CN109476678A

CN109476678A - Heterocyclic compound and organic illuminating element comprising it

Info

Publication number: CN109476678A
Application number: CN201880002765.5A
Authority: CN
Inventors: 金永锡; 权赫俊; 金旼俊; 金公谦; 金正凡
Original assignee: LG Chemical Co Ltd
Current assignee: LG Corp
Priority date: 2017-02-14
Filing date: 2018-02-12
Publication date: 2019-03-15
Anticipated expiration: 2038-02-12
Also published as: WO2018151479A3; KR102056535B1; KR20180093819A; WO2018151479A2; CN109476678B

Abstract

This specification is related to the heterocyclic compound indicated by chemical formula 1 and comprising its organic illuminating element.

Description

Heterocyclic compound and organic illuminating element comprising it

Technical field

The South Korea patent application 10-2017- that this application claims submitted on 2 14th, 2017 to Koran Office No. 0019961 priority, its contents are contained in this manual.

This specification is related to heterocyclic compound and the organic illuminating element comprising it.

Background technique

Under normal conditions, organic light emission phenomenon refers to the phenomenon that converting electrical energy into luminous energy using organic substance.Using having The organic illuminating element of machine luminescence phenomenon usually has comprising anode and cathode and positioned at the knot of the organic matter layer between them Structure.Wherein, in order to improve the efficiency and stability of organic illuminating element, organic matter layer is made of multilayered structure in most cases, And above-mentioned multilayered structure is made of respectively different substances, for example, can be by hole injection layer, hole transmission layer, luminescent layer, electricity The formation such as sub- transport layer, electron injecting layer.For the structure of such organic illuminating element, if applied between electrodes Making alive, then hole is injected into organic matter layer from anode, and electronics is injected into organic matter layer from cathode, when institute's injected holes and electricity It will form exciton (exciton) when son meets, light will be issued when the exciton transits to ground state again.

The lasting new material for requiring exploitation to be used for above-mentioned organic illuminating element.

Summary of the invention

This specification provides heterocyclic compound and the organic illuminating element comprising it.

According to an embodiment of this specification, the heterocyclic compound indicated by following chemical formula 1 is provided.

[chemical formula 1]

In above-mentioned chemical formula 1,

X1 is O or S,

L1 be Direct Bonding, substituted or unsubstituted arlydene or substituted or unsubstituted heteroarylidene,

Y1 and Y3 be N, Y2 CR13, Y4 CR14 or Y2 and Y4 be N, Y1 CR14, Y3 CR13,

Above-mentioned R13 is the group in conjunction with above-mentioned L1,

R2 and R3 or R3 and R4 is the group in conjunction with the * of following chemical formula 2,

The group in conjunction with the * of following chemical formula 2, R1, R5 to R12 and R14 be not mutually the same or not into R4 by above-mentioned R2 Together, hydrogen, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl or adjacent group are each independently It can be bonded to each other and form substituted or unsubstituted ring,

N is 1 or 2,

When n is 2, two L1 are same or different to each other,

[chemical formula 2]

In above-mentioned chemical formula 2,

It * is the position in conjunction with the R2 and R3 of above-mentioned chemical formula 1 or R3 and R4,

Ar1 is substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl,

R15 to R18 is same or different to each other, and is each independently hydrogen, substituted or unsubstituted aryl or substitution or not Substituted heteroaryl or adjacent group can be bonded to each other and form substituted or unsubstituted ring.

In addition, according to an embodiment of this specification, a kind of organic illuminating element is provided comprising: the first electricity Pole, and the second electrode that has opposed with above-mentioned first electrode and have between above-mentioned first electrode and second electrode 1 Layer or more organic matter layer, 1 layer or more the heterocyclic compound comprising being indicated by above-mentioned chemical formula 1 in above-mentioned organic matter layer.

It can be used as the material of the organic matter layer of organic illuminating element according to the heterocyclic compound of an embodiment of this specification Material, by using the heterocyclic compound, can be realized in organic illuminating element the raising of efficiency, lower driving voltage and/ Or the raising of life characteristic.

Detailed description of the invention

Fig. 1 illustrates the organic illuminating elements 10 according to the embodiment of this specification.

Fig. 2 illustrates the organic illuminating element 11 of another embodiment according to this specification.

Fig. 3 is the mass spectrum of compound 1 that manufactures in the synthesis example 1 of this specification.

Fig. 4 is the mass spectrum of compound 2 that manufactures in the synthesis example 2 of this specification.

Fig. 5 is the mass spectrum of compound 3 that manufactures in the synthesis example 3 of this specification.

Fig. 6 is the mass spectrum of compound 4 that manufactures in the synthesis example 4 of this specification.

Fig. 7 is the mass spectrum of compound 5 that manufactures in the synthesis example 5 of this specification.

Fig. 8 is the mass spectrum of compound 6 that manufactures in the synthesis example 6 of this specification.

Fig. 9 is the mass spectrum of compound 7 that manufactures in the synthesis example 7 of this specification.

Figure 10 is the mass spectrum of compound 8 that manufactures in the synthesis example 8 of this specification.

Figure 11 is the mass spectrum of compound 9 that manufactures in the synthesis example 9 of this specification.

Figure 12 is the mass spectrum of compound 10 that manufactures in the synthesis example 10 of this specification.

Figure 13 is the mass spectrum of compound 11 that manufactures in the synthesis example 11 of this specification.

Figure 14 is the mass spectrum of compound 12 that manufactures in the synthesis example 12 of this specification.

Figure 15 is the mass spectrum of compound 13 that manufactures in the synthesis example 13 of this specification.

Figure 16 is the mass spectrum of compound 14 that manufactures in the synthesis example 14 of this specification.

Figure 17 is the mass spectrum of compound 15 that manufactures in the synthesis example 15 of this specification.

Figure 18 is the mass spectrum of compound 16 that manufactures in the synthesis example 16 of this specification.

Figure 19 is the mass spectrum of compound 17 that manufactures in the synthesis example 17 of this specification.

Figure 20 is the mass spectrum of compound 18 that manufactures in the synthesis example 18 of this specification.

Figure 21 is the mass spectrum of compound 19 that manufactures in the synthesis example 19 of this specification.

Figure 22 is the mass spectrum of compound 20 that manufactures in the synthesis example 20 of this specification.

Figure 23 is the mass spectrum of compound 21 that manufactures in the synthesis example 21 of this specification.

Figure 24 is the mass spectrum of compound 22 that manufactures in the synthesis example 22 of this specification.

Figure 25 is the mass spectrum of compound 23 that manufactures in the synthesis example 23 of this specification.

Figure 26 is the mass spectrum of compound 24 that manufactures in the synthesis example 24 of this specification.

Symbol description

10,11: organic illuminating element

20: substrate

30: first electrode

40: luminescent layer

50: second electrode

60: hole injection layer

70: hole transmission layer

80: electron transfer layer

90: electron injecting layer

Specific embodiment

In the following, being illustrated in more details to this specification.

This specification provides the heterocyclic compound indicated by above-mentioned chemical formula 1.

The heterocyclic compound indicated by above-mentioned chemical formula 1 according to an embodiment of this specification be benzofuran [3, 4-d] pyrimidine, benzofuran [2,3-d] pyrimidine, benzothiophene simultaneously [3,4-d] pyrimidine or benzothiophene simultaneously [2,3-d] pyrimidine 2 Number position is by structure of the L1 in conjunction with the N of indolocarbazole, therefore the flowing of electronics is smooth, and above-mentioned chemical formula 2 is upper It states in chemical formula 1 in conjunction with R2 and R3 or R3 and R4, therefore the steric hindrance (steric hindrance) of above-mentioned chemical formula 1 Reduce and stable structure, therefore include the organic illuminating element of above-mentioned chemical formula 1 driving voltage it is low, efficiency is excellent, the service life is long.

In this specification, when pointing out a certain constituent element of certain a part of "comprising", as long as no especially opposite record, Then mean that other constituent elements can be further included, rather than other constituent elements are excluded.

It not only include a certain component and another when pointing out that a certain component is located at another component "upper" in this specification The case where one component contacts, include thes case where that there are other components between two components.

In the following, being illustrated to the illustration of the substituent group of this specification, but not limited to this.

Above-mentioned " substitution " this term refers to that the hydrogen atom for being incorporated into the carbon atom of compound is replaced by other substituent groups, As long as substituted position hydrogen atom can there is no limit the substitutive position of substituted position, i.e. substituent group, when replacing 2 When a above, 2 or more substituent groups be can be the same or different from each other.

" substituted or unsubstituted " this term refers to by selected from deuterium, halogen group, itrile group, nitro, acyl in this specification Imido grpup, amide groups, carbonyl, ester group, hydroxyl, substituted or unsubstituted alkyl, substituted or unsubstituted naphthenic base, substitution or not Substituted alkoxy, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkyl sulfenyl ( Alkyl thioxy), substituted or unsubstituted artyl sulfo (Aryl thioxy), replace or do not take Generation alkyl sulfoxide base (Alkyl sulfoxy), substituted or unsubstituted aryl sulfoxid es base (Aryl sulfoxy), substituted or unsubstituted alkenyl, substituted or unsubstituted silicyl, substitution Or unsubstituted boryl, substituted or unsubstituted amido, substituted or unsubstituted aryl phosphino-, substituted or unsubstituted phosphine oxide 1 or 2 or more substituent group in base, substituted or unsubstituted aryl and substituted or unsubstituted heterocycle replaces, or Person is replaced by the substituent group that 2 or more substituent groups in foregoing illustrative substituent group are formed by connecting, or takes without any Dai Ji.For example, " substituent group that 2 or more substituent groups are formed by connecting " can be xenyl.That is, xenyl can be aryl, It can also be construed to the substituent group that 2 phenyl are formed by connecting.

In this specification,Refer to the position in conjunction with other substituent groups or binding site.

In this specification, halogen group can be fluorine, chlorine, bromine or iodine.

In this specification, the carbon atom number of imide is not particularly limited, but preferably carbon atom number is 1 to 30.Specifically For, it can be the compound of following structure, but not limited to this.

In this specification, about amide groups, the nitrogen of amide groups can be by hydrogen, the straight chain of carbon atom number 1 to 30, branch or ring Shape alkyl or the aryl of carbon atom number 6 to 30 replace.Specifically, can be the compound of following structural formula, but do not limit In this.

In this specification, the carbon atom number of carbonyl is not particularly limited, but preferably carbon atom number is 1 to 30.Specifically, It can be the compound of following structure, but not limited to this.

In this specification, about ester group, the oxygen of ester group can be by the straight chain, branch or cyclic alkyl of carbon atom number 1 to 25 Or the aryl of carbon atom number 6 to 30 replaces.Specifically, can be the compound of following structural formula, but not limited to this.

In this specification, abovementioned alkyl can be linear chain or branched chain, and carbon atom number is not particularly limited, but preferably 1 to 30.As a specific example, there are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, normal-butyl, isobutyl group, tert-butyl, Zhong Ding Base, 1- methyl butyl, 1- ethyl-butyl, amyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, n-hexyl, 1- methyl Amyl, 2- methyl amyl, 4- methyl -2- amyl, 3,3- dimethylbutyl, 2- ethyl-butyl, heptyl, n-heptyl, 1- methyl oneself Base, cyclopentyl-methyl, cyclohexyl methyl, octyl, n-octyl, t-octyl, 1- methylheptyl, 2- ethylhexyl, 2- propylpentyl, N-nonyl, 2,2- dimethyl heptyl, 1- ethyl propyl, 1,1- dimethyl propyl, isohesyl, 2- methyl amyl, 4- methylhexyl, 5- methylhexyl etc., but not limited to this.

In this specification, naphthenic base is not particularly limited, but the naphthenic base of preferably carbon atom number 3 to 30, specifically, There are cyclopropyl, cyclobutyl, cyclopenta, 3- methylcyclopentyl, 2,3- dimethylcyclopentyl, cyclohexyl, 3- methylcyclohexyl, 4- first Butylcyclohexyl, 2,3- Dimethylcyclohexyl, 3,4,5- trimethylcyclohexyls, 4- tert-butylcyclohexyl, suberyl, cyclooctyl etc., But not limited to this.

In this specification, above-mentioned alkoxy can be straight chain, branch or ring-type.The carbon atom number of alkoxy does not limit especially It is fixed, but preferably carbon atom number is 1 to 30.Specifically, can be methoxyl group, ethyoxyl, positive propoxy, isopropoxy, positive fourth Oxygroup, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyl oxygen, isoamoxy, positive hexyloxy, 3,3- diformazan Base butoxy, 2- ethyl-butoxy, n-octyloxy, positive nonyl epoxide, n-decyloxy, benzyloxy, to methylbenzyloxy etc., but not It is defined in this.

In this specification, amido can be selected from-NH₂, alkyl amine group, N- alkylaryl amido, arylamine group, N- aryl heteroaryl Base amido, N- miscellaneous alkyl aryl amido and heteroaryl amido, carbon atom number are not particularly limited, but preferably 1 to 30.As The specific example of amido has methylamino, dimethyl amido, ethyl amido, diethyl amido, phenyl amido, naphthalene amido, connection Phenyl amido, anthryl amido, 9- methylanthryl amido, diphenyl amido, N- phenyl napthyl amido, xylyl amido, N- benzene Base tolyl amido, triphenyl amido, N- phenylbiphenylyl amido, N- phenyl napthyl amido, N- xenyl naphthalene amido, N- naphthalene Base fluorenyl amido, N- phenyl phenanthryl amido, N- xenyl phenanthryl amido, N- phenylfluorenyl amido, N- phenyl terphenyl amido, N- phenanthryl fluorenyl amido, N- xenyl fluorenyl amido etc., but not limited to this.

In this specification, N- alkylaryl amido refers to the amido for replacing on the N of amido and having alkyl and aryl.

In this specification, N- aryl heteroaryl amido refers to the amido for replacing on the N of amido and having aryl and heteroaryl.

In this specification, N- miscellaneous alkyl aryl amido refers to the amido for replacing on the N of amido and having alkyl and heteroaryl.

In this specification, alkyl amine group, N- aryl alkyl amido, alkyl sulfenyl ( Alkyl Thioxy), alkyl sulfoxide base (Alkyl sulfoxy), the alkyl in N- miscellaneous alkyl aryl amido with The illustration of above-mentioned alkyl is identical.Specifically, having methylsulfany, ethylsulfanyl, tert. butyl-sulphenyl, hexyl as alkyl sulfenyl Sulfenyl, octylthio etc. have methyl sulfoxide base as alkyl sulfoxide baseEthyl-sulfoxide base, propyl sulfoxide group, fourth Base sulfoxide group etc., but not limited to this.

In this specification, above-mentioned alkenyl can be linear chain or branched chain, and carbon atom number is not particularly limited, but preferably 2 to 30.As concrete example, have vinyl, 1- acrylic, isopropenyl, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- pentenyl, 2- pentenyl, 3- pentenyl, 3-methyl-1-butene base, 1,3- butadiene, allyl, 1- phenylethylene -1- base, 2- phenyl second Alkene -1- base, 2,2- talan -1- base, 2- phenyl -2- (naphthalene -1- base) ethylene -1- base, bis- (hexichol -1- base) ethylene-of 2,2- 1- base,Base, styryl etc., but not limited to this.

In this specification, silicyl specifically has trimethyl silyl, triethylsilyl, tertbutyldimethylsilyl chloride Silylation, vinyldimethylsilyl, propyl-dimethyl silicyl, triphenyl-silyl, diphenylsilyl group, Phenyl silyl groups etc., but not limited to this.

In this specification, boryl can be-BR₁₀₀R₁₀₁, above-mentioned R₁₀₀And R₁₀₁It is same or different to each other, it can be respectively independent Ground is selected from hydrogen, deuterium, halogen group, itrile group, the monocycle of substituted or unsubstituted carbon atom number 3 to 30 or polycyclic naphthenic base, takes The monocycle of the alkyl of linear chain or branched chain of generation or unsubstituted carbon atom number 1 to 30, substituted or unsubstituted carbon atom number 6 to 30 Or monocycle or the polycyclic heteroaryl of polycyclic aryl and substituted or unsubstituted carbon atom number 2 to 30.

In this specification, oxidation phosphino- specifically has diphenyl phosphine oxide base, dinaphthyl oxidation phosphino- etc., but is not limited to This.

In this specification, aryl is not particularly limited, but the aryl of preferably carbon atom number 6 to 30, and above-mentioned aryl can be with For monocyclic or polycycle.

When above-mentioned aryl be monocyclic aryl in the case where, carbon atom number is not particularly limited, but preferably carbon atom number be 6 to 30.Specifically, can be phenyl, xenyl, terphenyl etc., but not limited to this as monocyclic aryl.

When above-mentioned aryl is polycycle aryl, carbon atom number is not particularly limited, but preferably carbon atom number is 10 to 30. Specifically, as polyaromatic, can for naphthalene, anthryl, phenanthryl, triphenyl, pyrenyl, Fu base (phenalenyl), base,Base and fluorenyl etc., but not limited to this.

In this specification, above-mentioned fluorenyl can be substituted, and adjacent group can be bonded to each other and form ring.

When above-mentioned fluorenyl is substituted, Ke Yiwei AndDeng.But not limited to this.

In this specification, " adjacent " group refers to be replaced on the atom that the atom replaced with the substituent group is directly connected to Substituent group, with the substituent group in stereochemical structure immediate substituent group or the substituent group replace atom on replace Other substituent groups.For example, being taken on same carbon in substituted 2 substituent groups in adjacent position (ortho) and aliphatic ring in phenyl ring 2 substituent groups in generation can be construed to " adjacent " group.

In this specification, aryloxy group, artyl sulfo, aryl sulfoxid es base, N- aryl alkyl amido, N- aryl heteroaryl amido It is identical as the illustration of above-mentioned aryl with the aryl in aryl phosphino-.Specifically, having phenoxy group, to toluene as aryloxy group Oxygroup, toloxyl, 3,5- Dimehtyl-phenoxy, 2,4,6- trimethylbenzene oxygroup, to tert-butyl benzene oxygroup, 3- biphenyl oxygen Base, 4- biphenylyloxy, 1- naphthoxy, 2- naphthoxy, 4- methyl-1-naphthoxy, 5- methyl-2- naphthoxy, 1- anthracene oxygroup, 2- anthracene Oxygroup, 9- anthracene oxygroup, 1- phenanthryl oxygroup, 3- phenanthryl oxygroup, 9- phenanthryl oxygroup etc. have phenylsulfartyl, 2- first as artyl sulfo Base phenylsulfartyl, 4- tert-butyl-phenyl sulfenyl etc., as aryl sulfoxid es base, have phenylsulfone base, to methyl sulfoxide base etc., but simultaneously It is not limited to this.

It is substituted or unsubstituted monoarylamine base, substituted or unsubstituted as the example of arylamine group in this specification Diaryl amido or substituted or unsubstituted triaryl amido.Aryl in above-mentioned arylamine group can be monocyclic aryl, It may be polyaromatic.The above-mentioned arylamine group comprising 2 or more aryl may include monocyclic aryl, polyaromatic, It or simultaneously include monocyclic aryl and polyaromatic.For example, the aryl in above-mentioned arylamine group can be selected from the example of above-mentioned aryl Show.

In this specification, heteroaryl includes the hetero atom of 1 or more non-carbon, specifically, above-mentioned hetero atom can be with Atom comprising 1 or more in O, N, Se and S etc..Carbon atom number is not particularly limited, but preferably carbon atom number be 2 to 30, above-mentioned heteroaryl can be monocyclic or polycycle.As the example of heterocycle, there are thienyl, furyl, pyrrole radicals, miaow Oxazolyl, thiazolyl,Oxazolyl,Di azoly, bipyridyl, pyrimidine radicals, triazine radical, triazolyl, acridinyl, is rattled away at pyridyl group Piperazine base, pyrazinyl, quinolyl, quinazolyl, quinoxalinyl, phthalazinyl, Pyridopyrimidine base, pyrido-pyrazine base, pyrazine are simultaneously Pyrazinyl, isoquinolyl, indyl, carbazyl, benzoOxazolyl, benzimidazolyl, benzothiazolyl, benzo carbazole base, benzene It is bithiophene base, dibenzothiophene, benzofuranyl, phenanthroline (phenanthroline), thiazolyl, differentOxazolyl,Di azoly, thiadiazolyl group, benzothiazolyl, phenothiazinyl and dibenzofuran group etc., but not limited to this.

In this specification, as the example of heteroaryl amido, substituted or unsubstituted single heteroaryl amido replaces or not Substituted di (hetero) arylamine group or substituted or unsubstituted three heteroaryls amido.Above-mentioned includes the miscellaneous of 2 or more heteroaryls Arylamine group may include bicyclic heteroaryl, polyheteroaromatic or simultaneously comprising bicyclic heteroaryl and polyheteroaromatic.Example Such as, the heteroaryl in above-mentioned heteroaryl amido can be selected from the illustration of above-mentioned heteroaryl.

In this specification, the illustration of N- aryl heteroaryl amido and the heteroaryl in N- miscellaneous alkyl aryl amido with it is above-mentioned The illustration of heteroaryl is identical.

In this specification, arlydene refers to the aryl on aryl there are two binding site, i.e. divalent group.They are in addition to dividing The explanation of above-mentioned aryl Wei not can be applicable in other than divalent group.

In this specification, heteroarylidene refers to the aryl on heteroaryl there are two binding site, i.e. divalent group.They are removed It is respectively that can be applicable in the explanation of above-mentioned heteroaryl other than divalent group.

In this specification, adjacent group is bonded to each other in the substituted or unsubstituted ring that is formed, and " ring " refers to substitution Or unsubstituted hydrocarbon ring or substituted or unsubstituted heterocycle.

In this specification, hydrocarbon ring can be aromatic series, aliphatic or aromatic series and aliphatic condensed ring, in addition to it is above-mentioned not It is that can be selected from the illustration of above-mentioned naphthenic base or aryl other than 1 valence.

In this specification, aromatic ring can be selected from above-mentioned aryl other than not being 1 valence for monocycle or polycyclic Illustration.

In this specification, heterocycle includes the hetero atom of 1 or more non-carbon, specifically, above-mentioned hetero atom can wrap Atom containing 1 or more in O, N, Se and S etc..Above-mentioned heterocycle can be monocycle or polycyclic, can be aromatic series, fat Race or aromatic series and aliphatic condensed ring can the illustrations selected from above-mentioned heteroaryl or heterocycle other than not being 1 valence.

According to an embodiment of this specification, above-mentioned chemical formula 1 can be by any of following chemical formula 1-1 to 1-4 It indicates.

[chemical formula 1-1]

[chemical formula 1-2]

[chemical formula 1-3]

[chemical formula 1-4]

Above-mentioned chemical formula 1-1 into 1-4,

The definition of X1, L1, n, Y1 to Y4, R1, R2 and R4 to R12 are identical as above-mentioned chemical formula 1,

The definition of Ar1 and R15 to R18 is identical as above-mentioned chemical formula 2.

According to an embodiment of this specification, in above-mentioned chemical formula 1, Y1 and Y3 are N, Y2 CR13, Y4 CR14.

According to an embodiment of this specification, in above-mentioned chemical formula 1, Y2 and Y4 are N, Y1 CR14, Y3 CR13.

According to an embodiment of this specification, above-mentioned R13 is the group in conjunction with above-mentioned L1.

According to an embodiment of this specification, above-mentioned chemical formula 1 is by any of following chemical formula 1-5 to 1-12 table Show.

[chemical formula 1-5]

[chemical formula 1-6]

[chemical formula 1-7]

[chemical formula 1-8]

[chemical formula 1-9]

[chemical formula 1-10]

[chemical formula -11]

[chemical formula 1-12]

Above-mentioned chemical formula 1-5 into 1-12,

The definition of X1, L1, n, R1, R2, R4 to R12 and R14 are same as described above, the definition of Ar1 and R15 to R18 with it is above-mentioned Chemical formula 2 is identical.

According to an embodiment of this specification, above-mentioned chemical formula 1 is by any of following chemical formula 1-13 to 1-20 table Show.

[chemical formula 1-13]

[chemical formula 1-14]

[chemical formula 1-15]

[chemical formula 1-16]

[chemical formula 1-17]

[chemical formula 1-18]

[chemical formula 1-19]

[chemical formula 1-20]

Above-mentioned chemical formula 1-13 into 1-20,

The definition of L1, n, R1, R2, R4 to R12 and R14 are same as described above,

According to an embodiment of this specification, above-mentioned chemical formula 1 is by any of following chemical formula 1-21 to 1-28 table Show.

[chemical formula 1-21]

[chemical formula 1-22]

[chemical formula 1-23]

[chemical formula 1-24]

[chemical formula 1-25]

[chemical formula 1-26]

[chemical formula 1-27]

[chemical formula 1-28]

Above-mentioned chemical formula 1-21 into 1-28,

The definition of L1, n, R1, R2, R4 to R12 and R14 are same as described above,

According to an embodiment of this specification, above-mentioned R14 is substituted or unsubstituted aryl.

According to an embodiment of this specification, above-mentioned R14 is aryl.

According to an embodiment of this specification, above-mentioned R14 is phenyl or naphthyl.

According to an embodiment of this specification, above-mentioned Ar1 is aryl or is substituted with aryl or unsubstituted heteroaryl Base.

According to an embodiment of this specification, above-mentioned Ar1 is phenyl, xenyl, naphthalene, phenanthryl, fluoranthene base, triphenylene It base, pyrenyl, pyridyl group, pyrimidine radicals, the triazine radical being substituted with aryl or is substituted with aryl or unsubstituted quinazolyl.

According to an embodiment of this specification, above-mentioned Ar1 is phenyl, xenyl, naphthalene, phenanthryl, fluoranthene base, triphenylene Base, pyrenyl, pyridyl group, pyrimidine radicals, the triazine radical being substituted by phenyl or by the substituted or unsubstituted quinazoline of phenyl or naphthyl Base.

According to an embodiment of this specification, above-mentioned chemical formula 1 can be selected from following compounds.

According to an embodiment of this specification, a kind of organic illuminating element is provided comprising: first electrode, with it is upper It states that first electrode is opposed and the second electrode that has and has 1 layer or more between above-mentioned first electrode and second electrode Organic matter layer, one layer or more in above-mentioned organic matter layer includes above-mentioned heterocyclic compound.

According to an embodiment of this specification, the organic matter layer of the organic illuminating element of this specification can be by single layer knot It is configured to, can also be formed by the multilayered structure for being laminated with 2 layers or more of organic matter layer.For example, organic light emission member of the invention Part can have comprising hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, The structure as organic matter layer such as electron injecting layer.But it's not limited to that for the structure of organic illuminating element, may include more The organic layer of few or more layer.

For example, the structure of the organic illuminating element of this specification can have structure as depicted in figs. 1 and 2, but not It is defined in this.

Fig. 1 instantiates the organic hair for being sequentially laminated with first electrode 30, luminescent layer 40 and second electrode 50 on the base plate 20 The structure of optical element 10.Above-mentioned Fig. 1 may be used also according to the exemplary configuration of the organic illuminating element of an embodiment of this specification To include other organic matter layers.

Fig. 2 is instantiated is sequentially laminated with first electrode 30, hole injection layer 60, hole transmission layer 70, hair on the base plate 20 Photosphere 40, electron transfer layer 80, electron injecting layer 90 and second electrode 50 organic illuminating element structure.Above-mentioned Fig. 2 is this The exemplary configuration of the embodiment of specification can also include other organic matter layers.

According to an embodiment of this specification, above-mentioned organic matter layer includes hole transmission layer, above-mentioned hole transmission layer packet Containing the heterocyclic compound indicated by above-mentioned chemical formula 1.

According to an embodiment of this specification, above-mentioned organic matter layer includes electron transfer layer, electron injecting layer or simultaneously Carry out the layer of electron-transport and injection, above-mentioned electron transfer layer, electron injecting layer or the layer for carrying out electron-transport and injection simultaneously Include above-mentioned heterocyclic compound.

According to an embodiment of this specification, above-mentioned organic matter layer includes luminescent layer, and above-mentioned luminescent layer includes by above-mentioned The heterocyclic compound that chemical formula 1 indicates.

According to an embodiment of this specification, above-mentioned organic matter layer includes luminescent layer, and above-mentioned luminescent layer includes by above-mentioned Material of main part of the heterocyclic compound that chemical formula 1 indicates as luminescent layer.

In an embodiment of this specification, above-mentioned organic matter layer includes the heterocyclic compound indicated by above-mentioned chemical formula 1 Object may include other organic compounds, metal or metallic compound as dopant as material of main part.

Above-mentioned dopant can be one or more of the compound selected from following illustrations, and but not limited to this.

According to an embodiment of this specification, above-mentioned organic matter layer can also be comprising passing selected from hole injection layer, hole 1 layer or more in defeated layer, luminescent layer, electron transfer layer and electron injecting layer.

In the organic illuminating element of this specification, 1 layer or more in the organic matter layer heterocyclic compound comprising this specification, The heterocyclic compound indicated by above-mentioned chemical formula 1 can use well known material and method in the technical field in addition to this Manufacture.

When above-mentioned organic illuminating element includes multiple organic matter layers, above-mentioned organic matter layer can be by same substance or difference Substance is formed.

For example, the organic illuminating element in this specification can be by stacking gradually first electrode, organic matter on substrate Layer and second electrode and manufacture.At this point it is possible to manufacture as follows: using such as sputtering method (sputtering) or electronics The physical vapor depositions methods such as beam evaporation method (e-beam evaporation) (PVD:physical Vapor Deposition) are in base Evaporation metal or conductive metal oxide or their alloy on plate and form first electrode, then this first electricity Extremely upper organic matter layer of the formation comprising hole injection layer, hole transmission layer, luminescent layer and electron transfer layer, it is organic at this later Vapor deposition can be used as the substance of second electrode in nitride layer.In addition to the method described above, the second electricity can also successively be deposited on substrate Pole substance, organic matter layer, first electrode substance manufacture organic illuminating element.In addition, indicating miscellaneous about by above-mentioned chemical formula 1 Cycle compound not only can use vacuum vapour deposition when manufacturing organic illuminating element, can also be using solution coating method come shape At organic matter layer.Herein, so-called solution coating method refer to spin-coating method, dip coating, knife coating, ink jet printing method, silk screen print method, Spray-on process, rolling method etc., but not limited to this.

According to an embodiment of this specification, above-mentioned first electrode is anode, and above-mentioned second electrode is cathode.

According to another embodiment of this specification, above-mentioned first electrode is cathode, and above-mentioned second electrode is anode.

As above-mentioned anode material, generally for enabling hole successfully to inject to organic matter layer, preferably work function Big substance.As the specific example for the anode material that can be used in the present invention, just like metals such as vanadium, chromium, copper, zinc, gold or Their alloy；Such as zinc oxide, indium oxide, tin indium oxide (ITO), indium zinc oxide (IZO) metal oxide；Such as ZnO:Al or SnO₂: the combination of the metals such as Sb and oxide；Such as poly- (3 methyl thiophene), poly- [3,4- (ethylidene -1,2- dioxy) thiophene] (PEDOT), electroconductive polymers such as polypyrrole and polyaniline etc., but not limited to this.

As above-mentioned cathode substance, generally for electronics is easily injected into organic matter layer, preferably work function is small Substance.It is golden just like magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminium, silver, tin and lead etc. as the specific example of cathode substance Category or their alloy；Such as LiF/Al or LiO₂Multilayered structures substance such as/Al, Mg/Ag etc., but not limited to this.

Above-mentioned hole injection layer is the layer in the hole that injection carrys out self-electrode, as hole injecting material, preferably followingization Close object: the ability with transporting holes has hole injection effect from anode, for the excellent of luminescent layer or luminescent material Hole inject effect, prevent the exciton generated in luminescent layer from migrating to electron injecting layer or electron injection material, and film Forming ability is excellent.It is preferred that HOMO (highest occupied molecular orbital(HOMO), the highest occupied of hole injecting material Molecular orbital) between the work function of anode material and the HOMO of surrounding organic matter layer.As hole infusion The concrete example of matter has metalloporphyrin (porphyrin), Oligopoly thiophene, aryl amine system organic matter, six nitriles, six azepine benzophenanthrene system to have It is organic matter, anthraquinone and polyaniline and polythiophene that machine object, quinacridone (quinacridone), which are organic matter, (perylene), It is electroconductive polymer etc., but not limited to this.

Above-mentioned hole transmission layer is to receive the hole from hole injection layer and by the layer of hole transport to luminescent layer, as Hole transporting material is the substance that can be received the hole from anode or hole injection layer and transfer them to luminescent layer, empty Mobility big substance in cave is suitable.As concrete example, there are aryl amine system organic matter, electroconductive polymer and deposit simultaneously In conjugate moiety and the block copolymer of non-conjugated portion etc., but not limited to this.

Above-mentioned electronic barrier layer be prevent from entering hole injection layer by luminescent layer from electron injecting layer injected electrons and It can be improved the service life of element and the layer of efficiency, when necessary, well known material can be used and be formed in luminescent layer and hole note Enter the part appropriate between layer.

As the luminescent substance of above-mentioned luminescent layer, be can be received respectively from hole transmission layer and electron transfer layer hole and Electronics and the substance for making it combine and issuing the light of visible light region, preferably for the high object of the quantum efficiency of fluorescence or phosphorescence Matter.As concrete example, there is 8-hydroxyquinoline aluminum complex (Alq₃)；Carbazole based compound；Two polystyrene-based (dimerized Styryl) compound；BAlq；10- hydroxy benzo quinoline metal compound；BenzoAzoles, benzothiazole and benzimidazole system Close object；Poly- (to phenylene vinylidene) (PPV) is macromolecule；Loop coil (spiro) compound；Polyfluorene, rubrene etc., but not It is defined in this.

Above-mentioned luminescent layer may include material of main part and dopant material.Material of main part has aromatic fused ring derivative or contains Heterocyclic compound etc..Specifically, having anthracene derivant, pyrene derivatives, naphthalene derivatives and five as aromatic fused ring derivative Benzene derivative, phenanthrene compound, fluoranthene compound etc. have carbazole derivates, dibenzofurans derivative as nitrogen-containing heterocgcies Object, ladder type furan compoundPyrimidine derivatives etc., but not limited to this.

As above-mentioned dopant material, there are aromatic amine derivative, styrylamine compounds, boron complexes, fluoranthene Close object, metal complex etc..Specifically, there is substituted or unsubstituted arylamino as aromatic amine derivative Aromatic fused ring derivative, have pyrene with arylamino, anthracene,Two indeno pyrenes (Periflanthene) etc., as benzene second Enamine compound is to replace the compound for having at least one aryl vinyl on substituted or unsubstituted arylamine, by selected from virtue 1 or 2 or more substituent group in base, silicyl, alkyl, naphthenic base and arylamino is substituted or unsubstituted.Specifically, There are styryl amine, styryl diamines, styryl triamine, styryl tetramine etc., but not limited to this.In addition, making For metal complex, there are complex of iridium, platinum complex etc., but not limited to this.

Above-mentioned hole blocking layer be prevent from entering electron injecting layer by luminescent layer from hole injection layer injected holes and It can be improved the service life of element and the layer of efficiency, when necessary, well known material can be used and be formed in luminescent layer and electronics note Enter the part appropriate between layer.

Above-mentioned electron transfer layer is to receive the electronics from electron injecting layer and by the layer of electron-transport to luminescent layer, as Electron-transporting material is can to receive well the electronics from cathode and transfer them to the substance of luminescent layer, electron transfer The big substance of rate is suitable.As concrete example, there is the Al complex of 8-hydroxyquinoline, comprising Alq₃Complex, it is organic from By based compound, flavonol-metal complex etc., but not limited to this.Electron transfer layer can be such as institute in the prior art It is used together as use with the cathode substance of any desired.In particular, the example of suitable cathode substance is that have low function Function and the common substance associated with aluminium layer or silver layer.Specifically, have caesium, barium, calcium, ytterbium and samarium, for each substance, Accompany with aluminium layer or silver layer.

Above-mentioned electron injecting layer is the layer for the electronics that injection carrys out self-electrode, preferably following compound: has transmission electronics Ability, there is the electron injection effect from cathode, there is excellent electron injection effect for luminescent layer or luminescent material, Prevent generated exciton in luminescent layer from migrating to hole injection layer, and film Forming ability is excellent.Specifically, there is fluorenes Ketone, anthraquinone bismethane (Anthraquinodimethane), diphenoquinone, thiopyrandioxide,Azoles, twoAzoles, triazole, miaow Azoles, tetrabasic carboxylic acid, fluorenylidene-methane, anthrone etc. and their derivative, metal complex and nitrogenous five-membered ring derivative etc., but It's not limited to that.

As above-mentioned metal complex, have 8-hydroxyquinoline lithium, bis- (8-hydroxyquinoline) zinc, bis- (8-hydroxyquinoline) copper, It is bis- (8-hydroxyquinoline) manganese, three (8-hydroxyquinoline) aluminium, three (2- methyl -8-hydroxyquinoline) aluminium, three (8-hydroxyquinoline) galliums, double (10- hydroxy benzo [h] quinoline) beryllium, bis- (10- hydroxy benzo [h] quinoline) zinc, bis- (2- methyl -8- quinoline) gallium chlorides, bis- (2- Methyl -8- quinoline) (o-cresol) gallium, bis- (2- methyl -8- quinoline) (1- naphthols) aluminium, bis- (2- methyl -8- quinoline) (beta naphthals) Gallium etc., but not limited to this.

The organic illuminating element of this specification can be top emission type, bottom emission type or double according to used material To light emitting-type.

It, can also be in organic solar batteries other than organic illuminating element according to an embodiment of this specification Or the heterocyclic compound in organic transistor comprising being indicated by above-mentioned chemical formula 1.

Embodiment

In the following, enumerating embodiment in order to illustrate this specification and being described in detail.But according to this specification Embodiment can be deformed into other various forms, the range of this specification should not be interpreted as being defined in it is following in detail The embodiment stated.The embodiment of this specification is provided to be more fully explained this specification to those skilled in the art 's.

The basic synthesis of following reaction equations 1 to 8 can be passed through according to the heterocyclic compound of an embodiment of this specification Process (scheme) manufacture, but not limited to this.

[reaction equation 1]

[reaction equation 2]

[reaction equation 3]

[reaction equation 4]

[reaction equation 5]

[reaction equation 6]

[reaction equation 7]

[reaction equation 8]

In above-mentioned reaction equation 1 to 8, defining for X1, R14, L1 and n is identical as the definition in above-mentioned chemical formula 1, Ar1's It defines identical as the definition in above-mentioned chemical formula 2.

According to an embodiment of this specification, above-mentioned intermediate A-1 and A-2 can be made by following reaction equations 9 and 10 It makes, but not limited to this.

[reaction equation 9]

[reaction equation 10]

In above-mentioned reaction equation 9 and 10, the definition of X1 and R14 are identical as the definition in above-mentioned chemical formula 1.

The synthesis of 1. compound A-1-1 of Production Example

In round-bottomed flask, by 2,4- dichloro benzo [4,5] thieno [3,4-d] pyrimidine (10g, 0.04mol), phenyl boric acid (4.8g, 0.04mol), calcium carbonate (8.3g, 0.06mol) and Pd (PPh₃)₄(1.8g, 4mol%) is dissolved in anhydrous tetrahydro furan After water, flowed next time 4 hours in 80 DEG C of temperature conditions.After reaction, the temperature of reactant is cooled to room temperature, is extracted with chloroform It takes.After the organic layer of extraction removes moisture removal with anhydrous magnesium sulfate, is recrystallized and changed with ethyl acetate (Ethyl acetate) It closes object A-1-1 (9.53g, 82%).

The synthesis of 2. compound A-1-2 of Production Example

In above-mentioned Production Example 1, phenyl boric acid is replaced to obtain in addition to this by identical method using 1- naphthalenylboronic acid Compound A-1-2.

The synthesis of 3. compound A-1-3 of Production Example

In above-mentioned Production Example 1, phenyl boric acid is replaced to pass through identical method in addition to this using 2- naphthalenylboronic acid Close object A-1-3.

The synthesis of 4. compound A-1-4 of Production Example

In above-mentioned Production Example 1, [1,1'- xenyl] -4- ylboronic acid is used to replace phenyl boric acid, in addition to this, by identical Method obtain compound A-1-4.

The synthesis of 5. compound A-2-1 of Production Example

In above-mentioned Production Example 1,2,4- dichloro benzo [4,5] thiophene is replaced using 2,4- dichloro benzofuran [3,2-d] pyrimidine Simultaneously [3,4-d] pyrimidine obtains compound A-2-1 by identical method in addition to this to pheno.

The synthesis of 6. compound A-2-2 of Production Example

In above-mentioned Production Example 1,2,4- dichloro benzo [4,5] thiophene is replaced using 2,4- dichloro benzofuran [3,2-d] pyrimidine Pheno simultaneously [3,4-d] pyrimidine replaces phenyl boric acid to obtain compound A- by identical method in addition to this using 1- naphthalenylboronic acid 2-2。

The synthesis of 7. compound A-2-3 of Production Example

In above-mentioned Production Example 1,2,4- dichloro benzo [4,5] thiophene is replaced using 2,4- dichloro benzofuran [3,2-d] pyrimidine Pheno simultaneously [3,4-d] pyrimidine replaces phenyl boric acid to obtain compound A- by identical method in addition to this using 2- naphthalenylboronic acid 2-3。

The synthesis of 8. compound A-2-4 of Production Example

In above-mentioned Production Example 1,2,4- dichloro benzo [4,5] thiophene is replaced using 2,4- dichloro benzofuran [3,2-d] pyrimidine Simultaneously [3,4-d] pyrimidine, use [1,1'- xenyl] -4- ylboronic acid replace phenyl boric acid to pass through identical method in addition to this to pheno Obtain compound A-2-4.

The synthesis of 9. compound A-3-1 of Production Example

In above-mentioned Production Example 1,2,4- dichloro benzo is replaced using 2,4- dichloro benzo [4,5] thieno [2,3-d] pyrimidine [4,5] thieno [3,4-d] pyrimidine obtains compound A-3-1 by identical method in addition to this.

The synthesis of 10. compound A-3-2 of Production Example

In above-mentioned Production Example 1,2,4- dichloro benzo is replaced using 2,4- dichloro benzo [4,5] thieno [2,3-d] pyrimidine [4,5] thieno [3,4-d] pyrimidine replaces phenyl boric acid to pass through identical method in addition to this using 1- naphthalenylboronic acid Close object A-3-2.

The synthesis of 11. compound A-3-3 of Production Example

In above-mentioned Production Example 1,2,4- dichloro benzo is replaced using 2,4- dichloro benzo [4,5] thieno [2,3-d] pyrimidine [4,5] thieno [3,4-d] pyrimidine replaces phenyl boric acid to pass through identical method in addition to this using 2- naphthalenylboronic acid Close object A-3-3.

The synthesis of 12. compound A-3-4 of Production Example

In above-mentioned Production Example 1,2,4- dichloro benzo is replaced using 2,4- dichloro benzo [4,5] thieno [2,3-d] pyrimidine [4,5] thieno [3,4-d] pyrimidine uses [1,1'- xenyl] -4- ylboronic acid to replace phenyl boric acid, in addition to this, by identical Method obtain compound A-3-4.

The synthesis of 13. compound A-4-1 of Production Example

In above-mentioned Production Example 1,2,4- dichloro benzo [4,5] thiophene is replaced using 2,4- dichloro benzofuran [2,3-d] pyrimidine Simultaneously [3,4-d] pyrimidine obtains compound A-4-1 by identical method in addition to this to pheno.

The synthesis of 14. compound A-4-2 of Production Example

In above-mentioned Production Example 1,2,4- dichloro benzo [4,5] thiophene is replaced using 2,4- dichloro benzofuran [2,3-d] pyrimidine Pheno simultaneously [3,4-d] pyrimidine replaces phenyl boric acid to obtain compound A- by identical method in addition to this using 1- naphthalenylboronic acid 4-2。

The synthesis of 15. compound A-4-3 of Production Example

In above-mentioned Production Example 1,2,4- dichloro benzo [4,5] thiophene is replaced using 2,4- dichloro benzofuran [2,3-d] pyrimidine Pheno simultaneously [3,4-d] pyrimidine replaces phenyl boric acid to obtain compound A- by identical method in addition to this using 2- naphthalenylboronic acid 4-3。

The synthesis of 16. compound A-4-4 of Production Example

In above-mentioned Production Example 1,2,4- dichloro benzo [4,5] thiophene is replaced using 2,4- dichloro benzofuran [2,3-d] pyrimidine Simultaneously [3,4-d] pyrimidine, use [1,1'- xenyl] -4- ylboronic acid replace phenyl boric acid to pass through identical method in addition to this to pheno Obtain compound A-4-4.

The synthesis of 17. compound B- (a) -1 of Production Example

In round-bottomed flask, by compound A-1-1 (10g, 0.034mol), 5,6- indoline simultaneously [2,3-b] carbazole (8.6g, 0.034mol), potassium phosphate (14.3g, 0.067mol) are dissolved in DMAC N,N' dimethyl acetamide (N, the N- of 100ml Dimethylacetamide it in), is flowed next time 1 hour in 160 DEG C of temperature conditions.After reaction, temperature is cooled to room temperature, Reactant is poured into water after solid is precipitated and is filtered.The solid of filtering is dissolved in chloroform and is extracted.The organic layer of extraction is used After anhydrous magnesium sulfate removes moisture removal, compound B- (a) -1 is obtained with ethyl acetate (Ethyl acetate) recrystallization (14.8g, 85%).

The synthesis of 18. compound B- (a) -2 of Production Example

In above-mentioned Production Example 17, compound A-1-1 is replaced to pass through identical method in addition to this using compound A-2-2 Obtain compound B- (a) -2.

The synthesis of 19. compound B- (b) -1 of Production Example

In above-mentioned Production Example 17, using 5,11- indoline, simultaneously [3,2-b] carbazole replaces 5,6- indoline simultaneously [2,3- B] carbazole, replace compound A-1-1 to obtain compound B- (b)-by identical method in addition to this using compound A-3-2 1。

The synthesis of 20. compound B- (b) -2 of Production Example

In above-mentioned Production Example 17, using 5,11- indoline, simultaneously [3,2-b] carbazole replaces 5,6- indoline simultaneously [2,3- B] carbazole, replace compound A-1-1 to obtain compound B- by identical method in addition to this using compound A-4-3 (b)-2。

The synthesis of 21. compound B- (c) -1 of Production Example

In above-mentioned Production Example 17, using 5,8- indoline, simultaneously [2,3-c] carbazole replaces 5,6- indoline simultaneously [2,3-b] Carbazole replaces compound A-1-1 to obtain compound B- (c) -1 by identical method in addition to this using compound A-2-2.

The synthesis of 22. compound B- (c) -2 of Production Example

In above-mentioned Production Example 17, using 5,8- indoline, simultaneously [2,3-c] carbazole replaces 5,6- indoline simultaneously [2,3-b] Carbazole replaces compound A-1-1 to obtain compound B- (c) -2 by identical method in addition to this using compound A-3-1.

The synthesis of 23. compound B- (d) -1 of Production Example

In above-mentioned Production Example 17, using 5,12- indoline, simultaneously [3,2-a] carbazole replaces 5,6- indoline simultaneously [2,3- B] carbazole, replace compound A-1-1 to obtain compound B- (d)-by identical method in addition to this using compound A-1-3 1。

The synthesis of 24. compound B- (d) -2 of Production Example

In above-mentioned Production Example 17, using 5,12- indoline, simultaneously [3,2-a] carbazole replaces 5,6- indoline simultaneously [2,3- B] carbazole, replace compound A-1-1 to obtain compound B- (d)-by identical method in addition to this using compound A-4-1 2。

The synthesis of 1. compound 1 of synthesis example

Compound B- (a) -1 (10g, 0.019mol), 1- bromonaphthalene (4g, 0.019mol) and phosphoric acid are added in round-bottomed flask Bis- (tri-tert-butylphosphine) palladiums (0.02g, 0.2mol%) are added in potassium (8.2g, 0.038mol), the side Bian Huiliu, and further reflux 4 is small When.After reaction, temperature is cooled to room temperature, the solid of precipitation is filtered.Then, the solid of filtering is dissolved in chlorine Extraction in imitative.After the organic layer of extraction removes moisture removal with anhydrous magnesium sulfate, with ethyl acetate (Ethyl acetate) recrystallization Obtain compound 1 (concrete example 1-2) 9.7g (78%).([M+H]=643)

Fig. 3 is the mass spectrum of the compound 1 manufactured in above-mentioned synthesis example 1.

The synthesis of 2. compound 2 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced to obtain chemical combination by identical method in addition to this using 2- chlorine pyrimidine Object 2 (concrete example 1-12).([M+H]=595)

Fig. 4 is the mass spectrum of the compound 2 manufactured in above-mentioned synthesis example 2.

The synthesis of 3. compound 3 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced to pass through in addition to this using chloro- 4, the 6- diphenyl -1,3,5-triazines of 2- Same procedure obtains compound 3 (concrete example 1-17).([M+H]=748)

Fig. 5 is the mass spectrum of the compound 3 manufactured in above-mentioned synthesis example 3.

The synthesis of 4. compound 4 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 1- bromobenzene, replaces compound B- (a)-using compound B- (a) -2 1, in addition to this, compound 4 (concrete example 1-120) is obtained by same procedure.([M+H]=628)

Fig. 6 is the mass spectrum of the compound 4 manufactured in above-mentioned synthesis example 4.

The synthesis of 5. compound 5 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 9- bromine phenanthrene, replaces compound B- (a)-using compound B- (a) -2 1, in addition to this, compound 5 (concrete example 1-124) is obtained by identical method.([M+H]=727)

Fig. 7 is the mass spectrum of the compound 5 manufactured in above-mentioned synthesis example 5.

The synthesis of 6. compound 6 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using the chloro- 4- phenylquinazoline of 2-, uses compound B- (a) -2 replacementization It closes object B- (a) -1 and compound 6 (concrete example 1-134) is obtained by identical method in addition to this.([M+H]=755)

Fig. 8 is the mass spectrum of the compound 6 manufactured in above-mentioned synthesis example 6.

The synthesis of 7. compound 7 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 3- chlorine fluoranthene, replaces compound B- using compound B- (b) -1 (a) -1 compound 7 (concrete example 2-74) ([M+H]=768), in addition to this, is obtained by same procedure

Fig. 9 is the mass spectrum of the compound 7 manufactured in above-mentioned synthesis example 7.

The synthesis of 8. compound 8 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 1- bromine pyrene, replaces compound B- (a)-using compound B- (b) -1 1, in addition to this, compound 8 (concrete example 2-76) is obtained by identical method.([M+H]=768)

Figure 10 is the mass spectrum of the compound 8 manufactured in above-mentioned synthesis example 8.

The synthesis of 9. compound 9 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using the chloro- 4- of 2- (naphthalene -2- base) quinoline, uses -1 generation of compound B- (b) For compound B- (a) -1, in addition to this, compound 9 (concrete example 2-84) is obtained by same procedure.([M+H]=822)

Figure 11 is the mass spectrum of the compound 9 manufactured in above-mentioned synthesis example 9.

The synthesis of 10. compound 10 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 1- bromobenzene, replaces compound B- (a)-using compound B- (b) -2 1, in addition to this, compound 10 (concrete example 2-188) is obtained by method identical with above-mentioned 3-1).([M+H]=628)

Figure 12 is the mass spectrum of the compound 10 manufactured in above-mentioned synthesis example 10.

The synthesis of 11. compound 11 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 2- bromine triphenylene, replaces compound B- using compound B- (b) -2 (a) -1 compound 11 (concrete example 2-194), in addition to this, is obtained by same procedure.([M+H]=778)

Figure 13 is the mass spectrum of the compound 11 manufactured in above-mentioned synthesis example 11.

The synthesis of 12. compound 12 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 4- chlorine pyrimidine, replaces compound B- using compound B- (b) -2 (a) -1 compound 12 (concrete example 2-200), in addition to this, is obtained by identical method.([M+H]=629)

Figure 14 is the mass spectrum of the compound 12 manufactured in above-mentioned synthesis example 12.

The synthesis of 13. compound 13 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 2- bromonaphthalene, replaces compound B- (a)-using compound B- (c) -1 1, in addition to this, compound 13 (concrete example 3-122) is obtained by identical method.([M+H]=678)

Figure 15 is the mass spectrum of the compound 13 manufactured in above-mentioned synthesis example 13.

The synthesis of 14. compound 14 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 3- chloropyridine, replaces compound B- using compound B- (c) -1 (a) -1 compound 14 (concrete example 3-129), in addition to this, is obtained by identical method.([M+H]=628)

Figure 16 is the mass spectrum of the compound 14 manufactured in above-mentioned synthesis example 14.

The synthesis of 15. compound 15 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 2- chloro-quinazoline, replaces compound B- using compound B- (c) -1 (a) -1 compound 15 (concrete example 3-133), in addition to this, is obtained by same procedure.([M+H]=679)

Figure 17 is the mass spectrum of the compound 15 manufactured in above-mentioned synthesis example 15.

The synthesis of 16. compound 16 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 9- bromine phenanthrene, replaces compound B- (a)-using compound B- (c) -2 1, in addition to this, compound 16 (concrete example 3-56) is obtained by same procedure.([M+H]=693)

Figure 18 is the mass spectrum of the compound 16 manufactured in above-mentioned synthesis example 16.

The synthesis of 17. compound 17 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 4- chloropyridine, replaces compound B- using compound B- (c) -2 (a) -1 compound 17 (concrete example 3-62), in addition to this, is obtained by same procedure.([M+H]=595)

Figure 19 is the mass spectrum of the compound 17 manufactured in above-mentioned synthesis example 17.

The synthesis of 18. compound 18 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using chloro- 4, the 6- diphenyl -1,3,5-triazines of 2-, uses compound B- (c) -2 compound 18 (concrete example 3-68) is obtained by same procedure in addition to this instead of compound B- (a) -1.([M+H]= 749)

Figure 20 is the mass spectrum of the compound 18 manufactured in above-mentioned synthesis example 18.

The synthesis of 19. compound 19 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 2- bromonaphthalene, replaces compound B- (a)-using compound B- (d) -1 1, in addition to this, compound 19 (concrete example 4-37) is obtained by identical method.([M+H]=693)

Figure 21 is the mass spectrum of the compound 19 manufactured in above-mentioned synthesis example 19.

The synthesis of 20. compound 20 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using bromo- 1, the 1'- biphenyl of 4-, replaces chemical combination using compound B- (d) -1 Object B- (a) -1 obtains compound 20 (concrete example 4-38) by identical method in addition to this.([M+H]=719)

Figure 22 is the mass spectrum of the compound 20 manufactured in above-mentioned synthesis example 20.

The synthesis of 21. compound 21 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using the chloro- 4- phenylquinazoline of 2-, uses compound B- (d) -1 replacementization It closes object B- (a) -1 and compound 21 (concrete example 4-49) is obtained by same procedure in addition to this.([M+H]=772)

Figure 23 is the mass spectrum of the compound 21 manufactured in above-mentioned synthesis example 21.

The synthesis of 22. compound 22 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using bromo- 1, the 1'- biphenyl of 4-, replaces chemical combination using compound B- (d) -2 Object B- (a) -1 obtains compound 22 (concrete example 4-157) by same procedure in addition to this.([M+H]=654)

Figure 24 is the mass spectrum of the compound 22 manufactured in above-mentioned synthesis example 22.

The synthesis of 23. compound 23 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 2- chloropyridine, replaces compound B- using compound B- (d) -2 (a) -1 compound 23 (concrete example 4-162), in addition to this, is obtained by identical method.([M+H]=578)

Figure 25 is the mass spectrum of the compound 23 manufactured in above-mentioned synthesis example 23.

The synthesis of 24. compound 24 of synthesis example

In above-mentioned synthesis example 1,1- bromonaphthalene is replaced using 2- chlorine pyrimidine, replaces compound B- using compound B- (d) -2 (a) -1 compound 24 (concrete example 4-165), in addition to this, is obtained by same procedure.([M+H]=579)

Figure 26 is the mass spectrum of the compound 24 manufactured in above-mentioned synthesis example 24.

Comparative example 1

It will be withThickness thin film be coated with the glass substrate of ITO (tin indium oxide, indium tin oxide) and put Enter in the distilled water dissolved with dispersing agent, is washed using ultrasonic wave.At this moment, detergent uses Fei Xier company (Fischer Co.) product, distilled water use filter (Filter) the filtering 2 times steamings manufactured by Millipore Corp. (Millipore Co.) Distilled water.After ITO is washed 30 minutes, it is repeated 2 times with distilled water and carries out 10 minutes ultrasonic washings.Terminate in distillation water washing Afterwards, after being carried out ultrasonic washing with the solvent of isopropyl alcohol, acetone and methanol and dried, it is delivered to plasma washing machine. In addition, after five minutes by aforesaid substrate cleaning, delivering the substrate to vacuum evaporation plating machine using oxygen plasma.

After substrate is installed on vacuum chamber, pressure of foundation is made to become 1 × 10^-6Torr, then by organic matter on above-mentioned ITO It successively forms a film, that is, use following DNTPD as hole injection and transport layerAs hole transport and electronics Barrier layer and use following NPBThe following CBP for being chiefly used in red phosphorescent material of main part substance under normal circumstances are made Based on material (95wt%) use, as dopant, be deposited altogetherAbove-mentioned Dp-6 (5wt%), as electron-transport Layer uses Alq₃ LiF is used as cathodeAlAnd it successively forms a film.In above process, The evaporation rate of organic matter maintains/ sec, LiF are maintainedThe evaporation rate of/sec, aluminium maintainThe vapor deposition of/sec Speed.

Comparative example 2 to 8

Above-mentioned CBP is replaced to pass through identical method system in addition to this using following compound A to G in above-mentioned comparative example 1 Make organic illuminating element.

Embodiment 1 to 24

In above-mentioned comparative example 1, above-mentioned CBP is replaced using the compound 1 to 24 manufactured in above-mentioned synthesis example 1 to 24 respectively, In addition to this, organic illuminating element is made by identical method.

The organic illuminating element made into above-mentioned comparative example 1 to 8 and embodiment 1 to 24 applies 10mA/cm²Electric current, Measure driving voltage, current efficiency and service life, T95 indicates the time required when brightness is decreased to 95% from original intensity.By its As a result it is shown in following table 1.

[table 1]

In above-mentioned table 1, above-mentioned comparative example 1 is to have used the above-mentioned CBP as previous luminescent layer material of main part as having Machine light-emitting component, above-mentioned comparative example 2 and 3 are that the compound of above-mentioned chemical formula 2 will be combined on the R1 and R2 of above-mentioned chemical formula 1 The organic illuminating element of material of main part as luminescent layer.

In addition, comparative example 4 and 5 is used in having for the compound for being combined with carbazole on the position Y1 of the application chemical formula 1 Machine light-emitting component, comparative example 6 to 8 are to replace Yin for being combined with substituted aryl on the position Y3 of the application chemical formula 1 Diindyl and carbazole and the compound formed are used as the organic illuminating element of the material of main part of luminescent layer.

The organic illuminating element of above-described embodiment 1 to 24 is will to be combined on the position Y2 or Y3 of the application chemical formula 1 Indolocarbazole, i.e., the compound for being combined with chemical formula 2 on the R2 and R3 or R3 and R4 of above-mentioned chemical formula 1 and being formed are used as The organic illuminating element of the material of main part of luminescent layer.

Know that the intramolecular electronics flowing of the heterocyclic compound of the application chemical formula 1 is smooth, steric hindrance is few and structure is steady It is fixed, therefore using the organic illuminating element of its above-described embodiment 1 to 24 compared with the organic illuminating element of comparative example 1 to 8, it drives Dynamic voltage is low, and efficiency is excellent, and the service life is long.

Claims

1. a kind of heterocyclic compound indicated by following chemical formula 1:

Chemical formula 1

In the chemical formula 1,

X1 is O or S,

L1 is Direct Bonding, substituted or unsubstituted arlydene or substituted or unsubstituted heteroarylidene,

Y1 and Y3 be N, Y2 CR13, Y4 CR14 or Y2 and Y4 be N, Y1 CR14, Y3 CR13,

The R13 is the group in conjunction with the L1,

Into R4, the group in conjunction with the * of following chemical formula 2, R1, R5's R2 to R12 and R14 are not same or different to each other, respectively From independently being hydrogen, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl or adjacent group can be with that This in conjunction with and form substituted or unsubstituted ring,

N is 1 or 2,

When n is 2, two L1 are same or different to each other,

Chemical formula 2

In the chemical formula 2,

It * is the position in conjunction with the R2 and R3 of the chemical formula 1 or R3 and R4,

R15 to R18 is same or different to each other, and is each independently hydrogen, substituted or unsubstituted aryl or substituted or unsubstituted Heteroaryl or adjacent group can be bonded to each other and form substituted or unsubstituted ring.

2. heterocyclic compound according to claim 1, wherein the chemical formula 1 is appointed by following chemical formula 1-1 into 1-4 One expression:

Chemical formula 1-1

Chemical formula 1-2

Chemical formula 1-3

Chemical formula 1-4

The chemical formula 1-1 into 1-4,

The definition of X1, L1, n, Y1 to Y4, R1, R2 and R4 to R12 are identical as the chemical formula 1,

The definition of Ar1 and R15 to R18 is identical as the chemical formula 2.

3. heterocyclic compound according to claim 1, wherein the chemical formula 1 is appointed by following chemical formula 1-5 into 1-12 One expression:

Chemical formula 1-5

Chemical formula 1-6

Chemical formula 1-7

Chemical formula 1-8

Chemical formula 1-9

Chemical formula 1-10

Chemical formula 1-11

Chemical formula 1-12

The chemical formula 1-5 into 1-12,

The definition of X1, L1, n, R1, R2 and R4 to R12 are identical as the chemical formula 1,

The definition of Ar1 and R15 to R18 is identical as the chemical formula 2,

R14 is substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl.

4. heterocyclic compound according to claim 1, wherein the R14 is aryl.

5. heterocyclic compound according to claim 1, wherein the Ar1 is aryl or is substituted with aryl or unsubstituted Heteroaryl.

6. heterocyclic compound according to claim 1, wherein the chemical formula 1 is selected from following compounds:

7. a kind of organic illuminating element comprising: first electrode, it is opposed with the first electrode and have second electrode, And have 1 layer or more of organic matter layer between the first electrode and second electrode, 1 layer in the organic matter layer with Upper includes heterocyclic compound described in any one of claims 1 to 6.

8. organic illuminating element according to claim 7, wherein the organic matter layer includes hole transmission layer, the sky Cave transport layer includes the heterocyclic compound.

9. organic illuminating element according to claim 7, wherein the organic matter layer includes electron transfer layer, electronics note Enter layer or carry out the layer of electron-transport and injection simultaneously, the electron transfer layer, electron injecting layer or carries out electronics biography simultaneously Defeated and injection layer includes the heterocyclic compound.

10. organic illuminating element according to claim 7, wherein the organic matter layer includes luminescent layer, the luminescent layer Include the heterocyclic compound.