CN104418828A

CN104418828A - hole transporting material

Info

Publication number: CN104418828A
Application number: CN201410438855.2A
Authority: CN
Inventors: 深川弘彦; 清水贵央; 高桥纯平; 新内聡畅; 土屋和彦
Original assignee: Kanto Chemical Co Inc
Current assignee: Kanto Chemical Co Inc
Priority date: 2013-08-30
Filing date: 2014-08-29
Publication date: 2015-03-18
Also published as: TW201514160A; JP6348380B2; JP2015205860A; KR20150026960A

Abstract

The invention provides a new compound which is large in band gap and good in electrical stability and thermal stability, and can be used for a hole transporting layer of an organic EL element, and also provides an organic EL element which comprises a hole transporting layer containing the new compound, and is long in service life and high in luminous efficiency. The compound is shown in the general formula (1). In the general formula (1), R1-R4 are respectively and independently selected from hydrogen, alkyl with substituents and a halogen group, the R1-R4 are respectively independent, and one or more of the R1-R4 can exist, if more of the R1-R4 exist, the R1-R4 can be same or different groups, X1 and X2 respectively and independently represent aromatic nucleus groups which can be provided with substituents, Z1 and Z2 respectively and independently represent O or S, and n is an integer in a range from 1 to 8.

Description

Hole mobile material

Technical field

The present invention relates to the providing of novel material, novel material the application as organic EL hole mobile material and use the organic El device of novel material.

Background technology

Organic electroluminescent is (following, be denoted as organic EL) element owing to having emissive type, visual angle is wide, identification good, low voltage drive, face are luminous, can slimming and lightweight, can the feature such as multicolor displaying, therefore can be used as indicating meter and illumination uses.

Organic EL is usually stacked according to the position relationship of anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode over the transparent substrate and form.

The luminescence of organic EL produces through following process: (I) hole and electronics are injected into from electrode, (II) transmits institute's injected holes and electronics, (III) hole and electronics compound in luminescent layer, (IV) luminescent material forms excited electronic state, and (V) is from excited electronic state radiation bright dipping.

When luminescent material obtains energy and forms excited state, singlet excited (S ₁) and triplet excited state (T ₁) generate with the ratio of 1:3.

When returning to ground state from excited state, energy discharges in the form of light and produces luminescence.Fluorescent material is only from S ₁conversion of energy be light, and from T in phosphor material ₁energy be also converted into light, therefore compared with fluorescent material being used for the situation of element, situation phosphor material being used for element more can expect high efficiency (non-patent literature 1, non-patent literature 2).

At this, the method use that phosphor material is contained in material of main part to make it.From hole and electronics compound the luminescent layer formed by material of main part and luminescent material of electrode injection, the energy trasfer of the material of main part be excited is to luminescent material, luminescent material, by this energy excitation, discharges with the form of luminous energy, thus can realize efficient luminescence.

In order to realize the efficient energy trasfer of autonomous agent material to phosphor material (guest materials), be better the T of main body ₁energy is greater than the T of the phosphor material as object ₁energy (non-patent literature 3).The T of guest materials ₁when energy is larger, usually occurs to shift to the backward energy of main body from object, the high efficiency of phosphorescence luminescence may be hindered.

Report so far in a large number for the material of main part of luminescent layer, can exemplify (non-patent literatures 4) such as such as carbazole compounds.Carbazole compound has larger T ₁energy, CBP etc. can be preferably used as material of main part (non-patent literature 5).But, the T of guest materials ₁when energy is large, even if also may be raised the efficiency by CBP.So, sometimes adopt and make T ₁the CDBP (non-patent literature 3) that energy is larger.

In order to improve the composite efficiency of one of the factor of the external quantum efficiency as organic EL, needing the transmission adjusting hole and electronics to balance, making institute's injected holes and electronics compound efficiently in luminescent layer.

In order to the transmission adjusting hole and electronics balances, must consider that balance is raised on the basis of the multiple factors such as hole-injecting material, the hole mobility of hole mobile material and the thickness of electron injection material, the electronic mobility of electron transport material, the charge injection potential barrier of bed interface and each film.

But the transporting of the hole that material itself has and electronics is different according to material, and at the interface of the layer formed with different materials, generation charge injection potential barrier, therefore hole and electronics not easily compound evenly in luminescent layer.As the situation of charge injection, transmission balanced differences, the extreme many and not compound situation etc. of just passing of situation that a side in hole or electronics is few, a side can be considered, but when electric charge flows out to reference electrode, the layer of block charge is set in addition, electric charge is stayed in luminescent layer, improve the method for composite efficiency.Usually, the electric charge flowed out is stopped and being stayed by electric charge in luminescent layer of task is born by hole transmission layer and electron transfer layer mostly.

To the characteristic required by the hole mobile material of the composite efficiency for improving organic EL except hole transport ability is high, electron-transporting low except, importantly the value of band gap and ionizing potential (IP), electron affinity energy (Ea) has suitable value.Ionizing potential it is desirable to the work function of anode or the value between the ionizing potential of hole-injecting material and the ionizing potential of luminescent material, can reduce the hole injection barrier to luminescent layer thus.

Electron affinity energy it is desirable to larger than the electron affinity energy of luminescent material, can obtain electronic blocking effect thus.Sometimes the HOMO energy level with the ionizing potential (IP) of one of the index as charge injection synonym is substantially adopted, with the lumo energy of electron affinity energy (Ea) synonym substantially.

The general material being used as anode is tin indium oxide (ITO), and work function is 4.8 ~ 5.0eV.Such as, if the ionizing potential of luminescent material or material of main part is 5.6eV, then in order to reduce hole injection barrier, be better that the hole mobile material of about 5.1 ~ 5.5eV is used for hole transmission layer.

In addition, in order to alleviate hole injection barrier, can hole injection layer be set.If therefore the ionizing potential change of luminescent material or material of main part, then also change the value of the ionizing potential required by hole mobile material.

As hole mobile material, known α-NPD, TPD, m-MTDATA, 3DTAPBP (being expressed as 3BTPD in some document) etc. are primarily of tertiary amine and the material be combined to form of phenyl and the compound of dibenzothiophene class etc. (non-patent literature 4, non-patent literature 5, non-patent literature 6, non-patent literature 7, patent documentation 1).In addition, report by changing hole mobile material, the external quantum efficiency of organic EL, the example (non-patent literature 8) of component life change.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent spy table 2011-527122 publication

Non-patent literature

Non-patent literature 1: " nature (Nature) ", 395,151 (1998)

Non-patent literature 2: " nature (Nature) ", 403,750 (2000)

Non-patent literature 3:Appl.Phys.Lett., 83,569 (2003)

Non-patent literature 4:Appl.Phys.Lett., 69,2160 (1996)

Non-patent literature 5: monthly magazine indicating meter other volume (month Inter ディスプレイ Do Books) " OLED display ", 51 pages (1998)

Non-patent literature 6:Appl.Phys.Lett., 55,1489 (1989)

Non-patent literature 7:J.Light & vis.Env.Mol.32, No.2,2008,75

Non-patent literature 8:Appl.Phys.Lett., 103,143306 (2013)

The summary of invention

Invent technical problem to be solved

The present invention is to provide new compound for problem.In addition, to provide, band gap is large, electric stability and good thermal stability, also can be used for the compound of hole transmission layer of organic EL for problem.

In addition, with long lifetime of possessing the hole transmission layer comprising above-claimed cpd is provided and the high organic EL of luminous efficiency for problem.

The technical scheme that technical solution problem adopts

Invention has been various discussion, result successfully synthesizes the new compound represented with shown general formula (1) below, also find that this compound is very useful as the hole mobile material of organic EL, such as hole transmission layer, the high efficiency of organic EL, long lifetime can be realized, thus complete the present invention.

That is, the present invention relates to following content.

[1] with formula (1)

[changing 1]

The compound represented;

In formula,

R ¹~ R ⁴independently for being selected from hydrogen, the group of substituent alkyl and halogen radical can being had,

R ¹~ R ⁴independently can exist one or more, when existing multiple, can be identical or different group,

X ¹and X ²independently for substituent fragrant ring type group can be had,

Z ¹and Z ²be independently O or S,

N is the integer of 1 ~ 8.

[2] compound as described in [1], wherein, R ¹~ R ⁴for hydrogen.

[3] compound as described in [1] or [2], wherein, n is 2.

[4] compound as described in any one in [1] ~ [3], wherein, X ¹and X ²for substituent phenyl can be had.

[5] compound as described in any one in [1] ~ [4], wherein, this compound is with formula (1-I)

[changing 2]

Represent.

[6] compound as described in [5], wherein, the binding site of nitrogen is 4 of dibenzothiophene.

[7] compound as described in [5], wherein, the binding site of nitrogen is 2 of dibenzothiophene.

[8] compound as described in any one in [1] ~ [4], wherein, this compound is with formula (1-II)

[changing 3]

Represent.

[9] compound as described in [8], wherein, the binding site of nitrogen is 4 of diphenylene-oxide.

[10] compound as described in [8], wherein, the binding site of nitrogen is 2 of diphenylene-oxide.

[11] compound as described in [5], wherein, this compound with chemical formula (1-I a),

[changing 4]

Chemical formula (1-I b),

[changing 5]

Chemical formula (1-I c),

[changing 6]

Or

(1-I d) for chemical formula

[changing 7]

Represent.

[12] compound as described in [8], wherein, this compound with chemical formula (1-II a),

[changing 8]

Chemical formula (1-II b),

[changing 9]

Chemical formula (1-II c),

[changing 10]

Or

(1-II d) for chemical formula

[changing 11]

Represent.

[13] method of the compound described in any one in [1] ~ [12] is manufactured, wherein,

Comprise in order to general formula (2)

[changing 12]

Represent compound or its salt with

With general formula (3)

[changing 13]

The compound represented carries out the operation of N-arylation reaction;

In formula (2),

R independently represents the R with [1] ¹~ R ⁴same implication,

X represents the X with [1] ¹and X ²same implication,

Z represents the Z with [1] ¹and Z ²same implication;

In formula (3),

N represents the implication same with [1],

HAL is halogen radical.

[14] organic electroluminescent device, it be comprise anode, negative electrode and between this two electrode with the organic electroluminescent device of layer that organic compound is formed, it is characterized in that,

The described layer formed with organic compound comprises the compound described in any one in [1] ~ [12].

[15] organic electroluminescent device, it comprises anode, negative electrode and the organic electroluminescent device at this two interelectrode charge transfer material, it is characterized in that,

Described charge transfer material comprises the compound described in any one in [1] ~ [12].

[16] organic electroluminescent device, it comprises anode, negative electrode and the organic electroluminescent device at this two interelectrode hole transmission layer, it is characterized in that,

Described hole transmission layer comprises the compound described in any one in [1] ~ [12].

[17] organic electroluminescent device, it comprises anode, negative electrode and the organic electroluminescent device at this two interelectrode luminescent layer, hole transmission layer, it is characterized in that,

The guest materials that described luminescent layer comprises material of main part and formed by luminescent material,

Described material of main part is two charge-transporting materials in electron transporting material or electronics and hole,

[18] organic electroluminescent device as described in [17], is characterized in that, luminescent material is phosphor material.

The effect of invention

By the present invention, new compound can be provided.In addition, also can provide that band gap is large, electric stability and good thermal stability, also can be used for the compound of the hole transmission layer of organic EL.

In addition, the long lifetime possessing the hole transmission layer comprising above-claimed cpd can also be provided and the high organic EL of luminous efficiency.

Compound of the present invention has the reason of characteristic as above and unclear, but according to the investigation of contriver, thinks that adjacent phenylene skeleton destroys the planarity of the centre portions of compound, expand the band gap of compound of the present invention, be conducive to increasing T simultaneously ₁energy, so bending skeleton may make electrical specification worsen on the contrary.Be not limited only to this, compound surprisingly of the present invention, by having adjacent phenylene skeleton and ADP thiophthene skeleton, ADP furans skeleton or ADP thiophthene skeleton and ADP and both furans skeletons, unexpectedly has high T ₁energy, and electric stability and good thermal stability, also possess suitable HOMO, lumo energy, charge transport ability.This can think by adjacent phenylene skeleton and ADP thiophthene skeleton or ADP and furans skeleton combines and produces Overlay.

Compound of the present invention possesses above-mentioned performance, particularly can well for the hole injection layer of organic EL.That is, suitable HOMO energy level alleviates the hole injection barrier of anode or hole injection layer and hole transmission layer, also can alleviate the hole injection barrier to luminescent layer from hole transmission layer.In addition, suitable lumo energy prevention is flowed out to reference electrode at the excess electron of the non-compound of luminescent layer from the negative electrode injected electrons of organic EL, can promote hole and electronics compound in luminescent layer.Thus, the composite efficiency of hole and electronics improves, and can obtain the effect that the external quantum efficiency of organic EL is improved.In addition, the electric stability of compound of the present invention, thermostability are considered to the long lifetime being conducive to element.Therefore, by the present invention, can provide and have high external quantum efficiency and long-life organic EL concurrently.

The mode carried out an invention

The present invention relates to

With general formula (1)

[changing 14]

The compound represented;

In formula,

X ¹and X ²independently for substituent fragrant ring type group can be had,

N is the integer of 1 ~ 8.

R in general formula (1) ¹~ R ⁴be independently hydrogen, substituent alkyl or halogen radical can be had.As the substituting group can with substituent alkyl, such as alkyl, alkoxyl group, halogen radical etc. can be exemplified, but be not limited in this.

R ¹~ R ⁴in the substituent alkyl that has can be straight-chain or ring-type.The viewpoints such as film-forming properties when making from the solvability to general organic solvent, organic EL, the alkyl of straight-chain is better carbon number 1 ~ 18, from the viewpoint such as second-order transition temperature, steric hindrance, is more preferably carbon number 1 ~ 6.The alkyl of the straight-chain of carbon number 1 ~ 18 refers to methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl.

The alkyl of ring-type is better carbon number 3 ~ 18, from the viewpoint such as second-order transition temperature, steric hindrance, is more preferably carbon number 3 ~ 8.The alkyl of ring-type can exemplify the cycloalkyl such as such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl, ring undecyl, cyclo-dodecyl, ring tridecyl, ring tetradecyl, ring heptadecyl, cyclohexyl, or the multi-ring alkyl such as bicyclic alkyl, tricyclic alkyl.

R ¹~ R ⁴in the substituting group with substituent alkyl can replace more than 2, respectively can be different.

For the alkyl selected as the substituting group can with substituent alkyl, the viewpoints such as film-forming properties when making from the solvability to general organic solvent, organic EL, be better the alkyl as main chain and the total carbon number as its substituent alkyl be 1 ~ 18, from the viewpoint such as second-order transition temperature, steric hindrance, being more preferably and amounting to carbon number is 1 ~ 6.

As can have substituent alkyl substituting group select alkyl when, as having substituent alkyl, such as 1-methylethyl can be exemplified, 1-methyl-propyl, 1-ethyl propyl, 1-n-propyl propyl group, 1-methyl butyl, 1-ethyl-butyl, 1-butyl, 1-normal-butyl butyl, 1-methyl amyl, 1-ethyl pentyl group, 1-n-propyl amyl group, 1-n-pentyl amyl group, 1-methylhexyl, 1-ethylhexyl, 1-n-propyl hexyl, 1-normal-butyl hexyl, 1-n-pentyl hexyl, 1-n-hexyl hexyl, 1-methylheptyl, 1-ethylheptyl, 1-n-propyl heptyl, 1-normal-butyl heptyl, 1-n-pentyl heptyl, 1-n-heptyl heptyl,

1-Methyl Octyl, 1-ethyloctanyl, 1-n-propyl octyl group, 1-normal-butyl octyl group, 1-n-pentyl octyl group, 1-n-hexyl octyl group, 1-n-heptyl octyl group, 1-n-octyl octyl group, 1-Nonyl, 1-ethylnonanyl, 1-n-propyl nonyl, 1-normal-butyl nonyl, 1-n-pentyl nonyl, 1-n-hexyl nonyl, 1-n-heptyl nonyl, 1-n-octyl nonyl, 1-n-nonyl nonyl, 1-methyldecyl, sec.-propyl, the tertiary butyl, 2-methyl butyl, 2-ethyl-butyl,

2-n-propyl amyl group, 2-methylhexyl, 2-ethylhexyl, 2-n-propyl hexyl, 2-normal-butyl hexyl, 2-methylheptyl, 2-ethylheptyl, 2-n-propyl heptyl, 2-normal-butyl heptyl, 2-n-pentyl heptyl, 2-Methyl Octyl, 2-ethyloctanyl, 2-n-propyl octyl group, 2-normal-butyl octyl group, 2-n-pentyl octyl group, 2-n-hexyl octyl group, 2-Nonyl, 2-ethylnonanyl, 2-n-propyl nonyl, 2-normal-butyl nonyl, 2-n-pentyl nonyl, 2-n-hexyl nonyl, 2-n-heptyl nonyl,

2-methyldecyl, 2,3-dimethylbutyls, 2,3,3-trimethyl butyl, 3-methyl butyl, 3-methyl amyl, 3-ethyl pentyl group, 4-methyl amyl, 4-ethylhexyl, 2,3-dimethyl amyl groups, 2,4-dimethyl amyl groups, 2,4,4-tri-methyl-amyl, 2,3,3,4-tetramethyl-amyl group, 3-methylhexyl, 2,5-dimethylhexanyl, 3-ethylhexyl, 3,5,5-trimethyl, 4-methylhexyl, 6-methylheptyl, 3,7-dimethyl octyl groups, 6-Methyl Octyl etc.

For the alkoxyl group selected as the substituting group can with substituent alkyl, the viewpoints such as film-forming properties when making from the solvability to general organic solvent, organic EL, be better alkyl and be 1 ~ 18 as the total carbon number of its substituent alkoxyl group, from the viewpoint such as second-order transition temperature, steric hindrance, being more preferably and amounting to carbon number is 1 ~ 6.

The halogen radical selected as the substituting group can with substituent alkyl can exemplify fluorine-based, chloro, bromo, iodo, from the viewpoint of electric stability, thermostability, synthesis difficulty, is better wherein fluorine-based.

As R ¹~ R ⁴in halogen radical, be better fluorine-based.

As mentioned above, R ¹~ R ⁴select hydrogen, alkyl or halogen radical, if but the judgements such as the difficulty of Universal electric stability, thermostability, film-forming properties, synthesis and purifying, preferably hydrogen or methyl.In addition, when selecting methyl, consider that then electric stability increases, so preferably if be replaced in 2 and/or 4 of the reflecting point as dibenzothiophene and diphenylene-oxide.

Dibenzothiophene and diphenylene-oxide are axisymmetric structure, so when representing the binding site of dibenzothiophene and the binding site of the position of substitution and diphenylene-oxide and the position of substitution, dibenzothiophene and diphenylene-oxide separately 1 with 9,2 with 8,3 with 7 and 4 of equal value respectively with 6.Therefore, such as " be replaced in 2 of dibenzothiophene " and conceptually also comprise " being replaced in 8 of dibenzothiophene " and " being replaced in 2 and 8 of dibenzothiophene ".Similarly, such as " be replaced in 2 of diphenylene-oxide " and conceptually also comprise " being replaced in 8 of diphenylene-oxide " and " being replaced in 2 and 8 of diphenylene-oxide ".

The X of general formula (1) ¹and X ²select from the viewpoint of the effect of the electronics effect such as HOMO energy level, lumo energy, band gap of compound and the physical property such as fusing point, second-order transition temperature effect and steric hindrance.Therefore, as with X ¹and X ²what represent has substituent fragrant ring type group, can exemplify the aromatic heterocycle of the aromatic hydrocarbyl of carbon number 6 ~ 30, carbon number 1 ~ 30.

At this, as with X ¹and X ²the aromatic hydrocarbyl of the carbon number 6 ~ 30 represented, the aromatic cyclic hydrocarbon group of 6 π-electron systems, 10 π-electron systems, 12 π-electron systems, 14 π-electron systems can be exemplified, specifically can exemplified by phenyl, xenyl, naphthyl, terphenyl, anthryl, Azulene base, fluorenyl, pyrenyl, phenanthryl, naphthacenyl (Japanese: Na Off スリ Le) etc., from the viewpoint obtaining suitable electronics effect, wherein particularly preferably phenyl, naphthyl, xenyl.

In addition, when xenyl, if part corresponding to the ortho position that in this xenyl, phenyl be combined with each other imports the alkyl such as methyl, biphenyl backbone bends because of steric hindrance, can suppress the expansion of pi-conjugated system, obtains suitable electronics effect, therefore particularly preferably 2,2 '-dimethyl-1,1 '-biphenyl.

As with X ¹and X ²the aromatic heterocycle represented, specifically thienyl can be exemplified, furyl, pyrryl, thiazolyl, isothiazolyl, pyrazolyl, oxazolyl, isoxazolyl, pyridyl, pyridazinyl, oxadiazolyl, imidazolyl, triazinyl, thiadiazolyl group, benzothiazolyl, benzimidazolyl-, benzoxazolyl, Ben Bing oxadiazolyl, benzotriazole base, diazosulfide base, selenole base, thieno-[2, 3-b] thienyl, thieno-[3, 2-b] thienyl, thieno-[3, 4-b] thienyl, 9-oxo fluorenyl, carbazyl, dibenzo thiophenyl, silicon fluorenyl, selenium fluorenyl, xanthenyl, phenanthroline base, phenazinyl, phenoxazinyl (Japanese: Off ェニキサジリ Le) etc.From the viewpoint obtaining suitable electronics effect, wherein particularly preferably dibenzo thiophenyl or dibenzofuran group etc.

The substituting group can with substituent fragrant ring type group can replace more than 2, can distinguish difference.

As the substituting group can with substituent fragrant ring type group, the alkyl of straight chain or branch or ring-type, halogen radical, amino, nitro, cyano group can be exemplified.In addition, as alkyl, from the viewpoint that can obtain suitable stereoeffect, be better methyl, ethyl, propyl group, sec.-propyl etc.In addition, as halogen, from the viewpoint of synthesis difficulty, be better fluorine-based.

The phenyl at two ends of adjacent phenylene in connection general formula (1) and the binding site of the adjacent phenylene side of the nitrogen of dibenzothiophene can optional positions.

The phenyl at two ends of adjacent phenylene in connection general formula (1) and the binding site of the adjacent phenylene side of the nitrogen of diphenylene-oxide can optional positions.

The binding site of the diphenylene-oxide side of the binding site connecting the dibenzothiophene in general formula (1) and the diphenylene-oxide side of the nitrogen of adjacent phenylene and the nitrogen being connected diphenylene-oxide and adjacent phenylene can be optional position, from the viewpoint of the difficulty of synthesis, it is better 2 or 4 of dibenzothiophene and diphenylene-oxide.

Be present in phenyl position close to each other as the adjacent phenylene of center framework in general formula (1), therefore phenyl is difficult to be arranged in same plane.Therefore, the planarity collapse at molecular structure center, can form wide bandgap.Therefore, the quantity of adjacent phenylene is not particularly limited in principle, but uses vacuum vapour deposition to make the viewpoint of compound subliming when making from element, and the numeral of n is better 1 ~ 8, from the viewpoint of the suitable electronics effect such as dibenzothiophene and diphenylene-oxide, be more preferably 1 ~ 4.

In this specification sheets, R in structure ¹~ R ⁴illustrate 1 respectively, but this expression can be multiple, when having multiple, respectively can be identical or different.Such as, R ¹can exist one or more, there is multiple R ¹when, the plurality of R ¹can be identical or different.For R ²~ R ⁴too.

Z is passed through with the compound that general formula (1) represents ¹or Z ²for S or Z ¹and Z ²be S simultaneously, can dibenzothiophene be had.

Z is passed through with the compound that general formula (1) represents ¹or Z ²for O or Z ¹and Z ²be O simultaneously, can diphenylene-oxide be had.

The compound represented with general formula (1) can have dibenzothiophene and diphenylene-oxide simultaneously.

From the viewpoint of synthesis difficulty, in the compound represented with general formula (1), be better with general formula (1-I)

[changing 15]

With general formula (1-II)

[changing 16]

The compound represented.

X is comprised as in general formula (1) ¹, X ²the general formula of concrete form, such as following compound can be exemplified.

[changing 17]

As the compound in general formula (1) during n=1 ~ 8, following compound can be exemplified.

[changing 18]

In general formula (1) when such as n=2, as the position of nitrogen being connected to the adjacent phenylene of center framework, following example can be exemplified.

[changing 19]

Z is comprised as in general formula (1) ¹and Z ²heterocycle, the position of nitrogen that is namely connected with dibenzothiophene or diphenylene-oxide, following example can be exemplified.

[changing 20]

As in general formula (1) when such as n=2, as comprising Z ¹and Z ²heterocycle, the replacement position of nitrogen that is namely connected with dibenzothiophene or diphenylene-oxide, following example can be exemplified.

[changing 21]

In addition, as the object lesson of compound of the present invention, such as following compound can be exemplified.

[changing 22]

[changing 23]

[changing 24]

[changing 25]

[changing 26]

[changing 27]

In the present invention, from viewpoints such as charge injection and transport property, electric stability and thermostabilitys, as the example of particularly preferred compound, can exemplify with following chemical formula (1-I a) ~ (1-I d) and (1-II a) ~ (compound that 1-II d) represents.

[changing 28]

[changing 29]

[changing 30]

[changing 31]

[changing 32]

[changing 33]

[changing 34]

[changing 35]

Organic EL Material needs thermotolerance, and one of its index is second-order transition temperature (Tg).When the Tg of material is low, even if at ambient temperature, if through long-time, also may crystallization and become uneven film, charge transmission etc. is had an impact.Therefore, the Tg of organic EL Material is more high better.The Tg of the α-NPD be widely used as hole mobile material is low to moderate 95 DEG C.In addition, the Tg of TPD, m-MTDATA, 3DTAPBP is also respectively 60 DEG C, 75 DEG C, 75 DEG C, is considered to all lower.In contrast, compound of the present invention is better have the Tg of more than 100 DEG C.

Compound of the present invention has described characteristic, is particularly suitable for the hole transmission layer of organic EL, can make organic EL high efficiency, long lifetime.

Particularly compound of the present invention is used for hole transmission layer and by T ₁its lower green ~ red illuminating material of energy Ratios is used for, in the organic EL of luminescent layer, can preventing self-luminescent material from moving to the backward energy of hole mobile material, therefore combining efficient rate and extremely long driving life-span.Such as, can exemplify based on the compound represented with chemical formula (1) and Ir (ppy) ₃deng the organic EL of combination.

(synthesis for compound)

Compound of the present invention is such as by the method synthesis shown in following reaction formula.

[changing 36]

Namely, such as, by ADP thiophthene derivative or ADP benzofuran derivs, the compound or its salt represented with general formula (2) and the adjacent crystalline 1,2-phenylene derivatives (skeleton) of halo, the N-arylation reaction of compound that such as represents with general formula (3), synthesize compound of the present invention.

In this specification sheets, unless otherwise specified, R represents and R ¹~ R ⁴same implication, when existing multiple, independently represents and described R ¹~ R ⁴same implication.

Unless otherwise specified, X represents and X ¹and X ²same implication, when existing multiple, independently represents and X ¹and X ²same implication.

Unless otherwise specified, Z represents and Z ¹and Z ²same implication, when existing multiple, independently represents and Z ¹and Z ²same implication.

ADP thiophthene derivative or ADP benzofuran derivs, the representative synthetic method of compound that such as represents with following general formula (2a) are described.

[changing 37]

The compound represented with general formula (2a) as shown in following reaction formula with halogenating reaction halogenation is carried out to dibenzothiophene, diphenylene-oxide or their derivative, then carry out the halogenation dibenzothiophene that represents with following general formula (4) or halogenation dibenzofuran derivative and the N-arylation reaction with amino aromatic hydrocarbon represented with following general formula (5) and synthesize.

[changing 38]

Halogenating reaction such as has makes the halogen such as bromine, the iodine method of direct reaction and the method for use halogenating agent in the presence of a catalyst.Halogenating agent has chlorizating agent, bromizating agent, iodinating agent.As chlorizating agent, such as N-chlorosuccinimide (NCS) etc. can be exemplified; As bromizating agent, such as N-bromo-succinimide (NBS), dibromo isocyanuric acid (DBI) etc. can be exemplified; As iodinating agent, such as N-N-iodosuccinimide (NIS), 1,3-bis-iodo-5 can be exemplified, 5 '-T10 (DIH) etc.

The halogenation dibenzothiophene that the position of substitution of halogen is different or halogenation diphenylene-oxide such as synthesize by method shown below.

In order to obtain 4 compounds be halogenated of halogenation dibenzothiophene or halogenation diphenylene-oxide, the such as method shown in following reaction formula can be exemplified.

[changing 39]

That is, the dihalide ethane such as 1,2-ethylene dichloride, glycol dibromide or 1,2-ethylidene periodide can be used, halogenation is carried out to the carbon of anionization, by the method, preferentially can carry out halogenation to 4 of dibenzothiophene or diphenylene-oxide.

In order to obtain 2 compounds be halogenated of dibenzothiophene or diphenylene-oxide, the such as method shown in following reaction formula can be exemplified.

[changing 40]

Such as, by making to react as a kind of NBS of halogenating agent and dibenzothiophene or diphenylene-oxide, 2 of dibenzothiophene or diphenylene-oxide by preferential halogenation.By adjusting the amount of halogenating agent, the halogen radical of more than 2 also can be introduced.

In addition, if use application examples as J.Org.Chem., 2006,71, the method shown in following reaction formula of method described in 6291, then can synthesize 1 dibenzothiophene or diphenylene-oxide or its derivative be halogenated.

[changing 41]

In addition, if use application examples as Tetrahedron, 2002,58, the method etc. shown in following reaction formula of method described in 1709, then can synthesize 3 dibenzothiophene or diphenylene-oxide or its derivative be halogenated.

[changing 42]

Then, as shown in following reaction formula, for halogenation dibenzothiophene or halogenation diphenylene-oxide with introduce amino fragrant ring type group, carry out application examples such as Buchwald-Hartwig to react (such as, Org.Synth., 2002,78,23), Ullmann reaction (such as, Angew.Chem., Int.Ed.2003,42,5400) N-arylation reaction etc., thus the compound represented with above-mentioned general formula (2a) can be synthesized.

[changing 43]

As shown in following reaction formula, use and introduce amino dibenzothiophene or the fragrant ring type group of dibenzofuran derivative and halogenation, carry out N-arylation, also can synthesize the compound of above-mentioned general formula (2a) equally.

[changing 44]

As shown in following reaction formula, if the dibenzothiophene using arbitrary position to be halogenated or diphenylene-oxide and such as alkyl Grignard reagent etc., alkyl etc. can be introduced to dibenzothiophene or diphenylene-oxide.

[changing 45]

As shown in following reaction formula, if use Suzuki linked reaction (such as Chem.Rev., 1995,95,2457) etc., also can introduce fragrant ring type group to dibenzothiophene or diphenylene-oxide.In addition, boric acid derivatives can be R ^afor the arbitrary boric acid derivatives that hydrogen, methyl, sec.-propyl etc. are selected as required.

[changing 46]

The substituent R represented with following general formula (2b) is not for ADP thiophthene derivative during H or ADP benzofuran derivs synthesize by applying above-mentioned reaction yet.

Such as, by the method shown in following reaction formula, the compound with substituent R represented with following general formula (2b) can be synthesized.

[changing 47]

The adjacent crystalline 1,2-phenylene derivatives of halogenation, the synthesis of compound that such as represents with following general formula (3) are described.

[changing 48]

The adjacent phenylene skeleton of n=1 such as synthesizes by following method.

[changing 49]

In addition, if use 1-bromo-3-chlorobenzene or 1-bromo-4-chlorobenzene to replace the bromo-2-chlorobenzene of 1-of initial substance, then the compound that the position of the chlorine introducing adjacent phenylene is different can also be synthesized.

The adjacent phenylene skeleton of n=2 such as synthesizes by following method.

[changing 50]

In addition, as described above, if change initial substance, the compound that the position of the chlorine introducing adjacent phenylene is different can be synthesized.

In addition, by carrying out following reaction, the compound that adjacent phenylene introduces bromine can be synthesized, by method similar to the above, also the binding site of synthetic bromide can also be introduced into the compound of optional position.

[changing 51]

In addition, the chemical formula (3b) that the position of the halogen of adjacent phenylene end is different or the compound shown in (3c) are by the method synthesis shown in following reaction formula.

[changing 52]

[changing 53]

The adjacent phenylene skeleton of n=3 such as synthesizes by following method.

[changing 54]

The adjacent phenylene skeleton of n=4 such as synthesizes by following method.

[changing 55]

The adjacent phenylene skeleton of n=5 such as synthesizes by following method.

[changing 56]

The adjacent phenylene skeleton of n=6 such as synthesizes by following method.

[changing 57]

By the N-arylation reaction of the adjacent phenylene and ADP benzofuran derivs that carry out halogenation, compound of the present invention can be synthesized.

[changing 58]

Here the synthesis method shown in is only example, is not limited in this.

(for evaluation of physical property)

The measurement example of the purity of compound is as undertaken by high performance liquid chromatography (HPLC) etc.High performance liquid chromatography applies pressure to the moving phase importing sample, and solvent is passed into moving phase with high flow rate, with post separating sample (mixture), detects the sample be separated with detector, thus measure the method for the purity of sample.

Post can use positive class, anti-phase class.Positive class chromatography refers to the separation system that the polarity of stationary phase is higher than the polarity of moving phase, and stationary phase adopts aluminum oxide etc., and moving phase adopts the solvent that hexane isopolarity is little.Anti-phase class chromatography refers to the separation system that the polarity of moving phase is higher than the polarity of stationary phase, and stationary phase adopts the silicon-dioxide etc. through hydrophobic treatment, and moving phase adopts methyl alcohol and acetonitrile polar solvent.

Detector can use various equipment according to the physical property of sample.Such as, absorption photometric detector (UV/VIS), fluorimetric detector (FLD), mass spectrometer (MS) etc. can be exemplified.

The mensuration of the molecular weight of compound is undertaken by mass spectrometry (MS).Mass spectroscopy is carried out as follows: apply high-voltage in a vacuum to the sample imported from sample introduction part, thus by sample ion, be separated by ion according to specific charge, detected by test section.

Sample introduction part directly can be connected with gas chromatograph (GC/MS), high performance liquid chromatograph (LC/MS), capillary electrophoresis (CE/MS), while mensuration MS, also can carry out the mensuration of purity.Sometimes also adopt the direct injection of sample direct ion (direct injection) mode (DI/MS).

Ion source adopts various Ionized mode.Such as, electron ionization method (EI), Fast atom impingement method (FAB), electro-spray ionization method (ESI), inductively coupled plasma method (ICP) etc. can be exemplified.

The qualification of compound can use nuclear magnetic resonance spectrum (NMR).

During NMR measures, according to the bonding state etc. of atom, the information of chemical shiftsum coupling can be understood, therefore can obtain the intrinsic collection of illustrative plates of compound, authenticating compound.Measure by a small amount of sample dissolution is carried out in various deuterated solvent.

The evaluation of the thermostability of compound measures (DSC) by means of differential scanning calorimetry and carries out.DSC measures and carries out with the heat difference of standard test specimen by detecting when thermal distortion such as sample generation phase transition and meltings.By DSC, fusing point and the second-order transition temperature of compound can be understood.

By measuring ultraviolet-visible absorption spectroscopy (UV/VIS), fluorescence spectrum (PL), the phosphorescence spectrum of compound, not only can understand the distinctive UV absorbing wavelength of compound, wavelength of fluorescence, phosphorescent wavelength, also can understand the band gap of compound, fluorescent quantum yield, T ₁the information such as energy.

HOMO energy level, the lumo energy of compound measure by cyclic voltammetry (CV).In addition, as the concept same with HOMO energy level, ionizing potential (IP) also can be adopted to measure, and IP is measured by photoelectric spectrophotometry.

In addition, also can use and obtain optical band gap according to UV absorbing wavelength, calculate the method for lumo energy (or Ea) according to HOMO energy level (or IP).

(for organic EL)

The feature of organic EL of the present invention is, compound of the present invention is used for hole mobile material, such as hole transmission layer.

In general, organic EL is stacked and form according to the position relationship of anode, hole injection layer, hole transmission layer (electron blocking layer), luminescent layer, electron transfer layer (hole trapping layer), electron injecting layer, negative electrode on substrate.

Organic EL does not need all to be formed by organism, and electrode and hole injection layer, electron injecting layer etc. may adopt inorganic materials.

In addition, formed in the layer of organic EL, any one in hole injection layer, electron transfer layer, electron injecting layer is omitted sometimes.

Organic EL has from the bottom emitting type element of substrate-side taking-up light and the top emission type from the side contrary with substrate taking-up light, and organic EL of the present invention can adopt wherein any one mode.

Substrate material used also can be different according to top emission type element and bottom emitting type element.Bottom emitting type element adopts transparent substrate.On the other hand, top emission type not only can adopt transparent substrate, also can adopt opaque substrate.

Substrate material used can use the various glass such as silica glass, soda-lime glass, PYREX (registered trademark).In addition, also the various plastic bases such as polycarbonate, acrylic resin, polyethylene terephthalate can be used.In addition, also they can be combinationally used two or more.

In general, the anode of bottom emitting type element adopts transparent conductive material.

In addition, top emission type is not particularly limited, sometimes can uses reflexive electrode.The effect of anode is by hole injected hole input horizon or hole transmission layer.Therefore, the various metallic substance that anode employing work function is larger or various alloys etc. play the material of anodize.Such as, gold, copper(I) iodide, stannic oxide, Al-Doped ZnO (ZnO:Al), tin indium oxide (ITO), indium zinc oxide (IZO), fluorine doped tin oxide (FTO) etc. can be exemplified.Wherein, from viewpoint that is transparent and work function, be better ITO, IZO, FTO.

Material for hole injection layer is selected from the viewpoint such as relation, charge transmission of the IP of the work function of anode and hole transmission layer.Such as, can exemplify with the compound of following chemical formulation.Wherein, be better following poly-(3,4-ethene-dioxythiophene): poly-(styrene sulfonate) (PEDOT:PSS), following copper phthalocyanine (CuPc), molybdenum oxide (MoO _x), vanadium oxide (V ₂o ₅) etc., sometimes preferably use PEDOT:PSS.As long as have suitable IP and the compound of charge transmission, no matter be low molecule or polymer, various organic compound, mineral compound can be selected.In addition, but also two or more combinationally uses these materials.

[changing 59]

[changing 60]

Hole transmission layer can use compound of the present invention.This compound has the center framework of adjacent phenylene and ADP and furans skeleton, thus has wide bandgap, suitable HOMO energy level, lumo energy, electric stability, good thermal stability.Therefore, the composite efficiency of the electric charge in luminescent layer can be improved, with higher luminous efficiency, long-life organic EL can be realized, therefore preferably.

Luminous efficiency represents with external quantum efficiency, and the theoretic ultimate value of organic EL is different according to the specific refractory power of glass or organic membrane, but general element is about 20%, therefore more better close to 20%, if but guarantee that about 15% is just enough.

Compound of the present invention can be used alone, and also can mix one kind or two or more existing hole transport ability materials'use, also can be stacked more than 1 layer or 2 layers.As hole transport ability material, can exemplify such as with the compound of following chemical formulation.

[changing 61]

[changing 62]

[changing 63]

[changing 64]

Luminescent layer can use fluorescent material or phosphor material.For luminescent material, luminescent material (object) also can be made to be contained in the material of main part carrying out transferring charge and charge recombination and to use.

Material of main part can use the material of two charge-transportings with hole transport ability and electron-transporting.In addition, the electronic stopping performance of hole transport ability material of the present invention, therefore material of main part also can use the material of electron-transporting.

When as guest materials selection phosphor material, be better the T according to material of main part ₁energy is higher than the T of guest materials ₁the condition of energy selects material of main part.

As material of main part, can exemplify such as with the compound of following chemical formulation.

(material of main part)

[changing 65]

[changing 66]

For luminescent material, in order to effectively carry out the energy trasfer of autonomous agent material, be better that the emission wavelength of material of main part is overlapping with the absorbing wavelength of guest materials.In addition, when guest materials is phosphor material, be better the T of material of main part ₁energy is greater than the T of guest materials ₁energy.

Luminescent material is not particularly limited, and as fluorescent material, can exemplify such as with the compound of following chemical formulation.

(fluorescent material)

[changing 67]

[changing 68]

As phosphor material, can exemplify such as with the compound of following chemical formulation.

(phosphor material)

[changing 69]

[changing 70]

As the material for electron transfer layer, can exemplify such as with the compound of following chemical formulation.If arrange the electron transfer layer with suitable lumo energy between luminescent layer and negative electrode or electron injecting layer, then can alleviate the electron injection potential barrier to electron transfer layer from negative electrode or electron injecting layer, and alleviate from electron transfer layer to the electron injection potential barrier of luminescent layer.In addition, if this material has suitable HOMO energy level, then can stop in the non-compound of luminescent layer to the hole that reference electrode flows out, hole is closed in luminescent layer, improve the composite efficiency in luminescent layer.But electron injection potential barrier can not throw into question and in the sufficiently high situation of the electron transport ability of luminescent layer, sometimes also omit this layer.When compound of the present invention is used for hole transmission layer, sometimes also electron transport material can be used as material of main part.

[changing 71]

[changing 72]

[changing 73]

Material for electron injecting layer is selected from viewpoints such as the lumo energies of the work function of negative electrode and electron transfer layer.When not establishing electron transfer layer, consider that the lumo energy of luminescent material or material of main part described later is selected.Electron injection material can be organic compound, also can be mineral compound.

When electron injecting layer is formed by mineral compound, such as basic metal or alkaline-earth metal and lithium fluoride, Sodium Fluoride, Potassium monofluoride, cesium fluoride, cesium carbonate etc. can be used.

The negative electrode of organic EL bears the effect of injecting electronics to electron injecting layer or electron transfer layer.Negative electrode adopts work function less various technologic materials, various alloys etc. to play the material of the effect of negative electrode.Such as, aluminium, silver, magnesium, calcium, gold, tin indium oxide (ITO), indium zinc oxide (IZO), magnesium indium alloy (MgIn), silver alloys etc. can be exemplified.

When adopting bottom emitting mode, negative electrode can use the opaque electrode formed by metal.In addition, negative electrode also can adopt reflecting electrode.

When adopting top emitting mode, negative electrode can use the transparency electrode of ITO, IZO etc.At this, the work function of ITO is large, therefore electron injection difficulty, and in order to form ito film, adopting sputtering method or ion-beam evaporation, but may damage electron transfer layer etc. when film forming.So the destruction to electron transfer layer during in order to improve electron injection and reduce film forming, also can arrange magnesium layer or copper phthalocyanine layer between electron transfer layer and ITO.

Embodiment

Below, the present invention will be described in more detail with reference to embodiment, but this specific object lesson of the present invention that is example, the present invention is not limited to this.

Even if use identical material, when the element of organic EL forms different, external quantum efficiency and life-span also can be different values certainly.

In addition, when evaluating apparatus is different with evaluation environment, even if element forms identical, also different results may be obtained.

Based on such situation, the evaluation for the material of organic EL be better formed with identical element, identical evaluating apparatus, identical evaluation environment carry out.

[synthesis of compound]

Synthesis example 1

Synthesized with following chemical formula by synthesis path shown below that ((1-I a) for the compound that 1-I a) represents.

[changing 74]

The compound 2c-I represented with following chemical formula (2c-I) has been synthesized by method shown below.

[changing 75]

To possess stirrer through argon displacement 300mL Shu Lunke (Schlenk) pipe in add 4-bromine dibenzothiophene (13.16g, 50mmol), aniline (4.66g, 50mmol), acid chloride (225mg, 1.0mmol), toluene (150mL), tri-butyl phosphine (202mg, 1.0mmol) with potassium tert.-butoxide (5.61g, 50mmol), stir 7 hours at 100 DEG C after airtight.Then, let cool by reaction vessel near room temperature, uncap, add water (150mL) wherein.Content is moved to separating funnel, after making organic phase and aqueous phase separation, removes aqueous phase, then organic phase is washed.Organic phase with sodium sulfate is dry.Then, filter sodium sulfate by crossing, concentrated organic phase.By concentrated mixture silica gel column chromatography (developing solvent: the hexanes/ch=3/1) purifying obtained, obtain the above-claimed cpd 2c-I (receipts amount 10.7g, yield 77.8%) as target.

¹H-NMR、DMSO-d6、δ:6.85(t、J＝7.3Hz、1H)、6.98(d、J＝7.8Hz、8H)、7.23(t、J＝8.3Hz、2H)、7.32(d、J＝7.8Hz、1H)、7.45(t、J＝7.8Hz、1H)、7.50-7.53(m、2H)、8.01-8.03(m、2H)、8.17(s、1H)、8.33-8.35(m、1H)

The compound 3b represented with following chemical formula (3b) has been synthesized by method shown below.

[changing 76]

To possess stirrer through argon displacement 300mL four-hole boiling flask in add 2,2 '-'-dibromobiphenyl (7.50g, 24.0mmol) and diethyl ether (100mL), stir, be cooled to-15 DEG C.Drip 1.6M n-Butyl Lithium/hexane solution (30.0mL, 48.0mmol) wherein.Stir after 1 hour, add trimethyl borate (4.99g, 48mmol), removing cooling bath, stirs 18 hours from-15 DEG C while being warming up to room temperature.Successively add distilled water (50mL) on a small quantity, reaction is stopped, under reduced pressure remove diethyl ether and hexane.According to prolong, after again argon displacement being carried out to container, add distilled water (50mL), m-dibromobenzene (16.98g, 72mmol), tetrakis triphenylphosphine palladium (0.555g, 0.48mmol), salt of wormwood (6.634g, 48mmol) with toluene (100mL), reflux 5 hours.After being cooled to room temperature, content is moved to separating funnel, make organic phase and aqueous phase separation, remove aqueous phase, then organic phase is washed.Organic phase with sodium sulfate is dry.Then, filter sodium sulfate by crossing, concentrated organic phase.By the mixture of gained silica gel column chromatography (developing solvent: hexane) purifying, obtain the above-claimed cpd 3b (receipts amount 6.12g, yield 53.9%) as target.

¹H-NMR、CDCl ₃δ:6.85(t、J＝7.3Hz、6H)、6.89-7.00(m、8H)、7.08(d、J＝8.2Hz、4H)、7.22-7.00(m、4H)、7.31-7.45(m、8H)、7.7(d、J＝7.3Hz、2H)、7.98(d、J＝7.8Hz、2H)、8.13(d、J＝7.3Hz、2H)

Synthesized by method shown below with following chemical formula (compound 1-I a that 1-I a) represents.

[changing 77]

To possess stirrer through argon displacement 100mL Shu Lunke pipe in add compound 2c-I (N-phenyl dibenzo [b, d] thiophene-4-amine) (3.30g, 12.0mmol), compound 3b (3; 3 " '-two bromo-1,1 ': 2 '; 1 ": 2 "; 1 " '-quaterphenyl) (12.79g, 6.0mmol), acid chloride (27mg, 0.12mmol), toluene (50mL), tri-butyl phosphine (24mg, 0.12mmol) with potassium tert.-butoxide (1.35g, 12.0mmol), stir 7 hours at 100 DEG C after airtight.Then, let cool by reaction vessel near room temperature, uncap, add water (50mL) wherein.Content is moved to separating funnel, after making organic phase and aqueous phase separation, removes aqueous phase, then organic phase is washed.Organic phase with sodium sulfate is dry.Then, filter sodium sulfate by crossing, concentrated organic phase.By concentrated mixture silica gel column chromatography (developing solvent: the hexanes/ch=3/1) purifying obtained, obtain above-claimed cpd 1-I a (receipts amount 4.98g, yield 97.3%) as target.

¹H-NMR、CDCl ₃δ:6.23(t、J＝1.8Hz、2H)、6.53(d、J＝7.8Hz、2H)、6.60(d、J＝7.3Hz、4H)、6.74(d、J＝9.6Hz、2H)、6.88-6.92(m、6H)、7.00-7.13(m、12H)、7.38(t、J＝7.8Hz、2H)、743-7.50(m、4H)、7.84(d、J＝7.3Hz、2H)、8.15(d、J＝6.9Hz、2H)、8.33(d、J＝6.9Hz、2H)

Synthesis example 2

Synthesized by synthesis path shown below with following chemical formula (compound 1-I b that 1-I b) represents.

[changing 78]

The compound represented with following chemical formula (2d-I) has been synthesized by method shown below.

[changing 79]

To possess stirrer through argon displacement 300mL Shu Lunke (Schlenk) pipe in add 2-bromine dibenzothiophene (13.16g, 50mmol), aniline (4.66g, 50mmol), acid chloride (225mg, 1.0mmol), toluene (150mL), tri-butyl phosphine (202mg, 1.0mmol) with potassium tert.-butoxide (5.61g, 50mmol), stir 18 hours at 100 DEG C after airtight.Then, let cool by reaction vessel near room temperature, uncap, add water (150mL) wherein.Content is moved to separating funnel, after making organic phase and aqueous phase separation, removes aqueous phase, then organic phase is washed.Organic phase with sodium sulfate is dry.Then, filter sodium sulfate by crossing, concentrated organic phase.By concentrated mixture silica gel column chromatography (developing solvent: the hexanes/ch=3/1) purifying obtained, obtain the above-claimed cpd 2d-I (receipts amount 7.85g, yield 57.1%) as target.

Compound is identified with MS spectrum.

Synthesized by method shown below with following chemical formula (compound 1-I b that 1-I b) represents.

[changing 80]

To possess stirrer through argon displacement 100mL Shu Lunke pipe in add compound 2d-I (N-phenyl dibenzo [b, d] thiophene-2-amine) (1.58g, 6.0mmol), compound 3b (3; 3 " '-two bromo-1,1 ': 2 '; 1 ": 2 "; 1 " '-quaterphenyl) (1.39g, 3.0mmol), acid chloride (27mg, 0.12mmol), toluene (50mL), tri-butyl phosphine (24mg, 0.12mmol) with potassium tert.-butoxide (0.67g, 6.0mmol), stir 7 hours at 100 DEG C after airtight.Then, let cool by reaction vessel near room temperature, uncap, add water (50mL) wherein.Content is moved to separating funnel, after making organic phase and aqueous phase separation, removes aqueous phase, then organic phase is washed.Organic phase with sodium sulfate is dry.Then, filter sodium sulfate by crossing, concentrated organic phase.By concentrated mixture silica gel column chromatography (developing solvent: the hexanes/ch=3/1) purifying obtained, obtain above-claimed cpd 1-I b (receipts amount 2.06g, yield 80.5%) as target.

¹H-NMR、CDCl ₃δ:6.25(s、2H)、6.56(d、J＝7.8Hz、2H)、6.66(d、J＝8.2Hz、4H)、6.77-6.81(m、4H)、6.90(t、J＝7.3Hz、2H)、7.96-6.99(m、2H)、7.06-7.17(m、12H)、7.38(t、J＝7.4Hz、2H)、7.46(d、J＝7.4Hz、2H)、7.96(d、J＝1.8Hz、2H)、7.74(d、J＝8.7Hz、2H)、7.97(d、J＝7.8Hz、2H)、8.02(d、J＝7.8Hz、2H)

Synthesis example 3

Synthesized by synthesis path shown below with following chemical formula (compound 1-I c that 1-I c) represents.

[changing 81]

The compound represented with following chemical formula (3c) has been synthesized by method shown below.

[changing 82]

To possess stirrer through argon displacement 300mL four-hole boiling flask in add 2,2 '-'-dibromobiphenyl (7.50g, 24.0mmol) and diethyl ether (100mL), stir, be cooled to-15 DEG C.Drip 1.6M n-Butyl Lithium/hexane solution (30.0mL, 48.0mmol) wherein.Stir after 1 hour, add trimethyl borate (4.99g, 48mmol), removing cooling bath, stirs 18 hours from-15 DEG C while being warming up to room temperature.Successively add distilled water (50mL) on a small quantity, reaction is stopped, under reduced pressure remove diethyl ether and hexane.According to prolong, after again argon displacement being carried out to container, add distilled water (50mL), paradibromobenzene (16.98g, 72mmol), tetrakis triphenylphosphine palladium (0.555g, 0.48mmol), salt of wormwood (6.634g, 48mmol) with toluene (100mL), reflux 5 hours.After being cooled to room temperature, content is moved to separating funnel, make organic phase and aqueous phase separation, remove aqueous phase, then organic phase is washed.Organic phase with sodium sulfate is dry.Then, filter sodium sulfate by crossing, concentrated organic phase.By the mixture of gained silica gel column chromatography (developing solvent: hexane) purifying, obtain the above-claimed cpd 3c (receipts amount 3.21g, yield 28.9%) as target.

¹H-NMR、CDCl ₃δ:6.51-6.54(m、4H)、7.18-7.19(m、2H)、7.23-7.26(m、4H)、7.37-7.45(m、6H)

Synthesized by method shown below with following chemical formula (compound 1-I c that 1-I c) represents.

[changing 83]

To possess stirrer through argon displacement 100mL Shu Lunke pipe in add compound 2c-I (N-phenyl dibenzo [b, d] thiophene-4-amine) (1.65g, 6.0mmol), compound 3c (4; 4 " '-two bromo-1,1 ': 2 '; 1 ": 2 "; 1 " '-quaterphenyl) (1.39g, 3.0mmol), acid chloride (13mg, 0.06mmol), toluene (30mL), tri-butyl phosphine (12mg, 0.06mmol) with potassium tert.-butoxide (1.35g, 12.0mmol), stir 7 hours at 100 DEG C after airtight.Then, let cool by reaction vessel near room temperature, uncap, add water (30mL) wherein.Content is moved to separating funnel, after making organic phase and aqueous phase separation, removes aqueous phase, then organic phase is washed.Organic phase with sodium sulfate is dry.Then, filter sodium sulfate by crossing, concentrated organic phase.By concentrated mixture silica gel column chromatography (developing solvent: the hexanes/ch=3/1) purifying obtained, obtain above-claimed cpd 1-I c (receipts amount 2.12g, yield 82.8%) as target.

¹H-NMR、CDCl ₃δ:6.51-6.57(m、8H)、6.85-6.92(m,6H)、7.12-7.21(m、8H)、7.33-7.41(m、8H)、7.85-7.87(m、2H)、8.11(dd、J＝0.9Hz,J＝7.8Hz、2H)、8.29-8.31(m、2H)

Synthesis example 4

The compound 2c-II represented with following chemical formula (2c-II) has been synthesized by synthesis path shown below.

[changing 84]

First, synthesized by method shown below with following chemical formula (4a-II)

[changing 85]

The compound represented.

Under an argon, in the 500mL Shu Lunke pipe possessing stirrer, add 33.6g (0.2mol) diphenylene-oxide and 200mL dewater after diethyl ether, this reaction soln is cooled to 0 DEG C under ice-cold.After dripping 1.6M n-Butyl Lithium/hexane solution 138mL (0.22mol) wherein, the lower reaction of backflow 16 hours, by 4 complex anions of diphenylene-oxide.

Then, after the anionites of diphenylene-oxide is cooled to-8 DEG C, adds the powder of 50.8g (0.2mol) iodine wherein, while slowly returning to room temperature, stir 15 hours.

Reaction mixture is injected water, after diethyl ether, the organic layer of gained is washed, use anhydrous sodium sulfate drying.Then, after heating up in a steamer desolventizing, the residue hexane of gained is carried out recrystallization.

By above operation, obtain the above-claimed cpd 4a-II as target using the amount of receipts 24.8g, yield 42%.The qualification of compound is passed through ¹h-NMR and mass spectroscopy are carried out, molecular ion peak (M ⁺294) consistent with target compound.

¹H-NMR(DMSO-d ₆)δ7.23(t、J＝7.8Hz、1H)、7.45(t、J＝6.8Hz、1H)、7.58(t、J＝7.4Hz、1H)、7.80(d、J＝8.2Hz)、7.91(dd、J＝7.8Hz、1.4Hz、1H)、8.17(d、J＝8.7Hz、2H)

Then, the compound 2c-II represented with following chemical formula (2c-II) has been synthesized by method shown below.

[changing 86]

Under an argon, in the 300mL Shu Lunke pipe possessing stirrer, compound 4a-II (4-iodine diphenylene-oxide) 15g (51.0mmol), aniline 4.83g (52.0mmol), potassium tert.-butoxide 7.14g (63.8mmol), Pd is added ₂(dba) ₃0.47g (0.51mmol) and dehydrated toluene 80mL, carries out degassed.Then, add tri-butyl phosphine 0.1g (0.51mmol) and sealing of jumping a queue, stir 28 hours at 85 DEG C.Then, let cool by reaction vessel near room temperature, uncap, add water (150mL) wherein.Content is moved to separating funnel, after making organic phase and aqueous phase separation, removes aqueous phase, then organic phase is washed.Organic phase with sodium sulfate is dry.Then, filter sodium sulfate by crossing, concentrated organic phase.By concentrated mixture silica gel column chromatography (developing solvent: the hexanes/ch=3/1) purifying obtained, obtain the above-claimed cpd 2c-II (receipts amount 6.26g, yield 47.4%) as target.

The qualification of compound is undertaken by mass spectroscopy, and molecular ion peak is consistent with target compound.

Synthesis example 5

The compound 2d-II represented with following chemical formula (2d-II) has been synthesized by synthesis path shown below.

[changing 87]

The compound 4b-II represented with following chemical formula (4b-II) has been synthesized by method shown below.

[changing 88]

To possess stirrer through argon displacement 100mL Shu Lunke pipe in add diphenylene-oxide (3.36g, 20mmol), NBS (3.92g, 22mmol), zirconium chloride (0.10g, 0.44mmol) and DMF (40mL), stir 18 hours at 70 DEG C.Reaction solution is added in water (200mL), solid is separated out, be suspended under state stir 30 minutes.Filter suspension liquid, slowly fall down the hot water (100mL) of 90 DEG C above the solid the filter paper of gained.After reclaiming the solid on filter paper, dry, obtain 4.1g target compound 4b-II (yield 83%).

The compound 2d-II represented with following chemical formula (2d-II) has been synthesized by method shown below.

[changing 89]

To possess stirrer through argon displacement 100mL Shu Lunke pipe in add compound 4b-II (2-bromine diphenylene-oxide) (2.47g, 10mmol), aniline (1.12g, 12mmol), acid chloride (90mg, 0.4mmol), toluene (50mL), tri-butyl phosphine (81mg, 0.4mmol) with potassium tert.-butoxide (2.24g, 20mmol), stir 18 hours at 100 DEG C after airtight.Then, let cool by reaction vessel near room temperature, uncap, add water (50mL) wherein.Content is moved to separating funnel, after making organic phase and aqueous phase separation, removes aqueous phase, then organic phase is washed.Organic phase with sodium sulfate is dry.Then, filter sodium sulfate by crossing, concentrated organic phase.By concentrated mixture silica gel column chromatography (developing solvent: the hexanes/ch=3/1) purifying obtained, obtain the above-claimed cpd 2d-II (receipts amount 1.32g, yield 51%) as target.

Synthesis example 6

The compound 3d represented with following chemical formula (3d) has been synthesized by synthesis path shown below.

[changing 90]

To possess stirrer through argon displacement 300mL four-hole boiling flask in add 3-chlorophenylboronic acid (10.5g, 67.3mmol), 2,2 '-'-dibromobiphenyl (10.0g, 32.1mmol), tetrakis triphenylphosphine palladium (0.777g, 0.67mmol), salt of wormwood (9.3g, 67mmol), toluene (100mL) and (100mL), stir 6 hours at 100 DEG C.Reaction solution is moved to separating funnel, and after removing aqueous phase, add water cleaning organic phase, again removed by aqueous phase.After organic phase with sodium sulfate drying, carry out filtering, concentrating, be separated above-claimed cpd 3d (receipts amount 7.79g, 20.8mmol, yield 65%) with silica gel column chromatography (developing solvent: hexane).

Synthesis example 7

The compound 3e represented with following chemical formula (3e) has been synthesized by synthesis path shown below.

[changing 91]

To possess stirrer through argon displacement 200mL four-hole boiling flask in add 4-chlorophenylboronic acid (6.25g, 40mmol), 2,2 '-'-dibromobiphenyl (6.24g, 20mmol), tetrakis triphenylphosphine palladium (1.16g, 1.0mmol), salt of wormwood (5.53g, 40mmol), toluene (40mL) and (40mL), stir 6 hours at 100 DEG C.Reaction solution is moved to separating funnel, and after removing aqueous phase, add water cleaning organic phase, again removed by aqueous phase.After organic phase with sodium sulfate drying, carry out filtering, concentrating, be separated above-claimed cpd 3e (receipts amount 4.84g, 12.9mmol, yield 65%) with silica gel column chromatography (developing solvent: hexane).

Synthesis example 8

Synthesized by synthesis path shown below with chemical formula (compound 1-II a that 1-II a) represents.

[changing 92]

To possess stirrer through argon displacement 100mL Shu Lunke pipe in add compound 2c-II (1.04g, 4.0mmol), compound 3d (0.75g, 2.0mmol), acid chloride (36mg, 0.16mmol), toluene (50mL), tri-butyl phosphine (32mg, 0.16mmol) with potassium tert.-butoxide (0.90g, 8.0mmol), stir 18 hours at 100 DEG C after airtight.Then, let cool by reaction vessel near room temperature, uncap, add water (50mL) wherein.Content is moved to separating funnel, after making organic phase and aqueous phase separation, removes aqueous phase, then organic phase is washed.Organic phase with sodium sulfate is dry.Then, filter sodium sulfate by crossing, concentrated organic phase.By concentrated mixture silica gel column chromatography (developing solvent: the hexanes/ch=3/1) purifying obtained, obtain above-claimed cpd 1-II a (receipts amount 0.57g, yield 34.8%) as target.

¹H-NMR、DMSO-d ₆、δ:6.22(t、J＝1.8Hz、2H)、6.50(d、J＝7.8Hz、2H)、6.60(d、J＝7.8Hz、4H)、6.73(dd、J＝1.4Hz、8.0Hz、2H)、6.83(d、J＝7.8Hz、2H)、6.89(t、J＝7.8Hz、2H)、6.93-6.95(m、2H)、7.00-7.12(m、12H)、7.24(t、J＝7.8Hz、2H)、7.37-7.48(m、6H)、7.93(dd、J＝0.92Hz、7.8Hz、2H)、8.12(d、J＝7.3Hz、2H)

Synthesis example 9

Synthesized by synthesis path shown below with chemical formula (compound 1-II b that 1-II b) represents.

[changing 93]

To possess stirrer through argon displacement 100mL Shu Lunke pipe in add compound 2c-II (1.09g, 4.0mmol), compound 3e (0.75g, 2.0mmol), acid chloride (50mg, 0.22mmol), toluene (50mL), tri-butyl phosphine (45mg, 0.22mmol) with potassium tert.-butoxide (1.25g, 11.2mmol), stir 18 hours at 100 DEG C after airtight.Then, let cool by reaction vessel near room temperature, uncap, add water (50mL) wherein.Content is moved to separating funnel, after making organic phase and aqueous phase separation, removes aqueous phase, then organic phase is washed.Organic phase with sodium sulfate is dry.Then, filter sodium sulfate by crossing, concentrated organic phase.By concentrated mixture silica gel column chromatography (developing solvent: the hexanes/ch=3/1) purifying obtained, obtain above-claimed cpd 1-II b (receipts amount 0.89g, yield 54.2%) as target.

¹H-NMR、DMSO-d ₆、δ:6.42(s、8H)、6.83(d、J＝7.3Hz、4H)、6.91(t、J＝7.3Hz、2H)、7.04(dd、J＝0.92Hz、7.8Hz、2H)、7.12-7.17(m、6H)、7.25(t、J＝7.8Hz、2H)、7.32-7.50(m、12H)、7.87(dd、J＝0.92Hz、7.8Hz、2H)、8.04(d、J＝7.4Hz、2H)

Synthesis example 10

Synthesized by synthesis path shown below with following chemical formula (compound 1-II c that 1-II c) represents.

[changing 94]

To possess stirrer through argon displacement 100mL Shu Lunke pipe in add compound 2d-II (1.04g, 4.0mmol), compound 3d (0.93g, 2.0mmol), acid chloride (27mg, 0.12mmol), toluene (50mL), tri-butyl phosphine (24mg, 0.12mmol) with potassium tert.-butoxide (0.90g, 8.0mmol), stir 7 hours at 100 DEG C after airtight.Then, let cool by reaction vessel near room temperature, uncap, add water (50mL) wherein.Content is moved to separating funnel, after making organic phase and aqueous phase separation, removes aqueous phase, then organic phase is washed.Organic phase with sodium sulfate is dry.Then, filter sodium sulfate by crossing, concentrated organic phase.By concentrated mixture silica gel column chromatography (developing solvent: the hexanes/ch=3/1) purifying obtained, obtain above-claimed cpd 1-II c (receipts amount 1.47g, yield 89.6%) as target.

¹H-NMR、DMSO-d ₆、δ:6.18(t、J＝1.8Hz、2H)、6.55(d、J＝7.8Hz、2H)、6.61(d、J＝7.3Hz、4H)、6.73(dd、J＝1.3Hz、7.3Hz、2H)、6.78(dd、J＝2.3Hz、8.7Hz、2H)、6.87(t、J＝7.8Hz、2H)、6.97(d、J＝6.8Hz、2H)、7.06-7.18(m、12H)、7.30(t、J＝7.8Hz、2H)、7.45-7.52(m、6H)、7.68(d、J＝8.2Hz、2H)、7.99(d、J＝7.8Hz、2H)

Synthesis example 11

Synthesized by synthesis path shown below with following chemical formula (compound 1-II d that 1-II d) represents.

[changing 95]

To possess stirrer through argon displacement 100mL Shu Lunke pipe in add compound 2d-II (1.45g, 5.59mmol), compound 3e (1.00g, 2.66mmol), acid chloride (50mg, 0.22mmol), toluene (50mL), tri-butyl phosphine (45mg, 0.22mmol) with potassium tert.-butoxide (1.25g, 11.2mmol), stir 18 hours at 100 DEG C after airtight.Then, let cool by reaction vessel near room temperature, uncap, add water (50mL) wherein.Content is moved to separating funnel, after making organic phase and aqueous phase separation, removes aqueous phase, then organic phase is washed.Organic phase with sodium sulfate is dry.Then, filter sodium sulfate by crossing, concentrated organic phase.By concentrated mixture silica gel column chromatography (developing solvent: the hexanes/ch=3/1) purifying obtained, obtain above-claimed cpd 1-II d (receipts amount 1.90g, yield 87.0%) as target.

¹H-NMR、DMSO-d ₆、δ:6.52(d、J＝8.7Hz、4H)、6.62(d、J＝8.7Hz、4H)、6.80-6.86(m、6H)、7.03(dd、J＝2.3Hz、8.7Hz、2H)、7.10(t、J＝8.3Hz、4H)、7.24-7.31(m、4H)、7.36-7.48(m、10H)、7.58(d、J＝8.2Hz、2H)、7.69(d、J＝2.3Hz、2H)、7.97(d、J＝7.8Hz、2H)

Embodiment 1

For synthesis in above-mentioned synthesis example 1 with above-mentioned chemical formula (in compound 1-I a that 1-I a) represents, above-mentioned synthesis example 2 synthesis with above-mentioned chemical formula (in compound 1-I b that 1-I b) represents and synthesis example 3 synthesis with above-mentioned chemical formula, (compound 1-I c that 1-I c) represents, has carried out DSC mensuration.

Comparative example 1

For comparative compound 3DTAPBP, carry out DSC mensuration.

Tg Sum decomposition temperature is shown in table 1.

[table 1]

As shown in table 1, known compound of the present invention has the Tg of more than 100 DEG C, and decomposition temperature is high, is the material of good thermal stability.

Embodiment 2 and comparative example 2

The film forming the film formed by compound 1-I a, the film formed by compound 1-I b, the film formed by compound 1-I c respectively on a quartz substrate and formed by above-mentioned 3DTAPBP (comparative compound).The UV-2500PC using Shimadzu Scisakusho Ltd (SHIMADZU society) to make for these films measures UV/vis spectrum, calculates optical energy band gap.Result is shown in table 2.

[table 2]

Embodiment 3

For the film formed by compound 1-I a, the film formed by compound 1-I b, the film formed by compound 1-I c and the film that formed by 3DTAPBP, use the FluoroMax-4 of Horiba Ltd (HORIBA society) respectively, use the excitation light source of wavelength 300nm, under the low temperature of 77K, measure emmission spectrum.Can observe phosphorescence luminescence under low temperature, therefore according to the measurement result of the emmission spectrum under low temperature, the triplet excited state (T about each film can be obtained ₁) the information of energy.Observe phosphorescence spectrum to remove fluorescence radiation composition, the delay of 200 milliseconds is set after excitation light irradiation to measure the emmission spectrum under low temperature.In addition, to the Ir (mppy) as luminescent material ₃also measure phosphorescent emissions wavelength, calculate T ₁energy.

T is calculated according to the above results ₁energy and the result obtained is shown in following table 3.

[table 3]

From the viewpoint keeping energy here, the T of hole transport layer material ₁energy is better the T being greater than guest materials ₁energy.From the result of above-mentioned table 3, the hole transmission layer of inclusion compound 1-I a, compound 1-I b or compound 1-I c is in use Ir (mppy) ₃as the triplet excited state (T that can keep here when guest materials ₁) energy.Therefore, the hole transmission layer by possessing inclusion compound 1-I a, compound 1-I b or compound 1-I c and use Ir (mppy) can be inferred ₃as the luminescent layer of guest materials, the organic EL that luminous efficiency is high can be obtained.

(organic EL)

Embodiment 4

Substrate is formed by known method anode successively that formed by ITO (tin indium oxide), the hole injection layer of the thick 30nm formed by above-mentioned PEDOT:PSS, second hole transmission layer of the thick 20nm formed by above-mentioned α-NPD, the hole transmission layer of the thick 10nm formed by compound 1-I a, uses above-mentioned Ir (mppy) ₃as guest materials, above-mentioned Bepp2 is used to be set to the luminescent layer of the thick 35nm of 6 % by weight as the content of the guest materials in material of main part, luminescent layer, the electron transfer layer of the thick 40nm formed by TPBi, the electron injecting layer of the thick 1nm formed by LiF film, the negative electrode formed by Al film.

Embodiment 5

Except compound 1-I a is replaced with except compound 1-I b, operate similarly to Example 4, form organic EL.

Comparative example 3

Except the material of hole transmission layer is replaced with except above-mentioned 3DTAPBP, operate similarly to Example 4, form organic EL.

For the embodiment 4,5 of gained and the organic EL of comparative example 3, determine external quantum efficiency and component life.The results are shown in following table 4.

[table 4]

Embodiment 6

For the compound of synthesis in synthesis example 8 ~ 11, carry out DSC mensuration.

Comparative example 4

For as comparative compound 3DTAPBP, the comparative compound DBTPB of existing hole mobile material and comparative compound α-NPD, carry out DSC mensuration.

[changing 96]

The result of fusing point and second-order transition temperature is shown in following table 5.

[table 5]

Compound	Tg(℃)	Fusing point (DEG C)	Decomposition temperature (DEG C)
				1-IIa	103	203	＞400
1-IIb	104	-	＞400
				1-IIc	118	193	＞400
1-IId	123	258	＞400
				3DTAPBP	75	-	＞400
DBTPB	127	-	＞400
				α-NPD	95	280	＞400

Known compound of the present invention has the Tg of more than 100 DEG C, and decomposition temperature is high, is the material of good thermal stability.

Embodiment 7

Form the film formed by compound 1-II a of synthesis in above-mentioned synthesis example 8 ~ 11, the film formed by compound 1-II b, the film formed by compound 1-II c, the film become by compound 1-II D-shaped, the film formed by 3DTAPBP (comparative compound) and the film formed by DBTPB (comparative compound) respectively on a quartz substrate.Use the UV-2500PC of Shimadzu Scisakusho Ltd to measure UV/vis spectrum for these films, and the FP-6500 using JASCO company (JASCO society) to make measure PL spectrum.By the known UV maximum absorption wavelength of its result, PL spectrum and optical energy band gap.

The results are shown in following table 6.

[table 6]

Compound	UV(nm)	PL(nm)	Eg(eV)
				1-IIa	209、266、289	396	3.30
1-IIb	209、289、322	401	3.21
				1-IIc	302	410	3.14
1-IId	302	412	3.14
				3DTAPBP	285、353	408	3.60
DBTPB	237、285、353	406	3.00

Embodiment 8

For the film formed by compound 1-II a, the film formed by compound 1-II b, the film formed by 3DTAPBP (comparative compound) and the film that formed by DBTPB (comparative compound), use the FluoroMax-4 of Horiba Ltd respectively, use the excitation light source of wavelength 300nm, under the low temperature of 77K, measure emmission spectrum.Can observe phosphorescence luminescence under low temperature, therefore according to the measurement result of the emmission spectrum under low temperature, observing phosphorescence spectrum to remove composition, the delay of 200 milliseconds is set after excitation light irradiation to measure the emmission spectrum under low temperature.In addition, to the following Ir (mppy) as luminescent material ₃also measure phosphorescent emissions wavelength, calculate T ₁energy.

[changing 97]

Result is shown in table 7.

[table 7]

Compound	T ₁(eV)
		1-IIa	2.59
1-IIb	2.63
		3DTAPBP	2.70
DBTPB	2.37
		Ir(mppy) ₃	2.37

From the viewpoint retaining energy, the T of hole transport layer material ₁energy is better the T being greater than guest materials (luminescent material) ₁energy.From the result of above-mentioned table 7, the hole transmission layer of inclusion compound 1-II a or compound 1-II b is in use Ir (mppy) ₃as the triplet excited state (T that can keep here when guest materials ₁) energy.Therefore, the hole transmission layer by possessing inclusion compound 1-II a or compound 1-I b and use Ir (mppy) can be inferred ₃as the luminescent layer of guest materials, the organic EL that luminous efficiency is high can be obtained.

" organic EL "

Embodiment 9

Substrate is formed by known method anode successively that formed by ITO (tin indium oxide), the hole injection layer formed by PEDOT:PSS, second hole transmission layer of the thick 20nm formed by α-NPD, the hole transmission layer of the thick 10nm formed by compound 1-II a, uses Ir (mppy) ₃as guest materials, use above-mentioned Bepp ₂content as the guest materials in material of main part, luminescent layer is set to the luminescent layer of the thick 25nm of 6 % by weight, the electron transfer layer of the thick 35nm formed by above-mentioned TPBI, the electron injecting layer of the thick 8nm formed by LiF film, the negative electrode formed by Al film.

[changing 98]

Comparative example 5

Except the material of hole transmission layer is replaced with except above-mentioned DBTPB, operate similarly to Example 9, form organic EL.Have rated external quantum efficiency and component life.

Embodiment 10

For using the organic EL with compound 1-II a of diphenylene-oxide, under same organic EL condition, have rated external quantum efficiency and component life.

The result of comparative example 5 and embodiment 10 is shown in following table 8.The conditions such as the thickness of each organic layer of organic EL are different from embodiment, but the result of the 3DTAPBP recorded in non-patent literature 8 is shown in the lump.

[table 8]

Compound	External quantum efficiency	Component life LT90
			1-IIa	22.3	460
DBTPB	20.0	260
			3DTAPBP	18.7	11(※LT50)

As shown in table 8, each element compound 1-II a with diphenylene-oxide being used for hole transmission layer shows than using the better element characteristic of the element with the 3DTAPBP of identical center framework.Even if particularly use the life-span of the element of 3DTAPBP to be also as short as 11 hours at LT50, the element of compound of the present invention is used to show the life-span of 460 hours at LT90.In addition, knownly also significantly to improve in external quantum efficiency.In addition, even if confirmation and use describe compared with the middle element with the DBTPB of best element characteristic introduced of same document (non-patent literature 8) of the performance of 3DTAPBP, compound of the present invention also has life-span, the equal excellent element characteristic of efficiency.

Claims

1. with formula (1)

[changing 1]

The compound represented;

In formula,

X ¹and X ²independently for substituent fragrant ring type group can be had,

Z ¹and Z ²be independently O or S,

N is the integer of 1 ~ 8.

2. compound as claimed in claim 1, is characterized in that, R ¹~ R ⁴for hydrogen.

3. compound as claimed in claim 1 or 2, it is characterized in that, n is 2.

4. the compound as described in any one in claims 1 to 3, is characterized in that, X ¹and X ²for substituent phenyl can be had.

5. the compound as described in any one in Claims 1 to 4, is characterized in that,

With formula (1-I)

[changing 2]

Represent.

6. compound as claimed in claim 5, it is characterized in that, the binding site of nitrogen is 4 of dibenzothiophene.

7. compound as claimed in claim 5, it is characterized in that, the binding site of nitrogen is 2 of dibenzothiophene.

8. the compound as described in any one in Claims 1 to 4, is characterized in that,

With formula (1-II)

[changing 3]

Represent.

9. compound as claimed in claim 8, it is characterized in that, the binding site of nitrogen is 4 of diphenylene-oxide.

10. compound as claimed in claim 8, it is characterized in that, the binding site of nitrogen is 2 of diphenylene-oxide.

11. compounds as claimed in claim 5, is characterized in that,

With chemical formula (1-I a),

[changing 4]

Chemical formula (1-I b),

[changing 5]

Chemical formula (1-I c),

[changing 6]

Or

(1-I d) for chemical formula

[changing 7]

Represent.

12. compounds as claimed in claim 8, is characterized in that,

With chemical formula (1-II a),

[changing 8]

Chemical formula (1-II b),

[changing 9]

Chemical formula (1-II c),

[changing 10]

Or

(1-II d) for chemical formula

[changing 11]

Represent.

The method of the compound described in any one in 13. manufacturing claims 1 ~ 12, is characterized in that, comprises in order to general formula (2)

[changing 12]

Represent compound or its salt with

With general formula (3)

[changing 13]

The compound represented carries out the operation of N-arylation reaction;

In formula (2),

R independently represents the R with claim 1 ¹~ R ⁴same implication,

X represents the X with claim 1 ¹and X ²same implication,

Z represents the Z with claim 1 ¹and Z ²same implication,

In formula (3),

N represents the implication same with claim 1,

HAL is halogen radical.

14. organic electroluminescent devices, it be comprise anode, negative electrode and between this two electrode with the organic electroluminescent device of layer that organic compound is formed, it is characterized in that,

The described layer formed with organic compound comprises the compound described in any one in claim 1 ~ 12.

15. organic electroluminescent devices, it comprises anode, negative electrode and the organic electroluminescent device at this two interelectrode charge transfer material, it is characterized in that,

Described charge transfer material comprises the compound described in any one in claim 1 ~ 12.

16. organic electroluminescent devices, it comprises anode, negative electrode and the organic electroluminescent device at this two interelectrode hole transmission layer, it is characterized in that,

Described hole transmission layer comprises the compound described in any one in claim 1 ~ 12.

17. organic electroluminescent devices, it comprises anode, negative electrode and the organic electroluminescent device at this two interelectrode luminescent layer, hole transmission layer, it is characterized in that,

18. organic electroluminescent devices as claimed in claim 17, it is characterized in that, luminescent material is phosphor material.