JP6663820B2 - Indolylbenzothiadiazole derivative, method for producing indolylbenzothiadiazole derivative, and organic fluorescent material - Google Patents
Indolylbenzothiadiazole derivative, method for producing indolylbenzothiadiazole derivative, and organic fluorescent material Download PDFInfo
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- JP6663820B2 JP6663820B2 JP2016153851A JP2016153851A JP6663820B2 JP 6663820 B2 JP6663820 B2 JP 6663820B2 JP 2016153851 A JP2016153851 A JP 2016153851A JP 2016153851 A JP2016153851 A JP 2016153851A JP 6663820 B2 JP6663820 B2 JP 6663820B2
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- OUWAJDMFSQXBIB-UHFFFAOYSA-N N1C(=CC2=CC=CC=C12)C1=CC=CC2=C1N=NS2 Chemical class N1C(=CC2=CC=CC=C12)C1=CC=CC2=C1N=NS2 OUWAJDMFSQXBIB-UHFFFAOYSA-N 0.000 title claims description 54
- 239000000463 material Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 28
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 28
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 27
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 125000003545 alkoxy group Chemical group 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000003368 amide group Chemical group 0.000 claims description 21
- 125000003277 amino group Chemical group 0.000 claims description 21
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 21
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 21
- 125000005843 halogen group Chemical group 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 21
- 125000004104 aryloxy group Chemical group 0.000 claims description 18
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 claims description 9
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 claims description 7
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 7
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 7
- 239000007850 fluorescent dye Substances 0.000 claims description 7
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- JOTJVGRMHKCMFF-UHFFFAOYSA-N 4-bromo-1,2,3-benzothiadiazole Chemical compound BrC1=CC=CC2=C1N=NS2 JOTJVGRMHKCMFF-UHFFFAOYSA-N 0.000 claims description 4
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 3
- 238000000059 patterning Methods 0.000 claims description 3
- 150000004867 thiadiazoles Chemical class 0.000 claims 1
- 239000007787 solid Substances 0.000 description 30
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 230000000638 stimulation Effects 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical group C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 8
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 238000006862 quantum yield reaction Methods 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000001041 indolyl group Chemical group 0.000 description 4
- -1 p-toluenesulfonyl) group Chemical group 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 description 2
- KYKBVPGDKGABHY-UHFFFAOYSA-N 4-bromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=CC2=NSN=C12 KYKBVPGDKGABHY-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- OPDCMCHRJBVEHM-UHFFFAOYSA-N CC1=C(NC2=CC=CC=C12)C1=CC=CC2=NSN=C21 Chemical compound CC1=C(NC2=CC=CC=C12)C1=CC=CC2=NSN=C21 OPDCMCHRJBVEHM-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229920001109 fluorescent polymer Polymers 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- SMURSSZMVCOKOO-UHFFFAOYSA-N tert-butyl 3-methylindole-1-carboxylate Chemical compound C1=CC=C2C(C)=CN(C(=O)OC(C)(C)C)C2=C1 SMURSSZMVCOKOO-UHFFFAOYSA-N 0.000 description 2
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 2
- PQTFSKCVBISUCX-UHFFFAOYSA-N (3-methyl-1h-indol-2-yl)boronic acid Chemical compound C1=CC=C2C(C)=C(B(O)O)NC2=C1 PQTFSKCVBISUCX-UHFFFAOYSA-N 0.000 description 1
- LHRXMNLVUCTIBU-UHFFFAOYSA-N 4-(3-methyl-1H-indol-2-yl)-1,2,3-benzothiadiazole Chemical class CC1=C(NC2=CC=CC=C12)C1=CC=CC2=C1N=NS2 LHRXMNLVUCTIBU-UHFFFAOYSA-N 0.000 description 1
- LGELKHRSKOMOEH-UHFFFAOYSA-N C(=O)(OC(C)(C)C)N1SC2=C(N1)C(=CC=C2)C=1NC2=CC=CC=C2C=1C Chemical compound C(=O)(OC(C)(C)C)N1SC2=C(N1)C(=CC=C2)C=1NC2=CC=CC=C2C=1C LGELKHRSKOMOEH-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- UELITFHSCLAHKR-UHFFFAOYSA-N acibenzolar-S-methyl Chemical compound CSC(=O)C1=CC=CC2=C1SN=N2 UELITFHSCLAHKR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 230000031070 response to heat Effects 0.000 description 1
- 230000035440 response to pH Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
Description
本発明は、インドリルベンゾチアジアゾール誘導体、インドリルベンゾチアジアゾール誘導体の製造方法及び有機蛍光材料に関する。 The present invention relates to an indolylbenzothiadiazole derivative, a method for producing an indolylbenzothiadiazole derivative, and an organic fluorescent material.
固体蛍光性の有機分子が機械的刺激により発光色を変化させ、加熱や溶媒蒸気にさらすことにより元の発光色に戻る現象は蛍光メカノクロミズムと呼ばれ、近年徐々に報告例が増えているが珍しい現象である（非特許文献１、特許文献１、２）。 The phenomenon in which solid fluorescent organic molecules change the emission color by mechanical stimulation and return to the original emission color by heating or exposure to solvent vapor is called fluorescence mechanochromism, and the number of reports is gradually increasing in recent years. This is a rare phenomenon (Non-Patent Document 1, Patent Documents 1 and 2).
機械的刺激を加えることにより発光特性が変化する固体蛍光性の有機分子は、通常、元の状態に戻すために加熱や溶媒蒸気にさらす必要があり、この点で不便である。また、このような分子は従来、多くの工程を経て合成されており、簡便な方法で合成できる固体蛍光性の有機分子が待ち望まれている。さらに、蛍光性有機分子は溶液中で高効率発光する（高い蛍光量子収率を示す）場合であっても固体状態では濃度消光によりほとんど発光しなくなる。このため、熱や光などの外部刺激により発光特性が変化する分子は、一般に、固体状態での発光効率（蛍光量子収率）が低いという問題がある。 Solid-fluorescent organic molecules whose light-emitting properties are changed by the application of mechanical stimulus usually require heating or exposure to solvent vapor to restore the original state, which is inconvenient in this respect. In addition, such a molecule has been conventionally synthesized through many steps, and a solid fluorescent organic molecule that can be synthesized by a simple method has been awaited. Furthermore, even when the fluorescent organic molecule emits light with high efficiency in a solution (having a high fluorescence quantum yield), it hardly emits light in the solid state due to concentration quenching. For this reason, molecules whose luminescence characteristics change due to external stimuli such as heat or light generally have a problem that luminescence efficiency (fluorescence quantum yield) in a solid state is low.
本発明は、上記問題に鑑み、機械的刺激により発光色を変化させた後に、加熱や溶媒蒸気にさらすだけでなく、室温付近で自発的に元の発光色に戻ることができ、短段階で簡便に合成でき、且つ、固体状態で高い蛍光量子収率を示す蛍光性有機分子を提供することを課題とする。 The present invention has been made in view of the above problems, and after changing the emission color by mechanical stimulation, not only exposure to heating and solvent vapor, but also can return to the original emission color spontaneously near room temperature, An object of the present invention is to provide a fluorescent organic molecule which can be easily synthesized and has a high fluorescence quantum yield in a solid state.
本発明者らは鋭意研究を重ねた結果、上記課題は、下記式（１）で表されるインドリルベンゾチアジアゾール誘導体を提供することによって解決できることを見出した。 As a result of intensive studies, the present inventors have found that the above problem can be solved by providing an indolylbenzothiadiazole derivative represented by the following formula (1).
本発明は一側面において、下記式（１）で表されるインドリルベンゾチアジアゾール誘導体である。
また、Ｒ5は、アルキルオキシカルボニル基、アリールオキシカルボニル基、アシル基、アルキルスルホニル基またはアリールスルホニル基である。
また、Ｒ9は、ハロゲン原子、ヒドロキシ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、ニトロ基、アミノ基、アミド基、カルボキシ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、ホルミル基、シアノ基、アルキル基、シクロアルキル基、アラルキル基またはアリール基である。）
One aspect of the present invention is an indolylbenzothiadiazole derivative represented by the following formula (1).
R 5 is an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group.
R 9 represents a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amide group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group. , An alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. )
本発明のインドリルベンゾチアジアゾール誘導体は一実施形態において、前記Ｒ5が、ピバロイル基、ベンゾイル基、トシル基、または、下記式（２）から選択される群のうちのいずれか１つである。
本発明は別の一側面において、下記式（３）で表されるインドリルベンゾチアジアゾール誘導体である。
本発明は更に別の一側面において、下記式（４）で表されるインドリルベンゾチアジアゾール誘導体である。
本発明は更に別の一側面において、下記式（５）で表されるインドリルベンゾチアジアゾール誘導体である。
本発明のインドリルベンゾチアジアゾール誘導体は別の一実施形態において、前記Ｒ9が、メチル基、エチル基またはイソプロピル基である。 In another embodiment of the indolylbenzothiadiazole derivative of the present invention, R 9 is a methyl group, an ethyl group or an isopropyl group.
本発明は更に別の一側面において、下記式（６）で表されるボロン酸と、下記式（７）で表されるブロモベンゾチアジアゾールとを反応させることで、前記式（１）に記載のインドリルベンゾチアジアゾール誘導体を得るインドリルベンゾチアジアゾール誘導体の製造方法である。
また、Ｒ5は、アルキルオキシカルボニル基、アリールオキシカルボニル基、アシル基、アルキルスルホニル基またはアリールスルホニル基である。
また、Ｒ9は、ハロゲン原子、ヒドロキシ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、ニトロ基、アミノ基、アミド基、カルボキシ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、ホルミル基、シアノ基、アルキル基、シクロアルキル基、アラルキル基またはアリール基である。）
In a further aspect of the present invention, a boronic acid represented by the following formula (6) is reacted with a bromobenzothiadiazole represented by the following formula (7) to obtain a compound represented by the formula (1). This is a method for producing an indolylbenzothiadiazole derivative to obtain an indolylbenzothiadiazole derivative.
R 5 is an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group.
R 9 represents a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amide group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group. , An alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. )
本発明は更に別の一側面において、本発明のインドリルベンゾチアジアゾール誘導体を有機蛍光色素として用いた有機蛍光材料である。 In still another aspect, the present invention is an organic fluorescent material using the indolylbenzothiadiazole derivative of the present invention as an organic fluorescent dye.
本発明の有機蛍光材料は一実施形態において、蛍光パターニング材料、蛍光スイッチング材料または蛍光センサー材料である。 In one embodiment, the organic fluorescent material of the present invention is a fluorescent patterning material, a fluorescent switching material, or a fluorescent sensor material.
本発明の蛍光性有機分子によれば、以下の効果が得られる。
・短段階で簡便に合成できる。
・固体状態でも濃度消光を起こさず、良好な蛍光量子収率で発光する。
・機械的刺激により発光色を変化させた後に、加熱や溶媒蒸気にさらすだけでなく、室温付近で自発的に元の発光色に戻ることができる。
・熱やｐＨ、或いは光に応答して発光色が変化する蛍光性高分子材料の作製にも応用することができる。
According to the fluorescent organic molecule of the present invention, the following effects can be obtained.
-Can be easily synthesized in a short stage.
-Emit light with good fluorescence quantum yield without concentration quenching even in the solid state.
-After changing the luminescent color by mechanical stimulation, it can return to the original luminescent color spontaneously near room temperature, in addition to heating and exposing to solvent vapor.
-It can be applied to the production of a fluorescent polymer material whose emission color changes in response to heat, pH, or light.
（インドリルベンゾチアジアゾール誘導体）
本発明のインドリルベンゾチアジアゾール誘導体は、下記式（１）で表される。
また、Ｒ5は、アルキルオキシカルボニル基、アリールオキシカルボニル基、アシル基、アルキルスルホニル基またはアリールスルホニル基である。
また、Ｒ9は、ハロゲン原子、ヒドロキシ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、ニトロ基、アミノ基、アミド基、カルボキシ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、ホルミル基、シアノ基、アルキル基、シクロアルキル基、アラルキル基またはアリール基である。）
(Indolyl benzothiadiazole derivative)
The indolylbenzothiadiazole derivative of the present invention is represented by the following formula (1).
R 5 is an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group.
R 9 represents a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amide group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group. , An alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. )
本発明のインドリルベンゾチアジアゾール誘導体は、電子供与基としてのインドリル基と、電子求引基としてのベンゾチアジアゾール基を有し、さらにインドリル基の窒素原子上に前述のＲ5基を有している。通常の蛍光性有機分子は、溶液状態で効率良く発光する場合でも固体状態では多分子間で芳香環や複素環がスタッキングすることで濃度消光が起こるため、蛍光量子収率が低下する。本発明のインドリルベンゾチアジアゾール誘導体は、電子豊富なインドリル基から電子不足なベンゾチアジアゾール環への電荷移動に基づく蛍光を示し、嵩高い電子求引性置換基であるＲ5基（アルキルオキシカルボニル基、アリールオキシカルボニル基、アシル基、アルキルスルホニル基またはアリールスルホニル基）が固体状態におけるベンゾチアジアゾール環の多分子間でのスタッキングを抑制するため、式（１）の状態において固体状態で良好な蛍光量子収率（約１５〜６０％）を示す。本化合物は、結晶状態において、固体発光するが蛍光メカノクロミズムを示さない無置換体と同じく、ベンゾチアジアゾール環を逆平行にしてスタッキングしているが、ベンゾチアジアゾール環が水平方向にずれた状態にある（後述の図３）。このため、蛍光メカノクロミズムが発現し、機械的刺激により発光色を変化させた後に元の発光色に放置するだけで戻ることができ、加熱や蒸気にさらすといった操作が不要となる。本発明のインドリルベンゾチアジアゾール誘導体によれば、溶液中だけでなく、固体状態でも濃度消光を起こさず高効率発光することができる。また、インドール誘導体とベンゾチアジアゾール誘導体の置換基を変更するのみで蛍光発光色の異なる各種誘導体を簡便に合成することができる。また、これらを高分子材料にドープすることで、熱やｐＨ、光等の外部刺激に応答して発光色が変化する蛍光性高分子材料への応用が可能となる。 The indolyl benzothiadiazole derivative of the present invention has an indolyl group as an electron donating group and a benzothiadiazole group as an electron withdrawing group, and further has the aforementioned R 5 group on the nitrogen atom of the indolyl group. . Even when a normal fluorescent organic molecule emits light efficiently in a solution state, in a solid state, concentration quenching occurs due to stacking of aromatic rings and heterocycles among multiple molecules, so that the fluorescence quantum yield decreases. The indolyl benzothiadiazole derivative of the present invention exhibits fluorescence based on charge transfer from an electron-rich indolyl group to an electron-deficient benzothiadiazole ring, and has a bulky electron-withdrawing substituent, R 5 group (alkyloxycarbonyl group). , An aryloxycarbonyl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group) suppresses the stacking of the benzothiadiazole ring among multiple molecules in the solid state, so that a good fluorescence quantum in the solid state in the state of the formula (1) is obtained. The yield (about 15-60%) is shown. In the crystalline state, the benzothiadiazole ring is stacked antiparallel to the unsubstituted compound that emits solid light but does not show fluorescence mechanochromism in the crystalline state, but the benzothiadiazole ring is shifted horizontally. (FIG. 3 described below). For this reason, fluorescence mechanochromism develops, and after changing the emission color by mechanical stimulation, it is possible to return to the original emission color only by leaving the original emission color, and an operation such as heating or exposing to steam becomes unnecessary. According to the indolylbenzothiadiazole derivative of the present invention, high-efficiency light emission can be achieved without concentration quenching not only in a solution but also in a solid state. Further, various derivatives having different fluorescence emission colors can be easily synthesized only by changing the substituents of the indole derivative and the benzothiadiazole derivative. Further, by doping these into a polymer material, application to a fluorescent polymer material whose emission color changes in response to external stimuli such as heat, pH, and light becomes possible.
また、Ｒ5は、ピバロイル基、ベンゾイル基、トシル（ｐ−トルエンスルホニル）基、または、下記式（２）から選択される群のうちのいずれか１つであってもよい。
また、本発明のインドリルベンゾチアジアゾール誘導体は、下記式（３）で表されてもよい。
また、本発明のインドリルベンゾチアジアゾール誘導体は、下記式（４）で表されてもよい。
また、本発明のインドリルベンゾチアジアゾール誘導体は、下記式（５）で表されてもよい。
本発明のインドリルベンゾチアジアゾール誘導体は、前記Ｒ9が、メチル基、エチル基またはイソプロピル基であってもよい。 In the indolylbenzothiadiazole derivative of the present invention, R 9 may be a methyl group, an ethyl group or an isopropyl group.
（インドリルベンゾチアジアゾール誘導体の製造方法）
次に、本発明のインドリルベンゾチアジアゾール誘導体の製造方法について詳述する。前述の式（１）で表されるインドリルベンゾチアジアゾール誘導体は、下記式（６）で表されるボロン酸と、下記式（７）で表されるブロモベンゾチアジアゾールとを、例えば、パラジウム触媒を用いた鈴木−宮浦クロスカップリング反応等の公知の方法で反応させることで得られる。
また、Ｒ5は、アルキルオキシカルボニル基、アリールオキシカルボニル基、アシル基、アルキルスルホニル基またはアリールスルホニル基である。
また、Ｒ9は、ハロゲン原子、ヒドロキシ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、ニトロ基、アミノ基、アミド基、カルボキシ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、ホルミル基、シアノ基、アルキル基、シクロアルキル基、アラルキル基またはアリール基である。）
(Production method of indolylbenzothiadiazole derivative)
Next, the method for producing the indolylbenzothiadiazole derivative of the present invention will be described in detail. The indolylbenzothiadiazole derivative represented by the above formula (1) is obtained by reacting a boronic acid represented by the following formula (6) with a bromobenzothiadiazole represented by the following formula (7), for example, by using a palladium catalyst. It can be obtained by a known method such as the Suzuki-Miyaura cross coupling reaction used.
R 5 is an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group.
R 9 represents a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amide group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group. , An alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. )
（有機蛍光材料）
本発明のインドリルベンゾチアジアゾール誘導体を有機蛍光色素として用いて有機蛍光材料を作製することができる。当該有機蛍光色素を、例えばポリマーにドープすることで、機械的刺激（物理的な力による変形等）を加えることで特性の発光色に変化し、放置することで元の色に戻る有機蛍光材料が得られる。また、これを応用して加熱、光照射による光酸発生、または、酸添加によるｐＨ制御等の外部刺激を受けた部位のみ色調が変化する有機蛍光材料を得ることもできる。
(Organic fluorescent material)
An organic fluorescent material can be produced using the indolylbenzothiadiazole derivative of the present invention as an organic fluorescent dye. An organic fluorescent material that changes its emission color by applying a mechanical stimulus (such as deformation due to physical force) by doping the organic fluorescent dye into a polymer, for example, and then returns to the original color when left to stand Is obtained. Further, by applying this, it is also possible to obtain an organic fluorescent material in which the color tone changes only in a portion that has been subjected to an external stimulus such as heating, generation of photoacid by light irradiation, or pH control by addition of acid.
さらに、前述の有機蛍光材料を、例えば、蛍光パターニング材料、蛍光スイッチング材料または蛍光センサー材料等に用いることができる。 Further, the above-described organic fluorescent material can be used as, for example, a fluorescent patterning material, a fluorescent switching material, a fluorescent sensor material, or the like.
固体状態や溶液状態において機械的刺激や周囲の極性環境に応じて発光色が変化する前述の有機蛍光材料は、具体的には、高感度な蛍光検出を利用した下記の用途に応用することができる。
・書き込み、消去可能な蛍光記憶材料
・材料中の部分的な歪みの検出(自発的に発光色が戻ることで繰り返し利用可能)
・高分子材料の劣化(極性変化)の検出
・高分子重合の経時変化、高分子材料の重合度評価
・生体内の極性変化を可視化する蛍光プローブ
The above-mentioned organic fluorescent material, whose emission color changes in response to mechanical stimulation or surrounding polar environment in a solid state or solution state, can be specifically applied to the following applications utilizing high-sensitivity fluorescence detection. it can.
・ Writable and erasable fluorescent storage material ・ Detection of partial distortion in the material (can be used repeatedly by returning the emission color spontaneously)
・ Detection of deterioration (polarity change) of polymer material ・ Change over time of polymer polymerization, evaluation of polymerization degree of polymer material ・ Fluorescent probe to visualize polarity change in living body
以下に、本発明を実施例でさらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
（実施例１：Ｎ−Ｂｏｃ−３−メチルインドリルベンゾチアジアゾール１ａの合成とその蛍光メカノクロミズム）
Ｎ−Ｂｏｃ−３−メチルインドールにテトラヒドロフラン（ＴＨＦ）中、−２０℃でリチウムジイソプロピルアミド（ＬＤＡ）を作用させた後、ホウ酸トリイソプロピルを加えて１時間半反応させることで、Ｎ−Ｂｏｃ−３−メチルインドール−２−ボロン酸を得た。なお、「Ｂｏｃ」は下記式（８）で示すように、ｔｅｒｔ−ブトキシカルボニル基を示す。次に、得られたボロン酸を単離することなくテトラキス（トリフェニルホスフィン）パラジウム（２０ｍｏｌ％）存在下、４−ブロモ−２，１，３−ベンゾチアジアゾールとジオキサン／炭酸カリウム水溶液混合溶媒中、９５℃で４時間反応させることで、インドリルベンゾチアジアゾール誘導体１ａを収率８４％で得た（図１）。合成した１ａの発光特性を測定したところ、１ａは固体状態で発光極大波長４８５ｎｍで発光し、その蛍光量子収率は０．４６であった。また、トルエン中では発光極大波長５２３ｎｍ、蛍光量子収率０．４３での発光が観測された。
N-Boc-3-methylindole was reacted with lithium diisopropylamide (LDA) at -20 ° C in tetrahydrofuran (THF) at -20 ° C, and triisopropyl borate was added to react for 1.5 hours. 3-Methylindole-2-boronic acid was obtained. Note that “Boc” represents a tert-butoxycarbonyl group as shown by the following formula (8). Next, in a mixed solvent of 4-bromo-2,1,3-benzothiadiazole and dioxane / potassium carbonate aqueous solution in the presence of tetrakis (triphenylphosphine) palladium (20 mol%) without isolation of the obtained boronic acid, By reacting at 95 ° C. for 4 hours, an indolylbenzothiadiazole derivative 1a was obtained with a yield of 84% (FIG. 1). When the emission characteristics of the synthesized 1a were measured, 1a emitted light at a maximum emission wavelength of 485 nm in a solid state, and its fluorescence quantum yield was 0.46. In toluene, light emission with a maximum emission wavelength of 523 nm and a fluorescence quantum yield of 0.43 was observed.
また、以下に１ａの融点、赤外線吸収スペクトル（ＫＢｒ法）:ＩＲ（ＫＢｒ）、1Ｈ ＮＭＲスペクトル、13Ｃ ＮＭＲスペクトルの測定結果を示す。
１ａ：
融点>140℃（分解）
IR (KBr): vmax 3072, 3051, 2998, 2983, 2933, 2915, 2864, 1720, 1601, 1534, 1473, 1457, 1391, 1353, 1333, 1273, 1236, 1203, 1170, 1151, 1128, 1112, 1064, 1008, 912, 901, 872, 851, 842, 832, 810, 757, 742 cm-1.
1H NMR (300 MHz, CDCl3): δ (ppm) 8.29 (d, J = 8.7 Hz, 1H), 8.04 (dd, J = 1.1, 8.7 Hz, 1H), 7.57 (dd, J = 6.8, 8.7 Hz, 1H), 7.61 - 7.55 (m, 2H), 7.40 (ddd, J = 1.5, 7.5, 8.7 Hz, 1H), 7.31 (dt, J = 1.1, 7.5 Hz, 1H), 2.21 (s, 3H), 0.98 (s, 9H).
13C NMR (126 MHz, CDCl3): δ (ppm) 154.9, 154.8, 149.9, 136.7, 130.9, 130.3, 129.3, 129.0, 128.2, 125.1, 122.6, 120.9, 119.1, 118.0, 115.5, 82.4, 27.4, 9.4.
In addition, the measurement results of the melting point of 1a, infrared absorption spectrum (KBr method): IR (KBr), 1 H NMR spectrum, and 13 C NMR spectrum are shown below.
1a:
Melting point> 140 ℃ (decomposition)
IR (KBr): v max 3072, 3051, 2998, 2983, 2933, 2915, 2864, 1720, 1601, 1534, 1473, 1457, 1391, 1353, 1333, 1273, 1236, 1203, 1170, 1151, 1128, 1112 , 1064, 1008, 912, 901, 872, 851, 842, 832, 810, 757, 742 cm -1 .
1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 8.29 (d, J = 8.7 Hz, 1H), 8.04 (dd, J = 1.1, 8.7 Hz, 1H), 7.57 (dd, J = 6.8, 8.7 Hz, 1H), 7.61-7.55 (m, 2H), 7.40 (ddd, J = 1.5, 7.5, 8.7 Hz, 1H), 7.31 (dt, J = 1.1, 7.5 Hz, 1H), 2.21 (s, 3H) , 0.98 (s, 9H).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 154.9, 154.8, 149.9, 136.7, 130.9, 130.3, 129.3, 129.0, 128.2, 125.1, 122.6, 120.9, 119.1, 118.0, 115.5, 82.4, 27.4, 9.4 .
固体蛍光色素１ａに対し、スパチュラで擦ることによる機械的刺激を加えたところ、その発光色は青緑色から黄緑色へと長波長シフトした。また、機械的刺激により変化した発光色は室温下１０秒程度放置することで自発的に元の発光色へ戻った（図２）。通常、機械的刺激により発光色が可逆的に変化する蛍光メカノクロミズムを示す分子は、元の状態に戻すために加熱や溶媒蒸気にさらす必要がある。機械的刺激により変化した発光色が室温下短時間で自発的に元の色に戻るのは極めて珍しい現象である。 When a mechanical stimulus was applied to the solid fluorescent dye 1a by rubbing with a spatula, the emission color shifted from blue-green to yellow-green with a longer wavelength. The luminescent color changed by the mechanical stimulus spontaneously returned to the original luminescent color when left at room temperature for about 10 seconds (FIG. 2). Usually, molecules exhibiting fluorescent mechanochromism, whose emission color is reversibly changed by mechanical stimulation, need to be heated or exposed to a solvent vapor in order to return to the original state. It is an extremely rare phenomenon that the luminescent color changed by a mechanical stimulus returns to the original color spontaneously in a short time at room temperature.
そこで、１ａの単結晶を作成し、Ｘ線結晶構造解析を行ったところ、結晶状態において１ａは、固体発光するが蛍光メカノクロミズムを示さない無置換体２ａと同じく、ベンゾチアジアゾール環を逆平行にしてスタッキングしていることが明らかとなった。しかし１ａは、ベンゾチアジアゾール環が水平方向にずれた状態にあり、このことが蛍光メカノクロミズムの発現に寄与していると推察される（図３）。 Therefore, a single crystal of 1a was prepared and subjected to X-ray crystal structure analysis. In the crystalline state, 1a had a benzothiadiazole ring made antiparallel to the unsubstituted 2a which emits solid light but does not show fluorescence mechanochromism. It was clear that they were stacking. However, in 1a, the benzothiadiazole ring was shifted in the horizontal direction, which is presumed to have contributed to the development of fluorescent mechanochromism (FIG. 3).
（実施例２：各種置換基を有するインドリルベンゾチアジアゾール誘導体の合成とその蛍光メカノクロミズム）
発光色および機械的刺激により変化した発光色の持続時間を調節することを目的として、種々の置換基を有する３−メチルインドリルベンゾチアジアゾール誘導体を合成した。なお、以下の検討ではいずれも合成した化合物の単離精製法を確立しておらず、収率には改善の余地がある。まず、ベンゾチアジアゾール環にメチル基、ホルミル基、シアノ基を有する１ｂ−１ｄの合成を行った（図４）。無置換体１ａの合成と同様に、Ｎ−Ｂｏｃ−３−メチルインドールから合成したボロン酸に対し、置換基Ｒ6の異なる種々のブロモベンゾチアジアゾールをパラジウム触媒存在下で反応させることで、カップリング体１ｂ−１ｄを収率５１−７１％で得た（図４）。合成した１ｂ−１ｄのトルエン中での蛍光スペクトルを測定したところ、Ｒ6にメチル基を有する１ｂは１ａと同程度の発光極大波長（５２３ｎｍ）であり、ホルミル基やシアノ基を有する１ｃ、１ｄでは４０ｎｍ程度長波長シフトした。
(Example 2: Synthesis of indolyl benzothiadiazole derivative having various substituents and its fluorescence mechanochromism)
In order to control the emission color and the duration of the emission color changed by mechanical stimulation, 3-methylindolylbenzothiadiazole derivatives having various substituents were synthesized. In any of the following studies, no method for isolating and purifying the synthesized compound has been established, and there is room for improvement in the yield. First, 1b-1d having a methyl group, a formyl group, and a cyano group on the benzothiadiazole ring was synthesized (FIG. 4). As in the synthesis of the unsubstituted product 1a, the coupling is performed by reacting boronic acid synthesized from N-Boc-3-methylindole with various bromobenzothiadiazoles having different substituents R 6 in the presence of a palladium catalyst. The product 1b-1d was obtained in a yield of 51-71% (FIG. 4). When the fluorescence spectrum of the synthesized 1b-1d in toluene was measured, 1b having a methyl group at R 6 had the same emission maximum wavelength (523 nm) as 1a, and 1c and 1d having a formyl group and a cyano group. In this case, the wavelength was shifted by about 40 nm.
また、以下に１ｂ、１ｃ及び１ｄで表されるインドリルベンゾチアジアゾール誘導体の融点、赤外線吸収スペクトル（ＫＢｒ法）:ＩＲ（ＫＢｒ）、1Ｈ ＮＭＲスペクトル、13Ｃ ＮＭＲスペクトルの測定結果をそれぞれ示す。 The melting points, infra-red absorption spectra (KBr method): IR (KBr), 1 H NMR spectrum and 13 C NMR spectrum of the indolylbenzothiadiazole derivatives represented by 1b, 1c and 1d are shown below.
１ｂ：
融点>160℃（分解）
IR (KBr): vmax 3070, 3053, 2982, 2932, 2914, 2861, 1720, 1596, 1456, 1354, 1335, 1243, 1214, 1147, 1093, 1077, 1008, 884, 874, 854, 844, 818, 755, 741, 689, 669 cm-1.
1H NMR (500 MHz, CDCl3): δ (ppm) 8.27 (d, J = 8.2 Hz, 1H), 7.56 (d, J = 8.0 Hz, 1H), 7.46 (d, J = 7.3 Hz, 1H), 7.45 (d, J = 7.3 Hz, 1H), 7.38 (dd, J = 7.3, 8.2 Hz, 1H), 7.29 (dd, J = 7.3, 8.0 Hz, 1H), 2.80 (s, 3H), 2.19 (s, 3H), 1.02 (s, 9H).
13C NMR (126 MHz, CDCl3): δ (ppm) 155.4, 154.8, 150.0, 136.6, 131.3, 131.1, 130.4, 129.3, 127.9, 125.5, 124.9, 122.5, 119.0, 117.7, 115.4, 82.4, 27.4, 18.0, 9.4.
1b:
Melting point> 160 ℃ (decomposition)
IR (KBr): v max 3070, 3053, 2982, 2932, 2914, 2861, 1720, 1596, 1456, 1354, 1335, 1243, 1214, 1147, 1093, 1077, 1008, 884, 874, 854, 844, 818 , 755, 741, 689, 669 cm -1 .
1 H NMR (500 MHz, CDCl 3 ): δ (ppm) 8.27 (d, J = 8.2 Hz, 1H), 7.56 (d, J = 8.0 Hz, 1H), 7.46 (d, J = 7.3 Hz, 1H) , 7.45 (d, J = 7.3 Hz, 1H), 7.38 (dd, J = 7.3, 8.2 Hz, 1H), 7.29 (dd, J = 7.3, 8.0 Hz, 1H), 2.80 (s, 3H), 2.19 ( s, 3H), 1.02 (s, 9H).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 155.4, 154.8, 150.0, 136.6, 131.3, 131.1, 130.4, 129.3, 127.9, 125.5, 124.9, 122.5, 119.0, 117.7, 115.4, 82.4, 27.4, 18.0 , 9.4.
１ｃ：
融点>140℃（分解）
IR (KBr): vmax 3072, 3048, 2985, 2935, 2912, 2852, 1720, 1698, 1589, 1573, 1539, 1471, 1455, 1390, 1352, 1331, 1262, 1241, 1215, 1145, 1092, 1073, 1007, 873, 850, 802, 756, 741, 688 cm-1.
1H NMR (300 MHz, CDCl3): δ (ppm) 10.80 (s, 1H), 8.33 (d, J = 6.9 Hz, 1H), 8.26 (dd, J = 1.4, 7.9 Hz, 1H), 7.76 (d, J = 6.9 Hz, 1H), 7.62 (dd, J = 1.3, 8.2 Hz, 1H), 7.44 (ddd, J = 1.4, 8.2, 8.8 Hz, 1H), 7.33 (ddd, J = 1.3, 7.9, 8.8 Hz, 1H), 2.25 (s, 3H), 1.08 (s, 9H).
13C NMR (126 MHz, CDCl3): δ (ppm) 188.8, 155.3, 152.9, 149.8, 136.8, 134.2, 132.3, 130.19, 130.16, 128.0, 126.8, 125.8, 122.9, 119.6, 119.4, 115.5, 83.1, 27.5, 9.5.
1c:
Melting point> 140 ℃ (decomposition)
IR (KBr): v max 3072, 3048, 2985, 2935, 2912, 2852, 1720, 1698, 1589, 1573, 1539, 1471, 1455, 1390, 1352, 1331, 1262, 1241, 1215, 1145, 1092, 1073 , 1007, 873, 850, 802, 756, 741, 688 cm -1 .
1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 10.80 (s, 1H), 8.33 (d, J = 6.9 Hz, 1H), 8.26 (dd, J = 1.4, 7.9 Hz, 1H), 7.76 ( d, J = 6.9 Hz, 1H), 7.62 (dd, J = 1.3, 8.2 Hz, 1H), 7.44 (ddd, J = 1.4, 8.2, 8.8 Hz, 1H), 7.33 (ddd, J = 1.3, 7.9, 8.8 Hz, 1H), 2.25 (s, 3H), 1.08 (s, 9H).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 188.8, 155.3, 152.9, 149.8, 136.8, 134.2, 132.3, 130.19, 130.16, 128.0, 126.8, 125.8, 122.9, 119.6, 119.4, 115.5, 83.1, 27.5 , 9.5.
１ｄ：
融点>140℃（分解）
IR (KBr): vmax 3101, 3074, 3054, 2989, 2938, 2910, 2860, 2225, 1717, 1583, 1541, 1456, 1382, 1367, 1355, 1336, 1274, 1241, 1215, 1143, 1093, 1007, 969, 885, 862, 850, 837, 817, 756, 742, 688, 667 cm-1.
1H NMR (500 MHz, CDCl3): δ (ppm) 8.24 (d, J = 8.2 Hz, 1H), 8.15 (d, J = 7.3 Hz, 1H), 7.65 (d, J = 7.3 Hz, 1H), 7.62 (d, J = 7.6 Hz, 1H), 7.44 (dd, J = 7.6, 8.2 Hz, 1H), 7.34 (dd, J = 7.4, 8.2 Hz, 1H), 2.24 (s, 3H), 1.13 (s, 9H).
13C NMR (126 MHz, CDCl3): δ (ppm) 154.2, 152.9, 149.7, 136.8, 135.8, 133.6, 130.1, 129.5, 127.6, 126.0, 123.0, 119.8, 119.5, 115.5, 115.4, 104.8, 83.4, 27.6, 9.5.
1d:
Melting point> 140 ℃ (decomposition)
IR (KBr): v max 3101, 3074, 3054, 2989, 2938, 2910, 2860, 2225, 1717, 1583, 1541, 1456, 1382, 1367, 1355, 1336, 1274, 1241, 1215, 1143, 1093, 1007 , 969, 885, 862, 850, 837, 817, 756, 742, 688, 667 cm -1 .
1 H NMR (500 MHz, CDCl 3 ): δ (ppm) 8.24 (d, J = 8.2 Hz, 1H), 8.15 (d, J = 7.3 Hz, 1H), 7.65 (d, J = 7.3 Hz, 1H) , 7.62 (d, J = 7.6 Hz, 1H), 7.44 (dd, J = 7.6, 8.2 Hz, 1H), 7.34 (dd, J = 7.4, 8.2 Hz, 1H), 2.24 (s, 3H), 1.13 ( s, 9H).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 154.2, 152.9, 149.7, 136.8, 135.8, 133.6, 130.1, 129.5, 127.6, 126.0, 123.0, 119.8, 119.5, 115.5, 115.4, 104.8, 83.4, 27.6 , 9.5.
合成した１ｂ−１ｄはいずれも固体状態で発光し、１ｂ−１ｄは蛍光メカノクロミズムを示した（図５）。メチル基を有する１ｂとホルミル基を有する１ｃはそれぞれ、機械的刺激を加えることで緑色から黄色、黄色から橙色に発光色が変化し、どちらも室温下２分程度で元の発光色に戻った。また、シアノ基を有する１ｄでは機械的刺激により発光色が橙色から赤色に変化し、室温下で元の発光色に戻るまで１０分以上必要であった。 All of the synthesized 1b-1d emitted light in a solid state, and 1b-1d exhibited fluorescent mechanochromism (FIG. 5). The emission color of 1b having a methyl group and 1c having a formyl group changed from green to yellow and yellow to orange, respectively, upon application of mechanical stimulation, and both returned to the original emission color in about 2 minutes at room temperature. . In the case of 1d having a cyano group, the emission color changed from orange to red due to mechanical stimulation, and it took 10 minutes or more to return to the original emission color at room temperature.
次に、インドール環の窒素原子上の置換基が異なる各種化合物を合成するため、１ａの脱Ｂｏｃ化を行った。すなわち、１ａをジクロロメタン中、過剰量のトリフルオロ酢酸（ＴＦＡ）と室温で１６時間反応させ、４−（３−メチル−１Ｈ−インドール−２−イル）−２，１，３−ベンゾチアジアゾール３ａを収率９９％で得た（図６）。 Next, in order to synthesize various compounds having different substituents on the nitrogen atom of the indole ring, de-Bocation of 1a was performed. That is, 1a is reacted with an excess amount of trifluoroacetic acid (TFA) in dichloromethane at room temperature for 16 hours to give 4- (3-methyl-1H-indol-2-yl) -2,1,3-benzothiadiazole 3a. It was obtained with a yield of 99% (FIG. 6).
また、以下に３ａの融点、赤外線吸収スペクトル（ＫＢｒ法）:ＩＲ（ＫＢｒ）、1Ｈ ＮＭＲスペクトル、13Ｃ ＮＭＲスペクトルの測定結果を示す。 The melting point of 3a, infrared absorption spectrum (KBr method): IR (KBr), 1 H NMR spectrum and 13 C NMR spectrum are shown below.
３ａ：
融点123 - 124℃
IR (KBr): vmax 3482, 3381, 3054, 2963, 2861, 1645, 1588, 1541, 1523, 1481, 1463, 1445, 1435, 1394, 1380, 1367, 1332, 1309, 1250, 1238, 1184, 1163, 1154, 1127, 1108, 1051, 904, 884, 858, 841, 807, 791, 746, 740, 687 cm-1.
1H NMR (500 MHz, CDCl3): δ (ppm) 10.47 (br s, 1H), 7.80 (d, J = 8.8 Hz, 1H), 7.81 (d, J = 7.3 Hz, 1H), 7.61 (d, J = 7.6 Hz, 1H), 7.56 (dd, J = 7.3, 8.8 Hz, 1H), 7.41 (dd, J = 0.9, 8.0 Hz, 1H), 7.22 (ddd, J = 0.9, 7.0, 7.6 Hz, 1H), 7.12 (ddd, J = 0.9, 7.0, 8.0 Hz, 1H), 2.56 (s, 3H).
13C NMR (126 MHz, CDCl3): δ (ppm) 155.4, 152.6, 135.9, 130.0, 129.8, 129.2, 126.3, 125.5, 123.1, 119.4, 119.1, 118.9, 111.5, 111.1, 11.4.
3a:
123-124 ° C
IR (KBr): v max 3482, 3381, 3054, 2963, 2861, 1645, 1588, 1541, 1523, 1481, 1463, 1445, 1435, 1394, 1380, 1367, 1332, 1309, 1250, 1238, 1184, 1163 , 1154, 1127, 1108, 1051, 904, 884, 858, 841, 807, 791, 746, 740, 687 cm -1 .
1 H NMR (500 MHz, CDCl 3 ): δ (ppm) 10.47 (br s, 1H), 7.80 (d, J = 8.8 Hz, 1H), 7.81 (d, J = 7.3 Hz, 1H), 7.61 (d , J = 7.6 Hz, 1H), 7.56 (dd, J = 7.3, 8.8 Hz, 1H), 7.41 (dd, J = 0.9, 8.0 Hz, 1H), 7.22 (ddd, J = 0.9, 7.0, 7.6 Hz, 1H), 7.12 (ddd, J = 0.9, 7.0, 8.0 Hz, 1H), 2.56 (s, 3H).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 155.4, 152.6, 135.9, 130.0, 129.8, 129.2, 126.3, 125.5, 123.1, 119.4, 119.1, 118.9, 111.5, 111.1, 11.4.
得られた３ａに対し、２当量の水素化ナトリウム存在下、置換基Ｒ10の異なる種々のクロロギ酸エステル（２当量）をＴＨＦ中室温で１２〜１９時間反応させることで、Ｒ10にエチル基（Ｅｔ）、イソプロピル基（ｉ−Ｐｒ）、イソブチル基（ｉ−Ｂｕ）、ベンジル基（Ｂｎ）を有するインドリルベンゾチアジアゾール誘導体１ｅ−１ｈを収率５０−７３％で得た（図７）。いずれもトルエン溶液中での発光極大波長は同程度であった。 The obtained 3a, 2 equivalents of sodium hydride presence, a variety of different chloroformate of substituent R 10 (2 eq) is reacted 12-19 hours at room temperature in THF, ethyl R 10 group (Et), an indolylbenzothiadiazole derivative 1e-1h having an isopropyl group (i-Pr), an isobutyl group (i-Bu), and a benzyl group (Bn) was obtained in a yield of 50-73% (FIG. 7). In each case, the emission maximum wavelength in the toluene solution was almost the same.
また、以下に１ｅ、１ｆ、１ｇ及び１ｈで表されるインドリルベンゾチアジアゾール誘導体の融点、赤外線吸収スペクトル（ＫＢｒ法）:ＩＲ（ＫＢｒ）、1Ｈ ＮＭＲスペクトル、13Ｃ ＮＭＲスペクトルの測定結果をそれぞれ示す。 The melting points, infra-red absorption spectrum (KBr method): IR (KBr), 1 H NMR spectrum, and 13 C NMR spectrum of the indolylbenzothiadiazole derivatives represented by 1e, 1f, 1g, and 1h are shown below. Show.
１ｅ：
融点97 - 98℃
IR (KBr): vmax 3049, 2978, 2930, 2912, 2869, 1733, 1601, 1538, 1479, 1456, 1412, 1379, 1328, 1320, 1302, 1281, 1226, 1198, 1161, 1128, 1117, 1025, 889, 848, 830, 810, 742, 704, 676 cm-1.
1H NMR (300 MHz, CDCl3): δ (ppm) 8.26 (d, J = 8.6 Hz, 1H), 8.04 (dd, J = 0.9, 8.7 Hz, 1H), 7.70 (dd, J = 7.0, 8.7 Hz, 1H), 7.61 - 7.53 (m, 2H), 7.41 (ddd, J = 1.2, 7.2, 8.6 Hz, 1H), 7.33 (ddd, J = 0.9, 7.2, 8.2 Hz, 1H), 4.03 - 3.90 (m, 2H), 2.21 (s, 3H), 0.68 (t, J = 7.0 Hz, 3H).
13C NMR (126 MHz, CDCl3): δ (ppm) 154.82, 154.77, 151.4, 136.4, 130.9, 130.5, 129.3, 129.2, 127.7, 125.3, 122.9, 121.1, 119.2, 118.6, 115.5, 62.4, 13.3, 9.4.
1e:
Melting point 97-98 ° C
IR (KBr): v max 3049, 2978, 2930, 2912, 2869, 1733, 1601, 1538, 1479, 1456, 1412, 1379, 1328, 1320, 1302, 1281, 1226, 1198, 1161, 1128, 1117, 1025 , 889, 848, 830, 810, 742, 704, 676 cm -1 .
1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 8.26 (d, J = 8.6 Hz, 1H), 8.04 (dd, J = 0.9, 8.7 Hz, 1H), 7.70 (dd, J = 7.0, 8.7 Hz, 1H), 7.61-7.53 (m, 2H), 7.41 (ddd, J = 1.2, 7.2, 8.6 Hz, 1H), 7.33 (ddd, J = 0.9, 7.2, 8.2 Hz, 1H), 4.03-3.90 ( m, 2H), 2.21 (s, 3H), 0.68 (t, J = 7.0 Hz, 3H).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 154.82, 154.77, 151.4, 136.4, 130.9, 130.5, 129.3, 129.2, 127.7, 125.3, 122.9, 121.1, 119.2, 118.6, 115.5, 62.4, 13.3, 9.4 .
１ｆ：
融点108 - 109℃
IR (KBr): vmax 3072, 3044, 2975, 2926, 2874, 2857, 1731, 1604, 1535, 1457, 1392, 1368, 1339, 1317, 1267, 1230, 1203, 1166, 1130, 1103, 1064, 1010, 899, 852, 834, 803, 766, 757, 707, 675 cm-1.
1H NMR (500 MHz, CDCl3): δ (ppm) 8.30 (d, J = 8.6 Hz, 1H), 8.05 (dd, J = 1.1, 8.8 Hz, 1H), 7.70 (dd, J = 7.0, 8.8 Hz, 1H), 7.59 (d, J = 8.0 Hz, 1H), 7.56 (dd, J = 1.1, 7.0 Hz, 1H), 7.41 (dd, J = 7.2, 8.6 Hz, 1H), 7.32 (dd, J = 7.2, 8.0 Hz, 1H), 4.78 (quin, J = 6.3 Hz, 1H), 2.21 (s, 3H), 0.90 (d, J = 6.3 Hz, 3H), 0.52 (d, J = 6.3 Hz, 3H).
13C NMR (126 MHz, CDCl3): δ (ppm) 154.9, 154.8, 150.8, 136.6, 130.9, 130.4, 129.23, 129.21, 128.0, 125.2, 122.9, 121.1, 119.1, 118.4, 115.6, 70.3, 21.5, 20.7, 9.4.
1f:
Melting point 108-109 ℃
IR (KBr): v max 3072, 3044, 2975, 2926, 2874, 2857, 1731, 1604, 1535, 1457, 1392, 1368, 1339, 1317, 1267, 1230, 1203, 1166, 1130, 1103, 1064, 1010 , 899, 852, 834, 803, 766, 757, 707, 675 cm -1 .
1 H NMR (500 MHz, CDCl 3 ): δ (ppm) 8.30 (d, J = 8.6 Hz, 1H), 8.05 (dd, J = 1.1, 8.8 Hz, 1H), 7.70 (dd, J = 7.0, 8.8 Hz, 1H), 7.59 (d, J = 8.0 Hz, 1H), 7.56 (dd, J = 1.1, 7.0 Hz, 1H), 7.41 (dd, J = 7.2, 8.6 Hz, 1H), 7.32 (dd, J = 7.2, 8.0 Hz, 1H), 4.78 (quin, J = 6.3 Hz, 1H), 2.21 (s, 3H), 0.90 (d, J = 6.3 Hz, 3H), 0.52 (d, J = 6.3 Hz, 3H) ).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 154.9, 154.8, 150.8, 136.6, 130.9, 130.4, 129.23, 129.21, 128.0, 125.2, 122.9, 121.1, 119.1, 118.4, 115.6, 70.3, 21.5, 20.7 , 9.4.
１ｇ：
融点138 - 140℃
IR (KBr): vmax 3074, 3042, 3014, 2974, 2955, 2926, 2893, 2874, 1729, 1602, 1535, 1466, 1457, 1404, 1381, 1351, 1325, 1269, 1229, 1204, 1166, 1130, 1112, 1064, 1030, 1013, 965, 945, 900, 854, 830, 810, 768, 758, 707, 675 cm-1.
1H NMR (300 MHz, CDCl3): δ (ppm) 8.28 (d, J = 8.7 Hz, 1H), 8.04 (dd, J = 1.1, 8.7 Hz, 1H), 7.70 (dd, J = 6.8, 8.7 Hz, 1H), 7.64 - 7.56 (m, 2H), 7.42 (ddd, J = 1.2, 7.5, 8.7 Hz, 1H), 7.33 (dt, J = 1.1, 7.5 Hz, 1H), 3.84 (dd, J = 7.0, 10.4 Hz, 1H), 3.57 (dd, J = 6.2, 10.4 Hz, 1H), 2.21 (s, 3H), 1.31 - 1.15 (m, 1H), 0.54 (d, J = 5.3 Hz, 3H), 0.52 (d, J = 5.3 Hz, 3H).
13C NMR (126 MHz, CDCl3): δ (ppm) 154.8, 154.7, 151.6, 136.5, 130.8, 130.4, 129.2, 129.1, 127.6, 125.3, 122.9, 121.1, 119.1, 118.7, 115.5, 73.0, 27.2, 18.64, 18.57, 9.5.
1g:
138-140 ° C
IR (KBr): v max 3074, 3042, 3014, 2974, 2955, 2926, 2893, 2874, 1729, 1602, 1535, 1466, 1457, 1404, 1381, 1351, 1325, 1269, 1229, 1204, 1166, 1130 , 1112, 1064, 1030, 1013, 965, 945, 900, 854, 830, 810, 768, 758, 707, 675 cm -1 .
1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 8.28 (d, J = 8.7 Hz, 1H), 8.04 (dd, J = 1.1, 8.7 Hz, 1H), 7.70 (dd, J = 6.8, 8.7 Hz, 1H), 7.64-7.56 (m, 2H), 7.42 (ddd, J = 1.2, 7.5, 8.7 Hz, 1H), 7.33 (dt, J = 1.1, 7.5 Hz, 1H), 3.84 (dd, J = 7.0, 10.4 Hz, 1H), 3.57 (dd, J = 6.2, 10.4 Hz, 1H), 2.21 (s, 3H), 1.31-1.15 (m, 1H), 0.54 (d, J = 5.3 Hz, 3H), 0.52 (d, J = 5.3 Hz, 3H).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 154.8, 154.7, 151.6, 136.5, 130.8, 130.4, 129.2, 129.1, 127.6, 125.3, 122.9, 121.1, 119.1, 118.7, 115.5, 73.0, 27.2, 18.64 , 18.57, 9.5.
１ｈ：
融点116 - 118℃
IR (KBr): vmax 3059, 3050, 3035, 2940, 2917, 2860, 1723, 1598, 1534, 1498, 1456, 1398, 1349, 1329, 1309, 1268, 1230, 1202, 1161, 1127, 1115, 1064, 1038, 1028, 1014, 979, 957, 934, 901, 849, 837, 827, 809, 754, 734, 693, 677 cm-1.
1H NMR (300 MHz, CDCl3): δ (ppm) 8.31 (d, J = 8.7 Hz, 1H), 7.86 (dd, J = 1.2, 8.7 Hz, 1H), 7.63 - 7.54 (m, 2H), 7.50 (dd, J = 1.2, 6.8 Hz, 1H), 7.41 (ddd, J = 1.5, 7.5, 8.7 Hz, 1H), 7.33 (dt, J = 1.2, 7.5 Hz, 1H), 7.25 - 7.19 (m, 1H), 7.19 - 7.13 (m, 2H), 6.77 - 6.72 (m, 2H), 4.93 (d, J = 12.0 Hz, 1H), 4.88 (d, J = 12.0 Hz, 1H), 2.18 (s, 3H).
13C NMR (126 MHz, CDCl3): δ (ppm) 154.58, 154.55, 151.3, 136.6, 134.0, 130.9, 130.5, 129.2, 128.8, 128.44, 128.36, 128.0, 127.4, 125.4, 123.0, 121.2, 119.2, 118.9, 115.6, 68.5, 9.5.
1h:
Melting point 116-118 ℃
IR (KBr): v max 3059, 3050, 3035, 2940, 2917, 2860, 1723, 1598, 1534, 1498, 1456, 1398, 1349, 1329, 1309, 1268, 1230, 1202, 1161, 1127, 1115, 1064 , 1038, 1028, 1014, 979, 957, 934, 901, 849, 837, 827, 809, 754, 734, 693, 677 cm -1 .
1 H NMR (300 MHz, CDCl 3 ): δ (ppm) 8.31 (d, J = 8.7 Hz, 1H), 7.86 (dd, J = 1.2, 8.7 Hz, 1H), 7.63-7.54 (m, 2H), 7.50 (dd, J = 1.2, 6.8 Hz, 1H), 7.41 (ddd, J = 1.5, 7.5, 8.7 Hz, 1H), 7.33 (dt, J = 1.2, 7.5 Hz, 1H), 7.25-7.19 (m, 1H), 7.19-7.13 (m, 2H), 6.77-6.72 (m, 2H), 4.93 (d, J = 12.0 Hz, 1H), 4.88 (d, J = 12.0 Hz, 1H), 2.18 (s, 3H ).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 154.58, 154.55, 151.3, 136.6, 134.0, 130.9, 130.5, 129.2, 128.8, 128.44, 128.36, 128.0, 127.4, 125.4, 123.0, 121.2, 119.2, 118.9 , 115.6, 68.5, 9.5.
合成した１ｅ−１ｈはいずれも固体状態で発光するとともに、蛍光メカノクロミズムを示した（図８）。エチル基を有する１ｅは、機械的刺激を加えることで固体発光色が青緑色から黄緑色に変化し、変化した発光色は約１分後に元の色に戻った。イソプロピル基を有する１ｆの場合は、固体発光色が青色から黄色に変化し、約３０秒後に元の色に戻った。イソブチル基を有する１ｇは発光色が戻る速度が最も大きく、機械的刺激により緑色から黄色に変化した発光色は直ちに（約３秒後）元に戻った。同様に、ベンジル基を有する１ｈは、緑色から黄色に変化した発光色が室温下１分程度で元に戻った。このように、カルバミン酸エステルの置換基を変更することによって、発光色および機械的刺激により変化した発光色が元に戻るまでの時間を調節することができた。 All of the synthesized 1e-1h emitted light in a solid state and exhibited fluorescence mechanochromism (FIG. 8). In the case of 1e having an ethyl group, the solid emission color changed from blue-green to yellow-green upon application of a mechanical stimulus, and the changed emission color returned to the original color after about 1 minute. In the case of 1f having an isopropyl group, the solid emission color changed from blue to yellow, and returned to the original color after about 30 seconds. The emission color of 1 g having an isobutyl group was the fastest to return the luminescent color, and the luminescent color changed from green to yellow due to mechanical stimulation returned immediately (after about 3 seconds). Similarly, for 1h having a benzyl group, the emission color changed from green to yellow was restored in about 1 minute at room temperature. As described above, by changing the substituent of the carbamate, it was possible to adjust the emission color and the time until the emission color changed by the mechanical stimulus returns to the original state.
クロロギ酸エステルを用いた１ｅ−１ｈの合成と同様に、３ａに水素化ナトリウム存在下、塩化ピバロイル、塩化ベンゾイル、または塩化ｐ−トルエンスルホニルをＴＨＦ中室温で一晩反応させることで、ピバロイル（Ｐｉｖ）基、ベンゾイル（Ｂｚ）基、トシル（Ｔｓ）基を有するインドリルベンゾチアジアゾール誘導体１ｉ−１ｋをそれぞれ収率４１％、４６％、４０％で得た（図９）。 As in the synthesis of 1e-1h using chloroformate, pivaloyl chloride (Piv) was reacted with pivaloyl chloride, benzoyl chloride, or p-toluenesulfonyl chloride in THF at room temperature overnight in the presence of sodium hydride. ), A benzoyl (Bz) group, and an indolyl benzothiadiazole derivative 1i-1k having a tosyl (Ts) group were obtained at yields of 41%, 46%, and 40%, respectively (FIG. 9).
また、以下に１ｉ、１ｊ及び１ｋで表されるインドリルベンゾチアジアゾール誘導体の融点、赤外線吸収スペクトル（ＫＢｒ法）:ＩＲ（ＫＢｒ）、1Ｈ ＮＭＲスペクトル、13Ｃ ＮＭＲスペクトルの測定結果をそれぞれ示す。 The melting points, infra-red absorption spectrum (KBr method): IR (KBr), 1 H NMR spectrum and 13 C NMR spectrum of the indolylbenzothiadiazole derivatives represented by 1i, 1j and 1k are shown below.
１ｉ：
融点95.6 - 96.2℃
IR (KBr): vmax 3065, 2970, 2927, 2864, 1715, 1475, 1449, 1327, 1299, 1220, 1172, 1126, 908, 856, 841, 823, 810, 776, 756, 750, 638, 619 cm-1.
1H NMR (500 MHz, CDCl3): δ (ppm) 8.05 (dd, J = 0.9, 8.4 Hz, 1H), 7.70 (dd, J = 6.9, 8.4 Hz, 1H), 7.64 (dd, J = 0.8, 7.2 Hz, 1H), 7.60 (dd, J = 0.9, 6.9 Hz, 1H), 7.53 (dd, J = 0.8, 8.2 Hz, 1H), 7.33 (ddd, J = 0.8, 7.8, 8.2 Hz, 1H), 7.25 (ddd, J = 0.8, 7.8, 8.2 Hz, 1H), 2.28 (s, 3H), 0.96 (s, 9H).
13C NMR (126 MHz, CDCl3): δ (ppm) 184.9, 155.1, 153.4, 136.4, 131.1, 130.5, 129.4, 129.2, 127.1, 124.3, 121.4, 121.3, 119.4, 116.5, 112.2, 43.9, 27.8, 9.9.
1i:
95.6-96.2 ° C
IR (KBr): v max 3065, 2970, 2927, 2864, 1715, 1475, 1449, 1327, 1299, 1220, 1172, 1126, 908, 856, 841, 823, 810, 776, 756, 750, 638, 619 cm -1 .
1 H NMR (500 MHz, CDCl 3 ): δ (ppm) 8.05 (dd, J = 0.9, 8.4 Hz, 1H), 7.70 (dd, J = 6.9, 8.4 Hz, 1H), 7.64 (dd, J = 0.8 , 7.2 Hz, 1H), 7.60 (dd, J = 0.9, 6.9 Hz, 1H), 7.53 (dd, J = 0.8, 8.2 Hz, 1H), 7.33 (ddd, J = 0.8, 7.8, 8.2 Hz, 1H) , 7.25 (ddd, J = 0.8, 7.8, 8.2 Hz, 1H), 2.28 (s, 3H), 0.96 (s, 9H).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 184.9, 155.1, 153.4, 136.4, 131.1, 130.5, 129.4, 129.2, 127.1, 124.3, 121.4, 121.3, 119.4, 116.5, 112.2, 43.9, 27.8, 9.9 .
１ｊ：
融点191.2 - 191.6℃
IR (KBr): vmax 3052, 2913, 2858, 1673, 1598, 1598, 1535, 1473, 1453, 1390, 1351, 1331, 1230, 1201, 1152, 1051, 1024, 902, 874, 853, 829, 812, 761, 748, 716, 697, 669 cm-1.
1H NMR (500 MHz, CDCl3): δ (ppm) 7.80 - 7.76 (m, 1H), 7.69 - 7.64 (m, 2H), 7.54 - 7.52 (m, 2H), 7.44 (d, J = 7.3 Hz, 2H), 7.34 - 7.28 (m, 2H), 7.21 (t, J = 9.1 Hz, 1H), 7.05 (t, J = 7.9 Hz, 2H), 2.33 (s, 3H).
13C NMR (126 MHz, CDCl3): δ (ppm) 169.6, 154.6, 153.6, 137.3, 135.1, 131.94, 131.88, 130.4, 130.1, 129.2, 129.0, 127.5, 126.6, 125.1, 122.9, 121.0, 119.3, 118.9, 114.6, 9.7.
1j:
191.2-191.6 ° C
IR (KBr): v max 3052, 2913, 2858, 1673, 1598, 1598, 1535, 1473, 1453, 1390, 1351, 1331, 1230, 1201, 1152, 1051, 1024, 902, 874, 853, 829, 812 , 761, 748, 716, 697, 669 cm -1 .
1 H NMR (500 MHz, CDCl 3 ): δ (ppm) 7.80-7.76 (m, 1H), 7.69-7.64 (m, 2H), 7.54-7.52 (m, 2H), 7.44 (d, J = 7.3 Hz , 2H), 7.34-7.28 (m, 2H), 7.21 (t, J = 9.1 Hz, 1H), 7.05 (t, J = 7.9 Hz, 2H), 2.33 (s, 3H).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 169.6, 154.6, 153.6, 137.3, 135.1, 131.94, 131.88, 130.4, 130.1, 129.2, 129.0, 127.5, 126.6, 125.1, 122.9, 121.0, 119.3, 118.9 , 114.6, 9.7.
１ｋ：
融点177.5 - 178.3℃
IR (KBr): vmax 3067, 2975, 2921, 1597, 1537, 1452, 1371, 1360, 1222, 1188, 1173, 1132, 1121, 1089, 1018, 951, 900, 830, 820, 811, 757, 683, 667 cm-1.
1H NMR (500 MHz, CDCl3): δ (ppm) 8.30 (d, J = 8.2 Hz, 1H), 8.11 (dd, J = 0.9, 8.8 Hz, 1H), 7.73 (dd, J = 7.0, 8.8 Hz, 1H), 7.61 (dd, J = 0.9, 7.0 Hz, 1H), 7.50 (d, J = 8.0 Hz, 1H), 7.40 (dd, J = 7.2, 8.2 Hz, 1H), 7.32 (dd, J = 7.2, 8.0 Hz, 1H), 7.27 (d, J = 8.2 Hz, 2H), 6.96 (d, J = 8.2 Hz, 2H), 2.26 (s, 3H), 2.02 (s, 3H).
13C NMR (126 MHz, CDCl3): δ (ppm) 154.63, 154.62, 144.4, 137.4, 135.1, 132.2, 131.5, 131.3, 129.2, 128.8, 126.7, 125.38, 125.35, 123.8, 122.1, 121.5, 119.4, 115.8, 21.5, 9.7.
1k:
177.5-178.3 ° C
IR (KBr): v max 3067, 2975, 2921, 1597, 1537, 1452, 1371, 1360, 1222, 1188, 1173, 1132, 1121, 1089, 1018, 951, 900, 830, 820, 811, 757, 683 , 667 cm -1 .
1 H NMR (500 MHz, CDCl 3 ): δ (ppm) 8.30 (d, J = 8.2 Hz, 1H), 8.11 (dd, J = 0.9, 8.8 Hz, 1H), 7.73 (dd, J = 7.0, 8.8 Hz, 1H), 7.61 (dd, J = 0.9, 7.0 Hz, 1H), 7.50 (d, J = 8.0 Hz, 1H), 7.40 (dd, J = 7.2, 8.2 Hz, 1H), 7.32 (dd, J = 7.2, 8.0 Hz, 1H), 7.27 (d, J = 8.2 Hz, 2H), 6.96 (d, J = 8.2 Hz, 2H), 2.26 (s, 3H), 2.02 (s, 3H).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 154.63, 154.62, 144.4, 137.4, 135.1, 132.2, 131.5, 131.3, 129.2, 128.8, 126.7, 125.38, 125.35, 123.8, 122.1, 121.5, 119.4, 115.8 , 21.5, 9.7.
窒素原子上にアシル基またはトシル基を有する１ｉ−１ｋも固体状態で発光し、蛍光メカノクロミズムを示した（図１０）。ピバロイル基を有する１ｉでは、固体発光色が機械的刺激により黄色から橙色に変化し、室温下２分程度で元の発光色に戻った。ベンゾイル基を有する１ｊでは、黄色から黄橙色への蛍光メカノクロミズムを示し、発光色は室温下２分程度で元に戻った。また、トシル基を有する１ｋも同様に、機械的刺激により青緑色から黄緑色へ発光色が変化し、その発光色は元に戻るのに室温下１０分以上要した。 1i-1k having an acyl group or a tosyl group on the nitrogen atom also emitted light in a solid state and exhibited fluorescent mechanochromism (FIG. 10). In 1i having a pivaloyl group, the solid emission color changed from yellow to orange due to mechanical stimulation, and returned to the original emission color in about 2 minutes at room temperature. 1j having a benzoyl group exhibited fluorescence mechanochromism from yellow to yellow-orange, and the emitted color returned to its original state in about 2 minutes at room temperature. Similarly, for 1k having a tosyl group, the emission color changed from blue-green to yellow-green due to mechanical stimulation, and it took 10 minutes or more at room temperature to return to the original emission color.
（実施例３：Ｎ−Ｂｏｃ−３−置換インドリルベンゾチアジアゾール１ｌ、１ｍの合成とその蛍光メカノクロミズム）
実施例１と同様に、Ｎ−Ｂｏｃ−３−置換インドールにテトラヒドロフラン（ＴＨＦ）中、−２０℃でリチウムジイソプロピルアミド（ＬＤＡ）を作用させた後、ホウ酸トリイソプロピルを加えて１時間半反応させることで、Ｎ−Ｂｏｃ−３−置換インドール−２−ボロン酸を得た。次に、得られたボロン酸を単離することなくテトラキス（トリフェニルホスフィン）パラジウム（２０ｍｏｌ％）存在下、４−ブロモ−２，１，３−ベンゾチアジアゾールとジオキサン／炭酸カリウム水溶液混合溶媒中、９５℃で４時間反応させることで、インドリルベンゾチアジアゾール誘導体１ｌ、１ｍをそれぞれ収率４８％、６４％で得た。合成した１ｌ、１ｍのトルエン中での発光スペクトルを測定したところ、どちらも１ａよりわずかに短波長シフトした位置に発光極大が観測された（図１１）。
(Example 3: Synthesis of N-Boc-3-substituted indolylbenzothiadiazole 1 l, 1 m and its fluorescence mechanochromism)
In the same manner as in Example 1, lithium diisopropylamide (LDA) is allowed to act on N-Boc-3-substituted indole in tetrahydrofuran (THF) at −20 ° C., and triisopropyl borate is added to react for 1.5 hours. This gave N-Boc-3-substituted indole-2-boronic acid. Next, in a mixed solvent of 4-bromo-2,1,3-benzothiadiazole and dioxane / potassium carbonate aqueous solution in the presence of tetrakis (triphenylphosphine) palladium (20 mol%) without isolation of the obtained boronic acid, By reacting at 95 ° C. for 4 hours, indolyl benzothiadiazole derivatives 11 and 1 m were obtained in a yield of 48% and 64%, respectively. When the emission spectra of the synthesized 1 l and 1 m toluene were measured, in each case, the emission maximum was observed at a position slightly shifted in wavelength from 1a (FIG. 11).
また、以下に１ｌ、１ｍの融点、赤外線吸収スペクトル（ＫＢｒ法）:ＩＲ（ＫＢｒ）、1Ｈ ＮＭＲスペクトル、13Ｃ ＮＭＲスペクトルの測定結果をそれぞれ示す。
１ｌ：
融点128.0 - 128.6 ℃（分解）
IR (KBr): vmax 2969, 1732, 1601, 1538, 1454, 1411, 1392, 1369, 1332, 1286, 1254, 1223, 1149, 1116, 1089, 1018, 905, 878, 846, 815, 796, 763, 743, 705 cm-1.
1H NMR (500 MHz, CDCl3): δ (ppm) 8.31 (d, J = 8.5 Hz, 1H), 8.04 (dd, J = 8.8, 1.3 Hz, 1H), 7.69 (dd, J = 8.8, 6.6 Hz, 1H), 7.63 (d, J = 7.6 Hz, 1H), 7.56 (dd, J = 6.6, 1.1 Hz, 1H), 7.39 (dd, J = 8.5, 7.6 Hz, 1H), 7.30 (t, J = 7.6 Hz, 1H), 2.68 (dt, J = 21.8, 7.6 Hz, 1H), 2.53 (dt, J = 21.8, 7.6 Hz, 1H), 1.20 (t, J = 7.6 Hz, 3H), 0.97 (s, 9H).
13C NMR (126 MHz, CDCl3): δ (ppm) 155.0, 154.9, 149.9, 136.9, 130.3, 129.3, 128.7, 128.3, 124.9, 124.2, 122.6, 121.0, 119.2, 115.6, 82.4, 27.4, 17.8, 15.3.
The following shows the melting points of 1 l and 1 m, and the measurement results of infrared absorption spectrum (KBr method): IR (KBr), 1 H NMR spectrum, and 13 C NMR spectrum, respectively.
1l:
128.0-128.6 ° C (decomposition)
IR (KBr): v max 2969, 1732, 1601, 1538, 1454, 1411, 1392, 1369, 1332, 1286, 1254, 1223, 1149, 1116, 1089, 1018, 905, 878, 846, 815, 796, 763 , 743, 705 cm -1 .
1 H NMR (500 MHz, CDCl 3 ): δ (ppm) 8.31 (d, J = 8.5 Hz, 1H), 8.04 (dd, J = 8.8, 1.3 Hz, 1H), 7.69 (dd, J = 8.8, 6.6 Hz, 1H), 7.63 (d, J = 7.6 Hz, 1H), 7.56 (dd, J = 6.6, 1.1 Hz, 1H), 7.39 (dd, J = 8.5, 7.6 Hz, 1H), 7.30 (t, J = 7.6 Hz, 1H), 2.68 (dt, J = 21.8, 7.6 Hz, 1H), 2.53 (dt, J = 21.8, 7.6 Hz, 1H), 1.20 (t, J = 7.6 Hz, 3H), 0.97 (s , 9H).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 155.0, 154.9, 149.9, 136.9, 130.3, 129.3, 128.7, 128.3, 124.9, 124.2, 122.6, 121.0, 119.2, 115.6, 82.4, 27.4, 17.8, 15.3 .
１ｍ：
融点>145℃（分解）
IR (KBr): vmax 3075, 3015, 2973, 2931, 2873, 1721, 1600, 1536, 1456, 1417, 1366, 1331, 1274, 1236, 1210, 1157, 1110, 1087, 999, 903, 868, 851, 818, 811, 769, 754 cm-1.
1H NMR (500 MHz, CDCl3): δ (ppm) 8.34 (d, J = 8.2 Hz, 1H), 8.05 (dd, J = 8.8, 1.0 Hz, 1H), 7.80 (d, J = 7.9 Hz, 1H), 7.69 (dd, J = 8.8, 6.7 Hz, 1H), 7.52 (dd, J = 6.7, 1.0 Hz, 1H), 7.36 (dd, J = 8.2, 7.9 Hz, 1H), 7.27 (t, J = 7.9 Hz, 1H), 2.93 (sept, J = 7.3 Hz, 1H), 1.42 (d, J = 7.3 Hz, 3H), 1.26 (d, J = 7.3 Hz, 3H), 0.95 (s, 9H).
13C NMR (126 MHz, CDCl3): δ (ppm) 155.1, 154.8, 149.8, 137.2, 129.3, 129.21, 129.20, 128.6, 128.0, 127.7, 124.6, 122.2, 121.1, 120.7, 115.8, 82.4, 27.4, 26.3, 22.6, 22.3.
1m:
Melting point> 145 ° C (decomposition)
IR (KBr): v max 3075, 3015, 2973, 2931, 2873, 1721, 1600, 1536, 1456, 1417, 1366, 1331, 1274, 1236, 1210, 1157, 1110, 1087, 999, 903, 868, 851 , 818, 811, 769, 754 cm -1 .
1 H NMR (500 MHz, CDCl 3 ): δ (ppm) 8.34 (d, J = 8.2 Hz, 1H), 8.05 (dd, J = 8.8, 1.0 Hz, 1H), 7.80 (d, J = 7.9 Hz, 1H), 7.69 (dd, J = 8.8, 6.7 Hz, 1H), 7.52 (dd, J = 6.7, 1.0 Hz, 1H), 7.36 (dd, J = 8.2, 7.9 Hz, 1H), 7.27 (t, J = 7.9 Hz, 1H), 2.93 (sept, J = 7.3 Hz, 1H), 1.42 (d, J = 7.3 Hz, 3H), 1.26 (d, J = 7.3 Hz, 3H), 0.95 (s, 9H).
13 C NMR (126 MHz, CDCl 3 ): δ (ppm) 155.1, 154.8, 149.8, 137.2, 129.3, 129.21, 129.20, 128.6, 128.0, 127.7, 124.6, 122.2, 121.1, 120.7, 115.8, 82.4, 27.4, 26.3 , 22.6, 22.3.
合成した１ｌ、１ｍはいずれも固体状態で発光するとともに、蛍光メカノクロミズムを示した。また、固体蛍光色素１ｌ、１ｍに対し、スパチュラで擦ることによる機械的刺激を加えた。その結果、エチル基を有する１ｌでは、固体発光色が青緑色から黄緑色へと変化し、発光色は室温下１０分程度放置することで自発的に元の発光色へ戻った。また、イソプロピル基を有する１ｍも同様に、固体発光色が青緑色から黄緑色へと変化し、発光色は室温下２分程度放置することで自発的に元の発光色へ戻った（図１２）。 Each of the synthesized 1l and 1m emitted light in a solid state and exhibited fluorescent mechanochromism. In addition, mechanical stimulation by rubbing with a spatula was applied to 1 l and 1 m of the solid fluorescent dye. As a result, in 1 l having an ethyl group, the solid emission color changed from blue-green to yellow-green, and the emission color spontaneously returned to the original emission color by being left at room temperature for about 10 minutes. Similarly, the solid emission color of 1 m having an isopropyl group changed from blue-green to yellow-green, and the emission color spontaneously returned to the original emission color by being left at room temperature for about 2 minutes (FIG. 12). ).
Claims (9)
また、Ｒ5は、アルキルオキシカルボニル基、アリールオキシカルボニル基、アシル基、アルキルスルホニル基またはアリールスルホニル基である。
また、Ｒ9は、ハロゲン原子、ヒドロキシ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、ニトロ基、アミノ基、アミド基、カルボキシ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、ホルミル基、シアノ基、アルキル基、シクロアルキル基、アラルキル基またはアリール基である。） An indolylbenzothiadiazole derivative represented by the following formula (1).
R 5 is an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group.
R 9 represents a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amide group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group. , An alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. )
また、Ｒ5は、アルキルオキシカルボニル基、アリールオキシカルボニル基、アシル基、アルキルスルホニル基またはアリールスルホニル基である。
また、Ｒ9は、ハロゲン原子、ヒドロキシ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、ニトロ基、アミノ基、アミド基、カルボキシ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、ホルミル基、シアノ基、アルキル基、シクロアルキル基、アラルキル基またはアリール基である。） An indolylbenzothiadiazole derivative represented by the above formula (1) is obtained by reacting a boronic acid represented by the following formula (6) with a bromobenzothiadiazole represented by the following formula (7). A method for producing a thiadiazole derivative.
R 5 is an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group.
R 9 represents a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amide group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group. , An alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. )
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