JP2012176924A - Bisbinaphthylacetylene compound, method for producing the same, luminescent material for electroluminescent element, and fluorescent pigment - Google Patents
Bisbinaphthylacetylene compound, method for producing the same, luminescent material for electroluminescent element, and fluorescent pigment Download PDFInfo
- Publication number
- JP2012176924A JP2012176924A JP2011041938A JP2011041938A JP2012176924A JP 2012176924 A JP2012176924 A JP 2012176924A JP 2011041938 A JP2011041938 A JP 2011041938A JP 2011041938 A JP2011041938 A JP 2011041938A JP 2012176924 A JP2012176924 A JP 2012176924A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- bisbinaphthylacetylene
- group
- producing
- atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 15
- 239000000049 pigment Substances 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 238000005401 electroluminescence Methods 0.000 claims description 13
- -1 acetylene compound Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- ZDWYFWIBTZJGOR-UHFFFAOYSA-N bis(trimethylsilyl)acetylene Chemical group C[Si](C)(C)C#C[Si](C)(C)C ZDWYFWIBTZJGOR-UHFFFAOYSA-N 0.000 claims description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 5
- 238000005259 measurement Methods 0.000 description 13
- 238000004949 mass spectrometry Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 description 1
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 description 1
- MBIZXFATKUQOOA-UHFFFAOYSA-N 1,3,4-thiadiazole Chemical group C1=NN=CS1 MBIZXFATKUQOOA-UHFFFAOYSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004672 ethylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MHJUNMARMFAUBI-UHFFFAOYSA-N n-phenyliminobenzamide Chemical compound C=1C=CC=CC=1C(=O)N=NC1=CC=CC=C1 MHJUNMARMFAUBI-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006252 n-propylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、新規なビスビナフチルアセチレン化合物、その製造方法及び、当該ビスビナフチルアセチレン化合物のエレクトロルミネッセンス素子用発光材料や蛍光顔料などへの用途に関する。 The present invention relates to a novel bisbinaphthylacetylene compound, a method for producing the same, and use of the bisbinaphthylacetylene compound as a light-emitting material for an electroluminescent element, a fluorescent pigment, and the like.
クリセン、アントラセン等の骨格を有する多環芳香族炭化水素化合物（ＰＡＨ）誘導体は有機エレクトロルミネッセンス（ＥＬ）素子や発光素子用の材料としての利用が注目されており、近年盛んに研究がなされている（例えば、特許文献１、２参照）。 Polycyclic aromatic hydrocarbon compounds (PAH) derivatives having a skeleton such as chrysene and anthracene are attracting attention as materials for organic electroluminescence (EL) elements and light-emitting elements, and have been actively studied in recent years. (For example, refer to Patent Documents 1 and 2).
このようなＥＬ素子や発光素子用の材料、あるいは蛍光顔料などへ用途展開するにあたり、当該用途に最適な構造を有した材料を取得する必要があり、その中で新規の多環芳香族炭化水素化合物（ＰＡＨ）誘導体の開発に有用な化合物の合成は上記材料の候補化合物として提案できるものである。 In developing applications for materials for such EL elements and light-emitting elements, or fluorescent pigments, it is necessary to obtain materials having a structure optimal for the application, among which new polycyclic aromatic hydrocarbons are required. Synthesis of compounds useful for the development of compound (PAH) derivatives can be proposed as candidate compounds for the above materials.
上記クリセンやアントラセンは安価に大型の有機ＥＬを生産するには不向きで、これに代わる高分子材料（インク材料）が検討されている。しかしながら、高分子材料を用いると、有機ＥＬは電子輸送層 / 発光層 / 正孔輸送層のヘテロ構造を有しているが、各層間の材料同士が溶解しやすくなってしまうという課題が存在する。 The above-mentioned chrysene and anthracene are not suitable for producing large-sized organic EL at low cost, and polymer materials (ink materials) as alternatives are being studied. However, when a polymer material is used, the organic EL has a heterostructure of an electron transport layer / a light emitting layer / a hole transport layer, but there is a problem that the materials between the layers are easily dissolved. .
本発明の目的は、新規の多環芳香族炭化水素化合物（ＰＡＨ）誘導体の開発に有用な新規なビスビナフチルアセチレン化合物とその製造方法を提供することにあり、このような化合物の入手が可能となれば、エレクトロルミネッセンス（ＥＬ）素子用発光材料や蛍光顔料などへの用途に向けた研究開発が活発化されることが期待できる。 An object of the present invention is to provide a novel bisbinaphthylacetylene compound useful for the development of a novel polycyclic aromatic hydrocarbon compound (PAH) derivative and a method for producing the same, and the availability of such a compound. Then, it can be expected that research and development for applications to light emitting materials for electroluminescent (EL) elements and fluorescent pigments will be activated.
本発明者らは、新規の多環芳香族炭化水素化合物（ＰＡＨ）合成に有用な中間体の創製を目指して鋭意検討した結果、本発明の２，２−ビス（ビナフチル）アセチレン誘導体を見出し、本発明を完成させるに至った。 As a result of intensive studies aimed at creating an intermediate useful for the synthesis of a novel polycyclic aromatic hydrocarbon compound (PAH), the present inventors have found the 2,2-bis (binaphthyl) acetylene derivative of the present invention, The present invention has been completed.
すなわち、本発明は下記化（１）で示される新規な２，２−ビス（ビナフチル）アセチレン誘導体、及びその製造方法に関する。 That is, the present invention relates to a novel 2,2-bis (binaphthyl) acetylene derivative represented by the following chemical formula (1) and a method for producing the same.
（化（１）中、Ｒ１〜Ｒ２６は各々独立して、水素原子、ハロゲン原子または、炭素数１〜１２のアルキル基、アルケニル基、アリール基のいずれかの置換基を示し、Ｒ１〜Ｒ２６は互いに炭素原子を介して結合していても良い。）で示されるビスビナフチルアセチレン化合物は、従来知られていない新規化合物である。 (In Chemical Formula (1), R 1 ~R 26 independently represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group having 1 to 12 carbon atoms, indicates one of the substituents of aryl group, R 1 -R 26 may be bonded to each other via a carbon atom.) The bisbinaphthylacetylene compound represented by the above formula is a novel compound that has not been known so far.
上記化（１）で示されるビスビナフチルアセチレン化合物は分子骨格内に三重結合を有するためその反応性は高く、付加反応等で三重結合部位に容易に置換基を導入することが可能である。 Since the bisbinaphthylacetylene compound represented by the above formula (1) has a triple bond in the molecular skeleton, its reactivity is high, and a substituent can be easily introduced into the triple bond site by an addition reaction or the like.
また、本発明は上記ビスビナフチルアセチレン化合物誘導体を含んでなるエレクトロルミネッセンス（ＥＬ）素子用発光材料や、ビスビナフチルアセチレン化合物誘導体を含んでなる蛍光顔料に関する。 The present invention also relates to a light-emitting material for an electroluminescence (EL) device comprising the bisbinaphthylacetylene compound derivative and a fluorescent pigment comprising the bisbinaphthylacetylene compound derivative.
上記化（１）で示される本発明に係るビスビナフチルアセチレン誘導体化合物において、化（１）中のＲ１〜Ｒ２６で水素原子を除いた置換基としては、例えばフェニル基、ナフチル基、ビフェニル基、チエニル基、フリル基、ピリジン基、ピリミジン基、ピラジン基、ピリダジン基、トリアジン基、ピロール基、ピロゾール基、イミダゾール基、１，２，３−トリアゾール基、１，２，４−トリアゾール基、チアゾール基、オキサゾール基、１，２，３−オキサジアゾール基、１，３，４−チアジアゾール基、イソベンゾフラニル基などの芳香族基が挙げられる。これらの芳香族基は、必要に応じて置換基を有していてもよい。その他の置換基としてはフッ素原子、塩素原子、臭素原子、ヨウ素原子、シアノ基、ニトロ基、カルボキシル基、アミノ基、Ｎ―アルキルアミノ基、Ｎ，Ｎ−ジアルキルアミノ基、炭素数が１〜１２の直鎖、分岐あるいは環状アルキル基（メチル基、エチル基、ｎ−プロピル基、ｉｓｏ―プロピル基、ｔｅｒｔ―ブチル基、ｎ−オクチル基、シクロプロピル基など）、炭素数１〜１２の直鎖あるいは分岐アルキルオキシ基（メチルカルボニル基、エチルカルボニル基、ｎ−プロピルカルボニル基など）、炭素数直１〜１２の鎖あるいは分岐アルキルオキシカルボニル基（メチルオキシカルボニル基、エチルオキシカルボニル基など）などが挙げられる。 In the bisbinaphthylacetylene derivative compound according to the present invention represented by the above chemical formula (1), examples of the substituent in which R 1 to R 26 in the chemical formula (1) exclude a hydrogen atom include a phenyl group, a naphthyl group, and a biphenyl group. , Thienyl group, furyl group, pyridine group, pyrimidine group, pyrazine group, pyridazine group, triazine group, pyrrole group, pyrozole group, imidazole group, 1,2,3-triazole group, 1,2,4-triazole group, thiazole Groups, oxazole groups, 1,2,3-oxadiazole groups, 1,3,4-thiadiazole groups, and isobenzofuranyl groups. These aromatic groups may have a substituent if necessary. Other substituents include fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, carboxyl group, amino group, N-alkylamino group, N, N-dialkylamino group, 1 to 12 carbon atoms. Linear, branched or cyclic alkyl group (methyl group, ethyl group, n-propyl group, iso-propyl group, tert-butyl group, n-octyl group, cyclopropyl group, etc.), linear chain having 1 to 12 carbon atoms Or a branched alkyloxy group (such as a methylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group), a chain having 1 to 12 carbon atoms, or a branched alkyloxycarbonyl group (such as a methyloxycarbonyl group or an ethyloxycarbonyl group). Can be mentioned.
なおＲ１〜Ｒ２６は互いに炭素原子やヘテロ原子を介して結合していても良い。
上記化（１）で示される本発明に係るビスビナフチルアセチレン誘導体は化（２）に示すように１，１’―ビナフチル−２−トリフルオロメタンスルホン酸誘導体とビストリメチルシリルアセチレンとをパラジウム触媒下、１２０℃で反応させることにより容易に得ることができる。また、１，１’―ビナフチル−２−トリフルオロメタンスルホン酸誘導体はラセミ体を利用しても光学活性体を利用しても良い。
R 1 to R 26 may be bonded to each other via a carbon atom or a hetero atom.
As shown in the chemical formula (2), the bisbinaphthylacetylene derivative according to the present invention represented by the above chemical formula (1) comprises 1,1′-binaphthyl-2-trifluoromethanesulfonic acid derivative and bistrimethylsilylacetylene in the presence of a palladium catalyst. It can be easily obtained by reacting at ° C. The 1,1′-binaphthyl-2-trifluoromethanesulfonic acid derivative may be a racemate or an optically active substance.
また、本発明のビスビナフチルアセチレン誘導体は多環芳香族炭化水素化合物（ＰＡＨ）誘導体の開発に有用な中間体であるのみならず、その構造において縮環した芳香環が三重結合で結合した共役構造を有している。そのため、本発明のビスビナフチルアセチレン誘導体の一部は蛍光特性を有している。 Further, the bisbinaphthylacetylene derivative of the present invention is not only an intermediate useful for the development of polycyclic aromatic hydrocarbon compound (PAH) derivatives, but also a conjugated structure in which condensed aromatic rings are bonded by triple bonds in the structure. have. Therefore, some of the bisbinaphthylacetylene derivatives of the present invention have fluorescence characteristics.
すなわち、本発明に係るビスビナフチルアセチレン誘導体は蛍光材料としてエレクトロルミネッセンス（ＥＬ）素子用発光材料、特に、現在市場が求めている有機ＥＬディスプレイ用に、期待の持たれる化合物である。
また、本発明に係るビスビナフチルアセチレン誘導体は、蛍光顔料としても大いに期待の持たれる化合物である。
That is, the bisbinaphthylacetylene derivative according to the present invention is a promising compound for a light emitting material for an electroluminescence (EL) element, particularly for an organic EL display that is currently demanded by the market as a fluorescent material.
In addition, the bisbinaphthylacetylene derivative according to the present invention is a compound that has great expectations as a fluorescent pigment.
本発明は以下の効果を奏する。
（１）本発明のビスビナフチルアセチレン誘導体は多環芳香族炭化水素化合物（ＰＡＨ）誘導体の開発に有用な中間体である。
（２）本発明に係るビスビナフチルアセチレン誘導体は、有機ＥＬディスプレイ用などの蛍光材料として期待の持たれる化合物である。
（３）本発明に係るビスビナフチルアセチレン誘導体は、蛍光顔料として期待の持たれる化合物である。
The present invention has the following effects.
(1) The bisbinaphthylacetylene derivative of the present invention is an intermediate useful for the development of polycyclic aromatic hydrocarbon compound (PAH) derivatives.
(2) The bisbinaphthylacetylene derivative according to the present invention is a compound expected as a fluorescent material for organic EL displays.
(3) The bisbinaphthylacetylene derivative according to the present invention is a compound that is expected as a fluorescent pigment.
以下に本発明を実施例によってさらに詳細に説明するが、この実施例は本発明を限定するものではない。 The present invention will be described in more detail with reference to the following examples, but the examples are not intended to limit the present invention.
なお化合物の分析については下記の機器を使用して実施した。
［測定機器］
比旋光度測定は、ＪＡＳＣＯ製 ＤＩＰ−３７０（波長589 nm、ナトリウム D線）を用いて行なった。
１Ｈ−ＮＭＲ測定は、ＪＥＯＬ製 ＡＬ−４００を用いて行なった。
１３Ｃ−ＮＭＲ測定は、ＪＥＯＬ製 ＡＬ−４００を用いて行なった。
質量分析は、ＪＥＯＬ製 ＭＳ７００を使用しイオン化法をＥＩモードにて行なった。
赤外吸光測定は、ＪＡＳＣＯ製 ＦＴ／ＩＲ−４１００を用いて行なった。
In addition, about the analysis of the compound, it implemented using the following apparatus.
[measuring equipment]
The specific rotation was measured using DIP-370 (wavelength 589 nm, sodium D line) manufactured by JASCO.
1 H-NMR measurement was performed using AL-400 manufactured by JEOL.
13 C-NMR measurement was performed using AL-400 manufactured by JEOL.
For mass spectrometry, MS700 manufactured by JEOL was used, and the ionization method was performed in the EI mode.
The infrared absorption measurement was performed using FT / IR-4100 manufactured by JASCO.
実施例１ （-）−２，２−ｂｉｓ（ｂｉｎａｐｈｙｌ）ａｃｅｔｙｌｅｎｅの合成
（R）−１，１’−ビナフチル −２−トリフルオロメタンスルホン酸（２１８ｍｇ，０．５４ｍｍｏｌ）、ビストリメチルシリルアセチレン（１９４μｌ，０．８１ｍｍｏｌ）、酢酸パラジウム（１２ｍｇ，０．０５４ｍｍｏｌ）、トリシクロヘキシルホスフィンテトラフルオロボレート（４０ｍｇ，０．１１ｍｍｏｌ）、炭酸カリウム（１４９ｍｇ，１．０８ｍｍｏｌ）、炭酸銀（７５ｍｇ，０．２７ｍｍｏｌ）をシュレンク管に入れアルゴン雰囲気下、反応溶媒としてＮ，Ｎ−ジメチルアセトアミド（２ｍｌ）加え、１２０℃で２時間還流した。室温まで冷却後、ジエチルエーテルにて抽出を行い、飽和食塩水で洗浄した。
溶媒を除去し、残査をシリカゲルカラムクロマトグラフィー（ヘキサン／酢酸エチル＝２０／１）で精製することにより黄色結晶の表記化合物３９．１ｍｇ（２７％）を得た。
Example 1 Synthesis of (−)-2,2-bis (binaphyl) acetylene (R) -1,1′-binaphthyl-2-trifluoromethanesulfonic acid (218 mg, 0.54 mmol), bistrimethylsilylacetylene (194 μl, 0 .81 mmol), palladium acetate (12 mg, 0.054 mmol), tricyclohexylphosphine tetrafluoroborate (40 mg, 0.11 mmol), potassium carbonate (149 mg, 1.08 mmol), silver carbonate (75 mg, 0.27 mmol) in a Schlenk tube In an argon atmosphere, N, N-dimethylacetamide (2 ml) was added as a reaction solvent and refluxed at 120 ° C. for 2 hours. After cooling to room temperature, the mixture was extracted with diethyl ether and washed with saturated brine.
The solvent was removed, and the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 20/1) to obtain 39.1 mg (27%) of the title compound as yellow crystals.
得られた化合物について、図１、図２及び図３に示すように、比旋光度測定、１H-NMR測定、１３C-NMR測定、質量分析（ＭＳ）、赤外吸光測定を実施し、以下に示す結果を得た。この結果より、得られた化合物は（−）−２，２−ｂｉｓ（ｂｉｎａｐｈｙｌ）ａｃｅｔｙｌｅｎｅであることを確認した。 About the obtained compound, as shown in FIG. 1, FIG. 2 and FIG. 3, specific rotation measurement, 1 H-NMR measurement, 13 C-NMR measurement, mass spectrometry (MS), infrared absorption measurement were carried out, The following results were obtained. From this result, it was confirmed that the obtained compound was (−)-2,2-bis (binaphyl) acetylene.
分析結果
（比旋光度測定）
［α］Ｄ ２６ -２７６ （ｃ ０．３５， ＣＨＣｌ３）
（１Ｈ−ＮＭＲ測定）
１Ｈ−ＮＭＲ （４００ＭＨｚ， ＣＤＣｌ３）
δ ６．６５ （２Ｈ， ｄ， Ｊ ＝ ８．４ Ｈｚ）， ７．１６ （２Ｈ， ｄ， Ｊ ＝ ８．３ Ｈｚ）， ７．２１−７．２４ （６Ｈ， ｍ）， ７．３６−７．４１ （４Ｈ，
ｍ）， ７．４７ （２Ｈ， ｔ， Ｊ ＝ ７．３ Ｈｚ）， ７．５８ （２Ｈ， ｔ， Ｊ ＝ ７．３ Ｈｚ）， ７．６３ （２Ｈ， ｄ， Ｊ ＝ ８．３ Ｈｚ）， ７．７８ （２Ｈ，
ｄ， Ｊ ＝ ８．３ Ｈｚ）， ７．９７ （４Ｈ， ｄ， Ｊ ＝ ７．３２ Ｈｚ）
Analysis result (specific rotation measurement)
[Α] D 26 -276 (c 0.35, CHCl 3 )
(1 H-NMR measurement)
1 H-NMR (400 MHz, CDCl 3 )
δ 6.65 (2H, d, J = 8.4 Hz), 7.16 (2H, d, J = 8.3 Hz), 7.21-7.24 (6H, m), 7.36- 7.41 (4H,
m), 7.47 (2H, t, J = 7.3 Hz), 7.58 (2H, t, J = 7.3 Hz), 7.63 (2H, d, J = 8.3 Hz) , 7.78 (2H,
d, J = 8.3 Hz), 7.97 (4H, d, J = 7.32 Hz)
（１３Ｃ−ＮＭＲ測定）
１３Ｃ−ＮＭＲ （１００ＭＨｚ， ＣＤＣｌ３）
δ ９３．７３， １２１．４０， １２５．２５， １２５．６３， １２５．８７， １２６．２１， １２６．３５， １２６．４０， １２６．８０， １２７．３７，
１２７．８１， １２７．９４， １２８．０８， １２８．３５， １２８．４９， １３２．５２， １３２．６５， １３２．７２， １３３．４６， １３６．５８， １４０．４４
( 13C -NMR measurement)
13 C-NMR (100 MHz, CDCl 3 )
δ 93.73, 121.40, 125.25, 125.63, 125.87, 126.21, 126.35, 126.40, 126.80, 127.37,
127.81, 127.94, 128.08, 128.35, 128.49, 132.52, 132.65, 132.72, 133.46, 136.58, 140.44
（質量分析）
ＭＳ （ｒｅｌａｔｉｖｅ ｉｎｔｅｎｓｉｔｙ） ｍ／ｚ ５３０ （Ｍ＋， ９１）， ２６５ （１００），
ＨＲＭＳ ｃａｌｃｄ ｆｏｒ Ｃ４２Ｈ２６， ５３０．２０３４ ｆｏｕｎｄ ５３０．２０３０
(Mass spectrometry)
MS (relative intensity) m / z 530 (M +, 91), 265 (100),
HRMS calcd for C 42 H 26 , 530.034 found 530.030
（赤外吸光測定）
ＩＲ （ＫＢｒ） ３０５３， ２９１６， ２８４９ ｃｍ−１
(Infrared absorption measurement)
IR (KBr) 3053, 2916, 2849 cm -1
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011041938A JP5734703B2 (en) | 2011-02-28 | 2011-02-28 | Bisbinaphthylacetylene compound, process for producing the same, luminescent material for electroluminescent element, and fluorescent pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011041938A JP5734703B2 (en) | 2011-02-28 | 2011-02-28 | Bisbinaphthylacetylene compound, process for producing the same, luminescent material for electroluminescent element, and fluorescent pigment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012176924A true JP2012176924A (en) | 2012-09-13 |
| JP5734703B2 JP5734703B2 (en) | 2015-06-17 |
Family
ID=46979054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011041938A Active JP5734703B2 (en) | 2011-02-28 | 2011-02-28 | Bisbinaphthylacetylene compound, process for producing the same, luminescent material for electroluminescent element, and fluorescent pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5734703B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007530429A (en) * | 2003-07-15 | 2007-11-01 | スリーエム イノベイティブ プロパティズ カンパニー | Manufacturing method of semiconductor device and organic thin film transistor |
-
2011
- 2011-02-28 JP JP2011041938A patent/JP5734703B2/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007530429A (en) * | 2003-07-15 | 2007-11-01 | スリーエム イノベイティブ プロパティズ カンパニー | Manufacturing method of semiconductor device and organic thin film transistor |
Non-Patent Citations (5)
| Title |
|---|
| JPN6015001557; Ｌｉ， Ｃ．-Ｊ．， ｅｔ ａｌ．: Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ Ｖｏｌ． ３７， Ｎｏ． ２６, 1996, ｐｐ ４４５９-４４６２ * |
| JPN6015001561; Ｔａｙａｍａ， Ｅ． ｅｔ ａｌ．: Ｔｅｔｒａｈｅｄｒｏｎ Ｖｏｌ． ５８, 2002, ｐｐ ８３０７-８３１２ * |
| JPN6015001562; Ｇｉｌ-Ｍｏｌｔｏ， Ｊ．， ｅｔ ａｌ．: Ａｄｖ． Ｓｙｎｔｈ． Ｃａｔａｌ． Ｖｏｌ． ３４８, 2006, ｐｐ １８７４-１８８２ * |
| JPN7015000140; Ｗａｎｇ， Ｄ．， ｅｔ ａｌ．: Ｃｈｅｍ． Ｃｏｍｍｕｎ． , 1998, ｐｐ １７４７-１７４８ * |
| JPN7015000141; Ｍａｔｉｖｅｔｓｋｙ， Ｊ． Ｍ．， ｅｔ ａｌ．: Ａｄｖ． Ｆｕｎｃｔ． Ｍａｔｅｒ． Ｖｏｌ． １９, 2009, ｐｐ ２４８６-２４９４ * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5734703B2 (en) | 2015-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20210083134A (en) | Narrowband red phosphorescent tetradentate platinum(II) complexes | |
| JP5164902B2 (en) | Method for synthesizing 9-aryl-10-iodoanthracene derivative and method for synthesizing luminescent material | |
| JP5959171B2 (en) | PI-conjugated organoboron compound and method for producing the same | |
| CN102459149B (en) | Amine derivative and organic electroluminescent elements | |
| JP2012151149A (en) | Functional electronic element containing boron-containing compound | |
| JP2008056630A (en) | Phosphorus-cross-linked stilbene and method for producing the same | |
| JP4320434B2 (en) | Organoboron π-electron compound and material containing the same | |
| JP5147103B2 (en) | Method for synthesizing benzometall and novel diyne compound | |
| Hammerstroem et al. | Synthesis and characterization of luminescent 2, 7-disubstituted silafluorenes | |
| Lu et al. | Dithienylethene-bridged gold (I) isocyanide complexes: Synthesis, photochromism and “turn-on” fluorescent switching behavior | |
| CN111777614A (en) | Organic electroluminescent compound and application thereof | |
| JP5734703B2 (en) | Bisbinaphthylacetylene compound, process for producing the same, luminescent material for electroluminescent element, and fluorescent pigment | |
| Matsuura et al. | Synthesis and Optical Properties of C, N-Swapped Boranils Derived from Potassium Acyltrifluoroborates | |
| Nakashima et al. | Fluorescence and phosphorescence of a series of silicon-containing six-membered-ring molecules | |
| CN113583056A (en) | 6/5/6 tetradentate cyclometalated platinum or palladium complex luminescent material based on spirofluorene-spirofluorene structure and application thereof | |
| Wang et al. | A novel heteroterfluorene for efficient blue and white OLEDs | |
| WO2015199141A1 (en) | Coumalin-based condensed ring compound exhibiting luminescence/semiconductor properties, and method for manufacturing same | |
| JP6319888B2 (en) | Platinum complex and luminescent material containing the same | |
| JP5521210B2 (en) | Compound having triarylamine moiety and fused ring moiety, and production method thereof | |
| CN113201022A (en) | Small conjugated phosphorescent metal iridium (III) complex with isomer and preparation method and application thereof | |
| JP2010064976A (en) | New silole compound and method for producing the same | |
| CN110938017A (en) | Organic molecular material with long afterglow effect based on benzene ring unit and preparation method thereof | |
| JP4273180B2 (en) | Chiral arylene-linked dicarbazole derivatives and process for producing the same | |
| Gu et al. | Synthesis and characterization of 2′, 7′-diarylspiro [cyclopentane-1, 9′-fluorene] derivatives | |
| JP4139904B2 (en) | 9-substituted fluorene derivative and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140130 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150120 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150122 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150225 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150407 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150415 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5734703 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |