CN103183664B - Naphthacridine derivate, preparation method and application thereof, and organic light-emitting device - Google Patents
Naphthacridine derivate, preparation method and application thereof, and organic light-emitting device Download PDFInfo
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- CN103183664B CN103183664B CN201110460054.2A CN201110460054A CN103183664B CN 103183664 B CN103183664 B CN 103183664B CN 201110460054 A CN201110460054 A CN 201110460054A CN 103183664 B CN103183664 B CN 103183664B
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- 0 CC(C)(C=C1)C=Cc2c1c(C=CC(C)(*)C=C1)c1[n]2 Chemical compound CC(C)(C=C1)C=Cc2c1c(C=CC(C)(*)C=C1)c1[n]2 0.000 description 2
- JHOUNPVONDLYLK-UHFFFAOYSA-N Brc(cc1)c(cc2)c3c1N(c(cc1)ccc1-c1ccccc1)c(cc1)c4c3c2ccc4c1Br Chemical compound Brc(cc1)c(cc2)c3c1N(c(cc1)ccc1-c1ccccc1)c(cc1)c4c3c2ccc4c1Br JHOUNPVONDLYLK-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a compound shown in a formula (I), wherein R1, R2, R3, R4, R5, m, n, p and q have meanings described in a specification. The invention further relates to a preparation method of the compound shown in the formula (I), organic electroluminescent material comprising the compound, and application of the compound in the technical field of organic electroluminescent lighting and display.
Description
Technical field
The present invention relates to organic electroluminescent field, more specifically, relate to the application in organic electroluminescent luminous and technique of display field of a kind of naphthacridine derivative, its preparation method, the electroluminescent organic material that comprises described compound and described compound.
Background technology
Recently, use the organic electroluminescence device (OLED) of phosphorescent metal title complex to develop rapidly.In classical phosphorescent OLED device, except luminescent dye, also need to select suitable material of main part.Phosphorescent coloring is conventionally separately as luminescent layer, but is entrained in material of main part, forms Subjective and Objective luminescence system, to weaken the high density quenching effect of triplet excitons.In order to realize effective transmission ofenergy, conventionally require the energy gap of material of main part to be greater than dyestuff and triplet E
twill be higher than the triplet E of dye molecule
t.Like this could be smoothly T
1state energy is passed to phosphorescent coloring or triplet excitons is limited to dye molecule from material of main part, thereby realizes high efficiency phosphorescent emissions.In addition the second-order transition temperature T of material of main part,
gthe film-forming properties and the thermostability that are related to material.T
gthe material poor heat stability that temperature is low and easily crystallization or reunion, will reduce the life-span of device greatly, seriously reduces device efficiency.Therefore, need searching to there is wide energy gap, high triplet and high T
gtemperature, thus higher luminous efficiency and current efficiency and the material of main part of low driving voltage more can be obtained.
Summary of the invention
An object of the present invention is to solve one or more the above-mentioned problems in the prior art.
The invention provides a kind of new naphthacridine derivative, its structural formula is suc as formula shown in (I),
Wherein
R
1representative replaces or unsubstituted C
6-C
30aryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
10alkyl, C
1-C
10alkoxyl group or C
6-C
20the group of aryl, described substituting group is again optionally by one or more C
1-C
10alkyl replaces;
R
2represent independently of one another hydrogen, replacement or unsubstituted C
6-C
30aryl or replacement or unsubstitutedly contain the heteroatomic C that one or two is selected from N, O or S
5-C
30heteroaryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
10alkyl, C
1-C
10alkoxyl group or C
6-C
20the group of aryl;
R
3represent independently of one another hydrogen, replacement or unsubstituted C
6-C
30aryl or replacement or unsubstitutedly contain the heteroatomic C that one or two is selected from N, O or S
5-C
30heteroaryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
10alkyl, C
1-C
10alkoxyl group or C
6-C
20the group of aryl;
R
4represent independently of one another hydrogen, replacement or unsubstituted C
6-C
30aryl or replacement or unsubstitutedly contain the heteroatomic C that one or two is selected from N, O or S
5-C
30heteroaryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
10alkyl, C
1-C
10alkoxyl group or C
6-C
20the group of aryl;
R
5represent independently of one another hydrogen, replacement or unsubstituted C
6-C
30aryl or replacement or unsubstitutedly contain the heteroatomic C that one or two is selected from N, O or S
5-C
30heteroaryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
10alkyl, C
1-C
10alkoxyl group or C
6-C
20the group of aryl; And
M, n, p and q represent 0,1,2,3 or 4 independently of one another.
Find unexpectedly, the material of main part that formula of the present invention (I) compound can be used as luminescent layer is for organic electroluminescence device, thereby makes the organic electroluminescence device that comprises this material have lower driving voltage and/or higher luminous efficiency and current efficiency.
The present invention also provides the method for a kind of preparation formula (I) compound, comprising:
(A1) as [R
2]
mwith [R
5]
qidentical and [R
3]
nwith [R
4]
pwhen identical, optionally under the existence of thinner and optionally under the existence of alkali and catalyzer, the halo naphtho-acridine compounds of formula (II) is reacted with the aromatic amine of formula (III), production (I-A1) compound,
Wherein
X represents halogen; And
R
1as above definition,
Wherein
R
2, R
3, m and n as above define,
R wherein
1, R
2, R
3, m and n as above define; Or
(A2) as [R
2] m and [R
5]
qand/or [R
3]
nwith [R
4]
pwhen different, optionally under the existence of thinner and optionally under the existence of alkali and catalyzer, the halo naphtho-acridine compounds of formula (II) is reacted with the aromatic amine of formula (III), production (I-A2 ') compound, then optionally under the existence of thinner and optionally under the existence of alkali and catalyzer, the aromatic amine of formula (I-A2 ') compound and formula (III ') is reacted, production (I-A2) compound
R wherein
1, R
2, R
3, m and n as above define,
R wherein
4, R
5, p and q as above define,
R wherein
1, R
2, R
3, R
4, R
5, m, n, p and q as above define.
In addition, the present invention also provides a kind of formula (II) compound,
Wherein
R
1as above define with X.
In addition, the present invention also provides the purposes of formula of the present invention (I) compound as phosphorescent light body material or hole mobile material.
The present invention also provides a kind of light emitting composition, comprises formula of the present invention (I) compound and a kind of phosphorescent coloring, and described phosphorescent coloring is selected from the complex compound of Ir, Pt, Os, Ru, Re or Pd.
In addition, the present invention also provides a kind of organic electroluminescence device, comprises negative electrode, anode and organic function layer, and this organic function layer comprises at least one luminescent layer, and at least one deck in this luminescent layer comprises formula of the present invention (I) compound.
Organic materials of the present invention can be used as material of main part in organic electroluminescence device, has higher current efficiency and luminous efficiency, effectively reduces in addition driving voltage.
Embodiment
Term as used herein " alkyl " and the alkyl group in combination definition (such as alkoxyl group, haloalkyl etc.) can be straight or branched, it preferably has rudimentary carbon skeleton, for example contain 1-18 carbon atom, preferred 1-12 carbon atom, more preferably 1-8 carbon atom, further preferred 1-6 carbon atom, an especially 1-4 carbon atom.Described alkyl can be, for example methyl, ethyl, propyl group (as n-propyl or sec.-propyl), butyl (as normal-butyl, isobutyl-or the tertiary butyl), amyl group (as n-pentyl, isopentyl or neo-pentyl), hexyl are (as n-hexyl, isohexyl, 3-methyl amyl, 2,2-dimethylbutyl or 2,3-dimethylbutyl) and heptyl (as n-heptyl, 1-methyl hexyl or Isosorbide-5-Nitrae-dimethyl amyl group).
Term as used herein " alkoxyl group " refers to the group of the Sauerstoffatom being connected with alkyl.It preferably has rudimentary carbon skeleton, for example, contain 1-18 carbon atom, preferred 1-12 carbon atom, more preferably 1-8 carbon atom, further preferred 1-6 carbon atom, an especially 1-4 carbon atom.Described alkyl can be, for example methoxyl group, oxyethyl group, propoxy-or isopropoxy
Term as used herein " aryl " is not for containing heteroatomic monocycle or condensed ring aroma system, for example it comprises 1 aromatic ring or comprises 2-5 condensed ring, preferably 2-4 condensed ring, more preferably 2-3 condensed ring, wherein each ring preferably contains 4-7 annular atoms, more preferably contains 5-6 annular atoms.Aryl preferably has rudimentary carbon skeleton, for example, contain 6-18 carbon atom, preferred 6-12 carbon atom, more preferably 6-10 carbon atom.Described aryl can be, for example phenyl, naphthyl, xenyl, anthryl, naphthane and, indenyl, fluorenyl, phenanthryl, benzo phenanthryl, pyrenyl, perylene base, naphthacenyl and fluoranthene base.The preferred 1-naphthyl of described naphthyl or 2-naphthyl; The preferred 9-phenanthryl of described phenanthryl; The preferred 2-xenyl of described xenyl, 3-xenyl or 4-xenyl; The preferred 1-fluorenyl of described fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl or 9-fluorenyl; The preferred 1-anthryl of described anthryl, 2-anthryl or 9-anthryl; The preferred 2-pyrenyl of described pyrenyl.
Described naphthyl phenyl preferred 1-naphthyl phenyl of the present invention or 2-naphthyl phenyl.
Term as used herein " heteroaryl " preferably has rudimentary carbon skeleton, for example, contain 6-18 carbon atom, preferred 6-12 carbon atom, more preferably 6-10 carbon atom, and contain 1 to 4 annular atoms that is selected from N, O and S.Heteroaryl can be 5 or 6 bicyclic heteroaryls or with 2,3 or 4 phenyl ring are thick and polyheteroaromatic, and it can be fractional saturation.Described heteroaryl can be, bicyclic heteroaryl for example, as furyl, thiophenyl, pyrryl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl group, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazine base, triazolyl, tetrazyl, furan cluck base, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl; Polyheteroaromatic, as benzofuryl, benzo thiophenyl, isobenzofuran-base, benzimidazolyl-, benzothiazolyl, benzisothiazole base, benzoisoxazole base, benzoxazolyl, pseudoindoyl, indyl, indazolyl, diazosulfide base, quinolyl, isoquinolyl, cinnolines base, quinazolyl, quinolizinyl, quinoxalinyl, carbazyl, phenanthridinyl and benzo dioxolyl.
Term as used herein " halogen " is fluorine, chlorine, bromine or iodine.The group being replaced by halo represent by halogen, preferably by fluorine, chlorine and/or bromine, especially by fluorine and/or cl part, replaced or replace completely the group of (for example monosubstituted, two replace or three replace), for example CF
3, CHF
2, CH
2f, CF
3cF
2, CH
2fCHCl, CCl
3, CHCl
2, CH
2cH
2cl, OCF
3, OCHF
2, OCH
2f, CF
3cF
2o, OCH
2cF
3and OCH
2cH
2cl etc.
Term as used herein " cycloalkyl " is not containing heteroatoms, and the example has cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group.
The substituting group of mentioning by way of example (" the first substituting group level "), if it comprises hydrocarbonaceous part, optionally in hydrocarbonaceous part, be further substituted (" the second substituting group level "), for example, by one of substituting group for the first substituting group level definition, replaced.Corresponding further substituting group level is also possible.Preferably, substituted group only comprises one, two or three substituting group levels.Preferably, each substituting group level of the present invention contains maximum 20 carbon atoms, 18 carbon atoms for example, preferred maximum 12 carbon atoms, more preferably maximum 8 carbon atoms, further preferred maximum 6 carbon atoms, especially maximum 4 carbon atoms.
Group of the present invention is not preferably substituted or mono-to trisubstituted, more preferably by monosubstituted to two replacements.
In the present invention, the all possible steric isomer being limited by its concrete spatial form is contained in the definition of formula (I) completely, as enantiomer, diastereomer and cis-trans isomer, if suitable, the present invention had both comprised pure steric isomer, comprised again its isomer mixture.
For the various substituent possible combination of formula (I), must follow the rule of compound structure, formula (I) does not comprise chemically infeasible any compound well known by persons skilled in the art.
The restriction of in the context of the invention, compound group being done is also correspondingly applicable to other theme of the present invention, comprises preparation method, application, composition and the organic electroluminescence device etc. of giving out light.
Formula of the present invention (I) compound has following formula structure,
Wherein
R
1representative replaces or unsubstituted C
6-C
30aryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
10alkyl, C
1-C
10alkoxyl group or C
6-C
20the group of aryl, described substituting group is again optionally by one or more C
1-C
10alkyl replaces;
R
2represent independently of one another hydrogen, replacement or unsubstituted C
6-C
30aryl or replacement or unsubstitutedly contain the heteroatomic C that one or two is selected from N, O or S
5-C
30heteroaryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
10alkyl, C
1-C
10alkoxyl group or C
6-C
20the group of aryl;
R
3represent independently of one another hydrogen, replacement or unsubstituted C
6-C
30aryl or replacement or unsubstitutedly contain the heteroatomic C that one or two is selected from N, O or S
5-C
30heteroaryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
10alkyl, C
1-C
10alkoxyl group or C
6-C
20the group of aryl;
R
4represent independently of one another hydrogen, replacement or unsubstituted C
6-C
30aryl or replacement or unsubstitutedly contain the heteroatomic C that one or two is selected from N, O or S
5-C
30heteroaryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
10alkyl, C
1-C
10alkoxyl group or C
6-C
20the group of aryl;
R
5represent independently of one another hydrogen, replacement or unsubstituted C
6-C
30aryl or replacement or unsubstitutedly contain the heteroatomic C that one or two is selected from N, O or S
5-C
30heteroaryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
10alkyl, C
1-C
10alkoxyl group or C
6-C
20the group of aryl; And
M, n, p and q represent 0,1,2,3 or 4 independently of one another.
Find unexpectedly, compound of the present invention can be used as electro-phosphorescent main body material in organic electroluminescence device, particularly as the bipolar host material of doping type luminescent device, thereby make the organic electroluminescence device that comprises described compound there is lower driving voltage and/or higher luminous efficiency and current efficiency.
Above-mentioned formula (I) provides the broad definition of the compounds of this invention.In the structural formula that context provides, the preferred substituents of group or range specification are as follows:
R
1preferably representative replaces or unsubstituted C
6-C
20aryl, is wherein having in substituent situation, and described substituting group is preferably one or more C of being selected from
1-C
8alkyl or C
6-C
20the group of aryl, described substituting group is again optionally by one or more C
1-C
8alkyl replaces;
R
2preferably represent independently of one another hydrogen or replacement or unsubstituted C
6-C
20aryl, is wherein having in substituent situation, and described substituting group is preferably one or more C of being selected from
1-C
8alkyl or C
6-C
20the group of aryl;
R
3preferably represent independently of one another hydrogen or replacement or unsubstituted C
6-C
20aryl, is wherein having in substituent situation, and described substituting group is preferably one or more C of being selected from
1-C
8alkyl or C
6-C
20the group of aryl;
R
4preferably represent independently of one another hydrogen or replacement or unsubstituted C
6-C
20aryl, is wherein having in substituent situation, and described substituting group is preferably one or more C of being selected from
1-C
8alkyl or C
6-C
20the group of aryl;
R
5preferably represent independently of one another hydrogen or replacement or unsubstituted C
6-C
20aryl, is wherein having in substituent situation, and described substituting group is preferably one or more C of being selected from
1-C
8alkyl or C
6-C
20the group of aryl; And
M, n, p and q preferably represent 0,1,2,3 or 4 independently of one another.
R
1more preferably representative replaces or unsubstituted C
6-C
18aryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from more preferably
1-C
6alkyl or C
6-C
18the group of aryl, described substituting group is again optionally by one or more C
1-C
6alkyl replaces;
R
2more preferably represent independently of one another hydrogen or replacement or unsubstituted C
6-C
18aryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from more preferably
1-C
6alkyl or C
6-C
18the group of aryl;
R
3more preferably represent independently of one another hydrogen or replacement or unsubstituted C
6-C
18aryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from more preferably
1-C
6alkyl or C
6-C
18the group of aryl;
R
4more preferably represent independently of one another hydrogen or replacement or unsubstituted C
6-C
18aryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from more preferably
1-C
6alkyl or C
6-C
18the group of aryl;
R
5more preferably represent independently of one another hydrogen or replacement or unsubstituted C
6-C
18aryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from more preferably
1-C
6alkyl or C
6-C
18the group of aryl; And
M, n, p and q more preferably represent 0,1,2 or 3 independently of one another.
R
1, R
2, R
3, R
4and R
5further preferably represent independently of one another phenyl, tolyl, xylyl, xenyl, naphthyl, naphthyl phenyl, anthryl, fluoranthene base, benzo anthryl, phenanthryl, fluorenyl, 9,9-dimethyl fluorenyl or benzo fluorenyl; And
M, n, p and q further preferably represent 0,1,2 or 3 independently of one another.
R
1, R
2, R
3, R
4and R
5especially preferably representative is selected from following group independently of one another:
M, n, p and q especially preferably represent 0,1,2 or 3 independently of one another.
More specifically preferably, the example of formula of the present invention (I) compound comprises following I-1 to I-50 compound:
In the context of the invention, each substituting group wide in range, preferred, preferred, further preferred, especially preferred and more specifically preferred definition can be bonded to each other on demand.This expression the present invention includes the compound of general formula (I), wherein, for example, substituent R
1there is preferred definition and substituent R
2and R
3there is general definition, or, for example, substituent R
2there is preferred definition, substituent R
3have preferred definition, all the other substituting groups have wide in range definition.For the sake of simplicity, the not concrete statement of these various combinations out, but should be thought and comprises within the scope of the invention.In addition, the present invention is also correspondingly applicable to prepare its various intermediates for the definition of formula (I) compound, comprise the intermediate of preparing its intermediate.
The method of formula produced according to the present invention (I) compound comprises:
(A1) as [R
2]
mwith [R
5]
qidentical and [R
3]
nwith [R
4]
pwhen identical, optionally under the existence of thinner and optionally under the existence of alkali and catalyzer, the halo naphtho-acridine compounds of formula (II) is reacted with the aromatic amine of formula (III), production (I-A1) compound,
Wherein
X represents halogen; And
R
1as above definition,
Wherein
R
2, R
3, m and n as above define,
R wherein
1, R
2, R
3, m and n as above define; Or
(A2) as [R
2]
mwith [R
5]
qand/or [R
3]
nwith [R
4]
pwhen different, optionally under the existence of thinner and optionally under the existence of alkali and catalyzer, the halo naphtho-acridine compounds of formula (II) is reacted with the aromatic amine of formula (III), production (I-A2 ') compound, then optionally under the existence of thinner and optionally under the existence of alkali and catalyzer, the aromatic amine of formula (I-A2 ') compound and formula (III ') is reacted, production (I-A2) compound
R wherein
1, R
2, R
3, m and n as above define,
R wherein
4, R
5, p and q as above define,
R wherein
1, R
2, R
3, R
4, R
5, m, n, p and q as above define.
In aforesaid method (A1), the mol ratio of formula (II) compound and the reaction of formula (III) compound is generally change in 1: 1 to 1: 3, preferably 1: 1.5 to 1: 2.5, more preferably 1: 2.
In aforesaid method (A2), what formula (II) compound and formula (III) compound reacted is generally 1: 0.5 to 1: 1.2 in mol ratio, preferably 1: 0.8 to 1: 1.1, more preferably 1: 1, and the mol ratio that the aryl boride of (I-A2 ') compound and formula (III ') reacts is generally 1: 0.5 to 1: 1.2, preferably 1: 0.8 to 1: 1.1, more preferably 1: 1.
Aforesaid method (A1) and (A2) in, suitable catalyzer can be the transition-metal catalyst of linked reaction that can catalysis halogenated aromatic compound, Pd compound for example, as Pd (dppf) Cl
2, Pd (PPh
3)
2cl
2, Pd (PPh
3)
4, Pd (dba)
2or Pd (OAc)
2, preferred Pd (PPh
3)
4.Also optionally in above-mentioned catalyzer, add organophosphorus ligand to form catalyst system, organophosphorus ligand is tri-butyl phosphine, tributylphosphine or triphenylphosphine for example.
Aforesaid method (A1) and (A2) in, suitable alkali can be alkali (soil) metal carbonate, alkali (soil) metal hydroxides or alkali (soil) metal alkoxide, preferred bases alkali metal hydroxide, alkali metal alcoholates, more preferably sodium tert-butoxide, potassium tert.-butoxide, sodium ethylate or sodium methylate.
Aforesaid method (A1) and (A2) in, suitable thinner can be all organic solvents that are inertia to participating in the material of this reaction.Preferably use hydro carbons, for example sherwood oil, normal hexane, Skellysolve A, benzene, toluene and dimethylbenzene; Halohydrocarbon, for example methylene dichloride, trichloromethane, tetracol phenixin, chlorobenzene and orthodichlorobenzene; Ketone, for example acetone and methyl isopropyl Ketone; Ether, for example ether, tetrahydrofuran (THF), diox, glycol dimethyl ether and diglyme; Carboxylicesters, for example ethyl acetate; And nitrile, for example acetonitrile; Alcohol, for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and the trimethyl carbinol; Acid amides, for example dimethyl formamide; And sulfone, for example tetramethylene sulfone; Also have sulfoxide, for example dimethyl sulfoxide (DMSO).Preferably use acetonitrile, methyl-sulphoxide, tetrahydrofuran (THF), dimethyl formamide or toluene.More preferably use toluene.
Formula of the present invention (II) compound is new, and it can be prepared by the following method, comprising:
(B) optionally under the existence of thinner, the naphthacridine compound of formula (IV) is reacted with halogenating agent,
R wherein
1as above definition.
In aforesaid method (B), suitable halogenating agent can be Br
2, Cl
2, I
2or N-bromo-succinimide (NBS).
In aforesaid method (B), suitable thinner can be all organic solvents that are inertia to participating in the material of this reaction.Preferably use hydro carbons, for example sherwood oil, normal hexane and Skellysolve A; Ketone, for example acetone and methyl isopropyl Ketone; Halohydrocarbon, for example methylene dichloride, trichloromethane, tetracol phenixin, chlorobenzene and orthodichlorobenzene; Ether, for example ether, tetrahydrofuran (THF), diox, glycol dimethyl ether and diglyme; Nitrile, for example acetonitrile; Acid amides, for example dimethyl formamide; And sulfone, for example tetramethylene sulfone; Also have sulfoxide, for example dimethyl sulfoxide (DMSO).Preferred CH
2cl
2.
Formula of the present invention (IV) compound can be prepared by the following method, comprising:
(C) optionally under the existence of thinner and optionally under the existence of catalyzer, make reduce-ring-closure reaction of formula (V) acetyl halide compound,
R wherein
1as above definition.
In aforesaid method (C), suitable thinner can be PtCl for example
2.
In aforesaid method (C), suitable thinner can be all organic solvents that are inertia to participating in the material of this reaction.Preferably use hydro carbons, for example sherwood oil, normal hexane, Skellysolve A, benzene, toluene and dimethylbenzene; Ketone, for example acetone and methyl isopropyl Ketone; Ether, for example ether, tetrahydrofuran (THF), diox, glycol dimethyl ether and diglyme; Carboxylicesters, for example ethyl acetate; Nitrile, for example acetonitrile; Acid amides, for example dimethyl formamide; And sulfone, for example tetramethylene sulfone; Also have sulfoxide, for example dimethyl sulfoxide (DMSO).Preferred toluene.
Formula of the present invention (V) compound can be prepared by the following method, comprising:
(D) optionally under the existence of alkali and optionally under the existence of catalyzer, make the reaction of formula (VI) compound ethynyl trimethyl silane,
R wherein
1as above definition.
In aforesaid method (D), suitable catalyzer can be the combination of organic Pd catalyzer and cuprous salt, and wherein organic Pd catalyzer can be selected from Pd (dppf) Cl
2, Pd (PPh
3)
2cl
2, Pd (PPh
3)
4, Pd (dba)
2and Pd (OAc)
2, be preferably Pd (PPh
3)
2cl
2or Pd (PPh
3)
4, Pd (PPh most preferably
3)
4.Also optionally in above-mentioned catalyzer, add organophosphorus ligand to form catalyst system, organophosphorus ligand is tri-butyl phosphine, tributylphosphine or triphenylphosphine for example.Described cuprous salt includes, but not limited to CuI and CuBr.
In aforesaid method (D), suitable alkali can be organic bases, preferably organic amine, more preferably triethylamine, diisopropylethylamine, N-methylmorpholine, pyridine or 1,8-diazabicylo [5.4.0], 11 carbon-7-alkene (DBU).Triethylamine most preferably.
Formula of the present invention (VI) compound can be prepared by the following method, comprising:
(E) optionally under the existence of thinner and optionally under the existence of activator, make formula (VII) compound that Corey-Fuchs reaction occur,
R wherein
1as above definition.
In aforesaid method (E), suitable activator can be organic phosphine, triphenylphosphine.
In aforesaid method (E), suitable thinner can be all organic solvents that are inertia to participating in the material of this reaction.Preferably use hydro carbons, for example sherwood oil, normal hexane, Skellysolve A, benzene, toluene and dimethylbenzene; Halohydrocarbon, for example methylene dichloride, trichloromethane, tetracol phenixin, chlorobenzene and orthodichlorobenzene; Ether, for example ether, tetrahydrofuran (THF) ， diox, glycol dimethyl ether and diglyme; Carboxylicesters, for example ethyl acetate; Nitrile, for example acetonitrile; Acid amides, for example dimethyl formamide; And sulfone, for example tetramethylene sulfone; Also have sulfoxide, for example dimethyl sulfoxide (DMSO).Preferred benzene.
Formula of the present invention (VII) can be prepared by the following method, comprising:
(F), optionally under the existence of thinner and optionally under the existence of alkali, make formula (VIII) compound and CO
2reaction,
R wherein
1as above definition.
In aforesaid method (F), suitable alkali can be C
1-6lithium alkylide or two (C
1-6alkyl) amido lithium, preferably n-Butyl Lithium, tert-butyl lithium or lithium diisopropyl amido, more preferably n-Butyl Lithium.
In aforesaid method (F), suitable thinner can be all organic solvents that are inertia to participating in the material of this reaction.Preferably use hydro carbons, for example sherwood oil, normal hexane, Skellysolve A, benzene, toluene and dimethylbenzene; Ether, for example ether, tetrahydrofuran (THF), diox, glycol dimethyl ether and diglyme; And acid amides, for example dimethyl formamide.Preferred ether, tetrahydrofuran (THF) or normal hexane.
Formula of the present invention (VIII) compound can be prepared by the following method, comprising:
(G) optionally under the existence of thinner, optionally under the existence of alkali and optionally under the existence of catalyzer, the aniline of formula (IX) is reacted with adjacent bromo-iodobenzene,
R
1-NH
2(IX)
R wherein
1as above definition.
In aforesaid method (G), suitable catalyzer can be the transition-metal catalyst of linked reaction that can catalysis halogenated aromatic compound, and Pd compound for example, as Pd (dppf) Cl
2, Pd (PPh
3)
2cl
2, Pd (PPh
3)
4, Pd (dba)
2or Pd (OAc)
2, preferred Pd (PPh
3)
4.Also optionally in above-mentioned catalyzer, add organophosphorus ligand to form catalyst system, organophosphorus ligand is tri-butyl phosphine, tributylphosphine or triphenylphosphine for example.
Aforesaid method (G), suitable alkali can be alkali (soil) metal carbonate, alkali (soil) metal hydroxides or alkali (soil) metal alkoxide, preferred bases alkali metal hydroxide, alkali metal alcoholates, more preferably sodium tert-butoxide, potassium tert.-butoxide, sodium ethylate or sodium methylate.
Suitable thinner can be all organic solvents that are inertia to participating in the material of this reaction.Preferably use hydro carbons, for example sherwood oil, normal hexane, Skellysolve A, benzene, toluene and dimethylbenzene; Halohydrocarbon, for example methylene dichloride, trichloromethane, tetracol phenixin, chlorobenzene and orthodichlorobenzene; Ketone, for example acetone and methyl isopropyl Ketone; Ether, for example ether, tetrahydrofuran (THF), diox, glycol dimethyl ether and diglyme; Carboxylicesters, for example ethyl acetate; And nitrile, for example acetonitrile; Alcohol, for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and the trimethyl carbinol; Acid amides, for example dimethyl formamide; And sulfone, for example tetramethylene sulfone; Also have sulfoxide, for example dimethyl sulfoxide (DMSO).Preferably use acetonitrile, methyl-sulphoxide, tetrahydrofuran (THF), dimethyl formamide or toluene.More preferably use toluene.
Formula of the present invention (IX) compound is known, and it is commercially available and/or can prepares by currently known methods.
Formula of the present invention (III) compound is known, and it is commercially available and/or can prepares by currently known methods.For example, can prepare by following method, comprise:
(HI) optionally under the existence of thinner and optionally under the existence of organic phosphine, make the aromatic nitro compound generation ring-closure reaction of formula (X),
R wherein
2, R
3, m and n as above define; Or
(H2) optionally under the existence of thinner and optionally under the existence of catalyzer, make a kind of known formula (III) compound that Suzuki reaction occur, be converted into alternative formula (III) compound.
In aforesaid method (H1), suitable organic phosphine can be for example P (C
1-6alkoxyl group)
3, preferred P (C
1-4alkoxyl group)
3, more preferably P (OEt)
3.
In aforesaid method (H2), suitable catalyzer can be the transition-metal catalyst of linked reaction that can catalysis halogenated aromatic compound, and Pd compound for example, as Pd (dppf) Cl
2, Pd (PPh
3)
2cl
2, Pd (PPh
3)
4, Pd (dba)
2or Pd (OAc)
2, preferred Pd (PPh
3)
4.Also optionally in above-mentioned catalyzer, add organophosphorus ligand to form catalyst system, organophosphorus ligand is tri-butyl phosphine, tributylphosphine or triphenylphosphine for example.
In aforesaid method (H2), suitable alkali can be alkali (soil) metal carbonate, alkali (soil) metal hydroxides or alkali (soil) metal alkoxide, preferred bases alkali metal hydroxide, alkali metal alcoholates, more preferably sodium tert-butoxide, potassium tert.-butoxide, sodium ethylate or sodium methylate.
In aforesaid method (H2), suitable thinner can be all organic solvents that are inertia to participating in the material of this reaction.Preferably use hydro carbons, for example sherwood oil, normal hexane, Skellysolve A, benzene, toluene and dimethylbenzene; Halohydrocarbon, for example methylene dichloride, trichloromethane, tetracol phenixin, chlorobenzene and orthodichlorobenzene; Ketone, for example acetone and methyl isopropyl Ketone; Ether, for example ether, tetrahydrofuran (THF), diox, glycol dimethyl ether and diglyme; Carboxylicesters, for example ethyl acetate; And nitrile, for example acetonitrile; Alcohol, for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and the trimethyl carbinol; Acid amides, for example dimethyl formamide; And sulfone, for example tetramethylene sulfone; Also have sulfoxide, for example dimethyl sulfoxide (DMSO).Preferably use acetonitrile, methyl-sulphoxide, tetrahydrofuran (THF), dimethyl formamide or toluene.More preferably use toluene.
Formula of the present invention (III ') compound can with method preparation like preparation formula (III) compounds.
Formula of the present invention (X) compound can be prepared by the following method, comprising:
(I) optionally under the existence of thinner and optionally under the existence of catalyzer, the aryl boron ester of formula (XI) is reacted with the aromatic nitro-compound of formula (XII),
Wherein
R
6and R
7represent independently of one another hydrogen or C
1-C
8alkyl (preferred C
1-C
6or R alkyl),
6and R
7represent together C
2-C
6alkylidene group (preferred C
3-C
4alkylidene group); And
R
2as above define with m,
Wherein
L represents a leavings group, preferably halogen, more preferably chlorine, bromine or iodine;
R
3as above define with n.
In aforesaid method (I), suitable catalyzer can be for all for catalysis Suzuki reaction conventional catalyst, and Pd compound for example, as Pd (dppf) Cl
2, Pd (PPh
3)
2cl
2, Pd (PPh
3)
4, Pd (dba)
2or Pd (OAc)
2, preferred Pd (PPh
3)
4.Also optionally in above-mentioned catalyzer, add organophosphorus ligand to form catalyst system, organophosphorus ligand is tri-butyl phosphine, tributylphosphine or triphenylphosphine for example.
In aforesaid method (I), suitable alkali can be alkali (soil) metal carbonate, alkali (soil) metal hydroxides or alkali (soil) metal alkoxide, preferred bases (soil) metal carbonate, more preferably salt of wormwood, sodium carbonate, cesium carbonate or calcium carbonate.
In aforesaid method (I), suitable thinner can be all organic solvents that are inertia to participating in the material of this reaction.Preferably use hydro carbons, for example sherwood oil, normal hexane, Skellysolve A, benzene, toluene and dimethylbenzene; Halohydrocarbon, for example methylene dichloride, trichloromethane, tetracol phenixin, chlorobenzene and orthodichlorobenzene; Ketone, for example acetone and methyl isopropyl Ketone; Ether, for example ether, tetrahydrofuran (THF), diox, glycol dimethyl ether and diglyme; Carboxylicesters, for example ethyl acetate; And nitrile, for example acetonitrile; Alcohol, for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and the trimethyl carbinol; Acid amides, for example dimethyl formamide; And sulfone, for example tetramethylene sulfone; Also have sulfoxide, for example dimethyl sulfoxide (DMSO).Preferably use acetonitrile, methyl-sulphoxide, tetrahydrofuran (THF), dimethyl formamide or toluene.More preferably use toluene.
Formula of the present invention (XI) and formula (XII) compound are known, and it is commercially available and/or can prepares by currently known methods.
The present invention also provides a kind of formula (II) compound,
Wherein
R
1as above define with X.
The present invention also provides the purposes of formula of the present invention (I) compound as phosphorescent light body material or hole mobile material.
The present invention also provides a kind of light emitting composition, comprises formula of the present invention (I) compound and a kind of phosphorescent coloring, and described phosphorescent coloring is selected from the complex compound of Ir, Pt, Os, Ru, Re or Pd.
The present invention also provides a kind of organic electroluminescence device, comprises negative electrode, anode and organic function layer, and this organic function layer comprises at least one luminescent layer, and at least one deck in this luminescent layer comprises formula of the present invention (I) compound.
Formula (I) compound is preferably as the material of main part of luminescent layer.More preferably, in luminescent layer, also doped with phosphorescent coloring, the doping of this phosphorescent coloring is generally about 2-20 % by weight, preferred 2-15 % by weight, more preferably 3-12 % by weight, most preferably 5-10 % by weight, all gross weight based on luminescent layer (material of main part+phosphorescent coloring) meter.
Suitable phosphorescent coloring can be phosphorescent coloring as known in the art, comprises the complex compound of the heavy metals such as Ir, Pt, Os, Ru, Re, Pd, preferably the complex compound of Ir or Pt, most preferably green glow dyestuff Ir (ppy)
3and Ir (ppy)
2(acac), red dye PtOEP and blue phosphorescent dyestuff FIrpic etc.Their concrete structure formula is as follows:
Generally speaking, organic electroluminescence device comprises the multilayer organic function layer between negative electrode and anode, and it comprises hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer etc., and wherein luminescent layer generally includes material of main part and dyestuff.Beyond content cited in lower general remark and embodiment, other technology contents that includes organic electroluminescence devices well known by persons skilled in the art, for example making method and general one-tenth grade, and are also applicable in the present invention.
Substrate can be used the substrate in traditional organic luminescent device, for example: glass or plastics.
Anode material can adopt transparent high conductivity material, for example indium tin oxygen (ITO), indium zinc oxygen (IZO), tindioxide (SnO
2), zinc oxide (ZnO) etc.
Thickness of hole transport layer is generally at 5nm-5 μ m, can adopt various tri-arylamine group materials, N for example, N '-bis-(3-tolyl)-N, N '-phenylbenzene-[1,1-xenyl]-4,4 '-diamines (TPD) and N, N ' phenylbenzene-N, N '-bis-(1-naphthyl)-(1,1 '-xenyl)-4,4 '-diamines (NPB), preferably NPB.
Luminescent layer can be also that single layer structure can be also multilayered structure; Every layer of luminescent layer can be also doped structure for single-shot light body luminescent material structure; Luminescent dye can be selected phosphor material; Glow color is not limit, can for as red, yellow, blue, green etc.
Negative electrode can adopt metal and composition thereof structure, as Mg:Ag and Ca:Ag etc., can be also electron injecting layer/metal-layer structure, as LiF/Al, Li
2the common cathode construction such as O.
If no special instructions, in the present invention various pharmaceutical chemicalss used as the raw materials such as adjacent bromo-iodobenzene, tert-butyl lithium, carbazole, phenylo boric acid, naphthalene boronic acids are all commercially available raw materials.
Now provide following examples to illustrate in greater detail the present invention, but should not be understood as limitation of the present invention.
preparation Example
Instrument and equipment
Mass spectrum in the present embodiment adopts ZAB-HS type mass spectrograph to measure (manufacture of Britain Micromass company), and ultimate analysis adopts vario EL type elemental analyser to measure (manufacture of Britain ElementarAnalysensysteme GmbH company).
Embodiment 1: the preparation of formula (I) compound
1. the preparation of Compound I-1
By the carbazole of the compound of 47.5g compound formula II-1,34.2g formula III-1,0.575gPd (dba)
2, 20g sodium tert-butoxide and 2.0g 10 % by weight tri-butyl phosphine solution be added to be equipped with and be dissolved in 400mL toluene there-necked flask; logical nitrogen protection; reflux 6 hours is until without raw material; cooling; the mixed solution that adds 30ml concentrated hydrochloric acid and 100ml water, stirs separatory, and organic layer is dry; be spin-dried for, post separation obtains obtaining white solid 48.25g.MS (m/e): 647, yield 75.0%.
Ultimate analysis (C48H29N3): theoretical value C:89.00%, H:4.51%, N:6.49%; Measured value C:89.08%, H:4.53%, N:6.39%
2. the preparation of Compound I-2
With with the similar method preparation formula I-2 in preparation Compound I-1, different is to use the formula II-2 compound of same molar to replace formula II-1 compound.MS(m/e)：697.8。
Ultimate analysis (C52H31N3): theoretical value C:89.50%, H:4.48%, N:6.02%; Measured value C:89.62%, H:4.52%, N:5.86%
3. the preparation of Compound I-17
By the carbazole of the compound of 55.1g formula II-3,34.2g formula III-1,0.575g Pd (dba)
2, 20g sodium tert-butoxide and 2.0g 10 % by weight tri-butyl phosphine solution be added to be equipped with and be dissolved in 400mL toluene there-necked flask; logical nitrogen protection; reflux 6 hours is until without raw material; cooling; the mixed solution that adds 30ml concentrated hydrochloric acid and 100ml water, stirs separatory, and organic layer is dry; be spin-dried for, post separation obtains obtaining white solid 54.82g.MS (m/e): 723.8, yield 75.0%.
Ultimate analysis (C54H33N3): theoretical value C:89.60%, H:4.60%, N:5.80%; Measured value C:89.88%, H:4.62%, N:5.50%
4. the preparation of Compound I-18
By the carbazole of the compound of 55.1g formula II-4,34.2g formula III-1,0.575g Pd (dba)
2, 20g sodium tert-butoxide and 2.0g 10 % by weight tri-butyl phosphine solution be added to be equipped with and be dissolved in 400mL toluene there-necked flask; logical nitrogen protection; reflux 6 hours is until without raw material; cooling; the mixed solution that adds 30ml concentrated hydrochloric acid and 100ml water, stirs separatory, and organic layer is dry; be spin-dried for, post separation obtains obtaining white solid 54.82g.MS (m/e): 723.8, yield 75.0%.
Ultimate analysis (C54H33N3): theoretical value C:89.60%, H:4.60%, N:5.80%; Measured value C:89.88%, H:4.62%, N:5.50%
5. the preparation of Compound I-26
By the carbazole of the compound of 48.9g formula II-5,34.2g formula III-1,0.575gPd (dba)
2, 20g sodium tert-butoxide and 2.0g 10 % by weight tri-butyl phosphine solution be added to be equipped with and be dissolved in 400mL toluene there-necked flask; logical nitrogen protection; reflux 6 hours is until without raw material; cooling; the mixed solution that adds 30ml concentrated hydrochloric acid and 100ml water, stirs separatory, and organic layer is dry; be spin-dried for, post separation obtains obtaining white solid 54.82g.MS (m/e): 723.8, yield 75.0%.
Ultimate analysis (C49H31N3): theoretical value C:88.93%, H:4.72%, N:6.35%; Measured value C:88.73%, H:4.71%, N:6.56%
6. the preparation of Compound I-27
By the compound of the compound of 47.5g formula II-1,49.0g formula III-2,0.575gPd (dba)
2, 20g sodium tert-butoxide and 2.0g 10 % by weight tri-butyl phosphine solution be added to be equipped with and be dissolved in 400mL toluene there-necked flask; logical nitrogen protection; reflux was controlled extremely without raw material in 6 hours; cooling; the mixed solution that adds 30ml concentrated hydrochloric acid and 100ml water, stirs separatory, and organic layer is dry; be spin-dried for, post separation obtains obtaining white solid 60.1g.MS (m/e): 799.9, yield 75.0%.
Ultimate analysis (C60H37N3): theoretical value C:90.09%, H:4.66%, N:5.25%; Measured value C:90.20%, H:4.70%, N:5.10%
7. the preparation of Compound I-28
By the compound of the compound of 47.5g formula II-1,49.0g formula III-3,0.575gPd (dba)
2, 20g sodium tert-butoxide and 2.0g 10 % by weight tri-butyl phosphine solution be added to be equipped with and be dissolved in 400mL toluene there-necked flask; logical nitrogen protection; reflux 6 hours is until without raw material; cooling; the mixed solution that adds 30ml concentrated hydrochloric acid and 100ml water, stirs separatory, and organic layer is dry; be spin-dried for, post separation obtains obtaining white solid 60.1g.MS (m/e): 799.9, yield 75.0%.
Ultimate analysis (C60H37N3): theoretical value C:90.09%, H:4.66%, N:5.25%; Measured value C:90.18%, H:4.69%, N:5.13%
8. the preparation of Compound I-41
By the compound of the compound of 55.1g formula II-3,48.6g formula III-2,0.575gPd (dba)
2, 20g sodium tert-butoxide and 2.0g 10 % by weight tri-butyl phosphine solution be added to be equipped with and be dissolved in 400mL toluene there-necked flask; logical nitrogen protection; reflux 6 hours is until without raw material; cooling; the mixed solution that adds 30ml concentrated hydrochloric acid and 100ml water, stirs separatory, and organic layer is dry; be spin-dried for, post separation obtains obtaining white solid 54.82g.MS (m/e): 723.8, yield 75.0%.
Ultimate analysis (C66H41N3): theoretical value C:90.49%, H:4.72%, N:4.80%; Measured value C:90.88%, H:4.62%, N:4.50%
9. the preparation of Compound I-45
By the compound of the compound of 47.5g formula II-1,63.8g formula III-4,0.575gPd (dba)
2, 20g sodium tert-butoxide and 2.0g 10 % by weight tri-butyl phosphine solution be added to be equipped with and be dissolved in 400mL toluene there-necked flask; logical nitrogen protection; reflux 6 hours is until without raw material; cooling; the mixed solution that adds 30ml concentrated hydrochloric acid and 100ml water, stirs separatory, and organic layer is dry; be spin-dried for, post separation obtains obtaining white solid 73.3g.MS (m/e): 978, yield 75.0%.
Ultimate analysis (C74H347N3): theoretical value C:90.86%, H:4.84%, N:4.30%; Measured value C:90.60%, H:4.80%, N:5.40%.
10. the preparation of Compound I-3
(1) preparation of intermediate compound I-A2 '-1
By the compound of 47.5g formula II-1,16.7g carbazole III-1,0.575gPd (dba)
2, 9.6g sodium tert-butoxide and 2.0g 10 % by weight tri-butyl phosphine solution be added to be equipped with and be dissolved in 400mL toluene there-necked flask; logical nitrogen protection; reflux 6 hours is until without raw material; cooling; the mixed solution that adds 30ml concentrated hydrochloric acid and 100ml water, stirs separatory, and organic layer is dry; be spin-dried for, post separation obtains obtaining white solid 20g.MS (m/e): 561, yield 35.6%.
(2) preparation of product I-3
By the compound of the compound of 56.1g formula I-A2 '-1,24.3g formula III-2,0.575gPd (dba)
2, 9.6g sodium tert-butoxide and 2.0g 10 % by weight tri-butyl phosphine solution be added to be equipped with and be dissolved in 600mL toluene there-necked flask; logical nitrogen protection; reflux 6 hours is until without raw material; cooling; the mixed solution that adds 30ml concentrated hydrochloric acid and 100ml water, stirs separatory, and organic layer is dry; be spin-dried for, post separation obtains obtaining white solid 57.9g.MS (m/e): 723.8, yield 80.0%.
Ultimate analysis (C54H33N3): theoretical value C:89.60%, H:4.60%, N:5.80%; Measured value C:89.80%, H:4.64%, N:5.56%
The preparation of 12. Compound I-7
By the compound of the compound of 56.1g formula I-A2 '-1,24.3g formula III-3,0.575gPd (dba)
2, 9.6g sodium tert-butoxide and 2.0g 10 % by weight tri-butyl phosphine solution be added to be equipped with and be dissolved in 600mL toluene there-necked flask; logical nitrogen protection; reflux 6 hours is until without raw material; cooling; the mixed solution that adds 30ml concentrated hydrochloric acid and 100ml water, stirs separatory, and organic layer is dry; be spin-dried for, post separation obtains obtaining white solid 57.9g.MS (m/e): 723.8, yield 80.0%.
Ultimate analysis (C54H33N3): theoretical value C:89.60%, H:4.60%, N:5.80%; Measured value C:89.80%, H:4.64%, N:5.56%
The preparation of 13. Compound I-33
By the compound of the compound of 56.1g formula I-A2 '-1,31.9g formula III-4,0.575gPd (dba)
2, 9.6g sodium tert-butoxide and 2.0g 10 % by weight tri-butyl phosphine solution be added to be equipped with and be dissolved in 600mL toluene there-necked flask; logical nitrogen protection; reflux 6 hours is until without raw material; cooling; the mixed solution that adds 30ml concentrated hydrochloric acid and 100ml water, stirs separatory, and organic layer is dry; be spin-dried for, post separation obtains obtaining white solid 57.9g.MS (m/e): 723.8, yield 80.0%.
Ultimate analysis (C30H37N3): theoretical value C:90.09%, H:4.66%, N:5.25%; Measured value C:89.80%, H:4.64%, N:5.56%.
Preparation in accordance with the present invention, with aforementioned specific embodiment similarly, also prepare compound Compound I-1 to other compound in I-50.These compounds are summarized in following table:
Embodiment 2: the preparation of formula (II) compound
1. the preparation of Compound I I-5
Compound in this example is prepared by following reaction scheme:
(1) preparation of compound VI II-1
Under nitrogen protection; the p-methylphenyl amine (10.7g, 0.1mol), adjacent bromo-iodobenzene (70.8g, 0.25mol), the sodium tert-butoxide (48g that in 500ml there-necked flask, add formula IX-1; 0.5mol), with 300ml dry toluene, then add Pd (dba)
2(0.57g, 1mmol) and tri-butyl phosphine (2ml10 % by weight toluene solution, 2mmol), reaction system reflux 24 hours, TLC detection reaction completes.After system cools to room temperature, solution, with silica gel and diatomite filtration (toluene), is drained to solvent, crude product, through column chromatography separated (petrol ether/ethyl acetate), obtains white solid 29g, yield approximately 70%.
(2) preparation of compound VI I-1
Under nitrogen protection; the compound VI II-1 that 4.2g is as above made (10mmol) is dissolved in the THF that 50ml is dry; with dry ice-propanone, bathe and reaction system is cooled to-78 ℃; (2.4M solution, 24mmol), adds rear continuation and at-78 ℃, reacts 1.5 hours slowly to drip 10ml n-BuLi; add the dry ice that 1g is dry; then be slowly warmed up to room temperature, and at room temperature react 3h, add saturated NH
4cl solution cancellation reaction, ethyl acetate extraction product, anhydrous Mg
2sO
4dry, drain solvent and obtain crude product, through column chromatography separated (petrol ether/ethyl acetate), obtain white solid 2.3g, yield 84%.
(3) preparation of compound VI-1
In the dry voltage-resistant reactor of a 250ml, add the compound VI I-1 (5g as above making, 17.5mmol), carbon tetrabromide (11.6g, 35mmol), reaction system, through three find time-nitrogen circulation, then adds 100ml dry benzene, and mixture stirs 5 minutes, add triphenylphosphine (18.34g, 70mmol).Reaction mixture is vigorous stirring reaction 48h at 150 ℃, etc. system, cools to room temperature, adds CH
2cl
2solubilizing reaction mixture.Crude product obtains white solid 4.6g, yield 60% through column chromatography for separation (pure sherwood oil).
(4) preparation of compound V-1
A. under nitrogen protection, by dibromo compound (4.4g, 10mmol), the PdCl of the formula VI-1 as above making
2(PPh
3)
2(0.7g, 1mmol) and CuI (0.38g, 2mmol) join one and fill the trimethylsilyl acetylene (5.7ml that contains formula (VII), in the withstand voltage 250ml reaction flask of 100ml triethylamine solution 40mmol), reaction mixture is heated to 100 ℃, and at this temperature, reaction response is 20 hours.After system cool to room temperature, add 100ml CH
2cl
2, then use each washed twice of saturated ammonium chloride solution and water, dry.Thick product obtains light brown solid 3.56g, yield 75% by column chromatography separation.
B. above-mentioned solid is dissolved in to 30ml CH
2cl
2, slowly drip the 15ml CH of 10g 4-butyl ammonium fluoride trihydrate
2cl
2solution, the about 1h of stirring reaction at room temperature after adding, TLC detection reaction completes.This solution is filtered by a silica gel short column, drain the white solid 2.4g that solvent obtains formula V-1, approach theoretical yield.
(5) preparation of compound IV-1
Under nitrogen protection, the compound V-1 that 2.4g (7.5mmol) is as above made is dissolved in the toluene that 50mL is dry, adds 0.1gPtCl
2(0.38mmol, 5%eq).The about 6h reaction that refluxes is complete.Reaction solution, without precipitation, with short silicagel column decolouring, obtains orange solids compound 1.2g, yield 50%.
(6) preparation of formula II-5 compound
In there-necked flask, add compound IV-1 that 3.31g (10mmol) as above makes and be dissolved in 60ml methylene dichloride, slowly be added dropwise to 3.2g (20mmol) bromine, drip off stirring at room 1 hour, then reflux is 4 hours, point plate is without raw material, the mixing solutions that adds 5g sodium bisulfite and 20ml water, stirs separatory, organic layer anhydrous magnesium sulfate drying, then silicagel column decolouring, filtrate is spin-dried for, and by a small amount of ethyl acetate, boils, and then room temperature is filtered.Obtain the yellow solid of 4.25g, MS (m/e): 489, yield 86.9%.
2. the preparation of Compound I I-1
With with preparation Compound I I-5 similar method preparation formula II-1, different is to use the aniline IX-2 of same molar to replace p-methylphenyl amine IX-1.MS(m/e)：475.1。
3. the preparation of Compound I I-3
With with preparation Compound I I-5 similar method preparation formula II-3, different is to use the 4-p-diaminodiphenyl IX-3 of same molar to replace p-methylphenyl amine IX-1.MS(m/e)：551.2。
4. the preparation of Compound I I-6
With with preparation Compound I I-5 similar method preparation formula II-6, different is to use 9 of same molar, 9-dimethyl-2-fluorenamine IX-4 replaces p-methylphenyl amine IX-1.MS(m/e)：591.3。
5. the preparation of Compound I I-4
With with preparation Compound I I-5 similar method preparation formula II-4, different is to use the 3-p-diaminodiphenyl IX-5 of same molar to replace p-methylphenyl amine IX-1.MS(m/e)：551.2。
6. the preparation of Compound I I-7
With with preparation Compound I I-5 similar method preparation formula II-7, different is to use the naphthalidine IX-6 of same molar to replace p-methylphenyl amine IX-1.MS(m/e)：525.2。
Embodiment 3: the preparation of formula (III) compound
1. the preparation of compound III-2
The compound of 27.5g formula X-1 and 15g triethyl-phosphite are added in there-necked flask to reflux 12 hours, step-down is subsequently steamed except unnecessary triethyl-phosphite, and then adding 100ml volume ratio is the ethanolic soln of 1: 1, filters, solid alcohol sherwood oil recrystallization, obtains pale solid 14.6g.MS (m/e): 243, yield 60.0%.
2. the preparation of compound III-5
With with the similar method preparation formula III-5 in preparation compound III-2, different is to use compounds X-2 of same molar to replace compounds X-1.
3. the preparation of compound III-6
With with the similar method preparation formula III-6 in preparation compound III-2, different is to use compounds X-3 of same molar to replace compounds X-1.
4. the preparation of compound III-4
With with the similar method preparation formula III-4 in preparation compound III-2, different is to use compounds X-4 of same molar to replace compounds X-1.
5. the preparation of compound III-3
By 24.6g 3-bromine carbazole, 17.5g phenylo boric acid and 0.5g Pd (PPh
3)
4be dissolved in 400mL dioxane solution, 24.2g salt of wormwood is dissolved in 20mL water and is added in above reaction solution, 70 ℃ of stirring reaction 3h, TLC monitors reaction end.React complete, separate organic phase, organic layer is washed three times and used anhydrous Na
2sO
4after dry, carry out column chromatography, eluent is sherwood oil: methylene dichloride=20: 1 (V
1/ V
2), obtain solid 15.1g.
6. the preparation of compound III-7
With with the similar method preparation formula III-7 in preparation compound III-3, different is to use 3 of 0.5 times of molar weight, 6-dibromo carbazole replaces compound 3-bromine carbazole.
7. the preparation of compound III-8
With with the similar method preparation formula III-8 in preparation compound III-3, different is to use the 2-naphthalene boronic acids of same molar to replace compound phenylo boric acid.
8. the preparation of compound III-9
With with the similar method preparation formula III-9 in preparation compound III-3, different is to use 9 of same molar, 9-dimethyl-2-fluorenes boric acid replaces compound phenylo boric acid.
Embodiment 4: the preparation of compounds X
1. the preparation of compounds X-1
By the phenylo boric acid of 27.8g compounds X II-1,13.2g formula XI-1 and 0.55g Pd (PPh
3)
4be dissolved in 330mL toluene in the mixed solution with 220mL ethanol, 24.2g salt of wormwood is dissolved in 110mL water and is added in above reaction solution, 70 ℃ of stirring reaction 3h, TLC monitors reaction end.React complete, separate organic phase, organic layer is washed three times and used anhydrous Na
2sO
4after dry, carry out column chromatography, eluent is sherwood oil: methylene dichloride=20: 1 (V
1/ V
2), obtain white solid 20.7g.MS (m/e): 259, yield 80.0%.
2. the preparation of compounds X-2
By 1-naphthalene boronic acids and the 0.55gPd (PPh of 27.8g compounds X II-1,16.2g formula XI-2
3)
4be dissolved in the mixed solution of 330mL toluene and 220mL ethanol, 24.2g salt of wormwood is dissolved in 110mL water and is added in above reaction solution, 70 ℃ of stirring reaction 3h, TLC monitors reaction end.React complete, separate organic phase, organic layer is washed three times and used anhydrous Na
2sO
4after dry, carry out column chromatography, eluent is sherwood oil: methylene dichloride=20: 1 (V
1/ V
2), obtain white solid 24.7g.MS (m/e): 309, yield 80.0%.
3. the preparation of compounds X-3
By 2-naphthalene boronic acids and the 0.55gPd (PPh of 27.8g compounds X II-1,16.2g formula XI-3
3)
4be dissolved in 330mL toluene in the mixed solution with 220mL ethanol, 24.2g salt of wormwood is dissolved in 110mL water and is added in above reaction solution, 70 ℃ of stirring reaction 3h, TLC monitors reaction end.React complete, separate organic phase, organic layer is washed three times and used anhydrous Na
2sO
4after dry, carry out column chromatography, eluent is sherwood oil: methylene dichloride=20: 1 (V
1/ V
2), obtain white solid 24.7g.MS (m/e): 309, yield 80%.
4. the preparation of compounds X-4
By the phenylo boric acid of 35.4g compounds X II-2,13.2g formula XI-1 and 0.55g Pd (PPh
3)
4be dissolved in 330mL toluene in the mixed solution with 220mL ethanol, 24.2g salt of wormwood is dissolved in 110mL water and is added in above reaction solution, 70 ℃ of stirring reaction 3h, TLC monitors reaction end.React complete, separate organic phase, organic layer is washed three times and used anhydrous Na
2sO
4after dry, carry out column chromatography, eluent is sherwood oil: methylene dichloride=20: 1 (V
1/ V
2), obtain white solid 28.0g.MS (m/e): 351, yield 80%.
Embodiment 5: the preparation of Compound I X
By 34.1g 9,9-dimethyl-2-fluorenes boric acid, 17.2g para-bromoaniline and 0.55g Pd (PPh
3)
4be dissolved in 400mL dioxane solution, 24.2g salt of wormwood is dissolved in 20mL water and is added in above reaction solution, 70 ℃ of stirring reaction 3h, TLC monitors reaction end.React complete, separate organic phase, organic layer is washed three times and used anhydrous Na
2sO
4after dry, carry out column chromatography, eluent is sherwood oil: methylene dichloride=20: 1 (V
1/ V
2), obtain brown solid 15.1g.MS (m/e): 285, yield 60%.
The preparation of embodiment 6. compounds X II
1. the preparation of compounds X II-1
By phenylo boric acid and the 0.55gPd (PPh of the bromo-2-oil of mirbane of the Isosorbide-5-Nitrae of 28.0g two, 13.20g
3)
4be dissolved in 330mL toluene in the mixed solution with 220mL ethanol, 24.2g salt of wormwood is dissolved in 110mL water and is added in above reaction solution, after 70 ℃ of stirring reaction 1.5h, TLC monitors reaction end.React complete, separate organic phase, organic layer is washed three times and used anhydrous Na
2sO
4after dry, carry out column chromatography, eluent is sherwood oil: methylene dichloride=20: 1 (V
1/ V
2), obtain white solid 13.9g.MS (m/e): 278, yield 50.0%.
5. the preparation of compounds X II-2
By 4-biphenyl boric acid and the 0.55gPd (PPh of the bromo-2-oil of mirbane of Isosorbide-5-Nitrae-bis-of 28.0g, 19.8g
3)
4be dissolved in 330mL toluene in the mixed solution with 220mL ethanol, 24.2g salt of wormwood is dissolved in 110mL water and is added in above reaction solution, after 70 ℃ of stirring reaction 1.5h, TLC monitors reaction end.React complete, separate organic phase, organic layer is washed three times and used anhydrous Na
2sO
4after dry, carry out column chromatography, eluent is sherwood oil: methylene dichloride=20: 1 (V
1/ V
2), obtain white solid 17.7g.MS (m/e): 354, yield 50.0%.
application Example
In the present embodiment, the structure of OLED device is: organic luminous layer (EL)/electron transfer layer (the ETL)/negative electrode (metal electrode) of substrate/anode (ITO)/hole transmission layer (HTL)/dopant dye.
The material structure formula of using in the present embodiment is as follows:
In element manufacturing of the present invention, select glass substrate, ITO (tin indium oxide) makes anode material.
In element manufacturing of the present invention, selected hole mobile material is TCTA (4,4 ', 4 "-tri-(N-carbazyl) triphenylamine (4,4 ', 4 "-tri (N-carbazolyl) triphenylamine)).
In element manufacturing of the present invention, selected electron injection material is LiF, and cathode material is Al.
Device of the present invention is made as follows:
The sheet glass that will be coated with ITO transparency conducting layer (100-200nm) in commercial clean-out system (10% KOH solution) with 20KHz frequency supersound process, in deionized water, rinse, at acetone: supersound washing in alcohol mixed solvent (volume ratio 1: 1), under thousand grades of clean environments, 90 ℃ are baked to and remove moisture content completely, by UV-light and 200mg/L ozone clean, and with low energy positively charged ion bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 * 10
-5to 9 * 10
-3pa, on above-mentioned anode tunic, vacuum evaporation TCTA is as hole transmission layer, and evaporation speed is 0.1nm/s, and evaporation thickness is 50nm;
On hole transmission layer, vacuum evaporation formula of the present invention (I) compound or CBP are as material of main part and Ir (ppy)
3as phosphorescent coloring, the weight ratio of material of main part and phosphorescent coloring is 100: 9, forms the luminescent layer (as shown in table 1 below) of device, and evaporation speed is 0.1nm/s, and evaporation total film thickness is 30nm;
Vacuum evaporation one deck BCP on luminescent layer, its evaporation speed is 0.1nm/s, evaporation total film thickness is 30nm; Then evaporation one deck Alq3, its evaporation speed is 0.1nm/s, evaporation total film thickness is 30nm, forms electron transfer layer;
The Al layer that the LiF of vacuum evaporation 0.5nm is 150nm as electron injecting layer and thickness on electron transfer layer is as the negative electrode of device.
Table 1: device performance
Result by Application Example can find out, the device that adopts compound of the present invention to prepare has obtained current efficiency and the luminous efficiency that relative prior art is higher, effectively reduces in addition driving voltage.
Although describe the present invention in conjunction with the embodiments, but the present invention is not limited to above-described embodiment, should be appreciated that under the guiding of the present invention's design, those skilled in the art can carry out various changes and modifications, and these changes and improvements also belong to content of the present invention.
Claims (8)
1. formula (I) compound,
Wherein
R
1representative replaces or unsubstituted C
6-C
18aryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
6alkyl or C
6-C
18the group of aryl, described substituting group is again optionally by one or more C
1-C
6alkyl replaces;
R
2represent independently of one another hydrogen or replacement or unsubstituted C
6-C
18aryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
6alkyl or C
6-C
18the group of aryl;
R
3represent independently of one another hydrogen or replacement or unsubstituted C
6-C
18aryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
6alkyl or C
6-C
18the group of aryl;
R
4represent independently of one another hydrogen or replacement or unsubstituted C
6-C
18aryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
6alkyl or C
6-C
18the group of aryl;
R
5represent independently of one another hydrogen or replacement or unsubstituted C
6-C
18aryl, is wherein having in substituent situation, and described substituting group is one or more C that are selected from
1-C
6alkyl or C
6-C
18the group of aryl; And
M, n, p and q represent 0,1,2 or 3 independently of one another.
2. the formula of claim 1 (I) compound, wherein
R
1, R
2, R
3, R
4and R
5representative is independently of one another selected from following group:
M, n, p and q represent 0,1,2 or 3 independently of one another.
3. the formula of claim 1 (I) compound, is selected from following compound:
4. a method of preparing formula (I) compound of claim 1, comprising:
(A1) as [R
2]
mwith [R
5]
qidentical and [R
3]
nwith [R
4]
pwhen identical, optionally under the existence of thinner and optionally under the existence of alkali and catalyzer, the halo naphtho-acridine compounds of formula (II) is reacted with the aromatic amine of formula (III), production (I-A1) compound,
Wherein
X represents halogen; And
R
1as claim 1 defines,
Wherein
R
2, R
3, m and n define as claim 1,
R wherein
1, R
2, R
3, m and n define as claim 1; Or
(A2) as [R
2]
mwith [R
5]
qand/or [R
3]
nwith [R
4]
pwhen different, optionally under the existence of thinner and optionally under the existence of alkali and catalyzer, the halo naphtho-acridine compounds of formula (II) is reacted with the aromatic amine of formula (III), production (I-A2 ') compound, then optionally under the existence of thinner and optionally under the existence of alkali and catalyzer, the aromatic amine of formula (I-A2 ') compound and formula (III ') is reacted, production (I-A2) compound
R wherein
1, R
2, R
3, m and n define as claim 1,
R wherein
4, R
5, p and q define as claim 1,
R wherein
1, R
2, R
3, R
4, R
5, m, n, p and q define as claim 1.
5. formula (II) compound,
Wherein
R
1as claim 1 defines, X defines as claim 4.
6. the formula of claim 1 (I) compound is as the purposes of phosphorescent light body material or hole mobile material.
7. a light emitting composition, comprises formula (I) compound and a kind of phosphorescent coloring of claim 1, and described phosphorescent coloring is selected from the complex compound of Ir, Pt, Os, Ru, Re or Pd.
8. an organic electroluminescence device, comprises negative electrode, anode and organic function layer, and this organic function layer comprises at least one luminescent layer, and at least one deck in this luminescent layer comprises formula (I) compound of claim 1.
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| CN103539737B (en) * | 2013-10-23 | 2017-03-08 | Tcl集团股份有限公司 | A kind of azepine phenanthro- fluorene kind derivative, preparation method and electroluminescent fluorescent luminescent device |
| US20170018719A1 (en) * | 2014-03-12 | 2017-01-19 | Idemitsu Kosan Co., Ltd. | Compound, material for organic electroluminescence element, ink composition, organic electroluminescence element, and electronic device |
| CN105777715B (en) * | 2016-03-30 | 2018-03-30 | 阜阳欣奕华材料科技有限公司 | A kind of compound, organic electroluminescence device and display device |
| CN105859687B (en) * | 2016-03-30 | 2018-05-25 | 阜阳欣奕华材料科技有限公司 | A kind of compound, organic electroluminescence device and display device |
| CN106349212A (en) * | 2016-08-24 | 2017-01-25 | 长春海谱润斯科技有限公司 | Naphtho-thioxanthene derivative as well as preparation method and application thereof |
| CN112687823B (en) * | 2020-12-27 | 2022-07-08 | 浙江华显光电科技有限公司 | Composition and organic electroluminescent element comprising same |
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|---|---|---|---|---|
| CN1490312A (en) * | 2003-09-05 | 2004-04-21 | �廪��ѧ | Carbazole derivative and its application in electroluminescent device |
| CN101412907A (en) * | 2007-10-17 | 2009-04-22 | 中国科学院理化技术研究所 | Electroluminescent organic material, synthetic method and use thereof |
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| JP2001244076A (en) * | 2000-03-01 | 2001-09-07 | Toyota Central Res & Dev Lab Inc | Organic elemctroluminescent element manufactured by using acridine derivative compound |
| JP4769551B2 (en) * | 2005-11-10 | 2011-09-07 | 凸版印刷株式会社 | Coating type low molecular carrier transportable material, light emitting material and ink |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1490312A (en) * | 2003-09-05 | 2004-04-21 | �廪��ѧ | Carbazole derivative and its application in electroluminescent device |
| CN101412907A (en) * | 2007-10-17 | 2009-04-22 | 中国科学院理化技术研究所 | Electroluminescent organic material, synthetic method and use thereof |
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