CN103889975A - Benzocarbazole compounds and electroluminescent devices involving them - Google Patents

Benzocarbazole compounds and electroluminescent devices involving them Download PDF

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CN103889975A
CN103889975A CN201280050907.8A CN201280050907A CN103889975A CN 103889975 A CN103889975 A CN 103889975A CN 201280050907 A CN201280050907 A CN 201280050907A CN 103889975 A CN103889975 A CN 103889975A
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alkyl
aryl
replacement
unsubstituted
yuan
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李孝姃
金慧美
李秀镛
朴景秦
李琇炫
安熙春
金南均
丘宗锡
权赫柱
李暻周
金奉玉
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Rohm and Haas Electronic Materials Korea Ltd
Rohm and Haas Electronic Materials LLC
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Abstract

The present invention relates to novel organic electroluminescence compounds and an organic electroluminescence device containing the same. The compounds according to the present invention have high luminous efficiency and long operation lifetime. Therefore, they can produce an organic electroluminescence device having enhanced power consumption efficiency.

Description

Benzo carbazole compound and the electroluminescent device that comprises them
Technical field
The present invention relates to novel organic electroluminescent compounds and comprise the organic electroluminescence device of this compound.
Background technology
Electroluminescent (EL) device is a kind of selfluminous element, and its advantage with respect to the display device of other types has been to provide wider angle of visibility, higher contrast gradient and has had the time of response faster.Eastman Kodak Co (Eastman Kodak) is by being used small molecules (aromatic diamine) and aluminum complex as the material that forms luminescent layer, first developed a kind of organic EL device [Appl.Phys.Lett. (Applied Physics journal) 51,913,1987].
The most important factor that determines luminous efficiency in organic EL device is luminescent material.Up to now, fluorescent material is widely used as luminescent material.But from electroluminescent mechanism, development phosphor material is in theory luminous efficiency to be improved to one of the best way of 4 times.Iridium (III) complex compound is well-known phosphor material, comprises two (2-(2'-benzothienyl)-pyridine root closes-N, C3') (methyl ethyl diketone acid group closes) iridium ((acac) Ir (btp) 2), three (2-phenylpyridine) iridium (Ir (ppy) 3) and two (4,6-difluorophenyl pyridine root closes-N, C2) pyridine carboxylic acid root close (picolinato) iridium (Firpic), respectively as red, green and blue material.Particularly, recently in Japan, Europe and the U.S., people study a large amount of phosphor materials.
Up to now, known 4,4'-N, N'-bis-carbazoles-biphenyl (CBP) is the substrate material that is widely used as phosphorus most.In addition, known organic EL device uses bathocuproine (BCP) and two (2-methyl-oxine closes (quinolinate)) (4-phenylphenol) aluminium (III) (BAlq) for hole blocking layer; Japan Pioneer Co., Ltd (Pioneer) etc. has developed a kind of high-performance organic EL device, and it has adopted the derivative of BAlq as substrate material.
Although these materials provide the good characteristics of luminescence, they have following some shortcomings.Due to their lower second-order transition temperatures and poor thermostability, when they can be degraded during in a vacuum in high temperature deposition process.Because the power efficiency of organic EL device is definite by [(π/voltage) × current efficiency], power efficiency and voltage are inversely proportional to, and reduce power consumption thereby therefore must improve power efficiency.Although the organic EL device that contains phosphor material provides the current efficiency (cd/A) higher than the organic EL device that contains fluorescent material, but compared with adopting the organic EL device of fluorescent material, adopt the organic EL device of conventional phosphor material (as BAlq or CBP) to there is higher driving voltage.Therefore, adopt the El element of conventional phosphor material there is no advantage in power efficiency (lm/w).In addition, the working life of this organic EL device is short.
Korean patent application JP No.2010-0023783 discloses a kind of carbazole compound replacing with amido, and uses the green fluorescence organic EL device of this carbazole compound as hole mobile material.In addition, described document also discloses the benzo carbazole compound replacing with carbazole group, and uses the phosphorescence organic EL device of this benzo carbazole compound as substrate material.But what this device was launched is green glow.
Japanese Patent Application Laid-Open No.2000-286056 discloses a kind of carbazole compound being condensed by aromatic ring, and comprises the organic EL device of the polymkeric substance of this compound.But what this device was launched is green glow or orange coloured light.
Japanese Patent Application Laid-Open No.1999-144866 discloses a kind of two carbazole compounds and has comprised the organic EL device of this two carbazole compound.But it only discloses this compound as hole mobile material.
Summary of the invention
Technical problem
The object of this invention is to provide a kind of organic electroluminescent compounds, this compound makes device have high-luminous-efficiency and long service live and has suitable chromaticity coordinates; The present invention also provides a kind of organic electroluminescence device of described compound as luminescent material that adopt, and it has high-level efficiency and long lifetime.
The method of dealing with problems
The present inventor finds that the compound that can represent by following general formula 1 realizes above-mentioned purpose:
Figure BDA0000492037920000031
Wherein
Figure BDA0000492037920000032
L 1represent singly-bound, replacement or unsubstituted (C6-C30) arylidene or replacement or unsubstituted 3 yuan to 30 yuan heteroarylidenes;
Ar 1to Ar 3represent independently of one another CR 11or N, prerequisite is Ar 1to Ar 3different times table CH;
X Dai Biao – O-,-S-,-CR 12r 13-,, Huo – NR 14-;
R 1, R 2, R 11, Ar 1and Ar 2represent independently of one another hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted 3-30 unit heteroaryl ,-NR 15r 16,-SiR 17r 18r 19,-SR 20,-OR 21, cyano group or nitro;
R 12to R 14represent independently of one another to replace or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted 3 yuan to 30 yuan heteroaryls;
R 15to R 21represent independently of one another hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted 3 yuan to 30 yuan heteroaryls; Or they are connected form monocycle or encircle more with adjacent substituting group, (C5-C30) alicyclic ring or aromatic ring, the heteroatoms that its carbon atom can be selected from nitrogen, oxygen and sulphur by least one substitutes;
A represents the integer of 1-6; When a is while being equal to or greater than 2 integer, each R 1identical or different;
B represents the integer of 1-3; When b is while being equal to or greater than 2 integer, each R 2identical or different;
Described Heterocyclylalkyl and assorted (Asia) aryl contain at least one and are selected from the heteroatoms of B, N, O, S, P (=O), Si and P.
The beneficial effect of the invention
Organic electroluminescent compounds of the present invention has high-luminous-efficiency and long service live.Therefore, this compound can be produced the organic electroluminescence device of the power consumption efficiency with enhancing.
Embodiments of the present invention
To describe the present invention below in detail.But below describing is for explaining the present invention, instead of in order to limit the scope of the invention in any way.
The present invention relates to the organic electroluminescent compounds representing with above-mentioned general formula 1, comprise the electroluminescent organic material of described organic electroluminescent compounds, and comprise the organic electroluminescence device of described material.
Wherein, (" C1-C30) (Asia) alkyl " refer to (Asia) alkyl of line style or the branching with 1-30 carbon atom, the preferred 1-20 of quantity of its carbon atom, more preferably 1-10, should comprise methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, tertiary butyl etc. by (Asia) alkyl; " (C2-C30) thiazolinyl " refers to the thiazolinyl of line style or the branching with 2-30 carbon atom, the preferred 2-20 of quantity of its carbon atom, more preferably 2-10, this thiazolinyl comprises vinyl, 1-propenyl, 2-propenyl, 1-butylene base, crotyl, 3-butenyl, 2-methyl but-2-ene base etc.; " (C2-C30) alkynyl " refers to the alkynyl of line style or the branching with 2-30 carbon atom, the preferred 2-20 of quantity of its carbon atom, more preferably 2-10, this alkynyl comprises ethynyl, 1-proyl, 2-propynyl, ethyl acetylene base, 2-butyne base, 3-butynyl, 1-methylpent-2-alkynyl etc.; " (C3-C30) cycloalkyl " refers to monocycle or the polynuclear hydrocarbon with 3-30 carbon atom, the preferred 3-20 of quantity of its carbon atom, and more preferably 3-7, this cycloalkyl comprises cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc.; " 3 yuan of-7 yuan of Heterocyclylalkyls " refer to the cycloalkyl with at least one heteroatoms and 3-7 ring skeletal atom, described heteroatoms is selected from B, N, O, S, P (=O), Si and P, preferably O, S and N, this Heterocyclylalkyl comprises tetrahydrofuran (THF), tetramethyleneimine, tetramethylene sulfide (thiolan), tetrahydropyrans etc.; " (C6-C30) (Asia) aryl " is derived from monocycle or the condensed ring of aromatic hydrocarbons with 6-30 carbon atom, wherein the quantity of carbon atom is preferably 6-20, more preferably 6-15, should (Asia) aryl comprise phenyl, xenyl, terphenyl, naphthyl, fluorenyl, phenanthryl, anthryl, indenyl, benzo [9,10] phenanthryl, pyrenyl, naphthacenyl (tetracenyl), perylene base (perylenyl),
Figure BDA0000492037920000041
base (chrysenyl), naphtho-naphthyl (naphthacenyl), fluoranthene base (fluoranthenyl) etc.; " 3 yuan-30 yuan assorted (Asia) aryl " is the aryl with at least one heteroatoms (preferably 1-4 heteroatoms) and 3-30 ring skeletal atom, and described heteroatoms is selected from B, N, O, S, P (=O), Si and P; This assorted (Asia) aryl is monocycle or the condensed ring that condenses with at least one phenyl ring; This assorted (Asia) aryl preferably has 5-20 ring skeletal atom, more preferably have 5-10 encircles skeletal atom; This assorted (Asia) aryl can be fractional saturation; This assorted (Asia) aryl can be connected to form at least one heteroaryl or aromatic yl group and heteroaryl by singly-bound; This assorted (Asia) aryl comprises mononuclear type heteroaryl, comprises furyl, thienyl, pyrryl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl group, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazine base, triazolyl, tetrazyl, furazan base (furazanyl), pyridyl, pyrazinyl, pyrimidyl, pyridazinyl etc.; And condensed ring type heteroaryl, comprise benzofuryl, benzothienyl, isobenzofuran-base, dibenzofuran group, dibenzothiophene base, benzimidazolyl-, benzothiazolyl, benzisothiazole base, benzoisoxazole base, benzoxazolyl, pseudoindoyl, indyl, indazolyl, diazosulfide base, quinolyl, isoquinolyl, cinnolines base, quinazolyl, quinoxalinyl, carbazyl, phenoxazinyl, phenanthridinyl, benzo dioxolyl etc.In addition, " halogen " comprises F, Cl, Br and I.
The hydrogen atom that " replacement " in term used herein " replacement or unsubstituted " refers in certain functional group is replaced by another atom or group (being substituting group).
The L of general formula 1 1, R 1, R 2, R 11to R 21, Ar 1and Ar 2the substituting group of assorted (Asia) aryl of the alkyl replacing described in group, (Asia) aryl of replacement, replacement, ring (Asia) alkyl, the Heterocyclylalkyl of replacement and the aralkyl of replacement of replacement is that at least one is selected from the group of lower group: deuterium independently of one another; Halogen; Unsubstituted or replaced by halogen (C1-C30) alkyl; (C6-C30) aryl; Unsubstituted or with (C1-C30) alkyl and/or (C6-C30) aryl replace 3 yuan to 30 yuan heteroaryls; (C3-C30) cycloalkyl; 5 yuan to 7 yuan Heterocyclylalkyls; Three (C1-C30) alkyl silyl; Three (C6-C30) aryl silyl; Two (C1-C30) alkyl (C6-C30) aryl silyl; (C1-C30) alkyl two (C6-C30) aryl silyl; (C2-C30) thiazolinyl; (C2-C30) alkynyl; Cyano group; N-carbazyl; Two (C1-C30) alkylamino; Two (C6-C30) arylamino; (C1-C30) alkyl (C6-C30) arylamino; Two (C6-C30) aryl boron carbonyl; Two (C1-C30) boron alkyl carbonyl; (C1-C30) alkyl (C6-C30) aryl boron carbonyl; (C6-C30) aryl (C1-C30) alkyl; (C1-C30) alkyl (C6-C30) aryl; Carboxyl; Nitro and hydroxyl.
Organic electroluminescent compounds of the present invention can be represented by following formula 2 or 3:
Wherein
X, R 1, R 2, a, b, L 1, A 1to A 3, Ar 1and Ar 2as above defined in general formula 1.Specifically, organic electroluminescent compounds of the present invention can be by following formula 4 to 9 expressions:
Figure BDA0000492037920000061
Figure BDA0000492037920000071
Wherein
X, R 1, R 2, a, b, L 1, A 1to A 3, Ar 1and Ar 2as above defined in general formula 1.
Specifically, L 1represent singly-bound or (C6-C30) arylidene; Ar 1to Ar 3represent independently of one another CR 11or N, prerequisite is Ar 1to Ar 3different times table CH; X representative-NR 14-; R 11represent hydrogen, deuterium, (C1-C30) alkyl, (C6-C30) aryl or 3-30 unit heteroaryl; R 14represent (C1-C30) alkyl, (C6-C30) aryl or 3-30 unit heteroaryl; And R 1, R 2, Ar 1and Ar 2represent independently of one another hydrogen, deuterium, halogen, (C1-C30) alkyl, (C6-C30) aryl or 3-30 unit heteroaryl.L 1in arylidene, R 1, R 2, R 11, R 14, Ar 1and Ar 2in alkyl, the group that aryl and heteroaryl can be selected from lower group by least one replaces: deuterium, halogen, (C1-C30) alkyl, halo (C1-C30) alkyl, (C6-C30) aryl, 3 yuan to 30 yuan heteroaryls, 3 yuan to the 30 yuan heteroaryls that quilt (C6-C30) aryl and/or (C1-C30) alkyl replace, (C3-C30) cycloalkyl, three (C1-C30) alkyl silyl, three (C6-C30) aryl silyl, two (C1-C30) alkyl (C6-C30) aryl silyl, (C1-C30) alkyl two (C6-C30) aryl silyl, (C6-C30) aryl (C1-C30) alkyl and (C1-C30) alkyl (C6-C30) aryl.
Specifically, L 1represent singly-bound, phenylene, naphthylidene, biphenylene, sub-tetrad phenyl (terphenylene), anthrylene, sub indenyl, fluorenylidene, phenanthrylene, sub-benzo [9,10] phenanthryl, sub-pyrenyl, sub-perylene base, Asia base, sub-naphthacenyl, sub-fluoranthene base, phenylene-naphthylidene (phenylene-naphthylene), furylidene, sub-thienyl, sub-pyrryl, sub-imidazolyl, sub-pyrazolyl, sub-thiazolyl, sub-thiadiazolyl group, sub-isothiazolyl, Ya isoxazolyl, Ya oxazolyl, Ya oxadiazolyl, sub-triazinyl, sub-tetrazine base, sub-triazolyl, sub-furazan base, pyridylidene, sub-pyrazinyl, sub-pyrimidyl, sub-pyridazinyl, sub-benzofuryl, sub-benzothienyl, sub-isobenzofuran-base, sub-benzimidazolyl-, sub-benzothiazolyl, sub-benzisothiazole base, sub-benzoisoxazole base, sub-benzoxazolyl, sub-pseudoindoyl, sub-indyl, sub-indazolyl, sub-diazosulfide base, quinolinediyl, sub-isoquinolyl, sub-cinnolines base, sub-quinazolyl, sub-quinoxalinyl, sub-carbazyl, sub-phenanthridinyl, sub-benzo dioxolyl, sub-dibenzofuran group or sub-dibenzo acyl phenyl (dibenzocyophenylene).
In addition R, 1, R 2, R 11, Ar 1and Ar 2represent independently of one another hydrogen, halogen, (C1-C30) alkyl or be selected from following group:
Figure BDA0000492037920000081
Wherein R 21to R 28represent independently of one another halogen, (C1-C30) alkyl, (C6-C30) aryl, 3 yuan to 30 yuan heteroaryls or (C3-C30) cycloalkyl.
Organic electroluminescent compounds of the present invention comprises following compound:
Figure BDA0000492037920000082
Figure BDA0000492037920000091
Figure BDA0000492037920000101
Figure BDA0000492037920000111
Figure BDA0000492037920000131
Organic electroluminescent compounds of the present invention can be prepared by following reaction scheme.
[reaction scheme 1]
Figure BDA0000492037920000132
Wherein Z, X, R 1, R 2, a, b, L 1, Ar 1to Ar 3, Ar 1and Ar 2as general formula 1 above defines, and Hal represents halogen.
In addition, the invention provides the organic electroluminescent compounds electroluminescent organic material that comprises general formula 1, and comprise the organic electroluminescence device of described material.Above-mentioned materials can only include according to organic electroluminescent compounds of the present invention, or also can comprise the conventional material that is generally used for electroluminescent organic material.Described organic electroluminescence device comprises at least one deck organic layer between the first electrode, the second electrode and described the first electrode and the second electrode.The compound that described organic layer comprises at least one general formula 1 of the present invention.In addition, described organic layer comprises luminescent layer, wherein comprises the compound of general formula 1 as substrate material.
In the time that the organic electroluminescent compounds of general formula 1 is used as to the substrate material in luminescent layer, described layer comprises at least one phosphorescent dopants.For not concrete restriction of the phosphorescent dopants of organic electroluminescence device of the present invention, but for according to the represented compound of the following general formula 10 of the optional freedom of the phosphorescent dopants of organic electroluminescence device of the present invention:
M 1L 101L 102L 103 (10)
Wherein M 1be selected from Ir, Pt, Pd and Os; L 101, L 102and L 103be selected from independently of one another following structure:
R 201to R 203represent independently of one another hydrogen, deuterium, unsubstituted or (C1-C30) alkyl being replaced by halogen, (C6-C30) aryl or halogen unsubstituted or that replaced by (C1-C30) alkyl;
R 204to R 219represent independently of one another hydrogen, deuterium, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C1-C30) alkoxyl group, replacement or unsubstituted (C3-C30) cycloalkyl, replacement or unsubstituted (C2-C30) thiazolinyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted list-or two-(C1-C30) alkylamino, replacement or unsubstituted list-or two-(C6-C30) arylamino, 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 of one another hydrogen, deuterium, unsubstituted or (C1-C30) alkyl or (C6-C30) aryl unsubstituted or that replaced by (C1-C30) alkyl of being replaced by halogen;
R 224and R 225represent independently of one another hydrogen, deuterium, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or halogen, or R 224and R 225can be connected to form with adjacent substituting group (C5-C30) alicyclic ring or the aromatic ring of monocycle or many rings;
R 226represent to replace or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted 5 yuan to 30 yuan heteroaryls or halogen;
R 227to R 229represent independently of one another hydrogen, deuterium, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or halogen;
Q represents
Figure BDA0000492037920000151
r 231to R 242represent independently of one another hydrogen, deuterium, unsubstituted or (C1-C30) alkyl, (C1-C30) alkoxyl group, halogen, replacement or unsubstituted (C6-C30) aryl, cyano group or replacement or unsubstituted (C5-C30) cycloalkyl of being replaced by halogen, or R 231to R 242in each Tong Guo alkylidene group or alkenylene be connected to form volution or condensed ring with adjacent substituting group, or can pass through alkylidene group or alkenylene and R 207or R 208be connected to form saturated or undersaturated condensed ring.Doping agent in general formula 10 preferably includes following:
Figure BDA0000492037920000152
Figure BDA0000492037920000161
Except the compound that general formula 1 represents, organic electroluminescence device of the present invention also can comprise that at least one is selected from the compound of the compound of compound based on arylamine and styrene-based base arylamine.
In organic electroluminescence device of the present invention, described organic layer also can comprise at least one and be selected from the organometallic metal of the periodic table of elements the 1st family's metal, group II metal, period 4 transition metal, period 5 transition metal, lanthanide series metal and d-transition element, or at least one complex compound that comprises described metal.Described organic layer can comprise luminescent layer and charge generation layer.
In addition, except compound of the present invention, described organic electroluminescence device can carry out transmitting white by further comprising at least one deck luminescent layer, and described luminescent layer comprises blue light electroluminescent compounds, ruddiness electroluminescent compounds or green glow electroluminescent compounds.
Preferably, in organic electroluminescence device of the present invention, can on the internal surface of one or two electrode, place one deck at least and be selected from the layer (hereinafter referred to as " upper layer ") of chalcogenide layer, metal halide and metal oxide layer.Particularly, preferably the chalkogenide of silicon or aluminium (comprising oxide compound) layer is placed on the anode surface of electroluminescent medium layer, metal halide or metal oxide layer are placed on the cathode surface of electroluminescent medium layer.Described upper layer provides job stability for organic electroluminescence device.Preferably, described chalkogenide comprises SiO x(1≤X≤2), AlO x(1≤X≤1.5), SiON, SiAlON etc.; Described metal halide comprises LiF, MgF 2, CaF 2, rare earth metal fluorochemical etc.; Described metal oxide comprises Cs 2o, Li 2o, MgO, SrO, BaO, CaO etc.
Preferably, in organic electroluminescence device of the present invention, the mixing zone of the mixing zone of electric transmission compound and reductibility doping agent or hole transport compound and oxidisability doping agent can be placed at least one surface in electrode pair.In this case, electric transmission compound is reduced into negatively charged ion, and electronics injects from mixing zone and is transferred to electroluminescent medium and becomes and be more prone to like this.In addition, hole transport compound is oxidized to positively charged ion, thereby hole is injected from mixing zone and is transferred to electroluminescent medium and becomes and be more prone to.Preferably, described oxidisability doping agent comprises various Lewis acids and acceptor compound, and described reductibility doping agent comprises basic metal, alkali metal compound, alkaline-earth metal, rare earth metal and composition thereof.Can adopt reductibility dopant layer to prepare the electroluminescent device with two-layer or more multi-layered electroluminescence layer transmitting white as charge generation layer.
The luminosity of the device of describing the preparation method of described organic electroluminescent compounds, described compound in detail and comprising the compounds of this invention below with reference to following examples:
embodiment 1: prepare compd A-47
Figure BDA0000492037920000171
the preparation of compound 1-1
Bromo-Isosorbide-5-Nitrae-bis-2-oil of mirbane (30.0 grams, 106.8 mmoles), 1-naphthalene boronic acids (220.0 grams, 128.1 mmoles), Na 2cO 3(34.0 grams, 320.4 mmoles), and tetrakis triphenylphosphine palladium (0) [Pd (PPh 3) 4] (6.17 grams, 5.3 mmoles) add to after toluene (640 milliliters)/EtOH (160 milliliters), reaction mixture is stirred 3 hours at 90 DEG C.After stirring finishes, complete reaction cool to room temperature by adding pure water (160 milliliters), then use distilled water and ethyl acetate (EA) to extract.Concentrated gained organic layer, separates by post [dichloromethane/hexane (MC/ hexane)], obtains compound 1-1 (30 grams, 86%).
the preparation of compound 1-2
Compound 1-1 (47.5 grams, 144.75 mmoles), triethyl-phosphite ([P (OEt) 3] after (300 milliliters) and 1,2-dichlorobenzene (200 milliliters) mix, this reaction mixture is stirred 1 day at 150 DEG C.After reaction finishes, concentrated this reaction mixture extracting with EA under reduced pressure, and concentrated organic layer.By the separating obtained organic layer of post (MC/ hexane), obtain compound 1-2 (16 grams, 37%).
the preparation of compound 1-3
Compound 1-2 (15.5 grams, 52.3 mmoles), (11.7 milliliters of iodobenzenes, 104.7 mmoles), CuI (5.0 grams, 26.2 mmoles), quadrol (EDA) (1.8 milliliters, 26.2 mmoles), and Cs 2cO 3after (51.2 grams, 157.0 mmoles) add in toluene (250 milliliters), this reaction mixture is stirred 1 day.With EA abstraction reaction mixture, carry out underpressure distillation, then separate by post (MC/ hexane), obtain compound 1-03 (7.9 grams, 40%).
the preparation of compound 1-4
By (7.84 grams of compound 1-3,21.1 mmoles) be dissolved in after tetrahydrofuran (THF) (THF) (200 milliliters), reaction mixture is cooled to-78 DEG C, and by (10.1 milliliters of the 2.5M n-BuLi in hexane, 25.3 mmoles) add slowly this reaction mixture to, and this reaction mixture is stirred 1 hour.At the same temperature, by B (Oi-Pr) 3(6.3 milliliters, 27.4 mmoles) add this reaction mixture to, and this reaction mixture is stirred 1 day.After reaction finishes, carry out cancellation reaction mixture by adding 2M HCl, with distilled water and EA extraction, and concentrated organic layer.Gained organic layer is carried out to recrystallization with MC and hexane, obtain compound 1-4 (5.54 grams, 78%).
the preparation of compound 1-5
Cyanuryl chloride (36 grams, 195 mmoles) is joined in flask, and uses THF(360 milliliter) dissolve.By reaction mixture Slow cooling to 0 DEG C, and PhMgBr (160 milliliters) is slowly added to this reaction mixture.In the time being increased to room temperature, reaction mixture being stirred 2 hours, and add distilled water to complete reaction.Extract organic layer with EA, use MgSO 4be dried organic layer to remove remaining moisture, and use MC/MeOH recrystallization, to obtain compound 1-5 (30 grams, 57%).
prepare compd A-47
By compound 1-4 (3.0 grams, 11.2 mmoles), compound 1-5 (4.5 grams, 13.5 mmoles), Pd (PPh 3) 4(648 milligrams, 0.561 mmole) and Na 2cO 3(3.6 grams, 33.6 mmoles) are dissolved in after toluene (80 milliliters)/EtOH (20 milliliters)/distilled water (20 milliliters), and this reaction mixture refluxed is stirred 1 day.Pure water is added to this reaction mixture, and filter this reaction mixture under reduced pressure.With MC dissolving gained solid, and separate by post (MC/ hexane), obtain compd A-47 (3.5 grams, 60%).
The measured value 524.61 of MS/FAB; Calculated value 524.20
embodiment 2: prepare compd A-48
the preparation of compound 2-1
Compound 1-4 (7.3 grams, 21.65 mmoles), the bromo-4-phenyl-iodide of 1-(18.3 grams, 64.95 mmoles), Pd (PPh 3) 4(1.25 grams, 1.08 mmoles) and Na 2cO 3(6.9 grams, 64.95 mmoles) add in flask, and with THF (200 milliliters)/EtOH (32 milliliters) dissolving, reaction mixture are stirred 3 hours at 90 DEG C.After stirring finishes, slowly add pure water to complete reaction, by reaction mixture cool to room temperature, then use distilled water and ethyl acetate (EA) to extract.Concentrated gained organic layer, and separate by post, compound 2-1 (6.7 grams, 68%) obtained.
the preparation of compound 2-2
Add compound 2-1 (6.7 grams, 14.94 mmoles) to flask, and with THF (100 milliliters) dissolving, reaction mixture is cooled to-78 DEG C.After 10 minutes, the 2.5Mn-BuLi in hexane (7.1 milliliters, 17.93 mmoles) is slowly added to this flask, and this reaction mixture is stirred 1 hour.At the same temperature, by B (Oi-Pr) 3(5.15 milliliters, 22.4 mmoles) slowly add this reaction mixture to, and this reaction mixture is stirred 24 hours.After stirring finishes, carry out cancellation reaction mixture by adding 1MHCl, with distilled water and EA extraction.Concentrated gained organic layer, and gained organic layer is carried out to recrystallization with MC and hexane, obtain compound 2-2 (4 grams, 65%).
prepare compd A-48
Compound 2-2 (2.39 grams, 8.95 mmoles), compound 1-5 (4.079 grams, 9.84 mmoles), Pd (PPh 3) 4(0.516 gram, 0.44 mmole) and K 2cO 3(3.7 grams, 26.7 mmoles) add in flask, and with toluene (50 milliliters)/EtOH (13 milliliters) dissolving, reaction mixture are refluxed 24 hours at 120 DEG C.By adding pure water to complete after reaction, by reaction mixture cool to room temperature, then use distilled water and ethyl acetate (EA) to extract.Concentrated gained organic layer, and gained organic layer is carried out to recrystallization with EA and MeOH, obtain compd A-48 (1.8 grams, 35%).
The measured value 600.71 of MS/FAB; Calculated value 600.23
embodiment 3: prepare compd A-1
Figure BDA0000492037920000201
the preparation of compound 3-1
Bromo-1-2-oil of mirbane (100 grams, 495 mmoles), 1-naphthalene boronic acids (102 grams, 593 mmoles), Pd (PPh 3) 4(23 grams, 19.9 mmoles) and K 2cO 3(171 grams, 1237 mmoles) add in flask, and dissolve after this reaction mixture by adding toluene (1.2 liters)/EtOH (600 milliliters), and reaction mixture is stirred 3 hours at 90 DEG C.After stirring finishes, complete reaction by slow interpolation pure water, and extract organic layer with EA, use MgSO 4dry organic layer is to remove remaining moisture.By the separating obtained organic layer of post, obtain compound 3-1 (106 grams, 86%).
the preparation of compound 3-2
Add compound 3-1 (106 grams, 425 mmoles) to flask and dissolve after this compound by adding triethyl-phosphite (500 milliliters), this reaction mixture is stirred 24 hours at 150 DEG C.After having reacted, remove residual solvent by water distilling apparatus, and filter by post, obtain compound 3-2 (55 grams, 60%).
the preparation of compound 3-3
At 0 DEG C, by (20 grams of compound 3-2,92 mmoles) be dissolved in after dimethyl formamide (DMF), by (16.3 grams of N-bromosuccinimides (NBS), 92 mmoles) slowly add this reaction mixture, and this reaction mixture is stirred 24 hours.After having reacted, extract organic layer with EA, and use MgSO 4dry organic layer is to remove remaining moisture.By the separating obtained organic layer of post, obtain compound 3-3 (23.5 grams, 87%).
the preparation of compound 3-4
By compound 3-3 (20 grams, 6.5 mmoles), phenyl-iodide (15 milliliters, 135 mmoles), CuI (6.4 grams, 33.6 mmoles), quadrol (2.3 milliliters, 33.6 mmoles) and K 2pO 4(43 grams, 202.5 mmoles) add in flask and dissolve after this reaction mixture by adding toluene (300 milliliters), by this reaction mixture 120 DEG C of stirrings 24 hours.After having reacted, extract organic layer with EA, and use MgSO 4dry organic layer is to remove remaining moisture.By the separating obtained organic layer of post, obtain compound 3-4 (19 grams, 76%).
the preparation of compound 3-5
Add compound 3-4 (19 grams, 51 mmoles) to flask, and with THF (300 milliliters) dissolving, reaction mixture is cooled to-78 DEG C.After 10 minutes, the 2.5Mn-BuLi in hexane (24.4 milliliters, 61.2 mmoles) is slowly added to this flask, and this reaction mixture is stirred 1 hour.At the same temperature, slowly add triisopropyl borate ester (14.1 milliliters, 61.2 mmoles) to this reaction mixture, and this reaction mixture is stirred 24 hours.After stirring finishes, carry out cancellation reaction mixture by adding 1M HCl, with distilled water and EA abstraction reaction mixture, and use MgSO 4dry reaction mixture is to remove remaining moisture.Concentrated gained organic layer, and gained organic layer is carried out to recrystallization with MC and hexane, obtain compound 3-5 (12 grams, 70%).
prepare compd A-1
Compound 3-5 (8.2 grams, 24.3 mmoles), compound 1-5 (5.43 grams, 20.1 mmoles), Pd (PPh 3) 4(0.93 gram, 0.81 mmole) and K 2cO 3(8.4 grams, 60.8 mmoles) add in flask, and with toluene (70 milliliters)/EtOH (30 milliliters) dissolving, reaction mixture are stirred 24 hours at 120 DEG C.By adding pure water to complete after reaction, extract organic layer with EA, and use MgSO 4dry organic layer is to remove remaining moisture.Gained organic layer is carried out to recrystallization with EA and MeOH, obtain compd A-1 (2.3 grams, 23%).
The measured value 524.61 of MS/FAB; Calculated value 524.20
embodiment 4: prepare compd A-49
Figure BDA0000492037920000221
the preparation of compound 4-1
Compound 3-5 (22 grams, 65 mmoles), the bromo-4-phenyl-iodide of 1-(28 grams, 98.95 mmoles), Pd (PPh 3) 4(3.7 grams, 3.2 mmoles) and Na 2cO 3(20.7 grams, 195 mmoles) add in flask, and dissolve after this reaction mixture by adding toluene (330 milliliters)/EtOH (150 milliliters), and reaction mixture is stirred 3 hours at 90 DEG C.After stirring finishes, complete reaction by adding pure water, and extract organic layer with EA, use MgSO 4dry organic layer is to remove remaining moisture.By the separating obtained organic layer of post, obtain compound 4-1 (25 grams, 86%).
the preparation of compound 4-2
Compound 4-1 (25 grams, 55.7 mmoles) is dissolved in after tetrahydrofuran (THF) (THF) (300 milliliters), reaction mixture is cooled to-78 DEG C.After 10 minutes, add slowly the 2.5M n-BuLi in hexane (29 milliliters, 72.41 mmoles) to this reaction mixture, and this reaction mixture is stirred 1 hour.At the same temperature, slowly add triisopropyl borate ester (19.2 milliliters, 83.5 mmoles) to this reaction mixture, and this reaction mixture is stirred 24 hours.After stirring finishes, carry out cancellation reaction mixture by adding 1M HCl, with distilled water and EA extraction organic layer, and use MgSO 4dry organic layer is to remove remaining moisture.Gained organic layer is carried out to recrystallization with MC and hexane, obtain compound 4-2 (16.5 grams, 71%).
prepare compd A-49
Compound 4-2 (16.5 grams, 40 mmoles), compound 1-5 (8 grams, 29.8 mmoles), Pd (PPh 3) 4(1.7 grams, 1.5 mmoles) and K 2cO 3(12.4 grams, 89.4 mmoles) add in flask, and with toluene (150 milliliters)/EtOH (75 milliliters) dissolving, reaction mixture are refluxed 24 hours at 120 DEG C.By adding pure water to complete after reaction, extract organic layer with EA, and use MgSO 4dry organic layer is to remove remaining moisture.Gained organic layer is carried out to recrystallization with EA and MeOH, obtain compd A-49 (6 grams, 32%).
The measured value 600.71 of MS/FAB; Calculated value 600.23
embodiment 5: the preparation of compd B-1
Figure BDA0000492037920000231
the preparation of compound 5-1
By 2-bromo nitrobenzene (29.3 grams, 145 mmoles), 1-naphthalene boronic acids (30 grams, 174 mmoles), Pd (PPh 3) 4(6.7 grams, 5.8 mmoles) and Na 2cO 3(38 grams, 362 mmoles) add to after toluene (550 milliliters)/EtOH (180 milliliters)/distilled water (180 milliliters), and reaction mixture is stirred 2 hours at 110 DEG C.After cool to room temperature, extract this reaction mixture with distilled water and EA, and use MgSO 4dry this reaction mixture is to remove remaining moisture.Concentrated gained organic layer, and separate by post (MC/ hexane), compound 5-1 (30 grams, 82%) obtained.
the preparation of compound 5-2
Mixing cpd 5-1 (26.5 grams, 106 mmoles) and CCl 4(250 milliliters), are cooled to-5 DEG C, and add FeCl 3(1.7 grams, 10.6 mmoles) and dropwise add Br 2(17 grams, 176 mmoles).After stirring is spent the night, use Na 2s 2o 3this reaction mixture of solution cancellation, and wash 2MNaOH solution washing with water, then extract this reaction mixture with distilled water and MC, and use MgSO 4dry this reaction mixture is to remove remaining moisture.Concentrated gained organic layer, and separate by post (MC/ hexane), compound 5-2 (31 grams, 90%) obtained.
the preparation of compound 5-3
Mixing cpd 5-2 (31 grams, 95 mmoles), P (OEt) 3(150 milliliters), and 1,2-dichlorobenzene (150 milliliters), and stir and spend the night at 140 DEG C.After having reacted, concentrated this reaction mixture extracting with EA under reduced pressure.Concentrated gained organic layer, and separate by post (MC/ hexane), compound 5-3 (15 grams, 52%) obtained.
the preparation of compound 5-4
Compound 5-3 (7.5 grams, 25.3 mmoles), phenyl-iodide (7.5 milliliters, 51 mmoles), CuI (5.4 grams, 12.7 mmoles), quadrol (EDA) (0.88 milliliter, 12.7 mmoles) and Cs 2cO 3(23 grams, 76 mmoles) add to after toluene (125 milliliters), and reaction mixture is stirred 1 day at 120 DEG C.Extract this reaction mixture with distilled water and EA, and use MgSO 4dry this reaction mixture is to remove remaining moisture.Concentrated gained organic layer, and separate by post (MC/ hexane), compound 5-4 (7.9 grams, 84%) obtained.
the preparation of compound 5-5
By (7.5 grams of compound 5-4,79 mmoles) be dissolved in after tetrahydrofuran (THF) (THF) (75 milliliters), reaction mixture is cooled to-78 DEG C, and by (10 milliliters of the 2.5M n-BuLi in hexane, 103 mmoles) add slowly this reaction mixture to, and this reaction mixture is stirred 1 hour.At the same temperature, by B (Oi-Pr) 3(6.8 milliliters, 119 mmoles) add this reaction mixture to, and this reaction mixture is stirred 1 day.After stirring finishes, carry out cancellation reaction mixture by adding 2M HCl, and with distilled water and EA extraction.Concentrated gained organic layer, and gained organic layer is carried out to recrystallization with MC and hexane, obtain compound 5-5 (5 grams, 75%).
the preparation of compound 5-6
Cyanuryl chloride (50 grams, 91 mmoles) is joined in flask, and uses THF(1.3 liter) dissolve.Reaction mixture is cooled to 0 DEG C, and the PhMgBr in diethyl ether (225 milliliters) solution is slowly added into this reaction mixture by 3M.Be increased to after room temperature, reaction mixture stirred 3 hours, and add distilled water to complete reaction.Extract organic layer with EA, and use MgSO 4dry organic layer is to remove remaining moisture, and this organic layer of underpressure distillation.By using MC as eluting solvent, on silicon-dioxide, filter this mixture, obtain crude product 5-6 (37 grams, 63%), this product purity is high, is enough in step, use below.
the preparation of compd B-1
Compound 5-5 (6.5 grams, 19.2 mmoles), compound 5-6 (4.3 grams, 16 mmoles), Pd (PPh 3) 4(0.9 gram, 0.8 mmole) and K 2cO 3(6.6 grams, 48 mmoles) are dissolved in after toluene (100 milliliters)/EtOH (24 milliliters)/distilled water (24 milliliters), and reaction mixture is stirred 1 day at 100 DEG C.Add distilled water and after distillation, with MC dissolving gained solid, and separate by post (MC/ hexane) under reduced pressure, obtaining compd B-1 (5.4 grams, 64%).
The measured value 524.61 of MS/FAB; Calculated value 524.20
embodiment 6: the preparation of compd B-39
Figure BDA0000492037920000251
the preparation of compound 6-1
Compound 5-5 (22 grams, 65 mmoles), the bromo-4-phenyl-iodide of 1-(28 grams, 98.95 mmoles), Pd (PPh 3) 4(3.7 grams, 3.2 mmoles) and Na 2cO 3(20.7 grams, 195 mmoles) add in flask, and dissolve after this mixture by adding toluene (330 milliliters)/EtOH (150 milliliters), and reaction mixture is stirred 3 hours at 90 DEG C.After stirring completes, complete reaction by slowly adding pure water to reaction mixture, cool to room temperature, and extract this reaction mixture with distilled water and EA.Concentrated gained organic layer, and separate by post, compound 6-1 (25 grams, 86%) obtained.
the preparation of compound 6-2
Add compound 6-1 (25 grams, 55.7 mmoles) to flask, and with THF (300 milliliters) dissolving, reaction mixture is cooled to-78 DEG C.After 10 minutes, the 2.5Mn-BuLi in hexane (29 milliliters, 72.4 mmoles) is slowly added to this flask, and this reaction mixture is stirred 1 hour.At the same temperature, by B (Oi-Pr) 3(19.2 milliliters, 83.5 mmoles) slowly add this reaction mixture to, and this reaction mixture is stirred 24 hours.After stirring finishes, carry out cancellation reaction mixture by adding 1MHCl, and with distilled water and EA extraction.Concentrated gained organic layer, and gained organic layer is carried out to recrystallization with MC and hexane, obtain compound 6-2 (16.5 grams, 71%).
the preparation of compd B-39
Compound 6-2 (16.5 grams, 40 mmoles), compound 5-6 (8 grams, 29.8 mmoles), Pd (PPh 3) 4(1.7 grams, 1.5 mmoles) and K 2cO 3(12.4 grams, 89.4 mmoles) add in flask, and dissolve after this mixture by adding toluene (150 milliliters)/EtOH (75 milliliters), and reaction mixture is stirred 24 hours at 120 DEG C.Complete reaction by slow interpolation pure water, cool to room temperature, and extract this reaction mixture with distilled water and EA.Concentrated gained organic layer, and gained organic layer is carried out to recrystallization with EA and MeOH, obtain compd B-39 (6 grams, 32%).
The measured value 600.71 of MS/FAB; Calculated value 600.23
device embodiment 1: use the manufacture of the OLED device of compound of the present invention
Manufacture OLED device with compound of the present invention.With trieline, acetone, ethanol and distilled water successively to for Organic Light Emitting Diode (OLED) device ((the Samsung Corning of SCP company of Korea S, Republic of Korea)) glass baseplate on transparency electrode tin indium oxide (ITO) film (15 ohm-sq) carry out ultrasonic cleaning, be then stored in Virahol.Then, ITO base material is arranged in the substrate holder (holder) of vacuum phase deposition equipment.By N 1, N 1 '-([1,1 '-biphenyl]-4,4 '-bis-bases) two (N 1-(naphthalene-1-yl)-N 4, N 4-diphenyl benzene-Isosorbide-5-Nitrae-diamines) introduce in the chamber of described vacuum phase deposition equipment, then the constant pressure of described equipment is controlled to reach 10 -6holder.Then, apply electric current to described chamber to evaporate the material of above-mentioned introducing, thereby on ITO base material, form the hole injection layer that thickness is 60 nanometers.Then, by N, N '-bis-(4-xenyl)-N, N '-bis-(4-xenyl)-4,4 '-benzidine is introduced in another chamber of described vacuum phase deposition equipment, by applying electric current to evaporate to this chamber, thereby on described hole injection layer, form the hole transmission layer that thickness is 20 nanometers.Afterwards, compd A-1 is introduced in a chamber of vacuum phase deposition equipment as substrate material, and Compound D-7 are introduced in another chamber as doping agent.Bi-material is evaporated with different speed, and deposit in the doping of 4 % by weight doping agents (taking the gross weight of substrate material and doping agent as benchmark), thereby on hole transmission layer, form the luminescent layer that thickness is 30 nanometers.Then, 2-(4-(9,10-bis-(naphthalene-2-yl) anthracene-2-yl) phenyl)-1-phenyl-1H-benzo [d] imidazoles is introduced in a chamber, and quinoline is closed to lithium (Liq) and introduce in another chamber.Two kinds of materials are evaporated with identical speed, and deposit respectively with the doping of 50 % by weight, to form the electron transfer layer of thickness as 30 nanometers on luminescent layer.Then, the quinoline that has deposited thickness and be 2 nanometers on electron transfer layer closes lithium as after electron injecting layer, is the Al negative electrode of 150 nanometers by another vacuum phase deposition equipment deposit thickness on electron injecting layer.Thereby, prepared OLED device.Preparation OLED device all material used, passes through before use 10 -6purifying is carried out in vacuum-sublimation under holder condition.
Preparation OLED device under the driving voltage of 5.9V, launch brightness be 740 international candles/square metre ruddiness and current density be 5.3 milliamperes/centimetre 2.In addition 90% the time that, drops to this brightness in the brightness of 5000 nits is at least 100 hours.
device embodiment 2: use the manufacture of the OLED device of compound of the present invention
Use the method identical with device embodiment 1 to prepare OLED device, difference is to use compd A-47 as substrate material, uses Compound D-7 as doping agent.
Preparation OLED device under the driving voltage of 3.5V, launch brightness be 1430 international candles/square metre ruddiness and current density be 12.31 milliamperes/centimetre 2.In addition 90% the time that, drops to this brightness in the brightness of 5000 nits is at least 80 hours.
device embodiment 3: use the manufacture of the OLED device of compound of the present invention
Use the method identical with device embodiment 1 to prepare OLED device, difference is to use compd A-48 as substrate material, uses Compound D-11 as doping agent.
Preparation OLED device under the driving voltage of 3.0V, launch brightness be 835 international candles/square metre ruddiness and current density be 13.6 milliamperes/centimetre 2.In addition 90% the time that, drops to this brightness in the brightness of 5000 nits is at least 30 hours.
device embodiment 4: use the manufacture of the OLED device of compound of the present invention
Use the method identical with device embodiment 1 to prepare OLED device, difference is to use compd A-49 as substrate material, uses Compound D-7 as doping agent.
Preparation OLED device under the driving voltage of 6.1V, launch brightness be 2100 international candles/square metre ruddiness and current density be 16.2 milliamperes/centimetre 2.In addition 90% the time that, drops to this brightness in the brightness of 5000 nits is at least 70 hours.
device embodiment 5: use the manufacture of the OLED device of compound of the present invention
Use the method identical with device embodiment 1 to prepare OLED device, difference is to use compd B-1 as substrate material, uses Compound D-7 as doping agent.
Preparation OLED device under the driving voltage of 3.8V, launch brightness be 1010 international candles/square metre ruddiness and current density be 6.6 milliamperes/centimetre 2.In addition 90% the time that, drops to this brightness in the brightness of 5000 nits is at least 50 hours.
device embodiment 6: use the manufacture of the OLED device of compound of the present invention
Use the method identical with device embodiment 1 to prepare OLED device, difference is to use compd B-39 as substrate material, uses Compound D-11 as doping agent.
Preparation OLED device under the driving voltage of 2.9V, launch brightness be 420 international candles/square metre ruddiness and current density be 5.46 milliamperes/centimetre 2.In addition 90% the time that, drops to this brightness in the brightness of 5000 nits is at least 20 hours.
comparative example 1: use conventional electroluminescent compounds to manufacture OLED device
Use the method identical with device embodiment 1 to prepare OLED device, difference is to use 4,4 '-bis-(carbazole-9-yl) biphenyl (CBP) is as substrate material, with carrying out depositing light emitting layer as doping agent in Compound D-7, and between luminescent layer and electron transfer layer, with two (2-methyl-oxine closes (quinolinato)) (p-phenyl phenol) aluminium (III) (Balq) deposit thickness be the hole blocking layer of 10 nanometers.
Preparation OLED device under the driving voltage of 7.8V, launch brightness be 1000 international candles/square metre ruddiness and current density be 14.1 milliamperes/centimetre 2.
comparative example 2: use conventional electroluminescent compounds to manufacture OLED device
Use the method identical with device embodiment 1 to prepare OLED device, difference is to use 4,4 '-bis-(carbazole-9-yl) biphenyl (CBP) is as substrate material, with carrying out depositing light emitting layer as doping agent in Compound D-11, and between luminescent layer and electron transfer layer, with two (2-methyl-oxine closes (quinolinato)) (p-phenyl phenol) aluminium (III) hole blocking layers that (Balq) deposit thickness is 10nm.
Preparation OLED device under the driving voltage of 8.2V, launch brightness be 1000 international candles/square metre ruddiness and current density be 20.4 milliamperes/centimetre 2.In addition 90% the time that, drops to this brightness in the brightness of 5000 nits is at least 10 hours.
Electroluminescent compounds of the present invention has the more excellent characteristics of luminescence than conventional material.In addition, adopt organic electroluminescent compounds of the present invention not only to there is the excellent characteristics of luminescence as the device of substrate material, and by reducing driving voltage, power efficiency is increased.
Claims (according to the amendment of the 19th article of treaty)
1. the organic electroluminescent compounds being represented by following general formula 1:
Figure FDA0000492037960000011
Wherein
Z represents
Figure FDA0000492037960000012
L 1represent singly-bound, replacement or unsubstituted (C6-C30) arylidene or replacement or unsubstituted 3 yuan to 30 yuan heteroarylidenes;
A 1to A 3represent independently of one another CR 11or N, prerequisite is A 1to A 3different times table CH;
X Dai Biao – O-,-S-,-CR 12r 13-,, Huo – NR 14-;
R 1, R 2, R 11, Ar 1and Ar 2represent independently of one another hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted 3-30 unit heteroaryl ,-NR 15r 16,-SiR 17r 18r 19,-SR 20,-OR 21, cyano group or nitro;
R 12to R 14represent independently of one another to replace or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted 3 yuan to 30 yuan heteroaryls;
R 15to R 21represent independently of one another hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted 3 yuan to 30 yuan heteroaryls; Or they are connected form monocycle or encircle more with adjacent substituting group, (C5-C30) alicyclic ring or aromatic ring, the heteroatoms that its carbon atom can be selected from nitrogen, oxygen and sulphur by least one substitutes;
A represents the integer of 1-6; When a is while being equal to or greater than 2 integer, each R 1identical or different;
B represents the integer of 1-3; When b is while being equal to or greater than 2 integer, each R 2identical or different;
Described Heterocyclylalkyl and assorted (Asia) aryl contain at least one and are selected from the heteroatoms of B, N, O, S, P (=O), Si and P.
2. organic electroluminescent compounds as claimed in claim 1, is characterized in that, described organic electroluminescent compounds is selected from lower group: the compound that following formula 2 and 3 represents:
Figure FDA0000492037960000021
Wherein
X, R 1, R 2, a, b, L 1, A 1to A 3, Ar 1and Ar 2as in claim 1 define.
3. organic electroluminescent compounds as claimed in claim 1, is characterized in that, the L of general formula 1 1, R 1, R 2, R 11to R 21, Ar 1and Ar 2the substituting group of assorted (Asia) aryl of the alkyl replacing described in group, (Asia) aryl of replacement, replacement, ring (Asia) alkyl, the Heterocyclylalkyl of replacement and the aralkyl of replacement of replacement is that at least one is selected from the group of lower group: deuterium independently of one another; Halogen; Unsubstituted or replaced by halogen (C1-C30) alkyl; (C6-C30) aryl; Unsubstituted or with (C1-C30) alkyl or (C6-C30) aryl replace 3 yuan to 30 yuan heteroaryls; (C3-C30) cycloalkyl; 5 yuan to 7 yuan Heterocyclylalkyls; Three (C1-C30) alkyl silyl; Three (C6-C30) aryl silyl; Two (C1-C30) alkyl (C6-C30) aryl silyl; (C1-C30) alkyl two (C6-C30) aryl silyl; (C2-C30) thiazolinyl; (C2-C30) alkynyl; Cyano group; N-carbazyl; Two (C1-C30) alkylamino; Two (C6-C30) arylamino; (C1-C30) alkyl (C6-C30) arylamino; Two (C6-C30) aryl boron carbonyl; Two (C1-C30) boron alkyl carbonyl; (C1-C30) alkyl (C6-C30) aryl boron carbonyl; (C6-C30) aryl (C1-C30) alkyl; (C1-C30) alkyl (C6-C30) aryl; Carboxyl; Nitro and hydroxyl.
4. organic electroluminescent compounds as claimed in claim 1, is characterized in that, L 1represent singly-bound or (C6-C30) arylidene, A 1to A 3represent independently of one another CR 11or N, prerequisite is A 1to A 3different times table CH, X representative-NR 14-, R 11represent hydrogen, deuterium, (C1-C30) alkyl, (C6-C30) aryl or 3-30 unit heteroaryl, R 14represent (C1-C30) alkyl, (C6-C30) aryl or 3-30 unit heteroaryl, and R 1, R 2, Ar 1and Ar 2represent independently of one another hydrogen, deuterium, halogen, (C1-C30) alkyl, (C6-C30) aryl or 3-30 unit heteroaryl, L 1in arylidene, R 1, R 2, R 11, R 14, Ar 1and Ar 2in alkyl, the group that aryl and heteroaryl can be selected from lower group by least one replaces: deuterium, halogen, (C1-C30) alkyl, halo (C1-C30) alkyl, (C6-C30) aryl, 3 yuan to 30 yuan heteroaryls, 3 yuan to the 30 yuan heteroaryls that quilt (C6-C30) aryl and/or (C1-C30) alkyl replace, (C3-C30) cycloalkyl, three (C1-C30) alkyl silyl, three (C6-C30) aryl silyl, two (C1-C30) alkyl (C6-C30) aryl silyl, (C1-C30) alkyl two (C6-C30) aryl silyl, (C6-C30) aryl (C1-C30) alkyl and (C1-C30) alkyl (C6-C30) aryl.
5. organic electroluminescent compounds as claimed in claim 1, is characterized in that, the described compound being represented by general formula 1 is selected from lower group:
Figure FDA0000492037960000031
Figure FDA0000492037960000041
Figure FDA0000492037960000071
Figure FDA0000492037960000081
6. an organic electroluminescence device that comprises compound as claimed in claim 1.
Illustrate or state (according to the amendment of the 19th article of treaty)
According to the statement of PCT19 amendment
Obvious input error has been corrected in this amendment.
The modification right of international application no No.PCT/KR2012/007022 requires 1 and 4 to obtain the specification sheets of original PCT application and the support of claim.
In this amendment, revise original rights and required 1, make free radical Z wherein quote following structure:
Figure QDA0000492037950000021
this has obtained the support of the general formula (3) of claim 2; And " Ar capable 10-11 1to Ar 3" be corrected as " A 1to A 3", this has obtained the support of the six membered heteroaryl core of the compound of general formula as exemplified in claim 5 (1).
Original rights is required 4 to be modified as claim 4, with " Ar capable 2-3 1to Ar 3" be corrected as " A 1to A 3", this has obtained the support of the six membered heteroaryl core of the compound of general formula as exemplified in claim 5 (1).

Claims (6)

1. the organic electroluminescent compounds being represented by following general formula 1:
Figure FDA0000492037910000011
Wherein
Z represents
Figure FDA0000492037910000012
L 1represent singly-bound, replacement or unsubstituted (C6-C30) arylidene or replacement or unsubstituted 3 yuan to 30 yuan heteroarylidenes;
Ar 1to Ar 3represent independently of one another CR 11or N, prerequisite is Ar 1to Ar 3different times table CH;
X Dai Biao – O-,-S-,-CR 12r 13-,, Huo – NR 14-;
R 1, R 2, R 11, Ar 1and Ar 2represent independently of one another hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted 3-30 unit heteroaryl ,-NR 15r 16,-SiR 17r 18r 19,-SR 20,-OR 21, cyano group or nitro;
R 12to R 14represent independently of one another to replace or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted 3 yuan to 30 yuan heteroaryls;
R 15to R 21represent independently of one another hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or replacement or unsubstituted 3 yuan to 30 yuan heteroaryls; Or they are connected form monocycle or encircle more with adjacent substituting group, (C5-C30) alicyclic ring or aromatic ring, the heteroatoms that its carbon atom can be selected from nitrogen, oxygen and sulphur by least one substitutes;
A represents the integer of 1-6; When a is while being equal to or greater than 2 integer, each R 1identical or different;
B represents the integer of 1-3; When b is while being equal to or greater than 2 integer, each R 2identical or different;
Described Heterocyclylalkyl and assorted (Asia) aryl contain at least one and are selected from the heteroatoms of B, N, O, S, P (=O), Si and P.
2. organic electroluminescent compounds as claimed in claim 1, is characterized in that, described organic electroluminescent compounds is selected from lower group: the compound that following formula 2 and 3 represents:
Figure FDA0000492037910000021
Wherein
X, R 1, R 2, a, b, L 1, A 1to A 3, Ar 1and Ar 2as in claim 1 define.
3. organic electroluminescent compounds as claimed in claim 1, is characterized in that, the L of general formula 1 1, R 1, R 2, R 11to R 21, Ar 1and Ar 2the substituting group of assorted (Asia) aryl of the alkyl replacing described in group, (Asia) aryl of replacement, replacement, ring (Asia) alkyl, the Heterocyclylalkyl of replacement and the aralkyl of replacement of replacement is that at least one is selected from the group of lower group: deuterium independently of one another; Halogen; Unsubstituted or replaced by halogen (C1-C30) alkyl; (C6-C30) aryl; Unsubstituted or with (C1-C30) alkyl or (C6-C30) aryl replace 3 yuan to 30 yuan heteroaryls; (C3-C30) cycloalkyl; 5 yuan to 7 yuan Heterocyclylalkyls; Three (C1-C30) alkyl silyl; Three (C6-C30) aryl silyl; Two (C1-C30) alkyl (C6-C30) aryl silyl; (C1-C30) alkyl two (C6-C30) aryl silyl; (C2-C30) thiazolinyl; (C2-C30) alkynyl; Cyano group; N-carbazyl; Two (C1-C30) alkylamino; Two (C6-C30) arylamino; (C1-C30) alkyl (C6-C30) arylamino; Two (C6-C30) aryl boron carbonyl; Two (C1-C30) boron alkyl carbonyl; (C1-C30) alkyl (C6-C30) aryl boron carbonyl; (C6-C30) aryl (C1-C30) alkyl; (C1-C30) alkyl (C6-C30) aryl; Carboxyl; Nitro and hydroxyl.
4. organic electroluminescent compounds as claimed in claim 1, is characterized in that, L 1represent singly-bound or (C6-C30) arylidene, Ar 1to Ar 3represent independently of one another CR 11or N, prerequisite is Ar 1to Ar 3different times table CH, X representative-NR 14-, R 11represent hydrogen, deuterium, (C1-C30) alkyl, (C6-C30) aryl or 3-30 unit heteroaryl, R 14represent (C1-C30) alkyl, (C6-C30) aryl or 3-30 unit heteroaryl, and R 1, R 2, Ar 1and Ar 2represent independently of one another hydrogen, deuterium, halogen, (C1-C30) alkyl, (C6-C30) aryl or 3-30 unit heteroaryl, L 1in arylidene, R 1, R 2, R 11, R 14, Ar 1and Ar 2in alkyl, the group that aryl and heteroaryl can be selected from lower group by least one replaces: deuterium, halogen, (C1-C30) alkyl, halo (C1-C30) alkyl, (C6-C30) aryl, 3 yuan to 30 yuan heteroaryls, 3 yuan to the 30 yuan heteroaryls that quilt (C6-C30) aryl and/or (C1-C30) alkyl replace, (C3-C30) cycloalkyl, three (C1-C30) alkyl silyl, three (C6-C30) aryl silyl, two (C1-C30) alkyl (C6-C30) aryl silyl, (C1-C30) alkyl two (C6-C30) aryl silyl, (C6-C30) aryl (C1-C30) alkyl and (C1-C30) alkyl (C6-C30) aryl.
5. organic electroluminescent compounds as claimed in claim 1, is characterized in that, the described compound being represented by general formula 1 is selected from lower group:
Figure FDA0000492037910000031
Figure FDA0000492037910000041
Figure FDA0000492037910000051
Figure FDA0000492037910000061
Figure FDA0000492037910000071
Figure FDA0000492037910000081
6. an organic electroluminescence device that comprises compound as claimed in claim 1.
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