JP2022026256A - Compound - Google Patents
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- JP2022026256A JP2022026256A JP2020129634A JP2020129634A JP2022026256A JP 2022026256 A JP2022026256 A JP 2022026256A JP 2020129634 A JP2020129634 A JP 2020129634A JP 2020129634 A JP2020129634 A JP 2020129634A JP 2022026256 A JP2022026256 A JP 2022026256A
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- substituent
- alkyl group
- alkynyl
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 41
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 72
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 35
- 125000005843 halogen group Chemical group 0.000 claims abstract description 21
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 19
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims description 81
- 125000003118 aryl group Chemical group 0.000 claims description 35
- 125000001072 heteroaryl group Chemical group 0.000 claims description 34
- 125000003342 alkenyl group Chemical group 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 125000003277 amino group Chemical group 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 125000004414 alkyl thio group Chemical group 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052796 boron Inorganic materials 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 50
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 0 **C(C(*)=C1*)=*2C1=*C1=C(*)C(*)=C3C4=C(*)*=C(*)*4*2(*)*13 Chemical compound **C(C(*)=C1*)=*2C1=*C1=C(*)C(*)=C3C4=C(*)*=C(*)*4*2(*)*13 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000008213 purified water Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000013058 crude material Substances 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000010446 mirabilite Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000002428 photodynamic therapy Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000032 diagnostic agent Substances 0.000 description 2
- 229940039227 diagnostic agent Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229960004657 indocyanine green Drugs 0.000 description 2
- MOFVSTNWEDAEEK-UHFFFAOYSA-M indocyanine green Chemical compound [Na+].[O-]S(=O)(=O)CCCCN1C2=CC=C3C=CC=CC3=C2C(C)(C)C1=CC=CC=CC=CC1=[N+](CCCCS([O-])(=O)=O)C2=CC=C(C=CC=C3)C3=C2C1(C)C MOFVSTNWEDAEEK-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004297 night vision Effects 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PJWNCRJSQLQBMQ-LJUMEUDFSA-N CC(C)c1c[nH]c2c3[nH]c(/C=C4\N=C(c([nH]cc5C(C)C)c5-c5c6cccc5)C6=C4C(C)C)c(C(C)C)c3c(cccc3)c3c12 Chemical compound CC(C)c1c[nH]c2c3[nH]c(/C=C4\N=C(c([nH]cc5C(C)C)c5-c5c6cccc5)C6=C4C(C)C)c(C(C)C)c3c(cccc3)c3c12 PJWNCRJSQLQBMQ-LJUMEUDFSA-N 0.000 description 1
- QRHOWVDPHIXNEN-UHFFFAOYSA-N Ethyl 2-hydroxy-4-methylpentanoate Chemical compound CCOC(=O)C(O)CC(C)C QRHOWVDPHIXNEN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- YIAJTHPUOIWKMT-UHFFFAOYSA-N NNc1cc(cccc2)c2cc1NN Chemical compound NNc1cc(cccc2)c2cc1NN YIAJTHPUOIWKMT-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- ZGCHATBSUIJLRL-UHFFFAOYSA-N hydrazine sulfate Chemical compound NN.OS(O)(=O)=O ZGCHATBSUIJLRL-UHFFFAOYSA-N 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
Images
Abstract
Description
本発明は、新規の化合物に関するものである。本発明の化合物は、近赤外域以上に吸収
・発光特性を有するものであり、例えば近赤外発光マーカー、インジケーター、バイオイ
メージング、センサー、波長変換フィルム、発光トランジスター、OLED、電気化学発
光セル、フォトダイナミックセラピー、光美容、ナイトビジョンディスプレイ、セキュリ
ティー、偽造防止用途等の部材として好適に用いることができる。
The present invention relates to novel compounds. The compound of the present invention has absorption / emission characteristics higher than those in the near-infrared region. For example, near-infrared emission markers, indicators, bioimaging, sensors, wavelength conversion films, emission transistors, OLEDs, light-chemical emission cells, and photographs. It can be suitably used as a member for dynamic therapy, optical beauty, night vision display, security, anti-counterfeiting, and the like.
これまで目視による選別、認識等が主流であったが、科学技術の発展とともに、高齢化
や少子化に伴う労働力の減少も相重なって、ロボットを利用した選別・認識へとシフトし
つつある。目視による選別・認識では可視光を利用するしか出来ないが、ロボットを利用
した場合には目視では捉えられない近赤外発光も利用することが可能となり、選別・識別
精度の向上が期待できる。さらに近赤外光は細胞を透過するので、バイオイメージングや
バイオセンサー、医療診断薬、PDTなど医療分野への展開も期待できる。近赤外発光色
素としては、燐光色素として、Ir、Pt、Osなどの金属錯体、蛍光色素として、インドシア
ニングリーン(ICG)、フタロシアニン(Pc)、4,4-ジフルオロー4-ボラー3ア、
4アージアザーs-インデカン(BODIPY)色素が知られている。中でも、BODI
PYは強い吸光度と高い発光量子収率を有することから、特に注目を集めている。
例えば、非特許文献1にはBis-naphthobipyrrolylmethene骨格を有するBODIPY誘導体が
報告されており、NIR領域に強い吸収と、発光を有することが報告されている。また、非
特許文献2には酸素上に水酸基を一つ有するO-BODIPYが赤色領域に吸収と発光を有するこ
とが示されている。
しかしながら、実用化にはさらなる性能向上が求められている。
Until now, visual selection and recognition have been the mainstream, but with the development of science and technology, the labor force is declining due to the aging population and declining birthrate, and there is a shift to robot-based selection and recognition. .. Visible light can only be used for visual sorting and recognition, but near-infrared light emission that cannot be visually captured can also be used when using a robot, and improvement in sorting and identification accuracy can be expected. Furthermore, since near-infrared light passes through cells, it can be expected to be applied to the medical field such as bioimaging, biosensors, medical diagnostic agents, and PDT. Near-infrared luminescent dyes include metal complexes such as Ir, Pt, and Os as phosphorescent dyes, indocyanine green (ICG), phthalocyanine (Pc), and 4,4-difluoro-4-boler 3a as fluorescent dyes.
4 Earth Others-BODIPY dyes are known. Above all, BODI
PY has attracted particular attention because of its strong absorbance and high emission quantum yield.
For example, Non-Patent
However, further performance improvement is required for practical use.
本発明者は、上記非特許文献1及び非特許文献2で開示された化合物では、2座配位子
のため安定性が劣ることを見出した。
The present inventor has found that the compounds disclosed in Non-Patent
本発明者は、上記課題を解決すべく検討を重ねた結果、特定の構造を三座配位させるこ
とにより、ホウ素錯体を安定化し、上記課題を解決することを見出した。本発明は、この
ような知見に基づいて達成されたものであり、以下を要旨とする。
As a result of repeated studies to solve the above-mentioned problems, the present inventor has found that the boron complex is stabilized and the above-mentioned problems are solved by coordinating a specific structure with a tridentate. The present invention has been achieved based on such findings, and the gist thereof is as follows.
[1]式(1)で表される化合物。 [1] A compound represented by the formula (1).
[R1~R8はそれぞれ独立に、水素原子、ハロゲン原子、置換基を有していてもよい
アルキル基、置換基を有していてもよいカルボキシル基、アルケニル基、アルキニル基、
置換基を有していてもよい、芳香族炭化水素環又は芳香族複素環を表し、
R1~R8はそれぞれ隣接する基同士と結合し環を形成していてもよく、
XはN原子又はCR9を表し、
Yはアルキニル基、F原子、OR10、置換基を有していてもよい、アルキル基、芳香
族炭化水素環又は芳香族複素環を表し、
R9は、水素原子、シアノ基、カルボニル基、カルボキシル基、ハロゲン原子、アルキ
ル基、アルキニル基、アルケニル基、アリール基、ヘテロアリール基、アルキルチオ基、
スルホニル基又はアミノ基を表し、アルキル基、アルキニル基、アルケニル基、アリール
基、ヘテロアリール基及びアミノ基は置換基を有していてもよく、
R10は、水素原子、カルボニル基、アルキル基、アリール基又はヘテロアリール基を
表し、アルキル基、アリール基及びヘテロアリール基は置換基を有していてもよい。]
[2]式(2)で表される、[1]に記載の化合物。
[R 1 to R 8 are independent hydrogen atoms, halogen atoms, an alkyl group which may have a substituent, a carboxyl group which may have a substituent, an alkenyl group, an alkynyl group, and the like.
Represents an aromatic hydrocarbon ring or an aromatic heterocycle which may have a substituent.
R 1 to R 8 may be bonded to adjacent groups to form a ring.
X represents N atom or CR 9 and represents
Y represents an alkynyl group, an F atom, an OR 10 , an alkyl group optionally having a substituent, an aromatic hydrocarbon ring or an aromatic heterocycle.
R 9 is a hydrogen atom, a cyano group, a carbonyl group, a carboxyl group, a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkylthio group,
Representing a sulfonyl group or an amino group, an alkyl group, an alkynyl group, an alkenyl group, an aryl group, a heteroaryl group and an amino group may have a substituent.
R 10 represents a hydrogen atom, a carbonyl group, an alkyl group, an aryl group or a heteroaryl group, and the alkyl group, the aryl group and the heteroaryl group may have a substituent. ]
[2] The compound according to [1], which is represented by the formula (2).
[式(2)において、
V及びWはそれぞれ独立に、置換基を有していてもよい、芳香族炭化水素環又は芳香族
複素環を表し、
R1‘~R4‘、R7´~R8´はそれぞれ独立に、水素原子、ハロゲン原子、置換基
を有していてもよいアルキル基、置換基を有していてもよいカルボキシル基、アルケニル
基、アルキニル基、置換基を有していてもよい、芳香族炭化水素環又は芳香族複素環を表
し、
X及びYは式(1)と同義である。]
[3][1]に記載の式(1)で表される化合物及び式(3)で表される化合物を含むもので
ある、組成物。
[In equation (2)
V and W each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle which may have a substituent.
R 1'to R 4'and R 7'to R 8'independently each have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and a carboxyl group which may have a substituent. Represents an aromatic hydrocarbon ring or an aromatic heterocycle which may have an alkenyl group, an alkynyl group or a substituent.
X and Y are synonymous with equation (1). ]
[3] A composition comprising the compound represented by the formula (1) and the compound represented by the formula (3) according to [1].
[式(3)において、
V2及びW2はそれぞれ独立に、置換基を有していてもよい、芳香族炭化水素環又は芳
香族複素環を表し、
R21~R24、R27~R28はそれぞれ独立に、水素原子、ハロゲン原子、置換基
を有していてもよいアルキル基、置換基を有していてもよいカルボキシル基、アルケニル
基、アルキニル基、置換基を有していてもよい、芳香族炭化水素環又は芳香族複素環を表
し、
X2はN原子又はCR29を表し、
Y2はアルキニル基、F原子、OR20、置換基を有していてもよい、アルキル基、芳
香族炭化水素環又は芳香族複素環を表し、
R29は、水素原子、シアノ基、カルボニル基、カルボキシル基、ハロゲン原子、アル
キル基、アルキニル基、アルケニル基、アリール基、ヘテロアリール基、アルキルチオ基
、スルホニル基又はアミノ基を表し、アルキル基、アルキニル基、アルケニル基、アリー
ル基、ヘテロアリール基及びアミノ基は置換基を有していてもよく、
R20は、水素原子、カルボニル基、アルキル基、アリール基又はヘテロアリール基を
表し、アルキル基、アリール基及びヘテロアリール基は置換基を有していてもよい。]
[In equation (3)
V 2 and W 2 each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle which may have a substituent.
R 21 to R 24 and R 27 to R 28 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a carboxyl group which may have a substituent, an alkenyl group, and an alkynyl. Represents an aromatic hydrocarbon ring or an aromatic heterocycle that may have a group, a substituent,
X 2 represents N atom or CR 29
Y 2 represents an alkynyl group, an F atom, OR 20 , an alkyl group optionally having a substituent, an aromatic hydrocarbon ring or an aromatic heterocycle.
R 29 represents a hydrogen atom, a cyano group, a carbonyl group, a carboxyl group, a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkylthio group, a sulfonyl group or an amino group, and represents an alkyl group or an alkynyl group. The group, alkenyl group, aryl group, heteroaryl group and amino group may have a substituent.
R 20 represents a hydrogen atom, a carbonyl group, an alkyl group, an aryl group or a heteroaryl group, and the alkyl group, the aryl group and the heteroaryl group may have a substituent. ]
本発明は、近赤外吸収又は発光を有する特定構造の新規化合物を提供するものである。 The present invention provides a novel compound having a specific structure having near-infrared absorption or light emission.
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。
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.
本発明の新規の化合物は下記式(1)で表される。
式(1)において、
R1~R8はそれぞれ独立に、水素原子、ハロゲン原子、置換基を有していてもよいア
ルキル基、置換基を有していてもよいカルボキシル基、アルケニル基、アルキニル基、置
換基を有していてもよい、芳香族炭化水素環又は芳香族複素環を表し、
R1~R8はそれぞれ隣接する基同士と結合し環を形成していてもよい。
XはN原子又はCR9を表し、
Yはアルキニル基、F原子、OR10、置換基を有していてもよい、アルキル基、芳香
族炭化水素環又は芳香族複素環を表す。
R9は、水素原子、シアノ基、カルボニル基、カルボキシル基、ハロゲン原子、アルキ
ル基、アルキニル基、アルケニル基、アリール基、ヘテロアリール基、アルキルチオ基、
スルホニル基又はアミノ基を表し、アルキル基、アルキニル基、アルケニル基、アリール
基、ヘテロアリール基及びアミノ基は置換基を有していてもよい。
R10は、水素原子、カルボニル基、アルキル基、アリール基又はヘテロアリール基を
表し、アルキル基、アリール基及びヘテロアリール基は置換基を有していてもよい。
In equation (1)
Each of R 1 to R 8 independently has a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a carboxyl group which may have a substituent, an alkenyl group, an alkynyl group, and a substituent. Represents an aromatic hydrocarbon ring or an aromatic heterocycle which may be
R 1 to R 8 may be bonded to adjacent groups to form a ring.
X represents N atom or CR 9 and represents
Y represents an alkynyl group, an F atom, an OR 10 , an alkyl group which may have a substituent, an aromatic hydrocarbon ring or an aromatic heterocycle.
R 9 is a hydrogen atom, a cyano group, a carbonyl group, a carboxyl group, a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkylthio group,
Representing a sulfonyl group or an amino group, an alkyl group, an alkynyl group, an alkenyl group, an aryl group, a heteroaryl group and an amino group may have a substituent.
R 10 represents a hydrogen atom, a carbonyl group, an alkyl group, an aryl group or a heteroaryl group, and the alkyl group, the aryl group and the heteroaryl group may have a substituent.
(R1~R8)
R1~R8は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有していてもよい
アルキル基、置換基を有していてもよいカルボキシル基、アルケニル基、アルキニル基、
置換基を有していてもよい、芳香族炭化水素環又は芳香族複素環を表す。R1~R8はそ
れぞれ隣接する基同士と結合し環を形成していてもよい。
アルキル基の炭素数は1以上16以下であることが好ましく、12以下であることがよ
り好ましい。これらの範囲であることで溶解性向上し凝集が抑制できる傾向にある。
アルキル基が有していてもよい置換基は、ハロゲン、アルキル基、カルボニル基、カル
ボキシル基、ヒドロキシル基、シリル基、シロール基などが挙げられ、これらの中でもア
ルキル基が好ましい。
置換基を有していてもよい芳香族炭化水素環は、単環又は縮合環であってもよく、特に
限定されない。具体的には、ベンゼン、ナフタレン、フェナントレン等が挙げられる。こ
れらの中でも、ベンゼンが、立体障害を緩和する傾向にあるため好ましい。
置換基を有していてもよい芳香族複素環は、単環又は縮合環であってもよく、特に限定
されない。具体的には、ピロール、チオフェン、ピリジン、チアゾール、イミダゾール等
が挙げられる。これらの中でも、チオフェンが長波長となる傾向にあるため好ましい。
芳香族炭化水素環、芳香族複素環が有していてもよい置換基は特に限定されないが、ア
ルキル基、アルコキシル基、アミノ基などが挙げられ、これらの中でもアルキル基が好ま
しい。
R1~R8の中でも、R1は安定性の観点から、置換基を有していてもよい、芳香族炭
化水素又は芳香族複素環基であることが好ましい。R4、R7及びR3は溶解性の観点か
ら、置換基を有していてもよいアルキル基が好ましく、R5及びR6は性能の観点から結
合し環を形成していることが好ましい。
(R 1 to R 8 )
R 1 to R 8 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a carboxyl group which may have a substituent, an alkenyl group, an alkynyl group, and the like.
Represents an aromatic hydrocarbon ring or an aromatic heterocycle which may have a substituent. R 1 to R 8 may be bonded to adjacent groups to form a ring.
The number of carbon atoms of the alkyl group is preferably 1 or more and 16 or less, and more preferably 12 or less. Within these ranges, solubility is improved and aggregation tends to be suppressed.
Examples of the substituent that the alkyl group may have include a halogen, an alkyl group, a carbonyl group, a carboxyl group, a hydroxyl group, a silyl group, a silol group and the like, and among these, an alkyl group is preferable.
The aromatic hydrocarbon ring which may have a substituent may be a monocyclic ring or a condensed ring, and is not particularly limited. Specific examples thereof include benzene, naphthalene and phenanthrene. Among these, benzene is preferable because it tends to alleviate steric hindrance.
The aromatic heterocycle which may have a substituent may be a monocyclic ring or a condensed ring, and is not particularly limited. Specific examples thereof include pyrrole, thiophene, pyridine, thiazole, and imidazole. Among these, thiophene tends to have a long wavelength, which is preferable.
The substituent that the aromatic hydrocarbon ring or aromatic heterocycle may have is not particularly limited, and examples thereof include an alkyl group, an alkoxyl group, and an amino group, and among these, an alkyl group is preferable.
Among R 1 to R 8 , R 1 is preferably an aromatic hydrocarbon or an aromatic heterocyclic group which may have a substituent from the viewpoint of stability. From the viewpoint of solubility, R 4 , R 7 and R 3 are preferably alkyl groups having a substituent, and R 5 and R 6 are preferably bonded to form a ring from the viewpoint of performance. ..
(X)
XはN原子又はCR9を表す。R9は、水素原子、シアノ基、カルボニル基、カルボキ
シル基、ハロゲン原子、アルキル基、アルキニル基、アルケニル基、アリール基、ヘテロ
アリール基、アルキルチオ基、スルホニル基又はアミノ基を表し、アルキル基、アルキニ
ル基、アルケニル基、アリール基、ヘテロアリール基及びアミノ基は置換基を有していて
もよい。
アルキル基は特に限定されないが、炭素数が1以上20以下であることが好ましく、1
2以下であることがより好ましい。これらの範囲であることで、合成プロセスが容易とな
り安価に合成できる傾向にある。
アルキル基が有していてもよい置換基は、ハロゲン原子、水酸基、アミノ基、アルキル
基、アルコキシル基、カルボニル基、カルボキシル基、芳香族炭化水素基、芳香族複素環
基などが挙げられ、これらの中でも溶解性及び凝集抑制の観点からアルキル基が好ましい
。
アルキニル基は特に限定されないが、炭素数が1以上10以下であることが好ましく、
5以下であることがより好ましい。これらの範囲であることで、溶解性に優れ、凝集を抑
制できる傾向にある。
アルキニル基が有していてもよい置換基は、アルキル基、芳香族炭化水素基、芳香族複
素環基などが挙げられ、これらの中でも溶解性及び凝集抑制の観点からアルキル基が好ま
しい。
アルケニル基が有していてもよい置換基は、アルキル基、芳香族炭化水素基、芳香族複
素環基などが挙げられ、これらの中でも溶解性及び凝集抑制の観点からアルキル基が好ま
しい。
アリール基は単環又は縮合環であってもよく、特に限定されない。具体的には、フェニ
ル基、ナフチル基、フェナントリル基等が挙げられる。これらの中でも、フェニル基が溶
解性の観点より好ましい。
ヘテロアリール基は、単環又は縮合環であってもよく、特に限定されない。具体的には
、チエニル基、ピリジル基、ピラジル基等が挙げられる。これらの中でも、チエニル基が
溶解性の観点より好ましい。
アリール基、ヘテロアリール基が有していてもよい置換基は特に限定されないが、トリ
フルオロメチル基、カルボキシル基、カルボニル基、アルキル基、アルコキシル基、アミ
ノ基、ジアルキルアミノ基などが挙げられ、これらの中でもカルボキシル基が好ましい。
アミノ基は、NR30R31で表され、R30及びR31はそれぞれ独立に、水素原子
、アルキル基、アリール基又はヘテロアリール基を表す。アルキル基、アリール基又はヘ
テロアリール基は置換基を有していてもよい。R30及びR31の具体例としては、R9
のアルキル基、アリール基又はヘテロアリール基と同義であり、有していてもよい置換基
及び好ましい範囲も同じである。
R9は上記の中でもアルキル基であることが好ましく、置換基としてハロゲン原子を有
していることがより好ましい。さらに、トリフルオロメチル基であることが、脂溶性の向
上、波長調整及び合成容易性の観点から好ましい。
(X)
X represents N atom or CR 9 . R 9 represents a hydrogen atom, a cyano group, a carbonyl group, a carboxyl group, a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkylthio group, a sulfonyl group or an amino group, and represents an alkyl group or an alkynyl group. The group, alkenyl group, aryl group, heteroaryl group and amino group may have a substituent.
The alkyl group is not particularly limited, but preferably has 1 or more and 20 or less carbon atoms.
It is more preferably 2 or less. Within these ranges, the synthesis process tends to be easy and cheap.
Examples of the substituent that the alkyl group may have include a halogen atom, a hydroxyl group, an amino group, an alkyl group, an alkoxyl group, a carbonyl group, a carboxyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group and the like. Of these, an alkyl group is preferable from the viewpoint of solubility and inhibition of aggregation.
The alkynyl group is not particularly limited, but preferably has 1 or more and 10 or less carbon atoms.
It is more preferably 5 or less. Within these ranges, the solubility is excellent and the aggregation tends to be suppressed.
Examples of the substituent that the alkynyl group may have include an alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group and the like, and among these, an alkyl group is preferable from the viewpoint of solubility and inhibition of aggregation.
Examples of the substituent that the alkenyl group may have include an alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group and the like, and among these, an alkyl group is preferable from the viewpoint of solubility and inhibition of aggregation.
The aryl group may be a monocyclic ring or a condensed ring, and is not particularly limited. Specific examples thereof include a phenyl group, a naphthyl group, a phenanthryl group and the like. Among these, the phenyl group is preferable from the viewpoint of solubility.
The heteroaryl group may be a monocyclic ring or a fused ring, and is not particularly limited. Specific examples thereof include a thienyl group, a pyridyl group and a pyrazil group. Among these, the thienyl group is preferable from the viewpoint of solubility.
The substituent which the aryl group and the heteroaryl group may have is not particularly limited, and examples thereof include a trifluoromethyl group, a carboxyl group, a carbonyl group, an alkyl group, an alkoxyl group, an amino group and a dialkylamino group. Of these, a carboxyl group is preferable.
The amino group is represented by NR 30 R 31 , where R 30 and R 31 independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, respectively. The alkyl group, aryl group or heteroaryl group may have a substituent. Specific examples of R 30 and R 31 include R 9
It is synonymous with the alkyl group, aryl group or heteroaryl group of the above, and the substituents which may be possessed and the preferable range are also the same.
Among the above, R 9 is preferably an alkyl group, and more preferably has a halogen atom as a substituent. Further, a trifluoromethyl group is preferable from the viewpoint of improving lipophilicity, wavelength adjustment and easiness of synthesis.
(Y)
Yはアルキニル基、F原子、OR10、置換基を有していてもよい、アルキル基、芳香
族炭化水素環又は芳香族複素環を表す。アルキル基、芳香族炭化水素環、芳香族複素環は
置換基を有していてもよく、各基の具体例及び有していてもよい置換基は、R1~R8で
例示したアルキル基、芳香族炭化水素環、芳香族複素環とそれぞれ同義であり、好ましい
範囲も同義である。
R10は、水素原子、カルボニル基、アルキル基、アリール基又はヘテロアリール基を
表し、アルキル基、アリール基及びヘテロアリール基は置換基を有していてもよい。これ
らの各基は、R9のカルボニル基、アルキル基、アリール基又はヘテロアリール基と同義
であり、有していてもよい置換基及び好ましい範囲も同じである。
Yは合成上の観点から、F原子またはOR10が好ましく、特にF原子又はOHが好ま
しい。
(Y)
Y represents an alkynyl group, an F atom, an OR 10 , an alkyl group which may have a substituent, an aromatic hydrocarbon ring or an aromatic heterocycle. The alkyl group, the aromatic hydrocarbon ring, and the aromatic heterocycle may have a substituent, and specific examples of each group and the substituent that may have the substituent are the alkyl groups exemplified in R 1 to R 8 . , Aromatic hydrocarbon ring and aromatic heterocycle, respectively, and the preferred range is also synonymous.
R 10 represents a hydrogen atom, a carbonyl group, an alkyl group, an aryl group or a heteroaryl group, and the alkyl group, the aryl group and the heteroaryl group may have a substituent. Each of these groups is synonymous with a carbonyl group, an alkyl group, an aryl group or a heteroaryl group of R9, and may have a substituent and a preferable range.
From the viewpoint of synthesis, Y is preferably an F atom or OR 10 , and particularly preferably an F atom or OH.
式(1)は、式(2)で表される化合物であることが、化合物の安定性の観点からさら
に好ましい。
It is more preferable that the formula (1) is a compound represented by the formula (2) from the viewpoint of the stability of the compound.
式(2)において、
V及びWはそれぞれ独立に、置換基を有していてもよい、芳香族炭化水素環又は芳香族
複素環を表し、
R1´~R4´、R7´~R8´はそれぞれ独立に、水素原子、ハロゲン原子、置換基
を有していてもよいアルキル基、置換基を有していてもよいカルボキシル基、アルケニル
基、アルキニル基、置換基を有していてもよい、芳香族炭化水素環又は芳香族複素環を表
し、
X及びYは式(1)と同義である。
In equation (2)
V and W each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle which may have a substituent.
R 1'to R 4'and R 7'to R 8'independently each have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and a carboxyl group which may have a substituent. Represents an aromatic hydrocarbon ring or an aromatic heterocycle which may have an alkenyl group, an alkynyl group or a substituent.
X and Y are synonymous with equation (1).
V及びWはそれぞれ独立に、置換基を有していてもよい、芳香族炭化水素環又は芳香族
複素環を表す。具体的には、式(1)のR1~R8として挙げた置換基を有していてもよ
い、芳香族炭化水素環又は芳香族複素環と同義であり、好ましい範囲も同じである。
R1´~R4´、R7´~R8´はそれぞれ独立に、水素原子、ハロゲン原子、置換基
を有していてもよいアルキル基、置換基を有していてもよいカルボキシル基、アルケニル
基、アルキニル基、置換基を有していてもよい、芳香族炭化水素環又は芳香族複素環を表
す。具体的には、式(1)のR1~R8として挙げた各基又は環と同義であり、好ましい
範囲も同じである。
V and W each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle which may have a substituent. Specifically, it is synonymous with an aromatic hydrocarbon ring or an aromatic heterocycle which may have the substituents listed as R 1 to R 8 of the formula (1), and the preferable range is also the same.
R 1'to R 4'and R 7'to R 8'independently each have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and a carboxyl group which may have a substituent. Represents an aromatic hydrocarbon ring or an aromatic heterocycle which may have an alkenyl group, an alkynyl group or a substituent. Specifically, it has the same meaning as each group or ring listed as R 1 to R 8 in the formula (1), and the preferable range is also the same.
式(1)で表される化合物の質量平均分子量は特に限定されないが、10000以下で
あることが好ましい。ただし、樹脂などに担持させる場合は、その限りではない。
The mass average molecular weight of the compound represented by the formula (1) is not particularly limited, but is preferably 10,000 or less. However, this does not apply when the product is supported on a resin or the like.
式(1)で表される化合物の具体例を以下に示すが、これらに限定されるものではない
。
[式(1)で表される化合物の製造方法]
式(1)で表される化合物の製造方法は特に限定されず、公知の方法が適用できる。例
えば、Yong Ni and Jishan Wu, Org.Biomo.Chem.,2014, 12, 3774、Aurore Loudet and K
evin Burgess, Che. Rev.,2007, 107, 4891等が挙げられる。
[Method for producing a compound represented by the formula (1)]
The method for producing the compound represented by the formula (1) is not particularly limited, and a known method can be applied. For example, Yong Ni and Jishan Wu, Org.Biomo.Chem., 2014, 12, 3774, Aurora Loudet and K
evin Burgess, Che. Rev., 2007, 107, 4891 and the like.
[組成物]
式(1)で表される化合物は、式(3)で表される化合物と共に組成物として用いても
よい。
The compound represented by the formula (1) may be used as a composition together with the compound represented by the formula (3).
式(3)において、
V2及びW2はそれぞれ独立に、置換基を有していてもよい、芳香族炭化水素環又は芳
香族複素環を表し、
R21~R24、R27~R28はそれぞれ独立に、水素原子、ハロゲン原子、置換基
を有していてもよいアルキル基、置換基を有していてもよいカルボキシル基、アルケニル
基、アルキニル基、置換基を有していてもよい、芳香族炭化水素環又は芳香族複素環を表
す。
X2はN原子又はCR29を表し、
Y2はアルキニル基、F原子、OR20、置換基を有していてもよい、アルキル基、芳
香族炭化水素環又は芳香族複素環を表し、
R29は、水素原子、シアノ基、カルボニル基、カルボキシル基、ハロゲン原子、アル
キル基、アルキニル基、アルケニル基、アリール基、ヘテロアリール基、アルキルチオ基
、スルホニル基又はアミノ基を表し、アルキル基、アルキニル基、アルケニル基、アリー
ル基、ヘテロアリール基及びアミノ基は置換基を有していてもよく、
R20は、水素原子、カルボニル基、アルキル基、アリール基又はヘテロアリール基を
表し、アルキル基、アリール基及びヘテロアリール基は置換基を有していてもよい。
In equation (3)
V 2 and W 2 each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle which may have a substituent.
R 21 to R 24 and R 27 to R 28 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a carboxyl group which may have a substituent, an alkenyl group, and an alkynyl. Represents an aromatic hydrocarbon ring or an aromatic heterocycle which may have a group or a substituent.
X 2 represents N atom or CR 29
Y 2 represents an alkynyl group, an F atom, OR 20 , an alkyl group optionally having a substituent, an aromatic hydrocarbon ring or an aromatic heterocycle.
R 29 represents a hydrogen atom, a cyano group, a carbonyl group, a carboxyl group, a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkylthio group, a sulfonyl group or an amino group, and represents an alkyl group or an alkynyl group. The group, alkenyl group, aryl group, heteroaryl group and amino group may have a substituent.
R 20 represents a hydrogen atom, a carbonyl group, an alkyl group, an aryl group or a heteroaryl group, and the alkyl group, the aryl group and the heteroaryl group may have a substituent.
V2及びW2は式(2)のV、Wとそれぞれ同義であり、好ましい範囲も同義である。
R21~R24、R27~R28は式(2)のR1´~R4´、R7´~R8´とそれ
ぞれ同義であり、好ましい範囲も同義である。また、R29は式(2)のR9、R20は
式(2)のR10とそれぞれ同義であり、好ましい範囲も同義である。
Y2の置換基を有していてもよい、アルキル基、芳香族炭化水素環又は芳香族複素環は
、式(1)のYの置換基を有していてもよい、アルキル基、芳香族炭化水素環又は芳香族
複素環とそれぞれ同義であり、好ましい範囲も同義である。
V 2 and W 2 are synonymous with V and W in the formula (2), respectively, and the preferable range is also synonymous.
R 21 to R 24 and R 27 to R 28 are synonymous with R 1'to R 4'and R 7'to R 8'in the equation (2), respectively, and the preferable ranges are also synonymous. Further, R 29 has the same meaning as R 9 in the formula (2) and R 20 has the same meaning as R 10 in the formula (2), and the preferable range also has the same meaning.
The alkyl group, aromatic hydrocarbon ring or aromatic heterocycle which may have a substituent of Y 2 may have a substituent of Y of the formula (1), an alkyl group and an aromatic. They are synonymous with hydrocarbon rings or aromatic heterocycles, respectively, and the preferred range is also synonymous.
式(1)及び式(3)で表される化合物を含む組成物は、それぞれの化合物を混合して
組成物としてもよく、式(1)で表される化合物の製造時に式(3)で表される化合物も
同時に得ることができるため、両化合物を含む組成物として用いてもよい。
The composition containing the compounds represented by the formulas (1) and (3) may be mixed with each other to form a composition, which is represented by the formula (3) at the time of producing the compound represented by the formula (1). Since the represented compound can be obtained at the same time, it may be used as a composition containing both compounds.
[部材]
本発明の式(1)で表される化合物は、近赤外域以上に吸収・発光特性を有するもので
あり、例えば近赤外発光マーカー、インジケーター、バイオイメージング、センサー、波
長変換フィルム、発光トランジスター、OLED、電気化学発光セル、フォトダイナミッ
クセラピー、光美容、ナイトビジョンディスプレイ、セキュリティー、偽造防止用途、医
療診断薬、PDTなど医療分野等の部材として好適に用いることができる。
[Element]
The compound represented by the formula (1) of the present invention has absorption / emission characteristics in the near-infrared region or higher, and is, for example, a near-infrared emission marker, an indicator, bioimaging, a sensor, a wavelength conversion film, a light emitting transistor, and the like. It can be suitably used as a member in the medical field such as OLED, electrochemical light emitting cell, photodynamic therapy, photobeauty, night vision display, security, anti-counterfeiting application, medical diagnostic agent, and PDT.
2L容四頸反応器に、窒素気流下室温にて、水酸化ナトリウム(32.6g, 2.6equiv.)を精製
水(200mL)で撹拌溶解し、内温-14℃に冷却後、臭素(65.1g, 1.3equiv.)を内温-10℃以
下で40 分間掛けて滴下し、内温-14~-11℃で40 分間撹拌した。次いで、Ethyl DL-leu
cate 化合物1(50.19g, 0.3133mol)のジクロロメタン(200mL)溶液を、内温-9℃以下で2
6 分間掛けて滴下し、1 時間掛けて内温0℃まで昇温後、室温へ戻しながら一夜撹拌継続
した。
10%チオ硫酸ナトリウム水溶液(200mL)を注ぎquenchし、不溶物をCelite で吸引濾過し
、ジクロロメタンでリンスした。濾液の油水を分離し、水層をジクロロメタン(400mL)で
抽出した。2つのハロゲン層を合わせ、half-brine(200mL)で洗浄後、無水硫酸マグネシ
ウムで乾燥、ろ過し、ろ液を濃縮し褐色液体の粗体(70.0g)を得た。
この粗体をシリカゲルカラムクロマトグラフィー(ジクロロメタンで溶出)に附し、フラ
クションを回収、濃縮し、化合物2 (32.30g,無色透明液体,収率 65.2%)を得た。
Sodium hydroxide (32.6 g, 2.6 equiv.) Is stirred and dissolved in purified water (200 mL) in a 2 L volume four-neck reactor at room temperature under a nitrogen stream, cooled to an internal temperature of -14 ° C, and then bromine (65.1 g). , 1.3equiv.) Was added dropwise at an internal temperature of -10 ° C or lower for 40 minutes, and the mixture was stirred at an internal temperature of -14 to -11 ° C for 40 minutes. Then Ethyl DL-leu
cate A solution of compound 1 (50.19 g, 0.3133 mol) in dichloromethane (200 mL) at an internal temperature of -9 ° C or lower is 2
The mixture was dropped over 6 minutes, heated to an internal temperature of 0 ° C over 1 hour, and then stirred overnight while returning to room temperature.
A 10% aqueous sodium thiosulfate solution (200 mL) was poured and quenched, and the insoluble material was suction filtered with Celite and rinsed with dichloromethane. The oily water of the filtrate was separated and the aqueous layer was extracted with dichloromethane (400 mL). The two halogen layers were combined, washed with half-brine (200 mL), dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated to obtain a crude brown liquid (70.0 g).
This crude material was subjected to silica gel column chromatography (eluted with dichloromethane), and the fraction was recovered and concentrated to obtain Compound 2 (32.30 g, colorless transparent liquid, yield 65.2%).
250mL 容四頸反応器に、窒素気流下室温にて、2,3-dihydroxynaphthalene 化合物3 (
18.40g,0.114mol)のエタノール(6.1mL)懸濁液に、抱水ヒドラジン(18.4mL, 3.3equiv.)、
硫酸ヒドラジニウム(6.13g, 0.41equiv.)を加え、4 時間還流撹拌した。
室温へ冷却後、エタノール(64mL)を加え、氷浴にて1 時間冷却撹拌した。乾燥窒素気流
下結晶を吸引濾取し、エタノール(64mL)でリンスし、乾燥窒素気流下10 分間通風乾燥し
、粗体の化合物4 (13.4g,微褐色粉体, 収率 62.0%)を得た。
In a 250 mL four-neck reactor, at room temperature under a nitrogen stream, 2,3-dihydroxynaphthalene compound 3 (
In a suspension of 18.40 g, 0.114 mol) of ethanol (6.1 mL), hydrazine hydrate (18.4 mL, 3.3 equiv.),
Hydrazinium sulfate (6.13 g, 0.41 equiv.) Was added, and the mixture was stirred under reflux for 4 hours.
After cooling to room temperature, ethanol (64 mL) was added, and the mixture was cooled and stirred in an ice bath for 1 hour. Crystals were collected by suction filtration under a dry nitrogen stream, rinsed with ethanol (64 mL), and air-dried for 10 minutes under a dry nitrogen stream to obtain crude compound 4 (13.4 g, light brown powder, yield 62.0%). rice field.
2L容四頸反応器に、窒素気流下室温にて、化合物4(13.40g, 71.19mmol)をエタノール(
500mL)に撹拌溶解し、ケトエステル2(33.90g, 3.01equiv.)を加え、24 時間還流撹拌し
た。室温へ冷却後、エタノールを減圧留去し、粗体の化合物5 (44.3g)を得た。
In a 2 L volume four-neck reactor, add compound 4 (13.40 g, 71.19 mmol) to ethanol (13.40 g, 71.19 mmol) at room temperature under a nitrogen stream.
The mixture was stirred and dissolved in 500 mL), ketoester 2 (33.90 g, 3.01 equiv.) Was added, and the mixture was stirred under reflux for 24 hours. After cooling to room temperature, ethanol was distilled off under reduced pressure to obtain crude compound 5 (44.3 g).
2L容四頸反応器に、窒素気流下室温にて、5(44.30g, <71.19mmol)をエタノール(712mL)
に撹拌溶解し、p-トルエンスルホン酸一水和物(135.4g, 10.0equiv.)を加え、5 時間還流
撹拌した。室温へ冷却後、エタノールを減圧留去し、酢酸エチル(500mL)と精製水(200mL)
を注ぎ、暫く撹拌後、油水を分離し、水層を酢酸エチル(500mL)で抽出した。2つの有機
層を合わせ、精製水(300mL)、brine(200mL)で順次洗浄後、無水芒硝乾燥、ろ過し、ろ液
を濃縮し、褐色粘体の粗体(41.9g)を得た。この粗体をシリカゲルカラムクロマトグラフ
ィー(酢酸エチル/ヘキサン=1/4 )に附し、フラクションを回収、濃縮し、化合物6 (8.
80g,黄土色固体,収率 28.4%)を得た。
In a 2 L volume four-neck reactor, add 5 (44.30 g, <71.19 mmol) to ethanol (712 mL) at room temperature under a nitrogen stream.
The mixture was stirred and dissolved, p-toluenesulfonic acid monohydrate (135.4 g, 10.0equiv.) Was added, and the mixture was stirred under reflux for 5 hours. After cooling to room temperature, ethanol was distilled off under reduced pressure, and ethyl acetate (500 mL) and purified water (200 mL) were distilled off.
After pouring and stirring for a while, the oil and water were separated, and the aqueous layer was extracted with ethyl acetate (500 mL). The two organic layers were combined, washed successively with purified water (300 mL) and brine (200 mL), dried over anhydrous Glauber's salt and filtered, and the filtrate was concentrated to obtain a crude brown viscous body (41.9 g). This crude material was subjected to silica gel column chromatography (ethyl acetate / hexane = 1/4), fractions were collected and concentrated, and compound 6 (8.
80 g, ocher solid, yield 28.4%) was obtained.
500mL 容四頸反応器に窒素気流下室温にて、化合物6(8.80g, 20.25mmol)をエチレング
リコール(176mL)に撹拌溶解し、水酸化ナトリウム(5.35g, 6.6equiv.)を加え、3 時間還
流撹拌した。
室温へ冷却後、精製水(400mL)を加え、ジクロロメタン(400mL×2 回)抽出した。2つの
有機層を合わせ、精製水(200mL)、brine(100mL)で順次洗浄後、無水芒硝乾燥、ろ過し、
ろ液を濃縮し、褐色粘体の粗体(20.9g)を得た。この粗体をシリカゲルカラムクロマトグ
ラフィー(ジクロロメタンで溶出)に附し、フラクションを回収、濃縮し、化合物7 (2.49
g,黄土色固体,収率 42.3%)を得た。
Compound 6 (8.80 g, 20.25 mmol) was stirred and dissolved in ethylene glycol (176 mL) in a 500 mL four-necked reactor at room temperature under a nitrogen stream, and sodium hydroxide (5.35 g, 6.6 equiv.) Was added for 3 hours. The mixture was refluxed and stirred.
After cooling to room temperature, purified water (400 mL) was added, and dichloromethane (400 mL × 2 times) was extracted. The two organic layers are combined, washed sequentially with purified water (200 mL) and brine (100 mL), dried over anhydrous Glauber's salt, and filtered.
The filtrate was concentrated to give a crude brown viscous body (20.9 g). This crude was subjected to silica gel column chromatography (eluted with dichloromethane) to recover and concentrate fractions to compound 7 (2.49).
g, ocher solid, yield 42.3%) was obtained.
500mL 容四頸反応器に窒素気流下室温にて、化合物7(2.480g, 2.0equiv.)をジクロロ
メタン(248mL)に撹拌溶解し、オルト蟻酸トリエチル(1.266g, 2.0equiv.)を加え氷冷撹拌
とし、オキシ塩化燐(655mg, 4.270mmol)のジクロロメタン(2mL)溶液を滴下した。
室温へ戻しながら一夜撹拌後、精製水(100mL)を加えquench し油水を分離した。有機層
を減圧濃縮し、残渣をシリカゲルカラムクロマトグラフィー(ジクロロメタンで溶出)に附
し、フラクションを回収、濃縮し、化合物8(1.680g,暗緑色粘体固体,収率 62.7%)を得た
。
Compound 7 (2.480 g, 2.0 equiv.) Is stirred and dissolved in dichloromethane (248 mL) in a 500 mL four-neck reactor at room temperature under a nitrogen stream, triethyl orthoate (1.266 g, 2.0 equiv.) Is added, and ice-cooled stirring is performed. Then, a solution of phosphorus oxychloride (655 mg, 4.270 mmol) in dichloromethane (2 mL) was added dropwise.
After stirring overnight while returning to room temperature, purified water (100 mL) was added and quenched to separate the oily water. The organic layer was concentrated under reduced pressure, the residue was subjected to silica gel column chromatography (eluted with dichloromethane), and the fraction was recovered and concentrated to obtain Compound 8 (1.680 g, dark green viscous solid, yield 62.7%).
1L 容四頸反応器に窒素気流下室温にて、化合物8(1.656g, 2.640mmol)をジクロロメタ
ン(330mL)に溶解し氷冷撹拌とし、トリエチルアミン(11.0mL, 30equiv.)を滴下し10 分間
撹拌した。次いで三弗化硼素ジエチルエーテル錯体(14.9mL, 45equiv.)を13 分間掛けて
滴下し、室温へ戻しながら一夜撹拌継続した。ジクロロメタン(140mL)で希釈した後、再
度氷冷撹拌とし、希塩酸(160mL)を注ぎquenchした。油水を分離し、無水芒硝乾燥後、濾
過、濾液を濃縮し、黒緑色ペースト状物の粗体(14.7g)を得た。その粗体をシリカゲルカ
ラムクロマトグラフィー(ジクロロメタン/ヘキサン=1/4)に附し、フラクションを回収
、濃縮し、NIR-Ir-10 (723mg,暗緑色固体,収率 42.9%)を得た。NIR-Ir-10は式(1)及び
式(3)で表される化合物の混合物であった。
また、NIR-Ir-10の各蛍光固定波長における励起スペクトル、発光スペクトル及び吸収
スペクトルの測定を行った。測定結果を図1~3に示す。なお、各測定は以下のように実
施した。
励起スペクトル:日本分光株式会社の紫外可視近赤外分光光度計FP-8700を用い、10
-5mol/Lの脱気した塩化メチレン溶液を調液し、蛍光固定波長を設定し測定した。
吸収スペクトル:日立製作所のU3900分光光度計を用い、10-5mol/Lの脱
気した塩化メチレン溶液を調液し測定した
発光スペクトル:日本分光株式会社の紫外可視近赤外分光光度計FP-8700を用い、10
-5mol/Lの脱気した塩化メチレン溶液を調液し、測定した。日本分光株式会社の紫
外可視近赤外分光光度計FP-8700を用い、10-5mol/Lの脱気した塩化メチレン溶液
を調液し、固定波長を設定し測定した。
In a 1 L volume four-necked reactor at room temperature under a nitrogen stream, compound 8 (1.656 g, 2.640 mmol) was dissolved in dichloromethane (330 mL) and stirred on ice, and triethylamine (11.0 mL, 30 equiv.) Was added dropwise and stirred for 10 minutes. did. Then, boron trifluoride diethyl ether complex (14.9 mL, 45equiv.) Was added dropwise over 13 minutes, and stirring was continued overnight while returning to room temperature. After diluting with dichloromethane (140 mL), the mixture was stirred again with ice cold, and dilute hydrochloric acid (160 mL) was poured and quenched. The oil and water were separated, dried over anhydrous Glauber's salt, filtered, and the filtrate was concentrated to obtain a crude black-green paste (14.7 g). The crude material was subjected to silica gel column chromatography (dichloromethane / hexane = 1/4), and fractions were collected and concentrated to obtain NIR-Ir-10 (723 mg, dark green solid, yield 42.9%). NIR-Ir-10 was a mixture of compounds represented by the formulas (1) and (3).
In addition, the excitation spectrum, emission spectrum, and absorption spectrum of each fluorescence fixed wavelength of NIR-Ir-10 were measured. The measurement results are shown in FIGS. 1 to 3. Each measurement was carried out as follows.
Excitation spectrum: Using the ultraviolet-visible near-infrared spectrophotometer FP-8700 manufactured by JASCO Corporation, 10
A degassed methylene chloride solution of -5 mol / L was prepared, and a fixed fluorescence wavelength was set for measurement.
Absorption spectrum: Using a U3900 spectrophotometer manufactured by Hitachi, Ltd., a degassed methylene chloride solution of 10-5 mol / L was prepared and measured. Using 10
A -5 mol / L degassed methylene chloride solution was prepared and measured. Using an ultraviolet-visible near-infrared spectrophotometer FP-8700 manufactured by JASCO Corporation, a degassed methylene chloride solution of 10-5 mol / L was prepared, and a fixed wavelength was set for measurement.
Claims (3)
R1~R8はそれぞれ独立に、水素原子、ハロゲン原子、置換基を有していてもよいア
ルキル基、置換基を有していてもよいカルボキシル基、アルケニル基、アルキニル基、置
換基を有していてもよい、芳香族炭化水素環又は芳香族複素環を表し、
R1~R8はそれぞれ隣接する基同士と結合し環を形成していてもよく、
XはN原子又はCR9を表し、
Yはアルキニル基、F原子、OR10、置換基を有していてもよい、アルキル基、芳香
族炭化水素環又は芳香族複素環を表し、
R9は、水素原子、シアノ基、カルボニル基、カルボキシル基、ハロゲン原子、アルキ
ル基、アルキニル基、アルケニル基、アリール基、ヘテロアリール基、アルキルチオ基、
スルホニル基又はアミノ基を表し、アルキル基、アルキニル基、アルケニル基、アリール
基、ヘテロアリール基及びアミノ基は置換基を有していてもよく、
R10は、水素原子、カルボニル基、アルキル基、アリール基又はヘテロアリール基を
表し、アルキル基、アリール基及びヘテロアリール基は置換基を有していてもよい。] A compound represented by the formula (1).
Each of R 1 to R 8 independently has a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a carboxyl group which may have a substituent, an alkenyl group, an alkynyl group, and a substituent. Represents an aromatic hydrocarbon ring or an aromatic heterocycle which may be
R 1 to R 8 may be bonded to adjacent groups to form a ring.
X represents N atom or CR 9 and represents
Y represents an alkynyl group, an F atom, an OR 10 , an alkyl group optionally having a substituent, an aromatic hydrocarbon ring or an aromatic heterocycle.
R 9 is a hydrogen atom, a cyano group, a carbonyl group, a carboxyl group, a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkylthio group,
Representing a sulfonyl group or an amino group, an alkyl group, an alkynyl group, an alkenyl group, an aryl group, a heteroaryl group and an amino group may have a substituent.
R 10 represents a hydrogen atom, a carbonyl group, an alkyl group, an aryl group or a heteroaryl group, and the alkyl group, the aryl group and the heteroaryl group may have a substituent. ]
V及びWはそれぞれ独立に、置換基を有していてもよい、芳香族炭化水素環又は芳香族
複素環を表し、
R1‘~R4‘、R7´~R8´はそれぞれ独立に、水素原子、ハロゲン原子、置換基
を有していてもよいアルキル基、置換基を有していてもよいカルボキシル基、アルケニル
基、アルキニル基、置換基を有していてもよい、芳香族炭化水素環又は芳香族複素環を表
し、
X及びYは式(1)と同義である。] The compound according to claim 1, which is represented by the formula (2).
V and W each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle which may have a substituent.
R 1'to R 4'and R 7'to R 8'independently each have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and a carboxyl group which may have a substituent. Represents an aromatic hydrocarbon ring or an aromatic heterocycle which may have an alkenyl group, an alkynyl group or a substituent.
X and Y are synonymous with equation (1). ]
である、組成物。
V2及びW2はそれぞれ独立に、置換基を有していてもよい、芳香族炭化水素環又は芳
香族複素環を表し、
R21~R24、R27~R28はそれぞれ独立に、水素原子、ハロゲン原子、置換基
を有していてもよいアルキル基、置換基を有していてもよいカルボキシル基、アルケニル
基、アルキニル基、置換基を有していてもよい、芳香族炭化水素環又は芳香族複素環を表
し、
X2はN原子又はCR29を表し、
Y2はアルキニル基、F原子、OR20、置換基を有していてもよい、アルキル基、芳
香族炭化水素環又は芳香族複素環を表し、
R29は、水素原子、シアノ基、カルボニル基、カルボキシル基、ハロゲン原子、アル
キル基、アルキニル基、アルケニル基、アリール基、ヘテロアリール基、アルキルチオ基
、スルホニル基又はアミノ基を表し、アルキル基、アルキニル基、アルケニル基、アリー
ル基、ヘテロアリール基及びアミノ基は置換基を有していてもよく、
R20は、水素原子、カルボニル基、アルキル基、アリール基又はヘテロアリール基を
表し、アルキル基、アリール基及びヘテロアリール基は置換基を有していてもよい。] A composition comprising the compound represented by the formula (1) and the compound represented by the formula (3) according to claim 1.
V 2 and W 2 each independently represent an aromatic hydrocarbon ring or an aromatic heterocycle which may have a substituent.
R 21 to R 24 and R 27 to R 28 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a carboxyl group which may have a substituent, an alkenyl group, and an alkynyl. Represents an aromatic hydrocarbon ring or an aromatic heterocycle that may have a group, a substituent,
X 2 represents N atom or CR 29
Y 2 represents an alkynyl group, an F atom, OR 20 , an alkyl group optionally having a substituent, an aromatic hydrocarbon ring or an aromatic heterocycle.
R 29 represents a hydrogen atom, a cyano group, a carbonyl group, a carboxyl group, a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkylthio group, a sulfonyl group or an amino group, and represents an alkyl group or an alkynyl group. The group, alkenyl group, aryl group, heteroaryl group and amino group may have a substituent.
R 20 represents a hydrogen atom, a carbonyl group, an alkyl group, an aryl group or a heteroaryl group, and the alkyl group, the aryl group and the heteroaryl group may have a substituent. ]
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