CN103189469A - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents
Novel organic electroluminescent compounds and organic electroluminescent device using the same Download PDFInfo
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- CN103189469A CN103189469A CN2011800519605A CN201180051960A CN103189469A CN 103189469 A CN103189469 A CN 103189469A CN 2011800519605 A CN2011800519605 A CN 2011800519605A CN 201180051960 A CN201180051960 A CN 201180051960A CN 103189469 A CN103189469 A CN 103189469A
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- 0 Cc(cc1C)cc(C)c1N(c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2)c(cc1)ccc1-[n]1c(c(*2)c(cc3)-c4c2cccc4)c3c2ccccc12 Chemical compound Cc(cc1C)cc(C)c1N(c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2)c(cc1)ccc1-[n]1c(c(*2)c(cc3)-c4c2cccc4)c3c2ccccc12 0.000 description 2
- NQNOPDIJKLALEZ-UHFFFAOYSA-N Brc1ccc2c(c(C=CCC3)c3c(C3CC3)c3)c3[nH]c2c1 Chemical compound Brc1ccc2c(c(C=CCC3)c3c(C3CC3)c3)c3[nH]c2c1 NQNOPDIJKLALEZ-UHFFFAOYSA-N 0.000 description 1
- YYJFJRLAJZTKPC-UHFFFAOYSA-N CC(C)(C)c(cc1)ccc1N(c(cc1)ccc1-[n]1c2ccc(cccc3)c3c2c2c1C1Nc3ccccc3C1(C)C=C2)c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2 Chemical compound CC(C)(C)c(cc1)ccc1N(c(cc1)ccc1-[n]1c2ccc(cccc3)c3c2c2c1C1Nc3ccccc3C1(C)C=C2)c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2 YYJFJRLAJZTKPC-UHFFFAOYSA-N 0.000 description 1
- AZDOWZCSCFCREH-UHFFFAOYSA-N CC(C)(C)c(cc1)ccc1N(c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2)c(cc1)ccc1-[n](c1cc(Br)ccc11)c2c1c1ccccc1c(C1CC1)c2 Chemical compound CC(C)(C)c(cc1)ccc1N(c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2)c(cc1)ccc1-[n](c1cc(Br)ccc11)c2c1c1ccccc1c(C1CC1)c2 AZDOWZCSCFCREH-UHFFFAOYSA-N 0.000 description 1
- HELDQWQOEDQSEJ-UHFFFAOYSA-N CC(C)(C)c(cc1)ccc1N(c(cc1)ccc1N(C(C)(C1C=C2)C=C2c2ccccc2[N+]([O-])=O)c2c1c1ccccc1cc2)c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2 Chemical compound CC(C)(C)c(cc1)ccc1N(c(cc1)ccc1N(C(C)(C1C=C2)C=C2c2ccccc2[N+]([O-])=O)c2c1c1ccccc1cc2)c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2 HELDQWQOEDQSEJ-UHFFFAOYSA-N 0.000 description 1
- SIOYEXJSDABLRB-UHFFFAOYSA-N CC(C1)C(N(c2ccccc2)c(cc2)ccc2-[n]2c(c3c(cc4)-c(cccc5)c5SCC3)c4c3c2cccc3)=CC=C1[n]1c(cccc2)c2c2c1cccc2 Chemical compound CC(C1)C(N(c2ccccc2)c(cc2)ccc2-[n]2c(c3c(cc4)-c(cccc5)c5SCC3)c4c3c2cccc3)=CC=C1[n]1c(cccc2)c2c2c1cccc2 SIOYEXJSDABLRB-UHFFFAOYSA-N 0.000 description 1
- DMKDDHDLCQIGBD-UHFFFAOYSA-N CC12c(ccc(c3ccccc33)c4[n]3-c(cc3)ccc3N(c3ccccc3)c(cc3)cc5c3[s]c3ccccc53)c4OC1C=CC=C2 Chemical compound CC12c(ccc(c3ccccc33)c4[n]3-c(cc3)ccc3N(c3ccccc3)c(cc3)cc5c3[s]c3ccccc53)c4OC1C=CC=C2 DMKDDHDLCQIGBD-UHFFFAOYSA-N 0.000 description 1
- IGHMSLXMZADZDJ-UHFFFAOYSA-N C[BrH]c(ccc(Br)c1)c1[N+]([O-])=O Chemical compound C[BrH]c(ccc(Br)c1)c1[N+]([O-])=O IGHMSLXMZADZDJ-UHFFFAOYSA-N 0.000 description 1
- JFUNQQBLYFJSIM-UHFFFAOYSA-N [O-][N+](c1cc(Br)ccc1-c1cccc2ccccc12)=O Chemical compound [O-][N+](c1cc(Br)ccc1-c1cccc2ccccc12)=O JFUNQQBLYFJSIM-UHFFFAOYSA-N 0.000 description 1
- BDSZOXTYVXIAFH-UHFFFAOYSA-N c(cc1)ccc1N(c(cc1)ccc1-[n]1c(c2c(cc3)c(cccc4)c4[n]2-c2ccccc2)c3c2c1cccc2)c(cc1c2c3cccc2)ccc1[n]3-c1cccc2c1cccc2 Chemical compound c(cc1)ccc1N(c(cc1)ccc1-[n]1c(c2c(cc3)c(cccc4)c4[n]2-c2ccccc2)c3c2c1cccc2)c(cc1c2c3cccc2)ccc1[n]3-c1cccc2c1cccc2 BDSZOXTYVXIAFH-UHFFFAOYSA-N 0.000 description 1
- OYGBZBLYLLXFJK-UHFFFAOYSA-N c(cc1)ccc1N(c(cc1)ccc1-[n]1c(c2c(cc3)c(cccc4)c4[n]2-c2ccccc2)c3c2c1cccc2)c(cc1c2ccccc22)ccc1[n]2-c1ccccc1 Chemical compound c(cc1)ccc1N(c(cc1)ccc1-[n]1c(c2c(cc3)c(cccc4)c4[n]2-c2ccccc2)c3c2c1cccc2)c(cc1c2ccccc22)ccc1[n]2-c1ccccc1 OYGBZBLYLLXFJK-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other heteroatoms
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur
Abstract
Provided are novel organic electroluminescent compounds and an organic electroluminescent device using the same. Because the organic electroluminescent device using the organic electroluminescent compound as a hole transport material or a hole injection material exhibits good luminous efficiency and excellent lifetime properties, it is used to manufacture OLED devices having superior operating lifetimes and that consume less power due to improved power efficiency.
Description
Technical field
The present invention relates to new organic electroluminescent compounds and the organic electroluminescence device that comprises this compound, the organic electroluminescence device that relates more specifically to be suitable as the new organic electroluminescent compounds of hole mobile material or hole-injecting material and use this compound.
Technical background
Be extensive use of liquid-crystal display (LCD) at present, it is to have reduce power consumption and light-weighted non-emissivity indicating meter, but its not satisfactory performance that has complicated operational system and comprise time of response and contrast gradient.Therefore, organic electroluminescence device just receives publicity as flat-panel monitor of future generation at present, and they are furtherd investigate.
In display device, electroluminescent (EL) device is preferred, because they provide contrast gradient and the quick speed of response of wide visual angle, excellence as the self-emission display device.Eastman Kodak Co (Eastman Kodak) has at first developed a kind of organic EL device in 1987, this device uses low molecular weight aromatic diamines and aluminum complex as the material [Appl.Phys.Lett.51,913,1987] that forms electroluminescence layer.
The luminous mechanism of organic electroluminescence device is: when electric charge is injected into the organic layer that is formed between electron injection electrode (negative electrode) and the hole injecting electrode (anode), form electron-hole pair, and luminous when electron-hole pair is buried in oblivion.Described device can form at flexible transparent base material (for example plastics), also can compare operation under the low voltage of plasma display panel or inorganic EL display (10V or lower), needs less power consumption and has excellent color.
The organic materials of organic EL device can be divided into electroluminescent material and charge transfer material substantially.Described electroluminescent material directly relates to electroluminescent color and luminous efficiency, needs following several characteristics, for example low degradation property, uniform thin film formability and the stability the when high mobility in solid-state high-fluorescence quantum yield, electronics and hole, vacuum moulding machine.
Simultaneously, hole injection and transport material comprise copper phthalocyanine (CuPc), NPB, TPD, MTDATA(4,4', 4''-three (3-methyl phenyl phenyl amino) triphenylamine) etc.The hole is injected or transport layer uses the device of these materials in efficient and operation lifetime problem to be arranged.This is because when organic El element drives under high current condition, has produced thermal stresses between anode and hole injection layer.Described thermal stresses has obviously reduced the working life of device.In addition, have very high hole migration owing to be used for the organic materials of hole injection layer, can break the charge balance of described hole-electronics, and reduce quantum yield (cd/A).
The known amorphous compound that makes film have good stability has improved the working life of organic EL device.Second-order transition temperature (T
g) be measuring of amorphous state.The second-order transition temperature of MTDATA is 76 ° of C, can not have high amorphous state.These materials are aspect the working life of organic el device and luminous efficiency and unsatisfactory, and this is injected by the hole and the transport property decision.
Summary of the invention
Technical problem
Therefore, the present invention is directed to the problem that prior art exists, an object of the present invention is to provide to have than conventional hole and inject or the better luminous efficiency of hole mobile material and device work-ing life and have the organic electroluminescent compounds of excellent backbone structure, and provide and adopt this new organic electroluminescent compounds as the new organic electroluminescence device of hole injection layer or hole transmission layer.
Technical scheme
The invention provides the organic electroluminescent compounds that following Chemical formula 1 is represented, and the organic electroluminescence device that comprises described organic electroluminescent compounds.In the hole injection layer of organic electroluminescence device or hole transmission layer, contain organic electroluminescent compounds of the present invention, thereby reduced the running voltage of device and increased the luminous efficiency of device.
In one aspect, the invention provides the organic electroluminescent compounds of representing with following Chemical formula 1.
Chemical formula 1
X
1And X
2Represent CR independently
3Or N;
Y
1And Y
2Represent independently chemical bond ,-O-,-S-,-C (R
11R
12)-,-Si (R
13R
14)-or-N (R
15)-, only gets rid of Y
1And Y
2Be the situation of chemical bond simultaneously;
R
1To R
3Explain hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C2-C30) heteroaryl, replacement or unsubstituted (C3-C30) cycloalkyl, replacement or unsubstituted 5-unit independently to 7-unit Heterocyclylalkyl, replacement or unsubstituted (C6-C30) aryl (C1-C30) alkyl, replacement or unsubstituted (C1-C30) alkyl silyl, cyano group, nitro or hydroxyl, and when having two or more R
1Or R
2The time, they are interconnected to form ring structure;
L represents to replace or unsubstituted (C6-C30) arylidene or replacement or unsubstituted (C2-C30) heteroarylidene, and when having two or more L, they are interconnected to form ring structure;
Ar
1And Ar
2Expression replaces or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C2-C30) heteroaryl independently, perhaps
Y
3And Y
4Represent independently chemical bond ,-O-,-S-,-C (R
16R
17)-,-Si (R
18R
19)-or-N (R
20)-, only gets rid of Y
3And Y
4Be the situation of chemical bond simultaneously;
R
11To R
20Represent hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted (C2-C30) heteroaryl independently, perhaps they can be respectively be connected to form alicyclic ring, monocycle or many cyclophanes ring by replacement or unsubstituted (C3-C30) alkylidene group that has or do not have condensed ring or the replacement that has or do not have condensed ring or unsubstituted (C3-C30) alkenylene and adjacent substituting group;
M and n represent the integer of 0-4 independently, when m and n are during more than or equal to 2 integer, and each R
1With L can be identical or different;
P represents the integer of 0-2, when p=2, and each R
2Can be identical or different; And
Described Heterocyclylalkyl, heteroaryl and heteroarylidene comprise one or more B of being selected from, N, O, S, P (=O), the heteroatoms of Si and P;
The substituting group that term used herein " alkyl " and other contain " alkyl " part comprises straight chain and a chain portion, and " cycloalkyl " comprises monocyclic hydrocarbon and polynuclear hydrocarbon, for example replaces or unsubstituted adamantyl or replacement or unsubstituted (C7-C30) bicyclic alkyl.Term used herein " aryl " refers to by removing the organic group that hydrogen atom obtains from aromatic hydrocarbon, comprises 4 yuan to 7 yuan, is specially monocycle or the condensed ring of 5 yuan or 6 yuan, even can also comprise the structure by singly linked a plurality of aryl.Their object lesson includes but not limited to: phenyl, naphthyl, xenyl (biphenyl), terphenyl (terphenyl), anthryl, indenyl, fluorenyl, phenanthryl (phenanthryl), benzo [9,10] phenanthryl (triphenylenyl), pyrenyl, perylene base (perylenyl),
Base (chrysenyl), naphthacenyl (naphthacenyl), fluoranthene base (fluoranthenyl) etc.Described naphthyl comprises 1-naphthyl and 2-naphthyl, described anthryl comprises 1-anthryl, 2-anthryl and 9-anthryl, described fluorenyl comprises 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl, and described naphthacenyl (naphthacenyl) comprises 1-naphthacenyl, 2-naphthacenyl and 9-naphthacenyl.Described pyrenyl comprises 1-pyrenyl, 2-pyrenyl and 4-pyrenyl, described xenyl comprises 2-xenyl, 3-xenyl and 4-xenyl, described terphenyl comprises right-terphenyl-4-base, right-terphenyl-the 3-base, right-terphenyl-the 2-base ,-terphenyl-4-base ,-terphenyl-3-base and-terphenyl-2-base, described fluorenyl comprises 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.
Term used herein " heteroaryl " expression comprise 1-4 be selected from B, N, O, S, P, P (=O), the heteroatoms of Si and Se is as the aromatic ring frame atom, and other aromatic ring frame atoms aromatic yl group that is carbon.It can be 5 yuan of obtaining with one or more phenyl ring condensations or 6 yuan of bicyclic heteroaryls or polyheteroaromatic, and can be fractional saturation.In the present invention, " heteroaryl " comprises one or more heteroaryls by singly linked structure.Described heteroaryl comprises divalent aryl, and wherein the heteroatoms in the ring can be oxidized or quaternized to form for example N-oxide compound or quaternary ammonium salt.Their object lessons include, but are not limited to, and bicyclic heteroaryl is furyl, thienyl, pyrryl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl group, isothiazolyl, isoxazolyl, oxazolyl, oxadiazole base, triazinyl, tetrazine base, triazolyl, furazan base (furazanyl), pyridyl, pyrazinyl, pyrimidyl, pyridazinyl etc. for example; Polyheteroaromatic is benzofuryl (benzofuranyl) for example, the benzo thiophenyl, dibenzofuran group, the dibenzo thiophenyl, isobenzofuran-base, benzimidazolyl-, benzothiazolyl, the benzisothiazole base, benzoisoxazole base benzoxazolyl, pseudoindoyl, indyl, indazolyl, the diazosulfide base, quinolyl, isoquinolyl, cinnolines base (cinnolinyl), quinazolyl, quinoxalinyl (quinoxalinyl), carbazyl, phenanthridinyl (phenanthridinyl), benzo dioxolyl (benzodioxolyl), acridyl, the phenanthroline base, phenazinyl, phenothiazinyl phenoxazinyl etc.; And N-oxide compound (for example pyridyl N-oxide compound, quinolyl N-oxide compound); Or its quaternary ammonium salt etc.Pyrryl comprises: 1-pyrryl, 2-pyrryl and 3-pyrryl; Pyridyl comprises 2-pyridyl, 3-pyridyl and 4-pyridyl; Indyl comprises 1-indyl, 2-indyl, 3-indyl, 4-indyl, 5-indyl, 6-indyl and 7-indyl; Pseudoindoyl comprises 1-pseudoindoyl, 2-pseudoindoyl, 3-pseudoindoyl, 4-pseudoindoyl, 5-pseudoindoyl, 6-pseudoindoyl and 7-pseudoindoyl; Furyl comprises 2-furyl and 3-furyl; Benzofuryl comprises 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuryl and 7-benzofuryl; Isobenzofuran-base comprises 1-isobenzofuran-base, 3-isobenzofuran-base, 4-isobenzofuran-base, 5-isobenzofuran-base, 6-isobenzofuran-base and 7-isobenzofuran-base; Quinolyl comprises 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl and 8-quinolyl; Isoquinolyl comprises 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl and 8-isoquinolyl; Quinoxalinyl comprises 2-quinoxalinyl, 5-quinoxalinyl and 6-quinoxalinyl; Carbazyl comprises 1-carbazyl, 2-carbazyl, 3-carbazyl, 4-carbazyl and 9-carbazyl; Phenanthryl comprises 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 6-phenanthryl, 7-phenanthryl, 8-phenanthryl, 9-phenanthryl and 10-phenanthryl; Acridyl comprises 1-acridyl, 2-acridyl, 3-acridyl, 4-acridyl and 9-acridyl; The phenanthroline base comprises 1,7-phenanthroline-2-base, 1,7-phenanthroline-3-base, 1,7-phenanthroline-4-base, 1,7-phenanthroline-5-base, 1,7-phenanthroline-6-base, 1,7-phenanthroline-8-base, 1,7-phenanthroline-9-base, 1,7-phenanthroline-10-base, 1,8-phenanthroline-2-base, 1,8-phenanthroline-3-base, 1,8-phenanthroline-4-base, 1,8-phenanthroline-5-base, 1,8-phenanthroline-6-base, 1,8-phenanthroline-7-base, 1,8-phenanthroline-9-base, 1,8-phenanthroline-10-base, 1,9-phenanthroline-2-base, 1,9-phenanthroline-3-base, 1,9-phenanthroline-4-base, 1,9-phenanthroline-5-base, 1,9-phenanthroline-6-base, 1,9-phenanthroline-7-base, 1,9-phenanthroline-8-base, 1,9-phenanthroline-10-base, 1,10-phenanthroline-2-base, 1,10-phenanthroline-3-base, 1,10-phenanthroline-4-base, 1,10-phenanthroline-5-base, 2,9-phenanthroline-1-base, 2,9-phenanthroline-3-base, 2,9-phenanthroline-4-base, 2,9-phenanthroline-5-base, 2,9-phenanthroline-6-base, 2,9-phenanthroline-7-base, 2,9-phenanthroline-8-base, 2,9-phenanthroline-10-base, 2,8-phenanthroline-1-base, 2,8-phenanthroline-3-base, 2,8-phenanthroline-4-base, 2,8-phenanthroline-5-base, 2,8-phenanthroline-6-base, 2,8-phenanthroline-7-base, 2,8-phenanthroline-9-base, 2,8-phenanthroline-10-base, 2,7-phenanthroline-1-base, 2,7-phenanthroline-3-base, 2,7-phenanthroline-4-base, 2,7-phenanthroline-5-base, 2,7-phenanthroline-6-base, 2,7-phenanthroline-8-base, 2,7-phenanthroline-9-base and 2,7-phenanthroline-10-base; Phenazinyl comprises 1-phenazinyl and 2-phenazinyl; Phenothiazinyl comprises 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl and lysivane base; Phenoxazinyl comprises 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phenoxazinyl and 10-phenoxazinyl; Oxazolyl comprises 2-oxazolyl, 4-oxazolyl and 5-oxazolyl; Oxadiazole comprises 2-oxadiazole base and 5-oxadiazole base; The furazan base comprises 3-furazan base; Dibenzofuran group comprises 1-dibenzofuran group, 2-dibenzofuran group, 3-dibenzofuran group and 4-dibenzofuran group; The dibenzo thiophenyl comprises 1-dibenzo thiophenyl, 2-dibenzo thiophenyl, 3-dibenzo thiophenyl and 4-dibenzo thiophenyl.
Term used herein " (C1-C30) alkyl " comprises (C1-C20) alkyl or (C1-C10) alkyl, and term " (C6-C30) aryl " comprises (C6-C20) aryl or (C6-C12) aryl.Term " (C2-C30) heteroaryl " comprises (C2-C20) heteroaryl or (C2-C12) heteroaryl, and term " (C3-C30) cycloalkyl " can comprise (C3-C20) cycloalkyl or (C3-C7) cycloalkyl.Term " (C2-C30) alkenyl or alkynyl " comprises (C2-C20) alkenyl or alkynyl or (C2-C10) alkenyl or alkynyl.
In statement used herein " replacement or unsubstituted " or " being with or without substituting group ", the unsubstituted substituting group of term " (substituting group is arranged) of replacement " expression further is substituted base and replaces.R
1, R
2, R
3, L, Ar
1, Ar
2And R
11To R
20Substituting group one or more substituting groups that can be respectively be selected from down group further replace: deuterium, halogen, halogen replaces or unsubstituted (C1-C30) alkyl, (C6-C30) aryl, (C6-C30) aryl replaces or unsubstituted (C2-C30) heteroaryl, 5-unit to 7-unit Heterocyclylalkyl, the 5-unit that condenses with one or more aromatic rings to 7-unit Heterocyclylalkyl, (C3-C30) cycloalkyl, (C6-C30) cycloalkyl that condenses with one or more aromatic rings, (C2-C30) thiazolinyl, (C2-C30) alkynyl;
Cyano group, carbazyl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl ,-OR
21,-SR
22,-NR
23R
24,-PR
25R
26,-SiR
27R
28R
29, nitro and hydroxyl, and Y
11And Y
12Represent independently chemical bond ,-C (R
31R
32)-,-O-,-S-or-N (R
33)-, only gets rid of Y
11And Y
12It all is the situation of chemical bond; And R
21To R
29And R
31To R
33Expression (C1-C30) alkyl, (C6-C30) aryl, (C2-C30) heteroaryl or (C3-C30) cycloalkyl independently.
In Chemical formula 1, ring A
Condense expression 6-unit's aromatic ring or 6-membered nitrogen-containing heteroaryl ring, ring B with the indoline ring
A condenses with ring, expression 5-unit or 6-unit ring, ring C
B condenses with ring, expression 6-unit's aromatic ring or 6-membered nitrogen-containing heteroaryl ring.
Wherein, R
2, R
11To R
15, and the definition of p identical with Chemical formula 1.
Specifically, L represents (C6-C30) arylidene; Ar
1And Ar
2Independently expression (C6-C30) aryl, (C2-C30) heteroaryl,
Y
3And Y
4Independently expression-O-,-S-,-C (R
16R
17)-or-N (R
20)-; R
16, R
17And R
20Expression (C1-C30) alkyl, (C6-C30) aryl or (C2-C30) heteroaryl, perhaps R independently
16With
17Can be by replacing or unsubstituted (C3-C30) alkylidene group that is with or without condensed ring or by replacing or unsubstituted (C3-C30) alkenylene that is with or without condensed ring is connected to form alicyclic ring or monocycle or many cyclophanes ring; R
1Expression hydrogen, (C6-C30) aryl or (C2-C30) heteroaryl perhaps can pass through
Perhaps
Be connected with adjacent substituting group; The arylidene of L, Ar
1And Ar
2Aryl, heteroaryl, R
16, R
17And R
20Alkyl, aryl or heteroaryl, R
1Aryl or heteroaryl can further be replaced by one or more substituting groups that are selected from down group: deuterium, halogen, halogen replace or unsubstituted (C6-C30) aryl, (C1-C30) alkyl, (C6-C30) aryl replaces or unsubstituted (C2-C30) heteroaryl, 5-unit to 7-unit Heterocyclylalkyl, 5-unit to the 7-unit Heterocyclylalkyl that condenses with one or more aromatic rings,
Carbazyl, and-NR
23R
24, Y
11And Y
12Expression-C (R independently
31R
32)-,-O-,-S-or-N (R
30)-; R
23, R
24, R
31, R
32And R
33Expression (C1-C30) alkyl, (C6-C30) aryl or (C2-C30) heteroaryl independently.
Organic electroluminescent compounds of the present invention can be enumerated as following compound, but they are not construed as limiting the present invention:
Organic electroluminescent compounds of the present invention for example prepares shown in the following proposal 1, but is not limited thereto.
[scheme 1]
Wherein, A, B, C, R
1, L, Ar
1, Ar
2, m is identical with the definition of Chemical formula 1 with n.
In addition, the invention provides a kind of organic electroluminescence device, wherein organic electroluminescent compounds of the present invention is as hole-injecting material or hole mobile material.
When the organic electroluminescent compounds of representing when Chemical formula 1 of the present invention was used for hole injection layer or hole transmission layer, it can be used for making because the power efficiency of improvement consumes the still less OLED device of power.
Organic electroluminescence device of the present invention comprises first electrode; Second electrode; Insert one or more layers organic layer between described first electrode and second electrode, described organic layer comprises one or more organic electroluminescent compounds that Chemical formula 1 is represented.
In addition, except one or more organic electroluminescent compounds layers that comprise Chemical formula 1, organic layer also can comprise one or more layers electroluminescence layer.Electroluminescence layer also can comprise one or more doping agents or matrix.The doping agent or the matrix that are used for organic electroluminescence device of the present invention have no particular limits, but optional from following Chemical formula 2-6:
Chemical formula 2
M
1L
101L
102L
103
Wherein,
M
1Expression Ir, Pt, Pd or Os;
Ligand L
101, L
102And L
103Be independently selected from following structure:
R
201To R
203Represent that independently hydrogen, deuterium, halogen replacement or unsubstituted (C1-C30) alkyl, (C1-C30) alkyl replace or unsubstituted (C6-C30) aryl or halogen;
R
204To R
219Represent hydrogen independently, deuterium, replace or unsubstituted (C1-C30) alkyl, replace or unsubstituted (C1-C30) alkoxyl group, replace or unsubstituted (C3-C30) cycloalkyl, replace or unsubstituted (C2-C30) thiazolinyl, replace or unsubstituted (C6-C30) aryl, replace or unsubstituted list-(C1-C30) alkylamino or replacement or unsubstituted two-(C1-C30) alkylaminos, replace or unsubstituted list-(C6-C30) arylamino or replacement or unsubstituted two-(C6-C30) arylaminos, SF
5, replacement or unsubstituted three (C1-C30) alkyl silyl, replacement or unsubstituted two (C1-C30) alkyl (C6-C30) aryl silyl, replacement or unsubstituted three (C6-C30) aryl silyl, cyano group or halogen;
R
220To R
223Represent independently that hydrogen, deuterium, halogen replace or unsubstituted (C1-C30) alkyl or (C1-C30) alkyl replace or unsubstituted (C6-C30) aryl;
R
224And R
225Represent that independently hydrogen, deuterium, replacement or unsubstituted (C1-C30) alkyl, halogen replace or unsubstituted (C6-C30) aryl or halogen, perhaps R
224And R
225Can be connected to form alicyclic ring, monocycle or many cyclophanes ring by replacement or unsubstituted (C3-C12) alkylidene group that has or do not have condensed ring or the replacement that has or do not have condensed ring or unsubstituted (C3-C12) alkenylene and adjacent substituting group;
R
226Expression replaces or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C2-C30) heteroaryl or halogen;
R
227To R
229Represent hydrogen, deuterium, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or halogen independently; And
Wherein, R
231To R
242Represent that independently hydrogen, deuterium, halogen replace or unsubstituted (C1-C30) alkyl, (C1-C30) alkoxyl group, halogen, replacement or unsubstituted (C6-C30) aryl, cyano group, replacement or unsubstituted (C3-C30) cycloalkyl, perhaps they can be connected to form volution or condensed ring by alkylidene group or alkenylene and adjacent substituting group, perhaps by alkylidene group or alkenylene and R
207Or R
208Be connected to form saturated or unsaturated condensed ring.
Chemical formula 3
Wherein,
Z represents-O-,-S-,-C (R
41R
42)-,-Si (R
43R
44)-or-N (R
45)-;
Y
21And Y
22Represent CH or N independently;
Y
23And Y
24Represent independently chemical bond ,-O-,-S-,-C (R
41R
42)-,-Si (R
43R
44)-or-N (R
45)-, only gets rid of Y
23And Y
24It all is the situation of chemical bond;
R
31And R
32Represent hydrogen independently, deuterium, halogen, replace or unsubstituted (C1-C30) alkyl, replace or unsubstituted (C6-C30) aryl, replace or unsubstituted (C2-C30) heteroaryl, replace or unsubstituted (C3-C30) cycloalkyl, replace or unsubstituted 5-unit to 7-unit Heterocyclylalkyl, replace or unsubstituted (C6-C30) aryl (C1-C30) alkyl, replace or unsubstituted (C1-C30) alkyl silyl, replace or unsubstituted (C6-C30) aryl silyl, replace or unsubstituted (C1-C30) alkyl (C6-C30) aryl silyl, cyano group, nitro or hydroxyl, perhaps they can be connected to form alicyclic ring with adjacent substituting group by replacement or unsubstituted (C3-C30) alkylidene group that is with or without condensed ring or the replacement that is with or without condensed ring or unsubstituted (C3-C30) alkenylene, monocycle or many cyclophanes ring;
R
41To R
45Represent hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C2-C30) heteroaryl, replacement or unsubstituted 5-unit independently to 7-unit's Heterocyclylalkyl or be with or without substituent replacement or unsubstituted (C3-C30) cycloalkyl, perhaps they can be connected to form ring with adjacent substituting group respectively;
R and q represent the integer of 0-4 independently, and when r and q be during more than or equal to 2 integer, each R
31And R
32Can be identical or different, perhaps they can be connected to form ring with adjacent substituting group respectively;
Described Heterocyclylalkyl and heteroaryl comprise one or more B of being selected from, N, O, S, P (=O), the heteroatoms of Si and P.
Chemical formula 4
(Cz-L
2)
a-M
Chemical formula 5
(Cz)
b-L
2-M
Wherein,
Cz is selected from following structure:
Ring G represents (C6-C30) alicyclic ring, (C6-C30) aromatic ring or (C2-C30) hetero-aromatic ring;
R
51And R
53Represent hydrogen independently, deuterium, halogen, replace or unsubstituted (C1-C30) alkyl, replace or unsubstituted (C6-C30) aryl, replace or unsubstituted (C2-C30) heteroaryl, replace or unsubstituted 5-unit to 7-unit Heterocyclylalkyl, replacement or unsubstituted (C6-C30) aryl Cycloalkylfused with one or more replacements or unsubstituted (C3-C30), the 5-unit that condenses with one or more replacements or unsubstituted aromatic ring to 7-unit Heterocyclylalkyl, replace or unsubstituted (C3-C30) cycloalkyl, (C3-C30) cycloalkyl that condenses with one or more replacements or unsubstituted aromatic ring, replace or unsubstituted (C6-C30) aryl (C1-C30) alkyl, cyano group, nitro, hydroxyl,-BR
61R
62,-PR
63R
64,-P (=O) R
65R
66, R
67R
68R
69Si-,-NR
70R
71Or-YR
72Perhaps they can be by replacing or unsubstituted (C3-C30) alkylidene group that is with or without condensed ring or replacement or unsubstituted (C3-C30) alkenylene and the adjacent substituting group that is with or without condensed ring are connected to form alicyclic ring, monocycle or many cyclophanes ring, and the carbon atom of formed alicyclic ring, monocycle or many cyclophanes ring is selected from one or more heteroatomss replacements of nitrogen, oxygen, sulphur; And each R
52And R
53Can be identical or different mutually;
Y represents O or S;
R
61To R
72Represent hydrogen independently, deuterium, halogen, replace or unsubstituted (C1-C30) alkyl, replace or unsubstituted (C6-C30) aryl, replace or unsubstituted (C2-C30) heteroaryl, replace or unsubstituted 5-unit to 7-unit Heterocyclylalkyl, replacement or unsubstituted (C6-C30) aryl Cycloalkylfused with one or more replacements or unsubstituted (C3-C30), the 5-unit that condenses with one or more replacements or unsubstituted aromatic ring to 7-unit Heterocyclylalkyl, replace or unsubstituted (C3-C30) cycloalkyl, (C3-C30) cycloalkyl that condenses with one or more replacements or unsubstituted aromatic ring, replace or unsubstituted (C6-C30) aryl (C1-C30) alkyl, cyano group, nitro or hydroxyl;
L
2Expression chemical bond, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted (C2-C30) heteroaryl;
M represents to replace or unsubstituted (C6-C30) aryl or replacement or unsubstituted (C2-C30) heteroaryl;
A, b, c and d represent the integer of 0-4 independently.
Chemical formula 6
Wherein,
A
1To A
19Represent CR independently
81Or N;
X represents-C (R
82R
83)-,-N (R
84)-,-S-,-O-,-Si (R
85) (R
86)-,-P (R
87)-,-P (=O) (R
88)-or-B (R
89)-;
Ar
11Expression replaces or unsubstituted (C6-C40) arylidene or replacement or unsubstituted (C2-C40) heteroarylidene; Only get rid of e=0 and A
15To A
19Be CR simultaneously
81Situation;
R
81To R
89Represent hydrogen independently, deuterium, halogen, replace or unsubstituted (C1-C30) alkyl, replace or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C6-C30) aryl Cycloalkylfused with one or more replacements or unsubstituted (C3-C30), replace or unsubstituted (C2-C30) heteroaryl, replace or unsubstituted 5-unit to 7-unit Heterocyclylalkyl, the 5-unit that condenses with one or more replacements or unsubstituted aromatic ring to 7-unit Heterocyclylalkyl, replace or unsubstituted (C3-C30) cycloalkyl, (C3-C30) cycloalkyl that condenses with one or more replacements or unsubstituted aromatic ring, cyano group, trifluoromethyl,-NR
91R
92,-BR
93R
94,-PR
95R
96,-P (=O) R
97R
98, R
99R
100R
101Si-, R
102Y
21-, R
103C (=O)-, R
104C (=O) O-, replacement or unsubstituted (C6-C30) aryl (C1-C30) alkyl, replacement or unsubstituted (C2-C30) thiazolinyl, replacement or unsubstituted (C2-C30) alkynyl, carboxyl, nitro or hydroxyl, perhaps they can be by replacing or unsubstituted (C3-C30) alkylidene group that is with or without condensed ring or replacement or unsubstituted (C3-C30) alkenylene and the adjacent substituting group that is with or without condensed ring are connected to form alicyclic ring, monocycle or many cyclophanes ring;
R
91To R
98Expression replaces or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted (C2-C30) heteroaryl independently;
R
99To R
101Expression replaces or unsubstituted (C1-C30) alkyl or replacement or unsubstituted (C6-C30) aryl independently;
Y
21Expression S or O;
R
102Expression replaces or unsubstituted (C1-C30) alkyl or replacement or unsubstituted (C6-C30) aryl;
R
103Expression replaces or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C1-C30) alkoxyl group, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted (C6-C30) aryloxy;
R
104Expression replaces or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C1-C30) alkoxyl group, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted (C6-C30) aryloxy;
E represents the integer of 0-2.
Described Heterocyclylalkyl, heteroaryl and heteroarylidene comprise one or more B of being selected from, N, O, S, P (=O), the heteroatoms of Si and P;
In the used term of Chemical formula 2-6 " replacement or unsubstituted ", the unsubstituted substituting group of term " replacement " expression is substituted base and further replaces.Described substituting group represents to be selected from one or more substituting groups of the represented identical group of group in the Chemical formula 1.
Specifically, Chemical formula 2-6 can be used following compound:
Organic electroluminescence device of the present invention comprises the organic electroluminescent compounds that Chemical formula 1 is represented, also can comprise the compound that one or more are selected from aromatic amine compound and styryl amine compound, the object lesson of described aromatic amine compound and styryl amine compound is as described in the 212nd to 224 section in the specification sheets of korean patent application 10-2008-0060393 number, but is not limited thereto.
In organic electroluminescence device of the present invention, except the organic electroluminescent compounds that Chemical formula 1 is represented, organic layer can comprise that also one or more are selected from metal or the complex compound of the transition metal of organo-metallic, period 4 and the period 5 of the periodic table of elements the 1st family, the 2nd family, lanthanide series metal and d-transition element.Described organic layer can comprise electroluminescence layer and charge generation layer.
Can realize having the organic electroluminescence device of the dot structure of independent light-emitting mode, wherein pattern parallelization (pattern) comprises the organic electroluminescent compounds of Chemical formula 1 of the present invention as the organic electroluminescence device of sub-pixel simultaneously, and described one or more sub-pixels comprise the metallic compound that one or more are selected from Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag.
In addition, except the organic electroluminescent compounds that described Chemical formula 1 is represented, described organic layer also can comprise the organic electro luminescent layer of one or more emission blue light, green glow or ruddiness simultaneously, to realize the organic electroluminescence device of emission white light.The example of the compound of blue light-emitting, green glow or ruddiness can be korean patent application 10-2008-0123276,10-2008-0107606 or 10-2008-0118428 number described compound, but is not limited thereto.
In organic electroluminescence device of the present invention, the layer (hereinafter referred to as " upper layer ") that is selected from chalcogenide layer, metal halide and metal oxide layer can be arranged on the internal surface of one or two electrode in the electrode pair.More particularly, the metal chalcogenide of silicon or aluminium (comprising oxide compound) layer can place on the anode surface of electroluminescent medium layer, and metal halide or metal oxide layer can place on the cathode surface of described electroluminescent medium layer.Thereby obtain job stability.For example, chalkogenide can be SiO
x(1≤x≤2), AlO
x(1≤x≤1.5), SiON, SiAlON etc.For example, metal halide can be LiF, MgF
2, CaF
2, rare earth metal fluorochemical etc.For example, metal oxide can be Cs
2O, Li
2O, MgO, SrO, BaO, CaO etc.
In organic electroluminescence device of the present invention, the mixing zone of electric transmission compound and reductibility doping agent also preferably is set, perhaps the mixing zone of hole transport compound and oxidisability doping agent at least one surface of prepared electrode pair.In this case, because the electric transmission compound is reduced into negatively charged ion, thereby promotes electronics from the mixing zone injection and be transferred to electroluminescent medium.In addition, because the oxidized formation positively charged ion of hole transport compound, thereby promote the hole from the mixing zone injection and be transferred to electroluminescent medium.Preferred oxidisability doping agent comprises various Lewis acids and acceptor compound.Preferred reductibility doping agent comprises basic metal, alkali metal compound, alkaline-earth metal, rare earth metal and composition thereof.In addition, the electroluminescent device that emits white light with two-layer or more multi-layered electroluminescence layer can use the reductibility dopant layer to prepare as charge generation layer.
The useful effect of invention
According to the present invention, organic electroluminescent compounds can be used as hole mobile material or hole-injecting material, thereby the organic electroluminescence device that obtains can have good illumination efficiency, and have an excellent material performance in work-ing life, and can be used for making and have very excellent operation life and owing to having improved the OLED device that power efficiency reduces watt consumption.
The embodiment of invention
Hereinafter further describe organic electroluminescent compounds of the present invention with reference to representative compounds of the present invention, and preparation method thereof with the electroluminescent properties of device.But these embodiment only are used for describing the embodiment purpose, do not limit the scope of the invention.
[preparation example 1] preparation compound 1
The preparation of compound 1-1
In 500mL toluene, add 2-iodobenzene 30g (120.4mmol), 4-bromophenyl boric acid 26g (132.5mmol), Pd (PPh
3)
46.9g (6.02mmol) and the Na of 2M
2CO
3150mL, mixture is 100 ℃ of heating.After 4 hours, mixture is at room temperature cooled off, and use ethyl acetate extraction.Cleaning with distilled water, use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 1-1,28g (100.68mmol, 83.33%) by the post separation.
The preparation of compound 1-2
In the 300mL triethyl-phosphite, add compound 1-128g (100.68mmol), and stirred 6 hours at 150 ℃.After the room temperature cooling, the mixture reduction vaporization, and use ethyl acetate extraction.The gained material cleans with distilled water.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 1-2,11g (44.69mmol, 44.38%) by the post separation.
The preparation of compound 1-3
Mixing cpd 1-230g (101.29mmol), iodobenzene 41.3g (202.59mmol), CuI9.6g (50.64mmol), Cs
2CO
382.5g (253.2mmol) and toluene 600mL, and 50 ℃ of heating.Add quadrol 6.8mL (101.29mmol) in mixture, backflow stirs the mixture.After 14 hours, mixture at room temperature cools off, and to wherein adding distilled water.With ethyl acetate extraction gained mixture.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 1-3,32g (85.96mmol, 84.86%) by the post separation.
The preparation of compound 1-4
Compound 1-332g (85.96mmol) is dissolved in 300mL THF, and in mixture, slowly adds n-Butyl Lithium 37.8mL (94.55mmol, 2.5M is in hexane) at-78 ℃.After 1 hour, in mixture, add trimethyl borate 12.4mL (111.7mmol).After at room temperature stirring the mixture 12 hours, to adding distilled water through in the stirred mixture, use the ethyl acetate extraction mixture.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 1-4,20g (59.31mmol, 69.00%) by the post separation.
The preparation of compound 1-5
Mixing cpd 1-420g (59.31mmol), 1-bromo-2-oil of mirbane 14.3g (71.17mmol), Pd (PPh
3)
42.7g (2.37mmol), the Na of 2M
2CO
375mL, toluene 300mL and ethanol 70mL reflux and stir.After 5 hours, mixture at room temperature cools off, and adds distilled water in mixture.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 1-5,20g (48.25mmol, 81.36%) by the post separation.
The preparation of compound 1-6
After adding the 200mL triethyl-phosphite to compound 1-520g (48.25mmol), mixture stirred 6 hours at 150 ℃, and cooling at room temperature.After carrying out underpressure distillation, use the ethyl acetate extraction mixture, the gained material cleans with distilled water.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 1-6,7g (18.30mmol, 37.93%) by the post separation.
The preparation of compound 1
Mixing cpd 1-67g (18.30mmol), 4-bromo-N, N-phenylbenzene aniline 11.9g (36.60mmol), CuI1.7g (9.15mmol), K
3PO
411.6g (54.90mmol) and toluene 100mL, and 50 ℃ of heating.Add quadrol 1.2mL (18.30mmol) afterwards in mixture, backflow stirs the mixture.After 14 hours, mixture at room temperature cools off, and adds distilled water in mixture.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 1,8g (17.44mmol, 95.33%) by the post separation.
MS/FAB measured value 576, theoretical value 575.70
[preparation example 2] preparation compound 15
The preparation of compound 2-1
In the two neck RBF of 1L, add 1-bromo-2-oil of mirbane 15g (0.074mol) afterwards, mix 9,9-dimethyl-9H-fluorenes-2-ylboronic acid 23g (0.096mol), Pd (PPh
3)
44.2g (0.003mol), Na
2CO
3(2M) 111mL and ethanol 111mL.After mixture adds 200mL toluene, with mixture 120 ℃ of stirring heating 3 hours.After reaction is finished, clean the gained material with distilled water, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, obtain compound 2-1 by the column chromatography purifying, 22g (95%).
The preparation of compound 2-2
Add compound 2-124g (0.076mol) afterwards to the two neck RBF of 1L, in mixture, add triethyl-phosphite 200mL and 1,2-dichlorobenzene 200mL, 140 ℃ of stirring heating 12 hours.After reaction is finished, solvent distillation.Clean the gained material with distilled water, and use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, obtain compound 2-2 by the column chromatography purifying, 7g (33%).
The preparation of compound 15
Mixing cpd 2-27g (18.30mmol), N-(4-bromophenyl)-N-phenylnaphthalene-2-amine (N-(4-bromophenyl)-N-phenylnaphthalene-2-amine) 13.7g (36.60mmol), CuI1.7g (9.15mmol), K
3PO
411.6g (54.90mmol) and toluene 100mL, and 50 ℃ of heating.Add quadrol 1.2mL (18.30mmol) in mixture, backflow stirs the mixture.After 14 hours, mixture at room temperature cools off, and adds distilled water in mixture.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 15,8g (17.44mmol, 95.33%) by the post separation.
MS/FAB measured value 577, theoretical value 576.73
[preparation example 3] preparation compound 22
The preparation of compound 3-1
Mix 2-bromo-9H-carbazole 7g (18.30mmol), N-(4-(9H-carbazole-9-yl) phenyl)-4-bromo-N-phenylaniline 13.7g (36.60mmol), CuI1.7g (9.15mmol), K
3PO
411.6g (54.90mmol) and toluene 100mL, and 50 ℃ of heating.Add quadrol 1.2mL (18.30mmol) afterwards, backflow stirs the mixture.After 14 hours, mixture at room temperature cools off, and adds distilled water in mixture.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 3-1,8g (17.44mmol, 95.33%) by the post separation.
The preparation of compound 3-2
Mixing cpd 3-112g (37.42mmol), 2-(methylthio group) phenyl-boron dihydroxide 7.5g (44.69mmol), Pd (PPh
3)
42.15g (1.6mmol), the Na of 2M
2CO
3Aqueous solution 45ml and THF200ml reflux then and stir.After 5 hours, mixture is at room temperature cooled off, and use ethyl acetate extraction.The gained material cleans with distilled water.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 3-2,10g (27.36mmol, 73.47%) by the post separation.
The preparation of compound 3-3
In 100ml acetic acid, add compound 3-210g (27.36mmol), and in mixture, slowly add H
2O
2(2.65ml 30.09mmol, 35%).Mixture at room temperature stirred 12 hours, and acetic acid is fallen in underpressure distillation.With dichloromethane extraction gained material, and use NaHCO
3The solution neutralization.Use MgSO
4Removal moisture obtains compound 3-3,10g (26.21mmol, 95.79%) after also under reduced pressure distilling.
The preparation of compound 22
Compound 3-310g (26.21mmol) mixes with trifluoromethanesulfonic acid 70mL, stirs 5 hours at 100 ℃.At room temperature cool off through stirred mixture, join the mixture (pyridine: distilled water=1:5) of 100mL.Mixture refluxes and stirs also after the cooling at room temperature pressure filtration gained solid.Obtain compound 22,6g (17.16mmol, 65.47%) by the post separation.
MS/FAB measured value 682, theoretical value 681.84
[preparation example 4] preparation compound 32
The preparation of compound 4-1
The Na that mixes dibenzo [b, d] thiophene-4-ylboronic acid 10g (43.84mmol), bromo nitryl benzene 8.85g (43.84mmol), 2M
2CO
3Solution 70ml, toluene 200ml and ethanol 70ml, and reflux and stir.After 5 hours, mixture is at room temperature cooled off, and use the ethyl acetate extraction mixture.The gained material cleans with distilled water.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 4-1,10g (32.74mmol, 74.68%) by the post separation.
The preparation of compound 4-2
Mixing cpd 4-110g (32.74mmol) and 100mL triethyl-phosphite, and 150 ℃ of stirrings 7 hours.At room temperature cooling mixture and carrying out after the underpressure distillation uses ethyl acetate to obtain compound 4-2 by recrystallization, 7g (25.60mmol, 78.19%).
The preparation of compound 32
Mixing cpd 4-27g (25.60mmol), N-(4-bromophenyl)-N, 9-phenylbenzene-9H-carbazole-3-amine 10.44g (51.21mmol), CuI2.5g (12.80mmol), K
3PO
416.30g (76.82mmol) and toluene 200mL, and 50 ℃ of heating.In mixture, add quadrol 1.72mL (25.60mmol).Mixture refluxes and stirred 12 hours, cooling at room temperature, and use ethyl acetate extraction.Use NaHCO
3Solution cleans the gained material.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 32,8g (22.89mmol, 89.41%) by the post separation.
MS/FAB measured value 682, theoretical value 681.84
[preparation example 5] preparation compound 41
The preparation of compound 5-1
2-(phenyl amino) phenylformic acid 50g (0.23mol) is dissolved in after the MeOH of 1L, mixture is added in the ice bath, and stirred 10 minutes at 0 ℃.Slowly add SOCl at 0 ℃
260mL (0.58mol) afterwards, mixture reflux to stir 12 hours at 90 ℃.After reaction is finished, clean the gained mixture with distilled water, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, use ethyl acetate to obtain compound 5-1 as the eluting solvent purifying, 47g (92%) by column chromatography.
The preparation of compound 5-2
Compound 5-190g (0.3mol) is added after the THF of 1.5L, slowly add MeMgBr (3.0M) 462mL (1.38mol) in mixture, mixture at room temperature stirred 12 hours.After reaction is finished, use in the distilled water and the gained mixture, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, use ethyl acetate to obtain compound 5-2 as the eluting solvent purifying, 80g (90%) by column chromatography.
The preparation of compound 5-3
The H that compound 5-280g (0.35mol) is added 1.7L
3PO
4Afterwards, mixture at room temperature stirred 12 hours.After reaction is finished, use in the distilled water and the mixture of gained.Filter the solid that produces, water cleans simultaneously.Use the methylene dichloride dissolved solids, with NaOH extraction and neutralization.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, use hexane to obtain compound 5-3 by recrystallization, 64g (87%).
The preparation of compound 5-4
With compound 5-364g (0.30mol), bromobenzene 52.8g (0.33mol), Pd (OAc)
21.37g (6.11mmol), P (t-Bu)
350%7.3mL (15.28mmol) and NaOt-Bu58g (0.61mol) are dissolved in the 1.2L toluene, and mixture stirred 12 hours at 120 ℃.After reaction is finished, use in the distilled water and the gained mixture, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, use ethyl acetate to obtain compound 5-4 as the eluting solvent purifying, 71g (81%) by column chromatography.
The preparation of compound 5-5
Compound 5-420g (0.07mol) is dissolved among the DMF of 800mL, stirred 10 minutes at 0 ℃.Slowly after the DMF solution of the 350mL of adding NBS12.5g (0.07mol), mixture stirred 6 hours at 0 ℃.After reaction is finished, use in the distilled water and the gained mixture, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, use ethyl acetate to obtain compound 5-5 as the eluting solvent purifying, 21g (84%) by column chromatography.
The preparation of compound 5-6
With compound 5-520g (0.054mol), 2-chloroaniline 8.4g (0.065mol), Pd (OAc)
22,370mg (1.64mmol), P (t-Bu)
350%3.6mL (5.49mmol) and Cs
2CO
335.7g (0.109mol) be dissolved in the 300mL toluene, stirred 4 hours at 120 ℃.After reaction is finished, use in the distilled water and the gained mixture, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, use ethyl acetate to obtain compound 5-6 as the eluting solvent purifying, 13.6g (60%) by column chromatography.
The preparation of compound 5-7
With compound 5-612.6g (0.03mol), Pd (OAc)
21.37mg (6.13mmol), Tetrafluoroboric acid two-tertiary butyl-(methyl) phosphine 3g (12.26mmol) and Cs
2CO
350g (0.15mol) is dissolved in the DMA of 240mL, stirs 4 hours at 190 ℃.After reaction is finished, use in the distilled water and the gained mixture, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, use ethyl acetate to obtain compound 5-7 as the eluting solvent purifying, 7g (70%) by column chromatography.
The preparation of compound 41
Mixing cpd 5-77g (25.60mmol), N-(phenylbenzene-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluorenes-2-amine 10.44g (51.21mmol), CuI2.5g (12.80mmol), K
3PO
416.30g (76.82mmol) and toluene 200mL, and 50 ℃ of heating.In mixture, add quadrol 1.72mL (25.60mmol).After mixture reflux to stir 12 hours, cooling mixture at room temperature, and use ethyl acetate extraction.Use NaHCO
3Solution cleans the gained material.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 41,8g (22.89mmol, 89.41%) by the post separation.
MS/FAB measured value 811, theoretical value 810.04
[preparation example 6] preparation compound 51
The preparation of compound 6-1
Compound 2-28.1g (0.028mol) is added among the two neck RBF of 1L, add the DMF of 300mL in the mixture.Mixture refluxes at 0 ℃ and stirred 10 minutes.NBS5.08g (0.028mol) is dissolved in the DMF of 300mL and mixture is joined after the reactant lentamente, mixture refluxes at 0 ℃ and stirred 6 hours.After reaction is finished, use in the distilled water and the gained mixture, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, use ethyl acetate to obtain compound 6-1 as the eluting solvent purifying, 9g (87%) by column chromatography.
The preparation of compound 6-2
Mixing cpd 6-17g (18.30mmol), N-(4-bromophenyl)-N-phenylnaphthalene-2-amine 13.7g (36.60mmol), CuI1.7g (9.15mmol), K
3PO
411.6g (54.90mmol) and toluene 100mL, and 50 ℃ of heating.In mixture, add quadrol 1.2mL (18.30mmol), reflux and stir.After 14 hours, mixture at room temperature cools off, and adds distilled water in mixture.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 6-2,8g (17.44mmol, 95.33%) by the post separation.
The preparation of compound 51
Mixing cpd 6-27g (18.30mmol), 9H-carbazole 13.7g (36.60mmol), CuI1.7g (9.15mmol), K
3PO
411.6g (54.90mmol) and toluene 100mL, and 50 ℃ of heating.In mixture, add quadrol 1.2mL (18.30mmol), reflux and stir.After 14 hours, mixture at room temperature cools off, and adds distilled water in mixture.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 51,8g (17.44mmol, 95.33%) by the post separation.
MS/FAB measured value 742, theoretical value 741.92
[preparation example 7] preparation compound 53
The preparation of compound 7-1
2-bromine dibenzo [b, d] thiophene 74g (216.3mmol) is dissolved among the THF of 1.5L, slowly adds n-Butyl Lithium 86.5mL (216.3mmol, 2.5M is in hexane) at-78 ℃.After 1 hour, in mixture, add trimethyl borate 28.9mL (259.6mmol), at room temperature stirred 12 hours.In mixture, add distilled water, described mixture ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, use ethyl acetate and hexane to carry out recrystallization and obtain compound 7-1,40g (136.8mmol, 62.96%).
The preparation of compound 7-2
Mixing cpd 7-140g (136.8mmol), iodonitrobenzene 37.4g (150.5mmol), Pd (PPh
3)
46.32g (5.47mmol), the Na of 2M
2CO
3170mL and toluene 700mL stirred 4 hours at 100 ℃.After mixture at room temperature cools off, to wherein adding distilled water, and with the described mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 7-2,28g (72.86mmol, 52.94%) by the post separation.
The preparation of compound 7-3
Mixing cpd 7-228g (72.86mmol) and 300mL triethyl-phosphite, and 150 ℃ of stirrings 12 hours.Mixture at room temperature cools off and carries out after the underpressure distillation, uses the described mixture of ethyl acetate extraction, and cleans the gained material with the gained material.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 7-3,11g (31.22mmol, 43.05%) by the post separation.
The preparation of compound 53
Mixing cpd 7-37g (18.30mmol), 4-bromo-N-(4-(dibenzo [b, d] thiophene-4-yl) phenyl)-N-phenylaniline 13.7g (36.60mmol), CuI1.7g (9.15mmol), K
3PO
411.6g (54.90mmol) and toluene 100mL, and 50 ℃ of heating.Add quadrol 1.2ml (18.30mmol), and reflux and stir.After 14 hours, mixture at room temperature cools off, and adds distilled water in mixture.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 53,8g (17.44mmol, 95.33%) by the post separation.
MS/FAB measured value 699, theoretical value 698.90
[preparation example 8] preparation compound 54
The preparation of compound 8-1
Mix 2,5-, two bromo nitrobenzene 50g (177.99mol), 1-naphthalene boronic acids 36.7g (213.59mmol), Pd (PPh
3)
410.28g (8.89mmol), the Na of 2M
2CO
3(533.97mmol), toluene 700mL and ethanol 200mL, stirred 5 hours at 100 ℃.After mixture at room temperature cools off, to wherein adding distilled water, and with the described mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 8-1,50g (152.36mmol, 85.60%) by the post separation.
The preparation of compound 8-2
Mixing cpd 8-150g (152.36mmol) and triethyl-phosphite 500mL stirred 7 hours at 150 ℃.Mixture is after the room temperature cooling and carrying out underpressure distillation, with the described mixture of ethyl acetate extraction.The gained material cleans with distilled water.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 8-2,30g (101.29mmol, 66.64%) by the post separation.
The preparation of compound 8-3
Mixing cpd 8-230g (101.29mmol), N-(4-(9H-carbazole-9-yl) phenyl)-4-bromo-N-(the 4-tertiary butyl-phenyl) aniline 41.3g (202.59mmol), CuI9.6g (50.64mmol), Cs
2CO
382.5g (253.2mmol) and toluene 600mL, and 50 ℃ of heating.Add quadrol 6.8mL (101.29mmol), and reflux and stir.After 14 hours, mixture at room temperature cools off, and adds distilled water in mixture.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 8-3,32g (85.96mmol, 84.86%) by the post separation.
The preparation of compound 8-4
Compound 8-332g (85.96mmol) is dissolved among the THF of 300mL, and slowly adds n-Butyl Lithium 37.8mL (94.55mmol, 2.5M is in hexane) at-78 ℃.After 1 hour, in mixture, add trimethyl borate 12.4mL (111.7mmol).After at room temperature stirring the mixture 12 hours, in mixture, add distilled water, use the ethyl acetate extraction mixture.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 8-4,20g (59.31mmol, 69.00%) by the post separation.
The preparation of compound 8-5
Mixing cpd 8-420g (59.31mmol), 1-bromo-2-oil of mirbane 14.3g (71.17mmol), Pd (PPh
3)
42.7g (2.37mmol), the Na of 2M
2CO
375mL, toluene 300mL and ethanol 70mL reflux and stir.After 5 hours, mixture at room temperature cools off, and adds distilled water in mixture.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 8-5,20g (48.25mmol, 81.36%) by the post separation.
The preparation of compound 8-6
Mixing cpd 8-520g (48.25mmol) and 200mL triethyl-phosphite, and 150 ℃ of stirrings 6 hours.Mixture is after the room temperature cooling and carrying out underpressure distillation, with the described mixture of ethyl acetate extraction.The gained material cleans with distilled water.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 8-6,7g (18.30mmol, 37.93%) by the post separation.
The preparation of compound 54
Mixing cpd 8-630g (101.29mmol), iodobenzene 41.3g (202.59mmol), CuI9.6g (50.64mmol), Cs
2CO
382.5g (253.2mmol) and toluene 600mL, and 50 ℃ of heating.In mixture, add quadrol 6.8mL (101.29mmol), reflux and stir.After 14 hours, mixture at room temperature cools off, and adds distilled water in mixture.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 54,32g (85.96mmol, 84.86%) by the post separation.
MS/FAB measured value 848, theoretical value 847.06
[preparation example 9] preparation compound 58
The preparation of compound 9-1
Mix 1-naphthalene boronic acids 10.2g (59.4mmol), 1-bromo-2-oil of mirbane 10.0g (49.5mmol), Pd (PPh
3)
41.7g (1.4mmol), the K of 2M
2CO
3Aqueous solution 75mL, toluene 200mL and ethanol 100mL reflux and stirred 12 hours.Mixture cleans with distilled water, and uses ethyl acetate extraction.Use anhydrous MgSO
4After removal moisture also under reduced pressure distills, on the gained residue, obtain compound 9-1,9.0g (73.7%) by the post separation.
The preparation of compound 9-2
Compound 9-19.0g (36.1mmol) and N-bromosuccinimide 7.6g (43.3mmol) are dissolved among the methylene dichloride 300mL, at room temperature stirred 12 hours.After underpressure distillation gained solid, clean with distilled water, methyl alcohol and hexane, obtain compound 9-2,9.6g (81.3%).
The preparation of compound 9-3
Mixing cpd 9-29.6g (29.3mmol) and Fe[C
2O
4] 2H
2O(two oxalic acid hydrate iron) 72.2g (175.5mmol) was 205 ℃ of heating 30 minutes.After mixture at room temperature cools off, with the described mixture of ethyl acetate extraction, clean the gained material with distilled water.Use the toluene recrystallization to obtain compound 9-3,5.2g (60.5%).
The preparation of compound 9-4
Mixing cpd 9-330g (101.29mmol), 4-bromo-N-phenyl-N-(4-(9-phenyl-9H-carbazole-3-yl) phenyl) aniline) 41.3g (202.59mmol), CuI9.6g (50.64mmol), Cs
2CO
382.5g (253.2mmol) and toluene 600mL, and 50 ℃ of heating.In mixture, add quadrol 6.8mL (101.29mmol), reflux and stir.After 14 hours, mixture at room temperature cools off, and adds distilled water in mixture.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 9-4,32g (85.96mmol, 84.86%) by the post separation.
The preparation of compound 9-5
Compound 9-423.1g (62.07mmol) is dissolved in the THF of 500mL, and in mixture, slowly adds n-Butyl Lithium 29.79mL (74.48mmol, 2.5M is in hexane) at-78 ℃.After 1 hour, in mixture, add trimethyl borate 10.38mL (93.10mmol).After at room temperature stirring the mixture 12 hours, in mixture, add distilled water, use the ethyl acetate extraction mixture.Use MgSO
4After removal moisture also under reduced pressure distills, use ethyl acetate and hexane to carry out recrystallization and obtain compound 9-5,14g (67%).
The preparation of compound 9-6
Mixing cpd 9-514g (41.79mmol), 2-methyl-bromobenzoate 13.51g (45.97mmol), Pd (PPh
3)
41.9g (1.67mmol), the Na of 2M
2CO
360mL and toluene 200mL reflux and stir.After 12 hours, mixture at room temperature cools off, and adds distilled water in mixture.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 9-6,8.8g (42%) by the post separation.
The preparation of compound 9-7
Compound 9-68.8g (17.53mmol) is dissolved among the THF of 200mL, and in mixture, adds methylmagnesium-bromide 14.60mL (43.82mmol, 3.0M is in diethyl ether).At 60 ℃ of heated mixt.After 6 hours, mixture at room temperature cools off, and to wherein adding distilled water.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 9-7,6.6g (74%) by the post separation.
The preparation of compound 58
Mixing cpd 9-76.6g (13.14mmol), acetic acid 50mL and phosphoric acid 50mL stirred 5 hours at 50 ℃.Mixture at room temperature cools off and neutralizes with NaOH solution.With this mixture of ethyl acetate extraction.Use MgSO
4After removal moisture also under reduced pressure distills, obtain compound 58,5.1g (80%) by the post separation.
MS/FAB measured value 819, theoretical value 818.01
[preparation example 10] preparation compound 122
The preparation of compound 10-1
Mix 2-bromo-9,9-dimethyl-9H-fluorenes 60g (0.219mol), 2-chloroaniline 56g (0.439mol), Pd (OAc)
21.5g (0.006mol), P (t-Bu)
314mL (0.021mol) and CsCO
3143g (0.439mol) adds toluene 600mL in mixture.Mixture stirred 12 hours at 120 ℃.After reaction is finished, clean the gained material with distilled water, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, obtain compound 10-1 by column purification, 65g (92%).
The preparation of compound 10-2
To compound 10-165g (0.20mol), Pd (OAc)
22.3g (0.01mol), Tetrafluoroboric acid two-tertiary butyl-(methyl) phosphine 5.9g (0.02mol) and Na
2CO
3Add in the mixture of 64g (0.60mol) after the DMA of 1000mL, mixture stirred 16 hours at 190 ℃.After reaction is finished, clean the gained material with distilled water, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, obtain compound 10-2 by column purification, 31g (54%).
The preparation of compound 10-3
To compound 10-217g (0.061mol), CuI2.3g (0.012mol), quadrol 3.3mL (0.049mol) and K
3PO
3Add in the mixture of 16g (0.074mol) after the toluene 130mL, mixture stirred 12 hours at 120 ℃.After reaction is finished, clean the gained material with distilled water, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, obtain compound 10-3 by column purification, 7.8g (72%).
The preparation of compound 122
Compound 10-34g (0.009mol), 4-(diphenyl amino) phenyl-boron dihydroxide 3.1g (0.010mol), Pd (PPh
3)
4527mg (0.4mmol), K
2CO
3(2M) mixture of 14mL, EtOH14mL and toluene 28mL stirred 8 hours at 120 ℃.After reaction is finished, clean the gained material with distilled water, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, obtain compound 122 by column purification, 2.6g (47%).
MS/FAB measured value 603, theoretical value 602.76
[preparation example 11] preparation compound 132
The preparation of compound 11-1
Compound 4-210g (36.6mmol), iodo-4-bromobenzene 20g (73.2mmol), CuI3.5g (18.3mmol), quadrol 4.5mL (73.2mmol), K
3PO
419.4g (91.5mmol) and the mixture of toluene 200mL spend the night 120 ℃ of stirrings.After reaction is finished, clean the gained material with distilled water, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, obtain compound 11-1 by column purification, 7.7g (49%).
The preparation of compound 132
Compound 11-17g (16.3mmol), 4-(diphenyl amino) phenyl-boron dihydroxide 5.6g (19.6mmol), Pd (PPh
3)
40.95g (0.82mmol), K
2CO
36g (40.8mmol), toluene 60mL, EtOH20mL and H
2The mixture of O20mL spends the night 100 ℃ of stirrings.After reaction is finished, clean the gained material with distilled water, use ethyl acetate extraction.Use MgSO
4Remove the moisture of organic layer and with after the rotatory evaporator removal solvent, obtain compound 132 by column purification, 5.4g (56%).
MS/FAB measured value 593, theoretical value 592.75
Following compound is the compound according to preparation embodiment 1-11 preparation.
[embodiment 1] uses organic electroluminescent compounds of the present invention to prepare the OLED device
The electroluminescent material of the application of the invention prepares the OLED device.At first, (15 Ω/) (available from SCP company (Samsung-Corning)) carry out ultrasonic cleaning with trieline, acetone, ethanol and distilled water to the transparency electrode ito thin film that is used for OLED successively that will be made by glass, and are stored in the Virahol before use.Then, the ITO substrate is contained in the substrate holder of vacuum sediment equipment, with 2-TNATA (4,4', 4 " three (N, N-(2-naphthyl)-phenyl amino) triphenylamine) place the cell (cell) of vacuum sediment equipment; exhaust then makes indoor vacuum tightness be up to 10
-6Holder.Then, applying electric current with evaporation 2-TNATA to described cell, is the hole injection layer of 60nm thereby form thickness at the ITO substrate.Then, compound 1 being put into another cell of vacuum sediment equipment, evaporate compound 1 by applying electric current to described cell, is the hole transmission layer of 20nm thereby form thickness at described hole injection layer.
After forming hole injection layer and hole transmission layer, form electroluminescence layer in the above, specific as follows.Will be as the CBP[4 of matrix, 4'-N, N'-two carbazoles-biphenyl] be placed in the cell of vacuum vapor deposition equipment, will be as (piq) of doping agent
2Ir (acac) [two-(1-phenyl isoquinolin quinoline base) iridium (III) acetyl pyruvates] is placed in another chamber of vacuum vapor deposition equipment.With different two kinds of materials of speed evaporation, like this with 4-weight % thick electroluminescence layer of vapour deposition 30nm on hole transmission layer.
Afterwards, with two (2-methyl-8-quinoline ester (quinolinato)) (the p-phenyl phenol root closes (phenolato)) aluminium (III) (BAlq) vapour deposition to the electroluminescence layer as the hole barrier layer, thickness is 10nm.Three (oxine)-aluminium (III) that vapour deposition 20nm is thick on electroluminescence layer are (Alq3) as electron transfer layer.Then, the Liq(quinoline thick at vapour deposition 1nm closes lithium) as electron injecting layer after, use another vacuum vapor deposition equipment to form the thick Al negative electrode of 150nm, to make OLED.
The every kind of compound that is used for OLED passes through 10
-6Purifying is carried out in vacuum-sublimation under the holder condition.
As a result of, confirming that electric current flows under the voltage of 6.9V is 13.8mA/cm
2, launched 1020cd/m
2Ruddiness.
[embodiment 2] use organic electroluminescent compounds of the present invention to prepare the OLED device
Make the OLED device as same procedure as described in the embodiment 1, difference is to use compound 19 as hole mobile material.
As a result of, confirming that electric current flows under the voltage of 6.7V is 14.3mA/cm
2, launched 1060cd/m
2Ruddiness.
[embodiment 3] use organic electroluminescent compounds of the present invention to prepare the OLED device
Make the OLED device as same procedure as described in the embodiment 1, difference is to use compound 31 as hole mobile material.
As a result of, confirming that electric current flows under the voltage of 6.7V is 13.9mA/cm
2, launched 1044cd/m
2Ruddiness.
[embodiment 4] use organic electroluminescent compounds of the present invention to prepare the OLED device
Make the OLED device as same procedure as described in the embodiment 1, difference is to use compound 69 as hole mobile material.
As a result of, confirming that electric current flows under the voltage of 6.8V is 14.2mA/cm
2, launched 1015cd/m
2Ruddiness.
[embodiment 5] use organic electroluminescent compounds of the present invention to prepare the OLED device
Make the OLED device as same procedure as described in the embodiment 1, difference is to use compound 1 as hole mobile material, and uses organic iridium complex (Ir (ppy)
3[three (2-phenylpyridine) iridium] as the electroluminescent doping agent on the electroluminescence layer, content is 15 weight %.
As a result, confirming that electric current flows under the voltage of 6.6V is 3.8mA/cm
2, launched 1065cd/m
2Green glow.
[embodiment 6] use organic electroluminescent compounds of the present invention to prepare the OLED device
Make the OLED device as same procedure as described in the embodiment 5, difference is to use compound 20 as hole mobile material.
As a result, confirming that electric current flows under the voltage of 6.6V is 3.9mA/cm
2, launched 1070cd/m
2Green glow.
[embodiment 7] use organic electroluminescent compounds of the present invention to prepare the OLED device
Make the OLED device as same procedure as described in the embodiment 5, difference is to use compound 31 as hole mobile material.
As a result, confirming that electric current flows under the voltage of 6.7V is 3.7mA/cm
2, launched 1085cd/m
2Green glow.
[embodiment 8] use organic electroluminescent compounds of the present invention to prepare the OLED device
Make the OLED device as same procedure as described in the embodiment 5, difference is to use compound 42 as hole mobile material.
As a result, confirming that electric current flows under the voltage of 6.6V is 3.5mA/cm
2, launched 1055cd/m
2Green glow.
[embodiment 9] use organic electroluminescent compounds of the present invention to prepare the OLED device
Make the OLED device as same procedure as described in the embodiment 5, difference is to use compound 43 as hole mobile material.
As a result, confirming that electric current flows under the voltage of 6.6V is 3.6mA/cm
2, launched 1080cd/m
2Green glow.
[embodiment 10] use organic electroluminescent compounds of the present invention to prepare the OLED device
Make the OLED device as same procedure as described in the embodiment 5, difference is to use compound 14 to replace 4,4', and 4 " three (N, N-(2-naphthyl)-phenyl amino) triphenylamine (2-TNATA) is as hole mobile material.
As a result, confirming that electric current flows under the voltage of 6.6V is 3.7mA/cm
2, launched 1050cd/m
2Green glow.
[embodiment 11] use organic electroluminescent compounds of the present invention to prepare the OLED device
N
1, N
1'-([1,1'-phenylbenzene]-4,4'-two bases) two (N
1-(naphthalene-1-yl)-N
4, N
4-diphenyl benzene-1, the 4-diamines) as hole-injecting material, in the chamber, be vented to up to 10 then
-6The vacuum of holder.Apply electric current with evaporation N to cell then
1, N
1'-([1,1'-phenylbenzene]-4,4'-two bases) two (N
1-(naphthalene-1-yl)-N
4, N
4-diphenyl benzene-1, the 4-diamines), thereby form the thick hole injection layer of 60nm at the ITO substrate.Then, compound 122 being put into another cell of vacuum moulding machine device, evaporate compound 122 by applying electric current to described cell, is the hole transmission layer of 20nm thereby form thickness at described hole injection layer.
After forming hole injection layer and hole transmission layer, form electroluminescence layer in the above, specific as follows.In a cell of vacuum vapor deposition equipment, add respectively H-31 add as matrix and in another cell D-58 as doping agent after, two cells mix with the different rates evaporation and with 15 weight %, thereby at the thick electroluminescence layer of hole transmission layer deposition 30nm.Afterwards 2-(4-(9,10-two (naphthalene-2-yl) anthracene-2-yl) phenyl)-1-phenyl-1H-benzo [d] imidazoles is put into the cell of hole transmission layer, (Liq) puts into another cell with the quinolinic acid lithium.Two cells mix with identical speed evaporation and with 50 weight %, are the hole transmission layer of 30nm with the deposit thickness.Then, the thick quinoline of vapour deposition 1nm close lithium (Liq) as electron injecting layer after, use another vacuum vapor deposition equipment to form the thick Al negative electrode of 150nm, to make OLED.
The every kind of compound that is used for OLED passes through 10
-6Purifying is carried out in vacuum-sublimation under the holder condition.
As a result, confirming that electric current flows under the voltage of 5.4V is 11.5mA/cm
2, launched 6200cd/m
2Green glow.
[embodiment 12] use organic electroluminescent compounds of the present invention to prepare the OLED device
Use embodiment 11 described same procedure to make the OLED device, difference is compound 132 as hole mobile material, and H-1 is as matrix, and D-71 is as doping agent.
As a result, confirming that electric current flows under the voltage of 4.0V is 6.32mA/cm
2, launched 3300cd/m
2Green glow.
[embodiment 13] use organic electroluminescent compounds of the present invention to prepare the OLED device
Use embodiment 11 described same procedure to make the OLED device, difference is compound 138 as hole mobile material, and H-34 is as matrix, and D-31 is as doping agent.
As a result, confirming that electric current flows under the voltage of 3.6V is 2.8mA/cm
2, launched 1500cd/m
2Green glow.
[embodiment 14] use organic electroluminescent compounds of the present invention to prepare the OLED device
Use embodiment 11 described same procedure to make the OLED device, difference is compound 149 as hole mobile material, and H-39 is as matrix, and D-31 is as doping agent.
As a result, confirming that electric current flows under the voltage of 3.1V is 1.59mA/cm
2, launched 500cd/m
2Green glow.
[embodiment 15] use organic electroluminescent compounds of the present invention to prepare the OLED device
Use embodiment 11 described same procedure to make the OLED device, difference is compound 109 as hole mobile material, and H-45 is as matrix, and D-6 is doped to 4 weight % as doping agent.
As a result, confirming that electric current flows under the voltage of 4.0V is 7.5mA/cm
2, launched 1065cd/m
2Ruddiness.
[embodiment 16] use organic electroluminescent compounds of the present invention to prepare the OLED device
Use embodiment 15 described same procedure to make the OLED device, difference is compound 141 as hole mobile material, and H-49 is as matrix, and D-6 is as doping agent.
As a result, confirming that electric current flows under the voltage of 5.2V is 17.0mA/cm
2, launched 2210cd/m
2Ruddiness.
[embodiment 17] use organic electroluminescent compounds of the present invention to prepare the OLED device
Use embodiment 15 described same procedure to make the OLED device, difference is compound 142 as hole mobile material, and H-52 is as matrix, and D-6 is as doping agent.
As a result, confirming that electric current flows under the voltage of 5.6V is 32.1mA/cm
2, launched 3700cd/m
2Ruddiness.
[embodiment 18] use organic electroluminescent compounds of the present invention to prepare the OLED device
Use embodiment 15 described same procedure to make the OLED device, difference is compound 149 as hole mobile material, and H-53 is as matrix, and D-9 is as doping agent.
As a result, confirming that electric current flows under the voltage of 6.0V is 12.9mA/cm
2, launched 1710cd/m
2Ruddiness.
[comparative example 1] uses the electroluminescent material of prior art to make the OLED device
Make the OLED device with the method identical with embodiment 1, different is to use N in a cell of vacuum vapor deposition equipment, N'-two (Alpha-Naphthyl)-N, and N'-phenylbenzene-4,4'-diamines [NPB] replace compound of the present invention as hole mobile material.
As a result, confirming that electric current flows under the voltage of 8.2V is 20.0mA/cm
2, launched 1000cd/m
2Ruddiness.
[comparative example 2] uses the electroluminescent material of prior art to make the OLED device
Make the OLED device with the method identical with embodiment 5, different is to use N in a cell of vacuum vapor deposition equipment, N'-two (Alpha-Naphthyl)-N, and N'-phenylbenzene-4,4'-diamines [NPB] replace compound of the present invention as hole mobile material.
As a result, confirming that electric current flows under the voltage of 6.0V is 5.0mA/cm
2, launched 1183cd/m
2Green glow.
[comparative example 3] uses the electroluminescent material of prior art to make the OLED device
Use embodiment 11 described same procedure to make the OLED device, difference is that NPB is used as hole mobile material, and H-1 is as matrix, and D-30 is as doping agent.
As a result, confirming that electric current flows under the voltage of 3.0V is 4.62mA/cm
2, launched 1000cd/m
2Green glow.
[comparative example 4] uses the electroluminescent material of prior art to make the OLED device
Use embodiment 15 described same procedure to make the OLED device, difference is that NPB is used as hole mobile material, and H-46 is as matrix, and D-9 is as doping agent.
As a result, confirming that electric current flows under the voltage of 4.6V is 13.2mA/cm
2, launched 1000cd/m
2Ruddiness.
Confirmation is than traditional material, and organic electroluminescent compounds of the present invention shows excellent electroluminescent character.By increasing triplet state, organic electroluminescent compounds of the present invention can stop very effectively and prevents that the triplet exciton migration from leaving electroluminescence layer.Therefore, also has a benefit, because the electroluminescent efficiency of the excellence of phosphorescence has been made very excellent OLED device.
Though described preferred implementation of the present invention for illustration purposes, it will be understood by those skilled in the art that various improvement, increase and alternative also are possible, they do not deviate from the scope and spirit of the present invention that appended claims limits.
Industrial applicability
According to the present invention, organic electroluminescent compounds can be used as hole mobile material or hole-injecting material, thereby the organic electroluminescence device that obtains can have good illumination efficiency, and have an excellent material performance in work-ing life, and can be used for making and have very excellent operation life and owing to having improved the OLED device that power efficiency reduces watt consumption.
Claims (10)
1. organic electroluminescent compounds of being represented by following Chemical formula 1:
Chemical formula 1
X
1And X
2Represent CR independently
3Or N;
Y
1And Y
2Represent independently chemical bond ,-O-,-S-,-C (R
11R
12)-,-Si (R
13R
14)-or-N (R
15)-, only gets rid of Y
1And Y
2It all is the situation of chemical bond;
R
1To R
3Represent hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C2-C30) heteroaryl, replacement or unsubstituted (C3-C30) cycloalkyl, replacement or unsubstituted 5-unit independently to 7-unit Heterocyclylalkyl, replacement or unsubstituted (C6-C30) aryl (C1-C30) alkyl, replacement or unsubstituted (C1-C30) alkyl silyl, cyano group, nitro or hydroxyl, and when having two or more R
1Or R
2The time, they are interconnected to form ring structure;
L represents to replace or unsubstituted (C6-C30) arylidene or replacement or unsubstituted (C2-C30) heteroarylidene, and when having two or more L, they are interconnected to form ring structure;
Y
3And Y
4Represent independently chemical bond ,-O-,-S-,-C (R
16R
17)-,-Si (R
18R
19)-or-N (R
20)-, only gets rid of Y
3And Y
4It all is the situation of chemical bond;
R
11To R
20Represent hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted (C2-C30) heteroaryl independently, perhaps they can be respectively be connected to form alicyclic ring, monocycle or many cyclophanes ring by replacement or unsubstituted (C3-C30) alkylidene group that has or do not have condensed ring or the replacement that has or do not have condensed ring or unsubstituted (C3-C30) alkenylene and adjacent substituting group;
M and n represent the integer of 0-4 independently, when m and n are during more than or equal to 2 integer, and each R
1With L can be identical or different;
P represents the integer of 0-2, when p=2, and each R
2Can be identical or different; And
Described Heterocyclylalkyl, heteroaryl and heteroarylidene comprise one or more B of being selected from, N, O, S, P (=O), the heteroatoms of Si and P.
2. organic electroluminescent compounds as claimed in claim 1 is characterized in that, described R
1, R
2, R
3, L, Ar
1, Ar
2And R
11To R
20Substituting group one or more substituting groups that can be respectively be selected from down group further replace: deuterium, halogen, halogen replaces or unsubstituted (C1-C30) alkyl, (C6-C30) aryl, (C6-C30) aryl replaces or unsubstituted (C2-C30) heteroaryl, 5-unit to 7-unit Heterocyclylalkyl, the 5-unit that condenses with one or more aromatic rings to 7-unit Heterocyclylalkyl, (C3-C30) cycloalkyl, (C6-C30) cycloalkyl that condenses with one or more aromatic rings, (C2-C30) thiazolinyl, (C2-C30) alkynyl;
Cyano group, carbazyl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl ,-OR
21,-SR
22,-NR
23R
24,-PR
25R
26,-SiR
27R
28R
29, nitro and hydroxyl, and Y
11And Y
12Represent independently chemical bond ,-C (R
31R
32)-,-O-,-S-or-N (R
33)-, only gets rid of Y
11And Y
12It all is the situation of chemical bond; And R
21To R
29And R
31To R
33Expression (C1-C30) alkyl, (C6-C30) aryl, (C2-C30) heteroaryl or (C3-C30) cycloalkyl independently.
5. organic electroluminescence device, described device comprises each described organic electroluminescent compounds among the claim 1-4.
6. organic electroluminescence device as claimed in claim 5 is characterized in that, described organic electroluminescent compounds is as hole-injecting material or hole mobile material.
7. organic electroluminescence device as claimed in claim 6 is characterized in that, this device comprises first electrode; Second electrode; Insert one or more layers organic layer between described first electrode and second electrode, described organic layer comprises one or more organic electroluminescent compounds that Chemical formula 1 is represented.
8. organic electroluminescence device as claimed in claim 7, it is characterized in that described organic layer also comprises one or more metals or the complex compound of transition metal, lanthanide series metal and the d-transition element of the organo-metallic, period 4 and the period 5 that are selected from the 1st family in the periodic table of elements, the 2nd family.
9. organic electroluminescence device as claimed in claim 7 is characterized in that, described organic layer comprises electroluminescence layer and charge generation layer.
10. organic electroluminescence device as claimed in claim 7 is characterized in that, described organic layer also comprises the organic electro luminescent layer of one or more layers red-emitting, green glow and blue light, with the emission white light.
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KR10-2010-0083318 | 2010-08-27 | ||
KR10-2011-0083247 | 2011-08-22 | ||
KR1020110083247A KR20120042633A (en) | 2010-08-27 | 2011-08-22 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
PCT/KR2011/006314 WO2012026780A1 (en) | 2010-08-27 | 2011-08-26 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
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Family
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JP (1) | JP2013537556A (en) |
KR (1) | KR20120042633A (en) |
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TW (1) | TW201213504A (en) |
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TW201213504A (en) | 2012-04-01 |
JP2013537556A (en) | 2013-10-03 |
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