JP4035613B2 - Method for producing orthometalated iridium complex - Google Patents
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- 229910052741 iridium Inorganic materials 0.000 title claims description 56
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000013110 organic ligand Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 22
- -1 iridium halide Chemical class 0.000 claims description 12
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical class C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 claims description 10
- QLPKTAFPRRIFQX-UHFFFAOYSA-N 2-thiophen-2-ylpyridine Chemical class C1=CSC(C=2N=CC=CC=2)=C1 QLPKTAFPRRIFQX-UHFFFAOYSA-N 0.000 claims description 6
- LPCWDYWZIWDTCV-UHFFFAOYSA-N 1-phenylisoquinoline Chemical class C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 LPCWDYWZIWDTCV-UHFFFAOYSA-N 0.000 claims description 5
- 150000002397 1-phenylpyrazoles Chemical class 0.000 claims description 3
- NRSBAUDUBWMTGL-UHFFFAOYSA-N 2-(1-benzothiophen-2-yl)pyridine Chemical class S1C2=CC=CC=C2C=C1C1=CC=CC=N1 NRSBAUDUBWMTGL-UHFFFAOYSA-N 0.000 claims description 3
- PCFUWBOSXMKGIP-UHFFFAOYSA-N 2-benzylpyridine Chemical class C=1C=CC=NC=1CC1=CC=CC=C1 PCFUWBOSXMKGIP-UHFFFAOYSA-N 0.000 claims description 3
- VLRSADZEDXVUPG-UHFFFAOYSA-N 2-naphthalen-1-ylpyridine Chemical class N1=CC=CC=C1C1=CC=CC2=CC=CC=C12 VLRSADZEDXVUPG-UHFFFAOYSA-N 0.000 claims description 3
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 3
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical class C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 150000002504 iridium compounds Chemical class 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims 1
- WUHYYTYYHCHUID-UHFFFAOYSA-K iridium(3+);triiodide Chemical compound [I-].[I-].[I-].[Ir+3] WUHYYTYYHCHUID-UHFFFAOYSA-K 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000539 dimer Substances 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000002955 isolation Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002503 iridium Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WITMXBRCQWOZPX-UHFFFAOYSA-N 1-phenylpyrazole Chemical compound C1=CC=NN1C1=CC=CC=C1 WITMXBRCQWOZPX-UHFFFAOYSA-N 0.000 description 3
- KJNZQKYSNAQLEO-UHFFFAOYSA-N 2-(4-methylphenyl)pyridine Chemical compound C1=CC(C)=CC=C1C1=CC=CC=N1 KJNZQKYSNAQLEO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229940093475 2-ethoxyethanol Drugs 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 2
- 230000001815 facial effect Effects 0.000 description 2
- 238000007122 ortho-metalation reaction Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical class [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Description
本発明は、有機ＥＬ素子等に用いられる発光素子用材料として有用なトリスオルトメタル化イリジウム錯体（以下、単にオルトメタル化イリジウム錯体ともいう）の製造方法に関する。The present invention relates to a method for producing a trisorthometalated iridium complex (hereinafter, also simply referred to as an orthometalated iridium complex) useful as a light emitting element material used for an organic EL element or the like.
有機ＥＬ素子は次世代の携帯情報端末などのディスプレイ素子として注目されており、近年になって発光素子の材料開発が活発に進められるようになってきた。その中でも、トリス（２−フェニルピリジン）イリジウム錯体に代表されるオルトメタル化イリジウム錯体は、発光効率の観点から有望視されており、特に注目されている発光素子材料である。 Organic EL elements are attracting attention as display elements for next-generation portable information terminals and the like, and in recent years, material development of light-emitting elements has been actively promoted. Among them, ortho-metalated iridium complexes represented by tris (2-phenylpyridine) iridium complexes are promising from the viewpoint of light emission efficiency, and are light-emitting element materials that have attracted particular attention.
このオルトメタル化イリジウム錯体を、ハロゲン化イリジウムを原料に一段階で合成する方法としては、例えば、３塩化イリジウムと有機配位子を加熱還流下、２４時間反応させる方法が知られている（非特許文献１）。
この一段階合成法は下記の反応式（１）のように推定される多段階反応を一気に進めようとするものであるが、中間生成物である、ハロゲン配位子で架橋されたイリジウムダイマー（以下、架橋ダイマーともいう）の生成した段階で反応がほとんど進行しなくなるため、副生成物である架橋ダイマー（Ｄ−１）が多量に生成し、目的物であるオルトメタル化イリジウム錯体（Ａ−１）の収率が極めて低い等の問題点があった。
As a method for synthesizing this orthometalated iridium complex from iridium halide as a raw material in one step, for example, a method of reacting iridium trichloride and an organic ligand under heating under reflux for 24 hours is known (non- Patent Document 1).
In this one-step synthesis method, a multi-step reaction estimated as shown in the following reaction formula (1) is attempted at once, but an intermediate product, an iridium dimer crosslinked with a halogen ligand ( Hereinafter, the reaction hardly proceeds at the stage where the cross-linked dimer is generated), so that a large amount of the cross-linked dimer (D-1) as a by-product is generated and the ortho-metalated iridium complex (A-) as the target product is formed. There was a problem that the yield of 1) was extremely low.
このような副生成物の生成を抑制するために、脱ハロゲン化剤である銀塩の存在下で反応させる方法も提案されているが（非特許文献２）、吸湿性の銀塩を使用するために操作性が悪く、またこの方法では、生成した塩化銀とオルトメタル化イリジウム錯体を分離・精製する工程が新たに必要になるなどの問題があった。 In order to suppress the formation of such a by-product, a method of reacting in the presence of a silver salt which is a dehalogenating agent has been proposed (Non-patent Document 2), but a hygroscopic silver salt is used. Therefore, the operability is poor, and this method has a problem that a process for separating and purifying the generated silver chloride and the orthometalated iridium complex is newly required.
本発明は、上記従来技術の事情に鑑みなされたものであって、ハロゲン化イリジウムと有機配位子を反応させて、オルトメタル化イリジウム錯体を製造する方法において、副生成物である架橋ダイマーの生成を抑制し、一段階では合成困難とされていたオルトメタル化イリジウム錯体を、脱ハロゲン化剤を使用することなく高収率、高純度かつ短時間に製造し得る方法を提供することを目的とする。 The present invention has been made in view of the above-described prior art, and in a method for producing an orthometalated iridium complex by reacting an iridium halide with an organic ligand, a by-product of a crosslinked dimer is obtained. It is an object to provide a method capable of producing an ortho-metalated iridium complex, which has been difficult to synthesize in one step, with high yield, high purity and in a short time without using a dehalogenating agent. And
本発明者らは、上記課題を鋭意検討した結果、ハロゲン化イリジウム化合物と有機配位子とから一段階でオルトメタル化イリジウム錯体を製造する反応においては、反応系の有機配位子の物質量が極めて重要な因子となり、この有機配位子を化学量論的に大過剰用いると、意外にも反応が活性化され、反応時間が著しく短縮化されるだけでなく、副生成物である架橋ダイマーの生成を効果的に抑制できることを見いだし、本発明を完成するに至った。 As a result of intensive studies on the above problems, the present inventors have determined that the amount of organic ligand in the reaction system in the reaction of producing an orthometalated iridium complex from a halogenated iridium compound and an organic ligand in one step. Is an extremely important factor, and if this organic ligand is used in a large stoichiometric excess, the reaction is unexpectedly activated and the reaction time is notably shortened. It has been found that the production of dimers can be effectively suppressed, and the present invention has been completed.
この出願によれば、以下の発明が提供される。 According to this application, the following invention is provided.
（１）ハロゲン化イリジウムとイリジウム−窒素結合およびイリジウム−炭素結合を形成し得る２座有機配位子を反応させて、トリスオルトメタル化イリジウム錯体を製造する方法において、有機配位子の使用量をハロゲン化イリジウム化合物に対して化学量論的に３０当量以上とすることを特徴とするトリスオルトメタル化イリジウム錯体の製造方法。(1) In a method for producing a trisorthometalated iridium complex by reacting iridium halide with a bidentate organic ligand capable of forming an iridium-nitrogen bond and an iridium-carbon bond, the amount of the organic ligand used Is a stoichiometric amount of 30 equivalents or more with respect to the iridium halide compound. A method for producing a trisorthometalated iridium complex.
（２）該反応が、極性溶媒中、マイクロ波照射下で行なわれることを特徴とする（１）に記載のトリスオルトメタル化イリジウム錯体の製造方法。(2) The method for producing a trisorthometalated iridium complex according to (1), wherein the reaction is performed in a polar solvent under microwave irradiation.
（３）有機配位子が、２−フェニルピリジン誘導体、２−フェニルキノリン誘導体、７，８−ベンゾキノリン誘導体、２−（２−チエニル）ピリジン誘導体、１−フェニルピラゾール誘導体、１−フェニルイソキノリン誘導体、２−（２−ベンゾチオフェニル）ピリジン誘導体、２−ベンジルピリジン誘導体及び２−（１−ナフチル）ピリジン誘導体から選ばれる少なくとも一種の化合物であることを特徴とする（１）又は（２）に記載のトリスオルトメタル化イリジウム錯体の製造方法。(3) Organic ligand is 2-phenylpyridine derivative, 2-phenylquinoline derivative, 7,8-benzoquinoline derivative, 2- (2-thienyl) pyridine derivative, 1-phenylpyrazole derivative, 1-phenylisoquinoline derivative (1) or (2), characterized in that it is at least one compound selected from 2-, 2- (2-benzothiophenyl) pyridine derivatives, 2-benzylpyridine derivatives and 2- (1-naphthyl) pyridine derivatives. A process for producing the described trisorthometalated iridium complex.
本発明方法によれば、副生成物である架橋ダイマーの生成を抑制し、一段階では合成困難とされていたオルトメタル化イリジウム錯体を高収率、高純度かつ短時間に製造することができる。 According to the method of the present invention, it is possible to produce an orthometalated iridium complex, which has been difficult to synthesize in one step, in a high yield, high purity and in a short time by suppressing the formation of a crosslinked dimer as a by-product. .
本発明のトリスオルトメタル化イリジウム錯体（以下、単にオルトメタル化イリジウム錯体ともいう）の製造方法は、ハロゲン化イリジウム化合物とイリジウム−窒素結合およびイリジウム−炭素結合を形成し得る２座有機配位子を反応させて、オルトメタル化イリジウム錯体を製造するに当たり、当該有機配位子の使用量をハロゲン化イリジウムに対して化学量論的に３０当量以上とすることを特徴とする。 The method for producing a trisorthometalated iridium complex (hereinafter, also simply referred to as an orthometalated iridium complex) according to the present invention comprises a bidentate organic ligand capable of forming an iridium-nitrogen bond and an iridium-carbon bond with an iridium halide compound. In producing an orthometalated iridium complex, the amount of the organic ligand used is stoichiometrically 30 equivalents or more with respect to iridium halide.
原料ハロゲン化イリジウムとしては、３ハロゲン化イリジウム、４ハロゲン化イリジウム、６ハロゲン化イリジウムが好ましく使用される。このような化合物としては、例えば、（ＮＨ４）３ＩｒＣｌ６、（ＮＨ４）２ＩｒＣｌ６、Ｎａ３ＩｒＣｌ６、Ｎａ２ＩｒＣｌ６、Ｋ３ＩｒＣｌ６、Ｋ２ＩｒＣｌ６、（ＮＨ４）３ＩｒＢｒ６、（ＮＨ４）２ＩｒＢｒ６、Ｎａ３ＩｒＢｒ６、Ｎａ２ＩｒＢｒ６、（ＮＨ４）３ＩｒＩ６、（ＮＨ４）２ＩｒＩ６、Ｎａ３ＩｒＩ６、Ｎａ２ＩｒＩ６、ＩｒＣｌ３、ＩｒＢｒ３、ＩｒＩ３、ＩｒＣｌ４、ＩｒＢｒ４、ＩｒＩ４、Ｈ３ＩｒＣｌ６、Ｈ２ＩｒＣｌ６、などが挙げられる。これらのハロゲン化イリジウム化合物には結晶水もしくは結晶溶媒がついていても良く、該反応には水和物が好ましく用いられる。また、イリジウムの価数は、特に問わないが、３価と４価が好ましく、より望ましくは３価である。 As the raw material iridium halide, iridium trihalide, iridium tetrahalide, and iridium hexahalide are preferably used. Examples of such compounds include (NH 4 ) 3 IrCl 6 , (NH 4 ) 2 IrCl 6 , Na 3 IrCl 6 , Na 2 IrCl 6 , K 3 IrCl 6 , K 2 IrCl 6 , (NH 4 ) 3 IrBr 6, (NH 4) 2 IrBr 6, Na 3 IrBr 6, Na 2 IrBr 6, (NH 4) 3 IrI 6, (NH 4) 2 IrI 6, Na 3 IrI 6, Na 2 IrI 6, IrCl 3, IrBr 3 , IrI 3 , IrCl 4 , IrBr 4 , IrI 4 , H 3 IrCl 6 , H 2 IrCl 6 , and the like can be given. These iridium halide compounds may have crystal water or a crystal solvent, and hydrates are preferably used in the reaction. Further, the valence of iridium is not particularly limited, but trivalent and tetravalent are preferable, and more desirably trivalent.
本発明で用いる有機配位子は、イリジウム−窒素結合およびイリジウム−炭素結合からなる結合を少なくとも２つ形成し得る２座有機配位子である。The organic ligand used in the present invention is a bidentate organic ligand capable of forming at least two bonds composed of an iridium-nitrogen bond and an iridium-carbon bond.
このような配位子の例としては、例えば、２−フェニルピリジン誘導体、２−フェニルキノリン誘導体、７，８−ベンゾキノリン誘導体、２−（２−チエニル）ピリジン誘導体、１−フェニルピラゾール誘導体、１−フェニルイソキノリン誘導体、２−（２−ベンゾチオフェニル）ピリジン誘導体、２−ベンジルピリジン誘導体及び２−（１−ナフチル）ピリジン誘導体の他、国際公開第０１/０４１５１２号、国際公開第０２/１５６４５号、特許公開２００１-２４７８５９号に記載の有機配位子等を挙げることができる。 Examples of such ligands include, for example, 2-phenylpyridine derivatives, 2-phenylquinoline derivatives, 7,8-benzoquinoline derivatives, 2- (2-thienyl) pyridine derivatives, 1-phenylpyrazole derivatives, 1 -Phenylisoquinoline derivative, 2- (2-benzothiophenyl) pyridine derivative, 2-benzylpyridine derivative and 2- (1-naphthyl) pyridine derivative, as well as WO 01/041512 and WO 02/15645 And organic ligands described in Japanese Patent Publication No. 2001-247859.
有機配位子の使用量は、副生成物である架橋ダイマーの生成を抑制するために、ハロゲン化イリジウムに対し、化学量論的に３０当量以上、好ましくは５０当量以上、更に好ましくは１００当量以上とすることが必要である。有機配位子の使用量が３０当量未満であると、後記する比較例にみるように架橋ダイマーが多量に副生し、所望とするオルトメタル化イリジウム錯体の収率が低下する。このように、有機配位子の使用量をハロゲン化イリジウムに対して化学量論的に３０当量以上とした場合、副生ダイマーの生成量が効果的に抑制され、オルトメタル化イリジウム錯体が主生成物になることは、従来全く知られていない事柄であり、本発明者らの、数多くの緻密な実験の積み重ねによって初めて見いだされた新規な知見である。
本発明がこのような手段を講じることにより、副生ダイマーの生成量が効果的に抑制され、オルトメタル化イリジウム錯体が高収率、高純度、かつ短時間で得られる理由は、現時点では定かではないが、大過剰に添加した有機配位子が単に配位子として機能するだけでなく、塩基としても機能し、オルトメタル化反応における有機配位子からの脱プロトン過程を促進しているためと推定している。
The amount of the organic ligand used is stoichiometrically 30 equivalents or more, preferably 50 equivalents or more, more preferably 100 equivalents, relative to the iridium halide in order to suppress the formation of by-product crosslinked dimers. This is necessary. When the amount of the organic ligand used is less than 30 equivalents, a large amount of cross-linked dimer is by-produced as seen in Comparative Examples described later, and the yield of the desired orthometalated iridium complex is lowered. Thus, when the amount of the organic ligand used is stoichiometrically 30 equivalents or more with respect to the iridium halide, the amount of by-product dimer is effectively suppressed, and the orthometalated iridium complex is mainly used. Being a product is a matter that has never been known before, and is a new finding that has been found for the first time by the accumulation of numerous detailed experiments by the present inventors.
The reason why the production amount of the by-product dimer is effectively suppressed by taking such measures in the present invention, and the reason why the orthometalated iridium complex is obtained in a high yield, high purity, and in a short time is unclear at present. However, the organic ligand added in large excess not only functions as a ligand, but also functions as a base, promoting the deprotonation process from the organic ligand in the orthometalation reaction. For the reason.
また、本発明においては、加熱手段は特に制約されないが、反応を円滑するために、マイクロ波を照射することが好ましい。マイクロ波の照射時間は、マイクロ波反応装置の出力や有機配位子や用いる溶媒等に依存するが、１〜６０分が望ましく、より好ましくは１〜２０分である。マイクロ波の波長に特に制限はないが、２０００〜３０００ＭＨｚ、好ましくは２４００〜２５００ＭＨｚである。マイクロ波発振装置としては、市販されている従来公知の発振装置が全て適用できる。また、加熱手段として、オイルバス、マントルヒーター等を用いても良い。その場合の反応時間は、１〜２４時間が望ましく、より好ましくは１〜１０時間である。窒素雰囲気下、アルゴン雰囲気下で反応を行うのも好ましい。 In the present invention, the heating means is not particularly limited, but it is preferable to irradiate microwaves in order to facilitate the reaction. Although the microwave irradiation time depends on the output of the microwave reactor, the organic ligand, the solvent used, and the like, it is preferably 1 to 60 minutes, more preferably 1 to 20 minutes. Although there is no restriction | limiting in particular in the wavelength of a microwave, It is 2000-3000 MHz, Preferably it is 2400-2500 MHz. As the microwave oscillating device, all commercially available conventionally known oscillating devices can be applied. Moreover, you may use an oil bath, a mantle heater, etc. as a heating means. In this case, the reaction time is desirably 1 to 24 hours, and more preferably 1 to 10 hours. It is also preferable to carry out the reaction in a nitrogen atmosphere or an argon atmosphere.
本発明においては、該反応を更に円滑に進めるために、反応溶媒として、極性溶媒を用いることが望ましい。このような溶媒としては、メタノール、エタノール、１−プロパノール、エチレングリコール、グリセリン、２−メトキシエタノール、２−エトキシエタノール、Ｎ,Ｎ−ジメチルホルムアミドなどが挙げられるが、特に高沸点のエチレングリコール、グリセリン、２−メトキシエタノール、２−エトキシエタノール、Ｎ,Ｎ−ジメチルホルムアミド、もしくは、それらを含む混合溶媒を用いることが望ましい。最も好ましく用いられるのは、エチレングリコール、グリセリンである。 In the present invention, it is desirable to use a polar solvent as a reaction solvent in order to proceed the reaction more smoothly. Examples of such a solvent include methanol, ethanol, 1-propanol, ethylene glycol, glycerin, 2-methoxyethanol, 2-ethoxyethanol, N, N-dimethylformamide, etc., and particularly high-boiling ethylene glycol and glycerin. 2-methoxyethanol, 2-ethoxyethanol, N, N-dimethylformamide, or a mixed solvent containing them is desirable. Most preferably used are ethylene glycol and glycerin.
本発明の反応温度、反応圧力、反応時間は、使用する原料、マイクロ波の波長、溶媒などによって異なるが、通常、反応温度は２０〜３００℃、好ましくは１００〜２５０℃、さらに好ましくは１５０〜２５０℃、反応圧力は１〜３０ａｔｍ、好ましくは１〜５ａｔｍである。 The reaction temperature, reaction pressure, and reaction time of the present invention vary depending on the raw material used, the wavelength of the microwave, the solvent, etc., but the reaction temperature is usually 20 to 300 ° C., preferably 100 to 250 ° C., more preferably 150 to The reaction pressure is 250 ° C. and 1 to 30 atm, preferably 1 to 5 atm.
該反応においては、反応後の溶液を濃縮することにより、オルトメタル化イリジウム錯体の収率を上げることができ、また、大過剰に使用した有機配位子については、蒸留、分留、抽出、ろ過、洗浄、再結晶、カラムクロマトグラフィー等の操作を単独あるいは組み合わせることで、反応系から容易に分離回収し再利用することができる。 In the reaction, the yield of the orthometalated iridium complex can be increased by concentrating the solution after the reaction, and the organic ligand used in large excess is distilled, fractionated, extracted, By alone or in combination with operations such as filtration, washing, recrystallization, column chromatography, etc., they can be easily separated and recovered from the reaction system and reused.
本発明によって得られたオルトメタル化イリジウム錯体については、通常の後処理に従って処理した後、必要があれば精製してあるいは精製せずに高純度品とすることができる。後処理の方法としては、例えば、抽出、冷却、水または有機溶媒を添加することによる晶析、反応混合物からの溶媒を留去する操作等を単独あるいは組み合わせて行うことができる。精製の方法としては再結晶、蒸留、昇華あるいはカラムクロマトグラフィー等を単独あるいは組み合わせて行うことができる。 The orthometalated iridium complex obtained by the present invention can be made into a high-purity product after treatment according to ordinary post-treatment, and if necessary, purified or not purified. As a post-treatment method, for example, extraction, cooling, crystallization by adding water or an organic solvent, an operation of distilling off the solvent from the reaction mixture, and the like can be performed alone or in combination. As a purification method, recrystallization, distillation, sublimation, column chromatography or the like can be performed alone or in combination.
本発明により製造されるオルトメタル化イリジウム錯体については、フェイシャル型とメリジオナル型の異性体が存在するが、どちらの構造でも構わず、またそれらの混合体でも構わない。より好ましいのは、フェイシャル型のオルトメタル化イリジウム錯体である。 The orthometalated iridium complex produced according to the present invention includes facial and meridional isomers, either of which may be used, or a mixture thereof. More preferred is a facial ortho-metalated iridium complex.
本発明により製造されたオルトメタル化イリジウム錯体については、架橋ダイマーの含有率が極めて低く（または検出限界以下であり）、該イリジウム錯体を発光素子の発光層もしくは発光層を含む複数の有機化合物層に含有されることで、従来よりも発光効率や耐久性で優れた発光素子を得ることができる。 The orthometalated iridium complex produced according to the present invention has a very low content of cross-linked dimer (or is below the detection limit), and the iridium complex is a light emitting layer of a light emitting device or a plurality of organic compound layers including a light emitting layer By containing in, the light emitting element excellent in luminous efficiency and durability than before can be obtained.
以下に、本発明によって製造されるオルトメタル化イリジウム錯体の代表例を示すが、本発明はこれに限定されるものではない。
Below, although the representative example of the ortho metalation iridium complex manufactured by this invention is shown, this invention is not limited to this.
次に、本発明を実施例により詳細に説明する。 Next, the present invention will be described in detail with reference to examples.
実施例１（２−フェニルピリジンをＩｒＣｌ３・３Ｈ２Ｏに対し化学量論的に１００当量添加し、マイクロ波照射下で該反応を行なった場合）
ＩｒＣｌ３・３Ｈ２Ｏを５０ｍｇ、２−フェニルピリジンを２．２ｇ、エチレングリコール１５ｍｌをナスフラスコに入れた。このナスフラスコをマイクロ波発振装置（ＨＩＴＡＣＨＩ製、ＭＲ−２５０）に入れ、反応装置の上部には還流冷却管を取り付けた。還流冷却管の上部からはテフロン（登録商標）管を通じて、この溶液にアルゴンガスを２０分間通気した。その後、マイクロ波（２４５０ＭＨｚ）を５分間照射した。この溶液を室温まで冷却した後、アルゴンガスを止め、沈殿してきた黄色結晶をろ別し、水、ペンタンで洗浄した後、減圧乾燥した。プロトンＮＭＲ（５００ＭＨｚ）による分析の結果、得られた黄色結晶は所望のオルトメタル化イリジウム錯体（Ａ−１）であり、代表的な副生成物であるハロゲン配位子で架橋したイリジウムダイマーは全く検出されなかった。オルトメタル化イリジウム錯体（Ａ−１）の単離収率は６０％であった。
（Ａ−１）のプロトンＮＭＲデータ（重ジクロロメタン中）δ：7.92(d, 3H), 7.67(d,
3H), 7.65(dd, 3H), 7.57(d, 3H), 6.93(dd, 3H), 6.86(dd, 3H), 6.79(dd, 3H),
6.74(d, 3H).
Example 1 (when 2-phenylpyridine is added in a stoichiometric amount of 100 equivalents to IrCl 3 .3H 2 O and the reaction is performed under microwave irradiation)
50 mg of IrCl 3 .3H 2 O, 2.2 g of 2-phenylpyridine, and 15 ml of ethylene glycol were placed in an eggplant flask. This eggplant flask was placed in a microwave oscillator (manufactured by HITACHI, MR-250), and a reflux condenser was attached to the upper part of the reactor. From the top of the reflux condenser, argon gas was bubbled through this solution for 20 minutes through a Teflon (registered trademark) tube. Thereafter, microwaves (2450 MHz) were irradiated for 5 minutes. The solution was cooled to room temperature, then the argon gas was stopped, the precipitated yellow crystals were filtered off, washed with water and pentane, and then dried under reduced pressure. As a result of analysis by proton NMR (500 MHz), the obtained yellow crystal is the desired orthometalated iridium complex (A-1), and the iridium dimer crosslinked with a halogen ligand, which is a typical byproduct, is completely present. Not detected. The isolation yield of the orthometalated iridium complex (A-1) was 60%.
Proton NMR data of (A-1) (in deuterated dichloromethane) δ: 7.92 (d, 3H), 7.67 (d,
3H), 7.65 (dd, 3H), 7.57 (d, 3H), 6.93 (dd, 3H), 6.86 (dd, 3H), 6.79 (dd, 3H),
6.74 (d, 3H).
実施例２（２−フェニルピリジンを（ＮＨ４）３ＩｒＣｌ６に対し化学量論的に１００当量添加し、マイクロ波照射下で該反応を行なった場合）
（ＮＨ４）３ＩｒＣｌ６の水和物を６５ｍｇ、２−フェニルピリジンを２．２ｇ、エチレングリコール１５ｍｌをナスフラスコに入れた。このナスフラスコをマイクロ波発振装置（ＨＩＴＡＣＨＩ製、ＭＲ−２５０）に入れ、反応装置の上部には還流冷却管を取り付けた。還流冷却管の上部からはテフロン（登録商標）管を通じて、この溶液にアルゴンガスを２０分間通気した。その後、マイクロ波（２４５０ＭＨｚ）を５分間照射した。この溶液を室温まで冷却した後、アルゴンガスを止め、沈殿してきた黄色結晶をろ別し、水、ペンタンで洗浄した後、減圧乾燥した。プロトンＮＭＲ（５００ＭＨｚ）による分析の結果、得られた黄色結晶は所望のオルトメタル化イリジウム錯体（Ａ−１）であり、代表的な副生成物であるハロゲン配位子で架橋したイリジウムダイマーは全く検出されなかった。オルトメタル化イリジウム錯体（Ａ−１）の単離収率は６５％であった。
Example 2 (when 2-phenylpyridine is added in a stoichiometric amount of 100 equivalents to (NH 4 ) 3 IrCl 6 and the reaction is performed under microwave irradiation)
65 mg of (NH 4 ) 3 IrCl 6 hydrate, 2.2 g of 2-phenylpyridine, and 15 ml of ethylene glycol were placed in an eggplant flask. This eggplant flask was placed in a microwave oscillator (manufactured by HITACHI, MR-250), and a reflux condenser was attached to the upper part of the reactor. From the top of the reflux condenser, argon gas was bubbled through this solution for 20 minutes through a Teflon (registered trademark) tube. Thereafter, microwaves (2450 MHz) were irradiated for 5 minutes. The solution was cooled to room temperature, then the argon gas was stopped, the precipitated yellow crystals were filtered off, washed with water and pentane, and then dried under reduced pressure. As a result of analysis by proton NMR (500 MHz), the obtained yellow crystal is the desired orthometalated iridium complex (A-1), and the iridium dimer crosslinked with a halogen ligand, which is a typical byproduct, is completely present. Not detected. The isolation yield of the orthometalated iridium complex (A-1) was 65%.
実施例３及び４（３０等量以上）、比較例１〜３（３０当量未満）
実施例１において、２−フェニルピリジンの使用量を表２のように代えた以外は、実施例１と同様にして実験を行った。ただし、比較例４はマイクロ波の照射時間を３０分にした。その結果を表２に示す。なお、表２には実施例１及び２の結果と、後述の実施例５〜９の結果も併記した。
Examples 3 and 4 (30 equivalents or more), Comparative Examples 1 to 3 (less than 30 equivalents)
The experiment was performed in the same manner as in Example 1 except that the amount of 2-phenylpyridine used in Example 1 was changed as shown in Table 2. However, in Comparative Example 4, the microwave irradiation time was 30 minutes. The results are shown in Table 2. In Table 2, the results of Examples 1 and 2 and the results of Examples 5 to 9 described later are also shown.
実施例５（２−（ｐ−トリル）ピリジンをＩｒＣｌ３・３Ｈ２Ｏに対し、化学量論的に１００当量用いた場合）
実施例１において、２−フェニルピリジンを２−（ｐ−トリル）ピリジンに代え、合成実験を行った。オルトメタル化イリジウム錯体（Ａ−２）の単離収率は６７％であった。
Example 5 (when 2- (p-tolyl) pyridine is used in a stoichiometric amount of 100 equivalents with respect to IrCl 3 .3H 2 O)
In Example 1, 2-phenylpyridine was replaced with 2- (p-tolyl) pyridine, and a synthetic experiment was conducted. The isolation yield of the orthometalated iridium complex (A-2) was 67%.
実施例６（２−（２−チエニル）ピリジンをＩｒＣｌ３・３Ｈ２Ｏに対し、化学量論的に１００当量用いた場合）
実施例１において、２−フェニルピリジンを２−（２−チエニル）ピリジンに代え、合成実験を行った。オルトメタル化イリジウム錯体（Ａ−５）の単離収率は３６％であった。
Example 6 (when 2- (2-thienyl) pyridine is used in a stoichiometric amount of 100 equivalents with respect to IrCl 3 .3H 2 O)
In Example 1, 2-phenylpyridine was replaced with 2- (2-thienyl) pyridine, and a synthetic experiment was performed. The isolation yield of the orthometalated iridium complex (A-5) was 36%.
実施例７（１−フェニルピラゾールをＩｒＣｌ３・３Ｈ２Ｏに対し化学量論的に１００当量用いた場合）
実施例１において、有機配位子を１−フェニルピラゾールに代え、合成実験を行った。オルトメタル化イリジウム錯体（Ａ−１０）の単離収率は５７％であった。
Example 7 (when 1-phenylpyrazole is used in a stoichiometric amount of 100 equivalents with respect to IrCl 3 .3H 2 O)
In Example 1, the organic ligand was replaced with 1-phenylpyrazole, and a synthesis experiment was performed. The isolation yield of the orthometalated iridium complex (A-10) was 57%.
実施例８（有機配位子として７，８−ベンゾキノリンをＩｒＣｌ３・３Ｈ２Ｏに対し化学量論的に５０当量用いた場合）
実施例１において、有機配位子を７，８−ベンゾキノリンに代え、合成実験を行った。オルトメタル化イリジウム錯体（Ａ−７）の単離収率は８４％であった。
Example 8 (when 7,8-benzoquinoline is used as an organic ligand in a stoichiometric amount of 50 equivalents with respect to IrCl 3 .3H 2 O)
In Example 1, the organic ligand was replaced with 7,8-benzoquinoline, and a synthetic experiment was conducted. The isolation yield of the orthometalated iridium complex (A-7) was 84%.
実施例９（有機配位子をＩｒＣｌ３・３Ｈ２Ｏに対し化学量論的に１００当量添加し、オイルバスを用いて加熱し該反応を行なった場合）
ＩｒＣｌ３・３Ｈ２Ｏを１００ｍｇ、２−フェニルピリジンを４．４ｇ、エチレングリコール１５ｍｌを二口フラスコに入れ、この溶液にアルゴンガスを２０分間通気した。その後、オイルバスを用いてこの反応溶液を加熱還流（５時間）した。この溶液を室温まで冷却した後、アルゴンガスを止め、沈殿してきた黄色結晶をろ別し、水、ペンタンで洗浄した後、減圧乾燥した。オルトメタル化イリジウム錯体（Ａ−１）の単離収率は６８％であった。
Example 9 (when an organic ligand is added in a stoichiometric amount of 100 equivalents to IrCl 3 .3H 2 O and heated using an oil bath to carry out the reaction)
The IrCl 3 · 3H 2 O 100mg, placed 2-phenylpyridine 4.4 g, ethylene glycol 15ml in a two-neck flask, and argon gas was bubbled for 20 minutes into this solution. Thereafter, this reaction solution was heated to reflux (5 hours) using an oil bath. The solution was cooled to room temperature, then the argon gas was stopped, the precipitated yellow crystals were filtered off, washed with water and pentane, and then dried under reduced pressure. The isolation yield of the orthometalated iridium complex (A-1) was 68%.
1) ppyHは2-フェニルピリジン、tpyHは2-(p-トリル)ピリジン、thpyHは2-(2-チエニル)ピリジン、ppzHは1-フェニルピラゾール、bzqHは7,8-ベンゾキノリンをそれぞれ表す。
2) ハロゲン化イリジウムに対する有機配位子の使用量を表す。
3) (A)は目的物であるオルトメタル化イリジウム錯体を表し、(D)は架橋ダイマーを表す。
4) マイクロ波の照射時間を３０分にした。
5) オイルバスを用いた通常の加熱還流法で行った。
1) ppyH represents 2-phenylpyridine, tpyH represents 2- (p-tolyl) pyridine, thpyH represents 2- (2-thienyl) pyridine, ppzH represents 1-phenylpyrazole, and bzqH represents 7,8-benzoquinoline.
2) Represents the amount of organic ligand used relative to iridium halide.
3) (A) represents the ortho-metalated iridium complex as the target product, and (D) represents a crosslinked dimer.
4) The microwave irradiation time was 30 minutes.
5) It was carried out by a normal heating reflux method using an oil bath.
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|---|---|---|---|---|
| DE10325820A1 (en) * | 2003-06-07 | 2004-12-23 | Covion Organic Semiconductors Gmbh | Process for the production of high-purity, tris and bis-ortho-metallated organometallic compounds |
| DE10350606A1 (en) * | 2003-10-30 | 2005-06-09 | Covion Organic Semiconductors Gmbh | Process for the preparation of heteroleptic, ortho-metallated organometallic compounds |
| US6870054B1 (en) * | 2003-12-05 | 2005-03-22 | Eastman Kodak Company | Synthesis for organometallic cyclometallated transition metal complexes |
| JP5080729B2 (en) * | 2004-09-28 | 2012-11-21 | 富士フイルム株式会社 | Organic electroluminescence device |
| CN101263151B (en) | 2005-09-12 | 2011-09-07 | 新日铁化学株式会社 | Process for production of ortho-metallized complex of iridium with homoligand |
| DE102005057963A1 (en) * | 2005-12-05 | 2007-06-06 | Merck Patent Gmbh | Process for the preparation of ortho-metallated metal compounds |
| EP2471800B1 (en) | 2009-08-27 | 2014-01-15 | National Institute of Advanced Industrial Science And Technology | Iridium complex and light emitting material formed from same |
| JP2014214127A (en) * | 2013-04-26 | 2014-11-17 | 株式会社半導体エネルギー研究所 | Synthesis method for phosphorescent organic metal iridium complex |
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