JP2021123568A - Iridium complex - Google Patents
Iridium complex Download PDFInfo
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- JP2021123568A JP2021123568A JP2020018711A JP2020018711A JP2021123568A JP 2021123568 A JP2021123568 A JP 2021123568A JP 2020018711 A JP2020018711 A JP 2020018711A JP 2020018711 A JP2020018711 A JP 2020018711A JP 2021123568 A JP2021123568 A JP 2021123568A
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- 229910052741 iridium Inorganic materials 0.000 title abstract description 20
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title abstract description 20
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical group OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 85
- 125000005842 heteroatom Chemical group 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 125000001424 substituent group Chemical group 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 11
- 125000004104 aryloxy group Chemical group 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003282 alkyl amino group Chemical group 0.000 claims description 7
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 7
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 7
- 125000001769 aryl amino group Chemical group 0.000 claims description 7
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 7
- 125000005104 aryl silyl group Chemical group 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical group N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 6
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 6
- 125000005647 linker group Chemical group 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000002883 imidazolyl group Chemical group 0.000 claims description 4
- 125000002971 oxazolyl group Chemical group 0.000 claims description 4
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 4
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000005281 excited state Effects 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 235000002597 Solanum melongena Nutrition 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 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 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- FCEUOTOBJMBWHC-UHFFFAOYSA-N benzo[f]cinnoline Chemical group N1=CC=C2C3=CC=CC=C3C=CC2=N1 FCEUOTOBJMBWHC-UHFFFAOYSA-N 0.000 description 3
- HCAUQPZEWLULFJ-UHFFFAOYSA-N benzo[f]quinoline Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=N1 HCAUQPZEWLULFJ-UHFFFAOYSA-N 0.000 description 3
- BMWYMEQOMFGKSN-UHFFFAOYSA-N benzo[g]cinnoline Chemical group N1=NC=CC2=CC3=CC=CC=C3C=C21 BMWYMEQOMFGKSN-UHFFFAOYSA-N 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 150000002503 iridium Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- QKHBRTOZTSOCKN-UHFFFAOYSA-N phenanthro[9,10-c]pyridazine Chemical group N1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=N1 QKHBRTOZTSOCKN-UHFFFAOYSA-N 0.000 description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 3
- 235000019798 tripotassium phosphate Nutrition 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229940093475 2-ethoxyethanol Drugs 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 108091005461 Nucleic proteins Proteins 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000005577 anthracene group Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 102000039446 nucleic acids Human genes 0.000 description 2
- 108020004707 nucleic acids Proteins 0.000 description 2
- 150000007523 nucleic acids Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 125000005581 pyrene group Chemical group 0.000 description 2
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NCWDBNBNYVVARF-UHFFFAOYSA-N 1,3,2-dioxaborolane Chemical compound B1OCCO1 NCWDBNBNYVVARF-UHFFFAOYSA-N 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- RAXGUPNDDNULQO-UHFFFAOYSA-N 1-bromo-3-(3-iodophenyl)benzene Chemical group BrC1=CC=CC(C=2C=C(I)C=CC=2)=C1 RAXGUPNDDNULQO-UHFFFAOYSA-N 0.000 description 1
- XCMGDNMMLIJSQA-UHFFFAOYSA-N 2-(3-bromophenyl)-1,3-benzothiazole Chemical compound BrC1=CC=CC(C=2SC3=CC=CC=C3N=2)=C1 XCMGDNMMLIJSQA-UHFFFAOYSA-N 0.000 description 1
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 1
- AGIIMNQWNPUJPT-UHFFFAOYSA-N 4-(4-bromophenyl)butanoic acid Chemical compound OC(=O)CCCC1=CC=C(Br)C=C1 AGIIMNQWNPUJPT-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- USVZFSNDGFNNJT-UHFFFAOYSA-N cyclopenta-1,4-dien-1-yl(diphenyl)phosphane (2,3-dichlorocyclopenta-1,4-dien-1-yl)-diphenylphosphane iron(2+) Chemical compound [Fe++].c1cc[c-](c1)P(c1ccccc1)c1ccccc1.Clc1c(cc[c-]1Cl)P(c1ccccc1)c1ccccc1 USVZFSNDGFNNJT-UHFFFAOYSA-N 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PPIQQNDMGXNRFA-UHFFFAOYSA-N methyl 2-phenylbutanoate Chemical compound COC(=O)C(CC)C1=CC=CC=C1 PPIQQNDMGXNRFA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229950009215 phenylbutanoic acid Drugs 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000006836 terphenylene group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- Electroluminescent Light Sources (AREA)
- Plural Heterocyclic Compounds (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、核酸、タンパク質、多糖などの生体物質に容易に導入することが可能なイリ
ジウム錯体に関する。
The present invention relates to iridium complexes that can be easily introduced into biological materials such as nucleic acids, proteins and polysaccharides.
照明やディスプレイなど、有機電界発光素子を利用する各種電子デバイスが実用化され
ている。大型のディスプレイや照明に用いることのできる有機電界発光素子を効率よく製
造するプロセスとして、塗布法が研究されている。塗布法は、真空蒸着法に比べて安定し
た層を容易に形成できる利点があるため、ディスプレイや照明装置の量産化や大型デバイ
スへの適用が期待されている。有機電界発光素子を塗布法で製造するためには、発光ドー
パント使を含むすべての材料は溶解してインクとして使用できるものである必要がある。
Various electronic devices that use organic electroluminescent elements, such as lighting and displays, have been put into practical use. A coating method is being studied as a process for efficiently manufacturing an organic electroluminescent device that can be used for large displays and lighting. Since the coating method has an advantage that a stable layer can be easily formed as compared with the vacuum deposition method, it is expected to be mass-produced for displays and lighting devices and applied to large-scale devices. In order to manufacture an organic electroluminescent device by the coating method, all the materials including the light emitting dopant use must be able to be dissolved and used as ink.
発光ドーパントとしては、その用途に合わせて、赤、緑、青のそれぞれの発光色が求め
られるが、赤色には、アリールキノリン誘導体やアリールイソキノリン誘導体を配位子と
するイリジウム錯体が用いられている。さらに、発光波長を調整したり、溶解性を高めた
りする目的で、Ｎ原子を２つ有するアリールキノキサリン誘導体、アリールキナゾリン誘
導体などのアリールナフチリジン誘導体を配位子としたイリジウム錯体も提案されている
（例えば、特許文献１）。
As the luminescent dopant, each luminescent color of red, green, and blue is required according to its use, and for red, an iridium complex having an arylquinoline derivative or an arylisoquinoline derivative as a ligand is used. .. Further, for the purpose of adjusting the emission wavelength and improving the solubility, an iridium complex having an arylnaphthylidine derivative such as an arylquinoxaline derivative having two N atoms and an arylquinazoline derivative as a ligand has also been proposed ( For example, Patent Document 1).
近年、イリジウム錯体のもつ、励起一重項状態から励起三重項状態への項間交差が起き
やすく、励起三重項状態から比較的長い減衰寿命で発光する特徴や、励起三重項状態が酸
素によって失活しやすい特徴を、生化学的な用途に応用することが試みられ、イリジウム
錯体を生体に投与する検討がなされている。イリジウム錯体を生体に投与する際には、核
酸、タンパク質、多糖などの生体物質にイリジウム錯体を結合させることが効率的であり
、これらの生体物質への結合部位として、Ｎ−ヒドロキシスクシンイミドエステル基を用
いることが報告されている（例えば、非特許文献１及び２）。
In recent years, intersystem crossing from the excited singlet state to the excited triplet state of the iridium complex is likely to occur, and the excited triplet state emits light with a relatively long decay lifetime, and the excited triplet state is deactivated by oxygen. Attempts have been made to apply the easy-to-use characteristics to biochemical applications, and studies have been made on the administration of iridium complexes to living organisms. When administering an iridium complex to a living body, it is efficient to bind the iridium complex to a biological substance such as nucleic acid, protein, or polysaccharide, and an N-hydroxysuccinimide ester group is used as a binding site for these biological substances. It has been reported to be used (for example, Non-Patent Documents 1 and 2).
しかしながら、前述の先行技術では、発光や吸収の波長が短く、生体の窓と呼ばれる、
生体内の物質や水に吸収されにくい６５０−１０００ｎｍの波長域に対応していなかった
り、励起状態が熱的に失活されやすかったりするため、イリジウム錯体を生化学的用途に
用いた場合に十分な性能が得られていなかった。そのため、６５０−１０００ｎｍの波長
域に対応し、熱的に失活しにくく、かつ、生体物質に導入が容易なイリジウム錯体が求め
られていた。
However, in the above-mentioned prior art, the wavelengths of light emission and absorption are short, and it is called a window of a living body.
It does not correspond to the wavelength range of 650-1000 nm, which is difficult to be absorbed by substances and water in the living body, and the excited state is easily deactivated by heat, so it is sufficient when the iridium complex is used for biochemical applications. Performance was not obtained. Therefore, there has been a demand for an iridium complex that corresponds to a wavelength range of 650 to 1000 nm, is less likely to be thermally deactivated, and is easily introduced into a biological substance.
本発明は、生体の窓と呼ばれる波長域に対応し、励起状態が安定で、生体物質への結合
部位であるＮ−ヒドロキシスクシンイミドエステル基を有するイリジウムを提供するもの
である。
The present invention provides an iridium having an N-hydroxysuccinimide ester group, which corresponds to a wavelength range called a window of a living body, has a stable excited state, and is a binding site for a biological substance.
本発明者は、上記課題に鑑み鋭意検討した結果、含窒素複素環を含む縮合環にアリール
基が置換したアリールキノリン誘導体、アリールイソキノリン誘導体、アリールナフチリ
ジン誘導体を配位子として２つ有し、Ｎ−ヒドロキシスクシンイミドエステル基がスペー
サを介して、イリジウムに結合または配位するアリール基またはヘテロアリール基に連結
された配位子を１つ有するイリジウム錯体が、発光や吸収の波長を赤色から赤外に有し、
生体の窓と呼ばれる波長域に対応し、励起状態が熱的に失活しにくく、かつ、生体物質に
容易に導入可能であることを見出し、本発明を完成するに至った。
As a result of diligent studies in view of the above problems, the present inventor has two arylquinolin derivatives, arylisoquinolin derivatives, and arylnaphthylidine derivatives in which an aryl group is substituted in a fused ring containing a nitrogen-containing heterocycle as ligands, and N -The iridium complex having one ligand linked to an aryl group or a heteroaryl group in which the hydroxysuccinimide ester group is bonded or coordinated to iridium via a spacer changes the wavelength of emission or absorption from red to infrared. Have and
We have found that the excited state is not easily thermally deactivated and can be easily introduced into a biological substance corresponding to a wavelength range called a window of a living body, and have completed the present invention.
本発明のイリジウム錯体は、キノリン環、イソキノリン環、キノキサリン、キナゾリン
、シンノリン等のキナゾリン環等の含窒素複素環を含む縮合環にアリール基が置換した配
位子を２つ有するため、赤色から赤外の比較的長波長に発光や吸収を示し、さらに、励起
状態が熱的に失活しにくい光物性を有する。また、本発明のイリジウム錯体は、Ｎ−ヒド
ロキシスクシンイミドエステル基を、イリジウム金属及び配位子のπ共役系構造から離れ
た位置に１つ有するため、生体物質内の第一級アミンに対して１つのイリジウム錯体を、
上記の優れた光物性を保ったまま、容易に導入することが可能である。
The iridium complex of the present invention has two ligands in which an aryl group is substituted on a condensed ring containing a nitrogen-containing heterocycle such as a quinoline ring, an isoquinoline ring, a quinoxaline, a quinazoline, a cinnoline, etc., and thus is red to red. It emits light and absorbs light at a relatively long outside wavelength, and has optical properties that make it difficult for the excited state to be thermally deactivated. Further, since the iridium complex of the present invention has one N-hydroxysuccinimide ester group at a position away from the π-conjugated structure of the iridium metal and the ligand, it is 1 with respect to the primary amine in the biological material. Two iridium complexes,
It can be easily introduced while maintaining the above-mentioned excellent optical physical characteristics.
即ち、本発明の要旨は、以下の通りである。
［１］下記式（１）で表される化合物。
That is, the gist of the present invention is as follows.
[1] A compound represented by the following formula (1).
［上記式中、環Ａ、環Ｃは、ベンゼン環を表す。
環Ｂは、キノリン環、イソキノリン環、ナフチリジン環のいずれかを表す。
環Ｄは、ピリジン環、ピラジン環、ピリミジン環、イミダゾール環、オキサゾール環、
チアゾール環のいずれかを表す。
環Ａ〜Ｄは、置換基を有していても良く、置換基は、フッ素原子、塩素原子、臭素原子
、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数７〜４０の（ヘ
テロ）アラルキル基、炭素数１〜２０のアルコキシ基、炭素数３〜２０の（ヘテロ）アリ
ールオキシ基、アルキル基の炭素数が１〜２０であるアルキルシリル基、アリール基の炭
素数が６〜２０であるアリールシリル基、炭素数２〜２０のアルキルカルボニル基、炭素
数７〜２０のアリールカルボニル基、炭素数２〜２０のアルキルアミノ基、炭素数６〜２
０のアリールアミノ基、または炭素数３〜２０の（ヘテロ）アリール基のいずれか、また
はこれらの組み合わせである。また、環Ａ〜Ｄに結合する隣り合う置換基どうしが結合し
てさらに環を形成しても良い。
[In the above formula, ring A and ring C represent a benzene ring.
Ring B represents any of a quinoline ring, an isoquinoline ring, and a diazanaphthalene ring.
Ring D is a pyridine ring, a pyrazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring,
Represents one of the thiazole rings.
Rings A to D may have a substituent, and the substituents are a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and 7 carbon atoms. ~ 40 (hetero) aralkyl group, alkoxy group having 1 to 20 carbon atoms, (hetero) aryloxy group having 3 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms of alkyl group, carbon of aryl group An arylsilyl group having 6 to 20 carbon atoms, an alkylcarbonyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, an alkylamino group having 2 to 20 carbon atoms, and 6 to 2 carbon atoms.
It is either an arylamino group of 0, or a (hetero) aryl group having 3 to 20 carbon atoms, or a combination thereof. Further, adjacent substituents bonded to the rings A to D may be bonded to each other to further form a ring.
Ｚ１は、直接結合または２価の芳香族連結基を表す。
Ｒ１は、３つ以上の単結合を介してＺ１とＮ−ヒドロキシスクシンイミドエステル基を
つなぐ基を表す。］
［２］式（１）が式（２）で表される化合物である［１］に記載の化合物。
Z 1 represents a direct bond or a divalent aromatic linking group.
R 1 represents a group that connects Z 1 with an N-hydroxysuccinimide ester group via three or more single bonds. ]
[2] The compound according to [1], wherein the formula (1) is represented by the formula (2).
［式（２）中、ａは０〜４の整数である。
Ｒ２は、フッ素原子、塩素原子、臭素原子、炭素数１〜２０のアルキル基、炭素数７〜
４０の（ヘテロ）アラルキル基、炭素数１〜２０のアルコキシ基、炭素数３〜２０の（ヘ
テロ）アリールオキシ基、アルキル基の炭素数が１〜２０であるアルキルシリル基、アリ
ール基の炭素数が６〜２０であるアリールシリル基、炭素数２〜２０のアルキルカルボニ
ル基、炭素数７〜２０のアリールカルボニル基、炭素数２〜２０のアルキルアミノ基、炭
素数６〜２０のアリールアミノ基、または炭素数３〜２０の（ヘテロ）アリール基を表す
。
[In equation (2), a is an integer from 0 to 4.
R 2 is a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms, and 7 to 20 carbon atoms.
40 (hetero) aralkyl groups, alkoxy groups having 1 to 20 carbon atoms, (hetero) aryloxy groups having 3 to 20 carbon atoms, alkylsilyl groups having 1 to 20 carbon atoms, and aryl groups having 1 to 20 carbon atoms. Arylsilyl group having 6 to 20, alkylcarbonyl group having 2 to 20 carbon atoms, arylcarbonyl group having 7 to 20 carbon atoms, alkylamino group having 2 to 20 carbon atoms, arylamino group having 6 to 20 carbon atoms, Alternatively, it represents a (hetero) aryl group having 3 to 20 carbon atoms.
環Ａ、環Ｂ、環Ｄ、Ｚ１、Ｒ１は、式（１）における環Ａ、環Ｂ、環Ｄ、Ｚ１、Ｒ１と
同義である。］
［３］式（２）が式（３）で表される化合物である［２］に記載の化合物。
Ring A, ring B, ring D, Z 1, R 1 is as defined ring A, ring B in formula (1), ring D, and Z 1, R 1. ]
[3] The compound according to [2], wherein the formula (2) is represented by the formula (3).
［上記式中、ａ、環Ａ、環Ｂ、環Ｄ、Ｚ１、Ｒ１、Ｒ２は、式（２）における環Ａ、環Ｂ
、環Ｄ、Ｚ１、Ｒ１と同義である。］
[In the above formula, a, ring A, ring B, ring D, Z 1 , R 1 , and R 2 are rings A and ring B in formula (2).
, Ring D, Z 1 , and R 1 . ]
本発明により、赤色から赤外の比較的長波長に発光や吸収を示し、励起状態が熱的に失
活しにくいイリジウム錯体を、生体物質内の第一級アミンに、その物性を保ったまま、容
易に導入することができる。
According to the present invention, an iridium complex that emits light or absorbs light in a relatively long wavelength from red to infrared and is not easily deactivated thermally in an excited state is converted into a primary amine in a biological material while maintaining its physical characteristics. , Can be easily introduced.
以下に、本発明の実施の形態を詳細に説明するが、本発明は以下の実施の形態に限定さ
れるものではなく、その要旨の範囲内で種々に変形して実施することができる。
なお、本明細書において（ヘテロ）アラルキル基、（ヘテロ）アリールオキシ基、（ヘ
テロ）アリール基とは、それぞれヘテロ原子を含んでいてもよいアラルキル基、ヘテロ原
子を含んでいてもよいアリールオキシ基、ヘテロ原子を含んでいてもよいアリール基、を
表す。「ヘテロ原子を含んでいてもよい」とは、アリール基、アラルキル基又はアリール
オキシ基の主骨格を形成する炭素原子のうち１又は２以上の炭素原子がヘテロ原子に置換
されていることを表し、ヘテロ原子としては窒素原子、酸素原子、硫黄原子、リン原子、
ケイ素原子等が挙げられ、中でも耐久性の観点から窒素原子が好ましい。
本発明のイリジウム錯体は下記式（１）で表される。
Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
In the present specification, the (hetero) aralkyl group, the (hetero) aryloxy group, and the (hetero) aryl group are an aralkyl group that may contain a heteroatom and an aryloxy group that may contain a heteroatom, respectively. Represents an aryl group, which may contain a heteroatom. "May contain a heteroatom" means that one or more carbon atoms forming the main skeleton of an aryl group, an aralkyl group or an aryloxy group are substituted with a heteroatom. , Heteroatoms include nitrogen atom, oxygen atom, sulfur atom, phosphorus atom,
Examples thereof include a silicon atom, and among them, a nitrogen atom is preferable from the viewpoint of durability.
The iridium complex of the present invention is represented by the following formula (1).
［上記式中、環Ａ、環Ｃは、ベンゼン環を表す。
環Ｂは、キノリン環、イソキノリン環、ナフチリジン環を表す。
環Ｄは、ピリジン環、ピラジン環、ピリミジン環、イミダゾール環、オキサゾール環、
チアゾール環を表す。
環Ａ〜Ｄは、置換基を有していても良く、置換基は、フッ素原子、塩素原子、臭素原子
、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数７〜４０の（ヘ
テロ）アラルキル基、炭素数１〜２０のアルコキシ基、炭素数３〜２０の（ヘテロ）アリ
ールオキシ基、アルキル基の炭素数が１〜２０であるアルキルシリル基、アリール基の炭
素数が６〜２０であるアリールシリル基、炭素数２〜２０のアルキルカルボニル基、炭素
数７〜２０のアリールカルボニル基、炭素数２〜２０のアルキルアミノ基、炭素数６〜２
０のアリールアミノ基、または炭素数３〜２０の（ヘテロ）アリール基のいずれか、また
はこれらの組み合わせである。また、環Ａ〜Ｄに結合する隣り合う置換基どうしが結合し
てさらに環を形成しても良い。
Ｚ１は、直接結合または２価の芳香族連結基を表す。
Ｒ１は、３つ以上の単結合を介してＺ１とＮ−ヒドロキシスクシンイミドエステル基を
つなぐ基を表す。］
[In the above formula, ring A and ring C represent a benzene ring.
Ring B represents a quinoline ring, an isoquinoline ring, and a diazanaphthalene ring.
Ring D is a pyridine ring, a pyrazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring,
Represents a thiazole ring.
Rings A to D may have a substituent, and the substituents are a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and 7 carbon atoms. ~ 40 (hetero) aralkyl group, alkoxy group having 1 to 20 carbon atoms, (hetero) aryloxy group having 3 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms of alkyl group, carbon of aryl group An arylsilyl group having 6 to 20 carbon atoms, an alkylcarbonyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, an alkylamino group having 2 to 20 carbon atoms, and 6 to 2 carbon atoms.
It is either an arylamino group of 0, or a (hetero) aryl group having 3 to 20 carbon atoms, or a combination thereof. Further, adjacent substituents bonded to the rings A to D may be bonded to each other to further form a ring.
Z 1 represents a direct bond or a divalent aromatic linking group.
R 1 represents a group that connects Z 1 with an N-hydroxysuccinimide ester group via three or more single bonds. ]
＜環Ａ〜Ｄ＞
環Ａ、環Ｃは、置換基を有していても良いベンゼン環を表す。環Ａ、環Ｃに結合する隣
り合う置換基どうしが結合してさらに環を形成しても良い。さらに環を形成した場合、環
Ａ、環Ｃのベンゼン環と合わせて、ナフタレン環、アントラセン環、フェナントレン環、
ピレン環、ペリレン環、フルオレン環、カルバゾール環、ジベンゾフラン環、ジベンゾチ
オフェン環等のベンゼン環構造を有する縮合環を形成する。
<Ring A to D>
Ring A and ring C represent a benzene ring which may have a substituent. Adjacent substituents bonded to rings A and C may be bonded to each other to further form a ring. When a ring is further formed, a naphthalene ring, an anthracene ring, phenanthrene ring, etc. are combined with the benzene ring of the ring A and the ring C.
It forms a fused ring having a benzene ring structure such as a pyrene ring, a perylene ring, a fluorene ring, a carbazole ring, a dibenzofuran ring, and a dibenzothiophene ring.
環Ａ、環Ｃは、溶解性の観点からは、置換基どうしが結合してさらに環を形成しないこ
とが好ましい。一方、発光や吸収波長をより長波長にできる観点からは、置換基どうしが
結合してさらに環を形成することが好ましい。環Ａ、環Ｃを含む縮合環としては、励起状
態が熱的に失活しにくい点で、ナフタレン環、アントラセン環、フェナントレン環、ピレ
ン環、ペリレン環、フルオレン環、カルバゾール環、ジベンゾフラン環、ジベンゾチオフ
ェン環が好ましく、ナフタレン環、フルオレン環がさらに好ましい。
From the viewpoint of solubility, it is preferable that the substituents of the rings A and C do not bond with each other to form a ring. On the other hand, from the viewpoint that the emission and absorption wavelengths can be made longer, it is preferable that the substituents are bonded to each other to further form a ring. The fused ring containing rings A and C is a naphthalene ring, an anthracene ring, phenanthrene ring, pyrene ring, perylene ring, fluorene ring, carbazole ring, dibenzofuran ring, and dibenzo because the excited state is not easily deactivated. The thiophene ring is preferable, and the naphthalene ring and the fluorene ring are more preferable.
環Ｂは、置換基を有していても良いキノリン環、イソキノリン環、ナフチリジン環のい
ずれかを表す。ナフチリジン環の２つの窒素原子の位置はいずれでもよいが、１，４−ナ
フチリジン（キノキサリン環）、１，３−ナフチリジン（キナゾリン環）、１，２−ナフ
チリジン（シンノリン環）、１，５−ナフチリジンが、より励起状態が熱的に失活しにく
く好ましい。
Ring B represents any of a quinoline ring, an isoquinoline ring, and a naphthylidine ring which may have a substituent. The positions of the two nitrogen atoms on the diazanaphthalene ring may be any, but 1,4-naphthalene (quinoxaline ring), 1,3-naphthalene (quinazoline ring), 1,2-naphthalene (cinnoline ring), 1,5-naphthyline However, it is preferable that the excited state is less likely to be thermally deactivated.
環Ｂに結合する隣り合う置換基どうしが結合してさらに環を形成しても良い。さらに環
を形成した場合、環Ｂと合わせて、アザアントラセン環、ジアザアントラセン環、アザフ
ェナントレン環、ジアザフェナントレン環、アザトリフェニレン環、ジアザトリフェニレ
ン環等を形成する。環Ｂは、溶解性の観点からは、置換基どうしが結合してさらに環を形
成しないことが好ましい。一方、発光や吸収波長をより長波長にできる観点からは、置換
基どうしが結合してさらに環を形成することが好ましい。環Ｂを含む縮合環としては、励
起状態が熱的に失活しにくい点で、アザアントラセン環、ジアザアントラセン環、アザフ
ェナントレン環、ジアザフェナントレン環、アザトリフェニレン環、ジアザトリフェニレ
ン環がさらに好ましい。
Adjacent substituents bonded to ring B may be bonded to each other to further form a ring. When a ring is further formed, it forms an azaanthracene ring, a diazaanthracene ring, an azaphenanthrene ring, a diazaphenanthrene ring, an azatriphenylene ring, a diazatriphenylene ring and the like together with the ring B. From the viewpoint of solubility, it is preferable that the substituents of the ring B do not bond with each other to form a ring. On the other hand, from the viewpoint that the emission and absorption wavelengths can be made longer, it is preferable that the substituents are bonded to each other to further form a ring. As the fused ring containing ring B, the azaanthracene ring, the diazaanthracene ring, the azaphenanthrene ring, the diazaphenanthrene ring, the azatriphenylene ring, and the diazatriphenylene ring are further added because the excited state is not easily deactivated by heat. preferable.
環Ｄは、置換基を有していても良いピリジン環、ピラジン環、ピリミジン環、イミダゾ
ール環、オキサゾール環、チアゾール環のいずれかを表す。環Ｄに結合する隣り合う置換
基どうしが結合してさらに環を形成しても良い。さらに環を形成した場合、環Ｄと合わせ
て、キノリン環、イソキノリン環、キノキサリン環、キナゾリン環、ベンゾイミダゾール
環、ベンゾオキサゾール環、ベンゾチアゾール環を形成する。環Ｂを含む縮合環としては
、励起状態が熱的に失活しにくい点で、アザアントラセン環、ジアザアントラセン環、ア
ザフェナントレン環、ジアザフェナントレン環、アザトリフェニレン環、ジアザトリフェ
ニレン環が好ましく、ベンゾチアゾール環がさらに好ましい。
Ring D represents any one of a pyridine ring, a pyrazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, and a thiazole ring which may have a substituent. Adjacent substituents bonded to ring D may be bonded to each other to further form a ring. When a ring is further formed, it forms a quinoline ring, an isoquinoline ring, a quinoxaline ring, a quinazoline ring, a benzimidazole ring, a benzoxazole ring, and a benzothiazole ring together with the ring D. As the fused ring containing ring B, an azaanthracene ring, a diazaanthracene ring, an azaphenanthrene ring, a diazaphenanthrene ring, an azatriphenylene ring, and a diazatriphenylene ring are preferable because the excited state is not easily deactivated. , The benzothiazole ring is more preferred.
環Ａ〜Ｄが有しても良い置換基は、フッ素原子、塩素原子、臭素原子、炭素数１〜２０
のアルキル基、炭素数２〜２０のアルケニル基、炭素数７〜４０の（ヘテロ）アラルキル
基、炭素数１〜２０のアルコキシ基、炭素数３〜２０の（ヘテロ）アリールオキシ基、ア
ルキル基の炭素数が１〜２０であるアルキルシリル基、アリール基の炭素数が６〜２０で
あるアリールシリル基、炭素数２〜２０のアルキルカルボニル基、炭素数７〜２０のアリ
ールカルボニル基、炭素数２〜２０のアルキルアミノ基、炭素数６〜２０のアリールアミ
ノ基、または炭素数３〜２０の（ヘテロ）アリール基のいずれか、またはこれらの組み合
わせである。
環Ａ〜Ｄが有しても良い置換基は、溶解性の点から、炭素数１〜２０のアルキル基、炭
素数７〜４０の（ヘテロ）アラルキル基であることが好ましい。
The substituents that the rings A to D may have are a fluorine atom, a chlorine atom, a bromine atom, and 1 to 20 carbon atoms.
Alkyl group, alkenyl group having 2 to 20 carbon atoms, (hetero) aralkyl group having 7 to 40 carbon atoms, alkoxy group having 1 to 20 carbon atoms, (hetero) aryloxy group having 3 to 20 carbon atoms, alkyl group An alkylsilyl group having 1 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, an alkylcarbonyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, and 2 carbon atoms. An alkylamino group of ~ 20, an arylamino group of 6 to 20 carbon atoms, or a (hetero) aryl group of 3 to 20 carbon atoms, or a combination thereof.
The substituents that the rings A to D may have are preferably an alkyl group having 1 to 20 carbon atoms and a (hetero) aralkyl group having 7 to 40 carbon atoms from the viewpoint of solubility.
＜Ｚ１＞
Ｚ１は、直接結合または２価の芳香族連結基を表す。Ｚ１は、製造が容易な点で、直接
結合であることが好ましい。Ｚ１は、Ｎ−ヒドロキシスクシンイミドエステル基をイリジ
ウム金属から遠ざけることができる点で、２価の芳香族連結基であることが好ましく、励
起状態が熱的に失活しにくい点で、フェニレン基、ビフェニレン基、テルフェニレン基、
フルオレンジイル基のいずれかが好ましい。
<Z 1 >
Z 1 represents a direct bond or a divalent aromatic linking group. Z 1 is preferably directly bonded because it is easy to manufacture. Z 1 is preferably a divalent aromatic linking group because it can keep the N-hydroxysuccinimide ester group away from the iridium metal, and it is difficult for the excited state to be thermally deactivated. Biphenylene group, terphenylene group,
Any of the full orange yl groups is preferred.
＜Ｒ１＞
Ｒ１は、３つ以上の単結合を介してＺ１とＮ−ヒドロキシスクシンイミドエステル基を
つなぐ基を表す。Ｒ１は、下記式（４）で表されることが好ましい。
<R 1 >
R 1 represents a group that connects Z 1 with an N-hydroxysuccinimide ester group via three or more single bonds. R 1 is preferably represented by the following formula (4).
［式中、Ｑは、―ＣＲ３Ｒ４―、―Ｏ―、―ＣＯ―、―ＮＲ５―、及び―Ｓ―からなる群
より選ばれるいずれかの基を表し、ｎは２以上、３０以下の整数を表す。
Ｒ３〜Ｒ５は、各々独立して、水素原子、又は置換基を有していてもよい炭素数１〜２
０のアルキル基を表す。
ｎ個のＱは、同じでもよく、また異なっていてもよい。］
中でも、化学的な耐久性に優れる点で、―ＣＲ２Ｒ３―を含むことが好ましい。
Wherein, Q is, -CR 3 R 4 -, - O -, - CO -, - NR 5 -, and represents any one group selected from the group consisting of -S-, n is 2 or more, 30 Represents the following integers.
Each of R 3 to R 5 has 1 to 2 carbon atoms which may independently have a hydrogen atom or a substituent.
Represents an alkyl group of 0.
The n Qs may be the same or different. ]
Above all, it is preferable to contain —CR 2 R 3 — from the viewpoint of excellent chemical durability.
本発明のイリジウム錯体は、式（１）中のＺ１が環Ｃであるベンゼン環に結合すること
が好ましい。すなわち、式（２）で表されることが溶解性の観点から好ましい。
The iridium complex of the present invention is preferably bonded to a benzene ring in which Z 1 in the formula (1) is ring C. That is, it is preferable that it is represented by the formula (2) from the viewpoint of solubility.
［式（２）中、ａは０〜４の整数である。
Ｒ２は、フッ素原子、塩素原子、臭素原子、炭素数１〜２０のアルキル基、炭素数７〜
４０の（ヘテロ）アラルキル基、炭素数１〜２０のアルコキシ基、炭素数３〜２０の（ヘ
テロ）アリールオキシ基、アルキル基の炭素数が１〜２０であるアルキルシリル基、アリ
ール基の炭素数が６〜２０であるアリールシリル基、炭素数２〜２０のアルキルカルボニ
ル基、炭素数７〜２０のアリールカルボニル基、炭素数２〜２０のアルキルアミノ基、炭
素数６〜２０のアリールアミノ基、または炭素数３〜２０の（ヘテロ）アリール基を表す
。
[In equation (2), a is an integer from 0 to 4.
R 2 is a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms, and 7 to 20 carbon atoms.
40 (hetero) aralkyl groups, alkoxy groups having 1 to 20 carbon atoms, (hetero) aryloxy groups having 3 to 20 carbon atoms, alkylsilyl groups having 1 to 20 carbon atoms, and aryl groups having 1 to 20 carbon atoms. Arylsilyl group having 6 to 20, alkylcarbonyl group having 2 to 20 carbon atoms, arylcarbonyl group having 7 to 20 carbon atoms, alkylamino group having 2 to 20 carbon atoms, arylamino group having 6 to 20 carbon atoms, Alternatively, it represents a (hetero) aryl group having 3 to 20 carbon atoms.
環Ａ、環Ｂ、環Ｄ、Ｚ１、Ｒ１は、式（１）における環Ａ、環Ｂ、環Ｄ、Ｚ１、Ｒ１と
同義である。］
Ｒ２は、溶解性の点から、炭素数１〜２０のアルキル基、炭素数７〜４０の（ヘテロ）
アラルキル基であることが好ましい。
本発明のイリジウム錯体は、式（２）中の環Ｄが、置換基どうしが結合してベンゼン環
を形成したチアゾール環、すなわち、ベンゾチアゾール環である、すなわち、式（３）で
表されることが、励起状態が熱的に失活しにくい点で好ましい。
Ring A, ring B, ring D, Z 1, R 1 is as defined ring A, ring B in formula (1), ring D, and Z 1, R 1. ]
R 2, from the viewpoint of solubility, the alkyl group having 1 to 20 carbon atoms, of 7 to 40 carbon atoms (hetero)
It is preferably an aralkyl group.
The iridium complex of the present invention is a thiazole ring in which the ring D in the formula (2) is bonded to each other to form a benzene ring, that is, a benzothiazole ring, that is, it is represented by the formula (3). This is preferable because the excited state is less likely to be thermally deactivated.
［式（３）中、ａ、環Ａ、環Ｂ、環Ｄ、Ｚ１、Ｒ１、Ｒ２は、式（２）における環Ａ、環
Ｂ、環Ｄ、Ｚ１、Ｒ１と同義である。］
以下に、本発明のイリジウム錯体の好ましい具体例を示すが、本発明はこれらに限定さ
れるものではない。
[In formula (3), a, ring A, ring B, ring D, Z 1 , R 1 , and R 2 are synonymous with rings A, ring B, ring D, Z 1 , and R 1 in formula (2). be. ]
Hereinafter, preferred specific examples of the iridium complex of the present invention will be shown, but the present invention is not limited thereto.
以下、実施例を示して本発明について更に具体的に説明する。本発明は以下の実施例に
限定されるものではなく、本発明はその要旨を逸脱しない限り任意に変更して実施できる
。
［反応１］
Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to the following examples, and the present invention can be arbitrarily modified and implemented without departing from the gist thereof.
[Reaction 1]
３００ｍＬナスフラスコに、中間体１（ＷＯ２０１６１９４７８４Ａ記載の方法にて合
成した。３．８ｇ）、３−クロロシンノリン（１．０ｇ）、［テトラキス（トリフェニル
ホスフィン）パラジウム（０）］（０．１５ｇ）、２Ｍリン酸三カリウム水溶液（１３ｍ
Ｌ）、トルエン（２６ｍＬ）およびエタノール（１３ｍＬ）を加え、１０５℃のオイルバ
スで５時間撹拌した。室温まで冷却後、水相を除去し、残りの液を減圧濃縮して得られた
残渣をシリカゲルカラムクロマトグラフィー（中性シリカゲル、酢酸エチル／ヘキサン＝
１／４）で精製したところ、淡黄色固体として中間体２を２．６ｇ得た。
Intermediate 1 (synthesized by the method described in WO2016194784A. 3.8 g), 3-chlorosinnoline (1.0 g), [Tetrakis (triphenylphosphine) palladium (0)] (0.15 g) in a 300 mL eggplant flask. ), 2M tripotassium phosphate aqueous solution (13m)
L), toluene (26 mL) and ethanol (13 mL) were added, and the mixture was stirred in an oil bath at 105 ° C. for 5 hours. After cooling to room temperature, the aqueous phase was removed, the remaining liquid was concentrated under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (neutral silica gel, ethyl acetate / hexane =).
When purified in 1/4), 2.6 g of Intermediate 2 was obtained as a pale yellow solid.
［反応２］
５００ｍＬナスフラスコに、２−（３−ブロモフェニル）ベンゾチアゾール（１１．３
ｇ）、ビス（ピナコラート）ジボロン（１１．４ｇ）、酢酸カリウム（１１．４ｇ）、ジ
クロロ（１，１’−ビス（ジフェニルホスフィノ）フェロセン）パラジウム・ジクロロメ
タン付加物（１．０ｇ）及びジメチルスルホキシド（１００ｍＬ）を入れ、８５℃で３．
５時間撹拌した。室温まで冷却後、水（３００ｍＬ）およびジクロロメタン（３００ｍＬ
）を加えて分液洗浄した。油相を回収し減圧濃縮して得られた残渣をシリカゲルカラムク
ロマトグラフィー（中性シリカゲル、ジクロロメタン／ヘキサン＝１／１）で精製したと
ころ、３−［ベンゾチアゾール−２−イル］フェニル−４，４，５，５−テトラメチル−
１，３，２−ジオキサボロランを１１．９ｇ得た。
2- (3-Bromophenyl) benzothiazole (11.3) in a 500 mL eggplant flask
g), bis (pinacolato) diboron (11.4 g), potassium acetate (11.4 g), dichloro (1,1'-bis (diphenylphosphino) ferrocene) palladium-dichloromethane adduct (1.0 g) and dimethyl sulfoxide Add (100 mL) and at 85 ° C. 3.
The mixture was stirred for 5 hours. After cooling to room temperature, water (300 mL) and dichloromethane (300 mL)
) Was added and the liquid was separated and washed. The oil phase was recovered and concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (neutral silica gel, dichloromethane / hexane = 1/1). As a result, 3- [benzothiazole-2-yl] phenyl-4, 4,5,5-tetramethyl-
11.9 g of 1,3,2-dioxaborolane was obtained.
［反応３］
５００ｍＬナスフラスコに、３−［ベンゾチアゾール−２−イル］フェニル−４，４，
５，５−テトラメチル−１，３，２−ジオキサボロラン（１２．９ｇ）、３−ブロモ−３
‘−ヨード−１，１’−ビフェニル（１４．４ｇ）、［テトラキス（トリフェニルホスフ
ィン）パラジウム（０）］（２．０ｇ）、２Ｍリン酸三カリウム水溶液（５０ｍＬ）、ト
ルエン（１００ｍＬ）およびエタノール（３５ｍＬ）を加え、１０５℃のオイルバスで５
時間撹拌した。室温まで冷却後、水相を除去し、残りの液を減圧濃縮して得られた残渣を
シリカゲルカラムクロマトグラフィー（中性シリカゲル、ジクロロメタン／ヘキサン＝１
／１）で精製したところ、淡褐色固体として中間体３を１５．８ｇ得た。これ以上の精製
はせずに次の反応を行った。
3- [Benzothiazole-2-yl] phenyl-4,4 in a 500 mL eggplant flask
5,5-Tetramethyl-1,3,2-dioxaborolane (12.9 g), 3-bromo-3
'-Iodo-1,1'-biphenyl (14.4 g), [Tetrakis (triphenylphosphine) palladium (0)] (2.0 g), 2M tripotassium phosphate aqueous solution (50 mL), toluene (100 mL) and ethanol Add (35 mL) and in an oil bath at 105 ° C for 5
Stir for hours. After cooling to room temperature, the aqueous phase was removed, the remaining liquid was concentrated under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (neutral silica gel, dichloromethane / hexane = 1).
When purified in 1/1), 15.8 g of Intermediate 3 was obtained as a light brown solid. The following reaction was carried out without further purification.
［反応４］
下部に側管が付いたジムロートを備えた３００ｍＬナスフラスコに、中間体３（１５．
８ｇ）、塩化イリジウムｎ水和物（フルヤ金属社製、５．６ｇ）、水（３０ｍＬ）および
２−エトキシエタノール（１３０ｍＬ）を入れ、オイルバスの温度１３５℃で４時間撹拌
し、その後１４５℃に昇温しさらに１．５時間撹拌した。この間側管から凝結した溶媒液
を一部抜出続けた。その後室温まで冷却し、析出した固体をろ取し、メタノール（３００
ｍＬ）で洗浄したところ、橙色固体の中間体を１５．２ｇ得た。
Intermediate 3 (15.) in a 300 mL eggplant flask with a Dimroth with a side tube at the bottom.
8 g), iridium chloride n hydrate (5.6 g manufactured by Furuya Metal Co., Ltd.), water (30 mL) and 2-ethoxyethanol (130 mL) are added, and the mixture is stirred at an oil bath temperature of 135 ° C. for 4 hours, and then at 145 ° C. The temperature was raised to 1 and the mixture was further stirred for 1.5 hours. During this time, a part of the condensed solvent solution was continuously extracted from the side tube. Then, the mixture is cooled to room temperature, the precipitated solid is collected by filtration, and methanol (300) is collected.
When washed with mL), 15.2 g of an orange solid intermediate was obtained.
［反応５］
３００ｍＬナスフラスコに、中間体４（７．０ｇ）、２−エトキシエタノール（８４ｍ
Ｌ）、炭酸ナトリウム（８．７ｇ）、アセチルアセトン（３．２ｇ）を入れ、１３５℃で
３０分間撹拌した。その後室温まで冷却した後溶媒を減圧下除去し、得られた残渣をシリ
カゲルカラムクロマトグラフィー（中性シリカゲル、ジクロロメタン／ヘキサン＝１／１
）で精製したところ、橙色固体の中間体５を７．３ｇ得た。
Intermediate 4 (7.0 g), 2-ethoxyethanol (84 m) in a 300 mL eggplant flask
L), sodium carbonate (8.7 g) and acetylacetone (3.2 g) were added, and the mixture was stirred at 135 ° C. for 30 minutes. Then, after cooling to room temperature, the solvent was removed under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (neutral silica gel, dichloromethane / hexane = 1/1).
), 7.3 g of an orange solid intermediate 5 was obtained.
［反応６］
５００ｍＬナスフラスコに、４−（４−ブロモフェニル）酪酸（１０．６ｇ）、メタノ
ール（２００ｍＬ）を入れ、撹拌しながら濃硫酸（２．５ｍＬ）を滴下した後、９０℃の
オイルバスに浸し、３時間撹拌した。室温まで冷却した後水（２００ｍＬ）とジクロロメ
タン（１５０ｍＬ）を加え分液洗浄した。油相を硫酸マグネシウムで乾燥させ、ろ過後減
圧濃縮したところ、無色油状の４−（４−ブロモフェニル）酪酸メチルを１１．２ｇ得た
。
4- (4-Bromophenyl) butyric acid (10.6 g) and methanol (200 mL) were placed in a 500 mL eggplant flask, concentrated sulfuric acid (2.5 mL) was added dropwise with stirring, and the mixture was immersed in an oil bath at 90 ° C. The mixture was stirred for 3 hours. After cooling to room temperature, water (200 mL) and dichloromethane (150 mL) were added for liquid separation washing. The oil phase was dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give 11.2 g of colorless and oily methyl 4- (4-bromophenyl) butyrate.
［反応７］
５００ｍＬフラスコに、４−（４−ブロモフェニル）酪酸メチル（１１．２ｇ）、ビス
（ピナコラート）ジボロン（１２．７ｇ）、酢酸カリウム（１２．８ｇ）、ジクロロ（１
，１’−ビス（ジフェニルホスフィノ）フェロセン）パラジウム・ジクロロメタン付加物
（１．１ｇ）及びジメチルスルホキシド（１００ｍＬ）を入れ、８５℃で５時間撹拌した
。室温まで冷却後、水（３００ｍＬ）およびジクロロメタン（１５０ｍＬ）を加えて分液
洗浄し、さらにジクロロメタン（１００ｍＬ）で抽出した。油相を回収し減圧濃縮して得
られた残渣をシリカゲルカラムクロマトグラフィー（中性シリカゲル、酢酸エチル／ヘキ
サン＝１／４）で精製したところ、無色油状の４−（４，４，５，５−テトラメチル−１
，３，２−ジオキサボロラン−２−イル）フェニル酪酸メチルを１１．９ｇ得た。
Methyl 4- (4-bromophenyl) butyrate (11.2 g), bis (pinacolat) diboron (12.7 g), potassium acetate (12.8 g), dichloro (1) in a 500 mL flask.
, 1'-bis (diphenylphosphino) ferrocene) palladium / dichloromethane adduct (1.1 g) and dimethyl sulfoxide (100 mL) were added, and the mixture was stirred at 85 ° C. for 5 hours. After cooling to room temperature, water (300 mL) and dichloromethane (150 mL) were added for liquid separation washing, and the mixture was further extracted with dichloromethane (100 mL). When the oil phase was recovered and concentrated under reduced pressure, the obtained residue was purified by silica gel column chromatography (neutral silica gel, ethyl acetate / hexane = 1/4) and found to be colorless and oily 4- (4,4,5,5). − Tetramethyl-1
, 3,2-Dioxaborolan-2-yl) Methyl phenylbutyrate was obtained in an amount of 11.9 g.
［反応８］
２００ｍＬナスフラスコに、中間体５（４．３ｇ）、中間体２（２．８ｇ）およびフェ
ニルシクロヘキサン（０．５ｍＬ）を入れ、２３０℃に予熱されたオイルバスに浸し２時
間撹拌した後、２４０℃に昇温しさらに５時間撹拌した。途中、２４０℃で１時間撹拌時
にジイソプロピルエチルアミン（０．２ｍＬ）を加えた。室温まで冷却した後シリカゲル
カラムクロマトグラフィー（中性シリカゲル、ジクロロメタン／ヘキサン＝６／４）で精
製を行い、暗赤色固体の中間体６を０．６５ｇ得た。
Intermediate 5 (4.3 g), intermediate 2 (2.8 g) and phenylcyclohexane (0.5 mL) were placed in a 200 mL eggplant flask, immersed in an oil bath preheated to 230 ° C., stirred for 2 hours, and then 240. The temperature was raised to ° C., and the mixture was further stirred for 5 hours. On the way, diisopropylethylamine (0.2 mL) was added with stirring at 240 ° C. for 1 hour. After cooling to room temperature, purification was performed by silica gel column chromatography (neutral silica gel, dichloromethane / hexane = 6/4) to obtain 0.65 g of intermediate 6 as a dark red solid.
［反応９］
１００ｍＬナスフラスコに、中間体６（０．６５ｇ）、４−（４，４，５，５−テトラ
メチル−１，３，２−ジオキサボロラン−２−イル）フェニル酪酸メチル（０．５１ｇ）
、［テトラキス（トリフェニルホスフィン）パラジウム（０）］（０．１ｇ）、２Ｍリン
酸三カリウム水溶液（５ｍＬ）、トルエン（５ｍＬ）およびエタノール（５ｍＬ）を加え
、１００℃のオイルバスで３時間撹拌した。室温まで冷却後、減圧濃縮して得られた残渣
を水（１００ｍＬ）およびジクロロメタン（１５０ｍＬ）で分液洗浄した。油相を硫酸マ
グネシウムで乾燥後、ろ過し溶媒を減圧除去した。得られた残渣を１，２−ジメトキシエ
タン（２０ｍＬ）に室温で溶解し、この溶液にメタノール（２００ｍＬ）を撹拌しながら
滴下した。析出した固体をろ取し、メタノール（５０ｍＬ）で洗浄し乾燥したところ、茶
色固体として中間体７を０．６０ｇ得た。
Intermediate 6 (0.65 g), 4- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenylbutyrate methyl (0.51 g) in a 100 mL eggplant flask
, [Tetrakis (triphenylphosphine) palladium (0)] (0.1 g), 2M tripotassium phosphate aqueous solution (5 mL), toluene (5 mL) and ethanol (5 mL), and stir in an oil bath at 100 ° C. for 3 hours. bottom. After cooling to room temperature, the residue obtained by concentration under reduced pressure was separated and washed with water (100 mL) and dichloromethane (150 mL). The oil phase was dried over magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The obtained residue was dissolved in 1,2-dimethoxyethane (20 mL) at room temperature, and methanol (200 mL) was added dropwise to this solution with stirring. The precipitated solid was collected by filtration, washed with methanol (50 mL) and dried to obtain 0.60 g of Intermediate 7 as a brown solid.
［反応１０］
１００ｍＬナスフラスコに、中間体７（０．６０ｇ）、テトラヒドロフラン（６０ｍＬ
）を入れ、これに水（６０ｍＬ）に水酸化ナトリウム（０．１９５ｇ）を溶かした水溶液
を加え、４５℃のオイルバスで２時間撹拌した。その後、水（６ｍＬ）に水酸化ナトリウ
ム（４．０ｇ）を溶かした水溶液を滴下し、さらに４時間撹拌した。室温まで冷却した後
、１Ｎ塩酸で中和したのち、ジクロロメタン（１００ｍＬ）で抽出した。減圧下溶媒を除
去して得られた残渣に、１，２−ジメトキシエタン（８ｍＬ）を加えて溶解させた得た溶
液に、メタノール（１５０ｍＬ）を室温で加え２０分間撹拌した。その後、析出した固体
をろ過し、メタノール（５０ｍＬ）で洗浄し乾燥したところ、濃茶色固体の中間体８を０
．５９ｇ得た。
Intermediate 7 (0.60 g), tetrahydrofuran (60 mL) in a 100 mL eggplant flask
) Was added, an aqueous solution prepared by dissolving sodium hydroxide (0.195 g) in water (60 mL) was added thereto, and the mixture was stirred in an oil bath at 45 ° C. for 2 hours. Then, an aqueous solution prepared by dissolving sodium hydroxide (4.0 g) in water (6 mL) was added dropwise, and the mixture was further stirred for 4 hours. After cooling to room temperature, the mixture was neutralized with 1N hydrochloric acid and then extracted with dichloromethane (100 mL). Methanol (150 mL) was added to the obtained solution obtained by adding 1,2-dimethoxyethane (8 mL) to the residue obtained by removing the solvent under reduced pressure at room temperature, and the mixture was stirred for 20 minutes. Then, the precipitated solid was filtered, washed with methanol (50 mL) and dried, and the dark brown solid intermediate 8 was 0.
.. I got 59g.
［反応１１］
１００ｍＬナスフラスコに、中間体８（０．５９ｇ）、Ｎ−ヒドロキシフタルイミド（
６２ｍｇ）及び乾燥ジクロロメタン（２．５ｍＬ）を入れ、氷水浴に浸し撹拌しながら、
ジシクロヘキシルカルボジイミド（１１１ｍｇ）を投入し、２時間撹拌した。その後反応
液をそのままシリカゲルカラムクロマトグラフィー（中性シリカゲル、ジクロロメタンの
み）で精製した。得られた粗体は１，２−ジメトキシエタン（８ｍＬ）に溶解させ、この
溶液にメタノール（１００ｍＬ）を室温で滴下して得られた固体をろ過し乾燥させた。濃
茶色固体として化合物１を０．５７ｇ得た。
Intermediate 8 (0.59 g), N-hydroxyphthalimide (in a 100 mL eggplant flask)
62 mg) and dry dichloromethane (2.5 mL) are added, soaked in an ice water bath and stirred.
Dicyclohexylcarbodiimide (111 mg) was added and stirred for 2 hours. Then, the reaction solution was purified by silica gel column chromatography (neutral silica gel, dichloromethane only) as it was. The obtained crude product was dissolved in 1,2-dimethoxyethane (8 mL), methanol (100 mL) was added dropwise to this solution at room temperature, and the obtained solid was filtered and dried. 0.57 g of Compound 1 was obtained as a dark brown solid.
Claims (3)
環Ｂは、キノリン環、イソキノリン環、ナフチリジン環のいずれかを表す。
環Ｄは、ピリジン環、ピラジン環、ピリミジン環、イミダゾール環、オキサゾール環、
チアゾール環のいずれかを表す。
環Ａ〜Ｄは、置換基を有していても良く、置換基は、フッ素原子、塩素原子、臭素原子
、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数７〜４０の（ヘ
テロ）アラルキル基、炭素数１〜２０のアルコキシ基、炭素数３〜２０の（ヘテロ）アリ
ールオキシ基、アルキル基の炭素数が１〜２０であるアルキルシリル基、アリール基の炭
素数が６〜２０であるアリールシリル基、炭素数２〜２０のアルキルカルボニル基、炭素
数７〜２０のアリールカルボニル基、炭素数２〜２０のアルキルアミノ基、炭素数６〜２
０のアリールアミノ基、または炭素数３〜２０の（ヘテロ）アリール基のいずれか、また
はこれらの組み合わせである。また、環Ａ〜Ｄに結合する隣り合う置換基どうしが結合し
てさらに環を形成しても良い。
Ｚ１は、直接結合または２価の芳香族連結基を表す。
Ｒ１は、３つ以上の単結合を介してＺ１とＮ−ヒドロキシスクシンイミドエステル基を
つなぐ基を表す。］ A compound represented by the following formula (1).
Ring B represents any of a quinoline ring, an isoquinoline ring, and a diazanaphthalene ring.
Ring D is a pyridine ring, a pyrazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring,
Represents one of the thiazole rings.
Rings A to D may have a substituent, and the substituents are a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and 7 carbon atoms. ~ 40 (hetero) aralkyl group, alkoxy group having 1 to 20 carbon atoms, (hetero) aryloxy group having 3 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms of alkyl group, carbon of aryl group An arylsilyl group having 6 to 20 carbon atoms, an alkylcarbonyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, an alkylamino group having 2 to 20 carbon atoms, and 6 to 2 carbon atoms.
It is either an arylamino group of 0, or a (hetero) aryl group having 3 to 20 carbon atoms, or a combination thereof. Further, adjacent substituents bonded to the rings A to D may be bonded to each other to further form a ring.
Z 1 represents a direct bond or a divalent aromatic linking group.
R 1 represents a group that connects Z 1 with an N-hydroxysuccinimide ester group via three or more single bonds. ]
Ｒ２は、フッ素原子、塩素原子、臭素原子、炭素数１〜２０のアルキル基、炭素数７〜
４０の（ヘテロ）アラルキル基、炭素数１〜２０のアルコキシ基、炭素数３〜２０の（ヘ
テロ）アリールオキシ基、アルキル基の炭素数が１〜２０であるアルキルシリル基、アリ
ール基の炭素数が６〜２０であるアリールシリル基、炭素数２〜２０のアルキルカルボニ
ル基、炭素数７〜２０のアリールカルボニル基、炭素数２〜２０のアルキルアミノ基、炭
素数６〜２０のアリールアミノ基、または炭素数３〜２０の（ヘテロ）アリール基を表す
。
環Ａ、環Ｂ、環Ｄ、Ｚ１、Ｒ１は、式（１）における環Ａ、環Ｂ、環Ｄ、Ｚ１、Ｒ１と
同義である。］ The compound according to claim 1, wherein the formula (1) is a compound represented by the formula (2).
R 2 is a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms, and 7 to 20 carbon atoms.
40 (hetero) aralkyl groups, alkoxy groups having 1 to 20 carbon atoms, (hetero) aryloxy groups having 3 to 20 carbon atoms, alkylsilyl groups having 1 to 20 carbon atoms, and aryl groups having 1 to 20 carbon atoms. Arylsilyl group having 6 to 20, alkylcarbonyl group having 2 to 20 carbon atoms, arylcarbonyl group having 7 to 20 carbon atoms, alkylamino group having 2 to 20 carbon atoms, arylamino group having 6 to 20 carbon atoms, Alternatively, it represents a (hetero) aryl group having 3 to 20 carbon atoms.
Ring A, ring B, ring D, Z 1, R 1 is as defined ring A, ring B in formula (1), ring D, and Z 1, R 1. ]
、環Ｄ、Ｚ１、Ｒ１と同義である。］ The compound according to claim 2, wherein the formula (2) is a compound represented by the formula (3).
, Ring D, Z 1 , and R 1 . ]
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