.72, 131.99, 133.41, 133.84, 135.26, 135.55, 135.74, 160.80; HR MS (FAB, positive ion mode) [M] + (C 26 H 13 N 3 O): Calculated 383.1059 , Measured value 383.11072.
(2-2): yellow solid, 1 H NMR (CDCl 3 ): d 2.52 (s, 3H), 7.23 and 7.53 (AA'XX ', 4H), 7.64 (d, J = 8.4 Hz, 1H), 7.74 (d, J = 1.5, 8.1 Hz, 1H), 7.78 (dd, J = 1.5, 8.4 Hz, 1H), 7.83 (d, J = 7.5 Hz, 1H), 7.89 (d, J = 1.5 Hz, 1H) , 7.93 (d, J = 1.5 Hz, 1H); 13 C NMR (CDCl 3 ): d 15.06, 85.66, 86.72, 95.82, 99.21, 115.77, 115.81, 116.30, 116.51, 116.83, 117.47, 119.27, 121.02, 125.52, 127.55, 128.38, 131.77, 132.12, 132.35, 133.41, 135.26, 135.59, 135.75, 141.62; HR MS (FAB, positive ion mode) [M] + (C 26 H 13 N 3 S): calculated 399.0830, actual 399.0854 .
(2-3): Orange solid, 1 H NMR (CDCl 3 ): d 3.03 (s, 6H), 6.66 and 7.50 (AA'XX ', 4H), 7.58 (dd, J = 0.6, 8.1 Hz, 1H) , 7.72 (dd, J = 1.8, 8.4 Hz, 1H), 7.72 (dd, J = 1.8, 8.1 Hz, 1H), 7.82 (dd, J = 0.6, 8.4 Hz, 1H), 7.84 (d, J = 1.2 Hz, 1H), 7.92 (d, J = 1.2 Hz, 1H); 13 C NMR (CDCl 3 ): d 40.09, 84.71, 86.31, 96.27, 101.93, 107.73, 111.58, 115.00, 115.85, 116.35, 116.77, 116.82, 119.16, 119.78, 127.73, 129.45, 131.55 (x2), 133.37, 133.58, 135.20, 135.44, 135.74, 150.90; HR MS (FAB, positive ion mode) [M] + (C 27 H 16 N 4 ): Calculated 396.1375 , Measured value 396.1392
(2-4): Yellow solid, 1 H NMR (CDCl 3 ): d 7.01 and 7.45 (AA'XX ', 4H), 7.06-7.16 (m, 6H), 7.27-7.33 (m, 4H), 7.60 ( d, J = 8.1 Hz, 1H), 7.73 (dd, J = 1.8, 6.6 Hz, 1H), 7.76 (dd, J = 1.5, 6.9 Hz, 1H), 7.83 (d, J = 8.4 Hz, 1H), 7.87 (d, J = 1.5 Hz, 1H), 7.93 (d, J = 1.5 Hz, 1H); 13 C NMR (CDCl 3 ): d 85.10, 86.56, 96.00, 100.24, 113.49, 115.51, 115.82, 116.31, 116.61 , 116.80, 119.22, 120.52, 121.31, 124.08, 125.40, 127.62, 128.81, 129.49, 131.69, 131.92, 133.19, 133.40, 135.24, 135.51, 135.74, 146.71, 149.18; HR MS (FAB, positive ion mode) [M] + (C 37 H 20 N 4 ): Calculated value 520.1688, Actual value 520.1672.

式（3‐1〜4）、（4‐1〜4）および（5‐1〜4）で表される化合物の製造例   Production examples of compounds represented by formulas (3-1 to 4), (4-1 to 4) and (5-1 to 4)

上記式（3‐1〜4）で表される化合物の製造例について説明する。
反応（1）：化合物（2‐1'〜4'）の合成
アルゴン雰囲気下、５−ブロモ−2−ヨードテレフタロニトリル（2.00 g、1 eq.）のEt3N / THF = 1 / 1（体積比）（40 ml）溶液に Pd(PPh3)2Cl4（169 mg、0.04 eq.）とCuI（23 mg、0.02 eq.）を室温で加え、5分攪拌した。この溶液に化合物（1‐1''）（794 mg、1.0 eq.）のTHF溶液（20 ml）を室温で加え、室温にて1時間攪拌した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ベンゼン）で精製することにより、目的化合物（2‐1'） 1.72 g（収率85％）を得た。 Production examples of the compound represented by the above formula (3-1 to 4) will be described.
Reaction (1): Synthesis of Compound (2-1′-4 ′) Et 3 N / THF = 1/1 of 5-bromo-2-iodoterephthalonitrile (2.00 g, 1 eq.) Under argon atmosphere Pd (PPh 3 ) 2 Cl 4 (169 mg, 0.04 eq.) And CuI (23 mg, 0.02 eq.) Were added to the solution (volume ratio) (40 ml) at room temperature and stirred for 5 minutes. To this solution was added a THF solution (20 ml) of compound (1-1 ″) (794 mg, 1.0 eq.) At room temperature, and the mixture was stirred at room temperature for 1 hour, and then the solvent was distilled off under reduced pressure. The resulting mixture was purified by silica gel column chromatography (benzene) to obtain 1.72 g (yield 85%) of the target compound (2-1 ′).

上述した化合物（1‐1''）の代わりに（1‐2''）、（1‐3''）および（1‐4''）を使用する以外は同様の操作を行い、目的化合物（2‐2'）1.59 g（収率75％）、目的化合物（2‐3'）1.43 g（収率68％）および目的化合物（2‐4'）2.22 g（収率78％）を得た。   The same procedure is performed except that (1-2 ″), (1-3 ″) and (1-4 ″) are used instead of the compound (1-1 ″) described above, and the target compound ( 2-2 ') 1.59 g (yield 75%), 1.43 g (68% yield) of the target compound (2-3') and 2.22 g (78% yield) of the target compound (2-4 ') were obtained. .

反応（2）：上記式（3‐1〜4）で表される化合物の合成
アルゴン雰囲気下、化合物（2‐1'）（265 mg、1 eq.）のEt3N / THF = 1 / 1（体積比）（10 ml）溶液に Pd(PPh3)2Cl4（22 mg、0.04 eq.）とCuI（3 mg、0.02 eq.）を室温で加え、5分攪拌した。この溶液にエチニルベンゼン（160 mg、2.0 eq.）のTHF溶液（5 ml）を室温で加え、12時間加熱還流した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ヘキサン / ベンゼン = 1 : 2）で精製することにより、目的化合物（3‐1） 251 mg（収率89％）を得た。 Reaction (2): Synthesis of the compound represented by the above formula (3-1-4) Et 3 N / THF = 1/1 of the compound (2-1 ′) (265 mg, 1 eq.) Under an argon atmosphere (Volume ratio) (10 ml) To the solution, Pd (PPh 3 ) 2 Cl 4 (22 mg, 0.04 eq.) And CuI (3 mg, 0.02 eq.) Were added at room temperature and stirred for 5 minutes. To this solution was added a THF solution (5 ml) of ethynylbenzene (160 mg, 2.0 eq.) At room temperature, and the mixture was heated to reflux for 12 hours, and then the solvent was evaporated under reduced pressure. The resulting mixture was purified by silica gel column chromatography (hexane / benzene = 1: 2) to obtain 251 mg (yield 89%) of the target compound (3-1).

上述した化合物（2‐1'）の代わりに（2‐2'）、（2‐3'）および（2‐4'）を使用する以外は同様の操作を行い、目的化合物（3‐2）292 mg（収率99％）、目的化合物（3‐3）278 mg（収率95％）および目的化合物（3‐4）335 mg（収率86％）を得た。   Perform the same operation except that (2-2 '), (2-3') and (2-4 ') are used in place of the compound (2-1') described above to obtain the target compound (3-2) 292 mg (99% yield), 278 mg (95% yield) of the target compound (3-3) and 335 mg (86% yield) of the target compound (3-4) were obtained.

このようにして得られた式（3‐1〜4）で表される化合物のスペクトル特性は以下の通りであった。
（3‐1）：淡黄色固体、1H NMR (CDCl3): d 3.86 (s, 3H), 6.92 and 7.56 (AA'XX', 4H), 7.37-7.45 (m, 3H), 7.61-7.64 (m, 2H), 7.85 (s, 1H), 7.87 (s, 1H); 13C NMR (CDCl3): d 55.41, 83.40, 84.06, 99.93, 101.00, 113.04, 114.35, 115.67, 115.73, 118.57, 118.90, 121.14, 126.04, 127.14, 128.62, 130.02, 132.20, 133.97, 135.32, 135.61, 161.11; HR MS (FAB, 正イオンモード) [M]+(C25H14N2O): 計算値358.1106, 実測値358.1123.
（3‐2）：黄色固体、1H NMR (CDCl3): d 2.51 (s, 3H), 7.24 and 7.52 (AA'XX', 4H), 7.36-7.45 (m, 3H), 7.60-7.64 (m, 2H), 7.86 (s, 1H), 7.87 (s, 1H); 13C NMR (CDCl3): d 15.01, 84.04, 84.34, 100.18, 100.47, 115.60, 115.64, 116.93, 118.72, 118.93, 121.09, 125.59, 126.38, 126.75, 128.63, 130.07, 132.21, 132.41, 135.46, 135.62, 142.30; HR MS (FAB, 正イオンモード) [M]+(C25H14N2S): 計算値374.0878, 実測値374.0893.
（3‐3）：橙色固体、1H NMR (CDCl3): d 3.03 (s, 6H), 6.66 and 7.48 (AA'XX', 4H), 7.36-7.44 (m, 3H), 7.59-7.63 (m, 2H), 7.79 (s, 1H), 7.82 (s, 1H); 13C NMR (CDCl3): d 40.06, 83.63, 84.23, 99.29, 103.41, 107.09, 111.58, 115.83, 115.97, 117.85, 118.72, 121.26, 124.89, 127.81, 128.58, 129.85, 132.11, 133.70, 134.92, 135.55, 151.11; HR MS (FAB, 正イオンモード) [M]+(C26H17N3): 計算値371.1422, 実測値371.1397.
（3‐4）：橙色固体、1H NMR (CDCl3): d 7.00 (AA'XX', 2H), 7.08-7.16 (m, 6H), 7.28-7.34 (m, 5H), 7.39-7.45 (m, 4H), 7.60-7.64 (m, 2H), 7.84 (s, 1H), 7.86 (s, 1H); 13C NMR (CDCl3): d 83.84, 84.10, 99.81, 101,63, 112.74, 115.70, 115.76, 118.41, 118.83, 121.05, 121.14, 124.27, 125.56, 125.75, 127.19, 128.60, 129.54, 129.97, 132.16, 133.30, 135.26, 135.59, 146.59, 149.55; HR MS (FAB, 正イオンモード) [M]+(C36H21N3): 計算値495.1735, 実測値495.1709. The spectral characteristics of the compounds represented by the formulas (3-1 to 4) thus obtained were as follows.
(3-1): pale yellow solid, 1 H NMR (CDCl 3 ): d 3.86 (s, 3H), 6.92 and 7.56 (AA'XX ', 4H), 7.37-7.45 (m, 3H), 7.61-7.64 (m, 2H), 7.85 (s, 1H), 7.87 (s, 1H); 13 C NMR (CDCl 3 ): d 55.41, 83.40, 84.06, 99.93, 101.00, 113.04, 114.35, 115.67, 115.73, 118.57, 118.90 , 121.14, 126.04, 127.14, 128.62, 130.02, 132.20, 133.97, 135.32, 135.61, 161.11; HR MS (FAB, positive ion mode) [M] + (C 25 H 14 N 2 O): calculated value 358.1106, actual value 358.1123.
(3-2): Yellow solid, 1 H NMR (CDCl 3 ): d 2.51 (s, 3H), 7.24 and 7.52 (AA'XX ', 4H), 7.36-7.45 (m, 3H), 7.60-7.64 ( m, 2H), 7.86 (s, 1H), 7.87 (s, 1H); 13 C NMR (CDCl 3 ): d 15.01, 84.04, 84.34, 100.18, 100.47, 115.60, 115.64, 116.93, 118.72, 118.93, 121.09, 125.59, 126.38, 126.75, 128.63, 130.07, 132.21, 132.41, 135.46, 135.62, 142.30; HR MS (FAB, positive ion mode) [M] + (C 25 H 14 N 2 S): calculated value 374.0878, actual value 374.0893 .
(3-3): Orange solid, 1 H NMR (CDCl 3 ): d 3.03 (s, 6H), 6.66 and 7.48 (AA'XX ', 4H), 7.36-7.44 (m, 3H), 7.59-7.63 ( m, 2H), 7.79 (s, 1H), 7.82 (s, 1H); 13 C NMR (CDCl 3 ): d 40.06, 83.63, 84.23, 99.29, 103.41, 107.09, 111.58, 115.83, 115.97, 117.85, 118.72, 121.26, 124.89, 127.81, 128.58, 129.85, 132.11, 133.70, 134.92, 135.55, 151.11; HR MS (FAB, positive ion mode) [M] + (C 26 H 17 N 3 ): calculated value 371.1422, actual value 371.1397.
(3-4): Orange solid, 1 H NMR (CDCl 3 ): d 7.00 (AA'XX ', 2H), 7.08-7.16 (m, 6H), 7.28-7.34 (m, 5H), 7.39-7.45 ( m, 4H), 7.60-7.64 (m, 2H), 7.84 (s, 1H), 7.86 (s, 1H); 13 C NMR (CDCl 3 ): d 83.84, 84.10, 99.81, 101,63, 112.74, 115.70 , 115.76, 118.41, 118.83, 121.05, 121.14, 124.27, 125.56, 125.75, 127.19, 128.60, 129.54, 129.97, 132.16, 133.30, 135.26, 135.59, 146.59, 149.55; HR MS (FAB, positive ion mode) [M] + (C 36 H 21 N 3 ): Calculated 495.1735, Found 495.1709.

反応（3）：上記式（4‐1〜4）で表される化合物の合成
アルゴン雰囲気下、化合物（2‐1'）（265 mg、1 eq.）のEt3N / THF = 1 / 1（体積比）（10 ml）溶液に Pd(PPh3)2Cl4（22 mg、0.04 eq.）とCuI（3 mg、0.02 eq.）を室温で加え、5分攪拌した。この溶液に2−エチニルベンゾニトリル（200 mg、2.0 eq.）のTHF溶液（5 ml）を室温で加え、12時間加熱還流した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ベンゼン）で精製することにより、目的化合物（4‐1） 184 mg（収率61％）を得た。 Reaction (3): Synthesis of the compound represented by the above formula (4-1 to 4) Et 3 N / THF = 1/1 of the compound (2-1 ′) (265 mg, 1 eq.) Under an argon atmosphere (Volume ratio) (10 ml) To the solution, Pd (PPh 3 ) 2 Cl 4 (22 mg, 0.04 eq.) And CuI (3 mg, 0.02 eq.) Were added at room temperature and stirred for 5 minutes. To this solution was added 2-ethynylbenzonitrile (200 mg, 2.0 eq.) In THF (5 ml) at room temperature, and the mixture was heated to reflux for 12 hours. The solvent was evaporated under reduced pressure. The obtained mixture was purified by silica gel column chromatography (benzene) to obtain 184 mg (yield 61%) of the target compound (4-1).

上述した化合物（2‐1'）の代わりに（2‐2'）、（2‐3'）および（2‐4'）を使用する以外は同様の操作を行い、目的化合物（4‐2）261 mg（収率83％）、目的化合物（4‐3）275 mg（収率88％）および目的化合物（4‐4）291 mg（収率71％）を得た。   Perform the same operation except that (2-2 '), (2-3') and (2-4 ') are used in place of the compound (2-1') described above to obtain the target compound (4-2). As a result, 261 mg (yield 83%), target compound (4-3) 275 mg (yield 88%) and target compound (4-4) 291 mg (yield 71%) were obtained.

このようにして得られた式（4‐1〜4）で表される化合物のスペクトル特性は以下の通りであった。
（4‐1）：緑黄色固体、1H NMR (CDCl3): d 3.86 (s, 3H), 6.93 and 7.58 (AA'XX', 4H), 7.54 (td, J = 1.5, 7.8 Hz, 1H), 7.65 (td, J = 1.5, 7.8 Hz, 1H), 7.74 (dd, J = 1.5, 7.8 Hz, 1H), 7.77 (dd, J = 1.5, 7.8 Hz, 1H), 7.89 (s, 1H), 7.99 (s, 1H); 13C NMR (CDCl3): d 55.43, 83.46, 89.32, 94.64, 101.93, 112.88, 114.38, 115.36, 115.45, 115.57, 116.96, 118.76, 118.89, 124.48, 124.95, 128.37, 130.00, 132.67, 132.87, 133.14, 134.07, 135.36, 136.38, 161.25; HR MS (FAB, 正イオンモード) [M]+(C26H13N3O): 計算値383.1059, 実測値383.1078.
（4‐2）：黄色固体、1H NMR (CDCl3): d 2.52 (s, 3H), 7.24 and 7.53 (AA'XX', 4H), 7.55 (td, J = 1.5, 8.1 Hz, 1H), 7.66 (td, J = 1.5, 7.8 Hz, 1H), 7.75 (dd, J = 1.2, 7.8 Hz, 1H), 7.78 (dd, J = 1.2, 7.8 Hz, 1H), 7.91 (s, 1H), 8.00 (s, 1H); 13C NMR (CDCl3): d 14.97, 84.32, 89.23, 94.83, 101.35, 115.32, 115.38, 115.54, 116.69, 116.96, 118.90, 124.80, 124.86, 125.49, 127.97, 130.05, 132.48, 132.69, 132.88, 133.15, 135.29, 135.50, 136.40, 142.52; HR MS (FAB, 正イオンモード) [M]+(C26H13N3S): 計算値399.0830, 実測値399.0823.
（4‐3）：赤色固体、1H NMR (CDCl3): d 3.04 (s, 6H), 6.66 and 7.49 (AA'XX', 4H), 7.52 (td, J = 1.5, 7.8 Hz, 1H), 7.64 (td, J = 1.5, 7.8 Hz, 1H), 7.73 (dd, J = 1.2, 8.4 Hz, 1H), 7.76 (dd, J = 1.2, 8.4 Hz, 1H), 7.82 (s, 1H), 7.94 (s, 1H); 13C NMR (CDCl3): d 40.04, 83.84, 89.59, 94.11, 104.51, 106.91, 111.58, 115.42, 115.53, 115.69, 117.00, 117.99, 118.70, 123.27, 125.09, 129.02, 129.82, 132.64, 132.83, 133.07, 133.83, 134.93, 136.33, 151.24; HR MS (FAB, 正イオンモード) [M]+(C27H16N4): 計算値396.1375, 実測値396.1366.
（4‐4）：橙色固体、1H NMR (CDCl3): d 7.00 and 7.44 (AA'XX', 4H), 7.09-7.16 (m, 6H), 7.28-7.34 (m, 4H), 7.53 (td, J = 1.5, 7.8 Hz, 1H), 7.65 (td, J = 1.5, 7.8 Hz, 1H), 7.74 (dd, J = 1.2, 8.1 Hz, 1H), 7.77 (dd, J = 1.2, 8.1 Hz, 1H), 7.87 (s, 1H), 7.98 (s, 1H); 13C NMR (CDCl3): d 83.93, 89.39, 94.55, 102.63, 112.50, 115.41, 115.51, 116.98, 118.02, 118.58, 118.83, 120.93, 124.17, 124.36, 124.98, 125.62, 128.43, 129.55, 129.95, 132.66, 132.86, 133.12, 133.42, 135.92, 136.37, 146.54, 149.71; HR MS (FAB, 正イオンモード) [M]+(C37H20N4): 計算値520.1688, 実測値520.1674. The spectral characteristics of the compounds represented by the formulas (4-1 to 4) thus obtained were as follows.
(4-1): Greenish yellow solid, 1 H NMR (CDCl 3 ): d 3.86 (s, 3H), 6.93 and 7.58 (AA'XX ', 4H), 7.54 (td, J = 1.5, 7.8 Hz, 1H) , 7.65 (td, J = 1.5, 7.8 Hz, 1H), 7.74 (dd, J = 1.5, 7.8 Hz, 1H), 7.77 (dd, J = 1.5, 7.8 Hz, 1H), 7.89 (s, 1H), 7.99 (s, 1H); 13 C NMR (CDCl 3 ): d 55.43, 83.46, 89.32, 94.64, 101.93, 112.88, 114.38, 115.36, 115.45, 115.57, 116.96, 118.76, 118.89, 124.48, 124.95, 128.37, 130.00, 132.67, 132.87, 133.14, 134.07, 135.36, 136.38, 161.25; HR MS (FAB, positive ion mode) [M] + (C 26 H 13 N 3 O): calculated value 383.1059, actual value 383.1078.
(4-2): Yellow solid, 1 H NMR (CDCl 3 ): d 2.52 (s, 3H), 7.24 and 7.53 (AA'XX ', 4H), 7.55 (td, J = 1.5, 8.1 Hz, 1H) , 7.66 (td, J = 1.5, 7.8 Hz, 1H), 7.75 (dd, J = 1.2, 7.8 Hz, 1H), 7.78 (dd, J = 1.2, 7.8 Hz, 1H), 7.91 (s, 1H), 8.00 (s, 1H); 13 C NMR (CDCl 3 ): d 14.97, 84.32, 89.23, 94.83, 101.35, 115.32, 115.38, 115.54, 116.69, 116.96, 118.90, 124.80, 124.86, 125.49, 127.97, 130.05, 132.48, 132.69, 132.88, 133.15, 135.29, 135.50, 136.40, 142.52; HR MS (FAB, positive ion mode) [M] + (C 26 H 13 N 3 S): calculated value 399.0830, actual value 399.0823.
(4-3): Red solid, 1 H NMR (CDCl 3 ): d 3.04 (s, 6H), 6.66 and 7.49 (AA'XX ', 4H), 7.52 (td, J = 1.5, 7.8 Hz, 1H) , 7.64 (td, J = 1.5, 7.8 Hz, 1H), 7.73 (dd, J = 1.2, 8.4 Hz, 1H), 7.76 (dd, J = 1.2, 8.4 Hz, 1H), 7.82 (s, 1H), 7.94 (s, 1H); 13 C NMR (CDCl 3 ): d 40.04, 83.84, 89.59, 94.11, 104.51, 106.91, 111.58, 115.42, 115.53, 115.69, 117.00, 117.99, 118.70, 123.27, 125.09, 129.02, 129.82, 132.64, 132.83, 133.07, 133.83, 134.93, 136.33, 151.24; HR MS (FAB, positive ion mode) [M] + (C 27 H 16 N 4 ): calculated value 396.1375, actual value 396.1366.
(4-4): Orange solid, 1 H NMR (CDCl 3 ): d 7.00 and 7.44 (AA'XX ', 4H), 7.09-7.16 (m, 6H), 7.28-7.34 (m, 4H), 7.53 ( td, J = 1.5, 7.8 Hz, 1H), 7.65 (td, J = 1.5, 7.8 Hz, 1H), 7.74 (dd, J = 1.2, 8.1 Hz, 1H), 7.77 (dd, J = 1.2, 8.1 Hz , 1H), 7.87 (s, 1H), 7.98 (s, 1H); 13 C NMR (CDCl 3 ): d 83.93, 89.39, 94.55, 102.63, 112.50, 115.41, 115.51, 116.98, 118.02, 118.58, 118.83, 120.93 , 124.17, 124.36, 124.98, 125.62, 128.43, 129.55, 129.95, 132.66, 132.86, 133.12, 133.42, 135.92, 136.37, 146.54, 149.71; HR MS (FAB, positive ion mode) [M] + (C 37 H 20 N 4 ): Calculated value 520.1688, measured value 510.11674.

反応（4）：上記式（5‐1〜4）で表される化合物の合成
アルゴン雰囲気下、化合物（2‐1'）（265 mg、1 eq.）のEt3N / THF = 1 / 1（体積比）（10 ml）溶液に Pd(PPh3)2Cl4（22 mg、0.04 eq.）とCuI（3 mg、0.02 eq.）を室温で加え、5分攪拌した。この溶液に2−エチニルテレフタロニトリル（239 mg、2.0 eq.）のTHF溶液（5 ml）を室温で加え、12時間加熱還流した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（クロロホルム）で精製することにより、目的化合物（5‐1） 186 mg（収率58％）を得た。 Reaction (4): Synthesis of compound represented by formula (5-1-4) above Et 3 N / THF = 1/1 of compound (2-1 ′) (265 mg, 1 eq.) Under argon atmosphere (Volume ratio) (10 ml) To the solution, Pd (PPh 3 ) 2 Cl 4 (22 mg, 0.04 eq.) And CuI (3 mg, 0.02 eq.) Were added at room temperature and stirred for 5 minutes. To this solution was added 2-ethynyl terephthalonitrile (239 mg, 2.0 eq.) In THF (5 ml) at room temperature, and the mixture was heated to reflux for 12 hours. The solvent was evaporated under reduced pressure. The resulting mixture was purified by silica gel column chromatography (chloroform) to obtain 186 mg (yield 58%) of the target compound (5-1).

上述した化合物（2‐1'）の代わりに（2‐2'）、（2‐3'）および（2‐4'）を使用する以外は同様の操作を行い、目的化合物（5‐2）200 mg（収率60％）、目的化合物（5‐3）209 mg（収率63％）および目的化合物（5‐4）279 mg（収率65％）を得た。   Perform the same operation except that (2-2 '), (2-3') and (2-4 ') are used in place of the compound (2-1') described above to obtain the target compound (5-2). There were obtained 200 mg (yield 60%), target compound (5-3) 209 mg (yield 63%) and target compound (5-4) 279 mg (yield 65%).

このようにして得られた式（5‐1〜4）で表される化合物のスペクトル特性は以下の通りであった。
（5‐1）：黄緑色固体、1H NMR (CDCl3): d 3.87 (s, 3H), 6.94 and 7.59 (AA'XX', 4H), 7.80 (dd, J = 1.5, 8.1 Hz, 1H), 7.88 (d, J = 8.1 Hz, 1H), 7.92 (s, 1H), 8.00 (s, 1H), 8.04 (d, J = 1.5 Hz, 1H); 13C NMR (CDCl3): d 55.45, 83.48, 91.61, 91.89, 102.81, 112.67, 114.40, 115.15, 115.32, 115.50, 116.06, 117.06, 118.81, 119.11, 119.25, 123.24, 126.42, 129.28, 132.73, 133.55, 134.17, 135.46, 136.02, 136.51, 161.35; HR MS (FAB, 正イオンモード) [M]+(C27H12N4O): 計算値408.1011, 実測値408.1034.
（5‐2）：金色固体、1H NMR (CDCl3): d 2.53 (s, 3H), 7.25 and 7.54 (AA'XX', 4H), 7.81 (dd, J = 1.5, 8.1 Hz, 1H), 7.88 (d, J = 8.1 Hz, 1H), 7.94 (s, 1H), 8.01 (s, 1H), 8.04 (d, J = 1.5 Hz, 1H); HR MS (FAB, 正イオンモード) [M]+(C27H12N4S): 計算値424.0783, 実測値424.0758.
（5‐3）：暗赤色固体、1H NMR (CDCl3): d 3.06 (s, 6H), 6.67 and 7.51 (AA'XX', 4H), 7.79 (dd, J = 1.5, 8.1 Hz, 1H), 7.86 (d, J = 8.1 Hz, 1H), 7.87 (s, 1H), 7.96 (s, 1H), 8.03 (d, J = 1.5 Hz, 1H); HR MS (FAB, 正イオンモード) [M]+(C28H15N5): 計算値421.1327, 実測値421.1315.
（5‐4）：橙赤色固体、1H NMR (CDCl3): d 7.00 and 7.45 (AA'XX', 4H), 7.10-7.16 (m, 6H), 7.29-7.35 (m, 4H), 7.80 (dd, J = 1.5, 8.1 Hz, 1H), 7.87 (d, J = 8.1 Hz, 1H), 7.90 (s, 1H), 7.98 (s, 1H), 8.03 (d, J = 1.5 Hz, 1H); 13C NMR (CDCl3): d 83.99, 91.71, 91.79, 103.57, 112.18, 115.17, 115.35, 115.50, 116.06, 117.02, 118.60, 119.02, 119.20, 120.76, 122.87, 124.44, 125.67, 126.43, 129.33, 129.57, 132.67, 133.50, 133.54, 135.37, 135.99, 136.50, 146.43, 149.85; HR MS （FAB, 正イオンモード） [M]+(C38H19N5): 計算値545.1640, 実測値545.1641. The spectral characteristics of the compounds represented by the formulas (5-1 to 4) thus obtained were as follows.
(5-1): Yellow-green solid, 1 H NMR (CDCl 3 ): d 3.87 (s, 3H), 6.94 and 7.59 (AA'XX ', 4H), 7.80 (dd, J = 1.5, 8.1 Hz, 1H ), 7.88 (d, J = 8.1 Hz, 1H), 7.92 (s, 1H), 8.00 (s, 1H), 8.04 (d, J = 1.5 Hz, 1H); 13 C NMR (CDCl 3 ): d 55.45 , 83.48, 91.61, 91.89, 102.81, 112.67, 114.40, 115.15, 115.32, 115.50, 116.06, 117.06, 118.81, 119.11, 119.25, 123.24, 126.42, 129.28, 132.73, 133.55, 134.17, 135.46, 136.02, 136.51, 16135; MS (FAB, positive ion mode) [M] + (C 27 H 12 N 4 O): Calculated value 408.11011, Measured value 408.1034.
(5-2): Golden solid, 1 H NMR (CDCl 3 ): d 2.53 (s, 3H), 7.25 and 7.54 (AA'XX ', 4H), 7.81 (dd, J = 1.5, 8.1 Hz, 1H) , 7.88 (d, J = 8.1 Hz, 1H), 7.94 (s, 1H), 8.01 (s, 1H), 8.04 (d, J = 1.5 Hz, 1H); HR MS (FAB, positive ion mode) (M ] + (C 27 H 12 N 4 S): Calculated 424.0833, Found 424.0758.
(5-3): Dark red solid, 1 H NMR (CDCl 3 ): d 3.06 (s, 6H), 6.67 and 7.51 (AA'XX ', 4H), 7.79 (dd, J = 1.5, 8.1 Hz, 1H ), 7.86 (d, J = 8.1 Hz, 1H), 7.87 (s, 1H), 7.96 (s, 1H), 8.03 (d, J = 1.5 Hz, 1H); HR MS (FAB, positive ion mode) [ M] + (C 28 H 15 N 5 ): calculated 421.1327, found 421.1315.
(5-4): Orange-red solid, 1 H NMR (CDCl 3 ): d 7.00 and 7.45 (AA'XX ', 4H), 7.10-7.16 (m, 6H), 7.29-7.35 (m, 4H), 7.80 (dd, J = 1.5, 8.1 Hz, 1H), 7.87 (d, J = 8.1 Hz, 1H), 7.90 (s, 1H), 7.98 (s, 1H), 8.03 (d, J = 1.5 Hz, 1H) ; 13 C NMR (CDCl 3 ): d 83.99, 91.71, 91.79, 103.57, 112.18, 115.17, 115.35, 115.50, 116.06, 117.02, 118.60, 119.02, 119.20, 120.76, 122.87, 124.44, 125.67, 126.43, 129.33, 129.57, 132.67, 133.50, 133.54, 135.37, 135.99, 136.50, 146.43, 149.85; HR MS (FAB, positive ion mode) [M] + (C 38 H 19 N 5 ): calculated value 545.1640, actual value 545.1641.

式（5‐5〜9）で表される化合物の製造例   Production Example of Compound Represented by Formula (5-5-9)

上記式（5‐5〜9）で表される化合物の製造例について説明する。
反応（1）：化合物（2‐5'〜9'）の合成
アルゴン雰囲気下、５−ブロモ−2−ヨードテレフタロニトリル（140 mg、1 eq.）のEt3N / THF = 1 / 1（体積比）（20 ml）溶液に Pd(PPh3)2Cl4（12 mg、0.04 eq.）とCuI（1.6 mg、0.02 eq.）を室温で加え、5分攪拌した。この溶液に化合物（1‐5''）（134 mg、1.0 eq.）のTHF溶液（10 ml）を室温で加え、室温にて1時間攪拌した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ベンゼン）で精製することにより、目的化合物（2‐5'） 194 mg（収率88％）を得た。 Production examples of the compound represented by the above formula (5-5 to 9) will be described.
Reaction (1): Synthesis of Compound (2-5 ′ to 9 ′) 5-Bromo-2-iodoterephthalonitrile (140 mg, 1 eq.) Et 3 N / THF = 1/1 (under argon atmosphere) (Volume ratio) (20 ml) To the solution, Pd (PPh 3 ) 2 Cl 4 (12 mg, 0.04 eq.) And CuI (1.6 mg, 0.02 eq.) Were added at room temperature and stirred for 5 minutes. To this solution was added a THF solution (10 ml) of compound (1-5 ″) (134 mg, 1.0 eq.) At room temperature, and the mixture was stirred at room temperature for 1 hour, and then the solvent was evaporated under reduced pressure. The resulting mixture was purified by silica gel column chromatography (benzene) to obtain 194 mg (yield 88%) of the target compound (2-5 ′).

上述した化合物（1‐5''）の代わりに（1‐6''）、（1‐7''）、（1‐8''）および（1‐9''）を使用する以外は同様の操作を行い、目的化合物（2‐6'）135 mg（収率71％）、目的化合物（2‐7'）213 mg（収率72％）、目的化合物（2‐8'）295 mg（収率89％）および目的化合物（2‐9'）301 mg（収率78％）を得た。   Same except that (1-6 ''), (1-7 ''), (1-8 '') and (1-9 '') are used instead of the compound (1-5 '') mentioned above The target compound (2-6 ′) 135 mg (yield 71%), the target compound (2-7 ′) 213 mg (yield 72%), the target compound (2-8 ′) 295 mg ( Yield 89%) and 301 mg (yield 78%) of the target compound (2-9 ′) were obtained.

反応（2）：上記式（5‐6〜9）で表される化合物の合成
アルゴン雰囲気下、化合物（2‐5'）（90 mg、1 eq.）のEt3N / THF = 1 / 1（体積比）（10 ml）溶液に Pd(PPh3)2Cl4（22 mg）とCuI（3 mg）を室温で加え、5分攪拌した。この溶液に2−エチニルテレフタロニトリル（52 mg、2.0 eq.）のTHF溶液（5 ml）を室温で加え、12時間加熱還流した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（クロロホルム）で精製することにより、目的化合物（5‐5） 58 mg（収率64％）を得た。 Reaction (2): Synthesis of compound represented by formula (5-6-9) above Et 3 N / THF = 1/1 of compound (2-5 ′) (90 mg, 1 eq.) Under argon atmosphere (Volume ratio) (10 ml) To the solution, Pd (PPh 3 ) 2 Cl 4 (22 mg) and CuI (3 mg) were added at room temperature and stirred for 5 minutes. To this solution was added a THF solution (5 ml) of 2-ethynylterephthalonitrile (52 mg, 2.0 eq.) At room temperature, and the mixture was heated to reflux for 12 hours, and then the solvent was evaporated under reduced pressure. The obtained mixture was purified by silica gel column chromatography (chloroform) to obtain 58 mg (yield: 64%) of the target compound (5-5).

上述した化合物（2‐5'）の代わりに（2‐6'）、（2‐7'）、（2‐8'）および（2‐9'）を使用する以外は同様の操作を行い、目的化合物（5‐6）84 mg（収率83％）、目的化合物（5‐7）100 mg（収率84％）、目的化合物（5‐8）152 mg（収率72％）および目的化合物（5‐9）92 mg（収率61％）を得た。   The same operation was performed except that (2-6 ′), (2-7 ′), (2-8 ′) and (2-9 ′) were used instead of the compound (2-5 ′) described above, Objective compound (5-6) 84 mg (yield 83%), objective compound (5-7) 100 mg (yield 84%), objective compound (5-8) 152 mg (yield 72%) and objective compound 92 mg (61% yield) of (5-9) was obtained.

このようにして得られた式（5‐5〜9）で表される化合物のスペクトル特性は以下の通りであった。
（5‐5）：黄色固体、1H NMR (CDCl3): d 7.13-7.20 (m, 6H), 7.58-7.63 (m, 6H), 7.82 (dd, J = 1.2, 8.1 Hz, 1H), 7.89 (d, J = 8.1 Hz, 1H), 7.96 (s, 1H), 8.03 (s, 1H), 8.04 (d, J = 1.2 Hz, 1H); 13C NMR (CDCl3): d 84.73, 91.09, 91.38, 107.18, 115.28, 115.42, 115.74, 116.02, 117.07, 117.54, 118.57, 119.22, 119.26, 120.08, 121.42, 121.84, 123.68, 124.03, 125.39, 126.29, 128.51, 132.85, 133.60, 133.83, 134.18, 135.67, 136.05, 136.57, 148.06, 149.55; HR MS （FAB, 正イオンモード） [M]+(C40H17N7): 計算値 595.1545, 実測値595.1554.
（5‐6）：暗赤色固体、1H NMR (CDCl3): d 3.82 (s, 6H), 6.84 and 7.39 (AA'XX', 4H), 6.88 and 7.11 (AA'XX', 8H), 7.80 (dd, J = 1.5, 8.1 Hz, 1H), 7.85-7.88 (m, 2H), 7.97 (s, 1H), 8.03 (d, J = 1.5 Hz, 1H); 13C NMR (CDCl3): d 55.48, 83.95, 91.67, 91.85, 104.40, 110.21, 114.93, 115.24, 115.44, 115.52, 116.08, 117.03, 117.97, 118.38, 119.00, 119.21, 122.51, 126.52, 127.63, 129.59, 132.63, 133.54, 135.27, 136.00, 136.52, 139.23, 150.67, 156.88; HR MS （FAB, 正イオンモード） [M]+(C40H23N5O2): 計算値605.1852, 実測値605.1855.
（5‐7）：橙赤色固体、1H NMR (CDCl3): d 7.13 (AA'XX', 2H), 7.26 (AA'XX', 4H), 7.35 (tt, J = 1.2, 7.2 Hz, 2H), 7.43-7.62 (m, 14H), 7.80 (dd, J = 1.5, 8.1 Hz, 1H), 7.87 (d, J = 8.1 Hz, 1H), 7.92 (s, 1H), 8.00 (s, 1H), 8.04 (d, J = 1.5 Hz, 1H); 13C NMR (CDCl3): d 84.11, 91.72, 91.85, 103.43, 112.77, 115.18, 115.36, 115.50, 116.07, 117.07, 118.69, 119.08, 119.25, 121.46, 122.99, 125.71, 126.46, 126.80, 127.20, 128.21, 128.82, 129.31, 132.70, 133.55, 133.62, 135.44, 136.02, 136.54, 137.18, 140.28, 145.65, 149.58; HR MS （FAB, 正イオンモード） [M]+(C50H27N5): 計算値697.2266, 実測値697.2263.
（5‐8）：橙色固体、1H NMR (CDCl3): d 7.16 and 7.55 (AA'XX', 4H), 7.27 and 7.57 (AA'XX', 8H), 7.68-7.76 (m, 8H), 7.82 (dd, J = 1.5, 8.1 Hz, 1H), 7.88 (d, J = 8.1 Hz, 1H), 7.93 (s, 1H), 8.01 (s, 1H), 8.04 (d, J = 1.52 Hz, 1H); 13C NMR (CDCl3): d 84.27, 91.57, 92.05, 102.58, 110.71, 114.24, 115.12, 115.31, 115.50, 116.04, 117.09, 118.86, 118.93, 119.15, 119.27, 122.69, 123.37, 125.46, 126.38, 127.23, 128.43, 129.02, 132.68, 132.71, 133.57, 133.74, 134.81, 135.48, 136.02, 136.54, 144.56, 146.85, 148.87; HR MS （FAB, 正イオンモード） [M]+(C52H25N7): 計算値747.2171, 実測値747.2163.
（5‐9）：暗赤色固体、1H NMR (CDCl3): d 3.86 (s, 6H), 6.98 and 7.52 (AA'XX', 8H), 7.10 and 7.49 (AA'XX', 4H), 7.22 and 7.53 (AA'XX', 8H), 7.80 (dd, J = 1.5, 8.1 Hz, 1H), 7.87 (d, J = 8.1 Hz, 1H), 7.91 (s, 1H), 7.99 (s, 1H), 8.03 (d, J = 1.5 Hz, 1H); 13C NMR (CDCl3): d 55.34, 84.09, 91.74, 91.81, 103.60, 112.38, 114.22, 115.19, 115.37, 115.51, 116.07, 117.05, 118.63, 119.06, 119.23, 121.05, 122.90, 125.82, 126.47, 127.72, 127.82, 129.35, 132.68, 132.84, 133.54, 133.58, 135.41, 136.01, 136.53, 136.87, 145.05, 147.70, 159.05; HR MS （FAB, 正イオンモード） [M]+(C52H31N5O2): 計算値757.2478, 実測値757.2482. The spectral characteristics of the compounds represented by the formulas (5-5 to 9) thus obtained were as follows.
(5-5): yellow solid, 1 H NMR (CDCl 3 ): d 7.13-7.20 (m, 6H), 7.58-7.63 (m, 6H), 7.82 (dd, J = 1.2, 8.1 Hz, 1H), 7.89 (d, J = 8.1 Hz, 1H), 7.96 (s, 1H), 8.03 (s, 1H), 8.04 (d, J = 1.2 Hz, 1H); 13 C NMR (CDCl 3 ): d 84.73, 91.09 , 91.38, 107.18, 115.28, 115.42, 115.74, 116.02, 117.07, 117.54, 118.57, 119.22, 119.26, 120.08, 121.42, 121.84, 123.68, 124.03, 125.39, 126.29, 128.51, 132.85, 133.60, 133.83, 134.18, 05.67 , 136.57, 148.06, 149.55; HR MS (FAB, positive ion mode) [M] + (C 40 H 17 N 7 ): calculated value 595.1545, actual value 595.1554.
(5-6): dark red solid, 1 H NMR (CDCl 3 ): d 3.82 (s, 6H), 6.84 and 7.39 (AA'XX ', 4H), 6.88 and 7.11 (AA'XX', 8H), 7.80 (dd, J = 1.5, 8.1 Hz, 1H), 7.85-7.88 (m, 2H), 7.97 (s, 1H), 8.03 (d, J = 1.5 Hz, 1H); 13 C NMR (CDCl 3 ): d 55.48, 83.95, 91.67, 91.85, 104.40, 110.21, 114.93, 115.24, 115.44, 115.52, 116.08, 117.03, 117.97, 118.38, 119.00, 119.21, 122.51, 126.52, 127.63, 129.59, 132.63, 133.54, 135.27, 136.00, 136.27, 136.00 , 139.23, 150.67, 156.88; HR MS (FAB, positive ion mode) [M] + (C 40 H 23 N 5 O 2 ): Calculated 605.1852, Found 605.1855.
(5-7): orange red solid, 1 H NMR (CDCl 3 ): d 7.13 (AA'XX ', 2H), 7.26 (AA'XX', 4H), 7.35 (tt, J = 1.2, 7.2 Hz, 2H), 7.43-7.62 (m, 14H), 7.80 (dd, J = 1.5, 8.1 Hz, 1H), 7.87 (d, J = 8.1 Hz, 1H), 7.92 (s, 1H), 8.00 (s, 1H ), 8.04 (d, J = 1.5 Hz, 1H); 13 C NMR (CDCl 3 ): d 84.11, 91.72, 91.85, 103.43, 112.77, 115.18, 115.36, 115.50, 116.07, 117.07, 118.69, 119.08, 119.25, 121.46 , 122.99, 125.71, 126.46, 126.80, 127.20, 128.21, 128.82, 129.31, 132.70, 133.55, 133.62, 135.44, 136.02, 136.54, 137.18, 140.28, 145.65, 149.58; HR MS (FAB, positive ion mode) [M] + (C 50 H 27 N 5 ): Calculated 697.2266, Found 697.2263.
(5-8): Orange solid, 1 H NMR (CDCl 3 ): d 7.16 and 7.55 (AA'XX ', 4H), 7.27 and 7.57 (AA'XX', 8H), 7.68-7.76 (m, 8H) , 7.82 (dd, J = 1.5, 8.1 Hz, 1H), 7.88 (d, J = 8.1 Hz, 1H), 7.93 (s, 1H), 8.01 (s, 1H), 8.04 (d, J = 1.52 Hz, 13 C NMR (CDCl 3 ): d 84.27, 91.57, 92.05, 102.58, 110.71, 114.24, 115.12, 115.31, 115.50, 116.04, 117.09, 118.86, 118.93, 119.15, 119.27, 122.69, 123.37, 125.46, 126.38, 127.23, 128.43, 129.02, 132.68, 132.71, 133.57, 133.74, 134.81, 135.48, 136.02, 136.54, 144.56, 146.85, 148.87; HR MS (FAB, positive ion mode) [M] + (C 52 H 25 N 7 ): Calculated 747.2171, Measured 747.2163.
(5-9): dark red solid, 1 H NMR (CDCl 3 ): d 3.86 (s, 6H), 6.98 and 7.52 (AA'XX ', 8H), 7.10 and 7.49 (AA'XX', 4H), 7.22 and 7.53 (AA'XX ', 8H), 7.80 (dd, J = 1.5, 8.1 Hz, 1H), 7.87 (d, J = 8.1 Hz, 1H), 7.91 (s, 1H), 7.99 (s, 1H ), 8.03 (d, J = 1.5 Hz, 1H); 13 C NMR (CDCl 3 ): d 55.34, 84.09, 91.74, 91.81, 103.60, 112.38, 114.22, 115.19, 115.37, 115.51, 116.07, 117.05, 118.63, 119.06 , 119.23, 121.05, 122.90, 125.82, 126.47, 127.72, 127.82, 129.35, 132.68, 132.84, 133.54, 133.58, 135.41, 136.01, 136.53, 136.87, 145.05, 147.70, 159.05; HR MS (FAB, positive ion mode) [M ] + (C 52 H 31 N 5 O 2 ): calculated value 757.2478, actual value 757.22482.

式（6）で表される化合物の製造例   Production Example of Compound Represented by Formula (6)

上記式（6）で表される化合物の製造例について説明する。
反応（1）：上記式（3''）で表される化合物の合成
アルゴン雰囲気下、非特許文献５に従って調製した化合物（3'''）（498 mg、1 eq.）のEt3N（15 ml）溶液に Pd(PPh3)2Cl4（27 mg、0.04 eq.）とCuI（4 mg、0.02 eq.）を室温で加え、5分攪拌した。この溶液にトリメチルシリルアセチレン（0.2 ml、1.5 eq.）を室温で加え、12時間加熱還流した後、溶媒を減圧下留去した。得られた混合物は、シリカゲルカラムクロマトグラフィー（ヘキサン / ベンゼン = 3 : 1）で精製を行った。精製されたトリメチルシリル誘導体のクロロホルム（8 ml）溶液に2M KOH 水溶液（1 ml）を加え、さらに反応溶液が均一になるまでメタノールを加えた。この反応溶液を室温で30分攪拌した後、水を加え、クロロホルムにより抽出した。有機層は無水MgSO4で乾燥し、ろ過後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ヘキサン / ベンゼン = 3 : 1）で精製することにより、目的化合物（3''）378 mg（収率85％）を得た。 Production examples of the compound represented by the above formula (6) will be described.
Reaction (1): Synthesis of Compound Represented by Formula (3 ″) Above Et 3 N of Compound (3 ′ ″) (498 mg, 1 eq.) Prepared according to Non-Patent Document 5 under an argon atmosphere 15 ml) Pd (PPh 3 ) 2 Cl 4 (27 mg, 0.04 eq.) And CuI (4 mg, 0.02 eq.) Were added at room temperature and stirred for 5 minutes. Trimethylsilylacetylene (0.2 ml, 1.5 eq.) Was added to this solution at room temperature, and the mixture was heated to reflux for 12 hours, and then the solvent was evaporated under reduced pressure. The obtained mixture was purified by silica gel column chromatography (hexane / benzene = 3: 1). 2M KOH aqueous solution (1 ml) was added to a purified solution of the trimethylsilyl derivative in chloroform (8 ml), and methanol was further added until the reaction solution became homogeneous. The reaction solution was stirred at room temperature for 30 minutes, water was added, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous MgSO 4 and filtered, and then the solvent was distilled off under reduced pressure. The obtained mixture was purified by silica gel column chromatography (hexane / benzene = 3: 1) to obtain 378 mg (yield 85%) of the target compound (3 ″).

反応（2）：化合物（3'）の合成
アルゴン雰囲気下、５−ブロモ−2−ヨードテレフタロニトリル（251 mg、1 eq.）のEt3N / THF = 1 / 1（体積比）（50 ml）溶液に Pd(PPh3)2Cl4（22 mg、0.04 eq.）とCuI（3 mg、0.02 eq.）を室温で加え、5分攪拌した。この溶液に化合物（3''）（350 mg、1.0 eq.）のTHF溶液（10 ml）を室温で加え、室温にて1時間攪拌した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ヘキサン / ベンゼン = 1 : 1）で精製することにより、目的化合物（3'）313 mg（収率62％）を得た。 Reaction (2): Synthesis of Compound (3 ′) 5-Bromo-2-iodoterephthalonitrile (251 mg, 1 eq.) Et 3 N / THF = 1/1 (volume ratio) under an argon atmosphere (50 ml) Pd (PPh 3 ) 2 Cl 4 (22 mg, 0.04 eq.) and CuI (3 mg, 0.02 eq.) were added at room temperature and stirred for 5 minutes. To this solution was added a THF solution (10 ml) of compound (3 ″) (350 mg, 1.0 eq.) At room temperature, and the mixture was stirred at room temperature for 1 hour, and then the solvent was evaporated under reduced pressure. The obtained mixture was purified by silica gel column chromatography (hexane / benzene = 1: 1) to obtain 313 mg (yield 62%) of the target compound (3 ′).

反応（3）：上記式（6）で表される化合物の合成
アルゴン雰囲気下、化合物（3'）（300 mg、1 eq.）のEt3N / THF = 1 / 1（体積比）（50 ml）溶液に Pd(PPh3)2Cl4（20 mg）とCuI（3 mg）を室温で加え、5分攪拌した。この溶液に2−エチニルテレフタロニトリル（137 mg、2.0 eq.）のTHF溶液（10 ml）を室温で加え、6時間加熱還流した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ベンゼン）で精製することにより、目的化合物（6）234 mg（収率70％）を得た。 Reaction (3): Synthesis of the compound represented by the above formula (6) Et 3 N / THF = 1/1 (volume ratio) of the compound (3 ′) (300 mg, 1 eq.) Under an argon atmosphere (50 ml) Pd (PPh 3 ) 2 Cl 4 (20 mg) and CuI (3 mg) were added to the solution at room temperature and stirred for 5 minutes. To this solution was added 2-ethynyl terephthalonitrile (137 mg, 2.0 eq.) In THF (10 ml) at room temperature, and the mixture was heated to reflux for 6 hours. The solvent was evaporated under reduced pressure. The obtained mixture was purified by silica gel column chromatography (benzene) to obtain 234 mg (yield 70%) of the target compound (6).

このようにして得られた式（6）で表される化合物のスペクトル特性は以下の通りであった。
（6）：橙色固体、1H NMR (CDCl3): d 0.86 (t, J = 6.0 Hz, 3H), 1.25-1.76 (m, 12H), 2.81 (t, J = 7.5 Hz, 2H), 3.01 (s, 6H), 6.84 and 7.48 (AA'XX', 4H), 7.79 (dd, J = 1.5, 7.8 Hz, 1H), 7.87 (d, J = 7.8 Hz, 1H), 7.82 (s, 1H), 7.94 (s, 1H), 8.03 (d, J = 1.5 Hz, 1H).
1) G. Bidan, A. De Nicola, V. Enee, and S. Guillerez, Chem. Mater., 1998, 104, 1052-1058. The spectral characteristics of the compound represented by the formula (6) thus obtained were as follows.
(6): Orange solid, 1 H NMR (CDCl 3 ): d 0.86 (t, J = 6.0 Hz, 3H), 1.25-1.76 (m, 12H), 2.81 (t, J = 7.5 Hz, 2H), 3.01 (s, 6H), 6.84 and 7.48 (AA'XX ', 4H), 7.79 (dd, J = 1.5, 7.8 Hz, 1H), 7.87 (d, J = 7.8 Hz, 1H), 7.82 (s, 1H) , 7.94 (s, 1H), 8.03 (d, J = 1.5 Hz, 1H).
1) G. Bidan, A. De Nicola, V. Enee, and S. Guillerez, Chem. Mater., 1998, 104, 1052-1058.

式（7）で表される化合物の製造例   Production Example of Compound represented by Formula (7)

上記式（7）で表される化合物の製造例について説明する。
反応（1）：化合物（4'）の合成
アルゴン雰囲気下、５−ブロモ−2−ヨードテレフタロニトリル（792 mg、1 eq.）のEt3N / THF = 1 / 2（体積比）（45 ml）溶液に Pd(PPh3)2Cl4（67 mg、0.04 eq.）とCuI（9 mg、0.02 eq.）を室温で加え、5分攪拌した。この溶液に市販の化合物（4''）（500 mg、1.0 eq.）のTHF溶液（10 ml）を室温で加え、室温にて1時間攪拌した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ヘキサン / ベンゼン = 1 : 1）で精製することにより、目的化合物（6'）739g（収率75％）を得た。 Production examples of the compound represented by the formula (7) will be described.
Reaction (1): Synthesis of Compound (4 ′) 5-Bromo-2-iodoterephthalonitrile (792 mg, 1 eq.) Et 3 N / THF = 1/2 (volume ratio) under an argon atmosphere (45 ml) Pd (PPh 3 ) 2 Cl 4 (67 mg, 0.04 eq.) and CuI (9 mg, 0.02 eq.) were added at room temperature and stirred for 5 minutes. A commercially available compound (4 ″) (500 mg, 1.0 eq.) In THF (10 ml) was added to this solution at room temperature, and the mixture was stirred at room temperature for 1 hour, and then the solvent was distilled off under reduced pressure. The obtained mixture was purified by silica gel column chromatography (hexane / benzene = 1: 1) to obtain 739 g (yield 75%) of the target compound (6 ′).

反応（2）：上記式（7）で表される化合物の合成
アルゴン雰囲気下、化合物（6'）（300 mg、1 eq.）のEt3N / THF = 1 / 1（体積比）（50 ml）溶液に Pd(PPh3)2Cl4（20 mg、0.04 eq.）とCuI（3 mg、0.02 eq.）を室温で加え、5分攪拌した。この溶液に2−エチニルテレフタロニトリル（220 mg、2.0 eq.）のTHF溶液（15 ml）を室温で加え、6時間加熱還流した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ベンゼン）で精製することにより、目的化合物（7）212 mg（収率60％）を得た。 Reaction (2): Synthesis of the compound represented by the above formula (7) Et 3 N / THF = 1/1 (volume ratio) of the compound (6 ′) (300 mg, 1 eq.) Under an argon atmosphere (50 ml) Pd (PPh 3 ) 2 Cl 4 (20 mg, 0.04 eq.) and CuI (3 mg, 0.02 eq.) were added at room temperature and stirred for 5 minutes. To this solution was added a THF solution (15 ml) of 2-ethynylterephthalonitrile (220 mg, 2.0 eq.) At room temperature, and the mixture was heated to reflux for 6 hours, and then the solvent was evaporated under reduced pressure. The obtained mixture was purified by silica gel column chromatography (benzene) to obtain 212 mg (yield 60%) of the target compound (7).

このようにして得られた式（7）で表される化合物のスペクトル特性は以下の通りであった。
（7）：赤色固体、1H NMR (CDCl3): d 4.31 (s, 5H), 4.41 (t, J = 1.8 Hz, 2H), 4.64 (t, J = 1.8 Hz, 2H), 7.81 (dd, J = 1.5, 7.8 Hz, 1H), 7.87 (d, J = 7.8 Hz, 1H), 7.89 (s, 1H), 7.99 (s, 1H), 8.04 (d, J = 1.5 Hz, 1H).
13C NMR (CDCl3): d 29.69, 61.66, 70.46, 70.51, 72.37, 81.08, 91.71, 91.80, 103.96, 115.17, 115.45, 115.51, 116.06, 117.07, 118.66, 119.10, 119.22, 122.69, 126.51, 129.58, 132.67, 133.55, 135.43, 136.00, 1326.59. The spectral characteristics of the compound represented by the formula (7) thus obtained were as follows.
(7): Red solid, 1 H NMR (CDCl 3 ): d 4.31 (s, 5H), 4.41 (t, J = 1.8 Hz, 2H), 4.64 (t, J = 1.8 Hz, 2H), 7.81 (dd , J = 1.5, 7.8 Hz, 1H), 7.87 (d, J = 7.8 Hz, 1H), 7.89 (s, 1H), 7.99 (s, 1H), 8.04 (d, J = 1.5 Hz, 1H).
13 C NMR (CDCl 3 ): d 29.69, 61.66, 70.46, 70.51, 72.37, 81.08, 91.71, 91.80, 103.96, 115.17, 115.45, 115.51, 116.06, 117.07, 118.66, 119.10, 119.22, 122.69, 126.51, 129.58, 132.67 , 133.55, 135.43, 136.00, 1326.59.

式（8）で表される化合物の製造例   Production Example of Compound represented by Formula (8)

上記式（8）で表される化合物の製造例について説明する。
反応（1）：上記式（5''）で表される化合物の合成
アルゴン雰囲気下、非特許文献６，７，８に従って調製した化合物（5'''）（920 mg、1 eq.）のEt3N（30 ml）溶液に Pd(PPh3)2Cl4（46 mg、0.04 eq.）とCuI（6.2 mg、0.02 eq.）を室温で加え、5分攪拌した。この溶液にトリメチルシリルアセチレン（0.4 ml、1.5 eq.）を室温で加え、1時間攪拌した後、溶媒を減圧下留去した。得られた混合物は、シリカゲルカラムクロマトグラフィー（ヘキサン / ベンゼン = 2 : 1）で精製を行った。精製されたトリメチルシリル誘導体のクロロホルム（15 ml）溶液に2M KOH 水溶液（1.6 ml）を加え、さらに反応溶液が均一になるまでメタノールを加えた。この反応溶液を室温で30分攪拌した後、水を加え、クロロホルムにより抽出した。有機層は無水MgSO4で乾燥し、ろ過後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ヘキサン / ベンゼン = 2 : 1）で精製することにより、目的化合物（5''）230 mg（収率31％）を得た。 Production examples of the compound represented by the above formula (8) will be described.
Reaction (1): Synthesis of Compound Represented by Formula (5 ″) Above Compound (5 ′ ″) (920 mg, 1 eq.) Prepared according to Non-Patent Documents 6, 7, and 8 under an argon atmosphere Pd (PPh 3 ) 2 Cl 4 (46 mg, 0.04 eq.) And CuI (6.2 mg, 0.02 eq.) Were added to the Et 3 N (30 ml) solution at room temperature, and the mixture was stirred for 5 minutes. Trimethylsilylacetylene (0.4 ml, 1.5 eq.) Was added to this solution at room temperature and stirred for 1 hour, and then the solvent was evaporated under reduced pressure. The resulting mixture was purified by silica gel column chromatography (hexane / benzene = 2: 1). 2M KOH aqueous solution (1.6 ml) was added to a purified solution of the trimethylsilyl derivative in chloroform (15 ml), and methanol was further added until the reaction solution became homogeneous. The reaction solution was stirred at room temperature for 30 minutes, water was added, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous MgSO 4 and filtered, and then the solvent was distilled off under reduced pressure. The obtained mixture was purified by silica gel column chromatography (hexane / benzene = 2: 1) to obtain 230 mg (yield 31%) of the target compound (5 ″).

反応（2）：化合物（5'）の合成
アルゴン雰囲気下、５−ブロモ−2−ヨードテレフタロニトリル（159 mg、1 eq.）のEt3N / THF = 1 / 2（体積比）（30 ml）溶液に Pd(PPh3)2Cl4（20 mg）とCuI（3 mg）を室温で加え、5分攪拌した。この溶液に化合物（5''）（220 mg、1.0 eq.）のTHF溶液（10 ml）を室温で加え、1時間攪拌した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ヘキサン / ベンゼン = 1 : 1）で精製することにより、目的化合物（5'）70 mg（収率22％）を得た。 Reaction (2): Synthesis of Compound (5 ′) 5-Bromo-2-iodoterephthalonitrile (159 mg, 1 eq.) Et 3 N / THF = 1/2 (volume ratio) under an argon atmosphere (30 ml) Pd (PPh 3 ) 2 Cl 4 (20 mg) and CuI (3 mg) were added to the solution at room temperature and stirred for 5 minutes. To this solution was added a THF solution (10 ml) of compound (5 ″) (220 mg, 1.0 eq.) At room temperature and stirred for 1 hour, and then the solvent was distilled off under reduced pressure. The obtained mixture was purified by silica gel column chromatography (hexane / benzene = 1: 1) to obtain 70 mg (yield 22%) of the target compound (5 ′).

反応（3）：上記式（8）で表される化合物の合成
アルゴン雰囲気下、化合物（5'）（50 mg、1 eq.）のEt3N / THF = 1 / 1（体積比）（10 ml）溶液に Pd(PPh3)2Cl4（20mg）とCuI（3 mg）を室温で加え、5分攪拌した。この溶液に2−エチニルテレフタロニトリル（23 mg、2.0 eq.）のTHF溶液（5 ml）を室温で加え、6時間加熱還流した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ベンゼン）で精製することにより、目的化合物（8）7 mg（収率13％）を得た。 Reaction (3): Synthesis of Compound Represented by Formula (8) Above Et 3 N / THF = 1/1 (volume ratio) of compound (5 ′) (50 mg, 1 eq.) (10% by volume) in an argon atmosphere ml) Pd (PPh 3 ) 2 Cl 4 (20 mg) and CuI (3 mg) were added to the solution at room temperature and stirred for 5 minutes. To this solution was added a THF solution (5 ml) of 2-ethynylterephthalonitrile (23 mg, 2.0 eq.) At room temperature, and the mixture was heated to reflux for 6 hours, and then the solvent was evaporated under reduced pressure. The obtained mixture was purified by silica gel column chromatography (benzene) to obtain 7 mg (yield 13%) of the target compound (8).

このようにして得られた式（8）で表される化合物のスペクトル特性は以下の通りであった。
（8）：青色固体、1H NMR (CDCl3): d 0.89 (t, J = 6.9 Hz, 6H), 1.24-1.65(m, 16H), 2.81 (t, J = 7.5 Hz, 4H), 6.59 (s, 1H), 7.82 (dd, J = 1.5, 8.1 Hz, 1H), 7.88 (d, J = 8.1 Hz, 1H), 7.93 (s, 1H), 8.01 (s, 1H), 8.04 (d, J = 1.5 Hz, 1H).
1) C. -S. Wang, A. S. Batsanov, M. R. Bryce, J. A. K. Howard, Synthesis, 1998, 11, 1615-1618. 2) H. Shen, Y. Hu, and X. Xu, Faming Zhuanli Shenqing Congkai Shuomingshu, 2002, 16. 3) M. Iyoda, Y. Kuwatani, E. Ogura, K. Hara, H. Suzuki, T. Takano, K. Takeda, J.-i. Takano, K. Ugawa, M. Yoshida, H. Matsuyama, H. Nishikawa, I. Ikemoto, T. Kato, N. Yoneyama, J.-I. Nishijo, A. Miyazaki, and T. Enoki, Heterocycles, 2001, 54, 833-848. The spectral characteristics of the compound represented by the formula (8) thus obtained were as follows.
(8): Blue solid, 1 H NMR (CDCl 3 ): d 0.89 (t, J = 6.9 Hz, 6H), 1.24-1.65 (m, 16H), 2.81 (t, J = 7.5 Hz, 4H), 6.59 (s, 1H), 7.82 (dd, J = 1.5, 8.1 Hz, 1H), 7.88 (d, J = 8.1 Hz, 1H), 7.93 (s, 1H), 8.01 (s, 1H), 8.04 (d, J = 1.5 Hz, 1H).
1) C. -S.Wang, AS Batsanov, MR Bryce, JAK Howard, Synthesis, 1998, 11, 1615-1618. 2) H. Shen, Y. Hu, and X. Xu, Faming Zhuanli Shenqing Congkai Shuomingshu, 2002, 16. 3) M. Iyoda, Y. Kuwatani, E. Ogura, K. Hara, H. Suzuki, T. Takano, K. Takeda, J.-i. Takano, K. Ugawa, M. Yoshida, H. Matsuyama, H Nishikawa, I. Ikemoto, T. Kato, N. Yoneyama, J.-I. Nishijo, A. Miyazaki, and T. Enoki, Heterocycles, 2001, 54, 833-848.

式（9）で表される化合物の製造例   Production Example of Compound represented by Formula (9)

上記式（9）で表される化合物の製造例について説明する。
反応（1）：化合物（6'）の合成
アルゴン雰囲気下、５−ブロモ−2−ヨードテレフタロニトリル（58 mg、1 eq.）のEt3N / THF = 1 / 2（体積比）（15 ml）溶液に Pd(PPh3)2Cl4（20 mg）とCuI（3 mg）を室温で加え、5分攪拌した。この溶液に非特許文献９，１０，１１に従って調製した化合物（6''）（135 mg、1.0 eq.）のTHF溶液（10 ml）を室温で加え、室温にて1時間攪拌した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ベンゼン）で精製することにより、目的化合物（6'）119 mg（収率70％）を得た。 Production examples of the compound represented by the formula (9) will be described.
Reaction (1): Synthesis of Compound (6 ′) 5-Bromo-2-iodoterephthalonitrile (58 mg, 1 eq.) Et 3 N / THF = 1/2 (volume ratio) under an argon atmosphere (15 ml) Pd (PPh 3 ) 2 Cl 4 (20 mg) and CuI (3 mg) were added to the solution at room temperature and stirred for 5 minutes. To this solution was added a THF solution (10 ml) of the compound (6 ″) (135 mg, 1.0 eq.) Prepared according to Non-Patent Documents 9, 10, and 11 at room temperature, and the mixture was stirred at room temperature for 1 hour. Was distilled off under reduced pressure. The resulting mixture was purified by silica gel column chromatography (benzene) to obtain 119 mg (yield 70%) of the target compound (6 ′).

反応（2）：上記式（9）で表される化合物の合成
アルゴン雰囲気下、化合物（6'）（100 mg、1 eq.）のEt3N / THF = 1 / 2（体積比）（15 ml）溶液に Pd(PPh3)2Cl4（20 mg）とCuI（3 mg）を室温で加え、5分攪拌した。この溶液に2−エチニルテレフタロニトリル（31 mg、2.0 eq.）のTHF溶液（5 ml）を室温で加え、6時間加熱還流した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（クロロホルム）で精製することにより、目的化合物（9）68 mg（収率63％）を得た。 Reaction (2): Synthesis of the compound represented by the above formula (9) Et 3 N / THF = 1/2 (volume ratio) of the compound (6 ′) (100 mg, 1 eq.) Under an argon atmosphere (15 ml) Pd (PPh 3 ) 2 Cl 4 (20 mg) and CuI (3 mg) were added to the solution at room temperature and stirred for 5 minutes. To this solution was added a THF solution (5 ml) of 2-ethynylterephthalonitrile (31 mg, 2.0 eq.) At room temperature, and the mixture was heated to reflux for 6 hours, and then the solvent was evaporated under reduced pressure. The resulting mixture was purified by silica gel column chromatography (chloroform) to obtain 68 mg (yield 63%) of the target compound (9).

このようにして得られた式（9）で表される化合物のスペクトル特性は以下の通りであった。
（9）：緑色固体、1H NMR (CDCl3): d 1.57 (s, 36H), 7.81 (dd, J = 1.2, 8.1 Hz, 1H), 7.83 (t, J = 1.8 Hz, 2H), 7.89 (d, J = 8.1 Hz, 1H), 7.96 (s, 1H), 8.02 (s, 1H), 8.04 (d, J = 1.2 Hz, 1H), 8.10 (d, J = 1.8 Hz, 4H), 9.10 (d, J = 4.5 Hz, 2H), 9.11 (d, J = 4.5 Hz, 2H), 9.37 (d, J = 4.5 Hz, 2H), 9.82 (d, J = 4.5 Hz, 2H), 10.25 (s, 1H).
J.-W. Ka and C.-H. Lee, Tetrahedron Lett., 2000, 41, 4609-4613. D. Bonifazi, G. Accorsi, N. Armaroli, F. Song, A. Palkar, L. Echegoyen, M. Scholl, P. Seiler, B. Jaun, and F. Diederich, Helv. Chim. Acta, 2005, 88, 1839-1884. T. E. O. Screen, I. M. Blake, L. H. Rees, W. Clegg, S. J. Borwick, and H. L. Anderson, J. Chem. Soc., Perkin Trans. 1, 2002, 320-329. The spectral characteristics of the compound represented by the formula (9) thus obtained were as follows.
(9): Green solid, 1 H NMR (CDCl 3 ): d 1.57 (s, 36H), 7.81 (dd, J = 1.2, 8.1 Hz, 1H), 7.83 (t, J = 1.8 Hz, 2H), 7.89 (d, J = 8.1 Hz, 1H), 7.96 (s, 1H), 8.02 (s, 1H), 8.04 (d, J = 1.2 Hz, 1H), 8.10 (d, J = 1.8 Hz, 4H), 9.10 (d, J = 4.5 Hz, 2H), 9.11 (d, J = 4.5 Hz, 2H), 9.37 (d, J = 4.5 Hz, 2H), 9.82 (d, J = 4.5 Hz, 2H), 10.25 (s , 1H).
J.-W.Ka and C.-H. Lee, Tetrahedron Lett., 2000, 41, 4609-4613. D. Bonifazi, G. Accorsi, N. Armaroli, F. Song, A. Palkar, L. Echegoyen, M. Scholl, P. Seiler, B. Jaun, and F. Diederich, Helv. Chim. Acta, 2005, 88 , 1839-1884. TEO Screen, IM Blake, LH Rees, W. Clegg, SJ Borwick, and HL Anderson, J. Chem. Soc., Perkin Trans. 1, 2002, 320-329.

式（10）で表される化合物の製造例   Production Example of Compound represented by Formula (10)

上記式（10）で表される化合物の製造例について説明する。
反応（1）：化合物（7'）の合成
アルゴン雰囲気下、５−ブロモ−2−ヨードテレフタロニトリル（35 mg、1 eq.）のEt3N / THF = 1 / 1（体積比）（10 ml）溶液に Pd(PPh3)2Cl4（20 mg）とCuI（3 mg）を室温で加え、5分攪拌した。この溶液に非特許文献９，１０，１１に従って調製した化合物（7''）（105 mg、1.0 eq.）のTHF溶液（10 ml）を室温で加え、室温にて1時間攪拌した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（ヘキサン / 塩化メチレン = 1 : 1）で精製することにより、目的化合物（7'）79 mg（収率63％）を得た。 Production examples of the compound represented by the formula (10) will be described.
Reaction (1): Synthesis of Compound (7 ′) In an argon atmosphere, 5-bromo-2-iodoterephthalonitrile (35 mg, 1 eq.) Et 3 N / THF = 1/1 (volume ratio) (10 ml) Pd (PPh 3 ) 2 Cl 4 (20 mg) and CuI (3 mg) were added to the solution at room temperature and stirred for 5 minutes. To this solution was added a THF solution (10 ml) of the compound (7 ″) (105 mg, 1.0 eq.) Prepared according to Non-Patent Documents 9, 10, and 11 at room temperature, and the mixture was stirred at room temperature for 1 hour. Was distilled off under reduced pressure. The obtained mixture was purified by silica gel column chromatography (hexane / methylene chloride = 1: 1) to obtain 79 mg (yield 63%) of the target compound (7 ′).

反応（2）：上記式（10）で表される化合物の合成
アルゴン雰囲気下、化合物（7'）（70 mg、1 eq.）のEt3N / THF = 1 / 2（体積比）（15 ml）溶液に Pd(PPh3)2Cl4（20 mg）とCuI（3 mg）を室温で加え、5分攪拌した。この溶液に2−エチニルテレフタロニトリル（18 mg、2.0 eq.）のTHF溶液（5 ml）を室温で加え、6時間加熱還流した後、溶媒を減圧下留去した。得られた混合物をシリカゲルカラムクロマトグラフィー（塩化メチレン）で精製することにより、目的化合物（9）47 mg（収率63％）を得た。 Reaction (2): Synthesis of the compound represented by the above formula (10) Et 3 N / THF = 1/2 (volume ratio) of the compound (7 ′) (70 mg, 1 eq.) Under an argon atmosphere (15 ml) Pd (PPh 3 ) 2 Cl 4 (20 mg) and CuI (3 mg) were added to the solution at room temperature and stirred for 5 minutes. To this solution was added 2-ethynyl terephthalonitrile (18 mg, 2.0 eq.) In THF (5 ml) at room temperature, and the mixture was heated to reflux for 6 hours, and then the solvent was evaporated under reduced pressure. The resulting mixture was purified by silica gel column chromatography (methylene chloride) to obtain 47 mg (yield 63%) of the target compound (9).

このようにして得られた式（10）で表される化合物のスペクトル特性は以下の通りであった。
（10）：緑色固体、1H NMR (CDCl3): d 1.55 (s, 36H), 7.13 and 7.40 (AA'XX', 4H), 7.37-7.39 (m, 10H), 7.54-7.65 (m, 2H), 7.86 (t, J = 1.5 Hz, 2H), 7.90 (s, 1H), 7.93 (s, 1H), 8.09 (d, J = 0.9 Hz, 1H), 8.14 (d, J = 1.5 Hz, 4H), 8.93 (d, J = 4.5 Hz, 2H), 8.96 (d, J = 4.5 Hz, 2H), 9.13 (d, J = 4.5 Hz, 2H), 9.73 (d, J = 4.5 Hz, 2H). The spectral characteristics of the compound represented by the formula (10) thus obtained were as follows.
(10): Green solid, 1 H NMR (CDCl 3 ): d 1.55 (s, 36H), 7.13 and 7.40 (AA'XX ', 4H), 7.37-7.39 (m, 10H), 7.54-7.65 (m, 2H), 7.86 (t, J = 1.5 Hz, 2H), 7.90 (s, 1H), 7.93 (s, 1H), 8.09 (d, J = 0.9 Hz, 1H), 8.14 (d, J = 1.5 Hz, 4H), 8.93 (d, J = 4.5 Hz, 2H), 8.96 (d, J = 4.5 Hz, 2H), 9.13 (d, J = 4.5 Hz, 2H), 9.73 (d, J = 4.5 Hz, 2H) .

実施例１から実施例８で得られた化合物の溶液状態での発光特性（蛍光量子収率（φf）、発光極大波長（λem）、吸収極大波長（λabs）およびモル吸光係数（logε）を表1に示す。 Luminescence characteristics (fluorescence quantum yield (φ f ), emission maximum wavelength (λ em ), absorption maximum wavelength (λ abs ) and molar extinction coefficient (logε) of the compounds obtained in Example 1 to Example 8 in the solution state ) Is shown in Table 1.

上記表１において、a) すべての測定は295Kで行った。また、b) 蛍光量子収率は、硫酸キニーネ（φf ＝ 0.55 in 0.1 M H2SO4）を基準物質として用いた相対値である。c) 蛍光スペクトルは、クロロホルム溶液（10-7 M）として、蛍光光度計（日立F4500）を用いて測定した。d) 紫外可視吸収スペクトルは、クロロホルム溶液（10-5 M）として、分光光度計（島津UV-3100PC）を用いて測定した。 In Table 1 above: a) All measurements were performed at 295K. B) The fluorescence quantum yield is a relative value using quinine sulfate (φ f = 0.55 in 0.1 MH 2 SO 4 ) as a reference substance. c) The fluorescence spectrum was measured with a fluorometer (Hitachi F4500) as a chloroform solution (10 −7 M). d) The UV-visible absorption spectrum was measured using a spectrophotometer (Shimadzu UV-3100PC) as a chloroform solution (10 -5 M).

実施例１から実施例８で得られた化合物のフィルムおよび固体（粉末）状態での発光特性（蛍光量子収率（φf）および発光極大波長（λem））を表2に示す。 Table 2 shows the emission characteristics (fluorescence quantum yield (φ f ) and emission maximum wavelength (λ em )) of the compounds obtained in Examples 1 to 8 in the film and solid (powder) state.

上記表２において、a) すべての測定は295Kで行った。また、b) フィルムの調製法：各化合物をポリマーのTHF溶液（10 wt%）に溶解し（10-3 M）、得られた溶液をスピンコーター（ミカサMS-A100）にセットした円形カバーガラス（Φ12mm）に５滴垂らして、3000 rpmで20秒間回転させた。その後、減圧下（10 mmHg）1時間吸引し、THFを留去した。ここで、c) PST：ポリスチレン、PMMA：ポリメチルメタクリレートを示す。d) 蛍光量子収率および発光極大波長は、有機EL量子収率測定装置（浜松フォトニクスC9920-01）を用いて測定した。 In Table 2 above: a) All measurements were made at 295K. B) Film preparation method: Circular cover glass in which each compound was dissolved in a polymer THF solution (10 wt%) (10 -3 M) and the resulting solution was set on a spin coater (Mikasa MS-A100). 5 drops were dropped on (Φ12 mm) and rotated at 3000 rpm for 20 seconds. Thereafter, the mixture was sucked under reduced pressure (10 mmHg) for 1 hour, and THF was distilled off. Here, c) PST: polystyrene, PMMA: polymethylmethacrylate. d) The fluorescence quantum yield and the emission maximum wavelength were measured using an organic EL quantum yield measuring apparatus (Hamamatsu Photonics C9920-01).

Claims (5)

式（１）で表されることを特徴とする分子末端に電子供与基を導入したポリシアノオリゴフェニレンエチニレン化合物。
（式中、Dは窒素、酸素、硫黄、鉄、コバルト、ニッケルの1種もしくは2種以上を含む芳香族電子供与基を示し、mは1から4の整数を示し、nは0もしくは1から5の整数を示す。） A polycyano oligophenylene ethynylene compound having an electron donating group introduced at the molecular end, which is represented by the formula (1).
(In the formula, D represents an aromatic electron donating group containing one or more of nitrogen, oxygen, sulfur, iron, cobalt, nickel, m represents an integer of 1 to 4, and n represents 0 or 1 Indicates an integer of 5.) 上記式（１）で表される分子末端に電子供与基を導入したポリシアノオリゴフェニレンエチニレン化合物において、mは１もしくは２、nは0、1もしくは2であることを特徴とするポリシアノオリゴフェニレンエチニレン化合物。   A polycyano oligophenylene ethynylene compound in which an electron donating group is introduced at the molecular end represented by the above formula (1), wherein m is 1 or 2, and n is 0, 1 or 2 Phenylene ethynylene compounds. 上記式（１）においてDが式（２）で表されることを特徴とする請求項1および2記載の分子末端に電子供与基を導入したポリシアノオリゴフェニレンエチニレン化合物。
（式中、Xは、OR、SRもしくはNR2を示し、ここでRは炭素数１〜１４の置換もしくは無置換のアルキル基、アリール基もしくはアラルキル基を示す。） 3. The polycyano oligophenylene ethynylene compound having an electron donating group introduced at the molecular end according to claim 1 or 2, wherein D in the formula (1) is represented by the formula (2).
(In the formula, X represents OR, SR or NR 2 , wherein R represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group having 1 to 14 carbon atoms.) 上記式（１）においてDが式（３）、（４）、（５）、（６）、（７）のいずれかで表されることを特徴とする請求項1および2記載の分子末端に電子供与基を導入したポリシアノオリゴフェニレンエチニレン化合物。
（式中、RおよびQは炭素数１〜１４の置換もしくは無置換のアルキル基、アリール基もしくはアラルキル基を示す。）
（式中、Rは炭素数１〜１４の置換もしくは無置換のアルキル基、アリール基もしくはアラルキル基を示す。）
（式中、Rは炭素数１〜１４の置換もしくは無置換のアルキル基、アリール基もしくはアラルキル基を示す。）
（式中、RおよびQは炭素数１〜１４の置換もしくは無置換のアルキル基、アリール基もしくはアラルキル基を示す。） 3. In the above formula (1), D is represented by any one of formulas (3), (4), (5), (6), and (7). A polycyano oligophenylene ethynylene compound into which an electron donating group is introduced.
(In the formula, R and Q represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group having 1 to 14 carbon atoms.)
(In the formula, R represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group having 1 to 14 carbon atoms.)
(In the formula, R represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group having 1 to 14 carbon atoms.)
(In the formula, R and Q represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group having 1 to 14 carbon atoms.) 陽極と陰極と、これら両極間に介在させた有機薄膜層とを有する有機エレクトロルミネッセンス素子にあって、前記有機薄膜層が、請求項１〜４いずれかに記載の分子末端に電子供与基を導入したポリシアノオリゴフェニレンエチニレン化合物を含むことを特徴とする有機エレクトロルミネッセンス素子。   An organic electroluminescence device having an anode, a cathode, and an organic thin film layer interposed between the two electrodes, wherein the organic thin film layer introduces an electron donating group into a molecular end according to any one of claims 1 to 4. An organic electroluminescent device comprising the polycyano oligophenylene ethynylene compound prepared.
JP2008052688A 2008-03-03 2008-03-03 Polycyano-oligophenylene ethynylene compounds with electron-donating groups introduced at the molecular ends Expired - Fee Related JP5540342B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008052688A JP5540342B2 (en) 2008-03-03 2008-03-03 Polycyano-oligophenylene ethynylene compounds with electron-donating groups introduced at the molecular ends

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2008052688A JP5540342B2 (en) 2008-03-03 2008-03-03 Polycyano-oligophenylene ethynylene compounds with electron-donating groups introduced at the molecular ends

Publications (2)

Publication Number Publication Date
JP2009209073A true JP2009209073A (en) 2009-09-17
JP5540342B2 JP5540342B2 (en) 2014-07-02

Family

ID=41182585

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2008052688A Expired - Fee Related JP5540342B2 (en) 2008-03-03 2008-03-03 Polycyano-oligophenylene ethynylene compounds with electron-donating groups introduced at the molecular ends

Country Status (1)

Country Link
JP (1) JP5540342B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019234563A1 (en) * 2018-06-05 2019-12-12 Tubitak Cyano-derivatized oligonophenylacetylene-based fluorescent small molecules suitable for use in organic light-emitting diode applications and their use in organic light-emitting diode applications

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0625658A (en) * 1992-07-07 1994-02-01 Idemitsu Kosan Co Ltd Organic electroluminescent element
JP2004101729A (en) * 2002-09-06 2004-04-02 Nippon Oil Corp Thin film
JP2005350479A (en) * 2005-07-25 2005-12-22 National Institute Of Advanced Industrial & Technology Zinc(ii) porphyrin derivative

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0625658A (en) * 1992-07-07 1994-02-01 Idemitsu Kosan Co Ltd Organic electroluminescent element
JP2004101729A (en) * 2002-09-06 2004-04-02 Nippon Oil Corp Thin film
JP2005350479A (en) * 2005-07-25 2005-12-22 National Institute Of Advanced Industrial & Technology Zinc(ii) porphyrin derivative

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JPN6013021333; Ｏｃｈｉ，　Ｔａｋａｎｏｒｉ　ｅｔ　ａｌ．: 'Ｒｏｄ-ｓｈａｐｅｄ　ｏｌｉｇｏｐｈｅｎｙｌｅｎｅｅｔｈｙｎｙｌｅｎｅｓ　ｍｏｄｉｆｉｅｄ　ｂｙ　ｄｏｎｏｒ　ａｎｄ　ａｃｃｅｐｔｏｒ　ｇｒｏｕｐｓ　ｉｎ　ａ　ｂｌｏｃｋ　ｍａｎｎｅｒ：　ｓｙｎｔｈｅ' Ｃｈｅｍｉｓｔｒｙ　Ｌｅｔｔｅｒｓ ３６（６）, 2007, ７９４-７９５ *
JPN6013021335; Ｙａｍａｇｕｃｈｉ，　Ｙｏｓｈｉｈｉｒｏ　ｅｔ　ａｌ．: 'Ｎｅｗ　ｆｌｕｏｒｏｐｈｏｒｅｓ　ｗｉｔｈ　ｒｏｄ-ｓｈａｐｅｄ　ｐｏｌｙｃｙａｎｏ　pi-ｃｏｎｊｕｇａｔｅｄ　ｓｔｒｕｃｔｕｒｅｓ：Ｓｙｎｔｈｅｓｉｓ　ａｎｄ　ｐｈｏｔｏｐｈｙｓｉｃａｌ　ｐｒｏｐ' Ｏｒｇａｎｉｃ　Ｌｅｔｔｅｒｓ ８（４）, 2006, ７１７-７２０ *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019234563A1 (en) * 2018-06-05 2019-12-12 Tubitak Cyano-derivatized oligonophenylacetylene-based fluorescent small molecules suitable for use in organic light-emitting diode applications and their use in organic light-emitting diode applications

Also Published As

Publication number Publication date
JP5540342B2 (en) 2014-07-02

Similar Documents

Publication Publication Date Title
Liu et al. Nondoped blue fluorescent organic light-emitting diodes based on benzonitrile-anthracene derivative with 10.06% external quantum efficiency and low efficiency roll-off
KR101593465B1 (en) Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
TW574342B (en) Anthracene derivatives and organic electroluminescent devices made by using the same
JP2020512303A (en) Novel compound and organic light emitting device using the same
Wang et al. Construction of high efficiency non-doped deep blue emitters based on phenanthroimidazole: remarkable substitution effects on the excited state properties and device performance
Schrögel et al. Meta-linked CBP-derivatives as host materials for a blue iridium carbene complex
RU2434836C2 (en) Condensed cyclic aromatic compound for organic light-emitting device and organic light-emitting device containing said compound
TW201204808A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
JP7410571B2 (en) Compounds, luminescent materials, delayed phosphors, organic light emitting devices, oxygen sensors, molecular design methods and programs
TW201120186A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2020228359A1 (en) Organic light-emitting material containing tetraphenylbenzene, preparation, and application
TW201204809A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
Yamaguchi et al. Synthesis, structures, and photophysical properties of silicon and carbon-bridged ladder oligo (p-phenylenevinylene) s and related π-electron systems
KR101521483B1 (en) Boron complex for electroluminescent materials, method for preparing the same and organic light emitting diode comprising the same
Zhan et al. Prying into the limit of CIE value for TPE-based blue AIEgens in organic light-emitting diodes
Kumar et al. High T g fluoranthene-based electron transport materials for organic light-emitting diodes
Colombo et al. Introduction of a triphenylamine substituent on pyridyl rings as a springboard for a new appealing brightly luminescent 1, 3-di-(2-pyridyl) benzene platinum (ii) complex family
JP4320434B2 (en) Organoboron π-electron compound and material containing the same
Ye et al. AIEE-active blue-emitting molecules derived from methoxyl-decorated triarylcyclopentadienes: Synthesis, crystal structures, photophysical and electroluminescence properties
CN111454265B (en) Fused heterocyclic compound and preparation method and application thereof
JP5540342B2 (en) Polycyano-oligophenylene ethynylene compounds with electron-donating groups introduced at the molecular ends
KR20150037133A (en) Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
TW201219537A (en) Organic light emitting device and materials for use in same
Girase et al. Unipolar 1-phenylimidazo [1, 5-a] pyridine: a new class of ultra-bright sky-blue emitters for solution-processed organic light emitting diodes
KR101294332B1 (en) Novel organic semiconductor compound, manufacturing mentod thereof and use using the same

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20110301

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20110415

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20130411

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20130528

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20130725

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20131022

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20131108

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20140128

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20140204

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20140411

R150 Certificate of patent or registration of utility model

Ref document number: 5540342

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

LAPS Cancellation because of no payment of annual fees